Strong Ferromagnetic Coupling Research Articles

Binuclear Coordination Assemblies of Metal Tetraphenylporphyrins (M = Mn, Fe, and In) with Anionic Thioindigo Bridges as Promising Magnetic Systems with Tunable Properties.

A series of hybrids comprising two metal (Mn, Fe, and In) tetraphenylporphyrins axially substituted with anionic bidentate trans-thioindigo ligands (TI) were obtained. Substitution of the axial chloride anion by an oxygen atom of the dye forms short M-O bonds. Crystalline binuclear assemblies (TI•-)·{[MnIITPP]0·[MnIIITPP]+}·xC6H4Cl2 (x = 2 for 1 or 1 for 2) and (TI2-){[MIIITPP]+}2·xC6H4Cl2 (M = Fe and x = 2 for 3, M = In and x = 1 for 4) were synthesized. The thioindigo (TI2-) dianion and metal (FeIII and InIII) atoms in TPPs maintain their initial charge states during the formation of 3 and 4, allowing the separation of paramagnetic FeIII or diamagnetic InIII ions by a diamagnetic TI2- bridge. Strong antiferromagnetic coupling is observed between FeIII (S = 5/2) centers in complex 3. Partial reduction of MnIII to MnII occurs upon the formation of 1 and 2, leading to assemblies containing three paramagnetic centers: MnII (S = 5/2), MnIII (S = 2), and TI•- radical anion (S = 1/2). Orthogonal arrangement of TPP and TI molecules in 1 provides strong ferromagnetic coupling. Weak antiferromagnetic coupling is realized in 2 due to the rotation of the TI bridge.

Understanding the nature of the magnetic coupling in transition metal doped Bi2Se3

In this paper, we employ electronic structure theory to investigate the nature of the exchange coupling in transition metal doped Bi2Se3. We focus on V, Cr, Mn, and Fe, which have been under scrutiny for the realization of the quantum anomalous Hall effect. For simplicity, we model the doping process as happening inside a single layer of Bi within a single quintuple layer inside a three-formula-unit conventional hexagonal cell and consider situations of full coverage or half coverage. Due to the covalent nature of the chemical bond between transition metal atoms and selenium, this simple model is capable of describing the fundamental features of the intraplane exchange coupling, while offering a clearer analysis of the response to structural, magnetic, and electronic perturbations. In agreement with recent literature, our results confirm that the van Vleck mechanism has a very marginal contribution to the exchange coupling. Depending on the filling of the 3d shell and on the details of the electronic structure, several other mechanisms compete and cooperate to induce the magnetic order. For V, double exchange and superexchange cooperate to have the strongest ferromagnetic coupling among the investigated elements, followed by Cr where only superexchange is active. For Mn, superexchange and double exchange compete to create an extremely weak ferromagnetic order. For Fe, a strong antiferromagnetic coupling caused by the double exchange is observed to dominate over the ferromagnetic Ruderman-Kittel-Kasuya-Yosida interaction, but the high sensitivity of this competition to the doping concentration suggests that our conclusion may not hold in the dilute limit. Overall, Fe doping seems to offer the most intriguing competition of exchange mechanisms that can be tuned by adjusting the doping concentration and the details of the host, as, e.g., by replacing Se with Te or Bi with Sb. Published by the American Physical Society 2024

Magnetocaloric effect and phase transformation of Zn-doped Ni–Mn–Ti all-d metal Heusler alloys

Ni–Mn–Ti Heusler alloys have gained a great consideration recently due to their important magnetoresistance and magnetocaloric properties. Herein, the structure, martensitic transition (MT), and magnetocaloric effect (MCE) of Ni50-xZnxMn35Ti15 (x = 0, 2, 4, and 6) Heusler alloys have been studied. XRD results show that the studied alloy with x = 0 display a monoclinic (5 M) martensite phase. Besides, the examined alloy with x = 2 presents a combination of monoclinic (5 M) martensite and cubic (B2) austenite phases, whereas the alloys with x = 4 and x = 6 exhibit only a cubic (B2) austenite phase. By increasing Zn content x up to 6, the Curie temperature of austenite decreases from 283 K to 132 K, and the MT temperatures decrease from ferromagnetic austenite to weak-magnetic martensite, which is apparently due to the exchange interaction of Mn–Mn and the low power of d-d hybridization between the A/C and B(D) sites. The best maximum magnetic entropy change (ΔSM, max) and refrigeration capacity (RC) are for the studied alloy with x = 4 (5.22 J kg−1K−1 and 217 J kg−1 at 120 kOe, respectively). The Zn addition not only facilitates the formation of B2-type Heusler phases but also offer the possibility to tune the MT and establish strong ferromagnetic coupling.

