Solid State Communications,Vol. 11, pp. 291-294, 1972. Pergamon Press.

Printed in Great Britain

THERMODYNAMIC STABILITY OF THIN FERROELECTRIC FILMS

I.P. Batra and B.D. Silverman

IBM Research Laboratory, San Jose, California

(Received 15 March 1972 by H. Suhl)

It is shown that the residual depolarization field in a ferroelectric

thin film which arises from the incomplete cancellation of polarization
and compensation charge in a semiconducting electrode, introduces
modifications in the spontaneous polarization and transition tempera-
ture. It is also found that below a certain critical thickness the
ferroelectric polar state is thermodynamically unstable. For triglycine
sulphate the critical thickness is calculated to be 0.4 ;zm.

IT IS well known that a ferroelectric material resulting in a polarization that is essentially

(FE) can experience a depolarization field that
results from incomplete compensation of the
polarization charge. Such depolarization field
has been invoked to explain a number of phenomena
observed in ferroelectric materials. I Recently it
has been pointed out that the observed poor
retentivity and reverse switching in ferroelectric
thin films can be related to the nonvanishing of the
depolarization field. 2
The purpose of the present communication is
to show that the depolarization field introduces
modifications in the intrinsic or thermodynamic
properties of the FE namely; the spontaneous
polarization and transition temperature. It will
be shown that the stability of the polar phase
depends rather critically on the close cancellation
of the polarization and compensation charges.
The uncompensated depolarization field in a
FE is 10 7 to I0 a V/cm and hence the presence
of compensation charge is required for material
stability. Even though the compensation charge
can closely cancel the depolarization field to
one part in 10" or more, the residual depolarization
field could still be sufficiently large to lead to
observable effects. For a FE of large thickness,
the cancellation can be nearly perfect in bulk,
the depolarization field being essentially zero and
equal to the bulk value. When the thickness of
the FE becomes small, however, significant
depolarization fields result in a depression of
the spontaneous polarization and transition
temperature. In what follows it will be shown
that below a certain critical thickness the
ferroelectric polar state is thermodynamically
unstable, a
Ivanchik 4 has considered a partially conducting
laminar crystal of BaTiO 3 and shown that the
spontaneous polarization and transition tempera-
ture are plate thickness dependent. Following
this work, there have been several papers s in the
Russian literature which have extended these
ideas by treating the semiconductor-ferroelectric
contact and the implications with respect to
thermodynamic stability of the ferroelectric. The
authors of these papers treat the case for which
there is space charge distribution in the electrode
as well as in the ferroelectric. They all also
assume that the value of the polarization at the
interface is equal to zero. This seems unnecess-
arily restrictive and should lead to polarization
values in the ferroelectric film that are lower
than allowed by choosing a finite discontinuity
in polarization at the interface. In the present
work we will assume no space charge distribution
in the ferroelectric and hence the polarization

291
292 THERMODYNAMIC S T A B I L I T Y OF THIN F E R R O E L E C T R I C FILMS Vol. l l , No. 1

The e l e c t r i c field Ef i n s i d e the F E is

written

Ef = 47: ( T - To )P + ~ P ~ . (2)
C

F o r a c r y s t a l of infinite t h i c k n e s s the p o l a r i z -
a t i o n c h a r g e s are fully c o m p e n s a t e d and E r = 0.
The s p o n t a n e o u s p o l a r i z a t i o n is then given by

Ps ~", T) = ~v/[4-~-(To - T) , (3)

