Physics of the Solid State, Vol. 45, No. 7, 2003, pp. 1284–1287.

Translated from Fizika Tverdogo Tela, Vol. 45, No. 7, 2003, pp. 1225–1227.
Original Russian Text Copyright © 2003 by Chupis.

MAGNETISM
AND FERROELECTRICITY

Enhancement of the Magnetoelectric Effect

in Thin Ferroelectric Films
I. E. Chupis
Verkin Institute of Low-Temperature Physics and Engineering, National Academy of Sciences of Ukraine, pr. Lenina 47,
Kharkov, 61103 Ukraine
e-mail: chupis@ilt.kharkov.ua
Received November 6, 2002

Abstract—The enhancement of the nonlinear magnetoelectric effect in a magnetic field is predicted for a fer-
roelectric film in a system consisting of ferroelectric and paraelectric layers in the vicinity of the size-induced
ferroelectric phase transition. This effect is assumed to be maximum in semiconductor ferroelectrics. © 2003
MAIK “Nauka/Interperiodica”.

1. INTRODUCTION 2. THEORETICAL ANALYSIS

Ferroelectrics do not belong to the class of materials
with a linear magnetoelectric effect in which the magne-
toelectric interaction manifests itself most strongly. By
contrast, ferroelectrics are characterized by nonlinear
magnetoelectric effects, including an insignificant shift
in the Curie temperature in an external magnetic field
[1, 2]. The magnetic field primarily affects the electronic
subsystem by varying the electron states (the Zeeman
effect); as a result, the crystal lattice undergoes deforma-
tion and polarization due to the electron–phonon interac-
tion and the Jahn–Teller effect [3, 4]. The ions in the
crystal lattice are also directly affected by the magnetic
field; however, this effect is considerably weaker than the
action of the magnetic field on the electronic subsystem.
As a consequence, the temperature shift of the ferroelec-
tric transition in response to a magnetic field in semicon-
ductor ferroelectrics [1] is one order of magnitude larger
than that in dielectrics [2].
It is known that the higher the dielectric susceptibil-
ity, the greater the magnetoelectric susceptibility (see,
for example, [5]). Recent studies revealed giant dielec-
tric susceptibilities for structures consisting of thin fer-
roelectric (PbTiO3) and paraelectric layers [6, 7]. It is
found that the dielectric susceptibility of a thin ferro-
electric layer is three orders of magnitude higher than
the susceptibility of the bulk sample. This effect is
explained by domain-wall pinning at defects and the
size-induced ferroelectric phase transition [8–10].
Since the effect under investigation is observed in sys-
tems composed of alternating ferroelectric and
paraelectric layers that do not interact with each other,
the same effect can be observed for an individual ferro-
electric film.
In this work, we demonstrated that, in a ferroelectric
film without electric polarization at the boundary, the
magnetoelectric effect is considerably enhanced in the
vicinity of the size-induced phase transition.
Let us consider a cubic-ferroelectric film of thick-
ness l (0 < z < l) with the electric polarization P directed
along the film plane (x, y) in an external constant mag-
netic field H, whose direction is insignificant in the fur-
ther consideration. The free energy of the system can be
represented in the form
l
a 2 b 4 λ ∂P 2 1 2 2
– --- P + --- P + ---  ------ + --- γ P H dz. (1)
1
F = ---
l ∫ 2 4 2  ∂z  2
0
Here, a = a0(Tc – T) is a constant, a0 > 0, and Tc is the
Curie temperature for a bulk sample. The last term in
functional (1) is the magnetoelectric energy of interac-
tion of the electric polarization with the magnetic field.
The equation for equilibrium values of the polariza-
tion can be derived by varying the polarization P in
functional (1). As a result, we obtain
aP – bP + λP'' – γPH = 0.
3 2
(2)
It is assumed that the electric polarization is absent
at the boundary of the film (this corresponds to the
experimental situation where the ferroelectric layers
alternate with paraelectric layers); that is,
P ( z = 0, l ) = 0. (3)
We are interested here in the magnetoelectric suscepti-
bility α = (∂P/∂H), for which an equation can be
derived by differentiating Eq. (2) with respect to the
magnetic field H:
λα'' + ( a – 3bP s )α – 2γHP s = 0.
2
(4)
Hereafter, the magnetic field will be considered weak.
Hence, in Eq. (4), only the terms linear with respect to

