High Tc superconductivity in layered hydrides XH15 (X = Ca,Sr, Y,La) under high pressures

The theoretical predictions and experimental synthesis of H₃S and LaH₁₀ superconductors with record high superconducting transition temperatures (T_c) have promoted the hydrogen-based superconducors to be a research hotspot in the field of solid-state physics. Here, we predict an unprecedented layered structure CaH₁₅, with high T_c of 189 K at 200 GPa using ab initio calculations. As concerns the novel structure, one layer is made of a hydrogen nonagon, the other layer consists of a Ca atom and six H₂ molecular units surrounding the Ca atom. This layered structure was also found in SrH₁₅, YH₁₅, and LaH₁₅ at high pressures, each materials exhibit high T_c especially YH₁₅ can reach above 200 K at 220 GPa. It represents the second class of layered superhydrides with high value of T_c after pentagraphene like HfH₁₀.     

高压下氢基高温超导体研究的新进展

富氢材料被认为是室温超导体的最佳候选体系,是物理学、材料科学等多学科的热点研究领域之一。理论和实验研究发现的新型共价氢化物H3S和笼状氢化物LaH10的超导转变温度(T_c)均超过200 K,进一步推动了对富氢化合物超导电性的探索。最近,通过高压实验合成的碳质硫氢化物在288 K的室温下实现了零电阻,让人们看到了室温超导的曙光。本文结合课题组在此领域的主要成果,介绍了3类典型富氢化合物的结构及超导特性,包括近期首次在层状氢化物中发现的具有类五角石墨烯结构的富氢超导体HfH₁₀,其超导转变温度高达213~234 K。     

Photothermal-chemical synthesis of P-S-H ternary hydride at high pressures

The recent discovery of room temperature superconductivity (283 K) in carbonaceous sulfur hydride (C-S-H) has attracted much interest in ternary hydrogen rich materials. In this report, ternary hydride P-S-H was synthesized through a photothermal-chemical reaction from elemental sulfur (S), phosphorus (P) and molecular hydrogen (H₂) at high pressures and room temperature. Raman spectroscopy under pressure shows that H₂S and PH₃ compounds are synthesized after laser heating at 0.9 GPa, and a ternary van der Waals compound P-S-H is synthesized with further compression to 4.6 GPa. The P-S-H compound is probably a mixed alloy of PH₃ and (H₂S)₂H₂ with a guest-host structure similar to the C-S-H system. The ternary hydride can persist up to 35.6 GPa at least and shows two phase transitions at approximately 23.6 GPa and 32.8 GPa, respectively.     

Pressure-induced superconducting ternary hydride H3SXe: A theoretical investigation

In general, heavy elements contribute only to acoustic phonon modes, which are less important for the superconductivity of hydrides. However, it was revealed that the heavier elements could enhance the phonon-mediated superconductivity in ternary hydrides. In the H₃S–Xe system, a novel H₃SXe compound was discovered by first-principle calculations. The structural phase transitions of H3SXe under high pressures were studied. The R-3m phase of H₃SXe was predicted to appear at pressures above 80 GPa, which transitions to C2/m, P-3m1, and Pm-3m phases at pressures of 90, 160, and 220 GPa, respectively. It has been anticipated that the Pm-3m-H₃SXe phase with a similar structural feature as that of Im-3m-H₃S is a potential high-temperature superconductor with a T_c of 89 K at 240 GPa. The T_c value of H₃SXe is lower than that of H₃S at high pressure. The “H₃S” host lattice of Pm- 3m-H₃SXe is a crucial factor influencing the T_c value. The Xe atoms could accelerate the hydrogen-bond symmetrization. With the increase of the atomic number, the T_c value linearly increases in the H₃S–noble-gas-element system. This indicates that the superconductivity can be modulated by changing the relative atomic mass of the noble-gas element.     

