Surface plasmon polariton propagation across a gentle silver step

Surface plasmon polaritons (SPPs) are excited with light of wavelength lambda (1) = 632.8 nm on or near a gentle Ag/Ag step structure using focused beam, prism coupling and detected using a bare, sharpened fibre tip. The tip-sample separation is controlled by means of an evanescent optical field at wavelength lambda (2) = 543.5 nm in a photon scanning tunnelling microscope (PSTM). The SPP propagation properties are first characterised on both the thin and thick sections of the Ag film structure either side of the step, both macroscopically, using attenuated total reflection, and microscopically from the PSTM images; the two techniques yield very good agreement. It is found that the SPP propagation length is similar to 10-11 mum across the step in each direction (thick to thin and vice versa) as observed in the PSTM images. Thus, with reference to the propagation lengths of 14.2 and 11.7 mum for the thick and thin planar parts of the Ag film respectively, it is concluded that the SPPs negotiate the step reasonably successfully. Importantly, also, it is shown that images may be produced, displaying SPPs with either an artificially enhanced (similar to 15-20 mum) or truncated (5-8 mum) propagation length across the step. Consideration of such images leads us to suggest the possibility that the photon tunnelling occurs in a local water environment. (C) 2001 Elsevier Science B.V. All rights reserved.

ANISOTROPY OF OPTICAL-CONSTANTS OF YBCO

Otto configuration attenuated total reflection (ATR) measurements of the excitation of surface plasmons in the infrared have been carried out on YBCO films deposited on MgO (100) substrates. The dielectric constants for YBCO at 3.392 mu m are determined to be -10 + 15i for c-axis material. The anisotropic nature of the cuprate is seen from films with other orientations: nearly a-axis material has constants of 4.0 + 7.0i. It is thus not metallic in its optical response along the c-axis which lies parallel to the substrate plane. Ellipsometric measurements in the visible on c-axis material point to a maximum surface plasmon energy of 1 eV.

The interaction of surface plasmon polaritons with a silver film edge

A prism coupling arrangement is used to excite surface plasmons at the surface of a thin silver aim and a photon scanning tunnelling microscope is used to detect the evanescent field above the silver surface. Excitation of the silver/ air mode of interest is performed at lambda(1) = 632 . 8 nm using a tightly focused beam, while the control of the tip is effected by exciting a counter-propagating surface plasmon field at a different wavelength. lambda(2) = 543 . 5 nm, using an unfocused beam covering a macroscopic area. Propagation of the red surface plasmon is evidenced by an exponential tail extending away from the launch site, but this feature is abruptly truncated if the surface plasmon encounters the edge of the silver film - there is no specularly reflected 'beam'. Importantly, the radiative decay of the surface mode at the film edge is observable only at larger tip-sample separations, emphasizing the importance of accessing the mesoscopic regime.

Application of surface plasmon polaritons in the laser ablation and characterisation of thin aluminium films

Surface modification of thin aluminium films is both produced and characterised by exciting surface plasmon polaritons in an attenuated total reflection geometry: silica prism/aluminium/aluminium oxide system. The modification is performed, under ambient conditions, by exposure to a low fluence (

Contrasting damage characteristics in direct incidence and surface plasmon mediated single-shot laser ablation of aluminium films

Thin, oxidised Al films grown an one face of fused silica prisms are exposed. tinder ambient conditions, to single shots from an excimer laser operating at wavelength 248 nm. Preliminary characterisation of the films using attenuated total reflection yields optical and thickness data for the Al and Al oxide layers; this step facilitates the subsequent, accurate tuning of the excimer laser pulse to the: surface plasmon resonance at the Al/(oxide)/air interface and the calculation of the fluence actually absorbed by the thin film system. Ablation damage is characterised using scanning electron, and atomic force microscopy. When the laser pulse is incident, through the prism on the sample at less than critical angle, the damage features are molten in nature with small islands of sub-micrometer dimension much in evidence, a mechanism of film melt-through and subsegment blow-off due to the build up of vapour pressure at the substrate/film interface is appropriate. By contrast, when the optical input is surface plasmon mediated, predominately mechanical damage results with the film fragmenting into large flakes of dimensions on the order of 10 mu m. It is suggested that the ability of surface plasmons to transport energy leads to enhanced, preferential absorption of energy at defect sites causing stress throughout the film which exceeds the ultimate tensile stress for the film: this in turn leads to film break-up before melting can onset. (C) 1998 Elsevier Science B.V.

