The formation and the evolution of electronic metallic states localized at the surface, commonly termed 2D electron gas (2DEG), represents a peculiar phenomenon occurring at the surface and interface of many transition metal oxides (TMO). Among TMO, titanium dioxide (TiO2), particularly in its anatase polymorph, stands as a prototypical system for the development of novel applications related to renewable energy, devices and sensors, where understanding the carrier dynamics is of utmost importance. In this study, angle-resolved photo-electron spectroscopy (ARPES) and X-ray absorption spectroscopy (XAS) are used, supported by density functional theory (DFT), to follow the formation and the evolution of the 2DEG in TiO2 thin films. Unlike other TMO systems, it is revealed that, once the anatase fingerprint is present, the 2DEG in TiO2 is robust and stable down to a single-unit-cell, and that the electron filling of the 2DEG increases with thickness and eventually saturates. These results prove that no critical thickness triggers the occurrence of the 2DEG in anatase TiO2 and give insight in formation mechanism of electronic states at the surface of TMO.
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.
Here, we discuss the key features of electrocatalysis with mitrofanovite (Pt3Te4), a recently discovered mineral with superb performances in hydrogen evolution reaction. Mitrofanovite is a layered topological metal with spin-polarized topological surface states with potential applications for spintronics. However, mitrofanovite is also an exceptional platform for electrocatalysis, with costs of the electrodes suppressed by 47% owing to the partial replacement of Pt with Te. Remarkably, the Tafel slope in nanostructured mitrofanovite is just 33 mV/dec, while reduced mitrofanovite has the same Tafel slope (36 mV/dec) as state-of-the-art electrodes of pure Pt. Mitrofanovite also affords surface stability and robustness to CO poisoning. Accordingly, these findings pave the way for the advent of mitrofanovite for large-scale hydrogen production.
V2O3 has long been studied as a prototypical strongly correlated material. The difficulty in obtaining clean, well ordered surfaces, however, hindered the use of surface sensitive techniques to study its electronic structure. Here we show by means of X-ray diffraction and electrical transport that thin films prepared by pulsed laser deposition can reproduce the functionality of bulk V2O3. The same films, when transferred in-situ, show an excellent surface quality as indicated by scanning tunnelling microscopy and low energy electron diffraction, representing a viable approach to study the metal-insulator transition in V2O3 by means of angle-resolved photoemission spectroscopy. Combined, these two aspects pave the way for the use of V2O3 thin films in device-oriented heterostructures.
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.
We report on a two-dimensional (2D) V1–xPtxSe2 alloy that exhibits ferromagnetic order and Rashba spin–orbit coupling. Although ferromagnetism is absent in 1T-VSe2 because of the competition with the charge density wave phase, we demonstrate theoretically and experimentally that the substitution of vanadium by platinum in VSe2 (10–50%) to form a homogeneous 2D alloy restores ferromagnetic order down to one monolayer of V0.65Pt0.35Se2. Moreover, the presence of platinum atoms gives rise to Rashba spin–orbit coupling in (V,Pt)Se2, providing an original platform to study the interplay between ferromagnetism and spin–orbit coupling in the 2D limit.
TaSe3 is a layered van der Waals semimetal with several inverted band gaps throughout the entire Brillouin zone and nontrivial Z2 topological indices, which place it at the boundary between a strong and a weak topological phase. Our transport experiments reveal a quadratic nonsaturating magnetoresistance (MR) with values reaching 104% at 1.8 K and 14 T, whose origins have to be searched in the material's band structure. Here we combine angle-resolved photoelectron spectroscopy experiments, also with spin resolution, with ab initio calculations based on density functional theory in order to draw a connection between the Fermi surface topology and the measured transport properties. Simulations based on the calculated Fermi surface clarify that electron-hole compensation plays an important role for the observed MR in the bulk material. At the surface, the position of Fermi level differs, and it can be controlled by alkali metal deposition which accounts not only for the energy shift of the bands but it slightly modifies the dispersion of the valence and conduction bands. We propose that the observed band-gap renormalization might offer a route for engineering the topological phase in TaSe3, alternative to strain.
