2D Magnetism Research Articles

From Stoner to local moment magnetism in atomically thin Cr2Te3

The field of two-dimensional (2D) ferromagnetism has been proliferating over the past few years, with ongoing interests in basic science and potential applications in spintronic technology. However, a high-resolution spectroscopic study of the 2D ferromagnet is still lacking due to the small size and air sensitivity of the exfoliated nanoflakes. Here, we report a thickness-dependent ferromagnetism in epitaxially grown Cr2Te3 thin films and investigate the evolution of the underlying electronic structure by synergistic angle-resolved photoemission spectroscopy, scanning tunneling microscopy, x-ray absorption spectroscopy, and first-principle calculations. A conspicuous ferromagnetic transition from Stoner to Heisenberg-type is directly observed in the atomically thin limit, indicating that dimensionality is a powerful tuning knob to manipulate the novel properties of 2D magnetism. Monolayer Cr2Te3 retains robust ferromagnetism, but with a suppressed Curie temperature, due to the drastic drop in the density of states near the Fermi level. Our results establish atomically thin Cr2Te3 as an excellent platform to explore the dual nature of localized and itinerant ferromagnetism in 2D magnets.

Cr silicate as a prototype for engineering magnetic phases in air-stable two-dimensional transition-metal silicates

Identifying environmentally inert, ferromagnetic two-dimensional (2D) materials with high Curie temperatures (T c) down to the single layer limit has been an obstacle to fundamental studies of 2D magnetism and application of 2D heterostructures to spin-polarized devices. To address this challenge, the growth, structure and magnetic properties of a 2D Cr-silicate single layer on Pt(111) was investigated experimentally and theoretically. The layer was grown by sequentially depositing SiO and Cr followed by annealing in O2. Scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), and low energy electron microscopy all indicated a well-ordered layer that uniformly covered the surface, with STM and LEED indicating that the silicate relaxed to its favored lattice constant. Further experimental characterizations demonstrated that the Cr was nominally 3+ but with a lower electron density than typical trivalent Cr compounds. Comparison with theory identified a Cr2Si2O9 structure that resembles a single layer of a dehydrogenated dioctahedral silicate. Magnetic circular dichroism in x-ray absorption spectroscopy revealed a ferromagnetically ordered state up to at least 80 K. Theoretical analysis revealed that the Cr in a dehydrogenated Cr-silicate/Pt(111) is more oxidized than Cr in freestanding Cr2Si2O9H4 layers. This greater oxidation was found to enhance ferromagnetic coupling and suggests that the magnetism may be tuned by doping. The 2D Cr-silicate is the first member of a broad series of possible layered first-row transition metal silicates with magnetic order; thus, this paper introduces a new platform for investigating 2D ferromagnetism and the development of magnetoelectronic and spintronic devices by stacking 2D atomic layers.

A novel vardenafil analog in a healthcare product: Preparation, characterization, and quantification

Objective: This study is aimed to develop a qualitative and quantitative method to detect a novel vardenafil analogue from a healthcare product, which is claimed to enhance sexual function. Method: The unknown compound was detected by non-targeted screening using ultra-high performance liquid chromatography-quadrupole-time-of-flight mass spectrometry (UPLC-Q-TOF-MS). MS2 spectra showed that the characteristic fragment ions of this unknown compound were highly similar to those of vardenafil. This compound was subsequently isolated by silica gel column chromatography and characterized by 1D (dimension) and 2D nuclear magnet resonance (NMR) specta, ultra-violet (UV) spectra, and fourier transform infrared (IR) spectra. A quantitative method for analyzing this identified compound in various healthcare product was developed based on high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS).Results: The unknown compound was identified as 2-(5-((4-ethylpiperazin-1-yl)sulfonyl)-2-propoxyphenyl)-5-methyl-7-propylimidazo.[5,1-f] [1,2,4]triazin-4(3H)-one based on the spectroscopic data. Quantitative results revealed that the matrix calibration curves of this compound had a good linear ranges of 2～50 ng/mL in pressed candy (R2 = 0.998), energy coffee (R2 = 0.999), and health wine (R2 = 0.997), respectively. The matrix effects, recoveries, and limit of quantitation (LOQ) of this compound all met the requirements of quantitative validation. Finally, the content of this compound in 5 batches of positive samples ranged from 1.24 to 7.20 g/kg. Conclusion: This study identified a novel vardenafil analog from a healthcare product and named it O-propyl vardenafil, and this compound was distinguished from vardenafil by the replacement of the ethyl group with a propyl group at the aryl alkyl ether moiety. Our developed quantitative method could meet practical needs. The high positive rate (16.67%) in 30 samples suggested that the related regulators should be alert to O-propyl vardenafil in routine test since it has not been detected ever before.

