Methylammonium-Free Perovskite Photovoltaic Modules.

Chu, Liang; Cao, Jinguo; Wu, Congcong · ACS Nano · 2025

review · Level V

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Abstract

For perovskite photovoltaic industrialization, it is essential to simultaneously achieve high conversion efficiency, long-term stability, and scalable fabrication of modules. Halide perovskites with the ABX<sub>3</sub> structure are composed of A-site monovalent cations, (e.g., formamidinium (FA<sup>+</sup>), methylammonium (MA<sup>+</sup>), and Cs<sup>+</sup>), B-site divalent cations (predominantly Pb<sup>2+</sup>), and X-site halide anions. Though the incorporated MA cations can facilitate the nucleation and growth of perovskite films, their volatility undermines the thermal stability. α-FAPbI<sub>3</sub> exhibits an optimal bandgap, but both it and α-CsPbI<sub>3</sub> are susceptible to converting into the nonphotoactive δ-phase at room temperature. However, their FACsPbI<sub>3</sub> alloy effectively counteracts the imperfections in the tolerance factor, enabling the formation of a room-temperature photoactive phase. Hence, the development of large-area, high-quality, and MA-free perovskite films remains a substantial challenge for efficient photovoltaic modules. This review first discusses the impact of A-site cations on the phase stability of perovskite structures and subsequently examines the film growth mechanism. Then, we summarize the MA-free perovskite photovoltaic modules and highlight advances in the CsPbX<sub>3</sub> (Br<sup>-</sup>/I<sup>-</sup>), FAPbI<sub>3</sub>, and FACsPbX<sub>3</sub> systems. Finally, we propose potential directions and challenges toward perovskite photovoltaic industrialization.