一种新型三苯胺类空穴传输材料的合成与性能研究

摘要以2，7-二碘-9，9-二甲基芴为原料分别经过Buchwald-Hartwig交叉偶联反应、Ullmann反应，对目标化合物9，9-二甲基N2，N7二苯基N2，N7二-对甲苯基-9H-芴-2，7-二胺（d-TPA）进行合成研究。通过¹H NMR、¹³C NMR以及HRMS-ESI等表征方法确定结构的正确性。研究表明：以铜粉为催化剂的Ullmann反应收率为85%，是最高效的合成方法。通过X射线衍射（XRD）测试和循环伏安法（CV）测试，结果表明：该材料为非晶材料，成膜性较好，且目标化合物的HOMO轨道能级值为-5.23 eV，与常用阳极材料ITO功函相近且化学稳定性较好，有利于空穴由阳极向空穴传输层的注入。将目标化合物用作空穴传输材料制备了有机发光二级管（OLED）并进行性能测试表征，结果显示：所得器件的启亮电压为3.8 V，最大发光亮度为21 412 cd/m²，最大电流效率为4.78 cd/A，表明该化合物有望成为一种性能优异的新型空穴传输材料。

	Service

	把本文推荐给朋友
	加入我的书架
	加入引用管理器
	Email Alert
	RSS
	作者相关文章
	张松林
	李巍
	冯文慧
	汪天洋
	刘东志
	周雪琴

关键词：三苯胺合成 Ullmann反应非晶材料 OLED 空穴传输材料

Abstract： Using 2,7-diiodo-9,9-dimethylindole as starting material, the Buchwald-Hartwig cross-coupling reaction and Ullmann reaction were used to obtain the target compound 9,9-dimethyl-N2, N7-diphenyl-N2, N7-di-P-tolyl-9H-fluorene-2,7-diamine(d-TPA). The elucidation of chemical structure was proved by ¹H NMR, ¹³C NMR and HRMS-ESI. It is shown that the Ullmann reaction with copper powder as the catalyst is the most efficient synthetic method (yield 85%). From the results of X-ray diffraction (XRD) and cyclic voltammetry (CV), the material was amorphous and has the ability to form a good thin film. And the compound has a highest occupied molecular orbit (HOMO) energy level of -5.23 eV, which is similar to the common anode material ITO work function and has good chemical stability, which is beneficial for the injection of hole carriers to the counter electrode. Organic lighting-emitting diodes (OLED) using the compound as hole transport material was prepared and characterized. The results show that the device has a light-emitting voltage of 3.8 V, a maximum luminance of 21 412 cd/m² and a maximum current efficiency of 4.78 cd/A. From the results, it has been proved that the compound is expected to be a novel hole transport material with excellent performance.

Keywords： triphenylamine； synthesis； Ullmann reaction； amorphous material； OLED； hole transport material

Received 2019-05-20;

Fund:国家自然科学基金资助（21776207和21576195）。

Corresponding Authors: 周雪琴,E-mail:zhouxueqin@tju.edu.cn。 Email: zhouxueqin@tju.edu.cn

About author: 张松林(1992-),男,硕士研究生,主要研究方向为有机光电功能材料。

引用本文:

张松林, 李巍, 冯文慧, 汪天洋, 刘东志, 周雪琴.一种新型三苯胺类空穴传输材料的合成与性能研究[J]. 化学工业与工程, 2020,37(3): 23-30

Zhang Songlin, Li Wei, Feng Wenhui, Wang Tianyang, Liu Dongzhi, Zhou Xueqin.Synthesis and Properties of a Novel Triphenylamine Hole Transport Material[J]. Chemcial Industry and Engineering, 2020,37(3): 23-30

