Materials Letters 64 (2010) 1921

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Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t

Structural and optical properties of Al-doped SnO2 nanowires

M. Lei, Q.R. Hu, S.L. Wang, W.H. Tang
Department of Physics, Center for Optoelectronics Materials and Devices, Zhejiang Sci-Tech University, Xiasha College Park, Hangzhou 310018, China

a r t i c l e i n f o a b s t r a c t

Article history: We report a facile thermal evaporation method for the syntheses of Al-doped SnO2 nanowires using Al-
Received 5 June 2009 doped SnO2 nanoparticles as precursors. High-density, single-crystalline Al-doped SnO2 nanowires were
Accepted 29 September 2009 directly grown on the 6H-SiC substrates without any catalyst. X-ray diffraction patterns show that the Al
Available online 6 October 2009
dopants are incorporated into the rutile SnO2 nanowires. The X-ray photoelectron spectra conrm the SnO2
nanowires doped with 5 at.% Al. The photoluminescence spectra of the Al-doped SnO2 nanowires exhibit that
Keywords:
Nanomaterials
the large blue shift of the emission band can be observed in the Al-doped SnO2 nanowires compared with
Chemical vapor deposition undoped nanowires. The distortion of the crystal lattices caused by incorporation of Al atoms at the
Optical materials and properties interstitials should be responsible for the large blue shift of the emission band.
2009 Elsevier B.V. All rights reserved.

1. Introduction 2. Experimental

Tin oxide (SnO2) has been widely used in large scale applications
including at panel displays, solar cells, gas sensing devices, eld
emission transistors and light emitting diodes due to its special
properties including wide band gap, excellent chemical and thermal
stability, and natural non-stoichiometry [15]. Recently, the perfor-
mance of SnO2 has been found to improve by using low-dimensional
metal-doped SnO2 nanostructures. Various magnetic metal-, transition
metal- and rare earth metal-doped SnO2 nanostructures mainly
including lms and nanoparticles have successfully fabricated, and
related diluted magnetic semiconductor properties, high lithiumion
capacity, enhanced gas sensing and humidity sensitive properties,
excellent electrocatalytic activity and stability are successfully achieved
[613]. Compared with the more attentions to syntheses and properties
of metal-doped nanolms and nanoparticles, the metal-doped SnO2
nanowires have achieved less attention. Very recently, more studies
have focused on the synthesis of metal-doped SnO2 nanowires and their
applications due to its enhanced excellent eld emission property, and
transparent metallic conductivity [1417]. The metal-doped nanowires
can process high carrier concentrations, low oxygen vacancies and low
resistivities, which makes them more suitable for transparent conduct-
ing oxides (TCO) materials. Here, we report a facile route to synthesize
single-crystalline Al-doped SnO2 nanowires. The structure and photo-
luminescence (PL) property of the Al-doped SnO2 nanowires were
investigated in detail, and presented some novel features.
Corresponding author. Tel./fax: +86 571 86843222.
E-mail address: whtang@zstu.edu.cn (W.H. Tang).
Al-doped SnO2 nanoparticles with 20 at.% Al were used as source
material. The Al-doped SnO2 nanoparticles were rst synthesized by a
hydrothermal method reported in the literature [18]. In the experi-
ments, an alumina boat containing 2 g Al-doped SnO2 nanoparticles was
loaded in the center of horizontal alumina tube. The 6H-SiC substrates
were placed on the downstream end of the alumina tube. After
evacuating the furnace to the pressure of 10 2 Torr, Ar was used as
carrier gas at a ow rate of 50 sccm to facilitate the reaction. Then the
furnace temperature was ramped to 1550 C and held for 90 min. After
the system was cooled down to room-temperature, white product was
found to deposit on the 6H-SiC substrate. The morphology of the
nanowires was characterized using eld emission scanning electron
microscopy (SEM, FEI XL-30). The X-ray diffraction (XRD) pattern was
measured using a Rigaku X-ray diffractometer (Cu K radiation,
= 1.5418 at 40 kV and 160 mA). The composition of the nanowires
was analyzed by X-ray photoelectron spectra (XPS) recorded on a
VGESCALAB MKII X-ray photoelectron spectrometer. The microstruc-
ture of the nanowires is further characterized by transmission electron
microscope (TEM JEOL 2010F). PL spectra of the products were collected
using the HeCd laser as the excitation source.
3. Results and discussion
Fig. 1a shows the representative image of the Al-doped SnO2
nanowires. Straight nanowires with high purity are found to deposit
on the substrates. The enlarged SEM image reveals that these
nanowires are of smooth surface and uniform size along growth
direction. The average diameter and length of the nanowires are
around 80 nm and 5 m, which is similar to those of undoped SnO2
nanowires (not shown here). Fig. 1cd shows the XRD patterns of the
Al-doped and undoped SnO2 nanowires, respectively. It is found that

0167-577X/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2009.09.058
20 M. Lei et al. / Materials Letters 64 (2010) 1921

Fig. 1. (ab) SEM image of the Al-doped SnO2 nanowires with different magnication. (cd) XRD patterns of Al-doped and undoped SnO2 nanowires, respectively.

