Pyroelectric materials
Pyroelectric materials
Pyroelectric materials
M R SRINIVASAN
Materials ScienceGroup, Tam Institute of FundamentalResearch,Bombay400005, India
Abstract. Thispaper presentsa reviewof pyroelectricmaterials.The physicsof pyroclcctric
materials is described.Variouspyroelectricmaterialsare compared for their efficiencyin the
detection of radiation. Current trends in pyroelectricmaterialtechnologyare highlighted.
Keywords. Pyroelectricity,ferroelectricity;piezoelectricity.
1. Introduction
It has been known for a long time that some crystals exhibit electric polarization when
their temperature is changed. This phenomenon is known as pyroelectricity and arises
out of the temperature dependence of spontaneous polarization in these crystals. The
pyroelectric polarization, however, does not persist for a long time and gets neutralized
due to imperfect insulation and the presence of free charges in the crystal. While all the
ferroelectric crystals are necessarily pyroelectric, the converse need not be true. A built-
in asymmetry in the crystal structure hindering the polarization reversal or a high
coercive field exceeding the limit of electrical breakdown might prevent a pyroelectric
from being a ferroelectric.
Quantitatively, the pyroelectric effect could be described by the equation
AP¢= plAT,
where AT denotes the change in temperature, AP~(i= 1, 2, 3) are the changes in the
components of polarization P in the three-dimensional space and Pi are the
corresponding pyroelectric coelIicients, p is a vector property and by Neuman's
principle ought to remain invariant under all the symmetry operations of the crystal
(Nye 1962). Hence pyroelectricity can be exhibited only by crystals belonging to the ten
polar classes 1, 2 m, 2 mm, 3, 3 m, 4, 4 mm, 6 and 6 mm.
It may be pointed out here that in some crystals polarization may appear under the
influence of hydrostatic pressure and this is a special case of piezoelectric effect. Since
hydrostatic pressure is a scalar-like temperature this polarization linearly proportional
to the hydrostatic pressure can also be treated on par with pyroelectricity. Thus the
piezoelectric effect under hydrostatic pressure can occur only in the above mentioned
ten polar classes. In general the piezoelectric effect has the mathematical character of a
third rank tensor and is restricted only to 20 non-centrosymmetric classes excluding the
class 432. Thus the symmetry permits all the pyroelectric crystals to be piezoelectric
while the converse is not true. Therefore it is possible to imagine two possible
contributions to pyroelectricity in the following way. Experimentally to observe
pyroelectricity one can heat the crystal and observe the change in polarization. The
experiment could be performed in two ways. Either the shape and size of the crystal can
317
318 M R Srinivasan
be kept fixed during the heating or the crystal may be released so that thermal
expansion can occur quite freely. Obviously the magnitude of the effect observed in-the
two cases will be different. In the first case the crystal is clamped and the observed effect
may be regarded as the primary pyroelectricity. In the second case, in addition to the
primary etfect, there is pyroelectric effect due to the variation of piezoelectrically-
induced polarization with temperature. This is known as the secondary pyroelectricity.
The secondary pyroelectricity is found to contribute substantially to the total effect.
Hence for a free crystal the total pyroelectric effect could be written as
(dP/dT)o, • = (d P/dT)s, e + (d P/dS)r,E (dS/dT)~,, E (1)
where o, S and E denote the stress, strain and electric field respectively. Equation (1)
could be written as
p~.e = pS.~+ (d P / d o ) r ' ~ ( d o / d S ) r "~ (dS/dT)o, E
= pS, E + AT,
, , i ~ ,F.rT,
~ j ~ , , ~E' j ~~O,E , (2)
2. Theory of pyroelectricity
The lattice dynamical theory of primary pyroelectricity for the ease of ionic crystals
was first formulated by Max Born in the year 1945 (Born 1945). In this paper, Born had
indicated that primary pyroelectric coefficient would be proportional to T, though in his
later treatise on lamce dynamics he predicted the T a law for the pyroelectric coefficient
(Born and Huang 1954). Recently Szigeti has brought out clearly many salient features
of the theory, especially the r~,le of mechanical and electrical anharmonicity in primary
pyroeleetricity which in fact was overlooked by Born (Szigeti 1975, 1976).
In the case of ionic crystals, there are two important mechanisms of polarization.
One being responsible for absorption in the infrared i.e. the lattice or ionic polarization
and the other in the ullraviolet i.e. the electronic polarization. In the very simplest and
crude model known as the rigid ion model, the electron cloud around the ion is assumed
to be rigid and consequently there is no contribution from electronic polarization. For
such a model, the total dipole moment of the crystal is given by
M = ~e,Q°,
a
where Q, are the active normal coordinates i.e. those which produce uniform
polarization in the direction of M. :q are suitable normalizing constants.