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 ENHANCEMENT OF THE MAGNETOELECTRIC EFFECT IN THIN FERROELECTRIC FILMS 1285

the magnetic field H remain and we assume that P = dn(u, m) is the delta amplitudinis. We determine the con-
Ps. The spontaneous polarization Ps satisfies Eq. (2) in stants c1 and c2 from boundary conditions (7); that is,
the magnetic field H = 0 with boundary conditions (3)
and, at temperatures T < Tc, can be represented in the α t 2m ( 1 + m ) [ K ( 1 – m ) – 2E ]
form [10] c 2 = -----------------------------------
- -------------------------------------------------------- ,
(1 – m) [ K ( 1 – m ) – ( 1 + m )E ] (10)

P s ( z ) = P st -------------sn  ---------------------, m .
2m z c 1 = 0.
(5)
1 + m  l0 1 + m 
Here, E is the complete elliptic integral of the second
Here, Pst = (a/b)1/2 is the spontaneous polarization of a kind.
thick film; l0 = (λ/a)1/2 is the correlation length; and The mean value of the magnetoelectric susceptibil-
sn(u, m) is the elliptic sine, for which the parameter m ity α in a ferroelectric film,
is determined from the equation
l 2K
l = 2l 0 1 + m K ( m ), 0 ≤ m ≤ 1, 1 1
(6)
l ∫
α = --- α ( z ) dz = ------- α ( u ) du ,
2K ∫
0 0
where K(m) is the complete elliptic integral of the first
kind. can be determined from expressions (8)–(10). As a
result, we obtain
After changing over to the variable u = z/ l 0 1 + m ,
the equation for the magnetoelectric susceptibility and
α t 2m ( 1 + m )
the corresponding boundary conditions take the follow- α = --------------------------------------------------
-. (11)
ing form: ( 1 + m )E – ( 1 – m )K

α'' + [ 1 + m – 6m sn ( u, m ) ]α
2 For the parameter m 1, the magnitude of K increases
logarithmically, K(1 – m) 0, and E 1. From
= –2 2m ( 1 + m )α t sn ( u, m ), (7) expression (11), we find that α αt. The value m =
γH 1 corresponds to a bulk sample. In this case, as follows
α t = – ---------- , α ( u = 0, 2K ) = 0. from relationship (6), we have l Ⰷ l0.
ab
The value m 0 corresponds to a size-induced
Here, αt is the magnetoelectric susceptibility of the phase transition [9, 10]. In this situation, the following
bulk sample, which can be easily obtained from Eq. (4) relationships are satisfied:
for uniform electric polarization.
The solution to Eq. (7) has the form K ( 0 ) = E ( 0 ) = π/2,
(12)
α ( u ) = c1 α1 + c2 α2 + α3 , (8) E ( 1 + m ) – K ( 1 – m ) ≅ 3πm/4.

where α1 and α2 are the solutions of the homogeneous For the mean magnetoelectric susceptibility
equation and α3 is the solution of the inhomogeneous described by relationship (11), we derive the expression
equation:
4 2α
α 1 = cn ( u, m )dn ( u, m ), α ≅ ---------- -------t- . (13)
3π m
1+m
α 2 = u – -------------E ( amu, m ) cn ( u, m )dn ( u, m ) It follows from relationship (6) that, at m 0, the
1–m
film thickness l tends to the least value l πl0 = lc,
for which the spontaneous polarization becomes zero.
+ ( 1 – m ) sn ( u, m ) [ dn ( u, m ) + m cn ( u, m ) ], (9)
–1 2 2 2
For l < lc, the spontaneous polarization is nonexistent.
Therefore, the transition from the ferroelectric phase to
α3 = –αt ( 1 – m ) 2m ( 1 + m )
–2
the paraelectric phase at a constant temperature T < Tc
can occur with a decrease in the film thickness (the so-
 [ ( 1 – m )u – 2E ( amu, m ) ]cn ( u, m )dn ( u, m ) called size-induced phase transition). For a film thick-
 ness l > lc, the temperature of the ferroelectric phase
×  + ( 1 + m )sn ( u, m )cn ( u, m )dn ( u, m )
2 2

 transition Tcl depends on the thickness [9, 10]:

 + sn ( u, m ) [ dn ( u, m ) + m cn ( u, m ) ].
3 2 2 2

l c0 2 λ
In expressions (9), E(amu, m) is the elliptic integral of T cl = T c 1 –  ----
- , l c0 = π ----------- , (14)
the second kind, cn(u, m) is the elliptic cosine, and  l a0 T c

