A plasmônica é a área que faz a junção entre fotônica e nanoestruturas. As implicações tecnológicas resultantes do acoplamento entre campos eletromagnéticos e oscilações eletrônicas em um material condutor fazem desta área uma das mais excitantes da óptica atualmente. Neste contexto, o objetivo deste trabalho é o projeto, fabricação e caracterização de nanoestruturas metálicas visando aplicações em óptica difrativa, incluindo filtros e lentes. Inicialmente, uma extensa revisão bibliográfica permitiu definir quais tipos de estruturas seriam abordadas, levando em conta tanto a capacidade computacional para fazer a modelagem numérica quanto a infraestrutura necessária na fabricação dos elementos. A primeira estrutura analisada foi um filtro óptico baseado em ressonância de modo guiado e ressonância plasmônica. Foram projetados e fabricados três filtros operando no azul, verde e vermelho. Resultados experimentais mostraram eficiência acima de 80% e largura de banda em torno de 20 nm, consideravelmente menor que os ~60 nm obtidos previamente na literatura considerando estrutura semelhante. Foi possível verificar as cores puras associadas à ressonância de modo guiado. Além disso, foi demonstrado como gerar as três cores primárias - azul, verde e vermelho - usando apenas o filtro vermelho. A segunda estrutura proposta consiste em uma lente tipo zonas de Fresnel integrada com um filme metálico. Resultados numéricos identificaram uma estrutura ressonante do tipo Fabry-Perot que possibilita uma redução dos lóbulos laterais gerada pela lente por um fator 3.0 na polarização TM e 4.8 na polarização TE. A estrutura foi fabricada usando litografia por nanoimpressão. Por fim, a terceira estrutura analisada foi um holograma binário baseado em metassuperfície, cuja célula básica é composta de um ressoador tipo nanorod. Foi proposta uma geometria na qual a diferença de fase entre os elementos é igual a π independente do comprimento de onda. Assim, o holograma pode operar em uma faixa espectral definida pela largura de banda transmitida. É descrito o inicio da fabricação do elemento usando litografia por feixe de elétrons. / Plasmonics is a field of study that merge photonics and nanostructures. The advanced technological implications makes it one of the most exciting field in Optics in current days. Therefore the objective of this study is the design and fabrication of metallic nanostructures aiming at applications in diffractive optics. Firstly, an extensive literature review allowed to define what types of structures would be addressed, taking into account both software simulations and the require infrastructure for the elements\' fabrication. The first analyzed structure was an optical color filter based on guided mode resonance and surface plasmon resonance. Three filters, operating in blue, green and red, were designed and fabricated using interferometric lithography. Experimental results show above 80% efficiency and ~20 nm bandwidth, which is significantly smaller than ~60 nm previously obtained in the literature with similar structures. It was possible to show the pure colors associated with the modal resonance. Furthermore, it was shown how to obtain the primary red, blue, and green colors using only the red filter. The second structure proposed consists of Fresnel zones plates integrated with a metallic film. Numerical results show a resonant structure which enables side lobe reduction by a factor 3.0 in the TM polarization and 4.8 in the TE polarization. This structure was fabricated using nanoimprint lithography. The third analyzed structure was a binary hologram based on metasurface whose basic cell is composed of a nanorod metallic resonator. The phase difference between two elements is equal to π, regardless of the wavelength; thus, the hologram operates in a spectral band defined by transmitted bandwidth. The first steps of its fabrication process using electron beam lithography are presented and described.

