Bottom‐Up Templated and Oriented Crystallization for Inverted Triple‐Cation Perovskite Solar Cells with Stabilized Nickel‐Oxide Interface

Abstract Inverted‐structure perovskite solar cells (PSCs) are known for their superior device stability. However, based on nickel‐oxide (NiOx) substrate, disordered crystallization and bottom interface instability of perovskite film are still the main factors that compromise the power conversion efficiency (PCE) of PSCs. Here, 2D perovskite of thiomorpholine 1,1‐dioxide lead iodide (Td2PbI4) is introduced as a template to prepare 3D perovskite thin film with high crystal orientation and large grain size via a bottom‐up growth method. By adding TdCl to the precursor solution, pre‐crystallized 2D Td2PbI4 seeds can accumulate at the bottom interface, lowering the barrier of nucleation, and templating the growth of 3D perovskite films with improved (100) orientation and reduced defects during crystallization. In addition, 2D Td2PbI4 at the bottom interface also hinders the interfacial redox reaction and reduces the hole extraction barrier on the buried interface. Based on this, the Td‐0.5 PSC achieves a PCE of 22.09% and an open‐circuit voltage of 1.16 V. Moreover, Td‐0.5 PSCs show extremely high stability, which retains 84% of its initial PCE after 500 h of continuous illumination under maximum power point operating conditions in N2 atmosphere. This work paves the way for performance improvement of inverted PSCs on NiOx substrate.