Superconductivity at 253 K in lanthanum-yttrium ternary hydrides
Dmitrii V. Semenok, Ivan A. Troyan, Alexander G. Kvashnin, Anna G. Ivanova, Michael Hanfland, Andrey V. Sadakov, Oleg A. Sobolevskiy, Kirill S. Pervakov, Alexan… 展开作者
Dmitrii V. Semenok, Ivan A. Troyan, Alexander G. Kvashnin, Anna G. Ivanova, Michael Hanfland, Andrey V. Sadakov, Oleg A. Sobolevskiy, Kirill S. Pervakov, Alexander G. Gavriliuk, Igor S. Lyubutin, Konstantin V. Glazyrin, Nico Giordano, Denis N. Karimov, Alexander B. Vasiliev, Ryosuke Akashi, Vladimir M. Pudalov, Artem R. Oganov
Polyhydrides offer intriguing perspectives as high-temperature superconductors. Here we report the high-pressure synthesis of a series of lanthanum-yttrium ternary hydrides: cubic hexahydride $(La,Y)H_{6}$ with a critical temperature $T_{C}$ = 237 +/- 5 K and decahydrides $(La,Y)H_{10}$ with a maximum $T_{C}$ ~${253 K}$ and an extrapolated upper critical magnetic field $B_{C2(0)}$ up to ${135 T}$ at 183 GPa. This is one of the first examples of ternary high-$T_{C}$ superconducting hydrides. Our experiments show that a part of the atoms in the structures of recently discovered ${Im3m}$-$YH_{6}$ and ${Fm3m}$-$LaH_{10}$ can be replaced with lanthanum (~70 %) and yttrium (~25 %), respectively, with a formation of unique ternary superhydrides containing incorporated $La@H_{24}$ and $Y@H_{32}$ which are specific for ${Im3m}$-$LaH_{6}$ and ${Fm3m}$-$YH_{10}$. Ternary La-Y hydrides were obtained at pressures of 170-196 GPa via the laser heating of $P6_{3}$${/mmc}$ lanthanum-yttrium alloys in the ammonia borane medium at temperatures above 2000 K. A novel tetragonal $(La,Y)H_{4}$ was discovered as an impurity phase in synthesized cubic $(La,Y)H_{6}$. The current-voltage measurements show that the critical current density $J_{C}$ in $(La,Y)H_{10}$ may exceed $2500 A/mm^{2}$ at 4.2 K, which is comparable with that for commercial superconducting wires such as ${NbTi}$, $Nb_{3}$${Sn}$. Hydrides that are unstable in a pure form may nevertheless be stabilized at relatively low pressures in solid solutions with superhydrides having the same structure.
We synthesized lanthanum hydride (LaHx) by laser heating of lanthanum in hydrogen atmosphere at pressure P = 170 GPa. The sample shows a superconducting step at 209 K and 170 GPa and temperature dependence of resistance. By releasing the pressure to 150 GPa, the superconducting transition temperature Tc increases to 215 K - the record Tc. This finding supports a way of achieving Tc higher than the one in H3S (203 K) in hydrides with sodalite-like structures, first proposed for CaH6 (Tc=245 K) and later for yttrium and lanthanum hydrides where higher, room temperature superconductivity is expec…
Rare-earth hydrides can exhibit high-temperature superconductivity under high pressure. Here, we apply a crystal structure prediction method to the current record-holding $T_c$ material, LaH$_{10}$, and a candidate for even higher $T_c$, YH$_{10}$. We find a pressure-induced phase transition from the experimentally observed cubic LaH$_{10}$ phase to a new hexagonal phase at around 420 GPa. This hexagonal phase could explain experimental observations of hcp impurities in fcc samples. We find that YH$_{10}$ forms similar structures to LaH$_{10}$ and discuss the sensitivity of superconductivity c…
The high critical temperature phase of lanthanum hydrides deserves special attention because this phase displays the highest observed critical temperature. We focus on the evaluation of the critical temperature, isotope coefficient, and their pressure dependence of this phase (Fm3m phase of the LaH10 compound). By combining the method of two coupling constants, describing the interaction with the optical and acoustic modes, and two characteristic frequencies with first-principle calculations we are able to analyze the role of the light hydrogen in the amplitude of the critical temperature in t…
Recently, the discovery of room-temperature superconductivity (SC) was experimentally realized in the fcc phase of LaH$_{10}$ under megabar pressure. Specifically, the isotope effect of $T_{\rm c}$ was measured by the replacement of hydrogen (H) with deuterium (D), demonstrating a driving role of phonons in the observed room-temperature SC. Herein, based on the first-principles calculations within the harmonic approximation, we reveal that (i) the identical electron-phonon coupling constants of fcc LaH$_{10}$ and LaD$_{10}$ decrease monotonously with increasing pressure and (ii) the isotope ef…