O interesse por aplicações que utilizam efeitos de plásmons poláritons de superfície (SPP) vem crescendo, pois as ondas SPPs apresentam enorme potencial no desenvolvimento de filtros e biossensores ópticos. A sensibilidade da ressonância de plásmons em nanoestruturas permite o estudo em tempo real de variações mínimas em índice de refração, solutos e antígenos. Neste trabalho foram aplicadas técnicas de nanofabricação (litografia por feixe de elétrons e íons) para o desenvolvimento de estruturas plasmônicas e sua posterior caracterização. As estruturas foram utilizadas para verificar propriedades de absorção e fluorescência em moléculas opticamente ativas - Porfirina e Rodamina 6G. As estruturas - conjuntos de fendas e matrizes de buracos circulares com diversos períodos - foram fabricadas em um filme fino de ouro (Au) sobre substrato de vidro (Borofloat 33 - Schott), usando um feixe de íons de Gálio (FEI Quanta Quanta 3D 200i). A transmissão óptica foi estudada na região de 400nm a 900nm (VIS-NIR). Os resultados experimentais foram comparados com simulações computacionais. O estudo da absorção molecular da porfirina foi conduzido observando-se a variação na intensidade da transmissão. Ao alterar a concentração da porfirina sobre as estruturas, foi possível caracterizar a curva de absortividade ε(λ) da porfirina para concentrações entre 100 μg/ml e 500 μg/ml em quantidades mínimas de analito (20 μl). A técnica de microscopia confocal foi empregada no estudo da fluorescência da Rodamina 6G diluída num filme fino de PMMA sobre as estruturas. Ao avaliar a fluorescência da Rodamina 6G na reflexão das estruturas, observou-se o efeito de quenching devido a emissão de plásmons. Os resultados obtidos poderão ser utilizados de apoio a trabalhos futuros, desenvolvidos em plasmônica aplicada a biossensores. / The interest in applications that use the effects of surface plasmon polaritons (SPP) has been increasing. SPPs waves have an enormous potential for the construction of optical filters and biosensors. The sensitivity of plasmon resonance in nano-structures allows studying in real-time minimal variations in the refractive index, solutes and antigens. In this work, we have studied nanofabrication techniques (electron and ion beam lithography) and the characterization of plasmonic structures. Plasmonic effects were used as biosensors of absorption and fluorescence in optically active molecules - Porphyrin and Rhodamine 6G. The structures - sets of slits and arrays of circular holes with different periods - were manufactured in gold (Au) thin film on a glass substrate (Borofloat 33 - Schott) using a galium ion beam equipment (FIB FEI Quanta Quanta 3D 200i). Optical transmission was studied in the region of 400 nm to 900 nm (VIS-NIR). The characterization of structures was realized used the Ocean Optics USB-2000 spectrometer. The experimental results were compared to computer simulations. The study of molecular absorption of porphyrin was conducted by observing the variation in intensity of transmission. By changing the porphyrin concentration in the structures, it was possible to characterize the porphyrin absorptivity curve ε(λ) in concentrations between 100 μg/ml and 500 μg/ml in minimum amounts of analyte (20 μl). Confocal microscopy was used to study the fluorescence of Rhodamine 6G on plasmonic structures. The plasmon quenching effect was observed in the evaluation of the fluorescence of Rhodamine 6G in the reflection of the structures. The results will support future works linking plasmonics and biosensors.

Most of the time, in a nano-fabrication facility, the efforts of a researcher are devoted to optimising the fabrication process in order to avoid defects and obtain the best result in terms of precision and quality of the fabricated device. However, it is inevitable that during the sample fabrication, a variable intrinsic amount of disorder is introduced. This feature can be exploited to develop novel applications spanning different areas of optics. A perfect unclonable cryptographic system based on new integrated optical fingerprints chip is presented and a proof of concept is provided. The role of disorder at the nanoscale is further studied in the fabrication processes such as electron beam lithography and dry-etching. In this scenario, the randomness is the starting point to develop new technologies for structural coloration and holograms.

