Breaking New Ground: MBene Route toward Selective Vinyl Double Bond Hydrogenation in Nitroarenes.

Doping, or incremental substitution of one element for another, is an effective way to tailor a compound's structure as well as its physical and chemical properties. Herein, we replaced up to 30% of Ni with Co in members of the family of layered LiNiB compounds, stabilizing the high-temperature polymorph of LiNiB while the room-temperature polymorph does not form. By studying this layered boride with in situ high-temperature powder diffraction, we obtained a distorted variant of LiNi0.7Co0.3B featuring a perfect interlayer placement of [Ni0.7Co0.3B] layers on top of each other─a structural motif not seen before in other borides. Because of the Co doping, LiNi0.7Co0.3B can undergo a nearly complete topochemical Li deintercalation under ambient conditions, resulting in a metastable boride with the formula Li0.04Ni0.7Co0.3B. Heating of Li0.04Ni0.7Co0.3B in anaerobic conditions led to yet another metastable boride, Li0.01Ni0.7Co0.3B, with a CoB-type crystal structure that cannot be obtained by simple annealing of Ni, Co, and B. No significant alterations of magnetic properties were detected upon Co-doping in the temperature-independent paramagnet LiNi0.7Co0.3B or its Li-deintercalated counterparts. Finally, Li0.01Ni0.7Co0.3B stands out as an exceptional catalyst for the selective hydrogenation of the vinyl C═C bond in 3-nitrostyrene, even in the presence of other competing functional groups. This research showcases an innovative approach to heterogeneous catalyst design by meticulously synthesizing metastable compounds.

Strong enhancement of magnetic ordering temperature and structural/valence transitions in EuPd3S4 under high pressure.

We present a comprehensive study of the inhomogeneous mixed-valence compound, EuPd3S4, by electrical transport, X-ray diffraction, time-domain 151Eu synchrotron Mössbauer spectroscopy, and X-ray absorption spectroscopy measurements under high pressure. Electrical transport measurements show that the antiferromagnetic ordering temperature, TN, increases rapidly from 2.8 K at ambient pressure to 23.5 K at ~19 GPa and plateaus between ~19 and ~29 GPa after which no anomaly associated with TN is detected. A pressure-induced first-order structural transition from cubic to tetragonal is observed, with a rather broad coexistence region (~20 GPa to ~30 GPa) that corresponds to the TN plateau. Mössbauer spectroscopy measurements show a clear valence transition from approximately 50:50 Eu2+:Eu3+ to fully Eu3+ at ~28 GPa, consistent with the vanishing of the magnetic order at the same pressure. X-ray absorption data show a transition to a fully trivalent state at a similar pressure. Our results show that pressure first greatly enhances TN, most likely via enhanced hybridization between the Eu 4f states and the conduction band, and then, second, causes a structural phase transition that coincides with the conversion of the europium to a fully trivalent state.

Electronic signatures of successive itinerant, antiferromagnetic transitions in hexagonal La2Ni7.

We use high-resolution angle-resolved photoemission spectroscopy (ARPES) and density functional theory (DFT) calculations to study the electronic and magnetic properties of La2Ni7, an itinerant magnetic system with a series of three magnetic transition temperatures upon cooling, which end in a weak antiferromagnetic ground state. Our APRES data reveal several electron and hole pockets that have hexagonal symmetry near the Γ point. We observe significant reconstruction of the band structure upon successive magnetic transitions atT1∼ 61 K,T2∼ 57 K andT3∼ 42 K. Several features observed in ARPES data were reasonably well reproduced by DFT calculations, while others were not. In particular, the flat band nearEFpredicted by DFT in antiferromagnet (AFM) state, was seemingly absent in ARPES data. Our results detail the effects of magnetic ordering on the electronic structure in a Ni-based weak AFM and highlight challenges of current computational methods.

