Molecular engineering push-pull structural versatility in the triphenylamine-thienodioxine-based hole transporting materials for high-performance organic and perovskite solar cells

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This study proposes a push-pull molecular engineering approach to fabricate versatile hole-transporting materials (HTMs) for photovoltaic cells. Herein, we introduce a D-π-A strategy for fabricating four highly functional small molecules of thienodioxine core-based HTMs (CJ06C1 to CJ06C4), via core functionalization with diversified electron-withdrawing acceptor moieties. The engineered HTMs are evaluated by employing quantum calculations to analyze the structure-property relationships from optoelectronic, electrochemical, and solvability attributes. The findings reveal that acceptor-integrated HTMs unveil excellent band alignment with active perovskite layer with deeper HOMO energy levels (-4.96 eV to 5.02 eV), transparency in the visible portion λmaxabs<521, which entail appropriate photophysical attributes. In comparison to the reference HTM (CJ06), the acceptor-integrated HTMs have exhibited potentially higher hole mobility rate, accredited to smaller hole reorganization energies (0.15 eV to 0.21 eV), greater transfer integral values (0.26 eV to 0.31 eV) and greater hole hopping rates (1.08×1028 S−1 to 3.70×1028 S−1). The electron-excitation investigation exhibited stronger electronic coupling, smaller hole-electron spatial overlapping, and higher charge transference length (19.42 Å to 21.14 Å) in the fabricated HTMs. Thus ensued a significant upsurge in intrinsic charge transference (74.22–99.74 %) and lower exciton binding energies, leading to easy charge dissociation and low recombination chances compared to the parent HTM (CJ06C1). Moreover, the findings from dipole moments (12.56 D to 13.05 D) and solvation-free energy (-91.08 kJ/mol) to −108.1 kJ/mol),imply easier processability and aptness for film formation. Overall, this study ensures the efficiency of thienodioxine core functionalization with acceptor moieties for fabricating state-of-the-art HTMs. The promising attributes of fabricated HTMs pave the way for forthcoming perovskite solar cells.