Superconductivity in pressurized trilayer La4Ni3O10-δ single crystals.

The pursuit of discovering new high-temperature superconductors that diverge from the copper-based model1-3 has profound implications for explaining mechanisms behind superconductivity and may also enable new applications4-8. Here our investigation shows that the application of pressure effectively suppresses the spin-charge order in trilayer nickelate La4Ni3O10-δ single crystals, leading to the emergence of superconductivity with a maximum critical temperature (Tc) of around 30 K at 69.0 GPa. The d.c. susceptibility measurements confirm a substantial diamagnetic response below Tc, indicating the presence of bulk superconductivity with a volume fraction exceeding 80%. In the normal state, we observe a strange metal behaviour, characterized by a linear temperature-dependent resistance extending up to 300 K. Furthermore, the layer-dependent superconductivity observed hints at a unique interlayer coupling mechanism specific to nickelates, setting them apart from cuprates in this regard. Our findings provide crucial insights into the fundamental mechanisms underpinning superconductivity, while also introducing a new material platform to explore the intricate interplay between the spin-charge order, flat band structures, interlayer coupling, strange metal behaviour and high-temperature superconductivity.

Ultrathin quantum light source with van der Waals NbOCl2 crystal.

Interlayer electronic coupling in two-dimensional materials enables tunable and emergent properties by stacking engineering. However, it also results in significant evolution of electronic structures and attenuation of excitonic effects in two-dimensional semiconductors as exemplified by quickly degrading excitonic photoluminescence and optical nonlinearities in transition metal dichalcogenides when monolayers are stacked into van der Waals structures. Here we report a van der Waals crystal, niobium oxide dichloride (NbOCl2), featuring vanishing interlayer electronic coupling and monolayer-like excitonic behaviour in the bulk form, along with a scalable second-harmonic generation intensity of up to three orders higher than that in monolayer WS2. Notably, the strong second-order nonlinearity enables correlated parametric photon pair generation, through a spontaneous parametric down-conversion (SPDC) process, in flakes as thin as about 46 nm. To our knowledge, this is the first SPDC source unambiguously demonstrated in two-dimensional layered materials, and the thinnest SPDC source ever reported. Our work opens an avenue towards developing van der Waals material-based ultracompact on-chip SPDC sources as well as high-performance photon modulators in both classical and quantum optical technologies1-4.

Synthesis of paracrystalline diamond.

Solids in nature can be generally classified into crystalline and non-crystalline states1-7, depending on whether long-range lattice periodicity is present in the material. The differentiation of the two states, however, could face fundamental challenges if the degree of long-range order in crystals is significantly reduced. Here we report a paracrystalline state of diamond that is distinct from either crystalline or amorphous diamond8-10. The paracrystalline diamond reported in this work, consisting of sub-nanometre-sized paracrystallites that possess a well-defined crystalline medium-range order up to a few atomic shells4,5,11-13, was synthesized in high-pressure high-temperature conditions (for example, 30 GPa and 1,600 K) employing face-centred cubic C60 as a precursor. The structural characteristics of the paracrystalline diamond were identified through a combination of X-ray diffraction, high-resolution transmission microscopy and advanced molecular dynamics simulation. The formation of paracrystalline diamond is a result of densely distributed nucleation sites developed in compressed C60 as well as pronounced second-nearest-neighbour short-range order in amorphous diamond due to strong sp3 bonding. The discovery of paracrystalline diamond adds an unusual diamond form to the enriched carbon family14-16, which exhibits distinguishing physical properties and can be furthered exploited to develop new materials. Furthermore, this work reveals the missing link in the length scale between amorphous and crystalline states across the structural landscape, having profound implications for recognizing complex structures arising from amorphous materials.

Atomically Unraveling Highly Crystalline Self-Intercalated Tantalum Sulfide with Correlated Stacking Registry-Dependent Magnetism.

