SOLID

STATE
ELSEVIER
IONICS
Solid State Ionics 78 (1995) 249-258

Correlations between structural and electrical properties

of BaCeO, studied by coupled in-situ Raman scattering
and impedance spectroscopy
S. Loridant, L. Abello, E. Siebert, G. Lucazeau
Laboratoire d’lonique et d’Electrochimie des Solides, ENSEEG, BP 75, 38402 Saint Martin d’H&es, France

Received 12 December 1994; accepted for publication 1 March 1995

Abstract

Coupled impedance and Raman measurements were achieved on a ceramic of undoped BaCeO, in the 25-600°C
temperature range under air, argon, nitrogen and carbon dioxide. The sample was studied both in micro and normal Raman
spectroscopy. At 600°C in air, the conductivity of the compound decreases from 3 X lop7 to 1.5 X 10d7 S cm-’ after a
thermal cycle. The nature of the charge carriers is only briefly discussed. The simultaneous measurement of the Raman
spectra and of the impedance diagrams has allowed to show that a large part of the variations of the conductivity is due to
the structural changes induced by the temperature variation. Reciprocally, this coupled study contributes to the understanding
of the phase transition mechanism. The resistance of the compound and the intensity of the 133-110 cm-’ Raman band
vary in the same way when the temperature is raised or lowered between 400 and 600°C. These observations could be
related to the growth of the domains of the tetragonal phase. Their kinetics of growth is favored at 600°C but their
thermodynamic stability should be maximum at about 450°C: actually, as it can be deduced from the reduction of the
fullwidth of the Raman bands and from their intensity, the long range ordering takes place at about 450°C while the
nucleation process would start at a lower temperature. This process should start between 180 and 350°C and is characterized
by the variation of the frequencies of the modes at low energy. Thus, the increase of the resistance when the sample is
maintained at 600°C should be related to the ordering of the tetragonal phase and the large fluctuations in the electric signal
which are observed between 200 and 450°C could be related to the fluctuation of the sizes of domains. Finally, some
preliminary results related to the influence of water and of carbon dioxide are mentioned.

Keywords: Impedance spectroscopy; Raman spectroscopy; Ionic conduction; Phase transition

1. Introduction been mainly performed by using ex-situ and in-situ

IR, Temperature Programmed Desorption methods
The protonic conduction in Ln3+ doped BaCeO,, [8-101 or by weight changes [ll]. The nature of the
SrCeO, and mixed perovskite ceramics has stimu- conductivity has given rise to many debates and it is
lated a large number of works because of the poten- not yet clear if the protonic conductivity is the
tial use of these materials in fuel cells and sensors dominant one. Depending on the temperature, the
[l-7]. The incorporation of protons is ensured by conductivity by oxygen ions and even by electrons
H,O or H, at high temperature and its control has could become predominant. The chemical purity of

