# Fileset

[Advanced Science - 2025 - Li - Intrinsic Photo‐Crosslinkable Semiconductive Small‐Molecule Crystals i‐PSSCs for.pdf](https://mdr.nims.go.jp/filesets/33194cbb-1e05-4dfc-9378-e1e787108b4d/download)

## Creator

Huaqing Li, Xiaoguang Hu, Lei Zhang, Qingqing Sun, Chuan Liu, Linlin Zhang, Takeo Minari, [Xuying Liu](https://orcid.org/0000-0001-9190-4651)

## Rights

[Creative Commons BY Attribution 4.0 International](https://creativecommons.org/licenses/by/4.0/)

## Other metadata

[Intrinsic Photo‐Crosslinkable Semiconductive Small‐Molecule Crystals (i‐PSSCs) for Patterning Electronic Devices](https://mdr.nims.go.jp/datasets/b207dff0-1b0f-45f0-a5fd-e1d52bfda312)

## Fulltext

Intrinsic Photo‐Crosslinkable Semiconductive Small‐Molecule Crystals (i‐PSSCs) for Patterning Electronic DevicesRESEARCH ARTICLEwww.advancedscience.comIntrinsic Photo-Crosslinkable SemiconductiveSmall-Molecule Crystals (i-PSSCs) for Patterning ElectronicDevicesHuaqing Li, Xiaoguang Hu,* Lei Zhang, Qingqing Sun, Chuan Liu, Linlin Zhang,Takeo Minari, and Xuying Liu*Precise patterning of small-molecule semiconductive crystals without externalchemical additives remains a significant challenge. Herein, intrinsicphoto-crosslinkable semiconductive small-molecule crystals (i-PSSCs) aredesigned and synthesized by associating[1]benzothieno[3,2-b]benzothiophene core with diacetylene-ended groups. Thei-PSSCs undergo self-crosslinking directly upon UV light irradiation to yieldmicron-scale patterned crystalline films through a combination ofphoto-crosslinking and solvent rinsing. The molecular packing remains intactbefore and after patterning. Therefore, the electrical performance of theorganic thin-film transistors fabricated from both pristine and patternedi-PSSCs films shows minimal difference, with maximum field-effect mobilitiesof 0.46 and 0.25 cm2 V−1 s−1, respectively. Moreover, the i-PSSCs in atransistor array exhibit high sensitivity and selective response to UV patterns,enabling bio-inspired vision systems that mimic human retinal extraction ofimage descriptors. This work offers a valuable strategy for developing i-PSSCsfor UV-selective artificial vision applications.H. Li, X. Hu, Q. Sun, L. Zhang, X. LiuSchool of Materials Science and EngineeringZhengzhou UniversityZhengzhou 450001, ChinaE-mail: xghu@zzu.edu.cn; liuxy@zzu.edu.cnL. ZhangBeijingAdvanced InnovationCenter for SoftMatter Science andEngineer-ingBeijingUniversity of Chemical TechnologyBeijing 100029, ChinaC. LiuState Key Laboratory ofOptoelectronicMaterials andTechnologiesSchool of Electronics and InformationTechnologySunYat-senUniversityGuangzhou510275, ChinaT.MinariPrintedElectronicsGroup, ResearchCenter for FunctionalMaterialsNational Institute forMaterials Science (NIMS)Tsukuba, Ibaraki 305-0044, JapanThe ORCID identification number(s) for the author(s) of this articlecan be found under https://doi.org/10.1002/advs.202504711© 2025 The Author(s). Advanced Science published by Wiley-VCHGmbH. This is an open access article under the terms of the CreativeCommons Attribution License, which permits use, distribution andreproduction in any medium, provided the original work is properly cited.DOI: 10.1002/advs.2025047111. IntroductionOrganic semiconductors have gar-nered significant attention for theirpotential in flexible electronics,[1] or-ganic optoelectronics,[2,3] and sensortechnologies[4] due to their mechanicalflexibility, cost-effectiveness, and tunablechemical structures. These materials play acrucial role in the active layers of electronicdevices, where precise patterning withcontrolled position and thickness is essen-tial for minimizing crosstalk and leakagecurrents, enhancing device integration,and improving performance consistency.[5]As such, the development of effective pat-terning technologies has become a criticalaspect of fabricating high-performanceorganic semiconductor devices.Traditional patterning methods, such asphotolithography, are ill-suited for organicsemiconductors due to the harsh conditionsrequired, including high temperatures, photoresist residues,and chemical etching treatments.[6] Solution-based processes,[7]on the other hand, offer several advantages, including low-temperature fabrication and scalability, which are crucial forproducing large-area flexible devices.[8] Techniques like inkjetprinting,[9] microcontact printing,[10] and selective surface en-ergy engineering[11,12] have been explored, enabling the cre-ation of high-resolution patterns.