Influence of Al Doping on Thermoelectric Properties of CuInTe2

doi:10.11900/0412.1961.2025.00269

Acta Metall Sin

2026, Vol. 62

Issue (6): 1137-1146 DOI: 10.11900/0412.1961.2025.00269

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Influence of Al Doping on Thermoelectric Properties of CuInTe₂

YANG Erkuo¹(

), ZHANG Zeyu¹, WANG Yasong¹, PENG Wei¹, LI Changyun¹, LI Guangshu², KANG Huijun²(

), WANG Tongmin²(

)

1 School of Engineering, China University of Petroleum-Beijing at Karamay, Karamay 834000, China
2 Key Laboratory of Solidification Control and Digital Preparation Technology (Liaoning Province), School of Materials Science and Engineering, Dalian University of Technology, Dalian 116024, China

Cite this article:

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. Acta Metall Sin, 2026, 62(6): 1137-1146.

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Abstract

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 CuIn_0.8Al_0.2Te₂ 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 CuIn_1-_xAl_xTe₂ compounds demonstrates the efficacy of In-site doping in CuInTe₂.

Key words: CuInTe₂ thermoelectric materials doping Seebeck coefficient

Received: 16 September 2025

ZTFLH:

TM913

Fund: 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)

Corresponding Authors: KANG Huijun, professor, Tel: (0411)84709500, E-mail: kanghuijun@dlut.edu.cn;
WANG Tongmin, professor, Tel: (0411)84706790, E-mail: tmwang@dlut.edu.cn;
YANG Erkuo, Tel: (0990)6633320, E-mail: yangerkuo@cupk.edu.cn

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	YANG Erkuo
	ZHANG Zeyu
	WANG Yasong
	PENG Wei
	LI Changyun
	LI Guangshu
	KANG Huijun
	WANG Tongmin

URL:

https://www.ams.org.cn/EN/10.11900/0412.1961.2025.00269 OR https://www.ams.org.cn/EN/Y2026/V62/I6/1137

Fig.1 Substitutions elements of CuInTe₂ highlighted in periodic table

Fig.2 XRD patterns of CuIn_1-_xAl_xTe₂ (x = 0, 0.01, 0.03, 0.1, 0.2, 0.3, and 0.5) powders at 303 K (a) and its enlargement of (220) peaks (b)

Fig.3 SEM images and corresponding EDS element distribution mappings of longitudinal (a) and transverse (b) sections of CuIn_0.97Al_0.03Te₂ sample

Fig.4 Low (a) and high (b) magnified SEM images and corresponding EDS element distribution mappings of CuIn_0.8Al_0.2Te₂ sample

Fig.5 TEM characteristics of nanoprecipitate phases and interface between nanoprecipitate phase and the matrix
(a) TEM image
(b, c) SAED patterns of upper right corner (b) and bottom left corner (c) of Fig.5a
(d) enlarged TEM image corresponding to the rectangle area A in Fig.5a
(e) HRTEM image corresponding to the rectangle area C in Fig.5d
(f) inverse fast Fourier transform (IFFT) of the rectangle area D in Fig.5e
(g-i) geometric phase analyses (GPA) of ε_xx (g), ε_yy (h), and ε_xy (i) for Fig.5f (ε_xx—normal strain along the x-axis, ε_yy —normal strain along the y-axis, ε_xy —shear strain along the xy-axis)
(j) HRTEM image corresponding to the rectangle area B in Fig.5a
(k) fast Fourier transform (FFT) of the rectangle area E in Fig.5j
(l) IFFT of the rectangle area E in Fig.5j
(m-o) GPA of ε_xx (m), ε_yy (n), and ε_xy (o) for Fig.5l

Fig.6 Electrical transport properties of CuIn_1-_xAl_xTe₂ (x = 0, 0.01, 0.03, 0.1, 0.2, and 0.3)
(a) temperature (T) dependent electrical conductivity (σ)
(b) temperature dependent Seebeck coefficient (S)
(c) doped‐content dependent carrier concentration (n) and mobility (μ)
(d) temperature dependent power factor (PF)

Fig.7 Thermal transport properties of CuIn_1-_xAl_xTe₂ (x = 0, 0.01, 0.03, 0.1, 0.2, and 0.3)
(a) total thermal conductivity (κ_T)
(b) electrical thermal conductivity (κ_e)
(c) lattice thermal conductivity (κ_L)
(d) comparation of the lattice thermal conductivity with other system^{[16,20,21,30,36,40-45]}

Table 1 Mass field fluctuation (Γ_M), strain field fluctuation (Γ_S), and total scattering parameter (Γ_tot) of CuIn_1-_xAl_xTe₂ (x = 0.01, 0.03, 0.1, 0.2, and 0.3)

