Near-field imaging of surface-plasmon vortex-modes around a single elliptical nanohole in a gold film

We present scanning near-field images of surface plasmon modes around a single elliptical nanohole in 88 nm thick Au film. We find that rotating surface plasmon vortex modes carrying extrinsic orbital angular momentum can be induced under linearly polarized illumination. The vortex modes are obtained only when the incident polarization direction differs from one of the ellipse axes. Such a direct observation of the vortex modes is possible thanks to the ability of the SNOM technique to obtain information on both the amplitude and the phase of the near field. The presence of the vortex mode is determined by the rotational symmetry breaking of the system and it can be considered the counterpart of the photonic spin Hall effect. Finite element method calculations show that such a vorticity originates from the presence of nodal points where the phase of the field is undefined, leading to a circulation of the energy flow. The configuration producing vortex modes corresponds to a nonzero total topological charge (+1)

Optical emission spectroscopy study of the expansion dynamics of a laser generated plasma during the deposition of thin films by laser ablation

The dynamics of the expanding plasma produced by excimer laser ablation of different materials such as silicon, silicon carbide, graphite and tin powder were studied by means of time integrated, spatially resolved emission spectroscopy and fast photography imaging of the expanding plasma. Experiments were performed both in vacuum and in different pure background atmosphere (i.e. oxygen or nitrogen) and, finally, in gaseous mixtures (i.e. in O2/Ar and N2/Ar mixtures). These investigations were performed to gather information on the nature of the chemical species present in the plasma and on the occurrence of chemical reactions during the interaction between the plasma and the background gas. Then, we tried to correlate the plasma expansion dynamics to the structural and physical properties of the deposited materials. Experimental results clearly indicate that there is a strong correlation between the plasma expansion dynamics and the structural properties of the deposited thin films. In this respect, the investigations performed by means of fast photography and of optical emission spectroscopy revealed themselves as powerful tools for an efficient control of the deposition process itself

Time resolved imaging studies of the plasma produced by laser ablation of silicon in O2/Ar atmosphere

The dynamics of the expansion plasma produced by excimer laser ablation of a silicon target into oxygen and mixed O2/Ar atmosphere were studied by means of time-resolved imaging of the expanding plume. Experiments were performed in pure oxygen, ranging between 0.13 and 13.33 Pa, and at different O2/Ar ratios at a fixed total pressure of 13.33 Pa. The occurrence of a shock wave (SW) generated by the supersonic expansion of the plasma was observed at high pressure values. The presence of the SW had a strong influence on the structure of SiOx thin films. In fact, silicon dioxide thin films were always obtained in presence of the SW, irrespective of the oxygen content in the gaseous mixture. On the contrary, suboxide thin films were obtained when the expansion occurred at lower pressure values (no SW presence). The temperature rise following the developing of the SW, is supposed to enhance the oxygen molecules dissociation by increasing the efficiency of the silicon oxidation reaction

Surface-enhanced Raman scattering of SnO2_{2} bulk material and colloidal solutions

Surface enhanced Raman scattering (SERS) effects on tin dioxide in the form of bulk material, nanostructured thin films and colloidal solutions were investigated. Raman spectra are characterized by the three Raman scattering peaks at 478, 633, and 776 \invcm, assigned to the E$_g$, A$_{1g}$ and B$_{2g}$ modes, typical of rutile SnO$_2$. In presence of the silver nanoparticles, in addition to the enhancement intensity of some of the fundamental tin dioxide rutile Raman features, the appearance of a new Raman scattering peak at about 600 cm$^{-1}$ is observed. This spectral features is observed, in presence of silver nanoparticles, also in other SnO$_2$ based system such as pulsed laser deposited thin films, with different stoichiometry, and in water colloidal solutions. The observed SERS effects are explained in terms of electric-field gradient mechanism that are generated near a metal surface. In particular, the appearance of a peak near 600 \invcm is attributed to the Raman activation of the infrared E$_u$ transverse optical (TO) mode.Comment: 7 pages, 6 figure

Metal Nanoparticles Deposited on Porous Silicon Templates as Novel Substrates for SERS

