Self-assembled monolayers based spintronics: from ferromagnetic surface functionalization to spin-dependent transport.

Chemically functionalized surfaces are studied for a wide range of applications going from medicine to electronics. Whereas non-magnetic surfaces have been widely studied, functionalization of magnetic surfaces is much less common and has almost never been used for spintronics applications. In this article we present the functionalization of La2/3Sr1/3MnO3, a ferromagnetic oxide, with self-assembled monolayers for spintronics. La2/3Sr1/3MnO3 is the prototypical half-metallic manganite used in spintronics studies. First, we show that La2/3Sr1/3MnO3 can be functionalized by alkylphosphonic acid molecules. We then emphasize the use of these functionalized surfaces in spintronics devices such as magnetic tunnel junctions fabricated using a nano-indentation based lithography technique. The observed exponential increase of tunnel resistance as a function of alkyl chain length is a direct proof of the successful connection of molecules to ferromagnetic electrodes. For all alkyl chains studied we obtain stable and robust tunnel magnetoresistance, with effects ranging from a few tens to 10 000%. These results show that functionalized electrodes can be integrated in spintronics devices and open the door to a molecular engineering of spintronics.

Unidirectional Spin-Dependent Molecule-Ferromagnet Hybridized States Anisotropy in Cobalt Phthalocyanine Based Magnetic Tunnel Junctions.

Organic or molecular spintronics is a rising field of research at the frontier between condensed matter physics and chemistry. It aims to mix spin physics and the richness of chemistry towards designing new properties for spin electronics devices through engineering at the molecular scale. Beyond the expectation of a long spin lifetime, molecules can be also used to tailor the spin polarization of the injected current through the spin-dependent hybridization between molecules and ferromagnetic electrodes. In this Letter, we provide direct evidence of a hybrid interface spin polarization reversal due to the differing hybridization between phthalocyanine molecules and each cobalt electrode in Co/CoPc/Co magnetic tunnel junctions. Tunnel magnetoresistance and anisotropic tunnel magnetoresistance experiments show that interfacial hybridized electronic states have a unidirectional anisotropy that can be controlled by an electric field and that spin hybridization at the bottom and top interfaces differ, leading to an inverse tunnel magnetoresistance.

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.

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.

Giant electroresistance of super-tetragonal BiFeO3-based ferroelectric tunnel junctions.

Ferroelectric tunnel junctions enable a nondestructive readout of the ferroelectric state via a change of resistance induced by switching the ferroelectric polarization. We fabricated submicrometer solid-state ferroelectric tunnel junctions based on a recently discovered polymorph of BiFeO3 with giant axial ratio ("T-phase"). Applying voltage pulses to the junctions leads to the highest resistance changes (OFF/ON ratio >10,000) ever reported with ferroelectric tunnel junctions. Along with the good retention properties, this giant effect reinforces the interest in nonvolatile memories based on ferroelectric tunnel junctions. We also show that the changes in resistance scale with the nucleation and growth of ferroelectric domains in the ultrathin BiFeO3 (imaged by piezoresponse force microscopy), thereby suggesting potential as multilevel memory cells and memristors.

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.

Unveiling self-assembled monolayers' potential for molecular spintronics: spin transport at high voltage.

Molecular magnetic tunnel junctions using self-assembled monolayers (SAMs) as tunnel barriers show stable and efficient spin transport properties. Large tunnel magnetoresistance with a flat bias voltage dependence of the magnetoresistance is observed in La(2/3) Sr(1/3) MnO(3) /dodecylphosphonic acid SAM/Co nanocontacts. This opens the door to spintronic tailoring though SAM engineering and could also lead to new venues for spin injection in organic devices.

Self-assembled monolayer-functionalized half-metallic manganite for molecular spintronics.

