Theoretical description of ferroelectric and pyroelectric hystereses in the disordered

ferroelectric-semiconductor films
A. N. Morozovska, E. A. Eliseev, D. Remiens, and C. Soyer

Citation: Journal of Applied Physics 100, 014109 (2006); doi: 10.1063/1.2213172

View online: http://dx.doi.org/10.1063/1.2213172
View Table of Contents: http://scitation.aip.org/content/aip/journal/jap/100/1?ver=pdfcov
Published by the AIP Publishing

Articles you may be interested in

Enhanced pyroelectric coefficient of antiferroelectric-ferroelectric bilayer thin films
J. Appl. Phys. 105, 061610 (2009); 10.1063/1.3055350

Model for ferroelectric semiconductors thin films accounting for the space varying permittivity
J. Appl. Phys. 97, 024104 (2005); 10.1063/1.1834728

Improved ferroelectric and pyroelectric properties in Mn-doped lead zirconate titanate thin films
J. Appl. Phys. 94, 5228 (2003); 10.1063/1.1613370

Competition between ferroelectric and semiconductor properties in Pb ( Zr 0.65 Ti 0.35 ) O 3 thin films deposited
by sol–gel
J. Appl. Phys. 93, 4776 (2003); 10.1063/1.1562009

Ferroelectric polarization in stretched piezo- and pyroelectric poly(vinylidene fluoride-hexafluoropropylene)

copolymer films
J. Appl. Phys. 92, 7442 (2002); 10.1063/1.1524313

[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
216.165.95.69 On: Sun, 07 Dec 2014 20:50:55
 JOURNAL OF APPLIED PHYSICS 100, 014109 共2006兲

Theoretical description of ferroelectric and pyroelectric hystereses

in the disordered ferroelectric-semiconductor films
A. N. Morozovskaa兲
V. Lashkaryov Institute of Semiconductor Physics, National Academy of Science of Ukraine, 41,
prospect Nauki, 03028 Kiev, Ukraine
E. A. Eliseevb兲
Institute for Problems of Materials Science, National Academy of Science of Ukraine, 3, Krjijanovskogo,
03142 Kiev, Ukraine
D. Remiens and C. Soyer
IEMN, UMR 8520, DOAE/ MIMM, Universite de Valenciennes et du Hainaut-Cambresis, Le Mont Houy,
59313 Valenciennes Cedex 9, France
共Received 3 February 2006; accepted 7 May 2006; published online 12 July 2006兲
We have modified the Landau-Khalatnikov approach and shown that both the polar lattice and the
screened charged defects determine the response of disordered ferroelectric semiconductors. This
system exhibits the spatially inhomogeneous switching under the external field while the
Landau-Khalatnikov model describes homogeneous switching with the sharp pyroelectric
coefficient peak near the thermodynamic coercive field value. Our model gives more realistic
pyroelectric hysteresis loop shape without any peaks near the coercive field and describes both
qualitatively and quantitatively typical Pb共Zr, Ti兲O3 and 共Sr, Ba兲Nb2O6 films pyroelectric hysteresis
loops. © 2006 American Institute of Physics. 关DOI: 10.1063/1.2213172兴

I. INTRODUCTION electro-optic, piezoelectric, and pyroelectric devices, and

memory elements.2,9,10 However, the task on how to create
The main peculiarity of ferroelectric materials is hyster-
esis of their dielectric permittivity ␧, displacement D, and ferroelectric material with predetermined dielectric and/or
pyroelectric coefficient ␥ over electric field E0 applied to the pyroelectric properties is solved mainly empirically. The cor-
sample.1,2 Ferroelectric D共E0兲, dielectric ␧共E0兲, and pyro- rect theoretical consideration and modeling of related prob-
electric ␥共E0兲 hysteresis loops in an inhomogeneous lems seem rather useful both for science and applications. It
ferroelectric-semiconductor film have several characteristic could answer fundamental questions about the nature of
features depicted in Fig. 1共a兲.
In particular, ferroelectric hysteresis loops measured in
PbZrxTi1−xO3 films doped with donor additives of Nb, Nd,3,4
and relaxor ferroelectric films 关e.g., SrxBa1−xNb2O6
共SBN-x兲, PbZr1−xTixO3 : La共PZT: La兲, and PbMg1/3Nb2/3O3兴
have rather sloped and slim shape with low coercive fields
共see, e.g., Refs. 5–8兲, not the square one. Aforementioned
ferroelectric hysteresis loops are obtained by the conven-
tional Sawyer-Tower method2,9,10 at low frequencies of the
changing applied field. In these materials low frequency di-
electric hysteresis loops were obtained from the measure-
ments of the capacity dependence on the applied voltage.11–13
The loops of pyroelectric hysteresis are usually obtained by
means of pyroelectric response measurements under the pe-
riodic modulation of thermal flux when applied electric field
varies independently with much lower frequency.13 Pyroelec-
tric loops usually are sloped and slim; no maxima of pyro-
electric response near the coercive field are observed.13,14
Nowadays such typical ferroelectric semiconductors
such as BaTiO3 ceramics, disordered and relaxor SBN-x,
FIG. 1. Dielectric ␧共E0兲, ferroelectric D共E0兲, and pyroelectric ␥共E0兲 hyster-
PbZrxTi1−xO3 关PZT共x / 1 − x兲兴 solid solutions slightly doped esis loops. Different plots correspond to the data obtained for a
with Fe, Cr or La, Nb, Nd, Ce, etc., their films, multilayers, semiconductor-ferroelectric film 共a兲, the Landau-Khalatnikov model 共b兲, and
and heterostructures are widely used in sensors, actuators, our coupled equations 共c兲 for a bulk sample 共␻1 Ⰶ ␻2 are two frequencies of
applied electric field兲. Note that the Landau-Khalatnikov thermodynamic
coercive field EC is at least several times greater than the experimentally
a兲
Electronic mail: morozo@i.com.ua observed values EC1 and EC2 共sometimes the loops observed in the films
b兲
Electronic mail: eliseev@i.com.ua with thickness 50 nm– 5 ␮m are shifted on the value Ei = EC2 − EC1兲.

0021-8979/2006/100共1兲/014109/12/$23.00 100, 014109-1 © 2006 American Institute of Physics