However, in reality the electrons are deformed during the lattice vibrations as they
experience short range forces and also the dipolar field due to ions. The electron
deformation is not just linearly proportional to lattice displacements but involves
higher terms as well. Hence when one takes into consideration the electronic
polarization also, the dipolemoment of the crystal is given by
An important point to note is that % includes both the effects due to lattice
displacements and also the first order effects due to electron deformation. The above
expression for the dipolemoment clearly implies the presence of electrical anharmo-
nicity in the crystal.
For the ease of harmonic crystal, the potential energy is proportional to the square of
the normal coordinates. In reality crystals are not harmonic and the mechanical
anharmonicity has to be taken into account. For such a crystal the potential energy
involves the cubic and higher powers of the normal coordinates
Here Cj is the contribution of the jth mode to the specific heat and is given by
~ioJ~(O~j/OT), ~j being the average occupation number of the phonons with energy hwj.
From the above expression, it could be shown that under Debye's approximation
(which actually involves invoking some properties of fljj and boj~ it., ,',helong wavelength
limit), the primary pyroelectric coefficient obeys T 3 law. But as ha~ been rightly pointed
320 M R Srinivasan
out by Szigeti, in the case of complex polyatomic crystals, optic modes can have very
low frequencies and hence the T 3 behaviour is observed only at very low temperatures.
At this stage, it is also necessary to emphasize the role of both electrical and mechanical
anharmonicity in primary pyroelectricity. Since the primary pyroelectric effect does not
involve thermal expansion, for quite some time, it was regarded that only the electrical
anharmonicity was responsible for primary pyroelectricity. It may be mentioned that
thermal expansion is the result of mechanical anharmonicity. However, from the
expression for primary pyroelectric coefficient, it is evident that the part played by
mechanical anharmonicity cannot be neglected.
the incident energy required to produce a signal equal to that of detector noise). The
voltage responsivity as well as the detectivity depend not only on the particular
pyroelectric material but also on the characteristics of the amplifier employed for
detecting the pyroelectric voltage. The detailed theory of pyroelectric detector has been
discussed by several workers (Lang 1971; Liu 1978). It is sufficient for our purpose to
know that the voltage responsivity is proportional to p(ec)-1 while the detectivity is
proportional to p(c(etan6)l/2) -l, where p is the pyroelectric coefficient, e is the
dielectric constant, tan 6 is the loss tangent and c is the specific heat. Hence p(ec)- ~and
p(c(e tan ~)~/2)-~ could be regarded as the figures of merit of pyroelectric materials.
Clearly, in the case of pyroelectric materials which are also ferroelectric the dielectric
constant and the pyroelectric coefficient are strong functions of temperature and so is
their figure of merit. It could be shown that the figure of merit is maximum at the
temperature corresponding to the stability limit of the ferroelectric phase (Liu 1978).
4. Pyroelectric materials
p FM-R FM-D*
Material T(°C) ~ ( x 10 - s ) c s p ( x 10 -1°) ( x 10 -4) Reference
(1) (2) (3) (4) (5) (6) (7) (8) (9)
Tablel. (contd)
Material (1) (2) (3) (4) (5) (6) (7) (8) (9)
PLZT - 515 3"5 -- 8'0 -- -- -- Garn and
(0/65/35) S h a r p (1974)
i T s = 38o~c~
PLZT -- 600 3.9 -- 7"95 -- -- -- Garn and
(2/65/35) S h a r p (1974)
(T~ = 310~C)
PLZT 0 740 4.8 ..... 4-8 x 107 0.25 1.28 Beerman
(4/60/40) 25 870 5.6 2-6 7-85 3"0 x 107 0'25 1"18 (1975)
( T o = 218°C) 50 1020 6.3 . . . . 2"0 × 107 0-24 1,09
100 1400 7-6 . . . . 1 3 × 107 0-21 1.06
PLZT - 680 5.2 - - 7.90 . . . . Beerman
(4/65/35) (1975)
(T~ = 225°C)
PLZT 25 1400 10.0 2'6 7.83 5 1 × 107 0-23 2.8 Beerman
(6"5/65/35) (1975)
( ~ = 145"'C)
PLZT - 1860 13.0 -- 7.82 . . . . . Garn and
(7/65/35) S h a r p (19747
( ~ = 145~C)
PLZT - 3800 l 7.0 -- 7.80 . . . . Garn and
(8/65/35) S h a r p (1974)
(~ = lOffC)
Srtl - x}Ba~Nb~06 Beerman
(SB~) (1975)
