Journal of Asian Ceramic Societies 2 (2014) 253257

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Journal of Asian Ceramic Societies
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Synthesis and photocatalytic properties of -ZnWO
4
nanocrystals in
tungsten zinc borate glasses
Tatsuya Ida, Kenji Shinozaki, Tsuyoshi Honma, Takayuki Komatsu

Department of Materials Science and Technology, Nagaoka University of Technology, 1603-1 Kamitomioka-cho, Nagaoka 940-2188, Japan
a r t i c l e i n f o
Article history:
Received 5 February 2014
Received in revised form12 May 2014
Accepted 18 May 2014
Available online 14 June 2014
Keywords:
Glass
Crystallization
-ZnWO
4
Nanocrystals
Photoluminescence
Photocatalytic activity
a b s t r a c t
Tungsten oxide (WO
3
)-containing glasses of WO
3
ZnOB
2
O
3
were prepared using a conventional melt
quenching method, and -ZnWO
4
nanocrystals were synthesized through the crystallization of glasses.
A glass with the composition of 20WO
3
50ZnO30B
2
O
3
showed the bulk crystallization of -ZnWO
4
nanocrystals with a diameter of 10 nm. Broad and asymmetric emission peaks were observed at the
wavelength of 475nm, i.e., blue emissions, in the photoluminescence spectra for the samples with
-ZnWO
4
nanocrystals. From the degradation of the intensity of optical absorption under ultraviolet light
(= 254 nm) irradiations for the solution consisting of crystallized particles with -ZnWO
4
nanocrystals
and methylene blue, it was claried that -ZnWO
4
nanocrystals formed have photocatalytic activities.
The formation of -ZnWO
4
nanocrystals is discussed from the viewpoint of the glass-forming tendency.
2014 The Ceramic Society of Japan and the Korean Ceramic Society. Production and hosting by
Elsevier B.V. All rights reserved.
1. Introduction
Tungstate compounds have received much attention because of
their unique functions, e.g., ZnWO
4
for scintillator [1] and photo-
catalyst [2], Sc
2
(WO
4
)
3
showing negative thermal expansion [3],
Eu
3+
-doped (La,Gd)
2
(WO
4
)
3
for phosphors [4], and KYb(WO
4
)
2
for
solid state laser host [5]. It is of importance to control the morphol-
ogy, size, and quality of tungstate crystals for practical applications.
Onthe other hand, glasses containing tungstenoxide (WO
3
) suchas
WO
3
TeO
2
and K
2
OWO
3
TeO
2
have been synthesized, and their
structure and properties have also received much attention [613].
For instance, the electronic polarizability of oxide ions (i.e., optical
basicity) in WO
3
is very high [14,15], and thus, WO
3
-based glasses
showlarge third-order optical nonlinearities [10,16].
It is known that the crystallization of glass is an effective
method for the fabrication of transparent materials with desired
shapes and also nanostructures [1719], and the crystallization
technique has been applied to WO
3
-based glasses in order to fab-
ricate glass-ceramics (crystallized glasses) consisting of functional

Corresponding author. Tel.: +81 258479313.

