Dopant‐Free Hole Transport Material Based on Non‐Covalent Interaction for Efficient Perovskite Solar Cells

Abstract Hole transport materials (HTMs) have a critical impact on the performance of perovskite solar cells (PSCs). Especially, the dopant‐free HTMs could avoid the usage of hygroscopic dopants and reduce costs, which are important for device stability. Most of the current organic dopant‐free HTMs are polycyclic aromatic hydrocarbons‐based planar conjugated structures. Yet, the synthesis of conjugated fused heterocycles is often complicated. In this work, intramolecular non‐covalent interaction is introduced to construct two organic HTMs (DCT and DTC), which can be facilely obtained through simple reactions. Compared to DTC with hexyl chain on the central benzene ring, DCT with hexyloxy chains shows better planarity in the core structure, as a result of the intramolecular non‐covalent interactions between oxygen on hexyloxy and sulfur atom on the adjacent thiophene, as reflected from its single crystal structure. Moreover, DCT in a pristine state shows a decent hole mobility comparable to the doped Spiro‐OMeTAD. Ultimately, conventional devices using dopant‐free DCT as HTM show a high efficiency of 22.50%, with excellent long‐term stability, and light and thermal stability. The results show that the noncovalent interaction is a useful and simple design strategy for dopant‐free HTMs, that can effectively improve the efficiency and stability of PSCs.