The use of single crystals has been fundamental to the development of semiconductor microelectronics and solid-state science1. Whether based on inorganic2,3,4,5 or organic6,7,8 materials, the devices that show the highest performance rely on single-crystal interfaces, with their nearly perfect translational symmetry and exceptionally high chemical purity. Attention has recently been focused on developing simple ways of producing electronic devices by means of printing technologies. ‘Printed electronics’ is being explored for the manufacture of large-area and flexible electronic devices by the patterned application of functional inks containing soluble or dispersed semiconducting materials9,10,11. However, because of the strong self-organizing tendency of the deposited materials12,13, the production of semiconducting thin films of high crystallinity (indispensable for realizing high carrier mobility) may be incompatible with conventional printing processes. Here we develop a method that combines the technique of antisolvent crystallization14 with inkjet printing to produce organic semiconducting thin films of high crystallinity. Specifically, we show that mixing fine droplets of an antisolvent and a solution of an active semiconducting component within a confined area on an amorphous substrate can trigger the controlled formation of exceptionally uniform single-crystal or polycrystalline thin films that grow at the liquid–air interfaces. Using this approach, we have printed single crystals of the organic semiconductor 2,7-dioctylbenzothieno[3,2-b]benzothiophene (C8-BTBT) (ref. 15), yielding thin-film transistors with average carrier mobilities as high as 16.4 cm2 V−1 s−1. This printing technique constitutes a major step towards the use of high-performance single-crystal semiconductor devices for large-area and flexible electronics applications.
Subscribe to Journal
Get full journal access for 1 year
only $3.83 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
Teal, G. K. Single crystals of germanium and silicon—basic to the transistor and integrated circuit. IEEE Trans. Electron. Dev. 23, 621–639 (1976)
Tsui, D. C., Stormer, H. L. & Gossard, A. C. Two-dimensional magnetotransport in the extreme quantum limit. Phys. Rev. Lett. 48, 1559–1562 (1982)
De Poortere, E. P. et al. Enhanced electron mobility and high order fractional quantum Hall states in AlAs quantum wells. Appl. Phys. Lett. 80, 1583–1585 (2002)
Ohtomo, A. & Hwang, H. Y. A high-mobility electron gas at the LaAlO3/SrTiO3 heterointerface. Nature 427, 423–426 (2004)
Tsukazaki, A. et al. Observation of the fractional quantum Hall effect in an oxide. Nature Mater. 9, 889–893 (2010)
Sundar, V. C. et al. Elastomeric transistor stamps: reversible probing of charge transport in organic crystals. Science 303, 1644–1646 (2004)
Briseno, A. L. et al. Patterning organic single-crystal transistor arrays. Nature 444, 913–917 (2006)
Takeya, J. et al. Very high-mobility organic single-crystal transistors with in-crystal conduction channel. Appl. Phys. Lett. 90, 102120 (2007)
Yan, H. et al. A high-mobility electron-transporting polymer for printed transistors. Nature 457, 679–686 (2009)
Rivnay, J. et al. Large modulation of carrier transport by grain-boundary molecular packing and microstructure in organic thin films. Nature Mater. 8, 952–958 (2009)
Noh, Y.-Y., Zhao, N., Caironi, M. & Sirringhaus, H. Downscaling of self-aligned, all-printed polymer thin-film transistors. Nature Nanotechnol. 2, 784–789 (2007)
Whitesides, G. M. & Grzybowski, B. Self-assembly at all scales. Science 295, 2418–2421 (2002)
Lim, J. A., Lee, H. S., Lee, W. H. & Cho, K. Control of the morphology and structural development of solution-processed functionalized acenes for high-performance organic transistors. Adv. Funct. Mater. 19, 1515–1525 (2009)
