Nanostructured SnO2 is a promising material for the scalable production of portable gas sensors. To fully exploit their potential, these gas sensors need a faster recovery rate and higher sensitivity ...at room temperature than the current state of the art. Here we demonstrate a chemiresistive gas sensor based on vertical SnOx nanopillars, capable of sensing < 5 ppm of H2 at room temperature and 10 ppt at 230 °C. We test the sample both in vacuum and in air and observe an exceptional improvement in the performance compared to commercially available gas sensors. In particular, the recovery time for sensing NH3 at room temperature is more than one order of magnitude faster than a commercial SnO2 sensor. The sensor shows an unique combination of high sensitivity and fast recovery time, matching the requirements on materials expected to foster widespread use of portable and affordable gas sensors.
Iron phthalocyanines (FePc) adsorbed onto a Ag(110) substrate self-assemble into different monolayer phases going from rectangular to different oblique phases, with increasing molecular density. We ...have investigated the oxygen uptake capability of the different phases and their associated magneto-structural changes. Our study combines scanning tunneling microscopy and spectroscopy (STM/STS), X-ray magnetic circular dichroism (XMCD), and density functional theory (DFT) calculations. STM measurements reveal that the oxygenation reaction of the FePc/Ag(110) generally involves a displacement and a rotation of the molecules, which affects the electronic state of the Fe centers. The oxygen intercalation between FePc and the substrate is greatly obstructed by the steric hindrance in the high-density phases, to the point that a fraction of oblique phase molecules cannot change their position after oxidizing. Depending on the oxidation state and adsoption geometry, the STS spectra show clear differences in the Fe local density of states, which are mirrored in the XAS and XMCD experiments. Particularly, XMCD spectra of the oxidized phases reflect the distribution of FePc species (nonoxygenated, oxygenated-rotated, and oxygenated-unrotated) in the different cases. Sum rule analysis yields the effective spin (m s eff) and orbital (m L) magnetic moments of Fe in the different FePc species. Upon oxygenation, the magnetic moment of FePc molecules increases about an order of magnitude, reaching m TOT ∼ 2.2 μB per Fe atom.
The electronic structure and the geometric arrangement of picene molecules adsorbed on Ag(111) were studied by means of photoemission and near-edge X-ray absorption fine-structure spectroscopies ...(NEXAFS). While the valence band of a picene monolayer shows a clear metallic state that evolves with alkali metal doping, in the case of a picene multilayer there is no evidence of metallic states evolving with doping. Our data suggest that the bulk ultrahigh-vacuum films of K x picene are in an insulating phase, and we attribute this behavior to a strong electron–electron Coulomb interaction that is instead screened in the monolayer. The NEXAFS profiles of different picene layers show a coverage-dependent orientation, from flat molecules (monolayer) to an orientation of ∼40° of the molecular long axis with respect to the substrate surface (multilayer). The observed molecular orientations are in disagreement with the expected crystal structure of the bulk material and may explain the presence of insulating states in strongly correlated doped picene multilayers.
We present the results of a joint experimental and theoretical investigation concerning the effect of crystal packing on the electronic properties of the H2OEP molecule. Thin films, deposited in ...ultra high vacuum on metal surfaces, are investigated by combining valence band photoemission, inverse photoemission, and X-ray absorption spectroscopy. The spectra of the films are compared, when possible, with those measured in the gas phase. Once many-body effects are included in the calculations through the GW method, the electronic structure of H2OEP in the film and gas phase are accurately reproduced for both valence and conduction states. Upon going from an isolated molecule to the film phase, the electronic gap shrinks significantly and the lowest unoccupied molecular orbital (LUMO) and LUMO + 1 degeneracy is removed. The calculations show that the reduction of the transport gap in the film is entirely addressable to the enhancement of the electronic screening.
