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Synthesis and enhanced luminescence of uniform and well-dispersed
quasispherical YVO4:Ln3+ (Ln ¼ Eu, Dy) nanoparticles by a solvothermal
method†
Guang Jia,*a Cuimiao Zhang,a Shiwen Ding,a Liyong Wang,a Lanfen Lia and Hongpeng You*b
Published on 04 November 2011 on http://pubs.rsc.org | doi:10.1039/C1CE05725A

Received 14th June 2011, Accepted 1st October 2011

DOI: 10.1039/c1ce05725a

Uniform and well-dispersed quasi-spherical YVO4:Ln3+ (Ln ¼ Eu, Dy) nanoparticles have been
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successfully synthesized through a solvothermal approach using EG and PVP as solvent and surfactant,
respectively. SEM and TEM images indicate that the as-obtained quasispheres are composed of tiny
packed nanocrystallites. The YVO4:Eu3+ and YVO4:Dy3+ samples show strong red and yellow light
emissions under ultraviolet excitation. The luminescence intensities of the phosphors are greatly
enhanced by co-doping Ba2+ ions into the YVO4 host lattice. Nitrogen adsorption–desorption
measurements reveals that the as-synthesized luminescent quasi-spherical nanoparticles have a porous
structure, which might find potential applications in the fields of luminescence, drug delivery, and
disease therapy.

Introduction synthesize YVO4 phosphors.23,24 However, the uniformity and

In recent years, rare earth materials have been widely used as
high-performance luminescent devices, catalysts, and other
functional materials based on the electronic, optical, and chem-
ical characteristics arising from their 4f electrons.1–5 Among
various rare earth compounds, lanthanide ion (Ln3+) doped
yttrium orthovanadate (YVO4) phosphors have attracted inten-
sive attention due to their excellent thermal, mechanical, and
optical properties and have been widely applied in light phosphor
powders, flat panel displays, and field emission display devices.6–9
Moreover, investigations show that nanoscaled YVO4:Ln3+
phosphors, especially water soluble nanocrystals, have a signifi-
cant promise in biological fields.10,11 Over the past decades, much
research attention has been devoted to the investigation of the
YVO4:Ln3+ phosphors with high efficiency.12,13 Moreover,
various morphologies of YVO4 have been synthesized according
to different synthesis methods, such as nanocrystals,10,14,15
nanowires,12,16 microflowers,17 thin films,18 core–shell struc-
tures,19,20 nanobelts and octahedral microcrystals.21,22 To our
knowledge, there have been few reports on the synthesis of
uniform and well-dispersed quasi-spherical YVO4 nanoparticles.
Recently, solvothermal methods have been developed to
a
College of Chemistry and Environmental Science, Hebei University,
Baoding, 071002, P. R. China. E-mail: guangjia2001@yahoo.cn; Tel:
+864315971111
b
State Key Laboratory of Rare Earth Resource Utilization, Changchun
Institute of Applied Chemistry, Chinese Academy of Sciences,
Changchun, 130022, P. R. China. E-mail: hpyou@ciac.jl.cn
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c1ce05725a
dispersion of as-synthesized YVO4 samples are desired to be
increased. YVO4:Ln3+ phosphors are proven to be an effective
luminescent probe for drug delivery systems. To date, some
delivery systems have been successfully fabricated by the
combination of YVO4:Ln3+ and mesoporous silica because the
mesoporous structure is an essential parameter for drug
carriers.25–27 To date, the YVO4:Ln3+ luminescent materials with
porous structure have been seldom reported. If the uniform, well-
dispersed, and mesoporous YVO4:Ln3+ phosphors can be
obtained, they can be directly utilized to be drug carrier and have
great potential in the drug delivery and disease therapy fields.
Recently, Tian and Wang’s groups have reported the enhanced
photoluminescence of YVO4:Ln3+ by co-doping large-sized
divalent ions, such as Sr2+, Ba2+, and Pb2+ ions.28,29 However, the
exact luminescent mechanisms for the enhancement lumines-
cence are not very clear at present and need to be explored.
In the past decade years, the synthesis of inorganic nano-/
micromaterials with well-defined and controllable morphologies
has attracted considerable attention, because the properties of
such materials are closely related to geometrical factors such as
morphology, dimensionality, and size. Many synthesis tech-
niques have been developed to fabricate the inorganic functional
materials, such as sol-gel processes, precipitation, combustion,
microemulsion, chemical vapor technique, and so forth. Among
the various synthesis routes, the solvothermal method, as
a typical solution approach, has been proven to be an effective
and convenient process in preparing various inorganic materials
with a variety of controllable morphologies and architec-
tures.30,31 In addition, ethylene glycol (EG) and polyvinyl
pyrrolidone (PVP) are considered to be an effective solvent and