[13] However, a significant chal-lenge persists: organic semiconductors are inherently vulnerableto solvent-induced degradation, particularly during subsequentsolution-based deposition steps. This instability can lead to par-tial dissolution of patterned films, compromising device perfor-mance, reproducibility, and reliability. One promising strategyto address this issue is the photo-crosslinking of organic smallmolecules and polymers, which enhances their resistance tosolvents.In situ photo-crosslinking not only improves the solvent re-sistance of organic semiconductor films but also enables pat-terning through solvent rinsing, achieving both improved sta-bility and precision. Several photo-crosslinkers, such as azide,[14]diazirine,[15] thiol-ene,[16] and diacetylene,[17] have been incorpo-rated into organic semiconductors to enable photolithographicpatterning. Recent studies have demonstrated that blendingpolymer semiconductors with these photo-crosslinkers allowsAdv. Sci. 2025, e04711 e04711 (1 of 8) © 2025 The Author(s). Advanced Science published by Wiley-VCH GmbHhttp://www.advancedscience.commailto:xghu@zzu.edu.cnmailto:liuxy@zzu.edu.cnhttps://doi.org/10.1002/advs.202504711http://creativecommons.org/licenses/by/4.0/http://creativecommons.org/licenses/by/4.0/http://crossmark.crossref.org/dialog/?doi=10.1002%2Fadvs.202504711&domain=pdf&date_stamp=2025-08-30www.advancedsciencenews.com www.advancedscience.comScheme 1. Synthetic routes of compounds 6, 7, and 8.for the formation of patterned films with channel lengths assmall as 2 μm.[18] Azide- and diazirine-based photo-crosslinkers,in particular, can crosslink both semiconducting and dielec-tric polymers, as well as nanoparticles, through light-inducedcarbene insertions into molecular chains.[19] However, multi-component photoresists for polymeric semiconductors can suf-fer from phase separation, which compromises material stabilityand device reproducibility in large-area arrays. To address thesechallenges, photo-crosslinkable single-component semiconduc-tors have been developed by integrating photoactive groups suchas aliphatic azides[20] and cinnamates[21] into the side chainsof conjugated polymers. These materials undergo crosslinkingunder UV or electron-beam irradiation, enabling the forma-tion of insoluble submicron or micron-scale patterns. In con-trast to polymer-based systems,[14,22] small-molecule semicon-ductors provide superiormolecular uniformity and crystalline or-der, which not only improve film quality and reproducibility butalso enable higher charge carrier mobility.[23] Crucially, preserv-ing the molecular packing during photo-crosslinking is essentialfor maintaining the high performance of the patterned films.In this work, we introduce a class of intrinsic photo-crosslinkable semiconductive small-molecule crystals (i-PSSCs).The 𝜋-conjugated core [1]benzothieno[3,2-b]benzothiophene(BTBT) is used to ensure high crystallinity and mobility, whilediacetylene (DA) photo-crosslinkable groups are incorporated tofacilitate crosslinking under UV light. Blade-coated crystallinethin films of molecule 6 were successfully photo-patterned uponexposure to UV light (254 nm, 1 mW cm−2) and subsequentdeveloping treatment, and their tight intermolecular herring-bone packing was retained. Notably, organic thin-film transis-tors (OTFTs) fabricated from molecule 6 films exhibited similarperformance before and after photopatterning, with maximumcharge mobilities of 0.46 and 0.25 cm2 V−1 s−1, respectively. Fur-thermore, the OTFT array exhibited high sensitivity and selectiv-ity to UV (365 nm) patterns, effectively extracting image descrip-tors from “H”-shaped characters, demonstrating its potential forUV-selective bio-inspired vision systems, such as artificial retinalimaging.2. Results and Discussion2.1. Synthesis of 6, 7, and 8The target compounds were synthesized fromBTBT (1) via a five-step process as shown in Scheme 1. First, a Friedel-Crafts acyla-tion reaction was conducted to introduce two bromoacyl chains atpositions 2 and 7 of the BTBT core. The keto group in compound2 was then reduced using a sodium borohydride/anhydrous alu-minum chloride (III) system, yielding compound 3.[24] Subse-quently, the alkyne precursors 5 were synthesized in a two-stepsequence[25] beginning with the alkylation of compound 3 withtrimethylsilylacetylene, followed by desilylation with potassiumcarbonate inmethanol. Finally, compounds 6, 7, and 8 containingDA units were obtained through Sonogashira coupling reactionof compound 5 with iodoalkyne.