Search

Ultrahigh power factor is achieved for SnSe/Bi composite film by easy scalable route at 580 K, which can further explored for other metals as well.

Hybrid inorganic/organic heterointerfaces are promising systems for next-generation photocatalytic, photovoltaic, and chemical-sensing applications. Their performance relies strongly on the development of robust and reliable surface passivation and functionalization protocols with (sub)molecular control. The structure, stability, and chemistry of the semiconductor surface determine the functionality of the hybrid assembly. Generally, these modification schemes have to be laboriously developed to satisfy the specific chemical demands of the semiconductor surface. The implementation of a chemically independent, yet highly selective, standardized surface functionalization scheme, compatible with nanoelectronic device fabrication, is of utmost technological relevance. Here, we introduce a modular surface assembly (MSA) approach that allows the covalent anchoring of molecular transition-metal complexes with sub-nanometer precision on any solid material by combining atomic layer deposition (ALD) and selectively self-assembled monolayers of phosphonic acids. ALD, as an essential tool in semiconductor device fabrication, is used to grow conformal aluminum oxide activation coatings, down to sub-nanometer thicknesses, on silicon surfaces to enable a selective step-by-step layer assembly of rhenium(I) bipyridine tricarbonyl molecular complexes. The modular surface assembly of molecular complexes generates precisely structured spatial ensembles with strong intermolecular vibrational and electronic coupling, as demonstrated by infrared spectroscopy, photoluminescence, and X-ray photoelectron spectroscopy analysis. The structure of the MSA can be chosen to avoid electronic interactions with the semiconductor substrate to exclusively investigate the electronic interactions between the surface-immobilized molecular complexes.

Magnetic topological insulators (MTIs) have recently become a subject of poignant interest; among them, Z

Oxygen reduction reaction (ORR) is a crucial process that drives the operation of several energy storage devices. ORR can proceed on the neat carbon surface in the absence of a catalyst, and its electrochemical activity is determined by its microstructure and chemical composition. Oxygen functional groups unavoidably existing on the carbon surface can serve as adsorption sites for ORR intermediates; the presence of some oxygen functionalities gives rise to an increase in the density of electronic states (DOS) at the Fermi level (FL). Both factors should have a positive impact on the electron transfer rate that was demonstrated for ORR in aqueous media. To study the O-groups effect on the aprotic ORR, which is now of interest due to the extensive development of aprotic metal-air batteries, we use model oxidized carbon electrodes (HOPG and single-layer graphene). We demonstrate that oxygen functionalities (epoxy, carbonyl, and lactone) do not affect the rate of one-electron oxygen reduction in aprotic media in the absence of metal cations since their introduction practically does not increase DOS at FL. However, in Li+-containing electrolytes, oxygen groups enhance both the rate of second electron transfer and carbon degradation due to its oxidation by LiO2 yielding carbonate species.

We investigate the oxidation mechanism of the layered model system GeAs.

Scanning photoelectron microscopy (SPEM) and photoemission electron microscopy (PEEM) allow local surface analysis and visualising ongoing reactions on a µm-scale. These two spatio-temporal imaging methods are applied to polycrystalline Rh, representing a library of well-defined high-Miller-index surface structures. The combination of these techniques enables revealing the anisotropy of surface oxidation, as well as its effect on catalytic hydrogen oxidation. In the present work we observe, using locally-resolved SPEM, structure-sensitive surface oxide formation, which is summarised in an oxidation map and quantitatively explained by the novel step density (SDP) and step edge (SEP) parameters. In situ PEEM imaging of ongoing H2 oxidation allows a direct comparison of the local reactivity of metallic and oxidised Rh surfaces for the very same different stepped surface structures, demonstrating the effect of Rh surface oxides. Employing the velocity of propagating reaction fronts as indicator of surface reactivity, we observe a high transient activity of Rh surface oxide in H2 oxidation. The corresponding velocity map reveals the structure-dependence of such activity, representing a direct imaging of a structure-activity relation for plenty of well-defined surface structures within one sample., Surface oxide formation under reaction conditions may change the catalytic activity of a catalyst. Here, the authors explore the effect of atomic structure of Rh surfaces on the surface oxide formation and its influence on catalytic activity in hydrogen oxidation, revealing a high transient activity.

