NOVELTY - The semiconductor film comprises copper, zinc, tin, a first substitutional metal and at least one chalcogen.    USE - As semiconductor film used in a photovoltaic device (claimed) e.g. solar cells.    ADVANTAGE - Compared to conventional techniques for making copper-zinc-tin-sulfur films, the present electrodeposition is more cost-effective and more readily adaptable to large-scale commercial production. The electrodeposition affords control over film composition, structure, morphology, and light-absorbing properties without the problems associated with the use of high temperature synthesis methods. The broad range of bandgaps and different majority charge carrier characteristics of the semiconductor films provides photovoltaic devices exhibiting greater spectral range and more efficient light collection.    DETAILED DESCRIPTION - INDEPENDENT CLAIMS are included for the following:    (1) a photovoltaic device (100) comprising: (a) a substrate (102); (b) a first semiconductor film (104) disposed over the substrate, the first semiconductor film comprising copper, zinc, tin, a first substitutional metal and at least one chalcogen; and (c) at least one additional semiconductor film (106) disposed over the substrate, where the first semiconductor film and the additional semiconductor film comprise different majority charge carriers;    (2) forming a semiconductor film, involving: (a) exposing a substrate to an electrolytic bath, the electrolytic bath comprising a copper-containing species, a zinc-containing species, a tin-containing species and a first substitutional metal-containing species; (b) depositing a metallic film on the substrate by electrodeposition, the metallic film comprising copper, zinc, tin and a first substitutional metal; and (c) exposing the metallic film to a source of at least one chalcogen to form the semiconductor film.    DESCRIPTION OF DRAWING(S) - The figure shows a photovoltaic cell.    Photovoltaic device (100)    Substrate (102)    First semiconductor film (104)    Additional semiconductor film (106)    Window layer (108)