溶剂蒸汽退火辅助微距升华法制备C8-BTBT单晶

摘要/Abstract

摘要： 有机半导体单晶由于具有内部长程有序的分子排列结构、缺陷及晶界少等优点,表现出优异的光电性能,是实现有机半导体器件实用化的一种重要材料。目前,研究者们已经发展出多种可应用于有机单晶的生长方法,其中,微距升华法是一种可以在大气环境下采用蒸镀的方式制备有机微/纳单晶的方法。然而,当将这种方法应用于C8-BTBT时发现,由于分子的熔点较低,蒸镀得到的是分子直接从液态凝固为无定形/多晶的结构。在本工作中,通过使用溶剂蒸汽退火的方式对其进行后处理,成功地将这种无定形/多晶结构转化为分立的单晶。为了表征所得到的晶体形貌和结构,分别使用光学显微镜、X射线衍射和原子力显微镜等仪器对其进行了表征,发现所制备的晶体结构具备单晶的典型特征。

关键词: 有机单晶, 微距升华法, 溶剂蒸汽退火, 有机半导体, C8-BTBT, 晶体生长

Abstract: Organic semiconductor single crystal has excellent device performance due to its long-range ordered molecular arrangement, few defects and grain boundaries. It is considered as a candidate to realize the practicability of organic semiconductor devices. At present, researchers have developed a variety of methods that can be applied in the growth of organic single crystals. Micro-spacing sublimation is a method to prepare organic micro/nano single crystals by sublimating organic semiconductor molecules onto substrates under ambient conditions. However, when C8-BTBT was treated by this method, amorphous/polycrystalline islands instead of single crystals were obtained due to the low melting point of C8-BTBT. In this work, these amorphous/polycrystalline islands are successfully transformed into discrete single crystals by solvent vapor annealing. The morphology and structure of the obtained crystals were characterized by optical microscope, X-ray diffraction characterization and atomic force microscope. The results show that the prepared crystals have typical characteristics of single crystals.

Key words: organic single crystal, micro-spacing sublimation, solvent vapor annealing, organic semiconductor, C8-BTBT, crystal growth

中图分类号:

史少辉, 方震宇, 汪宏. 溶剂蒸汽退火辅助微距升华法制备C8-BTBT单晶[J]. 人工晶体学报, 2022, 51(1): 42-48.

SHI Shaohui, FANG Zhenyu, WANG Hong. Preparation of C8-BTBT Single Crystals by Solvent Vapor Annealing Assisted Micro-Spacing Sublimation[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2022, 51(1): 42-48.

