JOURNAL OF APPLIED PHYSICS VOLUME 89, NUMBER 11 1 JUNE 2001

Lattice contraction and cation ordering of ZrTiO4

in the normal-to-incommensurate phase transition
Young K. Kim and Hyun M. Janga)
Department of Materials Science and Engineering and National Research Laboratory (NRL)
for Ferroelectric Phase Transitions, Pohang University of Science and Technology (POSTECH),
Pohang 790-784, Republic of Korea
共Received 1 December 2000; accepted for publication 4 March 2001兲
It is known that microwave dielectric ZrTiO4 undergoes a normal-to-incommensurate phase
transition 共NICPT兲 near 1125 °C. The role of the cation ordering and its relation to the anomalous
lattice contraction observed in the NICPT were studied by x-ray diffraction and Raman scattering of
ZrTiO4 specimens prepared employing various cooling rates between 1250 and 1000 °C. It was
shown that the lattice parameter b underwent a substantial change even if the long-range cation
ordering was absent. Analysis of the Raman spectra indicated that the compositional
fluctuation-induced line broadening was mainly responsible for the extrapolated linewidth at 0 K,
suggesting that the observed lattice contraction was initiated by the local short-range cation
ordering. Based on thermodynamic arguments, the anomalous lattice contraction of ZrTiO4 was
attributed to a direct consequence of the gradient coupling between the two order parameters that
describe a compositional modulation and a displacive modulation in the NICPT. © 2001 American
Institute of Physics. 关DOI: 10.1063/1.1368871兴

I. INTRODUCTION formed ZrTiO4 forms an incommensurate 共IC兲 phase. Ac-

Microwave technology has made remarkable progress,
along with the recent development of advanced communica-
tion systems that include microcellular communications and
global positioning systems 共GPS兲. In particular, dielectric
resonators have achieved an important position as the key
element in microwave integrated circuits and in microwave
filters. Microwave devices are required to have small size,
high-level temperature stability, and low power loss.1,2
Therefore dielectric materials for the resonator should pos-
sess 共i兲 high-dielectric permittivities, 共ii兲 small temperature
coefficients of resonant frequency 共TCF ⭐ ⫾ 10 ppm/°C兲,
and 共iii兲 high unloaded quality factors 共Q factor兲 for a stable
resonant frequency. Zirconium titanate 共ZrTiO4 兲-based di-
electrics meet all these requirements and have been widely
used as dielectric resonators 共e.g., Sn-modified ZrTiO4 兲3 that
are important parts of microwave filters and frequency-
controlled oscillators. Accordingly, extensive efforts have
been made for the study of physicochemical factors that
greatly influence dielectric characteristics of ZrTiO4 -based
materials.4–16 These factors include crystal structure, phase
transition characteristics, and appropriate chemical additives.
It is known that the high-temperature phase of ZrTiO4
polymorphs has the ␣-PbO2 structure with the space group
Pbcn and undergoes a cation-positional ordering upon
cooling.5,6 Unlike Ba-based complex perovskites that also
form an important class of microwave dielectrics 关e.g.,
Ba共Mg1/3Ta2/3兲O3 , BMT兴, the translational lattice periodicity
of the transformed ZrTiO4 phase is not in accordance with
that of the high-temperature form.5,6 Therefore the trans-
a兲
Author to whom correspondence should be addressed; electronic mail:
hmjang@postech.ac.kr
cording to the study done by Christoffersen and Davies,6 the
IC phase of ZrO2 can be viewed as a commensurately 1:1
cation-ordered structure with the interface modulation along
the a axis by faulted boundaries. A variety of unusual prop-
erties are associated with this nonintegral periodicity in the
IC phase.7 It is now known that ZrTiO4 dielectric undergoes
two consecutive phase transitions upon cooling the high-
temperature normal form. They are 共i兲 the normal-to-
incommensurate phase transition 共NICPT兲 at near 1125 °C
and 共ii兲 the incommensurate-to-commensurate phase transi-
tion 共ICPT兲 that recovers the usual integral periodicity near
840 °C.8–10
However, unlike usual displacive-type IC phase transi-
tions found in NaNO2 , K2 SeO4 , and BaMnF4 , the phase
transition kinetics of ZrTiO4 is known to be very sluggish
because the NICPT is governed by the cation-positional or-
dering that subsequently leads to a lattice distortion.5,8–11
Therefore for the kinetic study of the NICPT in ZrTiO4 , one
has to employ a very slow cooling rate or use a prolonged
annealing 共more than four weeks兲 below the transition
temperature.11
In addition to this kinetic feature, ZrTiO4 exhibits a sub-
stantial degree of the lattice contraction along the b axis
during a slow cooling from the high-temperature phase field.
McHale and Roth11,12 attributed this observation to a modu-
lation of the anion packing in response to the positional or-
dering of Zr and Ti cations. However, this kind of lattice
contraction was also observed when there was no indication
of long-range cation ordering, as evidenced by the absence of
the satellite reflection under the condition of enhanced cool-
ing rate.13 Therefore one cannot solely attribute this lattice
contraction to a direct consequence of the long-range order-
ing associated with the NICPT. However, there has been no