Freestanding low pressure chemical vapor deposition (LPCVD) silicon nitride (SiN) membrane resonators are widely investigated as Nano-Electromechanical System (NEMS) for their outstandingly low mechanical dissipation and high mechanical quality (Q) factor. The high Q-factor brings better sensitivities to force, displacement, and temperature excitations. However, integrated actuation methods are not trivial to implement on this platform and are required to harness their high Q-factor in practical applications. The first goal of this research is to develop a recipe for fabricating large area low stress LPCVD SiN membrane since commercial membranes are relatively expensive and have limited flexibility in terms of geometries. Starting from 4 inches, 500 μm thick, (100) single crystal silicon wafers double-side coated with 100 nm LPCVD SiN, we successfully fabricate five different sizes (i.e., 1 mm, 1.5 mm, 3 mm, 6 mm and 12 mm) of square shape membrane chips. The developed recipe is universally applicable for any size (i.e., under 12 mm) of square shape SiN membrane from the same type of wafer. All recipe parameters are presented in this work, along with experienced challenges and their associated solutions. The second part of this work is to develop an on-chip actuation method for these resonators. We develop a new method for creating acoustic waves in the silicon substrate using metal – silicon nitride – silicon capacitors. Acoustic waves due to the voltage-dependent mechanical stress arising from charge attractions was already observed previously in silicon substrate p-n junction resonators but is observed here for the first time in a capacitively coupled metal-dielectric-semiconductor (MDS) assembly. In the MDS system, we model three main possible actuation regimes, i.e., depletion, accumulation, and thermal expansion. Both depletion and accumulation rely on electrostatic attraction forces in MDS capacitors when an AC electrical current flows through. The same current can also generate thermal expansion forces resulting from resistive dissipation in the silicon. This contribution, however, is found to be negligible. In experimental measurements on 1.5 mm membranes in high vacuum, the accumulation MDS is found to perform better than the depletion one in terms of membrane actuation amplitude. With 2 V drive voltage, the membrane achieves up to 10 nm displacement for fundamental mode (1, 1). The contribution of thermal expansion forces is found to be negligible, with resonator temperature changes smaller than 4 mK. A comparison of energy dissipation between a conventional external piezo actuation method and our approach is also presented, through which we find that both methods have comparable power consumption.

Organic Photovoltaic devices (OPV) are considered to be attractive candidates for clean and renewable energy source because of their potential for low cost of fabrication, easy processing, and their mechanical flexibility. The device efficiency of OPV cells are limited by several factors. Among them are: (i) donor-acceptor interface, (ii) morphology of the materials, (iii) electrode-organic semiconductor (OSC) interface and (iv) device architecture such as active material thickness and electrode separation. Although, the donor-acceptor interface has been studied in detail, the commonly prevalent vertical OPV device structure does not allow a good understanding of the other key issues as the vertical structure limits one of the electrode to be a transparent electrode as well as introducing inseparable relation between the electrodes separation and the active material thickness. In addition, it is also well known that the charge transport in OSC is anisotropic and the charge mobility is better in lateral direction rather than vertical direction. In order to address some of these issues, we fabricated OPV devices in a planar device structure where cathode and anode of dissimilar metals are in-plane with each other and their photovoltaic behaviors were studied. We used poly(3-hexylthiophene) and [6,6]- pheny1 C61-butyric acid methy1 ester (P3HT:PCBM) blend as an active material. In particular, we present a detailed study about the effects of the structural parameters such as the channel length, the active layer thickness, and the work function of the electrodes on the open circuit voltage (Voc), short circuit current (Isc), fill factor (FF) and the power conversion efficiency (PCE). In order to determine the suitable anode and cathode for the planar organic photovoltaic (P-OPV) structure, we first fabricated and measured organic field effect transistor (OFET) devices with different contacts and studied the effect of barrier height at the iv P3HT:PCBM/electrode interface on the device output and transport properties. The study showed a clear effect of varying the contact material on the charge injection mechanism and on the carriers mobilities. The results have also shown that Au with high hole mobility and on current in the p-channel can be used as an anode (holes extractor) in the P-OPV device while In, Cr, and Ti that showed a reasonable value of electron mobility can be good candidates for cathode (electron extractor). We also found that, Ag, Al, and Mg showed large barrier which resulted in large threshold voltage in the I-V curve making them undesired cathode materials in the P-OPV device. We then fabricated P-OPV devices with Au as an anode material and varied the cathode material to study the effect of the interface between the P3HT:PCBM layer and the cathode material. When Al, Mg, or Ag used as a cathode material no PV behavior was observed, while PV behavior was observed for In, Cr, and Ti cathode materials. The PV behavior and the characteristic parameters including Voc, Isc, FF and PCE were affected by varying the cathode material. The results have shown that the P-OPV device performance can be affected by the cathode material depending on the properties and the work function of the metal. We have also studied the effect of varying the P3HT:PCBM layer thickness at a fixed channel length for Cr and Ti cathode materials and Au as anode. While Voc and FF values do not change, Isc and PCE increase with increasing the layer thickness due to the increase of the light absorption and charges generation. Moreover, we studied the effect of varying the channel length at a fixed film thickness; and showed that the values of Isc and PCE increase with decreasing channel length while Voc and FF maintain the same value. In this thesis we will also present the results on experimentally defining and testing the illuminated area in the P-OPV device by using different measurement set-ups and different v electrodes patterns. The results prove that the illuminated area in the P-OPV device is the area enclosed between the two electrodes. Lastly, we will present the effect of the P3HT:PCBM ratio on the P-OPV device performance. We show that 1:2 ratio is the optimized ratio for the P-OPV device. The detailed results in this thesis show a potential opportunity to help improving and understanding the design of OPV device by understanding the effects of the device structural parameters.

