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

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 ^[2]; ^[3]; ^[2]; ^[2]; ^[2]; ^[2]; ^[2]; ^[2]; Uher, Ctirad ^[3]; ^[2]; ^[2]

Northwestern Univ., Evanston, IL (United States); Northwestern University
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.

View Accepted Manuscript (DOE)

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

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

Grant/Contract Number:: SC0014520

OSTI ID:: 1867601

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

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (70)

On the Design of High-Efficiency Thermoelectric Clathrates through a Systematic Cross-Substitution of Framework Elements Shi, Xun; Yang, Jiong; Bai, Shengqiang Advanced Functional Materials, Vol. 20, Issue 5 https://doi.org/10.1002/adfm.200901817	journal	March 2010
Hierarchical Chemical Bonds Contributing to the Intrinsically Low Thermal Conductivity in α-MgAgSb Thermoelectric Materials Ying, Pingjun; Li, Xin; Wang, Yancheng Advanced Functional Materials, Vol. 27, Issue 1 https://doi.org/10.1002/adfm.201604145	journal	October 2016
High Thermoelectric Performance in the Wide Band‐Gap AgGa _1‐ _x Te ₂ Compounds: Directional Negative Thermal Expansion and Intrinsically Low Thermal Conductivity Su, Xianli; Zhao, Na; Hao, Shiqiang Advanced Functional Materials, Vol. 29, Issue 6 https://doi.org/10.1002/adfm.201806534	journal	December 2018
Origin of the Distinct Thermoelectric Transport Properties of Chalcopyrite ABTe ₂ (A = Cu, Ag; B = Ga, In) Cao, Yu; Su, Xianli; Meng, Fanchen Advanced Functional Materials, Vol. 30, Issue 51 https://doi.org/10.1002/adfm.202005861	journal	September 2020
Chalcopyrite CuGaTe2: A High-Efficiency Bulk Thermoelectric Material Plirdpring, Theerayuth; Kurosaki, Ken; Kosuga, Atsuko Advanced Materials, Vol. 24, Issue 27 https://doi.org/10.1002/adma.201200732	journal	June 2012
High-Performance Pseudocubic Thermoelectric Materials from Non-cubic Chalcopyrite Compounds Zhang, Jiawei; Liu, Ruiheng; Cheng, Nian Advanced Materials, Vol. 26, Issue 23 https://doi.org/10.1002/adma.201400058	journal	April 2014
Compromise and Synergy in High-Efficiency Thermoelectric Materials Zhu, Tiejun; Liu, Yintu; Fu, Chenguang Advanced Materials, Vol. 29, Issue 14 https://doi.org/10.1002/adma.201605884	journal	March 2017
Design of Domain Structure and Realization of Ultralow Thermal Conductivity for Record‐High Thermoelectric Performance in Chalcopyrite Zhang, Jian; Huang, Lulu; Zhu, Chen Advanced Materials, Vol. 31, Issue 52 https://doi.org/10.1002/adma.201905210	journal	November 2019
Weighted Mobility Snyder, G. Jeffrey; Snyder, Alemayouh H.; Wood, Maxwell Advanced Materials, Vol. 32, Issue 25 https://doi.org/10.1002/adma.202001537	journal	May 2020
Intrinsically High Thermoelectric Performance in AgInSe ₂ n-Type Diamond-Like Compounds Qiu, Pengfei; Qin, Yuting; Zhang, Qihao Advanced Science, Vol. 5, Issue 3 https://doi.org/10.1002/advs.201700727	journal	December 2017
High‐Performance Thermoelectric SnSe: Aqueous Synthesis, Innovations, and Challenges Shi, Xiao‐Lei; Tao, Xinyong; Zou, Jin Advanced Science, Vol. 7, Issue 7 https://doi.org/10.1002/advs.201902923	journal	February 2020
Self-Tuning the Carrier Concentration of PbTe/Ag2Te Composites with Excess Ag for High Thermoelectric Performance Pei, Yanzhong; May, Andrew F.; Snyder, G. Jeffrey Advanced Energy Materials, Vol. 1, Issue 2 https://doi.org/10.1002/aenm.201000072	journal	February 2011