[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
216.165.95.69 On: Sun, 07 Dec 2014 20:50:55
 014109-2 Morozovska et al.
lattice-defect correlations and possible self-organization in
the system and help tailor ferroelectric-semiconductor mate-
rials.
Conventional phenomenological approaches15,16 with
material parameters obtained from first-principles
calculations17,18 can be successfully applied to the pure ferro-
electric materials,19,20 but they give significantly incomplete
picture of the dielectric, ferroelectric, and pyroelectric hys-
tereses in the doped or inhomogeneous ferroelectric semi-
conductors 关compare Fig. 1共b兲 with Fig. 1共a兲兴.
In particular, the Landau-Khalatnikov approach, which
evolved for the single domain pure ferroelectric
dielectrics,21,22 describes homogeneous switching but pre-
sents neither domain pinning nor domain nucleation nor do-
main movement. The calculated values of thermodynamic
coercive field1 are significantly larger than its experimental
values for real ferroelectrics.9,23 Observed hysteresis loops
usually look much thinner and sloped than the Landau-
Khalatnikov ones.2,7,9,24–26 Also equations of the Landau-
Khalatnikov type describe homogeneous pyroelectric coeffi-
cient switching with the sharp peak near the thermodynamic
coercive field value. We could not find any experiment in
which the pyroelectric coefficient peak near the coercive
field had been observed. Usually the pyroelectric hysteresis
loops of doped ferroelectrics have typical slim shape with
coercive field values much lower than the thermodynamic
ones. Therefore, the modification of the Landau-Khalatnikov
approach for inhomogeneous ferroelectric semiconductors
seems necessary.27
In our recent papers28–32 we have considered the dis-
placement fluctuations and extrinsic conductivity caused by
charged defects and thus modified the Landau-Khalatnikov
approach for the inhomogeneous ferroelectric semiconduc-
[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
216.165.95.69 On: Sun, 07 Dec 2014 20:50:55
J. Appl. Phys. 100, 014109 共2006兲
FIG. 2. Spatial distribution of displacement D, free car-
riers with charge density n, and sluggish defects with
charged density ␳S in an inhomogeneous ferroelectric-
semiconductor film.
tors. The derived system of three coupled equations gives the
correct description of dielectric and ferroelectric hysteresis
loop shapes and experimentally observed coercive field val-
ues 关see Fig. 1共c兲兴. In this paper we evolve the proposed
model29 for pyroelectric response and demonstrate that the
pyroelectric hysteresis loops of ferroelectric semiconductor
films with charged defects could be successfully described
by using six coupled equations.
II. THEORETICAL DESCRIPTION
A. The model and basic assumptions
The proposed model has been evolved under the follow-
ing assumptions.
• We consider n-type ferroelectric-semiconductor film
with sluggish randomly distributed impurity centers
or/and growth defects. The charge density of defects
␳S共r兲 is characterized by the positive average value ¯␳S
and random fluctuations ␦␳S共r兲, i.e., ␳S共r兲 = ¯␳S
+ ␦␳S共r兲 关see Fig. 2共a兲兴.
• Movable screening charge distribution ␦n共r , t兲 with
the Debye screening radius RD surrounds each charged
center 关see Fig. 2共b兲兴, so free carrier charge density
n共r , t兲 = n̄ + ␦n共r , t兲 is characterized by the negative av-
erage value n̄ and modulation ␦n共r , t兲.
• Hereinafter the overbar designates the averaging of the
function f over the film volume V : f = f̄ + ␦ f共r , t兲. By
definition f̄共t兲 = 共1 / V兲兰V f共r , t兲dr and ␦ f共r , t兲 = 0, where
f = 兵n , ␳S , E , D , . . . 其. The charged defects distribution is
quasihomogeneous 共i.e., ␦␳2S = const, 共␦␳S兲x,y = 0 for ev-
ery z inside the film −l / 2 艋 z 艋 l / 2兲. The average dis-
tance between defects is d = a / 冑3 Nd 共a is the lattice
 014109-3 Morozovska et al.
constant and 0 ⬍ Nd Ⰶ 1 is defect concentration兲. For a
micrometer-thick film with 0.1% 艋 Nd 艋 10%, one es-
timates that d Ⰶ l 关see Fig. 2共a兲兴.
• The film occupies the region −l / 2 艋 z 艋 l / 2. We sup-
pose that the potentials of electrodes are given, so that
the external field E0共t兲 is applied along the polar axis
z. Screening charge distribution is deformed in the ex-
ternal field E0共t兲, and the system “defect center ␦␳S
+ screening cloud ␦n” causes electric field, current,
and displacement fluctuations.
• The defect sluggishness means that 兩⳵␦␳S共r兲 / ⳵t兩
Ⰶ 兩⳵␦n共r , t兲 / ⳵t兩 and 兩⳵␦␳S共r兲 / ⳵t兩 Ⰶ 兩dE0 / ldt兩.
• The period of the changing external field is small
enough for the validity of the quasistatic approxima-
tion rot E = 0 rot H = 0. Thus, Maxwell’s equations for
the quasistatic inner electric field E共r , t兲 and displace-
ment D共r , t兲 have the form:
⳵D
div D = 4␲关␳S共r兲 + n共r,t兲兴, + 4␲jc = 0.
⳵t
Here E共r , t兲 ⬅ ezE0共t兲 + ␦E共r , t兲 and D共r , t兲 ⬅ ezD共t兲
+ ␦D共r , t兲. Maxwell’s equations 共1兲 have to be supple-
mented by the material expression for macroscopic
free-carrier current charge density jc ⬇ ␮nE − ␬ grad n.
One should take into account only electron mobility ␮
and diffusion coefficient ␬, allowing for the defect
sluggishness. Hereinafter n̄ ⬍ 0, ␮ ⬍ 0, and ␬ ⬎ 0.
• We use the Landau-Khalatnikov equation for the dis-
placement z-component relaxation as the equation of
state but take into account the charged defects and
correlation effects 关i.e., ⳵2Dz / ⳵r2 ⫽ 0, because
Dz共r , t兲 = D共t兲 + ␦D共r , t兲兴:
⳵Dz ⳵ 2D z
⌫ + ␣Dz + ␤Dz3 − ␭ 2 = Ez .
⳵t ⳵r
Parameter ⌫ ⬎ 0 is the kinetic coefficient, ␣ ⬍ 0 and
␤ ⬎ 0 are material parameters, and ␭ ⬎ 0 is the gradi-
ent coefficient of the hypothetical pure 共free of de-
fects兲 uniaxial ferroelectric. For perovskites one can
use the coupled Landau-Khalatnikov equations for
three components Dz,x,y共r , t兲 instead of one equation
共2兲 共see, e.g., free energy in Ref. 9兲. Hereinafter we
suppose that only the coefficient ␣ = −␣T共TC − T兲 es-
sentially depends on temperature in usual form:
⳵␣ / ⳵T = ␣T.1 The temperature dependence of other co-
efficients ␤, ␭, and ⌫ could be neglected within the
framework of the Landau-Ginsburg phenomenology
for the second order phase transitions.1 The tempera-
ture dependence ⳵n̄ / ⳵T could be neglected at tempera-
tures T Ⰷ Ea / kB ⬃ 50 K.33,34
The spatial distribution and temporal evolution of the
displacement D共r , t兲 in the film are determined by the non-
linear system 共1兲 and 共2兲 supplemented by the initial distri-
butions of all fluctuating variables 共e.g., definite distribution
of charged defects兲 and boundary conditions. In the Appen-
dix we show that the system 共1兲 and 共2兲 is complete, because
the quantities ␦n and ␦E can be expressed via the fluctua-
tions of displacement ␦D and ␦␳s共r兲. The study of the do-
[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
216.165.95.69 On: Sun, 07 Dec 2014 20:50:55
J. Appl. Phys. 100, 014109 共2006兲
main wall pinning by the given distribution of charged de-
fects and domain nucleation during spontaneous
displacement reversal is beyond the scope of this paper.
Therefore, hereinafter we consider only the averaged quanti-
ties. In the general case hypothetical complete exact system
for average values and all their correlations could contain
infinite number of differential equations and thus is not the
simpler problem than the numerical solution of the stochastic
differential equations.35 Allowing for the aforementioned ap-
proximations and assumptions, we have no special reason to
consider an exact system. Instead we propose to deal with
much simpler incomplete system for the average measurable
quantities D̄, ␦D2, etc., and to estimate/postulate some cor-
relations such as the following.
• At small external electric field E0共t兲 in comparison
with microscopic one, we assume that
− ␦␳S␦n共t兲 ⬇ ␩共t兲␦␳2S 关0 艋 ␩共t,E0兲 ⬍ 1兴, 共3兲
共1兲
because each charged region ␦␳S is surrounded by the
electron density ␦n in accordance with the Debye
screening mechanism, but the smooth part of charge
density ␦n accommodated near the surfaces in the
layer with thickness ⌳ and related to the spontaneous
displacement screening does not correlate with random
charged defect distribution ␦␳S 关see Fig. 2共b兲, Appen-
dix, and Ref. 29 for details兴.
• Taking into account that under the conditions d Ⰶ l and
d Ⰶ ⌳ the frequency spectrum of fluctuations ␦D and
␦␳S has well localized maximum at spatial frequency
2␲ / d, one obtains that
⳵ 2␦ D 1 ⳵ 2␦ D 1
␦D 2 ⬇ − 2 ␦D ,
2
␦␳S 2 ⬇ − 2 ␦␳S␦D. 共4兲
⳵r d ⳵r d
共2兲
See Appendix and Figs. 2共a兲 and 3 for illustration in
one-dimensional case.
B. Coupled equations for average quantities
In our papers,29–31 we modify the classical Landau-
Khalatnikov equation 共3兲 for bulk samples and obtain the
system of coupled equations for average displacement D̄ and
its mean-square fluctuation ␦D2 and correlation with charge
defect density fluctuations ␦D␦␳S. In the present paper we
evolve coupled equations for a finite film with thickness l
and quasihomogeneous distribution of charged defects 共see
Appendix for details兲.
The average pyroelectric coefficient ¯␥ can be easily ob-
tained by the differentiation of the coupled system29 on the
temperature T. In this way we obtained coupled equations for
the average displacement D̄, its mean-square fluctuation ␦D2
and correlation ␦D␦␳S, pyroelectric coefficient ¯␥ = ⳵D̄ / ⳵T,
and its correlations with displacement fluctuations ␦␥␦D
= ␦D⳵␦D / ⳵T and charge defect density fluctuations ␦␥␦␳S
= ⳵␦D␦␳S / ⳵T:
⳵D̄
⌫ + 共␣ + 3␤␦D2兲D̄ + ␤D̄3 = E0共t兲 + Ei共l,t兲, 共5兲
⳵t
 014109-4 Morozovska et al. J. Appl. Phys. 100, 014109 共2006兲

