Available online at ScienceDirect

ScienceDirect
J. Mater. Sci. Technol., 2014, -(-), 1e6

Growth Mechanism, Modified Morphology and Optical Properties

of Coral-like BaTiO3 Architecture through CTAB Assisted Synthesis
Pengjun Zhao1,2), Lei Wang1), Liang Bian1)**, Jinbao Xu1)*, Aimin Chang1), Xinqian Xiong1,2),
Fanglong Xu1,2), Jiaqi Zhang1,2)
1) Key Laboratory of Functional Materials and Devices for Special Environments of CAS, Xinjiang Key Laboratory of Electronic
Information Materials and Devices, Xinjiang Technical Institute of Physics & Chemistry of CAS, Urumqi 830011, China
2) University of Chinese Academy of Sciences, Beijing 100049, China
[Manuscript received September 21, 2013, in revised form December 4, 2013, Available online xxx]

Three-dimensional hierarchical structure coral-like BaTiO3 nanoparticles have been self-assembled by a facile one
step hydrothermal method. Cetyltrimethyl ammonium bromide (CTAB), Ba(OH)2$8H2O and tetrabutyl titanate
have been used as precursors. The prepared BaTiO3 exhibits cubic perovskite phase at room temperature, and
the coral-like architecture is a micro-nano hiberarchy consisted of dendrimer-like structure and trunk-like
structure. By adjusting the hydrothermal duration and the precursor substances, a surfactant induced
mechanism is proposed to understand the self-assembly process. UV-vis measurement demonstrates that the
as-prepared BaTiO3 nanoparticles exhibit dozens of times overwhelming absorptive character compared to the
ordinary nanospheres at ultraviolet band, which is benefited from the coral-like porous framework. Moreover,
halogen anions( F
, Cl
, Br
, and I
) have been chosen to adjust the coral-like BaTiO3 physical properties.
Results show the halogen doping produces distinct modulation effect on the grain size, UV-vis absorbance
and photoluminescence properties of the materials. The coral-like BaTiO3 nanoparticle and its halogen
modified ramifications offer significant opportunities to develop nano-laser devices, photon detectors,
photocatalyst based on BaTiO3 perovskite materials.

KEY WORDS: BaTiO3; Halogen doping; Hydrothermal synthesis; Coral-like; Cetyltrimethyl ammonium bromide (CTAB); Optical properties

1. Introduction or perovskite, the research on their nanostructure is really

Synthesis of nanocrystals with distinctive architecture has
been an important branch of nanotechnology since extraordinary
morphology in nanoscale would lead to a remarkable physical as
well as chemical performance[1,2]. For instance, the catalytic
property of nano-catalyst greatly depends on its exposed crys-
tallographic plane[3e6], and nanocrystals with a larger length-
diameter ratio are usually with better ability to transmit the
holeeelectron paris[7e9]. During the past few years, various
types of monometal oxide nanocrystal materials (TiO2, ZnO,
SnO2, MnO2) have been prepared by either physical or chemical
techniques, such as nanorods, nanoflowers, nanoneedles, and so
on[10e15]. However, for compound metal oxidate, such as spinel
*
Corresponding author. Prof., Ph.D.; Tel.: þ86 15099668125
**
Corresponding author. Ph.D.; Tel.: þ86 18309912357; E-mail
addresses: bianliang@ms.xjb.ac.cn (L. Bian), Xujb@ms.xjb.ac.cn (J. Xu).
1005-0302/$ e see front matter Copyright Ó 2014, The editorial office of
Journal of Materials Science & Technology. Published by Elsevier
Limited. All rights reserved.
http://dx.doi.org/10.1016/j.jmst.2014.04.002
insufficient[16,17].
BaTiO3 is of valuable traditional technological importance
owing to its high dielectric constant and ferroelectric
response[18e21]. Recently, the scope of the application of BaTiO3
materials has been expanded with the development of modern
nanotechnology, and the topic of design and synthesis of BaTiO3
in micro-nano scale is considered indispensable to the high
integration electronics and electrical engineering because of the
size effect. For instance, the piezoelectricity will enhance 20%
and 500% when the BaTiO3 size decreases to 8 mm and 5 nm,
respectively compared to the bulk materials[22].
BaTiO3 as a new kind of supercapacitor and nanogenerator
has been reported based on BaTiO3 nanotubes[23e25].
The micro-nano hierarchical structure materials, which are a
kind of micro-scale nanoparticle composed of nanoscale sub-
structures, exhibit many particularly excellent performance, such
as super-hydrophobic properties, electrochemically catalytic ac-
tivity, antireflective properties, gas sensing performance, etc.,
due to their unique multiscale structure effects[26e28].
However, present manuscripts are mainly focused on the single
nano structures such as the nanospheres, nanotubes, nanobelts

