When Machine Learning Meets 2D Materials: A Review.

The availability of an ever-expanding portfolio of 2D materials with rich internal degrees of freedom (spin, excitonic, valley, sublattice, and layer pseudospin) together with the unique ability to tailor heterostructures made layer by layer in a precisely chosen stacking sequence and relative crystallographic alignments, offers an unprecedented platform for realizing materials by design. However, the breadth of multi-dimensional parameter space and massive data sets involved is emblematic of complex, resource-intensive experimentation, which not only challenges the current state of the art but also renders exhaustive sampling untenable. To this end, machine learning, a very powerful data-driven approach and subset of artificial intelligence, is a potential game-changer, enabling a cheaper - yet more efficient - alternative to traditional computational strategies. It is also a new paradigm for autonomous experimentation for accelerated discovery and machine-assisted design of functional 2D materials and heterostructures. Here, the study reviews the recent progress and challenges of such endeavors, and highlight various emerging opportunities in this frontier research area.

Evidence of Temperature-Dependent Interplay between Spin and Orbital Moment in van der Waals Ferromagnet VI3.

van der Waals materials provide a versatile toolbox for the emergence of new quantum phenomena and fabrication of functional heterostructures. Among them, the trihalide VI3 stands out for its unique magnetic and structural landscape. Here we investigate the spin and orbital magnetic degrees of freedom in the layered ferromagnet VI3 by means of temperature-dependent X-ray absorption spectroscopy and X-ray magnetic circular and linear dichroism. We detect localized electronic states and reduced magnetic dimensionality, due to electronic correlations. We furthermore provide experimental evidence of (a) an unquenched orbital magnetic moment (up to 0.66(7) µB/V atom) in the ferromagnetic state and (b) an instability of the orbital moment in the proximity of the spin reorientation transition. Our results support a coherent picture where electronic correlations give rise to a strong magnetic anisotropy and a large orbital moment and establish VI3 as a prime candidate for the study of orbital quantum effects.

Observation of Termination-Dependent Topological Connectivity in a Magnetic Weyl Kagome Lattice.

Engineering surfaces and interfaces of materials promises great potential in the field of heterostructures and quantum matter designers, with the opportunity to drive new many-body phases that are absent in the bulk compounds. Here, we focus on the magnetic Weyl kagome system Co3Sn2S2 and show how for the terminations of different samples the Weyl points connect differently, still preserving the bulk-boundary correspondence. Scanning tunneling microscopy has suggested such a scenario indirectly, and here, we probe the Fermiology of Co3Sn2S2 directly, by linking it to its real space surface distribution. By combining micro-ARPES and first-principles calculations, we measure the energy-momentum spectra and the Fermi surfaces of Co3Sn2S2 for different surface terminations and show the existence of topological features depending on the top-layer electronic environment. Our work helps to define a route for controlling bulk-derived topological properties by means of surface electrostatic potentials, offering a methodology for using Weyl kagome metals in responsive magnetic spintronics.

Artificial Aging of Thin Films of the Indium-Free Transparent Conducting Oxide SrVO3.

SrVO3 (SVO) is a prospective candidate to replace the conventional indium tin oxide (ITO) among the new generation of transparent conducting oxide (TCO) materials. In this study, the structural, electrical, and optical properties of SVO thin films, both epitaxial and polycrystalline, are determined during and after heat treatments in the 150-250 °C range and under ambient environment in order to explore the chemical stability of this material. The use of these relatively low temperatures speeds up the natural aging of the films and allows following the evolution of their related properties. The combination of techniques rather sensitive to the film surface and of techniques sampling the film volume will emphasize the presence of a surface oxidation evolving in time at low annealing temperatures, whereas the perovskite phase is destroyed throughout the film for treatments above 200 °C. The present study is designed to understand the thermal degradation and long-term stability issues of vanadate-based TCOs and to identify technologically viable solutions for the application of this group as new TCOs.

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.

Electronic Properties of Fully Strained La1-x Sr x MnO3 Thin Films Grown by Molecular Beam Epitaxy (0.15 ≤ x ≤ 0.45).

