Antiferromagnetic Exchange Coupling Research Articles

The Role of Rare-Earth Atoms in the Anisotropy and Antiferromagnetic Exchange Coupling at a Hybrid Metal-Organic Interface.

Magnetic anisotropy and magnetic exchange interactions are crucial parameters that characterize the hybrid metal-organic interface, a key component of an organic spintronic device. It is shown that the incorporation of 4f RE atoms to hybrid metal-organic interfaces of CuPc/REAu2 type (RE = Gd, Ho) constitutes a feasible approach toward on-demand magnetic properties and functionalities. The GdAu2 and HoAu2 substrates differ in their magnetic anisotropy behavior. Remarkably, the HoAu2 surface promotes the inherent out-of-plane anisotropy of CuPc, owing to the match between the anisotropy axis of substrate and molecule. Furthermore, the presence of RE atoms leads to a spontaneous antiferromagnetic exchange coupling at the interface, induced by the 3d-4f superexchange interaction between the unpaired 3d electron of CuPc and the 4f electrons of the RE atoms. It is shown that 4f RE atoms with unquenched quantum orbital momentum ( ), as it is the case of Ho, induce an anisotropic interfacial exchangecoupling.

Metal-Halide Covalency, Exchange Coupling, and Slow Magnetic Relaxation in Triangular (CpiPr5)3U3X6 (X = Cl, Br, I) Clusters.

The actinide elements are attractive alternatives to transition metals or lanthanides for the design of exchange-coupled multinuclear single-molecule magnets. However, the synthesis of such compounds is challenging, as is unraveling any contributions from exchange coupling to the overall magnetism. To date, only a few actinide compounds have been shown to exhibit exchange coupling and single-molecule magnetism. Here, we report triangular uranium(III) clusters of the type (CpiPr5)3U3X (1-X; X = Cl, Br, I; CpiPr5 = pentaisopropylcyclopentadienyl), which are synthesized via reaction of the aryloxide-bridged precursor (CpiPr5)2U2(OPhtBu)4 with excess Me3SiX. Spectroscopic analysis suggests the presence of covalency in the uranium-halide interactions arising from 5f orbital participation in bonding. The dc magnetic susceptibility data reveal the presence of antiferromagnetic exchange coupling between the uranium(III) centers in these compounds, with the strength of the exchange decreasing down the halide series. Ac magnetic susceptibility data further reveal all compounds to exhibit slow magnetic relaxation under zero dc field. In 1-I, which exhibits particularly weak exchange, magnetic relaxation occurs via a Raman mechanism associated with the individual uranium(III) centers. In contrast, for 1-Br and 1-Cl, magnetic relaxation occurs via an Orbach mechanism, likely involving relaxation between ground and excited exchange-coupled states. Significantly, in the case of 1-Cl, magnetic relaxation is sufficiently slow such that open magnetic hysteresis is observed up to 2.75 K, and the compound exhibits a 100-s blocking temperature of 2.4 K. This compound provides the first example of magnetic blocking in a compound containing only actinide-based ions, as well as the first example involving the uranium(III) oxidation state.

Effect of iron layer thickness on the interlayer exchange coupling in Fe/MgO (001) superlattices

We describe the effect of the Fe layer thickness on the antiferromagnetic interlayer exchange coupling in [Fe/MgO]N superlattices. An increase in coupling strength with increasing Fe layer thickness is observed, which highlights the need for including the extension of both layers when discussing the interlayer exchange coupling in superlattices. Published by the American Physical Society 2024

The enhancement of low-temperature excitation of magnons via interlayer exchange coupling in perpendicularly magnetized [Co/Pd] multilayers

In this study, we analyze the correlation between magnetization and magnetoresistance of perpendicularly anisotropic [Co/Pd] multilayered films with different thicknesses of Pd layers tPd = 0.6–2.0 nm in a wide range of temperatures, T = 4–300 K. We revealed that electron scattering by magnons makes a significant contribution to the magnetoresistance of the multilayers regardless of the layer thickness. Contrary to expectations, the effect of magnon magnetoresistance (MMR) increases with decreasing temperature below T = 50 K in the films with tPd = 0.8 and 1.0 nm. The revealed low-temperature MMR increase, which is most pronounced in the [Co0.5/Pd1.0] multilayers, is associated with the enhanced magnon excitation due to antiferromagnetic exchange coupling between the Co layers. The latter ensures an atypical shape of the magnetization curves of the [Co0.5/Pd1.0] multilayers at low temperatures in a perpendicular magnetic field, which combine a quadratic hysteresis loop of a perpendicularly anisotropic ferromagnet and an anomalous magnetization drop resulting from a violation of the ordering of magnetic moments and their amplified oscillations initiated by the interlayer exchange coupling.

