Advertisement

Journal of Materials Science

, Volume 52, Issue 1, pp 113–137 | Cite as

Selection of electroactive copolymers synthesized from 3-octylthiophene/biphenyl at low potentials as precursors for nanostructured thin-film formation

  • Sophia Karamanou
  • Johannis Simitzis
Original Paper

Abstract

Electrically conducting copolymers of 3-octylthiophene and biphenyl in equimolar ratio were synthesized and also homopolymers for comparison reasons by potentiostatic electropolymerization, and the polymers were deposited as coatings. Based on various criteria, a proper copolymer was selected and the homopolymer of poly(3-octylthiophene) (P3OT) for comparison reasons, in order to investigate their ability to prepare nanostructured thin films. The latter were synthesized by spin coating from solutions of the polymers in anisole. The polymers were characterized by proper methods such as size-exclusion chromatography (SEC), scanning electron microscopy/energy-dispersive spectroscopy (SEM/EDAX), X-ray diffraction (XRD), differential scanning calorimetry (DSC), ultraviolet–visible spectroscopy (UV–Vis), dynamic light scattering (DLS), atomic force microscopy (AFM), and cyclic voltammetry including also the determination of the limiting viscosity number [η] and their electrical conductivity (σ). The selected copolymer and the (P3OT) are mainly amorphous having also regions with order, the copolymer is soluble in more solvents, (P3OT) has higher σ, and both polymers form nanostructured thin films containing nanoparticles with ellipsoid morphology. Generally, the copolymers exhibit comparable properties with those of (P3OT); however, they are far cheaper. Besides the novelty to extend electroactive polymers in new application directions such as nanostructured materials, a further novelty consists of a proposed methodology based on the experimental data, in order to estimate different parameters at molecular level, especially for the macromolecules in solution. The energy gap E g (band gap) of the polymers as nanostructured thin films was determined by cyclic voltammetry indicating semiconductor behavior, which was also confirmed by their electrical conductivity.

Keywords

Differential Scanning Calorimetry Dynamic Light Scattering High Occupied Molecular Orbital Lower Unoccupied Molecular Orbital HDPE 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Notes

Acknowledgements

The authors thank G. Bokias, Associate Professor of the Department of Chemistry of University of Patras, for kindly helping in the SEC measurements, S. Pispas of Theoretical and Physical Chemistry Institute of National Hellenic Research Foundation for kindly helping in the DLS measurements, and Professor D. Manolakos of the School of Mechanical Engineering of NTUA, for kindly helping in the AFM measurements.

Compliance with ethical standards

Conflict of interest

This research has been co-financed by the European Union (European Social Fund–ESF) and Greek National funds through the Operational Program “Education and Lifelong Learning” of the National Strategic Reference Framework (NSRF)–Research Funding Program: Heracleitus II. Investing in knowledge society through the European Social Fund. The authors declare that they have no conflict of interest.

Supplementary material

10853_2016_315_MOESM1_ESM.docx (28 kb)
Supplementary material 1 (DOCX 27 kb)