The structural, electronic, and magnetic properties of Sr-hole-doped epitaxial La1-x Sr x MnO3 (0.15 ≤ x ≤ 0.45) thin films deposited using the molecular beam epitaxy technique on 4° vicinal STO (001) substrates are probed by the combination of X-ray diffraction and various synchrotron-based spectroscopy techniques. The structural characterizations evidence a significant shift in the LSMO (002) peak to the higher diffraction angles owing to the increase in Sr doping concentrations in thin films. The nature of the LSMO Mn mixed-valence state was estimated from X-ray photoemission spectroscopy together with the relative changes in the Mn L2,3 edges observed in X-ray absorption spectroscopy (XAS), both strongly affected by doping. CTM4XAS simulations at the XAS Mn L2,3 edges reveal the combination of epitaxial strain, and different MnO6 crystal field splitting give rise to a peak at ∼641 eV. The observed changes in the occupancy of the eg and the t2g orbitals as well as their binding energy positions toward the Fermi level with hole doping are discussed. The room-temperature magnetic properties were probed at the end by circular dichroism.

Evidence of magnetism-induced topological protection in the axion insulator candidate EuSn2P2.

We unravel the interplay of topological properties and the layered (anti)ferromagnetic ordering in EuSn2P2, using spin and chemical selective electron and X-ray spectroscopies supported by first-principle calculations. We reveal the presence of in-plane long-range ferromagnetic order triggering topological invariants and resulting in the multiple protection of topological Dirac states. We provide clear evidence that layer-dependent spin-momentum locking coexists with ferromagnetism in this material, a cohabitation that promotes EuSn2P2 as a prime candidate axion insulator for topological antiferromagnetic spintronics applications.

ZnO Thin Films Growth Optimization for Piezoelectric Application.

The piezoelectric response of ZnO thin films in heterostructure-based devices is strictly related to their structure and morphology. We optimize the fabrication of piezoelectric ZnO to reduce its surface roughness, improving the crystalline quality, taking into consideration the role of the metal electrode underneath. The role of thermal treatments, as well as sputtering gas composition, is investigated by means of atomic force microscopy and x-ray diffraction. The results show an optimal reduction in surface roughness and at the same time a good crystalline quality when 75% O2 is introduced in the sputtering gas and deposition is performed between room temperature and 573 K. Subsequent annealing at 773 K further improves the film quality. The introduction of Ti or Pt as bottom electrode maintains a good surface and crystalline quality. By means of piezoelectric force microscope, we prove a piezoelectric response of the film in accordance with the literature, in spite of the low ZnO thickness and the reduced grain size, with a unipolar orientation and homogenous displacement when deposited on Ti electrode.

Magnetoelectric Coupling at the Ni/Hf0.5Zr0.5O2 Interface.

Composite multiferroics containing ferroelectric and ferromagnetic components often have much larger magnetoelectric coupling compared to their single-phase counterparts. Doped or alloyed HfO2-based ferroelectrics may serve as a promising component in composite multiferroic structures potentially feasible for technological applications. Recently, a strong charge-mediated magnetoelectric coupling at the Ni/HfO2 interface has been predicted using density functional theory calculations. Here, we report on the experimental evidence of such magnetoelectric coupling at the Ni/Hf0.5Zr0.5O2(HZO) interface. Using a combination of operando XAS/XMCD and HAXPES/MCDAD techniques, we probe element-selectively the local magnetic properties at the Ni/HZO interface in functional Au/Co/Ni/HZO/W capacitors and demonstrate clear evidence of the ferroelectric polarization effect on the magnetic response of a nanometer-thick Ni marker layer. The observed magnetoelectric effect and the electronic band lineup of the Ni/HZO interface are interpreted based on the results of our theoretical modeling. It elucidates the critical role of an ultrathin NiO interlayer, which controls the sign of the magnetoelectric effect as well as provides a realistic band offset at the Ni/HZO interface, in agreement with the experiment. Our results hold promise for the use of ferroelectric HfO2-based composite multiferroics for the design of multifunctional devices compatible with modern semiconductor technology.

Stabilization of an Enantiopure Sub-monolayer of Helicene Radical Cations on a Au(111) Surface through Noncovalent Interactions.