0167-2738/95/$09.50 0 1995 Elsevier Science B.V. All rights reserved

SSDZ 0167-2738(95)00112-3
250 S. Loridant et al. /Solid
the ceramic, its microstructure, the presence of car-
bon dioxide in the ambient atmosphere [12], its
thermal history could favor one or the other of the
possible conductivity mechanisms. In particular, the
compound can decompose slightly into BaCO, and
CeO, when heated in presence of CO, and water
[8,12], and its conductivity is expected to be strongly
altered by such a reaction even if it is partial.
Finally, it should be thermodynamically unstable
under 600°C [13] and could decompose into BaO and
ceria even in the air.
Undoped BaCeO, has not been much studied. In
particular, it is not clear at all if its conductivity at
high temperature, as for nonstoichiometric ceria [18-
201, is purely electronic or if oxygen conductivity
takes place as for zirconia. In any case, the absence
of electrode reaction semicircle in the impedance
spectra of undoped BaCeO, was interpreted [21] as
the evidence of an electronic contribution. Moreover,
the water contained in the ambient atmosphere could
introduce a protonic contribution even for the un-
doped material.
Two structural modifications ’ of the tmdoped
BaCeO, (orthorhombic + tetragonal and tetragonal
+ cubic) were evidenced by Raman spectroscopy
and were reported in [14,15]. These structural changes
were not confirmed by standard XRD (X-ray diffrac-
tion) measurements: this disagreement can be ex-
plained by the fact that XRD is not convenient for
the identification of dispersed segregated phases or
for characterizing slight structural changes involving
displacements of light atoms. The doping of the
cerate with Nd3+ ions was shown to down shift the
transition temperature [16]. Recent neutron diffrac-
tion measurements [17] on doped barium cerate have
not confirmed our Raman conclusions. The neutron
study shows that Nd-doped BaCeO, retains the or-
thorhombic structure (Pmcn space group) up to 16%
Nd. One of the aims of this paper is to show that
’ After submission of this paper a neutron study of a powder of
BaCeO, between 373 and 1273 K has been published 1281. The
existence of structural modifications is confirmed. As shown in
this paper differences of 100 K in temperatures of transitions are
meaningless. The main contradiction comes from the attribution of
the intermediate phase to rhomboedral phase group ( LY= 90.156”).
This group was also proposed as possible in our previous paper
but was eliminated on the basis of glazer classification.
State Ionics 78 (1995) 249-258
only a structural modification can explain both the
evolution of the Raman spectra and of the electrical
properties.
The electrical measurements were not repro-
ducible from one experiment to the other. For this
reason, it was felt necessary to perform electrical
measurements under given conditions (temperature,
atmosphere) and to characterize simultaneously the
chemical and the structural changes which could be
induced by the temperature changes and by the
ambient atmosphere. This paper reports the results
obtained by coupling impedance measurements and
Raman spectroscopy on undoped BaCeO,. This work
is not concerned with a discussion on the nature of
the charge carriers but aims to show that establishing
the correlations between the electrical and the struc-
tural variations can help to understand some of the
resistance variations and reciprocally contribute to
the understanding of the phase transition mecha-
nisms. In particular, instead of limiting the search of
pseudo-critical laws in the frequency variations in
order to define the transition temperature, we shall
show that depending on the spectroscopic parameter,
different processes governing the transition can be
followed.
2. Experimental
2.1. Samples
A ceramic of BaCeO, was prepared via the solid
state reaction of high purity powders of BaCO, and
CeO, (RhBne-Poulenc). The mixture was first treated
at 1400°C for six hours. After milling, the pellets
were obtained by pressing, followed by sintering at
1600°C for 10 h. A disc of 0.6 mm thickness and of
6.5 mm diameter was prepared. Its density measured
with a pycnometer was found to be slightly smaller
than the expected one (5.64 instead of 6.29 i.e. 91%
of the theoretical density). The ceramic was also
water treated at 600°C. This treatment consisted of
pouring one drop of water on the ceramic and to
maintain the sample at 600°C in a closed cell for 10
h.
Different mixtures of CeO, and BaCeO, have
been prepared and studied by Raman spectroscopy in
order to get reliable data for dosing CeO,. Powders
 S. Loridant et al. /Solid State Ionics 78 (1995) 249-258 251

of BaCO, and BaCeO, were also mixed in different
proportions in order to get reliable data for dosing
BaCO,. Powders presenting small deviations toward
the theoretical composition were also prepared in
order to have typical reference spectra.
was submitted to the following atmospheres: ambient
air, argon U, nitrogen (high purity), water vapor. No
me~mements of partial pressures or of flows were
performed. Coupled data were acquired every 10°C
from 25 up to 600°C.

