abstract: In engineering, buckling is mechanical instability of walls or columns under compression and usually is a problem that engineers try to prevent. In everyday life buckles (wrinkles) on different substrates are ubiquitous -- from human skin to a rotten apple they are a commonly observed phenomenon. It seems that buckles with macroscopic wavelengths are not technologically useful; over the past decade or so, however, thanks to the widespread availability of soft polymers and silicone materials micro-buckles with wavelengths in submicron to micron scale have received increasing attention because it is useful for generating well-ordered periodic microstructures spontaneously without conventional lithographic techniques. This thesis investigates the buckling behavior of thin stiff films on soft polymeric substrates and explores a variety of applications, ranging from optical gratings, optical masks, energy harvest to energy storage. A laser scanning technique is proposed to detect micro-strain induced by thermomechanical loads and a periodic buckling microstructure is employed as a diffraction grating with broad wavelength tunability, which is spontaneously generated from a metallic thin film on polymer substrates. A mechanical strategy is also presented for quantitatively buckling nanoribbons of piezoelectric material on polymer substrates involving the combined use of lithographically patterning surface adhesion sites and transfer printing technique. The precisely engineered buckling configurations provide a route to energy harvesters with extremely high levels of stretchability. This stiff-thin-film/polymer hybrid structure is further employed into electrochemical field to circumvent the electrochemically-driven stress issue in silicon-anode-based lithium ion batteries. It shows that the initial flat silicon-nanoribbon-anode on a polymer substrate tends to buckle to mitigate the lithiation-induced stress so as to avoid the pulverization of silicon anode. Spontaneously generated submicron buckles of film/polymer are also used as an optical mask to produce submicron periodic patterns with large filling ratio in contrast to generating only ~100 nm edge submicron patterns in conventional near-field soft contact photolithography. This thesis aims to deepen understanding of buckling behavior of thin films on compliant substrates and, in turn, to harness the fundamental properties of such instability for diverse applications. / Dissertation/Thesis / Ph.D. Mechanical Engineering 2014

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-09-28T19:52:37Z No. of bitstreams: 1 lucianadeoliveirainhan.pdf: 10066254 bytes, checksum: 82e429358b8bc970ef70d2d5e1556880 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-10-09T19:25:07Z (GMT) No. of bitstreams: 1 lucianadeoliveirainhan.pdf: 10066254 bytes, checksum: 82e429358b8bc970ef70d2d5e1556880 (MD5) / Made available in DSpace on 2017-10-09T19:25:07Z (GMT). No. of bitstreams: 1 lucianadeoliveirainhan.pdf: 10066254 bytes, checksum: 82e429358b8bc970ef70d2d5e1556880 (MD5) Previous issue date: 2017-04-19 / O trabalho propõe uma análise da produção artística desenvolvida pela artista e litógrafa mineira Lotus Lobo desde o final da década de 1960 até os dias de hoje, com matrizes de rótulos de embalagens descartadas pelas estamparias mineiras (especialmente de Juiz de Fora), em um momento de substituição de tecnologias de impressão. Destaco sua aproximação com a Pop Art — cuja produção, em geral, também dialoga com as artes gráficas ligadas ao contexto sócioindustrial —, mostrando as influências e as disparidades que impedem seu trabalho de ser meramente caracterizado como tal. Procuro refletir sobre duas direções de seu trabalho: a produção da artista plástica, por meio da apropriação das imagens dessas matrizes e de materiais de refugo industrial, como as maculaturas; e a pesquisadora que tenta manter viva a memória do design gráfico mineiro do início do século XX, seja por projetos acadêmicos ou iniciativas individuais, independentes, demonstrando a alta criatividade de sua produção artística e o lastro de suas contribuições. / This paper proposes an analysis of the artistic production developed by the artist and lithographer Lotus Lobo from the late 1960s to the present day, with matrices of packaging labels discarded by the printmakers of Minas Gerais (especially from Juiz de Fora), at a time when printing technologies were being replaced. I highlighted her proximity to Pop Art — whose works also dialogue with the graphic arts linked to the industrial context — showing the influences and the disparities that prevent her work from being characterized as Pop. I try to reflect on two directions of her work: the production of the plastic artist, through the appropriation of the images of these matrices and materials refused by the industry, as the stained printings (maculaturas); and the researcher who tries to keep alive the memory of the graphic design of Minas Gerais of the early twentieth century, either by academic projects or through independent initiatives, demonstrating the high creativity of her artistic production and the wide range of her contributions.

