Disorder-Broadened Phase Boundary with Enhanced Amorphous Superconductivity in Pressurized In2Te5.

As an empirical tool in materials science and engineering, the iconic phase diagram owes its robustness and practicality to the topological characteristics rooted in the celebrated Gibbs phase law free variables (F) = components (C) - phases (P) + 2. When crossing the phase diagram boundary, the structure transition occurs abruptly, bringing about an instantaneous change in physical properties and limited controllability on the boundaries (F = 1). Here, the sharp phase boundary is expanded to an amorphous transition region (F = 2) by partially disrupting the long-range translational symmetry, leading to a sequential crystalline-amorphous-crystalline (CAC) transition in a pressurized In2Te5 single crystal. Through detailed in situ synchrotron diffraction, it is elucidated that the phase transition stems from the rotation of immobile blocks [In2Te2]2+, linked by hinge-like [Te3]2- trimers. Remarkably, within the amorphous region, the amorphous phase demonstrates a notable 25% increase of the superconducting transition temperature (Tc), while the carrier concentration remains relatively constant. Furthermore, a theoretical framework is proposed revealing that the unconventional boost in amorphous superconductivity might be attributed to an intensified electron correlation, triggered by a disorder-augmented multifractal behavior. These findings underscore the potential of disorder and prompt further exploration of unforeseen phenomena on the phase boundaries.

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.

High-Tc Ferromagnetic Semiconductor in Thinned 3D Ising Ferromagnetic Metal Fe3GaTe2.

Emergent phenomena in exfoliated layered transition metal compounds have attracted much attention in the past several years. Especially, pursuing a ferromagnetic insulator is one of the exciting goals for stimulating a high-performance magnetoelectrical device. Here, we report the transition from a metallic to high-Tc semiconductor-like ferromagnet in thinned Fe3GaTe2, accompanied with competition among various magnetic interactions. As evidenced by critical exponents, Fe3GaTe2 is the first layered ferromagnet described by a 3D Ising model coupled with long-range interactions. An extra magnetic phase from competition between ferromagnetism and antiferromagnetism emerges at a low field below Tc. Upon reducing thickness, the Curie temperature (Tc) monotonically decreases from 342 K for bulk to 200 K for 1-3 nm flakes, which is the highest Tc reported as far as we know. Furthermore, a semiconductor-like behavior has been observed in such 1-3 nm flakes. Our results highlight the importance of Fe3GaTe2 in searching for ferromagnetic insulators, which may benefit spintronic device fabrication.

Ultrasmall single-layered NbSe2 nanotubes flattened within a chemical-driven self-pressurized carbon nanotube.

Pressure can alter interatomic distances and its electrostatic interactions, exerting a profound modifying effect on electron orbitals and bonding patterns. Conventional pressure engineering relies on compressions from external sources, which raises significant challenge in precisely applying pressure on individual molecules and also consume substantial mechanical energy. Here we report ultrasmall single-layered NbSe2 flat tubes (< 2.31 nm) created by self-pressurization during the deselenization of NbSe3 within carbon nanotubes (CNTs). As the internal force (4-17 GPa) is three orders of magnitude larger than the shear strength between CNTs, the flat tube is locked to prevent slippage. Electrical transport measurements indicate that the large pressure within CNTs induces enhanced intermolecular electron correlations. The strictly one-dimensional NbSe2 flat tubes harboring the Luttinger liquid (LL) state, showing a higher tunneling exponent [Formula: see text] than pure CNTs ([Formula: see text]). This work suggests a novel chemical approach to self-pressurization for generating new material configurations and modulating electron interactions.

High, Multiple, and Nonvolatile Polarizations in Organic-Inorganic Hybrid [(CH3)3(CH2CH2Cl)N]2InCl5·H2O for Memcapacitor.

Dielectrics with high, nonvolatile, and multiple polarizations are required for fabricating memcapacitors that enable high parallelism and low energy consumption in artificial neuromorphic computing systems as artificial synapses. Conventional ferroelectric materials based on displacive and order-disorder types generally have difficulty meeting these requirements due to their low polarization values (∼150 µC/cm2) and persistent electrical hysteresis loops. In this study, we report a novel organic-inorganic hybrid (CETM)2InCl5·H2O (CETM = (CH3)3(CH2CH2Cl)N) exhibiting an intriguing polarization vs electric field (charge vs voltage) "hysteresis loop" and a record-high nonvolatile polarization over 30 000 µC/cm2 at room temperature. The polarization is highly dependent on the period and amplitude of the ac voltage, showing multiple nonvolatile states. Electrochemical impedance spectroscopy, time-dependent current behavior, disparate resistor response in the dehydrated derivative (CETM)2InCl5, and the negative temperature dependence of ionic conductance support that the memcapacitor behavior of (CETM)2InCl5·H2O stems from irreversible long-range migration of protons. First-principles calculations further confirm this and clarify the microscale mechanism of anisotropic polarization response. Our findings may open up a new avenue for developing memcapacitors by harnessing the benefits of ion migration in organic-inorganic hybrids.

High anisotropy in electrical and thermal conductivity through the design of aerogel-like superlattice (NaOH)0.5NbSe2.

Interlayer decoupling plays an essential role in realizing unprecedented properties in atomically thin materials, but it remains relatively unexplored in the bulk. It is unclear how to realize a large crystal that behaves as its monolayer counterpart by artificial manipulation. Here, we construct a superlattice consisting of alternating layers of NbSe2 and highly porous hydroxide, as a proof of principle for realizing interlayer decoupling in bulk materials. In (NaOH)0.5NbSe2, the electric decoupling is manifested by an ideal 1D insulating state along the interlayer direction. Vibration decoupling is demonstrated through the absence of interlayer models in the Raman spectrum, dominant local modes in heat capacity, low interlayer coupling energy and out-of-plane thermal conductivity (0.28 W/mK at RT) that are reduced to a few percent of NbSe2's. Consequently, a drastic enhancement of CDW transition temperature (>110 K) and Pauling-breaking 2D superconductivity is observed, suggesting that the bulk crystal behaves similarly to an exfoliated NbSe2 monolayer. Our findings provide a route to achieve intrinsic 2D properties on a large-scale without exfoliation.

Two-Dimensional Pb Square Nets from Bulk (RO)nPb (R = Rare Earth Metals, n = 1,2).

All two-dimensional (2D) materials of group IV elements from Si to Pb are stabilized by carrier doping and interface bonding from substrates except graphene which can be free-standing. The involvement of strong hybrid of bonds, adsorption of exotic atomic species, and the high concentration of crystalline defects are often unavoidable, complicating the measurement of the intrinsic properties. In this work, we report the discovery of seven kinds of hitherto unreported bulk compounds (RO)nPb (R = rare earth metals, n = 1,2), which consist of quasi-2D Pb square nets that are spatially and electronically detached from the [RO]δ+ blocking layers. The band structures of these compounds near Fermi levels are relatively clean and dominantly contributed by Pb, resembling the electron-doped free-standing Pb monolayer. The R2O2Pb compounds are metallic at ambient pressure and become superconductors under high pressures with much enhanced critical fields. In particular, Gd2O2Pb (9.1 µB/Gd) exhibits an interesting bulk response of lattice distortion in conjunction with the emergence of superconductivity and magnetic anomalies at a critical pressure of 10 GPa. Our findings reveal the unexpected facets of 2D Pb sheets that are considerably different from their bulk counterparts and provide an alternative route for exploring 2D properties in bulk materials.

Anomalous enhancement of charge density wave in kagome superconductor CsV3Sb5 approaching the 2D limit.

