Surface etching by ion sputtering can be used to pattern surfaces. Recent studies using the high-spatial-resolution capability of the scanning tunnelling microscope revealed in fact that ion bombardment produces repetitive structures at nanometre scale, creating peculiar surface morphologies ranging from selfaffine patterns to 'fingerprint'-like and even regular structures, for instance waves (ripples), chequerboards or pyramids. The phenomenon is related to the interplay between ion erosion and diffusion of adatoms (vacancies), which induces surface re-organization. The paper reviews the use of sputter etching to modify 'in situ' surfaces and thin films, producing substrates with well defined vertical roughness, lateral periodicity and controlled step size and orientation.

No abstract

Successful attempts to deposit SMMs in UHV conditions\ud have been carried out with a tetranuclear iron(III) cluster [ 9 ]\ud and lanthanide bis-phthalocyaninato (LnPc 2 ) complexes. [ 10 , 11 ]\ud For the latter the seminal works of Ishikawa et al. [ 12 ] showed\ud that slow dynamics of the magnetization in these mononuclear\ud complexes is originated directly from their strong single ion\ud anisotropy. Very recently a structural and magnetic characterization\ud of a sub-monolayer deposit TbPc 2 based on synchrotronlight\ud techniques has confi rmed that this magnetic anisotropy is\ud retained on surface. [ 13 ] The absence of the observation of typical\ud slow dynamics of the magnetization has been attributed to the\ud long time-scale of the X-ray based experiments.\ud We report here a synchrotron-based investigation on neutral\ud TbPc 2 evaporated thick and thin fi lms evidencing that the thick\ud fi lm of TbPc 2 is characterized by slow relaxation of the magnetization\ud and opening of a butterfl y hysteresis cycle at temperatures\ud as high as 15 K but not observed for the thin fi lm. These\ud differences are accompanied with a drastic change in the orientation\ud of the TbPc 2 molecules in the two fi lm

Ship engines in the open ocean and Arctic typically combust heavy fuel oil (HFO), resulting in light-absorbing particulate matter (PM) emissions that have been attributed to black carbon (BC) and conventional, soluble brown carbon (brC). We show here that neither BC nor soluble brC is the major light-absorbing carbon (LAC) species in HFO-combustion PM. Instead, "tar brC" dominates. This tar brC, previously identified only in open-biomass-burning emissions, shares key defining properties with BC: it is insoluble, refractory, and substantially absorbs visible and near-infrared light. Relative to BC, tar brC has a higher Angstrom absorption exponent (AAE) (2.5-6, depending on the considered wavelengths), a moderately-high mass absorption efficiency (up to 50% of that of BC), and a lower ratio of sp 2-to sp 3-bonded carbon. Based on our results, we present a refined classification of atmospheric LAC into two sub-types of BC and two sub-types of brC. We apply this refined classification to demonstrate that common analytical techniques for BC must be interpreted with care when applied to tar-containing aerosols. The global significance of our results is indicated by field observations which suggest that tar brC already contributes to Arctic snow darkening, an effect which may be magnified over upcoming decades as Arctic shipping continues to intensify.

We show that dissociative oxygen adsorption on Ag͑001͒ induces below room temperature a missing row 2ͱ2ϫͱ2 reconstruction of the substrate. As demonstrated by the analysis of the photoelectron diffraction patterns, the oxygen atoms sit thereby in a c(2ϫ2) arrangement in the previous fourfold hollow sites nearly coplanar with the Ag atoms, while rows of substrate atoms are removed along the ͓100͔ directions. Annealing the crystal above 350 K restores the p(1ϫ1) symmetry and the oxygen moves to 0.6 Å above the fourfold hollow site. It becomes then more oxidic in nature, as demonstrated by the shift of the O 1s level from 530.3 eV to 528.3 eV. The phase transition affects also the O 2s and O 2p levels as well as the surface component of Ag 3d 5/2 . The vibrational frequency of the oxygen adatoms against the surface decreases at the phase transition, in accord with the larger adsorption distance. The higher temperature phase is active towards CO and C 2 H 4 oxidation, while the low-temperature phase is not. When cooling the sample below room temperature the reconstructed phase is restored. The time constant of this process as well as the chemical reactivity of the high-temperature phase are weakly reproducible since they depend on the previous history, i.e., presumably on the subsurface oxygen content of the sample.

We explore the effect of re-radiation in surface-enhanced Raman scattering (SERS) through polarization-sensitive experiments on self-organized gold nanowires on which randomly oriented Methylene Blue molecules are adsorbed. We provide the exact laws ruling the polarized, unpolarized, and parallel- and cross-polarized SERS intensity as a function of the field polarizations. We show that SERS is polarized along the wire-to-wire nanocavity axis, independently from the excitation polarization. This proves the selective enhancement of the Raman dipole component parallel to the nanocavity at the single molecule level. Introducing a field enhancement tensor to account for the anisotropic polarization response of the nanowires, we work out a model that correctly predicts the experimental results for any excitation/detection polarization and goes beyond the E(4) approximation. We also show how polarization-sensitive SERS experiments permit one to evaluate independently the excitation and the re-radiation enhancement factors accessing the orientation-averaged non-diagonal components of the molecular Raman polarizability tensor.

No abstract

Here we report the experimental observation of circular dichroism in the second-harmonic field (800-400 nm conversion) generated by self-organized gold nanowire arrays with subwavelength periodicity (160 nm). Such circular dichroism, raised by a nonlinear optical extrinsic chirality, is the evident signature of the sample morphology. It arises from the curvature of the self-assembled wires, producing a lack of symmetry at oblique incidence. The results were compared, both in the optical linear and nonlinear regime, with a reference sample composed of straight wires. Despite the weak extrinsic optical chirality of our samples (not observable by our optical linear measurements), high visibility (more than 50%) was obtained in the second-harmonic generated field.