The Effects of Bi Alloying in Cu Delafossites: A Density Functional Theory Study

Recently, Cu delafossites, CuMO₂, have received much attention as photo-catalysts for hydrogen production by water splitting due to their unique properties such as stability in most aqueous solutions and p-type conductivity with excellent hole mobility. However, due to their large optical bandgaps, they can absorb sun light only in the ultraviolet region. Hence, it is necessary to tailor their optical properties to enhance their optical absorption in the visible light regions. In this paper, we report on the effects of Bi alloying on the electronic and optical properties of Cu delafossites by density functional theory. We find that Bi alloying can lead to improved optical absorption as compared to the pristine Cu delafossites. We further find that the lone pair Bi-6s electrons create occupied delocalized anti-bonding states on the top of the valence band, leading to further improved hole mobility.