E-mail address: komatsu@mst.nagaokaut.ac.jp (T. Komatsu).
Peer review under responsibility of The Ceramic Society of Japan and the Korean
Ceramic Society.
2187-0764 2014 The Ceramic Society of Japan and the Korean Ceramic Society.
Production and hosting by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jascer.2014.05.006
WO
3
-based compounds [2023]. For instance, Maczka et al. [20]
reported that a glass in the Cs
2
OMgOWO
3
P
2
O
5
systemexhibits
a prominent nanocrystallization during thermal treatments, pro-
viding Cs(Mg
0.25
W
1.75
)O
6
nanocrystals with the size of 410nm.
Aleksandrov et al. [21] synthesizedglasscrystal composite materi-
als withthe LaBWO
6
crystalline phase throughthe crystallizationof
25La
2
O
3
50WO
3
25B
2
O
3
glass. It is of interest to synthesize nano-
scaled tungstate compounds through the crystallization of glasses
and to clarify physical and chemical properties for practical device
applications.
In this study, we focus our attention on the synthesis and opti-
cal properties of ZnWO
4
nanocrystals through the crystallization
of glasses. Unfortunately, for ZnWO
4
, it is impossible to prepare
bulky glasses (not very thin or small akes) with the same com-
position as this crystal, i.e., a glass of 50ZnO50WO
3
. In order
to design the crystallization of ZnWO
4
, therefore, glass-forming
oxides such as SiO
2
and B
2
O
3
must be added. In the present study,
we use the ternary system of WO
3
ZnOB
2
O
3
, although its glass-
forming region is narrow as reported by Imaoka [24]. ZnWO
4
crystals have been synthesized by using various techniques such
as solid state reaction and mechanochemical methods [1,2,2527].
However, there has been no report on the crystallization of ZnWO
4
in glasses. Some electrical, thermal, and optical properties of
WO
3
ZnOB
2
O
3
glasses have been reported so far [6,9], but any
crystallization behavior has not been reported. Recently, Alek-
sandrov et al. [28] examined the structure and crystallization
behavior of MoO
3
ZnOB
2
O
3
glasses and found that some glasses
show the bulk crystallization of -ZnMoO
4
nanocrystals with a
diameter of 5nmand Eu
3+
-doped -ZnMoO
4
nanocrystals show
enhanced photoluminescence emissions. Considering the chemi-
cal similarity of tungsten (W) and molybdenum(Mo) elements, the
254 T. Ida et al. / Journal of Asian Ceramic Societies 2 (2014) 253257
crystallization of ZnWO
4
nanocrystals would be expected in
WO
3
ZnOB
2
O
3
glasses. As one of the optical properties of ZnWO
4
nanocrystals synthesized in this study, photocatalytic activities
for the decomposition of methylene blue under ultraviolet (UV)
light were examined. There have been some reports on the pho-
tocatalytic activities of ZnWO
4
powders [2,2931]. For instance,
Huang and Zhu [2] reported that ZnWO
4
powders prepared by cal-
cining co-precipitated precursors exhibit excellent photocatalytic
activities. Garadkar et al. [29] synthesized ZnWO
4
nanoparticles
(10nm) by using a simple microwave assisted technique and
found that they exhibit highly enhanced photocatalytic activity
toward rhodamine B and methylene blue samples.
2. Experimental
Compositions (mol%) examined in this study are 10WO
3

50ZnO40B
2
O
3
, 20WO
3
50ZnO30B
2
O
3
, 30WO
3
50ZnO20B
2
O
3
,
30WO
3
40ZnO30B
2
O
3
, and30WO
3
30ZnO40B
2
O
3
. Commercial
powders of reagent grade WO
3
, ZnO, and B
2
O
3
were used as start-
ing materials and were melted in a platinum crucible at 1250

