This dissertation focuses on four research topics: self-assembly of colloidal nanoparticles, surface modifications of the properties of ionically self-assembled multilayer films, surface enhanced Raman spectroscopy of functionalized gold nanoparticles, and two photon uncaging in gel. Those techniques are used for development of novel nanofabrication methods for top-down and bottom-up assembly of nanostructures, by modifying the properties of nanopatterned surfaces with photoactive ligands, and other technologies. First I describe the development of an improved method for nanosphere lithography, a variation of the convective self-assembly technique. The method exhibited high reproducibility and yielded high quality monolayer crystals by withdrawing a meniscus of liquid polystyrene spheres solution and subsequent evaporation of the solvent. The monolayer crystal was used as an evaporation mask to create surface arrays of gold nanotriangular particles. Metal nanoparticles, with sharp features or narrow gaps, exhibit strong plasmonic properties. I took advantage of those properties to attempt to create patchy modifications of the surface functionalization of gold nanotriangular particles treated with photosensitive molecules. Two molecules denoted, P3-DTC, and LIP3, were used as functional molecules attached to the gold nanoparticles. After interaction with 356nm UV light, part of those molecules cleaves off the surface of the nanoparticles rendering the surface modified with a new functional group. The modification takes place only at the plasmonic hot spots of those nanoparticles, resulting in a patchy modification of the properties of the nanoparticles. I built polymer Ionically Self-assembled Multilayer (ISAM) films using a Layer-by-Layer deposition technique and treated them to alter their surface adhesion properties. Poly (allylamine hydrochloride) (PAH), and poly (styrene sulfonate) (PSS) are a very well-studied system of polyelectrolytes for LbL deposition. ISAM films built from those polyelectrolytes are rich in amine groups to which nanoparticles, cells, tissue cultures, ligands can be made to adhere. In my work I developed a method for selective modification of the surface adhesiveness, by neutralizing the amine groups trough acetylation with acetic anhydride. With resolution from a few microns to a few hundred nanometers, I selectively passivated some areas of the ISAM film while others I left unaltered. I tested the effect of the acetic anhydride passivation by performing Horse Radish Peroxidase (HRP) test which quantifies the amount of free amines on the surface of the film. I also demonstrated the patchy modification of surface adhesiveness by introducing gold nanospheres which attached only to the amine active areas of the modified ISAM film. Photoactivatable fluorophores, i.e. compounds and other entities that may transform into a fluorescent form on absorption of a photon can be employed in multidimetional volume patterning. I studied the photoactivation of aryl azides in gelatin matrix. Specifically, I used Azidocoumarin 151 as a test molecule to undergo two-photon activation, and then measured the resulting photoluminescence. The activation of the Azidocoumarin 151 can be used to create arbitrary 3D patterns of modified functionality inside the gel. The activated molecules can be used as sites for further modification of the patterning inside the volume of the gel. Possible modifications include attaching biomolecules, nanoparticles, or individual cells. / Ph. D.

Shrinking the feature size of very large scale integrated circuits (VLSI) with advanced lithography has been a holy grail for the semiconductor industry. However, the gap between manufacturing capability and the expectation of design performance becomes critically challenged in sub-16nm technology nodes. To bridge this gap, design for manufacturing (DFM) is a must to co-optimize both design and lithography process at the same time. DFM for advanced lithography could be defined very differently under different circumstances. In general, progress in advanced lithography happens along three different directions: (1) New patterning technique (e.g., layout decomposition for different patterning techniques); (2) New design methodology (e.g., lithography aware standard cell design and physical design); (3) New illumination system (e.g., layout fracturing for EBL system, stencil planning for EBL system). In this dissertation, we present our research results on design for manufacturing (DFM) with multiple patterning lithography (MPL) and electron beam lithography (EBL) addressing these three DFM research directions in advanced lithography. For the research direction of new patterning technique, we study the layout decomposition problems for different patterning technique and explore four important topics: (1) layout decomposition for triple patterning; (2) density balanced layout decomposition for triple patterning; (3) layout decomposition for triple patterning with end-cutting; (4) layout decomposition for quadruple patterning and beyond. We present the proof that triple patterning layout decomposition is NP-hard. Besides, we propose a number of CAD optimization and integration techniques to solve different problems. For the research direction of new design methodology, we will show the limitation of traditional design flow. That is, ignoring triple patterning lithography (TPL) in early stages may limit the potential to resolve all the TPL conflicts. We propose a coherent framework, including standard cell compliance and detailed placement, to enable TPL friendly design. Considering TPL constraints during early design stages, such as standard cell compliance, improves the layout decomposability. With the pre-coloring solutions of standard cells, we present a TPL aware detailed placement where the layout decomposition and placement can be resolved simultaneously. In addition, we propose a linear dynamic programming to solve TPL aware detailed placement with maximum displacement, which can achieve good trade-off in terms of runtime and performance. For the EBL illumination system, we focus on two topics to improve the throughput of the whole EBL system: (1) overlapping aware stencil planning under MCC system; (2) L-shape based layout fracturing for mask preparation. With simulations and experiments, we demonstrate the critical role and effectiveness of DFM techniques for the advanced lithography, as the semiconductor industry marches forward in the deeper sub-micron domain. / text