FIG. 3. 1D spatial distribution and frequency spectrum

of ␦D共z , t兲 and ␦␳S共z兲 calculated for average distance
between defects d = 10, screening layer thickness ⌳
= 30, film thickness l ⬇ 260, lattice constants, and
charged defect linear concentration ⬃10%. Dashed
peaks correspond to the model 1D spectrum when iden-
tical defects are regularly distributed with distance d
between them 共see dashed curves兲. Solid curves are
computer simulation of the spectrum with random de-
fects with average distance d between them. Note that
␦D共z , t兲 low frequency peak with half-width ⬃2␲ / ⌳
corresponds to the smooth displacement variation in the
screening layer with thickness ⌳.

⌫R ⳵␦D2 temperature maximum.1 Thus the film thickness decrease

+ 共␣R + 3␤D̄2兲␦D2 + ␤共␦D2兲2 leads to the degradation of their ferroelectric and dielectric
2 ⳵t
properties27 up to the appearance of relaxor features.38
= E0共t兲 冉 ␦D␦␳S
n̄
冊
− ␦Ei +
4 ␲ k BT
n̄e
␦␳S共␦␳S + ␦n兲, 共6兲
Bratkovsky and Levanyuk20 predicted the existence of
built-in field in a finite ferroelectric film within the frame-
work of phenomenological consideration. The field had a
⳵␦D␦␳S rather general nature. Our statistical approach confirms their
⌫R + 共␣R + 3␤D̄2 + ␤␦D2兲␦D␦␳S assumption and gives the possible expression of the field
⳵t
existing in the inhomogeneous ferroelectric-semiconductor
␦ ␳ S␦ n film. Another partial case, when the inner electric field is
= − E0共t兲 , 共7兲
n̄ induced by the film-substrate misfit strain, has been consid-
ered in the paper.39
⳵¯␥ The renormalization ⌫R ⬅ ⌫ + ␶m of the Khalatnikov ki-
⌫ + 共␣ + 3␤␦D2 + 3␤D̄2兲¯␥ = − 共␣T + 3␤␦␥2兲D̄, 共8兲 netic coefficient in 共6兲, 共7兲, 共9兲, and 共10兲 is connected with
⳵t
the free-carrier relaxation with characteristic time ␶m
⳵␦␥␦D = 1 / 8␲␮n̄. The renormalization of coefficients ␣R ⬅ ␣ + 共␭
⌫R + 2共␣R + 2␤␦D2 + 3␤D̄2兲␦␥␦D + kBT / 4␲n̄e兲 / d2 and ␣RT ⬅ ␣T + kB / 4␲n̄ed2 are caused by
⳵t
correlation and screening effects 关see 共4兲, Appendix, and Ref.

冋
= E0共t兲
␦␥␦␳S
n̄
− 共␣RT + 6␤D̄¯␥兲␦D2
30兴. The coefficient ␣ = −␣T共TC − T兲 is negative in the perfect
ferroelectric phase without defects 共␦␳2S = 0, TC ⬎ T兲. For the

册
partially disordered ferroelectric with random defects 共␦␳2S
4␲kB ⬎ 0兲, coefficient ␣R is positive; moreover, ␣R Ⰷ 兩␣兩, ␣RT
+ ␦␳S共␦␳S + ␦n兲 , 共9兲
n̄e Ⰷ ␣T, and usually the ratio ␰ = −␣R / ␣ Ⰷ 1.29 For example, for
Pb共Zr, Ti兲O3 solid solution, ␣ ⬃ −共0.4– 2兲 ⫻ 10−2,9 gradient
⳵␦␥␦␳S term ␭ ⬇ 5 ⫻ 10−16 cm2, screening radius RD
⌫R + 共␣R + ␤␦D2 + 3␤D̄2兲␦␥␦␳S ⬃ 共10 – 10−4兲 cm,15 average distance between defects d
−6
⳵t
⬃ 共10−6 – 10−4兲 cm, and thus ␣R ⬇ kBT / 4␲n̄ed2 ⬃ 102. The
= − 共␣RT + 2␤␦␥␦D + 6␤D̄¯␥兲␦D␦␳S . 共10兲 source of fluctuations ␦␳S共␦␳S + ␦n兲 in 共6兲 and 共9兲 originates
from the correlation between diffusion current and displace-
The built-in electric field Ei共l , t兲 = 兩共4␲␭ / l兲共␦n兲x,y兩−l/2
in 共5兲
+l/2
ment fluctuations 关see 共A19兲 in Appendix兴.
and its deviation ␦Ei = 兩共2␲ / ln̄兲关兰z dz共␦n + ␦␳S兲兴x,y兩−l/2
z
in 共6兲
2 +l/2
0 Let us introduce the following dimensionless variables
are inversely proportional to the film thickness l; thus they
in the system 共5兲–共10兲: Dm = D̄ / DS disorder parameter ⌬m
vanish in the bulk material.29 For a finite film built-in field
= ␦D2 / D2S, Km = −␦D␦␳S / DSn̄, ␥m = ¯␥ / ␥S, ⌸m = ␦␥␦D / DS␥S,
Ei共l , t兲 is induced by the smooth part of space charges ␦n
and M m = −␦␥␦␳S / ␥Sn̄, where DS共T兲 = 冑−␣共T兲 / ␤ is bulk
accommodated near the nonequivalent boundaries z = ± l / 2
共e.g., near the substrate with bottom electrode and free sur- spontaneous displacement and ␥S = dDS共T兲 / dT is bulk pyro-
face with upper electrode depicted in Fig. 3兲. Such layers are electric coefficient. Note that n̄ = −¯␳s allowing for the sample
created by the screening carries.15,18 Built-in field value com- electroneutrality. Dimensionless system 共5兲–共10兲 acquires the
pletely determines the horizontal shift of hysteresis loops form
observed in the ferroelectric films with thickness from dozen
of nanometers up to several microns.36,37 It is known that
built-in field diffuses paraelectric-ferroelectric phase transi- ⳵Dm
+ 共− 1 + 3⌬m兲Dm + ␤Dm
3
= Ee共␶兲 + Em共l兲, 共11兲
tion, in particular, it shifts and smears dielectric permittivity ⳵␶
[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
216.165.95.69 On: Sun, 07 Dec 2014 20:50:55
 014109-5 Morozovska et al. J. Appl. Phys. 100, 014109 共2006兲

␶R ⳵⌬m g, and ratio T / TC. It appeared that under the conditions w

+ 共␰ + 3Dm
2
兲⌬m + ⌬m
2
= − Ee共␶兲关Km + ␦Em共l兲兴 ⬍ 1, g Ⰷ 1, and ␰ Ⰷ 1, the scaling parameter gR2 / ␰ deter-
2 ⳵␶
mines the loop shape. Built-in field Em determines loop hori-
+ gR2 , 共12兲 zontal shift, whereas ␦Em determines their vertical asymme-
try. However, the visible vertical asymmetry exists only
⳵Km
␶R + 共␰ + 3Dm
2
+ ⌬m兲Km = − E0共␶兲R2 , 共13兲 under unlikely condition 兩␦Em兩 艌 1. The loop shape and po-
⳵␶ sition are almost independent over ␦Em under the condition
兩␦Em兩 ⬍ ⬍ 1. The loop asymmetry becomes more pronounced
⳵␥m
+ 共− 1 + 3⌬m + 3Dm
2
兲␥m = − 共1 + 3⌸m兲Dm
2
, 共14兲 with R2 increasing. Within the framework of our model, pos-
⳵␶ sible asymmetry is the main difference between the ferro-
electric loops calculated for the film in comparison with the
⳵⌸m
␶R + 2共␰ + 2⌬m + 3Dm
2
兲⌸m ones considered in Ref. 29 for the bulk material.
⳵␶

