The clathrate-like or caged compounds have attracted continuing interest due to their structural flexibility as well as fertile physical properties. Here we report a pressure-induced reemergence of superconductivity in BaIr2Ge7 and Ba3Ir4Ge16, two new caged superconductors with two-dimensional building blocks of cage structures. After suppressing the ambient-pressure superconducting (SC-I) state, a new superconducting (SC-II) state emerges unexpectedly, with Tc increased to a maximum of 4.4 K and 4.0 K for BaIr2Ge7 and Ba3Ir4Ge16, respectively. Combined with high-pressure synchrotron x-ray diffraction and Raman measurements, we propose that the reemergence of superconductivity in the caged superconductors can be ascribed to a pressure-induced phonon softening linked to the cage shrink.
Here we report a pressure-induced reemergence of superconductivity in recently discovered superconductor K2Mo3As3, which is the first experimental case observed in quasi-one-dimensional superconductors. We find that, after full suppression of the ambient-pressure superconducting (SC-I) state at 8.7 GPa, an intermediary non-superconducting state sets in and prevails to the pressure up to 18.2 GPa, however, above this pressure a new superconducting (SC-II) state appears unexpectedly. High pressure x-ray diffraction measurements demonstrate that the pressure-induced dramatic change of the lattice…
Quasi-two-dimensional kagome metals AV3Sb5 (A = K, Rb, and Cs) have attracted much recent interest due to exotic quantum phenomena such as unconventional superconductivity, topological charge order and giant anomalous Hall effect. Here we report pressure-induced reemergent superconductivity in CsV3Sb5 by electrical transport measurements under high pressures up to 47.9 GPa. We show that the superconducting critical temperature Tc is first enhanced by pressure and reaches its first maximum ~ 8.9 K at 0.8 GPa, then the Tc is suppressed by pressure and cannot be detected above 7.5 GPa, forming a …
The pressure-induced reemergence of the second high-Tc superconducting phase (SC-II) in the alkali-metal intercalated AxFe2-ySe2 (A = K, Rb, Cs, Tl) remains an enigma and proper characterizations on the superconducting- and normal-state properties of the SC-II phase were hampered by the intrinsic inhomogeneity and phase separation. To elucidate this intriguing problem, we performed a detailed high-pressure magnetotransport study on the recently discovered (Li1-xFex)OHFe1-ySe single crystals, which have high Tc~40 K and share similar Fermi surface topology as AxFe2-ySe2, but are free from the s…
We report the synthesis and superconducting properties of a layered cage compound Ba3Rh4Ge16. Similar to Ba3Ir4Ge16, the compound is composed of 2D networks of cage units, formed by noncubic Rh-Ge building blocks, in marked contrast to the reported rattling compounds. The electrical resistivity, magnetization, specific heat capacity, and muSR measurements unveiled moderately coupled s-wave superconductivity with a critical temperature Tc = 7.0 K, the upper critical field ~ 2.5 T, the electron-phonon coupling strength ~ 0.80, and the Ginzburg-Landau parameter ~ 7.89. The mass reduction by the s…
Sc5Rh6Sn18 with a cage-type quasiskutterudite crystal lattice and type II superconductivity, with superconducting transition temperature Tc = 4.99 K, was investigated under hydrostatic high-pressure (HP) using electrical transport, synchrotron X-ray diffraction (XRD) and Raman spectroscopy. Our data show that HP enhance the metallic nature and Tc of the system. Tc is found to show a continuous increase reaching to 5.24 K at 2.5 GPa. Athough the system is metallic in nature, Raman spectroscopy investigations at ambient pressure revealed the presence of three weak modes at 165.97, 219.86 and 230…
Boron-based clathrate materials, typically with three-dimensional networks of B atoms, have tunable properties through substitution of guest atoms, but the tuning of B cages themselves has not yet been developed. By combining crystal structural search with the laser-heated diamond anvil cell technique, we successfully synthesized a new B-based clathrate boride, LaB8, at ~108 GPa and ~2100 K. The novel structure has a B-richest cage, with 26 B atoms encapsulating a single La atom. LaB8 demonstrates phonon-mediated superconductivity with an estimated transition temperature of 14 K at ambient pre…