The emergence of Dirac semimetals has stimulated growing attention, owing to the considerable technological potential arising from their peculiar exotic quantum transport related to their nontrivial topological states. Especially, materials showing type-II Dirac fermions afford novel device functionalities enabled by anisotropic optical and magnetotransport properties. Nevertheless, real technological implementation has remained elusive so far. Definitely, in most Dirac semimetals, the Dirac point lies deep below the Fermi level, limiting technological exploitation. Here, it is shown that kitkaite (NiTeSe) represents an ideal platform for type-II Dirac fermiology based on spin-resolved angle-resolved photoemission spectroscopy and density functional theory. Precisely, the existence of type-II bulk Dirac fermions is discovered in NiTeSe around the Fermi level and the presence of topological surface states with strong (≈50%) spin polarization. By means of surface-science experiments in near-ambient pressure conditions, chemical inertness towards ambient gases (oxygen and water) is also demonstrated. Correspondingly, NiTeSe-based devices without encapsulation afford long-term efficiency, as demonstrated by the direct implementation of a NiTeSe-based microwave receiver with a room-temperature photocurrent of 2.8 µA at 28 GHz and more than two orders of magnitude linear dynamic range. The findings are essential to bringing to fruition type-II Dirac fermions in photonics, spintronics, and optoelectronics.
Due to their peculiar quasiparticle excitations, topological metals have high potential for applications in the fields of spintronics, catalysis, and superconductivity. Here, by combining spin- and angle-resolved photoemission spectroscopy, scanning tunneling microscopy/spectroscopy, and density functional theory, we discover surface-termination-dependent topological electronic states in the recently discovered mitrofanovite Pt3Te4. Mitrofanovite crystal is formed by alternating, van der Waals bound layers of Pt2Te2 and PtTe2. Our results demonstrate that mitrofanovite is a topological metal with termination-dependent (i) electronic band structure and (ii) spin texture. Despite their distinct electronic character, both surface terminations are characterized by electronic states exhibiting strong spin polarization with a node at the Γ point and sign reversal across the Γ point, indicating their topological nature and the possibility of realizing two distinct electronic configurations (both of them with topological features) on the surface of the same material.
By means of electrocatalytic tests, surface-science techniques and density functional theory, we unveil the physicochemical mechanisms ruling the electrocatalytic activity of recently discovered mitrofanovite (Pt3Te4) mineral. Mitrofanovite represents a very promising electrocatalyst candidate for energy-related applications, with a reduction of costs by 47% compared to pure Pt and superior robustness to CO poisoning. We show that Pt3Te4 is a weak topological metal with the Z2 invariant, exhibiting electrical conductivity (∼4 × 106 S/m) comparable with pure Pt. In hydrogen evolution reaction (HER), the electrode based on bulk Pt3Te4 shows a very small overpotential of 46 mV at 10 mA cm–2 and a Tafel slope of 36–49 mV dec–1 associated with the Volmer–Heyrovsky mechanism. The outstanding ambient stability of Pt3Te4 also provides durability of the electrode and long-term stability of its efficient catalytic performances.
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.
The ZrSiS family of compounds hosts various exotic quantum phenomena due to the presence of both topological nonsymmorphic Dirac fermions and nodal-line fermions. In this material family, the LnSbTe (Ln = lanthanide) compounds are particularly interesting owing to the intrinsic magnetism from magnetic Ln which leads to new properties and quantum states. In this work, the authors focus on the previously unexplored compound SmSbTe. The studies reveal a rare combination of a few functional properties in this material, including antiferromagnetism with possible magnetic frustration, electron correlation enhancement, and Dirac nodal-line fermions. These properties enable SmSbTe as a unique platform to explore exotic quantum phenomena and advanced functionalities arising from the interplay between magnetism, topology, and electronic correlations.
We investigated the relationship between ferromagnetism and metallicity in strained La0.67Ca0.33MnO3 films grown on lattice-mismatched NdGaO3 (001) by means of spectroscopic techniques directly sensitive to the ferromagnetic state, to the band structure, and to the chemical state of the atoms. In this system, the ferromagnetic metallic (FMM) phase spatially coexists with an insulating one in most of the phase diagram. First, the observation of an almost 100% spin polarization of the photoelectrons at the Fermi level in the fundamental state provides direct evidence of the half-metallicity of the FMM phase, a result that has been previously observed through direct probing of the valence band only on unstrained, phase-homogeneous La0.67Sr0.33MnO3. Second, the spin polarization results to be correlated with the occupancy at the Fermi level for all the investigated temperature regimes. These outcomes show that the half-metallic behavior predicted by a double-exchange model persists even in phase-separated manganites. Moreover, the correlation between metallicity and ferromagnetic alignment is confirmed by X-ray magnetic circular dichroism, a more bulk-sensitive technique, allowing one to explain transport properties in terms of the conduction through aligned FMM domains.
