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.

Superlattices of Gadolinium and Bismuth Based Thallium Dichalcogenides as Potential Magnetic Topological Insulators.

Using relativistic spin-polarized density functional theory calculations we investigate magnetism, electronic structure and topology of the ternary thallium gadolinium dichalcogenides TlGdZ2 (Z= Se and Te) as well as superlattices on their basis. We find TlGdZ2 to have an antiferromagnetic exchange coupling both within and between the Gd layers, which leads to frustration and a complex magnetic structure. The electronic structure calculations reveal both TlGdSe2 and TlGdTe2 to be topologically trivial semiconductors. However, as we show further, a three-dimensional (3D) magnetic topological insulator (TI) state can potentially be achieved by constructing superlattices of the TlGdZ2/(TlBiZ2)n type, in which structural units of TlGdZ2 are alternated with those of the isomorphic TlBiZ2 compounds, known to be non-magnetic 3D TIs. Our results suggest a new approach for achieving 3D magnetic TI phases in such superlattices which is applicable to a large family of thallium rare-earth dichalcogenides and is expected to yield a fertile and tunable playground for exotic topological physics.

Mn-Rich MnSb2 Te4 : A Topological Insulator with Magnetic Gap Closing at High Curie Temperatures of 45-50 K.

Ferromagnetic topological insulators exhibit the quantum anomalous Hall effect, which is potentially useful for high-precision metrology, edge channel spintronics, and topological qubits.  The stable 2+ state of Mn enables intrinsic magnetic topological insulators. MnBi2 Te4 is, however, antiferromagnetic with 25 K Néel temperature and is strongly n-doped. In this work, p-type MnSb2 Te4 , previously considered topologically trivial, is shown to be a ferromagnetic topological insulator for a few percent Mn excess. i) Ferromagnetic hysteresis with record Curie temperature of 45-50 K, ii) out-of-plane magnetic anisotropy, iii) a 2D Dirac cone with the Dirac point close to the Fermi level, iv) out-of-plane spin polarization as revealed by photoelectron spectroscopy, and v) a magnetically induced bandgap closing at the Curie temperature, demonstrated by scanning tunneling spectroscopy (STS), are shown. Moreover, a critical exponent of the magnetization ß ≈ 1 is found, indicating the vicinity of a quantum critical point. Ab initio calculations reveal that Mn-Sb site exchange provides the ferromagnetic interlayer coupling and the slight excess of Mn nearly doubles the Curie temperature. Remaining deviations from the ferromagnetic order open the inverted bulk bandgap and render MnSb2 Te4 a robust topological insulator and new benchmark for magnetic topological insulators.

New Universal Type of Interface in the Magnetic Insulator/Topological Insulator Heterostructures.

Magnetic proximity effect at the interface between magnetic and topological insulators (MIs and TIs) is considered to have great potential in spintronics as, in principle, it allows realizing the quantum anomalous Hall and topological magneto-electric effects (QAHE and TME). Although an out-of-plane magnetization induced in a TI by the proximity effect was successfully probed in experiments, first-principles calculations reveal that a strong electrostatic potential mismatch at abrupt MI/TI interfaces creates harmful trivial states rendering both the QAHE and TME unfeasible in practice. Here on the basis of recent progress in formation of planar self-assembled single layer MI/TI heterostructure (T. Hirahara et al. Nano Lett. 2017 , 17 , 3493 - 3500 ), we propose a conceptually new type of the MI/TI interfaces by means of density functional theory calculations. By considering MnSe/Bi2Se3, MnTe/Bi2Te3, and EuS/Bi2Se3 we demonstrate that, instead of a sharp MI/TI interface clearly separating the two subsystems, it is energetically far more favorable to form a built-in interface via insertion of the MI film inside the TI's surface quintuple layer (e.g., Se-Bi-Se-[MnSe]-Bi-Se) where it forms a bulk-like MI structure. This results in a smooth MI-to-TI connection that yields the interface electronic structure essentially free of trivial states. Our findings open a new direction in studies of the MI/TI interfaces and restore their potential for the QAHE and TME observation.

TCNQ Physisorption on the Topological Insulator Bi2 Se3.

