Spin-polarized Surface Research Articles

Chiral electrolytes for rechargeable metal batteries

Charge transfer at the liquid (electrolyte)-solid (metal) interfaces is of fundamental importance to metal electrochemical deposition that further determines the reversibility and kinetics of energy-dense rechargeable metal batteries (RMBs). We demonstrate the fast charge transfer at the electrolyte-metal interfaces for lithium metal by designing and synthesizing electrolytes with chiral solvents: R (or S)-1,2-dimethoxypropane (R-DMP or S-DMP) and R (or S)-4-methyl-1,3-dioxolane (R-MDOL or S-MDOL). The chiral-induced spin selectivity is considered to produce spin-polarized metal surfaces, enabling the improvement in charge transfer rate and efficiency. The deposited Li metal in chiral electrolytes shows smooth and uniform morphologies, as well as high initial (>95%) and average (∼99.2%) Coulombic efficiency for Li metal stripping/plating process, thus prolonging the life-span of batteries using thin lithium anode (50 μm) to 400 cycles till 80% capacity retention. This work provides a distinct approach to regulate metal deposition beyond the limitation of ion de-solvation.

Visualization of spin-polarized surface resonances in Pb-based ternary topological insulators

The formation of the topological surface state originates from bulk band inversion at the top of the valence band and the bottom of the conduction band. The transition between normal and topological insulators is known as a topological phase transition. Here we show spin-polarized electronic states of Pb-based ternary topological insulators Pb(Bi1-xSbx)2Te4 (x = 0.55, 0.70, 0.79) investigated by spin- and angle-resolved photoemission spectroscopy and first-principles calculations. We visualize a pair of spin-polarized surface resonances dispersing along the upper edge of projected bulk bands in occupied states. Interestingly, a branch of the spin-polarized surface resonances continuously connects to the topological surface state. The coexistence of the topological surface state and the spin-polarized surface resonances can be explained by considering the topological phase transition.

Manipulating Charge-to-Spin conversion via insertion layer control at the interface of topological insulator and ferromagnet

Strong spin–orbit coupling and highly spin-polarized surface states in topological insulators (TIs) are key parameters that explain their extremely high charge-to-spin conversion (CSC) efficiency at interfaces with ferromagnetic materials (FMs). This study focused on the influence of the insertion layer on the proximity effect occurring in a Co4Fe4B2/Bi2Se3 interface. Various insertion layers, including Au, MgO, and Se, were introduced to modulate the proximity effect from TI to FM and vice versa. X-ray photoelectron spectroscopy and transmission electron microscopy revealed that the Se insertion layer effectively suppresses the formation of an additional Bi layer, reducing intermixing against Co4Fe4B2. Electrical transport properties such as RXX and RXY under a vertical magnetic field show that the Se-inserted structure features the lowest anomalous Hall angle and exhibits a pristine topological surface state, indicating its potential for improving CSC efficiency. The Se-inserted structure exhibits the highest spin Hall angle among various heterostructures, according to results obtained from spin-torque ferromagnetic resonance. These findings highlight the importance of selecting an insertion layer and controlling the interface to optimize the spin-transport properties of TI-based spintronic devices and provide insights into the design of future spin devices.

Spin-Charge-Lattice Coupling across the Charge Density Wave Transition in a Kagome Lattice Antiferromagnet.