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.
Dirac semimetals are classified into different phases based on the types of Dirac fermions. Tuning the transition among different types of Dirac fermions in one system remains a challenge. Recently, KMgBi was predicted to be located at a critical state in which various types of Dirac fermions can be induced owing to the existence of a flatband. Here, we carried out systematic studies on the electronic structure of KMgBi single crystals by combining angle-resolve photoemission spectroscopy and scanning tunneling microscopy/spectroscopy. The flatband was clearly observed near the Fermi level. We also revealed a small bandgap of ∼20 meV between the flatband and the conduction band. These results demonstrate the critical states of KMgBi that transition among various types of Dirac fermions can be tuned in one system.
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.
In non-magnetic materials the combination of inversion symmetry breaking (ISB) and spin-orbit coupling (SOC) determines the spin polarization of the band structure. However, a local spin polarization can also arise in centrosymmetric crystals containing ISB subunits. This is namely the case for the nodal-line semimetal ZrSiTe where, by combining spin- and angle-resolved photoelectron spectroscopy with ab initio band structure calculations, we reveal a complex spin polarization. In the bulk, the valence and conduction bands exhibit opposite spin orientations in two spatially separated two-dimensional ZrTe sectors within the unit cell, yielding no net polarization. We also observe spin-polarized surface states that are well separated in energy and momentum from the bulk bands. A layer-by-layer analysis of the spin polarization allows us to unveil the complex evolution of the signal in the bulk states near the surface, thus bringing the intertwined nature of surface and bulk effects to the fore.
The advent of topological semimetals enables the exploitation of symmetry-protected
topological phenomena and quantized transport. Here, we present homogeneous rectifiers,
converting high-frequency electromagnetic energy into direct current, based on low-energy
Dirac fermions of topological semimetal-NiTe2, with state-of-the-art efficiency already in the
first implementation. Explicitly, these devices display room-temperature photosensitivity as
high as 251 mA W−1 at 0.3 THz in an unbiased mode, with a photocurrent anisotropy ratio of
22, originating from the interplay between the spin-polarized surface and bulk states. Device
performances in terms of broadband operation, high dynamic range, as well as their high
sensitivity, validate the immense potential and unique advantages associated to the control of
nonequilibrium gapless topological states via built-in electric field, electromagnetic polar-
ization and symmetry breaking in topological semimetals. These findings pave the way for the
exploitation of topological phase of matter for high-frequency operations in polarization-
sensitive sensing, communications and imaging.
Research on ultrathin quantum materials requires full control of the growth and surface quality of the specimens in order to perform experiments on their atomic structure and electron states leading to ultimate analysis of their intrinsic properties. We report results on epitaxial FeSe thin films grown by pulsed laser deposition (PLD) on CaF2 (001) substrates as obtained by exploiting the advantages of an all-in-situ ultra-high vacuum (UHV) laboratory allowing for direct high-resolution surface analysis by scanning tunnelling microscopy (STM), synchrotron radiation X-ray photoelectron spectroscopy (XPS) and angle-resolved photoemission spectroscopy (ARPES) on fresh surfaces. FeSe PLD growth protocols were fine-tuned by optimizing target-to-substrate distance d and ablation frequency, atomically flat terraces with unit-cell step heights are obtained, overcoming the spiral morphology often observed by others. In-situ ARPES with linearly polarized horizontal and vertical radiation shows hole-like and electron-like pockets at the Γ and M points of the Fermi surface, consistent with previous observations on cleaved single crystal surfaces. The control achieved in growing quantum materials with volatile elements such as Se by in-situ PLD makes it possible to address the fine analysis of the surfaces by in-situ ARPES and XPS. The study opens wide avenues for the PLD based heterostructures as work-bench for the understanding of proximity-driven effects and for the development of prospective devices based on combinations of quantum materials.
