ARTICLE IN PRESS

Journal of Crystal Growth 266 (2004) 539–544

Shape-controlled synthesis and characterization of

BaZrO3 microcrystals
Zhouguang Lua,b, Yougen Tangb, Limiao Chena,b, Yadong Lia,*
a
Department of Chemistry, Key Laboratory of Atomic and Molecular Nanosciences (Ministry of Education, China),
Tsinghua University, Haidain District, Beijing 100084, PR China
b
Colleage of Chemistry and Chemical Engineering, Central South University, Changsha, Hunan 410083, PR China

Received 11 December 2003; accepted 18 February 2004

Communicated by M. Roth

Abstract

A facile modified hydrothermal approach has been exploited to rationally synthesize perovskite-structured BaZrO3
microcrystals with the shapes of truncated rhombic dodecahedron and sphere. The polarity variation by ethanol
introduction to the solutions plays a significant role in determining the geometric morphology of the final products. The
BaZrO3 microcrystals can serve as host materials for rare earth photoluminescence, and shape-dependent luminescence
properties of an Eu-doped material has been observed. Controlling the size and shape of perovskite oxides is of great
importance both in basic and applied science due to their strong structure-dependent physical properties.
r 2004 Elsevier B.V. All rights reserved.

PACS: 81.10; 81.20.K; 77.84; 61.10.Nz; 81.10.Aj; 78.55. Kz

Keywords: A1. Photoluminescence; A1. Shape control; A2. Hydro-thermal; B1. Barium Zirconate; B1. Perovskites; B1. Rare earth
compounds

1. Introduction polyhedrons [11], nanocubes [12], nanowires [12–

A wide range studies has been performed,
predominantly during the past decade, on per-
ovskite ceramics due to their excellent optical and
electrical properties and intrinsic capability of
hosting functional ions of various sizes [1–8].
Perovskite compounds with controllable and uni-
form size and shape, such as nanotubes [9,10],
*Corresponding author. Tel: +86-10-62772350; fax: +86-10-
62788765.
E-mail address: ydli@mail.tsinghua.edu.cn (Y. Li).
14], nanorods [15] and monodispersed nanoparti-
cles [16,17] have attracted vast attention due to
their unique size and shape dependent properties.
The family of complex ferroelectric oxides, such as
BaTiO3, Pb(Zr,Ti)O3 and BaZrO3, has far reach-
ing applications in the electronics industry as well
as a good substrate for the manufacturing of high
temperature superconductors [18]. To control the
morphology of oxides, a variety of aqueous and
gas phase reaction methods have been tried.
Here we describe a facile hydrothermal route to
the large-scale synthesis of ultrafine BaZrO3

0022-0248/$ - see front matter r 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jcrysgro.2004.02.107
 ARTICLE IN PRESS

540 Z. Lu et al. / Journal of Crystal Growth 266 (2004) 539–544

microcrystals with morphology of truncated
rhombic dodecahedron. More specifically, the size
and shape of the final products could be manipu-
lated with ease by programming the growth
parameters in the initial synthetic scheme, such
as reactant concentration, reaction duration and
solvent constitution. Since perovskite-type oxides
have also shown interesting results in use as host
materials for rare earth luminescence [19–23], these
microsize polyhedral crystals are functionalized by
introducing rare earth ions into the crystal lattice,
which endows the microcrystals luminescent prop-
erties and provides new opportunities for BaZrO3
ceramics applications.
final products was characterized with a Hitachi H-
800 transmission electron microscope (TEM)
operated at 200 kV and a scanning electron
microscope (SEM) equipped with the Strata
DB235 Focusing Ion Beam (FIB). The photo-
luminescence measurements were carried out using
a Hitachi F-4500 fluorescence spectrophotometer
employing Hamamatsu R928F photomulitplier as
the light detector, gratings with a groove density of
600 lines/mm and a 150 W Xe arc discharge lamp
as the excitation light source. The excitation
spectra were corrected for the beam intensity
variation in the Xe light-source used.

2. Experimental section 3. Results and discussion

2.1. Synthesis Fig. 1 represents the X-ray diffraction pattern of

All reagents were analytically pure and used
without further purification. The hydrothermal
reactions were carried out in a stainless-steel
autoclave with a Teflon liner (50 ml in total
capacity) under autogenous pressure. In a typical
procedure, a Ba(OH)2 solution was made in
distilled water, which was then mixed with
ZrOCl2
8H2O and KOH to obtain a slurry. The
slurry had the molar composition of
H2O:Ba:Zr=277:1.1:1 and the pH was controlled
above 13 by 0.5 M KOH solution. The slurry was
put into an autoclave, and the autoclave was filled
with deionized water up to 80% of the total
volume, sealed and heated at 130 C for one day.
After natural cooling, the product was filtered,
washed with dilute acetic acid and distilled water
an as-synthesized sample. All reflections can be
readily indexed to a phase-pure cubic perovskite
BaZrO3 with lattice constants a ¼ 4:18 A, ( compa-
tible with the literature value of a ¼ 4:1815
(JCPDS 741299).
Figs. 2a and b show typical scanning electron
microscope (SEM) images of the obtained pro-
duct. It is very remarkable that all particles are
uniform both in shape (rhombic dodecahedron)
and size (B2 mm in diameter, B1.5 mm in edge
length). In addition, every rhombodecahedron
particulate is composed of 12 well-defined crystal
1800
110
1600
1400

several times and dried at room temperature.

