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  • ReceivedMay 17, 2018
  • AcceptedJun 20, 2018
  • PublishedAug 10, 2018

Abstract


Funding

the National Key Research and Development Program of China(2018YFB0703601)

the National Natural Science Foundation of China(51625205)

the Key Research Program of Chinese Academy of Sciences(KFZD-SW-421)

Program of Shanghai Subject Chief Scientist(16XD1403900)

Youth Innovation Promotion Association

CAS(2016232)

Shanghai Sailing Program(18YF1426700)


Acknowledgment

This review is supported by the National Key Research and Development Program of China (2018YFB0703600), the National Natural Science Foundation of China (51625205), the Key Research Program of Chinese Academy of Sciences (KFZD-SW-421), Program of Shanghai Subject Chief Scientist (16XD1403900), Youth Innovation Promotion Association, CAS (2016232) and Shanghai Sailing Program (18YF1426700).


Interest statement

The authors declare no conflict of interest.


Contributions statement

Shi X and Chen L designed the topic and framework of this review; Wei TR, Qin Y and Qiu P collected and organized the data; Wei TR and Qin Y wrote the review with the support from Qiu P, Shi X and Chen L. All authors contributed to the general discussion.


Author information

Tian-Ran Wei is an assistant professor at Shanghai Institute of Ceramics, Chinese Academy of Sciences (SICCAS). He obtained his PhD degree in materials science and engineering from Tsinghua University in 2017. His current research focuses on advanced thermoelectric materials and the underlying transport mechanisms.


Xun Shi is a Professor in SICCAS, China. He received his BSc (2000) in Tsinghua University and PhD (2005) in the University of Chinese Academy of Sciences. He worked at the University of Michigan (USA) as a postdoctor from 2007 to 2009. Then he joined the R&D center in General Motors. At 2010, he came back SICCAS. His current research focuses on advanced thermoelectric materials.


References

[1] Nolas G S, Sharp J, Goldsmid H J. Thermoelectrics: Basic Principles and New Materials Developments. Berlin: Springer, 2001. Google Scholar

[2] Uher C (eds.). Materials Aspect of Thermoelectricity. Boca Raton: CRC Press, 2017. Google Scholar

[3] Zhu T, Liu Y, Fu C, et al. Compromise and synergy in high-efficiency thermoelectric materials. Adv Mater, 2017, 291605884 CrossRef PubMed Google Scholar

[4] Yang J, Xi L, Qiu W, et al. On the tuning of electrical and thermal transport in thermoelectrics: an integrated theory–experiment perspective. NPJ Comput Mater, 2016, 215015 CrossRef ADS Google Scholar

[5] Slack G A. New Materials and Performance Limits for Thermoelectric Cooling. In: Rowe D M (eds.). CRC Handbook of Thermoelectrics. Boca Raton: CRC Press, 1995:407-440. Google Scholar

[6] Snyder GJ, Toberer ES. Complex thermoelectric materials. Nat Mater, 2008, 7105-114 CrossRef PubMed ADS Google Scholar

[7] He J, Tritt TM. Advances in thermoelectric materials research: Looking back and moving forward. Science, 2017, 357eaak9997 CrossRef PubMed Google Scholar

[8] Tan G, Zhao LD, Kanatzidis MG. Rationally designing high-performance bulk thermoelectric materials. Chem Rev, 2016, 11612123-12149 CrossRef PubMed Google Scholar

[9] Liu W, Yin K, Zhang Q, et al. Eco-friendly high-performance silicide thermoelectric materials. Natl Sci Rev, 2017, 4611-626 CrossRef Google Scholar

[10] Liu W, Jie Q, Kim HS, et al. Current progress and future challenges in thermoelectric power generation: From materials to devices. Acta Mater, 2015, 87357-376 CrossRef Google Scholar

[11] Li JF, Pan Y, Wu CF, et al. Processing of advanced thermoelectric materials. Sci China Technol Sci, 2017, 601347-1364 CrossRef Google Scholar

[12] Qiu P, Shi X, Chen L. Cu-based thermoelectric materials. Energy Storage Mater, 2016, 385-97 CrossRef Google Scholar

[13] Xiao XX, Xie WJ, Tang XF, et al. Phase transition and high temperature thermoelectric properties of copper selenide Cu2−xSe (0≤x≤ 0.25). Chin Phys B, 2011, 20087201 CrossRef ADS Google Scholar

[14] Liu H, Shi X, Xu F, et al. Copper ion liquid-like thermoelectrics. Nat Mater, 2012, 11422-425 CrossRef PubMed ADS Google Scholar

[15] Liu H, Yuan X, Lu P, et al. Ultrahigh thermoelectric performance by electron and phonon critical scattering in Cu2Se1−xIx. Adv Mater, 2013, 256607-6612 CrossRef PubMed Google Scholar

[16] He Y, Day T, Zhang T, et al. High thermoelectric performance in non-toxic earth-abundant copper sulfide. Adv Mater, 2014, 263974-3978 CrossRef PubMed Google Scholar

[17] He Y, Lu P, Shi X, et al. Ultrahigh thermoelectric performance in mosaic crystals. Adv Mater, 2015, 273639-3644 CrossRef PubMed Google Scholar

[18] He Y, Zhang T, Shi X, et al. High thermoelectric performance in copper telluride. NPG Asia Mater, 2015, 7e210 CrossRef Google Scholar

[19] Zhao L, Wang X, Fei FY, et al. High thermoelectric and mechanical performance in highly dense Cu2−xS bulks prepared by a melt-solidification technique. J Mater Chem A, 2015, 39432-9437 CrossRef Google Scholar

[20] Zhao LL, Wang XL, Wang JY, et al. Superior intrinsic thermoelectric performance with zT of 1.8 in single-crystal and melt-quenched highly dense Cu2−xSe bulks. Sci Rep, 2015, 57671 CrossRef PubMed ADS Google Scholar

