Abstract
A series of copolymers of thiazoloisoindigo (TzII) with different chalcogenophene trimers were synthesized to systematically investigate the chalcogen effect on their charge transport properties. When only the middle thiophene ring of terthiphene (T-T-T) is replaced by heavier chalcogenophenes, a preference (expressed by the ratio of μe/μh) towards electron transport was observed descending from T-T-T to T-Se-T then to T-Te-T (Se and Te stand for selenophene and tellurophene, respectively). On the other hand, with the increased number of heavier chalcogenophenes, a preference toward hole transport was observed descending from Se-T-Se to Se-Se-Se then to Se-Te-Se. This phenomenon is well-explained by the balance between the aromatic resonance energy of the chalcogenophenes and the electronegativity of the chalcogens. Specifically, P(TzII-T-Se-T) displayed relatively balanced ambipolar property (μhmax and μemax of 3.77 and 1.59 cm2·V−1·s−1 with a μe/μh of 0.42), while P(Tzll-Se-Te-Se) exhibited the best preference to hole transfer with a μe/μh of 0.09. P(Tzll-T-Te-T) exhibited the best preference to electron transfer with a μe/μh, of 16 and the μemax of 0.64 cm2·V−1·s−1 which is the highest electron mobility among the known conjugated polymers containing tellurophenes.
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References
Planells, M.; Schroeder, B. C.; McCulloch, I. Effect of chalcogen atom substitution on the optoelectronic properties in cyclopentadithiophene polymers. Macromolecules 2014, 47, 5889–5894.
Lee, J.; Han, A. R.; Kim, J.; Kim, Y.; Oh, J. H.; Yang, C. Solution-processable ambipolar diketopyrrolopyrrole-selenophene polymer with unprecedentedly high hole and electron mobilities. J. Am. Chem. Soc. 2012, 134, 20713–20721.
Hendriks, K. H.; Li, W.; Wienk, M. M.; Janssen, R. A. J. Small-bandgap semiconducting polymers with high near-infrared photoresponse. J. Am. Chem. Soc. 2014, 136, 12130–12136.
Chen, Z.; Lemke, H.; Albert-Seifried, S.; Caironi, M.; Nielsen, M. M.; Heeney, M.; Zhang, W.; McCulloch, I.; Sirringhaus, H. High mobility ambipolar charge transport in polyselenophene conjugated polymers. Adv. Mater. 2012, 22, 2371–2375.
Kim, Y. M.; Lim, E.; Kang, I. N.; Jung, B. J.; Lee, J.; Koo, B. W.; Do, L. M.; Shim, H. K. Solution-processable field-effect transistor using a fluorene- and selenophene-based copolymer as an active layer. Macromolecules 2006, 39, 4081–4085.
Kong, H.; Chung, D. S.; Kang, I. N.; Park, J. H.; Park, M. J.; Jung, I. H.; Park, C. E.; Shim, H. K. New selenophene-based semiconducting copolymers for high performance organic thin-film transistors. J. Mater. Chem. 2009, 19, 3490–3499.
Al-Hashimi, M.; Han, Y.; Smith, J.; Bazzi, H. S.; Alqaradawi, S. Y. A.; Watkins, S. E.; Anthopoulos, T. D.; Heeney, M. Influence of the heteroatom on the optoelectronic properties and transistor performance of soluble thiophene-, selenophene- and tellurophene-vinylene copolymers. Chem. Sci. 2016, 7, 1093–1099.
Huang, F. B. Z. S.; Geng, Y. H.; Wang, X. H.; Wang, L. X.; Ma, Y. G.; Hou, J. H.; Hu, W. P.; Pei, J.; Dong, H. L.; Wang, S.; Li, Z.; Shuai, Z. G.; Li, Y. F.; Cao, Y. Study on optoelectronic polymers: an overview and outlook. Acta Polymerica Sinica (in Chinese) 2019, 50, 988–1046.
