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pp.661-668
Cu(In,Ga)Se2(CIGS) photovoltaic thin films were electrodeposited on Mo/glass substrates with an aqueous solution containing 2 mM CuCl2, 8 mM InCl3, 20 mM GaCl3 and 8mM H2SeO3 at the electrodeposition potential of -0.6 to -1.0 V(SCE) and pH of 1.8. The best chemical composition of Cu1.05In0.8Ga0.13Se2 was found to be achieved at -0.7 V(SCE). The precursor Cu-In-Ga-Se films were annealed for crystallization to chalcopyrite structure at temperatures of 100-500˚C under Ar gas atmosphere. The chemical compositions, microstructures, surface morphologies, and crystallographic structures of the annealed films were analyzed by EPMA, FE-SEM, AFM, and XRD, respectively. The precursor Cu-In-Ga-Se grains were grown sparsely on the Mo-back contact and also had very rough surfaces. However, after annealing treatment beginning at 200˚C, the empty spaces between grains were removed and the grains showed well developed columnar shapes with smooth surfaces. The precursor Cu-In-Ga-Se films were also annealed at the temperature of 500˚C for 60 min under Se gas atmosphere to suppress the Se volatilization. The Se amount on the CIGS film after selenization annealing increased above the Se amount of the electrodeposited state and the MoSe2 phase occurred, resulting from the diffusion of Se through the CIGS film and interaction with Mo back electrode. However, the selenization-annealed films showed higher crystallinity values than did the films annealed under Ar atmosphere with a chemical composition closer to that of the electrodeposited state.
