Doping driven remarkable microstructural evolution of PbS thin films grown by a single-step chemical bath deposition process at 60 degrees C is reported. The undoped films were discontinuous with octahedral-shaped crystallites after 30 min of deposition, whereas Cu doping led to a distinctly different surface microstructure characterized by densely packed elongated crystallites. A mechanism, based on the time sequence study of microstructural evolution of the films, and detailed XRD and Raman measurements, has been proposed to explain the contrasting microstructure of the doped films. The incorporation of Cu forms an interface layer, which is devoid of Pb. The excess Cu ions in this interface layer at the initial stages of film growth strongly interact and selectively stabilize the charged {111} faces containing either Pb or S compared to the uncharged {100} faces that contain both Pb and S. This interaction interferes with the natural growth habit resulting in the observed surface features of the doped films. Concurrently, the Cu-doping potentially changed the optical properties of the films: A significant widening of the bandgap from 1.52 eV to 1.74 eV for increase in Cu concentration from 0 to 20% was observed, making it a highly potential absorber layer in thin film solar cells. (c) 2017 Elsevier B.V. All rights reserved.