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.

Atomic Force Microscopy beyond Topography: Chemical Sensing of 2D Material Surfaces through Adhesion Measurements.

Developing new functionalities of two-dimensional materials (2Dms) can be achieved by their chemical modification with a broad spectrum of molecules. This functionalization is commonly studied by using spectroscopies such as Raman, IR, or XPS, but the detection limit is a common problem. In addition, these methods lack detailed spatial resolution and cannot provide information about the homogeneity of the coating. Atomic force microscopy (AFM), on the other hand, allows the study of 2Dms on the nanoscale with excellent lateral resolution. AFM has been extensively used for topographic analysis; however, it is also a powerful tool for evaluating other properties far beyond topography such as mechanical ones. Therefore, herein, we show how AFM adhesion mapping of transition metal chalcogenide 2Dms (i.e., MnPS3 and MoS2) permits a close inspection of the surface chemical properties. Moreover, the analysis of adhesion as relative values allows a simple and robust strategy to distinguish between bare and functionalized layers and significantly improves the reproducibility between measurements. Remarkably, it is also confirmed by statistical analysis that adhesion values do not depend on the thickness of the layers, proving that they are related only to the most superficial part of the materials. In addition, we have implemented an unsupervised classification method using k-means clustering, an artificial intelligence-based algorithm, to automatically classify samples based on adhesion values. These results demonstrate the potential of simple adhesion AFM measurements to inspect the chemical nature of 2Dms and may have implications for the broad scientific community working in the field.

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.

Tunable Charge Transport and Spin Dynamics in Two-Dimensional Conjugated Metal-Organic Frameworks.

Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) have attracted increasing interest in electronics due to their (semi)conducting properties. Charge-neutral 2D c-MOFs also possess persistent organic radicals that can be viewed as spin-concentrated arrays, affording new opportunities for spintronics. However, the strong π-interaction between neighboring layers of layer-stacked 2D c-MOFs annihilates active spin centers and significantly accelerates spin relaxation, severely limiting their potential as spin qubits. Herein, we report the precise tuning of the charge transport and spin dynamics in 2D c-MOFs via the control of interlayer stacking. The introduction of bulky side groups on the conjugated ligands enables a significant dislocation of the 2D c-MOFs layers from serrated stacking to staggered stacking, thereby spatially weakening the interlayer interactions. As a consequence, the electrical conductivity of 2D c-MOFs decreases by 6 orders of magnitude, while the spin density achieves more than a 30-fold increase and the spin-lattice relaxation time (T1) is increased up to ∼60 µs, hence being superior to the reference 2D c-MOFs with compact stackings whose spin relaxation is too fast to be detected. Spin dynamics results also reveal that spinless polaron pairs or bipolarons play critical roles in the charge transport of these 2D c-MOFs. Our strategy provides a bottom-up approach for enlarging spin dynamics in 2D c-MOFs, opening up pathways for developing MOF-based spintronics.

Bistable Spin-Crossover Nanoparticles for Molecular Electronics.

The field of spin-crossover complexes is rapidly evolving from the study of the spin transition phenomenon to its exploitation in molecular electronics. Such spin transition is gradual in a single-molecule, while in bulk it can be abrupt, showing sometimes thermal hysteresis and thus a memory effect. A convenient way to keep this bistability while reducing the size of the spin-crossover material is to process it as nanoparticles (NPs). Here, the most recent advances in the chemical design of these NPs and their integration into electronic devices, paying particular attention to optimizing the switching ratio are reviewed. Then, integrating spin-crossover NPs over 2D materials is focused to improve the endurance, performance, and detection of the spin state in these hybrid devices.

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.

Accelerating water oxidation - a mixed Co/Fe polyoxometalate with improved turnover characteristics.

Water oxidation is a bottleneck reaction for the establishment of solar-to-fuel energy conversion systems. Earth-abundant metal-based polyoxometalates are promising heterogeneous water oxidation catalysts that can operate in a wide pH range. However, detailed structure-reactivity relationships are not yet comprehensively understood, hampering the design and synthesis of more effective polyoxometalate-based oxidation catalysts. Here we report the synthesis of an ordered, mixed-metal cobalt-iron Weakley archetype [CoII2(H2O)2FeIII2(CoIIW9O34)2]14- (Co2Fe2-WS), which unexpectedly highlights the strong influence of the central, coordinatively saturated metal ions on the catalytic water oxidation characteristics. The resulting species exhibits catalytic turnover frequencies which are up to 4× higher than those of the corresponding archetype tetracobalt-oxo species [CoII2(H2O)2CoII2(PW9O34)2]10- (Co4-WS). It is further striking that the system becomes catalytically inactive when one of the central positions is occupied by a WVI ion as demonstrated by [CoII2(H2O)2CoIIWVI(CoIIW9O34)2]12- (Co3W-WS). Importantly, this study demonstrates that coordinatively saturated metal ions in this central position, which at first glance appear insignificant, do not solely have a structural role but also impart a distinctive structural influence on the reactivity of the polyoxometalate. These results provide unique insights into the structure-reactivity relationships of polyoxometalates with improved catalytic performance characteristics.