Optimum Carrier Concentration in n-Type PbTe Thermoelectrics Pei, Yanzhong; Gibbs, Zachary M.; Gloskovskii, Andrei Advanced Energy Materials, Vol. 4, Issue 13 https://doi.org/10.1002/aenm.201400486	journal	May 2014
Mechanically Robust BiSbTe Alloys with Superior Thermoelectric Performance: A Case Study of Stable Hierarchical Nanostructured Thermoelectric Materials Zheng, Yun; Zhang, Qiang; Su, Xianli Advanced Energy Materials, Vol. 5, Issue 5 https://doi.org/10.1002/aenm.201401391	journal	November 2014
Progressive Regulation of Electrical and Thermal Transport Properties to High-Performance CuInTe ₂ Thermoelectric Materials Luo, Yubo; Yang, Junyou; Jiang, Qinghui Advanced Energy Materials, Vol. 6, Issue 12 https://doi.org/10.1002/aenm.201600007	journal	April 2016
The Role of Zn in Chalcopyrite CuFeS ₂ : Enhanced Thermoelectric Properties of Cu _1- _x Zn _x FeS ₂ with In Situ Nanoprecipitates Xie, Hongyao; Su, Xianli; Zheng, Gang Advanced Energy Materials, Vol. 7, Issue 3 https://doi.org/10.1002/aenm.201601299	journal	October 2016
New and Old Concepts in Thermoelectric Materials Sootsman, Joseph R.; Chung, Duck Young; Kanatzidis, Mercouri G. Angewandte Chemie International Edition, Vol. 48, Issue 46, p. 8616-8639 https://doi.org/10.1002/anie.200900598	journal	November 2009
A comprehensive review on Bi ₂ Te ₃ ‐based thin films: Thermoelectrics and beyond Tang, Xinfeng; Li, Ziwei; Liu, Wei Interdisciplinary Materials, Vol. 1, Issue 1 https://doi.org/10.1002/idm2.12009	journal	January 2022
Introduction to Thermoelectricity Goldsmid, H. Julian Springer Series in Materials Science https://doi.org/10.1007/978-3-662-49256-7	book	January 2016
Enhancement of thermoelectric performance by tuning selenium content in the Cu2SnSe3 compound Gurukrishna, K.; Rao, Ashok; Jiang, Zhao-Ze Intermetallics, Vol. 122 https://doi.org/10.1016/j.intermet.2020.106803	journal	July 2020
Charge-carrier-mediated lattice softening contributes to high zT in thermoelectric semiconductors Slade, Tyler J.; Anand, Shashwat; Wood, Max Joule, Vol. 5, Issue 5 https://doi.org/10.1016/j.joule.2021.03.009	journal	May 2021
High performance bulk thermoelectrics via a panoscopic approach He, Jiaqing; Kanatzidis, Mercouri G.; Dravid, Vinayak P. Materials Today, Vol. 16, Issue 5 https://doi.org/10.1016/j.mattod.2013.05.004	journal	May 2013
Physical insights on the low lattice thermal conductivity of AgInSe2 Zhu, Yingcai; Wei, Bin; Liu, Junyan Materials Today Physics, Vol. 19 https://doi.org/10.1016/j.mtphys.2021.100428	journal	July 2021
Large enhancement of thermoelectric performance of CuInTe 2 via a synergistic strategy of point defects and microstructure engineering Luo, Yubo; Yang, Junyou; Jiang, Qinghui Nano Energy, Vol. 18 https://doi.org/10.1016/j.nanoen.2015.09.015	journal	November 2015
Synergistically Optimizing Carrier Concentration and Decreasing Sound Velocity in n-type AgInSe ₂ Thermoelectrics Zhu, Yingcai; Liu, Yong; Wood, Max Chemistry of Materials, Vol. 31, Issue 19 https://doi.org/10.1021/acs.chemmater.9b03011	journal	September 2019
Rationally Designing High-Performance Bulk Thermoelectric Materials Tan, Gangjian; Zhao, Li-Dong; Kanatzidis, Mercouri G. Chemical Reviews, Vol. 116, Issue 19 https://doi.org/10.1021/acs.chemrev.6b00255	journal	August 2016
All-Inorganic Halide Perovskites as Potential Thermoelectric Materials: Dynamic Cation off-Centering Induces Ultralow Thermal Conductivity Xie, Hongyao; Hao, Shiqiang; Bao, Jinke Journal of the American Chemical Society, Vol. 142, Issue 20 https://doi.org/10.1021/jacs.0c03427	journal	April 2020
