Philosophiae Doctor - PhD / The rapid increase in global energy demand in recent decades coupled with the adverse environmental impact of conventional fuels has led to a high demand for alternative energy sources that are sustainable and efficient. Renewable solar energy technologies have received huge attention in recent decades with the aim of producing highly efficient, safe, flexible and robust solar cells to withstand harsh weather conditions. c-Si has been the material of choice in the development of conventional inorganic solar cells owing to it superior properties, abundance and higher efficiencies. However, the associated high costs of Si processing for solar cells have led to a gravitation towards alternative organic solar cells which are cheaper and easy to process even though they suffer from stability and durability challenges. In this work, combination of both inorganic and organic materials to form hybrid solar cells is one of the approaches adopted in order to address the challenges faced by solar cell development.

Si nanowires have potential applications in a variety of technologies such as micro and nanoelectronics, sensors, electrodes and photovoltaic applications due to their size and specific surface area. Au particle-assisted vapour-liquid-solid or VLS growth method remains the dominant process for Si nanowire growth. A comprehensive kinetic model that addresses all experimental observations and provides a physico-chemical model of the VLS growth method is thus essential. The work done as part of this research is divided into two sections. A steady state kinetic model was first developed for the steady state growth rate of Si nanowires using SiCl4 and SiH4 as precursors. The steady state refers to a balance between the rates of injection and ejection of Si into the Au droplet. This balance results in a steady state supersaturation under which wire growth proceeds. In particular evaporation and reverse reaction of Si from the Au droplet and modes of crystal growth for wire growth have been considered in detail for the first time. The model is able to account for both, the radius independent and radius dependent growth rates reported in the literature. It also shows that the radius dependence previously attributed to purely thermodynamic considerations could also as well be explained just by steady state kinetics alone. Expressions have been derived for the steady state growth rate that require the desolvation energy, activation energy for precursor dissociation and supersaturation prevalent in the particle as inputs for calculation. In order to evaluate this model the incubation and growth of Si nanowires were studied on sapphire substrates in an indigenously built automated MOCVD reactor. Sapphire was chosen as the substrate, as opposed to Si which is commonly used, so as to ensure that the vapour phase is the only source of Si. A classical incubation period for nucleation, of the order of 4-8 minutes, was experimentally observed for the first time. Using the change in this incubation period with temperature a value of 15kT was determined to be the desolvation energy for growth using SiH4. The steady state growth rate of Si nanowires were measured and compared with the predictions of the model using the values of activation energies so determined. The thesis based on the current research work is organized as follows: Chapter 1 introduces the research area followed by a brief outline of the overall work Chapter 2 provides a summary of current literature, and puts the research described in this thesis in perspective. The diameter dependent growth rate of NWs which was initially solely attributed to the Gibbs-Thomson effect is first summarized. Experimental observations to the contrary are then highlighted. These contradictions provided the incentive for the research described in this thesis. Following a summary of the growth rate theories, the experimental observations on incubation available in the literature are summarized. All the other variants of the VLS method are also discussed. Chapter 3 describes the design, construction and working of an indigenously built semi- automated CVD reactor. This CVD reactor was used to conduct the Si NW growth experiments over sapphire substrates. Chapter 4 develops the physical chemistry model for Au catalyzed Si nanowire growth using SiCl4 and SiH4 precursors. The model originated from the contradictions present in the literature over the rate limiting step of the VLS growth mechanism and the steady state growth rate dependence on wire diameter. The development starts with explaining the thermodynamics of the steady state VLS process. The significance of the model lies in the detailed analysis of the all the atomistic process occurring during the VLS growth. In particular the evaporation and reverse reaction of Si from Au-Si droplet is explained in detail and possibly for the first time. Expressions for steady state growth rate by various modes, such as layer by layer growth (LL), by multilayer growth (ML) and growth by movement of a rough interface at the L-S growth interface are derived and presented. Chapter 5 discusses the results which emerge out the kinetic model from the previous chapter. Under a single framework of equations, the model is successful in explaining both the diameter independent and diameter dependent growth of NWs. As one of the major outcomes of the model, the growth rates of Si NWs are predicted and trends in growth rate are found to agree with those experimentally observed. Growth rate dependencies on pressure and temperature are implicitly included in the equations derived. An estimate of supersaturation has been extracted for the first time using the framework of equations. Chapter 6 contains the experimental results of the Si NW growth over sapphire substrates. An incubation period in the order of 3-8 minutes has been observed for Si NW growth on sapphire. The data has been compared with existing literature data and interpreted using classical transient nucleation theory. The incubation period data has been utilized to extract the kinetic parameter, QD, which is the desolvation enegy. These parameters and the measured steady state growth rates have been used to estimate the supersaturation existing in the droplet using the framework developed in chapters 4 and 5. Chapter 7 summarizes the outcome of the current research and highlights the future directions for the research problem addressed in this thesis.