0021-8979/2001/89(11)/6349/7/$18.00 6349 © 2001 American Institute of Physics

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6350 J. Appl. Phys., Vol. 89, No. 11, 1 June 2001 Y. K. Kim and H. M. Jang

clear and systematic study on this important subject related

to the NICPT.
In view of these facts, the main objective of the present
study is to clarify the role of the cation ordering and its
relation to the lattice contraction that occurs during the
NICPT in ZrTiO4 . For this purpose we have carefully ad-
justed the degree of the cation ordering by employing vari-
ous cooling rates during the NICPT. The degree of the long-
range ordering was studied by examining x-ray diffraction
共XRD兲 patterns while information on the short-range cation
ordering was obtained by analyzing the line shape of relevant
Raman bands.

II. EXPERIMENTAL PROCEDURE

The starting materials used for the preparation of high-
purity ZrTiO4 are zirconium-n-propoxide 共70% solution in
isopropyl alcohol, Aldrich Chemicals兲 and Ti-isopropoxide
共99.999%, Aldrich Chemicals兲. For subsequent chemical
processing steps we have closely followed the procedure
used by Hirano and his coworkers14 for the sol-gel synthesis
of Sn-modified ZrTiO4 .
The dried powder was calcined at 800 °C for 4 h. After
the calcination, an additional ball-milling step was added to
ensure a fine particle size. The dried powders were first
pressed as disks and then cold-isostatically pressed under
190 MPa pressure. The pressed pellets were sintered at
1500 °C for 4 h. The sintered specimens were cooled with an
initial cooling rate of 300 °C/h down to 1250 °C. Various
cooling rates were employed for the subsequent cooling be-
tween 1250 and 1000 °C to critically assess the effect of the
cooling rate on the NICPT. Except for one particular pellet
that was directly quenched by immersing it into water at
1250 °C, all other specimens were then air-quenched imme-
diately after they had reached 1000 °C.
XRD patterns of various ZrTiO4 specimens were re-
corded using a diffractometer 共M18XCE, MAC Science, Ja-
pan兲 equipped with a graphite monochromator. To correct a
possible zero-shift in the XRD pattern, software called
17
‘‘UNITCELL’’ was used. The lattice parameters were calcu-
lated from the XRD data and were refined using a least-
squares program.
The Raman spectra for various ZrTiO4 specimens were
obtained using a NRS2100 Raman spectrometer 共JASCO,
Japan兲 equipped with a triple-grating monochromator and a
Coherent Innova 90C Ar⫹ -laser operating at 514.5 nm. It has
a spectral resolution of 1 cm⫺1 . A LN2 -cooled charge
coupled device system was used as a detector. The Raman