Understanding spin and lattice excitations in a metallic magnetic ordered system forms the basis to unveil the magnetic and lattice exchange couplings and their interactions with itinerant electrons. Kagome lattice antiferromagnet FeGe is interesting because it displays a rare charge density wave (CDW) deep inside the antiferromagnetic ordered phase that interacts with the magnetic order. We use neutron scattering to study the evolution of spin and lattice excitations across the CDW transition T_{CDW} in FeGe. While spin excitations below ∼100 meV can be well described by spin waves of a spin-1 Heisenberg Hamiltonian, spin excitations at higher energies are centered around the Brillouin zone boundary and extend up to ∼180 meV consistent with quasiparticle excitations across spin-polarized electron-hole Fermi surfaces. Furthermore, c-axis spin wave dispersion and Fe-Ge optical phonon modes show a clear hardening below T_{CDW} due to spin-charge-lattice coupling but with no evidence of a phonon Kohn anomaly. By comparing our experimental results with density functional theory calculations in absolute units, we conclude that FeGe is a Hund's metal in the intermediate correlated regime where magnetism has contributions from both itinerant and localized electrons arising from spin polarized electronic bands near the Fermi level.

Chiral whispering gallery modes and chirality-dependent symmetric optical force induced by a spin-polarized surface wave of photonic Dirac semimetal.

Dirac degeneracy is a fourfold band crossing point in a three-dimensional momentum space, which possesses Fermi-arc-like surface states, and has extensive application prospects. In this work, we systematically study the exceptional effects of the robust chiral surface wave supported by photonic Dirac semimetal acts on the dielectric particles. Theoretical results show that orthogonal electromagnetic modes and helical or chiral whispering gallery modes (WGMs) of dielectric particles can be efficiently excited by the unidirectional spin-polarized surface wave. More importantly, optical forces exerted by the spin-polarized surface wave exhibit chirality-dependent symmetric behavior and high chiral Q factor with precise size selectivity. Our findings may provide potential applications in the area of chiral microcavity, spin optical devices, and optical manipulations.

Fresh sodium storage of FeCoNi alloys confined in biomass carbon revealed by operando magnetometry

Focusing on the commercialization of sodium ion batteries (SIBs), the biggest challenge is discovering proper anode materials with high availability and safety. Among various materials, alloying metal anodes can achieve high-capacity sodium storage. However, transition metals, such as Fe, Co, Ni, etc. are considered to be inactive alloying with Na. Herein, by introducing trimetallic FeCoNi alloy nanoparticles confined in waste wool-derived carbon based on a sulfhydryl domain-limiting strategy, we synthesize porous N, S co-doped biomass carbon-coated trimetallic FeCoNi alloy composites (FeCoNi@NSC). Surprisingly, the optimal FeCoNi@NSC anode displays superior reversible specific capacities of 439.4 mAh·g−1 at 0.1 A·g−1, and an excellent cycling life of up to1000 cycles at 4 A·g−1, which is similar to that of the current reported tin/antimony/germanium/bismuth-based anodes. Besides the capacity contribution of biomass carbon, the combination of in situ magnetometry, high-resolution transmission electron microscopy and electrochemical impedance characterization techniques reveal that the rising capacity originates from spin-polarized surface capacitance, extra capacity of transition metal oxides, and low-voltage capacity of solid electrolyte interphase, as quantificated by monitoring the variation in magnetism of surface capacitance. This work provides a breakthrough concept for novel anode materials of SIBs choices.

Robust fully spin-polarized nodal chain in 3D metal-organic framework

The identification of fully spin-polarized topological phases in magnetic inorganic materials has attracted significant attention. In this study, through first-principles calculations, we characterize CrCl2(pyz)2, a metal-organic framework (MOF), as a nodal chain semimetal. Our results reveal a ferromagnetic ground state in this material, presenting as a half-metal with a single spin channel near the Fermi level. Specifically, the spin-down states form a nodal chain close to the Fermi level, consisting of three nodal loops protected by glide mirror symmetry on distinct planes. Furthermore, fully spin-polarized drumhead surface states corresponding to these nodal loops are identified on the material's surfaces. Remarkably, we observe the persistence of the fully spin-polarized nodal chain even when tuning the ligand rotation angle of the MOF. Furthermore, our investigation delves into the influence of spin-orbit coupling (SOC) on the system, revealing that it has minimal impact on the nodal chain. The robustness of the nodal chain in the presence of SOC underscores its intriguing and resilient nature, indicating its potential utility in various electronic applications. Ultimately, the robust realization of a fully spin-polarized nodal chain in this magnetic MOF system holds promise for applications in the realm of spintronics.

