Correction for ‘The mechanism of the molecular CISS effect in chiral nano-junctions’ by Thi Ngoc Ha Nguyen et al., Chem. Sci., 2024, 15, 14905–14912, https://doi.org/10.1039/D4SC04435E
Quantum dots consisting of an axial Zn0.97Mg0.03Te insertion inside a large-bandgap Zn0.9Mg0.1Te nanowire core are fabricated in a molecular-beam epitaxy system by employing the vapor-liquid-solid growth mechanism. In addition, this structure is coated with a thin ZnSe radial shell that forms a type-II interface with the dot semiconductor. The resulting radial electron-hole separation is evidenced by several distinct effects that occur in the presence of the ZnSe shell, including the optical emission redshift of about 250 meV, a significant decrease in emission intensity, an increase in the excitonic lifetime by one order of magnitude, and an increase in the biexciton binding energy. The type-II nanowire quantum dots where electrons and holes are radially separated constitute a promising platform for potential applications in the field of quantum information technology.
The perpendicular magnetocrystalline anisotropy, magnetoelastic properties as well as the Gilbert damping factor in Co2Fe0.4Mn0.6Si thin films were found to depend on a magnetic layer thickness, and they can be also tuned by the application of additional Ag buffer layer. The tetragonal distortion of a magnetic layer was found to increase with decreasing thickness, and after the application of an additional Ag buffer layer, the character of this distortion was changed from tensile to compressive in the plane of a film. A correlation between the tetragonal distortion and perpendicular magnetocrystalline anisotropy was found. However, the magnitude of the observed tetragonal distortion for most samples seems to be too small to explain alone the experimentally found large magnitude of the perpendicular magnetocrystalline anisotropy. For these samples, other mechanisms including both surface and volume effects must be taken into account.
Metal-reducing bacteria have adapted the ability to respire extracellular solid surfaces instead of soluble oxidants. This process requires an electron transport pathway that spans from the inner membrane, across the periplasm, through the outer membrane, and to an external surface. Multiheme cytochromes are the primary machinery for moving electrons through this pathway. Recent studies show that the chiral-induced spin selectivity (CISS) effect is observable in some of these proteins extracted from the model metal-reducing bacteria, Shewanella oneidensis MR-1. It was hypothesized that the CISS effect facilitates efficient electron transport in these proteins by coupling electron velocity to spin, thus reducing the probability of backscattering. However, these studies focused exclusively on the cell surface electron conduits, and thus, CISS has not been investigated in upstream electron transfer components such as the membrane-associated MtrA, or periplasmic proteins such as small tetraheme cytochrome (STC). By using conductive probe atomic force microscopy measurements of protein monolayers adsorbed onto ferromagnetic substrates, we show that electron transport is spin selective in both MtrA and STC. Moreover, we have determined the spin polarization of MtrA to be ∼77% and STC to be ∼35%. This disparity in spin polarizations could indicate that spin selectivity is length dependent in heme proteins, given that MtrA is approximately two times longer than STC. Most significantly, our study indicates that spin-dependent interactions affect the entire extracellular electron transport pathway.
The anisotropic magnetoelastic (ME) properties of epitaxial Co2Fe0.4Mn0.6Si (CFMS) Heusler alloy thin films with thicknesses ranging from 8 to 100 nm were investigated using the strain-modulated ferromagnetic resonance (SMFMR) technique. The calculation of the first cubic magnetocrystalline (MC) constant $K_{1}$ and the two cubic ME constants $b_{1}$ and $b_{2}$ was carried out assuming the cubic symmetry of the magnetic layer. A significant negative perpendicular MC anisotropy, of the order of 105 J/m3, was also observed. The investigated parameters were found to be dependent on the thickness of the magnetic layer. The thinnest magnetic layers showed the strongest cubic MC anisotropy and the weakest anisotropy of ME properties. These findings highlight the importance of considering the magnetic layer thickness when evaluating the anisotropy in the ME properties of Heusler alloy thin films.
