Somayyeh Alidoust, V. Ongun Özçelik
Hybrid organic-inorganic perovskite heterostructures are emerging platforms for energy conversion and optoelectronic devices, yet the effects of composition and surface terminations on band alignment remain poorly understood. Here, using high-throughput first-principles calculations, we systematically reveal the effect of composition and surface termination on the band alignment of 820 heterostructures formed between poly(3-hexylthiophene) (P3HT) variants and conventional and mixed-cation metal halide perovskites. Band edge analysis predicts concentration dependent band alignments, with most Pb and Sn based perovskites exhibiting Type II and III behavior while mixed-cation CsMASnBr3 uniquely forms Type-I junctions with all P3HT variants. Explicit interface calculations reveal that surface termination can reverse the predicted alignment in conventional tin perovskites, while the mixed cation perovskite preserves Type-I alignment with P3HT regardless of termination. Despite negligible charge transfer, termination dependent band offsets produce markedly different carrier confinement, establishing design principles for engineering P3HT/perovskite interfaces.