ISSN 10637745, Crystallography Reports, 2009, Vol. 54, No. 6, pp. 917–919. © Pleiades Publishing, Inc., 2009.

Original Russian Text © V.M. Fridkin, 2009, published in Kristallografiya, 2009, Vol. 54, No. 6, pp. 965–967.

Dedicated to the memory of V.L. Indenbom

MeanField Theory about the Critical Size in Ferroelectricity
V. M. Fridkin
Shubnikov Institute of Crystallography, Russian Academy of Sciences, Leninskiі pr. 59, Moscow, 119333 Russia
email: fridkin@ns.crys.ras.ru
Received February 24, 2009

Abstract—The problem of critical size in ferroelectric crystals and films is considered within the meanfield
theory. It is shown that, when the boundary conditions are correctly chosen, the critical size can be either very
small or even absent; i.e., ferroelectricity can exist in one unit cell.
PACS numbers: 64.70.Nd, 77.80.Bh
DOI: 10.1134/S1063774509060029

INTRODUCTION developed the phenomenological theory of ferroelec

The critical size Lcr is considered to be the maxi tricity [3, 4]. As a result, two factors determining the
mum film thickness (or crystal size), which is incom critical size were revealed: surface energy and screen
patible with the existence of ferroelectricity. ing energy. At the film thickness at which one of these
energies becomes comparable or exceeds the lattice
In 1994 Onsager, using the Ising model, indicated
the presence of spontaneous polarization in a 2D energy, ferroelectricity disappears.
cubic lattice with dipoles (spins) in sites and showed The same factors lead to the socalled size effect,
that this monolayer oriented phase is transformed into i.e., a successive change in the ferroelectric properties
an unoriented one during the secondorder phase (for example, a decrease in the Curie temperature) at
transition [1]. Later, Landau and Vdovichenko mathe
matically justified this conclusion in a simpler way [2]. film thinning. The experimental search for the critical
However, these studies cannot be considered proof of size is one of the fundamental problems of the ferro
the existence of ferroelectricity in one monolayer (or electricity physics. Several dozen studies were devoted
unit cell) because they disregard the mechanisms to it. However, the critical size had not been directly
responsible for the critical size existence. found until the end of the 1990s. Figure 1 shows the
At the end of the 1940s, Ginzburg, based on the values of the minimum ferroelectric film thickness
Landau theory of secondorder phase transition, obtained in different studies from 1970 to 2002.
V. Fridkin Nature (P[VDFTrFE])

Iev lev P(VDFTrFE) Ferr. Lett.

Marayuma (PZT) [19]

1000 10
Karasawa (PTO) [17]

Tybell (PZT) [20]

Yanase (PZT) [16]
Li et al. [15]

8
Batra and Silverman (TGS) [13]

Thickness, nm

Zembilgotov [22]

Fong Science (PZT)

Li [18]
Thickness, nm

100 6
J. Scott [14]

4
10
2
0
1 1996 1998 2000 2002 2004
1997 1999 2001 2003 2006
1970 1975 1980 1985 1990 1995 2000
Year of publication

Fig. 1. Study of the Lcr value over the last 30 years.

