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Journal of Non-Crystalline Solids xxx (2008) xxxxxx

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Journal of Non-Crystalline Solids

journal homepage: www.elsevier.com/locate/jnoncrysol

Synthesis and characterization of 3CSiC nanowires

G. Attolini *, F. Rossi, M. Bosi, B.E. Watts, G. Salviati
IMEM-CNR Institute, viale Usberti 37/A, 43100 Parma, Italy

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

Available online xxxx Silicon carbide nanowires have been synthesized by carbothermal reduction, from carbon monoxide and
single crystal silicon. Transmission electron microscopy and cathodoluminescence studies conrm the
PACS: growth of a cubic b-SiC core, coated with an amorphous oxide shell. Planar defects, as stacking faults
61.46.km and rotational twins, are present on (1 1 1) planes. The formation of short thick rods or long thin wires,
68.37.d depending on the growth temperature and time, is discussed.
61.72.Nn 2008 Elsevier B.V. All rights reserved.

Keywords:
Silicon carbide
Nanowires
Planar defects

1. Introduction 2. Experimental

Recently, many studies have reported the preparation and char-
acterization of 1D nanostructures such as nanowires (NWs) of oxi-
des, nitrides, carbides, IIIVs, metals and silicon [1]. NWs often
present chemical, physical, electrical, optical, and mechanical
properties better than the bulk material, opening up new elds
of fundamental research and nano-technological applications [2].
Cubic silicon carbide (b-SiC) is a wide band-gap semiconductor,
which displays elevated hardness, electron mobility, thermal con-
ductivity and resistance to chemical attack [3]. Hence, b-SiC NWs
are interesting because their good physical and chemical proper-
ties make them a promising material for devices operating in harsh
environment [4]. Functionalized NWs have the potential to act as
highly sensitive biochemical detector elements [5].
Many methods are being used to prepare SiC NWs, on silicon
substrates, using a catalyst: chemical vapor deposition [6], vacuum
evaporation of SiC [7], direct synthesis from Si and C powders [8].
In this article we report on the properties of b-SiC NWs, pre-
pared by a reaction between single crystalline Si and CO using Ni
catalyst. The synthesis is based on the carbothermal reduction of
silica present as the native oxide on the surface of Si. The structural
properties of the NWs investigated by scanning and transmission
electron microscopies are discussed.
The growth of SiC NWs on (1 0 0) Si substrates was performed in
an open-tube under a ow of CO and with N2 or Ar as carrier gases,
at temperatures between 1050 and 1100 C.
The substrate was cleaned with organic solvents in an ultra-
sonic bath, dipped in a 0.01 M solution of nickel nitrate in ethanol
and dried in an oven at 60 C. The native silicon dioxide present on
the substrate surface was not removed before treatment with the
nickelsalt solution.
The sample was placed in an open-ended tube, previously
purged to remove air, which in turn was put inside a horizontal
furnace. After the desired temperature prole was obtained, the
tube was moved to position the substrate at the center of the fur-
nace. When the temperature had stabilized the carbon monoxide
was introduced into the tube and the growth proceeded for 15
and 90 min.
At the growth temperature, carbon transport takes place in
three stages: (i) CO adsorption on the silicon dioxide, (ii) diffusion
through the SiO2 and (iii) reaction with the silicon [9,10]. We can
suppose that the reaction at the interface SiO2/Si is the following:
4COg 6Si 4SiCs 2SiO2 s 1

The morphology and density of the NWs were examined by

Scanning Electron Microscopy (SEM). The crystalline structure
was investigated by powder X-ray diffraction (XRD) and by con-
* Corresponding author. Tel./fax: +39 0521269267. ventional transmission electron microscopy (TEM) at 200 kV. The
E-mail address: giovanni@imem.cnr.it (G. Attolini). optical emission was studied by SEM-Cathodoluminescence (CL).

0022-3093/$ - see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jnoncrysol.2008.05.064

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3. Results and discussion
SEM images of the wires are shown in Fig. 1a and Fig. 2a. The
growth conditions (temperature, TG, and time, tG) determine the
NW size. At TG = 1100 C, tG = 90 min. an ensemble of roughly
aligned rods is obtained (Fig. 1a), with diameters up to 2 lm and
lengths of about 40 lm. At TG = 1050 C, tG = 15 min. (Fig. 2(a)) a
dense network of high quality, long, interwoven bers is obtained,
several hundreds of microns long with uniform diameters under
80 nm.
The rod-like nanostructures showed an efcient CL emission
(see the panchromatic image in Fig. 1(a)). The room temperature
CL spectrum (not shown here) revealed a broad peak centered at
about 2.34 eV, related to the indirect band-gap transition in b-
SiC, and an intense blue band at about 2.68 eV. Blue luminescence
from cubic SiC whiskers and nanocrystallites has been reported in
the literature [11], but the contribution of an SiO2 related emission
in this spectral region [12] also should be considered. This assign-
ment is supported by TEM observations (see Fig. 1(b)), which re-
veal a core-shell structure of the rods, with a b-SiC crystalline
core and an amorphous oxide shell.
This coreshell system can be modied by varying the growth
conditions. In particular, a decrease of tG and TG resulted in a reduc-
tion of the oxide layer to a few nm. This is conrmed by TEM
images of the thin and long NWs, having only a nanometric oxide
shell (see Fig. 2(b)).
The NWs have a <1 1 1> growth axis and planar defects on (1 1 1)
planes (stacking faults and rotational twins); similar defects have
been reported previously [13,14]. Selected area electron diffraction
(SAED) from single NWs (inset in Fig. 2b) indicates that the main
phase is 3C-SiC. The XRD spectrum in Fig. 3, with the peaks in-
dexed as b-SiC, after a Reitveld renement carried out using the
MAUD program gives a value of 4.361 for the lattice parameter.
No evidence of other polytypes phases is observed but the shoulder
on the additional 111 peak at 33.7 is indicative of stacking faults
and is in good agreement with Ref. [15].
4. Conclusions
Silicon carbide nanowires have been grown by a carbothermal
method based on the reaction between carbon monoxide and the

Fig. 1. (a) SEM and panchromatic CL images of a rod ensemble, grown at 1100 C. (b) TEM image, showing the rods have a coreshell structure.

Fig. 2. (a) SEM image of a NW network, grown at 1050 C. (b) Bright eld TEM image. Inset: SAED pattern of a single wire in [0 1 1] zone axis. The main spots correspond to the
b-SiC polytype. The dotted and dashed hexagons outline a pair of twins.

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G. Attolini et al. / Journal of Non-Crystalline Solids xxx (2008) xxxxxx
Fig. 3. XRD pattern of SiC wires on a 100 Si substrate with the cubic SiC indexed ()
and the extra stacking fault peak (s.f.).
native oxide on the silicon substrate, using nickel nitrate as the
catalyst.
Structural studies using scanning and transmission electron
microscopies reveal that the growth habits vary markedly as the
temperature is raised from 1050 to 1100 C. At lower temperatures
long thin wires grow but at higher the wires tend to align but their
diameters vary considerably. They have a coreshell structure con-
sisting of a silicon carbide core enveloped by amorphous oxide.
Please cite this article in press as: G. Attolini et al., J. Non-Cryst. Solids (2008), doi:10.1016/j.jnoncrysol.2008.05.064
3
Stacking faults and twins are observed, mainly in the (1 1 1) basal
plane.
Acknowledgments
The authors thank Dr. D. Calestani for his assistance in SEM
characterization. This work was partially funded by a project of
the Italian Ministry of Foreign Affairs for ItalyJapan bilateral
cooperation.
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