Hydrogen adsorption on zinc-terminated ZnO(0001) surface at varying coverages and its effects on electronic and optical properties: a DFT+U study

Abstract Spin-polarized density functional theory implementing Hubbard corrections (DFT + U) were utilized to study H adsorption of different coverages on Zn-terminated ZnO(0001) surface. Changes in electronic and optical properties were observed upon H adsorption of varying coverages, namely with 0.25 monolayer (ML), 0.50 ML, 1 ML, and 2 ML coverage. In terms of surface structure, H atoms were found to adsorb on top of Zn forming Zn–H bond lengths ranging from 1.54–1.73 Å for certain coverages. On the other hand, O–H bond length values are 2.41 Å and 2.37 Å for 0.50 ML and 2 ML coverage respectively. Additionally, for 0.50 ML, the most stable configuration is when one H atom adsorbs on top of Zn and the other near the hollow site. At low coverage (0.25 ML and 0.50 ML), H prefers to interact with topmost layer Zn atoms resulting to shifts in the electronic bands relative to the pristine surface’s. In addition, at high coverage (1 ML and 2 ML), shifting of bands are observed and are mainly guided by Zn–H atom interaction for 1 ML and weak H–O atom interaction for 2 ML. The observed decrease in band gap as the coverage was increased from 1 ML to 2 ML is supported by the red shift in the absorption plot. However, for low H coverage adsorption, the optical plots deviate due to emergence of flat bands. Changes in electronic properties such as shifts in conduction band minimum and decrease in measured band gap occur as guided by the interaction of adsorbed H atoms with the surface atoms and are supported with obtained optical plots. These findings present the tunability of Zn-terminated ZnO(0001) polar surface properties depending on H coverage.