Photoluminescence and structural defects of ZnO films deposited by reactive magnetron sputtering with unconventional Ar-O2 gas mixture formation

ZnO is a well-known traditional industrial material which has high potential to become one of the key components for the next generation of future electronics, LED emitters, visible light photocatalysis and others. In its pristine form ZnO has relatively wide band gap of approximately 3.4 eV, but a lot of emerging applications requires some level of electronic structure engineering and structure optimisation. Studies show that ZnO properties strongly depend on the intrinsic defects type and concentrations. Both characteristics usually are depending on the synthesis method. Accordingly, there is great interest to develop new methods which would allow to obtain ZnO with optimised band gap and other properties. In current, study ZnO films were deposited using reactive magnetron sputtering with unconventional Ar-O2 gas mixture supply control: Ar flow was controlled to maintain total gas pressure at 1x10-2 mbar, whereas O2 flow rate was actively adjusted to maintain the selected intensity of optical zinc emission from the working cathode zone. Applying such ZnO formation method it was possible to stabilise reactive magnetron sputtering process over wide range of conditions. Elemental composition analysis by XPS revealed that despite large variations in Zn emission peak intensity within tested experimental conditions all films had nearly identical Zn:O ratios but at the same time their structural and optical properties differed significantly. The colour of the films varied from highly transparent yellowish-greenish, to intense orange, to opaque black. XRD analysis showed that films consisted of single polycrystalline wurtzite phase with varying orientations. PL spectroscopy analysis revealed that films had a lot of various defects including oxygen and zinc vacancies, interstitials and surface defects. Wide variation of ZnO properties obtained by different reactive sputtering conditions demonstrates the potential of the proposed method to control the formation of various intrinsic defects and to tailor their concentration.