16.

Dielectrics and Ferroelectrics

p r
Total dipole moment
For a neutral system, p is independent of the choice of the coordinate origin.
Dipole field:
( )
( )
2
5
3 r
r

=
p r r p
E r
H
2
O
Macroscopic Electric Field
E
0
= external (applied) field
Macroscopic field
( ) ( )
0
1
C
dV
V
=
}
E r e r V
C
= volume of crystal cell
e(r) = microscopic field
E due to a volume of uniform P is equal to that due to a surface charge density
o = n P
For any point between the plates & far from the edges
1
4 E t o =
4 P t =
0 1
= + E E E
0
4 P t = E z
E
1
= field due to = n P.
Depolarization Field, E
1

Inside an ellipsoidal body, P uniform E
1
uniform
0 1
= + E E E
E
1
= depolarization field If P is uniform, then
Along the principal axes 1 j j j
E N P =
N
j
= depolarization factor
4
j
j
N t =

ellipsoid of revolution
_ = P E
= dielectric susceptibility
Along a principal axis of an ellipsoid: 0 1
E E E = +
0
E NP =
( )
0
P E NP _ =
0
1
E
N
_
_
=
+
Local Electric Field at an Atom
Consider a simple cubic crystal of spherical shape.
0 1 0
4
3
t
= + = E E E E P
If all dipoles are equal to
The macroscopic field in a sphere is
In general, E = E
loc
.
p = p z
the dipole field at the center of the sphere is
2 2
5
3
j j
dipole
j
j
z r
p
r

=

E
2 2 2
5
2
j j j
j
j
z x y
p
r

=

Cubic symmetry
2 2 2
5 5 5
j j j
j j j
j j j
x y z
r r r
= =


0
dipole
= E

0 loc
= E E = E
For an abitrary symmetry
0 1 2 3 loc
= + + + E E E E E
E
2
= Lorentz cavity field
(due to charges on surface of cavity)
E
3
= field of atoms inside cavity
E
1
+ E
2
= field of body with hole.
E
1
+ E
2
+ E
3
= field of all other atoms at one atom.
( )
2
1 2 3
5
0
3
j j j j j
j
j
r
r
=

+ + =

p r r p
E E E
Sites 10a (~50A) away can be replaced by 2 surface integrals:
1 over the outer ellipsoidal surface,
the other over the cavity defining E
2
.
Lorentz Field, E
2

( ) ( )
2
2
0
cos
2 sin cos a a d
a
t
u
t u u u =
}
P
E
4
3
t
= P
1
= E
1 2
0 + = E E

Field of Dipoles inside Cavity, E
3

E
3
is only field that depends on crystal structure.
For cubic crystals
3
0 = E

0 1
4
3
loc
t
= + + E E E P
4
3
t
= + E P
Lorentz relation
Dielectric Constant and Polarizability
For an isotropic / cubic medium, is a scalar:
4 E P
E
t
c
+
= 1 4t _ = +
P
E
_ =
4
D E
E t

=
1
4
c
t

=
For a non-cubic medium, & are tensors:
P E
v v
_ = 4
v v v
c o t _ = +
Polarizability of an atom:
loc
o = p E
is in general a tensor
j j
j
N =

P p
( )
j o j
j
l c
j N o =

E Polarization:
For cubic medium, Lorentz relation applies :
4
3
j j
j
N
t
o
| |
= +
|
\ .