Nanomaterials are the heart of nanoscience and nanotechnology. Research into nanostructures has been vastly expanding worldwide and their application spreading into numerous branches of science and technology. The incorporation of these materials in commercial products is revolutionising the current technological market. Nanomaterials have gained such enormous universal attention due to their unusual properties, arising from their size in comparison to their bulk counterparts. These nanosized structures have found applications in major devices currently under development including fuel cells, computer chips, memory devices, solar cells and sensors. Due to their aforementioned importance nanostructures of various materials and structures are being actively produced and investigated by numerous research groups around the world. In order to meet the market needs the commercialisation of nanomaterials requires nanomaterial fabrication mechanisms that will employ cheap, easy and low temperature fabrication methods combined with environmentally friendly technologies. This thesis investigates low temperature growth of various one-dimensional nanostructures for their potential application in chemical sensors. It proposes and demonstrates novel materials that can be applied as catalysts for nanomaterial growth. In the present work, zinc oxide (ZnO) and silicon (Si) based nanostructures have been fabricated using low temperature growth methods including hydrothermal growth for ZnO nanowires and plasma-enhanced chemical vapour deposition (PECVD) technique for Si nanostructures. The structural, optical and electrical properties of these materials have been investigated using various characterisation techniques. After optimising the growth of these nanostructures, gas and biosensors have been fabricated based on Si and ZnO nanostructures respectively in order to demonstrate their potential in chemical sensors. For the first time, in this thesis, a new group of materials have been investigated for the catalytic growth of Si nanostructures. Interesting growth observations have been made and theory of the growth mechanism proposed. The lowest growth temperature in the published literature is also demonstrated for the fabrication of Si nanowires via the PECVD technique. Systematic studies were carried out in order to optimise the growth conditions of ZnO and Si nanostructures for the production of uniformly shaped nanostructures with consistent distribution across the substrate. v The surface structure and distribution of the variously shaped nanostructures has been analysed via scanning electron microscopy. In addition, the crystallinity of these materials has been investigating using Raman and X-ray diffraction spectroscopies and transmission electron microscopy. In addition to the fabrication of these one-dimensional nanomaterials, their potential application in the chemical sensors has been tested via production of a glucose biosensor and an isopropyl alcohol vapour gas sensor based on ZnO and Si nanostructures respectively. The operation of the devices as sensors has been demonstrated and the mechanisms explored.

L'objectif de ce travail de recherche est la réalisation de dispositifs à base de nanofils de silicium, réalisés par la méthode des espaceurs. La synthèse des nanofils est effectuée à partir d'une couche de silicium polycristallin, déposée par la technique LPCVD (Low Pressure Chemical Vapor Deposition). Ces nanofils sont ensuite intégrés dans les dispositifs électroniques tels que des résistances ou des transistors réalisés suivant deux configurations différentes « bottom-gate » et « step-gate ». Les caractéristiques électriques de ces deux types de transistors ont mis en évidence des propriétés électriques suffisantes pour leur utilisation en tant que capteurs. Une simulation permet d'expliquer l'effet de l'apport de charges électriques à la surface des nanofils sur la concentration d'électrons dans la couche active. Les dispositifs sont tout d'abord utilisés pour la mesure du pH, et montrent une sensibilité de détection supérieure à la sensibilité nernstienne. Pour une utilisation du dispositif en tant que biocapteur, une fonctionnalisation de la surface des nanofils est nécessaire pour permettre l'accrochage de sondes d'ADN. La détection électronique de l'hybridation sondes/cibles de brins d'ADN complémentaires est démontrée avec un faible seuil de détection. Enfin, afin d'augmenter la surface d'échange entre le nanofil et les espèces chargées, un procédé de fabrication de résistances à base de nanofils suspendus est développé. Des tests de détection en présence d'ammoniac ont mis en évidence une réponse linéaire sur une gamme de concentrations. Les résistances à base de nanofils suspendus présentent une plus grande sensibilité que celles à base de nanofils non suspendus, mettant en avant l'effet important de la surface des nanofils. Tous ces résultats permettent de démontrer la faisabilité de capteurs chimiques et biologiques à base de nanofils de silicium à partir des techniques conventionnelles de la microélectronique en utilisant un procédé de fabrication « bas-coût ». / The goal of this research work is the realization of devices based on silicon nanowires, realized using sidewall spacer formation technique. Nanowires are synthesized form a polycrystalline silicon layer deposited by LPCVD technique (Low Pressure Chemical Vapor Deposition). These nanowires are then integrated into electronic devices such as resistors and transistors made using two different configurations “bottom-gate” and “step-gate”. The electrical characteristics of these two types of transistors have shown adequate electrical properties for their use as sensors. A simulation is made, to explain how additional electrical charges on the surface of the nanowires, affect the electron concentration inside the active layer. The devices are firstly used for the pH measurement, and have shown sensitivity higher than the Nernstian sensitivity detection. For a use as biosensor, nanowires are functionnalized to allow the binding of DNA probes. Electronic detection of hybridization complementary probe/target DNA strands is demonstrated with a low detection limit. Finally, in order to increase the exchange surface between the nanowires and charged species, resistors based on suspended nanowires were developed. Different tests were performed in the presence of ammonia and showed a linear response over a range of concentrations. Resistors based on suspended nanowires highlighted greater sensitivity than those based on unsuspended nanowires, bringing out the important effect of the surface of the nanowires. All these results demonstrate the feasibility of chemical and biological sensors based on silicon nanowires compatible with conventional microelectronics techniques using a low-cost process.

