Two-dimensional materials prospects for non-volatile spintronic memories.

Non-volatile magnetic random-access memories (MRAMs), such as spin-transfer torque MRAM and next-generation spin-orbit torque MRAM, are emerging as key to enabling low-power technologies, which are expected to spread over large markets from embedded memories to the Internet of Things. Concurrently, the development and performances of devices based on two-dimensional van der Waals heterostructures bring ultracompact multilayer compounds with unprecedented material-engineering capabilities. Here we provide an overview of the current developments and challenges in regard to MRAM, and then outline the opportunities that can arise by incorporating two-dimensional material technologies. We highlight the fundamental properties of atomically smooth interfaces, the reduced material intermixing, the crystal symmetries and the proximity effects as the key drivers for possible disruptive improvements for MRAM at advanced technology nodes.

Artificial Graphene Spin Polarized Electrode for Magnetic Tunnel Junctions.

2D materials offer the ability to expose their electronic structure to manipulations by a proximity effect. This could be harnessed to craft properties of 2D interfaces and van der Waals heterostructures in devices and quantum materials. We explore the possibility to create an artificial spin polarized electrode from graphene through proximity interaction with a ferromagnetic insulator to be used in a magnetic tunnel junction (MTJ). Ferromagnetic insulator/graphene artificial electrodes were fabricated and integrated in MTJs based on spin analyzers. Evidence of the emergence of spin polarization in proximitized graphene layers was observed through the occurrence of tunnel magnetoresistance. We deduced a spin dependent splitting of graphene's Dirac band structure (∼15 meV) induced by the proximity effect, potentially leading to full spin polarization and opening the way to gating. The extracted spin signals illustrate the potential of 2D quantum materials based on proximity effects to craft spintronics functionalities, from vertical MTJs memory cells to logic circuits.

Thirty Gigahertz Optoelectronic Mixing in Chemical Vapor Deposited Graphene.

The remarkable properties of graphene, such as broadband optical absorption, high carrier mobility, and short photogenerated carrier lifetime, are particularly attractive for high-frequency optoelectronic devices operating at 1.55 µm telecom wavelength. Moreover, the possibility to transfer graphene on a silicon substrate using a complementary metal-oxide-semiconductor-compatible process opens the ability to integrate electronics and optics on a single cost-effective chip. Here, we report an optoelectronic mixer based on chemical vapor-deposited graphene transferred on an oxidized silicon substrate. Our device consists in a coplanar waveguide that integrates a graphene channel, passivated with an atomic layer-deposited Al2O3 film. With this new structure, 30 GHz optoelectronic mixing in commercially available graphene is demonstrated for the first time. In particular, using a 30 GHz intensity-modulated optical signal and a 29.9 GHz electrical signal, we show frequency downconversion to 100 MHz. These results open promising perspectives in the domain of optoelectronics for radar and radio-communication systems.

Measuring the nonlinear refractive index of graphene using the optical Kerr effect method.

By means of the ultrafast optical Kerr effect method coupled to optical heterodyne detection (OHD-OKE), we characterize the third-order nonlinear response of graphene and compare it to experimental values obtained by the Z-scan method on the same samples. From these measurements, we estimate a negative nonlinear refractive index for monolayer graphene, n2=-1.1×10-13 m2/W. This is in contradiction to previously reported values, which leads us to compare our experimental measurements obtained by the OHD-OKE and the Z-scan method with theoretical and experimental values found in the literature and to discuss the discrepancies, taking into account parameters such as doping.

Interdependency of subsurface carbon distribution and graphene-catalyst interaction.

The dynamics of the graphene-catalyst interaction during chemical vapor deposition are investigated using in situ, time- and depth-resolved X-ray photoelectron spectroscopy, and complementary grand canonical Monte Carlo simulations coupled to a tight-binding model. We thereby reveal the interdependency of the distribution of carbon close to the catalyst surface and the strength of the graphene-catalyst interaction. The strong interaction of epitaxial graphene with Ni(111) causes a depletion of dissolved carbon close to the catalyst surface, which prevents additional layer formation leading to a self-limiting graphene growth behavior for low exposure pressures (10(-6)-10(-3) mbar). A further hydrocarbon pressure increase (to ∼10(-1) mbar) leads to weakening of the graphene-Ni(111) interaction accompanied by additional graphene layer formation, mediated by an increased concentration of near-surface dissolved carbon. We show that growth of more weakly adhered, rotated graphene on Ni(111) is linked to an initially higher level of near-surface carbon compared to the case of epitaxial graphene growth. The key implications of these results for graphene growth control and their relevance to carbon nanotube growth are highlighted in the context of existing literature.

