Intrinsic Photo‐Crosslinkable Semiconductive Small‐Molecule Crystals (i‐PSSCs) for Patterning Electronic Devices

Precise patterning of small-molecule semiconductive crystals without external chemical additives remains a significant challenge. Herein, intrinsic photo-crosslinkable semiconductive small-molecule crystals (i-PSSCs) are designed and synthesized by associating [1]benzothieno[3,2-b]benzothiophene core with diacetylene-ended groups. The i-PSSCs undergo self-crosslinking directly upon UV light irradiation to yield micron-scale patterned crystalline films through a combination of photo-crosslinking and solvent rinsing. The molecular packing remains intact before and after patterning. Therefore, the electrical performance of the organic thin-film transistors fabricated from both pristine and patterned i-PSSCs films shows minimal difference, with maximum field-effect mobilities of 0.46 and 0.25 cm² V^-1 s^-1, respectively. Moreover, the i-PSSCs in a transistor array exhibit high sensitivity and selective response to UV patterns, enabling bio-inspired vision systems that mimic human retinal extraction of image descriptors. This work offers a valuable strategy for developing i-PSSCs for UV-selective artificial vision applications.