Pseudoferroelectricity: A possible scenario for doped ZnO

Alexander K. Tagantsev

Citation: Applied Physics Letters 93, 202905 (2008); doi: 10.1063/1.3036537

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 APPLIED PHYSICS LETTERS 93, 202905 共2008兲

Pseudoferroelectricity: A possible scenario for doped ZnO

Alexander K. Tagantseva兲
Ceramics Laboratory, Swiss Federal Institute of Technology (EPFL), CH-1015 Lausanne, Switzerland
共Received 27 October 2008; accepted 6 November 2008; published online 21 November 2008兲
A phenomenological Landau-theory model, where a crystal on cooling from a state with polar
symmetry exhibits a maximum of dielectric permittivity and polarization-field hysteresis loops, is
offered. The model is equivalent to that of a true ferroelectric in a weak external dc bias. Permittivity
maximum occurs as a result of crossing the Widom line. In the model, the role of the external bias
plays an intrinsic internal bias originating from a weak polarity of the high temperature state of the
material. The results obtained show that the ferroelectriclike phenomena reported for doped ZnO are
compatible with a Landau-theory description. © 2008 American Institute of Physics.
关DOI: 10.1063/1.3036537兴

Zinc oxide 共ZnO兲, which adopts the polar wurtzite struc-
ture, is a polar material with a number of technical applica-
tions. Some years ago Onodera et al.1 reported a surprising
ferroelectriclike behavior in Li-substituted ZnO, showing a
polarization hysteresis loop and an associated anomaly in the
temperature-dependent dielectric permittivity. More recent
experimental data show results that may be interpreted as
manifestations of ferroelectricity in ZnO, with Mg, Be, Co,
Cr, and V substituted on the cation site.2–5 However, there
are a number of problems with the interpretation of these
effects in terms of ferroelectricity. First, the effects are weak
and, second, there is no evident mechanism for ferroelectric-
ity in the system. Finally, the most disturbing issue is that
there seems a contradiction between the presumed ferroelec-
tric phase transition and the symmetry aspect of the problem,
specifically the polar 6mm group point symmetry of ZnO.
The basic feature of any ferroelectric phase transition is
a symmetry breaking associated with the appearance of a
polar axis or the appearance of a new polar axis. In the
former case, the phase transition occurs between structures
of nonpolar and polar symmetries so that the high-symmetry
phase must be nonpolar. In the latter case, the high-symmetry
phase can be polar, but a new polar axis appears perpendicu-
lar to the existing polar axis in the high-symmetry phase.
Only the second case is compatible with ZnO, with the rel-
evant transition from 6mm to m. However, the ferroelectric-
like phenomena in 共001兲-textured Li-substituted ZnO films
suggest dielectric anomalies in the polar 共001兲 direction of
wurtzite ZnO.6 It thus appears that neither of the
ferroelectric-transition cases is compatible with the anoma-
lies found in these materials; the body of experimental evi-
dence appears incompatible with the symmetry criteria of
ferroelectricity.
The conclusion of the previous paragraph might urge
workers to abandon the search for an explanation of the data
in terms of effects relevant to ferroelectricity, in favor of
electret or charge transport effects. The goal of the present
paper is to show that despite the apparent contradiction, one
cannot exclude the possibility of a ferroelectriclike scenario
for the observations in doped ZnO.
The demonstration of this possibility is based on a well-
known fact that the application of a weak dc electric field to
a兲
Electronic mail: alexander.tagantsev@epfl.ch.
a material exhibiting a ferroelectric phase transition 共along
the direction revealing the spontaneous polarization兲 may
leave some characteristic features of the transition qualita-
tively intact. For example, the maximum in the temperature
dependence of the dielectric permittivity and the polarization
hysteresis loops in the ferroelectric phase can still be observ-
able. A remarkable feature of such system is that, under the
dc bias, it will exhibit a polar symmetry at any temperature.
The basic idea of the present paper is that a similar behavior
may appear without applied electric field, but rather originat-
ing from an intrinsic internal bias imposed by the weak po-
larity of the material at higher temperatures.
We start our discussion in the next paragraph by demon-
strating that, within the Landau theory, ferroelectric behavior
in the presence of an applied field shows a susceptibility
maximum which is similar to that reported for doped ZnO.
That is followed by a demonstration, within a simple model
system, that the role of polarity in a high-temperature non-
ferroelectric phase can be expected to mimic the effect of an
applied field as the material passes through a polarizing
structural instability. We then discuss the polarization-field
hysteresis loops in the system. Finally the possible relevance
to a material adopting a high-temperature wurzite structure is
discussed.
Let us consider a uniaxial ferroelectric with the II order
phase transition described by the Landau expansion
␣ 2 ␤ 4
F= P + P , 共1兲
2 4
which yields the equation of state via the condition
⳵F
E= . 共2兲
⳵P
Here P and E are the electric field and the polarization di-
rected along the ferroelectric axis, respectively; ␣ = A共T
− Tc兲; T and Tc are the temperature and the transition tem-
perature, respectively; and A and ␤ are positive constants.
The E-T phase diagram of this system is schematically
shown in Fig. 1共a兲. There, the solid line shows the field-
induced I order phase transition between the two possible
polarization states of the system at T ⬍ Tc. On crossing this
line by changing the electric field at a given temperature, one
induces ferroelectric switching. By monitoring the polariza-
tion change induced by the electric field, which oscillates

