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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.
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Neutron diffraction and spectroscopy offer unique insight into structures and properties of solids and molecular materials. All neutron instruments located at the various neutron sources are distinct, even if their designs are based on similar principles, and thus, they are usually less familiar to the community than commercial X-ray diffractometers and optical spectrometers. Major neutron instruments in the USA, which are open to scientists around the world, and examples of their use in coordination chemistry research are presented here, along with a list of similar instruments at main neutron facilities in other countries. The reader may easily and quickly find from this minireview an appropriate neutron instrument for research. The instruments include single-crystal and powder diffractometers to determine structures, inelastic neutron scattering (INS) spectrometers to probe magnetic and vibrational excitations, and quasielastic neutron scattering (QENS) spectrometers to study molecular dynamics such as methyl rotation on ligands. Key and unique features of the diffraction and neutron spectroscopy that are relevant to inorganic chemistry are reviewed.
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The kagome metals display an intriguing variety of electronic and magnetic phases arising from the connectivity of atoms on a kagome lattice. A growing number of these materials with vanadium-kagome nets host charge-density waves (CDWs) at low temperatures, including ScV6Sn6, CsV3Sb5, and V3Sb2. Curiously, only the Sc version of the RV6Sn6 materials with a HfFe6Ge6-type structure hosts a CDW (R = Gd-Lu, Y, Sc). In this study, we investigate the role of rare earth size in CDW formation in the RV6Sn6 compounds. Magnetization measurements on our single crystals of (Sc,Lu)V6Sn6 and (Sc,Y)V6Sn6 establish that the CDW is suppressed by substituting Sc by larger Lu or Y. Single-crystal X-ray diffraction reveals that compressible Sn-Sn bonds accommodate the larger rare earth atoms within loosely packed R-Sn-Sn chains without significantly expanding the lattice. We propose that Sc provides extra room in these chains crucial to CDW formation in ScV6Sn6. Our rattling chain model explains why both physical pressure and substitution by larger rare earth atoms hinder CDW formation despite opposite impacts on lattice size. We emphasize the cooperative effect of pressure and rare earth size by demonstrating that pressure further suppresses the CDW in a Lu-doped ScV6Sn6 crystal. Our model not only addresses why a CDW only forms in the RV6Sn6 materials with tiny Sc but also advances our understanding of why unusual CDWs form in the kagome metals.
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Materials hosting kagome lattices have drawn interest for the diverse magnetic and electronic states generated by geometric frustration. In the AV_{3}Sb_{5} compounds (A=K, Rb, Cs), stacked vanadium kagome layers give rise to unusual charge density waves (CDW) and superconductivity. Here we report single-crystal growth and characterization of ScV_{6}Sn_{6}, a hexagonal HfFe_{6}Ge_{6}-type compound that shares this structural motif. We identify a first-order phase transition at 92 K. Single crystal x-ray and neutron diffraction reveal a charge density wave modulation of the atomic lattice below this temperature. This is a distinctly different structural mode than that observed in the AV_{3}Sb_{5} compounds, but both modes have been anticipated in kagome metals. The diverse HfFe_{6}Ge_{6} family offers more opportunities to tune ScV_{6}Sn_{6} and explore density wave order in kagome lattice materials.
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We describe the crystal structure and elementary magnetic properties of a previously unreported ternary intermetallic compound, Cr4PtGa17, which crystallizes in a rhombohedral unit cell in the noncentrosymmetric space group R3m. The crystal structure is closely related to those of XYZ half-Heusler compounds, where X, Y, and Z are reported to be single elements only, occupying three different face-centered-cubic sublattices. The new material, Cr4PtGa17, can be most straightforwardly illustrated by writing the formula as (PtGa2)(Cr4Ga14)Ga (X = PtGa2, Y = Cr4Ga14, Z = Ga); that is, the X and Y sites are occupied by clusters instead of single elements. The magnetic Cr occupies a breathing pyrochlore lattice. Ferromagnetic ordering is found below TC â¼ 61 K, by both neutron diffraction and magnetometer studies, with a small, saturated moment of â¼0.25 µB/Cr observed at 2 K, making Cr4PtGa17 the first ferromagnetically ordered material with a breathing pyrochlore lattice. A magnetoresistance of â¼140% was observed at 2 K. DFT calculations suggest that the material has a nearly half-metallic electronic structure. The new material, Cr4PtGa17, the first realization of both a half-Heusler-type structure and a breathing pyrochlore lattice, might pave a new way to achieve novel types of half-Heusler compounds.
