Magnetic methods in studies of new superconducting hydrides in a diamond anvil cell.

This short perspective article summarizes the growing experimental evidence supporting the original claims about hydrogen-rich "superhydrydes" as members of a new family of nearly room temperature BCS superconductors, with hydrogen sub-lattice pre-compressed to the metallic and superconducting state, exactly as predicted in earlier and more recent theoretical works.

The stability of FeHx and hydrogen transport at Earth's core mantle boundary.

Iron hydride in Earth's interior can be formed by the reaction between hydrous minerals (water) and iron. Studying iron hydride improves our understanding of hydrogen transportation in Earth's interior. Our high-pressure experiments found that face-centered cubic (fcc) FeHx (x ≤ 1) is stable up to 165 GPa, and our ab initio molecular dynamics simulations predicted that fcc FeHx transforms to a superionic state under lower mantle conditions. In the superionic state, H-ions in fcc FeH become highly diffusive-like fluids with a high diffusion coefficient of ∼3.7 × 10-4 cm2 s-1, which is comparable to that in the liquid Fe-H phase. The densities and melting temperatures of fcc FeHx were systematically calculated. Similar to superionic ice, the extra entropy of diffusive H-ions increases the melting temperature of fcc FeH. The wide stability field of fcc FeH enables hydrogen transport into the outer core to create a potential hydrogen reservoir in Earth's interior, leaving oxygen-rich patches (ORP) above the core mantle boundary (CMB).

Synthesis, Structure, and Electric Conductivity of Higher Hydrides of Ytterbium at High Pressure.

While most of the rare-earth metals readily form trihydrides, due to increased stability of the filled 4f electronic shell for Yb(II), only YbH2.67, formally corresponding to YbII(YbIIIH4)2 (or Yb3H8), remains the highest hydride of ytterbium. Utilizing the diamond anvil cell methodology and synchrotron powder X-ray diffraction, we have attempted to push this limit further via hydrogenation of metallic Yb and Yb3H8. Compression of the latter has also been investigated in a neutral pressure-transmitting medium (PTM). While the in situ heating of Yb facilitates the formation of YbH2+x hydrides, we have not observed clear qualitative differences between the systems compressed in H2 and He or Ne PTM. In all of these cases, a sequence of phase transitions occurred within ca. 13-18 GPa (P3̅1m-I4/m phase) and around 27 GPa (to the I4/mmm phase). The molecular volume of the systems compressed in H2 PTM is ca. 1.5% larger than of those compressed in inert gases, suggesting a small hydrogen uptake. Nevertheless, hydrogenation toward YbH3 is incomplete, and polyhydrides do not form up to the highest pressure studied here (ca. 75 GPa). As pointed out by electronic transport measurements, the mixed-valence Yb3H8 retains its semiconducting character up to >50 GPa, although the very low remnant activation energy of conduction (<5 meV) suggests that metallization under further compression should be achievable. Finally, we provide a theoretical description of a hypothetical stoichiometric YbH3.

Anomalous High-Temperature Superconductivity in YH6.

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, the synthesis of one of the best-known high-TC superconductors-yttrium hexahydride I m 3 ¯ m -YH6 is reported, which displays a superconducting transition at ≈224 K at 166 GPa. The extrapolated upper critical magnetic field Bc2 (0) of YH6 is surprisingly high: 116-158 T, which is 2-2.5 times larger than the calculated value. A pronounced shift of TC in yttrium deuteride YD6 with the isotope coefficient 0.4 supports the phonon-assisted superconductivity. Current-voltage measurements show that the critical current IC and its density JC may exceed 1.75 A and 3500 A mm-2 at 4 K, respectively, which is higher than that of the commercial superconductors, such as NbTi and YBCO. The results of superconducting density functional theory (SCDFT) and anharmonic calculations, together with anomalously high critical magnetic field, suggest notable departures of the superconducting properties from the conventional Migdal-Eliashberg and Bardeen-Cooper-Schrieffer theories, and presence of an additional mechanism of superconductivity.

