Bulk high-temperature superconductivity in pressurized tetragonal La2PrNi2O7.

The Ruddlesden-Popper (R-P) bilayer nickelate, La3Ni2O7, was recently found to show signatures of high-temperature superconductivity (HTSC) at pressures above 14 GPa (ref. 1). Subsequent investigations achieved zero resistance in single-crystalline and polycrystalline samples under hydrostatic pressure conditions2-4. Yet, obvious diamagnetic signals, the other hallmark of superconductors, are still lacking owing to the filamentary nature with low superconducting volume fraction2,4,5. The presence of a new 1313 polymorph and competing R-P phases obscured proper identification of the phase for HTSC6-9. Thus, achieving bulk HTSC and identifying the phase at play are the most prominent tasks. Here we address these issues in the praseodymium (Pr)-doped La2PrNi2O7 polycrystalline samples. We find that substitutions of Pr for La effectively inhibit the intergrowth of different R-P phases, resulting in a nearly pure bilayer structure. For La2PrNi2O7, pressure-induced orthorhombic to tetragonal structural transition takes place at Pc ≈ 11 GPa, above which HTSC emerges gradually on further compression. The superconducting transition temperatures at 18-20 GPa reach T c onset = 82.5 K and T c zero = 60 K , which are the highest values, to our knowledge, among known nickelate superconductors. Importantly, bulk HTSC was testified by detecting clear diamagnetic signals below about 75 K with appreciable superconducting shielding volume fractions at a pressure of above 15 GPa. Our results not only resolve the existing controversies but also provide directions for exploring bulk HTSC in the bilayer nickelates.

Low-dimensional metal-organic frameworks: a pathway to design, explore and tune magnetic structures.

The magnetic structure adopted by a material relies on symmetry, the hierarchy of exchange interactions between magnetic ions and local anisotropy. A direct pathway to control the magnetic interactions is to enforce dimensionality within the material, from zero-dimensional isolated magnetic ions, one-dimensional (1D) spin-chains, two-dimensional (2D) layers to three-dimensional (3D) order. Being able to design a material with a specific dimensionality for the phenomena of interest is non-trivial. While many advances have been made in the area of inorganic magnetic materials, organic compounds offer distinct and potentially more fertile ground for material design. In particular magnetic metal-organic frameworks (mMOFs) combine magnetism with non-magnetic property functionality on the organic linkers within the structural framework, which can further be tuned with mild perturbations of pressure and field to induce phase transitions. Here, it is examined how neutron scattering measurements on mMOFs can be used to directly determine the magnetic structure when the magnetic ions are in a 2D layered environment within the wider 3D crystalline framework. The hydrated formate, in deuterated form, Co(DCOO)2·2D2O, which was one of the first magnetic MOFs to be investigated with neutron diffraction, is reinvestigated as an exemplar case.

Anomalous continuum scattering and higher-order van Hove singularity in the strongly anisotropic S = 1/2 triangular lattice antiferromagnet.

The S = 1/2 triangular lattice antiferromagnet (TLAF) is a paradigmatic example of frustrated quantum magnetism. An ongoing challenge involves understanding the influence of exchange anisotropy on the collective behavior within such systems. Using inelastic neutron scattering (INS) and advanced calculation techniques, we have studied the low and high-temperature spin dynamics of Ba2La2CoTe2O12 (BLCTO): a Co2+-based Jeff = 1/2 TLAF that exhibits 120° order below TN = 3.26 K. We determined the spin Hamiltonian by fitting the energy-resolved paramagnetic excitations measured at T > TN, revealing exceptionally strong easy-plane XXZ anisotropy. Below TN, the excitation spectrum exhibits a high energy continuum having a larger spectral weight than the single-magnon modes, suggesting a scenario characterized by a spinon confinement length that markedly exceeds the lattice spacing. We conjecture that this phenomenon arises from the proximity to a quantum melting point, even under strong easy-plane XXZ anisotropy. Finally, we highlight characteristic flat features in the excitation spectrum, which are connected to higher-order van Hove singularities in the magnon dispersion directly induced by easy-plane XXZ anisotropy. Our results provide a rare experimental insight into the nature of highly anisotropic S = 1/2 TLAFs between the Heisenberg and XY limits.

Controlling Noncollinear Ferromagnetism in van der Waals Metal-Organic Magnets.