scattering was done using a 180° backscattering geometry.
To closely monitor temperature variations between 77 and
450 K, the specimens were attached to a cold stage in a
Joule-Thomson miniature refrigerator 共MMR Tech.兲 using
thermally conducting grease.
III. RESULTS AND DISCUSSION
A. XRD study of long-range cation ordering
As discussed previously, the normal-to-incommensurate
phase transition 共NICPT兲 occurring near 1125 °C accompa-
nies the positional ordering of Ti and Zr cations. This posi-
FIG. 1. X-ray diffraction patterns of ZrTiO4 ceramics prepared employing
various cooling rates: 共a兲 1 °C/h, 共b兲 5 °C/h, 共c兲 10 °C/h, 共d兲 50 °C/h, 共e兲
100 °C/h, 共f兲 300 °C/h, and 共g兲 rapidly quenched. The cooling was per-
formed between 1250 and 1000 °C, and the two satellite peaks marked with
filled stars represent superlattice reflections.
tional order–disorder transition can be monitored by exam-
ining satellite peaks in the XRD patterns.18 Figure 1 shows
XRD patterns of ZrTiO4 specimens prepared employing
various cooling rates. The cooling was performed between
1250 and 1000 °C. Except for the specimen ‘‘g’’ which was
directly quenched by immersing it into water at 1250 °C, all
other specimens were air-quenched immediately after they
had reached 1000 °C. As shown in the XRD patterns, the
existence of two satellite peaks is evident in the specimens
cooled with a cooling rate equal to or less than 10 °C/h. The
two satellite peaks appeared at 25.37° and 26.86° are caused
by the (0111̄) and (2001̄) superlattice reflections, respec-
tively. In addition to this, the intensity of these peaks in-
creases with decreasing cooling rate. It is well-known that
the integrated intensity of the superlattice reflection is pro-
portional to the square of the long-range order parameter.18
Therefore it is clear that the long-range cation ordering oc-
curs only when the disordered ZrTiO4 is cooled with a cool-
ing rate less than a certain critical value 共⬃10 °C/h兲 and that
the long-range order parameter increases with decreasing
cooling rate.
Since the cation ordering eventually leads to the transi-
tion to an IC phase, the degree of structural deformation can
be described by the incommensurate deviation factor 共␦兲7–10
which is a measure of the structural deviation from the com-
mensurate superlattice. The deviation factor ␦ of the incom-
mensurately ordered ZrTiO4 was estimated using the (2001̄)
satellite reflection. As shown in Fig. 2, the deviation factor
remains constant and is essentially independent of the cool-
ing rate.
Contrary to our observation, Park and coworkers
reported9 that the cooling rate strongly influenced the devia-