再
Figures 4 and 5 demonstrate the typical changes of py-

= − Ee共␶兲M m − ␰ 冋冉 冊 TC
T
− 1 + 6Dm␥m ⌬m 册 roelectric and ferroelectric hysteresis loops caused by the
increase of charged defect disordering 共note that gR2 / ␰

+g 冉 冊
TC
T
− 1 R2 ,冎 共15兲
⬃ ␦␳2S / ¯␳2S兲. They prove that disorder parameters ␦␥2 ⬃ ␦D2
exist near the coercive field, where D̄ → 0.
Let us underline that in contrast to the Landau-
Khalatnikov equations describing homogeneous switching
⳵M m
␶R + 共␰ + ⌬m + 3Dm
2
兲M m with ␦D2 ⬅ 0 near the coercive field, our coupled equations
⳵␶

冋冉 冊 册
TC
=− ␰ − 1 + 6Dm␥m + 2⌸m Km .
T
In accordance with our estimations29,30 fluctuation dimen-
sionless amplitude g = 4␲kBTn̄␤共␩−1 − 1兲 / ␣2e varies in the
range from 102 to 104 for typical ferroelectric semiconduc-
tors and ␩共␶ , Ee兲 ⬃ 共10−2 − 1兲. In general case the correlator
R2 = −␦␳S␦n共␶兲 / n̄2 = ␩共␶兲␦␳2S / ¯␳2S varies in the range 共0; 1兲, be-
cause its amplitude is proportional to the charged defect dis-
ordering ␦␳2S / ¯␳2S 关use 共3兲 and sample electroneutrality condi-
tion n̄ = −¯␳s兴. The ratio ␰ = −␣R / ␣ ⬇ ␣RTT / ␣T共TC − T兲 ⬃ 102,
relaxation time ␶R = ⌫R / ⌫ ⬃ 1, and dimensionless time ␶
= −t / ␣. Also dimensionless external field Ee = E0 / EC, built-in
field Em = Ei / EC, and its deviation ␦Em = ␦Ei / EC are intro-
duced in 共7兲 and 共8兲 共EC = −␣冑−␣ / ␤ is proportional to the
coercive field of the perfect material with ␦␳2S = 0兲. Note that
Em is almost independent over disordering R2 as caused by
the smooth part of space charges ␦n, whereas ␦Em is propor-
tional to the defect disordering R2, namely, ␦Em ⬃ 共␩−1
− 1兲R2 in our model 关see Figs 2 and 3 and 共3兲兴.
Hereinafter we discuss only the system response near the
equilibrium states, e.g., for the harmonic applied field E0共t兲
= Ea sin共␻t兲 the dimensionless frequency w = −⌫␻ / ␣ should
be smaller than unity. Additionally we assume that the series
⬁
␩共␶ , Ee兲 = ␩0 + 兺i=1 ␩i共w , Ea兲sin共mw␶兲 quickly converges and
␩0 Ⰷ 兩␩i兩, so we can substitute unknown functions R2共␶兲,
g共␶兲, Em共␶兲, and ␦Em共␶兲 by their stationary parts R20, g0, Em0,
and ␦Em0 and then omit subscript “0” for the sake of sim-
plicity. However, we realize that it is only the first approxi-
mation, in fact, correlation ␩共␶兲 ⬃ ␦␳S␦n共␶兲 should slightly
decrease with external field frequency or amplitude increase.
This result could be explained allowing for the fact that the
dipole correlations “sluggish defect ␦␳S + mobile carriers ␦n”
weaken with the frequency or amplitude increase.
Thus the system 共11兲–共16兲 steady-state behavior is deter-
mined by the dimensionless built-in fields Em, ␦Em, and fre-
quency w as well as by the aforementioned parameters ␰, R2,
[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
216.165.95.69 On: Sun, 07 Dec 2014 20:50:55
reveal inhomogeneous ferroelectric and pyroelectric response
switching.29 Namely, when the external field reaches the co-
共16兲 ercive value, the sample splits into the oppositely polarized
regions, so that it is nonpolarized as a whole. Every polar-
ized region causes displacement and pyroelectric coefficient
fluctuations ␦␥ and ␦D.
It is clear from Figs. 4 and 5 that the increase of gR2 / ␰
value leads to the essential decrease and smearing of pyro-
electric coefficient peaks near coercive field and to the de-
crease of the coercive field value 共compare the Landau-
Khalatnikov loops with the other ones兲. At R2 艌 0.5
pyroelectric coefficient peaks near coercive field completely
disappear and typical pyroelectric hysteresis loop looks like
the ferroelectric one. At R2 艌 0.7 the coercive field is much
smaller than its thermodynamic value at R2 = 0. Thus pyro-
electric and ferroelectric loops become sloped, much thinner,
and little lower under the increase charged defects disorder-
ing ␦␳2S. This effect is similar to the well-known square to
slim transition of the ferroelectric hysteresis loops in relaxor
ferroelectrics.24
The changes of dielectric permittivity hysteresis caused
by the increase of charged defect disordering are presented in
Fig. 6. It is clear that disordering R2 increase shifts and
smears dielectric permittivity maximum and thus leads to the
degradation of the film ferroelectric and dielectric properties.
Built-in field mainly shifts the hysteresis loops in the film.
Let us underline that we do not know any experiment in
which pyroelectric coefficient peaks near coercive field had
been observed. Moreover, usually pyroelectric hysteresis
loops in doped ferroelectrics have typical “slim” shape with
coercive field values much lower than the thermodynamic
one.13,14 Though simplifications and approximations have
been made 共e.g., Refs. 3 and 4兲, our approach qualitatively
explains available experimental results. The quantitative
comparison of our numerical modeling with typical PZT and
SBN-pyroelectric loops is presented in the next section.
 014109-6 Morozovska et al. J. Appl. Phys. 100, 014109 共2006兲

FIG. 4. Hysteresis loops of pyroelectric coefficient

¯␥ / ␥S and its correlation ␦␥␦D / 共␥SDS兲 共a兲 and order pa-
rameter D̄ / DS and disorder parameter ␦D2 / D2S 共b兲 for
small values of R2 = 0, 0.1, 0.2, 0.3, and 0.4. Other pa-
rameters: g = 100, ␰ = 100, T / TC = 0.45, w = 0.025, Em
= 0.05, and ␦Em = 0.5R2.

FIG. 5. Hysteresis loops of pyroelectric coefficient

¯␥ / ␥S and its correlation ␦␥␦D / 共␥SDS兲 共a兲 and order pa-
rameter D̄ / DS and disorder parameter ␦D2 / D2S 共b兲 for
higher values of R2 = 0.5, 0.7, and 0.9. Other param-
eters: g = 100, ␰ = 100, T / TC = 0.45, w = 0.025, Em = 0.05,
and ␦Em = 0.5R2.