MgAl2O4 capping effects on the magnetic properties of TbFeCo films

We investigate MgAl2O4 (MAO) capping effects on the magnetic properties of TbFeCo films. Compared with TbFeCo films, a shift of compensation point to lower temperatures together with significantly reduced saturation magnetization is found in the case of MAO capping. An antiferromagnetic exchange coupling is observed in TbFeCo/MAO structures. This can be well explained by a double layer model with opposite phases. An exchange energy density of ∼ 0.5 erg/cm2 is obtained, which is comparable but lower than that of TbFeCo bilayers with opposite phases. Our findings may be useful for developing ultrathin TbFeCo/MAO heterostructure-based spintronic devices.

Room-Temperature Entanglement of the Nickel-Radical Molecular Complex (Et3NH)[Ni(hfac)2L] Reinforced by the Magnetic Field

Bipartite entanglement is comprehensively investigated in the mononuclear molecular complex (Et3NH)[Ni(hfac)2L], where HL denotes 2-(2-hydroxy-3-methoxy-5-nitrophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-3-oxide-1-oxyl and hfacH stands for hexafluoroacetylacetone. From the magnetic point of view, the molecular compound (Et3NH)[Ni(hfac)2L] consists of an exchange-coupled spin-1 Ni2+ magnetic ion and a spin-12 nitronyl-nitroxide radical substituted nitrophenol. The nickel-radical molecular complex affords an experimental realization of a mixed spin-(12, 1) Heisenberg dimer with a strong antiferromagnetic exchange coupling, J/kB = 505 K, and two distinct g-factors, gRad = 2.005 and gNi = 2.275. By adopting this set of magnetic parameters, we demonstrate that the Zeeman splitting of a quantum ferrimagnetic ground-state doublet due to a weak magnetic field may substantially reinforce the strength of bipartite entanglement at low temperatures. The molecular compound (Et3NH)[Ni(hfac)2L] maintains sufficiently strong thermal entanglement, even at room temperature, vanishing only above 546 K. Specifically, the thermal entanglement in the nickel-radical molecular complex retains approximately 40% of the maximum value, corresponding to perfectly entangled Bell states at room temperature, which implies that this magnetic compound provides a suitable platform of a molecular qubit with potential implications for room-temperature quantum computation and quantum information processing.

Strain-controlled Néel temperature and exchange bias enhancements in IrMn/CoFeB bilayers

We propose a numerical method, where first-principles calculations are combined with modified Monte Carlo simulations, and study the Néel temperature of antiferromagnetic IrMn and exchange bias effect in antiferromagnet/ferromagnet IrMn/CoFeB bilayers manipulated by the applications of tensile and compressive strains. The results show that both tensile and compressive strains linearly change the magnetic moment of Mn and the magnetocrystalline anisotropy of IrMn, and meanwhile, the uniaxially easy-axis directions under tensile and compressive strains are perpendicular. The strain-triggered increase in antiferromagnetic exchange coupling between Mn–Mn pairs is revealed and induces an up to 1.5 times enhancement of the Néel temperature of IrMn. Furthermore, the spontaneous and conventional exchange bias effects can be both observed under large tensile strains, also sensitive to the cooling field, and strongly enhanced roughly by 800% under 8 T in the application of 1.5% strain, which can be interpreted by the strain-induced high magnetocrystalline anisotropies. Thus, the tensile strains are better for controlling and optimizing the Néel temperature of IrMn and further exchange bias properties in IrMn-based heterostructures. This work establishes the correlations between microscopically and macroscopically magnetic responses to strain, indicating that strain can be an intriguing means of extrinsic manipulation of exchange bias, which is of importance for spintronic device applications.

