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The journey of conducting polymers from discovery to application

Nature Materials volume 19, pages 922–928 (2020)Cite this article

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Shirakawa, MacDiarmid and Heeger received the 2000 Nobel Prize in Chemistry for the discovery of conducting polymers. Here we summarize the impact of (semi)conducting polymers on fundamental research, synthetic accessibility at scale, industrial applicability and the future.

Before the discovery of polyacetylene, the CP prototype was the inorganic material poly(sulfur nitride) (SN)x (Fig. 1a), a material exhibiting intrinsic (thus without doping) metallic conductivity where electrons in a partially filled conduction band move freely at long (ballistic) distances2. In (SN)x all bonds have equal length, meaning that the bond length alternation (BLA) along the chain is zero, a key feature to achieve high conductivity. However, it has been suggested that the structure of polyacetylene is more energetically stable when the chain has a BLA ≠ 0, which opens an energy gap (Eg) between the top of the valence band and bottom of the conduction band (Fig. 1b), resulting in insulating behaviour. The effect of doping a polymer — for instance, by exposing it to halogen vapours, as done by the three Nobel Laureates — is to reduce the energy gap and enhance the carrier density to achieve a different degree of semiconducting (or even metallic) behaviour (Fig. 1b) and tuning the material’s colour (Fig. 1c). Organic chemists also realized that the use of (hetero)aromatic rings enabled the design of undoped polymers with tailorable intrinsic (semi)conducting properties. Thus, starting from the discovery in the 1980s of important CPs such as polyaniline and polypyrrole (Fig. 1d), the field exploded in the 1990s with the realization of several structures via different synthetic strategies (Fig. 1e). Equally important for the properties and application of CPs is the way the isolated polymeric chains interact with each other in condensed phase, forming supramolecular assemblies that determine the processability, opto-electronic characteristics, and film morphology. Unlike inorganic (semi)conductors, where the atoms are held by strong covalent bonds, CPs consist of discrete macromolecules that are bound together via weaker supramolecular π–π, van der Waals and dipolar interactions. These forces are collectively strong enough in first-generation CPs to prevent their processing with solution-based methodologies. However, molecular engineering by side-chain modification and use of particular heteroatoms has unlocked these processing techniques, giving CPs a paramount advantage over ‘hard’ inorganic analogues3. Synthesis efforts in this field have been driven both by the need to understand charge transport mechanisms and structure–property relationships in these solids, as well as by more practical goals — such as replacing heavy metal wires and lead batteries in airplanes and cars with lighter materials, developing new functional coatings to dissipate static electricity and shield electromagnetic radiation, and realizing new displays. Efforts have also been directed to the development of CPs with a very low intrinsic carrier density (semiconductor) and enabling coupled electronic/ionic transport for exploration in electronic circuits, light emission, clean energy production, and bioelectronics, as described in the following sections.

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Fig. 1: Structures, synthesis and properties of CPs.
Fig. 2: Applications of conducting polymers.
Fig. 3: Ongoing fundamental studies and exploration of applications.

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Acknowledgements

The authors are grateful to Shenzhen Science and Technology Innovation Commission (KQTD20140630110339343), AFOSR (FA9550-18-1-0320), and ONR (N00014-20-1-2116).

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Authors and Affiliations

  1. Department of Materials Science and Engineering, Southern University of Science and Technology (SUSTech), Shenzhen, Guangdong, China

    Xugang Guo

  2. Flexterra Corporation, Skokie, IL, USA

    Antonio Facchetti

  3. Department of Chemistry and the Materials Research Center, Northwestern University, Evanston, IL, USA

    Antonio Facchetti

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  1. Xugang Guo
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Correspondence to Xugang Guo or Antonio Facchetti.

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Competing interests

A.F. is the founder and chief technology officer of Flexterra Corporation and has been a scientific advisor of Raynergy Teck. X.G. declares no competing interests.

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Guo, X., Facchetti, A. The journey of conducting polymers from discovery to application. Nat. Mater. 19, 922–928 (2020). https://doi.org/10.1038/s41563-020-0778-5

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