Weak Electron–Phonon Coupling and Enhanced Thermoelectric Performance in n-type PbTe–Cu2Se via Dynamic Phase Conversion

Ming Wu; Hong Hua Cui; Songting Cai; Shiqiang Hao; Yukun Liu; Trevor P. Bailey; Yinying Zhang; Zixuan Chen; Yubo Luo; Ctirad Uher; Christopher Wolverton; Vinayak P. Dravid; Yan Yu; Zhong Zhen Luo; Zhigang Zou; Qingyu Yan; Mercouri G. Kanatzidis

doi:10.1002/aenm.202203325

Weak Electron–Phonon Coupling and Enhanced Thermoelectric Performance in n-type PbTe–Cu₂Se via Dynamic Phase Conversion

Ming Wu, Hong Hua Cui, Songting Cai, Shiqiang Hao, Yukun Liu, Trevor P. Bailey, Yinying Zhang, Zixuan Chen, Yubo Luo, Ctirad Uher, Christopher Wolverton, Vinayak P. Dravid, Yan Yu, Zhong Zhen Luo^*, Zhigang Zou, Qingyu Yan^*, Mercouri G. Kanatzidis^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

41 Scopus citations

Abstract

This study investigates Ga-doped n-type PbTe thermoelectric materials and the dynamic phase conversion process of the second phases via Cu₂Se alloying. Introducing Cu₂Se enhances its electrical transport properties while reducing its lattice thermal conductivity (κ_lat) via weak electron–phonon coupling. Cu₂Te and CuGa(Te/Se)₂ (tetragonal phase) nanocrystals precipitate during the alloying process, resulting in Te vacancies and interstitial Cu in the PbTe matrix. At room temperature, Te vacancies and interstitial Cu atoms serve as n-type dopants, increasing the carrier concentration and electrical conductivity from ≈1.18 × 10¹⁹ cm⁻³ and ≈1870 S cm⁻¹ to ≈2.26 × 10¹⁹ cm⁻³ and ≈3029 S cm⁻¹, respectively. With increasing temperature, the sample exhibits a dynamic change in Cu₂Te content and the generation of a new phase of CuGa(Te/Se)₂ (cubic phase), strengthening the phonon scattering and obtaining an ultralow κ_lat. Pb_0.975Ga_0.025Te-3%CuSe exhibits a maximum figure of merit of ≈1.63 at 823 K, making it promising for intermediate-temperature device applications.

Original language	English (US)
Article number	2203325
Journal	Advanced Energy Materials
Volume	13
Issue number	1
DOIs	https://doi.org/10.1002/aenm.202203325
State	Published - Jan 6 2023

Funding

M.W. and H.‐H.C. contributed equally to this work. This work was supported in part by the National Key Research and Development Program of China (No. 2020YFA0710303). At Northwestern work was supported in part by the Department of Energy, Office of Science, Basic Energy Sciences under Grant No. DE‐SC0014520, (sample preparation, synthesis, XRD, TE measurements, TEM measurements, DFT calculations). This study was supported in part by the National Natural Science Foundation of China (Nos. 52102218, U1905215, and 52072076) and the Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China (No. 2021ZZ127). The authors acknowledge the Minjiang Scholar Professorship (GXRC‐21004), the EPIC facility of Northwestern University's NUANCE Center, which received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS‐1542205), the MRSEC program (NSF DMR‐1720139) at the Materials Research Center, International Institute for Nanotechnology (IIN), Keck Foundation, State of Illinois, through IIN, and the Office of Science of the U.S. Department of Energy under Contract Nos. DE‐AC02‐06CH11357 and DE‐AC02‐05CH11231. The high temperature Hall effect measurements made at the University of Michigan were supported by a grant from the U. S. Department of Energy (Grant No. DE‐SC0018941). The authors also acknowledge the access to facilities for high‐performance computational resources at Northwestern University and Singapore MOE AcRF Tier 1 RG128/21, Singapore A*STAR project A19D9a0096. M.W. and H.-H.C. contributed equally to this work. This work was supported in part by the National Key Research and Development Program of China (No. 2020YFA0710303). At Northwestern work was supported in part by the Department of Energy, Office of Science, Basic Energy Sciences under Grant No. DE-SC0014520, (sample preparation, synthesis, XRD, TE measurements, TEM measurements, DFT calculations). This study was supported in part by the National Natural Science Foundation of China (Nos. 52102218, U1905215, and 52072076) and the Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China (No. 2021ZZ127). The authors acknowledge the Minjiang Scholar Professorship (GXRC-21004), the EPIC facility of Northwestern University's NUANCE Center, which received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the MRSEC program (NSF DMR-1720139) at the Materials Research Center, International Institute for Nanotechnology (IIN), Keck Foundation, State of Illinois, through IIN, and the Office of Science of the U.S. Department of Energy under Contract Nos. DE-AC02-06CH11357 and DE-AC02-05CH11231. The high temperature Hall effect measurements made at the University of Michigan were supported by a grant from the U. S. Department of Energy (Grant No. DE-SC0018941). The authors also acknowledge the access to facilities for high-performance computational resources at Northwestern University and Singapore MOE AcRF Tier 1 RG128/21, Singapore A*STAR project A19D9a0096.

