La spectroscopie Raman exaltée de surface (SERS) est largement utilisée comme un outil non-intrusif et sans marquage pour identifier les empreintes spectrales moléculaires dans des applications comme la pharmacologie, la salubrité des aliments, etc. Cette thèse présente un micro-capteur SERS basé sur un guide d'ondes hybride constitué de fentes métalliques (Au/Al) et de rubans diélectriques (Si3N4) et sur une méthode pour promouvoir la capacité de détection SERS en plaçant des nanoparticules métalliques dans la fente du capteur. L'étude théorique du capteur est principalement menée par la méthode des différences finies dans le domaine temps en trois dimensions (3D-FDTD) qui fournit la réponse électromagnétique à large bande des nanostructures métalliques. Les facteurs d'exaltation du capteur sont estimés par l’approximation |E|4. Les expériences sont basées principalement sur la fabrication de fentes métalliques, qui est réalisée par la lithographie à faisceau d'électrons (EBL), et sur la caractérisation de la capacité de détection SERS des capteurs. Les résultats montrent que les signaux Raman donnés par les capteurs SERS sont détectables. Les nanoparticules métalliques, qui sont situées dans le capteur, peuvent améliorer considérablement la capacité de détection SERS. En combinant le capteur SERS avec les éléments photoniques et électroniques, un système de détection SERS entièrement intégré sur une puce peut être développé dans un proche avenir pour des détections SERS portables et stables / Surface-enhanced Raman spectroscopy (SERS) is widely used as a non-intrusive and label-free tool to identify the molecular spectral fingerprints in pharmacology, biology, etc. This thesis presents a SERS sensor based on the hybrid waveguide made of metallic (Au/Al) slots and dielectric (Si3N4) strips and a method to improve the SERS-detection capacity by placing metallic nanoparticles into the sensor’s slot. The theoretical investigation of the sensor is mainly conducted by the 3D finite-difference time-domain method (3D-FDTD) which provides the broadband electromagnetic response of metallic nanostructures. The enhancement factors in the sensor’s slot are estimated based on the |E|4-approximation. The experiments are mainly the fabrication of metallic slots, which is conducted by the electron beam lithography (EBL), and the characterization of the SERS-detection capacity of the sensors. The results show that the Raman signals given out by the SERS sensors are detectable. Metallic nanoparticles, which are located in the sensor’s slot, can improve dramatically the SERS-detection capacity. By combining the SERS sensor with the extended photonic and electronic elements, a fully integrated-on-chip SERS detection system on a chip can be developed in the near future for portable and stable SERS detections

Xanthene dyes are common fluorophores which have been widely used as molecular probes. The xanthene fluorophores can be used as highly selective optical sensors to detect disease biomarkers. A new fluorogenic dye containing an alpha, beta-unsaturated aldehyde moiety exhibits selective fluorescent signal enhancement in the presence of cysteine or peptides containing N-terminal cysteine residues. The mechanism is based on synergistic covalent and supramolecular interactions. A unique rhodamine boronic acid indicator is used in an optimized data collection protocol for wavelength- and time-dependent selectivity of various saccharides and nucleosides. One indicator is thereby capable of selectively distinguishing structurally related analytes in mixtures. Moreover, the rhodamine-based boronic acid responds linearly to increasing riboside concentrations in urine samples, potentially enabling the screening for inborn purine metabolism disorders.

