In order to prepare n-type CuGaSe2 as-grown, p-type CuGaSe2 single crystals were at first doped by Ge implantation. Thermal healing of the implantation damage in vacuum resulted in strong electrical compensation of the material, but not in n-type conduction. This limitation was overcome by annealing of implanted samples in Zn atmosphere, resulting in n-type conduction of CuGaSe2 with a carrier concentration at room temperature of up to 1016 cm−3. The samples were analyzed by photoluminescence, resistivity, and Hall effect measurements. It was found that the Zn–Ge codoping minimizes the formation of Cu vacancies, which act as acceptor levels and lead to self-compensation, by the formation of ZnCu defects. Furthermore, the number of electrically active Ge dopants is increased by a rise of the GeGa concentration compared to the GeCu defect density. The possibility of n-type conduction in Ga-rich CuIn1−xGaxSe2 compounds opens the possibility of the preparation of homojunction photovoltaic devices and might lead to improved solar cell performance of large band-gap chalcopyrites.

Hall-effect and photoluminescence measurements have been carried out on Sn-doped CuGaSe2 single crystals. The doping was performed either during chemical vapor transport growth with iodine or by a diffusion step at temperatures between 200 and 400 °C. Room temperature resistivity can be varied in the range between 10−2 and 106 Ω cm. Hall-effect data can be explained using a model containing two acceptor levels, one of which is very shallow, and a donor level. Due to doping the concentration of the first acceptor, whose activation energy is 59 meV, is decreased and the donor concentration is increased, but no n-type conductivity was observed. The photoluminescence spectra can be explained by an acceptor level of 50 meV, two donor levels of 80 and 110 meV, respectively, and a deep state of 400 meV. VCu, VSe, VSe complexes, and Sn on cation lattice sites are suggested as origins of these states.

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