Electrical resistivity, magnetic susceptibility, and specific heat measurements on single crystals of La$Tr_{2}$Al$_{20}$ ($Tr$ = Ti, V, Nb, and Ta) revealed that these four compounds exhibit weak-coupling superconductivity with transition temperatures $T_{\rm c}$ = 0.46, 0.15, 1.05, and 1.03 K, respectively. LaTi$_{2}$Al$_{20}$ is most probably a type-I superconductor, which is quite rare among intermetallic compounds. Single-crystal X-ray diffraction suggests "rattling" anharmonic large-amplitude oscillations of Al ions (16$c$ site) on the Al$_{16}$ cage, while no such feature is suggested f…
We report the single-crystal synthesis and detailed investigations of the cage-type superconductor Sc5Ru6Sn18, using powder x-ray diffraction (XRD), magnetization, specific-heat and muon-spin relaxation (muSR) measurements. Sc5Ru6Sn18 crystallizes in a tetragonal structure (space group I41/acd) with the lattice parameters a = 1.387(3) nm and c = 2.641(5) nm. Both DC and AC magnetization measurements prove the type-II superconductivity in Sc5Ru6Sn18 with Tc = 3.5(1) K, a lower critical field H_c1 (0) = 157(9) Oe and an upper critical field, H_c2 (0) = 26(1) kOe. The zero-field electronic specif…
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…
Low-energy rattling modes and their effects on superconductivity are studied in the cage compound GaxV2Al20. A series of polycrystalline samples of 0 < x =< 0.6 are examined through resistivity, magnetic susceptibility, and heat capacity measurements. A weak-coupling BCS superconductivity is observed below Tc = 1.4-1.7 K for all the samples. For small Ga contents below 0.20, approximately 30% of the cages are occupied by rattling Al atoms having an Einstein temperature TE of 23 K, probably with most Ga atoms substituting for the cage-forming Al atoms. For higher Ga contents, approximately 0.05…
We have examined the superconducting ground state properties of the caged type compound Sc$_5$Rh$_6$Sn$_{18}$ using magnetization, heat capacity, and muon-spin relaxation or rotation ($μ$SR) measurements. Magnetization measurements indicate type-II superconductivity with an upper critical field $μ_0H_{c2}(0)$ = 7.24 T. The zero-field cooled and field cooled susceptibility measurements unveil an onset of diamagnetic signal below $T_{\bf c}$ = 4.4 K. The interpretation of the heat capacity results below $T_{\bf c}$ using the $α-$BCS model unveils the value of $α$ = 2.65, which gives the dimensio…
Located at crystal voids, interstitial anion electrons (IAEs) have diverse topologies, which may be tuned to achieve new properties. Elucidating the role of IAEs in electron-phonon coupling (EPC), and using it to design new electride superconductors, leads to the current prediction of superconducting Li8Au at high pressure. We suggest that the occurence of high-temperature superconductivity in electrides requires high-symmetry structures with hydrogen-like cages, an electron acceptor element to balance charges, and isolated IAEs coupled with medium-frequency vibrations. The uniquely designed L…
Polycrystalline samples of four intermetallic compounds: MV$_2$Al$_{20}$ (M = Sc, Y, La, and Lu) were synthesized using an arc-melting technique. The crystal structures were analyzed by means of powder x-ray diffraction and Rietveld analysis, and the physical properties were studied by means of heat capacity, electrical resistivity and magnetic susceptibility measurements down to 0.4 K. For ScV$_2$Al$_{20}$, LuV$_2$Al$_{20}$, and YV$_2$Al$_{20}$, superconductivity was observed with critical temperatures T$_c$ = 1.00 K, 0.57 K, and 0.60 K, respectively. Superconductivity for the Lu compound is …
All samples are synthesized through standard solid state reaction route and are quenched to room temperature systematically at 7000C, 5000C, 3000C and room temperature (RT); named as 700Q, 500Q, 300Q and RTQ respectively. The structural and magnetic properties are studied. Careful Reitveld analysis of XRD patterns revealed that though all samples except 700Q are crystallized in single phase with space group P4/nmm, the presence of interstitial Fe (Feint) at 2c site is increased from 5% for RTQ to 8% for 500Q. The 700Q sample is crystallized in Fe7Se8 phase. The transport and magnetization resu…