Topological insulators are promising candidates for spintronic applications due to their topologically protected, spin-momentum locked and gapless surface states. The breaking of the time-reversal symmetry after the introduction of magnetic impurities, such as 3d transition metal atoms embedded in two-dimensional molecular networks, could lead to several phenomena interesting for device fabrication. The first step towards the fabrication of metal-organic coordination networks on the surface of a topological insulator is to investigate the adsorption of the pure molecular layer, which is the aim of this study. Here, the effect of the deposition of the electron acceptor 7,7,8,8-tetracyanoquinodimethane (TCNQ) molecules on the surface of a prototypical topological insulator, bismuth selenide (Bi2 Se3 ), is investigated. Scanning tunneling microscope images at low-temperature reveal the formation of a highly ordered two-dimensional molecular network. The essentially unperturbed electronic structure of the topological insulator observed by photoemission spectroscopy measurements demonstrates a negligible charge transfer between the molecular layer and the substrate. Density functional theory calculations confirm the picture of a weakly interacting adsorbed molecular layer. These results reveal significant potential of TCNQ for the realization of metal-organic coordination networks on the topological insulator surface.

Magnetic Properties of Metal⁻Organic Coordination Networks Based on 3d Transition Metal Atoms.

The magnetic anisotropy and exchange coupling between spins localized at the positions of 3d transition metal atoms forming two-dimensional metal⁻organic coordination networks (MOCNs) grown on a Au(111) metal surface are studied. In particular, we consider MOCNs made of Ni or Mn metal centers linked by 7,7,8,8-tetracyanoquinodimethane (TCNQ) organic ligands, which form rectangular networks with 1:1 stoichiometry. Based on the analysis of X-ray magnetic circular dichroism (XMCD) data taken at T = 2.5 K, we find that Ni atoms in the Ni⁻TCNQ MOCNs are coupled ferromagnetically and do not show any significant magnetic anisotropy, while Mn atoms in the Mn⁻TCNQ MOCNs are coupled antiferromagnetically and do show a weak magnetic anisotropy with in-plane magnetization. We explain these observations using both a model Hamiltonian based on mean-field Weiss theory and density functional theory calculations that include spin⁻orbit coupling. Our main conclusion is that the antiferromagnetic coupling between Mn spins and the in-plane magnetization of the Mn spins can be explained by neglecting effects due to the presence of the Au(111) surface, while for Ni⁻TCNQ the metal surface plays a role in determining the absence of magnetic anisotropy in the system.

Magneto-Spin-Orbit Graphene: Interplay between Exchange and Spin-Orbit Couplings.

A rich class of spintronics-relevant phenomena require implementation of robust magnetism and/or strong spin-orbit coupling (SOC) to graphene, but both properties are completely alien to it. Here, we for the first time experimentally demonstrate that a quasi-freestanding character, strong exchange splitting and giant SOC are perfectly achievable in graphene at once. Using angle- and spin-resolved photoemission spectroscopy, we show that the Dirac state in the Au-intercalated graphene on Co(0001) experiences giant splitting (up to 0.2 eV) while being by no means distorted due to interaction with the substrate. Our calculations, based on the density functional theory, reveal the splitting to stem from the combined action of the Co thin film in-plane exchange field and Au-induced Rashba SOC. Scanning tunneling microscopy data suggest that the peculiar reconstruction of the Au/Co(0001) interface is responsible for the exchange field transfer to graphene. The realization of this "magneto-spin-orbit" version of graphene opens new frontiers for both applied and fundamental studies using its unusual electronic bandstructure.

Spin-Orbit Coupling Induced Gap in Graphene on Pt(111) with Intercalated Pb Monolayer.

Graphene is one of the most promising materials for nanoelectronics owing to its unique Dirac cone-like dispersion of the electronic state and high mobility of the charge carriers. However, to facilitate the implementation of the graphene-based devices, an essential change of its electronic structure, a creation of the band gap should controllably be done. Brought about by two fundamentally different mechanisms, a sublattice symmetry breaking or an induced strong spin-orbit interaction, the band gap appearance can drive graphene into a narrow-gap semiconductor or a 2D topological insulator phase, respectively, with both cases being technologically relevant. The later case, characterized by a spin-orbit gap between the valence and conduction bands, can give rise to the spin-polarized topologically protected edge states. Here, we study the effect of the spin-orbit interaction enhancement in graphene placed in contact with a lead monolayer. By means of angle-resolved photoemission spectroscopy, we show that intercalation of the Pb interlayer between the graphene sheet and the Pt(111) surface leads to formation of a gap of ∼200 meV at the Dirac point of graphene. Spin-resolved measurements confirm the splitting to be of a spin-orbit nature, and the measured near-gap spin structure resembles that of the quantum spin Hall state in graphene, proposed by Kane and Mele [ Phys. Rev. Lett. 2005 , 95 , 226801 ]. With a bandstructure tuned in this way, graphene acquires a functionality going beyond its intrinsic properties and becomes more attractive for possible spintronic applications.

Spin Orientation of Two-Dimensional Electrons Driven by Temperature-Tunable Competition of Spin-Orbit and Exchange-Magnetic Interactions.