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 202905-2 Alexander K. Tagantsev Appl. Phys. Lett. 93, 202905 共2008兲

FIG. 2. 共a兲 A model nonpolar structure with a ferroelectric instability with

FIG. 1. 共a兲 Schematic of the field-temperature 共E-T兲 phase diagram for a respect to displacements 共in the plane of the drawing兲 of cations shown with
uniaxial ferroelectric with the II order phase transition. The solid line is the black circles. Anions are shown with open circles. 共b兲 A model structure
line of the I order phase transition corresponding to the ferroelectric switch- obtained from 共a兲 by adding the atoms shown with gray circles. Now the
ing. The solid point shows the position of the critical point corresponding to environment of the ferroelectric black cations can be viewed as weakly
the ferroelectric. The dashed lines are the so-called Widom lines. On cross- polar. The structure shown in 共b兲 may exhibit the ferroelectriclike response
ing these lines 共e.g., along the dotted lines兲 the lattice contribution to the when characterized in field directed as shown in Fig. 1共b兲.
dielectric susceptibility passes through a maximum, as shown in 共b兲. 共b兲
Schematic of the temperature dependence of the lattice contribution to the
differential susceptibility ␹ of a ferroelectric with the II order: 共1兲 no dc bias us modify this structure by adding the gray atoms, as shown
applied, 共2兲 under a small dc bias E1, and 共3兲 under a dc bias E2 that is larger
than E1. The position of the maximum in curves 共2兲 and 共3兲 as function of
in Fig. 2共b兲. In this structure, the “ferroelectric” black cations
the dc bias corresponds to the Widom line shown in Fig. 1共a兲. are now in a polar environment. However, since the nearest
environment is centrosymmetric, this polarity can be consid-
ered weak. The asymmetry imposed by the gray atoms can
about the zero value, at T ⬍ Tc one gets a P-E hysteresis be incorporated in the phenomenological framework by in-
loop. The point at T = Tc and E = 0 is the critical point. By troducing a weak intrinsic internal bias. Such situation can
crossing this point in any direction on the E-T plane, one be described within a Landau expansion obtained by modi-
finds discontinuities of the second derivatives of the thermo- fying Eq. 共1兲 as follows:
dynamic potential. For example, crossing this point under the
condition of vanishing electric field, one finds the Curie– ␣ 2 ␤ 4
Weiss anomaly of the dielectric susceptibility with a singu- F= P + P − PEint . 共4兲
larity at T = Tc. The diagram also contains the so-called Wi- 2 4
dom lines 共or overcritical traces of the critical point兲 shown Here the internal field Eint takes into account the “weakly
with the dashed lines. On crossing these lines the dielectric polar” environment of the ferroelectric cation. In this system,
susceptibility passes through a maximum. Using Eqs. 共1兲 and the polarization response, calculated using Eqs. 共2兲 and 共4兲,
共2兲 and the definition of the susceptibility as 共⳵2F / ⳵ P2兲−1, the can be viewed as that of a ferroelectric with a weak intrinsic
equation for these lines is found in the form internal bias.
The model presented above lifts the contradiction be-
16 tween the maximum in the temperature dependence of the
E2 = ␣3 . 共3兲 dielectric susceptibility and the polarity of the “high-
27␤
temperature phase.” The next issue to be discussed is the
Thus, if, at a fixed value of the bias field, the temperature appearance of P-E hysteresis loops on cooling through the
variation of the dielectric susceptibility is monitored, one “transition temperature.” It is clear that in our model the
finds a dependence with a maximum. One readily shows that ferroelectric switching in a weakly polar crystal will proceed
the maximum height decreases with increasing the bias field as in the ferroelectric, which is exposed to the combination
and the maximum broadens. This is illustrated Fig. 1共b兲. of switching field and an additional dc bias 共or internal bias兲.
A remarkable feature of the situation discussed above is If the latter is not too large, P-E hysteresis loops are to be
that, under the bias, even at temperatures above the suscep- observed below the transition temperature, however, with a
tibility maximum the ferroelectric exhibits a polar structure. voltage offset common for materials with an internal bias
Such behavior, namely, the diffuse anomaly of the second 共see, e.g., Ref. 8兲. Actually, one might take this as a finger-
derivative of the thermodynamic potential without any print of this kind of system. However, in reality, this is un-
change in the crystal symmetry, in principle, can occur in likely to be observed. The reason is that the crystal, grown
