Made available in DSpace on 2014-10-09T12:52:11Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:57:49Z (GMT). No. of bitstreams: 0 / O presente trabalho descreve os processos de preparação do aluminato de bário e cálcio, material emissor de elétrons, empregados nos catodos do tipo impregnado para utilização em uma válvula de microondas do tipo TWT. Os catodos investigados constituem-se de uma pastilha de tungstênio porosa impregnada com aluminato de bário e cálcio com proporção molar 5:3:2. Para a síntese do aluminato, utilizaram-se três diferentes métodos: reação em estado sólido, precipitação e cristalização. A termogravimetria auxiliou na consolidação dos procedimentos de preparação dos aluminatos de modo a definir os parâmetros de pirólise/calcinação. Verificou-se que a técnica que apresentou melhores características de síntese foi o método da cristalização, pois esta apresentou uma menor temperatura de formação do aluminato (800ºC) em atmosfera oxidante (O2), quando comparada às técnicas de reação em estado sólido e de precipitação (temperatura de 1000ºC em atmosfera redutora – H2). Utilizou-se o conceito da distribuição da função trabalho prática (PWFD) de Miram para a caracterização termiônica dos catodos impregnados. Empregando-se este método, foi possível traçar o perfil termiônico do catodo com aluminato de bário e cálcio. As curvas PWFD apresentaram a função trabalho média do catodo aluminato de, aproximadamente, 2,00 eV. / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Triarylborane Functionalized Dicyanovinyl and Acetylacetone Based Molecular Platforms: Building Blocks for Multiple Anion Sensors and Efficient Phosphorescence Emitters The main objective of this thesis is to design a simple strategy for triarylborane based multiple anion sensors and development of triarylborane incorporated phosphorescent metal complexes. The thesis consists of eight chapters and the contents of each chapter are given below. Chapter 1 This chapter gives a general introduction to recent advances relevant to the theme of the thesis. A review of the fundamental characteristics of triarylboranes and their applications in various fields such as chemical sensors and optoelectronics is presented. Advances in boron chemistry in the areas such as anion sensors, solid state emissive and phosphorescence materials are discussed in detail. The scope of the thesis is outlined at the end of the chapter. Chapter 2 The second chapter deals with the general experimental techniques and synthetic procedures followed in this thesis. Chapter 3 This chapter deals with a rational design strategy for differential identification of fluoride and cyanide ions using TAB based sensors. In general, most of the triarylboranes give similar optical responses towards fluoride and cyanide ions as they follow similar sensing mechanism. In order to circumvent this problem, two TAB-DCV conjugates (1 and 2) are designed and synthesised. The DCV unit is highly specific for cyanide ion owing to the presence of electrophilic carbon center. Probes 1 and 2 differ in steric crowding around the boron center. The less crowded boron center in 1 binds with fluoride as well as with cyanide ions giving similar optical response (luminescence is quenched in presence of F¯ and CN¯). In the case of 2, selectivity of boron center towards fluoride is tuned by increasing the steric crowding around the boron unit. The dicyanovinyl unit acts as selective sensing site for cyanide ions. As a result, 2 gives different fluorogenic response towards the anions F¯ and CN¯ which were considered as interfering anions in TAB based sensor chemistry. Thus, a modular design principle is developed for differential identification of fluoride and cyanide ions using TAB. Chapter 4 In this chapter, detailed photophysical studies of TAB-amine-DCV conjugates and colorimetric discrimination of fluoride and cyanide ions are discussed. Presence of amine based donor between the two electron deficient sites enhances the electronic conjugation in 3−5. Since there are two different acceptor sites with a common donor, two distinct charge transfer transition bands are observed in the visible region of electromagnetic spectrum. The absorption and emission spectra of these compounds show pronounced sensitivity to solvent polarity, signifying large excited state dipolmonents. Anion binding studies confirms that these compounds are highly selective towards fluoride and cyanide ions. Fluoride ions selectively interact with boron center and block the corresponding charge transfer transition thereby leading to a distinct colour change which is observable by naked eye. On the other hand, cyanide interacts with boron as well as DCV unit and blocks both the charge transfer transitions which