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2014-12

Effect of Zn2+ ions on the structure,

morphology and optical properties of CaWO4
microcrystals
Journal of Sol-Gel Science and Technology, New York : Springer, v. 72, n. 3, p. 648-654, Dec. 2014
http://www.producao.usp.br/handle/BDPI/50892
Downloaded from: Biblioteca Digital da Produo Intelectual - BDPI, Universidade de So Paulo

J Sol-Gel Sci Technol (2014) 72:648654

DOI 10.1007/s10971-014-3550-y

BRIEF COMMUNICATION

Effect of Zn2+ ions on the structure, morphology and optical

properties of CaWO4 microcrystals
M. A. P. Almeida J. R. O. Lima C. Morila-Santos
P. N. Lisboa Filho M. Siu Li E. Longo
L. S. Cavalcante

Received: 19 July 2014 / Accepted: 15 October 2014 / Published online: 30 October 2014
 Springer Science+Business Media New York 2014

Abstract The effect of zinc ions (Zn2?) on the structure,

morphology and optical properties of (Ca1-xZnx)WO4
microcrystals with (x = 0, 0.01, 0.02, and 0.03) obtained by
the microwave-hydrothermal method at 170 C for 1 h is
reported in this letter. These microcrystals were characterized
by X-ray diffraction (XRD), Rietveld refinement, energy
dispersive X-rays spectroscopy (EDXS) and field emission
scanning electron microscopy (FE-SEM) images. The optical
properties were investigated by ultravioletvisible (UVVis)
diffuse reflectance spectroscopy and photoluminescence (PL)
measurements. XRD patterns and Rietveld refinement data
Electronic supplementary material The online version of this
article (doi:10.1007/s10971-014-3550-y) contains supplementary
material, which is available to authorized users.

indicated that all the (Ca1-xZnx)WO4 microcrystals present a

tetragonal structure and a reduction of lattice parameters and
unit cell volume occurs with the increase of Zn2?. EDXS
data confirms that the elemental chemical composition was
achieved for (Ca1-xZnx)WO4 microcrystals. FE-SEM images
showed that the replacement of Ca2? by the Zn2? promotes a
reduction of average crystals size and considerable changes
in crystal shape starting from dumbbell-like to decorative
ball-like (Ca1-xZnx)WO4 microcrystals. UVVis spectra
evidenced a small increase in optical band gap values (from
5.72 to 5.76 eV). Finally, PL emission of (Ca1-xZnx)WO4
microcrystals was improved until x = 0.02 due to the presence of defects at medium range and new intermediate
electronic levels in the band gap associated to the Zn2?
content.

M. A. P. Almeida
J. R. O. Lima
Coordenacao de Ciencias e Tecnologia, Universidade Federal do
Maranhao, Sao Lus, MA 65080-805, Brazil

Keywords CaWO4
Microcrystals
Zinc
Distortions

Photoluminescence

C. Morila-Santos
Departamento de Fsica, Universidade Federal do Ceara,
Campus do Pici, Fortaleza, CE 60455-760, Brazil
P. N. Lisboa Filho
MAvDF UNESP-Universidade Estadual Paulista, Bauru,
SP 17033-360, Brazil
M. Siu Li
Instituto de Fsica de Sao Carlos, Universidade de Sao Paulo,
Sao Carlos, SP CEP. 13560-970, Brazil
E. Longo
Instituto de Qumica, UNESP (Universidade Estadual Paulista),
Araraquara, SP 14800-900, Brazil
L. S. Cavalcante (&)
CCN-DQ-GERATEC, Universidade Estadual do Piau, R. Joao
Cabral, N. 2231, P.O. Box 381, Teresina, PI 64002-150, Brazil
e-mail: laeciosc@bol.com.br

123

1 Introduction
The increase in world population brought with it a range of
problems to be solved by future researchers. In this context,
materials chemistry has as a main function the development of
new several synthesis methods to obtain functional micro-,
meso- and nanomaterials with different electronic applications to improve the human life quality [13]. In the last few
years a considerable number of papers regarding metal tungstates (MeWO4; Me = Ca2?, Sr2?, Ba2?, Mn2?, Fe2? and
Zn2?, all divalent cations) has been published [49]. The
higher interest in these materials is due their electronic properties in diverse fields such as optical [10], sensors [11], catalysts [12], magnetic [13], and medical [14]. The electronic
structure of metal tungstates can be classified into two large

