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Orientador: Carlos José Leopoldo Constantino / Banca: Sérgio Antônio Marques de Lima / Banca: Henrique de Santana / Banca: Rômulo Augusto Ando / Banca: Marystela Ferreira / Resumo: O presente trabalho abrange a síntese de nanopartículas metálicas com propriedades plasmônicas específicas incorporadas a filmes finos nanoestruturados de moléculas de interesse, como metaloporfirinas e outras. Nanopartículas de ouro (AuNPs 16 nm) foram incorporadas a filmes Langmuir-Blodgett (LB) de metaloporfirina visando o efeito SERS (espalhamento Raman amplificado em superfície). A incorporação das AuNPs se deu por codeposição, a partir das interações entre as AuNPs (presentes na subfase do filme de Langmuir) e as moléculas de metaloporfirina (espalhadas na interface ar/água). Nanopartículas de ouro recobertas com sílica (Au-SHINs), com tamanhos diferentes (40 e 100 nm) e mesma espessura de recobrimento (10 nm), também foram incorporadas em filmes LB e em solução aquosa visando o efeito SEF (fluorescência amplificada em superfície). Três variáveis foram aplicadas para aumentar a fluorescência: tamanho de nanopartícula, agregação e temperatura da amostra. Resultados teóricos e experimentais mostraram que as Au-SHINs 100 nm apresentam uma intensidade de amplificação cerca de 3 vezes maior e um espalhamento 2 ordens de grandeza maior que as Au-SHINs 40 nm, levando a maiores fatores de amplificação (EF). Além disso, a agregação das Au-SHINs com eletrólito e a diminuição da temperatura da amostra também resultou em maiores EF. Visando uma aplicação ambiental, AuNPs 100 nm e Au-SHINs 100 nm recobertas com 4 nm de sílica foram aplicadas na detecção do herbicida ametrina. Soluçõ... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The present work covers the synthesis of metallic nanoparticles with specific plasmonic properties incorporated into nanostructured thin films of target molecules, as metalloporphyrins and others. Gold nanoparticles (AuNPs 16 nm) were incorporated into Langmuir-Blodgett (LB) films of metalloporphyrin aiming the SERS effect (surface-enhanced Raman spectroscopy). AuNPs were incorporated by co-deposition, taking advantage of the interaction between the AuNPs (in the Langmuir film subphase) and the metalloporphyrin molecules (sprayed at the air/water interface). Gold shell-isolated nanoparticles (Au-SHINs), with different sizes (40 and 100 nm) and same silica shell thickness (10 nm), were also incorporated into LB films and in aqueous solution targeting the SEF effect (surface-enhanced fluorescence). Three variables were applied to increase the fluorescence: size of nanoparticle, aggregation and sample temperature. Theoretical and experimental results showed that the Au-SHINs 100 nm have an enhancement intensity about 3 times higher and a scattering 2 orders of magnitude higher than the Au-SHINs 40 nm, leading to higher enhancement factors (EF). Besides, the aggregation of Au-SHINs with electrolyte and the sample temperature decreased also resulted to higher EF. Aiming an environmental application, AuNPs 100 nm and Au-SHINs 100 nm coated with 4 nm of silica were applied to detect the herbicide ametryn. Ethanolic solution with concentration of 10-5 mol/L in AuNPs and Au-SHINs coll... (Complete abstract click electronic access below) / Doutor

Made available in DSpace on 2014-06-11T19:35:08Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-10-24Bitstream added on 2014-06-13T18:46:25Z : No. of bitstreams: 1 ledemi_yag_dr_araiq.pdf: 4381823 bytes, checksum: a988190ae336a68b630fd0469bbb9ed7 (MD5) / Les travaux présentés dans ce manuscrit concernent l’étude de nouvelles vitrocéramiques transparentes à base de chalco-halogénures dopées par des ions de terres pour la luminescence dans le visible. L’addition de différents halogénures d’alcalins à des verres du système Ga2S3-GeS2 a été étudiée avec l’objectif d’étendre leur transparence vers l’ultraviolet. Des verres du système Ga2S3- GeS2-CsCl complètement transparents dans le visible (400-750 nm) jusqu’au moyen infrarouge (11,5 μm) ont été obtenus. Des vitrocéramiques transparentes et homogènes ont ensuite été préparées de manière contrôlée à partir de plusieurs verres à différentes teneurs en CsCl dans le système Ga2S3-GeS2-CsCl. Des nanocristallites de taille homogène et uniformément dispersées dans la matrice amorphe sont formées de manière reproductible par des traitements thermiques appropriés. Une étude d’un point de vue structural de la cristallisation a été réalisée par diffraction de rayons X et résonance magnétique nucléaire à l’état solide sur les noyaux 71Ga et 133Cs. Le rôle d’agent de nucléation du gallium a été mis en évidence dans cette matrice avec la cristallisation d’une phase Ga2S3. Un meilleur comportement mécanique a également été observé pour les matériaux composites préparés. Des vitrocéramiques dopées par des ions de terres rares (praséodyme Pr3+ et néodyme Nd3+) ont été synthétisées dans le système Ga2S3-GeS2-CsCl. L’évolution de la luminescence dans le visible des ions Pr3+ et Nd3+ a été étudiée en fonction des conditions de traitement thermique. Au vu des résultats obtenus, il semble que l’ion Pr3+ ne soit pas incorporé dans les cristallites. Une augmentation de la luminescence de l’ion Nd3+ a en revanche été constatée, suggérant une incorporation partielle de ces ions dans une phase cristalline... (Résumé complet accès électronique ci - dessous) / Vitrocerâmicas transparentes baseadas em novas composições de calco-halogenetos dopadas com íons de terras raras foram produzidas com o objetivo de gerar luz no visível. A adição de diferentes halogenetos alcalinos em vidros do sistema Ga2S3-GeS2 foi estudada com a finalidade de aumentar a sua janela de transparência no ultravioleta. Vidros no sistema Ga2S3- GeS2-CsCl totalmente transparentes no visível (400-750 nm) até a região do infravermelho médio (11,5μm) foram obtidos. Vitrocerâmicas transparentes e homogêneas foram em seguida preparadas a partir de vidros variando a concentração de CsCl no sistema Ga2S3-GeS2-CsCl. As condições dos tratamentos térmicos (temperaturas e tempos) foram estabelecidas permitindo o controle dos processos de nucleação e crescimento dos cristalitos dentro da matriz vítrea. Nanocristalitos uniformemente distribuídos e com tamanho homogêneo foram obtidos e confirmados por microscopia eletrônica de varredura (MEV) e microscopia eletrônica de transmissão (MET). Estudos estruturais foram realizadas nas vitrocerâmicas utilizando-se as técnicas de difração de raios X e resonância magnetica nuclear do sólido do 133Cs e 71Ga. Foi evidenciado o papel do agente de nucleação do gálio neste material, com a cristalização da fase Ga2S3. Um aumento da resistência mecânica foi também observado nestes materiais em comparação aos vidros de base. Em seguida, vitrocerâmicas dopadas com íons de terras raras (praseodímio Pr3+ e neodímio Nd3+) foram sintetizadas no sistema Ga2S3-GeS2-CsCl. A luminescência dos íons Pr3+ e Nd3+ no visível foi estudada em função dos tratamentos térmicos aplicados aos materiais. