Synchrotron radiation photoemission spectroscopy of the oxygen modified CrCl3 surface.

We investigate the experimentally challenging CrCl3 surface by photon energy dependent photoemission (PE). The core and valence electrons after cleavage of a single crystal, either in a ultra-high vacuum (UHV) or in air, are studied by keeping the samples at 150 °C, aiming at confirming the atomic composition with respect to the expected bulk atomic structure. A common spectroscopic denominator revealed by data is the presence of a stable, but only partially ordered Cl-O-Cr surface. The electronic core levels (Cl 2p, Cr 2p and 3p), the latter ones of cumbersome component determination, allowed us to quantify the electron charge transfer to the Cr atom as a net result of this modification and the increased exchange interaction between metal and ligand atoms. In particular, the analysis of multiplet components by the CMT4XPS code evidenced the charge transfer to be favored, and similarly the reduced crystal field due to the established polarization field. Though it is often claimed that a significant amount of Cl and Cr atomic vacancies has to be included, such a possibility can be excluded on the basis of the sign and the importance of the shift in the binding energy of core level electrons. The present methodological approach can be of great impact to quantify the structure of ordered sub-oxide phases occurring in mono or bi-layer Cr trihalides.

Mechanical exfoliation and layer number identification of single crystal monoclinic CrCl3.

After the recent finding that CrI3, displays ferromagnetic order down to its monolayer, extensive studies have followed to pursue new two-dimensional (2D) magnetic materials. In this article, we report on the growth of single crystal CrCl3 in the layered monoclinic phase. The system after mechanical exfoliation exhibits stability in ambient air (the degradation occurs on a time scale at least four orders of magnitude longer than is observed for CrI3). By means of mechanical cleavage and atomic force microscopy (AFM) combined with optical identification, we demonstrate the systematic isolation of single and few layer flakes onto 270 nm and 285 nm SiO2/Si (100) substrates with lateral size larger than graphene flakes isolated with the same method. The layer number identification has been carried with statistically significant data, quantifying the optical contrast as a function of the number of layers for up to six layers. Layer dependent optical contrast data have been fitted within the Fresnel equation formalism determining the real and imaginary part of the wavelength dependent refractive index of the material. A layer dependent (532 nm) micro-Raman study has been carried out down to two layers with no detectable spectral shifts as a function of the layer number and with respect to the bulk.

Effect of carrier tunneling on the structure of Si nanowires fabricated by metal assisted etching.

The metal assisted etching mechanism for Si nanowire fabrication, triggered by doping type and level and coupled with choice of metal catalyst, is still very poorly understood. We explain the different etching rates and porosities of wires we observe based on extensive experimental data, using a new empirical model we have developed. We establish as a key parameter, the tunneling through the space charge region (SCR) which is the result of the reduction of the SCR width by level of the Si wafer doping in the presence of the opposite biases of the p- and n-type wafers. This improved understanding should permit the fabrication of high quality wires with predesigned structural characteristics, which hitherto has not been possible.

Depth profiling of melting and metallization in Si(111) and Si(001) surfaces.

An original approach for measuring the depth profile of melting and metallization of the Si(111) and Si(001) surfaces is proposed and applied. The different probing depths of the Auger electron and electron energy loss (EELS) spectroscopies are exploited to study the number of molten and metallic layers within 5-30 Å from the surface up to about 1650 K. Melting is limited to 3 atomic layers in Si(001) in the range 1400-1650 K while the number of molten layers grows much faster (5 layers at about 1500 K) in Si(111) as also indicated by the L(3)-edge shift observed by EELS. The relationship between melting and metallization is briefly discussed.

Broadband optical ultrafast reflectivity of Si, Ge and GaAs.

Ultrafast optical reflectivity measurements of silicon, germanium, and gallium arsenide have been carried out using an advanced set-up providing intense subpicosecond pulses (35 fs FWHM, [Formula: see text] = 400 nm) as a pump and broadband 340-780 nm ultrafast pulses as a white supercontinuum probe. Measurements have been performed for selected pump fluence conditions below the damage thresholds, that were carefully characterized. The obtained fluence damage thresholds are 30, 20.8, 9.6 mJ/[Formula: see text] for Si, Ge and GaAs respectively. Ultrafast reflectivity patterns show clear differences in the Si, Ge, and GaAs trends both for the wavelength and time dependences. Important changes were observed near the wavelength regions corresponding to the [Formula: see text], [Formula: see text] singularities in the joint density of states, so related to the peculiar band structure of the three systems. For Ge, ultrafast reflectivity spectra were also collected at low temperature (down to 80 K) showing a shift of the characteristic doublet peak around 2.23 eV and a reduction of the recovery times.

Structural, electrical, electronic and optical properties of melanin films.

We present thick, uniform and rather flat melanin films obtained using spray deposition. The morphology of the films was investigated using Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM). Temperature-dependent electrical resistance of melanin thin films evidenced a semiconductor-like character and a hysteretic behavior linked to an irreversible process of water molecule desorption from the melanin film. X-ray Photoelectron Spectroscopy (XPS) was carried out to analyze the role of the functional groups in the primary and secondary structure of the macromolecule, showing that the contribution of the 5,6-dihydroxyindole-2-carboxylic acid (DHICA) subunit to the molecule is about 35%. Comparison of the optical absorption of the thick (800nm) and thin (80nm) films showed a spectral change when the thickness increases. From in vacuum photoconductivity (PC) measured at controlled temperatures, we suggest that the melanin films exhibit a possible charge transport mechanism by means of delocalized pi states along the stacked planar secondary structure.