(La,Sr)MnO(3) manganite (LSMO) has emerged as the standard ferromagnetic electrode in organic spintronic devices due to its highly spin-polarized character and air stability. Whereas organic semiconductors and polymers have been mainly envisaged to propagate spin information, self-assembled monolayers (SAMs) have been overlooked and should be considered as promising materials for molecular engineering of spintronic devices. Surprisingly, up to now the first key step of SAM grafting protocols over LSMO surface thin films is still missing. We report the grafting of dodecyl (C12P) and octadecyl (C18P) phosphonic acids over the LSMO half-metallic oxide. Alkylphosphonic acids form ordered self-assembled monolayers, with the phosphonic group coordinated to the surface and alkyl chains tilted from the surface vertical by 43° (C12P) and 27° (C18P). We have electrically characterized these SAMs in nanodevices and found that they act as tunnel barriers, opening the door toward the integration of alkylphosphonic acid//LSMO SAMs into future molecular/organic spintronic devices such as spin OLEDs.

A ferroelectric memristor.

Memristors are continuously tunable resistors that emulate biological synapses. Conceptualized in the 1970s, they traditionally operate by voltage-induced displacements of matter, although the details of the mechanism remain under debate. Purely electronic memristors based on well-established physical phenomena with albeit modest resistance changes have also emerged. Here we demonstrate that voltage-controlled domain configurations in ferroelectric tunnel barriers yield memristive behaviour with resistance variations exceeding two orders of magnitude and a 10 ns operation speed. Using models of ferroelectric-domain nucleation and growth, we explain the quasi-continuous resistance variations and derive a simple analytical expression for the memristive effect. Our results suggest new opportunities for ferroelectrics as the hardware basis of future neuromorphic computational architectures.

Atomic and electronic structure of the BaTiO3/Fe interface in multiferroic tunnel junctions.

Artificial multiferroic tunnel junctions combining a ferroelectric tunnel barrier of BaTiO(3) with magnetic electrodes display a tunnel magnetoresistance whose intensity can be controlled by the ferroelectric polarization of the barrier. This effect, called tunnel electromagnetoresistance (TEMR), and the corollary magnetoelectric coupling mechanisms at the BaTiO(3)/Fe interface were recently reported through macroscopic techniques. Here, we use advanced spectromicroscopy techniques by means of aberration-corrected scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS) to probe locally the nanoscale structural and electronic modifications at the ferroelectric/ferromagnetic interface. Atomically resolved real-space spectroscopic techniques reveal the presence of a single FeO layer between BaTiO(3) and Fe. Based on this accurate description of the studied interface, we propose an atomistic model of the ferroelectric/ferromagnetic interface further validated by comparing experimental and simulated STEM images with atomic resolution. Density functional theory calculations allow us to interpret the electronic and magnetic properties of these interfaces and to understand better their key role in the physics of multiferroics nanostructures.

Solid-state memories based on ferroelectric tunnel junctions.

Ferroic-order parameters are useful as state variables in non-volatile information storage media because they show a hysteretic dependence on their electric or magnetic field. Coupling ferroics with quantum-mechanical tunnelling allows a simple and fast readout of the stored information through the influence of ferroic orders on the tunnel current. For example, data in magnetic random-access memories are stored in the relative alignment of two ferromagnetic electrodes separated by a non-magnetic tunnel barrier, and data readout is accomplished by a tunnel current measurement. However, such devices based on tunnel magnetoresistance typically exhibit OFF/ON ratios of less than 4, and require high powers for write operations (>1 × 10(6) A cm(-2)). Here, we report non-volatile memories with OFF/ON ratios as high as 100 and write powers as low as ∼1 × 10(4) A cm(-2) at room temperature by storing data in the electric polarization direction of a ferroelectric tunnel barrier. The junctions show large, stable, reproducible and reliable tunnel electroresistance, with resistance switching occurring at the coercive voltage of ferroelectric switching. These ferroelectric devices emerge as an alternative to other resistive memories, and have the advantage of not being based on voltage-induced migration of matter at the nanoscale, but on a purely electronic mechanism.