Insight into the Photoluminescence and Morphological Characteristics of Transition Metals (TM = Mn, Ni, Co, Cu)-doped ZnO Semiconductor: a Comparative Study

In this work, undoped and transition metal (TM = Mn, Ni, Co, Cu)-doped ZnO thin films were grown on Si substrate using the ultrasonic spray pyrolysis technique, adhering to the same deposition conditions to compare their morphological and photoluminescent characteristics. X-ray Photoelectron Spectroscopy (XPS), Atomic Force Microscopy (AFM), and Photoluminescence (PL) spectroscopy were used to investigate the chemical composition, morphology, and luminescence properties, respectively. XPS results indicate that Mn and Ni ions have bivalent and trivalent electronic states coexisting in the ZnO lattice, Cu ions have both monovalent and bivalent states, and Co ions have only bivalent states. Besides, there is a considerable increase in the level of oxygen vacancies observed upon TM doping. The topographic and phase-contrast AFM images, supported by their associated statistical parameters and mean height distribution histograms, reveal that TM doping increases the tendency for crystalline grains to coalesce in 3D, resulting in a more roughened surface, larger grains with prominent boundaries, increased porosity, and an inhomogeneous height distribution. PL spectra of TM-ZnO show a broadening of the ZnO band gap accompanied by different luminescence behavior compared to pure ZnO regarding both UV and visible emissions. CuZnO is characterized by a green luminescence, CoZnO and MnZnO by a red luminescence, and ZnO and NiZnO by a broad visible luminescence. The possible mechanism for defect luminescence in each TM-ZnO sample was systematically investigated. The chromaticity color coordinates of the PL emissions show that the films provide different color regions well distributed on the CIE chromaticity diagram. The findings regarding the coexistence of two valence states of TM doping, the level of oxygen vacancies, the grain coalescence process, and the luminescence characteristics are carefully correlated and dis-cussed herein.