Investigating the activation of passive metals by a combined in-situ AFM and Raman spectroscopy system: a focus on titanium.

Understanding the main steps involved in the activation of passive metals is an extremely important subject in the mechanical and energy industry and generally in surface science. The titanium-H2SO4 system is particularly useful for this purpose, as the metal can either passivate or corrode depending on potential. Although several studies tried to hypothesise the surface state of the electrode, there is no general consensus about the surface state of Ti in the active-passive transition region. Here by combining in-situ atomic force microscopy (AFM) and Raman spectroscopy, operating in an electrochemical cell, we show that the cathodic electrification of Ti electrodes causes the dissolution of the upper TiO2 portion of the passive film leaving the electrode covered by only a thin layer of titanium monoxide. Fast anodic reactions involved the acidification of the solution and accumulation of sulphur containing anions. This produces a local increase of the solution turbidity, allowing to distinguish favourable regions for the precipitation of TiOSO4·2H2O. These results give a clear answer to the long-stated question of the physical origin behind the formation of negative polarization resistances, sometimes occurring in corroding systems, and a rationale about the proton-induced degradation of passive surfaces in presence of sulphur containing species.

Modification of large area Cu2O/CuO photocathode with CuS non-noble catalyst for improved photocurrent and stability.

In this work, a three-layered heterostructure Cu2O/CuO/CuS was obtained through a low-cost and large-area fabrication route comprising electrodeposition, thermal oxidation, and reactive annealing in a sulfur atmosphere. Morphological, microstructural, and compositional analysis (AFM, SEM, XRD, EDS, XPS) were carried out to highlight the surface modification of cuprous oxide film after oxidation and subsequent sulfurization. Impedance, voltammetric, and amperometric photoelectrochemical tests were performed on Cu2O, Cu2O/CuO, and Cu2O/CuO/CuS photocathodes in a sodium sulfate solution (pH 5), under 100 mW cm-2 AM 1.5 G illumination. A progressive improvement in terms of photocurrent and stability was observed after oxidation and sulfurization treatments, reaching a maximum of - 1.38 mA cm-2 at 0 V versus RHE for the CuS-modified Cu2O/CuO electrode, corresponding to a ~ 30% improvement. The feasibility of the proposed method was demonstrated through the fabrication of a large area photoelectrode of 10 cm2, showing no significant differences in characteristics if compared to a small area photoelectrode of 1 cm2.

Anion intercalated graphite: a combined electrochemical and tribological investigation by in situ AFM.

The intercalation of graphite by electrochemical methods is an efficient strategy to produce massive graphene flakes. In fact, when graphite is biased inside an acidic solution, anions enter inside the stratified structure of the electrode and reduce the layer-to-layer interaction. Consequently, a gentle sonication is sufficient to disperse the graphene flakes inside the electrolyte. In view of an optimisation of the production protocol, a detailed analysis of the intercalation mechanism at the molecular length scale is mandatory. In the last 30 years, electrochemical (EC) scanning probe microscopies (e.g. EC-STM and in situ AFM) have been widely exploited in this research topic. In fact, these techniques have the possibility of combining the EC characterisation (e.g. cyclic-voltammetry, CV) with mechanical characterisation (e.g. adhesion and friction) and topography acquisition with high (molecular) lateral resolution. In this work, we investigate the tribological properties of the basal surface of graphite before and after the anion intercalation. By comparing the results acquired after the extraction of the graphite electrode from the EC cell with those collected inside the EC cell during the CV by an in situ AFM, we show how some features deriving from anisotropic friction can be exploited to unveil the very early stage of graphite exfoliation.

Temporal analysis of blister evolution during anion intercalation in graphite.