Van der Waals (vdW) magnets both allow exploration of fundamental 2D physics and offer a route toward exploiting magnetism in next generation information technology, but vdW magnets with complex, noncollinear spin textures are currently rare. We report here the syntheses, crystal structures, magnetic properties and magnetic ground states of four bulk vdW metal-organic magnets (MOMs): FeCl2(pym), FeCl2(btd), NiCl2(pym), and NiCl2(btd), pym = pyrimidine and btd = 2,1,3-benzothiadiazole. Using a combination of neutron diffraction and bulk magnetometry we show that these materials are noncollinear magnets. Although only NiCl2(btd) has a ferromagnetic ground state, we demonstrate that low-field hysteretic metamagnetic transitions produce states with net magnetization in zero-field and high coercivities for FeCl2(pym) and NiCl2(pym). By combining our bulk magnetic data with diffuse scattering analysis and broken-symmetry density-functional calculations, we probe the magnetic superexchange interactions, which when combined with symmetry analysis allow us to suggest design principles for future noncollinear vdW MOMs. These materials, if delaminated, would prove an interesting new family of 2D magnets.

Cs2Fe2(MoO4)3-A Strongly Frustrated Magnet with Orbital Degrees of Freedom and Magnetocaloric Properties.

We report an in-depth study of the thermodynamic and magnetocaloric properties of a strongly frustrated magnet, Cs2Fe2(MoO4)3. The underlying structure belongs to the double trillium lattice, which consists of two FeII (S = 2) sites with easy-axis and easy-plane single-ion anisotropy. Detailed 57Fe Mössbauer spectroscopic investigations along with ligand-field calculations support the existence of disparate ground states. The antiferromagnetic ordered structure is presented by the propagation vector k = (0,0,0) with noncollinear magnetic moments of 2.97 µB (Fe1) and 0.17 µB (Fe2), respectively. Strong and disordered magnetic correlations exist in the temperature regime between T N ≈ 1.0 K and |θCW| ≈ 22 K. The large degeneracy of the ground state is investigated in terms of its magnetocaloric response. Magnetization and specific heat measurements indicate a significant magnetocaloric cooling efficiency, making this rare-earth-free compound a promising candidate for cryogenic magnetic refrigeration applications, with refrigeration capacity of 79 J kg-1 for Δ(µ0 H) = 8 T.

Neutron Instruments for Research in Coordination Chemistry.

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.

Noncentrosymmetric Triangular Magnet CaMnTeO6: Strong Quantum Fluctuations and Role of s0 versus s2 Electronic States in Competing Exchange Interactions.

Noncentrosymmetric triangular magnets offer a unique platform for realizing strong quantum fluctuations. However, designing these quantum materials remains an open challenge attributable to a knowledge gap in the tunability of competing exchange interactions at the atomic level. Here, a new noncentrosymmetric triangular S = 3/2 magnet CaMnTeO6 is created based on careful chemical and physical considerations. The model material displays competing magnetic interactions and features nonlinear optical responses with the capability of generating coherent photons. The incommensurate magnetic ground state of CaMnTeO6 with an unusually large spin rotation angle of 127°(1) indicates that the anisotropic interlayer exchange is strong and competing with the isotropic interlayer Heisenberg interaction. The moment of 1.39(1) µB, extracted from low-temperature heat capacity and neutron diffraction measurements, is only 46% of the expected value of the static moment 3 µB. This reduction indicates the presence of strong quantum fluctuations in the half-integer spin S = 3/2 CaMnTeO6 magnet, which is rare. By comparing the spin-polarized band structure, chemical bonding, and physical properties of AMnTeO6 (A = Ca, Sr, Pb), how quantum-chemical interpretation can illuminate insights into the fundamentals of magnetic exchange interactions, providing a powerful tool for modulating spin dynamics with atomically precise control is demonstrated.

Line-Graph Approach to Spiral Spin Liquids.

Competition among exchange interactions is able to induce novel spin correlations on a bipartite lattice without geometrical frustration. A prototype example is the spiral spin liquid, which is a correlated paramagnetic state characterized by subdimensional degenerate propagation vectors. Here, using spectral graph theory, we show that spiral spin liquids on a bipartite lattice can be approximated by a further-neighbor model on the corresponding line-graph lattice that is nonbipartite, thus broadening the space of candidate materials that may support the spiral spin liquid phases. As illustrations, we examine neutron scattering experiments performed on two spinel compounds, ZnCr_{2}Se_{4} and CuInCr_{4}Se_{8}, to demonstrate the feasibility of this new approach and expose its possible limitations in experimental realizations.

