World Scientific Lecture Notes in Physics - Vol.

76

Effective Field Approach

to Phase Transitions and
Some Applications to
Ferroelectrics (2nd Edition)

Julio A Gonzalo
Effective Field Approach
to Phase Transitions and
Some Applications to
Ferroelectrics (2nd Edition)
World Scientific Lecture Notes in Physics
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 World Scientific Lecture Notes in Physics - Vol. 76

Effective Field Approach

to Phase Transitions and
Some Applications to
Ferroelectrics (2nd Edition)

Julio A Gonzalo
Universidad Automa de Madrid, Spain

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EFFECTIVE FIELD APPROACH TO PHASE TRANSITIONS AND SOME

APPLICATIONS TO FERROELECTRICS (2nd Edition)
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To the Virgin Mary, Queen of all things created by God,
including beautiful phase transitions.

To my parents
 Preface

The effective field approach to a phase transition, used by Pierre Weiss at

the beginning of this century to describe theoretically ferromagnetic tran-
sitions in iron, nickel, and cobalt, is the second oldest (surpassed in this
respect only by Van der Waals theory of liquid-vapor transitions) and cer-
tainly the simplest approach to investigate cooperative phenomena of this
kind. Early in the effort to describe satisfactorily the rich variety of physical
phenomena accompanying a phase transition, it was realized that the role
of fluctuations, introduced by Einstein in 1905 (the same year in which he
introduced special relativity and the first successful explanation of the pho-
toelectric effect), was crucial to investigate the subtleties of the behavior of
systems undergoing phase changes at temperatures very close to the transi-
tion temperature. Of course, the concept of effective field, being an average
or mean field, leaves out completely thermodynamic fluctuations. Never-
theless, the effective field approach gives in most cases a good qualitative
description of the cooperative phenomena, and in some cases, ferroelectric
transitions being an outstanding example, it even gives a fairly good quan-
titative description. It took some time for prominent theorists to realize
that deviations of "classical" (effective field) behavior in ferroelectrics and
dipolar ferromagnets should show up in the form of logarithmic corrections,
which are very hard to detect experimentally.
This work, which could as well be entitled "Pedestrian approach to
Phase Transitions," obviously does not aim at a comprehensive discussion
of the effective field approach to phase transitions in general and less so at a
discussion that goes deeply beyond this approach to such a broad and active
field of contemporary research. It attempts at a simple presentation of the
approach, at a very elementary level in most cases, to a number of interest-
ing phase transitions, mostly solid-state transitions, with special attention,

vii
viii Effective Field Approach to Phase Transitions

in the second half of the book, to some work in ferroelectric systems inflect-
ing, unavoidably, the research interest of the author. This material formed
the basis for a short graduate course on "Phase Transitions" imparted by
the author at the Universidad Autonoma de Madrid, in 1989.
I would like to thank Professor J. Palacios and Professor S. Velayos,
former teachers of mine at the University of Madrid, who introduced me
to this field; Drs. B.C. Prazer, K. Okada, M. Ray, and G. Shirane, from
whom I learned much on ferroelectrics and phase transitions at Brookhaven
National Laboratory and at Puerto Rico Nuclear Center; I. Lefkowitz and
K.A. Miiller to whom I am also indebted; and many of my former graduate
students from whom I have also learned a good deal.

Madrid, January 15, 1990

Julio A. Gonzalo
 Preface to the Second Edition

This second edition of Effective Field Approach to Phase Transitions

includes additional sections, Parts III-IV, in which additional papers involv-
ing the efFecitve field approach to Ferroelectric Transitions published in the
period 1991-2005 are included.
It is for me a pleasure to give proper credit to the various main
authors of these papers: to my younger Spanish colleagues R. Ramirez,
G. Lifante, M. de la Pascua, B. Noheda, T. Iglesias, J.R. Fernadez del
Castillo, N. Duan, C. Arago, M.I. Marques, and J. Garcia, some of them
at UAM or other Universities in Madrid; and to my long time friends and
colleagues from abroad, including G. Shirane (BNL, recently deceased),
D. Cox (BNL), C.W. Garland (MIT), J.O. Tocho (La Plata), W. Windsch
(Leipzig), M. Koralewski (Poznan), Y.L. Wuag (Shanghai), B. Mroz
(Poznan), L. Cross (Penn State), R. Guo (Penn State), and C.L. Wang
(Sandong).

Madrid, November 15, 2005

Julio A. Gonzalo
 Contents

Preface vii

Preface to the Second Edition ix

Part 1 Mean Field Approach to Cooperative Phenomena 1

1.1 An overview 3
1.2 Liquid-vapor transitions 11
1.3 Ferromagnetic transitions 21
1.4 Superconductive transitions 31
1.5 Order-disorder transitions in alloys 37
1.6 Ferroelectric transitions 45
1.7 Superfluid transitions 53
1.8 Ferroelastic transitions 61
1.9 Landau theory and effective field approach. Role of
fluctuations 67
1.10 Equation of state and the scaling function 81
Appendix: Effective field approach to superconductors 91

Part 2 Some Applications to Ferroelectrics: 1970-1991 101

2.1 Behavior at T = Tc of pure ferroelectric systems with
second order phase transition 103
2.2 Effects of dipolar impurities in small amounts 119
2.3 Mixed ferro-antiferroelectric systems and other mixed
ferroelectric systems 129
2.3.1 Comment on "Ferroelectricity in zinc cadmium
telluride" 137

xi
xii Effective Field Approach to Phase Transitions

2.4 Relaxation phenomena near Tc 141

2.5 Polarization reversal in ferroelectric systems 147
2.6 Polarization switching by domain wall motion 155
2.7 Switching current pulse shape 163
2.8 Elementary excitations in ferroelectrics: Dipole waves . . . 169
2.9 Low-temperature behavior of ferroelectrics 179
2.10 Logarithmic corrections 183

Part 3 Some Applications to Ferroelectrics: 1991-1997 189

3.1 Pressure dependence of the free energy expansion
coefficients in PbTi03 and BaTi03, and tricritical
point behavior 191
3.2 Ultrasonic study of the ferroelectric phase transition
in R b D 2 P 0 4 197
3.3 New technique for investigating ferroelectric phase
transitions: The photoacoustic effect 207
3.4 Tricritical point behavior and quadrupole interactions
in ferroelectrics 215
3.5 Frequency and temperature dependence of sound velocity
in TGS near Tc 221
3.6 Dipolar and higher order interactions in ferroelectric
TSCC 229
3.7 Thermal hysteresis and quadrupole interactions in
ferroelectric transitions 237
3.8 Specific heat and quadrupole interactions in uniaxial
ferroelectrics 243
3.9 Field-dependent temperature shift of the dielectric losses
peak in TGS 249
3.10 Discontinuity and quasitricritical behavior near Tc in
ferroelectric triglycine selenate 255
3.11 Scaling equation of state for ferroelectric triglycine selenate
atr«Tc 265
3.12 Composition dependence of the ferroelectric-paraelectric
transition in the mixed system PbZri-^Ti^Os 273
3.13 Observations of two ferroelectric response times in TGSe
at T <TC 283
3.14 Equation of state for pressure and temperature induced
transition in ferroelectric telluric acid ammonium
phosphate 289
 Contents xiii

3.15 Neutron diffraction investigation of the F R L - F R H transition

in Nb-doped PbZr^^Ti^Oa with x = 0.035 299
3.16 O3 tilt and Pb/(Zr/Ti) displacement order parameters
in Zr-rich PbZri.^Ti^Os from 20 to 500 K 305
3.17 Dielectric characterization of the phase transitions in
Pb 1 „j //2 (Zr 1 _ x Ti a; ) 1 _ y Nb y O3(0.03 < x < 0.04, 0.025 <
y < 0.05) 319

Part 4 Some Applications to Ferrolectrics: 1998-2005 335

4.1 Scaling and metastable behavior in uniaxial
ferroelectrics 337
4.2 Energy conversion with Zr-rich lead Zirconate/Titanate
ceramics 351
4.3 Microscopic characterization of low-field switching in
ferroelectric TGS 357
4.4 Brillouin scattering studies of ferroelectric triglycine
selenate sound velocity versus uniaxial pressure
at T ~ Tc 367
4.5 Piezoelectric resonance investigation of Zr-rich PZT
at room temperature 377
4.6 Transition temperature dependence in perovskite ceramics
as a function of grain size 385
4.7 A monoclinic ferroelectric phase in the Pb(Zri_ a: Ti a ;)03
solid solution 389
4.8 Tetragonal-to-monoclinic phase transition in ferroelectric
perovskite: The structure of PbZro.52Tio.48O3 397
4.9 Evolution of the ferroelectric transition character of
partially deuterated triglycine selenate 419
4.10 Composition dependence of transition temperature
in mixed ferroelectric-ferroelectric systems 427
4.11 Temperature dependence of mode Gruneisen parameters
in ferroelectric perovskites at T = Tc 435
4.12 Quantum tunneling versus zero point energy in double-well
potential model for ferroelectric phse transitions 439

Index 451
 Part 1
Mean Field Approach to
Cooperative Phenomena
 Chapter 1.1

An Overview

What are cooperative phenomena? In physics, cooperative phenomena

mean global changes in the structure and physical properties of a system
that takes place cooperatively when some external variable, in most cases
temperature, is changed continuously in a certain interval. Consider a solid
for instance. By warming it up moderately one expects to observe a small
dilatation of its overall dimensions, which is reflected at the microscopic
level by small increases, of the order of one part in 10,000 or less, per
degree Kelvin in the unit cell parameters. The same can be said of the
specific heat. If the ambient temperature of the solid is low in comparison
with its characteristic Debye temperature, the specific heat will increase
smoothly according to Debye's T 3 law. If the ambient temperature is above
the Debye temperature, one may expect a small increase with T due to
anharmonic contributions, which are, in general, small. But ordinarily we
do not expect a drastic change in any physical property of the solid if the
increase in temperature is small. This is precisely what happens when a
cooperative phenomenon in the system takes place: some physical proper-
ties, specific heat, lattice parameters, etc., manifest pronounced changes,
continuous or discontinuous, as the system approaches the phase transition
point. Very often the system goes from a lower temperature ordered phase
to a higher temperature disordered phase, and the phase change takes place
in such a way that as the disorder increases it becomes easier to increase
further the disorder in the system. That is why the term "cooperative phe-
nomena" is in order.
This is, of course, familiar to any student of condensed matter physics.
What is perhaps not so familiar is the high degree of underlying simi-
larity among apparently very different kinds of phase transition, such as

3
 Effective Field Approach to Phase Transitions

Table 1.1.1. Cooperative phenomena.

Transition Conjugated Discovery First successful theory

variables

Liquid/vapour P-V T. Andrews, 1872 J. van der Waals, 1874

Ferromagnetic/ H-M P. Curie, 1895 P. Weiss, 1907
paramagnetic
Superconductor/normal ()-N K. Onnes, 1906 J. Bardeen, L. Cooper, J.
Schrieffer, 1957
Order/disorder (alloys) ()-< G. Tamman, 1919 W. Bragg, E. Williams, 1934
Ferroelectric/par aelectric E- P J. Valasek, 1921 W. Mason, 1947
Superfluid/normal ()-N W. Keesom, N. Bogoliubov, 1946
A. Keesom, 1935
Ferroelastic/paraelastic X-x — K. Aizu, 1969

Conjugated variables: P = pressure, V = volume, H = magnetic field, M = magne-

tization, N = number of bound Cooper pairs per unit volume in a superconductor,
C — (R — W)/(R + W), R = number of rightly located atoms, W = number of wrongly
located atoms in an order-disorder alloy, E = electric field, P = polarization, X = stress,
x = strain, N = number of (Bose) condensed atoms in a superfluid.

the liquid-vapor transition, the ferromagnetic transition, and the order-

disorder transition in alloys, to name a few. Table 1.1.1 gives a more com-
prehensive list of phase transitions (cooperative phenomena) in a number
of systems, making explicit the pair of conjugated variables involved (whose
product is either an energy or a dimensionless number if the magnitudes of
the variables are normalized), the year of discovery of the first quantitative
characterization, and the year of publication of the first simple theory for
the cooperative phenomenon in question.
While the first successful theories quoted in the last column of
Table 1.1.1 are not exactly equivalent, all of them have much in common.
The theory of P. Weiss for the ferromagnetic/paramagnetic transition can
be taken as a prototype because of its extreme simplicity. We will see in
subsequent sections that the effective field concept can be used as the basis
to reformulate in very simple terms the theories of most cooperative phe-
nomena listed in the table.
There are many excellent monographs dealing with the modern theories
of phase transitions and critical phenomena. 1_4 The ground covered by the
literature on this subject is very broad. Our purpose (a modest one) is to
introduce the reader to the effective field theories of phase transitions, and
we do not need to enter into the many important subtleties of these mod-
ern theories. A few introductory remarks are probably in order, however,
 An Overview 5

concerning some of the basic features of phase transitions:

(i) Symmetry breaking. A phase transition is usually accompanied by

a breakdown of symmetry. For instance, a ferromagnet at a temperature
above its transition temperature (Tc = Curie temperature) has zero mag-
netization in zero field; it is symmetric, i.e., does not have any preferred
direction with respect to the magnetization. As we lower T below T c , how-
ever, a spontaneous magnetization develops in a specific direction. The
forward and backward directions along the line of magnetization become
inequivalent and, consequently, the earlier symmetry breaks down. Some
ferromagnets are multiaxial, and lowering T below Tc may break down the
crystal in several domains with magnetizations along mutually perpendicu-
lar axes. Others are uniaxial and they can break only into domains pointing
in one direction or in the opposite direction (180° apart). But in both cases
it suffices to apply a very small magnetic field along one preferred direction
during the slow cooling process to get a single-domain crystal. It may be
noted, on the other hand, that not all phase transitions are accompanied
by symmetry breaking: for instance, in a liquid-vapor transition the sys-
tem remains isotropic below the transition temperature, only its density
(volume) changes drastically.
(ii) Continuity or discontinuity. The phase transition can take place
either in a continuous fashion (usually these transitions are called second
order transitions) or in a discontinuous fashion (first order transitions).
For instance, in ferroelectric systems, in which the order parameter is the
electric polarization, going from T < Tc to T > T c , the polarization can
go to zero continuously or discontinuously. In some cases it is possible to
use a variable external force (a uniaxial stress to the crystal along a given
direction) to change the nature of the transition from first order to second
order. If we can change the variable external force in arbitrarily small steps
we go from first order to second order passing through a threshold point
between the two cases, which is called a "tricritical point."
(iii) Dimensionality and universality classes. A physical system can be
thought of as being made up of chains of atoms (or groups of atoms) which
when they are close together in a single plane make up a surface, and many
surfaces together parallel to each other form a three-dimensional lattice. For
instance, in a ferromagnetic crystal the relevant units are the atomic spins of
certain atoms periodically arranged in space. If the arrangement of the spins
is such that they form parallel chains widely separated from each other, the
dimensionality of the system is said to be one. If the arrangement of the
6 Effective Field Approach to Phase Transitions

spins is in parallel sheets widely separated from the next sheets the dimen-
sionality is three. But, in addition, we have to consider the dimensionality
of the ferromagnetic units themselves, the atomic spins, which are responsi-
ble for the development of a non-zero order parameter (the magnetization)
at T < Tc. In some systems, the combined cooperative interaction and
local crystal field interaction force the spins to point up or down in a spe-
cific direction, which implies an order parameter dimensionality one (Ising
case). In other cases, moving from one spin to the next involves a rotation
within a single plane, which repeats itself going to the following next spin
and so on, implying an order parameter dimensionality two (X-Y case).
Still in other ferromagnetic systems the allowed direction for the spins is
not restricted to a line or to a plane but may be in any spatial direction,
i.e., they have order parameter dimensionality three (Heisenberg case). It
has been one of the great theoretical discoveries of the late 1960s and early
1970s to establish that the critical behavior at a phase transition (i.e.,
the behavior of the order parameter and its associated susceptibilities very
close to the transition temperature, where fluctuations play a major role)
is entirely determined by the dimensionality of the system together with
the dimensionality of the order parameter. There would be, therefore, nine
physically realizable universality classes, if all 3 x 3 combinations would
involve a phase transition at T > OK. This, however, is not the case, e.g.,
the one-dimensional Ising case does not have a phase transition at T > OK.
(iv) Anomalies in physical properties near Tc. The three main variables
involved in a phase transition are the order parameter (for instance, in a
ferroelectric, the polarization), the conjugated field (e.g., the electric field),
and the temperature. (It is possible also to substitute the temperature for
another variable, for instance, a pressure sufficient to trigger the transition,
in the case of a ferroelectric, keeping the temperature fixed, but this case is
less general.) However, the fact that a phase transition takes place makes
itself patent very often in anomalies of many other physical properties of
the system. In a typical second order ferroelectric transition, the polariza-
tion decreases at first very smoothly from its saturation value at T = OK,
then the decrease begins to be more pronounced as Tc is approached, and
finally it goes down very steeply to zero as T —> Tc. The associated suscep-
tibility (dielectric constant) diverges as Tc is approached from both sides.
Measured values of e(Tc) = (4dF/d£)r c up to 106 have been reported in
some ferroelectric systems. The entropy presents also a marked temperature
dependence, and the excess specific heat associated with it presents, like-
wise, a characteristic peak at T = Tc. The unit cell lattice parameters show
 An Overview 7

anomalous behavior with temperature near T c , and so do the correspond-

ing thermal expansion coefficients. For instance, in some uniaxial cases the
thermal expansion in the direction of the ferroelectric axis decreases with
T at T > Tc, while the thermal expansion in directions perpendicular to
this axis increase with T. The elastic constants dj(T) also show anoma-
lies, detected by ultrasonic or Brillouin scattering measurements, near T c .
The refractive indices, birefringence, and optical activity are also connected
to the order parameter (polarization) and they show anomalous behavior
near Tc. Finally, even transport coefficients such as thermal and electric
conductivities often present pronounced anomalies in the vicinity of the
phase transition.
(v) Law of corresponding states. A very interesting feature of many
phase transitions is that, uning normalized variables, i.e., a dimension-
less order parameter (dividing by its saturation value) and a dimension-
less temperature (dividing by the transition temperature), one can fit in a
single curve sets of data for many different systems undergoing the same
type of phase transition. It is said that the collection of systems fulfills a
"law of corresponding states," even if the absolute values of order param-
eter and transition temperature of individual systems differ widely. This is
shown in Fig. 1.1.1 for a colletion of liquid-vapor phase transitions, as illus-
trated by E.A. Gugenheim 5 in 1945, and in Fig. 1.1.1 for the three metallic
ferromagnets6 Fe, Ni, and Co. In the first case, the order parameter is the

0.90
T
/Tc
0.80

0*70

0.60

0 0.4 0.8 1.2 1.6 2-0 2.4

Fig. 1.1.1. Law of corresponding states for liquid-vapor systems.

 Effective Field Approach to Phase Transitions

1.0 0.8 0.6 0/. 0.2 0 0.2 0J. 0.6 0.8 1.0
— Ms/Mso -M</MSO *-

Fig. 1.1.2. Law of corresponding states for ferromagnetic systems.

normalized density of the system. In the second case, the order parameter
is the normalized spontaneous magnetization, which can point out in either
of two opposite directions. In Fig. 1.1.2, one gets something that resembles
Fig. 1.1.1 but is much more symmetric. This reflects the fact that, from the
physical point of view, positive and negative magnetizations are equivalent
with respect to their zero mean value, while the vapor and liquid state den-
sities are not so symmetrically equivalent with respect to its non-zero mean
value.
(vi) Similarities and differences. It must be emphasized, therefore, that
all types of phase transitions show striking similarities, but they show also
characteristic differences among each other. For instance, from a formal
point of view, ferroelectric and ferromagnetic transitions are much closer
to each other than either of them is to the liquid-vapor phase transition,
for instance. This is illustrated in Fig. 1.1.3, where the phase diagram for
a liquid-vapor transition (H 2 0) is compared with the diagrams for a ferro-
magnet (Fe) and a ferroelectric (TGS).
(vii) Direct and indirect approaches. Phase transitions take place in
macroscopic, ./V-body systems made up of a very large number of atoms
or molecules (typically N = 10 22 ). A direct solution using the general
methods of statistical mechanics (together with considerable mathemati-
cal skills) is sometimes possible. An example is Onsager's solution of the
two-dimensional Ising model for zero magnetic field, but this is far from the
general situation. Another approach is to seek indirect approximate solu-
tions, exploiting existing or realistically assumed symmetries of the system,
which result in drastic simplification of the problem at hand. The effective
 An Overview 9

218+ (a) H20

atm \
Liquid-vapour
(HO)
2
P

^ water/
ice \ / vapor
1 »-
273°K 647 K T
Ferromagnet (Tc,0)
(b) Fe
(Fe)
ferro para
magnet T magnet

0 1044 K
,1 (c) TGS
Ferroelectric . (T c ,0)
ferro . para
CTGS) electric \ electric
©
322 K

Fig. 1.1.3. Phase diagrams for liquid-vapor, ferromagnetic, and ferroelectric transitions.

Table 1.1.2. Critical exponents.

Definition Ferromagnet Ferroelectric Effective field

(Ni) (TGS) model

m a (Tc-Tf, h=0 0 = 0.33 0 = 0.50 0 = 1/2

m a hx/s, T = TC (5 = 4.2 5 = 3.0 5= 3
X = {dm/dh) oc (T - T c ) —t 7 = 1-32 7 = 1.0 7=1
T,h-*0
Coc(T-Tc)-Q, h = 0 a= - 0 . 1 0 a«0 a = 0

m = order parameter, T c = transition tempertature, h = field conjugated to order

parameter (H, E), x = susceptibility, C = specific heat.

field approach, which assumes complete homogeneity throughout the sys-

tem, or, at least, throughout any single domain in it, is a case in point. It
is often convenient to start with the indirect, simplified approach, and then
proceed to the direct approach whenever possible.
(viii) Critical exponents. To conclude this introductory overview, we
give Table 1.1.2 including the definitions of the most common static critical
exponents, along with experimental values for a ferromagnet (Ni), a ferro-
electric (TGS = triglycine sulfate), and the effective field results, which will
be repeatedly obtained in subsequent sections.
10 Effective Field Approach to Phase Transitions

It is well t o recall t h a t critical fluctuations at \T — Tc\/Tc < 1 0 - 3 play

a much more prominent role in an itinerant ferromagnet, such as Ni, t h a n
in a uniaxial ferroelectric, such as T G S .

References

1. H.E. Stanley, Introduction to Phase Transitions and Critical Phenomena

(Oxford University Press, Oxford, 1971).
2. P. Pfeuty and G. Toulouse, Introduction to the Renormalization Group and to
Critical Phenomena (Wiley, New York, 1978).
3. Shang-Ken Ma, Modern Theory of Critical Phenomena (W.A. Benjamin,
Reading, MA, 1976).
4. C. Comb and M.S. Green (eds.), Phase Transitions and Critical Phenomena
(Academic Press, London, 1972).
5. E.A. Guggenheim, J. Chem. Phys. 13, 253 (1945).
6. A.J. Dekker, Solid State Physics (Prentice Hall, Englewood Cliffs, NJ, 1962).
7. L. Onsager, Phys. Rev. 65, 117 (1944).
 Chapter 1.2

Liquid—Vapor Transitions

The condensation of a sufficiently dense vapor into a liquid under the influ-
ence of increasing pressure and/or lowering temperature is a familiar phe-
nomenon and a prototype of phase transitions. It was first quantitatively
investigated by the Scottish physicist T. Andrews 1 in 1869. A few years
later, the Dutch J.D. Van der Waals, 2 in his doctoral dissertation, produced
a satisfactory theoretical description of the liquid-vapor phase transitions
and a generalized equation of state for real gases, which received great
acclaim by contemporary physicists and was soon translated into English,
French, and German. In essence, he modified successfully the ideal gas equa-
tion of state, relating pressure, volume for the constituent molecules, and
no interaction among them, by introducing two corrective terms, one to
account for the finite volume of the molecules and another to account for
their mutual attraction.
The Van der Waals theory can be viewed3 as an example of effective
mean field (in this case, rather, of effective mean potential) approach to a
phase transition. Suppose each molecule in a gas feels an effective mean
interaction potential due to all other molecules in the gas which is of
the form

[7( r ) = / 0 0 ' fOT

u
r
< ^ (l)
v
[ u < 0 otherwise. '

This means that each molecule is assumed to have a "hard core" of

radius ro, where the potential is infinitely repulsive and weakly attractive
(thus u < 0) outside of this core. Obviously, at r > ro it should have a
certain dependence with the distance, r, to the center of the molecule, but
for the sake of simplicity it is considered to be averaged out throughout
the space occupied by the gas. Consequently, the value of U(r) must be

li
 12 Effective Field Approach to Phase Transitions

U( r) a
1

(r ^

Fig. 1.2.1. Effective interaction potential of an individual molecule in a gas. Note that
u(r) depends on the density of molecules in the gas.

dependent on the density of molecules within the volume occupied by the

gas. Figure 1.2.1 shows the shape of U(r).
The pressure is given by

{dA/8V)T = kBT \d(lnZ)/dV], (2)

where A is the free energy, V the volume, kB Boltzmann's constant, T the

temperature, and Z the partition function, and we have used the fact that
A = kB In Z.
The global partition function Z for the gas can be thought of as the
product of the N single-particle partition functions, defined by

ZSP ex dr exp U(r) 0 = 1/feT, (3)

/ * / \2m

where we omit a proportionality factor, the integrals are extended to

momentum (p) and position (r) space, as usual, m is the mass of a sin-
gle particle, and T is the temperature. The integral / ( . . . ) dp does give a
factor that is independent of V, and, therefore, does not contribute to P.
The integral / ( . . . ) dr, on the other hand, can be written as

Kxcie-°° + {V~ Kxci)e -0U -/3u

(V - Kxd)e (4)
 Liquid- Vapor Transitions 13

where Vexci is the "excluded volume" corresponding to the "hard cores" of

all molecules in the gas interacting with a single molecule. Then, taking
into account that Zsp = Z1' ,

P = NkBT— [\n(V - K x c l ) - 0u]. (5)

Now we make the reasonable assumptions that (i) Vexc\ is proportional to

the total number of molecules in the gas and (ii) u, which as mentioned
before corresponds to an attractive interaction, is proportional to the den-
sity of molecules in the gas. Therefore,

Kxci « N, i.e., Kexci = (b/NA)N, (6)

2
u « (-N/V), i.e., u = -(a/N A)(N/V). (7)

Here, b and a are constants whose physical meaning will become apparent
later on, defined in terms of Avogadro's number NA, which is the number
of molecules in a mole of gas. Making use of Eqs. (6) and (7) in Eq. (5)
we get

1 pa(N/NA)^
P = NkBT 2 (8)
_V-(N/NA)b ^ NV

which, for n = N/NA = 1 (i.e., one mole of gas), leads to

(P + a / K L ) (^moi -b) = NAkBT = RT, (9)

which is the Van der Waals equation, where a = a/NA has the dimensions
of attractive energy (PV) times volume (V) per mole of gas and b those of
excluded volume per mole.
It may be noted that for P » a/V^ ol and Vmo\ 2> b, i.e., a mole of a gas
occupying a sufficiently large volume at a moderately high temperature,
Eq. (9) reduces to the ideal gas equation,

PVmol = RT. (10)

To investigate in more detail the Van der Waals equation, we simplify the
notation by writing V instead of Vmo\ and a instead of a, implicitly assuming
14 Effective Field Approach to Phase Transitions

that we are referring in what follows to one mole of gas (i.e., n = N/N& =
1). Equation (9) can then be written as

(PV2 + a){V - b) = RTV2

or, equivalently,

v-r^wsv-^-o, p j \pj \p
mi
which reflects in a visible way the cubic character of the Van der Waals
equation. Each pair of values (T, P) corresponds, in general, to three dif-
ferent solutions for (V"). We may note that for small T the three solutions
are real; for a certain T = Tc, the three solutions become a single solution
with V = Vc, P = P c ; finally, for large T a pair of roots become complex
and a single real solution remains.
This implies that there is a critical point, characterized by Pc, Vc, Tc,
which can be used as a point of reference to describe the behavior of the
gas. Let us write

(V - Vc)3 = V3 - 3VCV2 + 3V2V - yc3 = 0 &tV = Vc. (12)

We can compare Eq. (12) with Eq. (11) and equate the respective coeffi-
cients of V3, V2, V, and V° at the critical point. Thus,

(6 + i£r c /Pc) = 3Vrc, (13)

2
a/Pc = 3VC , (14)
3
ab/Pc = Vc . (15)

From Eqs. (14) and (15),

Vc = Zb. (16)

From Eqs. (14) and (16),

Pc = a/3V2 = a/276 2 . (17)

Finally, from Eqs. (13), (16), and (17),

RTC - (3VC - b)Pc = (9b-b)(a/27b2) =~ . (18)

 Liquid-Vapor Transitions 15

These results give a direct physical meaning to the constants a and b char-
acteristic of a given mass (a mole) of a gas, in terms of its volume Vc and
its pressure Pc at the critical temperature Tc at which the phase transition
between the liquid state and the vapor state takes place. The same relation-
ships for Vc, Pc, and RTC can be alternatively obtained taking as a starting
point

PC = P(VC), (dP/dv)Tc = a, (d2p/dv2)Tc=o,

which indicates that the function P(V) has an inflection point precisely at
T = TC.
We may define z = PV/RT and note that, for a Van der Waals gas,
making use of Eqs. (16)-(18),

zc = PCVC/RTC = 3/8, (19)

which is lower but of the same order of magnitude than

z = PV/RT = 1 (ideal gas). (20)

Real gases, or vapors, may differ considerably one from another in their
critical pressure (Pc), critical volume (Vc), and critical temperature (T c ).
However a law of corresponding states can be established measuring P, V,
and T, in units of Pc, Vc, and T c , respectively. Dividing Van der Waals
equation (n = 1)

(p+±yV-b) = RT (21)

by (1/3)PCVC, one obtains

[(P/Pc) + (a/PcVc2) (Vc/V)2] [3(V/VC) - 3(6/14)] = 3RT/PCVC, (22)

which reduces to

(P + 3 / V 2 ) ( 3 F - l ) = 8 T ; P = P/PC, V==V/VC, T = T/TC,

(23)
taking into account that, using Eqs. (16)-(18),

(a/PcV2) = 3, 3b/Vc = l, 3RTC/PCVC = 3(8/3). (24)

Equation (23) clearly implies a single function P(V, T) for all gases, as
far as they can be considered Van der Waals gases, and therefore a law
16 Effective Field Approach to Phase Transitions

V=V/Vc

Fig. 1.2.2. Shape of surface P(V,T) for a Van der Waals gas.

of corresponding states using the dimensionless units (P/Pc), (V/Vc), and

(T/Tc) as illustrated in the introductory section.
Figure 1.2.2 depicts the shape of the surface P(V,T) and shows cross
sections for constant T. On this surface, at constant T such that T/Tc 3> 1
the cross-sectional curves correspond to hyperboles (PV = constant) indi-
cating ideal gas-like behavior. At constant T = Tc, the curve passes through
C, the critical point, which is an inflection point. At constant T < Tc, the
curves contain maxima and minima that enclose a region of coexistence of
phases between them, indicated by a dotted line.
Table 1.2.1 gives experimental data of the constants a, b, and zc = RTC
for a few representative fluids, and gives also the Van der Waals value
for zc. It can be seen that, in spite of differences of more than an order of
magnitude (related to the attractive interaction energy between molecules),
the values of zc remain close to each other and to the Van der Waals value
z = 3/8 given by Eq. (19).
 Liquid-Vapor Transitions 17

Table 1.2.1. Parameters a, b, and z c for some real fluids.

Fluid a (l 2 atm/mol 2 ) 6 (1/mol) zc = PCVC/RTC

H20 5.464 0.0305 0.230

C02 3.592 0.0427 0.273
A 1.345 0.0322 0.291
He 0.341 0.0237 0.308
Van der Waals — — 0.375

As mentioned in the introductory section, the behavior near the phase

transition is usually described by the various critical exponents. To this end
it is convenient to rewrite the Van der Waals equation in terms of the new
variables

p = P - 1 = (P - Pc)/Pc, (25)
v = V-l = (V- Vc)/Vc, (26)
t = T-l = (T- Tc)/Tc. (27)

Substituting these definitions in Eq. (23), we get

= 8(1 +t) 3
P (28)
~ (2 + 3v) (1 + vf '

which is particularly useful to describe the behavior of the Van der Waals
gas near the critical point, where we know that p < l , « > 1 , and t <€. 1.
(a) Coexistence curve. At any T < Tc, the function p(y) has a minimum
and a maximum between which the vapor and liquid phases coexist. The
boundary of the coexistence region (see Fig. 1.2.1) looks like a downward
parabola with its apex at the critical point. The coexistence curve is the
locus of the points on p(v,t) for which (dp/dv)t = 0, and therefore making
the volume derivative in Eq. (28) and simplifying

{2 + 3
- 4 ( 1 + t) + {1 + ^ = - 4 ( 1 + t) + <p{v) = 0. (29)

The function 4>(v) can be expanded in a power series around the critical
point (v = 0) as follows:

<p(v) = <p(0) + yy<//(0> + ^ " ( O ) ? ; 2 • • • = 4 + 0 + 3v2 • • • (30)

18 Effective Field Approach to Phase Transitions

Retaining the lowest power of v <C 1 in the expansion and substituting in

Eq. (29) we get

«2 -1(-«)
or
1/2
v= H)1/2 (31)
{i) '
which shows that the critical exponent /? = 1/2 characterizes the tempera-
ture dependence of the order parameter (v) for a Van der Waals gas. As we
know, however, critical fluctuations, ignored in the Van der Waals picture,
contribute to produce a critical exponent /3 somewhat different from 1/2 in
real gases.
(b) Critical isotherm. At T = T c , the behavior of p(v), as given by
Eq. (28), corresponds to the critical isotherm (t = 0). Again we can make
a power series expansion of p(v) around the critical point as follows:

P(v) = P(0) + ^P'(0)v + ^p"(0)v2 + ^p'"(0)v3L = (~9/6)v3L.

Therefore, we obtain

V=~\v\ a t T = Tc, (32)

which implies a critical exponent 5 = 3, according to the pertinent defini-

tion, for the Van der Waals gas.
(c) Compressibility. The compressibility of a fluid is defined by KT =
— {l/V)(dV/dP)T- Therefore, in the vicinity of the critical point, we can
write down

KrK
- iv) (I) i d v / ^
or

K^x w -Pc[dp/dv)T. (33)

Taking the volume derivative of p(v) as given by Eq. (28) we get

g g _ _ 8(1 + 0 3
 Liquid-Vapor Transitions 19

which for T > Tc and n « l gives

% - U (35,

and therefore substituting in Eq. (33)

K?1 « - P c ( - 6 t ) = 6 ^ ( T - T c ), T > Tc, (36)

which yields a critical exponent 7 = 1 for the temperature dependence

of the compressibility at T > Tc. It is easy to repeat the calculation for
T < Tc, where v is not zero, but is given by Eq. (31). In this case, one gets

K^nU^iTc-T), T<TC. (37)

(d) Specific heat. Since the specific heat is defined by C = T(dS/dT),

where S is the entropy, and this can be given in terms of the free energy
by S = —(dA/dT), to calculate C we need an appropriate expansion of
A(T, V) in the vicinity of the critical point. The expansion can be written as

A^A0{T) + \[^yV-Vcf..- (38)

where A(T) is the non-singular part of the free energy and

d2A ' 1 B (dA\ 1 / dP\ I, T, 1,
V (39)
5 P = V dV (OV) = V VW) = vt-*^
and K^1 is given by Eq. (36) for T > Tc, and Eq. (37) for T < Tc. Then,
for T < Tc,

A « A0(T) + ~ 1 2 § ( T - TC)(V - VC)2A,

8A_ dA0(T) IP
b
~ dT~ dT + 6 K K ( c)

dA0(T) t &PCVC (V-VcV L

dT Tc V Vc

and using PCVC/TC = (3/8)i? = (3/8)NkB, from Eq. (19), and v2 = {V -

Vc)2/V2 = (4/3)(T c - T)/Tc, from Eq. (31), we get

C ( T < T C ) = T ( | | ) « C O + 3JV*BQ^... (40)

20 Effective Field Approach to Phase Transitions

On the other hand, for T > Tc the order parameter v is equal to zero,
and

C(T>Tc)^r(g)«Co- (41)

Co = —(dAo(T)/dT) is the non-singular part of the specific heat and is

expected to be nearly the same at T < Tc as at T > T c . Therefore, the
jump in specific heat from a finite value at T < Tc to another, different
finite value at T > Tc is given by

AC(T C ) = 3NkB (42)

and the specific heat critical exponent for a Van der Waals gas must be
zero.

References

1. T. Andrews, Phil. Trans. 159, 575-591 (1869).

2. J.D. Van der Waals, On the Continuity of the Liquid and Gaseous States,
Doctoral dissertation (1873).
3. H.E. Stanley, Introduction to Phase Transitions and Critical Phenomena
(Oxford University Press, Oxford, 1971).
 Chapter 1.3

Ferromagnetic Transitions

A ferromagnetic material is characterized by presenting a "spontaneous"

magnetization (i.e., a magnetization under zero external magnetic field)
at temperatures below a certain critical temperature Tc. In ferromagnets,
the magnetization versus magnetic field curve shows hysteresis, as shown
in Fig. 1.3.1. Hysteresis means memory, i.e., the ability to "remember" in
which direction a sufficiently strong external magnetic field last pointed
before dropping to zero field. That is why ferromagnets are widely used in
computer memories, among other things.
There are "hard" ferromagnets (large Hc) and "soft" ferromagnets
(small Hc), which are useful for one type of application or another. Of
course, the phenomenon of magnetism has been known to man from ancient
times, but only toward the end of the 19th century was the ferromagnetic
transition investigated quantitatively as a function of temperature by P.
Curie at the University of Paris. He found experimentally that the suscep-
tibility x = 4ir(dM/dH) of a ferromagnet depends on temperature accord-
ing to the simple law x(T) = C/(T — 6) where C is a constant (the Curie
constant), and 6 is the critical temperature below which spontaneous mag-
netization shows up. We can distinguish two main types of ferromagnets:
metallic (for instance, Fe, Ni, Co, and many alloys containing these ele-
ments) and oxides (e.g., Fe 2 03).
P. Weiss1 put forward in 1907 the famous "molecular field" hypothe-
sis, which assumes that within each "domain" (homogeneously magnetized
region of a ferromagnetic sample) the existence of an effective field,

HeS = H + 7 M
tends to produce a parallel arrangement of the atomic dipoles. This effective
or molecular field is made up of two contributions: the external field and

21
22 Effective Field Approach to Phase Transitions

B =H + 4*M

' 0 H

Fig. 1.3.1. Typical hysteresis loop for a ferromagnet as X < T c . At H = 0, B$ = 47rMs,

M s = spontaneous magnetization. At B = 0, H = Hc = coercive field (cgs units).

an additional field that is proportional to the magnetization, the coefficient

7 being a constant.
Consider a system formed by N elementary magnetic moments (per unit
volume) on a three-dimensional lattice. If the dipoles can be oriented only
in either one of two possible (up or down) directions, corresponding, for
instance, to spin s = ±Y2, or, more generally, to what is called the Ising
case (one-dimensional order parameter), there are only two possible values
for the interaction energy of every single dipole and the effective field

f +u = (H + 7 M ) M (dipole "down"),
l^i = \ (1)
\-u = -(H + 7M)/i (dipole "up"),
where /i is the atomic dipole magnetic moment. Figure 1.3.2 shows a planar
arrangement of dipoles predominantly oriented in the "up" direction. At
T = 0 K, the tendency for the dipoles is to attain the lowest energy, with
all dipoles pointing "up." (We ignore, for the moment, the zero point energy,
which, because of the uncertainty principle, precludes a perfect alignment
of all dipoles in one direction.) At T > OK, the ther nal energy tends to
produce some misalignment of the dipoles, which imp] es a lowering of the
effective field (through a lowering of M) and, correspondingly, a lowering
of the interaction energy \ui\, which favors further the misalignment.
 Ferromagnetic Transitions 23

Fig. 1.3.2. Planar arrangement of elementary magnetic moments predominantly ori-

ented in the "up" direction (energy + w) with a single moment oriented in the "down"
direction (energy — ui).

The partition function for a dipole is given by

Z = J2 exp(-w i /fc B r) = exp(w/fcBT) + exp(-uj/kBT). (2)

i

Therefore, the number of "up" and "down" dipoles, according to ele-

mentary statistical mechanics, is given by

N! = TV (up) = (N/Z)exp(u/kBT),
(3)
N2 = JV(down) = (N/Z) exp(-oj/kBT),
and the net magnetization (per unit volume) is given by

y ZJH- ^exp(w/kBT) + exp(-u/kBT)

= %tanh^-ltt, (4)

where Eqs. (l)-(3) have been used. Equation (4) involves, in implicit form,
an equation of state for the ferromagnet in question, which can be rewrit-
ten as

— =tanh I — ^ 7 — - £ ) , wthTc = - V - - (5)

Equation (5) implies that, for T = OK, H — 0, the spontaneous mag-

netization is given by

MB(0) = M s 0 = Nfi, (6)

24 Effective Field Approach to Phase Transitions

corresponding to the fact that tanh(oo) = 1. It also implies that, for T = Tc,
H = 0, the spontaneous magnetization becomes zero,

MS(TC) = 0

due to the fact that the only solution of Ms/Nfi = tanh((M s /A//x)(T c /T))
is zero. This confirms the definition of Tc in terms of 7, N, /z, and fce given
with Eq. (5).
As mentioned before, Eq. (4) gives an implicit equation of state M =
M(H,M,T). It is easy to get directly from Eq. (4) an explicit equation of
state H = H{M, T) as follows

^ = ( | ) 7 % t a n h - ( ^ ) - 7 M , (7)

which, expanding tanh (M/Nfi) in a power series, becomes

/ M_\ 1 (MX M
H 7./V/Z •JNH
5 \NVLJ 'Nil
(8)
The power series expansion makes clear the analogy of this equation of
state with the phenomenological equation of state in Landau's theory of
phase transitions (see Chapter 1.9).
The critical exponents for a Weiss ferromagnet can be easily obtained
from the equation of state as follows.
(a) Spontaneous magnetization. For H = 0, we can obtain MS(T), by
means of Eq. (7), solving

(Ms/Ms0)
(9)
t a n h - 1 (M s /M s 0 )

Since 1 < (Ms/Ms0) < 0 for T < Tc, we can choose values of (Ms/Ms0)
as closely spaced as desired and tabulate the corresponding values of (T/Tc).
Figure 1.3.3 depicts the behavior of the (reduced) spontaneous magnetiza-
tion as a function of (reduced) temperature calculated in this way.
At T < Tc, (Ms/Ms0) < 1, Eq. (9) becomes

T (Ms/Msi
(10)
(Ms/Msi 1 + i(M s /M s0 ) 2 +
 Ferromagnetic Transitions 25

Ms/Mso

T / Tc

Fig. 1.3.3. Spontaneous magnetization as a function of temperature.

and, consequently,

T 1 / M.
Tc ~ 3 VMs0 (11)

which implies
1/2
Ms
V3 1- for T < Tc. (12)
Ms0
Therefore, the critical exponent describing the temperature dependence
of the spontaneous magnetization just below Tc is (see Table 1.1.2)

/? = 0 1 n M 8 / 0 1 n | T c - T | = (13)
2'
which is the same as that describing the coexistence curve for a Van der
Waals gas. We note that this result is approximately valid only for dipo-
lar uniaxial ferromagnets (to be distinguished from the normal exchange
ferromagnets like Ni or Fe 2 03). Dipolar ferromagnets have low transition
temperatures of the order of IK, while exchange ferromagnets have usu-
ally much higher transition temperatures, up to 103 K. For instance, for Fe,
26 Effective Field Approach to Phase Transitions

which is an "exchange ferromagnet," the critical exponent is j3 « 1/3, due

to critical fluctuations near Tc, and is not taken into account in the Weiss
model.
(b) Critical isotherm. Likewise, for T = Tc, Eq. (8) gives

Iffi S ... (14)

which yields a critical exponent

5 = d\n\H\/dln\M\ =3 (15)

again identical to that for a Van der Waals gas.

(c) Magnetic susceptibility. For T > T c , Ms = 0,

1
- J_ dH ~ l T
*r ( 1 •7A/ju (T-rc), (16)
X ~ 47T 8M ~ 47T 47T 4TTT C

which is the Curie-Weiss law,

H<r-«>,
where

1 7 (17)
C 4TTTC '
9 = TC (Curie temperature). (18)

For T > Tc, M s = 0, and taking into account Eq. (12),

1 1 T J_\ 1 /Ms\2 1 ••yNfi

+
X iV^y 3 \Mv) Nn A-K

_ 1 T T 27
3 1 (T - r ) , (19)
~ 4TT 7 2; 47rrc c

which is fully analogous to Eq. (16) but has a coefficient twice as large
as before (T — T c ). Then, the critical exponent describing the temperature
dependence of the low amplitude susceptibility, both for T > Tc and for
 Ferromagnetic Transitions 27

T <TC, is given by
7 = d l n X - 7 d l n | T - T c | = l. (20)
(d) Specific heat. The zero external field ferromagnetic internal energy
can be written as

Q(T) = -l-Hev{T)Ms{T) = -\lM2s{T). (21)

Then, the transition heat will be given by

AQ = Q{TC) - Q(0) = i 7 M s 2 0 = ^ V = \Nk*Tc (22)

making use of Eq. (5).

The transition entropy, on the other hand, is given by

AS= [ °dQ(T)/T=- f i72(Ms/T)dMs (23)

Jo Jps0 l
and making use of the equation of state for H = 0,
r°
AS = - 7 - / V V / [tanh" 1 (Ms/Nfi)/Tc]d(Ms/Nfi)

= NkB / [tanh - 1 x] dx
Jo
nl
1
= NkB x tanh 1 x + — ln(l — x2 = NkBln2, (24)
o
where x = Ms/N/j,. Then, the jump in specific heat at Tc = T, associated
with the disappearance of spontaneous polarization, is given by
1 /dMB2\ 1
ACpySTe(jjf)T=rc ~2 7 V dT
(25)

and, taking into account that d M 2 / d T = -3iV 2 /i 2 /T c , from Eqs. (12)

and (15),

AC(T C ) = ^NkB. (26)

Since the specific heat at T > Tc (where the spontaneous magnetization

becomes zero) is finite, this implies a critical exponent
a = dliiAC/d\n\T-Tc\ =0 (27)
for a Weiss ferromagnet.
28 Effective Field Approach to Phase Transitions

From the above expressions of Tc, C, and MSQ in terms of the basic
parameters of the theory

Tc = jNp,2/kB, (28)
2
C = 4TrNfi /kB, (29)
M s 0 = N/j,. (30)

These parameters can be obtained directly in terms of macroscopically

observable quantities as

7 = 47rT c /c, (31)

H = kBC/4irMs0, (32)
N = 4wM*0/kBC. (33)

It is instructive t o compare numerical values for these basic parameters,

obtained from available experimental d a t a on T c , C, and MSQ, for various
ferromagnets. This is done in Table 1.3.1 for Fe, Ni and Co.
All numerical values 2 ' 3 are given in cgs units; fiB = eh/2mc = 0.927 x
1 0 " 2 0 erg/oersted; N** = z/vc = pNA/M, with p = 7.86, 8.9, 8.9, and
M = 55.85, 58.71, 58.93 for Fe, Ni, a n d Co, respectively.
T h e column giving (fi//j,B), i.e., the corresponding atomic dipole
moment in units of Bohr magneton (/ZB), shows numbers close to one, as
it should be expected. T h e last column, giving the ratio of N, obtained
from the experimental d a t a for MSQ and C, to the number of atoms per
unit volume 7VC = z/a3, shows numbers not very different from unity. It
is remarkable to see how a very simple theory, such as the Weiss theory,
with a very limited number of basic parameters, can give a coherent and
fairly decent quantitative account of the ferromagnetic behavior in these
and other simple ferromagnets.
T h e column giving numerical values for 7, the effective field coefficient,
shows large numbers, between 10 3 and 10 4 , for Fe, Ni, and Co. O n t h e basis
of pure magnetic dipole-dipole interaction one would expect something of

Table 1.3.1.

N
Tc C Ms0 7 M W/4) WW)
3 20 22
Fe 1043 2.24 1752 5.85 x 10 1.40 x 10~ 1.51 12.47 x 10 1.47
Ni 1400 2.32 1446 7.58 x 103 1.76 x lO" 20 1.90 8.20 x 1022 0.90
Co 485 0.61 510 9.91 x 103 1.32 x lO" 20 1.43 3.85 x 1022 0.42
 Ferromagnetic Transitions 29

the order of the Lorentz factor 7 = 47r/3, and in any case 0 < 7 < A-K. Thus,
there is a difference of two to three orders of magnitude between the Weiss
"molecular field" and a purely dipolar magnetic field. This was observed by
Weiss, but a satisfactory explanation did not come until many years later,
when, in 1928, Heisenberg4 proposed a quantum-mechanical "exchange"
interaction between neighboring atoms as the origin of the effective field,
capable of justifying values of 7 ~ 103.
In Heisenberg's argument, the interaction energy between two neighbor-
ing magnetic atoms, i.e., atoms with non-zero spin, would be given by

E = K±Je, (34)

where K is the Coulomb energy, not relevant for our present purpose, and

J e = J ^ ( 1 ) ^ ( 2 ) ^ ^ ( 2 ) ^ ( 1 ) dvi dv2 (35)

is the "exchange" energy, or energy associated with the exchange of elec-

trons (1) and (2) between neighboring atoms "a" and "b". Here,

yab=e2f—+ — - — - — ) (36)
\rab J"i2 7T>i ra2/

is the electrostatic interaction potential, including terms between atoms

(fab)i between electrons (1*12), and between each atom and the electron of
the other atom ( r b i , ^ ) - The signs ± in Eq. (34) correspond, respectively,
to anti-parallel and parallel spins, and E- < E+ only if J e > 0. The actual
value of J e depends on the ratio of r a b to the orbital radius for the electrons.
Thus, for Cr and Mn (small r a b) Je < 0, and an anti-ferromagnetic (anti-
parallel) arrangement between neighboring spins is favored, while for Fe,
Ni, and Co (large r a b) Jc > 0, and a ferromagnetic (parallel) arrangement
is favored.
It was found convenient to write the exchange energy of one atom (i)
with all of its nearest neighbors (j) as

V = -2j2JijSiSj, (37)
3

which, for all z nearest neighbors in equivalent positions, gives, after aver-
aging over the Sj components,

V = -2Jez[Sxi{Sxj) + Syi(Syj) + Szi{Szj)}. (38)

30 Effective Field Approach to Phase Transitions

Now, identifying the z direction with the ferromagnetic axis, where from
(Sx) = {Sy} = 0, (Sx) = M/gfiBN,

V = -2zJeSziM/gnBN, (39)

where g is the appropriate gyromagnetic ratio a n d /ZB is Bohr's magneton.

M is the magnetization per unit volume and N the number of atoms per
unit volume.
On the other hand, according to the effective field hypothesis,

V = HeS^i = - ( 7 M ) (gSzitiB). (40)

Equating Eqs. (39) and (40), we get

7 = - ^ - (41)
7 (41)
Ng^l
from which, if we are able to calculate Je solving the integral with the appro-
priate wave functions in Eq. (35), we would be in a position to evaluate the
effective field coefRcient 7, assuming t h a t the number of nearest neighbors
(z) and the density of ferromagnetic atoms (N) are known from crystallo-
graphic data. T h e evaluation of the integral in J e for complex atoms is not
an easy task, and only approximate numerical results are available in most
cases. However, these numerical results support values of 7 = 10 3 , of the
right order of magnitude for exchange ferromagnets. As pointed out above,
purely uniaxial dipolar ferromagnets, such as LiTbF4 (with a Tc of 2.9 K ) , 5
actually exist, in which t h e effective field is of magnetic dipolar origin. In
these systems values of 7 ss 1 can be expected.

References

1. P. Weiss, J. Phys. 6, 667 (1907).

2. A.J. Dekker, Solid State Physics (Prentice Hall, Englewood Cliffs, NJ, 1962).
3. Van der Ziel, Solid State Physical Electronics (Prentice Hall, Englewood Cliffs,
NJ, 1961).
4. W. Heisenberg, Z. Physik 49, 619 (1928).
5. G. Ahlers, A. Kornblit and H.J. Guggenheim, Phys. Rev. Lett. 34, 1227 (1975).
 Chapter 1.4

Superconductive Transitions

The superconductive state, 1 which is realized in many pure materials

and compounds including the recently discovered high-temperature oxide
superconductors, 2 is characterized by certain striking features. It shows
no measurable DC electrical resistivity as long as the DC current does not
exceed a certain, so-called, critical current. In other words, under these con-
ditions, it behaves as a perfect conductor that does not dissipate heat via
the Joule effect. It behaves also as a perfect diamagnet, provided the exter-
nal magnetic field, which gives rise to electrical surface currents, does not
exceed a critical value, beyond which the perfect diamagnetism (i.e., exclu-
sion of the magnetic field from the interior of the sample) disappears. In
addition, the superconductive state is usually characterized by the presence
of an energy gap 2A, centered at the Fermi energy, in the quasi-continuum
of possible energy levels for the individual electrons. This means that no
single electron with energy e such that |e — ep| < A can leave or enter
the crystal while it is in the superconducting state. These features of the
superconductive state are observable only at temperatures T < Tc, above
which a phase transition takes place leading to the "normal" state.
The formal theory 3 of the superconductive transition, based on the con-
cept of electron pairing due to attractive electron-electron interaction medi-
ated by phonons, is fairly well studied and we will point out here a few
relevant results, referring the reader to the abundant literature available on
this subject. 4 One can start with the Frolich hamiltonian, which includes
one term giving the energy of the system of non-interacting electrons and
phonons plus another term giving the energy of interaction of all pairs of
electrons characterized by momentum k, k! and a spin s, s', successively
absorbing and emitting phonons with energy huq and momentum q. Then,
assuming that only pairs of electrons with opposite momenta (k = —k')

31
32 Effective Field Approach to Phase Transitions

and opposite spin (s' = — s) give non-zero contributions in the interaction

energy term, one gets the Bardeen-Cooper-Schrieffer (BCS) hamiltonian,

V
HBCS = HT + HV = Y^£kctsCks - 2 H kk'Ck's'C-k'sC~ks'Cks, (1)

where HT is the kinetic energy term, mks = <4-scks is the operator giving
the number of individual electrons in terms of creation and annihilation
operators of electrons with momentum A;(energy ek) and spin s, Hy is the
potential energy of the paired electrons (k, s and k', s'), Vkk' includes
the (attractive) electron-phonon interaction energy and the (repulsive)
screened Coulomb electron-electron interaction, and c^,5,,clfc,s,c_fcs/,Cfcs
is the operator giving the pair density of electrons in terms of the c + and
c operators. The form of Vkk' > using second order perturbation theory, is
given by

V - \Mq\2hujq
Vkk' — -£-, 75 77 Co _ Ukk', \1)
(ek - £fc-g)2 - (hwq)2
in which the denominator of the first (electron-phonon interaction) term
can, if {ek — £k-q) is sufficiently small, give rise to a net attractive contri-
bution overcoming the repulsive contribution of the second term. Here, ujq
is the frequency of the phonon involved and q = k' — k is its momentum.
Making a Bogolubov-Valatin transformation from the operators c+, c to
new mixed operators of the form 7 = uc ± vc+, 7 + = uc+ ± vc, where u
and v are such that u2 + v2 = 1, putting HBCS in terms of the new 7 + , 7
operators, and choosing the coefficients u and v in such a way as to eliminate
the off-diagonal products 7+7+ and 77, one can show that

-HBCS = ^ 2ekvl + ^ (u\ - vl)ek(mk + m_fc)

ks:s k

^ Vkk'Uk'Vk'UkVk(l - mk' - m-k')(l -mk- m_fe) (3)

kk'

from which one can get the energy required to create a quasi-particle exci-
tation (a Cooper pair) by means of Ek — 8(HBCS)I'd(m,k)• The choice of u
and v, which eliminates the off-diagonal 7+7+ and 77 products, implies

2ekukvk - (u2 - vl) ^ Vkk'Uk'Vk' [1 - {mk) - (m_fc/)]

k'
= 2ekukvk - (u2k - v2k)Ak = 0, (4)
 Superconductive Transitions 33

where A^ is the temperature-dependent energy gap, depending on Vkk<

(which is zero except for |efe| = \ek — S\ < hujo, with WD the phonon
Debye frequency, being a constant V otherwise) and on (mk) — (m^k) =
l/(e £ f c / f c B T + 1 ) , which is the familiar Fermi-Dirac distribution function for
electrons. Doing some algebra, from Eq. (4) one gets

1 = ±VD(Q / {tanh[(e 2 + A2)^2/2kBT]/(e2 + A 2 ) 1 / 2 }de (5)

sufficient to define the temperature dependence of the energy gap A(T),

which can be chosen as the order parameter of the superconducting tran-
sition. A(T) becomes zero above a certain Tc, where the sample goes over
from the superconducting to the normal state, and below Tc is determined
by V, the strength of the electron-phonon interaction potential, and £>(£)
the electronic density of states at e = £, £ being the chemical potential.
In the weak coupling limit (1/VD 3> 1), Eq. (5) can be used to obtain
approximations for the gap as

A 0 « hojB/smh(l/VD) » 2fc B e D e- 1 / v ' 1 3 , for T ^ OK, (6)

0 D being the Debye temperature, and as

A«2\/2A;BTC[1-(T/TC)]1/2, for T < T c , (7)

which describes approximately the behavior of the order parameter in the

vicinity of the transition temperature for type I (second order transition)
superconductors, under zero external magnetic field. The behavior of the
specific heat near Tc can also be obtained from

C = d(HBCS)/dT

= dJ2 Ek-(^Ek- ^ j (1 - 2/(exP(£fe/fcBT) + l)) AT. (8)

This expression, which is non-zero but finite at T < Tc since

<A2fe)=A2=2(2fcBTc)2[l-(T/Tc)]
by Eq. (7), and is zero at T > Tc, leads to a finite jump in specific heat
at T = Tc

AC « 27VfcB, (9)
which implies a zero specific heat critical exponent for type I
superconductors.
34 Effective Field Approach to Phase Transitions

Conventional metallic superconductors have been the subject of inten-

sive research for several decades, but the efforts to push up the transition
temperature, Tc, in systems of this class have found only modest rewards,
since it has proved almost impossible to increase the transition temperature
beyond a few years after the discovery by Muller and Bednorz 2 of super-
conducting oxides with Tc above 30 K, several families of compounds with
transition temperatures ranging from 30 to 125 K have been discovered and
the expectations of getting compounds with even higher Tc are still high.
These new compounds are in general very anisotropic, and they differ con-
siderably from the metallic superconductors in several important respects
(see Table 1.4.1).
Perhaps the first question that comes to mind in considering the new
oxide superconductors is the following: is their pairing mechanism the
same, i.e., electron-phonon interaction, compared to the older, conven-
tional superconductors? And, if this is not the case: which is the pairing
mechanism in the new superconductors? In answering the first question, it
seems to be clear that the upper theoretical limit in Tc for strong electron-
phonon coupled superconductors is about 40 K, well below the observed
Tc = 125 K. Therefore, electron-phonon coupling alone does not seem suf-
ficient to explain Cooper pairing in the new superconducting materials. In
addition, no isotope effect on Tc has been unambiguously observed in them,
indicating that the value of the Debye temperature, which enters the expres-
sion of Ts in the electron-phonon picture, does not influence appreciably the
strength of the attractive interaction responsible for the electron pairing.
Several mechanisms5 have been proposed as candidates for the pair-
ing mechanism, including (i) charge density waves, (ii) spin density waves,
(iii) excitons, and (iv) resonating valence bonds. The theoretical situation
is far from clear for the time being, but some proposals (e.g., the resonating
valence bond picture) seem to be losing ground, due to the fact that the
onsite Coulomb correlation energy seems to be large enough in these mate-
rials. Others seem to be gaining support from inelastic neutron diffraction

Table 1.4.1. Superconductive parameters for some bcc elements

(cgs-emu units).

Superconductor Tc Bso fj, = ksTc/Bso N = B s0 /47r/i

V 5.3 1020 0.71 x 10~ 1 8 1.14 x 10 2 0

Nb 9.26 1980 0.64 x . 1 0 - 1 8 2.44 x 10 2 0
Ta 4.48 830 0.74 x 1 0 " 1 8 0.88 x 10 2 0
 Superconductive Transitions 35

data, which appear to support a significant role for magnetic pairing. In any
case, it appears not unlikely that once a realistic expression for the effec-
tive interaction V between two electrons is obtained, the observed behavior
might be understood within the framework of a generalized BCS theory,
which properly takes into account the highly anisotropic character of these
materials.
For a three-dimensional crystal, one can write, as can be seen from
Eq. (4),

Afc = ^ ^ A , t a n h ( f / 2 f c B r c ) , (10)
k' ^k'

where Vkk' is the electron pairing potential

Vkk, =V(q = k- #,&,&) = ^2J2<k'\e~ii9+G)r\k^k\ei{q+G')r\k')

G G'
oo
4we2 5c,GI+--l duJMe-Hq + G,q + G',„>)
x
2
« + G| * Jo W + I&I + I&'
(11)
where G, G' are reciprocal lattice vectors and £*, the single particle energy

£fc = ( £ i - A i ) 1 / 2 (12)
and

£ £
^ M = S h o n o » + £e"xcito» + plLmo» + s~pi» + ' " " (13)

Equation (10) implies a set of coupled equations that define the k depen-
dent anisotropic gap A(fc), the solution of which would give the value of
the transition temperature T c .
For a two-dimensional system, 5 such as the one of the layered oxide
superconductors, with m layers in the xy plane, Eq. (10) can be formally
rewritten as

&j{h,kz) = - Y, Yl J2 Vn' (« = \kt ~ KlQz = kz-k'z,u = ^ - fy)

1
x M l U ^ W - ' , (14)

where j , j ' are over the m layers, £j and £j/ are single-particle energies of
electrons in the planes j and j ' , with wave vectors k and k!, respectively,
36 Effective Field Approach to Phase Transitions

0.2 QA 0.6 0.8

Composition, x

Fig. 1.4.1. Plots of (6 — a)/a, c and Tc vs. composition x in (Yi_;ELaa;)Ba2Cu307

(according to Ref. 6).

and, if the electron pairing takes place in conducting layers isolated from
each other, V,y can be substituted by

V for j = j ' ,
Vjj'fijj' (15)
0 for j ± f.

To give an example of the trend in transition t e m p e r a t u r e with structure

and composition, we show in Fig. 1.4.1 d a t a on the superconducting oxide
(Yi_ a : La a ; )Ba2Cu307 with 0 < x < 1, by N a t a r a j a n and Subbarao. 6
It can be seen t h a t the transition t e m p e r a t u r e ranges from T c = 92 K
for pure Y B a 2 C u 3 0 7 to TC = 7 3 K for pure L a B a 2 C u 3 0 7 .

References

1. J.R. SchriefFer, Superconductivity (W.A. Benjamin, New York, 1964).

2. J.G. Bednorz and K.A. Muller, Z. Physik B64, 189 (1986).
3. J. Bardeen, L.N. Cooper and J.R. SchriefFer, Phys. Rev. 108, 1175 (1957).
4. P.L. Taylor, A Quantum Approach to the Solid State (Prentice Hall, Englewood
Cliffs, NJ, 1970).
5. See, e.g., S.S. Jha, Phase Transitions 19, 3 (1989).
6. S. Natarajan and G.V. Subbarao, Phase Transitions 19, 61 (1989).
 Chapter 1.5

Order-Disorder Transitions in Alloys

There are two kinds of solid solutions 1 : interstitial (e.g., carbon in iron)
and substitutional (e.g., silver in gold). The ones in which we are interested
here, because they can show order-disorder transitions, are the substitu-
tional solid solutions. Some binary systems, composed of only two kinds
of atoms, say A and B, form a continuum of solid solutions with the same
structure for all compositions (from 100% A atoms to 100% B atoms). When
like atoms (AA, BB) attract each other more strongly than unlike atoms
(AB), the tendency to separate into two phases is pronounced. When, on the
other hand, unlike atoms attract each other more strongly than like atoms,
ordered structures, i.e., superlattices L (ABABAB...) have a high probabil-
ity to be formed. The mutual solubility2 of two metals capable of forming an
alloy can be described in terms of a simple model, which assumes that the
cohesive energy is the sum of interactions between all pairs of neighboring
atoms. The existence of order-disorder transitions in alloys was reported by
G. Tamman in 1919 on the grounds of indirect evidence provided by pro-
nounced anomalies in certain physical properties. With the development
of X-ray crystallographic techniques, direct evidence for the ordered and
disordered phases became available. W.L. Bragg and E.J. Williams 3 pro-
posed in 1934 the first satisfactory theoretical model to describe this type of
phase transitions, which, as will be shown in this chapter, is based upon the
same kind of approach as other effective field theories previously discussed.
Figure 1.5.1 shows the unit cell of CuZn in the ordered phase (T < Tc)
and in the disordered phase (T > T c ), in which every point in the lattice
is occupied randomly by Cu and Zn atoms with 50% probability for either
one of these atoms. At T = OK, if the temperature has been lowered down
sufficiently slowly so that the system has remained in intermediate states of
quasi-thermal-equilibrium, the structure of the alloy is one of almost perfect

37
38 Effective Field Approach to Phase Transitions

T<Tc T>T C

f^TT^T
--6./
OZn £zn,Cu
#Cu 0Cu,Zn
Ordered phase Disordered phase
Fig. 1.5.1. Unit cell of CuZn in the ordered and disordered phases.

order. (Note, on the other hand, that a rapid quenching of the system from
T > Tc to T « OK will produce a state largely disordered, because the
characteristic relaxation times at very low temperatures become very large,
and the disordered structure, which is far from the one with minimum free
energy at these temperatures, becomes relatively stable.) If the tempera-
ture of the ordered structure is slowly increased again toward Tc, the degree
of order of the sample will decrease gradually first, and more rapidly as Tc
is approached, showing the characteristic behavior of a cooperative effect:
an increase of disorder gives rise to more and more disorder.
Figure 1.5.2 shows, schematically, anomalies in physical properties [spe-
cific heat, CP(T), electrical resistivity, p(T)], which give indirect evidence of
the order-disorder transition in a metallic alloy, as well as direct experimen-
tal evidence [X-ray or neutron diffraction intensity IhkiiT) corresponding
to superlattice reflections] of the transition.
As mentioned earlier, the Bragg-Williams (1934) theory assumes that
the degree of order (and disorder) in the alloy sample is homogeneously
distributed over long distances. Since the order-disorder process is driven
by the difference between local potential energy between pairs of unlike
(AB) neighboring atoms and like (AA, BB) neighboring atoms, assuming
a homogeneous distribution of order is equivalent to assuming an effec-
tive potential, which depends on the average degree of order at a given
 Order-Disorder Transitions in Alloys 39

Cp(T) /•(T) Ihki(T)

Jc Jc

Fig. 1.5.2. Anomalies in physical properties, CP(T) = specific heat, p(T) = electrical
resistivity, Ihkl(T) = diffraction intensity of superlattice reflection, accompanying order-
disorder transition.

temperature. Thus, this assumption is in complete analogy with the effec-

tive field assumption in Weiss's theory of ferromagnetism, for instance.
Consider a simple case such as that of /3-brass, whose unit cell is shown
in Fig. 1.5.1. In the ordered phase there are two interpenetrating simple
cubic lattices in which each atom A is surrounded by eight nearest neighbor
atoms B and vice versa. In the disordered phase each atomic position can
be occupied by either A or B atoms with equal probability (50%), and the
unit cell of the crystal becomes body centred cubic. In the fully ordered
state all A atoms occupy a positions and all B atoms occupy /3 positions.
In a partially ordered state there will be R (right) A atoms in a positions
and W (wrong) A atoms in j3 positions. Consequently, there will be also R
atoms B in j3 positions and W atoms B in a positions. Then we can define
an "order parameter" as

C
N ~ N ' (1)

where N = R + W is the total number of A or B atoms in the crystal. The

order parameter ( represents correctly the degree of order of the system
and can take any value from ( = 1 for R = N (fully ordered state) to C = 0
for R = 1/2 (fully disordered state). Evidently, values of R < 1/2 should be
excluded because in that case one would recover some order in the system
by interchanging the labels of R and W.
Our aim is to investigate the temperature dependence C(^) °f the order
parameter. In thermal equilibrium, the free energy is a minimum, and we
40 Effective Field Approach to Phase Transitions

can write

AF » AE - TASc{ ss 0, (2)

where AE is any small change in internal energy associated with small

changes in R and W, T the temperature, and A5cf the corresponding small
change in configurational entropy. We have neglected the small change in
thermal entropy A5th corresponding to changes in lattice vibrations. If we
now take a minimum change in R (and W) corresponding to the interchange
of one A atom initially in a "right" position by a B atom also initially in a
"right" position we have

AW = -AR = 2 (3)

and we can write Eq. (2) as

$(R, W) - kBTA ln[(N\/R\W\)] « 0. (4)

Therefore, taking into account that N is large (of the order of 1022 a t /
3
cm ) and so are R and W, we can use Stirling's formula to approximate

Aln[(N\/RlW\)] « AfTVlnJV - RlnR - Win W] « 2[lni? - InW]

using Eq. (3) and taking into account that N = R + W is a constant. Then
we have, from Eq. (4)

$(R, W) - 2kBTA \n[(R/W)} * 0 (5)

and, consequently,

[R/W) = exp[${W, R)/2kBT], (6)

which, when substituted into Eq. (1), provides a relationship between

C(.R, W) and $(R, W).
On the other hand, we can get another expression of $(R,W), tak-
ing into account the assumed large-scale homogeneity of the system, as
a properly averaged function of $ A B , $AA, $ B B , which are the possible
pair potentials between a given atom and its nearest neighbors. Taking
into account that the respective probabilities for atoms to be in "right"
or "wrong" positions are {R/N) and (W/N), respectively, the change in
internal energy corresponding to an interchange of two neighboring atoms
 Order-Disorder Transitions in Alloys 41

located at "right" positions is given by

&{R,W) = -z ($AA + $ B B - 2$AB)

W
($AA + $BB - 2$AB) ( -Jj

R-W_
= z ( 2 $ A B - *AA - 2$BB) = $oC, (7)
N
where z is the number of nearest neighbors, $ 0 = Z{2$AB — $ A A — $ B B ]
and ( — (R — W)/N; according to Eq. (1) $o means the change in internal
energy corresponding to interchanging two unlike atoms in the perfectly
ordered state (i.e., at very low temperature) where this change has the
largest value. It may be noted that, actually, Bragg and Williams assumed
the relationship between &(R, W) and £ given by Eq. (7) rather than deduc-
ing it from the assumed large-scale homogeneity of the degree of order in
the system.
Consequently, we can write
1/2'
R-W _ (R/W)1'2 - (R/W)-1'2
c= R + W ~ (R/W)1/2 + (R/W)-1/2 ~ tan
*<#
(8)

and, therefore, using Eqs. (5) and (7)

"(*o/4fcn)
C = tanh (9)

which is the desired equation of state giving the temperature dependence

of the order parameter £. The transition temperature, at which (and above
it) the order parameter becomes zero, is given, in terms of <&o = 2 $ A B —
$AA-$BB, by

Tc = $O/4/=B. (10)

Equation (9) can be written in more explicit form as

(tanh" 1 C)/C = Tc/T, (11)

which allows one, expanding in a power series, as usual, the hyperbolic
tangent, to get £(T) in the vicinity of the transition temperature as
1/2
C(T) = v/3[(T c -T)/T] (12)
42 Effective Field Approach to Phase Transitions

The extra specific heat associated with the order-disorder process can
be calculated in the following way. Let us consider the extra specific heat
per atom, rather then per unit volume or unit mass. As shown above, the
interchange of a pair of atoms located at "right" positions (AR = —2) leads
to a change in internal energy AE = $(R, W) = $ 0 C Therefore,

cLB _ AE_ _ _$oC

(13)
dR ~ AR ~ ~ 2
and, using the definition of C in Eq. (1),

dE = ~dR=- J-/V$oC dC- (14)

The extra specific heat per atom is given, then, by

1 dE 1. dC
AC (15)
"=NdT =l * ^
where (d£/dT) can be obtained, near and below T c , from Eq. (12), as

dC _ v ^ (Tc-Ty1/2 (Tc
(16)
dT 2 V T I \T2

leading to

AC P « -kkBB ( ^ ) (T < T c ), (17)

2 {T

where the expression for T c , Eq. (10), has been used. Equation (17) implies
a finite jump at T = Tc in extra specific heat

[ACp}Tc « |fcB, " (18)

a result encountered before, due to the fact that at T > Tc the order
parameter is zero, and, accordingly,

ACp = 0 (T>Tc). (19)

Fluctuations, and other complications not taken into account in the

simple Bragg-Williams theory, contribute to produce a more pronounced
temperature dependence of the specific heat peak accompanying order-
disorder phase transitions in alloys.
 Order-Disorder Transitions in Alloys 43

The transition heat per atom, given by the integral of the extra specific
heat is, using Eqs. (15) and (10),

L o
ACp(T)dT=^
4 JO
^ , (20)

a result that is fairly well fulfilled by the experimental data. Transition tem-
peratures for order-disorder in alloys range in hundreds of degrees Kelvin.
For instance, for (/3-brass *CuZn), the transition temperature is Tc = 740 K.
Therefore, according to Eq. (10),

$ 0 = z [2$ A B - *AA - 2 $ B B ] = 4fcBrc « 0.25 eV. (21)

As mentioned before, the theory of Bragg and Williams does not take
into account the possible existence of short-range order. It only considers
long-range order, homogeneously distributed throughout the crystal. It can
be easily illustrated with an example that overlooking short-range order
leads to trouble. For instance, consider the case depicted in Fig. 1.5.3.
The planar lattice shown would appear as disordered in the Bragg-
Williams theory, because each point in the lattice has equal probability of
being occupied by A or B atoms. On the other hand, from a local point
of view, it is clear that this arrangement possesses a high degree of order,
almost perfect if one does not consider the discontinuity indicated by the
vertical dotted line.
These considerations led Bethe 4 and others to introduce a short-range
order parameter, a, defined as follows. Let us call P(AnnA) the probability
that an A atom has an A atom as nearest neighbor, and P(AnnB) the
probability that an A atom has a B atom as its nearest neighbor. Then, we

o o o o • • •
• • • # 0 0 0 0
o o o o • • •
• • • • o o o o
o o o o • • •
• • • • o o o o
o o o o • • •
• • • • o o o o
Fig. 1.5.3. Planar lattice showing zero order from the long-range order point of view,
and a high degree of order from the short-range order point of view.
44 Effective Field Approach to Phase Transitions

define a in such a way that

P(AnnA) = (1 + a)/2, (22)

P(AnnB) = (1 - a)/2. (23)
This implies that a = 1 corresponds to perfect order and a = 0 to
perfect disorder. Then, dividing Eq. (22) by Eq. (23) and writing in the
appropriate Boltzmann's factors,

which, to simplify matters, can be written, assuming that $AA = $ B B , as

{TZ~) =exp($SR/fcBT). (25)

This implies

In ( ^ f ) = $ S R /fc B T, (26)

which can be compared with the result in Eq. (11)

t a n h ' 1 C _ $o/4

which gives the long-range order parameter £ (in the Bragg-Williams the-
ory). The concept of short-range order can be incorporated into the basic
framework of the long-range order theory leading to improvements in the
calculated specific heat peak, which in this way comes closer to the exper-
imentally observed peak.

References

1. See, e.g., G. Tamman, The States of Aggregation (Van Nostrand, New York,
1925).
2. See, e.g., A.J. Dekker, Solid State Physics (Prentice Hall, Englewood Cliffs,
NJ, 1962).
3. W.L. Bragg and E. Williams, Proc. Roy. Soc. (London) A145, 699 (1934).
4. H.A. Bethe, Proc. Roy. Soc. (London) A150, 552 (1935).
 Chapter 1.6

Ferroelectric Transitions

In 1921, J. Valasek,1 an American investigator, discovered anomalous

dielectric properties in crystals of Rochelle salt, or "sal de la Seignette"
(sodium potassium tartrate tetrahydrate) in the vicinity of 24°C, which
were correctly interpreted as analogous to those accompanying a ferro-
magnetic transition. This led him to name the temperature at which the
dielectric constant presented a sharp peak as the Curie temperature. Some
years later, in the United States of America, C.B. Sawyer and C.H. Tower2
observed for the first time hysteresis loops in the P (electric polarization)
versus E (electric field) dependence for Rochelle salt. This confirmed the
analogy with ferromagnetic transitions. In 1943, G. Busch and P. Scherrer3
(working in Switzerland) discovered peaks in the dielectric constant of KDP
(potassium dihydrogen phosphate) and several isomorphs at temperatures
below room temperature. In 1943, during the Second World War, Wainer
and Salomon (in the United States), Ogawa (in Japan), and Whul and
Goldman (in Russia) found anomalous dielectric properties 4 in ceramic
samples of barium titanate, which were similar in many respects to the
anomalous properties previously found in Rochelle salt and KDP.
After the war, several investigators, especially B. Matthias at Bell Labs.
and R. Pepinski at the University of Pennsylvania, and their coworkers, dis-
covered a multitude of new materials with phase transitions accompanied
by dielectric anomalies. The use of the term "ferroelectrics," instead of the
original term "seignetteelectrics" became widespread for these materials,
and their number has kept growing. At present, the number of known fer-
roelectrics is in several hundreds and new ferroelectrics are often added to
the list. In part, the initial drive to find new ferroelectrics was prompted by
the excellent piezoelectric properties of these materials, which make them
useful in "sonar" devices for submarine detection.

45
46 Effective Field Approach to Phase Transitions

A ferroelectric crystal can be defined as a piezoelectric possessing a

spontaneous electric polarization that is reversible under the action of an
external electric field. Out of the 32 existing crystal classes, 20 are piezo-
electric (i.e., non-centrosymmetric). Twenty out of these 32 are pyroelectric
(i.e., they possess a temperature-dependent spontaneous polarization).
Those pyroelectrics in which the polarization can be switched back and
forth along the polar axis under the action of an external electric field are
called ferroelectrics.
It may be noted that at T < T c the coercive field, i.e., the minimum
value of the external electric field sufficient to reverse the spontaneous polar-
ization, may become very large, even larger than the threshold dielectric
breakdown field. On the other hand, in some crystals the molecular units
can decompose chemically or can become altered at temperatures well below
the expected Curie temperature for the phase transition, where its esti-
mated coercive field is still too large. In this case, according to the previous
definition, the crystal would not be ferroelectric, but a "frustrated" ferro-
electric, in spite of the fact that it has a spontaneous polarization. So, the
definition is artificial to some extent, because sample perfection and exper-
imental conditions can be determinant, in many respects, of the realization
or not of polarization reversal.
One of the main characteristics of a ferroelectric is its nonlinear response
to an external electric field. Figure 1.6.1 shows P vs. E curves for a typical
ferroelectric at temperatures below the transition, close to the transition

D=E+4itP

Fig. 1.6.1. P vs. E curves and Ps(T) for a typical second order transition ferroelectric
crystal.
 Ferroelectric Transitions 47

and above it, and the characteristic temperature dependence of the spon-
taneous polarization. These curves can be easily displayed on the screen of
an oscilloscope by means of a simple Sawyer-Tower circuit if the sample
shows little electrical conductivity.
If the conductivity is appreciable, the P vs. E curves would become
distorted and it would be necessary to introduce a variable resistor at the
reference capacitor in the Sawyer-Tower circuit to be able to get phase
compensation and recover good looking hysteresis loops. The nonlinear fer-
roelectric polarization of the crystal in response to the external field is
manifest, except at T > T c . The dielectric constant, which is denned as
e = AndP/dE (esu-cgs units), shows also a markedly nonlinear behavior
and a strong temperature dependence in the vicinity of the transition. This
is shown in Fig. 1.6.2.
Ferroelectric transitions are usually accompanied by pronounced anoma-
lies near Tc in many other physical properties: structural properties (unit
cell dimensions, atomic positions), thermal properties (specific heat, ther-
mal conductivity), elastic properties (sound velocity and attenuation, elas-
tic constants), optical properties (refractive indices, birefringence, optical
activity), etc. This fact makes ferroelectric crystals useful in a variety of
applications.
In the case of uniaxial systems with rigid elementary dipoles reorientable
in either one or the other of two opposite directions, the effective field
approach to ferroelectric transitions 5 is completely analogous to the Weiss
theory for ferromagnets described in one of the preceding chapters. The

Fig. 1.6.2. Dielectric response (e) as a function of field and low-amplitude dielectric
constant e(T) for a typical second order transition ferroelectric crystal.
48 Effective Field Approach to Phase Transitions

effective field is given by

EeS = E + (3P, (1)

where E is the external field and /3P (with /? a generalized Lorentz factor
depending on the geometry of the dipole lattice and P the electric polar-
ization per unit volume) is the cooperative field due to partially ordered
system of dipoles, which gives rise to a non-zero dipolar field on any point
of the lattice. The energies associated with the two possible orientations of
a given dipole are, therefore, w = ±(E + (3P)/J,, where fi is the elementary
dipole moment. The partition function is the sum of only two Boltzmann
factors with Wi — (+w) or (—w), i = 1,2, and the number of dipoles point-
ing in the direction favored and opposed by the effective field is given,
respectively, by

Ni = (N/Z) exp(w/kBT), N2 = (N/Z) exp(-oj/kBT). (2)

The polarization is then given by

{E
P=(N1- N2)n = N^ tanh + ^ . (3)

Taking into account that as T approaches Tc from below at E = 0,

P = Ps approaches zero, one gets

• Tc = / ? V A B (4)

and, therefore,
P ~TCE + (3P~
= tanh (5)
Nft~ T pNp
The equation of state obtained in Eq. (5) in implicit form can be made
explicit as

t a n h / 3 P
^ = | ^ " ( i | ) - - ^
It is easy from here to get the behavior of the spontaneous polarization
(E = 0) and the polarization along the critical isotherm (T = Tc) in the
vicinity of Tc, as was done in the ferromagnetic case.
Spontaneous polarization:

A = V3[1-(T/T C )] 1/2 . (7)

PsO
 Ferroelectric Transitions 49

Hence,
d In Ps = 1
^ <91n|T c -T| 2'
It has been observed experimentally for triglycine sulfate that, in the
interval 10~ 2 > (AT/T C ) > 1 0 - 4 , the experimental value of the exponent
P is 0.5, within experimental error.

Critical isotherm:

E=±(J3Nri{P/Ntf. (8)

Hence,
s=
JhTp=3>
which again agrees very well with the experimentally observed value for
triglycine sulfate and other second order transition ferroelectrics.
The dielectric constant at T near Tc can be obtained similarly, with the
following results:

e-\T) = ^-(T-Tc) = ±(T-Tc), T>TC, (9)

e-t(T) = ^f-(T-Tc) = ^(T-Tc), T>TC. (10)

Therefore,
d In E-1
7 = 7 =
ainfr-T c |
is in good agreement, within experimental error, with the observed values
in the interval 1 0 - 2 > AT/T C > 10~ 4 for several second order transition
ferroelectrics. The factor of two between the Curie-Weiss laws, Eqs. (9)
and (10), for T > Tc and T <TC, has been also confirmed by experimental
data, taking into account small adiabatic corrections.
The specific heat and other thermal properties of a ferroelectric sys-
tem can be calculated as was done in the ferromagnetic case, from the
temperature-dependent internal energy associated with the ordering of the
dipole system,

Q(T) = ~EMT)Ps(T) = -i/?P2(T) (11)

50 Effective Field Approach to Phase Transitions

with the following results:

AQ = Q(TC) - Q(0) = -NkBTc (transition heat), (12)

-I
AS =
Jo
d \pPs(T) T = NkB In 2 (transition entropy), (13)

[ACP]n = Tc ( — J = -NkB (specific heat jump at T c ). (14)

Therefore, the jump in specific heat at the transition is finite and,

consequently,
, d In Cp
a = a=
dln\T-Tc\=°-
Experimental data for specific heat at various second order ferroelectric
transitions show finite peaks and finite discontinuities at T = Tc, but they
show also departures from the simple picture given by the effective field
approach described here.
It may be noted that, as previously mentioned, spatial fluctuations of
the order parameter (polarization) become prominent in the vicinity of the
Curie point, and, as shown by simple arguments (see Chapter 1.9) and
also by renormalization group theory, they should give rise to logarithmic
corrections to the mean field results. These corrections are difficult to see in
dielectric measurements, and furthermore can be masked by other effects,
but have been seen unambiguously in specific heat data on triglycine sulfate
taken by a.c. calorimetry.
From experimental data for the transition temperature Tc = (3N[i2 /ks,
the Curie constant, C = AnNfi2/k&, and the saturation (low T) sponta-
neous polarization, PSQ = N/J,, one can get the basic ferroelectric parameters

H= 4TT TC/C, (15)

H = kBC/4irPs0, (16)
N = 4irP*0/kBC, (17)

for a number of representative ferroelectric cystals and then make com-

parisons with independently observable experimental quantities whenever
possible.
 Ferroelectric Transitions 51

Table 1.6.1. Basic parameters for selected ferroelectric crystals.

T c (K) C(K) P* P n JVc z N"

(/tC/cm2) (10_18esu) (1022cm-3)

PbTi03 765 4.1 x 10 5 57 2.34 X 1 0 ~ 2 26.3 0.649 1 1.56

BaTi03 393 1.4 x 10 5 27 3.47 X 1 0 - 2 18.9 0.426 1 1.56
KNb03 708 2.4 x 10 5 30 3.21 X 1 0 ~ 2 29.3 0.307 1 1.56
TGS 322 3.5 X 10 3 3.5 1.13 3.72 0.282 2 0.31
TGSe 295 4.0 x 10 3 4.2 0.92 3.48 0.361 2 0.30
TGFB 346 2.6 X 10 3 3.2 1.65 3.00 0.317 2 0.33
LiNbO-3 1468 2.5 X 10 5 55 7.38 X 1 0 ~ 2 16.6 0.99 2 1.05
LiTa03 891 1.6 X 10 5 43 6.99 X 1 0 - 2 13.6 0.95 2 1.05
KH2PO4 123 3.3 X 10 3 5.0 0.468 2.41 0.620 4 1.04
RbH2P04 147 4.1 x 10 3 5.6 0.450 2.68 0.627 4 0.95
KH2As04 97 3.3 X 10 3 5.0 0.369 2.41 0.620 4 0.96

* l / i C / c m 2 = 3000 e s u / c m 2 .
**NC = z/vc, vc = unit cell volume, z = the number of molecule units per unit cell.

In Table 1.6.1, we have done this for four groups of ferroelectric iso-
morphs belonging to the following important ferroelectric families:
Perovskite family (PbTi0 3 , BaTi0 3 , KNb0 3 ).
TGS family (triglycine sulfate, selenate and fluorberillate).
Lithium niobate family (LiNb0 3 , LiTa0 3 ).
KDP family (potassium and rubidium dihydrogen phosphates, potas-
sium dihydrogen arsenate).
It may be noted that the values for fi and N obtained using Eqs. (16) and
(17) are very reasonable. The \x values are of the order of Debye units (one
electron charge times an angstrom) and the N values compare fairly satis-
factorily in most cases with the values given in the last column, obtained
from X-ray diffraction data for the lattice parameters, z being the number of
molecule units per unit cell. The /? values are always such that 0 < j3 < 4ir,
as they should be if dipole-dipole interactions are involved. Also, j3 values
for crystals within the same family, and, therefore, with the same structure
and the same microscopic geometry, are very close to each other. The fi
values obtained for ferrqelectrics are two orders of magnitude larger than
the corresponding fi for ferromagnets discussed in Chapter 1.3. All this
lends support to the assumption that the "molecular field" in the case of
ferroelectrics is indeed the field due to dipole-dipole interactions.
52 Effective Field Approach to Phase Transitions

References

1. Valasek, J. Phys. Rev. 17, 475 (1921).

2. C.B. Sawyer and C.H. Tower, Phys. Rev. 35, 269 (1930).
3. G. Busch and P. Scherrer, Helv. Phys. Acta 6, 234 (1933).
4. See, e.g., F. Jona and G. Shirane, Ferroelectric Crystals (Pergamon Press,
New York, 1962).
5. See, e.g., W.P. Mason, Piezoelectric Crystals and their Application to Ultra-
sonics (Van Nostrand, New York, 1950).
6. K. Ema, K. Hamano and Y. Ikeda, J. Phys. Soc. Japan 46, 345 (1979).
7. See, e.g., Landolt-Bornstein, Crystal and Solid State Physics, Vol. 3 (Springer-
Verlag, New York, 1969).
 Chapter 1.7

Superfluid Transitions

Superfluidity,1 perhaps even more than superconductivity, is one of the

truly striking phenomena observable in condensed matter physics. At suffi-
ciently low temperatures, normal liquid helium presents a phase transition
to the superfluid state, in which it can remain in motion with apparently
no loss of energy due to viscous losses, and can even defy gravity through
capillary action unopposed by viscosity. The peculiar characteristics of the
superfluid state are determined by the zero point motion of helium atoms,
much more important in helium than in any of the heavier atoms. This gives
rise to the phenomenon of Bose condensation. 4 He atoms can form super-
fluid Cooper pairs, analogous to the electron Cooper pairs connected with
the superconducting transition. They behave like quasi-bosons in the sense
that they obey Bose-Einstein statistics, but conserving their total number,
in contrast to normal bosons, like, e.g., photons, phonons, or magnons. In
the condensed superfluid state 4 He atoms can perform together a friction-
less collective motion.
Some of the striking physical properties of 4 He can be summarized as
follows:
(i) At T > 4.2 K, it forms a normal gas or vapor, and, when the tem-
perature is lowered down to T = 4.2 K, a normal vapor-liquid transition
takes place, at which the boiling of the liquid can be clearly observed. In
the temperature interval 2.1 < T < 4K, the liquid remains in a normal
condition, in which boiling and evaporation are taking place as usual (this
is the so-called liquid He I state). At T = 2.1 K, however, the boiling of the
liquid stops abruptly and the surface of the liquid becomes quiet, remain-
ing so down to 0 K (this is the so-called He II or superfluid state). The
specific heat of 4 He presents a sharp peak at Tc = 2.1 K, called the A point
because plots of CP(T) vs. T resemble the greek letter lambda. The sharp

53
54 Effective Field Approach to Phase Transitions

specific heat peak is the signature of the transition from the normal to the
superfluid state.
(ii) The viscosity of liquid 4 He at T < T c , which, like the viscosity of any
other liquid can be measured observing the flux of liquid through a capillary
tube, drops suddenly by a factor of the order of 106, i.e., practically to a
value of zero. After the Bose condensation, all 4 He are capable of moving
collectively without internal friction.
(iii) Below the A point, 4 He atoms are capable of flowing upwards, in
the form of a thin film, over the walls of a vertical cylindrical container at
speeds of the order of 30 cm/s.
In spite of paramount contributions by Bogolubov, Feynman, and oth-
ers, the formal theory of superfluidity is still, in more than one respect, an
open problem.
We will outline a simple calculation that puts limits on the order param-
eter (the number of helium atoms condensed into the ground state) as
a function of temperature, using Bose-Einstein statistics. According to
Planck's distribution law, the average number of quasi-bosons in the excited
state characterized by energy Ep = h2k2/2M is given by

n (1)
P = e/3(BP-C)_i'

where (3 = 1/ksT and ( is the chemical potential which warrants that

Ylp np < N (the total number of helium atoms in the system) must be
conserved. We may note that C < 0 in Eq. (1), which would imply np < 0,
not meaningful from a physical point of view.
The total number of particles, TV, will be given2 by the sum of those
particles in the ground state no plus all the other particles in any of the p
excited states. Therefore, at T = OK,

/V = n 0 ( 0 ) + ^ ^ - I = n 0 ( 0 ) , (2)
p

while at T > OK,

/v=n0(T) + ^ e / 3 ( g p _ 1 c ) _ i . (3)
p

Because, as mentioned above, C < 0, the sum on the right-hand side of

Eq. (3) is such that:

(4)
S eXp[/3(£p - C)] - 1 " ^ eMPEp] - 1'
 Superfluid Transitions 55

which can be easily calculated transforming it first to an integral

L3 \ ink2 dfc
= 1. (5)
4p- exp[/?£p] - 1 J0+ { 8ir3Jexp[f3h2k2/2M]-l
Making the change to a new variable t = 3h2k2/2M, dt = {/3h2/
2M)2kdk, the result of the integration is

r t1'2
[(L3/87T3)27r(2M//3/i2)3/2] /
Jo
= [(L 3 /87r 3 )27r(2M//?/i 2 ) 3 / 2 r(3/2)C(3/2)], (6)

where the product r(3/2)£(3/2) is a pure number given by (0.0587) x 47r2.

