Equivalent doping of Te leads to optimized electrical and thermal transport properties in thermoelectric Cu₂MnSnSe₄ alloys

Abstract

Quaternary chalcogenides have garnered considerable interest within the field of thermoelectric due to their intrinsic low thermal conductivity, wide bandgap and high element enrichment advantages. In this work, the thermoelectric performance of Cu₂MnSnSe₄ was enhanced by co-optimizing the carrier concentration and lattice thermal conductivity through self-doping with Cu and doping with Te. A series of Cu₂MnSnSe₄ and Cu_2.1Mn_0.9SnSe_4-xTe_x (x = 0, 0.01, 0.05, 0.10) samples were prepared by ball-milling and hot-pressing methods. The carrier concentration of the samples was significantly increased after Cu self-doping, leading to optimized electrical transport performance. The notable reduction in lattice thermal conductivity was attributed to the scattering effect caused by Te substitution-induced point defects. At 673 K, the lattice thermal conductivity of the Cu_2.1Mn_0.9SnSe_3.9Te_0.1 sample obtained the lowest value of 0.62 W m^-1K^-1. Finally, it achieved a maximum zT ~ 0.5 at 673 K in the Cu_2.1Mn_0.9SnSe_3.9Te_0.1 sample, roughly twice that of the Cu₂MnSnSe₄ sample.

Keywords

Cu₂MnSnSe₄ alloys / Te-doping / electrical properties / thermal conductivity / thermoelectric performance

References

[1] Wang X,Wu M,Yang X.Ultrasonication-assisted fabrication of porous ZnO@C nanoplates for lithium-ion batteries.Microstructures2022;2:2022016

[2] Zhang S.High entropy design: a new pathway to promote the piezoelectricity and dielectric energy storage in perovskite oxides.Microstructures2023;3:2023003

[3] Liu X,Dai L.Influence of halide choice on formation of low-dimensional perovskite interlayer in efficient perovskite solar cells.Energy Environ Mater2022;5:670-82

[4] Bell LE.Cooling, heating, generating power, and recovering waste heat with thermoelectric systems.Science2008;321:1457-61

[5] Xiao Y.Seeking new, highly effective thermoelectrics.Science2020;367:1196-7

[6] Cao T,Zou J.Advances in conducting polymer-based thermoelectric materials and devices.Microstructures2021;1:2021007

[7] Mao J,Ding Z.High thermoelectric cooling performance of n-type Mg₃Bi₂-based materials.Science2019;365:495-8

[8] Snyder GJ.Complex thermoelectric materials.Nat Mater2008;7:105-14

[9] Vijay V,Archana J.Synergistic effect of grain boundaries and phonon engineering in Sb substituted Bi₂Se₃ nanostructures for thermoelectric applications.J Colloid Interface Sci2022;612:97-110

[10] Wu Y,Chen Z.Manipulation of band degeneracy and lattice strain for extraordinary PbTe thermoelectrics.Research2020;2020:8151059 PMCID:PMC7000992

[11] Kim SI,Mun HA.Dense dislocation arrays embedded in grain boundaries for high-performance bulk thermoelectrics.Science2015;348:109-14

[12] Liu WD,Liu Q,Shao Z.High-performance GeTe-based thermoelectrics: from materials to devices.Adv Energy Mater2020;10:2000367

[13] Han MK,Jin Y.A synergistic effect of metal iodide doping on the thermoelectric properties of Bi₂Te₃.Inorg Chem Front2017;4:881-8

[14] Feng L,Liu K.Highly deformable Ag₂Te_1-xSe_x-based thermoelectric compounds.Mater Today Phys2023;33:101051

[15] Heremans JP,Toberer ES.Enhancement of thermoelectric efficiency in PbTe by distortion of the electronic density of states.Science2008;321:554-7

[16] Zheng J,Wang D,Gao X.Synergistically enhanced thermoelectric properties in n-type Bi₆Cu₂Se₄O₆ through inducing resonant levels.Acta Mater2022;232:117930

[17] Zhang Z,Chen H.Entropy engineering induced exceptional thermoelectric and mechanical performances in Cu_2-yAg_yTe_1-2xS_xSe_x.Acta Mater2022;224:117512