[21] Nunna R, Qiu P, Yin M, et al. Ultrahigh thermoelectric performance in Cu2Se-based hybrid materials with highly dispersed molecular CNTs. Energy Environ Sci, 2017, 101928-1935 CrossRef Google Scholar

[22] Olvera AA, Moroz NA, Sahoo P, et al. Partial indium solubility induces chemical stability and colossal thermoelectric figure of merit in Cu2Se. Energy Environ Sci, 2017, 101668-1676 CrossRef Google Scholar

[23] Zhao K, Blichfeld AB, Chen H, et al. Enhanced thermoelectric performance through tuning bonding energy in Cu2Se1–xSx liquid-like materials. Chem Mater, 2017, 296367-6377 CrossRef Google Scholar

[24] Zhao K, Qiu P, Song Q, et al. Ultrahigh thermoelectric performance in Cu2−ySe0.5S0.5 liquid-like materials. Mater Today Phys, 2017, 114-23 CrossRef Google Scholar

[25] Yang L, Chen ZG, Han G, et al. Te-Doped Cu2Se nanoplates with a high average thermoelectric figure of merit. J Mater Chem A, 2016, 49213-9219 CrossRef Google Scholar

[26] Butt S, Xu W, Farooq MU, et al. Enhanced thermoelectricity in high-temperature β-phase copper(I) selenides embedded with Cu2Te nanoclusters. ACS Appl Mater Interfaces, 2016, 815196-15204 CrossRef Google Scholar

[27] Gahtori B, Bathula S, Tyagi K, et al. Giant enhancement in thermoelectric performance of copper selenide by incorporation of different nanoscale dimensional defect features. Nano Energy, 2015, 1336-46 CrossRef Google Scholar

[28] Liu ML, Chen IW, Huang FQ, et al. Improved thermoelectric properties of Cu-doped quaternary chalcogenides of Cu2CdSnSe4. Adv Mater, 2009, 213808-3812 CrossRef Google Scholar

[29] Shi XY, Huang FQ, Liu ML, et al. Thermoelectric properties of tetrahedrally bonded wide-gap stannite compounds Cu2ZnSn1−xInxSe4. Appl Phys Lett, 2009, 94122103 CrossRef ADS Google Scholar

[30] Liu R, Xi L, Liu H, et al. Ternary compound CuInTe2: a promising thermoelectric material with diamond-like structure. Chem Commun, 2012, 483818 CrossRef PubMed Google Scholar

[31] Plirdpring T, Kurosaki K, Kosuga A, et al. Chalcopyrite CuGaTe2: A high-efficiency bulk thermoelectric material. Adv Mater, 2012, 243622-3626 CrossRef PubMed Google Scholar

[32] Zhang J, Liu R, Cheng N, et al. High-performance pseudocubic thermoelectric materials from non-cubic chalcopyrite compounds. Adv Mater, 2014, 263848-3853 CrossRef PubMed Google Scholar

[33] Liu R, Chen H, Zhao K, et al. Entropy as a gene-like performance indicator promoting thermoelectric materials. Adv Mater, 2017, 291702712 CrossRef PubMed Google Scholar

[34] Luo Y, Yang J, Jiang Q, et al. Progressive regulation of electrical and thermal transport properties to high-performance CuInTe2 thermoelectric materials. Adv Energy Mater, 2016, 61600007 CrossRef Google Scholar

[35] Liu Y, García G, Ortega S, et al. Solution-based synthesis and processing of Sn- and Bi-doped Cu3SbSe4 nanocrystals, nanomaterials and ring-shaped thermoelectric generators. J Mater Chem A, 2016, 52592-2602 CrossRef Google Scholar

[36] Skoug EJ, Cain JD, Morelli DT. High thermoelectric figure of merit in the Cu3SbSe4-Cu3SbS4 solid solution. Appl Phys Lett, 2011, 98261911 CrossRef ADS Google Scholar

[37] Liu R, Qin Y, Cheng N, et al. Thermoelectric performance of Cu1−xδAgxInTe2 diamond-like materials with a pseudocubic crystal structure. Inorg Chem Front, 2016, 31167-1177 CrossRef Google Scholar

[38] Li Y, Liu G, Cao T, et al. Enhanced thermoelectric properties of Cu2SnSe3 by (Ag,In)-Co-doping. Adv Funct Mater, 2016, 266025-6032 CrossRef Google Scholar

[39] Shi X, Xi L, Fan J, et al. Cu−Se bond network and thermoelectric compounds with complex diamondlike structure. Chem Mater, 2010, 226029-6031 CrossRef Google Scholar

[40] Li Y, Liu G, Li J, et al. High thermoelectric performance of In-doped Cu2SnSe3 prepared by fast combustion synthesis. New J Chem, 2016, 405394-5400 CrossRef Google Scholar

[41] Ma R, Liu G, Li J, et al. Effect of secondary phases on thermoelectric properties of Cu2SnSe3. Ceramics Int, 2017, 437002-7010 CrossRef Google Scholar

[42] Suekuni K, Kim FS, Nishiate H, et al. High-performance thermoelectric minerals: Colusites Cu26V2M6S32 (M=Ge, Sn). Appl Phys Lett, 2014, 105132107 CrossRef ADS Google Scholar

[43] Kikuchi Y, Bouyrie Y, Ohta M, et al. Vanadium-free colusites Cu26A2Sn6S32 (A = Nb, Ta) for environmentally friendly thermoelectrics. J Mater Chem A, 2016, 415207-15214 CrossRef Google Scholar

[44] Bouyrie Y, Ohta M, Suekuni K, et al. Enhancement in the thermoelectric performance of colusites Cu26A2E6S32 (A=Nb, Ta; E=Sn, Ge) using E-site non-stoichiometry. J Mater Chem C, 2017, 54174-4184 CrossRef Google Scholar

[45] Lu X, Morelli DT, Xia Y, et al. High performance thermoelectricity in earth-abundant compounds based on natural mineral tetrahedrites. Adv Energy Mater, 2013, 3342-348 CrossRef Google Scholar