Surface Spin Polarization in the Magnetic Response of GeTe Rashba Ferroelectric

We experimentally investigate magnetization reversal curves for a GeTe topological semimetal. In addition to the known lattice diamagnetic response, we observe narrow magnetization loop in low fields, which should not be expected for non-magnetic material. The diamagnetic hysteresis loop is unusual, so the saturation level is negative in positive fields, and the loop is passed clockwise, in contrast to standard ferromagnetic behavior. We show, that the experimental hysteresis curves cannot be obtained from standard ferromagnetic ones by adding/subtracting of any linear dependence, or even by considering several interacting magnetic phases. The latter possibility is also eliminated by the remanence plots technique (Henkel or \\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\delta M$$\\end{document} plots). We explain our results as a direct consequence of the correlation between ferroelectricity and spin-polarized surface states in GeTe, similarly to magnetoelectric structures.

Optimizing Electron Spin-Polarized States of MoSe2/Cr2Se3 Heterojunction-Embedded Carbon Nanospheres for Superior Sodium/Potassium-Ion Battery Performances.

The principal challenges faced by sodium-ion batteries (SIBs) and potassium-ion batteries (KIBs) revolve around identifying suitable host materials capable of accommodating metal ions with larger dimensions and addressing the issue of sluggish chemical kinetics. Herein, a MoSe2/Cr2Se3 heterojunction uniformly embedded is fabricated in nitrogen-doped hollow carbon nanospheres (MoSe2/Cr2Se3@N-HCSs) as an electrode material for SIBs and KIBs. Cr2Se3 exhibits spontaneous antiparallel alignment of magnetic moments. Mo2+ doping is employed to regulate the electron spin states of Cr2Se3. Moreover, the MoSe2 and Cr2Se3 heterojunctions induce a lattice mismatch at the heterostructure interface, resulting in spin-polarized states or localized magnetic moments at the interface, potentially contributing to spin-polarized surface capacitance. MoSe2/Cr2Se3@N-HCSs demonstrate a high capacity of 498 mAh g-1 at 0.1 A g-1 with good cycling stability (capacity of 405 mAh g-1 and a coulombic efficiency of 99.8% after 1000 cycles). Additionally, density functional theory (DFT) calculations simulate the accumulation of spin-polarized charges at the MoSe2/Cr2Se3@N-HCSs heterojunction interface, dependent on the surface electron density of the antiferromagnetic Cr2Se3 and the surface spin polarization near the Fermi level. After regulating the electron spin states through Mo-doping, the band gap of the material decreases. These significant findings provide novel insights into the design and synthesis of electrode materials with exceptional performance characteristics for batteries.

Coexistence of electron and phonon topology in conjunction with quantum transport device modeling

The escalating research in the field of topology necessitates an understanding of the underlying rich physics behind the materials possessing unique features of non-trivial topology in both electronic and phononic states. Due to the interaction between electronic quasiparticles and spin degrees of freedom, the realization of magnetic topological materials has opened up a new frontier with unusual topological phases, however, these are rarely reported alongside phononic quasiparticle excitations. In this work, by first-principles calculations and symmetry analysis, the intermetallic ferromagnetic compounds MnGaGe and MnZnSb with the coexistence of exceptional topological features in the electronic and phononic states are proposed. These compounds host nodal surface on ky=π plane in bulk Brillouin zone in the electronic and phononic spectra protected by the combination of time-reversal symmetry and nonsymmorphic two-fold screw-rotation symmetry. In the former case, a spin-polarized nodal surface is present in the majority and minority spin channels and found to be robust to ground-state magnetic polarization. The presence of nodal line features is analyzed in both the quasiparticle spectra, whose non-trivial nature is confirmed by the Berry phase calculation. The incorporation of spin–orbit coupling in the electron spectra introduces distinctive characteristics in the transport properties, facilitating the emergence of anomalous Hall conductivity through Berry curvature in both bulk and monolayer. Furthermore, the monolayer has been proposed as a two-terminal device model to investigate the quantum transport properties using the non-equilibrium Green’s function approach. This superlative combination of observations and modeling sets the path for a greater level of insight into the behavior and aspects of topological materials at the atomic scale.