Temperature dependence of the mid-infrared dielectric function of YBCO in the ab plane

We have excited mid-infrared surface plasmons in two YBCO thin films of contrasting properties using attenuated total reflection of light and found that the imaginary part of the dielectric function decreases linearly with reduction in temperature. This result is in contrast with the commonly reported conclusion of infrared normal reflectance studies. If sustained it may clarify the problem of understanding the normal state properties of YBCO and the other cuprates. The dielectric function of the films, epsilon = epsilon(1) + i epsilon(2), was determined between room temperature and 80K: epsilon(1) was found to be only slightly temperature dependent but somewhat sample dependent, probably as a result of surface and grain boundary contamination. The imaginary part, epsilon(2), (and the real part of the conductivity, sigma(1),) decreased linearly with reduction in temperature in both films. Results obtained were: for film 1: epsilon(1) = - 14.05 - 0.0024T and epsilon(2) - 4.11 + 0.086T and for film 2: epsilon(1) = - 24.09 + 0.0013T and epsilon(2) = 7.66 + 0.067T where T is the temperature in Kelvin. An understanding of the results is offered in terms of temperature-dependent intrinsic intragrain inelastic scattering and temperature-independent contributions: elastic and inelastic grain boundary scattering and optical interband (or localised charge) absorption. The relative contribution of each is estimated. A key conclusion is that the interband (or localised charge) absorption is only similar to 10%. Most importantly, the intrinsic scattering rate, 1/tau, decreases linearly with fall in temperature, T, in a regime where current theory predicts dependence on frequency, omega, to dominate. The coupling constant, lambda, between the charge carriers and the thermal excitations has a value of 1.7, some fivefold greater than the far infrared value. These results imply a need to restate the phenomenology of the normal state of high temperature superconductors and seek a corresponding theoretical understanding.

SURFACE-PLASMON ENHANCED LASER-ABLATION OF THIN METAL-FILMS

Surface plasmon enhancement of laser ablation of thin Al films is examined with a view to its application in metal film patterning and nano-structuring. Al films, deposited on silica prisms, are first characterized by attenuated total reflection using a broadband UV source and appropriate interference filter. The films are subsequently subjected to excimer laser radiation of wavelength 248 nm under conditions both of direct incidence from the air side of the film, and of surface plasmon excitation in which light is incident through the prism at greater than critical angle. For a given level of ablation damage in a particular film the fluence required using the surface plasmon technique is 3-5 times less than that needed when direct incidence is used. This is roughly in line with the energy absorbed in the film. From a practical standpoint it is clear that ablation of metal films can be achieved with much lower fluences than has hitherto been possible, thus reducing the requirements on laser output and relaxing the power handling constraints on any input optical elements.

INTERPLAY OF CAF2 SUBSTRATE ROUGHENING AND FILM DEPOSITION RATE ON RADIATIVE SCATTERING OF SURFACE-PLASMON POLARITONS FROM AG FILMS

The radiative decay of surface plasmon polaritons has been investigated in an attempt to characterize the surface roughness of Ag films prepared under different conditions. The polaritons were excited by the method of attenuated total reflection of light. The films were deposited on the face of a 60-degrees BK-7 glass prism at a rate that was deliberately fixed in two different ranges (centred on 0.1 and 10 nm s-1) and in some cases a CaF2 underlayer was used to roughen the film surfaces. The intensity of the scattered light emitted from the opposite face of the films was measured as a function of direction for each using the same sensitivity scale and was correlated with the preparation of the film. It was found that on nominally smooth substrates fast-deposited thinner films give out more light and are deduced to have greater short wavelength (300-600 nm) roughness amplitude. There is also evidence for long wavelenth (7 mum) periodic roughness due to the prism substrate itself. On CaF2 roughened surfaces the light output from the films is further increased and the peak intensity is backward directed with respect to the exciting laser beam direction. Here roughness on a lateral scale of 350 nm is responsible. Also, elastic scattering of surface plasmon polaritons at grain boundaries reduces the light output from fast deposited, small grain, films on CaF2 roughened surfaces. Overall, a consistent picture of roughness induced radiative polariton decay emerges for all cases studied.

SURFACE-MODE ENHANCED PHOTOCURRENT FROM PTSI/N-SI SCHOTTKY-BARRIER DETECTORS

Using the Otto geometry of attenuated total reflection (prism-air gap-sample), front illuminated PtSi/Si Schottky barrier detectors are shown to exhibit enhanced photocurrent at surface plasmon resonance in the near infrared region. Correlation of the measured photocurrent with the calculated transmittance of light into the Si substate is demonstrated. The transmittance, which is due to surface plasmon re-radiation, is the optical parameter of principal importance in photosignal generation since the photon energies used here are greater than the silicon intrinsic bandgap. The results presented here indicate clearly the important features in optimizing surface plasmon enhancement in photodetection both above and below the silicon absorption edge.

