In an approach to creating molecular-scale structures on glass surfaces via self assembly, a strongly-dimerizing ureido-[2-(4-pyrimidone)] (UPy) quadruple hydrogen-bonding array was chemically immobilized on silica surfaces by way of a triethoxysilane functionality. The unreacted surface silanols were then thoroughly passivated with a monofunctional organosilane, resulting in isolated UPy binding sites on the glass surface. These binding sites were found to selectively bind the strongly fluorescent perylenediimide (PDI) functionalized UPy molecules from solution, thus non-covalently linking the fluorophore to the surface. The association between the self-complementary molecules was exceptionally strong, both in solution and at the surface, such that effective hydrogen-bonding was retained after most solvent treatments. The binding was also reversible, however, so that washes with polar protic and dipolar aprotic solvents with high hydrogen-bonding capabilities, such as water, alcohols, and DMSO, resulted in the removal of the non-covalently bound fluorophore-tagged UPy. The UPy:UPy dimer system was also investigated in solution, using pyrene intramolecular excimer formation as a monitor of the dissociation of the pyrene heterodimers into homodimers incapable of forming excimers at micromolar concentrations. In addition, the energy transfer process in solution between pyrene and perylenediimide fluorophores linked through UPy dimerization was studied, with the intention using FRET-based measurements on the surface at single-molecule levels in order to determine the distances between UPy binding sites. Energy transfer was found to occur, but the observed photophysical behavior was complicated by possible secondary processes, which steady-state fluorescence measurements were unable to elucidate. The benefit of using this UPy system for attaching molecules to a surface lies in its reversibility of binding and versatility in manner of molecules which van be retained on the modified surface with a strong association. In this way molecular-scale features could conceivably be constructed on a surface by self-assembly, with the option of further chemical reactions to lock them in place, thus creating structures beyond the accessibility range of the conventional lithographic methods.

Photovoltaics (PV) offers a unique opportunity to solve energy and environmental problems simultaneously since the solar energy is essentially free, unlimited, and not localized any part of the world. Currently, more than 90% of PV modules are produced from crystalline Si. However, wafer preparation of cast multicrystalline Si materials account for more than 40% of the PV module manufacturing cost, which can be significantly reduced by introducing the ribbon-type Si materials. Edge-defined film-fed grown (EFG) and String Ribbon Si materials are among the promising candidates for the cost-effective PV because they are grown directly from the Si melt, which eliminates the need for ingot slicing and chemical etch for surface preparation. However, the growth of these ribbon Si materials leads to relatively high concentration of metallic impurities and structural defects, resulting in very low as-grown carrier lifetime of less than 5 µs. Therefore, the challenge is to produce high-efficiency cells on EFG and String Ribbon Si by enhancing the carrier lifetime during the cell processing and to understand the effect of electrically active defects on cell performance through in-depth device characterization and modeling. The research tasks of this thesis focus on the understanding, development, and implementation of defect passivation to enhance the bulk carrier lifetime in ribbon Si materials for achieving high-efficiency cells. It is shown in this thesis that the release of hydrogen from SiNx layer is initially rapid and then slows down with time. However, the dissociation of hydrogen from defects continues at the same pace. Therefore, a short firing provides an effective defect passivation. An optimized hydrogenation process produces a record high-efficiency ribbon Si cells (4.0 cm2) with photolithography (18.3%) and screen-printed (16.8%) contacts. However, active defects are still present even after the optimized hydrogenation process. An analytical model is developed to assess the impact of inhomogeneously distributed active defects on cell performance, and the model is applied to establish the roadmap for achieving high-efficiency ribbon Si cells in the presence of defects. Finally, PC1D simulations reveal that the successful implementation of the surface texturing can raise the cell efficiency to 18%.