results in disappearance of colour. Hence, compounds 4 and 5 exhibit different colorimetric signals for fluoride and cyanide ions. Since the absorption bands of 3 do not fall in the visible region, it does not show any colorimetric response towards the aforementioned anions. The anion sensing mechanisms are established by 1H, and 19F NMR studies. Chapter 5 This chapter presents a systematic study of the effect of length of π-electronic conjugation on the optical properties and anion sensing abilities of a series of TAB-oligothiophene-DCV conjugates (6−8). Their absorption as well as emission bands undergo redshift upon increasing the number of thiophene units between TAB and DCV units as the π-electronic conjugation in 6−8 is greatly dependent on the number of thiophene units. Their fluorescence emission is highly sensitive to solvent polarity. In the case of 6, the emission band undergoes a redshift with reduced intensity. In the case of 7 the emission band undergoes a redshift but the intensity is not affected by solvent polarity. In the case of 8, the emission band undergoes redshift with enhanced intensity in polar solvents. Interestingly, 7 and 8 show solvent viscosity dependent fluorescence. Structural reorganisation is restricted in viscous medium and results in enhanced emission for 7 and 8. Further, these compounds exhibit selective response towards the fluoride and cyanide ions with different colorimetric responses. Test strips made up of probes 7 and 8 have potential application in identifying fluoride and cyanide ions in aqueous medium. Chapter 6 This chapter describes synthesis and optical characterisation of triarylborane incorporated acetylacetone (acacH) ligands (9, 10) and their borondifluoride complexes (11, 12). AcacH ligands and BF2 complexes show solvent dependent emission phenomena due to the involvement of charge transfer transition. Their optical properties are highly dependent on molecular conformations. Complex with duryl spacer (12) exhibits more red shifted emission in polar solvents due to the enhanced charge transfer transition facilitated by twisted rigid geometry. In presence of fluoride and cyanide ions, the borondifluoride complexes are not stable. The anions concomitantly interact with tricoordinate boron as well as acac-BF2 unit to give rise to complex pattern of photoluminescence spectral changes during the titration experiment. The binding pathway and the possible species involved are established with the help of 1H, 19F and 11B NMR spectral studies in presence of the anions. Complexes 11 and 12 act as selective chemodosimetric sensors for fluoride and cyanide ions. Chapter 7 In this chapter, the synthesis and optical characterisations of triarylborane conjugated cyclometalated platinum complexes are discussed. A series of square planar platinum complexes are synthesised with different cyclometalating ligands. Complexes (13−18) exhibit a range of luminescence from green to red in solution as well as in the solid state. Their emission intensities are highly sensitive towards atmospheric oxygen suggesting that they originate from a triplet excited state. A maximum of 85% quantum yield is observed for complex 15 in solution state while complex 14 showed a maximum of 58% quantum yield in solid state. Complexes with rigid molecular conformation (14, 16 and 18) showed higher luminescence quantum yield than those having phenyl spacer (13, 15 and 17). The sterically encumbered boryl (-BMes2) group significantly reduces π-π stacking between the square planar entities. Thus, complexes 13−18 show bright luminescence in solid state compared to model complexes without boryl group. The effect of Lewis acidic boron center on luminescence behaviour is explored by fluoride binding studies. Chapter 8 This chapter is divided into two parts. Part-I describes the synthesis and optical characterisation of triarylborane conjugated cyclometalated iridium complexes (19−24). They are brightly luminescent in solution state with high sensitivity towards atmospheric oxygen. Complex 20 shows a highest quantum yield of 91%. Interestingly, under ambient atmospheric conditions, they exhibit a rare type of dual emission. Life time data suggest that the lower energy emission band originates from cyclometalated iridium based triplet excited state while higher energy emission band originates from boryl ased singlet excited state. Fluoride binding at the boron site results in luminescence quenching; evidently, tri-coordinate boron has a major contribution to the luminescence features of these iridium complexes. Part-II deals with synthesis of triarylborane conjugated pyrazole ligand (25) and its binuclear iridium complexes (26−28) in which two iridium centers are bridged by hydroxo as well as pyrazolato ligands. These binuclear iridium complexes exhibit higher luminescence quantum yield than TAB-acac-Iridium complexes (mononuclear complexes; part I). Binding of fluoride ions at the boron center has a minor impact on their luminescence nature. High sensitivity of their luminescence towards atmospheric oxygen indicates the involvement of triplet excited state in their emission process.