Abstract
Dip-coating is a low-cost, high-throughput technique for the deposition of organic semiconductors over large area on various substrates. Tremendous studies have been done and many parameters such as withdrawal speed, solvent type and solution concentration have been investigated. However, most of the depositions were ribbons or dendritic crystals with low coverage of the substrate due to the ignorance of the critical role of dynamic solution-substrate interactions during dip-coating. In this study, meniscus angle (MA) was proposed to quantify the real-time in-situ solution-substrate interactions during dip-coating. By proper surface treatment of the substrate, the value of MA can be tuned and centimeter-sized, continuous and highly ordered organic semiconductor thin films were achieved. The charge transport properties of the continuous thin films were investigated by the construction of organic field-effect transistors. Maximum (average) hole mobility up to 11.9(5.1) cm2 V−1s−1 was obtained. The average mobility was 82% higher than that of ribbon crystals, indicating the high crystallinity of the thin films. Our work reveals the critical role of dynamic solution-substrate interactions during dip-coating. The ability to produce large-area, continuous and highly ordered organic semiconductor thin films by dip-coating could revival the old technique for the application in various optoelectronics.
摘要
浸渍提拉法是一种低成本、大面积、高效制备有机半导体 薄膜的技术. 针对该技术中提拉速度、溶剂类型、溶液浓度等参 数的研究报道已很多. 但由于忽略了提拉过程中溶液-衬底相互作 用这个关键因素, 提拉得到的沉积物绝大多数为带状或树枝状晶 体, 覆盖率较低. 本文提出用弯月面角(MA)来量化浸渍提拉过程 中溶液与衬底的实时相互作用的强弱. 通过对衬底进行适当的表 面处理, 可以调节MA值, 从而可以获得厘米级、连续、高度有序 的有机半导体薄膜, 并构建了有机场效应晶体管(OFETs), 研究了 连续薄膜的电荷输运特性. 最大(平均) 空穴迁移率可达 11.9(5.1) cm2 V−1 s−1. 统计显示连续薄膜的平均迁移率比带状晶体 高82%, 表明所制备的薄膜具有高结晶度. 该工作揭示了浸渍提拉 过程中动态溶液-衬底相互作用在薄膜沉积过程中扮演的关键角 色, 给出了衡量二者之间相互作用强弱的量化指标, 为浸渍提拉法 制备大面积、连续、高度有序的有机半导体薄膜的研究及其在各 种光电器件领域的应用提供了理论和技术支撑.
Article PDF
Similar content being viewed by others
References
Diao Y, Shaw L, Bao Z, et al. Morphology control strategies for solution-processed organic semiconductor thin films. Energy Environ Sci, 2014, 7, 2145–2159
Gu X, Shaw L, Gu K, et al. The meniscus-guided deposition of semiconducting polymers. Nat Commun, 2018, 9: 534
Qian J, Jiang S, Li S, et al. Solution-processed 2D molecular crystals: Fabrication techniques, transistor applications, and physics. Adv Mater Technol, 2018, 4: 1800182
Yang F, Cheng S, Zhang X, et al. 2D organic materials for optoelectronic applications. Adv Mater, 2017, 30: 1702415
Yao Y, Zhang L, Leydecker T, et al. Direct photolithography on molecular crystals for high performance organic optoelectronic devices. J Am Chem Soc, 2018, 140, 6984–6990
Jiang H, Zhao H, Zhang KK, et al. High-performance organic single-crystal field-effect transistors of indolo[3,2-b]carbazole and their potential applications in gas controlled organic memory devices. Adv Mater, 2011, 23, 5075–5080
Usta H, Kim D, Ozdemir R, et al. High electron mobility in [1] benzothieno[3,2-b][1]benzothiophene-based field-effect transistors: Toward n-type BTBTs. Chem Mater, 2019, 31, 5254–5263
Schunemann C, Wynands D, Eichhorn KJ, et al. Evaluation and control of the orientation of small molecules for strongly absorbing organic thin films. J Phys Chem C, 2013, 117, 11600–11609
Jeong H, Han S, Baek S, et al. Dense assembly of soluble acene crystal ribbons and its application to organic transistors. ACS Appl Mater Interfaces, 2016, 8, 24753–24760
Wang W, Wang L, Dai G, et al. Controlled growth of large-area aligned single-crystalline organic nanoribbon arrays for transistors and light-emitting diodes driving. Nano-Micro Letters, 2017, 9: 52
Wang Z, Guo H, Li J, et al. Marangoni effect-controlled growth of oriented film for high performance C8-BTBT transistors. Adv Mater Interfaces, 2019, 6: 1801736
Yuan Y, Giri G, Ayzner AL, et al. Ultra-high mobility transparent organic thin film transistors grown by an off-centre spin-coating method. Nat Commun, 2014, 5: 3005
