### 含杂原子的并五苯类似物合成及场效应性能研究

1. a 中国科学院化学研究所有机固体实验室 北京 100190;
b 北京科技大学材料与工程学院 北京 100083
• 投稿日期:2012-04-23 发布日期:2012-05-16
• 通讯作者: 于贵, 刘云圻 E-mail:yugui@iccas.ac.cn; liuyq@iccas.ac.cn
• 基金资助:

项目受国家自然科学基金(Nos. 20825208, 21021091)资助.

### Synthesis of Pentacene Analogues Containing Heteroatoms and Study of Their Field-effect Performance

Zhu Minlianga, Luo Haoa,b, Wang Lipingb, Yu Guia, Liu Yunqia

1. a Laboratory of Organic Solids, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China;
b School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China
• Received:2012-04-23 Published:2012-05-16
• Supported by:

Project supported by the National Natural Science Foundation of China (Nos. 20825208, 21021091)

N,N'-二苯基-1,4-苯二胺为原料, 合成了含硫和氮杂原子的并五苯类似物, 用可见-紫外吸收光谱和电化学测试对这类化合物进行表征, 确定了其光学带隙及轨道能级, 与并五苯相比它们具有低的最高占用分子轨道能级. 得到了三苯并二噻嗪的单晶结构, 分子具有平面结构, 分子间具有强的π…π相互作用和N…S相互作用. 首次将该类并五苯类似物应用于有机薄膜场效应晶体管中, 器件显示好的场效应特性, 迁移率为0.01 cm2·V-1·s-1.

Pentacene analogues containing nitrogen and sulfur heteroatoms were synthesized using N,N'-diphenylbenzene- 1,4-diamine as a starting material. Ring-closing reaction of N,N'-diphenylbenzene-1,4-diamine with sulfur powder resulted in formation of [1,4]benzothiazino[2,3-b]phenothiazine (compound 1). Catalytic amounts of iodine and reflux temperature of o-dichlorobenzene were necessary. 3H,10aH-[1,4]Benzothiazino[2,3-b]phenothiazine (compound 2) were obtained by oxidization and dehydrogenation of compound 1. The compounds 1 and 2 were purified by vacuum sublimation and characterized by UV-vis absorption spectra and cyclic voltammetry. Their optical energy gaps, energy levels of highest occupied molecular orbitals (HOMOs), and the lowest unoccupied ones were calculated. The HOMO energy levels of the compounds 1 and 2 are -5.85 and -5.42 eV, respectively. The absorption spectra of the compound 2 in thin film shows an obvious red-shift compared with that in CH2Cl2 solution, which indicates strong molecular interactions in thin film. Moreover, the crystal structure of the compound 2 was obtained and it has a planar structure. Strong π…π and N…S interactions between adjacent molecules were observed. However, there is no S…S, CH…π interactions, or hydrogen bond, which leads to no OFET performance of the compound 2. Organic field-effect transistors (OFETs) were fabricated using compound 1 as a semiconducting layer. Bottom-gate and top-contact OFET devices were fabricated by vacuum deposition on polystyrene (PS) or octadecyltrichlorosilane (OTS)-treated SiO2/Si substrates. The OFET devices fabricated on OTS-treated SiO2/Si substrates showed a good field-effect performance with a mobility of 0.01 cm2·V-1·s-1 and a current on/off ratio of 6.6×103. However, the OFET devices fabricated on the PS modified SiO2/Si substrates exhibited a lower mobility of 2.5×10-3 cm2·V-1·s-1. AFM images were used to understand field-effect performance of the OFET devices fabricated on PS or OTS-treated SiO2/Si substrates. All OFET devices were tested under air. A higher field-effect performance of the pentacene analogues semiconductor could likely be achieved through proper control in functional group and device fabrication.