The present invention provides methods to sputter deposit films comprising alkali metal compounds. At least one target comprising one or more alkali metal compounds and at least one metallic component is sputtered to form one or more corresponding sputtered films. The at least one target has an atomic ratio of the alkali metal compound to the at least one metallic component in the range from 15:85 to 85:15. The sputtered film(s) incorporating such alkali metal compounds are incorporated into a precursor structure also comprising one or more chalcogenide precursor films. The precursor structure is heated in the presence of at least one chalcogen to form a chalcogenide semiconductor. The resultant chalcogenide semiconductor comprises up to 2 atomic percent of alkali metal content, wherein at least a major portion of the alkali metal content of the resultant chalcogenide semiconductor is derived from the sputtered film(s) incorporating the alkali metal compound(s). The chalcogenide semiconductors are useful in microelectronic devices, including solar cells.

A photoelectric conversion element of an embodiment includes a first electrode, a second electrode, a light-absorbing layer having a compound containing group I-III-VI elements between the first electrode and the second electrode, and an n-type layer between the light-absorbing layer and the second electrode. A group IV element is contained in the light-absorbing layer closer to the n-type layer. A maximum peak of the concentration of group IV element exists in a region down to a depth of 0.2 m from a main surface of the light-absorbing layer facing to the n-type layer toward the first electrode.

A method (200) and deposition zone apparatus (300) for fabricating thin-film optoelectronic devices (100), the method comprising: providing a potassium-nondiffusing substrate (110), forming a back-contact layer (120); forming at least one absorber layer (130) made of an ABC chalcogenide material, adding at least two different alkali metals, and forming at least one front-contact layer (150) wherein one of said at least two different alkali metals is potassium and where, following forming said front-contact layer, in the interval of layers (470) from back-contact layer (120), exclusive, to front-contact layer (150), inclusive, the comprised amounts resulting from adding at least two different alkali metals are, for potassium, in the range of 500 to 10000 ppm and, for the other of said at least two different alkali metals, in the range of 5 to 2000 ppm and at most and at least 1/2000 of the comprised amount of potassium. The method (200) and apparatus (300) are advantageous for more environmentally-friendly production of photovoltaic devices (100) on flexible substrates with high photovoltaic conversion efficiency and faster production rate.