Introducing carbon diffusion barriers for uniform, high-quality graphene growth from solid sources.

Carbon diffusion barriers are introduced as a general and simple method to prevent premature carbon dissolution and thereby to significantly improve graphene formation from the catalytic transformation of solid carbon sources. A thin Al2O3 barrier inserted into an amorphous-C/Ni bilayer stack is demonstrated to enable growth of uniform monolayer graphene at 600 °C with domain sizes exceeding 50 µm, and an average Raman D/G ratio of <0.07. A detailed growth rationale is established via in situ measurements, relevant to solid-state growth of a wide range of layered materials, as well as layer-by-layer control in these systems.

X-ray magnetic dichroism and tunnel magneto-resistance study of the magnetic phase in epitaxial CrVOxnanoclusters.

Epitaxial clusters of chromium and chromium-vanadium oxides are studied by tunnel magneto-resistivity measurements, x-ray absorption spectrometry and circular magnetic circular dichroism. They turn out to carry a small magnetic moment that follows a super-paramagnetic behavior. The chromium ion contribution to this magnetization is mainly due to an original magnetic Cr2O3-like phase, whereas usual Cr2O3is known to be anti-ferromagnetic in the bulk. For mixed clusters, vanadium ions also contribute to the total magnetization and they are coupled to the chromium ion spins. By measuring the dichroic signal at different temperatures, we get insight into the possible spin configurations of vanadium and chromium ions: we propose that the magnetic dipoles observed in the clusters assembly could be related to ionic spins that couple at a very short range, as for instance in short one-dimensional spins chains.

Combined spin filtering actions in hybrid magnetic junctions based on organic chains covalently attached to graphene.

We present a bias-controlled spin-filtering mechanism in spin-valves including a hybrid organic chain/graphene interface. Wet growth conditions of oligomeric molecular chains would usually lead, during standard CMOS-compatible fabrication processes, to the quenching of spintronics properties of metallic spin sources due to oxidation. We demonstrate by X-ray photoelectron spectroscopy that the use of a protective graphene layer fully preserves the metallic character of the ferromagnetic surface and thus its capability to deliver spin polarized currents. We focus here on a small aromatic chain of controllable lengths, formed by nitrobenzene monomers and derived from the commercial 4-nitrobenzene diazonium tetrafluoroborate, covalently attached to the graphene passivated spin sources thanks to electroreduction. A unique bias dependent switch of the spin signal is then observed in complete spin valve devices, from minority to majority spin carriers filtering. First-principles calculations are used to highlight the key role played by the spin-dependent hybridization of electronic states present at the different interfaces. Our work is a first step towards the exploration of spin transport using different functional molecular chains. It opens the perspective of atomic tailoring of magnetic junction devices towards spin and quantum transport control, thanks to the flexibility of ambient electrochemical surface functionalization processes.

Almost Perfect Spin Filtering in Graphene-Based Magnetic Tunnel Junctions.

We report on large spin-filtering effects in epitaxial graphene-based spin valves, strongly enhanced in our specific multilayer case. Our results were obtained by the effective association of chemical vapor deposited (CVD) multilayer graphene with a high quality epitaxial Ni(111) ferromagnetic spin source. We highlight that the Ni(111) spin source electrode crystallinity and metallic state are preserved and stabilized by multilayer graphene CVD growth. Complete nanometric spin valve junctions are fabricated using a local probe indentation process, and spin properties are extracted from the graphene-protected ferromagnetic electrode through the use of a reference Al2O3/Co spin analyzer. Strikingly, spin-transport measurements in these structures give rise to large negative tunnel magneto-resistance TMR = -160%, pointing to a particularly large spin polarization for the Ni(111)/Gr interface PNi/Gr, evaluated up to -98%. We then discuss an emerging physical picture of graphene-ferromagnet systems, sustained both by experimental data and ab initio calculations, intimately combining efficient spin filtering effects arising (i) from the bulk band structure of the graphene layers purifying the extracted spin direction, (ii) from the hybridization effects modulating the amplitude of spin polarized scattering states over the first few graphene layers at the interface, and (iii) from the epitaxial interfacial matching of the graphene layers with the spin-polarized Ni surface selecting well-defined spin polarized channels. Importantly, these main spin selection effects are shown to be either cooperating or competing, explaining why our transport results were not observed before. Overall, this study unveils a path to harness the full potential of low Resitance.Area (RA) graphene interfaces in efficient spin-based devices.

