Margarita Hernández

Silver substrates for surface enhanced Raman scattering: Correlation between nanostructure and Raman scattering enhancement

The fabrication of substrates for Surface Enhanced Raman Scattering (SERS) applications matching the needs for high sensitive and reproducible sensors remains a major scientific and technological issue. We correlate the morphological parameters of silver (Ag) nanostructured thin films prepared by sputter deposition on flat silicon (Si) substrates with their SERS activity. A maximum enhancement of the SERS signal has been found at the Ag percolation threshold, leading to the detection of thiophenol, a non-resonant Raman probe, at concentrations as low as 10−10M, which corresponds to enhancement factors higher than 7 orders of magnitude. To gain full control over the developed nanostructure, we employed the combination of in-situ time-resolved microfocus Grazing Incidence Small Angle X-ray Scattering with sputter deposition. This enables to achieve a deepened understanding of the different growth regimes of Ag. Thereby an improved tailoring of the thin film nanostructure for SERS applications can be realized.

Assessment of femtosecond laser induced periodic surface structures on polymer films

In this work we present the formation of laser induced periodic surface structures (LIPSS) on spin-coated thin films of several model aromatic polymers including poly(ethylene terephthalate), poly(trimethylene terephthalate) and poly carbonate bis-phenol A upon irradiation with femtosecond pulses of 795 and 265 nm at fluences well below the ablation threshold. LIPSS are formed with period lengths similar to the laser wavelength and parallel to the direction of the laser polarization vector. Formation of LIPSS upon IR irradiation at 795 nm, a wavelength at which the polymers absorb weakly, contrasts with the absence of LIPSS in this spectral range upon irradiation with nanosecond pulses. Real and reciprocal space characterization of LIPSS obtained by Atomic Force Microscopy (AFM) and Grazing Incidence Small Angle X-ray Scattering (GISAXS), respectively, yields well correlated morphological information. Comparison of experimental and simulated GISAXS patterns suggests that LIPSS can be suitably described considering a quasi-one-dimensional paracrystalline lattice and that irradiation parameters have an influence on the order of such a lattice. Fluorescence measurements, after laser irradiation, provide indirect information about dynamics and structure of the polymer at the molecular level. Our results indicate that the LIPSS are formed by interference of the incident and surface scattered waves. As a result of this process, heating of the polymer surface above its glass transition temperature takes place enabling LIPSS formation.

NDE ultrasonic methods to characterise the porosity of mortar

Premature damage of mortar and concrete structures, due to environmental action, demands procedures to estimate durability of this type of components. Mortar or concrete composition (e.g. grain size, type and percentage of sand) may have some influence in the durability, but it is mainly related to porosity, which determines the interaction between aggressive agents and material. In this work, several IDE ultrasonic methods to estimate porosity of mortar are presented and evaluated. In these methods, porosity is related to (1) the material structural noise, (2) sound velocity and (3) ultrasonic attenuation. In all these methods, mortar is consider to be formed by only two phases: solid and pores.

Ion migration assisted inscription of high refractive index contrast waveguides by femtosecond laser pulses in phosphate glass

In this Letter, we report on the successful fabrication of low loss, high refractive index contrast waveguides via ion migration upon femtosecond laser writing in phosphate glass. Waveguides were produced in two different phosphate glass compositions with high and low La(2)O(3) content. In the La-rich glass, a large refractive index increase in the guiding region was observed due to the incoming migration of La accompanied by the out-diffusion of K. The much smaller refractive index change in the La-less glass is caused by rearrangements of the glass structure. These results confirm the feasibility of adapting the glass composition for enabling the laser writing of high refractive index contrast structures via spatially selective modification of the glass composition.

Application of micromechanics to the characterization of mortar by ultrasound.

Mechanical properties of concrete and mortar structures can be estimated by ultrasonic non-destructive testing. When the ultrasonic velocity is known, there are standardized methods based on considering the concrete a homogeneous material. Cement composites, however, are heterogeneous and porous, and have a negative effect on the mechanical properties of structures. This work studies the impact of porosity on mechanical properties by considering concrete a multiphase material. A micromechanical model is applied in which the material is considered to consist of two phases: a solid matrix and pores. From this method, a set of expressions is obtained that relates the acoustic velocity and Youngs modulus of mortar. Experimental work is based on non-destructive and destructive procedures over mortar samples whose porosity is varied. A comparison is drawn between micromechanical and standard methods, showing positive results for the method here proposed.

