Poli-líquidos iônicos e complexos solúveis de Eu3+ e Tb3+ : bioimageamento celular seletivo

Dissertação (mestrado)—Universidade de Brasília, Instituto de Química, Programa de Pós-Graduação em Química, 2015.

Electro-optical characterization of IC compatible microcantilevers

The aim of this work is to simulate and optically characterize the piezoelectric performance of complementary metal oxide semiconductor (CMOS) compatible microcantilevers based on aluminium nitride (AlN) and manufactured at room temperature. This study should facilitate the integration of piezoelectric micro-electro-mechanical systems (MEMS) such as microcantilevers, in CMOS technology. Besides compatibility with standard integrated circuit manufacturing procedures, low temperature processing also translates into higher throughput and, as a consequence, lower manufacturing costs. Thus, the use of the piezoelectric properties of AlN manufactured by reactive sputtering at room temperature is an important step towards the integration of this type of devices within future CMOS technology standards. To assess the reliability of our fabrication process, we have manufactured arrays of free-standing microcantilever beams of variable dimension and studied their piezoelectric performance. The characterization of the first out-of-plane modes of AlN-actuated piezoelectric microcantilevers has been carried out using two optical techniques: laser Doppler vibrometry (LDV) and white light interferometry (WLI). In order to actuate the cantilevers, a periodic chirp signal in certain frequency ranges was applied between the device electrodes. The nature of the different vibration modes detected has been studied and compared with that obtained by a finite element model based simulation (COMSOL Multiphysics), showing flexural as well as torsional modes. The correspondence between theoretical and experimental data is reasonably good, probing the viability of this high throughput and CMOS compatible fabrication process. To complete the study, X-ray diffraction as well as d33 piezoelectric coefficient measurements were also carried out.

Study on the practical realization of a device able to generate an in-space 3D luminous image

Gli ologrammi sono parte integrante della cultura pop a partire dagli anni 50, tanto che ad oggi sentirne parlare non desta più scalpore. Dal lato pratico, invece, solo negli ultimi anni sono state fatte ricerche approfondite con lo scopo di realizzarli. Fra i dispositivi attualmente in commercio, in pochi sono degni di nota e presentano numerose limitazioni, questo perché è molto difficile riuscire a progettare un sistema che permetta di illuminare dei punti specifici in uno spazio tridimensionale per lunghi periodi. In questa tesi si illustrano i principi di funzionamento ed il progetto per un nuovo dispositivo, diverso da quelli fino ad ora realizzati, che sfrutti il decadimento spontaneo di atomi di rubidio eccitati tramite due fasci laser opportunamente incrociati. Nel punto di incrocio si produce luce visibile a 420 nm. Con un opportuno sistema di specchi che muovono velocemente il punto di intersezione tra i due fasci è possibile realizzare un vero ologramma tridimensionale visibile da quasi ogni angolazione.

Development of thermochemiluminescence-based sensitive probes: synthesis, optimization, and characterization of c2- and c7-substituted acridine-containing 1,2-dioxetanes

After initial efforts in the late 1980s, the interest in thermochemiluminescence (TCL) as an effective detection technique has gradually faded due to some drawbacks, such as the high temperatures required to trigger the light emission and the relatively low intensities, which determined a poor sensitivity. Recent advances made with the adoption of variably functionalized 1,2-dioxetanes as innovative luminophores, have proved to be a promising approach for the development of reagentless and ultrasensitive detection methods exploitable in biosensors by using TCL compounds as labels, as either single molecules or included in modified nanoparticles. In this PhD Thesis, a novel class of N-substituted acridine-containing 1,2-dioxetanes was designed, synthesized, and characterized as universal TCL probes endowed with optimal emission-triggering temperatures and higher detectability particularly useful in bioanalytical assays. The different decorations introduced by the insertion of both electron donating (EDGs) and electron withdrawing groups (EWGs) at the 2- and 7-positions of acridine fluorophore was found to profoundly affect the photophysical properties and the activation parameters of the final 1,2-dioxetane products. Challenges in the synthesis of 1,2-dioxetanes were tackled with the recourse to continuous flow photochemistry to achieve the target parent compound in high yields, short reaction time, and easy scalability. Computational studies were also carried out to predict the olefins reactivity in the crucial photooxygenation reaction as well as the final products stability. The preliminary application of TCL prototype molecule has been performed in HaCaT cell lines showing the ability of these molecules to be detected in real biological samples and cell-based assays. Finally, attempts on the characterization of 1,2-dioxetanes in different environments (solid state, optical glue and nanosystems) and the development of bioconjugated TCL probes will be also presented and discussed.