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2 P. Zhao et al.: J. Mater. Sci. Technol., 2014,
Fig. 1 FESEM images (aec) and XRD patterns (d) of the undoped coral-like BaTiO3 nanoparticles.
and so on[29,30]. A few papers have been reported in the object of
BaTiO3 particles with complex micro-nano hierarchical structure.
In this work, coralline-like nanocrystals of BaTiO3 have been
successfully developed through a facile one step hydrothermal
approach under the assistance of cetyltrimethyl ammonium
bromide (CTAB). Formation mechanism of BaTiO3 nanocoral
structures was proposed. Halogen anions effects on structural
and optical characteristics of the original coral-like BaTiO3
material were discussed.
2. Experimental
All the reaction agents were analytically pure and purchased
from Aladdin, Shanghai. In a typical synthesis procedure of
BaTiO3, 35 ml deionized water was heated to boiling to remove
the soluble carbon dioxide. Next, 0.1 g CTAB was added to the
pretreated deionized water. After magnetic stirring for 10 min, the
homogeneous solution was obtained. Then, 2 g Ba(OH)2$8H2O
(6 mmol) was dissolved into the above solution. Afterward, 2 ml
tetrabutyl titanate was dispersed by vigorous stirring for 10 min
and then transferred into a 50 ml Teflon-lined stainless-steel
autoclave. The autoclave was heated in an oven at 180  C for
12 h. After the reaction was completed, the sealed autoclave was
cooled in the air. The resulting products were washed sequentially
with ethanol, and distilled water for several times. Finally, the
final product was dried under vacuum at 50  C overnight for
further characterization.
For the halogen modified samples, KF, KCl, KBr and KI with
a 20% molar ratio of tetrabutyl titanate was dissolved into the
precursor solution, and the other experimental parameters
remained constant.
The phase composition of the samples was determined on an
X-ray diffractometer (Bruker D8-Advance, Germany) with
CuKa radiation (l ¼ 0.15406 nm). The morphology of the
prepared samples was investigated by field-emitting scanning
electron microscopy (FESEM, ZEISS SUPRA55VP, Germany).
Elements contents were measured through the Oxford in-
struments energy dispersive spectrometer (EDS). Absorption
properties of the products were recorded by UV-vis spectra
Please cite this article in press as: P. Zhao, et al., Journal of Materials Science & Technology (2014), http://dx.doi.org/10.1016/j.jmst.2014.04.002
-(-), 1e6
(Shimadzu UV-3600 spectrometer, Japan). Photoluminescence
(PL) spectra were taken at room temperature with a fluorescence
spectrophotometer (Hitachi F-7000, Japan) conventional photon
counting system with 325.0 nm exciting. Before UV-vis and PL
measurements, the products were washed with 0.1 mol/l formic
acid and ethanol.
3. Results and Discussion
3.1. Structure and morphology of coral-like BaTiO3
nanocrystalline
The FESEM images and X-ray diffraction (XRD) patterns of
the BaTiO3 nanocrystals obtained by one step hydrothermal
method are shown in Fig. 1. Main phase of the as-obtained
product can be well indexed to the cubic phase of BaTiO3
(JCPDS No. 89-2475). Besides BaTiO3, there is a little BaCO3
presented in the diffraction pattern, which could be easily elimi-
nated through washing the powders with diluted hydrochloric
acid[31]. No other visible peaks for impurities were detected.
A low-magnification FESEM image reveals that the nano-
particle has a homogeneous coral-like architecture, as shown in
Fig. 1(a). As can be seen from the image shown in Fig. 1(b) and
(c), each cluster of coral-like BaTiO3 nano architecture shows
numerous dendrimer-like and trunk-like substructures. The
dendrimer-like structure, grown on the trunk-like structure, is with
a length of about 200 nm and a diameter of 70 nm. For another, the
length of the trunk structure is about 1 mm, and its diameter is
70 nm. The sundry fractal structures have been demonstrated to be
with potential applications on luminous absorption, catalysis,
enhancing fluorescence effect and so on[32e35].
3.2. Formation mechanism of the coral-like BaTiO3
To investigate the growth mechanism, a series of experiments
were performed by adjusting the hydrothermal reaction time.
Fig. 2 shows the typical morphology of products obtained by
treating the precursor solution at different stages.
 P. Zhao et al.: J. Mater. Sci. Technol., 2014,
Fig. 2 FESEM images of undoped BaTiO3 obtained from various hydrothermal treatment time: (a) 3 h, (b) 6 h, (c) 9 h, (d) 15 h.
Products at the preliminary synthetic stage (Fig. 2(a)) are
nanospheres displaying aggregation. As the time for hydrother-
mal reaction increasing, “trunk” section of the fasciphyllum
mentioned above appears, and their length as well as the di-
ameters is already similar to that of 12 h. Yet, only a few of the
dendrimer-like sections grow on the trunk, and their size is far
from being enough. Unreacted solid precursors were observed in
the background of both Fig. 2(a) and (b), indicating incomplete
deposition of the generated BaTiO3 particles. Directly after the
hydrothermal time for 9 h (Fig. 2(c)), short “dendrimer”
germinated on the surface of the central trunk, and the un-
precipitated particles are rare. Concomitantly, for this synthesis
time reaches 12 h, slinky coral-like BaTiO3 barium titanate
particles are formed (see Fig. 1(c)). However, it seems that the
coral-like skeleton structure collapses when the retention time
