Interfacial Spin Polarization Research Articles

Anchoring Atomically Precise Chiral Bismuth Oxido Nanoclusters on Gold: The Role of Amino Acid Linkers.

The adsorption of chiral molecules onto metallic surfaces triggers electron spin polarization at the interface, paving the way for applications in chiral opto-spintronics. However, the spin effects sensitively depend on the binding and ordering of the chiral species on surfaces. This study explores the adsorption of chiral thioether-functionalized atomically precise bismuth oxido nanoclusters (BiO-NCs) on gold (Au) surfaces, extending the conventional approach of using thiol-containing molecules and complexes to nanoclusters. Starting from the precursor [Bi38O45(NO3)20(dmso)28](NO3)4·4dmso (A), chiral BiO-NCs were synthesized by substituting the nitrates with N-(tert-butoxycarbonyl)-l-methionine (Boc-l-Met-O-) ligands to obtain [Bi38O45(Boc-l-Met-O)24] (2). The full exchange of nitrate by the Boc-l-methionine ligand was demonstrated by powder X-ray diffractograms, dynamic light scattering, electrospray ionization mass spectrometry, nuclear magnetic resonance, infrared, circular dichroism, and X-ray photoelectron spectroscopy. Compared to previously reported [Bi38O45(Boc-l-Phe-O)24(dmso)9] (1), BiO-NC 2 shows differences in the growth mode on a Au surface as revealed by scanning electron microscopy, wherefore a stronger binding of BiO-NC 2 is assumed. Anchoring of BiO-NC 2 to the Au surface through thioether groups induced a discernible change in the optical response of the Au surface analyzed by spectroscopic ellipsometry (SE). From the numerical modeling of the SE parameters, a layer thickness of ∼2 nm, corresponding to a monolayer of BiO-NC 2, was estimated for the samples prepared by dip coating. Thus, strong adsorption of BiO-NC 2 to the Au surface is concluded, which is an essential prerequisite for chiral-induced interface spin polarization.

Non-stoichiometry induced 2H–1T phase interfaces and room-temperature ferromagnetism in defective molybdenum selenide

Magnetic semiconducting materials offer tremendous prospects for spin electronics but is challenging to achieve room-temperature ferromagnetism with unambiguous origin. Herein, a non-stoichiometry strategy is proposed to induce tunable magnetization in MoSe2−x nanoflowers via vacancy-controlled 2H–1T phase transition. The resultant MoSe2−x exhibits robust room-temperature ferromagnetism with significant positive correlation to the content of 1T phase and 2H–1T interfaces. Significant magnetic hysteresis and Curie transition above room temperature have been achieved, confirming the ferromagnetic feature of MoSe2−x. To examine the origin of ferromagnetism, formation energy and spin-polarized calculations have been conducted, indicating that the Se vacancy is beneficial for the formation of the 1T phase and interfacial spin polarization. Localized magnetic moments induced at the 2H–1T interfaces exhibit enhanced magnetism as compared to the net moments from the 1T orbital splitting, giving rise to strong coupling bound magnetic polarons. This work not only advances the understanding on the origin of magnetism in magnetic semiconductors, but also provides an effective route to generate ferromagnetism by defect and/or interface engineering that could be applied to multiferroics, spintronics, and valleytronics.

Revealing the key role of molecular packing on interface spin polarization at two-dimensional limit in spintronic devices.

Understanding spinterfaces between magnetic metals and organic semiconductors is essential to unlock the great potentials that organic materials host for spintronic applications. Although plenty of efforts have been devoted to studying organic spintronic devices, exploring the role of metal/molecule spinterfaces at two-dimensional limit remains challenging because of excessive disorders and traps at the interfaces. Here, we demonstrate atomically smooth metal/molecule interfaces through nondestructively transferring magnetic electrodes on epitaxial grown single-crystalline layered organic films. Using such high-quality interfaces, we investigate spin injection of spin-valve devices based on organic films of different layers, in which molecules are packed in different manners. We find that the measured magnetoresistance and the estimated spin polarization increase markedly for bilayer devices compared with their monolayer counterparts. These observations reveal the key role of molecular packing on spin polarization, which is supported by density functional theory calculations. Our findings provide promising routes toward designing spinterfaces for organic spintronic devices.