[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
216.165.95.69 On: Sun, 07 Dec 2014 20:50:55
 014109-7 Morozovska et al.
FIG. 6. Hysteresis loops of dielectric permittivity ¯␧ / 兩␣兩 for different R2
values: R2 = 0, 0.1, 0.2, 0.3, and 0.4 共a兲 and R2 = 0.5, 0.6, 0.7, 0.8, and 0.9 共b兲.
Other parameters: g = 100, ␰ = 100, T / TC = 0.45, w = 0.025, Em = 0.05, and
␦Em = 0.5R2. Calculations were performed using 共A29兲–共A31兲 derived in
Appendix.
C. Comparison with experimental results and
discussion
Dopants, as well as numerous unavoidable oxygen O−2
vacancies, can play a role of randomly distributed charged
defects in “soft” PZT. Really, it is known that low level
共0.001%–1.0%兲 donor additives La, Nb, Nd, or Ce soften
PZT dielectric and pyroelectric properties at room tempera-
ture. Ferroelectric and pyroelectric hysteresis loops have
relatively high ␥ and D remnant values but reveal low coer-
cive fields in soft PZT.9,23 Usually pyroelectric hysteresis
loops of PZT are rather slim and sloped even at low frequen-
cies ␻ ⬃ 共0.1– 10兲 Hz,9 any pyroelectric coefficient maxi-
mum near the coercive field is absent.13,14
Investigated Pt– PZT– Pt/ Ti– SiO2 / Si structures with
oriented PZT layer were manufactured by radio frequency
magnetron sputtering in the system under the conditions de-
scribed previously.26 The sputtering target obtained by
uniaxial cold pressing includes the mixture of PbO, TiO2,
and ZrO2 in a stochiometric composition. The structure in-
cludes the top 150 nm Pt electrode, 1.9 ␮m layer of oriented
[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
216.165.95.69 On: Sun, 07 Dec 2014 20:50:55
J. Appl. Phys. 100, 014109 共2006兲
PZT, and bottom Pt/ Ti bilayer 共150 nm of Pt and 10 nm of
Ti兲 deposited onto the oxidized 共350 nm of SiO2兲 共100兲
n-type Si 350 ␮m substrate.
For PZT–Si-substrate structure it is necessary to design
the bottom electrode, which possesses not only a stable and
high enough electrical conductivity but also simultaneously
prevents the interfacial reactions between electrode, PZT,
and SiO2 components in PZT-film and Si-substrate surround-
ings under rather high temperature. The layer of Ti plays an
important role in limiting the diffusion of Ti in Pt/ Ti inter-
mediate bilayer through Pt layer into the PZT layer and di-
rectly into SiO2 layer, and also in correction of poor adhesion
of Pt layer. The annealing treatment of the
Pt/ TiOx / SiO2 / Si-substrate structure just before PZT deposi-
tion was performed for substrate stabilization, and postan-
nealing treatment of PZT film was performed for crystalliz-
ing the film in the polar perovskite phase. The top Pt
electrode has 1 mm2 area.
The pyroelectric response U␲ ⬃ ¯␥ of the
Pt– PZT– Pt/ Ti– SiO2 / Si structure with oriented 2-␮m-thick
PZT共46/ 54兲 : Nb film was obtained with the help of modu-
lated thermal flux method.13 During the measurements qua-
sistatic applied voltage varied in the range 共−11 V, +11 V兲
with low frequency ␻ ⬃ 0.2 Hz; the temperature T changes
with the frequency about 20 Hz. Ferroelectric and dielectric
hysteresis loops are measured for the same PZT films by
using the conventional Sawyer-Tower method and imped-
ance analyzer at higher frequencies ␻ ⬃ 1 Hz. Note that a
film capacity is proportional to the dielectric permittivity ¯␧
共see equations for ¯␧ in the end of Appendix兲. Stabilized loops
共i.e., obtained after many circles兲 and our calculations are
compared in Fig. 7.
It is clear from Fig. 7共b兲 that ferroelectric loop is slightly
asymmetrical, i.e., built-in electric field Ei ⫽ 0, whereas the
pyroelectric loop measured at lower frequency look almost
symmetrical. Note that sometimes even stabilized loops are
asymmetrical. For instance even rather thick films of disor-
dered ferroelectric SBN grown on different substrates typi-
cally reveal shifted ferroelectric and pyroelectric loops.14
The pyroelectric loop of 6-␮m-thick SBN-0.5 film on
Si– SiO2 substrate is compared with our calculations in Fig.
8.
It is clear from Figs. 7 and 8 that our model both quali-
tatively and quantitatively describes pyroelectric hysteresis
loops in thick soft PZT and relaxor SBN films. Our modeling
of ferroelectric and dielectric hysteresis loops was performed
earlier 共see, e.g., Ref. 29兲. Thus, despite used simplifications
and approximations may require more background, verifica-
tion, and/or specification, the modeling based on the coupled
equations 关共5兲–共10兲兴 gives realistic coercive field values and
typical pyroelectric hysteresis loop shape, in contrast to the
Landau-Khalatnikov approach, that describes the homoge-
neous pyroelectric coefficient switching. Taking into account
that the inhomogeneous switching of spontaneous polariza-
tion and pyroelectric response occurs in the inhomogeneous
and disordered ferroelectrics semiconductors, the proposed
coupled equations can be more relevant for the phenomeno-
 014109-8 Morozovska et al. J. Appl. Phys. 100, 014109 共2006兲

FIG. 7. Typical pyroelectric 共a兲 and ferroelectric 共b兲

loops of 2-␮m-thick PZT共46/ 54兲 : Nb film in on
Ti– SiO2 / Si substrate. Squares are experimental data
measured at T = 300 K; solid curves are our calculation
with the fitting parameters R2 = 0.5, g = 100, ␰ = 100, and
Em = −0.03 and w = 0.11 共a兲, w = 0.6 共b兲, and w = 0.4 共c兲.
All other parameters correspond to the ones for perfect
PZT共46/ 54兲 solid solution 共Ref. 9兲.

logical description of their polar and pyroelectric properties

than the models based on the Landau-Khalatnikov phenom-
jc = 兺
␳m=␳S,n
共␮m␳mE − ␬m grad ␳m兲 ⬇ ␮nE − ␬ grad n.

enology.
共A2兲
Here jc is the macroscopic free-carrier current and ␳s共r兲 is
the fluctuating charge density of the sluggish defects. One
could take into account only electron mobility ␮ and diffu-
APPENDIX sion coefficient ␬, allowing for the defect sluggishness.
Hereinafter n ⬍ 0, ␮ ⬍ 0, and ␬ ⬎ 0. As the equation of state,
We assume that the period of the changing external field we use the Landau-Khalatnikov equation for the displace-
is small enough for the validity of the quasistatic approxima- ment z-component relaxation but take into account the
tion rot E = 0 and rot H = 0. Thus, Maxwell’s equations for charged defects and correlation effects 共i.e., ⳵2Dz / ⳵r2 ⫽ 0兲:
the quasistatic electric field E and displacement D have the
form ⳵Dz ⳵ 2D z
⌫ + ␣Dz + ␤Dz3 − ␭ 2 = Ez . 共A3兲
⳵t ⳵r
div D = 4␲关␳S共r兲 + n共r,t兲兴,
Parameter ⌫ ⬎ 0 is the kinetic coefficient and ␣ ⬍ 0, ␤ ⬎ 0,
and ␭ ⬎ 0 are material parameters of the hypothetical pure
⳵D 共free of defects兲 sample.
+ 4␲jc = 0. 共A1兲
⳵t The Debye screening radius RD = 冑␬ / 4␲n␮
冑
⬇ 兩kBT / 4␲ne兩 in accordance with the Einstein relation
*

They have to be supplemented by the material expression for ␮ / ␬ ⬇ e / kBT* 共electron charge e ⬍ 0兲.33,34 Hereafter we sup-
current charge density: pose that homogeneous external field E0共t兲 is applied along

FIG. 8. Pyroelectric response U␲ ⬃ ¯␥ 共a兲 and electro-

optic modulation ⌬ni ⬃ ¯␧D̄ 关共b兲 at ␻ ⬃ 1 kHz兴 obtained
for 6-␮m-thick SBN-0.5 film on Si– SiO2 substrate.
Squares are experimental data measured by Kostsov et
al. 共Ref. 14兲 at room temperature; solid curve is our
calculation with the fitting parameters R2 = 0.58, g
= 100, ␰ = 100, and Em = −0.013 and w = 0.08 共a兲 and w
= 0.2 共b兲. All other parameters correspond to the ones
for perfect SBN-0.5 共Ref. 1兲.