In self-intercalated two-dimensional (ic-2D) materials, understanding the local chemical environment and the topology of the filling site remains elusive, and the subsequent correlation with the macroscopically manifested physical properties has rarely been investigated. Herein, highly crystalline gram-scale ic-2D Ta1.33S2 crystals were successfully grown by the high-pressure high-temperature method. Employing combined atomic-resolution scanning transmission electron microscopy annular dark field imaging and density functional theory calculations, we systematically unveiled the atomic structures of an atlas of stacking registries in a well-defined √3(a) × âˆš3(a) Ta1.33S2 superlattice. Ferromagnetic order was observed in the AC' stacking registry, and it evolves into an antiferromagnetic state in AA/AB/AB' stacking registries; the AA' stacking registry shows ferrimagnetic ordering. Therefore, we present a novel approach for fabricating large-scale highly crystalline ic-2D crystals and shed light on a powerful means of modulating the magnetic order of ic-2D systems via stacking engineering, i.e., stackingtronics.

BaCu, a Two-Dimensional Electride with Cu Anions.

The electron-rich characteristic and low work function endow electrides with excellent performance in (opto)electronics and catalytic applications; these two features are closely related to the structural topology, constituents, and valence electron concentration of electrides. However, the synthesized electrides, especially two-dimensional (2D) electrides, are limited to specific structural prototypes and anionic p-block elements. Here we synthesize and identify a distinct 2D electride of BaCu with delocalized anionic electrons confined to the interlayer spaces of the BaCu framework. The bonding between Cu and Ba atoms exhibits ionic characteristics, and the adjacent Cu anions form a planar honeycomb structure with metallic Cu-Cu bonding. The negatively charged Cu ions are revealed by the theoretical calculations and experimental X-ray absorption near-edge structure. Physical property measurements reveal that BaCu electride has a high electronic conductivity (ρ = 3.20 µΩ cm) and a low work function (2.5 eV), attributed to the metallic Cu-Cu bonding and delocalized anionic electrons. In contrast to typical ionic 2D electrides with p-block anions, density functional theory calculations find that the orbital hybridization between the delocalized anionic electrons and BaCu framework leads to unique isotropic physical properties, such as mechanical properties, and work function. The freestanding BaCu monolayer with half-metal conductivity exhibits low exfoliation energy (0.84 J/m2) and high mechanical/thermal stability, suggesting the potential to achieve low-dimensional BaCu from the bulk. Our results expand the space for the structure and attributes of 2D electrides, facilitating the discovery and potential application of novel 2D electrides with transition metal anions.

Centrosymmetry-Breaking Morphotropic Phase Boundary: A Pathway to Highly Sensitive and Strong Pressure-Responsive Nonlinear Optical Switches.

The quest for high-performance piezoelectric materials has been synonymous with the pursuit of the morphotropic phase boundary (MPB), yet the full potential of MPBs remains largely untapped outside of the realm of ferroelectrics. In this study, we reveal a new class of MPB by creating continuous molecular-based solid solutions between centro- and noncentrosymmetric compounds, exemplified by (tert-butylammonium)1-x(tert-amylammonium)xFeCl4 (0 ≤ x ≤ 1), where the MPB is formed due to disorder of molecular cations. Near the MPB, we discovered an exceptionally sensitive nonlinear optical material in the centrosymmetric phase, capable of activation at pressures as low as 0.12-0.27 GPa, and producing tunable second-harmonic generation (SHG) signals from zero to 18.8 times that of KH2PO4 (KDP). Meanwhile, synchrotron diffraction experiments have unveiled a third competing phase (P212121) appearing at low pressure, forming a triple-phase point near the MPB, thereby providing insight into the mechanism underpinning the nonlinear optical (NLO) switch behavior. These findings highlight the opportunity to harness exceptional physical properties in symmetry-breaking solid solution systems by strategically designing novel MPBs.

Pressure-Stabilized High-Entropy (FeCoNiCuRu)S2 Sulfide Anode toward Simultaneously Fast and Durable Lithium/Sodium Ion Storage.

Pressure-stabilized high-entropy sulfide (FeCoNiCuRu)S2 (HES) is proposed as an anode material for fast and long-term stable lithium/sodium storage performance (over 85% retention after 15 000 cycles @10 A g-1 ). Its superior electrochemical performance is strongly related to the increased electrical conductivity and slow diffusion characteristics of entropy-stabilized HES. The reversible conversion reaction mechanism, investigated by ex-situ XRD, XPS, TEM, and NMR, further confirms the stability of the host matrix of HES after the completion of the whole conversion process. A practical demonstration of assembled lithium/sodium capacitors also confirms the high energy/power density and long-term stability (retention of 92% over 15 000 cycles @5 A g-1 ) of this material. The findings point to a feasible high-pressure route to realize new high-entropy materials for optimized energy storage performance.