In situ ATR-FTIR study of H2O and D2O adsorption on TiO2 under UV irradiation

The adsorption of water and deuterium oxide on TiO2 surfaces was investigated in the dark as well as under UV(A) irradiation using in situ ATR-FTIR spectroscopy under oxygen and oxygen free conditions. Adsorption of H2O-D2O mixtures revealed an isotopic exchange reaction occurring onto the surface of TiO2 in the dark. Under UV(A) irradiation, the amount of both OH and OD groups was found to be increased by the presence of molecular oxygen. Furthermore, the photocatalytic formation of hydroperoxide under oxygenated condition has been recorded utilizing Attenuated Total Reflection Fourier Transformed Infrared (ATR-FTIR) spectroscopy which appeared as new band at 3483 cm-1. Different possible mechanisms are discussed in terms of the source of hydroxyl groups formed and/or hydration water on the TiO2 surface for the photocatalytic reaction and photoinduced hydrophilicity.

Identification of a novel determinant for membrane association in hepatitis C virus nonstructural protein 4B.

Nonstructural protein 4B (NS4B) plays an essential role in the formation of the hepatitis C virus (HCV) replication complex. It is a relatively poorly characterized integral membrane protein predicted to comprise four transmembrane segments in its central portion. Here, we describe a novel determinant for membrane association represented by amino acids (aa) 40 to 69 in the N-terminal portion of NS4B. This segment was sufficient to target and tightly anchor the green fluorescent protein to cellular membranes, as assessed by fluorescence microscopy as well as membrane extraction and flotation analyses. Circular dichroism and nuclear magnetic resonance structural analyses showed that this segment comprises an amphipathic alpha-helix extending from aa 42 to 66. Attenuated total reflection infrared spectroscopy and glycosylation acceptor site tagging revealed that this amphipathic alpha-helix has the potential to traverse the phospholipid bilayer as a transmembrane segment, likely upon oligomerization. Alanine substitution of the fully conserved aromatic residues on the hydrophobic helix side abrogated membrane association of the segment comprising aa 40 to 69 and disrupted the formation of a functional replication complex. These results provide the first atomic resolution structure of an essential membrane-associated determinant of HCV NS4B.

Étude des propriétés de transport dans les hydrogels de curdlan

Les hydrogels de polysaccharide sont des biomatériaux utilisés comme matrices à libération contrôlée de médicaments et comme structures modèles pour l’étude de nombreux systèmes biologiques dont les biofilms bactériens et les mucus. Dans tous les cas, le transport de médicaments ou de nutriments à l’intérieur d’une matrice d’hydrogel joue un rôle de premier plan. Ainsi, l’étude des propriétés de transport dans les hydrogels s’avère un enjeu très important au niveau de plusieurs applications. Dans cet ouvrage, le curdlan, un polysaccharide neutre d’origine bactérienne et formé d’unités répétitives β-D-(1→3) glucose, est utilisé comme hydrogel modèle. Le curdlan a la propriété de former des thermogels de différentes conformations selon la température à laquelle une suspension aqueuse est incubée. La caractérisation in situ de la formation des hydrogels de curdlan thermoréversibles et thermo-irréversibles a tout d’abord été réalisée par spectroscopie infrarouge à transformée de Fourier (FT-IR) en mode réflexion totale atténuée à température variable. Les résultats ont permis d’optimiser les conditions de gélation, menant ainsi à la formation reproductible des hydrogels. Les caractérisations structurales des hydrogels hydratés, réalisées par imagerie FT-IR, par microscopie électronique à balayage en mode environnemental (eSEM) et par microscopie à force atomique (AFM), ont permis de visualiser les différentes morphologies susceptibles d’influencer la diffusion d’analytes dans les gels. Nos résultats montrent que les deux types d’hydrogels de curdlan ont des architectures distinctes à l’échelle microscopique. La combinaison de la spectroscopie de résonance magnétique nucléaire (RMN) à gradients pulsés et de l’imagerie RMN a permis d’étudier l’autodiffusion et la diffusion mutuelle sur un même système dans des conditions expérimentales similaires. Nous avons observé que la diffusion des molécules dans les gels est ralentie par rapport à celle mesurée en solution aqueuse. Les mesures d’autodiffusion, effectuées sur une série d’analytes de diverses tailles dans les deux types d’hydrogels de curdlan, montrent que le coefficient d’autodiffusion relatif décroit en fonction de la taille de l’analyte. De plus, nos résultats suggèrent que l’équivalence entre les coefficients d’autodiffusion et de diffusion mutuelle dans les hydrogels de curdlan thermo-irréversibles est principalement due au fait que l’environnement sondé par les analytes durant une expérience d’autodiffusion est représentatif de celui exploré durant une expérience de diffusion mutuelle. Dans de telles conditions, nos résultats montrent que la RMN à gradients pulsés peut s’avérer une approche très avantageuse afin de caractériser des systèmes à libération contrôlée de médicaments. D’autres expériences de diffusion mutuelle, menées sur une macromolécule de dextran, montrent un coefficient de diffusion mutuelle inférieur au coefficient d’autodiffusion sur un même gel de curdlan. L’écart mesuré entre les deux modes de transport est attribué au volume différent de l’environnement sondé durant les deux mesures. Les coefficients d’autodiffusion et de diffusion mutuelle similaires, mesurés dans les deux types de gels de curdlan pour les différents analytes étudiés, suggèrent une influence limitée de l’architecture microscopique de ces gels sur leurs propriétés de transport. Il est conclu que les interactions affectant la diffusion des analytes étudiés dans les hydrogels de curdlan se situent à l’échelle moléculaire.

