J Pkys. Ckcm Solids Vol59. No. 5. pp. 659-666.

1998
0 1998Elsevier Science Ltd
Pergamon PII: 50022~36!37@7)00227-8 hinted in Gnat Britain. All rights reserved
0022-3697r98 $19.00 + 0.00

STRUCTURAL EVOLUTION AND CHARACTERIZATION OF BaTi03

NANOPARTICLES SYNTHESIZED FROM POLYMERIC PRECURSOR

WOO-SEOK CH0-t
Takayanagi Particle Surface Project, ERATO, Japan Science and Technology Corporation& 3-l-2 Musashino. Akishima,
Tokyo 196, Japan

(Received 22 August 1997; accepted 14 October 1997)

Abstract-We synthesized barium titanate (BaTiOr) particles by heat-treating the polymeric precursors in air at
500-900C andproposed a model for the BaTiO) formation from the polymeric precursors. The model contained a
series of steps such as the transformation of the precursor to amorphous barium titanate, three-dimensional
nucleation and growth, and solid-state reaction. We investigated the crystal structure of the particles (20 nm in
size.), processed at 600C. using X-ray powder diffractometry (XRD) and Raman spectroscopy. The XRD
measurement indicated formation of cubic BaTiOr, and the Raman spectrum indicated that the particles of 20 nm
size might have had a tetragonrd symmetry. For the particles heated at 5OOC,XRD and Raman spectroscopy data
suggested the presence of a high-temperature hexagonal phase at room temperature. High-resolution transmission
electron microscopy indicated that the peaks that were ascribed to the above phase, in the Raman and XRD spectra,
may originate from (111) planar defects in the particles. 0 1998Elsevier Science Ltd. All rights reserved.

Keywords: A. ceramics, B. chemical synthesis, C. electron microscopy, D. defects, D. microstructure

1. INTRODUCTION properties of the powder may vary as different

preparation methods are used. The selection of the
Barium titanate (BaTiOs) with a perovskite structure has
preparation method is usually based upon the desired
been of practical interest for more than 40 years because
properties of the final material. The polymeric precursor
of its attractive electrical properties. The significance
method, in which a solution of ethylene glycol, citric
of this material is mainly due to the wide variety of
acid and metal ions is polymerized to form a polyester-
applications for which it is used, such as capacitors,
type resin, has recently received considerable attention
positive temperature coefficient thermistors, high-density
because of its simplicity. The metal ions can be
optical data storage, piezoelectric devices, and semi-
immobilized in a rigid polyester network, and therefore,
conductors [l-4]. The various applications have
the immobilization of the metal ions can greatly reduce
generated many scientific investigations aimed at
the segregation of a particular metal during the
preparing and characterizing the material. BaTi03
processing. Thus, this method has a distinct advantage
powders are usually prepared by conventional methods,
over most other methods, in that very pure mixed oxides
consisting of repeated ball-milling and solid-state
can be prepared [ 111. Further, powders with nanosizes
reaction of BaC03 and TiOr powders [5, 61. For most
make the BaTiOs system very attractive for developing
applications, the controlled preparation of high-purity
new ceramic devices, where the physical properties
BaTi03 powder is necessary to ensure its reproducible
depend on the particle size. For these reasons, knowledge
properties.
of the nucleation and growth is very important in order to
Recently, wet chemical techniques such as sol-gel [7],
control the particle size. Since fine particles of BaTiOs
coprecipitation [8], hydrothermal [9], and polymeric
are expected to form directly by thermal decomposition
precursor methods [lo] replaced the classical solid-state
of the precursors, where Ba and Ti are dispersed quasi-
reaction for the synthesis of BaTiOs. The advantage of
atomically, it is clear that the model of solid-state reaction
the wet chemical preparative techniques is the quasi-
between the particles of BaCOs and Ti02 does not
atomic dispersion of Ba and Ti in liquid precursors, which
describe the formation of BaTiOs from the polymeric
facilitates synthesis of the crystallized powder with
precursor systems. This is one of the subjects that we treat
nanosizes and high purity at low temperatures. The
in this study.
BaTiOs has several crystallographic modifications
tPresent address; Division of Ceramics, Korea Institute of [ 121. BaTi03 exists in a tetragonal ferroelectric phase,
Science and Technology, P.O. Box 131, Cheongryang, Seoul
with a high dielectric constant at room temperature, and
130-650, Korea.
$.Formerly the Research Development Corporation of Japan undergoes a phase transformation at approximately