extends to 15 h (Fig. 2(d)). The possible reason is that the
transformation is a coarsening process induced by Ostwald
ripening (OR) process[36,37] for extreme long time hydrothermal
treatment: there was large distribution of sectional radius for the
coral-like BaTiO3 particles, leading substance of the relatively
slender position to dissolve and then re-precipitate on surfaces of
the coarser parts.
Product prepared without addition of CTAB is shown in
Fig. 3(a). Only near-spherical nanoparticle with the diameter of
w30 nm was found. Thus, the CTAB might act as a kind of
morphology control agent during the crystalline process of the
coral-like BaTiO3.
On the basis of investigations on the products presented
above, a surfactant induced growth mechanism is proposed, as
shown in Fig. 3(b). The synthesis of nanostructured coral-like
BaTiO3 involves several main steps. At the preliminary stage
of the synthetic process, Ba2þ, CTAB, and Ti(H2O)64þ hydro-
lyzed from tetrabutyl titanate coexist under aqueous alkaline
conditions. As the temperature increases and time grows,
Ti(H2O)64þ and Ba2þ generate crystalline state BaTiO3 spheres.
Numerous earlier literature have tested and verified that BaTiO3
could be capable of crystallizing at 150  C even less than 3 h
under the absence of Ba(OH)2 and tetrabutyl titanate[38e40].
Because of the two following reasons, CTAB molecules adhere
Please cite this article in press as: P. Zhao, et al., Journal of Materials Science & Technology (2014), http://dx.doi.org/10.1016/j.jmst.2014.04.002
-(-), 1e6 3
to surfaces of BaTiO3 spheres in preparation for the next self-
assembly stage. First, the surface of BaTiO3 spheres is hydro-
philic due to functionalization with eOH groups. Functional e
OH groups are able to incorporate hydrophobic groups on CTAB
through coordination interaction[41]; Second, the high surface
energy of the new nucleated BaTiO3 makes it effortless to absorb
substance such as CTAB molecules.
Concentration of CTAB in the reaction solution is 54 mmol/l,
which is much larger than its second critical micelle concentra-
tion (CMC-2). Surfactant molecules are tending to assemble into
tubular-like micelle[42], leading to the formation of CTAþe
BaTiO3eCTAþ stacked structures. From the foregoing discus-
sion, nucleated BaTiO3 spheres are assembled to quasi-one-
dimensional structure under the assistance of CTAB. Thus, the
central trunk structure is formed.
Along with the growth of the trunk, a mass of inevitable lattice
defects generate on its external surface. Afterwards, dissociative
CTAþeBaTiO3eCTAþ bilayer precipitates on the defect sites to
grow along other directions, generating the dendrimer-like sec-
tion. After all the prodromic BaTiO3 substance has rolled up into
the “coral reef”, finally products with coral-like porous structure
were fabricated.
3.3. Optical properties
Room temperature UV-vis absorption spectrum of coral-like
BaTiO3 nanoparticles in the range of 300e450 nm is shown in
the top curve of Fig. 4. The band gap energy of synthesized
sample can be calculated from the optical absorption edge onset
(l) using band gap energy relation of E (eV) ¼ 1240/l (nm),
where l is absorption edge and E is band gap energy of synthe-
sized sample. Optical band gap of the sample is 3.32 eV. However,
for some specific optoelectronic applications, the band gap of the
materials should be controlled or modulated at a precise range.
Hence, we introduced halogen anions to the coral-like BaTiO3
architecture to modulate the matrix’s energy band structure, op-
tical absorption properties and some other physical properties.
In the measured range, all the products exhibit a broad
absorption band around 300e400 nm. Nevertheless, there is a
4 P. Zhao et al.: J. Mater. Sci. Technol., 2014,
Fig. 3 (a) FESEM image of BaTiO3 nanoparticles without CTAB, (b) the schematic representation of the proposed mechanism for the synthesis of
coral-like BaTiO3.
considerable difference among their respective absorption in-
tensity. All the coral-like BaTiO3 nanoparticles exhibit several
times extremely stronger absorption than the BaTiO3 nano-
spheres. Among them, undoped coral-like BaTiO3 sample shows
the strongest uptake intensity. The strong absorption band for
undoped BaTiO3 particles arises from the idiosyncratic coral-like
morphology. Stacking of the dendritic structure powders leads to
a porous skeleton. This framework provides favorable scattering
circumstance, and the optical distance can be prolongated to a
great extent, resulting in the enhancement of absorption intensity.
For the doped samples, their order from strong to weak is:
Cl
> Br
> F
> I
. The reason lies in the particle sizes and
the crystal structure of the respective modified nanoparticles.
Fig. 5 demonstrates the transformation of sizes and appear-
ance for the halogen doped BaTiO3 particles. All of the four
samples’ sizes are smaller than the undoped product. From
Fig. 5(b)e(d), it could be concluded that the decrease in the
particle size is caused by fracturing of the coral-like backbone
(the circle in Fig. 5(b)). That is because the increase of impurities
radius level accompanied with the increase in number of lattice
defects in the BaTiO3 matrix, which increased the lattice strain
and disturbed the crystallites’ regular growth process[43].
Particularly, F
ion has the minimum radius among halogen
ions, however, particle size in Fig. 5(a) is tinier than the Cl

