Chemical Physics Letters 372 (2003) 451–454

www.elsevier.com/locate/cplett

Synthesis and luminescence properties of SnO2 nanoparticles

Feng Gu a, Shu Fen Wang a, Chun Feng Song a, Meng Kai L€
u a,*, Yong Xin Qi b,
Guang Jun Zhou c, Dong Xu a, Duo Rong Yuan a
a
State Key Laboratory of Crystal Materials, Shandong University, Jinan 250100, PR China
b
College of Materials Science and Technology, Shandong University, Jinan 250100, PR China
c
Shandong Supervision and Inspection Institute for Product Quality, Jinan 250100, PR China
Received 28 January 2003; in final form 11 March 2003

Abstract

Nanometer-scale SnO2 particles have been synthesized by a simple sol–gel method. The samples were characterized
by X-ray diffraction, Fourier transform infrared (FTIR), UV–Vis absorption and photoluminescence spectroscopy. The
as-prepared SnO2 nanoparticles appear to be single tetragonal crystalline phase and the diameter is about 2.6 nm. The
origin of luminescence is assigned to the recombination of electrons in singly occupied oxygen vacancies with photo-
excited holes in the valence band.
Ó 2003 Elsevier Science B.V. All rights reserved.

1. Introduction and transistors [8]. Applications of SnO2 have re-

Recently, there has been considerable interest in
photoluminescent properties of many metal oxides
such as TiO2 [1], ZnO [2], WO3 [3], and In2 O3 [4],
because they could possibly be used, for example,
as nanoscopic optical storage elements or as
probes in living systems [5]. However, compara-
tively few studies, to the best of our knowledge,
have been carried concerning the luminescence of
nanoscaled SnO2 crystallites. Nanometric SnO2
particles are a technologically important class of
materials with a wide range of applications in gas
sensors [6], transparent conducting electrodes [7]
*
Corresponding author. Fax: +86-5318565403.
E-mail address: mklu@icm.sdu.edu.cn (M. Kai L€
u).
cently been extended to solar cells because of the
optical conduction of SnO2 films [9].
Nanocrysalline semiconductors, including
SnO2 , have been the subjects of numerous inves-
tigations in the past decades. If the semiconductor
particles become smaller than the Bohr radius of
the exciton, so-called quantum size effects occur
[10–12]. As a result of these quantum size effects,
the band gap of the semiconductor increases, and
at the edges of the valence and conduction band
discrete energy levels occur. These quantum size
effects have stimulated great interest in both basic
and applied research. In recent years, with respect
to SnO2 , considerable efforts have been focused
on its synthesis of thin films or particles and the
exploration of their novel properties. A variety
of methods, such as chemical vapor deposi-
tion (CVD) [13], magnetron sputtering [14], and

0009-2614/03/$ - see front matter Ó 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0009-2614(03)00440-8
452 F. Gu et al. / Chemical Physics Letters 372 (2003) 451–454

thermal evaporation [15], are available to pre- 3. Results and discussion

pare SnO2 thin films or nanoparticles. And the
synthesis of SnO2 with one-dimensional (1D)
nanostructures has also been reported [16,17].
Sol–gel processing is a relatively simple way of
preparing chemically homogeneous, high-purity
and phase-pure powders at a lower temperature. A
considerable amount of recent work has been de-
voted to probe new properties of sol–gel derived
inorganic nanoscaled materials. A few publica-
tions described the fabrication of SnO2 powders by
sol–gel method, however, it is a challenge to find
an efficient and simple way to prepare SnO2
powders with particle size about several nano-
meters by using this method. Furthermore, few
reports have been published on the luminescent
characteristics of nanoscaled SnO2 powders. In the
present paper, a sol–gel method for the prepara-
tion of nanocrystalline SnO2 powders, without
addition of any mineralizer, was reported, and
its luminescent property was investigated.
XRD pattern of the as-prepared SnO2 samples
at 400 °C for 2 h are shown in Fig. 1. All the
diffraction lines are assigned to tetragonal rutile
crystalline phases of tin oxide. The XRD pattern is
in excellent agreement with a reference pattern
(Powder Diffraction File No. 41-1445) of tin oxide.
The crystallite size of the prepared powders cal-
culated from XRD line broadening using Debye–
Scherrer equation is about 2.6 nm.
Fig. 2 shows the FTIR spectrum of the pre-
pared SnO2 samples calcined at 400 °C. From this
spectrum, it can be observed apparently at 600
cm1 that strong band associated with the anti-
symmetric Sn–O–Sn strenching mode of the sur-
face-bridging oxide formed by condensation of
adjacent surface hydroxyl groups. The absorption
in 3444 cm1 indicates that the presence of hy-
droxy, which is probably due to the fact that the

