Structural Isomeric Effect on Spin Transport in Molecular Semiconductors

Abstract Molecular semiconductor (MSC) is a promising candidate for spintronic applications benefiting from its long spin lifetime caused by light elemental‐composition essence and thus weak spin‐orbit coupling (SOC). According to current knowledge, the SOC effect, normally dominated by the elemental composition, is the main spin‐relaxation causation in MSCs, and thus the molecular structure‐induced SOC change is one of the most concerned issues. In theoretical study, molecular isomerism, a most prototype phenomenon, has long been considered to possess little difference on spin transport previously, since elemental compositions of isomers are totally the same. However, here in this study, quite different spin‐transport performances are demonstrated in ITIC and its structural isomers BDTIC experimentally, for the first time, though the charge transport and molecular stacking of the two films are very similar. By further experiments of electron‐paramagnetic resonance and density‐functional‐theory calculations, it is revealed that noncovalent‐conformational locks (NCLs) formed in BDTIC can lead to enhancement of SOC and thus decrease the spin lifetime. Hence, this study suggests the influences from the structural‐isomeric effect must be considered for developing highly efficient spin‐transport MSCs, which also provides a reliable theoretical basis for solving the great challenge of quantificational measurement of NCLs in films in the future.