Recent advances in nanofabrication techniques have opened up new avenues and numerous possible applications in both nanoscale electrochemistry and analytical nanoscience by enabling the fabrication of reproducible nanoelectrodes with different new geometries. Nanoelectrodes exhibit advantages including enhanced mass transport, higher current densities, improved signal-to-noise ratios, and lower ohmic drop. In this dissertation, the use of nanoelectrodes in the electrochemical response properties investigations or in the spectroelectrochemical studies is the unifying factor among all the chapters. First (in Chapter 4), we presented a direct comparison between the electrochemical characteristics of two finite nanoelectrodes arrays with different geometries: 6 × 6 recessed nanodiscs and nanorings microarrays. Using computational methods, it was demonstrated that the electrode geometry’s parameters have a drastic influence on the mass transport properties of the nanoelectrodes. The results presented here are the first combination of experimental and numerical studies that elucidate the transport on nanoring electrode arrays. The comparison of the electrochemical behavior between nanostructures using full 3D simulations is also unique. Second, we have provided a comprehensive numerical study on the redox cycling performance properties of a 6 × 6 recessed nanorings-ring electrode array configuration. The simulation results were in good agreement with the experimental data. After validating the model against experiments, a comprehensive computational investigation revealed avenues to optimize the performance of the structure in terms of geometric parameters and scan rates. The second half of this dissertation is comprised of the spectroelectrochemical studies. The combination of surface plasmon resonance with electrochemistry presents new paths to investigateredox reaction events at the electrode surface since it brings an additional dimension to the classical electrochemical approaches. Third, we have reported a novel active plasmonic device based on a new switching mechanism for the nanohole electrodes array to bridge between photonics and electronics at nanoscales. The inner surfaces of the nanohole electrodes in the array were coated with an electroconductive polymer, polypyrrole, (PPy). Then, it was shown that light transmitted through the PPy- modified nanohole electrodes can be easily tuned and controled by applying an external potential. We were also able to switch on and off the transmitted light intensity through the modified nanohole arrays by potential steps, demonstrating the potential of this platform to be incorporated into optoelectronic devices. Finally, we have fabricated larger area plasmonic periodic nanopillar 3D electrodes using a rapid, high-throughput, and cost-effective approach: the laser interference lithography. Then, the electrochemical behavior of these electrodes was investigated both experimentally and computationally. The properties were ‘compared with a flat electrode with an equivalent geometric area. Afterward, we have successfully probed the changes in the concentration of a reversible redox pair near the electrode surface induced by various applied potentials, in an in-situ EC-SPR experiment. / Graduate

