We present a detailed analysis of the electronic properties of graphene/Eu/Ni(111). By using angle- and spin-resolved photoemission spectroscopy and ab initio calculations, we show that the intercalation of Eu in the graphene/Ni(111) interface gives rise to a gapped freestanding dispersion of the 𝜋𝜋* Dirac cones at the K point with an additional lifting of the spin degeneracy due to the mixing of graphene and Eu states. The interaction with the magnetic substrate results in a large spin-dependent gap in the Dirac cones with a topological nature characterized by a large Berry curvature and a spin-polarized Van Hove singularity, whose closeness to the Fermi level gives rise to a polaronic band.
Metallic ferromagnetic transition metal dichalcogenides have emerged as important building blocks for scalable magnetic and memory applications. Downscaling such systems to the ultrathin limit is critical to integrate them into technology. Here, we achieved layer-by-layer control over the transition metal dichalcogenide Cr1.6Te2 by using pulsed laser deposition, and we uncovered the minimum critical thickness above which room-temperature magnetic order is maintained. The electronic and magnetic structures are explored experimentally and theoretically, and it is shown that the films exhibit strong in-plane magnetic anisotropy as a consequence of large spin-orbit effects. Our study elucidates both magnetic and electronic properties of Cr1.6Te2 and corroborates the importance of intercalation to tune the magnetic properties of nanoscale materials' architectures.
In the field of hydrogen production, MoS2 demonstrates good catalytic properties for the hydrogen evolution reaction (HER) which improve when doped with metal cations. However, while the role of sulfur atoms as active sites in the HER is largely reported, the role of metal atoms (i.e. molybdenum or the dopant cations) has yet to be studied in depth. To understand the role of the metal dopant, we study MoS2 thin films doped with Co and Mn ions. We identify the contribution of the electronic bands of the Mn and Co dopants to the integral valence band of the material using in situ resonant photoemission measurements. We demonstrate that Mn and Co dopants act differently: Mn doping favors the shift of the S–Mo hybridized band towards the Fermi level, while in the case of Co doping it is the less hybridized Co band that shifts closer to the Fermi level. Doping with Mn increases the effectiveness of S as the active site, thus improving the HER, while doping with Co introduces the metallic site of Co as the active site, which is less effective in improving HER properties. We therefore clarify the role of the dopant cation in the electronic structure determining the active site for hydrogen adsorption/desorption. Our results pave the way for the design of efficient materials for hydrogen production via the doping route, which can be extended to different catalytic reactions in the field of energy applications.
4Hb-TaS2 is a superconductor that exhibits unique characteristics such as time-reversal symmetry breaking, hidden magnetic memory, and topological edge modes. It is a naturally occurring heterostructure comprising of alternating layers of 1H-TaS2 and 1T-TaS2. The former is a well-known superconductor, while the latter is a correlated insulator with a possible non- trivial magnetic ground state. In this study, we use angle resolved photoemission spectroscopy to investigate the normal state electronic structure of this unconventional superconductor. Our findings reveal that the band structure of 4Hb-TaS2 fundamentally differs from that of its constituent materials. Specifically, we observe a significant charge transfer from the 1T layers to the 1H layers that drives the 1T layers away from half-filling. In addition, we find a substantial reduction in inter-layer coupling in 4Hb-TaS2 compared to the coupling in 2H-TaS2 that results in a pronounced spin-valley locking within 4Hb-TaS2.
The relation between crystal symmetries, electron correlations and electronic structure steers the formation of a large array of unconventional phases of matter, including magneto-electric loop currents and chiral magnetism1,2,3,4,5,6. The detection of such hidden orders is an important goal in condensed-matter physics. However, until now, non-standard forms of magnetism with chiral electronic ordering have been difficult to detect experimentally7. Here we develop a theory for symmetry-broken chiral ground states and propose a methodology based on circularly polarized, spin-selective, angular-resolved photoelectron spectroscopy to study them. We use the archetypal quantum material Sr2RuO4 and reveal spectroscopic signatures that, despite being subtle, can be reconciled with the formation of spin–orbital chiral currents at the surface of the material8,9,10. As we shed light on these chiral regimes, our findings pave the way for a deeper understanding of ordering phenomena and unconventional magnetism.
Long-range electronic ordering descending from a metallic parent state constitutes a rich playground to study the interplay of structural and electronic degrees of freedom. In this framework, kagome metals are in the most interesting regime where both phonon and electronically mediated couplings are significant. Several of these systems undergo a charge density wave transition. However, to date, the origin and the main driving force behind this charge order is elusive. Here, we use the kagome metal ScV6Sn6 as a platform to investigate this problem, since it features both a kagome-derived nested Fermi surface and van-Hove singularities near the Fermi level, and a charge-ordered phase that strongly affects its physical properties. By combining time-resolved reflectivity, first principles calculations and photo-emission experiments, we identify the structural degrees of freedom to play a fundamental role in the stabilization of charge order, indicating that ScV6Sn6 features an instance of charge order predominantly originating from phonons.
