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Journal of Alloys and Compounds 454 (2008) 261267

Synthesis and characteristics of Fe3+-doped SnO2 nanoparticles via


solgel-calcination or solgel-hydrothermal route
L.M. Fang a , X.T. Zu a,b, , Z.J. Li a , S. Zhu c , C.M. Liu a , W.L. Zhou e , L.M. Wang c,d
a

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

ions-doped SnO2 nanoparticles, such as mechanical alloying


[20], solgel [3,11,14,18], co-precipitation [13,16], and chemical vapor deposition [21,22]. The solgel method is the most
effective method due to its capability in controlling the textural and surface properties of metal oxides. This method is
mainly based on the hydrolysis and polycondensation of a metal
salt, which ultimately yields hydroxide or oxide under certain conditions [19]. Generally, solgel-derived precipitates are
amorphous in nature. So calcination in air is needed for the transformation from amorphous to rutile phase to complete. However,
the calcination process generally lead to serious particle agglomeration, grain growth, and thus, a small total surface area, which
decreases the sensitivity to a number of reducing gases. The
hydrothermal processing represents an alternative to the calcination for the crystallization of SnO2 under mild temperatures.
In the hydrothermal treatment, grain size, particle morphology, crystallinity, and surface chemistry can be controlled via
processing variables such as sol composition, pH, reaction temperature and pressure, aging time, and nature of solvent and
additive. It provides a facilitated route to prepare uniform, welldispersed, and well-crystallized SnO2 nanoparticles. However,
the hydrothermal method has not been used for the preparation of
Fe3+ -doped SnO2 nanoparticles. It is well known that the method
of preparing Fe3+ -doped SnO2 nanoparticles can determine the
physico-chemical, optoelectronic properties and sensitivity for
gasses, and the effects of Fe3+ doping on SnO2 can be quite
different according to the synthetic procedures, so a comparative study on the properties of Fe3+ -doped SnO2 nanoparticles
prepared by different routes is necessary.
In the present work, Fe3+ -doped SnO2 nanoparticles were
prepared by solgel calcination and solgel-hydrothermal
routes, respectively, and the physico-chemical and optoelectronic properties were compared. The results demonstrate
that Fe3+ -doped SnO2 nanoparticles prepared by solgelhydrothermal route are better dispersed and have a narrower size
distribution with larger specific surface area than that prepared
by the normal solgel route.
2. Experimental
2.1. Synthesis of samples
SnCl4 5H2 O and FeCl3 6H2 O were used as tin and iron sources, respectively.
First, citric acid was added to 96 ml of H2 O until the pH 1.5 at 50 C with
magnetic stirring; then, 17.529 g of SnCl4 5H2 O were added and dissolved.
Secondly, FeCl3 6H2 O (the Fe molar content in samples was 0, 1.0, 5.0, 10.0,
15.0, and 20.0 mol%) and 10 ml polyglycol were added to the above solution. It
was stirred for 10 min and a sol formed. Thirdly, 30 ml NH3 H2 O (15 mol/l) was
added dropwise to the above sol under magnetic stirring within 30 min. Then,
the hydrolysis product was stirred for 30 min to form a gel. Finally, the gel was
treated by the following two routes, respectively.
2.1.1. The calcination process
The gel was filtered, and dried at 110 C for 12 h. After that, the powders were
further calcined at 350 C in air for 1 h. Then, the Fe3+ -doped SnO2 nanoparticles
were obtained. The products were denoted as SGC-series.
2.1.2. The hydrothermal process
The gel was transferred into a Teflon-lined autoclave for hydrothermal reaction at 150 C (the pressure in the hydrothermal process should about 0.4 MPa)

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.

2.2. Characterization of samples


The crystalline phase of Fe3+ -doped SnO2 particles were determined by
X-ray diffraction (XRD, Cu K, 40 kV, 60 mA, Rigaku D/max-2400). The morphologies of samples were characterized using a JEOL 2010 F field emission
gun electron microscope (TEM) with an accelerating voltage of 200 keV. The
specific surface area of the prepared samples was calculated from the adsorption isotherm of nitrogen at 77 K on the basis of the BrunauerEmmettTeller
method (BET; Tristar3000, Micromeritics). The chemical structure information
of the particles was collected by FT-IR spectra (Nicolet 560 Spectrometer). Diffuse reflectance spectra (DRS) was recorded by a Shimadzu
UV-2101 apparatus, equipped with an integrating sphere, using BaSO4 as
reference.