[18] Hu L,Wu H.Entropy engineering of SnTe: multi-principal-element alloying leading to ultralow lattice thermal conductivity and state-of-the-art thermoelectric performance.Adv Energy Mater2018;8:1802116

[19] Sun Y,Yao J.High symmetry structure and large strain field fluctuation lead enhancement of thermoelectric performance of quaternary alloys by tuning configurational entropy.Chem Eng J2023;462:142185

[20] Liu M,Zhu J.High performance GeTe thermoelectrics enabled by lattice strain construction.Acta Mater2023;244:118565

[21] Song Q,Chen H.Enhanced carrier mobility and thermoelectric performance in Cu₂FeSnSe₄ diamond-like compound via manipulating the intrinsic lattice defects.Mater Today Phys2018;7:45-53

[22] Zhang YX,Ge ZH.Excellent thermoelectric properties and stability realized in copper sulfides based composites via complex nanostructuring.Acta Mater2022;233:117972

[23] Zhuang HL,Pei J.High ZT in p-type thermoelectric (Bi,Sb)₂Te₃ with built-in nanopores.Energy Environ Sci2022;15:2039-48

[24] Wang T,Wang H.Quaternary chalcogenides: promising thermoelectric material and recent progress.Sci China Mater2020;63:8-15

[25] Song Q,Hao F.Quaternary Pseudocubic Cu₂TMSnSe₄ (TM = Mn, Fe, Co) chalcopyrite thermoelectric materials.Adv Elect Mater2016;2:1600312

[26] Zhang J,Cheng N.High-performance pseudocubic thermoelectric materials from non-cubic chalcopyrite compounds.Adv Mater2014;26:3848-53

[27] Song Q,Chen H.Improved thermoelectric performance in nonstoichiometric Cu_2+δMn_1−δSnSe₄ quaternary diamondlike compounds.ACS Appl Mater Interfaces2018;10:10123-31

[28] Mehmood F,Su W.Improved thermoelectric performance of in-doped quaternary Cu₂MnSnSe₄ alloys.Phys Status Solidi2022;16:2200049

[29] Sun Y,Wang H.Enhancement of thermoelectric performance of Cu₂MnSnSe₄ alloys by regulation of lattice strain.Chem Eng J2024;486:150158

[30] Mukherjee B,Malagutti MA.Thermoelectric performance in disordered Cu₂ZnSnSe₄ nanostructures driven by ultra-low thermal conductivity.J Alloys Compd2023;933:167756

[31] Chen Q,Zhan H.Enhanced thermoelectric performance of chalcogenide Cu₂CdSnSe₄ by ex-situ homogeneous nanoinclusions.J Materiomics2016;2:179-86

[32] Cheng Y,Huang T,Wen G.Potassium ferrate enhanced active manganese oxide filter material to remove BPA: influence of NH⁴⁺, Mn²⁺.Sep Purif Technol2024;341:126903

[33] Henríquez R,Grez Moreno P.Solvothermal synthesis of Cu₂ZnSnSe₄ nanoparticles and their visible-light-driven photocatalytic activity.Nanomaterials2024;14:1079 PMCID:PMC11243532

[34] Xie S,Chen Q,Wang Q.Realizing super-high piezoelectricity and excellent fatigue resistance in domain-engineered bismuth titanate ferroelectrics.Adv Funct Mater2024;34:2312645

[35] Chetty R,Mallik RC.Thermoelectric properties of indium doped Cu₂CdSnSe₄.Intermetallics2016;72:17-24

[36] Wei K.Synthesis and characterization of nanostructured stannite Cu₂ZnSnSe₄ and Ag₂ZnSnSe₄ for thermoelectric applications.ACS Appl Mater Interfaces2015;7:9752-7

[37] Song Q,Zhao K,Shi X.Crystal structure and thermoelectric properties of Cu₂Fe_1-xMn_xSnSe₄ diamond-like chalcogenides.ACS Appl Energy Mater2020;3:2137-46

[38] Dong Y,Martin J.Synthesis, crystal structure, and transport properties of quaternary tetrahedral chalcogenides.J Mater Chem C2015;3:10436-41