Materials Chemistry and Physics 115 (2009) 172–178

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Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Synthesis of assembled ZnO structures by precipitation method in

aqueous media
S. Sepulveda-Guzman a,b,∗ , B. Reeja-Jayan c , E. de la Rosa d , A. Torres-Castro a,b ,
V. Gonzalez-Gonzalez a,b , M. Jose-Yacaman e
a
Centro de Innovación, Investigación y Desarrollo en Ingeniería y Tecnología, UANL Km. 10 de la nueva carretera al Aeropuerto Internacional de Monterrey,
PIIT Monterrey, Apodaca NL, Mexico
b
Facultad de Ingeniería Mecánica y Eléctrica de la UANL, Ciudad Universitaria San Nicolás de los Garza, Nuevo León C.P. 66451, Mexico
c
Texas Materials Institute, The University of Texas at Austin, 1 University Station C0803, USA
d
Centro de Investigaciones en Óptica, A.C. Loma del Bosque #115 Col. Lomas del Campestre, León Gto. C.P. 37150, Mexico
e
Physics and Astronomy Department, University of Texas at San Antonio, 1604 Campus San Antonio, TX 78249, USA

a r t i c l e i n f o a b s t r a c t

Article history: In this work, arrays of submicron ZnO structures were successfully synthesized using a one-step
Received 5 August 2008 aqueous precipitation method. Snowflake-like and flower-like morphologies were obtained by chang-
Received in revised form 15 October 2008 ing the reaction temperature. X-ray diffraction (XRD) patterns indicated that the ZnO arrays have a
Accepted 16 November 2008
wurtzite crystal structure. A possible growth mechanism based on the analysis done by scanning elec-
tron microscopy (SEM), transmission electron microscopy (TEM), high-resolution transmission electron
Keywords:
microscopy (HRTEM), and high-angle annular dark field (HAADF) is proposed. Our findings suggest that
Zinc oxide
the growth mechanism of the ZnO arrays is by self-aggregation, and that such an oriented aggregation is
Microstructure
Nanomaterials
enhanced by increasing the reaction temperature. The results also revealed that the aggregation process
Chemical growth introduces several structural defects such as differences in mass distribution and crystalline structure.
In order to study the surface chemical composition the samples were also characterized by XPS. The
results showed the presence of Zn(OH)2 and absorbed carbon species on the ZnO surface. In addition, the
photoluminescence characterization showed that on UV excitation ( = 360 nm) all samples present the
characteristic UV emission centered at 390 nm, and for the sample synthesized at 60 ◦ C, a visible emission
was also observed.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction properties of nanowires are modified by varying morphological fac-

Zinc oxide (ZnO) is a direct band gap semiconductor with a
room temperature wide band gap of 3.37 eV and a large excitonic
(electron–hole) binding energy of 60 meV, larger than the thermal
energy at room temperature (26 meV). In addition, ZnO is biocom-
patible, and can be used in bio-applications without coating [1].
These properties make ZnO an interesting material with poten-
tial applications such as sensors [2], UV lasers [3], piezoelectric
[4], luminescent phosphor, photonic crystals [5], and photovoltaics
[6]. A lot of research has been conducted on tuning the electrical
and optical properties of ZnO. Sadhu et al. studied the doping of
ZnO with rare earth ions such as Eu3+ in order to produce white
light emission, but also observed that the optical properties were
altered by changing morphological parameters such as particle size
and shape [7]. Chang et al. [8] also reported that photoluminescence
∗ Corresponding author.
E-mail addresses: ssepulveda@mail.uanl.mx, selenura@gmail.com
(S. Sepulveda-Guzman).
tors such as diameter and length. On the other hand, the design of
structures by the assembly of nanoparticles has also received great
attention in recent years because their resulting properties depend
on their microstructure, morphology and surface. Branched struc-
tures are also very important because of the increased number of
connection points, providing a means for parallel connectivity and
interconnection of functional elements in applications like solar
cells. Higher conversion efficiencies have recently been reported
for dye sensitized solar cells when flower-like ZnO particles were
used as electrode material [9]. In addition, the process of assem-
bly of structures allows the study of several growth mechanisms,
such as the self-aggregation processes in ZnO structures, which
are difficult to elucidate in isolated particles [10]. Several methods
like chemical vapor deposition (CVD) and physical vapor deposi-
tion (PVD) have been developed to assemble ZnO nanoparticles
into complex structures such as flower-like and web-like agglom-
erates [11–13]. However, in order to obtain the final structure
these methods usually require multiple steps, high temperature and
sophisticated equipment. In contrast, low-temperature wet chem-
ical processes such as precipitation, hydrolysis, and hydrothermal

