How Does Bridging Core Modification Alter the Photovoltaic Characteristics of Triphenylamine‐Based Hole Transport Materials? Theoretical Understanding and Prediction

Abstract Perovskite solar cells have gained immense interest from researchers owing to their good photophysical properties, low‐cost production, and high power conversion efficiencies. Hole transport materials (HTMs) play a dominant role in enhancing the power conversion efficiencies (PCEs) and long diffusion length of holes and electrons in perovskite solar cells. In hole transport materials, modification of π‐linkers has proved to be an efficient approach for enhancing the overall PCE of perovskite solar cells. In this work, π‐linker modification of a recently synthesized H−Bi molecule ( R ) is achieved with novel π‐linkers. After structural modifications, ten novel HTMs ( HB1–HB10 ) with a D−π−D backbone are obtained. The structure–property relationship, and optoelectronic and photovoltaic characteristics of these newly designed hole transport materials are examined comprehensively and compared with reference molecules. In addition, different geometric parameters are also examined with the assistance of density functional theory (DFT) and time‐dependent DFT. All the designed molecules exhibit narrow HOMO–LUMO energy gaps ( E g =2.82–2.99 eV) compared with the R molecule ( E g =3.05 eV). The designed molecules express redshifting in their absorption spectra with low values of excitation energy, which in return offer high power conversion efficiencies. Further, density of states and molecular electrostatic potential analysis is performed to locate the different charge sites in the molecules. The reorganizational energies of holes and electrons are found to have good values, suggesting that these novel designed molecules are efficient hole transport materials for perovskite solar cells. In addition, the low binding energy values of the designed molecules (compared with R ) offer high current charge density. Finally, complex study of HB9:PC 61 BM is also undertaken to understand the charge transfer between the molecules of the complex. The results of all analyses advocate that these novel designed HTMs are promising candidates for the construction of future high‐performance perovskite solar cells.