Rashba Semiconductors Research Articles

Pushing the Thickness Limit of the Giant Rashba Effect in Ferroelectric Semiconductor GeTe.

Ferroelectric Rashba semiconductors (FERSCs) such as α-GeTe are promising candidates for energy-efficient information technologies exploiting spin-orbit coupling (SOC) and are termed spin-orbitronics. In this work, the thickness limit of the Rashba-SOC effect in α-GeTe films is investigated. We demonstrate, using angle-resolved photoemission spectroscopy (ARPES) and first-principles calculations performed on pristine GeTe, that down to 1 nm, GeTe(111) films on a Sb-covered Si(111) substrate continuously exhibit a giant Rashba effect characterized, at 1 nm, by a constant of 5.2 ± 0.5 eV·Å. X-ray photoemission spectroscopy (XPS) allows the understanding of the persistence of the Rashba effect by evidencing a compensation of Ge vacancy defects resulting from the insertion of Sb interfacial atoms in the early stage growth of the GeTe(111) films.

Nonvolatile Electric Control of Rashba Spin Splitting in Sb/In2Se3 Heterostructure.

Ferroelectric Rashba semiconductors (FRS) are highly demanded for their potential capability for nonvolatile electric control of electron spins. An ideal FRS is characterized by a combination of room temperature ferroelectricity and a strong Rashba effect, which has, however, been rarely reported. Herein, we designed a room-temperature FRS by vertically stacking a Sb monolayer on a room-temperature ferroelectric In2Se3 monolayer. Our first-principles calculations reveal that the Sb/In2Se3 heterostructure exhibits a clean Rashba splitting band near the Fermi level and a strong Rashba effect coupled to the ferroelectric order. Switching the electric polarization direction enhances the Rashba effect, and the flipping is feasible with a low energy barrier of 22 meV. This Rashba-ferroelectricity coupling effect is robust against changes of the heterostructure interfacial distance and external electric fields. Such a nonvolatile electrically tunable Rashba effect at room temperature enables potential applications in next-generation data storage and logic devices operated under small electrical currents.

Photo-induced non-collinear interlayer RKKY coupling in bulk Rashba semiconductors

The interplay between light-matter, spin-orbit, and magnetic interactions allows the investigation of light-induced magnetic phenomena that are otherwise absent without irradiation. We present our analysis of light-driven effects on the interlayer exchange coupling mediated by a bulk Rashba semiconductor in a magnetic multilayer. The collinear magnetic exchange coupling mediated by the photon-dressed spin-orbit coupled electrons of BiTeI develops light-induced oscillation periods and displays new decay power laws, both of which are enhanced with an increasing light-matter coupling. For magnetic layers with non-collinear magnetization, we find a non-collinear magnetic exchange coupling uniquely generated by light-driving of the multilayer. As the non-collinear magnetic exchange coupling mediated by the photon-dressed electrons of BiTeI is unique to the irradiated system and it is enhanced with increasing light-matter coupling, this effect offers a promising platform of investigation of light-driven effects on magnetic phenomena in spin-orbit coupled systems. In this platform, light properties, such as its intensity, can serve as external knobs for inducing non-collinear couplings of the interlayer exchange and for modulating the collinear couplings. Both of these effects signify the photo-generated modification in the spin textures of spin-orbit coupled electrons in BiTeI.

Thermoelectric transport properties in Janus Rashba semiconductors of monolayer Si2AsSb and Si2SbBi

Thermoelectric transport properties in Janus Rashba semiconductors of monolayer Si2AsSb and Si2SbBi

Ferroelectric Control of Spin‐Orbitronics

AbstractSpin‐orbit coupling refers to the relativistic interaction between the spin and orbital motions of electrons. This interaction leads to numerous intriguing phenomena, including spin‐orbit torques, spin–momentum locking, topological spin textures, etc., that have recently gained prominence in the field of spin‐orbitronics. In particular, the emerging ferroelectric control is recognized and validated as an effective means to enhance energy efficiency across a broad spectrum of spin‐orbitronic devices. Here, cutting‐edge research on ferroelectric control of spin‐orbitronics (FECSO) by means of spontaneous polarization, reversible ferroelectric switching, and multiferroic coupling, are comprehensively reviewed. Two fascinating topics are mainly discussed: topological spin texture and spin‐charge interconversion. The classification of control mechanisms for different interactions in FECSO is summarized first. Then, from the perspective of material classification, the ferroelectric‐controlled spin‐orbit coupling with tunable topological spin texture in oxide systems, magnetic metal multilayers, and 2D van der Waals materials is reviewed. Subsequently, the ferroelectric‐tunable spin‐charge interconversion on heavy metal layers, oxide interfaces, and ferroelectric Rashba semiconductors is highlighted. In the end, the challenges and forthcoming prospects of FECSO are discussed. This work may provide pertinent and forward‐thinking guidance to accelerate the ongoing advancement of this field.