In the past few years, the chirality and magnetism of molecules have received notable interest for the development of novel molecular devices. Chiral helicenes combine both these properties, and thus their nanostructuration is the first step toward developing new multifunctional devices. Here, we present a novel strategy to deposit a sub-monolayer of enantiopure thia[4]helicene radical cations on a pre-functionalized Au(111) substrate. This approach results in both the paramagnetic character and the chemical structure of these molecules being maintained at the nanoscale, as demonstrated by in-house characterizations. Furthermore, synchrotron-based X-ray natural circular dichroism confirmed that the handedness of the thia[4]helicene is preserved on the surface.

Defect Engineering for Tuning the Photoresponse of Ceria-Based Solid Oxide Photoelectrochemical Cells.

Solid oxide photoelectrochemical cells (SOPECs) with inorganic ion-conducting electrolytes provide an alternative solution for light harvesting and conversion. Exploring potential photoelectrodes for SOPECs and understanding their operation mechanisms are crucial for continuously developing this technology. Here, ceria-based thin films were newly explored as photoelectrodes for SOPEC applications. It was found that the photoresponse of ceria-based thin films can be tuned both by Sm-doping-induced defects and by the heating temperature of SOPECs. The whole process was found to depend on the surface electrochemical redox reactions synergistically with the bulk photoelectric effect. Samarium doping level can selectively switch the open-circuit voltages polarity of SOPECs under illumination, thus shifting the potential of photoelectrodes and changing their photoresponse. The role of defect chemistry engineering in determining such a photoelectrochemical process was discussed. Transient absorption and X-ray photoemission spectroscopies, together with the state-of-the-art in operando X-ray absorption spectroscopy, allowed us to provide a compelling explanation of the experimentally observed switching behavior on the basis of the surface reactions and successive charge balance in the bulk.

Improved Structural Properties in Homogeneously Doped Sm0.4Ce0.6O2-δ Epitaxial Thin Films: High Doping Effect on the Electronic Bands.

The study of ionic materials on nanometer scale is of great relevance for efficient miniaturized devices for energy applications. The epitaxial growth of thin films can be a valid route to tune the properties of the materials and thus obtain new degrees of freedom in materials design. High crystal quality SmxCe1-xO2-δ films are here reported at a high doping level up to x = 0.4, thanks to the good lattice matching with the (110) oriented NdGaO3 substrate. X-ray diffraction and transmission electron microscopy demonstrate the ordered structural quality and absence of Sm segregation at the macroscopic and atomic level, respectively. Therefore, in epitaxial thin films, the homogeneous doping can be obtained even with the high dopant content not always approachable in bulk form, getting even an improvement of the structural properties. In situ spectroscopic measurements by X-ray photoemission and X-ray absorption show the O 2p band shift toward the Fermi level, which can favor the oxygen exchange and vacancy formation on the surface when the Sm doping is increased to x = 0.4. X-ray absorption spectroscopy also confirms the absence of ordered oxygen vacancy clusters and further reveals that the 5d eg and t2g states are well separated by the crystal field in the undistorted local structure even in the case of a high doping level up to x = 0.4.

Molecular Beam Epitaxy of Two-Dimensional Vanadium-Molybdenum Diselenide Alloys.

Two-dimensional (2D) alloys represent a versatile platform that extends the properties of atomically thin transition-metal dichalcogenides. Here, using molecular beam epitaxy, we investigate the growth of 2D vanadium-molybdenum diselenide alloys, VxMo1-xSe2, on highly oriented pyrolytic graphite and unveil their structural, chemical, and electronic integrities via measurements by scanning tunneling microscopy/spectroscopy, synchrotron X-ray photoemission, and X-ray absorption spectroscopy (XAS). Essentially, we found a critical value of x = ∼0.44, below which phase separation occurs and above which a homogeneous metallic phase is favored. Another observation is an effective increase in the density of mirror twin boundaries of constituting MoSe2 in the low V concentration regime (x ≤ 0.05). Density functional theory calculations support our experimental results on the thermal stability of 2D VxMo1-xSe2 alloys and suggest an H phase of the homogeneous alloys with alternating parallel V and Mo strips randomly in-plane stacked. Element-specific XAS of the 2D alloys, which clearly indicates quenched atomic multiplets similar to the case of 2H-VSe2, provides strong evidence for the H phase of the 2D alloys. This work provides a comprehensive understanding of the thermal stability, chemical state, and electronic structure of 2D VxMo1-xSe2 alloys, useful for the future design of 2D electronic devices.