In the currently accepted picture, when graphite is immersed and polarized in a diluted sulfuric acid electrolyte, the surface undergoes an invasive process due to the intercalation of solvated sulphate anions inside the crystal. The following evolution of CO, CO2 and O2 promotes the surface swelling and the growth of blisters. Here, we give evidence that the appearance of blisters affects the graphite surface as soon as the oxygen potential is reached, i.e. before the traditionally accepted anion intercalation stage, which instead is demonstrated slowing the blister development. These results suggest a new picture of the solvated anion intercalation in graphite with respect to the current interpretative model.

Spin polarized surface resonance bands in single layer Bi on Ge(1 1 1).

The spin features of surface resonance bands in single layer Bi on Ge(1 1 1) are studied by means of spin- and angle-resolved photoemission spectroscopy and inverse photoemission spectroscopy. We characterize the occupied and empty surface states of Ge(1 1 1) and show that the deposition of one monolayer of Bi on Ge(1 1 1) leads to the appearance of spin-polarized surface resonance bands. In particular, the C 3v symmetry, which Bi adatoms adopt on Ge(1 1 1), allows for the presence of Rashba-like occupied and unoccupied electronic states around the [Formula: see text] point of the Bi surface Brillouin zone with a giant spin-orbit constant [Formula: see text] eV · Å.

Electron spectroscopy investigation of the oxidation of ultra-thin films of Ni and Cr on Fe(0 0 1).

We investigated the room temperature oxidation of ultra-thin Ni and Cr films grown on Fe(0 0 1). In particular, we characterized the degree of crystallinity and the stoichiometry of the oxide layers and addressed the chemical stability of the interface with the highly reactive Fe substrate by means of low-energy electron diffraction and x-ray and UV photoemission spectroscopy. In the Ni case we detected, upon oxidation, the formation of a Fe(3)O(4) layer covering the Ni oxide, due to the diffusion of Fe cations towards the surface. At high temperature and in ultra-high vacuum conditions, the Ni oxide dissolved and the Fe oxide layer was reduced to FeO. In the Cr case, we observed the formation of a thin Cr(2)O(3) oxide layer, showing a diffraction pattern compatible with a defective γ-Cr(2)O(3) phase. A thicker Cr oxide layer could be produced by oxidizing the sample at 300 °C, at the expense of the incorporation of trace amounts of Fe cations.

Enhanced atom mobility on the surface of a metastable film.

A remarkable enhancement of atomic diffusion is highlighted by scanning tunneling microscopy performed on ultrathin metastable body-centered tetragonal Co films grown on Fe(001). The films follow a nearly perfect layer-by-layer growth mode with a saturation island density strongly dependent on the layer on which the nucleation occurs, indicating a lowering of the diffusion barrier. Density functional theory calculations reveal that this phenomenon is driven by the increasing capability of the film to accommodate large deformations as the thickness approaches the limit at which a structural transition occurs. These results disclose the possibility of tuning surface diffusion dynamics and controlling cluster nucleation and self-organization.

Direct observation of spin-resolved full and empty electron states in ferromagnetic surfaces.

We present a versatile apparatus for the study of ferromagnetic surfaces, which combines spin-polarized photoemission and inverse photoemission spectroscopies. Samples can be grown by molecular beam epitaxy and analyzed in situ. Spin-resolved photoemission spectroscopy analysis is done with a hemispherical electron analyzer coupled to a 25 kV-Mott detector. Inverse photoemission spectroscopy experiments are performed with GaAs crystals as spin-polarized electron sources and a UV bandpass photon detector. As an example, measurements on the oxygen passivated Fe(100)-p(1×1)O surface are presented.

Confinement effects in π-bonded chains at group IV semiconductor (111) surfaces.

The degree of 1D character of surface chains at group IV (111)-2 × 1 reconstructed surfaces is established by surface sensitive optical spectroscopy. Optical experiments on a diamond C(111)-2 × 1 surface show that the absorption peak related to dangling-bond transitions exhibits a marked blueshift upon oxygen exposure of the clean surface. Such behaviour is analogous to that observed on a clean Si(111)-2 × 1 surface. For both surfaces the experimental finding is interpreted in terms of quantum confinement of surface electrons in quasi-one-dimensional π-bonded chains, whose length decreases with oxygen uptake. A different behaviour is observed in Ge(111)-2 × 1, where only a very slight blueshift of the surface-state optical transition is detected upon oxidation. The almost negligible blueshift in Ge(111)-2 × 1 is consistent with a significant coupling between the π-bonded chains resulting in a much less pronounced one-dimensional character of Ge(111)-2 × 1 surface electrons compared to diamond and silicon reconstructed surfaces.