crystals without an external electric field. For example, a without special precautions, will contain close fractions of
diffuse anomaly of the specific heat in 共CH3NH3兲5Bi2Cl11 volumes with the different orientations of the polar axis 共i.e.,
associated with the Widom line was documented by Strukov of the intrinsic internal bias兲; in ceramics, this will always
et al.7 A conceivable situation for finding the Widom-line occur. Thus, the measured P-E hysteresis loop will be the
dielectric anomaly in a material 共without an additional elec- average of those with different signs of the voltage offset. If
tric field being applied兲 may occur in crystals which, in the the internal bias does not substantially exceed the half-width
high-temperature state, are only slightly polar distorted. This of the local loop, the resulting loop will look rather similar to
situation can be illustrated with model structures shown in the “normal” ferroelectric loop. This is illustrated in Fig. 3. It
Fig. 2. Here, in Fig. 2共a兲, a nonpolar structure is shown. Let is clear that double hysteresis loops may appear in the sys-
this structure exhibit a second order ferroelectric phase tran- tem in the case of larger values of the internal bias.
sition associated with displacements of black cations in the Thus, the presented model of a ferroelectric distorted
plane of the figure. In this structure, the ferroelectricity can with a weak intrinsic internal bias makes possible a Landau-
be described
This article withasthe
is copyrighted free energy
indicated givenReuse
in the article. of 共1兲.
by Eq. Now let
AIP content theory-based
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14.139.196.4 On: Thu, 02 Oct 2014 10:37:39
 202905-3 Alexander K. Tagantsev
FIG. 3. 共a兲 A P-E hysteresis loop. 共b兲 Loop calculated as the half-sum of
two loops obtained from 共a兲 by x-axis shifts of Ec and −Ec. 共c兲 Loop calcu-
lated as the half-sum of two loops obtained from 共a兲 by x-axis shifts of 1.2Ec
and −1.2Ec.
anomaly and conventional P-E hysteresis loops in a material
exhibiting a polar crystalline symmetry in the high-
temperature phase. This analysis suggests that the behavior
of doped ZnO might be rationalized in terms of a
ferroelectric-based scenario. A possible test for the relevance
of the scenario presented here to the effects reported on
doped ZnO is to monitor the P-E hysteresis loops in a non-
twinned single crystal of the material. If this scenario is rel-
evant, an offset of the loops along the E axis should be
observed, with the sign of the offset being correlated with the
orientation of the polar axis in the experiment.
This paper does not address the microscopic phenomena
behind the dielectric response of doped ZnO, however we
would like to scrutinize the ZnO structure from the point of
view of the phenomenological model developed above. In
the wurtzite structure, every Zn atom is in the tetrahedral
position, with the distances to the four nearest neighboring
oxygens 共a1 = a2 = a3 = 1.97 Å, a3 = 1.99 Å兲 共Ref. 9兲 equal to
within 1%. Thus, its local symmetry can be view as distorted
4̄3m nonpolar point group. Ferroelectricity with this symme-
try of the paraelectric phase has been documented for
boracites.10 The description of such ferroelectricity affected
by the intrinsic internal bias requires a more involved Lan-
dau potential than that given by Eq. 共4兲, however a qualita-
tively similar physical situation can be expected.
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Appl. Phys. Lett. 93, 202905 共2008兲
In conclusion, a diffuse maximum in the temperature
dependence of the dielectric susceptibility and the appear-
ance of P-E hysteresis in a material exhibiting a polar crys-
talline symmetry at any temperature can be described in
terms of a Landau-theory-based approach. The evolution of
the properties of the material on decreasing the temperature
is interpreted as a result of crossing the Widom line. The
origin of the Widom line is suggested to be an intrinsic in-
ternal bias caused by a weak polar asymmetry of the envi-
ronment for the ferroelectric active element. The wurtzite
structure of ZnO does not exclude a possibility of the
Widom-line relevant phenomenological scenario offered in
the paper. However, the experimental information presently
available does not suffice to identify the true mechanism
behind the findings reported for doped ZnO.
The author is grateful to Alexandra Carvalho and Joe
Trodahl for reading the manuscript and for useful sugges-
tions for its improvement. This project was supported by the
Swiss National Science Foundation.
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