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surfactant in the solvothermal process to control the
morphology, particle size, and distribution of the products. To
date, an EG solvent accompanied with a PVP surfactant have
been widely applied to prepare various inorganic functional
materials with a variety of controllable morphologies and
architectures via a solvothermal method, such as CdS colloidal
spheres,32 ZnSe microspheres and microflowers,33 Fe3O4 micro-
spheres,34 PbSe and NiSe2 hollow spheres,35 etc. However, to the
best of our knowledge, little attention has been paid to the
preparation of rare earth compounds by this facile and efficient
synthesis route.
In the present study, uniform, well-dispersed, and mesoporous
quasispherical YVO4:Ln3+ (Ln ¼ Eu, Dy) nanoparticles have
Published on 04 November 2011 on http://pubs.rsc.org | doi:10.1039/C1CE05725A
been successfully synthesized through a solvothermal approach
at relatively low temperature by using EG and PVP as solvent
and surfactant. The formation process and luminescence prop-
erties of the products were investigated in detail. Moreover, this
synthesis route may be of great significance in the preparation of
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other uniform and well-defined rare earth functional materials.
Results and discussion
Phase identification, morphology, and formation process
Fig. 1 shows the XRD patterns of the YVO4, YVO4:Eu3+, and
YVO4:Dy3+ samples prepared at 120  C for 24 h (pH ¼ 10). The
diffraction peaks of all the three samples can be well indexed to
the tetragonal phase of YVO4 (JCPDS No. 17-0341). No addi-
tional peaks of other phases can be detected, revealing the
formation of tetragonal YVO4 phase. Compared with the
pure YVO4 phase, the diffraction peaks of YVO4:Eu3+ and
YVO4:Dy3+ samples (Fig. 1b, c) shift slightly to the lower angle
side, indicating that the Eu3+ and Dy3+ ions with bigger radii have
been effectively doped into the YVO4 host lattice due to the
Fig. 1 XRD patterns of (a) YVO4, (b) YVO4:Eu3+, (c) YVO4:Dy3+
samples prepared at 120  C for 24 h. The standard data of tetragonal
YVO4 (JCPDS No. 17-0341) is presented as a reference.
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Bragg equation 2dsinq ¼ l (d is the distance between two crystal
planes, q is the diffraction angle of an observed peak, and l is the
X-ray wavelength). The XRD patterns of the YVO4:Eu3+, Ba2+,
and YVO4:Dy3+, Ba2+ samples show that the diffraction peaks of
the two samples agree well with the pure tetragonal phase of
YVO4, and no impurity peak can be observed (Fig. S1, ESI†).
This result indicates that the Ba2+ can also be effectively doped
into the YVO4 host lattice.
SEM and TEM were used to characterize the morphology and
crystal structure of the products. Fig. 2a shows typical SEM
images of YVO4 sample prepared at 120  C for 24 h, which
reveals that the sample consists of uniform and well-dispersed
quasi-spherical nanoparticles with the average diameter in the
range of 70–100 nm. From the enlarged SEM image of the
sample (Fig. 2b), it can be seen that the surfaces of the quasi-
spheres are rough in nature. The TEM image of the YVO4
sample exhibits the quasi-spherical morphology with good
dispersion (Fig. 2c), agreeing well with the SEM images. More-
over, the TEM image indicates that an individual quasi-sphere is
not a single particle but the assembly of tiny packed YVO4
nanocrystallites, which can be confirmed by the nitrogen
adsorption/desorption analysis (Fig. 4). It should be mentioned
that the morphologies of Eu3+, Dy3+, and Ba2+ doped samples are
identical to the pure YVO4 sample (not shown). The SAED
pattern (Fig. 2d) taken from a single quasi-sphere can be indexed
as the (200), (112), (312), and (400) reflections of the tetragonal
phase of YVO4, which agrees well with the XRD results.15,19,36
Generally, successful syntheses of nano/microcystals in
a solution-based system not only depends on the intrinsic
structure of the target compounds but also requires more
fastidious control of the reaction conditions such as reaction
temperature and time, the pH value of initial solution, organic
additives, and so forth.37,38 In our present study, the influence on
the reaction conditions, such as reaction temperature and time,
the pH value of initial solution, the amount of PVP, etc. was
investigated. Fig. 3a shows the SEM image of the YVO4 sample
prepared at 120  C for 48 h. It can be seen from Fig. 3a that the
morphology and dispersion of the sample have no obvious
change except for the slight increase of the particle size by
increasing the reaction time. At relatively lower reaction
Fig. 2 (a, b) SEM, (c) TEM images, and (d) SAED pattern of quasi-
spherical YVO4 nanoparticles.
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formation and assembly of YVO4 nanocrystallites into mono-