Propagation of electrons along helical molecules adsorbed on surfaces comes along with a robust spin polarization effect called chirality induced spin selectivity CISS. However, experiments on the molecular scale that allow a true correlation of spin effects with the molecular structure are quite rare. Here we have studied the structure of self-assembled chiral molecules and the electronic transmission and spin polarization of the current through the system by means of ambient scanning tunneling microscopy and spectroscopy in heterostructures of various α-helix polyalanine-based molecules (PA) adsorbed on Al2O3/Pt/Au/Co/Au substrates with perpendicular magnetic anisotropy. We have found a phase separation of the molecules into well-ordered enantiopure 2D hexagonal phases and quasi-1D heterochiral-dimer structures, which allows for the analysis of the spin polarization with almost atomic precision of PA in different phases. The spin polarization reaches up to 75% for chemisorbed molecules arranged in a hexagonal phase. On the contrary, for weakly coupled PA molecules without cysteine anchoring groups in a quasi-1D phase, a spin polarization of around 50% was found. Our results show that both the intermolecular interaction as well as the coupling to the substrate are important and point out that collective effects within the molecules and at the interfaces are required to achieve a high chiral induced spin selectivity.
A strain modulated ferromagnetic resonance technique was applied to determine two cubic magnetoelastic constants of the epitaxially grown 30-nm-thick ${\mathrm{Co}}_{2}{\mathrm{Fe}}_{x}{\mathrm{Mn}}_{1\ensuremath{-}x}\mathrm{Si}$ magnetic layers with different Fe and Mn contents, which were deposited on a MgO substrate with a 20-nm-thick Cr buffer layer---MgO (001) $\ensuremath{\parallel}$ Cr(001) $\ensuremath{\parallel} {\mathrm{Co}}_{2}{\mathrm{Fe}}_{x}{\mathrm{Mn}}_{1\ensuremath{-}x}\mathrm{Si}$ (001). It was found that, for the samples with the Fe content $x=0.4$ or higher, the magnitudes of the two cubic magnetoelastic constants are clearly different, showing that the magnetoelastic properties of these samples are different than in the case of isotropic samples for which these two constants are expected to be equal. The magnitude of the cubic magnetocrystalline anisotropy constant reveals an evident maximum at the composition of $x=0.4$, which corresponds to the minimum of the minor spin density of states, and thus the correlation between the cubic magnetocrystalline anisotropy and the electronic band structure. For all the investigated samples, a large perpendicular component of the magnetocrystalline anisotropy was observed as well as inhomogeneous broadening of the ferromagnetic resonance linewidth.
Polyalanine molecules (PA) with an α-helix conformation have recently attracted a great deal of interest, as the propagation of electrons through the chiral backbone structure comes along with spin polarization of the transmitted electrons. By means of scanning tunneling microscopy and spectroscopy under ambient conditions, PA molecules adsorbed on surfaces of epitaxial magnetic Al2O3/Pt/Au/Co/Au nanostructures with perpendicular anisotropy were studied. Thereby, a correlation between the PA molecules ordering at the surface with the electron tunneling across this hybrid system as a function of the substrate magnetization orientation as well as the coverage density and helicity of the PA molecules was observed. The highest spin polarization values, P, were found for well-ordered self-assembled monolayers and with a defined chemical coupling of the molecules to the magnetic substrate surface, showing that the current-induced spin selectivity is a cooperative effect. Thereby, P deduced from the electron transmission along unoccupied molecular orbitals of the chiral molecules is larger as compared to values derived from the occupied molecular orbitals. Apparently, the larger orbital overlap results in a higher electron mobility, yielding a higher P value. By switching the magnetization direction of the Co layer, it was demonstrated that the non-spin-polarized STM can be used to study chiral molecules with a submolecular resolution, to detect properties of buried magnetic layers and to detect the spin polarization of the molecules from the change in the magnetoresistance of such hybrid structures.