X-ray photoemission spectroscopy investigation of the interaction between 4-mercaptopyridine and the anatase TiO2 surface.

In polymer-metal oxide hybrid solar cells, an extremely careful engineering of the interface is required to ensure good device performances. Recently, very promising results have been obtained by functionalizing titanium dioxide (TiO2) by means of 4-mercaptopyridine (4-MPy) molecules, showing the beneficial effect of these molecules on the interface morphology. This study investigates the nature of the interaction of 4-MPy molecules with the TiO2 surface by means of X-ray photoemission spectroscopy. In order to mimic the device processing conditions, our analysis is carried out on molecules adsorbed from solution on a nanocrystalline surface. According to our analysis, 4-MPy molecules (C5H5NS) are likely bound with the oxide through the nitrogen atom. The bonding precedes either via a covalent interaction with Lewis surface sites, or via hydrogen mediation, possibly in the form of hydrogen bonds. Interestingly, in the latter case, we also observe strong changes in the spectroscopic features attributed to the thiol group.

Charge transfer between isomer domains on n+-doped Si(111)-2 × 1: energetic stabilization.

Domains of different surface reconstruction-negatively or positively buckled isomers-have been previously observed on highly n-doped Si(111)-2 × 1 surfaces by angle-resolved ultraviolet photoemission spectroscopy and scanning tunneling microscopy/spectroscopy. At low temperature, separate domains of the two isomer types are apparent in the data. It was argued in the previous work that the negative isomers have a lower energy of their empty surface states than the positive isomers, providing a driving force for the formation of the negative isomers. In this work we show that the relative abundance of these two isomers shows considerable variation from sample to sample, and it is argued that the size of the isomer domains is likely to be related to this variation. A model is introduced in which the electrostatic effect of charge transfer between the domains is computed, yielding total energy differences between the two types of isomer. It is found that the transfer of electrons from domains of positive isomers to negative ones leads to an energetic stabilization of the negative isomers. The model predicts a dependence of the isomer populations on doping that is in agreement with most experimental results. Furthermore, it accounts, at least qualitatively, for the marked lineshape variation from sample to sample observed in photoemission spectra.

Coexistence of negatively and positively buckled isomers on n+-doped Si(111) − 2 × 1.

A long-standing puzzle regarding the Si(111) − 2 × 1 surface has been solved. The surface energy gap previously determined by photoemission on heavily n-doped crystals was not compatible with a strongly bound exciton known from other considerations to exist. New low-temperature angle-resolved photoemission and scanning tunneling microscopy data, together with theory, unambiguously reveal that isomers with opposite bucklings and different energy gaps coexist on such surfaces. The subtle energetics between the isomers, dependent on doping, leads to a reconciliation of all previous results.

Growth-related properties and postgrowth phenomena in organic molecular thin films.

The problem of monitoring the structural and morphological evolutions of thin films of organic molecular materials during their growth by organic molecular beam epitaxy and in the postgrowth stage is addressed here by a combination of in situ optical reflectance anisotropy measurements, ex situ optical and morphological investigations, and theoretical simulation of the material optical response. For alpha-quaterthiophene, a representative material in the class of organic molecular semiconductors, the results show that molecules crystallize in the first stage of growth in metastable structures, even when deposition is carried out at room temperature. In the postdeposition stage, the film structure evolves within a few days to the known equilibrium structure of the low temperature polymorph. When deposition is carried out at low substrate temperatures, an evolution of the film morphology is also demonstrated.