abstract: Semiconductor nanostructures are promising building blocks for light management in thin silicon solar cells and silicon-based tandems due their tunable optical properties. The present dissertation is organized along three main research areas: (1) characterization and modeling of III-V nanowires as active elements of solar cell tandems, (2) modeling of silicon nanopillars for reduced optical losses in ultra-thin silicon solar cells, and (3) characterization and modeling of nanoparticle-based optical coatings for light management. First, the recombination mechanisms in polytype GaAs nanowires are studied through photoluminescence measurements coupled with rate equation analysis. When photons are absorbed in polytype nanowires, electrons and holes quickly thermalize to the band-edges of the zinc-blende and wurtzite phases, recombining indirectly in space across the type-II offset. Using a rate equation model, different configurations of polytype defects along the nanowire are investigated, which compare well with experiment considering spatially indirect recombination between different polytypes, and defect-related recombination due to twin planes and other defects. The presented analysis is a path towards predicting the performance of nanowire-based solar cells. Following this topic, the optical mechanisms in silicon nanopillar arrays are investigated using full-wave optical simulations in comparison to measured reflectance data. The simulated electric field energy density profiles are used to elucidate the mechanisms contributing to the reduced front surface reflectance. Strong forward scattering and resonant absorption are observed for shorter- and longer- aspect ratio nanopillars, respectively, with the sub-wavelength periodicity causing additional diffraction. Their potential for light-trapping is investigated using full-wave optical simulation of an ultra-thin nanostructured substrate, where the conventional light-trapping limit is exceeded for near-bandgap wavelengths. Finally, the correlation between the optical properties of silicon nanoparticle layers to their respective pore size distributions is investigated using optical and structural characterization coupled with full-wave optical simulation. The presence of scattering is experimentally correlated to wider pore size distributions obtained from nitrogen adsorption measurements. The correlation is validated with optical simulation of random and clustered structures, with the latter approximating experimental. Reduced structural inhomogeneity in low-refractive-index nanoparticle inter-layers at the metal/semiconductor interface improves their performance as back reflectors, while reducing parasitic absorption in the metal. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2019

Titanium dioxide (TiO2) thin films have a long history in silicon photovoltaics (PV) as antireflection (AR) coatings due to their excellent optical properties and low deposition cost. This work explores several novel areas where TiO2 thin films could be use to enhance silicon (Si) solar cell performance while reducing device fabrication costs. Amorphous, anatase and rutile TiO2 thin films are deposited using ultrasonic spraydeposition (USD) and chemical vapour deposition (CVD) systems, both designed and constructed by the author. Initial experiments confirmed that no degradation in the bulk minority carrier lifetime (????bulk) occurred during high-temperature processing, although the stability of the USD-deposited TiO2 films was dependent on the furnace ambient. A major disadvantage of TiO2 AR coatings is that they afford little surface passivation. In this work, a novel method of achieving excellent surface passivation on TiO2-coated silicon wafers is presented. This involved growing a 6 nm-thick SiO2 layer at the TiO2:Si interface by oxidising the wafer after TiO2 film deposition. The increase in surface passivation afforded by the interfacial SiO2 layer results in a decrease in the emitter dark saturation current density (J0e) by nearly two orders of magnitude to 4.7 ??? 7.7 ??~ 10???14 A/cm2. This demonstrates the compatibility of the TiO2/SiO2 stack with high-efficiency solar cells designs. By varying the film deposition and annealing conditions, TiO2 refractive indices in the range of 1.726 ??? 2.633 (at ???? = 600 nm) could be achieved. Subsequently, a double-layer antireflection (DLAR) coating was designed comprised of low and high TiO2 refractive index material. The best experimental weighted average reflectance (Rw) achieved was 6.5% on a planar silicon wafer in air. TiO2 DLAR coatings are ideally suited to multicrystalline silicon (mc-Si) wafers, which do not respond well to chemical texturing. Modelling performed for a glass and ethyl vinyl acetate (EVA) encapsulated buried-contact solar cell indicated that a TiO2 DLAR coating afforded a 7% increase in the short circuit current density, when compared to a standard, commercially-deposited TiO2 single-layer AR coating. Finally, it is demonstrated that chemical reactions with phosphorus prevent TiO2 from acting as a successful phosphorus diffusion barrier or dopant source. The applicability of TiO2 thin films to various silicon solar cell structures is discussed.