C
for 20min in an electric furnace. The melts were poured onto an
iron plate and pressed to a thickness of 1.5mm by another iron
plate. The glass transition, T
g
, and crystallization peak, T
p
, temper-
atures were determined using differential thermal analysis (DTA)
(Rigaku, TG8120) at a heating rate of 10K/min. Glass samples were
heat-treated at different temperatures in an electric furnace in
air, and the crystalline phase present in the crystallized samples
was identied by X-ray diffraction(XRD) analysis (CuKradiation).
Morphologies of crystals inthecrystallizedsamples wereexamined
from high resolution transmission electron microscope (HRTEM,
JEM-2100F) observations.
Photoluminescence (PL) emission and excitation (PLE) spectra
were measured at room temperature with a spectrouo-
rophotometer (Shimadzu RF-5300PC). Photocatalytic activities of
heat-treated samples were evaluated by the degradation of methy-
lene blue (MB) under UV light (wavelength: =254nm). First,
heat-treated samples were pulverized by using an agate mortar,
and powders (100mg) were mixed with a methylene blue solu-
tion (concentration: 5ppm, volume: 100mL) in a beaker. UV light
(UV lamp; Toshiba, GL15-F) was irradiated onto the mixtures, and
optical absorption spectra of solutions were measured by using a
spectrophotometer (ShimadzuUV-3150). The total irradiationtime
of UV light was 180min, and solutions were stirred by using a
magnetic stirrer during UV light irradiations.
3. Results and discussion
3.1. Formation of -ZnWO
4
nanocrystals
The melt-quenched samples with the compositions
of 30WO
3
50ZnO20B
2
O
3
, 30WO
3
40ZnO30B
2
O
3
, and
30WO
3
30ZnO40B
2
O
3
include some amounts of crystals. On the
other hand, the melt-quenchedsamples of 10WO
3
50ZnO40B
2
O
3
and 20WO
3
50ZnO30B
2
O
3
have a good optical transparency. In
the XRD patterns for these two samples, only broad halo peaks
being typical for glassy materials were observed. These results
about the glass-forming tendency in the ternary WO
3
ZnOB
2
O
3
system is well consistent with that reported by Imaoka [24]. It is,
therefore, conrmed fromthe present study that the glass-forming
tendency in the samples with WO
3
contents of more than 30mol%
is weak. Considering the purpose of this study, it is favorable
to use glasses with WO
3
and ZnO contents as large as possible.
We, therefore, determined to use 20WO
3
50ZnO30B
2
O
3
glass
(designated here as 20WZB glass) and to examine its crystallization
behavior.
20WO
3
-50ZnO-30B
2
O
3
T
p1
=667C
T
p2
=748C
T
p3
=811C
E
x
o
.
E
n
d
o
.
500 600 700 800
Temperature /
o
C
Bulk
T
g
=490
o
C
Fig. 1. DTA curve of bulk 20WO
3
50ZnO30B
2
O
3
glass. Heating rate was 10K/min.
Tg andTp are the glass transitionandcrystallizationpeaktemperatures, respectively.
The optical photograph for the bulk glass is also included.
Fig. 1 shows the DTA pattern for the bulk 20WZB glass. An
endothermic dip corresponding to the glass transition and three
exothermic peaks corresponding tothe crystallizationare observed
clearly, providing the values of T
g
=490

C, T
p1
=667

C, T
p2
=748

C,
and T
p3
=811

C. The optical photograph for the 20WZB glass is

includedinFig. 1, indicatingcolorless inthe visible light region. This
suggests that the valence of Wions in the 20WZB glass is mainly
W
6+
. Even if W
5+
ions providing a color of brown are present in the
20WZB glass, their amount would be very small. From the optical
absorption spectrum, it was estimated that the 20WZB glass has
an optical absorption edge of the wavelength of =354nm (i.e.,
3.50eV).
Fig. 2 shows the XRD patterns for the samples obtained by
different heat treatment temperatures in the 20WZB glass. The
XRD peaks observed for the sample heat-treated at 680

C for
20 30 40 50 60 70
I
n
t
e
n
s
i
t
y
/
a
r
b
.
u
n
i
t
s
-ZnWO
4
680
o
C, 3h
2 /deg.
760
o
C, 3h
: Zn
4
O(BO
2
)
6
815
o
C, 3h
20WO
3
-50ZnO-30B
2
O
3
Fig. 2. XRD powder patterns for the samples heat-treated at 680, 760, and 815

C
for 3h in 20WO
3
50ZnO30B
2
O
3
glass.
T. Ida et al. / Journal of Asian Ceramic Societies 2 (2014) 253257 255
20WO
3
-50ZnO-30B
2
O
3
Heat-treated
610
o
C, 3 h
-ZnWO
4
20 30 40 50 60 70
2 /deg.
I
n
t
e
n
s
i
t
y

/
a
r
b
.

u
n
i
t
s
570
o
C, 3 h
530
o
C, 3 h
(111)
Fig. 3. XRDpowder patterns for the samples heat-treated at 530, 570, and 610

C for
3 h in 20WO
3
50ZnO30B
2
O
3
glass. The optical photographs for the heat-treated
samples are also included.
3h are assigned to -ZnWO
4
crystals (ICDD: No. 01-075-8594).
For the samples heat-treated at 760 and 815

C, the formation
of Zn
4
O(BO
2
)
6
crystals is observed besides -ZnWO
4
. The results
shown in Fig. 2 indicate that the initial crystalline phase appearing
in the crystallization of 20WZB glass is -ZnWO
4
. In order to exam-
ine the crystallization behavior of -ZnWO
4
crystals, the 20WZB
glass was heat-treated at temperatures lower than the rst crystal-
lization peak temperature of T
p1
=667

C, and the XRD patterns for

the samples obtained are shown in Fig. 3. It is seen that the samples
heat-treated at 570 and 610

