# Elucidating the role of Sn-substitution and Pb-$\Box$ in regulating stability and carrier concentration in CH$_3$NH$_3$Pb$_{1-X-Y}$Sn$_X$$\Box_Y$I$_3$

## TL;DR

This study uses density functional theory to explore how Sn substitution and Pb vacancies influence the stability and charge properties of a mixed lead-tin iodide perovskite, revealing how composition affects its electronic type and stability.

## Contribution

It provides a detailed computational analysis of the effects of Sn substitution and Pb vacancies on perovskite stability and carrier type, validated against experimental data.

## Key findings

- Pb-vacancies become unfavorable above 250K due to bond linearity loss.
- Sn substitution favors n-type conduction, while Pb-vacancies favor p-type in different host conditions.
- Increasing Sn concentration shifts the material from n-type to p-type.

## Abstract

We address the role of Sn-substitution and Pb-vacancy (Pb-$\Box$) in regulating stability and carrier concentration of CH$_3$NH$_3$Pb$_{1-X-Y}$Sn$_X$$\Box_Y$I$_3$ perovskite using density functional theory, where the performance of the exchange-correlation functional is carefully analyzed, and validated w.r.t. available experimental results. We find the most stable configuration does not prefer any Pb at 50\% concentration of Sn. However, the Pb-$\Box$s become unfavourable above 250K due to the reduced linearity of Sn-I bonds. For n-type host the Sn substitution is more preferable than Pb-$\Box$ formation, while for p-type host the trend is exactly opposite. The charge states of both Sn and Pb-$\Box$ are found to be dependent on the Sn concentration, which in turn alters the perovskite from n-type to p-type with increasing $X$ ($>$0.5).