[1] Yang X, Wang H, Cai B, et al. Progress in hole-transporting materials for perovskite solar cells[J]. Journal of Energy Chemistry, 2018, 27(3):650-672
[2] Zhao X, Wang M. Organic hole-transporting materials for efficient perovskite solar cells[J]. Materials Today Energy, 2018, 7:208-220
[3] Bakr Z H, Wali Q, Fakharuddin A, et al. Advances in hole transport materials engineering for stable and efficient perovskite solar cells[J]. Nano Energy, 2017, 34:271-305
[4] Xiang N, Gao Z, Tian G, et al. Novel fluorene/indole-based hole transport materials with high thermal stability for efficient OLEDs[J]. Dyes and Pigments, 2017, 137:36-42
[5] Krucaite G, Volyniuk D, Simokaitiene J, et al. Naphthyl substituted triphenylamine derivatives as hole transporting materials for efficient red PhOLEDs[J]. Dyes and Pigments, 2019, 162:196-202
[6] Matebese F, Taziwa R, Mutukwa D. Progress on the synthesis and application of CuSCN inorganic hole transport material in perovskite solar cells[J]. Materials, 2018, doi:10.3390/ma11122592
[7] Rodriguez-Seco C, Cabau L, Vidal-Ferran A, et al. Advances in the synthesis of small molecules as hole transport materials for lead halide perovskite solar cells[J]. Accounts of Chemical Research, 2018, 51(4):869-880
[8] Zhang J, He Y, Min J. Recent progress in hybrid perovskite solar cells based on p-type small molecules as hole transporting materials[J]. Acta Physico-Chimica Sinca, 2018, 34(11):1221-1238
[9] 李园园, 张月, 王丽. 钙钛矿太阳能电池中空穴传输材料的研究进展[J]. 河南大学学报:自然科学版, 2017, 47(4):434-452 Li Yuanyuan, Zhang Yue, Wang Li. Research progress on hole transport materials for perovskite solar cells[J]. Journal of Henan University:Natural Science, 2017, 47(4):434-452(in Chinese)
[10] Liu X, Shi X, Liu C, et al. A simple carbazole-triphenylamine hole transport material for perovskite solar cells[J]. The Journal of Physical Chemistry C, 2018, 122(46):26337-26343
[11] Wu Y, Wang Z, Liang M, et al. Influence of nonfused cores on the photovoltaic performance of linear triphenylamine-based hole-transporting materials for perovskite solar cells[J]. ACS Applied Materials & Interfaces, 2018, 10(21):17883-17895
[12] Pina J, Seixas de Melo J S, Batista R M F, et al. Triphenylamine-benzimidazole derivatives:Synthesis, excited-state characterization, and DFT studies[J]. The Journal of Organic Chemistry, 2013, 78(22):11389-11395
[13] 姜姗姗. 含芴环化合物的合成及光学性能研究[D]. 太原:山西大学, 2011 Jiang Shanshan. Synthesis and optical performance of compound containing fluorene-based[D]. Taiyuan:Shanxi University, 2011(in Chinese)
[14] 李伟杰, 刘彬, 孙明礼. 4,5-二氮杂芴光电材料的合成及薄膜器件的应用[J]. 南京邮电大学学报:自然科学版, 2013, 33(5):1673-5439 Li Weijie, Liu Bin, Sun Mingli. The synthesis, properties and thin film device applications for 4,5-diazafluorene derivatives[J]. Journal of Nanjing University of Posts and Telecommunications:Natural Science, 2013, 33(5):1673-5439(in Chinese)
[15] 罗炫, 常冠军, 张林, 等. 含芴聚亚胺酮的合成与表征[J]. 合成化学, 2009, 17(1):15-18 Luo Xuan, Chang Guanjun, Zhang Lin, et al. Synthesis and characterization of fluorene-polyimine ketones[J]. Chinese Journal of Synthetic Chemistry, 2009, 17(1):15-18(in Chinese)
[16] Okumoto K, Shirota Y. Development of new hole-transporting amorphous molecular materials for organic electroluminescent devices and their charge-transport properties[J]. Materials Science and Engineering:B, 2001, 85(2/3):135-139
[17] Zhang J, Xu B, Johansson M B, et al. Constructive effects of alkyl chains:A strategy to design simple and non-spiro hole transporting materials for high-efficiency mixed-ion perovskite solar cells[J]. Advanced Energy Materials, 2016, doi:10.1002/aenm.201502536
[18] Tan C, Feng R, Peng X. Synthesis and electrochemical properties of 2, 6-bis(6-aryl-[1, 2, 4]-triazolo[3, 4-b] [1, 3, 4]-thiadiazole-3-yl)pyridines[J]. Chinese Chemical Letters, 2007, 18(5):505-508
[19] Yang Z, Xu B, He J, et al. Solution-Processable and thermal-stable triphenylamine-based dendrimers with truxene cores as hole-transporting materials for organic light-emitting devices[J]. Organic Electronics, 2009, 10(5):954-959
[20] Thesen M W, Krueger H, Janietz S, et al. Investigation of spacer influences in phosphorescent-emitting nonconjugated PLED systems[J]. Journal of Polymer Science Part A:Polymer Chemistry, 2010, 48(2):389-402
[21] 李英俊, 赵楠, 李丽娜, 等. 结构不对称三芳胺类化合物的合成、表征及性质研究[J]. 有机化学, 2012, 32(5):949-952 Li Yingjun, Zhao Nan, Li Lina, et al. Synthesis, characterization and properties of some novel structural asymmetric triarylamines[J]. Chinese Journal of Organic Chemistry, 2012, 32(5):949-952(in Chinese)