In the industry of metal cutting tools the conditions are extreme; the temperature can vary thousand degrees rapidly and the pressure can be tremendously high. To survive this kind of stress the cutting tool must be both hard and tough. In order to obtain these properties different coatings are used on a base of cemented carbide, WC-Co. Common coatings are hard ceramics like titanium nitride and titanium carbon-nitride with an outer layer of aluminium oxide. In this thesis the possibility of using titanium dioxide as an interlayer between titanium carbon-nitride and aluminium oxide to control the morphology and phase of aluminium oxide is investigated. Of the different aluminium oxide phases only the alpha-Al2O3 is stable. The titanium carbon-nitride coatings are made by CVD (chemical vapour deposition); also the alumina is deposited by CVD. The titanium dioxide was deposited by atomic layer deposition (ALD) which is a sequential CVD technique that allows a lower deposition temperature and better control of the film growth than CVD. The obtained thin films were analyzed using XRD, Raman spectroscopy, ESCA and SEM. To test the adhesion of the coatings the samples were sand blasted. A thin interlayer of titanium dioxide causes the aluminium oxide to grow as alpha-Al2O3, thinner TiO2 gave better adhesion.

Chemical Vapour Deposition (CVD) diamond detectors were modelled for dosimetry of radiotherapy beams. This was achieved by employing the EGSnrc Monte Carlo (MC) method to investigate certain properties of the detector, such as size, shape and electrode materials. Simulations were carried out for a broad 6 MV photon beam, and water phantoms with both uniform and non-uniform voxel dimensions. A number of critical MC parameters were investigated for the development of a model that can simulate very small voxels. For a given number of histories (100 million), combinations of the following parameters were analyzed: cross section data, boundary crossing algorithm and the HOWFARLESS option, with the rest of the transport parameters being kept at default values. The MC model obtained with the optimized parameters was successfully validated against published data for a 1.25 MeV photon beam and CVD diamond detector with silver/carbon/silver structure with thicknesses of 0.07/0.2/0.07 cm for the electrode/detector/electrode, respectively. The interface phenomena were investigated for a 6 MV beam by simulating different electrode materials: aluminium, silver, copper and gold for perpendicular and parallel detector orientation with regards to the beam. The smallest interface phenomena were observed for parallel detector orientation with electrodes made of the lowest atomic number material, which was aluminium. The simulated percentage depth dose and beam profiles were compared with experimental data. The best agreement between simulation and measurement was achieved for the detector in parallel orientation and aluminium electrodes, with differences of approximately 1%. In summary, investigations related to the CVD diamond detector modelling revealed that the EGSnrc MC code is suitable for simulation of small size detectors. The simulation results are in good agreement with experimental data and the model can now be used to assist with the design and construction of prototype diamond detectors for clinical dosimetry. Future work will include investigating the detector response for different energies, small field sizes, different orientations other than perpendicular and parallel to the beam, and the influence of each electrode on the absorbed dose.