659
660 WOO-SEOKCHO
12OC, when its structure becomes cubic. The cubic
structure of BaTiOs is stable up to 1460C. Above this
temperature, a hexagonal structure is stable. Interesting
results were reported on the crystal structure of BaTiOs
nanoparticles. One is that the phase transformation
of tetragonal to cubic BaTiOs occurs even at room
temperature as the size of crystals decreases. Another is
that the hexagonal phase exists at room temperature in
nanoparticles prepared from the polymeric precursors.
The presence of the cubic phase at room temperature
was studied extensiveiy [13-151, but there are still
considerable discrepancies in the reported boundary
size between the cubic and tetragonal phases.
Uchino er al. [13] discovered that cubic BaTiOs
particles, which were obtained from hydrothermal
solution systems, could be stable at room temperature if
the crystallite size was smaller than approximately 100 nm.
Yen et al. [ 151repted that the critical crystallite size for the
tetragonal-to-cubic phase transformation of BaTiOs nano-
particles was about 30 nm. This discrepancy may be due
to the misunderstanding of the structure of BaTi03
nanoparticles.
Difficulties were encountered in the techniques used to
analyse the phase, though the BaTiOs particles with such
nanosizes were investigated extensively by X-ray
powder diffraction and electron diffraction methods. In
general, line broadening in X-ray powder diffraction
measurements occurs in very small crystallites. Such a
phenomenon acts as an obstacle for the structural
characterization, particularly for BaTi03, which has a
small tetragonality (c/a is 1.011) [ 161. The value of the
lattice constant from electron diffraction can not be
accurately determined and is generally estimated with
0
an error of about 0.05 A. The intrinsic characteristic
may make the structural characterization difficult,
considering the lattice parameter of BaTi03 (a = 3.994 A,
c = 4.038 A).
In contrast with the extensive studies of the cubic-
tetragonal transformation at room temperature, only a
few investigations have been made on the stabilization of
the hexagonal BaTiOs at room temperature. Eror et al.
[ 171reported the presence of the hexagonal phase at room
temperature based on Raman spectra. In fact, Raman
spectroscopy in general has a better resolution than the
X-ray powder and electron diffraction methods and is
sensitive to the bond length and angle between cation and
anion. The diffraction and scattering methods yield
no topographic information, but high-resolution
transmission electron microscopy has demonstrated the
possibility of revealing the atomic details of structures
[ 181.The features mentioned above raise many questions
that must be answered to clarify the structure of BaTiO,
nanoparticles. For this reason, the structure of nano-
particles should be characterized using various analytical
techniques.
In this study, we report the phase and microstructure
evolutions of nanoparticles that were prepared from the
Ba-Ti metal polymeric precursor, through various
temperatures, to propose a model for the nucleation
and growth of BaTiOs from the polymeric precursor.
We then describe and discuss a series of experiments
designed to identify the crystal structure of the BaTiOs
nanoparticles.
2. EXPERIMENTAL PROCEDURE
2.1. Synthesis of BaTi powders from Ba-Ti
precursors
In our experiments, we dissolved BaCOs at 80C in a
titanium solution (Ba: Ti = 1:l) which we prepared by
dissolving titanium tetraisopropoxide (Ti[OCH(CHs)&)
into a solution of citric acid (I-IOOCCH,C(OH)
(COOH)CHZCOOH)and ethylene glycol @IOCH&I-120H),
mixed in a molar mtio of 1:4.We heated this solution at 90C
with a constant stirring rate of 200 rpm, until it became
transparent. We then heated this prepared pale-yellow
solution at 200C for 5 h to promote polymerization and
remove excess solvents. With continued heating at this
temperature, the solution became more viscous, with a
change in color from pale yellow to brown, but without
any visible formation of precipitation or turbidity, and
finally solidified into a dark-brown, glassy resin. Charring
the resin at 400C for 2 h in an electric furnace resulted in
a black solid mass, which was lightly ground into a
powder, using a Teflon rod. The powder obtained in
this way is referred to as the precursor. With
the furnace, we heat-treated the precursor at 500 to
900C in air, in an A1203 boat, and cooled it to room
temperature.
2.2. Characterization
We characterized the products by X-ray powder
diffraction and Raman scattering techniques to identify
the resultant phases. An X-ray powder diffractometer
(Model MXP3VA, MAC Science Co., Ltd., Tokyo, Japan)
was used with CuKcr radiation at 40 kV and 40 mA and
scan rates of 0.25 and 4/min from 15 to 90 28. We fitted
the X-ray diffraction peak profile (in this case, a scan rate
of 0.25/min was selected) with Lorentzian curves, after
the separation of CuKa, and CuKaz, to estimate their
exact half-value width. We excited the Raman spectra
with the 5 14.5-nm line of an Ar ion laser and measured
the spectra at room temperature in a backscattering
geometry, using microprobe optics (designed by Atago
Bussan Co., Ltd., Tokyo, Japan). We focused the laser
beam onto the sample surface with a 90 X objective lens
to a spot of several microns. We analysed the scattered
light using a Jobin Yvon/Atago Bussan T&t000 triple
spectrometer and collected it with a liquid-nitrogen-
cooled charge-coupled device (CCD) detector. The
 Structural evolution and characterization of BaTiOl nanopanicles 661