Tuning the Intermediate Valence Behavior in the Zintl Compound Yb14ZnSb11 by Incorporation of RE3+ [Yb14-xRExZnSb11 (0.2 ≤ x ≤ 0.7), RE = Sc, Y, La, Lu and Gd].

The solid solutions of Yb14-xRExZnSb11 (RE = Sc, Y, La, Lu, and Gd; 0.2 ≤ x ≤ 0.7) were prepared to probe the intermediate valency of Yb in Yb14ZnSb11. The substitution of Yb with RE3+ elements should reduce or remove the intermediate valency of the remaining Yb ions. Large crystals are grown from Sn-flux, and the structure and magnetic susceptibility are presented. All compounds crystallize in the Ca14AlSb11 structure type and the RE3+ ions show Yb site substitution preferences that correlate with size. Two compositions of Yb14-xYxZnSb11 were investigated [x = 0.38(3), 0.45(3)] by temperature-dependent magnetic susceptibility and the broad feature in magnetic susceptibility measurements at 85 K in pristine Yb14ZnSb11 attributed to valence fluctuation decreases and is absent for x = 0.45(3). In compounds with nonmagnetic RE3+ substitutions (Sc, Y, La, and Lu), temperature-dependent magnetic susceptibility shows a transition from intermediate valency fluctuation toward temperature-independent (Y, La, and Lu) or Curie-Weiss behavior and possibly low temperature heavy Fermion behavior (Sc). In the example of the magnetic rare earth substitution, RE = Gd, the Curie-Weiss-dependent magnetic moment of Gd3+ is consistent with x. Hall resistivity of Yb14-xYxZnSb11 showed that the carrier concentration decreases with x and the signature of the low-T intermediate valence state seen for x = 0 is suppressed for x = 0.38 and gone for x = 0.45.

Path Less Traveled: A Contemporary Twist on Synthesis and Traditional Structure Solution of Metastable LiNi12B8.

Achieving kinetic control to synthesize metastable compounds is a challenging task, especially in solid-state reactions where the diffusion is slow. Another challenge is the unambiguous crystal structure determination for metastable compounds when high-quality single crystals suitable for single-crystal X-ray diffraction are inaccessible. In this work, we report an unconventional means of synthesis and an effective strategy to solve the crystal structure of an unprecedented metastable compound LiNi12B8. This compound can only be produced upon heating a metastable layered boride, HT-Li0.4NiB (HT: high temperature), in a sealed niobium container. A conventional heating and annealing of elements do not yield the title compound, which is consistent with the metastable nature of LiNi12B8. The process to crystallize this compound is sensitive to the annealing temperature and dwelling time, a testament to the complex kinetics involved in the formation of the product. The unavailability of crystals suitable for single-crystal X-ray diffraction experiments prompted solving the crystal structure from high-resolution synchrotron powder X-ray diffraction data. This compound crystallizes in a new structure type with space group I4/mmm (a = 10.55673(9) Å, c = 10.00982(8) Å, V = 1115.54(3) Å3, Z = 6). The resulting complex crystal structure of LiNi12B8 is confirmed by scanning transmission electron microscopy and solid-state 11B and 7Li NMR spectroscopy analyses. The extended Ni framework with Li/Ni disorder in its crystal structure resulted in the spin-glass or cluster glass type magnetic ordering below 24 K. This report illustrates a "contemporary twist" to traditional methodologies toward synthesizing a metastable compound and provides a recipe for solving structures by combining the complementary characterization techniques in the cases where the traditionally used single-crystal X-ray diffraction method is nonapplicable.

Tuning of Cr-Cr Magnetic Exchange through Chalcogenide Linkers in Cr2 Molecular Dimers.

