Multistep magnetization switching in orthogonally twisted ferromagnetic monolayers.

The advent of twist engineering in two-dimensional crystals enables the design of van der Waals heterostructures with emergent properties. In the case of magnets, this approach can afford artificial antiferromagnets with tailored spin arrangements. Here we fabricate an orthogonally twisted bilayer by twisting two CrSBr ferromagnetic monolayers with an easy-axis in-plane spin anisotropy by 90°. The magnetotransport properties reveal multistep magnetization switching with a magnetic hysteresis opening, which is absent in the pristine case. By tuning the magnetic field, we modulate the remanent state and coercivity and select between hysteretic and non-hysteretic magnetoresistance scenarios. This complexity pinpoints spin anisotropy as a key aspect in twisted magnetic superlattices. Our results highlight control over the magnetic properties in van der Waals heterostructures, leading to a variety of field-induced phenomena and opening a fruitful playground for creating desired magnetic symmetries and manipulating non-collinear magnetic configurations.

Nonvolatile Electric Control of Antiferromagnet CrSBr.

van der Waals magnets are emerging as a promising material platform for electric field control of magnetism, offering a pathway toward the elimination of external magnetic fields from spintronic devices. A further step is the integration of such magnets with electrical gating components that would enable nonvolatile control of magnetic states. However, this approach remains unexplored for antiferromagnets, despite their growing significance in spintronics. Here, we demonstrate nonvolatile electric field control of magnetoelectric characteristics in van der Waals antiferromagnet CrSBr. We integrate a CrSBr channel in a flash-memory architecture featuring charge trapping graphene multilayers. The electrical gate operation triggers a nonvolatile 200% change in the antiferromagnetic state of CrSBr resistance by manipulating electron accumulation/depletion. Moreover, the nonvolatile gate modulates the metamagnetic transition field of CrSBr and the magnitude of magnetoresistance. Our findings highlight the potential of manipulating magnetic properties of antiferromagnetic semiconductors in a nonvolatile way.

Thermo-Magnetostrictive Effect for Driving Antiferromagnetic Two-Dimensional Material Resonators.

Magnetostrictive coupling has recently attracted interest as a sensitive method for studying magnetism in two-dimensional (2D) materials by mechanical means. However, its application in high-frequency magnetic actuators and transducers requires rapid modulation of the magnetic order, which is difficult to achieve with external magnets, especially when dealing with antiferromagnets. Here, we optothermally modulate the magnetization in antiferromagnetic 2D material membranes of metal phosphor trisulfides (MPS3), to induce a large high-frequency magnetostrictive driving force. From the analysis of the temperature-dependent resonance amplitude, we provide evidence that the force is due to a thermo-magnetostrictive effect, which significantly increases near the Neél temperature, due to the strong temperature dependence of the magnetization. By studying its angle dependence, we find the effect is observed to follow anisotropic magnetostriction of the crystal lattice. The results show that the thermo-magnetostrictive effect results in a strongly enhanced thermal expansion force near the critical temperature of magnetostrictive 2D materials, which can enable more efficient actuation of nano-magnetomechanical devices and can also provide a route for studying the high-frequency coupling among magnetic, mechanical, and thermodynamic degrees of freedom down to the 2D limit.

Charge Transfer and Asymmetric Coupling of MoSe2 Valleys to the Magnetic Order of CrSBr.

van der Waals heterostructures composed of two-dimensional (2D) transition metal dichalcogenides and vdW magnetic materials offer an intriguing platform to functionalize valley and excitonic properties in nonmagnetic TMDs. Here, we report magneto photoluminescence (PL) investigations of monolayer (ML) MoSe2 on the layered A-type antiferromagnetic (AFM) semiconductor CrSBr under different magnetic field orientations. Our results reveal a clear influence of the CrSBr magnetic order on the optical properties of MoSe2, such as an anomalous linear-polarization dependence, changes of the exciton/trion energies, a magnetic-field dependence of the PL intensities, and a valley g-factor with signatures of an asymmetric magnetic proximity interaction. Furthermore, first-principles calculations suggest that MoSe2/CrSBr forms a broken-gap (type-III) band alignment, facilitating charge transfer processes. The work establishes that antiferromagnetic-nonmagnetic interfaces can be used to control the valley and excitonic properties of TMDs, relevant for the development of opto-spintronics devices.

