O confinamento da luz em escala nanométrica, em especial para estruturas metálicas, é conferido graças à ação coletiva dos elétrons livres desses materiais que ao entrarem em ressonância com a frequência da radiação incidente geram campos intensos o suficiente para permitir que uma parcela da luz atravesse as cavidades que formam as estruturas, desafiando os limites clássicos da óptica impostos pela teoria escalar da difração. Designa-se a tal ação coletiva dos elétrons na literatura como plasmons polaritons de superfície, ou SPP da sigla em inglês para Surface Plasmon Polariton, conceito há muito estudado em Física do Estado Sólido. Porém, somente a algumas décadas com o domínio sobre a fabricação de estruturas em escala nanométrica, tornou-se possível a análise experimental e a contribuição de SPP na observação de fenômenos em nano-óptica. A ressonância de plasmons em nanoestruturas confere considerável sensibilidade ao índice de refração dos meios próximos a elas, o que abre mais um canal para estudos no campo da interação entre radiação-matéria. Dentre eles há interação de plasmons com íons de terras-raras (ITR). Estes últimos por apresentarem bandas de absorção estreitas e bem definidas, são excelentes opções como elementos na análise da interação destes com os SPPs gerados nas nanoestruturas. Uma maneira de estabelecer o contato direto entre o campo plasmônico e os ITRs é incorpora-los ao substrato no qual o filme metálico onde as nanoestruturas são fabricadas é depositado. Vidros óxidos à base de Telúrio e Germânio reúnem condições favoráveis para esse propósito, por terem alta solubilidade às terras-raras, janela de transparência relativamente larga (0,4 - 5μm) podendo ser analisados desde o visível até o infravermelho e baixa energia de fônon. O presente trabalho consistiu no esforço de criar uma plataforma para estudo direto de interações SPP com o ITR a partir da nano fabricação via técnica de feixe de íons e medir a luz emitida por processo de conversão ascendente do Érbio diretamente pela nanoestrutura devido ao decaimento do íon em SPP e na consequente remissão através da transmissão óptica extraordinária (TOE). A partir de tais medidas há fortes evidências de que a radiação emitida pelo Érbio apresenta a mesma polarização do campo plasmônico originado nas nanoestruturas. / The confinement of light at the nanoscale, especially for metallic structures is achieved due the collective action of free electrons from the material that resonate with the frequency of the incident radiation, generating enhanced fields enough to allow a portion of the light to cross the cavities that form such structures, challenging the classical limits of optics imposed by the scalar diffraction theory. Such collective action of the electrons is known in the literature as surface plasmon polariton (SPP), a concept which has already been studied in Solid State Physics, but only a few decades ago, with the development of fabrication of nanoscale structures has enabled the experimental analysis and the contribution due SPP on the observation of nanoptics phenomena. The plasmon resonance from nanostructures offers considerable sensitivity to the refractive index from the media that surround them, which opens another topic in matter-radiation interaction. There are interactions of plasmons with rare earth ions (REI). The latter class of emitters, presents narrow and well-defined absorption bands, which make them excellent options as probes to the analysis of interaction with the SPPs generated in the nanostructures. To establish direct contact between the plasmonic field and the REIs consists in embedding them into the substrate for the metallic thin film where the structures are assembled. Tellurium and Germanium oxide based glasses gather the conditions for this purpose, because they present high solubility to rare earths, a relatively wide transparency window (0.4 - 5 μm), which enables spectral analysis from visible to infrared, and low phonon energy. The present work consisted in the effort to create a direct platform to study the SPP interactions with the REI from the milling of the samples by ion beam technique; to measure the light emitted from the Erbium\'s upconversion process directly through the nanostructure due the ion decay to SPP and in the consequent remission by extraordinary optical transmission (EOT). From such measurements there are strong evidences that the radiation emitted by Erbium ions presents the same polarization from the plasmonic field originated in nanostructures.