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In materials showing a linear magnetoelectric (ME) effect, unconventional functionalities can be anticipated such as electric control of magnetism and nonreciprocal optical responses. Thus, the search for new linear ME materials is of interest in materials science. Here, using a recently proposed design principle of linear ME materials, which is based on the combination of local structural asymmetry and collinear antiferromagnetism, we demonstrate that an anion-deficient fluorite derivative, Mn3Ta2O8, is a new linear ME material. This is evidenced by the onset of magnetic-field-induced electric polarization in its collinear antiferromagnetic phase below TN = 24 K. Furthermore, we also find an antiferroelectric-like phase transition at TS = 55 K, which is attributable to an off-center displacement of magnetic Mn2+ ions. The present study shows that Mn3Ta2O8 is a rare material that exhibits both ME and antiferroelectric-like transitions. Thus, Mn3Ta2O8 may provide an opportunity to investigate the physics associated with complicated interactions between magnetic (spin) and electric dipole degrees of freedom.
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Superconductivity in FeSe emerges from a nematic phase that breaks four-fold rotational symmetry in the iron plane. This phase may arise from orbital ordering, spin fluctuations or hidden magnetic quadrupolar order. Here we use inelastic neutron scattering on a mosaic of single crystals of FeSe, detwinned by mounting on a BaFe2As2 substrate to demonstrate that spin excitations are most intense at the antiferromagnetic wave vectors QAF = (±1, 0) at low energies E = 6-11 meV in the normal state. This two-fold (C2) anisotropy is reduced at lower energies, 3-5 meV, indicating a gapped four-fold (C4) mode. In the superconducting state, however, the strong nematic anisotropy is again reflected in the spin resonance (E = 3.6 meV) at QAF with incommensurate scattering around 5-6 meV. Our results highlight the extreme electronic anisotropy of the nematic phase of FeSe and are consistent with a highly anisotropic superconducting gap driven by spin fluctuations.
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A new member of the descloizite family, a cobalt vanadate, SrCo(VO4)(OH), has been synthesized as large single crystals using high-temperature and high-pressure hydrothermal methods. SrCo(VO4)(OH) crystallizes in the orthorhombic crystal system in space group P212121 with the following unit cell parameters: a = 6.0157(2) Å, b = 7.645(2) Å, c = 9.291(3) Å, V = 427.29(2) Å3, and Z = 4. It contains one-dimensional Co-O-Co chains of edge-sharing CoO6 octahedra along the a-axis connected to each other via VO4 tetrahedra along the b-axis forming a three-dimensional structure. The magnetic susceptibility of SrCo(VO4)(OH) indicates an antiferromagnetic transition at 10 K as well as unusually large spin orbit coupling. Single-crystal magnetic measurements in all three main crystallographic directions displayed a significant anisotropy in both temperature- and field-dependent data. Single-crystal neutron diffraction at 4 K was used to characterize the magnetically ordered state. The Co2+ magnetic spins are arranged in a staggered configuration along the chain direction, with a canting angle that follows the tipping of the CoO6 octahedra. The net magnetization along the chain direction, resulting in ferromagnetic coupling of the a-axis spin components in each chain, is compensated by an antiferromagnetic interaction between nearest neighbor chains. A metamagnetic transition appears in the isothermal magnetization data at 2 K along the chain direction, which seems to correspond to a co-alignment of the spin directions of the nearest neighbor chain. We propose a phenomenological spin Hamiltonian that describes the canted spin configuration of the ground state and the metamagnetic transition in SrCo(VO4)(OH).
