2D Co-Directed Metal-Organic Networks Featuring Strong Antiferromagnetism and Perpendicular Anisotropy.

Antiferromagnetic spintronics is a rapidly emerging field with the potential to revolutionize the way information is stored and processed. One of the key challenges in this field is the development of novel 2D antiferromagnetic materials. In this paper, the first on-surface synthesis of a Co-directed metal-organic network is reported in which the Co atoms are strongly antiferromagnetically coupled, while featuring a perpendicular magnetic anisotropy. This material is a promising candidate for future antiferromagnetic spintronic devices, as it combines the advantages of 2D and metal-organic chemistry with strong antiferromagnetic order and perpendicular magnetic anisotropy.

Spectroscopic Evidence of Kondo-Induced Quasiquartet in CeRh_{2}As_{2}.

CeRh_{2}As_{2} is a new multiphase superconductor with strong suggestions for an additional itinerant multipolar ordered phase. The modeling of the low-temperature properties of this heavy-fermion compound requires a quartet Ce^{3+} crystal-field ground state. Here, we provide the evidence for the formation of such a quartet state using x-ray spectroscopy. Core-level photoelectron and x-ray absorption spectroscopy confirm the presence of Kondo hybridization in CeRh_{2}As_{2}. The temperature dependence of the linear dichroism unambiguously reveals the impact of Kondo physics for coupling the Kramer's doublets into an effective quasiquartet. Nonresonant inelastic x-ray scattering data find that the |Γ_{7}^{-}⟩ state with its lobes along the 110 direction of the tetragonal structure (xy orientation) contributes most to the multiorbital ground state of CeRh_{2}As_{2}.

2D Materials by Design: Intercalation of Cr or Mn between two VSe2 van der Waals Layers.

Insertion of metal layers between layered transition-metal dichalcogenides (TMDs) enables the design of new pseudo-2D nanomaterials. The general premise is that various metal atoms may adopt energetically favorable intercalation sites between two TMD sheets. These covalently bound metals arrange in metastable configurations and thus enable the controlled synthesis of nanomaterials in a bottom-up approach. Here, this method is demonstrated by the insertion of Cr or Mn between VSe2 layers. Vacuum-deposited transition metals diffuse between VSe2 layers with increasing concentration, arranging in ordered phases. The Cr3+ or Mn2+ ions are in octahedral coordination and thus in a high-spin state. Measured and computed magnetic moments are high for dilute Cr atoms, but with increasing Cr concentration the average magnetic moment decreases, suggesting antiferromagnetic ordering between Cr ions. The many possible combinations of transition metals with TMDs form a library for exploring quantum phenomena in these nanomaterials.

Large-Area Synthesis of Ferromagnetic Fe5- x GeTe2 /Graphene van der Waals Heterostructures with Curie Temperature above Room Temperature.

Van der Waals (vdW) heterostructures combining layered ferromagnets and other 2D crystals are promising building blocks for the realization of ultracompact devices with integrated magnetic, electronic, and optical functionalities. Their implementation in various technologies depends strongly on the development of a bottom-up scalable synthesis approach allowing for realizing highly uniform heterostructures with well-defined interfaces between different 2D-layered materials. It is also required that each material component of the heterostructure remains functional, which ideally includes ferromagnetic order above room temperature for 2D ferromagnets. Here, it is demonstrated that the large-area growth of Fe5- x GeTe2 /graphene heterostructures is achieved by vdW epitaxy of Fe5- x GeTe2 on epitaxial graphene. Structural characterization confirms the realization of a continuous vdW heterostructure film with a sharp interface between Fe5- x GeTe2 and graphene. Magnetic and transport studies reveal that the ferromagnetic order persists well above 300 K with a perpendicular magnetic anisotropy. In addition, epitaxial graphene on SiC(0001) continues to exhibit a high electronic quality. These results represent an important advance beyond nonscalable flake exfoliation and stacking methods, thus marking a crucial step toward the implementation of ferromagnetic 2D materials in practical applications.

On-Surface Design of a 2D Cobalt-Organic Network Preserving Large Orbital Magnetic Moment.