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / An experiment of surface and subsurface drip irrigation in figs was held in Santa Maria, Rio Grande do Sul state, with aim of evaluate the disposables materials efficiency for protecting water emitters in subsuperface irrigation against root intrusion. The experiment was conducted in a randomized block design with four replications. The treatments were five irrigation options: A - no irrigation, B - drip tape; C - surface drip, D - subsurface drip-protected with rice husk, and E - subsurface drip-protected with polyethylene terephthalate (PET) bottles. In subsurface irrigation the effect of the emitter protections was analyzed on root intrusion and response variables of fig trees (fruits diameter and number per plant, plant production and productivity, and final dry mass of roots). For the process of root intrusion in buried emitters, an index of root intrusion (IRI) was created and after an index of root intrusion (IIR) subsurface was determined. The final dry mass of roots was determined in all treatments. It was found that the PET bottle protect the emitters in subsurface irrigation against obstruction by root intrusion. The use of rice husk is an inadequate technique for protecting emitters in subsurface irrigation, because it provides favorable conditions for root intrusion, which significantly to reduce flow of the emitters. The root intrusion due to the use of rice hull around the emitters in subsurface irrigation can negatively affect the fig tree response variables, which, in periods of insufficient rainfall, does not allow greater productivity than that obtained without irrigation. The lack of supplementary irrigation, when dry periods occur during the harvest period, reduces the fruits diameter, average weight, and the number of fruits per plant. The root dry mass per plant is not significantly influenced by any form of irrigation, that is, the values found were similar to values found in non-irrigated soil at any level from surface to the 40 cm soil depth. / Um experimento de irrigação por gotejamento superficial e subsuperficial em figueira foi realizado em Santa Maria, estado do Rio Grande do Sul, com o objetivo de avaliar a eficiência de materiais descartáveis, na proteção dos emissores de água em irrigação subsuperficial ao processo de intrusão radicular. O experimento foi conduzido no delineamento de blocos ao acaso, com quatro repetições. Os tratamentos avaliados foram cinco formas de irrigação: A sem irrigação; B fita gotejadora; C - gotejador superficial; D gotejador subsuperficial protegido por casca de arroz e, E - gotejador subsuperficial protegido por garrafa PET. Na irrigação subsuperficial foi analisado o efeito das proteções dos emissores, ao processo de intrusão radicular e associado às variáveis respostas da cultura da figueira (número e diâmetro de frutos por planta, produção por planta e produtividade, massa seca final de raízes). Para o processo de intrusão radicular nos emissores enterrados, foi criado um índice de intrusão radicular (IIR) e após, determinado índice de intrusão radicular (IIR) subsuperficial. Foi determinada a massa seca final das raízes em todos os tratamentos. Verificou-se que a garrafa PET protege os emissores em irrigação subsuperficial a obstrução pelo processo de intrusão radicular. O uso da casca de arroz como protetor de emissores em irrigação subsuperficial é uma técnica inadequada para esse fim, propiciando condições favoráveis ao processo de intrusão radicular, fato que compromete significativamente a vazão dos emissores. A intrusão radicular, decorrente do uso de casca de arroz em torno dos emissores em irrigação subsuperficial, pode afetar negativamente as variáveis respostas da planta da figueira, o que em períodos de precipitação insuficiente não permite obter produtividade maior do que a obtida sem irrigação. A falta de irrigação complementar quando os períodos com precipitação insuficiente ocorrem durante o subperíodo da colheita dos frutos, tende a diminuir o diâmetro e o peso médio dos frutos, o número de frutos colhidos por planta e a produção de frutos das figueiras. A massa seca de raiz por planta não é influenciada significativamente em figueiras por nenhuma forma de irrigação, sendo similar aos valores encontrados em solo não irrigado em qualquer nível até 40 cm de profundidade do solo.