both XRD patterns can be well indexed as rutile SnO2 (ICDD-PDF No.
41-1445) and no other crystalline forms are detected. We further
observe that the intensity of (101) and (110) peak is increased and
decreased, respectively, compared with that of undoped SnO2
nanowires. Moreover, careful examination detects an obvious low
angle shift of the Al-doped nanowires relative to that of undoped
nanowires. The shift of the (101) peaks to lower angle is (2) =
0.15, revealing increase in the both lattice constants and cell volume.
The Al atoms would be incorporated at the interstitials and thus lead
to the lattice distortion. XPS analysis was used to further determine
the composition of the Al-doped SnO2 nanowires. The ne XPS spectra
of O1s, Sn3d and Al2p are shown in Fig. 2ac, respectively. The binding
energies centered at 531, 487, 495, 75 eV for O1s, Sn3d5/2, Sn3d3/2 and
Al2p, respectively, are in good agreement with the calculated value of
the relative elements. The Al content is estimated to be about 5 at.%
from half-quantication calculation.
Fig. 3a shows TEM image of the Al-doped SnO2 nanowires, further
revealing that the nanowires are of smooth surface and uniform size
along growth direction. The EDS spectrum indicates the nanowires are
composed of Sn, O and Al elements. The Al content is about 5 at.%. The
Cu signal comes from the Cu grid. The indexed FFT pattern (Fig. 3c)
shows the single-crystalline nature of the nanowires. Fig. 3d shows
HRTEM image of the region denoted in Fig. 3a. Two sets of lattice
fringes with spacing distance of 0.33 and 0.17 nm, normal to each
other, corresponding to the (110) and (211) planes of rutile SnO2
(ICDD-PDF No. 41-1445). Combined FFT pattern and HRTEM analysis,
the growth direction is along [301], which is different from [121]
direction of the undoped nanowires.
Fig. 4ab shows the room-temperature PL spectra of undoped
and Al-doped SnO2 nanowires, respectively. The near band-edge
(NBE) emission is not found in these two samples due to their non-
stoichiometry nature. The PL of the undoped sample indicates a strong
yellow emission centered at 576 nm with a small orange emission at
629 nm. It had been demonstrated that the yellow emission originates
from large amount of ionized oxygen vacancies (Vo), and the orange
emission results from the tin interstitial (Sni) [19,20]. Nevertheless,
green and yellow emission band centered at 537 and 575 nm are
observed in the Al-doped sample, as shown in Fig. 4b. There is a large
blue shift of PL emission in Al-doped sample, compared with that of
undoped sample. We deduce that distortion of crystal lattice of Al-doped
sample should be the main reason for the large blue shift of emission.
The XRD pattern has indicated that the Al atoms are incorporated at the
interstitials, which further results in the increase of cell volume and
distortion of crystal lattice. As is well known, distortion of crystal lattice
can result in large tensile stress, which can further inuence optical
properties. We deduce that the large blue shift is associated with tensile
stress in the Al-doped SnO2 nanowires. The deep-level emission induced
by ionized oxygen vacancies and tin interstitials would move to the

Fig. 2. XPS spectra of Al-doped SnO2 nanowires: (a) O1s region; (b) Sn3d region; (c) Al2p region.
 M. Lei et al. / Materials Letters 64 (2010) 1921
Fig. 3. (a) Typical TEM image of the Al-doped SnO2 nanowires. (b) EDX spectrum collected from the nanowires. (c) The corresponding FFT pattern of the denoted region of the
nanowires. (d) HRTEM image of the nanowires.
Fig. 4. PL spectra of (a) undoped SnO2 nanowires and (b) Al-doped SnO2 nanowires.
short wavelength range due to the strong tensile stress. The tensile
stress-caused blue shift is often encountered in other doped metal
oxides semiconductors such as doped ZnO nanowires [21,22]. Never-
theless, the exact mechanism is unknown and needs to be further
investigated.
4. Conclusions
We have reported a novel route to straight Al-doped SnO2 nanowires
using Al-doped SnO2 nanoparticles as precursor. These nanowires are of
smooth surface and uniform size along growth direction. The average
diameter and length of the nanowires are around 80 nm and 5 m,
respectively. The lower angle shift of the XRD pattern was observed in
the Al-doped SnO2 nanowires, indicating that the Al doping would
expand the lattice constants of the SnO2. XPS and EDS analysis conrms
that Al content is estimated to be about 5 at.%. The HRTEM image and
FFT pattern reveal that these Al-doped SnO2 nanowires consist of single-
crystalline rutile SnO2 grown along the [301] direction. In addition, large
blue shift of PL emission is observed in Al-doped nanowires, compared
21
with that of undoped sample. We deduce that the large tensile stress-
caused by distortion of crystal lattice is main reason for the interesting
blue shift of the emission band.
Acknowledgement
This work was supported by the National Natural Science
Foundation of China (60571029, 50672088) and the Innovative
Youth Team of Natural Science Foundation of Zhejiang Province
(R4090058).
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