Signatures of superconductivity near 80 K in a nickelate under high pressure.

Although high-transition-temperature (high-Tc) superconductivity in cuprates has been known for more than three decades, the underlying mechanism remains unknown1-4. Cuprates are the only unconventional superconductors that exhibit bulk superconductivity with Tc above the liquid-nitrogen boiling temperature of 77 K. Here we observe that high-pressure resistance and mutual inductive magnetic susceptibility measurements showed signatures of superconductivity in single crystals of La3Ni2O7 with maximum Tc of 80 K at pressures between 14.0 GPa and 43.5 GPa. The superconducting phase under high pressure has an orthorhombic structure of Fmmm space group with the [Formula: see text] and [Formula: see text] orbitals of Ni cations strongly mixing with oxygen 2p orbitals. Our density functional theory calculations indicate that the superconductivity emerges coincidently with the metallization of the σ-bonding bands under the Fermi level, consisting of the [Formula: see text] orbitals with the apical oxygen ions connecting the Ni-O bilayers. Thus, our discoveries provide not only important clues for the high-Tc superconductivity in this Ruddlesden-Popper double-layered perovskite nickelates but also a previously unknown family of compounds to investigate the high-Tc superconductivity mechanism.

From Insulator to Superconductor: A Series of Pressure-Driven Transitions in Quasi-One-Dimensional TiS3 Nanoribbons.

Transition metal trichalcogenides (TMTCs) offer remarkable opportunities for tuning electronic states through modifications in chemical composition, temperature, and pressure. Despite considerable interest in TMTCs, there remain significant knowledge gaps concerning the evolution of their electronic properties under compression. In this study, we employ experimental and theoretical approaches to comprehensively explore the high-pressure behavior of the electronic properties of TiS3, a quasi-one-dimensional (Q1D) semiconductor, across various temperature ranges. Through high-pressure electrical resistance and magnetic measurements at elevated pressures, we uncover a distinctive sequence of phase transitions within TiS3, encompassing a transformation from an insulating state at ambient pressure to the emergence of an incipient superconducting state above 70 GPa. Our findings provide compelling evidence that superconductivity at low temperatures of ∼2.9 K is a fundamental characteristic of TiS3, shedding new light on the intriguing high-pressure electronic properties of TiS3 and underscoring the broader implications of our discoveries for TMTCs in general.

Superatomic-Charge-Density-Wave in Cluster-Assembled Au6Te12Se8 Superconductors.

Superatomic crystals are a class of hierarchical materials composed of atomically precise clusters assembled via van der Waals or covalent-like interactions. Au6Te12Se8, an all-inorganic superatomic superconductor exhibiting superatomic-charge-density-wave (S-CDW), provides the first platform to study the response of its collective quantum phenomenon to the external pressure in superatomic crystals. We reveal a competition between S-CDW and superconductivity in an ultra-narrow pressure range. Distinct from conventional CDW ordering, S-CDW shows the lowest threshold (0.1 GPa) toward external pressure that is 1-2 orders of magnitude lower than other atomic compounds. Prominently, a second superconducting phase emerges above 7.3 GPa with a threefold enhancement in the transition temperature (Tc) to 8.5 K, indicating a switch of the conduction channel from the a- to b-axis. In situ synchrotron diffractions and theoretical calculations reveal a pressure-mediated mesoscopic slip of the superatoms and a 2D-3D transition of the Fermi surface topology, which well explains the observed dimensional crossover of conductivity and re-entrant superconductivity.

Pressure-induced phase transitions and superconductivity in a quasi-1-dimensional topological crystalline insulator α-Bi4Br4.

Great progress has been achieved in the research field of topological states of matter during the past decade. Recently, a quasi-1-dimensional bismuth bromide, Bi4Br4, has been predicted to be a rotational symmetry-protected topological crystalline insulator; it would also exhibit more exotic topological properties under pressure. Here, we report a thorough study of phase transitions and superconductivity in a quasihydrostatically pressurized α-Bi4Br4 crystal by performing detailed measurements of electrical resistance, alternating current magnetic susceptibility, and in situ high-pressure single-crystal X-ray diffraction together with first principles calculations. We find a pressure-induced insulator-metal transition between ∼3.0 and 3.8 GPa where valence and conduction bands cross the Fermi level to form a set of small pockets of holes and electrons. With further increase of pressure, 2 superconductive transitions emerge. One shows a sharp resistance drop to 0 near 6.8 K at 3.8 GPa; the transition temperature gradually lowers with increasing pressure and completely vanishes above 12.0 GPa. Another transition sets in around 9.0 K at 5.5 GPa and persists up to the highest pressure of 45.0 GPa studied in this work. Intriguingly, we find that the first superconducting phase might coexist with a nontrivial rotational symmetry-protected topology in the pressure range of ∼3.8 to 4.3 GPa; the second one is associated with a structural phase transition from monoclinic C2/m to triclinic P-1 symmetry.