Mn3Si2Te6 is a rare example of a layered ferrimagnet. It has recently been shown to host a colossal angular magnetoresistance as the spin orientation is rotated from the in- to out-of-plane direction, proposed to be underpinned by a topological nodal-line degeneracy in its electronic structure. Nonetheless, the origins of its ferrimagnetic structure remain controversial, while its experimental electronic structure, and the role of correlations in shaping this, are little explored to date. Here, we combine x-ray and photoemission-based spectroscopies with first-principles calculations to probe the elemental-selective electronic structure and magnetic order in Mn3Si2Te6. Through these, we identify a marked Mn-Te hybridization, which weakens the electronic correlations and enhances the magnetic anisotropy. We demonstrate how this strengthens the magnetic frustration in Mn3Si2Te6, which is key to stabilizing its ferrimagnetic order, and find a crucial role of both exchange interactions extending beyond nearest-neighbors and antisymmetric exchange in dictating its ordering temperature. Together, our results demonstrate a powerful methodology of using experimental electronic structure probes to constrain the parameter space for first-principles calculations of magnetic materials, and through this approach, reveal a pivotal role played by covalency in stabilizing the ferrimagnetic order in Mn3Si2Te6.
Polarization dependent x-ray absorption spectroscopy was used to study the magnetic ground state and the orbital occupation in bulk-phase VI3 van der Waals crystals below and above the ferromagnetic and structural transitions. X-ray natural linear dichroism and x-ray magnetic circular dichroism spectra acquired at the V $L_{2,3}$ edges are compared against multiplet cluster calculations within the frame of the ligand field theory to quantify the intra-atomic electronic interactions at play and evaluate the effects of symmetry reduction occurring in a trigonally distorted VI6 unit. We observed a non zero linear dichroism proving the presence of an anisotropic charge density distribution around the V3+ ion due to the unbalanced hybridization between the vanadium and the ligand states. Such hybridization acts as an effective trigonal crystal field, slightly lifting the degeneracy of the $t_{2g}^2$ ground state. However, the energy splitting associated to the distortion underestimates the experimental band gap, suggesting that the insulating ground state is stabilized by Mott correlation effects rather than via a Jahn–Teller mechanism. Our results clarify the role of the distortion in VI3 and establish a benchmark for the study of the spectroscopic properties of other van der Waals halides, including emerging 2D materials with mono and few-layers thickness, whose fundamental properties might be altered by reduced dimensions and interface proximity.
We present a study of a sub-nanometre interlayer of crystalline silicon nitride at the Ni/Si interface. We performed transmission electron microscopy measurements complemented by energy dispersive X-ray analysis to investigate to what extent the nitride layer act as a barrier against atom diffusion. The results show that discontinuous silicide areas can form just below the nitride layer, whose composition is compatible with that of the nickel disilicide. The Ni–Si reaction is tentatively attributed to the thermal strain suffered by the interface during the deposition of Ni at low temperature.
Transition metal dichalcogenides exhibit many fascinating properties including superconductivity, magnetic orders, and charge density wave. The combination of these features with a non-trivial band topology opens the possibility of additional exotic states such as Majorana fermions and quantum anomalous Hall effect. Here, we report on photon-energy and polarization dependent spin-resolved angle-resolved photoemission spectroscopy experiments on single crystal 1T-VSe2, revealing an unexpected band inversion and emergent Dirac nodal arc with spin-momentum locking. Density functional theory calculations suggest a surface lattice strain could be the driving mechanism for the topologically nontrivial electronic structure of 1T-VSe2.
Kagome materials have emerged as a setting for emergent electronic phenomena that encompass different aspects of symmetry and topology. It is debated whether the XV6Sn6 kagome family (where X is a rare-earth element), a recently discovered family of bilayer kagome metals, hosts a topologically non-trivial ground state resulting from the opening of spin–orbit coupling gaps. These states would carry a finite spin Berry curvature, and topological surface states. Here we investigate the spin and electronic structure of the XV6Sn6 kagome family. We obtain evidence for a finite spin Berry curvature contribution at the centre of the Brillouin zone, where the nearly flat band detaches from the dispersing Dirac band because of spin–orbit coupling. In addition, the spin Berry curvature is further investigated in the charge density wave regime of ScV6Sn6 and it is found to be robust against the onset of the temperature-driven ordered phase. Utilizing the sensitivity of angle-resolved photoemission spectroscopy to the spin and orbital angular momentum, our work unveils the spin Berry curvature of topological kagome metals and helps to define its spectroscopic fingerprint.
We report on the growth and characterization of epitaxial YBa2Cu3O7−δ (YBCO) complex oxide thin films and related heterostructures exclusively by Pulsed Laser Deposition (PLD) and using first harmonic Nd:Y3Al5O12 (Nd:YAG) pulsed laser source (λ = 1064 nm). High-quality epitaxial YBCO thin film heterostructures display superconducting properties with transition temperature ∼ 80 K. Compared with the excimer lasers, when using Nd:YAG lasers, the optimal growth conditions are achieved at a large target-to-substrate distance d. These results clearly demonstrate the potential use of the first harmonic Nd:YAG laser source as an alternative to the excimer lasers for the PLD thin film community. Its compactness as well as the absence of any safety issues related to poisonous gas represent a major breakthrough in the deposition of complex multi-element compounds in form of thin films.
Here, we present an integrated ultra-high-vacuum (UHV) apparatus for the growth of complex materials and heterostructures. The specific growth technique is the Pulsed Laser Deposition (PLD) by means of a dual-laser source based on an excimer KrF ultraviolet and solid-state Nd:YAG infra-red lasers. By taking advantage of the two laser sources—both lasers can be independently used within the deposition chambers—a large number of different materials—ranging from oxides to metals, to selenides, and others—can be successfully grown in the form of thin films and heterostructures. All of the samples can be in situ transferred between the deposition chambers and the analysis chambers by using vessels and holders’ manipulators. The apparatus also offers the possibility to transfer samples to remote instrumentation under UHV conditions by means of commercially available UHV-suitcases. The dual-PLD operates for in-house research as well as user facility in combination with the Advanced Photo-electric Effect beamline at the Elettra synchrotron radiation facility in Trieste and allows synchrotron-based photo-emission as well as x-ray absorption experiments on pristine films and heterostructures.
