Remodeling Perovskite Solar Cells: Superior Dopant‐Free Hole Transport Materials for Improved Efficiency and Stability

Perovskite solar cells (PSCs) have several benefits, such as their high repeatability and well‐specified chemical architectures. However, their use is limited since there are not enough hole‐transporting materials (HTMs) with the right energy output, light absorption, and optoelectronic characteristics to make them a viable alternative. By engineering thiophene‐bridged acceptors into benzodithiophene (BDT) donor core with phenoxazine (POZ) side donors, this work logically designs a sequence of HTMs (BDT‐POZ‐Y1 to BDT‐POZ‐Y5) with the aim of filling this gap and exploring their possible uses in PSCs. In order to determine the relationships between structure and properties based on the charge movement, photophysical, and electrical characteristics, simulations using density functional theory (DFT) are conducted. In order to promote open circuit voltage and charge separation as well, the results demonstrate that all the newly crafted HTMs have low‐lying HOMOs, which are in optimal energy level alignment with the benchmark Y6 acceptor. Highly current‐density PSCs benefit from absorption spectra that encompass the UV–visible range. An important consequence of the push–pull process in HTMs is the dominance of intramolecular charge transfer due to modest fluctuations of dipole moments and bandgaps with the acceptor material, guaranteeing strong exciton dissociation and effective photocurrent production. This study provides the groundwork for the development of future high‐performance PSCs by providing molecular‐level knowledge of the design of innovative HTMs and their compatibility with acceptor materials.