Observation of large spin-polarized Fermi surface of a magnetically proximitized semiconductor quantum well

The magnetic proximity effect (MPE) attracts much attention as a promising way for introducing ferromagnetism into a nonmagnetic electron-transport channel. Although the range of MPE is generally limited to the interface, it is extended to several tens of nm in high-quality semiconductor bilayers consisting of a nonmagnetic quantum well (QW) and an underlying ferromagnetic semiconductor (FMS) layer. To elucidate the mechanism of this long-range MPE, it is essential to observe the magnetically proximitized electronic structure of the nonmagnetic semiconductor. Here, by investigating the Shubnikov - de Haas oscillations in nonmagnetic n-type InAs QW / FMS (Ga,Fe)Sb bilayers, we successfully observe the spin-polarized Fermi surface of the InAs QW. The spontaneous spin-splitting energy in the conduction band of the InAs QW reaches 18 meV when applying a negative gate voltage. This large and gate-tunable spin-polarized Fermi surface of a magnetically proximitized InAs QW provides an ideal platform for novel spintronic and topological devices.

Spin-Polarized Surface Capacitance Effects Enable Fe3 O4 Anode Superior Wide Operation-Temperature Sodium Storage.

Fe3 O4 is widely investigated as an anode for ambient sodium-ion batteries (SIBs), but its electrochemical properties in the wide operation-temperature range have rarely been studied. Herein, the Fe3 O4 nanoparticles, which are well encapsulated by carbon nanolayers, are uniformly dispersed on the graphene basal plane (named Fe3 O4 /C@G) to be used as the anode for SIBs. The existence of graphene can reduce the size of Fe3 O4 /C nanoparticles from 150 to 80nm and greatly boost charge transport capability of electrode, resulting in an obvious size decrease of superparamagnetic Fe nanoparticles generated from the conversion reaction from 5 to 2nm. Importantly, the ultra-small superparamagnetic Fe nanoparticles (≈2nm) can induce a strong spin-polarized surface capacitance effect at operating temperatures ranging from -40 to 60°C, thus achieving highly efficient Na-ion transport and storage in a wide operation-temperature range. Consequently, the Fe3 O4 /C@G anode shows high capacity, excellent fast-charging capability, and cycling stability ranging from -40 to 60°C in half/full cells. This work demonstrates the viability of Fe3 O4 as anode for wide operation-temperature SIBs and reveals that spin-polarized surface capacitance effects can promote Na-ion storage over a wide operation temperature range.

Electric field-dependent photoexcited spin-polarized electron transport in Bi2Se3 topological insulator

Three-dimensional (3D) topological insulators (TIs) exhibit spin-polarized surface states in which the spin of electrons is locked to their momentum. The helical surface states can be explored from circularly polarized light-induced spin photocurrent, a phenomenon called circular photogalvanic effect (CPGE). In this work, we fabricate a TI transistor with the Bi2Se3 channel layer synthesized using vapor deposition. The photocurrent response of Bi2Se3 TI is characterized under horizontal and longitudinal electric fields. CPGE and linear photogalvanic effect (LPGE) contribute to the surface state photocurrent at room temperature. The longitudinal electric field provides kinetic energy to the electrons so that the transition of electrons to higher energy bands in momentum space occurs. Under a photon excitation with the energy far above the TI bandgap, we observed a photocurrent difference between left and right circularly polarized light excitation. The photocurrent variation with gate voltage (longitudinal field) is also investigated. Adjusting the Fermi level with the gate bias leads to changes in the population of bulk state carriers and spin electrons in surface states. By shifting the gate bias toward negative, the CPGE current increases because of the reduced scattering with bulk carriers. Our work reveals that longitudinal and horizontal electric fields can manipulate the helical spin-polarized photocurrent of Bi2Se3. From the asymmetry of circularly polarized photoconductive differential current (CPDC) under the horizontal field, we found evidence of spin-polarized electron transition to other conduction band valleys at room temperature under a high-energy photon excitation.

