L. E. Bell, Cooling, heating, generating power, and recovering waste heat with thermoelectric systems, Science, vol.321, pp.1457-1461, 2008.


G. S. Nolas, J. Sharp, and J. Goldsmid, Thermoelectrics: basic principles and new materials developments, 2013.

Y. Pei, X. Shi, A. Lalonde, H. Wang, L. L. Chen et al., Convergence of electronic bands for high performance bulk thermoelectrics, Nature, vol.473, pp.66-69, 2011.

J. R. Sootsman, D. Y. Chung, and M. G. Kanatzidis, New and Old Concepts in Thermoelectric Materials, Angew. Chemie Int, vol.48, pp.8616-8639, 2009.


K. F. Hsu, Cubic AgPb m SbTe 2+m : Bulk Thermoelectric Materials with High Figure of Merit, Science, pp.818-821, 2004.

K. Suekuni, K. Tsuruta, T. Ariga, and M. Koyano, Thermoelectric Properties of Mineral Tetrahedrites Cu 10 Tr 2 Sb 4 S 13 with Low Thermal Conductivity, Appl. Phys. Express, vol.5, p.51201, 2012.

X. Lu, D. T. Morelli, Y. Xia, F. Zhou, V. Ozolins et al., High Performance Thermoelectricity in Earth-Abundant Compounds Based on Natural Mineral Tetrahedrites, Adv. Energy Mater, vol.3, pp.342-348, 2013.


W. Lai, Y. Wang, D. T. Morelli, and X. Lu, From Bonding Asymmetry to Anharmonic Rattling in Cu 12 Sb 4 S 13 Tetrahedrites: When Lone-Pair Electrons Are Not So Lonely, Adv. Funct. Mater, vol.25, pp.3648-3657, 2015.

R. Chetty, A. Bali, M. H. Naik, G. Rogl, P. Rogl et al., Thermoelectric properties of Co substituted synthetic tetrahedrite, Acta Mater, vol.100, pp.266-274, 2015.

P. Lemoine, C. Bourgès, T. Barbier, V. Nassif, S. Cordier et al., High temperature neutron powder diffraction study of the Cu 12 Sb 4 S 13 and Cu 4 Sn 7 S 16 phases, vol.247, pp.83-89, 2017.
URL : https://hal.archives-ouvertes.fr/hal-01475817

Y. Kosaka, K. Suekuni, K. Hashikuni, Y. Bouyrie, M. Ohta et al., Effects of Ge and Sn substitution on the metal-semiconductor transition and thermoelectric properties of Cu 12 Sb 4 S 13 tetrahedrite, Phys. Chem. Chem. Phys, vol.19, pp.8874-8879, 2017.


D. P. Weller and D. T. Morelli, Rapid synthesis of zinc and nickel co-doped tetrahedrite thermoelectrics by reactive spark plasma sintering and mechanical alloying, J. Alloys Compd, vol.710, pp.794-799, 2017.

T. Barbier, P. Lemoine, S. Gascoin, O. I. Lebedev, A. Kaltzoglou et al.,

R. I. Powell, E. Smith, and . Guilmeau, Structural stability of the synthetic thermoelectric ternary and nickel-substituted tetrahedrite phases, J. Alloys Compd, vol.634, pp.253-262, 2015.
URL : https://hal.archives-ouvertes.fr/hal-02184183


S. Harish, D. Sivaprahasam, M. Battabyal, and R. Gopalan, Phase stability and thermoelectric properties of Cu 10.5 Zn 1.5 Sb 4 S 13 tetrahedrite, J. Alloys Compd, vol.667, pp.323-328, 2016.


T. Barbier, P. Lemoine, S. Martinet, M. Eriksson, M. Gilmas et al., Up-scaled synthesis process of sulphur-based thermoelectric materials, RSC Adv, vol.6, pp.10044-10053, 2016.
URL : https://hal.archives-ouvertes.fr/hal-02184702


C. Bourgès, Y. Bouyrie, A. R. Supka, R. Orabi, P. Lemoine et al., High-Performance Thermoelectric Bulk Colusite by Process Controlled Structural Disordering, J. Am. Chem. Soc, vol.140, pp.2186-2195, 2018.