[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
216.165.95.69 On: Sun, 07 Dec 2014 20:50:55
 014109-9 Morozovska et al. J. Appl. Phys. 100, 014109 共2006兲

the polar z axis. The film occupies the region −l / 2 艋 z 共A7兲–共A9兲: ␦n = 共1 / 4␲兲 div共␦D兲 − ␦␳S, ␦n␦Ez = −n̄E0 − 共⳵ / ⳵t兲
艋 l / 2. We suppose that the potentials of electrodes are given, ⫻关D̄共t兲 / 4␲␮兴, and ␦Ez = −共1 / 4␲␮n̄兲共⳵ / ⳵t兲␦D − 共␦n / n̄兲E0共t兲
so that the inner field satisfies the condition + 共␬ / ␮n̄兲共⳵ / ⳵z兲␦n + 共␦n␦Ez − ␦n␦Ez兲 / n̄. Then the spatial dis-
1
l
冕 l/2

−l/2
Ez共r,t兲dz = E0共t兲. 共A4兲
tribution and temporal evolution of the displacement D共r , t兲
are determined by the nonlinear system 共A10兲 and 共A11兲
allowing for the fact that 共A11兲 could be rewritten in the
Hereinafter we introduce the representation form

D共r,t兲 = ezD共t兲 + ␦D共r,t兲, E共r,t兲 = ezE0共t兲 + ␦E共r,t兲,

冉 ⌫+
1⳵
4␲␮n̄ ⳵t
冊
␦D + 共␣ + 3␤D̄2兲␦D + 3␤D̄共␦D2 − ␦D2兲
␳S共r兲 = ¯␳S + ␦␳S共r兲, n共r,t兲 = n̄ + ␦n共r,t兲.
An overbar designates the averaging of the function f over
共A5兲
+ ␤␦D3 − ␭ +冉 ␬
冊
⳵ 2␦ D
4␲␮n̄ ⳵r2
the film volume V: f̄共t兲 = 共1 / V兲兰V f共r , t兲dr. By definition ␬ ⳵␦␳S E0共t兲 ␦n␦Ez − ␦n␦Ez
␦ f共r , t兲 = 0, where f = 兵n , ␳S , E , D , . . . 其. Here ez is the unit vec- =− − ␦n − . 共A12兲
␮n̄ ⳵ z n̄ n̄
tor directed along the z axis, Ē is the applied uniform field
E0共t兲, and Ēx,y = 0. However, in our opinion, only the adopted for the stochastic
The spatial distribution of the deviations ␦ f共r , t兲 consists differential equation implicit numerical schemes can be used
of the part caused by spontaneous displacement in order to obtain the numerical solutions of 共A6兲–共A11兲
screening,1,15 space-charged layers localized in the ultrathin supplemented by the appropriate distributions of fluctuations
screening regions near the electrodes/substrate,15,16 and the ␦␳S共r兲 and boundary conditions for ␦D共z = ± l / 2兲, which is
one caused by microscopic modulation ␦␳s with quasihomo- beyond the scope of this paper. Similar problems for the
geneous spatial distribution. For the micrometer-thick ferroelectric ideal insulators were considered in details ear-
sample the averaging over sample volume is equivalent to lier 共see, e.g., Refs. 40 and 41兲. Therefore, hereinafter we
the statistical averaging with homogeneous distribution func- consider only the average characteristics.
tion. Using the distribution function properties under the av- The coupled equations for ␦D2 and ␦D␦␳S could be ob-
eraging, we obtained from 共A1兲–共A3兲 the equations for the tained directly from 共A12兲 after multiplying over ␦D or ␦␳S
average quantities and their fluctuations: and averaging. Along with 共A10兲 they have the form
n̄ = − ¯␳S , 共A6兲 ⳵D̄ ⳵ 2␦ D
⌫ + 共␣ + 3␤␦D2兲D̄ + ␤D̄3 = ␭ 2 + E0共t兲, 共A13兲
⳵t ⳵r
div共␦D兲 = 4␲共␦n + ␦␳S兲, 共A7兲

␮n̄E0 + ␮␦n␦Ez +
⳵ D̄共t兲
= 0, ␮␦n␦Ex,y = 0, 共A8兲
冉 ⌫+
1
4␲␮n̄ ⳵t 2
冊
⳵ ␦D2
+ 关␣ + 3␤D̄2共t兲兴␦D2 + ␤␦D4
⳵t 4␲

␮共␦nE0ez + n̄␦E兲 + ␮共␦n␦E − ␦n␦E兲 − ␬ grad ␦n

+ 3␤D̄␦D3 = ␭ + 冉 ␬
4␲␮n̄
冊
⳵ 2␦ D ␬
␦D 2 −
⳵r ␮n̄
␦D
⳵␦␳S
⳵z
1 ⳵ ␦D␦n ␦n␦Ez − ␦n␦Ez
+ ␦D = 0, 共A9兲 − ␦D 共A14兲
4␲ ⳵t − E0
n̄ n̄

⌫
⳵D̄
⳵t
⳵ 2␦ D
+ 共␣ + 3␤␦D2兲D̄ + ␤D̄3 − ␭ 2 = E0共t兲,
⳵r
共A10兲 冉 ⌫+
1⳵
4␲␮n̄ ⳵t
冊
␦D␦␳S + 关␣ + 3␤D̄2共t兲兴␦D␦␳S

⳵
⌫ ␦D + 共␣ + 3␤D̄2兲␦D + 3␤D̄共␦D2 − ␦D2兲 + ␤␦D3
⳵t
+ ␤␦D3␦␳S + 3␤D̄␦D2␦␳S = ␭ + 冉 ␬
4␲␮n̄
冊 ⳵ 2␦ D
␦␳S 2
⳵r
⳵ 2␦ D ␬ ⳵␦␳2S ␦ ␳ S␦ n ␦n␦Ez − ␦n␦Ez
−␭ = ␦Ez . 共A11兲 − − E0 − ␦␳S .
⳵r2 2␮n̄ ⳵z n̄ n̄
Note that the absence of the space charge average density 共A15兲
0 = n̄ + ¯␳s in 共A6兲 means the sample electroneutrality. The
term ␮共␦n␦E − ␦n␦E兲 in 共A8兲 can be interpreted as the fluc- Using the Bogolubov method,42 the fourth and the third
tuating circular electric currents around charged defects, power correlations in 共A14兲 and 共A15兲 could be approxi-
which do not contribute into the average macroscopic cur- mated as
rent. Also we denote ␦Dz ⬅ ␦D in 共A11兲. ␦ D 4 ⬇ 共 ␦ D 2兲 2, ␦D3 ⬇ 0,
The system of Eqs. 共A6兲–共A11兲 is complete, because the
quantities ␦n and ␦E can be expressed via the fluctuations of
displacement ␦D and ␦␳s共r兲, namely, in accordance with ␦D共␦n␦E − ␦n␦E兲 ⬇ ␦D共␦n␦E − ␦n␦E兲 = 0,
[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
216.165.95.69 On: Sun, 07 Dec 2014 20:50:55
 014109-10 Morozovska et al. J. Appl. Phys. 100, 014109 共2006兲

␦ D 3␦ ␳ S ⬇ ␦ D 2␦ D ␦ ␳ S, ␦D2␦␳S ⬇ 0, Lagrange theorem about the mean point, one obtains that

⳵ 2␦ D 1 ⳵ 2␦ D 1
␦␳S共␦n␦E − ␦n␦E兲 ⬇ ␦␳S共␦n␦E − ␦n␦E兲 = 0. 共A16兲 ␦D 2 ⬇ − 2 ␦D ,
2
␦␳S 2 ⬇ − 2 ␦␳S␦D. 共A18兲
⳵r d ⳵r d
The expressions for other correlations in 共A13兲 and 共A14兲 When using integration over parts and equality ␦n
were derived in Ref. 29 for the bulk sample. In the present = 共1 / 4␲兲div共␦D兲 − ␦␳S, we transformed the terms

冉 冊冏 冏
paper we approximate them for a finite film with thickness l
with the quasihomogeneous distribution of charged defects ␬ ⳵ ␬ +l/2

关i.e., ␦␳2S = const, 共␦␳S兲x,y = 0 for every z from the region

␦D ␦␳S = 共␦D␦␳S兲x,y
␮n̄ ⳵z ␮n̄l −l/2
−l / 2 艋 z 艋 l / 2兴.
In accordance with 共A7兲 built-in field Ei ⬅ ␭⳵2␦D / ⳵r2 4␲␬
− ␦␳S共␦␳S + ␦n兲
acquires the form ␮n̄