J Sol-Gel Sci Technol (2014) 72:648654

groups. The first group have a scheelite-type tetragonal

structure, where the tungsten (W) atoms are coordinated to
four oxygen atoms forming tetrahedral [WO4] clusters, while
the metals (Me = Ca2?, Sr2?, and Ba2? ions) are coordinated
to eight oxygen atoms forming deltahedral [MeO8] clusters.
The second group have a wolframite-type monoclinic structure, where both the W and (Me = Mn2?, Fe2?, Ni2?, and
Zn2? ions) are coordinated to six oxygen atoms forming
octahedral [WO6]/[MeO6] clusters [1518].
Among these various tungstates, the calcium tungstate
(CaWO4) crystals in pure form have attracted more attention because of their excellent optical properties [1921].
X-ray, electron beam and UV irradiation cause a high
efficiency material emission of blue light [22]. Therefore,
CaWO4 makes it a self-active promising material for the
white laser applications and scintillation counters [23]. In
addition, CaWO4 crystals when doped with other ions such
as lanthanide and transition metals can generate multi-color
emissions by single-wavelength light excitation, which
lead to various applications, such as solid-state lighting
devices, field emission displays as well as luminescent
labels [24, 25].
The literature [26] has reported the preparation of
(Ca1-xZnx)WO4 nanoparticles of several different compositions with (x = 0, 0.005, 0.01, 0.05, 0.09, and 0.1) by the
precipitation method using a citric acid capping agent for
kinetic control of the grain size. Moreover, these authors
have observed a reduction in the intensity of photoluminescence (PL) at room temperature, which is attributed to
micro-structural factors.
This letter reports the successful synthesis of a series of
(Ca1-xZnx)WO4 microcrystals with (x = 0; 0.01, 0.02, and
0.03) by the microwave-hydrothermal (MH) method at
170 C for 1 h resulting in different shapes (dumbbells;
cocoa; custard apple and decorative ball). Moreover, our
(Ca1-xZnx)WO4 microcrystals exhibited a considerable
improvement in PL emission until x = 0.02 due to the
presence of defects at medium range and new intermediate
electronic levels related to 3d orbitals (Zn) present between
5d orbitals (W) (conduction band) and 2p orbitals (O).

2 Experimental details
2.1 Synthesis of (Ca1-xZnx)WO4 crystals
(Ca1-xZnx)WO4 microcrystals with (x = 0, 0.01, 0.02, and
0.03) were synthesized using the methodology published in
paper [27], using appropriate amounts of the following
reagents: 1 9 10-3 mols of sodium tungstate dihydrate

