Improved thermoelectric performance of α- and β- Cu2Se through suppression of hole density using extrinsic copper vacancies

Yin, Zhixiong; Lu, Ruiming; Bailey, Trevor P.; Ma, Tao; Uher, Ctirad; Poudeu, Pierre F.P.

doi:10.1016/j.cej.2024.157558

Title: Improved thermoelectric performance of α- and β- Cu₂Se through suppression of hole density using extrinsic copper vacancies

Journal Article · 09 November 2024 · Chemical Engineering Journal

DOI: https://doi.org/10.1016/j.cej.2024.157558 · OSTI ID:2503970

Yin, Zhixiong ^[1]; Lu, Ruiming ^[1]; Bailey, Trevor P. ^[1]; Ma, Tao ^[1]; Uher, Ctirad ^[1]; Poudeu, Pierre F.P. ^[1]

University of Michigan, Ann Arbor, MI (United States)

Modulating Cu⁺ ion disorder in Cu₂Se can enable control over the polymorphism and the carrier density leading to enhanced thermoelectric properties for both α- and β-Cu₂Se. Here we report that the incorporation of Cr³⁺ into the Cu₂Se crystal lattice facilitates the stabilization of α-Cu₂Se at 300 K leading to a large (~140%) reduction in the carrier density both below and above the phase transition. This is attributed to the reduction in the density of intrinsic copper interstitials (Cu$$^{•}_{i}$$) within the Cu_(2-δ-λ)(Cr$$^{··}_{Cu}$$)λ(V$$^{'}_{Cu}$$)δ(Cu$$^{π}_{i}$$)_δ-2λ(h^•)_δ-2λSe crystal lattice. Such optimization of the carrier density led to a large (63%) increase in the thermopower and a drastic (46%) reduction in the total thermal conductivity for both α- and β-Cu₂Se matrices. Consequently, a significant enhancement of the thermoelectric performance is observed in the entire temperature range from 300 K to 773 K. This results in high average ZT values for both α-Cu₂Se (ZT_ave = 0.60) and β-Cu₂Se (ZT_ave = 0.97), which paves the way for both near room temperature and high temperatures applications. Furthermore, this work provides a new approach to optimize the thermoelectric performance of Cu₂Se-based materials by leveraging the interaction between mobile intrinsic Cu$$^{·}_{i}$$ and extrinsic V$$^{'}_{Cu}$$ to suppress the hole density.

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Research Organization:: University of Michigan, Ann Arbor, MI (United States)

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

Grant/Contract Number:: SC0018941

OSTI ID:: 2503970

Journal Information:: Chemical Engineering Journal, Journal Name: Chemical Engineering Journal Vol. 501; ISSN 1385-8947

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Improved thermoelectric performance of α- and β- Cu2Se through suppression of hole density using extrinsic copper vacancies

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Title: Improved thermoelectric performance of α- and β- Cu₂Se through suppression of hole density using extrinsic copper vacancies