J Sol-Gel Sci Technol (2010) 56:340–344
DOI 10.1007/s10971-010-2311-9
ORIGINAL PAPER
Nano-sized polycrystalline bismuth silicon oxide powder
by sol–gel technique
Bansi Lal • Sasmita K. Patro • Shivani Singh
Received: 19 February 2010 / Accepted: 16 August 2010 / Published online: 31 August 2010
Ó Springer Science+Business Media, LLC 2010
Abstract Bismuth silicon oxide (Bi12SiO20, BSO) nano
crystalline powder was prepared by sol–gel technique using
bismuth nitrate and tetraethyl orthosilicate as starting
materials. The prepared samples were sintered at various
temperatures (750 °C maximum) and characteristic sillenite
single cubic phase with crystallite size *38 nm (calculated
from room temperature powder XRD measurements) was
realized at 750 °C sintering temperature. SEM analysis
showed that the powder contains the nano-sized particles
with almost spherical morphology. The observed frequen-
cies in room temperature FTIR spectrum could be assigned
to Bi–O, Si–O and Bi–O–Si bonds. The FWHM (full width
at half maximum) of the diffraction peaks decreased while
the intensity of FTIR absorption lines increased with the
increase in the sintering temperature indicating better bond
formation and crystallization. The thermograph of the
samples recorded in the temperature range 50–1,000 °C
showed almost no weight loss after *575 °C further con-
firmed the conclusion arrived at from XRD and FTIR
analysis. The samples sintered at 750 °C showed about 50%
absorbance in 400–600 nm region which was consistent
with the pale yellow color of the sample. Broad blue
emission centered *478 nm was observed when excited by
350 nm radiation from a Xe-lamp. The intensity of this
broad emission band increased while its FWHM decreased
B. Lal
S. K. Patro
S. Singh
Centre for Laser Technology, Indian Institute of Technology
Kanpur, Kanpur 208016, India
B. Lal (&)
Department of Physics, Lovely Professional University,
Phagwara 144402, India
e-mail: bansi@iitk.ac.in
123
with the increase in sintering temperature. Self-trapped
excitons could be responsible for this emission.
Keywords Bismuth silicon oxide
BSO

Nano-crystallites
Nano-powder
Sol–gel
1 Introduction
Bismuth silicon oxide (Bi12SiO20, BSO) with the sillenite
structure Bi12MO20 (M = Si, Ge, Ti), has unique combi-
nation of electric and optical properties [1] making it quite
useful in a number of technologically important applica-
tions such as spatial light modulators [2], optical image
converter [3] optical data processing [4], holographic
recording medium [5] and so on. Most of these applications
are based on the single crystals of BSO which can be
grown by well-known techniques [6–12]. Alternately, thin
films or polycrystalline powders of adequate density and
transparency could be used in some of these applications
and many reports on this aspect have been published
recently. Thin films prepared by sputtering [13], epitaxial
growth [14], pulsed laser deposition [15] and sol–gel
technique [16, 17] have been investigated. Parallely, sev-
eral studies on the preparation and characterization of
powder BSO have been reported in the literature. Sule-
imenova et al. [18] used thermal technique DSC to inves-
tigate the process of Bi12MO20 formation from oxides
while Chehab et al. [19] investigated the pathways of
sillenite-phase formation by high temperature X-ray dif-
fractometery. Vasconcelos et al. [20] prepared BSO pow-
der by mechanical alloying while Carrasco et al. [21]
investigated the intermediate phase formation in ball
milling synthesis. The dielectric properties of BSO powder
prepared by solid state reaction was investigated by Valant
J Sol-Gel Sci Technol (2010) 56:340–344 341

et al. [22] while Vasconcelos et al. [23] studied the optical

properties of the powder samples prepared by mechanical
alloying. He et al. [24] investigated the photocatalytic
properties of BSO powder prepared by chemical solution
decomposition method. The present work describes the
preparation of nano- sized polycrystalline BSO powder in
bulk by the sol–gel technique. XRD, SEM, FTIR, TG and
photoluminescence techniques were used to characterize
the samples.