649

[(Na2WO4
2H2O); Aldrich, 99 %], 1 9 10-3 mols of calcium acetate monohydrate [Ca(C2H3O2)2
H2O; Aldrich,
99 %] to obtain pure CaWO4 microcrystals. The doped
(Ca1-xZnx)WO4 microcrystals were obtained using
1 9 10-3 mols of sodium tungstate dihydrate [(Na2
WO4.2H2O); Aldrich, 99 %], 99, 98 and 97 % of 1 9 10-3
mols of calcium acetate monohydrate [Ca(C2H3O2)2
H2O;
Aldrich, 99 %] and 1, 2 and 3 % of 1 9 10-3 mols of zinc
acetate monohydrate [Zn(C2H3O2)2
H2O, Aldrich, 99 %],
respectively. These specific reaction mixtures were
homogenized and transferred to a Teflon autoclave, which
was sealed and placed in the MH system using 2.45 GHz
microwave radiation with maximum power of 800 W. The
reactional mixture was heated at 170 C for 1 h. After that,
the autoclave was naturally cooled to room temperature.
The resulting suspensions were washed with deionized
water several times to remove any remaining Na? ions, and
dried with acetone and heated at 50 C for 6 h.
2.2 Characterizations
The (Ca1-xZnx)WO4 microcrystals with (x = 0, 0.01,
0.02, and 0.03) were structurally characterized by X-ray
diffraction (XRD) patterns using a D/Max-2500PC diffractometer (Rigaku, Japan) with CuKa radiation
) in the 2h range from 10 to 70 with a
(k = 1.5406 A
scanning velocity of 2/min. Rietveld analysis was conducted in a 2h range from 10 to 110 with a scanning
velocity of 1/min and a step of 0.02. The Fourier
transform Raman (FTRaman) spectroscopy was recorded with a Bruker-RFS 100 (Germany). The Raman
spectra were obtained using a 1,064 nm line with
Nd:YAG laser, keeping its maximum output power at
100 mW and performed in the range from 50 to
1,000 cm-1. Elementary qualitative analysis for Ca, Zn,
W, and O was performed using energy dispersive X-rays
spectroscopy (EDXS). The crystal shapes and sizes were
observed by field emission scanning electron microcopy
(FE-SEM) through a Supra 35-VP (Carl Zeiss, Germany)
operated at 15 kV. UVVis diffuse reflectance spectra
were taken using a Varian spectrophotometer, model
Cary 5G (USA) in diffuse reflectance mode. PL measurements were taken using a Monospec 27 monochromator (Thermal Jarrel Ash, USA) coupled to a R446
photomultiplier (Hamamatsu, Japan). A krypton ion laser
(Coherent Innova 90K, USA) (k = 350 nm) was used as
an excitation source, keeping its maximum output power
at 500 mW and maximum power of 40 mW on the
powders after the laser beam was passed through an
optical chopper. PL measurements were performed at
room temperature.

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J Sol-Gel Sci Technol (2014) 72:648654

3 Results and discussion

3.1 X-ray diffraction and Rietveld refinement analyses
Figure 1ad illustrates the XRD patterns of (Ca1-xZnx)
WO4 microcrystals with (x = 0, 0.01, 0.02, and 0.03)
obtained by MH method.
The degree of structural orderdisorder at long-range or
periodicity of (Ca1-xZnx)WO4 microcrystals was verified
by the XRD technique. XRD patterns illustrated in Fig. 1a
d indicated that all (Ca1-xZnx)WO4 microcrystals with
(x = 0, 0.01, 0.02, and 0.03) have a scheelite-type tetragonal structure with space group (I41/a) and point-group
6
) in good agreement with the Inorganic
symmetry (C4h
Crystal Structure Database (ICSD) No. 18135 [28]. Secondary phases were not observed in the diffractograms,
revealing that the MH processing were able to promote the
formation of the pure phase. Moreover, the presence of
strong and sharp diffraction peaks is a typical characteristic
of materials structurally ordered at long-range.
Structural refinements using the Rietveld method [29]
with GSAS software [30] confirmed that all (Ca1-xZnx)
WO4 microcrystals with (x = 0, and 0.01) have a tetragonal structure without secondary phases; (Fig. 2a, b and
Figs. S1(a,b)) for (Ca1-xZnx)WO4 microcrystals with
(x = 0.02 and 0.03) are in the support information.
Rietveld refinement was based on the CaWO4 phase
with a scheelite-type tetragonal structure as described in
the Crystallographic Information File (CIF) No. 18135
[28]. All structural refinements (Fig. 2a, b and Figs.

Fig. 2 Rietveld refinements of (Ca1-xZnx)WO4 microcrystals with

Zn2? concentrations: a 0 and b 0.01, respectively

Fig. 1 XRD patterns of (Ca1-xZnx)WO4 microcrystals with Zn2?

concentrations: a 0, b 0.01, c 0.02 and d 0.03 obtained by the MH
method at 170 C for 1 h, respectively. The vertical lines indicate the
relative positions of diffraction peaks described in ICSD No. 18135