Multiple antiferromagnetic phases and magnetic anisotropy in exfoliated CrBr3 multilayers

In twisted two-dimensional (2D) magnets, the stacking dependence of the magnetic exchange interaction can lead to regions of ferromagnetic and antiferromagnetic interlayer order, separated by non-collinear, skyrmion-like spin textures. Recent experimental searches for these textures have focused on CrI3, known to exhibit either ferromagnetic or antiferromagnetic interlayer order, depending on layer stacking. However, the very strong uniaxial anisotropy of CrI3 disfavors smooth non-collinear phases in twisted bilayers. Here, we report the experimental observation of three distinct magnetic phases—one ferromagnetic and two antiferromagnetic—in exfoliated CrBr3 multilayers, and reveal that the uniaxial anisotropy is significantly smaller than in CrI3. These results are obtained by magnetoconductance measurements on CrBr3 tunnel barriers and Raman spectroscopy, in conjunction with density functional theory calculations, which enable us to identify the stackings responsible for the different interlayer magnetic couplings. The detection of all locally stable magnetic states predicted to exist in CrBr3 and the excellent agreement found between theory and experiments, provide complete information on the stacking-dependent interlayer exchange energy and establish twisted bilayer CrBr3 as an ideal system to deterministically create non-collinear magnetic phases.

High-harmonic generation in spin and charge current pumping at ferromagnetic or antiferromagnetic resonance in the presence of spin–orbit coupling

One of the cornerstone effects in spintronics is spin pumping by dynamical magnetization that is steadily precessing (around, for example, the z-axis) with frequency ω 0 due to absorption of low-power microwaves of frequency ω 0 under the resonance conditions and in the absence of any applied bias voltage. The two-decades-old ‘standard model’ of this effect, based on the scattering theory of adiabatic quantum pumping, predicts that component of spin current vector is time-independent while and oscillate harmonically in time with a single frequency ω 0 whereas pumped charge current is zero in the same adiabatic limit. Here we employ more general approaches than the ‘standard model’, namely the time-dependent nonequilibrium Green’s function (NEGF) and the Floquet NEGF, to predict unforeseen features of spin pumping: namely precessing localized magnetic moments within a ferromagnetic metal (FM) or antiferromagnetic metal (AFM), whose conduction electrons are exposed to spin–orbit coupling (SOC) of either intrinsic or proximity origin, will pump both spin and charge I(t) currents. All four of these functions harmonically oscillate in time at both even and odd integer multiples of the driving frequency ω 0. The cutoff order of such high harmonics increases with SOC strength, reaching in the one-dimensional FM or AFM models chosen for demonstration. A higher cutoff can be achieved in realistic two-dimensional (2D) FM models defined on a honeycomb lattice, and we provide a prescription of how to realize them using 2D magnets and their heterostructures.

Coupling between magnetic and transport properties in magnetic layered material Mn2-xZnxSb

We synthesized single crystals for Mn2-xZnxSb (0 ≤ x ≤ 1) and studied their magnetic and electronic transport properties. This material system displays rich magnetic phase tunable with temperature and Zn composition. In addition, two groups of distinct magnetic and electronic properties, separated by a critical Zn composition of x = 0.6, are discovered. The Zn-less samples are metallic and characterized by a resistivity jump at the magnetic ordering temperature, while the Zn-rich samples lose metallicity and show a metal-to-insulator transition-like feature tunable by magnetic field. Our findings establish Mn2-xZnxSb as a promising material platform that offers opportunities to study how the coupling of spin, charge, and lattice degrees of freedom governs interesting transport properties in 2D magnets, which is currently a topic of broad interest.

Gate-Tunable Renormalization of Spin-Correlated Flat-Band States and Bandgap in a 2D Magnetic Insulator.