2 Experimental

2.1 Sample preparation

Bismuth nitrate (Bi(NO3)3 5H2O, Loba Chemie), tetraethyl

orthosilicate (C8H20O4Si, Otto Kemi), acetic acid
(CH3COOH, Qualigens Fine Chemicals) and 2-methoxy
ethanol (C3H8O2, Spectrochem Pvt. Ltd.) were the starting
materials for this synthesis. Figure 1 summarizes the var-
ious steps involved in the preparation of powder BSO. 10 g
of bismuth nitrate was dissolved in 10 mL of glacial acetic
acid by stirring at 30 °C for 3 h. Tetraethyl orthosilicate
(0.39 mL) was added drop by drop to the above solution
under continuous stirring. The resulting solution was then
diluted with 5 mL of 2-methoxyethanol to adjust the vis-
cosity of the solution and stirring continued for 5 h to yield
a clear transparent/homogenous solution. The solution thus
obtained turned into gel on storing it at room temperature
for about 2 days. This gel dried at 130 °C, was made into
powder by hand grounding it in a pestle-mortar. The yellow
powder thus obtained was sintered in air for about 8 h (at
each temperature) at various temperatures (750 °C maxi-
mum) using a horizontal electrical furnace.
2.2 Characterization
Powder XRD spectra in the range 15–75° were recorded
by JSO-Debye flex 2002 X-ray diffractometer using
1.5418° Å Cu-Ka radiation, 3 min-1 scanning speed and
0.03 step size while SEM analysis was carried out using
ZEISS Supra 40 VP FESEM system.
FTIR spectra in 400–4,000 cm-1 region were recorded
with Bruker Optics USA Model Vertex-70 spectropho-
tometer using the KBr pellet (*1 wt% sample) method.
Thermal analysis (Model Netzsch STA 409 PC/PG) in
the temperature range 50–1,000 °C was carried out in
nitrogen atmosphere with a heating rate of 5 °C/min.
Room temperature absorbance of the powder samples in
the spectral range 200–600 nm was measured on Cary
5000 spectrophotometer.
Room temperature photoluminescence spectra in the
range 300–600 nm were recorded with Jobin–yvon Model
Fig. 1 Summary of the various steps involved in sol–gel synthesis of
BSO powder
Fluorolog-3 fitted with Xe lamp as the excitation source.
Correction factors were applied to eliminate the errors due
to system response.
3 Results and discussion
3.1 Powder XRD and SEM
Powder XRD patterns recorded for the samples sintered at
various temperatures in the 300–750 °C range are shown in
Fig. 2. As seen in this figure, only one broad peak with
(hkl) value (310) was observed for the samples sintered at
300 °C. The number of the observed peaks as well as their
intensity increased with the increase in the sintering tem-
perature and at 750 °C well defined diffraction peaks were
observed which were indexed as Bi12SiO20 cubic phase
(JCPDF Card 37-0485). This improvement in the crystal-
line nature of powder with the increase in sintering tem-
perature was also indicated by the decrease in the FWHM
(full width at half maximum) of the diffraction peaks with
the increase in sintering temperature. The crystallite size
was calculated by well-known Scherrer formula using the
data from the most dominating peak at (310) and the results
are summarized in Table 1. As seen in this table the
crystallite size increased with increase in the sintering

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size in 10–20 nm range) almost spherically shaped parti-

cles. On the other hand, the powder sintered at 750 °C
(Fig. 3b) was mostly composed of less spherically shaped
particles of bigger size ([20 nm) along with some \5 nm
sized spherical particles. The bigger sized particles look
like composed of smaller sized spherical particles implying
that the agglomeration could be dominating process in case
of BSO as reported in many other polycrystalline materials
[25, 26].

