Silicon photovoltaics is the dominant contribution to the global solar energy production. As increasing conversion efficiency has become one of the most important factors to lower the cost of photovoltaic systems, the idea of making a multijunction solar cell based on a silicon bottom cell has attracted broad interest. Here the potential of using dilute nitride GaNPAs alloys for a lattice-matched 3-terminal 2-junction Si-based tandem solar cell through multiscale modeling is investigated. To calculate the electronic band structure of dilute nitride alloys with relatively low computational cost, the sp^3 d^5 s^* s_N tight-binding model is chosen, as it has been demonstrated to obtain quantitatively correct trends for the lowest conduction band near Γ, L, and X for dilute-N GaNAs. A genetic algorithm is used to optimize the sp^3 d^5 s^* tight-binding model for pure GaP and GaAs for their optical properties. Then the optimized sp^3 d^5 s^* s_N parametrizations are obtained for GaNP and GaNAs by fitting to experimental bandgap values. After that, a virtual crystal approach gives the Hamiltonian for GaNPAs alloys. From their tight-binding Hamiltonian, the first-order optical response functions of dilute nitride GaNAs, GaNP, and GaNPAs are calculated. As the N mole fraction varies, the calculated critical optical features vary with the correct trends, and agree well with experiment. The calculated optical properties are then used as input for the solar device simulations based on Silvaco ATLAS. For device simulation, a bottom cell model is first constructed to generate performance results that agree well with a demonstrated high-efficiency Si heterojunction interdigitated back contact (IBC) solar cell reported by Kaneka. The front a-Si/c-Si interface is then replaced by a GaP/Si interface for the investigation of the sensitivity of the GaP/Si interface to interface defects in terms of degradation of the IBC cell performance, where we find that an electric field that induces strong band bending can significantly mitigate the impact of the interfacial traps. Finally, a lattice-matched 3-terminal 2-junction tandem model is built for performance simulation by stacking a dilute nitride GaNP(As) cell on the Si IBC cell connected through a GaP/Si interface. The two subcells operate quasi-independently. In this 3-terminal tandem model, traps at the GaP/Si interface still significantly impact the performance of the Si subcell, but their effects on the GaNP subcell are relatively small. Assuming the interfacial traps are well passivated, the tandem efficiency surpasses that of a single-junction Si cell, with values close to 33% based on realistic parameters.

Accurate forecasting of electricity prices has been a key factor for bidding strategies in the electricity markets. The increase in renewable generation due to large scale PV and wind deployment in California has led to an increase in day-ahead and real-time price volatility. This has also led to prices going negative due to the supply-demand imbalance caused by excess renewable generation during instances of low demand. This research focuses on applying machine learning models to analyze the impact of renewable generation on the hourly locational marginal prices (LMPs) for California Independent System Operator (CAISO). Historical data involving the load, renewable generation from solar and wind, fuel prices, aggregated generation outages is extracted and collected together in a dataset and used as features to train different machine learning models. Tree- based machine learning models such as Extra Trees, Gradient Boost, Extreme Gradient Boost (XGBoost) as well as models based on neural networks such as Long short term memory networks (LSTMs) are implemented for price forecasting. The focus is to capture the best relation between the features and the target LMP variable and determine the weight of every feature in determining the price.

The impact of renewable generation on LMP forecasting is determined for several different days in 2018. It is seen that the prices are impacted significantly by solar and wind generation and it ranks second in terms of impact after the electric load. The results of this research propose a method to evaluate the impact of several parameters on the day-ahead price forecast and would be useful for the grid operators to evaluate the parameters that could significantly impact the day-ahead price prediction and which parameters with low impact could be ignored to avoid an error in the forecast.

Photovoltaic (PV) energy has shown tremendous improvements in the past few decades showing great promises for future sustainable energy sources. Among all PV energy sources, III-V-based solar cells have demonstrated the highest efficiencies. This dissertation investigates the two different III-V solar cells with low (III-antimonide) and high (III-nitride) bandgaps.

III-antimonide semiconductors, particularly aluminum (indium) gallium antimonide alloys, with relatively low bandgaps, are promising candidates for the absorption of long wavelength photons and thermophotovoltaic applications. GaSb and its alloys can be grown metamorphically on non-native substrates such as GaAs allowing for the understanding of different multijunction solar cell designs. The work in this dissertation presents the molecular beam epitaxy growth, crystal quality, and device performance of AlxGa1−xSb solar cells grown on GaAs substrates. The motivation is on the optimization of the growth of AlxGa1−xSb on GaAs (001) substrates to decrease the threading dislocation density resulting from the significant lattice mismatch between GaSb and GaAs. GaSb, Al0.15Ga0.85Sb, and Al0.5Ga0.5Sb cells grown on GaAs substrates demonstrate open-circuit voltages of 0.16, 0.17, and 0.35 V, respectively. In addition, a detailed study is presented to demonstrate the temperature dependence of (Al)GaSb PV cells.