Y. Kikuchi, Y. Bouyrie, M. Ohta, K. Suekuni, M. Aihara et al., Vanadium-free colusites Cu 26 A 2 Sn 6 S 32 (A = Nb, Ta) for environmentally friendly thermoelectrics, J. Mater. Chem. A, vol.4, pp.15207-15214, 2016.

K. Suekuni, H. I. Tanaka, F. S. Kim, K. Umeo, and T. Takabatake, Glasslike versus crystalline thermophysical properties of the Cu-S based minerals: Tetrahedrite and colusite, J. Phys

. Soc and . Japan, , vol.84, p.103601, 2015.

F. S. Kim, K. Suekuni, H. Nishiate, M. Ohta, H. I. Tanaka et al., Tuning the charge carrier density in the thermoelectric colusite, J. Appl. Phys, vol.119, p.175105, 2016.

K. Suekuni, F. S. Kim, H. Nishiate, M. Ohta, H. I. Tanaka et al., Highperformance thermoelectric minerals: Colusites Cu 26 V 2 M 6 S 32, vol.105, p.132107, 2014.

C. Bourgès, M. Gilmas, P. Lemoine, N. E. Mordvinova, O. I. Lebedev et al., Structural analysis and thermoelectric properties of mechanically alloyed colusites, J. Mater. Chem. C, vol.4, pp.7455-7463, 2016.


P. Lemoine, V. Kumar, G. Guélou, V. Nassif, B. Raveau et al., Thermal Stability of the Crystal Structure and Electronic Properties of the High Power Factor Thermoelectric Colusite Cu 26 Cr 2 Ge 6 S 32, Chem. Mater, vol.32, pp.830-840, 2020.
URL : https://hal.archives-ouvertes.fr/hal-02498319


C. Candolfi, G. Guélou, C. Bourgés, A. R. Supka, A. R. Rabih et al.,

S. Koichiro and . Guilmeau, Disorder-driven glasslike thermal conductivity in colusite Cu 26 V 2 Sn 6 S 32 investigated by Mössbauer spectroscopy and inelastic neutron, Phys. Rev. Mater. Accepted, 2020.

M. S. Lee, S. Takenouchi, and H. Imai, Syntheses of stannoidite and mawsonite and their genesis in ore deposits, Econ. Geol, vol.70, pp.834-843, 1975.


V. Kumar, T. Barbier, V. Caignaert, B. Raveau, R. Daou et al., Copper Hyper-Stoichiometry: The Key for the Optimization of Thermoelectric Properties in Stannoidite Cu 8+x Fe 3-x Sn 2 S 12, J. Phys. Chem. C, vol.121, 2017.

R. Zhang, K. Chen, B. Du, and M. J. Reece, Screening for Cu-S based thermoelectric materials using crystal structure features, J. Mater. Chem. A, vol.5, p.5013, 2017.


P. Qiu, T. Zhang, Y. Qiu, X. Shi, and L. Chen, Sulfide bornite thermoelectric material: a natural mineral with ultralow thermal conductivity, Energy Environ. Sci, vol.7, pp.4000-4006, 2014.

G. Guélou, A. V. Powell, and P. Vaqueiro, Ball milling as an effective route for the preparation of doped bornite: Synthesis, stability and thermoelectric properties, J. Mater. Chem. C, vol.3, pp.10624-10629, 2015.

V. Kumar, T. Barbier, P. Lemoine, B. Raveau, V. Nassif et al., The crucial role of selenium for sulphur substitution in the structural transitions and thermoelectric properties of Cu 5 FeS 4 bornite, Dalt. Trans, vol.46, pp.2174-2183, 2017.
URL : https://hal.archives-ouvertes.fr/hal-01470480


S. O. Long, A. V. Powell, P. Vaqueiro, and S. Hull, High Thermoelectric Performance of Bornite through Control of the Cu(II) Content and Vacancy Concentration, Chem. Mater, vol.30, pp.456-464, 2018.