This thesis undertakes the development, characterization and optimization of boron diffusion for silicon solar cells. Heavy diffusions (sheet resistance < 40 Ohm/square) to form a back surface field, and light diffusions (sheet resistance > 100 Ohm/square) to form oxide-passivated emitters were developed. Test structures and solar cells were fabricated to assess uniformity, lifetime and recombination effects due to the light and heavy boron diffusions. It was found that the growth of a thin ~200 ??, thermal oxide, during stabilization ??? immediately prior to the boron diffusion - was required to maintain high lifetime and reduce surface recombination (reducing the emitter saturation current density) for all boron diffusions. The heavy boron diffusion process was incorporated into the single side buried contact solar cell processing sequence. The solar cells fabricated had both boron diffused and Al/Si alloyed P+ regions for comparison. This research conclusively showed that boron diffused solar cells had significantly higher open circuit voltage compared to Al/Si alloyed devices. Fabrication of n-type solar cells, and their subsequent characterization by overlayed secondary electron image and the electron beam induced current map showed that the Al/Si alloy varied in depth from 5 to 25 micrometers deep. Methodology and characterization for light, oxide-passivated boron diffusions are also presented. This study yielded boron diffused emitters (sheet resistance > 100 Ohm/square) with low emitter saturation current. It was observed that this was possible only when the thermal oxidation after the boron diffusion was minimal, less than 1,000 ??. This was due to the segregation effect of boron with oxide, decreasing the surface concentration that in turn decreased the electric field repulsion of electrons from the surface. Device modelling of n-type solar cells is presented where the parameters of the modelling include the results of the light, oxide-passivated boron diffusions. This modelling shows n-type-base material with light oxide-passivated boron diffusion has higher potential conversion efficiency than forming a solar cell from phosphorous diffused p-type material.

In this thesis, the structural, optical and electrical properties of crystalline silicon quantum dots (SiQDs) are examined for application to silicon based tandem cells. The approach has been to concentrate on all silicon devices by taking advantage of quantum confinement in low-dimensional Si. RF magnetron co-sputtering provided the capability of creating superlattice structures in conjunction with high temperature annealing, to form Si nanocrystals in an oxide matrix. Structural techniques, including Fourier transform infrared spectroscopy (FTIR), micro-Raman spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), and Secondary ion mass spectroscopy (SIM) were employed to gather structural information about the SiQD/SiO2 SLs. The result combine presents that the packing density of Si QDs, correlated to the oxygen content of the silicon rich oxide layer can be control independently. The effect of Si nanocrystallite density on Raman scattering is investigated. The preliminary results present that a decrease in the oxygen content (x) results in an increased sharpness of the Strokes-mode peak of nanocrystalline Si, attributed to an increase in the proportion of crystalline Si because of the increased number of SiQDs. However the influence of the surface region on the crystallite core intensity scattering becomes dominant, when SiQD size diameter is very small (less than 3 nm). The present work shows that a decrease in x-content leading to an increase of the SiQD concentration, initially results in the enhancement of the lateral conductivity in the SiQD superlattice material. In this work, the Al contacting scheme, using a prolonged heat treatment technique at elevated temperature less than the eutectic point of Al and Si (577C) has been successfully applied to making Ohmic contacts on both SiQD SLs in oxide and nitride matrices. Activation energy (Ea) of SiQDs, extracted from a linear Arrhenius plot is investigated in the present work in order to expand the understanding of engineering electrical injection in laterally active paths. It is found that a lower barrier height of dielectric matrix influences to the lateral electron transport of the SiQDs in such dielectric matrix. PL results confirm that the band gap of surface oxidized SiQDs widens due to quantum confinement. The present results reveal that the strong peak (Q-peak) due to quantum confinement is more effective in the emission with increasing SiQD concentration. The surface oxide is believed to play an important role in the reduction of SiQD luminescence due to a trapped exiciton. It is concluded that SiQDs surface oxide accompanied by a SiO2 matrix may not provide a good passivation in very small SiQD size. However the energy band gap and conductivity of the SiQDs are tunablity, in the optimum range of SiQD size and concentration. This observation may be important for future nanoelectronics applications.

