Described herein are two projects focusing on developing and investigating two types of nanoparticles (NPs) grown by the seeded growth method from a conducting metallopolymer for photovoltaic (PV) applications. Core/shell CdS/ZnS NPs are proven to resist the photo-oxidation of PV devices, while CuInxGa(1-x)Se2 (CIGS) NPs are expected to optimize the efficiency of PV devices. / text

Solution deposition of thin film photovoltaic materials leads to large variations in the morphological and chemical compositions of the film. In order to improve device functionality, it is important to understand how morphology and chemical composition affects charge generation, separation, and collection. This PhD work will first study bulk methods in order to characterize materials in solution and films. The results are then correlated with microscopy studies examining morphology. Other methods used in this PhD work will directly couple spectra and microscopy. Microscopic regions of such films and devices can be illuminated using scanning confocal microscopy or near-field scanning optical microscopy (NSOM), which allows for one to directly probe regions of the film at or below the optical diffraction limit. By scanning the sample over a fixed laser spot we can simultaneously create image maps of the topographical, electrical and optical properties. This technique, known as laser beam induced current (LBIC) allows one to directly probe a local area of a device with 100-300nm resolution. Along with bulk device efficiency studies, near field and confocal data of inorganic and organic materials are investigated. These include devices fabricated with a blend of P3HT (poly[3-hexylthiophene]) and perylene diimide derivatives, and Cu(InxGa1-x)Se2 [CIGS] nanoparticle devices. Finally, we use a new device architecture, a lateral organic photovoltaic (LOPV) in order to spatially resolve transport in functional organic devices. / text

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.

Sir Henry Wilson remains one of the most controversial British Army generals of the Great War. A colourful character in life, he attracted admirers and detractors in equal measure; in death, his reputation was ruined by a biography based on his personal diaries. The Wilson of the historiography is, at best, a politician rather than a soldier, at worst an ambitious Francophile intriguer. This thesis looks beyond this accepted characterisation, reassessing his role in the formation of British and Allied strategy in the final months of the war. Wilson attained influence, and subsequently power, when Lloyd George consulted him after failing to persuade Britain’s leading generals to change their strategic focus. The thesis re-examines Wilson’s policy critique, which led to the creation of the Supreme War Council, and negated plans for a major Allied offensive on the Western Front in 1918. This thesis aims to shine new light on Wilson’s work on the Council, with an analysis of its policy recommendations. The research will also explore the manpower crisis, the key issue for the entente in this period, and Wilson’s contribution to the establishment of Allied unity of command. The diplomatic skills Wilson deployed to defuse serious strains between the entente powers will be examined, with particular reference to his time as Chief of the Imperial General Staff. His contribution to the debate on Britain’s post-war imperial grand strategy will also be evaluated. The thesis will refute the long-established onedimensional view of Wilson and suggest that he played a more influential role in British strategic development than has hitherto been acknowledged.

This project will be a part of the LODESTAR experiment. LODESTAR is one of the experiments scheduled to fly on the REXUS/BEXUS 26 high altitude balloon flight. The primary objective of the experiment is to investigate the effects of cosmic radiation on CIGS solar cells. The objective of this project is to build a mechanical design that can fulfill all requirements set by the ESA user manual. The mechanical design will first be drawn in mechanical CAD, where the drawing will be constructed from the ESA requirements. Later the design will be simulated in order to choose appropriate materials and a design that can withstand all simulations. Lastly the design will be built according to the drawings and tested according to the simulations. The mechanical design withstood all the simulations and verification tests with no visual deformation, except for the simulation and verification of the drop test. Both the drop simulation and verification test resulted in deformation in one of the aluminium plates. Since this mechanical design is constructed to be used only once, small deformations is within the margin of error. The deformation resulted by the simulation and verification of the drop test matched with a high precision. This is a good confirmation of the results of the drop test. In conclusion, the executed tests gave very promising results. Therefor the design constructed fits all the requirements to travel with solar panels in stratospheric conditions. / LODESTAR -BEXUS Project