The design of antiferromagnetic nanomaterials preserving large orbital magnetic moments is important to protect their functionalities against magnetic perturbations. Here, we exploit an archetype H6HOTP species for conductive metal-organic frameworks to design a Co-HOTP one-atom-thick metal-organic architecture on a Au(111) surface. Our multidisciplinary scanning probe microscopy, X-ray absorption spectroscopy, X-ray linear dichroism, and X-ray magnetic circular dichroism study, combined with density functional theory simulations, reveals the formation of a unique network design based on threefold Co+2 coordination with deprotonated ligands, which displays a large orbital magnetic moment with an orbital to effective spin moment ratio of 0.8, an in-plane easy axis of magnetization, and large magnetic anisotropy. Our simulations suggest an antiferromagnetic ground state, which is compatible with the experimental findings. Such a Co-HOTP metal-organic network exemplifies how on-surface chemistry can enable the design of field-robust antiferromagnetic materials.

Engineering Periodic Dinuclear Lanthanide-Directed Networks Featuring Tunable Energy Level Alignment and Magnetic Anisotropy by Metal Exchange.

The design of lanthanide multinuclear networks is an emerging field of research due to the potential of such materials for nanomagnetism, spintronics, and quantum information. Therefore, controlling their electronic and magnetic properties is of paramount importance to tailor the envisioned functionalities. In this work, a multidisciplinary study is presented combining scanning tunneling microscopy, scanning tunneling spectroscopy, X-ray absorption spectroscopy, X-ray linear dichroism, X-ray magnetic circular dichroism, density functional theory, and multiplet calculations, about the supramolecular assembly, electronic and magnetic properties of periodic dinuclear 2D networks based on lanthanide-pyridyl interactions on Au(111). Er- and Dy-directed assemblies feature identical structural architectures stabilized by metal-organic coordination. Notably, despite exhibiting the same +3 oxidation state, there is a shift of the energy level alignment of the unoccupied molecular orbitals between Er- and Dy-directed networks. In addition, there is a reorientation of the easy axis of magnetization and an increment of the magnetic anisotropy when the metallic center is changed from Er to Dy. Thus, the results show that it is feasible to tune the energy level alignment and magnetic anisotropy of a lanthanide-based metal-organic architecture by metal exchange, while preserving the network design.

Tuning the Magnetic Anisotropy of Lanthanides on a Metal Substrate by Metal-Organic Coordination.

Taming the magnetic anisotropy of lanthanides through coordination environments is crucial to take advantage of the lanthanides properties in thermally robust nanomaterials. In this work, the electronic and magnetic properties of Dy-carboxylate metal-organic networks on Cu(111) based on an eightfold coordination between Dy and ditopic linkers are inspected. This surface science study based on scanning probe microscopy and X-ray magnetic circular dichroism, complemented with density functional theory and multiplet calculations, reveals that the magnetic anisotropy landscape of the system is complex. Surface-supported metal-organic coordination is able to induce a change in the orientation of the easy magnetization axis of the Dy coordinative centers as compared to isolated Dy atoms and Dy clusters, and significantly increases the magnetic anisotropy. Surprisingly, Dy atoms coordinated in the metallosupramolecular networks display a nearly in-plane easy magnetization axis despite the out-of-plane symmetry axis of the coordinative molecular lattice. Multiplet calculations highlight the decisive role of the metal-organic coordination, revealing that the tilted orientation is the result of a very delicate balance between the interaction of Dy with O atoms and the precise geometry of the crystal field. This study opens new avenues to tailor the magnetic anisotropy and magnetic moments of lanthanide elements on surfaces.

Magnetism at the interface of non-magnetic Cu and C60.

The signature of magnetism without a ferromagnet in a non-magnetic heterostructure is novel as well as fascinating from a fundamental research point of view. It has been shown by Al'Mari et al. that magnetism can be induced at the interface of Cu/C60 due to a change in the density of states. However, the quantification of such an interfacial magnetic moment has not been performed yet. In order to quantify the induced magnetic moment in Cu, we have performed X-ray magnetic circular dichroism (XMCD) measurements on Cu/C60 multilayers. We have observed room temperature ferromagnetism in the Cu/C60 stack. Further XMCD measurements show that a ∼0.01 µB per atom magnetic moment has been induced in Cu at the Cu/C60 interface.

The Synthesis of a Quasi-One-Dimensional Iron-Based Telluride with Antiferromagnetic Chains and a Spin Glass State.