A set of three Cr-dimer compounds, Cr2Q2(en)4X2 (Q: S, Se; X: Br, Cl; en: ethylenediamine), with monoatomic chalcogenide bridges have been synthesized via a single-step solvothermal route. Chalcogenide linkers mediate magnetic exchange between Cr3+ centers, while bidentate ethylenediamine ligands complete the distorted octahedral coordination of Cr centers. Unlike the compounds previously reported, none of the chalcogenide atoms are connected to extra ligands. Magnetic susceptibility studies indicate antiferromagnetic coupling between Cr3+ centers, which are moderate in Cr2Se2(en)4X2 and stronger in Cr2S2(en)4Cl2. Fitting the magnetic data requires a biquadratic exchange term. High-frequency EPR spectra showing characteristic signals due to coupled S = 1 spin states could be interpreted in terms of the "giant spin" Hamiltonian. A fourth compound, Cr2Se8(en)4, has a single diatomic Se bridge connecting the two Cr3+ centers and shows weak ferromagnetic exchange interactions. This work demonstrates the tunability in strength and type of exchange interactions between metal centers by manipulating the interatomic distances and number of bridging chalcogenide linkers.

Emergence of Fermi arcs due to magnetic splitting in an antiferromagnet.

The Fermi surface plays an important role in controlling the electronic, transport and thermodynamic properties of materials. As the Fermi surface consists of closed contours in the momentum space for well-defined energy bands, disconnected sections known as Fermi arcs can be signatures of unusual electronic states, such as a pseudogap1. Another way to obtain Fermi arcs is to break either the time-reversal symmetry2 or the inversion symmetry3 of a three-dimensional Dirac semimetal, which results in formation of pairs of Weyl nodes that have opposite chirality4, and their projections are connected by Fermi arcs at the bulk boundary3,5-12. Here, we present experimental evidence that pairs of hole- and electron-like Fermi arcs emerge below the Neel temperature (TN) in the antiferromagnetic state of cubic NdBi due to a new magnetic splitting effect. The observed magnetic splitting is unusual, as it creates bands of opposing curvature, which change with temperature and follow the antiferromagnetic order parameter. This is different from previous theoretically considered13,14 and experimentally reported cases15,16 of magnetic splitting, such as traditional Zeeman and Rashba, in which the curvature of the bands is preserved. Therefore, our findings demonstrate a type of magnetic band splitting in the presence of a long-range antiferromagnetic order that is not readily explained by existing theoretical ideas.

Topological magnetic hysteresis in single crystals of CeAgSb2ferromagnet.

Closed-topology magnetic domains are usually observed in thin films and in an applied magnetic field. Here we report the observation of rectangular cross-section tubular ferromagnetic domains in thick single crystals of CeAgSb2in zero applied field. Relatively low exchange energy, small net magnetic moment, and anisotropic in-plane crystal electric fields lower the domain wall energy and allow for the formation of the closed-topology patterns. The tubular domain structure irreversibly transforms into a dendritic pattern upon cycling the magnetic field. This transition between closed and open topologies results in a 'topological magnetic hysteresis'- the actual hysteresis in magnetization, not due to the imperfections and pinning, but due to the difference in the pattern morphology. Similar physics was suggested before in pure type-I superconductors and is believed to be a generic feature of other nonlinear single (present case), or two-phase (type-I superconductor) systems where the effects similar to demagnetization (shape-dependent macroscopic variation of properties) lead to pattern formation.

A Low-Temperature Structural Transition in Canfieldite, Ag8SnS6, Single Crystals.

Canfieldite, Ag8SnS6, is a semiconducting mineral notable for its high ionic conductivity, photosensitivity, and low thermal conductivity. We report the solution growth of large single crystals of Ag8SnS6 of mass up to 1 g from a ternary Ag-Sn-S melt. On cooling from high temperature, Ag8SnS6 undergoes a known cubic (F4̅3m) to orthorhombic (Pna21) phase transition at ≈460 K. By studying the magnetization and thermal expansion between 5-300 K, we discover a second structural transition at ≈120 K. Single crystal X-ray diffraction reveals the low-temperature phase adopts a different orthorhombic structure with space group Pmn21 (a = 7.662 9(5) Å, b = 7.539 6(5) Å, c = 10.630 0(5) Å, Z = 2 at 90 K) that is isostructural to the room-temperature forms of the related Se-based compounds Ag8SnSe6 and Ag8GeSe6. The 120 K transition is first-order and has a large thermal hysteresis. On the basis of the magnetization and thermal expansion data, the room-temperature polymorph can be kinetically arrested into a metastable state by rapidly cooling to temperatures below 40 K. We last compare the room- and low-temperature forms of Ag8SnS6 with its argyrodite analogues, Ag8TQ6 (T = Si, Ge, Sn; Q = S, Se), and identify a trend relating the preferred structures to the unit cell volume, suggesting smaller phase volume favors the Pna21 arrangement. We support this picture by showing that the transition to the Pmn21 phase is avoided in Ge alloyed Ag8Sn1-xGexS6 samples as well as in pure Ag8GeS6.