Lanthanum hydride is the superconductor with the highest known critical temperature. It is believed that the superconductivity is of standard BCS-type, with electrons forming Cooper pairs and opening the superconducting band gap. Here we show that the BCS electron pairing is in competition with an alternative pairing: covalent bonding. We show that the covalent pairing is favored at lower pressures, the superconducting cubic phase becomes unstable as pressure is reduced. Previous calculations based on static relaxation neglect three factors, all of which are important in stabilizing the cubic …
Imaging magnetic flux trapping in lanthanum hydride using diamond quantum sensors
Beijing National Laboratory for Condensed Matter Physics and Institute of Physics, Chinese Academy of Sciences（中国科学院物理研究所与凝聚态物理国家实验室）；School of Physical Sciences, University of Chinese Academy of Sciences（中国科学院大学物理科学学院）；Department of Physics, Hefei University of Technology（合肥工业大学物理系）；Center for High Pressure Science and Technology Advanced Research（高压科学和技术先进研究中心）
Inspired by the high critical temperature in yttrium superhydride and the low stabilized pressure in superconducting cerium superhydride, we carry out four independent runs to synthesize yttrium-cerium alloy hydrides. The phases examined by the Raman scattering and x-ray diffraction measurements. The superconductivity is detected with the zero-resistance state at the critical temperature in the range of 97-140 K at pressures ranging from 114 GPa to 120$\pm$4 GPa. The maximum critical temperature of the synthesized hydrides is larger than those reported for cerium hydrides, while the correspond…
Motivated by the recent claim of hot superconductivity with critical temperatures up to 550 K in La + x hydrides (arXiv:2006.03004), we investigate the high-pressure phase diagram of possible compounds that may have formed in the experiment, using first-principles calculations for evolutionary crystal structure prediction and superconductivity. Starting from the hypothesis that the observed T$_c$ may be realized by successive heating upon a pre-formed LaH$_{10}$ phase, we examine plausible ternaries of lanthanum, hydrogen and other elements present in the diamond anvil cell: boron, nitrogen, c…
The discovery of superconductivity at 203 K in H3S brought attention back to conventional superconductors whose properties can be described by the Bardeen-Cooper-Schrieffer (BCS) and the Migdal-Eliashberg theories. These theories predict that high, and even room temperature superconductivity (RTSC) is possible in metals possessing certain favorable parameters such as lattice vibrations at high frequencies. However, these general theories do not suffice to predict real superconductors. New superconducting materials can be predicted now with the aid of first principles calculations based on Dens…
We report ab-initio calculations of the superconducting properties of two high-Tc sodalite-like clathrate yttrium hydrides, YH6 and YH10, within the fully anisotropic ME theory, including Coulomb corrections. For both compounds we find almost isotropic superconducting gaps, resulting from a uniform distribution of the electron-phonon coupling over phonon modes and electronic states of mixed Y and H character. The Coulomb screening is rather weak, resulting in a Morel-Anderson pseudopotential mu*= 0:11, at odds with claims of unusually large Tc in lanthanum hydrides. The corresponding critical …
The Meissner effect, magnetic field expulsion, is a hallmark of superconductivity. Associated with it, superconductors exclude applied magnetic fields. Recently Minkov et al. presented experimental results reportedly showing "definitive evidence of the Meissner effect" in sulfur hydride and lanthanum hydride under high pressure [1], and more recently Eremets et al. argued that "the arguments against superconductivity (in hydrides) can be either refuted or explained" [2]. Instead, we show here that the evidence presented in those papers does not support the case for superconductivity in these m…