Magnetic Interactions of the Centrosymmetric Skyrmion Material Gd_{2}PdSi_{3}.

The experimental realization of magnetic skyrmion crystals in centrosymmetric materials has been driven by theoretical understanding of how a delicate balance of anisotropy and frustration can stabilize topological spin structures in applied magnetic fields. Recently, the centrosymmetric material Gd_{2}PdSi_{3} was shown to host a field-induced skyrmion crystal, but the skyrmion stabilization mechanism remains unclear. Here, we employ neutron-scattering measurements on an isotopically enriched polycrystalline Gd_{2}PdSi_{3} sample to quantify the interactions that drive skyrmion formation. Our analysis reveals spatially extended interactions in triangular planes, and large ferromagnetic interplanar magnetic interactions that are modulated by the Pd/Si superstructure. The skyrmion crystal emerges from a zero-field helical magnetic order with magnetic moments perpendicular to the magnetic propagation vector, indicating that the magnetic dipolar interaction plays a significant role. Our experimental results establish an interaction space that can promote skyrmion formation, facilitating identification and design of centrosymmetric skyrmion materials.

VERDI: VERsatile DIffractometer with wide-angle polarization analysis for magnetic structure studies in powders and single crystals.

The VERsatile DIffractometer will set a new standard for a world-class magnetic diffractometer with versatility for both powder and single crystal samples and capability for wide-angle polarization analysis. The instrument will utilize a large single-frame bandwidth and will offer high-resolution at low momentum transfers and excellent signal-to-noise ratio. A horizontal elliptical mirror concept with interchangeable guide pieces will provide high flexibility in beam divergence to allow for a high-resolution powder mode, a high-intensity single crystal mode, and a polarized beam option. A major science focus will be quantum materials that exhibit emergent properties arising from collective effects in condensed matter. The unique use of polarized neutrons to isolate the magnetic signature will provide optimal experimental input to state-of-the-art modeling approaches to access detailed insight into local magnetic ordering.

Magnetic phase diagram of (Mo2/3RE1/3)2AlC, RE=Tb and Dy, studied by magnetization, specific heat, and neutron diffraction analysis.

We report the results of magnetization, heat capacity, and neutron diffraction measurements on (Mo2/3RE1/3)2AlC with RE = Dy and Tb. Temperature and field-dependent magnetization as well as heat capacity were measured on a powder sample and on a single crystal allowing the construction of the magnetic field-temperature phase diagram. To study the magnetic structure of each magnetic phase, we applied neutron diffraction in a magnetic field up to 6 T. For (Mo2/3Dy1/3)2AlC in zero field, a spin density wave is stabilized at 16 K, with antiferromagnetic ordering at 13 K. Furthermore, we identify the coexistence of ferromagnetic and antiferromagnetic phases induced by magnetic fields for both RE = Tb and Dy. The origin of the field induced phases is resulting from the competing ferromagnetic and antiferromagnetic interactions.

Chloride Reduction of Mn3+ in Mild Hydrothermal Synthesis of a Charge Ordered Defect Pyrochlore, CsMn2+Mn3+F6, a Canted Antiferromagnet with a Hard Ferromagnetic Component.

Geometrically frustrated systems play an important role in studying new physical phenomena and unconventional thermodynamics. Charge ordered defect pyrochlores AM2+M3+F6 offer a convenient platform for probing the interplay between electron distribution over M2+ and M3+ sites and structural distortions; however, they are limited to compounds with M2+/3+ = V, Fe, Ni, and Cu due to difficulties in the simultaneous stabilization of other 3d elements in the +2 and +3 oxidation states. Herein, we employ Cl- anions under hydrothermal conditions for the mild reduction of Mn2O3 in concentrated HF to obtain the CsMn2+Mn3+F6 composition as a phase pure sample and study its properties. The magnetism of CsMn2F6 was characterized by measuring the magnetic susceptibility and isothermal magnetization data, and a magnetic transition to a canted antiferromagnet state was found at 24.1 K. We determined the magnetic structure of CsMn2F6 using powder neutron diffraction, which revealed successive long-range ordering of the Mn2+ and Mn3+ sites that is accompanied by a second transition. The role and strength of magnetic exchange interactions were characterized using DFT calculations.