The electronic properties of hole- and electron-doped manganites were probed by a combination of x-ray absorption and photoemission spectroscopies. Hole-doped La0.7Ba0.3MnO3 and electron-doped La0.7Ce0.3MnO3 thin films were epitaxially grown on SrTiO3 substrates by means of pulsed laser deposition. Ex-situ x-ray diffraction demonstrated the substrate/film epitaxy relation and in-situ low energy electron diffraction provided evidence of high structural order of film surfaces. By combining synchrotron x-ray absorption and x-ray photoemission spectroscopy, evidence of Mn ions into a 2+ state as a result of the Ce substitution in the electron-doped manganites was provided. Angular resolved photo-emission spectroscopy (ARPES) results showed a predominance of z2-orbitals at the surface of both hole- and, unexpectedly, electron-doped manganites thus questioning the validity of the commonly accepted scenario describing the electron filling in manganites’ 3d orbitals in oxide manganites. The precise determination of the electronic and orbital properties of the terminating layers of oxide manganites paves the way for engineering multi-layered heterostructures thus leading to novel opportunities in the field of quantum electronics.
Trigonal tellurium, a small-gap semiconductor with pronounced magneto-electric and magneto-optical responses, is among the simplest realizations of a chiral crystal. We have studied by spin- and angle-resolved photoelectron spectroscopy its unconventional electronic structure and unique spin texture. We identify Kramers–Weyl, composite, and accordionlike Weyl fermions, so far only predicted by theory, and show that the spin polarization is parallel to the wave vector along the lines in k space connecting high-symmetry points. Our results clarify the symmetries that enforce such spin texture in a chiral crystal, thus bringing new insight in the formation of a spin vectorial field more complex than the previously proposed hedgehog configuration. Our findings thus pave the way to a classification scheme for these exotic spin textures and their search in chiral crystals.
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.
The electronic properties of strontium ruthenate SrRuO3perovskite oxide thin filmsare modified by epitaxial strain, as determined by growing on different substrates by pulsedlaser deposition. Temperature dependence of the transport properties indicates that tensilestrain deformation of the SrRuO3unit cell reduces the metallicity of the material as well as itsmetal-insulator-transition (MIT) temperature. On the contrary, the shrinkage of the Ru–O–Rubuckling angle due to compressive strain is counterweighted by the increased overlap of theconduction Ru-4d orbitals with the O-2p ones due to the smaller interatomic distances resulting intoan increased MIT temperature, i.e., a more conducting material. In particular, in the more metallicsamples, the core level X-ray photoemission spectroscopy lineshapes show the occurrence of anextra-peak at the lower binding energies of the main Ru-3d peak that is attributed to screening,as observed in volume sensitive photoemission of the unstrained material.
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.
The electronic properties of anatase titanium dioxide (TiO2) thin films epitaxially grown on LaAlO3 substrates are investigated by synchrotron-x-ray spectroscopy [x-ray absorption spectroscopy (XAS), x-ray photoemission spectroscopy (XPS), and angle-resolved photoemission spectroscopy (ARPES)] and infrared spectroscopy. The Ti3+ fraction in TiO2−x is varied either by changing the oxygen pressure during deposition or by postgrowth annealing in ultrahigh vacuum (UHV). Structural investigation of the TiO2 thin films provides evidence of highly uniform crystallographic order in both as-grown and in situ UHV-annealed samples. The increased amount of Ti3+ as a consequence of UHV annealing is calibrated by in situ XPS and XAS analysis. The as-grown TiO2 samples, with a low Ti3+ concentration, show distinct electronic properties with respect to the annealed films, namely, absorption in the midinfrared (MIR) region correlated with polaron formation, and another peak in the visible range at 1.6 eV correlated with the presence of localized defect states (DSs). With the increasing level of Ti3+ induced by the postannealing process, the MIR peak disappears, while the DS peak is redshifted to the near-infrared region at about 1.0 eV. These results indicate the possibility of tailoring the optical absorption of anatase TiO2 films from the visible to the near-infrared region.
