ZINC OXIDE NANOWIRES SYNTHESIZED BY THERMAL EVAPORATION METHOD WITH

AND WITHOUT CATALYST

Syahida Suhaimi*a, Samsudi Sakrania, Tashi Dorjia, Peshawar O. Aminb
a)
Department of Physics, Faculty of Science, Universiti Teknologi Malaysia, 81310 Johor Bahru, Malaysia.
b)
Department of Physics, School of Science Education, University of Sulaimani, Sulaimani, Iraq.

ABSTRACT

The fabrication of zinc oxide nanowires and their characterization are presented in this paper. Gold catalyst was employed on certain set of experiments.
The sample were fabricated within a horizontal quartz tube under controlled supply of O2 and Ar gases and heated at 700oC up to 1200oC. Initially, the
tube was evacuated around 1 torr using a mechanical pump and the gas is allowed to pass at a known flow rate so that the evaporated source will be
driven to the Silicon substrate. The substrate was previously cleaned and deposited with gold nanoparticles using a dipping process to act as a catalyst
during vapor-liquid-solid mechanism. Another set of samples was prepared without the aid of gold catalyst and the process involved is called self-
catalytic growth. The structural morphology of both catalyst and catalyst-free samples was characterized using scanning electron microscopy and field
emission scanning electron microscopy, whilst the field emission properties of the nanowires were measured using photoluminescence spectroscopy at
room temperature. Both SEM and FESEM results showed that the optimal conditions for the growth of ZnO nanowires with gold catalyst were
identified as follows: 90 mins growth time and gas flow rate ranging from 1.1 to 5.0 sccm. High aspect ratio of around 10.5 and low surface density
were also observed. Catalyst-free ZnO:Al nanowires showed a randomly orientated nanowires with varying nanostructures as the dopant concentrations
were increased from 0 to 2.4 at%. Interesting features were observed at 2.4 at%, shown by a perfect hexagonal similar to pencil-like shape. This was
further analysed by EDX which confirmed an optimal level of dopant concentration for the synthesis of ZnO:Al nanorods. The measured diameters
were roughly between 260 to 350 nm and the length about 720 nm. From The results showed the importance of Al doping that played an important role
on the morphology of ZnO nanostructures. This may led to potential applications in sensor and biological applications.

KEYWORDS: Hot-tube thermal evaporation, ZnO nanowires, Al doped nanowires, Vapor-liquid-solid mechanism.

different sets; coated with Au catalyst and uncoated

1. INTRODUCTION
Zinc Oxide (ZnO) is a II-IV semiconductor
compounds which has a wide bandgap of 3.4 eV. It has a
unique position among semiconducting oxides due to its
piezoelectricity and transparent conducting properties that
have made it to become a very versatile and promising
material. There has been increasing interest in ZnO
nanostructures such as nanowires, nanorods, nanobelts and
nanotubes due to their unique physical properties and
potential application [1]. Nanowires are grown in many
ways since it was first introduced into the nanotechnology
world in the late 60s. Several methods have been widely
used by previous researchers in order to grow the
nanostructures including laser-assisted chemical vapor
deposition (CVD) [2-5], oxide-assisted CVD [6], thermal
CVD [7], metal-catalyzed molecular beam epitaxy (MBE)
[8-10] and chemical beam epitaxy (CBE) [11]. Since the
structural, optical, magnetic and electrical properties of ZnO
are dependent on growth parameters, hence their
applications. So, the prime interest here is to synthesize
catalyst and catalyst free doped and undoped ZnO
nanosturctures and learn the influence of dopant
concentrations on the structural and optical properties. Over
the time, researchers have used various dopants to dope
ZnO NSs. Doping semiconductor NWs with foreign
elements to manipulate their electrical and magnetic
properties is an important aspect for the realization of
various types of advanced nanodevices [12]. Aluminum
(Al) is one dopant that can be used to enhance phonon
scattering promoted by Al induced grain reinforcement. The
conductivity of the doped NWs is also increased. This study
is aimed at establishing the intermediate growth conditions
for ZnO nanowires arrays on Si (100) substrates with two
.
substrates with a highlight on the substrate tilt angle, argon
flow rate and concentration of doping material.
2. EXPERIMENTAL
Randomly oriented, catalytic growth of ZnO nanowire
was fabricated by means of a hot tube thermal evaporation
process in a horizontal-tube furnace reactor. Pure ZnO
powders (purity 99.99%) were placed in an alumina boat
and heated to 960 C. The ZnO vapour was carried
downstream by a 1.1 to 5.0 sccm Ar flow and condensed
along the colder regions of the furnace tube where the Au-
coated substrates were placed. Typical substrate tilt angles
were set at 0 and 30, with their temperatures expected to
fall below 1000 C. The Ar pressure was set to 10 mbar
during growth and 0.1 bar during the temperature ramps, to
provide pressure-based growth interruptions and avoid non-
steady-state effects [15]. It is believed that the nanowires
are generated directly from the vapour phase in the absence
of a metal catalyst, and this process is often called vapour-
solid (VS) growth. To generate the vapour phases of the
source materials, vacuum conditions are sometimes needed.
This is because some materials may not sublimate in the
normal atmosphere. An effective way to generate the
vapour source materials in a normal atmosphere is to add
additional materials to react with the source materials. For
example, ZnO powder does not sublimate in a normal
atmosphere at 1000 C. By adding carbon powder to react
with the ZnO source, Zn or Zn-suboxide vapor phases can
be easily generated at 1000 C. Various forms of ZnO
nanostructures grow in the low-temperature zone. In this
case, vacuum conditions, carrying gases and catalysts are all
unnecessary. Fig. 1 shows the experimental set up for
synthesizing ZnO nanowires.