[46] Heo J, Laurita G, Muir S, et al. Enhanced thermoelectric performance of synthetic tetrahedrites. Chem Mater, 2014, 262047-2051 CrossRef Google Scholar

[47] Lu X, Morelli DT, Wang Y, et al. Phase stability, crystal structure, and thermoelectric properties of Cu12Sb4S13–xSex solid solutions. Chem Mater, 2016, 281781-1786 CrossRef Google Scholar

[48] Lu X, Morelli DT, Xia Y, et al. Increasing the thermoelectric figure of merit of tetrahedrites by co-doping with nickel and zinc. Chem Mater, 2015, 27408-413 CrossRef Google Scholar

[49] Prem Kumar DS, Chetty R, Femi OE, et al. Thermoelectric properties of Bi doped tetrahedrite. J Elec Mater, 2017, 462616-2622 CrossRef ADS Google Scholar

[50] Zhao LD, Berardan D, Pei YL, et al. Bi1−xSrxCuSeO oxyselenides as promising thermoelectric materials. Appl Phys Lett, 2010, 97092118 CrossRef ADS Google Scholar

[51] Liu Y, Zhao LD, Liu Y, et al. Remarkable enhancement in thermoelectric performance of BiCuSeO by Cu deficiencies. J Am Chem Soc, 2011, 13320112-20115 CrossRef PubMed Google Scholar

[52] Li F, Li JF, Zhao LD, et al. Polycrystalline BiCuSeO oxide as a potential thermoelectric material. Energy Environ Sci, 2012, 57188-7195 CrossRef Google Scholar

[53] Li J, Sui J, Pei Y, et al. A high thermoelectric figure of merit ZT>1 in Ba heavily doped BiCuSeO oxyselenides. Energy Environ Sci, 2012, 58543-8547 CrossRef Google Scholar

[54] Lan JL, Zhan B, Liu YC, et al. Doping for higher thermoelectric properties in p-type BiCuSeO oxyselenide. Appl Phys Lett, 2013, 102123905 CrossRef ADS Google Scholar

[55] Pei YL, He J, Li JF, et al. High thermoelectric performance of oxyselenides: intrinsically low thermal conductivity of Ca-doped BiCuSeO. NPG Asia Mater, 2013, 5e47 CrossRef Google Scholar

[56] Sui J, Li J, He J, et al. Texturation boosts the thermoelectric performance of BiCuSeO oxyselenides. Energy Environ Sci, 2013, 62916-2920 CrossRef Google Scholar

[57] Pei YL, Wu H, Wu D, et al. High thermoelectric performance realized in a BiCuSeO system by improving carrier mobility through 3D modulation doping. J Am Chem Soc, 2014, 13613902-13908 CrossRef PubMed Google Scholar

[58] Li Z, Xiao C, Fan S, et al. Dual vacancies: an effective strategy realizing synergistic optimization of thermoelectric property in BiCuSeO. J Am Chem Soc, 2015, 1376587-6593 CrossRef PubMed Google Scholar

[59] Liu Y, Zhao LD, Zhu Y, et al. Synergistically optimizing electrical and thermal transport properties of BiCuSeO via a dual-doping approach. Adv Energy Mater, 2016, 61502423 CrossRef Google Scholar

[60] Ren GK, Wang SY, Zhu YC, et al. Enhancing thermoelectric performance in hierarchically structured BiCuSeO by increasing bond covalency and weakening carrier–phonon coupling. Energy Environ Sci, 2017, 101590-1599 CrossRef Google Scholar

[61] Yang D, Su X, Yan Y, et al. Manipulating the combustion wave during self-propagating synthesis for high thermoelectric performance of layered oxychalcogenide Bi1–xPbxCuSeO. Chem Mater, 2016, 284628-4640 CrossRef Google Scholar

[62] Toberer ES, Baranowski LL, Dames C. Advances in thermal conductivity. Annu Rev Mater Res, 2012, 42179-209 CrossRef ADS Google Scholar

[63] Tritt T M. Thermal Conductivity: Theory, Properties and Applications. New York: Plenum, 2004. Google Scholar

[64] Kittel C. Introduction to Solid State Physics. New York: John Wiley & Sons Inc., 1996. Google Scholar

[65] Toberer ES, Zevalkink A, Snyder GJ. Phonon engineering through crystal chemistry. J Mater Chem, 2011, 2115843-15852 CrossRef Google Scholar

[66] Wang X, Qiu P, Zhang T, et al. Compound defects and thermoelectric properties in ternary CuAgSe-based materials. J Mater Chem A, 2015, 313662-13670 CrossRef Google Scholar

[67] Qiu P, Zhang T, Qiu Y, et al. Sulfide bornite thermoelectric material: a natural mineral with ultralow thermal conductivity. Energy Environ Sci, 2014, 74000-4006 CrossRef Google Scholar

[68] Weldert KS, Zeier WG, Day TW, et al. Thermoelectric transport in Cu7PSe6 with high copper ionic mobility. J Am Chem Soc, 2014, 13612035-12040 CrossRef PubMed Google Scholar

[69] Aydemir U, Pöhls JH, Zhu H, et al. YCuTe2: a member of a new class of thermoelectric materials with CuTe4-based layered structure. J Mater Chem A, 2016, 42461-2472 CrossRef Google Scholar

[70] Bhattacharya S, Basu R, Bhatt R, et al. CuCrSe2: a high performance phonon glass and electron crystal thermoelectric material. J Mater Chem A, 2013, 111289-11294 CrossRef Google Scholar

[71] Li W, Ibáñez M, Zamani RR, et al. Cu2HgSnSe4 nanoparticles: synthesis and thermoelectric properties. CrystEngComm, 2013, 158966 CrossRef Google Scholar

[72] Chetty R, Dadda J, de Boor J, et al. The effect of Cu addition on the thermoelectric properties of Cu2CdGeSe4. Intermetallics, 2015, 57156-162 CrossRef Google Scholar