V2O3 presents a complex interrelationship between the metal–insulator transition and the structural rhombohedral-monoclinic one in temperature, as a function of sample thickness. Whilst in bulk V2O3 the two transitions coincide on the temperature scale, at 15 nm thickness a fully independent Mott-like transition occurs at lower temperature, with no corresponding structural changes perhaps related to epitaxial strain. It is therefore of relevance to investigate the thin and ultrathin film growth to pinpoint the chemical, electronic and structural phase phenomenology and the role of the interface with the substrate. Here we present results on the thickness dependent properties of V2O3 from 1 nm up to 40 nm thick as grown on c-plane Al2O3 substrates by exploiting variable sampling depth probes. The surface morphology of stoichiometric ultra-thin V2O3 layers evolves from islands-like to continuous flat film with thickness, with implications on the overall properties.
Phase transitions are key in determining and controlling the quantum properties of correlated materials. Here, by using the combination of material synthesis and photoelectron spectroscopy, we demonstrate a genuine Mott transition undressed of any symmetry breaking side effects in the thin films of V2O3. In particular and in contrast with the bulk V2O3, we unveil the purely electronic dynamics approaching the metal–insulator transition, disentangled from the structural transformation that is prevented by the residual substrate-induced strain. On approaching the transition, the spectral signal evolves slowly over a wide temperature range, the Fermi wave-vector does not change, and the critical temperature is lower than the one reported for the bulk. Our findings are fundamental in demonstrating the universal benchmarks of a genuine nonsymmetry breaking Mott transition, extendable to a large array of correlated quantum systems, and hold promise of exploiting the metal–insulator transition by implementing V2O3 thin films in devices.
The occurrence of oxygen-driven metal–insulator-transition (MIT) in SrNbO3 (SNO) thin films epitaxially grown on (110)-oriented DyScO3 has been reported. SNO films are fabricated by the pulsed laser deposition technique at different partial O2 pressure to vary the oxygen content and their structural, optical, and transport properties are probed. SNO unit cell has been found to shrink vertically as the oxygen content increases but keeping the epitaxial matching with the substrate. The results of Fourier-transform infra-red spectroscopy show that highly oxygenated SNO samples (i.e., grown at high oxygen pressure) show distinct optical conductivity behavior with respect to oxygen deficient films, hence demonstrating the insulating character of the formers with respect to those fabricated with lower pressure conditions. Tailoring the optical absorption and conductivity of strontium niobate epitaxial films across the MIT will favor novel applications of this material.
The understanding of the origin of a two-dimensional electron gas (2DEG) at the surface of anatase TiO2 remains a challenging issue. In particular, in TiO2 ultra-thin films, it is extremely difficult to distinguish intrinsic effects, due to the physics of the TiO2, from extrinsic effects, such as those arising from structural defects, dislocations, and the presence of competing phases at the film/substrate interface. It is, therefore, mandatory to unambiguously ascertain the structure of the TiO2/substrate interface. In this work, by combining high angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), density functional theory calculations, and multislice image simulations, we have investigated the nature of strainless anatase TiO2 thin films grown on LaAlO3 substrate. In particular, the presence of oxygen vacancies in anatase TiO2 has been proved to stabilize the formation of an extra alloy layer, Ti2AlO4, by means of interface rearrangement. Our results, therefore, elucidate why the growth of anatase TiO2 directly on LaAlO3 substrate has required the deposition of a TiOx extra-layer to have a 2DEG established, thus confirming the absence of a critical thickness for the TiO2 to stabilize a 2DEG at its surface. These findings provide fundamental insights on the underlying formation mechanism of the 2DEG in TiO2/LAO hetero-interfaces to engineer the 2DEG formation in anatase TiO2 for tailored applications.
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.
The properties of half-metallic manganite thin films depend on the composition and structure in the atomic scale, and consequently, their potential functional behavior can only be based on fine structure characterization. By combining advanced transmission electron microscopy, electron energy loss spectroscopy, density functional theory calculations, and multislice image simulations, we obtained evidence of a 7 nm-thick interface layer in La0.7Sr0.3MnO3 (LSMO) thin films, compatible with the formation of well-known dead layers in manganites, with an elongated out-of-plane lattice parameter and structural and electronic properties well distinguished from the bulk of the film. We observed, for the first time, a structural shift of Mn ions coupled with oxygen vacancies and a reduced Mn valence state within such layer. Understanding the correlation between oxygen vacancies, the Mn oxidation state, and Mn-ion displacements is a prerequisite to engineer the magnetotransport properties of LSMO thin films.
In this work, we apply for the first time ambient pressure operando soft X-ray absorption spectroscopy (XAS) to investigate the location, structural properties, and reactivity of the defective sites present in the prototypical metal–organic framework HKUST-1. We obtained direct evidence that Cu+ defective sites form upon temperature treatment of the powdered form of HKUST-1 at 160 °C and that they are largely distributed on the material surface. Further, a thorough structural characterization of the Cu+/Cu2+ dimeric complexes arising from the temperature-induced dehydration/decarboxylation of the pristine Cu2+/Cu2+ paddlewheel units is reported. In addition to characterizing the surface defects, we demonstrate that CO2 may be reversibly adsorbed and desorbed from the surface defective Cu+/Cu2+ sites. These findings show that ambient pressure soft-XAS, combined with state-of-the-art theoretical calculations, allowed us to shed light on the mechanism involving the decarboxylation of the paddlewheel units on the surface to yield Cu+/Cu2+ complexes and their reversible restoration upon exposure to gaseous CO2.