Carbon nanotubes (CNTs) have become one of the most interesting allotropes of carbon due to their intriguing mechanical, electrical, thermal and optical properties. The synthesis and electron emission properties of CNT arrays have been investigated in this work. Vertically aligned CNTs of different densities were synthesized on copper substrate with catalyst dots patterned by nanosphere lithography. The CNTs synthesized with catalyst dots patterned by spheres of 500 nm diameter exhibited the best electron emission properties with the lowest turn-on/threshold electric fields and the highest field enhancement factor. Furthermore, CNTs were treated with NH3 plasma for various durations and the optimum enhancement was obtained for a plasma treatment of 1.0 min. CNT point emitters were also synthesized on a flat-tip or a sharp-tip to understand the effect of emitter geometry on the electron emission. The experimental results show that electron emission can be enhanced by decreasing the screening effect of the electric field by neighboring CNTs. In another part of the dissertation, vertically aligned CNTs were synthesized on stainless steel (SS) substrates with and without chemical etching or catalyst deposition. The density and length of CNTs were determined by synthesis time. For a prolonged growth time, the catalyst activity terminated and the plasma started etching CNTs destructively. CNTs with uniform diameter and length were synthesized on SS substrates subjected to chemical etching for a period of 40 minutes before the growth. The direct contact of CNTs with stainless steel allowed for the better field emission performance of CNTs synthesized on pristine SS as compared to the CNTs synthesized on Ni/Cr coated SS. Finally, fabrication of large arrays of free-standing vertically aligned CNT/SnO2 core-shell structures was explored by using a simple wet-chemical route. The structure of the SnO2 nanoparticles was studied by X-ray diffraction and electron microscopy. Transmission electron microscopy reveals that a uniform layer of SnO2 is conformally coated on every tapered CNT. The strong adhesion of CNTs with SS guaranteed the formation of the core-shell structures of CNTs with SnO2 or other metal oxides, which are expected to have applications in chemical sensors and lithium ion batteries.

The work is focused on research and development of a suitable method for creating a selective emitter for the visible and near infrared region so that they are able to work optimally together with silicon photovoltaic cells in a thermophotovoltaic system. The aim of the work was to develop a new method of creating very fine structures outside the current standard, which will increase the emissivity of the base material to meet the needs of a selective emitter for the VID and NIR region. The methods available to us for the creation of structures were chosen, from which we eliminated all unsuitable ones and we introduced the optimal procedure and parameters for their creation for the selected method. In this work, we focused on both ceramic and metallic materials, whose heat resistance and selective properties are key to this work. Part of the development of the emitter structures was also the need for pretreatment of the substrate itself, where great emphasis was placed on the purity of materials and surface roughness. Since ceramic materials cannot achieve a surface roughness so low that the desired structures can be formed, these materials have been purposefully used primarily for the purpose of combining the base material with thin layers of other high temperature material. Their compatibility and suitability were verified in terms of adhesion and subsequent heat resistance. The main material for the formation of fine structures was purposefully chosen tungsten, for which we verified the influence of the formed structure on the emissivity as well as the thermal stability during long-term exposure to high temperatures. The work thus represents not only a new method of creating very fine structures, which are not normally formed in such subtlety, but also opens the way to new possibilities of combining more materials to achieve the required selectivity of the thermophotovoltaic emitter.

Thermal radiation is a fundamental heat transfer process, with certain basic aspects still not fully understood. Furthermore, tailoring its properties has potential to affect a wide range of applications, particularly thermophotovoltaics (TPV) and radiative cooling. TPV converts heat into electricity using thermal radiation to illuminate a photovoltaic diode, with no moving parts. With its realistic efficiency limit up to 50% (heat source at 1200 ^oC), TPV has garnered substantial interest. However, state-of-the-art TPV demonstrations are still well below theoretical limits, because of losses from generating and efficiently converting or recycling thermal radiation. In this thesis, tailored integrated photonic crystal structures are numerically simulated to enhance the efficiency of solar TPV. Next, a high-temperature thin-film Si-based selective absorber and emitter is designed, fabricated and experimentally characterized. It exhibits great potential to open up new applications, as it lends itself to large-scale production with substantial mechanical flexibility and excellent spectral selectivity for extended time periods, even when operating under high operating temperatures (600 ^oC) for up to 6 hours, with partial degradation after 24 hours. To perform this high-temperature characterization, an emittance measurement setup has been built; its performance agrees well with numerical simulations. Second, a unique passive cooling mechanism known as radiative cooling is developed to reduce the operating temperature of the photovoltaic diode. The significant effect of radiative cooling as a complement for an all-passive-cooling TPV system is proposed and numerically analyzed under a range of conditions. Furthermore, an outdoor experiment has been performed to demonstrate the effect of radiative cooling on a concentrating photovoltaic system, which can potentially be applied to the thermal management of a TPV system. In summary, this work paves the way towards the development of reliable, quiet, lightweight, and sustainable TPV and radiatively cooled power sources for outdoor applications.