x = 0-52 25 380 6.5 2.1 5.2 1.6 × 10 s 0"81 4-0
( ~ = 115'C)
x = 0"33 25 1800 11 ..... 1-2 x 108 0'29 5"8
(~ = 62C)
x = 0"25 -25 1600 5.6 - -- 9.0 x 10 ~ 0.17 2.5
(T~ = 30"C) 0 2500 12.0 . . . . 5.1 x 107 0.23 4.1
25 5000 37.0 . . . . 1-9 x l 0 T 0-32 7.7
50 12000 10.0 . . . . 6.5 x 106 0.04 1.2
Table 1. (contd)
Material (1) (2) (3) (4) (5) (6) (7) (8) (9)
Pb4.TsBao.25Ge3011 60 2-0 -- -- 10t4 -- -- Watton et al
(T~= 101°C) (1976)
Pb4.7oBao.3Ge3Oll 81 3'2 -- -- 10j'* -- -- Walton et al
(T, = 70°C) (1976)
Na NO2 25 7-4 0"5 2"1 2.2 -- 3"2 -- Garn and
(T, = 163°C) Sharp (1974)
Polyvinyl- -- 5"33 if01 . . . . . . . . Garn and
chloride (pvc) Sharp (1974)
Polyvinyl -- 5"0 0.10 2"3 1-38 -- ff87 -- Garn and
fluoride (PvF) 0-18 Sharp (1974)
Polyvinylidene - - 11-0 0-30 2-4 1.76 -- -- -- Garn and
fluoride (PvF2) Sharp (1974)
Polyacryl- -- 7.7 0.005. . . . . . Garn and
nitrile (PAW) 0-01 Sharp (1974)
Poly (4-nitro- -- 6.2 0-006 . . . . . . . Garn and
styrene) Sharp (1974)
atactic
Polyacry. . . . 0-01 . . . . . . . . Garn and
lamide (P^A) Sharp (1974)
(1) T(°C): Temperature in °C at which measurements are made; (2) ~: Dielectric constant;
(3) p: Pyroelectric coeflicient in Coul/cm2/K°; (4) c: Volume specific heat in J/em3/K°;
(5) s: Density in g/era3; (6) p: Ac resistivity in ohm-cm; (7) FM-R: Figure of merit for voltage
responsivity given by p(Ec)- J; (8) FM-D*: Figure of merit for detectivity given by p p~/2c- t;
(9) Ref.: Reference
Table I clearly indicates that TGS and Li2SO4 • H 2 0 are g o o d materials for pyroelectric
detection. But the main problem is their hygroscopic nature, which restricts the
operating conditions. Therefore LiTaO3 is generally preferred. The problem is rather
crucial for vidicon applications, where the material ought to be not only physically and
chemically stable in the temperature and pressure conditions o f the tube but also have
low thermal diffusivity, to obtain g o o d spatial resolution. That is why PVF2 is gaining
m u c h attention for vidicon applications on account o f its low thermal diffusivity as
c o m p a r e d to that Of TGS and LiTaO3, and also the ease with which thin target materials
can be prepared.
Similarly for application in laser optics, the choice o f the material is governed by its
vulnarability to radiation damage. Invariably crystals like TGS are not employed.
Materials with high curie temperature are f o u n d to be resistant to radiation damage.
The p h e n o m e n o n o f surface damage by laser pulses is not very well understood. Thus
the LiTaO3 detector is f o u n d to be satisfactory in the 1 m W - 3 W average power levels
from 10"6/~m C.W CO2 laser, but is damaged by a single 1/3 J pulse with a duration o f
200 msec. But a PZTO 1306 detector is not damaged even after fifty pulses. It has been
observed that polycrystalline ceramic pyroelectric materials are more resistant to
radiation damage than single crystals. Strontium barium niobates are another class o f
pyroelectric materials which are extensively employed in laser detection.
The temperature at which the detector has to be operated also determines the choice
o f the pyroelectric material. For better sensitivity o f the detector, the curie temperature
Pyroelectric materials 325
must be as close to that of the operating temperature (in such a case, it also becomes
necessary to take special care to avoid depoling in the material). In this sense, it is useful
to have pyroelectric materials whose curie temperature could be changed by changing
the composition, doping etc. This accounts for the interest in materials like SBN,~:TN,
PbsGesOlt, XGS-rGSE and PLZT ceramics. Of late ceramic-plastic composites and
improper ferroelectrics are found to have good potential of becoming efficient
pyroelectric materials. (Harrison and Liu 1980; Newnham et al 1980; Shaulov et al
1980). The Pz'r-plastic composite has a figure of merit six times more than that of Pz'r.
The absence of dielectric divergence in improper ferroelectrics makes it possible to have
a high figure of merit. The rare earth molybdates, propionates and boracites are found
to be superior to TGS.
Acknowledgement
The Author is thankful to Prof R Vijayaraghavan and Dr M S Multani for their kind
interest.
References