Neste trabalho estão apresentadas novas estratégias para funcionalizar superfícies de ouro baseadas na sustentação de bicamadas lipídicas em superfícies de sensores de imagem por Ressonância de Plasmons de Superfície (SPRi) e a construção de um biosensor para detecção de citocromo c. SPRi é uma técnica ótica de gravimetria em tempo real. Por meio de medidas de variações de índice de refração (n) próximas a uma interface, a adsorção e desorção de moléculas podem ser mensuradas. Inicialmente testamos várias estratégias para encontrar um suporte adequado que se ligasse na superfície de ouro e que oferecesse sustentação e estabilidade para a bicamada de fosfolipídeo biotinilado. Estudos de FT-IR e MEV mostraram que a quitosana facilita a formação de uma bicamada íntegra de fosfolipídeos, de tal modo, que a mesma alcança valores de espessura próximos àqueles previstos, ~ 34,5 Å. Além disso, mostramos que esse sistema apresenta vantagens perante outros modelos, tais como, (poli-lisina/fosfolipídeos) e (tiol hidrofóbico/fosfolipídeo). Utilizando-se o complexo químico biotina/estreptoavidina conseguimos imobilizar o anticorpo anti cit c na bicamada, mantendo-o afastado da superfície de ouro. A construção do biosensor foi acompanhada com experimentos de SPRi. O limite de detecção de citocromo c atingido foi de 10-11mol/L. Um sensor construído somente com BSA e anticorpo anti cit c apresentou sensibilidade semelhante. Esta sensibilidade é em torno de três ordens de grandeza superior aos experimentos de imunoblotting usualmente utilizados para detecção de cit c. A principal limitação deste biosensor, tal como de outros imunoensaios, está intimamente ligada às vantagens e desvantagens dos anticorpos como ferramentas analíticas. / In this work we developed new strategies to functionalize gold surfaces based on the support of lipid bilayers on the surfaces of surface plasmon resonance imaging sensors (SPRi) and the construction of a biosensor for detection of cytochrome c. SPRi is an optical gravimetric real time technique. Through measurements of changes in refractive index (n) in close proximity to an interface, the adsorption and desorption of molecules can be measured. Initially we tested several strategies for finding a suitable medium that would adsorb on the gold surface and also support and stabilize a biotinylated phospholipid bilayer. Studies of FT-IR and SEM showed that chitosan induces the formation of an intact phospholipid bilayer, so that it reaches thickness values close to those expected, ~ 34.5 Å. Furthermore, we showed that this system has advantages in relation to other models, such as (poli-lisine/phospholipids) and (thiol hydrophobic / phospholipid). Using the chemical complex biotin/streptavidin anti cyt c antibody could be immobilized in the bilayer, keeping it away from the gold surface. The construction of the biosensor was accompanied with SPRi experiments. The limit of detection of cytochrome c was achieved from 10-11mol / L. A sensor built only with BSA and anti cyt c showed similar sensitivity. This sensitivity is about three orders of magnitude higher than the immunoblotting experiments commonly used for detection of cyt c. The main limitation of this biosensor, like in other immunoassays, is linked to the advantages and disadvantages of antibodies as analytical tools.