C for 3h showXRD peaks assigned to

-ZnWO
4
crystals. It should be pointed out that XRDpeaks are very
broad, suggesting that the size of -ZnWO
4
crystals might be small.
The average particle size of -ZnWO
4
crystals formed in the heat-
treated (610

C, 3h) sample was estimated fromthe peak width of

XRD patterns using the Scherrers equation, in which the (111)
plane was used, and the value of 13nm was obtained. A TEM
photograph for the heat-treated (610

C, 3h) sample is shown in

Fig. 4. The sample for TEMobservations was prepared by grinding
plate-shaped crystallized glass, and the edge of grain particles was
observed. It is seen that crystals having a diameter of around 10nm
are present, being consistent with the average size (13nm) of -
ZnWO
4
crystals estimated from the Scherrers equation. The XRD
and TEMresults, therefore, demonstrate that -ZnWO
4
nanocrys-
tals are formed initially in the crystallization of 20WZB glass.
The optical absorption spectrum for the transparent heat-treated
(570

C, 3h) sample with -ZnWO

4
nanocrystals was measured,
and an optical absorption edge of =350nm (i.e., 3.54eV) was
obtained. This value is almost the same as that (=354nm) for the
base 20WZBglass. Garadkar et al. [29] reportedthe optical bandgap
(E
g
) of E
g
=3.4eV for ZnWO
4
nanoparticles (10nm). Huang and
Zhu[2] reportedthe value of E
g
=3.02eVfor ZnWO
4
powders witha
diameter of 200500nm. The sample obtained in this study is com-
posed of the glassy phase and -ZnWO
4
nanocrystals, and further
studies would be necessary to determine the optical band gap of
-ZnWO
4
nanocrystals themselves. At this moment, the amount of
Fig. 4. TEM photograph for the sample heat-treated at 610

C for 3h in
20WO
3
50ZnO30B
2
O
3
glass.
-ZnWO
4
nanocrystals has not beendetermined. However, consid-
ering the chemical composition of 20WO
3
50ZnO30B
2
O
3
glass,
after the formation of -ZnWO
4
nanocrystals with the ratio of
ZnO/WO
3
=1, thechemical compositionof theresidual glassyphase
would be close to 30ZnO30B
2
O
3
with the ratio of ZnO/B
2
O
3
=1.
This would be a reason for the formation of Zn
4
O(BO
2
)
6
crys-
tals with the ratio of ZnO/B
2
O
3
=0.67 as the second crystalline
phase.
The glass of 20WO
3
50ZnO30B
2
O
3
includes a relatively small
amount (i.e., 30mol%) of B
2
O
3
which is a glass former. The stability
of boratestructures depends onthedelocalizationof formal charges
of B
n
O
m
anions as a result of their polymerization [32]. Considering
the amount of B
2
O
3
content, it is expected that the degree of the
polymerization of BOB bonds would be small (i.e., short). Fur-
thermore, it is recognized that the polymerized borates are often
less stable for high-valence andsmall-sizedcations [32,33]. Cations
of higher valence such as WO
3
, MoO
3
, and Nb
2
O
5
can formrather
rigid coordination polyhedra with oxygen atoms. In the binary
systems such as WO
3
B
2
O
3
, MoO
3
B
2
O
3
, and Nb
2
O
5
B
2
O
3
, it is
expected that the glass formation would be extremely difcult.
Indeed, any wide glass-forming region has not been reported in
these binary borate systems [28]. On the other hand, the glass for-
mation has been conrmed in the binary systemof ZnOB
2
O
3
[28],
i.e., in the compositions of (43.963.6)ZnO(56.136.4)B
2
O
3
[28],
consequentlyprovidingtheglass formationintheternarysystemof
WO
3
ZnOB
2
O
3
. This information on the glass-forming tendency
suggests that it might be difcult to create rigid network struc-
ture with strong chemical bonds such as WOB in the ternary
WO
3
ZnOB
2
O
3
system. Furthermore, it is considered that the
formation of compounds containing both WO
3
and ZnO such as
-ZnWO
4
, but containing no boron atoms, would be enhanced in
WO
3
ZnOB
2
O
3
glasses. The above structural concept in glasses
is an important clue for the design and control of crystallization
in borate glasses. Indeed, various functional nanocrystals have
been formed easily through the crystallization of borate glasses,
e.g., -ZnMoO
4
nanocrystals in MoO
3
ZnOB
2
O
3
glasses [28], fer-
roelectric Sr
x
Ba
1x
Nb
2
O
6
nanocrystals in SrOBaONb
2
O
5
B
2
O
3
glasses [34], ferroelectric Ba
1x
RE
2x/3
Nb
2
O
6
nanocrystals (RE: Sm,
Eu, Gd, Dy, Er) in RE
2
O
3
BaONb
2
O
5
B
2
O
3
glasses [17], and
CaF
2
nanocrystals in CaF
2
NaFCaOAl
2
O
3
B
2
O
3
SiO
2
glasses
[35].
256 T. Ida et al. / Journal of Asian Ceramic Societies 2 (2014) 253257
Fig. 5. Excitation spectrum (a) monitored by the emission of =482nm and pho-
toluminescence spectrum (b) at the excitation of =267nm for the heat-treated
(664