III-nitride semiconductors are promising candidates for high-efficiency solar cells due to their inherent properties and pre-existing infrastructures that can be used as a leverage to improve future nitride-based solar cells. However, to unleash the full potential of III-nitride alloys for PV and PV-thermal (PVT) applications, significant progress in growth, design, and device fabrication are required. In this dissertation, first, the performance of

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InGaN solar cells designed for high temperature application (such as PVT) are presented showing robust cell performance up to 600 ⁰C with no significant degradation.

In the final section, extremely low-resistance GaN-based tunnel junctions with different structures are demonstrated showing highly efficient tunneling characteristics with negative differential resistance (NDR). To improve the efficiency of optoelectronic devices such as UV emitters the first AlGaN tunnel diode with Zener characteristic is presented. Finally, enabled by GaN tunnel junction, the first tunnel contacted InGaN solar cell with a high VOC value of 2.22 V is demonstrated.

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.

III-V multijunction solar cells have demonstrated record efficiencies with the best device currently at 46 % under concentration. Dilute nitride materials such as GaInNAsSb have been identified as a prime choice for the development of high efficiency, monolithic and lattice-matched multijunction solar cells as they can be lattice-matched to both GaAs and Ge substrates. These types of cells have demonstrated efficiencies of 44% for terrestrial concentrators, and with their upright configuration, they are a direct drop-in product for today’s space and concentrator solar panels. The work presented in this dissertation has focused on the development of relatively novel dilute nitride antimonide (GaNAsSb) materials and solar cells using plasma-assisted molecular beam epitaxy, along with the modeling and characterization of single- and multijunction solar cells.

Nitrogen-free ternary compounds such as GaInAs and GaAsSb were investigated first in order to understand their structural and optical properties prior to introducing nitrogen. The formation of extended defects and the resulting strain relaxation in these lattice-mismatched materials is investigated through extensive structural characterization. Temperature- and power-dependent photoluminescence revealed an inhomogeneous distribution of Sb in GaAsSb films, leading to carrier localization effects at low temperatures. Tuning of the growth parameters was shown to suppress these Sb-induced localized states.

The introduction of nitrogen was then considered and the growth process was optimized to obtain high quality GaNAsSb films lattice-matched to GaAs. Near 1-eV single-junction GaNAsSb solar cells were produced. The best devices used a p-n heterojunction configuration and demonstrated a current density of 20.8 mA/cm2, a fill factor of 64 % and an open-circuit voltage of 0.39 V, corresponding to a bandgap-voltage offset of 0.57 V, comparable with the state-of-the-art for this type of solar cells. Post-growth annealing was found to be essential to improve Voc but was also found to degrade the material quality of the top layers. Alternatives are discussed to improve this process. Unintentional high background doping was identified as the main factor limiting the device performance. The use of Bi-surfactant mediated growth is proposed for the first time for this material system to reduce this background doping and preliminary results are presented.

The state of the solar industry has reached a point where significant advancements in efficiency will require new materials and device concepts. The material class broadly known as the III-N's have a rich history as a commercially successful semiconductor. Since discovery in 2003 these materials have shown promise for the field of photovoltaic solar technologies. However, inherent material issues in crystal growth and the subsequent effects on device performance have hindered their development. This thesis explores new growth techniques for III-N materials in tandem with new device concepts that will either work around the previous hindrances or open pathways to device technologies with higher theoretical limits than much of current photovoltaics. These include a novel crystal growth reactor, efforts in production of better quality material at faster rates, and development of advanced photovoltaic devices: an inversion junction solar cell, material work for hot carrier solar cell, ground work for a selective carrier contact, and finally a refractory solar cell for operation at several hundred degrees Celsius.

Multiple quantum well (MQW) structures have been employed in a variety of solid state devices. The InGaAs/GaAs material system is of special interest for many optoelectronic applications. This study examines epitaxial growth and defect creation in InGaAs/GaAs MQWs at its initial stage. Correlations between physical properties, crystal perfection of epitaxial structures, and growth conditions under which desired properties are achieved appear as highly important for the realization and final performance of semiconductor based devices.