P E P
4
1
3
j
j
j
j
j
j
N
N
o
_
t
o
=

1 4
2 3
j
j
j
N
c t
o
c

=
+
Clausius-Mossotti relation
Electronic Polarizability
Dipolar: re-orientation of
molecules with permanent dipoles
Ionic: ion-ion displacement
Electronic: e-nucleus displacement
In heterogeneous materials, there is also an interfacial polarization.
At high frequencies, electronic contribution dominates.
e.g., optical range:
( )
1 4
2 3
j
j
j
elec o c N tr ni
c t
o
c

=
+

2
2
1
2
n
n

=
+
Classical Theory of Electronic Polarizability
( )
2
0 loc
m x x eE e + = Bounded e subject to static E
loc
:
Steady state:
2
0
loc
e E
x
me
=
Static electronic polarizability:
( )
loc
p
el
E
o =
2
2
0
e
me
=
loc
e x
E

=
( )
2
0
sin
loc
m x x eE t e e + = Bounded e subject to oscillatory E
loc
:
( )
0
2 2
0
loc
e E
x
m e e
=

Oscillatory solution :
0
sin x x t e =
Electronic polarizability: ( )
( )
2
2 2
0
e
el
m
o
e e
=

Quantum theory: ( )
2
2 2
i j
i j
j
e
el
m
f
o
e e
=

f
i j
= oscillator strength of dipole
transition between states i & j.
Structural Phase Transitions
At T = 0, stable structure A has lowest free energy F = U for a given P.
High P favors close-packing structures which tend to be metallic.
E.g., H & Xe becom metallic under high P.
Let B has a softer (lower ) phonon spectrum than A.
S
B
> S
A
due to greater phonon occupancy for B.
- T
C
s.t. F
B
= U
B
T S
B
> F
A
= U
A
T S
A
T > T
C

( phase transition A B unless T
C
> T
melt
)
F
B
(T
C
) = F
A
(T
C
)
Near T
C
, transition can be highly stress sensitive.
Ferroelectrics: spontaneous P.
Unusual (T).
Piezoelectric effect.
Pyroelectric effect.
Electro-optical effects such as optical frequency doubling.
Ferroelectric Crystals
PbTiO
3

Ferroelectric : P vs E plot shows hysteresis.
Ferroelectric T
C
Paraelectric
Pyroelectric effects (P T ) are often
found in ferroelectrics where P is not
affected by E less than the breakdown field.
E.g., LiNbO
3
is pyroelectric at 300K.
High T
C
= 1480K.
Large saturation P = 50 C/cm
2
.
Can be poled
(given remanent P by E at T >1400K).
Classification of Ferroelectric Crystals
2 main classes of ferroelectrics:
order-disorder: soft (lowest
TO
) modes diffusive at transition.
e.g., system with H-bonds: KH
2
PO
4
.
displacive: soft modes can propagate at transition.
e.g., ionic crytsls with perovskite, or ilmenite structure.
T
C
nearly doubled on HD.
Due to quantum effect involving mass-dependent de Broglie wavelength.
n-diffraction for T < T
C
, H
+
distribution along H-bond asymmetric.
T > T
C
T < T
C
: displaced
Most are in between
Order-disorder
Displacive
BaTiO
3

At 300K, P
S
= 810
4
esu cm
2
.
V
C
= (4 10
8
)
3
= 64 10
24
cm
3
.
p ~ 510
18
esu cm
Moving Ba
2+
& Ti
4+
w.r.t. O
2
by = 0.1A gives p /cell = 6e ~ 310
18
esu cm
In LiNbO
3
, is 0.9A for Li & 0.5A for Nb larger p.
Displacive Transitions
2 viewpoints on displacive transitions:
Polarization catastrophe
( E
loc
caused by u is larger than elastic restoring force ).
Condensation of TO phonon
(t-indep displacement of finite amplitude)
Happens when
TO
= 0 for some q = 0.