Polarimetry, as applied to chemical analysis, deals with the determination of the extent and direction that an optically active chemical species will rotate incident linearly polarized light. Although well developed for physical sensing, the technique of fiber optic polarimetry for chemical sensing remains in its infancy. This thesis is concerned with the design and development of an optical fiber polarimeter which measures the optical rotation of linearly polarized light that occurs in a sensing region between two multi-mode optical fibers. Over short distances, the polarization preserving capabilities of large-core multi-mode optical fibers were investigated. Polarimetric analyses were performed using sucrose and quinine hydrochloride. The instrument has a resolution of 0.08·, and is an excellent platform for an LC or FIA detector. Its more intriguing future lies in evanescent field sensor applications and studies of chiroptical surface interactions. / Master of Science

Approved for public release, distribution is unlimited / In this thesis, a series of experiments were performed to characterize the material properties of InGaAs/GaAs for use in a two-color quantum-well IR photodetector (QWIP) design. Results from room temperature studies using cathodoluminescence and photoluminescence indicated light emission at 858 nm and 1019 nm from GaAs and InGaAs, respectively. Using a direct transport imaging technique, an edge dislocation pattern was observed and shown to be confined to the InGaAs layer of the material. A dislocation density measurement was performed and was shown to be less than 2000 lines/cm. Quantitative intensity level measurements indicated fluctuation in the region of dislocations to be less than 30% of the signal to background level. Finally, a spot mode study using the direct transport imaging method was performed to evaluate the feasibility of using this technique for contact-less diffusion length measurements. / Civilian, Department of Air Force

[pt] A poluição atmosférica é um problema mundial latente e é prejudicial à saúde, à visibilidade e ao clima. Devido a estes fatores, diversos estudos e pesquisas foram desenvolvidos para caracterizar a sua composição química, concentração, tamanho de partículas, etc. Com o objetivo de construir instrumentos adequados para o controle da qualidade do ar, mas estes instrumentos são sofisticados, complicados e de alto custo. Esta dissertação refere-se ao estudo de viabilidade para a utilização de componentes optoeletrônicos simples, tais como diodos emissores de luz (LED) e fotodetectores ópticos, como sensores de medição da variação da concentração de poluentes particulados atmosféricos em relação ao tempo. O principio de medição baseia-se nas propriedades ópticas da luz: reflexão, refração e absorção que ocorre quando um feixe de luz incide sobre as partículas de um poluente qualquer, dando lugar à atenuação da intensidade do feixe incidente, que é proporcional à concentração de poluente. Selecionaram-se LED e fotodetectores, segundo as informações dadas nas especificações fornecidas pelo fabricante. Formaram-se quatro tipos diferentes de Pares Emissores-Detectores, (Pares E-D), onde cada LED trabalhava com um fotodetector específico. As avaliações foram feitas em função dos Pares E-D nas condições recomendadas pelo fabricante e, selecionaram-se dois tipos diferentes de Pares E-D, que apresentaram melhores características físicas, tempo de resposta (11 e 16µs), o nível do sinal gerado pelo fotodetector (entre 2,50V e 3,50V), e estabilidade em uma faixa de temperatura de 20oC à 30oC. Para testar o funcionamento dos Pares E-D como sensores de medição da variação da concentração dos poluentes particulados atmosféricos foi construída uma maquete instrumentada com oito Pares (E-D), quatro de cada tipo dos Pares E-D selecionados previamente. Teve-se cuidado na disposição física dos Pares E-D para evitar interferências de luz. Para diminuir o ruído do circuito, a placa Protoboard foi substituída por uma placa impressa. A razão sinal/ruído foi de 3,242V/0,020V, (162:1). Foi desenvolvido um programa especifico no software LabVIEW, com o propósito de registrar os sinais gerados pelos fotodetectores a cada 10 µs e armazená-los em uma base de dados para posterior análise. A maquete instrumentada e o software de aquisição representam um sistema de medição para a caracterização da dispersão dos poluentes particulados atmosféricos. Para verificar o desempenho da maquete instrumentada e do software de