Effect of Molecular Substitution and Isomerization on Charge-Transport Parameters in Molecular Organic Semiconductors

Charge transport in an organic semiconductor is strongly dependent on the molecular packing motif, which could be modified by the molecular substitutions and molecular isomerization. We constructed a series of benzodithiophene-based organic semiconductor molecules with different silyethyne substitutions and isomers. The existence of different conformations of these molecules is supported by a low isomerization energy barrier from density functional theory. By using Marcus semiclassical theory calculation, we make a comprehensive assessment for the effect of molecular substitution and isomerization on charge transport. We found that the hole mobility of cis-isomer molecular packing can be enhanced by increasing the length of silylethyne substitutions. We demonstrated that a favorable charge-transport material would possess an identical direction of induced ring currents, stable induced magnetic fields, and dominant π-π stacking interaction in their molecular packing motif to ensure good π-overlap area. Our findings will provide direct guidance for developing organic semiconductor materials.