Ultralow Thermal Conductivity in Diamondoid Structures and High Thermoelectric Performance in (Cu _{1– x} Ag _x )(In _{1– y} Ga _y )Te ₂ Xie, Hongyao; Hao, Shiqiang; Bailey, Trevor P. Journal of the American Chemical Society, Vol. 143, Issue 15 https://doi.org/10.1021/jacs.1c01801	journal	April 2021
Codoping in SnTe: Enhancement of Thermoelectric Performance through Synergy of Resonance Levels and Band Convergence Tan, Gangjian; Shi, Fengyuan; Hao, Shiqiang Journal of the American Chemical Society, Vol. 137, Issue 15 https://doi.org/10.1021/jacs.5b00837	journal	April 2015
Remarkable Roles of Cu To Synergistically Optimize Phonon and Carrier Transport in n-Type PbTe-Cu ₂ Te Xiao, Yu; Wu, Haijun; Li, Wei Journal of the American Chemical Society, Vol. 139, Issue 51 https://doi.org/10.1021/jacs.7b11662	journal	December 2017
Chemical Insights into PbSe– x %HgSe: High Power Factor and Improved Thermoelectric Performance by Alloying with Discordant Atoms Hodges, James M.; Hao, Shiqiang; Grovogui, Jann A. Journal of the American Chemical Society, Vol. 140, Issue 51 https://doi.org/10.1021/jacs.8b11050	journal	November 2018
Origin of Intrinsically Low Thermal Conductivity in Talnakhite Cu _17.6 Fe _17.6 S ₃₂ Thermoelectric Material: Correlations between Lattice Dynamics and Thermal Transport Xie, Hongyao; Su, Xianli; Zhang, Xiaomi Journal of the American Chemical Society, Vol. 141, Issue 27 https://doi.org/10.1021/jacs.9b05072	journal	June 2019
Large Thermal Conductivity Drops in the Diamondoid Lattice of CuFeS ₂ by Discordant Atom Doping Xie, Hongyao; Su, Xianli; Hao, Shiqiang Journal of the American Chemical Society, Vol. 141, Issue 47 https://doi.org/10.1021/jacs.9b10983	journal	November 2019
Shifting up the optimum figure of merit of p-type bismuth telluride-based thermoelectric materials for power generation by suppressing intrinsic conduction Hu, Li-Peng; Zhu, Tie-Jun; Wang, Ya-Guang NPG Asia Materials, Vol. 6, Issue 2 https://doi.org/10.1038/am.2013.86	journal	February 2014
High-performance nanostructured thermoelectric materials Li, Jing-Feng; Liu, Wei-Shu; Zhao, Li-Dong NPG Asia Materials, Vol. 2, Issue 4 https://doi.org/10.1038/asiamat.2010.138	journal	October 2010
Convergence of electronic bands for high performance bulk thermoelectrics Pei, Yanzhong; Shi, Xiaoya; LaLonde, Aaron Nature, Vol. 473, Issue 7345, p. 66-69 https://doi.org/10.1038/nature09996	journal	May 2011
High-performance bulk thermoelectrics with all-scale hierarchical architectures Biswas, Kanishka; He, Jiaqing; Blum, Ivan D. Nature, Vol. 489, Issue 7416, p. 414-418 https://doi.org/10.1038/nature11439	journal	September 2012
Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals Zhao, Li-Dong; Lo, Shih-Han; Zhang, Yongsheng Nature, Vol. 508, Issue 7496, p. 373-377 https://doi.org/10.1038/nature13184	journal	April 2014
Strained endotaxial nanostructures with high thermoelectric figure of merit Biswas, Kanishka; He, Jiaqing; Zhang, Qichun Nature Chemistry, Vol. 3, Issue 2 https://doi.org/10.1038/nchem.955	journal	January 2011
Non-equilibrium processing leads to record high thermoelectric figure of merit in PbTe–SrTe Tan, Gangjian; Shi, Fengyuan; Hao, Shiqiang Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms12167	journal	July 2016
Discovery of high-performance low-cost n-type Mg3Sb2-based thermoelectric materials with multi-valley conduction bands Zhang, Jiawei; Song, Lirong; Pedersen, Steffen Hindborg Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms13901	journal	January 2017
Broad temperature plateau for thermoelectric figure of merit ZT>2 in phase-separated PbTe0.7S0.3 Wu, H. J.; Zhao, L. -D.; Zheng, F. S. Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5515	journal	July 2014