Here we report on a new kind of compound, XδIr4X12-δ (X = P, As), the first hole-doped skutterudites superconductor. We provide atomic resolution images of the caging As atoms using scanning transmission electron microscopy (STEM). By inserting As atoms into the caged structure under a high pressure, superconductivity emerges with a maximum transition temperature (Tc) of 4.4 K (4.8 K) in IrAs3 (IrP3). In contrast to all of the electron-doped skutterudites, the electronic states around the Fermi level in XδIr4X12-δ are dominated by the caged X atom, which can be described by a simple body-cente…
Effects of the choice of the exchange-correlation functional on high-temperature superconductivity predictions in covalent-cage M(BN)5 family
City University of Hong Kong（香港城市大学）；Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences（中国科学院深圳先进技术研究院）；University of Chinese Academy of Sciences（中国科学院大学）；Pritzker School of Molecular Engineering, The University of Chicago（芝加哥大学普里茨克分子工程学院）；Shenzhen Polytechnic University（深圳职业技术大学）；Zhejiang University（浙江大学）
In order to clarify the mechanism of the enhancement of superconducting transition temperature $T_{\rm c}$ due to anharmonic local oscillation of a guest ion in a cage composed of host atoms, i.e., {\it rattling}, we analyze the anharmonic Holstein model by applying the Migdal-Eliashberg theory. From the evaluation of the normal-state electron-phonon coupling constant, it is found that the strong coupling state is developed, when the bottom of a potential for the guest ion becomes wide and flat. Then, $T_{\rm c}$ is enhanced with the increase of the anharmonicity in the potential, although $T_…
S-band metals such as alkali and alkaline earth metals do not undergo a superconducting transition (SCT) at an ambient pressure, but their high-pressure phases do. In contrast, room temperature stable electride electride (C12A7:e-) in which anionic electrons in the crystallographic sub-nanometer-size cages have high s-character exhibits SCT at 0.2-0.4K at an ambient pressure. In this paper we report that crystal and electronic structure of C12A7:e- are close to those of the high pressure superconducting phase of alkali and alkaline earth metals and the SCT of both materials is induced when ele…
Recent theoretical and experimental studies of hydrogen-rich materials at megabar pressures (i.e., >100 GPa) have led to the discovery of very high-temperature superconductivity in these materials. Lanthanum superhydride LaH$_{10}$ has been of particular focus as the first material to exhibit a superconducting critical temperature (T$_c$) near room temperature. Experiments indicate that the use of ammonia borane as the hydrogen source can increase the conductivity onset temperatures of lanthanum superhydride to as high as 290 K. Here we examine the doping effects of B and N atoms on the superc…
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 $P4/mmm$-…
Rattling-induced superconductivity in the beta-pyrochlore oxide RbOs2O6 is investigated under high pressures up to 6 GPa. Resistivity measurements in a high-quality single crystal show that the superconducting transition temperature Tc increases gradually from 6.3 K at ambient pressure to 8.8 K at 3.5 GPa, surprisingly remains almost constant at 8.8 \pm 0.1 K in a wide pressure range between 3.5 (Po) and 4.8 GPa, and suddenly drops to 6.3 K at Ps = 4.9 GPa, followed by a gradual decrease with further pressure increase. Two anomalies in the temperature dependence of the normal-state resistivity…
Evolutionary structure searches revealed a plethora of stable and low-enthalpy metastable phases in the S-P-H ternary phase diagram under pressure. A wide variety of crystalline structure types were uncovered ranging from those possessing one-dimensional chains, two-dimensional sheets based on S-H or S-P-H square lattices as well as S-H or P-H honeycombs, and cage-like structures. Some of the cage-like structures could be derived from doping the high-pressure high-temperature superconducting $Im\bar{3}m$ H$_3$S phase with phosphorous. Most of the discovered compounds were metallic, however tho…