disperse nanosized quasispheres, which may be similar to the
formation of CdS,32 Fe3O4,34 and CoFe2O442 nanospheres via the
solvothermal process. The formation of the YVO4 nanoparticle-
based quasispheres may be described as follows: initially, Y3+
ions in the reaction medium formed complex coordinate bonds
with PVP, which reacted with the VO43 ions, forming YVO4
monomers. After the nucleation, the YVO4 monomers grew into
YVO4 nanocrystallites stabilized by PVP. Driven by the mini-
mization of the total energy of the system, the initially formed
primary nanocrystallites, which then acted as the cores for the
subsequent assembly of the new ones, might aggregate together
Published on 04 November 2011 on http://pubs.rsc.org | doi:10.1039/C1CE05725A

to form uniform quasi-spherical YVO4 particles.33,43 However,

the amount of PVP should be controlled in a proper range and
excessive PVP additive results in the serious aggregation for the
nanoparticles (Fig. 3f).
The surface area and porosity of the as-obtained YVO4 sample
were investigated by nitrogen adsorption–desorption isotherms,
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as shown in Fig. 4. It can be seen that the YVO4 sample show

similar N2 adsorption and desorption isotherms and typical H1
hysteresis loops, which are properties of typical mesoporous
materials. The BET surface area of the sample is about 163.7 m2
g1, and the pore volume is 0.43 cm3 g1. The result reveals that
Fig. 3 SEM images of the samples prepared at (a) 120  C for 48 h, (b)
180  C for 24 h, (c) 220  C for 24 h, and 120  C for 24 h, (d) pH ¼ 12, (e) the YVO4 quasispheres have a porous structure and are
deionized water as solvent, (f) 0.88 g of PVP as surfactant. composed of a porous network of tiny and aggregated nano-
particles with a porosity arising from the interparticle space,44,45
which is in accordance with the TEM observation (Fig. 2). As we
temperatures (lower than 120  C), the YVO4 quasi-spherical know, the highly efficient drug carrier generally requires some
nanoparticles can not be obtained. With the increase of the unique characteristics, such as uniform morphology, porous
reaction temperature to 180  C (24 h), the sample becomes badly- structure, large surface areas, good dispersion, etc.45 The as-
dispersed in distribution due to the aggregation of nanoparticles synthesized YVO4:Ln3+ luminescent materials exactly meet the
(Fig. 3b). By increasing the reaction temperature to 220  C, the above requirements and may be potentially applied in the drug
as-obtained sample exhibits an irregular shape and a broad size delivery field.
distribution (Fig. 3c). By further increasing the reaction The energy dispersive X-ray (EDX) spectra were further used
temperature, the product exhibits serious agglomeration and to investigate the as-obtained YVO4:Eu3+ and YVO4:Eu3+, Ba2+
broader size distribution (not shown). The pH value in the samples (Fig. 5). The EDX spectrum of the YVO4:Eu3+ sample
reaction system is another critical external parameter in deter- (Fig. 5a) confirms the presence of yttrium (Y), oxygen (O),
mining the architectural features of the inorganic crystals.38,39 vanadium (V), and europium (Eu) elements. No other impurity
When the pH value of the initial solution increases to 12, the peaks can be detected, which can effectively support the XRD
particle size increases obviously and the nanoparticles tend to results of the sample. Compared with YVO4:Eu3+, the Ba2+ peak
assemble into quasi-octahedral crystals (Fig. 3d). The tendency can be detected in the EDX spectrum of the YVO4:Eu3+, Ba2+
from quasi-spherical to octahedral morphology of the product sample (Fig. 5b). The result indicates that Ba2+ has been
can be ascribed to the preferential ionic interaction with strong
alkaline conditions in the solvothermal process. The similar
phenomenon often occurs in lanthanide orthovanadates as
reported in previous literatures.21,22,40
Ethylene glycol (EG) has proven to be an effective solvent in
solvothermal processes and has been widely used to fabricate
various inorganic materials with a variety of controllable
morphologies and architectures, such as CdS,32 ZnSe,33
Fe3O4,34,41 etc. In order to identify the role of EG in the forma-
tion of YVO4 quasispheres, the product obtained in aqueous
solution (without EG in the reaction system) was characterized
by SEM, as shown in Fig. 3e. The result indicates that the as-
synthesized sample consists of aggregated, tiny, and irregular
nanoparticles instead of the uniform and well dispersed quasi-
spherical particles (Fig. 2), which indicates that the EG solvent
plays a crucial role in the formation of YVO4 sample. In addi-
tion, the PVP additive also plays an important role in the Fig. 4 Nitrogen adsorption/desorption isotherms for YVO4 sample.