The study investigates the effect of deep cryogenic treatment (DCT) on a high-alloyed ferrous alloy (HAFA) and its effectiveness on carbide evolution and chemical shifts of alloying elements. With ex-situ and in-situ observations ranging from the microscopic to the nanoscopic level, we uncover the atomistic mechanism by which DCT affects carbide precipitation, resulting in a 50% increase in carbide volume fraction. Synchrotron-based scanning photoelectron microscopy provides insight into the agglomeration of carbon during exposure to DCT. We find that Mo plays a crucial role in DCT through its modification of chemical bonding states, which is postulated to originate from the loosely-formed primordial Mo2C carbides formed during exposure to cryogenic temperatures. These in turn provide energetically favorable nucleation zones that accelerate the formation of M7C3 carbides, which serve as intermediate states for the formation of M23C6 carbides, which most strongly impact the mechanical properties. These results are supported by atom probe tomography, showing the preferential formation of Mo-rich M7C3 carbides in DCT samples, resulting from greater solute mobility. This work clarifies the fundamental mechanisms on how DCT affects HAFA, solving a long-elusive problem.

Here, we present a proof-of-concept experiment where phase engineering at the nanoscale of 2D transition metal dichalcogenides (TMDC) flakes (from semiconducting 2H phase to metallic 1T phase) can be achieved by thermal annealing of a TMDC/Au/mica system. The local dewetting of Au particles and resulting tensile strain produced on the TMDC flakes, strongly bound to the Au surface through effective S-Au bonds, can induce a local structural phase transition. An important role is also played by the defects induced by the thermal annealing: when vacancies are present, the threshold strain needed to trigger the phase transition is significantly reduced. Scanning photoelectron microscopy (SPEM) was revealed to be the perfect tool to monitor the described phenomena.

The morphology of the heterogeneous CrxTi1-xSe2 and CrxTi1-xS2 single crystals has been studied using X-ray scanning photoemission microscopy (SPEM) and angular resolved photoemission spectroscopy (ARPES). A direct method of SPEM provided us the insight into the origin of the blurred ARPES images for Cr0.78Ti0.36Se2 single crystal. Using SPEM, we confirmed the formation of the CrSe2-based structural fragments inside the CrxTi1-xSe2 single crystals with x ≥ 0.75. The chemical composition of the forming structural fragments depends on the chalcogen (S, Se) forming the crystal lattice.

Oxidation mechanism and kinetics of the layered model system GeAs.

As a semiconductor ferroelectric, GeTe has become a focus of renewed attention due to the recent discovery of giant Rashba splitting. It already has a wide range of applications, from thermoelectricity to data storage. Its stability in ambient air, as well as the structure and properties of an oxide layer, define the processing media for device production and operation. Here, we studied a reaction between the GeTe (111) surface and molecular oxygen for crystals having solely inversion domains. We evaluated the reaction kinetics both ex situ and in situ using NAP XPS. The structure of the oxide layer is extensively discussed, where, according to HAADF-STEM and STEM-EDX, nanoscale phase separation of GeO2 and Te is observed, which is unusual for semiconductors. We believe that such behaviour is closely related to the ferroelectric properties and the domain structure of GeTe.

