Skip to main content
×
Home
    • Aa
    • Aa

Control of thermal and optoelectronic properties in conjugated poly(3-alkylthiophenes)

  • Victor Ho (a1), Bryan S. Beckingham (a1), Hoi H. Ng (a1) and Rachel A. Segalman (a1)
Abstract
Abstract

The optoelectronic and thermal properties of conjugated polymers are frequently tuned via direct synthetic modification of the conjugated repeat unit. It is also well known that these properties are inherently tied to the crystal structure, a factor which is difficult to predict upon slight chemical modification. We show that the crystal structure of random copolymers of 3-alkylthiophenes can be controlled, which in turn affects the optoelectronic properties. Furthermore, we show that the melting transitions smoothly vary between that of the two homopolymers. As such, the composition of copolymers is a convenient handle to predictably control the thermal properties, crystalline morphology, and optoelectronic properties simultaneously.

Copyright
Corresponding author
Address all correspondence to Rachel A. Segalman at segalman@berkeley.edu
Linked references
Hide All

This list contains references from the content that can be linked to their source. For a full set of references and notes please see the PDF or HTML where available.

1. I. Osaka and R.D. McCullough : Advances in molecular design and synthesis of regioregular polythiophenes. Acc. Chem. Res. 41, 1202 (2008).

2. R.L. Elsenbaumer , K.Y. Jen , and R. Oboodi : Processible and environmentally stable conducting polymers. Synth. Met. 15, 169 (1986).

3. V. Causin , C. Marega , A. Marigo , L. Valentini , and J.M. Kenny : Crystallization and melting behavior of poly(3-butylthiophene), poly(3-octylthiophene), and poly(3-dodecylthiophene). Macromolecules 38, 409 (2005).

4. S. Malik and A.K. Nandi : Crystallization mechanism of regioregular poly(3-alkyl thiophene)s. J. Polym. Sci. B, Polym. Phys. 40, 2073 (2002).

5. R.J. Kline , D.M. DeLongchamp , D.A. Fischer , E.K. Lin , L.J. Richter , M.L. Chabinyc , M.F. Toney , M. Heeney , and I. McCulloch : Critical role of side-chain attachment density on the order and device performance of polythiophenes. Macromolecules 40, 7960 (2007).

6. E.E. Sheina , S.M. Khersonsky , E.G. Jones , and R.D. McCullough : Highly conductive regioregular alkoxy-functionalized polythiophenes. Chem. Mater. 17, 3317 (2005).

7. X.M. Hong and D.M. Collard : Liquid crystalline regioregular semifluoroalkyl-substituted polythiophenes. Macromolecules 33, 6916 (2000).

8. V. Ho , B.W. Boudouris , and R.A. Segalman : Tuning polythiophene crystallization through systematic side chain functionalization. Macromolecules 43, 7895 (2010).

9. B.W. Boudouris , V. Ho , L.H. Jimison , M.F. Toney , A. Salleo , and R.A. Segalman : Real-time observation of poly(3-alkylthiophene) crystallization and correlation with transient optoelectronic properties. Macromolecules 44, 6653 (2011).

10. V. Ho , B.W. Boudouris , B.L. McCulloch , C.G. Shuttle , M. Burkhardt , M.L. Chabinyc , and R.A. Segalman : Poly(3-alkylthiophene) diblock copolymers with ordered microstructures and continuous semiconducting pathways. J. Am. Chem. Soc. 133, 9270 (2011).

11. S.N. Patel , A.E. Javier , K.M. Beers , J.A. Pople , V. Ho , R.A. Segalman , and N.P. Balsara : Morphology and thermodynamic properties of a copolymer with an electronically conducting block: poly(3-ethylhexylthiophene)-block-poly(ethylene oxide). Nano Lett. 12, 4901 (2012).

12. M.C. Iovu , M. Jeffries-El , R. Zhang , T. Kowalewski , and R.D. McCullough : Conducting block copolymer nanowires containing regioregular poly(3-Hexylthiophene) and polystyrene. J. Macromol. Sci., Pure Appl. Chem. 43, 1991 (2006).

13. P.T. Wu , G. Ren , and S.A. Jenekhe : Crystalline random conjugated copolymers with multiple side chains: tunable intermolecular interactions and enhanced charge transport and photovoltaic properties. Macromolecules 43, 3306 (2010).

14. Y. Zhang , K. Tajima , and K. Hashimoto : Nanostructure formation in poly(3-hexylthiophene-block-3-(2-ethylhexyl)thiophene)s. Macromolecules 42, 7008 (2009).

15. B. Burkhart , P.P. Khlyabich , and B.C. Thompson : Influence of the ethylhexyl side-chain content on the open-circuit voltage in rr-poly(3-hexylthiophene-co-3-(2-ethylhexyl)thiophene) copolymers. Macromolecules 45, 3740 (2012).

16. R.S. Loewe , P.C. Ewbank , J. Liu , L. Zhai , and R.D. McCullough : Regioregular, head-to-tail coupled poly(3-alkylthiophenes) made easy by the GRIM method: investigation of the reaction and the origin of regioselectivity. Macromolecules 34, 4324 (2001).