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Published on 04 November 2011 on http://pubs.rsc.org | doi:10.1039/C1CE05725A
Fig. 5 EDX spectra of (a) YVO4:Eu3+ and (b) YVO4:Eu+, Ba2+ samples.
incorporated into the YVO4 host lattice during the synthesis
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process, which agrees well with the XRD result (Fig. S1, ESI†). It
should be noted that a similar situation holds for the YVO4:Dy3+,
Ba2+ sample.
Luminescence properties
Fig. 6a, b shows the excitation and emission spectra of the YVO4:
Eu3+ and YVO4:Eu3+, Ba2+ samples. The excitation spectra
(Fig. 6a) consist of a strong absorption band at about 278 nm
Fig. 6 PL excitation and emission spectra of (a, b) YVO4:Eu3+, YVO4:
Eu+, Ba2+ and (c, d) YVO4:Dy3+, YVO4:Dy+, Ba2+ samples.
576 | CrystEngComm, 2012, 14, 573–578
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and several weak lines. The strong absorption band is assigned to
the charge transfer overlap of VO43 absorption and charge
transfer transition between Eu3+ and O2.46 The weak lines in the
longer wavelengths are attributed to the f–f transitions within the
4f6 configuration of the Eu3+ ions, respectively. The absorption
intensity of the f–f transitions of the Eu3+ is very weak in
comparison with that of the VO43 groups, indicating that the
excitation of the Eu3+ ions is mainly through the VO43 groups,
i.e., by the energy transfer from the VO43 groups to Eu3+
ions.15,22 Upon excitation at 278 nm, the emission spectra
(Fig. 6b) of the two samples exhibit several groups of emission
lines at about 537, 592, 618, 651, and 696 nm, which are ascribed
to the 5D1–7F1 and 5D0–7FJ (J ¼ 1, 2, 3, 4) transitions of the Eu3+
ions, respectively. No emission from the VO43 groups was
observed, indicating that the energy transfer from the VO43
groups to Eu3+ ions is very efficient. The emission spectrum is
dominated by the 5D0–7F2 (618 nm) transition of the Eu3+ ions,
which is an electric-dipole allowed transition and hypersensitive
to the environment. It can be seen from Fig. 6a, b that the YVO4:
Eu3+ and YVO4:Eu3+, Ba2+ samples show similar spectral
patterns without any emission band shift, but one can clearly
observe that the YVO4:Eu3+, Ba2+ sample has a higher photo-
luminescence intensity than that of YVO4:Eu3+. When Ba2+ ions
are incorporated into the YVO4:Eu3+ lattice, the energy transfer
from excited states of O2 (the charge transfer states) to Eu3+ ions
obviously enhances.28,29 On the other hand, the charge-to-radius
ratio of the Ba2+ ions is smaller than that of the Y3+ ions. When
the Ba2+ is substituted into the Y3+ site in the lattice, a tight
binding of the oxygen electrons toward the Y3+ is expected to be
released. Hence, the charge transfer state excitation band of Eu3+
is enhanced by co-doping Ba2+ ions into the YVO4 lattices,
leading to the enhanced emission of Eu3+ ions. Hence, the
luminescent intensity of YVO4:Eu3+ is increased by the Ba2+
incorporation into the lattices. The similar enhancement lumi-
nescence phenomenon has also been observed in the YVO4:Dy3+,
Ba2+ sample (Fig. 6c, d).
Fig. 6 c,d displays the excitation and emission spectra for the
YVO4:Dy3+ and YVO4:Dy3+, Ba2+ samples. The excitation
spectra (Fig. 6c) mainly consist of an intense band with
a maximum at 310 nm, which are due to the absorption of the
VO43 groups. Upon 310 nm excitation, there are two dominant
bands in the emission spectra of the two samples (Fig. 6d). The
yellow band (573 nm) corresponds to the hypersensitive transi-
tion 4F9/2–6H13/2 and the blue band (482 nm) corresponds to the
4
F9/2–6H15/2 transition of Dy3+ ions. There is a very weak emission
band located at about 662 nm, which corresponds to the
4
F9/2–6H11/2 transition.14,17 In addition, one can see that the
YVO4:Dy3+, Ba2+ sample shows identical spectral patterns and
higher luminescence intensity in comparison with the YVO4:Dy3+
sample, which is similar to the YVO4:Eu3+, Ba2+ sample (Fig. 6a,
b). On the basis of the results mentioned above, it can be
concluded that Ba2+ is an effective co-dopant to enhance the
