Influence of Al Doping on Thermoelectric Properties of CuInTe2
Received date: 2025-09-16
Revised date: 2026-03-09
Online published: 2026-03-26
Supported by
National Natural Science Foundation of China(52271025);National Natural Science Foundation of China(51927801);National Natural Science Foundation of China(U22A20174);Science and Technology Planning Project of Liaoning Province(2023JH2/101700295);Innovation Foundation of Science and the Technology of Dalian(2023JJ12GX021);Innovation Outstanding Young Talent Program of Karamay(XQZX20230103)
The low electrical conductivity exhibited by CuInTe2, coupled with its relatively high lattice thermal conductivity, results in a suboptimal thermoelectric figure of merit (ZT) and conversion efficiency, thereby hindering its potential for commercial application in the field of thermoelectricity. A series of Al-doped CuInTe2 compounds were successfully prepared using solid-state reaction and spark plasma sintering techniques in this study. The influence of aluminum doping on the structure and thermoelectric performance was systematically investigated. Al doping remarkably enhances electrical transport performance by increasing carrier concentration. Meanwhile, Al doping induces substitutional point defects, dislocations, strain fluctuations, and nanoprecipitations of CuInAl4Te8, which act as additional barriers to phonon transport, leading to a reduction in the lattice thermal conductivity. Consequently, a minimum lattice thermal conductivity of 0.72 W/(m·K) at 823 K was obtained for CuIn0.8Al0.2Te2 sample, and a maximum ZT value of 0.88, an enhancement of 115% than pristine CuInTe2. The average ZT values at 323-823 K and 523-823 K were 0.34 and 0.60, respectively, representing approximately 127% and 122% compared with pristine CuInTe2. The remarkable enhancement of ZT and average ZT values for CuIn1-xAlxTe2 compounds demonstrates the efficacy of In-site doping in CuInTe2.
Key words： CuInTe2; thermoelectric materials; doping; Seebeck coefficient
YANG Erkuo , ZHANG Zeyu , WANG Yasong , PENG Wei , LI Changyun , LI Guangshu , KANG Huijun , WANG Tongmin . Influence of Al Doping on Thermoelectric Properties of CuInTe2[J]. Acta Metall Sin, 2026 , 62(6) : 1137 -1146 . DOI: 10.11900/0412.1961.2025.00269
| [1] | Qin Y X, Qin B C, Hong T, et al. Grid-plainification enables medium-temperature PbSe thermoelectrics to cool better than Bi2Te3[J]. Science, 2024, 383: 1204 |
| [2] | Wang C Y, Ma Q Y, Xue H R, et al. Tetrahedral distortion and thermoelectric performance of the Ag-substituted CuInTe2 chalcopyrite compound[J]. ACS Appl. Energy Mater., 2020, 3: 11015 |
| [3] | Kucek V, Drasar C, Navratil J, et al. Thermoelectric properties of Ni-doped CuInTe2[J]. J. Phys. Chem. Solids, 2015, 83: 18 |
| [4] | Sadia Y, Lifshitz I, Sebaoun D, et al. Transport properties of Cd- and Ni-doped CuIn(S,Se,Te)2-based semiconductors[J]. ACS Appl. Electron. Mater, 2024, 6: 2870 |
| [5] | Yang J F, Chen S P, Du Z L, et al. Lattice defects and thermoelectric properties: The case of p-type CuInTe2 chalcopyrite on introduction of zinc[J]. Dalton Trans., 2014, 43: 15228 |
| [6] | Luo Y B. Investigation on the chalcopyrite CuInTe2 based thermoelectric materials[D]. Wuhan: Huazhong University of Science and Technology, 2016 |
| 罗裕波. 黄铜矿结构CuInTe2基热电材料研究[D]. 武汉: 华中科技大学, 2016 | |
| [7] | Xiong Q H, Wu H, Zhang K Q, et al. Realizing high thermoelectric performance and thermal stability in CuInTe2 through heavy dose Mg doping[J]. Acta Mater., 2024, 278: 120268 |