Nanoscale lithography is the key component of the semiconductor device fabrication process. For the sub-10 nm node device, the conventional deep ultraviolet (DUV) photolithography approach is limited by the diffraction nature of light even with the help of double or multiple patterning. The upcoming extreme ultraviolet (EUV) photolithography can overcome this resolution limit by using very short wavelength (13.5nm) light. Because of the prohibitive cost of the tool and the photomask, the EUV lithography is only suitable for high volume manufacturing of high value. Several alternative lithography technologies are proposed to address the cost issue of EUV such as directed self-assembly (DSA), nanoimprint lithography (NIL), scanning probe lithography, maskless plasmonic photolithography, optical maskless lithography, multiple electron-beam lithography, etc.<div><br></div><div>Electron-beam lithography (EBL) utilizes a focused electron beam to write patterns dot by dot on the silicon wafer. The beam size can be sub-nanometers and the resolution is limited by the resist not the beam size. However, the major drawback of EBL is its low throughput. The throughput can be increased by using large current but at the cost of large beam size. This is because the interaction between electrons in the pathway of the electron beam. To address the trade-off between resolution and throughput of EBL, the multiple electron-beam lithography was proposed to use an array of electron-beams. Each beam has a not very large beam current to maintain good resolution but the total current can be very high to improve the throughput. One of the major challenges is how to create a uniform array of electron beamlets with large brightness.<br></div><div><br></div><div>This dissertation shows a novel low-cost high-throughput multiple electron-beam lithography approach that uses plasmonic enhanced photoemission beamlets as the electron beam source. This technology uses a novel device to excite and focus surface electromagnetic and electron waves to generate millions of parallel electron beamlets from photoemission. The device consists of an array of plasmonic lenses which generate electrons and electrostatic micro-lenses which guide the electrons and focus them into beams. Each of the electron beamlets can be independently controlled. During lithography, a fast spatial optical modulator will dynamically project light onto the plasmonic lenses individually to control the switching and brightness of electron beamlets without the need of a complicated beamlet-blanking array and addressable circuits. The incident photons are first converted into surface electromagnetic and electron waves by plasmonic lens and then concentrated into a diffraction-unlimited spot to excite the local electrons above their vacuum levels. Meanwhile, the electrostatic micro-lens will extract the excited electrons to form a finely focused beamlet, which can be rastered across a wafer to perform lithography. The scalable plasmonic enhanced photoemission electron-beam sources are designed and fabricated. An array of micro-scale electrostatic electron lenses are designed and fabricated using typical micro-electro-mechanical system (MEMS) fabrication method. The working distance (WD) defined as the gap from the electron lens to the underneath silicon wafer is regulated using a gap control system. A vacuum system is designed and constructed to host the multiple electron-beam system. Using this demo system, the resolution of the electron beams is confirmed to be better than 30 nm from the lithography results done on poly methyl methacrylate (PMMA) and hydrogen silsesquioxane (HSQ) resists. According to simulation results, the electron beam spot size can be further optimized to be better than 10 nm.<br></div><div><br></div><div>This scheme of high-throughput electron-beam lithography with multiple plasmonic enhanced photoemission beamlets has the potential to be an alternative approach for the sub-10 nm node lithography. Because of its maskless nature, it is cost effective and especially suitable for low volume manufacturing and prototype demonstration.<br></div><div><br></div><div><br></div>

Ce travail de thèse présente une étude théorique, numérique et expérimentale de l’intégration sur un guide d’onde diélectrique de chaînes de nanoparticules d’or supportant des résonances « plasmon de surface localisé ». Les guides d’onde à plasmon de surface localisé procurent un confinement sub-longueur d’onde de la lumière, ce qui permet d’envisager la réalisation de composants optiques ultra-compacts. Cependant, leurs pertes optiques élevées restreignent leur application à de courtes distances de propagation, contrairement aux guides d’onde diélectriques. Une combinaison judicieuse des deux types de guide doit donc permettre de bénéficier de leurs avantages respectifs. Dans un premier temps, nous avons étudié théoriquement les propriétés des chaînes des nanoparticules grâce à un modèle analytique basé sur l’approximation de dipôles ponctuels couplés, que nous avons développé. Cette étude a permis de déterminer la forme et les dimensions des nanoparticules qui ont ensuite été introduites dans un logiciel de FDTD pour simuler le couplage entre la chaîne de nanoparticules et le guide diélectrique (SOI ou en Si3N4). De cette étude numérique, nous avons déduit les géométries des structures à fabriquer. Les structures réalisées ont été caractérisées à l’aide d’un banc de transmission résolue spectralement, mis en place pendant cette thèse, et d’un système de mesures en champ proche optique en collaboration avec le LNIO (Troyes). Pour la première fois, nous avons montré expérimentalement les propriétés d’une chaîne courte de nanoparticules intégrée sur un guide SOI, ainsi que le phénomène de guides couplés entre une chaîne longue de nanoparticules et un guide SOI. Une valeur record de la constante de couplage a été obtenue, et ce, aux longueurs d’onde des télécoms (proche infrarouge). L’énergie lumineuse transportée par le mode TE du guide SOI peut ainsi être entièrement transférée au guide plasmonique en 4 ou 5 nanoparticules, soit une distance de propagation de moins de 600 nm. Nous avons également étudié les propriétés de réseaux de Bragg à base de plasmon de surface localisé en confrontant les résultats de mesures de transmission résolue spectralement aux résultats théoriques d’un modèle analytique basé à la fois sur l’approximation de dipôle ponctuel en régime quasi-statique et la théorie des modes couplés. Ces travaux ouvrent la voie à des applications de pinces optiques, de capteurs ou de spaser, qui bénéficieront de l’intégration de nanoparticules métalliques dans les circuits photoniques. / This PhD work presents a theoretical, numerical and experimental study of the integration of a gold nanoparticle chain supporting "localized surface plasmon resonances" on a dielectric waveguide. The localized surface plasmon allows a sub-wavelength confinement of light which could lead to the achievement of ultra-compact optical components. However, the high level of optical losses restricts their application to short propagating distances unlike dielectric waveguides. A judicious combination of both types of guides should therefore allow taking profit of their respective advantages. Firstly, we have theoretically studied the properties of nanoparticles chains using an analytical model that we have developed following the coupled dipoles approximation. This has helped us to determine the shape and size of nanoparticles, which have been further used in a FDTD software, to simulate the coupling between the chain and the dielectric waveguide (SOI or Si3N4). Using this numerical study, we have deduced the geometries of structures to be fabricated. The realized structures have been characterized using a spectrally resolved transmission set-up, built during this thesis, and an optical near field measurement set-up (collaboration LNIO Troyes). For the first time, we have experimentally shown the properties of short nanoparticle chains integrated on a SOI waveguide as well as the existence of a coupled waveguide phenomenon between long nanoparticle chains and SOI waveguides. A record value has been obtained for the coupling constant at telecom wavelengths (near infrared). The light energy carried by the TE mode of the SOI waveguide can be completely transferred into the plasmonic waveguide via the first 4 or 5 nanoparticles of the chain, which means a distance of less than 600 nm. We have also studied the properties of Bragg gratings based on localized surface plasmon. Experimental results from spectrally resolved transmission measurements have been compared to theoretical results obtained from an analytical model based on the point dipole approximation in quasi-static regime, on one hand, and using the coupled mode theory, on the other hand. This work opens the way for applications to optical tweezers, sensors or spasers, which will benefit from the integration of metal nanoparticles in photonic circuits.