Chiral crystal YbNi3Ga9 is known as an intermediate valence compound in which a strong hybridization between the 4f orbitals and the conduction band is present. The Co-substitution to YbNi3Ga9 works as a hole doping that reduces the Kondo temperature and enhances the effective mass of itinerant charge carriers. Using angle-resolved photoelectron spectroscopy, the complex band structure of Yb(Ni1−xCox)3Ga9 (x=0,0.1) is revealed. A Yb2+ 4f7/2 band and evidences of hybridization to valence bands are found near the Fermi level. Both YbNi3Ga9 and the Co-substituted compound exhibit double hexagonal Fermi surfaces centered at the Γ¯-point, surrounded by a large snowflake-like surface, and a triangular electron-like surface along the Γ¯M¯ direction. By changing the incident photon energy, the band dispersion along the c-axis and the barrel-shaped Fermi surface is observed.
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.
We present the results of a photon energy and polarization dependent angle-resolved photoemission spectroscopy (ARPES) study on high quality, epitaxial SrNbO3 thin films prepared in situ by pulsed laser deposition (PLD). We show that the Fermi surface is composed of three bands mainly due to t(2g) orbitals of Nb 4d, in analogy with the 3d-based perovskite systems. The bulk band dispersion for the conduction and valence states obtained by density functional theory (DFT) is generally consistent with the ARPES data. The small discrepancy in the bandwidth close to the Fermi level seems to result from the interplay of correlation effects and the presence of vacancies. The ARPES results are complemented by soft x-ray photoemission spectroscopy measurements in order to provide indications on the chemical states and the stoichiometry of the material.
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.
The layered van der Waals antiferromagnet MnBi2Te4 has been predicted to combine the band ordering of archetypical topological insulators such as Bi2Te3 with the magnetism of Mn, making this material a viable candidate for the realization of various magnetic topological states. We have systematically investigated the surface electronic structure of MnBi2Te4(0001) single crystals by use of spin- and angle-resolved photoelectron spectroscopy experiments. In line with theoretical predictions, the results reveal a surface state in the bulk band gap and they provide evidence for the influence of exchange interaction and spin-orbit coupling on the surface electronic structure.
Electronic correlation is believed to play an important role in exotic phenomena such as insulator-metal transition, colossal magnetoresistance, and high-temperature superconductivity in correlated electron systems. Recently, it has been shown that electronic correlation may also be responsible for the formation of unconventional plasmons. Herewith, using a combination of angle-dependent spectroscopic ellipsometry, angle resolved photoemission spectroscopy, and Hall measurements, all as a function of temperature supported by first-principles calculations, the existence of low-loss high-energy correlated plasmons accompanied by spectral weight transfer, a fingerprint of electronic correlation, in topological insulator (Bi0.8Sb0.2)2Se3 is revealed. Upon cooling, the density of free charge carriers in the surface states decreases whereas that in the bulk states increases, and the recently reported correlated plasmons are key to explaining this phenomenon. Our result shows the importance of electronic correlation in determining correlated plasmons and opens an alternative path in engineering plasmonic-based topologically insulating devices.
We combine time-resolved pump-probe magneto-optical Kerr effect and photoelectron spectroscopy experiments supported by theoretical analysis to determine the relaxation dynamics of delocalized electrons in half-metallic ferromagnetic manganite La1−xSrxMnO3. We observe that the half-metallic character of La1−xSrxMnO3 determines the timescale of both the electronic phase transition and the quenching of magnetization, revealing a quantum isolation of the spin system in double-exchange ferromagnets extending up to hundreds of picoseconds. We demonstrate the use of time-resolved hard x-ray photoelectron spectroscopy as a unique tool to single out the evolution of strongly correlated electronic states across a second-order phase transition in a complex material.
A proper understanding on the charge mobility in organic materials is one of the key factors to realize highly functionalized organic semiconductor devices. So far, however, although a number of studies have proposed the carrier transport mechanism of rubrene single crystal to be band-like, there are disagreements between the results reported in these papers. Here, we show that the actual dispersion widths of the electronic bands formed by the highest occupied molecular orbital are much smaller than those reported in the literature, and that the disagreements originate from the diffraction effect of photoelectron and the vibrations of molecules. The present result indicates that the electronic bands would not be the main channel for hole mobility in case of rubrene single crystal and the necessity to consider a more complex picture like molecular vibrations mediated carrier transport. These findings open an avenue for a thorough insight on how to realize organic semiconductor devices with high carrier mobility.
