Imide-Functionalized Thiazole-Based Polymer Semiconductors: Synthesis, Structure-Property Correlations, Charge Carrier Polarity, and Thin-Film Transistor Performance

Shi, Yongqiang1,2,3; Guo, Han1,2; Qin, Minchao4; Wan, Yuxi1,2; Zhao, Jiuyang1,2; Sun, Huiliang1,2; Wang, Hang1,2; Wang, Yulun1,2; Zhou, Xin1,2; Facchetti, Antonio5,6; Lu, Xinhui4; Zhou, Ming3; Guo, Xugang1,2

2018-11-13

10.1021/acs.chemmater.8b03670

CHEMISTRY OF MATERIALS   影响因子和分区

0897-4756

1520-5002

Imide-functionalized arenes, exemplified by naphthalene diimides (NDIs), perylene diimides (PDIs), and bithiophene imides (BTIs), are the most promising building blocks for constructing high-performance n-type polymers. In order to reduce the steric hindrance associated with NDI- and PDI-based polymers and to address the high-lying LUMO issue of BTI-based polymers, herein a highly electron-deficient imidefunctionalized bithiazole, N-alky1-5,5 '-bithiazole-4,4 '-dicarboximide (BTzI), was successfully synthesized via an efficient C-H activation. Single crystal of BTzI model compound showed a planar backbone with close pi-stacking distances (3.2-3.3 angstrom). The N,N'-bis (2 -alkyl)-2,2 '-bithiazolethieny1-4,4 ',10,10 '-tetracarboxdiimide (DTzTI) was also used for constructing polymer semiconductors. Compared to DTzTI, BTzI is more electron-deficient, rendering it highly appealing for enabling n-type polymers. On the basis of BTzI and DTzTI, a series of polymers, including acceptor-acceptor homopolymers, and donor-acceptor and donor-acceptor-acceptor copolymers, were synthesized, which feature different contents of acceptor units in polymeric backbones. As imide content increases, the polymer FMO levels were gradually lowered, yielding a transition of charge carrier from ambipolarity to unipolar n-type in organic thin-film transistors (OTFTs). The acceptor-acceptor homopolymer PBTzI possesses the deepest LUMO/HOMO level of -3.94/-6.17 eV, enabling minimal off-current (I-off) of 10(-10)-10(-11) A in OTFTs. The highest electron mobility of 1.61 cm(2) V-1 s(-1) accompanied by small I-off of 10(-10) -10(-11) A and high on-current/off-current ratio (I-on/I-off) of 10(7)-10(8) was achieved from OTFTs using PDTzTI homopolymer, showing the pronounced advantages of acceptor-acceptor homopolymer approach for developing unipolar n-type polymer semiconductors. The correlations between the FMO levels and the transistor performances underscore the significance of FMO tuning for enabling unipolar electron transport. The results demonstrate that imide-functionalized thiazoles are excellent units for constructing high-performance n-type polymers. Moreover, the synthetic routes to these highly electron-deficient imide-functionalized thiazoles and the polymer structure-property correlations developed here are informative for materials invention in organic electronics.

SCI ; EI

英语

第一 ; 通讯

Research Grant Council of Hong Kong[14314216]

Chemistry ; Materials Science

Chemistry, Physical ; Materials Science, Multidisciplinary

WOS:000450696100066

AMER CHEMICAL SOC

20184305986375

Activation analysis ; Amines ; Charge carriers ; Electron transport properties ; Field effect transistors ; Homopolymerization ; Naphthalene ; Organic polymers ; Semiconducting organic compounds ; Single crystals ; Thin film circuits ; Thin films

Electricity: Basic Concepts and Phenomena:701.1 ; Semiconductor Devices and Integrated Circuits:714.2 ; Organic Compounds:804.1 ; Organic Polymers:815.1.1 ; Crystalline Solids:933.1

MATERIALS SCIENCE

Web of Science

1.Southern Univ Sci & Technol SUSTech, Dept Mat Sci & Engn, 1088 Xueyuan Rd, Shenzhen 518055, Guangdong, Peoples R China
2.Southern Univ Sci & Technol SUSTech, Shenzhen Key Lab Printed Organ Elect, 1088 Xueyuan Rd, Shenzhen 518055, Guangdong, Peoples R China
3.Southwest Petr Univ, Sch Mat Sci & Engn, Chengdu 610500, Sichuan, Peoples R China
4.Chinese Univ Hong Kong, Dept Phys, Hong Kong 999077, Hong Kong, Peoples R China
5.Northwestern Univ, Dept Chem, 2145 Sheridan Rd, Evanston, IL 60208 USA
6.Northwestern Univ, Mat Res Ctr, Evanston, IL 60208 USA

Shi, Yongqiang,Guo, Han,Qin, Minchao,et al. Imide-Functionalized Thiazole-Based Polymer Semiconductors: Synthesis, Structure-Property Correlations, Charge Carrier Polarity, and Thin-Film Transistor Performance[J]. CHEMISTRY OF MATERIALS,2018,30(21):7988-8001.

Shi, Yongqiang.,Guo, Han.,Qin, Minchao.,Wan, Yuxi.,Zhao, Jiuyang.,...&Guo, Xugang.(2018).Imide-Functionalized Thiazole-Based Polymer Semiconductors: Synthesis, Structure-Property Correlations, Charge Carrier Polarity, and Thin-Film Transistor Performance.CHEMISTRY OF MATERIALS,30(21),7988-8001.

Shi, Yongqiang,et al."Imide-Functionalized Thiazole-Based Polymer Semiconductors: Synthesis, Structure-Property Correlations, Charge Carrier Polarity, and Thin-Film Transistor Performance".CHEMISTRY OF MATERIALS 30.21(2018):7988-8001.