doped ones, and comparable as the Br
doped sample. This
phenomenon might be related to different doping types for hal-
ogens. The phase structures of the samples provide indirect proof
to support this inference.
Fig. 4 UV-vis absorption spectrum of the as-prepared BaTiO3 and the
halogen modified nanoparticles.
Please cite this article in press as: P. Zhao, et al., Journal of Materials Science & Technology (2014), http://dx.doi.org/10.1016/j.jmst.2014.04.002
-(-), 1e6
Fig. 6 displays XRD patterns of the products doped by F
,
Cl
, Br
and I
. Similar to the undoped coral-like BaTiO3, the
main features of halogen doped BaTiO3 diffraction peaks are
consistent with the standard pattern of JCPDS 89-2475
(BaTiO3), and trace quantity of BaCO3 phase. No other impurity
phases can be seen in the XRD patterns, indicating that the
halogen atoms have been dispersed into the crystal lattice of
BaTiO3. As a rule, the existence of impurity atom causes lattice
distortion and induces the shift of peak positions in XRD pat-
terns. In order to inspect the diffraction peak shifts caused by the
halogen doping, (320) diffraction peaks located in the high angle
are shown in Fig. 6(b). It is worth noting that all of the four peaks
shift toward lower angles compared to the undoped sample. The
shift extent is F
> I
> Br
> Cl
. One possible reason is that
there are two different doping types for halogens: Cl
, Br
and
I
ions belong to substitution doping, while the F
ion belongs
to interstitial doping. Ionic radius of the Cl
, Br
and I
is larger
than that of O2
, while that of F
is smaller. According to the
classical Bragg equation, when bigger atoms (Cl
, Br
and I
)
substitute for smaller ones (O2
), the host lattice expands, and
the main diffraction peak shifts toward lower angles. What’s
more, there is a positive correlation between the shift extents and
ionic radius difference, which is indicated by the diffraction peak
positions of Cl
, Br
and I
doped samples.
Abnormal shift of F
manifests that the doping type might be
interstitial doping. When the O2
ion is substituted with the
smaller F
ions, shrinking of the host lattice can be induced,
whereas F
ions occupying interstitial sites, leading to the
expansion of the host lattice. In detail, the semi-quantitative
analysis of the respective elements contents can be obtained
from the EDS (Table 1). Normalized percentages for F, Cl, Br
and I are 3.00, 0.18, 0.16 and 0.26. It is shown that the content of
F atoms is much higher than that of the other halogen atoms,
which is account for the largest shift of the F
doped sample.
What’s more, the absorption edges of the halogen modified
samples exhibit the significant red shift which approaches the
visible light region. The calculated bands value is 3.32 eV for
raw coral-like BaTiO3, 3.28 eV for Cl doped BaTiO3, 3.34 eV
for F doped sample, 3.22 eV for Br doped product, and 3.18 eV
for I doped particles, respectively. Similar to some other anion
doped modification[44,45], hybridized orbitals consist of O 2p and
halogen ions’ 2p orbitals are able to shift the top of the valence
band to negative orientation, while without affecting the poten-
tial of the conduction band. The result shows that a smaller band
gap for the doping metal oxides forms. Furthermore, halogen
doping is capable of diminishing the recombination process of
 P. Zhao et al.: J. Mater. Sci. Technol., 2014, -(-), 1e6 5