Controlling Magnetism with Light in a Zero Orbital Angular Momentum Antiferromagnet.

Antiferromagnetic materials feature intrinsic ultrafast spin dynamics, making them ideal candidates for future magnonic devices operating at THz frequencies. A major focus of current research is the investigation of optical methods for the efficient generation of coherent magnons in antiferromagnetic insulators. In magnetic lattices endowed with orbital angular momentum, spin-orbit coupling enables spin dynamics through the resonant excitation of low-energy electric dipoles such as phonons and orbital resonances which interact with spins. However, in magnetic systems with zero orbital angular momentum, microscopic pathways for the resonant and low-energy optical excitation of coherent spin dynamics are lacking. Here, we consider experimentally the relative merits of electronic and vibrational excitations for the optical control of zero orbital angular momentum magnets, focusing on a limit case: the antiferromagnet manganese phosphorous trisulfide (MnPS_{3}), constituted by orbital singlet Mn^{2+} ions. We study the correlation of spins with two types of excitations within its band gap: a bound electron orbital excitation from the singlet orbital ground state of Mn^{2+} into an orbital triplet state, which causes coherent spin precession, and a vibrational excitation of the crystal field that causes thermal spin disorder. Our findings cast orbital transitions as key targets for magnetic control in insulators constituted by magnetic centers of zero orbital angular momentum.

Tweaking the Optoelectronic Properties of S-Doped Polycyclic Aromatic Hydrocarbons by Chemical Oxidation.

Peri-thiaxanthenothiaxanthene, an S-doped analog of peri-xanthenoxanthene, is used as a polycyclic aromatic hydrocarbon (PAH) scaffold to tune the molecular semiconductor properties by editing the oxidation state of the S-atoms. Chemical oxidation of peri-thiaxanthenothiaxanthene with H2 O2 led to the relevant sulfoxide and sulfone congeners, whereas electrooxidation gave access to sulfonium-type derivatives forming crystalline mixed valence (MV) complexes. These complexes depicted peculiar molecular and solid-state arrangements with face-to-face π-π stacking organization. Photophysical studies showed a widening of the optical bandgap upon progressive oxidation of the S-atoms, with the bis-sulfone derivative displaying the largest value (E00 =2.99 eV). While peri-thiaxanthenothiaxanthene showed reversible oxidation properties, the sulfoxide and sulfone derivatives mainly showed reductive events, corroborating their n-type properties. Electric measurements of single crystals of the MV complexes exhibited a semiconducting behavior with a remarkably high conductivity at room temperature (10-1 -10-2  S cm-1 and 10-2 -10-3  S cm-1 for the O and S derivatives, respectively), one of the highest reported so far. Finally, the electroluminescence properties of the complexes were tested in light-emitting electrochemical cells (LECs), obtaining the first S-doped mid-emitting PAH-based LECs.

Tunable Strong Coupling of Mechanical Resonance between Spatially Separated FePS3 Nanodrums.

Coupled nanomechanical resonators made of two-dimensional materials are promising for processing information with mechanical modes. However, the challenge for these systems is to control the coupling. Here, we demonstrate strong coupling of motion between two suspended membranes of the magnetic 2D material FePS3. We describe a tunable electromechanical mechanism for control over both the resonance frequency and the coupling strength using a gate voltage electrode under each membrane. We show that the coupling can be utilized for transferring data between drums by amplitude modulation. Finally, we also study the temperature dependence of the coupling and how it is affected by the antiferromagnetic phase transition characteristic of this material. The presented electrical coupling of resonant magnetic 2D membranes holds the promise of transferring mechanical energy over a distance at low electrical power, thus enabling novel data readout and information processing technologies.

Chemical Design and Magnetic Ordering in Thin Layers of 2D Metal-Organic Frameworks (MOFs).

Through rational chemical design, and thanks to the hybrid nature of metal-organic frameworks (MOFs), it is possible to prepare molecule-based 2D magnetic materials stable at ambient conditions. Here, we illustrate the versatility of this approach by changing both the metallic nodes and the ligands in a family of layered MOFs that allows the tuning of their magnetic properties. Specifically, the reaction of benzimidazole-type ligands with different metal centers (MII = Fe, Co, Mn, Zn) in a solvent-free synthesis produces a family of crystalline materials, denoted as MUV-1(M), which order antiferromagnetically with critical temperatures that depend on M. Furthermore, the incorporation of additional substituents in the ligand results in a novel system, denoted as MUV-8, formed by covalently bound magnetic double layers interconnected by van der Waals interactions, a topology that is very rare in the field of 2D materials and unprecedented for 2D magnets. These layered materials are robust enough to be mechanically exfoliated down to a few layers with large lateral dimensions. Finally, the robustness and crystallinity of these layered MOFs allow the fabrication of nanomechanical resonators that can be used to detect─through laser interferometry─the magnetic order in thin layers of these 2D molecule-based antiferromagnets.

