Improving optical and morphological properties of Mn-doped ZnO via Ar ion sputtering followed by high-temperature UHV annealing

Using the ultrasonic spray pyrolysis technique, pure (ZnO) and manganese (4at%)-doped zinc oxide (ZnMnO) thin films were synthesized and treated with Ar+ sputtering in the UHV (ultra-high vacuum) system. In this regard, XRD (X-ray diffraction), XPS (X-ray photoelectron spectroscopy), PL (photoluminescence), and AFM (atomic force microscopy) techniques were applied to investigate the electronic and photonic properties of ZnO. XRD and XPS allowed us to identify the successful incorporation of Mn as a substitute for Zn, while PL and AFM images reveal a high tendency for crystalline grains on the ZnMnO surface to aggregate to form small grains. However, bandgap narrowing, a redshift with considerable fluctuations in excitonic emission, and a perfect quenching of visible emission (400–640 nm) were observed. Investigations into defect-related emission in ZnMnO and ZnO compounds were conducted. The PL spectra of the prepared samples were measured and analyzed using Gaussian fitting. The PL of undoped ZnO exhibited an intense broad band with a peak at 550 nm. Two effects were shown to occur as a result of Mn doping: (i) a sharp quenching of self-activated PL with a progressive red-shift of the quenching’s spectral boundary; (ii) the appearance of a new emission band with a peak at 1.64 eV (756 nm), which dominates the PL spectrum and is noted in a band diagram; as well as a slight shift in the main line of ZnO, which is located at energy 3.275 eV (378.57nm).