CIGS2, solar cells, open circuit voltage, photoelectrochemical, PEC, hydrogen


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.


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Graduation Date





Dhere, Neelkanth


Doctor of Philosophy (Ph.D.)


College of Engineering and Computer Science


Mechanical, Materials and Aerospace Engineering

Degree Program

Materials Science and Engineering








Release Date

January 2006

Length of Campus-only Access


Access Status

Doctoral Dissertation (Open Access)