The recently discovered kagome metals AV3Sb5 (A = Cs, Rb, K) exhibit a variety of intriguing phenomena, such as a charge density wave (CDW) with time-reversal symmetry breaking and possible unconventional superconductivity. Here, we report a rare non-monotonic evolution of the CDW temperature (TCDW) with the reduction of flake thickness approaching the atomic limit, and the superconducting transition temperature (Tc) features an inverse variation with TCDW. TCDW initially decreases to a minimum value of 72 K at 27 layers and then increases abruptly, reaching a record-high value of 120 K at 5 layers. Raman scattering measurements reveal a weakened electron-phonon coupling with the reduction of sample thickness, suggesting that a crossover from electron-phonon coupling to dominantly electronic interactions could account for the non-monotonic thickness dependence of TCDW. Our work demonstrates the novel effects of dimension reduction and carrier doping on quantum states in thin flakes and provides crucial insights into the complex mechanism of the CDW order in the family of AV3Sb5 kagome metals.

Superconductivity in an Orbital-Reoriented SnAs Square Lattice: A Case Study of Li0.6 Sn2 As2 and NaSnAs.

Searching for functional square lattices in layered superconductor systems offers an explicit clue to modify the electron behavior and find exotic properties. The trigonal SnAs3 structural units in SnAs-based systems are relatively conformable to distortion, which provides the possibility to achieve structurally topological transformation and higher superconducting transition temperatures. In the present work, the functional As square lattice was realized and activated in Li0.6 Sn2 As2 and NaSnAs through a topotactic structural transformation of trigonal SnAs3 to square SnAs4 under pressure, resulting in a record-high Tc among all synthesized SnAs-based compounds. Meanwhile, the conductive channel transfers from the out-of-plane pz orbital to the in-plane px +py orbitals, facilitating electron hopping within the square 2D lattice and boosting the superconductivity. The reorientation of p-orbital following a directed local structure transformation provides an effective strategy to modify layered superconducting systems.

Surface microstructures of lunar soil returned by Chang'e-5 mission reveal an intermediate stage in space weathering process.

The lunar soils evolution over time is mainly caused by space weathering that includes the impacts of varying-sized meteoroids and charged particles implantation of solar/cosmic winds as well. It has long been established that space weathering leads to the formation of outmost amorphous layers (50-200 nm in thickness) embedded nanophase iron (npFe0) around the mineral fragments, albeit the origin of the npFe0 remains controversial . The Chang'e-5 (CE-5) mission returned samples feature the youngest mare basalt and the highest latitude sampling site , providing an opportunity to seek the critical clues for understanding the evolution of soils under space weathering. Here, we report the surface microstructures of the major minerals including olivine, pyroxene, anorthite, and glassy beads in the lunar soil of CE-5. Unlike the previous observations, only olivine in all crystals is surrounded by a thinner outmost amorphous SiO2 layer (∼10 nm thick) and embedded wüstite nanoparticles FeO (np-FeO, 3-12 nm in size) instead of npFe0. No foreign volatile elements deposition layer and solar flare tracks can be found on the surface or inside the olivine and other minerals. This unique rim structure has not been reported for any other lunar, terrestrial, Martian, or meteorite samples so far. The observation of wüstite FeO and the microstructures support the existence of an intermediate stage in space weathering for lunar minerals by thermal decomposition.

Delicate superconductivity in nodal-line NaAlGe single crystal.

Nodal-line superconductor NaAlSi with a transition temperature (Tc) of 7 K has attracted considerable attention in recent years, whereas its Ge counterpart, NaAlGe, does not superconduct down to the lowest temperature regardless of their similar atomic and electrical structures. To tackle this enigma, we resort to the growth of NaAlGe single crystal and characterize its ground state. Interestingly, when hole doped by oxidation or extracting Na, single-crystalline NaAlGe transforms from a semimetal/semiconductor to a superconductor (Tc=1.8∼3.3 K) with zero resistivity and a diamagnetic shielding fraction over 100%, but without a thermodynamic response in heat capacity. Continuous x-ray diffraction reveals a transient new structure with a largercaxis, which is suggested to have arisen from the minor loss of Na and to be responsible for the emergence of the delicate superconductivity. Our findings place NaAlGe on an equal footing with NaAlSi and provide an alternative for studying the intriguing relationship between superconductivity and nodal-line topology.