Functional engineering of hybrid heterostructures for application in electronic, optical and optoelectronic nanostructured devices

Interfacing materials with different intrinsic chemical-physical characteristics allows for the generation of a new system with multifunctional features. Here, this original concept is implemented for tailoring the functional properties of bi-dimensional black phosphorus (2D bP or phosphorene) and organic light-emitting transistors (OLETs). Phosphorene is highly reactive under atmospheric conditions and its small-area/lab-scale deposition techniques have hampered the introduction of this material in real-world applications so far. The protection of 2D bP against the oxygen by means of functionalization with alkane molecules and pyrene derivatives, showed long-term stability with respect to the bare 2D bP by avoiding remarkable oxidation up to 6 months, paving the way towards ultra-sensitive oxygen chemo-sensors. A new approach of deposition-precipitation heterogeneous reaction was developed to decorate 2D bP with Au nanoparticles (NP)s, obtaining a “stabilizer-free” that may broaden the possible applications of the 2D bP/Au NPs interface in catalysis and biodiagnostics. Finally, 2D bP was deposited by electrospray technique, obtaining oxidized-phosphorous flakes as wide as hundreds of µm2 and providing for the first time a phosphorous-based bidimensional system responsive to electromechanical stimuli. The second part of the thesis focuses on the study of organic heterostructures in ambipolar OLET devices, intriguing optoelectronic devices that couple the micro-scaled light-emission with electrical switching. Initially, an ambipolar single-layer OLET based on a multifunctional organic semiconductor, is presented. The bias-depending light-emission shifted within the transistor channel, as expected in well-balanced ambipolar OLETs. However, the emitted optical power of the single layer-based device was unsatisfactory. To improve optoelectronic performance of the device, a multilayer organic architecture based on hole-transporting semiconductor, emissive donor-acceptor blend and electron-transporting semiconductor was optimized. We showed that the introduction of a suitable electron-injecting layer at the interface between the electron-transporting and light-emission layers may enable a ≈ 2× improvement of efficiency at reduced applied bias.

Organic microcavity light-emitting diodes with metal mirrors: dependence of the emission wavelength on the viewing angle

Organic microcavity light-emitting diodes typically exhibit a blueshift of the emitting wavelength with increasing viewing angle. We have modeled the shift of the resonance wavelength for several metal mirrors. Eight metals (Al, Ag, Cr, Ti, Au, Ni, Pt, and Cu) have been considered as top or bottom mirrors, depending on their work functions. The model fully takes into account the dependence of the phase change that occurs on reflection on angle and wavelength for both s and p polarization, as well as on dispersion in the organic layers. Different contributions to the emission wavelength shift are discussed. The influence of the thickness of the bottom mirror and of the choice and thickness of the organic materials inside the cavity has been investigated. Based on the results obtained, guidelines for a choice of materials to reduce blueshift; are given. (C) 2002 Optical Society of America.

Effects of light and temperature on isoprene emission at different leaf developmental stages of eschweilera coriacea in central Amazon

Isoprene emission from plants accounts for about one third of annual global volatile organic compound emissions. The largest source of isoprene for the global atmosphere is the Amazon Basin. This study aimed to identify and quantify the isoprene emission and photosynthesis at different levels of light intensity and leaf temperature, in three phenological phases (young mature leaf, old mature leaf and senescent leaf) of Eschweilera coriacea (Matamatá verdadeira), the species with the widest distribution in the central Amazon. In situ photosynthesis and isoprene emission measurements showed that young mature leaf had the highest rates at all light intensities and leaf temperatures. Additionally, it was observed that isoprene emission capacity (Es) changed considerably over different leaf ages. This suggests that aging leads to a reduction of both leaf photosynthetic activity and isoprene production and emission. The algorithm of Guenther et al. (1999) provided good fits to the data when incident light was varied, however differences among E S of all leaf ages influenced on quantic yield predicted by model. When leaf temperature was varied, algorithm prediction was not satisfactory for temperature higher than ~40 °C; this could be because our data did not show isoprene temperature optimum up to 45 °C. Our results are consistent with the hypothesis of the isoprene functional role in protecting plants from high temperatures and highlight the need to include leaf phenology effects in isoprene emission models.

Metal-Nitride-oxide-semiconductor light-emitting devices for general lighting.