Enhancement of thermoelectric performance across the topological phase transition in dense lead selenide.

Alternative technologies are required in order to meet a worldwide demand for clean non-polluting energy sources. Thermoelectric generators, which generate electricity from heat in a compact and reliable manner, are potential devices for waste heat recovery. However, thermoelectric performance, as encapsulated by the figure of merit ZT, has remained at around 1.0 at room temperature, which has limited practical applications. Here, we study the effects of pressure on ZT in Cr-doped PbSe, which has a maximum ZT of less than 1.0 at a temperature of about 700 K. By applying external pressure using a diamond anvil cell, we obtained a room-temperature ZT value of about 1.7. From thermoelectric, magnetoresistance and Raman measurements, as well as density functional theory calculations, a pressure-driven topological phase transition is found to enable this enhancement. Experiments also support the appearance of a topological crystalline insulator after the transition. These findings point to the possibility of using compression to increase not just ZT in existing thermoelectric materials, but also the possibility of realizing topological crystalline insulators.

Evidence for Superconductivity above 260 K in Lanthanum Superhydride at Megabar Pressures.

Recent predictions and experimental observations of high T_{c} superconductivity in hydrogen-rich materials at very high pressures are driving the search for superconductivity in the vicinity of room temperature. We have developed a novel preparation technique that is optimally suited for megabar pressure syntheses of superhydrides using modulated laser heating while maintaining the integrity of sample-probe contacts for electrical transport measurements to 200 GPa. We detail the synthesis and characterization of lanthanum superhydride samples, including four-probe electrical transport measurements that display significant drops in resistivity on cooling up to 260 K and 180-200 GPa, and resistivity transitions at both lower and higher temperatures in other experiments. Additional current-voltage measurements, critical current estimates, and low-temperature x-ray diffraction are also obtained. We suggest that the transitions represent signatures of superconductivity to near room temperature in phases of lanthanum superhydride, in good agreement with density functional structure search and BCS theory calculations.

Unusual Pressure-Induced Periodic Lattice Distortion in SnSe_{2}.

We performed high-pressure x-ray diffraction (XRD), Raman, and transport measurements combined with first-principles calculations to investigate the behavior of tin diselenide (SnSe_{2}) under compression. The obtained single-crystal XRD data indicate the formation of a (1/3,1/3,0)-type superlattice above 17 GPa. According to our density functional theory results, the pressure-induced transition to the commensurate periodic lattice distortion (PLD) phase is due to the combined effect of strong Fermi surface nesting and electron-phonon coupling at a momentum wave vector q=(1/3,1/3,0). In contrast, similar PLD transitions associated with charge density wave (CDW) orderings in transition metal dichalcogenides (TMDs) do not involve significant Fermi surface nesting. The discovered pressure-induced PLD is quite remarkable, as pressure usually suppresses CDW phases in related materials. Our findings, therefore, provide new playgrounds to study the intricate mechanisms governing the emergence of PLD in TMD-related materials.

Dramatic enhancement of spin-spin coupling and quenching of magnetic dimensionality in compressed silver difluoride.

Meta-GGA calculations of the ambient and high-pressure polymorphs of silver difluoride indicate that the compression-induced structural changes lead to a 3.5-fold increase in the strength of antiferromagnetic spin-spin interactions resulting in coupling constant values higher than those found for record-holding oxocuprates(ii).

Emergent superconductivity in an iron-based honeycomb lattice initiated by pressure-driven spin-crossover.

The discovery of iron-based superconductors (FeSCs), with the highest transition temperature (Tc) up to 55 K, has attracted worldwide research efforts over the past ten years. So far, all these FeSCs structurally adopt FeSe-type layers with a square iron lattice and superconductivity can be generated by either chemical doping or external pressure. Herein, we report the observation of superconductivity in an iron-based honeycomb lattice via pressure-driven spin-crossover. Under compression, the layered FePX3 (X = S, Se) simultaneously undergo large in-plane lattice collapses, abrupt spin-crossovers, and insulator-metal transitions. Superconductivity emerges in FePSe3 along with the structural transition and vanishing of magnetic moment with a starting Tc ~ 2.5 K at 9.0 GPa and the maximum Tc ~ 5.5 K around 30 GPa. The discovery of superconductivity in iron-based honeycomb lattice provides a demonstration for the pursuit of transition-metal-based superconductors via pressure-driven spin-crossover.