Large and nonlinear electric field response in a two-dimensional ferroelectric Rashba material

The achievement of electrical spin control is highly desirable. One promising strategy involves electrically modulating the Rashba spin orbital coupling effect in materials. A semiconductor with high sensitivity in its Rashba constant to external electric fields holds great potential for short channel lengths in spin field-effect transistors, which is crucial for preserving spin coherence and enhancing integration density. Hence, two-dimensional (2D) Rashba semiconductors with large Rashba constants and significant electric field responses are highly desirable. Herein, by employing first-principles calculations, we design a thermodynamically stable 2D Rashba semiconductor, YSbTe<sub>3</sub>, which possesses an indirect band gap of 1.04 eV, a large Rashba constant of 1.54 eV·Å and a strong electric field response of up to 4.80 e·Å<sup>2</sup>. In particular, the Rashba constant dependence on the electric field shows an unusual nonlinear relationship. At the same time, YSbTe<sub>3</sub> has been identified as a 2D ferroelectric material with a moderate polarization switching energy barrier (~ 0.33 eV per formula). By changing the electric polarization direction, the Rashba spin texture of YSbTe<sub>3</sub> can be reversed. These outstanding properties make the ferroelectric Rashba semiconductor YSbTe<sub>3</sub> quite promising for spintronic applications.

A Novel Ferroelectric Rashba Semiconductor.

Fast, reversible, and low-power manipulation of the spin texture is crucial for next generation spintronic devices like non-volatile bipolar memories, switchable spin current injectors or spin field effect transistors. Ferroelectric Rashba semiconductors (FERSC) are the ideal class of materials for the realization of such devices. Their ferroelectric character enables an electronic control of the Rashba-type spin texture by means of the reversible and switchable polarization. Yet, only very few materials are established to belong to this class of multifunctional materials. Here, Pb1- xGexTe is unraveled as a novel FERSC system down to nanoscale. The ferroelectric phase transition and concomitant lattice distortion are demonstrated by temperature dependent X-ray diffraction, and their effect on electronic properties are measured by angle-resolved photoemission spectroscopy. In few nanometer-thick epitaxial heterostructures, a large Rashba spin-splitting is exhibiting a wide tuning range as a function of temperature and Ge content. This work defines Pb1- xGexTe as a high-potential FERSC system for spintronic applications.

Bipolar Rashba Semiconductors: A Class of Nonmagnetic Materials for Electrical Spin Manipulation.

The realization of the electrical control of spin is highly desirable. One promising approach is by regulating the Rashba spin-orbit coupling effect of materials through external electric fields. However, this method requires materials to possess either a high electric field response and a large Rashba constant or the simultaneous presence of Rashba splitting and ferroelectric polarization. These stringent requirements result in a scarcity of suitable materials. In order to surpass these limitations and exploit a new prospect for spin manipulation via the Rashba effect, a conceptual class of materials named bipolar Rashba semiconductors (BRS) is proposed, whose valence band and conduction band possess opposite spin texture directions when approaching the Fermi level. The unique electronic structure of BRS makes it feasible to reverse the spin precession by simply applying a gate voltage. The existence of BRS is confirmed through first-principles calculations on the two-dimensional (2D) material AlBiS3.

Inverse Janus design of two-dimensional Rashba semiconductors

Inverse Janus design of two-dimensional Rashba semiconductors

Spectroscopic ellipsometry and raman spectroscopy of Bi1-xSbxTeI solid solutions with x≤0.1

Spectroscopic ellipsometry supported by reflectivity measurements and Raman spectroscopy are applied at room temperature to n-type Rashba semiconductors BiTeI and Bi1-xSbxTeI with nominal compositions x = 0.05 and 0.1. Complementary four probe Hall measurements are made using standard ac technique and the concentration of free carriers is determined. The Raman spectra, including TO-LO resonances are found to occupy a frequency range below 250 cm−1 in the studied materials. The pseudodielectric function, retrieved at different angles of incidence is analyzed focusing on the free carrier absorption (intraband transitions) and the optical transitions between the Rashba-split branches of the conduction band (intersubband vertical transitions). The former transitions with screened plasma frequency anchored to the zero-crossing point of the real part of the pseudodielectric function are described within a simple Drude model and the important parameters such as electron effective mass, electron mobility and high frequency dielectric constant are obtained. Anchored to the Rashba energy, the intersubband transitions obtained for each material by refining the pseudodielectric function from Drude contribution, appear in the imaginary part as a broad peak in the photon energy range between 0.15 and 0.4 eV. A noticeable red shift of this peak for Bi0.9Sb0.1TeI as compared to BiTeI is proposed to be a manifestation of the reduction of the spin splitting after part of Bi atoms is replaced by lighter Sb atoms.