Ferroionic inversion of spin polarization in a spin-memristor

Magnetoelectric coupling in artificial multiferroic interfaces can be drastically affected by the switching of oxygen vacancies and by the inversion of the ferroelectric polarization. Disentangling both effects is of major importance toward exploiting these effects in practical spintronic or spinorbitronic devices. We report on the independent control of ferroelectric and oxygen vacancy switching in multiferroic tunnel junctions with a La0.7Sr0.3MnO3 bottom electrode, a BaTiO3 ferroelectric barrier, and a Ni top electrode. We show that the concurrence of interface oxidation and ferroelectric switching allows for the controlled inversion of the interface spin polarization. Moreover, we show the possibility of a spin-memristor where the controlled oxidation of the interface allows for a continuum of memresistance states in the tunneling magnetoresistance. These results signal interesting new avenues toward neuromorphic devices where, as in practical neurons, the electronic response is controlled by electrochemical degrees of freedom.

Giant magnetoresistance ratio in a current-perpendicular-to-plane spin valve based on an inverse Heusler alloy Ti2NiAl.

A Ti2NiAl inverse Heusler alloy based current-perpendicular-to-plane (CPP) spin valve (SV) with various kinds of atomic terminated interfaces has been designed to explore the potential application of Heusler alloys in spintronics devices. By performing first principles calculations combined with the nonequilibrium Green’s function, it is revealed that spin magnetic moments of interfacial atoms suffer a decrease, and the electronic structure shows that the TiNiB-terminated structure possesses the largest interface spin polarization of ≈55%. Our study on spin-transport properties indicates that the total transmission coefficient at the Fermi level mainly comes from the contribution from the spin up electrons, which are regarded as the majority of the spin electrons. When the two electrodes of the CPP-SV device are in parallel magnetization configuration, the interface containing Ti and Ni atoms possesses a higher spin up transmission coefficient than the interface containing Ti and Al atoms. The device with the TiNiB-terminated interface possesses the largest magnetoresistance ratio of 3.28 × 105, and it has great application potential in spintronics devices.

Nonmonotonic bias dependence of local spin accumulation signals in ferromagnet/semiconductor lateral spin-valve devices

We find extraordinary behavior of the local two-terminal spin accumulation signals in ferromagnet (FM)/semiconductor (SC) lateral spin-valve devices. With respect to the bias voltage applied between two FM/SC Schottky tunnel contacts, the local spin-accumulation signal can show nonmonotonic variations, including a sign inversion. A part of the nonmonotonic features can be understood qualitatively by considering the rapid reduction in the spin polarization of the FM/SC interfaces with increasing bias voltage. In addition to the sign inversion of the FM/SC interface spin polarization, the influence of the spin-drift effect in the SC layer and the nonlinear electrical spin conversion at a biased FM/SC contact are discussed.

First-principles study on the structure, magnetism, and electronic properties in inverse Heusler alloy Ti2FeAl/GaAs(100) heterojunction

Abstract The interface structure stability, atomic displacement, atom-resolved magnetism, electronic properties, and spin polarization of 12 possible atomic terminations in Ti2FeAl/GaAs(100) heterojunction are comprehensively investigated by implementing the first-principles calculations. All of the lowest-energy interface structures are theoretically favorable to stability from interface formation energy examinations. The interface Fe atoms will shrink inwards, whereas the interface Ti atom will be moved outwards inversely. Therefore, an uneven interface atomic layer is observed in the heterojunction, which can lead to further spin-electronic scattering and reduction of the spin polarization. The competition among antiferromagnetic coupling between Fe and Ti atoms, d-electronic localization, and the relaxing effect of the interface metal atoms plays an important role in the atomic magnetic moment at the interface. The ideal half-metallicity observed in bulk has been destroyed by the undesirable interface states. In the TiAl-Ti-Ga-Top interface structure, the spin-polarization ratio reaches 77.2%, which suggests that the tunnel magnetoresistance value can be close to 300% at low temperature. The TiAl-Ti-Ga-Top interface structure with Ti-Ga atoms top-connected termination is a promising candidate for applications in magnetic tunnel junction devices.