Unconventional excitonic states with phonon sidebands in layered silicon diphosphide.

Complex correlated states emerging from many-body interactions between quasiparticles (electrons, excitons and phonons) are at the core of condensed matter physics and material science. In low-dimensional materials, quantum confinement affects the electronic, and subsequently, optical properties for these correlated states. Here, by combining photoluminescence, optical reflection measurements and ab initio theoretical calculations, we demonstrate an unconventional excitonic state and its bound phonon sideband in layered silicon diphosphide (SiP2), where the bound electron-hole pair is composed of electrons confined within one-dimensional phosphorus-phosphorus chains and holes extended in two-dimensional SiP2 layers. The excitonic state and emergent phonon sideband show linear dichroism and large energy redshifts with increasing temperature. Our ab initio many-body calculations confirm that the observed phonon sideband results from the correlated interaction between excitons and optical phonons. With these results, we propose layered SiP2 as a platform for the study of excitonic physics and many-particle effects.

Stability and Semiconducting Behavior of Magnesium Polysulfides by Nonequivalent sp3 Hybridizations.

The Mg/S battery has attracted enormous interest in recent years due to its high theoretical capacity, low cost, and high security. However, the understanding of many intermediate magnesium polysulfides in the Mg/S battery remains elusive. Combining extensive structural search and first-principles calculations, we investigate the phase stability, structural character, and electronic structure of magnesium polysulfides in a wide range from MgS to MgS8. The pyrite-type MgS2 (space group: Pa3̅) is predicted to be stable. Five magnesium polysulfides, MgSx (x = 3, 4, 5, 6, and 8), are found to be metastable, with formation enthalpies slightly above the convex hull. S2 dimer, "V"-like S3, and highly distorted Sx chains are found for the polysulfides with bond lengths close to or slightly longer than S8 and bond angles similar to S8. A wide range of band gaps (0.77-2.82 eV) are revealed for the polysulfides due to the contribution of the nonequivalent sp3 hybridization of the S atoms in Sx2-. Our results can help to further understand the electrochemical process in the Mg/S battery.

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.

Disproportionation of SO_{2} at High Pressure and Temperature.

Materials once suffered at high-pressure and high-temperature (HPHT) conditions often exhibit exotic phenomena that defy conventional wisdom. The behaviors of sulfur dioxide (SO_{2}), one of the archetypal simple molecules, at HPHT conditions have attracted a great deal of attention due to its relevance to the S cycle between deep Earth and the atmosphere. Here we report the discovery of an unexpected disproportionation of SO_{2} via bond breaking into elemental S and sulfur trioxide (SO_{3}) at HPHT conditions through a jointly experimental and theoretical study. Measured x-ray diffraction and Raman spectroscopy data allow us to solve unambiguously the crystal structure (space group R3[over ¯]c) of the resultant SO_{3} phase that shows an extended framework structure formed by vertex-sharing octahedra SO_{6}. Our findings lead to a significant extension of the phase diagram of SO_{2} and suggest that SO_{2}, despite its abundance in Earth's atmosphere and ubiquity in other giant planets, is not a stable compound at HPHT conditions relevant to planetary interiors, providing important implications for elucidating the S chemistry in deep Earth and other giant planets.

Inference of a "Hot Ice" Layer in Nitrogen-Rich Planets: Demixing the Phase Diagram and Phase Composition for Variable Concentration Helium-Nitrogen Mixtures Based on Isothermal Compression.