123

S1(a,b)) showed a good correlation between observed and

calculated XRD patterns (YObs - YCalc lines), indicating
the reliability of the results. More details on these obtained
data are displayed in Table S1 as presented in support
information.
In these tables, fit parameters (RF2, v2, and S) suggest that
refinement results are very reliable. Table S1 shows that the
replacement of Ca atoms (atomic radius = 180 pm) by Zn
atoms (atomic radius = 134 pm) promotes a reduction in the
lattice parameters and unit cell volume of crystals [26].
Considerable variations in the atomic positions related to the
oxygen (O) atoms can be observed while the calcium (Ca)
atoms, zinc (Zn) atoms and tungsten (W) atoms remain fixed
in their positions in the tetragonal structure. These data
suggest the existence of structural distortions on the deltahedral [CaO8]/[ZnO8] clusters and tetrahedral [WO4] clusters belonging to the (Ca1-xZnx)WO4 microcrystals with a

J Sol-Gel Sci Technol (2014) 72:648654

651

tetragonal structure (x = 0, 0.01, 0.02, and 0.03) arising

from coupling with microwaves and differences between
their electronic densities. Lattice parameters and atomic
positions obtained from Rietveld refinements were used to
model the lattice of the pure CaWO4 crystal and (Ca1-x
Znx)WO4 microcrystals with (x = 0.03) by means of the
Visualization for Electronic and Structural Analysis
(VESTA) program (version 3.1.8 for Windows) [31], as
shown in support information (Figs. S2(a,b)).
3.2 FEG-SEM images analyses
Figure 3ad illustrate the FE-SEM images for (Ca1-x
Znx)WO4 microcrystals with (x = 0, 0.01, 0.02, and 0.03)
obtained by the MH method at 170 C for 1 h,
respectively.
FEG-SEM images are of fundamental importance for
understanding the shape evolution and the growth process
of CaWO4 microcrystals with the substitution of the Ca2?
by Zn2?. Figure 3a shows a large quantity of dumbbelllike CaWO4 microcrystals grown after MH processing at
170 C for 1 h. These superstructures have an average
size of approximately 8.5 lm which are formed by the
aggregation of several nanocrystals, as can be seen in
Figs. S3(a). This anisotropic growth of CaWO4 microcrystals occurs by means of a self-assembly process with
several partially oriented nanocrystals. When 1 % of Ca2?
are replaced by Zn2? as can be observed in Fig. 3b, a
modification in the crystal shape from to dumbbell-like
crystals to cocoa-like crystals and a considerable reduction in average crystal size to approximately 4.2 lm.
Figure 3c clearly shows a decrease in average size to
approximately 2.5 lm with further increasing substitution
of Ca2? by Zn2? (x = 0.02). The replacement of Ca2? by
Zn2? promotes a quasi-unidirectional or quasi-isotropic
growth by formation of quasi-sphere or custard apple-like
crystals; this behavior can be attributed to the smaller
atomic radius of zinc relative to the calcium atom atomic
radius. Figure 3d shows isotropic growth due to the presence of sphere-like or decorative ball-like (Ca0.97
Zn0.03)WO4 microcrystals and a slight decrease in average
size to approximately 2.1 lm. Therefore, to minimize the
overall energy of the system, a great number of these seed
particles must aggregate [32].
3.3 Growth mechanism of (Ca1-xZnx)WO4 crystals

Fig. 3 FE-SEM images of (Ca1-xZnx)WO4 microcrystals with Zn2?

concentrations: a 0, b 0.01, c 0.02 and d 0.03 obtained by the MH
method at 170 C for 1 h, respectively

Figure 4ad illustrate a schematic representation of all

stages involved in the synthesis and growth mechanism of
(Ca1-xZnx)WO4 microcrystals with (x = 0, 0.01, 0.02, and
0.03) obtained by MH method at 170 C for 1 h,
respectively.