Jiang H, Zhang KK, Ye J, et al. Atomically flat, large-sized, two-dimensional organic nanocrystals. Small, 2013, 9, 990–995
Nikolka M, Nasrallah I, Rose B, et al. High operational and environmental stability of high-mobility conjugated polymer field-effect transistors through the use of molecular additives. Nat Mater, 2017, 16, 356–362
Sele CW, Kjellander BKC, Niesen B, et al. Controlled deposition of highly ordered soluble acene thin films: Effect of morphology and crystal orientation on transistor performance. Adv Mater, 2009, 21, 4926–4931
Li L, Gao P, Wang W, et al. Growth of ultrathin organic semiconductor microstripes with thickness control in the monolayer precision. Angew Chem Int Ed, 2013, 52, 12530–12535
Liu N, Ma W, Tao J, et al. Cable-type supercapacitors of three-dimensional cotton thread based multi-grade nanostructures for wearable energy storage. Adv Mater, 2013, 25, 4925–4931
Wu K, Li H, Li L, et al. Controlled growth of ultrathin film of organic semiconductors by balancing the competitive processes in dip-coating for organic transistors. Langmuir, 2016, 32, 6246–6254
Li L, Gao P, Schuermann KC, et al. Controllable growth and field-effect property of monolayer to multilayer microstripes of an organic semiconductor. J Am Chem Soc, 2010, 132, 8807–8809
Li L, Gao P, Baumgarten M, et al. High performance field-effect ammonia sensors based on a structured ultrathin organic semi-conductor film. Adv Mater, 2013, 25, 3419–3425
Chai Z, Abbasi SA, Busnaina AA. Scalable directed assembly of highly crystalline 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) films. ACS Appl Mater Interfaces, 2018, 10: 18123–18130
Zhao H, Wang Z, Dong G, et al. Fabrication of highly oriented large-scale tips pentacene crystals and transistors by the marangoni effect-controlled growth method. Phys Chem Chem Phys, 2015, 17, 6274–6279
Ghosh M, Fan F, Stebe KJ. Spontaneous pattern formation by dip coating of colloidal suspensions on homogeneous surfaces. Langmuir, 2007, 23: 2180–2183
Zhang K, Marszalek T, Wucher P, et al. Crystallization control of organic semiconductors during meniscus-guided coating by blending with polymer binder. Adv Funct Mater, 2018, 28: 1805594
Deng W, Zhang X, Dong H, et al. Channel-restricted meniscus self-assembly for uniformly aligned growth of single-crystal arrays of organic semiconductors. Mater Today, 2019, 24, 17–25
Nam S, Jeong YJ, Jung J, et al. Direct printing of soluble acene crystal stripes by a programmed dip-coating process for organic field-effect transistor applications. J Mater Chem C, 2018, 6, 799–807
Zheng S, Xiong X, Zheng Z, et al. Solution-grown large-area C60 single-crystal arrays as organic photodetectors. Carbon, 2018, 126, 299–304
Yang Z, Song P, Feng F, et al. Influence of dip-coating temperature upon film thickness in chemical solution deposition. IEEE Trans Appl Supercond, 2018, 28: 7500205
Takahashi K, Shan B, Xu X, et al. Engineering thin films of a tetrabenzoporphyrin toward efficient charge-carrier transport: Selective formation of a brickwork motif. ACS Appl Mater Interfaces, 2017, 9, 8211–8218
Xu X, Deng W, Zhang X, et al. Dual-band, high-performance phototransistors from hybrid perovskite and organic crystal array for secure communication applications. ACS Nano, 2019, 13, 5910–5919
Jang J, Nam S, Im K, et al. Highly crystalline soluble acene crystal arrays for organic transistors: Mechanism of crystal growth during dip-coating. Adv Funct Mater, 2012, 22, 1005–1014
Ebata H, Izawa T, Miyazaki E, et al. Highly soluble [1]benzothieno [3,2-b]benzothiophene (BTBT) derivatives for high-performance, solution-processed organic field-effect transistors. J Am Chem Soc, 2007, 129, 15732–15733
Yu X, Yu J, Zhou J, et al. Organic field-effect transistors with a sandwich structure from inserting 2,2′,2″-(1,3,5-benzenetriyl)tris [1-phenyl-1h-benzimidazole] in the pentacene active layer. Eur Phys J Appl Phys, 2013, 62: 20101