Ni, Z.; Dong, H.; Wang, H.; Ding, S.; Zou, Y.; Zhao, Q.; Zhen, Y.; Liu, F.; Jiang, L.; Hu, W. Quinoline-flanked diketopyrrolopyrrole copolymers breaking through electron mobility over 6 cm2·V−1·s−1 in flexible thin film devices. Adv. Mater. 2018, 350, 1704843.
Ni, Z.; Wang, H.; Dong, H.; Dang, Y.; Zhao, Q.; Zhang, X.; Hu, W. Mesopolymer synthesis by ligand-modulated direct arylation polycondensation towards n-type and ambipolar conjugated systems. Nat. Chem. 2019, 11, 271–277.
Ni, Z.; Wang, H.; Zhao, Q.; Zhang, J.; Wei, Z.; Dong, H.; Hu, W. Ambipolar conjugated polymers with ultrahigh balanced hole and electron mobility for printed organic complementary logic via a two-step CH activation strategy. Adv. Mater. 2019, 31, 1806010.
Yang, J.; Zhao, Z.; Wang, S.; Guo, Y.; Liu, Y. Insight into high-performance conjugated polymers for organic field-effect transistors. Chem 2018, 4, 2748–2785.
Sung, M. J.; Luzio, A.; Park, W. T.; Kim, R.; Gann, E.; Maddalena, F.; Pace, G.; Xu, Y.; Natali, D.; de Falco, C.; Dang, L.; McNeill, C. R.; Caironi, M.; Noh, Y. Y.; Kim, Y. H. High-mobility naphthalene diimide and selenophene-vinylene-selenophene-based conjugated polymer: n-channel organic field-effect transistors and structure-property relationship. Adv. Fcnat. Mater. 2016, 26, 4984–4997.
Zhao, Z.; Yin, Z.; Chen, H.; Zheng, L.; Zhu, C.; Zhang, L.; Tan, S.; Wang, H.; Guo, Y.; Tang, Q.; Liu, Y. High-performance, air-stable field-effect transistors based on heteroatom-substituted naphthalenediimide-benzothiadiazole copolymers exhibiting ultrahigh electron mobility up to 8.5 cm2·V−1·s−1. Adv. Mater. 2017, 29, 1602410.
Yang, L.; Gu, W.; Lv, L.; Chen, Y.; Yang, Y.; Ye, P.; Wu, J.; Hong, L.; Peng, A.; Huang, H. Triplet tellurophene-based acceptors for organic solar cells. Angew. Chem. Int. Ed. 2018, 54, 1096–1102.
Jung, E. H.; Bae, S.; Yoo, T. W.; Jo, W. H. The effect of different chalcogenophenes in isoindigo-based conjugated copolymers on photovoltaic properties. Polym. Chem. 2014, 5, 6545–6550.
Park, K. H.; Cheon, K. H.; Lee, Y. J.; Chung, D. S.; Kwon, S. K.; Kim, Y. H. Isoindigo-based polymer field-effect transistors: effects of selenophene-substitution on high charge carrier mobility. Chem. Commun. 2015, 51, 8120–8122.
Kang, I.; Yun, H. J.; Chung, D. S.; Kwon, S. K.; Kim, Y. H. Record high hole mobility in polymer semiconductors via side-chain engineering. J. Am. Chem. Soc. 2013, 135, 14896–14899.
Kim, K. H.; Park, S.; Yu, H.; Kang, H.; Song, I.; Oh, J. H.; Kim, B. J. Determining optimal crystallinity of diketopyrrolopyrrole-based terpolymers for highly efficient polymer solar cells and transistors. Chem. Mater. 2014, 26, 6963–6970.
Kaur, M.; Yang, D. S.; Shin, J.; Lee, T. W.; Choi, K.; Cho, M. J.; Choi, D. H. A novel tellurophene-containing conjugated polymer with a dithiophenyl diketopyrrolopyrrole unit for use in organic thin film transistors. Chem. Commun. 2013, 49, 5495–5497.
Kaur, M.; Lee, D. H.; Yang, D. S.; Um, H. A.; Cho, M. J.; Kang, J. S.; Choi, D. H. Diketopyrrolopyrrole-bitellurophene containing a conjugated polymer and its high performance thin-film transistor sensor for bromine detection. Chem. Commun. 2014, 55, 14394–14396.