[73] Suzumura A, Watanabe M, Nagasako N, et al. Improvement in thermoelectric properties of Se-Free Cu3SbS4 compound. J Elec Mater, 2014, 432356-2361 CrossRef ADS Google Scholar

[74] Li J, Tan Q, Li JF. Synthesis and property evaluation of CuFeS2−x as earth-abundant and environmentally-friendly thermoelectric materials. J Alloys Compd, 2013, 551143-149 CrossRef Google Scholar

[75] Li W, Lin S, Zhang X, et al. Thermoelectric properties of Cu2SnSe4 with intrinsic vacancy. Chem Mater, 2016, 286227-6232 CrossRef Google Scholar

[76] Vining CB, Laskow W, Hanson JO, et al. Thermoelectric properties of pressure-sintered Si0.8Ge0.2 thermoelectric alloys. J Appl Phys, 1991, 694333-4340 CrossRef ADS Google Scholar

[77] Caillat T, Borshchevsky A, Fleurial JP. Properties of single crystalline semiconducting CoSb3. J Appl Phys, 1996, 804442-4449 CrossRef ADS Google Scholar

[78] Liu HL, He Y, Shi X, et al. Recent progress in “phonon-liquid” thermoelectric materials. Chin Sci Bull (Chin Ver), 2013, 582603-2608 CrossRef Google Scholar

[79] Qiu W, Xi L, Wei P, et al. Part-crystalline part-liquid state and rattling-like thermal damping in materials with chemical-bond hierarchy. Proc Natl Acad Sci USA, 2014, 11115031-15035 CrossRef PubMed ADS Google Scholar

[80] Qiu W, Wu L, Ke X, et al. Diverse lattice dynamics in ternary Cu-Sb-Se compounds. Sci Rep, 2015, 513643 CrossRef PubMed ADS Google Scholar

[81] Li B, Wang H, Kawakita Y, et al. Liquid-like thermal conduction in intercalated layered crystalline solids. Nat Mater, 2018, 17226-230 CrossRef PubMed ADS arXiv Google Scholar

[82] Voneshen DJ, Walker HC, Refson K, et al. Hopping time scales and the phonon-liquid electron-crystal picture in thermoelectric copper selenide. Phys Rev Lett, 2017, 118145901 CrossRef PubMed ADS Google Scholar

[83] Skoug EJ, Morelli DT. Role of lone-pair electrons in producing minimum thermal conductivity in nitrogen-group chalcogenide compounds. Phys Rev Lett, 2011, 107235901 CrossRef PubMed ADS Google Scholar

[84] Sun Y, Xi L, Yang J, et al. The “electron crystal” behavior in copper chalcogenides Cu2X (X = Se, S). J Mater Chem A, 2017, 55098-5105 CrossRef Google Scholar

[85] Zou D, Xie S, Liu Y, et al. Electronic structures and thermoelectric properties of layered BiCuOCh oxychalcogenides (Ch = S, Se and Te): first-principles calculations. J Mater Chem A, 2013, 18888-8896 CrossRef Google Scholar

[86] Do D, Ozolins V, Mahanti SD, et al. Physics of bandgap formation in Cu–Sb–Se based novel thermoelectrics: the role of Sb valency and Cu d levels. J Phys-Condens Matter, 2012, 24415502 CrossRef PubMed ADS Google Scholar

[87] Qin Y, Qiu P, Liu R, et al. Optimized thermoelectric properties in pseudocubic diamond-like CuGaTe2 compounds. J Mater Chem A, 2016, 41277-1289 CrossRef Google Scholar

[88] Song Q, Qiu P, Hao F, et al. Quaternary pseudocubic Cu2TMSnSe4 (TM = Mn, Fe, Co) chalcopyrite thermoelectric materials. Adv Electron Mater, 2016, 21600312 CrossRef Google Scholar

[89] Zeier WG, Zevalkink A, Gibbs ZM, et al. Thinking like a chemist: intuition in thermoelectric materials. Angew Chem Int Ed, 2016, 556826-6841 CrossRef PubMed Google Scholar

[90] Zhao K, Blichfeld AB, Eikeland E, et al. Extremely low thermal conductivity and high thermoelectric performance in liquid-like Cu2Se1−xSx polymorphic materials. J Mater Chem A, 2017, 518148-18156 CrossRef Google Scholar

[91] Zhao K, Zhu C, Qiu P, et al. High thermoelectric performance and low thermal conductivity in Cu2−yS1/3Se1/3Te1/3 liquid-like materials with nanoscale mosaic structures. Nano Energy, 2017, 4243-50 CrossRef Google Scholar

[92] Xie Y. Mosaic crystals leading a new route to achieve ultrahigh thermoelectric performance. Sci China Mater, 2015, 58431-432 CrossRef Google Scholar

[93] Ge ZH, Liu X, Feng D, et al. High-performance thermoelectricity in nanostructured earth-abundant copper sulfides bulk materials. Adv Energy Mater, 2016, 61600607 CrossRef Google Scholar

[94] Jiang B, Qiu P, Eikeland E, et al. Cu8GeSe6-based thermoelectric materials with an argyrodite structure. J Mater Chem C, 2017, 5943-952 CrossRef Google Scholar

[95] Qiu PF, Wang XB, Zhang TS, et al. Thermoelectric properties of Te-doped ternary CuAgSe compounds. J Mater Chem A, 2015, 322454-22461 CrossRef Google Scholar

[96] Bhattacharya S, Bohra A, Basu R, et al. High thermoelectric performance of (AgCrSe2)0.5(CuCrSe2)0.5 nano-composites having all-scale natural hierarchical architectures. J Mater Chem A, 2014, 217122-17129 CrossRef Google Scholar

[97] Hwang JY, Mun HA, Kim SI, et al. Effects of doping on transport properties in Cu–Bi–Se-based thermoelectric materials. Inorg Chem, 2014, 5312732-12738 CrossRef PubMed Google Scholar

