Fabrication and structural, optical, and electrical characterization of multisource evaporated copper-gallium-selenide polycrystalline thin films.

Theoretical considerations for the use of chalcopyrite ternary I-III-VI₂ compounds in heterojunction photovoltaic conversion devices are presented, followed by an in-depth study of the structural, optical, and electrical characteristics of multi-source evaporated CuGaSe₂ thin films as determined by processing. Film composition was identified as the primary variable for affecting the microstructure and optical-electrical behavior of the films. Film composition was in turn dependent upon elemental flux rates and substrate related effects. Films deposited on glass and bare alumina substrates were richer in selenium than films deposited on molybdenum coated substrates. Cu-poor, near stoichiometeric, and Cu-rich compositions were obtained by varying the Cu/Ga flux ratio. Cu-poor films deposited on bare ceramic substrates were characterized by secondary impurity phase content and a tendency for cubic CuGaSe₂ formation. The cubic nature of optically thin films deposited on glass was substantiated by a lack of crystal field splitting of the valence band as observed by optical absorption measurements. Cubic-tetragonal phase behavior was monitored on optically opaque samples by observation of intensity-independent (112)/(111) x-ray diffraction peak shifts. Cu-poor films on glass were also characterized by surfaces pitting at substrate temperatures in excess of 450°C which may be related to the high surface energy of gallium. Cu-poor films deposited on molybdenum coated alumina substrates exhibited less impurity phase formation and were largely single-phase tetragonal CuGaSe₂. Cu-rich films on all substrates contained CuₓSe impurities and tetragonal CuGaSe₂