核扩展萘二酰亚胺-插烯四硫富瓦烯衍生物的设计合成与性能研究  

Design,Synthesis and Property Study of aπ-Expanded Naphthalene Diimide-Vinylogous Tetrathiafulvalene Derivative

作　　者：何萌萌 张瑞 谢玉龙 葛从伍 高希珂[2] He Mengmeng;Zhang Rui;Xie Yulong;Ge Congwu;Gao Xike(College of Chemistry and Materials Science,Sichuan Normal University,Chengdu 610066;State Key Laboratory of Organometallic Chemistry,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,Shanghai 200032;School of Chemistry and Materials Science,University of Science and Technology of China,Hefei 230026)

机构地区：[1]四川师范大学化学与材料科学学院,成都610066 [2]中国科学院上海有机化学研究所、金属有机化学国家重点实验室,上海200032 [3]中国科学技术大学化学与材料科学学院,合肥230026

出　　处：《化学学报》2024年第9期954-961,共8页Acta Chimica Sinica

基　　金：国家自然科学基金(No.22225506);中国科学院战略性先导科技专项B类(No.XDB0520101);上海市启明星计划(21QA1411100);中国科学院青年创新促进会(No.2022252)资助项目.

摘　　要：与p-型有机场效应晶体管(OFET)相比,目前n-型OFET仍面临器件性能低及稳定性差等问题.利用萘二酰亚胺(NDI)核π-扩展策略,设计合成了邻苯二硫酚取代的萘二酰亚胺-插烯四硫富瓦烯衍生物(BDTNDI-DTYA)2,通过溶液旋涂成膜法制备了基于(BDTNDI-DTYA)2的底栅顶接触结构的OFET器件.研究结果表明(BDTNDI-DTYA)2表现出n-型半导体特性,其薄膜未经处理时器件的平均电子迁移率为0.04 cm^(2)•V^(-1)•s^(-1),以热退火(160℃)和添加剂(薁)升华两种方式分别对(BDTNDI-DTYA)2的薄膜进行处理后,薄膜器件的平均电子迁移率分别提升至1.00和0.98 cm^(2)•V^(-1)•s^(-1).研究表明OFET器件性能的显著提升均得益于薄膜结晶性的提高和形貌的改善.设计合成了高性能的n-型有机半导体材料(BDTNDI-DTYA)2,并以薁为调节剂对OFET的活性层结构形貌进行了有效调控,为有机半导体材料的设计合成及其OFET器件性能的提升提供了新思路.Organic field-effect transistors(OFETs)is the basic unit of complementary logic circuit,however,the development of n-type OFETs lags behind of p-type ones due to the barrier of electron injection and the interference from oxygen and water,which hinders the development of complementary logic circuit.Therefore,the design and synthesis of high-performance n-type organic semiconductors and the improvement of device performance and stability have important scientific significance.In this work,a novel naphthalene diimide(NDI)-vinylogous tetrathiafulvalene derivative(BDTNDIDTYA)2 was designed and synthesized via aπ-expanded strategy by fusing the benzene-1,2-dithiol(BDT)and 2-(1,3-dithiol-2-ylidene)acetonitrile(DTYA)moieties onto the NDI core.The chemical structure of the compound was characterized by 1H NMR,13C NMR,Fourier transform infrared spectroscopy(FT-IR)and high-resolution mass spectrometry(HRMS).The thermal,optical and electrochemical properties of(BDTNDI-DTYA)2 were characterized by differential scanning calorimetry(DSC),thermogravimetric analysis(TGA),ultraviolet-visible(UV-Vis)absorption spectra and cyclic voltammetry(CV).The energy levels of the highest occupied molecular orbital(HOMO)and the lowest unoccupied molecular orbital(LUMO)of(BDTNDI-DTYA)2 calculated from CV were-5.66 and-4.01 eV,respectively.The edge absorption of(BDTNDI-DTYA)2 in thin film showed obvious red-shift(68 nm)relative to that in CHCl3 solution,indicating strong intermolecular interactions in solid state.The bottom-gate and top-contact(BGTC)OFETs based on(BDTNDI-DTYA)2 fabricated by spin-coating method,showed n-type electron transporting characteristics.The average electron mobility of the untreated devices was 0.04 cm^(2)•V^(-1)•s^(-1)when measured in nitrogen atmosphere and was increased of up to 1.00 cm^(2)•V^(-1)•s^(-1)when the thin films of(BDTNDI-DTYA)2 were thermal annealed at 160℃.On the other hand,azulene was used as an additive to treat the thin films of(BDTNDI-DTYA)2 via sublimation,the average electron mobility o

关 键 词：萘二酰亚胺 n-型有机场效应晶体管 电子迁移率 结构-性能关系 添加剂 

分 类 号：TB322[一般工业技术—材料科学与工程] TN386[电子电信—物理电子学]