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.

High Entropy van der Waals Materials.

By breaking the restrictions on traditional alloying strategy, the high entropy concept has promoted the exploration of the central area of phase space, thus broadening the horizon of alloy exploitation. This review highlights the marriage of the high entropy concept and van der Waals systems to form a new family of materials category, namely the high entropy van der Waals materials (HEX, HE = high entropy, X = anion clusters) and describes the current issues and next challenges. The design strategy for HEX has integrated the local feature (e.g., composition, spin, and valence states) of structural units in high entropy materials and the holistic degrees of freedom (e.g., stacking, twisting, and intercalating species) in van der Waals materials, and is successfully used for the discovery of high entropy dichalcogenides, phosphorus tri-chalcogenides, halogens, and MXene. The rich combination and random distribution of the multiple metallic constituents on the nearly regular 2D lattice give rise to a flexible platform to study the correlation features behind a range of selected physical properties, e.g., superconductivity, magnetism, and metal-insulator transition. The deliberate design of structural units and their stacking configuration can also create novel catalysts to enhance their performance in a bunch of chemical reactions.

Caging-Pnictogen-Induced Superconductivity in Skutterudites IrX3 (X = As, P).

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-centered tight-binding model, implying a distinct pairing mechanism. Our density functional theory (DFT) calculations reveal an intimate relationship between the pressure-dependent local-phonon mode and the enhancement of Tc. The discovery of XδIr4X12-δ provides an arena to investigate the uncharted territory of hole-doped skutterudites, and the method proposed here represents a new strategy of carrier doping in caged structures, without introducing extra elements.

Discovery of amantadine formate: Toward achieving ultrahigh pyroelectric performances in organics.

Pyroelectrics are a class of polar compounds that output electrical signals upon changes in temperature. With the rapid development of flexible electronics, organic pyroelectrics are highly desired. However, most organics suffer from low pyroelectric coefficients or low working temperatures. To date, the realization of superior pyroelectric performance in all-organics has remained a challenge. Here, we report the discovery of amantadine formate, an all-organic pyroelectric with ultrahigh voltage figures of merit (F v), surpassing those of all other known organics and commercial triglycine sulfate, LiTaO3 as well around room temperature. The key to the high F v is attributed to large pyroelectric coefficients in a favorable temperature range resulting from a ferroelectric-paraelectric phase transition of second order at 327 K, small dielectric constant, and moderate heat capacity. In addition, amantadine formate is relatively lightweight, soft, transparent, low-cost, and non-toxic, adding value to its potential applications in flexible electronics. Our results demonstrate that a new type of pyroelectrics can exist in organic compounds.

Spatially Separated Superconductivity and Enhanced Charge-Density-Wave Ordering in an IrTe2 Nanoflake.

The interplay among collective electronic states like superconductivity (SC) and charge density wave (CDW) is of significance in transition metal dichalcogenides. To date, a consensus on the relationship between SC and CDW has not been established in IrTe2. Here we use the Au-assisted exfoliation method to cleave IrTe2 down to 10 nm. A striking feature is the concurrence of phase separation in a single piece of nanoflake, i.e., the superconducting (P3̅m1) and CDW (P3̅) phases. In the former area, the dimensional fluctuations suppress the CDW ordering and induce SC at 3.5 K. The CDW area at the phase boundary shows enhanced TCDW at 605 K (TCDW = 280 K in the bulk phase), which is accompanied by a unique wrinkle. Detailed analyses suggest that the strain-induced bond breaking of Te-Te dimers favors the CDW. Our works provide compelling evidence of competition between SC and CDW in IrTe2.

Competition of Superconductivity and Charge Density Wave in Selective Oxidized CsV_{3}Sb_{5} Thin Flakes.

