Effect of Te and In Co-doping on Thermoelectric Properties of Cu2SnSe3 Compounds

doi:10.15541/jim20220039

Abstract

Abstract:

Recently, Cu₂SnSe₃-based compounds, as a new environment-friendly thermoelectric material, have attracted worldwide attentions. However, the pristine Cu₂SnSe₃ compound possesses relatively low carrier concentration and thus an inferior electronic transport properties. To optimize the thermoelectric properties of Cu₂SnSe₃- based compounds, herein, two series of Cu₂SnSe_3-_xTe_x (x=0-0.2) and Cu₂Sn_1-_yIn_ySe_2.9Te_0.1 (y=0.005-0.03) samples were synthesized through traditional melting-annealing technique combined with plasma activated sintering (PAS). The role of Te and In co-doping on the thermoelectric properties of Cu₂SnSe₃-based compounds were systematically investigated. The solubility limit of Te in the Cu₂SnSe_3-_xTe_x compounds is around 0.10. The substitution of Te on Se site significantly increases the effective mass of charge carrier from 0.2m_e for pristine Cu₂SnSe₃ compound to 0.45m_e for Cu₂SnSe_2.9Te_0.1 compound, which improves the power factor of the material. Cu₂SnSe_2.99Te_0.01 compound attains the maximum power factor of 1.37 μW·cm^-1·K^-2 at 300 K. To further improve the electronic transport properties of the material, Cu₂SnSe_2.9Te_0.1 was chosen as the matrix and In was selected to dope on Sn site. We found that doping with In significantly improves the carrier concentration of Cu₂SnSe₃-based compounds from 5.96×10¹⁸ cm^-3 for Cu₂SnSe_2.9Te_0.1 to 2.06×10²⁰ cm^-3 for Cu₂Sn_0.975In_0.025Se_2.9Te_0.1, which promotes the participation of multiple valence bands in the electronic transport. All these produce the great enhancements on the electrical conductivity, effective mass of charge carriers and power factor. As a result, Cu₂Sn_0.995In_0.005Se_2.9Te_0.1 compound obtains the maximum power factor of 5.69 μW·cm^-1·K^-2 at 473 K. Due to the significant improvement of electrical transport performance and the decrease in lattice thermal conductivity, the maximum ZT of 0.4 is achieved for Cu₂Sn_0.985In_0.025Se_2.9Te_0.1 compound at 773 K, which is 4 times higher than that of pristine Cu₂SnSe₃ compound.

Key words: Cu₂SnSe₃-based compound, Te doping, In doping, thermoelectric property

CLC Number:

TQ174

REN PeiAn, WANG Cong, ZI Peng, TAO Qirui, SU Xianli, TANG Xinfeng. Effect of Te and In Co-doping on Thermoelectric Properties of Cu₂SnSe₃ Compounds[J]. Journal of Inorganic Materials, 2022, 37(10): 1079-1086.

Figures/Tables 11

Fig. 1 Powder XRD patterns of Cu2SnSe3-xTex samples after PAS sintering (a) and corresponding enlarge view near 2θ=53° (b)

Fig. 2 Field emission scanning electron microscopies of freshly fractured surfaces of samples Cu2SnSe3 (a) and Cu2SnSe2.9Te0.1 (b)

Fig. 3 Backscattered electron images of the polished surfaces for samples Cu2SnSe2.9Te0.1 (a) and Cu2SnSe2.85Te0.15 (b) with elemental distribution mappings of Cu2SnSe2.9Te0.1(c-f)

Fig. 4 Temperature dependent electrical conductivity (a), Seebeck coefficient (b) and power factor (c) of Cu2SnSe3-xTex samples

Table 1 Electrical conductivities (σ), Seebeck coefficients (S), carrier concentrations (n) and carrier mobilities (μ) of Cu2SnSe3-xTex samples at room temperature

Sample	σ/(×10⁴, S·m^-1)	S/ (μV·K^-1)	n/(×10¹⁷, cm^-3)	μ/(cm²· V^-1·s^-1)
Cu₂SnSe₃	0.02	472.18	6.25	24.92
Cu₂SnSe_2.99Te_0.01	0.08	408.07	24.34	21.04
Cu₂SnSe_2.96Te_0.04	0.13	294.12	53.77	15.68
Cu₂SnSe_2.93Te_0.07	0.07	402.62	40.29	10.14
Cu₂SnSe_2.9Te_0.1	0.11	298.21	59.63	11.67
Cu₂SnSe_2.85Te_0.15	0.10	356.49	21.27	27.98
Cu₂SnSe_2.8Te_0.2	0.13	241.73	24.05	21.64

Fig. 5 Relationship between carrier concentration and Seebeck coefficient for Cu2SnSe3-xTex and Cu2Sn1-yInySe2.9Te0.1 samples Colorful figure is available on website

Fig. 6 Temperature dependent thermal conductivity for Cu2SnSe3-xTex samples

Fig. 7 Temperature dependent ZT for Cu2SnSe3-xTex samples

Fig. 8 Temperature dependent electrical conductivity (a), Seebeck coefficient (b) and power factor (c) for Cu2Sn1-yInySe2.9Te0.1 samples

Table 2 Electrical conductivities (σ), Seebeck coefficients (S), carrier concentrations (n) and carrier mobilities (μ) of Cu2Sn1-yInySe2.9Te0.1 samples at room temperature

Sample	σ/(×10⁴, S·m^-1)	S/ (μV·K^-1)	n/(×10¹⁹, cm^-3)	μ/(cm²·V^-1·s^-1)
Cu₂SnSe_2.9Te_0.1	0.11	298.21	0.59	11.68
Cu₂Sn_0.995In_0.005Se_2.9Te_0.1	0.97	220.50	4.35	13.95
Cu₂Sn_0.99In_0.01Se_2.9Te_0.1	1.26	185.79	7.15	10.99
Cu₂Sn_0.985In_0.015Se_2.9Te_0.1	1.50	159.47	11.36	8.25
Cu₂Sn_0.98In_0.02Se_2.9Te_0.1	1.67	152.91	10.54	10.08
Cu₂Sn_0.975In_0.025Se_2.9Te_0.1	2.07	130.39	20.60	6.28
Cu₂Sn_0.97In_0.03Se_2.9Te_0.1	2.27	120.35	20.00	7.09

Fig. 9 Temperature dependent thermal conductivity (a) and ZT (b) for Cu2Sn1-yInySe2.9Te0.1 samples

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Effect of Te and In Co-doping on Thermoelectric Properties of Cu₂SnSe₃ Compounds

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