Azo-Cyanamide Bridged Dinuclear Iron Complexes Exhibiting no Electronic Coupling but Moderate Magnetic Coupling between the two Iron Centers.

To investigate the effect of long-distance organic ligand on electronic coupling between metallic atoms, the mononuclear and dinuclear complexes [Cp(dppe)Fe(apc)] (1), [{Cp(dppe)Fe}2(μ-adpc)] (2), [{CpMe5(dppe)Fe}2(μ-adpc) (3) and their oxidized complexes [Cp(dppe)Fe(apc)][PF6] (1[PF6]), [{Cp(dppe)Fe}2(μ-adpc)][PF6] (2[PF6]2), [{CpMe5(dppe)Fe}2(μ-adpc)][PF6]2 (3[PF6]2) (Cp=1,3-cyclopentadiene, CpMe5=1,2,3,4,5-pentamethylcyclopentadiene, dppe=1,2-bis(diphenylphosphino)ethane), apc-=4-azo(phenylcyanamido)benzene and adpc2-=4,4'-azodi(phenylcyanamido)) were synthesized and characterized by cyclic voltammetry, UV-vis, single-crystal X-ray diffraction and Mössbauer spectra. Electrochemical measurements showed no electronic coupling between the two terminal Fe units, However, the investigation results of the magnetic properties of the two-electron oxidized complexes indicate the presence of moderate antiferromagnetic coupling across 18 Å distance.

Magnetic tunability in tetragonal Mn–Rh–Ir–Sn inverse Heusler compounds

Gaining control over magnetic structure has been an ongoing challenge in materials that form complex, nanoscale, and non-collinear magnetic configurations. Recently, it was predicted that tuning the ratio of the Dzyaloshinskii–Moriya interaction to the uniaxial magnetic anisotropy in tetragonal inverse Heuslers through changes in composition could allow a range of interesting magnetic states to be accessed, from simple ferrimagnetism, to helical and antiskyrmionic phases. Here, we show tunability of the magnetic phase behavior in the Mn–Rh–Sn system through Ir substitution on the Rh substructure. Iridium substitution correlates to an increase in the strength of ferromagnetic exchange couplings, at the expense of antiferromagnetic exchange couplings. However, we do not observe the complex non-collinear magnetic phases proposed previously, likely due to the extremely narrow composition window where these phases are predicted to form in a bulk sample. This work highlights the sensitivity of complex magnetic structures to stoichiometry, which makes them difficult to discover empirically.

Antiferromagnetic interlayer exchange coupled Co68B32/Ir/Pt multilayers

Synthetic antiferromagnetic structures can exhibit the advantages of high velocity similarly to antiferromagnets with the additional benefit of being imaged and read-out through techniques applied to ferromagnets. Here, we explore the potential and limits of synthetic antiferromagnets to uncover ways to harness their valuable properties for applications. Two synthetic antiferromagnetic systems have been engineered and systematically investigated to provide an informed basis for creating devices with maximum potential for data storage, logic devices, and skyrmion racetrack memories. The two systems considered are (system 1) CoB/Ir/Pt of N repetitions with Ir inducing the negative coupling between the ferromagnetic layers and (system 2) two ferromagnetically coupled multilayers of CoB/Ir/Pt, coupled together antiferromagnetically with an Ir layer. From the hysteresis, it is found that system 1 shows stable antiferromagnetic interlayer exchange coupling between each magnetic layer up to N = 7. Using Kerr imaging, the two ferromagnetic multilayers in system 2 are shown to undergo separate maze-like switches during hysteresis. Both systems are also studied as a function of temperature and show different behaviors. Micromagnetic simulations predict that in both systems the skyrmion Hall angle is suppressed with the skyrmion velocity five times higher in system 1 than system 2.

The interplay of covalency, cooperativity, and coupling strength in governing C-H bond activation in Ni2E2 (E = O, S, Se, Te) complexes.