0254-0584/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2008.11.030
 S. Sepulveda-Guzman et al. / Materials Chemistry and Physics 115 (2009) 172–178 173

process are cost-effective and scalable and have been used in the
synthesis of a wide variety of ZnO nanostructures. The precipitation
method in particular has been successfully used to design differ-
ent structures of ZnO. Kawano et al. [14] observed a change in the
growth mechanism when the preparation method changed from
acidic to basic route. One-dimensional nanoparticles (rods) were
prepared by changing the addition sequence of reagents. The con-
trolled growth of ZnO structures by the assembly of particles has
also been reported using a precipitation method assisted by poly-
mers or surfactants [15–17]. In addition, arrays of tower-like and
tube-like ZnO structures have also been synthesized by wet chem-
ical methods. However, in order to obtain such structures a harsh
process was required [18]. The effect of reaction parameters such
as pH and reaction time on morphology has also been elucidated
[19–21]. Nevertheless, the synthesis of assembled ZnO structures in
large volumes using simpler and economical wet chemical meth-
ods is still a challenge. In this work we prepared ZnO assemblies
by a wet chemical approach without any template or surfactant.
The morphology of the assembled ZnO structures was modified by
the change of reaction temperature. In addition, structural char-
acterization of the synthesized assemblies was studied by X-ray
diffraction (XRD), scanning electron microscopy (SEM), transmis-
sion electron microscopy (TEM) and high-angle annular dark field
(HAADF) techniques. Surface chemical composition was also ana-
lyzed by X-ray photoelectron spectroscopy (XPS).