Then, making use of this result in Eq. (3) we get:

MT) > 1 _ (0.587)(L/fc) 3 (2Mfc B ) 3 / 2 3/2

If we define
2/3
{h/LfN
T* 3 2 (8)
0.587(2MfcB) /

we can rewrite Eq. (7) as

n iT) 3/2
°N >-l-(l)
-
,
\TC,
(9)
where it is clear that T* means an upper bound for the transition temper-
ature. In other words, at T = OK, no(0) = N, and all the atoms (or atom
pairs) are in the condensed ground state, which is the ordered superfluid
state. At T > Tc, on the other hand, we may expect that no(T) is at its
minimum allowed value, and the atom system becomes disordered. It may
be noted that the analogy between the result of Eq. (9) and the result of the
spin-wave model for ferromagnets, which gives the temperature dependence
of the order parameter (magnetization), is

{
Ms0 \T*J '
where T* — Je/ksA2/3, A being a numerical constant equal to 0.117 for
the simple cubic lattice.
56 Effective Field Approach to Phase Transitions

We can estimate a rough upper limit for the transition temperature

of 4 He to the superfluid state making use of Eq. (8) and the fact that
p( 4 He) = 0.145 g/cm 3 , i.e., {N/L3) = p/M = 2.18 x 10 22 . We thus get

T c *( 4 He)=3.1K, (11)

which is somewhat larger than the experimental value Tc = 2.18K. The

ratio is (T c *)/(T c ) exp « 1.42, and the analogy with the ferromagnetic case
can be taken a step further because, using the effective field result of Chap-
ter 1.3 Tc = ( 7 ) A ^ 2 / A ; B = 2zJe(Sz)2/kB, one gets a ratio

(TC*)/(TC*) = pziSzfA2'3]-1 « 1.39

for a simple cubic lattice (z — 6) of spin(5 z ) = 1/2. It is not clear whether

the coincidence of (TC*)/(TC) ratios for the superfluid and the ferromagnetic
transitions has a good physical foundation or not, but in case it does, it
would lend some support to attempts to apply the effective field concept to
describe superfluidity.
Let us briefly review2 the formal theory of Bogolubov for superfluid
liquid helium. We will show how at low enough temperatures the ther-
mal excitations likely to be excited in the system are collective, boson-like
excitations, consistent with a ground state made up of superfluid Coopers
pairs, while at temperatures above a certain transition temperature single-
particle excitations become more likely, giving rise to the disappearance of
the superfluid state.
The starting point is the hamiltonian, analogous to the BCS hamilto-
nian, introduced in Chapter 1.4 to describe superconductivity:

H = HT + Hv = J2 Ekatak + - ^ Vqa+_qa++qak,ak, (12)

k k,k',q

where Ek = h2k2/2M, Vq is an effective attractive potential between pairs

of 4 He atoms and the a+, a are, respectively, creation and annihilation
operators. If we assume that in the superfluid state the majority of the 4 He
atoms are in the (paired) ground state, i.e., iVo ~> {N — No), and we take
into account commutation relations for the boson creation and annihilation
operators,

[ak,ak'] = Sk,k', [ainat J = lak,ak>] = 0, (13)

 Superfluid Transitions 57

we can write

Hy « ^V0[a^a^aoa0] + - ^ ] V0 [a% aka£a0] + - ^ ] V0[a^a^IQa0]

k,0,0 0,fc',0

+ - Y^ Vk [aoataoak] + 2 S V k
~' [at'aoak'ao\
fc,0,fc 0,k',-k'

+ 2 1 3 Vq[a±qa+aoa0] + ^ Y V-q[aoaoaqa-q]' (14)

0,0,9 q,-q,q

where, under the assumption that N0 > (N-N0), we have kept only those
terms in the sum
V a
Y i t-qat'+q - ak'ak
k,k' ,q

that contain at least one pair of factors aoao or a J a j corresponding to the

densely populated ground state. Since we expect that iVo is a macroscopic
number we can make the substitutions

ao"(ao"a0)a0 = aJ(a 0 ao" - l)a0 = ajaoa^oo - a^ao —> NQ - N0 « iVg,

a 0 ao -> VNOT/NQ - 1 « AT0,
a+a+ -» v / T V o T l / N o T 2 « JV0,

and taking into account that Vk = V-k> we get

+ 2 N V
Hv ~ ^N0V0 2 ° ° Y akak + 22No Y V a a
ktk
k

+ -N0^2vq[aqa-gatqa+]. (15)
q

Then, we can rewrite the total hamiltonian as follows:

H « -N0V02 + Y (&k + N0Vk)a+ak + ^ Y N0Vk(aka„k + a+ fe a fc ),

k
(16)
where we can now make use of Bogolubov's procedure to transform it into
a simplified hamiltonian. To this end we define the new operators
ak = (cosh6k)ak - (sinh0fe)a+fc; a £ = (cosh#fc)a£ - (sinh0fc)a_fc,
(17)
58 Effective Field Approach to Phase Transitions

with 9k being a free parameter to be specified later. Here, the new operators
ak and a_fc fulfill the commutation relation

[ak,a^,\ = fa,k'- (18)

We can write, making use of the definitions in Eq. (17),

^hcukOtlak = ^/iw f c [(cosh 20fc)a^afc + (sinh20fc)]

k k

- - ^ M f e ( s i n h 26k)(aka-k + atkal) (19)

k

and notice that the right-hand sides of Eqs. (16) and (19) have the same
form, provided that we identify

htok cosh 20k = Ek + N0Vk, (20)

hu!k sinh 26k = -N0Vk. (21)

Since 8k was taken to be an adjustable parameter in the definitions of

a~l and ak we can choose it in such a way that Eqs. (20) and (21) are
satisfied. Consequently,

(hwkf = (Ek + N0Vk)2 - (N0Vk)2 (22)

and, therefore,

uj{k) =wk = ±[El+ 2EkN0Vk]1/2. (23)

The elementary excitations of the system described by Eq. (23) are

boson, or phonon-like,
-, 1/2 / T. N 1/2
Wfc «
h
-
^ l " ' " ' -(*£) " (24)

for
2 „ 4MN0Vk
Ek < 2N0Vk; i.e., k2 <

and they are free-particle-like,

1/2 1/2
h2k2
(JRJ - (25)
h 2M = (-
\2M
 Superfluid Transitions 59

for

Ek»2N0Vk; i . e . , ^ » ^ ^ .
a
We do not know the exact shape of Vk = V(k) as a function of wave
vector k, but, if Vk « VQ at small k and Vfe drops rapidly as \k\ goes beyond
a certain value fcc, the picture of oj(k) will show a linear increase at the
beginning, then a maximum followed by a minimum, and then a parabolic
increase typical of a free particle excitation. This implies an energy gap for
the creation of free particles. At low enough t e m p e r a t u r e s the system will
be in the condensed superfluid state. When, on the other hand, the ther-
mal energy k^T rises beyond a certain value k#Tc, free particle excitations
(broken Cooper pairs) become dominant and superfluidity disappears.

References

1. J. Wilks, The Properties of Liquid and Solid Helium (Clarendon Press, Oxford,
1967).
2. Ph.L. Taylor, A Quantum Approach to the Solid State (Prentice Hall,
Englewood Cliffs, NJ, 1970).
 Chapter 1.8

Ferroelastic Transitions

Ferroelasticity 1 can be regarded as the mechanical analog of ferroelectric-

ity and ferromagnetism. In a ferroelastic crystal, at temperatures near the
transition temperature Tc the strain (x) or elastic response to a uniaxial
stress (X) is highly nonlinear, and at T < Tc hysteresis loops in a; vs. X can
be observed, analogous to ferroelectric hysteresis loops in P vs. E or mag-
netic in M vs. H. Also, in the absence of external uniaxial stress and below
the transition temperature, a spontaneous strain, defined with respect to
either the crystal or the unit cell dimensions in the "prototype," high-
temperature phase, is developed by the crystal. This spontaneous strain is
accompanied by a lowering of the point group symmetry of the crystal, as
in the ferroelectric and ferromagnetic cases. It may be noticed that "sec-
ondary" ferroelasticity is usually present in order-disorder ferroelectrics,
accompanying the onset of ferroelectricity and being driven by it. We may
say that in order-disorder ferroelectrics the microscopic unit cell itself car-
ries the elementary dipole moment above as well as below T c , while in pure
order-disorder ferroelastics the unit cell does not carry any dipole moment
above or below Tc but presents a symmetry lowering distortion with respect
to the symmetry of the whole crystal in the high-temperature phase.
Figure 1.8.1 shows a ferroelastic hysteresis loop in which a suitably
oriented uniaxial stress switches a ferroelastic crystal from a given ferroe-
lastic orientation state to the opposite orientation state, e.g., from pseu-
dotetragonal orthorhombic slightly tilted to the right to pseudotetragonal
orthorhombic slightly tilted to the left, and vice versa.
Also shown is the temperature dependence of the average spontaneous
strain, for a single domain crystal, which in this case is the average tilt
angle that would bring back the crystal from orthorhombic to tetragonal.
As in the ferroelectric and ferromagnetic cases, in a single large crystal,

61
62 Effective Field Approach to Phase Transitions

Fig. 1.8.1. (a) Ferroelastic hysteresis loop (x = strain, X = uniaxial stress), (b) Tem-
perature dependence of spontaneous strain xs (T).

domains with opposite or different orientation of the usually very small

spontaneous strain can coexist, separated by domain walls. Macroscopic
measurements of the spontaneous strain require, therefore, the use of single
domain crystals.
The concept of "ferroelasticity," as applied to non-metallic crystals
developing spontaneous strains below a certain transition temperature, was
first introduced by K. Aizu in 1969.2 He later gave a unified symmetry
classification of ferroelectrics, ferroelastics, and ferromagnets, and investi-
gated the possible point group-subgroup pairs in which the disappearance
of one symmetry element could give rise to a continuous or second order
phase transition. Subsequently, several authors developed phenomenologi-
cal lattice-dynamical theories of ferroelasticity, in which the mechanisms by
which spontaneous strain arise are softening of zero-wave vector acoustic
modes, optical mode softening, the cooperative Jahn-Teller effect, etc. It
may be noticed that, in ferroelastic as well as in ferroelectric transitions,
two extreme cases of transitions are traditionally considered:
(a) The purely order-disorder transition, in which the microscopic strain
of a single unit cell (ferroelastic) or the microscopic dipole moment per unit
cell (ferroelectric) are temperature independent, and their value fixed for
all temperatures (below as well as above T c ).
(b) The purely displacive transition, in which the microscopic strain and
the microscopic dipole moment are markedly temperature dependent, espe-
cially in the vicinity of Tc, giving rise to a soft-mode behavior. In practice,
however, most phase transitions have a mixed (order-disorder) (displacive)
 Ferroelastic Transitions 63

character. The properties of ferroelastics in general have been recovered by

J.C. Toledano. 3
As a good example of well-understood pure ferroelastic transitions, we
will consider a ferroelastic transition driven by the cooperative Jahn-Teller
effect. A prototypical system displaying this type of cooperative transition
is the perovskite crystal PrAlC>3. The transition can be investigated in sys-
tems like this by a variety of techniques: optical spectroscopy, Raman and
Brillouin scattering, X-ray and neutron diffraction, strain-stress character-
ization, EPR, etc.
We will outline, first, the basis of the basic features of the formal theory
worked out by Eliot 4 and Pytte 5 for these systems and then we will see
that the simple effective field approach can also be satisfactorily applied
to ferroelastic transitions of this kind. The mechanism that drives a coop-
erative Jahn-Teller transition is that of electron-phonon interaction. To
understand it one may consider the fact that a lattice distortion splits the
levels of a degenerate electronic state. This is accompanied by a decrease
in electronic energy if the temperature is low enough to favor a substantial
difference in population between the lower energy split levels and the higher
energy ones. In this case, the overall energy of the system may become lower
when the decrease in energy due to population of lower energy electronic
states overcomes the increase in energy due to the lattice distortion. Then,
the distortion becomes energetically favorable, and a ferroelastic phase tran-
sition takes place precisely at the temperature at which the gain in free
energy in the electron system is equal to the loss in energy in the phonon
system associated with the lattice distortion. The simplest conceivable case
is that of the interaction of a doublet with a non-degenerated phonon mode.
The corresponding hamiltonian is

H = ^hw(q) a+aq + - + ^exp(iqRna(q)Sz(n)(aq + o+)), (1)

L J
q q,n

where a+, aq are respectively the annihilation and creation operators for the
phonon with wave vector q, Rn is the position vector for the nth ion of the
unit cell, Sz(n) is the pseudo-spin operator that determines the electronic
state of the ion located at Rn, and a(q) is a coupling coefficient between
the pseudo-spin and the vibrational state specified by q. Introducing the
displaced "mixed mode" annihilation operator

7+ • »(g)
it = <9 + &hio(q)"
; q (2)
64 Effective Field Approach to Phase Transitions

and the corresponding creation operator, Eq. (1) becomes

-9> (3)
hco(q)

in which the pseudo-spin part is identical to the Ising hamiltonian and,

therefore, describes correctly the behavior of an order-disorder system
undergoing a second order transition.
Let us investigate the effective field approach to pure second order fer-
roelastic transitions. The effective stress will be given by

X e ff = X + CX, (4)
where X is the external stress, c an effective field constant with the dimen-
sions of an elastic compliance, and x the average strain in the crystal. The
energy per unit cell associated with the unit cell distortion x, either in the
direction favored by the effective stress or in the opposite direction, will
then be given by

w = ±vc(X + cx)x, (5)

where vc is the unit cell volume, and x = xso has a fixed, temperature-
independent value in the simple case considered. Proceeding then as in
previous chapters, we get
(N1-N2)x=^=unh vc(X + cx)x
= tanh (6)
Nx ZsO kBT T xs0
where
Tc = cvcx2/kB- (7)
For X = 0, x is reduced to the spontaneous strain, x s , whose tempera-
ture dependence is then given by
{x/xs0) = T_
(8)
tanh (x/xso) T '
The critical exponents /3, 5, 7, and a can be obtained in the usual
manner and can be shown to be identical to those found, for instance, in
the ferroelectric transition (Chapter 1.6). As in the case of ferroelectrics, the
behavior of order-disorder ferroelastic crystals in the vicinity of Tc is well
described by the classical effective field exponents, except for the presence
of small logarithmic corrections, which will be discussed briefly at the end
of Chapter 1.9.
 Ferroelastic Transitions 65

1.0 -*»—•-
LU
£ a75h
o(c-a^ytc-a)0 t
| 0.5r —cos2 2 #
a.
S 02 5

X
Q
° 01^
0 0.4 0.5 0.6 0.7 0.8 0.9 1.0
T/Tc
Fig. 1.8.2. Squared order parameter as a function of temperature in PrAlC>3 determined
by optical absorption (•), strain (o), and E P R (-).

It was previously mentioned that PrA103 provides a good example of

second order transition, driven by the cooperative Jahn-Teller effect. Fig-
ure 1.8.2 shows6 the temperature dependence of the square of the normal-
ized spontaneous strain, (az)2 = (xs/xso)2, as a function of normalized
temperature, (T/Tc), as measured by means of various experimental tech-
niques at temperature T <TC = 151K.
The theoretical prediction of Eq. (8), not shown in Fig. 1.8.2, fulfills
extremely well the observed behavior of (<xz)2 = (a;s/a;so)2 as a function of
temperature.
We may inquire about the reasonableness of the relationship afforded by
Eq. (7) between the transition temperature and the physical parameters, c
(elastic compliance), vc (unit cell volume), and x = XSQ (unit cell distortion).
This can be done by writing

c« kBTc/vcx2 (9)

and substituting numerical values appropriate for PrA103- Using Tc =

151K, vc = a3 = (4 x 1 0 - 8 ) 3 and x = 10""2, one gets

CK3.2X 10 1 2 dyn/cm , (10)

which is of the right order of magnitude for a perovskite crystal like Pr AIO3.
66 Effective Field Approach to Phase Transitions

It may finally be mentioned t h a t the "martensitic" transformations,

such as those found in metallic systems like Fe-Ni, and also in some alkali
halides, in which a change takes place from a bbc structure to a fee struc-
ture, and vice versa, resemble in some respects ferroelastic transitions, b u t
involve much more drastic distortions at the unit cell level, and, therefore,
cannot be properly classed together with ferroelastic transitions.

References

1. V.K. Wadhawan, Phase Transitions 3, 3 (1982).

2. K. Aizu, J. Phys. Soc. Japan 27, 387 (1969).
3. J.C. Toledano, Ann. Telecomm. 29, 1 (1974).
4. R.J. Eliott, R.T. Harley, W. Hayes, and S.R.P. Smith, Proc. Roy. Soc.
(London) A328, 217 (1972).
5. E. Pytte, Ferroelectrics 7, 193 (1974).
6. See, e.g., review by P.A. Fleury and K. Lyons, in K.A. Miiller and H. Thomas
(eds), Structural Phase Transitions I (Springer-Verlag, Berlin, 1981).
 Chapter 1.9

Landau Theory and Effective Field

Approach. Role of Fluctuations

A very general theory 1 of phase transitions was developed by the great

Russian physicist L.D. Landau in 1937 that established the conceptual
framework for a considerable part of later theoretical work on phase tran-
sitions and is in many respects a basis for the effective field (or mean field)
approach to phase transitions.
Let us consider the simplest possible case: that of a physical system
undergoing a phase transition in which there is only one (mono-
dimensional) order parameter (77) and its conjugated field (h). Landau
theory assumes that its thermodynamic potential (generalized free energy)
can be expanded in a power series of the order parameter at temperatures
in the vicinity of the critical temperature. We can distinguish two cases,
vanishing field and non-vanishing field.
Case (a): h = 0,7] = rjo — If the thermodynamic potential or free energy
is such that F(r], h) = F(—r), —h), which is a reasonable assumption, we can
retain only the even powers in the series expansion of F in terms of 77. Then,
we have

F0 = F0 + ^Ar12 + ^Br14 + ^Cr16--- (1)

where Fo includes all contributions to F unrelated to the onset of order-

disorder in the system (and, therefore, is weakly temperature dependent),
A = A(T) is a temperature dependent coefficient (which must be so for rea-
sons discussed in what follows), and B, C, etc., are assumed to be constant
or weakly temperature dependent coefficients.
In equilibrium,

dF/drj = 0, d2F/drj2 > 0. (2)

67
68 Effective Field Approach to Phase Transitions

This means that

[An + Brf + Cr?\ n=Vo = r,0(A + Br,2 + C^) = 0 (3)

and

A + Wr,l + 5 C ^ > 0. (4)

Taking into account that the higher order coefficient, C, must be such
that C > 0 for F(n) to be stable at higher values of n, we can conclude
from Eqs. (3) and (4), first, that at

T > Tc -> 770 = 0 -f A > 0 (5)

and at

T < Tc - no ± 0 - A(?) (6)

where the question mark indicates that we do not know in advance the sign
of A for T < Tc, but we can investigate what constraints are put on it by
the different possible values of the sign in coefficient B, knowing that, as
mentioned above, C > 0. We can distinguish three possibilities for T < Tc,
and make use again of Eqs. (3) and (4), to get

(i) B > 0 -> jjg = -A/B -+ A < 0, (7)

(ii) B = 0 -> r$ = - 4 / C - • A < 0, (8)
(in) B < 0 - • rjg « - ^ [ - B ± (B2 - 4AC)1/2] -* A < B2/AC. (9)

The first possibility (i) corresponds to an ordinary critical point, since

A goes from A > 0 at T > Tc to A < 0 at T < Tc and we can write it as

A = Ao(T-Tc) + --- (10)

and neglect higher order terms in (T — Tc)n for T in the close vicinity of
T c . Obviously, from Eqs. (7) and (10),

m(T) = (A0/B)1/2(Tc-T)1'2, (11)

which indicates a critical exponent (3 = 1/2 identical to the exponent (3

obtained by the effective field approach in previous chapters.
The second possibility (ii) corresponds to a tricritical point, which
belongs still to a continuous phase transition but, near which, the tem-
perature dependence of the order parameter near and below Tc makes it
 Landau Theory and Effective Field Approach 69

to go to zero in a sharper manner that in (i). Near a tricritical point from

Eqs. (8) and (10),

r1o(T) = (A0/C)l^(Tc-T)1/\ (12)

which gives a non-classical critical exponent /? = 1/4. Case (ii) is a bor-

derline case between a continuous transition [case (i)] and a discontinuous
transition [case (iii)] as shown below.
The third possibility (iii) corresponds to a discontinuous phase transi-
tion, since the expression for the order parameter 770 (T) in Eq. (9) has real
solutions only for

A = A0(TC -T)< B2/4C (13)

and these are possible only for T < To, such that

[B2-4A0(T0-TC)C}=0. (14)

Therefore, r/o goes over from

T=(T0)_, 770 = [-B/2C]1'2 (15)

to

T=(T0)+, 7,0 = 0 (16)

in a discontinuous manner. Of course, the discontinuity will be small if To

is very close to T c , and large otherwise. Discontinuous or first order phase
transitions are usually accompanied by "thermal hysteresis," that is, the
transition occurs at a given temperature Tc when the temperature of the
system is raised, and at another (lower) temperature To — AT(th. h.) when
the temperature of the system is lowered. This is an indication that there
is a temperature range AT(th. h.) in the ordered and disordered phases
coexisting and that there are metastable states. The ratio AT(th. h.)/7b
[or, alternatively AT(th. h.)/T c ] is a good indicator of how much weakly
or strongly first order a phase transition is. We can conclude that the sign
of the coefficient B in the power expansion of F{T]Q) is very important
in determining the character (continuous or discontinuous) of the phase
transition. It may be noted that sometimes its value can be influenced
by means of another external field (e.g., mechanical pressure in the case
of ferroelectric transition) producing gradual changes from B < 0, through
B = 0 (tricritical point), to B > 0. This is possible in cases where the phase
70 Effective Field Approach to Phase Transitions

io(T)(ii) ^oCTKiii)

~(Tc-T)^

Fig. 1.9.1. Temperature dependence of the order parameter in the three cases of
(i) ordinary critical point, (ii) tricritical point, and (iii) discontinuous (first order) phase
transition.

transition at the starting point (zero or ambient pressure in our case) is only
weakly first order.
Figure 1.9.1 shows esquematically the temperature dependence of the
order parameter r)o(T), which would correspond to the spontaneous mag-
netization in the ferromagnetic case, the spontaneous polarization in the
ferroelectric case, the spontaneous strain in the ferroelectric case, etc., for
the three cases discussed above.
Case (b): h ^ 0,T] = r] — In this case, the field h conjugated to the
order parameter must satisfy

dF/dr] (17)

and, therefore, we can write

1
F = F0 -A0{T-Tc)r? + \Br1i+1-Cr1^ rjh (18)

in equilibrium we have

dF/dr] = 0, d2F/drj2 > 0 (19)

and, therefore,

h = A0{T - TC)TI + Brf + Crf (20)

which is the equation of state of the system, fully analogous to the equation
of state obtained by the effective field approach in previous chapters.
We may analyze the critical exponents to be expected for the two cases
of continuous phase transitions corresponding to (i) ordinary critical point
(OCP) and (ii) tricritical point (TCP).
 Landau Theory and Effective Field Approach 71

(i) Ordinary critical point: B > 0, T = Tc — As shown above, the critical

exponent describing the temperature dependence of the (spontaneous) order
parameter is obtained from Eq. (20) for h = 0,T < T c , where rjo <C %
(max), with the result

Vo(T) = (AQ/Bf'2(Tc - Tf'\ i.e., /? = \. (21)

The critical isotherm exponent (T = Tc) is given by

h = Brf, r] = (B)- 1 / 3 /! 1 / 3 , i.e., 5 = 3. (22)

The susceptibility exponent (T >TC,T< Tc) is given by

X-\T) = (dh/dr,) =A0(T- Tc) + ZBnl + •••

= A0(T- Tc) for T>TC ( ^ = 0) (23)
= 2A0(TC - T) {r,l = (A0/B)(TC - T)) i.e., 7 = 7 ' = 1.
(24)

The specific heat exponent, taking into account that

S = -8F/dT = S0- [(dA/dT)V2 + A(dr,2/dT)]h=0 = S0 - 0

for T>TC (25)
2
= So - 2A0[-A0(T - Tc)/B] = S0 + 2(A 0/B)(T - Tc)
for T <TC (26)

is given by

Cp = T{dS/dT)p = Cp0 for T > Tc (27)

2
= C p0 + 2T(A 0/B) for T < T c , i.e., a = a' = 0 (28)

because there is no divergence at T = Tc, but only a discontinuous jump

between (T c )_ and (T c )+,

ACP = CP(TC) - Cp0 = 2TC(A2/B). (29)

It may noted that the following equalities2 between critical exponents are
fulfilled:

(3{8-l)=i (Widom), (30)

13(5 + 1) = 2-a' (Griffiths), (31)
2/3 + 7' + a' = 2 (Fisher-Rooshbrook). (32)
72 Effective Field Approach to Phase Transitions

(ii) Tricritical point: B = 0, T « Tc — The spontaneous order parameter

dependence on temperature is now given (h — 0, T < Tc) by

Vo(T) = (A0/C)1/\Tc-T)1/4, i.e.,/? = 1/4. (33)

The critical isotherm exponent (T = TC) by

h = Crf, r, = ( C ) " 1 / 5 ^ / 5 , i.e., 6 = 5. (34)

The susceptibility exponent (T >TC,T< Tc) by

X _ 1 ( r ) = (9/1/^77) = A 0 (T - Tc) + 5Cr/4 + • • •

= 4>CT-rc) forT>Tc (772 = 0) (35)

= A0(TC-T) for T<TC (V* = (A0/C)(TC-T)). (36)

The specific heat exponent, using

S = -dF/OT = S0 - [(dA/dTtf + A(dr,2/dT)]h=0

= So - 0 for T > Tc (37)
1 2 1 2
= So-^A0(A0/C) / (Tc-T) / for T < Tc (38)

for T > T<C ;

TAoiAo/Cf^iTc-T)-1'2 for T < Tc,

(39)

a = 0, a' = 1/2.

It can be easily checked that the equalities given by Eqs. (30)-(32) are
also fulfilled by the tricritical point critical exponents.

1.9.1. Fluctuations of the Order Parameter

We will devote the final part of this chapter to investigating the role of
fluctuations 3 in the simplest case of an uniaxial system undergoing a phase
transition with a single order parameter. This implies, of course, a gener-
alization of approach with respect to the mean field approach.
 Landau Theory and Effective Field Approach 73

By definition,

2 _ jr^eM-HT^y/NkBT}^
71 (40)
- J^expi-^T^/NkBT}^ '

where <1>(T, 77) is the chemical potential of a volume v involving N unit

cells. We can assumme, therefore, that

$(T, V) = $0 + \a{T - TcW + \ ^ L . (41)

Very near T c , in a second order phase transition, we can omit the last
term in the right-hand side of Eq. (41), an omission that will be shown to
be fully justified later.
Then, making

|a(T - Tc)/kBT v2, (42)

we can write the numerator in Eq. (40) as

i a ( T - T c ) l - 3 / 2 rOO 2 , 2NJ na{T-Tcy-m

x2 exp(—x ) dx — x constant
NkBT / -00 NkBT
(43)
and the denominator as
-1/2 -1/2
\<*{T-TC, \a(T - Tc)
NkBT I
J —c
x2 exp(—x 2 )dx
NkBT
x constant.
(44)
Thus,

2 2NkBT
V = —r^—^TT x constant, (45)
a(T - Tc)

which diverges as T —> Tc. Hence, fluctuations become important as one

approaches the critical temperature.
We can decompose 77 in a Fourier series

V(r) = ^ Vkexp(-ikr), (46)

74 Effective Field Approach to Phase Transitions

where nk = n*_k, and, therefore,

Vk = ak + ibk, (47)
7]-k = ak- ibk. (48)

It can be further assumed that the thermodynamic potential is a func-

tion not only of even powers of the order parameter, n, but also of even
powers of its spatial derivative, Vrj, since wave-like spatial oscillations of
the order parameter add energy to the system. Then, we can write,

<l> = F0v+ [ [F(rj2, V\..., (Vr?)2, (Vry)4, ...) - F0] dV, (49)
Jv
where, neglecting higher order terms, the density of thermodynamic poten-
tial depending on n is given by

F - F0 « \a{T - Tc)rf{r)L + \s{Vn)2L (50)

and, therefore,

$ = 3>o + / \a(T -Tc)r?{r)L+l-5{VV)2L dv

1
Y,WT-Tc) + 5k2}r)kr,„kL (51)
k

taking into account that

exp(ikir) exp(ik,2r) dv = I „ , . ' (52)

/ 1
0 otherwise.
Note that we consider the coefficient S, in front of the lowest order term
in V?7, as weakly or not temperature dependent.
In uniaxial ferroelectrics, for instance, it is necessary to take into account
the energy contribution due to the spatial dependence of the field (E) asso-
ciated with the order parameter (P). We have

P(r) = J2pk exp(ifcr), Pz(r) = ] T P z k exp(ikr), (53)

k k

E(r) =J2Ek e
Mikr), E
z{r) = ^ E z k exp(ifcr). (54)
k k

Then, taking into account Maxwell's equations V x E = 0, VZ? =

V(E + 4?rP) = 0, one gets

kxEk=0, k\\Ek
 Landau Theory and Effective Field Approach 75

and

Ek = -47rVP fe , kEk = -4wkPk. (55)

Therefore,

l
-Jp(r)E{r)dv = -V-YJPzkEzk = -2KvY,(nr) P2VkV-k (56)

since in the uniaxial system with axis along the z direction we have

Pzx = PVk (57)

and

Ezk = -4irpr)k (58)

due to Eq. (56), using cos2 6 = {kz/\k\)2.

Including a term like that in Eq. (56) in <3? one gets

$ = F0v + -v J2 HT ~ Tc) + Sk2 + 4TT COS2 0p2]rikTi-k (59)

k

Now, we introduce this result in Gibbs relationship given by

$ _ $ 0 ~ -kBT In Z, (60)

where
oo
(61)
/
exp[-(* - $0)/fcBT] J J d % dV_k.
-OO 7.
Using rfc = a | + b\, where ak and 6^ are denned by Eqs. (47) and (48)
for k < fcmax, we can rewrite Z, changing from drjk dr/^k to 2irrk drk, as
/•oo
/•OO r
Z = /I exp
exp - » V ( a ( r - T c ) + tf

+ 47rp2 cos2 0)rl/2kBT 27rJ|r f c dr f c

-• fe
_^^ />oo
7T
TT / exp(-mr^)27rr fc dr fc = TT [exp(-mr£)]~
k Jo m

n 27rfeBr
[a(T - T c ) + <5A:2 + 47rp2 cos2 0]'
(62)
76 Effective Field Approach to Phase Transitions

Henceforth,

In ^BT_ _ ln(a(T _ Tj + Sk2 + 4np2 cog2 ^

(63)
where the first term within J^fc is independent of r\, and its contribution
can be added directly to $ 0 making if $01 • Since allowed values of k form
a quasi-continuum we can write
/*7r
/•7T />27r
rZIT ffk,
Kmax
$ « $01 + kBT / / / ln[a(T - Tc) + <5A;2 + 4TTP2 0]
7o Jo Jo

x f - ^ J (k sin 6> df?)(A; dp) dfc, (64)

where (v/8ir3) is the density of points in the reciprocal lattice, 0 < 6 < TT,
0 < <p < 2TT, and sin 6 6.6 = -d(cos0).
We can now evaluate the entropy as

S = -— = S0-kBT2n k2dk
8K3) Jo
rL ad (cos 6)
-etc
X + 4np2 cos2 6
i+i [a(T - Tc) + *fc2]

*-(s)(^)r^
/• +1 ad(cos 6>)
(65)

The second integral can then be easily carried out, resulting in

•-*- m^i: cos e/y/{a{T - Tc) +

A;2 dfc

6k2/top2)
.-|1
tan
y/(a{T - Tc) + 5k2/top2)

= S0- 1^) (£) l ^ fc2d^4^2/(a(T-Tc) + ^ )

x tan - 1 ^ ^ / ( a ^ - T J + Jfc2). (66)
 Landau Theory and Effective Field Approach 77

The region of interest is T = Tc, where k = 0; therefore, one can make

the approximation

t a n - 1 y/4np2/(a(T - Tc) + 5k2) « tan _ 1 (oo) (67)

and then write

„ „ fkBTv\ ( a \ / - — ^ n fkm™ k2 dk
(68)
y/a{T - Tc) + 6k2

and, for the specific heat,

kBT2a2 k2dk
ACp = • (69)
vTdf ~ Cp0 +
Sn3/2p J JQ (a(T - Tc) + 5k2)3/2

Sufficiently close to Tc, a(T — Tc) becomes much smaller than <5fc^ax, and
then

(kBT2a2\{a{T-Tc)/8f/2
p p0+
~ ° ^ 87r3/2p J (a(T - Tc))3/2
- {6/a{T-Tc)f/2k2dk
Jo [1 + (S/a(T - Tc))k2f2
kBT2a2\ / 1 \ rmax x2dx
Cp0+
\J^72jJ{s^J i (1+x2)3/2
fkBT2a2\ ( 1 \ Jo
Cp0 +
V"8^7^; [smj
2
r x2dx fXm" _ x dx
(70)
J0 (l + x2)V2J0 (1 + x 2 ) 3 /

where

x = [S/a(T - Tc)]k. (71)

We can approximate the two definite integrals in Eq. (70) by means of

1/2 1/2
y/S[l = 1/3, [In x}*-"™ = In , (72)
OtTr T-Tr
78 Effective Field Approach to Phase Transitions

which, substituted into Eq. (70), give

1/2
1+ 1 l n/ S 1 T-Tr (73)
3 2 fe "'ma;* ~ All
2 V Tc

where (T - T c )/T c < 1, and therefore ln((T - Tc)/Tc) < 0, which implies
' T _ T
1, T-Tc
ln

Using this result and consolidating constant terms together with Cpo
into C'p0, we can finally write

kBT2a2 T-Tr
AC ~ a + ( ) In (74)

in which logarithmic correction terms show up. The calculation is fairly

laborious but the final result is a rewarding one.
This expression, Eq. (74), can be used to analyze experimental data for
the specific heat of ferroelectric triglycine sulfate (TGS). Figure 1.9.2 shows

6C,relative units

(T-Tcl,K-
Fig. 1.9.2. Extra specific heat of ferroelectric triglycine sulfate (TGS) above T c , after
subtracting the non-singular part, as a function of ln(T — T c ).
 Landau Theory and Effective Field Approach 79

these d a t a in appropriate form for analysis of t h e logarithmic correction

t e r m near a n d above T c .
T h e above result indicates t h a t t h e effects of fluctuations become promi-
nent when

5
s
*->i, ' - ^ ( £ ) (!)'• <75>
where fcmax = 7r/6, with b t h e lattice constant in t h e polar axis direction.
Equation (75) establishes a criterion t o determine how close t o Tc fluc-
tuations become significant. For T G S , we can see in Fig. 1.9.2 t h a t at
A T < 20 K fluctuations become appreciable. Then, using t h e fact t h a t
aEc = (47r/C)T c « 1 for T G S a n d t h a t b = 12.6 x 1 0 _ 8 c m , we can get an
estimate of the coefficient 6 by means of Eq. (75),

™ - K ( S ) ( 1 V i.e.,<5«10-16esu. (76)
y
322 \{l)) Vl2.6x 1 0 " V ' '
This numerical estimate justifies, for the case of T G S , a t least, neglecting
the t e r m 1 / 2 / V in Eq. (41), because, using f3 = 1 / 3 P S Q 3 « 2.8 x 1 0 _ 1 3 e s u
for T G S , one can check directly t h a t

J/3P4 « «5(VP)2 « SfcLx-P2 * s(j) P2 (77)

since substituting numbers on t h e left-hand side of the inequality is several
orders of magnitude smaller t h a n t h e right-hand side.

References

1. See, e.g., L.D. Landau and E.M. Lifshitz, Statistical Physics, 3rd ed.
(Pergamon Press, Oxford, 1980).
2. See, e.g., P. Pfeuty and G. Toulouse, Introduction to the Renormalization
Group and to Critical Phenomena (John Wiley, New York, 1977).
3. See, e.g., B.A. Strukov and A.P. Levanyuk, Principios de ferroelectricidad
(Ed. Universidad Autnoma de Madrid, Madrid, 1988) (Translated from the
original in Russian by F. Agullo Rueda).
4. K. Ema, Y. Ikeda, M. Katayama and K. Hamano, J. Phys. Soc. Japan 49B,
181 (1980).
 Chapter 1.10

Equation of State and the

Scaling Function*

The scaling hypothesis has been the starting point for most recent devel-
opments in the physics of critical phenomena. 1-5 Several attempts to
obtain explicit scaling functions h(x), which specify the corresponding equa-
tion of state, have been made, 6 - 9 most of them showing good agreement
with selected experimental data, and/or numerical calculations for specific
theoretical models. One particularly simple expression10 can be obtained
directly from the scaling assumption together with the additional assump-
tion that the critical point $ = (di/dM 1 / | S ) = constant (with k = H/M).
This simple expression was shown to be in fair agreement with experimen-
tal data for several transitions, 10 ' 11 and with numerical results 10 for the
Ising and Heisenberg models. It was later subject to criticism 13 on the
grounds that, in general, one should make allowance for $ = $(a;), being
x = t/M1^, thus restricting its applicability to regions where $ could be
expected to remain very nearly a constant.
In the present work, it will be shown that two different approximate
expressions for the scaling function near a magnetic critical point can be
obtained along paths of constant k or constant t. These two expressions
will be shown to describe more accurately h(x) in regions near the critical
isotherm (t = 0) and near the H = 0 line.
It is useful to start the discussion by considering the mean field model
case, which, in spite of lacking the complexities characteristic of most real
systems, affords a convenient testing ground.
Consider, for instance, an ideal ferromagnetic system whose behavior
could be described by the Weiss theory (mean field). Its equation of state

*Work previously published under the title "Complementary expressions for the scaling
function near a magnetic critical point", J.A. Gonzalo, J. Phys. C: Solid State Phys. 1 3 ,
241 (1980). Copyright © 1980 IOP Publishing Ltd.

81
82 Effective Field Approach to Phase Transitions

can be written as

H = (l + t) t a n h - 1 M - M, (1)

where H = [H]/[H}0, M = [M]/[M]0, and t = (T - Tc)/Tc are dimension-

less variables representing the magnetic field, the magnetization, and the
temperature difference to the Curie point, respectively. The critical expo-
nents have their classical values /3 = 1/2,5 = 3,7 = 1. Dividing both sides
of Eq. (1) by M 3 and developing t a n h - 1 M in a power series, near the
critical point, we have

H 1 t /tanh_1M n 1 .A 1
= —l 1- I 1 M
M3 3 M2 V M 3
) M2
_1
/tanh M \ 1

and taking into account that near the critical point M? <g; 1 and i < l , one
obtains as a first approximation

h = \ +x (h = H/M5, x = t/M1/l3), (3)

which is consistent with the scaling assumption

H = Msh(t/M1/0), i.e., h = h(x) or x = x(h). (4)

From Eq. (2) it is clear that the scaling assumption may lead to incorrect
results for h w 1/3 or x « —1/3, corresponding, respectively, to very small
x ox h (i.e., to x or h comparable to M2 or t). In those cases, the terms
in parentheses in Eq. (2) cannot be neglected "a priori.'" Also, whenever
derivatives of the main variables are evaluated (for instance, % _1 at H = 0,
t > 0), approximations like Eq. (3) may lead to incorrect results.
Equation (1) can be rewritten in terms of the variables k = H/M, t,
and M, in either of the two following forms:

t= (l + fc)(M/tanh_1M) - 1, (5a)
-1
k= ( l + i ) ( t a n h M/M) - 1, (5b)

from which the special derivatives $ — (d£/dM 1 / /3 )/ c and ip — (dt/dMs~1)t,

taken, respectively, at k = constant and t = constant, can be easily
 Equation of State and the Scaling Function 83

computed

* = (1 + jfe) [tanh - 1 M - M(\ - M 2 ) - 1 ] / 2 M ( t a n h " 1 M ) 2 , (6)

2 1 1 3
ip = (1 +1) [M(l - M )- - tanh" M] / 2 M . (7)

For M 2 <S 1, they become, respectively,

$»-I(l + fc), (8)

^ « |(l+t), (9)

approaching a constant (with the same absolute value for both cases) when
fcCl and t < l , i.e., in the vicinity of the critical point (k = 0, t = 0).
Let us turn our attention now to the more general case of scaling with
non-classical critical exponents, where, in general, 1/(3 ^ (S — 1) and con-
sequently 7 = 3(5 — 1) ^ 1. We will discuss the possibility of obtaining
two expressions for the scaling function obtained taking $ = constant and
ip = constant, which should be valid in two neighborhoods of the critical
point located near the t = 0 and H = 0 lines, respectively.
(i) From

k = H/M = Ms~lh(x), (10)

one can get, by differentiation at k = k(Ml/^,t) = constant,

*=(-*>-) =yV™1/0=x-3(6-1)*®- (11)

w } ( }
\dMW)k dk/dt h'{xy
In a certain close vicinity of the critical point where M1^ -C 1, 0 <
k < l , a very weak dependence of $ on M 1 ^ and k may be expected (in
analogy with the mean-field case). Hence, taking $ « $o along x = 0, we
can integrate Eq. (11), obtaining
X
[* !£*idx
Jo h(x)
= 3(8 - 1) [
'Jo ^ - * o
^—dx,
i.e.,
0(6-1)
h(x) ( x -$
(12)
h(0) V -*o
or taking h(0) = ( - $ 0 ) w _ 1 ) ,

h(x)=(x-^0fS-1) = (x-%y. (13)

84 Effective Field Approach to Phase Transitions

The integration has been performed along lines of constant k with origin
in the critical isotherm (x = 0) either toward the low-temperature phase
(x < 0) or toward the high-temperature phase (x > 0). Then, we should
expect less accurate results as we approach x = 3>o and x « +oo, which
are farther away from x = 0, where <&o has been defined.
(ii) From

t = Ml^x{h), (14)

by differentiation at t = t(Ms~1, k) = constant,

( dfc
i II n, \ l dt/dM'-rS-l
ill,
1
i t i i v f
= 1 x{h)
\dMs-l)t dt/dk (3{8-l)x'{h)' l
'

In order to proceed as in (i) to take H = 0 as the starting line we need

to know whether ip (H = 0) is well behaved for M&~1 <C 1, 0 < \t\ <C 1,
or not. The answer can be obtained from ip — d(H/M)/d(Ms~1)\ =
(dH/dM - H/M)/(5 - VjM ' making use of the standard expansion 4
61

H(M) = XolM + a3M3 + a?>M5 + • • •. w h i c h should be valid for HmO, \t\

fixed. One gets I/J = 2as(6 — l)~1M3~s, which remains finite at t < 0 (where
M —> Ms) but diverges at t > 0 (where M —> 0). Then one must distinguish
between these two cases.
Integrating Eq. (15) along lines of constant |i| with origin in h = hi, we
obtain, if tp\ does not depend too drastically on h,

Jhi x(h) (3(6 - 1) Jh. h-ij>i

i.e.,

l//3(<5-l)
x(h) ( h — ip.,
(16)

For t < 0 (a; < 0), we can take Hi = 0; hence, hi = Hi/M^ = 0 and

_ xl-HiiM. _ r:W-i> _ r^_ ls_1} =

x ( X m
^ ~ (6 - l)Ml- ~ (6 - l)(t/x(0))W-V ~ 6 - l ~ V°-

If the upper limit of integration in Eq. (16) remains h -C 1, we should

not expect large departures of i[>(h) from ^o- Thus, for t < 0,

-x(h) (y>o - hyw*-1) 1/7

 Equation of State and the Scaling Function 85

For t > 0 (x > 0), on the other hand, we cannot take Hj = 0 (Mi = 0) as
the starting line, since for S > 3 we would have hf =* r " 1 ^ ^ - 1 ) / - ^ - 1 -+
oo and V/" = 2<i3(# — l) - 1 /Af/~ 3 —> oo along this line (we note that hf »
V>i" as iWj —» 0). It may be argued, however, that taking an arbitrary large
hf = constant as the starting line (which can hence be set arbitrarily close
to H = 0 at t = 0, but departs increasingly from H = 0 as t increases) one
can write

•£W._ (ft-^i) i e 0<x=(h-4,+)

1
h (17b)

using a;+ = (/i+ — ^ " ) 1 /' ? (' J_ 1 ). It seems reasonable to expect that expression
(17a) for t < 0, and the less satisfactory approximation (17b) for t > 0,
should work reasonably well for h « 0 and /i « /i^~, respectively, but also
that they fail as we move away from H = 0.
It was pointed out that the simple expression given by Eq. (13) appears
to be in fair agreement with experimental data for various systems (ferro-
magnetic and non-ferromagnetic) as well as with numerical calculations of
h(x) for the Ising and Heisenberg models. However, as previously indicated,
one may expect difficulties at and near the H = 0 line, both for t < 0 and
t > 0, since </>o was defined at x = 0, which is as far as it can be from
x = $o (for t < 0) and x — +oo (for t > 0), respectively.
In particular, for t < 0, x —> <&, Eq. (13) would imply an infinite zero-
field susceptibility at the coexistence curve when j3(S — 1) = 7 > 1, i.e.,
OH
Xk1 =
dM H=0

= [SM'-^x-Qo)™-1)
- (6 - l)M*-\x - fco)**4-1'-1]^. (18)
On the other hand, for t > 0, x —• 00, the power series expansion of
h(x), defined by Eq. (13) is given by

hk{x) = (x- $ o ) W _ 1 ) = x^-V{l + [(3(6 - l X - S o ) ] * " 1 + £ } (19)

at variance 12 with the well-known Griffiths expansion 4

h(x) = a^C- 1 ) ] T Hxx2W-V = xW-V [H, + H2x-2? + L] (20)

except in the leading term. The latter series converges for M < M0(t), thus
establishing an upper value for M. Equation (13) then leads to incorrect
86 Effective Field Approach to Phase Transitions

results at, and presumably very near to, the H = 0 line, as anticipated.
Let us now look at the results that are obtained using Eqs. (17a) and (17b)
instead, in which ip is defined toward the H = 0 line.
For t < 0, x -> -(^o) 1 / / 3 ( < 5 _ 1 ) , from Eq. (17a),
dH
xr1 dM H=0

+ 6M*-\-X)W-V}x_{Mims_iy (21)

The first term on the right-hand side is zero for H = 0, and putting
MS-1 = (Ml/f>)f)(6-l) = (_x)-W-l) (_t)/3(*-l) (22)

within the second term, we have

Xr 1 = ( * - l ) ( - t ) W - 1 ) = r - 1 | t P , (23)

which is non-vanishing and shows the correct temperature dependence. For

t > 0, on the other hand, we may try using Eq. (17), and argue that as hf
is made arbitrarily large, Mi becomes arbitrarily small, hence approaching
the if = 0 line. Then,

X,-1 = {SM'-^WW-V+tf] - (8-l)M*-l{x)W-»}x^Xi

x^M5'1^) - (5 - l)(t)W-V]. (24)

Now, taking into account that Mf^hf = Hi/Mi K, x t _ 1 as Mi —> 0,

we get

Xt
i _ u\P(s-i)
(t)W-i) = r;1|tpr. (25)

Combining Eqs. (23) and (25), we obtain the following ratio of critical
amplitudes:

r + / r _ = (6- I). (26)

It can thus be concluded that, while hk{x) from Eq. (13) and b{x)
from Eqs. (17a) and (17b) are only approximations of the scaling function
h(x), they show asymptotically correct behavior at the t = 0 and H = 0
lines, respectively, and, together, they appear to give a simple and accurate
representation of h{x) (see Fig. 1.10.1). However, since both the scaling
assumption and the assumptions that $ = constant and tp = constant are
 Equation of State and the Scaling Function 87

/<0
^

CP t

/>0
m
Fig. 1.10.1. Vicinity of the critical point (CP) in the t-H plane, schematically showing
(unshaded) regions where h(x), as given in Eq. (13), is a valid approximation for the
scaling function.

asymptotic approximations themselves, an evaluation of the scaling func-

tion based upon these assumptions cannot be expected to give an exact
representation of h(x) everywhere. Most available sets of scaling provide
exact representation of h(x) everywhere. Most available sets of scaling data
M(H,T), which tend to have more experimental point for t —> 0 than for
H —> 0, are more in consonance with hk(x).
A comparison of h(x) = hk(x), the scaling function given by Eq. (13),
with recent, very accurate, experimental data on nickel by Oddou et al.13
shows excellent agreement in the entire range of the data. This is shown in
Table 1.10.1, where

7 = [In /i]/[ln(l + x) (27)

is calculated from the experimental values of h = h/ho, and x = x/xo, using

ho = 0.228 and XQ = 4.087 (this amounts to a change in normalization
parameters [H]o and [M] 0 ). The numerical values of 7 obtained in this
way do not deviate appreciably from the experimental value 7 = 1.32,
compatible with the experimental values for /? = 0.379 ± 0.003 and S =
4.48 ± 0.09 [i.e., f3(5 - 1) = 1.32 ± 0.05]. Note that these values for (3 and 5
are in excellent agreement with those obtained by means of renormalization
group calculations for the three-dimensional Heisenberg model. 14
The numerical values of 7 = In h/ ln(l +2;) are obtained from Ni data 13 ;
h = h/ho, where ho = 0.228, directly from the data for x = 0; x = X/XQ,
 Effective Field Approach to Phase Transitions

Table 1.10.1. Critical exponent 7 from h(x) for Ni.

X h X h 7
-3.5 0.018 -0.856 0.079 1.310
-3 0.039 -0.734 0.171 1.333
-2 0.096 -0.489 0.421 1.289
-1 0.159 -0.245 0.679 1.284
0 0.228 0 1 —
1 0.303 0.245 1.329 1.298
2 0.384 0.489 1.684 1.309
3 0.468 0.734 2.052 1.306
4 0.561 0.979 2.460 1.319
5 0.654 1.223 2.868 1.319
6 0.750 1.468 3.289 1.318
7 0.846 1.713 3.710 1.314
8 0.954 1.957 4.184 1.320

where XQ = 4.087, from best fit to 7 = 1.32 ± 0.05 (experimental) with the
highest point x = 8, h = 0.954. This illustrates the good overall fit of the
scaling function h(x) = (x + l ) 7 to the best available data for Ni.
It may be noted that Eq. (26) predicts a ratio ( r + / r _ ) = (8 — 1) = 3.48
for nickel (isotropic Heisenberg system). Available estimates using the
renormalization group approach 15 for the three-dimensional dipolar (n = 1)
and Ising models lead to ( r + / r _ ) D i P = 2 and ( r + / r _ ) i s i n g = 5.07, comp-
ared with ( r + / r _ ) D i p = 2 and ( r + / r _ ) I s i n g = 3.82 obtained from Eq. (26).
It is customary to analyze the interdependence of the scaling function
h(x) by means of the parametric representation
H = H(0)r05, M = M(6)r0, t = t(0)r, (28)
where, in particular, the linear form of Ho and Lister is specified by
H(0) = A{\ - 62), M(6) = KB, t{9) = (1 - b262). (29)
The linear model, i.e., Eq. (29), substituted into the scaling equation
H{6)/Ms{6) = /i[*(6>)/M1//3((9)] (30)

establishes the form of the function h(x). We can check the consistency of
the linear model's fit to the data for Ni as follows:
(a) When the system crosses the critical point x = t/M1/13 changes sign
from x < 0 (at T < Tc) to x > 0 (at T > Tc) going through x = 0, where

x = t{e)/M1/0(e) = (i-b2e2)/Ke = o, ec = r 1 = 0.7543. (31)

 Equation of State and the Scaling Function 89

(b) At the same time, h(x) = H/M5 goes from h(x) < h(0) to h(x) >
h(0) crossing the critical point (see below) from T < Tc to T > Tc. In the
linear model, on the other hand, h(x) goes through a maximum at
2
d \ H(9) 1 d A9(l-9 )
= 0, 9m= (j~) = 0-7969. (32)
d9 M5{9) ~ d9
Then for 9 > 9C, up to 9 — 9m, h{x) is still increasing in spite of
the fact that already T > Tc, and for 9 = 9m, h(x) decreases instead of
increasing, reaching values lower than that corresponding to 9 — 9C. This
shows that, while this model produces a good overall fit to the data, it
leads to inconsistencies precisely nearest the critical point. Changing the
value of 9C toward that of 9m would probably worsen the overall fit to the
data. On the other hand, the simpler scaling function given by Eq. (13)
gives an overall fit to the data as good as that for the linear model, and
a better fit in the close neighborhood of the critical point, being free from
the inconsistencies mentioned above. It is fairly obvious that h(x) = H/M
goes over from h(x) < h(0) to h{x) > h(0) in crossing the critical point
from T < Tc to T > Tc. Indeed, at the H = 0 line (which is the one that
crosses the critical point) we have

lim (H/M5) =0 for t < 0 {x < 0) (33)

and, for t > 0 (x > 0),

hin (H/M*) t 7 i < \\mo(H/M*)tn+v 0<tn<tn+1 (34)

since M n + 1 < M„ for the same H. In other words, with the linear model,
the critical point (H = 0, t = 0, M = 0) can only be reached by setting the
dummy variable r, which does not enter h(x) or x, equal to zero. The set
of values H{9) = 0, t(9) = 0, M(9) = 0 is inaccessible for the same for this
model.

References

1. B.J. Widom, J. Chem. Phys. 43, 3998 (1965).

2. Domb and D.L. Hunter, Proc. Phys. Soc. 86, 1147 (1965).
3. L.P. Kadanoff, Physics (NY) 2, 263 (1966).
4. R.B. Griffiths, Phys. Rev. 158, 176 (1967).
5. M.E. Fisher, Rep. Prog. Phys. 30, 615 (1967).
90 Effective Field Approach to Phase Transitions

6. M.S. Green, M. Vicentini-Missoni and J.M.H. Levett Sengers, Phys. Rev.

Lett. 18, 1113 (1967).
7. A. Arrot and J.E. Noakes, Phys. Rev. Lett. 19, 786 (1967).
8. J. Ho, Phys. Rev. Lett. 26, 1485 (1971).
9. S. Milosevic and H.E. Stanley, Phys. Rev. B 6 , 986, 1002 (1972).
10. J.A. Gonzalo, Phys. Rev. B 8 , 3482 (1973).
11. A. Cammanasio and J.A. Gonzalo, Solid State Commun. 16, 1169 (1975).
12. T.N. Caphart and M.E. Fisher, Phys. Rev. B l l , 1262 (1975).
13. J.L. Oddou, J. Berthier and P. Peretto, Phys. Rev. B17, 222 (1978).
14. C. Domb and M.S. Green, Phase Transitions and Critical Phenomena, Vol. 6
(New York: Academic Press, 1977).
15. A. Aharony and P.C. Hohenberg, Phys. Rev. B 1 3 , 3081 (1976).
 Appendix: Effective Field Approach
to Superconductors

It is obvious that the phenomena of superconductivity and superfluidity are

basically quantum-mechanical phenomena which, for a rigorous theoretical
description, require the explicit use of quantum-mechanical language. How-
ever, it may be of some interest to show that, once the existence of Cooper
pairs is assumed, an intuitive and simple effective field approach can also
be used for these phase transitions, leading, as shown below, to reasonable
estimates of some basic physical parameters (densities of Cooper pairs).
(a) Superconductors. Up to this point, we have outlined the formal BCS
approach to superconductive transitions. In what follows we will try to
introduce an effective field approach to the superconductive transition, using
the critical magnetic field as the order parameter. This approach is some-
what unorthodox and admittedly over-simplified, but may be intuitively
useful to illustrate in a simple way the features that the superconductive
transition has in common with other phase transitions, such as the ferro-
magnetic transition for instance.
The basic concept to describe a superconductive transition is that the
of "Cooper pair": two electrons of opposite momenta and opposite spin
attract each other due to the combined effect of the polarization of the
lattice ions surrounding them and also to a minor extent due to the spin-
spin interaction.
Figure A.l illustrates how the polarization of the lattice ions can give
rise to an effective attractive force between two "over-screened" electrons
of opposite momenta at a given instant of time. At the instant of capture
in the picture, electron (1) is shown with the surrounding ions over-drawn
to itself, while electron (2) is shown with the surrounding ions over-drawn
away from itself, giving rise to effective charges slightly positive for e(l)
and strongly negative for e(2) at that particular instant. At a later instant,

91
92 Effective Field Approach to Phase Transitions

o o o o o o o o
O /© £ N O Netjittractive O 9 y ? O
O V ? W O * force ~" O ^ ( 4 O
O O O O O O O O
Fig. A.l. Pictorial description of the electron-phonon-electron attractive interaction
between electrons e(l) and e(2) in a superconductor.

the oscillations of the lattice ions surrounding the electrons will bring out
a reversal of the sign and the size of the effective charges for e(l) and e(2),
the process repeating itself again and again.
Thus, schematically, we may picture a Cooper pair as a bound pair of
electrons with opposite spins moving around each other in a circular path.
This should give rise to a dipolar (orbital) magnetic moment fi, associ-
ated with the current loop formed by the two moving electrons. Figure A.2
depicts an "ideal" Cooper pair together with its associated orbital dipole
moment.
But the weak electron-phonon-electron interaction is capable of over-
coming the Coulomb repulsion only for pairs of electrons that are physically
far away from each other, so that the polarization of the lattice becomes
more effective. This limits the total number of electrons with opposite
momenta and spin which can go into pairs to a certain maximum num-
ber N of possible bound pairs, such that for these pairs k + fco > kp (where
|/CD| is the maximum momentum for the phonon within the Debye sphere

7C: s*=-s

Fig. A.2. Pictorial representation of Cooper pair with associated dipole moment fi.
Dotted arrows indicate the mutual attractive force between electrons e(l) and e(2).
 Appendix 93

and kp the maximum momentum for individual electrons within the Fermi
sphere) and the electron that has absorbed the phonon can go into an unoc-
cupied state outside the Fermi sphere after absorbing the phonon. (We are
talking of Debye sphere and Fermi sphere as approximations to the actual
Brillouin zone and Fermi surface, respectively, to make matters simple.)
Since in any solid |/CD| -C |&F|, only a small fraction of the total number of
electrons within the Fermi sphere can go into pairs under the most favor-
able conditions, i.e., under T = OK. At higher temperatures, the random
thermal motion of the ions in the lattice will tend to break down more and
more pairs until at a given critical temperature T = Tc all pairs will be
broken and the transition from the superconductive to the normal state
will have taken place.
In this way, our basic assumptions to try an effective field approach to
the superconductive transition are: (i) each Cooper pair carries with it a
diamagnetic (orbital) dipole moment fi, which is expected to interact col-
lectively with all other dipole moments so as to minimize the total free
energy, giving rise to a macroscopic magnetization; (ii) there is a maximum
number N of possible bound Cooper pairs at T = 0 K, and, as the temper-
ature rises, Cooper pairs break down into individual electrons, which, free
to move, tend to oppose the macroscopic magnetization of the remaining
pairs. Let us write the magnetic field as

B = H + 4wM, (1)

where H would correspond to an external magnetic field and M to the

magnetization per unit volume M = Nfi. For H = 0, we have

Bs = 4TTMS = 4TTNSMS (effective field) (2)

where Ms is the spontaneous diamagnetic magnetization. There are two

possible states for each pair of electrons with \k\ in the range allowed to
form Cooper pairs: bound pair state and broken pair state. The respective
population densities for broken and bound pairs at a certain T will then be
given by

TVi = (N/Z) exp(Bsfi/kBT), (3)

N2 = (N/Z) exp(-B B /VfcBT), (4)
where the partition function is given by

Z = exp(Bsn/kBT) + exp(-Bsn/kBT) and N = Nt + N2.

94 Effective Field Approach to Phase Transitions

Subtracting Eq. (4) from Eq. (3), we get

N2 - Ni = exp(g sM /fc B T) - exp(- J B s/ x/fc B r) /5s/x\
(5)
N2 + N! exp(Bs(i/kBT)+exp(-Bsfi/kBT) \kBT J
and taking into account that

A7r(N2 - Njfi = BB, AwNfi = Bs0 (6)

where Bs0 is the spontaneous magnetic field (order parameter) at T = OK,
we get the equation of state for the system

S^ t< " h l^J =lanh ^57 1 '

= t.fl.nh I I = f-.flnh I
P)
where

Tc = 5SOMAB = 4irNn2/kB. (8)

We may note that the above results imply an energy "gap" at T = 0 K
between the bound and broken state of a Cooper pair given by

- A 0 = Bs0n = kTc, i.e., 2A 0 = AkBTc, (9)

which is in very good agreement with the relationship between the exper-
imentally observed Ao (using infrared absorption spectroscopy) and the
experimental value of To, for many type I superconductive transitions. The
precise BCS result, somewhat different from the approximate result given
in Eq. (7), is 2A 0 « 3.5fcBTc, which is fairly close to the one in Eq. (9).
From Eq. (7) it is easy to get the critical exponent for the temperature
dependence of the order parameter at T < Tc. This is done, as usual, by
expanding the hyperbolic tangent in a power series and keeping only the
first two terms for T near and below T c , where the argument is small,
resulting in

Bs(T)/Bs(0) « V3[l + (T/Tc)}1/2, (10)

which gives the effective field critical exponent (3 = 1/2.

In a similar way the finite jump in the specific heat per unit volume at
T — Tc can be obtained as

AC«^VfcB, (11)

which implies a critical exponent a = 0, in agreement with the experimen-

tally observed behavior.
 Appendix 95

Using Eqs. (6) and (8) one can obtain numerical values for /z and N as
follows:

/x = kBTc/Bs0, (12)
N = Bs0/iTTfi. (13)

Here one can substitute the known experimental values of Tc and Bs0 to
obtain numerical estimates of \i and N. For instance, using Tc = 7.19 K and
Bs0 = 800 gauss for superconductive Pb, one gets // = 1.23 x 10~ 18 (cgs-
emu units) and iV — 5.12 x 10 19 Cooper pairs/cm 3 , which are reasonable
numbers.
Table A.l gives numerical values for fi, using Eq. (12), and for N, using
Eq. (13), from the experimental values for Tc and Bs0, quoted by Ashcroft
and Mermin, 1 corresponding to the bcc superconductive series
One can compare the values of N obtained from Tc and Bs0 by means
of Eq. (11). For instance, for Nb, AC/Cn{Tc) = 1.9 and Cn(Tc) = 7 T C =
(7.56 x 103)(9.26) = 7.0 x 10 4 erg/cm 3 , according to Ref. 1.
Then,

N = [ l . 9 C n ( T c ) ] / ! * B = 6.42 x 10 20 , (14)

which is not in perfect agreement with N — 2.44 x 10 20 , given in Table A.l,

but is not badly in disagreement either.
Due to the fact that Cooper pairs are thought to be of macroscopic size
in comparison with atomic dimensions, we can, in principle, make a classical
analysis of the elementary diamagnetic dipole moment g associated with it
in terms of current i carried by the two electrons moving at velocity v in a
circular path of radius r enclosing an area S as follows:

"-«-Hs?y-(!)"=(!y- <si»
Table A.l Superconductive parameters for some bcc elements
(cgs-emu units).

Superconductor Tc Bso /J- = fceTc/Bst) N = Bso/4irn

18
V 5.3 1020 0.71 x 1 0 - 1.14 x 10 2 0
Nb 9.26 1980 0.64 x 1 0 ~ 1 8 2.44 x 10 2 0
Ta 4.48 830 0.74 x 1 0 " 1 8 0.88 x 10 2 0
96 Effective Field Approach to Phase Transitions

where u = v/r is the angular velocity. On the other hand, the energy gap
can be written as

A 0 = hu (16)

and, consequently, the radius r and the velocity can be eliminated from
Eqs. (15) and (16) as

r=[(V(e/c))(/VA0)]1/2 (17)

and

v = ur= (Ao/ft) [(h/(e/c)) ( M / A 0 ) ] V * (18)

in terms of constants and /i, which are known. For Nb we get, using p =
0.64 x 10 18 and the experimental value for A 0 = 2.42 x 10~ 15 erg,

r N b = 4.16 x 10~6cm, (19)

6
Vm = 9.6 x 10 cm/s. (20)

The orders of magnitude for r and v are, in principle, not unreasonable,

as discussed below.
Let us assume that the effective mass of the Cooper pair electrons in the
case of superconducting Nb is (m*/m) times larger than the bare electron
mass. For instance, for Nb m* « 12m at the normal state (T > T c ), and
it is likely that m* be even larger at the superconducting state, where
the electrons are "dressed" by neighboring ions as they move, due to the
electron-phonon interaction. We may now compute directly the fraction of
electrons into the first Brillouin zone gone into Cooper pairs (N/N-QZ), and
the value of the Fermi velocity (VF) for Nb, and compare them with the
results previously obtained. Assuming a spherical Fermi surface of radius
AIF for the electron states, and a thin outer shell of thickness kg for those
electrons forming Cooper pairs, we have

N _ 47rfcgfcg kg A0hs
( ]
NZB~ fkF kF ^SFf'/h

which gives (N/NBZ) m terms of observable quantities, such as Ao, m*, £y,
and s « ( C n / p ) l / 2 , the longitudinal sound velocity for the phonons. For
Nb, using A 0 = 2.42 x 10" 15 erg, m* = 12(9.1 x 10" 2 8 )g, eF = 5.32 eV and
 Appendix 97

s = (1.47 x 10 1 2 /8.4) 1 / 2 cm/s, we get

( f ) « 10.1X10- (22)

which is reasonably close to

(£) »««'»-' (23)

V v c / Nb
1 22
obtained using N = 2.44 x 1020 from Table A.l and Nc = v- = 5.5 x 10 .
The Fermi velocity is given by

vF = (2e F /m*) (24)

For Nb, this equation gives

(«F)Nb«3.9xl07cm/s, (25)

which is somewhat larger, but of the same order of magnitude than

0)Nb « 0.96 x 107 cm/s (26)

obtained by the simple arguments in Eq. (20).

Of course, the effective field approach to superconductivity outlined
above is overly simplistic to cope with the complexities of the superconduct-
ing phase transition. The semi-quantitative numerical agreements pointed
out in this chapter therefore cannot be taken too literally. Nevertheless,
it is remarkable that such a simple approach is able to describe in such a
semi-quantitative way the features of some simple type I superconductors.
(b) Superfluids. Let us try such a necessarily over-simplified description
of the superfluid transition from the effective field viewpoint. Two neigh-
boring helium atoms feel a net attractive force (through a Lennard-Jones
interaction potential, for instance), which is countered by the centrifugal
force associated with their motion around each other (even at OK, because
of their zero-point energy) and they can form a stable superfluid Cooper
pair. Like in the superconducting case, Cooper pairs can be either in the
bound state or in the broken state, which works so as to suppress superflu-
idity. When a semicircular vibrating wire of radius R is slowly rotated back
and forth through superfluid helium well below T c , 2 the wire experiences a
very low drag force. As the rotation velocity increases, however, there is a
sudden, very large increase of drag force due to pair breaking at a certain
98 Effective Field Approach to Phase Transitions

characteristic speed of the wire, i>max- The relative speed of two helium
atoms at this point may be estimated as

vp = (vmax/R)r0, (27)

where r0 is the nearest-neighbor separation between helium atoms. Since all

bound Cooper pairs may be thought of as acting cooperatively to oppose a
pair breaking, the energy necessary to break a pair may be assumed to be

2w = {Fs)vp = (NsMvP)vpj (28)

where Fs is a generalized "effective field," conjugated with the velocity v,

given in terms of the density of Cooper pairs present at NS(T) and the
momentum of each helium atom within a pair. Prom here we can proceed
like in previous sections to get

^ - ^ = tanh (J?-) = tanh (»«MW»* £_) , (29)

v ;
N Ns0 \kBTj \ T iVs0y
which determines, in this simplified picture, the temperature dependence
of the order parameter (superfluid Cooper pair density). Equation (29) can
be written as
Ns
= t a n (T Ns \
(30)
c

^ Hr^J'
where

Tc = Ns0Mvl/2kB. (31)

Thus, we can get for the superfluid energy gap

^ A = Ns0Mv2p = 2kBTc, (32)

which is analogous to the expression obtained in Chapter 1.4 for the super-
conducting gap.
The maximum number of Cooper pairs in 4 He is given by

N = p/2M = 1.09 x 10 22 pairs/cm 3 (p = 0.145g/cm 3 ), (33)

which can be compared to ATs0 from Eq. (31) using the experimental values
for Tc = 2.18K and for vp = (vmax/R)r0, where vmax = 0.9cm/s, R =
0.15cm, and VQ = 2.51 x 10 _ 8 cm may be used, resulting in vp — 1.5 x
10 _ 7 cm/s. 3
 Appendix 99

W i t h these d a t a

Ns0 = 2kBTc/Mvl « 0.40 x 10 2 2 p a i r s / c m 3 , (34)

which is not far from t h e experimental maximum number of possible Cooper

pairs at OK in 4 H e given by Eq. (33).

References

1. N.W. Ashcroft and N.D. Mermin, Solid State Physics (Holt, Rinehart and
Winston, New York, 1976).
2. J.P. Carney, A.M. Guenault, G.R. Pickett and G.F. Spencer, Phys. Rev. Lett.
62, 3042 (1989).
3. This can be extrapolated from data for noble gas crystals. See table in N.W.
Ashcroft and D. Mermin, Solid State Physics, p. 401 (Holt, Rinehart and
Winston, New York, 1976).
 Part 2
Some Applications to
Ferroelectrics: 1970-1991
 Chapter 2.1

Behavior at T = Tc of P u r e
Ferroelectric Systems with Second
Order Phase Transition*

The second order transition in ferroelectric triglycine sulfate (TGS) seems

to be a very good test case for the mean field theory. Previous work 1 ' 2
has shown that the behavior of the dielectric constant and the sponta-
neous polarization is in agreement with the mean field predictions. The
present investigation, partially reported in a previous letter, 3 aimed at
a more complete analysis of the order-disorder cooperative transition by
means of a detailed study of the variation of polarization with electrical
field, as well as with the temperature near the critical point. Accurate
data of P versus E near Tc allow the determination of critical exponents
through log-log graphic representations. In addition, once the two funda-
mental parameters /? and d, defined by (-PS)TRSTC = const, x [1 — (T/Tcyf and
1 6
(P)T^TC = const, x E / , are determined, the way is open for the search of
a "law of corresponding states" in terms of the properly "scaled" variables.
The sample preparation and experimental procedure were described in
previous communications. The determination of the Curie temperature was
done in two different ways. First, a plot of the squared spontaneous polar-
ization (Ps2) vs. temperature was made, which showed an almost perfect
linear behavior yielding Tc by extrapolation to Ps2 = 0. Alternatively, the
method described by Kouvel and Fisher 4 was used, yielding the same result
within experimental accuracy. It has been noted by Reese5 that corrections
due to the electrocaloric effect should be considered. While the accurate

*Work previously published under the title "Equation of state for the cooperative transi-
tion of triglycine sulfate near T," J.A. Gonzalo, Phys. Rev. B 1, 3125 (1970). Copyright
© 1970. The American Physical Society.

103
104 Effective Field Approach to Phase Transitions

determination of these corrections near Tc is not easy, reasonable estimates

indicate that our results would not be substantially altered by them. It may
also be noted that perfect compensation of the P vs. E hysteresis loops very
near Tc could not be fully achieved with the Sawyer-Tower circuit, possibly
due to a field dependence of the conductivity of the crystal. This behavior
actually sets limits of AT = Tc - T at +0.22 and -0.04°C within which a
reliable determination of P for very small E was not possible.
As is well known, an increase of the amplitude of the ac field applied
to the sample for displaying the P vs. E curve produces a relatively small
increase of the absolute value of the polarization with respect to the cor-
responding values for our ac amplitude. However, the relative variation of
the polarization as a function of temperature was checked for various field
amplitudes and it was found to be the same, the absolute values being
different only by a constant factor. This effect might be attributed to a
consistently partial switching of the ferroelectric domains at low ac ampli-
tudes. The constant ac field amplitude chosen in our case, E = 190V/cm,
was relatively low, which helps to keep down the electrocaloric effect in the
vicinity of Tc.
The experimental results below T c , as described in a previous letter, 3
were shown to yield the value of the critical exponents S and (3, along with
four other exponents indicating the field and temperature dependence of
both derivatives of the polarization with respect to field and temperature.
The experimental values obtained from log-log plots of the data are given in
Table 2.1.1 and compared with those calculated from the mean field model,
using the expression6 where EQ « 4.4 x 106 V/cm is the saturation internal
field and N/u, = 4.3 /iC/cm 2 is the saturation polarization. It is interesting
to note that, as it should be expected (see Appendix), the ratio of the two
critical exponents relating the same derivative of the free energy to field
and temperature is constant.
In Table 2.1.2 a summary of data for polarization and field at various
temperatures below and above Tc is given. These data were "scaled" to
determine p = P/t^6 and e = E/t0S, and plotted using a log-log scale.
It can be seen from Fig. 2.1.1 that the scaling of the data is quite good,
giving the evidence of the existence of a law of corresponding states. From
this, the sequence of critical exponents, found directly and reported in a
previous short communication, 3 results in an automatic fashion. What is
more important, however, is the fact that this log-log representation, which
shows the critical behavior over a wide range of three decades in the reduced
field e, shows clearly the asymptotic behavior of the equation of state for
 Behavior at T = Tc of Pure Ferroelectric Systems 105

Table 2.1.1. Experimental critical exponents from TGS compared with mean field
theory predictions.

Defining Experimental value Mean field relationship Theoretical

relationship value

(i^teO-eTs = 1/5 = 0.32 ± 0.02 (P)t=o = p e ) 1 ^ 1 1

73 73
= 5 = 3

( P ) e = 0 ~ ei* 74 = P = 0.50 ± 0.03 (P) e =o = ( 3 t ) 1 / 2 74 = / 3 = -

1-P2)
( — | ~e77 77 = 0.66 ± 0 . 0 5 77 = - -
V9e/t=0 9e / t=o

~e~>s 78 = - i = 0.95 ±0.10 f^) -P2)

= £• 78 = - 1
de
)e=0 \9eJe=0 (t-p2)
dp dp\ tanh p(l-p2)
_1
1
; e79 79 = - 0 . 3 3 ± 0.05 — 79 = — x
9tJt=o ' " " "" \dt)t=o
9p\ -tanh_1p(l-p2) 1
-eTio 710 = - 0 . 4 5 ± 0 . 1 0
\dt)e=0 a«/ e =o' (*- P 2 ) 71
° =
"2

Table 2.1.2. Polarization vs. field for T G S from hysteresis loops in the vicinity of the
Curie temperature.

Below Curie temperature Above Curie temperature

2 2
P(/iC/cm ) AT ( x l O " °C) E• ( V / c m ) P(/iC/cm2) A T ( x l O - 2 °C) E (V/cm)

0.217 4.2 49.7 0.1085 2.3 12.7

0.217 10.7 27.7 0.1085 8.7 21.1
0.217 17.1 9.3 0.1085 15.2 30.3
0.244 4.2 73.0 0.1085 21.7 40.2
0.244 10.7 46.9 0.163 2.3 33.1
0.244 17.1 24.5 0.163 8.7 49.3
0.271 4.2 101.8 0.163 15.2 60.6
0.271 10.7 72.4 0.163 21.7 71.9
0.271 17.1 46.4 0.217 2.3 69.8
0.271 30.1 7.0 0.217 8.7 88.1
0.298 4.2 137.9 0.217 15.2 104.3
0.298 10.7 104.5 0.217 21.7 117.7
0.298 17.1 74.6 0.298 2.3 131.8
0.298 30.1 25.4 0.298 8.7 148.7
0.326 4.2 182.7 0.298 15.2 166.4
0.326 10.7 144.5 0.298 21.7 186.1
0.326 17.1 104.6
0.326 30.1 53.8
0.326 43.0 9.9

(1 - t) t a n h _ 1 ( P ) -P,E = E/E0, t = 1 - (T/Tc), P = P/Np,.

106 Effective Field Approach to Phase Transitions

r—I I I I rl -I—I—I I I I 11

e. E/h-(T/T c |l^ 8

Fig. 2.1.1. Log-log plot of the scaled polarization vs. scaled electric field for ferroelectric
TGS near the Curie temperature. The full line is renormalized mean field equation of
state with m = 0.450, n = 0.139.

both small and large e, above and below T c . This asymptotic character is
in complete analogy with the observations of Green et al.7 for liquid-vapor
transitions in a good number of systems. We have also recently examined
very accurate data 8 ' 9 from ferromagnetic transitions, and the asymptotic
trend for small and large scaled magnetic fields is seen again to be fully
analogous.
The asymptotic behavior can be summarized as follows:
Below Tc:

pe—o = const., (la)

Pe-,00 = const, x e1/5. (lb)

Above Tc:

pe-»o = const, x e, (2a)

pe-,oo = const, x e ' . 1 (2b)
 Behavior at T = T c of Pure Ferroelectric Systems 107

The implications of these expressions are obvious: (la) means that for
E <C t@s, below Tc, we are approaching the coexistence curve, i.e., P s =
const, x t13; (lb) and (2b) mean that for E » t&& we are approaching
the critical isotherm, i.e., P = const, x El/S; finally, (2a) means that for
E < t0S, above Tc, we are approaching AP/AE = const, x f 7 , with
—7 = (3-/36 = —7, which in our case merely expresses the Curie-Weiss law.
The basic expression of the mean field model for ferroelectrics can be
written as

Em = (lmt) tanh _ 1 (p) - P,

where t = |1 — (T/Tc)\; the negative sign applies at T < Tc and the positive
sign at T > Tc. This equation can be expanded in the following way:

Efi=(p+ i p 3 + ^P5A\ id (P + i p 3 + ^ P 5 A ) - P

3 2 1 l 2
Putting e = eE/t / and p3= +tP/t
M = HP + gP Ml3 / + 5P 5 (1 ^ ) + A

Obviously, if t < 1 (for instance, 1.0 x 10" 5 < t < 3.0 x 10" 3 in our
experiment), this expression reduces itself to

e_ = p f^p2 - 1J for T < Tc, (3a)

e+ = P (\p2 + l) for T > Tc. (3b)

To check these equations against the experimental results it has been

found necessary to introduce proportionality factors for e and p in the above
equations. They become
1
me- = np If —np
2 2—

me+ = np ( -n2p2 + 1 j .

To introduce these proportionality factors is equivalent to modifying

the normalization parameters in such a way that (Nfx)/n replaces (Nfi),
108 Effective Field Approach to Phase Transitions

and Eo/rn replaces EQ. The best fit to the data is obtained with

m = 0.450, n = 0.139.

Figure 2.1.1 shows a plot of the mean field equation of state in scal-
ing form, along with the experimental data. The agreement is very good
except for a few points for T < Tc in the intervening region between small
and large e, which fall slightly above the theoretical curve. The estimated
experimental errors go from 5 to 1% as p increases and from 10 to 2% as e
increases.
The realization that the asymptotic behavior specified by Eqs. (la)-(2b)
is not only characteristic of our ferroelectric cooperative transition, but also
of liquid-vapor and magnetic cooperative transitions, strongly suggesting
the convenience of using it along with Widom's homogeneity requirements
to specify the equation of state for the system under consideration through-
out Tc and in its vicinity.
Since the formulation of the homogeneity assumption 10 for the free
energy of a cooperative system undergoing a second order phase transition,
considerable progress has been made in the understanding of the critical
phenomena. 11 Griffiths12 has studied the problem of constructing explicit
analytic expressions for the equation of state relating the scaled exten-
sive variable (polarization, magnetization, volume, etc.) to the intensive
variable (electric field, magnetic field, pressure, etc.), respectively, for the
case of rational critical exponents. Very recently, several empirical 9 ' 13 and
parametric 14 expressions have been proposed to fit the equation of state
of some real systems. We wish to construct a compact expression of the
free energy in a simple way, matching the critical exponents sequence both
above Tc and below it, as well as the asymptotic behavior indicated in the
preceding paragraph, from the law of corresponding states.
Let us assume, following Widom 10 and Griffiths,12 that the free energy
about the critical point can be given simultaneously by

F{X,t) = X^+^'s ^ + a^x^)+a4xWs) +A

forX1//3,5»<(T>Tc), (4a)

h + hf^j+ht^) +A
for t0S > X (T < T c ). (4b)
 Behavior atT = Tc of Pure Ferroelectric Systems 109

Here, X = X/X0 is the reduced intensive variable and t = 1 — (T/Tc)

the reduced temperature. (It may be noted that while the expansion (4b)
is very familiar in the literature since the introduction of the homogeneity
assumption, relatively less attention has been paid to the complementary
expansion (4a); Ho and Litster have made use of the latter in their recent
work9 on CrBr3.)
These expansions ensure a sequence of critical exponents of the expected
form
X(6+l)/6-(l//36)
(F)t=0 « X^)l\ S = (dF/dt)t=o
(5a)
,X(S+l)/5-2(l/0S)^
C = (d2F/dt2)t=0 R
t0(6+l)-06
(F)T=0«^+1), Y = (dF/dX)x=0
(5b)
Yx = (d2F/dX% ! = 0 w t«*+i)-2/M,
where the "gap" exponents are (1/A) = 1/(36 and A = (36, respectively.
The last two expressions of (5b) are easily recognizable as the defining
equations for the indices (3 and —7 = (3 — A, respectively. Let us call Y the
partial derivative of the free energy with respect to the variable X. Its mean-
ing will be, of course, that of the respective extensive variable in the various
cases (polarization, magnetization, volume, etc.). Prom (4a) we obtain

OF t t
Y Xl's a\ + a 2 a3
dX Xl/Ps x1/?6

+ Xl's ai + a,2 t t
1 + 3a 3 1 36 +A
x /^ x //
t
x - (36) (6a)
\Xl/Ps

X
dx &i+26 2 363
w] +L (6b)

or, in other words,

y = Y/t" = xlls[Cl + c2(x-1/(jS) + c 3 (ar 1 / / 3 5 ) 2 + L]

for x = X/tps > 1 (T > T c ), (7)
2
y=[di+ d2(x) + d3(x) + L] for x «; 1 (T < T c ). (8)
Our aim is to get a single expression for y which combines Eqs. (7) and
(8) at T < Tc, approaching each of them for the limiting cases of x » 1
110 Effective Field Approach to Phase Transitions

and x <^C 1. One can write formally

y = x1/sip1(x-1/f3d) + %fa(x) for T < Tc (9)

1
y = z / ^ (a;-i//M) for T < Tc (10)

where ipi and tp2 stand for the factors within brackets in Eqs. (7) and (8).
This is our equation of state which already involves the correct sequence
of critical exponents throughout the series expansion of ip\ in powers of
x-i/ps a n ( j 0 f ^,2 m p 0 w e r s 0 f x. Below Tc, according to Eqs. (4a) and (4b),
ipi{x~1/^d)2 should predominate for x 3> 1, and ^(x) for x -C 1. Above
T c , it is clear that the spontaneous order ceases to be non-zero for x = 0,
so it is reasonable to eliminate the contribution from ip2(x). At this point,
the empirical asymptotic behavior indicated in the preceding paragraph
should be incorporated. Below T c , for x -C 1, 4>2(x) should approach a
constant, and for x 3> 1, ipi(x~1//3S) should also approach a constant,
according to (la) and (lb), respectively. Above T c , ipi(x) does not exist
and V'i(£~1/'8'5) should approach a value proportional to a;1_(1/'5)forI < 1 ,
remaining the same as below Tc for x 3> 1. One could try different functional
expressions for tp2 and tp\, all of them susceptible to being expanded in the
power series of the required form. In principle, a logarithm, a binomial, or
an exponential would meet this requirement. However, after testing these
three forms against the experimental data, not only for TGS but also for
magnetic and liquid-vapor systems, one comes to the conclusion that the
logarithm changes too slowly with x and the exponential, on the other
hand, too rapidly, in order to satisfy the asymptotic behavior indicated.
On this ground, only the binomial forms are left as satisfactory ones. The
simplest binomial forms one can think of, meeting the above-mentioned
requirements, are

1+ -I/PS' -P6{l-1/S)
ip1(x-1/0S
) = A
fe)
/

1
T \ "

if \
-(l/06)(l-0)
5 (11a)

Mx) = B
r\i\ (lib)

The exponents -08(1-1/5) inEq. (11a) and -(l/05)(l-0) inEq. (lib)

are the simplest ones that keep the homogeneity of Eq. (9) from x/x\ <S 1
to x/x2 3> 1 through the whole range in x. Also, the former is automatically
required by condition (2b).
 Behavior at T = TC of Pure Ferroelectric Systems 111

As a check of the "phenomenological" equation of state obtained, the

principal critical exponents may be calculated. Below T c , from Eqs. (6)-
(10), one obtains

x < 1, Y « fo^ » Btp, (12)

1 5 1 5
x>i, y « V'IX /' « AI / , (13)
1 s 1
x «i, ay/sx = x ' d^1/dx + (1/5) x^ /^-Vi
+ t0dil>2/dX = Cit13-^ = di"7'. (14)

Similarly, above T c ,

a; < 1, y « ^ i ^ 1 / 5 » 0, (15)
1 / < 5 1 5
i»l, y » ^ « AX / , (16)
(1/ )_
a; « 1, 8Y/8X = X^^/dX + {1/5) X * Vi
- 4 7
= C^ " = C2^ . (17)

The constants that appear in Eqs. (14) and (17) are, respectively,
_ A 1-/3 B A

It is interesting to note that 7 = 7', also supported by available experi-

mental evidence.
Figure 2.1.2 shows that the use of Eqs. (11a) and (lib) in the equation
of state given by (9) and (10) leads to excellent agreement with the exper-
imental data for ferroelectric TGS, below Tc as well as above Tc in this
case, y = p (scaled polarization) and x = e (scaled electric field). Only four
dimensionless numerical parameters have been used, their values being

A = 2.12, Xl=ei= 0.907,

B = 1.87, x2 = e2 = 1.425. (18)
For various liquid-vapor systems, it was earlier reported by Green et al.7
that the data suggest a scaling law asymptotic behavior as that indicated by
Eqs. (1) and (2). Using Green and coworkers' critical exponents, j3 = 0.35
and 5 = 5.0, one could try to fit Eqs. (9) and (10) to the data, given
in the chemical potential-density representation, in order to determine A,
x\, B, and x2. Since the scattering of the experimental points (collected
from many authors on many different systems and temperature intervals)
is fairly high, it does not seem to be justified. However, accurate data 1 5
for He 4 are available. By using the tabulated data of Roach, 15 one can
112 Effective Field Approach to Phase Transitions

• • E/ll-(T/T e l|/3S

Fig. 2.1.2. Log-log plot of the scaled polarization vs. scaled electric field for ferroelectric
TGS near T c . Pull line is the phenomenological equation of state with A = 2.12, B = 1.87,
xi = 0.907, x2 = 1.425.

calculate the fundamental critical exponents in the pressure-volume repre-

sentation. Since the transition occurs at a very low temperature, it is not
surprising that the asymmetry of the experimental data is considerable. It
is convenient to bypass this difficulty by using the following definitions:

(^gas — Miq) cx AT13 (along coexistence curve), (19)

V{-AP) - V(AP) - V(AP) oc AP1/S (along critical isotherm), (20)

where V is the volume, T is the temperature, and P is the pressure.

In this way, a nicely defined straight line for two decades up to the
vicinity of the critical point is obtained in the log-log plot, which yields /?.
The analog plot for S is only approximately linear in the last decade up to
the vicinity of the critical point, and since the trend suggests an increasing
value of S, we extrapolate to the closest value that does not violate Griffith's
inequality, taking a' w 0. This results in

(3 = 0.411 and 5 = 3.84 (21)

 Behavior at T = TC of Pure Ferroelectric Systems 113

These numerical values are somewhat different from those obtained by

Roach 15 and Vicentini-Missoni13 but it should be taken into account that
they used the density instead of the volume and neglected the asymme-
try. By using the exponents given by Eq. (21), one can scale the data
corresponding to several isotherms above and below T c . The results are
seen in Fig. 2.1.3(a) where the phenomenological equation of state is
represented, with

AV/Vc , AP/Pc
y= v = a—
Ifi and x — p ~ t06

where V = 14.49cc (per gram), Tc = 5.193K, Pc = 1710.0Torr. The equa-

tion that best fits the data has been obtained by using the dimensionless

err T l '•• "I '"T-« I ' 1 • I T T I ' I —i—i—i i i i .)• pivpn— -» i -i-X-r-f'TlJ
60 - -***^^**-
50 $' 0.41 *~~^9^ '
<H. 4.0
- S " 3.43 ZlIi-4-fl-"'~0r* '.
^ 30
' _ C > - - - ^ H ^ ^ ^ V A 5 ^ r A T (T < Tc 1 AT(T>TC) "
1-
T Zp „ » " " ^ * T > Tc O 0.053*K • O.OOS'K -
- ~~k~^ * 0.027 A 0.027
<> - \P^ V 0.004 T 0.071
<]

> 1.0 . (Rooch) .

o.e
'' */
' / • -
^ / 4
0.6 .. i . - j u j ' . hrf.ij.l.M.1. . 1 . 1 . 1 , l.l.UJ,! ..j L. . i . i . i .~
r
r„ .1.1
10°
p=a£/|i-(T/T c i|^
( o ) Liquid—vopor H«

I ' I ' I ' I'l

10 10'
* i ./38
(b) Ferromo«Mtic Ni.

Fig. 2.1.3. Log-log plots of scaled quantities for (a) liquid-vapor He 4 , volume versus
pressure; (b) ferromagnetic Ni, magnetization versus magnetic field (averaged data). Full
lines are phenomenological equations of state with (a) A — 1.92, B = 1.83, x\ = 7.57,
x2 = 11.3; and (b) A = 1.18, B - 1.42, x i = 0.334, x2 = 0.360.
114 Effective Field Approach to Phase Transitions

parameters
4 = 1.92, x1=p1=7.57,
l }
B = 1.83, ar 2 =p2 = H.3.
An estimate of the experimental errors from Roach's data indicates that
they go from 7 to 2% as v increases, and from 20 to 4% as p increases.
Finally, accurate data for the ferroparamagnetic transition in Ni, by
Kouvel and Comly,8 have also been examined. The result is shown it
Fig. 2.1.3(b). Again, the corresponding phenomenological equation of state
is plotted with
M/M0 , , H/H0
V = m= t0 and x = h= ,
6
where M0 = 58.6emu/g, H0 = kTc/fi0 = 15.2 x 10 Oe. The equation that
best fits the data is obtained with
A = 1.183, an = fti = 0.334,
(
B = 1.421, x2 = h2 = 0.360. '
Since no tables are given in Ref. 8, we cannot give an estimate of the
relative errors. However, they must be small, given the small scattering of
points in the graphs.
In Table 2.1.3, a comparison is made of the main critical exponents and
coefficients for TGS, He 4 , and Ni, along with those of the mean field theory.
The principal conclusions of the present work may be stated briefly as
follows:

1. The scaled data for P versus E from TGS in the vicinity and at both
sides of Tc satisfy very approximately the mean field theory predictions.
2. A phenomenological equation of state has been constructed, based on
the homogeneity assumption, which is simpler than previous proposals

Table 2.1.3. Comparison of critical exponents and coef-

ficients (see text) for various real systems and the mean
field model.