2. Experimental

SnO2 nanopowders were successfully prepared

by means of dissolving of tin chloride (hydrous
SnCl4
5H2 O (A.R.)) in distilled water. In a typical
synthesis, an aqueous ammonia solution (2 M) was
added to the above solution dropwise. The drop-
ping rate must be well controlled for the chemical Fig. 1. XRD pattern for SnO2 particles calcined at 400 °C.
homogeneity. The resulting opal gel were col-
lected, washed with distilled water, and then dried
at 80 °C for several hours. Heating treatments of
the synthesized SnO2 nanopowders were con-
ducted at 400, 500, and 600 °C for 2 h, respec-
tively.
The crystalline structure of the material was
analyzed by X-ray diffraction (XRD) using a
Japan RigaKu D/MAX 2200PC diffractometer
with Cu-Ka radiation ( ¼ 0.15418 nm) and graph-
ite monochromator. The absorption spectra of the
samples were measured on a spectrophotometer
(U-3500). The excitation and photoluminescence
(PL) spectra were measured with a Hitachi M-850
fluorescence spectrometer. The Fourier transform
infrared (FTIR) spectra of the samples were col- Fig. 2. FTIR spectrum for SnO2 nanoparticles calcined at
lected using a 5DX FTIR spectrometer. 400 °C.
 F. Gu et al. / Chemical Physics Letters 372 (2003) 451–454
spectrum was not recorded in situ and some
readsorption water from the ambient atmosphere
has occurred. These bands further confirm that the
SnO2 phase can be indeed formed after calcining at
400 °C for 2 h.
For semiconductor nanoparticles, the quantum
confinement effect is expected, and the absorption
edge will be shifted to a higher energy when the
particle size decreases. The value of the absorption
edge of the samples calcined at 400 °C is 298 nm
(about 4.2 eV) (shown in Fig. 3). Due to a larger
particle size for samples treated at 500 and 600 °C,
the absorption edge appears red-shift to some ex-
tent. Considering the blue shift of the absorption
positions from the bulk SnO2 , the absorption onsets
of the present samples can be assigned to the direct
transition of electron in the SnO2 nanocrytals.
Fig. 4 shows the room-temperature excitation
and emission spectra of the as-synthesized SnO2
nanoparticles. The excitation spectrum shows one
strong band at 300 nm (kem ¼ 400 nm), which is
consistent with the results of absorption spectra.
The emission spectrum presents two bands at 400
and 430 nm, respectively. Earlier reports have in-
dicated that SnO2 thin films exhibited a broad
dominant peak near 396 nm (3.1 eV) [18]. Since the
emission maximums (400 nm at 3.1 eV and 430 nm
at 2.9 eV) are both lower than the band gap of the
SnO2 nanocrystal, about 4.1 eV, the visible emis-
Fig. 3. Absorption spectrum for the SnO2 nanoparticles at
400 °C.
453
Fig. 4. Excitation and emission spectra of the samples calcined
at 400 °C for 2 h: (a) kem ¼ 400 nm; (b) kex ¼ 270 nm.
sion cannot be assigned to the direct recombina-
tion of a conduction electron in the Sn 4p band
and a hole in the O 2p valence band. The peaks at
430 nm might originate from the luminescence
centers formed by such tin interstitials or dangling
in the present SnO2 nanoparticles, but that is not
yet clear. We attribute the emission at 400 nm to
electron transition mediated by defects levels in the
band gap, such as oxygen vacancies. This is proved
by the fact that the temperature behavior of lu-
minescence spectra of the nanoscaled SnO2 pow-
ders is similar with those from nanocrystals of
SrTiO3 , TiO2 , ZnO, and BaTiO3 [19–22]. In the
present SnO2 nanocrystals, the intrinsic defects,
such as oxygen vacancies, which act as luminescent
centers, can form defect levels located highly in the
