化学学报 ›› 2015, Vol. 73 ›› Issue (1): 23-28.DOI: 10.6023/A14110806 上一篇    下一篇

研究论文

溶剂蒸汽退火法制备有机小分子半导体单晶

吴君辉, 袁艺, 高明圆, 王哲, 江雷   

  1. 北京航空航天大学 化学与环境学院 北京 100191
  • 投稿日期:2014-11-22 发布日期:2015-01-08
  • 通讯作者: 王哲 E-mail:wangzhe@buaa.edu.cn
  • 基金资助:

    项目受国家自然科学基金(Nos. 21174008, 51273009)和973 计划(No. 2013CB933000)资助.

Preparation of Single Crystals of Small Molecule Organic Semiconductor via Solvent Vapor Annealing

Wu Junhui, Yuan Yi, Gao Mingyuan, Wang Zhe, Jiang Lei   

  1. School of Chemistry and Environment, BeiHang University, Beijing 100191, China
  • Received:2014-11-22 Published:2015-01-08
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos. 21174008, 51273009) and the 973 Program (No. 2013CB933000).

溶剂蒸汽退火(Solvent Vapor Annealing, SVA)是一种经济高效的小分子半导体晶体生长制备方法. 本工作通过该方法制备出了多种小分子有机半导体单晶, 通过偏光显微镜, XRD, TEM 和 AFM对得到的单晶的形貌和晶体结构进行了表征. 此外, 我们对退火所用溶剂的溶解度、蒸汽退火的环境温度和聚合物介质的引入等影响因素进行了讨论. 研究发现, SVA过程中随着退火溶剂对有机半导体的溶解度增大, 得到的晶体尺寸也随之增大; 此外, 当退火温度升高, 晶体生长速度加快, 但当温度接近溶剂蒸汽的沸点时, 晶体极易产生缺陷; 聚合物的引入可以大大促进SVA进程, 并且生长得到的有机半导体单晶缺陷更少, 尺寸更大.

关键词: 有机半导体, 单晶, 溶剂蒸汽退火

Solvent vapor annealing (SVA) is a solution-assisted method which is economical and efficient to improve crystallinity in organic molecular thin films. By exposing thin films of organic semiconductors (OSCs) to an environment saturated with solvent vapors, the OSC molecules will reorganize in a higher degree of order. Here, single crystals of anthracene, TIPS-PEN (6,13-bis(triisopropylsilylethynyl) pentacene) and rubrene are grown using this method from their spun coated films. After obtaining the OSC single crystals, polarized optical microscopy (POM), X-ray diffraction (XRD), selected area electron diffraction (SAED) and atomic force microscopy (AFM) are used to characterize the morphologies and crystalline structures of the crystals. The influence factors such as solvent, temperature and the polymer medium are discussed. The solubility of the annealing solvent plays a significant role in the growth of OSC crystals during SVA. The higher the solubility of the solvent, the easier to acquire large size single crystals. Among the three solvents we used, chloroform is the most suitable solvent for anthracene film to generate single crystals as anthracene is more soluble in chloroform than in other two solutions. Moreover, with the increasing of the temperature, the crystals grow faster, but when approaching the boiling point of the solvent, the crystals will get more defects. We find that the yielded crystals in 45 ℃ are large in size and with fewer defects. That temperature is the optimum temperature in this system for SVA. When mixed with polymer, the SVA process will be improved greatly, and we can get large-size and high-quality OSC single crystals. First, we consider the substrate is modified by the polymer. This modifying of the interface makes OSC molecules easier to migrate, thus will enhance the growth of crystals. At the same time, with the solvent vapor absorbed, the added polymer can also act as a solvent with lower solubility during SVA, which provides a mild environment for OSC molecules to nucleate and grow.

Key words: organic semiconductors, single crystals, solvent vapor annealing