The characterization of graphene by electron and optical spectroscopy is well established and has led to numerous breakthroughs in material science. Yet, it is interesting to note that these ...characterization methods are almost never carried out on the same sample, i.e., electron spectroscopy uses epitaxial graphene while optical spectroscopy relies on cleaved graphene flakes. In order to bring coherence and convergence to this branch, a universal and easy-to-prepare substrate is needed. Here we suggest that chemical vapour deposition (CVD) grown graphene on thin monocrystalline Ir(111) films, which are grown heteroepitaxially on Si(111) wafers with an yttria stabilized zirconia (YSZ) buffer layer, perfectly meets these needs. We investigate graphene prepared in this way by low-energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), near edge X-ray absorption fine structure (NEXAFS) spectroscopy, angle-resolved photoemission spectroscopy (ARPES), resonance Raman spectroscopy, and scanning tunnelling microscopy (STM). Our results highlight the excellent crystalline quality of graphene, comparable to graphene prepared on Ir(111) bulk single crystals. This synthesis route allows for large-area, inexpensive growth on standardized disposable substrates, suitable for both optical and electron spectroscopic characterization, which meets the needs of many researchers in the field.
The electronic properties of graphene can be modified by the local interaction with a selected metal substrate. To probe this effect, Scanning Tunneling Microscopy is widely employed, particularly by ...means of local measurement via lock-in amplifier of the differential conductance and of the field emission resonance. In this article we propose an alternative, reliable method of probing the graphene/substrate interaction that is readily available to any STM apparatus. By testing the tunneling current as function of the tip/sample distance on nanostructured graphene on Ni(100) and Ir (100), we demonstrate that I(z) spectroscopy can be quantitatively compared with Density Functional Theory calculations and can be used to assess the nature of the interaction between graphene and substrate. This method can expand the capabilities of standard STM systems to study graphene/substrate complexes, complementing standard topographic probing with spectroscopic information.
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The formation and conformational adaptation of self-assembled monolayer of 2H-tetraphenylporphyrins (2H-TPPs) on metal surfaces, as well as their metalation processes in ultra-high vacuum (UHV), are ...reviewed. By means of XPS, NEXAFS and STM measurements we demonstrate that, after the annealing at 550 K, a temperature-induced chemical modification of 2H-TPP monolayer on Ag(111) occurs, resulting in the rotation of the phenyl rings parallel to the substrate plane. Moreover, independently of the conformation, we report three different methods to metalate 2H-TPP monolayers in UHV. Experimental evidence indicates that the presence of a metal atom in the TPP macrocycle influences both the conformation of the molecule and its adsorption distance.
•Au on Bi2Se3(0001) at RT forms islands according to the Volmer–Weber growth mode.•No lone Au atoms or islands smaller than ∼2 nm are observed on the Bi2Se3 surface.•Au on Bi2Se3 coalesces into ...larger and thicker islands when annealed (100–250 °C).•The topological surface state of Bi2Se3 is weakly affected by the presence of Au.•At the Au/Bi2Se3 interface there is a weak chemical instability.•Bi diffuses toward the surface of Au islands.•A chemical interaction between Au and Se is limited at the interfacial region.•Au on Bi2Se3 is inert towards CO and CO2 exposure (in the 10−8 mbar range).
We report a combined microscopy and spectroscopy study of Au deposited on the Bi2Se3(0001) single crystal surface. At room temperature Au forms islands, according to the Volmer–Weber growth mode. Upon annealing to 100 °C the Au deposits are not stable and assemble into larger and thicker islands. The topological surface state of Bi2Se3 is weakly affected by the presence of Au. Contrary to other metals, such as Ag or Cr, a strong chemical instability at the Au/Bi2Se3 interface is ruled out. Core level analysis highlights Bi diffusion toward the surface of Au islands, in agreement with previous findings, while chemical interaction between Au and atomic Se is limited at the interfacial region. For the investigated range of Au coverages, the Au/Bi2Se3 heterostructure is inert towards CO and CO2 exposure at low pressure (10−8 mbar) regime.
Nanostructured SnO
is a promising material for the scalable production of portable gas sensors. To fully exploit their potential, these gas sensors need a faster recovery rate and higher sensitivity ...at room temperature than the current state of the art. Here we demonstrate a chemiresistive gas sensor based on vertical SnO
nanopillars, capable of sensing < 5 ppm of H
at room temperature and 10 ppt at 230 °C. We test the sample both in vacuum and in air and observe an exceptional improvement in the performance compared to commercially available gas sensors. In particular, the recovery time for sensing NH
at room temperature is more than one order of magnitude faster than a commercial SnO
sensor. The sensor shows an unique combination of high sensitivity and fast recovery time, matching the requirements on materials expected to foster widespread use of portable and affordable gas sensors.