samples were dispersed in ethanol, placed on a microgrid,

and observed using high-resolution transmission electron

microscopy (HRTEM; JEM-20lOF, JEOL, Tokyo,
Japan) at 200 kV. Energy dispersive spectroscopy
(EDS) was applied in the electron microscope. X-ray
photoelectron spectroscopy (XPS; JPS9OOOMC, JEOL,
Tokyo, Japan, 10 kV, 10 mA) data were obtained using a
MgKo source. We deconvolved overlapping XPS peaks
using a computer routine.

3. RESULTS AND DISCUSSION

3.1. Structural evolution of BaTi particle

To understand the fundamental issues of BaTi03
crystallization, we heated the precursor at various
temperatures. Fig. 1 shows XRD patterns of three
samples obtained by heating the precursor in air at 500
to 900C for 8 h. We detected the first appearance of
BaTi03 in the sample heated at .500C (Fig. l(a)). Fig. 2. Representative HRTEM micrograph of the BaTiO?
particles processed at 600C.
However, we could not match the XRD pattern of the
sample with any of the known BaTiO, crystalline phases
with tetragonal [I61 or cubic structure [19]. Additional This particle size is well below the critical size of 30 nm
week peaks (indicated by *) always appeared around [ 151, at which the transformation from tetragonal to cubic
28 = 26 and 41, besides those of the main phase, which symmetry occurs at room temperature. According to the
was identified as one of tetragonal or cubic phases. In the previous studies [ 13- 151, the structure of BaTi may be
previous studies on BaTi03 synthesis from polymeric cubic at room temperature. However, it can not be
precursors, these peaks have been ascribed to an inter- concluded solely from the XRD result whether the
mediate phase [IO, 201. However, the additional peaks sample has a cubic symmetry or not, considering the
were consistent with those of the high-temperature line broadening in XRD measurements that is significant
hexagonal BaTi03 [21]. We identified this sample further for such nanoparticles. This could be confirmed using
in section 3.3. Raman spectroscopy. We described the characterization
The XRD results in Fig. l(b) indicate the dominant of the structure in Section 3.2.
formation of a cubic phase of BaTi03, when heated for The precursor completely transformed into tetragonal
8 h at 600C. We could not observe the peak separation of BaTi07 after 8 h at 9OOC, as indicated by the separated
200 and 002 around 20 = 45 in the XRD pattern. Particle 002 and 200 peaks in Fig. 1(c).
size of the powder was about 20 nm, as shown in Fig. 2. We investigated the microstructural development of
BaTiOl crystallites using HRTEM. The sample, fired for
8 h at 5OOC, tended to agglomerate when collected
onto a specimen grid for HRTEM observations
(Fig. 3(a)). Further investigation revealed that much of
the precursor was not yet transformed into free particles,
which may have been responsible for the agglomeration.
112 The HRTEM micrograph in Fig. 3(b) supports this
111 002 211
explanation. Fig. 3(b) also shows the initial crystalliza-
001 tion process of BaTiOl in an amorphous barium titanate
102 matrix, which was confirmed by EDS analysis. The
100 201 22%
amorphous state may have been responsible for a large
$1
-J. IL 210 L 12 decrease in XRD peak intensities (Fig. I(a)). Fig. 2
indicates the formation of well-defined BaTi03 particles
PI h i,h A-
of about 20-nm size, when heated for 8 h at 600C. From
(a) u * \ the above results, we can postulate that the formation of
20 40 60 the crystalline BaTiO? particles might be consistent with
28 (de@ Avrami-type nucleation and growth [22, 231: i.e.,
Fig. I. XRD patterns of powders obtained by heating the
particles continuously nucleated three-dimensionally in
precursor in air for 8 h at (a) 500C. (b) 600% and (c) 900C. the amorphous matrix as indicated by arrows in Fig. 3(a).
662 WOO-SEOK CHO