Unveiling a Chemisorbed Crystallographically Heterogeneous Graphene/L10-FePd Interface with a Robust and Perpendicular Orbital Moment.

A crystallographically heterogeneous interface was fabricated by growing hexagonal graphene (Gr) using chemical vapor deposition (CVD) on a tetragonal FePd epitaxial film grown by magnetron sputtering. FePd was alternately arranged with Fe and Pd in the vertical direction, and the outermost surface atom was identified primarily as Fe rather than Pd. This means that FePd has a high degree of L10-ordering, and the outermost Fe bonds to the carbon of Gr at the interface. When Gr is grown by CVD, the crystal orientation of hexagonal Gr toward tetragonal L10-FePd selects an energetically stable structure based on the van der Waals (vdW) force. The atomic relationship of Gr/L10-FePd, which is an energetically stable interface, was unveiled theoretically and experimentally. The Gr armchair axis was parallel to FePd [100]L10, where Gr was under a small strain by chemical bonding. Focusing on the interatomic distance between the Gr and FePd layers, the distance was theoretically and experimentally determined to be approximately 0.2 nm. This shorter distance (≈0.2 nm) can be explained by the chemisorption-type vdW force of strong orbital hybridization, rather than the longer distance (≈0.38 nm) of the physisorption-type vdW force. Notably, depth-resolved X-ray magnetic circular dichroism analyses revealed that the orbital magnetic moment (Ml) of Fe in FePd emerged at the Gr/FePd interface (@inner FePd: Ml = 0.16 µB → @Gr/FePd interface: Ml = 0.32 µB). This interfacially enhanced Ml showed obvious anisotropy in the perpendicular direction, which contributed to interfacial perpendicular magnetic anisotropy (IPMA). Moreover, the interfacially enhanced Ml and interfacially enhanced electron density exhibited robustness. It is considered that the shortening of the interatomic distance produces a robust high electron density at the interface, resulting in a chemisorption-type vdW force and orbital hybridization. Eventually, the robust interfacial anisotropic Ml emerged at the crystallographically heterogeneous Gr/L10-FePd interface. From a practical viewpoint, IPMA is useful because it can be incorporated into the large bulk perpendicular magnetic anisotropy (PMA) of L10-FePd. A micromagnetic simulation assuming both PMA and IPMA predicted that perpendicularly magnetized magnetic tunnel junctions (p-MTJs) using Gr/L10-FePd could realize 10-year data retention in a small recording layer with a circular diameter and thickness of 10 and 2 nm, respectively. We unveiled the energetically stable atomic structure in the crystallographically heterogeneous interface, discovered the emergence of the robust IPMA, and predicted that the Gr/L10-FePd p-MTJ is significant for high-density X nm generation magnetic random-access memory (MRAM) applications.

Synthesis of emerging 2D layered magnetic materials.

van der Waals atomically thin magnetic materials have been recently discovered. They have attracted enormous attention as they present unique magnetic properties, holding potential to tailor spin-based device properties and enable next generation data storage and communication devices. To fully understand the magnetism in two-dimensions, the synthesis of 2D materials over large areas with precise thickness control has to be accomplished. Here, we review the recent advancements in the synthesis of these materials spanning from metal halides, transition metal dichalcogenides, metal phosphosulphides, to ternary metal tellurides. We initially discuss the emerging device concepts based on magnetic van der Waals materials including what has been achieved with graphene. We then review the state of the art of the synthesis of these materials and we discuss the potential routes to achieve the synthesis of wafer-scale atomically thin magnetic materials. We discuss the synthetic achievements in relation to the structural characteristics of the materials and we scrutinise the physical properties of the precursors in relation to the synthesis conditions. We highlight the challenges related to the synthesis of 2D magnets and we provide a perspective for possible advancement of available synthesis methods to respond to the need for scalable production and high materials quality.

Band-Gap Landscape Engineering in Large-Scale 2D Semiconductor van der Waals Heterostructures.

