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 −COPh
F
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.