In this paper, results on preparation of stable and uniform SERS solid substrates using macroporous silicon (pSi) with deposited silver and gold are presented. Macroporous silicon is produced by anodisation of p-type silicon in hydrofluoric acid. The as prepared pSi is then used as a template for Ag and Au depositions. The noble metals were deposited in three different ways: by immersion in silver nitrate solution, by drop-casting silver colloidal solution and by pulsed laser ablation (PLA). Substrates obtained by different deposition processes were evaluated for SERS efficiency using methylene blue (MB) and rhodamine 6G (R6G) at 514.5, 633 and 785 nm. Using 514.5 nm excitation and R6G the limits of detection (LOD) for macroporous Si samples with noble metal nanostructures obtained by immersion of pSi sample in silver nitrate solution and by applying silver colloidal solution to pSi template were 10–9 M and 10–8 M respectively. Using 633 nm laser and MB the most noticeable SERS activity gave pSi samples ablated with 30000 and 45000 laser pulses where the LODs of 10–10 M were obtained. The detection limit of 10–10 M was also reached for 4 mA cm–2-15 min pSi sample, silver ablated with 30000 pulses. Macroporous silicon proved to be a good base for the preparation of SERS substrates

Correlating topography and viscoelastic properties of Elastin-Like Polypeptide scaffolds probed at the nanoscale: Intermodulation Atomic Force Microscopy

The synthesis and property characterization of soft biomaterials has taken precedence in recent years. Although bulk physical-chemical properties are well known for these bio-materials, nanoscale properties still need to be probed and evaluated to fine tune the bio-compatibility (structural as well as functional) with natural tissues for regenerative medicine, prosthetics and other biological applications. In this study, we focus on a popular soft biomaterial, ELastin-like polypeptide (ELP) which has been prepared under different pH conditions. We explore the topographical features of the ELP at the nanoscale using Atomic Force Microscopy (AFM). Additionally, we employ a non linear mode of AFM called Intermodulation-AFM (ImAFM) to correlate the elastic properties (Young\u27s modulus) of ELP probed at the nanoscale with the topographical features which gives us a deep insight into the mechanical properties offered by ELP when the structural features are altered by change in the ELP synthesis conditions. The noteworthy point is that we measure theses properties at a spatial resolution of 0.9 nm. Finally, we explain the change in the structural features of ELP with varying pH through atomistic Molecular Dynamics Simulations. We follow the interaction mechanisms of the amino acid sequences and crosslinkers with proteins as they form the backbone and sidechain of the ELP at different pH

SERS detection and DFT calculation of 2-naphthalene thiol adsorbed on Ag and Au probes

Two different surface enhanced Raman scattering (SERS) sensors are described, tested and compared against the detection of 2-naphthalenethiol (2NPT, a volatile compound) in both solution state as well as vapor phase. The first sensor is based on an optical fiber properly modeled to induce the adhesion of colloidal Ag nanoparticles on its surface. Excitation and detection of the Raman signal is performed through the optical fiber that can be used as in situ probe for the detection of molecules adsorbed on the SERS sensitized surface. The second SERS sensor is based on nanostructured substrates consisting of Au nanoparticles produced by pulsed laser deposition in presence of a controlled Ar atmosphere. Details at the nanometer scale were observed by SEM and TEM imaging to understand the size and structure of the islands formed as a function of deposition parameters that were selected in order to maximize their SERS response. The sensitivity of the substrates to volatile species was tested by letting evaporate controlled drops of a methanol solution of 2NPT in a chamber of known volume, where the substrate was placed. After complete evaporation of the drops, this provided an in-situ environment suitable for vapor phase measurements at known concentration. SERS spectra were collected after exposing the substrates to the environment within the chamber (vapor phase measurements) or dipping them in a solution for condensed state measurements. The complete absence of the SH stretching peak in the SERS spectra proves the covalent bonding of 2NPT to the metal substrates via the sulfur atom. DFT calculations, including metal-sulfur interaction, provide a good description of the observed SERS spectra. The reported data allow concluding that our SERS substrates are suitable for detection of volatile compounds

SERS and DFT study of indigo adsorbed on silver nanostructured surface

Surface-enhanced Raman spectroscopy has emerged as a widely used tool in the identification of organic dyes in works of art. Indigo is among the most used organic pigment, its identification can therefore give important information about the provenience and the making of the investigated work of art. In this work, we combine Surface Enhanced Raman Spectroscopy (SERS) experiments with density functional theory (DFT) computations of the Raman frequencies of indigo and an indigo molecule adsorbed onto a silver surface made of 16 silver atoms. The SERS spectrum of a molecule adsorbed on a metallic surface, in fact, can differ from the corresponding Raman one. The knowledge and the comprehension of the SERS spectrum then are mandatory in dyes identification. Experimental SERS spectra were acquired using ad hoc SERS active substrates consisting of pulsed laser ablated silver nanoparticles deposited onto a polishing sheet. The polishing sheet surface roughness is able to remove some pigments grains from the surface of a work of art without damage. DFT calculations provide a good description of the observed SERS spectra, in particular, the indigo-Ag16 structure gives a better description with respect to structures where only one or two silver atoms attached to the indigo molecule are considered