L
-iLr "7
X IP
and t r a n s i t i o n occurs at a temperature TQ.
FIG. 1. F e r r o e l e c t r i c / s e m i c o n d u c t o r short F o r a F E of finite e x t e n t , a s shown in F i g . l ,
c i r c u i t geometry under c o n s i d e r a t i o n .
Ef is different from z e r o and is o b t a i n e d a s
will be uniform. T h e finite p o l a r i z a t i o n d i s - f o l l o w s . T h e e l e c t r i c field d i s t r i b u t i o n in the
c o n t i n u i t y at the i n t e r f a c e will t h e r e f o r e r e s u l t e l e c t r o d e , E ~ (x) is obtained from P o i s s o n ' s
in a n o n v a n i s h i n g c o n t r i b u t i o n to the d e p o l a r - e q u a t i o n and the c o n d i t i o n that the t o t a l current
i z a t i o n field near the i n t e r f a c e j u s t i n s i d e the (drift diffusion) is zero. One o b t a i n s
f e r r o e l e c t r i c . T h e e l e c t r i c a l c o n d i t i o n s will 47r,oo (L + 2 x )
be t r e a t e d e x p l i c i t l y and in the p r e s e n t p a p e r E e (x) = - sinh,~,,
we have t a k e n the two e l e c t r o d e s to be short
c i r c u i t e d . T h e point of the p r e s e n t p a p e r is to
show that, under the short c i r c u i t c o n d i t i o n , the L l
--..~ x ~-- (4)
d e p o l a r i z a t i o n f i e l d s , r e s u l t i n g from i n c o m p l e t e 2 2
c o m p e n s a t i o n , e s t a b l i s h lower t r a n s i t i o n tempera- where A is the s c r e e n i n g length which for non-
tures than a t t a i n e d in b u l k m a t e r i a l . T r i g l y c i n e d e g e n e r a t e c a r r i e r s t a t i s t i c s is given by
s u l p h a t e (TGS) will be u s e d a s an i l l u s t r a t i v e
e x a m p l e . We ignore i m p u r i t i e s and s u r f a c e s t a t e s X = ~/(e~kT/4~e2ne) . (5)
in what f o l l o w s . The p r e s e n c e of a s i g n i f i c a n t The s o l u t i o n has been c h o s e n to s a t i s f y the
s u r f a c e charge s t a t e d e n s i t y could reduce the
c o n d i t i o n s : E~ (- L / 2 ) = O, Ee ( - 1/2) =
d e p o l a r i z a t i o n field e x p e r i e n c e d by the ferro- - (4rr/~e)P~, where Pa is the e x c e s s c h a r g e per
electric. unit a r e a of the e l e c t r o d e . The field in the F E
c a n then be written Ef = - 4 7 r ( P o - P). A r e l a t i o n -
C o n s i d e r an F E of t h i c k n e s s l having a s h i p b e t w e e n the e l e c t r o d e c o m p e n s a t i o n c h a r g e ,
homogeneous d o m a i n l e s s s t r u c t u r e and s a n d w i c h e d Po, and the p o l a r i z a t i o n , P is o b t a i n e d by i m p o s i n g
b e t w e e n e l e c t r o d e s of t h i c k n e s s (L - 0 / 2 a s
the s h o r t c i r c u i t condition:
shown in F i g . 1. The F E is d e s c r i b e d by the f -~12 o
following thermodynamic free e n e r g y function
-g/2
One c a n then write
F(P,T) = F(O,7) ~2rr ( r - r o ) P 2 + -~
1 ~p4. (1)
Ef = - 4 7 r P I 1 - O(X,l)l, (6)
Here P is the s p a t i a l l y uniform p o l a r i z a t i o n , T where
the temperature, C the Curie c o n s t a n t , To the
C u r i e - W e i s s t e m p e r a t u r e , ~: a c o n s t a n t ( a s s u m e d
p o s i t i v e ) , and F(0,7") the p o l a r i z a t i o n i n d e p e n d e n t
part of the free e n e r g y . The p o l a r i z a t i o n vector
i12 cscht
P is d i r e c t e d a l o n g one of the c r y s t a l l o g r a p h i c
a x e s only; and higher order terms in the polari-
z a t i o n are a s s u m e d to be n e g l i g i b l y s m a l l . T h e s e When I-~ ~ or X - . O , then 0 = i and the d e p o l a r -
are r e a s o n a b l e a s s u m p t i o n s , s a y for TGS, a ferro- i z a t i o n field is e q u a l to zero. T h i s is the c a s e of
e l e c t r i c which e x h i b i t s a s e c o n d order p h a s e
transition. 6
Vol. 11, No. 1 THERMODYNAMIC S T A B I L I T Y OF THIN F E R R O E L E C T R I C FILMS 293

c o m p l e t e s u r f a c e charge c o m p e n s a t i o n and is the The p a r a m e t e r s a p p r o p r i a t e for TGS are: 6 ~: =