LO
>
TO
& need not be considered .
In perovskite structures, environment of O
2
ions is not cubic large E
loc
.
displacive transition to ferro- or antiferro-electrics favorable.
Catastophe theory:
Let E
loc
= E + 4 P / 3 at all atoms.
In a 2
nd
order phase transition, there is no latent heat.
The order parameter (P) is continuous at T
C
.
8
1
3
4
1
3
j j
j
j j
j
N
N
t
c
o
t
o
+
=

C-M relation:
Catastophe condition:
3
4
j j
j
N o
t
=

8
1
3
4
1
3
j j
j
j j
j
N
N
t
c
o
t
o
+
=

4
3
3
1
j j
j
N s
t
o =

3 6
3
s
s

=
1
s
~
for s 0
C
s
T T

~

C
T T
c

~

(paraelectric)
Soft Optical Phonons
LST relation
( )
( )
2
2
0
TO
LO
c
e
e c

=

TO
0 (0)
no restoring force: crystal unstable
E.g., ferroelectric BaTiO
3
at 24C has
TO
= 12 cm
1
.
Near T
C
,
( )
1
0
C
T T
c


2
TO C
T T e if
LO
is indep of T
SrTiO
3
from n scatt
SbSI
from Raman scatt
Landau Theory of the Phase Transition
Landau free energy density:
2 4 6
0 2 4 6
1 1 1
2 4 6
g g g g + + + + = + E P P P P
Comments:
Assumption that odd power terms vanish is valid if crystal has center of inversion.
Power series expansion often fails near transition (non-analytic terms prevail) .
e.g., C
p
of KH
2
PO
4
has a log singularity at T
C
.
The Helmholtz free energy F(T, E) is defined by
( )
3 5
2 4 6
0 ; , g g g F T =V = + + + + P P E P P E
Transition to ferroelectric is facilitated by setting ( )
2 0
g T T =
0
0 ,
C
T T > s
(This T dependence can be explained by thermal expansion & other anharmonic effects )
g
2
~ 0
+
lattice is soft & close to instability.
g
2
< 0 unpolarized lattice is unstable.
( )
2
0 2
1
; ,
1
2
j
j
j
g g
j
F T

=
+ + =

P E P P E
Second-Order Transition
For g
4
> 0, terms g
6
or higher bring no new features & can be neglected.
( )
3 5
0 4 6
0 T T g g = + + + + P P E P
E = 0 ( )
3
0 4
0 T T g = + P P P
S
= 0 or
( )
2
0
4
S
T T
g

= P
Since , g
4
> 0, the only real solution when T > T
0
, is P
S
= 0 (paraelectric phase).
This also identifies T
0
with T
C
.
For T < T
0
, ( )
0
4
S
P T T
g

=
minimizes F ( T, 0 ) (ferroelectric phase).
LiTaO
3

First-Order Transition
For g
4
< 0, the transition is 1
st
order and term g
6
must be retained.
( )
3 5
0 4 6
0 T T g g = + + + + P P E P
E = 0 ( )
3 5
0 4 6
0 T T g g = + P P P
P
S
= 0 or
( )
2 2
4 4 6 0
6
1
4
2
S
g g g T T
g

(
=

P
BaTiO
3
(calculated)
For E = 0 & T > T
C
, g
4
& higher terms can be neglected: ( )
0
T T = E P
( )
0
4 4
1 1
P
E T T
t t
c

= + = +

T
0
= T
C
for 2
nd
order trans.
T
0
< T
C
for 1
st
order trans.
Fundamental types of structural phase
transitions from a centrosymmetric prototpe
Perovskite
Lead zirconate-lead titanate (PZT) system
Widely used as ceramic piezoelectrics.
Ferroelectric Domains
Atomic displacements
of oppositely polarized
domains.
Domains with
180 walls
BaTiO face c axis.
E
a
// c axis.
Piezoelectricity
Ferroelectricity Piezoelectricity (not vice versa)
Unstressed
d o _ = + P E
= stress (tensor)
d = piezoelectric constant (tensor)
= dielectric susceptibility
e = elastic compliance constant (tensor)
d o = + e s E
i
i
e
d
E
o
o
o
| | c
=
|
c
\ .
= 1,, 6
Unstressed: 3-fold symmetry
A
+
3
B
3

PiezoE not FerroE
e.g., SiO
2

d ~ 10
7
cm/statvolt
BaTiO
3
:
d = 10
5
cm/statvolt
PVF
2
films are flexible & often used as ultrsonic transducers