C, 3h) sample containing -ZnWO

4
nanocrystals in 20WO
3
50ZnO30B
2
O
3
glass. The optical photograph (c) for the heat-treated sample with a blue photolu-
minescence is also included.
3.2. Photoluminescence of -ZnWO
4
nanocrystals
The excitation spectrumof the heat-treated (664

C, 3h) sample
containing-ZnWO
4
nanocrystals is showninFig. 5(a), inwhichthe
emissionof =482nmwas monitored. Abroadexcitationemission
peakedat 270nmis observed. APL spectrumat the excitationof
=267nmfor the sample is shown in Fig. 5(b). A broad and asym-
metric emission peaked at 475nmis observed, providing a blue
color (Fig. 5(c)). A blue emission in -ZnWO
4
has been considered
to be related to WO
6
polyhedra [3638]. A molecular orbital model
for the octahedral (WO
6
)
6
oxyanion complex (O
h
point symme-
try) shows that the highest occupied state with a t
1g
symmetry
is associated with the 2p orbital of oxygen and the excited state
consists of an electron at the W 5d orbital with a t
2g
symmetry
[38]. That is, the excitation and emission spectra in -ZnWO
4
are
related to an electronic transition between the O(2p) and W(5d)
states in the WO
6
group. Zinc tungstate -ZnWO
4
has the wol-
framite crystal structure, in which the WO
6
octahedral complex
has an asymmetric shape with short, medium, and long WO bond
distances [38]. The deformation of WO
6
octahedra in -ZnWO
4
would be related to the appearance of the broad and asymmetric
emission and PL spectra shown in Fig. 5. It is, therefore, concluded
that -ZnWO
4
nanocrystals formed through the crystallization
of 20WO
3
50ZnO30B
2
O
3
glass have the electronic state being
similar to -ZnWO
4
crystals synthesized by other preparation
techniques.
Fig. 6. SEMphotographs for the pulverized particles (a) for the heat-treated (610

C,
3 h) sample and for particles (b) obtained by etching in 1N HNO
3
solution for the
heat-treated sample in 20WO
3
50ZnO30B
2
O
3
glass.
3.3. Photocatalytic properties of -ZnWO
4
nanocrystals
For the photocatalytic activity of -ZnWO
4
nanocrystals, the
crystallized samples obtained by a heat treatment at 610