O-Doped Nanographenes: A Pyrano/Pyrylium Route Towards Semiconducting Cationic Mixed-Valence Complexes.

Herein we report an efficient synthesis to prepare O-doped nanographenes derived from the π-extension of pyrene. The derivatives are highly fluorescent and feature low oxidation potentials. Using electrooxidation, crystals of cationic mixed-valence (MV) complexes were grown in which the organic salts organize into face-to-face π-stacks, a favorable solid-state arrangement for organic electronics. Variable-temperature electron paramagnetic resonance (EPR) measurements and relaxation studies suggest a strong electron delocalization along the longitudinal axis of the columnar π-stacking architectures. Electric measurements of single crystals of the MV salts show a semiconducting behavior with a remarkably high conductivity at room temperature. These findings support the notion that π-extension of heteroatom-doped polycyclic aromatic hydrocarbons is an attractive approach to fabricate nanographenes with a broad spectrum of semiconducting properties and high charge mobilities.

Pressure-Induced Collapse of the Charge Density Wave and Higgs Mode Visibility in 2H-TaS_{2}.

The pressure evolution of the Raman active electronic excitations of the transition metal dichalcogenides 2H-TaS_{2} is followed through the pressure phase diagram embedding incommensurate charge-density-wave and superconducting states. At high pressure, the charge-density wave is found to collapse at 8.5 GPa. In the coexisting charge-density-wave and superconducting orders, we unravel a strong in-gap superconducting mode, attributed to a Higgs mode, coexisting with the expected incoherent Cooper-pair breaking signature. The latter remains in the pure superconducting state reached above 8.5 GPa. Our report constitutes a new observation of such Raman active Higgs mode since the long-standing unique case 2H-NbSe_{2}.

Electronic, Structural and Functional Versatility in Tetrathiafulvalene-Lanthanide Metal-Organic Frameworks.

Tetrathiafulvalene-lanthanide (TTF-Ln) metal-organic frameworks (MOFs) are an interesting class of multifunctional materials in which porosity can be combined with electronic properties such as electrical conductivity, redox activity, luminescence and magnetism. Herein a new family of isostructural TTF-Ln MOFs is reported, denoted as MUV-5(Ln) (Ln=Gd, Tb, Dy, Ho, Er), exhibiting semiconducting properties as a consequence of the short intermolecular S⋅⋅⋅S contacts established along the chain direction between partially oxidised TTF moieties. In addition, this family shows photoluminescence properties and single-molecule magnetic behaviour, finding near-infrared (NIR) photoluminescence in the Yb/Er derivative and slow relaxation of the magnetisation in the Dy and Er derivatives. As such properties are dependent on the electronic structure of the lanthanide ion, the immense structural, electronic and functional versatility of this class of materials is emphasised.

Tunable, multifunctional opto-electrical response in multilayer FePS3/single-layer MoS2 van der Waals p-n heterojunctions.

The combination of specific van der Waals semiconductors in vertical stacks leads to atomically sharp heterointerfaces with unique properties, offering versatility and additional functionality for thin, flexible, optoelectronic devices. In this work, we demonstrate heterostructures built from single-layer MoS2 (n-type) and multilayer FePS3 (p-type) as multifunctional p-n junctions where robust photoluminescent light emission and broadband electrical photo-response coexist. This is made possible by the inherent properties of the materials involved and the precise energy band alignment at their interface, which preserves the photoluminescent emission provided by the single-layer MoS2 and confers exceptional tunability to the system. Indeed, through small changes in the applied voltage across the junction, the interplay between photoluminescence and photocurrent generation can be tuned, allowing for a precise control of the light emission of single-layer MoS2 - from severely quenched to an order of magnitude enhancement. Additionally, the broadband photo-response of the system presents an enhanced performance under ultraviolet illumination, in contrast to other van der Waals heterostacks containing single-layer semiconductors. Furthermore, this photo-response can be adjusted by the application of an external electric field, enabling photocurrent generation under both reverse and forward bias, thereby contributing to the overall functionality and versatility of the system.

