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PHYSICAL REVIEW B 69, 180101共R兲 共2004兲

Griffiths-like ac nonlinearity in a disordered antiferroelectric

Eugene V. Colla and M. B. Weissman*
Department of Physics, University of Illinois at Urbana-Champaign, 1110 West Green Street, Urbana, Illinois 61801-3080, USA

Wai-Hung Chan and Haydn Chen

Department of Physics and Materials Science, City University of Hong Kong, Kowloon, Hong Kong
共Received 12 March 2004; published 13 May 2004兲
Large nonlinear effects are found in a well-defined temperature range above the Neel point in a disordered
antiferroelectric. The sign of the nonlinear susceptibility is opposite to that expected for clusters with internal
ferroelectric interactions, indicating that the effect involves antiferroelectric clusters. An extended regime of
third-harmonic generation which looks nonanalytic as a function of ac bias amplitude down to small fields is
found, indicating that the distribution of cluster sizes extends to very large values, as expected for a Griffiths
phase. However, the dependence of the susceptibility on dc fields shows no nonanalyticity, indicating that there
is no true Griffiths phase.

DOI: 10.1103/PhysRevB.69.180101 PACS number共s兲: 77.80.⫺e, 77.80.Bh, 77.80.Dj

Many decades ago Griffiths1 and McCoy2 independently
proposed that disorder can lead to a well-defined regime, at
temperatures above that of long-range ordering, with ordered
clusters whose size distribution has a tail extending to arbi-
trarily large values, thus allowing the free energy and some
response functions to be nonanalytic functions of field at
zero field.1,2 There has been surprisingly little direct experi-
mental investigation of this prediction, particularly for mate-
rials with antiferro long-range order.3– 6 The most relevant
experiments3 on a disordered antiferromagnet find deviations
from critical scaling in the expected Griffiths regime in the
linear ac susceptibility, but do not investigate nonlinear ef-
fects or dependencies on dc fields. Here we show that a
slightly disordered material with an incommensurate antifer-
roelectric ordered phase7 exhibits strongly nonlinear re-
sponse in a rather sharply defined regime extending to T *
above the temperature T N at which the antiferroelectric order
sets in. Although we find no thermodynamic nonanalyticity,
we do find an extended pseudo-nonanalytic regime of non-
linear ac response.
We studied a ceramic of Pb0.97La0.02(Zr0.60Sn0.30Ti0.10)O3 ,
called PLZST, prepared by a mixed oxide method, as de-
scribed elsewhere.8 This material forms an incommensurate
antiferroelectric 共AFE兲 phase below T N ⫽435 K, determined
from a sharp peak in the T-dependent susceptibility ␧ ⬘ (T). 7
The composition is not far from one at which ferroelectric
共FE兲 order is stable, and the AFE phase shows hysteresis
loops with polarization switching to a FE-like state at rela-
tively low electric fields, e.g., E⫽20 kV/cm. 7
The disk-shaped sample used here had thickness about 0.3
mm and contact pads on each side with about 3 mm diam-
eter. Its linear and nonlinear susceptibilities were measured
by applying a signal to one side of the capacitor, while the
other side was held at virtual ground by an op-amp 共AD549兲
used as a charge-to-voltage converter with a feedback ca-
pacitor of either 4 or 10 nF. All fields and linear susceptibili-
ties given here have an overall calibration uncertainty of
about 20% from uncertainty about the capacitor geometry.
There is also some spread in the field values due to edge
effects. The applied signals consisted of relatively pure sine
waves from commercial signal generators, sometimes at two
frequencies and sometimes with dc offsets. In order to accu-
rately measure harmonic generation at ac fields less than
about 30 V/cm it was necessary to inject a balancing current
from the voltage source via a capacitor to the virtual ground
to cancel the fundamental and also most of the harmonic
distortion of the sine-wave generators. Compensation ad-
justed by eye to remove the fundamental was much better
than needed to remove that spurious harmonic content.
␧ ⬘ (T) shows a sort of plateau between T N and T *
⫽475 K, as shown in Fig. 1. This regime has been dubbed a
multiple cell cubic paraelectric state based on a variety of
imaging results, including diffuse superlattice diffraction
peaks at wave vectors not far from those of the long-range
AFE order formed below T N . 9 Those results suggest the for-
mation of AFE clusters which suppress ␧ below the value
which it would have in the absence of this clustering. The
loss tangent ␧ ⬙ /␧ ⬘ remains under about 0.004 in the plateau
when the sample is zero-field cooled, so the plateau is not a
simple kinetic effect, in contrast to many disordered cluster
systems which show kinetic freezing, e.g., Ref. 10.
As seen in Fig. 1, ␧ ⬘ becomes anomalously sensitive to
E dc in the plateau regime. The upper onset temperature of
this sensitivity is sharp and coincides well with the T * , the
upper end of the plateau. The sign of the nonlinearity is
positive, as in the lower-T results for which E dc converts
AFE to FE order. The apparent T N , the peak of ␧ ⬘ , has little
dependence on E dc . Although a strong sensitivity of ␧ ⬘ 共and
even more of ␧ ⬙ ) to E – T history is found below about 465
K, in the upper part of the plateau the history dependence of
␧ ⬘ is negligible 共see Fig. 1兲, indicating that the onset of
strong dependence on dc field is also primarily an equilib-
rium rather than a kinetic effect. The sharpness of the onset
of nonlinear effects from clusters whose order resembles the
long-range order formed at lower T is reminiscent of the
Griffiths picture.1,2
The nonlinear ac response was investigated directly by
looking at third-harmonic 共3␻兲 generation driven by sinu-
soidal ac excitation. Figure 1 also shows the 3␻ signal gen-