压力下碱金属铁硒基超导体中的现象与物理

在凝聚态物理研究中, 压力作为对物质状态调控的独立变量得到了广泛的应用. 压力对发现物质的新现象、新规律及对其形成机理的理解和对相关理论的验证起到了重要的作用, 尤其在超导电性的研究中取得了巨大的成功. 文章简要的介绍了通过利用压力手段对具有相分离结构的碱金属铁硒基超导体A_xFe_2-ySe₂ (A=K, Rb, Tl/Rb)开展的系列研究所取得的实验结果, 以及其他一些文献中报道的在此方面的主要实验与理论研究工作, 包括压力导致的超导再进入现象和其产生的量子临界机理、其特有的反铁磁绝缘体相在该类超导体实现超导电性中的作用、化学负压力对超导电性的影响、构成该类超导体的反铁磁序与其寄居的超晶格的关系等.     

Study of optical response of spinel oxide by utilizing IR-THz spectromicroscopy

We performed a spectromicroscopic measurement on LiV₂O₄ in IR-THz (25 meV–1.5 eV) from 6–300 K under high pressures up to 20 GPa by using a DAC at the spectromicroscopy station (BL43IR) at SPring-8. At 40 K, a clear metal–insulator change was observed above 6 GPa in the optical conductivity spectra. The newly developed peak structure around 1 eV reflects the pseudo-gap forming under pressure at 40 K.     

Li2C2中电声耦合及超导电性的第一性原理计算研究

通过第一性原理密度泛函和超导Eliashberg理论计算, 我们研究了Li₂C₂在Cmcm相的电子结构和电声耦合特性, 预言这种材料在常压和5GPa下是由电声耦合导致的转变温度分别为13.2 K 和9.8 K的超导体, 为实验上探索包含一维碳原子链的材料中是否可能存在超导电性、发现新的超导体提供了理论依据. 如果理论所预言的Li₂C₂超导电性得到实验的证实, 这将是锂碳化物中转变温度最高的超导体, 高于实验观测到的LiC₂的1.9 K和理论预言的单层LiC₆的8.1 K超导转变温度.     

Hf-C体系的高压结构预测及电子性质第一性原理模拟

本论文中, 采用晶体结构预测软件USPEX结合第一性原理方法全面地搜索了Hf-C体系在高压下的晶体结构, 预测得到了两种新的化合物及HfC在高压下的相变路径. 压力低于100 GPa 时, 除了常压下的结构HfC, Hf₃C₂, Hf₆C₅, 并没有得到新的热力学稳定结构. 在200 GPa时, 预测得到了一种新化合物——Hf₂C, 空间群为I4/m; 且HfC的结构发生了相变, 空间群由Fm3m变为C2/m. 在300 GPa时, 预测得到了另一种新化合物——HfC₂, 空间群为Immm. 而在400 GPa时, HfC的结构再次发生相变, 空间群为Pnma. 通过能量计算, 得到了Hf-C体系的组分-压力相图: 在压力分别低于15.5 GPa和37.7 GPa时, Hf₃C₂和Hf₆C₅是稳定的; 压力分别大于102.5 GPa和215.5 GPa时, Hf₂C和HfC₂变成稳定化合物; HfC的相变路径为Fm3m→C2/m→Pnma, 相变压力分别为185.5 GPa 和322 GPa. 经结构优化后, 得到了这四种高压新结构的晶体学数据, 如晶格常数、原子位置等, 并分析了其结构特点. 对于Hf-C 体系中的高压热力学稳定结构, 分别计算了其弹性性质和声子谱曲线, 证明是力学稳定和晶格动力学稳定的. 采用第一性原理软件VASP模拟高压结构的能带结构、态密度、电子局域函数和Bader 电荷分析, 发现HfC(C2/m, Pnma结构), Hf₂C 和HfC₂ 中Hf-C 键具有强共价性、弱金属性和离子性, 且C-C 间存在共价作用.     