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J. Appl. Phys., Vol. 89, No. 11, 1 June 2001
FIG. 2. The incommensurate deviation factor ␦ plotted with the unit of a*
for three different cooling rates.
tion factor of ZrTiO4 . This apparent inconsistency seems to
be caused by the difference in the cooling condition. Park
et al. carried out their cooling experiment between 1400 °C
and room temperature by employing various cooling rates.
Thus the ZrTiO4 specimens must have underwent the
incommensurate-to-commensurate phase transition 共ICPT兲
near 840 °C. The wave vector relevant to the incommensu-
rate ZrTiO4 undergoes a rapid change near the ICPT point,
which in turn causes a significant variation in the incommen-
surate deviation factor depending on the cooling rate.7,10
Contrary to this, we have rapidly quenched the incommen-
surate ZrTiO4 specimens at 1000 °C to completely suppress
any further transition to the commensurate phase. Accord-
ingly, the deviation factor is expected to be independent of
the cooling rate 共between 1250 and 1000 °C兲 in this case.
Figure 3 shows the effect of the cooling rate between
1250 and 1000 °C on the variation of the lattice parameters.
Taking the lattice parameter of the ‘‘quenched’’ specimen 共at
1250 °C兲 as a standard reference of the high-temperature
phase, one can realize a large variation of the lattice param-
eter b with the cooling rate during the NICPT. One interest-
ing feature of the experimental result presented in Fig. 3 is
that the lattice parameter b changes noticeably even for the
FIG. 3. Variation of the lattice parameters with the cooling rate between
1250 and 1000 °C.
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Y. K. Kim and H. M. Jang 6351
specimens cooled with a rate faster than 10 °C/h. In this case,
one does not expect any long-range cation ordering because
of the absence of the satellite superlattice reflection, as
shown in Fig. 1. Therefore contrary to our common belief,
the anomalous lattice contraction also occurs even if the
long-range cation ordering is absent.
It is known that ZrTiO4 is composed of hexagonally
close-packed oxygen (r O2⫺ ⫽1.40 Å兲 layers and small sized
cations (r Ti4⫹ ⫽0.605 Å, and r Zr4⫹ ⫽0.72 Å兲 that occupy
50% of the available octahedral sites formed by the close-
packed layers.19,20 Therefore the basic framework of the
ZrTiO4 structure can be viewed as hexagonally packed oxy-
gen layers. In view of this, the observed rapid contraction in
the lattice parameter b during the cooling to the
incommensurate-phase field is likely to be caused by a dis-
tortion in the anion sublattice.11 However, XRD only detects
a long-range ordering and thus is not able to give informa-
tion on the short-ranged local structure. Moreover, it is not
susceptible to any variation in the displacement of oxygen
atoms. Therefore we have employed the Raman scattering
method to obtain more detailed information on the structural
variation that occurs during the cooling from the high-
temperature disordered region 共⬎1125 °C兲.
B. Raman scattering study
1. Splitting of Raman bands
The high-temperature cation-disordered ZrTiO4 is repre-
sented by the ␣-PbO2 structure with the space group Pbcn
and the point group mmm. The normal vibration modes, as
obtained by applying the group factor analysis, predict that
the high-temperature phase has 18 distinct Raman-active op-
tical phonon modes.21,22 The representation for the Raman-
active normal modes (⌫ RA) can be written using the follow-
ing nondegenerate irreducible representations:
⌫ RA⫽4A g ⫹5B 1g ⫹4B 2g ⫹5B 3g . 共1兲
Figure 4 presents room-temperature Raman spectra of
ZrTiO4 specimens prepared employing various cooling rates
between 1250 and 1000 °C and subsequently quenched at
1000 °C. As shown in the figure, the number of visible Ra-
man bands decreases with increasing cooling rate. The de-
crease in the number of visible bands seems to be closely
related to the broadening of Raman bands for the specimens
prepared employing higher cooling rates. One of the out-
standing features of the spectra presented in Fig. 4 is that the
band splitting at a low-frequency range 共below 600 cm⫺1 兲
tends to increase with decreasing cooling rate. This splitting
becomes pronounced in the specimens cooled with the rate
⭐10 °C/h. Comparing the result of Fig. 4 with that of Fig. 1,
one can conclude that the band splitting observed at low
cooling rates is directly associated with the appearance of the
superlattice reflection in the XRD patterns. This clearly indi-
cates that the Raman band splitting is a consequence of the
cation ordering that occurs during the NICPT.
Comparing the spectrum of the quenched specimen 共g兲
with 共d兲, 共e兲, and 共f兲, one can further realize that new bands
appear even in the rapidly cooled specimens, as marked in
Fig. 4 with arrows. Figure 1 indicates the absence of long-
6352 J. Appl. Phys., Vol. 89, No. 11, 1 June 2001 Y. K. Kim and H. M. Jang

FIG. 5. Fitting result of the Raman spectra obtained using the specimen
cooled at a rate of 1 °C/h. The experimental data 共filled squares兲 and the
calculated profile 共solid lines兲 show a good agreement.