>Magister Scientiae - MSc / Solar cells offer SA an additional energy source. While Si cells are abundantly available they are not at an optimal efficiency and the cost is still high. One technology that can enhance their performance is SiNW. However, material properties such as the diameter, porosity and length determine their effectiveness during application to solar cell technology. One method of growing SiNW uses Sn catalysts on a Si substrate. As the properties of the Sn nanoparticle govern the properties of the SiNW, this thesis investigates their formation and properties by depositing a Sn layer on a Si wafer and then subjecting it to different temperatures, during process the layer forms into nanoparticles. At each temperature the morphology, composition and crystallinity will be determined using XPS, SEM, TEM and EDS. Thus, in Chapter 1 there is an overview, Chapter 2 deals with techniques used in this study, Chapter 3 will give the quantitative and qualitative results on the XPS analysis and Chapter 4 will illustrate the structural behaviour of the annealed Sn film samples.

Silicon is the most important semiconducting material for optoelectronics owing to its suitable and tunable physical properties. Even though there are several alternatives, silicon based solar cells are still the most widely produced and commercially feasible system. Extensive efforts have been spent in order to increase the efficiency and decrease the cost of these systems. The studies that do not focus on replacement of the semiconducting material, mostly concentrate on the developments that could be brought by nanotechnological approaches. In this aspect, utilization of silicon nanowires has been predicted to improve the efficiency of the silicon based solar cell technology. Moreover, besides solar cells, silicon nanowires have been investigated for many other electronic systems such as thermoelectrics, light emitting diodes, biological/chemical sensors, photodetectors and lithium ion v batteries. Therefore, production of silicon nanowires through a cost-effective and well controlled method could make important contributions to many fields. In this thesis, electroless etching method, which is a novel and solution based method enabling vertically aligned silicon nanowire array fabrication over large areas, is investigated. A detailed parametric study resulting in a full control over the resultant nanowire morphology is provided. The parameters affecting the structure have been determined as etching time, solution temperature, solution concentration, pressure and starting wafer characteristics. The results show that electroless etching method could replace the conventional silicon nanowire fabrication methods. It was shown that specific nanowire lengths for any application, can be obtained simply by adjusting the parameters of electroless etching system. One of the most crucial features of vertically aligned silicon nanowire arrays is their remarkable antireflective properties. The optical reflectivity measurements showed that 42% reflectivity of pristine polished silicon wafer decreases down to 1% following fabrication of silicon nanowire arrays on their surface. This unique characteristic reveals that these nanowires could be used as antireflective surfaces in solar cells. Moreover, it was determined that p-n heterojunctions that are formed by silicon nanowires, namely radial heterojunctions, would yield higher efficiencies compared to planar heterojunctions because of the dramatic increase in the charge carrier collection efficiency and orthogonal photon absorption. On this subject, n-type silicon nanowire arrays were fabricated by electroless etching followed by drop casting Poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate) (PEDOT:PSS) organic layer on these nanowires as the complementary layer, forming the radial heterojunction. The energy conversion efficiency of silicon nanowire / PEDOT: PSS device was found as 5.30%, while planar silicon / PEDOT: PSS control device displayed only 0.62% efficiency. Developments and optimizations in both the electroless etching method and solar cell models could lead to important developments in photovoltaic industry.