Quantum magnetism in Fe2Cu2 polymeric branched chains: insights from exactly solved Ising-Heisenberg model

The spin-1/2 Ising-Heisenberg branched chain, inspired by the magnetic structure of three isostructural polymeric coordination compounds [(Tp)2Fe2(CN)6X (bdmap)Cu2(H2O)] ⋅ H2O to be further denoted as Fe2Cu2 (Tp = tris(pyrazolyl)hydroborate, bdmapH = 1,3-bis(dimethylamino)-2-propanol, HX = acetic acid, propionic acid or trifluoroacetic acid), is rigorously studied using the transfer-matrix method. The overall ground-state phase diagram reveals three distinct phases: a quantum antiferromagnetic phase, a quantum ferrimagnetic phase and a classical ferromagnetic phase. In the zero-temperature magnetization curve, two quantum ground states are manifested as intermediate plateaus at zero and half of the saturation magnetization, while the magnetization reaches its saturated value within the classical ferromagnetic phase. The bipartite entanglement between nearest-neighbor Heisenberg spins is more pronounced in the quantum ferrimagnetic phase compared to the quantum antiferromagnetic phase due to a fully polarized nature of the Ising spins. A reasonable agreement between theoretical predictions for the spin-1/2 Ising-Heisenberg branched chain and experimental data measured for a temperature dependence of the magnetic susceptibility and a low-temperature magnetization curve suggests strong antiferromagnetic coupling between nearest-neighbor Cu2+-Cu2+ magnetic ions and moderately strong ferromagnetic coupling between nearest-neighbor Cu2+-Fe3+ magnetic ions in the polymeric compounds Fe2Cu2. A thermal entanglement between nearest-neighbor Cu2+-Cu2+ magnetic ions persists up to a relatively high threshold temperature T ≈ 224 K and undergoes a transient magnetic-field-driven strengthening.

Antiaromatic Molecules as Magnetic Couplers: A Computational Quest.

In this study, we investigate a set of organic diradical structures in which two oxo-verdazyl radicals are selected as radical spin centers that are connected (coupled) via six coupler molecules (CM), resulting in various magnetic (ferromagnetic (FM) or antiferromagnetic (AFM)) characteristics, as reflected by their exchange coupling constants (J). We have designed 12 diradicals with 6-antiaromatic couplers coupled with bis-oxo-verdazyl diradicals with meta-meta (m-m) and para-meta (p-m) positional connectivities. The nature of the magnetic coupling (ferromagnetic, nonmagnetic, or antiferromagnetic) and the magnitude of the exchange constant J depend on the type of coupler, the connecting point between each radical center and CM, the degree of aromaticity of the coupler, and the length of the through-bond distance between radical centers. The computed magnetic exchange coupling constants J for these diradicals at the B3LYP/6-311++G(d,p) and MN12SX/6-311++G(d,p) levels of theory are large for many of these structures, indicating strong ferromagnetic coupling (with positive J values). In some cases, magnetic couplings are observed with J > 1000 cm-1 (B3LYP/6-311++G(d,p)) and strong antiferromagnetic coupling (with negative J values) with J < -1000 cm-1 (B3LYP/6-311++G(d,p)). Similarly, in some cases, magnetic couplings are observed with J > 289 cm-1 (MN12SX/6-311++G(d,p)) and strong antiferromagnetic coupling (with negative J values) with J < -568 cm-1 (MN12SX/6-311++G(d,p)). Furthermore, while numerous studies have reported that the degree of aromaticity of molecular couplers often favors strong ferromagnetic coupling, displaying the high-spin character of diradicals in their ground states, the couplers chosen in this study are characterized as antiaromatic or nonaromatic. The current investigation provides evidence that, remarkably, antiaromatic couplers are able to enhance stability by favoring electronic diradical structures with very strong ferromagnetic coupling when the length of the through-bond distance and connectivity pattern between radical centers are selected in such a way that the FM coupling is optimized. The findings in this study offer new strategies in the design of novel organic materials with interesting magnetic properties for practical applications.