line-shape parameters 共i.e., the line broadening ⌫ and the

FIG. 4. Room-temperature Raman spectra of ZrTiO4 ceramics prepared
employing various cooling rates between 1250 and 1000 °C: 共a兲 1 °C/h, 共b兲
5 °C/h, 共c兲 10 °C/h, 共d兲 50 °C/h, 共e兲 100 °C/h, 共f兲 300 °C/h, and 共g兲 rapidly
quenched. The arrows indicate peak splittings.
range cation ordering in the specimens that correspond to the
spectra 共d兲, 共e兲, and 共f兲 in Fig. 4. Therefore the appearance of
new bands in the spectra 共d兲, 共e兲, and 共f兲 is not a consequence
of the long-range ordering but reflects a change in the local
symmetry, which is caused by the short-range cation order-
ing associated with the NICPT.
2. Analysis of line shape
Another prominent feature of the Raman spectra given in
Fig. 4 is that the line shape continuously changes with the
variation of cooling rate, reflecting changes in the local
structure with the cooling rate. Therefore we have quantita-
tively analyzed the line shape of the Raman spectra in Fig. 4
by applying the following spectral response function for the
damped harmonic oscillators:23
␹ ␻⌫
S共 ␻ 兲⫽ 兺i 共 ␻ 2 ⫺ ␻i2 兲 2 ⫹i ␻ 2 ⌫ 2 F 共 ␻ ,T 兲 , 共2兲
0i i
mode frequency ␻ 0 兲 obtained from these fittings are pre-
sented in Fig. 6 as a function of the cooling rate between
1250 and 1000 °C. The results show that the linewidth de-
creases while the mode frequency increases rather monoto-
nously with decreasing cooling rate. Figure 7 further corre-
lates the line-shape parameters with the lattice constant b.
Irrespective of the cooling rate, both the mode frequency and
the linewidth have a good linear correlation with the param-
eter b suggesting that the variation of ␻ 0 and ⌫ is directly
related to the lattice contraction occurring in the course of
the NICPT 共Fig. 3兲.
For an insulator in which cations with more than one
kind distribute randomly over the crystallographically
equivalent sites, the broadening of Raman band and the shift
of the mode frequency are generally attributed to the
followings:24,25 共i兲 the anharmonic decay of optical phonons
and 共ii兲 the scattering caused by compositional fluctuations.
The optical phonon can decay into two or more lower-energy
phonons via an anharmonic process, resulting in a reduced

where ␹ i is the amplitude in arbitrary units, ␻ 0i is the mode

frequency, and ⌫ i is the damping constant for the ith normal
mode. F( ␻ ,T) represents the Bose–Einstein population fac-
tor for the Stokes part and is given by
1
F 共 ␻ ,T 兲 ⫽ . 共3兲
1⫺exp共 ⫺ប ␻ /k B T 兲
The damping constant was corrected by the instrumental
linewidth obtained from an Ar⫹ -laser line.
Figure 5 presents the fitting result of the Raman spec-
trum obtained using the specimen cooled at a rate of 1 °C/h.
FIG. 6. Variation of the mode frequency, ␻ 0 , and the linewidth ⌫ of the
The spectral function given in Eq. 共2兲 did quantitatively fit room-temperature Raman band with the cooling rate between 1250 and
all the Raman spectra at frequencies around 800 cm⫺1 . The 1000 °C.

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J. Appl. Phys., Vol. 89, No. 11, 1 June 2001 Y. K. Kim and H. M. Jang 6353