Simplified feedback control system for scanning tunneling microscopy.

A Scanning Tunneling Microscope (STM) is one of the most important scanning probe tools available to study and manipulate matter at the nanoscale. In a STM, a tip is scanned on top of a surface with a separation of a few Å. Often, the tunneling current between the tip and the sample is maintained constant by modifying the distance between the tip apex and the surface through a feedback mechanism acting on a piezoelectric transducer. This produces very detailed images of the electronic properties of the surface. The feedback mechanism is nearly always made using a digital processing circuit separate from the user computer. Here, we discuss another approach using a computer and data acquisition through the universal serial bus port. We find that it allows successful ultralow noise studies of surfaces at cryogenic temperatures. We show results on different compounds including a type II Weyl semimetal (WTe2), a quasi-two-dimensional dichalcogenide superconductor (2H-NbSe2), a magnetic Weyl semimetal (Co3Sn2S2), and an iron pnictide superconductor (FeSe).

Pseudoelasticity of SrNi2P2 Micropillar via Double Lattice Collapse and Expansion.

The maximum recoverable strain of most crystalline solids is less than 1% because plastic deformation or fracture usually occurs at a small strain. In this work, we show that a SrNi2P2 micropillar exhibits pseudoelasticity with a large maximum recoverable strain of ∼14% under uniaxial compression via unique reversible structural transformation, double lattice collapse-expansion that is repeatable under cyclic loading. Its high yield strength (∼3.8 ± 0.5 GPa) and large maximum recoverable strain bring out the ultrahigh modulus of resilience (∼146 ± 19 MJ/m3), a few orders of magnitude higher than that of most engineering materials. The double lattice collapse-expansion mechanism shows stress-strain behaviors similar to that of conventional shape-memory alloys, such as hysteresis and thermo-mechanical actuation, even though the structural changes involved are completely different. Our work suggests that the discovery of a new class of high-performance ThCr2Si2-structured materials will open new research opportunities in the field of pseudoelasticity.

Flat band carrier confinement in magic-angle twisted bilayer graphene.

Magic-angle twisted bilayer graphene has emerged as a powerful platform for studying strongly correlated electron physics, owing to its almost dispersionless low-energy bands and the ability to tune the band filling by electrostatic gating. Techniques to control the twist angle between graphene layers have led to rapid experimental progress but improving sample quality is essential for separating the delicate correlated electron physics from disorder effects. Owing to the 2D nature of the system and the relatively low carrier density, the samples are highly susceptible to small doping inhomogeneity which can drastically modify the local potential landscape. This potential disorder is distinct from the twist angle variation which has been studied elsewhere. Here, by using low temperature scanning tunneling spectroscopy and planar tunneling junction measurements, we demonstrate that flat bands in twisted bilayer graphene can amplify small doping inhomogeneity that surprisingly leads to carrier confinement, which in graphene could previously only be realized in the presence of a strong magnetic field.

Discovery of a weak topological insulating state and van Hove singularity in triclinic RhBi2.