Current leading thin-film solar cell technologies, i.e., cadmium telluride (CdTe) and copper indium gallium diselenide (CIGS), employ elements which are either toxic (Cd), or rare and/or expensive (In, Te, Ga, and Cd). The aim of this thesis is to investigate new, abundant, non-toxic p-type semiconductors for potential solar absorber application. Two ternary chalcogenides, Cu���PSe��� and CuTaS���, were selected for their attractive calculated optical absorption properties. Thin films of both materials were synthesized using physical vapor deposition (PVD) techniques in conjunction with post-deposition annealing. Cu���PSe��� appears promising for solar absorber applications, with a measured optical bandgap of 1.2 eV, an absorption coefficient (��) reaching 10��� cm�����, Hall mobilities of 19.8���30.3 cm��/V���s, and carrier concentrations of 3.3���4.9 10����� cm�����. Optical characterization of CuTaS��� thin-films showed a rapid turn-on of absorption, with �� exceeding 10��� cm����� within 0.5 eV of the bandgap. To date, reproducible synthesis of CuTaS��� thin films has been problematic. Moreover, these films are insulating and thus not yet appropriate for thin-film solar cell absorber applications. / Graduation date: 2013

Graduation date: 1998

Thesis (M.S.)--University of Missouri--Rolla, 2007. / Vita. The entire thesis text is included in file. Title from title screen of thesis/dissertation PDF file (viewed April 17, 2007) Includes bibliographical references (p. 88-91).

This thesis focuses on liquid redox electrolytes in dye-sensitized solar cells (DSCs). A liquid redox electrolyte, as one of the key constituents in DSCs, typically consists of a redox mediator, additives and a solvent. This thesis work concerns all these three aspects of liquid electrolytes, aiming through fundamental insights to enhance the photovoltaic performances of liquid DSCs. Initial attention has been paid to the iodine concentration effects in ionic liquid (IL)-based electrolytes. It has been revealed that the higher iodine concentration required in IL-based electrolytes can be attributed to both triiodide mobility associated with the high viscosity of the IL, and chemical availability of triiodide. The concept of incompletely solvated ionic liquids (ISILs) has been introduced as a new type of electrolyte solvent for DSCs. It has been found that the photovoltaic performance of ISIL-based electrolytes can even rival that of organic solvent-based electrolytes. And most strikingly, ISIL-based electrolytes provide highly stable DSC devices under light-soaking conditions, as a result of the substantially lower vapor pressure of the ISIL system. A significant synergistic effect has been observed when both guanidinium thiocyanate and N-methylbenzimidazole are employed together in an IL-based electrolyte, exhibiting an optimal overall conversion efficiency. Tetrathiafulvalene (TTF) has been investigated as an organic iodine-free redox couple in electrolytes for DSCs. An unexpected worse performance has been observed for the TTF system, albeit it possesses a particularly attractive positive redox potential. An organic, iodine-free thiolate/disulfide system has also been adopted as a redox couple in electrolytes for organic DSCs. An impressive efficiency of 6.0% has successfully been achieved by using this thiolate/disulfide redox couple in combination with a poly (3, 4-ethylenedioxythiophene) (PEDOT) counter electrode material under full sunlight illumination (AM 1.5G, 100 mW/cm2). Such high efficiency can even rival that of its counterpart DSC using a state-of-the-art iodine-based electrolyte in the systems studied.The cation effects of lithium, sodium and guanidinium ions in liquid electrolytes for DSCs have been scrutinized. The selection of the type of cations has been found to exert quite different impacts on the conduction band edge (CB) of the TiO2 and also on the electron recombination kinetics, therefore resulting in different photovoltaic behavior. / QC 20120124