This thesis details an investigation of the suitability of commercially-available single crystal and polycrystalline diamond films made via chemical vapor deposition (CVD) that were not studied previously for use in radiotherapy dosimetry. Novel sandwich-type detectors were designed and constructed to investigate the dosimetric response of diamond films under clinical conditions. Relatively inexpensive diamond films were obtained from three manufacturers: Diamonex, Diamond Materials GmbH and Element Six. Spectrophotometry, Raman spectroscopy and bulk conductivity studies were used to characterize these films and correlate crystalline quality with detector performance. Novel detectors were designed and constructed to investigate detectors under clinical conditions, including Perspex encapsulations and PCBs to minimize fluence perturbations. The dosimetric response of these diamond detectors was examined using a 6 MV beam from a Varian Clinac 600C linear accelerator. Diamond detectors were evaluated by measuring a number of response characteristics. Polycrystalline CVD diamond films from Diamonex (100, 200, 400-μm thicknesses) were considered unsuitable for dosimetric applications due to their lack of stability, low sensitivity, high leakage currents, high priming dose and dependence on dose rate. High-quality polycrystalline diamond films from Diamond Materials (100, 200, 400-μm thicknesses) displayed characteristics that varied with film thickness. A 100-μm film featured slow response dynamics and high priming doses. Thicker films featured suitable dosimetric characteristics, e.g. negligible leakage currents, low priming doses, fast response dynamics and good sensitivity with small sensitive volumes. Element Six single crystal CVD diamond films (500-μm thicknesses) with small sensitive volumes (0.39 mm³) exhibited suitable characteristics for dosimetry. These films showed negligible leakage currents (< 1.25 pA), low priming doses (1–10 Gy), quick response dynamics, high sensitivity (47–230 nC Gy⁻¹) and were weakly dependent on dose rate and directional dependence (±1%). A relatively inexpensive single crystal CVD diamond film from Element Six that exhibited high sensitivity (230 nC Gy⁻¹ at 0.5 V μm⁻¹), amongst other favourable characteristics, was selected for further analyses. An appropriate operating voltage was determined before further clinically relevant measurements could be conducted. This included how changes in an applied electric field affected detector response, and determined whether an optimal operating voltage could be realized within the parameters of conventional instrumentation used in radiation therapy. The results of this study indicated a preference towards using 62.5 V (at ~0.13 V μm⁻¹) out of a range of 30.8–248.0 V for temporal response as required for modulated beams due to its minimal rise time (2 s) and fall time (2 s) yet sufficient sensitivity (37 nC Gy⁻¹) and weak dependence on polarity (±1.5%). Investigations were then performed on the same diamond detector to evaluate its performance under more clinically relevant conditions. Repeatability experiments revealed a temporary loss in sensitivity due to charge detrapping effects following irradiation, which was modelled to make corrections that improved short-term precision. It was shown that this detector could statistically distinguish between dose values separated by a single Monitor Unit, which corresponded to 0.77 cGy. Dose rate dependence was observed when using low, fixed doses in contrast to using stabilized currents and higher doses. Depth dose measurements using this detector compared well with ion chambers and diode dosimeters. Comparisons of initial measurements with values in the literature indicate encouraging results for fields sizes < 4 x 4 cm², but further measurements and comparisons with Monte Carlo calculations are required. Using this detector to make off-axis measurements in the edge-on orientation reduced perturbation of the beam due to its sandwich configuration and thin 150 nm Ag contacts. This diamond detector was found to be suitable for routine dosimetry with conventional radiotherapy instrumentation with a materials cost of < NZ$200.

An examination of the possibility of applying pulse pressure metalorganic chemical vapour deposition (PP-MOCVD) to conformal coating and an investigation of PP-MOCVD processing parameters were undertaken using the deposition of thin, conformal titanium dioxide (TiO₂) on 3-D featured and non-featured substrates. The characterisation of the conformality and wettability analysis of thin TiO₂ was carried out using titanium tetraisopropoxide (TTIP) dissolved in toluene as a precursor and featured silicon (Si) and silicon nitride (Si₃N₄) as substrates. The features on the substrates were in micro- and nano-scale with the aspect ratio up to 2:1. The processing parameters investigated were temperatures between 400 and 600°C, reactor base pressures from 50 to 200 Pa, injection volumes between 50 and 250 µl, precursor concentrations in the range of 0.15 to 0.50 mol% and pulsing times from 10 to 20 sec. The surface morphology and thickness were examined using a scanning electron microscope (SEM). The composition of the films was qualitatively identified by energy dispersive X-ray spectroscopy (EDS). X-ray diffraction (XRD) and Raman spectroscopy were used to analyse the phase and grain size. The surface roughness and grain size were evaluated using atomic force microscopy (AFM). The optical properties were characterised using UV-VIS light spectroscopy. The anti-sticking characteristic was examined by wettability analysis, measuring the contact angle of the film with water. The research examined the relationships between processing parameters and growth rate, conformality, surface roughness, grain size, phase and water contact angle. A new measurement for thin film conformality was derived based on a statistical analysis of a large number of film thickness measurements on a fracture surface over the lithographed features. The best conformality of 0.95 was obtained for micro-scale features at the lowest temperature in the range of investigation, 400℃, with pulse exposure characterised by a base pressure of 100 Pa, TTIP concentration of 0.50 mol%, injection volume of 50 µl and pulsing time of 10 sec. Conformality for micro-scale features was in the range of 0.82 to 0.97 over a wide range of deposition temperatures. Conformality was as low as 0.45 over nano-scale structures at the higher exposure rate. The conformality decreased as the temperature and precursor concentration increased. The precursor injection volume was found to have minor influences on conformality. The growth rate increased as the temperature increased and reached the maximum at the deposition temperature of 450℃ with the precursor concentration of 0.50 mol% and injection volume of 100 µl. The base pressure and relaxation time had slight influences on the growth rate over the deposition temperature range of 400 to 500℃. The growth rate was increased as the precursor concentration and precursor injection volume increased. The deposited TiO₂ films exhibited columnar growth and anatase phase. The base pressure and pulsing time had no obvious effects on grain size and surface roughness. The grain size decreased as the deposition temperature increased. The surface roughness increased as the deposition temperature increased. Contact angles of over 100° were found with conformality of over 0.80. The variation in contact angle was related to the surface morphology of the deposited films. The contact angle increased as the grain size decreased. High wettability was found for films in the mid-range of pulse exposure, in this study at pulse exposure of 53, or at high deposition temperature, in this case at 600°C. The as-deposited TiO₂ thin films were hydrophobic depending on the surface morphology, surface roughness and grain size.