2.2. Cell 2.3. Impedance measurements

Fig. 1 represents the cell which has been designed
for performing simultaneous Raman and impedance
spectroscopy measurements [23]. Its temperature can
be varied from 77 K up to 873 K and it is possible to
flush the cell with gas. The sample was covered with
Pt electrodes and placed in an alumina cup ensuring
electrical insulation and thermal regulation. The
whole set was placed on a heating sole. To allow the
photon penetration, a small window was managed in
the front electrode. In order not to perturb the electri-
cal measurements, the size of the aperture in the
electrode was limited to 0.5 mm. Such an aperture
affords micro Raman spectroscopy as well as normal
Raman spectroscopy for which the diameter of the
focus point is 1 and 20 p.m respectively. The sample
The impedance measurements were carried out
with a HP 4194A impedance meter in the 100 Hz-40
MHz frequency range. It has been checked that the
amplitude of the ac signal could be raised up to 1 V
without perturbing the measurements. The electrical
noise has been estimated from the impedance fluctu-
ations at 5000 I-Ix deduced from 20 independent
measurements.
2.4. Raman measurements
The spectra were obtained with the XY DILOR
spectrometer. The 514.5 rim exciting line of an argon
laser was focused on the sample through an objective
(G = 50) of a microscope and was then limited to 35

Objective lens

atmosphere
control
I/
eramic of
lace03

atmosphere
control

water water
cooling collmg

CUfTent
collectors

I I
u
coolant
u
programmer
connections
Ll
coolant

Fig. 1. Ceil used in coupled impedance and mi_Raman measurements.

252 S. Loridant et al. /Solid State Ionics 78 (1995) 249-258

mW in order to prevent the heating of the sample. A

conventional focusing system was also used with a
laser power of 45 mW. A systematic control of the
heating effect of the laser has been performed (at
2OO”C, 35 mW of incident power raises the tempera-
ture of the front face of the ceramic of 5°C [23]). The
spectra were systematically decomposed into indi-
vidual Lorentzian components (peak-fit program) in
order to derive precise spectral parameters. However,
in the 190-300°C temperature range, although there
is no doubt that spectral changes take place, two
different solutions give the same fit and this situation 700 600 500 400 300 200 100 0
leads to a large indetermination for some parameters. cm-’
Fig. 2. Raman spectrum of the initial ceramic used in this study
(lower curve) and Raman spectrum of a 90% BaCeO, + 10%
3. Results and Discussion CeO, sample (upper curve). The 460 cm-’ band allows to
estimate the proportion (in weight) of ceria in the ceramic.

3.1. Heterogeneities
local phase segregations could be related to small
The BaCeO, sample has been characterized by local variations of the BaO-CeO, ratio.
XRD and Raman spectroscopy before the deposition
of electrodes. Fig. 2 shows that it was orthorhombic 3.2. Electrical properties
and contained approximately 1.3 wt% of unreacted
ceria as deduced from the intensity of the 460 cm-’ Fig. 4a gives typical diagrams in the Nyquist
band. Note that ceria is completely absent when the representation. They were obtained in air and consist
compound is prepared via the melting of the oxides of one depressed semicircle. The resistance of the
[22]. When the mixture of the reactive oxides is not sample is directly given by the intersect of one
complete, it is possible to identify segregated phases depressed semi-circle with the real axis. At 6OO”C, it
by micro-Raman spectroscopy. In the present sam- is still pretty high, and taking into account the geo-
ple, the absence of such heterogeneities was checked metrical parameters, a conductivity of 3 lop7 S .
before. Fig. 3 gives examples of Raman spectra
which are obtained on different grains of a heteroge-
neous sample. Note that this sample corresponds to
the theoretical composition and contains no unre-
acted ceria. Typical spectra of a well-stabilized te-
tragonal phase (point 4) and of the orthorhombic
structure (points 1,2) are observed. Point 3 has an
intermediate structure. These structural differences
can be explained by the dispersion in the size of the
grains. The stabilization of the tetragonal phase at
room temperature can be due to the presence of
strains, defects and surface effects, likely more nu-
600 400 200 0
merous in small grains. These defects can lower the
cm- ’
transition temperature. Furthermore, small grains
Fig. 3. Micro-Raman spectra of a chemically pure sample present-
cannot release easily the thermal effect due to the
ing phase heterogeneities likely due to small local variations of
probing laser. The proportion of the tetragonal grains the BaO-CeO, ratio: point 1 and 2 correspond to grams having
seems to be more important for the powder corre- the orthorhombic structure; point 4 is a grain of a well-stabilized
sponding to the mixture BaO-(CeO,),,~,. Thus, these tetragonal structure; point 3 has an intermediate structure.
 S. Loridant et al./Solid State Ionics 78 (1995) 249-258 253

