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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.
Figure 1 Schematic of experimental setup Calculated and weighed mixture (Zn and Al) of 0.5g
was placed on to the substrate holder and the setup was then
In the above experiment, Zn or Zn suboxide play a crucial loaded into the quartz tube carefully so that it is positioned
role for the nucleation of ZnO nanostructures. This is at the centre of the furnace/quartz tube. With the help of
because that at a high temperature condition (T> 1100 C), rotary pump attached to the furnace, tube chamber was
carbon reduced ZnO into Zn or Zn suboxides by the initially evacuated to approximately 20 torr pressure. This
following reactions [15]: was important to remove undesirable gases which could be
present initially. At a reduced pressure, it was also possible
ZnO(s) + C(s) Zn(g) + CO(g) (1) to achieve the temperature very quickly. With the
programmable temperature controller, temperature of the
CO(g) + ZnO(s) CO2(g) + Zn(g) (2)
oven was set to desirable value of 700 oC.
Zn(g) + CO(g) ZnO(nanowire) + C(s) (3)
The choice of deposition temperature was arrived at by
C(g) + CO2(g) 2CO(g) (4) keeping in mind the melting point of Al being 660.32 oC.
This could ensure abundant Al vapours during the
In case of the sealed quartz tube the carbon powder deposition process. So, the need was to maintain the
might directly react with ZnO, whilst for the case of the temperature of the furnace just above melting point of both
open-end quartz tube carbon first react with oxygen to form Zn and Al. As the furnace temperature reached the set
CO. Zn and Zn suboxides have low melting temperatures value, high purity O2 and Ar in the ratio of 20:80 was
(approximately 419 C for both Zn and ZnOx, where x < 1)
introduced into the quartz tube. Flow rate of O2 was
compared to that of ZnO (1975 C) and should be in vapour
phases at 1100 C. At the low temperature site, Zn vapour maintained at 200 sccm (standard cubic centimeters per
generated by reactions (2) and (3) will condense on the second). The purity of O2 and Ar were 99.8% and 99.999%
inner wall of the quartz tube forming liquid droplets, which respectively. The duration of heating was maintained at 120
are ideal catalysts for ZnO nanowire growth through the minutes for all samples based on the preliminary results.
VLS mechanism. Carrying gases are not necessary for the The flow rate of reactant gas (O2) and carrier gas (Ar),
formation of ZnO nanostructures. Temperature is the duration of growth time, growth temperature and pressure
critical experimental parameter for the formation of were carefully set and monitored since slightest change in
different morphologies of ZnO nanostructures. these parameters may affect the result of the samples
obtained. Exactly at the end of 120 minutes of heating, the
The addition of carbon during the reaction causes Zn flow of reactant and carrier gases were stopped and the
vapour or droplets to partially oxidized and forming furnace was set to cool down to room temperature before
suboxides, which generally have low melting temperatures. removing the sample. Once the furnace got cooled to near
This suboxides (ZnOx) is formed because the amount of room temperature, the sample was removed from it. Greyish
oxygen contributing to the reaction in the open-end quartz white deposits were observed on the silicon substrate. The
tube is limited. Such a condition is reasonable since Zn same procedure was repeated for all samples of different
droplets co-exist with ZnO nanowire products in the early dopant concentrations.
stage of the nanowire formation. Either Zn droplets or
vaporized Zn suboxide droplets could be the nuclei for ZnO The grown of doped and undoped ZnO nanowires
nanowires. Similar to the oxide-assisted growth mechanism were characterized by a field emission scanning electron
Zn suboxides are more reactive than ZnO and may largely microscope (FESEM, JEOL JSM-6701F, Japan), combined
enhance the deposition of Zn oxides at the tips of ZnO with EDX for morphological and compositional analysis.
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
.
.