参考文献

[1] WANG C L, DONG H L, JIANG L, et al. Organic semiconductor crystals[J]. Chemical Society Reviews, 2018, 47(2): 422-500.
[2] CHEN Z, DUAN S M, ZHANG X T, et al. Organic semiconductor crystal engineering for high-resolution layer-controlled 2D crystal arrays[J]. Advanced Materials, 2021: 2104166.
[3] ZHANG Y, DONG H, TANG Q, et al. Organic single-crystalline p-n junction nanoribbons[J]. Journal of the American Chemical Society, 2010, 132(33): 11580-11584.
[4] QIU Y C, ZHAO Y Y, GAO H F, et al. Scalable single-crystalline organic 1D arrays for image sensor[J]. Small, 2021, 17(21): 2100332.
[5] ZHU L N, WANG Z, LU J, et al. Influence of SAM quality on the organic semiconductor thin film gas sensors[J]. Chemical Research in Chinese Universities, 2021: 1-6.
[6] ZHANG X J, DENG W, JIA R F, et al. Precise patterning of organic semiconductor crystals for integrated device applications[J]. Small, 2019, 15(27): 1900332.
[7] ZHANG X J, JIE J S, DENG W, et al. Alignment and patterning of ordered small-molecule organic semiconductor micro-/nanocrystals for device applications[J]. Advanced Materials, 2016, 28(13): 2475-2503.
[8] BRISENO A L, MANNSFELD S C B, LING M M, et al. Patterning organic single-crystal transistor arrays[J]. Nature, 2006, 444(7121): 913-917.
[9] QIAN J, JIANG S, LI S L, et al. Solution-processed 2D molecular crystals: fabrication techniques, transistor applications, and physics[J]. Advanced Materials Technologies, 2019, 4(5): 1800182.
[10] YE X, LIU Y, HAN Q X, et al. Microspacing in-air sublimation growth of organic crystals[J]. Chemistry of Materials, 2018, 30(2): 412-420.
[11] GUO Q, YE X, LIN Q, et al. Microspacing in-air sublimation growth of ultrathin organic single crystals[J]. Chem Mater, 2020: DOI: 10.1021/acs.chemmater.9b05215.
[12] 叶欣,刘阳,陶绪堂.“微距升华”晶体生长方法[J].人工晶体学报,2021,50(1):1-6.
YE X, LIU Y, TAO X T. A crystal growth method: microspacing in-air sublimation[J]. Journal of Synthetic Crystals, 2021, 50(1): 1-6(in Chinese).
[13] PRADEEP V V, MITETELO N, ANNADHASAN M, et al. Ambient pressure sublimation technique provides polymorph-selective perylene nonlinear optical microcavities[J]. Advanced Optical Materials, 2020, 8(1): 1901317.
[14] CAO Q J, LU C R, WANG Q, et al. Micro-spacing in-air sublimation of submillimeter-scaled rubrene nanoribbons and nanosheets for efficient optical waveguides[J]. Organic Electronics, 2020, 87: 105983.
[15] SHEN S, XIA G M, JIANG Z J, et al. Temperature controlling polymorphism and polymorphic interconversion in sublimation crystallization of 5-methoxy-salicylaldhyde azine[J]. Crystal Growth & Design, 2019, 19(1): 320-327.
[16] MOH A M, KHOO P L, SASAKI K, et al. Growth and characteristics of C8-BTBT layer on C-sapphire substrate by thermal evaporation[J]. Physica Status Solidi (a), 2018, 215(11): 1700862.
[17] DICKEY K C, ANTHONY J E, LOO Y L. Improving organic thin-film transistor performance through solvent-vapor annealing of solution-processable triethylsilylethynyl anthradithiophene[J]. Advanced Materials, 2006, 18(13): 1721-1726.
[18] LIU C, KHIM D Y, NOH Y Y. Organic field-effect transistors by a solvent vapor annealing process[J]. Journal of Nanoscience and Nanotechnology, 2014, 14(2): 1476-1493.
[19] WANG H, FONTEIN F, LI J, et al. Lithographical fabrication of organic single-crystal arrays by area-selective growth and solvent vapor annealing[J]. ACS Applied Materials & Interfaces, 2020, 12(43): 48854-48860.
[20] YU S G, JO Y R, KIM M W, et al. Growth kinetics of single crystalline C8-BTBT rods via solvent vapor annealing[J]. The Journal of Physical Chemistry C, 2020, 124(27): 14873-14880.
[21] WANG H, FONTEIN F, WANG Y D, et al. In situ observation of organic single micro-crystal fabrication by solvent vapor annealing[J]. Journal of Materials Chemistry C, 2021, 9(29): 9124-9129.
[22] LYU L, NIU D M, XIE H P, et al. The correlations of the electronic structure and film growth of 2, 7-diocty[1]benzothieno[3, 2-b]benzothiophene (C8-BTBT) on SiO₂[J]. Physical Chemistry Chemical Physics, 2017, 19(2): 1669-1676.
[23] SOEDA J, HIROSE Y, YAMAGISHI M, et al. Solution-crystallized organic field-effect transistors with charge-acceptor layers: high-mobility and low-threshold-voltage operation in air[J]. Advanced Materials, 2011, 23(29): 3309-3314.