A strain modulated ferromagnetic resonance technique was applied to determine two cubic magnetoelastic constants of the epitaxially grown 30-nm-thick Co2FexMn1???xSi magnetic layers with different Fe and Mn contents, which were deposited on a MgO substrate with a 20-nm-thick Cr buffer layer???MgO (001) II Cr(001) II Co2FexMn1???xSi (001). It was found that, for the samples with the Fe content x = 0.4 or higher, the magnitudes of the two cubic magnetoelastic constants are clearly different, showing that the magnetoelastic properties of these samples are different than in the case of isotropic samples for which these two constants are expected to be equal. The magnitude of the cubic magnetocrystalline anisotropy constant reveals an evident maximum at the composition of x = 0.4, which corresponds to the minimum of the minor spin density of states, and thus the correlation between the cubic magnetocrystalline anisotropy and the electronic band structure. For all the investigated samples, a large perpendicular component of the magnetocrystalline anisotropy was observed as well as inhomogeneous broadening of the ferromagnetic resonance linewidth.
Co 2 Fe 0.4 Mn 0.6 Si (CFMS) and Co 2 FeGa 0.5 Ge 0.5 (CFGG) Heusler alloys are among the most promising thin film materials for spintronic devices due to a high spin polarization, low magnetic damping and giant/tunneling magnetoresistance ratios. Despite numerous investigations of Heusler alloys magnetic properties performed up to now, magnetoelastic effects in these materials remain not fully understood; due to quite rare studies of correlations between magnetoelastic and other magnetic properties, such as magnetic dissipation or magnetic anisotropy. In this research we have investigated epitaxial CFMS and CFGG Heusler alloys thin films of thickness in the range of 15–50 nm. We have determined the magnetoelastic tensor components and magnetic damping parameters as a function of the magnetic layer thickness. Magnetic damping measurements revealed the existence of non-Gilbert dissipation related contributions, including two-magnon scattering and spin pumping phenomena. Magnetoelastic constant B 11 values and the effective magnetic damping parameter α eff values were found to be in the range of − 6 to 30 × 10 6 erg/cm 3 and between 1 and 12 × 10 –3 , respectively. The values of saturation magnetostriction λ S for CFMS Heusler alloy thin films were also obtained using the strain modulated ferromagnetic resonance technique. The correlation between α eff and B 11 , depending on magnetic layer thickness was determined based on the performed investigations of the above mentioned magnetic properties.
When an electron passes through a chiral molecule, there is a high probability for correlation between the momentum and spin of the charge, thus leading to a spin polarized current. This phenomenon is known as the chiral-induced spin selectivity (CISS) effect. One of the most surprising experimental results recently demonstrated is that magnetization reversal in a ferromagnet with perpendicular anisotropy can be realized solely by chemisorbing a chiral molecular monolayer without applying any current or external magnetic field. This result raises the currently open question of whether this effect is due to the bonding event, held by the ferromagnet, or a long-time-scale effect stabilized by exchange interactions. In this work we have performed vectorial magnetic field measurements of the magnetization reorientation of a ferromagnetic layer exhibiting perpendicular anisotropy due to CISS using nitrogen-vacancy centers in diamond and followed the time dynamics of this effect. In parallel, we have measured the molecular monolayer tilt angle in order to find a correlation between the time dependence of the magnetization reorientation and the change of the tilt angle of the molecular monolayer. We have identified that changes in the magnetization direction correspond to changes of the molecular monolayer tilt angle, providing evidence for a long-time-scale characteristic of the induced magnetization reorientation. This suggests that the CISS effect has an effect over long time scales which we attribute to exchange interactions. These results offer significant insights into the fundamental processes underlying the CISS effect, contributing to the implementation of CISS in state-of-the-art applications such as spintronic and magnetic memory devices.
ZnTe/CdSe/(Zn, Mg)Te core/double-shell nanowires are grown by molecular beam epitaxy by employing the vapor-liquid-solid growth mechanism assisted with gold catalysts. A photoluminescence study of these structures reveals the presence of an optical emission in the near infrared. We assign this emission to the spatially indirect exciton recombination at the ZnTe/CdSe type II interface. This conclusion is confirmed by the observation of a significant blue-shift of the emission energy with an increasing excitation fluence induced by the electron-hole separation at the interface. Cathodoluminescence measurements reveal that the optical emission in the near infrared originates from nanowires and not from two-dimensional residual deposits between them. Moreover, it is demonstrated that the emission energy in the near infrared depends on the average CdSe shell thickness and the average Mg concentration within the (Zn, Mg)Te shell. The main mechanism responsible for these changes is associated with the strain induced by the (Zn, Mg)Te shell in the entire core/shell nanowire heterostructure.
