Materials Letters 102–103 (2013) 59–61

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Co-precipitation preparation, characterization and optical properties

of blue CaSb2O6: Bi3+ nano-phosphor
Liumin Chen, Yumei Long, Yumin Qin, Weifeng Li n
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China

art ic l e i nf o a b s t r a c t

Article history: Bi3+ doped CaSb2O6 nanoparticles were prepared by the co-precipitation technique followed by heat-
Received 30 January 2013 treatment. The as-prepared samples were characterized by X-ray diffraction (XRD), scanning electron
Accepted 22 March 2013 microscopy (SEM) and photoluminescence (PL) spectra. It was found that the CaSb2O6:xBi nano-crystals
Available online 30 March 2013
exist in the hexagonal phase, and show sphere-like shape with diameters of 60–80 nm. The CaSb2O6:xBi
Keywords: exhibited a strong emission band with peak wavelength of 437 nm at room temperature, which can be
CaSb2O6:Bi effectively excited both at 295 and 336 nm. It is believed that the formation of defect clusters such as
Nanoparticles ½ðBiCa Þ−ðV Ca Þ′ and/or ½ðBiCa Þ−ðV Ca Þ−ðBiCa Þ would play an important role on the optical properties of
Phosphors CaSb2O6:xBi phosphors. The intense blue emission and a higher quenching concentration suggested the
Defects
potential application of nano-scaled CaSb2O6:xBi for lighting and display devices.
& 2013 Elsevier B.V. All rights reserved.

1. Introduction This work reported on the synthesis of CaSb2O6:Bi3+ phosphors

The development of lighting and display systems with higher
resolution and higher luminous efficiency continues to spur the
search for novel luminescence materials. Great efforts have been
dedicated to rare-earth ions as optical activators that present
stable emission due to f–f electron transition. As a matter of fact,
main group metal ions with s2 configuration are also excellent
luminescence centers and attractive luminescence properties have
been found [1,2]. The Bi3+ ion is of great importance as a
luminescence activator [2–5] and its emission is attributed to the
electron transition between the 6s2 ground states and the 6s6p
excited states. Because of the strong interaction with the sur-
rounding lattice and energy transfer from Bi3+ to Bi3+ or to another
activator in different host lattices, the emission spectra of Bi3+ ions
presents a broad band and the peak position of the band varies
from the UV region to the red region with differing host lattices
[4–7]. It is therefore expected that favorable optical properties can
be achieved by doping Bi3+ ion into appropriate matrixes.
The preparation and luminescence properties of MSb2O6:Bi
(M ¼Ca, Sr) have been reported previously [8–10]. The only
reported synthetic method is the solid state reaction. Due to the
volatility of Bi2O3 and the tendency of Bi3+ to be oxidized to Bi5+ in
the conventional sintering process, the visible emission quenching
of MSb2O6:Bi (M ¼Ca, Sr) at room temperature occurred [8,11].
n
Corresponding author. Tel.: +86 512 65880089.
E-mail address: liweifeng@suda.edu.cn (W. Li).
by the co-precipitation method, which claims for low calcination
temperature, short reaction time and mass-produced [12,13]. The
optical properties of the as-synthesized samples were studied and
the luminescence mechanism was also discussed.
2. Experimental
The CaSb2O6:xBi (x ¼0, 0.0025, 0.005, 0.0075, 0.01, 0.02, 0.06,
and 0.08) nanoparticles were prepared using the co-precipitation
method. The starting materials were Bi2O3, SbCl3, CaCl2  2H2O,
NaOH, and Na2C2O4, and they were all in analytical grade.
In a typical synthesis procedure of CaSb2O6:0.01Bi phosphor,
0.0117 g Bi2O3 was dissolved in 25 mL hydrochloric acid with
stirring and moderate heating. Then 0.7241 g of CaCl2  2H2O and
2.2812 g of SbCl3 were added sequentially into the obtained BiCl3
solution under stirring to form a clear and homogeneous mixture.
The mixture solution was added dropwise into 80 mL of aqueous
solution containing 3.52 g of NaOH and 0.737 g of Na2C2O4 with
continuous stirring, and the white precipitation was obtained.
After aging, filtration, washing and drying, the white precursor
was obtained. Finally, the precursor was calcined at 1000 1C for 4 h
in air.
The structure of the samples was characterized by XRD on a
X'Pert Pro MPD diffractometer (Pananalytical, Holland) using CuKα
radiation (λ¼1.5406 Å). The SEM images were taken on Hitachi
s-4700. The excitation and emission spectra were recorded on an
F-2500 fluorescence spectrometer (Hitachi, Japan) at room
temperature.

