Spin-Chirality-Driven Multiferroicity in van der Waals Monolayers.

Driven by the expected contribution of two-dimensional multiferroic systems with strong magnetoelectric coupling to the development of multifunctional nanodevices, here we propose, by means of first-principles calculations, vanadium-halide monolayers as a new class of spin-chirality-driven van der Waals multiferroics. The frustrated 120-deg magnetic structure in the triangular lattice induces a ferroelectric polarization perpendicular to the spin-spiral plane, whose sign is switched by a spin-chirality change. It follows that, in the presence of an applied electric field perpendicular to the monolayers, one magnetic chirality can be stabilized over the other, thereby allowing the long-sought electrical control of spin textures. Moreover, we demonstrate the remarkable role of spin-lattice coupling on magnetoelectricity, which adds to the expected contribution of spin-orbit interaction determined by an anion. Indeed, such compounds exhibit sizeable spin-driven structural distortions, thereby promoting the investigation of multifunctional spin-electric-lattice couplings.

Electron doping as a handle to increase the Curie temperature in ferrimagnetic Mn3Si2X6 (X = Se, Te).

By analysing the results of ab initio simulations performed for Mn3Si2X6 (X = Se, Te), we first discuss the analogies and the differences in electronic and magnetic properties arising from the anion substitution, in terms of size, electronegativity, band widths of p electrons and spin-orbit coupling strengths. For example, through mean-field theory and simulations based on density functional theory, we demonstrate that magnetic frustration, known to be present in Mn3Si2Te6, also exists in Mn3Si2Se6 and leading to a ferrimagnetic ground state. Building on these results, we propose a strategy, electronic doping, to reduce the frustration and thus to increase the Curie temperature (TC). To this end, we first study the effect of electronic doping on the electronic structure and magnetic properties and discuss the differences in the two compounds, along with their causes. Secondly, we perform Monte-Carlo simulations, considering from the first to the fifth nearest-neighbor magnetic interactions and single-ion anisotropy, and show that electron doping efficiently raises the TC.

γ-BaFe2O4: a fresh playground for room temperature multiferroicity.

Multiferroics, showing the coexistence of two or more ferroic orderings at room temperature, could harness a revolution in multifunctional devices. However, most of the multiferroic compounds known to date are not magnetically and electrically ordered at ambient conditions, so the discovery of new materials is pivotal to allow the development of the field. In this work, we show that BaFe2O4 is a previously unrecognized room temperature multiferroic. X-ray and neutron diffraction allowed to reveal the polar crystal structure of the compound as well as its antiferromagnetic behavior, confirmed by bulk magnetometry characterizations. Piezo force microscopy and electrical measurements show the polarization to be switchable by the application of an external field, while symmetry analysis and calculations based on density functional theory reveal the improper nature of the ferroelectric component. Considering the present findings, we propose BaFe2O4 as a Bi- and Pb-free model for the search of new advanced multiferroic materials.

Influence of Orbital Character on the Ground State Electronic Properties in the van Der Waals Transition Metal Iodides VI3 and CrI3.

Two-dimensional van der Waals magnetic semiconductors display emergent chemical and physical properties and hold promise for novel optical, electronic and magnetic "few-layers" functionalities. Transition-metal iodides such as CrI3 and VI3 are relevant for future electronic and spintronic applications; however, detailed experimental information on their ground state electronic properties is lacking often due to their challenging chemical environment. By combining X-ray electron spectroscopies and first-principles calculations, we report a complete determination of CrI3 and VI3 electronic ground states. We show that the transition metal-induced orbital filling drives the stabilization of distinct electronic phases: a wide bandgap in CrI3 and a Mott insulating state in VI3. Comparison of surface-sensitive (angular-resolved photoemission spectroscopy) and bulk-sensitive (X-ray absorption spectroscopy) measurements in VI3 reveals a surface-only V2+ oxidation state, suggesting that ground state electronic properties are strongly influenced by dimensionality effects. Our results have direct implications in band engineering and layer-dependent properties of two-dimensional systems.

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.

Curved Magnetism in CrI_{3}.

Curved magnets attract considerable interest for their unusually rich phase diagram, often encompassing exotic (e.g., topological or chiral) spin states. Micromagnetic simulations are playing a central role in the theoretical understanding of such phenomena; their predictive power, however, rests on the availability of reliable model parameters to describe a given material or nanostructure. Here we demonstrate how noncollinear-spin polarized density-functional theory can be used to determine the flexomagnetic coupling coefficients in real systems. By focusing on monolayer CrI_{3}, we find a crossover as a function of curvature between a magnetization normal to the surface to a cycloidal state, which we rationalize in terms of effective anisotropy and Dzyaloshinskii-Moriya contributions to the magnetic energy. Our results reveal an unexpectedly large impact of spin-orbit interactions on the curvature-induced anisotropy, which we discuss in the context of existing phenomenological models.