Dirac fermions play a central role in the study of topological phases, for they can generate a variety of exotic states, such as Weyl semimetals and topological insulators. The control and manipulation of Dirac fermions constitute a fundamental step toward the realization of novel concepts of electronic devices and quantum computation. By means of Angle-Resolved Photo-Emission Spectroscopy (ARPES) experiments and ab initio simulations, here, we show that Dirac states can be effectively tuned by doping a transition metal sulfide, BaNiS2, through Co/Ni substitution. The symmetry and chemical characteristics of this material, combined with the modification of the charge-transfer gap of BaCo1−xNixS2 across its phase diagram, lead to the formation of Dirac lines, whose position in k-space can be displaced along the Γ−M symmetry direction and their form reshaped. Not only does the doping x tailor the location and shape of the Dirac bands, but it also controls the metal-insulator transition in the same compound, making BaCo1−xNixS2 a model system to functionalize Dirac materials by varying the strength of electron correlations.
Probing the energy and spin electron properties of materials by means of photoemission spectroscopy gives insights into the low-energy phenomena of matter driven by spin orbit coupling or exchange interaction. The information that can be derived from complete photoelectron spectroscopy experiments, beyond E(k), is contained in the photoemission transition matrix elements that determine peak intensities. We present here a complete photoemission study of the spin-polarized bands of 2H−NbSe2, a material that presents a surface spin-texture. Circular dichroism in angular-resolved photoemission spectroscopy (CD-ARPES) data are compared with spin-polarized angular-resolved spectra (SARPES) as measured with linearly polarized radiation in a well-characterized experimental chirality, at selected photon energy values. CD-ARPES is due to a matrix element effect that depends strongly on photon energy and experimental geometry: we show that it cannot be used to infer intrinsic spin properties in 2H−NbSe2. On the other hand, SARPES data provide reliable direct information on the spin properties of the electron states. The results on 2H−NbSe2 are discussed, and general methodological conclusions are drawn on the best experimental approach to the determination of the spin texture of quantum materials.
Quantum materials are central for the development of novel functional systems that are often based on interface specific phenomena. Fabricating controlled interfaces between quantum materials requires adopting a flexible growth technique capable to synthesize different materials within a single-run deposition process with high control of structure, stoichiometry, and termination. Among the various available thin film growth technologies, pulsed laser deposition (PLD) allows controlling the growth of diverse materials at the level of single atomic layers. In PLD the atomic species are supplied through an ablation process of a stoichiometric target either in form of polycrystalline powders or of a single crystal. No carrier gases are needed in the deposition process. The ablation process is compatible with a wide range of background pressure. We present results of thin-film growth by PLD obtained by using an Nd:YAG infrared pulsed laser source operating at its first harmonics. With respect to the traditional PLD systems—based on excimer KrF UV-lasers—optimal conditions for the growth of thin films and heterostructures are reached at large target-to-substrate distance. Merits and limitations of this approach for growing oxide and non-oxide thin films are discussed. The merits of an Nd:YAG laser to grow very high-quality thin films suggest the possibility of implementing compact in-situ setups e.g. integrated with analytical instrumentation under ultra-high vacuum conditions.
We study the 2×2 charge density wave (CDW) in epitaxially-grown monolayer TiSe2. Our temperature-dependent angle-resolved photoemission spectroscopy measurements indicate a strong-coupling instability, but reveal how not all states couple equally to the symmetry-breaking distortion, with an electron pocket persisting to low temperature as a non-bonding state. We further show how the CDW order can be suppressed by a modest doping of around 0.06(2) electrons per Ti. Our results provide an opportunity for quantitative comparison with a realistic tight-binding model, which emphasises a crucial role of structural aspects of the phase transition in understanding the hybridisation in the ground state. Together, our work provides a comprehensive understanding of the phenomenology of the CDW in TiSe2 in the 2D limit.
Here, we present an integrated ultra-high vacuum apparatus—named MBE-Cluster —dedicated to the growth and in situ structural, spectroscopic, and magnetic characterization of complex materials. Molecular Beam Epitaxy (MBE) growth of metal oxides, e.g., manganites, and deposition of the patterned metallic layers can be fabricated and in situ characterized by reflection high-energy electron diffraction, low-energy electron diffraction, Auger electron spectroscopy, x-ray photoemission spectroscopy, and azimuthal longitudinal magneto-optic Kerr effect. The temperature can be controlled in the range from 5 K to 580 K, with the possibility of application of magnetic fields H up to ±7 kOe and electric fields E for voltages up to ±500 V. The MBE-Cluster operates for in-house research as well as user facility in combination with the APE beamlines at Sincrotrone-Trieste and the high harmonic generator facility for time-resolved spectroscopy.
Ambient pressure operando soft X-ray absorption spectroscopy (soft-XAS) was applied to study the reactivity of hydroxylated SnO2 nanoparticles towards reducing gases. H2 was first used as a test case, showing that gas phase and surface states can be simultaneously probed: soft-XAS at the O K-edge gains sensitivity towards the gas phase, while at the Sn M4,5-edges tin surface states are explicitly probed. Results obtained by flowing hydrocarbons (CH4 and CH3CHCH2) unequivocally show that these gases react with surface hydroxyl groups to produce water without producing carbon oxides, and release electrons that localize on Sn to eventually form SnO. The partially reduced SnO2-x layer at the surface of SnO2 is readily reoxidised to SnO2 by treating the sample with O2 at mild temperatures (> 200 °C), revealing the nature of “electron sponge” of tin oxide. The experiments, combined with DFT calculations, allowed devising a mechanism for dissociative hydrocarbon adsorption on SnO2, involving direct reduction of Sn sites at the surface via cleavage of C-H bonds, and the formation of methoxy- and/or methyl-tin species at the surface.