System 0 S PS A B

Ferroelectric TGS 0.50 3.0 1.50 2.12 1.87

Liquid-vapor He 4 0.41 3.8 1.57 1.92 1.83
Ferromagnetic Ni 0.38 4.6 1.74 1.18 1.42
Mean field 0.500 3.00 1.500 1.44 1.73
 Behavior at T = TC of Pure Ferroelectric Systems 115

and reflects in a natural way the different asymptotic behavior for low-
and high-scaled intensive variables (electric field in the case of TGS).
3. The application of this phenomenological equation of state to represen-
tative ferroelectric, liquid-vapor, and ferromagnetic transitions shows
fair agreement with the data in all three cases. In the case of TGS, the
agreement is excellent and improves that of the mean field theory. All
experimental points are within the estimated error limits. In the case of
He 4 there is appreciable scattering of points at low p above T c , and at
high p below Tc. However, taking into account the experimental uncer-
tainties, the agreement is fair. In the case of Ni, for which very accurate
data are available, the agreement is also fair, but some small systematic
deviations seem to be present, especially for T > Tc.

Appendix

From the inspection of Eqs. (3a) and (3b), it is readily seen that the two
critical exponents from the same derivative of the free energy, Fn^m =
dn+mF/Xndtm, are related in a simple way. Let us call -jh and 'jk+i as
exponents that define the dependence with X and t, respectively. They are

7fe = (6 + 1)/S - m{l/p8) - n,

(A.l)
7fc+i = 0(6 + 1)/S - n/35 - m,

as obtained by using Eq. (4a) for 7fc and Eq. (4b) for "fk+i- These exponents
define relationships

F a;XSk(X>t ; l//3«5) ;
1
m,n ^ (A.2)
F a- £7fc+l <tl/0S »X)
The ratio is then
Ik (S + l)/S - m(l/f3S) -- n
7fe+i " 0S(5 + 1)/S -nPd-m ~ [35 ~ C ° n S t (A 3)
'
This general equality is quite useful, and is already implicit it earlier
theoretical work (see Fisher's 12 work and references therein). By using
Eq. (A.3), one can easily construct equalities relating triads of critical expo-
nents. Let us take, for instance, the four most commonly used exponents,
i.e., 5 (critical isotherm), /? (coexistence curve), —7' (compressibility versus
temperature), and —a' (specific heat versus temperature). Four triads can
116 Effective Field Approach to Phase Transitions

be made in the following way:

[(1/5) + 1 ] / ( - a ' + 2) = 1/05, i.e., a ' + (3(1 + 5) = 2, (A.4)

[(1/5) - 1}/(-i) = 1//35, i.e., 7 ' +0(1-8) = O (A.5)

and eliminating successively (3 and (5 from Eqs. (A.4) and (A.5),

a' + 25 - i - 5(a' + 7') = 2, (A.6)

a' + 7 ' + 2/3 = 2. (A.7)

Expressions (A.4), (A.5), and (A.7) can be recognized as the equality

form of relationships introduced by Griffiths, W i d o m (also referred to as
the Kouvel-Rodbell relation), and Fisher-Rooshbrook. By using (A.3), any
desired relationship between three arbitrary critical exponents may be easily
obtained.
T h e series of experimental exponents available from T G S enable a direct
experimental check on the constancy of the exponent ratio specified by
Eq. (A.3). Table 2.1.3 shows t h a t the critical exponents associated with
Fifi = P, F2fi = dP/dE, and F\^ = dP/dT satisfy the expected ratio
Ik/lk+i = 3/2.

References

1. J.A. Gonzalo, Phys. Rev. 144, 662 (1966).

2. P.P. Craig, Phys. Lett. 20, 140 (1966).
3. J.A. Gonzalo, Phys. Rev. Lett. 2 1 , 749 (1968).
4. J.S. Kouvel and M.E. Fisher, Phys. Rev. 136, A1626 (1964).
5. W. Reese (private communication). It should be noted that precisely because
of the method we have used to determine T, in spite of the fact that the cor-
rections due to the electrocaloric effect can affect the absolute value of T,
the associate correction in (T — T c ) should go to zero as one approaches
T c , the temperature at which the hysteresis loops are recorded to practi-
cally disappear. Recently, very accurate experiments by E. Nakamura et al.
(Proceedings of the Second International Meeting on Ferroelectricity, Kyoto,
Japan, 1969), free from electrocaloric effects, establish conclusively the clas-
sical values previously reported for the exponents 7 and (3, the former even
at temperatures as close to T as T — Tc « 0.01° C.
6. J.A. Gonzalo and J.R. Lopez-Alonso, J. Phys. Chem. Solids 25, 303 (1964).
7. M.S. Green, M. Vicentini-Missoni and J.M.H. Levelt Sengers, Phys. Rev.
Lett. 18, 1113 (1967).
8. J.S. Kouvel and J.B. Comly, Phys. Rev. Lett. 20, 1237 (1968).
9. J.T. Ho and J.D. Litster, Phys. Rev. Lett. 22, 603 (1969).
10. B. Widom, J. Chem. Phys. 4 3 , 3898 (1965).
 Behavior atT = Tc of Pure Ferroelectric Systems 117

11. See, for example, M.E. Fisher, Rep. Progr. Phys. 30, 615 (1967).
12. R.B. Griffiths, Phys. Rev. 158, 176 (1967).
13. M. Vicentini-Missoni, J.M.H. Levelt Sengers and M.S. Green, Phys. Rev.
Lett. 22, 389 (1969).
14. P. Schofield, Phys. Rev. Lett. 22, 606 (1969).
15. P.R. Roach, Phys. Rev. 170, 213 (1968).
 Chapter 2.2

Effects of Dipolar Impurities

in Small Amounts*

It is well known1 that a-alanine doped triglycine sulfate (TGS-a) crystals

have outstanding pyroelectric properties at room temperature and have
been widely investigated as ideal materials for pyroelectric detectors. The
presence of an a-alanine concentration dependent effective internal bias
in these crystals stabilizes their excellent pyroelectric properties in a wide
temperature interval from room temperature to well above the transition
temperature, Tc « 49°C, of pure TGS, at which its crystal structure changes
from P2i to P2i/m.
Early work 2-4 on TGS-a implicitly assumed that, since the polarity of
this crystal was consistently recovered on going back and forth through
T c , the effective internal bias was roughly temperature independent. Later
experimental investigation of the temperature dependence of low-frequency
TGS-a hysteresis loops in the close vicinity of Tc showed a pronounced tem-
perature dependence of the internal bias, 5 which, from an approximately
constant value at T <C T c (proportional to the a-alanine content), drops
quickly, but continuously, as the temperature is raised through T c , and tends
asymptotically toward zero when the temperature is further increased. The
fact that it never actually reaches zero is consistent with the observed recov-
ery of the former polarity of the crystal when the temperature is lowered
again below T c . Since the above-mentioned work5 was first published, addi-
tional data on the temperature behavior of the dielectric constant 6 ' 7 and
the specific heat of TGS-a have confirmed (in contrast with the observed

*Work previously published under the title "Statistical theory of a-alanine doped
triglycine sulphate near Tc and comparison with experimental data," J.E. Lorenzo,
J.L. Martinez, and J.A. Gonzalo, Ferroelectrics 88, 101 (1988). Copyright © 1988.
Gordon and Breach Science Publishers S.A.

119
120 Effective Field Approach to Phase Transitions

temperature behavior of pure TGS under the effect of external fields of vari-
able intensity) the pronounced dependence of the effective internal bias in
TGS-a crystals. Figure 2.2.1 summarizes schematically the different effects
of external and internal biases in TGS.
Recent work9 analyzing the effect of hydrostatic pressure in pure and
a-alanine doped TGS suggests that the remarkable effectiveness of very
small amounts (30-100 ppm by weight in the sample) of a-alanine to pro-
duce a bias can be understood in terms of local extended defects, made

External Field

30 T 55 » T 55

cz
x!0" a

4» T SO
c

Fig. 2.2.1. A comparison of hysteresis loops, inverse dielectric constant and specific
heat behavior for pure TGS (with various external bias fields) and TGS-a (with various
alanine concentrations giving rise to different internal bias fields). Note that in all three
cases the effect of an internal bias field near and above T c is weaker than the correspond-
ing effect of a constant external field. The numbers in figures correspond to increasing
internal/external bias field magnitudes. Data are schematic plots of actual results from
the following sources: (Al) Ref. 6; (A2) Ref. 2; (Bl) and (B2) Ref. 8; (CI) Ref. 3;
(C2) this paper.
 Effects of Dipolar Impurities in Small Amounts 121

up of an a-alanine substituted unit cell and its surrounding mechanically

distorted neighbors, which act in such a way as to stabilize the polarity of
the crystal in going back and forth through the transition. Its authors do
not discuss the temperature dependence of the bias.
In the present paper, we report hysteresis loops and dielectric constant
observations of the internal bias field in TGS-a crystals with various a-
alanine concentrations through T c .
The temperature dependence of the effective internal bias field (E\,)
and the zero field polarization (PQ) can be analyzed within the framework
of the statistical theory of ferroelectrics, 10 ' 11 taking duly into account the
distinct response of the randomly distributed polar centers associated with
molecular units containing a-alanine (in contrast with response of normal,
all glycine units) and can be shown to describe correctly the observed tem-
perature dependence.
TGS-a single crystals, grown from different water solutions (7-20%
molar content), were kindly supplied by F. Jimenez (U. de Sevilla). They
were of reasonably large size and good optical quality. From them various
plates of area ranging from 0.3 to 2 cm 2 , and thickness ranging from 0.15 to
0.3 mm, were cut. Gold leaf electrodes were attached at the main surfaces
of these samples. A set of three samples spanning a relatively wide range of
a-alanine concentration (as determined from room temperature direct E\,
measurements) were selected for investigation.
A digital oscilloscope (Nicolet Explorer I) was used to observe the hys-
teresis loops in a wide frequency range (0.1-1000Hz). For dielectric constant
measurements an ESI Video Bridge model 2100 was used. The driving volt-
age amplitude for hysteresis loops measurements was 300 V, and 1V for
dielectric constant measurements. Constant external voltages up to 600 V
for hysteresis loops and up to 45 V for dielectric constant were applied to
the samples during the measurements. As it might be expected voltages of
opposite polarity showed opposite effect in the crystal dielectric response,
i.e., one polarity brings the data on TGS-a closer to those of pure TGS,
while the opposite polarity takes them away.
The temperature control of the sample holders in the thermal bath was
made with a Haake F3, which gives a thermal stability of ±0.005°C. In
most cases, however, we used slow thermal heating and cooling rates with
periodic temperature recordings. The temperature was measured by means
of a chromel-constantan thermocouple and a Keithly 195 digital voltmeter
with a resolution of ±0.5 /xV.
122 Effective Field Approach to Phase Transitions

The dependence of the hysteresis loops shape with the driving field
amplitude was first checked at room temperature, and a sufficiently large
amplitude (Eo « 2.5 kV/cm) was chosen for the measurements to be taken
at T « Tc in such a way that the influence of this parameter, as well as
the driving field frequency, were not very pronounced. In order to be able
to compare hysteresis loops data with dielectric constant data, both sets of
measurements were made at a frequency of 1 kHz.
Figure 2.2.2(a) shows a set of data of effective internal bias field E^ as a
function of temperature in an interval of ±5°C around Tc for three samples
which had room temperature internal bias field of 80 V/cm (#1), 390 V/cm
(#2), and 515 V/cm (#3). The room temperature E\> value is known to be
roughly proportional to the a-alanine content in the crystals; therefore,
these samples spanned a range of nearly one decade in maximum (room

«00

O Sample 3
4 BO
0 Sample 2
V Sample 1
-£ 360

>

u JUC

120

44 46 48 SO 52 6*
TEMPERATURE (*C)

1.0

0
44 46 46 SO 52 54

TEMPERATURE f'C)

Fig. 2.2.2. Variation of the internal bias field (a) and zero field polarization (b) with
temperature near Tc for three samples of increasing alanine content. Data points
labeled X correspond to sample 3 for lowering temperature.
 Effects of Dipolar Impurities in Small Amounts 123

temperature) E\> value. It was observed that there is a certain "thermal

hysteresis" between the rising and lowering temperature data. Sufficiently
away from Tc both sets of data for decreasing and increasing T coincide
very well. This might be, in principle, attributed to a pronounced temper-
ature dependence of the a-alanine polar centers' relaxation time near Tc.
A similar, and even more pronounced "thermal hysteresis" effect has been
observed in specific heat measurements 7 ' 8 and it has been seen that the
rising temperature data approach more closely the successive equilibrium
states, as inferred from the fact that, for cooling, if one waits for very long
times at a fixed T, the value of E\, approaches asymptotically the corre-
sponding i?b value for heating. This effect is still under investigation and
eventually the results would be published elsewhere. Figure 2.2.2(b) shows
the zero field polarization dependence with temperature. In this figure we
can see clearly the smooth decrease of the polarization through T c , which
is due to the presence of a-alanine polar centers in the crystal lattice.
Figure 2.2.3 gives a representation of Eb (normalized to its maximum
value) versus PQ (normalized to the zero field polarization at T = Tc)
obtained also from the same hysteresis loops at various temperatures. Only
data for rising temperature are shown. It can be seen that, at least for

| > H ^

y
•

' /
&S/
• Sample 3

<s> Sample 1
/
•

/<= ? Sample 1
- Theory
' •e,o E

1
O •< .8 1.2 1.6 2

p
o/Poc

Fig. 2.2.3. Plot of internal bias field normalized to its value, E^/E^MI versus zero
field polarization normalized to its critical temperature value, Poc = Po(Tc), for the
same three examples of Fig. 2.2.2. The continuous line gives the theoretical relationship
obtained from Eq. (15).
124 Effective Field Approach to Phase Transitions

the range of a-alanine concentration under investigation, the normalized

data fall approximately into the same universal curve, within experimental
accuracy (about 5% in the worst cases). We may infer from these data that
there is no interaction among a-alanine polar centers at the low levels of
concentration in the samples, roughly estimated to be in the lOppm range
by comparison with previous work.9 In the same figure we have plotted the
theoretical curve obtained from a simple statistical theory applicable to a
dipolar ferroelectric with a diluted concentration of randomly distributed
polar centers. The agreement between the experimental behavior of E^{PQ)
and the theoretical relationship, to be discussed below, is excellent.
Figure 2.2.4 shows the dielectric constant, s', as a function of temper-
ature for the same set of samples with varying concentration of a-alanine
at 1kHz and driving voltage amplitude IV. The frequency dependence
between 20 Hz and 20 kHz was relatively small. We also saw in these mea-
surements the same phenomenon of thermal hysteresis between sets of data
for rising and lowering temperatures.
Let us consider a ferroelectric crystal 10,11 with N normal ferroelectric
unit cells, each one possessing a normal dipole moment //, which can be
oriented parallel or antiparallel to the effective molecular field:

EeS = E + (3P, (1)

I 1 1 i i I
45 47 49 S) 53 55

TEMPERATURE (C )

Fig. 2.2.4. Plot of the dielectric constant versus temperature for the same three exam-
ples studied in hysteresis loops measurements. As an inset we can see the plot of the
dielectric loses versus temperature near Tc for the same samples.
 Effects of Dipolar Impurities in Small Amounts 125

where E is the external field, (3 the mean field coefficient (f3 = 4irTc/C,
with C = A T / A e - 1 = Curie constant), and P the polarization per unit
volume. At T < Tc, EeK is not zero even for E — 0. In equilibrium or
quasi-equilibrium conditions,

iVlPl2 = N2P21, (2)

where N\ is the number of unit dipoles pointing in the direction favored by

the effective local field and N2 the number of unit dipoles pointing in the
opposite direction. Taking into account that,

P12 = Po ex.p(-Eefffi/kBT), P21 = Po exp(EeS^/kBT),

(3)
Po = wexp(-Af//fc B T),

where p\2 and P21 are dipole jump probabilities per unit time between
asymmetric states for opposite directions, po is the jump probability per
unit time between symmetric states, and At/ is the height of the potential
barrier between states, and is a characteristic attempt frequency.
It is straightforward to get, knowing that Ni + N2 = N,

(E + f3P)v TCE + (3P

P=(N1- N2)n = tanh — N/j, t a n h (4)
kBT ~T (3N(i

where Tc = /3A//z2 /kB- We have here assumed for the sake of simplicity that
the dipoles are not deformable, and then that the value is the same for low
and high values of Eeff. For E = 0 we have,

—r- = tanh II3L (5)

Nfj, T NJJL

where Ps is the spontaneous polarization, corresponding to E = 0.

If we consider now a ferroelectric with a randomly distributed small
number of polar centers Na <C N (say N&/N « 10~ 4 or less) each one
characterized by a dipole moment \i& of unspecified magnitude, originally
incorporated with fixed orientation during the crystal growth process, we
can use the same reasoning as in Eqs. (4) and (5) to get the temperature
dependence of the zero field associated polarization P a < ?o- (In our case
the polar centers are the ones presumably associated with local, extended
defects made up of each a-alanine substituted unit cell and its surrounding,
126 Effective Field Approach to Phase Transitions

mechanically distorted, neighbors.) Then we can write,

Pa
tanh
•EeffMa
= tanh "/WW (6)

Taking into account that

Eh = f3Pa, EhM = (3NA^, (7)

where EbM is the bias field maximum value and that, for JVa -C N, Tc is
still given by Tc = f3N/j?/kB, we can rewrite Eq. (6) as

Eb Tc Ma Pp
= tanh
EbM

or

= Ma = I^tanh-^Eb/EbM]
(8)

On the other hand, for the normal glycine dipolar units under the influ-
ence of Eb and using Eq. (4), we have

T Eh + 0Po]
= tanh (9)
N/J,

and making the use of the fact [see Eq. (7)] that

Eb Eh JVaMa
(10)
0Nn EhM N fi '

we can rewrite Eq. (9) as

T Eh Nafi& P0"
—- = tanh
.T c EbM N n Nfi_
or
T Eh ^VaMa Po~
—- = tanh V/x. (11)
Tci SbM N fj,

We can eliminate a, the ratio of polar center dipole moment to normal

unit cell dipole moment (which is not necessarily constant), from Eqs. (8)
 Effects of Dipolar Impurities in Small Amounts 127

and (11) to get

—— t a n h - 1 [^1 N P0 T [Pol (12)

•C/bM
—-tanh - 1
Ebu To
Taking into account that the change in E\> occurs in the very close
vicinity of Tc (see Fig. 2.2.1) where T w Tc, and that there PQ/NH < 1, we
can approximate Eq. (12) by

Eh Eh I^Po_
tanh H P^
E\bM ^bM NaNn Nn Nil
N A /P0
(13)
Na3 \NIM

For T = Tc, we define Ehc = Eh (T = Tc) and P0c = P0 (T = Tc). Then,

Ebc/Eh = Ebc/Ebu = 0.5 in all cases, and Po/N/x = P0c/N(j,, changing with
the a-alanine concentration in such a way that the larger that concentration
is, the larger POC/NJJL becomes. Then, right at the transition temperature,
Eq. (13) reads,

N_\
(0.5) tanh" 1 (0.5) (14)
ATa3 Nn

and from Eqs. (13) and (14) we get

1/4
( # - ) tanh"
Pv_
(15)
PQC (0.5) t a n h - 1 (0.5)

This expression, obtained in a straightforward way from simple sta-

tistical physics considerations, fits very well the experimental data for all
samples examined, as shown in Fig. 2.2.3.
A good test for the results obtained from the statistical theory developed
in the last paragraph consists in checking whether it is able to give estimates
of the alanine concentration in the samples (not in the aqueous solutions
from which they were grown, where the concentration is, of course, much
higher) in agreement with the chemical analysis determinations previously
made by other authors 9 on samples with similar values of internal bias.
128 Effective Field Approach to Phase Transitions

From Eq. (14) we get

Since we know P 0 c experimentally (see Fig. 2.2.2(b) for T = Tc) and

Nfj, = ( P S ) M = 4 / i C / c m 2 = 1.2 x 10 3 esu, we can substitute in Eq. (15)
the values of (Poc/Nfi), which are 0.04 for sample # 1 , 0.075 for sample # 2 ,
and 0.09 for sample # 3 . These lead to values of Na/N ranging from 10~ 4
to 10~ 5 , i.e., 10-100ppm, which is in good agreement with those quoted by
Novik et al. for samples with room t e m p e r a t u r e internal bias in the same
range as those of our samples.

References

1. M.E. Lines and A. Glass, Principles and Applications of Ferroelectric and

Related Materials (Oxford University Press, Oxford, 1980).
2. K.L. Bye, P.W. Whipps and E.T. Keve, Ferroelectrics 4, 253 (1972).
3. K.L. Bye, P.W. Whipps, E.T. Keve and M.R. Josey, Ferroelectrics 7, 179
(1974).
4. E.T. Keve, Phillips Tech. Rev. 35, 247 (1975).
5. J.L. Martinez, A. Cintas, E. Dieguez and J.A. Gonzalo, Ferroelectrics Lett.
44, 221 (1983).
6. J.L. Martinez, J.E. Lorenzo, E. Dieguez and J.A. Gonzalo, Cryst. Lattice
Defects Amorph. Mater. (1987).
7. J. del Cerro, Private communication.
8. F. Jimenez, Ph.D. Thesis, Universidad de Sevilla (1987).
9. V.K. Novik, N.D. Gavrilova and G.T. Galstyan, Sov. Phys. Crystallogr. 28,
684 (1983).
10. J.A. Gonzalo and J.R. Lopez-Alonso, J. Phys. Chem. Solids 25, 303 (1964).
11. J.A. Gonzalo, Phys. Rev. B9, 3149 (1974).
 Chapter 2.3

Mixed Ferro-Antiferroelectric
Systems and Other Mixed
Ferroelectric Systems*

Considerable attention has been devoted in recent years to the investigation

of phase transitions in mixed crystals with competing interactions and, in
particular, to the mixed ferro-antiferroelectric system 1 (RDP)i_! (ADP)^
made up of rubidium and ammonium dihydrogen phosphate. The phase
diagram of this system is shown in Fig. 2.3.1. In this chapter, we will inves-
tigate first a simple two-sublattice classical model for ferro- and antifer-
roelectricity, which will be shown to describe consistently the transition
for pure RDP and pure ADP. Next, we will consider the behavior to be
expected for the phase transition classically, i.e., in the absence of quantum
fluctuations of the elementary dipole moments. Finally, we will introduce
the appropriate quantum corrections in the expressions for Tc and TN and
will show that satisfactory agreement with the observed phase diagrams is
obtained.
It is well known that crystals isomorphous with potassium dihydrogen
phosphate (KDP) often show ferroelectric or antiferroelectric phases at low
temperatures. The fact that an antiferroelectric arrangement of dipoles is
sometimes realized suggests that a simple two-sublattice model, similar to
the one for antiferromagnets, 2 may be useful to describe the phase transi-
tion in the KDP family. Since there are four chemical units (Z = 4) per
(conventional) tetragonal unit cell in KDP crystals, the system may be
thought of as a superposition of two interpenetrating bcc sublattices, each

*Work previously published under the title "Quantum effects and competing interac-
tions in crystals of the mixed rubidium and ammonium dihydrogen phosphate system,"
J.A. Gonzalo, Phys. Rev. B 39 (1989). Copyright © 1989. The American Physical Society.

129
130 Effective Field Approach to Phase Transitions

150 IROPVx lAOPl*

P£
(Telral

(Af£
JtOrtho)

'Dipolc glass
phase reported

0 0.2 0.4 0.6 0.8 1.0

RDP X AD p

Fig. 2.3.1. Phase diagram of (RDP)i_ ; E (ADP)x. Observed, solid line (see Ref. 1); theory
(including quantum effects); crosses [Eqs. (22) and (23) with xc = 0.22 and yN = 0.26,
respectively; see text].

containing two chemical units. Let us call A and B as these two sublat-
tices, and take into account that we must consider intralattice (AA, BB)
and interlattice (AB, BA) interactions. In the mean field approximation,
the local effective field acting on unit dipoles at points in lattice A and B,
respectively, will be

(£ eff )a = £ + aPa + /3Pb, (1)

(£eff)b - E + f3Pa + aPh, (2)

where E is the external field, a(AA) = a(BB) and /3(AB) = /3(BA) are
mean field coefficients, and Pa and Pb are the pertinent sublattice polar-
izations per unit volume.
Using these effective fields in the standard 3 mean field expression for
the polarization as a function of temperature we get

tanh (3)
Nfia kT

^..^(Ggte), (4)
 Mixed Ferro-Antiferroelectric Systems 131

where N is the total number of sublattice sites (or unit cells) per unit
volume, and /i a and /^b are the respective sublattice unit dipoles, which
in the ordered phase can be pointing parallel (ferroelectric case: \ia = /Ub)
or antiparallel (antiferroelectric case: \ia = —/^b) to each other, depending
on the geometry of the lattice. Since the two sublattices are chemically
identical, we take |/i a | = |/-*b|- From Eqs. (l)-(4), we get

kT P
E=— t a n h - 1 - A - - aPa - (3Pb, (5)
Ma N/J,a
kT Pu
E=— tanh-1-^-/3Pa-aPb, (6)
Mb Nfih
which, together, define an equation of state for E, P = P a + Pb and T.
Let us consider first the ferroelectric case, in which at T < Tc we have
a non-zero spontaneous polarization P s = P s a , Psb = 0 for E = 0. Adding
Eqs. (5) and (6), and taking into account that t a n h - 1 Z± ± t a n h - 1 Zi =
t a n h - 1 ( Z i ± ^2)/(l ± Z\Z-i) and that \i& — /J,\, = /z/2, we get

2£ = 2 - t a n h \ + A{Pa/N^iPh/Nfl)-(<* + P)(P* + P*)- W

It is easy to get from here the spontaneous polarization below the tran-
sition temperature, but not very far from it, as

P./^«VS(T C /T-I)V» 1 Tc=t±mi. (8)

The low amplitude (SE —* 5P <€! Nfj,) inverse dielectric constant e - 1 =

dE/AndP can be obtained from Eq. (7) with the following results:

e-1 = (T-ec)/C+, at T > GC(PS = 0),

2 (9)
C+ = 2nNfj, /k, e c = T<C l

and

e" 1 = (0C - T)/C-, at T < 6 C (P S = 0); C_ = Nnn2/k. (10)

Next, we consider the antiferroelectric case. At E = 0, we have now

Ps = Psa + Psb = 0, P s a = —Psb = PSs being the sublattice spontaneous
132 Effective Field Approach to Phase Transitions

polarization, obtained solving

4(Pss/A^) =T_ _ (a-p)N^
tanh- 1 {4(P ss /7V/i)/[l + 4(Pss/ArM)2]} TN' N
4fc ' [
'
which has a non-vanishing solution for Pss at T < T N , the antiferroelectric
transition temperature. Below TN, and not very far from it, we can get from
Eq. (11)
Pss/Nfi « (>/3/2)(l - T / T N ) 1 / 2 . (12)
The low-amplitude expression for £ _ 1 can be obtained from the sum of
Eqs. (5) and (6) for 5E -> SP <S Nfj,, resulting in

e-1 = ( T - 0 N ) / C + ) atT>TN(Pss=0),
2
C+ = 2irNn /k,

©N - —A r , (13)

and in another, more complicated expression, at T < TN, which leads to

e-1(T^)=s~1(T+)=-/3/S^
£-!(()) = oo, (i.e., e(0) = 0 ) . (14)

For RDP (ferroelectric, second order transition) we can get the sum of
the sublattice mean field coefficient from Eqs. (8) and (9), and the observed
values for 6 C = 147 K and C+ = 4.14 x 103 K, as

a + (3 = 87r6 c /C + = 0.89 > 0. (15)

For ADP (antiferroelectric, first order transition) we get the sum and
difference of a and /? from Eqs. (13) and (11), along4 with 0 N = —14K,
T N = 148 K, and C+ = 2.67 x 10 3 K, as

a +/3 = 87re N /C + = -0.13 < 0, (16)

a-(3 = 87TT N /C* + = 1.39 > 0, (17)

and, therefore, a = 0.63, /? = —0.76.

That the two-sublattice mean field relations obtained for KDP-type
crystals show a fair degree of internal consistency can be checked in several
ways. For instance, for RDP we get n = (kC+/2-!rN)1/2 « 6.2 x 10- 1 8 esu
from Eq. (9) and fx = P8B.t/N = 7.0 x 10 _ 1 8 esu from the low-temperature
(saturation) value of the spontaneous polarization P s a t « 5.6/xC/cm2 =
5.6 x 3000esu, ./V = ( c a 2 ) - 1 = 2.36 x 10 21 unit cells/cm 3 . For ADP we
 Mixed Ferro-Antiferroelectric Systems 133

can use Eq. (14) to get an independent estimate of j3 = e(T^)/8n. Using

e(Tj7) ~ 14 and e(T^) « 30, 4 one gets, respectively, /?_ = —0.55 and
j3+ = —1.19. These values average out very close to the one previously
obtained from Eqs. (16) and (17). It is of interest to point out that, since
a and /? depend on the tetragonality (c/a — 1) of the lattice (they should
be zero for a cubic lattice if they are originated by electric dipole-dipole
interactions) we are entitled to assume a = a(c/a — 1) and (3 = P{c/a — 1),
and we can use the calculated values for ADP, namely C<A — 0.63 and
j3K = -0.76, together with ( c / a - 1) A = 0.0067,1 to estimate a = 0.94 x 102
and (3 = -1.14 x 102. For RDP, on the other hand, {c/a - 1) = -0.041,
from which value we obtain estimates for OR = a(—0.41) = —3.90 and
PR = /?(-0.41) = 4.72, which imply (a + /3)R = 0.81, in fair agreement
with the value previously obtained from Eqs. (8) and (9).
Having set the grounds for calculating (classically) Tc and TN for the
pure ferroelectric case (RDP) and the pure antiferroelectric case (ADP),
we examine now the mixed crystal case. The simplest mixed case is that of
a ferroelectric (or antiferroelectric) and a non-ferroelectric isomorph. For
instance, 5 K x N b i _ x T a 0 3 or (TSCC)i_ :c (TSCB) :c . 6 Looking at the phase
diagram (Tc versus composition x) in these systems, one sees, not unexpect-
edly, a linear decrease of Tc with increasing x, which extrapolates approxi-
mately to Tc = 0 at x = 1. Quantum fluctuations, however, tend to depress
Tc already at a certain x < 1, suppressing the transition sometimes consid-
erably below x = 1.
In the mixed ferroelectric-antiferroelectric system, one expects an
approximately decrease in Tc at x > 0 and also a linear increase in TN
at x < 1. Since TC(RDP) = 147K, T N (ADP) = 148K, and AT(RDP)' =
2.36 x 10 21 and A^(ADP) = 2.37 x 10 21 are very close to each other, one
may expect a similar linear trend of transition temperature with composi-
tion from both sides toward zero.
Then, classically, from Eqs. (8) and (11), we have

kTZ(p) = ^ - N ^ , kT*c{x) = ^±IN(1 - x)n2 = fcTc*(0)(l - x),

(18)
A:TN(0) = ^ T A ^ 2 , kT^y) = ^-N{\ - y)»2 = fcTN(0)(l - y),
(19)

where y = 1 - x, and T*(0), T N (0) are the classical transition temper-

atures for the pure ferroelectric and antiferroelectric systems. Quantum
134 Effective Field Approach to Phase Transitions

mechanically, on the other hand, we have

huJoc I 2 + (n)Tc j = —~Nn2 for x = 0,

J«WON f 2 + <n>TN J = ^-J-N^2 for

» = 0.

where V^k^Oc and 1 / 2 ^ O N are the zero point energies and (n) is the average
number of energy quanta excited above the ground state at temperature T,
given by Planck's relationship. Therefore,

huoc/2 tanh[/iwoc/2fcTc(0)] = ^^-Nfj,2 = kT*{0),

/IWON/2 tanh[/iwON/2fcTN(0)] = ^ p - i V > 2 = kT£{0),

where Tc(0) and TN(0) are the quantum mechanical transition tempera-
tures, which reduce to Tc*(0) and T"N(0), respectively, for /iu>Oc/2A;Tc(0) -C 1
and hu)o^/2kT^(0) <S 1. The last two equations yield

Tc(0) = ( ^ 0 c / 2 f c ) / t a n h - 1 ( Z c ) ; Zc = /iwoc/2fcTc*(0), (20)

T N (0) = (/iw 0N /2fc)/tanh- 1 (Z N ); Z N = hu;ON/2kT^(0), (21)

and, therefore, we finally get

Tc(x) = T c ( 0 ) t a n h - 1 ( Z c ) / t a n h - 1 [ Z c / ( l - a;)], (22)

T N (0) = r N ( 0 ) t a n h _ 1 ( Z N ) / t a n h - 1 Z N / ( 1 - j/)]. (23)

Since Tc(xc) = 0 for Zc = 1 — a;c and TN(T/N) = 0 for ZN = 1 — 2/N, it

is sufficient to know the experimental values for xc and yN to completely
specify the phase diagram. For the (RDP) x (ADP)i_ x system, xc ~ 0.22,
2/N ~ 0.26 (see Fig. 2.3.1). The agreement between theory and experiment
for this mixed system is excellent, as seen in Fig. 2.3.1.

References

1. For a recent review, see, for example, H. Terauchi, Phase Transitions A7, 315
(1986) and references therein.
2. See, for example, A. Dekker, Solid State Physics (Prentice Hall, Englewood
Cliffs, NJ, 1962), pp. 484-488.
3. See, for example, J.A. Gonzalo and J.R. Lopez Alonso, J. Phys. Chem. Solids
95, 303 (1964); J.A. Gonzalo, Phys. Rev. B9, 3149 (1974).
 Mixed Ferro-Antiferroelectric Systems 135

4. Ferroelectrics and Related Substances, edited by K.H. Hellmege and A.M.

Hellwege, Landolt-Berstein, New Series, Group III, Vol. 16 (Springer-Verlag,
Berlin, 1981 and 1982).
5. U.T. Hochli, Ferroelectrics 35, 17 (1981); see also K.A. Miiller, Jpn. J. Appl.
Phys. (Suppl.) 24, 89 (1985).
6. W. Windsch, H. Braeter and B. Milsch, Ferroelectrics 47, 213 (1983).
 Chapter 2.3.1

Comment on "Ferroelectricity
in Zinc Cadmium Telluride"

Ferroelectricity in Zn^Cdi-^Te has recently been reported by R. Well

et al.1 for Zn content from 4 to 45%. This is very interesting because,
for the first time, ferroelectricity is found in materials crystallizing in the
zincblende configuration, either of the binary constituents making up the
mixed crystals being non-ferroelectric. Attempts by the authors 1 to fit
the experimental curves giving the transition temperature as a function
of Zn concentration, Tc(x), and the Curie constant as a function of Zn con-
centration, C(x), were unsuccessful because of the difficulty to match the
rapid decrease of Tc(x) for x < 0.04.
The aim of this comment is to show, hopefully, that the dipolar, effec-
tive field approach, 2 to ferroelectric transitions applied to this system can
give a fair description, at least in semi-quantitative terms, of the depen-
dence of transition temperature (Tc) upon concentration (x). The pure
CdTe structure is made up of Cd tetrahedra with Te atoms at their center.
Substitutional Zn atoms give rise to tetrahedra with 0, 1, 2, 3, and 4 zinc
atoms, with different probabilities determined by the average concentra-
tion i in a homogeneous sample. Obviously, 0 and 4 zinc atoms produce
symmetric tetrahedra with no dipole moment. It may be assumed also that
2 zinc atoms do not give rise to any dipole moment along (111). On the
other hand, 1 and 3 zinc atoms produce asymmetric tetrahedra with possi-
ble non-zero dipole moments pointing in (111) directions. The probability
of realization for tetrahedra with 1 zinc atom is p\x{l — x) 3 , and for tetra-
hedra with 3 zinc atoms it is p3 = x3(l — x). The effective field2 at a dipole
site will be, therefore,

Erf = E + frPi + foPs, (1)

137
138 Effective Field Approach to Phase Transitions

where E is the external field, (3\ and P3 are effective field coefficients, and
P\ and P3 are polarizations due to tetrahedra with 1 and 3 zinc atoms,
respectively. These polarizations are given2 by

Pi/Nun =tanh(EeStx1/kBT),
(2)
P3/N3fi3 = tanh(EeSfjL3/kBT),

where Nx = (4/o~ 3 ) x (1 - x) 3 , i\r3 = (4/a~ 3 )x 3 (l - x), and Hi, /j,3 are the
respective elementary dipole moments. Combining the relationships for P\
and P3 in Eqs. (2), one gets

PiNi/n t a n h - 1 (PI/NKH) + p3N3^3 tanh" 1 (P3/N3fi3)

= [(faNtvD/kBT] ( A P i + p3P3), (3)

which for T < T c , i.e., P i / A ^ i <C 1, P3/N3fi3 <C 1, leads to

Tc(x) = (PiNitf + foN^DkB = (pNn2/kB){x(l - x ) 3 + x 3 (l - x ) }

(4)

taking pi = /?2 — P, Mi = M3 = A*- Numerical values for /? = A-KTC/C, where

C is the Curie constant, for N = 4/a+ 3 , where 3 a+ 3 = l/2a 3 (CdTe) +
a 3 (Z n i Te) = 2.489xl0 2 2 cm 3 , and for (j. = [fc B C/4xiV{x(l-a;) 3 +x 3 (l-a:)}]
are easily obtained, and also for x = 0.25, p = 4.1 (close to the Lorentz value
4/3) and fi ss 3.0 x 10~ 18 esu. For other concentrations the g values differ

1 •"-

^
400 -
6.
E
1—
//
*c 200 // "
3
O
/

0.0 0.1 0.2 0.3 0.4 0.5

x, Proportion of Zn

Fig. 2.3.1.1. Curie temperature vs. x (Zn proportion).

 Comment on "Ferroelectricity in Zinc Cadmium Telluride" 139

from (3{x = 0.25) by no more t h a n 20% and the // values from fi(x — 0.25)
by no more t h a n 40%.
Figure 2.3.1.1 shows the calculated Tc(x) according to Eq. (4) with
(3Nfi2/kQ « 5.0 x 10 3 consistent with the parameter values above, within
the quoted uncertainties, along with experimental d a t a of Well et al.A No
errors bars are given for the d a t a in Ref. 1, b u t the overall agreement seems
to be fair. It may be noted t h a t the calculated spontaneous polarization for
x = 0.10, Ps = ATi/ii = ( 4 / a 3 ) x (1 - x ) 3 w 1.9 x 10 3 esu « 0 . 6 3 / i C / c m 2 ,
obtained with fj,(x) = 3.6 x 1 0 _ 1 8 e s u , is also compatible with the value
observed from hysteresis loops.

References

1. R. Weil, R. Nkum, E. Muranovich and L. Benguigui, Phys. Rev. Lett. 62, 2744
(1989).
2. J.A. Gonzalo, Phys. Rev. B39, 12297 (1989).
3. See, for example, N.W. Ashcroft and N.D. Mermin, Solid State Physics (Holt,
Rinehart and Winston, New York, 1976).
4. The vertical scale in Fig. 4 of Ref. 1 should be in /xC/cm 2 (private commu-
nication by R. Weil). Note also that the loop is not compensated for excess
conductivity.
 Chapter 2.4

Relaxation Phenomena
Near Tc*

Lithium tantalate is a ferroelectric compound with important technological

applications due to its nonlinear optical and photorefractive properties. 1
LiTaOs and its isomorph LiNb03 are high-temperature ferroelectric
materials, 2 with critical temperatures of 618 and 1140°C, respectively. Usu-
ally, they are ground with a slightly non-stoichiometric composition, 3 ' 4
which can vary in a narrow range around the congruent melting compo-
sition. The congruent melting composition gives rise to crystals with a
relative abundance of 2.8 of Li + vacancies. An important increase of the
dielectric constant is observed at low frequencies in the 400-900°C range.
The influence of charged mobile defects (such as Li + vacancies) on dielec-
tric properties has been studied for LiTaC>3,5 LiNb03, 6 and, more recently,
some perovskite-type crystals. 7 The transition temperature of LiTaC>3 is
inside the temperature range where dispersion on the dielectric constant
caused by mobile defects is important, and it is necessary to separate out
the ferroelectric contribution in order to study the critical instrinsic relax-
ation behavior near Tc.
The experimental real and imaginary parts of the dielectric constant
appear to show the sum of the contribution of mobile defects, which has
a 1/LO behavior, and a Debye-like ferroelectric contribution. In the present
work, which extends previous e(u) measurements up to 10 MHz, the ferro-
electric relaxation time is obtained for LiTaC>3 and it is analyzed in terms
of mean field theory predictions.

*Work previously published under the title "Ferroelectric relaxation of LiraO," C. Prieto
and J.A. Gonzalo, Solid State Commun. 61, 4373 (1987). Copyright © 1987. Pergamon
Press PLC.

141
142 Effective Field Approach to Phase Transitions

A very good optical quality single crystal of LiTaC-3 was donated by

G. Samara, from Sandia Laboratories. The sample was disk shaped, 9.6 mm
in diameter and 2.7 mm in thickness. Gold leaf electrodes were attached to
the main surfaces perpendicular to the ferroelectric c-axis.
Measurements were performed in a high-temperature furnace, which
allowed work at variable oxygen pressure. The sample temperature was
measured with a Pt/Pt-Rh(13%) thermocouple by a digital microvoltimeter
and remained constant within O.IK for each set of data. The capacitance
and dielectric losses of the sample were previously measured with an ESI-
2100 video-bridge from 20Hz to 20kHz at various temperatures near Tc.
In order to characterize the temperature-dependent relaxation of e(u>) well
above Tc, additional measurements were performed with a HP-4192A at
these temperatures from 10 Hz to 10 MHz.
The real part of the dielectric constant of LiTa03 is represented in
Fig. 2.4.1 for various temperatures, as a function of the frequency. At
very low frequencies there are 1/u contributions identified with mobile
charged defects motion. 5 The ferroelectric relaxation appears clearly when
the extrapolated 1/w contribution is subtracted from the experimental data
points.
Figure 2.4.2 shows the imaginary part of the dielectric constant corre-
sponding to the same data as in Fig. 2.4.1. It is possible to observe the
peaks' characteristic of ferroelectric relaxation in natural scale once the
mobile defects contribution has been subtracted.

10'

to2 io* 10*

FREQUENCY (Hz)

Fig. 2.4.1. Log-log plot of the real part of the dielectric constant as a function of
frequency for LiTaC>3 at three temperatures. Broken lines are ferroelectric contributions
(see text).
 Relaxation Phenomena Near T c 143

3 . V
U
.-ioi \
<*>
10s
X
V —
£

l!

V -•'""••
10' 0.8

10'
K \
/ '\>-. \ ft*

.
10' . - - ' • ? ""---..,«v"»-'e
10! 10* 10'
FREQUENCY (Hz)

Fig. 2.4.2. Log-log plots of the imaginary part of the dielectric constant as a function of
frequency for LiTaC>3 at three temperatures. Broken lines are ferroelectric contributions;
in this case, they have been represented in the left-hand natural scale (see text).

-1.0
log (AT/T)
Fig. 2.4.3. Log-log plot of temperature dependence of inverse ferroelectric relaxation
time vs. ( A T / T ) .

We can obtain at every temperature the characteristic time from the

maximum of the ferroelectric contribution to the imaginary part of the
dielectric constant as a function of the frequency, or from the inflection
point of the real part as a function of frequency.
Figure 2.4.3 is a log-log plot of the inverse relaxation time vs. (AT/T) to
show the critical exponent of this dependence, x = (logr _ 1 )/(log A T / T ) .
Mean field theory (neglecting fluctuations) gives for this exponent a value
144 Effective Field Approach to Phase Transitions

x = 1, which is approximately the observed value. The same behavior can

be observed if one analyzes the temperature dependence of the loss factor
at a fixed frequency.5
The observed relaxation behavior of an order-disorder ferroelectric may
be explained using a double-well potential model by means of a mean
field approach. The effective field on an elementary ferroelectric dipole is
jEeff = E + (3Pd, where Pd is the dipolar contribution to the polarization.
In thermal equilibrium, the number of dipoles in both directions and the
jump probabilities between the two equilibrium positions are related by

-/VlPl2 = ^V2P21- (1)

The expression for the jump probability is
p = vexp(-U/kBT) exp(P-EeS/kBT) = pQexp(nEeS/kBT), (2)
where U is the potential height barrier and fi is the electric dipolar moment.
The total number of dipoles is N = N1+N2 and the dipolar polarization
can be written as Pd = M-^2 — N\). In thermodynamical equilibrium we
have
Pd Nijl-expi-U/kaT)) _ u(E + pPd)
[)
N/i N1(l + exp(2U/kBT)) kBT
and for zero external field, Ps = Pd,

(4)
Nfi \kBTNij,J \TNfiJ
If a high enough external field E is applied in opposition to Ps the
reversion of this polarization gives a transitory current per unit area

— = N(pi2-p2i)-Pd(Pi2+P2i)- (5)

Using dimensionless variables, we have

% = -sinh(0(£+p)) -pcosh(0(£+p)), (6)

at r
where

From Eq. (6) it is possible to obtain expressions for the coercive field,
switching current, and switching time, as well as the ferroelectric relaxation
frequency as a function of temperature. An ac field E = EoeluJt with EQ
 Relaxation Phenomena Near Tc 145

much smaller than the coercive field will give rise to a small change in
spontaneous polarization

p = ps + Ap. (7)

Substituting in Eq. (6), and expanding the hyperbolic tangent,

Pa = tanh 0ps = 0pa-^ (Opsf (8)

and therefore

p s = (3(6»-l)) 1 /2. (9)

Using Eqs. (7) and (9) and the differential Eq. (6), one gets

At T T \TC-T4ir
where the ferroelectric relaxation time can be identified with Tr =
T ( 2 T / T C - T), resulting in

dAp 1 (c-eo_EoeMiujt)_Ap\ ( n )
At r r \ A-K

(Here eo is the high-frequency dielectric constant depending only on the

atomic polarization P ea -)
The solution of this differential equation, omitting the transitory term,
which decays rapidly, is

fd(*) = T - , £ , ~ £ ° -Eoexp(^t). (12)

Prom this it is possible to calculate the frequency dependence of the

dielectric constant as
v E + 47rAPea + 47rAFd / , e - e0 \ .{e - e0)uiTr
e =- = = Uo + , . o o - «-
E E V 1 + w2rr2) 1 + o;2rr2 '
(13)
which provides Debye-like relaxation behavior with characteristic ferroelec-
tric time r r , which can be expressed as

(rr)'1 = (2AT/T)(veM-U/kBT)). (14)

Near from T c , the exponential factor may be taken as a constant in com-

parison with (2AT/T).
146 Effective Field Approach to Phase Transitions

T h e same calculation is valid for T > Tc, where Ps = 0 and e « C/AT

(instead of 2C/AT).
T h e LiTaC>3 d a t a shown in Fig. 2.4.3 seem to agree well with the pre-
dictions of Eq. (14), obtained using a mean field approximation. Neverthe-
less, measurements have not been made at temperatures very close to T c ,
and we cannot conclude t h a t this behavior is valid in the closed vicinity
of T c . Note t h a t while L i T a 0 3 is usually considered a displacive ferroelec-
tric, recent works 8 ' 9 indicate t h a t it is more justified to take it as a mixed
order-disorder displasive ferroelectric.

References

1. A. Rauber, Current Topics in Material Science (North-Holland, Amsterdam,

1978).
2. A.M. Glass, Phys. Rev. 172, 564 (1968).
3. R.S. Roth, H.S. Parker, W.S. Brower and J.L. Waring, Fast Ion Transport in
Solids, Solid State Batteries and Devices (North-Holland, Amsterdam, 1973).
4. L.O. Svaasand, M. Eriksrud, G. Nakken and A.P. Grande, J. Cryst. Growth
22, 230 (1974).
5. C. Prieto, L. Arizmendi, J.A. Gonzalo, F. Jaque and F. Agullo-Lopez, Phys.
Rev. B 3 1 , 5483 (1985); Phys. Rev. B33, 7625 (1986).
6. C. Prieto, L. Arizmendi and J.A. Gonzalo, Jap. J. Appl. Phys. 24 (Suppl. 2),
1025 (1985).
7. T. Fernandez-Diaz, C. Prieto, J.L. Martinez, J.A. Gonzalo and M. Aguilar,
Ferroelectics 8 1 , 19 (1988).
8. E.J. Samuelsen and A.P. Grande, Z. Physik B 24, 207 (1976).
9. C. Prieto, L. Arizmendi and J.A. Gonzalo, Ferroelectrics 55, 63 (1984).
 Chapter 2.5

Polarization Reversal
in Ferroelectric Systems*

The process of ferroelectric polarization reversal under external field pulses

of variable strength has been widely investigated in the last three decades. 1
Among uniaxial ferroelectrics, triglycine sulfate (TGS) and its isomorphs
are probably the best studied experimentally. Pulvari and Kuebler2 and
Chynoweth 3 did preliminary work investigating the switching behavior at
low fields. Fatuzzo and Merz4 and Binggeli and Fatuzzo 5 extended the range
of observation up to intermediate and high fields. Further work by Hayashi,6
Jaskiewicz and Przeslawski,7 and Perez et al.s contributed to determine the
switching behavior at low and very low fields and questioned the validity of
the semiempirical model of Miller and Weinreich9 to describe satisfactorily
the observed behavior.
Recent renewed interest in time-dependent phenomena in cooperative
systems near phase transitions 10 justifies to some extent taking a new look
at the process of polarization reversal in ferroelectrics, with the aim of
obtaining a unified description of switching behavior from the low- to the
high-field regions.
Figure 2.5.1 shows the behavior of the inverse switching time of a uni-
axial ferroelectric like TGS as a function of field. It depicts, in schematic
form, actual data 4 ' 5 for TGS. Taking into account that there is a transition
region between the very low field region, where the process is extremely
slow, and the intermediate region, where the field dependence becomes
clearly linear, we can distinguish three regimes: (3) high-field regime, in
which (as discussed below) random switching occurs through the volume

*Work previously published under the title "Ferroelectric switching revisited," M.J.
Cebezuelo, J.E. Lorenzo, and J.A. Gonzalo, Ferroelectrics 87, 353 (1988). Copyright
© 1988. Gordon and Breach Science Publishers S.A.

147
148 Effective Field Approach to Phase Transitions

Fig. 2.5.1. Inverse switching time or maximum switching current in a sample of thick-
ness d as a function of pulse height of electric field for a uniaxial ferroelectric like TGS.
The high-field regime (3) is identified in this work with bulk random switching, the low-
field regime (2) with switching time limited by sidewise domain wall motion, and very
low-field regime (1) characterized by partial switching.

of the sample because the external field is strong enough to switch individ-
ual dipoles regardless of whether they are at the boundary of a micro (or
macro) domain or not; (2) low-field regime, in which switching occurs at
the walls of the initially preexistent microdomains (see below) which grow
in size under the influence of the external field at a growth rate limited by
the slow sidewise motion of the walls (the forward motion being much faster
and the sample thickness sufficiently small); and (1) very low field regime,
in which partial switching occurs also at the domain walls (this regime is
less interesting and will not be discussed further). Between regimes 2 and
3 there is a transition region labeled 2-3.
We may note that the switching time is related to the maximum of the
switching current, due to the fact that

/"* 1
2PS= / i(t)dt«-*mt8) i.e., im » 4P s i s " 1 (1)

and, since published data report alternative results on im and t" 1 , we will
convert data of im to data on t" 1 and vice versa using Eq. (1). Figure 2.5.1
indicates that the field dependence of i " 1 (or im) in the three regimes
 Polarization Reversal in Ferroelectric Systems 149

mentioned above can be simply given as:

Case (3):

im ex i " 1 cc(E- Ec3), Ec3 = large. (2)

Case (2):

i(xt~l <x{E- Ec2), Ec2 = very small (-C Ec3). (3)

Case (1): very small

im ex t'1 oc (E - Ecl), Ecl = very small (-C Ec2). (4)

We will see later that the threshold field values Ec have the meaning
of effective coercive fields for the bulk and domain wall (side wise motion)
switchings, respectively.
In a dipolar uniaxial ferroelectric, we may assume that each individ-
ual dipole can be reoriented, by means of an external field, between two
equivalent configurations in which the elementary dipole /J, is pointing in
the ± direction of the ferroelectric axis. The dipole is embedded in a local
field Eeff = E + (3P, where E is the external field, a mean field coefficient
(which may in principle be different for dipoles in the bulk of the sample
and dipoles at the domain wall), and P the polarization per unit volume.
To switch from one configuration to the other the dipole must overcome a
potential barrier AC/ (which may also differ for dipoles in the bulk and in a
domain wall, since the unit cells at the domain boundaries may be assumed
to be somewhat distorted). The transition probability per dipole per unit
time is

p± =vexp[-(AUmEeB/fi)kBT] = p0exp[±EeS(j,/kBT], (5)

where v is an attempt frequency (corresponding to a low lying lattice model

able to push the dipole atoms in the direction going from one configura-
tion to the other), kB is Boltzmann's constant, and T is the temperature.
In Eq. (5), p+ corresponds to the probability of jumping in the direction
favored by the effective local field and p- to the probability of jumping in
the opposite direction. The number of dipoles available for jumping in the
favored or opposite direction will be, of course, different if we are consider-
ing bulk switching (high fields) or domain wall switching (intermediate or
low fields). We will examine the rate equation, first for the bulk switching
case [case (3)], which can be done disregarding the domain structure, then
150 Effective Field Approach to Phase Transitions

for the sidewise domain wall motion switching [case (2)], and finally we will
discuss the transition region between high and low fields (2-3).

2.5.1. High Field — Case (3)

If at a given time there are Na dipoles per unit volume pointing opposite
to the field and Nb in the direction of the field, the rate equations can be
written down as

diVa
-NaPab + Nbpha (6)
dt
diVb
N a P a b - -WbPba, (7)
dt

where Na + Nh = N, pah = p03 exp[-(E - (33Pd)n/kBT], and pha

p03 exp[-(E + p3Pd)^i/kBT}.
Then, taking into account that Pd = (Nh — Na)[i,

dP d
Nuipab - Pba.) - Pd(Pab + Pb
dt
-(E + (33Pd)fi (E + foPd V
i{ N/J, sinh
fcRT
Pdcosh
knT
(8)

for I/T3 = 2po3 = 2wexp(—AU3/k-oT). We can write down this equation in

a more compact form, using Tc = /33Np?/k& and ESQ = P3Nn, as

dPf = j _f T±(E + (33Pd Tc(E + /33Pd

Nfi sinh Pd (9)
dt T3 \ T E.s0 T E.s0

The solution of this equation yields directly the switching current i(t) =
dPd/dt. Since the maximum switching current im = 4PS<71 corresponds to
(d 2 Pa/di 2 ) m = 0, it can be easily checked that at i — im we have

r
E.s0
--^S N/i
(10)

and, then making use of the fact that there is a threshold switching field
Ec3, corresponding to {dpd/dt)mc = 0, we can get, from Eqs. (9) and (10),
 Polarization Reversal in Ferroelectric Systems 151

for P d = Pdm = Pdmc,

a n h "' 1 ! ^ ^ ) '
Ec3 = foN^ ttanh ~ (' V " ) • (n)

This is the "bulk" coercive field, which is two orders of magnitude larger
than the ordinary "hysteresis loops" coercive field measured at low fields
and 60 Hz (which is determined by domain wall motion). Direct comparison
of Eq. (11) with the data of Binggeli and Fatuzzo 5 for TGS at high fields and
various temperatures shows good agreement. The temperature dependence
of Ec3(T) for T « Tc is very well fulfilled by the data, and the predicted
scale factor Es0 = f3Nfi = (4irTc/C)Ps0 1.2 x 10 4 esu/cm = 3.6 x 10 3 kV/cm
is well within a factor of two of the observed one.
The maximum switching current denned by Eq. (9) with (d2P<j/di2) =
0 can be expanded in terms of (E — Ec3), taking into account that
(E - Ec3)/Es0 <C 1 is always fulfilled, as

(t m ) 3 « 2(PS/Es0)v3 exp(-A V /fc B T)(T c /T)(£ - Ec3), (12)

which describes switching in regime (3) and will later be compared with
experimental data.

2.5.2. Low Field — Case (2)

As we have seen above, bulk switching becomes very ineffective when we

lower the strength of the driving field, until it stops for E < Ec3. Before
that point, however, another switching mechanism becomes effective. It is
well known that TGS crystals grown from water solution (usually at tem-
peratures well above room temperature) suffer a thermal shock when they
are taken out of the solution and it is also known that cooling shocks12 give
rise to many small spike-shaped microdomains (with polarization oppo-
site to that of the bulk crystal), which form a very regular array with
an average distance between neighboring microdomains of 0.01 cm. These
microdomains tend to be persistent and seem to be locally fixed, in such
a way that moderate external driving fields induce growth or decrease in
size, but not elimination of microdomains. It is also well known 12 that
at moderate fields, forward domain wall motion proceeds at a faster pace
than sidewise motion. Then, in order to write down the rate equation for
regime (2), under consideration, we may assume that, right after the begin-
ning of the driving field pulse, there is already formed a set of narrow
152 Effective Field Approach to Phase Transitions

microdomains running from one main surface to the other, which are grow-
ing sidewise until their walls meet those of their nearest neighbors. For
simplicity we may assume that the extended microdomains are equidistant
parallelepipeds arranged periodically with an average distance 2r m between
nearest neighbors. The rate equations are then, for t < tm.

\{r\ \ /'r\ / r P \
-n4 - + 1
( < * •

r + n4 - 7 Ph (13)
dt U
\ J v&, 1 \Pab
\KuJ \*>s/
dNb \{r\ (^ \ /' r \ / r T \
+n4 - + 1 r Pah -n4 - 7 Pb (14)
dt W J U
\l>s/ \v'«/ V&,/
where n is the number of microdomains per unit surface (then n =
1/2 r ^ ) , u is the lateral distance between neighboring unit cells [for TGS,
u — (ac sin/3) 1 / 2 ], d is the sample thickness, b is the unit cell parame-
ter along the ferroelectric axis, pab = po2exp(—(E — /3 2 -P)M/A;BT), pba =
P02exp(-(E + f32P)n/kBT). Subtracting Eq. (13) from Eq. (14), multiply-
ing by fi, and taking into account that N = Ns(d/b), we have
1/2 1/2
Pd T E + fcPd
sinh
dt T2 Ps ~T E,sO

1 E + f32Pd
cosh Ik (15)
T E,sO

where, to evaluate (r/u) in terms of (n/Ns) and the switched polarization

Pd, we have used

(r/u) = [2(Nh/N)/(n/Ns)]1/2, (16)

P/Ps = (Nh - Na)/N. (17)

It can be easily shown that making appropriate approximations in

Eq. (15) one gets
1/2
P3P*
sO
(» m ) 2 «64JV/i
fcPs
1/2 3/2
E-Et c2
xv2exy>(-AU2/kBT) (18)
3Sso

which gives the switching behavior in regime (2), dependent on the surface
density of preexistent microdomains through (n/Ns).
 Polarization Reversal in Ferroelectric Systems 153

2.5.3. Intermediate Field — Case (2-3)

High-field bulk switching (3) takes place at supersonic velocities, while

low-field domain wall switching (2) takes place at subsonic velocities. The
switching rate in (2) grows faster as the field increases, and eventually the
transition probability p eD will approach the maximum value of one when
the domain wall speed approaches the sound velocity, giving rise to a tran-
sition region from (im(E))2 to (im(E))3 in which the rate growth of im with
E small in comparison with either the subsonic rate (2) or the supersonic
one (3).

2.5.4. Very Low Field — Case (1)

As noted above, this corresponds to incomplete (partial) switching, and

sample characteristics, including thickness, should play a major role, mak-
ing it more difficult for theoretical analysis.
It would have been desirable to have a complete set of data on im(E) in
the same set of well-characterized samples (as to thickness and density of
microdomains in equilibrium) covering the whole range of fields from very
low (say E < 0.05kV/cm) to very high fields (say E > 50kV/cm).
However, combining the information provided by various authors, 2 - 6 ' 1 2
it appears that existing data provide sufficient support for a coherent pic-
ture of ferroelectric switching as given by Eqs. (12) and (18), which encom-
pass the range of maximum switching current (and switching time) from
low to very high fields. Table 2.5.1 illustrates this fact, displaying numerical
estimates of the basic parameters which determine the switching behavior of
TGS for 0.05 < E < 50kV/cm. We take (P s 0 /£ s o) = l//?3 = C/4TTT C = 1 as
a common factor in (i m )i_3- The dimensionless factor12 (ji/Ns)1/2 « 10~ 5
corresponding to the fraction of intervening dipoles is of the right order

Table 2.5.1.

Field im DF v AU Ec (3
(Hz) (eV) (kV/cm) (esu)

High (3) Eq. (12) 1 t „ ~ 1 . 2 x 1012 0-10 40 1

1/2 5
Low (2)* Eq. (18) (n/Ns) ~ 10" (vs/u) ~ 7 x 1 0 1 2 ~0.10 0.01 1 0 " 3 to 1 0 " 4

D F = Dipole fraction intervening in switching process (3)—(2); v (Hz) = a t t e m p t frequency;

AC/ = P o t e n t i a l barrier height; Ec = threshold switching field; /3 = m e a n field coefficient;
@i = ECi/(Pdm)i. For more details see references and m a i n t e x t .
154 Effective Field Approach to Phase Transitions

magnitude. Then assuming suitable a t t e m p t frequency values [I>TO, optic,

for regime (3) and VA, short wavelength acoustic, for regime (2)], we get
reasonable estimates for t h e potential barrier heights. It may be pointed
out, among other things, t h a t A t / from high-frequency relaxation d a t a 1 6
on e(w) at T < Tc gives A t / = 0.06 ev, in approximate agreement with
A t / = O.lOev from (z m )3 as a function of field; Ecs(T) agrees well with the
thermodynamic (Landau expansion of free energy) coercive fields, along
with /? 3 ss 1 « 4wTc/C. Ec2 is two orders of magnitude lower t h a n Ec3,
corresponding with the usual hysteresis loop coercive field value at room
temperature.

References

1. See, e.g., M.E. Lines and A. Glass, Principles and Applications of Ferro-
electrics and Related Materials (Clarendon Press, Oxford, 1977).
2. C.F. Pulvari and W. Kuebler, J. Appl. Phys. 29, 1742 (1958).
3. A.G. Chynoweth and W.L. Fledman, J. Phys. Chem. Solids 15, 225 (1960).
4. E. Fatuzzo and W.J. Merz, Phys. Rev. 116, 61 (1959).
5. B. Binggeli and E. Fatuzzo, J. Appl. Phys. 36, 1431 (1965).
6. M. Hayashi, J. Phys. Soc. Japan 33, 616 (1972).
7. A. Jaskiewicz and J. Przeslawski, Phys. Stat. Sol. (A) 56, 365 (1979).
8. R. Perez, E. Toribio, J.A. Gorri and L. Benadero, Ferroelectrics 74, 3 (1987).
9. R.C. Miller and G. Weinreich, Phys. Rev. 117, 1460 (1960).
10. J. Axe, Jpn. J. Appl. Phys. 24 (suppl. 24-2), 46 (1985).
11. See, e.g., A. Dekker, Solid State Physics (Prentice Hall, Englewood Cliffs,
NJ, 1962).
12. F. Jona and G. Shirane, Ferroelectrics Crystals (Pergamon Press, New York,
1962) and references therein.
13. H.H. Wieder, J. Appl. Phys. 35, 1224 (1964).
14. G. Luther, Phys. Stat. Sol. A 20, 227 (1973).
 Chapter 2.6

Polarization Switching
by Domain Wall Motion*

Ferroelectric polarization reversal under external field pulses 1-9 of variable

strength has been the subject of extensive research since the 1950s.
It may be noted that most previous works 1-9 studied ferroelectric
switching at room temperature. In this paper, switching measurements have
been undertaken near T c , with the aim of obtaining a description of the
field and temperature dependence of the maximum switching current (im)
at low fields.
We will summarize 11 and complement previous theoretical results for
low field switching in ferroelectrics, which will be compared later with our
experimental results.
It is well known that TGS single crystals grown from water solution
(usually at temperatures well above room temperature) suffer a thermal
shock when they are taken out of the solution and it is also known that
cooling shocks 11 give rise to many small spike-shaped microdomains (see
Chapter 2.5).
For simplicity, we may assume that the extended microdomains are
equidistant parallelepipeds arranged periodically with an average distance
2r m between nearest neighbors. For t < tm, the rate equations then are 11
(similar equations can be obtained for tm < t < ts)

£--[(:H(i)~+-(0(f)- (1)

*Work previously published under the title "Temperature dependence of polarization

reversal in TGS family crystals near T c , " M. de la Pascua, P. Sanchez, J.E. Lorenzo,
and J.A. Gonzalo, Ferroelectrics 94, 401 (1989). Copyright © 1989. Gordon and Breach
Science Publishers S.A.

155
156 Effective Field Approach to Phase Transitions

+n4 Pab - n4 Pba,, (2)

dt u

where Na and ATb are t h e number of unit cells per unit volume with ±
polarization, respectively, n is t h e number of microdomains per unit sur-
face (n = l / 2 r ~ 2 ) , u is t h e lateral distance between neighboring unit cells
(for T G S , u = (arcsin/3) 1 ' 2 , d is t h e sample thickness, b is t h e unit cell
parameter along the ferroelectric axis, and pab, pb& are t h e transition prob-
abilities (per dipole unit time):

Pab=PO2[{E + 02P)lM/kBT\,
Pba = m[-(E + (hPMksT],
P02 = £l2exp[-Av2/kBT],

where v2 is a n a t t e m p t frequency a n d /32 t h e domain mean field coefficient.

Subtracting Eq. (1) from Eq. (2), multiplying by /x, and taking into account
t h a t N = Ns (d/b), we have:

1/2 1/2
dPd 16 ( n_ Pd Tc (E + (32Pd
NfJL[l + sinh
dt T V EsQ

Tc(E + /32Pd
+ - cosh
T Eso } (3)

Since Nfj, 10->22 x 10 esu 3> 1/2, we can rewrite this equation as
follows:
1/2
dPd Pd TCE + 02Pd
const. 1 sinh (4)
dt Ps E>sO

T h e maximum value of (dPd/dt) occurs when t h e second derivative

vanishes:
-1/2
d2Pd TCE + 02Pd
dt 2 {I
const
Ps
— sinh
T Es0

+ u+ f
1/2
TCE + /3 2 P d
cosh (5)
T E,sO E.sO J dt
This implies, at t = t m ,

\TcE + foPd Pdn

tanh
E,sO
-2P S 1+
T ¥-
Es0 (6)
 Polarization Switching by Domain Wall Motion 157

and, therefore,
Pdm^\ Tc ft '
1/2 -2PS 1+
I —•— I = const. I 1 , „
dm Ps J 1 T Es0
1/2-
PdnO\TC (32~
1- -2R 1
Ps J ' T Es0
(7)
On the other hand, as shown below (see Eq. (13))

dm E - (32PS
1+ (8)
Ps 3/?2Ps
and we can write:
1/2
im « 6Av2 exp(-AEyfcT) ( jfj" N» (^j1' (^ ^

1/2 x 2 , -. 2 ^ - ! / 2
E - (32PS Tc E - f32Ps
1-4
3-BsO T 3Eso 3ESQ

(9)
2
At low fields [ ( £ - / 3 2 P s ) / 3 £ s 0 ] < 1, where /32PS = Ec2 = Ec is the low-
field regime coercive field and including all constant factors in C (constant
for each temperature), we get finally:

= C(E - Ecf'2. (10)

We show next that Wieder's empirical relation 13 for the asymmetry of

the switching current peak can be obtained from the present model. From
Eq. (6), we can obtain

^ /?2Pdm=tanh-i
+
_22 PK [U1 ++ ^ ^ Z k A (11)
T 3Eso Ps ) TEs0
and then
Pdm\ TC(32PS
E= — ^ o t a n h " 1 2 1+ /?2Pdm. (12)
J- C. T E.sO
Taking into account that f32Ps <C Eso = foPso, and therefore
tanh x « x, we can write
T Pdm\ TC(32PS
E « ^r-EsO -2PS 1+ /32Pdra = -3/3 2 P d m - 2ftP s .
T EtsO
(13)
158 Effective Field Approach to Phase Transitions

Dividing by QfoPs'

Pdm ( l
^E+l, (14)
2PS V 6/32Psy 3
which is the same result obtained empirically by Wieder 13
Pd
aE + b,
2PS
where the field E is defined with opposite sign.
The switching behavior of TGS crystals was studied by the conventional
technique in which one measures the current that flows through a series
resistors connected to the crystal as a function of time t. First, an electrical
square pulse is used to align all the dipoles in one direction, then a second
pulse of opposite polarity is used to measure the switching current as a func-
tion of time. The quantities of interest are: i m , the maximum switching cur-
rent; ts, the switching time; and tm, the time corresponding to i = im, which
should be larger than the rise time of the applied pulse. For a given temper-
ature the time ts decreases and the maximum switching current im increases
with increasing applied field, while the switched charge remains constant.
The sample was selected to have unbiased and undistorted hysteresis
loops (usually distortions are due to impurities and/or mechanical stresses).
The sample thickness was 0.1cm and surface area 0.21cm 2 . Gold foil elec-
trodes were attached directly to both main faces and all the measurements
were performed in dry air.
Figure 2.6.1 shows maximum switching current versus applied field, at
several temperatures. In Fig. 2.6.2(a), im vs. (E — Ec)z/2 has been plotted
obtaining a set of straight lines with different slopes corresponding to dif-
ferent temperatures. The data agree reasonably well with the theoretical
expression in Eq. (10). Both constants, C and Ec, have been computed by
means of a least squares fit method for each temperature.
In Fig. 2.6.2(b), ln(i m ) vs. 1/E has been represented, which should give
another collection of straight lines, according to the Miller-Weinreich model
(i and a have been computed by least squares fits, in the same way). Except
at very low fields, they appear to follow approximately straight lines in the
semilog representation.
The first question that arises is which the model fits better the exper-
imental data. Figure 2.6.2(a) and (b) does not solve clearly this problem.
Therefore, we have tried another kind of representation: i vs. C(E — Ec)3/2
(Fig. 2.6.3(a)), and im vs. i 0 0 exp(-Q!/£'). These plots allow us to see the
 Polarization Switching by Domain Wall Motion 159

4000 •

* t t I 'C « T * 4 Q . S -C
a T « l o *C 4 T * 4 2 »C
• T O O «C « T * 4 3 *C
4 T * « -C x T=44.S -C
• T O * «C
3000'

2000-

1000-

0 | * r ^ , « . ''** r
0.000 0.375 0.750 1.125 1.500

E (W/cm)

Fig. 2.6.1. Maximum switching current i m as a function of pulse height of applied

electric field for different temperatures.

* T t 0 «C 4 T E 4 0 . 1 *C
I T«10 -C 4 T H » -C
4 T s a o «C * T s 4 l «C
4 T = | i »C »r T S 4 4 . S *C
4 T t l l *C
3000-

<
^zooo

1000 ••• *
* • • • • • *

0.00 0.25 0.50 0.75 t.00

.3/2
(E-EC)J

Fig. 2.6.2(a). Maximum switching current (E - £c)3/2 for different

temperatures.

differences considerably better: the fit with the Miller-Weinreich theory

departs substantially more from the slope-one straight line than the result
of the statistical model given by Eq. (10), at least in this range of low
fields.
160 Effective Field Approach to Phase Transitions

A T= 0 + T=«o. J

*iv
*\ • »•
B Ts tD
* TsJO
1 Tt2»
• T»»J -C

4* '• *»# *\ * T;3S

n.
••.• * «
»-». 0 •t
V

*.
V,

3.0
0.0 3.5 7.0 HO
1/E (kV'cm)

Fig. 2.6.2(b). Natural logarithm of im vs. 1/E for the same temperatures.

4000 I 1 1 > i

A Ts 0 'C * T : < 0 , 5 -C O I
e T=io >c * T r < 2 «c
« Ts20 -c * T 5 4 S «C ° '
« T:J8 -c x T M 6 . J «C 0*
* Ts31 -C
3000

• °0' .

>°. *
2000
e

* * •

1000

0 1000 ' 2000 , . , ' 3000 ' 40

C(E-E C )

Fig. 2.6.3(a). Maximum switching current im vs. C(E — Ec)3/2. C and Ec have been
determined independently for each temperature, and the data are plotted in normal-
ized form.
 Polarization Switching by Domain Wall Motion 161

r— • T ' i — —i— r- —i

*
4 Ts 0 *C * T = 4 0 . S "C oj
0 T = 1 0 "C • TS42 «C
« TiJO ' C * T = <S -C °°
« T = « «C * T=<«5 'C * o
» T=3S ' C o
3000- • fl
o

*v *
< • .0 *
* o°*
=k 2 0 0 0 - Q
3

1000-

0- 1 "- "T i " -

1 — •>
1000 2000 3000 *000
i.exp(-a/E)

Fig. 2.6.3(b). Maximum switching current vs. ioo exp(—a/E). ioo and a have been
determined independently for each temperature, and the data are plotted in normalized
form.

Figure 2.6.3(b) departs from the expected results at (E — Ec) sa 0

because of incomplete switching. In other words, at low fields the area
under the switching curve is less than Ps. This behavior is not surprising.
The activation field in the Miller-Weinreich model, a, is nearly ten times
larger than Ec calculated with the present model, and does not agree with
Pulvari and Kuebler.2 On the other hand, the extrapolated value of Ec from
our switching data is proportional to the one measured from hysteresis loops
at ±50 Hz for temperatures in an interval of about 20 degrees below Tc. At
lower temperatures, 50 Hz hysteresis loops values for Ec are more likely
to correspond to the transition between low field switching (domain wall
motion at subsonic velocities) and high field switching (random polarization
reversal throughout the bulk of the crystal at supersonic velocities).
The dependence of maximum switching current of TGS crystals with
applied field at several temperatures has been investigated and it has been
shown to be in good agreement with the predictions of simple statistical
model. The predicted field dependence im(E) « C(T) (E - Ec(T)fl2 fits
data at T < Tc better than the usual expression im(E) « i^ exp(—a/E)
(Miller-Weinreich) and the predicted temperature dependence of the
162 Effective Field Approach to Phase Transitions

threshold field EC(T) « /32Ps(T) is also approximately fulfilled for low

field (subsonic) switching.

References

1. M.E. Lines and A. Glass, Principles and Applications of Ferroelectrics and

Related Materials (Clarendon Press, Oxford, 1977).
2. C.F. Pulvari and W. Kuebler, J. Appl. Phys. 29, 1742 (1958).
3. A.G. Chynoweth and W.L. Feldman, J. Phys. Chem. Solids 15, 225 (1960).
4. E. Fatuzzo and W.J. Merz, Phys. Rev. 116, 61 (1959).
5. B. Binggeli and E. Fatuzzo, J. Appl. Phys. 36, 1431 (1965).
6. M. Hayashi, J. Phys. Soc. Japan 33, 616 (1972).
7. A. Jaskiewicz and J. Przeslawski, Phys. Stat. Sol. 56, 365 (1979).
8. R. Perez, E. Toribio, J.A. Gorri and L. Benadero, Ferroelectrics 74, 3 (1987).
9. R.C. Miller and G. Weinreich, Phys. Rev. 117, 1460 (1960).
10. J. Axe, Jpn. J. Appl. Phys. 24 (Suppl. 24-2), 46 (1985).
11. M.J. Cabezuelo, J.E. Lorenzo and J.A. Gonzalo, Ferroelectrics 87, 353
(1988).
12. F. Jona and G. Shirane, Ferroelectrics Crystals (Pergamon Press, New York,
1962).
13. H.H. Wieder, J. Appl. Phys. 35, 1224 (1964).
 Chapter 2.7

Switching Current Pulse Shape*

Since the early work 1-6 on ferroelectric switching in crystals of the TGS
family, attempts were made to describe the shape of the switching current
pulse as a function of time. According to Pulvari and Kuebler, 1 the pulse
shape is well described by

j(t) = 2PS[^) exp

2 Um
where Ps is the spontaneous polarization, j is the switching current per unit
surface, and t the time required to reach j m a x - On the other hand, Fatuzzo
and Merz 3 fit the shape by the difference of two exponentials with the time
cosntants Ti and T^ as follows:

j(t) = J 0 [exp(-£/T 2 ) - e x p ( - t / T i ) ] ,
where jo is a constant.
Both expressions are of an empirical nature, and the criteria to fit the
data on j(t) were:

1. Making sure that the area under the curve is:

rta
jdt = 2Ps.
/o
./o
2. Insuring that the jmax(t) of the empirical expression occurs at the same
time as j m a x of experimental data.

*Work previously published under the title "Switching pulse shape in single crystals of
the TGS family," M. de la Pascua, G. Sanz, and J.A. Gonzalo, Proceedings of the 7th
International Meeting on Ferroelectricity, 1989. Copyright © 1989. Gordon and Breach
Science Publishers S.A.

163
164 Effective Field Approach to Phase Transitions

The expression for j(t) giving rise to a triangular (or smoothed trian-
gular) pulse can be obtained directly from the rate equations for polar-
ization change, assuming a certain distribution of preexisting reverted
microdomains. For sufficiently high fields (in the subsonic regime), jit)
for t < tm is given by 7

and for tm < t < ts by

i® = — {r~r)'
where ts is the switching time, defined as the time required for j to approx-
imately complete the switching process (for sufficiently high fields and cor-
respondingly symmetrical pulses, ts = 2tm). The symmetry of the switching
pulse depends strongly on the strength of the applied field: it goes from a
considerably asymmetric shape at low fields to an almost symmetric shape
at sufficiently high fields.5
Figure 2.7.1 gives j(t) for different applied fields. The statistical model
predicts triangular pulse shapes but, of course, does not fit the peak round-
ings of the experimental data. This triangular shape is due to the assump-
tion of an exactly periodic starting distribution of preexisting microdomains
in the sample.
For a gradual change in n (density of preexisting microdomains) with
position along a given direction of the sample (dn/dx — 0), we can describe
j(t) by means of a hyperbola that becomes asymptotically a straight line
at both sides of tm:

where JT{tm) is the maximum current density in the triangular fitting. The
rounding at t gives rise to a tail at t « 2tm.
In Fig. 2.7.2 we have plotted the predicted pulse shape after Pulvari-
Kuebler, Fatuzzo-Merz and our model along with the experimental data.
In conclusion, the pulse shape predicted taking as a starting point the
rate equations for polarization reversal at preexisting microdomain walls fits
fairly well the experimental data, better than previous empirical expressions
(Pulvari-Kuebler, Fatuzzo-Merz) and at least as well as the more elaborate
expression given later by Fatuzzo. 4 We note that our expression for j(t)
 Switching Current Pulse Shape 165

TIME (MS)

Fig. 2.7.1. Switching pulses at various fields for (a) triglycine selenate (at T = —20°C),
(b) triglycine sulfate (at T = 0°C), and (c) triglycine fluorberillate (Ref. 2). The predic-
tion given in Ref. 7 is a triangular pulse.
166 Effective Field Approach to Phase Transitions

• ocrciwtxrAi. DATA

_5> ' ' tin

TIME U s )

• ocmawEHTAi. OATA

PULVAn-KUEKXR

TIME ( M s)

Fig. 2.7.2. Experimental (symmetric) pulse shapes and theoretical fits (Pulvari—
Kuebler, Fatuzzo-Merz, this work) for (a) trigylcine selenate (at T = —20°C),
(b) triglycine sulfate (at T = 0°C), and (c) triglycine fluorberillate (Ref. 2).
 Switching Current Pulse Shape 167

is consistent with the law 8 j m « C(E-EC)3/2, rather t h a n with j m «

jo exp(—a/E). At least for the crystals of the T G S family investigated, the
power law expression gives a better description of the experimental behavior
of j m vs. E t h a n the exponential one in a relatively wide range of E.

References

1. C.F. Pulvari and W. Kuebler, J. Appl. Phys. 29, 1315 (1958).

2. C.F. Pulvari and W. Kuebler, J. Appl. Phys. 29, 1742 (1958).
3. E. Fatuzzo and W.J. Merz, Phys. Rev. 116, 61 (1959).
4. E. Fatuzzo, Phys. Rev. 127, 1999 (1962).
5. H.H. Wieder, J. Appl. Phys. 35, 1224 (1964).
6. B. Binggeli and E. Fatuzzo, J. Appl. Phys. 36, 1431 (1965).
7. M.J. Cabezualo, J.E. Lorenzo and J.A. Gonzalo, Ferroelectrics 87, 353 (1988).
8. M. de la Pascua, P. Sanchez, J.E. Lorenzo and J.A. Gonzalo, Ferroelectrics
94, 401 (1989).
 Chapter 2.8

Elementary Excitations
in Ferroelectrics: Dipole Waves

Low-temperature dipole-wave-like excitations in ferroelectrics, which are

analogous in certain respects to ferromagnetic dipolar spin waves (see, for
example, Ref. 1), might be expected on the grounds that, slightly above
zero temperature, collective-wave-like deviations of the elementary dipoles
from maximum alignment would require much less energy than the reversal
of single dipoles would. Ordinary acoustic phonons can coexist in a non-
interacting way with low-energy spin-wave-like excitations in solids pos-
sessing a spontaneous polarization. Consider a complex crystal in which
lattice points are occupied by rigidly bound groups of atoms instead of
single ions. Suppose that these groups of atoms possess permanent electric
dipole moments and that, below a certain transition temperature, there
is a non-zero spontaneous polarization and, therefore, an associated spon-
taneous local field. To find rigorously the ground state and the full spec-
trum of excited states of this system would demand the solution of the
many-body problem in one of its most difficult forms. One may reasonably
argue, however, that under favorable conditions the dipole wave excitations
can be considered as low-energy internal vibrational modes and then can
be treated separately from the normal low-temperature acoustic phonons,
which involve vibrations of the tightly bound group of atoms making up
a unit dipole. Intuitively, the energy required to produce long-wavelength
periodic deviations of the rigid dipoles from perfect alignment in the direc-
tion opposite to the field goes to zero as q goes to zero. We shall see below
that explicit separate consideration of the long-range dipole-dipole forces

*Work previously published under the title "Ferroelectric elementary excitations at low
temperatures: dipole waves," J.A. Gonzalo, J. Phys. C: Solid State Phys. 20, 3985 (1987).
Copyright © 1987. IOP Publishing Ltd.

169
170 Effective Field Approach to Phase Transitions

acting on a given elementary dipole gives rise to uq « Ssw(q)q2, which in

turn leads to T3'2 contributions to the low-temperature specific heat and a
low-temperature change in the spontaneous polarization. Ordinary acoustic
phonons give rise independently to a Debye T 3 contribution to the specific
heat and to a zero net contribution to the change in spontaneous polariza-
tion. (It is not uncommon to find reports in the literature of crystalline sys-
tems, e.g., some ammonium compounds, in which certain degrees of freedom
are "frozen" at T = 0 and then begin to be evident when the temperature
is raised, as vibrations of groups of atoms which were formerly behaving
as single point-like masses.) This effect, which shows up as a temperature-
dependent effective Debye temperature, is broadly ascribed to anharmonic
behavior. However, it is well known that high-energy internal modes of
molecular units in a solid are often relatively unaffected by the presence
of acoustic modes of very different energies. In the same way, it is pre-
fectly conceivable that the dipole waves, which are considered as very-low-
energy internal librational modes, behave as non-interacting modes with
respect to acoustic phonons of energy uiq « Sph{q)q, at least for temper-
atures low enough for the relevant (excited) wave vectors q to be such
that q < Ssw/Sph- This is equivalent to saying that short-range forces may
remain near equilibrium while long-range dipole-dipole forces (responsi-
ble for the dipole waves) are playing an active role. Of course, a definitive
check on the actual existence of excitations, which behave as u>q sa Ssw(q)q2,
must wait until systematic neutron scattering data well inside the Brillouin
zone are available (at low and high temperatures). In the ground state
(T = 0), dipole alignment should be maximum, but not perfect, because of
zero-point motion. The situation is partly analogous to that encountered
in dipolar (not exchange) ferromagnets. The main difference between ferro-
electric and (dipolar) ferromagnetic systems lies in the well-defined charac-
ter of the atomic magnetic dipole moment in the latter, in contrast with the
ill-defined electric dipole moment that makes up the complex primitive unit
cell in most ferroelectrics. A previous attempt to attack this problem 2 was
clearly insufficient and incomplete, partly because not enough experimental
evidence was available. A more systematic calculation is presented here, and
its results are compared with available experimental data on TGS. A sys-
tematic calculation of basic properties in ferroelectrics at low temperatures
is interesting in its own right, even though comparison with experiments is
difficult because of the somewhat conflicting results obtained by different
researchers (see discussion below).
 Elementary Excitations in Ferroelectrics: Dipole Waves 171

To investigate the anomalous low-temperature behavior in uniaxial fer-

roelectrics, we shall consider only the long-range dipole interactions, since
short-range interactions will give rise to normal behavior (Debye behavior
of the specific heat), which can be treated separately from the former.
A simple dipole-dipole interaction Hamiltonian (H = i?dipoie-dipoie) of
a system of N elementary electric dipole moments in a uniaxial ferroelectric
crystal under zero external field can be written as
„ v-^ l - 3 c o s 2 6 ^ ^
{i l
w I w
where #«' is the polar angle between l-V and the polar axis z, parallel
to the spontaneous polarization. The dipoles are assumed to be located
at regularly spaced fixed points in the crystal lattice and almost perfect
alignment is expected in the ferroelectric phase at low temperatures. If
we leave aside the short-range forces, the net restoring force due to all
neighboring dipoles on a given dipole can be represented adequately by
the spontaneous local field Es acting on the dipole. The usual mean field
approximation consists in assuming that every dipole in the crystal is under
the influence of an effective field Eeg = E + Es = E + (3P, where E is the
external field, Es the cooperative "spontaneous" field, and /3 a constant. The
last assumption is justified only at a temperature sufficiently lower than the
transition temperature Tc, so that lattice distortions are small, the unit cell
volume remains almost constant and the value of the order parameter is
very close to unity. The behavior of the system may change substantially
when appreciable anisotropic thermal expansion and new internal degrees
of freedom begin to enter the picture.
At any temperature higher than OK, every (n(t) undergoes, under the
influence of the spontaneous local field Es, a pseudo-regular precession (see,
for example, Ref. 3), which can be thought of as a regular precession around
Es accompanied by a small mutation of higher frequency, which might per-
haps be associated with an "uncertainty" in the /J,Z component, parallel
to Es.
We may anticipate that this motion is compatible with a low-
temperature specific heat that is proportional to T 3 / 2 , because we have
two kinetic degrees of freedom (motion of the tip of m towards z\\Es, and
motion perpendicular to z plus one potential energy degree of freedom,
defined by the angle a between \n and Es). The angular momentum Li(t)
associated with the motion of m (t) is perpendicular to [i\ = qd and to the
172 Effective Field Approach to Phase Transitions

velocity of its tip, and it is undergoing a regular precession. Therefore, from

Hiixi> = /z2 cos aw (2)

2
LtLv = L cos aw (3)

we obtain, dividing Eqs. (2) and (3),

7 2 = H2/L2 = imni/LiLv = constant, (4)

where, through the virial theorem,

e = 2Tk = 2V, Tk = V, L2/2I = M £ s cos 9. (5)

Here, Tk is the kinetic energy, V is the potential energy, / = Mr2 is

the moment of inertia of the dipole, M is its total mass, and 9 is the angle
between /z = qd and Es. For 9 small, and taking into account that within the
mean field approximation (see, for example, Ref. 2, and references therein)

fiEs = /3Nn2 = kBTc (6)

we obtain, after substituting Eq. (6) into Eq. (5) and Eq. (5) into Eq. (4),
2
7 w (d/r)2(q2/2MkBT). (7)

Consequently, we can substitute

WW = 72LiLi> (8)

in Eq. (1), leaving it in terms of angular momenta instead of elementary

dipole moments. We can now use directly the formalism of angular momen-
tum quantization (see, for example, Ref. 4) for a system of N quantized
processing dipoles to obtain

wq = 7 2 /i ] P Jw{l - exp[-iq(l - I']} = qi2h ^ Jw sin2 \q(i-i') (9)

1
We can use (nq) = [exp(hwq/kBT) — 1] (thermal average) in H to

H = H0 + J2 hu)2nq =H0 + ^ huq[exp(hujq/kBT) - l]"1. (10)

q g

(Note that a uniaxial ferroelectric is equivalent, for present purposes, to

a spin 1J2 ferromagnet and that in the intervening transformations we
 Elementary Excitations in Ferroelectrics: Dipole Waves 173

have neglected interactions between dipole waves.) To calculate the low-

temperature contributions of the dipolar waves to specific heat and spon-
taneous polarization, it is convenient to rewrite H as follows:

2 2 qdc
H - H0 = y^hwq{nq) h •y ha{q)Ja sin
2
<? q

qdc
= 2 , a(q)kB®Jo sin (11)
2

where

q(i-n
^ Jw sir
M) qdc
y~] Jw sir
2

1/3
Jo / J Jw) dc v, JV-I/3, e = /iVEJ»'AB. (12)

These are simple definitions which, for the time being, involve no
approximations. The a(q) are dimensionless parameters, in principle of
order unity, d is a characteristic length related to the unit-cell volume
(vc = iV _ 1 ), and 6 is a characteristic temperature, related to the strength
of the dipolar interaction in the geometry of the crystal lattice.
The low-temperature specific heat contribution due to dipole-wave-like
excitations is given by

ACv = nqkuJq
df ( ^ )

1 d a ( g ) ( e / r ) sin 2 (gd c /2)

(kBT f • d'q • (13)
8ir3dT exp[a( ( ? )(e/T) sm2(qdc/2)} 1
This can be written, using x = qdc/2, as

Nk T ag(@/T) sin 2 x
fix2 dx
ACV
df {& ° L BZ exp[a g (6/T) sin2 a;] - 1
(14)

where, for a given range of x, aq is an effective average of a{q) and ft < 4ir
is an effective integration solid angle. Since we are interested mainly in bulk
properties, the average takes care of the characteristic directional depen-
dence of u)q. We may assume a cylindrical Brillouin zone (BZ) for a uniaxial
174 Effective Field Approach to Phase Transitions

ferroelectric ("pill box" shaped for TGS) and then perform an approximate
integration in two steps.
(i) For 0 < q < <2DI, the central sphere with radius equal to the half-
height of the box, Q = 4w, sin2 a; w x2, and the first part of the integral
takes the form

/ a 9 (e/:Z> 4 {exp[a g (e/T)a: 2 ] - l } " 1 dx.

Jo

(ii) For qr>i < q < qt>2, the part of the cylindrical BZ outside the central
sphere, where qo2 is the half-diameter of the box, O = ^(qrti/q), sin2 x « 1
(if the ratio <7D2/(7DI is not abnormally large), and the second part of the
integral takes the form

XDI / a(9/T)ir{exp[a g (e/T)] - l } " 1 da;.

