RuX2 (X=P、As、Sb) 家族化合物中的压力诱导的超导和拓扑相变

作为热电材料 FeSb2 的姊妹材料，RuSb2 被广泛研究，但以前的工作主要集中在与 FeSb2 的比较上，尚未对 RuSb2 在压力下的性质进行深入研究。在本文中，我们研究了 RuSb2 在压力 下的性质，并探讨了其与 Ru 的磷族化合物 RuP2 和 RuAs2 之间晶体和电子结构的异同。我们 用晶体结构搜索方法结合第一性原理计算，发现该族化合物经历了一系列结构相变：（I）RuSb2： Pnnm → I4/mcm → I4/mmm；(II) RuP2：Pnnm → I41/amd → Cmcm；(III) RuAs2： Pnnm → P-62m。新发现的五个相在高压下都是热力学和动力学稳定的，并表现出金属性。RuSb2 和 RuP2 的四个高压相在泄压到零压后动力学依旧稳定。我们计算得到 RuSb2 的 I4/mcm 和 I4/mmm 相以及 RuP2 的 I41/amd 和 Cmcm 相的超导转变温度在 0 GPa 时分别约为 7.3 K、 10.9 K、13.0 K 和 10.1 K。另外，RuSb2 的 I4/mcm 和 I4/mmm 相以及 RuP2 的 I41/amd 相还具有拓扑非平庸的表面态。我们的研究表明，压力是调节 Ru 的磷族化合物结构、电子和超 导性质的有效方法。     

Electronic properties and topological phases of ThXY(X= Pb,Au, Pt and Y= Sb,Bi, Sn) compounds

The electronic properties and topological phases of Th XY(X = Pb, Au, Pt, Pd and Y = Sb, Bi, Sn) compounds in the presence of spin–orbit coupling, using density functional theory are investigated. The Th Pt Sn compound is stable in the ferromagnetic phase and the other Th XY compounds are stable in nonmagnetic phases. Band structures of these compounds in topological phases(insulator or metal) and normal phases within generalized gradient approximation(GGA) and Engel–Vosko generalized gradient approximation(GGA EV) are compared. The Th Pt Sn, Th Pt Bi, Th Pt Sb, Th Pd Bi, and Th Au Bi compounds have topological phases and the other Th XY compounds have normal phases. Band inversion strengths and topological phases of these compounds at different pressure are studied. It is seen that the band inversion strengths of these compounds are sensitive to pressure and for each compound a second-order polynomial fitted on the band inversion strengths–pressure curves.     

First principles study of the structural,electronic, mechanical and superconducting properties of WX (X=C,N)

The structural, electronic, mechanical and superconducting properties of tungsten carbide (WC) and tungsten nitride (WN) are investigated using first principles calculations based on density functional theory (DFT). The computed ground state properties, such as equilibrium lattice constant and cell volume, are in good agreement with the available experimental data. A pressure induced structural phase transition is observed in both tungsten carbide and nitride, from a tungsten carbide phase (WC) to a zinc blende phase (ZB), and from a zinc blende phase (ZB) to a wurtzite phase (WZ). The electronic structure reveals that these materials are metallic at ambient conditions. The calculated elastic constants obey the Born-Huang criteria, suggesting that they are mechanically stable at normal and high pressure. Also, the superconducting transition temperature is estimated for the WC and WN in stable structures at atmospheric pressure.     

A new 9 K superconducting organic salt composed of the bis (ethylenedithio) tetrathiafulvalene (ET) electron-donor molecule and the tetrakis (trifluoromethyl) cuprate (III) anion, [Cu(CF3)4]

We report the discovery of a second, higher-T_c superconducting organic charge-transfer salt derived from the electron-donor molecule BEDT-TTF (or ET), the novel organometallic anion [Cu(CF₃)₄]⁻, and the neutral solvent molecule 1, 1, 2-trichloroethane (TCE). We have very recently reported that this charge-transfer system yields a new superconducting phase salt, _L- (ET)₂Cu(CF₃)₄·TCE, with inductive onset T_crmc=4.0 K at ambient pressure. This phase salt ( denotes a particular packing arrangement of the ET organic donor molecules) is electrocrystallized in the habit of hexagonal plates. Crystals possessing a needle-like habit electrocrystallize simultaneously with these plates, and we find these needles to be a distinctly different superconducting phase with diamagnetic onset T_c=9.2±0.1 K at ambient pressure. On the basis of our experiments, we denote this new superconducting phase as _H−(ET)₂Cu(CF₃)₄·(TCE)_x,X<1.     