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J Sol-Gel Sci Technol (2014) 72:648654

Fig. 4 Proposed growth and formation mechanisms for the

(Ca1-xZnx)WO4 microcrystals with Zn2? concentrations: a electrostatic attraction of Ca2?/Zn2? and WO24 ions in solution and possible
interactions, b aggregation process for small nuclei, c small crystals

grow by self-assemble process due to specific conditions of the

chemical reaction and d final stage of crystals growth of dumbbell-,
cocoa-, custard apple-, decorative ball-like microcrystals

Figure 4a shows that due to the difference in the

electronic density between Ca2?/Zn2? and WO24 , a
strong electrostatic force attraction occurs between both
ions, which results in the formation of the first
(Ca1-xZnx)WO4 nuclei with (x = 0, 0.01, 0.02, and 0.03)
(see Fig. 4b) [33]. The increase in the precipitation rate
leads to the aggregation process for small nuclei, and
these small nuclei self-assemble due to specific conditions
of the chemical reaction such as: the counter-ion effect,
pH and aqueous solvent (see Fig. 4b, c). In the first case,
these nunits of CaWO4 nanocrystals are formed and can
be merged through a self-assembly process that leads to
the anisotropic growth of dumbbell-like CaWO4 microcrystals (see Figs. 3a, 4d) [34]. In second, third and fourth
case, the nunits of nanocrystals of these (Ca1-xZnx)
WO4 microcrystals with (x = 0.01, 0.02, and 0.03) are
formed as previously described and have a main selfassembly process also can possibly be governed by an
Ostwald-ripening (OR) process due to presence of large

pores in crystals [35]. Figure 4d shows these superstructures which are composed of several nanocrystals in
partial orientation by the aggregation process. Therefore, a
possible OR mechanism also governs the growth process
of these (Ca1-xZnx)WO4 microcrystals with (x = 0, 0.01,
0.02, and 0.03) (Fig. 4c). A dissolution process of the
microcrystals and a later recrystallization of nanocrystals
and microcrystals were verified. This thermodynamicallydriven spontaneous process occurs because larger crystals
are more energetically favored than smaller crystals. In
the OR mechanism, atoms on the crystal surface are
energetically less stable than atoms in the interior [36].
These results are in agreement with the explanations
reported by Tian et al. [37] about the growth mechanism
of nanostructured CaWO4 microcrystals. Finally, after
further growth, these (Ca1-xZnx)WO4 superstructures with
(x = 0, 0.01, 0.02, and 0.03) have the following defined
shapes, such as: dumbbell-, cocoa-, custard apple-, decorative ball-like microcrystals as shown in Fig. 4d.

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653

3.4 UVVis diffuse reflectance spectroscopy and PL

emission analyses
The optical band gap energy (Egap) was calculated by the
KubelkaMunk method [38], which is based on the transformation of diffuse reflectance measurements to estimate
Egap values with good accuracy for semiconductor oxides.
According to the literature [39], CaWO4 crystals exhibit an
optical absorption spectrum governed by direct electronic
transitions. In this phenomenon, after the electronic
absorption process, electrons located in minimum energy
states in the conduction band (CB) are able to go back to
maximum energy states of the valence band (VB) at distinct points in the Brillouin zone [39].
Thus, the Egap values for (Ca1-xZnx)WO4 microcrystals
with (x = 0, 0.01, 0.02, and 0.03) were calculated by
extrapolating the linear portion of UVVis curves. Figs.
S4(a-d) show the UVVis spectra for all the microcrystals
obtained at 170 C for 1 h and Fig. S4(e) shows the evolution of Egap values for (Ca1-xZnx)WO4 microcrystals
with (x = 0, 0.01, 0.02, and 0.03). The decrease in Egap
values can be attributed to structural defects at mediumrange and local bond distortions, yielding localized electronic levels within the forbidden band gap. A smaller Egap
was detected for (Ca1-xZnx)WO4 microcrystals with
x = 0.01 (see Fig. S4(b)), which suggests a high concentration of defects in the lattice these cocoa-like microcrystals. However, the existence of new intermediate
electronic levels related to 3d orbitals (Zn) present between
5d orbitals (W) (conduction band) and 2p orbitals (O) in
these crystals can be shown only by theoretical calculations
which will be reported in a future paper. An increase in
replacement of Ca2? by Zn2? into the CaWO4 lattice of
x = 0.02 and 0.03 promotes a slight increase in Egap values
(see Fig. S4(c, d, e)).
Figure 5ad illustrates the PL emission spectra of
(Ca1-xZnx)WO4 microcrystals with (x = 0, 0.01, 0.02, and
0.03) excited by a laser (k = 350 nm) at room temperature.
PL properties of (Ca1-xZnx)WO4 nanocrystals prepared
with citric acid are related to of surface structural disorder,
electro-negativity differences, and effective activation of
the mobile protons [26]. Moreover, these researchers have
observed that a PL quenching occurs associated with the
increased amount of Zn2?, when excited by a laser
(k = 265 nm) at room temperature. However, we have
observed a different PL behavior for (Ca1-xZnx)WO4
microcrystals due to microstructural changes and aggregation effects. In addition, morphological aspects are able
to dislocate crystal lattice planes as well as adjacent particles in aggregates, producing specific defects in the
crystals. In another recent work [40], the PL properties of
CaWO4 crystals were attributed to charge transfers from
the oxygen ligand to the central tungstate ligand inside the