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Superconductivity in the iron pnictides emerges from metallic parent compounds exhibiting intertwined stripe-type magnetic order and nematic order, with itinerant electrons suggested to be essential for both. Here we use x-ray and neutron scattering to show that a similar intertwined state is realized in semiconducting KFe_{0.8}Ag_{1.2}Te_{2} (K_{5}Fe_{4}Ag_{6}Te_{10}) without itinerant electrons. We find that Fe atoms in KFe_{0.8}Ag_{1.2}Te_{2} form isolated 2×2 blocks, separated by nonmagnetic Ag atoms. Long-range magnetic order sets in below T_{N}≈35 K, with magnetic moments within the 2×2 Fe blocks ordering into the stripe-type configuration. A nematic order accompanies the magnetic transition, manifest as a structural distortion that breaks the fourfold rotational symmetry of the lattice. The nematic orders in KFe_{0.8}Ag_{1.2}Te_{2} and iron pnictide parent compounds are similar in magnitude and in how they relate to the magnetic order, indicating a common origin. Since KFe_{0.8}Ag_{1.2}Te_{2} is a semiconductor without itinerant electrons, this indicates that local-moment magnetic interactions are integral to its magnetic and nematic orders, and such interactions may play a key role in iron-based superconductivity.
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The unconventional electronic ground state of Sr_{3}IrRuO_{7} is explored via resonant x-ray scattering techniques and angle-resolved photoemission measurements. As the Ru content approaches x=0.5 in Sr_{3}(Ir_{1-x}Ru_{x})_{2}O_{7}, intermediate to the J_{eff}=1/2 Mott state in Sr_{3}Ir_{2}O_{7} and the quantum critical metal in Sr_{3}Ru_{2}O_{7}, a thermodynamically distinct metallic state emerges. The electronic structure of this intermediate phase lacks coherent quasiparticles, and charge transport exhibits a linear temperature dependence over a wide range of temperatures. Spin dynamics associated with the long-range antiferromagnetism of this phase show nearly local, overdamped magnetic excitations and an anomalously large energy scale of 200 meV-an energy far in excess of exchange energies present within either the Sr_{3}Ir_{2}O_{7} or Sr_{3}Ru_{2}O_{7} solid-solution end points. Overdamped quasiparticle dynamics driven by strong spin-charge coupling are proposed to explain the incoherent spectral features of the strange metal state in Sr_{3}IrRuO_{7}.
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A new ternary selenide, Na2Mn3Se4, was prepared by a stoichiometric reaction between Na2Se4 and metallic Mn at 923 K. Crystal structure determination revealed a new structure type, built of alternating layers of Na+ ions and [Mn3Se4]2- anionic slabs. Band structure calculations indicate that Na2Mn3Se4 is an indirect band gap semiconductor with Eg = 1.59 eV, although a direct band gap is only marginally larger, at 1.64 eV. The material shows antiferromagnetic (AFM) ordering at 27 K, while the Weiss constant of â¼-400 K suggests much stronger nearest-neighbor AFM exchange between the Mn sites. This discrepancy is attributed to the strong spin frustration caused by a triangulated arrangement of the Mn sites in the [Mn3Se4]2- layer. The magnetic frustration leads to the stabilization of a complex AFM ordered structure with non-collinear arrangement of the Mn magnetic moments, as established from neutron diffraction data.
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To tune the magnetic properties of hexagonal ferrites, a family of magnetoelectric multiferroic materials, by atomic-scale structural engineering, we studied the effect of structural distortion on the magnetic ordering temperature (T_{N}) in these materials. Using the symmetry analysis, we show that unlike most antiferromagnetic rare-earth transition-metal perovskites, a larger structural distortion leads to a higher T_{N} in hexagonal ferrites and manganites, because the K_{3} structural distortion induces the three-dimensional magnetic ordering, which is forbidden in the undistorted structure by symmetry. We also revealed a near-linear relation between T_{N} and the tolerance factor and a power-law relation between T_{N} and the K_{3} distortion amplitude. Following the analysis, a record-high T_{N} (185 K) among hexagonal ferrites was predicted in hexagonal ScFeO_{3} and experimentally verified in epitaxially stabilized films. These results add to the paradigm of spin-lattice coupling in antiferromagnetic oxides and suggests further tunability of hexagonal ferrites if more lattice distortion can be achieved.
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In a type I Dirac or Weyl semimetal, the low-energy states are squeezed to a single point in momentum space when the chemical potential µ is tuned precisely to the Dirac/Weyl point. Recently, a type II Weyl semimetal was predicted to exist, where the Weyl states connect hole and electron bands, separated by an indirect gap. This leads to unusual energy states, where hole and electron pockets touch at the Weyl point. Here we present the discovery of a type II topological Weyl semimetal state in pure MoTe2, where two sets of Weyl points (, ) exist at the touching points of electron and hole pockets and are located at different binding energies above EF. Using angle-resolved photoemission spectroscopy, modelling, density functional theory and calculations of Berry curvature, we identify the Weyl points and demonstrate that they are connected by different sets of Fermi arcs for each of the two surface terminations. We also find new surface 'track states' that form closed loops and are unique to type II Weyl semimetals. This material provides an exciting, new platform to study the properties of Weyl fermions.