L'objectif de ce travail est de développer et d'évaluer de nouvelles résines originales biosourcées pour l'application lithographique. Pour atteindre cet objectif, nous avons sélectionné différents types de lignine et étudié l'influence du fractionnement de la lignine sur les propriétés finales de la résine obtenue. Le fractionnement de la lignine est réalisé à l’aide de solvants organiques sélectionnés pour leur polarité. Nous avons choisi ce polymère naturel en raison de la présence de nombreux groupes fonctionnels directement responsables de sa réactivité : molécules photosensibles et potentiellement réticulables. La lignine est également une bonne candidate car abondante sur Terre et sa valorisation actuelle en tant que matière première chimique est négligeable. Nous avons étudié la photoréactivité de la résine à base de lignine à 395 nm en utilisant des sources de lumière LED. Sur la base des observations FTIR et UV-VIS, nous avons étudié et quantifié les changements structurels survenus lors de l'exposition de la photorésine à la lumière. Cependant, ces changements étaient plus intenses au cours de l'irradiation conduite dans l'air par rapport à une atmosphère inerte. De plus, nous avons établi le lien entre la structure chimique de la lignine et sa réactivité décrite par les tests de sensibilité, de contraste et de résolution. Nous avons proposé des mécanismes cohérents basés sur des données de la littérature. Ainsi, la réticulation de la lignine se produit sous les photons des rayonnements UV-VIS entraînant la formation de structures intermédiaires, de chromophores ou de composés volatils de bas poids moléculaire. Enfin, nous avons démontré qu'il était possible de fabriquer par écriture laser directe des nanostructures mono-, bi- et tridimensionnelles dans la photorésine à base de lignine "juste fractionnée" par polymérisation à deux photons. / The goal of this work was to develop and to evaluate new, original and bio-based resist for lithographic application. To reach this purpose, we have selected various types of lignin and study the influence of lignin fractionation in different organic solvents on the final resist properties. We have chosen this photosensitive and crosslinkable polymer due to its great abundance and to its currently poor valorisation as a chemical feedstock, as well as the versatility of the functional groups that were directly responsible for its reactivity. We have investigated the photoreactivity of lignin-based resist at 395 nm, using LED light sources. Based on the FTIR and UV-vis monitoring, we have investigated and quantified the structural changes occurred during photoresist exposure to the light. However, they were more visible during the irradiation conducted in the air than in the inert atmosphere. Moreover, we have established the link between chemical structure of lignin and its reactivity observed by sensitivity, contrast and resolution tests. Additionally, we have proposed reasonable mechanisms based on literature data according to which lignin crosslinking occur under UV-visible photons. They comprised the formation of intermediates structures, chromophores, or low molecular weight volatile compounds, as well and crosslinking reactions. Finally, we have demonstrated that it was possible to fabricate one-, two- and three-dimensional structures from "just-fractionated" lignin photoresist by two-photon polymerisation achieved by direct laser writing.

Microfluidics has seen an explosion in growth in the past few years, providing researchers with new and exciting lab-on-chip platforms with which to perform a wide variety of biological and biochemical experiments. In this work, a volume quantification tool is developed, demonstrating the ability to measure the volume of individual cells at high resolution and while enabling microfluidic sample manipulations. Care is taken to maximise measurement sensitivity, range and accuracy, though novel use of buoyancy and dynamically tunable microchannels. This first demonstration of a microfluidic tunable volume sensor meant volume sensing over a much wider range, enabling the detection of ̴ 1 µm3 E.coli that would otherwise go undetected. Software was written that enables pressure-driven flow control on the scale of individual cells, which is used to great success in (a) sorting cells based on size measurement and (b) monitoring the growth of cells. While there are a number of macroscopic techniques capable of sorting cells, microscopic lab-on-chip equivalents have only recently started to emerge. In this work, a label-free, volume sensor operating at high resolution is used in conjunction with pressure-driven flow control to actively extract particle/cell subpopulations. Next, a microfluidic growth monitoring device is demonstrated, whereby a cell is flowed back and forth through a volume sensor. The integration of sieve valves allows cell media to be quickly exchanged. The combination of dynamic trapping and rapid media exchange is an important technological contribution to the field, one that opens the door to studies focusing on cell volumetric response to drugs and environmental stimuli. This technology was designed and fabricated in-house using soft lithography techniques readily available in most biotechnology labs. The main thesis body contains four scientific articles that detail this work (Chapters 2-5), all published in peer-reviewed scientific journals. These are preceded by an introductory chapter which provides an overview to the theory underlying this work, in particular the non-intuitive physics at the microscale and the Coulter principle.