c a s e t r e a t e d in the l i t e r a t u r e to e l u c i d a t e bulk
f e r r o e l e c t r i c p r o p e r t i e s . F o r no c o m p e n s a t i o n
whatsoever, 0 = 0andEf = 4rrP~107 -104
V / c m . F o r the p r e s e n t c a s e under c o n s i d e r a t i o n
0 "" 0.999 and Ef ~ 10" V/era. T h i s r e s i d u a l
d e p o l a r i z a t i o n field is s t i l l s u f f i c i e n t l y large to
l e a d to o b s e r v a b l e e f f e c t s . In g e n e r a l , 0 < 0 4 1
and E r ~ 0. The s p o n t a n e o u s p o l a r i z a t i o n can
then be w r i t t e n
-- ,
8.0 10 -1 ( e . s . u . / c m Q - a , To = 49.8~C, C =
3300 . F o r the s e m i c o n d u c t i n g e l e c t r o d e we
p i c k e d ne = 10~7/cm 3, ~e = 6.0. With t h e s e
numbers at room temperature, T = 25"~C we o b t a i n
X"- 9.2 x 10 -v cm and Ps (,%T) = 3.62~cc/cm a.
It is s e e n from F i g . 2 that ATo d e c r e a s e s a s l
i n c r e a s e s a c c o r d i n g to l -~. When ATo = To - T
= 24.8C a c r i t i c a l length lc is reached below
which the f e r r o e l e c t r i c polar p h a s e is u n s t a b l e
t h e r m o d y n a m i c a l l y . From equation ( l l ) we obtain

lc = 2AC = 0.41,ccm for TGS.

ce(To = T)
with

To* = To - Cll - 0(x,l)l Note that even for l ~,- 2 - 3 / 1 m there is a s i z a b l e

Thus for finite f e r r o e l e c t r i c t h i c k n e s s , the t r a n s i t i o n shift ( 4 - 6 C ) in the t r a n s i t i o n temperature.
t e m p e r a t u r e is t h i c k n e s s d e p e n d e n t and is l e s s
than the v a l u e for the infinite c r y s t a l . A l s o at 12.5 -
6.0

any temperature the c o r r e s p o n d i n g v a l u e of the

p o l a r i z a t i o n Ps (l,T) is lower than the bulk value,
Ps (,%T). T h i s is e a s i l y understood s i n c e the I0,0, 5.0
d e p o l a r i z a t i o n f i e l d is nothing more than a b i a s
field that is p r o p o r t i o n a l to and o p p o s i t e the -- 4.0

polarization. Ferroelectric stability requires

that the p h a s e t r a n s i t i o n occur at T* rather than
To. T h u s the t r a n s i t i o n temperature is d e p r e s s e d o 5.0 _o~ o
x ~"
by an amount

ATo -~ To - To* = cI1 - 0(x,l)l . (9) 12.0

2.5 5 ~..~
F o r the d i s c u s s i o n of r e s u l t s we c h o s e TGS 0
with s e m i c o n d u c t i n g e l e c t r o d e s , as an e x a m p l e . 0.0 - 1I ! ~ ",~....~...~
It is c o n v e n i e n t to use an a p p r o x i m a t e e x p r e s s i o n
0.0 2.0 4,0 6.0 8.0 10.0
for O()t,l), which is obtained when the s c r e e n i n g
FILM THICKNESS R(MICRONS}
length, h, is s m a l l compared with the e l e c t r o d e
thickness. That is,
FIG. 2. Graphs s h o w i n g the shift in t r a n s i t i o n
0(X,) ~- 1 - 2h , ;t << (L - l ) (10) t e m p e r a t u r e , s p o n t a n e o u s p o l a r i z a t i o n , and
eel 2 d e p o l a r i z a t i o n field a s a function of the ferro-
electric thickness.
U s i n g this value for 0 we o b t a i n

