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

A novel intrinsic photo‐crosslinkable semiconductive small molecule is designed and synthesized. The solution‐processed crystalline film can be patterned by in situ photopolymerization under UV light irradiation without external crosslinking agents, and the crystalline order and charge transport properties are preserved, demonstrating potential for high‐precision organic electronic devices. Abstract 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. A novel intrinsic photo-crosslinkable semiconductive small molecule is designed and synthesized. The solution-processed crystalline film can be patterned by in situ photopolymerization under UV light irradiation without external crosslinking agents, and the crystalline order and charge transport properties are preserved, demonstrating potential for high-precision organic electronic devices. Abstract 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 cm 2 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. Advanced Science, Volume 12, Issue 44, November 27, 2025.