[98] Ishiwata S, Shiomi Y, Lee JS, et al. Extremely high electron mobility in a phonon-glass semimetal. Nat Mater, 2013, 12512-517 CrossRef PubMed ADS Google Scholar

[99] Han CG, Zhang BP, Ge ZH, et al. Thermoelectric properties of p-type semiconductors copper chromium disulfide CuCrS2+x. J Mater Sci, 2013, 484081-4087 CrossRef ADS Google Scholar

[100] Gągor A, Pietraszko A, Kaynts D. Diffusion paths formation for Cu+ ions in superionic Cu6PS5I single crystals studied in terms of structural phase transition. J Solid State Chem, 2005, 1783366-3375 CrossRef ADS Google Scholar

[101] Miyatani S, Suzuki Y. On the electric conductivity of cuprous sulfide: experiment. J Phys Soc Jpn, 1953, 8680-681 CrossRef ADS Google Scholar

[102] Ema Y. Cu electromigration effect on Cu2−xSe film properties. Jpn J Appl Phys, 1990, 292098-2102 CrossRef ADS Google Scholar

[103] Bailey TP, Hui S, Xie H, et al. Enhanced ZT and attempts to chemically stabilize Cu2Se via Sn doping. J Mater Chem A, 2016, 417225-17235 CrossRef Google Scholar

[104] Qiu P, Agne MT, Liu Y, et al. Suppression of atom motion and metal deposition in mixed ionic/electronic conductors. Nat Commun, 2018, 92910 CrossRef Google Scholar

[105] Tang H, Sun FH, Dong JF, et al. Graphene network in copper sulfide leading to enhanced thermoelectric properties and thermal stability. Nano Energy, 2018, 49267-273 CrossRef Google Scholar

[106] Li W, Ibáñez M, Cadavid D, et al. Colloidal synthesis and functional properties of quaternary Cu-based semiconductors: Cu2HgGeSe4. J Nanopart Res, 2014, 162297 CrossRef ADS Google Scholar

[107] Navrátil J, Kucek V, Plecháček T, et al. Thermoelectric properties of Cu2HgSnSe4-Cu2HgSnTe4 solid solution. J Elec Materi, 2014, 433719-3725 CrossRef ADS Google Scholar

[108] Pavan Kumar V, Guilmeau E, Raveau B, et al. A new wide band gap thermoelectric quaternary selenide Cu2MgSnSe4. J Appl Phys, 2015, 118155101 CrossRef ADS Google Scholar

[109] Ibáñez M, Zamani R, LaLonde A, et al. Cu2ZnGeSe4 nanocrystals: synthesis and thermoelectric properties. J Am Chem Soc, 2012, 1344060-4063 CrossRef PubMed Google Scholar

[110] Doverspike K, Dwight K, Wold A. Preparation and characterization of copper zinc germanium sulfide selenide (Cu2ZnGeS4-ySey). Chem Mater, 1990, 2194-197 CrossRef Google Scholar

[111] Xie H, Su X, Zheng G, et al. The role of Zn in chalcopyrite CuFeS2: enhanced thermoelectric properties of Cu1−xZnxFeS2 with in situ nanoprecipitates. Adv Energy Mater, 2016, 71601299 CrossRef Google Scholar

[112] Li D, Li R, Qin XY, et al. Co-precipitation synthesis of Sn and/or S doped nanostructured Cu3Sb1−xSnxSe4−ySy with a high thermoelectric performance. CrystEngComm, 2013, 157166-7170 CrossRef Google Scholar

[113] Wei TR, Wang H, Gibbs ZM, et al. Thermoelectric properties of Sn-doped p-type Cu3SbSe4: a compound with large effective mass and small band gap. J Mater Chem A, 2014, 213527-13533 CrossRef Google Scholar

[114] Cheng N, Liu R, Bai S, et al. Enhanced thermoelectric performance in Cd doped CuInTe2 compounds. J Appl Phys, 2014, 115163705 CrossRef ADS Google Scholar

[115] Zhang J, Qin X, Li D, et al. Enhanced thermoelectric properties of Ag-doped compounds CuAgxGa1−xTe2 (0≤x≤0.05). J Alloys Compd, 2014, 586285-288 CrossRef Google Scholar

[116] Kucek V, Drasar C, Kasparova J, et al. High-temperature thermoelectric properties of Hg-doped CuInTe2. J Appl Phys, 2015, 118125105 CrossRef ADS Google Scholar

[117] Kucek V, Drasar C, Navratil J, et al. Thermoelectric properties of Ni-doped CuInTe2. J Phys Chem Solids, 2015, 8318-23 CrossRef ADS Google Scholar

[118] Shen J, Chen Z, lin S, et al. Single parabolic band behavior of thermoelectric p-type CuGaTe2. J Mater Chem C, 2016, 4209-214 CrossRef Google Scholar

[119] Li Y, Zhang T, Qin Y, et al. Thermoelectric transport properties of diamond-like Cu1−xFe1+xS2 tetrahedral compounds. J Appl Phys, 2014, 116203705 CrossRef ADS Google Scholar

[120] Li XY, Li D, Xin HX, et al. Effects of bismuth doping on the thermoelectric properties of Cu3SbSe4 at moderate temperatures. J Alloys Compd, 2013, 561105-108 CrossRef Google Scholar

[121] Yang C, Huang F, Wu L, et al. New stannite-like p-type thermoelectric material Cu3SbSe4. J Phys D-Appl Phys, 2011, 44295404 CrossRef ADS Google Scholar

[122] Skoug EJ, Cain JD, Majsztrik P, et al. Doping effects on the thermoelectric properties of Cu3SbSe4. Sci Adv Mat, 2011, 3602-606 CrossRef Google Scholar

[123] Chetty R, Bali A, Mallik RC. Thermoelectric properties of indium doped Cu2CdSnSe4. Intermetallics, 2016, 7217-24 CrossRef Google Scholar

