Doping and defects: The coloring mechanism of black plasma electrolytic oxidation (PEO) films on aluminum alloys

Plasma electrolytic oxidation (PEO) can be used to fabricate black ceramic films on aluminum alloy by adding transition-metal anions into the electrolyte. Although the coloration was attributed to transition-metal oxides, a thorough explanation of the relationship between oxides and black color was required. In this study, black PEO films were created by incorporating ammonium metavanadate or sodium tungstate into the electrolyte. The research focused on alumina band-gap modification to explain the mechanism of black coloring. The absorption spectrum and X-ray photoelectron spectroscopy (XPS) valence band characterization revealed that the bandgap of alumina after doping was significantly narrowed. The density of state of alumina, including before doping, after doping, and introducing point defect was simulated by first-principles density functional theory calculation. It was discovered that doping transition metals into alumina decrease the conduction band while defects in alumina cause an upper shift of the valence band. The narrowing of the bandgap resulted in the absorption of all visible light and the appearance of black.