Design and Processing as Ultrathin Films of a Sublimable Iron(II) Spin Crossover Material Exhibiting Efficient and Fast Light-Induced Spin Transition.

Materials based on spin crossover (SCO) molecules have centered the attention in molecular magnetism for more than 40 years as they provide unique examples of multifunctional and stimuli-responsive materials, which can be then integrated into electronic devices to exploit their molecular bistability. This process often requires the preparation of thermally stable SCO molecules that can sublime and remain intact in contact with surfaces. However, the number of robust sublimable SCO molecules is still very scarce. Here, we report a novel example of this kind. It is based on a neutral iron(II) coordination complex formulated as [Fe(neoim)2], where neoimH is the ionogenic ligand 2-(1H-imidazol-2-yl)-9-methyl-1,10-phenanthroline. In the first part, a comprehensive study, which covers the synthesis and magnetostructural characterization of the [Fe(neoim)2] complex as a bulk microcrystalline material, is reported. Then, in the second part, we investigate the suitability of this material to form thin films through high-vacuum sublimation. Finally, the retainment of all present SCO capabilities in the bulk when the material is processed is thoroughly studied by means of X-ray absorption spectroscopy. In particular, a very efficient and fast light-induced spin transition (LIESST effect) has been observed, even for ultrathin films of 15 nm.

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.

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 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.

Hybrid Heterostructures of a Spin Crossover Coordination Polymer on MoS2 : Elucidating the Role of the 2D Substrate.

Controlling the deposition of spin-crossover (SCO) materials constitutes a crucial step for the integration of these bistable molecular systems in electronic devices. Moreover, the influence of functional surfaces, such as 2D materials, can be determinant on the properties of the deposited SCO film. In this work, ultrathin films of the SCO Hofmann-type coordination polymer [Fe(py)2 {Pt(CN)4 }] (py = pyridine) onto monolayers of 1T and 2H MoS2 polytypes are grown. The resulting hybrid heterostructures are characterized by GIXRD, XAS, XPS, and EXAFS to get information on the structure and the specific interactions generated at the interface, as well as on the spin transition. The use of a layer-by-layer results in SCO/2D heterostructures, with crystalline and well-oriented [Fe(py)2 {Pt(CN)4 }]. Unlike with conventional Au or SiO2 substrates, no intermediate self-assembled monolayer is required, thanks to the surface S atoms. Furthermore, it is observed that the higher presence of Fe3+ in the 2H heterostructures hinders an effective spin transition for [Fe(py)2 {Pt(CN)4 }] films thinner than 8 nm. Remarkably, when using 1T MoS2 , this transition is preserved in films as thin as 4 nm, due to the reducing character of this metallic substrate. These results highlight the active role that 2D materials play as substrates in hybrid molecular/2D heterostructures.

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.

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.

Effect of Nonconstituent Additive Ions on the Controlled Crystallization of Lanthanide-Based Preyssler Polyoxometalates.

Preyssler-type polyoxometalates (POMs) encapsulating lanthanide ions have been shown to provide ideal examples of single-molecule magnets and spin-qubits. However, the advances in this area are limited by the quality and size of the crystals. In this work, the role of additives ions in the crystallization of these POMs from aqueous solutions has been investigated. More specifically, we have studied the influence of Al3+, Y3+, and In3+ on the crystallization process of K12[MP5W30O110] (where M = Gd and Y). The results show that the concentration of these ions in the solution plays an important role in controlling the crystallization rate of the grown POM crystals leading to a significant increase in their size, while showing very little or no tendency to be incorporated into the structure. This has allowed us to obtain pure Gd or Y crystals, as well as diluted magnetic crystals formed by the diamagnetic Y3+ POM doped with the magnetic Gd3+ ion.

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.

Iron(II) Complexes of 2,6-Di[4-(ethylcarboxy)pyrazol-1-yl]pyridine with Reversible Guest-Modulated Spin-Crossover Behavior.

