Insight into the structures and dynamics of organic semiconductors through solid-state NMR spectroscopy

Abstract

Organic semiconductors (OSCs) are of fundamental and technological interest, owing to their properties and functions in a range of optoelectronic devices, including organic light-emitting diodes, organic photovoltaics and organic field-effect transistors, as well as emerging technologies, such as bioelectronic devices. The solid-state organization of the subunits in OSC materials, whether molecular or polymeric, determines the properties relevant to device performance. Nevertheless, the systematic relationships between composition, structure and processing conditions are rarely fully understood, owing to the complexity of the organic architectures and the resulting solid-state structures. Characterization over different length scales and timescales is essential, especially for semi-ordered or amorphous regions, for which solid-state NMR (ssNMR) spectroscopy yields nanoscale insight that can be correlated with scattering measurements and macroscopic property analyses. In this Review, we assess recent results, challenges and opportunities in the application of ssNMR to OSCs, highlighting its role in state-of-the-art materials design and characterization. We illustrate how insight is obtained on local order and composition, interfacial structures, dynamics, interactions and how this information can be used to establish structure–property relationships. Finally, we provide our perspective on applying ssNMR to the next generation of OSCs and the development of new ssNMR methods.

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Fig. 1: Order within organic semiconductor materials.
Fig. 2: Molecules used to fabricate high-performance organic semiconductor materials.
Fig. 3: Length scales and timescales of characterization techniques.
Fig. 4: Quantifying order.
Fig. 5: Integrated analysis of organic semiconductors and determination of 3D structures.
Fig. 6: Characterizing packing interactions, local structures and bulk heterojunctions.
Fig. 7: Structure determination of an organic semiconductor–fullerene blend.
Fig. 8: Characterizing molecularly doped organic semiconductor materials.
Fig. 9: Characterizing phase transitions and molecular motions.

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Acknowledgements

The authors acknowledge funding support from the US Department of the Navy, Office of Naval Research (award nos. N00014-14-1-0580 and N00014-16-1-2520) and the Mitsubishi Chemical Center for Advanced Materials (MC-CAM). G.N.M.R. gratefully acknowledges the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant no. 795091. The authors thank M.R. Hansen for helpful discussions and for providing them with ssNMR spectra.

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M.S. and G.N.M.R. researched the literature and wrote the initial manuscript draft. All authors contributed to the discussion of the content and edited the manuscript before submission.

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Correspondence to G. N. Manjunatha Reddy or Bradley F. Chmelka or Guillermo C. Bazan.

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Seifrid, M., Reddy, G.N.M., Chmelka, B.F. et al. Insight into the structures and dynamics of organic semiconductors through solid-state NMR spectroscopy. Nat Rev Mater (2020). https://doi.org/10.1038/s41578-020-00232-5

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