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二维双过渡金属MXene相较于单一过渡金属MXene, 有着更高的可调控性, 在热电器件方面有着潜在的应用. 本文通过第一性原理的计算方法结合玻尔兹曼输运理论, 研究了新型二维双过渡金属MXene单层TiZrCO2和VYCO2的稳定性和热电性能. 结果表明, 两者的热电输运性能优良. 计算预测的结果: 在最优载流子浓度下, 300 K时, p型TiZrCO2功率因子为11.40 mW/(m·K2), 远高于n型, p型VYCO2功率因子 (2.80 mW/(m·K2))和n型(2.20 mW/(m·K2))大小类似. 300 K下, TiZrCO2和VYCO2的晶格热导率较低, 分别为5.08 W/(m·K)和3.22 W/(m·K), 并且随着温度升高进一步降低, 900 K时为2.14 W/(m·K)和1.09 W/(m·K). TiZrCO2和VYCO2的热电优值随温度升高而增大, 温度为900 K时, p型TiZrCO2和VYCO2的热电优值分别达到1.83和0.93, 优于两者n型的0.23和0.84. 双过渡金属MXene TiZrCO2和VYCO2相比单一过渡金属MXene(如Sc2C(OH)2, ZT = 0.5)具有更好的热电性能, 有潜力作为综合性能优良的新型热电材料. 本文采用的一套计算方法亦可为新型双过渡金属元素MXene热电性能探索提供一定借鉴.
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关键词:
- 双过渡金属MXene /
- 第一性原理 /
- 热电性能 /
- 晶格热导率
The quantum restriction effect of charge carriers in two-dimensional materials can significantly improve their power factors. MXene, as a new type of two-dimensional double transition metal material, has attracted extensive attention due to thermoelectric properties, and higher controllability than single transition metal MXene, which has potential applications in thermoelectric devices. In this work, new two-dimensional monolayer double transition metal MXene, i.e. TiZrCO2 and VYCO2, are designed and their stabilities, electronic and thermoelectric properties are studied by the first principles and Boltzmann transport theory. It has been shown that both are indirect bandgap semiconductors with mechanical, thermodynamic and kinetic stability, and their thermoelectric properties (Seebeck coefficients, electrical and electronic thermal conductivities and lattice thermal conductivities) in a temperature range from 300 K to 900 K are studied. For the optimal carrier concentration at 300 K, the p-type TiZrCO2 power factor is 11.40 mW/(m·K2), much higher than that of n-type one, and the VYCO2 power factor of p-type (2.80 mW/(m·K2)) and n-type (2.20 mW/(m·K2)) are similar to each other. At 300 K, TiZrCO2 and VYCO2 have low lattice thermal conductivities of 5.08 W/(m·K) and 3.22 W/(m·K), respectively, and the contributions of optical phonon to the lattice thermal conductivity are both about 30%, i.e. 2.14 W/(m·K) and 1.09 W/(m·K) at 900 K, respectively. At the same time, it is found that at 300 K, when the material size of TiZrCO2 and VYCO2 re within 12.84 nm and 5.47 nm respectively, their lattice thermal conductivities are almost unchanged, and can be adjusted by adjusting the compositions. At 900 K, the thermoelectric value of p-type TiZrCO2 and VYCO2 reach 1.83 and 0.93, respectively, which are better than those of n-type, 0.23 and 0.84. The double transition metals MXene TiZrCO2 and VYCO2 have better thermoelectric properties than the single transition metal MXene(such as Sc2C(OH)2, ZT = 0.5), and have the potential applications in new thermoelectric materials with excellent comprehensive properties. A set of calculation methods used in this paper can also provide some reference for exploring the thermoelectric properties of a new double transition metal element MXene.-
Keywords:
- double transition metal MXene /
- first principles /
- thermoelectric property /
- lattice thermal conductivity
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图 1 单层TiZrCO2和VYCO2 4×4×1超胞结构俯视图(a), (b)和侧视图 (c), (d)
Fig. 1. Top view (a), (b) and side view (c), (d) of monolayer TiZrCO2 and VYCO2 4×4×1 supercellular structure.