The recently discovered layered kagome metals AV_{3}Sb_{5} (A=K, Rb, and Cs) with vanadium kagome networks provide a novel platform to explore correlated quantum states intertwined with topological band structures. Here we report the prominent effect of hole doping on both superconductivity and charge density wave (CDW) order, achieved by selective oxidation of exfoliated thin flakes. A superconducting dome is revealed as a function of the effective doping content. The superconducting transition temperature (T_{c}) and upper critical field in thin flakes are significantly enhanced compared with the bulk, which are accompanied by the suppression of CDW. Our detailed analyses establish the pivotal role of van Hove singularities in promoting correlated quantum orders in these kagome metals. Our experiments not only demonstrate the intriguing nature of superconducting and CDW orders, but also provide a novel route to tune the carrier concentration through both selective oxidation and electric gating. This establishes CsV_{3}Sb_{5} as a tunable 2D platform for the further exploration of topology and correlation among 3d electrons in kagome lattices.

High-Entropy van der Waals Materials Formed from Mixed Metal Dichalcogenides, Halides, and Phosphorus Trisulfides.

The charge, spin, and composition degrees of freedom in a high-entropy alloy endow it with tunable valence and spin states, infinite combinations, and excellent mechanical performance. Meanwhile, the stacking, interlayer, and angle degrees of freedom in a van der Waals material bring to it exceptional features and technological applications. Integration of these two distinct material categories while keeping their merits would be tempting. On the basis of this heuristic thinking, we design and explore a new range of materials (i.e., dichalcogenides, halides, and phosphorus trisulfides) with multiple metallic constitutions and intrinsic layered structure, which are coined as high-entropy van der Waals materials. Millimeter-scale single crystals with a homogeneous element distribution can be efficiently acquired and easily exfoliated or intercalated in this materials category. Multifarious physical properties such as superconductivity, magnetic ordering, metal-insulator transition, and corrosion resistance have been exploited. Further research based on the concept of high-entropy van der Waals materials will enrich the high-throughput design of new systems with intriguing properties and practical applications.

Superconductivity from buckled-honeycomb-vacancy ordering.

Vacancies are prevalent and versatile in solid-state physics and materials science. The role of vacancies in strongly correlated materials, however, remains uncultivated until now. Here, we report the discovery of an unprecedented vacancy state forming an extended buckled-honeycomb-vacancy (BHV) ordering in Ir16Sb18. Superconductivity emerges by suppressing the BHV ordering through squeezing of extra Ir atoms into the vacancies or isovalent Rh substitution. The phase diagram on vacancy ordering reveals the superconductivity competes with the BHV ordering. Further theoretical calculations suggest that this ordering originates from a synergistic effect of the vacancy formation energy and Fermi surface nesting with a wave vector of (1/3, 1/3, 0). The buckled structure breaks the crystal inversion symmetry and can mostly suppress the density of states near the Fermi level. The peculiarities of BHV ordering highlight the importance of "correlated vacancies" and may serve as a paradigm for exploring other non-trivial excitations and quantum criticality.

A Highly Efficient and Stable Blue-Emitting Cs5 Cu3 Cl6 I2 with a 1D Chain Structure.

In the field of photonics, alkali copper(I) halides attract considerable attention as lead-free emitters. The intrinsic quantum confinement effects originating from low-dimensional electronic structure lead to high photoluminescence quantum yields (PLQYs). Among them, Cs3 Cu2 I5 is the most promising candidate, satisfying both high PLQY and air stability. In this study, a strategy to explore a new material meeting these requirements through the use of the mixed-anions of I- and Cl- is proposed. The expectation is maintained that the large difference in ionic radii between them likely results in the formation of a novel compound. Consequently, Cs5 Cu3 Cl6 I2 with a 1D zigzag chain structure is discovered. This material exhibits blue emission (≈462 nm) with a near-unity quantum yield of 95%. An electronic structure calculation reveals that the localized nature of the valence band maximum is crucial in obtaining efficient self-trapped exciton emission. Moreover, the iodine-bridged 1D connectivity significantly enhances the chemical stability of Cs5 Cu3 Cl6 I2 , compared with the pure chloride phase. The present findings provide a new perspective for developing air-stable alkali copper(I) halides with highly efficient luminescence.