Room-temperature local magnetoresistance effect in n-Ge devices with low-resistive Schottky-tunnel contacts

Two-terminal local magnetoresistance (MR) effect in n-type germanium (Ge) based lateral spin-valve (LSV) devices can be observed at room temperature. By using phosphorus δ-doped Heusler-alloy/Ge Schottky-tunnel contacts, the resistance-area product of the contacts is able to be less than 0.20 kΩ μm2, which is the lowest value in semiconductor based LSV devices. From the one-dimensional spin drift-diffusion model, the interface spin polarization of the Heusler-alloy/Ge contacts in the present LSV devices can be estimated to be ∼0.018 at room temperature. We experimentally propose that it is important for enhancing the local MR ratio in n-Ge based LSV devices to improve the interface spin polarization of the Heusler-alloy/Ge contacts.

Thermal stability of the spin injection in Co/Ag/Co lateral spin valves**Project supported by the National Natural Science Foundation of China (Grant Nos. 11304381 and 11374244), the Research Funds of Renmin University of China (Grant No. 17XNLF02), the Foundation for the Author of National Excellent Doctoral Dissertation of China (Grant No. 201443), and the Natural Science Foundation of Fujian Province of

Spin injection, spin diffusion, and spin detection are investigated in Co/Ag/Co lateral spin valves at room temperature. Clear spin accumulation signals are detected by the non-local measurement. By fitting the results to the one-dimensional diffusion equation, ∼8.6% spin polarization of the Co/Ag interface and ∼ 180 nm spin diffusion length in Ag are obtained. Thermal treatment results show that the spin accumulation signal drastically decreases after 100 °C annealing, and disappears under 200 °C annealing. Our results demonstrate that, compared to the spin diffusion length, the decrease and the disappearance of the spin accumulation signal are mainly dominated by the variation of the interfacial spin polarization of the Co/Ag interface.

Interface Characterization of Current-Perpendicular-to-Plane Spin Valves Based on Spin Gapless Semiconductor Mn2CoAl

Employing the first-principles calculations within density functional theory (DFT) combined with the nonequilibrium Green’s function, we investigated the interfacial electronic, magnetic, and spin transport properties of Mn2CoAl/Ag/Mn2CoAl current-perpendicular-to-plane spin valves (CPP-SV). Due to the interface rehybridization, the magnetic moment of the interface atom gets enhanced. Further analysis on electronic structures reveals that owing to the interface states, the interface spin polarization is decreased. The largest interface spin polarization (ISP) of 78% belongs to the MnCoT-terminated interface, and the ISP of the MnMnT1-terminated interface is also as high as 45%. The transmission curves of Mn2CoAl/Ag/Mn2CoAl reveal that the transmission coefficient at the Fermi level in the majority spin channel is much higher than that in the minority spin channel. Furthermore, the calculated magnetoresistance (MR) ratio of the MnCoT-terminated interface reaches up to 2886%, while that of the MnMnT1-terminated interface is only 330%. Therefore, Mn2CoAl/Ag/Mn2CoAl CPP-SV with an MnCo-terminated interface structure has a better application in a spintronics device.

Spin injection and detection in lateral spin valves with hybrid interfaces

Spin injection and detection in lateral spin valves with hybrid interfaces comprising a Co/Ag transparent contact and a Co/MgO/Ag junction (III) are investigated at room temperature in comparison with pure Co/Ag transparent contacts (I) and Co/MgO/Ag junctions (II). The measured spin-accumulation signals of a type III device are five times higher than those for type I. The extracted spin diffusion length in Ag is 180 nm for all three types of devices. The enhancement of the spin signal of the hybrid structure is mainly attributed to the increase of the interfacial spin polarization from the Co/MgO/Ag junction.

Thiol-functionalization of Mn5Ge3 thin films

Hybrid organic/inorganic interfaces could pave the way to chemically designed or new multifunctional electronic devices, in particular in the spintronics field where, for instance, the interfacial spin polarization can be tuned through chemical interactions and surface modifications. We report herein, for the very first time, the assays of self-assembled monolayers (SAMs) formation on Mn5Ge3 surface. Interestingly, Mn5Ge3 is a ferromagnetic metal possessing interesting features for spintronics such as a high Curie temperature, a capability to grow epitaxially on Ge germanium that is a key point for integration in the mainstream Si technology. Mn5Ge3 thin films are synthesized by molecular beam epitaxy under ultra-vacuum condition. We studied the Mn5Ge3 surface prior to deposition of SAMs, meaning the surface exposed to air and different solvents, by XPS and contact angle measurements leading to the value of the surface tension of this surface. Then SAMs of octanethiol and perfluorodecanethiol are formed on Mn5Ge3 surface at room temperature. The best experimental conditions to form the SAMs are found for an immersion time of 36 h and a concentration of 4 mM.