Evidence for a single-layer van der Waals multiferroic.

Multiferroic materials have attracted wide interest because of their exceptional static1-3 and dynamical4-6 magnetoelectric properties. In particular, type-II multiferroics exhibit an inversion-symmetry-breaking magnetic order that directly induces ferroelectric polarization through various mechanisms, such as the spin-current or the inverse Dzyaloshinskii-Moriya effect3,7. This intrinsic coupling between the magnetic and dipolar order parameters results in high-strength magnetoelectric effects3,8. Two-dimensional materials possessing such intrinsic multiferroic properties have been long sought for to enable the harnessing of magnetoelectric coupling in nanoelectronic devices1,9,10. Here we report the discovery of type-II multiferroic order in a single atomic layer of the transition-metal-based van der Waals material NiI2. The multiferroic state of NiI2 is characterized by a proper-screw spin helix with given handedness, which couples to the charge degrees of freedom to produce a chirality-controlled electrical polarization. We use circular dichroic Raman measurements to directly probe the magneto-chiral ground state and its electromagnon modes originating from dynamic magnetoelectric coupling. Combining birefringence and second-harmonic-generation measurements with theoretical modelling and simulations, we detect a highly anisotropic electronic state that simultaneously breaks three-fold rotational and inversion symmetry, and supports polar order. The evolution of the optical signatures as a function of temperature and layer number surprisingly reveals an ordered magnetic polar state that persists down to the ultrathin limit of monolayer NiI2. These observations establish NiI2 and transition metal dihalides as a new platform for studying emergent multiferroic phenomena, chiral magnetic textures and ferroelectricity in the two-dimensional limit.

Interplay between Single-Ion and Two-Ion Anisotropies in Frustrated 2D Semiconductors and Tuning of Magnetic Structures Topology.

The effects of competing magnetic interactions in stabilizing different spin configurations are drawing renewed attention in order to unveil emerging topological spin textures and to highlight microscopic mechanisms leading to their stabilization. The possible key role of the two-site exchange anisotropy in selecting specific helicity and vorticity of skyrmionic lattices has only recently been proposed. In this work, we explore the phase diagram of a frustrated localized magnet characterized by a two-dimensional centrosymmetric triangular lattice, focusing on the interplay between the two-ion anisotropy and the single-ion anisotropy. The effects of an external magnetic field applied perpendicularly to the magnetic layer, are also investigated. By means of Monte Carlo simulations, we find an abundance of different spin configurations, going from trivial to high-order Q skyrmionic and meronic lattices. In closer detail, we find that a dominant role is played by the two-ion over the single-ion anisotropy in determining the planar spin texture; the strength and the sign of single ion anisotropy, together with the magnitude of the magnetic field, tune the perpendicular spin components, mostly affecting the polarity (and, in turn, the topology) of the spin texture. Our analysis confirms the crucial role of the anisotropic symmetric exchange in systems with dominant short-range interactions; at the same time, we predict a rich variety of complex magnetic textures, which may arise from a fine tuning of competing anisotropic mechanisms.

Robust Magnetoelectric Effect in the Decorated Graphene/In2Se3 Heterostructure.

The magnetoelectric effect is a fundamental physical phenomenon that synergizes electric and magnetic degrees of freedom to generate distinct material responses like electrically tuned magnetism, which serves as a key foundation of the emerging field of spintronics. Here, we show by first-principles studies that ferroelectric (FE) polarization of an In2Se3 monolayer can modulate the magnetism of an adjacent transition-metal (TM)-decorated graphene layer via a ferroelectrically induced electronic transition. The TM nonbonding d-orbital shifts downward and hybridizes with carbon-p states near the Fermi level, suppressing the magnetic moment, under one FE polarization, but on reversed FE polarization this TM d-orbital moves upward, restoring the original magnetic moment. This finding of robust magnetoelectric effect in the TM-decorated graphene/In2Se3 heterostructure offers powerful insights and a promising avenue for experimental exploration of ferroelectrically controlled magnetism in two-dimensional (2D) materials.

Angle, Spin, and Depth Resolved Photoelectron Spectroscopy on Quantum Materials.

The role of X-ray based electron spectroscopies in determining chemical, electronic, and magnetic properties of solids has been well-known for several decades. A powerful approach is angle-resolved photoelectron spectroscopy, whereby the kinetic energy and angle of photoelectrons emitted from a sample surface are measured. This provides a direct measurement of the electronic band structure of crystalline solids. Moreover, it yields powerful insights into the electronic interactions at play within a material and into the control of spin, charge, and orbital degrees of freedom, central pillars of future solid state science. With strong recent focus on research of lower-dimensional materials and modified electronic behavior at surfaces and interfaces, angle-resolved photoelectron spectroscopy has become a core technique in the study of quantum materials. In this review, we provide an introduction to the technique. Through examples from several topical materials systems, including topological insulators, transition metal dichalcogenides, and transition metal oxides, we highlight the types of information which can be obtained. We show how the combination of angle, spin, time, and depth-resolved experiments are able to reveal "hidden" spectral features, connected to semiconducting, metallic and magnetic properties of solids, as well as underlining the importance of dimensional effects in quantum materials.