cm-l is obtained. The capacitance calculated from
the maximum frequency slightly varies with the tem-
perature. It is of the order of lo-l1 F indicating that
the observed semicircle can be related to bulk phe-
nomenon.
A large proportion of Ce3+ in our sample is
unlikely. A large deviation from stoichiometry seems
impossible for a compound having a low conductiv-
ity. Typically, for a stoichiometry of lo%, one would
expect both ionic and electronic conduction (via
polaronic hopping) and the ionic conductivity would
be similar to that reported in Ref. [6] for Gd doped
material. Assuming that the mechanism for generat-
ing electronic conductivity is associated with the
creation of vacancies and correlatively with the for-
mation of Ce3+ ions, a high electronic conductivity
is expected. For example, in CeO,,,, (40% of Ce3+),
the electronic conductivity is of 1 S . cm-’ at 600°C
[18]. As a further proof, the compound is yellowish
and does not change to a black coloration from 25 up
to 600°C this could mean that the content in Ce3+ is
nearly as small in BaCeO, as in non reduced CeO,.
In ceria, one must work with PO, = 10-l’ atm at
800°C to generate a concentration of vacancies x =
1O-4 [19]. At PO, = 1 atm by extrapolation of the
curve 800°C of Fig. 3 in [19], it should be x: = 10p5.
It can also be checked from [20] that the ionic
conductivity in ceria is quite large as soon as the
vacancy concentration reaches 5%. The conductivity
of our sample being very far from such values, we
believe that the concentration of Ce3+ is much
smaller than 1%. To end with, the ionic radius of
Ce3+ is about 1.034 instead of 0.80 for Ce4+ [26].
So, if the proportion of Ce3+ were lo%, the contrac-
tion of the crystallographic lattice would be about
5% and could be observed in XRD.
Previous measurements [21] undertaken on a simi-
lar ceramic also in ambient air had led to a much
higher conductivity. Such .a discrepancy suggested
that the ceramic is sensitive to the water content of
the ambient atmosphere and could be partially pro-
tonic conductor. This assumption was confirmed re-
cently by submitting undoped BaCeO, ceramics to
water at 600°C. The conductivity at 600°C of a water
treated sample is significantly increased (10m5 S .
cm-‘>. The thermal history of the sample also influ-
ences the conductivity. In order to clarify this point,
coupled in-situ Raman and impedance measurements
were performed.
4. Conductivity and structural changes as a func-
tion of the temperature
4.1. Thermal treatment at 600°C
Fig. 5 gives the resistance variation as a function
of the time when the sample is maintained at 600°C

(a) (b)

0 500000 1000000 1500000 1,l 1.15 1,2 1,25 1,3 1,35 1,4 1,45 I,5
1000/T (K)
Re(Z) (ohm)