Endohedral metallofullerene molecular nanomagnets.

Magnetic lanthanide (Ln) metal complexes exhibiting magnetic bistability can behave as molecular nanomagnets, also known as single-molecule magnets (SMMs), suitable for storing magnetic information at the molecular level, thus attracting extensive interest in the quest for high-density information storage and quantum information technologies. Upon encapsulating Ln ion(s) into fullerene cages, endohedral metallofullerenes (EMFs) have been proven as a promising and versatile platform to realize chemically robust SMMs, in which the magnetic properties are able to be readily tailored by altering the configurations of the encapsulated species and the host cages. In this review, we present critical discussions on the molecular structures and magnetic characterizations of EMF-SMMs, with the focus on their peculiar molecular and electronic structures and on the intriguing molecular magnetism arising from such structural uniqueness. In this context, different families of magnetic EMFs are summarized, including mononuclear EMF-SMMs wherein single-ion anisotropy is decisive, dinuclear clusterfullerenes whose magnetism is governed by intramolecular magnetic interaction, and radical-bridged dimetallic EMFs with high-spin ground states that arise from the strong ferromagnetic coupling. We then discuss how molecular assemblies of SMMs can be constructed, in a way that the original SMM behavior is either retained or altered in a controlled manner, thanks to the chemical robustness of EMFs. Finally, on the basis of understanding the structure-magnetic property correlation, we propose design strategies for high-performance EMF-SMMs by engineering ligand fields, electronic structures, magnetic interactions, and molecular vibrations that can couple to the spin states.

Room-temperature ferromagnetic semiconductor Fe-doped β-Ga2O3 thin films with high saturation magnetization and low coercivity.

Emergent ferromagnetism in β-Ga2O3 with an ultra-wide bandwidth and high electrical breakdown strength offers exciting opportunities for fabricating robust spintronic devices. One pertinent obstacle in the material has been the low saturation magnetization, which precludes its practical application in magnetic devices. In this work, large-scale Fe-doped β-Ga2O3 diluted magnetic semiconductor (DMS) films are synthesized using a polymer-assisted deposition method, and the effect of Fe doping on their structural and magnetic properties is investigated. Remarkably, the optimal sample exhibits a high saturation magnetization (70 emu cm-3 at 300 K), much larger than those in previously reported stable oxide DMS films, as well as a low coercivity (12 Oe at 300 K). Further analysis shows that our samples manifest a typical bound magnetic polaron (BMP) model and the high saturation magnetization originates from the strong ferromagnetic coupling between the BMPs which is enhanced by Ga vacancies. The Fe-doped β-Ga2O3 thin films with high saturation magnetization and low coercivity may provide a promising platform for related semiconductor spintronics.

Orthogonal magnetic orbitals in high spin Cu-VO units: structure, magnetism and EPR study of anisotropic heterometallic complexes.

Molecular-based magnetic materials are expected to serve as building blocks for quantum bits. To realize high-dimensional Hilbert space and addressability, we constructed anisotropic multi-level systems based on CuII and VIV with orthogonal magnetic orbitals. The crystal structures and intramolecular magnetic couplings of four CuIIVOII complexes [{CuVO(appen)2}2], [{CuVO(fhma)2EDA}2], [{CuVO(hfca)2EDA}2] and [CuVO(hfca)2DPEDA]n are characterized. Due to the orthogonal magnetic orbitals of CuII and VIV, the Cu-V pairs in the four complexes have strong ferromagnetic couplings, and the coupling strength is linearly related to the dihedral angle between the two equatorial planes of the two coordination polyhedra. Because of the triplet ground state, the system can be described by an effective Hamiltonian model consisting of two S = 1 spins coupled together. The anisotropy parameters of [{CuVO(hfca)2EDA}2] and [CuVO(hfca)2DPEDA]n were obtained by the simulation of X-band continuous wave electron paramagnetic resonance (cw-EPR) spectra, confirming that both complexes have zero-field splitting addressable on the relative energy scale. The results indicate that constructing multi-centre complexes based on orthogonal magnetic orbitals is a promising strategy for designing multidimensional quantum bits.