Spontaneous skyrmionic lattice from anisotropic symmetric exchange in a Ni-halide monolayer.

Topological spin structures, such as magnetic skyrmions, hold great promises for data storage applications, thanks to their inherent stability. In most cases, skyrmions are stabilized by magnetic fields in non-centrosymmetric systems displaying the chiral Dzyaloshinskii-Moriya exchange interaction, while spontaneous skyrmion lattices have been reported in centrosymmetric itinerant magnets with long-range interactions. Here, a spontaneous anti-biskyrmion lattice with unique topology and chirality is predicted in the monolayer of a semiconducting and centrosymmetric metal halide, NiI2. Our first-principles and Monte Carlo simulations reveal that the anisotropies of the short-range symmetric exchange, when combined with magnetic frustration, can lead to an emergent chiral interaction that is responsible for the predicted topological spin structures. The proposed mechanism finds a prototypical manifestation in two-dimensional magnets, thus broadening the class of materials that can host spontaneous skyrmionic states.

Band splitting with vanishing spin polarizations in noncentrosymmetric crystals.

The Dresselhaus and Rashba effects are well-known phenomena in solid-state physics, in which spin-orbit coupling splits spin-up and spin-down energy bands of nonmagnetic non-centrosymmetric crystals. Here, we discuss a phenomenon we dub band splitting with vanishing spin polarizations (BSVSP), in which, as usual, spin-orbit coupling splits the energy bands in nonmagnetic non-centrosymmetric systems. Surprisingly, however, both split bands show no net spin polarization along certain high-symmetry lines in the Brillouin zone. In order to rationalize this phenomenon, we propose a classification of point groups into pseudo-polar and non-pseudo-polar groups. By means of first-principles simulations, we demonstrate that BSVSP can take place in both symmorphic (e.g., bulk GaAs) and non-symmorphic systems (e.g., two dimensional ferroelectric SnTe). Furthermore, we identify a linear magnetoelectric coupling in reciprocal space, which could be employed to tune the spin polarization with an external electric field. The BSVSP effect and its manipulation could therefore form the basis for future spintronic devices.

Intrinsic Origin of Enhancement of Ferroelectricity in SnTe Ultrathin Films.

Previous studies showed that, as ferroelectric films become thinner, their Curie temperature (T_{c}) and polarization below T_{c} both typically decrease. In contrast, a recent experiment [Chang et al., Science 353, 274 (2016)SCIEAS0036-807510.1126/science.aad8609] observed that atomic-thick SnTe films have a higher T_{c} than their bulk counterpart, which was attributed to extrinsic effects. We find, using first-principles calculations, that the 0-K energy barrier for the polarization switching (which is a quantity directly related to T_{c}) is higher in most investigated defect-free SnTe ultrathin films than that in bulk SnTe, and that the 5-unit-cell (UC) SnTe thin film has the largest energy barrier as a result of an interplay between hybridization interactions and Pauli repulsions. Further simulations, employing a presently developed effective Hamiltonian, confirm that freestanding, defect-free SnTe thin films have a higher T_{c} than bulk SnTe, except for the 1-UC case. Our work, therefore, demonstrates the possibility to intrinsically enhance ferroelectricity of ultrathin films by reducing their thickness.

Ferroelectric Control of the Spin Texture in GeTe.

The electric and nonvolatile control of the spin texture in semiconductors would represent a fundamental step toward novel electronic devices combining memory and computing functionalities. Recently, GeTe has been theoretically proposed as the father compound of a new class of materials, namely ferroelectric Rashba semiconductors. They display bulk bands with giant Rashba-like splitting due to the inversion symmetry breaking arising from the ferroelectric polarization, thus allowing for the ferroelectric control of the spin. Here, we provide the experimental demonstration of the correlation between ferroelectricity and spin texture. A surface-engineering strategy is used to set two opposite predefined uniform ferroelectric polarizations, inward and outward, as monitored by piezoresponse force microscopy. Spin and angular resolved photoemission experiments show that these GeTe(111) surfaces display opposite sense of circulation of spin in bulk Rashba bands. Furthermore, we demonstrate the crafting of nonvolatile ferroelectric patterns in GeTe films at the nanoscale by using the conductive tip of an atomic force microscope. Based on the intimate link between ferroelectric polarization and spin in GeTe, ferroelectric patterning paves the way to the investigation of devices with engineered spin configurations.

