Thought Leaders

Designing Organic Semiconducting Materials - The Promise of Flexible Electronics

Most organic polymers (i.e. plastics) are insulators and are often used to isolate metallic conductors from other conducting materials. However, studies beginning in the 1960s revealed that the electrical conductivity of conjugated organic polymers (Figure 1) can be controlled through oxidation or reduction1. These initial discoveries have led to a modern class of organic materials with the conductivity of classical inorganic systems, but with many of the desirable properties of organic plastics, including mechanical flexibility and low production costs2-6.

Commonly studied conjugated polymers.
Figure 1. Commonly studied conjugated polymers.

Such organic materials, often called synthetic metals7,8, are semiconductors in their neutral state and exhibit increased conductivity upon oxidation or reduction. As a result, they have received considerable fundamental and technological interest, leading to their current use in such applications (Figure 2) as sensors, organic field effect transistors (OFETs), organic photovoltaic (OPV) devices, electrochromic devices, and organic light emitting-diodes (OLEDs)2-6. In addition, the flexible, plastic nature of the organic materials used as the active layers in such electronic devices has led to the realistic promise of flexible electronics in the near future9-12.

Free standing conjugated polymer film (A) and examples of electrochromics (B), OPV devices (C)13 and OLED devices (D)
Figure 2. Free standing conjugated polymer film (A) and examples of electrochromics (B), OPV devices (C)13 and OLED devices (D)14.

Molecular Design

One advantage of utilizing conjugated polymers for technological applications is the ability to tune the material properties at the molecular level4. This is typically accomplished through synthetic modification of the monomeric units, the combination of dissimilar units to make copolymeric systems, or in some cases through post-polymerization processes. The most promising organic semiconducting materials combine a number of critical properties, including processiblity, stability, conjugation length, band gap energy, and charge mobility. The ability to modify these properties is of the utmost importance for the efficient application of these materials. For example, soluble, stable systems are required for their physical processing and incorporation in technological devices, while the remaining properties determine the effectiveness of the polymer as an electronic material.

Physical Properties

The stability of conjugated polymers can be divided into electrochemical stability and stability of the polymer to chemical or photochemical reactions15,16. For example, neutral polyacetylene is considered to be electrochemically stable, but is susceptible to triplet oxygen insertion, resulting in chemical decomposition. Due to both environmental stability and ease of synthetic modification, polythiophenes are thought to be one of the most versatile classes of conjugated polymers and thus exhibit perhaps the greatest amount of synthetic diversity3-6.

Due to their rigid nature, conjugated materials exhibit limited solubility in comparison to saturated organic polymers. As a result, the majority of unfunctionalized systems are insoluble. Beginning in 1986, however, it was found that substitution of alkyl chains (butyl or longer) in the β-position of thiophenes resulted in soluble and fusible polymers5,6. The application of such flexible side chains to conjugated polymers in general has since resulted in large numbers of soluble materials that can be easily solution processed. It should be noted, though, that while such methods can be used to enhance solubility, there are a number of unintended consequences, the most significant of which is the addition of steric effects that can twist the polymer backbone out of planarity4,6.

Optical and Electronic Properties

The optical and electronic properties of these materials are determined by the extent of conjugation along the material backbone and thus a high degree of conjugation is essential. Conjugation length can be determined by several factors, of which the simplest are the overall length of the conjugation path and the molecule's planarity. As the conjugation length is dependent on the overlap of orbitals between neighboring π-bonds, it can be influenced by torsional strain along the backbone and significant deviations from planarity (i.e. > 40° between units)17 result in decreased conjugation4,6. In addition, as the potential conjugation path increases with molecular length, small molecules generally exhibit shorter conjugation lengths than polymeric materials. Extension of the conjugation length with molecular length is not infinite, however, as delocalization limits result in a maximum effective conjugation length (~20-30 rings in polythiophene)18,19. Further extending chain length can affect physical properties, but has little effect on electronic and optical properties.

Directly related to conjugation is the material's band gap (Eg), which is the energy between the filled valence and empty conduction bands and thus corresponds to the HOMO-LUMO gap of the solid state material4,20,21. As a result, it determines the lowest energy absorbance and the energy of any emission. Bond length alternation is considered to have one of the largest effects on the Eg of organic materials (greater alternation gives larger Eg)22,23. Materials based on aromatic rings, however, differ in that they have non-degenerate resonance structures (Figure 3). Here, the aromatic form has a larger Eg, but is more stable and thus represents the ground-state structure. For these systems, it is thought that increasing quinoidal character in the ground state has a greater effect than limiting bond length alternation22,23.

A) Aromatic and quinoid resonance structures of polythiophene; B) Low band gap polymers due to enhanced quinoidal character
Figure 3. A) Aromatic and quinoid resonance structures of polythiophene; B) Low band gap polymers due to enhanced quinoidal character4,24-26.