This master thesis deals with the use of microfluidics for the purpose of microfluidic enzymatic reactor for drug screening. At first it considers the issue from a theoretical point of view – describes microfluidics as a newly developing and promising field of production of microfluidic devices, materials, biomedical applications and advantages and disadvantages of microfluidics overall. Furthermore, it focuses on an area of analytical utilization of enzymes within enzyme reactors. In the first part of the experimental section, conditions for the testing of enzymes of xenobiotics metabolism in the liver were optimized, namely the model of coumarin metabolism via the spectrofluorimetry method. The second part of the experimental work dealt with optimization of the fabrication conditions of microfluidic chips from OSTE (off-stoichiometry Thiol Ene) via the soft lithography method. Subsequently, the functionality of the produced chips was tested. Based on the results of both parts of the experimental work, an evaluation was carried out to assess the suitability of their interconnection for future research – screening of microsomal enzyme activity and model biotransformation of drugs within the channels of the fabricated devices.

Tato dizertční práce se zabývá výrbou a charakterizací plasmonických nanostruktur. Její první část začíná krátkým úvodem do plasmoniky s navazujícím přehledem metod, které jsou v dnešní době nejčastěji používány k výrobě a charakterizaci plasmonických nanostruktur. Druhá část se pak zaměřuje na samotný výzkum, který byl v rámci PhD studia realizován. Cílem prvních experimentů bylo prozkouat možnosti použití elektronové litografie za variabilního tlaku v procesní komoře pro výrobu plasmonických nanostruktur na nevodivých substrátech jako je např. sklo. Jelikož se jedná o materiály, které jsou velice často používány k přípravě plasmonických struktur pacujících v oblasti viditelného světla. Druhá sekce pak diskutuje některé specifické aspekty přípravy plasmonických mikrostruktur elektronovou litografií pro THz oblast. Poslední část se pak zaměřuje na funkční vlastnosti plasmonických nanostruktur, převážně pak na kvantitativní charakterizaci fáze dalekého pole indukovaného plasmonickými nanostrukturami a jejich aplikacemi v oblasti optických metapovrchů - uměle připravených povrchů, které mohou být použity jako planární optické komponenty. Práce demonstruje a diskutuje různé experimentální přístupy použití mimoosové holografické mikroskopie pro jejich charakterizaci.

This work deals about the photovoltaic systems, especially with concentration of the sunlight in use of concentrators that are placed direct on the panel. Concentrated photovoltaics systems employ sunlight concentrated onto photovoltaic surfaces for the purpose of more efficient electrical power production. A photovoltaic cell with concentrator includes difractive optical elements that concentrate light on a photovoltaic chip Flat polycarbonate optical element has difractive gratings on its surface.

Tato diplomová práce se věnuje výrobě vrstev grafitu/grafenu a meření jejich transportních vlastností v závislosti na relativní vlhkosti. Grafenové šupinky byly nanášeny pomocí mechanického odlupování . Pro kontaktování grafenových šupinek byla využita elektronová litografie a na pozorování byly využity optická mikroskopie, mikroskopie atomárních sil a elektronová mikroskopie. V práci jsou popsány jednotlivé kroky výroby, analýzy a měření transportních vlastností nanesených grafenových šupinek.

This master’s thesis is focused on the subject of graphene modified with atomic hydrogen and its electronic transport properties. Structural and electronic properties of graphene and hydrogenated graphene are compared in the theoretical part of the thesis. The Raman spectroscopy technique is described, including characterization of typical Raman spectra of both unmodified and modified graphene. Samples used during experimental part of the thesis are prepared via laser and electron lithography, and are set to be measured in a vacuum chamber. Subsequently, electronic transport properties are measured before and after hydrogen modification of graphene. Finally, hydrogenated graphene is irradiated using electron beam and changes in its structure are analyzed with Raman spectroscopy techniques.