Fig. 4. Evolution of impedance diagrams for the non-treated BaCeO, ceramic in the Nyquist representation in the 420-600°C temperature
range (a) and representation of the conductivity of the sample in the Arrhenius plot (b).
254 S. Loridant et al. /Solid
6 “‘C”‘b”‘I”,I”..
0 200 400 600 800
Time (min)
Fig. 5. Resistance versus time of BaCeO, at 600°C under air: (a)
and (b) are two of the Raman spectra recorded during a 16 h
period. The spectrmn (b), characteristic of the tetragonal phase,
has gained in intensity.
during 1000 min, in air. The resistance increases
rapidly until it tends towards 9.5 X lo5 n after 800
min. The same result was observed in argon and
nitrogen atmospheres. The Raman spectra recorded
at the beginning and at the end of the thermal
treatment are also reported on the figure. It is obvi-
ous that no band due to any other compound is
observed, in particular the weak band of unreacted
ceria does not evolute. On the other hand, the Raman
signal of BaCeO, is substantially improved after
such a treatment. The spectrum in Fig. 5b is much
more intense and shows that the tetragonal phase is
the dominant structure while the spectrum in Fig. 5a
cm-’
Fig. 6. Evolution of Raman spectra of the undoped BaCeO,
State Ionics 78 (1995) 249-258
is characteristic of a disordered phase which prefig-
ures the cubic structure.
The increase of R is not due to a decomposition
but to the ordering of the intermediate tetragonal
phase. The corresponding orthorhombic-tetragonal
structural transition was mentioned as taking place at
133°C in our previous work [14]. Surprisingly, it
seems to develop at a much higher temperature in
this study.
4.2. Thermal cycles between 20 and 600°C
1000 Fig. 4a and Fig. 6 report respectively the evolu-
tion of impedance diagrams and Raman spectra
recorded for a non-treated BaCeO, sample during a
thermal cycle causing to raise the temperature from
20 to 6OO”C, maintain the sample at 600°C for 1000
min and then return to 20°C. The conductivity (Fig.
4b) is represented by the Arrhenius plot. Two very
close values (E, = 1.0 eV and 1.06 eV) for the
corresponding activation energies can be derived
from the slopes in the 350-600°C temperature range.
Such high energies are usually rather associated with
ionic conductivity. Below 4OO”C, the conductivity
cannot be determined with a good accuracy (Fig. 4a).
As stated in Refs. [14-161, only relative motions
of 0 and Ce atoms can give rise to Raman active
modes. Recent normal mode calculations [24] have
shown that bands above 300 cm-i involve mainly 0
displacements while those taking place at low fre-
quencies are rather motions of octaedra as a whole.
For instance, the A, mode at 133 cm-’ is mainly a
cm-’
sample between 160°C and 260°C.
 S. Loridant et al. /Solid State Ionics 78 (1995) 249-258 255

plet and which cannot be viewed as an envelope of

0 200 400 600
Temperature (“C)
Fig. 7. Evolution of the frequency of some modes versus tempera-
ture in the 60-130 cm-’ frequency range. Bands (c) and (d) are
attributed to the tetragonal structure.
libration of octaedra around the b axis while that at
114 cm-’ of the B,, symmetry is a libration mode
around the a axis (axis of the orthorhombic Pmna
space group).
Fig. 6 shows that a clear modification of the
spectra takes place in a narrow temperature range
near 190°C. These spectral changes are associated to
the orthorhombic-quadratic modification, The multi-
plet at about 100 cm-’ gives rise to a single band,
the width of which is smaller than the initial multi-
this multiplet. The background (baseline) and the
Rayleigh intensity increase from 160 up to 210°C
and then recover their initial level. This is correlated
with the electrical noise observed in impedance mea-
surements in this temperature range (see further).
The evolution of some spectral parameters as a
function of temperature is presented in Figs. 7 and 8.
As expected from the anharmonicity phenomena, the
frequencies start to decrease when the temperature is
raised (Fig. 7). This behavior is interrupted for the
133 cm-’ (curve a) and the 110 cm-’ (curve b)
modes in the 220-280°C range if (a) is connected to
(c) and (b) to (d). On the other hand, it is possible to
consider that (d) is the continuation of (a) and that a
new mode (c) has appeared above 300°C. (c) appears
only as a weak shoulder and thus, its frequency is
not determined with a good accuracy. Recent normal
mode calculations [24] favor the first interpretation
consisting of making of (d) a librational mode of
octaedra similar in both orthorhombic and tetragonal
structures. However, whatever the interpretation is,
the most important conclusion is that anomalies in
the frequency variations are encountered in the 220-
300°C range. As already stated, the frequency pa-
rameter changes are rather representative of short
range order (SRO) structural modifications. Such a
modification which is likely characteristic of small
domains seems to be completed at about 300°C.