Pattern formation in buckled membranes was studied along with the morphology of flowers formed at the tip of silicon nanowires and ripples formed in suspended graphene sheets. Nash's perturbation method was tested for a simple case where initial and final metrics embed smoothly and there is a smooth path from one surface to another and was found to work successfully. The method was tested in more realistic conditions where a smooth path was not known and the method failed. Cylindrical flower-like membranes with a metric of negative Gaussian curvature were simulated in three and four dimensions. These four dimensional flowers had 2 orders of magnitude less energy than their three dimensional counterparts. Simulations were used to show that the addition of a fourth spatial dimension did not relieve all bending energy from the cylindrical membranes. Patterns formed at the tip of silicon nanowires were studied and found to be of the Dense Branching Morphology type. The rate of branching is dependent on the curvature of the gold bubble on which they are grown. Graphene was simulated using the modified embedded atom method potential and buckles were found to form if the carbon bonds were stretched. An energy functional was found for the energy of a sheet with a metric different from that of flat space. / text

Central to the implementation of colloidal nanomaterials in commercial applications is the development of high throughput synthesis strategies for technologically relevant materials. Solution based synthesis approaches provide the controllability, high throughput, and scalability needed to meet commercial demand. A flow through supercritical fluid reactor was used to synthesize silicon nanowires in high yield with production rates of ~45 mg/hr. The high temperature and high pressure of the supercritical medium facilitated the decomposition of monophenylsilane and seeded growth of silicon nanowires by gold seeds. Crystalline nanowires with diameters of ~25 nm and lengths greater than 20 [micrometers] were routinely synthesized. Accumulation of nanowires in the reactor resulted in deposition of a conformal amorphous shell on the crystalline surface of the wire. X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and energy dispersive X-ray spectroscopy were used to determine the shell composition. The shell was identified as polyphenylsilane formed by polymerization of the silicon precursor monophenylsilane. A post synthesis etch was developed to remove the shell while still maintaining the integrity of the crystalline silicon nanowire core. Subsequent surface passivation was achieved through thermal hydrosilylation with a terminal alkene. The development colloidal nanomaterials into commercial applications also requires simple and robust bottom-up assembly strategies to facilitate device fabrication. A Langmuir-Blodgett trough was used to assemble continuous monolayers of hexagonally ordered spherical nanocrystals over areas greater than 1 cm². Patterned monolayers and multilayers of FePt nanocrystals were printed onto substrates using pre-patterned polydimethylsiloxane (PDMS) stamps and a modified Langmuir Schaefer transfer technique. Patterned features, including micrometer-size circles, lines, and squares, could be printed using this approach. The magnetic properties of the printed nanocrystal films were also measured using magnetic force microscopy (MFM). Room temperature MFM could detect a remanent (permanent) magnetization from multilayers (>3 nanocrystals thick) films of chemically-ordered L1₀ FePt nanocrystals. Grazing incidence small angle X-ray scattering was used to quantitatively characterize the grain size, crystal structure, lattice disorder, and edge-to-edge spacing of the nanocrystal films prepared on the Langmuir-Blodgett trough both on the air-water interface and after transfer. / text