The discovery of high-temperature conventional superconductivity in H3S with a critical temperature of Tc=203 K was followed by the recent record of Tc ~250 K in the face-centered cubic (fcc) lanthanum hydride LaH10 compound. It was realized in a new class of hydrogen-dominated compounds having a clathrate-like crystal structure in which hydrogen atoms form a 3D framework and surround a host atom of rare earth elements. Yttrium hydrides are predicted to have even higher Tc exceeding room temperature. In this paper, we synthesized and refined the crystal structure of new hydrides: YH4, YH6, and…
The discovery of superconductivity at 200 K in the hydrogen sulfide system at large pressures [1] was a clear demonstration that hydrogen-rich materials can be high-temperature superconductors. The recent synthesis of LaH$_{10}$ with a superconducting critical temperature (T$_{\text{c}}$) of 250 K [2,3] places these materials at the verge of reaching the long-dreamed room-temperature superconductivity. Electrical and x-ray diffraction measurements determined a weakly pressure-dependent T$_{\text{c}}$ for LaH$_{10}$ between 137 and 218 gigapascals in a structure with a face-centered cubic (fcc)…
Lanthanum, yttrium, and cerium hydrides are the three most well-known superconducting binary hydrides (La-H, Y-H, and Ce-H systems), which have gained great attention in both theoretical and experimental studies. Recent studies have shown that ternary hydrides composed of lanthanum and yttrium can achieve high superconductivity around 253 K. In this study we employ the evolutionary-algorithm-based crystal structure prediction (CSP) method and first-principles calculations to investigate the stability and superconductivity of ternary hydrides composed of (Y, Ce) and (La, Ce) under high pressure…
The 2014-2015 prediction, discovery, and confirmation of record high temperature superconductivity above 200K in H$_3$S, followed by the 2018 extension to superconductivity in the 250-280K range in lanthanum hydride, marks a new era in the longstanding quest for room temperature superconductivity: quest achieved, at the cost of supplying 1.5-2 megabars of pressure. Predictions of numerous high temperature superconducting metal hydrides $XH_n$ ($X$=metal) have appeared, but are providing limited understanding of what drives the high transition temperature T$_c$, or what limits T$_c$. We apply a…
Milestone experimental discovery of superconductivity above 200 K in highly-compressed sulphur hydride by Drozdov (Nature 525, 73 (2015)) sparked experimental and theoretical investigations of metallic hydrides. Since then, a dozen of superconducting binary and ternary polyhydrides have been discovered. For instance, there are three superconducting polyhydrides of thorium: Th4H15, ThH9, and ThH10 and four polyhydrides of yttrium: YH4, YH6, YH7, YH9. In addition to binary and ternary hydrogen-based metallic compounds, recently Eremets (arXiv:2109.11104) reported on the metallization of hydrogen…
Transmission of radio-frequency waves and nuclear magnetic resonance in lanthanum superhydrides
Center for High Pressure Science and Technology Advanced Research (HPSTAR)（高压科学和技术先进研究中心）；Helmholtz-Zentrum Dresden-Rossendorf（德累斯顿-罗斯多夫亥姆霍兹中心）；Technische Universität Dresden（德累斯顿工业大学）；Max Planck Institute for Chemical Physics of Solids（马克斯·普朗克固体化学物理研究所）；A.V. Shubnikov Institute of Crystallography of the Kurchatov Complex of Crystallography and Photonics (KKKiF)（库尔恰托夫晶体学与光子学综合体A.V.舒比尼科夫晶体学研究所）；Shanghai Advanced Research in Physical Sciences (SHARPS)（上海物理科学前沿研究院）
Room temperature superconductivity has been achieved under high pressure in an organically derived carbonaceous sulfur hydride with a critical superconducting transition temperature (Tc) of 288 kelvin. This development is part of a new class of dense, hydrogen rich materials with remarkably high critical temperatures. Metal superhydrides are a subclass of these materials that provide a different and potentially more promising route to very high Tc superconductivity. The most promising binary metal superhydrides contain alkaline or rare earth elements, and recent experimental observations of La…