Close-packed nitronyl nitroxide radicals by Au-S self-assembly: strong ferromagnetic coupling.

The study of the magnetism of tightly arranged nitronyl nitroxide (NN) radicals via Au-S self-assembly is interesting. In this study, a series of radicals (S-NN, D-NN, BS-NN, BD-NN) along with two types of nanomaterials (S-NPs, D-NPs) were synthesized. NN was chosen for the magnetic units. Their structures have been successfully synthesized and analyzed. The spin magnetic properties were characterized by electron paramagnetic resonance (EPR) and superconducting quantum interference device (SQUID) measurement. The analysis revealed that the self-assembled NN formed via Au-S bonds exhibits high packing density. Furthermore, it was gratifying to observe that the AuNPs exhibit ferromagnetism after the surface modification by NN. This results in strong ferromagnetic exchange interactions of S-NPs and D-NPs : J S-NPs = +279.715 K and J D-NPs = +254.913 K, respectively.

The effect of Nd content on the elemental interdiffusion mechanism of Nd–Dy–Fe–B magnets

In this work, the effect of Nd content on the interdiffusion mechanism of Nd/Dy elements in Nd-Dy-Fe-B magnets was elucidated by studying the differences in the magnetic properties, microstructure, and demagnetization process. As the Nd content increased, a uniform, continuous, and thicker layer of rare earth-rich (RE-rich) phase formed inside the magnets, which had a good magnetic isolation effect. During the demagnetization process, the strong ferromagnetic coupling effect between the main phase grains could be effectively weakened. At the same time, the thicker RE-rich phase layer could lead to a more obvious interdiffusion phenomenon of Nd/Dy elements, forming more (Nd, Dy)2Fe14B phases with high magnetocrystalline anisotropy fields, resulting in higher coercivity of the magnets. This paper elucidated the influence of Nd content on the interdiffusion mechanism of dual alloy Nd-Dy-Fe-B magnets, which had important significance for the preparation of high-performance Nd-Dy-Fe-B magnets.

Rational Design of an Air-Stable, High-Spin Diradical with Diazapyrene.

Stable carbon-based polyradicals exhibiting strong spin-spin coupling and slow depolarization processes are particularly attractive functional materials. A new molecular motif synthesized by a convenient method that allows the integration of stable, high-spin radicals to (hetero)aromatic polycycles has been developed, as illustrated by a non-Kekulé diradical showing a triplet ground state with long persistency (τ1/2 ≈31 h) in air. Compared to the widely used 1,3-phenylene, the newly designed (diaza)pyrene-4,10-diyl moiety is for the first time demonstrated to confer ferromagnetic (FM) spin coupling, allowing delocalized non-disjoint SOMOs. With the X-ray crystallography unambiguously proving the diradical structure, the triplet ground state was thoroughly characterized. A large ΔES-T of 1.1 kcal/mol, proving the strong FM coupling effect, was revealed consistently by superconducting quantum interference device (SQUID) measurements and variable-temperature electron paramagnetic resonance (EPR) spectroscopy, while the zero-field splitting and triplet nutation characters were examined by continuous-wave and pulsed EPR spectroscopy. A millisecond spin-lattice relaxation time was also detected. The current study not only offers a new molecular motif enabling FM coupling between carbon-based spins, but more importantly presents a general method for installing stable polyradicals into functional π-systems.

