Synthesis, structure, and optical properties of an alternating calix[4]arene-based meta-linked phenylene ethynylene copolymer

Novel alternating copolymers comprising biscalix[4]arene-p-phenylene ethynylene and m-phenylene ethynylene units (CALIX-m-PPE) were synthesized using the Sonogashira-Hagihara cross-coupling polymerization. Good isolated yields (60-80%) were achieved for the polymers that show M-n ranging from 1.4 x 10(4) to 5.1 x 10(4) gmol(-1) (gel permeation chromatography analysis), depending on specific polymerization conditions. The structural analysis of CALIX-m-PPE was performed by H-1, C-13, C-13-H-1 heteronuclear single quantum correlation (HSQC), C-13-H-1 heteronuclear multiple bond correlation (HMBC), correlation spectroscopy (COSY), and nuclear overhauser effect spectroscopy (NOESY) in addition to Fourier transform-Infrared spectroscopy and microanalysis allowing its full characterization. Depending on the reaction setup, variable amounts (16-45%) of diyne units were found in polymers although their photophysical properties are essentially the same. It is demonstrated that CALIX-m-PPE does not form ground-or excited-state interchain interactions owing to the highly crowded environment of the main-chain imparted by both calix[4]arene side units which behave as insulators inhibiting main-chain pi-pi staking. It was also found that the luminescent properties of CALIX-m-PPE are markedly different from those of an all-p-linked phenylene ethynylene copolymer (CALIX-p-PPE) previously reported. The unexpected appearance of a low-energy emission band at 426 nm, in addition to the locally excited-state emission (365 nm), together with a quite low fluorescence quantum yield (Phi = 0.02) and a double-exponential decay dynamics led to the formulation of an intramolecular exciplex as the new emissive species.

Implementação e validação do método de determinação de metais e fósforo por ICP-OES (inductively coupled plasma-optical emission spectometry) em biodiesel

O objectivo do presente trabalho foi desenvolver, implementar e validar métodos de determinação de teor de cálcio (Ca), magnésio (Mg), sódio (Na), potássio (K) e fósforo (P) em biodiesel, por ICP-OES. Este método permitiu efectuar o controlo de qualidade do biodiesel, com a vantagem de proporcionar uma análise multi-elementar, reflectindo-se numa diminuição do tempo de análise. Uma vez que o biodiesel é uma das principais fontes de energia renovável e alternativa ao diesel convencional, este tipo de análises revela-se extremamente útil para a sua caracterização. De acordo com a análise quantitativa e qualitativa e após a validação dos respectivos ensaios, apresentam-se, na Tabela 1 as condições optimizadas para cada elemento em estudo. As condições de trabalho do ICP-OES foram escolhidas tendo em conta as características do elemento em estudo, o tipo de equipamento utilizado para a sua análise, e de modo a obter a melhor razão sinal/intensidade de fundo. Para a validação dos ensaios foram efectuados ensaios de recuperação, determinados limites de detecção e quantificação, ensaios de repetibilidade e reprodutibilidade, e verificação das curvas de calibração. Na tabela 2 apresentam-se os comprimentos de onda escolhidos (livres de interferências) e respectivos limites de detecção e quantificação dos elementos analisados por ICP-OES, na posição radial e radial atenuado.

Sensor de glicose polarimétrico

Esta tese tem como principal objectivo a investigação teórica e experimental do desempenho de um sensor polarimétrico baseado num cristal líquido para medição da concentração de glicose. Recentemente uma série de sensores polarimétricos baseados em cristais líquidos foram propostos na literatura e receberam considerável interesse devido as suas características únicas. De facto, em comparação com outros moduladores electro-ópticos, o cristal líquido funciona com tensões mais baixas, tem baixo consumo de energia e maior ângulo de rotação. Além disso, este tipo de polarímetro pode ter pequenas dimensões que é uma característica interessante para dispositivos portáteis e compactos. Existem por outro lado algumas desvantagens, nomeadamente o facto do desempenho do polarímetro ser fortemente dependente do tipo de cristal líquido e da tensão a ele aplicada o que coloca desafios na escolha dos parâmetros óptimos de operação. Esta tese descreve o desenvolvimento do sensor polarimétrico, incluindo a integração dos componentes de óptica e electrónica, os algoritmos de processamento de sinal e um interface gráfico que facilita a programação de diversos parâmetros de operação e a calibração do sensor. Após a optimização dos parâmetros de operação verificou-se que o dispositivo mede a concentração da glicose em amostras com uma concentração de 8 mg/ml, com uma percentagem de erro inferior a 6% e um desvio padrão de 0,008o. Os resultados foram obtidos para uma amostra com percurso óptico de apenas 1 cm.