Jo

Using these rather rough approximations (which are needed to make

comparisons below with experimental data) and substituting the appropri-
ate results for the definite integrals, one obtains

ACV = B^'2 + B2(6g/T)2 expt-ef/T), (15)

where

Bt = 0.904ATfc B (2a£e) -3/2 , (16)

B2 = (23/2ir2)NkBrcA, (17)
2
e g = 2 a g e = 2ag/i 7 /fc B . (18)

Here, a§ is the mean value of aq for 0 < q < <?DI = 2xm/dc, and
a g the mean value of aq for QDI < q < </D2- The superscript C
refers to specific heat, to differentiate the ac from the corresponding
ap for spontaneous polarization to be introduced below. Note that the
q dependence of the aq for simple lattices is rather smooth, especially
for g —• 0 (see, for example, Ref. 1, and references therein). The param-
eters rc = { e x p ( a g 6 / T ) / [ e x p ( a g 0 / T ) - 1]}, very close to unity as long
as 0 g = a g 0 » T (which is the case for the experimental data to be
considered later), and A = (7r/2)[l — (QDI/QD2) 2 ], which is temperature
independent, are introduced to simplify the notation.
 Elementary Excitations in Ferroelectrics: Dipole Waves 175

The low-temperature change in spontaneous polarization from its max-

imum value at = 0 K is given by

AP2 = 5^A|if = ^ 7 A L 2 = 7 / i ^ n i =7/i]Tng

1 1 1 q

=
8 ^ JBZ exp(hojq/kBT)-ld q
- (19)

The same procedure used to evaluate AC leads now to

A P 2 = A i T 3 / 2 + A2, e x p ( - 9 g / T ) , (20)

where

A1 = 0.469iV 7 /i(2a^e)" 3 / 2 , (21)

A2 = (23/2ir2N>yhrpA) (22)

e g = 2agO = 2al>h12/kB. (23)

Here, again, QQ and a £ are mean values for the integration intervals
0 < q < <7DI and 0 < q < qc2, respectively. (Note that the approximate
integrand in the first interval, which contains x2 in the numerator instead
of x4, is slightly different from the previous integrand, while the approx-
imate integral in the second interval is exactly the same as before.) The
parameters T p « T c and A have the same meanings as those introduced in
calculating AC V .
Combining Eqs. (16)-(18) and Eqs. (20)-(23), we obtain

A1/B1 = 1.92{ar/aCy3/2>yh/kB, (24)

A2/B2 = {rP/rc)7h/kB = jh/kB, (25)

e g / O g = al/a% = 1; fcB0D = 2aDhj2. (26)

These simple relationships connect low-temperature spontaneous polar-

ization and specific heat behavior through the ratio ^h/kB « 5^/kB.
As mentioned in the introduction, the basic objective of this work is to
present a systematic theoretical description of the physical consequences
of spin-wave-like excitations in ferroelectric crystals, leaving aside a defini-
tive statement on whether they can be identified with the observed low-
temperature anomalies in some ferroelectrics.5'6 Alternative explanations,
such as impurity effects, have been suggested7 for the anomalous T 3 / 2
176 Effective Field Approach to Phase Transitions

specific heat behavior reported for some ferroelectrics. This latter work,
however, does not discuss either the exponential dependence with \/T
reported at a slightly higher temperature range, or spontaneous polarization
data apparently following the same pattern, 8 which was published shortly
afterwards. Further experimental work9 suggested a surface-to-volume ratio
of the specific heat T 3//2 term coefficient not confirmed by later work,10 in
which an excess observed specific heat contribution behaving as T n , with
1 < n < 2, was also reported. In contrast, very-low-temperature specific
heat measurements in various ferroelectrics 11 ' 12 using ultrapure samples
seem to support no excess low-temperature contributions, or extremely
small ones, above the normal T 3 Debye background. In connection with
the last data, it may be pointed out that the only exception among the five
crystals studied seems to be TGS, for which data are shown to be reduced
by a factor of 10. If one plots the points corresponding to T < I K on
the same scale as the data for the other samples and then extrapolates to
= OK, the result is a T 3 / 2 contribution slightly lower (by less than 30%)
but very similar to that originally reported. 5,6 In summary, while the exper-
imental situation is not yet clear, one may say that at least for TGS, after
all the available evidence (from both low-temperature specific heat and
spontaneous polarization data) has been considered, it is not unreasonable
to assume the presence of a T3'2 contribution followed by an exponential
contribution. In the following, we have used data of Lawless5,6 for B\ in
TGS (assuming that it is at least within an order magnitude of the true
experimental value) as well as the data of Vieira et al.s for A\.
Low-temperature specific heat data from ferroelectric TGS single
crystals 5,6 (in cgs units per unit volume) give

S i = 12.9, £2 = 9.1xl05, 6 g = 67K, (27)

and corresponding spontaneous polarization data 8 (in cgs esu units) give

A1 = 0.99 x 10" 4 , v4 2 =28, 6 g = 66K. (28)

Then, from Eqs. (24), (25), and (26), respectively, we obtain three inde-
pendent estimates of 7, in cgs esu units:

7 = 5.2xl05(c£/ag)3/2, 7 = 4.0xl0 6 , 7 = (l/aD)1/2x2xl06. (29)

The internal consistency of these data is excellent, since the ao and an

are dimensionless numbers of the order of unity.
Now, let us return to the theoretical expression for 7 in Eq. (7). Sub-
stituting in some values, we can check whether this theoretical value for
 Elementary Excitations in Ferroelectrics: Dipole Waves 177

7 based on the motion of molecular dipole units is or is not in agreement

with the experimental values in Eq. (29). Let us use, again in cgs esu units,
q w e = 4.8 x 10 1 0 , N = v'1 = 0.155 X 10 2 2 , d = n/e = Ps0/Ne «
1.7 x 1CT 8 , T PS vl/S « 8.6 x 1(T 8 , M = M m p = 321 x 1.67 x 1 0 " 2 4 and
kB Tc = 1.38 x 1 0 " 1 6 x 322. Substituting these values in Eq. (7), we obtain

7caic « 13 x 10 6 , (30)

which is in fairly good agreement with 7 [Eq. (29)].

It has been shown t h a t spin-wave-like elementary excitations in ferro-
electrics lead to extra low-temperature contributions to the specific heat of
the form

ACV(T) = B i T 3 / 2 + B 2 ( e g / r ) 2 e x P ( - 6 g / T ) ,

and low-temperature changes in the spontaneous polarization of the form

A P S ( T ) = AlT'il2 + A2 e x p ( - e g / T ) ,

where the coefficients in b o t h expressions are related to each other by

A1/B1 = l.92(a%/a$y3/2jh/kB,
A2/B2 = lh/kB,
e g / e g = 1, fcBeD = 2a D /i 7 2 .
T h e low-temperature d a t a available for T G S are in fair agreement with
these expressions.

References

1. J.R. Herringa and M. Marrenga, Physica A 38, 371 (1975).

2. J.A. Gonzalo, Ferroelectrics 20, 159 (1978).
3. A. Sommerfeld, Mechanics (New York: Academic Press, 1964).
4. P.L. Taylor, A Quantum Approach to the Solid State (Prentice-Hall, Engle-
wood Cliffs, NJ, 1970).
5. W.N. Lawless, Phys. Rev. Lett. 36, 478 (1976).
6. W.N. Lawless, Phys. Rev. B 14, 134 (1976).
7. S. Kirkpatrick and C M . Varma, Solid State Commun. 25, 821 (1978).
8. S. Vieira, C. de las Heras and J.A. Gonzalo, Phys. Rev. Lett. 4 1 , 1822 (1978).
9. W.N. Lawless, Phys. Rev. B 23, 2421 (1981).
10. M.C. Foot and A.C. Anderson, Ferroelectrics 62, 11 (1985).
11. H. Grimm, R. Villar and E. Gmelin, Proc. 17th Int. Conf. Low Temperature
Physics, ed. U. Eckern et al. (Amsterdam: North-Holland, 1984), p. 1377.
12. R. Villar, E. Gmelin and H. Grimm, private communication (1986).
 Chapter 2.9

Low-Temperature Behavior
of Ferroelectrics*

In previous work1 it was shown that quantized dipole-wave-like excitations,

analogous to dipolar ferromagnetic spin waves, can give a consistent descrip-
tion of the low-temperature specific heat and spontaneous polarization
behavior of ferroelectric crystals. The basic features of the dipole-dipole
hamiltonian and the main results relative to specific heat and polarization
will be summarized. An analysis of available experimental data in the light
of these results, previously restricted to triglycine sulfate,1 is extended here
to data on other displacive and/or order-disorder ferroelectrics, in par-
ticular lithium niobate (LiNbOs), barium titanate (BaTiOs), and sodium
nitrate (NaN02). The overall picture emerging from three independent esti-
mates of 7 = \n/L\ (where fi is the unit electric dipole moment and L the
angular momentum of the atoms making up the unit dipole in its preces-
sion with respect to the local spontaneous electric field) shows a fair degree
of consistency for all these crystals, taking into account the experimental
uncertainties and the approximations involved in the theoretical calculation.
The ground state of a normal, high T c ferroelectric, must show devi-
ations from perfect alignment of the elementary dipoles because of the
uncertainty principle. The connection established through 7 between the
electric dipole moment vector and the corresponding angular momentum
vector allows one to calculate the elementary excitations spectrum of the
lattice of interacting dipoles, assuming that these spin-wave-like excitations
are much lower in energy than the ordinary acoustic phonons. The quantum

*Work previously published under the title "Low T quantum effects in high T c Ferro-
electrics," J.A. Gonzalo, Ferroelectrics 79, 19 (1988). Copyright © 1988. Gordon and
Breach Science Publishers S.A.

179
180 Effective Field Approach to Phase Transitions

calculation is made in a way analogous to the one applicable2 for dipolar

ferromagnets. Under these assumptions, the dipole-dipole hamiltonian for
a lattice of N dipoles in a uniaxial ferroelectric under zero external field
can be written as

ll> \ \l i
\ J W
where On, is the polar angle between (l-l') and the polar z axis. Since1
each /ii (dipole moment) is perpendicular to its corresponding L\ (angular
momentum), 7 2 = fi2/L2 « constant, and H can be put in terms of the
i s . Making use of the standard commutation relations for angular momen-
tum, performing a Holstein-Primakoff transformation of L^ = Lx ± iLy in
terms of annihilation (a) and creation (a + ) operators of angular momentum
quanta, and changing from local to collective coordinates, one finally gets

H = £0 + ] P h[-j2h( Jo - Jq)\a+aq = e0 + ] P hioqnq, (2)

where Jq = J-q = ^2t Ju> exp{ig(Z — I')} for Bravais lattices and

toq = 212h J2 Jw sin2 \q{l - I') (3)

i

gives the dispersion relation for dipole waves, which for low |g| <C |QBZ| leads
to u) proportional to q2. This dispersion relation is used to get the expression
for low T contributions to the specific heat and change in spontaneous
polarization due to dipole waves.
As shown in Ref. 1, after making certain simplifying approximations, one
obtains for the specific heat and the polarization, using wq from Eq. (3),

(ACv)dw « -B1T3/2 + B2{@%/T)2 exp{-9g/T} (4)

and

(AP s ) d w « AXT^2 + A2 e x p { - e g / T } , (5)

respectively, where

Ai/B! = (1.92)(a 0 3 /aC)- 3 / 2 7 /i/fc B l (6)

p c
A2/B2 = (r /r )7h/kB = ^h/kB, (7)

©D/©D = <*o/«o = 1, fc9D - 2a D /i 7 2 . (8)

 Low-Temperature Behavior of Ferroelectrics 181

Table 2.9.1.

Crystal A X I(cgs u.) A2 (cgs u.) 0 g (K) Bi (cgs u.) B2 (cgs u.) eg(K) Refs.

LiNb03 1.47 x 10"4 56 130 28 18 x 10 5 128 3, 5

BaTi03 4.2 x 10"4 28 167 65 26 x 10 5 143 3, 5
NaNC-2 2.4 x 10"4 — — 41 16 x 10 5 81 4,6
TGS 1.0 x 10~ 4 28 66 13 9 x 10 5 67 3, 5

Table 2.9.2.

Crystal 7 x
(aoPi /« 0 -T 3 / 2 Eq. 7 Eq. 7 x (a
-C\-l/2
D ;
Eq.

LiNbC-3 0.36 x 10 6 (6) 4.0 x 10 6 (7) 2.9 x 10 6 (8)

BaTi03 0.44 x 10 6 (6) 1.4 x 10 6 (7) 3.3 x 10 6 (8)
NaN02 0.40 x 10 6 (6) — (7) 2.3 x 10 6 (8)
TGS 0.53 x 10 6 (6) 4.0 x 10 6 (7) 2.0 x 10 6 (8)

Here a0' , a D ' as well as 7 P ' C , are dimensionless numbers of order

unity, G D ' are characteristic temperatures, 7 = \/i/L\, and h and fee are
Planck's and Boltzmann's constants.
Since the A and B coefficients appearing in Eqs. (4) and (5) can be deter-
mined from available d a t a from some ferroelectrics one can make indepen-
dent estimates of 7 from Eqs. (6) and (8). Table 2.9.1 shows sets of A's and
£?'s d a t a from various sources for four oxide and non-oxide ferroelectrics.
From these d a t a and Eqs. (6)-(8) one gets three independent esti-
mates of 7, which show a fair degree of internal consistency as shown in
Table 2.9.2.

References

1. J.A. Gonzalo, J. Phys. C 20, 3985 (1987) and references therein.

2. J.R. Herringa and M. Marrenga, Physica A 38, 371 (1975).
3. J.A. Gonzalo, C. de las Heras and S. Vieira, Ferroelectrics 24, 101 (1980).
4. C. de Las Heras, J.A. Gonzalo and S. Vieira, Ferroelectrics 33, 13 (1981). (Note
that A has been determined directly from Fig. 2, because the corresponding
numerical value inTH appears to be mistaken. Numerical values for A and B
are not quoted, since they may be seriously affected by the strong secondary
pyroelectric contribution.)
5. W.N. Lawless, Phys. Rev. B 14, 134 (1976).
6. W.N. Lawless, Phys. Rev. B 25, 1730 (1982).
 Chapter 2.10

Logarithmic Corrections*

Radium dihydrogen phosphate (RbDP), a well-known ferroelectric iso-

morph of potassium dihydrogen phosphate (KDP), shows a second order
phase transition at Tc « 146 K at ambient pressure. Its dielectric, ther-
mal, structural, and lattice-dynamical properties have been extensively
studied. 1-9 The second order character of the transition, in contrast to that
of KDP, is generally agreed upon, while at the same time its proximity to
a tricritical point is stressed.
In their 1969 paper 10 on phase transitions of uniaxial ferroelectrics,
Larkin and Khmel'nitskii (LK) predicted logarithmic corrections to classi-
cal (Curie-Weiss) behavior of the dielectric constant and other anomalous
physical properties near T c , suggesting specifically triglycine sulfate (TGS)
and RbDP to test their theory. Logarithmic corrections in the specific heat
of TGS have been observed recently by Ema, 11 but no such corrections have
been unambiguously observed in the dielectric constant for this crystal as
far as we know. Recent dielectric constant measurements by Sandvold and
Courtens 12 on tris-sarcosine calcium chloride produced a good fit to an
empirical expression including logarithmic corrections compatible with LK
theory. No clear crossover to normal Curie-Weiss behavior was discernible
above Tc from these data.
The samples were cut from a single crystal grown from water solution in
the form of plates of 4 x 4 x 0.5 mm 3 with the main surfaces perpendicular
to the polar c-axis. Gold-leaf electrodes were directly attached to the main
surfaces. The sample holder was located within the evacuated cavity of
a cryostat filled with liquid N2. The slow spontaneous heating technique

*Work previously published under the title "Dielectric-constant logarithmic correction

in R.DH2PO above the Curie point," J.L. Martinez and J.A. Gonzalo, Phys. Rev. B 32,
400 (1985). Copyright © 1985. The American Physical Society.

183
184 Effective Field Approach to Phase TYansitions

was used in which the rate of heating of the evacuated sample cavity was
governed by liquid-nitrogen evaporation at a rate of about 0.5 K/min. At
regularly spaced time intervals we measured the capacitance and loss factor
(by means of an ESI universal video bridge) and the sample thermocouple
temperature (by means of a Fluke microvoltimeter). The relative precision
of the capacitance measurements was always better than 0.1% and the
relative precision of temperature readings better than 0.02 K. The residual
capacitance of the system to be subtracted from capacitance readings was
carefully determined using a set of single crystal cleaved plates of NaCl of
0.5 mm thickness and of varying area provided with gold-leaf electrodes,
and extrapolating linearly C for A (area) —• 0, obtaining 7.1 pF as residual
capacitance. The field amplitude used was 1 V/cm, considered sufficiently
low for this kind of measurement.
Measurements of sample capacitance and dielectric loss using an ac
amplitude of 1V were performed at the following frequencies: 20 Hz, 100 Hz,
1 kHz and 10kHz (all peak values fall within 5% of each other). In all cases
the temperature dependence was qualitatively the same: a gradual and rel-
atively small increase in capacitance below Tc followed by a much more pro-
nounced decrease above Tc, which did not quite fit the Curie-Weiss law in
the immediate vicinity of Tc. This is illustrated by the gradually decreasing
slope in e" 1 vs. T just above the transition temperature shown in Fig. 2.10.1
for 1 kHz, but the same feature was observable for all other frequencies at
which measurements were performed. Rounding due to impurity-induced
small bias or thermal gradients should show up as a bend in the slope in
the opposite direction. Previous work on RbDP by Gladkii and Sidnenko1
and by Peercy and Samara 4 do not show evidence of logarithmic correction.

TIKI

Fig. 2.10.1. Inverse dielectric constant vs. temperature for RDH2PO4 (F = 1 kHz,
V = lVrms).
 Logarithmic Corrections 185

On the other hand, our data contain many more points per degree, and the
bending of our data points for £ _ 1 vs. T is directly visible in a linear plot
only in an interval of about 5K above Tc. Roughly speaking the width of
the critical region should be of this order.
It may be pointed out that the peak value of the dielectric constant
in our data is substantially lower than others 2 - 4 previously reported. This
might be due to lower sample quality but in any case impurities and/or
defects usually give rise to bending of the e~l{T) curve in the opposite
direction. We have tried to fit the behavior of £ _ 1 (T) above the transition
to the expression of LK (Ref. 10) which can be written as

e~l = (AT/Cni + gHATo/C)}-1/3, (1)

where AT = T — Tc, C = Curie constant above T c , and g and ATo are

characteristic parameters of the material undergoing the second order phase
transition. Equation (1) can be rewritten as
- I / O
_! _ AT 9
£ InT
' C[l+g\n(AT0)}-^ l+5lnATo

= ^[l-</lnAT]-1/3. (2)

To determine the possible presence of the logarithmic correction term in

our data the most sensitive parameter by far is T c . To perform a preliminary
determination of T c , weighting properly the data closer to the transition,
one can use the following procedure: Assuming that a power law e~l =
A(AT)1 is approximately fulfilled, one can plot the ratio [£ _ 1 /(d£ _ 1 /dT)]
vs. temperature. If the assumption is correct one obtains a linear plot, and
from the extrapolation to £ _ 1 = 0 one obtains Tc directly. We followed
this procedure with our data, obtaining Tc = 145.90K. Using this Tc with
selected data for e~l encompassing an interval of 12 K above the transition
(at higher temperatures a trend toward normal Curie-Weiss behavior is
discernible) one can easily estimate the other parameters, g' PS —0.860
and C" « 1420. These parameter values were subsequently used as initial
values in a computer fit of Eq. (2) in which T c , g' and C" were left free to
change, to the full set of data for e _ 1 (T) in the whole temperature interval
omitting only the first three points corresponding to nearly flat £ _ 1 very
near T c . The parameters thus obtained were Tc = 145.85 K, g' = —0.86,
and C = 1425.36. The semi-logarithmic plot in Fig. 2.10.2 shows the good
fit of the theoretical expression for £ _ 1 (T) with the experimental values.
186 Effective Field Approach to Phase Transitions

Fig. 2.10.2. Semi-logarithmic plot of (e - £ 0 ) _ 1 vs. T for R b H 2 P 0 4 . The theoretical

curve is the LK expression [Eqs. (1) and (2)] with T c = 145.85, g' = - 0 . 8 6 , C" = 1425.36,
and eo = 3.5 (solid curve). Points are experimental data.

At temperatures for which A T > 12 K, the data appear to show a gradual

tendency toward Curie-Weiss behavior, which is slightly enhanced if one
subtracts from the e value eo ~ 4.5 ±1.5 estimated from room-temperature
measurements. Taking into account that the value for the Curie constant C
obtained from our data for 12 < AT < 40 K is C = 2.546 x 103 (lower by
13% than some previously reported 1 ) one can obtain from

C' = C(l+g In T 0 ) 1 / 3 = 1425.36 (3)

S' = 0 ( 1 + 5 In To)" 1 = -0.86 (4)

the corresponding values for the parameters in the LK expression

g m (—0.150) (dimensionless), (5)

AT 0 ?»237K. (6)

According to this, the value g is small and negative 13 and there would
be a change of sign in the product (g' In AT) in Eq. (2) at T = TQ = 237K
above T c , which, probably by a fortuitous coincidence, happens to fall very
close to the next high-temperature transition in RbDP (from tetragonal to
monoclinic), which takes place at T = 86°C. A negative g implies a diver-
gence of e _ 1 above Tc at AT = AT 0 exp(l/<?), in our case at AT RS 0.2K,
which is located in the critical region, below the temperature where (e - 1 ) e x p
becomes nearly flat, corresponding to experimental points excluded from
our fit.
 Logarithmic Corrections 187

LK state in their p a p e r 1 0 t h a t Eq. (1) is applicable for displacive-type

transitions, whereas e « \T - Tc\~l x In 1 / 3 \T - Tc\ is applicable for o r d e r -
disorder-type transitions. R b D P is generally considered to show an o r d e r -
disorder-type transition, like its isomorphs at ambient pressure, but there is
also experimental evidence 4 ' 1 4 t h a t it presents an u n d e r d a m p e d soft-mode
indicative, at least partially, of a displacive-type character of the transition.
In fact, the existence of double potential-well minima separated by energy
barriers does not exclude the possibility of relative displacements of these
minima, accompanied by changes in the height of the barrier, which could
give the transition a mixed (order-disorder) - (displacive) character. Thus,
the applicability of Eq. (1) to the R D P transition should not be ruled out
entirely on the grounds of its having order-disorder character.
T h e mean deviation
N
R = (1/iV) 22 \£TLpt - £i"c1alcl/£i"c1alc
i=l

for the logarithmic correction fit was i?LC = 0.0037, clearly better t h a n
the deviation for a power law ( e _ 1 = A ( A T ) 7 i ? P L = 0.0075). A t t e m p t s
to fit our d a t a with Curie-Weiss and power laws using background terms
linear in t e m p e r a t u r e gave definitely inferior fits to those obtained with a
logarithmic correction.

References

1. V.V. Gladkii and E.V. Sidnenko, Fiz. Tverd. Tela (Leningrad) 13, 1642
(1971) [Sov. Phys. — Solid State 13, 1374 (1971)]; see also M. Amin and
B.A. Strukov, Fiz. Tverd. Tela 10, 3148 [10, 2498 (1969)].
2. C. Pierre, J.P. Dufour and M. Remoissenet, Solid State Commun. 9, 1493
(1971).
3. B.A. Strukov, A. Baddur, V.N. Zinenko, A.V. Mishchenko and V.A. Kopstik,
Fiz. Tverd. Tela (Leningrad) 15, 1388 [Sov. Phys. — Solid State 15, 939
(1973)].
4. P S . Peercy and G.A. Samara, Phys. Rev. B 8, 2033 (1933).
5. P. Bastie, J. Lajzerowicz and R.J. Schneider, J. Phys. C 11, 1203 (1978).
6. F. Troussaut, P. Bastie, J. Bornarel and M. Vallade, Ferroelectrics 39, 1053
(1981).
7. P. Schnackenberg, J. Pipman, V.H. Schmidt and G.F. Tuthill, Ferroelectrics
39, 1045 (1981).
8. V.H. Schmidt, P.T. Schnackenberg, A.S. Western, A.G. Baker, C.R. Bacon
and W.P. Crummett, Ferroelectrics 24, 275 (1980).
188 Effective Field Approach to Phase Transitions

9. K. Gesi, K. Ozawa, T. Osaka and Y. Makita, J. Phys. Soc. Jpn. 52, 2538
(1983).
10. A.I. Larkin and D.E. Khmel'nitskii, Zh. Eksp. Teor. Fiz. 56, 2087 (1969)
[Sov. Phys. — JETP 29, 1123 (1969)].
11. K. Ema, J. Phys. Soc. Jpn. 52, 2798 (1983).
12. E. Sandvold and E. Courtens, Phys. Rev. B 27, 5660 (1983).
13. The negative value of g is somewhat unexpected. According to LK, however,
g = 37 = Tcbv/32n (As 3 ) 1 ' 2 , and, even if all the quantities involved are
positive, the square root implies a ± sign compatible with a negative g value.
On the other hand, a reasonably good fit can be obtained using C = 2250, a
positive g = 0.05, AT 0 = 20 K, and Tc = 145.2 (corresponding to g' = 0.0435
and C' = 2357), which presents a divergence at A T « 9.7 x 10 9 , very far
from Tc. The quality of the fit with the set of parameters in an interval of
AT w 20 K above T c is, however, definitely inferior to that obtained using
a negative g = —0.86 and C" = 1425, as indicated by a mean deviation (R)
about ten times larger in the former case.
14. P.S. Peercy, Phys. Rev. Lett. 3 1 , 379 (1973).
 Part 3
Some Applications to Ferroelectrics:
1991-1997
 Chapter 3.1

Pressure Dependence of the Free

Energy Expansion Coefficients in
P b T i 0 3 and B a T i 0 3 , and Tricritical
Point Behavior*
R. Ramirez, M.F. Lapefia, and J.A. Gonzalo
Departamento de Fisica Aplicada (C-IV),
Universidad Autonoma de Madrid,
E-28049 Madrid 34, Spain

Previous data for the pressure dependence of the order parameter for
BaTi03 at room temperature (RT) as well as new data for the pressure
dependence of the order parameter for PbTi03 at RT have been analyzed
within the framework of a phenomenological theory for ferroelectrics. It
is concluded that in BaTiC>3 a tricritical point is close but not accessible
at RT, while in P b T i 0 3 it is accessible at p = 1.75 x 10 1 0 dyn/cm 2 ,
allowing a full characterization of the pressure dependence of the free-
energy expansion coefficients.

It is well known 1 ' 2 t h a t rj, the order parameter [either the spontaneous
polarization P s or equivalently the unit-cell spontaneous strain z1'2 =
(c/a — 1) 1//2 ] of BaTiC>3, undergoes a weakly discontinuous first order tran-
sition under high hydrostatic pressure at room t e m p e r a t u r e (RT), which
indicates t h a t the crystal is not far from a tricritical point ( T C P ) at
RT and p*; 2.2 x 1 0 1 6 d y n / c m 2 . On the other hand, Raman-scattering
work 3 on P b T i 0 3 has indicated t h a t it undergoes a continuous second-
order phase transition under hydrostatic pressure at R T . Since the phase
transition of this crystal at ambient pressure is known to be first order,

*Work previously published in Phys. Rev. 42, 2604 (1990). Copyright © 1990. The
American Physical Society.

191
192 Effective Field Approach to Phase Transitions

this suggests a changeover from first order to second order at a certain

intermediate pressure. Recent X-ray diffraction data 4 indicate that at RT
and at p*, 1.75 x 10 1 0 dyn/cm 2 ( l P a = 10dyn/cm 2 ; l f r 8 k b a r ) , there is
a discontinuity in the slope of the order parameter rj [this time defined as
z1/2 = (c/a — 1)1//2] as a function of hydrostatic pressure, which can be
interpreted as the changeover from first order to second order behavior. It
may also be pointed out that unpublished X-ray diffraction data 5 on atomic
position shifts as a function of pressure seem to support this interpretation.
Figure 3.1.1 depicts the RT order-parameter pressure dependence of
PbTiC>3 and BaTiOs, showing the qualitative difference between both cases.
This difference of behavior will be subject to detailed analysis in this work,
within the framework of the phenomenological theory of ferroelectricity.6
Let us explicitly include the pressure dependence into the free-energy
expansion of the ferroelectric system in terms of even powers of the

(a)

Second order

(b)

Fig. 3.1.1. Order parameter [TJ = z 1 / 2 = (c/a - l ) 1 / 2 ] vs. pressure (p) at room tem-
perature for (a) PbTiC>3, showing discontinuity in slope at p = p c , identified as the
tricritical point, and (b) BaTiC>3, showing no such discontinuity at room temperature,
but displaying first order transition at p = p*.
 Pressure Dependence of the Free Energy Expansion Coefficients 193

polarization,

F(p) = F0(p) + \X{P)P2 + \aP)P4 + \C(P)P6 + L, (1)

where we assume

n ,n^(dx(p)\ n ,Tc(0) + [dTc(p)/dp]oP m

(2)
X(P) = X(O)+[-W)O, P = ^c(o) + idC(p)/dp)oP>
to) = e(o) + ( ^ ) , P = C(P-PC), (3)

which implies, for a first order transition at p = 0,

«0)<0, i.e.,c=(2®)o>0,

and

C(P), C(o) = C- (4)

From Eq. (1), taking into account that E = dF(p)/dP,

E = x(p)P + ttp)P3 + aP)P5+L, (5)

which, for E = 0, P = Ps, gives

O = X ( P ) P + £(P)P S 2 + C(O)P S 4 ,

and, therefore,

p?(p) = ( ^ ) {-^(P) ± [e(p) - 4CX(P)]1/2} (6)

where only the plus sign within curly brackets has a physical meaning.
To carry out the analysis of (i) the PbTi03 case, where we have identified
p = p c as the pressure corresponding to the TCP, i.e., to £(pc) = 0, and
(ii) the BaTiC-3 case, where p = p* is the pressure at which a first order
transition takes place under pressure at RT, we can get the relevant useful
194 Effective Field Approach to Phase Transitions

relationships as follows. Case (i): p = pc (TCP), f (pc) = 0,

Ps2=P s
2
(Pc)=(^) 1 / 2
, i - e . , C = ^ (7)

from Eq. (6) for £ = 0,

(8)
ifo
from Eq. (5) for E = 0, and

sn -e(o) (9)
^P Jo Pc
from Eq. (3). Case (ii): p = p* (first order transition), £(p*) < 0,

^ ( P ' ^ ^ A £V)=4CX(P*) (10)

from Eq. (6) for p = p*, where from

£(?*) = c ( p * - p c ) = [-4Cx(p*)] 1/2 . (11)

Combining Eq. (11) with

£(0)=c(0-pc), (12)

we can get p c and c in terms of known quantities.

Table 3.1.1 summarizes the relevant parameters for PbTiC-3 and BaTiOs
given in the literature. 2 ' 7 Using these data and the relationship given by
Eqs. (7)-(9) for P b T i 0 3 and Eqs. (10)-(12) for BaTi0 3 , one can obtain the
free-energy expansion coefficients, which have not been previously reported

Table 3.1.1. Transition parameters for PbTiOs and BaTiOs under hydrostatic
pressure. Numerical data for T c , (dT c /dp)o, C, and (dC/dp)o are from Ref. 2 except
the value in parentheses, which is from data in Ref. 7.

Crystal p (dyn/cm 2 ) T c (K) (dT c (p)/dp) 0 C (K) (dT c (p)/dp)o

(K cm 2 /dyn) (K cm 2 /dyn)

PbTiO 3 (0) 0 773 -7.1 x HT9 4.1 x 10 5 -9.1 x 10"6

PbTi03(pc) 1-75 x 10 1 0 649 — 2.5 X 10 5 —
BaTiO 3 (0) 0 395 -4.8 x 10"9 1.6 X 10 5 - 1 . 4 x lCT 6
BaTiQ 3 (p*) 2.2 x 10 1 0 287 — 1.3 xlO5 —
 Pressure Dependence of the Free Energy Expansion Coefficients 195

in the case of PbTiC>3 [where we have used a saturation spontaneous polar-

ization value -Pso(O) = 57/xC/cm 2 = 1.71 x 10 5 esu], as well as their pres-
sure dependence, which are given in Table 3.1.2. For BaTiC>3 we have taken
P s0 (0) = 25^C/cm 2 = 0.75 x 10 5 esu.
The pressure corresponding to the tricritical point of BaTiC>3 can be
obtained from Eq. (12) once c has been determined. It turns out to be
pc = 2.24 x 10 1 0 dyn/cm 2 , slightly larger and very close to p* = 2.20 x

Table 3.1.2. Free-energy expansion coefficients for P b T i 0 3 and B a T i 0 3 under

hydrostatic pressure.

Crystal p (dyn/cm 2 ) £ (esu) (d£/dp)o C (esu)

(esucm 2 /dyn)

PbTiO 3 (0) 0 -1.27 x 10~ 1 2 6.06 x 1 0 " 2 3 5.73 x 10-23

PbTi03(pc) 1-75 x 10 1 0 0 5.73 x 10"23
BaTiO 3 (0) 0 -6.79 x 1 0 " 1 3 30.4 x 1 0 - 2 3 2.33 x 10~26
BaTiQ 3 (p*) 2.2 x 10 1 0 0.09 x 1 0 ~ 1 3 2.33 x 10"26

(a) 0.26

(b) 30 * lo-«
25
•5~

1 20

s 15

10
a.
PL, 5
0
0 0.3 0.S 0.0 1.2 l.S l.B 2.1 2.4
P (GP«)

Fig. 3.1.2. Schematic representation of order parameter n(p,T) = Ps(p,T), for

(a) P b T i 0 3 and (b) B a T i 0 3 , showing a qualitative difference stemming from the fact
that the T C P falls on a different side of the RT isotherm for either system.
196 Effective Field Approach to Phase Transitions

1010 dyn/cm 2 . As pointed out above, however, the TCP is not accessible at
RT (T = 23°C), but it should be accessible at a slightly lower temperature.
Figure 3.1.2 summarizes, in a schematic way, the behavior of the order
parameter with pressure and temperature for the ferroelectric perovskites
PbTiOs and BaTiC>3. The qualitative difference between the pressure
behavior of both systems at RT isotherm for the former and the latter
system.
We may conclude that a consistent characterization of the pressure
dependence of the phase transition under hydrostatic pressure at RT is
possible within the simple framework of the phenomenological theory of
ferroelectricity. This is worked out under the assumptions implied in the
present discussion, i.e., a weak pressure and temperature dependence on
the pressure of the coefficients X(P) a n d £(p)-

Acknowledgments

One of us (R.R.) would like to thank R. Nelmes for his hospitality at the
University of Edinburgh, Edinburgh, United Kindom, where he became
acquainted with the study of pressure effects on phase transitions. We also
acknowledge helpful comments from B. Jimenez, from the Consejo Supe-
rior de Investigaciones Cientificas, Madrid, Spain. The financial support of
Comision Interministerial de Ciencia y Tecnologfa, Madrid, Spain, is also
acknowledged.

References

1. G.A. Samara, in Advances in High Pressure Research, edited by R.S. Bradley

(Academic, New York, 1969), Vol. 3, Chap. 3.
2. G.A. Samara, Ferroelectrics 2, 277 (1971).
3. J.A. Sanjurjo, E. Lopez-Cruz and G. Burns, Phys. Rev. B28, 7260 (1983).
4. R.J. Nelmes and A. Katrusiak, J. Phys. C 19, L725 (1986).
5. R.J. Nelmes, A. Katrusiak, H. Vincent and R. Ramirez (unpublished).
6. F. Jona and G. Shirane, Ferroelectric Crystals (Pergamon, New York, 1962).
7. R. Clarke and L. Benguigui, J. Phys. CIO, 1963 (1977).
 Chapter 3.2

Ultrasonic Study of the Ferroelectric

Phase Transition in R b D 2 P 0 4 *
Z. Hu and C.W. Garland
Department of Chemistry and Center
for Materials Science and Engineering,
Massachusetts Institute of Technology,
Cambridge, MA 02139, USA

J.A. Gonzalo
Departamento de Optica y Estructura de la Materia,
C-IV Universidad Autonoma de Madrid,
2804 9 Madrid, Spain

The velocity and attenuation of shear elastic waves have been measured
in the paraelectric phase of tetragonal R.DD2PO4. The softening of the
elastic stiffness C66 can be well described by a Curie-Weiss law. The
polarization relaxation time r exhibits conventional critical behavior:
T = TO(T — Tc)" 1 . Both TO and T c are very sensitive to deuteration.
The values Tc = 229.1 K and T 0 = 2.61 x 1 0 " 1 0 s K were obtained for
a RbD2P04 crystal that is 87% deuterated, whereas Tc = 147 K and
TO = 0.3 x 10" 1 0 sK have been reported for R b H 2 P 0 4 .

3.2.1. Introduction

Rubidium dihydrogen phosphate R b H 2 P 0 4 (RDP) and its tetragonal

deuterated counterpart RbD2PC>4 ( D R D P ) are isomorphs of the well-
known KH2PO4 (KDP) family. 1 A comparison of the acoustic behavior
of R D P and D R D P has been undertaken to increase our understanding
of t h e ferroelectric phase transition in K D P - t y p e crystals and t o provide

*Work previously published in Ferroelectrics 112, 217 (1990). Copyright © 2005.

Taylor & Francis Group.

197
198 Effective Field Approach to Phase Transitions

useful background data for the orientational glass-forming mixed systems

RDP/ADP and DRDP/DADP, where A = NHj. 2 - 3
RDP has a tetragonal structure at room temperature. DRDP can be
obtained with either monoclinic or tetragonal structures, depending on the
crystal growth conditions. 4 In this paper, we will be concerned only with
the tetragonal form of DRDP.
Upon cooling, both RDP and DRDP undergo ferroelectric phase tran-
sitions from tetragonal (space group 142c!) to orthorhombic (Fdd2). The
critical temperature Tc strongly depends on the amount of deuteration,
ranging from Tc ~ 147 K for pure RDP 5 to Tc ~ 223 K for a 80% deuterated
sample. 6 The ferroelectric transition in RDP is second order. 5 However, a
95% deuterated sample exhibits a well-defined first order discontinuity in
the dielectric constant at T\ > Tc.7 This crossover from second order to
first order upon deuteration implies that a tricritical point exists at an
intermediate deuteration concentration.
Ultrasonic and hypersonic shear waves are effective probes for studying
ferroelectric transitions in the KDP family.8 Approaching Tc from above,
the acoustic attenuation increases and the acoustic velocity decreases due
to piezoelectric coupling between the elastic strain and the electric polar-
ization. The acoustic properties of RDP have been investigated by sev-
eral groups, 9 - 1 1 but DRDP has not been studied previously. Very recently,
an impulsive stimulated Brillouin scattering study 5 has demonstrated that
the shear elastic behavior of RDP can be completely understood with
mean-field theory, in contradiction to earlier specific heat 12 and dielectric 13
measurements, which had indicated the presence of a logarithmic correc-
tion term.
In this paper, data are reported for a single crystal of DRDP; that is,
~87% deuterated. Analysis of the velocity and attenuation of the elastic
shear wave yields the elastic constant CQQ and the polarization relaxation
time r as functions of temperature in the paraelectric phase of DRDP. Our
results can be well described by mean-field theory. The effect of deuteration
on the static and dynamic critical behavior will be discussed and compared
with that observed for KDP and KH 3 (Se0 3 ) 2 -

3.2.2. Experimental

A single crystal of DRDP with tetragonal structure was grown by Inter-

active Radiation, Inc. The sample had dimensions of ~ 1 x 1 x 1.6 cm 3
 Ultrasonic Study of the Ferroelectric Phase Transition in RbDzPOi 199

and a pair of flat and parallel surfaces normal to the x-axis. The nominal
concentration of deuterium was stated to be 97%. From the value of Tc
determined from our ultrasonic measurements and the relation between Tc
and deuterium concentration given in Ref. 6, we estimate that the actual
deuteration of the sample is about 87%.
The absolute sound velocity u was measured at intervals of roughly 35 K
with an accuracy of ± 1 % using the Papadakis pulse-overlap technique. Rel-
ative changes in sound velocities as a function of temperature were deter-
mined with high precision using a computerized phase-sensitive detection
technique and a MATEC MBS 8000 system. 14 A lithium niobate transducer
(10 MHz fundamental frequency, 41° x-cut) was bonded to the sample with
Nonaq grease. The acoustic wave of interest is the transverse mode prop-
agating with wave vector parallel to the [100] axis and polarization vector
parallel to the [010] axis. This mode is associated with the shear elastic
constant c§§ = pu2. We have used p = 2.866g/cm 3 , the room temperature
mass density of RDP, 9 for all of our calculations. The effects of deuteration
and thermal expansion on the mass density are estimated to be less than
1.5% and have been neglected. At room temperature, the values (in units
of 10 9 N/m 2 ) of e n , c 44 , and c 66 are 61.9, 10.13, and 3.14 for our DRDP
sample, in comparison with 67.0, 10.27, and 3.59 for a pure RDP crystal. 9
Absolute attenuation values were obtained from a measurement of first
and second echo amplitudes when T was far away from Tc. Near Tc, changes
in attenuation were measured by following the amplitude of the first echo
as a function of temperature. All measurements were confined to the para-
electric phase since the echo pattern disappeared in the ferroelectric phase
due to domain-wall scattering. A cooling rate of about 0.1 K/min or slower
was used.

3.2.3. Results and Discussion

Figure 3.2.1 shows the elastic stiffness C66 of DRDP as a function of

temperature at various frequencies. As expected, the CQQ softens on cool-
ing toward the ferroelectric transition. The lowest observed CQQ value is
0.635 x 109 N/m 2 at 7\ = 230.28 K, which is about 1.2 K above the extrapo-
lated second order critical temperature Tc. The abrupt disappearance of the
echo pattern indicates that the sample undergoes a weak first order phase
transition at T\. Values of C66 obtained with three ultrasonic frequencies are
in excellent agreement and demonstrate the absence of velocity dispersion.
200 Effective Field Approach to Phase Transitions

i | • •• i
i • i •

3.0 -

2.5 j r -

2.0 -

1.5 -
3
3

1.0 -i -

0.5 -

n > i i i

240 260 280 300

T (K)

Fig. 3.2.1. Temperature dependence of the C66 elastic stiffness for 87% deuterated
D R D P at 10 (o), 31 (+), and 52MHz (A). The solid line is a Curie-Weiss fit using
Eq. (2).

Thus, we consider that these cee values represent the static behavior of the
system.
As for all KDP-family crystals, the lowest order Landau expansion of
the free energy can be expressed as 8

F = F0 + i a ( T - T0)Pi + i c g 6 e | + a36P3e6, (1)

where the order parameter P3 is the electric polarization along the 2-axis, eg
is the elastic strain, Cg6 the bare elastic stiffness, 036 the piezoelectric con-
stant, and To the temperature at which the crystal would undergo ordering
in the absence of piezoelectric coupling, a is proportional to the dielectric
Curie constant C (a = C/4ir). Prom Eq. (1), one can obtain 8

T-Tc
cm u
66 (2)
T-T0'
with

rp _ rp , Ca36
4-Trr0 '
(3)
 Ultrasonic Study of the Ferroelectric Phase Transition in RbD2P0i 201

where T c is the second order transition temperature at constant (zero)

stress. The ce6 elastic stiffness data for DRDP are well described by this
mean-field equation as shown in Fig. 3.2.1.
The least-squares fitting parameters c^6, T c , and T0 are 3.4 x 10 9 N/m ,
229.08K, and 223.97K, which can be compared with 4.2 x 10 9 N/m 2 ,
147.0 K, and 140.4 K for RDP. 5 Values of AT = Tc - T0 for RDP varying
from 0.2 to 6.6K have been obtained by different techniques (see Ref. 5),
and our value of AT = 5.1 K for DRDP is close to AT = 6.6 K for
RDP obtained from the stimulated Brillouin data. 5 Published values of
the dielectric Curie constant C for DRDP range from 3140 K (Ref. 7) to
3800 K (Ref. 6). Adopting an average value of 3470 K for C, one obtains
d36 = 2.5 x 10 4 esu, which is close to the value 036 = 3.0 x 10 4 esu for
RDP. 5 Indeed, all the parameters needed to describe the static c6e behav-
ior of DRDP are similar to those for RDP except T c , which is increased
~82 K by deuteration. The same conclusion is obtained from a comparison
of c66(T) data for KDP 1 5 and DKDP. 16
The ultrasonic attenuation in DRDP is shown in Fig. 3.2.2 as a func-
tion of temperature for three different frequencies. As in other KDP-type

50 |—r T

40

~30
E
U
"^
m
T>

"20

10

235 240 245 250

T (K)
0
Fig. 3.2.2. Attenuation
230 a of the C66 acoustic wave vs. temperature at frequencies of
10 (o), 31 (+), and 52MHz (A).
202 Effective Field Approach to Phase Transitions

crystals, there is a substantial increase in the attenuation as Tc is

approached. It was not possible to follow the ultrasonic echoes all the way
down to the transition for measurements at 31 and 52 MHz due to high
attenuation and serious pulse distortion.
In the low-frequency regime (LOT <C 1), the critical sound attenuation
associated with the soft CQQ mode is given by8
c
6 6 ~~ c 6 6 2 / A \
ac = a-a0= LO2T, (4)
zuc 66
where r is the polarization relaxation time at constant stress, u the sound
velocity, to = 2irf the angular frequency, and ao the noncritical background
attenuation.
We have tested the quadratic frequency scaling by plotting (a — ao)/to2
vs. T, as shown in Fig. 3.2.3. The values of ao are small and independent of
temperature. The validity of the quadratic frequency dependence for a c is
consistent with our elastic stiffness data, which exhibit no sign of frequency
dispersion.
Since the bare stiffness Cg6 is known from the Curie-Weiss fit to the
static CQQ(T) data, Eq. (4) and the data shown in Fig. 3.2.3 will yield the

**. J -i 1 , ,

^3.0

a
x
%
o
3 1.5

230 235 240 245 250

T (K)

Fig. 3.2.3. Values of (a - a0)/ui2 obtained at 10 (o), 31 (+), and 52 MHz (A) as a
function of temperature. The ao values in dB c m - 1 are 2 for 10 MHz, 6 for 31 MHz, and
3 for 5 MHz.
 Ultrasonic Study of the Ferroelectric Phase Transition in RbDiPOt, 203

-
-
^ 6

- AJHI"
-

- -
—

-y 230
m^

235
I
240
I
245 250
T (K)

Fig. 3.2.4. Polarization relaxation rate 1/r vs. temperature for 87% deuterated DRDP.
The solid line is the best fit with Eq. (5).

relaxation time r. Figure 3.2.4 shows that the critical relaxation rate 1/r
is a linear function of temperature, as expected for conventional van Hove
critical slowing down:

- = -{T-Tc). (5)
T T0

The linear fit shown in Fig. 3.2.4 corresponds to To = 2.61 x 10~ 1 0 sK

and Tc = 229.1 K. Comparing this T 0 value for DRDP with r 0 = 0.3 x
10~ 10 s K for RDP, 5 we obtain a deuteration amplitude ratio R = T^/T^ =
8.7 for RDP. This ratio is very similar to the values R = 8.3 for KDP 1 5 ' 1 6
and R = 7.5 for the ferroelastic system KH3(Se03)2- 17
For uniaxial ferroelectrics with soft acoustic modes, critical fluctua-
tions can be suppressed by the long-range interactions associated with
piezoelectric coupling between electric polarization and elastic strain. In
fact, renormalization group calculations 18 have shown that for KDP-type
systems the upper marginal dimensionality is 2.5. Therefore, mean-field
behavior without logarithmic .corrections is expected, as observed in RDP
and DRDP.
204 Effective Field Approach to Phase Transitions

T h e traditional microscopic theory for the ferroelectric phase transition

in the K D P family is based on an order-disorder model t h a t considers pro-
ton tunneling between two sites of adjacent t e t r a h e d r a (for a review, see
Ref. 19). P r o t o n motion plays an important role in triggering this transition,
as indicated by the large increase in transition t e m p e r a t u r e upon deutera-
tion. Another mechanism 2 0 for the K D P - t y p e transition has been proposed
in which the isotope effect on T c is caused by a geometric distortion of PO4
tetrahedra. R a m a n scattering in R D P and D R D P has given s u p p o r t 2 1 for
this new mechanism. Our dynamic result, i.e., a relaxation amplitude for
D R D P ~ 9 times larger t h a n t h a t for R D P , may also be explained qualita-
tively by this model: since the distortion of PO4 t e t r a h e d r a on deuteration
results in an increase in the energy barrier for the flip-flop motion of PO4,
the polarization relaxation time increases upon deuteration. Our results,
however, cannot distinguish which mechanism, proton tunneling or distor-
tion of PO4 tetrahedra, plays the essential role in the ferroelectric phase
transition.

Acknowledgments

We wish to t h a n k V. Hugo Schmidt for providing the D R D P sample. This

work was supported in p a r t by NSF grant DMR-87-10035 and in p a r t by
U.S.-Spain Joint Committee for Scientific and Technological Cooperation
award CCB8604012.

References

1. K. Gesi, K. Ozawa, T. Osaka and Y. Makita, J. Phys. Soc. Jpn. 52, 2538
(1983).
2. E. Courtens, Hely. Phys. Acta 56, 705 (1983).
3. H. Grimm, K. Parlinski, W. Schweika, E. Courtens and H. Arend, Phys. Rev.
B33, 4969 (1986).
4. M. Sumita, T. Osaka and Y. Makita, J. Phys. Soc. Jpn. 50, 154 (1981).
5. L.T. Cheng and K.A. Nelson, Phys. Rev. B37, 3603 (1988).
6. B.A. Strukov, A. Baddur. V.N. Zinenko and A.V. Mishchenko, Sov. Phys.
Sol. State 15, 939 (1973).
7. J.L. Martinez and J.A. Gonzalo, Solid State Commun. 52, 1 (1984).
8. E. Litov and C.W. Garland, Ferroelectrics 72, 19 (1987).
9. V. Mnatsakanyan, L.A. Shuvalor, I.S. Zheludev and I.V. Gavrilova, Sov.
Phys.-Cyst. 1 1 , 412 (1966).
 Ultrasonic Study of the Ferroelectric Phase Transition in RbD^PO^ 205

10. M.C. Pierre, J.P. Dufour and M. Remoissenet, Solid State Commun. 9, 1493
(1971).
11. G.P. Singh and B.K. Basu, Phys. Lett. 64A, 425 (1978).
12. M.A. Amin and B.A. Strukov, Sov. Phys. Solid State 10, 2498 (1969).
13. J.L. Martinez and J.A. Gonzalo, Phys. Rev. B32, 400 (1985).
14. P.W. Wallace and C.W. Garland, Rev. Sci. Instrum. 57, 3085 (1986).
15. C.W. Garland and D.B. Novotny, Phys. Rev. 177, 971 (1969).
16. E. Litov and E.A. Llchling, Phys. Rev. Lett. 21, 809 (1968).
17. C.W. Garland, G. Park and I. Tatsuzaki, Phys. Rev. B29, 221 (1984).
18. R.A. Cowley, Phys. Rev. B13, 4877 (1976); R. Folk, H. Iro and F. Schwabl,
Z. Phys. B25, 69 (1976).
19. V.H. Schmidt, Ferroelectrics 72, 157 (1987).
20. M. Tokunaga and I. Tatsuzaki, Phase Transitions 4, 97 (1984).
21. J.L. Martinez, J.M. Calleja and J.A. Gonzalo, Solid State Commun. 52, 499
(1984).
 Chapter 3.3

New Technique for Investigating

Ferroelectric Phase Transitions:
The Photoacoustic Effect*
Jorge 0 . Tochot, Rafael Ramirez, and J.A. Gonzalo
Departamento de Fisica Aplicada C-IV,
Universidad Autonoma de Madrid,
28049 Madrid, Spain

Measurements of the photoacoustic effect in properly oriented triglycine

sulfate crystals from 30 to 60° C show clearly the ferroelectric phase tran-
sition in this crystal manifested by the pronounced thermal expansion
anomalies. The same method is generally applicable to similar phase
transitions.

Of the large number of properties that can be studied by photoacoustic

(PA) techniques, the probing of thermoelastic properties of materials is
one of those less explored. 1 ' 2 Acoustic waves generated after the absorption
of modulated or pulsed optical radiation, the photoacoustic effect, provide
information of sound velocity, specific heat, thermal expansion, thermal
conductivity, and other related parameters in a very attractive way.
While studies in the gas phase are performed mainly by the use of mod-
ulated irradiation and microphone detection, 3 in condensed matter acous-
tic waves can be efficiently detected by piezoelectric transducers (PZTs)
in direct contact with the material, due to the good acoustical impedance
matching that they present. PZTs have frequency-dependent responses with
sharp resonances related mainly with its physical dimensions. Hundred

*Work previously published in Ferroelectrics 59, 14 (1991). Copyright ©1990. Taylor &
Francis Group.
t Permanent address: Centro de Investigaciones Opticas and Departamento de Fisica, La
Plata, Argentina.

207
208 Effective Field Approach to Phase Transitions

kilohertz resonance frequency is found for PZT transducers but several

hundreds of megahertz can be reached with polyvinylidene diflouride piezo-
electric films (PVF2). Such ranges of frequencies are easily generated with
pulsed laser excitation. 4
The PA signal from a sample may change due to several factors. In the
direct coupling method, the acoustic wave is related with the thermal expan-
sion AVth of the irradiated volume VQ. In the more studied isotropic case

AHh = (P/CpP)H,

where /3 is the volume expansion coefficient, Cp is the specific heat at con-

stant pressure, p is the density, and H is the heat deposited in the volume
VQ. This expansion creates a pressure wave that travels outwards at the
velocity of sound. Since the electrical signal generated in the transducer is
proportional to pressure,

PA signal = K(0/Cpp)(l - KT^Bb,

where A is the optical absorbance of the sample, EQ is the pulse laser energy,
and K is a constant that includes the response properties of the transducer.
This formula is valid for a small radius irradiated cylindrical region,1 and
for an optically and thermally thick sample. In this way, the PA detection
of phase transitions is possible if the thermal parameters change as the
experimental conditions change.
Triglycine sulfate (TGS) is a well-known ferroelectric, which is being
used as a pyroelectric detector. 5 It shows a second order phase transition 6
to the nonpolar high-temperature phase at Tc = 49.3°C. The point group
symmetry of the ferroelectric phase is monoclinic 2 and that of the nonpolar
phase is 2/m. Below the transition temperature, a spontaneous polarization
appears along the monoclinic b axis. Good optical quality, transparent single
crystals of TGS can be easily grown from water solution.
The acoustic detector and the electrical impedance adapter used in this
work were built at Max-Planck Institut fur Strahlenchemie by Braslaysky
following an early design of Patel and Tam. 2 PZT is 4 mm in diameter and
4 mm in length. TGS slabs, cut from different crystal, orientations with
typical dimensions of 5 x 5 x 1 mm 3 , were coupled to the detector with
a drop of vacuum grease. The temperature of the system was stabilized
better than 0.5°C. Laser pulses were attenuated by a polarizer to ener-
gies below 1 mJ and focused by a 15-cm focal length single cylindrical lens
(Fig. 3.3.1(a)). The volume irradiated in the sample was 5 x 0.2 x 1mm 3
 New Technique for Investigating Ferroelectric Phase Transitions 209

PA SIGNAL

f,o t.a 1.4

(b> WAVELENGTH (j*m) TIME DElAYC^s}

Fig. 3.3.1. (a) Top view of the experimental setup. CL, cylindrical lens; PZT, piezo-
electric transducer; E, energy meter; T, temperature sensor, (b) Optical absorbance of
TGS in the near-IR. (c) Time delay between the laser line and the first peak of the PA
signal for 6-cut TGS.

(Z, X, Y). The absorption in the near infrared (IR) of these samples allows
us to use 1.06-/jm laser pulses from a Nd:YAG laser (Fig. 3.3.1(b)).
The crystal attached to the PA detector was mounted on a micrometer
translation stage that provided a fine X position. Transducer signals were
observed in an oscilloscope, digitalized, and saved in a microcomputer.
Small changes along the X direction of the position of the irradiated
zone of the crystal, by translation of the whole-system crystal-detector
amplifier, produce differences in the delay between the laser line and the
arrival of the first acoustic signal to the detector. The sound velocity in TGS
210 Effective Field Approach to Phase Transitions

can be measured in this way for longitudinal waves propagating parallel to

different axis. Figure 3.3.1(c) shows the results for the 6-axis as an example.
Time-resolved PA signals from PZT detectors show ringing at the reso-
nance frequency and our attention is in the early part of the PA signal. In
this way, we avoid contamination by acoustic reflections in the boundaries
of the sample.
To check the polarity of the detection system we corn-pared directly
the signal obtained below and above the phase transition temperature in
a crystal where the 6-axis corresponds to the X direction with the sig-
nal obtained when the crystal is replaced by a spectrophotometric quartz
cuvette with 0.1 absorbance C0SO4 water solution in it and using a l m J ,
532 nm laser pulse. The electrical polarity of the detection system produces
negative-going first pulses when the expansion coefficient is positive.
The modification of the volume irradiated from the standard cylindrical
shape, with its axis in the direction of irradiation to a prism with its larger
side perpendicular to both the direction of irradiation and the acoustic-wave
propagation, allow us to measure the thermal properties in pure, crystallo-
graphic directions. In these conditions, the amplitude of the PA signal can
be written as
PAS = KotifiviyCp,

where on is the thermal expansion coefficient along the i direction of the

crystal and / is a function of sound velocity in the aforementioned direction
Vi. Such a function depends 1 ' 2 on the ratio between the pulse duration of
the laser and the transit time of the acoustic wave inside the irradiated
zone in our geometrical conditions d{v) — v1/2.
By measuring the PA signals in terms of temperature we follow the ther-
mal properties of the sample. Figure 3.3.2 shows several signals at different
temperatures for a sample where the experimental X direction corresponds
to the crystallographic 6-axis. The change in sign of the acoustical first sig-
nal can be clearly seen when the phase transition occurs. The amplitude of
the PA signal reflects the big change in the thermal expansion coefficient.
This fact can be confirmed by plotting the amplitude of the first PA signal
peaks versus temperature. Figure 3.3.3(a) shows the results for a crystal
oriented with 6-axis along the X direction. For comparison, we show the
relevant thermal expansion coefficient a/,, given by Shibuya and Hoshino,7
below the phase transition temperature and, with more resolution by Ema
et al.8 above the phase transition temperature. The PA signal was normal-
ized to fit the thermal expansion coefficient at 60° C.
 New Technique for Investigating Ferroelectric Phase Transitions 211

5 10
TIME (yu-s)

Fig. 3.3.2. Time-resolved PA signal of 6-cut TGS at different temperatures. The PA

signal at 50° C shows a shoulder at the wing of the first peak; similar "PA phase reversal"
has been previously reported [A.C. Tarn and C.K.N. Patel, Appl. Opt. 18, 3348 (1979)].

Figure 3.3.3(b) shows similar results for a sample oriented with the c-
axis along the X experimental direction. When this sample was rotated and
the a± direction (perpendicular to the a-axis) was in the X experimental
direction, the PA signal was more complicated due to mixing of waves with
different propagation velocities and polarities.
The PA signal reflects mainly the changes in the thermal expansion coef-
ficients along the direction perpendicular to both the irradiation direction
and the acoustic-wave propagation direction. While the specific heat and
the sound velocity also change through the phase transition, in the case of
TGS these changes are much smaller than that of the thermal expansion
coefficients.
The method can be used to directly measure the thermal expansion coef-
ficient. It is essentially different, for instance, from the capacitance method
212 Effective Field Approach to Phase Transitions

30 40 50 60
TEMPERATURE <° C)
30 40 50 60 70 80
TEMPERATURE C O

Fig. 3.3.3. Amplitudes of PA signal vs. temperature for (a) 6-cut TGS, first peak and
(b) c-cut TGS, first (o) and second (•) peaks. The continuous lines are published values
for the relevant thermal expansion coefficient (see Refs. 7, 8).

where it is necessary to register, with high accuracy, the changes in thick-

ness and in temperature in order to calculate the derivative dC~1/dT of
the capacitance. 9
We have measured sound velocity with axis selection in TGS, a trans-
parent material that allows us to register the time delay of acoustic waves
and the irradiation position with high accuracy, unlike the case of nontrans-
parent materials. 10
It can be concluded that the PA effect is a new, sensitive, and conve-
nient tool to investigate many phase transitions with pronounced thermal
expansion anomalies.

Acknowledgments

One of us (J.O. Tocho) has a sabbatical grant from the Ministerio de Edu-
cacion y Ciencia, Spain.
 New Technique for Investigating Ferroelectric Phase Transitions 213

References

1. A.C. Tam, Rev. Mod. Phys. 58, 381 (1986).

2. C.K.N. Patel and A.C. Tam, Rev. Mod. Phys. 53, 517 (1981).
3. H. Vargas and L.C.M. Miranda, Phys. Rep. 161, 43 (1988).
4. S.E. Braslaysky and K. Heihof, Handbook of Organic Photochemistry (CRC,
New York, 1989), Vol. 1, p. 327, and references therein.
5. K.L Bye, P.W. Whipps and E.T. Keeve, Ferroelectrics 11, 525
(1988).
6. Landolt-Bernstein, Crystal and Solid State Physics (Springer, New York,
1982), New Series, Group III, Vol. 16b, p. 223.
7. I. Shibuya and S. Hoshino, Jpn. J. Appl. Phys. 1, 249 (1962).
8. K. Ema, M. Katayama, Y. Ikeda and K. Hamano, J. Phys. Soc. Jpn. 46, 347
(1979).
9. H.K. Shiirmann, S. Gillespie, J.D. Gunton and T. Mihailisin, Phys. Lett.
45A, 417 (1973).
10. L. Narrai and W. Volken, Solid State Commun. 70, 223 (1989).
 Chapter 3.4

Tricritical Point Behavior and

Quadrupole Interactions in
Ferroelectrics*
Rafael Ramirez, Maria Fe Lapefia and Julio A. Gonzalo
Departamento de Fisica Aplicada, C-IV,
Universidad Autonoma, 28049 Madrid, Spain

It is shown that the generalization of the effective field expression to

take into account in addition to dipolar, quadrupolar, octopolar, and
higher order multipolar terms leads to a more general equation of state
that describes better the dependence of polarization on temperature and
external electric field. The cases of hydrogenated and deuterated mem-
bers of the TGS family are examined.

It is well known t h a t the usual mean field approach to ferroelectric transi-

tions takes into account dipole-dipole interactions only. T h e effective field
is assummed to be given by

Eefi = E + f3P, (1)

where E is t h e external field, (3 a mean field coefficient depending on the

geometry of the lattice, and P the polarization. This leads 1 to an equation
of s t a t e
T
e= — tanh_1p-p, (2)

where e = E/{3NpL, Tc = f3Nfi2/kB, p = P/Nfi, N being the number of

elementary dipoles per unit volume, and \i their dipole moment. Equa-
tion (2) for e = 0 fixes the behavior of the spontaneous polarization PS(T)

*Work previously published in Ferroelectrics 124, 1 (1991). Copyright © 1991. Taylor

& Francis Group.

215
216 Effective Field Approach to Phase Transitions

with temperature in the range 0 T < Tc (it may be noted that at low
temperature collective dipole wave-like excitations not taken into account
in the above equation of state may play a prominent role) and leads to a
continuous (second order) transition with well-defined universal features.
In this work, we consider a most general expression of the effective field

Eeff = £ + /3P + 7 P 3 . (3)

It is st right forward to show that in this case the equation of state
becomes
l
e = — tanh p - p - gp, (4)

where g = (7/'(3)(N)j,)2. It is in turn clear that, taking into account the

power series expansion of the inverse hyperbolic tangent,
1
, -1 * 3 5
tanh L
p = p + -p + -p5 •
6 (5)
3 5
For the g value going over from g < 1/3 to g > 1/3 we get a changeover from
continuous to discontinuous transition, and therefore a tricritical point.

Fig. 3.4.1. Reduced spontaneous polarization (Ps/Pso) vs. reduced temperature for
crystals in the TGS family. Curves are obtained from Eq. (6), and g values indicate
strength of quadrupolar interaction.
 Tricritical Point Behavior and Quadrupole Interactions in Ferroelectrics 217

Hysteresis loops spontaneous polarization data for triglicine sulfate,2

selenate, 3 and fluoberillate4 (TGS, TGSe, TGFB) are given in Fig. 3.4.1,
together with the theoretical spontaneous polarization curve from Eq. (4),
which, taking e — 0, is given by

£ = (l+flrf)[—£T-1, (6)
J-c Ltanh ps_
with g values g = 0, g = 1/12, g = 1/6, g = 1/4, and g — 1/3. One can see
that the behavior of ps(T) for TGS, TGSe, and TGFB can be described
much better with g values in the interval 0 < g < 1/3 than with 3 = 0,
which corresponds to the case of dipole-dipole interactions only.
In Fig. 3.4.2 the same data as in Fig. 3.4.1, in an expanded temperature
scale, are plotted along with the corresponding curves defined by Eq. (6)
with g values optimized to best fit the data. Since the value of Pso an(A the
value of g are not known in advance with sufficient precision, it is conve-
nient to design an unbiased procedure to determine both simultaneously.
To this end we may note that the ratio {psi/pS2) corresponding to the two
temperatures T\ and T2, close to T c , is independent of PSQ. Taking, for
instance, p s l at {T2/Tc) = 0.95 and P s 2 at (T2/Tc) = 0.99, plotting the

Fig. 3.4.2. Same data as in Fig. 3.4.1 in expanded temperature scale near T c ; curves
are from Eq. (6) with g values giving optimum fit to data for TGS, TGSe, and T G F B ,
respectively.
218 Effective Field Approach to Phase Transitions

Table 3.4.1.

Crystal Tx (K) g (dimensionless) P s 0 (^C/cm 2 )

TGS 322.4 0.19 4.08

TGSe 295.7 0.32 4.55
TGBF 346.2 0.28 4.86
DTGS 333.0 0.24 2.60
DTGSe 307.0 >l/3 3.50

ratio (psi/ps2) as a function of g at closely spaced Ag intervals in the range

0 < g < 1/3, and inserting experimental ratios (P s i/^s2) = {Psi/Ps2) cor-
responding to TGS, TGSe, and TGFB one gets directly the corresponding
g values, which are, respectively, g = 0.19 (TGS), g = 0.32 (TGSe), and
g = 0.28 (TGFB). Then one can automatically determine Pso from Psi/psi
and Ps2/Ps2, yielding, with excellent consistency, Pso = 4.08//C/cm (TGS),
P s 0 = 4.55 ^C/cm (TGSe), and Ps0 = 4.86/xC/cm (TGFB).
Table 3.4.1 summarizes the relevant data, transition temperature, sat-
uration polarization, and g values for crystals in the TGS family includ-
ing data 5 ' 6 for the deuterated compounds DTGS and DTGSe. The last
one shows a first order transition accompanied by thermal hysteresis and,
therefore, g > 1/3.
It is of some interest to compare the saturation spontaneous polarization
data obtained from fits of Eq. (6) as described above to estimates based
upon evaluation of iVM using the crystallographic unit cell volume vc, which
gives (N = 2vc = 2(abcsen/3) _1 ), Z = 2 being the member of molecular
units per unit cell and the Curie constant, C = e(T — Tc) = A-KN^I2/k& (for
T>TC). With these data

Ps0 =N^= (NkBC/4Tr)1/2. (7)

Table 3.4.2.

Crystal C (K) Ref. N Ref. P s 0 (^C/cm 2 )

(mol. units/cm 3 )

TGS 3560 6 3.12 x 10 2 1 9 3.7

TGSe 4050 7 2.99 x 10 2 1 10 3.8
TGBF 2630 4 3.16 x 10 2 1 11 3.2
DTGS 2550 8 3.12 x 10 2 1 — 3.1
DTGSe 3280 7 2.99 x 10 2 1 — 3.4
 THcritical Point Behavior and Quadrupole Interactions in Ferroelectrics 219

Table 3.4.2 gives the relevant d a t a for the same crystals belonging to the
T G S family as in Table 3.4.1, assumming t h a t unit cell volumes for D T G S
and D T G S e are not very different from those belonging to the hydrogenated
compounds. It can be seen t h a t the saturation polarization values obtained
in this way are in general somewhat lower b u t not very different from those
given in Table 3.4.1.
It can be noted t h a t deuteration increases the effective quadrupolar
interaction as well as the transition t e m p e r a t u r e from T G S (g = 0.19) to
D T G S (g = 0.24) and from T G S e (g = 0.32) to D T G S e (g > 1/3). This
means t h a t at certain fractional deuteration x, which appears t o be located
in the range 0 < x < 0.32, the crystal must show tricritical point behavior.

Acknowledgment

We wish t o acknowledge the financial support of C I C y T for this work.

References

1. See, for instance, J.A. Gonzalo, Phys. Rev. B l , 3125 (1970) and references
therein.
2. S. Tribewasser, IBM J. Res. Dev. 2, 212 (1958).
3. Z. Malek, J. Strajblova, J. Novotny and V. Mecerek, Czech. J. Phys. B 18,
1224 (1968).
4. H.H. Wieder and C. R. Parkeson, J. Phys. Chem. Solids 27, 247 (1966).
5. V.P. Konstantinova, J.M. Silvestrova, L.A. Shuvalov and V.A. Yurin, Bull.
Acad. Sci. USSR, Phys. (English Transl.) 1206 (1960).
6. J.A. Gonzalo, Phys. Rev. 144, 662 (1966).
7. K. Gesi, J. Phys. Soc. Jpn. 41, 565 (1976).
8. A. Cammasio and J.A. Gonzalo, Solid State Commun. 16 (1975).
9. E.A. Wood and A.N. Holden, Acta Cryst. 10, 145 (1957).
10. M. Yamada, Masters Thesis, Hokkaido University (1979).
11. F. Warkusz and K. Lukaszewicz, Bull. Acad. Polon. Sic, Ser. Sci. Chim. 2 1 ,
271 (1973).
 Chapter 3.5

Frequency and Temperature

Dependence of Sound Velocity
in TGS Near Tc*
M. de la Pascua t and Zhibing Hu
Department of Chemistry,
Massachusetts Institute of Technology, Cambridge,
Massachusetts 02139, USA

R. Ramirez, M. Koralewshi*, and J.A. Gonzalo

Departamento de Fisica Aplicada, C-IV,
Universidad Autonoma de Madrid,
28049-Madrid, Spain

Ultrasonics (10 and 50 MHz) and Brillouin (18.2 Hz and 19.2 Ghz) mea-
surements of the longitudinal sound velocity in TGS propagating along
the crystallographic c-axis (_L to the ferroelectric fr-axis) have been per-
formed in the vicinity of the transition temperature Tc = 49.3°C. The
data confirm a Debye-type relaxation behavior with a polarization relax-
ation time of the form T = A(TC — T)~* for T < Tc, which is in fair quan-
titative agreement with the relaxation time from dielectric measurements
at high frequencies.

Triglycine sulfate (TGS) shows a typical second order ferroelectric

transition 1 at Tc = 49.3°C. Sound velocities along various crystal direc-
tions have been previously measured by ultrasonics 2 and light scattering 3 " 5
techniques at a fixed frequency. In this work, we report high-resolution

*Work previously published in Ferroelectrics Letters 14, 91 (1992). Copyright © 1992.

Taylor & Francis Group.
tOn leave from Dpto. Fisica Aplicada, C-IV, Universidad Autonoma, 28049 Madrid,
Spain.
*On leave from Universitat im Adama Mickiewicka 60-780 Poznan, Poland.

221
222 Effective Field Approach to Phase Transitions

ultrasonics data and Brillouin scattering data taken at several frequen-

cies that confirm a Debye-type relaxation behavior and allow a compar-
ison of the anomalous temperature-dependent relaxation time obtained
from elastic measurements (ultrasonics and Brillouin) with the correspond-
ing anomalous relaxation time from high-frequency dielectric constant
measurements.
The samples used in both ultrasonics and Brillouin experiments were
properly oriented TGS parallelepipeds, cut from a large TGS single crystal
grown from water solution donated to us by Dr. J. Przeslawsky, Univer-
sity of Wroclaw (Poland). The experimental setups for ultrasonics (MIT,
Chemistry Department) and Brillouin scattering (UAM, Applied Physics
Department) were the same as those used in previous work by the MIT and
UAM groups.
Figure 3.5.1 shows the ultrasonic longitudinal sound velocity for waves
propagating along the c-axis (_L to the ferroelectric 6-axis) in a relatively
wide temperature range around Tc. It can be seen that the data for 10 MHz
(crosses) and 50 MHz (dots) differ from each other only in a narrow tem-
perature interval of less than one degree below Tc.
At T > Tc, the longitudinal sound velocity appears to be temperature
as well as frequency independent in the temperature range examined.

4150

4100 jlAtv

+ 10 MHz
• SO MHz
^4050

^4000
\ V i
3950

3900. 60
40 45 5
°T['C]55
Fig. 3.5.1. Longitudinal sound velocity along the c-axis of a TGS single crystal as a
function of temperature at the frequencies 10 MHz (+) and 50 MHz (•) from ultrasonics
measurements.
 Frequency and Temperature Dependence of Sound Velocity in TGS 223

«fau

4100 «K -
o 19.2 GBs „«
» 1&.Z GHz ,
a 14.8 GHz
\*?4050 (R'f. 5)

* s°
» . 0,8

39S0

J 1 I
""""SO SO m r.rn40 s0 e0

Fig. 3.5.2. Sound velocity along the c-axis of TGS as a function of temperature at
19.2 GHz (o), 18.2 GHz ( + ) , present work, and at 14.8 GHz ( • ) ; work reported in Ref. 5.

Figure 3.5.2 shows the hypersonic sound velocities obtained by Brillouin

scattering with Ar + laser (single mode) lines of wavelength 5145 A (corre-
sponding to 18.2 GHz) and 4880 A (corresponding to 19.2 GHz) along with
previous data from Yagi et al. obtained with a He-Ne laser line of wave-
length 6328 A (corresponding to 14.8 GHz). While the experimental uncer-
tainty showed by the data points is not negligible (due in part to the fact
that the frequency separation is small), it can be seen that the trend of
the sound velocity curves with frequencies is as it should be expected, i.e.,
the curve corresponding to the highest frequency (19.2 GHz) shows the
smaller dip with temperature, and the one corresponding to the lowest one
(14.8 GHz) shows the largest dip. The widths of the Brillouin peaks and
the intensity of the central quasi-elastic peak in our spectra (not shown
in Fig. 3.5.1) show basically the same temperature dependence reported
by Yagi et al.5 in their investigation at 14.8 GHz. It may be noted that
the hypersonic velocity curves of Fig. 3.5.2 are crossed by the ultrasonic
velocity curves of Fig. 3.5.1 at about seven degrees below the transition.
This should not be so under normal conditions, since at any given tempera-
ture the crystal should behave as consistently hardening (showing therefore
higher sound velocity) with increasing frequency in a relaxation process.
One possible explanation for the observed behavior is that, at the ultra-
sonic experimental frequencies of 10-50 MHz one is beginning to approach
the lower frequency region where piezoelectric resonance effects take place.
224 Effective Field Approach to Phase Transitions

Z.5 x 10' I I /

2.0

1.5 - /

1.0
- I
7
0.5 /

i i

0.05 0.10 0.15

AT = Tc - T [K]
Fig. 3.5.3. Inverse elastic relaxation time r 1(T) in the ferroelectric phase of temper-
ature difference to the Curie temperature (T c ).

These effects can give rise to a superimposed apparent hardening of the

crystal with lowering frequency (see Fig. 3.5.3).
An anomalous elastic behavior obeying Debye-type relaxation charac-
terized by a relaxation time r can be described by
—
Coo Co
C'(w) = C^ - (1)
1 + UJ2T2
(Coo - C0)tOT
C » (2)
1 + LU2T2 '
In terms of ultrasonics data the above equations become

(3)

F (4)
LU 1 + L02T2

where p is the density, v(to) the sound velocity, v^ = i>(oo), vp = u(0), and
a (a;) the attenuation.
On the other hand, in terms of Brillouin shifts, they become
2
2irAv 27rAt; 00 \ p[(27rAt;0O/|fc|)2 - (2TT At; 0 /|fc|) 2
=P (5)
|fc| 1 + UJ22-T2

n 5v {2TTAV\ p[(2TrAv00/\k\)2-(2TrAv0/\k\)2]ojT
PZ7T — - ' ' —
1 + L02T2
(6)
\k\ V |fc|
 Frequency and Temperature Dependence of Sound Velocity in TGS 225

where Av = v\k\/2ir is the Brillouin shift, and Sv = a\k\/2Av is the peak

full-width at half-maximum.
In Eqs. (l)-(6), C^ — pv"^ = p(2'wAv0O/\k\)2 should be basically the
same at T < Tc and T > Tc, being temperature independent in a certain
temperature range around T c . Co = pv2, = p(2nAvo/\k\)2, on the other
hand, should be markedly temperature dependent below Tc but almost
temperature independent above Tc. Below Tc the temperature dependence
of the relaxation time 5 is given by

T= A(T-TC)~ (7)

We can use the ultrasonics data of Fig. 3.5.1 to determine the temper-
ature dependence of T close to Tc. Knowing two sound velocities (corre-
sponding to two different frequencies t>i = ui/2ir and t>2 = U>2J2-K at a
given temperature), it is straightforward to get the relaxation time at this
temperature by means of Eq. (3) as follows:

v~ v\vr) [vl,+V>l)][vlo-V2{^)]
v
lo -V2{V2)
(8)
(l+47T2i/jV2)-1
Vo •v(v2) (l+47r2i/2r2)-1

since in our case WQO + v(v{), vx + v(v\), 2v0

Solving Eq. (8) for r one gets
1/2
VQO-V(VI,T)
v<x>—v(vi,T)
r(T) (9)
1 4TT2I/|
(S)'
Substituting the data of Fig. 3.5.1 in the useful interval in which v(vi,T)
and v(v2,T) are clearly distinguishable (0.03 < (Tc — T) < 0.15) one gets
experimental points for r _ 1 ( T ) as shown in Fig. 3.5.3. From these data one
gets the coefficient that appears in Eq. (7)

A = (4.6 ± 0.3) x 10 - l i (10)

which is in good agreement with the results previously obtained by Yagi

et a/.5 from Brillouin scattering data at 14.8 GHz.
From our Brillouin data at 18.2 and 19.2 GHz one can get also the
coefficient A taking advantage of the fact that the maximum width dvm
observed at a certain temperature T m for a given frequency OJ is given by
226 Effective Field Approach to Phase Transitions

Eq. (6) as

wr = l, i.e., T-1=A-1{Tc-Tm) = 2nAvm. (11)

Substituting here the experimental values Av = 19.2 GHz = LJ/2-K,

(Tc - T m ), 5K, one gets

,4 = (4.1 ±0.3) x HT 1 1 , (12)

in good agreement with the value previously obtained by Yagi et al.,5 and
also with the value deduced from our ultrasonic data, given by Eq. (10).
Finally, it is of interest to compare quantitatively the temperature
dependence of elastic relaxation (obtained from ultrasonics and Brillouin
data) with that of the dielectric relaxation (obtained from high-frequency
dielectric constant data) near T c . In principle, they should be the same
because in both cases the relaxation process is induced by the fluctuations
of the spontaneous polarizations. This can be done analyzing the high-
frequency dielectric constant data of Luther and Muser 6 on TGS through
the transition. Cole-Cole plots of the imaginary versus the real part of
the dielectric constant at several temperatures below T c give nearly perfect
semicircles, indicating a well-behaved Debye-type relaxation with a single
relaxation time. The dielectric time is given by

T-1 = CJT = A-1 (Tc-T), (13)

where, from the experimental data at AT, 2K, where LJT — 2irvr = 2n x
4.5 x 108 rad/s, one gets

2 T X 4 5 X 1
A=( 2 °9); (7.0 ± 2) x 1 0 " (14)

The agreement between the result given in Eq. (14) and in Eqs. (10)
and (12) is not unsatisfactory, taking into account the experimental uncer-
t a i n t i e s involved.

Acknowledgments

We would like to thank Prof. C. Garland for support and valuable criticism
in the early stages of this work. The financial support of CICyT is also
acknowledged.
 Frequency and Temperature Dependence of Sound Velocity in TGS 227

References

1. See Landau-Bornstein, Crystal and Solid State Physics, Vol. 16, pp. 223-236
(Springer Verlag, New York, 1982).
2. E.J. O'Brien and T.A. Litovitz, J. Appl. Phys. 35, 180 (1964).
3. R.W. Gammon and H.Z. Cummins, Phys. Rev. Lett. 17, 193 (1966).
4. T. Yagi, M. Tokunage and J. Tatsuzaki, J. Phys. Soc. Jpn. 37, 1717 (1974).
5. S.T. Yagi and T. Tatsuzaki, Ferroelectrics 52, 67 (1983).
6. G. Luther and H.E. Musser, Naturforsch. A 24, 389 (1969).
 Chapter 3.6

Dipolar and Higher Order

Interactions in Ferroelectric TSCC*

Gines Lifante and Julio A. Gonzalo

Departamento de Fisica Aplicada, C-IV,
Universidad Autonoma de Madrid, 28049 Madrid, Spain

Wolfgang Windsch
Fachbereich Physik, Universitat Leipzig,
0-7010 Leipzig, Germany

Relevant data on Tris-sarcosine calcium chloride (TSCC), including

temperature-dependent data of spontaneous polarization ( P = 0.27 /iC/
cm 2 ), dielectric permittivity (Curie constant at T > Tc, C = 59K,
and Curie temperature Tc = 125.4 K), and specific heat (AC P =
0.27 x 10 6 erg/Kcm 3 , specific heat jump at T = T c , after discounting
for logarithmic corrections), have been analyzed within the framework
of the effective field approach to ferroelectric transitions, resulting in
N = 1.01 x 10 21 dipoles/cm 3 and fj, = 0.80 x 10~ 1 8 esucm, in good
agreement with microscopic observations. Consideration of quadrupolar
(<7 =£ 0) and octopolar (h ^ 0) contributions to the effective field improve
the theoretical fit to (P/Pso) vs. (T/Tc) data.

T h e ferroelectric to paraelectric transition at about T C ,130K, in Tris-

sarcosine calcium c h l o r i d e 1 - 3 (TSCC) has features of an order-disorder 4 , 5
transition as well as of a displacive 6 - 8 transition, which is not uncommon
among phase transitions in uniaxial ferroelectrics. T h e crystal s y m m e t r y 9 a t
room t e m p e r a t u r e is orthorhombic D\h {Pnma) with four formula units per

*Work previously published in Ferroelectrics 135, 277 (1992). Copyright © 1992.

Taylor & Francis Group.

229
230 Effective Field Approach to Phase Transitions

unit cell and becomes orthorhombic C\v {Pn2\a) below Tc. The structural
data point out to the existence of two molecular groups per unit cell includ-
ing each a zwitter ion, which could be interpreted as evidence for two ele-
mentary dipolar groups per unit cell, or one dipolar group for every two
formula units.
In this work, we will analyze available spontaneous polarization, 1 dielec-
tric permittivity, 1 and specific heat 10 data on TSCC within the frame-
work of the effective field approach 11 to ferroelectric transitions to get
the relevant parameters /3 (effective field coefficient), /J, (elementary dipole
moment), and N (numbers of elementary dipole moments per unit vol-
ume) from macroscopic data alone and we will compare them with other
structural and microscopic information on these quantities.
As is well known, the effective field (or molecular field) approach
assumes, in the case of ferroelectrics,11 an effective field acting on each
individual dipole (/i)

EeS = E + /3P, (1)

where E denotes the external field, j3 an effective coefficient of proportion-

ality, depending on the crystal structure, and P the polarization. The term
(5P involves the dipolar contributions only to the effective field. It will be
seen later that higher order contributions can be considered, resulting in a
better description of the order parameter dependence on the temperature.
The simple effective field assumption leads in a straightforward manner to
the equation of state
P_
=- {Mw)}-
where Nfi = Poo is the saturation polarization and Tc = f3Nfi2lkQ the
transition temperature. Prom this equation of state a Curie-Weiss law for
the dielectric susceptibility follows immediately

e = e0 + ^ , C = ^ forT>Tc. (3)

Makita's data 1 on spontaneous polarization imply a low-temperature

(saturation) polarization
P s 0 = Nil = 0.27 ^C/cm 2 = 810esu/cm 2 . (4)

The same author's data on dielectric permittivity along the ferroelectric

axis indicate that the temperature dependence of this physical quantity for
 Dipolar and Higher Order Interactions in Ferroelectric TSCC 231

T > Tc is well fitted by

eb-£bo = ^ ^ r (Tc = 125.4 K), (5)

where mostly the electronic contribution is

£b0 = 5.4(T > T c ), (6)

the Curie constant is

C = 4 ^ = 59K.
KB
11
From these data alone we get
(3 = ^ = 26.7, (8)

18
/x=Mii=0.80xlO- esu, (9)
P"sO

and

N = — = 1.01 x 10 21 dipoles/cm 3 . (10)

The last numerical value can be immediately compared with the number
of formula units per unit volume, which is given by

Zv~l = Z{abc)~l = 2.44 x 10 21 formula units/cm 3 (11)

obtained using 1 a = 9.156(10)1, b = 17.460(5) A, and c = 10.265(5) A.

This is compatible, within experimental error, with the assumption that
there are two dipole units per unit cell in this crystal.
The jump in specific heat 10 at T = Tc is given by

AC P = 20 J/Kmol = 0.815 x 106 erg/cm 3 , (12)

where use has been made of the fact that the molecular weight of TSCC is
M = 377 and its density p = 1.53g/cm 3 .
However, the specific heat peak shows clearly that there is an upwards
curvature in Cp(T) for increasing T just below Tc, indicative of the need for
logarithmic corrections if one wants to compare with the purely effective
field jump

AC P (eff. field) = ^NkB- (13)

232 Effective Field Approach to Phase Transitions

We have estimated the approximately constant slope of AC P (T) well

below T c , where logarithmic corrections are presumably negligible and we
have obtained

AC P (eff. field); 0.27 x 106 erg/cm 3 . (14)

Substituting numerical values from Eqs. (10) and (14), as well as

Boltzmann's constant k-g = 1.38 x 10~ 16 erg/K, we get from Eq. (13)

N; 1.3 x 10 21 dipoles/cm 3 , (15)

in fair agreement with the value obtained in Eq. (10), taking into account
the uncertainties involved.
The results thus obtained for /i (dipole moment) and for the number of
elementary dipoles per unit cell can be compared with published ENDOR
data 12 in TSCC, which seem to support in a quantitative manner the values
obtained in Eqs. (9) and (10).
ENDOR investigations on manganese doped TSCC revealed a tilting of
the sarcosine zwitter ions type II, which are located in a general position
in case of transition to the ferroelectric phase. No positional changes could
be detected on the sarcosine zwitter ions of type I lying in the (010) mirror
planes above T c .
The tilting within the molecular planes [(011) and (011)] of the sarcosine
type II is not connected with the spontaneous polarization.
The tilt perpendicular to the molecular planes of sarcosine type II is
temperature dependent. It proceeds for sarc 6 and sarc 2 as well as sarc 3
and sarc 5 in the opposite direction so that the mirror plane is lost. A tilt
angle of 3.0° ± 0.5° was measured. The increase of the angle with decreasing
temperature indicates a displacement process responsible for the observed
spontaneous polarization.
With the help of CNDO calculations a dipole moment of 2.7 x 10~ 29 C m
(= 8.28 x 10~~18esu) was determined for the sarcosine zwitter ion.
Together with the tilting angle of 3° a spontaneous polarization of
0.33 /iC cm" 2 (= 1000esu/cm 2 ) along (010) was calculated, which is in
good agreement with the experimental values.
The sarcosine zwitter ions 1, 3, and 5 and 4, 2, and 6 are lying in different
planes along (100). All are connected by a strong chemical bonding to the
calcium ion, and the oxygens of the carboxyl group constitute a deformed
octahedron. For each set of three sarcosine zwitter ions as well as for the
calcium-(sarcosine) 6 complex one can combine the observed tilt to obtain
 Dipolar and Higher Order Interactions in Ferroelectric TSCC 233

the spontaneous polarization. In the first case, this would mean that there
are four polar units in the unit cell, whereas in the second case only two
polar units would be present. The calculations given here confirm the earlier
statement, which was based on EPR as well on Raman investigations, that
the Ca(sarc)6 complex is the polar entity in TSCC.
In the case of uniaxial ferroelectrics of the TGS family it has been shown
recently 13 that assuming an effective field

EeS = E + f3P + ^P3+5P5, (16)

which includes quadrupolar ( 7 ^ 0 ) , octupolar (5^0), etc., terms beyond

the purely dipolar (j3 / 0) term, allows a much better description of the
temperature dependence of the spontaneous polarization. Using Eeg from
Eq. (16) the expression for the spontaneous polarization becomes

P
1+ (17)
—— = tanh
*'j|)+A(l
where g = (7//3)(iV/i)2, h = (S/f3)(N^,)4:, etc. This can be written as

Tt^-Hp./N»)_1=g(gy+h(g_ +L (18)
Tc (Ps/Nfi) \NfiJ \Nn

Available experimental data 1 of (PS/N/J.) vs. (T/Tc) for TSCC have been
analyzed, and Fig. 3.6.1 shows that the agreement between experimental
points and the theoretical expression, Eq. (18), improves from the purely
dipolar (/? ^ 0, g = 0, h = 0) to the dipolar plus quadrupolar (/? ^ 0,
g 7^ 0, h = 0) to the dipolar plus quadrupolar plus octupolar expression
(/? ^ 0, g ^ 0, h ^ 0). It may be noted that the best fit is obtained with
g, 0.19 (<7TC = 1/3 for a tricritical point), and h = 0.15 (hue = 1/5 for a
higher order multicritical point).
In conclusion, we may say that a clear improvement in the description
of the temperature dependence of the order parameter (Ps) in TSCC is
obtained including quadrupolar and octupolar terms in the local effective
field at the dipole sites. It may be noted that a quadrupolar contribution
involves a field gradient, which may give rise to some "stretching" of the
elementary dipole moment, thus incorporating, at least partly, displacive
features in the physical description of the transition.
234 Effective Field Approach to Phase Transitions

1.0 - - r ^ - * '1nr;Ss£CLfi

•
%
2en- 0.6 - TSCC \ 6
\ 9
a.
\ - \ 1
g = 0 h = 0 M
a. 0.4 g = .215 h = 0 \\n
9 = .19 h = .15
0.2

1 . _i .„, i— > L- ( 1
""0.0 0.2 0.4 0.6 0.8 1.0
T/Tc

Fig. 3.6.1. Reduced spontaneous polarization (Ps/N[i) vs. reduced temperature (T/Tc).
Experimental points are from Makita (Ref. 1). Theoretical curves are given by Eq. (18)
with the successive sets of g and h values: (1) g = 0, h = 0; (2) g = 0.215, h = 0;
(3) g = 0.19, h = 0.15.

Acknowledgment

We wish t o acknowledge financial support for this work from C I C y T

(Comision Interministerial p a r a Ciencia y Tecnologia). One of us
(W. Windsch) is indebted to the Spanish M E C (Ministerio de Educacion y
Ciencia) for supporting a three-month stay a t UAM, Madrid.

References

1. Y. Makita, J. Phys. Soc. Jpn. 20, 2073 (1965).

2. M. Fujimoto, Cz. Pawlaczyk and I.G. Unruh, Phil. Mag. 60, 919 (1989).
3. J. Petzelt, A. A. Volkov, Yu. G. Goncharov, J. Albers and A. Klopperpieper,
Solid State Commun. 73, 5 (1990).
4. T. Chen and G. Schaack, J. Phys. C 17, 3801 (1984); ibid. 17, 3821 (1984).
5. V.H. Schmidt, Solid State Commun. 35, 649 (1980).
6. S.D. Prokhorova, G.A. Smolensky, I.G. Siny, E.G. Kuzminov, V.D. Mikvabia
and H. Arndt, Ferroelectrics 25, 629 (1980).
7. G.E. Feldkamp, J.F. Scott and W. Windsch, Ferroelectrics 39, 1163 (1981).
8. G.V. Kolzov, A.A. Volkov, J.F. Scott, G.E. Feldkamp and J. Petzelt, Phys.
Rev. B28, 255 (1983).
9. T. Ashida, S. Bando and M. Kakudo, Acta Cryst. B28, 1560 (1972).
10. T. Matsuo, M. Manson and S. Sunner, Acta Chem. Scand. A33, 781 (1979).
 Dipolar and Higher Order Interactions in Ferroelectric TSCC 235

11. See, for instance, Julio A. Gonzalo, Effective Field Approach to Phase Tran-
sitions and Some Applications to Ferroelectrics (World Scientific, Singapore,
1991).
12. H. Metz, R. Bottcher and W. Windsch, Chern. Phys. Lett. 182, 132 (1991).
13. R. Ramirez, M.F. la Pena and J.A. Gonzalo, Ferroelectrics (in press).
 Chapter 3.7

Thermal Hysteresis and Quadrupole

Interactions in Ferroelectric
Transitions*
Julio A. Gonzalo, Rafael Ramirez and Gines Lifante
Departamento de Fisica de Materiales,
C-IV Universidad Autonoma de Madrid,
28049-Madrid, Spain

Marcell Koralewski
Institute of Physics, Adam Mickiewicz University,
60-780 Poznan, Poland

It is shown that a self-consistent calculation of the maximum amount of

thermal hysteresis accompanying discontinous ferroelectric transitions
can be made if one takes into account the quadrupolar contribution to
the effective ferroelectric field. Comparison of calculated and observed
thermal hysteresis in several ferroelectrics belonging to different families
shows fair agreement.