gap, trapping electrons from the valence band to
make a contribution to the luminescence. Gener-
ally, in poly- and nano-crystalline oxides, oxygen
vacancies are known to be the most common de-
fects and usually act as radiative centers in lumi-
nescence processes. Also, the oxygen vacancies can
present in three different charge states: V0o , Vþo , and
Vþþ
o [23]. The oxygen vacancy is an intrinsic donor
in SnO2 . Because V0o is a very shallow donor, it is
expected that most oxygen vacancies will be in
their paramagnetic Vþ o state under flat-band con-
ditions [23].
As the calcining temperature increases from
400 to 600 °C, the particle size of SnO2 nanocrystal
becomes larger (from 2.6 to 8.8 nm). A decrease in
PL intensity in the luminescence spectra at 400 nm
can occur resulting from the reductions of both the
ratio surface area and concentration of oxygen
454 F. Gu et al. / Chemical Physics Letters 372 (2003) 451–454
Fig. 5. Temperature dependence of relative luminescence in-
tensity at 400 nm.
vacancies (shown in Fig. 5). Lowering the con-
centration of oxygen vacancies is owing to in-dif-
fused oxygen recombining with oxygen vacancies
[23]. Based on the above discussion, the oxygen
vacancies really play an important role on PL
emission via a recombination of Vþo electrons with
photoexcited holes in the valence band.
4. Conclusions
In conclusion, SnO2 nanoparticles have been
successfully prepared by a simple sol–gel method.
XRD measurement indicates that the diameter of
the as-prepared particle is about 2.6 nm. FTIR and
the UV–Vis absorptive spectra of the samples have
also been investigated. PL exhibits two bands at
400 and 430 nm, respectively. The luminescence is
related to the recombination of electrons in singly
occupied oxygen vacancies with photoexcited
holes in the valence band.
References
[1] Y.J. Liu, R.O. Claus, J. Am. Chem. Soc. 119 (22) (1997)
5273.
[2] K. Vanheusden, W.L. Warren, C.H. Seaeger, D.R. Jallant,
J.A. Voigt, B.E. Gnade, J. Appl. Phys. 79 (1996) 7983.
[3] R.M. Villarica, F. Nash, J. Chaiken, J. Osman, R.
Bussjager, in: Mater. Res. Soc. Symp. Proc., vol. 397,
1996 p. 347.
[4] H.J. Zhou, W.P. Cai, L.D. Zhang, Appl. Phys. Lett. 75
(1999) 495.
[5] L.A. Peyser, A.E. Vinson, A.P. Bartko, R.M. Dickson,
Science 291 (2001) 103.
[6] J. Watson, Sens. Actuators 5 (1984) 29.
[7] Y.S. He, J.C. Campbell, R.C. Murphy, M.F. Arendt, J.S.
Swinnea, J. Mater. Res. 8 (1993) 3131.
[8] G. Sberveglieri, Sens. Actuators B 6 (1992) 64.
[9] S. Ferrere, A. Zaban, B.A. Gregg, J. Phys. Chem. B. 101
(1997) 4490.
[10] L. Brus, J. Phys. Chem. 90 (1986) 2555.
[11] A. Henglein, Chem. Rev. 89 (1989) 1861.
[12] Y. Wang, N. Herron, J. Phys. Chem. 95 (1991) 525.
[13] R.D. Tarey, T.A. Raju, Thin Solid Films 128 (1995)
181.
[14] T. Minami, H. Nanto, S. Takata, Jpn. J. Appl. Phys. 27
(1988) L287.
[15] V. Schlosser, G. Wind, in: Proceedings of the 8th EC
photovoltaic Solar Energy Conference, Florence, Italy,
1998, p. 998.
[16] J.K. Jian, X.L. Chen, W.J. Wang, L. Dai, Y.P. Xu, Appl.
Phys. A 76 (2003) 291.
[17] Y.K. Liu, C.L. Zheng, W.Z. Wang, C.R. Yin, G.H. Wang,
Adv. Mater. 13 (2001) 1883.
[18] T.W. Kim, D.U. Lee, Y.S. Yoon, J. Appl. Phys. 88 (2000)
3759.
[19] W.F. Zhang, Z. Yin, M.S. Zhang, Z.L. Du, W.C. Chen,
J. Phys. Cond. Mat. 11 (1999) 5655.
[20] W.F. Zhang, M.S. Zhang, Z. Yin, Q. Chen, Appl. Phys. B
70 (2000) 261.
[21] W.F. Zhang, M.S. Zhang, Z. Yin, Phys. Stat. Sol. (a) 179
(2000) 319.
[22] D.W. Bahnemann, C. Kormann, M.R. Hoffmann, J. Phys.
Chem. 91 (1987) 3789.
[23] K. Vanheusden, W.L. Warren, C.H. Seager, D.R. Tallant,
J.A. Voigt, B.E. Gnade, J. Appl. Phys. 79 (1996) 7983.