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FIG. 1. ␧ ⬘ vs T, with E dc⫽0 and E ac

⬃16 V/cm, taken on cooling 共curve 3兲, and on
warming with E dc⫽0 共curve 2兲 after cooling in
E dc⫽9 kV/cm 共curve 1兲. The effective ␧ ( 3 ) ⬘
共curve 4兲 was measured by third-harmonic gen-
eration taken on cooling at 1 kHz with E ac
⬃471 V/cm at E dc⫽0.

erated by a 570 V/cm ac drive at 1 kHz. 共In order to facilitate gularity would be found, since in this electric 共as opposed to
amplitude comparisons among nonlinear effects measured by magnetic兲 system, local random fields are produced by ge-
different techniques and to approximately remove dependen- neric geometrical disorder, not requiring broken time-
cies on sample geometry, etc., we give the nonlinear results reversal symmetry.
in terms of apparent ␧ (2) and ␧ (3) , as would be found in a To see if there is an approach to a thermodynamic singu-
Taylor expansion for the polarization change: ⌬ P⫽␧⌬E larity at E⫽0, we measured harmonic generation and ␧ vs
⫹␧ (2) (⌬E) 2 ⫹␧ (3) (⌬E) 3 ... . However, these are not in gen- E dc , as shown in Fig. 3. If there were a thermodynamic
eral true ␧ (2) and ␧ (3) since the values depend on ac excita- Griffiths phase, one would expect the nonlinearity to peak at
E dc⫽0. However, varying E dc in the range ⫾375 V/cm with
tion amplitude, as we discuss in the following.兲 As T is low-
E ac⫽87 V/cm showed little change in the 3␻ generation.
ered, the 3␻ generation rises fairly rapidly but without a
Likewise we measured 2␻ generation 共i.e., ␧ (2) ) vs E dc and
definite kink at T * and falls abruptly on entering the long-
found only approximately linear dependence 共with some
range-ordered AFE phase. It is evident that, unlike in some inversion-symmetry-breaking offset, of unknown origin兲,
previous work reporting a field-induced antiferromagnetic
and similarly we found quadratic dependence of ␧ ⬘ on E dc ,
Griffiths phase,4 the clustered phase found above T N in this all consistent with analytic response.
disordered AFE material shows unusually large nonlinear The magnitude of the 3␻ generation was more than four
susceptibility down to zero applied dc field. The sign of the
in-phase nonlinear ac susceptibility was found to be positive,
as expected from the dependence of ␧ ⬘ on E dc .
Figure 2 shows apparent ␧ (3) inferred from the 3␻ re-
sponse as a function of E ac at 454 K. It is evident that, for
E ac above about 200 V/cm, V(3 ␻ ) does not scale as E 3 , but
rather as E n with n⫽2.61⫾0.1 as it would if the polarization
were not an analytic function of E. However, at lower E ac the
scaling is consistent 共within large error bars兲 with the ana-
lytic value, n⫽3. 共Hence we refer to the anomalous regime
as pseudo-nonanalytic.兲 The apparent exponent n is shown
versus T in the inset. Surprisingly, the sign of the out-of-
phase component shows that it leads rather than lags the
in-phase component. 共That does not violate thermodynamics,
unlike a linear ␧ ⬙ of the wrong sign!兲
The field scale of ⬃200 V/cm above which V(3 ␻ ) shows
anomalous scaling is far smaller than either the ⬃20 kV/cm
coercive fields found at lower T for the AFE-FE conversion
or the roughly 106 V/cm characteristic field at which single-
unit-cell polarization energies are comparable to k B T. It is FIG. 2. ␧ ( 3 ) ⬘ and ␧ ( 3 ) ⬙ at 1 kHz at 454 K are shown vs V ac ,
hard to see how such effects could arise without the presence along with a dashed-line power-law fit with n⫽2.61. The inset
of dynamically coherent clusters containing many thousands shows n vs T from similar fits over the T regime with large nonlin-
of unit cells. It is to be expected that no true zero-field sin- earity.

