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Patent Pending The present invention provides methods for making pnictide compositions, particularly photoactive and/or semiconductive pnictides. In many embodiments, these compositions are in the form of thin films grown on a wide range of suitable substrates to be incorporated into a wide range of microelectronic devices, including photovoltaic devices, photodetectors, light emitting diodes, betavoltaic devices, thermoelectric devices, transistors, other optoelectronic devices, and the like.