Superconductivity in the new polymerized C60 fullerite clathrate doped with simple metals was investigated through density functional theory methods. The phonon dispersion curves were systematically computed for the clathrate structures containing the guest dopants (Li, Na, K, Be, Mg, Ca, Al, Ga, Ge) in one of the two distinct cages, fullerene-like C60 and sodalite-like C24, exhibited by this structure. Only four of these structures, Li@C24, Na@C24, Ga@C24 and Be@C60, are dynamically stable in the harmonic approximation. They all show superconducting behavior, although their critical temperatu…
A unique platform for investigating the correlation between the antiferromagnetic (AFM) and superconducting (SC) states in high temperature superconductors is created by the discovery of alkaline iron selenide superconductors which are composed of an AFM insulating phase and a SC phase separated spatially. Our previous studies showed that pressure can fully suppress the superconductivity of ambient-pressure superconducting phase (SC-I) and AFM order simultaneously, then induce another superconducting phase (SC-II) at higher pressure. Consequently, the connection between the two superconducting…
Evidence for broken time reversal symmetry (TRS) has been found in the superconducting states of the $R_5$Rh$_6$Sn$_{18}$ (R = Sc, Y, Lu) compounds with a centrosymmetric caged crystal structure, but the origin of this phenomenon is unresolved. Here we report neutron diffraction measurements of single crystals with $R$=Lu, as well as measurements of the temperature dependence of the magnetic penetration depth using a self-induced tunnel diode-oscillator (TDO) based technique, together with band structure calculations using density functional theory. Neutron diffraction measurements reveal that…
We report a detailed study of specific heat, electrical resistivity and thermal expansion in combination with inelastic neutron and inelastic X-ray scattering to investigate the origin of superconductivity in the two silicon clathrate superconductors Ba8Si46 and Ba24Si100. Both compounds have a similar structure based on encaged barium atoms in oversized silicon cages. However, the transition temperatures are rather different: 8 K and 1.5 K respectively. By extracting the superconducting properties, phonon density of states, electron-phonon coupling function and phonon anharmonicity from these…
The uniquely characteristic macrostructures of binary hydrogen-clathrate compounds $M$H$_\textrm{n}$ formed at high pressure, a cage of hydrogens surrounding a central-atom host, is theoretically predicted in various studies to include structurally stable phonon-mediated superconductors. High superconductive transition temperatures $T$$_\textrm{C}$ have thus far been measured for syntheses with $M$ = La, Y, and Th. In compressed LaH$_\textrm{10}$, independent studies report $T$$_\textrm{C}$ of 250 K and over 260 K, a maximum in $T$$_\textrm{C}$ with pressure $P$, and normal-state resistance sc…
The rare-earth metal hydrides with clathrate structures have been highly attractive because of their promising high-$T_{\rm c}$ superconductivity at high pressure. Recently, cerium hydride CeH$_9$ composed of Ce-encapsulated clathrate H cages was synthesized at much lower pressures of 80$-$100 GPa, compared to other experimentally synthesized rare-earth hydrides such as LaH$_{10}$ and YH$_6$. Based on density-functional theory calculations, we find that the Ce 5$p$ semicore and 4$f$/5$d$ valence states strongly hybridize with the H 1$s$ state, while a transfer of electrons occurs from Ce to H …
Over the past decade, a combination of crystal structure prediction techniques and experimental synthetic work has thoroughly explored the phase diagrams of binary hydrides under pressure. The fruitfulness of this dual approach is demonstrated in the recent identification of several superconducting hydrides with $T_c$s approaching room temperature. We start with an overview of the computational procedures for predicting stable structures and estimating their propensity for superconductivity. A survey of phases with high $T_c$ reveals some common structural features that appear conducive to the…