C for
3h were used. The samples were pulverized by a agate mortar,
and the SEM photograph for the particles obtained is shown in
Fig. 6(a), indicating the particle size of 110mand sharp surfaces.
UV light (=254nm) was irradiated onto the solution consisting of
these particles and methylene blue. However, any degradation of
methylene blue, i.e., the decrease in the intensity of optical absorp-
tions, was not observed. That is, any photocatalytic activity was
not conrmed in the particles of the crystallized sample with -
ZnWO
4
nanocrystals. In the crystallized samples themselves, it is
considered that the area of -ZnWO
4
nanocrystals exposing at the
surface would be small, because many -ZnWO
4
nanocrystals are
surrounded by the residual glassy phase and also are present in the
interior of the particles.
In order to increase the exposure area of -ZnWO
4
nanocrys-
tals at the surface (i.e., the elimination of the glassy phase), the
pulverized particles were etched by using a 1N HNO
3
solution,
and the SEM photograph for the particles obtained is shown in
Fig. 6(b). It is seen that the surface state of the etched particles
(Fig. 6(b)) changes largely in comparison with that of non-etched
particles (Fig. 6(a)). The appearance of the rough surface shown
in Fig. 6(b) indicates that the glass of 20WO
3
50ZnO30B
2
O
3
is
etchedeffectively by a 1NHNO
3
solution. UVlight (=254nm) was
T. Ida et al. / Journal of Asian Ceramic Societies 2 (2014) 253257 257
500 600 700 800
0.3
0.4
0.5
0.6
0.7
0.8
30 min
20WO
3
-50ZnO-30B
2
O
3
Heat-treated
610
o
C, 3 h
Etching
1N HNO
3
, 30 min
Powders
0 min
60 min
90 min
120 min
180 min
Wavelength /nm
A
b
s
o
r
b
a
n
c
e
Fig. 7. Optical absorption spectra in the visible light region at roomtemperature for
the solution of etched (1N HNO
3
) powders and methylene blue under different UV
light (=254nm) irradiation times.
irradiated onto the solution of these etched particles and methy-
lene blue, and the results on the optical absorption spectra in the
visible light region at room temperature are shown in Fig. 7. It is
seen that the intensity of optical absorption due to the methylene
blue decreases with increasing UV light irradiation time. In partic-
ular, for the irradiation time of 180min, it is considered that the
methylene blue present in the solution is almost decomposed. The
results shown in Fig. 7, therefore, indicate that -ZnWO
4
nanocrys-
tals formed through the crystallization of 20WO
3
50ZnO30B
2
O
3
glass have photocatalytic activities. Similar experiments were car-
ried out for TiO
2
particles (Nippon Aerosil Co. P25, particle size:
21nm) inorder to conrmthe validity of our experiments applied
in this study, and it was found that the methylene blue present
in the solution was almost decomposed in the UV (=254nm)
irradiation time of 90min. Garadkar et al. [29] examined the pho-
tocatalytic activity of ZnWO
4
nanoparticles (10nm) synthesized
by a simple microwave assisted technique for the degradation of
methylene blue in a solution (100mL, 1.010
5
mol/L) under UV
light (=254nm) and found that the UV light irradiation time of
60min is enough for the decomposition of methylene blue. The
photocatalytic activity of -ZnWO
4
nanocrystals formed through
the crystallization of glasses in this study is, therefore, not so high
comparedwiththe data reportedsofar [29]. Inthis study, the glassy
phase that remained in the crystallized glasses were etched by
using a 1NHNO
3
solution, and -ZnWO
4
nanocrystals were taken.
It is required to clarify the surface state of -ZnWO
4
nanocrys-
tals taken by the etching process. Furthermore, it is of interest to
study photocatalytic properties and behaviors including interme-
diate products for our samples in more detail. It is also strongly
desired to pattern -ZnWO
4
nanocrystals more densely only at the
surface of bulk WO
3
ZnOB
2
O
3
glasses for practical applications,
for instance, by using laser-induced crystallization techniques [39].
4. Conclusions
The WO
3
-containing glasses based on the WO
3
ZnOB
2
O
3
sys-
temwere preparedusing a conventional melt quenching methodin
order to design crystallized glasses with -ZnWO
4
nanocrystals. It
was difcult to prepare glasses with a large amount (30mol%)
of WO
3
, but the melt-quenched sample with the composition
of 20WO
3
50ZnO30B
2
O
3
showed an optically transparent glass
(20WZB glass). The 20WZB glass showed the bulk crystallization
of -ZnWO
4
nanocrystals with a diameter of 10nm. Broad and
asymmetric emissions peaking at the wavelength of 475nm, i.e.,
blue emissions, inthe photoluminescence spectrumwere observed
in the samples with -ZnWO
4
nanocrystals. Fromthe degradation
of the absorption of methylene blue color under UV light irradi-
ations, it was claried that -ZnWO
4
nanocrystals formed have
photocatalytic activities.
Acknowledgements
This study was supported by the Grant-in-Aid for Scientic
Research from the Ministry of Education, Science, Sport, Culture,
and Technology, Japan (No. 23246114), and by Program for High
ReliableMaterials DesignandManufacturinginNagaokaUniversity
of Technology.
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