luminescence intensities of YVO4:Ln3+ phosphors.
The YVO4:Eu3+, Ba2+ and YVO4:Dy3+, Ba2+ samples show
intense red and yellow emissions under ultraviolet excitation,
which can be confirmed by the CIE (Commission Internationale
de I’Eclairage 1931 chromaticity) coordinates for the emission
spectra of the YVO4:Ln3+, Ba2+ (Ln ¼ Eu and Dy) samples
(Fig. 7). The chromaticity coordinates of YVO4:Eu+, Ba2+ and
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Fig. 7 CIE chromaticity diagram of YVO4:Eu+, Ba2+ (point a) and
YVO4:Dy+, Ba2+ (point b) samples.
YVO4:Dy3+, Ba2+ samples are x ¼ 0.611, y ¼ 0.335 and x ¼ 0.355,
y ¼ 0.405, locating in the red and yellow region, respectively. The
result is in good accordance with the YVO4:Ln3+ phosphors in
previous literatures.15
Fig. 8 Decay curves for the as-prepared samples: (a) YVO4:Eu3+, (b)
YVO4:Dy3+.
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The representative decay curves for the luminescence of the
Eu3+ (618 nm, 5D0–7F2) and Dy3+ (573 nm, 4F9/2–6H13/2) in the
YVO4:Eu3+ and YVO4:Dy3+ samples are shown in Fig. 8.
The decay curves for the luminescence of the Eu3+ and Dy3+ ions
can be well fitted into a double-exponential function as I ¼ A1exp
(t/s1) + A2exp(t/s2), in which s is the decay lifetime. The
double-exponential decay behavior of the activator is often
observed when the excitation energy is transferred from the
donor.15,20 The average lifetime of Eu3+ and Dy3+ in YVO4 host
lattices are determined to be 0.435 and 0.286 ms, respectively,
which are basically in agreement with the previous reports given
for the YVO4:Ln3+ (Ln ¼ Eu, Dy) phosphors.14,19,20,22 Moreover,
the similar decay curves can also be obtained for the YVO4:Eu3+,
Ba2+ and YVO4:Dy3+, Ba2+ samples (Fig. S2, ESI†).
Conclusions
In summary, a facile solvothermal method has been developed to
fabricate uniform and well-dispersed quasi-spherical YVO4
nanoparticles. The morphology, crystal structure, formation
process, and luminescence properties were characterized by
XRD, SEM, TEM, N2 adsorption–desorption isotherms, PL,
and kinetic decays, respectively. Under ultraviolet excitation, the
Eu3+ and Dy3+ doped YVO4 samples show strong red and yellow
emissions, respectively. By co-doping Ba2+ ions into the YVO4
host lattice, the samples show identical spectral patterns and
higher photoluminescence intensities. The possible luminescent
mechanisms for the enhancement luminescence were discussed in
detail. The as-synthesized products may find potential applica-
tions in fields such as luminescence, drug delivery, and disease
therapy due to their excellent dispersing, mesoporous, and
luminescence properties. Furthermore, this solvothermal route
may be expanded to the synthesis of other rare earth functional
materials.
Experimental
Ln(NO3)3 (Ln ¼ Y, Eu, and Dy) aqueous solutions were
obtained by dissolving Ln2O3 (99.99%) in dilute HNO3 solution
under heating with agitation. All other reagents used were of
analytical purity and were directly used without further
purification.
In a typical synthesis, 0.80 g of Na3VO4$12H2O (2 mmol) and
0.22 g of polyvinyl pyrrolidone (PVP, K-30, Ms z 30 000) were
added to 35 mL of ethylene glycol (EG) under stirring. Subse-
quently, 2 mL of 1 M Y(NO3)3 aqueous solution was added to
the above solution. Then NaOH solution (2 M) was introduced
to the stirred solution until pH ¼ 10. After additional agitation
for 10 min, the mixture was transferred to a 50 mL autoclave and
maintained at 120  C for 24 h. When the autoclave was naturally
cooled down to room temperature, the resulting precipitate was
collected, centrifuged, and washed with deionized water and
ethanol for several times respectively and finally dried at 60  C in
air. Different reaction conditions, such as reaction temperature
and time, amount of PVP, pH value, and solvent were selected to
investigate the effects of these factors on the morphological and
structural properties of the samples.
A similar process was employed to prepare YVO4:5%Eu3+,
YVO4:5%Eu3+, 5%Ba2+, YVO4:5%Dy3+, and YVO4:5%Dy3+, 5%
CrystEngComm, 2012, 14, 573–578 | 577