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In iron-based superconductors the interactions driving the nematic order (that breaks four-fold rotational symmetry in the iron plane) may also mediate the Cooper pairing. The experimental determination of these interactions, which are believed to depend on the orbital or the spin degrees of freedom, is challenging because nematic order occurs at, or slightly above, the ordering temperature of a stripe magnetic phase. Here, we study FeSe (ref. )-which exhibits a nematic (orthorhombic) phase transition at Ts = 90 K without antiferromagnetic ordering-by neutron scattering, finding substantial stripe spin fluctuations coupled with the nematicity that are enhanced abruptly on cooling through Ts. A sharp spin resonance develops in the superconducting state, whose energy (â¼4 meV) is consistent with an electron-boson coupling mode revealed by scanning tunnelling spectroscopy. The magnetic spectral weight in FeSe is found to be comparable to that of the iron arsenides. Our results support recent theoretical proposals that both nematicity and superconductivity are driven by spin fluctuations.
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We demonstrate that the action of physical pressure, chemical compression, or aliovalent substitution in ACo2As2 (A = Eu and Ca) has a general consequence of causing these antiferromagnetic materials to become ferromagnets. In all cases, the mixed valence triggered at the electropositive A site results in the increase of the Co 3d density of states at the Fermi level. Remarkably, the dramatic alteration of magnetic behavior results from the very minor (<0.15 electron) change in the population of the 3d orbitals. The mixed valence state of Eu observed in the high-pressure (HP) form of EuCo2As2 exhibits a remarkable stability, achieving the average oxidation state of +2.25 at 12.6 GPa. In the case of CaCo2As2, substituting even 10% of Eu or La into the Ca site causes ferromagnetic ordering of Co moments. Similar to HP-EuCo2As2, the itinerant 3d ferromagnetism emerges from electronic doping into the Co layer because of chemical compression of Eu sites in Ca0.9Eu0.1Co1.91As2 or direct electron doping in Ca0.85La0.15Co1.89As2. The results reported herein demonstrate the general possibility of amplifying minor localized electronic effects to achieve major changes in material's properties via involvement of strongly correlated electrons.
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Single crystals of Yb14-xRExMnSb11 (0 < x < 0.6, RE = Pr, Nd, Sm, and Gd) were synthesized by Sn flux. The compounds are iso-structural with Ca14AlSb11 (I41/acd), and their compositions were determined by wavelength-dispersive spectroscopy. Yb14MnSb11 is described as a partially screened d-metal Kondo system with the isolated [MnSb4](9-) tetrahedral cluster having a d(5) + hole configuration that results in four unpaired electrons measured in the ferromagnetically ordered phase. All of the Yb atoms in Yb14MnSb11 are present as Yb(2+), and the additional RE in Yb14-xRExMnSb11 is trivalent, contributing one additional electron to the structure and altering the magnetic properties. All compounds show ferromagnetic ordering in the range of 39-52 K attributed to the [MnSb4](9-) magnetic moment. Temperature-dependent DC magnetization measurements of Yb14-xPrxMnSb11 (0.44 ≤ x ≤ 0.56) show a sharp downturn right below the ferromagnetic transition temperature. Single-crystal neutron diffraction shows that this downturn is caused by a spin reorientation of the [MnSb4](9-) magnetic moments from the ab-plane to c-axis. The spin reorientation behavior, caused by large anisotropy, is also observed for similar x values of RE = Nd but not for RE = Sm or Gd at any value of x. In Pr-, Nd-, and Sm-substituted crystals, the saturation moments are consistent with â¼4 unpaired electrons attributed to [MnSb4](9-), indicating that local moments of Pr, Nd, and Sm do not contribute to the ferromagnetic order. In the case of RE = Pr, this is confirmed by neutron diffraction. In contrast, the magnetic measurements of RE = Gd show that the moments of Gd ferromagnetically order with the moments of [MnSb4](9-), and reduced screening of moments on Mn(2+) is evident. The sensitive variation of magnetic behavior is attributed to the various RE substitutions resulting in different interactions of the 4f-orbitals with the 3d-orbitals of Mn in the [MnSb4](9-) cluster conducted through 5p-orbitals of Sb.