[124] Kosuga A, Higashine R, Plirdpring T, et al. Effects of the defects on the thermoelectric properties of Cu–In–Te chalcopyrite-related compounds. Jpn J Appl Phys, 2012, 51121803 CrossRef Google Scholar

[125] Wei TR, Li F, Li JF. Enhanced thermoelectric performance of nonstoichiometric compounds Cu3−xSbSe4 by Cu deficiencies. J Elec Mater, 2014, 432229-2238 CrossRef ADS Google Scholar

[126] Goto Y, Naito F, Sato R, et al. Enhanced thermoelectric figure of merit in Stannite–Kuramite solid solutions Cu2+xFe1–xSnS4–y (x= 0–1) with anisotropy lowering. Inorg Chem, 2013, 529861-9866 CrossRef PubMed Google Scholar

[127] Zeier WG, Heinrich CP, Day T, et al. Bond strength dependent superionic phase transformation in the solid solution series Cu2ZnGeSe4−xSx. J Mater Chem A, 2014, 21790-1794 CrossRef Google Scholar

[128] Berman R. Thermal Conduction in Solids. Oxford: Clarendon Press, 1976. Google Scholar

[129] Li Y, Meng Q, Deng Y, et al. High thermoelectric performance of solid solutions CuGa1−xInxTe2 (x = 0–1.0). Appl Phys Lett, 2012, 100231903 CrossRef ADS Google Scholar

[130] Skoug EJ, Cain JD, Morelli DT, et al. Lattice thermal conductivity of the Cu3SbSe4-Cu3SbS4 solid solution. J Appl Phys, 2011, 110023501 CrossRef ADS Google Scholar

[131] Zeier WG, Pei Y, Pomrehn G, et al. Phonon scattering through a local anisotropic structural disorder in the thermoelectric solid solution Cu2Zn1–xFexGeSe4. J Am Chem Soc, 2013, 135726-732 CrossRef PubMed Google Scholar

[132] Liu FS, Wang B, Ao WQ, et al. Crystal structure and thermoelectric properties of Cu2Cd1−xZnxSnSe4 solid solutions. Intermetallics, 2014, 5515-21 CrossRef Google Scholar

[133] Li Z, Xiao C, Zhu H, et al. Defect chemistry for thermoelectric materials. J Am Chem Soc, 2016, 13814810-14819 CrossRef PubMed Google Scholar

[134] Chen H, Yang C, Liu H, et al. Thermoelectric properties of CuInTe2/graphene composites. CrystEngComm, 2013, 156648-6651 CrossRef Google Scholar

[135] Luo Y, Yang J, Jiang Q, et al. Large enhancement of thermoelectric performance of CuInTe2via a synergistic strategy of point defects and microstructure engineering. Nano Energy, 2015, 1837-46 CrossRef Google Scholar

[136] Dong Y, Wang H, Nolas GS. Synthesis, crystal structure, and high temperature transport properties of p-type Cu2Zn1–xFexSnSe4. Inorg Chem, 2013, 5214364-14367 CrossRef PubMed Google Scholar

[137] Dong Y, Wang H, Nolas GS. Synthesis and thermoelectric properties of Cu excess Cu2ZnSnSe4. Phys Status Solidi RRL, 2014, 861-64 CrossRef ADS Google Scholar

[138] Cho JY, Shi X, Salvador JR, et al. Thermoelectric properties of ternary diamondlike semiconductors Cu2Ge1+xSe3. J Appl Phys, 2010, 108073713 CrossRef ADS Google Scholar

[139] Xi L, Zhang YB, Shi XY, et al. Chemical bonding, conductive network, and thermoelectric performance of the ternary semiconductors Cu2SnX3 (X=Se, S) from first principles. Phys Rev B, 2012, 86155201 CrossRef ADS Google Scholar

[140] Fan J, Carrillo-Cabrera W, Akselrud L, et al. New monoclinic phase at the composition Cu2SnSe3 and its thermoelectric properties. Inorg Chem, 2013, 5211067-11074 CrossRef PubMed Google Scholar

[141] Fan J, Carrillo-Cabrera W, Antonyshyn I, et al. Crystal structure and physical properties of ternary phases around the composition Cu5Sn2Se7 with tetrahedral coordination of atoms. Chem Mater, 2014, 265244-5251 CrossRef Google Scholar

[142] Tan Q, Sun W, Li Z, et al. Enhanced thermoelectric properties of earth-abundant Cu2SnS3 via in doping effect. J Alloys Compd, 2016, 672558-563 CrossRef Google Scholar

[143] Huang T, Yan Y, Peng K, et al. Enhanced thermoelectric performance in copper-deficient Cu2GeSe3. J Alloys Compd, 2017, 723708-713 CrossRef Google Scholar

[144] Cho JY, Shi X, Salvador JR, et al. Thermoelectric properties and investigations of low thermal conductivity in Ga-doped Cu2GeSe3. Phys Rev B, 2011, 84085207 CrossRef ADS Google Scholar

[145] Shen Y, Li C, Huang R, et al. Eco-friendly p-type Cu2SnS3 thermoelectric material: crystal structure and transport properties. Sci Rep, 2016, 632501 CrossRef PubMed ADS Google Scholar

[146] Adhikary A, Mohapatra S, Lee SH, et al. Metallic ternary telluride with sphalerite superstructure. Inorg Chem, 2016, 552114-2122 CrossRef PubMed Google Scholar

[147] Vaqueiro P, Guélou G, Kaltzoglou A, et al. The influence of mobile copper ions on the glass-like thermal conductivity of copper-rich tetrahedrites. Chem Mater, 2017, 294080-4090 CrossRef Google Scholar

[148] Sun FH, Wu CF, Li Z, et al. Powder metallurgically synthesized Cu12Sb4S13 tetrahedrites: phase transition and high thermoelectricity. RSC Adv, 2017, 718909-18916 CrossRef Google Scholar

[149] Barbier T, Lemoine P, Gascoin S, et al. Structural stability of the synthetic thermoelectric ternary and nickel-substituted tetrahedrite phases. J Alloys Compd, 2015, 634253-262 CrossRef Google Scholar