Temperature dependence of bismuth structures under high pressure

It is unclear whether there is a liquid-liquid phase transition or not in the bismuth melt at high temperature and high pressure. If so, it will be necessary to confirm the boundary of the liquid-liquid phase transition and clarify whether it is a first-order phase transition. Here, based on x-ray absorption spectra and simulations, the temperature dependence of bismuth structures is investigated under different pressures. According to the similarity of characteristic peaks of x-ray absorption near edge structure (XANES) spectra, we estimate the possible temperature ranges of liquid-liquid phase transition to be 779-799 K at 2.74 GPa and 859-879 K at 2.78 GPa, 809-819 K at 3.38 GPa and 829-839 K at 3.39 GPa and 729-739 K at 4.78 GPa. Using ab initio molecular dynamics (AIMD) simulations, we obtain the stable structures of the bismuth melt at different temperatures and pressures, and calculated their electronic structures. Meanwhile, two stable phases (phase III-like and phase IV-like) of bismuth melts are obtained from different initial phases of bismuth solids (phase III and phase IV) under the same condition (3.20 GPa and 800 K). Assuming that the bismuth melt undergoes a phase transition from IV-like to III-like between 809 K and 819 K at 3.38 GPa, the calculated electronic structures are consistent with the XANES spectra, which provides a possible explanation for the first-order liquid-liquid phase transition.     

Electronic and magnetic properties of new quaternary oxybismuthides LaOMBi (where M = V, Cr, …, Ni, Cu) from first principles

For prediction of new parent phases for Fe-containing superconducting materials by means of the FPLAPW-GGA method the structural, electronic and magnetic properties of series of quaternary oxybismuthides LaOMBi (where M = V, Cr, …, Ni, Cu) are investigated for the first time. Our preliminary conclusion is that LaONiBi may be a suitable phase for search of new superconducting materials.     

Structural evolution and molecular dissociation of H2S under high pressures

Solid H$_{2}$S as the precursor for H$_{3}$S with incredible superconducting properties under high pressure, has recently attracted extensive attention. Here in this work, we propose two new phases of H$_{2}$S with $P$4$_{2}/n$ and $I$4$_{1}/a$ lattice symmetries in a pressure range of 0 GPa-30 GPa through first-principles structural searches, which complement the phase transition sequence. Further an $ab initio$ molecular dynamics simulation confirms that the molecular phase $P2/c$ of H$_{2}$S is gradually dissociated with the pressure increasing and reconstructs into a new $P$2$_{1}/m$ structure at 160 GPa, exhibiting the superconductivity with $T_{\rm c}$ of 82.5 K. Our results may provide a guidance for the theoretical study of low-temperature superconducting phase of H$_{2}$S.     

Superconductivity in new quaternary borocarbide system R–Re–B–C (R=Y, Gd, Tb and Lu)

We report here our observation of superconductivity in a new quaternary borocarbide system R–Re–B–C (R=Y, Gd, Tb and Lu). Samples of the nominal compositions RReBC exhibit superconductivity with T_c≈6 K in LuReBC which is high for an intermetallic. TbReBC and GdReBC exhibit superconductivity at ≈4 K. A magnetic transition is also observed in TbReBC around 30 K. From our measurements, we infer that superconductivity originates from a bulk quaternary superconducting phase in these materials.     

Superconducting behavior in compressed solid SiH4 with a layered structure

The electronic and lattice dynamical properties of compressed solid SiH4 have been calculated in the pressure range up to 300 GPa with density functional theory. We find two energetically preferred insulating phases with P2(1)/c and Fdd2 symmetries at low pressures. We demonstrate that the Cmca structure having a layered network is the most likely candidate of the metallic phase of SiH4 over a wide pressure range above 60 GPa. The superconducting transition temperature in this layered metallic phase is found to be in the range of 20-75 K.     

