Current Applied Physics 6S1 (2006) e266–e270

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Structure and electron charge-density analysis of nano-sized

BaTiO3 powder prepared by solvothermal method
Yong-Il Kim *, Kwon-Sang Ryu, Seung-Hoon Nahm, Jong-Seo Park
Korea Research Institute of Standards and Science, P.O. Box 102, Yuseong, Daejeon 305-600, Republic of Korea

Received 21 July 2005

Available online 9 March 2006

Abstract

The BaTiO3 powder with the average particle size of 20 nm were synthesized by a solvothermal method using Ba and Ti alkoxide
solutions as precursors. The structural parameters of BaTiO3 powder were successfully determined by the Rietveld refinement based
on the analysis of Raman spectra. The final weighted R-factor, Rwp, was 9.12% and the goodness-of-fit indicator, S (=Rwp/Re), was
1.28. The BaTiO3 powder consisted of cubic and tetragonal phases at room temperature. The weight fraction of cubic and tetragonal
phases based on the refined scale factors was 83.2% and 16.8%, respectively. The lattice parameters for cubic and tetragonal phases were
a (=b = c) = 4.0114(3) Å, and a (=b) = 3.9954(2) Å and c = 4.0327(2) Å, respectively. According to the analysis of the electron charge-
density distributions by maximum entropy method based on the observed structural factors to understand the chemical bonding nature
of BaTiO3 powder, the ferroelectric phase was stabilized by ionic and weak covalent bonding.
 2006 Elsevier B.V. All rights reserved.

PACS: 61.10.Nz; 77.84. s

Keywords: Nano BaTiO3 powder; Rietveld refinement; Maximum entropy method

1. Introduction It is well known that there are five crystal structures,

Since the ferroelectric behaviors of barium titanate
(BaTiO3) were reported in 1946 [1], BaTiO3 as an impor-
tant material has been widely used in the electronic indus-
try for various applications such as multilayer ceramic
capacitors, infrared detectors, piezoelectric transducers,
electro-optic devices, ferroelectric memories, etc. [2,3].
Nowadays the miniaturization and integration of micro-
electronics is requiring the reduction of the physical sizes of
BaTiO3 used as ferroelectric components. However, such a
requirement seems to have a significant effect on polariza-
tion of BaTiO3. Hence, the dependence of ferroelectric
properties on a crystallite size is of important and funda-
mental interest.
*
Corresponding author. Tel.: +82 42 868 5448; fax: +82 42 868 5032.
E-mail address: yikim@kriss.re.kr (Y.-I. Kim).
rhombohedral, orthorhombic, tetragonal, cubic and
hexagonal [4,5]. Of them the tetragonal phase exhibiting
ferroelectric properties is stable at and above room temper-
ature. However, as the crystallite size becomes finer, the
cubic phase which is non-polar and stable at above about
120 C may be existed at room temperature.
According to the Landau–Ginsburg–Devonshire (LGD)
theory for isolated particles [6], the structural change of
BaTiO3 from the tetragonal phase to the cubic one at room
temperature occurs in the range of a few nanometers to a
few tens of nanometers in diameter. The critical crystallite
size in the range from 10 to 200 nm were reported in previ-
ous reports and depended on the synthetic methods [7–9].
The BaTiO3 powder having the critical crystallite size at
room temperature may contain either tetragonal phase or a
mixture of tetragonal and cubic phases. It is essential to
establish a quantitative phase analysis of BaTiO3 powder
because material properties are strongly dependent on a

1567-1739/$ - see front matter  2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.cap.2006.01.053
 Y.-I. Kim et al. / Current Applied Physics 6S1 (2006) e266–e270 e267

phase (i.e. a portion of a system that is homogeneous in 3. Results and discussion