[26] The synthetic details are pro-vided in the Supporting Information (Figures S1–S33, Support-ing Information). Thermal gravimetric analysis revealed high de-composition temperatures of 453, 446, and 432 °C for 6, 7, and 8,respectively (Table 1), indicating their excellent thermal stability(Figure S36, Supporting Information).2.2. Crystal PackingSingle crystals of 6, 7, and 8 were grown by slow solvent evap-oration from THF/Hexane or toluene solutions, and their struc-tures are depicted in Figure 1. Compounds 6 and 7 crystallize inthe triclinic P-1 space group, while compound 8 adopts a mon-oclinic system with the space group P21/c. All three moleculesexhibit layered crystalline packing with each layer adopting a typ-ical herringbone packing. The intermolecular distances betweenadjacent molecules are measured at 6.03 and 8.64 Å for 6, and6.40 and 8.09 Å for 7. These close intermolecular distances facil-itate strong C─H∙∙∙𝜋 (2.869–2.872 Å) and S-𝜋 (3.359–3.493 Å)interactions between the neighboring molecules in both com-pounds (Figure S35, Supporting Information), which is expectedto enable efficient charge transfer in these molecules.[27] In con-trast, longer intermolecular distances (11.57 and 8.10 Å) areAdv. Sci. 2025, e04711 e04711 (2 of 8) © 2025 The Author(s). Advanced Science published by Wiley-VCH GmbH 21983844, 0, Downloaded from https://advanced.onlinelibrary.wiley.com/doi/10.1002/advs.202504711 by CochraneChina, Wiley Online Library on [30/08/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensehttp://www.advancedsciencenews.comhttp://www.advancedscience.comwww.advancedsciencenews.com www.advancedscience.comTable 1. Summary of the optical and electrochemical properties of 6, 7, and 8. Charge mobilities, threshold voltages, and on-off current ratios of OTFTswith the pristine thin film of 6 and 8, and the corresponding patterned thin film of 6.Compound EHOMOa) [eV] Egoptb) [eV] ELUMOc) [eV] UV irradiation µh, adv [µh, max]d) [cm2 v−1 s−1] Vth [V] Ion/Ioff6 −5.69 3.63 −2.06 Before 0.29 ± 0.081 (0.46) −30.68 ± 2.611 106–107After 0.10 ± 0.048 (0.25) −44.7 ± 2.352 105–1067 −5.69 3.63 −2.06 – – – –8 −5.68 3.63 −2.05 Before 0.01 ± 0.004 (0.015) −25.33 ± 2.132 104–105a)HOMO energy calculated by EHOMO =−(Eoxsample−EoxFc/Fc+ + 4.8);b)Band-gap energy obtained from the edge of the thin film absorption spectra;c)LUMO energy calculatedby subtracting the optical bandgap from HOMO;d)All average mobilities are based on 36 devices, and maximum values are shown in parentheses.observed in compound 8, which are too wide to support efficientcharge transfer. Additionally, the adjacent C≡C─C≡C groups incompounds 6 and 7 overlap with a distance of 3.79 and 3.44 Åbetween C1 and C4′, which is necessary and favorable for 1,4-coupling reaction.[28] Notably, the distance between C1 and C4′in compound 8 is particularly long (4.77 Å), making the reactionof adjacent DA segments highly unlikely.2.3. Optical and Electrochemical PropertiesThe optical property was investigated using UV–vis absorp-tion spectroscopy. Strong absorption bands in the UV region(230–340 nm) were observed for compounds 6, 7, and 8 indichloromethane (DCM, 2 × 10−5 m), with prominent peaks lo-cated at 313, 270, and 241 nm for the threemolecules (Figure S38,Supporting Information). The peaks are attributed to the 𝜋→𝜋*transition of the BTBT conjugated core.[29,30] Compared to the so-lution sample, thin films of 6 and 8 exhibit significant redshiftsin absorption, with intense peaks at 252 and 345 nm for film 6,and 220, 273, and 326 nm for film 8 (Figure S39, SupportingInformation). This redshift is strongly associated with the 𝜋–𝜋packing interaction between molecules in the aggregated state.Cyclic voltammetry (CV) measurements reveal the redox behav-iors of these compounds. The oxidation potentials of 6, 7, and 8Figure 1. Single-crystal X-ray structures and partial solid-state packing of 6, 7, and 8 with a typical herringbone packing. In the herringbone packingstructures, the alkyl chain details are omitted for simplification.Adv. Sci. 2025, e04711 e04711 (3 of 8) © 2025 The Author(s). Advanced Science published by Wiley-VCH GmbH 21983844, 0, Downloaded from https://advanced.onlinelibrary.wiley.com/doi/10.1002/advs.202504711 by CochraneChina, Wiley Online Library on [30/08/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensehttp://www.advancedsciencenews.comhttp://www.advancedscience.comwww.advancedsciencenews.com www.advancedscience.comwere