Skip to main content Accessibility help

Effects of alkyl chain positioning on conjugated polymer microstructure and field-effect mobilities

  • Bob C. Schroeder (a1), Christian B. Nielsen (a1), Paul Westacott (a2), Jeremy Smith (a3), Stephan Rossbauer (a3), Thomas D. Anthopoulos (a3), Natalie Stingelin (a2) and Iain McCulloch (a1) (a4)...


Solubilizing alkyl chains play a crucial role in the design of semiconducting polymers because they define the materials solubility and processability as well as both the crystallinity and solid-state microstructure. In this paper, we present a scarcely explored design approach by attaching the alkyl side chains on one side (cis-) or on both sides (trans-) of the conjugated backbone. We further investigate the effects of this structural modification on the solid-state properties of the polymers and on the charge-carrier mobilities in organic thin-film transistors.


Corresponding author

Address all correspondence to Bob C. Schroeder


Hide All
1.Sirringhaus, H.: Organic field-effect transistors: the path beyond amorphous silicon. Adv. Mater. 26, 1319 (2014).
2.Wu, W., Liu, Y., and Zhu, D.: π-conjugated molecules with fused rings for organic field-effect transistors: design, synthesis and applications. Chem. Soc. Rev. 39, 1489 (2010).
3.Nielsen, C.B. and McCulloch, I.: Recent advances in transistor performance of polythiophenes. Progr. Polym. Sci. 38, 2053 (2013).
4.Holliday, S., Donaghey, J.E., and McCulloch, I.: Advances in charge carrier mobilities of semiconducting polymers used in organic transistors. Chem. Mater. 26, 647 (2014).
5.Zhang, X., Bronstein, H., Kronemeijer, A.J., Smith, J., Kim, Y., Kline, R.J., Richter, L.J., Anthopoulos, T.D., Sirringhaus, H., Song, K., Heeney, M., Zhang, W., McCulloch, I., and DeLongchamp, D.M.: Molecular origin of high field-effect mobility in an indacenodithiophene-benzothiadiazole copolymer. Nat. Commun. 4, 3238 (2013).
6.Venkateshvaran, D., Nikolka, M., Sadhanala, A., Lemaur, V., Zelazny, M., Kepa, M., Hurhangee, M., Kronemeijer, A.J., Pecunia, V., Nasrallah, I., Romanov, I., Broch, K., McCulloch, I., Emin, D., Olivier, Y., Cornil, J., Beljonne, D., and Sirringhaus, H.: Approaching disorder-free transport in high-mobility conjugated polymers. Nature 515, 384 (2014).
7.Mei, J. and Bao, Z.: Side chain engineering in solution-processable conjugated polymers. Chem. Mater. 26, 604 (2014).
8.Lei, T., Wang, J.-Y., and Pei, J.: Roles of flexible chains in organic semiconducting materials. Chem. Mater. 26, 594 (2014).
9.Bronstein, H., Leem, D.S., Hamilton, R., Woebkenberg, P., King, S., Zhang, W., Ashraf, R.S., Heeney, M., Anthopoulos, T.D., de Mello, J., and McCulloch, I.: Indacenodithiophene-co-benzothiadiazole copolymers for high performance solar cells or transistors via alkyl chain optimization. Macromolecules 44, 6649 (2011).
10.Ong, B.S., Wu, Y., Liu, P., and Gardner, S.: High-performance semiconducting polythiophenes for organic thin-film transistors. J. Am. Chem. Soc. 126, 3378 (2004).
11.McCulloch, I., Heeney, M., Bailey, C., Genevicius, K., MacDonald, I., Shkunov, M., Sparrowe, D., Tierney, S., Wagner, R., Zhang, W., Chabinyc, M.L., Kline, R.J., McGehee, M.D., and Toney, M.F.: Liquid-crystalline semiconducting polymers with high charge-carrier mobility. Nat. Mater. 5, 328 (2006).
12.Biniek, L., Schroeder, B.C., Donaghey, J.E., Yaacobi-Gross, N., Ashraf, R.S., Soon, Y.W., Nielsen, C.B., Durrant, J.R., Anthopoulos, T.D., and McCulloch, I.: New fused bis-thienobenzothienothiophene copolymers and their use in organic solar cells and transistors. Macromolecules 46, 727 (2013).