Dinickel dichalcogenide complexes hold vital multifaceted significance across catalysis, electron transfer, magnetism, materials science, and energy conversion. Understanding their structure, bonding, and reactivity is crucial for all aforementioned applications. These complexes are classified as dichalcogenide, subchalcogenide, or chalcogenide based on metal oxidation and coordinated chalcogen, and due to the associated complex electronic structure, ambiguity often lingers about their classification. In this work, using DFT, CASSCF/NEVPT2, and DLPNO-CCSD(T) methods, we have studied in detail [(NiL)2(E2)] (L = 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecane; E = O, S, Se and Te) complexes and explored their reactivity towards C-H bond activation for the first time. Through a comprehensive analysis of the structure, bonding, and reactivity of a series of [(NiL)2(E2)] complexes with E = O, S, Se, and Te, our computational findings suggest that {Ni2O2} and {Ni2S2} are best categorised as dichalcogenide-type complexes. In contrast, {Ni2Se2} and {Ni2Te2} display tendencies consistent with the subchalcogenide classification, and this aligns with the earlier structural correlation proposed (Berry and co-workers, J. Am. Chem. Soc. 2015, 137, 4993) reports on the importance of the E-E bond strength. Our study suggests the reactivity order of {Ni2O2} > {Ni2S2} > {Ni2Se2} > {Ni2Te2} for C-H bond activation, and the origin of the difference in reactivity was attributed to the difference in the Ni-E bond covalency, and electronic cooperativity between two Ni centres that switch among the classification during the reaction. Further non-adiabatic analysis at the C-H bond activation step demonstrates a decrease in coupling strength as we progress down the group, indicating a correlation with metal-ligand covalency. Notably, the reactivity trend is found to be correlated to the strength of the antiferromagnetic exchange coupling constant J via developing a magneto-structural-barrier map - offering a hitherto unknown route to fine-tune the reactivity of this important class of compound.

Doping dependence of superconductivity on a honeycomb lattice within the framework of kinetic-energy-driven superconductivity

Unconventional superconductivity on a honeycomb lattice has received increasing interest since the discovery of graphene primarily due to the similarities between materials with a honeycomb lattice and cuprate superconductors. Many theoretical studies have been conducted on superconductivity on a honeycomb lattice, however, a consistent picture is still lacking. In this paper, we have extended the theory of kinetic-energy-driven superconductivity, which has been developed to investigate unconventional superconductivity in cuprate superconductors, to explore superconductivity on a honeycomb lattice within the t-J model. Our results demonstrate that the charge-carrier pair gap parameter with [Formula: see text]-wave symmetry exhibits a dome-like shape as a function of doping, with superconductivity emerging at a certain doping concentration and disappearing at high doping levels, similar to what has been observed in cuprate and cobaltate superconductors. Furthermore, the charge-carrier pair gap parameter decreases with increasing the value of [Formula: see text] (the ratio between the antiferromagnetic exchange coupling constant and the nearest-neighbor hopping integral), and approaches zero when [Formula: see text] reaches a sufficiently large value. This indicates that the antiferromagnetic order will suppress the superconducting state and a sufficiently strong exchange coupling will completely destroy the superconductivity. Taking into account our present results together with the corresponding results of cuprate and cobaltate superconductors, it appears that the dome-like shape of the doping dependence of the charge-carrier pair gap parameter may be a common feature in doped Mott insulators.

Metallophilic interactions and magnetism in heterobimetallic {Pt,M} lantern complexes

A small series of polymeric heterobimetallic {Pt,M} lantern complexes of the form [PtM(SAc)4DABCO]∞ (SAc = thioacetate, DABCO = 1,4-diazabicyclo[2,2,2]octane; M = Co (1), Ni (2), Zn (3)) has been synthesized, along with the discrete molecular analog of each polymer formed by replacing DABCO with quinuclidine (4–6). All compounds except 3 have been structurally characterized by single-crystal X-ray diffraction. Compound 1 shows a metallophilic Pt…Pt interaction of 3.1204(4) Å, while in 2 the same interaction is even shorter at 3.0944(10) Å. The electronic spectra of all compounds have been measured, which show d-d transitions of the 3d metal, Pt LMCT bands, and metal–metal charge transfer bands. Measurements of the temperature dependence of the magnetic susceptibility of 1 and 2 reveal antiferromagnetic exchange coupling between the 3d metal centers with J = −10 cm−1 for Co-containing 1 and J = −32 cm−1 between Ni centers for 2, both of which access the Pt…Pt metallophilic interactions.