The measurement of superconductivity at above 200K in compressed samples of hydrogen sulfide and lanthanum hydride at 250K is reinvigorating the search for conventional high temperature superconductors. At the same time it exposes a fascinating interplay between theory, computation and experiment. Conventional superconductivity is well understood, and theoretical tools are available for accurate predictions of the superconducting critical temperature. These predictions depend on knowing the microscopic structure of the material under consideration, and can now be provided through computational…
We present a study concerning the partial substitution of yttrium at the lanthanum site of the undoped LaFeAsO and superconducting LaFeAsO0.85F0.15 compounds. We prepared samples with a nominal yttrium content up to 70% producing simultaneous shrinkage of both the a- and c-lattice parameters by 1.8% and 1.7%, respectively. The chemical pressure provided by the partial substitution with this smaller ion size causes a lowering of the spin density wave temperature in the undoped compounds, as well as an increase of the superconducting transition temperatures in the doped ones. The 15% fluorine-do…
A parameter-free expression for the superconducting critical temperature of layered cuprates is derived which allows us to express Tc in terms of experimentally measured parameters. It yields Tc values observed in about 30 lanthanum, yttrium and mercury-based samples for different levels of doping. This remarkable agreement with the experiment as well as the unusual critical behaviour and the normal-state gap indicate that many cuprates are close to the Bose-Einstein condensation regime.
High Tc superconductivity in heavy Rare Earth Hydrides: correlation between the presence of the f states on the Fermi surface, nesting and the value of Tc
The use of high pressure to realize superconductivity in the vicinity of room temperature has a long history, much of it focused on achieving this in hydrogen rich materials. This paper provides a brief overview of the work presented at this May 2018 conference, together with background on motivation and techniques, the theoretical predictions of superconductivity in lanthanum hydride, and the subsequent experimental confirmation. Theoretical calculations using density functional based structure search methods combined with BCS type models predicted a new class of dense, hydrogen rich material…
Lanthanum hydride LaH$_{10}$ with a sodalitelike clathrate structure was experimentally realized to exhibit a room-temperature superconductivity under megabar pressures. Based on first-principles calculations, we reveal that the metal framework of La atoms has the excess electrons at interstitial regions. Such anionic electrons are easily captured to form a stable clathrate structure of H cages. We thus propose that the charge transfer from La to H atoms is mostly driven by the electride property of the La framework. Further, the interaction between La atoms and H cages induces a delocalizatio…
Clathrate hydride \emph{Fm}\={3}\emph{m}-LaH$_{10}$ has been proven as the most extraordinary superconductor with the critical temperature $T_c$ above 250 K upon compression of hundreds of GPa in recent years. A general hope is to reduce the stabilization pressure and maintain the high $T_c$ value of the specific phase in LaH$_{10}$. However, strong structural instability distorts \emph{Fm}\={3}\emph{m} structure and leads to a rapid decrease of $T_c$ at low pressures. Here, we investigate the phase stability and superconducting behaviors of \emph{Fm}\={3}\emph{m}-LaH$_{10}$ with enhanced chem…
We explore high-pressure phase stability and superconductivity of lanthanum hydrides $LaH_m$ (m=4-11,16). We predict stability of a hitherto unreported polyhydride $P6/mmm$-$LaH_{16}$ at pressures above 150 GPa; at 200 GPa its predicted superconducting $T_C$ is 156 K, critical field $μ_0$$H_C$(0) ~ 35 T and superconducting gap is up to 35 meV. We revisit superconductivity of the recently discovered $LaH_{10}$ and find its $T_C$ to be up to 259 K (170 GPa) from solving the Eliashberg equation and 271 K from solving the gap equation in SCDFT which also allowed us to compute the Coulomb pseudopot…