17. S.T. Turner , P. Pingel , R. Steyrleuthner , E.J.W. Crossland , S. Ludwigs , and D. Neher : Quantitative analysis of bulk heterojunction films using linear absorption spectroscopy and solar cell performance. Adv. Funct. Mater. 21, 4640 (2011).

18. F.C. Spano : Modeling disorder in polymer aggregates: the optical spectroscopy of regioregular poly 3-hexylthiophene thin films. J. Chem. Phys. 122, 234701 (2005).

19. F.C. Spano : Absorption in regio-regular poly(3-hexyl)thiophene thin films: fermi resonances, interband coupling and disorder. Chem. Phys. 325, 22 (2006).

20. D.T. Duong , M.F. Toney , and A. Salleo : Role of confinement and aggregation in charge transport in semicrystalline polythiophene thin films. Phys. Rev. B, Condens. Matter. 86, 205205 (2012).

21. J. Clark , C. Silva , R.H. Friend , and F.C. Spano : Role of intermolecular coupling in the photophysics of disordered organic semiconductors: aggregate emission in regioregular polythiophene. Phys. Rev. Lett. 98, 206406 (2007).

22. M.D. Barnes and M. Baghar : Optical probes of chain packing structure and exciton dynamics in polythiophene films, composites, and nanostructures. J. Polym. Sci. B, Polym. Phys. 50, 1121 (2012).

23. E.T. Niles , J.D. Roehling , H. Yamagata , A.J. Wise , F.C. Spano , A.J. Moule , and J.K. Grey : J-aggregate behavior in poly-3-hexylthiophene nanofibers. J. Phys. Chem. Lett. 3, 259 (2012).

26. T.J. Prosa , M.J. Winokur , J. Moulton , P. Smith , and A.J. Heeger : X-ray structural studies of poly(3-alkylthiophenes): an example of an inverse comb. Macromolecules 25, 4364 (1992).

27. N. Kayunkid , S. Uttiya , and M. Brinkmann : Structural model of regioregular poly(3-hexylthiophene) obtained by electron diffraction analysis. Macromolecules 43, 4961 (2010).

28. J. Rivnay , R. Noriega , R.J. Kline , A. Salleo , and M.F. Toney : Quantitative analysis of lattice disorder and crystallite size in organic semiconductor thin films. Phys. Rev. B, Condens. Matter. 84, 045203 (2011).

29. R. Noriega , J. Rivnay , K. Vandewal , F.P.V. Koch , N. Stingelin , P. Smith , M.F. Toney , and A. Salleo : A general relationship between disorder, aggregation and charge transport in conjugated polymers. Nat. Mater. 12, 1038 (2013).

30. P.J. Flory : Thermodynamics of crystallization in high polymers. IV. A theory of crystalline states and fusion in polymers, copolymers, and their mixtures with diluents. J. Chem. Phys. 17, 223 (1949).

31. G. Allegra and I.W. Bassi : Isomorphism in synthetic macromolecular systems. Adv. Polym. Sci. 6, 549 (1969).

32. N. Kamiya , M. Sakurai , Y. Inoue , and R. Chujo : Isomorphic behavior of random copolymers: thermodynamic analysis of cocrystallization of poly(3-hydroxybutyrate-co-3-h ydroxyvalerate). Macromolecules 24, 3888 (1991).

33. T. Matsumoto , K. Nakamae , N. Ogoshi , M. Kawasoe , and H. Oka : The crystallinity of ethylene-vinyl alcohol copolymers. Kobunshi Kagaku. 28, 610 (1971).

34. K. Nakamae , M. Kameyama , and T. Matsumoto : Elastic moduli of the crystalline regions in the direction perpendicular to the chain axis of ethylene-vinyl alcohol copolymers. Polym. Eng. Sci. 19, 572 (1979).

36. G. Natta : Progress in the stereospecific polymerization. Makromol. Chem. 35, 94 (1960).

37. J.A. Kreuz , B.S. Hsiao , C.A. Renner , and D.L. Goff : Crystalline homopolyimides and copolyimides derived from 3,3′,4,4′-biphenyltetracarboxylic Dianhydride/1,3-Bis(4-aminophenoxy)benzene/l,12-dodecanediamine. 1. Materials, preparation, and characterization. Macromolecules 28, 6926 (1995).

Recommend this journal

Email your librarian or administrator to recommend adding this journal to your organisation's collection.

MRS Communications
  • ISSN: 2159-6859
  • EISSN: 2159-6867
  • URL: /core/journals/mrs-communications
Please enter your name
Please enter a valid email address
Who would you like to send this to? *
×
Type Description Title
WORD
Supplementary Materials

Ho Supplementary Material
Supplementary Material

 Word (445 KB)
445 KB

Metrics

Altmetric attention score

Full text views

Total number of HTML views: 2
Total number of PDF views: 18 *
Loading metrics...

Abstract views

Total abstract views: 177 *
Loading metrics...

* Views captured on Cambridge Core between September 2016 - 20th September 2017. This data will be updated every 24 hours.