Fig.8 Thermoelectric figure of merit (ZT) values of CuIn_1-_xAl_xTe₂ (x = 0, 0.01, 0.03, 0.1, 0.2, and 0.3)
(a) temperature dependent ZT value
(b) average ZT value from 303 K to 823 K and from 573 to 823 K (ZT_{avg(303-823 K)} and ZT_{avg(573-823 K)})

[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 doi: 10.1126/science.adk9589
[2]	Wang C Y, Ma Q Y, Xue H R, et al. Tetrahedral distortion and thermoelectric performance of the Ag-substituted CuInTe₂chalcopyrite compound[J]. ACS Appl. Energy Mater., 2020, 3: 11015 doi: 10.1021/acsaem.0c01867
[3]	Kucek V, Drasar C, Navratil J, et al. Thermoelectric properties of Ni-doped CuInTe₂[J]. J. Phys. Chem. Solids, 2015, 83: 18 doi: 10.1016/j.jpcs.2015.03.012
[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 doi: 10.1021/acsaelm.3c00795
[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 doi: 10.1039/C4DT01909A
[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 doi: 10.1016/j.actamat.2024.120268
[8]	Yang E K, Jiang Q W, Li G S, et al. Enhancing thermoelectric performance of CuInTe₂via trace Ag doping at indium sites[J]. ACS Appl. Mater. Interfaces, 2023, 15: 49370 doi: 10.1021/acsami.3c11825
[9]	Cheng N, Liu R, Bai S, et al. Enhanced thermoelectric performance in Cd doped CuInTe₂compounds[J]. J. Appl. Phys., 2014, 115: 163705 doi: 10.1063/1.4872250
[10]	Kucek V, Drasar C, Kasparova J, et al. High-temperature thermoelectric properties of Hg-doped CuInTe₂[J]. J. Appl. Phys., 2015, 118: 125105 doi: 10.1063/1.4931600
[11]	Luo P F, You L, Yang J, et al. Effects of Mn substitution on thermoelectric properties of CuIn_1-_xMn_xTe₂[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 CuInTe_2-_xS_x (x = 0, 0.05, 0.1, 0.15) solid solution[J]. J. Inorg. Mater, 2017, 32: 1171 doi: 10.15541/jim20170051
	覃玉婷, 仇鹏飞, 史迅等. CuInTe_2-_xS_x (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 doi: 10.15541/jim20170051
[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 doi: 10.1002/aenm.v6.12
[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 doi: 10.1016/j.actamat.2016.11.049
[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 doi: 10.1063/1.5117500
[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 doi: 10.1021/acsaem.9b01241
[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 doi: 10.1016/j.nanoen.2016.12.023
[22]	Chen H J, Yang C Y, Liu H L, et al. Thermoelectric properties of CuInTe₂/graphene composites[J]. CrystEngComm, 2013, 15: 6648 doi: 10.1039/c3ce40334c
[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 doi: 10.1016/j.cej.2024.151588
[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 doi: 10.1126/sciadv.adp4372
[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 doi: 10.1039/D4CP03277B
[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 doi: 10.1002/adfm.v30.51
[29]	Su X L, Zhao N, Hao S Q, et al. High thermoelectric performance in the wide band-gap AgGa_1-_xTe₂ compounds: Directional negative thermal expansion and intrinsically low thermal conductivity[J]. Adv. Funct. Mater., 2019, 29: 1806534 doi: 10.1002/adfm.v29.6
[30]	Plirdpring T, Kurosaki K, Kosuga A, et al. Chalcopyrite CuGaTe₂: A high-efficiency bulk thermoelectric material[J]. Adv. Mater., 2012, 24: 3622 doi: 10.1002/adma.v24.27
[31]	Zhou G, Wang D. High thermoelectric performance from optimization of hole-doped CuInTe₂[J]. Phys. Chem. Chem. Phys., 2016, 18: 5925 doi: 10.1039/c5cp05129k pmid: 26593866
[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 doi: 10.1007/s10854-017-8427-8
[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 doi: 10.1016/j.jallcom.2021.159381
[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 doi: 10.1007/s11664-019-07234-2
[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 doi: 10.1016/j.nanoen.2015.09.015
[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 doi: 10.1016/j.jmst.2023.11.039
[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 doi: 10.1002/adfm.v34.17
[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 doi: 10.1016/j.actamat.2024.119777
[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 doi: 10.1002/aenm.v14.19
[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 doi: 10.1002/smll.v20.27
[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 doi: 10.1002/adfm.v34.26
[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 doi: 10.1021/acsaem.3c00198
[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 Cu_1-_xInTe₂ compounds[J]. Ceram. Int., 2017, 43: 16276 doi: 10.1016/j.ceramint.2017.08.213
[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

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