0167-577X/$ - see front matter & 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matlet.2013.03.109
60 L. Chen et al. / Materials Letters 102–103 (2013) 59–61
3. Results and discussion
Fig. 1 shows the XRD patterns of the as-prepared samples
doped with Bi3+ at different concentrations. All peaks of the as-
prepared samples agree well with the hexagonal structure (JCPDS
Card no. 46-1496), indicating that the doped Bi3+ does not change
the crystal structure or induce a new phase. The diffraction peaks
shift to lower theta values with introducing Bi (inset of Fig. 1)
because of the larger radius of Bi3+ (1.03 Å) compared to that of
Ca2+ (1 Å). Furthermore, it seems that Bi3+ ions have a larger
solubility in CaSb2O6 prepared by co-precipitation here than that
by the solid state reaction [8]. Fig. 2a and b presents SEM images of
Fig. 1. XRD patterns of CaSb2O6:xBi (x ¼ 0, 0.0025, 0.0075, 0.02, and 0.08). Inset is
the amplification of XRD patterns around 26.51.
Fig. 2. SEM images of (a) pure CaSb2O6 and (b) CaSb2O6:0.0075Bi.
the pure and 0.75 mol% Bi-doped CaSb2O6 samples, respectively,
which display that both the samples have uniform sphere-like
shape with particle size of 60–80 nm.
Excitation spectra of CaSb2O6:xBi phosphors via monitoring
437 nm emission are presented in Fig. 3. The excitation spectra of
Bi3+-doped samples consist of three broad bands and they are
located at 244, 295 and 336 nm. These absorption bands can be
attributed to the Bi3+-related absorption due to the their absence
in undoped CaSb2O6 sample. The intensities of all the excitation
bands are dependent on the Bi3+ concentration (inset of Fig. 3).
The ground state of Bi3+ is 1S0 and its excited states are 3P0, 3P1, 3P2
and 1P1 in order of increasing energy [14]. Due to the complete
spin forbiddance of the transition from 1S0 to 3P0 and 3P2, optical
absorption is ascribed to the electron transition from 1S0 to 3P1 and
1
P1 [15]. It is reported that the weak excitation band peaking at
244 nm is assigned to the 1S0–1P1 transition [8]. In this work, the
visible emission can effectively be excited at both 295 and 336 nm
at room temperature, which is different from previous reports
[8,10]. The excitation band at 295 nm is readily assigned to the
host lattice excitation because it agrees well with the band gap of
CaSb2O6. The appearance of the excitation band of the host lattice
in the excitation spectrum of Bi3+ indicates that there exists
energy transfer from host lattice to Bi3+ ions. The dominant bands
peaking at 336 nm have bigger half-widths than those of higher-
energy excitation bands and their peaks shift toward lower energy
with increasing Bi3+ concentration. This absorption band is attrib-
uted to 1S0–3P1 transition. Here, it is worth noting that the optimal
excitation intensities were achieved in CaSb2O6:0.06Bi and
CaSb2O6:0.0075Bi corresponding to the excitation wavelengths of
295 and 336 nm, respectively.
Fig. 4 shows the emission spectra of CaSb2O6:xBi (0≤x≤0.08)
phosphors excited at 336 nm, which exhibit strong blue emission
bands centered around 437 nm. The visible emission was ascribed
to 3P1–1S0 transition of Bi3+ pairs [8]. In fact, here the visible
emission is a superposition of several emission bands. The inset of
Fig. 4 displays two Gaussian components for CaSb2O6:0.0075Bi
with approximate peak wavelengths of 435 and 464 nm. The
maximal emission intensity is observed in the phosphor doped
with 0.75 mol% Bi3+.
It is believed that defects may play an important role on the
optical properties of CaSb2O6:xBi phosphors. As for the compound
CaSb2O6, there is only one crystallographic Ca2+ site for Bi3+. The
defect of ðBiCa Þd will be formed when Bi3+ was incorporated on Ca2
+
site. Considering the charge compensation of ðBiCa Þd , some other
Fig. 3. Excitation spectra of CaSb2O6:xBi via monitoring 437 nm emission.
 L. Chen et al. / Materials Letters 102–103 (2013) 59–61 61

which is one of the phenomenological characteristics of the

variation of the crystal field strength [16].

4. Conclusions

Nano-scaled CaSb2O6:xBi with sphere-like morphology has

been successfully synthesized by the co-precipitation method.
The as-prepared phosphors exhibit an intense blue emission at
room temperature. The blue emission is a superposition of at least
two emission bands and it could ascribe to the defect perturbation.
The optimal excitation intensities of 295 nm and 336 nm are
achieved in CaSb2O6:0.06Bi and in CaSb2O6:0.0075Bi, respectively.
It is believed that the defect clusters such as ½ðBiCa Þ−ðV Ca Þ′ and
½ðBiCa Þ−ðV Ca Þ−ðBiCa Þ play important roles on the optical properties
of CaSb2O6:Bi. The experimental results suggested that the
co-precipitation method is favorable for preparing the CaSb2O6:
Bi with desired optical properties.

Fig. 4. Emission spectra of CaSb2O6:xBi excited at 336 nm. Acknowledgments

This work was supported by the National NSF of China

defects such as cation vacancies ðV Ca Þ″ have to be formed. Upon (21005053) and the Priority Academic Program Development of
excitation of the host lattice (295 nm), the generated electrons and Jiangsu Higher Education Institutions.
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