Bulk PtSn4 has recently attracted the interest of the scientific community for the presence of electronic states exhibiting Dirac node arcs, enabling possible applications in nanoelectronics. Here, by means of surface-science experiments and density functional theory, we assess its suitability for catalysis by studying the chemical reactivity of the (0 1 0)-oriented PtSn4 surface toward CO, H2O, O2 molecules at room temperature and, moreover, its stability in air. We demonstrate that the catalytic activity of PtSn4 is determined by the composition of the outermost atomic layer. Specifically, we find that the surface termination for PtSn4 crystals cleaved in vacuum is an atomic Sn layer, which is totally free from any CO poisoning. In oxygen-rich environment, as well as in ambient atmosphere, the surface termination is a SnOx skin including SnO and SnO2 in comparable amount. However, valence-band states, including those forming Dirac node arcs, are only slightly affected by surface modifications. The astonishingly beneficial influence of surface oxidation on catalytic activity has been demonstrated by electrocatalytic tests evidencing a reduction of the Tafel slope, from 442 down to 86 mV dec−1, whose origin has been explained by our theoretical model. The use of surface-science tools to tune the chemical reactivity of PtSn4 opens the way toward its effective use in catalysis, especially for hydrogen evolution reaction and oxygen evolution reaction.
We investigate the temperature-dependent electronic structure of the van der Waals ferromagnet, CrGeTe3. Using angle-resolved photoemission spectroscopy, we identify atomic- and orbital-specific band shifts upon cooling through TC. From these, together with x-ray absorption spectroscopy and x-ray magnetic circular dichroism measurements, we identify the states created by a covalent bond between the Te 5p and the Cr eg orbitals as the primary driver of the ferromagnetic ordering in this system, while it is the Cr t2g states that carry the majority of the spin moment. The t2g states furthermore exhibit a marked bandwidth increase and a remarkable lifetime enhancement upon entering the ordered phase, pointing to a delicate interplay between localized and itinerant states in this family of layered ferromagnets.
Two-dimensional (2D) metallic states induced by oxygen vacancies (VOs) at oxide surfaces and interfaces provide opportunities for the development of advanced applications, but the ability to control the behavior of these states is still limited. We used angle resolved photoelectron spectroscopy combined with density-functional theory (DFT) to study the reactivity of VO-induced states at the (001) surface of anatase TiO2, where both 2D metallic and deeper lying in-gap states (IGs) are observed. The 2D and IG states exhibit remarkably different evolutions when the surface is exposed to molecular O2: while IGs are almost completely quenched, the metallic states are only weakly affected. DFT calculations indeed show that the IGs originate from surface VOs and remain localized at the surface, where they can promptly react with O2. In contrast, the metallic states originate from subsurface vacancies whose migration to the surface for recombination with O2 is kinetically hindered on anatase TiO2 (001), thus making them much less sensitive to oxygen dosing.
Among transition-metal dichalcogenides, mono and few-layers thick VSe2 has gained much recent attention following claims of intrinsic room-temperature ferromagnetism in this system, which have nonetheless proved controversial. Here, we address the magnetic and chemical properties of Fe/VSe2 heterostructure by combining element sensitive x-ray absorption spectroscopy and photoemission spectroscopy. Our x-ray magnetic circular dichroism results confirm recent findings that both native mono/few-layer and bulk VSe2 do not show intrinsic ferromagnetic ordering. Nonetheless, we find that ferromagnetism can be induced, even at room temperature, after coupling with a Fe thin film layer, with antiparallel alignment of the moment on the V with respect to Fe. We further consider the chemical reactivity at the Fe/VSe2 interface and its relation with interfacial magnetic coupling.
Band inversions are key to stabilising a variety of novel electronic states in solids, from topological surface states to the formation of symmetry-protected three-dimensional Dirac and Weyl points and nodal-line semimetals. Here, we create a band inversion not of bulk states, but rather between manifolds of surface states. We realise this by aliovalent substitution of Nb for Zr and Sb for S in the ZrSiS family of nonsymmorphic semimetals. Using angle-resolved photoemission and density-functional theory, we show how two pairs of surface states, known from ZrSiS, are driven to intersect each other near the Fermi level in NbGeSb, and to develop pronounced spin splittings. We demonstrate how mirror symmetry leads to protected crossing points in the resulting spin-orbital entangled surface band structure, thereby stabilising surface state analogues of three-dimensional Weyl points. More generally, our observations suggest new opportunities for engineering topologically and symmetry-protected states via band inversions of surface states.
Palladium ditelluride (PdTe2) is a novel transition‐metal dichalcogenide exhibiting type‐II Dirac fermions and topological superconductivity. To assess its potential in technology, its chemical and thermal stability is investigated by means of surface‐science techniques, complemented by density functional theory, with successive implementation in electronics, specifically in a millimeter‐wave receiver. While water adsorption is energetically unfavorable at room temperature, due to a differential Gibbs free energy of ≈+12 kJ mol−1, the presence of Te vacancies makes PdTe2 surfaces unstable toward surface oxidation with the emergence of a TeO2 skin, whose thickness remains sub‐nanometric even after one year in air. Correspondingly, the measured photocurrent of PdTe2‐based optoelectronic devices shows negligible changes (below 4%) in a timescale of one month, thus excluding the need of encapsulation in the nanofabrication process. Remarkably, the responsivity of a PdTe2‐based millimeter‐wave receiver is 13 and 21 times higher than similar devices based on black phosphorus and graphene in the same operational conditions, respectively. It is also discovered that pristine PdTe2 is thermally stable in a temperature range extending even above 500 K, thus paving the way toward PdTe2‐based high‐temperature electronics. Finally, it is shown that the TeO2 skin, formed upon air exposure, can be removed by thermal reduction via heating in vacuum.