Role of ion migrations in ultrafast laser written tellurite glass waveguides

We report on a strong cross migration of ions in a Tellurite (Te) based glass to form waveguides using a high repetition rate femtosecond laser. The tellurite glass matrix was modified using oxides of P, Na and Zn elements of which Te and Na ions play an important role to form waveguides upon laser irradiation. Tellurium was observed to migrate causing a positive index change zone whereas sodium cross migrates to the tellurium deficient zone forming a relatively low index change region. We have used micro-Raman analysis to scan across the waveguide cross-section to understand the state of the glass network and the relation between ion migration and glass densification for waveguiding. We have found that there is an increase in TeO3 units and reduction of TeO4 units in the Te rich zones enabling densification. This work will help guide the new commercial glass manufacturing industries that aim at producing mid-infrared transparent glasses like tellurite, tellurides and chalcogenides for the production of waveguide based devices.

Surface enhanced fluorescence of anti-tumoral drug emodin adsorbed on silver nanoparticles and loaded on porous silicon

Fluorescence spectra of anti-tumoral drug emodin loaded on nanostructured porous silicon have been recorded. The use of colloidal nanoparticles allowed embedding of the drug without previous porous silicon functionalization and leads to the observation of an enhancement of fluorescence of the drug. Mean pore size of porous silicon matrices was 60 nm, while silver nanoparticles mean diameter was 50 nm. Atmospheric and vacuum conditions at room temperature were used to infiltrate emodin-silver nanoparticles complexes into porous silicon matrices. The drug was loaded after adsorption on metal surface, alone, and bound to bovine serum albumin. Methanol and water were used as solvents. Spectra with 1 μm spatial resolution of cross-section of porous silicon layers were recorded to observe the penetration of the drug. A maximum fluorescence enhancement factor of 24 was obtained when protein was loaded bound to albumin, and atmospheric conditions of inclusion were used. A better penetration was obtained using methanol as solvent when comparing with water. Complexes of emodin remain loaded for 30 days after preparation without an apparent degradation of the drug, although a decrease in the enhancement factor is observed. The study reported here constitutes the basis for designing a new drug delivery system with future applications in medicine and pharmacy.

Gold coatings on polymer laser induced periodic surface structures: assessment as substrates for surface-enhanced Raman scattering

We report on the fabrication of gold coated nanostructured polymer thin films and on their characterization as substrates for surface enhanced Raman spectroscopy (SERS). Laser induced periodic surface structures (LIPSS) were obtained on thin polymer films of poly(trimethylene terephthalate) (PTT) upon laser irradiation with the fourth harmonic of a Nd:YAG laser (266 nm, pulse duration 6 ns) resulting in a period close to the incident wavelength. The nanostructured polymer substrates were coated with a nanoparticle assembled gold layer by pulsed laser deposition using the fifth harmonic of a Nd:YAG laser (213 nm, pulse duration 15 ns). Different deposition times resulted in thicknesses from a few nanometres up to several tens of nanometres. Analysis by atomic force microscopy and grazing incident small angle X-ray scattering showed that gold coating preserved the LIPSS relief. The capabilities of the produced nanostructures as substrates for SERS have been investigated using benzenethiol as a test molecule. The SERS signal is substantially larger than that observed for a gold-coated flat substrate. Advantages of this new type of SERS substrates are discussed.

On the measurement of frequency-dependent ultrasonic attenuation in strongly heterogeneous materials

This paper deals with the measurement of frequency-dependent ultrasonic attenuation in strongly heterogeneous materials, such as cementitious materials. To improve the measurement of this parameter on this kind of materials, a linear swept-frequency signal is used to drive an emitter transducer to conduct a through-transmission inspection in immersion. To filter out undesirable frequency content, time-frequency filtering and detection process are performed. The use of this method has been compared with two excitation techniques, the broadband and the narrowband pulses. The results obtained using the swept-frequency excitation together with the time-frequency filtering, allows the determination of the attenuation curves with high accuracy over a wide frequency range without the need for complicated equipment, and improves the effective bandwidth by using a unique pair of transducers.

Ultrasonic wave propagation in cementitious materials: a multiphase approach of a self-consistent multiple scattering model.

This paper examines ultrasonic wave propagation through strongly heterogeneous materials such as cementitious materials, and deals meanly with the formulation of a multiphase approach of a self-consistent multiple scattering model, the so-called dynamic generalized self-consistent model (DGSCM) proposed by Yang [J. Appl. Mech. 70(2003) 575-582]. This extended model can describe the influence of the size and volume fraction of aggregates on cementitious materials, as well as the interaction, contribution, and influence of entrapped air voids together with the aggregates on frequency-dependent parameters such as the phase velocity and the attenuation coefficient. To show the performance of this approach, theoretical predictions were compared with experimental ultrasonic measurements over a wide frequency range from several mortar specimens with different features in their microstructure properties and concentrations of aggregates up to 60%. The multiphase approaches of both the DGSCM and the Waterman-Truell model (WT) were also compared. The obtained results of the multiphase DGSCM were found to be significantly better than those obtained from the N-phase WT model for ultrasonic measurements from cementitious materials at high aggregate concentrations. The feasibility of material characterization using the multiphase approach of DGSCM was also discussed.