aquisição, foram feitas simulações de contaminação ambiental. Utilizando uma máquina geradora de fumaça, jogou-se fumaça sobre a maquete, foram obtidos resultados satisfatórios, já que trabalhando com os oito Pares E-D ativos, conseguiu-se obter 12500 dados por segundo para cada Par E-D. Estas quantidades de dados registrados pelo programa feito no software LabVIEW foram mais que suficientes para a construção das curvas de caracterização preliminares. / [en] The atmospheric pollution is a latent world-wide problem, and it is harmful to the health, visibility and climate. For these factors, several studies and researches have been developed to characterize the chemical composition of the pollutants, concentration, size of particles, etc, with the objective of constructing adjusted instruments for the control of the air quality, but these instruments are sophisticated, complicated and very expensive. This dissertation is a study about the feasibility to use simple optoelectronic components, such as light emitting diodes (LED) and optical photo detectors, as sensors for measuring the variation of the concentration of atmospheric particulate pollutants in relation to time. The measurement principle is based on the optic properties of the light: reflection, refraction and absorption that occur when a light beam arrives on particles of any pollutant, taking place the attenuation of the intensity of the incident beam, which is proportional to the pollutant concentration. LED and photo detectors were selected according to information given in the specifications supplied for the manufacturer. Four different types of Pairs formed Emitters-Detectors, (Pairs E-D), where each LED worked with a specific photo detector. The evaluations were made in function of the Pairs E-D according to the recommendation of the manufacturer and two types different of Pairs E-D were selected, which presented better physical characteristics, time of response (11 and 16µs), level of the signal generated by the photo detector, (between 2,50V and 3,50V), and stability in a range of temperatures between 20oC to 30oC. To test the functioning of the Pairs E-D as sensors for measuring of the variation of the concentration of the atmospheric particulate pollutants. It was built an instrumented reduced model with eight Pairs E-D was built, four of each type of the Pairs E-D selected previously. It was taken care of the physical disposition of the Pairs E-D to prevent light interferences. To reduce the noise of the circuit, the Protoboard was substituted by a circuit board printed. The relation signal/noise was 3,242V/0,020V, (162:1). A specific program was developed in the software LabVIEW. The goal was to register the signals generated by photo detectors at each 10µs, and to store the data for posterior analysis. The instrumented reduced model and the software to the data acquisition represent a system for measurement and the characterization of the dispersion of the atmospheric particulate pollutants. To verify the performance of the instrumented reduced model and the software for acquisition, simulations of ambient contamination were made. A FOG machine was used to generate smoke on the reduced model, The results were satisfactory. Working with the eight active E-D Pairs, it was possible to get 12500 data per second for each Pair E-D. This amount of registered data by the acquisition program in LabVIEW was enough for the construction of the preliminary curves of characterization for the E-D Pairs.

This thesis focuses on the synthesis, properties and applications of two types of contorted organic molecules: contorted molecular ribbons and conjugated corrals. We utilized the power of reaction chemistry to writing information into conjugated molecules with contorted structures and studied “structure-property” relationships. The unique properties of the molecules were expressed in electronic and optoelectronic devices such as field-effect transistors, solar cells, photodetectors, etc. In Chapter 2, I describe the design and synthesis of a new graphene ribbon architecture that consists of perylenediimide (PDI) subunits fused together by ethylene bridges. We created a prototype series of oligomers consisting of the dimer, trimer, and tetramer. The steric congestion at the fusion point between the PDI units creates helical junctions, and longer oligomers form helical ribbons. Thin films of these oligomers form the active layer in n-type field effect transistors. UV−vis spectroscopy reveals the emergence