In order to obtain optimally adherent films having the highest mid-infrared photoluminescence efficiency, nanostructured Cr2+:ZnSe films were deposited at room temperature on various substrates by magnetron radiofrequency co-sputtering of a SiO2 target covered by a given number of ZnSe and Cr chips, at different Argon pressures and radiofrequency powers. The deposition parameter effect on the compositional, structural, microstructural and optical properties of the films has been investigated using X-ray reflectivity and diffraction, optical transmission spectroscopy, transmission electron microscopy, and photoluminescence studies. The corresponding films are composed by highly textured cubic and hexagonal ZnSe phases and exhibit strong tensile in-plane residual stresses. The evolution of the tensile residual stress and porosity values are consistent with the optical properties of the layers, and in particular the evolutions of both optical gap and refractive index. The room temperature mid-infrared (2-3 mu m) photoluminescence measurements under direct excitation (1850 nm) revealed that chromium has been incorporated in the Cr2+ active state, and the corresponding fluorescence efficiency for an optimized thin film is only two times smaller than the one of a Cr2+ :ZnSe reference bulk single crystal. (C) 2010 Elsevier B.V. All rights reserved.