The redox process of pretreated Co3O4 thin film coatings has been studied by ambient pressure soft X-ray absorption spectroscopy. The Co3O4 coatings were composed of nanoparticles of about 10 nm in size as prepared by pulsed laser deposition. The thin film coatings were pretreated in He or in H2 up to 150 °C prior to exposure to the reactive gases. The reactivity toward carbon monoxide and oxygen was monitored by near-edge X-ray absorption fine structure (NEXAFS) spectroscopy during gas exposures. The results indicate that the samples pretreated in He show reactivity only at high temperature, while the samples pretreated in H2 are reactive also at room temperature. X-ray photoemission spectroscopy measurements in ultra-high vacuum and NEXAFS simulations with the CTM4XAS code further specify the results.
Cu2ZnSnS4 (CZTS) nanocrystals (NCs) were produced via hot-injection from metal chloride precursors. A systematic investigation of the influence of synthesis conditions on composition, size and microstructure of CZTS NCs is presented. The results show that the solvent amount (oleylamine) is a key parameter in the synthesis of this quaternary chalcogenide: a low solvent content leads to CZTS NCs with a prominent kesterite phase with the desired composition for use as absorber material in thin film photovoltaic cells. It is also observed that lowering the injection temperature (250 °C) favours formation of CZTS NCs in the wurtzite phase. The effect of different high temperature thermal treatments on the grain growth is also shown: large crystals are obtained with annealing in inert atmosphere, whereas nanocrystalline films are obtained introducing sulphur vapour during the heat treatment. A correlation between the grain dimension and the carbonaceous residues in the final films is investigated. It is shown that the grain growth is hindered by organic residues, amount and nature of which depend on the heat treatment atmosphere. In fact, oleylamine is removed by a complex pyrolytic process, which is affected by the presence of sulphur vapour. The latter favours the stability of oleylamine residuals against its non-oxidative release.
Currently, there is a flurry of research interest on materials with an unconventional electronic structure, and we have already seen significant progress in their understanding and engineering towards real-life applications. The interest erupted with the discovery of graphene and topological insulators in the previous decade. The electrons in graphene simulate massless Dirac Fermions with a linearly dispersing Dirac cone in their band structure, while in topological insulators, the electronic bands wind non-trivially in momentum space giving rise to gapless surface states and bulk bandgap. Weyl semimetals in condensed matter systems are the latest addition to this growing family of topological materials. Weyl Fermions are known in the context of high energy physics since almost the beginning of quantum mechanics. They apparently violate charge conservation rules, displaying the 'chiral anomaly', with such remarkable properties recently theoretically predicted and experimentally verified to exist as low energy quasiparticle states in certain condensed matter systems. Not only are these new materials extremely important for our fundamental understanding of quantum phenomena, but also they exhibit completely different transport phenomena. For example, massless Fermions are susceptible to scattering from non-magnetic impurities. Dirac semimetals exhibit non-saturating extremely large magnetoresistance as a consequence of their robust electronic bands being protected by time reversal symmetry. These open up whole new possibilities for materials engineering and applications including quantum computing. In this review, we recapitulate some of the outstanding properties of WTe2, namely, its non-saturating titanic magnetoresistance due to perfect electron and hole carrier balance up to a very high magnetic field observed for the very first time. It also indicative of hosting Lorentz violating type-II Weyl Fermions in its bandstructure, again first predicted candidate material to host such a remarkable phase. We primarily focus on the findings of our ARPES, spin-ARPES, and time-resolved ARPES studies complemented by first-principles calculations.
The band inversions that generate the topologically non-trivial band gaps of topological insulators and the isolated Dirac touching points of three-dimensional Dirac semimetals generally arise from the crossings of electronic states derived from different orbital manifolds. Recently, the concept of single orbital-manifold band inversions occurring along high-symmetry lines has been demonstrated, stabilising multiple bulk and surface Dirac fermions. Here, we discuss the underlying ingredients necessary to achieve such phases, and discuss their existence within the family of transition metal dichalcogenides. We show how their three-dimensional band structures naturally produce only small k z projected band gaps, and demonstrate how these play a significant role in shaping the surface electronic structure of these materials. We demonstrate, through spin- and angle-resolved photoemission and density functional theory calculations, how the surface electronic structures of the group-X TMDs PtSe2 and PdTe2 are host to up to five distinct surface states, each with complex band dispersions and spin textures. Finally, we discuss how the origin of several recently-realised instances of topological phenomena in systems outside of the TMDs, including the iron-based superconductors, can be understood as a consequence of the same underlying mechanism driving k z -mediated band inversions in the TMDs.
Materials exhibiting nodal‐line fermions promise superb impact on technology for the prospect of dissipationless spintronic devices. Among nodal‐line semimetals, the ZrSiX (X = S, Se, Te) class is the most suitable candidate for such applications. However, the surface chemical reactivity of ZrSiS and ZrSiSe has not been explored yet. Here, by combining different surface‐science tools and density functional theory, it is demonstrated that the formation of ZrSiS and ZrSiSe surfaces by cleavage is accompanied by the washing up of the exotic topological bands, giving rise to the nodal line. Moreover, while the ZrSiS has a termination layer with both Zr and S atoms, in the ZrSiSe surface, reconstruction occurs with the appearance of Si surface atoms, which is particularly prone to oxidation. It is demonstrated that the chemical activity of ZrSiX compounds is mostly determined by the interaction of the Si layer with the ZrX sublayer. A suitable encapsulation for ZrSiX should not only preserve their surfaces from interaction with oxidative species, but also provide a saturation of dangling bonds with minimal distortion of the surface.
