Plasmonic high-entropy carbides

Arrigo Calzolari; Corey Oses; Cormac Toher; Marco Esters; Xiomara Campilongo; Sergei P Stepanoff; Douglas E Wolfe; Stefano Curtarolo

doi:10.1038/s41467-022-33497-1

Plasmonic high-entropy carbides

Nat Commun. 2022 Oct 11;13(1):5993. doi: 10.1038/s41467-022-33497-1.

Authors

Arrigo Calzolari¹, Corey Oses^{2

3}, Cormac Toher^{3

4}, Marco Esters^{2

3}, Xiomara Campilongo³, Sergei P Stepanoff⁵, Douglas E Wolfe⁵, Stefano Curtarolo^{6

7}

Affiliations

¹ CNR-NANO Research Center S3, Modena, Italy. arrigo.calzolari@nano.cnr.it.
² Department of Mechanical Engineering and Materials Science, Duke University, Durham, NC, USA.
³ Center for Autonomous Materials Design, Duke University, Durham, NC, USA.
⁴ Department of Materials Science and Engineering and Department of Chemistry and Biochemistry, University of Texas at Dallas, Richardson, TX, USA.
⁵ Applied Research Laboratory, The Pennsylvania State University, University Park, PA, USA.
⁶ Department of Mechanical Engineering and Materials Science, Duke University, Durham, NC, USA. stefano@duke.edu.
⁷ Center for Autonomous Materials Design, Duke University, Durham, NC, USA. stefano@duke.edu.

Abstract

Discovering multifunctional materials with tunable plasmonic properties, capable of surviving harsh environments is critical for advanced optical and telecommunication applications. We chose high-entropy transition-metal carbides because of their exceptional thermal, chemical stability, and mechanical properties. By integrating computational thermodynamic disorder modeling and time-dependent density functional theory characterization, we discovered a crossover energy in the infrared and visible range, corresponding to a metal-to-dielectric transition, exploitable for plasmonics. It was also found that the optical response of high-entropy carbides can be largely tuned from the near-IR to visible when changing the transition metal components and their concentration. By monitoring the electronic structures, we suggest rules for optimizing optical properties and designing tailored high-entropy ceramics. Experiments performed on the archetype carbide HfTa₄C₅ yielded plasmonic properties from room temperature to 1500K. Here we propose plasmonic transition-metal high-entropy carbides as a class of multifunctional materials. Their combination of plasmonic activity, high-hardness, and extraordinary thermal stability will result in yet unexplored applications.