Ei = ␭ 冉 冊 冏
⳵␦D
⳵z x,y
=
4␲␭
l
共␦n + ␦␳S兲x,y 冏 +l/2

−l/2
⬇−
4␲␬
␮n̄
␦␳S共␦␳S + ␦n兲, 共A19兲

4␲␭ ␦D␦n 共␦␳s␦D兲 E0共t兲

⬇ 兩共␦n兲x,y兩−l/2
+l/2
. 共A17兲 − E0共t兲 = E0共t兲 − 兩共␦D2兲x,y兩−l/2
+l/2
.
l n̄ n̄ 8␲ln̄
For a finite film Ei is induced by the space charge layers 共A20兲
accommodated near the nonequivalent boundaries z = ± l / 2
of examined heterostructure 关␦n共z ⬇ + l / 2兲x,y ⫽ ␦n共z Keeping in mind that the charged defect distribution is quasi-
⬇ −l / 2兲x,y ⫽ 0兴. homogeneous 关i.e., 共␦␳S兲x,y ⬇ 0 for every z from the region
Let us estimate the averaged gradient term correlations −l / 2 艋 z 艋 l / 2兴, we derive that
␦D共⳵2␦D / ⳵r2兲 and ␦␳S共⳵2␦D / ⳵r2兲 using the Fourier repre-
sentation of their complex amplitudes ␦D̃共r , t兲 冏 ␬
␮n̄l
共␦D␦␳S兲x,y 冏 +l/2

−l/2
⬇ 0,
⳵␦␳2S
⳵z
1
冏
= 共␦␳2S兲x,y
l
冏 +l/2

−l/2
⬇ 0,
= Re关␦D共r , t兲兴 and ␦˜␳S共r , t兲 = Re关␦␳S共r , t兲兴, where
共A21兲

冕
⬁ ⬁

冏 冏 冏冋冕 册冏
1
␦D̃共r,t兲 = 2 兺 dkxdkyCm共kx,ky,t兲 共␦D2兲x,y +l/2
2␲ z 2 +l/2
4␲ m=1 ␦Ei = dz共␦n + ␦␳S兲

再冋 册冎
−⬁ =
8␲ln̄ −l/2 ln̄ z0
2␲m x,y −l/2
⫻exp i kxx + ky y + z 共 ␦ n + ␦ ␳ S兲 2
l ⬃ . 共A22兲
l
and
The constant z0 in 共A22兲 can be determined from the bound-
冕
⬁ ⬁
1
␦˜␳S共r兲 = 2 兺 dkxdky Pm共kx,ky兲 ary conditions for ␦Dx,y at z = 0.
4␲ m=1 Allowing for 共A16兲–共A22兲 three coupled equations

再冋 册冎
−⬁
共A13兲–共A15兲 for the average displacement D̄, its mean-
2␲m
⫻exp i kxx + ky y + z . square fluctuation ␦D2 and correlation ␦D␦␳S acquire the
l form
Using delta-function representation, we obtained that
⳵D̄
⌫ + 共␣ + 3␤␦D2兲D̄ + ␤D̄3 = E0共t兲 + Ei共l,t兲, 共A23兲
冕
⬁ ⬁
dkxdky ⳵t
兩␦D̃共r,t兲兩 = 2
兺
m=1 −⬁ 4␲2
兩Cm共kx,ky,t兲兩2 ,
⌫R ⳵␦D2
+ 共␣R + 3␤D̄2兲␦D2 + ␤共␦D2兲2
2 ⳵t
冕
⬁ ⬁
⳵2␦D̃
冉 冊
dkxdky
␦D̃* =− 兺 兩Cm共kx,ky,t兲兩2km
2
共kx,ky兲, ␦D␦␳S 4 ␲ k BT
⳵r2 m=1 −⬁ 4␲2 = E0共t兲 − ␦Ei + ␦␳S共␦␳S + ␦n兲,
n̄ n̄e
and 共A24兲

冕
⬁ ⬁
⳵2␦D̃ dkxdky *
␦˜␳*S =− 兺 2
P C mk m 共kx,ky兲, ⳵␦D␦␳S
⳵r2 4␲2 m ⌫R + 共␣R + 3␤D̄2 + ␤␦D2兲␦D␦␳S
m=1 −⬁ ⳵t
here km2
= k2x + k2y + 4␲2m2 / l2. Under the conditions d Ⰶ l and ␦ ␳ S␦ n
d Ⰶ ␭, the fluctuation spatial spectra 兩Cm共kx , ky , t兲兩2 and = − E0共t兲 . 共A25兲
n̄
兩Pm共kx , ky兲兩2 have well localized maximum at wave vector
兩km兩 ⬇ 2␲ / d 共one-dimensional case is depicted in Fig. 3兲. The coefficient ␣ in 共A24兲 and 共A25兲 is renormalized by
Thus in accordance with the Laplace integration method and gradient terms as ␣R = ␣ + 共␭ / d2 + ␬ / 4␲␮n̄d2兲. The renormal-
[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
216.165.95.69 On: Sun, 07 Dec 2014 20:50:55
 014109-11 Morozovska et al. J. Appl. Phys. 100, 014109 共2006兲