| [8] | Yang E K, Jiang Q W, Li G S, et al. Enhancing thermoelectric performance of CuInTe2 via trace Ag doping at indium sites[J]. ACS Appl. Mater. Interfaces, 2023, 15: 49370 |
| [9] | Cheng N, Liu R, Bai S, et al. Enhanced thermoelectric performance in Cd doped CuInTe2 compounds[J]. J. Appl. Phys., 2014, 115: 163705 |
| [10] | Kucek V, Drasar C, Kasparova J, et al. High-temperature thermoelectric properties of Hg-doped CuInTe2[J]. J. Appl. Phys., 2015, 118: 125105 |
| [11] | Luo P F, You L, Yang J, et al. Effects of Mn substitution on thermoelectric properties of CuIn1-xMnxTe2[J]. Chin. Phys., 2017, 26B: 097201 |
| [12] | Wang H X, Ying P Z, Yang J F, et al. Defects and thermoelectric performance of ternary chalcopyrite CuInTe2-based semiconductors doped with Mn[J]. Acta Phys. Sin., 2016, 65: 067201 |
| 王鸿翔, 应鹏展, 杨江锋 等. Mn掺杂后三元黄铜矿结构半导体CuInTe2的缺陷特征与热电性能[J]. 物理学报, 2016, 65: 067201 | |
| [13] | Yang E K, Yu L F, Li G S, et al. Second phases and dislocations to boost the thermoelectric properties of CuInTe2 by Sb doping at in site[J]. Chem. Mater., 2024, 36: 8753 |
| [14] | Qin Y T, Qiu P F, Shi X, et al. Thermoelectric properties for CuInTe2-xSx (x = 0, 0.05, 0.1, 0.15) solid solution[J]. J. Inorg. Mater, 2017, 32: 1171 |
| 覃玉婷, 仇鹏飞, 史 迅 等. CuInTe2-xSx (x = 0, 0.05, 0.1, 0.15)固溶体的热电性能[J]. 无机材料学报, 2017, 32: 1171 | |
| [15] | Luo Y B, Yang J Y, Jiang Q H, et al. Progressive regulation of electrical and thermal transport properties to high-performance CuInTe2 thermoelectric materials[J]. Adv. Energy Mater., 2016, 6: 1600007 |
| [16] | Zhou Y M, Wu H J, Pei Y L, et al. Strategy to optimize the overall thermoelectric properties of SnTe via compositing with its property-counter CuInTe2[J]. Acta Mater., 2017, 125: 542 |
| [17] | Hwang J, Lee M, Yu B K, et al. Enhancement of thermoelectric performance in a non-toxic CuInTe2/SnTe coated grain nanocomposite[J]. J. Mater. Chem., 2021, 9A: 14851 |
| [18] | Kim H, Kihoi S K, Shenoy U S, et al. High thermoelectric and mechanical performance achieved by a hyperconverged electronic structure and low lattice thermal conductivity in GeTe through CuInTe2 alloying[J]. J. Mater. Chem., 2023, 11A: 8119 |
| [19] | Huang R C, Huang Y, Zhu B, et al. Large enhancement of thermoelectric performance of InTe compound by sintering and CuInTe2 doping[J]. J. Appl. Phys., 2019, 126: 125108 |
| [20] | Yan Y C, Lu X, Wang G Y, et al. ZT = 1.1 in CuInTe2 solid solutions enabled by rational defect engineering[J]. ACS Appl. Energy Mater., 2020, 3: 2039 |
| [21] | Luo Y B, Jiang Q H, Yang J Y, et al. Simultaneous regulation of electrical and thermal transport properties in CuInTe2 by directly incorporating excess ZnX (X = S, Se)[J]. Nano Energy, 2017, 32: 80 |
| [22] | Chen H J, Yang C Y, Liu H L, et al. Thermoelectric properties of CuInTe2/graphene composites[J]. CrystEngComm, 2013, 15: 6648 |
| [23] | Xiong Q H, Yan Y C, Li N H, et al. Strong anharmonicity induced low lattice thermal conductivity and high thermoelectric performance in (CuInTe2)1-x (AgSbTe2)x system[J]. Appl. Phys. Lett., 2022, 121: 013903 |
| [24] | Wang Y Q, Zhang H, Wu Y, et al. Dual-optimization of transport properties enabled by high-pressure treatments for CuInTe2 thermoelectric materials[J]. Chem. Eng. J., 2024, 490: 151588 |
| [25] | Wang W, Liu S X, Wang Y, et al. Tailoring local chemical fluctuation of high-entropy structures in thermoelectric materials[J]. Sci. Adv., 2024, 10: eadp4372 |
| [26] | Nolas G S, Sharp J, Goldsmid H J. The phonon-glass electron-crystal approach to thermoelectric materials research[A]. Thermoelectrics: Basic Principles and New Materials Developments[M]. Berlin: Springer, 2001: 177 |