References

  1. 1.
    Fratoddi I, Bearzotti A, Venditti I, Cametti C, Russo MV (2016) Role of nanostructured polymers on the improvement of electrical response-based relative humidity sensors. Sens Actuators B 225:96–108CrossRefGoogle Scholar
  2. 2.
    Zhuang X, Mai Y, Wu D, Zhang F, Feng X (2015) Two dimensional soft nanomaterials: a fascinating world of materials. Adv Mater 27:403–427CrossRefGoogle Scholar
  3. 3.
    Zhang B, Zhao X (2009) Synthesis, characterization, and photochromic behaviors of polythiophene derivatives in the solid state. J Mater Sci 44:2765. doi: 10.1007/s10853-009-3361-7 CrossRefGoogle Scholar
  4. 4.
    Peet J, Heeger AJ, Bazan GC (2009) Plastic solar cells: self assembly of bulk heterojunction nanomaterials by spontaneous phase separation. Acc Chem Res 42:1700–1708CrossRefGoogle Scholar
  5. 5.
    Karbovnyk I, Olenych I, Kukhta A, Lugovskii A, Sasnouski G, Olenych Y, Luchechko A, Popov AI, Yarytska L (2015) Multicolor photon emission from organic thin films on different substrates. Radiat Meas 90:1–13Google Scholar
  6. 6.
    Vieira NCS, Figueiredo A, Fernandes EGR, Guimarges FEG, Zucolotto V (2013) Nanostructured polyaniline thin films as urea-sensing membranes in field-effect devices. Synth Met 175:108–111CrossRefGoogle Scholar
  7. 7.
    Berti F, Todros S, Lakshmi D, Whitcombe MJ, Chianella I, Ferroni M, Piletsky SA, Turner APF, Marrazza G (2010) Quasi-monodimensional polyaniline nanostructures for enhanced molecularly imprinted polymer-based sensing. Biosens Bioelectron 26:497–503CrossRefGoogle Scholar
  8. 8.
    Killard AJ (2010) Nanostructured conducting polymers for (electro)chemical sensors. In: Eftekhari A (ed) Nanostructured conductive polymers. Wiley, New Jersey, pp 563–598. doi: 10.1002/9780470661338 (published online) CrossRefGoogle Scholar
  9. 9.
    Bensebaa F (2013) Nanoparticle assembling and system integration (interface science and technology) In: Nanoparticle technologies, vol 19. Kindle Edition, Elsevier Ltd, Amsterdam, New York, Academic Press, National Research Council of Canada, pp 185–277. doi: 10.1016/B978-0-12-369550-5.00004-5
  10. 10.
    Peponi L, Puglia D, Torre L, Valentini L, Kenny JM (2014) Processing of nanostructured polymers and advanced polymeric based nanocomposites. Mater Sci Eng R 85:1–46CrossRefGoogle Scholar
  11. 11.
    Bockstaller MR, Mickiewicz RA, Thomas EL (2005) Block copolymer nanocomposites: perspectives for tailored functional materials. Adv Mater 17:1331–1349. doi: 10.1002/adma.200500167 CrossRefGoogle Scholar
  12. 12.
    Tran HD, Li D, Kaner RB (2009) One-dimensional conducting polymer nanostructures: bulk synthesis and applications. Adv Mater 2:1487–1499CrossRefGoogle Scholar
  13. 13.
    Long YZ, Li MM, Gu C, Wan M, Duvail JL, Liu Z, Fan Z (2011) Recent advances in synthesis, physical properties and applications of conducting polymer nanotubes and nanofibers. Prog Polym Sci 36:1415–1442CrossRefGoogle Scholar
  14. 14.
    Lecommandoux S, Garanger E (2016) Precision polymers with biological activity: design towards self-assembly and bioactivity. C R Chimie 19:143–147CrossRefGoogle Scholar
  15. 15.
    Malik S, Nandi AK (2002) Crystallization mechanism of regioregular poly(3-alkyl thiophene)s. J Polym Sci Part B 40:2073–2085CrossRefGoogle Scholar
  16. 16.
    Merlo JA, Frisbie CD (2003) Field effect conductance of conducting polymer nanofibers. J Polym Sci Part B 41:2674–2680CrossRefGoogle Scholar
  17. 17.
    Kim DH, Jang Y, Park YD, Cho K (2006) Controlled one-dimensional nanostructures in poly(3-hexylthiophene) thin film for high-performance organic field-effect transistors. J Phys Chem B 110:15763–15768CrossRefGoogle Scholar
  18. 18.
    Li D, Kaner RB (2005) Processable stabilizer-free polyaniline nanofiber aqueous colloids. Chem Commun 26:3286–3288CrossRefGoogle Scholar
  19. 19.
    Bai W, Wu C, Shang X, Liu X, Chen K, Lin J (2016) Self-assembly of poly(p-phenylene)-based flower-like 3D micro-nanostructures. React Funct Polym 101:75–81CrossRefGoogle Scholar