高压下NH_4ClO_4结构、电子及弹性性质的第一性原理研究

研究高压下NH_4ClO_4的结构和性质对于NH_4ClO_4在固体推进剂和炸药的安全应用具有重要意义.采用基于色散校正密度泛函理论的第一性原理方法,研究了0—15 GPa静水压力下NH_4ClO_4的晶体结构、分子结构、电子性质和弹性性质,计算结果与实验值具有较好的一致性.在压强为1,4和9 GPa时,NH_4ClO_4的晶体参数、键长和分子构型等均出现不连续变化,说明了在压强作用下结构发生变化.随着压强增加,氢键增多且作用增强,由分子内氢键向分子内和分子间的氢键转变;导带态密度峰值增加,电子局域性增强,晶体内N-H和Cl-O共价键作用增强,带隙增大,不同相变区域内带隙呈线性关系.0—15 GPa条件下NH_4ClO_4的弹性常数满足力学稳定性标准,采用Voigt-Reuss-Hill方法计算了体积模量B,剪切模量G和杨氏模量E,根据Cauchy压力和B/G值,说明NH_4ClO_4属于韧性材料,随着压强增加韧性增强.     

Ab initio studies of copper hydrides under high pressure

The crystal structure, electronic structure, and superconductivity of copper hydrides at high pressure have been studied by ab initio calculation. Consistent with experimental report, results show that the predicted stoichiometry Cu₂H with the P-3m1 space group is stable above 16.8 GPa. The stoichiometry of CuH with the Fm-3m space group is predicted to be synthesized above 30 GPa, but it is metastable and dynamical instable up to 120 GPa. The electronic band calculations reveal that Cu₂H is a good metal at a stable pressure range, whereas CuH is an insulator. Moreover, the other hydrogenrich compounds CuH₂ and CuH₃ are thermodynamically and dynamically unstable, respectively. The calculated superconducting transition temperature (T _c) of Cu₂H at 40 GPa is 0.028 K by using the Allen-Dynes modified McMillan equation.     

Superconductivity well above room temperature in compressed MgH6

It has been suggested that hydrogen-rich systems at high pressure may exhibit notably high super-conducting transition temperatures. One of the more interesting theoretical predictions was that hydrogen sulfide can be metallized and the high-temperature superconducting state can be induced. A record critical temperature (203 K) was later confirmed for H₃S in an experiment. In this paper, we investigated, within the framework of the Eliashberg formalism, the properties of compressed MgH₆, which is expected to be a very good candidate for room-temperature superconductivity. This applies particularly to the pressure range from 300 to 400 GPa, where the transition temperature is close to 400 K. Moreover, the estimated thermodynamic properties and the resulting dimensionless ratios exceed the predictions of the Bardeen–Cooper–Schrieffer theory. This behavior is attributed to the strong electron–phonon coupling and retardation effects existing in hydrogen-dominated materials under high pressure.     

Pressure- and temperature-dependent luminescence from Tm3+ ions doped in GdYTaO4

Luminescent properties of Tm³⁺-doped GdYTaO₄ are studied for exploring their potential applications in temperature and pressure sensing.Two main emission peaks from ³H₄→³H₆ transition of Tm³⁺are investigated.Intensity ratio between the two peaks evolves exponentially with temperature and has a highest sensitivity of 0.014 K^?1 at 32 K.The energy difference between the two peaks increases linearly with pressure increasing at a rate of 0.38 meV/GPa.Intensity ratio between the two peaks and their emission lifetimes are also analyzed for discussing the pressure-induced variation of the sample structure.Moreover,Raman spectra recorded under high pressures indicate an isostructural phase transition of GdYTaO₄ occurring at 4.46 GPa.     

A density-wave-like transition in the polycrystalline V3Sb2 sample with bilayer kagome lattice

Recently,transition-metal-based kagome metals have aroused much research interest as a novel platform to explore exotic topological quantum phenomena.Here we report on the synthesis,structure,and physical properties of a bilayer kagome lattice compound V₃Sb₂.The polycrystalline V₃Sb₂ samples were synthesized by conventional solid-state-reaction method in a sealed quartz tube at temperatures below 850℃.Measurements of magnetic susceptibility and resistivity revealed consistently a density-wave-like transition at Tdw≈160 K with a large thermal hysteresis,even though some sample-dependent behaviors were observed presumably due to the different preparation conditions.Upon cooling through Tdw,no strong anomaly in lattice parameters and no indication of symmetry lowering were detected in powder x-ray diffraction measurements.This transition can be suppressed completely by applying hydrostatic pressures of about 1.8 GPa,around which no sign of superconductivity was observed down to 1.5 K.Specific-heat measurements revealed a relatively large Sommerfeld coefficientγ=18.5 mJ·mol^-1·K^-2,confirming the metallic ground state with moderate electronic correlations.Density functional theory calculations indicate that V₃Sb₂ shows a non-trivial topological crystalline property.Thus,our study makes V₃Sb₂ a new candidate of metallic kagome compound to study the interplay between density-wave-order,nontrivial band topology,and possible superconductivity.     