Time reversal symmetric (TRS) invariant topological insulators (TIs) fullfil a paradigmatic role in the field of topological materials, standing at the origin of its development. Apart from TRS protected strong TIs, it was realized early on that more confounding weak topological insulators (WTI) exist. WTIs depend on translational symmetry and exhibit topological surface states only in certain directions making it significantly more difficult to match the experimental success of strong TIs. We here report on the discovery of a WTI state in RhBi2 that belongs to the optimal space group P[Formula: see text], which is the only space group where symmetry indicated eigenvalues enumerate all possible invariants due to absence of additional constraining crystalline symmetries. Our ARPES, DFT calculations, and effective model reveal topological surface states with saddle points that are located in the vicinity of a Dirac point resulting in a van Hove singularity (VHS) along the (100) direction close to the Fermi energy (EF). Due to the combination of exotic features, this material offers great potential as a material platform for novel quantum effects.

Topochemical Deintercalation of Li from Layered LiNiB: toward 2D MBene.

The pursuit of two-dimensional (2D) borides, MBenes, has proven to be challenging, not the least because of the lack of a suitable precursor prone to the deintercalation. Here, we studied room-temperature topochemical deintercalation of lithium from the layered polymorphs of the LiNiB compound with a considerable amount of Li stored in between [NiB] layers (33 at. % Li). Deintercalation of Li leads to novel metastable borides (Li∼0.5NiB) with unique crystal structures. Partial removal of Li is accomplished by exposing the parent phases to air, water, or dilute HCl under ambient conditions. Scanning transmission electron microscopy and solid-state 7Li and 11B NMR spectroscopy, combined with X-ray pair distribution function (PDF) analysis and DFT calculations, were utilized to elucidate the novel structures of Li∼0.5NiB and the mechanism of Li-deintercalation. We have shown that the deintercalation of Li proceeds via a "zip-lock" mechanism, leading to the condensation of single [NiB] layers into double or triple layers bound via covalent bonds, resulting in structural fragments with Li[NiB]2 and Li[NiB]3 compositions. The crystal structure of Li∼0.5NiB is best described as an intergrowth of the ordered single [NiB], double [NiB]2, or triple [NiB]3 layers alternating with single Li layers; this explains its structural complexity. The formation of double or triple [NiB] layers induces a change in the magnetic behavior from temperature-independent paramagnets in the parent LiNiB compounds to the spin-glassiness in the deintercalated Li∼0.5NiB counterparts. LiNiB compounds showcase the potential to access a plethora of unique materials, including 2D MBenes (NiB).

Characterization of the pressure coefficient of manganin and temperature evolution of pressure in piston-cylinder cells.

We report measurements of the temperature- and pressure-dependent resistance, R(T, p), of a manganin manometer in a 4He-gas pressure setup from room temperature down to the solidification temperature of 4He (Tsolid ∼ 50 K at 0.8 GPa) for pressures, p, between 0 GPa and ∼0.8 GPa. The same manganin wire manometer was also measured in a piston-cylinder cell (PCC) from 300 K down to 1.8 K and for pressures between 0 GPa and ∼2 GPa. From these data, we infer the temperature and pressure dependence of the pressure coefficient of manganin, α(T, p), defined by the equation Rp = (1 + αp)R0, where R0 and Rp are the resistances of manganin at ambient pressure and finite pressure, respectively. Our results indicate that upon cooling, α first decreases, then goes through a broad minimum at ∼120 K, and increases again toward lower temperatures. In addition, we find that α is almost pressure-independent at T ≳ 60 K up to p ∼ 2 GPa, but shows a pronounced p dependence at T ≲ 60 K. Using this manganin manometer, we demonstrate that p overall decreases with decreasing temperature in the PCC for the full pressure range and that the size of the pressure difference between room temperature and low temperatures (T = 1.8 K), Δp, decreases with increasing pressure. We also compare the pressure values inferred from the manganin manometer with the low-temperature pressure, determined from the superconducting transition temperature of elemental lead (Pb). As a result of these data and analysis, we propose a practical algorithm to infer the evolution of pressure with temperature in a PCC.