Rational Design of an Air‐Stable, High‐Spin Diradical with Diazapyrene

AbstractStable carbon‐based polyradicals exhibiting strong spin‐spin coupling and slow depolarization processes are particularly attractive functional materials. A new molecular motif synthesized by a convenient method that allows the integration of stable, high‐spin radicals to (hetero)aromatic polycycles has been developed, as illustrated by a non‐Kekulé diradical showing a triplet ground state with long persistency (τ1/2≈31 h) in air. Compared to the widely used 1,3‐phenylene, the newly designed (diaza)pyrene‐4,10‐diyl moiety is for the first time demonstrated to confer ferromagnetic (FM) spin coupling, allowing delocalized non‐disjoint SOMOs. With the X‐ray crystallography unambiguously proving the diradical structure, the triplet ground state was thoroughly characterized. A large ΔES‐T of 1.1 kcal/mol, proving the strong FM coupling effect, was revealed consistently by superconducting quantum interference device (SQUID) measurements and variable‐temperature electron paramagnetic resonance (EPR) spectroscopy, while the zero‐field splitting and triplet nutation characters were examined by continuous‐wave and pulsed EPR spectroscopy. A millisecond spin‐lattice relaxation time was also detected. The current study not only offers a new molecular motif enabling FM coupling between carbon‐based spins, but more importantly presents a general method for installing stable polyradicals into functional π‐systems.

Structural, Surface, Magnetic Study and Application of Nanoparticles CoFe2O4, ZnO and its Nanocomposite

Nanoparticles of CoFe2O4 and ZnO were synthesized using the citrate auto-combustion method. A nanocomposite CoFe2O4/ZnO (70:30) was prepared. XRD verified that the samples were synthesized in nanoscale with crystallite sizes of 66.01, 12.48, and 17.47, respectively. The HRTEM image of CoFe2O4 illustrates the cubic structure. FESEM showed that the shape of CoFe2O4, ZnO, and CoFe2O4/ZnO nanoparticles is nearly spherical in morphology. EDAX measurements illustrated that the samples were obtained with nominal compositions similar to their chemical formula. XPS spectra of the investigated CoFe2O4 confirmed the presence of Co2+ and Co3+ ions, as well as Fe3+ and Fe2+ ions. The saturation magnetization increased for CoFe2O4/ZnO than that of the parent CoFe2O4 due to strong ferromagnetic coupling. Antibacterial activity was recorded for the nanocomposite despite its absence from the two parents.

A Remarkably Unsymmetric Hexairon Core Embraced by Two High-Symmetry Tripodal Oligo-α-pyridylamido Ligands.

Oligo-α-pyridylamides offer an appealing route to polyiron complexes with short Fe-Fe separations and large room-temperature magnetic moments. A derivative of tris(2-aminoethyl)amine (H6tren) containing three oligo-α-pyridylamine branches and 13 nitrogen donors (H6L) reacts with [Fe2(Mes)4] to yield an organic nanocage built up by two tripodal ligands with interdigitated branches (HMes = mesitylene). The nanocage has crystallographic D3 symmetry but hosts a remarkably unsymmetric hexairon-oxo core, with a central Fe5(μ5-O) square pyramid, two oxygen donors bridging basal sites, and an additional Fe center residing in one of the two tren-like pockets. Bond valence sum (BVS) analysis, density functional theory (DFT) calculations, and electrochemical data were then used to establish the protonation state of oxygen atoms and the formal oxidation states of the metals. For this purpose, a specialized set of BVS parameters was devised for Fe2+-N3- bonds with nitrogen donors of oligo-α-pyridylamides. This allowed us to formulate the compound as [Fe6O2(OH)(H3L)L], with nominally four FeII ions and two FeIII ions. Mössbauer spectra indicate that the compound contains two unique FeII sites, identified as a pair of closely spaced hydroxo-bridged metal ions in the central Fe5(μ5-O) pyramid, and a substantially valence-delocalized FeII2FeIII2 unit. Broken-symmetry DFT calculations predict strong ferromagnetic coupling between the two iron(II) ions, leading to a local S = 4 state that persists to room temperature and explaining the large magnetic moment measured at 300 K. The compound behaves as a single-molecule magnet, with magnetization dynamics detectable in zero static field and dominated by an Orbach-like mechanism with activation parameters Ueff/kB = 49(2) K and τ0 = 4(2) × 10-10 s.

Tunable coupling in magnetic thin film heterostructures with a magnetic phase transition

The magnetic properties of permalloy-based trilayers of the form Py0.8Cu0.2/Py0.4Cu0.6/Py/IrMn were studied as the spacer layer undergoes a paramagnetic to ferromagnetic phase transition. We find the coupling between the free Py0.8Cu0.2 layer and the exchange bias pinned Py to be strongly temperature-dependent: there is negligible coupling above the Curie temperature of the Py0.4Cu0.6 spacer layer, strong ferromagnetic coupling below that temperature, and a tunable coupling between these extremes. Polarized neutron reflectometry was used to measure the depth profile of the magnetic order in the system, allowing us to correlate the order parameter with the coupling strength. The thickness dependence shows that these are interface effects with an inverse relationship to thickness, and that there is a magnetic proximity effect that enhances the Curie temperature of the spacer layer with characteristic length scale of about 7 nm. As a demonstration of potential functionality of such a system, the structure is shown to spontaneously flip from the antiparallel to parallel magnetic configuration once the spacer layer has developed long-range magnetic order.