Although silicon (Si) nanostructures exhibit size dependent light emission, which can be attributed to quantum confinement, the role of surface passivation is not yet fully understood. This understanding is central to the development of nanocrystal-based detectors. This study investigated the growth, surface chemistry, passivation with deuterium (D2), ammonia (ND3) and diborane (B2D6) and the resulting optical properties of Si nanostructures. Si nanocrystals less than 6 nm in diameter are grown on SiO2 surfaces in an ultra high vacuum chamber using hot-wire chemical vapor deposition and the as grown surfaces are exposed to atomic deuterium. Temperature programmed desorption (TPD) spectra show that that the nanocrystals surfaces are covered by a mix of monodeuteride, dideuteride and trideuteride species. The manner of filling of the deuteride states on nanocrystals differs from that for extended surfaces as the formation of the dideuteride and trideuteride species is facilitated by the curvature of the nanocrystal. No photoluminescence (PL) is observed from the as grown unpassivated nanocrystals. As the deuterium dose is increased, the PL intensity also begins to increase. This can be associated with increasing amounts of mono-, di- and trideuteride species on the nanocrystal surface, which results in better passivation of the dangling bonds and relaxing of the reconstructed surface. At high deuterium doses, the surface structure breaks down and amorphization of the top layer of the nanocrystal takes place. Amorphization reduces the PL intensity. Finally, as the nanocrystal size is varied, the PL peak shifts, which is characteristic of quantum confinement. The dangling bonds and the reconstructed bonds at the NC surface are also passivated and transformed with D and NDx by using deuterated ammonia (ND3), which is predissociated over a hot tungsten filament prior to adsorption. At low hot wire ND3 doses PL emission is observed at 1000 nm corresponding to reconstructed surface bonds capped by predominantly monodeuteride and Si-ND2 species. As the hot wire ND3 dose is increased, di- and trideuteride species form and intense PL is observed around 800 nm that does not shift with NC size and is associated with defect levels resulting from NDx insertion into the strained Si-Si bonds forming Si2=ND. The PL intensity at 800 nm increases as the ND3 dose is increased and the intensity increase is correlated to increasing concentrations of deuterides. At extremely high ND3 doses PL intensity decreases due to amorphization of the NC surface. In separate experiments, Si NCs were subjected to dissociative (thermal) exposures of ammonia followed by exposures to atomic deuterium. These NCs exhibited size dependent PL and this can be attributed to the prevention of the formation of Si2=ND species. Finally, deuterium-passivated Si NCs are exposed to BDx radicals formed by dissociating deuterated diborane (B2D6) over a hot tungsten filament and photoluminescence quenching is observed. Temperature programmed desorption spectra reveal the presence of low temperature peaks, which can be attributed to deuterium desorption from surface Si atoms bonded to subsurface boron atoms. The subsurface boron likely enhances nonradiative Auger recombination. / text

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Fluorescent carbon dots (C-dots) are well known for their low cell-cytotoxicity, biocompatibility, low preparation cost, excitation dependent photoluminescence, and excellent photostability. Typically, raw C-dots have low quantum efficiency and thus researchers have been utilizing biocompatible polymers such as polyethylene glycol (PEG) as a passivation agent in order to increase fluorescence signal. In this work, we report fluorescent self-passivated carbon nanodots (CNDs) synthesized from PEG by using it as a carbon source as well as a passivating agent. Importantly, the addition of graphene quantum dots (GQDs) during the synthesis of self-passivated CNDs can tune photoluminescence property. The results of bioimaging and cytotoxicity test of self-passivated CNDs hold promises for biomedicine applications.