Diblock copolymers like poly(styrene)-block-poly(2-vinylpyridine) pave the way for controllable self-assembled monolayers of nanoparticles. Using particular polymer weights and concentration, spherical micelles of PS-b-P2VP can be constructed with a non-polar PS corona and a polar P2VP core. Various precursor salts can be loaded into the core of the micelles due to interactions with the polar core which forms as the active site for nanoparticle growth. The PS corona protects the core from the atmosphere and non-polar solvents. The micelles can then act as nanobeakers for aqueous chemistry in two ways; spontaneous reactions between precursors result in nanoparticles or the trapping of precursor salts can be oxidized or reduced using polymer removal techniques like gas plasmas. In this way, reverse micelles are a facile method of growing metal, metal oxide or dielectric nanoparticles. Process parameters, such as concentration, molecular weights, nature of solvents and type of precursor salt, offer control over the periodicity and size of the monolayer of nanoparticles. Reverse micelle templating is a potentially useful nanofabrication method for tailor-made nanoparticles for use in electrical and optical devices which is not limited to form-factor of substrates. In this thesis, obstacles are identified that hinder the utility of PS-b-P2VP templated nanoparticles in device fabrication. The polymer is insulating which is detrimental to electrical applications. Additionally, the characterization of a monolayer of polymers, thus far, is limited to structural techniques such as SEM and AFM. This thesis sheds light on the mechanism of precursor loading in the micelle core, discusses the efficiency of different polymer removal techniques and uses vibrational spectroscopy for the characterization of monolayers of polymer, loaded polymer and nanoparticles. We have tested enhanced Raman methods using AFM probes to extend the resolution of normal Raman to view monolayers of empty polymers as well. Moreover, using FeCl3-loaded polymer micelles, the control offered by PS-b-P2VP templated growth on the crystal structure of nanoparticles is laid bare. The usefulness of the technique is further divulged by using ordered gamma-Fe2O3 nanoparticles in water-splitting photoanodes where they show an increased efficiency with the inclusion of nanoparticles and their periodicity. This is just an example of devices using reverse micelle templated nanoparticles, paving the way for future applications. The flexibility of this method is further revealed by constructing self-assembled Au/SnO2 nanojunctions within the PS-b-P2VP micelle cores. This was done by exploiting the spontaneous redox reaction between HAuCl4 and SnCl2 in an aqueous environment, and so can be replicated for other metals and metal oxides like Pt, Pd, Ag, TiO2 and ZnO2. The composite nanoparticles formed exhibit a tunable size and dispersion as typically seen with PS-b-P2VP micelles and so, can be used for various applications which require metal/metal oxide junctions. / Thesis / Doctor of Philosophy (PhD)

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No / The most important issue during synthesis of nanoparticles (NPs) is to avoid particle agglomeration and adhesion. There have been several attempts to use special substances such as organic surfactants, polymers and stable ligands for this purpose. In this study, silver NPs were synthesised with and without gelatin macromolecules, as a green natural biopolymer, which resulted in NPs with varying shapes and sizes. The effect of morphological characteristics on the antibacterial and antifungal properties of the synthesised NPs were studied, by comparing Gram-negative (Escherichia coli) versus Gram-positive (Staphylococcus aureus) bacteria as well as fungi (Candida albicans) by calculation of minimal inhibition concentration value. The results corresponded well with the assumptions on the effects of shape and size on the antibacterial and antifungal properties of the studied NPs.

