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.

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.

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.

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.

Titanium doped kagome superconductor CsV3-xTixSb5 and two distinct phases.

The vanadium-based kagome superconductor CsV3Sb5 has attracted tremendous attention due to its unexcepted anomalous Hall effect (AHE), charge density waves (CDWs), nematicity, and a pseudogap pair density wave (PDW) coexisting with unconventional strong-coupling superconductivity. The origins of CDWs, unconventional superconductivity, and their correlation with different electronic states in this kagome system are of great significance, but so far, are still under debate. Chemical doping in the kagome layer provides one of the most direct ways to reveal the intrinsic physics, but remains unexplored. Here, we report, for the first time, the synthesis of Ti-substituted CsV3Sb5 single crystals and its rich phase diagram mapping the evolution of intertwining electronic states. The Ti atoms directly substitute for V in the kagome layers. CsV3-xTixSb5 shows two distinct superconductivity phases upon substitution. The Ti slightly-substituted phase displays an unconventional V-shaped superconductivity gap, coexisting with weakening CDW, PDW, AHE, and nematicity. The Ti highly-substituted phase has a U-shaped superconductivity gap concomitant with a short-range rotation symmetry breaking CDW, while long-range CDW, twofold symmetry of in-plane resistivity, AHE, and PDW are absent. Furthermore, we also demonstrate the chemical substitution of V atoms with other elements such as Cr and Nb, showing a different modulation on the superconductivity phases and CDWs. These findings open up a way to synthesise a new family of doped CsV3Sb5 materials, and further represent a new platform for tuning the different correlated electronic states and superconducting pairing in kagome superconductors.

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.

Destabilization of the Charge Density Wave and the Absence of Superconductivity in ScV6Sn6 under High Pressures up to 11 GPa.

RV6Sn6 (R = Sc, Y, or rare earth) is a new family of kagome metals that have a similar vanadium structural motif as AV3Sb5 (A = K, Rb, Cs) compounds. Unlike AV3Sb5, ScV6Sn6 is the only compound among the series of RV6Sn6 that displays a charge density wave (CDW) order at ambient pressure, yet it shows no superconductivity (SC) at low temperatures. Here, we perform a high-pressure transport study on the ScV6Sn6 single crystal to track the evolutions of the CDW transition and to explore possible SC. In contrast to AV3Sb5 compounds, the CDW order of ScV6Sn6 can be suppressed completely by a pressure of about 2.4 GPa, but no SC is detected down to 40 mK at 2.35 GPa and 1.5 K up to 11 GPa. Moreover, we observed that the resistivity anomaly around the CDW transition undergoes an obvious change at ~2.04 GPa before it vanishes completely. The present work highlights a distinct relationship between CDW and SC in ScV6Sn6 in comparison with the well-studied AV3Sb5.

Pressure-Induced Metallization of Lead-Free Halide Double Perovskite (NH4 )2 PtI6.

Metallization has recently garnered significant interest due to its ability to greatly facilitate chemical reactions and dramatically change the properties of materials. Materials displaying metallization under low pressure are highly desired for understanding their potential properties. In this work, the effects of the pressure on the structural and electronic properties of lead-free halide double perovskite (NH4 )2 PtI6 are investigated systematically. Remarkably, an unprecedented bandgap narrowing down to the Shockley-Queisser limit is observed at a very low pressure of 0.12 GPa, showing great promise in optoelectronic applications. More interestingly, the metallization of (NH4 )2 PtI6 is initiated at 14.2 GPa, the lowest metallization pressure ever reported in halide perovskites, which is related to the continuous increase in the overlap between the valence and conduction band of I 5p orbital. Its structural evolution upon compression before the metallic transition is also tracked, from cubic Fm-3m to tetragonal P4/mnc and then to monoclinic C2/c phase, which is mainly associated with the rotation and distortions within the [PtI6 ]2- octahedra. These findings represent a significant step toward revealing the structure-property relationships of (NH4 )2 PtI6 , and also prove that high-pressure technique is an efficient tool to design and realize superior optoelectronic materials.

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.

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

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.

Fabrication and evaluation via nuclear quadrupole resonance of a palm cubic-anvil pressure cell.

A "palm" cubic-anvil pressure cell (PCAC) having an outer diameter of 60 mm, the smallest cubic-anvil cell to date, was fabricated to insert in a large-bore superconducting magnet. The pressure cell has a sample space of ϕ 2.5 × 1.5 mm2, which is fairly large for a pressure cell that can reach a high pressure above 4 GPa. Pressure homogeneity was monitored from the 63Cu nuclear-quadrupole-resonance linewidth of Cu2O up to 6.7 GPa. The linewidth first increased with increasing pressure up to 4 GPa and then saturated above 4 GPa. The pressure homogeneity was better than that of a piston-cylinder pressure cell. The PCAC is advantageous because a large sample space and high pressure homogeneity are secured even at high pressures.

Pressure effect on the magnetoresistivity of topological semimetal RhSn.

RhSn is a topological semimetal with chiral fermions. At ambient pressure, it exhibits large positive magnetoresistance (MR) and field-induced resistivity upturn at low temperatures. Here we report on the electrical transport properties of RhSn single crystal under various pressures. We find that with increasing pressure the temperature-dependent resistivity ρ(T) of RhSn varies minutely, whereas the value of MR at low temperatures decreases significantly. The ρ(T) data was fitted with the Bloch-Grüneisen model and the Debye temperature was extracted. Analyses of the nonlinear Hall conductivity with two-band model indicate that the carrier concentrations do not change significantly with pressure, but the mobilities for both electron and hole carriers are reduced monotonically, which can account for the significant reduction of MR under high pressures.

Nonmetallic metal toward a pressure-induced bad-metal state in two-dimensional Cu3LiRu2O6.

The novel two-dimensional honeycomb layered Cu3LiRu2O6 exhibits Pauli-like paramagnetic and Mott variable range hopping semiconduction behaviors, which contradict the large specific-heat Sommerfeld coefficient for metals, and indicate a possible spin-excitation induced nonmetallic metal. This nonmetallic feature can be significantly suppressed by pressure toward producing a bad-metal state, as reflected by the temperature-dependent resistivity response up to 35 GPa.

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.

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.

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.

Asymmetric ferromagnetic criticality in pyrochlore ferromagnet Lu2V2O7.

We study the ferromagnetic criticality of the pyrochlore magnet Lu2V2O7 at the ferromagnetic transition TC≈70K from the isotherms of magnetization M(H) via an iteration process and the Kouvel-Fisher method. The critical exponents associated with the transition are determined: ß = 0.32(1), γ = 1.41(1), and δ=5.38. The validity of these critical exponents is further verified by scaling all the M(H) data in the vicinity of TC onto two universal curves in the plot of M/|ε|ß versus H/|ε|ß+γ, where ε=T/TC-1. The obtained ß and γ values show asymmetric behaviors on the TTC sides, and are consistent with the predicted values of 3D Ising and cubic universality classes, respectively. This makes Lu2V2O7 a rare example in which the critical behaviors associated with a ferromagnetic transition belong to different universality classes. We describe the observed criticality from the Ginzburg-Landau theory with the quartic cubic anisotropy that microscopically originates from the anti-symmetric Dzyaloshinskii-Moriya interaction as revealed by recent magnon thermal Hall effect and theoretical investigations.