Three-Dimensional Anisotropic Carrier Mobility and Structure–Property Relationships for [1]Benzothieno[3,2-b][1]benzothiophene Derivatives: A Theoretical Study Three-Dimensional Anisotropic Carrier Mobility and Structure–Property Relationships for [1]Benzothieno[3,2-b][1]benzothiophene Derivatives: A Theoretical Study AITranslate

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DOI：https://doi.org/10.1021/acsaelm.3c00382

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Through the Marcus electron-transfer theory combined with the random walk technique for the charge-carrier diffusion process, we simulated the three-dimensional (3D) distributions of hole and electron mobilities for [1]benzothieno[3,2-b][1]benzothiophene (BTBT) and its derivatives. Our predicted mobility ranges agree well with the measured field-effect mobility of the BTBT derivatives. We further analyzed the charge-transfer mobility anisotropy of the studied compounds, and the optimum conducting-channel direction relative to the crystal axis was determined, which provides a reliable reference to assist in the performance optimization of field-effect transistors (FETs). Moreover, we analyzed in detail the influences of different substituents on the reorganization energies, ionization energies, electron affinities, frontier molecular orbital charge distributions, and solid-state packing motifs of the BTBT. It was found that the reorganization energies and energy barrier of charge injection effectively decreased with the fusion of the thiophene ring. However, the herringbone packing of BTBT is transformed to π stacking at a local site; as a result, the hole and electron mobilities of BTBT decreased slightly. In comparison, attaching electron-withdrawing −COPhF to BTBT not only increases the electron affinities significantly but also increases the electronic couplings and decreases the reorganization energy related to the electron transfer. It provides a promising way to design n-type or ambipolar organic semiconducting materials.