Measurements of elastoresistance under pressure by combining in-situ tunable quasi-uniaxial stress with hydrostatic pressure.

Uniaxial stress, as well as hydrostatic pressure are often used to tune material properties in condensed matter physics. Here, we present a setup that allows for the study of the combined effects of quasi-uniaxial stress and hydrostatic pressure. Following earlier designs for measurements under finite stress at ambient pressures [e.g., Chu et al., Science 337, 710 (2012)], the present setup utilizes a piezoelectric actuator to change stress in situ inside the piston-cylinder pressure cell. We show that the actuator can be operated over the full temperature (from 30 K up to 260 K) and pressure range (up to ≈2 GPa), resulting in a clear and measurable quasi-uniaxial strain. To demonstrate functionality, measurements of the elastoresistance (i.e., the change of resistance of a sample as a response to quasi-uniaxial strain) under finite hydrostatic pressure on the iron-based compound BaFe2As2 are presented as a proof-of-principle example and discussed in the framework of electronic nematicity. Overall, this work introduces the combination of in situ tunable quasi-uniaxial stress and large (up to ≈2 GPa) hydrostatic pressure as a powerful combination in the study of novel electronic phases. In addition, it also points toward further technical advancements which can be made in the future.

New materials physics.

This review presents a survey of, and guide to, new materials physics (NMP) research. It begins with an overview of the goals of NMP and then presents important ideas and techniques for the design and growth of new materials. An emphasis is placed on the use of compositional phase diagrams to inform and motivate solution growth of single crystals. The second half of this review focuses on the vital process of generating actionable ideas for the growth and discovery of new materials and ground states. Motivations ranging from (1) wanting a specific compound, to (2) wanting a specific ground state to (3) wanting to explore for known and unknown unknowns, will be discussed and illustrated with abundant examples. The goal of this review is to inform, inspire, an even entertain, as many practitioners of this field as possible.

Magnetoelastoresistance in WTe2: Exploring electronic structure and extremely large magnetoresistance under strain.

Strain describes the deformation of a material as a result of applied stress. It has been widely employed to probe transport properties of materials, ranging from semiconductors to correlated materials. In order to understand, and eventually control, transport behavior under strain, it is important to quantify the effects of strain on the electronic bandstructure, carrier density, and mobility. Here, we demonstrate that much information can be obtained by exploring magnetoelastoresistance (MER), which refers to magnetic field-driven changes of the elastoresistance. We use this powerful approach to study the combined effect of strain and magnetic fields on the semimetallic transition metal dichalcogenide [Formula: see text] We discover that WTe2 shows a large and temperature-nonmonotonic elastoresistance, driven by uniaxial stress, that can be tuned by magnetic field. Using first-principle and analytical low-energy model calculations, we provide a semiquantitative understanding of our experimental observations. We show that in [Formula: see text], the strain-induced change of the carrier density dominates the observed elastoresistance. In addition, the change of the mobilities can be directly accessed by using MER. Our analysis also reveals the importance of a heavy-hole band near the Fermi level on the elastoresistance at intermediate temperatures. Systematic understanding of strain effects in single crystals of correlated materials is important for future applications, such as strain tuning of bulk phases and fabrication of devices controlled by strain.

Bulk Superconductivity and Role of Fluctuations in the Iron-Based Superconductor FeSe at High Pressures.

The iron-based superconductor FeSe offers a unique possibility to study the interplay of superconductivity with purely nematic as well magnetic-nematic order by pressure (p) tuning. By measuring specific heat under p up to 2.36 GPa, we study the multiple phases in FeSe using a thermodynamic probe. We conclude that superconductivity is bulk across the entire p range and competes with magnetism. In addition, whenever magnetism is present, fluctuations exist over a wide temperature range above both the bulk superconducting and the magnetic transitions. Whereas the magnetic fluctuations are likely temporal, the superconducting fluctuations may be either temporal or spatial. These observations highlight similarities between FeSe and underdoped cuprate superconductors.