Investigation of electronic and magnetic properties in vacancy incorporated monolayer magnesium bromide for spintronics application: an ab-initio study

Alkaline earth-based half-metallic materials attracted spintronics researchers, owing to their outstanding long spin relaxation time and robustness against spin current leakage. Using first principles calculations, defect-induced monolayer magnesium bromide (Mg1−x δ xBr2; x = 0.11, 0.22, 0.33) systems have been studied for the first time. Among these systems, Mg0.89 δ 0.11Br2 showed half-metallic nature that finds application in ultra-fast spintronics. Exfoliation energy (0.12 J/m2) calculation revealed the possibility of exfoliation of the monolayer MgBr2 from its bulk. Phonon dispersion plot confirmed dynamical stability of the free-standing monolayer. The formation energy of Mg vacancy defect (VMg) under Br-rich condition (2 eV) showed, defect-induced favourability. Mg0.89 δ 0.11Br2 has been found to be in a ferromagnetic ground state with a remarkable large spin-up gap (4.84 eV), which limits spin leakage. In addition, significant magnetic anisotropy energy (MAE) per VMg (4.16 meV) has been observed along (100) easy axis direction with a strong ferromagnetic coupling. Electric field modulated electronic structure showed an optimal spin-up gap up to 0.3 V/Å, desirable for the device operation. Robustness of the half-metallicity was confirmed by strain-dependent density of states which is vital during its synthesis and deposition onto a substrate. Hence, from the electronic and magnetic studies, vacancy incorporated monolayer magnesium bromide showed potential applications in spintronics.

Orthorhombic and triclinic modifications of the arsenate Cu4O(AsO4)2 and isotypic phosphates Cu4O(PO4)2: strongly frustrated antiferromagnetics

A structural-magnetic models of the orthorhombic and triclinic modifications of the arsenates Cu4O(AsO4)2 and isotypic phosphates Cu4O(PO4)2 has been built and analyzed. Their base elements are the complicated ribbons composed of antiferromagnetic Cu4 tetrahedra. Structurally, these tetrahedra have no shared copper atoms; however, there are strong antiferromagnetic (AFM) and ferromagnetic (FM) couplings between them, both within the complicated ribbons and between them. It has been established that both modifications are strongly frustrated 3D antiferromagnetics due to competition between the nearest AFM interactions along the edges of the Cu4 tetrahedra and competition between interactions and a multiplicity of long-range secondary AFM and FM interactions. Additionally, a large number of weaker long-range interactions are competing among each other. However, there is a possibility of the ordering Dzyaloshinskii-Moriya (DM) interaction in the centrosymmetric orthorhombic modification (Pnma), because two of the three types of magnetic ions, Cu1 and Cu3, are in the partial position 4c, where the ions are not related by the inversion center. In the triclinic modification (P −1) of Cu4O(As(P)O4)2, all four copper ions are in the centrosymmetric equivalent position 2i, which prevents DM interactions. This centrosymmetry will allow magnetic interactions in the triclinic modification of Cu4O(As(P)O4)2 to be still frustrated at lower temperature. It is possible that the triclinic modification of these compounds is a quantum spin liquid.