This thesis covers different topics in the field of synthetic organic chemistry combined with the field of surface science and glycobiology. First, the text presents a series of orthogonally protected oligosaccharides (tri-, penta-, and heptasaccharides) of varying length and structures, which are synthesized with the aim of developing novel heterobifunctional biocompatible cross-linkers. Successful conjugation with different chemical handles is also described and used to illustrate the potential implementation of defined carbohydrate based compounds have potential use in biosensing applications. The results of incubation experiments using living cells indicate that the linker is incorporated into cell surfaces and enriched in microdomains. Second, synthesis of various saccharide-terminated alkane thiols immobilized on gold surfaces is reported. The protein adsorption and antifouling characteristics of these surfaces were investigated using model proteins and the common fouling organisms, Ulva linza and Balanus amphitrite. Further, oligo(lactose)-based thiols (di-, tetra-, and hexasaccharides) were synthesized and immobilized on gold nanoparticles to investigate how well these rigid, rod-like oligosaccharides can stabilize such nanoparticles for future use in constructing hybrid nanoparticles. Finally, the thesis describes synthesis of a systematic series of oligo(ethylene) glycols possessing either hydrogen- or methyl-terminated groups. Investigation of the fundamental characteristics of self-assembled monolayers, will give important insights into the design of protein repellant surfaces.

The content of this thesis is based upon the interaction of light with metallic nanoparticles arranged in different array geometries. An incident electric field (light) can force the conduction electrons of a metallic nanoparticle to oscillate. At particular frequencies, in the optical regime for gold and silver particles, absorption and scattering of the light by the particle is enhanced, corresponding to the particle plasmon resonance. The spectral position and width of the particle plasmon resonance of an isolated single particle may be tuned by adjusting its size and shape, thus changing the surface charge distribution. Periodic arrays of particles offer additional control over the frequency and width of the resonance attributed to the re-radiating (scattering) property of plasmonic particles. By fabricating arrays with a pitch comparable to the wavelength of an isolated single particle plasmon resonance, a coherent interaction between particles may be produced, known as surface lattice resonances (SLRs). The electromagnetic coupling between in-plane particle plasmon modes for different particle array geometries is explored through experiment and theory. Firstly, SLRs in square, hexagonal and honeycomb arrays are investigated by normal-incidence extinction measurements and compared to a simple-coupled dipole model. Secondly, to verify the nature of the coupling between the scattered electric field associated with particle resonances, the incident electric field polarization-dependence of the extinction of rectangular arrays and chains is studied. Thirdly, the optical response of square arrays with a symmetric two-particle basis is investigated, particularly the retardation of the scattered electric field between particles in a pair. Fourthly, square arrays with an asymmetric two-particle basis are fabricated to explore the symmetric (dipole moments of both particles are parallel) and anti-symmetric (dipole moment of both particles anti-parallel) SLRs, excited by normal-incidence light.