Solid-State Synapse Based on Magnetoelectrically Coupled Memristor.

Brain-inspired computing architectures attempt to emulate the computations performed in the neurons and the synapses in the human brain. Memristors with continuously tunable resistances are ideal building blocks for artificial synapses. Through investigating the memristor behaviors in a La0.7Sr0.3MnO3/BaTiO3/La0.7Sr0.3MnO3 multiferroic tunnel junction, it was found that the ferroelectric domain dynamics characteristics are influenced by the relative magnetization alignment of the electrodes, and the interfacial spin polarization is manipulated continuously by ferroelectric domain reversal, enriching our understanding of the magnetoelectric coupling fundamentally. This creates a functionality that not only the resistance of the memristor but also the synaptic plasticity form can be further manipulated, as demonstrated by the spike-timing-dependent plasticity investigations. Density functional theory calculations are carried out to describe the obtained magnetoelectric coupling, which is probably related to the Mn-Ti intermixing at the interfaces. The multiple and controllable plasticity characteristic in a single artificial synapse, to resemble the synaptic morphological alteration property in a biological synapse, will be conducive to the development of artificial intelligence.

Reduced interface spin polarization by antiferromagnetically coupled Mn segregated to the Co2MnSi /GaAs (001) interface

We have investigated the interfacial structure and its correlation with the calculated spin polarization in $\mathrm{C}{\mathrm{o}}_{2}\mathrm{MnSi}$/GaAs(001) lateral spin valves. $\mathrm{C}{\mathrm{o}}_{2}\mathrm{MnSi}$ (CMS) films were grown on As-terminated c($4\ifmmode\times\else\texttimes\fi{}4$) GaAs(100) by molecular beam epitaxy using different first atomic layers: MnSi, Co, and Mn. Atomically resolved $Z$-contrast scanning transmission electron microscopy (STEM) imaging and electron energy loss spectroscopy (EELS) were used to develop atomic structural models of the CMS/GaAs interfaces that were used as inputs for first-principles calculations to understand the magnetic and electronic properties of the interface. First-principles structures were relaxed and then validated by comparing experimental and simulated high-resolution STEM images. STEM-EELS results show that all three films have similar six atomic layer thick, Mn- and As-rich multilayer interfaces. However, the Co-initiated interface contains a $\mathrm{M}{\mathrm{n}}_{2}\mathrm{As}$-like layer, which is antiferromagnetic, and which is not present in the other two interfaces. Density functional theory calculations show a higher degree of interface spin polarization in the Mn- and MnSi-initiated cases, compared to the Co-initiated case, although none of the interfaces are half-metallic. The loss of half-metallicity is attributed, at least in part, to the segregation of Mn at the interface, which leads to the formation of interface states. The implications for the performance of lateral spin valves based on these interfaces are discussed briefly.

Tuning the interfacial charge, orbital, and spin polarization properties in La0.67Sr0.33MnO3/La1−xSrxMnO3 bilayers

The possibility of controlling the interfacial properties of artificial oxide heterostructures is still attracting researchers in the field of materials engineering. Here, we used surface sensitive techniques and high-resolution transmission electron microscopy to investigate the evolution of the surface spin-polarization and lattice strains across the interfaces between La0.66Sr0.33MnO3 thin films and low-doped manganites as capping layers. We have been able to fine tune the interfacial spin-polarization by changing the capping layer thickness and composition. The spin-polarization was found to be the highest at a critical capping thickness that depends on the Sr doping. We explain the non-trivial magnetic profile by the combined effect of two mechanisms: On the one hand, the extra carriers supplied by the low-doped manganites that tend to compensate the overdoped interface, favouring locally a ferromagnetic double-exchange coupling. On the other hand, the evolution from a tensile-strained structure of the inner layers to a compressed structure at the surface that changes gradually the orbital occupation and hybridization of the 3d-Mn orbitals, being detrimental for the spin polarization. The finding of an intrinsic spin-polarization at the A-site cation observed in x-ray magnetic circular dichroism (XMCD) measurements also reveals the existence of a complex magnetic configuration at the interface, different from the magnetic phases observed at the inner layers.