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The pressure effects on the antiferromagentic orders in iron-based ladder compounds CsFe_{2}Se_{3} and BaFe_{2}S_{3} have been studied using neutron diffraction. With identical crystal structure and similar magnetic structures, the two compounds exhibit highly contrasting magnetic behaviors under moderate external pressures. In CsFe_{2}Se_{3} the ladders are brought much closer to each other by pressure, but the stripe-type magnetic order shows no observable change. In contrast, the stripe order in BaFe_{2}S_{3} undergoes a quantum phase transition where an abrupt increase of Néel temperature by more than 50% occurs at about 1 GPa, accompanied by a jump in the ordered moment. With its spin structure unchanged, BaFe_{2}S_{3} enters an enhanced magnetic phase that bears the characteristics of an orbital selective Mott phase, which is the true neighbor of superconductivity emerging at higher pressures.
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An essential step toward elucidating the mechanism of superconductivity is to determine the sign or phase of the superconducting order parameter, as it is closely related to the pairing interaction. In conventional superconductors, the electron-phonon interaction induces attraction between electrons near the Fermi energy and results in a sign-preserved s-wave pairing. For high-temperature superconductors, including cuprates and iron-based superconductors, prevalent weak coupling theories suggest that the electron pairing is mediated by spin fluctuations which lead to repulsive interactions, and therefore that a sign-reversed pairing with an s_{±} or d-wave symmetry is favored. Here, by using magnetic neutron scattering, a phase sensitive probe of the superconducting gap, we report the observation of a transition from the sign-reversed to sign-preserved Cooper-pairing symmetry with insignificant changes in T_{c} in the S-doped iron selenide superconductors K_{x}Fe_{2-y}(Se_{1-z}S_{z})_{2}. We show that a rather sharp magnetic resonant mode well below the superconducting gap (2Δ) in the undoped sample (z=0) is replaced by a broad hump structure above 2Δ under 50% S doping. These results cannot be readily explained by simple spin fluctuation-exchange pairing theories and, therefore, multiple pairing channels are required to describe superconductivity in this system. Our findings may also yield a simple explanation for the sometimes contradictory data on the sign of the superconducting order parameter in iron-based materials.
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Magnetoelectric multiferroicity is not expected to occur in a cubic perovskite system because of the high structural symmetry. By versatile measurements in magnetization, dielectric constant, electric polarization, neutron and x-ray diffraction, Raman scattering, as well as theoretical calculations, we reveal that the A-site ordered perovskite LaMn(3)Cr(4)O(12) with cubic symmetry is a novel spin-driven multiferroic system with strong magnetoelectric coupling effects. When a magnetic field is applied in parallel (perpendicular) to an electric field, the ferroelectric polarization can be enhanced (suppressed) significantly. The unique multiferroic phenomenon observed in this cubic perovskite cannot be understood by conventional spin-driven microscopic mechanisms. Instead, a nontrivial effect involving the interactions between two magnetic sublattices is likely to play a crucial role.
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The intermetallic compounds R2Co2SiC (R = Pr, Nd) were prepared from the reaction of silicon and carbon in either Pr/Co or Nd/Co eutectic flux. These phases crystallize with a new stuffed variant of the W2CoB2 structure type in orthorhombic space group Immm with unit cell parameters a = 3.978(4) Å, b = 6.094(5) Å, c = 8.903(8) Å (Z = 2; R1 = 0.0302) for Nd2Co2SiC. Silicon, cobalt, and carbon atoms form two-dimensional flat sheets, which are separated by puckered layers of rare-earth cations. Magnetic susceptibility measurements indicate that the rare earth cations in both analogues order ferromagnetically at low temperature (TC ≈ 12 K for Nd2Co2SiC and TC ≈ 20 K for Pr2Co2SiC). Single-crystal neutron diffraction data for Nd2Co2SiC indicate that Nd moments initially align ferromagnetically along the c axis around â¼12 K, but below 11 K, they tilt slightly away from the c axis, in the ac plane. Electronic structure calculations confirm the lack of spin polarization for Co 3d moments.