3. Results and discussion


3.1. XRD analyses
The XRD patterns of Fe3+ -doped SnO2 nanoparticles are
shown in Fig. 1a and b, respectively. It clearly shows that
the rutile phase formed after calcined at 350 C in the SGC
series of samples (see Fig. 1a). However, rutile structured SnO2
crystallites have also been obtained by the SGH route without calcination (see Fig. 1b). The Fe-doping not only makes the
degradation of the crystallinity but also makes effects on the size
of the nanoparticles, similar results had been reported [2325].
The crystallite grain size of SnO2 can be estimated according
to Scherrer formula L = K/( cos ), where is the wavelength
of the X-ray radiation (Cu K = 0.15406 nm), K the constant
taken as 0.89, the line width at half maximum height and
is the diffracting angle. While the crystalline grain sizes of
SnO2 of the SGH series decreased from 5.98 to 3.85 nm when
the Fe3+ content increased from 0.0 to 20% (see Fig. 2), the
crystalline grain size of the SGC-series decreased from 17.55
to 7.20 nm (see Fig. 2). It is clear that the addition of Fe prevented the growth of crystalline grains of SnO2 , and the grain
size for the SnO2 by the solgel-calcination route with the same
Fe3+ content was larger than that by the solgel-hydrothermal
route.
In addition, no characteristic peaks for the ferric oxide crystal
phase were observed in all samples derived from both preparing
routes. At the same time, the addition of Fe3+ significantly influenced the crystallinity of SnO2 . Fig. 1 suggested a decrease of
crystallinity in the Fe3+ -doped SnO2 nanoparticles in comparison with the undoped sample by the decrease in the intensity
of SnO2 peaks. This means that a portion of Fe3+ formed stable
solid solutions with SnO2 , it could occupy regular lattice site in
SnO2 and that may cause the introduction of point defects and
change in stoichiometry due to charge imbalance. The effect
leads to a distortion of the crystal structure of the host com-

L.M. Fang et al. / Journal of Alloys and Compounds 454 (2008) 261267

263

aggregates also retarded the growth of SnO2 nanoparticles. This


means that a portion of Fe3+ formed stable solid solutions with
SnO2 . In addition, no diffraction peaks of ferric oxide could be
detected even after calcination at 800 C.
The above results suggested that the grain sizes of the Fe3+ doped SnO2 nanoparticles prepared by both methods depended
on the Fe3+ content, and Fe3+ could prevent the growth of crystal grains of SnO2 . Moreover, with solgel-hydrothermal route,
rutile phase was directly synthesized and the addition of Fe3+
was more effective in preventing the growth of crystalline grain
size, suggesting that solgel-hydrothermal route was a more
effective process for preparing Fe3+ -doped SnO2 nanoparticles
compared with the solgel-calcination route.
It is well known that calcination can improve the crystallinity of the samples, but increase the crystallite grain size
of SnO2 at the same time. In order to investigate the possible
crystallization process of SnO2 by increasing the calcinations
temperature, XRD analysis was carried out on the samples calcined at 350, 600, and 800 C, respectively. Typical diffraction
patterns obtained from samples of pure SnO2 and 10% Fe3+ doped SnO2 are shown in Figs. 3 and 4. The grain sizes of
SnO2 calculated by Scherrer formula are showed in Table 1.
Compared to pure SnO2 , the crystalline grain size of 10% Fe3+ -

Fig. 1. XRD patterns of Fe3+ -doped SnO2 nanoparticles: (a) SGC series and (b)
SGH series.

pound. Because of the interference of Fe3+ with SnO2 lattice, the


crystallinity of the Fe3+ -doped SnO2 nanoparticles were worse
than that of pure SnO2 . But when the Fe3+ content was high
(for example, 15 and 20%), a portion of Fe3+ should exist as
amorphous ferric oxide aggregates. The amorphous ferric oxide

Fig. 2. The crystalline grain sizes of SnO2 calculated from Scherrer formula.

Fig. 3. XRD patterns of samples from solgel-calcination route calcined at


different temperature: (a) SGC0 and (b) SGC10.

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L.M. Fang et al. / Journal of Alloys and Compounds 454 (2008) 261267

ticles prepared by solgel-hydrothermal process has a better


thermal stability against grain growth than that prepared by the
solgel-calcination process. This result suggested that solgelhydrothermal route led to a better atomically mixed structure
between Fe3+ and SnO2 , which retarded agglomeration of grains
due to the strong FeOSn linkage. In addition, no diffraction
peaks of ferric oxide could be detected even after calcination at
800 C.
3.2. TEM and BET surface areas

Fig. 4. XRD patterns of samples from solgel-hydrothermal route calcined at


different temperature: (a) SGH0 and (b) SGH10.
Table 1
The crystalline grain sizes of SnO2 calcined at different temperature
Samples

SGC0
SGC10
SGH0
SGH10

Crystalline grain sizes (nm)


