Applied Physics A

DOI: 10.1007/s00339-002-1476-7

Materials Science & Processing

g.w. meng1,2,
x.s. peng2
y.w. wang2
c.z. wang2
x.f. wang2
l.d. zhang2

Synthesis and photoluminescence

of aligned SiOx nanowire arrays
1 School

of Chemistry & Chemical Engineering, Anhui University, Hefei, Anhui 230039,

P.R. China
2 Institute of Solid State Physics, Chinese Academy of Sciences, Hefei, Anhui 230031, P.R. China

Received: 29 April 2002/Accepted: 30 April 2002

Published online: 10 September 2002 Springer-Verlag 2002

Aligned SiOx nanowire arrays standing on a Si substrate were successfully synthesized using a simple method by heating a single-crystalline Si slice covered
with SiO2 nanoparticles at 1000 C in a flowing Ar atmosphere. The SiOx nanowire
arrays were characterized by scanning electron microscopy and transmission electron
microscopy. The SiOx nanowires become progressively thinner from bottom to top.
The formation process of the SiOx nanowire arrays is closely related to a vaporsolid
mechanism. Room-temperature photoluminescence measurements under excitation at
260 nm showed that the SiOx nanowire arrays had a strong bluegreen emission at
500 nm (about 2.5 eV), which may be related to oxygen defects.
ABSTRACT

PACS 81.05Y; 78.55

Introduction

Recently, nanostructured arrays [14] have attracted much attention

in theoretical studies and for potential applications in nanotechnology and
nanodevices. These arrays have been
synthesized using different methods,
such as template methods (including
anodic-alumina templates [1, 2] and
polymer templates [3]), self-organization methods [4], and so on. Recently,
one-dimensional (1D) silica nanostructures have attracted considerable attention because of their potential application in the high-resolution optical heads
of scanning near-field optical microscopes and future nano-interconnection
integrated optical devices [5]. On the
basis of the vaporliquidsolid (VLS)
growth mechanism, silica nanowires
have been synthesized by laser ablation [5] and thermal evaporation [6]. In
contrast, silica nanotubes and nanofibers
have also been synthesized via a vaporphase process [7]. All the above-men-

tioned 1D-silica nanostructures were

randomly oriented. In this communication, we report a simple method for
the synthesis of aligned SiOx nanowire
arrays. These SiOx nanowire arrays,
grown on a Si substrate, were obtained
from a Si slice covered with SiO2
nanoparticles at 1000 C. We have also
studied the photoluminescence properties of these nanowire arrays and we
have found that there exists a bluegreen
emission from these arrays at room
temperature, peaking at 500 nm (about
2.5 eV).
2

Experimental

The experimental procedure

was as follows: A single-crystalline Si
slice was cleaned by H2 O2 and a HF
aqueous solution. The Si slice was then
placed in a ceramic boat and covered
with some SiO2 nanoparticles (about
70 nm in diameter). The boat was then
placed in a ceramic tube with a 25-mm
inner diameter and heated in an ap-

Fax: +86-551-559-1434, E-mail: gwmeng@mail.issp.ac.cn

paratus using siliconcarbon rods in

a horizontal electronic-resistance furnace. The system was rapidly heated
to 1000 C and kept at this temperature for 60 min in a flowing Ar atmosphere (160 sccm). After the system had
cooled to room temperature, a thin layer
of wool-like product was found on the
Si slice. The as-synthesized products
were characterized by SEM (JEOL JSM
6300), TEM (JEOL 2010, operated at
200 kV) and energy-dispersive X-ray
fluorescence (EDX) (EDAX, DX-4), attached to the JEOL 2010. For SEM
observations, the as-synthesized product was pasted on an Al substrate by
carbon conducting paste. For TEM investigations, the as-synthesized product
was briefly ultrasonicated in ethanol,
and then a drop of the suspension was
placed on a holey copper grid with
carbon film behind. The photoluminescence (PL) spectrum was obtained using
a Hitachi 850-fluorescence spectrophotometer excited at 260 nm with a filter at 310 nm and a Xe lamp at room
temperature.
3

Results and discussion

Figure 1a shows the SEM

morphology of the SiO2 nanoparticles on the Si substrate before heating
the system. Figure 1b and c show the
typical SEM morphologies of the assynthesized product. It can be observed
that all the nanowires are parallel to each
other and perpendicular to the Si substrate, and form self-oriented, regularly
aligned arrays. Furthermore, the diameter of each nanowire becomes smaller
and smaller from the bottom to the top,
which may be attributed to the decrease

Rapid communication

Appl. Phys. A 76, 119121 (2003)