Large bilinear magnetoresistance from Rashba spin-splitting on the surface of a topological insulator

In addition to the topologically protected linear dispersion, a band-bending-confined two-dimensional electron gas with tunable Rashba spin-splitting (RSS) was found to coexist with the topological surface states on the surface of topological insulators (TIs). Here, we report the observation of large bilinear magnetoresistance (BMR) in Bi2Se3 films decorated with transition metal atoms. The magnitude of the BMR sensitively depends on the type and amount of atoms deposited, with a maximum achieved value close to those of strong Rashba semiconductors. Our first-principles calculations reproduce the quantum well states and reveal sizable RSS in all Bi2Se3 heterostructures with broken inversion symmetry. Our results show that charge-spin interconversion through RSS states in TIs can be fine-tuned through surface atom deposition and easily detected via BMR for potential spintronic applications.

High-Throughput Inverse Design for 2D Ferroelectric Rashba Semiconductors.

A long-standing goal in spintronics is electric control of spin. Herein, we perform an inverse design to search for 2D ferroelectric Rashba semiconductors, whose spin texture can be precisely and readily reversed by switching ferroelectric polarization via the electric field. The inverse design involves defining and utilizing the design principles of the Rashba effect and ferroelectricity. After screening materials from a database based on the enabling design principles, we identify three potential types of structure that simultaneously possess the Rashba effect and ferroelectricity, including A2P2X6 type (space group P31m), ABP2X6 type (space group P3), and AB type (space group P3m1). By performing high-throughput density functional theory calculations of three types of structure and material screening by the optimizing design principles, we find that 14 AB monolayers are promising 2D ferroelectric Rashba semiconductors due to their pure Rashba effect in the conduction band minimum, thinnest 2D Rashba structure, and surmountable energy barriers for ferroelectric polarization. The electrically reversible spin texture makes ferroelectric Rashba semiconductors promising candidates for next-generation spintronics in the future.

Enhanced shift current bulk photovoltaic effect in ferroelectric Rashba semiconductor α-GeTe: ab initio study from three- to two-dimensional van der Waals layered structures

The ferroelectric Rashba semiconductors (FERSCs) are endowed with a unique combination of ferroelectricity and the spin degree of freedom, resulting in a long carrier lifetime and impressive bulk photovoltaic (BPV) efficiency that reached 25% in organometal halide perovskites. The BPV efficiency can be further improved by using low-dimensional ferroelectrics however, it is inhibited by the ferroelectric instability in low-dimensional perovskites and toxicity along with phase instability of the lead-halide perovskites. To address these challenges, the α-GeTe could be of great importance which is the simplest known lead-free FERSC with an intrinsic layered structure. Therefore, in this work, we investigate the BPV properties of three- to two-dimensional van der Waals structures of α-GeTe by calculating the shift current (SHC). We predict that the mono (1.56 Å) and bi-layers (5.44–6.14 Å) α-GeTe with the buckled honeycomb structure are dynamically stable and possess the characteristic features of the bulk up to the nanoscale limit. The SHC of ∼70 μA V−2 is calculated in bulk α-GeTe which is 20 times larger than that obtained in organometal halides in the visible light. The SHC increases with decreasing the number of layers, reaching a maximum amplitude of ∼300 μA V−2 at 2.67 eV in the monolayer which is more than double that obtained in monolayer GeS. We find that the SHC in monolayer α-GeTe can be further enhanced and redshifted by applying a compressive strain; which is correlated with the strong absorption of the xx-polarized light, stimulated by the more delocalized p x /y orbital character of the density of states. Furthermore, in the bilayer structures, the magnitude of the SHC is sensitive to the layers’ stacking arrangement and a maximum SHC (∼250 μA V−2) can be achieved with an AB-type stacking arrangement. Combining these results with the benefits of being environmental-friendly material makes α-GeTe a good candidate for next-generation solar cells application.

From Quantum Materials to Microsystems.

