CuxZnyS has p-type conductivity for a wide range of Cu content and a wide band gap (>3eV) with Zn-rich composition. In this work, CuxZnyS films were deposited by the photochemical deposition, where the film was deposited on the substrate immersed in the solution owing to reactions activated by UV light. The deposition solution contained 5 mM CuSO4, 25 mM ZnSO4 and 4130 mM Na2S2O3. The deposited film showed transmission larger than 70% in the visible range, and its band gap was about 3.7 eV. pn heterostructures were fabricated by depositing ZnO on the CuxZnyS film by the pulse-biased electrochemical deposition from a solution containing 100 mM Zn(NO3)(2). When the ZnO film thickness was larger than 1 urn, the heterostructures showed rectification properties and weak photovoltaic effects. (C) 2015 Elsevier Ltd. All rights reserved.