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Understanding the relationship between frontier orbital level offsets to optoelectronic and electronic properties of doped P3HT-based composites

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Abstract

One of the greatest advantages of organic/polymeric semiconductors is their ease of tunability of optoelectronic, electronic, and optical properties pre- and post-synthesis. Chemical doping has numerous advantages in comparison to the other routes due to being quick, cost-effective, and highly controllable. For dopants to ionize the host material, the frontier orbital offset should be carefully engineered to enable efficient charge transfer between dopant and host material. This work directly studies different frontier orbital levels between poly(3-hexylthiophene-2,5-diyl) (P3HT) and a variety of molecular dopants. Results show that the electrical conductivity decreases as the LUMO of the dopant increases; this could be explained by the increased energy barrier for electron transfer from the HOMO of the P3HT to the LUMO of the dopant acceptors. Among the several dopants investigated, this study reveals that the Seebeck coefficients decrease as the frontier orbital offsets (between P3HT HOMO and acceptor LUMO) decrease and the electrical conductivity increases. Optimal offsets are also identified where certain parameters exhibit the highest or lowest values.

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All data that were generated and/or analyzed during this study are included in this published article and its supplementary information files.

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Funding

This material is based upon work supported, in parts, by grant awards from the United States National Science Foundation (NSF Award # HRD-1547771). Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the US Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.

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Authors and Affiliations

  1. Sandia National Laboratories, Advanced Materials Laboratory, Albuquerque, NM, 87106, USA

    Harold O. Lee III & LaRico J. Treadwell

  2. Center for Materials Research, Norfolk State University, Norfolk, VA, 23504, USA

    Sam-Shajing Sun

Authors
  1. Harold O. Lee III
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  2. LaRico J. Treadwell
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  3. Sam-Shajing Sun
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Contributions

All the authors contributed to the conception, experiment, design, and analysis. Material preparation and data collection was performed by HOL. Analysis was performed by HOL, LJT, and SSS. The first draft of the manuscript was written by HOL, and all the authors commented on previous versions of the manuscript. All the authors read and approved the final manuscript.

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Correspondence to Sam-Shajing Sun.

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Lee, H.O., Treadwell, L.J. & Sun, SS. Understanding the relationship between frontier orbital level offsets to optoelectronic and electronic properties of doped P3HT-based composites. J Mater Sci: Mater Electron 33, 24276–24284 (2022). https://doi.org/10.1007/s10854-022-09148-y

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  • DOI: https://doi.org/10.1007/s10854-022-09148-y

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