C. Bourgès, P. Lemoine, O. I. Lebedev, R. Daou, V. Hardy et al., Acta Mater, vol.97, pp.180-190, 2015.

X. Chen, H. Wada, A. Sato, and M. Mieno, Synthesis, Electrical Conductivity, and Crystal Structure of Cu 4 Sn 7 S 16 and Structure, vol.139, pp.144-151, 1998.

J. F. Jemetio, P. Zhou, and H. Kleinke, Crystal structure, electronic structure and thermoelectric properties of Cu 4 Sn 7 S 16, vol.417, pp.55-59, 2006.


V. Kumar, L. Paradis-fortin, P. Lemoine, V. Caignaert, B. Raveau et al., Designing a Thermoelectric Copper-Rich Sulfide from a Natural Mineral: Synthetic Germanite Cu 22 Fe 8 Ge 4 S 32, Inorg. Chem, vol.56, pp.13376-13381, 2017.
URL : https://hal.archives-ouvertes.fr/hal-01640116

J. Rodriguez-carvajal, Recent advances in magnetic structure determination by neutron powder diffraction, Phys. B Condens. Matter, vol.192, pp.55-69, 1993.

T. Roisnel and J. Rodríguez-carvajal, WinPLOTR: A windows tool for powder diffraction pattern analysis, Mater. Sci. Forum, vol.378, pp.118-123, 2001.


P. Thompson, D. E. Cox, and J. B. Hastings, Rietveld Refinement of Debye-Scherrer Synchrotron X-Ray Data from Al 2 O 3, J. Appl. Crystallogr, vol.20, pp.79-83, 1987.

H. S. Kim, Z. M. Gibbs, Y. Tang, H. Wang, and G. J. Snyder, Characterization of Lorenz number with Seebeck coefficient measurement, APL Mater, vol.3, p.41506, 2015.


E. Alleno, D. Bérardan, C. Byl, C. Candolfi, R. Daou et al.,

O. Ravot, M. Rouleau, and . Soulier, Invited Article: A round robin test of the uncertainty on the measurement of the thermoelectric dimensionless figure of merit of Co 0.97 Ni 0.03 Sb 3, Rev. Sci. Instrum, vol.86, p.11301, 2015.

R. T. Tettenhorst and C. E. Corbato, Crystal Structure of Germanite, Am. Mineral, vol.69, pp.943-947, 1984.

K. Suekuni, Y. Shimizu, E. Nishibori, H. Kasai, H. Saito et al., Atomic-scale phonon scatterers in thermoelectric colusites with a tetrahedral framework structure, J. Mater. Chem. A, vol.7, pp.228-235, 2019.
URL : https://hal.archives-ouvertes.fr/hal-02274207

R. Orabi, P. Gougeon, P. Gall, B. Fontaine, M. Colin et al., X -ray Characterization, Electronic Band Structure, and Thermoelectric Properties of the Cluster Compound Ag 2 Tl 2 Mo 9 Se 11, Inorg. Chem, vol.53, pp.11699-11709, 2014.
URL : https://hal.archives-ouvertes.fr/hal-01082282

C. Suryanarayana, Mechanical alloying and milling, Prog. Mater. Sci, vol.46, pp.10-19, 2001.

V. Kumar, A. R. Supka, P. Lemoine, O. I. Lebedev, B. Raveau et al.,

. T-=-cr and W. ). Mo, Toward Functionalization of the Conductive, Network, Adv. Energy Mater, vol.9, p.1803249, 2019.


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V. Kumar, G. Guélou, P. Lemoine, B. Raveau, A. Supka et al., Copper-rich thermoelectric sulfides: size mismatch effect and chemical disorder in the, Angew. Chemie Int. Ed, vol.58, p.15455, 2019.
URL : https://hal.archives-ouvertes.fr/hal-02274210


, ? The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work