of an intense long-wavelength transition in the tetramer. From DFT calculations, we find that the HOMO−2 to LUMO transition is isoenergetic with the HOMO to LUMO transition in the tetramer. We probe these transitions directly using femtosecond transient absorption spectroscopy. The HOMO−2 to LUMO transition electronically connects the PDI subunits with the ethylene bridges, and its energy depends on the length of the oligomer. In Chapter 3, I describe an efficiency of 6.1% for a solution processed non-fullerene solar cell using a helical PDI dimer as the electron acceptor. Femtosecond transient absorption spectroscopy revealed both electron and hole transfer processes at the donor−acceptor interfaces, indicating that charge carriers are created from photogenerated excitons in both the electron donor and acceptor phases. Light-intensity-dependent current−voltage measurements suggested different recombination rates under short-circuit and open-circuit conditions. In Chapter 4, I discuss helical molecular semiconductors as electron acceptors that are on par with fullerene derivatives in efficient solar cells. We achieved an 8.3% power conversion efficiency in a solar cell, which is a record high for non-fullerene bulk heterojunctions. Femtosecond transient absorption spectroscopy revealed both electron and hole transfer processes at the donor-acceptor interfaces. Atomic force microscopy reveals a mesh-like network of acceptors with pores that are tens of nanometers in diameter for efficient exciton separation and charge transport. This study describes a new motif for designing highly efficient acceptors for organic solar cells. In Chapter 5, I compare analogous cyclic and acyclic π-conjugated molecules as n-type electronic materials and find that the cyclic molecules have numerous benefits in organic photovoltaics. We designed two conjugated cycles for this study. Each comprises four subunits; one combines four electron-accepting, redox-active, diphenyl-perylenediimide subunits, and the other alternates two electron-donating bithiophene units with two diphenyl-perylenediimide units. We compare the macrocycles to acyclic versions of these molecules and find that, relative to the acyclic analogs, the conjugated macrocycles have bathochromically shifted UV-vis absorbances and are more easily reduced. In blended films, macrocycle-based devices show higher electron mobility and good morphology. All of these factors contribute to the more than doubling of the power conversion efficiency observed in organic photovoltaic devices with these macrocycles as the n-type, electron transporting material. This study highlights the importance of geometric design in creating new molecular semiconductors. In Chapter 6, I describe a new molecular design that enables high performance organic photodetectors. We use a rigid, conjugated macrocycle as the electron acceptor in devices to obtain high photocurrent and low dark current. We directly compare the macrocyclic acceptor devices to an acyclic control device; we find that the superior performance of the macrocycle originates from its rigid, conjugated, and cyclic structure. The macrocycle’s rigid structure reduces the number of charged defects originating from deformed sp2 carbons and covalent defects from photo/thermo-activation. With this molecular design we are able to suppress dark current density while retaining high responsivity in an ultra-sensitive non-fullerene organic photodetector. Importantly, we achieve a detectivity of ~10^14 Jones at near zero bias voltage. This is without the need for extra carrier blocking layers commonly employed in fullerene-based devices. Our devices are comparable to the best fullerene-based photodetectors, and the sensitivity at low working voltages (< 0.1 V) is a record for non-fullerene OPDs.

Made available in DSpace on 2016-12-23T14:08:09Z (GMT). No. of bitstreams: 1 Felipe Carvalho da Silva.pdf: 4181457 bytes, checksum: 8aef395272a667525a72d34c5ffb865f (MD5) Previous issue date: 2012-07-25 / With recent discoveries by the oil industry related to the reserves in Brazilian pre-salt, flow measurement technology is being re-evaluated in view of the large CO2 concentrations found in these reserves. A technology that has accuracy levels similar to those obtained with flow meters currently used and also measures independent characteristics to the composition and thermodynamic properties of gases is optical flow measurement velocimetry (OFM). The present work is related to experimental