Multiphoton polymer cross-linking evolves as the core process behind high-resolution additive microfabrication with soft materials for implantable/wearable electronics, tissue engineering, microrobotics, biosensing, drug delivery, etc. Electrons and soft X-rays, in principle, can offer even higher resolution and printing rates. However, these powerful lithographic tools are difficult to apply to vacuum incompatible liquid precursor solutions used in continuous additive fabrication. In this work, using biocompatible hydrogel as a model soft material, we demonstrate high-resolution in-liquid polymer cross-linking using scanning electron and X-ray microscopes. The approach augments the existing solid-state electron/X-ray lithography and beam-induced deposition techniques with a wider class of possible chemical reactions, precursors, and functionalities. We discuss the focused beam cross-linking mechanism, the factors affecting the ultimate feature size, and layer-by-layer printing possibilities. The potential of this technology is demonstrated on a few practically important applications such as in-liquid encapsulation of nanoparticles for plasmonic sensing and interfacing of viable cells with hydrogel electrodes.

We combine spatially resolved scanning photoelectron spectroscopy with confocal Raman and optical microscopy to reveal how the oxidation of the buried graphene–Cu interface relates to the Cu crystallographic orientation. We analyze over 100 different graphene covered Cu (high and low index) orientations exposed to air for 2 years. Four general oxidation modes are observed that can be mapped as regions onto the polar plot of Cu surface orientations. These modes are (1) complete, (2) irregular, (3) inhibited, and (4) enhanced wrinkle interface oxidation. We present a comprehensive characterization of these modes, consider the underlying mechanisms, compare air and water mediated oxidation, and discuss this in the context of the diverse prior literature in this area. This understanding incorporates effects from across the wide parameter space of 2D material interface engineering, relevant to key challenges in their emerging applications, ranging from scalable transfer to electronic contacts, encapsulation, and corrosion protection.

The potential use of NiO in low-dimensional devices requires the upgrade of appropriate synthesis methods as well as the achievement of a deeper comprehension of the growth mechanisms and the prope...

Catalytic hydrogen oxidation on a polycrystalline rhodium foil used as a surface structure library is studied by scanning photoelectron microscopy (SPEM) in the 10−6 mbar pressure range, yielding spatially resolved X-ray photoemission spectroscopy (XPS) measurements. Here we report an observation of a previously unknown coexistence of four different states on adjacent differently oriented domains of the same Rh sample at the exactly same conditions. A catalytically active steady state, a catalytically inactive steady state and multifrequential oscillating states are simultaneously observed. Our results thus demonstrate the general possibility of multi-states in a catalytic reaction. This highly unusual behaviour is explained on the basis of peculiarities of the formation and depletion of subsurface oxygen on differently structured Rh surfaces. The experimental findings are supported by mean-field micro-kinetic modelling. The present observations raise the interdisciplinary question of how self-organising dynamic processes in a heterogeneous system are influenced by the permeability of the borders confining the adjacent regions., Catalytic reactions may exhibit oscillations in the reaction rate even at constant external parameters. Here, the authors observe and explain the coexistence of such oscillations and the steady states of catalytic activity in H2 oxidation on differently structured grains of a polycrystalline Rh foil.

Atomically thin transition-metal dichalcogenides (MoS2, WSe2, etc.) have long been touted as promising materials for gas detection because of their tunable band gaps; however, the sensing mechanism, based on a charge-transfer process, has not been fully explored. Here, we directly observe the effect of this charge transfer on the doping levels in MoS2 upon exposure to NOx by performing scanning photoelectron microscopy (SPEM) on a monolayer MoS2 transistor under bias conditions in a gas environment. By a comparison of the operando SPEM maps of the transistor with and without exposure to NOx gas, a downward shift in the Fermi level position could be detected, consistent with NOx gas making the MoS2 channel less n-type.