Complex thermoelectric materials Snyder, G. Jeffrey; Toberer, Eric S. Nature Materials, Vol. 7, Issue 2, p. 105-114 https://doi.org/10.1038/nmat2090	journal	February 2008
Thermoelectric materials step up Shi, Xun; Chen, Lidong Nature Materials, Vol. 15, Issue 7 https://doi.org/10.1038/nmat4643	journal	June 2016
On the tuning of electrical and thermal transport in thermoelectrics: an integrated theory–experiment perspective Yang, Jiong; Xi, Lili; Qiu, Wujie npj Computational Materials, Vol. 2, Issue 1 https://doi.org/10.1038/npjcompumats.2015.15	journal	February 2016
Superior thermoelectric performance in PbTe–PbS pseudo-binary: extremely low thermal conductivity and modulated carrier concentration Wu, Di; Zhao, Li-Dong; Tong, Xiao Energy & Environmental Science, Vol. 8, Issue 7 https://doi.org/10.1039/C5EE01147G	journal	January 2015
High thermoelectric performance from optimization of hole-doped CuInTe ₂ Zhou, Gang; Wang, Dong Physical Chemistry Chemical Physics, Vol. 18, Issue 8 https://doi.org/10.1039/c5cp05129k	journal	January 2016
New insight into the material parameter B to understand the enhanced thermoelectric performance of Mg ₂ Sn _1−x−y Ge _x Sb _y Liu, Weishu; Zhou, Jiawei; Jie, Qing Energy & Environmental Science, Vol. 9, Issue 2 https://doi.org/10.1039/c5ee02600h	journal	January 2016
Broad temperature plateau for high ZTs in heavily doped p-type SnSe single crystals Peng, Kunling; Lu, Xu; Zhan, Heng Energy & Environmental Science, Vol. 9, Issue 2 https://doi.org/10.1039/c5ee03366g	journal	January 2016
Optimized thermoelectric properties in pseudocubic diamond-like CuGaTe ₂ compounds Qin, Yuting; Qiu, Pengfei; Liu, Ruiheng Journal of Materials Chemistry A, Vol. 4, Issue 4 https://doi.org/10.1039/c5ta09584k	journal	January 2016
Thermoelectric performance of Cu _1−x−δ Ag _x InTe ₂ diamond-like materials with a pseudocubic crystal structure Liu, Ruiheng; Qin, Yuting; Cheng, Nian Inorganic Chemistry Frontiers, Vol. 3, Issue 9 https://doi.org/10.1039/c6qi00162a	journal	January 2016
Substitutional defects enhancing thermoelectric CuGaTe ₂ Shen, Jiawen; Zhang, Xinyue; Chen, Zhiwei Journal of Materials Chemistry A, Vol. 5, Issue 11 https://doi.org/10.1039/c6ta10770b	journal	January 2017
High thermoelectric performance of p-BiSbTe compounds prepared by ultra-fast thermally induced reaction Zheng, Gang; Su, Xianli; Xie, Hongyao Energy & Environmental Science, Vol. 10, Issue 12 https://doi.org/10.1039/c7ee02677c	journal	January 2017
Realizing high performance n-type PbTe by synergistically optimizing effective mass and carrier mobility and suppressing bipolar thermal conductivity Xiao, Yu; Wu, Haijun; Cui, Juan Energy & Environmental Science, Vol. 11, Issue 9 https://doi.org/10.1039/c8ee01151f	journal	January 2018
Ultralow thermal conductivity in diamondoid lattices: high thermoelectric performance in chalcopyrite Cu _0.8+y Ag _0.2 In _1−y Te ₂ Xie, Hongyao; Hao, Shiqiang; Cai, Songting Energy & Environmental Science, Vol. 13, Issue 10 https://doi.org/10.1039/d0ee02323j	journal	January 2020
Electronic Transport in Semimetallic Cerium Sulfide Cutler, M.; Leavy, J. F.; Fitzpatrick, R. L. Physical Review, Vol. 133, Issue 4A https://doi.org/10.1103/physrev.133.a1143	journal	February 1964
Electronic Transport in High-Resistivity Cerium Sulfide Cutler, M.; Leavy, J. F. Physical Review, Vol. 133, Issue 4A https://doi.org/10.1103/physrev.133.a1153	journal	February 1964