Van der Waals (vdW) chemistry in simple molecular systems may be important for understanding the structure and properties of the interiors of the outer planets and their satellites, where pressures are high and such components may be abundant. In the current study, Raman spectra and visual observation are employed to investigate the phase separation and composition determination for helium-nitrogen mixtures with helium concentrations from 20 to 95% along the 295 K isothermal compression. Fluid-fluid-solid triple-phase equilibrium and several equilibria of two phases including fluid-fluid and fluid-solid have been observed in different helium-nitrogen mixtures upon loading or unloading pressure. The homogeneous fluid in helium-nitrogen mixtures separates into a helium-rich fluid (F1) and a nitrogen-rich fluid (F2) with increasing pressure. The triple-phase point occurs at 295 K and 8.8 GPa for a solid-phase (N2)11He vdW compound, fluid F1 with around 50% helium, and fluid F2 with 95% helium. Helium concentrations of F1 coexisted with the (N2)11He vdW compound or δ-N2 in helium-nitrogen mixtures with different helium concentrations between 40 and 50% and between 20 and 40%, respectively. In addition, the helium concentration of F2 is the same in helium-nitrogen mixtures with different helium concentrations and decreases upon loading pressure. Pressure-induced nitrogen molecule ordering at 32.6 GPa and a structural phase transition at 110 GPa are observed in (N2)11He. In addition, at 187 GPa, a pressure-induced transition to an amorphous state is identified.

Hydrostatic pressure effect of photocarrier dynamics in GaAs probed by time-resolved terahertz spectroscopy.

Pressure effects on photocarrier dynamics such as interband relaxations and intraband cooling in GaAs have been investigated using in situ time-resolved terahertz spectroscopy with a diamond anvil cell. The interband photocarrier lifetime significantly decreases by nearly two orders of magnitude as the external hydrostatic pressure is increased up to 10 GPa. Considerable pressure tuning for the intervalley scattering processes has also been observed, and the time constants under different pressures are extracted based on the three-state rate model. This work provides new perspectives on tailoring nonequilibrium carrier dynamics in semiconductors using hydrostatic pressure and may serve as the impetus for the development of high-pressure terahertz spectroscopy.

Potassium-activated anionic copper and covalent Cu-Cu bonding in compressed K-Cu compounds.

Elemental copper and potassium are immiscible under ambient conditions. It is known that pressure is a useful tool to promote the reaction between two different elements by modifying their electronic structure significantly. Here, we predict the formation of four K-Cu compounds (K3Cu2, K2Cu, K5Cu2, and K3Cu) under moderate pressure through unbiased structure search and first-principles calculations. Among all predicted structures, the simulated x-ray diffraction pattern of K3Cu2 perfectly matches a K-Cu compound synthesized in 2004. Further simulations indicate that the K-Cu compounds exhibit diverse structural features with novel forms of Cu aggregations, including Cu dimers, linear and zigzag Cu chains, and Cu-centered polyhedrons. Analysis of the electronic structure reveals that Cu atoms behave as anions to accept electrons from K atoms through fully filling 4s orbitals and partially extending 4p orbitals. Covalent Cu-Cu interaction is found in these compounds, which is associated with the sp hybridizations. These results provide insights into the understanding of the phase diversity of alkali/alkaline earth and metal systems.

2D Sandwiched Nano Heterostructures Endow MoSe2 /TiO2- x /Graphene with High Rate and Durability for Sodium Ion Capacitor and Its Solid Electrolyte Interphase Dependent Sodiation/Desodiation Mechanism.

Nano heterostructures relying on their versatile construction and the breadth of combined functionality have shown great potential in energy storage fields. Herein, 2D sandwiched MoSe2 /TiO2- x /graphene nano heterostructures are designed by integrating structural and functional effects of each component, aiming to address the rate capability and cyclic stability of MoSe2 for sodium ion capacitors (SICs). These 2D nano heterostructures based on graphene platform can facilitate the interfacial electron transport, giving rise to fast reaction kinetics. Meanwhile, the 2D open structure induces a large extent of surface capacitive contribution, eventually leading to a high rate capability (415.2 mAh g-1 @ 5 A g-1 ). An ultrathin oxygen deficient TiO2- x layer sandwiched in these nano heterostructures provides a strong chemical-anchoring regarding the products generated during the sodiation/desodiation process, securing the entire cyclic stability. The associated sodiation/desodiation mechanism is revealed by operando and ex situ characterizations, which exhibits a strong solid electrolyte interphase (SEI) dependence. The simulations verify the dependent sodiation products and enhanced heterostructural chemical-anchoring. Assembled SICs based on these nano heterostructures anode exhibit high initial Coulombic efficiency, energy/power densities, and long cycle life, shedding new light on the design of nano heterostructure electrodes for high performance energy storage application.

Nitrogen Codoped Unique Carbon with 0.4 nm Ultra-Micropores for Ultrahigh Areal Capacitance Supercapacitors.

