Tetrabenzoporphyrin (BP) is a p-type organic semiconductor characterized by the large, rigid π-framework, excellent stability, and good photoabsorption capability. These characteristics make BP and its derivatives prominent active-layer components in organic electronic and optoelectronic devices. However, the control of the solid-state arrangement of BP frameworks, especially in solution-processed thin films, has not been intensively explored, and charge-carrier mobilities observed in BP-based materials have stayed relatively low as compared to those in the best organic molecular semiconductors. This work concentrates on engineering the solid-state packing of a BP derivative, 5,15-bis(triisopropylsilyl)ethynyltetrabenzoporphyrin (TIPS-BP), toward achieving efficient charge-carrier transport in its solution-processed thin films. The effort leads to the selective formation of a brickwork packing that has two dimensionally extended π-staking. The maximum field-effect hole mobility in the resulting films reaches 1.1 cm2 V-1 s-1, which is approximately 14 times higher than the record value for pristine free-base BP (0.070 cm2 V-1 s-1). This achievement is enabled mainly through the optimization of three factors; namely, deposition process, cast solvent, and self-assembled monolayer that constitutes the dielectric surface. On the other hand, polarized-light microscopy and grazing-incident wide-angle X-ray diffraction analyses show that there remains some room for improvement in the in-plane homogeneity of molecular alignment, suggesting even higher charge-carrier mobilities can be obtained upon further optimization. These results will provide a useful basis for the polymorph engineering and morphology optimization in solution-processed organic molecular semiconductors.
Keywords: brickwork packing; dip coating; organic thin-film transistors; polymorphism; self-assembled monolayers (SAMs); tetrabenzoporphyrin (BP).