Bright emitters with photoluminescence in the spectral region of 800–1600 nm are increasingly important as optical reporters for molecular imaging, sensing, and telecommunication and as active components in electrooptical and photovoltaic devices. Their rational design is directly linked to suitable methods for the characterization of their signal-relevant properties, especially their photoluminescence quantum yield (Φf ). Aiming at the development of bright semiconductor nanocrystals with emission >1000 nm, we designed a new NIR/IR integrating sphere setup for the wavelength region of 600–1600 nm. We assessed the performance of this setup by acquiring the corrected emission spectra and Φf of the organic dyes |trybe, IR140, and IR26 and several infrared (IR)-emissive Cd₁₋ₓHgₓTe and PbS semiconductor nanocrystals and comparing them to data obtained with two independently calibrated fluorescence instruments absolutely or relative to previously evaluated reference dyes. Our results highlight special challenges of photoluminescence studies in the IR ranging from solvent absorption to the lack of spectral and intensity standards together with quantum dot-specific challenges like photobrightening and photodarkening and the size-dependent air stability and photostability of differently sized oleate-capped PbS colloids. These effects can be representative of lead chalcogenides. Moreover, we redetermined the Φf of IR26, the most frequently used IR reference dye, to 1.1 × 10⁻³ in 1,2-dichloroethane DCE with a thorough sample reabsorption and solvent absorption correction. Our results indicate the need for a critical reevaluation of Φf values of IR-emissive nanomaterials and offer guidelines for improved Φf measurements.

No description available.

Lithium niobate (LiNbO3) is a human-made crystalline which is widely used in modern photonics due to its useful properties. In recent years, there has been significant progress in the development of lithium niobate on insulator (LNOI) technology, realizing a fully functional photonic integrated circuits, thanks to its capabilities in both electro-optics and second-order optical nonlinearity. To integrate laser source and amplifier onto the photonic integrated chips, rare-earth-ion doping has been considered while traditional laser source is difficult to integrate on chip. Among the rare-earth ions, erbium ions can provide laser source at 1550nm, which can meet the requirements of high-speed telecommunication band. In this thesis, we investigated a recent-made erbium-implanted LNOI sample through setting up a homebuilt microscope system. By exciting the erbium-implanted area with 980nm continuous wave laser, the emission light around 1550nm was collected and measured. Developing the setup with an automatic scanning code, the photoluminescence response of the implanted area on the sample was mapped. Conclusively, the investigation of the implanted samples demonstrated that the erbium-ion emitters could emit measurable photoluminescence signal around 1550 nm wavelength in spite of background noise and notably at room temperature. These results demonstrated the capability of the designed microscope while still need to be improved in terms of detectors sensitivity and signal to noise ratio. It also revealed the promising implantation of active Er ions into LNOI chips conveying the fabrication of Er photon sources on thin film lithium niobate in next step. / Lithiumniobat (LiNbO_3) är en konstgjord kristall som är allmänt använd inom modern fotonik på grund av dess användbara egenskaper. Under de senaste åren har det skett betydande framsteg inom utvecklingen av teknologin för litiumniobat på isolator (LNOI), vilket har resulterat i fullt fungerande fotoniska integrerade kretsar, tack vare dess förmågor inom både elektrooptik och optisk icke-linjäritet av andra ordningen. För att integrera laserskälla och förstärkare på de fotoniska integrerade kretsarna har överväganden gjorts om tillsats av sällsynta jordartsmetaller, eftersom det är svårt att integrera traditionella laserskällor på kretsar. Bland de sällsynta jordartsmetalljonerna kan erbiumjoner fungera