Tung, H.-H., Paul, E. L., Midler, M. & McCauley, J. A. Crystallization of Organic Compounds: An Industrial Perspective 179–205 (Wiley, 2009)
Ebata, H. et al. Highly soluble benzothieno[3,2-b]benzothiophene (BTBT) derivatives for high-performance, solution-processed organic field-effect transistors. J. Am. Chem. Soc. 129, 15732–15733 (2007)
Hiraoka, M. et al. On-substrate synthesis of molecular conductor films and circuits. Adv. Mater. 19, 3248–3251 (2007)
Hasegawa, T., Hiraoka, M. & Yamada, T. Double-shot inkjet printing of donor–acceptor-type organic charge-transfer complexes: wet/nonwet definition and its use for contact engineering. Thin Solid Films 518, 3988–3991 (2010)
Sirringhaus, H. et al. High-resolution inkjet printing of all-polymer transistor circuits. Science 290, 2123–2126 (2000)
Chen, Z., Liu, M., Liu, G.-y. & Tan, L. Evaporation induced two-dimensional buckling within liquid droplet. Appl. Phys. Lett. 95, 223104 (2009)
Deegan, R. D. et al. Capillary flow as the cause of ring stains from dried liquid drops. Nature 389, 827–829 (1997)
Uemura, T., Hirose, Y., Uno, M., Takimiya, K. & Takeya, J. Very high mobility in solution-processed organic thin-film transistors of highly ordered benzothieno[3,2-b]benzothiophene derivatives. Appl. Phys. Expr. 2, 111501 (2009)
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. 20, 3388–3392 (2008)
Pope, M. & Swenberg, C. E. Electronic Processes in Organic Crystals and Polymers 2nd edn, 59–66 (Oxford Science, 1999)
Faltermeier, D., Gompf, B., Dressel, M., Tripathi, A. K. & Pflaum, J. Optical properties of pentacene thin films and single crystals. Phys. Rev. B 74, 125416 (2006)
Ulman, A. An Introduction to Ultrathin Organic Films, from Langmuir-Blodgett to Self-Assembly 1st edn (Academic, 1991)
deMello, A. J. Control and detection of chemical reactions in microfluidic systems. Nature 442, 394–402 (2006)
We are grateful to Nippon Kayaku for providing C8-BTBT. We thank K. Takimiya and S. Horiuchi for discussions, H. Okamoto and H. Matsuzaki for help with optical measurements, K. Kobayashi for help with the X-ray measurements, and T. Iwadate for help with atomic-force microscopy and measurements of device characteristics. The synchrotron X-ray study was performed with the approval of the Photon Factory Program Advisory Committee (no. 2009S2-003). This work was supported by the New Energy and Industrial Technology Development Organization (NEDO) through a Grant for Industrial Technology Research and also by the Japan Society for the Promotion of Science (JSPS) through its Funding Program for World-Leading Innovative R&D on Science and Technology (FIRST Program).
The authors declare no competing financial interests.
The file contains Supplementary text and Supplementary Figures 1-5 with legends. (PDF 1373 kb)
The movie shows a top view of the droplet deposited by the AC-IJP on top of the predefined hydrophilic area containing a protuberance, in which the growth process of single-crystal film can be observed. (MOV 3121 kb)
The movie shows a top view of the droplet deposited by the AC-IJP on top of the predefined hydrophilic area with a rectangle shape, in which the growth process of polycrystalline film can be observed. (MOV 9088 kb)
About this article
Cite this article
Minemawari, H., Yamada, T., Matsui, H. et al. Inkjet printing of single-crystal films. Nature 475, 364–367 (2011) doi:10.1038/nature10313
Transactions on Electrical and Electronic Materials (2020)
In-plane 2-D patterning of microporous layer by inkjet printing for water management of polymer electrolyte fuel cell
Renewable Energy (2020)
Organic Electronics (2020)
High-performance, semiconducting membrane composed of ultrathin, single-crystal organic semiconductors
Proceedings of the National Academy of Sciences (2020)
Dyes and Pigments (2020)