Materials based on Cu₂O are potential p-type transparent semiconducting oxides. Developing an understanding of the mechanism leading to p-type behaviour is important. An accepted origin is the formation of Cu vacancies. However, the way in which this mechanism leads to p-type properties needs to be investigated. This paper presents a first principles analysis of the origin of p-type semiconducting behaviour in Cu₂O with 1.5 and 3% Cu vacancy concentrations. Plane wave density functional theory (DFT) with the Perdew–Burke–Ernzerhof (PBE) exchange–correlation functional is applied. In order to investigate the applicability of DFT, we firstly show that CuO, with 50% Cu vacancies cannot be described with DFT and in order to obtain a consistent description of CuO, the DFT+U approach is applied. The resulting electronic structure is consistent with experiment, with a spin moment of 0.64 μ_B and an indirect band gap of 1.48 eV for U = 7 eV. However, for a 3% Cu vacancy concentration in Cu₂O, the DFT and DFT+U descriptions of Cu vacancies are similar, indicating that DFT is suitable for a small concentration of Cu vacancies; the formation energy of a Cu vacancy is no larger than 1.7 eV. Formation of Cu vacancies produces delocalised hole states with hole effective masses consistent with the semiconducting nature of Cu₂O. These results demonstrate that the p-type semiconducting properties observed for Cu₂O are explained by a small concentration of Cu vacancies.

Surface contamination by microbes is a major public health concern. A damp environment is one of potential sources for microbe proliferation. Smart photocatalytic coatings on building surfaces using semiconductors like titania (TiO₂) can effectively curb this growing threat. Metal-doped titania in anatase phase has been proven as a promising candidate for energy and environmental applications. In this present work, the antimicrobial efficacy of copper (Cu)-doped TiO₂ (Cu-TiO₂) was evaluated against Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive) under visible light irradiation. Doping of a minute fraction of Cu (0.5 mol %) in TiO₂ was carried out via sol-gel technique. Cu-TiO₂ further calcined at various temperatures (in the range of 500–700 °C) to evaluate the thermal stability of TiO₂ anatase phase. The physico-chemical properties of the samples were characterized through X-ray diffraction (XRD), Raman spectroscopy, X-ray photo-electron spectroscopy (XPS) and UV–visible spectroscopy techniques. XRD results revealed that the anatase phase of TiO₂ was maintained well, up to 650 °C, by the Cu dopant. UV–vis results suggested that the visible light absorption property of Cu-TiO₂ was enhanced and the band gap is reduced to 2.8 eV. Density functional theory (DFT) studies emphasize the introduction of Cu⁺ and Cu²⁺ ions by replacing Ti⁴⁺ ions in the TiO₂ lattice, creating oxygen vacancies. These further promoted the photocatalytic efficiency. A significantly high bacterial inactivation (99.9999%) was attained in 30 min of visible light irradiation by Cu-TiO₂.