A full understanding of ion transport in porous carbon electrodes is essential for achieving effective energy storage in their applications as electrochemical supercapacitors. It is generally accepted that pores in the size range below 0.5 nm are inaccessible to electrolyte ions and lower the capacitance of carbon materials. Here, nitrogen-doped carbon with ultra-micropores smaller than 0.4 nm with a narrow size distribution, which represents the first example of electrode materials made entirely from ultra-microporous carbon, is prepared. An in situ electrochemical quartz crystal microbalance technique to study the effects of the ultra-micropores on charge storage in supercapacitors is used. It is found that ultra-micropores smaller than 0.4 nm are accessible to small electrolyte ions, and the area capacitance of obtained sample reaches the ultrahigh value of 330 µF cm-2 , significantly higher than that of previously reported carbon-based materials. The findings provide a better understanding of the correlation between ultra-micropore structure and capacitance and open new avenues for design and development of carbon materials for the next generation of high energy density supercapacitors.

Structural Diversity and Electronic Properties of 3d Transition Metal Tetraphosphides, TMP4 (TM = V, Cr, Mn, and Fe).

Transition-metal (TM) phosphides attract increasing attention with applications for energy conversion and storage, due to their outstanding physical, chemical, and electronic properties. The 3d transition metal tetraphosphides (TMP4, TM = V, Cr, Mn, and Fe) possess multiple allotropies and rich electronic properties. Here, we perform the investigations of the structural, electronic, and elastic properties for 3d-TMP4 (TM = V, Cr, Mn, and Fe) using density functional theory (DFT) calculations. These compounds are featured with alternating buckled phosphorus sheets with ten-numbered phosphorus rings and varied transition-metal layers. Hybrid DFT calculations reveal that TMP4 compounds exhibit a wide range of electrical properties, ranging from metallic behavior for VP4 to semiconducting behavior for CrP4 with the narrow direct band gap of 0.63 eV to enlarged semiconducting MnP4 and FeP4 with band gap of 1.6-2.1 eV. The bonding analysis indicates that P-P and TM-P covalent interactions dominate in the phosphorus sheets and TMP6 octahedrons, which are responsible for the structural and electronic diversity.

Tetracyanomethane under Pressure: Extended CN Polymers from Precursors with Built-in sp3 Centers.

Tetracyanomethane, C(CN)4, is a tetrahedral molecule containing a central sp3 carbon that is coordinated by reactive nitrile groups that could potentially transform to an extended CN network with a significant fraction of sp3 carbon. High-purity C(CN)4 was synthesized, and its physiochemical behavior was studied using in situ synchrotron angle-dispersive powder X-ray diffraction (PXRD) and Raman and infrared (IR) spectroscopies in a diamond anvil cell (DAC) up to 21 GPa. The pressure dependence of the fundamental vibrational modes associated with the molecular solid was determined, and some low-frequency Raman modes are reported for the first time. Crystalline molecular C(CN)4 starts to polymerize above ∼7 GPa and transforms into an interconnected disordered network, which is recoverable to ambient conditions. The results demonstrate feasibility for the pressure-induced polymerization of molecules with premeditated functionality.

Intrinsic defects and their effects on the optical properties in the nonlinear optical crystal CdSiP2: a first-principles study.

In view of their high nonlinear optical coefficients and good phase-matching properties, CdSiP2 (CSP) crystals are considered as one of the most promising materials in the field of nonlinear optical applications. However, the slight absorption losses around 1.34 µm and 1.78 µm under e-polarized light have been affecting its performance. In this study, first-principles calculations were performed to identify the effects of various charge defects on the absorption properties. Different intrinsic defects in the CSP crystal were calculated using the HSE method and compared according to the specific chemical environments in the experiments. The results show that the point defects of V, Si, and V, which can be spontaneously formed, are dominant in the Cd-poor environment. The combination of Si and V defects is the most favorable cluster in the Cd-poor case because of its relatively low formation energy. Furthermore, the antisite defect SiCd was found to be responsible for the main absorption peaks at 1.34 and 1.78 µm in the experimental spectra, whereas other defects and clusters, such as the defects Si and V, also contribute to these red shifted absorptions. Our results intend to provide a guideline for adjusting the optical absorption in CSP by modifying its defects.