Intensity (a.u.)

1200
Trivalent rare earth ions (Eu3+ 1% in molar 1000
ratio) were introduced into the perovskite lattice 800
by adding Eu2O3 into the ZrOCl2
8H2O solution
600
at the early stages of precursor preparation.
400 200 211
220
200 111 013
2.2. Characterization 022
0

The phase purity of as-prepared products was 20 30 40 50 60 70 80

evaluated using a Bruker D8 advance X-ray 2θ (deg)

diffractometer with monochromatized CuKa ra- Fig. 1. Powder XRD pattern of BaZrO3 mocrocrystals
( The morphology of the
diation (l ¼ 1:5418 A). prepared hydrothermally at 130 C for 24 h in aqueous solution.
 ARTICLE IN PRESS
Z. Lu et al. / Journal of Crystal Growth 266 (2004) 539–544
Fig. 2. (a) Low- and (b) high-magnification SEM images of
slightly truncated rhombic dodecahedral BaZrO3 microcrystals.
The arrow shown in (b) is indication of truncated corners. (c) A
TEM image of the same batch of BaZrO3 microcrystals. (d)
Simulated morphology evolution processes of the three states of
regular rhombic dodecahedron, truncated dodecahedron and
sphere.
faces, which can be readily indexed to {1 1 0}
planes (Fig. 2d (1)). Furthermore, their surfaces
are smooth, and some particles appear to vary in
appearance only due to different projections. A
single crystallite has four three-fold axes and three
four-fold axes and exhibits cubic symmetry be-
longing to the m3m point group class [24]. It is also
clear from Fig. 2b that some corners and edges of
these micrododecahedrons, particularly those de-
noted by arrows, are weakly truncated. Fig. 2c
shows a representative transmission electron mi-
croscope (TEM) image of this sample. Generally,
most of the particles adopt a hexagonal shape, but
slight differences come forth after careful exam-
ination. One type of particle exhibits a hexagonal
shape with clear edges and corners, representing
the regular rhombic dodecahedral crystals. An-
other type exhibits a hexagonal appearance, but
with ambiguous corners, indicating that the
rhombic dodecahedrons are slightly truncated
and the encounter of {1 0 0} and {1 1 1} faces, in
agreement with the contrast analysis in Fig. 2b. In
the third distinct type of particles the dodecahe-
drons are so heavily truncated that a sphere shape
is formed preferentially. 3D images of these three
541
types of microcrystals are presented in Fig. 2d
(images 1, 2 and 3, respectively).
Subsequent studies suggest that the morphology
and size of the final products can be manipulated
by adopting certain reaction conditions, such as
growth time, reactant concentration and solvent
constitution. For instance, the critical reaction
temperature for pure phase BaZrO3 is 130 C, and
there is no discriminating shape- and size-distinc-
tion between the accessible temperature range of
130–180 C. An optimized concentration is found
to be about 0.03 M using [Zr4+] as a standard and
the ratio [Zr4+]:[Ba2+]=1:1.1. Within a certain
concentration range, the size of particles can be
regulated by adjusting the growth time. Figs. 3a,
2c and 3b show the products corresponding to
growth times of 12, 24 and 48 h, respectively. Their
size has increased from less than 1.5–2 mm, and
then to about 3 mm linearly. It is worth noting that
these samples appear hexagonal and are slightly
truncated. The distinct TEM profiles result merely
from their different supporting crystal faces on the
carbon grids used for TEM observation. However,
when half volume of water is replaced by ethanol
as the actual solvent, the morphology of the
product becomes a mixture of pseudo-spherical
and hexagonal shapes as exhibited in Fig. 3c. In
addition, the particle diameter somewhat de-
creases, indicating heavy truncating of the final
products. When the volume ratio of ethanol to
water increases from 1 to 3, the products evolve
fully into BaZrO3 microspheres with a mean
diameter of 3 mm. Based on the SEM and TEM
studies mentioned above, the morphology evolu-
tion is assumed to follow the sequence as shown in
Fig. 2d.
The results presented above clearly suggest that
it is possible to tune the size and shape of
BaZrO3 microcrystals by controlling the experi-
mental conditions. This is believed to be
closely related to the different surface energies
associated with different crystallographic planes of
polyhedral crystals with a general sequence
gf1 1 1g ogf1 0 0g ogf1 1 0g [25,26]. Weakly truncated
rhombic dodecahedron bound by the unstable
{1 1 0} planes is formed in purely aqueous solu-
tion. When ethanol with a lower polarity is
introduced, the selective polarity-impact on
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542 Z. Lu et al. / Journal of Crystal Growth 266 (2004) 539–544