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FIG. 4. V(2 ␻ ,⍀) modulation of the second-harmonic response

FIG. 3. The field dependencies of the real parts of ␧, ␧ ( 2 ) , and
␧ (3)
are shown vs E dc . The zero for the change in ␧ ⬘ , ⌬␧ ⬘ , is
arbitrary. The coefficients were measured as described in the text at
T⫽454 K at 1 kHz.
by a low frequency bias is shown as a function of V( ␻ ) and V(⍀).
Squares are for varying V(⍀), triangles for varying V( ␻ ), each
with the other voltage fixed at 1 V. Closed 共open兲 symbols are the
in-phase 共out-of-phase兲 response, in ⍀.

times as large as would be expected from the cubic term of the V(⍀,2␻ ) was larger than inferred from the dc mea-
in the equilibrium response exhibited in both ␧ ⬘ (E dc) and surements and smaller than inferred from the 3␻ measure-
␧ (2) (E dc), raising questions as to the origin of the 3␻ ments. V(⍀,2␻ ) is clearly subquadratic in V( ␻ ) and slightly
generation. Since the pseudo-nonanalytic 3␻ response sublinear in V(⍀) for V( ␻ or ⍀)⬎1 V when the other volt-
is anomalously large 共compared to dc nonlinearity兲 it is age is held fixed at 1 V rms. Here the lowest field of the
by definition some sort of kinetic effect. The obvious guess anomalous scaling is below 30 V/cm, even lower than for the
would be that it comes from a power-law distribution of 3␻ effects. The response increased about logarithmically as a
coercive fields for small hysteresis loops, with the unusual function of ⍀, depending mainly on the ratio ␻/⍀, as shown
sign of the curvature coming from double-loop AFE-FE con- in Fig. 5. The dependence on overall frequency scale was
version effects like those seen at lower T. However, it would weak, again in sharp contrast to nonlinear effects in some
then be peculiar that the 3␻ response is predominantly in other disordered cluster materials.10
phase and difficult to explain the sign of the out-of-phase 3␻ These results neither fit expectations for an equilibrium
response. response nor for hysteresis loops. Instead, there appears to
We explored the relation between the large pseudo- be a two-stage nonlinear response, consisting of a large
nonanalytic 3␻ response and the smaller, cubic effects pseudo-nonanalytic response relaxing logarithmically to
of E dc by applying voltage at pairs of frequencies 共e.g.,
⍀/2␲ ⫽40 Hz and ␻ /2␲ ⫽400 Hz) to look for the ⍀ modu-
lation of the 2␻ nonlinear response, using a double lock-in
method. Some care is required in this procedure to get
the phase right for the ⍀ response, due to shifts produced
by several analog filters used to enlarge the dynamic range.
Given the large ratio ␻/⍀, one might expect that the ⍀
component would slowly sweep the effective E dc for the ␻
component, giving 2␻ generation quadratic in V( ␻ ) with
amplitude modulation in-phase with and linear in V(⍀) and
with magnitude given by the dependence of ␧ (2) on E dc . On
the other hand, nonlinearity due primarily to a distribution
of coercive fields should give asymmetric hysteresis 共a
2␻ signal兲 on the slopes of cos(⍀t), rather than on its
extrema 共which would show only the equilibrium effects兲,
giving primarily an out-of-phase variation of the 2␻
amplitude.
We found that the 2␻ amplitude varied primarily in-phase
with the cos(⍀t) signal, as shown in Fig. 4. Once again, the
out-of-phase response leads rather than lags. The amplitude FIG. 5. V(2 ␻ ,⍀) 共expressed as ␧ ( 3 ) ) vs ␻/⍀.

180101-3

COLLA, WEISSMAN, CHAN, AND CHEN
a smaller analytic value. That would account both for the
⍀-dependence of the amplitude and the peculiar sign of the
out-of-phase nonlinear response.
One may speculate 共vaguely兲 that there could be a
pseudo-nonanalytic Griffiths response 共with some rounding
near zero field due to random local fields兲, coming from the
sum of separate clusters, followed by a slow relaxation of
opposite sign, perhaps due to antiferroelectric intercluster in-
teractions. In the presence of a dc field, the system would
relax to a new equilibrium by growing new AFE correla-
tions. More work is needed to sort out these complicated
non-linear kinetics.
The regime between 435 and 475 K thus shows most but
not all the properties of a Griffiths phase. As shown before, it
has AFE clusters without long-range AFE order.9 It has an
abrupt onset, as seen both in a kink in ␧(T) and in its de-
pendence on E dc , with a thermodynamic rather than kinetic
*Electronic address: mbw@uiuc.edu
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PHYSICAL REVIEW B 69, 180101共R兲 共2004兲
origin. The transition to long-range order remains sharp, as
seen in ␧ ⬘ and even more clearly in the effective ␧ (3) . Two
distinct purely ac measurements of the nonlinearity show a
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analytic 共cubic兲 nonlinear response, indicating the absence of
any genuine thermodynamic singularity at E⫽0 within this
regime.
We thank NSF DMR 02-40644 and RGC CERG 9040688
for support at Illinois and Hong Kong, respectively. Some
work was carried out in the Center for Microanalysis of Ma-
terials, Univeristy of Illinois, which is partially supported by
the U.S. Department of Energy under Grant No. DEFG02-
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