We present a growth process relying on pulsed laser deposition for the elaboration of complex van der Waals heterostructures on large scales, at a 400 °C CMOS-compatible temperature. Illustratively, we define a multilayer quantum well geometry through successive in situ growths, leading to WSe2 being encapsulated into WS2 layers. The structural constitution of the quantum well geometry is confirmed by Raman spectroscopy combined with transmission electron microscopy. The large-scale high homogeneity of the resulting 2D van der Waals heterostructure is also validated by macro- and microscale Raman mappings. We illustrate the benefit of this integrative in situ approach by showing the structural preservation of even the most fragile 2D layers once encapsulated in a van der Waals heterostructure. Finally, we fabricate a vertical tunneling device based on these large-scale layers and discuss the clear signature of electronic transport controlled by the quantum well configuration with ab initio calculations in support. The flexibility of this direct growth approach, with multilayer stacks being built in a single run, allows for the definition of complex 2D heterostructures barely accessible with usual exfoliation or transfer techniques of 2D materials. Reminiscent of the III-V semiconductors' successful exploitation, our approach unlocks virtually infinite combinations of large 2D material families in any complex van der Waals heterostructure design.

Spin filtering by proximity effects at hybridized interfaces in spin-valves with 2D graphene barriers.

We report on spin transport in state-of-the-art epitaxial monolayer graphene based 2D-magnetic tunnel junctions (2D-MTJs). In our measurements, supported by ab-initio calculations, the strength of interaction between ferromagnetic electrodes and graphene monolayers is shown to fundamentally control the resulting spin signal. In particular, by switching the graphene/ferromagnet interaction, spin transport reveals magneto-resistance signal MR > 80% in junctions with low resistance × area products. Descriptions based only on a simple K-point filtering picture (i.e. MR increase with the number of layers) are not sufficient to predict the behavior of our devices. We emphasize that hybridization effects need to be taken into account to fully grasp the spin properties (such as spin dependent density of states) when 2D materials are used as ultimately thin interfaces. While this is only a first demonstration, we thus introduce the fruitful potential of spin manipulation by proximity effect at the hybridized 2D material / ferromagnet interface for 2D-MTJs.

Band-Structure Spin-Filtering in Vertical Spin Valves Based on Chemical Vapor Deposited WS2.

We report on spin transport in WS2-based 2D-magnetic tunnel junctions (2D-MTJs), unveiling a band structure spin filtering effect specific to the transition metal dichalcogenides (TMDCs) family. WS2 mono-, bi-, and trilayers are derived by a chemical vapor deposition process and further characterized by Raman spectroscopy, atomic force microscopy (AFM), and photoluminescence spectroscopy. The WS2 layers are then integrated in complete Co/Al2O3/WS2/Co MTJ hybrid spin-valve structures. We make use of a tunnel Co/Al2O3 spin analyzer to probe the extracted spin-polarized current from the WS2/Co interface and its evolution as a function of WS2 layer thicknesses. For monolayer WS2, our technological approach enables the extraction of the largest spin signal reported for a TMDC-based spin valve, corresponding to a spin polarization of PCo/WS2 = 12%. Interestingly, for bi- and trilayer WS2, the spin signal is reversed, which indicates a switch in the mechanism of interfacial spin extraction. With the support of ab initio calculations, we propose a model to address the experimentally measured inversion of the spin polarization based on the change in the WS2 band structure while going from monolayer (direct bandgap) to bilayer (indirect bandgap). These experiments illustrate the rich potential of the families of semiconducting 2D materials for the control of spin currents in 2D-MTJs.

A Local Study of the Transport Mechanisms in MoS2 Layers for Magnetic Tunnel Junctions.

MoS2-based vertical spintronic devices have attracted an increasing interest thanks to theoretical predictions of large magnetoresistance signals. However, experimental performances are still far from expectations. Here, we carry out the local electrical characterization of thin MoS2 flakes in a Co/Al2O3/MoS2 structure through conductive tip AFM measurements. We show that thin MoS2 presents a metallic behavior with a strong lateral transport contribution that hinders the direct tunnelling through thin layers. Indeed, no resistance dependence is observed with the flake thickness. These findings reveal a spin depolarization source in the MoS2-based spin valves, thus pointing to possible solutions to improve their spintronic properties.

Anisotropic Magneto-Coulomb Properties of 2D-0D Heterostructure Single Electron Device.

