Abstract
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-dioctyl[1]benzothieno[3,2-b][1]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.
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Acknowledgements
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).
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H. Minemawari was responsible for ink fabrication, inkjet printing, microscopic observations, X-ray diffraction measurements, and measurements of the device characteristics of all the films. T.Y. prepared substrates with the wet/non-wet surface patterning, assisted in inkjet printing and X-ray diffraction measurements, and performed atomic-force microscopy and device characteristics measurements. H. Matsui guided sample preparation and inkjet printing, and conducted DFT molecular orbital calculations. J.T. assisted with X-ray diffraction measurements and performed optical anisotropic absorption measurements. S.H. assisted with optical anisotropic absorption measurements. R.C. assisted in the ink fabrication. R.K. assisted with X-ray diffraction measurements. T.H. conceptualized and directed the research project, and wrote most of the manuscript. All the authors discussed the results and commented on the manuscript.
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Supplementary Information
The file contains Supplementary text and Supplementary Figures 1-5 with legends. (PDF 1373 kb)
Supplementary Movie 1
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)
Supplementary Movie 2
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)
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Minemawari, H., Yamada, T., Matsui, H. et al. Inkjet printing of single-crystal films. Nature 475, 364–367 (2011). https://doi.org/10.1038/nature10313
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DOI: https://doi.org/10.1038/nature10313
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