In-situ growth of high-performance (Ag, Sn) co-doped CoSb3 thermoelectric thin films

doi:10.1016/j.jmst.2021.04.007

Abstract

Abstract:

Owing to the unique features, such as mechanically robust, low-toxic, high stability, and high thermoelectric performance, CoSb₃-based skutterudite materials are among art-of-the state thermoelectric candidates. In this work, we develop a facile in-situ method for the growth of well-crystallinity (Ag, Sn) co-doped CoSb₃ thin films. This preparation method can efficiently control the dopant concentration and distribution in the thin films. Both the density functional theory calculation and the experimental results suggest that Sn and Ag dopants trend to enter the lattice and preferentially fill interstitial sites. Additionally, band structure calculation results suggest that the Fermi level moves into the conduction bands due to co-doping and eventually induces the increased electrical conductivity, which agrees with the optimization of carrier concentration. Moreover, an increase in the density of state after co-doping is responsible for the increased Seebeck coefficient. As a result, the power factors of (Ag, Sn) co-doped CoSb₃ thin films are greatly enhanced, and the maximum power factor achieves over 0.3 mW m^-1 K^-2 at 623 K, which is almost two times than that of the un-doped CoSb₃ film. Multiple microstructures, including Sb vacancies and Ag/Sn interstitial atoms as point defects, and a high density of lattice distortions coupled with nano-sized Ag-rich grains, lead to all scale phonon scatterings. As a result, a reduced thermal conductivity of ~0.28 W m^-1 K^-1 and a maximum ZT of ~0.52 at 623 K are obtained from (Ag, Sn) co-doped CoSb₃ thin films. This study indicates our facile in-situ growth can be used to develop high-performance dual doped CoSb₃ thins_.

Key words: CoSb₃ thin films, Thermoelectric, Magnetron sputtering, Co-doping

Zhuang-Hao Zheng, Jun-Yu Niu, Dong-Wei Ao, Bushra Jabar, Xiao-Lei Shi, Xin-Ru Li, Fu Li, Guang-Xing Liang, Yue-Xing Chen, Zhi-Gang Chen, Ping Fan. In-situ growth of high-performance (Ag, Sn) co-doped CoSb₃ thermoelectric thin films[J]. J. Mater. Sci. Technol., 2021, 92: 178-185.

Figures/Tables 6

Fig. 1. (a) XRD patterns of CoSb3 thin films. The right side is showing the patterns of (013) peaks with magnified XRD. (b) Influence of Sn doping content on the Lattice parameters. (c) Calculated formation energies of Ag, Sn, and Sn/Ag co-doping in different states of doping. The corresponding doping states are illustrated in Figure S2. (d) Raman spectra of un-doped and Ag/Sn co-doped CoSb3 based thin films.

Fig. 2. SEM images of (a) un-doped, (b) 0.2% Ag + 1.7% Sn co-doped, (c) 0.2% Ag + 2.3% Sn co-doped, and (d) 0.2% Ag + 3.2% Sn co-doped CoSb3 thin films. (e) Schematic illustration of CoSb3 growth (1) Sn layer deposited on the substrate; (2) Formation of (Ag, Sn) co-doping CoSb3 films;(3) Distribution of grains in CoSb3 films.

Fig. 3. STEM-HAADF image of the thin film with 0.2% Ag + 3.2% Sn; (a)-(b) images indicate the distribution of grain boundaries and nano-sized Ag-rich precipitates, c) schematic view of co-doped CoSb3 frame structure, (d)-(e) corresponding IFFT images of the area spotted in rectangle b1 & b2 in (b), (f) lattice distortion cores embedded in HRTEM image acquired from co-doped CoSb3 thin film,(g) Inverse FFT (IFFT) image of the area spotted in solid rectangle 1 in (f) and inset are the enlarged view of solid rectangle regions (b1) & (b2) in (g), (h) IFFT image of the area spotted in solid rectangle 2 in (f), (i)-(k) strain mapping of areas spotted in dashed rectangles b1, b2 & c1 in (g) and (h) showing the embedded lattice distortions, respectively.

Fig. 4. (a) Temperature dependence of σ of the CoSb3 thin films. (b) Measured n and μ of the thin films as a function of Sn doping content. (c) Temperature dependence of S and (d) S2σ of the CoSb3 thin films.

Fig. 5. Calculated band structures of (a) pristine and (b) Ag/Sn co-doped CoSb3 and corresponding DOS & PDOS of (c) pristine and (d) Ag/Sn co-doped CoSb3, respectively.

Fig. 6. Temperature dependence of (a) κ, (b) κl, (c) ZT of the thin films. (d) Comparison of ZT values among Yb-filled CoSb3 [44], pristine CoSb3 [45], and CoSb3 based thin films in this work. (e) Displacement as a function of loading force during a cyclic test of un-doped and co-doped CoSb3 thin films, with 0.2% Ag and 2.3% Sn. (f) Elastic modulus and hardness of un-doped and co-doped CoSb3 thin films, with 0.2% Ag and 2.3% Sn.

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In-situ growth of high-performance (Ag, Sn) co-doped CoSb₃ thermoelectric thin films

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