Monoclinic EuSn_{2}As_{2}: A Novel High-Pressure Network Structure.

The layered crystal of EuSn_{2}As_{2} has a Bi_{2}Te_{3}-type structure in rhombohedral (R3[over ¯]m) symmetry and has been confirmed to be an intrinsic magnetic topological insulator at ambient conditions. Combining ab initio calculations and in situ x-ray diffraction measurements, we identify a new monoclinic EuSn_{2}As_{2} structure in C2/m symmetry above ∼14 GPa. It has a three-dimensional network made up of honeycomblike Sn sheets and zigzag As chains, transformed from the layered EuSn_{2}As_{2} via a two-stage reconstruction mechanism with the connecting of Sn-Sn and As-As atoms successively between the buckled SnAs layers. Its dynamic structural stability has been verified by phonon mode analysis. Electrical resistance measurements reveal an insulator-metal-superconductor transition at low temperature around 5 and 15 GPa, respectively, according to the structural conversion, and the superconductivity with a T_{C} value of ∼4 K is observed up to 30.8 GPa. These results establish a high-pressure EuSn_{2}As_{2} phase with intriguing structural and electronic properties and expand our understandings about the layered magnetic topological insulators.

Pressure-induced phase transitions and superconductivity in a black phosphorus single crystal.

We report a thorough study of the transport properties of the normal and superconducting states of black phosphorus (BP) under magnetic field and high pressure with a large-volume apparatus that provides hydrostatic pressure to induce transitions from the layered A17 phase to the layered A7 phase and to the cubic phase of BP. Quantum oscillations can be observed at P ≥ 1 GPa in both resistivity and Hall voltage, and their evolutions with pressure in the A17 phase imply a continuous enlargement of Fermi surface. A significantly large magnetoresistance (MR) at low temperatures is observed in the A7 phase that becomes superconducting below a superconducting transition temperature Tc ∼ 6-13 K. Tc increases continuously with pressure on crossing the A7 to the cubic phase boundary. The strong MR effect can be fit by a modified Kohler's rule. A correlation between Tc and fitting parameters suggests that phonon-mediated interactions play dominant roles in driving the Cooper pairing, which is further supported by our density functional theory (DFT) calculations. The change of effective carrier mobility in the A17 phase under pressure derived from the MR effect is consistent with that obtained from the temperature dependence of the quantum oscillations. In situ single-crystal diffraction under high pressure indicates a total structural reconstruction instead of simple stretching of the A17 phase layers in the A17-to-A7-phase transition. This finding helps us to interpret transport properties on crossing the phase transition under high pressure.

Large Positive Zero-Field Splitting in the Cluster Magnet Ba3CeRu2O9.

We present the synthesis and magnetic characterization of a polycrystalline sample of the 6H-perovskite Ba3CeRu2O9, which consists of Ru dimers based on face-sharing RuO6 octahedra. Our low-temperature magnetic susceptibility, magnetization, and neutron powder diffraction results reveal a nonmagnetic singlet ground state for the dimers. Inelastic neutron scattering, infrared spectroscopy, and the magnetic susceptibility over a wide temperature range are best explained by a molecular orbital model with a zero-field splitting parameter D = 85 meV for the Stot = 1 electronic ground-state multiplet. This large value is likely due to strong mixing between this ground-state multiplet and low-lying excited multiplets, arising from a sizable spin molecular orbital coupling combined with an axial distortion of the Ru2O9 units. Although the positive sign for the splitting ensures that Ba3CeRu2O9 is not a single molecule magnet, our work suggests that the search for these interesting materials should be extended beyond Ba3CeRu2O9 to other molecular magnets based on metal-metal bonding.

Pressure-Induced Large Volume Collapse, Plane-to-Chain, Insulator to Metal Transition in CaMn2Bi2.