This thesis analyzes the chemical vapour deposition (CVD) growth of vertically aligned carbon nanotube (CNT) forests in order to understand how CNT forests grow, why they stop growing, and how to control the properties of the synthesized CNTs. In situ kinetics data of the growth of CNT forests are gathered by in situ optical microscopy. The overall morphology of the forests and the characteristics of the individual CNTs in the forests are investigated using scanning electron microscopy and Raman spectroscopy. The in situ data show that forest growth and termination are activated processes (with activation energies on the order of 1 eV), suggesting a possible chemical origin. The activation energy changes at a critical temperature for ethanol CVD (approximately 870°C). These activation energies and critical temperature are also seen in the temperature dependence of several important characteristics of the CNTs, including the defect density as determined by Raman spectroscopy. This observation is seen across several CVD processes and suggests a mechanism of defect healing. The CNT diameter also depends on the growth temperature. In this thesis, a thermodynamic model is proposed. This model predicts a temperature and pressure dependence of the CNT diameter from the thermodynamics of the synthesis reaction and the effect of strain on the enthalpy of formation of CNTs. The forest morphology suggests significant interaction between the constituent CNTs. These interactions may play a role in termination. The morphology, in particular a microscale rippling feature that is capable of diffracting light, suggest a non-uniform growth rate across the forest. A gas phase diffusion model predicts a non-uniform distribution of the source gas. This gas phase diffusion is suggested as a possible explanation for the non-uniform growth rate. The gas phase diffusion is important because growth by acetylene CVD is found to be very efficient (approximately 30% of the acetylene is converted to CNTs). It is seen that multiple mechanisms are active during CNT growth. The results of this thesis provide insight into both the basic understanding of the microscopic processes involved in CVD growth and how to control the properties of the synthesized CNTs.

This thesis focuses on surface science and bioengineering investigations, first for the development of an improved biomaterial for orthopaedic implant applications, and second, for the development of a biosensor device for biomedical diagnostics. A key component considered in this thesis was the covalent linkage of proteins to the material’s surface for retaining the protein’s immunological and biological activities and for generating a functional interface. Part 1 of this thesis investigated surface modification procedures for improving the bioactivity of titanium substrates. Titanium is first coated with a bioactive silica film grown by plasma enhanced chemical vapour deposition (PECVD), referred to as PECVD-Si-Ti. In previous studies, the bone-implant integration process was enhanced 1.6-fold for titanium implants coated with PECVD-Si films compared to uncoated titanium implants in vivo. However, in vitro studies carried out in this thesis showed that the growth of MG63 osteoblast-like cells was 7-fold higher on uncoated titanium compared to PECVD-Si coated titanium. Therefore, to improve cell growth on the surface and, by inference, the integration of PECVD-Si-Ti implants into bone tissue, the implant’s surface was functionalised with a mitogenic factor, insulin-like growth factor-1 (IGF-1). This was accomplished by modifying the PECVD-Si-Ti surface with an alkoxysilane, 3-isocyanatopropyl triethoxysilane (IPTES), and then by covalent bioconjugation of IGF-1 through isocyanate-amino chemistry. After 72 h of in vitro cell culture in serum-free medium, the growth of MG63 cells was enhanced 1.9-fold on IPTES functionalised PECVD-Si-Ti, which was loaded with covalently immobilised IGF-1 compared to IPTES functionalised PECVD-Si-Ti without IGF-1 (isocyanate reactive groups were quenched with ethanolamine hydrochloride). The attachment and adhesion of MG63 cells were also enhanced on PECVD-Si-Ti by the covalently immobilised IGF-1 in serum-free cell culture conditions. Therefore, the bioactivity of PECVD-Si-Ti was improved by covalently linking IGF-1 to the substrate surface through isocyanate-amino chemistry. Part 2 of this thesis involved the development of a new optical interferometric biosensor. The biosensor platform was constructed from electrochemically-prepared thin films of porous silicon that acted as a sensing matrix and transducer element. By reflective interferometry using white light, an enzyme-catalysed reaction was discovered (horseradish peroxidase (HRP) mediated oxidation of 3,3’,5,5’-tetramethylbenzidine (TMB)), which led to an acceleration in the rate of porous silicon corrosion and represented the biosensor’s readout signal. We discovered that another substrate, which is also oxidised by HRP, OPD, produces an even more pronounced readout signal. The HRP-OPD system was used in an immunoassay for detecting human IgG from an Intragam solution. An important part in the design of the biosensor was the surface functionalisation approach where anti-human IgG, referred to as the capture antibody, is immobilised on the porous silicon surface. The readout signal (produced from the capture of human IgG) was enhanced 4-fold on the porous silicon biosensing platform functionalised with covalently linked anti-human IgG through isocyanate-amino chemistry compared to the porous silicon biosensing platform functionalised with adsorbed anti-human IgG. The optimised biosensor was used to detect IgG from a total human protein concentration of Intragam to a sensitivity of 100 ng/ml. In summary, isocyanate-amino bioconjugate chemistry was used to covalently link either IGF-1 to PECVD-Si-Ti for improving the biological activity of the orthopaedic implant and to covalently link IgG to porous silicon for developing a sensitive biosensor for the detection of proteins. This surface chemistry approach is very useful for biomaterial and biosensing applications.