Plasmonics can achieve the tight optical confinement and localization in the subwavelength domain. Surface plasmon polaritons (SPPs) are closely related to coupling to emitters in excitation and emission, waveguiding, and active modulating on the nanoscale. Due to these phenomenon, plasmonic nanostructures can be used for applications, such as light emission, photodetection, optical sensing, and spectroscopy. Conventional plasmonic nanostructures can support plasmonic modes, and it is typically optimized for a single wavelength window with planar plasmonic structures. Recent studies have reported some in-plane composite nanostructures and core-shell geometries can induce multiple plasmonic responses. However, it is challenging to achieve the control of individual plasmonic response due to the interdependent spectral tunability with changes in their in-plane geometries. In this dissertation, the concept of out-of-plane engineered nanoantenna structures is introduced, numerically calculated, and experimentally demonstrated. The nanolaminated MIM plasmonic structures show multiresonant plasmonic responses in the same antenna and each wavelength band can be tunable individually with different thicknesses of dielectric layers. The nanolaminated plasmonic structures has been reported for a scalable Surface-enhanced Raman spectroscopy (SERS) substrate for single-molecule sensitive and label-free chemical analysis. Due to the strong optical field confinement, the nanolaminated SERS substrates achieve increased SERS enhancement factor (EF) up to 1.6 x 108 with proper partial etching of dielectric layers. Furthermore, the nanolaminated MIM plasmonic structures have been successfully integrated with micro-scale pillar arrays to control the surface wettability for ultrasensitive SERS measurements. The hierarchical micro/nano plasmonic surface has densely packed intrinsic SERS-active hot spots that give rise to SERS EFs exceeding 107. This platform can take full advantage of low surface energy to control and measure the analyte in water droplets. Leidenfrost evaporation-assisted SERS sensing on the hierarchical substrates provides the way for ultrafast and ultrasensitive biochemical detections without a need for additional surface modifications and chemical treatments. / Doctor of Philosophy / The life in the 21th century has benefited from the technical revolutions of computational power that is based on the manipulation/storage of electrons. As predicted in Moore's law, the size of electronic microchip would go down, and the computational power has been enhanced due to the increase of transistor integration density. However, the two major factors, such as energy dissipation of electrons and signal delay of electronic circuit, limit the communication speed of electronics. These barriers have caused slowdown in the performance of computational power. Photonic solutions have been offered to solve the limitations based on the larger bandwidth and a rare energy dissipation, compared to electronic counterparts. Moreover, optical communications typically demand much lighter channel to deliver similar power/information than practical electrical cables do. Thus, light manipulation/enhancement techniques are envisioned to overcome the limitations and guide to the methodology of interconnections between the electronic circuits and optical platforms. Plasmonics can achieve the nanoscale light confinement and localization in the subwavelength domain. This strong confinement is originated from the coupling between the photons and the electron gas on the metal that results in surface plasmon polariton (SPP). SPPs are closely related to coupling to emitters in excitation and emission, waveguiding, and active modulating on the nanoscale. Due to these phenomenon, plasmonic nanostructures can be used for applications, such as light emission, photodetection, optical sensing, and spectroscopy. In this dissertation, the concept of out-of-plane engineered nanoantenna structures is introduced, numerically calculated, and experimentally demonstrated. This vertically stacked nanoantenna structure is composed of metal-insulator-metal (MIM) laminates fabricated by physical vapor deposition techniques. Although conventional plasmonic nanostructures can support plasmonic modes, it is typically optimized for a single wavelength window. The nanolaminated MIM nanostructures, by contrast, can induce multiresonant plasmonic response in the same antenna with several advantages: (1) reduced individual footprint size and volume of nanoantenna, (2) accurate control of layer thicknesses by thin film deposition technique for resonance tuning, (3) easier integration with other functional materials as gap layers, and (4) efficient transport of charge carriers or heat in nanolaminated layers. As a result of the tight optical field confinement, the nanolaminated plasmonic structures can be used for sensing application called Surface-enhanced Raman spectroscopy (SERS), which is a promising sensing platform for label-free biochemical analysis at the single-molecule level. Partial oxide etching process enables the analyte molecules to accommodate in strong enhancement region of the nanolaminated structures, resulting in amplified unique Raman features of molecular compounds as a finger print. The SERS enhancement factor is increased by one order of magnitude achieving 1.6x108. Furthermore, the nanolaminated plasmonic structures have been integrated with micro-scale pillar arrays to control the surface wettability for ultrasensitive SERS measurements.