Christopher J. Arendse

Optimization, Yield Studies and Morphology of WO3Nano-Wires Synthesized by Laser Pyrolysis in C2H2and O2Ambients—Validation of a New Growth Mechanism

Laser pyrolysis has been used to synthesize WO3nanostructures. Spherical nano-particles were obtained when acetylene was used to carry the precursor droplet, whereas thin films were obtained at high flow-rates of oxygen carrier gas. In both environments WO3nano-wires appear only after thermal annealing of the as-deposited powders and films. Samples produced under oxygen carrier gas in the laser pyrolysis system gave a higher yield of WO3nano-wires after annealing than the samples which were run under acetylene carrier gas. Alongside the targeted nano-wires, the acetylene-ran samples showed trace amounts of multi-walled carbon nano-tubes; such carbon nano-tubes are not seen in the oxygen-processed WO3nano-wires. The solid–vapour–solid (SVS) mechanism [B. Mwakikunga et al., J. Nanosci. Nanotechnol., 2008] was found to be the possible mechanism that explains the manner of growth of the nano-wires. This model, based on the theory from basic statistical mechanics has herein been validated by length-diameter data for the produced WO3nano-wires.

Comparative study: the effect of annealing conditions on the properties of P3HT:PCBM blends

This paper presents a detailed study on the role of various annealing treatments on organic poly(3-hexylthiophene) and [6]-phenyl-C61-butyric acid methyl ester blends under different experimental conditions. A combination of analytical tools is used to study the alteration of the phase separation, structure and photovoltaic properties of the P3HT:PCBM blend during the annealing process. Results showed that the thermal annealing yields PCBM “needle-like” crystals and that prolonged heat treatment leads to extensive phase separation, as demonstrated by the growth in the size and quantity of PCBM crystals. The substrate annealing method demonstrated an optimal morphology by eradicating and suppressing the formation of fullerene clusters across the film, resulting in longer P3HT fibrils with smaller diameter. Improved optical constants, PL quenching and a decrease in the P3HT optical bad-gap were demonstrated for the substrate annealed films due to the limited diffusion of the PCBM molecules. An effective strategy for determining an optimized morphology through substrate annealing treatment is therefore revealed for improved device efficiency.

Thermally Induced Nano-Structural and Optical Changes of nc-Si:H Deposited by Hot-Wire CVD

We report on the thermally induced changes of the nano-structural and optical properties of hydrogenated nanocrystalline silicon in the temperature range 200–700 °C. The as-deposited sample has a high crystalline volume fraction of 53% with an average crystallite size of ~3.9 nm, where 66% of the total hydrogen is bonded as ≡Si–H monohydrides on the nano-crystallite surface. A growth in the native crystallite size and crystalline volume fraction occurs at annealing temperatures ≥400 °C, where hydrogen is initially removed from the crystallite grain boundaries followed by its removal from the amorphous network. The nucleation of smaller nano-crystallites at higher temperatures accounts for the enhanced porous structure and the increase in the optical band gap and average gap.

Optical and electronic properties of mixed halide (X = I, Cl, Br) methylammonium lead perovskite solar cells

We report on the fabrication and opto-electronic characterization of solution-processed planar heterojunction perovskite solar cells based on methylammonium (MA) lead halide derivatives, MAPbI3−xYx (Y = Cl, Br, I). Dissolving equimolar amounts of lead iodide (PbI2) and methylammonium iodide (H3CNH3I) together with various amounts of additional methylammonium halides, perovskite precursor solutions were obtained, which were used in the fabrication of three perovskite systems, MAPbI3, MAPbI3−xClx and MAPbI3−xBrx. The effect of the halide ratio in the perovskite formulations processed via a one-step deposition technique on optoelectronic properties and on photovoltaic performance of the formed perovskites was investigated. The perovskite film morphology, temperature-dependent photoluminescence properties, hysteresis behaviour in current–voltage characteristics and the photovoltaic performance as a function of chemical composition were studied using microscopic, spectroscopic and photovoltaic characterization techniques. The power conversion efficiency was found to be dependent on MAPbI3−xYx (Y = Cl, Br, I) perovskite film morphology. By controlling perovskite precursor composition and stoichiometry, highest power conversion efficiencies of 9.2, 12.5 and 5.4% were obtained for MAPbI3, MAPbI3−xClx and MAPbI3−xBrx devices, respectively. In addition, the physical parameters of the mixed halide perovskites such as the exciton binding energy, exciton–phonon interaction and bandgap were determined via temperature-dependent photoluminescence spectroscopy. Exciton binding and optical phonon energies of MAPbI3−xYx (Y = Cl, Br, I) were found to be in the ranges of 49–68 meV and 29–32 meV respectively. The solution-processed MA lead halide derivatives form highly crystalline materials with chemical versatility allowing the tuning of their optical and electronic properties depending on the nature and the ratio of the halides employed.