[150] Lu X, Morelli D. The effect of Te substitution for Sb on thermoelectric properties of tetrahedrite. J Elec Materi, 2014, 431983-1987 CrossRef ADS Google Scholar

[151] Kosaka Y, Suekuni K, Hashikuni K, et al. Effects of Ge and Sn substitution on the metal–semiconductor transition and thermoelectric properties of Cu12Sb4S13 tetrahedrite. Phys Chem Chem Phys, 2017, 198874-8879 CrossRef PubMed ADS Google Scholar

[152] Bouyrie Y, Sassi S, Candolfi C, et al. Thermoelectric properties of double-substituted tetrahedrites Cu12−xCoxSb4−yTeyS13. Dalton Trans, 2016, 457294-7302 CrossRef PubMed Google Scholar

[153] Sun FH, Dong J, Dey S, et al. Enhanced thermoelectric performance of Cu12Sb4S13−δ tetrahedrite via nickel doping. Sci China Mater, 2018, 611209-1217 CrossRef Google Scholar

[154] Chetty R, Bali A, Mallik RC. Tetrahedrites as thermoelectric materials: an overview. J Mater Chem C, 2015, 312364-12378 CrossRef Google Scholar

[155] Kim FS, Suekuni K, Nishiate H, et al. Tuning the charge carrier density in the thermoelectric colusite. J Appl Phys, 2016, 119175105 CrossRef ADS Google Scholar

[156] Suekuni K, Tsuruta K, Kunii M, et al. High-performance thermoelectric mineral Cu12−xNixSb4S13 tetrahedrite. J Appl Phys, 2013, 113043712 CrossRef ADS Google Scholar

[157] Lin H, Chen H, Shen JN, et al. Chemical modification and energetically favorable atomic disorder of a layered thermoelectric material TmCuTe2 leading to high performance. Chem Eur J, 2014, 2015401-15408 CrossRef PubMed Google Scholar

[158] Esmaeili M, Tseng YC, Mozharivskyj Y. Thermoelectric properties, crystal and electronic structure of semiconducting RECuSe2 (RE=Pr, Sm, Gd, Dy and Er). J Alloys Compd, 2014, 610555-560 CrossRef Google Scholar

[159] Yang G, Yao Y, Ma D. Structural, electronic, and thermoelectric properties of La2CuBiS5. Sci China Mater, 2017, 60151-158 CrossRef Google Scholar

[160] Gulay LD, Daszkiewicz M, Shemet VY. Crystal structure of ∼RCu3S3 and ∼RCuTe2 (R=Gd–Lu) compounds. J Solid State Chem, 2012, 186142-148 CrossRef ADS Google Scholar

[161] Oudah M, Kleinke KM, Kleinke H. Thermoelectric properties of the quaternary chalcogenides BaCu5.9STe6 and BaCu5.9SeTe6. Inorg Chem, 2014, 54845-849 CrossRef PubMed Google Scholar

[162] Kurosaki K, Uneda H, Muta H, et al. Thermoelectric properties of potassium-doped β-BaCu2S2 with natural superlattice structure. J Appl Phys, 2005, 97053705 CrossRef ADS Google Scholar

[163] Li J, Zhao LD, Sui J, et al. BaCu2Se2 based compounds as promising thermoelectric materials. Dalton Trans, 2015, 442285-2293 CrossRef PubMed Google Scholar

[164] Zhao LD, He J, Berardan D, et al. BiCuSeO oxyselenides: new promising thermoelectric materials. Energy Environ Sci, 2014, 72900-2924 CrossRef Google Scholar

[165] Lan JL, Liu YC, Zhan B, et al. Enhanced thermoelectric properties of Pb-doped BiCuSeO ceramics. Adv Mater, 2013, 255086-5090 CrossRef PubMed Google Scholar

[166] Li F, Wei TR, Kang F, et al. Enhanced thermoelectric performance of Ca-doped BiCuSeO in a wide temperature range. J Mater Chem A, 2013, 111942-11949 CrossRef Google Scholar

[167] Liu Y, Lan J, Xu W, et al. Enhanced thermoelectric performance of a BiCuSeO system via band gap tuning. Chem Commun, 2013, 498075-8077 CrossRef PubMed Google Scholar

  • Figure 1

    Timeline of zT for selected Cu-based superionic conductors [1327] (red), tetragonal [2837] (blue) and distorted [3849] (green) diamond-like materials and BiCuSeO oxyselenides (purple) [5061].

  • Figure 2

    (a) Thermal conductivity for Cu-based chalcogenides; (b) lattice thermal conductivity as a function of the primitive cell volume in a variety of Cu-based chalcogenides at 300 K. The dashed line shows a negative correlation between the lattice thermal conductivity and the primitive cell volume. Data are taken from Refs. [14,16,2931,42,45,6677].

  • Figure 3

    Liquid-like behavior in Cu-based materials. (a) Crystal structure of Cu2Se where Cu atoms flow among the interstitial sites of Se rigid sublattice, reproduced from Ref. [14], Copyright 2012, Nature Publishing Group; (b) schematic phonon DOS for solid and liquid-like materials, adapted from Ref. [12], Copyright 2016, Elsevier; (c) temperature dependence of the specific heat in Cu2Se and Cu2S; (d) atomic displacement parameter varying with temperature in Cu3SbSe3 and (e) trajectories of atoms from molecular dynamics simulations for Cu3SbSe3 at 400 K , reproduced from Ref. [79,80], Copyright 2014, National Academy of Sciences and Copyright 2014, Nature Publishing Group, respectively.

  • Figure 4

    Schematic diagram of the lone pair electrons situation in Cu3SbSe4, CuSbSe2, Cu3SbSe3 compounds, reproduced from Ref. [83], Copyright 2011, the American Physical Society.

