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中国物理学会期刊

超导三元氢化物CaYH12电子及空穴掺杂调控的第一性原理研究

First-principles study of regulation of electron and hole doping in superconducting ternary hydride CaYH12

CSTR: 32037.14.aps.74.20250180
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  • 近年来, 高压下的富氢化合物被认为是室温超导体的最佳候选体系之一, 如何降低富氢化合物稳定所需压力并保持其优异超导电性是目前该领域重要的科学问题. 研究利用第一性原理计算方法探索了电子及空穴掺杂对三元氢化物 Pm\bar 3m (CaYH12)动力学稳定性和超导电性的调控作用. 结果表明, 空穴掺杂可在晶格中产生“化学预压缩”效应, 消除其在较低压力下的虚频声子, 使其在较低压力下保持动力学稳定. 当空穴掺杂浓度达到1.1 e/cell时, Pm\bar 3m (CaYH12)的动力学稳定压力由180 GPa降至70 GPa, 且同时可以保持约194 K的超导转变温度. 由此可见, 空穴掺杂是一种实现 Pm\bar 3m (CaYH12)超导电性优化(低稳定压力、高温超导)的有效策略. 本工作为三元氢化物在较低压力下实现高温超导提供了新途径, 并为相关实验研究提供了理论支撑.

     

    In the past few decades, achieving room-temperature superconductivity has become an unremitting pursuit of scientists. Guided by the “chemical precompression” theory, hydrogen-rich compounds have emerged as the main candidates for high-temperature superconductors, positioning them at the forefront of superconducting materials research. Extensive computational studies have identified numerous binary hydrides with predicted superconducting transition temperatures (Tc) exceeding 200 K, such as CaH6, H3S, MgH6, YH6, YH9, YH10, and LaH10. Significantly, the high-Tc super-conductivities of H3S, LaH10, CaH6, YH6, YH9 have been experimentally confirmed. Compared with binary hydrides, ternary hydrides offer more diverse chemical compositions and structures, potentially leading to enhanced properties. Zhang et al. Zhang Z, Cui T, Hutcheon M J, et al. 2022 Phys. Rev. Lett. 128 047001 theoretically designed a series of AXH8-type (A = Sc, Ca, Y, Sr, La, Ba; X = Be, B, Al) ternary hydrides with “fluorite-type” backbone, which were predicted to have high-Tc values under moderate pressure. Among those ternary hydrides, LaBeH8 has been experimentally confirmed to achieve a Tc value of 110 K at 80 GPa. The Tc values of ternary clathrate hydrides of Li2MgH16 and Li2NaH17 have been predicted to greatly exceed the room temperature, while the required stabilization pressures all exceeded 200 GPa. Xie et al. Xie H, Duan D F, Shao Z J, et al. 2019 J. Phys. Condens. Matter. 31 245404 and Liang et al. Liang X W, Bergara A, Wang L Y, et al. 2019Phys. Rev. B 99 100505(R) independently predicted CaYH12 compounds with Pm\bar 3m and Fd\bar 3m space groups, both of which exhibited high-Tc above 200 K at about 200 GPa. Other ternary hydrides, such as La-B-H, K-B-H, La-Ce-H, and Y-Ce-H, have also been extensively investigated. At current stage, a major focus of superconducting hydrides is to achieve high-temperature superconductivity at lower pressures. In this study, taking Pm\bar 3m (CaYH12) as a representative, we systematically investigate the effects of electron and hole doping on the dynamical stability and superconductivity in ternary hydride by first-principal calculations. The Pm\bar 3m (CaYH12) exhibits a Tc value of 218 K at 200 GPa, which is consistent with that reported previously. When decompressing to below 180 GPa, imaginary phonons emerge. The analysis of doping simulations demonstrates that the electron doping exacerbates the softening of the imaginary phonons, whereas hole doping eliminates the imaginary frequencies. At the pressures of 130, 100 and 70 GPa, the Pm\bar 3m (CaYH12) phase can be stabilized by hole doping at the concentrations of 0.9, 0.8, and 1.1 e/cell, respectively. Further electron-phonon coupling calculations show that the Tc values of Pm\bar 3m (CaYH12) at 130, 100 and 70 GPa are 194, 209, and 194 K at the corresponding doping level, which are only 10–20 K less than the Tc at 200 GPa. At the pressure of 70 GPa, Tc slightly decreases to 189 K at a doping level of 1.2 e/cell, primarily due to the reduced ωlog compared with that in the case of 1.1 e/cell. And the enhanced λ at 1.2 e/cell is mainly contributed by the average electron-phonon coupling matrix element \langle I^2\rangle and average phonon frequency \langle \omega ^2\rangle ^1/2 , rather than the electronic density of states at the Fermi level N(εF). These results indicate that hole doping represents a promising and effective strategy for optimizing the superconductivity of Pm\bar 3m (CaYH12) by maintaining high-Tc at low pressures. Our study paves an avenue for realizing high-temperature superconductors at low pressure.

     

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