  20. 20.
    Petrelli C, Goos A, Ruhlandt-Senge K, Spencer JT (2016) Functionalization of boron nitride nanosheets (BNNSs) by organic polymers: formation of substituted polythiophene–BNNS structures. J Mater Sci 51:4952–4962. doi: 10.1007/s10853-016-9800-3 CrossRefGoogle Scholar
  21. 21.
    Potai R, Traiphol R (2015) Control over the photophysical properties of nanoparticles of regioregular poly(3-octylthiophene) using various poor solvents. Synth Met 203:1–9CrossRefGoogle Scholar
  22. 22.
    Ryu HW, Kim YS, Kim JH, Cheong IW (2014) Direct synthetic route for water-dispersible polythiophene nanoparticles via surfactant-free oxidative polymerization. Polymer 55:806–812CrossRefGoogle Scholar
  23. 23.
    Simitzis J, Karamanou S (2015) Electrochemical synthesis and characterization of electroactive copolymers deriving from five-ring with six-ring aromatic compounds and their perspectives for cost-effective optoelectronic applications: the system of 3-octylthiophene with biphenyl. In: Wythers MC (ed) Advances in materials science research, chapter 4, 21st edn. Nova Science Publishers, New York, pp 69–110Google Scholar
  24. 24.
    Walton DJ, Lorimer JP (2000) Polymers. Oxford Science Publications, Oxford University Press, Oxford, pp 135–136Google Scholar
  25. 25.
    Pan Z, Ge J, Li W, Peng J, Qiu F (2012) Transition from polythiophene-based one-dimensional nanofibers to spherical clusters in ultrafiltration. Soft mat Comm R Soc Chem. doi: 10.1039/c2sm26523k Google Scholar
  26. 26.
    Striegel AM, Yau WW, Kirkland JJ, Bly DD (2009) Modern size-exclusion liquid chromatography Practice of gel permeation and gel filtration chromatography, second Ed, John A Wiley & Sons INC, publication, New Jersey, pp 322-323, 328-334Google Scholar
  27. 27.
    Hamley IW (2000) Polymers, colloids, amphiphiles and liquid crystals. University of Leeds, School of Chemistry, pp 61–65Google Scholar
  28. 28.
    Udayakumar D, Vasudene A (2006) Synthesis and characterization of new light-emitting copolymers containing 3,4-dialkoxythiophenes. Synth Met 156:1168–1173CrossRefGoogle Scholar
  29. 29.
    Simitzis J, Triantou D, Soulis S (2008) Synthesis and characterization of electrically conducting copolymers based on benzene and biphenyl. J Appl Polym Sci 110:356–367CrossRefGoogle Scholar
  30. 30.
    Valaski R, Moreira LM, Micaroni L, Hummelgen IA (2003) The electronic behavior of poly(3-octylthiophene) electrochemically synthesized onto Au substrate. Braz J Phys 33:392–397CrossRefGoogle Scholar
  31. 31.
    Simitzis J, Triantou D, Soulis S (2010) Synthesis and characterization of electrically conducting copolymers based on biphenyl and thiophene. J Appl Polym Sci 118:1494–1506Google Scholar
  32. 32.
    Simitzis J, Soulis S, Triantou D (2012) Electrochemical synthesis and characterization of conducting copolymers of biphenyl with pyrrole. J Appl Polym Sci 125:1928–1941CrossRefGoogle Scholar
  33. 33.
    Mardalen J, Samuelsen EJ, Gautun OR, Carlsen PH (1992) X-ray scattering from oriented poly(3-alkylthiophenes). Synth Met 48:363–380CrossRefGoogle Scholar
  34. 34.
    Lanzi M, Bizzarri PC, Paganin L, Cesari G (2007) Highly processable ester-functionalized polythiophenes as valuable multifunctional and post-functionalizable conjugated polymers. Eur Pol J 43:72–83CrossRefGoogle Scholar
  35. 35.
    Simitzis J, Zoumboulakis L, Stamboulis A, Hinrichsen G (1993) The effects of the proportion of biphenyl-A1C13-CuC12 polymerization system on structure and electrical conductivity of insoluble polyphenylenes. Die Angewandte Makromolekulare Chemie 213:181–196CrossRefGoogle Scholar
  36. 36.
    Chen SA, Ni JM (1992) Structure/properties of conjugated conductive polymers. 1. Neutral poly(3-alkyl thiophene)s. Macromolecules 25:6081–6089CrossRefGoogle Scholar
  37. 37.