Ba2+ samples (molar ratio) by using a proper amount of Eu
(NO3)3, Dy(NO3)3, and Ba(NO3)2 solutions instead of Y(NO3)3
at the initial stage as described above.
The samples were characterized by powder X-ray diffraction
(XRD) performed on a D8 Focus diffractometer (Bruker). The
morphology and composition of the samples were inspected
using a scanning electron microscope (SEM; S-4800, Hitachi)
equipped with an energy-dispersive X-ray spectrum (EDX;
XFlash-Detector 4010, Bruker). Transmission electron micros-
copy (TEM) images and selected area electron diffraction
(SAED) pattern were obtained by an FEI Tecnai G2 S-Twin
transmission electron microscope. Nitrogen adsorption/desorp-
Published on 04 November 2011 on http://pubs.rsc.org | doi:10.1039/C1CE05725A
tion analysis was performed with a Micromeritics ASAP 2020M
apparatus. The specific surface area was determined by the
Brunauer–Emmett–Teller (BET) method. Photoluminescence
(PL) excitation and emission spectra were recorded with a Hita-
chi F-4500 spectrophotometer. The luminescence decay curves
were obtained from a Lecroy Wave Runner 6100 Digital Oscil-
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loscope (1 GHz) using a tunable laser (pulse width ¼ 4 ns, gate ¼
50 ns) as the excitation (Contimuum Sunlite OPO). All
measurements were performed at room temperature.
Acknowledgements
This work is financially supported by the University Scientific
Research Project of Hebei Education Department (Grant No.
2011171), Scientific Research and Development Project of
Baoding, Research Plan of the Natural Science Foundation of
Hebei University (Grant No. 2010-200), the Fund for Creative
Research Groups (Grant No. 20921002), and the National Basic
Research Program of China (973 Program, Grant No.
2007CB935502)
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