In situ high pressure single crystal X-ray diffraction study reveals that the quantum material CaMn2Bi2 undergoes a unique plane to chain structural transition between 2 and 3 GPa, accompanied by a large volume collapse. Puckered Mn-Mn honeycomb layer converts to quasi-one-dimensional (1D) zigzag chains above the phase transition pressure. Single crystal measurements reveal that the pressure-induced structural transformation is accompanied by a dramatic 2 orders of magnitude drop of resistivity. Although the ambient pressure phase displays semiconducting behavior at low temperatures, metallic temperature dependent resistivity is observed for the high pressure phase, as surprisingly, are two resistivity anomalies with opposite pressure dependences, while one of them could be a magnetic transition and the other originates from Fermi surface instability. Assessment of the total energies for hypothetical magnetic structures for high pressure CaMn2Bi2 indicates that ferrimagnetism is thermodynamically favored.

Anomalous anisotropic compression behavior of superconducting CrAs under high pressure.

CrAs was observed to possess the bulk superconductivity under high-pressure conditions. To understand the superconducting mechanism and explore the correlation between the structure and superconductivity, the high-pressure structural evolution of CrAs was investigated using the angle-dispersive X-ray diffraction (XRD) method. The structure of CrAs remains stable up to 1.8 GPa, whereas the lattice parameters exhibit anomalous compression behaviors. With increasing pressure, the lattice parameters a and c both demonstrate a nonmonotonic change, and the lattice parameter b undergoes a rapid contraction at ∼ 0.18-0.35 GPa, which suggests that a pressure-induced isostructural phase transition occurs in CrAs. Above the phase transition pressure, the axial compressibilities of CrAs present remarkable anisotropy. A schematic band model was used to address the anomalous compression behavior of CrAs. The present results shed light on the structural and related electronic responses to high pressure, which play a key role toward understanding the superconductivity of CrAs.

Charge disproportionation and the pressure-induced insulator-metal transition in cubic perovskite PbCrO3.

The perovskite PbCrO3 is an antiferromagnetic insulator. However, the fundamental interactions leading to the insulating state in this single-valent perovskite are unclear. Moreover, the origin of the unprecedented volume drop observed at a modest pressure of P = 1.6 GPa remains an outstanding problem. We report a variety of in situ pressure measurements including electron transport properties, X-ray absorption spectrum, and crystal structure study by X-ray and neutron diffraction. These studies reveal key information leading to the elucidation of the physics behind the insulating state and the pressure-induced transition. We argue that a charge disproportionation 3Cr(4+) → 2Cr(3+) + Cr(6+) in association with the 6s-p hybridization on the Pb(2+) is responsible for the insulating ground state of PbCrO3 at ambient pressure and the charge disproportionation phase is suppressed under pressure to give rise to a metallic phase at high pressure. The model is well supported by density function theory plus the correlation energy U (DFT+U) calculations.

High-Pressure Synthesis, Crystal Structure, and Magnetic and Transport Properties of a Six-Layered SrRhO3.

A SrRhO3 polytype with six-layered (6M) structure was synthesized under high pressure and high temperature. The crystal structure was obtained by refining X-ray powder diffraction with the monoclinic space group C2/c with lattice parameters a = 5.5650(1) Å, b = 9.5967(2) Å, c = 14.0224(4) Å, and ß = 92.846(2)°. It is isostructural with SrIrO3 synthesized under ambient pressure and consists of dimers of the face-shared Rh(2)O6 octahedra connected by their vertices to the corner-shared Rh(1)O6 octahedra along the c axis with a stacking of SrO3 layers in the sequence of CCHCCH, where C and H denote cubic and hexagonal closed packing, respectively. With increasing pressure, the 6M SrRhO3 transforms to an orthorhombic perovskite (Pv) phase, having a = 5.5673(1) Å, b = 5.5399(2) Å, c = 7.8550(2) Å in the space group Pbnm. A pressure-temperature phase diagram shows that the 6M-Pv phase boundary moves to lower temperatures with increasing pressure. Both the 6M and the Pv phases of SrRhO3 were characterized by magnetic susceptibility, resistivity, and thermopower; they are all metals with an enhanced and temperature-dependent magnetic susceptibility; no long-range magnetic order has been found. The polytype structures are normally found in ABO3 oxides with the geometric tolerance factor t > 1. SrRhO3 represents another example (in addition to SrIrO3) where the polytype 6M structure can be stabilized with a t < 1.

Charge Transfer Induced Multifunctional Transitions with Sensitive Pressure Manipulation in a Metal-Organic Framework.

