First-principles study of electronic transport and structural properties of Cu 12 Sb 4 S 13 in its high-temperature phase

Di Paola, Cono; Macheda, Francesco; Laricchia, Savio; Weber, Cedric; Bonini, Nicola

doi:10.1103/PhysRevResearch.2.033055

Title: First-principles study of electronic transport and structural properties of ${Cu}_{12} {Sb}_{4} S_{13}$ in its high-temperature phase

Journal Article · Fri Jul 10 00:00:00 EDT 2020 · Physical Review Research

DOI:https://doi.org/10.1103/PhysRevResearch.2.033055· OSTI ID:1638120

Di Paola, Cono; Macheda, Francesco; Laricchia, Savio; Weber, Cedric; Bonini, Nicola

We present an ab initio study of the structural and electronic transport properties of tetrahedrite, Cu₁₂Sb₄S₁₃, in its high-temperature phase. We show how this complex compound can be seen as the outcome of an ordered arrangement of S-vacancies in a semiconducting fematinite-like structure (Cu₃SbS₄). Our calculations confirm that the S-vacancies are the natural doping mechanism in this thermoelectric compound and reveal a similar local chemical environment around crystallographically inequivalent Cu atoms, shedding light on the debate on x-ray photoelectron spectroscopy measurements in this compound. To access the electrical transport properties as a function of temperature we use the Kubo-Greenwood formula applied to snapshots of first-principles molecular dynamics simulations. This approach is essential to effectively account for the interaction between electrons and lattice vibrations in such a complex crystal structure where a strong anharmonicity plays a key role in stabilizing the high-temperature phase. Our results show that the Seebeck coefficient is in good agreement with experiments and the phonon-limited electrical resistivity displays a temperature trend that compares well with a wide range of experimental data. The predicted lower bound for the resistivity turns out to be remarkably low for a pristine mineral in the Cu-Sb-S system but not too far from the lowest experimental data reported in literature. The Lorenz number turns out to be substantially lower than what is expected from the free-electron value in the Wiedemann-Franz law, thus providing an accurate way to estimate the electronic and lattice contributions to the thermal conductivity in experiments, of great significance in this very low thermal conductivity crystalline material.

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Research Organization:: King's College, London (United Kingdom)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 1638120

Alternate ID(s):: OSTI ID: 1638145

Journal Information:: Physical Review Research, Journal Name: Physical Review Research Vol. 2 Journal Issue: 3; ISSN 2643-1564

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: First-principles study of electronic transport and structural properties of Cu 12 Sb 4 S 13 in its high-temperature phase

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Title: First-principles study of electronic transport and structural properties of ${Cu}_{12} {Sb}_{4} S_{13}$ in its high-temperature phase