Skutterudite antimonides: Quasilinear bands and unusual transport Singh, David J.; Pickett, Warren E. Physical Review B, Vol. 50, Issue 15 https://doi.org/10.1103/physrevb.50.11235	journal	October 1994
Low-temperature transport properties of p -type CoSb 3 Morelli, D. T.; Caillat, T.; Fleurial, J. -P. Physical Review B, Vol. 51, Issue 15 https://doi.org/10.1103/physrevb.51.9622	journal	April 1995
Conduction-band structure of Bi 2 − x Sb x Se 3 mixed crystals by Shubnikov–de Haas and cyclotron resonance measurements in high magnetic fields Kulbachinskii, V. A.; Miura, N.; Nakagawa, H. Physical Review B, Vol. 59, Issue 24 https://doi.org/10.1103/physrevb.59.15733	journal	June 1999
Convergence of Conduction Bands as a Means of Enhancing Thermoelectric Performance of n -Type Mg 2 Si 1 − x Sn x Solid Solutions Liu, Wei; Tan, Xiaojian; Yin, Kang Physical Review Letters, Vol. 108, Issue 16 https://doi.org/10.1103/physrevlett.108.166601	journal	April 2012
Direct Measurement of the Thickness-Dependent Electronic Band Structure of MoS 2 Using Angle-Resolved Photoemission Spectroscopy Jin, Wencan; Yeh, Po-Chun; Zaki, Nader Physical Review Letters, Vol. 111, Issue 10 https://doi.org/10.1103/physrevlett.111.106801	journal	September 2013
Quasilinear dispersion in electronic band structure and high Seebeck coefficient in CuFe S 2 -based thermoelectric materials Xie, Hongyao; Su, Xianli; Hao, Shiqiang Physical Review Materials, Vol. 4, Issue 2 https://doi.org/10.1103/physrevmaterials.4.025405	journal	February 2020
High-Thermoelectric Performance of Nanostructured Bismuth Antimony Telluride Bulk Alloys Poudel, B.; Hao, Q.; Ma, Y. Science, Vol. 320, Issue 5876, p. 634-638 https://doi.org/10.1126/science.1156446	journal	May 2008
Ultrahigh power factor and thermoelectric performance in hole-doped single-crystal SnSe Zhao, L.-D.; Tan, G.; Hao, S. Science, Vol. 351, Issue 6269, p. 141-144 https://doi.org/10.1126/science.aad3749	journal	November 2015
Advances in thermoelectric materials research: Looking back and moving forward He, Jian; Tritt, Terry M. Science, Vol. 357, Issue 6358 https://doi.org/10.1126/science.aak9997	journal	September 2017
High thermoelectric cooling performance of n-type Mg ₃ Bi ₂ -based materials Mao, Jun; Zhu, Hangtian; Ding, Zhiwei Science, Vol. 365, Issue 6452 https://doi.org/10.1126/science.aax7792	journal	July 2019
Seeking new, highly effective thermoelectrics Xiao, Yu; Zhao, Li-Dong Science, Vol. 367, Issue 6483 https://doi.org/10.1126/science.aaz9426	journal	March 2020
Thermoelectric Materials, Phenomena, and Applications: A Bird's Eye View Tritt, Terry M.; Subramanian, M. A. MRS Bulletin, Vol. 31, Issue 3 https://doi.org/10.1557/mrs2006.44	journal	March 2006
Thermoelectric Properties of Chalcopyrite-Type CuGaTe ₂ with Ag Substituted into the Cu Sites Yusufu, Aikebaier; Kurosaki, Ken; Ohishi, Yuji Japanese Journal of Applied Physics, Vol. 52, Issue 8R https://doi.org/10.7567/jjap.52.081801	journal	August 2013

Similar Records

Thermoelectric properties of chalcopyrite type CuGaTe{sub 2} and chalcostibite CuSbS{sub 2}

Journal Article · Fri Dec 13 23:00:00 EST 2013 · Journal of Applied Physics · OSTI ID:22266158

Electronic structure theory of chalcopyrite alloys, interfaces, and ordered vacancy compounds

Journal Article · Sun Dec 31 23:00:00 EST 1995 · AIP Conference Proceedings · OSTI ID:451064

Related Subjects

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

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

Citation Formats

References (70)

Similar Records

Related Subjects

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