FIG. 8. Variation of the line-shape parameters plotted as a function of

FIG. 7. The line-shape parameters of the Raman band at 300 K plotted as a
function of the lattice parameter b: 共a兲 mode frequency ␻ 0 and 共b兲
linewidth ⌫.
lifetime of the optical phonon. It is known that the reduced
lifetime directly brings in the broadening of the Raman band
via the following relation: ␶ ⫽1/␲ c⌫.25 Since this reduced
lifetime is a consequence of an anharmonic decay, it strongly
depends on temperature.25,26
Assuming that the anharmonic decay of one optical pho-
non into two acoustic phonons is primarily responsible for
the variation of Raman line shape and taking cubic and quar-
tic anharmonic terms into consideration, Balkanski et al.27
presented the following relationships for the temperature-
dependent line shift and linewidth based on the work of
Klemens:26
␻ 0 共 T 兲 ⫽ ␻ (h)
0 ⫹⌬ 共 T 兲 ,
where
temperature: 共a兲 mode frequency ␻ 0 and 共b兲 linewidth ⌫.
the harmonic approximation. The parameters A and C in Eqs.
共5兲 and 共6兲 represent the contribution of the cubic anhar-
monic term to the line shape, whereas the parameters B and
D are related with the quartic anharmonic term.
The other factor that contributes to the variation of Ra-
man line shape is the compositional fluctuation-induced
anharmonicity.25 The origin of this compositional
fluctuation-induced line broadening is quite distinct from that
of the anharmonic decay of optical phonons described by
Klemens26 and Balkanski et al.27 Therefore one does not ex-
pect a simple additive rule in the description of the line shift
or the linewidth. However, it is clearly expected that the
anharmonicity at a low-temperature region is mainly caused
by the compositional fluctuation. On the basis of this argu-
ment one can thus satisfactorily separate one factor from the
共4兲
other.
Figure 8 shows the variation of the line-shape param-

冋 册 冋 册
eters 共␻ 0 and ⌫兲 with temperature. The solid lines corre-
2 3 3 spond to the computed results using Eqs. 共4兲, 共5兲, and 共6兲
⌬T⫽C 1⫹ ⫹D 1⫹ ⫹ 共5兲
e ⫺1
x
e ⫺1
y
共 e ⫺1 兲 2
y
with optimized fitting parameters. As shown in Fig. 8共a兲, the
difference in the mode frequency between 300 and 0 K is
and

冋 册 冋 册
independent of the cooling rate employed and is 3.19⫾0.48
2 3 3 cm⫺1 . To obtain the value at 0 K, the fitting was extrapolated
⌫ 共 T 兲 ⫽A 1⫹ ⫹B 1⫹ ⫹ . 共6兲 to 0 K. Compared with the values of the mode frequency at
e ⫺1
x
e ⫺1y
共 e ⫺1 兲 2
y
0 K 共extrapolated values兲, its temperature dependence is neg-
The parameters y and x in the above equations are defined as ligibly small: ⬃810 cm⫺1 versus ⬃3 cm⫺1 . Similarly, as
y⫽ប ␻ (h)
0 /3k B T and x⫽ប ␻ 0 /2k B T. ␻ 0 in Eq. 共4兲 denotes
(h) (h)
presented in Fig. 8共b兲, the difference in the linewidth be-
the intrinsic frequency of the zone-center optical phonon in tween 300 and 0 K is essentially independent of the cooling