Correlation‐Driven Magnetic Frustration and Insulating Behavior of TiF3

The halide perovskite TiF3, renowned for its intricate interplay between structure, electronic correlations, magnetism, and thermal expansion, is investigated. Despite its simple structure, understanding its low‐temperature magnetic behavior has been a challenge. Previous theories propose antiferromagnetic ordering. In contrast, experimental signatures for an ordered magnetic state are absent down to 10 K. The current study has successfully reevaluated the theoretical modeling of TiF3, unveiling the significance of strong electronic correlations as the key driver for its insulating behavior and magnetic frustration. In addition, frequency‐dependent optical reflectivity measurements exhibit clear signs of an insulating state. The analysis of the calculated magnetic data gives an antiferromagnetic exchange coupling with a net Weiss temperature of order 25 K as well as a magnetic response consistent with a S = 1/2 local moment per Ti3+. Yet, the system shows no susceptibility peak at this temperature scale and appears free of long‐range antiferromagnetic order down to 1 K. Extending ab initio modeling of the material to larger unit cells shows a tendency for relaxing into a noncollinear magnetic ordering, with a shallow energy landscape between several magnetic ground states, promoting the status of this simple, nearly cubic perovskite structured material as a candidate spin liquid.

Dirac-fermion-assisted interfacial superconductivity in epitaxial topological-insulator/iron-chalcogenide heterostructures

Over the last decade, the possibility of realizing topological superconductivity (TSC) has generated much excitement. TSC can be created in electronic systems where the topological and superconducting orders coexist, motivating the continued exploration of candidate material platforms to this end. Here, we use molecular beam epitaxy (MBE) to synthesize heterostructures that host emergent interfacial superconductivity when a non-superconducting antiferromagnet (FeTe) is interfaced with a topological insulator (TI) (Bi, Sb)2Te3. By performing in-vacuo angle-resolved photoemission spectroscopy (ARPES) and ex-situ electrical transport measurements, we find that the superconducting transition temperature and the upper critical magnetic field are suppressed when the chemical potential approaches the Dirac point. We provide evidence to show that the observed interfacial superconductivity and its chemical potential dependence is the result of the competition between the Ruderman-Kittel-Kasuya-Yosida-type ferromagnetic coupling mediated by Dirac surface states and antiferromagnetic exchange couplings that generate the bicollinear antiferromagnetic order in the FeTe layer.

Superexchange antiferromagnetism and cryogenic magnetocaloric effect in scheelite-type GdTi0.5Mo0.5O4 compound

Scheelite-type LnLiF4 compounds have become promising cryogenic magnetic refrigerants due to their giant low-field magnetocaloric effect (MCE). This work presents an example of a scheelite-type rare-earth transition metal oxide GdTi0.5Mo0.5O4. The magnetic interactions, magnetic phase transition (MPT) and MCE of GdTi0.5Mo0.5O4 compound were investigated through magnetization measurements and a mean-field approach. A mean-field model was used to elucidate the role of primarily superexchange antiferromagnetic (AFM) coupling on the magnetocaloric performance in this compound. From the analysis of the magnetization dependence, an isotropic AFM exchange coupling with energy scale εex = JnnS2 ≈ 1.7 K was estimated. The magnetic susceptibility reveals the occurrence of MPT from paramagnetic (PM) to AFM at the Néel temperature (TN ≈ 1.3 K). GdTi0.5Mo0.5O4 exhibits a large magnetic entropy change up to 43.3 J/(kg·K) at 1.3 K for μ0ΔH = 0−7 T, which makes it a cryogenic magnetic refrigerant with potential applications. Furthermore, a mean-field model with superexchange AFM above 3 K can well predict the MCE observed in GdTi0.5Mo0.5O4.