Cu(In,Ga)(Se,S)2 (CIGS) solar cells have attracted a lot of attention due to their high performance and the prospect for lower manufacturing costs over conventional crystalline silicon solar cells. All recent record efficiency CIGS absorbers have been deposited using vacuum processing which introduces high manufacturing costs. CIGS can also be compatible with low cost, atmospheric processing which can significantly reduce manufacturing costs. Recently, there has been some progress in developing atmospheric solution-based processes for CIGS. Among different solution approaches, deposition of molecular precursors can be advantageous in terms of simplicity and straightforward compositional control. Nonetheless, the developed methodologies involve highly toxic reagents or large impurity content in the device, limiting the potential for commercialisation. This thesis describes the development of a novel solution-based approach for the deposition of CIGS absorber layers. Metal chalcogenides are used as the starting precursors, which are free from detrimental impurities. These compounds contain strong covalent bonds and, consequently, they are insoluble in common solvents. Until recently, hydrazine, which is highly toxic and explosive, was the only solvent to effectively dissolve these types of precursors, limiting the feasibility of this approach for industrial applications. In this work, metal chalcogenides are dissolved in a safer solvent combination of 1,2-ethanedithiol and 1,2-ethylenediamine, completely eliminating hydrazine from the process. By using this solvent system, optically transparent solutions are formed which exhibit long-term stability. The precursor solutions are decomposed cleanly and they are converted to single phase CIGS upon selenisation. CuIn(S,Se)2 solar cells with power conversion efficiencies up to 8.0% were successfully fabricated by spray depositing the precursor solution, followed by a selenisation step. This progress has been made by continuously optimising the deposition, drying, and especially the selenisation configuration. Among other parameters, the working pressure during selenisation was found to have a dramatic effect on the material crystalline quality. Rapid thermal processing was also explored as an alternative selenisation configuration to tube furnace annealing and it was shown to improve the back contact/absorber interface. It has been demonstrated that Ga can easily be incorporated in the absorber for band-gap tuning and, consequently, for VOC enhancement of the solar cells. The structural properties of the films were investigated with Ga content, as well as the opto-electronic characteristics of the corresponding solar cells. The band-gap of the material was conveniently varied by simply adjusting the precursor ratio, allowing for fine compositional control. By using this technique, Cu(In,Ga)(Se,S)2 solar cells with conversion efficiencies of up to 9.8% were obtained. The solar cell performance in this work is limited by the porosity of the absorber and the back contact quality. Despite a significant improvement during the course of this work, the remaining porosity of the absorber causes selenium to diffuse towards the back forming a thick MoSe2 layer and causing a high series resistance in the device. A low cost, solution-based technique was also developed for the deposition of aluminium-doped zinc oxide films that can be used as the transparent conductive oxide layer in thin film solar cells. This methodology involves the use of an ultrasonic spray pyrolysis system, which is a very versatile and easily controlled deposition technique. Although the presence of oxygen makes the film closer to stoichiometric (fewer oxygen vacancies) good electronic and optical properties have been obtained by process optimisation. Films deposited with optimum conditions exhibited a sheet resistance of 23 Ω/sq, which can be further reduced by increasing the thickness with minimal transmittance losses. The simplicity, low toxicity and straightforward control make the proposed methodologies extremely potential for low cost and scalable deposition of thin film solar cells.

xv, 132 p. : ill. A print copy of this title is available from the UO Libraries, under the call number: SCIENCE TK7871.15.F5 H325 2007 / The effects of sulfur alloying on the electronic properties of CuIn(SeS) 2 and CuInGa(SeS) 2 materials has been investigated using sophisticated junction capacitance techniques including drive-level capacitance profiling and transient photocapacitance and photocurrent spectroscopies. CISSe and CIGSSe materials are used as absorber layers in thin-film photovoltaic devices. By characterizing the electronic properties of these materials we hope to understand how these materials can be improved to make thin-film devices with better conversion efficiencies. Sulfur widens the bandgap of these materials by moving the valence band to lower energies and the conduction band to higher energies. This significantly affects the electronic structure of these devices by increasing the activation energies of dominant acceptor levels and lowering room temperature free hole carrier densities. Using optical spectroscopies we observe a large, broad defect that also changes its apparent energetic depth with sulfur alloying. The occupation of this defect was controlled both optically and thermally, and showed a striking temperature dependence. This temperature dependence was measured by recording the relative defect signal, the ratio of the TPC signal in the defect regime to the above bandgap regime, as a function of temperature. As the temperature of the measurement was decreased, steps in the relative defect signal were observed, indicating the turning off of the thermal pathway that emptied trapped charge from the defect. Remarkably, such steps were seen at the same temperature in CISSe and CIGSSe devices with similar sulfur content. In addition, no steps were seen in CMS devices. This points to a defect state specific to the incorporation of sulfur in the absorber material. We hope that a better understanding of the electronic structure of these materials will assist in the creation of improved wide-bandgap thin-film photovoltaic devices. / Adviser: J. David Cohen