  • Figure 5

    (a) Partial charge density of the state plots of Cu2SnSe3 near the upper valence-band, reproduced from Ref. [39] Copyright 2010, the American Chemical Society; (b) band convergence in the pseudocubic diamond-like chalcogenides, reproduced from Ref. [32], Copyright 2014, Wiley-VCH GmBH&Co.

  • Figure 6

    (a) Phases varying with temperature for Cu2X compounds; (b) schematic depiction of high-temperature superionic crystal structure of Cu2S, reproduced from Ref. [16], Copyright 2014, Wiley-VCH GmBH&Co. The blue spheres represent sulfur atoms, and the liquid-like copper ions (yellow) travel freely within the sulfide sublattice. (c) zT as a function of temperature for Cu2X compounds [14,16,18].

  • Figure 7

    (a) Schematic depiction of mosaic structures, (b) TEM image for Cu2S0.5Te0.5 as a mosaic crystal, (c) zT values for mosaic and usual crystals. Figures are adapted from Ref. [17], Copyright 2015, Wiley-VCH GmBH&Co.

  • Figure 8

    Thermal conductivity and maximum zT for selected ternary superionic conductors: Cu7PSe6 [68], Cu7.6Ag0.4GeSe5.1Te0.9 [94], CuAgSe0.95Te0.05 [95], CuCrSe2-AgCrSe2 [96], 0.8Cu8S4-0.2Cu5FeS4 [67] and Cu1.7Bi4.7Se8 [97].

  • Figure 9

    (a) The crystal structures of Cu5FeS4 for the low temperature phase and high temperature phase. Reproduced from Ref. [67], Copyright 2014, the Royal Society of Chemistry; (b) Temperature dependence for the zT value for the mCu8S4−(1−m) Cu5FeS4 compound.

  • Figure 10

    High-temperature crystal structure for (a) Cu7PSe6 (reproduced from Ref. [68], Copyright 2014, the American Chemical Society) and (b) Cu8GeSe6 (reproduced from Ref. [94], Copyright 2017, the Royal Society of Chemistry); (c) lattice thermal conductivity as a function of the temperature for the two compounds [68,94].

  • Figure 11

    Crystal structure of diamond, zinc-blende ZnSe, chalcopyrite CuInSe2, stannite Cu3SbSe4 and Cu2ZnSnSe4.

  • Figure 12

    (a) Distortion parameter as a function of the lattice parameter a [28,72,87,106108,119,123,126,136,137]. (b) Temperature dependence of zT for tetragonal diamond-like compounds [28,29,87,112,119].

  • Figure 13

    Crystal structure of (a) Cu2SnSe3 (reproduced from Ref. [140], Copyright 2013, the American Chemical Society) and (b) Cu5Sn2Se7 (reproduced from Ref. [141], Copyright 2014, the American Chemical Society); (c) zT of distorted diamond-like Cu2SnSe3 [38], Cu5Sn2Se7 [141], Cu2SnS3 [142] and Cu2GeSe3 [143].

  • Figure 14

    (a) Crystal structure of tetrahedrites, reproduced from Ref. [47], Copyright 2016, American Chemical Society; (b) zT of tetrahedrites [4649,147153]; (c) crystal structure and (d) zT of colusites, reproduced from Ref. [43], Copyright 2016, the Royal Society of Chemistry.

  • Figure 15

    (a) The crystal structure for YCuTe2 in low temperature phase (P-3m1) and high temperature phase (P-3), reproduced from Ref. [69], Copyright 2016, the Royal Society of Chemistry. (b) Thermal conductivity and zT for YCuTe2 and TmCuTe2 [69,157,160].

  • Figure 16

    Crystal structure for (a) BaCu2Se2 (reproduced from Ref. [163], Copyright 2015, the Royal Society of Chemistry) and (b) BaCu5.9SeTe6 (reproduced from Ref. [161], Copyright 2014, American Chemical Society); (c) zT value as a function of the temperature for Ba1.925Na0.075Cu2Se2 and BaCu5.9Se(S)Te6, respectively [161,163].

  • Figure 17

    (a) Crystal structure of BiCuSeO, reproduced from Ref. [52] Copyright 2012, the Royal Society of Chemistry; (b) zT values for pristine [52], Bi-site-doped [50,5355,59,165] and cation-deficient [51,58] BiCuSeO compounds; (c) band gap variation and zT values for BiCuSe1−xTexO [167]; (d) schematic depiction of modulation doping and (e) mobility, reproduced from Ref. [57] Copyright 2014, American Chemical Society; (f) zT as a function of Bi0.875Ba0.125CuSeO samples before and after hot-forging [56,164].

  • Table 1   Space group, band gap and for selected I-III-VI, I-V-VI and I-II-IV-VI tetragonal diamond-like compounds

    Chemical

    formula

    Space group

    Eg (eV)

    zT, T (K)

    Ref.

    CuGaTe2

    I-42d

    1.2

    1.4, 923

    [31]

    CuInTe2

    I-42d

    1.02

    1.18, 850

    [30]

    CuFeS2 (n)

    I-42d

    0.34

    0.21, 573

    [74]

    Cu3SbSe4

    I-42m

    0.31

    1.26, 673

    [35]

    Cu3SbS4

    I-42m

    0.9

    0.10, 300

    [73]

    Cu2CdSnSe4

    I-42m

    0.98

    0.65, 700

    [28]

    Cu2ZnSnSe4

    I-42m

    1.41

    0.95, 850

    [29]

    Cu2HgSnSe4

    I-42m

    1.81

    0.2, 723

    [71]

    Cu2HgGeSe4

    I-42m

    /

    0.34, 733

    [106]

    Cu2HgSnTe4

    I-42m

    1.62

    /

    [107]

    Cu2MgSnSe4

    I-42m

    1.7

    0.42, 700

    [108]

    Cu2CdGeSe4

    I-42m

    1.2

    0.42, 723

    [72]

    Cu2ZnGeSe4

    I-42m

    1.4

    0.55, 723

    [109]

    Cu2ZnGeS4

    I-42m

    1.5

    /

    [110]

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