In this thesis, a novel method of reducing the rear surface recombination in copper indium gallium (di) selenide (CIGS) thin film solar cells, using atomic layer deposited (ALD) Al2O3, has been evaluated via qualitative opto-electrical characterization. The idea stems from the silicon (Si) industry, where rear surface passivation layers are used to boost the open-circuit voltage and, hence, the cell efficiency. To enable a qualitative assessment of the passivation effect, Al/Al2O3/CIGS metal-oxide-semiconductor (MOS) devices with 3-50 nm oxide thickness, some post-deposition treated (i.e. annealed), have been fabricated. Room temperature capacitance-voltage (CV) measurements on the MOS devices indicated a negative fixed charge density (Qf) within the Al2O3 layer, resulting in a reduced CIGS surface recombination due to field effect passivation. After annealing the Al2O3 passivation layers, the field effect passivation appeared to increase due to a more negative Qf. After annealing have also indications of a lower density of interface traps been seen, possibly due to a stronger or activated chemical passivation. Additionally, the feasibility of using ALD Al2O3 to passivate the surface of CIGS absorber layers has also been demonstrated by room temperature photoluminescence (PL) measurements, where the PL intensity was about 20 times stronger for a structure passivated with 25 nm Al2O3 compared to an unpassivated structure. The strong PL intensity for all passivated devices suggests that both the chemical and field effect passivation were active, also for the passivated as-deposited CIGS absorbers.

The objective of this thesis is to understand and improve optical and electrical confinement to achieve cost-effective high-efficiency thin p-type Si solar cells. Optical confinement is achieved by front surface texturing in conjunction with an internal reflective layer on the back surface. Electrical confinement is obtained through the use of a high-lifetime material coupled with high-quality passivation on both surfaces. This research is divided into five tasks. In the first task, Ga-doped Cz Si was investigated to achieve a high and stable lifetime. It was found that for 1 ohm-cm nominal-resistivity screen-printed Al-back surface filed (BSF) cells, the Ga-doped ingot gave ~1.5% higher absolute efficiency after light-soaking relative to the B-doped counterpart. The benefit of using Ga is therefore quite explicit. In the second task, the screen-printed Al-BSF was investigated to explore its potential and limitations for achieving high-efficiency cells. It was found that there exists a critical alloying temperature for a given Al-thickness, above which the Al-BSF becomes non-uniform and cell performance starts to degrade. This puts a limit on the quality of the Al-BSF that can be achieved. An alternative way of back passivation involving dielectric/metal layers was therefore explored. In Task three, two key requirements for achieving high-efficiency dielectric back-passivated cells were established through device modeling. These are (1) a formation of a high-quality BSF underneath the local back contact through vias in the dielectric and (2) a high-quality dielectric passivation with either a moderate positive charge density or a high negative charge density. Task four involved the development of a metallization technique through vias in the dielectric to achieve a high-quality contact and an efficient internal reflector in conjunction with a high-quality local BSF. Further, a novel dielectric system composed of a spin-on SiO<SUB>2</SUB> layer capped with SiN<SUB>x</SUB> was developed that exhibited excellent passivation and a moderate positive charge density. The final task involved fabrication and analysis of dielectric back-passivated cells. The new dielectric and process sequence developed in this thesis resulted in screen-printed solar cells with efficiency as high as 19% with the potential for 20% efficient cells on 100-µm thick Si substrates.