both of its physical and chemical properties). Likewise,
information regarding the crystal structure of nano-sized Fig. 1 shows the TEM micrographs of synthesized
BaTiO3 powder is fundamentally important in order to BaTiO3 powder with an average diameter of about
understand physical properties with respect to ferroelectric 20 nm. The selected-area electron diffraction (SAED) pat-
applications. Although the existence of cubic phase at tern (insert) consists of Debye-rings, showing that the poly-
room temperature has been reported previously [8–11], rel- crystalline phases exist. These rings might be indexed
atively little is known regarding the quantitative phase tetragonal or a mixture of tetragonal and cubic phases.
analysis and crystal structural refinement of nano-sized However, it is difficult to do the phase identification from
BaTiO3 powder [12]. In order to guess the ferroelectric the SEAD due to the small difference of lattice parameters
properties of BaTiO3 powder with the around critical sizes, between them.
it is necessary to determine the amount of phase quantita- The phase identification between the tetragonal and
tively and to get the structural information. cubic phases based on the X-ray diffraction histogram
In this work, we present a quantitative phase analysis of can be done in terms of the comparision of three peaks
nano-sized BaTiO3 powder by means of the Raman spec- at about 2h = 45 when CuKa radiations are used as char-
troscopy and the Rietveld refinement using X-ray powder acteristic X-ray sources: The two peaks, (0 2 0) and (0 0 2),
diffraction data. In order to understand chemical bonding of the tetragonal phase are clearly splitted if there is no
nature of nano-sized BaTiO3 powder, the electron charge- peak broadening due to the size effect of crystallite size,
density distributions were analyzed by maximum entropy while the (2 0 0) peak corresponding to cubic phase lies
method (MEM) based on the observed structural factors between these two peaks of tetragonal phase. However, if
obtained from the Rietveld refinement. the crystallite size of BaTiO3 powder decreases, the com-
pletely separated two peaks of tetragonal phase may be
2. Experimental appeared only one peak with a large full widths at half
maximum (FWHM) due to the peak broadening effects
The BaTiO3 powder samples were synthesized by the originating from the small crystallite size of BaTiO3. Hence
solvothermal method. Ba and Ti alkoxide precursor solu- it is very difficult to identify the phases of nano-sized
tions were prepared by dissolving the same molar amounts
of barium metal (Aldrich, 99%) and titanium isopropoxide
(Aldrich, 97%) in a mixed solvent of anhydrous benzene
(Aldrich, 99.8%) and anhydrous isopropanol (Aldrich,
99.5%). The precursors mixed with benzens at the ratio
of 0.5 mole were stirred with a magnetic stirrer for 3 h
and transferred into a stainless steel autoclave heated to
250 C for 72 h. After cooling down to room temperature,
the resultant precipitate was centrifuged and dried at 50 C
for 24 h in an oven. The final resultants were heated at
700 C for 3 h.
The primary particle sizes and morphology of BaTiO3
powder were investigated by a high resolution transmission
electron microscopy (TEM) (JEOL JEM-2010). The
Raman spectroscopy (Bruker RFS 100/S) with the
1064 nm lines of the exciting source from an Nd-YAG laser
were used to identify the phase.
The X-ray diffraction data were measured over the scat-
tering angle range 15 6 2h 6 130 at a 2h step of 0.01
using CuKa radiations with a graphite monochromator in
the reflection geometry at room temperature (Rigaku
Dmax2200V). The Rietveld refinement was made with
the RIETAN-2000 program [13].
The charge-density distribution of tetragonal phase in
BaTiO3 was analyzed by the maximum entropy method
(MEM) based on the observed structural factors derived
from the Rietveld refinement. The MEM analysis was
carried out in 64 · 64 · 64 pixels per lattice parameter by
Fig. 1. Transmission electron microscopy (TEM) micrographs of BaTiO3
a program package for electron density distribution powder synthesized by the solvothermal method showing the morphology
calculation by the maximum entropy method (MEED) and the selected-area electron diffraction (SAED) pattern (inset) of
[14,15]. BaTiO3 powder.
e268 Y.-I. Kim et al. / Current Applied Physics 6S1 (2006) e266–e270
BaTiO3 powder only by means of a search-match proce-
