Vapor deposition methods for depositing transition metal dichalcogenide (TMDC) films, such as rhenium sulfide thin films, are provided. In some embodiments TMDC thin films are deposited using a deposition cycle in which a substrate in a reaction space is alternately and sequentially contacted with a vapor phase transition metal precursor, such as a transition metal halide, a reactant comprising a reducing agent, such as NH3 and a chalcogenide precursor. In some embodiments rhenium sulfide thin films are deposited using a vapor phase rhenium halide precursor, a reducing agent and a sulfur precursor. The deposited TMDC films can be etched by chemical vapor etching using an oxidant such as O2 as the etching reactant and an inert gas such as N2 to remove excess etching reactant. The TMDC thin films may find use, for example, as 2D materials.