The binary polyhydrides of heavy rare earth lutetium that shares a similar valence electron configuration to lanthanum have been experimentally discovered to be superconductive. The lutetium polyhydrides were successfully synthesized at high pressure and high temperature conditions using a diamond anvil cell in combinations with the in-situ high pressure laser heating technique. The resistance measurements as a function of temperature were performed at the same pressure of synthesis in order to study the transitions of superconductivity (SC). The superconducting transition with a maximum onset…
A lithium-doped magnesium hydride Li$_2$MgH$_{16}$ was recently reported [Y. Sun $et$ $al$., Phys. Rev. Lett. {\bf 123}, 097001 (2019)] to exhibit the highest ever predicted superconducting transition temperature $T_{\rm c}$ under high pressure. Based on first-principles density-functional theory calculations, we reveal that the Li dopants locating in the pyroclore lattice sites give rise to the excess electrons distributed in interstitial regions. Such loosely bound anionic electrons are easily captured to stabilize a clathrate structure consisting of H cages. This addition of anionic electro…
Superconductivity of Tellurium Polyhydride with Tc above 90K
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences（中国科学院物理研究所凝聚态物理国家实验室）；School of Physics, University of Chinese Academy of Sciences（中国科学院大学物理学院）；Shanghai Key Laboratory of Material Frontiers Research in Extreme Environments (MFree), Shanghai Advanced Research in Physical Sciences (SHARPS)（上海极端环境材料前沿研究重点实验室（MFree），上海物理研究所先进物理科学中心）；Center for High Pressure Science & Technology Advanced Research (HPSTAR)（高压科学和技术先进研究中心（HPSTAR））；Department of Chemistry, Johann Wolfgang Goethe University（约翰·沃尔夫冈·歌德大学化学系）
Based on recent studies regarding high-temperature (high-$T_c$) La-Y ternary hydrides (e.g., $P{\bar{1}}$-La$_2$YH$_{12}$, $Pm{\bar{3}}m$-LaYH$_{12}$, and $Pm{\bar{3}}m$-(La,Y)H$_{10}$ with a maximum $T_c \sim 253$ K), we examined the phase and structural stabilities of the (LaH$_6$)(YH$_6$)$_y$ series as high-$T_c$ ternary hydride compositions using a genetic algorithm and $\it ab$ $\it initio$ calculations. Our evaluation showed that the $Pm\bar{3}m$-LaYH$_{12}$ reported in the previous study was unstable during decomposition into $R\bar{3}c$-LaH$_{6}$ + $Im\bar{3}m$-YH$_{6}$. We also discov…
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…
The theoretical exploration of the phase diagrams of binary hydrides under pressure using \emph{ab initio} crystal structure prediction techniques coupled with first-principles calculations has led to the \emph{in silico} discovery of numerous novel superconducting materials. This Perspective article focuses on the alkaline earth and rare earth polyhydrides whose superconducting critical temperature, $T_c$, was predicted to be above the boiling point of liquid nitrogen. After providing a brief overview of the computational protocol used to predict the structures of stable and metastable hydrid…
Intermetallic R$_3$T$_4$X$_{13}$ series consists of cage like structure and have been in focus due to their unconventional electronic ground states. In this work, we report the normal and superconducting state properties of a high quality single crystal of Lu$_3$Os$_4$Ge$_{13}$. Lu$_3$Os$_4$Ge$_{13}$ belongs to the above mentioned series and crystallizes in a cubic crystal structure with the space group $\it{Pm\bar{3}n}$. Using electrical transport, magnetization and heat capacity measurements, we show that Lu$_3$Os$_4$Ge$_{13}$ is a type-II multi-band superconductor ($T{_c} =3.1$~K) with unus…
Recently, the thorium hydride ThH9 possessing an H-rich clathrate structure has been experimentally synthesized to exhibit a superconducting transition temperature Tc of 146 K at 170-175 GPa, while the more H-rich clathrate thorium hydride ThH18 was theoretically predicted to reach a Tc of 296 K at 400 GPa. Using first-principles calculations, we find that ThH9 has a more ionic character between Th atoms and H cages than ThH18 and that the latter has a more substantial hybridization of the Th 6p semicore and H 1s states than the former. These different bonding characteristics of ThH9 and ThH18…