We performed spatially resolved near-ambient-pressure photoemission spectromicroscopy on graphene-coated copper in operando under oxidation conditions in an oxygen atmosphere (0.1 mbar). We investigated regions with bare copper and areas covered with mono- and bi-layer graphene flakes, in isobaric and isothermal experiments. The key method in this work is the combination of spatial and chemical resolution of the scanning photoemission microscope operating in a near-ambient-pressure environment, thus allowing us to overcome both the material and pressure gap typical of standard ultrahigh-vacuum X-ray photoelectron spectroscopy (XPS) and to observe in operando the protection mechanism of graphene toward copper oxidation. The ability to perform spatially resolved XPS and imaging at high pressure allows for the first time a unique characterization of the oxidation phenomenon by means of photoelectron spectromicroscopy, pushing the limits of this technique from fundamental studies to real materials under working conditions. Although bare Cu oxidizes naturally at room temperature, our results demonstrate that such a graphene coating acts as an effective barrier to prevent copper oxidation at high temperatures (over 300 °C), until oxygen intercalation beneath graphene starts from boundaries and defects. We also show that bilayer flakes can protect at even higher temperatures. The protected metallic substrate, therefore, does not suffer corrosion, preserving its metallic characteristic, making this coating appealing for any application in an aggressive atmospheric environment at high temperatures.

The non-IPR fulleride compound CsxC68 was investigated in analogy to previous experiments on CsxC58. While the vibrational properties as well as the electronic structure in the valence band range appear to be pretty similar to CsxC58, a striking difference could be observed by XPS and Photoemission Microscopy analysis: apparently, C68 forms different phases within a thick film including islands in which it is able to store more than 70 Cs atoms per fullerene cage and to keep these amounts even after annealing over 1100 K. This means that CsxC68 constitutes the highest alkali metal doping degree of any Fullerene species known so far. Spatially resolved photoemission analysis also revealed that the Cs-rich fulleride phases constitute a unique chemical state that has never been observed before.

The behavior of ultrathin layers of nickel (0.5 ≤ θNi ≤ 1.4 monolayers (ML)) on Rh(110) has been studied in oxidation/reduction experiments with O2 and H2 at T = 770 K. The reaction has been followed with Auger electron spectroscopy (AES), low-energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS) and scanning photoelectron microscopy (SPEM). The adsorption of oxygen leads to a large decrease (up to 90%) of the Ni signal in AES. Subsequent titration with hydrogen restores nearly the initial Ni signal. The peculiar behavior of Ni on Rh(110) upon O2 adsorption is attributed to a large nucleation barrier for Ni oxide formation on Rh(110). This barrier leads to the preferential formation of chemisorbed oxygen on Rh sites forcing Ni into subsurface sites. SPEM reveals that also small NiO particles with a diameter of ≈1 µm develop during O2 adsorption. For comparison, a Rh(110) surface with a thick Ni layer of an estimated thickness of about 8–9 ML has been prepared. On this thick Ni layer Ni oxide develops spontaneously during O2 adsorption in the in 10−6 mbar range at T = 770 K.

Graphene coating on the cobalt-chromium alloy was optimized and successfully carried out by a cold-wall chemical vapor deposition (CW-CVD) method. A uniform layer of graphene for a large area of the Co-Cr alloy (discs of 10 mm diameter) was confirmed by Raman mapping coated area and analyzing specific G and 2D bands, in particular, the intensity ratio and the number of layers were calculated. The effect of the CW-CVD process on the microstructure and the morphology of the Co-Cr surface was investigated by scanning X-ray photoelectron microscope (SPEM), atomic force microscopy (AFM), scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDS). Nanoindentation and scratch tests were performed to determine mechanical properties of Co-Cr disks. The results of microbiological tests indicate that the studied Co-Cr alloys covered with a graphene layer did not show a pro-coagulant effect. The obtained results confirm the possibility of using the developed coating method in medical applications, in particular in the field of cardiovascular diseases.

We present an in-depth analysis of the surface band alignment and local potential distribution of InP nanowires containing a p-n junction using scanning probe and photoelectron microscopy techniques. The depletion region is localized to a 15 nm thin surface region by scanning tunneling spectroscopy and an electronic shift of up to 0.5 eV between the n- A nd p-doped nanowire segments was observed and confirmed by Kelvin probe force microscopy. Scanning photoelectron microscopy then allowed us to measure the intrinsic chemical shift of the In 3d, In 4d, and P 2p core level spectra along the nanowire and the effect of operating the nanowire diode in forward and reverse bias on these shifts. Thanks to the high-resolution techniques utilized, we observe fluctuations in the potential and chemical energy of the surface along the nanowire in great detail, exposing the sensitive nature of nanodevices to small scale structural variations. (Less)