Chemical Vapour Deposition (CVD) diamond detectors were modelled for dosimetry of radiotherapy beams. This was achieved by employing the EGSnrc Monte Carlo (MC) method to investigate certain properties of the detector, such as size, shape and electrode materials. Simulations were carried out for a broad 6 MV photon beam, and water phantoms with both uniform and non-uniform voxel dimensions. A number of critical MC parameters were investigated for the development of a model that can simulate very small voxels. For a given number of histories (100 million), combinations of the following parameters were analyzed: cross section data, boundary crossing algorithm and the HOWFARLESS option, with the rest of the transport parameters being kept at default values. The MC model obtained with the optimized parameters was successfully validated against published data for a 1.25 MeV photon beam and CVD diamond detector with silver/carbon/silver structure with thicknesses of 0.07/0.2/0.07 cm for the electrode/detector/electrode, respectively. The interface phenomena were investigated for a 6 MV beam by simulating different electrode materials: aluminium, silver, copper and gold for perpendicular and parallel detector orientation with regards to the beam. The smallest interface phenomena were observed for parallel detector orientation with electrodes made of the lowest atomic number material, which was aluminium. The simulated percentage depth dose and beam profiles were compared with experimental data. The best agreement between simulation and measurement was achieved for the detector in parallel orientation and aluminium electrodes, with differences of approximately 1%. In summary, investigations related to the CVD diamond detector modelling revealed that the EGSnrc MC code is suitable for simulation of small size detectors. The simulation results are in good agreement with experimental data and the model can now be used to assist with the design and construction of prototype diamond detectors for clinical dosimetry. Future work will include investigating the detector response for different energies, small field sizes, different orientations other than perpendicular and parallel to the beam, and the influence of each electrode on the absorbed dose.

Thesis (Ph.D.)--Murdoch University, 2004. / Thesis submitted to the Division of Science and Engineering. Bibliography: 211-229.

