High Thermoelectric Performance in Chalcopyrite Cu1-xAgxGaTe2–ZnTe: Nontrivial Band Structure and Dynamic Doping Effect

Xie, Hongyao; Liu, Yukun; Zhang, Yinying; Hao, Shiqiang; Li, Zhi; Cheng, Matthew; Cai, Songting; Snyder, G. Jeffrey; Wolverton, Christopher; Uher, Ctirad; Dravid, Vinayak P.; Kanatzidis, Mercouri G.

doi:10.1021/jacs.2c02726

Title: High Thermoelectric Performance in Chalcopyrite Cu_1-xAg_xGaTe₂–ZnTe: Nontrivial Band Structure and Dynamic Doping Effect

Journal Article · Tue May 10 00:00:00 EDT 2022 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.2c02726· OSTI ID:1867601

^[1]; Liu, Yukun ^[1];

^[2];

^[1];

^[1]; Uher, Ctirad ^[2];

^[1];

^[1]

Northwestern Univ., Evanston, IL (United States)
Univ. of Michigan, Ann Arbor, MI (United States)

The understanding of thermoelectric properties of ternary I–III–VI₂ type (I = Cu, Ag; III = Ga, In; and VI = Te) chalcopyrites is less well developed. Although their thermal transport properties are relatively well studied, the relationship between the electronic band structure and charge transport properties of chalcopyrites has been rarely discussed. In this study, we reveal the unusual electronic band structure and the dynamic doping effect that could underpin the promising thermoelectric properties of Cu_1–xAg_xGaTe₂ compounds. Density functional theory (DFT) calculations and electronic transport measurements suggest that the Cu_1–xAg_xGaTe₂ compounds possess an unusual non-parabolic band structure, which is important for obtaining a high Seebeck coefficient. Moreover, a mid-gap impurity level was also observed in Cu_1–xAg_xGaTe₂, which leads to a strong temperature-dependent carrier concentration and is able to regulate the carrier density at the optimized value for a wide temperature region and thus is beneficial to obtaining the high power factor and high average ZT of Cu_1–xAg_xGaTe₂ compounds. We also demonstrate a great improvement in the thermoelectric performance of Cu_1–xAg_xGaTe₂ by introducing Cu vacancies and ZnTe alloying. The Cu vacancies are effective in increasing the hole density and the electrical conductivity, while ZnTe alloying reduces the thermal conductivity. As a result, a maximum ZT of 1.43 at 850 K and a record-high average ZT of 0.81 for the Cu_0.68Ag_0.3GaTe₂–0.5%ZnTe compound are achieved.

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Research Organization:: Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0014520; ECCS-2025633; DMR-1720139

OSTI ID:: 1867601

Journal Information:: Journal of the American Chemical Society, Vol. 144, Issue 20; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
chalcopyrite
nontrivial band structure
dynamic doping effect
Cu vacancy
ZnTe alloying

Title: High Thermoelectric Performance in Chalcopyrite Cu1-xAgxGaTe2–ZnTe: Nontrivial Band Structure and Dynamic Doping Effect

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References (53)

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Title: High Thermoelectric Performance in Chalcopyrite Cu_1-xAg_xGaTe₂–ZnTe: Nontrivial Band Structure and Dynamic Doping Effect