Three solvatomorphs of the iron(II) complex of 2,6-di[4-(ethylcarboxy)pyrazol-1-yl]pyridine (bpCOOEt2p) of formulas [Fe(bpCOOEt2p)2](ClO4)2·1.5MeNO2 (1), [Fe(bpCOOEt2p)2](ClO4)2·MeNO2 (2), and [Fe(bpCOOEt2p)2](ClO4)2·2MeNO2 (3) have been prepared and characterized. They show interesting spin-crossover (SCO) properties ranging from partial to complete thermal spin transitions and a light-induced excited spin-state trapping (LIESST) effect. In solvatomorph 2, a robust structure is formed with channels that enable the entrance or removal of solvent molecules by vapor diffusion without losing the crystallinity. Thus, solvent-exchanged samples [Fe(bpCOOEt2p)2](ClO4)2·MeNO2 (2·MeNO 2 ), [Fe(bpCOOEt2p)2](ClO4)2·MeCN (2·MeCN), [Fe(bpCOOEt2p)2](ClO4)2·0.5Me2CO (2·Me 2 CO), and [Fe(bpCOOEt2p)2](ClO4)2·MeCOOH (2·MeCOOH) were prepared by vapor diffusion of the solvents in a crystal of the compound previously heated to 400 K in a single-crystal to single-crystal (SCSC) fashion. Interestingly, this causes a change of spin state with a stabilization of the low-spin state in 2·Me 2 CO and the high-spin state in 2·MeCN. Therefore, the SCO properties of 2 can be tuned in a reversible way by exposure to different solvents.

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.

Redox and guest tunable spin-crossover properties in a polymeric polyoxometalate.

A bifunctionalized polyoxometalate (POM), [V6O19(C16H15N6O)2]2-, which contains a redox active hexavanadate moiety covalently linked to two tridentate 2,6-bis(pyrazol-1-yl)pyridine (1-bpp) ligands, has been prepared and characterized. Reaction of this hybrid molecule with Fe(ii) or Zn(ii) ions produces crystalline neutral 1D networks of formula Fe[V6O19(C16H15N6O)2]·solv (2) and Zn[V6O19(C16H15N6O)2]·solv (3) (solv = solvent molecules). Magnetic properties of 2 show an abrupt spin-crossover (SCO) with the temperature, which can be induced by light irradiation at 10 K (Light-Induced Excited Spin-State Trapping, LIESST effect). Interestingly, this porous and flexible structure enables reversible exchange of solvents in 2, which allows tuning the temperature of the thermal SCO. In 2 and 3, the hexavanadate unit can be reduced by electrochemical or chemical means in a reversible way. Chemical reduction and reoxidation by a postsynthetic method is accompanied by the insertion in the structure of the reductant and oxidant molecules (cobaltocene and tribromide, respectively), which provokes drastic changes in the spin state of Fe(ii). This leads to an elegant switching multifunctional material in which SCO properties of the Fe(ii) complexes coexist with the redox properties of the POM and can be tuned by a variety of stimuli such as temperature, light, solvent exchange or electron transfer. During the reduction process, 3 undergoes a single-crystal-to-single-crystal one-electron reduction, which confirms the presence of cobaltocenium cations by single crystal X-ray diffraction.

Two-dimensional magnetic behaviour in hybrid NiFe-layered double hydroxides by molecular engineering.

Layered double hydroxides (LDHs) are a class of two-dimensional (2D) anionic materials that exhibit remarkable chemical versatility, making them ideal building blocks in the design of complex multifunctional materials. In this line, a NiFe-LDH is probably one of the most important LDHs due to its interesting electrochemical and magnetic properties. However, no direct magnetic measurements of exfoliated NiFe-LDH nanosheets have been reported so far. Herein, we synthesize a hybrid NiFe-LDH family through anion exchange reactions using surfactant molecules in order to increase the interlayer space (ranging from 8 to 31.6 Å), minimizing the interlayer dipolar interactions. By intercalation with octadecylsulphate, we have managed to obtain the largest interlayer space reported for a NiFe-LDH while keeping a similar size, morphology and composition. This wide interlayer separation results in a decrease in temperatures at which spontaneous magnetization (TM) occurs and the blocking temperature (TB), as well as a decrease in the coercive fields (HC). In fact, an abrupt drop in all these magnetic parameters above 30 Å interlayer distance is observed, evidencing complete magnetic decoupling of the layers. We have further validated our molecular engineering approach by characterizing the hybrid materials by Mössbauer spectroscopy and comparing the magnetic analysis results with those for a liquid phase exfoliated NiFe-LDH sample. Overall, this work provides fundamental insights into the magnetism of NiFe-LDHs, showing the potential of molecular engineering for designing hybrid layered magnetic materials approaching the 2D magnetic limit.