measured at E1/2 OX = 1.24, 1.24, and 1.23 V, with reduc-tion waves observed at E1/2 red = −0.81, −0.81, and −0.78 V (vsFc+/Fc), respectively (Figure S41, Supporting Information). Thehighest occupiedmolecular orbital (HOMO) energy levels of 6, 7,and 8 were calculated from CV to be −5.69, −5.69, and −5.68 eV,respectively. Correspondingly, the lowest unoccupied molecularorbital (LUMO) energy levels were derived by subtracting the op-tical bandgap from HOMO, yielding −2.06, −2.06, and −2.05 eV(Table 1).2.4. Intrinsic Photo-Crosslinkable SemiconductiveSmall-Molecule Crystals (i-PSSCs)The processes for preparing i-PSSCs were illustrated inFigure 2a. Initially, a large-area crystalline semiconductor thinfilm was grown on a polystyrene (PS)-modified[31] SiO2/Si sub-strate using the solution shearing method. The film thicknesswas controlled in the range of 36–300 nm by adjusting the coat-ing speed (Figures S48 and S49, Supporting Information). Due tothe anisotropic crystallization behavior during blade coating, thefilms exhibited well-aligned ribbon-like crystalline domains ori-ented along the coating direction, as observed in atomic forcemi-croscopy (AFM), transmission electron microscopy (TEM), andpolarizing optical microscope (POM) (Figures S46–S49 and S51,Supporting Information). The patterned thin films of i-PSSCswere then obtained though successive UV light irradiation witha photomask and solvent rinsing. Notably, compound 7 did notform continuous films on the substrate, likely due to its extendedside chains (Figure S34, Supporting Information), which weakenintermolecular interactions and disrupt the ordered moleculararrangement.[32]Additionally, long side chains are likely to impact the wetta-bility and molecular spreading ability on the substrate.[33] Theschematic diagram of ideal topological polymerization (e.g., 6)is depicted in Figure 2b, where the adjacent DAs undergotopochemical 1,4-polymerization under UV irradiation, formingpoly(ene-yne) chains that crosslink the molecules while main-taining the ordered packing of the BTBT cores.[34,35] UV–vis ab-sorption measurement of the i-PSSCs films was performed dur-ing illumination (Figure 2c). A new absorption in the range of400–550 nm appeared and gradually increased during the illu-mination of 254 nm light (1 mW cm−2), indicating the crosslink-ing of DA units within the i-PSSCs film.[36] Correspondingly, Ra-man spectra showed significant stretching bands at 1512 and2108 cm−1 after 7 min of UV irradiation(Figure 2d), attributedto the double and triple bonds in the resulting C═C─C≡Cmoieties,[37] supporting the formation of crosslinked poly(ene-yne) chains. When the film was covered with a photomaskand irradiated with UV light, various patterns—including let-ters, Chinese characters, animals, and geometric shapes—weresuccessfully generated by immersing the film in acetonitrilefor 2 min to remove the unexposed areas (Figure 2e–h). Asshown in Figure 2i and Figure S44a,b (Supporting Informa-tion), the patterned edges are clearly defined in the AFM heightmaps, indicating that the i-PSSC films of compound 6 were ef-fectively crosslinked to resist solvent rinsing. To further evalu-ate the patterning fidelity, the line-edge roughness (LER) wasanalyzed based on AFM profiles across the pattern bound-aries, yielding an average LER of ≈65 nm. This result con-firms the potential of our system for high patterning preci-sion, which is suitable for phototransistor array fabrication andcompares favorably with other organic photopatterning meth-ods (Table S3, Supporting Information). In contrast, no signif-icant change in UV absorption was observed for thin film 8(Figure S56, Supporting Information) under 254 nm illumina-tion for 20 min. Additionally, no stretching bands appeared inthe Raman spectra, confirming that compound 8 did not undergotopological polymerization, consistent with itsmolecular packing(Figure 1).To further investigate the film quality of i-PSSCs after photo-crosslinking and assess the effect of molecular cross-linking onthe molecule packing, X-ray diffraction (XRD), POM, and AFMcharacterizations were carried out. The XRD patterns of filmsof molecule 6, before and after UV illumination, both exhibitthree diffraction peaks, which correspond to the (00L) plane fam-ily. This indicates that the ab plane of the crystal 6 is alignedparallel to the substrate (Figure 2j). After 7 min UV irradiation,the peak corresponding to (00L) shifted to a higher angle (2𝜃)from 3.26° to 3.37°, accompaniedwith a decrease in the interlayerstacking distance from 27.1 to 26.1 Å. The reduction in interlayerspacing suggests the occurrence of a polymerization reactionbetween the molecules.