Wei W, Yang C, Mai J, et al. High mobility solution-processed C8-BTBT organic thin-film transistors via UV-ozone interface modification. J Mater Chem C, 2017, 5, 10652–10659
Izawa T, Miyazaki E, Takimiya K. Molecular ordering of high-performance soluble molecular semiconductors and re-evaluation of their field-effect transistor characteristics. Adv Mater, 2008, 20: 3388–3392
Liu C, Minari T, Lu X, et al. Solution-processable organic single crystals with bandlike transport in field-effect transistors. Adv Mater, 2011, 23, 523–526
Gbabode G, Dohr M, Niebel C, et al. X-ray structural investigation of nonsymmetrically and symmetrically alkylated [1]benzothieno [3,2-b]benzothiophene derivatives in bulk and thin films. ACS Appl Mater Interfaces, 2014, 6, 13413–13421
Zhang Z, Peng B, Ji X, et al. Marangoni-effect-assisted bar-coating method for high-quality organic crystals with compressive and tensile strains. Adv Funct Mater, 2017, 27: 1703443
Janssen D, De Palma R, Verlaak S, et al. Static solvent contact angle measurements, surface free energy and wettability determination of various self-assembled monolayers on silicon dioxide. Thin Solid Films, 2006, 515, 1433–1438
Guo DY, Tsai Y, Yu TF, et al. Interfacial effects on solution-sheared thin-film transistors. J Mater Chem C, 2018, 6, 12006–12015
Kim O, Nam J. Confinement effects in dip coating. J Fluid Mech, 2017, 827: 1–30
Casalini S, Bortolotti CA, Leonardi F, et al. Self-assembled monolayers in organic electronics. Chem Soc Rev, 2017, 46, 40–71
Corrales TP, Bai M, del Campo V, et al. Spontaneous formation of nanopatterns in velocity-dependent dip-coated organic films: from dragonflies to stripes. ACS Nano, 2014, 8, 9954–9963
Brinker CJ. Dip coating. In: Schneller T, Schneller R, Kosec M, Payne D (eds.). Chemical Solution Deposition of Functional Oxide Thin Films. Berlin: Springer, 2013, 233–261
Tang Q, Tong Y, Li H, et al. High-performance air-stable bipolar field-effect transistors of organic single-crystalline ribbons with an air-gap dielectric. Adv Mater, 2008, 20, 1511–1515
Zhu X, Wang Q, Tian X, et al. Unidirectional and crystalline organic semiconductor microwire arrays by solvent vapor annealing with PMMA as the assisting layer. J Mater Chem C, 2018, 6, 12479–12483
Acknowledgements
The authors acknowledge financial support from the National Natural Science Foundation of China (51873148, 61674116 and 51633006), the Ministry of Science and Technology of China (2016YFA0202302) and the Natural Science Foundation of Tianjin (18JC-YBJC18400).
Author information
Authors and Affiliations
Contributions
Li R and Hu W conceived the idea and directed the project. Liu X carried out most of the experiments. Zhang Y performed some OFETs measurements. Zhang X performed the XRD measurements. Liu X and Li R wrote the paper. All authors analyzed the experimental results and contributed to the discussion.
Corresponding author
Additional information
Conflict of interest
The authors declare no conflict of interest.
Supplementary information
Experimental details and supporting data are available in the online version of the paper
Xuanyu Liu obtained her bachelor degree from Zhengzhou University in 2017. She is currently a graduate student in the School of Science, Tianjin University. Her main research interests are the solution processing of OSCs and their optoelectronic properties.
Rongjin Li is a Professor of Tianjin University. He received his PhD from the Institute of Chemistry, Chinese Academy of Sciences (CAS) in 2009 supervised by Prof. Wenping Hu. His research interests include OSCs, two dimensional molecular crystals and organic optoelectronic devices.
Rights and permissions
About this article
Cite this article
Liu, X., Zhang, Y., Zhang, X. et al. Continuous and highly ordered organic semiconductor thin films via dip-coating: the critical role of meniscus angle. Sci. China Mater. 63, 1257–1264 (2020). https://doi.org/10.1007/s40843-020-1297-7
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s40843-020-1297-7