Complex Metal Oxides as Emerging Inorganic Hole‐Transporting Materials for Perovskite Solar Cells

Abstract Perovskite solar cells (PSCs) have achieved revolutionary progress during the past decades with a rapidly boosting rate in power conversion efficiencies from 3.8% to 26.1%. However, high‐efficiency PSCs with organic hole‐transporting materials (HTMs) suffer from inferior long‐term stability and high costs. The replacement of organic HTMs with inorganic counterparts such as metal oxides can solve the above‐mentioned problems to realize highly robust and cost‐effective PSCs. Nevertheless, the widely used simple metal oxide‐based HTMs are limited by the low conductivity and poor light transmittance due to the fixed atomic environment. As an emerging family of inorganic HTMs, complex metal oxides with superior structural/compositional flexibility have attracted rapidly increasing interest recently, showing superior carrier conductivity/mobility and superb light transmittance. Herein, the recent advancements in the design and development of complex metal oxide‐based HTMs for high‐performance PSCs are summarized by emphasizing the superiority of complex metal oxides as HTMs over simple metal oxide‐based counterparts. Consequently, several distinct strategies for the design of complex metal oxide‐based HTMs are proposed. Last, the future directions and remaining challenges of inorganic complex metal oxide‐based HTMs for PSCs are also presented. This review aims to provide valuable guidelines for the further advancements of robust, high‐efficiency, and low‐cost PSCs.