<p> The properties and device applications of silicon thin films vacuum evaporated both onto single crystal silicon and onto silicon dioxide substrates have been investigated. </p> <p> The feasibility of obtaining device quality homoepitaxial silicon thin films by vacuum evaporation onto non heat-treated substrates having temperatures of 700°C has been demonstrated. A new technique, that of gas-doping, has been developed and has been shown to be capable of reproducibly introducing controlled concentrations of doping impurities in the range applicable to device fabrication into the deposited layers. The combined deposition-doping technique has been employed in the production of silicon layers containing impurity steps more abrupt than may be obtained by conventional fabrication techniques. </p> <p> The electrical properties of the vacuum evaporated homoepitaxial silicon layers have been shown to be comparable in most respects to those of bulk high purity single crystal silicon. The characteristics of rectifying and of varactor diodes prepared by the technique of vacuum evaporation combined with gas doping have been considered. </p> <p> Silicon films evaporated onto Si02 substrates have been shown to possess structures ranging from amorphous through randomly oriented polycrystalline to oriented polycrystalline as the substrate temperature is increased from 25°C to 850°C. The electrical characteristics of doped polycrystalline films obtained both by vacuum evaporation combined with gas doping and by the diffusion-annealing of amorphous films have been shown to be comparable with those reported for similar material deposited by chemical techniques. The experimentally observed properties of the disordered material have been qualitatively explained employing an inhomogeneous film model. The suitability of thin films of doped polycrystalline silicon on sio2 substrates for the production of high value resistors for monolithic integrated circuits has been considered. </p> / Thesis / Doctor of Philosophy (PhD)

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Silicon photonics offers great benefits in terms of cost, performance and power consumption. This is increasingly important as the demand for internet bandwidth continues to grow. Optical detection in silicon photonics is performed via the integration of germanium, one of the more challenging integration steps during fabrication. This thesis describes research into a novel technique to grow silicon-germanium on silicon and its application in waveguide detectors and research performed into the application of germanium at extended wavelengths of light. Chapter 1 provides a brief introduction to silicon photonics and chapter 2 covers background material on p-n and p-i-n detectors as well as germanium growth on silicon and it’s applications in silicon photonics. Chapter 3 presents work done on a germanium condensation technique using high fluence ion implantation, suitable for straightforward silicon-germanium fabrication. Using this technique a crystalline layer of silicon-germanium with a high concentration of 92% germanium was demonstrated. In addition a semi-empirical model was developed using a segregation coefficient, an enhanced linear oxidation rate and transient enhanced diffusion. This technique was then used to fabricate a photodetector for operation at a wavelength of 1310 nm. While the responsivity of the detector of 0.01 A/W was modest, this work presents the first demonstration of a detector fabricated in this way, and as such provides a foundation for future improved devices. Chapter 4 presents work done on p-i-n germanium detectors to increase their detection limit in the thulium doped fibre amplifier band. This work originally focused on using mid-bandgap lattice defects introduce via ion implantation to improve the detection limit. However, during this experimental work it was determined that the unimplanted samples had a responsivity of 0.07 A/W at 1850 nm and 0.02 A/W at 2000 nm which was higher than that of the defect implanted samples and so the unimplanted samples were investigated further. From this work it was found that the absorption of the germanium detectors was 0.003 μm-1 at 1900 nm, which is approximately a factor of 10 greater than that of bulk germanium. The increased responsivity and absorption coefficient were attributed to tensile strain in the germanium. In Chapter 5 Raman spectroscopy was employed in order to investigate the detectors described in chapter 4 and confirm the presence of tensile strain. When compared with Raman spectra from a bulk germanium sample it was found that the detectors were experiencing 0.27 to 0.48 % tensile strain, consistent with the enhanced absorption at extended wavelengths. Nanowire bridges were then fabricated in germanium and silicon-germanium and characterized using Raman spectroscopy. Germanium was found to have enhanced strain in the nanowire with an enhancement of up to 13.5 demonstrated, whereas for the silicon-germanium samples the structures were shown to reduce the compressive strain in the samples. It is concluded that strain engineering is a very promising route for the development of extended wavelength detectors integrated with silicon photonic systems. / Thesis / Doctor of Philosophy (PhD)