dure using the Joint Committee on Powder Diffraction
Standards (JCPDS) cards. Consequently, another
approach which is capable of doing the phase identification
for nano-sized BaTiO3 powder is required. The Raman
spectroscopy as a supplementary method in this study
was utilized for the phase identification of nano-sized
BaTiO3 powder.
Fig. 2 shows the Raman spectrum of BaTiO3 powder.
Among the Raman peaks, the peak around 304 cm 1 was
a typical peak representing the tetragonal BaTiO3 phase,
while the three broad peaks at about 258, 516 and
718 cm 1 were corresponded to the cubic BaTiO3 phase
[11,16–18]. The Raman results indicate that the BaTiO3
powder synthesized by the solvothermal method in this
study consist of a mixture of cubic and tetragonal phases.
The Rietveld refinement of BaTiO3 powder on the basis
of the Raman results was carried out. A mixture model of
tetragonal and cubic phases as an initial model was used on
condition that the synthesized BaTiO3 powder were stoi-
chiometrically composed of Ba, Ti and O. Each crystal
structural model was built with crystallographic data
reported by Harada et al. [19] and Buttner et al. [20],
respectively.
The preliminary Rietveld refinement began with a mix-
ture model of tetragonal and cubic phases. A Si (NIST
640c) powder as an external standard sample was used to
correct the zero-point shift for the measured diffraction
data. The initial Rietveld refinement cycles included the
zero-point shift, the unit-cell and background parameters
as variables. After a good match of peak positions was
achieved, the peak profile parameters including the peak
asymmetry were refined. No preferred orientation correc-
tion was applied. Even though the X-ray diffraction peaks
were broad due to the crystallite size effect of BaTiO3 pow-
der, the successful convergence of the Rietveld refinement
using a mixture model of tetragonal and cubic phases
Fig. 2. Raman spectrum of BaTiO3 powder at room temperature.
Fig. 3. Rietveld refinement patterns of BaTiO3 powder using X-ray
powder diffraction data for a mixture of tetragonal and cubic phases. Plus
(+) marks represent the observed intensities, and the solid line is
calculated ones. A difference (obs. cal.) plot is shown beneath. Tick
marks above the difference data indicate the reflection position. The upper
and lower tick marks above the difference data indicate the reflection
position for tetragonal and cubic phases, respectively.
was obtained as shown in Fig. 3. Of the converged reliabil-
ity-factors (R-factors), the final values of Rwp, Rp and S
(=Rwp/Re) converged to 9.12%, 6.81% and 1.28 respec-
tively, indicating a good fit to the experimental data. The
weight fraction of cubic and tetragonal phases based on
the refined scale factors was 83.2% and 16.8%, respectively.
Table 1 gives the refined structural parameters of BaTiO3
powder obtained from the Rietveld refinement. The lattice
parameters for cubic and tetragonal phases were a
(=b = c) = 4.0114(3) Å and a (=b) = 3.9954(2) Å and
c = 4.0327(2) Å, respectively.
Of the two phases, tetragonal and cubic, the tetragonal
phase is more interesting than cubic one because of the fer-
roelectric properties of tetragonal phase. Hence, the elec-
tron charge-density distributions using MEM method
were investigated only for the tetragonal phase. The
observed structural factors of 42 reflections derived from
the Rietveld refinement were used to perform the MEM
analysis as initial structural factors. The MEM analysis
was carried out in 64 · 64 · 64 pixels per tetragonal lattice.
In MEM analysis, the final converged reliability-factor, R,
was 1.78%, which was enough to determine the charge den-
sities of constituent atoms and their bonding nature. The
electron charge-density distributions of the (0 0 1), (2 0 0)
and (0 0 2) planes in the crystal structure of tetragonal
phase are shown in Fig. 4(b), (c) and (d), respectively. No
overlapping electron distributions were observed between
Ba–O bonding as shown in Fig. 4(b), indicating an ionic
bonding nature. On the other hand, the (2 0 0) and (0 0 2)
planes representing the electron charge-density distribu-
tions between Ti and O contour showed the electron over-
lapping between them. This means that weak covalent
bonding between Ti and O exists. The MEM results reveal
that the tetragonal phase of nano-sized BaTiO3 is stabilized
by ionic and weak covalent bonding.
 Y.-I. Kim et al. / Current Applied Physics 6S1 (2006) e266–e270 e269