High-Pressure Behavior of Silver Fluorides up to 40 GPa.

A combined experimental-theoretical study of silver(I) and silver(II) fluorides under high pressure is reported. For AgI, the CsCl-type structure is stable to at least 39 GPa; the overtone of the IR-active mode is seen in the Raman spectrum. Its AgIIF2 sibling is a unique compound in many ways: it is more covalent than other known difluorides, crystallizes in a layered structure, and is enormously reactive. Using X-ray diffraction and guided by theoretical calculations (density functional theory), we have been able to elucidate crystal structures of high-pressure polymorphs of AgF2. The transition from ambient pressure to an unprecedented nanotubular structure takes place via an intermediate orthorhombic layered structure, which lacks an inversion center. The observed phase transitions are discussed within the broader framework of the fluorite → cotunnite → Ni2In series, which has been seen for other metal difluorides.

Comment on "Observation of the Wigner-Huntington transition to metallic hydrogen".

Dias and Silvera (Research Article, 17 February 2017, p. 715) report on the observation of the Wigner-Huntington transition to metallic hydrogen at 495 gigapascals at 5.5 and 83 kelvin. Here, we show that the claim of metallic behavior is not supported by the presented data, which are scarce, contradictory, and do not prove the presence of hydrogen in the high-pressure cavity.

Decompression-Driven Superconductivity Enhancement in In2 Se3.

An unexpected superconductivity enhancement is reported in decompressed In2 Se3 . The onset of superconductivity in In2 Se3 occurs at 41.3 GPa with a critical temperature (Tc ) of 3.7 K, peaking at 47.1 GPa. The striking observation shows that this layered chalcogenide remains superconducting in decompression down to 10.7 GPa. More surprisingly, the highest Tc that occurs at lower decompression pressures is 8.2 K, a twofold increase in the same crystal structure as in compression. It is found that the evolution of Tc is driven by the pressure-induced R-3m to I-43d structural transition and significant softening of phonons and gentle variation of carrier concentration combined in the pressure quench. The novel decompression-induced superconductivity enhancement implies that it is possible to maintain pressure-induced superconductivity at lower or even ambient pressures with better superconducting performance.

Persistence of Mixed and Non-intermediate Valence in the High-Pressure Structure of Silver(I,III) Oxide, AgO: A Combined Raman, X-ray Diffraction (XRD), and Density Functional Theory (DFT) Study.

The X-ray diffraction data collected up to ca. 56 GPa and the Raman spectra measured up to 74.8 GPa for AgO, or AgIAgIIIO2, which is a prototypical mixed valence (disproportionated) oxide, indicate that two consecutive phase transitions occur: the first-order phase transition occurs between 16.1 GPa and 19.7 GPa, and a second-order phase transition occurs at ca. 40 GPa. All polymorphic forms host the square planar [AgIIIO4] units typical of low-spin AgIII. The disproportionated Imma form persists at least up to 74.8 GPa, as indicated by Raman spectra. Theoretical hybrid density functional theory (DFT) calculations show that the first-order transition is phonon-driven. AgO stubbornly remains disproportionated up to at least 100 GPa-in striking contrast to its copper analogue-and the fundamental band gap of AgO is ∼0.3 eV at this pressure and is weakly pressure-dependent. Metallization of AgO is yet to be achieved.

Synthesis of sodium polyhydrides at high pressures.

The only known compound of sodium and hydrogen is archetypal ionic NaH. Application of high pressure is known to promote states with higher atomic coordination, but extensive searches for polyhydrides with unusual stoichiometry have had only limited success in spite of several theoretical predictions. Here we report the first observation of the formation of polyhydrides of Na (NaH3 and NaH7) above 40 GPa and 2,000 K. We combine synchrotron X-ray diffraction and Raman spectroscopy in a laser-heated diamond anvil cell and theoretical random structure searching, which both agree on the stable structures and compositions. Our results support the formation of multicenter bonding in a material with unusual stoichiometry. These results are applicable to the design of new energetic solids and high-temperature superconductors based on hydrogen-rich materials.