The metal-organic framework {[Fe(2,2'-bipyridine)(CN)4]2Co(4,4'-bipyridine)}·4H2O (Fe2Co-MOF) with single-chain magnetism undergoes an intermetallic charge transfer that converts the Fe2Co charge/spin configurations from Fe(3+)LS-Co(2+)HS-Fe(3+)LS to Fe(2+)LS-Co(3+)LS-Fe(3+)LS (LS = low spin, HS = high spin) around 220 K under ambient pressure. A series of coherent phase transitions in structure, magnetism, permittivity and ferroelectricity are found to take place accompanying with the charge transfer, making Fe2Co-MOF a unique ferroelectric single-chain magnet at low temperature. Moreover, our detailed measurements of magnetization, dielectric constant, and Raman scattering under high pressures illustrate that the charge transfer as well as the resulting multifunctional transitions can be readily induced to occur at room temperature by applying a tiny external pressure of about 0.5 kbar. The present study thus provides a pressure well-controllable multifunctional material with potential applications in a broad temperature region across room temperature.

Ternary superhydrides for high-temperature superconductivity at low pressures.

Focusing on the ternary hydrides, the new hope of Room-Temperature Superconductivity, this perspective delves into the research background, highlights current challenges, and illuminates promising avenues for future studies.

Possible quantum-spin-liquid state in van der Waals cluster magnet Nb3Cl8.

The cluster magnet Nb3Cl8consists of Nb3trimmers that form an emergentS= 1/2 two-dimensional triangular layers, which are bonded by weak van der Waals interactions. Recent studies show that its room-temperature electronic state can be well described as a single-band Mott insulator. However, the magnetic ground state is non-magnetic due to a structural transition below about 100 K. Here we show that there exists a thickness threshold below which the structural transition will not happen. For a bulk crystal, a small fraction of the sample maintains the high-temperature structure at low temperatures and such remnant gives rise to linear-temperature dependence of the specific heat at very low temperatures. This is further confirmed by the measurements on ground powder sample orc-axis pressed single crystals, which prohibits the formation of the non-magnetic state. Moreover, the intrinsic magnetic susceptibility also tends to be constant with decreasing temperature. Our results suggest that Nb3Cl8with the high-temperature structure may host a quantum-spin-liquid ground state with spinon Fermi surfaces, which can be achieved by making the thickness of a sample smaller than a certain threshold.

Tunable positions of Weyl nodes via magnetism and pressure in the ferromagnetic Weyl semimetal CeAlSi.

The noncentrosymmetric ferromagnetic Weyl semimetal CeAlSi with simultaneous space-inversion and time-reversal symmetry breaking provides a unique platform for exploring novel topological states. Here, by employing multiple experimental techniques, we demonstrate that ferromagnetism and pressure can serve as efficient parameters to tune the positions of Weyl nodes in CeAlSi. At ambient pressure, a magnetism-facilitated anomalous Hall/Nernst effect (AHE/ANE) is uncovered. Angle-resolved photoemission spectroscopy (ARPES) measurements demonstrated that the Weyl nodes with opposite chirality are moving away from each other upon entering the ferromagnetic phase. Under pressure, by tracing the pressure evolution of AHE and band structure, we demonstrate that pressure could also serve as a pivotal knob to tune the positions of Weyl nodes. Moreover, multiple pressure-induced phase transitions are also revealed. These findings indicate that CeAlSi provides a unique and tunable platform for exploring exotic topological physics and electron correlations, as well as catering to potential applications, such as spintronics.

Crystal and magnetic structures and physical properties of a new pyroxene NaMnGe2O6 synthesized under high pressure.

A new pyroxene compound, NaMnGe(2)O(6), has been synthesized at 3 GPa and 800 °C and fully characterized by X-ray single-crystal diffraction, neutron powder diffraction, and measurements of magnetization and specific heat. NaMnGe(2)O(6) crystallizes into a monoclinic C2/c structure with unit-cell parameters a = 9.859(2) Å, b = 8.7507(18) Å, c = 5.5724(11) Å, and ß = 105.64(3)° at 153 K. A cooperative Jahn-Teller distortion is formed by an ordering of the longest Mn-O bonds between two neighboring octahedra along the chain direction. This feature distinguishes NaMnGe(2)O(6) from other pyroxene compounds without Jahn-Teller active cations and suggests that the Jahn-Teller distortion competes with the intrinsic local distortion in the pyroxene structure. No orbital order-disorder transition has been found up to 750 K. Like other alkali-metal pyroxenes with S > (1)/(2), NaMnGe(2)O(6) (S = 2) was found to undergo a long-range antiferromagnetic (AF) ordering at T(N) = 7 K due to intrachain and interchain exchange interactions. Due to the peculiar structural features and the corresponding magnetic coupling, the weak AF spin ordering gives way to a ferromagnetic-like state at a sufficiently high magnetic field. Specific-heat measurements demonstrated that a large portion of the magnetic entropy, >60%, has been removed above T(N) as a result of strong spin correlations within the quasi-one-dimensional Mn(3+)-spin chains. The Reitveld refinement of neutron powder diffraction data gives a commensurate magnetic structure defined by k = [0 0 0.5] with Mn moments aligned mainly along the c-axis with a small component along both a- and b-axes.