917
918
P/Pb
2 1
D − L /2
ξ= 
α ⎤
Lcr4 Lcr3
0 0.85 1 2
L/ξ
Fig. 2. Size effect and critical thickness in the meanfield
theory.
During this period, the size effect was studied and
the critical thickness was experimentally searched for
in epitaxial films (mainly with perovskite structures).
A method for obtaining ferroelectric films of
vinylidene fluoridetrifluoroethylene copolymer
P[VDF–TrFE] (70 : 30) using the Langmuir–
Blodgett technique was developed for the first time at
the Institute of Crystallography, Russian Academy of
Sciences, in 1994 [5, 6]. These films had ferroelectric
properties, including switching and firstorder ferro
electric phase transition [7]. Their structure was inves
tigated by scanning transmission microscopy with an
atomic resolution [8–10] and Xray, neutron, as well
as electron diffraction methods [10–12]. The phase
transition from the orthorhombic ferroelectric 2mm
phase into the paraelectric 6:m phase occurred at Т ≅
100°С. The Langmuir–Blodgett technique made it
possible to obtain for the first time hyperfine ferroelec
tric films like this as one monolayer (0.5 nm). Thus, it
became possible to study the size effect at the molecu
lar level and verify the existence of critical thickness
Lcr.
This problem was solved in 1998 in [5], where fer
roelectricity was found in two copolymer monolayers
(1 nm) and later in one monolayer. Thus, it was shown
that the critical thickness is absent in ferroelectric
copolymer. Figure 1 shows that, until 1998, the mini
mum thickness of the ferroelectric films studied was
on the order of 10 nm; in addition, it can be seen that
the results of [5] initiated a series of investigations
aimed at searching for the critical thickness Lcr for per
ovskite films, which turned out to be ≈4 –6 nm.
Some researchers (see, for example, [22]) have
attempted to estimate Lcr based on the Ginzburg–
Landau theory. In the absence of a depolarization field
FRIDKIN
(it was shown in [22] that this field does not affect the
Lcr value very much), the free energy can be written as
+ L /2
G = F0 + 1 ⎡α P 2 + β P 4 + γ P 6
L ∫ ⎢⎣ 2 4 6
(1)
2
+ D ⎛⎜ ∂ P ⎞⎟ ⎥ dz + D P+2 + P−2 .
( )
2 ⎝ ∂z ⎠ ⎦ 2δ
Here, D is the correlation factor; δ is the surfacecou
pling factor which determines the surface energy; P± is
the spontaneous polarization for z = ±L/2; and α, β,
and γ are the known Landau–Ginzburg coefficients.
The state equation derived from the free energy (1) has
the form of the Euler–Lagrange equation:
+ L /2
D ∂ P2 = α P ( z ) + β P 3( z ) + γ P 5( z ) − 4 π
2
∂z L ∫ P ( z ) dz . (2)
− L /2
The boundary conditions in [22] were taken to be
∂P ± 1 P( z ) = 0, z = ± L.
(3)
∂z δ 2
If the surfacecoupling factor is positive (δ > 0),
Р and the phasetransition temperature ТС decrease
with a decrease in L. Figure 2 (curve 1) shows the size
effect for δ > 0 as a dependence of the polarization
Р on the film thickness L. Here, Рb is the spontaneous
polarization in a bulk crystal (L = ∞) and the thickness
L is normalized to the correlation length ξ = (D / α)1/2 .
The lower branch of the numerical solution in Fig. 2 is
unstable. Figure 2 indicates the existence of critical
thickness Lcr3 at which the spontaneous polarization
disappears:
⎛ ⎞
1/2
Lcr3 ≅ 0.85ξ = 0.85 ⎜ D ⎟ . (3')
⎝α⎠
Assuming that D ~ 3 × 1 0 − 1 8 m2 and α ≥ 10 −1
(T = 300 К) for perovskites [23], we obtain Lcr3 ≤
5 nm. Thus, the Landau–Ginzburg theory can explain
both the size effect and the existence of critical thick
ness Lcr. Obviously, the Lcr value depends on the accu
racy of estimating the correlation factor D and the fac
tor δ [18, 23].
The ab initio estimation of Lcr for BaTiO3 leads to a
similar result. For example, in [24] Lcr was found to
exist and be equal to six unit cell sizes (Lcr ≈ 2.4 nm).
Until recently, it had been debated if the Gin
zburg–Landau theory can explain the absence of crit
ical size in the P[VDF–TrFE] ferroelectric copoly
mer. The answer was given for the first time in [25–27].
To correctly impose boundary conditions, one must
take into account the polarization Pm, which is
induced by the lattice mismatch between superfine
ferroelectric film and electrodes (called the mismatch
CRYSTALLOGRAPHY REPORTS Vol. 54 No. 6 2009
 MEANFIELD THEORY ABOUT THE CRITICAL SIZE IN FERROELECTRICITY
effect in [25]). Then Eq. (1) and boundary condi
tions (3) can be written as
+ L /2 2 5. A. V. Bune, V. M. Fridkin, S. Ducharme, et al., Nature
⎡α P + β P 4 + γ P 6 + D ⎛ ∂ P ⎞
2
G = F0 + 1 ∫ ⎜ ⎟
L ⎢⎣ 2 4 6 2 ⎝ ∂z ⎠
− L /2
− P ( z ) E ⎤ dz + D ⎡⎣( P+ + Pm ) + ( P− + Pm ) ⎤⎦ ,
2 2
⎥⎦ 2δ
∂P ± 1 P(z ) = −P , z = ± L. (5)
m
∂z δ 2 34, 465 (1996).
Figure 2 (curve 2) shows the size effect upon the mis
match obtained by a numerical solution of (4') and (5);
according to these data, the critical size Lcr4 Lcr3 may
⎛P ⎞
satisfy the relation Lcr4 ≤ 10 −8 ⎜ b ⎟ m.
⎝ Pm ⎠
On the assumption that Pb/ Pm = 10 −1, Lcr4 ≤ 1 nm;
therefore, the critical size Lcr can, in principle, be of
the monolayer thickness (or one cell size); i.e., it may
be absent.
Thus, the meanfield theory can explain the
absence of critical size in ferroelectric copolymer.
Unfortunately, the ab initio calculation of Lcr for fer
roelectric copolymer has still not happened.
ACKNOWLEDGMENTS
I am grateful to V.L. Ginzburg for discussing this
study.
This study was supported by INTAS grant no.
10000088091 and the Russian Foundation for Basic
Research, project no. 090200096.
This paper is dedicated to the memory of Vladimir
L’vovich Indenbom, a prominent theoretician and my
friend. Indenbom made significant contributions to
nearly all fields of solidstate physics. One such field is
the physics of phase transitions and ferroelectrics. I
hope that this study is worthy of his memory.
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Translated by A. Madonov
2009