P6322-type SrNiIO6: An ideal half-metallic candidate with a fully spin-polarized Weyl complex

Researchers are interested in magnetic topological materials because they can integrate magnetic and topological properties. Using the first-principles calculations, we identify the P6322-type SrNiIO6 as a dynamically stable half-metallic candidate with a completely spin-polarized Weyl complex formed by two hourglass charge-3 and six charge-1 Weyl points. Furthermore, distinct surface arcs linked the projections of two spin-polarized charge-3 Weyl points and six spin-polarized charge-1 Weyl points, resulting in a fully spin-polarized sextuple-helicoid surface arc mode on the (001) surface of P6322-type SrNiIO6. P6322-type SrNiIO6 with fully spin-polarized charge-3 and charge-1 Weyl points and a fully spin-polarized sextuple-helicoid surface arc mode is, without a doubt, a promising candidate for applications in spintronic and topological physics.

Giant and Tunable Out-of-Plane Spin Polarization of Topological Antimonene.

Topological insulators are bulk insulators with metallic and fully spin-polarized surface states displaying Dirac-like band dispersion. Due to spin-momentum locking, these topological surface states (TSSs) have a predominant in-plane spin polarization in the bulk fundamental gap. Here, we show by spin-resolved photoemission spectroscopy that the TSS of a topological insulator interfaced with an antimonene bilayer exhibits nearly full out-of-plane spin polarization within the substrate gap. We connect this phenomenon to a symmetry-protected band crossing of the spin-polarized surface states. The nearly full out-of-plane spin polarization of the TSS occurs along a continuous path in the energy-momentum space, and the spin polarization within the gap can be reversibly tuned from nearly full out-of-plane to nearly full in-plane by electron doping. These findings pave the way to advanced spintronics applications that exploit the giant out-of-plane spin polarization of TSSs.

Exceeding Theoretical Capacity in Exfoliated Ultrathin Manganese Ferrite Nanosheets via Galvanic Replacement‐Derived Self‐Hybridization for Fast Rechargeable Lithium‐Ion Batteries (Adv. Funct. Mater. 21/2023)

Exceeding Theoretical Capacity In article number 2300143, Won Bae Kim and co-workers report the rational design of hybrid ultrathin manganese ferrite nanosheets through interfacial modifications that can exceed the theoretically limited energy storage capacity by fully utilizing highly spin-polarized surface capacitance. This study potentially opens a new paradigm for ever-increasing performance of lithium-ion batteries in renewable energy storage.

Geometry-Induced Spin Filtering in Photoemission Maps from WTe_{2} Surface States.

We demonstrate that an important quantum material WTe_{2} exhibits a new type of geometry-induced spin filtering effect in photoemission, stemming from low symmetry that is responsible for its exotic transport properties. Through the laser-driven spin-polarized angle-resolved photoemission Fermi surface mapping, we showcase highly asymmetric spin textures of electrons photoemitted from the surface states of WTe_{2}. Such asymmetries are not present in the initial state spin textures, which are bound by the time-reversal and crystal lattice mirror plane symmetries. The findings are reproduced qualitatively by theoretical modeling within the one-step model photoemission formalism. The effect could be understood within the free-electron final state model as an interference due to emission from different atomic sites. The observed effect is a manifestation of time-reversal symmetry breaking of the initial state in the photoemission process, and as such it cannot be eliminated, but only its magnitude influenced, by special experimental geometries.

