First-principles studies of oxygen interstitial dopants in RbPbI$_3$ halide for perovskite solar cells

TL;DR

This study uses first-principles calculations to explore how interstitial oxygen atoms and molecules affect the structural, electronic, and optical properties of RbPbI3 perovskites, revealing potential for band-gap tuning and stability improvements.

Contribution

First to analyze the impact of interstitial oxygen dopants on RbPbI3 perovskites, providing insights into band-gap reduction and exotic metallic states relevant for solar cell optimization.

Findings

Oxygen doping significantly reduces the band gap from ~2.6 eV to ~1.0 eV.

Interstitial oxygen molecules can induce a metallic state in RbPbI3.

Oxygen incorporation can enhance efficiency, stability, and enable band-gap engineering.

Abstract

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.