Emergent quantum phenomena in two-dimensional van der Waal (vdW) magnets are largely governed by the interplay between exchange and Coulomb interactions. The ability to precisely tune the Coulomb interaction enables the control of spin-correlated flat-band states, band gap, and unconventional magnetism in such strongly correlated materials. Here, we demonstrate a gate-tunable renormalization of spin-correlated flat-band states and bandgap in magnetic chromium tribromide (CrBr3) monolayers grown on graphene. Our gate-dependent scanning tunneling spectroscopy (STS) studies reveal that the interflat-band spacing and bandgap of CrBr3 can be continuously tuned by 120 and 240 meV, respectively, via electrostatic injection of carriers into the hybrid CrBr3/graphene system. This can be attributed to the self-screening of CrBr3 arising from the gate-induced carriers injected into CrBr3, which dominates over the weakened remote screening of the graphene substrate due to the decreased carrier density in graphene. Precise tuning of the spin-correlated flat-band states and bandgap in 2D magnets via electrostatic modulation of Coulomb interactions not only provides effective strategies for optimizing the spin transport channels but also may exert a crucial influence on the exchange energy and spin-wave gap, which could raise the critical temperature for magnetic order.

Theoretical Study on the Raman Effect Due to Magnons in Two-Dimensional Magnets.

Raman spectroscopy is one of the most useful experimental tools for studying elementary excitations in two-dimensional (2D) materials. The Raman scattering due to phonons was widely employed for detecting structural evolutions, especially those caused by magnetic phase transitions in 2D magnets. A first-principles theory of the Raman scattering effect caused by magnons is still lacking. We theoretically study the magnon Raman effect in 2D magnet CrI3. We propose a first-principles method and have calculated the intensity of circularly polarized Raman signals due to different magnon modes in the CrI3 monolayer and bilayers. The calculated Raman intensities due to magnons in the CrI3 monolayer and the rhombohedral bilayer are consistent with the selection rule deduced from the magnon pseudoangular moment and the parity of magnon modes. We also find that the selection rule is violated in the symmetry-broken monoclinic bilayer due to interlayer coupling.

Giant Dzyaloshinskii-Moriya interaction, strong XXZ-type biquadratic coupling, and bimeronic excitations in the two-dimensional CrMnI6 magnet

Two-dimensional magnets have been discovered recently as a new class of quantum matter exhibiting a broad wealth of exotic phenomena, including notably various topological excitations rooted in emergent exchange couplings between the localized magnetic moments. By analyzing the anisotropies in the single-ion magnetization and two-body exchange couplings obtained from first-principles calculations, we reveal coexistence of both giant Dzyaloshinskii–Moriya interaction and strong anisotropic XXZ-type biquadratic coupling in a recently predicted monolayer CrMnI6 magnet. The former is induced by the spontaneous in-plane inversion symmetry breaking in the bipartite system, the latter is inherently tied to the distinct high-spin state of the Mn sublattice, while the large magnitudes of both stem from the significant spin-orbit coupling. Next, we use atomistic magnetics simulations to demonstrate the vital role of Dzyaloshinskii–Moriya interaction in harboring topological bimeronic excitations, and show that the biquadratic coupling favors a Berezinskii–Kosterlitz–Thouless-like transition as the system reduces its temperature from the paramagnetic phase. These findings substantially enrich our understanding of the microscopic couplings in 2D magnets, with appealing application potentials.

Exploring the Structural, Electronic, Magnetic, and Transport Properties of 2D Cr, Fe, and Zr Monoborides.

Compared to other 2D materials, MBenes are at an early stage of investigation in terms of both experimental and theoretical approaches. However, their wide range of possible 2D structures leads to novel and challenging properties and consequent applications. From all the possible stoichiometries, we performed a theoretical study of orthorhombic and hexagonal M2B2 MBenes within the framework of density functional theory. We found that both symmetries of Cr2B2, Fe2B2, and Zr2B2 show metallic behavior and could be grown under certain conditions as they were demonstrated to be dynamically stable. Moreover, the values of the magnetic moment observed, in specific ferromagnetic cases exceeding 2.5μB/M2B2, make them suitable as robust 2D magnets. Our findings represent an important step in the understanding of MBenes and open several windows to future research in fields like energy conversion and storage, sensing, catalysis, biochemistry, and nanotechnology, among others.