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6354 J. Appl. Phys., Vol. 89, No. 11, 1 June 2001
FIG. 9. The values of the mode frequency ␻ 0 and the line broadening ⌫
extrapolated to 0 K as a function of the lattice parameter b.
rate and has been estimated to be 10.78⫾2.3 cm⫺1 . The fact
that the temperature dependence of both ␻ 0 and ⌫ is irre-
spective of the cooling rate indicates that the variation of the
Raman line-shape parameters with temperature is not caused
by the change in the lattice parameter b or thus by the degree
of cation ordering but is originated from the temperature-
induced anharmonic decay of optical phonons. However, as
shown in Figs. 8共a兲 and 8共b兲, the effect of this anharmonic
decay is substantially smaller than the compositional fluctua-
tion effect caused by the cation disorder, as reflected in the
extrapolated values at 0 K.
One important feature of the line broadening presented
in Fig. 8共b兲 is that the linewidth extrapolated to 0 K increases
with increasing cooling rate. The extrapolated value rapidly
increases as the cooling rate increases from 1 to 50 °C/h. As
extensively discussed, the long-range cation ordering is ab-
sent in the ZrTiO4 prepared with the cooling rate faster than
10 °C/h 共Fig. 1兲. All these results clearly indicate that the
linewidth at 0 K increases with the degree of the cation dis-
order but decreases with the degree of the cation ordering.
This, in turn, indicates that the line broadening at 0 K is
mainly caused by the local positional disorder or thus by the
compositional fluctuation-induced anharmonicity.
Figure 9 correlates the line-shape parameters 共␻ 0 and ⌫兲
extrapolated to 0 K with the lattice parameter b. Similar to
the linear relationship observed at room temperature 共Fig. 7兲,
both the mode frequency and the linewidth have a good lin-
ear correlation with the parameter b irrespective of the cool-
ing rate. This further supports that the variation of ␻ 0 and ⌫
with the cooling rate is directly related to the lattice contrac-
tion observed during the cooling. By comparing this conclu-
sion with the role of the local cation ordering in the narrow-
ing of the linewidth 共or reversely, the role of cation disorder
in the line broadening兲, one can immediately realize the im-
portance of the short-range ordering in the early stage of the
anomalous lattice contraction.
From the analysis of XRD and Raman data, we therefore
conclude that the observed lattice contraction in the NICPT
is first induced by the local short-range cation ordering and
its coupling to the displacive modulation of oxygen layers.
This clearly explains the observation that the lattice param-
eter b undergoes a substantial variation even if the long-
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Y. K. Kim and H. M. Jang
range cation ordering is absent in the incommensurate phase
共Figs. 1 and 3兲.
C. Mechanism of the anomalous lattice contraction
It is known that thermodynamic stability of a modulated
structure is closely related to a coupling of two distinct phase
transition modes.28,29 Therefore we will examine the mecha-
nism of the anomalous lattice contraction in the incommen-
surate 共IC兲 phase in terms of a coupling of order parameters
involved. Heine and McConnell showed that an IC phase
could be stabilized by a gradient coupling of two relevant
order parameters.28 In general, two different phase-transition
modes having distinct physical origins do not mutually inter-
act because they do not possess the same symmetry. How-
ever, two distinct order parameters, when expressed in a k
space, have phase angles which are shifted by ␲/2, irrespec-
tive of their actual wave form.29 Therefore one order param-
eter and the gradient of the other order parameter having a
different physical origin could have the same symmetry,
thereby leading to a coupling between two distinct phase-
transition modes.
To examine this argument more concretely, let us write
the Gibbs free-energy function of an incommensurate system
in terms of two distinct order parameters, ␾ and ␺ .29
G 共 ␾ , ␺ 兲 ⫽L 共 ␾ 兲 ⫹L 共 ␺ 兲 ⫹G Ginzburg共 ␾ 兲 ⫹G Ginzburg共 ␺ 兲
⫹ ␨ 1 共 ␾␺ 兲 ⫹ ␨ gradient共 ␾ ⵜ ␺ ⫺ ␺ ⵜ ␾ 兲 , 共7兲
where the first two terms represent the Landau expansion and