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.     

Pressure-tuned collapse of the Mott-like state in Ca(n+1)Ru(n)O(3n+1) (n=1,2): Raman spectroscopic studies

We report a Raman scattering study of the pressure-induced collapse of the Mott-like phases of Ca3Ru2O7 (T(N)=56 K) and Ca2RuO4 (T(N)=110 K). The pressure dependence of the phonon and two-magnon excitations in these materials indicate (i) a T approximately 0 pressure-induced collapse of the antiferromagnetic (AF) insulating phase above P(*) approximately 55 kbar in Ca3Ru2O7 and P(*) approximately 5-10 kbar in Ca2RuO4, (ii) a remarkable insensitivity of the exchange interaction to pressure in both systems, and (iii) evidence for persistent AF correlations above the critical pressure of Ca2RuO4, suggestive of phase separation involving AF insulator and ferromagnetic metal phases.     

La4Au亚稳超导相的高压合成

本文报道了利用非晶合金的高压变态,合成新亚稳超导相La₄Au的结果,非晶La₈₀Au₂₀交结构,晶格参数为α=6.54?,b=7.71?,C=11.32?,超导临界温度T_c达5.5K,高于所有已知La-Au相的值。 关键词：     

Superconductivity,lattice transformations,and electronic instabilities in CuxMo3S4

The variations of the superconducting transition temperature (T_c) and of the lattice transformation temperature (T_L) with composition are reported for the Chevrel-phase system Cu_xMo₃S₄ (1 ≤ × ≤ 2). A complex low temperature phase diagram was found, containing at least three distinct low temperature phases, each exhibiting its own characteristic T_c (11 K, 6.5 K, 4.5 K), T_L (280 K - 125 K), and electronic transport behavior. Pressure-induced transformations between these three phases were observed at pressures below 25 kbar. Temperature-induced lattice distortion for compositions near Cu₂Mo₃S₄ was found to increase the T_c above that (< 1.1 K) of the high temperature, higher symmetry rhombohedral phase. This is apparently the first time the latter behavior has been observed: in all previous studies of other materials, the opposite behavior was reported.     

Pressure induced superconductivity in CaFe2As2

CaFe2As2 has been found to be exceptionally sensitive to the application of hydrostatic pressure and can be tuned to reveal all the salient features associated with FeAs superconductivity without introducing any disorder. The ambient pressure, 170 K, structural/magnetic, first-order phase transition is suppressed to 128 K by 3.5 kbar. At 5.5 kbar a new transition is detected at 104 K, increasing to above 300 K by 19 kbar. A low temperature, superconducting dome (T(c) approximately 12 K) is centered around 5 kbar, extending down to 2.3 kbar and up to 8.6 kbar. This superconducting phase appears to exist when the low pressure transition is suppressed sufficiently, but before the high pressure transition has reduced the resistivity too dramatically.     

Observations of abundant structural and electronic phases in potassium-doped single-layer p-quaterphenyl film

Scanning tunneling microscopy/spectroscopy is applied herein to study the pristine and potassium(K)-doped single-layer pquaterphenyl(P4P) films grown on the Au(111) substrate at the molecular level. Abundant complex structural and electronic phases are induced by various K doping. The Fermi-level pinning effect is observed at a low doping level. On the contrary,K_3P4P exhibits intriguing versatile phases and properties because charge carriers are effectively doped in. For example, two kinds of molecular vibration modes with energies below 100 meV are observed, indicating a possible strong electron-phonon coupling. The splitting of the lowest unoccupied molecular orbital state in K_3P4P illustrates an electronic correlation effect, and its strength varies for four different K_3P4P phases with different structures. In addition, the appearance of a Kondo resonance on the molecular vacancy/impurity implies a local molecular magnetic moment. Our results demonstrate that the complex electronic properties of an alkali metal-doped P4P/Au film stem from the existence of many competing interactions, such as electronelectron correlations and electron-vibration coupling, which can be effectively tuned via variable carrier doping and molecular structure. Our work also opens new routes toward engineering novel molecular devices and creating new electronic phases in strongly correlated molecular materials.     