som laserskälla vid 1550 nm, vilket uppfyller kraven för höghastighetstelekommunikationsbandet. I denna avhandling undersökte vi nyligen tillverkat ett LNOI-prov som hade implanterats med erbiumjoner genom att bygga upp ett hemgjort mikroskopsystem. Genom att excitera det erbium-implanterade området med en 980 nm kontinuerlig våglaser samlades och mättes utstrålningen vid 1550 nm. Genom att utveckla installationen med en automatisk skanningskod kartlades fotoluminescensresponsen hos det implanterade området på provet. Sammantaget visade undersökningen av de implanterade proverna att erbiumjonemitterare kunde avge mätbara fotoluminescenssignaler vid en våglängd omkring 1550 nm trots bakgrundsbuller och framför allt vid rumstemperatur. Dessa resultat bekräftade mikroskopets kapacitet, även om förbättringar behövs vad gäller detektorns känslighet och signal-till-brusförhållandet. De avslöjade också den lovande implanteringen av aktiva Er-joner i LNOI-kretsar och möjligheten att tillverka Er-fotonkällor på tunna filmer av litiumniobat i nästa steg.

Dans la première partie de cette thèse, nous tirons parti du concept de nano-antenne optique afind'apporter une solution innovante au problème d'interprétation de la microscopie champ procheoptique (SNOM). En effet, il est connu que certaines nano-antennes développent des réponsesoptiques dipolaires. Dans cette thèse nous démontrons comment l’utilisation d’une nano-ouverturepapillon (nano-antenne dipolaire), à l’extrémité d’une pointe SNOM, permet de détecter et collecteruniquement une seule composante du champ proche électrique. Ce résultat est démontré d’unpoint de vue théorique par l’utilisation de simulation FDTD (Finite Difference Time Domain) et d’unpoint de vue expérimental par la caractérisation, par cette pointe innovante, d´échantillonsdiélectriques (réseaux, cristaux photoniques) et métalliques (milieux désordonnés plasmoniques).Dans une deuxième partie, nous démontrons comment la sonde développée dans la premièrepartie, peut être utilisée comme détecteur du signal émis par un nano-émetteurs (NE) unique. Il estétudié dans cette partie l’effet de couplage entre ces deux objets. Dans un premier temps, après ladescription complète des grandeurs caractéristiques d’un NE, nous démontrons théoriquementl’effet de la pointe sur la réduction du temps de vie de l’état excité et l’augmentation de lafluorescence d’un NE, en régime saturé et non saturé. Puis dans un deuxième temps nousdémontrons expérimentalement comment cette sonde réduit le temps de vie de l’état excité deboites quantiques placées à son extrémité, en comparaison de pointes SNOM plus conventionnellestelle que la pointe diélectrique et la pointe à ouverture circulaire. / In the first part of this manuscript, we use in our advantage the concept of optical nano-antennas, toget new solutions on the interpretation problems of scanning near-field optical microscope (SNOM)images. Indeed, it is known that some of the developed nano-antennas can express dipolarbehaviours. In this manuscript, we show how a bowtie nano-aperture (dipolar nano-antenna)embedded at the apex of a SNOM probe, can be used to detect and collect only one component ofthe electric near-field. This result is demonstrated as well theoretically, by the use of FDTD (FiniteDifference Time Domain) codes, as experimentally, by the characterisation with this tip, of dielectricsamples (diffraction grating and photonic crystals) and metallic ones (random plasmonic medium).In a second part, we show how the tip previously described, can be used as a detector of the signalfrom single emitter (SE). We study in this part the coupling and interactions between those twoobjects. After a full description of a two level system characteristics, we show theoretically the effectof our probe on the reduction of the excited state life time and the enhancement of thefluorescence of the SE, in both regime, saturated and non-saturated. Then we describeexperimentally how our special tip reduces the excited state life time of quantum dots placed at theapex of it, respect to more conventional SNOM probes as the dielectric and the circular apertureones.