study, comparison of the speed readings from Pitot tube flow meters and optical velocimetry. This experimental study consists of qualifying and quantifying the velocity profiles among the possible configurations of flow in the wind tunnel, proposing methodology using flow conditioners and damping of the readings obtained with the Pitot tube, and analysis of readings taken with the optical sensor to evaluate the device installation effects in the results. The results indicate that transit-time optical flow meters for medium to high speed levels, could provide readcohesive flow even in a misalignment of up to ± 5 °, although it appears in the installation manual of the manufacturer guarantees of results meter when a misalignment of at most up to ±2º. Regarding the optical sensor intrusive effect in the readings simultaneous with the Pitot tube, it is perceived, in general, from approximately Re> 2,05x105, the intrusive effect of this influence is suppressed by other effects. Finally, for a proper flow study through Pitometry in order to make the comparison with the optical flow metering and achieve satisfactory results with the Pitot tube, the use of specific devices of flow conditioning and damping of the measured values had to be made / Com as recentes descobertas da indústria petrolífera brasileira, relacionadas às reservas no pré-sal, a tecnologia de medição de vazão está sendo reavaliada, tendo em vista as grandes concentrações de CO2 encontradas nessas reservas. A tecnologia de medição de vazão por velocimetria óptica (OFM) possui níveis de precisão semelhantes aos obtidos com os medidores de vazão utilizados atualmente. Essa tecnologia possui as características de independência com relação à composição química e às propriedades termodinâmicas dos gases. O presente trabalho se dedica ao estudo experimental de comparação das leituras de velocidade entre tubo de Pitot e medidor de vazão por velocimetria óptica. Para isso foi efetuada qualificação e quantificação dos perfis de velocidades em escoamento no túnel de vento, propondo metodologia de uso de retificadores de fluxo e amortecimento das leituras obtidas com o tubo de Pitot, e análises de leituras realizadas com o sensor óptico visando avaliar os efeitos de instalação do dispositivo nos resultados obtidos. Os resultados indicam que medidores de vazão ópticos por tempo de trânsito, para níveis médios e altos de velocidade, podem fornecer a leitura esperada da vazão mesmo estando num desalinhamento de ±5º, apesar de constar no manual de instalação do fabricante garantia destes resultados do medidor quando num desalinhamento de, no máximo, até ±2º. Com relação ao efeito intrusivo do sensor óptico nas leituras simultâneas com o tubo de Pitot, percebe-se, em geral, que a partir de aproximadamente Re> 2,05x105, o efeito intrusivo desta influência foi suprimido por outros efeitos. Por fim, para uma devida caracterização do escoamento por meio de pitometria, a fim de efetuar a comparação com a medição Laser, e alcançar satisfatórios resultados com o tubo de Pitot, foi necessário fazer uso de dispositivos específicos como retificadores de fluxo e de amortecimento (damping) dos valores medidos

Trends toward increased integration and miniaturization of optical system components have created pressure to consolidate widely disparate analog and digital functions onto fewer and fewer chips with a goal of eventually built into a single mixed-signal chip. Yet, because of those performance requirements, the frontend circuit has traditionally used III-V compound semiconductor technologies, but the low-level of integration with other digital ICs limits the sustainability of such end products for short-distance applications. On the other hand, their CMOS counter parts, despite having such advantages as low power consumption, high yield that lowers the cost of fabrication, and a higher degree of integration, have not performed well enough to survive in such a noisy environment without sacrificing other important attributes. In this research, a high-speed CMOS preamplifier was designed and fabricated through TSMC 0.18/spl mu/m mixed-signal non-epi CMOS technology, and a 20/spl mu/m diameter InGaAs thin-film Inverted-MSM photodetector with a responsivity of 0.15A/W at a wavelength of 1550/spl mu/m was post-integrated onto the circuit. The circuit has a overall transimpedance gain of 60dB/spl Omega/, and bit-error-rate data and eye-diagram measurement results taken as high as 10Gbit/s are reported in this dissertation.