Fig. 5 FESEM images of the halogen doped coral-like BaTiO3 nanoparticles: (a) F
doped, (b) Cl
doped, (c) Br
doped, (d) I
doped.

holeeelectron pairs by prolonging electron lifetime and lowering
recombination resistance of the semiconductor devices[46,47].
In addition, we found that the halogen modification is able to
enhance the visible emission intensity of the matrix, making this
low-cost BaTiO3 micro-nano hierarchical nanoparticles be able
to replace single crystal semiconductors in various optoelec-
tronic devices. As it is presented in Fig. 7, the PL spectra were
used to investigate the intermediate degree of the ordered-
disordered structure and determine energy levels within band
gap. Both of the undoped coral-like BaTiO3 sample and halogen
modified nanoparticles exhibit broaden emission profile bands
between 510 and 580 nm, corresponding to the green-yellow
light range. Moreover, all the emission peaks are around
525 nm. This mutual emission band can be ascribed to electrone
hole recombination of localized exciton oxygen vacancies,
because there are abundant surface defects in the hydrothermal
method samples[48]. However, significant enhancement was
detected from the halogen modified samples. The intensity is
increased about two times compared to the original coral-like
BaTiO3 nanoparticles. There are two possible main accounts
which can explain the potentiation. As was stated above, PL
emission profile bands reflect the disorder degree of the TieO
octahedron in the BaTiO3 crystal lattice. The mix of halogen
atoms aggravates this disorder degree, thus enhances the emis-
sion intensity. Meanwhile, the size effect also acts as an
important factor for the enhancement, and the PL yield decreases
as the nanocrystal size increases, especially for the quantum dots
system[49]. Reduction of particle size for halogen modified par-
ticles has been demonstrated from Fig. 5.

4. Conclusion

We developed a facile one step hydrothermal method to pre-

pare the novel micro-nano hierarchical coral-like BaTiO3 nano-
particles with the cubic perovskite phase. The obtained
distinctive coral-like particle is composed of two sections:
dendrimer-like structure with a length of about 200 nm and
trunk-like structure with a length of 1 mm, and both of their

Table 1 Elements content of the samples determined by EDS (at.%)

BTO-F BTO-Cl BTO-Br BTO-I

Barium 15.46 15.03 16.96 14.79

Oxygen 67.20 68.99 63.06 67.62
Fig. 6 (a) XRD patterns of the halogen doped coral-like BaTiO3 par- Titanium 14.34 15.80 19.82 17.34
ticles, (b) shifts of (320) diffraction peak caused by halogen Halogen 3.00 0.18 0.16 0.26
doping.

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6 P. Zhao et al.: J. Mater. Sci. Technol., 2014,
Fig. 7 Photoluminescence spectrum of the as-prepared BaTiO3 and the
halogen modified nanoparticles (UD ¼ undoped).
diameters are 70 nm. CTAB plays a key role in the formation of
the final morphology. A possible surfactant induced mechanism
is proposed based on the experimental data. UV-vis measurement
exhibits overwhelmingly strong intensity due to the unique
coral-like architecture. In addition, by introduction of halogen
anions, the particle size and optical absorption reduce, while the
photoluminescence intensity enhances significantly as the
halogen anion radius increases. Thus, all of the above properties
as well as the energy band structure can be controlled delicately.
This present work may broaden the potential applications of
BaTiO3 to laser devices, photon detectors, photocatalyst and
some other fields.
Acknowledgments
This work was financially supported by the One Hundred
Talents Project Foundation Program (1029271301), the Western
Light Talent Culture Project (Grant No. RCPY201206) of Chi-
nese Academy of Sciences, the National Natural Science Foun-
dation of China (Grant Nos. 41302029 and 41130746) and the
International Technology Cooperation Foundation of Autono-
mous Region (20136009).
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