[38] Furthermore, no significant changewas observed in the regular microstripe crystalline morphologyof the film after polymerization under POM (Figure S52, Sup-porting Information). Additionally, after polymerization, the sur-face root-mean-square (RMS) roughness slightly increased from0.59 to 0.67 nm, while the step height decreased from 2.66 to2.54 nm (Figures S48 and S54, Supporting Information), whichis consistent with the packing distance observed in the XRDresults.Grazing-incidence wide-angle X-ray scattering (GIWAXS) wasalso employed to gain insights into the molecular packing in thefilms of the i-PSSCs 6 before and after irradiation. The sharp anddiscrete Bragg diffraction patterns (Figure 2k,l) observed in bothout-of-plane and in-plane directions further confirm the highcrystallinity and long-range ordered packing of the i-PSSCs films,both before and after cross-linking. When the incident X-ray isperpendicular to the coating direction, diffraction spots corre-sponding to the (02L) plane, related to the b-axis, are observedalong the plane direction, revealing their ordered arrangement inthe b-axis direction. Importantly, the d-spacing of the (001) peakin the out-of-plane direction shifted from 26.3 Å (qz = 0.239 Å−1)before illumination to 25.6 Å (qz = 0.245 Å−1) after illumina-tion, which is consistent with the vertical height change of themolecules noted earlier. Thus, during the polymerization processof the i-PSSCs, the crystal order of the monomers remains in-tact, while the lattice parameters undergo slight changes. TEMimages in Figure 2m,p reveal a smooth surface morphology, andthe corresponding selected area electron diffraction (SAED) pat-terns in Figure 2n,o,q,r show consistent diffraction spots acrossdifferent areas of the film, further confirming the excellent crys-tal quality and orientation of the film 6 both before and aftercrosslinking. In summary, it is evident that the b-axis is thepreferred direction of crystal growth, and the molecule pack-ing in the thin film of molecule 6 remains intact after illumi-nation, providing optimal intermolecular interactions for chargetransport.Adv. Sci. 2025, e04711 e04711 (4 of 8) © 2025 The Author(s). Advanced Science published by Wiley-VCH GmbH 21983844, 0, Downloaded from https://advanced.onlinelibrary.wiley.com/doi/10.1002/advs.202504711 by CochraneChina, Wiley Online Library on [30/08/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensehttp://www.advancedsciencenews.comhttp://www.advancedscience.comwww.advancedsciencenews.com www.advancedscience.comFigure 2. a) The photo-patterning process of the i-PSSCs 6. b) Topochemical photochemical reaction of monomer 6. c) UV–vis spectra for illuminationtimes ranging from 0 to 8 min. d) Raman spectra of 6 for 0 and 7 min of illumination. e–h) Optical microscope images of patterned film 6. i) AFM imageabout the edges of the pattern in Figure S59a (Supporting Information). j) XRD patterns of 6 before and after illumination. k,l) GIWAXS images of 6with incident X-ray beams perpendicular to the coating direction of the films. m–o) TEM images of 6 before illumination and its corresponding SAEDpatterns recorded from the different positions marked in (m). p–r) TEM images of 6 after illumination and its corresponding SAED patterns recordedfrom the different positions marked in (p).2.5. Charge Transport Properties and ApplicationTo investigate the charge transfer characteristics of the i-PSSCs,bottom gate and top contact (BGTC) OTFTs (Figure S59, Sup-porting Information) were fabricated using the correspondingpatterned thin films as active layers. Detailed procedures are out-lined in the Supporting Information. In brief, a transparent rect-angular mask (length: 1000 μm, width: 500 μm) was placed ona crystalline film of molecule 6, which was scraped onto a PS-modified SiO2/Si substrate and exposed to 254 nm light. Afterdevelopment with acetonitrile, an electrode mask was alignedwith the semiconductor position, and thermally evaporated Ag(80 nm) was used as the source and drain electrodes. It is cru-cial that the crystal growth direction is parallel to the conduc-Adv. Sci. 2025, e04711 e04711 (5 of 8) © 2025 The Author(s). Advanced Science published by Wiley-VCH GmbH 21983844, 0, Downloaded from https://advanced.onlinelibrary.wiley.com/doi/10.1002/advs.202504711 