Influence of the Cubic Sublattice on Magnetic Coupling between the Tetrahedral Sites of Garnet.

We present a study on the nuclear and magnetic structures of two iron-based garnets with magnetic cations isolated on tetrahedral sites. Ca2YZr2Fe3O12 and Ca2LaZr2Fe3O12 offer an interesting comparison for examining the effect of increasing cation size within the diamagnetic backbone of the garnet crystal structure, and how such changes affect the magnetic order. Despite both systems exhibiting well-pronounced magnetic transitions at low temperatures, we also find evidence for diffuse magnetic scattering due to a competition between the nearest-neighbor, next nearest-neighbor, and so on, within the tetrahedral sites. This competition results in a complex noncollinear magnetic structure on the tetrahedral sublattice creating a mixture of ferro- and antiferromagnetic interactions above the long-range ordering temperature near 20 K and suggests that the cubic site of the garnet plays a significant role in mediating the superexchange interactions between tetrahedral cations.

Absence of long-range magnetic order in lithium-containing honeycombs in the Li-Cr-Sb(Te)-O phases.

Li3((LiCr)(Te/Sb))O6compounds where Cr atoms along with Li and Te or Sb are part of a honeycomb and are studied using magnetic susceptibility, specific heat, x-ray photoelectron spectroscopy and neutron diffraction. The oxides stoichiometries as determined from the neutron diffraction studies are Li4.47Cr0.53TeO6and Li3.88Cr1.12SbO6with a stable oxidation state of +3 for Cr. Both the compounds crystallize in space groupC2/mwith intermixing of cations at the 4gsites leaving the 2asites preferentially for Te or Sb. Again, the Li+ions alone predominantly occur in the interlayer sites. Both the compounds show a broad anomaly in specific heat at 8 K, which is robust against 8 T. A corresponding anomaly is absent in the magnetic susceptibility but recovers from its derivative, dχ(T)/dT. We ascertain the magnetic anomaly temperatures (Ta) of Li4.47Cr0.53TeO6and Li3.88Cr1.12SbO6as 5.9 K and 6.7 K respectively from specific heat. Although the physical properties indicated a low temperature anomaly, neutron diffraction data did not reveal a magnetic signal or a structural anomaly down to 1.5 K. This rules out a conventional long-range ordered magnetic ground state in either compounds. Combining the results from specific heat, neutron diffraction and electron paramagnetic resonance, we put forth a scenario of depleted honeycomb lattice of Cr3+with predominant short-range magnetic correlations as the magnetic ground states of the title compounds.

Canting of the Magnetic Moments on the Octahedral Site of an Iron Oxide Garnet in Response to Diamagnetic Cation Substitution.

Using neutron powder diffraction and magnetic susceptibility measurements, we report on the preparation and characterization of the temperature- and field-dependent properties of CaY2ZrFe4O12, a composition closely related to the high-temperature ferrimagnet Y3Fe5O12. By diluting the concentration of paramagnetic ions on the octahedral sublattice of the garnet structure, we find temperature-dependent canting of the magnetic moments. This reflects the importance of the octahedral sublattice in mediating the magnetic interactions between the tetrahedral sites and offers insight into a large number of competing magnetic interactions in the garnet structure.

Observation of novel charge ordering and spin reorientation in perovskite oxide PbFeO3.

PbMO3 (M = 3d transition metals) family shows systematic variations in charge distribution and intriguing physical properties due to its delicate energy balance between Pb 6s and transition metal 3d orbitals. However, the detailed structure and physical properties of PbFeO3 remain unclear. Herein, we reveal that PbFeO3 crystallizes into an unusual 2ap × 6ap × 2ap orthorhombic perovskite super unit cell with space group Cmcm. The distinctive crystal construction and valence distribution of Pb2+0.5Pb4+0.5FeO3 lead to a long range charge ordering of the -A-B-B- type of the layers with two different oxidation states of Pb (Pb2+ and Pb4+) in them. A weak ferromagnetic transition with canted antiferromagnetic spins along the a-axis is found to occur at 600 K. In addition, decreasing the temperature causes a spin reorientation transition towards a collinear antiferromagnetic structure with spin moments along the b-axis near 418 K. Our theoretical investigations reveal that the peculiar charge ordering of Pb generates two Fe3+ magnetic sublattices with competing anisotropic energies, giving rise to the spin reorientation at such a high critical temperature.

