APPLIED PHYSICS LETTERS 95, 092902 共2009兲

Imprint in ferroelectric materials due to space charges: A theoretical

analysis
M. B. Okatan and S. P. Alpaya兲
Department of Chemical, Materials, and Biomolecular Engineering, Materials Science and Engineering
Program, and Institute of Materials Science, University of Connecticut, Storrs, Connecticut 06269,
USA
共Received 10 June 2009; accepted 15 August 2009; published online 1 September 2009兲
Imprint is a degradation mechanism in ferroelectrics that results in the displacement of the
polarization hysteresis loop along the electric field axis. We develop a model using a nonlinear
thermodynamic analysis coupled with electrostatics to show that such internal voltage offsets can
originate from asymmetrically distributed trapped space charges. The electrostatic interactions are
established through a built-in polarization due to the space charges and the spontaneous polarization.
Numerical results for Ba0.8Sr0.2TiO3 show that the maximum electric field offset does not
necessarily occur due to charges trapped near the electrodes. © 2009 American Institute of Physics.
关DOI: 10.1063/1.3222871兴

Ferroelectrics possess a switchable nonzero polarization
that makes it possible for these materials to be used in non-
volatile memory applications. Furthermore, ferroelectrics can
sense changes in temperature, electric field, and stress state.
Therefore, these materials can be employed in a variety of
applications such as piezoelectric transducers and pyroelec-
tric IR detectors for night-vision applications. The dielectric
properties of ferroelectrics display a strong nonlinearity in
the presence of an external electric field and thus have found
applications in frequency-agile phase shifters and filters in
wireless telecommunications systems. One of the important
degradation mechanisms often observed in ferroelectrics is
imprint. The most common characteristic of imprint is the
displacement of the polarization hysteresis 共P-E兲 loop along
the electric field axis by ⌬E. This gives rise to an asymmetry
in the remnant polarization and also an effective variation in
the coercive field by the off-set, ⌬E. Imprint results from
exposing a poled ferroelectric material to a combination of
stimuli such as electric field, elevated temperatures, and UV
light.1–5 While the exact mechanisms of imprint are not
known, it is widely accepted that it results from trapped
charges, charged defects, and other defect dipole complexes,
as well as stress gradients.
The phenomena of imprint and possible mechanisms
have been discussed in a series of papers by Arlt and
Neumann,6 Grossman et al.,7,8 Mokry et al.,9 and Tagantsev
et al.10 The dynamics of the imprint process has been ana-
lyzed using Monte Carlo techniques.11 These and other inter-
face related phenomena are reviewed in Ref. 12. Accord-
ingly, the imprint can be explained by the formation of a
“dead” 共or passive兲 layer adjacent to the electrodes through
trapped charges introduced during processing and/or by in-
jection of free charges from the electrodes. Furthermore,
depletion effects arising from the ferroelectric-electrode con-
tacts may result in a voltage offset.12 The role of strain gra-
dients through the flexoelectric effect has also been
discussed.13 We note that nonlinear strain gradients and fer-
roelectrically dead layers may also form in epitaxial ferro-
electric films with misfit dislocations14 and these microstruc-
a兲
Author to whom correspondence should be addressed. Electronic mail:
p.alpay@ims.uconn.edu.
tural features may thus give rise to voltage offsets.12
In this study, we show that internal voltage offsets and
imprint can result from asymmetrically distributed trapped
space charges using a nonlinear thermodynamic analysis
coupled with electrostatics. The electrostatic interactions are
established through the built-in polarization due to the space
charges and the spontaneous polarization. Unlike the previ-
ous approaches,8,12 we do not assume a nonswitchable sur-
face capacitor 共a passive layer兲. Instead, we directly incorpo-
rate the density of the trapped space charges into the total
free energy density of the ferroelectric using a formalism
similar to the one employed by Bratkovsky and Levanyuk.15
This methodology has the advantage that it is applicable to
any ferroelectric materials system for which the thermody-
namic coefficients have been determined. We show that the
maximum electric field offset 共imprint兲 does not necessarily
arise from charges trapped near the electrodes but at a loca-
tion between the middle of the ferroelectric material and the
electrode. Our findings also demonstrate that the maximum
reduction of the hysteresis loops both along the polarization
and the electric field axes occurs for space charges located
exactly in the middle of an electrode-ferroelectric-electrode
capacitor structure shown in Fig. 1.
A monolithic/multilayered ferroelectric material can be
thought of to be composed of n-“sections” 共or “layers”兲 with
FIG. 1. 共Color online兲 A schematic representation of a monolithic ferroelec-
tric sandwiched between metallic electrodes with localized planar space
charges analyzed in this study.