In polycrystalline silicon (pc-Si) thin-film solar cells, defect passivation is critical to device performance. Isoelectronic or covalently bonded impurities, hydrogenic, extended defects and defects with localized levels in the bandgap (deep level defects) are typically introduced during the fabrication of, and/or are inherent to, pc-Si thin-film solar cells. These defects dramatically affect minority carrier lifetimes. Removing and/or passivating these defects is required to maximize minority carrier lifetimes and is typically done through thermal annealing and passivation techniques. For pc-Si thin-film solar cells on low temperature glass superstrates, rapid thermal annealing (RTA) and hydrogen plasma passivation (hydrogenation) are powerful techniques to achieve effective removal and passivation of these defects. In this thesis, three silicon thin-film solar cells structures on low-temperature glass are subjected to variations in RTA high-temperature plateaus, RTA plateau times, and hydrogen plasma passivation parameters. These solar cells are referred to as ALICIA, EVA and PLASMA. By varying the RTA plateau temperature and time at plateau, the trade-off between extensive dopant diffusion and maximum defect removal is optimized. To reduce the density of point defects and to electrically activate the majority of dopants, an RTA process is shown to be essential. For all three of the thin-film solar cell structures investigated in this thesis, a shorter, higher-temperature RTA process provides the best open-circuit voltage (Voc). Extensive RTA plateau times cause excessive dopant smearing, increasing n = 2 recombination and shunt resistance losses. Hydrogenation is shown to be an essential step to achieve maximum device performance by `healing' the defects inherent to pc-Si thin-film solar cells. If the hydrogen concentration is about 1-2 times the density of oxygen in the cells as measured by secondary ion mass spectroscopy (SIMS), the cells seem to respond best to hydrogenation, with good resultant Voc and short-circuit for all cells investigated in this thesis. The effect of hydrogen passivation on the Voc is spectacular, typically increasing it by a factor of 2 to 3.5. Hydrogen de-bonding from repeated thermal treatments at increasing temperature provides a deeper understanding of what defects exist and the nature of the defects that limit the cell voltage. The variation in RTA and hydrogenation process parameters produces significant empirical insight into the effectiveness of RTA processes for point defect removal, dopant activation, point defect and grain boundary passivation, and impurity passivation. SIMS measurements are used to determine the impurities present in the cells' bulk and the amount of hydrogen available to passivate defects. From the results presented it appears that pc-Si thin-film solar cells on low-temperature glass are a promising, and potentially lower-cost, alternative to Si wafer based cells.

The cost of crystalline silicon solar cells must be reduced in order for photovoltaics to be widely accepted as an economically viable means of electricity generation and be used on a larger scale across the world. There are several ways to achieve cost reduction, such as using thinner silicon substrates, lowering the thermal budget of the processes, and improving the efficiency of solar cells. This thesis examines the use of plasma enhanced chemical vapour deposited silicon nitride to address the criteria of cost reduction for n-type crystalline silicon solar cells. It focuses on the surface passivation quality of silicon nitride on n-type silicon, and injection-level dependent lifetime data is used extensively in this thesis to evaluate the surface passivation quality of the silicon nitride films. The thesis covers several aspects, spanning from characterisation and modelling, to process development, to device integration. The thesis begins with a review on the advantages of using n-type silicon for solar cells applications, with some recent efficiency results on n-type silicon solar cells and a review on various interdigitated backside contact structures, and key results of surface passivation for n-type silicon solar cells. It then presents an analysis of the influence of various parasitic effects on lifetime data, highlighting how these parasitic effects could affect the results of experiments that use lifetime data extensively. A plasma enhanced chemical vapour deposition process for depositing silicon nitride films is developed to passivate both diffused and non-diffused surfaces for n-type silicon solar cells application. Photoluminescence imaging, lifetime measurements, and optical microscopy are used to assess the quality of the silicon nitride films. An open circuit voltage of 719 mV is measured on an n-type, 1 Ω.cm, FZ, voltage test structure that has direct passivation by silicon nitride. Dark saturation current densities of 5 to 15 fA/cm2 are achieved on SiN-passivated boron emitters that have sheet resistances ranging from 60 to 240 Ω/□ after thermal annealing. Using the process developed, a more profound study on surface passivation by silicon nitride is conducted, where the relationship between the surface passivation quality and the film composition is investigated. It is demonstrated that the silicon-nitrogen bond density is an important parameter to achieve good surface pas-sivation and thermal stability. With the developed process and deeper understanding on the surface passivation of silicon nitride, attempts of integrating the process into the fab-rication of all-SiN passivated n-type IBC solar cells and laser doped n-type IBC solar cells are presented. Some of the limitations, inter-relationships, requirements, and challenges of novel integration of SiN into these solar cell devices are identified. Finally, a novel metallisation scheme that takes advantages of the different etching and electroless plating properties of different PECVD SiN films is described, and a preliminary evalua-tion is presented. This metallisation scheme increases the metal finger width without increasing the metal contact area with the underlying silicon, and also enables optimal distance between point contacts for point contact solar cells. It is concluded in this thesis that plasma enhanced chemical vapour deposited silicon nitride is well-suited for n-type silicon solar cells.