PHYSICS OF THE SOLID STATE Vol. 45 No. 7 2003

1286
where lc0 is the critical thickness of the film at T = 0. For
l < lc0, we have Tcl < 0; i.e., the transition to the ferro-
electric state becomes impossible. For small parame-
ters m, from relationship (6) for films with a nearly crit-
ical thickness, we obtain
2 2 αt
m ≅ ---  --- – 1 ,
4 l
α ≅ ---------- ----------------,
3  lc  π 3 l
--- – 1
lc
According to expressions (15), the magnetoelectric
susceptibility of the film with l > lc at a constant tem-
perature T < Tc should exceed the magnetoelectric sus-
ceptibility αt of the bulk sample at this temperature to
such an extent that the film thickness l will be close to
the critical thickness lc.
On the other hand, from the expression relating the
correlation length l0 to the temperature through the
parameter a and relationship (14), at temperatures close
to Tcl, we have
2 l ( T cl – T )
2 a magnetic field of approximately 10 T, the magneto-
m ≅ --- -----
- --------------------, T cl – T Ⰶ T c .
3l2 Tc
c0
At temperatures close to Tcl for l = lc = πl0, from expres-
sions (6), (7), (13), and (16) for the magnetoelectric
susceptibility of a ferroelectric, we obtain
4γH 1 the order of magnitude of the magnetoelectric suscepti-
α = – ------------------- -------------------- .
π 3a 0 b T cl – T
The magnetoelectric susceptibility αt of the bulk sam-
ple [see relationship (7)] exhibits a temperature depen-
dence similar to that described by expression (17) in the
vicinity of the Curie temperature Tc when a 0. Note
that the magnetoelectric susceptibility of the nonlinear
effect at temperatures close to the temperature of the
ferroelectric transition increases anomalously. By con-
trast, the magnetoelectric susceptibility of the linear
effect in magnetoelectrics decreases and becomes zero
at the magnetic transition temperature.
The parameter of the magnetoelectric interaction γ
can be evaluated from the shift in the Curie temperature
in a magnetic field in BaTiO3 [2]. This shift implies
renormalization of the parameter a = a0(Tc – T) in
expression (1) for the free energy (a a – γH2). As a
result, we obtain
a 0 ∆T c
γ = -----------------,
2
H For the effect considered above, the spontaneous
where |∆Tc | is the shift in the Curie temperature. For
BaTiO3, we have ∆Tc = 0.1 K at H = 10 T [2]. The
parameters a0 and b for BaTiO3 can be obtained using
their values for PbTiO3 [11] and the results of the
comparison of the corresponding data for these com-
CHUPIS
pounds [12]. As a result, for BaTiO3, we have a0 =
18.4 × 10–5 K–1 and b = 9.4 × 10–13 CGSE. We obtain
|γ | = 1.8 × 10–15 CGSE. Hence it follows that the mean
magnetoelectric susceptibility of BaTiO3 in the vicin-
ity of the size-induced phase transition can be esti-
mated as
l – l c Ⰶ l c . (15)
10 H
–7
α ≈ -------------------- . (19)
T cl – T
The same order of magnitude of the magnetoelectric
susceptibility was obtained for PbTiO3 at temperatures
close to the size-induced phase transition (Tcl ≅ 533 K
[6, 7]). In this case, we used the parameters a0 = 7.7 ×
10–5 K–1 and |b| = 4.27 × 10–13 CGSE [11] and the mag-
nitude of parameter γ for BaTiO3.
3. RESULTS AND DISCUSSION
An analysis of expression (19) demonstrates that, in
(16) electric susceptibility can reach values comparable to
the highest susceptibility of the linear magnetoelectric
effect known to date for magnetoelectrics (for example,
α ≈ 10–2 for LiCoPO4).
For estimation, we used the parameters a0 and b for
the bulk sample. Therefore, expression (19) also gives
(17) bility for the bulk sample at temperatures close to the
Curie point in the case when the temperature Tcl is
replaced by Tc in expression (19). In the model used
here, the coefficients in functional (1) were considered
to be independent of the sample size. In actuality, the
–1
Curie constant C ~ a 0 for a PbTiO3 thin film [7] is two
orders of magnitude larger than the Curie constant for
the bulk sample. Consequently, the magnetoelectric
susceptibility in the vicinity of the size-induced phase
transition should exceed the value predicted from
expression (19).
The shift in the Curie temperature in a magnetic
field for semiconductor ferroelectrics is one or two
orders of magnitude greater than that for BaTiO3 (for
example, ∆Tc ≅ 1 K for Pb1 – xGexTe in the magnetic
field H = 3 T). Therefore, the constant γ and, corre-
spondingly, the magnetoelectric susceptibility, accord-
ing to the estimate obtained from expression (19),
should be one order of magnitude larger than those for
nonconducting ferroelectrics.
(18)
electric polarization must go to zero at the layer
boundary. In particular, this condition is satisfied in
the case of contact with paraelectric layers. Therefore,
the effect studied in this work can be observed in fer-
roelectric films and paraelectric–ferroelectric multi-
layer systems [6, 7].
PHYSICS OF THE SOLID STATE Vol. 45 No. 7 2003
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Translated by N. Korovin

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