Finding ways to create and control the spin-dependent properties of two-dimensional electron states (2DESs) is a major challenge for the elaboration of novel spin-based devices. Spin-orbit and exchange-magnetic interactions (SOI and EMI) are two fundamental mechanisms that enable access to the tunability of spin-dependent properties of carriers. The silicon surface of HoRh2Si2 appears to be a unique model system, where concurrent SOI and EMI can be visualized and controlled by varying the temperature. The beauty and simplicity of this system lie in the 4f moments, which act as a multiple tuning instrument on the 2DESs, as the 4f projections parallel and perpendicular to the surface order at essentially different temperatures. Here we show that the SOI locks the spins of the 2DESs exclusively in the surface plane when the 4f moments are disordered: the Rashba-Bychkov effect. When the temperature is gradually lowered and the system experiences magnetic order, the rising EMI progressively competes with the SOI leading to a fundamental change in the spin-dependent properties of the 2DESs. The spins rotate and reorient toward the out-of-plane Ho 4f moments. Our findings show that the direction of the spins and the spin-splitting of the two-dimensional electrons at the surface can be manipulated in a controlled way by using only one parameter: the temperature.

Large-Scale Sublattice Asymmetry in Pure and Boron-Doped Graphene.

The implementation of future graphene-based electronics is essentially restricted by the absence of a band gap in the electronic structure of graphene. Options of how to create a band gap in a reproducible and processing compatible manner are very limited at the moment. A promising approach for the graphene band gap engineering is to introduce a large-scale sublattice asymmetry. Using photoelectron diffraction and spectroscopy we have demonstrated a selective incorporation of boron impurities into only one of the two graphene sublattices. We have shown that in the well-oriented graphene on the Co(0001) surface the carbon atoms occupy two nonequivalent positions with respect to the Co lattice, namely top and hollow sites. Boron impurities embedded into the graphene lattice preferably occupy the hollow sites due to a site-specific interaction with the Co pattern. Our theoretical calculations predict that such boron-doped graphene possesses a band gap that can be precisely controlled by the dopant concentration. B-graphene with doping asymmetry is, thus, a novel material, which is worth considering as a good candidate for electronic applications.

Manipulating the Topological Interface by Molecular Adsorbates: Adsorption of Co-Phthalocyanine on Bi2Se3.

Topological insulators are a promising class of materials for applications in the field of spintronics. New perspectives in this field can arise from interfacing metal-organic molecules with the topological insulator spin-momentum locked surface states, which can be perturbed enhancing or suppressing spintronics-relevant properties such as spin coherence. Here we show results from an angle-resolved photemission spectroscopy (ARPES) and scanning tunnelling microscopy (STM) study of the prototypical cobalt phthalocyanine (CoPc)/Bi2Se3 interface. We demonstrate that that the hybrid interface can act on the topological protection of the surface and bury the Dirac cone below the first quintuple layer.

Epitaxial B-Graphene: Large-Scale Growth and Atomic Structure.

Embedding foreign atoms or molecules in graphene has become the key approach in its functionalization and is intensively used for tuning its structural and electronic properties. Here, we present an efficient method based on chemical vapor deposition for large scale growth of boron-doped graphene (B-graphene) on Ni(111) and Co(0001) substrates using carborane molecules as the precursor. It is shown that up to 19 at. % of boron can be embedded in the graphene matrix and that a planar C-B sp(2) network is formed. It is resistant to air exposure and widely retains the electronic structure of graphene on metals. The large-scale and local structure of this material has been explored depending on boron content and substrate. By resolving individual impurities with scanning tunneling microscopy we have demonstrated the possibility for preferential substitution of carbon with boron in one of the graphene sublattices (unbalanced sublattice doping) at low doping level on the Ni(111) substrate. At high boron content the honeycomb lattice of B-graphene is strongly distorted, and therefore, it demonstrates no unballanced sublattice doping.

Observation of single-spin Dirac fermions at the graphene/ferromagnet interface.

With the discovery and first characterization of graphene, its potential for spintronic applications was recognized immediately. Since then, an active field of research has developed trying to overcome the practical hurdles. One of the most severe challenges is to find appropriate interfaces between graphene and ferromagnetic layers, which are granting efficient injection of spin-polarized electrons. Here, we show that graphene grown under appropriate conditions on Co(0001) demonstrates perfect structural properties and simultaneously exhibits highly spin-polarized charge carriers. The latter was conclusively proven by observation of a single-spin Dirac cone near the Fermi level. This was accomplished experimentally using spin- and angle-resolved photoelectron spectroscopy, and theoretically with density functional calculations. Our results demonstrate that the graphene/Co(0001) system represents an interesting candidate for applications in devices using the spin degree of freedom.