Potential electrolytes for dye-sensitized photoelectrochemical solar cells have been synthesized and their applicability has been investigated. Different experimental techniques were used in order to characterize the synthesized electrolytes, such as elemental analysis, electrospray ionisation/mass spectrometry, cyclic voltammetry, dynamic viscosity measurements, as well as impedance, Raman and NMR spectroscopy. Some crystal structures were characterized by using single crystal X-ray diffraction. In order to verify the eligibility of the ionic compounds as electrolytes for photoelectrochemical solar cells, photocurrent density/photovoltage and incident photon-to-current conversion efficiency measurements were performed, using different kinds of light sources as solar simulators. In electron kinetic studies, the electron transport times in the solar cells were investigated by using intensitymodulated photocurrent and photovoltage spectroscopy. The accumulated charge present in the semiconductor was studied in photocurrent transient measurements. The ionic liquids were successfully used as solar cell electrolytes, especially those originating from the diethyl and dibutyl-alkylsulphonium iodides. The highest overall conversion efficiency of almost 4 % was achieved by a dye-sensitized, nanocrystalline solar cell using (Bu2MeS)I:I2 (100:1) as electrolyte (Air Mass 1.5 spectrum at 100 W m-2), quite compatible with the standard efficiencies provided by organic solvent-containing cells. Several solar cells with iodine-doped metal-iodidebased electrolytes reached stable efficiencies over 2 %. The (Bu2MeS)I:I2-containing cells showed better long-term stabilities than the organic solvent-based cells, and provided the fastest electron transports as well as the highest charge accumulation. Several polypyridyl-ruthenium complexes were tested as solar cell sensitizers. No general improvements could be observed according to the addition of amphiphilic co-adsorbents to the dyes or nanopartices of titanium dioxide to the electrolytes. For ionic liquid-containing solar cells, a saturation phenomena in the short-circuit current densities emerged at increased light intensities, probably due to inherent material transport limitation within the systems. Some iodoargentates and -cuprates were structurally characterized, consisting of monomeric or polymeric entities with anionic networks or layers. A system of metal iodide crownether complexes were employed and tested as electrolytes in photoelectrochemical solar cells, though with poorer results. Also, the crystal structure of a copper-iodide-(12-crown-4) complex has been characterized / QC 20101013

Crystalline silicon (Si) wafers used as substrates in the semiconductor and photovoltaic (PV) industries are traditionally manufactured using a multi-wire slurry sawing (MWSS) technique. Due to its high productivity potential, the fixed abrasive diamond wire sawing (DWS) technique is of considerable interest to Si wafer producers. Although both sawing techniques are currently used in the industry, a fundamental understanding of the underlying process is still lacking, particularly for diamond wire sawing. Consequently, optimization of the wire sawing process is carried out largely based on experience and trial and error. This thesis aims to develop a systematic fundamental understanding of diamond wire sawing of Si materials used for PV applications. First of all, a comparative analysis of the characteristics of silicon wafers cut by slurry and fixed abrasive diamond wire sawing is presented. The analysis results indicate that fixed abrasive diamond wire sawing may be a viable alternative to slurry wire sawing. Modeling and experimental studies of single grit diamond scribing of Si are proposed to shed light on the basic cutting mechanisms. Although Si is brittle at room temperature, it is possible to properly control the cutting conditions to obtain a completely ductile mode of material removal. The effects of material anisotropy, abrasive grit shape, friction condition and external hydrostatic pressure on the ductile-to-brittle mode transition in cutting of single crystal Si (sc-Si) are systematically investigated. Multicrystalline Si (mc-Si) based solar cells take up the majority of the global PV market. Hard inclusions (Silicon carbide and Silicon nitride) in multicrystalline Si (mc-Si) ingots may cause wire breakage and negatively impact the process, surface/subsurface morphology and mechanical properties of the resulting wafer. Their effects are experimentally studied through the single grit diamond scribing on the mc-Si sample with high density of inclusions. Finally, it is identified that there is a correlation between the high dislocation density and the increase of fracture toughness in mc-Si. The increase in fracture toughness leads to greater capability of ductile mode of cutting and higher specific scribing energy in the brittle fracture regime. Results of these fundamental investigations are expected to generate useful knowledge for optimizing the diamond wire sawing process in order to achieve high productivity and minimum surface/subsurface damage.