T h e phenomenon of thermal hysteresis in discontinous phase transitions is

a ubiquitous one, not only in ferroelectrics but also in other systems under-
going a variety of phase transitions. Little theoretical attention has been
put, as far we know, in calculating the amount of thermal hysteresis, and in
correlating its value with t h a t of other physical parameters characterizing
the phase transition. Our purpose in this work is to show, within the frame-
work of a generalized effective field approach, t h a t it is possible to correlate
succesfully the amount of thermal hysteresis with the relative strength of
the quadrupolar interaction contributing to the effective field.

*Work previously published in Ferroelectrics Letters 15, 9 (1993). Copyright © 1993.

Taylor & Francis Group.

237
238 Effective Field Approach to Phase Transitions

It is well known that the observed thermal hysteresis may depend on the
particular experimental conditions, such as heating and cooling rates, and
on the particular experimental technique used. We are concerned here only
with the "ideal" (maximum) thermal hysteresis under quasi-equilibrium
conditions.
The effective field approach 1 to ferroelectric phase transitions, fully
analogous to the Weiss2 theory of ferromagnetism, is certainly the sim-
plest possible one, and in its simplest version (Eeg = E + f3P), which takes
into account only dipole interactions, is capable of describing fairly well the
main features of continous ferroelectric transitions. 3 In this work, we will
use a more general expression

EeS = E + 0P + 7 P 3 + SP5L (1)

for the effective field, in terms of an external field E and odd powers of
the polarization P, which correspond successively to contributions dipolar,
quadrupolar, octupolar, etc. The coefficients /?, 7, and S may be expected to
depend on the geometry of the lattice and on the spatial charge distribution
within the unit cell.
The equation of state 1 is given by

-^=tanh(^V (2)
w
Nfi \kBT J'
where P is the polarization, Pso = N[i is the low-temperature saturation
polarization, N being the number of elementary dipoles per unit volume
and fi the electric dipole moment, kB is Boltzmann's constant, and T the
temperature. Keeping terms only up to the quadrupolar contribution in
Eeg given by Eq. (1) one can rewritte Eq. (2) as
T
e= — tanh" 1 p-p-gp3, (3)
J-c

where e = E/PN/i, p = P/N/i, 9 = {-y/f3)(N[i)2, and Tc = pN(j,2/kB is the

Curie temperature. For e = 0, p = ps (spontaneous polarization), Eq. (3) is
conveniently rewritten as

7r(1+5Ps)t^^' P s =
w (4)

Here, g < | gives rise to continous (second order) transitions, while

g > \ gives rise to discontinuous (first order) ones. Since we are concerned
 Thermal Hysteresis and Quadrupole Interactions in Ferroelectric Transitions 239

0.8 -

i z r-——
^.^__—
^
~-—^ "~~-^-^^ ^--^9=0.50
0.6

^ ^ ^ ^ ^ ^ ^\ >v g=0.40
N^ g=0.45
^ ^ • ^ .
/
0.4 - ^\. N. -t> \ / s*
s '

\ //
J - '

3=1/3 \ i
/ ' ^""
0.2 \ , •;'_''
s t +
" 9
1
0.0
0.98 1.00 1.02
T/T c

Fig. 3.7.1. Reduced spontaneous polarization (Ps/Pso) vs. reduced temperature (T/Tc)
for g values above g = | .

here with discontinous transitions, for which thermal hysteresis may be

expected, we consider the case g > | .
Figure 3.7.1 shows p = {Ps/Ps0) as a function of (T/Tc) from Eq. (4)
for several g values just above g = 5. An increasing thermal hysteresis
for increasing g between Tc and a certain temperature T* is noticeable.
Figure 3.7.2 gives the discontinuous jump in spontaneous polarization p* =
(P*/Ps0) occurring at T = T* as well as the reduced thermal hysteresis

ATCcal
H (5)
Tc.
obtained from Eq. (4) as shown below, as a function of g.
The expression of (T*/Tc) as a function of p* can be easily obtained as
follows. Equation (4) establishes an explicit relation for (T/Tc) as a function
of ps = (Ps/.Psrj) and the transition temperature T* for rising T corresponds
to a minimum of (T/Tc) as a function of ps. Therefore,

d(T/T c ) 2gp*s 1 T*
(T*/Tc) +
dp s T=T* L(l+3(Ps*) 2 )

[(1 + 9Pf)P;(l - gpf)}-1 ( 0 0. (6)

240 Effective Field Approach to Phase Transitions

0.6

0.4

P>*

0.2

0.0
0.3
g
Fig. 3.7.2. Spontaneous polarization jump (P*/Pso) and thermal hysteresis (AT/TC)
as a function of g in the interval ~ < g < | ; g = (a//3)(N/j,)2 gives a measure of the
quadrupolar interaction contribution to the effective field.

Simplifying and eliminating (T*/Tc) we get

( ^ ) = ( i + f l ( p : ) 2 ) ( 3 f l ( p : ) 2 + i) (7)

Then substituing g in terms of p* from Eq. (4),

T*\ _1 1
= 2 3 ^tanh Ps\ (8)
Tj V Pt ) (l-Ps*)2J
which gives T* in terms of p* or vice versa.
It may be noted that, for sufficiently small p*, Eq. (8) further reduces to

1
l-i(rf) (9)

Equations (8) and (9) establish a conection between the ammount of ther-
mal hysteresis accompanying a ferroelectric phase transition and the value
of the discontinuous jump in spontaneous polarization occurring in the
same transition. As might be expected, the amount of thermal hysteresis
vanishes as p* approaches to zero. For 0 < g < | one has a continuous
(second order) transition, such as the one found3 in the undeuterated crys-
tals of the triglycine sulfate family TGS (sulfate) and TGFB (fmoberillate).
For g one has a continuous, tricritical point transition, which seems
 Thermal Hysteresis and Quadrupole Interactions in Ferroelectric Transitions 241

Table 3.7.1.

Crystal T c (K) T* (K) P s c (/iC/cm 2 ) Pso (/iC/cm 2 ) Refs.

DTGSe 307.0 307.8 1.5 3.5 4,5

KDP 122.56 122.70 2.2 5 6,7
BaTi03 374.3 390.4 15.5 27.0 9, 10

Crystal A T o b s (K) a A T o b s (K) b Refs. AT c a l (K)

DTGSe 0.8 5 0.6

KDP 0.6 0.14 8,6 0.25
BaTi03 3.7 1.6 11,9 3.2
a
From unit cell parameters as determined by X-ray work.
b
Prom dielectric constant measurements.

to be very close to TGSe (selenate). For g > | , as we have seen, one

has discontinuous (first order) phase transitions. They are realized in some
deuterated crystals of the triglycine sulfate family, such as DTGSe, as well
as in most crystals of the potassium dihydrogen phosphate family (KDP)
and the perovskite family.
Table 3.7.1 gives relevant data to characterize the thermal hysteresis
of the ferroelectric transition in DTGSe, KDP, and BaTiO-3. To determine
AT c a | we have proceeded as follows. First, from the known value of P s = P s c
at T = Tc (somewhat below T*, which is the transition temperature for
rising temperature) and the saturation spontaneous polarization, we have
obtained psc = Psc/Pso- From

'taBh^ftc _ J 1 (1Q)
ps J pic
[deduced from Eq. (4) for T = Tc], we have obtained a numerical value
for g. Then, from the functional relationship between g and p*, depicted in
Fig. 3.7.2, a numerical value for p* has been finally obtained, which, when
substituted in Eq. (8), leads directly to a calculated value for the thermal
hysteresis AT ca i. We have to do this instead of directly using p* experimen-
tal values because the spontaneous polarization is changing rapidly as T
approaches T*, and available data are rarely accurate.
Ar o bs (u.c.p.) from the temperature dependence of the unit cell parame-
ters as given by X-ray investigations, and ATODS(£), from dielectric constant
data for rising and lowering temperatures, agree reasonably well with AT ca i
for the crystals in Table 3.7.1. It must be noted that, in going through
the thermal hyateresis temperature interval, the crystal is in succesive
242 Effective Field Approach to Phase Transitions

metastable states and this may easily result in somewhat inaccurate numer-
ical values for AT 0 b s - In this respect the usual larger values given by unit
cell parameters measurements seem to be more reliable t h a n those given by
dielectric constant a n d / o r hysteresis loops measurements.
We may conclude t h a t if the relative strength of quadrupolar
contributions to the effective field in a ferroelectric are such t h a t
g = (a/P)(N/j,)2 > | one can expect appreciable thermal hysteresis in fer-
roelectric transitions as in fact observed. T h e relevance of quadrupolar-
like interactions in ferromagnets 1 2 and ferroelectrics 1 3 has been previously
recognized.
It should not be ruled out altogether t h a t higher order (octupolar, etc.)
interactions play a role at the phase transition. This would complicate the
calculation of the amount of thermal hysteresis and it will be left for fur-
ther work.

Acknowledgments

We wish to acknowledge the financial support of C I C y T for this work. One

of us (M.K.) would also like to acknowledge the D G I C y T .

References

1. J. A. Gonzalo, Effective Field Approach to Phase Transitions and Some Appli-

cations to Ferroelectrics (World Scientific, Singapore, 1991).
2. P. Weiss, J. Phys. 6, 667 (1907).
3. R. Ramirez, M. Fe Lapefia and J.A. Gonzalo, Ferroelectrics 124, 1 (1992).
4. Z. Malek, J. Strajblova, J. Novotny and V. Merecek, Czech. J. Phys. B18,
1224 (1968).
5. K. Gesi, J. Phys. Soc. Jpn. 41, 565 (1976).
6. B.A. Strukov, A. Baddur, V.A. Koptsik and LA. Velichko, Fiz. Tverd. Tela
14, 1034 (1972); Sov. Phys. Solid State 14, 885 (1972).
7. G.A. Samara, Ferroelectrics 5, 25 (1973).
8. J. Kobayashi, Y. Uesu, I. Mizutani and Y. Enomoto, Phys. Stat. Sol. (a) 3,
63 (1970).
9. J.A. Gonzalo and J.M. Rivera, Ferroelectrics 2, 31 (1971); J.M. Rivera and
J.A. Gonzalo, Rev. Mexicana de Fisica 19, 297 (1970).
10. S.H. Wemple, M. di Domenico Jr. and I. Camlibel, J. Phys. Chem. Solids
29, 1797 (1968).
11. R.G. Rhodes, Acta Crystallogr. 2, 417 (1949).
12. H.H. Chen and RM. Levy, Phys. Rev. B7, 4267 (1973).
13. Q.Z. Kai, Z.J. Bo and W.C. Lei, Ferroelectrics 101, 159 (1990).
 Chapter 3.8

Specific Heat and Quadrupole

Interactions in Uniaxial
Ferroelectrics*
Beatriz Noheda, Gines Lifante and Julio A. Gonzalo
Departamento de Fisica de Materiales, C-IV,
Universidad Autonoma de Madrid,
28049 Madrid, Spain

The inclusion of quadrupolar and higher order terms into the effec-
tive field in second order transition in uniaxial ferroelectrics is shown
to describe well the jump in specific heat at T, Tc, for crystals of the
TGS family. It is shown that the numerical values for the coefficient
g = (•y/p)(Nfi)2, corresponding to the quadrupolar interaction term,
obtained (a) from specific heat data and (b) from spontaneous polar-
ization data (both at T, T c ) are in good agreement with each other for
crystals of the TGS family.

It has been previously reported 1 t h a t introducing an effective field Ees =

E + f3P + jP3 + 5P5 • • • , which implicitly includes quadrupolar ( 7 P 3 ) ,
octopolar {SP5), and higher order terms in addition to the usual dipolar
{(3P) term, leads to an improved description of the phase transition 2 in
uniaxial ferroelectrics.
T h e resulting equation of state is given by

e = (^-Jtanh^p-{l+gp2 + hp4 + ---)p, (1)

where e = E/f3N(i is t h e dimensionless normalized field, T c = fiNfj? t h e

transition (Curie) t e m p e r a t u r e , p = P/Nfi the normalized polarization, and

*Work previously published in Ferroelectrics Letters 15, 109 (1993). Copyright © 1993.
Taylor & Francis Group.

243
244 Effective Field Approach to Phase Transitions

g = ('j/(3)(Nfi)2, h = (S/f3)(Nfi)4, etc., N being the number of elementary

dipole moments per unit volume and fi their electric dipole moment.
For E = 0, the temperature dependence of the spontaneous polarization
is given [Eq. (1)] by

^ = r^^(l+gP2s+hpl+L) = -J^(l+g>P*). (2)

Jc tanh ps tann ps
Near the transition temperature (T < T c ), this leads to p2; 3(1 — T/Tc)
for g' = 0 and

^d^1"!) for
^^°- (3)
This result will be used below to determine the behavior of the ferroelec-
tric specific heat jump from T < Tc to T > Tc, which will allow one to get
an independent determination of g from specific heat data, to be compared
with a previous determination of g from spontaneous polarization data.
To get the appropriate expression for the specific heat per unit volume
at T < Tc we may write down2 the ferroelectric internal energy per unit
volume in terms of the spontaneous polarization

Q(T) = - i / ? P 2 ( T ) , (4)

which allows one to get the differential of entropy

ts^yjfi, ( 5)
and, consequently, the ferroelectric specific heat per unit volume

^m-r(f)T-i«J»rt'(^). («
Substituting p2s (T < Tc) from Eq. (3) and using Tc = j3Nn2/kB we get

2
ACp(Tc) = - i / W ^ ^ ) =I ^ ^ B , (7)

at T < Tc and, of course,

ACp(Tc)=0, p 2 ( T > T c ) = 0, at T >Tc. (8)

 Specific Heat and Quadrupole Interactions in Uniaxial Ferroelectrics 245

Therefore, the relative importance of g is automatically reflected in the

specific heat jump at Tc, which is
3
(AC p ) m a x = (l)-iVfcB for g = 0 (dipolar interactions only) (9)

and becomes
3 1
(AC p ) m a x -> (OO)-ATA;B for g = - (tricritical point). (10)
Let us investigate the case of uniaxial ferroelectrics of the TGS family,
in particular triglycine sulfate (TGS), triglycine fmoberilate (TGFB), and
triglycine selenate (TGSe).
To get the corresponding numerical values for the quadrupolar inter-
action coefficient g the only information needed is the experimental value
of the jump in specific heat per unit volume at T = T c , i.e., (AC p ) m a x in
erg/cm 3 K, and the number of dipole moment per unit volume N = Z/vc
(with Z = 2, the number of formula units per unit cell, and vc = abcsma,
the monoclinic unit cell volume in terms of the lattice parameters a, 6, c
and the angle a, as given by X-ray diffraction data 3 ).
Relevant specific heat data for TGS, 4 " 6 TGFB, 7 and TGSe, 8 - 9 including
both a.c. calorimetry and adiabatic calorimetry measurements, are given in
Table 3.8.1, where the g(ACp) value from Eq. (7) is given by

1 Nk¥
ff=
3 (11)
2(AC„

The last column in Table 3.8.1 gives the g(Ps) value obtained from
the temperature dependence of the spontaneous polarization of TGS, 1 0 , 1 1
TGFB, 1 2 and TGSe 13 in the close vicinity of T c . These values are basically
confirmed by the g(ACp) values obtained from specific heat data.
A trend may be noted from TGS, which at ambient pressure is farthest
from the tricritical point (g = | ) , to TGSe, close to it at the same pressure.

Table 3.8.1.

Crystal Tc (K) (ACp)max N (ACp)max/(§JVKB) g(ACp) g(Ps)

(erg/cm 3 K) (dipoles/cm 3 K)

TGS 322.2 0.618 x 10 7 1.56 x 10 22 1.19 0.16 0.17

TGFB 346.2 1.35 x 10 7 1.58 x 10 22 4.18 0.25 0.27
TGSe 295.3 1.93 x 107 1.50 x 10 22 6.2.2 0.28 0.32
246 Effective Field Approach to Phase Transitions

'-5
tA cm
Vi N KB
5.0

2.5

0
0.010 0.00 5 0.00
(T c -T)Ac — "
Fig. 3.8.1. Plot of reduced specific heat vs. reduced temperature for uniaxial ferroelec-
tric crystals of the TGS family.

Figure 3.8.1 depicts the normalized ferroelectric specific heat data from
T G S , 4 - 6 TGFB, 7 and TGSe 8 ' 9 in a narrow vicinity of T c . The TGS data
indicate that (AC p ) m a x is only slightly larger than (3/2)./V&B, the value
corresponding to g = 0 (almost negligible contribution from quadrupolar
or higher order interactions). On the other hand, the TGSe data show
that (AC p ) m a x is about six times larger than (3/2)N1CB- This means that
the thermal energy release or absorption by the crystal is going through the
order-disorder phase transition taking place in a much shorter temperature
interval in the latter than in the former case, which might be some relevance
in connection with the working of devices making use of the rate of change
of spontaneous polarization near T c .
Figure 3.8.2 shows experimental data of g' = g + ftp2 + • • • , as a func-
tion of the squared reduced spontaneous polarization, Ps2 = (Ps/Nfi)2, for
TGS, 10 - 11 TGFB, 1 2 and TGSe 13 obtained using Eq. (2). It may be seen
that the TGS data, available in an extended range of temperature below
T c , and therefore going back to p 2 values close to one, show that higher
order multipolar contribution become non-negligible at low temperatures.
The g(Ps) value for TGSe from these data is perhaps too close to the tri-
critical value g = \ and is somewhat larger that the g(ACp) value given
above. More detailed and precise measurements of spontaneous polariza-
tion for this crystal, especially in the close vicinity of T c , would be certainly
welcome.
 Specific Heat and Quadrupole Interactions in Uniaxial Ferroelectrics 247

0.7 5
T6Se:Pso=4.14 ptC/em2,Tc = 295.VK
T6FB: Pso- 4.49 /iC/cm 2 , Tc = 34„6.2°K
TGS : Pso=4.28;uC/cm2,Tc = 321.20K
0.50
i
0.2 5 T6S
•-CH>oW^n^o^^ o o
°%o
0 0.50 1.00

Fig. 3.8.2. Plot of g' determined from experimental data on spontaneous polarization
at given temperatures using Eq. (2) as a function of squared spontaneous polarization.

It may pointed out that the inclusion of quadrupolar and higher order
terms in the effective field responsible for the ferroelectric phase transi-
tion improves the theoretical fit to temperature-dependent spontaneous
polarization 1 ' 14 in some second order transition uniaxial ferroelectrics,
describes semiquantitatively the amount of thermal hysteresis 15 in various
typical first order transition ferroelectrics, allows one to get a fair quan-
titative prediction of the composition at which a mixed ferroelectric/non-
ferroelectric system approaches the tricritical point, 16 and, as shown in this
work, produces a good correction between thermal data (specific heat) and
dielectric data (spontaneous polarization) in the vicinity of a ferroelectric
transition. All these results put together make a good case for the actual
applicability of the generalized effective field concept to ferroelectric phase
transitions.

Acknowledgment

Financial support from CITyT is gratefully acknowledged.

References

1. R. Ramirez, M.F. Lapena and J.A. Gonzalo, Ferroelectrics 124, 1 (1991) (we
note some fairly obvious typing mistakes in this paper).
248 Effective Field Approach to Phase Transitions

2. J. A. Gonzalo, Effective Field Approach to Phase Transitions and Some Appli-

cations to Ferroelectrics (World Scientific, Singapore, 1991), pp. 56-63.
3. See, for instance, Landolt-Bornstein, Group III, Vol. 16, Ferroelectrics and
Related Substances (Non-oxides) (Springer-Verlag, Heidelberg, 1982).
4. R. Tobon and J.E. Gordon, Ferroelectrics 17, 409 (1977).
5. S.A. Taraskin, B.A. Strukov and V.A. Meleshina, Sov. Phys. Solid State 12,
1089 (1970).
6. W. Reese and L. May, Ferroelectrics 4, 65 (1972).
7. V.A. Chernenko and I.N. Polanov, Sov. Phys. Solid State 2 1 , 1059 (1979).
8. B.A. Strukov, S.A. Taraskin and V.A. Koptsik, Sov. Phys. Crystallogr. 13,
541 (1968).
9. K. Ema, K. Harnano, K. Kurihara and T. Hatta, J. Phys. Soc. Jpn. 43, 1954
(1977).
10. S. Triebwasser, IBM J. Res. Dev. 2, 212 (1958).
11. A.G. Chynoweth, Phys. Rev. 117, 1235 (1960).
12. H.H. Wieder and C.R. Parkerson, J. Phys. Chem. Solids 27, 247 (1966).
13. Z. Malek, J. Strajblova, J. Novotny and V. Mecerek, Czech. J. Phys. 18, 1224
(1968).
14. G. Lifante, J.A. Gonzalo and W. Windsch, Ferroelectrics 135, 277 (1992).
15. J.A. Gonzalo, R. Ramirez, G. Lifante and M. Koralewski, Ferroelectrics Lett.
15, 9 (1993).
16. G. Lifante, J.A. Gonzalo and W. Windsch (to be published).
 Chapter 3.9

Field-Dependent Temperature Shift

of the Dielectric Losses Peak in TGS*
Tomas Iglesias, Beatriz Noheda,
Gines Lifante and Julio A. Gonzalo
Departamento de Fisica de Materiales,
C-IV Universidad Autonoma de Madrid,
28049 Madrid, Spain

Dielectric constant and loss factor measurements have been performed in

triglycine sulfate single crystals at the vicinity of the Curie temperature
( r c = 48.5° C) as a function of a.c. driving field (20 < v < 106 Hz) in a
wide range of field amplitude (50 > Eo > 0.15 V/cm). Well-defined shifts
of loss factor peak (Z) max ), increasing monotonously with the field, not
previously reported as far as we know, were observed and analyzed in
terms of the energy dissipated within the vanishing hysteresis loops at
T « Tc corresponding to the Eo « EC(T) coercive field.

Triglycine sulfate is a prototypical example of second order transition uni-

axial ferroelectric. 1 Its dielectric properties, 2 including the dielectric loss
factor, 3 ' 4 have been widely investigated, but no systematic study of the
field dependence of these properties has been previously performed. Such a
study may help to clarify some controversial 5 ' 6 previous results.
Properly oriented single crystal plates, with the main surfaces perpen-
dicular to the ferroelectric 6-axis, were cut from a large single crystal of good
optical quality grown from water solution in the s t a n d a r d way. Gold leaf
electrodes were attached to the main surfaces. While samples of various
thicknesses were examined, a conveniently thick cleaved sample of thick-
ness d « 0.2 cm was used for t h e measurements reported here. To check

*Work previously published in Ferroelectrics Letters 17, 3/4 (1994). Copyright © 1994.
Taylor &c Francis Group.

249
250 Effective Field Approach to Phase Transitions

the quality of the sample, hysteresis loops were observed through T = Tc

on the screen of a Nicolet 310 digital oscilloscope, which showed negligible
asymmetry. Capacitance and losses factor were measured with an automatic
Hewlett Packard Universal Bridge 4284 A with high accuracy. The temper-
ature of the sample, within the sample holder immersed in a large-capacity
water bath controlled by a Haake F-3, was measured by a chromel-alumel
thermocouple and recorded automatically by means of a Keithley 196 sys-
tem DMIM microvoltimeter.
Figure 3.9.1 shows the losses factor D = tan 5, along with inverse
dielectric constant, as a function of temperature in the vicinity of Tc =
48.56°C at a frequency v = 1kHz for the following a.c. field ampli-
tudes: EQ = 50,15,5,1.5, 0.5V/cm. It can be clearly seen that (a) D m a x
is unusually large for large fields and decreases sharply for small fields
down to values about 20 times smaller; (b) there is a shift in temperature
AT m = T(DmeiX) — Tc, which is also very substantial for large fields and
becomes practically vanishing for the lowest fields. Figure 3.9.2 is a blow up
of the region closest to Tc in Fig. 3.9.1, showing in more detail the behavior
for the three lowest field amplitudes.
Table 3.9.1 summarizes the main results contained in the data of
Figs. 3.9.1 and 3.9.2 and shows, in the last column, that in spite of the
large variations in AT m and EQ for the family of curves depicting D(T),
which span almost two orders of magnitude, the ratio ATm/Eo(sin 5)1/2
remains very approximately constant.
These results can be analyzed in terms of the energy dissipated at
T < Tc within the vanishing hysteresis loops corresponding to coercive
field values, EC(T), approximately matching the a.c. field value spanned by
EQ in V/cm.
The energy dissipated per unit volume and unit time by a dielectric
characterized by a complex dielectric constant e(u>) = e'{ui) — ie"(u>), where
s"(to)/e'(LO) = sin S, tan 5 = D, is given by 7

W = \^Ets"{u) = \~Ele'{^) sin 6. (1)

On the other hand, the energy dissipated per unit volume and time
within a hysteresis loop in a ferroelectric material is

W = ~PP?, (2)

where (3 = Es/PsAirTc/C is the effective mean field coefficient8 and Ps the

spontaneous polarization per unit volume at the corresponding tempera-
ture. Therefore, we can set, for a ferroelectric near a second order phase
 Field-Dependent Temperature Shift of the Dielectric Losses Peak in TGS 251

1.0 1 1 1

0.8 -- 1 KHz .
o o *
U O v
O
0.6 - .'
° •A - *
0 -
id «
fc<
w 0 B ".
v 0.4 - «° 0
C
O »
O
CO <* »• DJ
w
o IT °
oo
0.2 V B ,
-
H
j * — * * * * * * " " """o

•"•BffiB&SBf^L
i •
1 — -•' 1 ' " ^
£
10~
^ » 50 V/cm * 1.6 V/cm
"*\ • 15 V/cm • 0.5 V/cro
! , \ V • 5 V/cm • 0.15 V/cm

8 fv& „

*J
<J \."\5 -
CD

o
V\ "Av\
1 -
*• "a ^r
w
u ' \ $
>
i
44 46 48 50 52

Temperature ( C)
1
Fig. 3.9.1. Triglycine sulfate losses factor (D) and inverse dielectric constant (e ) as
a function of temperature for various a.c. field amplitudes.

transition, with e'(cj) fulfilling the Curie-Weiss law,

'1 C
Wm&x sin 5 n
~ 8TT ° V 2 T, - T,,

a 2 H^3/3f T
P2
1
s0)
T
J
<r T
m ^ -1 c j
(3)
8TT V c
252 Effective Field Approach to Phase Transitions

0,20 r- 1 r —1 1 :

°A 1 KHz
P 0.15 --
A
*
A
U
o A
1->

V *
0.10 r
O
«J 0 V
o »
0
w
CO 0 •«
m 0.05 -
m °- A° *
O 0 v
» •• .»« o o g ,
• *» ••

0.00 «
. ' i l l !
,-4
10 ••
1 •
• SO V/cm * 1-5 V/cm .
• » IS V/cro • 0.5 V/em
w * • « 5 V/cm • 0.1S V/cm
C 0
a • •
o •
*
* *
•

a
a ** ** -
J-. a
4)
?>
d > 1 i 1 1
48.2 48.3 48.4 48.5 48.6 48.7 48.8

Temperature (°C)
Fig. 3.9.2. Triglycine sulfate D and e~l vs. T as in Fig. 3.9.1 in the close vicinity of Tc
to show in more detail the curves corresponding to the lowest field amplitudes.

where W from Eqs. (1) and (3) is used and a(w) is defined as a dimen-
sionless coefficient of proportionality, equal or less than unity, which may
be expected to be somewhat frequency dependent, and PS(T) = V3Ps0 x
(1 - T/Tc) 1 / 2 has been substituted.
 Field-Dependent Temperature Shift of the Dielectric Losses Peak in TGS 253

Table 3.9.1. Losses factor of TGS near T c as a function of a.c.

field (1 kHz).

E0 (V/cm) A T m (°C) Dmax sin<5m ATm/E0(sm5n 11/2

50 2.52 0.87 0.66 0.062

15 0.94 0.78 0.62 0.079
5 0.26 0.47 0.43 0.076
1.5 0.04 0.18 0.18 0.068
0.5 0.01 0.06 0.06 0.085
0.15 — 0.04 0.04 —

Equation (3) leads to

AT m = AEoisinS^2, AT m = Tc - T m , (4)

where
1 2
A_(27r/3) / fy
(5)
a{uj) \kB
after substituting Ps0 = Nfi, C = A-K^L2 /k-Q (Curie constant), and Tc =
fUN^/k-Q (Curie temperature) in terms of microscopic quantities
into Eq. (3).
The data for AT m and i?o(sin S^)1/2 are plotted in log-log form in
Fig. 3.9.3, and the linear fit through the experimental points with slope
equal to one implies,

,4 o b s « 0.057, (6)

while, from Eq. (5), using fi = (fcBC/47rA'')1/2 = 1.58 x 10~ 18 esu cm,8 we
get

(27T/3)1/2 / 1 . 5 8 x l 0 " 1 8 \ 0.0165 ,. nn

Then a(to) is the order of and less than unity, as expected, and the
validity of Eq. (4) to describe the observed behavior is confirmed.
It may be concluded: (a) that a novel effect, the temperature shift with
field amplitude in the losses factor peak near a second order ferroelectric,
has been experimentally established; (b) the calculated linear behavior of
AT m (temperature shift) with E0 (field amplitude) is fulfilled by the present
data for TGS in a remarkable range, spanning more than two orders of
magnitude.
254 Effective Field Approach to Phase Transitions

(°C) ,o»

ICT1

10" 2

J L
10"' 10° 10* 10*
1/z
EQ (sin 5m) (volt/cm)
Fig. 3.9.3. Log-log plot or temperature shift AT m = Tc - T(D m a x ) as a function of
field amplitude times (sin5m) 1 / 2 where <5m = t a n - 1 ( D m a x ) . The straight line through
the experimental points is (AT m ) c a | using Bq. (4).

Further work at still lower a.c. field amplitudes and various frequencies
is under way.

Acknowledgments

We acknowledge the financial support of C I C y T (Spanish Scientific and

Technological Research Commission) under Materials Research G r a n t t o
investigate ferroelectric phase transitions.

References

1. See, for instance, F. Jona and G. Shirane, Ferroelectric Crystals (Macmillan,

New York, 1962).
2. See, for instance, Landolt-Bornstein, Group III; vol. 16, Ferroelectrics and
Related Substances (Non-Oxides) (Springer-Verlag, Heidlberg, 1982).
3. R.M. Hill and S.K. Ichiki, Phys. Rev. 132, 1603 (1963).
4. R. Garcia and J.A. Gonzalo, Phys. Rev. Lett. 50, 1501 (1983).
5. E. Courtens. Phys. Rev. Lett. 5 1 , 844 (1983).
6. J. Kortzler, Phys. Rev. Lett. 5 1 , 1811 (1983).
7. See, for instance, A.J. Dekker, Solid State Physics (Prentice Hall, Englewood
Cliffs, NJ, 1962).
8. See, for instance, J.A. Gonzalo, Effective Field Approach to Phase Transitions
and Some Applications to Ferroelectrics (World Scientific, Singapore, 1991).
 Chapter 3.10

Discontinuity and Quasitricritical

Behavior near Tc in Ferroelectric
Triglycine Selenate*
Tomas Iglesias, Beatriz Noheda,
Gines Lifante, and Julio A. Gonzalo
Departamento de Fisica de Materiales,
C-IV Universidad Autonoma de Madrid,
28049 Madrid, Spain

Marcel Koralewski
Institute of Physics, Adam Mickievichz University,
60-780 Poznan, Poland

Precise dielectric constant and hysteresis loops measurements at very low

heating and cooling rates (<~0.5°C/h) near Tc « 22.0CC in single crystals
of triglycine selenate reveal previously unobserved discontinuities and a
very small thermal hysteresis (AT « 0.05°C), indicative of a first order
transition very close to a tricritical point. The set of tricritical exponents
/ 3 « i , J « 5 , 7 « 1 , borne out by present data, and a « | (from
Ema's specific heat data) describe very well the observed behavior in
the vicinity of the phase transition.

Triglycine selenate 1 [ ( N H 2 C H 2 O O O H ) 3 H 2 S e 0 4 ] , hereafter TGSe, is a well-

known ferroelectric material pertaining to the triglycine sulfate (TGS) fam-
ily t h a t undergoes a typical order-disorder transition at about T c s=s 22° C;
the space group of the lower-temperature phase being P2\ and t h a t of the
higher-temperature phase P2\/m. T h e main features of the phase transition
in T G S e are like those of other members of the same ferroelectric family and,

*Work previously published in Phys. Rev. B 50, 10307 (1994). Copyright © 1994. The
American Physical Society.

255
256 Effective Field Approach to Phase Transitions

up to the present, it has been generally considered as a second order, 2 or

continuous, phase transition. Some prominent characteristics of the TGSe
transition make it worth further scrutiny. Its specific heat peak 3,4 is about
six times larger than the specific heat peak of TGS, which may be taken as
an indication that the transition is close to first order, if not first order. Also,
in contrast to TGS, a moderate amount of deuteration 5 induces a clear dis-
continuity at the transition, accompanied by sizable thermal hysteresis. The
fact that both deuteration and hydrostatic pressure are known to influence
the character of the transition has led Okada and Suzuki6 to investigate a
possible tetracritical point in this crystal, which, according to them, could
be attained at p « 2.3kbar and x = 0.38 (deuterium concentration).
In this work, we report precise dielectric constant and hysteresis loop
measurements, performed at very low heating and cooling rates (~0.5°C/h)
in the vicinity of the phase transition, from which we conclude that the
phase transition of TGSe is discontinuous (first order) at ambient pressure
and zero deuteration, with a small thermal hysteresis A T « 0.05°C. In
addition, we are able to show that tricritical exponents, (3 « | , 8 « 5, and
7 « 1, obtained from our data, together with the specific heat exponent
a « | , from Ema's data, 3 characterize the order-parameter behavior of the
system in a certain range of temperature below Tc.
The samples were parallelepipeds with surface area (perpendicular to
the fr-axis) ranging from 6 to 16 mm 2 , and thickness (along the fe-axis) rang-
ing from 2 to 6 mm, cut from a good optical quality TGSe single crystal
grown from aqueous solution. Gold leaf electrodes were attached directly
to the surfaces perpendicular to the ferroelectric 6-axis. The sample holder
was well sealed within a thick-walled copper container and was immersed
in a 15-1 temperature-controlled oil bath regulated by a Hake model F-3,
which operated in both the slow-heating and the slow-cooling modes at
a rate of about 0.5°C/h. The temperature was measured by means of a
chromel-alumel thermocouple with a Keithley digital microvoltmeter model
196 system DMM. Capacitance (C) and loss factor (D) were measured
at frequencies between 1kHz and 1MHz by a Hewlett-Packard precision
LCR meter model HP-4284-A with very good accuracy and stability. From
these data both the real and the imaginary parts of the dielectric constant
could be obtained. As discussed below, the very high loss factor (of the
order of unity) observable at the peak, just below the capacitance maxi-
mum, should be interpreted in terms of energy dissipation within the very
low coercive-field hysteresis loops at T near and below T c , driven by the
small (~2 V/cm) radiofrequency signal (in fact the high-£> values disappear
 Discontinuity and Quasitricritical Behavior Near T c 257

at T > T c ), rather than in terms of intrinsic Debye relaxation behavior,

which would take place only at much higher frequencies (~GHz). Hystere-
sis loops were observed by means of a simple Sawyer-Tower circuit with
phase compensation at a frequency of 10 Hz in a Nicolet model NIC-310
digital oscilloscope with high resolution (4000 points per loop). For reading
the polarization vs. field data from the loops it was important to deter-
mine precisely the true center, and this was done both by displaying the
digital information on the monitor of a desktop IBM PC computer and by
recording the trace of the loop with a precision Hewlett-Packard plotter.
Capacitance and hysteresis loop measurements could be taken instanta-
neously every second, and the resolution in temperature could be as high
as 10~ 4o C from point to point. Some of the capacitance and loss data were
taken with this resolution, but no such high resolution is needed for hystere-
sis loop data and, on the other hand, managing 4000 points per loop per sec-
ond would become impractical. It may be noted that using relatively thick
samples (~6 mm along the fr-axis) improves the reproducibility of the data.
Figure 3.10.1 shows the dielectric constant (e) and loss factor (D =
s"/e') for a relatively thick sample (4.5 mm) both during heating and cool-
ing the sample slowly at about 0.5°C/h. It may be noticed that at tem-
peratures above the transition the heating and cooling data points fall on
top of one another. A clear discontinuity in the heating curve of e(T) at
T ss 22.16°C corresponding to the peak value can be observed, accompanied
by a small thermal hysteresis of about AT « 0.045°C. At T sa 21.16°C,
1°C below the peak, another less pronounced discontinuity shows up in the
heating curve accompanied by a thermal hysteresis of about AT « 0.10°C.
Discontinuities appear also in the curves of D(T) at the same two tem-
peratures, but the peak value of D(T) is located at the lower one, which
is displaced by about 1°C with respect to the peak value of e(T). D(T)
drops discontinuously to a near-zero value just above the peak value of
s(T). The peak values of D are about 0.5 and 0.7 for heating and cooling,
respectively. Since these high values can be expected 7 for normal Debye
behavior only near the relaxation frequency (w ~ 2ir x 1 0 9 s - 1 ) , where
Anax ~ wr ~ 1, provided that e(w = 0) » E(LO = co), we may conclude
that they are due to energy dissipation within the low-coercive-field hys-
teresis loops driven by the low 1-kHz amplitude of the bridge oscillator at
temperatures below and very close to the transition temperature. If this is
the case, one would expect D to be proportional (for Ec < Eo, the driving
field amplitude) to the area enclosed by the loops, roughly proportional to
the spontaneous polarization after reaching the maximum, and near zero
258 Effective Field Approach to Phase Transitions

Temperature ( C)

Fig. 3.10.1. Dielectric constant (e) and dissipation factor (D) of TGSe as a function of
temperature ( / = 1kHz) [heating (•) and cooling (o)].

after the transition to the paraelectric phase is accomplished. The fact that
D drops discontinuously to zero at the transition may be taken as an indi-
cation that the spontaneous polarization also drops discontinuously to zero
at the transition. Subsequent measurements of spontaneous polarization
vs. temperature through the transition confirmed this interpretation and
showed that the ratio of T>max at AT = 1°C below the transition to D
just below transition is roughly the same as the ratio of P S 2 (AT = 1) to
P S 2 (AT = 0) = (P*) 2 - Measurements on good-quality single crystals of
triglycine sulfate under identical conditions showed no noticeable disconti-
nuity in a large peak with e m a x = e(T « Tc) « 2.8 x 105.
 Discontinuity and Quasitricritical Behavior Near Tc 259

14 16 18 20 22 24 26 28 30

•T

o ,
o
2.5 O -
o

2.0 "
o

1.5 \
CJ
4. 1.0
\
0.5
••
•
00 t • 1

Temperature (°C)

Fig. 3.10.2. Inverse dielectric constant ( e - 1 ) and spontaneous polarization (P s ) of TGSe

as a function of temperature [heating (•) and cooling (o)].

Figure 3.10.2 gives the inverse of the dielectric constant £ _ 1 (T), and the
spontaneous polarization PS(T), measured at 10 Hz as a function of temper-
ature in the vicinity of the transition. It can be seen that the spontaneous
polarization loops suddenly to almost zero at about the same temperature
as the transition discontinuity in e _ 1 (T). Furthermore, the ratio of the
slopes of £ - 1 ( T ) vs. T below and above the transition [(1/C_)/(1/C+) «
4.5] is close to the value of 4 corresponding to tricritical point behavior
and considerably higher than the value of 2 pertaining to a standard crit-
ical point. The behavior of the spontaneous polarization PS(T), obtained
from hysteresis loops under slow cooling, indicates a discontinuous drop at
260 Effective Field Approach to Phase Transitions

about the same temperature as the discontinuity in the dielectric constant.

It may be noted that due, at least, in part, to imperfect phase compen-
sation of the hysteresis loops some amount of rounding at the transition
is almost unavoidable. The estimated discontinuous jump in spontaneous
polarization from these data is P* ss 0.90/xC/cm 2 . The saturation spon-
taneous polarization Ps0 = Nfj, for TGSe has not been measured directly,
as far as we know, but a fair estimate can be obtained taking into account
that P s 0 « 4.20/xC/cm 2 for TGS, 8 and that the ratios

N{TGSe)/N(TGS) = NSe/Ns « 1.56 x 10 22 /1.5 x 10 22 ,

and
M(TGSe)MTGS) = [(NSeCs)/(NsCSe)}1/2,

where Cs e = 4050 K and Cs = 3650 K are the respective Curie constants,

C = 4nfi2/kB- Using these data 2 we get Pso ~ 4.50/xC/cm 2 , slightly larger
than the value Pso ~ 4.14/zC/cm 2 used in Ref. 4. Then we can get an
estimate of the maximum thermal hysteresis AT m a x to be expected in terms
of p* = P*/Ps0 « 0.20 from9
T*/Tc = 1 + AT m a x /T c =[1 - ( p : ) 4 / 5 ] - x = 1.00032, (1)

where T* = 295.16 K = 22.03°C is the (first order) transition temperature

and Tc = 295.06 K = 21.93°C the Curie temperature. The resultant value
for ATmax = 0.10°C is compatible with the observed thermal hysteresis
AT = 0.045°C.
The small discontinuities for TGSe in e(T) and PS(T) at the transition
and the barely observable thermal hysteresis just mentioned suggest that
quasitricritical behavior may be expected just below the transition tempera-
ture in this crystal. In this case the tricritical exponents for the spontaneous
polarization, the critical isotherm, the inverse dielectric constant, and the
specific heat would be given by

psoc(AT)", /3=]; eocp5, S = 5,

4
1 (2)
e-1«(AT)T> 7 = 1; ACpocAT~a, a = -,

instead of by (3 = 5, S = 3, 7 = 1, a = 0, which are the usual critical expo-

nents for a first order transition. These results can easily be obtained from
the equation of state relating field (e), polarization (p), and temperature
(T/Tc), in dimensionless units,

e = (T/Tc - \)p + bp3 + cp5L (T<TC, p < 1), (3)

 Discontinuity and Quasitricritical Behavior Near T c 261

10*

Critical exponents for TGSe

0=Ln(Ps)/Ln(AT)
a = Ln(AC p )/Ln(AT)
10'

E
o
\
o
a.
en
Q_
10° /
P|=Ps(T*)

T<Tr<T*

10"'
i<r2 10"' io° io'
AT=TC-T (°C)

Fig. 3.10.3. Log-log plots of spontaneous polarization (this work) [heating (•) and
cooling (o)] and ferroelectric specific heat [Ema's data (Ref. 3)], as a function of A T =
Tc—T (Ema's T c corresponds to our T*). Numerical values for the pertinent exponents
/3 and a are given. Spontaneous polarization data for T > Tc but T < T* (corresponding
to A T < 0) do not appear in this plot.

for the cases 6 = 0 (or b <C cp2) (tricritical-point behavior) and b > 0
(b » cp2) (normal critical point).
Figure 3.10.3 depicts, in log-log scales, the temperature dependence of
our data of spontaneous polarization for TGSe with Tc = 21.93°C. The
value obtained for the exponent (3 — 0.26 ± 0.02 is very close to the tri-
critical value (3 = j . In the same graph the specific-heat data for TGSe of
Ema 3 are plotted directly in a log-log scale. The ferroelectric contribution
to the specific heat, after subtracting the background (corresponding to
nonferroelectric contributions), given in Fig. 9 of Ema's paper 3 in arbitrary
units has been normalized by dividing ACP by the maximum value ACpm,
corresponding presumably to A T = T* - T — 0°C (with T* correspond-
ing to Ema's T c ). The value for a = 0.50 ± 0.02, obtained neglecting the
first few points with AT < 0.5CC, is in excellent agreement also with the
tricritical-point value a = \.
Finally, Fig. 3.10.4 shows the field dependence of the polarization at
a temperature T = 21.92°C just below Tc < T* = Tc + AT = 22.03°C.
262 Effective Field Approach to Phase Transitions

Critical e x p o n e n t s for TGSe

C\2
1/6=0.23 ±0.03
£
O (T * T c )
o
OH

;
P *=P s ('r )V

. • ' . l

10 100

E(V/cm)
Fig. 3.10.4. Log-log plot of polarization ( F ) vs. field (E) at T = 21.92°C, close to the
temperature corresponding to the tricritical isotherm, giving the exponent 1/5.

Again, the exponent value 1/5 = 0.23 ± 0.03 is very close to the tricriti-
cal value 1/5 = 1/5. The error quoted for 1/5 corresponds to 40 < E <
150V/cm, since deviations toward 1/5 = 0 for E —» 0 are expected for a
discontinuous transition, and also toward 1/(5 > 1/5 for E —> Emax due
to imperfect phase compensation of the hysteresis loop, originally compen-
sated at T > Tc. 1/5 has been taken, therefore, as the asymptotic value
away from E = 0, neglecting rounding effects in the loops.
The exponent 7 corresponding to e _ 1 (T) is not shown explicitly but it
is clear from the asymptotic linear behavior of e _ 1 above and below Tc that
its value is very close to 7 = 1, while possible logarithmic corrections very
near Tc are not excluded. As should be expected the observed exponents
fulfill very well Widom's equality,

/?(<J-1)«7, (4)

and the Griffiths equality

(3(5 + 1) « 2 - a. (5)

In summary, the results reported here clearly indicate that the ferroelec-
tric paraelectric transition of TGSe is first order and very close to tricritical.
It may be noted that the early literature on other important ferroelectric
crystals, like potassium dihydrogen phosphate and BaTiC>3, presented the
respective transitions as second order transitions, and only later did more
 Discontinuity and Quasitricritical Behavior Near Tc 263

precise measurements establish their first order character. Related previ-

ous work on the T G S e phase t r a n s i t i o n 1 0 - 1 4 did not substantiate either
the discontinuity at T = 20.0°C or a clear quasitricritical behavior. A
mean field approach is applicable to the case of T G S e (and other uniaxial
ferroelectrics) because long-range dipolar forces suppress the polarization
fluctuations.

Acknowledgments

We would like to t h a n k A. Czernecka (Poznan) for providing us with some

good samples of TGSe, and the C I C y T (Spanish Research Agency) for
financial support (Grant no. MAT90-0304).

References

1. See, for example, F. Jona and G. Shirane, Ferroelectric Crystals (Pergamon,

New York, 1962); B.T. Matthias, C.E. Miller and J. Remeika, Phys. Rev.
104, 849 (1956).
2. See, for example, Landolt-Bornstein, New Series, Group III, Vol. 16b, Ferro-
electrics and Related Substances: Non-oxides (Springer-Verlag, Berlin, 1982).
3. K. Ema, J. Phys. Soc. Jpn. 52, 2798 (1983).
4. B. Noheda, G. Lifante and J.A. Gonzalo, Ferroelectrics Lett. 15, 109 (1993).
5. K. Gesi, J. Phys. Soc. Jpn. 41, 1437 (1976).
6. K. Okada and I. Suzuki, Ferroelectrics 39, 1205 (1981).
7. G. Luther, C. Birkenheier, G. Brosowski, H.E. Miiser and H.E. Petersson,
Ferroelectrics 8, 569 (1974).
8. LA. G. Chynoweth, Phys. Rev. 117, 1235 (1960).
9. J.A. Gonzalo, R. Ramirez, G. Lifante and M. Koralewski, Ferroelectrics Lett.
15, 9 (1993).
10. K. Gesi and K. Ozawa, J. Phys. Soc. Jpn. 40, 599 (1976).
11. H. Yamashita, I. Todo and I. Tatsuzaki, J. Phys. Soc. Jpn. 44, 1261 (1978).
12. H. Yamashita, Y. Takeuchi and I. Tatsuzaki, J. Phys. Soc. Jpn. 49, 1894
(1980).
13. Y Takeuchi, H. Yamashita and I. Tatsuzaki, J. Phys. Soc. Jpn. 50, 9 (1981).
14. Y. Takeuchi, H. Yamashita and I. Tatsuzaki, J. Phys. Soc. Jpn. 50, 2022
(1981).
 Chapter 3.11

Scaling Equation of State for

Ferroelectric Triglycine Selenate
at T « Tc*
T. Iglesias, B. Noheda, B. Gallego,
J.R. Fernandez del Castillo G. Lifante and J.A. Gonzalo
Departamento de Fisica, de Materiales,
Universidad Autonoma de Madrid, 28049 Madrid, Spain

Digital data of polarization vs. field on triglycine selenate at closely

spaced temperature intervals (AT ss 0.015) in the vicinity of the quasi-
tricritical point of triglycine selenate have been collected. These data
fulfill very well the scaling equation of state e+ = rnp + (l/5)p 5 (where
e_ and e+ correspond to T < Tc and T > Tc, respectively), where
p = ( P s / P s 0 ) / { 1 - T/Tcy'A and e = {E/Ea0)/{1 - T/Tc}5'* are the
scaling variables, with tricritical exponents /3 = 1/4, <5 = 5.

Scaling theory, as is well known, was first introduced by W i d o m 1 to

describe the behavior of simple fluids near critical points, and later extended
t o describe the scaling equation of s t a t e of fluids2 and other systems
including ferromagnetic, order-disorder alloys, ferroelectrics, etc. Not many
investigations 3 ' 4 of the scaling equation of s t a t e in ferroelectric systems have
been reported, in p a r t due to the fact t h a t truly continuous second order
transitions in ferroelectrics are not very frequent.
No experimental investigation of the scaling equation of s t a t e of a fer-
roelectric near a tricritical point 5 has been previously reported, as far as
we know. In this chapter, we report digital hysteresis loop d a t a in the
vicinity of the ferro-paraelectric transition of triglycine selenate (TGSe),
which happens to be very close 6 to a tricritical point. T h e phase transition,

*Work previously published in Europhysics Letters 28, 91 (1994). Copyright © 1994.

E D P Sciences.

265
266 Effective Field Approach to Phase Transitions

occurring for undeuterated TGSe at about 22°C, shows a minute disconti-

nuity in the dielectric constant accompanied by a small thermal hysteresis of
about 0.05°C, which indicates the proximity to the tricritical point. Tricrit-
ical exponents /3 = log A P s /log AT « 1/4, 6 = (log AE/ log A P ) T c « 5,
a = logACp/logAT « 1/2, are observed, which differ from the classical
critical exponents (5 = 1/2, 5 = 3, a = 0 reported for the transition in
isomorphous triglycine sulfate (TGS). 3 The main objective of the present
work was to check whether the corresponding scaling equation of state (with
tricritical point exponents) describes satisfactorily the observed behavior,
using digital hysteresis loop data, which are expected to define the transi-
tion much better than manually obtained hysteresis loop data.
The samples were gold-electroded plates cut with main faces perpen-
dicular to the ferroelectric 6-axis from a large-optical-quality TGSe single
crystal grown from water solution. For the particular crystal for which
data are shown below the area was 10.5 mm 2 and the thickness 4.7 mm.
The sample holder was well sealed within a thick-walled copper container
immersed in a controlled-temperature oil bath regulated by a Haake, model
F-3, using slow heating and cooling rates (~0.5°C/h). The temperature
was measured by means of a chromel-alumel thermocouple with a Keithley
digital microvoltimeter, model 196. Hysteresis loops in the temperature
interval 294.5 < T < 296.3 K were observed and recorded by means of
a Nicolet, model NIC-310, digital oscilloscope connecting the sample to a
Sawyer-Tower circuit with phase compensation. For each loop, at every
temperature, 4000 points were recorded, thus ensuring high resolution in
the definition of the P vs. E curve. The frequency of the driving field was
10 Hz and the amplitude 425 V/cm. The true center of the loops was deter-
mined precisely by means of a simple computer program, 7 which ensured
symmetric ±PS and symmetric ±EC values simultaneously, Ps and Ec being
the spontaneous polarization and the coercive field, respectively.
Using a generalized effective field8
£ eff = E + (3P + 7 P 3 + SP5L, (1)
where E is the external field and P the polarization, in which successively
higher order terms in the polarization can be attributed to dipolar {(3P),
quadrupolar (7P 3 ), octopolar {SP5) etc., contributions, the equation of
state for a uniaxial ferroelectric can be written as
F1 T P
^ - = -tanh-1 —
p x 4
.^^te
1
+ 4
!™ ( Nn " £,'• L (2)
 Scaling Equation of State for Ferroelectric Triglycine Selenate 267

where PNfi = Eso, is the saturation spontaneous field and N/J, = Pso the
saturation spontaneous polarization, N being the number of elementary
dipoles per unit volume and fi the elementary dipole moment. In terms of
reduced variables e = E/Es0, p = P/Pso, this equation becomes

e = — tanh" 1 p - [1 + gp2 + hp4L}p, (3)

where
g^j(Nn)2, h=^(N^L. (4)

Expanding the inverse hyperbolic tangent in series for p <C 1 (i.e., close
to the transition), and grouping terms, we get

T.-1h(m-')'p+(iT.-h)'L- (5)

which for g « 1/3, fc<l (corresponding to transitions close to a tricritical

point), gives, in terms of scaled variables,
T5
P 1 (T P
(6)
{T/Tc - I } 5 / 4 {T/Tc - 1}V4 5 \T< {T/Tc - l}i/4
or
em«mp+(l/5)p5, (7)
where e m = e/{l - T/Tc}5/4 and mp = mp/{l - T/Tcy/4 correspond,
respectively, to T < Tc (ferroelectric phase) and T > Tc (paraelectric
phase). It will be shown below that Eq. (7), which is the tricritical point
(TCP) scaling equation of state for uniaxial ferroelectrics, describes quite
well the behavior of TGSe in the vicinity of T = TTCP •
Figure 3.11.1 shows a plot of the fourth power of the spontaneous polar-
ization (P s in yuC/cm2) as a function of temperature in the vicinity of the
transition at closely spaced temperature intervals. Imperfect phase com-
pensation of the hysteresis loops, which is unavoidable, because the con-
ductivity of the crystal is temperature dependent at T « Tc, gives rise to a
small residual contribution at temperatures just below and just above T c .
Thus, points with P < PTes (residual polarization) should not be considered
to describe the true scaling behavior. These data allow one to make a first
estimate of Tc = 295.818K and support the TCP exponent value (3 = 1/4
for TGSe. The small discontinuity expected for Pa(T) at T = T* (first order
transition temperature) is rounded off in this representation.
Figure 3.11.2 gives a plot of the fifth power of the polarization (also
in /LiC/cm2) as a function of field (in V/cm) for various temperatures in
268 Effective Field Approach to Phase Transitions

294.2 294.6 295.0 295.4 295.8 296.2

Fig. 3.11.1. Spontaneous polarization up to the fourth power for TGSe in the vicinity
of Tc ss 295.810 K. Due to unavoidable imperfect phase compensation of the hysteresis
loops, a small residual contribution at T close to T c can be observed.

0.20 :
• •>•«
. . ...
0.16 -
1 z
.^ j *
-—> . %o° »,
:
'a o-ia
u :
O

PH 0.08 r*
I
0.04 r
s* ,>» ^^-Yi>•
sK'BJilnT'TTTii 11 hi > 11111 11 u . L i
0.00 100 200 300 400
•ECV/cm)
Fig. 3.11.2. Polarization up to the fifth power vs. field at T = 295.749, 295.786, 295.810,
295.830, 295.848, 295.872 K in the vicinity of Tc m 295.810 K. A small residual contribu-
tion, corresponding to that shown in Fig. 3.11.1, is present at T close to T c .
 Scaling Equation of State for Ferroelectric THglycine Selenate 269

close vicinity of T c . The small residual contribution at T « Tc mentioned

before is also apparent, causing finite intercepts at E = 0 for the straight
lines approximating the relationship between P 5 and E. These data confirm
indirectly the previous estimate of Tc and support the TCP exponent value
8 » 5 for TGSe.
The scaled digital data from the full set of P vs. E curves in close
vicinity of Tc (below as well as above the phase transition) are given in
Fig. 3.11.3. It can be seen that these data fulfill quite well the behavior
predicted by Eq. (7) giving an excellent fit to both branches of the scaling
equation of state. As mentioned above, points with small P < Pres (residual
polarization) are expected to depart from the scaling behavior, and have
been omitted from the plot. It is clear that data for about 50 closely spaced
isotherms (Tn+i -Tn < 0.03°C) from T = 294.49 to 296.31 K collapse fairly
well on top of each other in spite of the large variation in absolute polariza-
tion value, more than two orders in magnitude. The T > Tc branch shows
systematic departures toward the low-field side for each isotherm from the
theoretical curve due to incompletely suppressed residual polarization, but
the envelope of sets of points belonging to different isotherms defines quite

1.80

Inp

0.80

-0.20

-1.20

-2.20
-8.80 -4.80 -0.80 3.20 7.20
In e

Fig. 3.11.3. Scaling equation of state for TGSe at T « T c , /3 = 1/4, 6 = 5. Experimental

points for T < Tc and T > T c are obtained from digital hysteresis loops in the interval
294.49 < T < 296.31 K. The continuous line is the tricritical scaling equation of state
e m = rap + ( 1 / 5 ) J 3 5 , with - for T < Tc and + for T > Tc. Here, p = ( P s / P s 0 ) / { 1 -
T/Tc}1/4 and e = (E/Es0)/{1-T/Tc}5/4 are the scaled field and the scaled polarization,
respectively. Points with E < 1/2 E m a x were used.
270 Effective Field Approach to Phase Transitions

well the general behavior in agreement with the theoretical curve. In order
to optimize the fit of Eq. (7) to the data, computer fits with Tc changing by
very small amounts (0.002 K) were made within certain intervals of the orig-
inal estimate of T T from the d a t a in Fig. 3.11.1. T h e best fit was obtained
for Tc = 295.810K, with P s 0 = 5.60/xC/cm 2 and Es0 = 40.5 V / c m . T h e set
of d a t a points with the highest p and e values correspond t o an isotherm
very close and just above the critical isotherm. T h e T < Tc branch shows
very good collapsing of d a t a toward low values (describing the behavior of
the spontaneous polarization away from T c ) but shows a distinct, albeit
small, systematic deviation from t h e tricritical point equation of s t a t e at
higher e values, probably related to the slightly discontinuous character of
the transition in TGSe, which is already of first order, 6 as indicated more
clearly by dielectric constant data.
It may be pointed out t h a t Eq. (7) properly speaking does not contain
adjustable parameters. T h e value of Tc is refined around a fixed transition
t e m p e r a t u r e given by various experimental observations. T h e value of P s o,
corresponding to the expected low-temperature spontaneous polarization
value, is also slightly refined from t h a t previously estimated, 6 combining
dielectric d a t a for T G S e and T G S . And, finally, t h e value of Eso = (3Pso,
where (3 = A-KTC/C is the dipolar mean field coefficient (not to be confused
with the spontaneous polarization critical exponent /3, which is j3 ~ 1/4
for T C P behavior), is also fixed in terms of the transition temperature, t h e
Curie constant, and the low-temperature spontaneous polarization.

Acknowledgments

We acknowledge the financial support of CICyT, grant PB93-1253, and the

Comunidad de Madrid, grant AE00138/94, for this work.

References

1. B. Widom, J. Chem. Phys. 3, 3898 (1965).

2. M.S. Green, M. Vicentini-Missoni and J.M.H. Levelt Sengers, Phys. Rev. Lett.
18, 1113 (1967).
3. J.A. Gonzalo, Phys. Rev. Lett. 2 1 , 749 (1968); Phys. Rev. B 1, 31225 (1970).
4. R. Ramirez, C. Prieto, J.L. Martinez and J.A. Gonzalo, Phase Transitions 9,
253 (1987).
5. For an in-depth theoretical discussion, see, e.g., J.D. Lawrie and S. Sarbach,
Theory of Tricritical Points, in Phase Transitions and Critical Phenomena,
 Scaling Equation of State for Ferroelectric Triglycine Selenate TJX

edited by C. Domb and J.L. Lebowitz, Vol. 9 (Academic Press, New York,
1984).
6. T. Iglesias, B. Noheda, G. Lifante and J.A. Gonzalo, Phys. Rev. B. (to be
published).
7. B. Gallego, J.R. Fernandez del Castillo, T. Iglesias, B. Noheda, G. Lifante and
J.A. Gonzalo, ISMPC-Physics and Computers (to be published).
8. R. Ramirez, M. Fe Lapen and J.A. Gonzalo, Ferroelectrics 124, 1 (1991).
 Chapter 3.12

Composition Dependence of the

Ferroelectric-Paraelectric Transition
in the Mixed System PbZri^Ti^Oa*
Beatriz Noheda, Noe Cereceda, Tomas Iglesias,
Gines Lifante and Julio A. Gonzalo
Depariamento de Fisica de Materiales, C-IV,
Universidad Autonoma de Madrid, 28049 Madrid, Spain

Hui Ting Chen and Yong Ling Wang

Shanghai Institute of Ceramics, Chinese Academy of Sciences,
1295 Ding Xi Road, Shanghai 200050, China

The dielectric constant and losses of good-quality ceramic samples

of Nb-doped ( l w t % N b 2 0 5 ) PbZn-^TixOs about the ferroelectric-
paraelectric transition for 0.03 < x < 0.09 have been measured with the
aim of investigating the behavior of the thermal hysteresis with composi-
tion and the possible existence of tricritical points in this mixed system.
The trend of the data, analyzed in terms of a generalized effective field
theory (EeB = E + (3P + 7 P 3 H ), indicates that two tricritical points,
at x = 0.26 and x = 0.51, are implied by the observed behavior at
lower x.

T h e mixed system P b ( Z r i _ a , T i a ; ) 0 3 , abbreviated P Z T , in which ferroelec-

tric and antiferroelectric transitions were reported by Shirane and Suzuki, 1 ' 2
has been widely investigated because of its outstanding piezoelectric and
pyroelectric properties. While the basic features of the ferroelectric phase
diagram have been well known for a long time, little attention has been
paid, as far as we know, t o the composition dependence of the character

*Work previously published in Phys. Rev. B 51, 22 (1995). Copyright © 1995. The
American Physical Society.

273
274 Effective Field Approach to Phase Transitions

(first or second order) of the ferroelectric-paraelectric transition. The char-

acter of the transition, and the possible existence of one or more tricrit-
ical points separating composition regions with discontinuous first order
transitions and continuous second order transitions can be investigated, in
good-quality ceramic samples of varying composition, by means of simple
dielectric constant and dielectric loss measurements. A decreasing trend
with changing composition in the transition thermal hysteresis, or better in
the difference between transition temperature (T*) and extrapolated Curie
temperature (T c ), is a clear indication that the system is approaching a
tricritical point.
We report dielectric measurements in Nb-doped (lwt% Nb2C>5) PZT
ceramics for 0.03 < x < 0.09, prepared and sintered at 1340°C for 1.5 h at
the laboratories of the Shanghai Institute of Ceramics, and for x = 0.22,
kindly provided by Dr. W. Wersing (Siemens AG). A straightforward anal-
ysis of the data using a generalized effective field approach, in which the
standard molecular field Eeg = E + (3P is generalized3 to include higher
order terms, i.e., Eeg = E + f3P + 7 P 3 + • • •, leads to estimates of tricrit-
ical compositions at x = 0.26 and 0.51, between which continuous (second
order) ferroelectric-paraelectric transitions are expected, the transitions 4 ' 5
corresponding to both ends, x = 0 and 1, of the phase diagram being clearly
discontinuous (first order). Interest in the ferroelectric properties of mixed
lead zirconate/titanate ceramics has been boosted recently by the prospects
of using PZT thin films in nonvolatile memories.6
The samples were thin disks (thickness ~ 1 mm, diameter ~ 1 cm) cut
from sintered and hot-pressed cylindrical samples with compositions x =
0.03, 0.06, 0.08, and 0.09, doped with 1 wt% N b 2 0 5 to improve the physical
properties of the ceramics. A high-temperature furnace built at the Crys-
tal Growth Laboratory of the UAM, Madrid, controlled by a Eurotherm
Temperature Controller/Programmer with high-resolution ramp (model
903P/IS/HDV), was used. The samples were thermally treated by keep-
ing them for several hours at temperatures of about 400° C before the
measurements, and the slow heating and cooling rates employed were of
the order of 20°C/h between room temperature and 400°C. The capaci-
tance and dissipation factor were measured during the heating and cooling
runs at regular intervals separated by about 0.1°C by means of an auto-
matic Hewlett-Packard Bridge Precision LCR Meter (model 4284A) with
an accuracy better than one part in 104 at a frequency of 1 kHz with a field
amplitude of 8.3 V/cm.
Figure 3.12.1 depicts the inverse dielectric constant e"x vs. temperature
for 0.03 < x < 0.09. The slope of e" 1 vs. T above the transition
 Ferroelectric-Paraelectric Transition in the Mixed System PbZr\^xTixOz 275

1
••'••• ' 1 i 1 r- — i —
}k>M \ ' ,»-o.f»!
j -" •
•
•
\ 1
i
•
I \ • 1
• 1
1
- j- I - •
-
J I : \ •
1
•

.
I . j
!
•

: 1 t
•

.
\ •
.
• I
I- \ / i
j
i •
• 1 < j- • -
j \ j 'j,
- 1 / - ; j • /-
1 \ / i 1 /
- - •
/ ! j • i / .
• \ I • / \ /
- •
J - j / •
' / -
• • V •
V
• - •
-- -• -
. . . L ,... 1 , 1, - i — 1 i ' .J •
' -~i
225 2S0 225 2S0 225 250 256 275
Tl-C! T(f) TCO ICC)

Fig. 3.12.1. Inverse dielectric constant e~x vs. temperature near the ferroelectric-
paraelectric transition for Pb(Zri_ x Tia;)03 doped with Nb ( l w t % N b 2 0 s ) for various
compositions in the range 0.03 < x < 0.09.

temperature T* is not equally well defined for all four compositions. This
leads, in some cases, to deviations from the ideal Curie-law behavior due to
differences in the compositional inhomogeneities, which causes uncertainties
in the Curie temperature Tc extrapolated at e _ 1 —> 0. In all cases the slope
was determined at an interval of about 20°C above T*, taking into account
numerically the derivative d e _ 1 / d T and avoiding the rounded region usu-
ally observed immediately above T*, which increases for increasing x.
Figure 3.12.2 shows dielectric loss data D = tan 5 vs. temperature for
the same samples. It may be noted that, for x = 0.03, no clearly defined
peaks are observed, but well-defined discontinuous jumps mark the phase
transition. The transition temperature T* for increasing T is therefore well
defined in every case by the dielectric loss data as well as by the dielectric
constant data.
Table 3.12.1 gives results for T*, T c , and AT = T* - Tc for PZT
compositions with 0.03 < x < 0.09 and lwt% Nb20s as well as 4 ' 5 for
P b Z r 0 3 (x = 0),PbTiO 3 (x = 1), and x = 0.22, for later use. It can be
seen that the trend of AT is decreasing with increasing x from x = 0.03 to
0.22, as an estimate of AT has been obtained from the difference between
^X-Dmax) for increasing and decreasing temperature.
These results can be analyzed by means of a generalized effective field
theory in which the standard expression for the effective field3 in terms of
276 Effective Field Approach to Phase Transitions

r — j — I — '•'" i— i — i —
»=0.03 n-0.06 j-O.OS \=0.0<>

0,10 \ - -- •- -
• •• •• •
• /

0.08 - •- - • •

' /'
• •
' 1 • • •

1
0.06 - -

i
•

;/ ;
*

i
t
0.04 - •y -
•

1\ '
•
V •

•
\ ; 1——' J \
0.02 • • •
V__: v_x
J * J~ ...... In, .....»_..-J__
225 250 22S 2SO 225 250 250 275
T(»C)
•rrc>
Fig. 3.12.2. Dielectric loss factor D vs. temperature for the same samples as in
Fig. 3.12.1.

Table 3.12.1. Transition temperatures and

Curie temperatures for P b ( Z r i _ : c T i : r ) 0 3 as a
function of x.

x Nb (%) T* (K) T c (K) A T (K)

0 * 503 460 43.0

0.03 1 502.2 486.9 15.3
0.06 1 505.5 496.5 9.0
0.08 1 517.4 510.0 7.4
0.09 1 531.7 524.8 6.9
0.22 * 571.7 [1.7]
1.00 * 763 720 43

* = negligible. A T estimated from loss peaks.

the polarization,
EeS = E + 0P, (1)
where (3 = 4TTTC/C is a dimensionless coefficient depending on the geometry
of the dipole lattice, is substituted by 7
EeS = E + (3P + 7 P 3 + L. (2)
With this substitution the equation of state relating P, E, and T,

tanh (3)
Nn kBT
 Ferroelectric-Paraelectric Transition in the Mixed System PbZri-xTix03 277

where N is the number of dipoles per unit volume, JJL the elementary dipole
moment, and KB Boltzmann's constant, leads directly to
/ P \'
TTTT— — \ 7^r \ t a n h
N/MJ
l + WMNny^—j L
(4)
here g = (•j/(3)(Nfj,)2 is a second dimensionless coefficient that plays a
decisive role in determining the character of the transition, g being 1/3 for
a tricritical point (TCP) transition.
For a pure system the Curie temperature is given by
pNfi2
Tc = (5)
KB

For a mixed system such as PZT, the composition-dependent Curie

temperature Tc(x) can be given in a first approximation 8 in terms of the
Curie temperatures of the components,

(Tc)z -= '-/c(O) (6)

KB

= TC{1) = PTNT^T
(TC)T - (7)
KB

PTNT^
Tc(x) ~-= Tc(0) ( ! - * ) + ( .PzNztfz

(8)

where the ratio

pTNTfi2T\ _TC(1)
2
JzNzfi zJ Tc(0)'
In our case, we will assume that this ratio is not too sensitive to small
amounts of doping, like 1 wt% N ^ O s .
Similarly, the dimensionless coefficient g, which determines the phase
transition character, and is given for a pure compound by
g = (1/(3)(Ntf (9)
can be given for a mixed system in terms of the coefficients g of the
components,
(g)z = 5(0) = hz/Pz)(Nzvz)2, (10)

G?)T = 5(1) = (1T/PT)(NTIJ-T)2, (11)

278 Effective Field Approach to Phase Transitions

as

9{x) = 9(0) [ ] +
\IZ/(3Z){NZ»Z

(1T/PT\ (NTHT\2 2
5(1) [ X) (12)
W / W \Nznz)
where the product of ratios

1T/PT £(1)
_lz/Pz_ .Nzuz. 5(0)'
and we again expect that this product is not affected substantially by small
amounts of doping with Nb.
As shown in previous work,9 within the framework of a generalized
effective field approach, the dimensionless quantities T*/Tc = 1 + AT/T C ,
g, and p* = P s (T*)/P s (0) are related among themselves by the relationships

3 tanh i„*p,
(l-fe*)2)"1 (13)
Ps

T * t a n h _ 1ip^ ;*
1 (Ps*)2- (14)

Numerical values for T*/Tc and g as a function of p* are given in

Table 3.12.2.
Figure 3.12.3 gives AT/TC as a function of g in an extended range
obtained by means of Eqs. (13) and (14). For g < 1/3, i.e., below the TCP
the transition is second order and no thermal hysteresis occurs under proper

Table 3.12.2. Numerical values for {T*/Tc)

and g as a function of p* = P s ( T * ) / P s ( 0 ) .

Ps (T'/Tc), Eq. (13) g, Eq. (14)

0 1 1/3
0.35 1.0036 0.3910
0.40 1.0066 0.4131
0.45 1.0114 0.4415
0.50 1.0191 0.4783
0.55 1.0314 0.5276
0.60 1.0508 0.5944
0.65 1.0803 0.6829
0.70 1.1387 0.8387
 Ferroelectric-Paraelectric Transition in the Mixed System PbZr\-xTixOz 279

0.10 •-J—T I I I I 1--1 • r-—• • J

0.W

0.06

0.04

0.02

0.00
0.00 0.20 0.40 0.W O.SO
g

Fig. 3.12.3. Plot of (AT/Tc), where A T = T* (transition temperature) - T c (Curie

temperature), vs. g = (7//3)(iV^) 2 (higher order effective field coefficient) after Eqs. (13)
and (14).

thermal equilibrium conditions. For g > 0.4, AT/T C increases fairly rapidly.
This relationship between AT/TC and g will be used later to calculate AT
for comparison with (AT%bs as a function of x.
To analyze our PZT results we begin by fitting Eq. (8) to the data in
Table 3.12.1 for 0.03 < x < 0.09. We get

Tc(x) = TC(0)[(1 - x) + Ax], A = 1.67, Tc(0) = 476.9K. (15)

This results in Tc(0) and T c (l) = Tc(0)A values that can be compared
with the Curie temperatures for the pure materials (no Nb) reported by
other authors. The ratio 4 - 5 (TC)T/(TC)Z ^ 1.56 is not far from A = 1.67 as
anticipated.
Next, we determine the relevant numerical parameters for Eq. (12). A
reasonable fit is obtained for

g(x) = s (0)[(l - xf + Bx2}, 5 = 1.46, g{0) = 0.534. (16)

Here, B and g(0) have been estimated from the set of numerical val-
ues of g(x) corresponding to 0.03 < x < 0.09, using the AT/T C values
given in Table 3.12.1 and the graph in Fig. 3.12.3. It may be noted that
g(l) = g{0)B = 0.779 so obtained is larger but not 7 far from (g)T = 0.62
at T = T*, independently determined for the pure titanate according to
280 Effective Field Approach to Phase Transitions

Table 3.12.1. On the other hand, g(0) = 0.534 is somewhat smaller than
(g)z = 0.72 at T = T* for the pure zirconate after Table 3.12.1. The possi-
bility that Nb doping slightly pushes some of the factors determining g for
the titanate and the zirconate in opposite directions is not to be expected,
a priori, but is not inconceivable.
Figure 3.12.4 shows the calculated curve for AT using Eq. (15) for Tc(x)
and Eq. (16) for g{x) and the functional relationship between AT/TC and
g plotted in Fig. 3.12.3, together with (AT) o b s for x = 0.03, 0.06, 0.08, and
0.09 (lwt% Nb20 5 doped), and for x = 0.22. A first tricritical point at
( £ T C P ) I = 0.26 is indicated by the calculated curve, and a second one at
( ^ T P T ) 2 — 0.51 (not shown in the graph) is also deduced from the same
equations for higher x values.
Thus, we may conclude that a mixed ferroelectric system like PZT can
accommodate more than one tricritical point in a wide enough range of com-
positions. Recent theoretical work10 on ferroelectric solid solutions suggests

16

14

12

10

1 •
4

o _i i i_

0.00 0.05 0.10 0.15 0.20 0.25 0.30

X

Fig. 3.12.4. AT = T* -T vs. x for P b ( Z r i _ a : T i a ; ) 0 3 . The curve is calculated from

Eqs. (15) and (16) using the plot of (AT/T C ) vs. g from Fig. 3.12.3, the solid circles are
experimental points for 0.03 < x < 0.09 (doped with 1 wt% Nb 2 Os) and 0 is for x = 0.22
(estimated from the shift in D m a x for heating and cooling runs). It is worth noticing that
the experimental point for x = 0.03 appears to be further from the theoretical value than
the rest. This may be due to the fact that Tc(x) has a slightly different behavior in the
low-x region 0 < x < 0.03 (Ref. 8).
 Ferroelectric-Paraelectric Transition in the Mixed System PbZr\^xTixOz 281

t h a t a detailed investigation of the lattice deformation through the tran-

sition may be useful to check the phase transition character of P Z T solid
solutions at x near the expected trictrical point compositions.

Acknowledgments

We would like to t h a n k Gen Shirane for many informative discussions on

structural aspects of this P Z T system, and Wolfram Wesing for providing us
the sample with x = 0.22. T h e financial support of I B E R D R O L A (through
Grant no. I N D E S / 9 4 ) and C I C y T (through Grant no. PB93-1253/94) is
gratefully acknowledged.

References

1. G. Shirane and K. Suzuki, J. Phys. Soc. Jpn. 7, 333 (1952).

2. E. Swaguchi, J. Phys. Soc. Jpn. 8, 615 (1953).
3. J.A. Gonzalo, Effective Field Approach to Ferroelectric Transitions and Some
Applications to Ferroelectrics (World Scientific, Singapore, 1991).
4. Z. Ujma and J. Handerek, Acta Phys. Pol. A 53, 665 (1978).
5. G.A. Samara, Ferroelectrics 2, 277 (1971).
6. S.L. Swartz and V.E. Wood, Condens. Matter News 1, 5 (1992); J.F. Scott,
J. Kammerdiner, M. Parris, S. Traynor, V. Ottenbacher, A. Shawabkeh and
W.F. Oliver, J. Appl. Phys. 64, 787 (1988).
7. G. Lifante, J.A. Gonzalo and W. Windsch, Ferroelectrics 146, 107 (1993).
8. B. Jaffe, W.R. Cook and H. Jaffe, Piezoelectric Ceramics (Academic,
New York, 1971), p. 136, Fig. 7.1.
9. J.A. Gonzalo, R. Ramirez, G. Lifante and M. Koralewski, Ferroelectrics Lett.
15, 9 (1993).
10. W. Windsch and H. Braeter, Acta Phys. Pol. 86, 393 (1994).
 Chapter 3.13

Observations of Two Ferroelectric

Response Times in TGSe at T < Tc*
J. Prezeslawski*, J.R. Fernandez del Castillo,
T. Iglesias and J.A. Gonzalo
Departamento de Fisica de Materiales, C-IV,
Universidad Autonoma de Madrid,
28049 Madrid, Spain
^Institute of Experimental Physics, University of Wroclaw, Poland

G. Shirane
Department of Physics, Brookhaven National Laboratory,
Upton, New York 11973, USA

Time-dependent dielectric constant measurements in ferroelectric

triglycine selenate reveal an existence of two characteristic response
times with distinct temperature dependences near T c . Possible reasons
connected with this behavior are considered.

Accurate time-dependent dielectric constant measurements have been per-

formed in good-quality single crystals of ferroelectric triglycine selenate
with the aim of investigating whether or not more t h a n one characteristic
time, possibly related t o the double correlation length observed in several
magnetic and structural transitions, can be observed. 1
Dielectric permittivity d a t a were collected by means of a H P Precision
L C R Meter 4384A connected to a computer (EQ = 1 V/cm, / m e a s = 1 kHz).
Samples were very slowly cooled t h r o u g h Tc, a n d t h e n kept for a long period
at constant t e m p e r a t u r e .

*Work previously published in Ferroelectrics 186, 329 (1996). Copyright © 1996.

Taylor & Francis Group.

283
284 Effective Field Approach to Phase Transitions

Figure 3.13.1 shows a typical plot of e * as a function of temperature

and indicates a pronounced change of e~l with time at the final fixed tem-
perature T = 22.307°C (AT = TC-T = 0.035°C).
Figure 3.13.2 presents Aei and temperature as a function of time for
data of Fig. 3.13.1.

Fig. 3.13.1. e " 1 vs. T for TGSe.

1E+5 ' I i ' i i l i ' i I ' i ' > I ' '

23

TfC)

1E+4 -i i i i i_ 22
15000 20000 25000 30000 35000
thlM(S)

Fig. 3.13.2. e and temperature vs. time for data of Fig. 3.13.1.
 Observations of Two Ferroelectric Response Times in TGSe 285

Figure 3.13.3 gives Aei = (e — £too) vs. time (same data as above) in
semilog scale from which a T\ is determined: Aei = Aeie~*/ T l , with the
result n ( A T = 0.035°C) = 14584s.
Figure 3.13.4 shows Aeo = (e — £i) vs. time (again the same data) in
semilog scale (after subtracting the previous contribution), from which a TQ

i i • i i i r | i i i j | i—n i | i i i M "

Ae1
\ T i =14684s
\ AT = 0.035 °C

1E+4 — \. _

-
^ ^^^"^

1 1 1 t I 1 1 1 i 1 i 1 1 1 i 1 1 \ I » I .i.i.fT'
12000 16000 20000 24000 28000
time(s)

Fig. 3.13.3. Aei = (e — £too) vs. time data as in Fig. 3.13.1.

•T-T'J'MI I T [ 1 1 I J \ IT 1 * | 1 1 1 1
1' *

Ae \
o
\ t„=2081s
~
\ AT=O.O35OC

1E+3 . \ _

a.-L.) i I i i 1 i l l i i.J L t x-j—I...I. )• r i 1 . i

12000 16000 20000 24000 28000
time (s)

Fig. 3.13.4. Aeo = (e - £i) vs. time data as in Fig. 3.13.1.

286 Effective Field Approach to Phase Transitions

is obtained through: Ae 0 = A e 0 i e - t / r 0 , resulting in r 0 (AT = 0.035°C) =

2081s.
Similar data for AT = 0.065, 0.18, and 0.31°C were collected and
analyzed.
Figure 3.13.5 displays graphically the data in Table 3.13.1. The data
indicate two distinct response times r^"1 ~ (AT)" 0 , where VQ « 0.5 ± 0.1
and Tj -1 ~ (AT)" 1 , where Vi « 1.0 ± 0.1, with different magnitudes and
temperature dependences. It may be noted that the estimated error bars
become considerable away from T c .
It is well known that noticeable changes of permittivity at a constant
temperature below Tc are related to the gradual tendency to attain the equi-
librium state of the domain structure. 2 This evolution of the domain struc-
ture has been described by a two-step mechanism. 3,4 The first step has been
observed as the shrinkage of small domains to the expense of larger domains
of opposite polarity. The second one consists of the decelerated formation of

1
" i "
1 V
r f „=c(AT) => "
v„«0.5 + 0.1
r , Jr'"<
H-" ,' i, »c (AI)V1

: A s v^l.O ± 0.1 •

,L
* *
,,l 1 ! > 1 1 1 1 1

1E-4 1E-3 A T / T c 1E-2

Fig. 3.13.5. Temperature dependence of two response times.

Table 3.13.1. Results for T, and TO at

various 0.035°C < A T < 0.31°C.

A T (°C) TO (s) TI (s)

0.035 2081 14584

0.065 1624 8577
0.18 1094 3811
0.31 1120 12665
 Observations of Two Ferroelectric Response Times in TGSe 287

At[s]
e
.
1500 X 100
- tOO kHz
# 500

1000
A
B * X
X
j ^
50 kHz D • 250 °
* x• . • 7400
>/^H, 25 kHz
0 17500
500
+ 32400
Xi» ^a A 44400
' i"^ i
I I ,
1000 2000 3000 4000

Fig. 3.13.6. Time evolution of Cole-Cole plots at a fixed temperature ( A T = 0.08° C).

a more and more periodic domain structure in the crystal. The rate of the
evolution process decreases at temperatures far below T c . In order to com-
pare our response times with time dependence of the reciprocal domain
width (density of domains), we have analyzed data reported for a TGS
crystal. 5 The comparison is, however, nondirect because of the differences
in the characteristics of the transition for TGS and TGSe. We have esti-
mated the two relaxation time values as about 1011 and 7530 s, respectively,
taking into account data collected at constant temperature 5 (AT = 0.4°C).
The time evolution of Cole-Cole plots can be observed also for TGSe
crystals at a fixed temperature below Tc. Our data (Fig. 3.13.6), which
were collected at AT = 0.08°C (E0 = 0.5V/cm), served for an evaluation
of relaxation time values of a dispersion strength Ae = (e s — e ^ ) . We have
obtained two values, 1613 and 9906 s. It may be noted that both values
would fit reasonably well with TO and TI in Table 3.13.1.
We think that this is the first attempt to investigate the possible exis-
tence of two scales in a characteristic parameter (time or length) at T « Tc
in an uniaxial ferroelectric. Triglycine selenate was choosen for investiga-
tions because its Tc is close to room temperature and because the rather
large specific heat anomaly 6 indicates a substantial contribution from fluc-
tuations near the transition temperature.

Acknowledgments

We acknowledge financial support from CICyT, Grant no. PB 93-1253, and

CAM, Grant no. AE 00138/94. One of us (J.P.) wishes to thank DGICyT
for financial support for a Sabbatical at UAM, SAB 94-0084.
288 Effective Field Approach to Phase Transitions

References

1. K. Hirota, G. Shirane, P.M. Gehring and C.F. Majkrzak, Phys. Rev. B49,
17, 11967 (1994).
2. J. Fousek, Czech. J. Phys, B15, 412 (1965); F. Gilletta, Phys. Stat. Sol. (a)
11, 721 (1972).
3. A. Jaskiewicz and W. Gruszczynska, Ferroelectrics 23 173 (1980).
4. N. Tomita, H. Orihara and Y. Ishibashi, J. Phys. Soc. Jpn. 58, 1190 (1989).
5. N. Nakatani, Jap. J. Appl. Phys. 24, L528 (1985).
6. K. Ema, K. Hamano, K. Kurihara and I. Hatta, J. Phys. Soc. Jpn. 43, 1954
(1977); K. Ema, J. Phys. Soc. Jpn. 52, 2798 (1983).
 Chapter 3.14

Equation of State for Pressure and

Temperature Induced Transition in
Ferroelectric Telluric Acid
Ammonium Phosphate*
Jose R. Fernandez del Castillo, Janusz Przeslawskr',
and Julio A. Gonzalo
Departamento de Fisica de Materiales, C-IV,
Universidad Autonoma de Madrid, 28049 Madrid, Spain

A careful experimental investigation of the ferroelectric-paraelectric

transition in uniaxial ferroelectric telluric acid ammonium phosphate
induced by pressure and by temperature in the vicinity of the phase
transition has been carried out. Dielectric constant and hysteresis loop
data allow the determination of the combined equation of state as a func-
tion of both temperature and pressure, relating accurately polarization,
field, pressure, and temperature in the neighborhood of the transition.

Solid-state pressure-induced phase transitions are similar to t e m p e r a t u r e

induced phase transitions in many respects. T h e analogy between the role
played by hydrostatic pressure in the former case and the role played by
thermal energy in t h e latter can be exploited to obtain a compact equation
of state describing simultaneously the pressure and t e m p e r a t u r e depen-
dence of the relevant pair of conjugated variables (polarization and electric
field in a ferroelectric). To make a proper quantitative investigation of the
equation of s t a t e in the vicinity of the transition, accurate d a t a , in terms
of the hydrostatic pressure as well as in terms of t e m p e r a t u r e , are needed.

*Work previously published in Phys. Rev. B: Rapid Commun. 53, R2903 (1996). Copy-
right © 1996. The American Physical Society.
tOn leave from the Institute of Experimental Physics, University of Wroclaw, 50-205
Wroclaw, Poland.

289
290 Effective Field Approach to Phase Transitions

Uniaxial ferroelectric telluric acid ammonium phosphate 1 8 (TAAP), chem-

ical formula |Te(OH) 6 | • |2NH 4 H 2 P0 4 | • |(NH 4 )2P0 4 |, is a good candidate
for investigation, because it has (for ambient pressure, 1 bar) a second order
phase transition 2 to the paraelectric state at Tc(0) sa 320K, conveniently
above room temperature, and also because it possesses a negative pres-
sure coefficient,4'5 dTc(p)/dp « 23.58°C/kbar, which allows investigation
of pressure-induced transitions at constant temperatures between room
temperature and 320 K. This crystal is monoclinic at room temperature
(Pn, Z = 2). At the ferroelectric transition the change in space group is
P2/n <-> Pn. The main feature of the atomic arrangement is the presence
of two distinct anionic groups: TeC-6 and P 0 4 . Two types of planes per-
pendicular to the [101] direction can be distinguished. In the first type, one
can find P 0 4 groups and NH 4 0„ polyhedra, while in the second one, one
has TeC>6 groups in addition to P 0 4 groupsand NH 4 0„ polyhedra. 6 Four
types of hydrogen bonds, N-H-O, linking P 0 4 tetrahedra are present. All of
them are asymmetric and the protons are ordered in the ferroelectric phase. 7
This ordering was confirmed also by the increase of Tc upon deuteration
and Raman studies, 8 which showed that the groups of Te06, P 0 4 , and NH 4
do not undergo changes that could trigger the phase transition.
In this work, we present and analyze high-resolution data (Ap ~ 1.5 bar
steps, in an interval of about 3kbar; A T sa 0.01°C steps, in intervals of
about 5°C) on the dielectric constant and hysteresis loops for TAAP single
crystals, undertaken with the aim of determining a combined pressure and
temperature equation of state.
The samples were small platelets, 3 x 2 x 1.2 mm 3 in size, cut from
a larger single crystal grown from water solution, coated with silver paste
electrodes deposited on the main surfaces. The sample holder, in which pres-
sure and temperature could be accurately controlled, as mentioned before,
was an adapted LC10 Unipress cell. Measurements of dielectric constant
and loss factor were performed with an HP Precission LCR Meter 4384A
{Emeas — 1 V/cm, / = 1kHz). Automatic data, together with tempera-
ture and pressure readings, were collected by means of a desk-top com-
puter. A Diamant-Drenck-Pepinsky bridge and a NICOLET 3 10 digital
oscilloscope were used to do the digitalized hysteresis loops measurements
(.Emeas = 1.8kV/cm, / = 50Hz). A computer program was used to correct
for internal bias in the hysteresis loops.
Figure 3.14.1 shows dielectric constant data as a function of pressure
through the transition at room temperature. The data can be fitted well
with a Curie-Weiss-type law with pressure.
 Equation of State for Transition in Ferroelectric TAAP 291

5 x 10- 4

4 x 10"
6.4
p (kbar)

Fig. 3.14.1. Inverse dielectric constant e - 1 as a function of hydrostatic pressure at T =

293 K for TAAP. Straight line indicates the Curie-Weiss behavior at p > pc = 5.13 kbar
(note that vertical scale starts at e _ 1 = 4 x 1 0 - 4 ) .