    Sugimoto R, Taketa S, Gu HB, Yoshino K (1986) Preparation of soluble polythiophene derivatives utilizing transition metal halides as catalysts and their property. Chem Press 1:635–638Google Scholar
  38. 38.
    Koenig JL (1980) Chemical microstructure of polymer chains. Wiley, New York, pp 27–28Google Scholar
  39. 39.
    Latonen RM, Kvarnstrom C, Ivaska A (2001) In situ UV–vis and FTIR attenuated total reflectance studies on the electrochemically synthesized copolymer from biphenyl and 3-octylthiophene. J Electroanal Chem 512:36–48CrossRefGoogle Scholar
  40. 40.
    Li X, Li J, Huang R (2009) Facile optimal synthesis of inherently electroconductive polythiophene nanoparticles. Chem Eur J 15:6446–6455CrossRefGoogle Scholar
  41. 41.
    Salzer U, Zhu R, Luten M, Isobe H, Pastushenko V, Perkmann T, Hinterdorfer P, Bosman GJCGM (2008) Vesicles generated during storage of red cells are rich in the lipid raft marker stomatin. Transfusion 48:451–462CrossRefGoogle Scholar
  42. 42.
    Marcus Y (1999) The properties of solvents, Wiley Series in solution Chemistry, Chapter 3, Physical properties of solvents, vol 4, John Wiley & Sons, Chichester, New York, pp 87,89,91Google Scholar
  43. 43.
    Rohrbaugh RH, Jurs PC (1987) Descriptions of molecular shape applied in studies of structure/activity and structure/property relationships. Anal Chim Acta 199:99–109CrossRefGoogle Scholar
  44. 44.
    Kiriy N, Jahne E, Adler HJ, Schneider M, Kiriy A, Gorodyska G, Minko S, Jehnichen D, Simon P, Fokin AA, Stamm M (2003) One-Dimensional Aggregation of Regioregular Polyalkylthiophenes. Nano Lett 3:707–712CrossRefGoogle Scholar
  45. 45.
    Hall DB, Underhill P, Torkelson JM (1998) Spin Coating of thin and ultrathin polymer films. Pol Engin Sci 38:2039–2045CrossRefGoogle Scholar
  46. 46.
    Zhang XW (2013) Doping and electrical properties of cubic boron nitride thin films: a critical review. Thin Solid Films 544:2–12CrossRefGoogle Scholar
  47. 47.
    Sperling LH (1992) Introduction to Physical Polymer Science, 2nd edn. Wiley, New York, pp 173–174Google Scholar
  48. 48.
    Schurz J (1974) Physikalische Chemie der Hochpolymeren Eine Einfuhrung. Springer-Verlag, Berlin, pp 43–46CrossRefGoogle Scholar
  49. 49.
    Vollmert B (1988) Grundriss der Makromolekularen Chemie, Vollmert E, Verlag Karlsruhe, Band IV pp. 3,12-20,32 and Band III pp. 167-168, 186-187Google Scholar
  50. 50.
    Miller RL (1999) Crystallographic Data and Melting Points for Various Polymers, In: Polymer Handbook, Brandrup J, Immergut EH, Grulke EA, Fourth Edition, John Wiley &Sons, INC, New York, pp. VI/16 VI/17Google Scholar
  51. 51.
    Nuraje N, Su K, Yang NL, Matsui H (2008) Liquid/liquid interfacial polymerization to grow single crystalline nanoneedles of various conducting polymers. ACS Nano 2:502–506CrossRefGoogle Scholar
  52. 52.
    Li Y, Cao Y, Gao J, Wang D, Yu G, Heeger AJ (1999) Electrochemical properties of luminescent and polymer light-emitting electrochemical cells. Synth Met 99:243–248CrossRefGoogle Scholar
  53. 53.
    Burghard M, Fischer CM, Roth S, Schlick U, Hanack M (1996) Charge transport in ultrathin Langmuir–Blodgett film devices: HOMO-mediated tunneling. Synth Met 76:241–244CrossRefGoogle Scholar
  54. 54.
    Ustamehmetoglu B (2014) Synthesis and characterization of thiophene and thiazole containing polymers. Electrochim Acta 122:130–140CrossRefGoogle Scholar
  55. 55.
    Jarosz T, Data P, Domagala W, Kuznik W, Kotwicad K, Lapkowski M (2014) Solubility controlled electropolymerisation and study of the impact of regioregularity on the spectroelectrochemical properties of thin films of poly(3-octylthiophenes). Electrochim Acta 122:66CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2016

Authors and Affiliations

  1. 1.Laboratory Unit “Advanced and Composite Materials”, Department III, “Materials Science and Engineering”, School of Chemical EngineeringNational Technical University of AthensZografou CampusGreece

Personalised recommendations