High-pressure synthesis, structure, and photoluminescence of a new KSbO3-type bismuth germanate Bi3Ge3O10.5.

A new Bi(3)Ge(3)O(10.5) compound has been synthesized under high pressure, P = 7 GPa, and 700 °C. Instead of the pyrochlore that is normally stabilized under high pressure, the Bi(3)Ge(3)O(10.5) crystallizes in a KSbO(3)-ype crystal structure. The crystal structure has been refined by the Rietveld method from synchrotron X-ray diffraction data. Moreover, we have also characterized the Bi(3)Ge(3)O(10.5) by X-ray photoelectron spectroscopy, photoluminescence, and specific heat.

Interplay between Charge-Density-Wave, Superconductivity, and Ferromagnetism in CuIr2-xCrxTe4 Chalcogenides.

We report the crystal structure, charge-density-wave (CDW), superconductivity (SC), and ferromagnetism (FM) in CuIr2-xCrxTe4 (0 ≤ x ≤ 2) chalcogenides. Powder x-ray diffraction (PXRD) results reveal that the CuIr2-xCrxTe4 series are distinguished between two structural types and three different regions: (i) layered trigonal structure region, (ii) mixed phase regions, and (iii) spinel structure region. Besides, Cr substitution for Ir site results in rich physical properties including the collapse of CDW, the formation of dome-shaped like SC, and the emergence of magnetism. Cr doping slightly elevates the superconducting critical temperature (Tsc) to its highest Tsc = 2.9 K around x = 0.06. As x increases from 0.3 to 0.4, the ferromagnetic Curie temperature (Tc) increases from 175 to 260 K. However, the Tc remains unchanged in the spinel range of 1.9 ≤ x ≤ 2. This finding provides a comprehensive material platform for investigating the interplay between CDW, SC, and FM multipartite quantum states.

Superconducting dome associated with the suppression and re-emergence of charge density wave states upon sulfur substitution in CuIr2Te4chalcogenides.

We report the path from the charge density wave (CDW)-bearing superconductor CuIr2Te4to the metal insulator transition (MIT)-bearing compound CuIr2S4by chemical alloying with the gradual substitution of S for Te. The evolution of structural and physical properties of the CuIr2Te4-xSx(0 ⩽x⩽ 4) polycrystalline system is systemically examined. The x-ray diffraction (XRD) results imply CuIr2Te4-xSx(0 ⩽x⩽ 0.5) crystallizes in a NiAs defected trigonal structure, whereas it adapts to the cubic spinel structure for 3.6 ⩽x⩽ 4 and it is a mixed phase in the doping range of 0.5

Thermochemical Mechanism of Optimized Lanthanum Chromite Heaters for High-Pressure and High-Temperature Experiments.

High-pressure heaters in large volume presses must reconcile potentially contradictory properties, and the whole high-pressure and high-temperature (HPHT) community has been engaged for years to seek a better heater. LaCrO3 (LCO)-based ceramic heaters have been widely applied in multianvil apparatus; however, their performance is far from satisfactory, motivating further research on the chemical optimization strategy and corresponding thermochemical mechanism. Here, we adopted a chemical-screening strategy and manufactured tubular heaters using the electrically, chemically, and mechanically optimized Sr-Cu codoped La0.9Sr0.1Cr0.8Cu0.2O3-δ (LSCCuO-9182). HPHT examinations of cylindrical LSCCuO-9182 heaters on Walker-type multianvil apparatuses demonstrated a small temperature gradient, robust thermochemical stability, and excellent compatibility with high-pressure assemblies below 2273 K and 10 GPa. Thermochemical mechanism analysis revealed that the temperature limitation of the LSCCuO-9182 heater was related to the autoredox process of the Cu dopant and Cr and the exchanging ionic migration of Cu and Mg between the LSCCuO-9182 heater and the MgO sleeve. Our combinatorial strategy coupled with thermochemical mechanism analysis makes the prioritization of contradictory objectives more rational, yields reliable LCO heaters, and sheds light on further improvement of the temperature limitation and thermochemical stability.