E-glass has been widely used as a reinforcing material for years, especially as a plastic reinforcer in the production of GRP (Glass Reinforced Plastic). Failure of GRP materials under stress came in to the picture quite recently. Since then studies have been conducted in an attempt to understand the causes and the underlying behaviour. / Except for the last section of the research (analysis using a kinetic approach) where glass fibre was cut out to weigh approximately 1.0g, standard sized specimens were soaked in the required acid solutions of desired concentrations for varying temperatures and time frames. Wherever tensile strength retention was measured, LLOYD instrument was employed. Leaching of the cations were analysed using Inductively Coupled Plasma – Optical Emission Spectroscopy (ICP-OES and also know and ICP-AES). / The scope of this project can be divided in to four sections; first section involved investigating the effects of malonic acid. The study of malonic acid was narrowed to investigating the trend in strength retention. A rapid strength loss was observed initially followed by a much steady decline in the strength. However the continuation of the loss of strength was unmistakable throughout the time period of exposure. Furthermore, temperature can be observed as a facilitating factor in this degradation reaction. / Secondly the corrosive effect of glyoxylic acid on E-glass fibre was studied. This was explored at two different temperatures for two specific time frames using various concentrations of the acid of interest. The influence of this acid on the glass fibre was found out in terms of strength retention and loss of cations from the glass matrix. The mildness of this acid was accentuated by the fact that 70% or more of the strength was retained at all the conditions employed. A minima in strength retention was observed at 2M acid concentration similar to the trends observed in the past (Betz and Jones 2003 and Jones and Chandler 1986). Leaching of cations reflected this trend. The large strength retention could be related to the fewer amounts of Ca and K leached from the glass matrix (Kumosa and Qui, 1997). Similar to malonic acid, an unusually large amount of B was leached out that could be due to the favourable orientation of the anion with the trivalent ions during the complex formation. Yet again temperature was found to enhance the degradation process. / Next the extent of passivation (if any) showed by malonic acid was investigated using E-glass fibre pre-treated in 5M malonic acid and post treated in known corrosive acids hydrochloric acid and oxalic acid. Passivation of malonic acid was put to test through examination of strength retention of the fibres under these conditions. This segment was carried out as an extension of a finding (a behaviour synonymous to passivation) shown by malonic that surfaced the previous year by the present researcher. Increasing the pre-treatment time showed a great improvement in the retained strength for all the post-treatment acid mediums. Furthermore, while Jones and Betz (2004) featured 20-40% strength retention within a short time frame in 3M HCl, the immense amount of strength retention (60-70%) preceding pre-treatment should definitely be noted. Similarly strength retention of about 80% was observed when post-treated with the severely corrosive oxalic acid. Hence its is clear that passivation can be induced through prolonged pre-treatment in 5M malonic acid that could inhibit the attack of corrosive acid at least for a period of time. / The last fragment of the study focussed on understanding and working out the mechanism behind the reactions between the E-glass fibre and acid medium in terms of kinetics. The acids utilized were 1.5M malonic acid and 3M glyoxylic acid and the assessments were made through the analysis of the weight changes brought about by the acid medium at various temperatures and time frames. In addition leaching patterns of cations were evaluated as this could contribute in achieving the objective. Maximum weight loss reached 4% in glyoxylic acid while that for malonic acid exceeded 20%. The general trend was that the glass fibres lost weight in both acids for a period of time followed by an evident weight gain. Furthermore the weight loss results fit the first order rate law. While the leaching of cations reflects the weight loss for the shorter time frames, steady loss of ions was visible even for the longer time frames where the weight has increased. The weight gain could be explained in terms of binding of anions to certain cations on the glass surface, accounting for the hindrance in the loss of cations at the longer time frames as well. About 50% of weight loss was associated to Ca while 20% was to Al, leaving 6% to B where as the rest of the ions had shown almost insignificant contribution to the weight loss.