高压下Ti_2AlX(X=C,N)的结构、力学性能及热力学性质

采用基于密度泛函理论的第一性原理方法,计算研究了压力对Ti_2AlC与Ti_2AlN结构、力学性能的影响.研究发现压力的增大会使体系的体积比降低,Ti_2AlC压缩性较Ti_2AlN好.力学性能研究发现,压力的增大使材料抵抗变形能力增强,体系的延展性有了很大的提升,当压力超过40 GPa后,Ti_2AlC与Ti_2AlN从脆性材料转变为延性材料,体模量与剪切模量的比值达到1.75,延展性有了很大的提升.通过准谐德拜模型,分析了压力与温度对Ti_2AlC与Ti_2AlN体模量、热容及热膨胀系数的影响.结果表明,随着温度的升高,Ti_2AlN与Ti_2AlC的体模量下降.定容热容与定压热容的变化趋势相同,但在高温下,定容热容遵循Dulong-Petit极限,温度对热容的影响效果较压力明显.温度与压力对Ti_2AlN与Ti_2AlC线膨胀系数的影响主要发生在低温区域.     

采用光谱技术研究[C4mim][BF4]的传压和测压性能

金刚石压腔是一种在实验室被频繁使用的高压产生装置,它在高压领域占据着重要地位。当金刚石压腔内传压介质只能提供非静水压环境时,利用传统的红宝石荧光光谱测压方法将很难准确测量样品压强,这也是目前超高压实验面临的普遍困难。若有一种兼具“传压”和“测压”双重功能的物质,根据“相邻位置、相近压强”原则,将能够解决在非静水压环境中测不准样品压强问题。显然,探寻兼具“传压”和“测压”双重功能的物质是一项非常重要的工作。本文将红宝石微粒与离子液体[C₄mim][BF₄]装入金刚石压腔,然后利用金刚石压腔压缩[C₄mim][BF₄]使其提供高压环境,同时采集红宝石的荧光光谱及其附近[C₄mim][BF₄]的拉曼光谱。通过分析红宝石特征荧光峰R₁的峰位,得到了[C₄mim][BF₄]在加压过程中提供的一系列高压环境的压强值。通过分析红宝石特征荧光峰R₁的峰宽,发现[C₄mim][BF₄]在0~6.26和6.26~21.43 GPa两个压强范围内可分别提供静水压环境和准静水压环境,表明[C₄mim][BF₄]在0~21.43 GPa范围内可以作为传压介质使用。此外,还发现[C₄mim][BF₄]在0~2.28,2.28~6.26,6.26~14.39和14.39~21.43 GPa四个压强范围内分别为“液相Ⅰ”、“液相Ⅱ”、“非晶相Ⅰ”和“非晶相Ⅱ”。通过分析[C₄mim][BF₄]中特征拉曼峰ν_(B-F)和ν_(ring)的峰位,发现在[C₄mim][BF₄]四个相态内ν_(B-F)和ν_(ring)的峰位随压强增加均满足线性变化关系,并给出了相应的压强与峰位关系函数,这些函数是[C₄mim][BF₄]用作压标物质的重要依据。综上所述,[C₄mim][BF₄]不仅具有“传压”功能,同时还具有“测压”功能,可同时用作“传压介质”和“压标物质”。研究结果为在非静水压环境中准确测量样品压强提供了重要依据,也为超高压条件下样品压强测量不准确问题提供了新的解决思路。     

静水压力对Al14Mn2P16磁光性质影响的密度泛函理论研究

采用第一性原理，研究不同静水压力（0~20 GPa）下Al₁₄Mn₂P₁₆的弹性与磁光性质.计算得到基态是铁磁态.弹性稳定性判据表明该体系是稳定的.研究发现磁矩随静水压力的增加而减小.静水压力低于5 GPa时，居里温度达到184 K，随着静水压力的增加略有下降；有趣的是，当静水压力高于5 GPa时，随着静水压力的增加，居里温度急剧下降，在18 GPa时消失.同时还发现随静水压力的增加可见光范围的吸收峰有明显的蓝移，当静水压力达到20 GPa时，可见光范围的吸收峰消失.     