Implementação de WDM com dispositivos semicondutores

Este trabalho utiliza uma estrutura pin empilhada, baseada numa liga de siliceto de carbono amorfo hidrogenado (a-Si:H e/ou a-SiC:H), que funciona como filtro óptico na zona visível do espectro electromagnético. Pretende-se utilizar este dispositivo para realizar a demultiplexagem de sinais ópticos e desenvolver um algoritmo que permita fazer o reconhecimento autónomo do sinal transmitido em cada canal. O objectivo desta tese visa implementar um algoritmo que permita o reconhecimento autónomo da informação transmitida por cada canal através da leitura da fotocorrente fornecida pelo dispositivo. O tema deste trabalho resulta das conclusões de trabalhos anteriores, em que este dispositivo e outros de configuração idêntica foram analisados, de forma a explorar a sua utilização na implementação da tecnologia WDM. Neste trabalho foram utilizados três canais de transmissão (Azul – 470 nm, Verde – 525 nm e Vermelho – 626 nm) e vários tipos de radiação de fundo. Foram realizadas medidas da resposta espectral e da resposta temporal da fotocorrente do dispositivo, em diferentes condições experimentais. Variou-se o comprimento de onda do canal e o comprimento de onda do fundo aplicado, mantendo-se constante a intensidade do canal e a frequência de transmissão. Os resultados obtidos permitiram aferir sobre a influência da presença da radiação de fundo e da tensão aplicada ao dispositivo, usando diferentes sequências de dados transmitidos nos vários canais. Verificou-se, que sob polarização inversa, a radiação de fundo vermelho amplifica os valores de fotocorrente do canal azul e a radiação de fundo azul amplifica o canal vermelho e verde. Para polarização directa, apenas a radiação de fundo azul amplifica os valores de fotocorrente do canal vermelho. Enquanto para ambas as polarizações, a radiação de fundo verde, não tem uma grande influência nos restantes canais. Foram implementados dois algoritmos para proceder ao reconhecimento da informação de cada canal. Na primeira abordagem usou-se a informação contida nas medidas de fotocorrente geradas pelo dispositivo sob polarização inversa e directa. Pela comparação das duas medidas desenvolveu-se e testou-se um algoritmo que permite o reconhecimento dos canais individuais. Numa segunda abordagem procedeu-se ao reconhecimento da informação de cada canal mas com aplicação de radiação de fundo, tendo-se usado a informação contida nas medidas de fotocorrente geradas pelo dispositivo sob polarização inversa sem aplicação de radiação de fundo com a informação contida nas medidas de fotocorrente geradas pelo dispositivo sob polarização inversa com aplicação de radiação de fundo. Pela comparação destas duas medidas desenvolveu-se e testou-se o segundo algoritmo que permite o reconhecimento dos canais individuais com base na aplicação de radiação de fundo.

Non-selective optical wavelength-division multiplexing devices based on a-SiC:H multilayer heterostuctures

In this paper we present results on the optimization of multilayered a-SiC:H heterostructures for wavelength-division (de) multiplexing applications. The non selective WDM device is a double heterostructure in a glass/ITO/a-SiC:H (p-i-n) /a-SiC:H(-p) /a-Si:H(-i')/a-SiC:H (-n')/ITO configuration. The single or the multiple modulated wavelength channels are passed through the device, and absorbed accordingly to its wavelength, giving rise to a time dependent wavelength electrical field modulation across it. The effect of single or multiple input signals is converted to an electrical signal to regain the information (wavelength, intensity and frequency) of the incoming photogenerated carriers. Here, the (de) multiplexing of the channels is accomplished electronically, not optically. This approach offers advantages in terms of cost since several channels share the same optical components; and the electrical components are typically less expensive than the optical ones. An electrical model gives insight into the device operation.

