The main objective of this research was to develop efficient CuIn1-xGaxS2 (CIGS2)/CdS thin film solar cells for photoelectrochemical (PEC) water splitting to produce very pure hydrogen and oxygen. Efficiencies obtained using CIGS2 have been lower than those achieved using CuInSe2 and CuIn1-xGaxSe2. The basic limitation in the efficiencies is attributed to lower open circuit voltages with respect to the bandgap of the material. Presently, the main mechanism used to increase the open circuit voltage of these copper chalcopyrites (CuInSe2 and CuInS2) is the addition of gallium. However, addition of gallium has its own challenges. This research was intended to (i) elucidate the advantages and disadvantages of gallium addition, (ii) provide an alternative technique to the photovoltaic (PV) community to increase the open circuit voltage which is independent of gallium additions, (iii) develop highly efficient CIGS2/CdS thin film solar cells and (iv) provide an alternative material in the form of CIGS2/CdS thin film solar cells and an advanced technology in the form of a multiple bandgap tandem for PEC water splitting. High gallium content was achieved by the incorporation of a highly excess copper composition. Attempts to achieve high gallium content produced reasonable but not the best solar cell performance. Few solar cells developed on a molybdenum back contact and an ITO/MoS2 transparent conducting back contact showed a PV conversion efficiency of 7.93% and 5.97%, respectively. The solar cells developed on the ITO/MoS2 back contact form the first generation CIGS2/CdS thin film solar cells and 5.97% is the first ever reported efficiency on an ITO/MoS2 transparent back contact. Reasons for the moderate performance of these solar cells were attributed to significant porosity and remnants of unsulfurized CuGa alloy in the bulk of CIGS2. This was the first attempt to a detailed study of materials and device characteristics of CIGS2/CdS thin film solar cells prepared starting with a highly excess copper content CIGS2 layer. Next, excess copper composition of 1.4 (equivalent to gallium content, x = 0.3) was chosen with the aim to achieve the best efficiency. The open circuit voltage was enhanced by depositing an intermediate layer of intrinsic ZnO between CdS and ZnO:Al layers. The systematic study of requirements for such a layer and further optimization of its thickness to achieve a higher open circuit voltage (which is the greatest challenge of the scientific community) forms an important scientific contribution of this research. The PV parameters for CIGS2/CdS thin film solar cell as measured officially at the National Renewable Energy Laboratory were: open circuit voltage of 830.5 mV, short circuit current density of 21.88 mA/cm2, fill factor of 69.13% and photovoltaic conversion efficiency of 11.99% which sets a new world record for CIGS2 cells developed using sulfurization and the open circuit voltage of 830.5 mV has become the "Voc champion value". New PEC setups with the RuS2 and Ru0.99Fe0.01S2 photoanodes were developed. RuS2 and Ru0.99Fe0.01S2 photoanodes were more stable in the electrolyte and showed better I-V characteristics than the RuO2 anode earlier used. Using two CIGS2/CdS thin film solar cells, a PEC efficiency of 8.78% was achieved with a RuS2 anode and a platinum cathode. Results of this research constitute a significant advance towards achieving practical feasibility and industrially viability of the technology of PEC hydrogen generation by water splitting.

Thin film solar cells have the potential to be an important contributor to the world energy demand in the 21st century. Among all the thin film technologies, CuInGaSe2 (CIGS) thin film solar cells have achieved the highest efficiency. However, the high price of photovoltaic (PV) modules has been a major factor impeding their growth for terrestrial applications. Reduction in cost of PV modules can be realized by several ways including choosing scalable processes amenable to large area deposition, reduction in the materials consumption of active layers, and attaining faster deposition rates suitable for in-line processing. Selenization-sulfurization of sputtered metallic Cu-In-Ga precursors is known to be more amenable to large area deposition. Sputter-deposited molybdenum thin film is commonly employed as a back contact layer for CIGS solar cells. However, there are several difficulties in fabricating an optimum back contact layer. It is known that molybdenum thin films deposited at higher sputtering power and lower gas pressure exhibit better electrical conductivity. However, such films exhibit poor adhesion to the soda-lime glass substrate. On the other hand, films deposited at lower discharge power and higher pressure although exhibit excellent adhesion show lower electrical conductivity. Therefore, a multilayer structure is normally used so as to get best from the two deposition regimes. A multi-pass processing is not desirable in high volume production because it prolongs total production time and correspondingly increases the manufacturing cost. In order to make manufacturing compliant with an in-line deposition, it is justifiable having fewer deposition sequences. Thorough analysis of pressure and power relationship of film properties deposited at various parameters has been carried out. It has been shown that it is possible to achieve a molybdenum back contact of desired properties in a single deposition pass by choosing iv the optimum deposition parameters. It is also shown that the film deposited in a single pass is actually a composite structure. CIGS solar cells have successfully been completed on the developed single layer back contact with National Renewable Energy Laboratory (NREL) certified device efficiencies > 11%. The optimization of parameters has been carried out in such a way that the deposition of back contact and metallic precursors can be carried out in identical pressure conditions which is essential for in-line deposition without a need for load-lock. It is know that the presence of sodium plays a very critical role during the growth of CIGS absorber layer and is beneficial for the optimum device performance. The effect of sodium location during the growth of the absorber layer has been studied so as to optimize its quantity and location in order to get devices with improved performance. NREL certified devices with efficiencies > 12% have been successfully completed.

Devices with ZnCdS/ZnS heterojunction partner layer have shown better blue photon response due to higher band gap of these compounds as compared to devices with CdS heterojunction partner layer. CdS heterojunction partner layer has shown high photovoltaic conversion efficiencies with CIGS absorber layer while efficiencies are lower with CuIn1-xGaxS2 (CIGS2). A negative conduction band offset has been observed for CdS/CIGS2 as compared to near flat conduction band alignment in case of CdS/CIGS devices, which results in higher interface dominated recombination. Moreover, it has been predicted that optimum band offsets for higher efficiency solar cells may be achieved for cells with alternative heterojunction partner such as ZnS. With varying ratio of Zn/ (Zn+Cd) in ZnxCd1-xS a range of bandgap energies can be obtained and thus an optimum band offset can be engineered. For reducing interface dominated recombination better lattice match between absorber and heterojunction partners is desirable. Although CdS has better lattice match with CuIn1-xGaxS2 absorber layer, same is not true for CuIn1-xGaxS2 absorber layers. Utilizing ZnxCd1-xS as heterojunction partner provides a range of lattice constant (between aZnS= ~5.4 Ǻ and aCdS= ~5.7 Ǻ) depending on Zn/(Zn+Cd). Therefore better lattice match can be obtained between heterojunction partner and absorber layer. Better lattice match will lead to lower interface dominated recombination, hence higher open circuit voltages. In the present study chemical bath deposition parameters are near optimized for high efficiency CIGS2 Solar cells. Effect of various chemical bath deposition parameters on device performance was studied and attempts were made to optimize the deposition parameters in order to improve the device performance.In/(In+Ga) ratio in absorber layer is varied to obtain good lattice match and optimum band alignment. Solar cells with conversion efficiencies comparable to conventional CdS/CIGS2 has been obtained with ZnxCd1-xS /CIGS2. High short current as well as higher open circuit voltages were obtained with ZnxCd1-xS as alternative heterojunction partner for CIGS2 solar cells as compared to SLG/Mo/CIGS2/ CdS / i-ZnO/ZnO:Al.