The spin–spin interactions between chiral molecules and ferromagnetic metals were found to be strongly affected by the chiral induced spin selectivity effect. Previous works unraveled two complementary phenomena: magnetization reorientation of ferromagnetic thin film upon adsorption of chiral molecules and different interaction rate of opposite enantiomers with a magnetic substrate. These phenomena were all observed when the easy axis of the ferromagnet was out of plane. In this work, the effects of the ferromagnetic easy axis direction, on both the chiral molecular monolayer tilt angle and the magnetization reorientation of the magnetic substrate, are studied using magnetic force microscopy. We have also studied the effect of an applied external magnetic field during the adsorption process. Our results show a clear correlation between the ferromagnetic layer easy axis direction and the tilt angle of the bonded molecules. This tilt angle was found to be larger for an in plane easy axis as compared to an out of plane easy axis. Adsorption under external magnetic field shows that magnetization reorientation occurs also after the adsorption event. These findings show that the interaction between chiral molecules and ferromagnetic layers stabilizes the magnetic reorientation, even after the adsorption, and strongly depends on the anisotropy of the magnetic substrate. This unique behavior is important for developing enantiomer separation techniques using magnetic substrates.
We propose a theoretical model to investigate the magnetic properties of cobalt-doped ZnO (ZnO:Co) thin films qualitatively. The model was built on the dilute Co dopants in the host of ZnO forming the magnetic Co+2 ions and the energy level of the magnetic ions crossing the band edge of ZnO resulting in a magnetic interaction between the Co+2 spins and the spins of the electrons from the conduction band of ZnO. The mechanism of the ferromagnetism revealed in the studied system is proposed here to be induced not only by the mediated conducting electrons via spin interactions but also by the Coulomb excitations, arising from the electrons localized by the oxygen vacancies. This approach of including Coulomb excitation in the modified carrier-mediated model could explain well the magnetic properties of ZnO:Co and solves the drawback of the carrier-mediated model in interpreting the appearance of ferromagnetism in the insulating ZnO:Co. We propose that the Coulomb excitations induced by the electrons captured by the oxygen vacancies are an essential element in the magnetic ZnO, which reveals the fact that the bound magnetic polaron model without considering the Coulomb excitation is insufficient to describe the magnetic properties of ZnO.
Kelvin-probe measurements on ferromagnetic thin film electrodes coated with self-assembled monolayers of chiral molecules reveal that the electron penetration from the metal electrode into the chiral molecules depends on the ferromagnet’s magnetization direction and the molecules’ chirality. Electrostatic potential differences as large as 100 mV are observed. These changes arise from the applied oscillating electric field, which drives spin-dependent charge penetration from the ferromagnetic substrate to the chiral molecules. The enantiospecificity of the response is studied as a function of the magnetization strength, the magnetization direction, and the handedness and length of the chiral molecules. These new phenomena are rationalized in terms of the chiral-induced spin selectivity (CISS) effect, in which one spin orientation of electrons from the ferromagnet penetrates more easily into a chiral molecule than does the other orientation. The large potential changes (>kT at room temperature) manifested here imply that this phenomenon is important for spin transport in chiral spintronic devices and for magneto-electrochemistry of chiral molecules.
Local magnetic imaging at nanoscale resolution is desirable for basic studies of magnetic materials and for magnetic logic and memories. However, such local imaging is hard to achieve by means of standard magnetic force microscopy. Other techniques require low temperatures, high vacuum, or strict limitations on the sample conditions. A simple and robust method is presented for locally resolved magnetic imaging based on short-range spin-exchange interactions that can be scaled down to atomic resolution. The presented method requires a conventional AFM tip functionalized with a chiral molecule. In proximity to the measured magnetic sample, charge redistribution in the chiral molecule leads to a transient spin state, caused by the chiral-induced spin-selectivity effect, followed by the exchange interaction with the imaged sample. While magnetic force microscopy imaging strongly depends on a large working distance, an accurate image is achieved using the molecular tip in proximity to the sample. The chiral molecules' spin-exchange interaction is found to be 150 meV. Using the tip with the adsorbed chiral molecules, two oppositely magnetized samples are characterized, and a magnetic imaging is performed. This method is simple to perform at room temperature and does not require high-vacuum conditions.