A two terminal optical signal and image processing p-i-n/p-i-n image and colour sensor

A two terminal optically addressed image processing device based on two stacked sensing/switching p-i-n a-SiC:H diodes is presented. The charge packets are injected optically into the p-i-n sensing photodiode and confined at the illuminated regions changing locally the electrical field profile across the p-i-n switching diode. A red scanner is used for charge readout. The various design parameters and addressing architecture trade-offs are discussed. The influence on the transfer functions of an a-SiC:H sensing absorber optimized for red transmittance and blue collection or of a floating anode in between is analysed. Results show that the thin a-SiC:H sensing absorber confines the readout to the switching diode and filters the light allowing full colour detection at two appropriated voltages. When the floating anode is used the spectral response broadens, allowing B&W image recognition with improved light-to-dark sensitivity. A physical model supports the image and colour recognition process.

ITO/SiOx/Si optical sensor with internal gain

A visible/near-infrared optical sensor based on an ITO/SiOx/n-Si structure with internal gain is presented. This surface-barrier structure was fabricated by a low-temperature processing technique. The interface properties and carder transport were investigated from dark current-voltage and capacitance-voltage characteristics. Examination of the multiplication properties was performed under different light excitation and reverse bias conditions. The spectral and pulse response characteristics are analysed. The current amplification mechanism is interpreted by the control of electron current by the space charge of photogenerated holes near the SiOx/Si interface. The optical sensor output characteristics and some possible device applications are presented.

Optical confinement and colour separation in a double colour laser scanned photodiode (D/CLSP)

Large area n-i-p-n-i-p a-SiC:H heterostructures are used as sensing element in a double colour laser scanned photodiode image sensor (D/CLSP). This work aims to clarify possible improvements, physical limits and performance of CLSP image sensor when used as non-pixel image reader. Here, the image capture device and the scanning reader are optimized and the effects of the sensor structure on the output characteristics discussed. The role of the design of the sensing element, the doped layer composition and thickness, the read-out parameters (applied voltage and scanner frequency) on the image acquisition and the colour detection process are analysed. A physical model is presented and supported by a numerical simulation of the output characteristics of the sensor.

Optical confinement and colour separation in a double colour laser scanned photodiode (D/CLSP)

Large area n-i-p-n-i-p a-SiC:H heterostructures are used as sensing element in a Double Color Laser Scanned Photodiode image sensor (D/CLSP). This work aims to clarify possible improvements, physical limits and performance of CLSP image sensor when used as non-pixel image reader. Here, the image capture device and the scanning reader are optimized and the effects of the sensor structure on the output characteristics discussed. The role of the design of the sensing element, the doped layer composition and thickness, the read-out parameters (applied voltage and scanner frequency) on the image acquisition and the color detection process are analyzed. A physical model is presented and supported by a numerical simulation of the output characteristics of the sensor.

Optical demultiplexer device operating in the visible spectrum

In this paper, we present results on the use of multilayered a-SiC:H heterostructures as a device for wavelength-division demultiplexing of optical signals. These devices are useful in optical communications applications that use the wavelength division multiplexing technique to encode multiple signals into the same transmission medium. The device is composed of two stacked p-i-n photodiodes, both optimized for the selective collection of photo generated carriers. Band gap engineering was used to adjust the photogeneration and recombination rate profiles of the intrinsic absorber regions of each photodiode to short and long wavelength absorption in the visible spectrum. The photocurrent signal using different input optical channels was analyzed at reverse and forward bias and under steady state illumination. A demux algorithm based on the voltage controlled sensitivity of the device was proposed and tested. An electrical model of the WDM device is presented and supported by the solution of the respective circuit equations.