Table 1
Refined structural parameters of BaTiO3 powder obtained from the Rietveld refinement using X-ray powder diffraction data at room temperature
Atom Site x y z g 100 * Uiso/Å2
Cubic phase
Ba 1a 0.0 0.0 0.0 1.0 1.40(2)
Ti 1b 0.5 0.5 0.5 1.0 1.08(1)
O 3c 0.0 0.5 0.5 1.0 0.11(3)
a = b = c = 4.0114(3) Å
a = b = c = 90

Tetragonal phase
Ba 1a 0.0 0.0 0.0 1.0 1.97(3)
Ti 1b 0.5 0.5 0.4651(2) 1.0 2.02(2)
O 1b 0.5 0.5 0.0078(3) 1.0 2.79(2)
O 2c 0.5 0.0 0.5240(5) 1.0 2.68(2)
a = b = 3.9954(2) Å
c = 4.0327(2) Å
a = b = c = 90

Phase fraction
Cubic 16.8(2)%
Tetragonal 83.2(2)%
The symbols, g and Uiso, represent the occupation factor and isotropic thermal parameter, respectively. The numbers in parentheses are the estimated
standard deviations of the last significant figure.

Fig. 4. Maximum entropy method (MEM) charge-density distributions of tetragonal phase in BaTiO3: (a) crystal structure, (b) (0 0 1), (c) (2 0 0) and (d)
(0 0 2) planes, respectively. The contour lines are drawn from 0.1 to 4.0 e/Å3 with 0.2 e/Å3 intervals.

4. Conclusion meters of nano-sized BaTiO3 powder synthesized by a

solvothermal method. The BaTiO3 powder with the
The combined approach based on the Raman analysis average crystallite size of about 20 nm was composed of
and the Rietveld refinement using X-ray powder diffraction a mixture of 83.2% cubic and 16.8% tetragonal phases.
data could be applied to get the crystal structural para- The lattice parameters for cubic and tetragonal phases were
e270 Y.-I. Kim et al. / Current Applied Physics 6S1 (2006) e266–e270
a (=b = c) = 4.0114(3) Å, and a (=b) = 3.9954(2) Å and
c = 4.0327(2) Å, respectively. The characteristic bonding
between constituent atoms in the tetragonal phase, ionic
(Ba–O) and weak covalent (Ti–O) bonding, was deter-
mined by the analysis of electron charge-density distribu-
tions obtained from the MEM/Rietveld method.
Acknowledgement
Authors acknowledge the Ministry of Science and Tech-
nology of Korea for financial support through Centre for
Nanoscale Mechatronics & Manufacturing.
References
[1] F. Jona, G. Shirane, Ferroelectric Crystal, Pergamon Press, Oxford,
1962, p. 108.
[2] G. Arlt, D. Henning, D. de With, J. Appl. Phys. 58 (1985) 1619.
[3] K. Knoshita, A. Yamaji, J. Appl. Phys. 47 (1976) 371.
[4] P.W. Forsbergh Jr., Phys. Rev. 76 (1949) 1187.
[5] G. Shirane, H. Danner, R. Pepinsky, Phys. Rev. 105 (1957) 856.
[6] J.F. Scott, H.M. Duiker, P.D. Beale, B. Pouligny, K. Dimmler,
M. Parris, D. Butler, S. Eaton, Physica B 150 (1988) 160.
[7] W.L. Zhong, Y.G. Wang, P.L. Zhang, B.D. Qu, Phys. Rev. B 50
(1994) 698.
[8] K. Uchino, E. Sadanaga, T. Hirose, J. Am. Ceram. Soc. 72 (1989)
1555.
[9] X. Li, W.-H. Shih, J. Am. Ceram. Soc. 80 (1997) 2844.
[10] F.S. Yen, H.I. Hasing, Y.H. Chang, Jpn. J. Appl. Phys. 34 (1995)
6149.
[11] R. Asiaie, W. Zhu, S.A. Akbar, P.K. Dutta, Chem. Mater. 8 (1996)
226.
[12] Y.-I. Kim, J.K. Jung, K.-S. Ryu, Mater. Res. Bull. 39 (2004) 1045.
[13] F. Izumi, T. Ikeda, Mater. Sci. Forum 321–324 (2000) 198.
[14] M. Sakata, R. Mori, S. Kumazawa, M. Takata, H. Toraya, J. Appl.
Cryst. 23 (1990) 526.
[15] S. Kumazawa, Y. Kubota, M. Takata, M. Sakata, J. Appl. Cryst. 26
(1993) 453.
[16] S. Tsunekawa, S. Ito, T. Mori, K. Ishikawa, Z.-Q. Li, Y. Kawazoe,
Phys. Rev. B 62 (2000) 3065.
[17] J. Javadpour, N.G. Eror, J. Am. Ceram. Soc. 71 (1988) 206.
[18] P.S. Dobal, A. Dixit, R.S. Katiyar, Z. Yu, R. Guo, A.S. Bhalla,
J. Appl. Phys. 89 (2001) 8085.
[19] R.H. Buttner, E.M. Maslen, Acta Cryst. B 48 (1992) 764.
[20] J. Harada, T. Pedersen, Z. Barnea, Acta Cryst. A 26 (1970) 336.