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.
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.
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.
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.
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.
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.