Fig. 3. (a) Representative HRTEM micrograph of the BaTjO

particles processed at 500C and (b) an enlarged electron
micrograph of the sample.

throughout the transformation, with the termination

caused by the impingement of adjacent particles growing
at a similar rate. An increase in the heat-treatment
temperature generates a grain growth by a conventional
solid-state reaction (Fig. 4(a) and 4(b)), where the driving
force is the decrease of total surface energies which
comes about grain contact and grain growth.
Hennings et al. [20] modeled BaTi03 formation from a
polymeric precursor by assuming a solid-state reaction
Fig. 4. Growth morphology of BaTiO, particles: (a) 8WC, and
between ultrafine particles of BaC03 and TiO*, although (b) 900C.
they did not show any evidence of the presence of isolated
BaC03 and TiOz. As shown in Fig. 3(b), the HRTEM Three-dimensional nucleation of crystalline barium
observatiqn exhibited a simple mixture of crystalline and titanate in the amorphous matrix.
amorphous barium titanate phases. This strongly suggests Crystal growth of BaTi from the randomly distrib-
that BaTi03 is not formed through a solid-state reaction uted nuclei.
between free BaC03 and TiOz ultrafine particles. Based Grain growth of BaTi03 by a solid-state reaction.
on the above results, we suggest that the following steps
In addition, the crystallization may start before the
represent the transformation to the crystalline BaTi03
complete transformation of the precursor into the
from the precursor:
amorphous barium titanate. However, this feature further
1. Transformation of the precursor to the amorphous complicates the model of the transformation process. In
barium titanate. the above discussion, therefore, we presented a simple
 Structural evolution and characterization
model based on the predominant reactions for the
formation of BaTi from the precursor.
3.2. Do BaTiOJ particles of about 20-nm size have
a cubic structure?
Half-value width (0.543 20) of the peak of 200 and 002
at about 45 20 is evidently broader than that (0.370 20)
of 111 at about 39 28, as shown in Fig. I(b). We also
confirmed that the half-value width of the peak at
about 45 20 was broader than (0.515 28) of 222 at
about 83 20. These results suggest that the crystal
structure of the BaTiOr might be basically tetragonal.
However, it is difficult to verify from the XRD result
whether the sample has a cubic structure or not, because
of the line broadening of XRD peaks, which is generally a
result of the combined effects of the crystallite size, non-
uniform strain, and instrumental broadening. Further-
more, the X-ray diffraction is not sensitive to the
structural change induced by the oxygen displacement
in BaTi03. Raman scattering has been utilized as a
powerful tool to investigate the tetragonal-cubic phase
transition [24-331. To characterize the subtle structure,
we collected Raman spectra at room temperature from
the samples which had been heat-treated at 600 and
9OOC.These samples showed Raman spectra similar to
those of the tetragonal BaTiOs (Fig. 5). Based on the
crystallography, Raman-active modes for tetragonal
BaTiOr (P4mm) are 4E(TO + LO) + 3A r(T0 + LO) +
1B,(TO + LO), while no Raman-active mode is predicted
for the cubic phase (P&m) [24, 251. However, many
investigators have observed Raman modes characteristic
of the P4mm point group above T, of about 130C
[26-331. With respect to these results, Noma et al. [34]