by CochraneChina, Wiley Online Library on [30/08/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensehttp://www.advancedsciencenews.comhttp://www.advancedscience.comwww.advancedsciencenews.com www.advancedscience.comFigure 3. a,b) Typical transfer and output curves, c) the optical image of patterned OTFT array, d) mobility distribution of 36 OTFT devices about thepatterned i-PSSCs 6. e,f) Typical transfer and output curves, g) the optical image of OTFT array, h) mobility distribution of 36 OTFT devices aboutthe pristine film of 6. i) The artificial vision system composed of a detection unit and schematic illustration of organic photodetector device based onpatterned film of 6. j) The transfer curves of the OPTs in various illumination intensities. k) Photo-response measurements of the device in the dark andunder illumination. l) Image detection of device array with an input image of letter “H” (under illumination with “H” type mask on top).tive channel. The mobility was measured in air and calculatedfrom the transfer curve in the saturation state. A 6 × 6 rectangu-lar array was selected from the same batch of devices for testing(Figure 3c). After analyzing 36 transfer curves (Figure S66, Sup-porting Information), the highest mobility of the patterned filmwas obtained as 0.25 cm2 V−1 s−1 and an on/off current ratio ap-proaching 106. The representative transfer and output I–V curvesof the fabricated OTFT are presented in Figure 3a,b.For comparison, the same test was carried out onBGTCOTFTsfabricated from the pristine thin film of 6. Similarly, 36 trans-fer curves were analyzed (Figure 3g), and the highest mobilityof the pristine film was found to be 0.46 cm2 V−1 s−1 and anon/off current ratio approaching 107. The I-V curves and OTFTimage are shown in Figure 3e,f. This suggests that the perfor-mance remains well-preserved after photo-patterning. Moreover,both pristine and patterned film-basedOTFTs exhibit narrow per-formance distributions, demonstrating excellent uniformity indevice performance (Figure 3d,h). The slight reduction in mo-bility and other parameters after illumination may be due to thediscontinuity of the cross-linked molecular chain, which gener-Adv. Sci. 2025, e04711 e04711 (6 of 8) © 2025 The Author(s). Advanced Science published by Wiley-VCH GmbH 21983844, 0, Downloaded from https://advanced.onlinelibrary.wiley.com/doi/10.1002/advs.202504711 by CochraneChina, Wiley Online Library on [30/08/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensehttp://www.advancedsciencenews.comhttp://www.advancedscience.comwww.advancedsciencenews.com www.advancedscience.comates a large number of defects that affect charge transfer. Themaximum mobilities of the OTFTs before and after crosslinkingwere 0.46 and 0.25 cm2 V−1 s−1, respectively. These values arelower than BTBT derivatives such as C8-BTBT and Ph-BTBT.[39–41]This can be attributed to the influence of diacetylene side chainson molecular packing, increased grain boundaries and misori-entation from solution-based film deposition, and additional de-fects or disorder introduced during the photo-crosslinking pro-cess. In addition, OTFTs were also fabricated with the film 8 asthe active layer, and the typical transfer and output curves areshown in Figure S62 (Supporting Information). Consistent withthe single-crystal analysis (Figure 1), the stacking of 8 hinderscharge transfer, resulting in an order-of-magnitude lower mobil-ity of 0.015 cm2 V−1 s−1. Therefore, only 6 effectively combinethe functions of both a semiconductor and an intrinsic photo-patternable crystal.The semiconducting properties of the i-PSSCs 6, associatedwith its photopatterning ability,make it a promising candidate forphototransistor applications. Organic phototransistors (OPTs) in-tegrate both light detection (Figure 3i) and electrical signal ampli-fication functions, with wide-ranging applications in fields suchas biology and communication.[42] To assess the feasibility ofOTFT devices in simulating visual neurons, source-drain cur-rentsweremeasured under 365 nmUV light at varying power lev-els. The typical transmission characteristics of the phototransis-tor under dark and illuminated conditions are shown in Figure 3j,where the current increases as the light power rises. The cur-rent changes result from the accumulation of photogeneratedcarriers around the source/drain, leading to band bending in thesemiconductor and reducing the potential barrier for hole injec-tion into the source electrode.