Frustrated Heisenberg J1-J2 model within the stretched diamond lattice of LiYbO2.

We investigate the magnetic properties of LiYbO2, containing a three-dimensionally frustrated, diamond-like lattice via neutron scattering, magnetization, and heat capacity measurements. The stretched diamond network of Yb3+ ions in LiYbO2 enters a long-range incommensurate, helical state with an ordering wave vector k=(0.384,±0.384,0) that "locks-in" to a commensurate k=(1/3,±1/3,0) phase under the application of a magnetic field. The spiral magnetic ground state of LiYbO2 can be understood in the framework of a Heisenberg J1-J2 Hamiltonian on a stretched diamond lattice, where the propagation vector of the spiral is uniquely determined by the ratio of J2/J1. The pure Heisenberg model, however, fails to account for the relative phasing between the Yb moments on the two sites of the bipartite lattice, and this detail as well as the presence of an intermediate, partially disordered, magnetic state below 1 K suggests interactions beyond the classical Heisenberg description of this material.

Cluster Frustration in the Breathing Pyrochlore Magnet LiGaCr_{4}S_{8}.

We present a comprehensive neutron scattering study of the breathing pyrochlore magnet LiGaCr_{4}S_{8}. We observe an unconventional magnetic excitation spectrum with a separation of high- and low-energy spin dynamics in the correlated paramagnetic regime above a spin-freezing transition at 12(2) K. By fitting to magnetic diffuse-scattering data, we parametrize the spin Hamiltonian. We find that interactions are ferromagnetic within the large and small tetrahedra of the breathing pyrochlore lattice, but antiferromagnetic further-neighbor interactions are also essential to explain our data, in qualitative agreement with density-functional-theory predictions [Ghosh et al., npj Quantum Mater. 4, 63 (2019)2397-464810.1038/s41535-019-0202-z]. We explain the origin of geometrical frustration in LiGaCr_{4}S_{8} in terms of net antiferromagnetic coupling between emergent tetrahedral spin clusters that occupy a face-centered-cubic lattice. Our results provide insight into the emergence of frustration in the presence of strong further-neighbor couplings, and a blueprint for the determination of magnetic interactions in classical spin liquids.

Mechanistic Insights into the Superexchange-Interaction-Driven Negative Thermal Expansion in CuO.

The negative thermal expansion (NTE) in CuO is explained via electron-transfer-driven superexchange interaction. The elusive connection between the spin-lattice coupling and NTE of CuO is investigated by neutron scattering and principal strain axes analysis. The density functional theory calculations show as the temperature decreases, the continuously increasing electron transfer accounts for enhancing the superexchange interaction along [101̅], the principal NTE direction. It is further rationalized that only when the interaction along [101̅] is preferably enhanced to a certain level compared to the other competing antiferromagnetic exchange pathways can the corresponding NTE occur. Outcomes from this work have implications for controlling the thermal expansion through superexchange interaction, via, for example, optical manipulation, electron or hole doping, etc.

Ferromagnetism Near Room Temperature in the Cleavable van der Waals Crystal Fe5GeTe2.

Two-dimensional materials with intrinsic functionality are becoming increasingly important in exploring fundamental condensed matter science and for developing advanced technologies. Bulk crystals that can be exfoliated are particularly relevant to these pursuits as they provide the opportunity to study the role of physical dimensionality and explore device physics in highly crystalline samples and designer heterostructures in a routine manner. Magnetism is a key element in these endeavors; however, relatively few cleavable materials are magnetic and none possess magnetic order at ambient conditions. Here, we introduce Fe5- xGeTe2 as a cleavable material with ferromagnetic behavior at room temperature. We established intrinsic magnetic order at room temperature in bulk crystals ([Formula: see text] = 310 K) through magnetization measurements and in exfoliated, thin flakes ([Formula: see text] ≈ 280 K) using the anomalous Hall effect. Our work reveals Fe5GeTe2 as a prime candidate for incorporating intrinsic magnetism into functional van der Waals heterostructures and devices near room temperature.