Evolution of superconductivity and charge order in pressurized RbV3Sb5

The kagome metals AV₃Sb₅(A=K,Rb,Cs)under ambient pressure exhibit an unusual charge order,from which superconductivity emerges.In this work,by applying hydrostatic pressure using a liquid pressure medium and carrying out electrical resistance measurements for RbV₃Sb₅,we find that the charge order becomes suppressed under a modest pressure pc(1.4 GPa3Sb₅.Our findings point to qualitatively similar temperature-pressure phase diagrams in KV₃Sb₅ and RbV₃Sb₅,{and suggest a close link}between the second superconducting dome and the high-pressure resistance anomalies.     

Synthesis of ternary compound in H-S-Se system at high pressures

The chemical reaction products of elemental sulfur (S), selenium (Se), and molecular hydrogen (H₂) at high pressures and room temperature are probed by Raman spectroscopy. Two known compounds H₂S and H₂Se can be synthesized after laser heating at pressures lower than 1 GPa. Under further compression at room temperature, an H₂S-H₂Se and an H₂S-H₂Se-H₂ van der Waals compounds are synthesized at 4 GPa and 6 GPa, respectively. The later is of guest-host structure and can be identified as (H₂S)_x(H₂Se)_(2-x)H₂. It can be maintained up to 37 GPa at least, and the stability of its H₂Se molecules is extended:the H-Se stretching mode can be detected at least to 36 GPa but disappears at 22 GPa in (H₂Se)₂H₂. The pressure dependence of S-H and Se-H stretching modes of this ternary compound is in line with that of (H₂S)₂H₂ and (H₂Se)₂H₂, respectively. However, its hydrogen subsystem only shows the relevance to (H₂S)₂H₂, indicating that this ternary compound can be viewed as H₂Se-replaced partial H₂S of (H₂S)₂H₂.     

Effect of lead addition to Bi-based 2222 superconducting cuprates Bi2-xPbxSr2(Y, Ce)2Cu2O10+δ

Bi_2-xPb_xSr₂(Y, Ce)₂Cu₂O_10+δ, a new family of lead containing Bi-2222 compounds has been synthesized and effects of annealing in high pressure of oxygen studied. Lead-free Bi₂Sr₂(Y, Ce)₂Cu₂O_10+δ synthesized under flowing oxygen is known to be non-superconducting, but annealing under high oxygen pressure (100 bar) at 500°C, induced superconductivity with T_c=25 K. On substitution of lead (x>0.4), the superconductivity appears even in samples synthesized under flowing oxygen (1 bar). T_c increases with oxygen annealing pressure for all compositions, and it also increases with Pb content at a given oxygen pressure. These findings are discussed.     

Inverted V-shaped evolution of superconducting temperature in SrBC under pressure

Based on density functional first-principles calculations and anisotropic Eliashberg equations, we have investigated the electronic structure, lattice dynamics, and phonon-mediated superconductivity in newly synthesized layered compound Sr BC under pressure. Different from Li BC and Mg B2, our calculations surprisingly reveal that Sr BC is isotropic in compressibility, due to the accumulation of substantial electrons in the interstitial region. We find that the Sr phonons strongly couple with B-2 pz orbital and the interstitial states, giving rise to a two-gap superconductivity in Sr BC, whose transition temperature shows an inverted V-shaped dependence on pressure. The maximal transition temperature is about 22 K at50 GPa. On both sides of 50 GPa, the transition temperature exhibits quasi-linear variation with positive and negative slopes, respectively. Such a variation of transition temperature is infrequent among phonon-mediated superconductors. The competition between enhanced electron–phonon matrix element and hardened phonons plays an essential role in governing the behavior of the critical temperature.