The expression “quantum materials” identifies materials whose properties “cannot be described in terms of semiclassical particles and low-level quantum mechanics”, i.e., where lattice, charge, spin and orbital degrees of freedom are strongly intertwined. Despite their intriguing and exotic properties, overall, they appear far away from the world of microsystems, i.e., micro-nano integrated devices, including electronic, optical, mechanical and biological components. With reference to ferroics, i.e., functional materials with ferromagnetic and/or ferroelectric order, possibly coupled to other degrees of freedom (such as lattice deformations and atomic distortions), here we address a fundamental question: “how can we bridge the gap between fundamental academic research focused on quantum materials and microsystems?”. Starting from the successful story of semiconductors, the aim of this paper is to design a roadmap towards the development of a novel technology platform for unconventional computing based on ferroic quantum materials. By describing the paradigmatic case of GeTe, the father compound of a new class of materials (ferroelectric Rashba semiconductors), we outline how an efficient integration among academic sectors and with industry, through a research pipeline going from microscopic modeling to device applications, can bring curiosity-driven discoveries to the level of CMOS compatible technology.

Ultrafast Thermalization Pathways of Excited Bulk and Surface States in the Ferroelectric Rashba Semiconductor GeTe.

A large Rashba effect is essential for future applications in spintronics. Particularly attractive is understanding and controlling nonequilibrium properties of ferroelectric Rashba semiconductors. Here, time- and angle-resolved photoemission is utilized to access the ultrafast dynamics of bulk and surface transient Rashba states after femtosecond optical excitation of GeTe. A complex thermalization pathway is observed, wherein three different timescales can be clearly distinguished: intraband thermalization, interband equilibration, and electronic cooling. These dynamics exhibit an unconventional temperature dependence: while the cooling phase speeds up with increasing sample temperature, the opposite happens for interband thermalization. It is demonstrated how, due to the Rashba effect, an interdependence of these timescales on the relative strength of both electron-electron and electron-phonon interactions is responsible for the counterintuitive temperature dependence, with spin-selection constrained interband electron-electron scatterings found both to dominate dynamics away from the Fermi level, and to weaken with increasing temperature. These findings are supported by theoretical calculations within the Boltzmann approach explicitly showing the opposite behavior of all relevant electron-electron and electron-phonon scattering channels with temperature, thus confirming the microscopic mechanism of the experimental findings. The present results are important for future applications of ferroelectric Rashba semiconductors and their excitations in ultrafast spintronics.

Electronic states driven by the crystal field in two-dimensional materials: The case of antimonene

The search for novel two-dimensional (2D) giant Rashba semiconductors is a crucial step in the development of spintronic technology. The electronic properties and growth mode of antimonene grown by molecular beam epitaxy were investigated using angle-resolved photoemission spectroscopy (ARPES) and scanning tunneling microscopy. Results reveal the semiconducting nature of antimonene and the presence of a highly mobile 2D hole gas (2DHG) near the Fermi level. The anisotropy factor and Fermi velocity of the 2DHG are sensitively dependent on the crystal structure and in-plane lattice parameters of antimonene. Antimonene with small lattice parameters exhibits a small anisotropy factor and electron effective mass. Furthermore, the perpendicular (out of plane) electric field breaks the inversion symmetry and, when combined with strong spin-orbit coupling, induces the spin splitting of the valence band of antimonene. ARPES and work function measurements shed light on the band alignment between antimonene and the substrates and confirmed the presence of a nonignorable interface dipole of approximately 0.2 eV. This dipole could be the cause of approximately 80 meV spin splitting at the valence-band maximum of antimonene, a value that is significantly greater than the thermal energy at room temperature. In addition, the spin-splitting degree depends on the interface dipole strength. The gate voltage can generate the out of plane electric field and regulate the spin state similar to an internal electric field. Our results suggest that antimonene and its van der Waals heterostructure system grown on substrates could be used to develop highly efficient spin field-effect transistors and nanospintronic devices.

Spin-Orbit Coupling in 2D Semiconductors: A Theoretical Perspective.

This theoretical Perspective reviews spin-orbit coupling (SOC), including the Rashba effect and Dresselhaus effect, in two-dimensional (2D) semiconductors. We first introduce the origin of the Rashba effect and Dresselhaus effect using the Hamiltonian models; we then summarize 2D Rashba semiconductors predicted by first-principles density functional theory (DFT) calculations, including AB binary monolayers, Janus monolayers, 2D perovskites, and so on. We also review various manipulating techniques of the Rashba effect on 2D semiconductors, such as external electric field, strain engineering, charge doping, interlayer interactions, proximity effect of substrates, and external magnetic field. We then briefly summarize the applications of SOC, including the generation, detection, and manipulation of spin currents in spin Hall effect transistors and spin field effect transistors. Finally, we conclude this Perspective and propose three promising research fields of SOC in low-dimensional semiconductors, including the nonlinear SOC Hamiltonian model, 2D ferroelectric SOC semiconductors, and 1D Rashba model and semiconductors. This theoretical Perspective enriches the fundamental understanding of SOC in 2D semiconductors and will help in the design of new types of spintronic devices in future experiments.

