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Among contemporary semiconductors, many of the best performing materials are based on [1]benzothieno[3,2- b][1]benzothiophene (BTBT). Alkylated derivatives of these small molecules not only provide high hole mobilities but also can be easily processed by thermal vacuum or solution deposition methods. Over the last decade, numerous publications have investigated molecular structures and charge transport properties to elucidate what makes these molecules so special. However, the race toward ever higher mobilities resulted in significantly deviating values, which exacerbates linking molecular structure to electronic properties. Moreover, a recently arisen debate on overestimation of organic field-effect transistor mobilities calls for a revaluation of these numbers. We synthesized and characterized four BTBT derivatives with either one or two alkyl chains (themselves consisting of either 8 or 10 carbon atoms) and investigated their spectroscopic, structural, and electrical properties. By employing two-probe, gated four-point probe and gated van der Pauw measurements, we compare field-effect mobility values at room and low temperatures and discuss their feasibility and viability. We attribute mobility changes to different angles between molecule planes and core-to-core double-layer stacking of asymmetric BTBT derivatives and show higher mobilities in the presence of more and longer alkyl chains. A so-called "zipper effect" brings BTBT cores in closer proximity promoting stronger intermolecular orbital coupling and hence higher charge transport.

Mobility Evaluation of [1]Benzothieno[3,2-b][1]benzothiophene Derivatives: Limitation and Impact on Charge Transport