Electronic phase transition, perpendicular magnetic anisotropy and high Curie temperature in Janus FeClF

How to enhance the spin polarization, the Curie temperature and the perpendicular magnetic anisotropy (PMA) is crucial for the applications of 2D magnets in spintronic devices. In this work, based on the experimental FeCl2 flakes and the predicted in-plane magnetic anisotropy (IMA) and lower Curie temperature of FeCl2 monolayer, we use first-principles and Monte Carlo simulation to explore the strain and carrier-doping effects on the electronic and magnetic properties of Janus FeClF monolayer. The structure is stable within −10% to 2% biaxial strain. Janus FeClF monolayer can experience transitions from a half-semiconductor to a spin gapless semiconductor (SGS) around the −6% compressive strain, and from the IMA to the PMA at the −7% compressive strain. The super-exchange Fe–F/Cl–Fe interaction induces the ferromagnetic coupling, and the Curie temperature can be considerably enhanced from 56 K to 281 K at the −10% compressive strain. The half-metallicity can be achieved whether under electron doping or hole doping. The Fe-d orbitals and the spin–orbit coupling interaction between occupied and unoccupied intraorbital states are responsible for the electronic phase transition and the magnetic anisotropy, respectively. Remarkably, the compressive −10% strain and the 0.02 e doping collectively increase the Curie temperature to near room temperature (286 K). The high spin polarization (exhibiting SGS and half-metal), the PMA and the near-room-temperature ferromagnetism induced by strain and doping make Janus FeClF a promising candidate for 2D spintronic applications, which will stimulate experimental and theoretical broad studies on this class of Janus monolayers FeXY (X,Y = F, Cl, Br, and X ≠ Y).

Chirality reversal of magnetic solitons in chiral Cr1/3TaS2

Ferromagnetism in two-dimensional (2D) materials provides an ideal platform to study emergent electromagnetic phenomena in low dimensions for future spintronics. In magnetic-element intercalated transition metal dichalcogenides, topologically nontrivial spin textures, such as chiral helimagnetic spin states and chiral soliton lattices, are realized due to the chiral lattice distortions induced by intercalated magnetic ions. Consequently, the magnetic chirality is predictably determined by the sign of antisymmetric exchange interaction (or Dzyaloshinskii–Moriya interaction, DMI) vector that is coupled to the underlying crystal chirality. Here, using cryogenic Lorentz phase microscopy, we directly observed the chirality reversal behavior of the chiral soliton lattices in Cr1/3TaS2 across the structural defects. We show that a partial 1 T stacking in 2H-TaS2 locally reduces DMI, leading to magnetic chirality reversal with direct atomic resolution imaging. Our experimental results show that manipulation of stacking sequence provides a viable way to control the chirality of topologically nontrivial soliton lattices in 2D magnets.

Multifunctional properties of a polar spin chain compound [N(C3H7)4][Cu(C8H4NO4)]·H2O exhibiting both one-dimensional magnetism and nonlinear optical activity

Functional materials with multiple properties are urgent to be explored to reach high requirements for applications nowadays. In this work, a new multifunctional one-dimensional (1D) chain compound [N(C3H7)4][Cu(ohpma)]·H2O 1 (ohpma = deprotonated N-(2-hydoxyphenyl)oxamic acid) exhibiting both 1D antiferromagnetic and nonlinear optical properties, which are both originated from the same polar [Cu(C8H4NO4)] magnetic units, has been successfully synthesized by evaporation at room temperature. Bis-polydentate nature of the (ohpma)3− ligand with constrained tridentate and bidentate coordination sites conducts Cu2+ ions coordinating in different geometries and forms 1D chains along the c axis, which are further separated by the [N(C3H7)4]+ cations. And the 1D magnetic chains further exhibit noncentrosymmetric polar arrangement. Nonlinear optical study shows polar compound 1 exhibits a discernible second-harmonic generation (SHG) efficiency and the calculation of the partial density of states indicates that the SHG efficiency of 1 is mainly originated from the polar [Cu(C8H4NO4)] magnetic units. Moreover, magnetic susceptibility shows a broad maximum around 70 K with strong intrachain interaction of J/kB = −113.0 K but no long-range order is observed down to 2 K, suggesting that 1 shows a good 1D magnetism. Both good 1D magnetism and SHG activity suggest that 1 could be as a potential multifunctional material, particularly.