| [27] | Seon S, Kim B, Park O, et al. Significant reduction of lattice thermal conductivity observed in CuInTe2-CuAlTe2 solid-solution alloys[J]. Phys. Chem. Chem. Phys., 2024, 26: 28858 |
| [28] | Cao Y, Su X L, Meng F C, et al. Origin of the distinct thermoelectric transport properties of chalcopyrite ABTe2 (A = Cu, Ag; B = Ga, In)[J]. Adv. Funct. Mater., 2020, 30: 2005861 |
| [29] | Su X L, Zhao N, Hao S Q, et al. High thermoelectric performance in the wide band-gap AgGa1-xTe2 compounds: Directional negative thermal expansion and intrinsically low thermal conductivity[J]. Adv. Funct. Mater., 2019, 29: 1806534 |
| [30] | Plirdpring T, Kurosaki K, Kosuga A, et al. Chalcopyrite CuGaTe2: A high-efficiency bulk thermoelectric material[J]. Adv. Mater., 2012, 24: 3622 |
| [31] | Zhou G, Wang D. High thermoelectric performance from optimization of hole-doped CuInTe2[J]. Phys. Chem. Chem. Phys., 2016, 18: 5925 |
| [32] | Li W X, Luo Y B, Zheng Y, et al. Enhancement of the thermoelectric performance of CuInTe2 via SnO2 in situ replacement[J]. J. Mater. Sci. Mater. Electron, 2018, 29: 4732 |
| [33] | Kim H, Kihoi S K, Lee H S. Point defects control in non-stoichiometric CuInTe2 compounds and its corresponding effects on the microstructure and thermoelectric properties[J]. J. Alloys Compd., 2021, 869: 159381 |
| [34] | Ahmed F, Tsujii N, Matsushita Y, et al. Influence of slight substitution (Mn/In) on thermoelectric and magnetic properties in chalcopyrite-type CuInTe2[J]. J. Electron. Mater., 2019, 48: 4524 |
| [35] | Luo Y B, Yang J Y, Jiang Q H, et al. Large enhancement of thermoelectric performance of CuInTe2 via a synergistic strategy of point defects and microstructure engineering[J]. Nano Energy, 2015, 18: 37 |
| [36] | Cheng J, Gan L, Zhang J W, et al. Thermoelectric properties of heavily co-doped β-FeSi2[J]. J. Mater. Sci. Technol., 2024, 187: 248 |
| [37] | Zhang X L, Huang M, Li H J, et al. Ultralow lattice thermal conductivity and improved thermoelectric performance in a Hf-free half-Heusler compound modulated by entropy engineering[J]. J. Mater. Chem., 2023, 11A: 8150 |
| [38] | Chauhan N S, Sara S G, Bhattacharya A, et al. Odd-stoichiometry and secondary phase relations in higher manganese silicides[J]. Adv. Funct. Mater., 2024, 34: 2313948 |
| [39] | Zhang Z W, Li J, Yao H H, et al. Identifying the promising n-type SmMg2Sb2-based Zintl phase thermoelectric material[J]. Acta Mater., 2024, 268: 119777 |
| [40] | Yu Y, Sheskin A, Wang Z Y, et al. Ostwald ripening of Ag2Te precipitates in thermoelectric PbTe: Effects of crystallography, dislocations, and interatomic bonding[J]. Adv. Energy Mater., 2024, 14: 2304442 |
| [41] | Yang H J, Wu L Q, Feng X B, et al. Optimization of mechanical and thermoelectric properties of SnTe-based semiconductors by Mn alloying modulated precipitation evolution[J]. Small, 2024, 20: 2310692 |
| [42] | Liu S B, Qin Y X, Wen Y, et al. Efforts toward the fabrication of thermoelectric cooling module based on n-type and p-type PbTe ingots[J]. Adv. Funct. Mater., 2024, 34: 2315707 |
| [43] | Zhou H, Cheng K, Meng X, et al. Layer-structured GaGeTe compound as a promising thermoelectric material[J]. ACS Appl. Energy Mater., 2023, 6: 4264 |
| [44] | Xia Z Z L, Wang G W, Zhou X Y, et al. Effect of the Cu vacancy on the thermoelectric performance of p-type Cu1-xInTe2 compounds[J]. Ceram. Int., 2017, 43: 16276 |
| [45] | Cai J F, Yang J X, Liu G Q, et al. Ultralow thermal conductivity and improved ZT of CuInTe2 by high-entropy structure design[J]. Mater. Today Phys., 2021, 18: 100394 |
/
| 〈 |
|
〉 |