110
(a) (b)

5 10000
LI
g 8000
E
z 6ooo
E!
_ 4000

90 n
200 500 600 300 400 500 600 400 450 500 550 600
Temperature (“C) Temperature (“C) Temperature (“C)
Fig. 8. Temperaturedependence of frequency (a), intensity (b) and FWHM (c) of the 110 cm- band of the tetragonal structure (named (d)
in the discussion) during the thermal cycle.
256 S. Loridant et al. /Solid
Fig. 8a, b and c gives the temperature dependence
of the frequency, the intensity and FWHM respec-
tively for the band (d) in the 300-600°C temperature
range. This band (which likely corresponds to the
133 cm-’ mode measured at room temperature) is
chosen because it is particularly sensitive to struc-
tural changes. The intensity of this band (Fig. 8b)
starts to increase and reaches a maximum at 400 or
450°C depending on the thermal protocol. For a
given short range structural organization such as
octahedra, for instance, the intensity parameter varia-
tions are representative of the overall symmetry of
the crystal. It can thus be concluded that the tetrago-
nal domains grow between 300 and 450°C and that
the actual tetragonal phase exists only around this
last temperature. This phase is particularly well de-
veloped after a thermalization at 6OO”C, which should
favor the kinetics of long range ordering. This model
is confirmed by the FWHM evolution (Fig. 8~). The
reduction of FWHM takes place only when the
ordering is achieved. From these Raman measure-
ments, it can be concluded that 340°C marks the end
of the short range evolution (nucleation), while 450°C
is the average temperature for long range ordering
(growth process).
It must be emphasized that such a temperature
dependence of the integrated Raman intensity is
unusual since no marked effect of the temperature is
generally expected for a compound not undergoing a
phase transition. The same temperature dependence
has been observed for PbF, 1271. However, at the
difference of the barium cerate, the gain of intensity
of PbFZ when approaching the transition temperature
was accompanied by a broadening of the band and
thus the gain of intensity was interpreted as being
due to the appearance of k # 0 phonons induced by
disorder. In BaCeO,, the gain of intensity and reduc-
tion of halfwidth is fully interpreted in terms of
ordering of an intermediate phase.
Fig. 9 shows the variation of BaCeO, conductiv-
ity as a function of the integrated intensity parame-
ter. In the 450-600°C temperature range, the conduc-
tivity can be correlated to the intensity parameter
with a good accuracy. Thus, the long range ordering
responsible for the observed intensity variations in
the Raman spectra is responsible for the decrease of
the conductivity. The fact that the frequency (Fig.
8a) does not reveal the same sensitivity between 400
State Ionics 78 (199.5) 249-258
log(l(counts))
Fig. 9. Correlation between conductivity and Raman integrated
intensity of the 110 cm-’ band (d) in the 450-600°C temperature
range during the temperature decrease.
and 600°C means that the local structure does not
vary anymore and that the changes in the mobility of
the particles participating in the ionic conductivity in
this temperature range is determined only by the
long range structure changes. In any case, if oxygen
vacancies are generated when heating the compound,
their concentration is not high enough to influence
the local structure. Note that we assume that a small
concentration of vacancies is preexisting in order to
allow an oxygen mobility. Magnetic and optical
measurements are in progress in order to check if
these oxygen vacancies are associated with Ce4+
vacancies or if they imply the presence of reduced
Ce3+ ions. As far as electronic contribution is con-
cerned, it is interesting to recall the conclusions
obtained by Tuller and Novick [18] on non-stoichio-
metric CeO,_ X. The oxygen vacancies order and the
corresponding SRO persist above the temperature Ti
of the order-disorder transition. The rate of SRO
increases with x (the order-disorder transformation
takes place at 450°C for CeO,,,, ). This SRO should
be responsible for the high activation energy for
electrical conductivity via small polaron hopping.
The same interpretation can be proposed for BaCeO,:
the conductivity decrease which accompanies the
tetragonal structural change can be related to the
blocking effect of the vacancies ordering (it should
block both electronic hopping and oxygen ion mobil-
ity). When the compound is heated further, an or-
der-disorder transition (tetragonal -+ cubic) takes
place as for ceria.
 S. Loridant et al. /Solid State Ionics 78 (199.5) 249-258 257

0
100 200 300 400 500 600 0 loo 200 300 400 500
Temperature (“C)
T (“C)
Fig. 10. Evolution of the impedance fluctuations versus tempera- Fig. 11. Evolution of the resistance of the water treated sample as
ture. 6 is the standard error of Z determined from 20 measure-
a function of the temperature.
ments.