ization of the Khalatnikov kinetic coefficient ⌫R ⬅ ⌫ + ␶m in ⳵␦␥␦␳S

共A24兲 and 共A25兲 is connected with the free carrier relaxation ⌫R + 共␣R + ␤␦D2 + 3␤D̄2兲␦␥␦␳S
⳵t
with characteristic time ␶m = 1 / 8␲␮n̄.
In contrast to the system 共A6兲–共A11兲, the system = − 共␣RT + 2␤␦␥␦D + 6␤D̄¯␥兲␦D␦␳S . 共A28兲
共A23兲–共A25兲 is not complete, namely, the correlation ␦␳S␦n,
built-in field average value Ei共l , t兲, and its fluctuation The system determining the dielectric permittivity ¯␧
␦Ei共l , t兲 are unknown. Differential equations or exact expres- = ⳵D̄ / ⳵E0 and its correlations ␦␧␦D = ␦D⳵␦D / ⳵E0 and
sions for these values should be obtained from 共A7兲–共A11兲. ␦␧␦␳S = ⳵␦D␦␳S / ⳵E0 has the form
In the general case hypothetical complete exact system for
⳵¯␧
average values and all their correlations could contain infi- ⌫ + 共␣ + 3␤␦D2 + 3␤D̄2兲␧
¯ = 1 − 6␤␦␧␦DD̄, 共A29兲
nite number of differential equations and thus is not the sim- ⳵t
pler problem than the solution of 共A7兲–共A11兲. Allowing for
made approximations 共A16兲 and 共A18兲 we have no special ⳵␦␧␦D
⌫R + 2共␣R + 2␤␦D2 + 3␤D̄2兲␦␧␦D
reason to derive an exact system. Instead we prefer to deal ⳵t
with much simpler approximate system and thus to estimate/
␦D␦␳S ␦␧␦␳S
postulate the correlation ␦␳S␦n as it was demonstrated in =− − E0共t兲 − 6␤␦D2D̄␧
¯, 共A30兲
Ref. 29 for a bulk sample. In Ref. 29 we derived that ¯␳s ¯␳S
−␦␳S␦n共t兲 ⬇ ␩␦␳2S 共0 艋 ␩ ⬍ 1兲 at small enough external field
amplitude. This result could also be applied to the film under ⳵␦␧␦␳S
⌫R + 共␣R + ␤␦D2 + 3␤D̄2兲␦␧␦␳S
small external electric field in comparison with microscopic ⳵t
ones, because each charged region ␦␳S is surrounded by the
electrons ␦n in accordance with the Debye screening mecha- ␦ ␳ S␦ n
= − ␤共2␦␧␦D + 6D̄␧
¯ 兲␦D␦␳S . 共A31兲
nism 关see Fig. 2共b兲兴, but the smooth part of charge density ␦n ¯␳S
accommodated near the surface and related to the spontane-
ous displacement screening does not correlate with random 1
M. E. Lines and A. M. Glass, Principles and Application of Ferroelectrics
charged defects distribution ␦␳S 关see solid curves in Fig. and Related Materials 共Clarendon, Oxford, 1977兲.
2
3共a兲兴. S. B. Lang, Phys. Today 58共8兲, 31 共2005兲.
3
D. Bolten, U. Bottger, T. Schneller, M. Grossmann, O. Lohse, and R.
The average pyroelectric coefficient ¯␥ = ⳵D̄ / ⳵T can be Waser, Integr. Ferroelectr. 32, 93 共2001兲.
4
obtained by the differentiation of the coupled system S. Aggarwai, I. G. Jenkins, B. Nagarai, C. J. Kerr, C. Cadney, R. Ramesh,
共A23兲–共A25兲 on the temperature T. We suppose that only the G. Velaskez, L. Boyer, and J. T. Evans, Jr., Appl. Phys. Lett. 75, 1787
共1999兲.
coefficient ␣ = −␣T共TC − T兲 essentially depends on tempera- 5
G. A. Smolenskii, V. A. Isupov, and A. I. Agranovskaya, Fiz. Tverd. Tela
ture in usual form: ⳵␣ / ⳵T = ␣T.1 The temperature dependence 共S.-Peterburg兲 1, 992 共1959兲.
of other coefficients ␤, ␭, and ⌫ could be neglected within 6
G. A. Samara, J. Phys.: Condens. Matter 15, R367 共2003兲.
7
the framework of the Landau-Ginsburg phenomenology for Y. Gao, K. Uchino, and D. Viehland, J. Appl. Phys. 92, 2094 共2002兲.
8
J. Wang, K. H. Wong, H. L. W. Chan, and C. L. Choi, Appl. Phys. A:
the second order phase transitions.1 The temperature depen- Mater. Sci. Process. 79, 551 共2004兲.
dence ⳵n̄ / ⳵T could be neglected at temperatures T Ⰷ Ea / kB 9
L. E. Cross, in Ferroelectric Ceramics, edited by N. Setter and E. L. Colla
⬃ 50 K.33,34 Also we neglect the temperature dependences 共Birkhauser, Basel, 1993兲.
10
⳵Ei / ⳵T and ⳵␦Ei / ⳵T allowing for the same reasons 关Ei ⬃ ␦n, J. F. Scott, Ferroelectric Memories 共Springer, Berlin, 2000兲.
11
U. Bottger, in Polar Oxides: Properties, Characterization, and Imaging,
␦Ei ⬃ 共␦n + ␦␳S兲2, n̄ ⬃ exp共−Ea / kBT兲兴. In this way we ob- edited by R. Waser, U. Böttger, and S. Tiedke 共Wiley-VCH, Weinheim,
tained three coupled equations for pyroelectric coefficient ¯␥ 2005兲, pp. 11–38.
12
= ⳵D̄ / ⳵T and its correlation with displacement fluctuations V. M. Ishchuk, V. L. Cherginets, O. V. Demirskaya, A. V. Aslanov, Zh. I.
Klitsova, T. S. Teplitskaya, and V. L. Sobolev, Ferroelectrics 298, 135
␦␥␦D = ␦D⳵␦D / ⳵T and charge defects density fluctuations 共2004兲.
␦␥␦␳S = ⳵␦D␦␳S / ⳵T: 13
S. L. Bravina, E. Cattan, N. V. Morozovsky, and D. Remiens, Semicond.
Phys., Quantum Electron. Optoelectron. 7, 263 共2004兲.
14
E. G. Kostsov, Ferroelectrics 314, 169 共2005兲.
15
V. M. Fridkin, Ferroelectrics Semiconductors 共Consultant Bureau, New
⳵¯␥ York, 1980兲.
⌫ + 共␣ + 3␤␦D2 + 3␤D̄2兲¯␥ = − 共␣T + 3␤␦␥2兲D̄, 16
⳵t V. B. Sandomirskii, Sh. S. Khalilov, and E. V. Chenskii, Fiz. Tekh. Polu-
provodn. 共S.-Peterburg兲 16, 440 共1982兲; Ferroelectrics 45, 107 共1982兲.
共A26兲 17
B. Meyer and D. Vanderbilt, Phys. Rev. B 63, 205426 共2001兲.
18
K. T. Li and V. Ch. Lo, J. Appl. Phys. 97, 034107 共2005兲.
19
A. Sharma, Z.-G. Ban, S. P. Alpay, and J. V. Mantese, J. Appl. Phys. 95,
3618 共2004兲.
20
⳵␦␥␦D A. M. Bratkovsky and A. P. Levanyuk, Phys. Rev. Lett. 94, 107601
⌫R + 2共␣R + 2␤␦D2 + 3␤D̄2兲␦␥␦D 共2005兲.
⳵t 21
V. Ch. Lo, J. Appl. Phys. 94, 3353 共2003兲.

冋
22
A. Gordon, S. Dorfman, and D. Fuks, Philos. Mag. B 82, 63 共2002兲.
␦␥␦␳S 23
B. Jaffe, W. R. Cook, and H. Jaffe, Piezoelectric Ceramics 共Academic,
= E0共t兲 − 共␣RT + 6␤D̄¯␥兲␦D2 London, 1971兲.
n̄

册
24
L. E. Cross, Ferroelectrics 76, 241 共1987兲.
25
4␲kB T. Tamura, K. Matsuura, H. Ashida, K. Konda, and S. Otani, Appl. Phys.
+ ␦␳S共␦␳S + ␦n兲 , 共A27兲 26
Lett. 74, 3395 共1999兲.
n̄e T. Haccart, E. Cattan, and D. Remiens, Semicond. Phys., Quantum Elec-
[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
216.165.95.69 On: Sun, 07 Dec 2014 20:50:55
 014109-12 Morozovska et al. J. Appl. Phys. 100, 014109 共2006兲

tron. Optoelectron. 5, 78 共2002兲. 35

D. Y. Gao, in Advances in Mechanics and Mathematics, edited by D. Y.
27
L. Baudry and J. Tournier, J. Appl. Phys. 97, 024104 共2005兲. Gao and R. W. Ogden 共Kluwer Academic, Dordrecht, 2003兲, pp. 261–312.
28 36
A. N. Morozovska, E. A. Eliseev, E. Cattan, and D. Remiens, Semicond. J. Rodrigues Contreras, H. Kohlstedt, U. Poppe, R. Waser, and Ch.
Phys., Quantum Electron. Optoelectron. 7, 251 共2004兲. Buchal, Appl. Phys. Lett. 83, 126 共2003兲.
29
A. N. Morozovska and E. A. Eliseev, J. Phys.: Condens. Matter 16, 8937 37
M. Shimizu, S. Nakashima, K. Kaibara, H. Fujisawa, and H. Niu, Ferro-
共2004兲; e-print cond-mat/0408647. electrics 241, 183 共2000兲.
30
A. N. Morozovska and E. A. Eliseev, Physica B 355, 236 共2005兲. 38
31 M. Tyunina and J. Levoska, Phys. Rev. B 70, 132105 共2004兲.
A. N. Morozovska and E. A. Eliseev, Phys. Status Solidi B 242, 947 39
M. D. Glinchuk and A. N. Morozovska, J. Phys.: Condens. Matter 16,
共2005兲.
32
A. N. Morozovska, Ferroelectrics 317, 37 共2005兲. 3517 共2004兲.
40
33
B. I. Shklovskii and A. L. Efros, Electronic Properties of Doped Semicon- R. C. Miller and G. Weinreich, Phys. Rev. 117, 1460 共1960兲.
41
ductors 共Springer, Berlin, 1984兲. W. Cao and L. E. Cross, Phys. Rev. B 44, 5 共1991兲.
42
34
A. Y. Shik, Electronic Properties of Inhomogeneous Semiconductors 共Gor- N. N. Bogolubov and D. V. Shirkov, Quantum Fields 共Nauka, Moscow,
don and Breach, New York, 1995兲. 1980兲.

[This article is copyrighted as indicated in the article. Reuse of AIP content is subject to the terms at: http://scitation.aip.org/termsconditions. Downloaded to ] IP:
216.165.95.69 On: Sun, 07 Dec 2014 20:50:55