Magnetic Transition in Monolayer VSe2 via Interface Hybridization.

Magnetism in monolayer (ML) VSe2 has attracted broad interest in spintronics, while existing reports have not reached consensus. Using element-specific X-ray magnetic circular dichroism, a magnetic transition in ML VSe2 has been demonstrated at the contamination-free interface between Co and VSe2. Through interfacial hybridization with a Co atomic overlayer, a magnetic moment of about 0.4 µB per V atom in ML VSe2 is revealed, approaching values predicted by previous theoretical calculations. Promotion of the ferromagnetism in ML VSe2 is accompanied by its antiferromagnetic coupling to Co and a reduction in the spin moment of Co. In comparison to the absence of this interface-induced ferromagnetism at the Fe/ML MoSe2 interface, these findings at the Co/ML VSe2 interface provide clear proof that the ML VSe2, initially with magnetic disorder, is on the verge of magnetic transition.

Evidence of Spin Frustration in a Vanadium Diselenide Monolayer Magnet.

Monolayer VSe2 , featuring both charge density wave and magnetism phenomena, represents a unique van der Waals magnet in the family of metallic 2D transition-metal dichalcogenides (2D-TMDs). Herein, by means of in situ microscopy and spectroscopic techniques, including scanning tunneling microscopy/spectroscopy, synchrotron X-ray and angle-resolved photoemission, and X-ray absorption, direct spectroscopic signatures are established, that identify the metallic 1T-phase and vanadium 3d1 electronic configuration in monolayer VSe2 grown on graphite by molecular-beam epitaxy. Element-specific X-ray magnetic circular dichroism, complemented with magnetic susceptibility measurements, further reveals monolayer VSe2 as a frustrated magnet, with its spins exhibiting subtle correlations, albeit in the absence of a long-range magnetic order down to 2 K and up to a 7 T magnetic field. This observation is attributed to the relative stability of the ferromagnetic and antiferromagnetic ground states, arising from its atomic-scale structural features, such as rotational disorders and edges. The results of this study extend the current understanding of metallic 2D-TMDs in the search for exotic low-dimensional quantum phenomena, and stimulate further theoretical and experimental studies on van der Waals monolayer magnets.

Giant magneto-electric coupling in 100 nm thick Co capped by ZnO nanorods.

Here we report a giant, completely reversible magneto-electric coupling of 100 nm polycrystalline Co layer in contact with ZnO nanorods. When the sample is under an applied bias of ±2 V, the Co magnetic coercivity is reduced by a factor 5 from the un-poled case, with additionally a reduction of total magnetic moment in Co. Taking into account the chemical properties of ZnO nanorods measured by X-rays absorption near edge spectroscopy under bias, we conclude that these macroscopic effects on the magnetic response of the Co layer are due to the microstructure and the strong strain-driven magneto-electric coupling induced by the ZnO nanorods, whose nanostructuration maximizes the piezoelectric response under bias.

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.

Enhanced Magnetic Hybridization of a Spinterface through Insertion of a Two-Dimensional Magnetic Oxide Layer.

Interfaces between organic semiconductors and ferromagnetic metals offer intriguing opportunities in the rapidly developing field of organic spintronics. Understanding and controlling the spin-polarized electronic states at the interface is the key toward a reliable exploitation of this kind of systems. Here we propose an approach consisting in the insertion of a two-dimensional magnetic oxide layer at the interface with the aim of both increasing the reproducibility of the interface preparation and offering a way for a further fine control over the electronic and magnetic properties. We have inserted a two-dimensional Cr4O5 layer at the C60/Fe(001) interface and have characterized the corresponding morphological, electronic, and magnetic properties. Scanning tunneling microscopy and electron diffraction show that the film grows well-ordered both in the monolayer and multilayer regimes. Electron spectroscopies confirm that hybridization of the electronic states occurs at the interface. Finally, magnetic dichroism in X-ray absorption shows an unprecedented spin-polarization of the hybridized fullerene states. The latter result is discussed also in light of an ab initio theoretical analysis.