Figure 3.14.2 gives similar dielectric constant data as a function of tem-

perature through the transition at several pressures, which also follow well
a Curie-Weiss law. It may be noted that £ m a x becomes smaller for lower
transition temperatures.
Figures 3.14.3(a) and (b) displays normalized square spontaneous polar-
ization as a function of temperature (a) at ambient pressure (lbar), and
pressure (b) at constant temperature T = 306.65 K. It may be noted that,
because of the lack of perfect compensation in the hysteresis loops, Tc and
p c are slightly overestimated.
Two sets of hysteresis loop data, one at constant pressure (ambient pres-
sure, i.e., lbar) and another at constant temperature (T = 306.65K, i.e.,
near and below the ambient pressure Curie temperature) are represented
in Fig. 3.14.4 in scaled form. They fit well a combined equation of state,
discussed below, which is easily deduced from basic considerations. It must
be noted that we are not aware of previous descriptions of observed pres-
sure and temperature behavior near a ferroelectric transition by means of
a single equation of state.
In an order-disorder ferroelectric phase the existence of microscopic
dipole moments reversible under the action of an external electric field can
292 Effective Field Approach to Phase Transitions

5 x 1(T4-

s-1
6 x 10-4-

4x 1(T4-

2x 10" 4 -
1 - 5.68 5 - 3.60
2 - 5.07 6 - 3.45
3 - 4.32 7 - 2.57
4 - 4.13 8 - 1.31

| ' I I | I I I | I I I |

28 32 36 40 44
T(°C)

Fig. 3.14.2. Isobars of the temperature dependence of the inverse dielectric constant
e~l for TAAP.

be associated with the presence of a double potential minimum along the

polar axis of the unit cell for specific constituent ions. In the paraelectric,
i.e., fully disordered, phase the jump probability per unit cell and unit time
of those specific ions between the two symmetric minima is usually given
by 7r(0) = ve~^lkaT, where v « k^Qr^/h is the attempt frequency and <f>
the potential barrier height between the two minima. If the barrier height
is increased by a small amount d(fi, the jump probability should decrease in
such a way that
d7r0(^) = - ( l / ^ ) 7 r 0 d ^ (1)

and then
ir0(<t>) = 7r 0 (0)e" (2)
Here, <f>* can be given in terms of the critical barrier height at which
the ferroelectric-paraelectric transition, induced either by rising tempera-
ture or rising hydrostatic pressure, takes place. In a transition induced by
temperature only (i.e., under ambient pressure) we have 9
<J>eS(Tc,0)=(3Nfi2=kBTc, (3)

where Tc is the transition temperature and Eaoft = /3Nfi2 is the electrostatic

energy of the spontaneous field acting on the unit dipole fi. In a transition
 Equation of State for Transition in Ferroelectric TAAP 293

Fig. 3.14.3. Normalized spontaneous polarization square (Ps/Pso)2 vs. pressure at T =

306.65 K (a), and vs. temperature at ambient pressure ( l b a r ) (b). P s o = 2.12/iC/cm 2 is
the saturation spontaneous polarization.

induced by pressure only (at 0 K) also

4>es{0,Pc) = (3N/J2 = Avcpc (4)

where pc is the critical hydrostatic pressure and Au c the associated

change in unit cell volume, vc, needed to bring about the pressure-induced
transition.
294 Effective Field Approach to Phase Transitions

-
- O Pd = Pd < e ' a t const - ,em P- ( T = 306.65 K ) S
• pd = pd ( e ) at const, pressure (1 bar). yf
3 -

- PrJ = P d / 1
-(T/Tc+p/pc)|1/2 y S
2 -

Jf
1 —

-
^F
Jw
0 —
/I Pso= 2 1 2 (xC/cm2
_ /f £^=9.90 10 5V/cm
-1 — :
/ e = e/|l-(Tn" c +p/p c )| 3 / 2
_ I I | I I I I /I 1 I I | I I I I | I I I I I I I I I | I 1 I 1 | I I I I

-4 -2 0 2 A 4 6 8 10
Ine
Fig. 3.14.4. Simultaneous scaling equation of state for the pressure-induced and the
temperature-induced ferroelectric transition in TAAP. The continuous line is the theo-
retical scaling equation of state e = ± p a + \p\, with a — sign for T < Tc and p < pc, and
a + sign for T > Tc and p > pc. Tc (p = l b a r ) = 317.25K, p c (T = OK) = 76.87kbar;
Pso = 2.12/iC/cm the saturation spontaneous polarization, and Eao = 9.90 X 10 5 V/cm,
the saturation spontaneous field, give the best fit to the theoretical equation of state.

Consequently, in the general case of T < Tc, p < pc, we may take

0* = ^eff(T,p)=/3A r /i 2 (^ r + ^ (5)
.-'c Pc
This expression is used in the following to get in a straightforward man-
ner a combined pressure/temperature equation of state for the ferroelectric
transition.
In equilibrium under zero external field at the paraelectric phase, where
the double potential minimum is symmetric, the number of dipoles per unit
volume pointing in the positive direction (A/2) and in the negative direction
(A^i) are related by A ^ ^ i = N1T12, and since iri2 = 7T2i = TTO, one has
JVi = N2 = N/2. In general, however, i.e., under an effective field
EeS = E + f3Pd + 7 P d 3 + 6 P%, (6)

one has

7T2i=?ro(0)e-^+/3Fd+LW^,
(7)
7T12 = 7 r 0 ( 0 ) e ( £ + ^ + L ^ \
 Equation of State for Transition in Ferroelectric TAAP 295

which, in equilibrium (N2iT2i = Nynn) leads to

(N2 N { E + + L)
^ = t ^ ^ » (8)
Nfi (N2 + N1)li
and, using Eq. (5), to the combined equation of state
-1
'E + pPtV
(9)
pNfx ,

or
E T P_
tanh"1 ( A j3Pd PZ + PH4 + L
Tc Pc
(10)

which can be written in dimensionless form as

l
tanh pd - p d ( l + gj + hpAd + L) (11)
Tc pc
where p is the pressure and pd is the reduced dipolar polarization and must
not be confused. Tc = Tc(p = 0) is the transition temperature at p = 0,
and pc = pc(T = 0) is the transition pressure at T = 0 K.
For a continuous second order transition, 10 close to the ordinary critical
point (pd <C 1), Eq. (11) can be put in scaled form as

e = ±Pd + gPJL (12)

where

3/2'
1 - \TC + it)

Pd 1/2-
(13)
+
te £)
As shown in Fig. 3.14.4, Eqs. (12) and (13) describe simultaneously the
pressure-induced and the temperature-induced ferroelectric transition of
TAAP simply and fairly accurately. From pc and Tc we estimated the unit
cell volume change associated with the phase transition as Au c = k^Tjpc =
0.565 A (the actual unit cell volume is vc = 922.731 ).
Table 3.14.1 illustrates the good fit of data for Tc(p) and pc(T) from
Figs. 3.14.1 and 3.14.2 to Eq. (9), in which (T/Tc+p/pc) play the same
296 Effective Field Approach to Phase Transitions

Table 3.14.1. H = heating; C = cooling; D = decreasing of pressure.

Tc = Tc(j> = 0) = 317.25 K and pc = pc(T = 0) = 76.87kbar were used
for all data. Tc{p ^ 0) is the actual transition temperature for a specific
pressure p ^ 0; pc(T ^ 0) is likewise the actual transition pressure for a
specific temperature T ^ 0.

Tc(P) (K) p (kbar) Tc(p)/Tc (P/Pc) {[Tc(p)/Tc]+(P/Pc)}

H 299.56 5.688 0.944 0.074 1.018
C 299.56 5.688 0.944 0.074 1.018
H 302.00 5.071 0.951 0.066 1.017
C 30.90 5.071 0.951 0.066 1.017
H 304.36 4.452 0.959 0.058 1.017
C 304.22 4.327 0.958 0.056 1.015
H 304.61 4.452 0.960 0.058 1.018
C 304.30 4.452 0.959 0.058 1.017
H 305.58 4.074 0.963 0.053 1.016
C 305.42 4.137 0.962 0.054 1.016
H 307.28 3.601 0.968 0.047 1.015
C 307.14 3.601 0.968 0.047 1.015
H 308.12 3.394 0.971 0.044 1.015
C 307.94 3.452 0.970 0.045 1.015
H 310.98 2.556 0.980 0.033 1.013
C 310.83 2.578 0.979 0.033 1.013
H 315.35 1.310 0.994 0.017 1.011
C 315.30 1.315 0.993 0.017 1.010

T(K) Pc(T) (T/Tc) Pc(T)/Pc {(T/Tc)+\p(T)/Pc}}

D 293.15 5.13 0.924 0.067 0.991

role as T/Tc in a transition at zero pressure and as p/pc in a transition a t

zero t e m p e r a t u r e .

Acknowledgments

We acknowledge t h e financial s u p p o r t of C I C y T (Grant no. PB93-1253).

One of us (J.P.) t h a n k s D G I C y T for financial s u p p o r t for a sabbatical
(SAB94-0084) at t h e Ferroelectric Materials Laboratory, U A M .

References

1. R.F. Weinland and H. Prause, Z. Anorg. Chem. 28, 49 (1901).

2. S. Guillot Gauthier, J.C. Peuzin, M. Olivier and G. Rolland, Ferroelectrics
52, 293 (1984).
 Equation of State for Transition in Ferroelectric TAAP 297

3. R. Sobiestianskas, J. Grigas and Z. Czapla, Phase Transitions. 37, 157 (1992).

4. M.N. Shashikala, H.L. Bhat and P.S. Narayanan, J. Phys. Condens. Matter
2, 5403 (1990).
5. S. Haussiihl and Y.F. Nicolau, Z. Phys. B 6 1 , 85 (1985).
6. M.T. Averbuch-Pouchot and A. Durif, Ferroelectrics 52, 271 (1984).
7. J. Gaillard, J. Gloux, P. Gloux, B. Lamotte and G. Rins, Ferroelectrics 54,
81 (1984).
8. M.N. Shashikala, B. Raghunata Chary, H.L. Bhat and P.S. Narayanan,
J. Raman Spectrosc. 20, 351 (1989).
9. See, e.g., J.A. Gonzalo, Effective Field Approach to Phase Transitions and
Some Applications to Ferroelectrics (World Scientific, Singapore, 1991).
10. T. Iglesias, B. Noheda, B. Gallego, J.R. Fernandez del Castillo, G. Lifante
and J.A. Gonzalo, Europhys. Lett. 28, 91 (1994).
 Chapter 3.15

Neutron Diffraction Investigation of

the FRL-FKH Transition in Nb-Doped
PbZri-^Ti^Oa with x = 0.035*
Beatriz Noheda, Tomas Iglesias,
Noe Cereceda and Julio A. Gonzalo
Departamento de Fisica de Materiales,
Universidad Autonoma, 28049 Madrid, Spain

Hui-Ting Cien and Yong Ling Wang

Shanghai Institute of Ceramics, Chinese Academy of Sciences,
1295 Ding Xi Road, Shanghai 200050, China

David E. Cox and Gen Shirane

Department of Physics, Brookhaven National Laboratory,
Upton, NY 11973-5000, USA

Neutron powder diffraction data have been collected in order to char-

acterize the F R L - ^ R H transition of Nb-doped, Zr-rich PZT. Data for
the first few diffraction peaks were obtained in the temperature range
270 < T < 350 K in order to make a detailed characterization of
the .FRL-JRH transition, which takes place for this composition at
TUT = 323 K. The temperature dependence of the Pb and Zr/Ti(Nb)
atomic shifts, and the rotation and distortion of the oxygen octahedra
through the transition was derived. The results are compared with pub-
lished data for PZT with x = 0.10, and indicate that (a) the change
in Zr/Ti(Nb) shift through TLH becomes more pronounced, and (b) the
distortion and tilt of the oxygen octahedra below TLH become more
important for x = 0.035 than for x = 0.10. It has been concluded that
the increment in the variation of the spontaneous polarization through

*Work previously published in Ferroelectrics 184, 251 (1996). Copyright © 1996.

Taylor & Francis Group.

299
300 Effective Field Approach to Phase Transitions

TLH with increasing Zr amount is mainly caused by the increase of the

Zr/Ti(Nb) displacement in the low-temperature rhombohedral phase.

3.15.1. Introduction

Ferroelectric ceramics of PZT with high Zr contents show striking elec-

tromechanical and pyroelectric properties, 1 which make them useful for
technological applications. These ceramics are often doped with small
amounts of Nb to reduce aging effects, and to increase the resistivity and
the dielectric constant. 2 ' 3 The structural investigation of Nb-doped ceramic
samples may at first seem to be an added complication, but it should be
emphasized that the incorporation of Nb improves the homogeneity and the
mechanical properties of the ceramic material, and enhances the electrical
resistivity, facilitating the dielectric measurements through the transition
undertaken in parallel with the structural work.
The basic features of the phase diagram of PZT solid solutions were
established by Shirane et al.4 and Barnett. 6 Michel et al.7 subsequently
made an X-ray and neutron powder diffraction study in which they estab-
lished the space groups of the two rhombohedral phases of PZT, as R3c for
the FRL phase with x = 0.1 (two formula units per unit cell) and as R3m
for the FRH phase with x = 0.42. Later, Glazer et al.8 carried out further
structural work on PZT (x = 0.10) and characterized the FRL phase in
terms of the tilting of oxygen octahedra 9 and the accompanying expansion
or contraction of oxygen triangles.
In the present work, we have analyzed neutron powder diffraction data
on PbZri_a;Ti303 with x = 0.035. The aim of this work is to make a
more detailed characterization of the shifts in the atomic positions through
the transition and to compare them with the data of Glazer et al.8 for an
undoped sample with x = 0.10.

3.15.2. Experimental

The sample was a sintered and hot pressed cylinder of PZT doped with 1.5%
by weight of Nb 2 Os about 1cm in height and 1cm in diameter, having a
nominal composition Pb 1 _j / / 2 (Zri_ x Ti x )i_j / Nbj / 03 with x = 0.035 and y =
0.039, prepared at the Shanghai Institute of Ceramics. Constituent oxides
were ground, pressed into pellets, and fired at 1346°C for 2 h. The neutron
diffraction runs were carried out on one of the triple-axis diffractometers
 Neutron Diffraction Investigation in Nb-Doped PbZr\~-xTixOz 301

at Brookhaven National Laboratory, New York, at intervals of 10 K over

the temperature range 270-350 K. Data were collected for the four (F R H )
and five (FRL) lowest angle peaks at nine different temperatures in this
temperature region, which spans the F R L - F R H transition (T LH ). Since the
ceramic sample was large, and no special orientation is to be expected
for this cubic/pseudocubic material, few reflections should, in principle, be
sufficient to determine properly the changes in atomic positions, taking into
account that neutron data are relatively free from systematic errors. The
neutron energy was 14.7 meV. The transition temperature TLH — 323 K
was previously determined from dielectric constant and thermal expansion
measurements. 1 °

3.15.3. Results and Discussion

The behavior of the atomic shifts in the rhombohedral phases (aRL =

5.85 A, a R L = 59°42') and FRU (a R H = 4.07A,a R H = 89°39') for the first
four peaks, (100), (110), (111), and (200), together with the superstructure
(3/2,1/2,1/2) peak at T < TLH (pseudocubic notation) was determined
in the following way. The unit vectors of the F R L phase (i?3c), ai,a2,a3,
with lengths ar = \/2a, where a is the pseudocubic unit cell parameter, and
rhombohedral angle aRL = 59°42', were used throughout. The oxygen tri-
angles were allowed to tilt as a whole perpendicular to (111) for TTH, while
the tilt angle was set equal to zero for TLH- The values reported by Glazer8
were taken as initial values for the Pb shifts, s, the Zr/Ti (Nb) shifts, t,
the O3 tilts perpendicular to (111), e, and the O3 expansion/contraction
within the plane perpendicular to (111), d. In the FRH phase we had three
unknown parameters (s, t, d) and four peaks at each temperature. In the Fn
phase we had, on the other hand, four unknown parameters (s, t, e, d) and an
additional fifth peak, the superstructure peak (3/2,1/2,1/2), which is essen-
tially dependent only on and vanishes at TLH- The atomic positions at each
temperature were refined via an iterative manual procedure by minimizing
R = Yl I^obs — -fcail/ X^obs- The final R values were smaller than 1.5%.
The scattering lenghts used were 6A = 4.928 (6pb = 0.940, other
dopants: Ca, vacant), bB = 0.695 (bZr = 0.716, bTi = -0.330, 6 Nb = 0.705,
other dopants: Hf), be = 0.578 (60 = 0.580, vacant) all in 10~ 12 cm units.
Isotropical temperature factors were assumed at each temperature.
The rhombohedral fractional positional parameters used in the R3c
phase (FRX) are the same as those used by Megaw and Darlington. 11
302 Effective Field Approach to Phase Transitions

b s
O—fer-
4~i Q, • t
^
-©^"O-—©
a)

•a -• •"
§
i 0.000 •
0.016 • O -d
• e

'£ o.oio —
b)

©—e—o—Q—-e-
35^£)
o.ooo-

T(K)
Fig. 3.15.1. Fractional shifts s and t for P b and Zr/Ti (Nb) along to the rhombohe-
dral axis [111] (a) and oxygen octahedra tilt, e, and distortion, d (b), as a function
of temperature through the -FRL~' ? RH, transition for Pbzi_y/2('Z'fl-xrrix)i-yNby03
(x = 0.035,y = 0.039). Dashed lines are from data by Glazer et al.s for the composition
x = 0.10, with T L H = 353 K.

Figure 3.15.1(a) shows the fractional shifts s and t for Pb, Zr/Ti (Nb)
with respect to the length Ch = \fvia of the long rhombohedral body diag-
onal and Fig. 3.15.1(b) the tilt e = (tan w)/4\/3, where is the tilt angle
around [111], and the O3 triangle distortion (2d = ±<5(0)/a r ), for the nine
temperatures, six below TLH and three above TLH- These results show that
the Pb and Zr/Ti(Nb) atomic shifts along [111] decrease by about 18 and
44%, respectively, above the transition, which implies a substantial change
in spontaneous polarization, and a high pyroelectric coefficient around the
phase transition. The oxygen triangle tilt angle decreases fairly abruptly
from about 5° to zero at the same temperature, as expected.
Table 3.15.1 summarizes these results and compares the s, t, d, e, and
R values obtained with those given by Glazer et al.8 for a PZT sample with
higher Ti content {x = 0.10).
 Neutron Diffraction Investigation in Nb-Doped PbZr\-xTixOz 303

Table 3.15.1. Refined atomic positional parameters between 270 and 350 K for
Nb-doped P b Z r i - ^ T i x O s (z = 0.035) containing 1.5% N b 2 O s by weight.

F RL (iJ3c) FRH(R3m) Glazer8

T(K) 270 280 290 300 310 320 330 340 350 298
s 0.0318 0.0322 0.0312 0.0324 0.0325 0.0320 0.0266 0.0263 0.0258 0.0316
t 0.0151 0.0148 0.0132 0.0148 0.0148 0.0158 0.0080 0.0081 0.0084 0.0114
-d 0.0028 0.0027 0.0027 0.0027 0.0027 0.0028 0.0011 0.0011 0.0011 0.0029
e 0.0147 0.0147 0.0145 0.0141 0.0138 0.0121 0.0137

Our analysis of the temperature dependence of the intensities of a few

neutron powder diffraction peaks from Nb-doped PbZri_ a : Ti x 03 through
the -FRL^-FRH transition indicates that the shifts of the Pb, Zr/Ti(Nb) ions
and the tilt and distortion of the O3 triangles show small but significant
changes with respect to those previously reported by Glazer et al.8 for a
PZT sample with higher Ti content (x = 0.10). The Pb shift (s) is somewhat
higher in our case in the FRL phase due to the longer octahedron edge, as
was pointed out by Megaw et al.11 The oxygen octahedra tilt (e) is higher
in our case, and the Zr/Ti(Nb) shifts (t) are substantially higher, which is
not in agreement with strict packing considerations. 11 It may be concluded
that the increase in AP S through TL-H with Zr content 1 is mainly due to
the increase of the Zr/Ti shifts in the FRL-

Acknowledgments

We acknowledge partial financial support from IBERDROLA (INDES/94)

and CICyT through grant PB93-1253. Work at Brookhaven is supported
by the US Department of Energy, Division of Materials Sciences, under
contract DE-ACO2-76CH00016.

References

1. M. Bernard, R. Briot and G. Grange, J. Solid State Chem. 31, 369 (1980).
2. R. Gerson and H. Jaffe, J. Phys. Chem. Solids 24, 979 (1963).
3. R. Gerson, J. Appl. Phys. 31, 188 (1960).
4. G. Shirane, K. Suzuki and A. Takeda, J. Phys. Soc. Jpn. 7, 12 (1952);
E. Sawaguchi, J. Phys. Soc. Jpn. 8, 615 (1953).
5. G. Shirane and A. Takeda, J. Phys. Soc. Jpn. 1, 5 (1952).
6. H. Barnett, J. Appl. Phys. 33, 1606 (1962).
304 Effective Field Approach to Phase Transitions

7. C. Michel, J.M. Moreau, G.D. Achenbach, R. Gerson and W.J. James, Solid
State Comm. 7, 865 (1969).
8. A.M. Glazer, S.A. Mabud and R. Clarke, Acta Cryst. B34, 1060 (1978).
9. A.M. Glazer, Acta Cryst. B 2 8 , 3384 (1972).
10. B. Noheda, T. Iglesias, G. Lifante, J.A. Gonzalo, J. de Frutos, H.T. Chen,
Y.L. Wang and G. Shirane, Electroceramics IV (Aachen Sept. 5-7, 1994).
11. H. Megaw and C.N.W. Darlington, Acta Cryst. A 3 1 , 161 (1975).
 Chapter 3.16

0 3 Tilt and Pb/(Zr/Ti) Displacement

Order Parameters in Zr-Rich
P b Z r i ^ T i ^ O s from 20 to 500 K*
Noe Cereceda, Beatriz Noheda, Tomas Iglesias,
Jose R. Fernandez-del-Castillo and Julio A. Gonzalo
Universidad Autonoma de Madrid, 28049 Madrid, Spain

Ning Duan and Yong Ling Wang

Shanghai Institute of Ceramics, Chinese Academy of Sciences,
1295 Ding Xi Road, Shanghai 200050, China

David E. Cox and Gen Shirane

Department of Physics, Brookhaven National Laboratory,
Upton, New York 11973-5000

Neutron diffraction and dielectric data have been collected from a poly-
crystalline sample of PbZri-xTi^Os (a; = 0.035) to determine the
temperature dependence of the two-order parameters associated with
the oxygen octahedral tilt and the Pb/(Zr/Ti) displacement, respec-
tively, through the sequence of phase transitions FRL-FRH-PC present
in this mixed system. The weak coupling between tilt and polarization
(displacements) is satisfactorily described within the framework of a
two-order-parameters statistical theory in which the respective effec-
tive fields involve two higher order terms in addition to a linear
term.

•Work previously published in Phys. Rev. B 55, 9 (1997). Copyright © 1997. The
American Physical Society.

305
306 Effective Field Approach to Phase Transitions

3.16.1. Introduction

Perovskite structures, which are cubic at high temperatures, frequently dis-

play a rich variety of phase transitions at lower temperatures 1 that usually
involve cation shifts and/or oxygen octahedra tilts, with respect to the
high-symmetry phase. These shifts and tilts are basically independent, in
the sense that one can appear in the absence of the other, but they can
couple weakly to each other. The mixed perovskite system PbZri-^Ti^Os
(generally denoted PZT) is especially interesting, 2 not only because it can
be prepared over the entire compositional range (0 < x < 1), with a variety
of distorted structures at room temperature, e.g., tetragonal {FT), zero-
tilt rhombohedral high-temperature (.FRH), nonzero-tilt rhombohedral low-
temperature (JFRL), and antiferroelectric orthorhombic {AFo) phases, but
also because 3 of its important technological applications.
The basic features of the phase diagram of PZT solid solutions were
established by Shirane et al.2 Barnett 4 pointed out the existence of an
additional low-temperature phase change for Zr-rich compositions, later
characterized as the F R L - ^ R H transition. Michel et al.5 determined the
space groups of the two rhombohedral phases as R3c (FRL) and R3m (FRR)
by means of X-ray and neutron powder diffraction at room temperature
using two compositions, x = 0.10 (-FRX, w ith two formula units per unit cell,
involving oxygen octahedra tilts) and x = 0.42 (-FRH, with one formula unit
per unit cell and zero tilt). In summary, the sequence of phase transitions in
Zr-rich PZT is FRL (rhombohedral R3c) —> FRH (rhombohedral R3m) —>
Pc (cubic). Later, Glazer et al.6 made a further neutron powder study on
PZT with x = 0.10, characterizing the FRL phase in terms of the tilting
of oxygen octahedra 7 and the expansion or contraction of the octahedra
triangles neighboring the shifted B cation (Zr/Ti).
Glazer7 has also made a general classification of tilted octahedra in per-
ovskites. He pointed out that the cation displacements, which are directly
related to the ferroelectric character of the perovskites, have only a small
effect on the lattice parameters and that, generally, the overall symmetries
follow those of the tilts.
Research has been done to describe the possible relations between the
atomic displacements in these materials. Megaw and Darlington 8 described
the perovskite structures in terms of four structural parameters, classifying
them by their space groups to allow comparisons. They found no correla-
tion between the cation displacements and the octahedra tilts in the space
groups R3c and R3m, to which rhombohedral PZT belongs. A study of such
 Oz Tilt and Pb/(Zr/Ti) Displacement Order Parameters 307

a correlation, if it exists, is important to determine which parameters are

the cause of the deformations and which parameters are only consequences.
Nevertheless, even if displacement and tilt are independent, they may be
coupled, mainly because of the shared-corner linkage between octahedra,
which is required by the packing.
We have recently reported some preliminary neutron diffraction
measurements 9 on a ceramic sample of PZT with x = 0.035 over a limited
temperature region around the phase transition between the two ferroelec-
tric rhombohedral phases, FRL and FRH, which occurs at a temperature
TLH ~ 323 K. This work allowed a detailed description of the structural
parameters that characterize the transition, namely the cation displace-
ments along the [111] axis, s (Pb) and t (Zr, Ti), the distortion of the
oxygen octahedra d, and a parameter e, which describes the rotation of the
oxygen octahedra around the [111] axis with a tilt angle, w, in the (111)
plane such that tan UJ = \/3e. 6 We have also reported some measurements
on the dielectric response of Zr-rich PZT (Ref. 10) in the temperature
region around the rhombohedral-cubic phase transition, -FRH--PC> which
occurs at « 5 1 0 K and is shown to be first order.
The weak coupling between tilt and displacements has been recently
studied by Dai et al.11 in PZT (x = 0.35) by means of dielectric constant,
hysteresis loops, and dilatometric and electron diffraction techniques. They
proposed that the inability of the oxygen octahedra to rotate coherently
within a rigid lattice generates random internal stresses, which constrain
the polarization. They found doubled hysteresis loops for this composition,
which appear to be relaxed with La and Nb doping.
To analyze in depth the coupling between tilt and displacements, it is
very convenient to use neutron diffraction data, especially to measure the
tilt angle, which is difficult to determine by other techniques. In the present
work, we investigate the temperature dependence of the two-order param-
eters associated with the octahedral tilting and the cation displacements
over a wide temperature range spanning both the -FRL--FRH and -FRH-PC
transitions, with special emphasis on the weak coupling between polar-
ization, directly associated with the cation shifts, and tilt in a Nb-doped
PbZri-^TirOs ceramic sample with x = 0.035. Nb doping is important,
among other things, to reduce the electrical conductivity and to facilitate
dielectric constant and polarization measurements.
The squared structure factor of the first superstructure peak, 1/2(311),
which can be expressed as
| F | 2 = 8[sin2(47re)[l + cos(247rd)] « 16 sin2(47re)
308 Effective Field Approach to Phase Transitions

is, in practice, directly proportional to the squared rotation parameter

e 2 . This allows us to define the temperature dependence of the tilt order
parameter as

Vs(T) = [IRLCTV/RUO)] 1 / 2 ,

where /RL is the integrated intensity of the superstructure 1/2(311) Bragg

reflection. We have accurately measured J]S(T) between 20 and 375K by
neutron diffraction.
Dielectric constant data, which show a small anomaly at TLH, and
pyroelectric charge measurements through TLH were used to character-
ize the small decrease in spontaneous polarization that accompanies the
•FRL~-FRH transition. Measurements of hysteresis loops, which were previ-
ously used to characterize the behavior of the polarization order parameter
Ps(T) = Ps(T)/Ps(0) at the T R H ^ P C (ferroelectric-paraelectric) transition,
were attempted at T < TLH, but were unsuccessful because of the high
values of the coercive field for the sample in this temperature range.
The combined neutron diffraction and dielectric data were used for a
theoretical analysis of the weak tilt-polarization coupling. Prior work by
Halemane et aL 12 ' 13 made use of Landau's theory to describe the simul-
taneous temperature dependence of tilt and polarization in PZT with a
different composition, x = 0.10, but no detailed information on the tem-
perature dependence of the tilt order parameter was available at this time.
We describe below an analysis of our data for PZT with x = 0.035 by means
of a simple two-order-parameters statistical theory, in which the effective
fields14 for both tilt and polarization involve linear, cubic, and fifth power
terms in the conjugate variable. In spite of its simplicity, this theoreti-
cal approach produces a simple relationship between tilt and polarization,
which is borne out quantitatively by the experimental data.

3.16.2. Experiment

The samples were high-quality polycrystalline ceramics prepared

at the Shanghai Institute of Ceramics, with nominal composition
Pbi_ 3/ /2(Zri_ a: Ti a ;)i_ 3/ Nbj / 03, with x = 0.035 and y = 0.039, confirmed
by chemical analysis. The constituent oxides were ground, pressed into pel-
lets, and fired at 1350°C for 2 h. Cylinders of about 1 cm in height and
1 cm in diameter were sintered and hot pressed for the neutron diffraction
runs, and thin plates of about 1 mm in thickness and 1 cm in diameter were
used for the dielectric measurements. Data were collected with neutrons
 O3 Tilt and Pb/(Zr/Ti) Displacement Order Parameters 309

of 14.7 meV energy for several low-angle peaks, including the superstruc-
ture peak 1/2(311) (Ref. 9) at one of the triple-axis diffractometers at the
Brookhaven National Laboratory HFBR between 20K and TLH — 323 K.
The dielectric constant data, capacitance and dissipation factor, were mea-
sured at regular intervals of about 0.1 K by means of an automatic Hewlett-
Packard Precision LCR Meter (Model 4284A) with a field amplitude of
8.3 V/cm to an accuracy better than one part in 104 at a frequency of 1 kHz.
The rate of temperature change was ~ 20 K/h for both heating and cooling
runs. The pyroelectric charge released through the FRL — -FRH transition was
measured with a Keithley Electrometer (Model 610C), and measurements of
hysteresis loops data were made with a modified Diamant-Pepinsky-Drenck
circuit with a Nicolet Digital Scope (Model NIC-310). The temperature for
the electrical measurements was measured in all cases by a chromel-alumel
thermocouple with a Keithley Digital Multimeter (Model 196).

3.16.3. Results

Figure 3.16.1 depicts the tilt order parameter rjs{T) obtained directly from
the neutron diffraction data. It can be seen that rjs(T) decreases gradually
1
1 ' 1 ' i ' i ' 1 ' 1 • 1 '

—•—
" * — • -
r
~~---<L

- ^ \

•
T T
LH

•
I 1 l 1 . 1 :___L u___J , 1 ii 1 i
0 50 100 150 ZOO 250 300 350 400
T(K)

Fig. 3.16.1. Tilt order parameter vs. temperature obtained from neutron diffraction
measurements on a ceramic sample of Nb-doped P b Z r i - ^ T i ^ O s with x = 0.035. The
tilt order parameter is denned as rja(T) = [ / R L ( T ' ) / 7 R L ( 0 ) ] 1 / 2 , where 7R.L corresponds
to the integrated intensity of the first superstructure peak (hkl) = 1/2(311) of the
rhombohedral unit cell. Dashed line indicates calculated metastable region between low-
temperature and high-temperature phases. The theoretical curves (full and dashed lines)
are calculated from Eq. (7) with x = 0.
310 Effective Field Approach to Phase Transitions

with increasing temperature, reaches a value of 7? S (T L H) = 0.59, and then

drops fairly abruptly to nearly zero for T > T L H — 323 K. As shown below,
a good fit of the data for rjs(T) between 20 K < T < T LH is obtained with an
extrapolated Curie temperature T ct = 178.2 K, much lower than the tran-
sition temperature TLH, and indicative of the pronounced first order char-
acter of the transition. The fit is done by varying the tilt saturation value,
7ys(0) = 7?so, and the effective Curie temperature, T ct , from estimated ini-
tial values to optimize the agreement between available experimental data
and the equation of state arrived at in Section 3.16.4. It may be noted
that, in our case, T?S(0) « rjs (20 K) is well defined beforehand, while T ct <
TLH = 323 K (transition temperature) is not, because it is inaccessible
experimentally. In Section 3.16.5, the fitting process is described in more
detail.
Figure 3.16.2(a) shows the inverse dielectric constant as a function of
temperature over a wide range, from slightly below TLH = 323 K to well
above Tpp = 509.6 K, the ferroelectric-paraelectric transition temperature.
In this case, the extrapolated Curie temperature, Tc = 489.9 K, is relatively
close to the transition temperature. A small anomaly in e _ 1 (T) at T >=
TLH marks the onset of the tilting of the oxygen octahedra.
Figure 3.16.2(b) presents the behavior of the spontaneous polarization
(displacement order parameter) Ps as a function of temperature over the
same wide range as in Fig. 3.16.2(a). Data of the hysteresis loops for
T > TLH in the region of Tpp are combined with pyroelectric charge mea-
surements made around TLH- They indicate, as expected, a small change
in spontaneous polarization at the onset of the tilting transition. It may be
noted that the numerical values for Tc and Tpp are not identical to those in
Fig. 3.16.2(a) but appear slightly shifted toward lower temperatures. This
may be due to the fact that in the measurements of the hysteresis loops,
extra heating of the sample under the relatively high driving field is known
to take place. The thermocouple, which is not in good thermal contact
with the sample, may register a temperature closer to that within the fur-
nace than that of the sample. The data, read automatically from the digital
scope, include extra polarization just above the true transition temperature.
As is well known, at first order discontinuous transitions in ferroelectric
perovskites, the single hysteresis loops evolve toward double loops, which,
when imperfectly compensated due to the high conductivity of the sample,
may give rise to tails in the apparent spontaneous polarization above the
transition temperature, whose precise value may become blurred. It should
be pointed out that the estimated ratio between the true (single crystal)
 O3 Tilt and Pb/(Zr/Ti) Displacement Order Parameters 311

3.0x1 0 3

2.5X10"3

2.0x1cr3

~„ 1.5X10'3

1.0x10J

5.0x10"*

0.0
35

30

25

• f *>

10

0
250 300 350 400 450 500 550 600
T(K)

Fig. 3.16.2. (a) Inverse dielectric constant vs. temperature (heating and cooling) for Nb-
doped P b Z r i _ a ; T i x 0 3 (x = 0.035) showing the - F R L - ^ R H transition associated with the
O3 tilt and the Fjm-Pc transition to the cubic paraelectric phase, (b) Spontaneous polar-
ization vs. temperature for Nb-doped P b Z r i - ^ T i x O s (x = 0.035). Since hysteresis loops
data show an increasingly large coercive field as T decreases and approaches T L H , making
measurements near this temperature impossible, pyroelectric charge measurements were
made. It may be noted that in ceramic rhombohedral perovskites the saturation polar-
ization is substantially lower than in single crystals, the ratio being P s (s.c.) RS 1.15 x Ps
(ceramic) (see text). Dashed line indicates calculated metastable region. The theoretical
curves (full and dashed lines) are calculated from Eq. (4) with e = 0.

polarization and the apparent (ceramic) polarization is about 1.15,15 which

has been used to correct the data shown in Fig. 3.16.2(b).

3.16.4. Theoretical Analysis

To analyze the phase transition sequence

^RL(?? S > 0;p s > 0; Aps > 0) -* FRB{r)s = 0;p s > 0; Ap s = 0)

-* Pcds =ps = Ap s = 0)
312 Effective Field Approach to Phase Transitions

we first examine separately the polarization order parameter (ps) and

the tilt order parameter (r]s) using a common order-disorder statistical
approach, and then we investigate the weak coupling between both order
parameters, which gives rise to the increase in the polarization order param-
eter (Aps) apparent at T < T LH [see Fig. 3.16.2(b)].

3.16.4.1. Polarization
If there are N interacting elementary dipoles per unit volume in the solid, of
which N2 are pointing one way and Ni in the opposite way, (Ni+N2) = N,
in thermal equilibrium we have

N2(kBeD/h)e-^/kBTe~E^^kBT = N1(kBeu/h)e-^kBTe-E^lx/kBT,
(1)
where (/cB©D/^)e * d / fcBT is the jump probability per unit time per unit
dipole, n, for an effective field Ees = 0, and fa is the height of the energy
barrier between the two potential minima corresponding to the two possible
orientations (Eeg = 0). The net dipolar polarization (practically identical
to the total polarization, P) would then be

Pd = (N2 -N1)n = Nn tanh(£ eff /Vfc B T), (2)

where fi, as before, is the elementary dipole moment per unit cell.
The effective field may be expanded in powers of the polarization, taking
into account that, for an external field E — 0, Eeg(P(\) = —Eeg(—Pd).
Thus,

EeS = E + pPd+1P$ + 5Pi + ---, (3)

where /3, 7, and 5 are constant (i.e., temperature independent) coefficients.

Using the dimensionless variables, e = E/(3N(j,, p = Pd/N/j, = P/Nn,
and substituting T c = (3Nfj?/kB, 9 = (-y/p)N2fi2, h = ( 7 / / ? ) i V V , we
obtain the equation of state

e = (T/Tc) t a n l T 1 p - p(l + gp2 + hp4 + L), (4)

which specifies completely the temperature dependence of the spontaneous

(e = 0) order parameter p(0) = pB. (This dimensionless field e should not
be confused, obviously, with the structural parameter e, which describes
the O3 rotation.)
 O3 Tilt and Pb/(Zr/Ti) Displacement Order Parameters 313

The temperature dependence of the inverse dielectric constant can

also be obtained easily from the equation of state, Eq. (4), as e _ 1 (T) —
(T c /C)(de/dp).

3.16.4.2. Tilt
Similarly, we can try to describe the temperature dependence of the tilt
order parameter in the FRL ferroelectric-antiferrodistortive phase, in which
the unit cell is doubled, using a statistical approach as follows. If there
are N' interactive unit cells per unit volume, consisting of N[ with the
two oxygen octahedra within the unit cell tilted in the sequence (+u>, —ui),
and A^j with the two oxygen octahedra tilted in the opposite sequence
(—IV,+UJ), the net "staggered" tilt per unit volume 6t of the pseudocubic
three-dimensional arrangement of cells is

0t = {N'2 - N[)2\LO\ = N'2\u\ tanh(|X eff \2\co\/kBT), (5)

where

\xeS\ = x + f3'et + 1'e3t+6'e5t (6)

is the generalized (torsional) field and |w| is the absolute value of the rota-
tion angle of a single oxygen octahedron in the unit cell (the other oxygen
octahedron within the unit cell will have, automatically, a rotation angle
with the same value in the opposite direction). Because the FRL phase
presents an antiferrodistortive deformation with respect to the higher tem-
perature rhombohedral phase, FRH, Xeg is an effective staggered field (tor-
sional field in our case), conjugate with the staggered tilt strain.
The equation of state in dimensionless variables is

tanh
x= ( — ) ~ l y - r t 1 + 9tV2 + htr?4 + L), (7)

where x = X/(5'N'2\u)\; r\ = #t/7V'2|a;|, which can also be interpreted

as {e(T))/(e(0K)}, due to the fact that e = tanw/4V3 « co/4,^3;
T ct = P'N'(2\Lo\)2/kB, gt = ( 7 '//?')(2H) 2 and ht = (5'/p')N'i(2\uj\)i.
Here, T ct < TLH is the effective Curie temperature for the transition involv-
ing O3 tilting, which is different from Tc < Tpp, the Curie temperature for
the ferroparaelectric transition involving Pb and Zr/Ti displacement or
order-disorder orientations.
The spontaneous (x = 0) tilt order parameter 77(0) = TJS = e s /e s o is
therefore given by Eq. (7) with x = 0. Note that e can be interpreted, in
314 Effective Field Approach to Phase Transitions

general, as a common tilt for all unit cells (displacive transition) at any given
temperature, or as an average tilt (e) for a statistical distribution of the tilts
through the lattice (order-disorder transition). Very often, transitions have
a mixed displacive/order-disorder character that should, to some extent,
be taken into account by a generalized effective field that includes terms
with higher order powers, as in Eq. (6).

3.16.4.3. Polarization-Tilt Coupling

Let us assume that there is a weak coupling between tilt and polarization,
or, in other words, that a unit cell tilted in one specific direction favors
atomic displacements in one of the two opposite directions perpendicular
to the plane of the tilt. In this case, the total interaction energy to be
substituted into Eq. (2) is Wa + Wt = Ees + Xeff2uj, instead of W^ = Eefffi
only, and we therefore have

wd wt] tanh \ w« 1 + tanh

&}-.
ps + Aps = tanh kBT (8)
kBT kBT tanh
1 + t a nh £T] [&
Taking into account that for E = 0, tanh[Wd/fcBT'] ps and
tanh[Wt/fcB?1 = rjs, we obtain directly from Eq. (8)

Ap s = ( l + p s 7 ? s ) - 1 ( l - P s ) ' 7 s , (9)

which relates the increase in polarization to the tilt in a very simple way.
The prefactor (1 + PsVs)^1 varies smoothly from 0.5 at T = OK to 1.0 at
T = TLH- The second factor (1 — pi) is zero at T = OK and is still much
less than unity at T = T L H if TLH is substantially lower than TFP as in the
present case.
Figure 3.16.3 shows the temperature dependence of the spontaneous
polarization and the tilt, in excellent agreement with the observed behavior.

3.16.5. Discussion and Conclusions

As mentioned above, the temperature dependence of the tilt order param-

eter, rjs(T), and the polarization order parameter, ps{T), are well described
by Eqs. (7) and (4) with x = 0 and e = 0, respectively. In Figs. 3.16.1,
3.16.2(b), and 3.16.3, which display Eqs. (7) and (4), full line indicates
equilibrium states (heating) and dashed line corresponds to ideal metastable
 O3 Tilt and Pb/(Zr/Ti) Displacement Order Parameters 315

T(K)
Fig. 3.16.3. Calculated temperature dependence of the tilt and polarization order
parameters for P Z T (x = 0.035) indicating that the extra polarization associated with
the tilt Aps is well described, below TLH by Ps = (1 +PsVs)~1 (1 — Ps )*?s, Eq. (9). See text
for details on the fitting procedure for TJS(T) and ps(T). Dashed lines indicate the cal-
culated metastable region between low-temperature and high-temperature phases. The
dotted line for ps(T) below TLH is the calculated polarization in the absence of tilt.

behavior (cooling). The fitting procedure was the following: the experimen-
tal values for Vs(T) = [/ RL (T)// RL (0)] 1 /2 and Ps(T) = P s (T)/P s (0), with
initial values for 7RL(0), Tct and P s (0), Tc chosen as discussed below, were
substituted, respectively, into

t_ (^)tanh-17b(r)/»h(T)-l
St 9t + htVs (10)

r_ (^)tanh-1Ps(T)/ps(T)-l
•9 + hpi (11)
P2s(T)
Here, the experimental values for g't, defined by the actual value of the
tilt at a given temperature, are plotted vs. r]2, using as normalized param-
eters / R L ( 0 ) and T ct . If Eqs. (7) and (4) describe correctly the observed
behavior, g[ vs. rj% and g' vs. p2 should result in linear plots, giving auto-
matically (<?t, ht) and (g, h). The quality of these least-square-fitted linear
plots was assessed through Rt = \Ag't/gt\2 and Rt = \Ag'/g\2, respectively,
summing up over all data points, where | A ^ | and \Ag'\ are the differences
316 Effective Field Approach to Phase Transitions

between experimental and calculated values. The values of I R L ( O K ) , T ct

needed to obtain rjs(T) and T/Tct, and Ps0,Tc to get PS(T) and T/Tc in
Eqs. (10) and (11), are not known experimentally, so the fitting procedure
is carried out by changing them to get the best linear fit. The initial values
are chosen from the experimental data knowing that J R L ( O K ) « I R L ( 2 0 K ) ,
T ct < T LH = 323K, P s 0 > Ps (430K), and Tc < TFP = 501.0K.
Then, varying T ct and / R L ( 0 ) [fixed in practice because the neutron
data include points for 7 R L ( 2 0 K ) KS TRL(OK) with very small statistical
error], we proceed to minimize the least-square error of the fit to get a final
Tct [see Fig. 3.16.4(a)]. Likewise, experimental values for g', defined by the
actual value of the spontaneous polarization at a given temperature, are
plotted vs. Pg, using as normalized parameters initial estimates for Pso and
Tc. Varying again (within narrow limits) Tc and Pso and optimizing the
linear fit, we get final values for Ps0 and Tc [see Fig. 3.16.4(b)].
This procedure leads to R < 10" 4 for I R L ( 2 0 K ) / I R L ( 0 K ) = 0.985
and T ct = 178.2 K with estimated uncertainties of the order of 1%, and
to R < 10" 4 for P s 0 = 33.0/uC/cm 2 , Tc = 480.0K (with estimated
uncertainties of the order of 5%). These fits resulted in linear plots giv-
ing gt = 5.1 ± 0.1, ht = —5.8 ± 0.2 for the tilt order parameter, and
g = 0.62 ± 0.25, h = —(O.^IJ;^) for the polarization order parameter.
It should be noted that the set of experimental data for TJS(T) covered the
range 0.06 < T / T L H < 1-00; while the available set for ps(T) covered only

• g' from experimental data of p,(T). £q,(11)

-4- • g't from experimental date o( .],(T) Eq.(10]
2
0.4- — l i n e a r ft g-= 0 * 3 - 0.15p,J
— - linear lit: g',= 5.1 - S.8 n,
-8-
0.3 1 . 1 1 1 1 1 r 1 r
0.0 0.2 0.4 0.6 0.8 1.0 0.2 0.3 0.4 0.5 0.6 0.7 0.
1,
P.'

Fig. 3.16.4. (a) Plot of (gQexp = /t[T/T ct ?7 s 2 ], where Tct and / R L ( 0 ) are adjusted by a
least-squares fit to get the best linear dependence of g[ vs. r£. IRL(T) are the actual mea-
sured values of temperature and integrated intensity. It may be noted that [/RL(0)] '
comes out very close to [i R L (20i<:)] 1 / 2 . (b) Plot of (g() ex p = f(T/Tc,p2s = Ps/Pso) vs.
p 2 , where T c and Pso are similarly adjusted. In this case P s o is still somewhat larger than
P s (T ~ 450 K), which is the maximum value actually measured. Points corresponding
to T > Tpp (transition temperature) have been omitted.
 O3 Tilt and Pb/(Zr/Ti) Displacement Order Parameters 317

0.85 < T/Tpp < 1.00. This is the main reason for the larger uncertainties
in the latter.
The occurrence of nonvanishing values gt > 1/3, ht < 0, and g > 1/3,
h < 0 in the expressions for 7ys(T) and ps(T) implies a first order (dis-
continuous) character for the transitions, in agreement with the observed
behavior. Physical meaning can be attributed to the effective field coeffi-
cients /3 t , 7t(st), St(ht) and /?, 7(5), 5(h) in Eqs. (6) and (3), considering
the effective field expressions as multipolar expansions. These expansions
include successive dipole-like (long range), quadrupole-like (short range),
octupole-like (shorter range) terms, summing up the contributions over the
whole lattice. However, detailed calculations of this kind in rhombohedral
perovskites are nontrivial.
The temperature dependence of the weak peak in e(T) at T « TLH
can be described only in a semiquantitative manner within the theoreti-
cal approach used here to describe ps(T) at the TRL~TRH transition. The
presently available information on the trend of AJ> S (TLH) with composition
(x) for x = 0.035,9a; = 0.10,6 and x — 0.40 (Ref. 16) indicates a tendency
to smooth out the discontinuity with increasing x. This behavior might also
be masked by the increasing compositional inhomogeneity of the samples.
It would be interesting to be able to predict theoretically the composition
dependence of T L H ( ^ ) and A P S ( T L H ( ^ ) ) in terms of gt(x) and ht(x), but
this is not possible at present.
In summary, the temperature dependence of the tilt order parameter of
PZT with x = 0.035, previously investigated in a narrow range near TLH, 9
has been determined by means of neutron diffraction in the whole temper-
ature range from T = 20 K to TLH = 323 K. The associated polarization
change PS{T) a t T « TLH has been determined.
It may be concluded that the simple two-order-parameters statistical
theory outlined in Section 3.16.4 accounts well for the coupling between
tilt and polarization determined by neutron diffraction and dielectric mea-
surements, especially in view of the fact that the data were obtained not
from single crystals, but from ceramic samples.

Acknowledgments

Financial support from CICyT (Grant no. PB93-1253/94), Iberdrola (Grant

no. INDES 94/95), and Comunidad de Madrid (Grant no. AE00138-94) is
gratefully acknowledged. Work at Brookhaven is supported by the U.S.
318 Effective Field Approach to Phase Transitions

D e p a r t m e n t of Energy, Division of Materials Sciences, under Contract no.

DE-AC02-76CH00016.

References

1. See, for instance, Ferroelectric and Related Substances: Oxides, Landolt-

Bornstein, New Series, Group 3, Vol. 16, Pt. a (Springer-Verlag, Berlin, 1981).
2. G. Shirane, K. Suzuki and A. Takeda. J. Phys. Soc. Jpn. 7, 12 (1952).
3. J.C. Burfoot and G.W. Taylor, Polar Dielectrics and their Applications
(Macmillan, London, 1979).
4. H. Barnett, J. Appl. Phys. 33, 1606 (1962).
5. C. Michel, J.M. Moreau, G.D. Achenbach, R. Gerson and W.J. James, Solid
State Commun. 7, 865 (1969).
6. A.M. Glazer, S.A. Mabud and R. Clarke, Acta Crystallogr. 5 34, 1060 (1978).
7. A.M. Glazer, Acta Crystallogr. B 28, 3384 (1972).
8. H.D. Megaw and C.N.W. Darlington, Acta Crystallogr. A 3 1 , 161 (1975).
9. B. Noheda, T. Iglesias, N. Cereceda, J.A. Gonzalo, H.T. Chen, Y.L. Wang,
D.E. Cox and G. Shirane, Ferroelectrics 184, 251 (1996).
10. B. Noheda, N. Cereceda, T. Iglesias, G. Lifante, J.A. Gonzalo, H.T. Chen
and Y.L. Wang, Phys Rev. B 5 1 , 16 388 (1995).
11. X. Dai, J.-F. Lie and D. Viehland, J. Appl. Phys. 77, 3354 (1995).
12. T.R. Halemane, M.J. Haun, L.E. Cross and R.E. Newnham, Ferroelectrics
62, 149 (1985).
13. T.R. Halemane, M.J. Haun, L.E. Cross and R.E. Newnham, Ferroelectrics
70, 153 (1986).
14. J.A. Gonzalo, Effective Field Approach to Phase Transitions and Some Appli-
cations to Ferroelectrics (World Scientific, Singapore, 1991).
15. D. Berlincourt and H.A. Krueger, J. Appl. Phys. 30, 1804 (1959).
16. A. Amin, R.E. Newnham, L.E. Cross and D.E. Cox, J. Solid State Chem.
37, 248 (1971).
 Chapter 3.17

Dielectric C h a r a c t e r i z a t i o n of t h e
P h a s e Transitions in
Pb 1 _ 2 / / 2 (Zr 1 _ i E Ti a ; ) 1 _ y Nb 2 / 03 (0.03 <
x < 0.04,0.025 < y < 0.05)*

Ning Duan, Noe Cereceda, Beatriz Noheda

and Julio A. Gonzalo
Departamento de Fisica de Materiales, C -IV,
Universidad Autonoma de Madrid, 28049 Madrid, Spain

The Curie temperature and the ideal thermal hysteresis of P b 1 _ v / 2 -

(Zri_ a; Ti a: )i_j / Nbj / 03 (0.03 <y< 0.05) ferroelectric ceramics have been
investigated as a function of composition at the FB,H~PC phase tran-
sition. Experimental results are analyzed using the generalized effec-
tive field approach and taking into account the composition dependence
of the dimensionless parameters g and h corresponding to the second
and third terms in the generalized effective field expansion. With this
approach we can describe reasonably well the composition dependence
of Tc(x,y) at the F R H - P C transition and thermal hysteresis AT(x,y) in
the narrow range of compositions investigated. The effects of the oxygen
octahedra tilt in the dielectric constant at the F R L - F R H transition have
also been investigated as a function of composition.

3.17.1. Introduction

Solid solutions of lead zirconate t i t a n a t e P b ( Z r i _ x T i x ) 0 3 (denoted P Z T )

are ferroelectric ceramic materials with perovskite structure which have
important practical applications in high-e capacitors, infrared pyroelectric

*Work previously published in J. Appl. Phys. 82, (2) (1997). Copyright © 1997.
American Institute of Physics.

319
320 Effective Field Approach to Phase Transitions

detectors, piezoelectric devices, and ferroelectric memories, using their out-

standing ferroelectric, piezoelectric, and pyroelectric properties.
Early studies were focused on the morphotropic phase boundary
(MPB), where the piezoelectric electromechanical coupling factor is very
high and shows anomalous behavior. In recent years, efforts have been
devoted to the Zr-rich PZT range of compositions, due to the abundant
phase boundaries between phases, including orthorhombic antiferroelectric
(A0), high-temperature rhombohedral ferroelectric ( F R H ) , low-temperature
rhombohedral ferroelectric (JPRL), and paraelectric (Pc) phases. 1-4 In par-
ticular, the rhombohedral ferroelectric region has attracted considerable
interest. The -FRL-^RH phase transition was first discovered by Barnett in
1962.5 The structures of the FRH and FRL phases were later reported by
Glazer and Mabud. 6 In these phases one finds rotations and distortions
of the oxygen octahedron (FRL phase) and only distortions (FRH phase),
respectively, in addition to the cation shifts. Later, several studies in the
FRL and the FRH structures were performed.7~9 These results indicated
that the increase of the spontaneous polarization near the F R L - F R H phase
transition is related to the O3 tilt coupling to cation shifts along the (111)
axis, and depends on the composition (Ti content) and the dopant con-
tent. Along with the structural research, other physical properties at the
FRL-FRH phase transition have also been investigated. 10 It was found that
the F R L - F R H transition has the following features: (a) the transition tem-
perature is close to room temperature; (b) there are small variations in
dielectric constant through the transformation; (c) there is a considerable
pyroelectric effect during the transition (AP « 2 fiC/cm , the pyroelec-
tric coefficient being ~ 1 0 - 7 / i C / c m 2 °C, higher than the usual value, which
is around 10~& fiC/cm2 °C). Applications based on the above outstand-
ing properties of the F R L - F R H phase transition are, for example, direct
energy conversion from heat to electricity through the FRL-.FRH phase
transition 11 ' 12 and its use in infrared detectors. Recently, Zr-rich PZT
thin films with F R L - F R H phase transitions have been reported to possess
prospective potentialities in the fields of IR detectors, energy converters,
and uncooled imaging systems. 13
On the other hand, the use of different dopants allows the enhancement
of specific properties and therefore results in wider applications. In the
case of Nb doping, for instance, substitution of a small amount of Nb 5 +
for Zr 4 + (or Ti 4 + ) increases the bulk resistivity and reduces aging effects,
because of the difference in chemical valence between N b 5 + and Zr 4 + , which
creates a considerable amount of lead vacancies. 14-17 The phase diagram of
 Dielectric Characterization of the Phase Transitions 321

Nb-doped Zr-rich PZT has been precisely measured. 18 " 20 The results show
that small amounts of Nb dopant shift the ferro-para phase boundary down,
and displace the F R L - F R H phase boundary to the left.
In this investigation, the composition dependence of the -FR.L_-PC and
FRL-FRK transition temperatures and the thermal hysteresis that accom-
panies the transitions have been investigated in a set of compositions with
x in the range of (0.03, 0.04) and y in the range of (0.02, 0.05). The results
have been analyzed in terms of the generalized effective theory used pre-
viously to study the composition dependence of T(x) for samples with a
fixed small amount of Nb (y = 0.026). It may be noted that an impor-
tant motivation for this work was to investigate the changes in the transi-
tion temperature of Zr-rich PZT with varying content of Ti and Nb, since
the latter substantially enhances the resistivity of the material, which has
important consequences in connection with its use as an energy converter of
thermal into electrical energy. A larger internal resistance results in larger
power output being obtainable. The range of Nb content has been chosen
to get FRL^-PRH transitions in a narrow range not much higher than room
temperature.

3.17.2. Experiment

The samples were prepared by the conventional ceramic process in Shanghai

Institute of Ceramics, China. They were calcined at 850° C for 2h and sin-
tered at 1340°C for 2h, then polished into thin disks (thickness of 1mm,
diameter of 1.49 cm) for later use. Dielectric constant data, capacitance,
and dissipation factor, were measured at regular temperature intervals sep-
arated by about 0.1°C, the temperature being controlled by an Eurotherm
Temperature Controller/Programmer with a high-resolution ramp (Model
903P/IS/HDV) by means of an automatic Hewlett-Packard Precision LCR
Meter (Model 4248A) with an accuracy of better than one part in 10°
at a frequency of 1kHz. The field amplitude was 8.0V/cm. The heating
and cooling rates were of the order of 20°C/h, between room temperature
and 300°C.

3.17.3. Results and Discussion

Figure 3.17.1 shows the behavior of the inverse dielectric constant with tem-
perature for different compositions around the FRL — Pc transition. From
322 Effective Field Approach to Phase Transitions

(100-x)/x/y
O 97.0/3.0/2.6
• 97.0/3.0/3.9
A 97.0/3.0/5.0

o.o- T
8.0-
O 96.5/3.5/2.6
D 96.5/3.5/3.9
6. 96.5/3.5/5.0
f

O 96.0/4.0/2.6
D 96.0/4.0/3.9
A 96.0/4.0/5.0

200 240 320 I ' l O

Fig. 3.17.1. Dielectric behavior vs. temperature for various P b i _ y / 2 ( ^ i - x T ^ i x ) i - y -

NbyC>3 compositions with 0.03 < 0.04 and 0.02 < 0.05 for the F R H - P c phase transition.

these data the ferroparaelectric phase transition temperature, T*, and the
Curie temperature, T c , can be obtained directly. The temperature at which
e _ 1 begins to decrease nonlinearly upon heating is denned as T*. The slope
of e~l vs. T above T* was fitted in a narrow temperature range near T*.
The Curie temperature, T c , is subsequently obtained extrapolating linearly
£ _ 1 (T) —> 0. It can be seen that Tc and T* decrease with the increase of
Nb content, y. The experimental results for T*, T c , and AT = T* - Tc,
corresponding to different niobium contents, are presented in Table 3.17.1
along with the dependence on Ti content. This notation for the extrapolated
Curie-Weiss temperature (Tc) and the transition temperature (T* > T c ) is
the same as that used in our previously published work 21 but differs from
that used by other authors, which is To and T c , respectively, for the Curie
temperature and the transition temperature.
 Dielectric Characterization of the Phase Transitions 323

Table 3.17.1. Experimental data for T*, T c , AT (all in K) for different P b ! _ a / 2 -

( Z r 1 _ x T i x ) 1 _ H N b „ 0 3 (0.03 < x < 0.04,0.026 < y < 0.05) compositions.

(100 - x)/x y (mol%)

2.6 3.9 5.0

T* Tc AT T* Tc AT T* Tc AT

97/3 503.5 489.9 13.6 487.8 473.3 14.5 478.1 458.7 19.4
96.5/3.5 501.7 491.2 10.5 489.3 475.1 14.2 484.8 470.1 14.7
96/4 502.8 493.9 8.9 494.5 478.4 16.1 492.5 479.7 12.8

We may note that there is some diffuse character in the transition peaks,
increasing with the Nb content, which may be attributable to small inhomo-
geneities in composition. 22-24 However, measurements at different frequen-
cies below 1 MHz show that the peak temperature is not seriously affected
by the change in frequency, which may be taken as an indication that the dif-
fuse character is not very pronounced in our samples. It allows us to deter-
mine the transition and Curie temperatures within a moderate error range.
Estimated asymmetric error bars, which vary from composition to compo-
sition and are larger when the Nb content is large, are given in the figures.
Figure 3.17.2 shows the dielectric constant and losses factor for the
-FRL-^RH transition. The temperature corresponding to the dielectric con-
stant and the losses factor peak value is well defined as the low-high
transition temperature, TLH, but the corresponding -FRL-JFRH "Curie tem-
perature," TCT, associated with a hypothetic Curie-Weiss behavior at
T > TLH J cannot be obtained directly from our data. Taking into account
that TLH increases with the increase of Nb and Ti content, TCT could be
expected to increase with increasing Nb and Ti content, but this point needs
further study.
The behaviors described in Fig. 3.17.1 and Table 3.17.1 can be analyzed
in the framework of the generalized effective field theory, 25 using an effective
field

Eeff = E + (3P + 7 P 3 + 5P5L, (1)

where E is the external field, P the polarization, and /?, 7, 5 are constants,
i.e., temperature-independent coefficients.
With the substitution of the dimensionless variables e = E//3Nfi,
normalized field; p = P/Nfi, normalized polarization; Tc = BNfi2/he;
2 2 4
g = (S//3)N fi ; and h = (<5//3)iVV > where N is the dipoles number per
324 Effective Field Approach to Phase Transitions

* W.,5/3.5/i • 9K!/i
750
« W..5/3.V3«> ' or-mo j
<• • K . J . * 5/2 6 ^ » 97:5/2.6 /

t-.M).

y /
/
550

X> /

J^
450

VK1-
20 40 W) 8ft 100 12(1 20 40 <>0 SO UKI U0 20 40 c.O Ml UK) 120

<• % M / S
" W4/3'» %.5/3.V3.9
0.04
* %/4/2.ii 96.5/3 5/>fc

H A^ H
0.02 T \\V
^*&®
11.01-

iKKl-
20 40 (.0 SO 100 120 20 40 (.0 80 100 120 20 40 00 SO 100 120
T(C) T(Q T(C)

Fig. 3.17.2. Dielectric behavior and losses factor vs. temperature for the same compo-
sition as in Fig. 3.17.1 at the •FR.L _ ^ ? RH phase transition.

unit volume, fx the dipole moment per unit cell, andfeethe Boltzmann
constant, we get the following equation of state for a pure system:

e = — tanh lp - p(l + gp2 + hp4 H ). (2)

-t c

For e = 0, p = ps (spontaneous polarization), the above equation is

rewritten as
l+gpj + hp4
1 (3)
Tc tanh ps/ps
If we consider a mixed system, like Nb-doped PZT, g and h become
composition dependent, as we will discuss below. Thus, Eq. (3) can be used
to describe the composition dependence of the FRH~-PC phase transition
temperature.

3.17.3.1. Composition Dependence of the FRU-PC

Phase Transition
We have pointed out, just before Eq. (2), that Tc for a ferroelectric com-
pound has a linear dependence on the number of dipoles per unit volume,
 Dielectric Characterization of the Phase Transitions 325

N. So, for a mixed system, a linear dependence of Tc on the molar content,

x or y, of the components can be supposed, if we consider the parameters
involved, {&} and {/J-i}, to be approximately constant in relatively narrow
ranges of x and y. The compositions that we have investigated in this work
are so close to each other that this constancy can be reasonably assumed.
Tc is, then, expressed by means of linear relationships in x and y. As a first
approximation, 21

Tc(x,y) =Tc(0,y)[{l-x) + Axx], y = constant, (4)

Tc(x,y)=Tc(x,y)[(l-y) + Ayy], x = constant, (5)

where x and y are fixed values of x and y, respectively. The coefficient Ax is

given by Ax = T c (l, 0)/T c (0,0) = .j3TNT^l'(3ZNZH2Z where the subscripts
T and Z correspond to pure PbTiC>2 and PbZrC>3, respectively. In such a
way we are sure to obtain the Tc of the pure compounds in the extremes of
the phase diagram (x = 0,1). No such simple relation can be written for Ay,
due to the reasons commented upon below. However, Ay can be understood
as a fitting parameter analogous to Ax. In Fig. 3.17.3(a), the experimental
values of Tc(x,y) vs. x are represented by different symbols along with
the linear least-squared fits, plotted as full lines. It may be noted that the
slopes are very similar for y = 0.026 and y = 0.039, which indicates that the
coefficient Ax is almost composition independent for y < 0.04. Table 3.17.2
gives numerical values for Ax extracted from the experimental data fits.
For Ay we cannot confidently use Eq. (5) in the whole composition range
(i.e., 0 < y < 1) because it is known that PbNb2C>6 has the tungsten-bronze
structure, which is quite different from the perovskite structure. Above the
transition temperature, its paraelectric phase is not cubic but tetragonal.
This means that Eq. (5) has no meaning in the high Nb range. However,
we may expect that small Nb constants (< 4mol%, in our case) do not
substantially change the perovskite structure, and, consequently, that we
can use Eq. (5) to describe the dependence of Tc(x, y) vs. y in the low Nb
constant range. The numerical values for Ay obtained by fitting the exper-
imental data are also given in Table 3.17.2, where we find this coefficient
is not too composition dependent for y < 0.04. The experimental data for
Tc(x, y) vs. y and their linear least-squares fits are plotted in Fig. 3.17.3(b)
by means of different symbols and full lines, respectively.
If we take into consideration the effects of x and y, simultaneously, on Tc,
the general expression for Tc(x,y) is given, combining Eqs. (4) and (5), by

Tc(x, y) = T c (0,0) • [(1 - x) + Axx][(1 - y) + Ayy}. (6)

326 Effective Field Approach to Phase Transitions

(a)
500 1 i ' "• i *-

. - • • ' • >

• ^0.026
• ,= 0.039
460 - • • • • • • ' ! ' " " " " ' * y=0.050 •

i Tc(x,y)=Tc(0,y)!(1-x)+AJ<x]

0.035 0.040

(b)

Tc(x,y)=Tc{x,0)[(1-y)+Ayy]

h-
• x= 0.030
• x= 0.035
460
* x= 0.040

0.02

Fig. 3.17.3. Plot of the Curie temperature Tc vs. x (a) and y (b). The full lines are best
fits to Eqs. (4) and (5), which are combined into Eq. (6). Points with different symbols
are experimental data.

Table 3.17.2. The calculated values for Ax and Ay in

Tc(x,y)=Tc(0,0)x [(l-x) + Ax[(l-y) + Ayy].

x (mol %) y (mol %)

3.0 1.84 2.6 -3.27

3.5 2.12 3.9 -3.36
4.0 4.78 5.0 -3.44
 Dielectric Characterization of the Phase Transitions 327

We may conclude that Eq. (6) describes fairly well the x and y depen-
dence of the Curie temperature for Nb-doped Zr-rich PZT.
On the other hand, we have defined, just before Eq. (2), the dimension-
less parameter g(x,y), which determines the more or less pronounced first
order character of the transition, 26 and is dependent on N2, the squared
number of dipoles per unit volume. Then, in an analogous way to that for
Tc(x,y), we get

g(x,y) = g(0,y)[(l-x)2+Bxx2}, y = constant, (7)

2 2
g(x,y) = g{x,0)[{l-y) + Byy ], x = constant, (8)

and
g(x, y) = 5 (0,0) [(1 - xf + Bxx2] [(1 - yf + Bvy2}. (9)

Note that x and y are small in all of our cases, so the higher order terms
involving xy, x2y, xy2, and x2y2 in the expansion of Eq. (9) are considerably
smaller than the terms in x and y, unless the coefficients Bx and By are
unexpectedly large. Neglecting terms of order higher than second order in
x and/or y we get

g(x, y) 9* 5 (0,0) [l - 2(x + y) + 4xy + (Bx + l)x 2 + (By + l)y2}, (10)

which indicates that, as a first approximation, g(x,y), unlike Tc(x,y),

should show a linear dependence on (x+y) in the range of our investigation.
Similarly, for parameter h, we have

h(x, y) = M0,0) [(1 - x) 4 + Cxx4} [(1 - yf + Cyy4}, (11)

2 2
h(x, y) =* h(0,0) [1 - 4(x + y) + 16xy + 6(x + y )], (12)

which indicates that, as a first approximation, h(x, y) should show a linear

dependence on (x + y) for x, y <g; 1.
We have used a set of data 2 1 in a more extended range of (0.03 < x <
0.09) at fixed y = 0.056 to get 5 (0,0) = 0.59, h(0,Q) = -0.12, Bx = 1.04,
and By = —1.70 for a reasonable fit to our present set of data. The result-
ing values have estimated errors of at least 20%. The values for (7(0,0)
and /i(0,0) are fully consistent with those obtained from hysteresis loops
data. 27 We should make it clear that the different procedures used in pre-
vious works, 21 ' 27 ' 28 to determine the dimensionless coefficients g and h,
give consistently relatively well-defined values for g but lead to consider-
able uncertainties for h, and do not rule out the possibility that higher
order coefficients are needed. These higher order coefficients might result
 Effective Field Approach to Phase Transitions

0.00 0,05 0-10 0 15 0.20

Fig. 3.17.4. Calculated composition dependence of the normalized spontaneous polar-

ization, p* = P*/Pso, at the -FRH^-PC phase transition temperature: (a) p* vs. x for
several y values; (b) p* vs. y for several x values. Dashed lines are indicative because the
y value is beyond our expected range of approximation.

in higher AT/TC at loss x values, where our theoretical curves depart most
from the data.
Substituting Eqs. (10) and (12) into Eq. (3) at the FRH to P Q transi-
tion temperature (T*) we get the relationship between (x,y) and p*, plot-
ted in Fig. 3.17.4(a) and (b). Also, we can get numerically the calculated
(x, y) dependence of AT/TC, which is plotted in Fig. 3.17.5(a) and (b). Full
lines correspond to 5(0,0) = 0.59 and /i(0.0) = -0.12, Bx = 1.04, and
By = -1.70 for y = 0.026, 0.039, 0.050 and x = 0, 0.05, 0.10, respectively.
Also plotted are our experimental data and additional experimental data
from Ref. 21.

3.17.3.2. Comments on the FRL--FRH Phase Transition

As we have mentioned before a small amount of Nb content can change
significantly the -FRL--FRH transition behavior and other characteristic
 Dielectric Characterization of the Phase Transitions 329

(a) "T~
D y= 0 026
O y= 0.039
A y= 0 050
• ref pi](y=C0?6:
calculated.

t °,C

(b) i < >

0.05- —y- D x= 0.030

! O >.-- 0.035
A x- 0.040
0 04-
I iJ • let [21]
calculated

0 03- Vt<?
x~0
0 02- „ / x=0.0f>
^ \ / x=0 1C
0.01-
*^v
•-'</-
0 00- —,—.— -, r-^f—^i—^. — I —
025

Fig. 3.17.5. Plot of AT/Tc vs. (x, y) from Eqs. (3), (10), and (12) for different composi-
tions (lines) together with the experimental d a t a and those from Ref. 21: (a) AT/TC vs.
x for different y values; (b) AT/TC vs. y for different x values. Dashed lines are indicative
because the y value is beyond our expected range of approximation.

properties such as the dielectric constant, the spontaneous polarization

jump (AP S ), and the phase transition order. It is known that the sponta-
neous polarization discontinuity at the -FRL--FRH phase transition for 95/5
type PZT ferroelectric ceramics arises due to the cation (Pb and Zr/Ti/Nb
ions) shifts along the (111) direction, because of the coupling effect between
oxygen's octahedra tilt (T?S), and the spontaneous polarization (P s ). The
spontaneous polarization discontinuity can be affected by the Ti and Nb
content. What we are interested in is how the composition, x and y, affects
the APS, and the transition temperature.
330 Effective Field Approach to Phase Transitions

Based on the generalized effective field approach, the spontaneous polar-

ization change can be shown to be a function of ps (normalized spontaneous
polarization) and rjs (normalized spontaneous tilt angle) as follows27:

Ap s = ( l + p s 7 7 s ) - 1 ( l - p s 2 ) ? ? s . (13)

In this equation, ps and rjs are related to temperature through 28

T_ = 1+gpl + hpj

Tc tanh_1ps/ps

and

J^_ = l+gtr£ + htVit (15)

TCT t a n h - 1 T]s/r]s
respectively.
In principle, T c , T C T, g, h, gt, and ht could be given in terms of the
composition, x and y, in a similar way to that discussed above for the
FRH-PC transition. So, Eq. (13) could, in theory, describe the composition
dependence of the spontaneous polarization discontinuity. We lack, how-
ever, enough experimental information to get it numerically. Sufficiently
detailed measurements of AP S for different compositions have not yet been
performed. This is left for further study. At present we have only dielectric
constant data, shown in Fig. 3.17.2, for different compositions. From them
we can see that increasing Ti or Nb content increases, as is well known,
the temperature at which the anomaly of the dielectric constant corre-
sponding to the F R L - ^ R H transition appears. An increase in the diffuse
character with the increase of Nb content can also be seen. In Fig. 3.17.6,
the FR.L_-FRH transition temperatures are plotted versus (x + y), with x
being the Ti content and y the Nb content, for the compositions investi-
gated in this work. The experimental data from Ref. 21, which correspond
toy = 0.026, and the phase boundary line for pure PZT 2 9 (y = 0) have also
been included. It can be seen that the F R L ^ ^ R H phase boundary is almost
unaffected by the substitution of Nb(y) instead of Ti(cc), for small amounts
of y (< 5mol%). This dependence supports the idea 20 that the Nb 5 + ions
substitute Zr 4 + ions and that they are not located at interstitial positions. 19
This is also consistent with the observed 27 weak coupling between O3 tilt
(responsible for the -FRL-JFRH transition) and the polarization.
 Dielectric Characterization of the Phase Transitions 331

ouu — I 1
I ' I ' 1 1 •
p
c y (% mol)
• 2.6
A 3.9
£ 200- \ • 5.0

I \ o 2.6 (ref.21)
mperat i

0 (ref.29) -
\
F
\ RH ^0
01 100- J ^ J

i- \

y
V

-
F
RL
0- 1
I 1 1 '
4 8 12
x+y (%mol)

Fig. 3.17.6. The effects of Nb contents on the F R L _ - F R H phase transition temperature

TLH- Different symbols correspond to different Nb contents and coincide with Jaffe's data
without Nb content (full lines). This means that the F R L - F R H transition temperature
for small Nb content (in our case < 5 mol%) is well defined by the curve corresponding
to pure PZT.

3.17.4. Summary

In summary, in the range of small amount of Ti(z) and Nb(y) content, the
Curie temperature of the Nb-doped PZT system can be described fairly
well within the framework of an effective field approach for a combination
of Ti and Nb content in the range x < 1, y < 1. The thermal hystere-
sis at the F R R - P C transition can be described by means of higher order
coefficients (g,h,...), determinant of the phase transition character. The
experimental errors in the determination of AT are considerable due to the
diffuse character of the transition.
The behavior of the dielectric constant as a function of Ti(x) and Nb(y)
at the F R L - F R H transition has been characterized experimentally in the
narrow range 0.03 < x < 0.04, 0.026 < y < 0.05, and the data indicate that
the anomaly at T L H becomes smoother and shifts toward higher tempera-
ture as the Nb content increases. The amount of shift in the phase boundary
332 Effective Field Approach to Phase Transitions

due to Nb doping (y) is equivalent to t h a t due to Ti(x) substitution, a fact

t h a t is related t o t h e secondary role of cation displacements in this transi-
tion. Our results provides useful information for choosing compositions for
specific applications.

Acknowledgments

We wish to acknowledge financial support from C I C y T (Grant no. P B 9 3 -

1253/94), Iberdrola (Grant no. INDES 94/95), Comunidad de Madrid
(Grant no. AE00138-94), and C E A O (UAM).

References

1. K. Roleder and J. Handerek, Phase Transitions 2, 285 (1982).

2. Y.L. Wang, Z.M. Cheng, Y.-R. Sun and X.-H. Dai, Physics B150, 168 (1988).
3. M.J. Haun, E. Furman, S.J. Jang and L.E. Cross, Ferroelectrics 99, 13, 27,
45, 55, 63 (1989).
4. V.A. Isupov, Ferroelectrics 143, 109 (1993).
5. H.M. Barnett, J. Appl. Phys. 33, 1606 (1962).
6. A.M. Glazer and S.A. Mabud, Acta Crystallogr. Sec. B 34, 1060 (1978).
7. X.H. Dai, J.F. Li and D. Vieland, J. Appl. Phys. 77, 3354 (1995).
8. D. Viehland, J.F. Li, X.H. Dai and Z. Xu, J. Phys. Chem. Solids 57, 1545
(1996).
9. B. Noheda, T. Iglesias, N. Cereceda, J.A. Gonzalo, H.T. Chen, Y.L. Wang,
D.E. Cox and G. Shirane, Ferroelectrics 184, 251 (1996).
10. X. Dai and Y.-L. Wang, Phys. Status Solidi A 124, 435 (1991).
11. J.A. Gonzalo, Y.L. Wang, B. Noheda, G. Lifante and M. Koralewski,
Ferroelectrics 153, 347 (1994).
12. D. Xunhu and Y.L. Wang, Ferroelectrics 109, 253 (1990).
13. R.C. Buchanan, J. Huang and J.E. Sundeen, Electroceramics V, Aveiro,
Portugal, 2-4 September 1996 (unpublished), pp. 309.
14. R. Gerson and H. Jaffe, J. Phys. Chem. Solids 24, 979 (1963).
15. S. Takahashi, Ferroelectrics 41, 143 (1982).
16. M. Hand, G.E. Kugel, J. Handerek and Z. Ujma, Ferroelectrics 135, 101
(1992).
17. W.L. Warren, J. Robertson, D.B. Dimos, B.A. Tuttle and D.M. Smyth, Fer-
roelectrics 153, 303 (1994).
18. Y.L. Wang, New Ceram. 11, 87 (1990) (in Japanese).
19. L. Benguigui, J. Solid State Chem. 3, 381 (1971).
20. Z. Ujma, D. Dmytrow and M. Pawelczyk, Ferroelectrics 120, 211 (1991).
21. B. Noheda, N. Cereceda, T. Iglesias, G. Lifante, J.A. Gonzalo, H.T. Chen,
Y.L. Wang, D.E. Cox and G. Shirane, Phys. Rev. B 51, 16388 (1995).
 Dielectric Characterization of the Phase Transitions 333

22. M. Yokosuka and M. Marutake, Jpn. J. Appl. Phys. 1 25, 981 (1986).
23. V.A. Isupov, Ferroelectrics 143, 109 (1993).
24. A.A. Bokov, Solid State Commun. 90, 687 (1994).
25. J.A. Gonzalo, Effective Field Approach to Phase Transitions and Some
Applications to Ferroelectrics (World Scientific, Singapore, 1991).
26. N. Cereceda, N. Duan, B. Noheda and J.A. Gonzalo, in Ref. 13, p. 193.
27. N. Cereceda, B. Noheda, T. Iglesias, J.R. Fernandez-del-Castillo,
J.A. Gonzalo, N. Duan and Y.L. Wang, Phys. Rev. B 55, 6174 (1997).
28. N. Duan, N. Cereceda, B. Noheda and J.A. Gonzalo, Ferroelectrics Lett. Sect.
22, 27 (1996).
29. B. Jaffe, W.R. Cook Jr. and H. Jaffe, Piezoelectric Ceramics (Academic,
London, 1971).
 Part 4
Some Applications
to Ferroelectrics: 1998-2005
 Chapter 4.1

Scaling and Metastable Behavior

in Uniaxial Ferroelectrics*
J.R. Fernandez del Castillo, B. Noheda, N. Cereceda
and J.A. Gonzalo
Department of Material Physics, C-IV,
Autonomous University of Madrid,
2804-9 Madrid, Spain

T. Iglesias
Department of Physics, Brookhaven National Laboratory, Upton,
New York 11973, USA

J. Przeslawski
Institute of Experimental Physics, University of Wroclaw,
Max Born Sr. 9, 50-205, Poland

Improved experimental resolution and computer-aided data analysis of

hysteresis loops at T ~ Tc in uniaxial ferroelectrics triglycene sulfate
(ordinary critical point) and triglycine selenate (quasitricritical point)
show that scaling holds in a wide range of scaled fields spanning many
orders of magnitude, well beyond the asymptotic region (\T — Tc\ —> 0),
and that the behavior of metastable experimental points (E < 0, P > 0)
approaches the theoretical branch of the respective scaling equation as
T->TC.

4.1.1. Introduction

As is well known, the revival of experimental and theoretical interest in

cooperative phenomena and continuous phase transitions, especially in

"Work previously published in Phys. Rev. B 52, (2) (1997). Copyright © 1997. The
American Physical Society.

337
338 Effective Field Approach to Phase Transitions

liquid-vapor, order-disorder alloys, and magnetic systems, has stimulated

a vast amount of work during the last three decades. 1 This work includes
more accurate sets of measurements close to the transitions than in previous
works, as well as the development of new theoretical concepts, such as scal-
ing, multicritical points, and the renormalization group theory. Ferroelectric
phase transitions, 2 in particular transitions in uniaxial order-disorder fer-
roelectrics like triglycine sulfate (TGS), have been shown3 many years ago
to present classical exponents (ft = 1/2, S = 3, 7 = 1, a = 0) and to obey a
classical (mean-field) equation of state. A prominent characteristic of this
kind of transition is the role long-range dipolar interactions play in them.
More recently,4 another uniaxial ferroelectric of the TGS family,
triglycine selenate (TGSe), was found to exhibit classical tricritical expo-
nents (ft = 1/4, S = 5, 7 = 1, a = 1/2) and to follow a quasitricritical
equation of state in which the tricritical exponents were used instead of the
former classical critical exponents.
In this work, we undertake, under substantially improved 3 ' 4 experimen-
tal conditions (automated data acquisition and analysis), digital resolution
in P, E, and T, a study of the equation of state of both uniaxial ferro-
electrics, TGS (ordinary critical point) and TGSe (quasitricritical point).
This have been done in order to (a) elucidate possible systematic deviations
from asymptotic scaling, (b) investigate the metastability 5 region at T < Tc,
and (c) to detect the presence, or lack of it, of logarithmic corrections 6 of
pure scaling in the pattern displayed by the data.
In this work, we present data that are substantially improved with
respect to those given in previously published work. 3,4 The improvements
include higher accuracy, a broader temperature range examined, and a much
closer set of points giving the P vs. E behavior at T very close to T c , both
above and below it. These improvements are important to investigate the
evolution of scaled data away from the close vicinity of Tc, where asymp-
totic scaling was previously detected, and allow us to explore the metastable
branch (E < 0, P > 0) of the P vs. E data, not previously investigated.

4.1.2. Experiment

Samples of different thicknesses and areas were cut from good optical
quality single crystals of TGS and TGSe grown from water solution. Sym-
metric and easily saturated loops were obtained with plates cleaved perpen-
dicular to the ferroelectric 6-axis and electrodes with goldleaf at the main
 Scaling and Metastable Behavior in Uniaxial Ferroelectrics 339

surfaces, which were about 0.5 cm 2 in surface and 1 mm in thickness. The

measurements were performed on a TGS sample of dimension 0.500 cm 2 x
0.140 cm and a TGSe sample of dimension 0.105 cm 2 x 0.044 cm (electrode
area x thickness, respectively). The temperature of the sample was con-
trolled using a temperature controller (Unipan 680) capable of producing
very slow linear heating and cooling ramps ( ~ l K / h in our case). Hys-
teresis loops were obtained using a Diament-Drench-Pepinsky 7 (DDP) cir-
cuit, with phase compensation only through change of auxiliary resistance.
The loops were recorded in a relatively wide temperature interval encom-
passing Tc for both crystals [TC(TGS) = (321.470±0.005)K, T c (TGSe) =
(294.683 ± 0.005) K] (calculated from the fit to the scaling equation of
state), using a digital oscilloscope (Nicolet NIC-310). For each loop, 4000
points were recorded at each temperature, which insured high resolution of
the P vs. E, hysteresis loops below T c and nonlinear curves above Tc.
It may be noted that special precautions must be taken to get good qual-
ity, symmetric, hysteresis loops. Phase compensation, achieved by varying
the auxiliary external resistance in the DDP circuit, must be performed as
close as possible to T c , because the resistivity of the crystal is temperature
dependent through the transition. In this way, the undesirable effects on
PS(T) and EC(T) due to under-compensation or overcompensation can be
minimized. The small asymmetry present in most loops, resulting from the
small bias due to inhomogeneous distribution of charged impurities, should
be taken care of, first, by annealing the sample for 20 h at T = 70°C, well
above T c , and, second, by shifting the center of the loop to the true center
of symmetry. This was achieved with a simple iterative computer program
to ensure that \+Ec\ = \— Ec\, \+Ps\ = \—Ps\ with Ps and Es the sponta-
neous polarization and the coercive field, respectively. Also important is the
choice of frequency for the driving field, which should be low (to approach
equilibrium conditions) but not too low in order to avoid excess ionic con-
duction. We have used a frequency around 50 Hz for most measurements.
The final, but very important factor, is the unavoidable thermal gradient
from the lower to upper surface of the sample that must be minimized.
The estimation of this gradient for our experimental setup gave the value
of ~0.01K/cm.

4.1.3. Results

Figures 4.1.1(a) and 4.1.2(a) show typical hysteresis loops for TGS and
TGSe in the vicinity of the transition. Thicker lines point which part from
340 Effective Field Approach to Phase Transitions

I ' I ' I ' I ' I ' I ' I '

-1.0 -A8 -0.5 -0.3 0.0 0.3 05 0.8 "W3
(a) E(V'on)

2.5-

o- 1.0-

-0.2 0.0 0.2 0.4 0.6 0.8* 1»3

(b) E(VJcm)

Fig. 4.1.1. (a) Digital hysteresis loop for TGS just below the transition. Thicker line
shows the points from each loop that are shown in (b) and are used as raw data in
what follows, (b) P (polarization) vs. E (field) at various temperatures close to T c for
triglycine sulfate (TGS) at 307 < T < 323 K. Only 10% of the experimental points at
each temperature are shown. Only one-fourth of the recorded temperatures are shown
for clarity of presentation. Vertical lines indicate intervening regions in which the data
are little affected either by rounding effects or imperfect phase compensation (see text).

each loop is taken to plot Figs. 4.1.1(b) and 4.1.2(b), which show the set
of P{E) below and above T c , for TGS and TGSe, respectively. The P(E)
values for E < 0, down to the inflection point in P vs. E correspond to
metastable states. The curves corresponding to T « Tc were determined,
as shown below (Figs. 4.1.3 and 4.1.4), from P3(E) for TGS and P5(E) for
TGSe. This allowed us to identify the critical and the tricritical isotherm,
 Scaling and Metastable Behavior in Uniaxial Ferroelectrics 341

I ' I ' 1
-2 0 2 ««»
E<V/cm>

I
;;#**'•
• i ' i '
3 4 7X10 3
(H) e (V / c m )

Fig. 4.1.2. (a) Digital hysteresis loop for TGSe just below the transition. Thicker line
shows again the points from each loop that are shown in (b) and are used as raw data
in what follows, (b) P (polarization) vs. E (field) at various temperatures close to Tc for
triglycine selenate (TGSe) at 284 < T < 298 K. Only 10% of the experimental points at
each temperature are shown. Only one-fourth of the recorded temperatures are shown
for clarity of presentation. Vertical lines indicate intervening regions in which data are
little affected either by rounding effects or imperfect phase compensation (see text).

respectively, through the observation of the straight lines which passes

through the origin (E = 0, P = 0). In our opinion, such plots are important
since they give a direct, unmanipulated experimental hysteresis loop.
In Figs. 4.1.3 and 4.1.4, we present P3(E) for TGS and P3(E) for TGSe,
respectively, which result in straight tines for E values higher than cer-
tain temperature-dependent threshold, and allow the identification of the
342 Effective Field Approach to Phase Transitions

0 100 200300400500600 700 800900 1000

E(V/cm)

Fig. 4.1.3. Normalized polarization up to the third power (p 3 ) vs. field (E) at various
temperatures (for 321 < T < 322.1 K) close to T c , defining the ordinary critical isotherm
(T = Tc = 321.470 K). The actual temperature corresponding to the experimental data
( P vs. E) closest to T c is indicated. Vertical lines show the range of fields used for the
linear fit of the critical isotherm.

0.12

I ' I ' I ' ) ' I ' I

0 1000 2000 3000 4000 5000 6000 7000 8000
EfWcm)

Fig. 4.1.4. Normalized polarization up to the fifth power ( P 5 ) vs. field (E) at various
temperatures (283.2 < T < 298K) close to Tc, defining the tricritical isotherm (T =
T c = 294.683 K). The actual temperature corresponding to the experimental data ( P vs.
E) closest to T c is indicated. Vertical lines show again the range of fields used for the
linear fit of the critical isotherm.
 Scaling and Metastable Behavior in Uniaxial Ferroelectrics 343

critical and tricritical isotherms, respectively, which pass through the origin
(E = 0,P = 0).
In Figs. 4.1.5 and 4.1.6 plot of Ps2 vs. T for TGS and Ps4 vs. T for
TGSe, respectively, gave a linear dependence, as it is to be expected for
ordinary critical and tricritical (or quasitricritical) behavior. Nevertheless,
the exact determination of Tc becomes somewhat more problematic in this

3-i
TGS
Te(Ps 2 ) = 321.331K
E = 928.5 V/cm
f = 50Hz

Fig. 4.1.5. Squared spontaneous polarization (P s 2 ) vs. T for TGS.

300
TGSe
Tc(Ps 4 )= 295.282 K
E = 7272.7 V/cm
f=50Hz

300
T(K)

Fig. 4.1.6. Fourth power of the spontaneous polarization (P s 4 ) vs. T for TGSe.
344 Effective Field Approach to Phase Transitions

case, because deviation from linear behavior due to the lack of perfect phase
compensation in the loops.

4.1.4. Equations of State

The equation of state for an uniaxial ferroelectric, which should follow a

classical Landau behavior asymptotically, 3 can be extended using a gener-
alized effective field expanded in terms of odd powers of the polarization

EeS = E + 0fP + jtP3 + SfP5 + • • • , (1)

where E is the external field, P the polarization, and (3{, 7f, <5f, are constant
coefficients depending only on the geometry of the crystal lattice and the
charge distribution within a unit cell.4 For a ferroelectric crystal with N
unit dipoles (/i) statistically oriented along the ferroelectric axis, with N\
in the direction of the field and N2 in the opposite direction (N1+N2 = N),
the polarization is given3 by

P=(N2-N1)^ = N^tanh(j^j, (2)

where fee is Boltzmann's constant and T the temperature. From this rela-
tionship it is straightforward to get the equation of state in terms of reduced
variables (e = E/Es0, Es0 = /?iV>; p = P/Ps0, Pso = M) as
T
e = — t a n h " 1 ^ ) - (1 + gp2 + hpA + • • • )p,
(3)
Pi Pi
1
and, expanding tanh p in powers of p, which is especially useful for a
subsequent investigation of the asymptotic equation (e < 1, p C 1, (T -
Tc)/Tc<l),weget

I + + k + (4)
'- ir' {li-'y {lrc- y --
This is the general equation of state for a dipolar uniaxial ferroelec-
tric, valid at the vicinity of ordinary as well as quasitricritical points. It is
analogous to the equation derived from Landau's theory, 5 but not identical
because it contains specific temperature dependences of the coefficients of
the successive powers of the polarization.
 Scaling and Metastable Behavior in Uniaxial Ferroelectrics 345

For TGS (ordinary critical point, g < 1/3), Eq. (4) can be written in
the scaling form as

T
±p +
(G $C[(T-Tc)/Tc,p] \p (5)

where e = e / | T - T c / T c | 3 / 2 and p = p/\T -Tc/T^l2 are the scaled vari-

ables, and

$C[(T-Tc)/Tc,p] =
1 (T~TC
3 V Tc
± I'9 T-Tr

1 (T-T<
(6)
~5 Tc.

In Eq. (5), the ± signs correspond to the T > Tc branch and the T < Tc
branch, respectively, and <J>C = [(T/Tc)Tc,p\, which becomes important only
for T below and away from T c , changes from $ c [0,p] —> 0 at T « Tc to
$c[—1,1] —» const at T w 0, always for e ^C 1. It may be noted that ESQ =
PN/x is in practice much larger than the breakdown field, and therefore the
behavior at e « 1 is not relevant experimentally.
For TGSe (quasitricritical point, g « 1/3), on the other hand, the term
in p 3 disappears, and Eq. (4) should be written in scaling form as

1 T
±P- <M(T-TC)/TC)P]U5, (7)
57;

where e = e/|(T - T c )/T c | 5 / 4 , p = p/\(T - Tc)/Tc\l'\ and

"1T-T C /T-Tc
$tc[(T-Tc)/rC)p]
[5 Tc ~h
±
[(H
1 /r-Tc\i 2
7 \ Tc ) \
p" «}• (8)

Note that scaled variables and $ tc [(2 1 - Tc)/Tc,p] are now defined dif-
ferently. Again, in Eq. (7) the ± signs correspond to the T > Tc branch and
T < Tc branch, respectively, and &tc[(T — Tc)/Tc,p], which also becomes
important only for T < Tc and toward the low-temperature region, goes
from $ c [0,1] -> 0 at T « Tc to $ c [ ( - l ) , p ] - • const, at T RS 0, always for
e < 1.
346 Effective Field Approach to Phase Transitions

Fig. 4.1.7. Scaled data l n p vs. l n e at T < Tc, including metastable data {E < 0,
P > 0) and at T > T c , for TGS (307 < T < 323K), where e = e / | ( T - T c ) / T c | 3 / 2 and
p s p/\(T — TcVTc] 1 ' 2 are the scaled field and the scaled polarization, respectively. The
continuous curve is the asymptotic equation of state [Eq. (9)] for an ordinary critical
point. The dashed line shows the expected asymptotic behavior as T —> OK. Note that
experimental data collapse on the asymptotic equation of state in a wide range (more
than ten orders of magnitude in scaled field and four orders in scaled polarization).

