Cadmium Telluride (CdTe) is a leading thin film photovoltaic (PV) material due to its near ideal bandgap of 1.45 eV and its high optical absorption coefficient. Advancements in efficiencies of CdTe/CdS solar cells over the past few decades have come from improving the short circuit current (JSC) and Fill Factor (FF) but the Open Circuit Voltage (VOC) has been stagnant. Further improvements in efficiencies should come from increased VOC’s. VOC’s can be improved by increasing the acceptor concentration and minority carrier lifetime. Both these parameters can be controlled by manipulating the native defect concentration in CdTe which can be achieved by varying CdTe stoichiometry. In this study, a deposition system called Elemental Vapor Transport was used to vary the CdTe stoichiometry with an intent to change the native defect concentration and therefore pave way to increase acceptor concentration and lifetimes. Elemental cadmium and tellurium were heated in dedicated zones and their vapors were transported to the substrate using a carrier gas. By varying the temperatures and flowrates of the carrier gas through the zones, the gas phase Cd/Te ratio was varied to deposit Cd-rich, Te-rich and stoichiometric films. Structural properties were investigated using Scanning Electron Microscopy (SEM), X-Ray Diffraction (XRD), and Transmission Electron Microscopy (EDS). Electrical characterization of completed devices was carried out by Current-Voltage (J-V), Capacitance-Voltage (C-V), and Spectral Response (SR) and Deep Level Transient Spectroscopy (DLTS) measurements. Cd-rich films showed smaller grain sizes and lesser degree of preferential orientation. Te-rich films showed increased acceptor concentration and carrier lifetimes and solar cells fabricated using these films showed higher VOC’s compared to Cd-rich and stoichiometric films .Higher degree of CdTe-CdS mixing was observed at the interface for films deposited at increased substrate temperatures.

The photovoltaic properties of CdTe-based thin films depend on recombination levels formed in the CdTe layer and at the heterojunction. The localized states are resultant of structural defects (metal sublattice, chalcogen sublattice, interstitial), controlled doping, deposition process, and/or post-deposition annealing. The photoluminescence study of CdTe thin films, from both the bulk and heterojunction, can reveal radiative states due to different defects or impurities. Identification of defects allows for potential explanation of their roles and influence on solar cell performance. A thorough understanding of the material properties responsible for solar cell performance is critical in further advancing the efficiency of devices. The presented work is a systematic investigation using photoluminescence to study CdTe thin films with varying deposition processes. The thin (polycrystalline) films explored in this study were deposited by either the elemental vapor transport technique (EVT) or close spaced sublimation (CSS). Two device architectures were investigated, the typical CdTe/CdS device and the CdSeXTe1-X (CST) alloy device. Post-deposition annealing processes were either laser or thermal. The study of the CdTe thin films is grouped in three general categories: (a) EVT films: Intrinsic and Extrinsic (Group V: Sb and P), (b) CST alloys, and (c) Post-deposition Laser Annealed (LA) films. The main goal of this dissertation is to understand the influence of fabrication procedures (deposition conditions, post deposition thermal and chemical treatments, added impurities, and device architecture) on the defect structure of the CdTe thin films. The behavior of the photoluminescence (PL), studied as a function of the measurement temperature and excitation intensity, provides insight to the mechanism causing the radiative recombination levels. Analysis of the PL spectra for CdTe films with intrinsic doping demonstrated stoichiometric control of native defects for both the Cd- and Te-rich conditions. PL spectra of CdTe:Sb films showed unique Sb-related bands. Also, impurity-related defects were identified in the CdTe:P spectra. Spectral analysis support the need for optimization of dopant concentration. The effects of selenium (Se) thickness and post-deposition processing on the formation of CST alloy were demonstrated in the changing PL spectra. The native defects (and complexes) identified in films with thermal anneal processing were the same as those identified in films with laser anneal post-deposition processing. The PL data were collected and other characterization techniques were used to support the defect assignments. A repository of material properties, which include the recombination levels along with structural defect assignment for each of the CdTe deposition processes, is provided. This project will lend the solar cell community information on CdTe defects for different processing conditions, ultimately influencing the fabrication of improved solar cells.