2. Experimental
Zinc nitrate (Zn(NO3 )2 ) and sodium hydroxide (NaOH) reagents were purchased
from Aldrich and used without any purification. In a typical process 12.5 ml of 0.2 M
Zn(NO3 )2 solution was added to 25 ml of deionized water. The mixture was trans-
ferred to an oil bath at the reaction temperature. Once the temperature was stabilized
12.5 ml of 4 M NaOH solution was added immediately to the mixture under vigor-
ous stirring. After the addition, the mixture was heated and stirred continuously
for 3 h. To study the effect of temperature, several experiments were carried out at
60 ◦ C, 70 ◦ C and 80 ◦ C. Each experiment produced an uniform ZnO precipitate that
was separated by centrifugation and washed with deionized water. The ZnO samples
were analyzed by SEM using a Hitachi S-4500II operating at 10 kV. TEM, HRTEM, and
HAADF were performed on a Philips Tecnai F20 and JEOL 2010F at 200 kV. Samples
were dispersed in ethanol at room temperature and sonicated for 10 min. Aliquots
were dropped on 3-mm diameter lacey carbon copper grids. The XRD patterns were
acquired using a SIEMENS D-5005 equipment provided with a Cu tube with K␣ radi-
ation at 1.54 Å, scanning in the 25–75◦ 2 range with increments of 0.03◦ and a swept
time of 8 s. The samples were analyzed by XPS on a PHI 5700 system equipped with
dual Mg X-ray source and monochromated Al X-ray source with depth profile and
angle-resolved capabilities. The charging effect was corrected by shifting the binding
energies, considering the C 1s signal at 284.6. Nonlinear fit, using Gaussian curves,
was performed, maintaining the full-width at half-maximum (FWHM) constant for
all components in a particular spectrum. The photoluminescence (PL) characteriza-
tion was performed at room temperature on a Jovin Yvon fluorometer under 360 nm
excitation from a 75 W UV Xe lamp. The spectra were acquired from ZnO powder
dispersed in ethanol in a quartz cuvette. In order to correct the electronic noise
Savitzky-Golay algorithm was applied to all spectra and finally normalized to the
maximum value.
3. Results and discussion
Fig. 1 shows the XRD patterns of as-synthesized powders at dif-
ferent temperatures, all diffraction peaks can be indexed to the
hexagonal phase of ZnO and agree very well to the reported data
(JCPDS 05-0664). This indicates that even the samples synthesized
at lower temperatures have a well-defined crystalline structure. In
addition, no other peak related with impurities was detected in the
XRD patterns. However, differences in the relative peak intensities
of the diffraction pattern of the three samples were observed, which
can be associated with a particular orientation for each sample.
3.1. Morphology and structural characterization
Fig. 2 shows the SEM images of the ZnO samples synthesized
at 60 ◦ C, 70 ◦ C, and 80 ◦ C revealing high-yield growth of assem-
Fig. 1. X-ray diffraction (XRD) patterns of the as-synthesized ZnO powders obtained
at different temperatures.
bled ZnO structures. The morphology and the average size of the
assemblies were very uniform in each case, as seen in the SEM
images acquired at lower magnification (Fig. 2a, c, and e). How-
ever the general morphology of the assembled ZnO structures was
strongly influenced by the reaction temperature. The ZnO arrays
obtained at 60 ◦ C seem to resemble flakes growing out of a common
nucleus (Fig. 2b). The sample obtained at 70 ◦ C contains flower-
like structures very different from those synthesized at 60 ◦ C. The
growth pattern of the particles seems to have a preferential direc-
tion, resembling leaves sticking out of a nucleus (Fig. 2d). This
morphology is evident in the sample synthesized at higher tem-
perature (Fig. 2e), which contains more defined structures, and
the pattern of growth is similar to that obtained at 70 ◦ C (Fig. 2c).
However, the structure is formed by uniform rods with common
nuclei, rather than leaf-like structures. These observations suggest
that the precipitation process can be a successful method to obtain
different ZnO arrays under milder conditions, in contrast to those
obtained at longer reaction time and higher temperature [18,19].
In addition, the average size of the resulting arrays decreased from
1 ␮m to 500 nm when the reaction temperature was increased from
60 ◦ C to 80 ◦ C. This might have been promoted by a higher number
of ZnO nuclei formed at the higher temperature during the pre-
cipitation process. The subsequent particle growth was restricted
resulting in a smaller particle size. In order to study the structure
and find evidence about the growth mechanism of the assembled
ZnO structures, analyses of HAADF, TEM and HRTEM were done.
Fig. 3 shows the HAADF images acquired from the ZnO assemblies.
The HAADF images show little diffraction effects, and hence con-
tain very useful information about the chemical composition and
the mass distribution [22]. The ZnO assemblies show a heteroge-
neous mass distribution according to the differences in brightness
observed in the respective HAADF images (Fig. 3). This observa-
tion is also related to some irregularities on the surface [23]. This
characteristic is stronger in the assembly synthesized at lower tem-
perature as was revealed by the irregular brightness in the flake-like
structure (Fig. 3a). The TEM images can provide details about the
structure of the ZnO assemblies. Fig. 4 shows bright-field TEM
174 S. Sepulveda-Guzman et al. / Materials Chemistry and Physics 115 (2009) 172–178

Fig. 2. Scanning electron microscope (SEM) images at low and high magnifications of the assembled ZnO structures synthesized at (a and b) 60 ◦ C; (c and d) 70 ◦ C, and (e and
f) 80 ◦ C.

images of the flake-like, leaf-like and rod-like structures obtained ture (Fig. 4a). The image also shows a fairly smooth surface as was
at different temperatures. Regular fringes spaced at 0.28 nm, which previously observed by HAADF analysis, which is attributed to the
corresponds to the (1 0 0) interplanar distance are clearly visible random attachment of ZnO nanoparticles to the flake-like structure,
in the HRTEM image of the sample synthesized at lower tempera- resulting in a rough surface. This effect is less evident in the sam-