Interplay between Optical Emission and Magnetism in the van der Waals Magnetic Semiconductor CrSBr in the Two-Dimensional Limit.

The van der Waals semiconductor metamagnet CrSBr offers an ideal platform for studying the interplay between optical and magnetic properties in the two-dimensional limit. Here, we carried out an exhaustive optical characterization of this material by means of temperature- and magnetic-field-dependent photoluminescence (PL) on flakes of different thicknesses down to the monolayer. We found a characteristic emission peak that is quenched upon switching the ferromagnetic layers from an antiparallel to a parallel configuration and exhibits a temperature dependence different from that of the peaks commonly ascribed to excitons. The contribution of this peak to the PL is boosted around 30-40 K, coinciding with the hidden order magnetic transition temperature. Our findings reveal the connection between the optical and magnetic properties via the ionization of magnetic donor vacancies. This behavior enables a useful tool for the optical reading of the magnetic states in atomically thin layers of CrSBr and shows the potential of the design of 2D heterostructures with magnetic and excitonic properties.

Ultrafast Coherent THz Lattice Dynamics Coupled to Spins in the van der Waals Antiferromagnet FePS3.

Coherent THz optical lattice and hybridized phonon-magnon modes are triggered by femtosecond laser pulses in the antiferromagnetic van der Waals semiconductor FePS3 . The laser-driven lattice and spin dynamics are investigated in a bulk crystal as well as in a 380 nm-thick exfoliated flake as a function of the excitation photon energy, sample temperature and applied magnetic field. The pump-probe magneto-optical measurements reveal that the amplitude of a coherent phonon mode oscillating at 3.2 THz decreases as the sample is heated up to the Néel temperature. This signal eventually vanishes as the phase transition to the paramagnetic phase occurs, thus revealing its connection to the long-range magnetic order. In the presence of an external magnetic field, the optically triggered 3.2 THz phonon hybridizes with a magnon mode, which is utilized to excite the hybridized phonon-magnon mode optically. These findings open a pathway toward the optical control of coherent THz photo-magnonic dynamics in a van der Waals antiferromagnet, which can be scaled down to the 2D limit.

A quantum spin liquid candidate isolated in a two-dimensional CoIIRhIII bimetallic oxalate network.

A quantum spin liquid (QSL) is an elusive state of matter characterized by the absence of long-range magnetic order, even at zero temperature, and by the presence of exotic quasiparticle excitations. In spite of their relevance for quantum communication, topological quantum computation and the understanding of strongly correlated systems, like high-temperature superconductors, the unequivocal experimental identification of materials behaving as QSLs remains challenging. Here, we present a novel 2D heterometallic oxalate complex formed by high-spin Co(ii) ions alternating with diamagnetic Rh(iii) in a honeycomb lattice. This complex meets the key requirements to become a QSL: a spin ½ ground state for Co(ii), determined by spin-orbit coupling and crystal field, a magnetically-frustrated triangular lattice due to the presence of antiferromagnetic correlations, strongly suppressed direct exchange interactions and the presence of equivalent interfering superexchange paths between Co centres. A combination of electronic paramagnetic resonance, specific heat and ac magnetic susceptibility measurements in a wide range of frequencies and temperatures shows the presence of strong antiferromagnetic correlations concomitant with no signs of magnetic ordering down to 15 mK. These results show that bimetallic oxalates are appealing QSL candidates as well as versatile systems to chemically fine tune key aspects of a QSL, like magnetic frustration and superexchange path geometries.

Magnetic Imaging and Domain Nucleation in CrSBr Down to the 2D Limit.

Recent advancements in 2D materials have revealed the potential of van der Waals magnets, and specifically of their magnetic anisotropy that allows applications down to the 2D limit. Among these materials, CrSBr has emerged as a promising candidate, because its intriguing magnetic and electronic properties have appeal for both fundamental and applied research in spintronics or magnonics. In this work, nano-SQUID-on-tip (SOT) microscopy is used to obtain direct magnetic imaging of CrSBr flakes with thicknesses ranging from monolayer (N = 1) to few-layer (N = 5). The ferromagnetic order is preserved down to the monolayer, while the antiferromagnetic coupling of the layers starts from the bilayer case. For odd layers, at zero applied magnetic field, the stray field resulting from the uncompensated layer is directly imaged. The progressive spin reorientation along the out-of-plane direction (hard axis) is also measured with a finite applied magnetic field, allowing evaluation of the anisotropy constant, which remains stable down to the monolayer and is close to the bulk value. Finally, by selecting the applied magnetic field protocol, the formation of Néel magnetic domain walls is observed down to the single-layer limit.