EBSD analysis of tungsten-filament carburization during the hot-wire CVD of multi-walled carbon nanotubes.

Filament condition during hot-wire chemical vapor deposition conditions of multi-walled carbon nanotubes is a major concern for a stable deposition process. We report on the novel application of electron backscatter diffraction to characterize the carburization of tungsten filaments. During the synthesis, the W-filaments transform to W2C and WC. W-carbide growth followed a parabolic behavior corresponding to the diffusion of C as the rate-determining step. The grain size of W, W2C, and WC increases with longer exposure time and increasing filament temperature. The grain size of the recrystallizing W-core and W2C phase grows from the perimeter inwardly and this phenomenon is enhanced at filament temperatures in excess of 1,400°C. Cracks appear at filament temperatures >1,600°C, accompanied by a reduction in the filament operational lifetime. The increase of the W2C and recrystallized W-core grain size from the perimeter inwardly is ascribed to a thermal gradient within the filament, which in turn influences the hardness measurements and crack formation.

Structural evolution of a Ta-filament during hot-wire chemical vapour deposition of Silicon investigated by electron backscatter diffraction

We report on the application of electron backscatter diffraction to investigate the structural changes of a tantalum filament operated at typical hot-wire chemical vapour deposition conditions for the synthesis of hydrogenated nanocrystalline silicon. Various tantalum-silicides, identified by electron backscatter diffraction, form preferentially along the length of the filament. The filament has a recrystallized Ta inner core and a TaSi2 layer encapsulated with a Si layer at the cooler ends. The αTa5Si3, metastable Ta5Si3 and Ta2Si phases formed in addition to recrystallized Ta and TaSi2 at the centre regions. Cracks and porosity were prevalent throughout the length of the filament. The microstructural evolution of the aged tantalum filament can be ascribed to the thermal gradient along the filament length, recrystallization of Ta and the variation of silicon content within the filament.

Adsorption of phosphoric acid anions on platinum (111)

The adsorption of phosphoric acid anions on the platinum (111) plane is investigated using Monte Carlo and density functional theory methods. The minimum energy structure is used to generate the adsorption configurations, indicating the preferred adsorption sites. The bond lengths was found from density functional theory calculations and used to gain further insight on the structure due to adsorption. From the density functional calculations the scanning tunnelling microscopy image of the specie with the lowest adsorption energy configuration and shortest bond length was produced.

Oxidation Reduction in Nanocrystalline Silicon Grown by Hydrogen-Profiling Technique

The deposition of a compact amorphous silicon/nano-crystalline silicon material is demonstrated by hot-wire chemical vapour deposition using a sequential hydrogen profiling technique at low hydrogen dilutions. Nano-crystallite nucleation occurs at the substrate interface that develops into a uniform, porous crystalline structure as the growth progresses. A further reduction in the H-dilution results in the onset of a dense amorphous silicon layer. The average crystalline volume fraction and nano-crystallite size in the sample bulk amounts to 30% and 6 nm, respectively, as probed by Raman spectroscopy using the 647 nm excitation. The change in hydrogen dilution is accompanied by a graded hydrogen concentration depth-profile, where the hydrogen concentration decreases as the growth progresses. The level of post-deposition oxidation is considerably reduced, as inferred from infrared spectroscopy. The presence of oxygen is mainly confined to the substrate interface as a result of thermal oxidation during thin film growth.

Depth-dependent crystallinity of nano-crystalline silicon induced by step-wise variation of hydrogen dilution during hot-wire CVD

To induce an amorphous surface in a nano-crystalline silicon (nc-Si:H) thin film, the hydrogen dilution was reduced step-wise at fixed time intervals from 90 – 50% during the hotwire chemical vapour deposition process. This contribution reports on the structural properties of the resultant nc-Si:H thin film as a function of the deposition time. Raman spectroscopy, confirmed by high resolution transmission spectroscopy, indicates crystalline uniformity in the growth direction, accompanied by the progression of an amorphous surface layer as the deposition time is increased. The silicon- and oxygen bonding configurations were probed using infrared spectroscopy and electron energy loss spectroscopy. The growth mechanism is ascribed to the improved etching rate by atomic hydrogen in nano-crystalline silicon towards the film/substrate interface region. The optical properties were calculated by applying the effective medium approximation theory, where the existence of bulk and interfacial layers, as inferred from cross-sectional microscopy, were taken into account.

Amorphous and nc-Si:H Intrinsic Thin Films for Solar Cells Applications

This contribution discusses the deposition process and properties of intrinsic silicon thin films processed by the hot wire chemical vapour deposition technique. We review some fundamental characterization techniques that are used to probe into the quality of the material and thus decide its susceptibility to be used as the intrinsic layer in solar cells industry. This paper covers the optical, structural and electrical properties of the material. Results from UV-visible and IR spectroscopy, XRD and Raman scattering, X-section TEM as well as dark and photo-currents are given. It is shown that the thermal activation energy is a good measure of the quality of the sample.