Fig. 3. High-angle annular dark field (HAADF) images of the ZnO assemblies obtained at (a) 60 ◦ C, (b) 70 ◦ C and (c) 80 ◦ C.
 S. Sepulveda-Guzman et al. / Materials Chemistry and Physics 115 (2009) 172–178 175

ple synthesized at 70 ◦ C. The HRTEM image clearly shows a fringe
spacing of 0.513 nm and 0.283 nm which corresponds to (0 0 1) and
(1 0 0) planes, respectively. Nevertheless, the sample synthesized at
80 ◦ C in contrast to that synthesized at lower temperature shows
a smooth surface and the corresponding HRTEM image revealed
that the arrays are formed by crystalline rods with a lattice spac-
ing of 0.287 nm, which corresponds to the (1 0 0) planes in ZnO.
The HRTEM image also shows that the rods grow along the [0 0 0 1]
direction, the polar c-axis of the ZnO crystal lattice (Fig. 4f) [24].
These observations revealed that the growth mechanism of ZnO
structures in aqueous solution can be modified by changing the
reaction temperature. This in turn changes the morphology of the
resulting ZnO arrays formed under different reaction conditions.
A growth mechanism is proposed in Fig. 5. During the precipi-
tation process ZnO nuclei were produced and in the absence of
any stabilizer agent, regular array-like structures were formed by
self-aggregation process as was indicated by HRTEM analysis. This
self-aggregation can proceed either by a randomly oriented or by a
highly oriented process, as reported in several works [25,26]. In this
case the oriented aggregation was highly favored by increasing the
reaction temperature as was observed in the sample synthesized at
80 ◦ C. This either resulted from the aggregation of primary nanopar-

