Materials Design via Optimized Intramolecular Noncovalent Interactions for High-Performance Organic Semiconductors

Guo, Xiaojie1; Liao, Qiaogan1; Manley, Eric F.2,3,5; Wu, Zishan1,6; Wang, Yulun1; Wang, Weida1; Yang, Tingbin1; Shin, Young-Eun4; Cheng, Xing1; Liang, Yongye1; Chen, Lin X.2,3,5; Baeg, Kang-Jun4; Marks, Tobin J.2,3; Guo, Xugang1

2016-04-12

10.1021/acs.chemmater.6b00850

CHEMISTRY OF MATERIALS   影响因子和分区

0897-4756

1520-5002

We report the design, synthesis, and implemention in semiconducting polymers of a novel head-to-head linkage containing the TRTOR (3-alkyl-3'-alkoxy-2,2'-bithiophene) donor subunit having a single strategically optimized, planarizing noncovalent S center dot center dot center dot O interaction. Diverse complementary thermal, optical, electrochemical, X-ray scattering, electrical, photovoltaic, and electron microscopic characterization techniques are applied to establish structure-property correlations in a TRTOR-based polymer series. In comparison to monomers having double S center dot center dot center dot O interactions, replacing one alkoxy substituent with a less electron-donating alkyl one yields TRTOR-based polymers with significantly depressed (0.2-0.3 eV) HOMOs. Furthermore, the weaker single S center dot center dot center dot O interaction and greater TRTOR steric encumberance enhances materials processability without sacrificing backbone planarity. From another perspective, TRTOR has comparable electronic properties to ring-fused 5H-dithieno[3,2-b:2',3'-d]pyran (DTP) subunits, but a centrosymmetric geometry which promotes a more compact and ordered structure than bulkier, axisymmetric DTP. Compared to monosubstituted TTOR (3-alkoxy-2,2'-bithiophene), alkylation at the TRTOR bithiophene 3-position enhances conjugation and polymer crystallinity with contracted pi-pi stacking. Grazing incidence wide-angle X-ray scattering (GIWAXS) data reveal that the greater steric hindrance and the weaker single S center dot center dot center dot O interaction are not detrimental to close packing and high crystallinity. As a proof of materials design, copolymerizing TRTOR with phthalimides yields copolymers with promising thin-film transistor mobility as high as 0.42 cm(2)/(V.s) and 6.3% power conversion efficiency in polymer solar cells, the highest of any phthalimide copolymers reported to date. The depressed TRTOR HOMOs imbue these polymers with substantially increased I-on/I-off ratios and Vac's versus analogous subunits with multiple electron donating, planarizing alkoxy substituents. Implementing a head-to-head linkage with an alkyl/alkoxy substitution pattern and a single S center dot center dot center dot O interaction is a promising strategy for organic electronics materials design.

SCI ; EI

英语

第一 ; 通讯

U.S. DOE[DE-AC02-06CH11357]

Chemistry ; Materials Science

Chemistry, Physical ; Materials Science, Multidisciplinary

WOS:000374196000061

AMER CHEMICAL SOC

20161802341059

Characterization ; Electronic properties ; Ions ; Semiconducting organic compounds ; Semiconducting polymers ; Solar cells ; Thin film transistors ; X ray scattering

Solar Cells:702.3 ; Semiconducting Materials:712.1 ; Compound Semiconducting Materials:712.1.2 ; Semiconductor Devices and Integrated Circuits:714.2 ; High Energy Physics:932.1 ; Materials Science:951

MATERIALS SCIENCE

Web of Science

1.S Univ Sci & Technol China, Dept Mat Sci & Engn, Shenzhen Key Lab Printed Organ Elect, 1088 Xueyuan Rd, Shenzhen 518055, Guangdong, Peoples R China
2.Northwestern Univ, Dept Chem, 2145 Sheridan Rd, Evanston, IL 60208 USA
3.Northwestern Univ, Mat Res Ctr, Argonne Northwestern Solar Energy Res Ctr, 2145 Sheridan Rd, Evanston, IL 60208 USA
4.Pukyong Natl Univ, Dept Graph Arts Informat Engn, 365 Sinseon Ro, Busan 48547, South Korea
5.Argonne Natl Lab, Chem Sci & Engn Div, 9700 S Cass Ave, Argonne, IL 60439 USA
6.Yale Univ, Dept Chem, 225 Prospect St, New Haven, CT 06520 USA

Guo, Xiaojie,Liao, Qiaogan,Manley, Eric F.,et al. Materials Design via Optimized Intramolecular Noncovalent Interactions for High-Performance Organic Semiconductors[J]. CHEMISTRY OF MATERIALS,2016,28(7):2449-2460.

Guo, Xiaojie.,Liao, Qiaogan.,Manley, Eric F..,Wu, Zishan.,Wang, Yulun.,...&Guo, Xugang.(2016).Materials Design via Optimized Intramolecular Noncovalent Interactions for High-Performance Organic Semiconductors.CHEMISTRY OF MATERIALS,28(7),2449-2460.

Guo, Xiaojie,et al."Materials Design via Optimized Intramolecular Noncovalent Interactions for High-Performance Organic Semiconductors".CHEMISTRY OF MATERIALS 28.7(2016):2449-2460.