Additional factors include backbone planarity, the heteroatom in heterocyclic systems, and monomer aromaticity (Figure 4)4,15,27-30. The effect of the heteroatom is thought to strongly correlate with its electron affinity, with higher affinities resulting in lower Eg values29. It has also been proposed that monomer aromaticity determines the confinement potential of the π-electrons. As the confinement within the ring becomes stronger, the delocalization length along the backbone decreases, resulting in larger Eg values30. The last factor to consider is interchain coupling that can occur via stacking in the solid state, resulting in increased electron delocalization and a reduction in Eg . Reduced molecular ordering can increase the spatial distance between polymer chains, reducing interchain coupling and increasing Eg. Such molecular ordering can also directly affect the materials charge mobility.

Illustrative examples of molecular effects on band gap.
Figure 4. Illustrative examples of molecular effects on band gap.

In conclusion, the combination of all the above factors determines the resultant material properties and the key to designing next generation organic materials is the enhancement of one or more of these factors. However, as many of these factors are interrelated, it can be challenging to selectively modify one factor without affecting others.


  1. S. C. Rasmussen, "Electrically Conducting Plastics: Revising the History of Conjugated Organic Polymers", In 100+ Years of Plastics. Leo Baekeland and Beyond; E. T. Strom and S. C. Rasmussen, Eds.; ACS Symposium Series, American Chemical Society: Washington, DC, 2011.
  2. Handbook of Conducting Polymers, 3rd ed., T. A. Skotheim and J. R. Reynolds, Eds.; CRC Press: Boca Raton, FL, 2007.
  3. Handbook of Thiophene-based Materials, I. F. Perepichka and D. F. Perepichka, Eds.; John Wiley & Sons: Hoboken, NJ, 2009.
  4. S. C. Rasmussen, K. Ogawa, and S. D. Rothstein, "Synthetic Approaches to Band Gap Control in Conjugated Polymeric Materials", In the Handbook of Organic Electronics and Photonics, H. S. Nalwa, Ed.; American Scientific Publishers: Stevenson Ranch, CA, 2008.
  5. J. Roncali, "Conjugated Poly(thiophenes): Synthesis, Functionalization, and Applications", Chem. Rev. 92, 711 (1992).
  6. S. C. Rasmussen, B. D. Straw, and J. E. Hutchison, "Tuning the Extent of Conjugation in Processable Polythiophenes Through Control of Side Chain Density and Regioregularity", In Semiconducting Polymers: Applications, Synthesis, and Properties; B. R. Hsieh, W. Wei, and M. Galvin, Eds.; ACS Symposium Series #735, American Chemical Society: Washington, D.C., 1999.
  7. A. G. MacDiarmid, ""Synthetic Metals": A Novel Role for Organic Polymers (Nobel Lecture)", Angew. Chem. Int. Ed. 40, 2581 (2001).
  8. A. G. MacDiarmid and A. J. Epstein, "Conducting Polymers: Past, Present, and Future...", Mat. Res. Soc. Symp. Porc. 328, 133 (1994).
  9. S. Logothetidisa and A. Laskarakis, "Towards the optimization of materials and processes for flexible organic electronics devices", Eur. Phys. J. Appl. Phys. 46, 12502 (2009).
  10. T. Sekitani and T. Someya, "Stretchable, Large-area Organic Electronics", Adv. Mater. 22, 2228 (2010).
  11. D. M. de Leeuw and E. Cantatore, "Organic electronics: Materials, technology and circuit design developments enabling new applications", Mat. Sci. Semicond. Process. 11, 199 (2008).
  12. K. J. Allen, "Reel to Real: Prospects for Flexible Displays" Proc. IEEE 93, 1394 (2005).
  13. W. J. Belcher, S. C. Rasmussen and P. C. Dastoor "Characterization of N-Functionalized poly(dithieno[3,2-b:2’,3’-d]pyrrole)s in Ternary Blend Bulk Heterojunction Structured Organic Electronic Devices", Polym. Prepr. 48(1), 11 (2007).
  14. S. J. Evenson, M. J. Mumm, K. I. Pokhodnya, and S.C. Rasmussen "Highly Fluorescent Dithieno[3,2-b:2',3'-d]pyrrole-based Materials: Synthesis, Characterization and OLED Device Applications", Macromolecules 44, in press (2011).
  15. D. M. de Leeuw , M. M. J. Simenon, A. R. Brown, and R. E. F. Einerhand, "Stability of n-type doped conducting polymers and consequences for polymeric microelectronic devices", Synth. Met. 87, 53 (1997).