Giant Rashba Splitting in Pb1-x Snx Te (111) Topological Crystalline Insulator Films Controlled by Bi Doping in the Bulk.

The topological properties of lead-tin chalcogenide topological crystalline insulators can be widely tuned by temperature and composition. It is shown that bulk Bi doping of epitaxial Pb1-x Snx Te (111) films induces a giant Rashba splitting at the surface that can be tuned by the doping level. Tight binding calculations identify their origin as Fermi level pinning by trap states at the surface.

Polar Nature of (CH3NH3)3Bi2I9 Perovskite-Like Hybrids.

High-quality single crystals of perovskite-like (CH3NH3)3Bi2I9 hybrids have been synthesized, using a layered-solution crystal-growth technique. The large dielectric constant is strongly affected by the polar ordering of its constituents. Progressive dipolar ordering of the methylammonium cation upon cooling below 300 K gradually converts the hexagonal structure (space group P63/mmc) into a monoclinic phase (C2/c) at 160 K. A well-pronounced, ferrielectric phase transition at 143 K is governed by in-plane ordering of the bismuth lone pair that breaks inversion symmetry and results in a polar phase (space group P21). The dielectric constant is markedly higher in the C2/c phase above this transition. Here, the bismuth lone pair is disordered in-plane, allowing the polarizability to be substantially enhanced. Density functional theory calculations estimate a large ferroelectric polarization of 7.94 µC/cm2 along the polar axis in the P21 phase. The calculated polarization has almost equal contributions of the methylammonium and Bi3+ lone pair, which are fairly decoupled.

Magnetic Structures of Heterometallic M(II)-M(III) Formate Compounds.

A study of the magnetic structure of the [NH2(CH3)2]n[FeIIIMII(HCOO)6]n niccolite-like compounds, with MII = CoII (2) and MnII (3) ions, has been carried out using neutron diffraction and compared with the previously reported FeII-containing compound (1). The inclusion of two different metallic atoms into the niccolite-like structure framework leads to the formation of isostructural compounds with very different magnetic behaviors due to the compensation or not of the different spins involved in each lattice. Below TN, the magnetic order in these compounds varies from ferrimagnetic behavior for 1 and 2 to an antiferromagnetic behavior with a weak spin canting for 3. Structure refinements of 2 and 3 at low temperature (45 K) have been carried out combining synchrotron X-ray and high-resolution neutron diffraction in a multipattern approach. The magnetic structures have been determined from the difference patterns between the neutron data in the paramagnetic and the magnetically ordered regions. These difference patterns have been analyzed using a simulated annealing protocol and symmetry analysis techniques. The obtained magnetic structures have been further rationalized by means of ab initio DFT calculations. The direction of the magnetic moment of each compound has been determined. The easy axis of the MII for compound 1 (FeII) is along the c axis; for compound 2 (CoII), the moments are mainly within the ab plane; finally, for compound 3 (MnII), the calculations show that the moments have components both in the ab plane and along the c axis.

Intertwined Rashba, Dirac, and Weyl Fermions in Hexagonal Hyperferroelectrics.

By means of density functional theory based calculations, we study the role of spin-orbit coupling in the new family of ABC hyperferroelectrics [Garrity, Rabe, and Vanderbilt Phys. Rev. Lett. 112, 127601 (2014)]. We unveil an extremely rich physics strongly linked to ferroelectric properties, ranging from the electric control of bulk Rashba effect to the existence of a three-dimensional topological insulator phase, with concomitant topological surface states even in the ultrathin film limit. Moreover, we predict that the topological transition, as induced by alloying, is followed by a Weyl semimetal phase of finite concentration extension, which is robust against disorder, putting forward hyperferroelectrics as promising candidates for spin-orbitronic applications.

Role of Polar Phonons in the Photo Excited State of Metal Halide Perovskites.

The development of high efficiency perovskite solar cells has sparked a multitude of measurements on the optical properties of these materials. For the most studied methylammonium(MA)PbI3 perovskite, a large range (6-55 meV) of exciton binding energies has been reported by various experiments. The existence of excitons at room temperature is unclear. For the MAPbX3 perovskites we report on relativistic Bethe-Salpeter Equation calculations (GW-BSE). This method is capable to directly calculate excitonic properties from first-principles. At low temperatures it predicts exciton binding energies in agreement with the reported 'large' values. For MAPbI3, phonon modes present in this frequency range have a negligible contribution to the ionic screening. By calculating the polarization in time from finite temperature molecular dynamics, we show that at room temperature this does not change. We therefore exclude ionic screening as an explanation for the experimentally observed reduction of the exciton binding energy at room temperature and argue in favor of the formation of polarons.