13.Fei, Z., Pattanasattayavong, P., Han, Y., Schroeder, B.C., Yan, F., Kline, R.J., Anthopoulos, T.D., and Heeney, M.: Influence of side-chain regiochemistry on the transistor performance of high-mobility, all-donor polymers. J. Am. Chem. Soc. 136, 15154 (2014).
14.Kline, R.J., DeLongchamp, D.M., Fischer, D.A., Lin, E.K., Richter, L.J., Chabinyc, M.L., Toney, M.F., Heeney, M., and McCulloch, I.: Critical role of side-chain attachment density on the order and device performance of polythiophenes. Macromolecules 40, 7960 (2007).
15.Zhang, L., Colella, N.S., Liu, F., Trahan, S., Baral, J.K., Winter, H.H., Mannsfeld, S.C.B., and Briseno, A.L.: Synthesis, electronic structure, molecular packing/morphology evolution, and carrier mobilities of pure oligo-/poly(alkylthiophenes). J. Am. Chem. Soc. 135, 844 (2013).
16.McCulloch, I., Ashraf, R.S., Biniek, L., Bronstein, H., Combe, C., Donaghey, J.E., James, D.I., Nielsen, C.B., Schroeder, B.C., and Zhang, W.: Design of semiconducting indacenodithiophene polymers for high performance transistors and solar cells. Acc. Chem. Res. 45, 714 (2012).
17.Tsao, H.N., Cho, D.M., Park, I., Hansen, M.R., Mavrinskiy, A., Yoon, D.Y., Graf, R., Pisula, W., Spiess, H.W., and Müllen, K.: Ultrahigh mobility in polymer field-effect transistors by design. J. Am. Chem. Soc. 133, 2605 (2011).
18.Lei, T., Dou, J.-H. and Pei, J.: Influence of alkyl chain branching positions on the hole mobilities of polymer thin-film transistors. Adv. Mater. 24, 6457 (2012).
19.Mei, J., Kim, D.H., Ayzner, A., Toney, M.F., and Bao, Z.: Siloxane-terminated solubilizing side chains: bringing conjugated polymer backbones closer and boosting hole mobilities in thin-film transistors. J. Am. Chem. Soc. 133, 20130 (2011).
20.Meager, I., Ashraf, R.S., Mollinger, S., Schroeder, B.C., Bronstein, H., Beatrup, D., Vezie, M.S., Kirchartz, T., Salleo, A., Nelson, J., and McCulloch, I.: Photocurrent enhancement from diketopyrrolopyrrole polymer solar cells through alkyl-chain branching point manipulation. J. Am. Chem. Soc. 135, 11537 (2013).
21.Himmelberger, S., Duong, D.T., Northrup, J.E., Rivnay, J., Koch, F.P.V., Beckingham, B.S., Stingelin, N., Segalman, R.A., Mannsfeld, S.C.B., and Salleo, A.: Role of side-chain branching on thin-film structure and electronic properties of polythiophenes. Adv. Funct. Mater. (2015). doi:10.1002/adfm.201500101.
22.Schroeder, B.C., Ashraf, R.S., Thomas, S., White, A.J.P., Biniek, L., Nielsen, C.B., Zhang, W., Huang, Z., Tuladhar, P.S., Watkins, S.E., Anthopoulos, T.D., Durrant, J.R., and McCulloch, I.: Synthesis of novel thieno[3,2-b]thienobis(silolothiophene) based low bandgap polymers for organic photovoltaics. Chem. Commun. 48, 7699 (2012).
23.Schroeder, B.C., Kirkus, M., Nielsen, C.B., Ashraf, R.S., and McCulloch, I.: Dithienosilolothiophene, a new polyfused donor for organic electronics, submitted (2015).
24.Schroeder, B.C., Huang, Z., Ashraf, R.S., Smith, J., D'Angelo, P., Watkins, S.E., Anthopoulos, T.D., Durrant, J.R., and McCulloch, I.: Silaindacenodithiophene-based low band gap polymers—the effect of fluorine substitution on device performances and film morphologies. Adv. Funct. Mater. 22, 1663 (2012).

Related content

Powered by UNSILO

Effects of alkyl chain positioning on conjugated polymer microstructure and field-effect mobilities

  • Bob C. Schroeder (a1), Christian B. Nielsen (a1), Paul Westacott (a2), Jeremy Smith (a3), Stephan Rossbauer (a3), Thomas D. Anthopoulos (a3), Natalie Stingelin (a2) and Iain McCulloch (a1) (a4)...


Altmetric attention score

Full text views

Total number of HTML views: 0
Total number of PDF views: 0 *
Loading metrics...

Abstract views

Total abstract views: 0 *
Loading metrics...

* Views captured on Cambridge Core between <date>. This data will be updated every 24 hours.

Usage data cannot currently be displayed.