  16. Y. Li and R. Qian, "Stability of conducting polymers from the electrochemical point of view", Synth. Met. 53, 149 (1993).
  17. J. L. Brédas, G. B. Street, B. Themans, and J. M. Andre, "Organic polymers based on aromatic rings (polyparaphenylene, polypyrrole, polythiophene): Evolution of the electronic properties as a function of the torsion angle between adjacent rings", J. Chem. Phys. 83, 1323 (1985).
  18. N. Sumi, H. Nakanishi, S. Ueno, K. Takimiya, Y. Aso, T. Otsubo, "Synthesis and Properties of a Series of the Longest Oligothiophenes up to the 48-mer", Bull. Chem. Soc. Jpn. 74, 979 (2001).
  19. T. Izumi, S. Kobashi, K. Takimiya, Y. Aso, T. Otsubo, "Synthesis and Spectroscopic Properties of a Series of ?-Blocked Long Oligothiophenes up to the 96-mer: Revaluation of Effective Conjugation Length", J. Am. Chem. Soc. 125, 5286 (2003).
  20. J. Roncali, "Synthetic Principles for Bandgap Control in Linear ?-Conjugated Systems", Chem. Rev. 97, 173 (1997).
  21. S. C. Rasmussen and M. Pomerantz, "Low Bandgap Conducting Polymers," in Conjugated Polymers: Theory, Synthesis, Properties, and Characterization, T. A. Skotheim and J. R. Reynolds, Eds.; Handbook of Conducting Polymers, 3rd Ed.; CRC Press: Boca Raton, FL, 2007
  22. J. L. Brédas, "Relationship between band gap and bond length alternation in organic conjugated polymers", J. Chem. Phys. 82, 3808 (1985).
  23. J. L. Brédas, "Aromatic Polymers: Evolution of Their Electronic Properties as a Function of Bond-Length Alternation and Torsion Angle Along the Chains", In Electronic Properties of Polymers and Related Compounds, H. Kuzmany, M. Mehring, and S. Roth, Eds., Springer Series in Solid-State Sciences, Springer-Verlang: Berlin, 1985.
  24. L. Wen, B. C. Duck, P. C. Dastoor, and S. C. Rasmussen "Poly(2,3-dihexylthieno[3,4-b]pyrazine) via GRIM Polymerization: The Simple Preparation of a Solution Processable, Low Band Gap Conjugated Polymer", Macromolecules, 41, 4576 (2008).
  25. J. P. Nietfeld, C. L. Heth, and S. C. Rasmussen "Poly(acenaphtho[1,2-b]thieno[3,4-e]-pyrazine): A New Low Band Gap Conjugated Polymer," Chem. Commun. 981 (2008).
  26. L. Wen, J. P. Nietfeld, C. M. Amb, and S. C. Rasmussen "New Tunable Thieno[3,4-b]pyrazine-based Materials", Synth. Met. 159, 2299 (2009).
  27. Y.-S. Lee and M. Kertesz, "The effect of heteroatomic substitutions on the band gap of polyacetylene and polyparaphenylene derivatives", J. Chem. Phys. 88, 2609 (1988).
  28. S. Y. Hong, S. J. Kwon, S. C. Kim, and D. S. Marynick, "Effects of Bridging Groups on Electronic Structures of Conjugated Cyclic Polymers", Synth. Met. 69, 701 (1995).
  29. G. R. Hutchison, Y.-J. Zhao, B. Delley, A. J. Freeman, M. A. Ratner, and T. J. Marks, "Electronic structure of conducting polymers: Limitations of oligomer extrapolation approximation and effects of heteroatoms", Phys. Rev. B, 68, 35204 (2003).
  30. V. Hernandez, C. Castiglioni, M. Del Zoppo, and G. Zerbi, "Confinement potential and p-electron delocalization in polyconjugated organic materials", Phys. Rev. B., 50, 9815 (1994).

Disclaimer: The views expressed here are those of the interviewee and do not necessarily represent the views of Limited (T/A) AZoNetwork, the owner and operator of this website. This disclaimer forms part of the Terms and Conditions of use of this website.


Please use one of the following formats to cite this article in your essay, paper or report:

  • APA

    Rasmussen, Seth. (2019, June 24). Designing Organic Semiconducting Materials - The Promise of Flexible Electronics. AZoM. Retrieved on October 05, 2022 from

  • MLA

    Rasmussen, Seth. "Designing Organic Semiconducting Materials - The Promise of Flexible Electronics". AZoM. 05 October 2022. <>.

  • Chicago

    Rasmussen, Seth. "Designing Organic Semiconducting Materials - The Promise of Flexible Electronics". AZoM. (accessed October 05, 2022).

  • Harvard

    Rasmussen, Seth. 2019. Designing Organic Semiconducting Materials - The Promise of Flexible Electronics. AZoM, viewed 05 October 2022,

Tell Us What You Think

Do you have a review, update or anything you would like to add to this article?

Leave your feedback
Your comment type