First-principles studies of oxygen interstitial dopants in RbPbI₃ halide for perovskite solar cells

Recent research on perovskite solar cells has caught much attention for the application in renewable energy materials. However, the effect of external dopants on the performance of perovskite solar cell is yet to be understood properly. Oxygen atom or molecule is important dopant to influence the stability of structural, electronic and optical properties as well as the performance of perovskite solar cells. RbPbX3-type perovskites have fantastic chemical stability and good power conversion efficiency. Here for the first time, we have studied the effect of interstitial oxygen atom (O1) and molecule (O2) on the structural properties, and hence the electronic structure of RbPbI3 from first principles. A significant reduction of the band gap from ~2.6 eV to ~ 1.0 eV, which is close to the optimal band gap, has been predicted when incorporating oxygen. This could in turn be applied to improve the optical properties for harvesting light if we can control the oxygen level appropriately. In addition, an exotic metallic state has been found in our calculations for interstitial oxygen molecule when there are strong O-O, O-Pb, and O-I bonds, indicating the complex nature of oxygen-doped perovskite solar cells. The comparison between oxygen atom and molecules is consistent with the previous report about oxygen-molecule passivation of perovskite solar cells. This indicated oxygen incorporation can not only improve efficiency and stability but also facilitate the optimal band-gap engineering. Our work has therefore provided an important and timely theoretical insight to the effect of oxygen dopants in perovskite solar cells. Moreover, these results also provide theoretical foundation for further simulations such as molecular dynamics.