0003-6951/2009/95共9兲/092902/3/$25.00 95, 092902-1 © 2009 American Institute of Physics

092902-2 M. B. Okatan and S. P. Alpay Appl. Phys. Lett. 95, 092902 共2009兲

different polarization values when space charges are local-
ized and discretely distributed at 共n − 1兲 planes.15 For this
most general case, the electrostatic boundary conditions gov-
erning the electrical response of ferroelectric heterostructures
with space charges and compositional variations are given by
共i兲 the continuity of the normal component of the electric
displacement field at each interlayer interface, i.e,
共Pi-Pi+1兲 + ␧0共ED,i − ED,i+1兲 = ␴ i = 1,2, . . . ,共n − 1兲,
and 共ii兲 the short circuit conditions 共both electrodes are held
at the same potential兲,
n
兺
i=1
ᐉiED,i = 0.
Here, Pi, ED,i, ᐉi, and ␴ are the polarization, the depolarizing
electric field in layer i, the thickness of layer i, and the planar
space charge density, respectively, and ␧0 is the permittivity
of free space.
The solution of the system of equations given in Eqs. 共1兲
and 共2兲 yields
looses its positive definiteness兲 is the thermodynamic coer-
cive field.
We define the following parameters to characterize the
thermodynamic hysteresis loops. The coercive electric field
on the left and right side of the hysteresis loop are Ecl and
Ecr, respectively. The coordinate of the center of the hyster-
esis loop 共and thus the electric field off-set兲 along the electric
field axis is ⌬E = 1 / 2共Ecr + Ecl兲. The width and the height of
the hysteresis response are Hw = Ecr − Ecl and Hh = Pup共⌬E兲
共1兲 − Pdown共⌬E兲, respectively. Here, Pup共⌬E兲 and Pdown共⌬E兲 are
the up 共positive兲 and down 共negative兲 polarizations at ⌬E,
respectively. The coordinate of the center of the hysteresis
loop along the polarization axis is defined through ⌬P
= 1 / 2关Pup共⌬E兲 + Pdown共⌬E兲兴.
共2兲
In this study, we consider a monolithic ferroelectric ma-
terial with composition Ba0.8Sr0.2TiO3 共BST 80/20兲 sand-
wiched between two metallic electrodes 共Fig. 1兲. We assume
that the material parameters such as Curie temperature TC
and constant C, and dielectric stiffness coefficients b and c
are linear functions of composition between corresponding
values of BaTiO3 and SrTiO3.16 We assume that there are

再
localized space charges with surface charge density ␴ and
n the plane where the space charges are placed is specified
1
ED,i = − Pi − 兺 ␣ j P j through ␣1 共Fig. 1兲. We note that for this system, Eqs. 共1兲
␧0 and 共5兲 are considerably simplified since there are no com-