[43,44] Compared to the dark con-dition, more holes participate in the charge transport process atthe same driving voltage (Figure S70, Supporting Information),which increases the photocurrent. Light irradiation can indepen-dently control the output current of OPTs. The measurement inFigure 3kwas performed by periodically switching theUV illumi-nation (4.3 mW cm−2, VDS = −40 V, VGS = 0 V) on and off, with atotal of 21 consistent ON–OFF current cycles observed (ON–OFFratio ≈102), demonstrating stable photodetector performance. Askeleton mask with the symbol “H” was used to cover the siliconwafer with a 7 × 7 imaging pixel matrix (Figure S72, Support-ing Information), and the output current from the light-exposedareas remained ≈10−8 A (Figure 3l). By recording the currentchanges across the matrix, the character shape can be accuratelyreproduced, highlighting the potential of patterned i-PSSCs asUV-selective neuromorphic visual sensors for bio-inspired elec-tronic systems.3. ConclusionIn conclusion, this work presents a strategy for developing i-PSSCs by combining a semiconductor BTBT core with photo-crosslinkable diacetylene groups. The molecule packing isstrongly influenced by the alkyl chain and terminal substituentson the DA units, neighboring DAs only overlapping in film 6,which has a terminal methyl group. As a result, only compound6 can self-crosslink under UV light irradiation, and the molecu-lar packing in the highly ordered crystalline film remains intactafter photo-patterning. Importantly, the electrical performance ofOTFTs based on the patterned crystalline films is comparable tothat of devices made from pristine crystalline films, with maxi-mummobility values of 0.25 and 0.46 cm2 V−1 s−1. Furthermore,the patterned thin films exhibit highUV responsiveness, openingnew avenues for application in UV-selective, bio-inspired neuro-morphic visual electronics.4. Experimental SectionExperimental details, NMR and HRMS spectra, TGA and DSC spec-tra, CV and optical absorption spectra, theoretical calculation, POM, AFM,XRD images, and CCDC 2415605 (6 at 293 K), 2415606 (7 at 100 K) and2415608 (8 at 293 K) contains the crystallographic data can be found inthe Supporting Information.Supporting InformationSupporting Information is available from the Wiley Online Library or fromthe author.AcknowledgementsThe work was supported by the National Natural Science Foundation ofChina (52373315 and 22005272), the Henan Science and Technology De-partment (222301420004). Theoretical calculation in this work was sup-ported by the National Supercomputing Center in Zhengzhou.Conflict of InterestThe authors declare no conflict of interest.Data Availability StatementThe data that support the findings of this study are available from the cor-responding author upon reasonable request.Keywordsintrinsic crosslinking, organic phototransistors, photopatterning, semi-conductive small-molecule crystalsReceived: March 14, 2025Revised: August 17, 2025Published online:[1] S. Wang, J. Xu, W. Wang, G.-J. N. Wang, R. Rastak, F. Molina-Lopez, J.W. Chung, S. Niu, V. R. Feig, J. Lopez, T. Lei, S.-K. Kwon, Y. Kim, A. M.Foudeh, A. Ehrlich, A. Gasperini, Y. Yun, B. Murmann, J. B.-H. Tok, Z.Bao, Nature 2018, 555, 83.[2] L. Zhu, M. Zhang, J. Xu, C. Li, J. Yan, G. Zhou, W. Zhong, T. Hao,J. Song, X. Xue, Z. Zhou, R. Zeng, H. Zhu, C.-C. Chen, R. C. I.MacKenzie, Y. Zou, J. Nelson, Y. Zhang, Y. Sun, F. Liu, Nat. Mater.2022, 21, 656.[3] Y.-T. Wang, W.-J. Sun, Y. Zhang, B.-Y. Zhang, Y.-T. Ding, Z.-Q. Zhang,L. Meng, K. Huang, W. Ma, H.-L. Zhang, Angew. Chem., Int. Ed. 2024,64, 202417643.Adv. Sci. 2025, e04711 e04711 (7 of 8) © 2025 The Author(s). Advanced Science published by Wiley-VCH GmbH 21983844, 0, Downloaded from https://advanced.onlinelibrary.wiley.com/doi/10.1002/advs.202504711 by CochraneChina, Wiley Online Library on [30/08/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensehttp://www.advancedsciencenews.comhttp://www.advancedscience.comhttps://www.ccdc.cam.ac.uk/services/structures?id=doi:10.1002/advs.202504711www.advancedsciencenews.com www.advancedscience.com[4] Z. Chen, X. Ding, J. Wang, X. Guo, S. Shao, K. Feng, Angew. Chem.,Int. Ed. 2025, 64, 202423013.[5] H. Shim, S. Jang, C. Yu,Matter 2022, 5, 23.[6] T. Park, M. Kim, E. K. Lee, J. Hur, H. Yoo, Small 2024, 20, 2306468.[7] K. Lu, X. Li, Q. Sun, X. Pang, J. Chen, T. Minari, X. Liu, Y. Song,Mater.Horiz. 2021, 8, 447.[8] Z. Wu, Y. Yan, Y. Zhao, Y. Liu, Small Methods 2022, 6, 2200752.