Aro ~ 2XC (ii) T h e s p o n t a n e o u s p o l a r i z a t i o n Ps s t a r t s out with

a v a l u e zero at I = Ic and i n c r e a s e s m o n o t o n i c a l l y

T- 2GI
~ ~/2 (12)
t o w a r d s the bulk value of 3.6/.tc/cm2 a s I i n c r e a s e s
The d e p o l a r i z a t i o n field, El, shows an i n t e r e s t i n g
d e p e n d e n c e on I. It goes to zero at I = Ic and a l s o
at l - , o ~ but has a maximum at I = l~ = 31c/2
E/ ~--P4vr]t'/2 [T -U]2XC]'/z(2}~)~'-I " (13) which is about 0.6/zm in this c a s e . T h i s b e h a v i o r
c a n be u n d e r s t o o d from e q u a t i o n (13) which s a y s
In F i g . 2 we have p l o t t e d ATo, Ps , and the that Ef ~- Ps ~ T 0 . In other words the E / c u r v e is
magnitude of E r a s a function of film t h i c k n e s s . e s s e n t i a l l y the product of the c u r v e s for Ps and
294 THERMODYNAMIC STABILITY OF THIN FERROELECTRIC FILMS Vot. 11, No. 1

ATo. Since one is increasing and the other is In conclusion it is emphasized that the
decreasing with l, one would expect a maximum
electrical conditions are significant in determining
in the product. The fact that the maximum occurs
the thermodynamic properties of thin ferroelectric
at a small value of I is due to a rapid decrease
films. Shorted electrodes do not provide exact
in P~ in this range.
charge cancellation of the depolarization field
and hence the transition temperature and polari-
The case of metallic electrodes can be
zation should be shifted to lower values than
treated with the use of F e r m i - D i r a c s t a t i s t i c s .
observed in the bulk. The effect predicted here
At the higher carrier concentration the screening
is similar to the one discussed by Ginzburg and
length is smaller and hence depolarization effects
P i t a e v s k i i 7 in connection with the A-point
are less severe. For screening lengths of approxi-
transition in superfluidity.
mately 1 A, the critical thickness will then be
only 1 per cent of the length just calculated for
the semiconducting electrode.

REFERENCES
1. DROUGARD M.E. and LANDAUER R., J. appl. Phys. 30, 1663 (1959); JANOVEC V., CZECHOSLOV.
J. Phys. 9, 468 (1959); TRIEBWASSER S., Phys. Rev. | ]8, 100 (1960); and CALLABY D.R., J. appl.
Phys. 36, 2751 (1965).
2. SHARMA B.S., Bull. Am. Phys. Soc. 17, 103 (1972); MEHTA R.R., SILVERMAN B.D. and JACOBS
J.T., ibid.
3. BATRA I.P. and SILVERMAN B . D , Bull. Am. Phys. Soc. 17, 103 (1972).
4. IVANCHIK I.I., Fizika tverd. Tela. 3, 3731 (1961), [Soviet Phys. Solid St. 3, 2705 (1962)].
5. KHOLODENKO L.P., Fizika tverd. Tela. 5, 897 (1963), [Soviet Phys. Solid St. 5, 660 (1963)];
GURO G.M., IVANCHIK I.I. and KOVTONYUK ibid. 10, 135 (1968) and 11, 1956 (1969)[ibid. 10,
100 (1968) and ] |, 1574 (1970)]; VUL B.M., GURO G.M. and IVANCHIK I.I., Fizika tekh. Poluprov.
4, 162 (1970) [Soviet Phys. Semicond. 4, 128 (1970)]; and CHENSKI E.V., Fizika tverd. Tela. 12,
586 (1970) [Soviet Phys. Solid St. 12, 446 (1970)].
6. TRIEBWASSER S., IBM J. Res. & Dev. 2, 212 (1958); JONA F. and SHIRANE G., Ferroelectric
Crystals, p.34, Pergamon P r e s s (1962).
7. GINZBURG V.L. and PITAEVSKII L.P., Zh. eksp. tcor. Fiz., 34, 1240 (1958) [Soviet Phys. JETP
7, 858 (1958)].

Es wird gezeigt, dass in einer dtinnen ferroeletrischen Schicht das

Depolarisationsfeld, das aus der unvollst~ndigen Kompensation der
Polarisationsladung durch Ladung in einer halbleitenden Elektrode
stammt, zus~tzliche Anderungen der spontanen Polarisation und der
0bergangstemperatur bewirkt. Es ergibt sich, dass unterhalb einer
bestimmten kritischen Dicke der polare Zustand des Ferroelektrikums
thermodynamisch unstabil wird. Ffir Triglycinsulfar turde eine kritische
Dicke yon 0.4/zm errechnet.