Renewed interest in the ferroelectric semi-conductor germanium telluride was recently triggered by the direct observation of a giant Rashba effect and a 30-year-old dream about a functional spin field-effect transistor. In this respect, all-electrical control of the spin texture in this material in combination with ferroelectric properties at the nanoscale would create advanced functionalities in spintronics and data information processing. Here, we investigate the atomic and electronic properties of GeTe bulk single crystals and their (111) surfaces. We succeeded in growing crystals possessing solely inversion domains of similar to 10 nm thickness parallel to each other. Using HAADF-TEM we observe two types of domain boundaries, one of them being similar in structure to the van der Waals gap in layered materials. This structure is responsible for the formation of surface domains with preferential Te-termination (similar to 68%) as we determined using photoelectron diffraction and XPS. The lateral dimensions of the surface domains are in the range of similar to 10-100 nm, and both Ge- and Te-terminations reveal no reconstruction. Using spin-ARPES we establish an intrinsic quantitative relationship between the spin polarization of pure bulk states and the relative contribution of different terminations, a result that is consistent with a reversal of the spin texture of the bulk Rashba bands for opposite configurations of the ferroelectric polarization within individual nanodomains. Our findings are important for potential applications of ferroelectric Rashba semiconductors in nonvolatile spintronic devices with advanced memory and computing capabilities at the nanoscale.

Adding submicrometer lateral resolution to the analytic capabilities of photoelectron spectroscopy was a milestone that opened up new opportunities to access lateral fluctuations in the chemical composition and electronic and magnetic structure of surfaces and interfaces and to explore exotic properties of nanostructured matter. To achieve a high spatial resolution while preserving the spectral resolution of this technique requires the very intense photon flux that has become available with the advent of third-generation synchrotron storage rings. The high spatial resolution of x-ray photoelectron microscopes, operated at synchrotron facilities, is achieved by either: (i) magnifying the image of the irradiated surface area using a suitable electron optical imaging system; or (ii) demagnifying the incident photon beam using x-ray photon optics. The contrast mechanisms in both instruments are based on photon absorption and the photon-induced electron emission is used to obtain spectroscopic information encoding the composition and electronic structure of the sample under investigation.

Performing electron based spectroscopies at ambient pressure environments, for instance, to investigate catalytic reactions, when the energy of the electrons is below 1.5 keV is extremely challenging. This limitation, known as the "pressure gap", was to some extent overcome about 15 years ago for X-ray photoelectron spectroscopy (XPS) experiments made at near ambient pressure, but only recently the first pioneering experiments at true ambient pressure with XPS have been realized. These investigations use graphene (Gr)-sealed cells to separate the ambient and vacuum environments by exploiting the properties of Gr to create a barrier for the transmission of liquids or gases and to be partially transparent to low energy photoelectrons. In such cells, the Gr membrane can be used as a bare substrate for other materials or can be an active part of a system. When nanoparticles are deposited or grown on the Gr membrane and exposed to an ambient pressure environment a raising question is if the areas of the nanoparticles directly in contact with Gr will experience the same environment conditions as the areas freely exposed to the atmospheric pressure. To answer to this question we have designed a pilot experiment where Ag nanoparticles are grown on one side of the Gr and ex-situ exposed to molecular oxygen to investigate the oxidation rate of the Ag atoms in contact with the Gr and those directly exposed to the oxygen molecules. Spatially resolved photoemission and high resolution scanning electron microscopy measurements have demonstrated that also the Ag atoms at the interface between Gr and Ag nanoparticles experiences the environment, showing, in our case, an oxidation comparable with that of the other areas of the nanoparticles. Graphical Abstract: [Figure not available: see fulltext.] © 2018, Springer Science+Business Media, LLC, part of Springer Nature.