Ashraf, R. S.; Meager, I.; Nikolka, M.; Kirkus, M.; Planells, M.; Schroeder, B. C.; Holliday, S.; Hurhangee, M.; Nielsen, C. B.; Sirringhaus, H.; McCulloch, I. Chalcogenophene comonomer comparison in small band gap diketopyrrolopyrrole-based conjugated polymers for high-performing field-effect transistors and organic solar cells. J. Am. Chem. Soc. 2015, 137, 1314–1321.
Shi, L.; Guo, Y.; Hu, W.; Liu, Y. Design and effective synthesis methods for high-performance polymer semiconductors in organic field-effect transistors. Mater. Chem. Front. 2017, 1, 2423–2456.
Quinn, J. T. E.; Zhu, J.; Li, X.; Wang, J.; Li, Y. Recent progress in the development of n-type organic semiconductors for organic field effect transistors. J. Mater. Chem. C 2017, 5, 8654–8681.
Wang, E. G.; Mammo, W.; Andersson, M. R. 25th Anniversary article: isoindigo- based polymers and small molecules for bulk heterojunction solar cells and field effect transistors. Adv. Mater. 2014, 26, 1801–1826.
Lei, T.; Wang, J. Y.; Pei, J. Design, synthesis, and structure-property relationships of isoindigo-based conjugated polymers. Acc. Chem. Res. 2014, 47, 1117–1126.
Lei, T.; Dou, J. H.; Ma, Z. J.; Yao, C. H.; Liu, C. J.; Wang, J. Y.; Pei, J. Ambipolar polymer field-effect transistors based on fluorinated isoindigo: high performance and improved ambient stability. J. Am. Chem. Soc. 2012, 134, 20025–8.
Kim, G.; Kang, S. J.; Dutta, G. K.; Han, Y. K.; Shin, T. J.; Noh, Y. Y.; Yang, C. A Thienoisoindigo-naphthalene polymer with ultrahigh mobility of 14.4 cm2/V·s that substantially exceeds benchmark values for amorphous silicon semiconductors. J. Am. Chem. Soc. 2014, 136, 9477–9483.
Huang, J.; Mao, Z.; Chen, Z.; Gao, D.; Wei, C.; Zhang, W.; Yu, G. Diazaisoindigo-based polymers with high-performance charge-transport properties: from computational screening to experimental characterization. Chem. Mater. 2016, 28, 2209–2218.
Lin, H. W.; Lee, W. Y.; Chen, W. C. Selenophene-DPP donor-acceptor conjugated polymer for high performance ambipolar field effect transistor and nonvolatile memory applications. J. Mater. Chem. 2012, 22, 2120–2128.
Wang, Z.; Liu, Z.; Ning, L.; Xiao, M.; Yi, Y.; Cai, Z.; Sadhanala, A.; Zhang, G.; Chen, W.; Sirringhaus, H.; Zhang, D. Charge mobility enhancement for conjugated DPP-selenophene polymer by simply replacing one bulky branching alkyl chain with linear one at each DPP unit. Chem. Mater. 2018, 39, 3090–3100.
Back, J. Y.; Yu, H.; Song, I.; Kang, I.; Ahn, H.; Shin, T. J.; Kwon, S. K.; Oh, J. H.; Kim, Y. H. Investigation of structure-property relationships in diketopyrrolopyrrole-based polymer semiconductors via side-chain engineering. Chem. Mater. 2015, 27, 1732–1739.
Han, A. R.; Dutta, G. K.; Lee, J.; Lee, H. R.; Lee, S. M.; Ahn, H.; Shin, T. J.; Oh, J. H.; Yang, C. ε-Branched flexible side chain substituted diketopyrrolopyrrole-containing polymers designed for high hole and electron mobilities. Adv. Funct. Mater. 0015, 55, 247–254.