The production and fabrication of semi-conductor core optical fibers was shown to be feasible and controllable. This was accomplished through the step sequence of fabrication and characterization of 4 fiber types, an experiment on controlling the grain length in the core and a simple model of the heat transfer during fabrication. Fibers were first made with a silicon core, followed by a phosphorous doped n-type silicon core, then a boron doped p-type silicon core, and a tellurium doped n-type gallium antimonide core. Characterization of the fibers was accomplished with energy dispersive spectroscopy (EDS) for compositional analysis, electron backscatter diffraction (EBSD) for crystal orientation and grain size, optical and electron microscopy for physical fiber quality and optical transmission for core optical quality. A model was developed to relate the heat transfer with the grain structure of the fiber core. All of the fibers fabricated had a polycrystalline core with either no detectable oxygen in the case of the silicon fibers or low amounts of oxygen diffusion into the core as in the case of the GaSb fibers. Fiber lengths ranged from 7 cm for the initial silicon fibers to 60 cm and outside diameters down to 100 µm for n and p type silicon fibers. Core diameters for all fiber types ranged from 10 – 200 µm depending on the fabrication parameters. Lengths of major grains in the core are dependent on the core diameter and the pulling speed. The grain lengths of the major grains in the core generally increase in length with an increase in core diameter. Grain lengths in all fibers are thought to be suitable for use in fabrication of electronic structures in the core region with even the smallest average grain length of around 300 µm. This grain structure satisfies the grain boundary requirements for fabrication of boundary free p-n junctions and other more complicated electronic structures. Small core diameter fibers had better physical quality with fewer cracks and longer continuous length than the larger core fibers. / Ph. D.

Master of Science / Department of Chemical Engineering / James H. Edgar / Silicon oxidation has been the cornerstone of the semiconductor industry for many years, so understanding and being able to predict the oxidation process is paramount. The most popular model to date is the Deal-Grove model for the thermal oxidation of planar silicon surfaces. The Deal-Grove model owes its popularity to the overall simplicity in which it was derived and the accuracy in which it predicts the oxidation of planar silicon geometries. Due to this popularity and accuracy it is desirable to extend the Deal-Grove model beyond flat surfaces to other geometries such as cylinders and spheres. Extending the Deal-Grove model to these types of geometries would allow the prediction of the oxidation of silicon nano-wires and silicon nanocrystals. Being able to predict the oxidation is attractive due to the recent progress of integration of silicon nano-wires and silicon nano-crystals into microelectronic devices. Prediction of the oxidation of silicon cylinders (nano-wires) and spheres (nano-crystals) by simply utilizing the established planar Deal-Grovel model results in highly exaggerated oxide thicknesses compared with empirical data. This exaggeration for small silicon cylinders and spheres is due to the effects of the reduction in the available surface area for oxidation along with the stress induced due to the volumetric expansion and viscous flow of the oxide on non-planar surfaces. These stress effects retard the oxidation rate in non-planar silicon geometries with respect to flat surfaces. This reduction in the oxidation rate reduction is caused by the normal compressive stress which is normal to the SiO[subscript]2/Si interface due to the volumetric expansion during oxidation. This compressive stress reduces the reaction rate constant at the SiO[subscript]2/Si interface and thus retards the overall oxidation rate for silicon cylinders and spheres with respect to planar silicon. The focus of this paper will be to contrast cylindrical and spherical versions of the Deal-Grove model to the well established planar version. Surface area and stress effects will also be explored as they help explain the reduction in the oxidation rate for non-planar silicon geometries.

In order to create more sensitive and accurate gas sensors, we have studied the interactions of gas mixtures on metal oxide nanoparticle decorated porous silicon interfaces. The nanoparticles control the magnitude and direction of electron transduction from the interaction of analyte gases to an extrinsic porous silicon semiconductor. These interactions can be predicted by the Inverse Hard Soft Acid Base (IHSAB) principle. Moreover, the metal oxide nanoparticles can be functionalized with nitrogen and sulfur, modifying the oxide’s band structure. These modifications are demonstrated to change analyte interactions in line with the IHSAB concept and allow for light enhanced sensors. Further we looked at how the analyte gases interact with other analyte gases on the surface of these sensors. Studying these systems does two things, first the research will lead to cheaper, more accurate gas sensors, and second it helps explore the role of nanoparticles in modifying the interactions between bulk materials (porous silicon) and molecules (analyte gases).

Measurements of the high temperature dielectric properties of ceramic materials at microwave frequencies have been made using two different experimental techniques.Data has been collected at frequencies from O.2GHz to 4.0GHz and for sample temperatures up to 1200°C. Detailed cross checking of the high temperature dielectric data obtained by the two techniques has been carried out with the help of other laboratories worldwide. An investigation of the applicability of dielectric mixture equations to practical measurement techniques is reported. The most reliabl~ estimates of permittivity were given by the Landau-Lifshitz, Looyenga equation or by a cube root extrapolation technique.Permittivity data obtained for a series of yttria stabilised zirconia samples, three differently processed silicon nitride samples and ten related glass compositions are presented. Analysis of the frequency and temperature dependence of both components of complex permittivity has been undertaken· in an attempt to identify the physical origins of the dielectric loss mechanisms. For the yttria doped zirconia samples results indicate two distinct loss mechanisms dominant over different temperature ranges. Below approximately 950K a hopping model involving short range motion of oxygen vacancies around fixed dopant ions is proposed. Above 950K thermally activated quantum mechanical tunneling of electrons is suggested as the dominant mechanism. A single loss mechanism for the entire temperature range involving the lattice loss of the silicon nitride network itself is indicated from the measurements of the hot pressed and pressureless sintered silicon nitride samples. For the reaction bonded silicon nitride samples there is evidence of a second loss mechanism due to additional ion impurities above 1410K. The measurements on the oxide glass systems add support to the belief that + 1 charged metal ions will dominate the dielectric properties of glass systems when present. The loss process has an increasing activation energy with increasing temperature which is seen to be consistent with ionic motion within the previously proposed random potential energy model. Differences in the complex permittivity with composition are attributed to variation in ionic size and metal ion-oxygen ion bond strength.