Recently superconductivity has been discovered at around 200~K in a hydrogen sulfide system and around 260~K in a lanthanum hydride system, both under pressures of about 200 GPa. These record-breaking transition temperatures bring within reach the long-term goal of obtaining room temperature superconductivity. We have used first-principle calculations based on density functional theory (DFT) along with Migdal-Eliashberg theory to investigate the electron-phonon mechanism for superconductivity in the $Fm\bar{3}m$ phase proposed for the LaH$_{10}$ superconductor. We show that the very high trans…
Yttrium Superhydrides Revisited: Advanced Experimental and Theoretical Studies of YH$_6$, YH$_9$ and YH$_{10}$
Center for High Pressure Science & Technology Advanced Research（高压科学前沿研究中心）；Institute of Theoretical and Computational Physics, Graz University of Technology（格拉茨工业大学理论与计算物理研究所）；University of Vienna, Faculty of Physics（维也纳大学物理学院）；V. L. Ginzburg Center for High-Temperature Superconductivity and Quantum Materials（V.L.金兹堡高温超导与量子材料中心）；Department of Applied Physics and Physico-Informatics, Keio University（庆应义塾大学应用物理与信息物理系）；Shanghai Key Laboratory of Material Frontiers Research in Extreme Environments (MFree), Shanghai Advanced Research in Physical Sciences (SHARPS)（极端环境材料前沿研究上海市重点实验室，上海物理科学研究院）；National Research University Higher School of Economics（国立研究型大学高等经济大学）
The Fermi energy, Ef of newly discovered high-Tc superconductor MgB2 and cuprates is estimated from the measured London penetration depth using a parameter-free expression. Ef of MgB2 and more than 30 lanthanum, yttrium and mercury-based cuprates appears to be about or below 100 meV, depending on doping. There is every evidence that the remarkable low value of Ef and the strong coupling of carriers with high-frequency phonons is the cause of high Tc in all newly discovered superconductors. Taking into account that the carriers mainly reside on oxygen in cuprates, on boron in magnesium diborade…
Room-temperature superconductivity has been one of the most challenging subjects in modern physics. Recent experiments reported that lanthanum hydride LaH$_{10{\pm}x}$ ($x$$<$1) raises a superconducting transition temperature $T_{\rm c}$ up to ${\sim}$260 (or 215) K at high pressures around 190 (150) GPa. Here, based on first-principles calculations, we reveal the existence of topological Dirac-nodal-line (DNL) states in compressed LaH$_{10}$. Remarkably, the DNLs protected by the combined inversion and time-reversal symmetry and the rotation symmetry create a van Hove singularity (vHs) near t…
Pressure-stabilized hydrides are a new rapidly growing class of high-temperature superconductors which is believed to be described within the conventional phonon-mediated mechanism of coupling. Here we report the synthesis of yttrium hexahydride Im3m-YH$_6$ that demonstrates the superconducting transition with T$_c$ = 224 K at 166 GPa, much lower than the theoretically predicted (>270 K). The measured upper critical magnetic field B$_c$$_2$(0) of YH$_6$ was found to be 116-158 T, which is 2-2.5 times larger than the calculated value. A pronounced shift of T$_c$ in yttrium deuteride YD$_6$ with…
Stability Analysis of Superconductivity in $\textit{P6/mmm}$-LaSc$_2$H$_{24}$ and its Experimental Reproducibility from La-Sc Alloys
Center for High Pressure Science & Technology Advanced Research（高压科学前沿研究中心）；Shanghai Key Laboratory of Material Frontiers Research in Extreme Environments (MFree), Shanghai Advanced Research in Physical Sciences (SHARPS)（极端环境材料前沿研究上海市重点实验室（MFree），上海物理科学研究院（SHARPS））；Department of Physics and Astronomy, Center for Materials Theory, Rutgers University（罗格斯大学物理与天文学系、材料理论中心）；Physics Department, Columbia University（哥伦比亚大学物理系）
Motivated by recent discovery of yttrium-based high-temperature ternary superconducting hydrides (e.g., CaYH$_{12}$, LaYH$_{12}$, and ScYH$_{6}$), we have employed evolutionary algorithm and first-principles calculations to comprehensively examine the structural stability and superconductivity of the YMgH$_{x}$ system at high pressure. The hydrogen content $x$ and the pressure are both important factors in the stability of these candidate structures. We find that the stability of hydrogen-rich materials frequently necessitates higher pressure. For instance, the pressures to stabilize $P4/mmm$-…