The report on the superconductivity of the two-legged spin ladders BaFe2S3 and BaFe2Se3 has established 123-type iron chalcogenides as a novel subgroup in the iron-based superconductor family and has stimulated the continuous exploration of other iron-based materials with new structures and potentially novel properties. In this paper, we report the systematic study of a new quasi-one-dimensional (1D) iron-based compound, Ba9Fe3Te15, including its synthesis and magnetic properties. The high-pressure synthesized Ba9Fe3Te15 crystallized in a hexagonal structure that mainly consisted of face-sharing FeTe6 octahedral chains running along the c axis, with a lattice constant of a = 10.23668 Å; this led to weak interchain coupling and an enhanced one-dimensionality. The systematic static and dynamic magnetic properties were comprehensively studied experimentally. The dc magnetic susceptibility showed typical 1D antiferromagnetic characteristics, with a Tmax at 190 K followed by a spin glass (SG) state with freezing at Tf ≈ 6.0 K, which were also unambiguously proved by ac susceptibility measurements. Additionally, X-ray magnetic circular dichroism (XMCD) experiments revealed an unexpected orbital moment for Fe2+, i.e., 0.84 µB per Fe in Ba9Fe3Te15. The transport property is electrically insulating, with a thermal activation gap of 0.32 eV. These features mark Ba9Fe3Te15 as an alternative type of iron-based compound, providing a diverse candidate for high-pressure studies in order to pursue some emerging physics.

Emergent magnetism at transition-metal-nanocarbon interfaces.

Charge transfer at metallo-molecular interfaces may be used to design multifunctional hybrids with an emergent magnetization that may offer an eco-friendly and tunable alternative to conventional magnets and devices. Here, we investigate the origin of the magnetism arising at these interfaces by using different techniques to probe 3d and 5d metal films such as Sc, Mn, Cu, and Pt in contact with fullerenes and rf-sputtered carbon layers. These systems exhibit small anisotropy and coercivity together with a high Curie point. Low-energy muon spin spectroscopy in Cu and Sc-C60 multilayers show a quick spin depolarization and oscillations attributed to nonuniform local magnetic fields close to the metallo-carbon interface. The hybridization state of the carbon layers plays a crucial role, and we observe an increased magnetization as sp3 orbitals are annealed into sp2-π graphitic states in sputtered carbon/copper multilayers. X-ray magnetic circular dichroism (XMCD) measurements at the carbon K edge of C60 layers in contact with Sc films show spin polarization in the lowest unoccupied molecular orbital (LUMO) and higher π*-molecular levels, whereas the dichroism in the σ*-resonances is small or nonexistent. These results support the idea of an interaction mediated via charge transfer from the metal and dz-π hybridization. Thin-film carbon-based magnets may allow for the manipulation of spin ordering at metallic surfaces using electrooptical signals, with potential applications in computing, sensors, and other multifunctional magnetic devices.

Unraveling Dzyaloshinskii-Moriya Interaction and Chiral Nature of Graphene/Cobalt Interface.

A major challenge for future spintronics is to develop suitable spin transport channels with long spin lifetime and propagation length. Graphene can meet these requirements, even at room temperature. On the other side, taking advantage of the fast motion of chiral textures, that is, Néel-type domain walls and magnetic skyrmions, can satisfy the demands for high-density data storage, low power consumption, and high processing speed. We have engineered epitaxial structures where an epitaxial ferromagnetic Co layer is sandwiched between an epitaxial Pt(111) buffer grown in turn onto MgO(111) substrates and a graphene layer. We provide evidence of a graphene-induced enhancement of the perpendicular magnetic anisotropy up to 4 nm thick Co films and of the existence of chiral left-handed Néel-type domain walls stabilized by the effective Dzyaloshinskii-Moriya interaction (DMI) in the stack. The experiments show evidence of a sizable DMI at the gr/Co interface, which is described in terms of a conduction electron mediated Rashba-DMI mechanism and points opposite to the spin orbit coupling-induced DMI at the Co/Pt interface. In addition, the presence of graphene results in (i) a surfactant action for the Co growth, producing an intercalated, flat, highly perfect face-centered cubic film, pseudomorphic with Pt and (ii) an efficient protection from oxidation. The magnetic chiral texture is stable at room temperature and grown on insulating substrate. Our findings open new routes to control chiral spin structures using interfacial engineering in graphene-based systems for future spin-orbitronics devices fully integrated on oxide substrates.

Imaging Nanometer Phase Coexistence at Defects During the Insulator-Metal Phase Transformation in VO2 Thin Films by Resonant Soft X-ray Holography.