Optical assays to detect cancer-associated molecular biomarkers in biological substrates are commonly performed with antibody-targeted organic dye contrast agents but the potential for precise quantification, long-term imaging, and multiplexed readouts is limited by chemical and optical instability, non-optimal spectral characteristics, and complicated synthetic chemistry of the dyes. This dissertation tested the hypothesis that a novel class of optical contrast agents termed polymer-protected Raman-encoded nanoparticle tags (PRENTs) provides practical advantages over existing optical technologies for molecular diagnostic applications. First, PRENTs were developed through a modular design utilizing gold-nanoparticle-Raman reporter complexes protected and functionalized by polyethylene glycol derivatives. PRENTs produced optical readouts through surface enhanced Raman scattering (SERS) that were brighter and more photostable than the fluorescence of semiconductor quantum dots under identical experimental conditions. Unique spectral signatures were produced with a broader class of Raman reporters than is possible with silica coated Raman tags. Spectral signatures and colloidal stability of PRENTs were unaffected by harsh chemical conditions that cause spectral changes and aggregation of dyes, quantum dots, and protein coated Raman tags. Antibody-targeted PRENTs specifically tagged cell surface cancer biomarkers on living cells at reasonable integration times. PRENTs were non-toxic to cells under conditions exceeding those required for sensitive molecular detection. Next, PRENTs were efficiently optimized for excitation with near-infrared light through inclusion of near-infrared chromophores as Raman reporters and exploitation of the size-dependent optical enhancement of gold nanoparticles. Third, the development of a slide-based Raman-linked immunosorbent assay using antibody-conjugated PRENTs enabled quantification of protein biomarkers with a dynamic range of 3 to 4 logs. In summary, this dissertation establishes PRENTs as novel optical tags with unique features useful for biomedical applications and provides insights for further assay development.

LACIT / Escoamentos bifásicos gás-líquido estão presentes em inúmeras aplicações de engenharia, como por exemplo, na produção de petróleo, onde óleo e gás escoam nas linhas de produção. A monitoração online do escoamento bifásico é de grande importância para operação segura e eficiente dos processos de produção. Assim, nos últimos anos tem-se buscando o desenvolvimento de técnicas simples e de baixo custo para monitoração do escoamento da produção. Das diversas formas que um escoamento bifásico se apresenta, o padrão de escoamento em golfadas é o mais comum nas linhas de produção. Este trabalho apresenta um sistema óptico infravermelho que mede especificamente a velocidade das bolhas de gás em um escoamento em golfadas. Esse sistema emprega componentes optoeletrônicos operando a 950 nm juntamente com uma peça adutora utilizada para manter estáticos o emissor e receptor de luz. O circuito eletrônico responsável pelo funcionamento do sensor é composto por três canais de medição modulados em frequências diferentes. Dessa forma pelo tempo de trânsito que uma bolha leva no percurso entre os canais, pode-se calcular a velocidade da bolha. Essa técnica óptica traz a vantagem de ser um sistema de medição não invasivo e pode ser utilizado para outros fluidos, mas é necessário adaptar o comprimento de onda de trabalho de acordo com as características do fluido a ser detectado. O sistema desenvolvido foi testado em uma planta piloto sob diversas condições operacionais e comparado com sensores de referência (wire-mesh e câmera de alta velocidade). Resultados obtidos mostram o bom desempenho do sistema com relação aos sensores de referência. / Gas-liquid two-phase flows are present in many engineering applications such as in petroleum production, where oil and gas stream in the production lines. The online monitoring of two-phase flow is of great importance for safe and efficient operation of production processes. Thus, in recent years there has been an attempt to develop simple and low cost techniques for flow production monitoring. Among the various ways a two-phase flow may occur in a pipe, the flow pattern known as slug flow is the most common in production lines. This work presents an infrared optical system that specifically measures the translational speed of gas bubbles in slugs flow. This system employs optoelectronic components operating at 950 nm along with a mechanical assembly used to assure optical alignment of light emitters and receivers. The electronic circuitry responsible for operating the sensor consists of three measuring channels modulated at different frequencies, thus by measuring the time lag a gas bubble needs to travel from one channel to another, one can calculate speed of gas bubble. This optical technique has the advantage of being a noninvasive measurement system and can be used for other fluids, but it is necessary to adapt the working wavelength according to the characteristics of the fluid to be detected. The developed system was tested in a pilot plant under various operating conditions and compared with reference sensors (wire-mesh and high-speed camera). Results show the good performance of the system with respect to the reference sensors.