A method is provided for forming an alkali metal-doped solution-processed metal chalcogenide. A first solution is formed that includes a first material group of metal salts, metal complexes, or combinations thereof, dissolved in a solvent. The first material group may include one or more of the following elements: copper (Cu), indium (In), and gallium (Ga). An alkali metal-containing material is added to the first solution, and the first solution is deposited on a conductive substrate. The alkali metal-containing material may be sodium (Na). An alkali metal-doped first intermediate film results, comprising metal precursors from corresponding members of the first material group. Then, thermally annealing is performed in an environment of selenium (Se), Se and hydrogen (H2), hydrogen selenide (H2Se), sulfur (S), S and H2, hydrogen sulfide (H2S), or combinations thereof. The metal precursors in the alkali metal-doped first intermediate film are transformed, and an alkali metal-doped chalcogenide layer is formed.