Recent Advances in Crystallographic Optimization for High-Performance Two-Dimensional Perovskite Photovoltaic Devices

Two-dimensional (2D) metal halide perovskites have attracted considerable interest for their markedly improved environmental stability and versatile compositional tunability compared to their three-dimensional (3D) counterparts. Nevertheless, the anisotropic charge transport caused by insulating organic spacers often leads to inefficient charge transport and limiting device performance. Precise control over crystallographic orientation, particularly achieving vertical alignment of the inorganic layers, is essential to facilitate out-of-plane charge transport and enhance device efficiency. This review systematically summarizes recent advances in understanding and controlling the crystallographic orientation of 2D perovskites, emphasizing manipulating strategies such as processing optimization, composition engineering, spacer design, solvent selection, and additive assistance to promote vertical alignment of inorganic layers and improve interlayer charge transport. We also discuss the influence of phase distribution, quantum well width, and crystal growth kinetics on device performance. Finally, we outline prevailing challenges and future opportunities for achieving the ideal microstructure and high-efficiency 2D perovskite solar cells.