Figure 4.1.7 gives lnp vs. lne for TGS, together with the asymptotic
equation of state corresponding to an ordinary critical point

e = ±p+(^-g\p3 (g = 0.24 ±0.05). (9)

It can be seen that for T <TC and away from Tc, scaling still holds well,
i.e., the data for different temperatures continue to collapse on a single
curve, but the coefficient of p3 changes gradually as it should, toward one,
marked as a dashed line in the figure, because T —> 0, p —> 1 (P s —> Pso)>
and p goes to unity, which results in lap going to zero. For T > Tc, the fit
to the asymptotic equation (9) is almost perfect in the whole experimental
range. It may be noted that the set of experimental points further up in
the graph corresponds to a particular temperature extremely close to T c ,
and that the nearest sets at both sides are substantially away form Tc, in
comparison. A sequence of sets at more closely spaced temperatures would
have closed the gap between neighboring set of isothermal points in the
graph.
 Scaling and Metastable Behavior in Uniaxial Ferroelectrics 347

Fig. 4.1.8. Scaled data l n p vs. lne, at T < Tc, including metastable data (E < 0,
P > 0) and at T > T c for TGSe (284 < T < 298K), where e = e/\(T - T c ) / T c | 3 / 2
and p = p / | ( T — TcJ/Tcl 1 ' 2 are the corresponding scaled field and scaled polarization,
respectively. The continuous curve is the asymptotic equation of state [Eq. (10)] for a
tricritical point. The dashed line shows the expected asymptotic behavior as T —> OK.
Again, the asymptotic equation is valid in a wide range of field and polarization.

Likewise, Fig. 4.1.8 gives, for TGSe, lnp vs. lne, wherep and e are now
defined in the way appropriate for tricritical point behavior, and shows the
asymptotic equation of state corresponding to a tricritical point.

e = ±p + \\-h)f {h = 0.14 ±0.05). (10)

Also in this case the agreement between theory and experiment is good
and scaling holds very well for all our data obtained for T > Tc. For the data
obtained below T c , the deviation from the asymptotic equation is smaller
than in the previous case, as expected. Note that experimental data in
both cases (TGS and TGSe) collapse on the asymptotic equation of state
in a wide range (more that six orders of magnitude). The coefficient of p5
changes again gradually toward one as p goes to unity with T —> 0.

4.1.5. Metastable Behavior

Figures 4.1.7 (TGS) and 4.1.8 (TGSe) also include points corresponding
to the metastable behavior (E < 0, P > 0) shown in the loops (see
348 Effective Field Approach to Phase Transitions

Figs. 4.1.1 and 4.1.2). It is well known that, due to the forward and side-
wise motion of domain walls,8 the ferroelectric coercive field, which deter-
mines the metastability region, is orders of magnitude lower than the ideal
(thermodynamic) coercive field. It may therefore be expected that, as Tc
is approached from below, the "contrast" between domains decreases, the
effective field at the domain boundaries approaches asymptotically to the
ideal (bulk) effective field value. If this is so, we may expect that the scaled
data corresponding to the metastable portions of the loops approach the
metastable branches of the scaling equations,

~e = -p+(^-g)p3 forTGS, (11)

-e = -p + (\-hjp5 forTGSc, (12)

which are represented as ln|p| vs. ln|e| in Figs. 4.1.7 and 4.1.8, returning
from the left and going down. It can be seen that the shapes of the curves
defined by the data are similar to those defined by Eqs. (11) and (12),
and that there is a clear tendency in both sets of data to move toward the
metastable branches of respective scaling equations.

4.1.6. Discussion

We may conclude that scaling holds in uniaxial ferroelectric TGS (TGSe)

at points substantially further away from critical (tricritical) point than
previous investigations. 3 ' 4 Deviations from asymptotic scaling for T < Tc
take place, gradually, toward the expected behavior when T —> T c , in accor-
dance with analytic expression, given by Eqs. (5) and (7), obtained within
a generalized effective field approach.
For points in metastable regions (E < 0, P > 0) the data show a clear
tendency, both for TGS and TGSe, to approach the metastable branches
of the corresponding scaling equations (solid line in Figs. 4.1.7 and 4.1.8).
No logarithmic corrections 6 are clearly visible in our scaled data. Such
corrections (predicted a long time ago9) are important for uniaxial ferro-
electrics but have not yet been fully elucidated experimentally by hysteresis
loop measurements. This might be taken to imply that the role of fluctua-
tions is less important in uniaxial ferroelectrics at T sa Tc than that of other
nonlinear electric or elastic interactions in the crystals. Around Tc ± 1K the
estimated error of polarization for a driving field amplitude is less than 3%,
 Scaling and Metastable Behavior in Uniaxial Ferroelectrics 349

Table 4.1.1. Scaling constant for uniaxial ferroelectrics TGS and TGSe.

Crystal Tc(K) C(K) Eso/Pso 4TTTC (°C) 9 h

(uC/cm2) (10 6 V/cm)

TGS 321.47 3650 4.2 4.41 1.16 1.10 0.24

TGSe 294.68 4050 4.5 2.89 0.76 0.91 «l/3 0.14

which sets an upper limit for possible logarithmic corrections. Nevertheless,

as it was previously mentioned it is quite difficult to achieve perfect phase
compensated loops at T ~ T c . To the best of our knowledge this is the first
experimental work exploring the metastable behavior at T w T c in uniaxial
ferroelectrics.
Table 4.1.1 summarizes scaling d a t a for T G S and TGSe. T h e respective
Curie constants are from previous dielectric constant measurements. 3 , 1 0 , 1 1
T h e consistency between /3 = ES0/PSQ and /3 = (AirTc)/C is much better
t h a n in the previous works. 3 ' 4

Acknowledgments

We acknowledge the financial support of C I C y T (Grant no. PB93-1253)

and the Comunidad de Madrid, Project no. AE00138/94. One of us (J.P.)
t h a n k s D G I C y T for financial support for a sabbatical (SAB94-0084) at the
Ferroelectric Materials Laboratory, UAM.

References

1. See, for example, H.E. Stanley, Introduction to Phase Transitions and Critical
Phenomena (Oxford University Press, New York, 1971).
2. See, for example, N. Goldenfeld, Lectures on Phases Transitions and the
Renormalization Group (Addison-Wesley, Reading, MA, 1992).
3. See, for example, F. Jona and G. Shirane, Ferroelectric Crystals (Pergamon,
New York, 1962).
4. J.A. Gonzalo, Phys. Rev. B 1, 3125 (1970).
5. T. Iglesias, B. Noheda, B. Gallego, J.R. Fernandez del Castillo, G. Lifante
and J.A. Gonzalo, Europhys. Lett. 28, 91 (1994), and references therein.
6. See, for example, L.D. Landau and E.M. Lifshitz, Statistical Physics, 3rd edn.
(Pergamon, Oxford, 1980).
7. A. Aharony and M.E. Fisher, Phys. Rev. B 8, 3342 (1973).
8. H. Diamant, K. Drenek and R. Pepinsky, Rev. Sci. Instrum. 28, 30 (1957).
350 Effective Field Approach to Phase Transitions

9. M.J. Cabezuelo, J.E. Lorenzo and J.A. Gonzalo, Ferroelectrics 87, 353
(1988).
10. A.I. Larkin and D.E. Khmelnitskii, Zh. Eksp. Teor. Fiz. 56, 2087 (1969) [Sov.
Phys. JETP 29, 1123 (1969)].
11. T. Iglesias, B. Noheda, G. Lifante and J.A. Gonzalo, Phys. Rev. B 50, 10307
(1994).
 Chapter 4.2

Energy Conversion with Zr-Rich

Lead Zirconate/Titanate Ceramics*
Ning Duan, Noe Cereceda, Beatriz Noheda,
Jose Raul Fernandez-del-Castillo and Julio A. Gonzalo
Departatnento de Fisica de Materiales,
Universidad Autonoma de Madrid,
28049 Madrid, Spain

The conversion efficiency and power output to convert thermal energy

to electrical energy by means of a ferroelectric-ferroelectric phase tran-
sition has been investigated. The material used was the ceramic mixed
system lead zirconate/titanate (PZT) with a high Zr-enriched composi-
tion (Zr/Ti = 97/3%). We have studied the performance dependence on
sample thickness and working frequency, the main relevant parameters
for a given PZT composition. The observed optimum values of efficiency
and power output are analyzed in terms of the two main characteris-
tic relaxation times of the process, the thermal time (sample thickness
dependent) and the electric time (thickness independent). Possible ways
of improving the overall performance are discussed.

Direct thermal t o electric energy conversion using Zr-rich lead zir-

c o n a t e / t i t a n a t e (PZT) ferroelectric ceramic plates by thermal cycling at
the phase transition between t h e two rhombohedral ferroelectric phases,
FRL (low-temperature phase) and F R H (high-temperature phase), has been
investigated by several a u t h o r s . 1 " 5 In these works, the advantages of using
these kinds of phase transitions for energy conversion applications have been
already pointed out, in comparison with other better known ferroelectric
transitions. 6 ~ 8 Ferroelectric energy conversion with poled P Z T , through the
fRH-i 7 RL first order transition occurs between two phases with nonzero

*Work previously published in Appl. Phys. Lett. 77, 13 (1997). Copyright © 1997.
American Institute of Physics.

351
352 Effective Field Approach to Phase Transitions

polarization, and is the only demonstrated case in which no external fields

are needed, unlike cases in which the ferroelectric-paraelectric (F-P)7 or
the ferroelectric-antiferroelectric (F-AF)6 transitions are used, requiring
external fields for cyclic operation. In these investigations, a polarized sam-
ple subject to thermal cycling is connected to an external load. By heating
and cooling the sample around the -FRH-^RL phase transition temperature
(7LH); positive and negative free charges are produced at the electrodes
of the ceramic plate, due to the temperature induced change in sponta-
neous polarization, which is measured as a voltage signal through the load
resistance.
It is well known that not all thermal energy transmitted to the ferroelec-
tric plate is converted into electricity, apart from the thermodynamic limi-
tation, r\ < rjc — A T / T m a x , because some of the thermal energy is wasted in
mechanical expansion/contraction of the material, heating metallic plates
in contact with the ceramic, and other processes.9 The actual efficiency
and the power output could be, however, considerably improved in several
ways, including the design of materials especially adequate for this purpose,
combining a small dielectric constant and a large polarization change at the
transition, and the so-called "multistage" operation. 10 It consists in using
a set of plates with changing composition and profiting from the wasted
energy from one sample for heating the next sample with a slightly lower
transition temperature. In this way, a set of PZT plates with gradually
changing compositions {x\ < X2 < ••• < xn), having transition tempera-
tures T L H ( ^ I ) < T\Jft{x2) < • • • < Tu$(xn), could be used. First, however,
a better understanding of the process itself taking place during conversion
in our system (PZT plate + experiment setup) is necessary.
In the present work, we have investigated the dependence with the sam-
ple thickness and the frequency of the output power and the efficiency of
plates with a single Zr-rich PZT composition.
The experimental apparatus used is the same as in Ref. 4, but several
improvements were made and the dynamic range was extended to lower
frequencies. The heating source was an IR lamp and the temperature oscil-
lations were created by a chopper. The center and the width of the temper-
ature window could be reliably controlled by changing the lamp intensity
as well as the frequency of the chopper, driven by a low-speed motor (range
from3mHz to 0.11 Hz).
The composition of the thin plates used in the present work was PZT
97/3 + 3.9mol%ofNb 2 0 5 , which has a transition temperature T LH « 49°C,
with a polarization change of about A P « 2/xC/m 2 .
 Energy Conversion with Zr-Rich Lead Zirconate/Titanate Ceramics 353

The specific output power is given by

energy/cycle IV
^out — -, J — , \L)
volume v
where energy/cycle is the total output energy per cycle, / is the frequency,
and v is the sample volume.
The efficiency of the conversion process can be obtained through

= ^ut = CIVdt „ IoAtlVdt (2)

V {)
Ein fi:::vpvCvdT~vpvCvAT>
where pv is the density, C p the average specific heat per unit mass over the
working temperature window, AT = T m a x — T m ; n , and At = 1 / / is the time
for one cycle.
For a given lamp intensity, the temperature interval, AT, can be
decreased by increasing the chopping frequency in such a way as to fix
it to the place where the maximum change of polarization occurs, increas-
ing, in this way, the efficiency [see Eq. (2)], which must be low enough
to allow most of the charge to be, first, liberated at the electrodes after
the heating/cooling period and, then, released through the load resistance.
Here, the two characteristic times of the process 10 are the electrical relax-
ation time (r e = pee = RC, where R is the optimized load resistance, equal
to the sample resistance, and C is the sample capacitance), depending only
on the material resistivity, pe, and its dielectric constant, e, and the ther-
mal relaxation time (-rth = pvCpd2/kth), which depends on the density pv,
the average specific heat Cp, over the working temperature window the
thermal conductivity kth, and the thickness of the sample d. Then, for a
given material, the optimum working frequency can be tuned to the sample
thickness. In principle, the lower the r t h the higher the working frequency
and the efficiency. However, we know that VoUt = Q/C = APsd/e, where
Q is the charge liberated at the surface of the sample, C the capacitance of
the sample, APS the change in spontaneous polarization, d the thickness,
and e the dielectric constant. Note that PZT around TLH has a conve-
niently very low s(T) value in comparison with e(T) near the Curie point,
contributing to a higher output voltage. We can expect, as it was found,
that, for the same composition, V^,ut increases linearly with the sample
thickness.
The total characteristic time of the process can be estimated from the
full-width at half-height of the voltage peak versus time obtained with a
frequency low enough to observe the full-peak real shape. These values
354 Effective Field Approach to Phase Transitions

• observed T
0- fitting: t= 25 d 2 + 6.4
T
e+Xr

8-

_ _ ^ ^
•

6-
V^r

4 - V- i '" r
' ~T
0.0 0.1 0.2 0.3 0.4

d (mm)
Fig. 4.2.1. Total optimum characteristic time observed vs. sample thickness. The full
line represents the best fit r t o tal = 6.4 + 25d 2 (T to t a i in seconds and d in mm) to the
data. The dotted line marks the level of all other contributions to the characteristic time
(independent of d), including the electrical characteristic time, Te.

are represented vs. thickness in Fig. 4.2.1. The only expected thickness
dependence comes through the contribution of the thermal characteristic
time, proportional to the squared thickness (rth oc d2). Then, we can easily
extract from Fig. 4.2.1 the observed value of r t o t — Tth, fitting the experimen-
tal data to Ttot = Ad2 + B (A = 25s/mm 2 , B = 6.4s), where the first term
represents Tth and the second term represents the contributions of the other
characteristic times of the process (independent of d). This value (6.4 s) is
much higher than the expected electrical timer (re = pe « 0.8 s). We call
residual time, r r , to the additional contributions to the total relaxation time,
after discounting r e , which are mainly related to the indirect heating of the
sample and to the thermal inertia of the whole system (setup + sample).
Figure 4.2.2 gives the pout as a function of frequency for three different
thickness (0.1, 0.2, and 0.4 mm) in the range of 3 < / < 110 mHz. It
is shown that the optimum pout and efficiency correspond to a frequency
of 0.04 Hz and a thickness of (0.2 ± 0.1) mm. Under these conditions, we
have obtained a peak voltage of ±83 V, an energy density per cycle of
7.5mJ/cm 3 , a specific output power of 0.75mW/cm 3 , and an efficiency
given by m = T]/r]c = 0.01, r/c being the Carnot efficiency. From the data
in Fig. 4.2.1, we have obtained a r t h = 25, which gives a r t h = I s for a
0.2 mm thickness, of the same order as r e , as can be expected near optimum
conditions.
 Energy Conversion with Zr-Rich Lead Zirconate/Titanate Ceramics 355

1.0 ( • • • ' 1 ' 1

1
A 0.4mm
> * \_ » 0.2mm
0.1mm
/ \
\

* 0.5-

0L,

•
i A =
* **"*&.
•
0.0 i ' ( l ' l ' — i — • — i

0.00 0.02 0.04 0.06 0.08 0.10 0.12

f(Hz)

Fig. 4.2.2. Specific power output vs. frequency for three different thicknesses.

There exists room for further improvement of the o u t p u t power and

the efficiency through a synchronized discharge operation. In it, charge is
accumulated u p to the m a x i m u m (in an open circuit), t h e n the circuit is
closed, and the charge is released t h r o u g h a proper load resistance, just
before the chopper changes to another half cycle. Preliminary results show
a m a x i m u m o u t p u t voltage 1.6 times t h a t of the value obtained by means
of a spontaneous discharge operation. This figure can be improved varying
the ratio open circuit t i m e / s h o r t circuit time.
In conclusion, it is perhaps somewhat p r e m a t u r e to make a final eval-
uation of ferroelectric materials as an energy converter, in view of the as
yet relatively low efficiencies found. We note, however, t h a t a better knowl-
edge about the conversion process in Zr-rich P Z T samples has improved
by a factor of 10 the efficiency of the specific power o u t p u t . This fact
may be indicative t h a t further improvements are possible by modifying
the operation mode (multistage/multicomposition operation, synchronized
discharge operation) and, perhaps more important, by identifying materials
with larger A P S , accompanied by moderate A T and low e ( T ) .

Acknowledgments

T h e authors are grateful to Eliaz Rodriguez and the Spanish C I C y T (Grant

no. PB93-1253) and I B E R D R O L A .
356 Effective Field Approach to Phase Transitions

References

1. J.Y. Lian, Masters Thesis, Shanghai Institute of Ceramics, Shanghai, China,

1985.
2. X.H. Dai and Y.L. Wang, Ferroelectrics 107, 253 (1990); X.H. Dai, Ph.D.
Thesis, Shanghai Institute of Ceramics, 1990.
3. Noe Cereceda, Masters Thesis, Universidad Autonoma de Madrid, Madrid,
Spain, 1996.
4. J.A. Gonzalo, Y.L. Wang, B. Noheda, G. Lifante and M. Koridewski,
Ferroelectrics 153, 347 (1994).
5. B. Noheda, Ph.D. Thesis, Universidad Autonoma de Madrid, Madrid, Spain,
1996.
6. R. Briot, P. Gotthard and M. Troccaz, Silic. Ind. 2, 33 (1982).
7. R.B Olsen, J. Energy 6, 91 (1982); Ferroelectrics 40, 17 (1982).
8. W.H. Clingeman and R.G. Moore, J. Appl. Phys. 32, 675 (1961).
9. A. Van der Ziel, J. Appl. Phys. 45, 675 (1974).
10. J.A. Gonzalo, Ferroelectrics 11, 423 (1976).
 Chapter 4.3

Microscopic Characterization of
Low-Field Switching in
Ferroelectric TGS*
Carmen Arago, J.R. Fernandez del Castillo,
Beatriz Noheda and Julio A. Gonzalo
Departamento de Fisica de Materiales, C-IV,
Universidad Autonoma de Madrid,
28049 Madrid, Spain

Low-field ( < l k V / c m ) switching has been investigated for thin plates

(0.06 < d < 0.15 cm) of triglycine sulfate by means of field pulses with
a linear rise time. The dependence of the maximum current density,
jm, with the field value Em at which this maximum occurs is j m =
B i ( £ m - . E c w i ) 3 / 2 , for 0.3 < Em < 0.5kV/cm, and j m ~ B 2 ( £ m - . E c w 2 ) ,
for 0.5 < -Em < l.OkV/cm. This is satisfactorily explained taking into
account the dominant role played by sidewise and forward domain wall
motion, respectively.

4.3.1. Introduction

Ferroelectric switching in triglycine sulfate (TGS) using external field pulses

has been investigated extensively by various authors 1 ~ 4 since the late 1940s.
While the high-field behavior was satisfactorily explained 5 by random bulk
switching of the individual dipoles, the low-field behavior was only ten-
tatively explored in terms of forward and sidewise domain wall motion
driven by the action of the switching fields with rectangular pulses. More
recently, the switching kinetics, especially in ferroelectric ceramics with
prospective applications for computer memories, have been investigated in

"Work previously published in J. Appl. Phys. 84, 7 (1998). Copyright © 1998.

American Institute of Physics.

357
358 Effective Field Approach to Phase Transitions

great detail. 6 ^ 8 The range of fields investigated in PZT thin films is high
(200-1000 kV/cm) and the switching time dependence of systems such as
the two-dimensional Ising model 7 and the finite size Kolmogorov-Avrami 8
model were also investigated.

4.3.2. Experimental

In this work, we are just concerned with low fields, below 1 kV/cm. A
Hewlett-Packard generator, model 33120A, has been used to apply alter-
natively negative and positive rectangular field pulses, E{t), which are
amplified with a Kepco bipolar amplifier, model BOP 1000M, capable of
producing, pulses of ±1000V and ±40 mA. As rectangular pulses are grad-
ually amplified they get an almost linear initial variable rise time, as shown
in Fig. 4.3.1, and we may consider the applied field as E(t) = (E0/t0)t
for the initial relevant part of the pulse. The switching current density,
j(t), is also shown in Fig. 4.3.1. As this curve can be approximated to an
isosceles triangle, 9 a simple relation between the maximum current den-
sity, jm = j(tm), and the switching time, ts, can be obtained at a fixed
temperature as
4^
m<tt = \jmts = 2Ps ts
/ 3m
Jo

t(ms)

Fig. 4.3.1. Plot of a positive field pulse, E(t), after amplification, and the corresponding
j(t), indicating the meaning of Em = -E(t m ) and j m = j(tm).
 Microscopic Characterization of Low-Field Switching in Ferroelectric TGS 359

where Ps is the spontaneous polarization. Both j m = j(tm) and Em = E(tm)

have been observed and measured from a Hewlett-Packard oscilloscope,
model 54603B.
Three samples were cut from single TGS crystals, grown from water
solution. Sample dimensions were di = 0.15cm, A\ = 1.1cm2; d% =
0.08 cm, A2 = 0.36 cm 2 ; and d3 = 0.06 cm, A3 = 0.64 cm 2 . The ferroelectric
axis was parallel to the direction of the applied field. All the experiments
were performed at RT (T ^ 20°C).

4.3.3. R e s u l t s a n d Discussion

Figure 4.3.2 shows the resulting curve j m vs. Em for the three samples. The
observed data display the expected low-field behavior, which is very similar
qualitatively to that observed with squared and shorter pulses by Fatuzzo
and Merz 3 in another range of field values.
In the initial regime (I), the maximum current density, jm(Em), grows
faster than linearly with Em from a threshold domain wall switching coer-
cive field, Ecw, to E^, E^ being the field corresponding to the transition
from regime I to regime II.
In the subsequent region (II), jm(Em) grows linearly with Em, i.e., for
Em > ££j, up to a much higher field, at which a change to bulk random
switching eventually would take place.

40- • 0.15cm 1.1 cm2 o

o
o 0.08 cm 0.36 cm2 0
•
• 0.06 cm 0.64 cm2
30- 0 •
0
o
E • •
my
20- (II)
E m •

10-
,"o«
"^ (1)
0- H«J* , . 1
0.2 0.6
Em(kV/cm)

Fig. 4.3.2. Maximum switching current, j m , vs. field, Em, for three TGS sample plates,
showing the different behaviors at regimes I and II.
360 Effective Field Approach to Phase Transitions

To describe microscopically the behavior depicted in Fig. 4.3.2, we

assume that domain wall switching proceeds from small remnant counter
polarized domains at one surface and that both forward and sidewise motion
are involved. We assume as well that the sidewise domain wall velocity,
u(swm) = Vi(E), has a field dependence different from that of the forward
domain wall velocity, u(fwm) = V2{E). At low fields above the threshold
Ecvr (known to be much smaller than Ecb, the random bulk coercive field),
the tips of preexisting microdomains are expected to arrive first at the
opposite surface. The lateral growth of the counter polarized domains is
then expected to proceed more slowly (v\ < t^)-
At a somewhat higher field, E^, the tips of the growing microdomains
arrive quickly at the opposite surface at about the same time as the lateral
walls of neighboring microdomains (which are considered to be spaced at
roughly regular intervals 10 ) meet each other. From E^ upwards the sidewise
domain wall motion is expected to became so fast that the lateral growth
keeps pace with the forward motion of the broad tip, causing the switching
process to be controlled by the forward domain wall motion that proceeds at
a lower rate (v\ > 1*2). In the following we make this argument quantitative,
starting from the general rate equations that give (dPd/dt) in response to
a field E = (Eo/to)t, and we show that good consistency with the observed
low-field switching behavior is obtained.
dA^ being the number of dipoles per unit of volume that contributes to
the switching in a time interval dt, the general rate equation is given by 5

dt T [v ^ a;
\T Es0 J

Here, (JVb + Na) = N is the total number of dipoles per unit of volume in
the whole crystal, 1/r is the transition probability for E —> 0 at T > Tc
(Curie temperature), E is the external field, (3P& the polarization field,
and Es0 = /3Nfj, the saturation field, with /3 = 47rTc/C, the mean field
coefficient, C the Curie constant, and /J, the elementary dipole moment.
Since at low fields all switching processes take place at domain walls no
screening effects need to be considered.
It must be noted that, for domain wall switching, only the two mono-
layers of unit cells in contact at the wall will participate in the switching
process. So, we call A^ w the number of dipoles per unit volume susceptible
 Microscopic Characterization of Low-Field Switching in Ferroelectric TGS 361

of being aligned with the field, and iVaw the number of dipoles per unit
volume already aligned. Therefore, iVbw + ^ a w = Nw will be much smaller
than N = l/vc, vc = abcsin$ being the volume of the unit cell. Here,
a — 9.15 A, b = 12.69 A, and c = 5.73 A are the dimensions of unit cell10
and /? = 105°, the monoclinic angle.
Particularizing the general rate equation for domain wall switching is
all we need to do to get the switching current time evolution. Then, con-
sidering quasi-cylindrical domain walls surrounding the initially grown up
microdomains (from the bottom to the top of the crystal plate),

n 2n[f(t) + s]d'
iV,bw
V
the density of dipoles of the outer monolayer to be aligned by the field, is
only slightly larger than
~2nf(t)d~
N —
Jv
aw — V sb
the density of dipoles of the inner already switched monolayer. We have
used in these expressions n = A/2ir(fm)2 as the number of prepolarized
nuclei in the surface area A of the plate, f being the maximum radius of
the growing domains. V is the total volume of the sample (V = Ad), d is the
thickness of the sample, and s = (ac sin /3) 1 / 2 a kind of average dimension
of the unit cell perpendicular to the ferroelectric axis.
Therefore, considering that r(t) ^> s,
2n 2-Kf(t)d n /2TRA
JV W = JV,bw NK iV,bw NK
V sb V\~)
and taking into account that Em + 0wPdn <C Eso, which implies
tanh x = x, we can write
iVibw •NK Tr. E„ Pw*>dn Tc Em + (3wPdn
tanh
Nhv/ - Na E.s0 T Ks0
which is sufficiently larger than one for domain wall switching /3W -C 1 (as
it is shown later), and allows us to neglect the second term in Eq. (1).
Substituting iVw and multiplying this equation by fi, we get

m =dPdft) JVW(*)M sinh/^+/wn (2)

di E.s0
To get Eq. (2) in final form we need to put Nw(t) in terms of Pd(t).
In an interval dt the net increase in the number of dipoles switched by the
362 Effective Field Approach to Phase Transitions

field is
n 27rdrSr
6NW =
V vr '
and, consequently,

(3)
< * - $ & ) ' » •

Integrating Eq. (3) from t = 0 to t = t (t <C i m ) and taking Pd(0) = —Pe,

at f (0) 2* 0,

2 7 r > « = -PdW-(-Ps) = P s ( l - ^

which connects f(t) with Pd(i) and allows us to put down the factor
7Vw(t)/x as

2n2nd TrnATX^/P^172'
fif(t) = 4M
i46 Nfi
1/2

«"- tr-o-t
1/2
(4)

where M is a time-independent factor.

The switching current, dP<±/dt, is obtained in final form substituting
Eq. (4) into Eq. (2) as

m_^_^_my^m±gm). (5)
Making use of the fact that j m [ £ m ( t m ) ] corresponds to the maximum
switching current for t — tm, Em = Em(tm) = (Eo/to)tm, which implies
'd2Pd
— Uj clTj X — t u i j
dr2
the time derivative of Eq. (5) leads directly to
1/2
Pd,
1
-,1/2

( l/2)(dP d /dt)m(l/P B ) ^(TcEm+pwPdm\

B) m^m,
(6)
J_ \T Es0 J
Eso
 Microscopic Characterization of Low-Field Switching in Ferroelectric TGS 363

which substituted into Eq. (5) for P<i{t) = P<±{tm) = Pdm, E = Em, and
taking into account that sinhx ~ x, for x -C 1, results in
-1/2 1/2
M (T, (l/2)(imim)/Ps
jm(Em)
T \T (Em + Pwjmtm)/Es0_

Tc Em + /? w P d
(7)
T Eso
We can distinguish two regimes in the behavior of jm(E„
(I) Em <C /?wjm*m leading to
1/2
jm(Em)
M (% ip\ fN^2fEm-Ecwl^/2
T \T ) \2f3wJ \PS E.sO
= Bi(Em — -E cw i) ' , (8)

where (3wPdm has been identified with Ecv,i, the domain wall coercive field
for this regime. This is the field dependence, jm(Em), found experimentally
in Fig. 4.3.2 for Em < E*m.
(II) Em » /3wjmtm resulting in

M Er, E,c w 2
jm(Em) B2 {Em — Ecv,2) (9)
T -^sO

now with the same field dependence found experimentally in Fig. 4.3.2 for
Em > -Em-
In Fig. 4.3.3 the experimental data for one of the samples are shown
together with their fits to the Eqs. (8) and (9). From these we get E^ =
0.5kV/cm, By = 199.83(mA/cm 2 )(kV/cm)- 3 / 2 , Ecvrl = 0.32kV/cm, and
B2 = 55.79 (mA/cm 2 )(kV/cm) and Ecvl2 = 0.22kV/cm, respectively.
This allows an estimation of a domain wall mean field coefficient, as
given, by /3W = E*J{jmtm) = E*J{2PS) = 0.0001, which is dimen-
sionless in esu CGS units. This is much smaller than the bulk effective
mean field coefficient for TGS, 0 = 4irTc/C = 1.1, as might have been
expected, because the cooperative effect of the unit dipoles on one side
of the wall compensates to a large extent that of the unit dipoles on the
other side.
We have used the corresponding basic parameters (see Ref. 9, p. 62,
Table 6.1) for TGS crystal in order to determine the frequencies T\ and T2
for the microscopic jump probabilities at both regimes and we find they are
«10 1 3 Hz, which is of the order of low-lying optical frequencies in TGS.
364 Effective Field Approach to Phase Transitions

40-
d = 0.08 cm o experimental data
35- s = 0 36 om2 fits

30-

)m " % ( E m" E e*2>

25-
£
20-

E
15-

10- f Jm = 8 1< E m- S cwl)

5-

rt s^
0 - 1 • 1 • 1 !•' | '1 | 1 | > 1 ' l •

0,2 0.3 0.4 0.5 0.6 0.7 OB 0.9 1

Em(kV/cm)

Fig. 4.3.3. Experimental data as in Fig. 4.3.2 for the sample with thickness 0.08 cm.
The continuous curves represent the fits obtained with the functional dependencies of
jm = Bi(Em - E d ) 3 / 2 , for Em < Em, and j m = B2(Em - Ecw2) for Em > Em.

The energy barriers for switching are in both cases small as might be
expected.
We may note as well that in the expression of B\ and £?2 there is a weak
dependence on the factor (n/A)1/2, through the factor M, which may point
out the relevance of the density of preexisting microdomains at the surface
of the crystal, related to the growing conditions of a given sample. This
would explain the differences in Fig. 4.3.2 for the three samples studied.
In subsequent measurements we have also observed that several factors as
temperature, humidity, and even the process of measure itself may produce
differences in the location of E^, but the general behavior for the two
regimes remains unchanged.
Summarizing, we have seen that a simple microscopic description of
low-field switching in TGS, showing a distinct change of regime in the
field dependence of the maximum switching current, is satisfactorily car-
ried out starting from the general rate equation, using common sense micro-
scopic considerations. The resulting expressions for jm(Em) predict well the
observed behavior, and a specific temperature dependence, which will be
the object of future works. It may be noted that this approach may be
useful to study low-field switching in ferroelectric thin films.
 Microscopic Characterization of Low-Field Switching in Ferroelectric TGS 365

Acknowledgments

T h e authors t h a n k Elias Rodriguez for his help with the experimental setup,
and J. Przeslawski, B. Mroz, and N. Cereceda for helpful suggestions. Finan-
cial support from C I C y T , Grant no. PB96-0037, is gratefully acknowledged.

References

1. C.F. Pulvari and W. Kuebler, J. Appl. Phys. 29, 1742 (1958).

2. A.G. Chynoweth and W.L. Feldman, J. Phys. Chem. Solids 15, 225 (1960).
3. E. Fatuzzo and W.J. Merz, Phys. Rev. 116, 61 (1959).
4. B. Binggeli and E. Fatuzzo, J. Appl. Phys. 36, 1431 (1965).
5. M.J. Cabezuelo, J.E. Lorenzo and J.A. Gonzalo, Ferroelectrics 87, 353 (1988).
6. J.F. Scott, L. Kammerdiner, M. Parris, S. Traynor, V. Ottenbacher,
A. Shawabkeh and W.F. Oliver, J. Appl. Phys. 64, 787 (1988).
7. H.M. Duiker and P.D. Beale, Phys. Rev. B 4 1 , 490 (1990).
8. H. Orihara and Y. Ishibashi, J. Phys. Soc. Jpn. 61, 1919 (1992).
9. J.A. Gonzalo, Effective Field Approach to Phase Transitions and Some Appli-
cations in Ferroelectrics (World Scientific, Singapore, 1991), pp. 175-199.
10. F. Jona and G. Shirane, Ferroelectric Crystals (Pergamon, New York, 1962),
pp. 48-55.
 Chapter 4.4

Brillouin Scattering Studies

of Ferroelectric Triglycine Selenate
Sound Velocity Versus Uniaxial
Pressure at T ~ T c *
J.R. Fernandez-del-Castillo and J.A. Gonzalo
Departamento de Fisica de Materiales, C-IV,
Universidad Autonoma de Madrid,
28049 Madrid, Spain

B . M r o z a n d Z. Tylczynski
Institute of Physics, A. Mickiewicz University,
Umultowska 85, 61-614 Poznan, Poland

Brillouin spectroscopy was used to study the influence of uniaxial pres-

sure ab, applied along the b polar direction, on transverse polarization
fluctuations in ferroelectric TGSe single crystals. The experiments were
performed with ab varying from 0 to 8 MPa at temperatures from 285 to
305 K. It was found that increasing pressure shifts the phase transition
temperature toward lower values, producing a slowing down of the relax-
ation process at T ~ TQ. It was also possible to induce the ferroelectric
to paraelectric phase transition at a constant temperature by varying
the uniaxial pressure.

4.4.1. Introduction

Analysis of Brillouin spectra from ferroelectric crystals undergoing o r d e r -

disorder transition is very most attractive method to study t h e so-called

•Work previously published in Physica B 262, 433 (1999). Copyright © 1999.

Elsevier B.V.

367
368 Effective Field Approach to Phase Transitions

transverse fluctuations of the order parameter, i.e., the coupling of elastic

properties with spontaneous polarization. Since the acoustic mode is piezo-
electrically coupled to these fluctuations, the strain related to the phonon
propagation induces local changes of polarization, which in turn affect the
sound velocity and the attenuation. Thus, the information about polariza-
tion relaxation time can be easily obtained from the anomalous changes of
the Brillouin line shift Av and its true width T going through the transition
temperature.
Several papers have been published on Brillouin scattering studies of
relaxation processes in various order-disorder ferroelectric systems like
TGS, 1 ' 2 TGSe, 3 RBHSO4,4 P b H P 0 4 , 5 and NH4HSO4.6 The common
features of the relevant results at the paraelectric to ferroelectric phase tran-
sition are the steps down in the phonon velocities propagating in the direc-
tions perpendicular to spontaneous polarization and associated changes in
maxima of the line width. The relaxation behavior associated with Ps could
then be well described within the Landau-Khalatnikov theory 7 giving a lin-
ear temperature dependence of the inverse relaxation time, r = A(Tc-T)^ 1 ,
with the slopes A of the order o f l O ~ n s K .
Most of the pressure studies on ferroelectric systems have been made
with hydrostatic pressure, which allows a much higher pressure applied
without cracking the sample. The results obtained for different order-
disorder ferroelectrics undergoing continuous phase transitions can be sum-
marized as follows: (i) the transition temperature depends linearly on the
applied pressure; (ii) the reciprocal dielectric constant at the paraelectric
phase follows the Curie-Weiss law and the Curie constant is almost pressure
independent; and (iii) close to the phase transition the square of sponta-
neous polarization is a linear function of both temperature and pressure. 8
The pressure dependence of the phase transition temperature (die/dp)
is usually of the order of a few K/kbar and its sign depends on the signs
and relative values of contributions (dTc/dau where £) an = p for i = 1-3)
given by the uniaxial stress applied along the main crystallographic direc-
tions. The influence of uniaxial pressure on the elastic properties of TGS
has been studied by Ramirez et al. using the Brillouin scattering technique. 9
Koralewski et al.,10 Stankowska et al.,11 and Hamed et al.12 reported on
the changes of dielectric properties of TGSe and DTGSe crystals under the
action of uniaxial pressure.
In this work, we present the results of combined uniaxial pres-
sure and temperature in the Brillouin scattering spectra of ferroelectric
(NH 2 CH2COOH) 3 H 2 Se04 (TGSe). At about 295 K TGSe undergoes a
 Brillouin Scattering Studies of Ferroelectric Triglycine Selenate 369

phase transition within the monoclinic system from the centrosymmetric

prototype point group 2/m to the ferroelectric 2 one. The experiments
have been performed with the uniaxial pressure (at,) and temperature T
varying from 0 to 8MPa, and from 285 to 305 K, respectively.
The studies presented here were undertaken: (i) to determine the influ-
ence of the uniaxial pressure on the temperature behavior of velocity of
the phonon coupled to the order parameter; (ii) to investigate the tem-
perature dependence of polarization relaxation time for different values of
uniaxial pressure 0-5; and (iii) to verify the hypothesis regarding the possi-
bility of shifting the system from ferroelectric phase to paraelectric phase at
constant temperature by applying a uniaxial pressure. We believe we have
accomplished the above objectives.

4.4.2. Experimental Procedure

Single crystals of TGSe were grown at the paraelectric phase (305 K)

from the water solution of the initial components at the stoichiomet-
ric proportion. Colorless and good-optical quality crystals were obtained.
Since our experiment was focused on the critical behavior of the quasi-
longitudinal phonon propagating along the c crystallographic direction, for
which the elastic anomaly (due to the transverse fluctuation of Ps) is most
pronounced, 3 the scattering geometry was the following. The sample was
illuminated along the direction of the bisectors of a*_ and c-axis. The scat-
tered light was observed at 90° to this direction and the uniaxial pressure o\,
was applied along ferroelectric direction b.
All surfaces of the samples of typical size 6 x 7 x 7 mm 3 were optically
polished. The flatness of the samples faces, especially those perpendicular to
the b direction, was checked with the Newton's rings method. It should be
noted that TGSe is a very delicate crystal to study under applied uniaxial
pressure. Any departure from perfect parallelism of the surfaces perpendic-
ular to the b direction led to sample cracking.
The incident light provided by a stabilized single-mode argon-ion laser
(Spectra Physics, Model 2020) operating at 514.5 nm was polarized per-
pendicularly to the scattering plane. The scattered light was analyzed at
90° using a piezoelectrically scanned triple pass Fabry-Perot interferom-
eter (Burleigh Model RC-110) with free spectral ranges (FSR) 44 and
24 GHz. With a normal finesse of about 45 the instrumental line width
Fi did not exceed 0.55GHz (for the smaller FSR). Any drifts due to the
370 Effective Field Approach to Phase Transitions

laser, electronics, or the Fabry-Perot were automatically compensated by a

PC-based data acquisition and control system (FPDACS-MUN, Canada). 13
The relation between the observed Brillouin line shift Av and the sound
velocity v is given by the Brillouin equation:

Av = \v(nf +nj - mns cos @)~1/2, (1)

where A is the wavelength of the incident light, rii and ns are refractive
indices for the incident and scattered light, respectively, and 0 is the scat-
tering angle.
The uniaxial pressure and temperature dependence of the Brillouin scat-
tering spectra of TGSe were collected using a vacuum-insulated container
constructed for this purpose. The container consists of a heating-cooling
holder inside which the sample was placed between two metal pistons. The
uniaxial pressure was applied by squeezing an accurately calibrated spring.
To avoid sample cracking a thin (15 /xm) metalized mylar foil was placed
between the sample and pressing pistons. The estimate error of the applied
stress was less than 3%. The temperature of the sample was regulated
with a stability of ±0.02 K using an Oxford (model ITC 4) temperature
controller. The thermocouple was glued to the sample using the thermo-
conductive paste.

4.4.3. Results and Discussion

In Fig. 4.4.1, we present the temperature dependence of the Brillouin line

shift Av proportional to the quasi-longitudinal phonon velocity W[ooi] and
the related changes of the true line width T obtained after deconvolution
with the instrumental line width (Fig. 4.4.1(b)). 14 A step-like anomaly was
observed when cooling the sample from the paraelectric phase to the fer-
roelectric phase. The uniaxial pressureCTJ,was shifting TQ toward lower
temperatures, as expected. However, the shift of the phase transition tem-
perature was found to be —0.15K/MPa, which is bigger than those reported
in Refs. 10 and 11 (—0.09K/MPa). In addition, a well-pronounced decreas-
ing of the step in velocity with increasing pressure was observed. The inset
in the Fig. 4.4.1(a) demonstrates that, for a^ of the order of 20MPa, this
step anomaly should decrease linearly to zero. The results presented the
Fig. 4.4.1 allowed us to estimate the temperature changes of the polariza-
tion relaxation time r for different uniaxial pressures.
 Brillouin Scattering Studies of Ferroelectric Triglycine Selenate

,,i , , , ! , , , (
as 280 S6 309 90S
T(K)

Fig. 4.4.1. Temperature dependence of Brillouin line shifts related to the quasi-
longitudinal phonon [0 0 1] for different constant values of uniaxial pressure (a) and
related changes of the line width (b). The vertical scale in the inset is in GHz. All lines
are guided on eye.

Assuming that a single relaxation time, r, is appropriate, it can be

determined by combining two equations, the first of which expresses15 the
dependence of the sound velocity, v, on frequency, to,

»2=^ + ( ^ - ^ V ( i + u V ) - 1 . (2)
Here, vx is a limiting high-frequency velocity and VQ is a sound veloc-
ity not affected by the transition. The second equation is a corresponding
expression for sound attenuation,

a = (2«)-3(^-VoVr(l+^2r2)-1. (3)
The relaxation time r is then given by
r=(2a)-lv-3(v2-v20), (4)
372 Effective Field Approach to Phase Transitions

S; l ,, U J . 1 u.,. | i... 1 .a.,

TT,M,1*''^'"r'-""« • ! •

*•

4 /

5 3
o
•
&2
V
JV /
// tf
rX
1
- aJy
jy Q a^ =
o
0 M?«, A » (1 jfifttaSO) 1 (H > s K
s s = 3;JMP4. A - (3,75*0.25} K M ' s K
i
JP 9 a = &9Mfti, A-=<2.aM&30) t4r»aK

10
(Tc-T) (K)

Fig. 4.4.2. Temperature dependencies of the inverse relaxation time, in the ferroelectric
phase, for different values of uniaxial pressure.

and can be calculated from the true width of the Brillouin line, which is
related to a by the relation: T = av. The obtained temperature dependen-
cies of the inverse relaxation times T " 1 are given in Fig. 4.4.2.
The observed changes follow the Landau-Khalatnikov expression r =
A(TQ — T ) _ 1 with slopes A increasing for rising stresses. This indicates the
role of the uniaxial pressure applied along the spontaneous polarization in
slowing down the relaxation process.
Attempts were undertaken to check the possibility of passing the fer-
roelectric phase transition at a fixed temperature, varying only the uniax-
ial pressure <7{,. The temperature of the sample was set at 293.20K, i.e.,
almost 2° below T o Brillouin spectra were then collected for several rising
values of <T(,. The obtained results are presented in Fig. 4.4.3. Both the line
shift Av and the line width T show the distinct anomalies at some criti-
cal pressure of about 4.2 MPa. The Brillouin shift increases with the rising
Ob, from about 15.5 GHz (ferroelectric phase) to about 15.8 GHz (paraelec-
tric phase). The anomaly in T as a function of a\, indicates additionally
that the ferroelectric phase to paraelectric phase transition took place. The
results presented in Fig. 4.4.3 allowed the estimation of the uniaxial pressure
dependence of the relaxation time. The result is given in Fig. 4.4.4. Despite
 Brillouin Scattering Studies of Ferroelectric Triglycine Selenate 373

r 1
1W» T l ' "r"'-'"-,Lr~T • i S ' 1 — • - 0,8
• •

A w •
• - 0,7
16,76

/ ° 5f* 0,8
1Am - o/ /I .
*• o,s
j£f«* &
IT*
-"•o
MR
"saw t/
J
\° \
:
- fta

•\&m
H
T = 293.2 K 0.2

ji™* Oil
T Z 3 4 5 6 7 8 S

Fig. 4.4.3. Brillouin line shift and its width versus uniaxial pressure at constant tem-
perature (293.2 K). Lines are guided on eye.

1 '
%.*
1.Z

• / "
1.0

/
k" •
/
/
* .
•
r
„,.-'
*" flL* • y
-
• •

jI
u r :
• * _ _ i i ' • ' •

a -afMPaji

Fig. AAA. The uniaxial pressure dependence of inverse relaxation time in the ferroelec-
tric phase.
374 Effective Field Approach to Phase Transitions

the rather poor accuracy, it may be said that r at constant temperature

under an uniaxial pressure (as the active thermodynamic force) follows the
rule: r = A(ac -a)'1, with the slope A= (2.9 ± 0.3)10 - 1 1 sMPa.

4.4.4. Conclusions

The results presented above lead to the following conclusions. The data
regarding the phonon velocity W[ooi] and its attenuation obtained by the
Brillouin scattering technique for different values of the uniaxial pres-
sure, <7b, indicate a strong coupling to the spontaneous polarization. This
is manifested (for er;, = 0) by the step-like change of i>[ooi] versus temper-
ature and accompanied by a distinct maximum of the Brillouin line width
at TQ . The same temperature dependencies obtained for o\, ^ 0 are less pro-
nounced: the step down in velocity becomes smaller with increasing uniaxial
pressure. With the assumption that these changes are proportional to <Jb, it
is estimated that for <7b of the order of 20 MPa the step change of velocity
at the actual phase transition temperature should become undetectable.
The temperature dependencies of the relaxation time r of the transverse
polarization fluctuations were found to be sensitive to the constant uniaxial
pressure applied along the polarization direction. The observed changes can
be described within the Landau-Khalatnikov theory giving r = A(TQ —
T ) _ 1 , with the slopes A proportional to the applied ov
Additionally, it was demonstrated that, by applying uniaxial pressures
at constant temperature, the crystal studied undergoes the phase transition
from the ferroelectric phase to the paraelectric phase.

Acknowledgments

We wish to acknowledge financial support from MEC through grant PB96-

0037. One of the authors (B.M.) wishes to thank the Spanish Ministry of
Education and Culture for supporting him with sabbatical grant (SAB95-
0460). We are indebted to Prof. M.J. Clouter for his help in developing the
hardware and the kind donation of software of FPDACS. Thanks are due
to A. Karayev for the samples preparation.

References

1. W. Gammon and H.Z. Cummins, Phys. Rev. Lett. 17, 193 (1966).
2. Luspin and J.P. Hauret, Ferroelectrics 15, 43 (1977).
 Brillouin Scattering Studies of Ferroelectric Triglycine Selenate 375

3. T. Yagi, M. Tokunaga and I. Tatsuzaki, J. Phys. Soc. Jpn. 40, 1659 (1076).
4. Y. Tsujimi, T. Yagi, H. Yamashita and I. Tatsuzaki, J. Phys. Soc. Jpn. 50,
184 (1981).
5. B. Lavrencic, M. Copic, M. Zgonik and J. Petzelt, Ferroelectrics 2 1 , 325
(1978).
6. Hikita and T. Ikeda, J. Phys. Soc. Jpn. 42, 351 (1977).
7. D. Landau and J.M. Khalatnikov, Sov. Phys. Dokl. 96, 469 (1954).
8. Jona and G. Shirane, Ferroelectric Crystals (Pergamon, London, 1962).
9. R. Ramirez, C. Prieto and J. Gonzalo, Ferroelectrics 100, 181 (1989).
10. J. Koralewski, Stankowska, T. Iglesias and J. Gonzalo, J. Phys.: Condens.
Matters, 4079 (1996).
11. J. Stankowska, I. Polovinko and J. Stankowski, Ferroelectrics 2 1 , 529 (1978).
12. E. Hamed, Phase Transitions 38, 43 (1992).
13. M.J. Clouter, Data Acquisition and Control System for Fabry-Perot Inter-
ferometry, User's Manual (Version 2.02, 1997). Memorial University of New-
foundland, St. John's, A1B 3X7 Canada.
14. A. Pinov, S.J. Candau, J.T. la Macchia and T.A. Litovitz, J. Acoust. Soc.
Am. 43, 131 (1968).
15. R. Blinc and B. Zeks, Soft Modes in Ferroelectrics and Antiferroelectrics
(North-Holland, New York).
 Chapter 4.5

Piezoelectric Resonance
Investigation of Zr-Rich P Z T
at Room Temperature*
N. Cereceda, B. Noheda, J.R. Fdez.-del-Castillo
and J.A. Gonzalo
Departamento de Fisica de Materiales,
Universidad Autonoma de Madrid, Cantoblanco,
28049 Madrid, Spain

J. De Frutos
ETSI Telecomunicacion (UPM), Ciudad Universitaria,
28040 Madrid, Spain

A.M. Gonzalez
EUIT Telecomunicacion (UPM), Ctra. Valencia,
28031 Madrid, Spain

We study the piezoelectric resonances in poled PZT ceramics by means

of a microscopic model. It connects the microscopic vibrations of the
ionic units, cooperatively producing the piezoelectric effect, with the
macroscopic piezoelectric parameters. The behavior at the resonance is
well described in a wide range of frequencies, allowing the calculation
of piezoelectric constants and the electromechanical coupling factors in
terms of microscopic quantities.

*Work previously published in J. Eur. Ceram. Soc. 19, 1259 (1999). Copyright © 1999.
Elsevier B.V.

377
378 Effective Field Approach to Phase Transitions

4.5.1. Introduction

The use of piezoelectric ceramics is quite extended, because of their reliabil-

ity in producing detectors, actuators, and different useful devices.1 However,
this cooperative effect is still not completely understood. Early attempts
made by Schrodinger, Larmor, and Born to use modern lattice dynamics
in the description of piezoelectricity were unequal to the task of predicting
anything better than a rough approach to the order of magnitude of the
piezoelectric effect in the simplest structures. 2 Piezoelectricity is a property
appearing in all 20 non-centrosymetric crystal classes, 3,4 and then includes
a lot of types of materials, among ferroelectrics.
The use of modern calculation techniques allowed some authors to
obtain valuable first-principle results for the piezoelectric parameters
in some simple compounds. 5,6 In perovskites the calculations based on
LAPW-LDA provide some explanations about the origin of ferroelectricity
and piezoelectricity in these materials. 7 Recently, some authors presented
calculations of piezoelectric properties in pure and mixed perovskites. 8 ' 9
All these calculations are not entirely based on first principles, because
they always use some input from experiments, such as the lattice constant,
which is critical to get stable structures.
Escaping from first-principles and ab initio calculations, we propose a
microscopic approach to the piezoelectric resonances. The model described
in this work is based on a classical forced and dumped oscillator and allows
the expression of the piezoelectric coefficients and the electromechanical
coupling factors in terms of microscopic quantities.
The material investigated in this work is the well-known PZT: a lead
zirconate-lead titanate solid solution (PbZri_ x Ti x 03). In the Zr-rich region
of compositions it presents a ferroelectric phase with rhombohedral geome-
try below the ferroelectric transition temperature. This phase is divided
into two other ferroelectric regions (FRL and FRH for low- and high-
temperature phases, respectively), in which the positions of cations and
oxygen octahedra play a fundamental role. 10,11 The transition temperature
(ILH) between them varies from room temperature up to 150°C, depending
on composition.4

4.5.2. Experimental

We have characterized the piezoelectric resonances in PZT 96.3/3.5 +

lwt.% ND2O5 ceramic samples. They were sintered at the Shanghai
 Piezoelectric Resonance Investigation of Zr-Rich PZT 379

Institute of Ceramics, Shanghai (China), by ordinary methods. The sam-

ples were silver-electroded and poled by applying 2kV/cm during 10 min
at 125°C in silicon oil medium.
The dielectric response was determined by means of a Hewlett-Packard
HP4194A-LF impedance analyzer, and characterized using a specially
designed software. 12,13 By this way we collected data for the elastic con-
stants, piezoelectric coefficients, and electromechanical coupling factors in
complex form.

4.5.3. Theoretical Model

The model simplifies the material assuming an arrangement of ions placed

into alternating layers of positive and negative charges along the ferro-
electric axis. In this approach, it is assumed that positive charges (+2)
correspond to the P b 2 + ions and the negative charges (—2) correspond to
the [(Zr/Ti)0 3 ] 2 - packed ions.
We assume the motion of these layers to be described by a forced-
dumped oscillator, where k(d)x± is the restoring force, M±~f(d)dx±/dt
is the viscous force, and qEes(d) exp{—icut} is the effective electric force,
driven by the external applied field, EQ exp{—iwt}. The net displacement,
x = x+ — X-, connects with the extension of the material, caused by, let us
say, an accordion effect.
The thickness dependence is included in the description, according to the
principle that piezoelectricity is a macroscopic cooperative phenomenon,
with the boundary conditions playing a fundamental role. The complex
dielectric response is
* ./i . .
£ =£cd + - ^ JT :—, (1)

where LjQk(d)/M is the characteristic frequency of the system, A(d) is the

amplitude of the resonance, 7(d) is the corresponding dumping factor, and
M is the effective mass, defined as 1/M — 1/M+ + 1/M_. Only these
thickness-dependent parameters are needed to characterize the resonance,
as shown below. The "clamped" dielectric constant, £ccj, does not depend
on sample thickness.

4.5.4. Results and Conclusions

As is known, disk geometry possesses thickness extensional and radial mode

vibrations. Figure 4.5.1 represents the dielectric response found for PZT
380 Effective Field Approach to Phase Transitions

5 e
f^*, MHz

Fig. 4.5.1. Thickness mode resonance in the P Z T 96.5/3.5 + lwt.% ND2O5 sample.
e' and e" represents real and imaginary parts of Eq. (1). The fitting parameters are
indicated in the plot.

96.5/3.5 + lwt.% ND2O5 ceramic during the thickness mode resonance

in a sample with d = 0.4 mm thickness and 2r = 1cm diameter. Points
and crosses represent the experimental points for real (e') and imaginary
(e") parts, respectively. Lines represent the corresponding theoretical fits,
according to Eq. (1). As can be seen, each fit reproduces adequately the
experimental behavior in a wide range of frequencies.
We studied both thickness and radial mode resonances for samples with
different sizes. Figure 4.5.2 reproduces the dependence of the parameters
wo, A, and 7 versus thickness for the longitudinal mode resonance. A similar
study has been made for radial mode resonance. Table 4.5.1 summarizes the
results.
The behavior found for the characteristic frequency, uio(d), agrees with
the expected one, because it is determined by the boundary conditions.
As can be observed from Fig. 4.5.1, there exists a "jump" in the dielec-
tric constant, Ae, which is not size-dependent and can be defined as
Ae' = e'(tj —> 0) — e'(u> —> 00) = A(d)/u>o{d). This jump is related to
the electromechanical coupling factor as follows: at the thickness mode res-
onance we expect e'(0) = £33 and £^d(oo) = £| 3 , so we may write, according
 Piezoelectric Resonance Investigation of Zr-Rich PZT 381

l/rf,tnm"'

Fig. 4.5.2. Thickness dependence of the fitting parameters A, Wod, and 7.

Table 4.5.1. Dependence of the fitting

parameters with thickness (d) and radius (r).

Thickness mode Radial mode

2
ocl/d oc 1/r 2
7 ocl/d2 ocl/r4
A ocl/d2 ex 1/r 2

to Meitzler 14.
Ae Ae
*? = £(0) Ae + £ c d '
(2)

which is the thickness electromechanical coupling factor.

We may interpret this as follows. Extrapolating to the case in which
the atomic chains consist of only two unit cells (d = 2a), there exists a
microscopic elastic constant, K^, and an associated characteristic frequency,
wo(2a). Then, for uJo{d) we may write

u20(d) = (Kd/M)(2a/d)2, (3)

382 Effective Field Approach to Phase Transitions

where a is the lattice parameter. In our samples we found that wo(2a)/27r =

2.8 x 1012 Hz, which is a reasonable value for a low-lying purely ionic mode
resonance.
For the total viscous force we consider that the cooperative effect during
the resonance leads to a sharing of the atomic viscous force and to a total
viscous force parameter expressed by
2
7(rf)=rd(2a/d) , (4)

where Td = 7(2a) is constant.

On the other hand, A(d) oc l/<i2 is connected with the fact that Ae is
constant:
A{d) _ A-wNg2 EeBJcQ/E
A £
W - -273T
u%{d)- ~—~nM ,,fiwl(d)
(A\ • W

In a centrosymmetric (non-piezoelectric) ionic crystal, the ratio

(Eeg/E) is given by Ae/3, combining Lorentz's and Claussious-Mossotti's
relations. 15 In a piezoelectric crystal the strength of Ees(d), driven by the
external field E, is shared by (n+n~) = [(d/2)/a\2 charged pairs. The effec-
tive electric field Eefi results in

EeS(d)/E=^[2a/d}2. (6)

From the above discussion, we may get the piezoelectric coefficient d^z
as follows:
5d/d _ x/2a _ 1 {q/M)(EeS(d)/E)
d33 = —£T = —ET = o ..,2/JN ' V)
~E~ ~ E ~~2 aujl{d)
and using Eqs. (5) and (6) we get

(8)
*-K^)^-
By using the values q = 2e, a = 4 A, Ka = 4 x 104 (dyn/cm) and
Ae d = 30, we get d33 = 101 x 1 0 - 1 2 C/N. This value is somewhat smaller
than I//133 = 320 x 10~ 12 C/N, used to estimate it, but it lies in an expected
value in accordance with the values in the literature.
The results and the above theoretical development are also applicable
to radial mode piezoelectric resonances. Figure 4.5.3 represents the results
found for the dielectric response through the radial mode resonance. As can
be observed, this resonance is narrower than the thickness one.
 Piezoelectric Resonance Investigation of Zr-Rich PZT 383

• |" HUlflM

600 1400

400 1200
S/ mJ2n
m i i i m l
1000
200

800
0
i

-200

•400
J2a_JL.'»<-
r /2,t
600

400

200
-600
Hmilllililll)ll1HIIII>|IIIHIIIIIIIItllllllltll[llllr THllllllll|IIIIIMIHlllllllllllll|llllllllllllllllllllllll|IIIMIIIIIIIIIIIIIHIIII

200 250 300 350

f=W2n, kHz

Fig. 4.5.3. Dielectric response, radial-mode piezoelectric resonance.

In order to calculate the piezoelectric coefficient d^i we use now the val-
ues KT = 4 x 104 dyn/cm and Ae r = 5, where the sub-index "r" indicates
"radial." Then, by using Eq. (8) applied to this resonance, we get ofai =
11.6 x 1 0 - 1 2 C/N, which is in good agreement with the observed one during
the standard characterization. The planar electromechanical coupling fac-
tor, kt, can be easily calculated by again using Meitzler criterion, 14 using
now e'cd = e'r(oo) = e^3, £'r(0) = ej 3 , and the relation eg3 = ej 3 (l - fct2).
Table 4.5.2 shows the final results obtained in comparison with the previ-
ously done macroscopic characterization.

Table 4.5.2. Comparison of the results obtained after

analysis with the "standard" method and with the
"microscopic" approach.

^33 <fei kt

Macrosc [<320]* 11.5 0.35 0.14

Microsc 101 11.6 0.35 0.12

*Not directly determined. Estimated using ^33 <

I//133. Parameters ^33 and 1^31 are given in units of
xHT12C/N.
384 Effective Field Approach to Phase Transitions

According to all these results, there is a simple description of the

piezoelectric resonance in t e r m s of microscopic quantities, establishing
connection between the usual interpretation (macroscopic) and the fun-
damentals of the material. In principle, this microscopic approach could be
used directly in other piezoelectric perovskites, and possibly in other piezo-
electric materials. Our description works quite well not only at frequencies
close to the resonances, but also far from them.

Acknowledgments

T h e authors wish to acknowledge the financial support from C I C y T (PB96-

0037), the Spanish Committee for Scientific and Technological Research,
and N A T O (CGR-0037).

References

1. J.C. Burfoot and G.W. Taylor, Polar Dielectrics and their Applications
(Macmillan, London, 1979).
2. W.G. Cady, Piezoelectricity. An Introduction to the Theory and Applications
of Electromechanical Phenomena in Crystals (Dover, New York, 1964).
3. W.P. Mason, Crystal Physics and Interaction Processes (Academic Press,
New York, 1966).
4. B. Jaffe, W.R. Cook and H. Jaffe, Piezoelectric Ceramics (Academic Press,
New York, 1971).
5. A.D. Corso, M. Posternack, R. Resta and A. Baldereschi, Phys. Rev B 50(15),
10715 (1994).
6. F. Bernardini, V.D. Fiorentini and D. Vanderbilt, Phys. Rev. B 56, R10024
(1997).
7. R.E. Cohen, Nature 358, 136-138 (1992).
8. G. Saghi-Szabo, R.E. Cohen and H. Krakauer, Ferroelectrics 194, 350 (1997).
9. E. Cockayne and K. Rabe, Phys. Rev. B 57(22), R13973 (1998).
10. A.M. Glazer, S.A. Mabud and R. Clarke, Acta Crystallogr. B34, 1060 (1978).
11. B. Noheda, T. Iglesias, N. Cereceda, J.A. Gonzalo, H.T. Chen, Y.L. Wang,
D.E. Cox and G. Shirane, Ferroelectrics 184, 251-255 (1996).
12. A.M. Gonzalez and C. Alemany, J. Phys. D: Appl. Phys. 29, 2476-2482
(1996).
13. C. Alemany, L. Pardo, B. Jimenez, F. Carmona, J. Mendiola and A.M.
Gonzalez, J. Phys. D: Appl. Phys. 27, 148-155 (1994).
14. A.H. Meitzler, H.M. Tiersten Jr. and H.F. Tiersten, IEEE Trans. Sonics
Ultrasonics SU20, 233-239 (1973).
15. A.J. Dekker, Solid State Physics (Prentice-Hall, Englewood Cliffs, NJ, 1962).
 Chapter 4.6

Transition Temperature Dependence

in Perovskite Ceramics
as a Function of Grain Size*
M.I. Marques, N. Cereceda and J.A. Gonzalo
Departamento de Fisica de Materiales,
C-IV Universidad Antonoma de Madrid, 28049 Madrid, Spain

Simple effective field arguments assuming a nonisotropic layer of thick-

ness Lc covering the ferroelectric bulk grain of perovskite ceramics are
used to determine an expression for the transition temperature TC(L) as
a function of grain linear size L. The surface to volume ratio increases as
L decreases, reducing the value of TC(L). Experimental data for BaTiC>3
ceramics as a function of grain size are described reasonably well by the
expression of TC(L) obtained this way.

4.6.1. Introduction

Grain size effects on the physical properties of ferroelectric ceramics have

been investigated by several a u t h o r s . 1 - 5 Results on B a T i 0 3 ceramics show
t h a t the ferroelectric (cubic-tetragonal) transition is suppressed for grain
sizes below about 0.09 /an. As the grain size decreases and the surface to
volume ratio of the grain decreases, one may expect t h a t in the ferroelectric
phase the unit cells near the surface order nonisotropically with respect to
the unit cells in the bulk of the grain. This may give rise to a weakening of
the overall cooperative interaction of the dipoles within the grain, resulting
in a lowering of transition t e m p e r a t u r e .

*Work previously published in Ferroelectrics Letters 25, 103 (1999). Copyright © 1999.
Taylor & Francis Group.

385
386 Effective Field Approach to Phase Transitions

In a recent review by Niepce 3 on permittivity of fine-grained BaTiC-3

ceramics, data by Henning 3 indicate that TC{L) ~ 25°C (298.15K) for Lc ~
0.8 fim. On the other hand, data by Uchino et al.4 show that TC(L) ~ 20°C
(293.15 K) for Lc ~ 0.095 /xm. The qualitative behavior of TC(L) in both
sets of data is the same, but the critical grain size to bring down Tc to room
temperature is different.
There are possible reasons for this discrepancy, but we will use the data
of Uchino et al.4 later for numerical comparison with our calculated TC(L),
based on simple effective field arguments, as shown below.

4.6.2. Theoretical Approach

For a single crystal or a large single grain, effective field arguments 6 lead to
the identification of kBTc, the thermal energy per unit dipole, with ESQIJL,
the interaction energy of the local spontaneous field at T = 0 K with the
unit electric dipole per unit cell. Therefore,
kBTc » Es0ii « pNv2, (1)
where Eso = (3Pso = /3N(i, /? = 4irTc/C being the effective field coefficient
that is given in terms of the observed transition temperature, T c , and the
observed Curie constant, C ( e _ 1 ~ (T-Tc)/C at T not far from T c ).
Consider a ceramic with cubic-like grains in which a ferroelectric bulk
central cube of volume (L — L c ) 3 surrounded by an nonisotropic surface layer
of volume [6(L - Lc)2{Lc/2) +12 (L - L c ) (Lc/2)2 + 8(L c /2) 3 ] (see Fig. 4.6.1).
For a cubic-like grain of arbitrary linear size L and surface layer of
thickness Lc, instead of Eq. (1), we would have

kBTc(L,Lc) = kBTc(oo,Lc)

3LC , ^ ,„ 3LCC Peb 2 ^ &

/?(Msi//i)2 . /3(/WA0 , 1(MCC/M) 2
+ +
(L-Lc) {L-Lcf {L-Lcf

(2)
with L » Lc, Eq. (2) results in
Tc(L,Lc)«Tc(oo,Lc), (3)

with L -> Lc and (/3cc//?)(/xcc//i)2 < 1, Eq. (2) gives

2n
/?cc/
T c (L,L c )«T c (oo,L c ) <T c (oo,L c ), (4)
7
 Transition Temperature Dependence in Perovskite Ceramics 387

(L-Lc)LcLc/4
bar

T • ^ - • w > ';-^Frw.

(L-Lc)(L-Lc)Lc/2 L-Lc
Layer

T
LcLcLc /8
comer cube

Fig. 4.6.1. Cubic-like perovskite grain (projection on plane) made up of a central bulk
ferroelectric region of volume (L — Lc)3, with unit cell dipole moment fi, surrounded by
surface nonisotropic layers with unit cell dipoles (—fisi) (as the one shown in white), edge
bars, with unit cell dipoles (±/z e b) (as the one shown in light gray), and corner cubes,
with unit cell dipoles (±/i C c) (as the one shown in black). Note that there are six surface
layers of volume (L — Lc)2Lc/2, 12 edge bars of volume (L — Lc)Ll/A, and eight corner
cubes of volume L;?/8. Effective field coefficients for the three zones are /3 sl , f3eb and /3CC,
respectively.

as expected. With arbitrary L in the interval Lc < L < oo we can compare

Eq. (2) with data for fine-grained BaTiOa ceramics by Uchino et al.4

4.6.3. Results

Figure 4.6.2 shows a fit of Eq. (2) to these data in semilog representation.
The parameter values for a best fit are given by

T c (oo,L c )=T c (oo) 401.72 ± 1.7 (K)

0.095 (/im)
(/V/3)(/WM) 2 1.018 ±0.016
(/W/?)(/W/i)2 0.98 ±0.012
(/W/?)(/WM) 2 0.8488 ± 0.0064

The fit is reasonably good and the values for (/Usi//x), (/ieb/A*), and
(/i cc //i) seem to be of order unity.
388 Effective Field Approach to Phase Transitions

420 .

s
400 -

360 .

T c (° K) ™ -
340 -

320 -

300 .

2ao -

0.1 1
L(Mfn)

Fig. 4.6.2. Fit of TC(L, Lc), Eq. (2), to experimental data by Uchino et al.4 on BaTiOs
ceramics.

Work on Monte Carlo simulations of fine grain effects on the transi-

tion t e m p e r a t u r e of three-dimensional finite-size Ising systems is currently
investigated for comparison with experimental data.

Acknowledgments

Financial support from C I C y T (PB96-0037) is acknowledged.

References

1. K. Kinoshita and A. Yamaji, J. Appl Phys. 47, 371 (1976).

2. G. Arlt, D. Hennings and G. de With, J. Appl. Phys. 58, 1619 (1985).
3. D. Hennings, Int. J. High Technol. Ceram. 3, 91 (1987).
4. K. Uchino, E. Sadanaga and T. Hirose, J. Am. Ceram. Soc. 72, 1555 (1989).
5. J.P. Niepce, Electrocerarmics 4, p. 29, Aachen, September 5-7 (1994).
6. See, for instance, J.A. Gonzalo, Effective Field Approach to Phase Transitions
and Some Applications to Ferroelectrics (World Scientific, Singapore, 1991).
 Chapter 4.7

A Monoclinic Ferroelectric P h a s e
in t h e Pb(Zr 1 _ a ; Ti a ; )03
Solid Solution*
B. Noheda, D.E. Cox and G. Shirane
Physics Department, Brookhaven National Laboratory,
Upton, New York 11973-5000, USA

J.A. Gonzalo
Dept. Fisica de Materiales, U.A.M., Cantoblanco,
28049 Madrid, Spain

L.E. Cross and S.-E. Park

Materials Research Laboratory,
The Pennsylvania State University,
Pennsylvania 16802-4800, USA

A previously unreported ferroelectric phase has been discovered in a

highly homogeneous sample of PbZro.52Tio.4gO3 by high-resolution syn-
chrotron X-ray powder diffraction measurements. At ambient tempera-
ture the sample has tetragonal symmetry (o t = 4.037 A, c t = 4.138 A),
and transforms below ~250 K into a phase that, unexpectedly, has mono-
clinic symmetry (a m = 5.717 A, bm = 5.703 A, c m = 4.143 A, j3 = 90.53°
at 20 K). The intensity data strongly indicate that the polar axis lies in
the monoclinic ac plane close to the pseudocubic [111] direction, which
would be an example of the species m3m(12)A2Fm predicted on sym-
metry grounds by Shuvalov.

*Work previously published in Appl. Phys. Lett. 74, 14 (1999). Copyright © 1999.
American Institute of Physics.

389
390 Effective Field Approach to Phase Transitions

The solid solution system Pb(Zri_ x Ti x )03 (PZT) has a complex phase dia-
gram containing a number of materials that exhibit useful ferroelectric and
piezoelectric properties. In particular, compositions near the morphotropic
phase boundary (MPB) around x « 0.45-0.5 have attracted considerable
interest for many years due to their high piezoelectric response. The PZT
phase diagram, as now accepted, was determined by Jaffe et al.1 (Fig. 4.7.1),
and nearly four decades of study on the physical and structural properties of
PZT have made possible the development of a phenomenological theory to
explain the stability of the phases and the properties of PZT over the entire
range of the phase diagram. 2 Nevertheless, many questions still remain. It
is generally accepted that for ferroelectric compositions with rhombohedral
and tetragonal symmetry on the two sides of the MPB the polar axis are
[111] and [001], respectively. However, very recently, based on neutron pow-
der diffraction data for several ferroelectric rhombohedral compositions in
the range of x « 0.12-0.40, Corker et al.s have proposed a model in which
random (100) Pb displacements are superimposed on those along the [111]
polar axis, which allows a much better structure refinement than achieved
with a normal long-range order model incorporating anisotropic tempera-
ture factors.
The MPB, which separates rhombohedral Zr-rich from tetragonal Ti-
rich PZT, is nearly vertical along the temperature scale, and many X-ray
diffraction studies have been reported over this region.4~9 This boundary is
not well defined since it appears to be associated with a phase coexistence

o to t o » «6 «5 So TO s o s o too
pbZrO, Molt % PbTlOj PfrTK),

Fig. 4.7.1. P Z T phase diagram after Jaffe et al.1

 A Monoclinic Ferroelectric Phase in the Pb(Zr\-xTix)C>2, Solid Solution 391

region whose width depends on the compositional homogeneity and on the

sample processing conditions. 7 ~ 10 Cao and Crosse 11 have modeled the width
of this region based on the free energy differences between the tetragonal
and rhombohedral phases, obtaining an inverse dependence with particle
size in a polycrystalline sample.
In the present work, we have utilized high-resolution synchrotron X-ray
powder techniques to study the structure of a composition close to the MPB
(x = 0.48) as a function of temperature, and we report the observation of
a low-temperature monoclinic phase in the PZT system.
A PZT composition with x — 0.48 was prepared by conventional solid-
state reaction techniques using appropriate amounts of reagent-grade pow-
ders of lead carbonate, zirconium oxide, and titanium oxide, with chemical
purities better than 99%. Pellets were pressed and heated to 1250°C at
a ramp rate of 10°C/min, and held at this temperature for 2 h. During
sintering, PbZrC-3 was used as a lead source in the crucible to minimize
volatilization of lead. The product was found to be a single phase within a
detection limit of <2% by conventional X-ray techniques.
High-resolution synchrotron X-ray powder diffraction measurements
were made at beam line XIA at the Brookhaven National Synchrotron
Light Source. An incident beam of wavelength 0.6896 A from a G e ( l l l )
double-crystal monochromator was used in combination with a Ge(220)
crystal and scintillation detector in the diffraction path. The resulting
instrumental resolution is about 0.01° on the 29 scale, an order of magni-
tude better than that of a laboratory instrument. For measurements above
room temperature, the pellet was mounted on a BN sample pedestal inside a
wire-wound BN tube furnace. The furnace temperature scale was calibrated
with a sample of CaF2. The accuracy of the temperature was estimated to
be within 10 K, and the temperature stability was ~2 K. For measurements
below room temperature, the pellet was mounted on a Cu sample holder and
loaded in a closed-cycle He cryostat, with an estimated temperature accu-
racy of 1K and stability of 0.1 K. Coupled 9-29 scans were performed over
selected angular regions with a 29 step interval of 0.005 or 0.01° depending
on the peak widths. The sample was rocked 1-2° during data collection to
improve powder averaging. The diffracted intensities were normalized with
respect to the incident beam monitor.
The evolution of the (111) and (220) reflections is shown as a func-
tion of temperature in Fig. 4.7.2. At the highest temperature reached
(736 K), the material is cubic and the sharpness of the peaks [full-width
at half-maximum (FWHM) ~0.02°] demonstrates the excellent quality of
392 Effective Field Approach to Phase Transitions

10ao
(a) <111)c X=0.48 (220) c
T-736 Kf
500

0
(b)
T=300K ioo^T

JM_ o

I50Z
e
o

•H U T _ *^*wn.i
0 0

500 T=20K 150

" i S m f i 17",0 " 27.3 ' 27",6 27.9 28.2°

29 (deg) 2B (deg)

Fig. 4.7.2. Evolution of the pseudocubic reflections (111) and (220) for x = 0.48 from
T = 736 (a) to 20 K (e).

the sample [Fig. 4.7.2(a)]. From a Williamson-Hall plot, 12 we estimate a

particle size of ~0.7/xm and a Ad/d of about 3 x 10~ 4 , corresponding to a
compositional inhomogeneity, Ax, better than ±0.5%.
On cooling, the symmetry changes to tetragonal at ~660 K and remains
tetragonal down to 300 K. There is no sign of any rhombohedral component
as shown by the absence of a Bragg peak at the rhombohedral (200) posi-
tion. However, some of the tetragonal peaks broaden as the temperature
is lowered, especially the (111) and (202) reflections [Fig. 4.7.2(b)]. Below
room temperature these reflections become distinctly asymmetric, and at
210 K the latter is clearly split into two roughly equal peaks, while the
(111) peak has a low angle shoulder [Fig. 4.7.2(c)]. As the temperature is
lowered further the splitting increases [Fig. 4.7.2(d)] until at 20 K the (202)
is well resolved into two peaks, and the (111) is seen to consist of a cen-
tral stronger peak with weaker shoulders on both low- and high-angle sides
[Fig. 4.7.2(e)]. The positions and intensity ratios of the peaks are very well
described by a monoclinic cell in which am and bm lie along the tetragonal
[110] and [110] directions (a m « 6m R^ a t \/2), and c m is close to the [001]
axis (c m « c t ), as illustrated in Fig. 4.7.3. The monoclinic cell has bm as
the unique axis, and the angle between am and c m is ~90.5° at 20 K.
 A Monoclinic Ferroelectric Phase in the Pb(Zr\-xTix)Oz Solid Solution 393

Fig. 4.7.3. Tetragonal and monoclinic unit cell representations.

Fig. 4.7.4. Lattice parameters of PZT with a composition x = 0.48 as a function of

temperature.

The lattice parameters are plotted in Fig. 4.7.4 over the entire tem-
perature range. At the low-temperature phase transition, am is slightly
elongated with respect to tetragonal aty/2, whereas bm « at\/2 continues
to decrease as the temperature is lowered, and c m « c t appears to reach a
broad maximum around the transition.
A direct phase transition from a tetragonal to monoclinic phase is rather
uncommon, and the existence of the latter is likely to be a direct conse-
quence of the proximity of the MPB. Consequently, one might expect the
394 Effective Field Approach to Phase Transitions

monoclinic phase to exist over a relatively narrow composition region. How-

ever, because of the asymmetrical peak broadening, which occurs between
300 and 210 K, we cannot altogether rule out the possibility of an orthor-
rombic phase in this region, although we feel this is unlikely.
In the tetragonal region of PZT the space group is Pimm, with the
polar axis along [001], while in the rhombohedral region, with space group
R3m, the polar axis is along the pseudocubic [111]. The most plausible space
group for the new monoclinic phase is Cm, which is a subgroup of PAmm
and R3m and allows the polar axis to lie anywhere between the [001] and
the [111] axes. A preliminary check of the peak intensities indicates that the
cation displacements lie close to the monoclinic [201] direction, i.e., close
to the rhombohedral [111] axis. If this is the case, monoclinic PZT would
be the first example of the ferroelectric species with P% — Py ^ P%, P%,
p2 p2 -^ (^ m3rn(12)A2Fm predicted from symmetry by Shuvalov.13 A
more detailed investigation of the structure is currently in progress, and the
extent of the monoclinic region will be investigated with additional samples
containing slightly different amounts of Ti.

Acknowledgments

We thank E. Sawaguchi for his efforts trying to locate his 1953 sample for
this work, and Evagelia Moshopoulou for her helpful comments. Support
by NATO (R.C.G.0037), Spanish CICyT (PB96-0037), and U.S. Depart-
ment of Energy, Division of Materials Science (Contract no. DE-AC02-
98CH10886) is also acknowledged.

References

1. B. Jaffe, W.R. Cook and H. Jaffe, Piezoelectric Ceramics (Academic, London,

1971), p. 136.
2. M.J. Haun, E. Furman, S.J. Jang and L.E. Cross, Ferroelectrics 99, 13 (1989).
3. D.L. Corker, A.M. Glazer, R.W. Whatmore, A. Stallard and F. Fauth,
J. Phys.: Condens. Matter 10, 6251 (1998).
4. G. Shirane and K. Suzuki, J. Phys. Soc. Jpn. 7, 333 (1952).
5. E. Sawaguchi, J. Phys. Soc. Jpn. 8, 615 (1953).
6. P. Ari-Gur and L. Benguigui, Solid State Commun. 15, 1077 (1974).
7. K. Kakewaga, O. Matsunaga, T. Kato and Y. Sasaki, J. Am. Ceram. Soc.
78, 1071 (1995).
8. J.C. Fernandes, D.A. Hall, M.R. Cockburn and G.N. Greaves, Nucl. lustrum.
Meth. Phys. Res. B 97, 137 (1995).
 A Monoclinic Ferroelectric Phase in the Pb(Zr\-xTix)03 Solid Solution 395

9. M. Hammer, C. Montry, A. Endriss and Michel J. Hoffmann, J. Am. Ceram.

Soc. 8 1 , 721 (1998).
10. A.P. Wilkinson, J. Xu, S. Pattanaik and J.L. Billinge, Chem. Mater. 10, 3611
(1998).
11. W. Cao and L.E. Cross, Phys. Rev. B 47, 4825 (1993).
12. G.K. Williamson and W.H. Hall, Acta Metall. 1, 22 (1953).
13. L.A. Shuvalov, J. Phys. Soc. Jpn. 28, 38 (1970).
 Chapter 4.8

Tetragonal-to-Monoclinic P h a s e
Transition in Ferroelectric Perovskite:
T h e s t r u c t u r e of PbZro.52Tio.4sO3*
B. Nohedat and J.A. Gonzalo
Departamento de Fisica de Materiales, UAM, Cantoblanco,
28049 Madrid, Spain

L.E. Cross, R. Guo and S.-E. Park

Materials Research Laboratory, The Pennsylvania State University,
Pennsylvania 16802-4800, USA

D.E. Cox and G. Shirane

Department of Physics, Brookhaven National Laboratory, Upton,
New York 11973-5000, USA

The perovskite-like ferroelectric system PbZri-^Ti^Oa (PZT) has a

nearly vertical morphotropic phase boundary (MPB) around x =
0.45-0.50. Recent synchrotron X-ray powder diffraction measurements
by Noheda et al. [Appl. Phys. Lett. 74, 2059 (1999)] have revealed a mon-
oclinic phase between the previously established tetragonal and rhom-
bohedral regions. In the present work, we describe a Rietveld analysis of
the detailed structure of the tetragonal and monoclinic PZT phases on a
sample with x = 0.48 for which the lattice parameters are, respectively,
at = 4.044 A, c t = 4.138 A, at 325 K, and am = 5.721 A, bm = 5.708 A,
c m = 4.138 A, (3 = 90.496°, at 20 K. In the tetragonal phase, the shifts of
the atoms along the polar [001] direction are similar to those in PbTiC>3

*Work previously published in Phys. Rev. B 74, 14 (2000). Copyright © 2000. The
American Physical Society.
f Visiting scientist at Brookhaven National Laboratory.

397
398 Effective Field Approach to Phase Transitions

but the refinement indicates that there are, in addition, local disor-
dered shifts of the Pb atoms of ~0.2 A perpendicular to the polar axis.
The monoclinic structure can be viewed as a condensation along one of
the (110) directions of the local displacements present in the tetragonal
phase. It equally well corresponds to a freezing-out of the local displace-
ments along one of the (100) directions recently reported by Corker et al.
[J. Phys.: Condens. Matter 10, 6251 (1998)] for rhombohedral PZT. The
monoclinic structure therefore provides a microscopic picture of the MPB
region in which one of the "locally" monoclinic phases in the "average"
rhombohedral or tetragonal structures freezes out, and thus represents
a bridge between these two phases.

4.8.1. Introduction

Perovskite-like oxides have been at the center of research on ferroelectric

and piezoelectric materials for the past 50 years because of their simple
cubic structure at high temperatures and t h e variety of high symmetry
phases with polar states found at lower temperatures. Among these mate-
rials the ferroelectric P b Z r i - x T i ^ O a (PZT) solid solutions have attracted
special attention since they exhibit an unusual phase b o u n d a r y t h a t divides
regions with rhombohedral and tetragonal structures, called the mor-
photropic phase b o u n d a r y (MPB) by Jaffe et al.1 Materials in this region
exhibit a very high piezoelectric response, and it has been conjectured
t h a t these two features are intrinsically related. T h e simplicity of the per-
ovskite structure is in part responsible for the considerable progress made
recently in the determination of t h e basic structural properties a n d sta-
bility of phases of some important perovskite oxides, based on ab initio
calculations (see, e.g., Refs. 2-9). Recently, such calculations have also
been used to investigate solid solutions and, in particular, P Z T , where the
effective Hamiltonian includes b o t h structural and compositional degrees
of freedom. 1 0 - 1 2
T h e P Z T phase diagram of Jaffe et al.,1 which covers only temperatures
above 300 K, has been accepted as the basic characterization of t h e P Z T
solid solution. T h e ferroelectric region of the phase diagram consists mainly
of two different regions: t h e Zr-rich rhombohedral region ( F R ) , which con-
tains two phases with space groups R3m and R3c, and t h e Ti-rich tetragonal
region ( F T ) , with space group PAmm.13 T h e two regions are separated by a
b o u n d a r y t h a t is nearly independent of t e m p e r a t u r e , the M P B mentioned
above, which lies at a composition close t o x = 0.47. Many structural
studies have been reported around t h e M P B , since t h e early 1950s, when
 Tetragonal-to-Monoclinic Phase Transition in Ferroelectric Perovskite 399

these solid solutions were first studied, 13 ' 14 since the high piezoelectric fig-
ure of merit that makes PZT so extraordinary is closely associated with
this line. 1 ' 15 The difficulty in obtaining good single crystals in this region,
and the characteristics of the boundary itself, make good compositional
homogeneity essential if single-phase ceramic materials are to be obtained.
Because of this, the MPB is frequently reported as a region of phase coex-
istence whose width depends on the sample processing conditions. 16 ~ 19
Recently, another feature of the morphotropic phase boundary has been
revealed by the discovery of a ferroelectric monoclinic phase (FM) in the
PbZri_3;Ti x 03 ceramic system. 20 Prom a synchrotron X-ray powder diffrac-
tion study of a composition with x = 0.48, a tetragonal-to-monoclinic phase
transition was discovered at ~300K. The monoclinic unit cell is such that
a m and bm lay along the tetragonal [110] and [110] directions (a m « bm ~
at\/2), and c m deviates slightly from the [001] direction (c m w c t ). 2 1 The
space group is Cm, and the temperature dependence of the monoclinic angle
(3 gives immediately the evolution of the order parameter for the tetragonal-
monoclinic (.FT--FM) transition. The polar axis of the monoclinic cell can in
principle be directed along any direction within the ac mirror plane, making
necessary a detailed structural study to determine its direction.
In the present work, we present such a detailed structure determina-
tion of the monoclinic phase at 20 K and the tetragonal phase at 325 K in
PZT with x = 0.48. The results show that the polarization in the monoclinic
plane lies along a direction between the pseudocubic [001]c and [ l l l ] c direc-
tions, corresponding to the first example of a species with P2 = Py ^ JR 2 .
A tentative phase diagram is presented in Fig. 4.8.1, which includes data
for the x = 0.48 composition together with those of the recently stud-
ied x = 0.50 composition. 22 The most striking finding, however, is that
the monoclinic cation displacements found here correspond to one of the
three locally disordered sites reported by Corker et al.23 for rhombohedral
compositions in the region x = 0.1-0.4, and thus provide a microscopic
model of the rhombohedral-to-monoclinic phase transition. This, together
with the fact that the space group of the new phase, Cm, is a subgroup of
both P4mm and R3m, suggests that FM represents an intermediate phase
connecting the well-known F T and F R ZT phases.

4.8.2. Experimental

A PZT sample with x = 0.48 was prepared by conventional solid-state

reaction techniques using appropriate amounts of reagent-grade powders of
400 Effective Field Approach to Phase Transitions

Fig. 4.8.1. Preliminary modification of the PZT phase diagram. The data of Jaffe et al.1
are plotted as open circles. The i " r — F M and PQ—FT transition temperatures for x = 0.48
and x = 0.50 are plotted as solid symbols. The F^-Fyi transition for x = 0.50 is reported
in Ref. 22.

lead carbonate, zirconium oxide, and titanium oxide, with chemical purities
better than 99.9%. Pellets were pressed and heated to 1250°C at a ramp
rate of 10°C/min, held at this temperature in a covered crucible for 2h,
and furnace cooled. During sintering, PbZrC-3 was used as a lead source in
the crucible to minimize volatilization of lead.
High-resolution synchrotron X-ray powder diffraction measurements
were made at beam line X7A at the Brookhaven National Synchrotron
Light Source. In the first set of measurements, an incident beam of wave-
length 0.6896 A from a Ge (111) double-crystal monochromator was used
in combination with a Ge (220) crystal and scintillation detector in the
diffraction path. The resulting instrumental resolution is about 0.01° on
the 29 scale, an order of magnitude better than that of a laboratory instru-
ment. Data were collected from a disk in symmetric flat-plate reflection
geometry over selected angular regions in the temperature range 20-736 K.
Coupled 9-29 scans were performed over selected angular regions with a 29
 Tetragonal-to-Monoclinic Phase Transition in Ferroelectric Perovskite 401

step interval of 0.01°. The sample was rocked 1-2° during data collection
to improve powder averaging.
Measurements above room temperature were performed with the disk
mounted on a BN sample pedestal inside a wire-wound BN tube furnace.
The furnace temperature was measured with a thermocouple mounted just
below the pedestal and the temperature scale calibrated with a sample of
CaF2. The accuracy of the temperature in the furnace is estimated to be
within 10 K, and the temperature stability about 2K. For low-temperature
measurements, the pellet was mounted on a Cu sample pedestal and loaded
in a closed-cycle He cryostat, which has an estimated temperature accuracy
of 2K and stability better than 0.1K. The diffracted intensities were nor-
malized with respect to the incident beam monitor.
For the second set of measurements aimed at the detailed determina-
tion of the structure, a linear position-sensitive detector was mounted on
the 28 arm of the diffractometer instead of the crystal analyzer, and a
wavelength of 0.7062 A was used. This configuration gives greatly enhanced
counting rates that make it feasible to collect accurate data from very
narrow-diameter capillary samples in Debye-Scherrer geometry, with the
advantage that systematic errors due to preferred orientation or texture
effects are largely eliminated. A small piece of the sintered disk was care-
fully crushed and sealed into a 0.2 mm diameter glass capillary. The latter
was loaded into a closed-cycle cryostat, and extended data sets were col-
lected at 20 and 325 K while the sample was rocked over a 10° range. With
this geometry the instrumental resolution is about 0.03° on the 28 scale.
Because lead is highly absorbing, the data were corrected for absorption
effects24 based on an approximate value of /xr = 1.4 determined from the
weight and dimensions of the sample.