abstract: It is well known that the overall performance of a solar cell is limited by the worst performing areas of the device. These areas are usually micro and nano-scale defects inhomogenously distributed throughout the material. Mitigating and/or engineering these effects is necessary to provide a path towards increasing the efficiency of state-of-the-art solar cells. The first big challenge is to identify the nature, origin and impact of such defects across length scales that span multiple orders of magnitude, and dimensions (time, temperature etc.). In this work, I present a framework based on correlative X-ray microscopy and big data analytics to identify micro and nanoscale defects and their impact on material properties in CuIn1-xGaxSe2 (CIGS) solar cells. Synchrotron based X-ray Fluorescence (XRF) and X-ray Beam Induced Current (XBIC) are used to study the effect that compositional variations, between grains and at grain boundaries, have on CIGS device properties. An experimental approach is presented to correcting XRF and XBIC quantification of CIGS thin film solar cells. When applying XRF and XBIC to study low and high gallium CIGS devices, it was determined that increased copper and gallium at grain boundaries leads to increased collection efficiency at grain boundaries in low gallium absorbers. However, composition variations were not correlated with changes in collection efficiency in high gallium absorbers, despite the decreased collection efficiency observed at grain boundaries. Understanding the nature and impact of these defects is only half the battle; controlling or mitigating their impact is the next challenge. This requires a thorough understanding of the origin of these defects and their kinetics. For such a study, a temperature and atmosphere controlled in situ stage was developed. The stage was utilized to study CIGS films during a rapid thermal growth process. Comparing composition variations across different acquisition times and growth temperatures required the implementation of machine learning techniques, including clustering and classification algorithms. From the analysis, copper was determined to segregate the faster than indium and gallium, and clustering techniques showed consistent elemental segregation into copper rich and copper poor regions. Ways to improve the current framework and new applications are also discussed. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2018

Cu(In,Ga)Se2 (CIGS) is a semiconductor material and the basis of the promising thin-film photovoltaic technology with the same name. The CIGS film has a typical thickness of 1-2 mm, and solar cells based on CIGS technology has recently reached efficiencies of 23.3%. Ultra-thin CIGS solar cells use sub-micrometer thick films that require significantly less material and can be manufactured in a shorter amount oftime than films with typical thicknesses. With decreasing thickness, both electrical and optical losses get more significant and lower the overall performance. Electrical losses can be decreased by increasing the overall film quality and by utilising a graded bandgap throughout the CIGS layer. The band gap can be changed by varying the[Ga]/([Ga]+[In]) (GGI) ratio. Higher overall film quality and a higher band-gap towards the back of the absorber are expected to increase the performance. In this work, sputtered CIGS solar cells were made with different CIGS layer thicknesses, that ranged between 550-950 nm. Increased heat during deposition was examined and shown to increase the film quality and performance for all thicknesses. Two different ways of doping CIGS with Na was examined and it was found that higher Na content lead to an increasing predominance of the (112) plane. The bandgap was graded by varying the GGI composition throughout the CIGS layer and depth profiles were made with Glow-Discharge Optical Emission Spectroscopy (GDOES). It was found that a sputtered CuGaSe2 (CGS)layer below the CIGS-layer lead to a steep increase of the GGI near the back contact. When CGS made up 10% of the total CIGS layer thickness, a significant increase in performance was observed for all thicknesses. CIGS-absorbers with a less graded region with low GGI, making up 30% or 60% of the total CIGS layer thickness were made. A decrease in GGI in that region, was shown to increase the current but lower the voltage. No substantial increase in total performance compared to a fully graded CIGS layer was seen regardless of layer thickness. For further work the optical losses needs to be addressed and work on increasing the optical path in the CIGS layer needs to be done.

Down-conversion (DC) and down-shifting (DS) layers are optical layers mounted on the top surface of a solar cell that can potentially increase the solar cell efficiency. The effect of DC and DS layers to enhance the performance of single-junction solar cells has been studied by means of simulation and experimental work. In this thesis a model is developed to study the effects of DC and DS layers by modifying the incident spectrum. The effect of the layers on ideal cells as well as commercial grade silicon and CIGS solar cells that are modeled in a device simulator is examined. Silicon nanocrystals (Si-nC) embedded in a silicon dioxide matrix to act as a DS layer were fabricated and characterized at McMaster University as part of this project. The measured optical properties as well as the photoluminescence measurements are used as input parameters to the optical model. The enhancement due to the Si-nC when coupled to silicon and CIGS solar cells is explored. Beside the DC and DS effects, there is also disturbance to the surface reflections due to the addition of a new layer to the top surface and is referred to as antireflection coating (ARC) effect. For the simulated silicon solar cell under the standard AM1.5G spectrum (1000W/m2), a maximum increase in Jsc of 8.4% is achieved for a perfect DS layer as compared to a reference cell, where 7.2% is due to ARC effect and only 1.2% is due to DS effect. On the other hand, there is an increase in Jsc of 19.5% for the CIGS solar cell when coupled to a perfect DS layer. The DS effect is dominant with 18%, while the ARC effect contributes only 1.5% to the total Jsc enhancement. Accurately characterizing DS layers coupled to solar cell requires knowledge of optical properties of the complete structure. Internal quantum efficiency is an important tool for characterizing DS systems, nevertheless, it is rarely reported. In addition, the ARC effect is not experimentally decoupled from the DS effect. In this work, a straightforward method for calculating the active layer contribution that minimizes error by subtracting optically-modeled electrode absorption from experimentally measured total absorption.