120

Applied Physics A Materials Science & Processing

CPS (arb. units)

Si

O
Cu
Cu

a SEM morphology of SiO2 nanoparticles on a Si substrate before heating. b A typical

low-magnification SEM morphology of the assynthesized product. c High-magnification SEM
image of the as-synthesized product
FIGURE 1

10

Energy (KeV)
a TEM image of a single nanowire. The inset is the corresponding SAED pattern recorded
from it. b The corresponding EDX spectrum

FIGURE 2

PL Intensity (arb. units.)

in SiOx vapor in the later deposition

process.
Figure 2a shows a TEM image of
a single nanowire. The inset is the
corresponding selected-area electron
diffraction (SAED) pattern recorded
from the nanowire. It can be seen that
the nanowire is about 70 nm in diameter and of an amorphous state, indicated by the highly diffusive SAED ring
pattern. The corresponding EDX spectrum shown in Fig. 2b reveals that the
nanowire consists of Si and O, with an
atomic ratio of Si : O = 1 : 1.4.
The PL spectrum from a bulk quantity of SiOx nanowire arrays is shown
in Fig. 3. There exists a strong blue
green emission from these nanowire arrays, with a peak at about 500 nm (about
2.5 eV). The PL of various silica glasses
and nanowires has been studied extensively [811], because amorphous SiO2
films are widely used as passivation or
insulation layers in integrated circuits.

300

400

500

600

700

800

wavelength
FIGURE 3

PL spectrum from a bulk quantity of SiOx nanowire arrays

Several luminescence bands in various

silica glasses and nanowires, with different peak energies ranging from 1.9
to 4.3 eV, have been observed. It has
been revealed that the 2.7 eV band can
be attributed to the neutral oxygen va-

cancy ( Si Si ), while the 3.0 eV

band corresponds to some intrinsic diamagnetic defect center, such as twofoldcoordinated silicon lone-pair centers
(O Si O). These defects are clearly
due to a high oxygen deficiency dur-

MENG et al.

Synthesis and photoluminescence of aligned SiOx nanowire arrays

ing sample preparation. These structure

defects are radioactive recombination
centers. Therefore, it is reasonable to believe that the bluegreen emission from
the SiOx nanowire arrays can be attributed to the above-mentioned defect
centers, which arise from the oxygen
deficiency.
It is well known that several models
exist to explain the growth mechanism
of crystalline whiskers or nanowires.
One is the vaporliquidsolid (VLS)
growth mechanism, in which the main
feature is the presence of intermediates
that serve as catalysts between the vapor feed and the solid growth at elevated
temperature, and a feature of the morphology is a catalyst particle located at the
end of the nanowire. A typical example
of nanowire growth controlled by the
VLS mechanism is GaAs [12]. Another
model is the conventional structuraldefect-growth mechanism [13]. In many
cases, structural defects may play an
important role in nucleation; in particular, a screw dislocation can serve
as the center of nucleation for MgO
nanowires [13]. The dislocation model
loses its meaning in our case because
these SiOx nanowire arrays are amorphous, and the growth of the SiOx nanowire
arrays does not match the VLS mechanism because no nanoparticles have been
observed on any ends of the nanowires.
From the synthesis process and experimental observations, we suggest that the
following reaction should be involved
in the nucleation and growth of SiOx

121

nanowires:
Si(g) + SiO2 2SiOx (g)

(1)

Firstly, SiOx molecules or clusters are generated from (1), and will
then deposit on the surface of the Si
slice. The deposited SiOx forms the nuclei for the growth of SiOx nanowires.
Next, the post-formed SiOx molecules
or clusters are absorbed on the nuclei
to form SiOx nanowires, or on the surface of the Si slice to form new nuclei, leading to the growth of new SiOx
nanowires. As for the array morphology, the nucleation and growth of
vertically aligned arrays are entirely
self-organized processes. The alignment mechanism is not clear. It may be
due to an effect between the nanowires,
which prevents the nanowires from
growing randomly. Determining the
nature of the mechanism will require
further theoretical and experimental
work.
4

Summary

In summary, SiOx nanowire

arrays were successfully synthesized
on a Si substrate from a Si slice covered with SiO2 nanoparticles. Blue
green photoluminescence peaked at
500 nm (about 2.5 eV) from these arrays, could be attributed to defect centers associated with oxygen deficiencies in the SiOx nanowire arrays. These
arrays may have potential application
in the future in nanodevices such as

nano-interconnection integrated optical

devices.
ACKNOWLEDGEMENTS This work
was supported by Natural Science Foundation of
China, Grant No. 19974055, and the Key Project
of National Fundamental Research.

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