Les couches minces de LiNbO3 (LN) avec des orientations du single cristallographique en dehors-du-plan et dans-le-plan sont nécessaires pour les dispositifs optiques et acoustiques. La technique PIMOCVD est adapté pour la déposition de couches minces de LN avec des orientations cristallographiques différentes sur des substrats monocristallins. Pour obtenir des couches avec une surface lisse et composé une phase pure de LN avec une concentration contrôlé de Li, les paramètres de déposition ont été ajustés.Un effort particulier a été mis dans la croissance de couches avec une orientation unique dans-le-plan. La qualité cristalline, la qualité de l’épitaxie, Li2O nonstoichiometrique, l’orientation dans-le-plan, le stress résiduel et le twinning ont été étudiés avec la diffraction des rayons X et la spectroscopie Raman. Couches de LN avec composition presque stoichiometrique on été obtenues. Les couches épaisses ont tendance à se fracturer et à former twins pour détendre les grands stress thermique. Les différences dans les mécanismes de relaxation et dans la capacité de supporter des stress dans les couches de X-, Y- et Z-LN sont discutés. Dans le cas des couches Z-LN le stress thermique sont equi-biaxial quand le stress dans les couches X- et Y- sont anisotropies. On a étudié aussi la structure des domaines ferroélectriques et la réponse piézoélectrique des couches. L’énergie de bande et l’indice de réfraction des couches de LN, mesuré pas elipsometrie spectrale, sont très proche de ceux du LN monocristallin. On démontre expérimentalement la présence d’une résonance à 5.5 GHz dans un résonateur à un seul port réalisé dans une couche de Z-LN/saphir de 150 nm d’épaisseur. / LiNbO3 (LN) thin films are attracting interest due to possibility to miniaturize, to integrate and to ameliorate the performance of acoustical and optical devices. These applications require LN films with single crystallographic out-of-plane and in-plane orientations. PIMOCVD technique was used for deposition of high quality of different crystallographic orientations LN thin films, offering a possibility to obtain films with various different cut on single crystalline substrates.In order to obtain films with smooth surface and consisting of pure LN phase with controlled Li concentration, the deposition parameters were tuned.A particular effort was done to obtain films with single in-plane orientation. The crystallinity, epitaxial quality, Li2O nonstoichiometry, in-plane orientation, residual stresses and twinning were studied by means of X-ray diffraction and Raman spectroscopy. The LN films with nearly stoichiometric composition were obtained. The thick films tend to crack and to form the twins in order to relax the high thermal stresses. The differences in relaxation mechanisms and in ability to withstand high stresses of X-, Y- and Z-LN films were discussed. In the case of Z-LN films the thermal stresses are equibiaxial, while the stresses in X- and Y- films are anisotropic. The ferroelectric domain structure and piezoelectric response of grown films were investigated. Energy gap and refractive indexes of LN films, measured by spectroscopic ellipsometry, were similar to those of single crystal. Acoustic resonance at 5.5 GHz in single-port resonators based on as-grown 150 nm thick Z-LN film on sapphire films was demonstrated experimentally.

This thesis presents the development of chemical vapour deposited (CVD) graphene and multi-walled carbon nanotubes (MWCNTs) as enabling technologies for flexible transparent conductors offering enhanced functionality. The technologies developed could be employed as thin film field emission sources, optical sensors and substrate-free wideband optical polarisers. Detailed studies were performed on CVD Fe and Ni catalysed carbon nanotubes and nanofibres on indium tin oxide, aluminium and alumina diffusion barriers. Activations energies of 0.5 and 1.5 eV were extracted supporting surface diffusion limited catalysis forCNTs and CNFs. For the first time an activation energy of 2.4 eV has been determined for Cu-catalysed growth of CVD graphene. Graphene was shown to deviate significantly from the more traditional rate-limited surface diffusion and suggests carbon-atom-lattice integration limited catalysis. An aligned dry-transferred MWCNT thin film fabrication technique was developed using MWCNTs of varied lengths to control the optical transparency and conductivity. A process based on the hot-press lamination of bilayer CVD graphene (HPLG) was also developed. Transport studies revealed that these thin films behave, in a macroscopic sense, similar to traditional c-axis conductive graphite and deviate toward tunnel dominated conduction with increasing degrees of network disorder. Various MWCNT-based thin film field emitters were considered. Solution processing was shown to augment the surface work function of the MWCNTs resulting in reduced turn-on electric fields. Integrated zinc oxide nanowires were investigated and were shown to ballast the emission, thereby preventing tip burn out, and offered lower than expected turn-on fields due to the excitation of a hot electron population. To obviate nearest neighbour electrostatic shielding effects an electrochemical catalyst activation procedure was developed to directly deposit highly aligned sparse carbon nanofibres on stainless steel mesh. Highly-aligned free-standing MWCNT membranes were fabricated through a solid-state peeling technique. Membranes were spanned across large distances thereby offering an ideal platform to investigate the unambiguous photoresponse of MWCNTs by removing all extraneous substrate interfaces, charge traps and nanotube-electrode Shottky barriers as well as using pure, chemically untreated material. Oxygen physisorbtion was repeatedly implicated through in-situ lasing and in-situ heated EDX measurements, FT-IR and low temperature transport and transfer measurements. A MWCNT membrane absorptive polariser was fabricated. Polarisers showed wideband operation from 400 nm to 1.1 μm and offered operation over greater spectral windows than commercially available polymer and glass-support dichroic films. Ab-initio simulations showed excellent agreement with the measured polarisation attributing the effect to long-axis selective absorption.