Electric-field control of reversible electronic and magnetic transitions in two-dimensional oxide monolayer magnets

Atomically thin oxide magnetic materials are highly desirable due to the promising potential to integrate two-dimensional (2D) magnets into next-generation spintronics. Therefore, 2D oxide magnetism is expected to be effectively tuned by the magnetic and electrical fields, holding prospective for future low-dissipation electronic devices. However, the electric-field control of 2D oxide monolayer magnetism has rarely been reported. Here, we present the realization of 2D monolayer magnetism in oxide (SrRuO3)1/(SrTiO3)N (N = 1, 3) superlattices that shows an efficient and reversible phase transition through electric-field controlled proton (H+) evolution. By using ionic liquid gating to modulate the proton concentration in (SrRuO3)1/(SrTiO3)1 superlattice, an electric-field induced metal-insulator transition was observed, along with gradually suppressed magnetic ordering and modulated magnetic anisotropy. Theoretical analysis reveals that proton intercalation plays a crucial role in both electronic and magnetic phase transitions. Strikingly, SrTiO3 layers can act as a proton sieve, which have a significant influence on proton evolution. Our work stimulates the tuning functionality of 2D oxide monolayer magnetism by voltage control, providing potential for future energy-efficient electronics.

Interplay of structure and magnetic ordering in a two-dimensional titanium monolayer: A first-principles study

Two-dimensional (2D) magnetic materials have attracted a lot of interest as ideal platforms for gaining fundamental insights into magnetism and as promising candidates for applications in spintronics. The potential of 2D magnets would be greatly enhanced by the efficient interaction between magnetism and other physical properties, such as electric, topological, and elastic properties. In this work, we use first-principles density functional theory to study the interplay between the structure and magnetic ordering of an elemental titanium monolayer in non-magnetic, ferromagnetic, and antiferromagnetic configurations crystallizing in square and honeycomb lattices. Our results reveal that planar structures favor ferromagnetic ordering whereas buckling of the monolayer favors antiferromagnetic ordering in the system. Our results are understood in terms of the coupling of the ZO phonon mode with the magnetic ordering of the material. Our results highlight the potential for creating novel devices where the magnetic moment and the magnetic state of the system can be tuned with atomic scale fluctuations of a free standing magnetic membrane.

Stable antiferromagnetic property and tunable electronic structure of two-dimensional MnPX3 (X = S and Se) from pristine structure to Janus phase

Transition-metal phosphorus trichalcogenides have been considered as very promising two-dimensional (2D) magnetic candidates up-to-date. We performed a systematical first-principles study on the electronic structures and magnetic properties of pristine MnPX3 (X = S and Se) and Janus Mn2P2S3Se3 monolayers. All monolayers behave as a direct-band-gap semiconductor in antiferromagnetic ground state which is caused by strong direct and indirect exchange interactions. It is found that the electronic structures and magnetic properties can be manipulated by Janus phase. The calculated band gap is 2.44 eV, 1.80 eV and 1.86 eV for MnPS3, MnPSe3 and Mn2P2S3Se3 with a valley polarization with consideration of spin–orbital coupling (SOC), respectively. In particular, significant energy-splittings emerge in the SOC-band structures of Janus Mn2P2S3Se3 due to its broken-inversion-symmetry. Estimated by Monte Carlo simulations, the Néel temperature is 96 K, 71 K and 79 K based on Ising model while halved down to 41 K, 33 K and 36 K on the basis of XY model for MnPS3, MnPSe3 and Mn2P2S3Se3, respectively, indicating the XY model should be more reliable to describe the spin dynamics. Our research offers an insight into the magnetic mechanism and paves a feasible path to modulate the magnetism for 2D magnets in realistic applications on spintronics.