<p>During the past two decades, soft lithographic techniques that circumvent the limitations of photolithography have emerged as important tools for the transfer of patterns with sub-micron dimensions. Among these techniques, microcontact printing (uCP) has shown special promise. In uCP, an elastomeric stamp is first inked with surface-reactive molecules and placed in contact with an ink-reactive surface, resulting in pattern transfer in the form of self-assembled monolayers in regions of conformal contact. The resolution in uCP is ultimately limited to the diffusion of ink and the elastomechanical properties of the bulk stamping material. </p> <p>One way to improve resolution is to eliminate diffusion by using inkless methods for pattern transfer. Inkless catalytic-uCP uses a chemical reaction between a stamp-immobilized catalyst and surface bearing cognate substrate to transfer pattern in the areas of conformal contact. By using pre-assembled cognate surfaces, the approach extends the range of surfaces readily amenable to patterning while obviating diffusive resolution limits imposed by traditional uCP. </p> <p>In this thesis, we report two methods using inkless catalytic uCP: biocatalytic-uCP utilizes an immobilized enzyme as a catalyst whereas catalytic-uCP utilizes an immobilized small molecule as a catalyst, such as an acid or base. Both catalytic techniques demonstrate pattern transfer at the microscale while using unconventional, acrylate-based stamp materials. Previous results produced with catalytic-uCP have shown pattern transfer with sub-50 nm edge resolution. In this demonstration of catalytic-uCP, we use the technique to demonstrate a bi-layered patterning technique for H-terminated silicon, the foremost material in semi-conductor fabrication. This technique simultaneously protects the underlying silicon surface from degradation while a highly-reactive organic overlayer remains patternable by acidic-functionalized PU stamps. Lines bearing widths as small as 150 nm were reproduced on the reactive SAM overlayer, which would not be possible without circumvention of diffusion. Before and after patterning, no oxidation of the underlying silicon was observed, preserving desired electronic properties throughout the whole process. This bi-patterning technique could be extended to other technologically-relevant surfaces for further application in organic-based electronic devices and other related technologies.</p> / Dissertation

The microelectronics industry strives for continued reduction in feature sizes to allow increased computing speed and power. This calls for continuous development of new materials. During the shift to 157 nm photolithography, it was discovered that fluorinated materials were necessary to provide sufficient transparency. Material design and synthesis to incorporate fluorine bearing norbornane based materials through an alternate means of polymerization to those used in traditional lithographic materials will be presented. Step and Flash Imprint Lithography represents a low cost alternative to optical lithography for production of nanoscale features. Sub-20 nm features have been produced using commercial tools however the contact between the imprint template and resist formulation leaves the template prone to fouling. A new imprint resist designed to facilitate wafer reworking and template cleaning is presented. The small amount of power available from deep ultraviolet light sources necessitates the use of systems that behave in a catalytic manner that is referred to as gain. The use of small molecules for gain necessitates a reliance on diffusion through the resist film and results in image bias. A polymeric material that undergoes depropagation catalyzed by a single photochemical event and causes a solubility change due to this event represents a system that possesses gain while removing diffusion bias. Progress towards such a system is presented. / text

The advent of highly sophisticated drugs designed to interfere with specific cellular functions has created the demand for “intelligent” carriers that can efficiently deliver therapeutic agents in response to a pathophysiogical condition. Nanoscale intelligent systems can maximize the efficacy of therapeutic treatments in numerous ways because they have the ability to rapidly detect and response to disease states directly at the site and sparing physiologically healthy cells and tissues, thereby improving a patient’s quality of life. Nanoparticle fabrication has primarily relied on emulsions, self-assembly and micelles based methods which inherently generate polydisperse spherical particles with little control over particle geometry. Despite significant progress in such drug delivery systems, critical limitations remain in synthesizing nanocarriers with highly controllable architecture (size, shape or aspect ratio) that can, at the same time, impart response-sensitive release mechanisms. These parameters are essential for controlling the in-vivo transport, bio-distribution, and drug release mechanisms. The objective of my dissertation is to employ the nanofabrication technique Step and Flash Imprint Lithography (S-FIL) to synthesize stimuli-responsive nanocarriers of precise architectures and composition. Applying S-FIL technology, fabrication of nanocarriers of a variety of shapes and sizes (down to 36nm length scale) that are also environmentally responsive by incorporating enzymatically-degradable peptides into the nanocarrier hydrogel matrix, to provide triggered release of encapsulated therapeutic agents in response to specific pathophysiological conditions, has been accomplished. Besides disease-responsive release, the two key properties of an effective nanocarrier are (a) efficient targeting to specific tissues and cells and (b) avoiding rapid clearance and remaining in circulation in the blood stream for a significant amount of time to increase particle uptake in target tissues. These two properties are expected to be dependent on the shape and size of the carriers. Using various shape and size S-FIL fabricated nanoparticles, the effects of particle geometry on intracellular uptake has also been evaluated. In this dissertation, I will present the extensive work that has been done in the fabrication and optimization of the S-FIL nanocarriers, evaluation of the nanocarrier’s in vitro properties, and evaluation of the effects of nanocarrier geometry on intracellular uptake. / text