Room-temperature ferroelectric switching of spin-to-charge conversion in germanium telluride

Since its birth in the 1990s, semiconductor spintronics has suffered from poor compatibility with ferromagnets as sources of spin. While the broken inversion symmetry of some semiconductors may alternatively allow for spin-charge interconversion, its control by electric fields is volatile. Ferroelectric Rashba semiconductors stand as appealing materials unifying semiconductivity, large spin-orbit coupling, and non-volatility endowed by ferroelectricity. However, their potential for spintronics has been little explored. Here, we demonstrate the non-volatile, ferroelectric control of spin-to-charge conversion at room temperature in epitaxial GeTe films. We show that ferroelectric switching by electrical gating is possible in GeTe despite its high carrier density. We reveal a spin-to-charge conversion as effective as in Pt, but whose sign is controlled by the orientation of the ferroelectric polarization. The comparison between theoretical and experimental data suggests that spin Hall effect plays a major role for switchable conversion. These results open a route towards devices combining spin-based logic and memory integrated into a silicon-compatible material.

First-principle studies on the ferroelectricity and gate-controlled Rashba spin-orbit coupling of d1T-phase transition-metal dichalcogenide monolayers

Two-dimensional ferroelectric Rashba semiconductors exhibit extraordinary orbital and spin structures. In this research, through first-principle calculations, we demonstrate the ferroelectricity of d1T-phase (distorted 1T-phase) transition-metal dichalcogenide monolayers and realize the manipulation of the Rashba spin-orbit coupling by means of gate voltage. Because of its large composition of out-of-plane atomic orbitals, the rotation of transition metal atoms induced symmetry breaking leads to larger Rashba spin splittings at Γ point of top valence band (560.4 meV Å for WS 2 , measured by the first derivative of the energy splitting to the wave vector), and it further increases under a vertical downward electric field and hole doping, which correspond to a positive gate voltage for the constructed device. In comparison, charge doping has a greater effect on Rashba parameters than electric field. These results are of great value to the spin-orbit electronics of two-dimensional materials and their applications in electrically controlled spintronics and memory devices. • The ferroelectricity and Rashba SOC of monolayer d1T-phase TMDs are demonstrated. • The Rashba parameter is evaluated by the first derivative of the energy splitting. • One factor of greater Rashba strength is larger vertical orbital composition. • Another origin is the gradient of potential energy affected by charge transfer. • The strength is tuned linearly by electric field and nonlinearly by charge doping.

Spin-Current Modulation in Hexagonal Buckled ZnTe and CdTe Monolayers for Self-Powered Flexible-Piezo-Spintronic Devices.

The next-generation spintronic device demands the gated control of spin transport across the semiconducting channel through the replacement of the external gate voltage source by the piezo potential, as experimentally demonstrated in Zhu et al. ACS Nano, 2018, 12 (2), 1811-1820. Consequently, a high level of out-of-plane piezoelectricity together with a large Rashba spin splitting is sought after in semiconducting channel materials. Inspired by this experiment, a new hexagonal buckled two-dimensional (2D) semiconductor, ZnTe, and its iso-electronic partner, CdTe, are proposed herewith. These 2D materials show a strong spin-orbit coupling (SOC), which is evidenced by a large Rashba constant of 1.06 and 1.27 eV·Å, respectively, in ZnTe and CdTe monolayers. Moreover, these Rashba semiconductors exhibit a giant out-of-plane piezoelectric coefficient (d33) = 88.68 and 172.61 pm/V, and can thereby generate a high piezo potential for gating purposes in spin field-effect transistors (spin-FETs). While the low elastic stiffness implies the mechanical flexibility or stretchability in these monolayers. The Rashba constants are found to be effectively modulated via external perturbations, such as strain and electric field. The wide band gap provides ample room for modulation in its electronic properties via external perturbations. Such scope is severely limited in previously reported narrow band gap Rashba semiconductors. The fascinating results found in this work indicate their great potential for applications in next-generation self-powered flexible-piezo-spintronic devices. Moreover, a new class of hexagonal buckled ZnX (X: S, Se, or Te) monolayers is proposed herein based on their previously synthesized bulk counterparts, while their electronic, mechanical, piezoelectric, and thermal properties have been thoroughly investigated using the state-of-art density functional theory (DFT).