Ferromagnetism emerged from non-ferromagnetic atomic crystals

The recently emerged ferromagnetic two-dimensional (2D) materials provide unique platforms for compact spintronic devices down to the atomic-thin regime; however, the prospect is hindered by the limited number of ferromagnetic 2D materials discovered with limited choices of magnetic properties. If 2D antiferromagnetism could be converted to 2D ferromagnetism, the range of 2D magnets and their potential applications would be significantly broadened. Here, we discovered emergent ferromagnetism by interfacing non-magnetic WS2 layers with the antiferromagnetic FePS3. The WS2 exhibits an order of magnitude enhanced Zeeman effect with a saturated interfacial exchange field ~38 Tesla. Given the pristine FePS3 is an intralayer antiferromagnet, the prominent interfacial exchange field suggests the formation of ferromagnetic FePS3 at interface. Furthermore, the enhanced Zeeman effect in WS2 is found to exhibit a strong WS2-thickness dependence, highlighting the layer-tailorable interfacial exchange coupling in WS2-FePS3 heterostructures, which is potentially attributed to the thickness-dependent interfacial hybridization.

Na3VAs2 monolayer: A two-dimensional intrinsic room-temperature ferromagnetic half-metal with large desired perpendicular magnetic anisotropy

Recent experiments have proved that the intrinsic two-dimensional (2D) magnetism has aroused strong interest in the application of advanced spintronics. However, low Curie temperature and low magnetic anisotropy energy (MAE) greatly limit their application range. By density functional theory calculation, we predict a stable 2D Na3VAs2 monolayer, which shows intrinsic ferromagnetic (FM) order and a large MAE (570 μeV per V atom). The Na3VAs2 monolayer has a local magnetic moment about 2 μB/V. Monte Carlo simulation shows that the Curie temperature (TC) of Na3VAs2 monolayer is up to 305 K based on anisotropic Heisenberg mode. More interestingly, the 2D Na3VAs2 monolayer shows an ideal half-metallic abundance, and it still maintains half-metallic characteristics under various strains. In addition, this monolayer has good dynamic, thermal, and mechanical stability. The excellent properties of the Na3VAs2 monolayer makes it great potential to be used in spintronic devices.

Extreme Air Sensitivity and Nonself-Limited Oxidation of Two-Dimensional Magnetic Tellurides

The two-dimensional (2D) self-intercalated van der Waals magnets, chromium tellurides (Cr1+δTe2), with room temperature ferromagnetism and exotic topological spin textures, have emerged as an attractive platform for the development of ultrathin spintronic devices. While many prior studies claim Cr1+δTe2 are air-stable, which is crucial for practical applications, we demonstrate that within only minutes of exposure to air dramatic changes occur in the Raman and X-ray photoelectron spectroscopy spectra of nanoplates at room temperature. Time-dependent magnetization measurements and transmission electron microscopy studies suggested the rapid oxidation is not self-limited and has distinct processes on the surfaces and edges. Density functional theory calculations confirmed the spontaneous oxygen adsorption on the surface and the thermodynamically favorable oxidation process. These findings demonstrate unambiguously that the surface of Cr1+δTe2 is extremely air-sensitive, highlighting the necessity of surface protection for fundamental studies of intrinsic 2D magnetism and practical applications of advanced spintronic devices.

Huge perpendicular magnetic anisotropy in a 12-fold planar hypercoordinate W@B12(NCCN)3 monolayer

Two-dimensional (2D) materials with planar hypercoordinate motifs are attractive in terms of both fundamental science and technological applications. Herein, we construct a stable hexagonal 2D W@B12(NCCN)3 monolayer using W@B12 cluster as a building block and –NCCN– as a bridge linker. Multi-center bonding analysis reveals that the abundant 3c–1e B–W–Β σ bonds are responsible for the stability of a 12-fold coordinated W@B12 wheel, which has the highest coordination number reported for a planar system. Moreover, 3c–1e Β−Ν−Β, 4c − 1e N–C–C–N, and 13c − 1e W–B12 π bonds together form big delocalized π bonds, endowing 2D W@B12(NCCN)3 with unusual stability. Remarkably, 2D W@B12(NCCN)3 is a robust ferromagnetic half-metal with a large orbital moment anisotropy of 1.3 μB, a high out-of-plane magnetic anisotropy energy of 199 meV/atom, and a high Curie temperature of 150 K, which provides a potential candidate for high-density memory devices. These findings provide vital guidance for the design of 2D magnets with planar hypercoordination and unusual functionality.