Fig. 4. Transmission electron microscope (TEM) images of the ZnO arrays synthesized at (a) 60 ◦ C, (b) 70 ◦ C, and (c) 80 ◦ C. High-resolution transmission electron microscope
(HRTEM) images of the structure base of the arrays obtained at (d) 60 ◦ C, (e) 70 ◦ C, and (f) 80 ◦ C.
176 S. Sepulveda-Guzman et al. / Materials Chemistry and Physics 115 (2009) 172–178
Fig. 5. Schematic representation of ZnO arrays formation by precipitation method
in aqueous solution.
ticles in an oriented mode or the particles may have first aggregated
randomly and then reoriented during the reaction to produce crys-
talline rods. However, this process is less likely to occur at lower
temperatures, in which case the randomly oriented aggregation or
imperfect oriented attachment process promoted the incorpora-
tion of structural defects on the ZnO as can be seen in the HRTEM
image of flake-like arrays. This observation is in agreement with
other reports and has been widely explained by Penn et al. [27].
3.2. XPS characterization
XPS characterization of the ZnO arrays was performed in order
to investigate the variation of the chemical composition of the sam-
Fig. 6. High-resolution Zn 2p3/2 XPS spectra and high-resolution O 1s XPS spectra for the samples synthesized at different temperatures.
ples as a function of the reaction temperature. Fig. 6a, b and c shows
the XPS deconvoluted spectra for Zn 2p3/2 core level for the samples
synthesized at 60, 70 and 80 ◦ C, respectively. In all cases the peak
was deconvoluted into two peaks, the dominant peak at 1021.2 eV
is associated with the Zn2+ in ZnO wurzite structure and the weaker
peak at 1022.3 eV is associated with some zinc hydroxide species
[28,29]. The deconvolution of XPS spectra for the O 1s core level
line shows the presence of three different peaks (Fig. 6). The main
peak centered at 530.2 eV is attributed to the O 1s level in the ZnO
wurzite structure surrounded by the Zn atoms with their full com-
plement of nearest-neighbor O2− ions [30]. The peak at 531.5 eV is
associated with the O 1s in the zinc hydroxide species and agrees
very well with the O 1s binding energy in other metal hydroxides
and oxyhydroxides [31]. The peak at 532.5 eV is associated with
adsorbed or chemisorbed oxygen species such as O2 , H2 O or CO
due to surface hydroxyl groups [32,33]. This suggests that besides
chemisorbed hydroxyl species due to the polar face of ZnO, Zn(OH)2
is also present on the surface. However, the Zn(OH)2 is present
in low concentration and only on the surface, since no evidence
of this compound was observed by XRD. In addition, the relative
abundance of Zn(OH)2 obtained from the Zn 2p3/2 spectrum, using
the atomic sensitive factors, indicates that the sample synthesized
at lower temperature contains a higher concentration of Zn(OH)2
(11%) when compared to that synthesized at higher temperature
(8%). It is possible that during the reaction at lower temperature a
partial ZnO precipitation occurred, forming other Zinc oxyhydrox-
ide species [34]. In addition to the Zn 2p3/2 and O 1s high-resolution
spectra, C 1s core level spectrum was also acquired. The deconvo-
lution of the C 1s peak is shown in Fig. 7. The peak at 284.6 eV is
indexed to C 1s whereas the peak at about 288.5 eV is associated
with C 1s of chemisorbed carbon species on the ZnO surface [30].
This observation is in agreement with the analysis of O 1s high-
resolution spectrum. The values of relative abundance for different
carbon species calculated from the high-resolution C 1s spectra sug-
 S. Sepulveda-Guzman et al. / Materials Chemistry and Physics 115 (2009) 172–178
Fig. 7. High-resolution C 1s spectra for the sample synthesized at different temper-
atures.
gest that the flake-like arrays, which were synthesized at lower
temperature, are more likely to interact with carbon species like
dissolved carbonic anhydride present in the water or solvent used
to purify the ZnO powder after reaction. This was possibly favored
by both the presence of Zn(OH)2 and the surface defects observed in
this sample during the morphological and structural analysis. XPS
results also indicate that the ZnO arrays have a potential for use in
catalytic reactions due to the high abundance of reactive sites, pro-
moted by surface defects. However, additional studies focused on
this application must be done.
3.3. Photoluminescence characterization
Fig. 8 shows the room temperature photoluminescence spectra
for the arrays synthesized at 60, 70 and 80 ◦ C. For the arrays synthe-
sized at higher temperature, 70 and 80 ◦ C, the spectra showed a UV
emission band (390 nm) which is the characteristic near band gap
Fig. 8. Photoluminescence spectra of the arrays synthesized at different tempera-
tures.
177
(NBG) of ZnO and is associated with the free recombination of exci-
tons. Whereas, for the arrays synthesized at 60 ◦ C besides the UV
emission centered at 390 nm a broad green visible emission cen-
tered at 580 nm is observed. The green visible emission bands in
ZnO samples has been observed before and commonly attributed
to the recombination of electrons in oxygen vacancies. The origin
of oxygen vacancies is still not fully understood. However, in this
case they could be produced by the structural defects incorporated
during crystal growth through self-aggregation process at low tem-
perature and by the presence of zinc oxyhydroxide species on the
surface of ZnO arrays which in turn creates nonstoichiometric ZnO.
These assumptions are in agreement with other reports [28,35,36]
and are in concurrence with the XPS results described before.
4. Conclusions
In this work, the assembly of submicron ZnO structures has
been demonstrated by a simple precipitation method in aqueous
medium within a considerably low reaction temperature range.
SEM analysis indicated a strong effect of the reaction temper-
ature on the morphology of the ZnO arrays. HAADF, TEM and
HRTEM analysis further clarified that morphological and structural
changes were introduced by changing the reaction temperature.
These results suggest that the growth mechanism was by self-
aggregation. These oriented and random aggregation processes
were dependent on the reaction temperature. A random aggrega-
tion process resulted in ZnO flake-like arrays with surface defects
and a high concentration of Zn(OH)2 , which created a reactive sur-
face as was shown by the XPS analysis. In addition, on UV excitation
( = 360 nm) all samples presented a UV emission peak character-
istic of ZnO. In addition, a visible emission band was observed for
the arrays synthesized at 60 ◦ C and it was attributed to structural
defects and the presence of oxyhydroxide species.
Acknowledgments
The authors wish to thank Dr. Y. Sun for XPS measurements, Dr. X.
Gao for TEM assistance and M. Ramirez for helping with sample syn-
thesis. We acknowledge financial support by the Welch foundation
and the ICNAM-CIMAV program. We are also thankful to Industrias
Penoles for support this project.
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