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Department of Applied Physics, University of Electronic Science and Technology of China, Chengdu 610054, PR China
b International Center for Material Physics, Chinese Academy of Sciences, Shengyang 110015, PR China
c Department of Nuclear Engineering and Radiological Sciences, University of Michigan, Ann Arbor, MI 48109-2104, USA
d Department of Materials Science and Engineering, University of Michigan, Ann Arbor, MI 48109-2104, USA
e Advanced Materials Research Institute, University of New Orleans, New Orleans, LA 70148, USA
Received 15 October 2006; received in revised form 3 December 2006; accepted 5 December 2006
Available online 29 December 2006
Abstract
Fe3+ -doped SnO2 nanoparticles were prepared by solgel-calcination and solgel-hydrothermal routes, respectively, and their microstructure as
well as physical and chemical properties have been characterized and compared. Based on XRD, TEM, and Fourier transform infrared (FT-IR) analyses, the SnO2 crystallites with the tetragonal rutile structure formed directly during a hydrothermal process. Compared with the solgel-calcination
route, solgel-hydrothermal route led to better dispersed nanoparticles with a narrower size distribution and a larger BrunauerEmmettTeller (BET)
surface area. Also, the Fe3+ -doped SnO2 nanoparticles prepared by solgel-hydrothermal route had a better thermal stability against agglomeration
and crystalline grain size growth than those prepared by the solgel-calcination route. XRD, EDS, and diffuse reflectance spectra (DRS) analyses
proved that the Fe3+ and SnO2 formed a solid solution in the nanoparticles with both processing routes. A significant red shift in the UV absorbing
band edge was observed with the increasing Fe3+ content.
2006 Elsevier B.V. All rights reserved.
Keywords: SnO2 ; Solgel; Hydrothermal; Calcination; Doping; Nanoparticles
1. Introduction
Nano-sized SnO2 particles, as an n-type semiconductor with
a wide band gap (Eg = 3.6 eV, at 25 C), have been attracting
much attention due to their transparency and sensitivity to reducing gases. They have a wide range of applications in gas sensors
[13], optoelectronic devices [45], dye-base solar cells [6], secondary lithium batteries electrode materials [7], and catalysts
[8]. One area of primary importance is the field of solid state
gas sensors for environmental monitoring, such as for CO, NO,
and C2 H5 OH, where SnO2 has been established as the predominant sensing material. It is generally accepted that increasing
the surface/bulk ratio by decreasing the grain size of rutile SnO2
nanoparticles is crucial for achieving high-sensitivity in gas sen-
Corresponding author at: Department of Applied Physics, University of Electronic Science and Technology of China, Chengdu 610054, PR China.
Tel.: +86 28 83201939; fax: +86 28 83201939.
E-mail address: xiaotaozu@yahoo.com (X.T. Zu).
0925-8388/$ see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jallcom.2006.12.014
sors. One of the other most common ways to modify the characteristics of the material is introducing dopants into the structure.
Many results have shown that several additives (cations: Fe, Cu,
Co, Cr, Al, Mn, Mg; anions: P, S) can lead to an increase of the
surface area of SnO2 -based powders [3,914]. The added active
elements stabilize the SnO2 surface, and promote a decrease in
grain size. It has been found that Fe3+ -doped SnO2 nanoparticles with lower crystallinity and high surface area have the
higher catalytic activity and sensor signal than both pure SnO2
and Fe2 O3 [15,16]. Thus, nanocrystalline Fe3+ /SnO2 have been
investigated as a material for oxygen, ethanol, hydrogen sulfide,
carbon monoxide, and water vapor gas sensors [3,9,17].
The properties of metal ions (including transition metal ions
and rare-earth elements)-doped SnO2 can be altered to different states due to many factors during the preparation process
[18,19]. Thus, the final products are related to both composition and the processing method used for synthesize the material.
To take advantage of the properties of metal ions-doped SnO2
nanoparticles, a number of attempts have been made by developing effective synthetic techniques in the preparation of metal
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L.M. Fang et al. / Journal of Alloys and Compounds 454 (2008) 261267
for 12 h. After that, the hydrothermal product was filtered and dried at 110 C
for 10 h. Then, the Fe3+ -doped SnO2 nanoparticles were obtained. The products
were marked SGH-series.