Structurally tuned superconductivity in heavy-fermion CeMIn5 (M=Co, Ir, Rh)

We discuss systematic trends in the high-temperature physical properties of the heavy Fermion superconductors (HFS) CeCoIn₅ (T_c=2.3 K, γ=300 mJ/molK²), CeIrIn₅ (T_c=0.4 K, γ=750 mJ/molK²), and CeRhIn₅ (P_c=16 kbar, T_c=2.1 K, γ=400 mJ/molK²) in terms of crystalline-electrical-field effects(CEF). We suggest the possibility that the interplay between the symmetry of the CEF ground-state (or low-T CEF scheme of levels) and the f–s hybridization could generate spin fluctuations relevant to the superconducting pairing mechanism in these materials. This hypothesis may provide insight into the fact that some crystal structures appear to favor superconductivity. Further, CeMIn₅ (M=Co, Ir, Rh) appear to be structural relatives of the cubic heavy Fermion superconductor CeIn₃, but with much higher T_c's. We argue that structural layering inherent in the tetragonal CeMIn₅ crystal structure determines the magnetic and electronic anisotropy responsible for the enhanced T_c's. We also describe similarities and differences between these compounds and the high-T_c cuprates.     

Superconducting Single-Layer T-Graphene and Novel Synthesis Routes

Single-layer superconductors are ideal materials for fabricating superconducting nano devices.However,up to date,very few single-layer elemental superconductors have been predicted and especially no one has been successfully synthesized yet.Here,using crystal structure search techniques and ab initio calculations,we predict that a single-layer planar carbon sheet with 4-and 8-membered rings called T-graphene is a new intrinsic elemental superconductor with superconducting critical temperature(T_c)up to around 20.8 K.More importantly,we propose a synthesis route to obtain such a single-layer T-graphene,that is,a T-graphene potassium intercalation compound(C_4 K with P4/mmm symmetry)is firstly synthesized at high pressure(11.5 GPa)and then quenched to ambient condition;and finally,the single-layer T-graphene can be either exfoliated using the electrochemical method from the bulk C4 K,or peeled off from bulk T-graphite C4,where C4 can be obtained from C4 K by evaporating the K atoms.Interestingly,we find that the calculated T_c of C4 K is about 30.4 K at 0 GPa,which sets a new record for layered carbon-based superconductors.The present findings add a new class of carbon-based superconductors.In particular,once the single-layer T-graphene is synthesized,it can pave the way for fabricating superconducting devices together with other 2 D materials using the layer-by-layer growth techniques.     

High-pressure elastic anisotropy and superconductivity of hafnium:A first-principles calculation

The elastic anisotropy and superconductivity upon hydrostatic compression of α, ω, and β Hf are investigated using first-principle methods. The results of elastic anisotropies show that they increase with increasing pressure for α andω phases, while decrease upon compression for β phase. The calculated superconducting transition temperatures are in excellent agreement with experiments. Electron–phonon coupling constants(λ) are increasing with pressure for α and ωphases, while decreasing for β phase. For β phase, the large values of λ are mainly due to the obvious TA1 soft mode.Under further compression, the TA1 soft vibrational mode will disappear gradually.     

Pressure-induced phase transition in transition metal trifluorides

As a fundamental thermodynamic variable, pressure can alter the bonding patterns and drive phase transitions leading to the creation of new high-pressure phases with exotic properties that are inaccessible at ambient pressure. Using the swarm intelligence structural prediction method, the phase transition of TiF₃, from R—3c to the Pnma phase, was predicted at high pressure, accompanied by the destruction of TiF₆ octahedra and formation of TiF₈ square antiprismatic units. The Pnma phase of TiF₃, formed using the laser-heated diamond-anvil-cell technique was confirmed via high-pressure x-ray diffraction experiments. Furthermore, the in situ electrical measurements indicate that the newly found Pnma phase has a semiconducting character, which is also consistent with the electronic band structure calculations. Finally, it was shown that this pressure-induced phase transition is a general phenomenon in ScF₃, VF₃, CrF₃, and MnF₃, offering valuable insights into the high-pressure phases of transition metal trifluorides.     

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.