Free electron laser-driven ultrafast rearrangement of the electronic structure in Ti.

High-energy density extreme ultraviolet radiation delivered by the FERMI seeded free-electron laser has been used to create an exotic nonequilibrium state of matter in a titanium sample characterized by a highly excited electron subsystem at temperatures in excess of 10 eV and a cold solid-density ion lattice. The obtained transient state has been investigated through ultrafast absorption spectroscopy across the Ti M2,3-edge revealing a drastic rearrangement of the sample electronic structure around the Fermi level occurring on a time scale of about 100 fs.

Visible light photoactivity of Polypropylene coated Nano-TiO2 for dyes degradation in water.

The use of Polypropylene as support material for nano-TiO2 photocatalyst in the photodegradation of Alizarin Red S in water solutions under the action of visible light was investigated. The optimization of TiO2 pastes preparation using two commercial TiO2, Aeroxide P-25 and Anatase, was performed and a green low-cost dip-coating procedure was developed. Scanning electron microscopy, Atomic Force Microscopy and X-Ray Diffraction analysis were used in order to obtain morphological and structural information of as-prepared TiO2 on support material. Equilibrium and kinetics aspects in the adsorption and successive photodegradation of Alizarin Red S, as reference dye, are described using polypropylene-TiO2 films in the Visible/TiO2/water reactor showing efficient dyes degradation.

Reflectivity enhancement in titanium by ultrafast XUV irradiation.

The study of highly photo-excited matter at solid state density is an emerging field of research, which is benefitting the development of free-electron-laser (FEL) technology. We report an extreme ultraviolet (XUV) reflectivity experiment from a titanium (Ti) sample irradiated with ultrafast seeded FEL pulses at variable incident photon fluence and frequency. Using a Drude formalism we relate the observed increase in reflectivity as a function of the excitation fluence to an increase in the plasma frequency, which allows us to estimate the free electron density in the excited sample. The extreme simplicity of the experimental setup makes the present approach potentially a valuable complementary tool to determine the average ionization state of the excited sample, information of primary relevance for understanding the physics of matter under extreme conditions.

Magnetic properties of ultrathin Ni81Fe19 films with Ta and Ru capping layers.

Magnetic properties of Ni81Fe19 (permalloy) ultrathin films with Ru and Ta capping layers (CLs) were investigated for applications to magnetic random access memory units (MRAM). The sample structure, which simulated an MRAM free layer, is Si- sub./SiO2/Ni81Fe19/Ru(Ta). The Ni81Fe19 thin films less than 3 nm thick with Ru CL show low coercive fields compared with the Ta capping layer. Both systems showed loss of momentum equivalent to magnetically dead layers of thickness (δ) ~0.6 nm for Ru cap layer and ~1.4 nm for Ta cap layer, respectively. Moreover, after annealing the thicknesses are slightly increased to an equivalent magnetic dead layer thickness of δ ~0:84 nm and ~1.80 nm for Ru and Ta CL, respectively. Our calculations showed that the presence of only 11% Ta concentration at the interface reduced the Ni momentum to zero, with the Ni­Ta coupling being anti-ferromagnetic; while 50% Ru intermixing at the interface reduced the Ni momentum to zero with the coupling between Ru and Ni being ferromagnetic. To find out more about the intermixing at the interface, the composition and chemical states were characterized by the x-ray photoelectron spectroscopy and peak decomposition technique. The result showed that the peak positions were different from the pure metallic case at the interface region, mainly because of the intermixing between two layers. In conclusion, the Ru capping layer might be important for MRAM use in terms of low coercive field and small δ layer thickness if compared with the Ta capping layer.

Control of structural, electronic, and optical properties of eumelanin films by electrospray deposition.

The capability to monitor finely the physical properties of eumelanin, an important class of biopolymers, involved in melanoma cancer pathologies, whose function and intrinsic disorder still collects the interest of many investigators, was achieved by means of electrospray deposition (ESD). By alleviating the problem of the solubility of melanin through the realization of high-quality films it was possible to spread light on the unknown biopolymer supramolecular organization. In fact, on the basis of scanning probe microscopies, electron spectroscopies, and transport properties, it was possible to delineate peculiar features of the melanin organization varying from heteropolymeric to oligomeric in character and eventually turning in a cross-linked secondary molecular structure.

Localization of the dopant in Ge:Mn diluted magnetic semiconductors by x-ray absorption at the Mn K edge.

A unitary picture of the structural properties of Mn(x)Ge(1-x) diluted alloys fabricated by either ion implantation or molecular beam epitaxy (MBE), at various growth temperatures (from 80 to about 623 K) and few per cent concentrations, is proposed. Analysis is based on synchrotron radiation x-ray absorption spectroscopy at the Mn K edge. When the growth temperature exceeds 330 K, the MBE samples show a high number of precipitated ferromagnetic nanoparticles, mainly Mn(5)Ge(3), nucleated from the previous occupation of interstitial tetrahedral sites. Efficient substitution is observed in the case of MBE samples made by alternate layers of GeMn alloys grown at T ≤ 433 K and undoped Ge thick layers. Similar good dilution properties are obtained by implanting Mn ions at low temperatures (80 K). Possible precursors to preferential mechanisms in the alloy formation are discussed on the basis of the present comparative study.