Effects of pressure and distortion on superconductivity in Tl2Ba2CaCu2O(8+δ).

The systematic evolution of the structural, vibrational, and superconducting properties of nearly optimally doped Tl2Ba2CaCu2O(8+δ) with pressure up to 30 GPa is studied by x-ray diffraction, Raman scattering, and magnetic susceptibility measurements. No phase transformation is observed in the studied pressure regime. The obtained lattice parameters and unit-cell volume continuously decrease with pressure by following the expected equation of state. The axial ratio of c/a exhibits an anomaly starting from 9 GPa. At such a pressure level, the deviation from the nonlinear variation of the phonon frequencies is detected. Both the above observations indicate the enhancement of the distortion upon compression. The superconducting transition temperature is found to exhibit a parabolic behavior with a maximum of 114 K around 7 GPa. We demonstrate that the interplay between the intrinsic pressure variables and distortion controls the superconductivity.

Origin of colossal magnetoresistance in LaMnO3 manganite.

Phase separation is a crucial ingredient of the physics of manganites; however, the role of mixed phases in the development of the colossal magnetoresistance (CMR) phenomenon still needs to be clarified. We report the realization of CMR in a single-valent LaMnO3 manganite. We found that the insulator-to-metal transition at 32 GPa is well described using the percolation theory. Pressure induces phase separation, and the CMR takes place at the percolation threshold. A large memory effect is observed together with the CMR, suggesting the presence of magnetic clusters. The phase separation scenario is well reproduced, solving a model Hamiltonian. Our results demonstrate in a clean way that phase separation is at the origin of CMR in LaMnO3.

Nuclear resonant inelastic X-ray scattering at high pressure and low temperature.

A new synchrotron radiation experimental capability of coupling nuclear resonant inelastic X-ray scattering with the cryogenically cooled high-pressure diamond anvil cell technique is presented. The new technique permits measurements of phonon density of states at low temperature and high pressure simultaneously, and can be applied to studies of phonon contribution to pressure- and temperature-induced magnetic, superconducting and metal-insulator transitions in resonant isotope-bearing materials. In this report, a pnictide sample, EuFe2As2, is used as an example to demonstrate this new capability at beamline 3-ID of the Advanced Photon Source, Argonne National Laboratory. A detailed description of the technical development is given. The Fe-specific phonon density of states and magnetism from the Fe sublattice in Eu(57)Fe2As2 at high pressure and low temperature were derived by using this new capability.

Electronic properties and metrology applications of the diamond NV- center under pressure.

The negatively charged nitrogen-vacancy (NV-) center in diamond has realized new frontiers in quantum technology. Here, the optical and spin resonances of the NV- center are observed under hydrostatic pressures up to 60 GPa. Our results motivate powerful new techniques to measure pressure and image high-pressure magnetic and electric phenomena. Additionally, molecular orbital analysis and semiclassical calculations provide insight into the effects of compression on the electronic orbitals of the NV- center.

Superconductivity in highly disordered dense carbon disulfide.

High pressure plays an increasingly important role in both understanding superconductivity and the development of new superconducting materials. New superconductors were found in metallic and metal oxide systems at high pressure. However, because of the filled close-shell configuration, the superconductivity in molecular systems has been limited to charge-transferred salts and metal-doped carbon species with relatively low superconducting transition temperatures. Here, we report the low-temperature superconducting phase observed in diamagnetic carbon disulfide under high pressure. The superconductivity arises from a highly disordered extended state (CS4 phase or phase III[CS4]) at ~6.2 K over a broad pressure range from 50 to 172 GPa. Based on the X-ray scattering data, we suggest that the local structural change from a tetrahedral to an octahedral configuration is responsible for the observed superconductivity.