Nano-structured CuS thin films were deposited on the functionalized -NH2-terminated self-assembled monolayers (SAMs) surface by chemical bath deposition (CBD). The deposition mechanism of CuS on the -NH2-terminated group was systematically investigated using field emission scanning electron microscope (FESEM), X-ray photoelectron spectroscope (XPS), UV-vis absorption. The optical, electrical and photoelectrochemical performance of CuS thin films incorporating with the X-ray diffraction (XRD) analysis confirmed the nanocrystalline nature of CuS with hexagonal crystal structure and also revealed that CuS thin film is a p-type semiconductor with high electrical conductivity (12.3 Omega/square). The functionalized SAMs terminal group plays a key role in the deposition of CuS thin films. The growth of CuS on the varying SAMs surface shows different deposition mechanisms. On -NH2-terminated surfaces, a combination of ion-by-ion growth and cluster-by-cluster deposition can interpret the observed behavior. On -OH- and -CH3-terminated surfaces, the dominant growth mechanism on the surface is cluster-by-cluster deposition in the solution. According to this principle, the patterned CuS microarrays with different feature sizes were successfully deposited on -NH2-terminated SAMs regions of -NH2/-CH3 patterned SAMs surface. (C) 2011 Elsevier Inc. All rights reserved.