We use resonant soft X-ray holography to image the insulator-metal phase transition in vanadium dioxide with element and polarization specificity and nanometer spatial resolution. We observe that nanoscale inhomogeneity in the film results in spatial-dependent transition pathways between the insulating and metallic states. Additional nanoscale phases form in the vicinity of defects which are not apparent in the initial or final states of the system, which would be missed in area-integrated X-ray absorption measurements. These intermediate phases are vital to understand the phase transition in VO2, and our results demonstrate how resonant imaging can be used to understand the electronic properties of phase-separated correlated materials obtained by X-ray absorption.

High-Pressure Synthesis and Ferrimagnetic Ordering of the B-Site-Ordered Cubic Perovskite Pb2FeOsO6.

Pb2FeOsO6 was prepared for the first time by using high-pressure and high-temperature synthesis techniques. This compound crystallizes into a B-site-ordered double-perovskite structure with cubic symmetry Fm3̅m, where the Fe and Os atoms are orderly distributed with a rock-salt-type manner. Structure refinement shows an Fe-Os antisite occupancy of about 16.6%. Structural analysis and X-ray absorption spectroscopy both demonstrate the charge combination to be Pb2Fe3+Os5+O6. A long-range ferrimagnetic transition is found to occur at about 280 K due to antiferromagnetic interactions between the adjacent Fe3+ and Os5+ spins with a straight (180°) Fe-O-Os bond angle, as confirmed by X-ray magnetic circular-dichroism measurements. First-principles theoretical calculations reveal the semiconducting behavior as well as the Fe3+(↑)Os5+(↓) antiferromagnetic coupling originating from the superexchange interactions between the half-filled 3d orbitals of Fe and t2g orbitals of Os.

On-Surface Synthesis of Organolanthanide Sandwich Complexes.

The synthesis of lanthanide-based organometallic sandwich compounds is very appealing regarding their potential for single-molecule magnetism. Here, it is exploited by on-surface synthesis to design unprecedented lanthanide-directed organometallic sandwich complexes on Au(111). The reported compounds consist of Dy or Er atoms sandwiched between partially deprotonated hexahydroxybenzene molecules, thus introducing a distinct family of homoleptic organometallic sandwiches based on six-membered ring ligands. Their structural, electronic, and magnetic properties are investigated by scanning tunneling microscopy and spectroscopy, X-ray absorption spectroscopy, X-ray linear and circular magnetic dichroism, and X-ray photoelectron spectroscopy, complemented by density functional theory-based calculations. Both lanthanide complexes self-assemble in close-packed islands featuring a hexagonal lattice. It is unveiled that, despite exhibiting analogous self-assembly, the erbium-based species is magnetically isotropic, whereas the dysprosium-based compound features an in-plane magnetization.

Covalency versus magnetic axiality in Nd molecular magnets: Nd-photoluminescence, strong ligand-field, and unprecedented nephelauxetic effect in fullerenes NdM2N@C80 (M = Sc, Lu, Y).

Nd-based nitride clusterfullerenes NdM2N@C80 with rare-earth metals of different sizes (M = Sc, Y, Lu) were synthesized to elucidate the influence of the cluster composition, shape and internal strain on the structural and magnetic properties. Single crystal X-ray diffraction revealed a very short Nd-N bond length in NdSc2N@C80. For Lu and Y analogs, the further shortening of the Nd-N bond and pyramidalization of the NdM2N cluster are predicted by DFT calculations as a result of the increased cluster size and a strain caused by the limited size of the fullerene cage. The short distance between Nd and nitride ions leads to a very large ligand-field splitting of Nd3+ of 1100-1200 cm-1, while the variation of the NdM2N cluster composition and concomitant internal strain results in the noticeable modulation of the splitting, which could be directly assessed from the well-resolved fine structure in the Nd-based photoluminescence spectra of NdM2N@C80 clusterfullerenes. Photoluminescence measurements also revealed an unprecedentedly strong nephelauxetic effect, pointing to a high degree of covalency. The latter appears detrimental to the magnetic axiality despite the strong ligand field. As a result, the ground magnetic state has considerable transversal components of the pseudospin g-tensor, and the slow magnetic relaxation of NdSc2N@C80 could be observed by AC magnetometry only in the presence of a magnetic field. A combination of the well-resolved magneto-optical states and slow relaxation of magnetization suggests that Nd clusterfullerenes can be useful building blocks for magneto-photonic quantum technologies.

