Jahn-Teller driven electronic instability in thermoelectric tetrahedrite

Long, S. O., Powell, A., Hull, S., Orlandi, F., Tang, C. C., Supka, A. R., Fornari, M. and Vaqueiro, P. ORCID: https://orcid.org/0000-0001-7545-6262 (2020) Jahn-Teller driven electronic instability in thermoelectric tetrahedrite. Advanced Functional Materials, 30 (12). 1909409. ISSN 1616-3028 doi: 10.1002/adfm.201909409

Abstract/Summary

Tetrahedrite, Cu12Sb4S13, is an abundant mineral with excellent thermoelectric properties owing to its low thermal conductivity. The electronic and structural origin of the intriguing physical properties of tetrahedrite, including its metal-to-semiconductor transition, remains largely unknown. This work presents the first determination of the low-temperature structure of tetrahedrite that accounts for its unique properties. Contrary to prior conjectures, our results show that the trigonal-planar copper cations remain in planar coordination below the metal-to-semiconductor transition. The atomic displacement parameters of the trigonal-planar copper cations, which have been linked to low thermal conductivity, increase by 200% above the metal-to-semiconductor transition. The phase transition is consequence of the orbital degeneracy of the highest occupied 3d cluster orbitals of the copper clusters found inside the sodalite cages in the cubic phase. This study reveals that a Jahn-Teller electronic instability leads to the formation of “molecular-like” Cu57+ clusters and suppresses copper rattling vibrations due to the strengthening of direct copper-copper interactions. Our first-principles calculations demonstrate that the structural phase transition opens a small band gap in the electronic density of states and eliminates the unstable phonon modes. The present results provide insights on the interplay between phonon transport, electronic properties and crystal structure in mixed-valence compounds.

Item Type	Article
URI	https://reading-clone.eprints-hosting.org/id/eprint/88295
Identification Number/DOI	10.1002/adfm.201909409
Refereed	Yes
Divisions	Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry Interdisciplinary centres and themes > Energy Research Interdisciplinary centres and themes > Chemical Analysis Facility (CAF) > Xray (CAF)
Uncontrolled Keywords	Jahn-Teller, thermoelectric, thermal conductivity, charge ordering, metal-insulator transition
Publisher	Wiley-Blackwell
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