Nanowires are high aspect ratio nanostructures with structural diameters on the order of nanometers to hundreds of nanometers. In this work, the optical properties of highly crystalline silicon nanowires grown by the Vapor-Liquid-Solid (VLS) method surrounded by a thin silicon shell are investigated for thin film solar cell applications. Crystalline core nanowires were surrounded by a conformal amorphous silicon shell and exhibited extremely high absorption of 95% at short wavelengths (??<550nm) and very low absorption of <2% at long wavelengths (??>780nm). Nanowires were disordered with average lengths ranging from 1.3 to 2.3 ??m. The absorption increased at longer wavelengths as a function of amorphous shell radial thickness, significantly higher than the absorption of a reference planar a-Si thin film. In addition, a new method to grow epitaxial silicon at low growth temperatures on glass substrates is demonstrated. Highly crystalline silicon nanowires with an average length of 800 nm were used as the seed crystal to grow an epitaxial silicon shell around, using a low temperature process. The nanowire core was grown at 400??C, and the shell was grown at about 150??C. Such epitaxial grown nanowire shells could be used as a building block for nanotechnology applications in which epitaxial silicon is required over large-area substrates such as glass. Furthermore, the epitaxial silicon shell nanowires exhibited absorption > 90% up to a wavelength of 600 nm, which was significantly higher than that of a planar 1 ??m nanocrystalline silicon film. The high absorption exhibited by nanowires with both amorphous and crystalline silicon shells makes them promising for use in photovoltaic and photodetector applications. Silicon nanowires were incorporated into thin film silicon n-i-p solar cells in two configurations: as a nanostructured back reflector, and in core-shell nanowire solar cells. First, domed-shaped nanostructures were fabricated by coating an array of silicon nanowires with a thick layer of amorphous silicon. After the nanostructures were coated with Ag and ZnO:Al, they were used as the backreflector in an n-i-p amorphous silicon solar cell. The nanostructured backreflector improved light scattering within the solar cell, leading to a short circuit current of 14.8mA/cm2, a 13% improvement over that of the planar device, which had a Jsc=13.1 mA/cm2. The overall conversion efficiency of nanostructured backreflector device was ?? = 8.87%, a strong improvement over that of the planar device (?? = 7.47%). Silicon nanowires were also incorporated into core-shell nanowire solar cells. The first device architecture investigated consisted of nanowires incorporated as the intrinsic absorption layer between a planar n+ layer and conformal p+ layer. However, the fabricated devices exhibited very low collection efficiencies of < 2% due to the presence of impurities incorporated by the catalyst used during nanowire growth. As a result, the device architecture was modified such that the nanowires provided high aspect ratio structure to enhance absorption in a shell material, but the nanowires themselves were not used as an active device component. Nanowire core-amorphous silicon shell solar cells, on average 525 nm long and about 350nm in total diameter, exhibited an impressive low total reflectance of <3% in the wavelength interval of 410 nm < ?? < 640nm and exceeded 10% only for ??>700 nm. As a result, the core-shell nanowire devices exhibited enhancement in quantum efficiency at low wavelengths, ?? < 500nm and high wavelengths, ?? > 600nm as compared to a planar device. The resulting short circuit current was 14.1 mA/cm2 compared to 12.3 mA/cm2 for the planar device, an improvement of ~15%. Nanowire core- nanocrystalline silicon shell solar cells were also fabricated using the same device architecture. Core-shell nanowires with an average length of 800 nm showed significant enhancement in quantum efficiency over all wavelengths as compared to a 1 ??m thick planar solar cell. The core-shell nanowire device had a short-circuit current of 16.2 mA/cm2 , a ~25% improvement over that of the planar thin film solar cell (Jsc=13.0 mA/cm2). Core-shell nanowire devices did, however, have lower open circuit voltage compared to the planar device. Non-conformal coverage was found to be a limiting factor in device performance, but further improvements can be expected with optimization of the n-i-p deposition conditions and nanowire density.

Silicon nanowires are a nanostructure consisting of elongated crystals of silicon. Like many nanostructures, silicon nanowires have properties that change with size. In particular, silicon nanowires have a band-gap that is tuneable with the diameter of the nanowire. They tend to absorb a large portion of the light incident upon them and they form a highly textured surface when grown on an otherwise flat substrate. These properties indicate silicon nanowires are good candidates for use in solar cells. Nanostructured silicon, in the form of nanocrystalline silicon, has been used to produce thin film solar cells. Solar cells produced using silicon nanowires could combine the properties of the silicon nanowires with the low material costs and good stability of nanocrystalline based solar cells. This thesis describes the process of optimisation of silicon nanowire growth on a plasma enhanced chemical vapour deposition system. This optimised growth of silicon nanowires is then used to demonstrate a prototype solar cell using silicon nanowires and amorphous silicon. Several steps had to be accomplished to reach this goal. The growth of silicon nanowires was optimised through a number of steps to produce a high density film covering a substrate. Developments were made to the standard deposition technique and it was found that by using pulsed plasma enhanced chemical vapour deposition the density of nanowire growth could be improved. Of a range of catalysts trialled, gold and tin were found to be the most effective catalysts for the growth of silicon nanowires. A range of substrates was investigated and the nanowires were found to grow with high density on transparent conductive oxide coated glass substrates, which would allow light to reach the nanowires when they were used as part of a solar cell. The silicon nanowires were combined with doped and intrinsic amorphous silicon layers with the aim to create thin film photovoltaic devices. Several device designs using silicon nanowires were investigated. The variant that showed the highest efficiency used doped silicon nanowires as a p-layer which was coated with intrinsic and n-type amorphous silicon. By the characterisation and optimisation of the silicon nanowires, a prototype silicon nanowire solar cell was produced. The analysis of these prototype thin film devices, and the nanowires themselves, indicated that silicon nanowires are a promising material for photovoltaic applications.