4.8.3. Phase Transitions

The evolution of the lattice parameters with temperature was briefly sum-
marized in Ref. 20, and a more complete analysis is presented below. The
results of the full structure analysis are described later.
A transition from the cubic to the tetragonal phase was observed at
~660K, in agreement with the phase diagram shown in Fig. 4.8.1. The
measurements made on the pellet in the cubic phase at 736 K demonstrate
the excellent quality of the sample, which exhibits diffraction peaks with
full-widths at half-maximum (FWHM) ranging from 0.01 to 0.03° as shown
402 Effective Field Approach to Phase Transitions

p
*> Zr o. 5 JU°3
(no
8.0

16.7 16.8 16.9 17.0 17.1

6.0 M (deg)
!
*o

g4.0
0 200 400 600 T(K)
2

2.0-
2Ad/d«5.810

rcos(8)=0.7l(f+5.8 10*sina
0.0
0.0 0.1 0.2 0.3 0.4
sin e

Fig. 4.8.2. The Williamson-Hall plot for P Z T {x = 0.48) derived from the measured
diffraction peak widths in the cubic phase (T = 736 K). Particle size and microstrain
are estimated from a linear fit (solid line). The plot for the (111) reflection in the cubic
phase demonstrates the excellent quality of the ceramic sample (peak width ~0.02°).
The plot of Ad/d vs. temperature is also shown as an inset.

for the (111) reflection plotted as the upper-right inset in Fig. 4.8.2. The
FWHM's (r) for several peaks were determined from least-squares fits to
a pseudo-Voigt function with the appropriate corrections for asymmetry
effects,25 and corrected for instrumental resolution. The corrected values
are shown in Fig. 4.8.2 in the form of a Williamson-Hall plot 26

r cos 6 = X/L + 2{Ad/d) sin 6, (1)

where A is the wavelength and L is the mean crystallite size. From the slope
of a linear fit to the data, the distribution of d spacings, Ad/d, is estimated
to be ~ 3 x 104, corresponding to a compositional inhomogeneity Ax of less
than ±0.003. From the intercept of the line on the ordinate axis the mean
crystallite size is estimated to be ~ 1 /j,m.
A tetragonal-to-monoclinic phase transition in PZT with x = 0.48 was
recently reported by Noheda et al.20 Additional data have been obtained
 Tetragonal-to-MonocUnic Phase Transition in Ferroelectric Perovskite 403

™>Zi0S2Ti0MO3
• i — • -

<4.15

H
84.054
• * — c m £
-•—a m /V2
0.50
•*— b _/V2

0.25 a,
o

0.00
200 400 600 800
T(K)

Fig. 4.8.3. Lattice parameters vs. temperature for PZT (x = 0.48) over the whole range
of temperatures from 20 to 750 K showing the evolution from the monoclinic phase to
the cubic phase via the tetragonal phase.

near the phase transition around 300 K, which have allowed a better deter-
mination of the phase transition to be made, as shown by the evolution
of the lattice parameters as a function of temperature in Fig. 4.8.3. The
tetragonal strain ct/at increases as the temperature decreases from the
Curie point (T « 660K), to a value of 1.0247 at 300K, below which peak
splittings characteristic of a monoclinic phase with a m sw bm « aty/2,
(3 ^ 90°, are observed (Fig. 4.8.3). As the temperature continues to decrease
down to 20 K, am (which is defined to lie along the [110] tetragonal direc-
tion) increases very slightly, and bm (which lies along the [110] tetragonal
direction) decreases. The c m lattice parameter reaches a broad maximum
value of 4.144 A between 240 and 210 K and then reaches a shallow min-
imum value of 4.137 A at 60 K. Over the same temperature region there
is a striking variation of Ad/d determined from Williamson-Hall plots at
various temperatures, as shown in the upper-left inset in Fig. 4.8.2. Ad/d
increases rapidly as the temperature approaches the FT-Fu transition at
300 K, in a similar fashion to the tetragonal strain, and then decreases
404 Effective Field Approach to Phase Transitions

rapidly below this temperature in the monoclinic region. Thus, the micros-
train responsible for the large increase in Ad/d is an important feature of
the phase transition, which may be associated with the development of local
monoclinic order, and is very likely responsible for the large electromechan-
ical response of PZT close to the MPB. 1
The deviation of the monoclinic angle /3 from 90° is an order parameter
of the FT~FM transition, and its evolution with temperature is also depicted
in Fig. 4.8.3. This phase transition presents a special problem due to the
steepness of the phase boundary (the MPB in Fig. 4.8.1). As shown in the
previous section, the compositional fluctuations are quite small in these
ceramic samples (x « ±0.003) but, even in this case, the nature of the
MPB implies an associated temperature uncertainty of AT « 100 K. There
is, therefore, a rather wide range of transition temperatures instead of a
single well-defined transition, so that the order parameter is smeared out
as a function of temperature around the phase change, thereby concealing
the nature of the transition.
Scans over the (220)c region for several different temperatures are plot-
ted in Fig. 4.8.4, which shows the evolution of phases from the cubic phase
at 687K (upper-left plot) to the monoclinic phase at 20K (lower-right plot),
passing through the tetragonal phase at intermediate temperatures. With
decreasing temperature, the tetragonal phase appears at ~660K and the
development of the tetragonal distortion can be observed on the left side
of the figure from the splitting of the (202)t and (220)t reflections. On the
right side of the figure, the evolution of the monoclinic phase, which appears
below ~300K, is shown by the splitting into the (222) m , (222) m , (400) m ,
and (040) m monoclinic reflections. It is quite evident from Fig. 4.8.4. that
the (202)t peak is much broader than the neighboring (220)t peak, for
example, and this "anisotropic" peak broadening is a general feature of
the diffraction data for both phases. Another feature of the patterns is the
presence of additional diffuse scattering between neighboring peaks, which
is particularly evident between tetragonal (00/) and (/i00) pairs, and the
corresponding monoclinic (00/) and (hhO) pairs.

4.8.4. Structure Determination

A detailed analysis of the 325 K tetragonal and 20 K monoclinic struc-

tures of PbZro.52Tio.48O3 was carried out by Rietveld refinement using the
GSAS program package. 27 The pseudo-Voigt peak shape function option
 Tetragonal-to-Monoclinic Phase Transition in Ferroelectric Perovskite 405

27.6 28.0 27.6 28.0

26 (deg)
Fig. 4.8.4. Temperature evolution of the pseudocubic (220) peak from the cubic (top
left) to the monoclinic (bottom right) phase.

was chosen25 and the background was estimated by linear interpolation

between fixed values. An important feature of the refinements was the need
to allow for the anisotropic peak broadening mentioned above. This was
accomplished by the use of the recently incorporated generalized model for
anisotropic peak broadening proposed by Stephens, 28 which is based on a
distribution of lattice parameters. It was also necessary to take into account
some additional diffuse scattering by modeling with a second, cubic, phase
with broad, predominately Gaussian, peaks. A similar strategy has been
adopted by Muller et al.29 in a recent study of PbHfo.4Tio.6O3. Although
in principle this could represent a fraction of untransformed cubic phase,
we suspect that the diffuse scattering is associated with locally disordered
406 Effective Field Approach to Phase Transitions

regions in the vicinity of domain walls. The refinements were carried out
with the atoms assigned fully ionized scattering factors.

4.8.4.1. Tetragonal Structure at 325 K

At 325 K, the data show tetragonal symmetry similar to that of P b T i 0 3 .

This tetragonal structure has the space group P4mm with Pb in 1(a) sites
at (0,0,2); Zr/Ti and 0(1) in 1(6) sites at (1/2,1/2, z); and 0(2) in 2(c)
sites at (1/2,0, z). For the refinement we adopt the same convention as that
used in Refs. 30 and 31 for P b T i 0 3 , with Pb fixed at (0,0,0). However,
instead of thinking in terms of shifts of the other atoms with respect to this
origin, it is more physically intuitive to consider displacements of Pb and
Zr/Ti from the center of the distorted oxygen cuboctahedra and octahedra,
respectively. We shall take this approach in the subsequent discussion.
The refinement was first carried out with individual isotropic (C/iso)
temperature factors assigned. Although a reasonably satisfactory fit was
obtained {RF? = 8.9%), Uiso for O(l) was slightly negative and Uiso for Pb
was very large, 0.026 A 2 , much larger than UiSO for the other atoms. Sim-
ilarly, high values for Pb(t/i so ) in Pb-based perovskites are well known in
the literature, and are usually ascribed to local disordered displacements,
which may be either static or dynamic. Refinement with anisotropic temper-
ature factors 32 (f/n and C/33) assigned to Pb (Table 4.8.1, model I) gave an
improved fit (.RF 2 = 6.1%) with Uu(— U22) considerably larger than [733
(0.032 and 0.013 A 2 , respectively), corresponding to large displacements
perpendicular to the polar [001] axis. A further refinement based on local
displacements of the Pb from the 1(a) site to the 4(d) sites at (x,x,0),
with isotropic temperature factors assigned to all the atoms, gave a small
improvement in the fit (RF2 = 6.0%) with x; 0.033, corresponding to local
shifts along the (110) axes, and a much more reasonable temperature factor
(Table 4.8.1, model II). In order to check that high correlations between the
temperature factor and local displacements were not biasing the result of
this refinement, we have applied a commonly used procedure consisting of
a series of refinements based on model II in which Pb displacements along
(110) were fixed but all the other parameters were varied. 34,35 Figure 4.8.5
shows unambiguously that there is well-defined minimum in the R factor
for a displacement of about 0.19 A, consistent with the result in Table 4.8.1.
A similar minimum was obtained for shifts along (110) directions with a
slightly higher R factor. Thus, in addition to a shift of 0.48 A for Pb along
the polar [001] axis toward four of its 0(2) neighbors, similar to that in
Table 4.8.1. Structure refinement results for tetragonal PbZro.52Tio.4sO3 at
parameters at = 4.0460(1) A, ct = 4.1394(1) A. Fractional occupancies N for a
P b in model II, where A^ = 0.25. Agreement factors, .Rwp, Rp2, and x 2 , are de

Model I, anisotropic lead temperature factors Model II,

X y z [/(A2) X y
Pb 0 0 0 C/11 = 0.0319(4) 0.0328(5) 0.0328
U33 = 0.0127(4)
Zr/Ti 0.5 0.5 0.4517(7) Uiso = 0.0052(6) 0.5 0.5
O(l) 0.5 0.5 -0.1027(28) Uiso = 0.0061(34) 0.5 0.5
0(2) 0.5 0 0.3785(24) Uiso = 0.0198(30) 0.5 0
JXwp 4.00%
RF2 6.11%
2 11.4
x
408 Effective Field Approach to Phase Transitions

~T

4.4 <110> local shifts

<100> local shifts

4.3

i£ 4.2

(A

4.1

T= 325 K
4.0 tetragonal phase

0.0 0.1 0.2 0.3

Lead shifts (A)
Fig. 4.8.5. Agreement factor Rv,p as a function of P b displacements for refinements with
fixed values of x along tetragonal (110) and (100) directions as described in text. The
well-defined minimum at £~0.19A confirms the result listed in Table 4.8.1 for model II.

PbTi03, 3 0 , 3 1 ' 3 6 there is a strong indication of substantial local shifts of

~0.2A perpendicular to this axis. The Zr/Ti displacement is 0.27 A along
the polar axis, once again similar to the Ti shift in PbTiC-3. Attempts to
model local displacements along (110) directions for the Zr/Ti atoms were
unsuccessful due to the large correlations between these shifts and the tem-
perature factor. Further attempts to refine the z parameters of the Zr and
Ti atoms independently, as Corker et al. were able to do, 23 were likewise
unsuccessful, presumably because the scattering contrast for X-rays is much
less than for neutrons.
From the values of the atomic coordinates listed in Table 4.8.1, it can be
inferred that the oxygen octahedra are somewhat more distorted than in
PbTiC-3, the 0(2) atoms being displaced 0.08 A toward the 0(2) plane
above. The cation displacements are slightly larger than those recently
reported by Wilkinson et al.37 for samples close to the MPB containing
a mixture of rhombohedral and tetragonal phases, and in excellent agree-
ment with the theoretical values obtained by Bellaiche and Vanderbilt 38
for PZT with x = 0.50 from first-principles calculations. As far as we are
 Tetragonal-to-Monoclinic Phase Transition in Ferroelectric Perovskite 409

Table 4.8.2. Selected Z r / T i - O and P b - O bond lengths in

the tetragonal and monoclinic structures. Models I and II
refer to the refinements with anisotropic temperature fac-
tors and local (110) displacements for Pb, respectively (see
Table 4.8.1). The standard errors in the bond lengths are
- 0 . 0 1 A.

Bond lengths (A)

Tetragonal Monoclinic
Model I Model II

Zr/Ti-0(1) 1.85 x 1 1.85 x 1 1.87 x 1

2.29 x 1 2.29 x 1 2.28 X1
Zr/Ti-0(2) 2.05 x 4 2.05 x 4 2.13 x 2
1.96 x 2
Pb-O(l) 2.89 x 4 2.90 x 2 2.90 x 2
2.71 x 1 2.60 x 1
Pb-0(2) 2.56 x 4 2.67 x 2 2.64 x 2
2.46 x 2 2.46 x 2

aware no other structural analysis of PZT compositions in the tetragonal

region has been reported in the literature.
Selected bond distances for the two models are shown in Table 4.8.2.
For model I, Zr/Ti has short and long bonds with 0(1) of 1.85 and 2.29 A,
respectively, and four intermediate-length 0(2) bonds of 2.05 A. There are
four intermediate-length Pb-O(l) bonds of 2.89A, four short Pb-0(2)
bonds of 2.56 A, and four much larger Pb-0(2) distances of 3.27 A. For
model II, the Z r / T i - 0 distances are the same, but the P b - 0 distances
change significantly. A Pb atom in one of the four equivalent (x, x, 0)
sites in Table 4.8.1 now has a highly distorted coordination, consisting of
two short and two intermediate Pb-0(2) bonds of 2.46 and 2.67 A, and
one slightly longer Pb-O(l) bond of 2.71 A (Table 4.8.2). The tendency of
P b 2 + , which has a lone sp electron pair, to form short covalent bonds with
a few neighboring oxygens is well documented in the literature. 23 ' 39 ~ 41
The observed and calculated diffraction profiles and the difference plot
are shown in Fig. 4.8.6 for a selected 26 range between 7° and 34° (upper
figure). The short vertical markers represent the calculated peak positions.
The upper and lower sets of markers correspond to the cubic and tetrag-
onal phases, respectively. We note that although agreement between the
observed and the calculated profiles is considerably better when the diffuse
scattering is modeled with a cubic phase, the refined values of the atomic
410 Effective Field Approach to Phase Transitions

10

ri 4H

?—MrH—fhttfrt
* > H " •» »——• :

I4
1, IXLLi
-tote
-—t
—i—
-*—-t-
1—
10 20 30
26 (deg.)

Fig. 4.8.6. Observed and calculated diffraction profiles from the Rietveld refinement
of the tetragonal (top) and monoclinic (bottom) phases of P Z T (x = 0.48) at 325 and
20 K, respectively. The difference plots are shown below, and the short vertical markers
represent the peak positions (the upper set corresponds to the cubic phase as discussed
in t h e text). The insets in each figure highlight the differences between the tetragonal
and the monoclinic phases for the pseudocubic (110) reflection, and illustrate the high
resolution needed in order to characterize the monoclinic phase.

coordinates are not significantly affected by the inclusion of this phase. The
anisotropic peak broadening was found to be satisfactorily described by two
of the four parameters in the generalized model for tetragonal asymmetry. 28

4.8.4.2. Monoclinic Structure at 20 K

As discussed above, the diffraction data at 20 K can be indexed unambigu-
ously on the basis of a monoclinic cell with the space group Cm. In this
case, Pb, Zr/Ti, and 0(1) are in 2(a) sites at (x, 0, z), and 0(2) in 4(6)
sites at (x, y, z). Individual isotropic temperature factors were assigned,
and Pb was fixed at (0, 0, 0). For monoclinic symmetry, the generalized
expression for anisotropic peak broadening contains nine parameters, but
 Tetragonal-to-Monoclinic Phase Transition in Ferroelectric Perovskite 411

when all of these were allowed to vary the refinement was slightly unsta-
ble and did not completely converge. After several tests in which some of
the less significant values were fixed at zero, satisfactory convergence was
obtained with three parameters (i? wp = 0.036, \2 — 11.5). During these
tests, there was essentially no change in the refined values of the atomic
coordinates. A small improvement in the fit was obtained when anisotropic
temperature factors were assigned to Pb (i? wp = 0.033, x 2 = 9.2). The final
results are listed in Table 4.8.3, and the profile fit and difference plot are
shown in the lower part of Fig. 4.8.6.
From an inspection of the results in Tables 4.8.1 and 4.8.3, it can be
seen that the displacements of the Pb and Zr/Ti atoms along [001] are
very similar to those in the tetragonal phase at 325 K, about 0.53 and
0.24 A, respectively. However, in the monoclinic phase at 20 K, there are also
significant shifts of these atoms along the monoclinic [100], i.e., pseudocubic
[110], toward their 0(2) neighbors in adjacent pseudocubic (110) planes, of
about 0.24 and 0.11 A, respectively, which corresponds to a rotation of
the polar axis from [001] toward pseudocubic [111]. The Pb shifts are also
qualitatively consistent with the local shifts of Pb along the tetragonal (110)
axes inferred from the results of model II in Table 4.8.1, i.e., about 0.2 A.
Thus, it seems very plausible that the monoclinic phase results from the
condensation of the local P b displacements in the tetragonal phase along
one of the (110) directions.
Some selected bond distances are listed in Table 4.8.2. The Zr/Ti-0(1)
distances are much the same as in the tetragonal structure, but the two
sets of Zr/Ti-0(2) distances are significantly different, 1.96 and 2.13 A,
compared to the single set at 2.04 A in the tetragonal structure. Except for

Table 4.8.3. Structure refinement results for monoclinic PbZro.52Tio.4sO3

at 20 K, space group Cm, lattice parameters a m — 5.72204(15) A, bm —
. 5.70957(14) A, cm = 4.13651(14) A, /3 = 90.498(1)°. Agreement factors
R w p = 3.26%, flF2 = 4.36%, x 2 = 9-3.

Xm Vm •^m C/iso (A 2 )

Pb 0 0 0 0.0139 a
Zr/Ti 0.5230(6) 0 0.4492(4) 0.0011(5)
O(l) 0.5515(23) 0 -0.0994(24) 0.0035(28)
0(2) 0.2880(18) 0.2434(20) 0.3729(17) 0.0123(22)
a
For P b , [/j so is the equivalent isotropic value calculated from the refined
anisotropic values [Un = 0.0253(7) A 2 , U22 = 0.0106(6) A 2 , t/33 =
0.0059(3) A 2 , U13 = 0.0052(4) A 2 ] .
412 Effective Field Approach to Phase Transitions

a shortening in the Pb-O(l) distance from 2.71 to 2.60 A, the Pb environ-

ment is quite similar to that in the tetragonal phase, with two close 0(2)
neighbors at 2.46 A, and two at 2.64 A.

4.8.5. Discussion

In the previous section, we have shown that the low-temperature mono-

clinic structure of PbZro.52Tio.4sO3 is derived from the tetragonal structure
by shifts of the Pb and Zr/Ti atoms along the tetragonal [110] axis. We
attribute this phase transition to the condensation of local (110) shifts of
Pb, which are present in the tetragonal phase along one of the four (110)
directions. In the context of this monoclinic structure it is instructive to
consider the structural model for rhombohedral PZT compositions with
x = 0.08-0.38 recently reported by Corker et al.23 on the basis of neutron
powder diffraction data collected at room temperature. In this study and
also an earlier study 42 of a sample with x = 0.1, it was found that sat-
isfactory refinements could only be achieved with anisotropic temperature
factors, and that the thermal ellipsoid for Pb had the form of a disk per-
pendicular to the pseudocubic [111] axis. This highly unrealistic situation
led them to propose a physically much more plausible model involving local
displacements for the Pb atoms of about 0.25 A perpendicular to the [111]
axis and a much smaller and more isotropic thermal ellipsoid was obtained.
Evidence for local shifts of Pb atoms in PZT ceramics has also been demon-
strated by pair-distribution function analysis by Teslic and coworkers.39
We now consider the refined values of the Pb atom positions with local
displacements for rhombohedral PZT listed in Table IV of Ref. 23. With
the use of the appropriate transformation matrices, it is straightforward to
show that these shifts correspond to displacements of 0.2-0.25 A along the
direction of the monoclinic [100] axis, similar to what is actually observed
for x = 0.48. It thus seems equally plausible that the monoclinic phase can
also result from the condensation of local displacements perpendicular to
the [111] axis.
The monoclinic structure can thus be pictured as providing a "bridge"
between the rhombohedral and tetragonal structures in the region of the
MPB. This is illustrated in Table 4.8.4, which compares the results for PZT
with x — 0.48 obtained in the present study with earlier results 43 for rhom-
bohedral PZT with x = 0.40 expressed in terms of the monoclinic cell.44 For
x = 0.48, the atomic coordinates for Zr/Ti, 0(1), and 0(2) are listed for
 Tetragonal-to-Monoclinic Phase Transition in Ferroelectric Perovskite 413

Table 4.8.4. Comparison of refined values of atomic coordinates in the monoclinic

phase with the corresponding values in the tetragonal and rhombohedral phases for
both the "ideal" structures and those with local shifts, as discussed in text.

Tetragonal, x = 0.48, Monoclinic, Rhombohedral (Ref. 43),

325 K x = 0.48, 20 K x = 0.40, :295 K
Ideal Local shifts8, As refined Local shifts' 3 Ideal

^Zr/Ti 0.500 0.530 0.523 0.520 0.540

ZZr/Ti 0.451 0.451 0.449 0.420 0.460
^O(l) 0.500 0.530 0.551 0.547 0.567
-0.103 -0.103 -0.099 0.093 -0.053
x
O(2) 0.250 0.280 0.288 0.290 0.310
2/0(2) 0.250 0.250 0.243 0.257 0.257
z
O(2) 0.379 0.379 0.373 0.393 0.433
am(A) 5.722 5.722 5.787
6m (A) 5.722 5.710 5.755
Cm (A) 4.139 4.137 4.081
/5(°) 90.0 90.50 90.45
a
Tetragonal local shifts of (0.03, 0.03, 0).
b
Hexagonal local shifts of (-0.02, 0.02, 0).

the "ideal" tetragonal structure (model I) and for a similar structure with
local shifts of (0.03, 0.03, 0) in the first two columns, and for the monoclinic
structure in the third column. The last two columns describe the rhombohe-
dral structure for x = 0.40 assuming local shifts of (—0.02, 0.02, 0) along the
hexagonal axes and the as refined "ideal" structure, respectively. It is clear
that the condensation of these local shifts gives a very plausible description
of the monoclinic structure in both cases. It is also interesting to note the
behavior of the corresponding lattice parameters; metrically the monoclinic
cell is very similar to the tetragonal cell except for the monoclinic angle,
which is close to that of the rhombohedral cell.
Evidence for a tetragonal-to-monoclinic transition in the ferroelectric
material PbFeo.5Nbo.5O3 has also been reported by Bonny et al.45 from
single crystal and synchrotron X-ray powder diffraction measurements. The
latter data show a cubic-tetragonal transition at ~376 K, and a second tran-
sition at ^355 K. Although the resolution was not sufficient to reveal any
systematic splitting of the peaks, it was concluded that the data were con-
sistent with a very weak monoclinic distortion of the pseudorhombohedral
unit cell. In a recent neutron and X-ray powder study, Lampis et al.46 have
shown that Rietveld refinement gives better agreement for the monoclinic
structure at 80 and 250 K than for the rhombohedral one. The resulting
414 Effective Field Approach to Phase Transitions

(a) (b) (c)

Fig. 4.8.7. Schematic illustration of the tetragonal (a), monoclinic (b), and rhombohe-
dral (c) distortions of the perovskite unit cell projected on the pseudocubic (110) plane.
The solid circles represent the observed shifts with respect to the ideal cubic structure.
The light gray circles represent the four locally disordered (100) shifts in the tetragonal
structure (a) and the three locally disordered shifts in the rhombohedral structure (c)
described by Corker et al.23 The heavy dashed arrows represent the freezing-out of one
of these shifts to give the monoclinic observed structure. Note that the resultant shifts
in the rhombohedral structure can be viewed as a combination of a [111] shift with local
(100) shifts, as indicated by the light gray arrows.

monoclinic distortion is very weak, and the large thermal factor obtained
for Pb is indicative of a high degree of disorder.
The relationships between the PZT rhombohedral, tetragonal, and mon-
oclinic structures are also shown schematically in Fig. 4.8.7, in which the
displacements of the Pb atom are shown projected on the pseudocubic
(110) mirror plane. The four locally disordered (110) shifts postulated in
the present work for the tetragonal phase are shown superimposed on the
[001] shift at the left [Fig. 4.8.7(a)] and the three locally disordered (100)
shifts proposed by Corker et al.23 for the rhombohedral phase are shown
superimposed on the [111] shift at the right [Fig. 4.8.7(c)]. It can be seen
that both the condensation of the [110] shift in the tetragonal phase and
the condensation of the [001] shift in the rhombohedral phase leads to the
observed monoclinic shift shown at the center [Fig. 4.8.7(b)]. We note that
although Corker et al. discuss their results in terms of (100) shifts and a
[111] shift smaller than that predicted in the usual refinement procedure,
they can be equally well described by a combination of shifts perpendicular
to the [111] axis and the [111] shift actually obtained in the refinement, as
is evident from [Fig. 4.8.7(c)].
We conclude, therefore, that the FM phase establishes a connection
between the PZT phases at both sides of the MPB through the com-
mon symmetry element, the mirror plane, and suggest that there is not
really a morphotropic phase boundary, but rather a "morphotropic phase,"
 Tetragonal-to-Monoclinic Phase Transition in Ferroelectric Perovskite 415

connecting the F T and F R phases of PZT. In the monoclinic phase the dif-
ference vector between the positive and negative centers of charge defines
the polar axis, whose orientation, in contrast to the case of the F T and F R
phases, cannot be determined on symmetry grounds alone. According to
this, from the results shown in Table 4.8.3, the polar axis in the monoclinic
phase is found to be tilted about 24° from the [001] axis toward the [111]
axis. This structure represents the first example of a ferroelectric material
with P 2 — Py ^ P 2 , (Px, Py, Pz) being the Cartesian components of the
polarization vector. This class corresponds to the so-called m3m(12)A2Fm
type predicted by Shuvalov.47 It is possible that this new phase is one of
the rare examples of a two-dimensional ferroelectric48 in which the unit
cell dipole moment switches within a plane containing the polar axis, upon
application of an electric field.
This FM phase has important implications; for example, it might explain
the well-known shifts of the anomalies of many physical properties with
respect to the MPB and thus help in understanding the physical properties
in this region, of great interest from the applications point of view.1 It has
been found that the maximum values of 1^33 for rhombohedral PZT with
x = 0.40 are not obtained for samples polarized along the [111] direction
but along a direction close to the perovskite [001] direction. 49 This points
out the intrinsic importance of the [111] direction in perovskites, whatever
the distortion present, and is consistent with Corker et al.'s model for the
rhombohedral phase, 23 and the idea of the rhombohedral-tetragonal tran-
sition through a monoclinic phase.
It is also to be expected that other systems with morphotropic phase
boundaries between two nonsymmetry-related phases (e.g., other per-
ovskites or tungsten-bronze mixed systems) may show similar intermediate
phases. In fact, an indication of symmetry lowering at the MPB of the PZN-
PT system has been recently reported by Pujishiro et al.50 From a different
point of view, a monoclinic ferroelectric perovskite also represents a new
challenge for first-principles theorists, until now used to dealing only with
tetragonal, rhombohedral, and orthorhombic perovskites.
A structural analysis of several other PZT compositions with x =
0.42-0.51 is currently in progress in order to determine the new PZT phase
diagram more precisely. In the preliminary version shown in Fig. 4.8.1
we have included data for a sample with x = 0.50 made under slightly
different conditions 22 at the Institute of Ceramic and Glass (ICG) in
Madrid, together with the data described in the present work for a sam-
ple with x — 0.48 synthesized in the Materials Research Laboratory at the
416 Effective Field Approach to Phase Transitions

Pennsylvania State University (PSU). As can be seen the results for these
two compositions show consistent behavior, and demonstrate t h a t the F M ~
FT phase b o u n d a r y lies along the M P B of Jaffe et al. Preliminary results for
a sample from P S U with x = 0.47 show unequivocally t h a t the monoclinic
features are present at 300 K. However, measurements on an ICG sample
with the same nominal composition do not show monoclinicity unambigu-
ously, but instead a rather complex poorly defined region from 300 to 400 K
between the rhombohedral and tetragonal phases. 2 2 T h e extension of the
monoclinic region and the location of the F R - F M phase b o u n d a r y are still
somewhat undefined, although it is clear t h a t the monoclinic region has a
narrower composition range as the t e m p e r a t u r e increases. T h e existence of
a quadruple point in the P Z T phase diagram is an interesting possibility.

Acknowledgments

We wish to gratefully acknowledge B. Jones for the excellent quality of the

x = 0.48 sample used in this work, and we t h a n k L. Bellaiche, A.M. Glazer,
E. Moshopoulou, C. Moure, and E. Sawaguchi for their helpful comments.
Support by NATO (Grant no. R.C.G. 970037), the Spanish C I C y T (Project
no. PB96-0037), and the U.S. Department of Energy, Division of Materials
Sciences (Contract no. DEAC02-98CH10886) is also acknowledged.

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21. The [110] and [110] directions are chosen so that the monoclinic angle (5 > 90°
to conform with usual crystallographic convention.
22. B. Noheda, J.A. Gonzalo, A.C. Caballero, C. Moure, D.E. Cox and
G. Shirane, cond-mat/9907286, Ferroelectrics (to be published).
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44. The rhombohedral unit cell can be expressed in terms of a monoclinic one
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cos0 = 1 — 2sin 2 (a/2)/cos(a/2) and aT and a are the R3m cell parameters.
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Y. Yamashita, Ferroelectrics (to be published).
 Chapter 4.9

Evolution of the Ferroelectric

Transition Character of Partially
Deuterated Triglycine Selenate*
Carmen Arago and Julio A. Gonzalo
Departamento de Fisica de Materiales C-IV,
Universidad Autonoma, 28049 Madrid, Spain

Automatically recorded hysteresis loops and dielectric constant data on

pure and partially deuterated triglycine selenate and sulfate are used
to characterize the transition evolution from quasi-tricritical to clearly
first order character. A quantitative assessment of the transition's dis-
placive degree is made through the first anharmonic contribution to the
effective field (g), obtained from hysteresis loop data. This character-
ization is complemented with the assessment by means of a general-
ized Rhodes-Wohlfarth parameter R = (NkBC/AwPso)1 involving the
Curie constant C and the saturation spontaneous polarization Pso as
done previously by other authors.

4.9.1. Introduction

First-principles local density approximation calculations 1 on ferroelectric

perovskites have shown t h a t cubic/tetragonal phase transitions in some of
these compounds, at first thought to be of the displacive kind, can be well
described as order/disorder-type transitions. On t h e other hand, general-
ized Rhodes-Wohlfarth empirical parameters, 2 ~ 4 analogous to those used
to characterize magnetic phase transitions, have been proposed to assess
quantitatively the displacive versus order/disorder degree of ferroelectric
transitions.

*Work previously published in Journal of Physics: Condensed Matter 12, 3737 (2000).
Copyright © 2000. Institute of Physics.

419
420 Effective Field Approach to Phase Transitions

In this work, we focus our attention on transitions in hydrogenated

and deuterated crystals of triglycine selenate (TGSe)i_ x (DTGSe)a; and
triglycine sulfate (TGS)i_ x (DTGS)a;, which are paradigmatic examples of
order/disorder transitions but are not free from typical features of displacive
systems such as the discontinuous, first order transition observed in DTGSe.
We will see that in these ferroelectrics (whose structure is so complicated
as to preclude ab initio calculations to substantiate the mixed displacive
order/disorder character) it is still possible to quantitatively characterize
the evolution of the displacive component involved in the phase transition.
The order/disorder features of a transition may be ascertained through
measurements of the transition entropy and the specific heat jump at T c .
The displacive characteristics are usually (if it is at all feasible) seen by
measuring underdamped soft modes in the vicinity of the transition by
means of infrared, Raman, or neutron scattering spectroscopies. Recently,
Dalai et al,b have pointed out that diffraction work and NMR data provide
convincing evidence that order/disorder and displacive features coexist in
H-bonded ferroelectric transitions. Characteristics of mixed order/disorder-
displacive phase transitions can be analyzed within the framework of a
generalized effective field approach in which the effective field is given by

EeS = E + (3PA + 7 P d 3 + dP%L.

The basic differences between a purely order/disorder and a purely dis-

placive transition, if such extreme cases are possible4 at all among ferroelec-
tric transitions, can be visualized in the following way. In an order/disorder
transition an ion (atom) or a group of ions (atoms) in the unit cell may
occupy either one of two "off center" (shifted) positions between neighbor-
ing ions (atoms). These two positions correspond to two potential well min-
ima separated by a relatively large energy barrier at the mid-point between
them. In the paraelectric phase the two potential minima are equivalent,
and they are equally populated. In the ferroelectric phase the cooperative
(dipolar) interaction between cells makes the two wells become asymmetric
and a spontaneous polarization sets in. Even at the order/disorder transi-
tion, if the two potential minima are deep enough and their separation is
well kept, harmonic oscillations around the equilibrium position may be well
defined and the normal modes may remain "hard." On the other hand, in a
displacive transition, corresponding to the case of a shallow well separated
by a weak potential barrier, the separation between the minima (at which
the potential may require additional anharmonic terms to be well speci-
fied) would evolve from the low-temperature ferroelectric phase toward the
 Evolution of the Ferroelectric Transition Character 421

transition point and beyond, into the paraelectric phase. At these higher
temperatures we would finally have one single effective minimum and the
anharmonic oscillations around equilibrium could result in "soft" modes.
Depending on the relative sign of higher order terms in the local poten-
tial, the dipole moment in the paraelectric phase (T > Tc) could be either
larger or slightly smaller than in the ferroelectric phase (T S OK).
Triglycine selenate, belonging to the triglycine sulfate family, is an inter-
esting uniaxial ferroelectric whose transition is very close to a tricritical
point. 6 - 8 Increasing deuteration changes the transition's features giving
rise to a clearly discontinuous transition with a thermal hysteresis AT =
0.8°C for x= 0.96, almost full deuteration. 9 The availability of accurate
dielectric and thermal data near the Curie temperature for both TGSe and
TGS is important to assess quantitatively the evolution with deuteration
of the degree of displacive character of the phase transition.

4.9.2. Experiment

The samples of TGSe and TGS were prepared at the Institute of Physics,
Adam Mickiewicz University, Poznan (Poland). They were cut from single
crystals grown from aqueous solution and their shape was almost paralleepi-
pedic. The thickness of these samples was between 0.6 and 1.0 mm and their
areas went from 3 to 25 mm 2 .
Hysteresis loops were measured at a frequency of 50 Hz with a DDP
bridge and they were observed with a Nicolet NIC-310 digital oscillo-
scope. The temperature was carefully controlled by means of an Unipan
680 controller that allowed very slow heating/cooling ramps maintaining
an accuracy of 0.01 K. The actual temperature inside the sample holder
was measured with a type-T thermocouple connected to a Keithley 196
voltmeter. The sample holder was well isolated and refrigerated by liquid
nitrogen. The whole measuring process was fully automated, which resulted
in a real improvement of the data acquisition. In fact, 4000 points were
recorded for each loop at temperature intervals of 0.25 K and even lower
(0.1K) as the transition temperature was approached. After data record-
ing, an iterative computer program was used to analyze the loops and to
obtain the spontaneous polarization Ps at each temperature.
Dielectric constant measurements were performed with an HP 428A
precision LCR meter at a low voltage of 1V and a frequency of 1 kHz. Also
these measurements were automatically programed and recorded.
422 Effective Field Approach to Phase Transitions

4.9.3. Results and Discussion

Figure 4.9.1 gives the spontaneous polarization Ps against the tem-

perature T for (a) (TGSe) 1 _ x (DTGSe) x , x = 0, 0.35, 0.80; and
(b) (TGS)i_ :E (DTGS) x , x = 0, 0.54, 0.77. It can be seen that the decrease
of spontaneous polarization approaching the transition temperature is more
pronounced for TGSe than for TGS, as corresponds to quasi-critical behav-
ior, and that for DTGSe the data appear to suggest a small discontinuity
at the transition.
Assuming an effective field of the form10

EeS = E + pPd[l + g(Pd/Nfi)2 + h(Pd/N^L], (1)

• x=0
TGSe1xDTGSex 0 x = 0 .35
• X = 0.80

T(°C)

• x= 0
~ TGS,J)TGSr "
2 5-
^ ^ ^ * W - * x=a.n
2.0-
^ < « ^£^ * «*>„
S w^ s & .
1.5- > . ^ ^Su
^ V^ «*%>o ^ v
1.0- \ % %

0.5-
\ :<> *A
« A

0.0-
°
1 • 1 1 • 1 ' 1 ' 1 '

T(°C)

Fig. 4.9.1. Spontaneous polarization Pso against temperature T for different deutera-
tion percentages in (a) triglycine selenate and (b) triglycine sulfate.
 Evolution of the Ferroelectric Transition Character 423

where E is the external applied field, Pa is the dipolar polarization, N the

number of dipoles per unit volume g, h a dimensionless coefficient, and //
the elementary dipolar moment, the dipoles could be either rigid [fi(T) =
^i(O) = fi(Tc) = constant] or deformable. In this latter case there are two
possibilities, /z(T)///(0) < 1 and /j,(T)/n(0) > l, depending on the signs of
higher order terms in the local potential.
From the equation of state

(2)
|r'-(ff)
in terms of reduced variables e = E//3N/1, p = Pd/Nfi, we obtain

e=Zrtanh-1p-p{l+gp2 + hp*L) (3)

-*-C

and with p = ps (the reduced spontaneous polarization) for e = 0, we have

g.ipl)sg+hp^mi^2im_^ (4)

We note that each hysteresis loop provides a spontaneous polarization

PS{T), which is normalized, ps(T) = P S (T)/P s 0 , with P s 0 = Nfj,, to be
introduced in Eq. (4).
Figure 4.9.2 gives g' against ps for (a) (TGSe)i_ a; (DTGSe) :c and
(b) (TGS)i_a;(DTGS) x for the different molar fractions. As the plots can
be linearly fitted we can determine g as the value at which each fitting
line crosses the g' axis. The coefficient g, representing the strength of the
quadrupolar interaction, 11-13 is a good indicator for the type of transition
of the ferroelectric crystal. In fact, g < 1/3 for a second order transition,
g > 1/3 for a first order transition, and g = 1/3 for a tricritical point.
We had checked in an earlier work 14 that increasing deuteration in TGS
determines an evolution of the transition to a tricritical point but staying
still far from it. In a similar way for TGSe, the first order character of the
ferroelectric transition becomes more evident 9 as the percentage of deuter-
ation grows. As the transition becomes more first order the g value grows, 13
reflecting likely changes in the local potential.
An entirely different parameter, R = /ic/A*o> analogous to the Rhodes-
Wohlfarth parameter for magnetic systems as previously mentioned, has
been proposed 3 ' 4 to characterize the ferroelectric transition type. Here, nc is
defined as the individual dipolar moment in the paraelectric phase, obtained
424 Effective Field Approach to Phase Transitions

g'=g + hpj

9'

• x=0
TGSe1.pTGSex <f x=0.35
• x=0.80
•—|—i—i—•—|—i—i—i—i—•—i—i—i—i—i—i—i—i
00 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 09 1.0

g' = g + hpf

• x=0
TGSUlpTGSx « x=0.54
& x=0.77
i—|—•—|—,—i—i—i—i—|—i—i—i—i—•—i—i—i—i
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

Fig. 4.9.2. Linear plot of g' against normalized spontaneous polarization pi for each
deuteration percentage in (a) triglycine selenate, and (b) triglycine sulfate.

from the Curie-Weiss constant, C = e(T — Tc), with e the low-field and low-
frequency dielectric constant, and fio is taken as the saturation individual
dipolar moment in the ferroelectric phase (T = OK), given by PSQ/N. SO
we can write
R= {NkBC/4nP^2.

It is evident that in an order/disorder ferroelectric, with rigid dipoles

approximately equal in the paraelectric phase and at saturation (T = OK),
the value of R must be near one. As the displacive character of the transi-
tion becomes more and more pronounced one expects that going through
Tc involves not only disordering the preferentially aligned dipoles but also
 Evolution of the Ferroelectric Transition Character 425

releasing their strain (related to the spontaneous field and to the anhar-
monic potential terms). It may be then expected that the generalized
Rhodes-Wohlfarth parameter becomes larger than one.
Table 4.9.1 shows the values obtained from hysteresis loops and dielec-
tric constant measurements for the six different samples.
Figure 4.9.3 gives R as a function of g for pure and deuterated TGS and
pure and deuterated TGSe. It can be seen that there is a linear correlation
between both parameters. In the plot we have noted g = 1/3 (which indi-
cates the crossover between continuous and discontinuous transitions) and
R = 1 (which is the borderline between the dipole behavior upon crossing
the transition). The above data show clearly that R grows when g grows
and that R > 1 favors the displacive character of the transition, which
becomes more likely to be first order (g > 1/3).

Table 4.9.1. Dielectric measurements and resulting parameters.

T c (K) AT(K) Ps0(MCcm-2) C(K) R

(TGSe)i_ a ; (DTGSe) : I 0 295.16 0.1 4.5 0.30 4166 0.87

0.35 297.79 0.2 4.3 0.33 4000 0.89
0.80 303.3 0.5 4 0.35 3703 0.92
(TGSJi-^DTGS), 0 322.18 — 4.2 0.21 3225 0.82
0.54 326.15 — 3.9 0.23 2941 0.84
0.77 330.4 — 3.6 0.25 2702 0.87

o (TGS^JDTGS),,
• (TGSe^JDTGSe),,

+-
R=1

-H+
R

i . L_

9
Fig. 4.9.3. Plot of Rhodes—Wohlfarth parameter R against g for triglycine selenate and
triglycine sulfate with different deuteration percentages. Each point can be identified
from the values recorded in Table 4.9.1.
426 Effective Field Approach to Phase Transitions

We may then conclude t h a t the parameter g, which can be easily

obtained from hysteresis loop d a t a for most ferroelectric crystals, gives a
good characterization of the transition in uniaxial, basically order/disorder
ferroelectrics (0 < g < 1/3) as well as in typically displacive ferroelectrics
(g = 1) like most pseudocubic ferroelectric perovskites. Cases like LiTaOs,
which can be considered a highly distorted perovskite, are good examples
of the coexistence of pronounced order/disorder and displacive features.
T h e case of Sn2P2S6, with a second order transition at T = 337K, is
another example of a transition t h a t can be said to be at the o r d e r / d i s o r d e r -
displacive crossover. 1 5

Acknowledgments

Financial support from D G I C y T , through grant no. PB96-0037, is grate-

fully acknowledged. We would like to t h a n k G. Shirane and J. M. Perez-
M a t o for helpful discussions and the latter for making available a preprint
of his work on the subject prior to publication.

References

1. W. Zhong, D. Vanderbilt and K.M. Rabe, Phys. Rev. Lett. 26, 1861 (1994).
2. M. Tokunaga, J. Phys. Soc Jpn. 57, 4275 (1988).
3. Y. Onodera and N. Sawashima, J. Phys. Soc. Jpn. 60, 1247 (1991).
4. J.M. Perez-Mato, S. Ivantchev, A. Garcia and I. Etxebarria, Proc. 9th Eur.
Meeting on Ferroelectricity, Prague (1999).
5. N. Dalai, A. Bussman-Holder and K.H. Michel, Proc. 9th Eur. Meeting on
Ferroelectricity, Prague (1999).
6. T. Iglesias, B. Noheda, G. Lifante, J.A. Gonzalo and M. Koralewski, Phys.
Rev. 5 50, 10307 (1994).
7. T. Iglesias, B. Noheda, B. Gallego, J.R. Fdez del Castillo, G. Lifante and
J.A. Gonzalo, Europhys. Lett. 28, 91 (1994).
8. B. Fugiel and M. Mierzwa, Phys. Rev. B 57, 777 (1998).
9. K. Gesi, J. Phvs. Soc. Jpn. 4 1 , 565 (1976).
10. J.A. Gonzalo, Effective Field Approach to Phase Transitions and Some Appli-
cations to Ferroelectrics (World Scientific, Singapore, 1991).
11. J.A. Gonzalo, R. Ramirez, G. Lifante and M. Koralewski, Fermelectr. Lett.
15, 9 (1993).
12. B. Noheda, G. Lifante and J.A. Gonzalo, Fermelectr. Lett. 15, 109 (1993).
13. B. Noheda, G. Lifante and J.A. Gonzalo, Fermelectr. Lett. 17, 25 (1994).
14. C. Arago, B. Noheda and J.A. Gonzalo, Prot. 9th Eur. Meeting on Fermelec-
tricity, Prague (1999).
15. J. Hlinka, T. Janssen and V. Dvorak, J. Phys.: Condens. Matter, 11, 3209
(1999).
 Chapter 4.10

Composition Dependence of
Transition Temperature in Mixed
Ferroelectric-Ferroelectric Systems'
Carmen Arago, Manuel I. Marques
and Julio A. Gonzalo
Departamento de Fisica de Materiales, C-IV,
Universidad Autonoma de Madrid,
28049 Madrid, Spain

The composition dependence of the transition temperature Tc(x) for

mixed crystals of triglycine sulfate (TGS) and deuterated triglycine sul-
fate (DTGS) has been investigated experimentally and analyzed theoret-
ically. A similar investigation has been carried out for triglycine selenate
(TGSe) and deuterated triglycine selenate (DTGSe). The experimental
results agree well with previous data by Brezina (TGS/DTGS) and Gesi
(TGSe/DTGSe). Classically, we would expect a linear dependence of
temperature Tc(x) = Tc(0) + Ax with composition x. However, Tc(x) is
clearly below the straight line, especially at x ~ 0.5. We show that an
effective field approach with quantum effects can justify well this lower-
ing of Tc(a;).The experimental data are also compared with classical and
quantum Monte Carlo simulations for mixed Ising systems. It is shown
that there is a good qualitative agreement with the observed behavior
in mixed crystals of the TGS family.

It is a well-known fact t h a t the critical t e m p e r a t u r e Tc for a ferroelec-

tric transition depends on the material's composition. Mixed systems,
ferroelectric-antiferroelectric 1 as well as ferroelectric-paraelectric, 2 ' 3 have
been analyzed earlier in order to explain theoretically the experimentally

"Work previously published in Phys. Rev. B 62, 13 (2000). Copyright © 2000. The
American Physical Society.

427
428 Effective Field Approach to Phase Transitions

observed transition temperature behavior. In the above-mentioned systems

a quantum effective field approach can explain the deviations of Tc(x) from
the expected classical results using just mean field considerations.
In the present work, we study partially deuterated triglycine sul-
fate ( T G S ) I _ ; C ( D T G S ) : E and partially deuterated triglycine selenate
(TGSe)i_ a: (DTGSe) a ; crystals considered as special cases of ferroelectric-
ferroelectric mixed systems with a small change (about 4%) in transition
temperature between Tc(0) and T c (l). Experimental data from earlier
works 4 - 7 show that the x dependence of Tc is clearly nonlinear. The lower-
ing of the experimental curve below the classically predicted straight line is,
in fact, very small when compared with the absolute values of the critical
temperatures. As noted below the experimental error in our Tc measure-
ments is ±0.1 K. In addition it must be noted that in Ref. 4 there is a
substantial scattering of the data points in the experimental results, prob-
ably caused by the difficulty to evaluate the actual composition of each
sample which very likely are not spatially homogeneous.
Entropy arguments, analogous to Vegard's rule for the melting temper-
ature vs. composition in alloys, might result in a nonlinearity of Tc(x). We
will see below that our Monte Carlo simulations with Ising mixed systems
do not support large enough deviations to explain the observed behavior in
our case.
The (TGSh-^DTGS);, and (TGSe)i_ x (DTGSe) x crystals have been
prepared at the Institute of Physics, Adam Mickiewicz University, Poznan
(Poland), with different nominal deuteration percentages. Their shape was
paralelepipedic with thickness between 0.6 and 1.6 mm and areas around
3-4mm 2 . Dielectric measurements, both hysteresis loops from which we
obtain PS(T) and dielectric constant e(T), have been performed in order
to determine the critical temperature Tc for each composition. Hysteresis
loops were obtained by using a DDP bridge and were observed with a
Nicolet 310 oscilloscope. The data recording process was fully automated.
Dielectric constant measures were performed with a Hewlett-Packard LCR
meter 4284A applying a voltage of 1V and a frequency of 1 kHz. The data
were automatically recorded.
The sample holder was a copper cylinder with three concentric compart-
ments. The inner compartment contained the sample in contact with the
electrodes and the thermocouple whose signal was measured by a Keitley
voltmeter model 196. In the intermediate cylinder were located the electric
connections to a temperature controller, Unipan type 680, with an accuracy
of ±0.1 K. The outside cylinder was used for refrigeration.
 Composition Dependence of Transition Temperature 429

A Gesi's data
(TGSeJ^DTGSe),,
Fitting curve for Gesi's data
35 35
A This work
Quantum effects
• Monte Carlo data with quantum effects
- ° — Clasical Monte Carlo data & classical approach.

30 30

o
o

25 25

20 -" 1— —I— —I— —I— 20

0.0 0.2 0.4 0.6 0.8 1.0

Deuteration molar fraction x

Fig. 4.10.1. Deuteration (molar fraction) x dependence of transition temperature Tc
for mixed crystals of triglycine sulfate ( T G S ) I _ : E ( D T G S ) X .

70 70
A Brezina's data (TGS)1x(DTGS)x
Fitting curve for Brezina's data
65 A This work
Quantum effects
• Monte Carlo data with quantum effects
Clasical Monte Carlo data & classical approach j r ^ - / A -
A

it* 55

45
0.0 0.2 0.4 0.6 0.8 1.0

Deuteration molar fraction x

Fig. 4.10.2. Deuteration (molar fraction) x dependence of transition temperature T c
for mixed crystals of triglycine selenate (TGSe)i_ x (DTGSe) : E .

Experimental results 5 ' 7 are reproduced in Figs. 4.10.1 and 4.10.2.

We have attempted a theoretical analysis similar to the one made
before with other mixed systems. In our case, we can think of the
ferroelectric-ferroelectric system as a mixture of two different ferroelectrics,
with well-defined individual dipolar moments /in (for the pure case) and /^D
430 Effective Field Approach to Phase Transitions

(for the completely deuterated case). In the classical approach, the transi-
tion temperature for each composition would be

T ; ( x ) = T c * ( 0 ) ( l - x ) + Tc*(l)*, (1)

T* being according to the standard effective field theory 8

Tc* = (3N»2/kB,

where (3 is the common mean field ccoefncient, N the common number of

dipoles per unit volume, and kB Boltzman's constant. The energy can be
written quantum mechanically as

hcoo Q + (n) T o ) = kBTc*

and it should be equated to the thermal energy kBT*.

Using Planck's distribution law in thermal equilibrium
i
(n)n = o(haj0/kBTc) _ J'

we have
1 1 kBT*(x)
2 e[hw0(x)/kBTc(x)] _ I ~ hiU0(x)

This equation can be rewritten as

1 = 2kBT*{x)
(2)
tanh[/iwo(a;)/2A;BTc(a;)] hwo(x)

and from here we obtain

T (x) = hw0(x)/2kB ,g,
c[
' ta,nh-1[hLO0(x)/2kBT*(x)]'

Taking Eq. (1) into Eq. (3) and identifying

aeff(x) (4)
= zk^W)
we get finally
a
rp I \ _ rp*(Q\ eff\%) /g\
c(X) c[ ) 1
- ~tanh- [aeS(x)/{(l-x) + [T*(l)/T*(OM]'
 Composition Dependence of Transition Temperature 431

which gives a relationship between the experimentally observed "quan-

tum transition temperature" Tc(x) for each composition and the "clas-
sic transition temperatures" Tc*(0) and Tc*(l) for pure and completely
deuterated compositions. Classical and quantum transition temperatures
are scarcely different for both extreme compositions x = 0 and x = 1.
aefi(x) defined by Eq. (4) gives the degree of the "quantum effect"
as a function of composition for the partially deuterated systems. This x
dependence can be associated to a certain WQ(X), which may be taken to
mean that the zero point quantum energy changes slightly with composi-
tion. This change becomes a maximum when the deuterated molar fraction
is x ~ 0.5 and a minimum for x = 0 and x = 1 (undiluted systems).
The interaction potential for identical dipoles (/XH or fir>) is perfectly peri-
odic. On the other hand, the interaction potential between different dipoles
(/ZH and /XD) is aperiodic and aleatory. This difference may be expected to
show up in the interatomic potential determining the zero point energy and
therefore the frequency OJQ. Later, we will see that the observed behavior of
Tc{x) can be taken care of through an expression for Awo(a;) reflecting the
aperiodic character of the system for x = 0.5.
The function Tc(x) given by Eq. (5) has been plotted at Figs. 4.10.1 and
4.10.2 for the mixed TGS and mixed TGSe systems, respectively. As can
be seen it agrees fairly well with the experimental data in both cases.
At this point, we can think of quantum effects as a good candidate
to explain the deviations from the expected linear behavior. It is not clear
whether the linear approximation is suitable to describe accurately the com-
position behavior in a purely classical scenario. Even if mean field approx-
imation describes well the critical behavior of long-range ferroelectrics we
do not know if it takes properly into account the effect of short-range inter-
actions between deuterated and nondeuterated dipoles.
Thus, we have considered a mixed Ising system with two species, each
with a different value of the critical temperature. The Ising model is more
appropriate for uniaxial ferroelectrics (such as crystals of the TGS) than
other models (e.g., Heisenberg) but we should note that in a ferroelectric
the true interactions are not nearest neighbors only, but long range as is
well known.
To simulate a change on transition temperature similar to the one
experimentally observed in (TGS)i_3;(DTGS) x , we have chosen the same
experimental ratio between the critical temperatures TC*(0)/TC*(1) « 0.96,
Tc*(l) being the critical temperature of the deuterated Ising system with an
interaction constant J = 1 and T* (0) the critical temperature of the pure
432 Effective Field Approach to Phase Transitions

component whose interaction constant J' = 0.96. So this gives rise to the
following interactions: deuterated-deuterated equal to 1, deuterated-pure
equal to (0.96) 1 / 2 , and pure-pure equal to 0.96.
First, we localize the value of the critical temperatures for different val-
ues of the concentration x. We determine this value as the point where
the susceptibility reaches its maximum. Nowadays, one of the best numer-
ical methods to determine critical temperatures by Monte Carlo simula-
tions is the histogram reweighting method, first introduced by Ferrenberg
and Swendsen. 9 ' 10 This method accumulates information about energy his-
tograms at a single temperature to determine the value of a certain prop-
erty, such as the susceptibility, at another point of the phase diagram. As
we are expected to be very close to the critical temperature we have used
the Wolff's single cluster algorithm, 11 ' 12 which is most convenient near the
critical temperature.
Simulations were performed for systems with 1000 spins and periodic
boundary conditions at fixed temperatures linearly extrapolated between
the values Tc*(0) and T*(l). More than 106 Monte Carlo steps (MCS) were
performed for each value of the concentration (x) leaving 105 MCS at the
beginning for thermalization. Five different realizations of the randomness
were considered for each concentration, resulting in very close values of the
critical temperature. We have used a canonical distribution of deuterated
dipoles: this means that the concentration of nondeuterated dipoles is kept
constant.
The deviations from linearity cannot be observed because they are inside
of our error estimation, which is around 0.01% smaller than the point size.
We may say, however, that there is a tendency for the critical temper-
ature to go slightly below the extrapolated linear value. In fact, when
the difference between extreme critical temperatures is made larger (by
about 33%), we are able to detect a decrease of 0.3% at x ~ 0.5 from
the linear behavior in our numerical simulations. In any case, even with a
large difference between the extreme critical temperatures, we are unable to
explain the relatively large value, around 1.7% obtained experimentally in
our ferroelectric-ferroelectric mixed systems. So we are justified in taking
into account possible quantum effects.
We consider 1 ' 3 the existence of a zero point energy, fkjJo{x)/2, where
LOQ(X) may be x dependent as noted before. From the point of view of the
Monte Carlo algorithm it is equivalent to introduce 13 an effective "quantum
transition temperature," which may be obtained from Eq. (2). Taking into
account that the maximum deviation AWQ(X) of zero point energy seems to
 Composition Dependence of Transition Temperature 433

occur at x ~ 0.5 we write

Au;o(z)
••4x(l-x), (6)
Aw 0 (0.5)

which implies Aw o (0) = 0 and Awo(l) = 0. It must be noted t h a t we have

Chosen [Awo(0.5)] M onte Carlo — [Awo(0.5)] E xperimental-
A possible justification for this x dependence of Awo might be t h a t for
x = 0 and i = l w e get something similar to perfect periodicity in the lat-
tice, with a well-defined zero point energy above the occupied potential min-
ima, while at x = 0.5 the aperiodicity is large and we may expect the largest
changes in the zero point energy, with respect to a perfect periodic system.
Results from Monte Carlo simulations, for classic and q u a n t u m approaches,
are also displayed at Figs. 4.10.1 and 4.10.2 for ( T G S ) i _ a : ( D T G S ) a ; and
( T G S e ) i _ x ( D T G S e ) a ; respectively. It can be easily observed t h a t t h e quan-
t u m effects d a t a match b o t h experimental d a t a and theoretical calculations.
We can conclude t h a t the q u a n t u m effect approach, which has proved
to fit anomalous behavior in other mixed systems, could justify the exper-
imental d a t a of the triglycine sulfate family. Also, we have shown t h a t in
Ising systems thermodynamics arguments cannot explain the decrease of
Tc(x) from a linear behavior, as in our partially deuterated crystals. Obvi-
ously, q u a n t u m effects are more likely to describe well large deviations as
those observed in mixed systems made up of very different components.

Acknowledgments

Financial support from D G I C y T (Grant no. PB96-0037) is gratefully

acknowledged.

References

1. J.A. Gonzalo, Phys. Rev. B 39, 12297 (1988).

2. W. Windsch, Ferroelectrics 47, 231 (1983).
3. J.A. Gonzalo, Ferroelectrics 168, 1 (1995).
4. B. Brezina and F. Smutny, Czech. J. Phys. 18, 393 (1968).
5. C. Arago, B. Noheda and J.A. Gonzalo, Ferroelectrics 238, 1 (2000).
6. K. Gesi, J. Phys. Soc. Jpn. 4 1 , 565 (1976).
7. C. Arago and J.A. Gonzalo, J. Phys.: Condens. Matter 12, 3737 (2000).
8. J.A. Gonzalo, Effective Field Approach (World Scientific, Singapore, 1991).
9. A.M. Ferrenberg and R.H. Swendsen, Phys. Rev. Lett. 61, 2635 (1988).
434 Effective Field Approach to Phase Transitions

10. A.M. Ferrenberg a n d D.P. L a n d a u , Phys. Rev. B 4 4 , 5081 (1991).

11. U. Wolff, Phys. Rev. Lett. 6 2 , 361 (1989).
12. J.S. W a n g a n d R . H . Swendsen, Physica A 1 6 7 , 565 (1990).
13. J . Dec a n d W . K l e e m a n n , Solid State Commun. 1 0 6 , 695 (1998).
 Chapter 4.11

Temperature Dependence
of Mode Griineisen Parameters in
Ferroelectric Perovskites at T = Tc*
Carmen Arago, Jorge Garcia and Julio A. Gonzalo
Departamento de Fisica de Materiales C-IV,
Universidad Autonoma de Madrid, 28049 Madrid, Spain

Jose de Frutos
Departamento de Fisica Aplicada,
Escuela Tecnica Superior de Ingenieriade Telecomunicacion,
Ciudad Universiraria s/n, 28040 Madrid, Spain

An approximate expression for the temperature dependence of the

Griineisen parameter 7 T O ( T ) for ferroelectric perovskites is obtained,
which implies a Curie-Weiss behavior in the vicinity of the transition
temperature. While no temperature-dependent data on 7TO (T) itself is
available, indirect estimates based upon the frequency and volume tem-
perature dependence seem to give reasonable results.

T h e mode Griineisen parameter is defined 1 as

dw/u)
7 =
dV/V

where duj is the frequency shift of the mode frequency w and dV is the
variation of the equilibrium volume V, produced in b o t h cases by changes
in pressure. In earlier works, 2 ' 3 the transverse optic Griineisen parameter
TToCO has been related to the frequency ratio x = WLO/WTO in several

"Work previously published in Phase Transitions 76, 3 (2002). Copyright © 2002.

Taylor & Francis Group.

435
436 Effective Field Approach to Phase Transitions

binary cubic crystals through a rather simple expression Ax2 + B, where

the coefficients A and B change for each family of binary compounds.
For a diatomic pseudocubic crystal, the equations of ionic motion can
be written as

mu = F- e.Eiocai. (1)

If we substitute the ionic displacement at the r site u(r) = uoe _lw *

and divide both members by u(r), Eq. (1) transforms for transverse and
longitudinal modes into

2 ,4ne2
-mwTO = / - y —, (2)
8 7 I
2 , , "e2 /ON
- m w L O = / + y —. (3)

Subtracting Eq. (2) from Eq. (3) we obtain

e2
W L O - < 4 O = 4 T T — =Q2, (4)

which in terms of x = WLO/^TO can be written as

x2 - 1 = ft2/<4o- (5)

Differentiating Eq. (4) we obtain

2wLo<9wLO - 2WTO<9WTO jLv_2n _o^

= I 47r—— 1 ( — — I == -fl

and then, dividing by WTO^WTO and introducing mode Griineisen parame-

ters according to their definition

. ,-{x2-l), .
\7TO/ "TO \ 7 T o / V7TO/
(6)
7LO-1/2 1 / ^ 2 1
x
TTO - 1 / 2
= —z
aH =*• 7TO = V 7LO - 27, )
/ + 2

Equation (6) is similar to Wakamura's expression, with the coefficients

A = 7LO — 1/2 and B = 1/2, respectively.
 Temperature Dependence of Mode Griineisen Parameters 437

Taking into account the Lyddane-Sachs-Teller relationship involving

the high- and low-frequency dielectric constant and the corresponding lon-
gitudinal and transverse frequencies we can write

7LO ~ 1/2 ^ £QQ 1 \ eo(T) 1

7TO - 1/2 e0(T)
7TO 7LO
+
Here we can make use of the Curie-Weiss law for the low-frequency
dielectric constant

C
eo(T) = T>TC,
T-Tc
and then we can obtain a similar expression for 7TO

C/£oo
7TO 7LO - 2) + T>TC, (7)
T-Tc

which gives a Curie-Weiss law like temperature dependence of the trans-

verse optical Griineisen parameter. Figure 4.11.1 shows schematically the
behavior of the inverse of longitudinal and transverse optical Griineisen
parameters. Note that the corresponding expression for 7 T O ( T ' < Tc) should
contain AC instead of C (for a first order transition) and (Tc - T) in the
denominator.

y-l
'LO
0.05

r \y'
\ 'TO

0.01 -

'
100 115
T(°C)
Fig. 4.11.1. Schematic behavior of the inverse Griineisen parameters for BaTiC>3. It
must be noted that as the longitudinal optical parameter is temperature independent,
the inverse of the transverse optical parameter behaves as a Curie-Weiss like law.
438 Effective Field Approach to Phase Transitions

T h e formal similarity between Eqs. (6) and (7) is a result of the

Lyddanne-Sachs-Teller relation, which results in

which is due to the t e m p e r a t u r e dependence of UITO, as it should be expected

for the soft mode t h a t is a signature of the first order ferroelectric transition.
If we approximate a perovskite-like BaTiOa as a binary compound 4
formed by two ionic groups, B a + + and TiO^~, we can evaluate, after d a t a
from several authors, 5 ~ 9 an approximated value of 7 x 0 — 20, and a sharp
discontinuity of the transverse optical Griineisen parameter between T c (the
Curie t e m p e r a t u r e obtained from e~l(T) for T > Tc) and Tg (the critical
t e m p e r a t u r e at which the discontinuity at e _ 1 ( T ) occurs), 7 x 0 ( ^ 0 ) — 100,
which is similar to the behavior of the inverse of the dielectric constant,
e _ 1 ( T ) , at the first order ferroelectric transitions.
We may conclude t h a t anomalous Curie-Weiss behavior in the tempera-
t u r e dependence of the Griineisen parameter 7 x 0 (T) must be expected near
ferroelectric or structural phase transitions characterized by soft modes.

Acknowledgments

We gratefully acknowledge the D G C I C y T for the G r a n t BFM2000-032.

References

1. N.W. Ashcroft and N.D. Mermin, Solid State Physics (Saunders College Pub-
lishing, New York, 1976).
2. K. Wakamura, Phys. Lett. A 118(8), 419 (1986).
3. T. Fernandez-Diaz and J.A. Gonzalo, Phys. Lett. A 123(7), 349 (1987).
4. J.A. Gonzalo, J. De Frutos and J. Garcia, Solid State Spectroscopies (World
Scientific, Singapore, 2002).
5. H.E. Kay and P. Vousden, Philos. Mag. 40, 1019 (1949).
6. G. Shirane and S. Hoshino, J. Phys. Soc. Jpn. 7, 5 (1952).
7. C.J. Johnson, Appl. Phys. Lett. 7(8), 221 (1965).
8. J.A. Gonzalo and J.M. Rivera, Ferroelectrics 2, 31-35 (1971).
9. A. Scalabrin, A.S. Chaves, D.S. Shim and S. Porto, Phys. Stat. Sol. (b) 79,
731 (1977).
 Chapter 4.12

Quantum Tunneling Versus Zero

Point Energy in Double-Well
Potential Model for Ferroelectric
Phase Transitions*
C.L. Wang1'4, C. Arago*, J. Garcia*
and J.A. Gonzalo*
^Department of Physics, Shandong University,
Jinan 250100, People's Republic of China
^Departamento de Fisica de Materiales, Facultad de Ciencias C-IV,
Universidad Autonoma de Madrid, 28049 Madrid, Spain

The Ising model in a transverse field, which involves quantum tunneling

in double potential wells, has been used for many years to describe fer-
roelectric phase transitions. An alternative model previously published
takes into account the effect of a non-negligible zero-point energy in
the double potential wells at the phase transition. A comparison of the
respective Curie temperatures, spontaneous polarizations, and suscepti-
bilities shows that both models are nearly equivalent. Quantitative dif-
ferences of the two methods are apparent at low temperature where the
saturation polarization value with non-negligible zero-point energy is
higher than the same quantity with the Ising model in a transverse field.

4.12.1. Introduction

T h e Ising model in a transverse field was first employed by de

Gennes 1 to describe order-disorder-type ferroelectrics. T h e model assumes

"Work previously published in Physica A 308, 337 (2002). Copyright © 2002.

Elsevier B.V.

439
440 Effective Field Approach to Phase Transitions

ferroelectrics to consist of pseudo-spins with interactions in a transverse

field. By including multi-spin interactions, this model can be used to
describe first order phase transitions in ferroelectrics.2 The Ising model
in a transverse field has also been applied successfully to study surface and
size effects in ferroelectrics. The influence of the surface on the Curie tem-
perature and on the excitation spectrum has been obtained in semiinfinite
systems. 3 ' 4 The dependence of Curie temperature on film thickness as well
as on surface variation of exchange constant and transverse field have been
studied under mean field theory 5 ' 6 and effective field theory. 7 ' 8 Later, this
model was extended to calculate polarization and susceptibility,9 as well as
dynamical property 10 and other properties of ferroelectric films. In recent
years, the Ising model in a transverse field has been used to investigate
the phase transition properties in ferroelectric superlattices, 11 pyroelectric
properties of ferroelectric multilayers, 12 and phase transition properties of
ferroelectric particles. 13
On the other hand, the effective field approach, which is analogous
to Weiss' theory for phase transition in ferromagnetism, is another the-
oretical method to describe phase transition properties in ferroelectrics
and other systems such as alloys and superconductors. 14 The inclusion
of quadrupolar and higher order terms into the effective field in sec-
ond order transitions in uniaxial ferroelectrics is shown to describe well
the jump in specific heat at the Curie temperature of the triglycine sul-
fate family crystals. 15 The thermal hysteresis accompanying discontinu-
ous ferroelectric transition can be estimated if one takes into account
the quadrupolar contribution to the effective field. The calculated val-
ues are in fair agreement with observed thermal hysteresis in several fer-
roelectrics belonging to different families.16 A general equation of state
using the effective field approach has been obtained for pressure- and
temperature-induced transitions in the ferroelectric triglycine selenate. 17
By including the zero-point energy, a simple quantum effective field
approach has been developed to explain the Curie temperature in mixed
ferroelectric system of rubidium/ammonium dihydrogen (RDP-ADP) 1 8
and tris-sarcosine calcium chloride/bromide (TSCC-TSCB). 19 Recently,
this quantum effective approach has successfully explained 20 the Curie
temperature deviations from those to be expected from the classical
limit in triglycine sulfate/deuterated, triglycine sulfate (TGS-DTGS), and
triglycine selenate/deuterated triglycine selenate (TGSe-DTGSe) mixed
crystals. 21 ' 22
 Double-Well Potential Model for Ferroelectric Phase Transitions 441

4.12.2. Effective Field Approach

The effective field approach to ferroelectric phase transitions is certainly

the simplest possible way to study phase transitions. In its simplest version
(Eeff = E + PP), which takes into account only dipole interactions, it is
capable of describing fairly well the main features of continuous ferroelectric
phase transitions. A more general expression of effective field is

£ eff = E + pP + 7 P 3 + SP5 + A, (1)

given in terms of an external field E and odd powers of the polarization

P, which correspond successively to dipolar, quadrupolar, octupolar con-
tributions, etc. The coefficients /3, 7, 6 may be expected to depend on the
geometry of the lattice and on the spatial charge distribution within the
unit cell. The equation of state is given by Gonzalo 14

P = J v, t a n h (fgf), (2)

where N is the number of elementary dipoles per unit volume and /i is

the electric dipole moment, fee is the Boltzmann constant, and T is the
absolute temperature. From this expression we can easily see that the low-
temperature saturated polarization is Pso = Nfi. For simplicity, keeping
terms only up to the dipole contribution in Eefi in Eq. (1), one can rewrite
Eq. (2) as

Pso = N/j, is the spontaneous polarization at low temperature. Taking into

account that as T approaches Tc from below at E = 0, P = Ps approaches
zero, as a result the Curie temperature

(4)

The equation of state given in Eq. (3) in implicit form can be made
explicit as

E
=ir,-*ri£)-',F- (5)
442 Effective Field Approach to Phase Transitions

The dielectric constant can be obtained easily from the above expression
as follows:

~-l
1 'dE' kBT N p
4ir 47T (7V M ) 2 -
(6)
9P. E^0 P2 4-7T'

For temperatures below the Curie temperature, i.e., at the ferroelec-

tric phase, the above equation can be rewritten in the vicinity of Curie
temperature as

1
£- = - ^ ( T - T c ) = -§(T-Tc), T<TC. (7)

Here, C = 4 x N2n/ks is the Curie-Weiss constant. When the tem-

perature is higher than the Curie temperature, at the paraelectric phase
(Ps = 0), we have

'-, = -5^?-S-£ (r - r ->- TiT

<- (8)

Quantum mechanically, the zero-point energy should be included, so we

have

hco0(^ + (n)T^=kBT;, (9)

where T* refers to the classical Curie temperature in Ref. 19:

(n) Tc = [exp(/iw0/fcBrc) - l ] " 1 (10)

is the thermal average of the number of energy quanta excited in each unit
dipole at temperature T = Tc, above the zero-point energy level EQ =
l/2fkoo, or Einstein energy.23 From Eqs. (9) and (10), we can have

h
knT* = ^ll (11)
B c V ;
tanh(/iw0/2A;BTc)'

From the above we can see that the zero-point energy rescales the real
temperature to T* or the quantum temperature scale. 24 ' 25 Therefore, the
 Double- Well Potential Model for Ferroelectric Phase Transitions 443

quantum Curie temperature can be obtained from Eq. (3) as

= H/2 (12)

or more explicitly in the form

— w^ . (13)
tanh- 1 (/iw 0 /2fc B ^At 2 )

Therefore, the dielectric constant at the paraelectric phase [Eq. (8)] can
be rewritten as

e -i = _^9 I A (14)

At zero temperature,

1 2
£- ( T = 0) = ^ ( i ^ 0 - ^ ) , (15)

which means that if the zero-point energy is large enough, there will be no
phase transition to the ferroelectric phase. Equation (14) is equivalent to
the famous Barret formula,26 which is used to explain the low-temperature
behavior of quantum ferroelectrics, such as SrTi03 and CaTiC>3 and their
solid solutions.

4.12.3. Ising Model in a Transverse Field

The starting point of the Ising model in a transverse field (IMTF) is the
double-well potential in hydrogen bonds in ferroelectric such as the potas-
sium dihydrogen phosphate. The spin-1/^ Hamiltonian IMTF in the general
form27 is

J s s
H = -J2 ViS* -\Y, ^ i J - 2» E w - (16)
where the first and third sums are over sites i and the second is over sites
i and j . The first term involves the transverse field O,, which is related
to the tunneling frequency. Sx and Sz are spin-1/^ operators, Sx describes
the tunneling effect, and Sz is related to the polarization. The third term
accounts for the coupling to an external electric field E{\ / / i s the dipole
444 Effective Field Approach to Phase Transitions

moment per Ising spin. With the usual notation, (...) denotes a thermal
average. The mean field equation derived from Eq. (16) is

where

Hi = H(ni,0,J2Jij(S-)+2fiE^ (18)
is the molecular field acting on spin at in the ith site. The polarization Pi
on site i is proportional to (S1?), namely Pi = 2/x(5f) and in the absence
of an applied field, Eqs. (17) and (18) give for this average
1/2
(sz) _ S j Msjp + 2/x£ tanhf [n? + {J13{SD + 2»E)2} \
w
2[n? + (j«(s;> + 2AtE)2] 1 2fcBr /•
(19)

In a uniform bulk material all fli are equal and in the nearest-neighbor-
exchange approximation all exchange constants J^ are equal to J. There-
fore, the spontaneous polarization is related to (Sz) at zero external field
in the form

2+ 2
2[n2 + (n0J(Sz))2}1/2 .tanhp
{ y 2kf »
T H,B
(20)
where no is the number of nearest neighbors. At temperatures close to the
Curie temperature, (5?) approaches zero, and the mean field value of the
Curie temperature Tc is found by solving

kBTc = P^ . (21)
tanh" 1 (2fi/n 0 J)
The dielectric susceptibility can be found from Eqs. (19) and (20) as
£ = (l/4n)(dP/dE). For the ferroelectric phase

e -i = I I ^L- (22)
WTTN[I2 /((S 2 )) 167T7V> 2 '
V ;

where the function f((Sf)) is introduced to simplify the above equation,

and has the form
ft2 (l-4(S2)2)(n0J)2-4ft2 .2'
f((Sz)) 2 2 2 no J 4kBT -(sy
[ft + (n 0 J(S )) ]
(23)
 Double-Well Potential Model for Ferroelectric Phase Transitions 445

and for paraelectric phase the dielectric constant becomes

_x 20. 1 UQJ
=•-1 : s^l (2A)
2
167rNfi ta,nh(n/2kBT) WTTN/J,2' y
'

4.12.4. Discussion and Comparison

First, we compare the expressions of the Curie temperatures obtained by

both the methods. If we ignore the tunneling term (i.e., the transverse field)
in the IMTF, the expression of Curie temperature [Eq. (21)] reduces to

kBTc = n0J/A. (25)

By comparison with Eq. (4) obtained in the effective field approach, we

can have the following relation for the parameters in the two models:

0Nfi2 = n0 J/4. (26)

Therefore, /3 corresponds to the dipole-dipole interaction J in the

IMTF. If the zero-point energy is included in the effective field approach, the
expression to determine the Curie temperature is Eq. (11) or (12). By com-
parison with Eq. (21) from IMTF, we can see that the tunneling frequency
is equivalent to the zero-point energy in the effective field theory, i.e.,

r)oj0 = n. (27)

Equations (25) and (26) can be further confirmed by the dielectric con-
stant at paraelectric phase [see Eq. (17) from effective field approach and
Eq. (24) from IMTF].
In Fig. 4.12.1, we present the Curie temperature from the two models
for comparison at different zero-point energies or tunneling frequencies.
Figure 4.12.1(a) is for effective field approach, and Fig. 4.12.1(b) for IMTF.
From the figure we easily see that the Curie temperatures are exactly the
same, even the critical behavior near the critical value of zero-point energy
or critical frequency, marked by arrows in the figures.
However, the two theoretical approaches do not always have exactly
the same corresponding expressions. An example is the polarization at low
temperature. From effective field theory, as temperature approaches zero,
(n) approaches zero; however, the energy does not tend to zero but to
446 Effective Field Approach to Phase Transitions

Fig. 4.12.1. Transition temperature as a function of zero-point energy (a) and as a

function of tunneling frequency (b).

l/2rjuJo, then the low-temperature spontaneous polarization is given by

P = iV M tanh(^, (28)

which is not the classical limit Nfx. It means that at zero temperature
there are still fluctuations, which prevent all dipole moments from aligning
completely in the same direction. From the above we can get the critical
value for the zero-point energy as
T]LOC = 2N/3/I2 (29)

From Eq. (20) of IMTF at temperatures close to zero temperature we

have a spin average given by

(Sz)o = \Vl-CM/n0J)2, (30)

which is not equal to 1/2, the classical limit. It means that not all spins are
pointing in the same direction. Also, the critical value obtained from the
 Double- Well Potential Model for Ferroelectric Phase Transitions 447

0.5

w
V
CM
0.3

j . i i 1 i 1 1 I 1
"o.O 0.1 02 0.3 0.4 0.6
x = ha> lANu.2^ or n/n J
o o

Fig. 4.12.2. The ground-state polarization from Ising model in transverse field and
effective field approach with zero-point energy.

above expression is
2QC = n0J. (31)

From Eqs. (29) and (31), we can see that the critical values are the same
if we recall expressions (25) and (26). The physics meaning behind the above
two equations are the same. The zero-temperature polarization at different
zero-point energies or tunneling is shown in Fig. 4.12.2 for comparison.
The difference vanishes when there is no zero-point energy or tunneling
frequency, and also near the critical value of the zero-point energy. The
larger difference appears around the middle of the critical value.
In order to give a comparison in the whole temperature range, the tem-
perature dependence of polarization and dielectric constant are shown in
Fig. 4.12.2. To enhance the difference, we choose fko/4Nfi2P = ^1/TIQJ =
0.35 in both diagrams. The difference in saturation polarization is largest
at zero temperature (Fig. 4.12.3(a)) and as the temperature increases, the
difference becomes smaller. The behavior of the polarization near the crit-
ical temperature is identical for both models. For the dielectric constants,
as shown in Fig. 4.12.3(b), the overall difference seems to be a little smaller
than that of polarization in Fig. 4.12.3(a), and there is no difference at the
paraelectric phase.

4.12.5. Conclusion

From the comparison, we can see that when the zero-point energy is
included in the effective field approach, the corresponding equations become
448 Effective Field Approach to Phase Transitions

0.20 =""
^ EFA+
0 0.15 IMTF

I . I .
10
x=0.35
& 0.10

0.05
•

0.00 i 1 i

0.0 0.5 1.0 1.5

(a) TTTc

1.4
•

1.2
yEFA+
1.0
• IMTF

i::
x=0.35

0.4

0.2
0.0 \^~ i I
0.0 0.5 1.0 1.5 2.0
(b) TTTc

Fig. 4.12.3. The temperature dependence of polarization (a) and dielectric constant
(b) at hui/iNn2!3 = a/no J = 0.35.

the same or very similar to the equations from Ising model in a transverse
field under mean field approximation. The effective field approach can be
used to describe phase transitions in ferroelectrics with classical behavior
as well as with quantum effects. The tunneling frequency in the Ising model
in a transverse field is then analogous to the zero-point energy. The results
from the two models can be said to be nearly equivalent, except the quan-
titative differences at low temperatures, when the zero-point energy or the
tunneling frequency are away from the critical value.

Acknowledgments

Financial supports from DGICyT through Grant no. PB96-0037 is grate-

fully acknowledged. C.L. Wang is financially supported by China Scholar-
ship Council to visit Universidad Autonoma de Madrid.
 Double- Well Potential Model for Ferroelectric Phase Transitions 449

References

1. P.G. Gennes, Solid State Commun. 1, 132 (1963).

2. C.L. Wang, Z.K. Qin and D.L. Lin, Phys. Rev. B 40, 680 (1989).
3. M.G. Cottam, D.R. Tilley and B. Zeks, J. Phys. C 17, 1793 (1984).
4. I. Tamura, E.F. Sarmento and T. Kaneyoshi, J. Phys. (717, 3207 (1984).
5. C.L. Wang, W.L. Zhong and P.L. Zhang, J. Phys.: Condens. Matter 3, 4743
(1992).
6. H.K. Sy, J. Phys.: Condens. Matter 5, 1213 (1993).
7. X.Z. Wang and Y. Zhao, Physica A 193, 133 (1993).
8. E.F. Sarmento and J.W. Tucker, J. Magn. Magn. Mater. 118, 133 (1993).
9. C.L. Wang, S.R.P. Smith and D.R. Tilley, J. Phys.: Condens. Matter 6, 9633
(1994).
10. C.L. Wang and S.R.R Smith, J. Phys.: Condens. Matter 8, 3075 (1996).
11. C.L. Wang and S.R.R Smith, J. Kor. Phys. Soc. 32, S382 (1998).
12. Y. Xin, C.L. Wang, W.L. Zhong and P.L. Zhang, Solid State Commun. 110,
265 (1999).
13. C.L. Wang, Y. Xin, X.S. Wang and W.L. Zhong, Phys. Rev. B 62, 11423
(2000).
14. J.A. Gonzalo, Effective Field Approach to Phase Transitions and Some
Applications to Ferroelectrics (World Scientific, Singapore, 1991).
15. B. Noheda, G. Lifante and J.A. Gonzalo, Ferroelectrics 15, 109 (1993).
16. J.A. Gonzalo, R. Ramirez, G. Lifante and M. Koralewski, Ferroelectrics 15
9 (1993).
17. J.R. Fernandez del Castillo, J.A. Gonzalo and J. Przeslawski, Physica B 292,
23 (2000).
18. J.A. Gonzalo, Phys. Rev. B 39, 12297 (1989).
19. J.A. Gonzalo, Ferroelectrics 168, 1 (1995).
20. C. Arago, M.I. Marques and J.A. Gonzalo, Phys. Rev. B 62, 8561 (2000).
21. C. Arago and J.A. Gonzalo, J. Phys.: Condens. Matter 12, 3737 (2000).
22. C. Arago and J.A. Gonzalo, Ferroelectrics Lett. 27, 83 (2000).
23. E.K.H. Salje, B. Wruk and S. Marais, Ferroelectrics 124, 185 (1991).
24. J. Dec and W. Kleemann, Solid State Commun. 106, 695 (1998).
25. W. Kleemann, J. Dec and B. Westwanski, Phys. Rev. B 58, 8985 (1989).
26. J.H. Barrett, Phys. Rev. 86, 118 (1952).
27. R. Blinc and B. Zeks, Soft Modes in Ferroelectrics and Antiferroelectrics
(North-Holland, Amsterdam, 1974).
 Index

Aizu, K., 4, 62 critical

alloys exponents, 9, 17-20, 24-27, 33, 64,
quenching, 38 68-72, 82, 83, 88, 94,
solubility, 37 103-105, 108-112, 114-116,
Andrews, T., 4, 11 143, 260, 266, 270, 338
isotherm, 18, 26, 48, 49, 71, 72, 81,
84, 107, 115, 260, 270, 342
/3-brass, 39, 43
magnetic field of superconductors,
Bardeen-Cooper-Schrieffer (BCS)
33
hamiltonian, 32 Curie constant, 21, 50, 125, 137, 138,
Bethe, H., 43 185, 186, 200, 201, 218, 229, 231,
Bogolubov, N., 4 253, 260, 270, 349, 360, 368, 386,
Bose condensation, 53, 54 419
Bose-Einstein statistics, 53, 54 Curie, P., 4
Bragg-Williams theory, 38, 42-44
Brillouin zone, 93, 96, 170, 173 Debye
frequency, 33, 257
charge density waves, 34 sphere, 92, 93
chemical potential, 33, 54, 73, 111 temperature, 3, 33, 34, 170
coexistence curve, 17, 25, 85, 107, deuteration effects, 421
112, 115 dielectric constant, 6, 45, 47, 49, 103,
composition dependence, 273 119-122, 124, 131, 141-143, 145,
183-185, 198, 222, 226, 241, 242,
compressibility, 18, 19, 115
250, 251, 256-260, 266, 270,
conjugated variables, 4, 289, 308
273-275, 283, 289-292, 300, 301,
continuity phase transition, 3, 5, 62,
307-311, 313, 319-321, 323,
68-70, 191, 241, 256, 337, 368, 441 329-331, 349, 352, 353, 368, 379,
Cooper pair, 4, 32, 34, 53, 56, 59, 380, 421, 424, 425, 428, 437, 438,
91-99 442, 443, 445, 447, 448
cooperative phenomena dielectric losses, 249
discovery, 4 dipole moment
first successful theory, 4 ferroelectric, 61, 62, 124

451
452 Effective Field Approach to Phase Transitions

ferromagnetic, 28 ferroelectric materials, 141, 250, 255,

of cooper pair, 92, 93, 95 296, 319, 349, 355, 398, 413, 415
dipole waves (ferroelectric) ferroelectric response times, 283
contribution to change in P s , 170, ferroelectricity, 61
171 in Zn^Cdi-^Te, 137
contribution to specific heat, 170, ferromagnetic materials
171 hard and soft, 21
in some materials, 176 uniaxial dipolar, 30
dipole-dipole hamiltonian, 171, 179, Fisher-Rooshbrook equality, 116
180 free energy
domains
in Landau theory, 67
ferroelectric, 104
of liquid-vapor systems, 12
ferromagnetic, 62
of order-disorder alloys, 4
frequency dependence, 221
effect of impurities
impurity concentration, 119
generalized (P, T) equation of state,
internal bias, 119
289
effect of impurity
Gibbs free energy, 75
modified equation of state, 131
grain size effects, 385
effective field
Griffiths equality, 262
in ferroelectrics, 103
Guggenheim, E.A., 7
in liquid-vapor systems, 7
in superconductors, 31
in superfiuids, 97 Heisenberg, W., 29, 81, 85, 87, 88, 431
inferromagnets, 21 Helium ( 4 He), 53, 54, 56, 98, 99
effective mass, 96, 379 homogeneity assumption, 108, 109,
elastic compliance, 64, 65 114
electron-electron interaction, 31, 32 hysteresis loops
electron-phonon interaction, 32-34, ferroelastic, 61
63, 96 ferroelectric, 45
elementary excitations ferromagnetic, 21
in ferroelectrics, 169
in superfiuids, 97 ideal gas, 11, 13, 16
energy conversion, 351
energy gap, 31, 33, 59, 94, 96, 98 Keesom, A., 4
equation of state Keesom, W., 4
of ferromagnets, 23
of liquid-vapor systems, 11 Landau, L. D., 67
excitons, 34 lattice parameter, 3, 6, 51, 245, 306,
382, 393, 397, 401, 403, 405, 407,
x - FRH transition in PZT, 299 411, 413
Fermi surface, 93, 96 lattice polarization, 48
Fermi velocity, 96, 97 law of corresponding states, 7, 8, 15,
Fermi-Dirac distribution function, 33 16, 103, 104, 108
ferroelasticity, 61, 62 Lennard-Jones potential, 97
 Index 453

logarithmic correction, 50, 64, 78, 79, renormalization group, 50, 87, 88,
183-185, 187, 198, 203, 229, 231, 203, 338
232, 262, 338, 348, 349 resonating valence bonds, 34
Lorentz factor, 29, 48
low field switching, 360 scaling and metastable behavior, 337
scaling assumption, 81, 82, 86
Miiller, K. A. and Bednorz, G. J., 34 scaling equation of state, 265-267,
magnetic susceptibility, 26 269
mixed ferro-antiferroelectric systems, solid solutions
129, 133, 427 interstitial, 37
mixed ferroelectric, 427 substitutional, 37
mode Griineisen parameter, 435, 436 specific heat, 3
in ferroelectrics, 49, 172
Onnes, K., 4 in ferromagnetics, 27
Onsager's solution, 8 in ferromagnets, 173
order parameters in liquid-vapor systems, 19
dimensionality, 5 in superconductors, 47
fluctuations, 67 specific heat and quadrupole
order-disorder transition in alloys, 4, interactions, 243
37, 42, 43 spin density waves, 34
ordinary critical point, 68, 70, 71, spontaneous magnetization, 5, 8,
295, 337, 338, 345, 346 21-25, 27, 70, 93
over-screening, 91 spontaneous polarization, 27, 46-48,
50, 70, 103, 125, 131, 132, 139, 145,
partition function, 12, 23, 48, 93 163, 169-171, 173-177, 179, 180,
photoacoustic effect, 207 191, 195, 208, 215-218, 226, 229,
piezoelectric resonances, 377, 378, 230, 232-234, 238-241, 243-247,
382-384 250, 257-261, 266-268, 270, 291,
piezoelectricity, 378, 379 293, 294, 299, 302, 308, 310, 311,
Planck's distribution law, 54, 430 314, 316, 320, 324, 328-330, 339,
polarization reversal 343, 352, 353, 359, 368, 372, 374,
coercive field, 46, 144 420-424, 439, 441, 444, 446
pulse shape, 163 spontaneous strain, 61, 62, 64, 65, 70,
switching current, high field, 147 191
switching current, low field, 147 superconductivity, 53, 56, 91, 97
pressure dependence, 191, 192, 195, superconductive materials
196 metallic, 34
pyroelectricity, 46, 119, 181, 208, 273, oxide, 31, 34, 36
300, 302, 308-311, 319, 320, 440 superfluidity, 4, 53, 54, 56, 59, 91, 97
PZT monoclinic phase, 394, 397 susceptibility
dielectric, 6, 230, 444
quantum tunneling, 439 magnetic, 26
quasitricritical behavior, 255, 260, 263 symmetry breaking, 5

real gas, 11, 15, 18 Tamman, G., 4, 37

relaxation (near T c ), 123, 141, 226 thermal hysteresis, 237-242
454 Effective Field Approach to Phase Transitions

tilts and displacements in PZT, 307 tricritical point, 5, 68-70, 72, 183,
transition entropy 191, 192, 195, 198, 215, 216, 219,
ferroelectric, 50, 420 233, 240, 245, 247, 259, 265-267,
ferromagnetic, 27 270, 273, 274, 277, 280, 337, 347,
transition heat 421, 423
ferroelectric, 43 two sublattice model
ferromagnetic, 27 antiferroelectric (afe) case, 131
transition temperature, 5 ferroelectric (fe) case, 131
in ferroelastics, 61, 62, 65 mixed (fe-afe) case, 129
in ferroelectric, 50
of ferromagnetic, 21 uniaxial pressure effects, 367
of order-disorder alloys, 41
of superconductors, 31 Valasek, J., 4, 45
of superfluids, 55 Van der Waals, J. D., 11
transition temperature (mixed virial theorem, 172
ferro-antiferroelectric systems)
classical, 133 Weiss, P., 4, 21
quantum mechanical, 134 Widom's equality, 262
transitions in complex ferroelectric
ceramics, 329
 Effective Field Approach
to Phase Transitions and
Some Applications to
Ferroeiectrics (2nd Edition)

This book begins by introducing the effective field

approach, the simplest approach to phase transitions.
It provides an intuitive approximation to the physics
of such diverse phenomena as liquid-vapor transitions,
ferromagnetism, superconductivity, order-disorder in
alloys, ferroelectricity, superfluidity and ferroelasticity.
The connection between the effective field approach
and Landau's theory is stressed.

The main coverage is devoted to specific applications

of the effective field concept to ferroelectric systems,
both hydrogen bonded ferroeiectrics, like those in the
TGS family, and oxide ferroeiectrics, like pure and
mixed perovskites.

6168 he
) 875-1

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