The potential for application of silicon nitride-based light sources to general lighting is reported. The mechanism of current injection and transport in silicon nitride layers and silicon oxide tunnel layers is determined by electro-optical characterization of both bi- and tri-layers. It is shown that red luminescence is due to bipolar injection by direct tunneling, whereas Poole-Frenkel ionization is responsible for blue-green emission. The emission appears warm white to the eye, and the technology has potential for large-area lighting devices. A photometric study, including color rendering, color quality and luminous efficacy of radiation, measured under various AC excitation conditions, is given for a spectrum deemed promising for lighting. A correlated color temperature of 4800K was obtained using a 35% duty cycle of the AC excitation signal. Under these conditions, values for general color rendering index of 93 and luminous efficacy of radiation of 112 lm/W are demonstrated. This proof of concept demonstrates that mature silicon technology, which is extendable to lowcost, large-area lamps, can be used for general lighting purposes. Once the external quantum efficiency is improved to exceed 10%, this technique could be competitive with other energy-efficient solid-state lighting options. ©2011 Optical Society of America OCIS codes: (230.2090) Electro-optical devices; (150.2950) Illumination.

Polarization strategies to improve the emission of a Si-based light source emitting at 1.55 um

We present a electroluminescence (EL) study of the Si-rich silicon oxide (SRSO) LEDs with and without Er3+ ions under different polarization schemes: direct current (DC) and pulsed voltage (PV). The power efficiency of the devices and their main optical limitations are presented. We show that under PV polarization scheme, the devices achieve one order of magnitude superior performance in comparison with DC. Time-resolved measurements have shown that this enhancement is met only for active layers in which annealing temperature is high enough (>1000 ◦C) for silicon nanocrystal (Si-nc) formation. Modeling of the system with rate equations has been done and excitation cross-sections for both Si-nc and Er3+ ions have been extracted.

Nutrient and light availability to white spruce seedlings in partial and clearcut harvested aspen stands

Abstract

Retinal damage induced by commercial light emitting diodes (LEDs).

Spectra of "white LEDs" are characterized by an intense emission in the blue region of the visible spectrum, absent in daylight spectra. This blue component and the high intensity of emission are the main sources of concern about the health risks of LEDs with respect to their toxicity to the eye and the retina. The aim of our study was to elucidate the role of blue light from LEDs in retinal damage. Commercially available white LEDs and four different blue LEDs (507, 473, 467, and 449nm) were used for exposure experiments on Wistar rats. Immunohistochemical stain, transmission electron microscopy, and Western blot were used to exam the retinas. We evaluated LED-induced retinal cell damage by studying oxidative stress, stress response pathways, and the identification of cell death pathways. LED light caused a state of suffering of the retina with oxidative damage and retinal injury. We observed a loss of photoreceptors and the activation of caspase-independent apoptosis, necroptosis, and necrosis. A wavelength dependence of the effects was observed. Phototoxicity of LEDs on the retina is characterized by a strong damage of photoreceptors and by the induction of necrosis.

Different origins of green-light photoluminescence emission in structurally ordered and disordered powders of calcium molybdate

A strong greenish-light photoluminescence (PL) emission was measured at room temperature for disordered and ordered powders of CaMoO4 prepared by the polymeric precursor method. The structural evolution from disordered to ordered powders was accompanied by XRD. Raman spectroscopy, and TEM imagery. High-level quantum mechanical calculations in the density functional framework were used to interpret the formation of the structural defects of disorder powders in terms of band diagram and density of states. Complex cluster vacancies [MoO3 center dot V-O(z)] and [CaO7 center dot V-O(z)] (where V-O(z) = V-O(X), V-O(center dot), V-O(center dot center dot)) were suggested to be responsible to the appearance of new states shallow and deeply inserted in the band gap. These defects give rise to the PL in disordered powders. The natural PL emission of ordered CaMoO4 was attributed to an intrinsic slight distortion of the [MoO4] tetrahedral in the short range.

Strong violet-blue light photoluminescence emission at room temperature in SrZrO3: Joint experimental and theoretical study

Ultrafine ordered and disordered SrZrO3 powders were prepared by the polymeric precursor method. The structural evolution from structural disorder to order was monitored by X-ray diffraction and X-ray absorption near-edge spectroscopy. Complex cluster vacancies [ZrO5 center dot V-O(Z)] and [SrOII center dot V-O(Z)] (where V-O(Z) = V-O(X), V-O(center dot) and V-O(center dot center dot)) were proposed for disordered powders. The intense violet-blue light photoluminescence emission measured at room temperature in the disordered powders was attributed to complex cluster vacancies. High-level quantum mechanical calculations within the density functional theory framework were used to interpret the experimental results. (C) 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

First principles calculations on the origin of violet-blue and green light photoluminescence emission in SrZrO3 and SrTiO3 perovskites

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)