3.2 Room temperature FTIR spectroscopy

The room temperature FTIR spectra recorded in the spec-

tral range 400–4,000 cm-1 for the samples sintered at
300–750 °C are shown in Fig. 4. The spectrum of the
sample sintered at 300 °C showed broad absorption bands
Fig. 2 Powder XRD spectra of the BSO samples sintered at various
temperatures around 3,500–1,050 cm-1 and relatively sharp lines at
1,600, 825, 600, 548 and 454 cm-1. The intensity of the
broad absorption bands decreased with the increase in the
Table 1 Crystallite size of BSO powder samples sintered at various sintering temperature and the observed absorptions spec-
temperatures calculated from powder XRD measurements trum (along with the transition assignment) of the sample
Sintering Crystallite sintered at 750 °C are given in Table 2. The week and
temperature (°C) size (nm) broad absorption peak at *3,465 cm-1 could be assigned
to OH stretching which could be either due to water
300 18
absorbed from atmosphere during measurement or due to
500 18
OH impurity which has been observed in single crystals of
700 26 BSO earlier [27]. The week peaks at 2,925–2,878 cm-1
750 38 due to C–H stretch could be due to hydrocarbons present in
the atmosphere surrounding the measurement area. On the
other hand the remaining observed peaks could be assigned
temperature from *18 nm at 300 °C to *38 nm at to Si–O, Bi–O or Si–O–Bi bonds. BSO, analogous to BGO
750 °C. This increase in the crystallite size with the [28], crystallizes in the cubic system with two chemical
increase in the sintering temperature could be partly due to formulae in a unit cell. In this unit cell heptacoordinated Bi
increase in the grain size and partly due to agglomeration. (5 oxygen atoms form an incomplete octahedral arrange-
This was further investigated by SEM. Typical micro- ment while the remaining two atoms form Bi–O bonds)
graphs of the powders sintered at 500–750 °C are shown in share corners with other identical Bi and SiO4 tetrahedra.
Fig. 3. As seen in this figure the powder sintered at 500 °C The intensity of these peaks increased with the increase
(Fig. 3a) was composed of nano-sized (average particle in sintering temperature indicating better bond formation

Fig. 3 SEM micrographs of

BSO samples sintered at
a 500 °C and b 750 °C

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Fig. 4 Room temperature FTIR spectra of the BSO samples sintered Fig. 5 Typical thermo-gram of the BSO powder
at 300 °C (dashed lines) and 750 °C (solid lines)

Table 2 Assignment of the IR frequencies observed in BSO powder

sample sintered at 750 °C
Observed frequencies (cm-1) Mode assignment

3,465 OH stretch
2,952 C–H stretch
2,878 C–H stretch
1,046 Si–O–Si stretching
960 (SiO4)-4 stretching vibration modes
825 Si–O bending
600 Bi–O vibration
548 Bi–O–Si stretching
454 Si–O out of plane bending

Fig. 6 Typical room temperature optical absorbance of BSO samples

sintered at 750 °C
and hence better crystallization as concluded from XRD
analysis. oxide while ‘‘almost no weight loss’’ zone after *550 °C
corresponds to the formation of BSO; further confirming
3.3 TG measurements the observations made in XRD and FTIR analysis.

The TG measurements carried out in the temperature range
50–1,000 °C (Fig. 5) showed slow weight loss (*3%) in
the temperature range 100–200 °C, *20% weight loss
from 200 to 300 °C, very little loss (*1%) from 300 to
*550 °C while there is almost no weight loss in
550–1,000 °C temperature range. The initial slow weight
loss could be due to evaporation of water and other organic
material while the relatively rapid weight loss in the tem-
perature range 200–300 °C could be due to decomposition
of the hydroxides of bismuth and silicon. On the other
hand, the slow weight loss observed from *300 to
*550 °C could be due to decomposition of the residual
nitrate of bismuth as well as sublimation of the bismuth
3.4 Optical absorption and emission
Optical absorbance (200–600 nm region) measured at
room temperature of the BSO powder sample sintered at
750 °C is shown in Fig. 6. As seen in this figure maximum
absorbance (1.4/cm, *5% transmission)) was observed
around 276 nm which started decreasing rapidly from
300 nm, reached a value of *0.4 (*40% transmission) at
400 nm and *0.3 (*30% transmission) at 500 nm; this
absorption in 400–600 nm was consistent with the pale
yellow color of the powder sintered at 750 °C.
Room temperature photoluminescence spectra (400–
650 nm region) excited with 350 nm radiation from a Xe

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Shivani Singh is gratefully acknowledged. Also, the preliminary work

carried out by Mr. Harsh Mishra as a part of his Assistantship is
thankfully acknowledged.

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Acknowledgments Financial assistance provided by BRNS, GOI
Mumbai to Ms. Sasmita Kumari Patro and by CSIR New Delhi to Ms.

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