Growth of Zinc Oxide Nanowires

on Silicon (100)
INTRODUCTION
 The unique and fascinating properties of
nanostructured materials have triggered
tremendous motivation among scientists to
explore the possibilities of using them in
industrial applications. In this article, they
report the preparation of ZnO nanowires on
Si (100) substrate by using an Au catalyzed
VLS process.
About the research:
 Fabrication of ZnO nanowires.
 SEM, TEM and AFM analysis.
 XRD, XPS and EDX analysis.
 PL analysis.
Fabrication of ZnO nanowires.
 There are at least four different stages
involved in the formation of ZnO
nanowires:
* Au film deposition.
* Alloy nanoparticles formation.
*Absorption and nucleation.
*Epitaxial growth of ZnO nanowires.
 Figure 1. Schematic
illustration of vapor-
liquid-solid nanowire
growth mechanism
(a) Au filmdeposition;
(b) alloy nanoparticles
formation;
(c) absorption and
nucleation;
(d) epitaxy growth
Au film deposition
 The (100) oriented Si wafers were
used as the substrates for nanowires
growth. After standard cleaning, a
layer of 70 Å thick Au thin film was
deposited on silicon substrate by rf-
magnetron sputtering.
Alloy nanoparticles formation

 The substrates with Au thin films

were annealed at 500 °C for 30 min
in vacuum in order to form Au
nanoparticles on the substrates.
Absorption and nucleation
 The ZnO nanowires might be nucleated on the
Au/Si alloy nanoparticles. As the temperature
increased to~900 °C, the ZnO was reduced by
graphite and CO(g). The corresponding
chemical reaction can be expressed as:

ZnO(s) + C(s)→ Zn(g) + CO(g) (1)

CO(g) + ZnO(s) → CO2(g) + Zn(g) (2)
 The gaseous products produced by
reactions (1) and (2) would adsorb and
condense on the alloy droplets.
Subsequently, the following reaction (3) is
catalyzed by the Au-Si alloy at solid- liquid
interface.

Zn(g) + CO(g) → 　 ZnO(s) + C(s) (3)

C(s) + CO2(g) → 2CO(g)

Epitaxial growth of ZnO nanowires

 The ZnO nanowires were grown on

the annealed Au-coated Si
substrates at temperatures from 850
to 950 °C for 1-30 min.
 SEM ,TEM and AFM
analysis
 The compositions of the alloy tips and ZnO
substrate surface were examined by SEM
(scanning electron microscope).

 The microscopic characterization indicates

the oblique ZnO nanowires with a hexagonal-
pole shape grown on the substrate as shown
in Figures2(a),
 Figure 2.
(a) The top view of
SEM images of ZnO
nanowires;
(b) the 45° tilted view
of SEM images of
ZnO nanowires;
(c) cross section
SEM images of ZnO
nanowires
 The TEM (transmission electron
microscopy ) images of single crystalline
ZnO nanowire clearly showed
microstructural features of the nanowires
as indicated in Figure 3.

 Typical nanowires have an alloy droplet at

the tip and the length up to 1-2 μm, and
the d-spacing of (002) crystal plane is 2.61
nm.
 Figure 3.
(a) TEM image of ZnO
nanowire with a Au-Si alloy
tip;
(b) High-resolution TEM
image of a single crystalline
ZnO nanowires and the
corresponding electron
diffraction pattern as shown
in inset.
 A selected area electron diffraction
(SAED) pattern (inset of Figure 3(b))
depicts the single crystalline nature of
ZnO nanowires.

 Atomic force microscopy (AFM) was

performed to observe the surface
morphology of annealed Au/Si
substrate.
 Figure 4. AFM image of Au-Si alloy
nanoparticles with mean diameter of 25 nm
 XRD, XPS and EDX analysis

 The XRD (X-ray diffraction) pattern of ZnO

nanowires reveals a wurtzite structure for
the nanowires (Figure 5). The lattice
constants of ZnO nanowires are a = b=
3.26 Å and
c = 5.22 Å.
 Figure 5. XRD pattern of ZnO nanowires grown
on a silicon (100) substrate.
 The composition of ZnO nanowires was
further determined by the XPS (X-ray
photoelectron spectroscopy).

 The two strong peaks located at 536.61 and

1026.00 eV are respectively due to the O (1s)
and Zn (2p3) binding energies for ZnO
nanowires (Figure 6).
 Figure 6. XPS spectra
of the synthesized ZnO
nanowires,
(a) full range surveyed
spectra;
(b) zinc 2P3 spectra;
(c) oxygen 1s spectra
 Nanowires were identified by EDX (energy
dispersive X-ray analysis) and the result is
shown in Figure 7.

 The EDX analysis provided precise

composition of the tip.
 Figure 7. EDX
spectra on
(a) tip of the ZnO
nanowires,
(b) ZnO nanowires
 The EDX spectra in Figure 7 (a) feature
peaks corresponding to elements Au, Si,
Zn and O peaks (the Cu peaks come from
the Cu TEM grid), which depict the
characteristic composition of a tip of a
nanowire.
 PL analysis

 Figure 8 shows the room temperature PL

spectrum of the ZnO nanowires. A strong
UV emission at around 381 nm and a green
light emission at 520 nm are observed.
 Figure 8. Photoluminescence spectra of ZnO
nanowires at room temperature
CONCLUSION
 In summary, they have synthesized tilted ZnO
nanowires on the Si (100) substrate by VLS
growth process using Au as catalyst. The
process leads to the formation of oblique ZnO
nanowires on the Si substrate without buffer
layer. The SEM and TEM analyses of ZnO
nanowires indicate that the ZnO nanowires
grow epitaxially as hexagonal poles along [001]
direction.
 The ZnO nanowires have diameters
ranged from 60 to 100 nm and lengths 1-
3 μm. The XRD, XPS and EDX analyses
provide the evidence for the presence of
small amounts of silicon in the nanowires.
The ZnO nanowires are stoichiometric
and are found to emit UV light at room
temperature.
Thank you for listening!!!