图 2 单层TiZrCO2 (a)和VYCO2 (b)声子色散曲线和声子态密度
Fig. 2. Phonon dispersion curve and phonon state density of monolayer TiZrCO2 (a) and VYCO2 (b).
图 3 单层TiZrCO2 (a)和VYCO2 (b)在HSE06泛函下的能带结构及态密度图
Fig. 3. Band structure and state density of monolayer TiZrCO2 (a) and VYCO2 (b) under HSE06 functional.
图 4 p型和n型单层TiZrCO2和VYCO2 Seebeck (a), (b)、电导率(c), (d)和功率因子(e), (f)随载流子浓度变化图
Fig. 4. Variations of monolayer TiZrCO2 and VYCO2 Seebeck(a), (b), conductivity (c), (d), and power factor (e), (f) with carrier concentration for p and n types.
图 5 单层TiZrCO2和VYCO2 (a)及MoS2 (b)晶格热导率随温度变化图
Fig. 5. The lattice thermal conductivity of monolayer TiZrCO2, VYCO2 (a) and MoS2 (b) varies with temperature.
图 6 不同温度下声学声子和光学声子对单层TiZrCO2 (a)和VYCO2 (b)总晶格热导率的贡献
Fig. 6. Contribution of acoustic phonons and optical phonons to the total lattice thermal conductivity of monolayer TiZrCO2 (a) and VYCO2 (b) at different temperatures.
图 8 不同温度下单层TiZrCO2和VYCO2晶格热导率随频率(a)(c)和平均自由程MFP(b)(d)的变化规律
Fig. 8. The thermal conductivity of monolayer TiZrCO2 and VYCO2 lattice changes with frequency (a)(c) and mean free path MFP(b)(d) at different temperatures.
图 7 300 K下单层TiZrCO2和VYCO2的声子速度 (a)(b)、声子寿命 (c)(d)和格林艾森常数 (e)(f)随频率的变化
Fig. 7. Phonon velocity (a) (b), phonon lifetime (c) (d), and Grüneisen parameter (e)(f) of monolayer TiZrCO2 and VYCO2 at 300 K with frequency.
图 9 单层TiZrCO2 (a)和VYCO2 (b)热电优值随载流子浓度变化图
Fig. 9. The thermoelectric value of monolayer TiZrCO2 (a) and VYCO2 (b) varies with carrier concentration.
表 1 单层TiZrCO2 和VYCO2的晶格常数a、弹性张量和带隙
Table 1. Lattice constants a, elastic tensors, and bandgaps of monolayer TiZrCO2 and VYCO2.
a/Å C11(C22)/(N·m–1) C12/(N·m–1) C66/(N·m–1) EPBE/eV EHSE06/eV TiZrCO2 3.19 247.64 87.88 0.01 0.74 1.50 VYCO2 3.32 78.41 38.93 0.20 1.10 2.15 
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表 2 300 K下单层TiZrCO2 和VYCO2的形变势能E1、弹性常量C、有效质量m*、弛豫时间τ(括号内数据为文献[35]的计算结果)
Table 2. Deformation potential energy E1, elastic constant C, effective mass m*, relaxation time τ of monolayer TiZrCO2 and VYCO2 at 300 K (the data in brackets are the calculation results of Ref. [35]).
Carrier type C/(J·m–2) E1/eV m*/me τ/fs TiZrCO2 Electro 248 10.8 2.69 6.39 Hole 248 2.7 0.75 366.56 VYCO2 Electro 78 3.7 1.67 27.48 Hole 78 4.81 0.94 28.96 MoS2 Electro 168(166) 8.34(8.61) 0.46(0.44) 42.51(40.9) Hole 168 3.81 0.56 167.3
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