Local control of superconductivity in a NbSe2/CrSBr van der Waals heterostructure.

Two-dimensional magnets and superconductors are emerging as tunable building-blocks for quantum computing and superconducting spintronic devices, and have been used to fabricate all two-dimensional versions of traditional devices, such as Josephson junctions. However, novel devices enabled by unique features of two-dimensional materials have not yet been demonstrated. Here, we present NbSe2/CrSBr van der Waals superconducting spin valves that exhibit infinite magnetoresistance and nonreciprocal charge transport. These responses arise from a unique metamagnetic transition in CrSBr, which controls the presence of localized stray fields suitably oriented to suppress the NbSe2 superconductivity in nanoscale regions and to break time reversal symmetry. Moreover, by integrating different CrSBr crystals in a lateral heterostructure, we demonstrate a superconductive spin valve characterized by multiple stable resistance states. Our results show how the unique physical properties of layered materials enable the realization of high-performance quantum devices based on novel working principles.

Magnetic order in 2D antiferromagnets revealed by spontaneous anisotropic magnetostriction.

The temperature dependent order parameter provides important information on the nature of magnetism. Using traditional methods to study this parameter in two-dimensional (2D) magnets remains difficult, however, particularly for insulating antiferromagnetic (AF) compounds. Here, we show that its temperature dependence in AF MPS3 (M(II) = Fe, Co, Ni) can be probed via the anisotropy in the resonance frequency of rectangular membranes, mediated by a combination of anisotropic magnetostriction and spontaneous staggered magnetization. Density functional calculations followed by a derived orbital-resolved magnetic exchange analysis confirm and unravel the microscopic origin of this magnetization-induced anisotropic strain. We further show that the temperature and thickness dependent order parameter allows to deduce the material's critical exponents characterising magnetic order. Nanomechanical sensing of magnetic order thus provides a future platform to investigate 2D magnetism down to the single-layer limit.

A fluorinated 2D magnetic coordination polymer.

Herein we show the versatility of coordination chemistry to design and expand a family of 2D materials by incorporating F groups at the surface of the layers. Through the use of a prefuntionalized organic linker with F groups, it is possible to achieve a layered magnetic material based on Fe(II) centers that are chemically stable in open air, contrary to the known 2D inorganic magnetic materials. The high quality of the single crystals and their robustness allow to fabricate 2D molecular materials by micromechanical exfoliation, preserving the crystalline nature of these layers together with the desired functionalization.

Probing the Spin Dimensionality in Single-Layer CrSBr Van Der Waals Heterostructures by Magneto-Transport Measurements.

2D magnetic materials offer unprecedented opportunities for fundamental and applied research in spintronics and magnonics. Beyond the pioneering studies on 2D CrI3 and Cr2 Ge2 Te6 , the field has expanded to 2D antiferromagnets exhibiting different spin anisotropies and textures. Of particular interest is the layered metamagnet CrSBr, a relatively air-stable semiconductor formed by antiferromagnetically-coupled ferromagnetic layers (Tc ∼150 K) that can be exfoliated down to the single-layer. It presents a complex magnetic behavior with a dynamic magnetic crossover, exhibiting a low-temperature hidden-order below T*∼40 K. Here, the magneto-transport properties of CrSBr vertical heterostructures in the 2D limit are inspected. The results demonstrate the marked low-dimensional character of the ferromagnetic monolayer, with short-range correlations above Tc and an Ising-type in-plane anisotropy, being the spins spontaneously aligned along the easy axis b below Tc . By applying moderate magnetic fields along a and c axes, a spin-reorientation occurs, leading to a magnetoresistance enhancement below T*. In multilayers, a spin-valve behavior is observed, with negative magnetoresistance strongly enhanced along the three directions below T*. These results show that CrSBr monolayer/bilayer provides an ideal platform for studying and controlling field-induced phenomena in two-dimensions, offering new insights regarding 2D magnets and their integration into vertical spintronic devices.