suggested that BaTiOj might undergo the phase
transition intrinsically, with an order-disorder behavior
and the well-known displacive behavior at 130C. We
could also find a change of the modes near T, in the
Raman spectroscopy studies. The intensity of the peak
around 303 cm- was assigned to the overlap of E(3TO)
+ E(2LO) + Br, which decreased with an increase of
temperature, and the mode disappeared above T,, where
200 400 600 800 1000
Reman sNft (cm-l)
Fig. 5. Raman spectra of the powders obtained by heating the
precursor at (a) 600C and (b) 900C.
of BaTiO, nanoparticles 663
the structure became cubic. Many researchers believe
that the Raman mode around 303 cm- is characteristic
of the tetragonal BaTi03 [34-361. The Raman peak
around 303 cm- (Fig. 5(a)) shows a large decrease in
intensity for the sample which was heat-treated at 600C
when compared with that (Fig. 5(b)), which was heat-
treated at 900C. This suggests that the tetragonal
structure may be slightly sustained in the sample heat-
treated at 600C. Thus, all the observed Raman peaks
could be assigned to the modes in tetragonal BaTi03.
Previous experiments on BaTiOs have shown that a
change in the transition from the tetragonal to the cubic
phase occurred with a decrease of crystallite size. Uchino
et al. [13] reported that BaTi03 revealed a drastic
decrease of the Curie temperature around a particle size
of 120 nm, and that the crystal symmetry was cubic even
at room temperature. Begg et al. [37] attempted to
determine the Curie point and transformation enthalpy
of BaTi03 as a function of tetragonality, using differential
scanning calorimetry (DSC). The DSC results appeared
to indicate a slight decrease in the Curie point, with
decreasing tetragonality, for powders with c/a > 1.008
at room temperature, while the average enthalpy of the
tetragonal-to-cubic transformation was observed to
drastically decrease with decreasing room-temperature
tetragonal distortion. However, the broadening and
intensity decrease of the DSC peaks for powders with
c/a < 1.008 at room temperature acted as an obstacle for
the correct analysis. Therefore, it was difficult to judge
from their DSC results whether the samples below c/a =
1.008 at room temperature showed the enthalpy of the
tetragonal-to-cubic transformation or not. We also
assumed that a sufficiently small crystallite size might
lead, thermodynamically, to disappearance of the
tetagonal structure. The high specific surface area of
very fine particles leads them to possess relatively large
amounts of excess surface energy per unit volume, when
compared to large single crystals. This excess surface
energy may contribute differentially to the relative free
energies of the tetragonal and cubic structures, and
possibly lead to room-temperature stabilization of the
cubic structure. In the previous studies, with the decreas-
ing particle size for BaTiOs powder, the subsequent
decrease in the tetragonality (c/a) at room temperature
and the Curie point may be interpreted in terms of the
surface energy mechanism. However, our observations
suggest that the BaTi03 particles of 20 nm in size may
have tetragonal structure.
3.3. Does hexagonal BaTi of high-temperature
phase exist at room temperature?
The Raman spectrum, with respect to the sample
prepared by heating the precursor at 500C is presented
in Fig. 6. It agrees with that reported by Eror et al. [ 171.
The spectrum was similar to that of the bulk tetragonal
664 WOO-SEOK CHO