the third and fourth terms take into account the Ginzburg
gradient energies. More specifically, they can be rewritten,
respectively, as
L 共 ␾ 兲 ⫽ 21 A 0 共 T⫺T C ␾ 兲 ␾ 2 ⫹ 41 B ␾ 4 ⫹¯
and 共8兲
G Ginzburg共 ␾ 兲 ⫽ 21 ␣ 共 ⵜ ␾ 兲 2 ⫹ 41 ␤ 共 ⵜ ␾ 兲 4 ⫹¯.
The last term of Eq. 共7兲 is the Lifshitz energy which de-
scribes the gradient interaction of the two distinct order pa-
rameters ␾ and ␺ .
Since the instability arising from a generation of the gra-
dient term in one of two order parameters is relieved by the
other order parameter, the following proportionality is estab-
lished in a modulated structure with the same proportionality
constant for both relations:29
␾ ⬀ⵜ ␺ and ␺ ⬀⫺ⵜ ␾ . 共9兲
Since an order parameter near its relevant transition point is
described by a sinusoidal wave, the following proportionality
can further be established after applying Eq. 共9兲:
␾ ⫽ ␾ 0 exp共 ⫹ik"r兲
⬀ⵜ ␺ ⫽ⵜ 兵 ␺ 0 exp共 ⫺ik"r兲 其
再 冉
⫽ ␺ 0 兩 k兩 exp ⫺i k"r⫹
␲
2 冊冎 . 共10兲
Thus the magnitude of one order parameter in a complex
plane is proportional to that of the other.
J. Appl. Phys., Vol. 89, No. 11, 1 June 2001
Using Eqs. 共8兲 and 共9兲 one can rewrite the gradient cou-
pling energy 共Lifshitz term兲 in the form of the Ginzburg
energy, namely,
␨ gradient共 ␾ ⵜ ␺ ⫺ ␺ ⵜ ␾ 兲 ⬀ ␨ gradient兵 共 ⵜ ␾ 兲 2 ⫹ 共 ⵜ ␺ 兲 2 其 .
On applying Eq. 共10兲 to Eq. 共11兲, one can readily obtain the
contribution of the gradient coupling energy to a Fourier
transform of the Gibbs free energy, namely,
G gradient⫽⫺2 兩 k兩 ␨ gradient␾ 0 ␺ 0 .
Equation 共12兲 predicts that the gradient coupling term gives a
negative contribution to the total free energy. Thus a modu-
lated incommensurate structure can be stabilized by the gra-
dient interaction or by the interactive coupling between ␾
and ⵜ ␺ , and vice versa.
In the case of ZrTiO4 , it is known that the two modula-
tions relevant to the normal-to-incommensurate transition are
the compositional modulation and the displacive
modulation.5,30 Therefore when ZrTiO4 is subjected to a
slow cooling from its high-temperature field, the composi-
tional modulation caused by the local ordering 共␾ 兲 will be
generated. Then, the displacive modulation and its gradient
共ⵜ ␺ 兲 will be created to stabilize this compositional modula-
tion. According to Eq. 共10兲, the magnitude of ␾ 共or ␺ 兲 is
proportional to that of ␺ 共or ␾ 兲. Thus the degree of the
compositional modulation increases with the degree of the
displacive modulation. Since the lattice contraction can be
viewed as an image of the displacive modulation, the spon-
taneous strain will be increased in response to the increase in
the degree of cation ordering 共␾ 兲. As quantitatively stated in
Eq. 共12兲, the stabilization of the free energy caused by this
gradient coupling is proportional to the magnitudes of these
order parameters. Therefore the anomalous lattice contrac-
tion observed in the course of the NICPT can be viewed as a
consequence of the gradient coupling between the two rel-
evant order parameters ␾ and ␺ .
IV. CONCLUSIONS
The role of the cation ordering and its relation to the
anomalous lattice contraction observed in the NICPT were
systematically studied by XRD and Raman scattering of
ZrTiO4 specimens prepared employing various cooling rates
between 1250 and 1000 °C.
The following conclusions were drawn from this study.
共i兲 The lattice parameter b underwent a substantial change
even if the long-range cation ordering, as evidenced in the
superlattice reflection, was absent in the incommensurate
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Y. K. Kim and H. M. Jang 6355
phase. 共ii兲 As indicated in the Raman line-shape parameters,
the anomalous lattice contraction was first induced by the
local short-range ordering, even in the absence of the long-
range cation ordering. 共iii兲 The observed anomalous lattice
共11兲
contraction of ZrTiO4 was explained in terms of the gradient
coupling between the two order parameters that de-
scribe a compositional modulation and a displacive modula-
tion in the NICPT.
共12兲 ACKNOWLEDGMENT
This work was supported by ‘‘University Fundamental
Research Fund, 1999’’ provided by the Ministry of Informa-
tion and Communication 共MIC兲, Republic of Korea.
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