Electron Density Analysis of Metal–Metal Bonding in a Ni4 Cluster Featuring Ferromagnetic Exchange

We present a combined experimental and theoretical study of the nature of the proposed metal-metal bonding in the tetranuclear cluster Ni4(NPtBu3)4, which features four nickel(I) centers engaged in strong ferromagnetic coupling. High-resolution single-crystal synchrotron X-ray diffraction data collected at 25 K provide an accurate geometrical structure and a multipole model electron density description. Topological analysis of the electron density in the Ni4N4 core using the quantum theory of atoms in molecules clearly identifies the bonding as an eight-membered ring of type [Ni-N-]4 without direct Ni-Ni bonding, and this result is generally corroborated by an analysis of the energy density distribution. In contrast, the calculated bond delocalization index of ∼0.6 between neighboring Ni atoms is larger than what has been found for other bridged metal-metal bonds and implies direct Ni-Ni bonding. Similar support for the presence of direct Ni-Ni bonding is found in the interacting quantum atom approach, an energy decomposition scheme, which suggests the presence of stabilizing Ni-Ni bonding interactions with an exchange-correlation energy contribution approximately 50% of that of the Ni-N interactions. Altogether, while the direct interactions between neighboring Ni centers are too weak and sterically constrained to bear the signature of a topological bond critical point, other continuous measures clearly indicate significant Ni-Ni bonding. These metal-metal bonding interactions likely mediate direct ferromagnetic exchange, giving rise to the high-spin ground state of the molecule.

Ta thickness effect on field-free switching and spin–orbit torque efficiency in a ferromagnetically coupled Co/Ta/CoFeB trilayer

Current induced spin–orbit torque (SOT) switching of magnetization is a promising technology for nonvolatile spintronic memory and logic applications. In this work, we systematically investigated the effect of Ta thickness on the magnetic properties, field-free switching and SOT efficiency in a ferromagnetically coupled Co/Ta/CoFeB trilayer with perpendicular magnetic anisotropy. We found that both the anisotropy field and coercivity increase with increasing Ta thickness from 0.15 nm to 0.4 nm. With further increase of Ta thickness to 0.5 nm, two-step switching is observed, indicating that the two magnetic layers are magnetically decoupled. Measurements of pulse-current induced magnetization switching and harmonic Hall voltages show that the critical switching current density increases while the field-free switching ratio and SOT efficiency decrease with increasing Ta thickness. Both the enhanced spin memory loss and reduced interlayer exchange coupling might be responsible for the β DL decrease as the Ta spacer thickness increases. The studied structure with the incorporation of a CoFeB layer is able to realize field-free switching in the strong ferromagnetic coupling region, which may contribute to the further development of magnetic tunnel junctions for better memory applications.

First principles study of Mo, W doped CrBr3 alloy compounds

Two-dimensional ferromagnetic semiconductors are considered to be the cornerstone of the next generation of electronic devices, but their application in practical devices is limited by their low Curie temperature (T C ). A monolayer of chromium tribromide (CrBr 3 ) as a member of two-dimensional ferromagnetic material chromium trihalide CrX 3 (X = I, Br, Cl) has found widespread applications in the latest years. Equivalent alloying of ferromagnetic materials is an effective way to increase T C . In this paper, the transition metals Mo and W were chosen to replace Cr atoms in monolayer CrBr 3 to construct alloy compounds Cr 8-x TM x Br 24 (TM = Mo/W, x = 1-4) and the electronic structures as well as magnetic properties were investigated via first principles calculations. Alloy compounds all maintain their original semiconductor properties, with Cr 8-x Mo x Br 24 (x = 2-4) and Cr 5 W 3 Br 24 transformed into direct bandgap semiconductors compared to intrinsic CrBr 3 . Additionally, the ferromagnetic (FM) coupling of alloy compounds is further enhanced. The strongest FM coupling is found in Cr 6 W 2 Br 24 , which is enhanced by 3 times. The magnetic anisotropic energy (MAE) values of alloy compounds are significantly higher. MAE value of Cr 4 W 4 Br 24 is up to 2357 µeV/Cr which is 11 times larger than a value without doping (202 µeV/Cr). T C of alloy compounds all increase, with Cr 4 W 4 Br 24 having a maximum T C of 100.3 K, which is 3 times larger than a value without doping (31 K). The findings increase the range of two-dimensional ferromagnetic semiconductors and offer a theoretical basis for the investigation of the spintronic devices based on CrBr 3 . • The magnetic anisotropy energy values of alloy compounds are significantly enhanced, reaching up to 2357 μeV/Cr. • Crystal field theory and PDOS diagram reveal the mechanism of ferromagnetic coupling enhancement. • Curie temperatures of the alloy compounds are all increased. The highest value is three times higher than intrinsic value.