No description available.

Human practices have resulted in great damage to the environment. Carbon-depletion, water and air pollution, as well as global warming are examples of the environmental footprints caused by several industries and their related applications. Detergency (cleaning) is widely practiced operation in household, industry and institutional sectors and thus consumes significant amounts of water, energy and chemicals and, therefore, contributes appreciably to the environmental destruction. This process is still not fully understood, on a molecular level, and not acceptably optimised. Therefore, this study is a contribution toward a better fundamental understanding and optimisation of protein stain removal from interfaces, which may ultimately result in the development of environmentally friendly and sustainable cleaning products and technologies. In this research, the cleaning of rubisco, a grassy protein stain, from different surfaces (hydrophobic, hydrophilic, and dyed) using different cleaning agent formulations was investigated. These studies encompassed experimental work and fundamental analysis in terms of mathematical modelling. The results revealed a consistent correlation between enzyme adsorption kinetics and stain cleanability. Higher adsorption and desorption absolute rates ( a k and d k ) resulted in higher enzyme mobility and thus higher stain cleanability regardless of the enzyme adsorbed amount. Surface chemistry underlying the stain has indirectly influenced stain cleanability through the alteration of enzyme adsorption kinetics. Such fundamental findings may aid in screening enzyme candidates for detergent formulations and may also assist in designing easily cleanable surfaces. Another fundamental finding is the cooperative cleaning mechanism of surfactant and enzyme of rubisco stain from different interfaces. The break down of intermolecular physical bonds between interfacial rubisco molecules by surfactants and the break down of the intramolecular covalent bonds by enzyme resulted in a higher protein displacement from interfaces. The overall protein removal by the two different actions of surfactant and enzyme showed a superiority of a biosurfactant-enzyme formulation. This finding may have significant implications on developing sustainable detergents that have superior cleaning performance and no or minimal environmental hazard. Overall, the findings reported in this Ph.D. thesis may form a basis for further comprehensive scientific research, which may ultimately provide detergent market with more efficient and optimum cleaning products and technologies.

<p>The aims of this study are to first immobilize positively charged gold nanorods to negatively charged cell culture surfaces. Second, to use polyelectrolytes for controlling the distance between gold nanorods and fluorophores. This is used to optimally determine the distance, of which maximum fluorescence enhancement is achieved, between gold nanorods and fluorophores. In order to approach these aims, we use UV/VIS absorption spectroscopy, fluorescence spectroscopy, atomic force microscopy, and ellipsometry. The results show that we could control the immobilization of gold nanorods on plastic microwell plates and create reproducible polyelectrolyte layers, in order to control the distance between the gold nanorods and fluorophores. In addition, the localized surface plasmon resonance wavelength red shifted as the PELs increased. In conclusion, we found that the maximum fluorescence enhancement of the fluorophores (Cy7) is about 2.3 times at a fluorophores-nanoparticles separation of approximately 9-12 nm. This work contributes some research information towards the design of optical biochip platforms based on plasmon-enhanced fluorescence.</p>

This thesis concerns the development of surface ligation techniques for the preparation of carbohydrate biosensors. Several methodologies were developed based on efficient photochemical insertion reactions which quickly functionalize polymeric materials, with either carbohydrates or functional groups such as alkynes or alkenes. The alkyne/alkene surfaces were then treated with carbohydrate azides or thiols and reacted under chemoselective Cu-catalyzed azide-alkyne cycloaddition (CuAAC) or photo-radical thiol-ene/yne click chemistry, thus creating a range of carbohydrate biosensor surfaces under ambient conditions. The methodologies were evaluated by quartz crystal microbalance (QCM) and surface plasmon resonance (SPR) flow through instrumentations with recurring injections of a range of lectins, allowing for real-time analysis of the surface interactions. The developed methods were proven robust and versatile, and the generated carbohydrate biosensors showed high specificities and good capacities for lectin binding.  The methods were then used to investigate how varying the glycan linker length and/or a sulfur-linkage affect the subsequent protein binding. The survey was further explored by investigating the impact of sulfur in glycosidic linkages on protein binding, through competition assays with various O/S-linked disaccharides in solution interactions with lectins. / QC 20120309