details of the twin boundary structure are given in refs.

[38] and [39]. Based on the above results, we postulate
that the stacking sequence in the regions of the defects is
similar to that of the high-temperature hexagonal
BaTi03, thereby generating the satellite peaks similar
to those of the high-temperature hexagonal structure in
the XRD patterns and Raman spectra. A similar effect has
been observed for cubic &Sic, when the presence of
stacking faults resulted in additional peaks in XRD
55 200 400 600 800 1000 1200 pattern, where the positions approximated those of the
Raman shift (cm ) hexagonal phases of Sic [40].
The question remains as to why the planar defects are
Fig. 6. Raman spectrum of the powder obtained by heating the present only in the BaTi03 particles prepared from
precursor for 8 h at 500C.
organic precursors, while they have not been found in
BaTi03 reported in the literature [3 l-331, except for the BaTi03 prepared in air by other methods. We suppose
additional bands at 153,640 and 1059 cm-. The 153 and that the reducing conditions, induced- by the thermal
640 cm- Raman peaks were attributed to the strong decomposition of organic substances in the present
scattering from the high - temperature hexagonal case, may generate metal ions with lower oxidation
phase BaTi03 [17]. The bands at 1059 cm- and states. We performed XPS studies in order to observe
153 cm- were ascribed to BaC03 1171, which was the state of oxidation of metal ions in the sample. No
always formed along with the hexagonal phase. How- change in the state of oxidation was observed in the
ever, we investigated the structure in greater detail, with sample processed at 600C. In contrast, we have found a
some questions that must be answered to clarify the change in the state of oxidation of the Ti ions for the
existence of the hexagonal phase. The most fundamental, sample processed at 500C. Fig. 8 shows an XPS
from our point of view, are the following: spectrum of Ti(2pin, 3/z) for the BaTiO, samples
which we obtained by heating the polymeric precursors
1. What is the particle size of the high-temperature
at 500C. We found that the Ti (2~) binding energies
hexagonal BaTi03 at room temperature?
for the sample were 458.5 and 464.3 eV, which are
2. Why does this phase appear only in the BaTi03
consistent with those [41, 421 reported for Ti+4. The
powders prepared from organic precursors?
additional states (457.2 eV for 2pj12, 462.7 eV for 2p &,
In our HRTEM observations, we found no hexagonal at the lower energy side of each mode, correspond to Ti+3
particles, only tetragonal BaTi03 particles. Almost all [41, 421. The amount of Tif3 ions in the sample was
particles contained numerous (111) planar defects as about 40%. This result may be explained by charge
shown in Fig. 7. In the region indicated by white compensation for the oxygen deficiencies induced by
arrows, the interplanar spacings of 4.9 and 7.0 A the reducing conditions. BaC03 also might have
(corresponding to (01 i0) and (0002) respectively, segregated as a result of Ti and oxygen deficiencies.
which are characteristic of the high-temperature Considering these results, one may expect that the crystal
hexagonal BaTi03) were observed. chemistry of BaTi03 can be altered. The formation of
Another important feature is that the particles con- oxygen and/or barium vacancies must be accompanied by
tained (111) twins indicated by a black arrow. We also
noted the similarity between the interfacial structure of
the (111) twin and the hexagonal phase of BaTi03. The
Jx2Pu3
Q

t
s
1
d

470 465 460 455 450

Binding energy (eV)

