Graduation Semester and Year




Document Type


Degree Name

Doctor of Philosophy in Materials Science and Engineering


Materials Science and Engineering

First Advisor

Michael Jin


This dissertation is composed of three studies related to chalcopyrite solar cells. The first study is on electronic activities of grain boundaries (GBs) in CuInSe2 (CIS). Despite being polycrystalline, chalcopyrite thin film solar cells have reached record power conversion efficiencies. This is against the classical understanding on the effect of GBs in semiconductor materials. Because GBs are expected to be recombination centers and barriers against the carrier flow, reducing the device efficiency. Therefore, a complete understanding on the electronic behavior of chalcopyrite GBs is missing. Moreover, the high efficiency chalcopyrite solar cells are grown with Na impurities which positively affect the performance of the solar cell, so-called sodium effect. Research on chalcopyrite GBs has been coupled with the effect of Na impurities, because Na has been found segregated at the GBs. The study presented in this dissertation was performed on GBs in a Na-free CIS. It is important to study the GBs in a Na-free chalcopyrite to avoid any uncontrolled effects of Na segregation at the GBs, for instance a possible Na-related secondary phase formation which would affect the conclusions drawn on the natural behavior of chalcopyrite GBs. In addition, it is known that Sigma3 GBs in chalcopyrite solar cells are abundant; therefore, it is meaningful to investigate the differences between Sigma3 and non-Sigma3 GBs. For this purpose, Sigma3, close to Sigma3 and Sigma9 GBs in a Bridgman-grown multicrystalline Na-free CIS wafer were identified by electron backscatter diffraction and their electronic properties were investigated by Kelvin probe force microscope and cathodoluminescence in scanning electron microscope. It is shown that the Sigma3 GB is neutral and it does not behave as a recombination center, whereas once the geometry of a GB deviates from the Sigma3 geometry, such as close to Sigma3 and Sigma9 GBs, the GB becomes charged and behaves as a recombination center. This result was concluded to be due to the increase in the amount of defects at the GB that introduce midgap states as the Sigma value increases. Our results indicate that the surprising high performance seen in the polycrystalline chalcopyrite solar cells is possibly due to the abundance of electrically inactive Sigma3 GBs in this material. To investigate the effect of Na on CIS GBs, projected work includes the characterization of Sigma3 and non-Sigma3 GBs in CIS wafers grown with increasing Na concentration. Consequently, it will be possible to answer the following questions on the impact of sodium-effect on GBs: Is there a certain Na concentration for Na to affect the GB electrical properties and how does it affect both Sigma3 and non-Sigma3 GBs? In the second study, the use of selenoamide instead of direct use of H2Se for atmospheric pressure selenization reaction is proposed and its feasibility is shown by fabricating CIS solar cells with up to 1.6% power conversion efficiency. In addition, observed In and Ga segregation towards the bottom of the CIS and CIGS thin films, respectively, are investigated through phase transformations occurring during the selenization and systematically designed annealing processes. The third study is on the effect of flow type on the growth kinetics of CdS thin films deposited by chemical bath deposition. CdS thin films are deposited on glass substrates under turbulent and laminar flow conditions only by changing the substrate's alignment with respect to the bottom of the beaker in unstirred bath. It is shown that the flow condition of the bath does not change the optical and structural properties of CdS; however, deposition under laminar flow is explained to be diffusion-limited, whereas it is feed-limited under turbulent flow.


Engineering | Materials Science and Engineering


Degree granted by The University of Texas at Arlington