The delicate interplay of electronic charge, spin, and orbital degrees of freedom is in the heart of many novel phenomena across the transition metal oxide family. Here, by combining high-resolution angle-resolved photoemission spectroscopy and first principles calculations (with and without spin-orbit coupling), the electronic structure of the rutile binary iridate,
IrO2, is investigated. The detailed study of electronic bands measured on a high-quality single crystalline sample and use of a wide range of photon energy provide a huge improvement over the previous studies. The excellent agreement between theory and experimental results shows that the single-particle DFT description of IrO2 band structure is adequate, without the need of invoking any treatment of correlation effects. Although many observed features point to a 3D nature of the electronic structure, clear surface effects are revealed. The discussion of the orbital character of the relevant bands crossing the Fermi level sheds light on spin-orbit-coupling-driven phenomena in this material, unveiling a spin-orbit-induced avoided crossing, a property likely to play a key role in its large spin Hall effect.
We study the low-energy surface electronic structure of the transition-metal dichalcogenide superconductor
PdTe2 by spin- and angle-resolved photoemission, scanning tunneling microscopy, and density-functional theory-based supercell calculations. Comparing PdTe2 with its sister compound PtSe2, we demonstrate how enhanced interlayer hopping in the Te-based material drives a band inversion within the antibonding p-orbital manifold well above the Fermi level. We show how this mediates spin-polarized topological surface states which form rich multivalley Fermi surfaces with complex spin textures. Scanning tunneling spectroscopy reveals type-II superconductivity at the surface, and moreover shows no evidence for an unconventional component of its superconducting order parameter, despite the presence of topological surface states.
PtTe2 is a novel transition-metal dichalcogenide hosting type-II Dirac fermions that displays application capabilities in optoelectronics and hydrogen evolution reaction. Here it is shown, by combining surface science experiments and density functional theory, that the pristine surface of PtTe2 is chemically inert toward the most common ambient gases (oxygen and water) and even in air. It is demonstrated that the creation of Te vacancies leads to the appearance of tellurium-oxide phases upon exposing defected PtTe2 surfaces to oxygen or ambient atmosphere, which is detrimental for the ambient stability of uncapped PtTe2-based devices. On the contrary, in PtTe2 surfaces modified by the joint presence of Te vacancies and substitutional carbon atoms, the stable adsorption of hydroxyl groups is observed, an essential step for water splitting and the water–gas shift reaction. These results thus pave the way toward the exploitation of this class of Dirac materials in catalysis.
Transition-metal dichalcogenides (TMDs) are renowned for their rich and varied bulk properties, while their single-layer variants have become one of the most prominent examples of two-dimensional materials beyond graphene. Their disparate ground states largely depend on transition metal d-electron-derived electronic states, on which the vast majority of attention has been concentrated to date. Here, we focus on the chalcogen-derived states. From density-functional theory calculations together with spin- and angle-resolved photoemission, we find that these generically host a co-existence of type-I and type-II three-dimensional bulk Dirac fermions as well as ladders of topological surface states and surface resonances. We demonstrate how these naturally arise within a single p-orbital manifold as a general consequence of a trigonal crystal field, and as such can be expected across a large number of compounds. Already, we demonstrate their existence in six separate TMDs, opening routes to tune, and ultimately exploit, their topological physics.
Extremely large magnetoresistance (XMR), observed in transition-metal dichalcogenides,
WTe2, has attracted recently a great deal of research interest as it shows no sign of saturation up to a magnetic field as high as 60 T, in addition to the presence of type-II Weyl fermions. Currently, there is a great deal of discussion on the role of band structure changes in the temperature-dependent XMR in this compound. In this contribution, we study the band structure of WTe2 using angle-resolved photoemission spectroscopy and first-principles calculations to demonstrate that the temperature-dependent band structure has no substantial effect on the temperature-dependent XMR, as our measurements do not show band structure changes upon increasing the sample temperature between 20 and 130 K. We further observe an electronlike surface state, dispersing in such a way that it connects the top of bulk holelike band to the bottom of bulk electronlike band. Interestingly, similarly to bulk states, the surface state is also mostly intact with the sample temperature. Our results provide valuable information in shaping the mechanism of temperature-dependent XMR in WTe2.
By combining bulk sensitive soft-x-ray angular-resolved photoemission spectroscopy and first-principles calculations we explored the bulk electron states of WTe2, a candidate type-II Weyl semimetal featuring a large nonsaturating magnetoresistance. Despite the layered geometry suggesting a two-dimensional electronic structure, we directly observe a three-dimensional electronic dispersion. We report a band dispersion in the reciprocal direction perpendicular to the layers, implying that electrons can also travel coherently when crossing from one layer to the other. The measured Fermi surface is characterized by two well-separated electron and hole pockets at either side of the Γ point, differently from previous more surface sensitive angle-resolved photoemission spectroscopy experiments that additionally found a pronounced quasiparticle weight at the zone center. Moreover, we observe a significant sensitivity of the bulk electronic structure of WTe2 around the Fermi level to electronic correlations and renormalizations due to self-energy effects, previously neglected in first-principles descriptions.