Fabrication and spintronics properties of 2D-0D heterostructures are reported. Devices based on graphene ("Gr")-aluminium nanoclusters heterostructures show robust and reproducible single-electron transport features, in addition to spin-dependent functionality when using a top magnetic electrode. The magnetic orientation of this single ferromagnetic electrode enables the modulation of the environmental charge experienced by the aluminium nanoclusters. This anisotropic magneto-Coulomb effect, originating from spin-orbit coupling within the ferromagnetic electrode, provides tunable spin valve-like magnetoresistance signatures without the requirement of spin coherent charge tunneling. These results extend the capability of Gr to act both as electrode and as a platform for the growth of 2D-0D mixed-dimensional van der Waals heterostructures, providing magnetic functionalities in the Coulomb blockade regime on scalable spintronic devices. These heterostructures pave the way towards novel device architectures at the crossroads of 2D material physics and spin electronics.

Insulator-to-Metallic Spin-Filtering in 2D-Magnetic Tunnel Junctions Based on Hexagonal Boron Nitride.

We report on the integration of atomically thin 2D insulating hexagonal boron nitride (h-BN) tunnel barriers into magnetic tunnel junctions (2D-MTJs) by fabricating two illustrative systems (Co/h-BN/Co and Co/h-BN/Fe) and by discussing h-BN potential for metallic spin filtering. The h-BN is directly grown by chemical vapor deposition on prepatterned Co and Fe stripes. Spin-transport measurements reveal tunnel magneto-resistances in these h-BN-based MTJs as high as 12% for Co/h-BN/h-BN/Co and 50% for Co/h-BN/Fe. We analyze the spin polarizations of h-BN/Co and h-BN/Fe interfaces extracted from experimental spin signals in light of spin filtering at hybrid chemisorbed/physisorbed h-BN, with support of ab initio calculations. These experiments illustrate the strong potential of h-BN for MTJs and are expected to ignite further investigations of 2D materials for large signal spin devices.

Sub-nanometer atomic layer deposition for spintronics in magnetic tunnel junctions based on graphene spin-filtering membranes.

We report on the successful integration of low-cost, conformal, and versatile atomic layer deposited (ALD) dielectric in Ni­Al2O3­Co magnetic tunnel junctions (MTJs) where the Ni is coated with a spin-filtering graphene membrane. The ALD tunnel barriers, as thin as 0.6 nm, are grown layer-by-layer in a simple, low-vacuum, ozone-based process, which yields high-quality electron-transport barriers as revealed by tunneling characterization. Even under these relaxed conditions, including air exposure of the interfaces, a significant tunnel magnetoresistance is measured highlighting the robustness of the process. The spin-filtering effect of graphene is enhanced, leading to an almost fully inversed spin polarization for the Ni electrode of −42%. This unlocks the potential of ALD for spintronics with conformal, layer-by-layer control of tunnel barriers in magnetic tunnel junctions toward low-cost fabrication and down-scaling of tunnel resistances.

Kinetic control of catalytic CVD for high-quality graphene at low temperatures.

Low-temperature (∼600 °C), scalable chemical vapor deposition of high-quality, uniform monolayer graphene is demonstrated with a mapped Raman 2D/G ratio of >3.2, D/G ratio ≤0.08, and carrier mobilities of ≥3000 cm(2) V(-1) s(-1) on SiO(2) support. A kinetic growth model for graphene CVD based on flux balances is established, which is well supported by a systematic study of Ni-based polycrystalline catalysts. A finite carbon solubility of the catalyst is thereby a key advantage, as it allows the catalyst bulk to act as a mediating carbon sink while optimized graphene growth occurs by only locally saturating the catalyst surface with carbon. This also enables a route to the controlled formation of Bernal stacked bi- and few-layered graphene. The model is relevant to all catalyst materials and can readily serve as a general process rationale for optimized graphene CVD.

Graphene-passivated nickel as an oxidation-resistant electrode for spintronics.

We report on graphene-passivated ferromagnetic electrodes (GPFE) for spin devices. GPFE are shown to act as spin-polarized oxidation-resistant electrodes. The direct coating of nickel with few layer graphene through a readily scalable chemical vapor deposition (CVD) process allows the preservation of an unoxidized nickel surface upon air exposure. Fabrication and measurement of complete reference tunneling spin valve structures demonstrate that the GPFE is maintained as a spin polarizer and also that the presence of the graphene coating leads to a specific sign reversal of the magneto-resistance. Hence, this work highlights a novel oxidation-resistant spin source which further unlocks low cost wet chemistry processes for spintronics devices.