Fig. 5 PL emission spectra at room temperature (Ca1-xZnx)WO4

microcrystals with Zn2? concentrations: a 0, b 0.01, c 0.02 and d 0.03
obtained by the MH method at 170 C for 1 h, respectively. The inset
show the shape and morphology of each individual crystal

[WO24 ] groups. Li et al. [41] have reported that the PL

emission of CaWO4 nanocrystals is improved by increase
of oxygen vacancies and the reduction in average particle
size decreases. Boyle et al. [42] have observed that the
coalescence of the CaWO4 particles promotes a significant
improvement in PL emission at room temperature. Our
previous research [27, 33] on the CaWO4 crystals, shows
that their PL properties are related mainly to distortions on
tetrahedral [WO4] clusters into the tetragonal lattice.
Therefore, for (Ca1-xZnx)WO4 microcrystals with (x = 0,
0.01, 0.02, and 0.03) even though they have a distortion
factor that modifies the crystal shape and leads to the formation of favorable intermediary levels with specific
electronic transitions which improve the PL emission
properties at room temperature (Fig. 5ad). The reduction
of the gap values occurs with an increase of Zn2? into the
tetragonal CaWO4 lattice. Finally, we show that these
distortions also reside on both tetrahedral [WO4] clusters
and deltahedral [CaO8] clusters, which are affected due to
replacement of Ca2? by Zn2?, mainly on the distorted
tetrahedral [WO4] clusters, according to our theoretical
calculations [27].

4 Conclusions
In summary, we have reported the easy obtention of
(Ca1-xZnx)WO4 microcrystals with (x = 0, 0.01, 0.02,
and 0.03) by the MH method at 170 C for 1 h. XRD
patterns and Rietveld refinement data prove that these
crystals have a scheelite-type tetragonal structure without

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deleterious phases with the incorporation of Zn2?. FESEM images and EDXS spectra revealed that the incorporation of Zn2? into the CaWO4 crystal matrix affects
the shape and causes a reduction in the average crystal
size. The growth process proposed for these (Ca1-xZnx)
WO4 microcrystals indicates that growth occurs by the
self-assembly of small nanocrystals, and the further
growth of superstructures occurs by means of aggregation.
The Ostwald ripening process leads to the growth of
crystals with different shapes, such as: dumbbell-, cocoa-,
custard apple-, decorative ball-like microcrystals. UVVis
diffuse reflectance spectra indicate that the replacement of
Ca2? by Zn2? promotes a decrease in Egap values up to
x = 0.01 (from 5.72 to 5.68 eV). These levels are basically composed of 2p orbitals (O) (above the VB) and
5d orbitals (W) and 3d orbitals (Zn) (below the CB).
Finally, optical properties of our microcrystals are related
mainly to distortions on tetrahedral [WO4] clusters the
tetragonal lattice and changes in crystal shape are affected
by the replacement of Ca2? by Zn2? which leads to the
formation of favorable intermediary levels with specific
electronic transitions and improve the PL emission
properties at room temperature.
Acknowledgments The Brazilian authors acknowledge the financial support of the Brazilian research financing institutions: CNPq
(479644/2012-8; 304531/2013-8), FAPESP (12/18597-0; 09/50303-4;
2013/07296-2), and CAPES.

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