dodecahedron bound by more stable {1 0 0} and

{1 1 1} planes. As the ratio of ethanol increases, a
highly stable spherical form becomes dominant.
However, when the initial concentration of Zr4+ is
reduced to 0.005 M or increased to 0.04 M, growth
of microcrystals tends to be irregular and they
agglomerate as shown in Figs. 3e and f, respec-
tively, which implies that nucleation and growth
are already not controlled kinetically.
Since perovskite-type oxides have shown inter-
esting results as host materials for rare earth
luminescence [19–23], we have applied a functio-
nalization approach to the BaZrO3 microcrystals
by a simple modification of the process. TEM/
SEM observations show that doping with Eu3+
does not change the bulk material characteristic
morphology. Fig. 4 presents the room temperature
photoluminescence (PL) excitation (a) and emis-
sion (b) spectra of the resulting phosphor with
spherical (green line), rhombic dodecahedral (red
line) and agglomerated (black line) shapes of the
microcrystals, respectively. The excitation spec-
trum exhibits a broad band centered at around
256 nm, which is attributed to charge transfer
between the Eu3+ cations and the surrounding
anions [27]. The emission spectrum line shape
exhibits transitions from the excited 5D0 state to
7
FJ (J ¼ 0; 1, 2, 3, 4) levels of the Eu3+ ion [28].
The most intense line at 608 nm is due to the

Fig. 3. TEM images of BaZrO3 microcrystals synthesized

under different conditions. (a and b) The same as in Fig. 2,
except that the growth time was shortened to 12 h and
prolonged to 48 h, respectively. (c and d) The same as in Fig.
2, except that half and three quarters volume ratio of water has
been replaced by ethanol used as solvent respectively. (e and f)
The same as in Fig. 2, except that the Zr4+ concentration has
been reduced to 0.005 M and increased to 0.04 M, respectively.

Fig. 4. Room temperature (a) excitation (lem ¼ 608 nm) and

various crystallographic facets of polyhedral BaZ- (b) emission (lex ¼ 256 nm) spectra of 1% Eu3+-doped BaZrO3
rO3 presumably greatly changes the crystal growth microcrystals with different shape (as denoted in inset by
orientation and thus results in heavily truncated different color).
 ARTICLE IN PRESS
Z. Lu et al. / Journal of Crystal Growth 266 (2004) 539–544
5
D0-7F2 transition, being expected from the
Judd-Ofelt selection rules [29,30]. In all three
samples the excitation and emission spectra are
similar in shape, and the bands differ only in their
intensities. Under identical measurement condi-
tions, the spherical particles comparatively have
the highest emission intensity, while the
agglomerated ones show the lowest intensity. It is
believed that the spherical morphology of micro-
crystals is required for both high-resolution screen-
ing and high-luminescence efficiency, because
phosphors with spherical morphology decrease
scattering of light from phosphor surfaces in
comparison with polyhedral particles [31,32].
In contrast, samples with aggregated microcrystal
morphology have more bulk defects, surface
cracks and inter-particle residual elastic
strains, which are detrimental to effective
emission and thus result in reduced luminescence
yield [32–34]. These observations clearly demon-
strate the shape dependent properties of these
BaZrO3 microcrystals.
4. Summary and conclusions
In summary, pure phase perovskite BaZrO3
microcrystals with controllable shape and size
have been synthesized at high yields via a modified
hydrothermal process. It has been found that
absolute aqueous solution favors the formation of
microcrystals with a rhombic dodecahedron shape.
By increasing the volume ratio of ethanol to water
in the solution, evolution of the morphology from
truncated dodecahedral to spherical can be in-
duced. Although much work remains to be done to
fully understand the fundamental basis of the
shape selectivity for this system, it is speculated
that the selective polarity-impact on various
crystallographic facets of polyhedral BaZrO3 are
crucial for the determination of the product
geometry. Shape dependent photoluminescence
has also been observed in these microcrystals,
which makes it clear that chemical synthesis of
perovskite oxides with well-controlled shapes, sizes
and structures is both scientifically and technolo-
gically important.
543
Acknowledgements
This work was supported by the NSFC
(20025102, 50028201, 20151001), the Foundation
for the Author of National Excellent Doctoral
Dissertation of P.R. China, and the State Key
Project of Fundamental Research for nanomater-
ials and nanostructures. The authors express their
thanks to Prof. Dong Qian and Dr. Hua Cheng
(Central South University) for their thoughtful
discussions.
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