| Description |
Cu(In,Ga)Se2 (CIGSe), CuZnSn(S,Se)4 (CZTSSe), etc., are the potential chalcogenide semiconductors being investigated for next-generation thin film photovoltaics (TFPV). While the champion cell efficiency of CIGSe has exceeded 20%, CZTSSe has crossed the 10% mark. This work investigates the effect of laser annealing on CISe films, and compares the electrical characteristics of CIGSe (chalcopyrite) and CZTSe (kesterite) solar cells. Chapter 1 through 3 provide a background on semiconductors and TFPV, properties of chalcopyrite and kesterite materials, and their characterization using deep level transient spectroscopy (DLTS) and thermal admittance spectroscopy (TAS). Chapter 4 investigates electrochemical deposition (nonvacuum synthesis) of CISe followed by continuous wave laser annealing (CWLA) using a 1064 nm laser. It is found that CWLA at ~ 50 W/cm2 results in structural changes without melting and dewetting of the films. While Cu-poor samples show about 40% reduction in the full width at half maximum of the respective x-ray diffraction peaks, identically treated Cu-rich samples register more than 80% reduction. This study demonstrates that an entirely solid-phase laser annealing path exists for chalcopyrite phase formation and crystallization. Chapter 5 investigates the changes in defect populations after pulse laser annealing in submelting regime of electrochemically deposited and furnace annealed CISe films. DLTS on Schottky diodes reveal that the ionization energy of the dominant majority carrier defect state changes nonmonotonically from 215±10 meV for the reference sample, to 330±10 meV for samples irradiated at 20 and 30 mJ/cm2, and then back to 215±10 meV for samples irradiated at 40 mJ/cm2. A hypothesis involving competing processes of diffusion of Cu and laser-induced generation of In vacancies may explain this behavior. Chapter 6 compares the electrical characteristics of chalcopyrite and kesterite materials. Experiments reveal CZTSe cell has an order of magnitude higher net carrier concentration and saturation current density, whereas five times smaller shunt resistance and depletion width at equilibrium compared to CIGSe. The TAS measurements suggest that the dielectric freezeout occurs at relatively higher temperatures (~ 150 K) and lower frequencies (< 1 MHz) for CZTSe cell. Both sample types show a broad DLTS signal, possibly indicating a parallel recombination process with carrier emissions. |