No description available.

Throughout this work several thin film resists have been studied with substantial focus on HafSOx and SU-8. The study of HafSOx has granted more insight into how inorganic, spin coated films form and react under the electron beam. These films have been shown to form a thin dense crust at the surface that could have interesting implications in the interaction of the electrons. Continuing to further understand the electron interactions within the resist, low voltage patterns were created allowing the accelerating voltage to be matched to the film. With this general knowledge, higher resolution films can be constructed with shorter patterning times. Both resists complement each other in that HafSOx produces incredibly thin, dense structures to be formed with features below 10 nm in all dimensions. SU-8 allows micron thick features to be created over several millimeters. This flexibility in feature size enabled the creation of large fractals that could improve neuron binding to artificial retina down to the smallest fractals reported that are interesting for their applications as antennas. The final facet of this work involved looking at other methods of making structures. This was done through adding differing salts to organic molecules that stack into unique crystals. This dissertation includes previously published co-authored material.

Durant la dernière décennie, la résonance de plasmon de surface (SPR) est devenue très populaire pour effectuer des analyses au cours d’un greffage chimique (ou biochimique) et étudier ainsi des réactions chimiques. Ce travail de thèse avait pour but de développer une méthode lithographique alternative, la nanoimpression assistée UV dite «douce», qui permet de fabriquer des réseaux de nanomotifs sur de très grandes surfaces (voir chapitre 1 - état de l’art) pour générer des nanostructures métalliques SPR intégrables. Les chapitres 2 et 3 étudient les paramètres expérimentaux de la nanoimpression pour obtenir des nanostructures hautement résolues et avec un minimum de défaut. Notre étude optique a été menée ensuite sur des réseaux de nanotrous imprimés dans des films d’or (chapitre 4). Le mécanisme physique du phénomène de transmission assistée par les plasmon est étudié de manière systématique d’après l’évolution de la position du pic de transmission avec les paramètres structuraux. Des mesures réalisées dans un système fluidique ont ensuite montré une réponse à un faible changement de l’indice de réfraction à la surface du réseau. Enfin, le dernier chapitre (chapitre 5) présente une nouvelle géométrie de biocapteurs optique basé sur une structure tri-couche dans une géométrie de type «nanocavité» à plasmon localisé (LSPR). Ces capteurs LSPR à nanocavités permettent d’améliorer le facteur de mérite d’un ordre de grandeur par rapport aux LSPR classiques. Leurs propriétés de résonance sont discutées à l’aide d’outils de simulation numérique. Enfin, nous démontrons qu’un tel capteur possède une grande sensibilité à la détection de biomolécules et serait donc adapté à l’étude d’interactions immunochimiques. / During the last decade, surface plasmon resonance (SPR) has become widely used to characterize a biological surface and to characterize binding events in the fields of chemistry and biochemistry. Research in this field has been favoured by the tremendous growth in nanofabrication methods among which soft lithographies are alternatively emerging. The purpose of this thesis work was to develop soft UV nanoimprint lithography, an emerging flexible technology allowing patterning on large area of subwavelength photonic nanostructures. The main advantages offered by soft UV nanoimprint lithography concern the simple patterning procedure and the low cost of the experimental setup (see state-of-art presented in chapter 1). Chapters 2 and 3 present the fabrication of master stamps, the study of nanoimprinting parameters coupled with the optimization of the etching process in order to get metallic nanostructures with limited pattern defects. The physical mechanisms of the transmission phenomenon exalted by surface plasmons were studied based on arrays of imprinted gold nanoholes (chapter 4). Extraordinary light transmission has been experimentally demonstrated. The geometrical effects on the position transmission peak were systematically analyzed. Proof-of-concept measurements performed in simple fluidic device indicate a response to small changes in refractive index in the surface vicinity. Finally, chapter 5 proposes a novel design for the optical sensor which is based on “nanocavities” exhibiting coupled localized plasmons. This LSPR sensor offers an improvement of one order of magnitude of the Figure of Merit compared to classical LSPR sensors. The resonance properties of these innovative nanocavities have been studied from numerical simulations and discussed based on their geometrical dependence. Since this system has demonstrated higher sensitivity for detection of biomolecules, it is thus fully adapted to study immunochemical binding interactions.