Whenever one is interested in making high temperature superconductor-based devices, the goodness of the sample surface in terms of structural and electrical properties is a strong issue. In fact, it is well known that the surface of high Tc superconducting samples is not bulk-representative, due to air contamination and to the possible presence of oxygen vacancies. In addition, the quality of the surface layer results to be crucial in surface sensitive measurements as in X-ray photoelectron and Angle-resolved photoemission spectroscopy. Recently, some studies have been dedicated to the realization of devices based on electron-doped cuprates, bilayers and nanowires, showing the actual possibility to realize good quality junctions by using these cuprates. In this work, we report on the fabrication of thin films of the electron-doped Nd2−xCexCuO4±δ compound and analyze the surface natural barrier of as-grown films by means of point contact spectroscopy measurements. Suitable treatments of samples in an ozone rich atmosphere have been developed in order to improve the surface quality of the films. Auger electron spectroscopy has been used to monitor the effectiveness of these treatments.
We report on the reproducible surface topological electron states in Bi2Se3 topological insulator thin films when epitaxially grown by Pulsed Laser Deposition (PLD) on (0 0 1)-oriented SrTiO3 (STO) perovskite substrates. Bi2Se3 has been reproducibly grown with single (0 0 1)-orientation and low surface roughness as controlled by ex-situ X-ray diffraction and in situ scanning tunnel microscopy and low-energy electron diffraction. Finally, in situ synchrotron radiation angle-resolved photo-emission spectroscopy measurements show a single Dirac cone and Dirac point at eV located in the center of the Brillouin zone likewise found from exfoliated single-crystals. These results demonstrate that the topological surface electron properties of PLD-grown Bi2Se3 thin films grown on (0 0 1)-oriented STO substrates open new perspectives for applications of multi-layered materials based on oxide perovskites.
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.
By means of angle‐resolved photoemission spectroscopy measurements, the electronic band structure of the three‐dimensional PbBi4Te7 and PbBi6Te10 topological insulators is compared. The measurements clearly reveal coexisting topological and multiple Rashba‐like split states close to the Fermi level for both systems. The observed topological states derive from different surface terminations, as confirmed by scanning tunneling microscopy measurements, and are well‐described by the density functional theory simulations. Both the topological and the Rashba‐like states reveal a prevalent two‐dimensional character barely affected by air exposure. X‐ray and valence band photoemission measurements suggest Rashba‐like states stem from the van der Waals gap expansion, consistently with density functional theory calculations.
Topological insulators (TIs) with an inverted bulk band and a strong spin-orbit coupling exhibit gapless topological surface states (TSSs) protected by time-reversal symmetry. Helical spin textures driven by spin-momentum locking offer the opportunity to generate spin-polarized currents and therefore TIs are expected to be used for future spintronic applications. For practical applications TIs are urgently required that are operable at room temperature due to a wide bulk band gap as well as a distinct topological surface state that is robust to atmospheric exposure. Here we show two distinguishable TSSs originating from different terminations on PbBi4Te4S3 by using spin- and angle-resolved photoemission spectroscopy. We find that one TSS is persistently observed, while the other becomes invisible upon intentional oxygen exposure. The result signifies the presence of a protected TSS buried under the topmost surface. Our finding paves the way for realizing a topological spintronics device under atmospheric conditions.
We report on the influence of spin-orbit coupling (SOC) in Fe-based superconductors via application of circularly polarized spin and angle-resolved photoemission spectroscopy. We combine this technique in representative members of both the Fe-pnictides (LiFeAs) and Fe-chalcogenides (FeSe) with tight-binding calculations to establish an ubiquitous modification of the electronic structure in these materials imbued by SOC. At low energy, the influence of SOC is found to be concentrated on the hole pockets, where the largest superconducting gaps are typically found. This effect varies substantively with the
kzdispersion, and in FeSe we find SOC to be comparable to the energy scale of orbital order. These results contest descriptions of superconductivity in these materials in terms of pure spin-singlet eigenstates, raising questions regarding the possible pairing mechanisms and role of SOC therein.