The global energy market is continuously changing due to changes in demand and fuel availability. Amongst the technologies considered as capable of fulfilling these future energy requirements, Photovoltaics (PV) are one of the most promising. Currently the majority of the PV market is fulfilled by crystalline Silicon (c-Si) solar cell technology, the so called 1st generation PV. Although c-Si technology is well established there is still a lot to be done to fully exploit its potential. The cost of the devices, and their efficiencies, must be improved to allow PV to become the energy source of the future. The surface of the c-Si device is one of the most important parts of the solar cell as the surface defines the electrical and the optical properties of the device. The surface is responsible for light reflection and charge carrier recombination. The standard surface finish is a thin film layer of silicon nitride deposited by Plasma Enhanced Chemical Vapour Deposition (PECVD). In this thesis an alternative technique of coating preparation is presented. The HiTUS sputtering tool, utilising a remote plasma source, was used to deposit the surface coating. The remote plasma source is unique for solar cells application. Sputtering is a versatile process allowing growth of different films by simply changing the target and/or the deposition atmosphere. Apart from silicon nitride, alternative materials to it were also investigated including: aluminium nitride (this was the first use of the material in solar cells) silicon carbide, and silicon carbonitride. All the materials were successfully used to prepare solar cells apart from the silicon carbide, which was not used due to too high a refractive index. Screen printed solar cells with a silicon nitride coating deposited in HiTUS were prepared with an efficiency of 15.14%. The coating was deposited without the use of silane, a hazardous precursor used in the PECVD process, and without substrate heating. The elimination of both offers potential processing advantages. By applying substrate heating it was found possible to improve the surface passivation and thus improve the spectral response of the solar cell for short wavelengths. These results show that HiTUS can deposit good quality ARC for silicon solar cells. It offers optical improvement of the ARC s properties, compared to an industrial standard, by using the DL-ARC high/low refractive index coating. This coating, unlike the silicon nitride silica stack, is applicable to encapsulated cells. The surface passivation levels obtained allowed a good blue current response.

To make solar energy mainstream, lower-cost and more efficient power generation is key. A lot of effort in the silicon photovoltaic industry has gone into using fewer raw materials (i.e., silicon) and using more inexpensive processing techniques and materials to reduce cost. Utilizing thinner substrates not only reduces cost, but improves cell efficiency provided both front and back surfaces are well-passivated. In the current work, a kerf-less process is developed in which ultra-thin (~25 [mu]m), flexible mono-crystalline silicon substrates can be obtained through an exfoliation technique from a thicker parent wafer. These substrates, when exfoliated, have thick metal backing which provides mechanical support to the thin silicon and enables ease of processing of the substrates for device fabrication. Optical, electrical, and reliability characterization studies for completed cells show this technology’s compatibility with a heterojunction solar cell process flow. Building on the promising results achieved on exfoliated substrates, further optimization work was carried out. Namely, an improved cleaning process was developed to remove front surface contamination on textured surfaces of exfoliated, flexible mono-crystalline silicon. This process is very effective at cleaning metallic and organic residues, without introducing additional contamination or degrading the supporting back metal used for ultra-thin substrate handling. Spectroscopic studies were performed to qualitatively and quantitatively understand the efficacy of different cleaning procedures in order to develop the new cleaning process. Results of the spectroscopic studies were further supported by comparing the electrical performance of cells fabricated with different cleans. To replace silver as contact metal with a cheaper substitute like nickel or copper, patterning and etching processes are generally used. A low-cost alternative is proposed, where a reusable shadow mask with a metal grid pattern is kept in contact with the surface of the substrate in a plasma-enhanced chemical vapor deposition chamber during silicon nitride deposition. This leaves a patterned silicon surface for selective metal growth by direct electro-deposition. The viability of this process flow is demonstrated by fabricating diffused junction n[superscript+]pp[superscript+] monofacial and bifacial cells and electrically characterizing them. Investigation of the factors limiting the efficiency of the cells was carried out by lifetime measurement experiments. / text