冋兺 册冎
j=1
n positional variations and n = 2.
+ 共n − j兲␣ j − 共n − i兲 ␴ , i = 1,2, . . . ,n, Variation of the magnitude of the offsets computed both
j=1 along the electric field and polarization axes 共⌬E and ⌬P,
respectively兲 as a function of the planar space charge density
共3兲
␴ and the location ␣1 are shown in Fig. 2. It is clearly seen
where ␣i = ᐉi / 兺nk=1ᐉk is the volume fraction of layer i. A simi- that both offsets are odd functions with respect to the axis
lar solution is presented in Ref. 16. Therefore, the total free passing through ␣1 = 0.5, i.e., the magnitude of the offsets are
energy density of an n-layered ferroelectric heterostructure is preserved but their signs are changed upon passing the mid-
given as section of the ferroelectric. At low values of ␴, both ⌬E and
⌬P are negligible and are enhanced with increasing ␴. We
冉 冊
n
1 1 1 note that ⌬P is extremely small 共⬃10−4 C / m2兲 and is thus
F兺 = 兺 ␣i F0,i + ai P2i + bi P4i + ci P6i − EextPi
i=1 2 4 6 insignificant within the ␣1 − ␴ domain considered in this
n
study compared to ⌬E. The displacements ⌬E and ⌬P ex-
1 hibit a strong dependency on the location of the localized
− 兺 ␣iED,i Pi , 共4兲 space charges. At ␴ = 0.1 C / m2, the maxima and minima in
2 i=1
⌬E occur at ␣1 = 0.2 and 0.8, respectively. ⌬E and ⌬P al-
where F0,i is the free energy density of the polarization-free ways have opposite signs with respect to each other such that
paraelectric phase and ai, bi, and ci are the dielectric stiffness for ⌬P the minimum and the maximum are when ␣1 = 0.2
coefficients of layer i. The temperature dependence of the and 0.8, respectively. For planar space charges localized at
coefficient ai is given by the Curie–Weiss law such that ai the midsection of the ferroelectric 共␣1 = 0.5兲 and near the
= 共T − TC,i兲 / ␧0Ci, where TC,i and Ci are the Curie temperature electrodes 共␣1 ⬇ 0 or 1兲 both offsets diminish.
and constant of layer i, respectively. Eext is the externally The introduction of space charges into a ferroelectric
applied electric field. material causes its hysteresis loop to shrink both along the
The equilibrium polarizations Pi are determined as solu- polarization 共height兲 and the electric field 共width兲 axes as
tions to the system of equations of state given as ⳵F兺 / ⳵ Pi shown in Figs. 3共a兲 and 3共b兲, respectively. Both of these
= 0 for i = 1 , 2 , . . . , n where reductions along the P and E axes are negligible either at low
⳵ F兺
⳵ Pi
= ai Pi + bi P3i + ci P5i − Eext +
1
␧0
冉 n
Pi − 兺 ␣ j P j 冊 values of ␴ or for space charges located near the electrode.
At a constant value of ␴, the maximum decrease in the P-E
loops occurs for ␴ located in the middle of the ferroelectric

冋兺 册
j=1
n capacitor structure.
␴ In this study, we presented a nonlinear thermodynamic
+ 共n − j兲␣ j − 共n − i兲 . 共5兲
2␧0 j=1
approach that incorporates electrostatic interactions arising
from the presence of localized space charges in a monolithic
The average polarization 具P典 can be calculated from the ferroelectric capacitor. It was shown that the thermodynamic
equilibrium polarizations as 具P典 = 兺ni=1␣i Pi. The external polarization hysteresis loops shift along the electric field axis
electric field, at which the determinant of the Hessian matrix and the direction, whether to the left or right, and the mag-
of the total free energy function F兺 becomes zero 共i.e., it nitude of the shift depends on the location and concentration
092902-3 M. B. Okatan and S. P. Alpay Appl. Phys. Lett. 95, 092902 共2009兲

