In some aspects, methods of forming a metal chalcogenide thin film are provided. According to some methods, a metal chalcogenide thin film is deposited on a substrate in a reaction space in a cyclical deposition process where at least one cycle includes alternately and sequentially contacting the substrate with a first vapor-phase metal reactant and a second vapor-phase chalcogen reactant. In some aspects, methods of forming three-dimensional structure on a substrate surface are provided. In some embodiments, the method includes forming a metal chalcogenide dielectric layer between a substrate and a conductive layer. In some embodiments the method includes forming an MIS-type contact structure including a metal chalcogenide dielectric layer.