[9] X. Ren, F. Qiu, W. Deng, X. Fang, Y. Wu, S. Yu, X. Liu, S. Grigorian, J.Shi, J. Jie, X. Zhang, X. Zhang, ACS Nano 2023, 17, 25175.[10] Y. Zhao, X. Fan, J. Feng, X. Wang, Y. Wu, B. Su, L. Jiang, Adv. Funct.Mater. 2018, 28, 1800470.[11] Y. Xiao, W. Deng, J. Hong, X. Ren, X. Zhang, J. Shi, F. Sheng, X. Zhang,J. Jie, Adv. Funct. Mater. 2023, 33, 2213788.[12] X. Liu, M. Kanehara, C. Liu, K. Sakamoto, T. Yasuda, J. Takeya, T.Minari, Adv. Mater. 2016, 28, 6568.[13] M. Yuan, Y. Qiu, H. Gao, J. Feng, L. Jiang, Y. Wu, J. Am. Chem. Soc.2024, 146, 7885.[14] X. Xue, C. Li, Q. Zhou, X. Yu, C. Gao, K. Chenchai, J. Liao, Z.Shangguan, X. Zhang, G. Zhang, D. Zhang, Adv. Mater. 2024, 36,2407305.[15] N. J. Porter, E. Danelius, T. Gonen, F. H. Arnold, J. Am. Chem. Soc.2022, 144, 8892.[16] T.-L. Pu, X.-Y. Wang, Z.-B. Sun, X.-Y. Dong, Q.-Y. Wang, S.-Q. Zang,Angew. Chem., Int. Ed. 2024, 63, 202402363.[17] A. Dhaka, I.-R. Jeon, O. Jeannin, E. Aubert, E. Espinosa, M.Fourmigué, Angew. Chem., Int. Ed. 2022, 61, 202116650.[18] Y.-Q. Zheng, Y. Liu, D. Zhong, S. Nikzad, S. Liu, Z. Yu, D. Liu, H.-C. Wu, C. Zhu, J. Li, H. Tran, J. B.-H. Tok, Z. Bao, Science 2021, 373,88.[19] H. Ye, H. Kwon, K. Y. Ryu, K. Wu, J. Park, G. Babita, I. Kim, C. Yang,H. Kong, S. H. Kim, Nanoscale Adv. 2024, 6, 4119.[20] W. Jiang, X. Yu, C. Li, X. Zhang, G. Zhang, Z. Liu, D. Zhang, Sci. China:Chem. 2022, 65, 1791.[21] N. M. Bojanowski, C. Huck, L. Veith, K.-P. Strunk, R. Bäuerle, C.Melzer, J. Freudenberg, I. Wacker, R. R. Schröder, P. Tegeder, U. H. F.Bunz, Chem. Sci. 2022, 13, 7880.[22] C. Gao, D. Shi, C. Li, X. Yu, X. Zhang, Z. Liu, G. Zhang, D. Zhang, Adv.Sci. 2022, 9, 2106087.[23] T. Okamoto, C. P. Yu, C. Mitsui, M. Yamagishi, H. Ishii, J. Takeya, J.Am. Chem. Soc. 2020, 142, 9083.[24] O. V. Borshchev, A. S. Sizov, E. V. Agina, A. A. Bessonov, S. A.Ponomarenko, Chem. Commun. 2017, 53, 885.[25] D. Listunov, C. Billot, E. Joly, I. Fabing, Y. Volovenko, Y. Génisson, V.Maraval, R. Chauvin, Tetrahedron 2015, 71, 7920.[26] J. He, C. Fang, R. A. Shelp, M. B. Zimmt, Langmuir 2017, 33, 459.[27] D. Liu, X. Wu, C. Gao, C. Li, Y. Zheng, Y. Li, Z. Xie, D. Ji, X. Liu, X.Zhang, L. Li, Q. Peng, W. Hu, H. Dong, Angew. Chem., Int. Ed. 2022,61, 202200791.[28] S. Otep, K. Ogita, N. Yomogita, K. Motai, Y. Wang, Y.-C. Tseng, C.-C. Chueh, Y. Hayamizu, H. Matsumoto, K. Ishikawa, T. Mori, T.Michinobu,Macromolecules 2021, 54, 4351.[29] P. Xie, T. Liu, J. Sun, J. Yang, Adv. Funct. Mater. 2022, 32, 2200843.[30] Y. Hou, H. Chen, W. Lian, H. Li, X. Hu, X. Liu, Adv. Funct. Mater. 2023,33, 2306056.[31] S. Lee, M. Jang, H. Yang, ACS Appl. Mater. Interfaces 2014, 6, 20444.[32] S. Inoue, K. Nikaido, T. Higashino, S. Arai, M. Tanaka, R. Kumai, S.Tsuzuki, S. Horiuchi, H. Sugiyama, Y. Segawa, K. Takaba, S. Maki-Yonekura, K. Yonekura, T. Hasegawa, Chem. Mater. 2022, 34, 72.[33] M. Li, P. J. Leenaers, M. M. Wienk, R. A. J. Janssen, J. Mater. Chem. C2020, 8, 5856.[34] F.-J. Lin, C.-H. Chang, D.-C. Huang, Y.-T. Tao, ACS Appl. Polym. Mater.2023, 5, 3173.[35] H. Ko, D.-G. Kang, Y.-J. Choi, Y. Wi, S. Kim, H. H. Pham, K. M. Lee,N. P. Godman, M. E. McConney, K.-U. Jeong, J. Am. Chem. Soc. 2024,146, 4393.[36] Y. Yao, H. Dong, F. Liu, T. P. Russell, W. Hu, Adv. Mater. 2017, 29,1701251.[37] F.-J. Lin, C.-W. Yang, H.-H. Chen, Y.-T. Tao, J. Am. Chem. Soc. 2020,142, 11763.[38] T. Kato, M. Yasumatsu, C. Origuchi, K. Tsutsui, Y. Ueda, C. Adachi,Appl. Phys. Express 2011, 4, 091601.[39] Y. Yuan, G. Giri, A. L. Ayzner, A. P. Zoombelt, S. C. B. Mannsfeld, J.Chen, D. Nordlund, M. F. Toney, J. Huang, Z. Bao, Nat. Commun.2014, 5, 3005.[40] P. Xie, T. Liu, J. Sun, J. Jiang, Y. Yuan, Y. Gao, J. Zhou, J. Yang, Sci. Bull.2020, 65, 791.[41] Z. Wang, X. Wu, S. Zhang, S. Yang, P. Gao, P. Huang, Y. Xiao, X. Shen,X. Yao, D. Zeng, J. Jie, Y. Zhou, F. Yang, R. Li, W. Hu, Proc. Natl. Acad.Sci. USA 2025, 122, 2419673122.[42] C. Wang, X. Zhang, W. Hu, Chem. Soc. Rev. 2020, 49, 653.[43] Q. Sun, H. Ge, S. Wang, X. Zhang, J. Zhang, S. Li, Z. Yao, L. Zhang,X. Liu,Mater. Horiz. 2024, 11, 5650.[44] B. Yao, Y. Li, Z. Fang, Y. Tan, S. Liu, Y. Peng, H. Xu, Synth. Met. 2017,233, 58.Adv. Sci. 2025, e04711 e04711 (8 of 8) © 2025 The Author(s). Advanced Science published by Wiley-VCH GmbH 21983844, 0, Downloaded from https://advanced.onlinelibrary.wiley.com/doi/10.1002/advs.202504711 by CochraneChina, Wiley Online Library on [30/08/2025]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons Licensehttp://www.advancedsciencenews.comhttp://www.advancedscience.com