First‐Principles Exploration of Charge Transfer and Optoelectronic Properties in Anthracene‐Based Hole Transporters for Perovskite Solar Cells: Insights Supported by Device‐Level Simulations

ABSTRACT The stability, effectiveness, and versatility of perovskite solar cells (PSCs) can only be improved with advanced solar materials, opening the door for future‐oriented green energy solutions. In this study, eight recently developed anthracene‐based triphenylamine hole transporting layers, HTLs, (PEH‐S1‐PEH‐S8), derived from the PEH‐R core with thiophene and acceptor substitutions, are systematically investigated using DFT and TD‐DFT calculations at B3LYP/6‐31G** level. These HTL materials' optical, electrical, and charge‐transport characteristics are thoroughly evaluated to understand the structure‐property relationship. The PEH‐S7 molecule facilitates the efficient transfer of electronic densities from HOMO to LUMO by elucidating the maximum absorbance at 730 nm, the highest oscillator frequency (f = 1.687), the greatest light harvesting efficacy (LHE = 0.979), and the highest electron affinity (EA = 2.96 eV) in tetrahydrofuran (THF) solvent with the highest open circuit voltage (V oc = 1.38 V). This also showed higher solar efficiency (19.89%) than commercial spiro‐OMeTAD. Comparing PEH‐S1‐PEH‐S8 to the PEH‐R, it is discovered that their electron and hole mobilities are higher. These findings show that the energy levels, reorganization energies, optical and charge‐transport properties of HTL materials can be successfully tuned by strategic peripheral substitution with thiophene and electron‐acceptor groups, thereby guiding the design of future high‐performance PSCs and practical device applications.