Optical properties and transport in PLD-GaN

We present structural, optical and transport data on GaN samples grown by hybrid, two-step low temperature pulsed laser deposition. The band gap of samples with good crystallinity has been deduced from optical spectra. Large below gap band tails were observed. In samples with the lowest crystalline quality the PL spectra are quite dependent on spot laser incidence. The most intense PL lines can be attributed to excitons bounded to stacking faults. When the crystalline quality of the samples is increased the ubiquitous yellow emission band can be detected following a quenching process described by a similar activation energy to that one found in MOCVD grown samples. The samples with the highest quality present, besides the yellow band, show a large near band edge emission which peaked at 3.47 eV and could be observed up to room temperature. The large width of the NBE is attributed to effect of a wide distribution of band tail states on the excitons. Photoconductivity data supports this interpretation.

Reward-risk efficiency in proportional reinsurance with different risk measures

We have studied, in particular under normality of the implied random variables, the connections between different measures of risk such as the standard deviation, the W-ruin probability and the p-V@R. We discuss conditions granting the equivalence of these measures with respect to risk preference relations and the equivalence of dominance and efficiency of risk-reward criteria involving these measures. Then more specifically we applied these concepts to rigorously face the problem of finding the efficient set of de Finetti’s variable quota share proportional reinsurance.

: SiC Multilayer Photonic Structures with Self Optical Bias Amplification

Characteristics of tunable wavelength pi'n/pin filters based on a-SiC:H multilayered stacked cells are studied both experimental and theoretically. Results show that the device combines the demultiplexing operation with the simultaneous photodetection and self amplification of the signal. An algorithm to decode the multiplex signal is established. A capacitive active band-pass filter model is presented and supported by an electrical simulation of the state variable filter circuit. Experimental and simulated results show that the device acts as a state variable filter. It combines the properties of active high-pass and low-pass filter sections into a capacitive active band-pass filter using a changing photo capacitance to control the power delivered to the load.

Structural and optical studies of Au doped titanium oxide films

Thin films of TiO2 were doped with Au by ion implantation and in situ during the deposition. The films were grown by reactive magnetron sputtering and deposited in silicon and glass substrates at a temperature around 150 degrees C. The undoped films were implanted with Au fiuences in the range of 5 x 10(15) Au/cm(2)-1 x 10(17) Au/cm(2) with a energy of 150 keV. At a fluence of 5 x 10(16) Au/cm(2) the formation of Au nanoclusters in the films is observed during the implantation at room temperature. The clustering process starts to occur during the implantation where XRD estimates the presence of 3-5 nm precipitates. After annealing in a reducing atmosphere, the small precipitates coalesce into larger ones following an Ostwald ripening mechanism. In situ XRD studies reveal that Au atoms start to coalesce at 350 degrees C, reaching the precipitates dimensions larger than 40 nm at 600 degrees C. Annealing above 700 degrees C promotes drastic changes in the Au profile of in situ doped films with the formation of two Au rich regions at the interface and surface respectively. The optical properties reveal the presence of a broad band centered at 550 nm related to the plasmon resonance of gold particles visible in AFM maps. (C) 2011 Elsevier B.V. All rights reserved.

Multilayer Architectures Based on a-SiC:H Material: Tunable Wavelength Filters in Optical Processing Devices

The characteristics of tunable wavelength filters based on a-SiC:H multilayered stacked pin cells are studied both theoretically and experimentally. The optical transducers were produced by PECVD and tested for a proper fine tuning of the cyan and yellow fluorescent proteins emission. The active device consists of a p-i'(a-SiC:H)-n/p-i(a-Si:H)-n heterostructures sandwiched between two transparent contacts. Experimental data on spectral response analysis, current-voltage characteristics and color and transmission rate discrimination are reported. Cyan and yellow fluorescent input channels were transmitted together, each one with a specific transmission rate and different intensities. The multiplexed optical signal was analyzed by reading out, under positive and negative applied voltages, the generated photocurrents. Results show that the optimized optical transducer has the capability of combining the transient fluorescent signals onto a single output signal without losing any specificity (color and intensity). It acts as a voltage controlled optical filter: when the applied voltages are chosen appropriately the transducer can select separately the cyan and yellow channel emissions (wavelength and frequency) and also to quantify their relative intensities. A theoretical analysis supported by a numerical simulation is presented.