FIG. 3. 共Color online兲 Variation of the 共a兲 height and 共b兲 width of the
hysteresis loop of BST 80/20 with space charges located at ␣1 and density ␴.
FIG. 2. 共Color online兲 Dependence of the offsets determined along 共a兲 the
electric field axis ⌬E and 共b兲 the polarization axis ⌬P on the density and Mantese 共United Technologies Research Center, CT兲 for
location of the space charges in BST 80/20.
many illuminating discussions.
1
of the space charges. Moreover, the hysteresis loops were G. E. Pike, W. L. Warren, D. Dimos, B. A. Tuttle, R. Ramesh, J. Lee, V. G.
found to shrink upon introducing space charges to the mono- Keramidas, and J. J. T. Evans, Appl. Phys. Lett. 66, 484 共1995兲.
2
W. L. Warren, D. Dimos, G. E. Pike, B. A. Tuttle, M. V. Raymond, R.
lithic ferroelectric material. These results clearly emphasize Ramesh, and J. J. T. Evans, Appl. Phys. Lett. 67, 866 共1995兲.
the need for careful synthesis of ferroelectrics as to minimize 3
B. H. Park, S. J. Hyun, C. R. Moon, B.-D. Choe, J. Lee, C. Y. Kim, W. Jo,
the concentration of trapped charges, charged defects such as and T. W. Noh, J. Appl. Phys. 84, 4428 共1998兲.
4
vacancies and interstitials, and other defect microstructures S.-H. Kim, D.-S. Lee, C. S. Hwang, D.-J. Kim, and A. I. Kingon, Appl.
that might give rise to imprint. The way these defects affect Phys. Lett. 77, 3036 共2000兲.
5
M. Alexe, C. Harnagea, D. Hesse, and U. Gosele, Appl. Phys. Lett. 79,
internal voltage offsets in ultrathin ferroelectric films with 242 共2001兲.
thicknesses close to the order of the correlation length of 6
G. Arlt and H. Neumann, Ferroelectrics 87, 109 共1988兲.
7
ferroelectricity may deviate from the results presented in this M. Grossmann, O. Lohse, D. Bolten, U. Boettger, T. Schneller, and R.
study. We also note that we have considered here a mon- Waser, J. Appl. Phys. 92, 2680 共2002兲.
8
odomain structure, although the emergence of a polydomain M. Grossmann, O. Lohse, D. Bolten, U. Boettger, and R. Waser, J. Appl.
Phys. 92, 2688 共2002兲.
state may also be possible,15 which would most likely be in 9
P. Mokry, A. K. Tagantsev, and J. Fousek, Phys. Rev. B 75, 094110
the form of “wedge” shaped domains.17,18 The present analy- 共2007兲.
10
sis is a thermodynamic methodology that establishes the A. K. Tagantsev, I. Stolichnov, N. Setter, and J. S. Cross, J. Appl. Phys.
driving force of the imprint process. We note that imprint is 96, 6616 共2004兲.
11
P. J. Schorn, U. Bottger, and R. Waser, Appl. Phys. Lett. 87, 242902
essentially a thermokinetic phenomenon. The complete the-
共2005兲.
oretical description of this complex process, therefore, has to 12
A. K. Tagantsev and G. Gerra, J. Appl. Phys. 100, 051607 共2006兲.
be achieved by combining thermodynamics with dynamic 13
H.-X. Cao, V. C. Lo, and Z.-Y. Li, Solid State Commun. 138, 404 共2006兲.
14
methods such as phase field modeling or Monte Carlo simu- I. B. Misirlioglu, S. P. Alpay, M. Aindow, and V. Nagarajan, Appl. Phys.
lations. For such calculations, the thermodynamic potentials Lett. 88, 102906 共2006兲.
15
A. M. Bratkovsky and A. P. Levanyuk, Phys. Rev. B 61, 15042 共2000兲.
as specified herein could certainly be the starting point. 16
M. B. Okatan, J. V. Mantese, and S. P. Alpay, Phys. Rev. B 79, 174113
共2009兲.
The authors gratefully acknowledge support by the U.S. 17
A. L. Roytburd and J. Slutsker, Appl. Phys. Lett. 89, 042907 共2006兲.
Army Research Office through Grant Nos. W911NF-05-1- 18
M. B. Okatan, A. L. Roytburd, J. V. Mantese, and S. P. Alpay, J. Appl.
0528 and W911NF-08-C-0124. The authors also thank J. V. Phys. 105, 114106 共2009兲.