Single‐Layered MoS2 Fabricated by Charge‐Driven Interlayer Expansion for Superior Lithium/Sodium/Potassium‐Ion‐Battery Anodes

Single-layered MoS2 is a promising anode material for lithium-ion batteries (LIBs), sodium-ion batteries (SIBs), and potassium-ion batteries (PIBs) due to its high capacity and isotropic ion transport paths. However, the low intrinsic conductivity and easy-agglomerated feature hamper its applications. Here, a charge-driven interlayer expansion strategy that Co2+ replaces Mo4+ in the doping form to endow MoS2 layers with negative charges, thus inducing electrostatic repulsion, together with the insertion of gaseous groups, to drive interlayer expansion which once breaks the confinement of interlayer van der Waals force, single-layered MoS2 is obtained and uniformly dispersed into carbon matrix arising from the transformation of carbonaceous gaseous groups under high vapor pressure, is proposed. Co atom doping helps enhance the intrinsic conductivity of single-layered MoS2 . Carbon matrix effectively prevents agglomeration of single-layered MoS2 . The doped Co atoms can be fully transformed into ultrasmall Co nanoparticles during conversion reaction, which enables strong spin-polarized surface capacitance and thus significantly boosts ion transport and storage. Consequently, the prepared material delivers superb Li/Na/K-ion storage performances, which are best in the reported MoS2 -based anodes. The proposed charge-driven interlayer expansion strategy provides a novel perspective for preparing single-layered MoS2, which shows huge potential for energy storage.

Design of molecular M[sbnd]N[sbnd]C dual-atom catalysts for nitrogen reduction starting from surface state analysis

Under electrocatalytic conditions, the state of a catalyst surface (e.g., adsorbate coverage) can be very different from a pristine form due to the existing conversion equilibrium between water and H- and O-containing adsorbates. Dismissing the analysis of the catalyst surface state under operating conditionsmay lead to misleading guidelines for experiments. Given that confirming the actual active site of the catalyst under operating conditions is indispensable to providing practical guidance for experiments, herein, we analyzed the relations between the Gibbs free energy and the potential of a new type of molecular metal-nitrogen-carbon (MNC) dual-atom catalysts (DACs) with a unique 5 N-coordination environment, by spin-polarized density functional theory (DFT) and surface Pourbaix diagram calculations. Analyzing the derived surface Pourbaix diagrams, we screened out three catalysts, N3-Ni-Ni-N2, N3-Co-Ni-N2, and N3-Ni-Co-N2, to further study the activity of nitrogen reduction reaction (NRR). The results display that N3-Co-Ni-N2 is a promising NRR catalyst with a relatively low ΔG of 0.49 eV and slow kinetics of the competing hydrogen evolution. This work proposes a new strategy to guide DAC experiments more precisely: the analysis of the surface occupancy state of the catalysts under electrochemical conditions should be performed before activity analysis.

Observation of Gapped Topological Surface States and Isolated Surface Resonances in PdTe2 Ultrathin Films.

The superconductor PdTe2 is known to host bulk Dirac bands and topological surface states. The coexistence of superconductivity and topological surface states makes PdTe2 a promising platform for exploring topological superconductivity and Majorana bound states. In this work, we report the spectroscopic characterization of ultrathin PdTe2 films with thickness down to three monolayers (ML). In the 3 ML PdTe2 film, we observed spin-polarized surface resonance states, which are isolated from the bulk bands due to the quantum size effects. In addition, the hybridization of surface states on opposite faces leads to a thickness-dependent gap in the topological surface Dirac bands. Our photoemission results show clearly that the size of the hybridization gap increases as the film thickness is reduced. The observation of isolated surface resonances and gapped topological surface states sheds light on the applications of PdTe2 quantum films in spintronics and topological quantum computation.