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 present a study on the growth and characterization of high-quality single-layer MoS2 with a single orientation, i.e. without the presence of mirror domains. This single orientation of the MoS2 layer is established by means of x-ray photoelectron diffraction. The high quality is evidenced by combining scanning tunneling microscopy with x-ray photoelectron spectroscopy measurements. Spin- and angle-resolved photoemission experiments performed on the sample revealed complete spin-polarization of the valence band states near the K and -K points of the Brillouin zone. These findings open up the possibility to exploit the spin and valley degrees of freedom for encoding and processing information in devices that are based on epitaxially grown materials.
The challenge of synthesizing graphene nanoribbons (GNRs) with atomic precision is currently being pursued along a one-way road, based on the synthesis of adequate molecular precursors that react in predefined ways through self-assembly processes. The synthetic options for GNR generation would multiply by adding a new direction to this readily successful approach, especially if both of them can be combined. We show here how GNR synthesis can be guided by an adequately nanotemplated substrate instead of by the traditionally designed reactants. The structural atomic precision, unachievable to date through top-down methods, is preserved by the self-assembly process. This new strategy’s proof-of-concept compares experiments using 4,4′′-dibromo-para-terphenyl as a molecular precursor on flat Au(111) and stepped Au(322) substrates. As opposed to the former, the periodic steps of the latter drive the selective synthesis of 6 atom-wide armchair GNRs, whose electronic properties have been further characterized in detail by scanning tunneling spectroscopy, angle resolved photoemission, and density functional theory calculations.
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.
Carbon nanomaterials exhibit extraordinary mechanical and electronic properties desirable for future technologies. Beyond the popular sp2‐scaffolds, there is growing interest in their graphdiyne‐related counterparts incorporating both sp2 and sp bonding in a regular scheme. Herein, we introduce carbonitrile‐functionalized graphdiyne nanowires, as a novel conjugated, one‐dimensional (1D) carbon nanomaterial systematically combining the virtues of covalent coupling and supramolecular concepts that are fabricated by on‐surface synthesis. Specifically, a terphenylene backbone is extended with reactive terminal alkyne and polar carbonitrile (CN) moieties providing the required functionalities. It is demonstrated that the CN functionalization enables highly selective alkyne homocoupling forming polymer strands and gives rise to mutual lateral attraction entailing room‐temperature stable double‐stranded assemblies. By exploiting the templating effect of the vicinal Ag(455) surface, 40 nm long semiconducting nanowires are obtained and the first experimental assessment of their electronic band structure is achieved by angle‐resolved photoemission spectroscopy indicating an effective mass below 0.1m0 for the top of the highest occupied band. Via molecular manipulation it is showcased that the novel oligomer exhibits extreme mechanical flexibility and opens unexplored ways of information encoding in clearly distinguishable CN‐phenyl trans–cis species. Thus, conformational data storage with density of 0.36 bit nm−2 and temperature stability beyond 150 K comes in reach.
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.
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.
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 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 prediction of Weyl fermions in the low-temperature noncentrosymmetric
1T′ phase of MoTe2 still awaits clear experimental confirmation. Here, we report angle-resolved photoemission (ARPES) data and ab initio calculations that reveal a surface state arc dispersing between the valence and the conduction band, as expected for a Weyl semimetal. However, we find that the arc survives in the high-temperature centrosymmetric 1T'' phase. Therefore, a surface Fermi arc is not an unambiguous fingerprint of a topologically nontrivial phase. We have also investigated the surface state spin texture of the
1T′ phase by spin-resolved ARPES, and identified additional topologically trivial spin-split states within the projected band gap at higher binding energies.
Topological Weyl semimetal (TWS), a new state of quantum matter, has sparked enormous research interest recently. Possessing unique Weyl fermions in the bulk and Fermi arcs on the surface, TWSs offer a rare platform for realizing many exotic physical phenomena. TWSs can be classified into type-I that respect Lorentz symmetry and type-II that do not. Here, we directly visualize the electronic structure of MoTe2, a recently proposed type-II TWS. Using angle-resolved photoemission spectroscopy (ARPES), we unravel the unique surface Fermi arcs, in good agreement with our ab initio calculations that have nontrivial topological nature. Our work not only leads to new understandings of the unusual properties discovered in this family of compounds, but also allows for the further exploration of exotic properties and practical applications of type-II TWSs, as well as the interplay between superconductivity (MoTe2 was discovered to be superconducting recently) and their topological order.
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.