Fig. 8. Ti (2p in, & XPS spectrum of BaTiOS powders obtained

Fig. 7. Lattice image of a BaTi particle. by heating the precursor for 8 h at 500C.
 Structural evolution and characterization
a change in the state of oxidation of the nearest-neighbor
Ti atoms from Ti+4 to Ti+3, in order to retain the local
charge balance. The above results suggest that the planar
defects can be formed due to the complex phenomena
associated with Ti+3 and oxygen and/or barium
vacancies.
Another question remains: when were the defects
introduced into the particle?. For such nanoparticles,
the defects are generally introduced during their growth.
However, the defect-formation behavior in the present
study appears to be different from that known previously.
XRD patterns of the precursor and the powder, calcined at
5OOC,are shown in Fig. 9 as a function of calcination
time. The precursor was amorphous in structure, as
shown by the broad continuum in the XRD in Fig. 9(a).
Crystallization has occurred during the heat treatment of
the precursor in air at 500C. Samples heated for 0 h at
500C (in this case, samples were cooled soon after
being heated to 500C) showed several broad XRD
peaks (Fig. 9(b)), which could not be satisfactorily
matched with any of the known crystalline phases in
the Ba-Ti-O-C-H system. The unknown phase always
formed before the formation of BaTi03. The amount of
the unknown phase first increased with treatment time,
then decreased as BaTiO3 appeared (Fig. 9(b-f)). Kumar
and Messing [43] identified the unknown phase as
BaZTi205C03. We questioned their identification,
where the valence of Ti were + 4. We have performed
XPS studies to observe the oxidation states of metal ions
in the sample obtained by heating the precursor for 2 h at
500C. Fig. 10 shows an XPS spectrum of Ti(2p i/~,3~) for
the sample. Ti(2p3n) binding energy for the sample was
found to be 457.5 eV and the full width at half maximum
l :BaTiO,
i indicate that the peaks in the XRD patterns and Raman
. obtained at 500C were consistent with the presence of
20 30 40 50 60
29 @leg)
Fig.9. XRD patterns of (a) precursorand powders obtained by
heatingthe precursorin air for(b) 0 h, (c) 2 h, (d) 8 h, (e) 12 h, (0
16 h, and (g) 24 h at 500C.
of @aTiOl nanoparticles 665
468 464 460 456 452 44
Binding energy (ev)
Fig. 10. Ti (2p,n, j/2) XPS spectrum of sample obtained by
heating the precursor for 2 h at 500C.
was 1.97 eV, which is consistent with those [41, 421
reported for Ti+. This suggests that only Tif3 ions may
be present as Ti species in the sample. The amount of
BaTi03 formation increased with a decrease in that of
Ti f3. The complete transformation of the precursor into
BaTi was finally achieved after 24 h (Fig. 9(g)), where
no Tif3 species was observed. In view of these results, a
new type of barium titanate, substituting Ti+3 for Ti+4
ions, should be considered as an intermediate phase. Our
X-ray diffraction and HRTEM results suggest that an
intermediate pase formed before the formation of BaTi03
and that these intermediates decreased with the
BaTi formation, but remained as defects in the
BaTi03 particles afterwards. The defects disappeared
with complete oxidation of Ti species from Ti+3 to
Ti+4, after the heat-treatment of 24 h at 500C.
A previous study [17] on the high-temperature
hexagonal BaTi03 particles at room temperature was
based on the assumption that the hexagonal phase was
stabilized by an increase in the surface energy, which is
significant for small particles. However, our observations
spectra, which were previously ascribed to the high-
temperature hexagonal phase, appear to be due to the
planar defects in the matrix with a tetragonal structure.
This is a more plausible explanation for the presence of
the satellite peaks.
4. CONCLUSIONS
We synthesized barium titanate (BaTi03) nanoparticles
by heat treating the polymeric precursors in air at 500 to
900C. XRD and Raman spectra of a BaTi03 powder
both tetragonal and hexagonal phases. However,
HRTEM observations did not show any hexagonal
particles. We found only tetragonal BaTi03 particles
containing numerous (111) planar defects. These defects
could generate the satellite peaks corresponding to the
666 WOO-SEOK CHO
high-temperature hexagonal structure in the XRD and
Ratnan spectra. We found Ti+ ions and suggested that
the crystal chemistry of BaTi03 could be altered to retain
the local charge balance. Thus, the presence of the defects
is accompanied by a change in the state of oxidation of
the Ti atoms.
The defect-formation behavior in the present study was
different from that known previously, where defects were
generally introduced during the growth of a particle.
X-ray diffraction and HRTBM studies indicated that an
intermediate phase, substituting Ti+ for TiG ions, formed
before the formation of BaTi03, and that these initially
formed intermediates decreased with the BaTiO, formation
but remained as defects in the BaTiO, particles afterwards.
We investigated the crystal structure of the particles
(20 nm in size) processed at 600C using XRD and
Raman spectroscopy. The XRD measurement indicated
formation of cubic BaTi03. However, we suggested that
the particles of 20 nm size may have a tetragonal
symmetry, based on observation of Raman spectroscopy.
BaTi formation in the present process is
summarized as follows:
1. Transformation of the precursor to amorphous barium
titanate.
2. Three-dimensional nucleation of crystalline barium
titanate, substituting Ti+ for Ti+4 ions as an
intermediate phase in the amorphous matrix.
3. Crystal growth of BaTi03 containing planar defects
from the randomly distributed nuclei.
4. Complete transformation into BaTiO.
5. Grain growth of BaTi by a solid-state reaction.
The previous studies for BaTi formation from a
polymeric precursor, which assumed a solid-state
reaction between ultrafine particles of BaC03 and TiOz
or Ba2Ti20sC03 as the intermediate phase, were not
appropriate.
Acknowledgements-The author is grateful for Professor K.
Takayanagi,the project leader of the Particle Surface Research
Project, for his kindness and generosity. The author would like to
thank Mr E. Hamada in the Research Project and Professor
Y. Gogotsi of the University of Illinois at Chicago for many
helpful discussions during the preparation of this paper. The
author wishes to express his thanks to Professor M. Yoshimura
and Professor M. Kakiiana, of the Tokyo Institute of
Technology, for making the X-ray diffraction and Raman
scattering equipments accessible. The author also extends his
thanks to Dr Y. Iijima, of JEOL Ltd., for assistance with X-ray
photoelectron spectroscopy.
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