NOVELTY - Making (I) a photovoltaic layer on a substrate, comprises: providing a substrate coated with an electrical contact layer; depositing a first layer of an ink onto the contact layer of the substrate, where the ink contains at least one metal compound; heating the first layer; depositing a second layer onto the first layer, the second layer comprises at least one copper chalcogenide or copper indium gallium selenide and/or sulfur (CIGS) material; and heating the layers, where the depositing of the copper chalcogenide or CIGS material is done by e.g. chemical vapor deposition.    USE - The process is useful: for making a photovoltaic layer; and to prepare semiconductor and optoelectronic materials, devices including thin film and band gap materials, devices and systems for energy conversion including solar cells.    ADVANTAGE - The process: provides stable semiconductors; allows control of the stoichiometry of the atoms in the semiconductors, particularly metal atoms; provides chemically and physically uniform semiconductor layers; can be operated at relatively low temperatures; and provides enhanced processability for solar cell production and has ability to be processed on a variety of substrates including polymers at relatively low temperatures.    DETAILED DESCRIPTION - Making (I) a photovoltaic layer on a substrate, comprises: providing a substrate coated with an electrical contact layer; depositing a first layer of an ink onto the contact layer of the substrate, where the ink contains at least one metal compound of formula (M1B(ER)3); heating the first layer; depositing a second layer onto the first layer, where the second layer comprises at least one copper chalcogenide or copper indium gallium selenide (CIGS) material; and heating the layers, where the depositing of the copper chalcogenide or CIGS material is done by chemical vapor deposition, metal-organic chemical vapor deposition, plasma enhanced chemical vapor deposition, atomic layer deposition, plasma-enhanced atomic layer deposition, sputtering, radio frequency sputtering, DC sputtering, magnetron sputtering, evaporation, electron beam evaporation and/or laser ablation.    M1B = In, Ga or Al;    E = S or Se; and    R = alkyl, (hetero)aryl, alkenyl, amido, silyl or inorganic and organic groups.    An INDEPENDENT CLAIM is also included for making (II) a photovoltaic layer on a substrate, comprising providing a substrate coated with an electrical contact layer, depositing a first layer of an ink onto the contact layer of the substrate, where the ink contains at least one polymeric precursor compounds, heating the first layer, depositing a second layer onto the first layer, where the second layer comprises at least one group 13 chalcogenide or CIGS material and heating the layers, where the depositing of the chalcogenide or CIGS material is done by chemical vapor deposition, metal-organic chemical vapor deposition, plasma enhanced chemical vapor deposition, atomic layer deposition, plasma-enhanced atomic layer deposition, sputtering, radio frequency sputtering, DC sputtering, magnetron sputtering, evaporation, co-evaporation, electron beam evaporation and/or laser ablation.