Small-Molecule Hole Transport Materials for >26% Efficient Inverted Perovskite Solar Cells

Chemically modifiable small-molecule hole transport materials (HTMs) hold promise for achieving efficient and scalable perovskite solar cells (PSCs). Compared to emerging self-assembled monolayers, small-molecule HTMs are more reliable in terms of large-area deposition and long-term operational stability. However, current small-molecule HTMs in inverted PSCs lack efficient molecular designs that balance both the charge transport capability and interface compatibility, resulting in a long-standing stagnation of power conversion efficiency (PCE) below 24.5%. Here, we report the comprehensive design of HTMs’ backbone and functional groups, which optimizes a simple planar linear molecular backbone with a high mobility exceeding 7.1 × 10^–4 cm² V^–1 S^–1 and enhances its interface anchoring capability. Owing to the improved surface properties and anchoring effects, the tailored HTMs enhance the interface contact at the HTM/perovskite heterojunction, minimizing nonradiative recombination and transport loss and leading to a high fill factor of 86.1%. Our work has overcome the persistent efficiency bottleneck for small-molecule HTMs, particularly for large-area devices. Consequently, the resultant PSCs exhibit PCEs of 26.1% (25.7% certified) for a 0.068 cm² device and 24.7% (24.4% certified) for a 1.008 cm² device, representing the highest PCE for small-molecule HTMs in inverted PSCs.