For nanoparticles active for chemical and energy transformations in static liquid environment, chemistries of surface or near-surface regions of these catalyst nanoparticles in liquid are crucial for fundamentally understanding their catalytic performances at a molecular level. Compared to catalysis at a solid-gas interface, there is very limited information on the surface of these catalyst nanoparticles under a working condition or during catalysis in liquid. Photoelectron spectroscopy is a surface-sensitive technique; however, it is challenging to study the surfaces of catalyst nanoparticles dispersed in static liquid because of the short inelastic mean free path of photoelectrons traveling in liquid. Here, we report a method for tracking the surface of nanoparticles dispersed in static liquid by employing graphene layers as an electron-transparent membrane to separate the static liquid containing a solvent, catalyst nanoparticles, and reactants from the high-vacuum environment of photoelectron spectrometers. The surfaces of Ag nanoparticles dispersed in static liquid sealed in such a graphene membrane liquid cell were successfully characterized using a photoelectron spectrometer equipped with a high vacuum energy analyzer. With this method, the surface of catalyst nanoparticles dispersed in liquid during catalysis at a relatively high temperature up to 150 °C can be tracked with photoelectron spectroscopy.

Modern scanning photoemission microscopes use zone plates to de-magnify the X-ray beam to nanometer size allowing spatially resolved XPS analysis of materials relevant in nanotechnology. So far these microscopes have been designed to operate in the ultra-high or high vacuum environments as all XPS systems; but at the beginning of this century the dream of K. Siegbahn, the inventor of XPS, to use it in the near ambient or ambient pressure regimes became a reality. Despite the fast development and spread of these setups designed for not spatially resolved experiments, now available both as synchrotron and laboratory facilities, it took more than a decade before a similar result could be extended to photoemission microscopy. The scanning photoemission microscope at Elettra is the first instrument where near ambient pressure conditions for in operando analysis can be fulfilled. This paper shows some recent results obtained at this microscope at different sample environment conditions.

The complementary capabilities of the Scanning PhotoElectron Microscopes (SPEM) and X-ray PhotoEmission Electron Microscopes (XPEEM), operated at Elettra, in terms of imaging and micro-spectroscopy have opened unique opportunities to explore properties of functional materials as a function of their morphology and dimensions and to follow modifications in their properties during their operation. This paper describes the present performance of SPEMs and XPEEMs at Elettra, illustrated by selected recent studies relevant to graphene science. Ongoing efforts for implementing SPEM set-ups allowing for in-situ investigations under realistic operating conditions and PEEM set-up for spin-filtered momentum microscopy are outlined and discussed as well.

The relatively small size of thin (one or few layers) graphene flakes makes it extremely difficult to study the behavior of suspended graphene by characterization techniques other than the electron microscopies. Herein, we exploited the capability of spatially resolved photoemission in combination with high resolution transmission electron microscopy to investigate the interaction of thermally evaporated Pt atoms on suspended and supported graphene. Spectroscopic and microscopic analyses reveal that the nucleation of nanometersized Pt particles in these two regions exhibit different trends. While only small nanometer-sized islands are present on the supported graphene, relatively larger clusters of islands were also found on the suspended flakes. The X-ray photoemission C 1s core levels acquired after the Pt deposition show an increase in the number of vacancies in the graphene sheets.

Suspended graphene flakes are exposed simultaneously to fluorine and sulfur ions produced by the μ-wave plasma discharge of the SF 6 precursor gas. The microscopic and spectroscopic analyses, performed by Raman spectroscopy, scanning electron microscopy and photoelectron spectromicroscopy, show the homogeneity in functionalization yield over the graphene flakes with F and S atoms covalently bonded to the carbon lattice. This promising surface shows potential for several applications ranging from biomolecule immobilization to lithium battery and hydrogen storage devices. The present co-doping process is an optimal strategy to engineer the graphene surface with a concurrent hydrophobic character, thanks to the fluorine atoms, and a high affinity with metal nanoparticles due to the presence of sulfur atoms.