Chalcopyrite AgInS2:Sn thin films were prepared by spray pyrolysis technique for a constant ratio of [Ag]/[In] = 1.5 and different SnCl4 concentrations (0.05, 0.1 and 0.2 ml) in the spray solution obtaining x = [SnCl4]/[Ag] + [In] = 0.01, 0.02, 0.04. All films were deposited at substrate temperature of 375 C. The deposited film for which x = 0.02 exhibited p-type conductivity, having band-gap energies of 1.87 and 2.01 eV. Photoluminescence (PL) studies reveal several PL bands located at 1.45, 1.68, 1.70, 1.80 and similar to 1.88 eV at 10 K. Each one of these PL structures are related to different defects, the 1.45 eV emission is related to indium vacancies, 1.80 eV emission to interstitial silver (Ag-in) or Indium in sites of silver (Ag-In) whereas, the other emissions (1.70 and 1.88 eV) are related with a donor-acceptor pair recombination and free to bound transition, respectively, due to sulphur vacancies. Sn in excess modifies the emission bands located at 1.70 and 1.88 eV; we found that Sit reduces sulphur vacancies and PL spectra are dominated by acceptor impurities.(c) 2007 Elsevier B.V. All rights reserved.