Complete photoemission experiments, enabling measurement of the full quantum set of the photoelectron final state, are in high demand for studying materials and nanostructures whose properties are determined by strong electron and spin correlations. Here the implementation of the new spin polarimeter VESPA (Very Efficient Spin Polarization Analysis) at the APE-NFFA beamline at Elettra is reported, which is based on the exchange coupling between the photoelectron spin and a ferromagnetic surface in a reflectometry setup. The system was designed to be integrated with a dedicated Scienta-Omicron DA30 electron energy analyzer allowing for two simultaneous reflectometry measurements, along perpendicular axes, that, after magnetization switching of the two targets, allow the three-dimensional vectorial reconstruction of the spin polarization to be performed while operating the DA30 in high-resolution mode. VESPA represents the very first installation for spin-resolved ARPES (SPARPES) at the Elettra synchrotron in Trieste, and is being heavily exploited by SPARPES users since autumn 2015.
We report the study of anatase TiO2(001)-oriented thin films grown by pulsed laser deposition on LaAlO3(001). A combination of in situ and ex situ methods has been used to address both the origin of the Ti3+-localized states and their relationship with the structural and electronic properties on the surface and the subsurface. Localized in-gap states are analyzed using resonant X-ray photoelectron spectroscopy and are related to the Ti3+ electronic configuration, homogeneously distributed over the entire film thickness. We find that an increase in the oxygen pressure corresponds to an increase in Ti3+ only in a well-defined range of deposition pressure; outside this range, Ti3+ and the strength of the in-gap states are reduced.
Transition-metal dichalcogenides (WTe2 and MoTe2) have recently drawn much attention, because of the
nonsaturating extremely large magnetoresistance (XMR) observed in these compounds in addition to the
predictions of likely type-II Weyl semimetals. Contrary to the topological insulators or Dirac semimetals where XMR is linearly dependent on the field, in WTe2 and MoTe2 the XMR is nonlinearly dependent on the field, suggesting an entirely different mechanism. Electron-hole compensation has been proposed as a mechanism of this nonsaturating XMR in WTe2, while it is yet to be clear in the case of MoTe2 which has an identical crystal structure of WTe2 at low temperatures. In this Rapid Communication, we report low-energy electronic structure and Fermi surface topology of MoTe2 using angle-resolved photoemission spectrometry (ARPES) technique and first-principles calculations, and compare them with that of WTe2 to understand the mechanism of XMR. Our measurements demonstrate that MoTe2 is an uncompensated semimetal, contrary to WTe2 in which compensated electron-hole pockets have been identified, ruling out the applicability of charge compensation theory for the nonsaturating XMR in MoTe2. In this context, we also discuss the applicability of other existing conjectures on the XMR of these compounds.
We report on epitaxial growth of Bi2Se3topological insulator thin films by Pulsed Laser Deposition(PLD). X-ray diffraction investigation confirms that Bi2Se3with a single (001)-orientation can beobtained on several substrates in a narrow (i.e., 20°C) range of deposition temperatures and at highdeposition pressure (i.e., 0.1 mbar). However, only films grown on (001)-Al2O3substrates show analmost-unique in-plane orientation.In-situspin-resolved angular resolved photoemission spectros-copy experiments, performed at the NFFA-APE facility of IOM-CNR and Elettra (Trieste), show asingle Dirac cone with the Dirac point atEB0:38 eV located in the center of the Brillouin zoneand the spin polarization of the topological surface states. These results demonstrate that the topolog-ical surface state can be obtained in PLD-grown Bi2Se3thin films.
The electronic structure of the chiral helimagnet
Cr1/3NbS2 has been studied with core level and angle-resolved photoemission spectroscopy (ARPES). Intercalated Cr atoms are found to be effective in donating electrons to the NbS2 layers but also cause significant modifications of the electronic structure of the host NbS2 material. In particular, the data provide evidence that a description of the electronic structure of Cr1/3NbS2 on the basis of a simple rigid band picture is untenable. The data also reveal substantial inconsistencies with the predictions of standard density functional theory. The relevance of these results to the attainment of a correct description of the electronic structure of chiral helimagnets, magnetic thin films/multilayers, and transition metal dichalcogenides intercalated with 3d magnetic elements is discussed.
Topological insulators are a promising class of materials for applications in the field of spintronics. New perspectives in this field can arise from interfacing metal–organic molecules with the topological insulator spin-momentum locked surface states, which can be perturbed enhancing or suppressing spintronics-relevant properties such as spin coherence. Here we show results from an angle-resolved photemission spectroscopy (ARPES) and scanning tunnelling microscopy (STM) study of the prototypical cobalt phthalocyanine (CoPc)/Bi2Se3 interface. We demonstrate that that the hybrid interface can act on the topological protection of the surface and bury the Dirac cone below the first quintuple layer.
The behaviour of electrons and holes in a crystal lattice is a fundamental quantum phenomenon, accounting for a rich variety of material properties. Boosted by the remarkable electronic and physical properties of two-dimensional materials such as graphene and topological insulators, transition metal dichalcogenides have recently received renewed attention. In this context, the anomalous bulk properties of semimetallic WTe2 have attracted considerable interest. Here we report angle- and spin-resolved photoemission spectroscopy of WTe2 single crystals, through which we disentangle the role of W and Te atoms in the formation of the band structure and identify the interplay of charge, spin and orbital degrees of freedom. Supported by first-principles calculations and high-resolution surface topography, we reveal the existence of a layer-dependent behaviour. The balance of electron and hole states is found only when considering at least three Te–W–Te layers, showing that the behaviour of WTe2 is not strictly two dimensional.