Slow magnetic relaxation behaviors and diamagnetic dilution studies of a carboxyl bridged dinuclear dysprosium(III) complex

By using a rigid bulky carboxylic ligand α-cyanocinnamic acid (CCA), a dinuclear dysprosium (III) complex [Dy2(CCA)6 (MeOH)4] (1) was synthesized. Single crystal X-ray crystallography reveals that the two eight-coordinate dysprosium ions are bridged by four deprotonated carboxyl groups, forming a centrosymmetric paddle-wheel-like structure. Dynamic magnetic property measurements indicate that complex 1 displays field-induced slow magnetic relaxation. The temperature-dependent relaxation times can be fitted using Orbach and Raman processes with parameters of n = 2.8 (2), C = 27 (8) s−1/Kn, τ0 = 5 (2) × 10−10 s and Ueff = 40 (3) cm−1. Magnetic studies on the diamagnetic YIII-diluted analogue [Dy0.206Y1.794(CCA)6 (MeOH)4] (2) reveal its slow magnetic relaxation behavior without external dc field and the antiferromagnetic coupling between the DyIII ions in 1. Fits on the obtained relaxation times of 2 lead to the parameters of n = 4.5 (3), C = 0.7 (2) s−1/Kn, τ0 = 2.8 (2) × 10−9 s and Ueff = 38 (2) cm−1. The results suggest that slow magnetic relaxation originates from the single-ion relaxation of DyIII ions. Moreover, the diamagnetic dilution can suppress other fast relaxation pathways at low temperature, on account of the elimination of magnetic coupling and dipolar interaction. Ab initio calculations were then performed on the single DyIII ion species {YDy} and indicate that the first excited Kramers doublets (KDs) lie at ca. 76 cm−1, which is slightly higher than the experimental Ueff value. The intramolecular magnetic interactions were also calculated and indicate a weak ferromagnetic dipole-diploe magnetic interaction and an antiferromagnetic exchange coupling.

The Stack Optimization of Magnetic Heterojunction Structures for Next-Generation Spintronic Logic Applications.

Magnetic heterojunction structures with a suppressed interfacial Dzyaloshinskii-Moriya interaction and a sustainable long-range interlayer exchange coupling are achieved with an ultrathin platinum insertion layer. The systematic inelastic light scattering spectroscopy measurements indicate that the insertion layer restores the symmetry of the system and, then, the interfacial Dzyaloshinskii-Moriya interaction, which can prevent the identical magnetic domain wall motions, is obviously minimized. Nevertheless, the strong interlayer exchange coupling of the system is maintained. Consequently, synthetic ferromagnetic and antiferromagnetic exchange couplings as a function of the ruthenium layer thickness are observed as well. Therefore, these optimized magnetic multilayer stacks can avoid crucial issues, such as domain wall tilting and position problems, for next-generation spintronic logic applications. Moreover, the synthetic antiferromagnetic coupling can open a new path to develop a radically different NOT gate via current-induced magnetic domain wall motions and inversions.

Frustrated magnetism of the spin-1 kagome antiferromagnet β-BaNi3(VO4)2(OH)2

We propose the newly synthesized β-BaNi3(VO4)2(OH)2 (space group: ) as a candidate for the spin-1 kagome Heisenberg antiferromagnet (KHA). The compound features a uniform kagome lattice of Ni2+ (S = 1) ions with a large interlayer distance. High-field measurements at low temperatures reveal a susceptibility local minimum at ∼9 T, resembling a 1/3 magnetization plateau as predicted by the pure S = 1 KHA model. Below ∼6 K, approximately 1% of the spins exhibit spin-glass order, which may be attributed to the nanocrystalline grain size of ∼50 nm. Despite the antiferromagnetic exchange coupling strength of ∼7 K, the majority of spins remain disordered down to ∼0.1 K as indicated by the observed power-law behaviors in magnetic specific heat . Our results demonstrate that the low-energy magnetic excitations in β-BaNi3(VO4)2(OH)2 are gapless, which contradicts the current theoretical expectations of the ideal model.

Phonon dichroism in proximitized graphene

We systematically investigate the phonon dichroism in proximitized graphene with broken time-reversal symmetry. We find that in the absence of any type of spin–orbit coupling, phonon dichroism vanishes. Linear and circular phonon dichroism occur in the presence of uniform (staggered) intrinsic spin–orbit coupling and ferromagnetic (antiferromagnetic) exchange coupling. All these situations can be distinguished by their specific behaviors of phonon absorption at the transition point. Our finding provides new possibilities to use phonon dichroism to identify the form of spin–orbit coupling and exchange coupling in proximitized graphene on various magnetic substrates.