Submitted in partial fulfilment of the requirements for
the degree of Doctor of Philosophy in the Faculty of science
Department of Chemistry
University of the Witwatersrand. November 2016.An overview of the evolution of synthesis and applications of indium nitride and gallium
nitride in modern science and technology is provided. The working principles and parameters
of chemical vapour deposition (CVD) synthesis technique are explored in this study.
In this study indium oxide, indium phosphate, indium nitride and gallium nitride materials are
prepared by CVD. The versatility of CVD on the fabrication of one-dimensional (1D)
structures is portrayed. Both change in dimensionality and change in size are achieved by a
CVD technique. 1D indium oxide (In2O3) nanowires, nanonails and nanotrees are synthesised
from vapour deposition of three-dimensional In2O3 microparticles. While 1D structures of the
novel indium phosphate known as triindium bisphosphate In3(PO4)2 were obtained from
reactions of In2O3 with ammonium phosphate. The effect of temperature, activated carbon
and the type of indium precursor on dimensionality of the synthesized materials is studied.
The inter-dependency between temperature and precursors is observed. The presence of
activated carbon at high temperatures encouraged growth of secondary structures via
production of excess indium droplets that act as catalysts. The combination of activated
carbon and high temperature was found responsible for the novel necklace, nanonail,
nanotree and nanocomb structures of In2O3.
Indium nitride (InN) has for the first time been made by a combined thermal/UV photoassisted
process. In2O3 was reacted with ammonia using two different procedures in which
either the ammonia was photolysed or both In2O3 and ammonia were photolysed. A wide
range of InN structures were made that was determined by the reaction conditions (time,
temperature). Thus, the reaction of In2O3 with photolysed NH3 gave InN rod like structures
that were made of cones (6 h/ 750 oC) or discs (6 h/ 800 oC) and that contained some In2O3
residue. Photolysis of In2O3 and NH3 by contrast gave InN nanobelts, InN tubes and pure InN
tubes filled with In metal (> 60 %). The transformation of the 3D In2O3 particles to the
tubular 1D InN was monitored as a function of time (1-6 h) and temperature (700-800 oC);
the product formed was very sensitive to temperature. The band gap of the InN tubes was
found to be 2.19 eV and of the In filled InN tubes to be 1.89 eV.
Gallium nitride (GaN) and indium gallium nitride (InGaN) nanostructures were synthesized
from thermal ammonification of gallium oxide (Ga2O3) as well ammonification of a mixture
of In2O3 and Ga2O3 respectively. The effect of temperature on preparation of high purity GaN
was studied. The GaN materials synthesized at 800 °C showed a mixture of the gallium oxide
and the gallium nitride phases from the XRD analysis. However at temperatures ≥ 900 °C
high quality GaN nanorods were obtained. The band-to-band ultraviolet optical emission
value of 3.21 eV was observed from the GaN nanorods. However, the preparation of InGaN
was complicated by the thermally stable In2O3. At lower temperatures inhomogeneous
materials consisting of GaN nanorods and In2O3 were obtained. While at high temperatures
(≥ 1050 °C) InGaN was obtained. However because indium has a high vapour pressure and a
low melting point only a minute amount of it was incorporated in the crystal lattice.
Hexagonally shaped nanoplates of In0.01Ga0.99N were successfully obtained. A shift in optical
emission to longer wavelengths was observed for the InGaN alloy. A blue optical emission
with the energy value of 2.86 eV was observed for the InGaN nanoplates.
The two n-type group III-nitrides (InN, GaN) prepared in this study were used for the
detection of CO, NH3, CH4 and NO2 gases in the temperature range between 250 and 350 °C.
The InN sensor and GaN sensor responses were compared to the response of the wellestablished
n-type SnO2 sensor under the same conditions. All the three sensors responded to
all the four gases. However, InN and GaN were much more selective in comparison to SnO2.
InN sensitivity to CO at 250 °C surpassed its sensitivity to any other gas at the studied
temperature range. Its response towards CO at 250 °C was about five times more than that of
SnO2 towards CO at the same temperature. While, GaN was the best CH4 sensor at 300 °C in
comparison to InN and SnO2 sensors at all temperatures. Meanwhile SnO2 responded
remarkably to both NH3 and CO across the studied temperature range with its performance
improving with increasing temperature. The ability for InN to respond to both NH3 and NO2
at 250 °C opens up the possibility for an application of InN as an ammonia sensor in diesel
engines. InN and SnO2 sensors were found susceptible to humidity interference in a real
environmental situation. On the contrary, GaN sensor presented itself as an ideal candidate
for indoor and outdoor environments as well as in bio-sensors because it showed robustness
and inertness towards humidity. InN and GaN by showing activity at high temperatures only,
presented themselves as good candidates for in-situ high temperate gas sensing applications.
Response and recovery times for all sensors showed improvement with increasing
temperature.MT201