Molecular beam epitaxy was utilized to grow InGaAs/GaAs MQW structures with a variation in deposition temperature T_dep among the samples to change crystalline and physical properties. High resolution x-ray diffraction and transmission electron microscopy were utilized to probe crystal properties, whereas photoluminescence spectroscopy evaluated optical response. An optimal growth temperature T_dep=505°C was found for 20% In composition. The density of 60° primary and secondary dislocation loops increased continuously at lower growth temperatures and reduced crystal perfection, as evaluated by lateral and vertical coherence lengths and diffuse scattering in reciprocal space maps. Likewise, the strength of non-radiative Shockley-Read-Hall recombination increased as deposition temperature was reduced. Elevated deposition temperature led to InGaAs decay in the structures and manifested in different crystalline defects with a rather isotropic distribution and no lateral ordering. High available thermal energy increased atomic surface diffusivity and resulted in growth surface instability against perturbations, manifesting in lateral layer thickness undulations. Carriers in structures grown at elevated temperature experience localization in local energy minima.InGaAs/GaAs MQW structures reveal correlation between their crystal quality and optical properties. It can be suggested that there is an optimal growth temperature range for each In composition with high crystal perfection and best physical response.

Increasing the conversion efficiencies of photovoltaic (PV) cells beyond the single junction theoretical limit is the driving force behind much of third generation solar cell research. Over the last half century, the experimental conversion efficiency of both single junction and tandem solar cells has plateaued as manufacturers and researchers have optimized various materials and structures. While existing materials and technologies have remarkably good conversion efficiencies, they are approaching their own limits. For example, tandem solar cells are currently well developed commercially but further improvements through increasing the number of junctions struggle with various issues related to material interfacial defects. Thus, there is a need for novel theoretical and experimental approaches leading to new third generation cell structures. Multiple exciton generation (MEG) and intermediate band (IB) solar cells have been proposed as third generation alternatives and theoretical modeling suggests they can surpass the detailed balance efficiency limits of single junction and tandem solar cells. MEG or IB solar cell has a variety of advantages enabling the use of low bandgap materials. Integrating MEG and IB with other cell types to make novel solar cells (such as MEG with tandem, IB with tandem or MEG with IB) potentially offers improvements by employing multi-physics effects in one device. This hybrid solar cell should improve the properties of conventional solar cells with a reduced number of junction, increased light-generated current and extended material selections. These multi-physics effects in hybrid solar cells can be achieved through the use of nanostructures taking advantage of the carrier confinement while using existing solar cell materials with excellent characteristics. This reduces the additional cost to develop novel materials and structures. In this dissertation, the author develops thermodynamic models for several novel types of solar cells and uses these models to optimize and compare their properties to those of existing PV cells. The results demonstrate multiple advantages from combining MEG and IB technology with existing solar cell structures.

Silicon solar cells with heterojunction carrier collectors based on a-Si/c-Si heterojunction (SHJ) have a potential to overcome the limitations of the conventional diffused junction solar cells and become the next industry standard manufacturing technology of solar cells. A brand feature of SHJ technology is ultrapassivated surfaces with already demonstrated 750 mV open circuit voltages (Voc) and 24.7% efficiency on large area solar cell. Despite very good results achieved in research and development, large volume manufacturing of high efficiency SHJ cells remains a fundamental challenge. The main objectives of this work were to develop a SHJ solar cell fabrication flow using industry compatible tools and processes in a pilot production environment, study the interactions between the used fabrication steps, identify the minimum set of optimization parameters and characterization techniques needed to achieve 20% baseline efficiency, and analyze the losses of power in fabricated SHJ cells by numerical and analytical modeling. This manuscript presents a detailed description of a SHJ solar cell fabrication flow developed at ASU Solar Power Laboratory (SPL) which allows large area solar cells with >750 mV Voc. SHJ cells on 135 um thick 153 cm2 area wafers with 19.5% efficiency were fabricated. Passivation quality of (i)a-Si:H film, bulk conductivity of doped a-Si films, bulk conductivity of ITO, transmission of ITO and the thickness of all films were identified as the minimum set of optimization parameters necessary to set up a baseline high efficiency SHJ fabrication flow. The preparation of randomly textured wafers to minimize the concentration of surface impurities and to avoid epitaxial growth of a-Si films was found to be a key challenge in achieving a repeatable and uniform passivation. This work resolved this issue by using a multi-step cleaning process based on sequential oxidation in nitric/acetic acids, Piranha and RCA-b solutions. The developed process allowed state of the art surface passivation with perfect repeatability and negligible reflectance losses. Two additional studies demonstrated 750 mV local Voc on 50 micron thick SHJ solar cell and < 1 cm/s effective surface recombination velocity on n-type wafers passivated by a-Si/SiO2/SiNx stack.