Keywords

Cu Se alloying
dynamic phase conversion
electron–phonon coupling
n-type PbTe
thermoelectrics

ASJC Scopus subject areas

Renewable Energy, Sustainability and the Environment
General Materials Science

Access to Document

10.1002/aenm.202203325

Cite this

Wu, M., Cui, H. H., Cai, S., Hao, S., Liu, Y., Bailey, T. P., Zhang, Y., Chen, Z., Luo, Y., Uher, C., Wolverton, C., Dravid, V. P., Yu, Y., Luo, Z. Z., Zou, Z., Yan, Q., & Kanatzidis, M. G. (2023). Weak Electron–Phonon Coupling and Enhanced Thermoelectric Performance in n-type PbTe–Cu₂Se via Dynamic Phase Conversion. Advanced Energy Materials, 13(1), Article 2203325. https://doi.org/10.1002/aenm.202203325

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abstract = "This study investigates Ga-doped n-type PbTe thermoelectric materials and the dynamic phase conversion process of the second phases via Cu2Se alloying. Introducing Cu2Se enhances its electrical transport properties while reducing its lattice thermal conductivity (κlat) via weak electron–phonon coupling. Cu2Te and CuGa(Te/Se)2 (tetragonal phase) nanocrystals precipitate during the alloying process, resulting in Te vacancies and interstitial Cu in the PbTe matrix. At room temperature, Te vacancies and interstitial Cu atoms serve as n-type dopants, increasing the carrier concentration and electrical conductivity from ≈1.18 × 1019 cm−3 and ≈1870 S cm−1 to ≈2.26 × 1019 cm−3 and ≈3029 S cm−1, respectively. With increasing temperature, the sample exhibits a dynamic change in Cu2Te content and the generation of a new phase of CuGa(Te/Se)2 (cubic phase), strengthening the phonon scattering and obtaining an ultralow κlat. Pb0.975Ga0.025Te-3%CuSe exhibits a maximum figure of merit of ≈1.63 at 823 K, making it promising for intermediate-temperature device applications.",

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author = "Ming Wu and Cui, {Hong Hua} and Songting Cai and Shiqiang Hao and Yukun Liu and Bailey, {Trevor P.} and Yinying Zhang and Zixuan Chen and Yubo Luo and Ctirad Uher and Christopher Wolverton and Dravid, {Vinayak P.} and Yan Yu and Luo, {Zhong Zhen} and Zhigang Zou and Qingyu Yan and Kanatzidis, {Mercouri G.}",

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Wu, M, Cui, HH, Cai, S, Hao, S, Liu, Y, Bailey, TP, Zhang, Y, Chen, Z, Luo, Y, Uher, C, Wolverton, C , Dravid, VP, Yu, Y, Luo, ZZ, Zou, Z, Yan, Q & Kanatzidis, MG 2023, 'Weak Electron–Phonon Coupling and Enhanced Thermoelectric Performance in n-type PbTe–Cu₂Se via Dynamic Phase Conversion', Advanced Energy Materials, vol. 13, no. 1, 2203325. https://doi.org/10.1002/aenm.202203325

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AU - Wu, Ming

AU - Cui, Hong Hua

AU - Cai, Songting

AU - Hao, Shiqiang

AU - Liu, Yukun

AU - Bailey, Trevor P.

AU - Zhang, Yinying

AU - Chen, Zixuan

AU - Luo, Yubo

AU - Uher, Ctirad

AU - Wolverton, Christopher

AU - Dravid, Vinayak P.

AU - Yu, Yan

AU - Luo, Zhong Zhen

AU - Zou, Zhigang

AU - Yan, Qingyu

AU - Kanatzidis, Mercouri G.

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AB - This study investigates Ga-doped n-type PbTe thermoelectric materials and the dynamic phase conversion process of the second phases via Cu2Se alloying. Introducing Cu2Se enhances its electrical transport properties while reducing its lattice thermal conductivity (κlat) via weak electron–phonon coupling. Cu2Te and CuGa(Te/Se)2 (tetragonal phase) nanocrystals precipitate during the alloying process, resulting in Te vacancies and interstitial Cu in the PbTe matrix. At room temperature, Te vacancies and interstitial Cu atoms serve as n-type dopants, increasing the carrier concentration and electrical conductivity from ≈1.18 × 1019 cm−3 and ≈1870 S cm−1 to ≈2.26 × 1019 cm−3 and ≈3029 S cm−1, respectively. With increasing temperature, the sample exhibits a dynamic change in Cu2Te content and the generation of a new phase of CuGa(Te/Se)2 (cubic phase), strengthening the phonon scattering and obtaining an ultralow κlat. Pb0.975Ga0.025Te-3%CuSe exhibits a maximum figure of merit of ≈1.63 at 823 K, making it promising for intermediate-temperature device applications.

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