Circular dichroism (CD) signals revealed in some materials may arise from different origins during measurements. Magnetic field dependent CD (MCD) emanating from the spin-polarized band provides direct insight into the spin–spin interband transitions in magnetic materials. On the contrary, natural CD effects which are artefactual signals resulting from the linear polarization (LP) components during the polarization modulation with a photo-elastic modulator in anisotropic polymer systems were usually observed. There is no simple method to reliably distinguish MCD effect due to spin polarized band structures from natural CD effect, which limits our understanding of the magnetic material/polymer hybrid structures. This paper aims to introduce a general strategy of averaging out the magnetic linear dichroism (MLD) contributions due to the anisotropic structure and disentangling MCD signal(s) from natural MCD signal(s). We demonstrate the effectiveness of separating MCD from natural MCD using rotational MCD measurement and presented the results of a sample with Co thin film on polymer Scotch tape (unplasticized polyvinyl chloride) glued on a quartz substrate. We demonstrate that the proposed method can be used as an effective tool in disentangling MCD and natural MCD effects, and it opens prospects to study the magnetic material /polymer hybrid systems.
This paper reports on structural and magnetic properties changes that occur after irradiation of Fe/Pt (111) multilayers with Ne+ ions. Multilayer samples of Al2O3 (0001)/Pt 100Å/(Fe X Å/Pt X Å)n/Pt 100Å structure with different individual layer thickness X (5 or 10Å) and different number of bilayers n (5, 10 or 15) were irradiated with Ne+ ions of 10 to 25keV energy and 1×1014÷1×1016 ions cm−2 dose range at room temperature. Irradiation parameters were estimated a priori using Tridyn software. As-deposited samples revealed presence of sharp interfaces. Structural properties changes were investigated using symmetrical and asymmetrical X-ray diffraction methods and magnetic properties changes were examined using vibrating sample magnetometer. Ion beam induced mixing of multilayers resulted in formation of disordered face centered cubic (fcc) FePt alloys of two different compositions (quasi-50:50 in the initial multilayer volume and Pt-rich in initial cover-layer volume). Non-regular changes in magnetic properties after ion irradiation were observed whilst retaining in-plane orientation of magnetization easy axis.
It is commonly assumed that recognition and discrimination of chirality, both in nature and in artificial systems, depend solely on spatial effects. However, recent studies have suggested that charge redistribution in chiral molecules manifests an enantiospecific preference in electron spin orientation. We therefore reasoned that the induced spin polarization may affect enantiorecognition through exchange interactions. Here we show experimentally that the interaction of chiral molecules with a perpendicularly magnetized substrate is enantiospecific. Thus, one enantiomer adsorbs preferentially when the magnetic dipole is pointing up, whereas the other adsorbs faster for the opposite alignment of the magnetization. The interaction is not controlled by the magnetic field per se, but rather by the electron spin orientations, and opens prospects for a distinct approach to enantiomeric separations.
A detailed magneto-photoluminescence study of individual (Cd, Mn) Te/(Cd, Mg) Te core/shell nanowires grown by molecular beam epitaxy is performed. First of all, an enhancement of the Zeeman splitting due to sp-d exchange interaction between band carriers and Mn-spins is evidenced in these nanostructures. Then, it is found that the value of this splitting depends strongly on the magnetic field direction with respect to the nanowire axis. The largest splitting is observed when the magnetic field is applied perpendicular and the smallest when it is applied parallel to the nanowire axis. This effect is explained in terms of magnetic field induced valence band mixing and evidences the light hole character of the excitonic emission. The values of the light and heavy hole splitting are determined for several individual nanowires based on the comparison of experimental results to theoretical calculations.