To pressure
meter
Rotary
Thermocouple pump
Figure 1 Schematic of experimental setup
In the above experiment, Zn or Zn suboxide play a crucial
role for the nucleation of ZnO nanostructures. This is
because that at a high temperature condition (T> 1100 C),
carbon reduced ZnO into Zn or Zn suboxides by the
following reactions [15]:
ZnO(s) + C(s) Zn(g) + CO(g) (1)
CO(g) + ZnO(s) CO2(g) + Zn(g) (2)
Zn(g) + CO(g) ZnO(nanowire) + C(s) (3)
C(g) + CO2(g) 2CO(g) (4)
In case of the sealed quartz tube the carbon powder
might directly react with ZnO, whilst for the case of the
open-end quartz tube carbon first react with oxygen to form
CO. Zn and Zn suboxides have low melting temperatures
(approximately 419 C for both Zn and ZnOx, where x < 1)
compared to that of ZnO (1975 C) and should be in vapour
phases at 1100 C. At the low temperature site, Zn vapour
generated by reactions (2) and (3) will condense on the
inner wall of the quartz tube forming liquid droplets, which
are ideal catalysts for ZnO nanowire growth through the
VLS mechanism. Carrying gases are not necessary for the
formation of ZnO nanostructures. Temperature is the
critical experimental parameter for the formation of
different morphologies of ZnO nanostructures.
The addition of carbon during the reaction causes Zn
vapour or droplets to partially oxidized and forming
suboxides, which generally have low melting temperatures.
This suboxides (ZnOx) is formed because the amount of
oxygen contributing to the reaction in the open-end quartz
tube is limited. Such a condition is reasonable since Zn
droplets co-exist with ZnO nanowire products in the early
stage of the nanowire formation. Either Zn droplets or
vaporized Zn suboxide droplets could be the nuclei for ZnO
nanowires. Similar to the oxide-assisted growth mechanism
Zn suboxides are more reactive than ZnO and may largely
enhance the deposition of Zn oxides at the tips of ZnO
nanowires during growth. Due to further oxidation of Zn or
Zn suboxides, the concentration of oxygen in the
droplets/tips increases, and thus ZnO deposits on the
.
interface between the droplets and substrate, resulting in the
growth ZnO nanowires.
The growth of doped ZnO nanowires without catalyst
is slightly differ and simpler compared to catalysed growth
process. High purity Zn (99.99%), Al (99.7%), and oxygen
(99.8%) were chosen as the source material. At temperature
about 500 oC, Zn would vaporize and get oxidized to ZnO
by oxygen. Presence of a small amount of Al is expected to
act as the dopant during the ZnO NSs growth which is
expected to form ZnO:Al ultimately. A cleaned substrate
(Si) was placed vertically above the sample holder.
Calculated and weighed mixture (Zn and Al) of 0.5g
was placed on to the substrate holder and the setup was then
loaded into the quartz tube carefully so that it is positioned
at the centre of the furnace/quartz tube. With the help of
rotary pump attached to the furnace, tube chamber was
initially evacuated to approximately 20 torr pressure. This
was important to remove undesirable gases which could be
present initially. At a reduced pressure, it was also possible
to achieve the temperature very quickly. With the
programmable temperature controller, temperature of the
oven was set to desirable value of 700 oC.
The choice of deposition temperature was arrived at by
keeping in mind the melting point of Al being 660.32 oC.
This could ensure abundant Al vapours during the
deposition process. So, the need was to maintain the
temperature of the furnace just above melting point of both
Zn and Al. As the furnace temperature reached the set
value, high purity O2 and Ar in the ratio of 20:80 was
introduced into the quartz tube. Flow rate of O2 was
maintained at 200 sccm (standard cubic centimeters per
second). The purity of O2 and Ar were 99.8% and 99.999%
respectively. The duration of heating was maintained at 120
minutes for all samples based on the preliminary results.
The flow rate of reactant gas (O2) and carrier gas (Ar),
duration of growth time, growth temperature and pressure
were carefully set and monitored since slightest change in
these parameters may affect the result of the samples
obtained. Exactly at the end of 120 minutes of heating, the
flow of reactant and carrier gases were stopped and the
furnace was set to cool down to room temperature before
removing the sample. Once the furnace got cooled to near
room temperature, the sample was removed from it. Greyish
white deposits were observed on the silicon substrate. The
same procedure was repeated for all samples of different
dopant concentrations.
The grown of doped and undoped ZnO nanowires
were characterized by a field emission scanning electron
microscope (FESEM, JEOL JSM-6701F, Japan), combined
with EDX for morphological and compositional analysis.
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