110 C

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-

The bright-field TEM and high resolution TEM (HRTEM)


images of pure SnO2 nanoparticles and Fe3+ -doped SnO2
nanoparticles prepared by SGC or SGH routes are shown in
Figs. 5 and 6, respectively. It could be seen that all SnO2 nanoparticles were not larger than 6 nm in diameter for SGH1, SGH5,
SGH15, and SGC15. Selected-area diffraction exhibited the
polycrystalline rings that were all from the rutile SnO2 structure as indexed in Fig. 5a. These rings are in agreement with
the peaks in the power XRD spectra as shown in Fig. 1. Moreover, there are no extra peaks from Fe or ferric oxides. Thus, the
Fe3+ ions are believed to be dissolved in the SnO2 structure. The
HRTEM image showed the crystallinity of the nanoparticles are
well-developed. The Fe3+ -doped SnO2 nanoparticles prepared
by solgel-hydrothermal route were uniform in size with narrow
size distribution, and were well dispersed. The average grain size
decreased when the Fe3+ content increased. It decreased from 6.0
to 3.0 nm when the Fe3+ content increased from 1 to 15%. This
result is similar to that obtained from the XRD analysis. But
for the SGC15 nanoparticles derived from solgel-calcination
route, it could be seen that the average grain size was not uniform, range from 2 to 6 nm. And unfavorable agglomeration
occurred (see Fig. 6).
The BET surface areas of the samples doped with different Fe3+ content are listed in Table 2. It could be seen that
the surface areas were strongly dependent on the preparation
route and the Fe3+ content. It increased with the increasing
of Fe3+ content, and it was clear that the BET surface areas
of samples obtained from solgel-hydrothermal method were
remarkably higher than that from solgel-calcination route. That
is because the samples prepared by solgel-hydrothermal route
were well-dispersed and less size with narrow distribution, but
the samples prepared by solgel-calcination route were agglomerated and larger in grain size. This result indicated that the
addition of Fe3+ into SnO2 matrix suppressed the reduction of
surface area and the suppression was more effective with higher
Fe3+ content. Compared with the solgel-calcination route, the
solgel-hydrothermal route was a more effective process to produce the SnO2 with large surface areas.

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.

SnO2 nanoparticles owned much greater surface-to-bulk ratio


than that of bulk materials. A large fraction of the atoms presented at the surface of SnO2 nanoparticles. An important effect
is associated with the depth of the surface space charge region
that is affected by gas adsorption in relation to the particle size.
When the particle size gets into the nano-range, the depletion
layer takes over the bulk, and it becomes difficult to distinguish
surface from bulk conduction. So the narrow size distribution,
excellent dispersibility and large surface areas are all favorable
for application in gas sensors and optoelectronic devices. The
characteristics of Fe3+ -doped SnO2 nanoparticles prepared by
solgel-hydrothermal route make the processing route particularly appealing.

3.3. Fourier transform infrared (FT-IR) spectroscopy


analyses
The FT-IR transmission spectra of samples are given in Fig. 7.
The absorption peaks at 3400 and 1640 cm1 were attributed to
vibration of hydroxyl due to the fact that SnO2 retained certain adsorbed water. Additionally, bands at 2930, 2850, and
1390 cm1 were assigned to CH vibrations. The CH could
be attributed to the organic trace residuals, which remained in
nanoparticles even after calcinations for the solgel-calcination
route. The band at approximately 2365 cm1 resulted from the
adsorption and interaction of atmospheric carbon dioxide with
water according to literature [26]. The bands observed in the

Fig. 6. HRTEM micrographs of SGC15.

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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.

range of 1059 cm1 were assigned to the vibration of different


types of surface hydroxyl groups. Lenaerts [27] had observed
that the bands at 1068 and 970 cm1 most strongly appeared
in the spectra of SnO2 taken in O2 at room temperature versus
450 C spectra. They ascribed these absorptions to Sn O and
Sn O modes of surface cationoxygen bonds. The SnOSn
vibration appeared in the range of 400700 cm1 as the result
of condensation reaction. The peaks at 660 and 560 cm1 are
attributed to the SnOSn antisymmetric vibrations. Compared
with the SGC series samples, the absorption peaks of 3400 cm1
were higher for the SGH series samples, suggesting that there
were more O H bonds on the Fe3+ -doped SnO2 nanoparticle
prepared by solgel-hydrothermal route than that prepared by
solgel-calcination route.
3.4. UVvis diffuse reectance spectroscopy (DRS)
analyses

Fig. 8. The diffuse reflectance spectra of samples: (a) SGC series and (b) SGH
series.

nanoparticles [2830]. Red shifts of this type could be attributed


to the charge-transfer transitions between the Fe3+ d-electrons
and the SnO2 conduction or valence band. On the other hand,
there was no separated phase of ferric oxide because its broad
band centered at 500 nm was not present [31]. This is another
evidence showing the Fe3+ were doped in the SnO2 nanoparticles
rather than existed as ferric oxide.
After comparing the DRS spectra, it can be seen that the
SGH-series had larger band gap than SGC-series. The larger
band gap was resulted from the well-known quantum size effect
of semiconductors [32]. The results of XRD and HRTEM have
proved that with same Fe3+ content, the crystalline grain size of
SnO2 from solgel-hydrothermal route was more uniform and
smaller than that prepared with the solgel-calcination route.
According to the size quantization, an increase in the band gap
happened with the decrease in particle dimensions [33].
4. Conclusion

The diffuse reflectance spectra of samples with different Fe3+


content are depicted in Fig. 8. The spectra of Fe3+ -doped SnO2
nanoparticles displayed a red shift in the band gap transition
with the increasing dopant content. It was reported that similar
shift was resulted from the incorporation of Fe3+ into the SnO2

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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