Ferromagnetism on an atom-thick & extended 2D metal-organic coordination network.

Ferromagnetism is the collective alignment of atomic spins that retain a net magnetic moment below the Curie temperature, even in the absence of external magnetic fields. Reducing this fundamental property into strictly two-dimensions was proposed in metal-organic coordination networks, but thus far has eluded experimental realization. In this work, we demonstrate that extended, cooperative ferromagnetism is feasible in an atomically thin two-dimensional metal-organic coordination network, despite only ≈ 5% of the monolayer being composed of Fe atoms. The resulting ferromagnetic state exhibits an out-of-plane easy-axis square-like hysteresis loop with large coercive fields over 2 Tesla, significant magnetic anisotropy, and persists up to TC ≈ 35 K. These properties are driven by exchange interactions mainly mediated by the molecular linkers. Our findings resolve a two decade search for ferromagnetism in two-dimensional metal-organic coordination networks.

Probing of three-dimensional spin textures in multilayers by field dependent X-ray resonant magnetic scattering.

In multilayers of magnetic thin films with perpendicular anisotropy, domain walls can take on hybrid configurations in the vertical direction which minimize the domain wall energy, with Néel walls in the top or bottom layers and Bloch walls in some central layers. These types of textures are theoretically predicted, but their observation has remained challenging until recently, with only a few techniques capable of realizing a three dimensional characterization of their magnetization distribution. Here we perform a field dependent X-ray resonant magnetic scattering measurements on magnetic multilayers exploiting circular dichroism contrast to investigate such structures. Using a combination of micromagnetic and X-ray resonant magnetic scattering simulations along with our experimental results, we characterize the three-dimensional magnetic texture of domain walls, notably the thickness resolved characterization of the size and position of the Bloch part in hybrid walls. We also take a step in advancing the resonant scattering methodology by using measurements performed off the multilayer Bragg angle in order to calibrate the effective absorption of the X-rays, and permitting a quantitative evaluation of the out of plane (z) structure of our samples. Beyond hybrid domain walls, this approach can be used to characterize other periodic chiral structures such as skyrmions, antiskyrmions or even magnetic bobbers or hopfions, in both static and dynamic experiments.

Reversal of Anomalous Hall Effect and Octahedral Tilting in SrRuO3 Thin Films via Hydrogen Spillover.

The perovskite SrRuO3 (SRO) is a strongly correlated oxide whose physical and structural properties are strongly intertwined. Notably, SRO is an itinerant ferromagnet that exhibits a large anomalous Hall effect (AHE) whose sign can be readily modified. Here, a hydrogen spillover method is used to tailor the properties of SRO thin films via hydrogen incorporation. It is found that the magnetization and Curie temperature of the films are strongly reduced and, at the same time, the structure evolves from an orthorhombic to a tetragonal phase as the hydrogen content is increased up to ≈0.9 H per SRO formula unit. The structural phase transition is shown, via in situ crystal truncation rod measurements, to be related to tilting of the RuO6 octahedral units. The significant changes observed in magnetization are shown, via density functional theory (DFT), to be a consequence of shifts in the Fermi level. The reported findings provide new insights into the physical properties of SRO via tailoring its lattice symmetry and emergent physical phenomena via the hydrogen spillover technique.

Inducing Single Spin-Polarized Flat Bands in Monolayer Graphene.

Due to the fundamental and technological implications in driving the appearance of non-trivial, exotic topological spin textures and emerging symmetry-broken phases, flat electronic bands in 2D materials, including graphene, are nowadays a relevant topic in the field of spintronics. Here, via europium doping, single spin-polarized bands are generated in monolayer graphene supported by the Co(0001) surface. The doping is controlled by Eu positioning, allowing for the formation of a K ¯ $\bar{\mathrm{K}}$ -valley localized single spin-polarized low-dispersive parabolic band close to the Fermi energy when Eu is on top, and of a π* flat band with single spin character when Eu is intercalated underneath graphene. In the latter case, Eu also induces a bandgap opening at the Dirac point while the Eu 4f states act as a spin filter, splitting the π band into two spin-polarized branches. The generation of flat bands with single spin character, as revealed by the spin- and angle-resolved photoemission spectroscopy (ARPES) experiments, complemented by density functional theory (DFT) calculations, opens up new pathways toward the realization of spintronic devices exploiting such novel exotic electronic and magnetic states.