According to the Fe molar content in samples (0, 1.0, 5.0, 10.0, 15.0,
and 20.0 mol%), the products were designed as SGC0, SGC1, SGC5, SGC10,
SGC15, and SGC20 for SGC series and SGH0, SGH1, SGH5, SGH10, SGH15,
and SGH20 for SGH series, respectively. To compare the effect of temperature
on the nanoparticle properties, both the SGC and SGH series of samples were
calcined at 350, 600, and 800 C in air for 1 h.
L.M. Fang et al. / Journal of Alloys and Compounds 454 (2008) 261267
263
Fig. 1. XRD patterns of Fe3+ -doped SnO2 nanoparticles: (a) SGC series and (b)
SGH series.
Fig. 2. The crystalline grain sizes of SnO2 calculated from Scherrer formula.
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L.M. Fang et al. / Journal of Alloys and Compounds 454 (2008) 261267
SGC0
SGC10
SGH0
SGH10
350 C
600 C
800 C
5.98
5.02
17.55
10.03
9.73
6.43
34.14
14.85
19.69
8.18
55.68
45.62
33.26
17.71
doped SnO2 was smaller. On the other hand, for the SGH series,
the addition of Fe3+ showed more significant inhibiting effect
on the increase of crystallite size. After calcination at 800 C,
the grain size of SGH10 was 17.71 nm, but it was 45.62 nm
for the SGC10. It is clear that the Fe3+ -doped SnO2 nanopar-
Table 2
The BET surface area of samples with different Fe3+ content
Samples
Fe content (mol%)
BET surface area (m2 /g)
SGC
SGH
SGC0
SGC1
SGC5
SGC15
SGH0
SGH1
SGH5
SGH15
0
30.2
1.0
34.6
5.0
47.0
15.0
68.9
0
206.1
1.0
211.7
5.0
237.1
15.0
259.8
L.M. Fang et al. / Journal of Alloys and Compounds 454 (2008) 261267
265
Fig. 5. Bright field TEM and HRTEM micrographs of samples: (a) SGH1, (b) SGH5, and (c and d) SGH15.
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L.M. Fang et al. / Journal of Alloys and Compounds 454 (2008) 261267
Fig. 7. FT-IR transmission spectra of samples: (a) SGC series and (b) SGH
series.
Fig. 8. The diffuse reflectance spectra of samples: (a) SGC series and (b) SGH
series.
Fe3+ -doped SnO2 nanoparticles were prepared by solgelcalcination and solgel-hydrothermal routes, respectively. The
SnO2 crystallites with the tetragonal rutile structure could form
directly during the hydrothermal process without calcination.
L.M. Fang et al. / Journal of Alloys and Compounds 454 (2008) 261267
Fe3+ formed stable solid solutions in SnO2 nanoparticles. Compared with solgel-calcination route, solgel-hydrothermal
route led to better dispersed spherical Fe3+ -doped SnO2
nanoparticles with narrower size distribution and larger specific
surface area. The composite nanoparticles prepared by the
solgel-hydrothermal route have better thermal stability against
agglomeration and particle growth than those prepared by
solgel-calcination route. The BET surface area of the SnO2
sample with 15% Fe3+ prepared by solgel-hydrothermal route
was increased to 259.8 m2 /g from 206.1 m2 /g of SGH0. Narrow
size distribution nanoparticles, excellent dispersibility and large
surface areas of Fe3+ -doped SnO2 nanoparticle prepared by
solgel-hydrothermal route make it particularly appealing in
applications for gas sensors and optoelectronic devices.
Acknowledgements
This study was supported financially by the NSAF Joint
Foundation of China (10376006) and by the Program for New
Century Excellent Talents in University (NCET-04-0899) and by
the Ph.D. Founding Support Program of Education Ministry of
China (20050614013) and by Program for Innovative Research
Team in UESTC.
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