Spin polarization properties at the spinterface of thiophene/Fe(100): First principles calculations

Based on density functional theory (DFT), the spin polarization properties of a thiophene molecule which is adsorbed at Fe (100) surface are discussed. A variety of horizontal and vertical adsorption configurations as well as their influences on the spin density distributions are studied in detail. The spin polarization comes from the [Formula: see text]-[Formula: see text] orbital coupling between the thiophene molecule and the electrode, which leads to the molecules’ energy level shifting and the density of states (DOS) broadening, so the two spin states near the Fermi level are exchange split. It is also found that the interfacial spin polarization is different under different contact configurations, and the biggest one will be obtained when the S atom is directly placed above the Fe atom at the horizontal direction. On the other hand, interface spin inversion can be obtained by adjusting the adsorption position, which will be helpful to build spin sensors.

Spin selection at organic spinterface by anchoring group

Control of organic interfacial spin polarization is crucial in organic spintronics. Based on ab initio theory, here we proposed a spin selection at organic interface via anchoring group by adsorbing an organic molecule onto Ni(111) surface. The results demonstrate that either a positive or negative interfacial spin polarization may be obtained by choosing different anchoring groups. The orbital analysis via the projected density of states shows that the interfacial spin polarization is sensitive to the hybridization of the outer orbital of the anchoring atom as well as its energy relative to the d orbital of the ferromagnetic atom. The work indicates a feasible way to realize spin selection at the organic spinterface by anchoring group.

Large magnetoelectric effect in organic ferroelectric copolymer-based multiferroic tunnel junctions

We report electrically controlled interfacial spin polarization, or the magnetoelectric effect in multiferroic tunnel junctions by employing organic ferroelectric copolymers, poly(vinylindene fluoride-trifluoroethylene) (P(VDF-TrFE)), as a tunneling barrier. First, we show that the ferroelectric domains and spontaneous ferroelectric polarization of the P(VDF-TrFE) films can be formed in a thin interlayer. Next, we demonstrate that the tunneling magnetoresistance in the unpolarized multiferroic tunnel junction severely quenches from 21% at 20 K to 0.7% at 296 K. Remarkably, we find that the interfacial spin polarization of the device, dubbed spinterface, can be gradually tuned by controlling the ferroelectric polarization with an applied electric field. Specifically, the tunneling electromagnetoresistance can reach around 1000% while the tunneling electroresistance reaches about 30% at 200 K. We speculate that the interface might act as a polarization-dependent spin filter causing the large spinterface effect. The result suggests that organic magnetoelectric-based information storage with four-state bits is feasible at room temperature.

Modulation of organic interfacial spin polarization by interfacial angle

Based on ab initio theory, we theoretically investigated the interfacial spin polarization by adsorbing a benzene-dithiolate molecule onto a nickel surface with different interfacial angles. A variable magnitude and even an inversion of the interfacial spin polarization are observed with the increase of the interfacial angle. The orbital analysis shows that the interfacial spin polarization is codetermined by two kinds of orbital hybridization between the molecule and the ferromagnet, the pz-d hybridization and the sp3-d hybridization, which show different dependence on the angle. These results indicate a new way to manipulate the spin polarization at organic spinterface.

Static magnetic proximity effect inPt/Ni1−xFexbilayers investigated by x-ray resonant magnetic reflectivity

We present x-ray resonant magnetic reflectivity (XRMR) as a very sensitive tool to detect proximity induced interface spin polarization in Pt/Fe, Pt/Ni$_{33}$Fe$_{67}$, Pt/Ni$_{81}$Fe$_{19}$ (permalloy), and Pt/Ni bilayers. We demonstrate that a detailed analysis of the reflected x-ray intensity gives insight in the spatial distribution of the spin polarization of a non-magnetic metal across the interface to a ferromagnetic layer. The evaluation of the experimental results with simulations based on optical data from ab initio calculations provides the induced magnetic moment per Pt atom in the spin polarized volume adjacent to the ferromagnet. We find the largest spin polarization in Pt/Fe and a much smaller magnetic proximity effect in Pt/Ni. Additional XRMR experiments with varying photon energy are in good agreement with the theoretical predictions for the energy dependence of the magnetooptic parameters and allow identifying the optical dispersion $\delta$ and absorption $\beta$ across the Pt L3-absorption edge.