Este trabalho teve como objetivo principal o estudo de técnicas de nanofabricação aplicadas a filmes semicondutores do grupo 111-V, crescidos pela técnica de epitaxia por feixe molecular. Padrões, visando o domínio da técnica e a produção de nano-estruturas foram criados em filmes de GaAs utilizando-se a técnica de litografia por feixe de elétrons e ataques químicos. Os padrões foram gerados a partir de um software especial de controle que, acoplado ao microscópio eletrônico de varredura, através de uma interface, permite o controle externo da varredura x-y do feixe de elétrons. Estudamos o comportamento da espessura do filme de elétron-resiste poli (metacrilato de metila) (PMMA) em função da temperatura, aplicando soluções com pesos moleculares variados sobre filmes semicondutores, dissolvidos em Xileno, Monoclorobenzeno e Acetona. Investigamos o uso do ultra-som nos processos de revelação do PMMA e no ataque químico de superfícies de GaAs. Através da análise do ataque químico empregando várias formulações a base de ácidos em GaAs (100) e (3 1 l)A e B, determinamos a velocidade de ataque em cada caso, classificando as propriedades obtidas para a superfície. Em GaAs (100) avaliamos a dependência entre a rugosidade da face atacada e o tempo de ataque para uma solução de NH4OH:H2O (pH=7). Os resultados por nós obtidos formam um conjunto de dados que servirão de apoio a trabalhos futuros, desenvolvidos em nano-fabricação aplicada a filmes de GaAs, crescido em planos diferentes do (100). / This work had as main objective the study of nanofabrication techniques applied to thin semiconductor 111-V films, grown by molecular beam epitaxy. Patterns were generated to verifying the domain of the technique in the production of nanostructures in GaAs films, by means of chemical attack and electro-lithography. The patterns were generated with special software that connects the electronic microscope(Leo 440), through an interface that allows the externa1 control of the x-y sweeping for the electron beam. We studied the behaviour of the thickness of the electron-resists films of poly-methyl-metacrilate in hnction of the Spinner rotation, applying solutions with varied molecular weights on semiconductor films, dissolved in Xilene, Monoclorobenzene and Acetone. We investigated the use of the ultra-sound in the processes of revelation of PMMA and in the chemical attack of surfaces of GaAs. Through the analysis of the chemical attack using severa1 formulations of acids in GaAs (100) and (311)A and B, we determined the attack rate in each case, classifying the properties obtained for the surface. In GaAs (100) we evaluated the dependence between the nano-rugosity of the attacked face with the time of attack for a solution of NH4OH:H2O2 (pH=7). The results obtained by us form a group of data that will support future works, to be developed in nanofabrication applied to GaAs thin films grown in plans different from the (100).

The formation of a functional surfaces combines the properties of a substrate and monolayer to produce a new hybrid that can combine aspects of each. Monolayers can be made on many surfaces, and well defined functionalized monolayers were assembled on for silicon(111) and polydicyclopentadiene (PDCPD). Acid terminated monolayers were assembled on silicon(111) and their functionalization chemistry explored. It was shown that using trifluoroacetic anhydride to generate an intermediate reactive anhydride, the surface could be functionalized with amines. It was further shown that using soft lithography these functionalized surfaces could be patterned. Mixed monolayers of methyl and olefin terminated surfaces on silicon(111) were used to develop a new soft lithographic technique with polydimethylsiloxane (PDMS). PDMS can be controllably etched using fluoride species. The surface is first activated by the attachment of the Grubbs' 1st generation catalyst. A PDMS microfluidic device is then placed on the surface. By using a cross metathesis reaction, the exposed channel can be pacified. The next step, a fluoride etchant is used to remove PDMS, exposing an unreacted surface. Polymer brushes were then grown by ring opening metathesis polymerization (ROMP) in this region. Functionalization of the emerging polymer PDCPD was conducted through two different routes. ROMP formed PDCPD has double bonds that can be functionalized. In the first process, the double bonds were reacted with bromine. This is a rapid reaction and proceeds to a significant depth in the material. Bromines can then be displaced with amines in a substitution reaction. This was demonstrated with a fluorinated amine that when examined by XPS were shown to be present only at the surface, further more we were able to pattern this surface too. Secondly, a process using epoxides was developed. The epoxidation reaction could not be quantified, but formation in the second step of an amine functionalized surfaces was observed by XPS. Further reaction of surface hydroxyls was also observed. This was also used to grow polyethylimine from the surface to sufficient thickness that it became observable by infrared spectroscopy.