When random fluctuations take place, both give rise

The impedance fluctuations were studied as a
function of the temperature. Fig. 10 gives the stan-
dard error S of 2 (6= iARe( + Aim(Z)‘)
the 20-600°C temperature range. This parameter
gives an indication on the noise corresponding
these electrical signals. It is interesting to note that
this noise seems to be maximum in the 250-450°C
range. It could be related to the domain size fluctua-
tions which could take place during the growth
process. It is interesting to note that for conductivity
data, the probing particles are mobile charges mov-
ing in the lattice (a small fraction of the atoms) while
in Raman spectroscopy, the probing particles are
photons. Both are sensitive to structural fluctuations.
to noise (background, Rayleigh scattering in Raman).
When BaCeO, is water treated, a single circle is
in still sufficient to describe most of the impedance
measurements in the 100 Hz-40 MHz frequency
to range. However, it becomes possible to measure a
resistance already at room temperature (Fig. 11).
When the sample is heated in a closed cell, the
resistance increases up to 200°C likely because a part
of the incorporated protons are weakly bound water
molecules, for instance, at grain boudaries as sug-
gested in [25]. Above 200°C the resistance decreases
up to 2 X lo4 R at 600°C and seems to vary as a
thermally activated process. The charge carriers could
be then the remaining protons. The Raman spectra

;I
1100 1000 900 800 700 600 400 200 0
c m-’ cm-’

Fig. 12. Raman spectra in the 30-1100 cm-’ frequency range of 90% BaCeOs + 10% BaCO, (a); BaCeOs under f&O 6) and BaCeO,
under CO, (c). The 1060 cm-’ band allows to estimate the proportion (in weight) of carbonate in (b) and (C).
258 S. Loridant et al. /Solid
for the water treated sample vary exactly in the same
way as for the non-treated one. The only difference
is the presence of a very weak band at 1060 cm-’
attributed to the presence of about 1% (in weight) of
BaCO, (Fig. 12). It shows that the carbonation of the
compound is more favored by the water treatment
than by heating the sample between 25 and 600°C in
a pure CO, atmosphere.
5. Conclusions
Coupled impedance and Raman measurements
performed on undoped BaCeO, ceramic have al-
lowed to show that a large part of the variations of
the electrical resistance is due to the structural
changes induced by the temperature variation. Recip-
rocally, this coupled study contributes to the under-
standing of the orthorhombic-tetragonal phase tran-
sition mechanism. The resistance and the intensity of
the 133-110 cm-’ Raman band vary in the same
way when the temperature is raised or lowered be-
tween 400 and 600°C. The following interpretation is
proposed: the increase of the intensity is due to the
growth of ordered domains of the tetragonal phase,
correlatively this explains the increase of the resis-
tance. The kinetics of growth of these domains seems
to be favored at 600°C but their thermodynamic
stability should be maximum at about 450°C. Actu-
ally, as it can be deduced from the reduction of the
fullwidth of the Raman bands and from their inten-
sity the long range ordering takes place at about
450°C while the nucleation process would start at a
lower temperature. This process should start between
180 and 350°C and is characterized by the variation
of the frequencies of the modes at low energy.
Finally, the large fluctuations in the impedance mea-
surements which are observed between 250 and
450°C could be related to the fluctuation of the sizes
of the domains. In a future work, these fluctuations
will be reinvestigated and the influence of the atmo-
sphere will be precised.
Acknowledgements
We are thankful to Dr P. Maestro @h&e-Poulenc
company) for his support in this study. M. Bonnat is
State Ionics 78 (1995) 249-258
acknowledged for his help in the implementation of
the cell.
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