Étude de l’effet d'agents potentiellement perturbateurs de la structure des biofilms sur la diffusion des macromolécules dans les biofilms de Streptococcus mutans : cas de l’EDTA et de l’aspirine

Le but de ce travail de mémoire était d'explorer des moyens pour augmenter la perméabilité des biofilms de Streptococcus mutans aux macromolécules en utilisant des agents potentiellement perturbateurs de la structure des biofilms. L’acide éthylènediamine tétraacétique (EDTA) ainsi que l’acide acétylsalicylique (aspirine) sont les agents perturbateurs choisis. Le changement de perméabilité des biofilms de S. mutans a été déterminé en mesurant les coefficients de diffusion globale du polyéthylène glycol (PEG) et de diffusion locale de dextrans. Les coefficients de diffusion globale ont été mesurés par spectroscopie infrarouge avec un échantillonnage par réflexion totale atténuée (ATR) alors que la spectroscopie par corrélation de fluorescence (SCF) a été utilisée pour la mesure des coefficients de diffusion locale. Les résultats ont démontré que l’incorporation de l’EDTA à une concentration de 7.5 (m/v) % dans la solution de diffusion permet d’améliorer les propriétés de transport du PEG dans les biofilms en augmentant sa pénétrabilité et son coefficient de diffusion globale. Par contre, aucune variation n’a été constatée dans la valeur du coefficient de diffusion locale de dextran fluorescent. Cette différence peut être expliquée, entre autres, par l'échelle des mesures et la nature différente des molécules diffusantes. L’aspirine n’a démontré aucun effet sur le transport du PEG à travers les biofilms de S. mutans. La pénétration accrue du PEG en présence de l’EDTA a été corrélée aux tests de viabilité des cellules bactériennes. En effet, la combinaison de la pénicilline G (PenG) avec l’EDTA 2 (m/v) % a eu comme effet l’augmentation du pouvoir biocide d’un facteur 3. De plus, les images de microscopie à épifluorescence et de microscopie confocale à balayage de laser ont démontré que les bactéries dans le cœur des microcolonies sont plus affectées par la PenG lorsque le milieu contient de l'EDTA. A la lumière des résultats obtenus, il s’avère que l’incorporation d'agents perturbateurs de la structure des biofilms est une option sérieuse à considérer dans l’éradication des biofilms microbiens. Plus d’études devront être effectuées afin d’investiguer l’effet d’autres molécules possédant les propriétés perturbatrices de la structure des biofilms sur la résistance de ces derniers aux agents antimicrobiens.

Spectroscopic imaging of arteries and atherosclerotic plaques

Fourier transform infrared (FTIR) spectroscopic imaging using a focal plane array detector has been used to study atherosclerotic arteries with a spatial resolution of 3-4 mum, i.e., at a level that is comparable with cellular dimensions. Such high spatial resolution is made possible using a micro-attenuated total reflection (ATR) germanium objective with a high refractive index and therefore high numerical aperture. This micro-ATR approach has enabled small structures within the vessel wall to be imaged for the first time by FTIR. Structures observed include the elastic lamellae of the tunica media and a heterogeneous distribution of small clusters of cholesterol esters within an atherosclerotic lesion, which may correspond to foam cells. A macro-ATR imaging method was also applied, which involves the use of a diamond macro-ATR accessory. This study of atherosclerosis is presented as an illustrative example of the wider potential of these A TR imaging approaches for cardiovascular medicine and biomedical applications. (C) 2004 Wiley Periodicals, Inc.