P-type transparent conducting oxides

Transparent conducting oxides constitute a unique class of materials combining properties of electrical conductivity and optical transparency in a single material. They are needed for a wide range of applications including solar cells, flat panel displays, touch screens, light emitting diodes and transparent electronics. Most of the commercially available TCOs are n-type, such as Sn doped In2O3, Al doped ZnO, and F doped SnO2. However, the development of efficient p-type TCOs remains an outstanding challenge. This challenge is thought to be due to the localized nature of the O 2p derived valence band which leads to difficulty in introducing shallow acceptors and large hole effective masses. In 1997 Hosono and co-workers (1997 Nature 389 939) proposed the concept of 'chemical modulation of the valence band' to mitigate this problem using hybridization of O 2p orbitals with close-shell Cu 3d (10) orbitals. This work has sparked tremendous interest in designing p-TCO materials together with deep understanding the underlying materials physics. In this article, we will provide a comprehensive review on traditional and recently emergent p-TCOs, including Cu(+)-based delafossites, layered oxychalcogenides, nd (6) spinel oxides, Cr(3+)-based oxides (3d (3)) and post-transition metal oxides with lone pair state (ns (2)). We will focus our discussions on the basic materials physics of these materials in terms of electronic structures, doping and defect properties for p-type conductivity and optical properties. Device applications based on p-TCOs for transparent p-n junctions will also be briefly discussed.