Um, H. A.; Lee, D. H.; Heo, D. U.; Yang, D. S.; Shin, J.; Baik, H.; Cho, M. J.; Choi, D. H. High aspect ratio conjugated polymer nanowires for high performance field-effect transistors and phototransistors. ACS Nano 2015, 9, 5264–5274.
Khim, D.; Cheon, Y. R.; Xu, Y.; Park, W. T.; Kwon, S. K.; Noh, Y. Y.; Kim, Y. H. Facile route to control the ambipolar transport in semiconducting polymers. Chem. Mater. 2016, 28, 2287–2294.
Lei, T.; Cao, Y.; Zhou, X.; Peng, Y.; Bian, J.; Pei, J. Systematic investigation of isoindigo-based polymeric field-effect transistors: design strategy and impact of polymer symmetry and backbone curvature. Chem. Mater. 2012, 24, 1762–1770.
Huang, J.; Chen, Z.; Mao, Z.; Gao, D.; Wei, C.; Lin, Z.; Li, H.; Wang, L.; Zhang, W.; Yu, G. Tuning frontier orbital energetics of azaisoindigo-based polymeric semiconductors to enhance the charge-transport properties. Adv. Electron. Mater. 2017, 3, 1700078.
Wood, S.; Wade, J.; Shahid, M.; Collado-Fregoso, E.; Bradley, D. D. C.; Durrant, J. R.; Heeney, M.; Kim, J. S. Natures of optical absorption transitions and excitation energy dependent photostability of diketopyrrolopyrrole (DPP)-based photovoltaic copolymers. Energ. Environ. Sci. 2015, 8, 3222–3232.
Lee, T. W.; Lee, D. H.; Shin, J.; Cho, M. J.; Choi, D. H. π-Conjugated polymers derived from 2,5-bis-(2-decyltetradecyl)-3,6-di(selenophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione for high-performance thin film transistors. Polym. Chem. 2015, 6, 1777–1785.
Li, C.; Zhang, H.; Mirie, S.; Peng, J.; Cai, M.; Wang, X.; Lan, Z.; Wan, X. A new approach to thiazoloisoindigo and derivatives using a lithium tetramethylpiperidine promoted cyclization to thiazoloisatin. Org. Chem. Front. 2018, 5, 442–446.
Li, C.; Un, H. I.; Peng, J.; Cai, M.; Wang, X.; Wang, J.; Lan, Z.; Pei, J.; Wan, X. Thiazoloisoindigo: a building block that merges the merits of thienoisoindigo and diazaisoindigo for conjugated polymers. Chem. Eur. J. 2018, 24, 9807–9811.
Bredas, J. L. Mind the gap! Mater. Horiz. 2014, 1, 17–19.
Vessally, E. Aromatic stability energy studies on five-membered heterocyclic C4H4M (M = O, S, Se, Te, NH, PH, AsH and SbH): DFT calculations. J. Struct. Chem. 2008, 49, 979–985.
Acknowledgments
We thank the research financial support from the National Natural Science Foundation of China (Nos. 22075105 and 51573204) and National Science Foundation of Shandong Province (No. ZR2018ZB0315). H. Zhang thanks the financial support from the National Natural Science Foundation of China (No. 51803230). Prof. J. Wang thanks the financial support from the Opening Project of Key Laboratory of Optoelectronic Chemical Materials and Devices of Ministry of Education, Jianghan University. The authors thank Dr. Chunming Yang for GIWAXS tests and beamline BL16B1 (Shanghai Synchrotron Radiation Facility) for providing beam time.
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Finely Tuned Electron/Hole Transport Preference of Thiazoloisoindigo-based Conjugated Polymers by Incorporation of Heavy Chalcogenophenes
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Li, CC., Xiong, M., Peng, JW. et al. Finely Tuned Electron/Hole Transport Preference of Thiazoloisoindigo-based Conjugated Polymers by Incorporation of Heavy Chalcogenophenes. Chin J Polym Sci 39, 838–848 (2021). https://doi.org/10.1007/s10118-021-2552-9
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DOI: https://doi.org/10.1007/s10118-021-2552-9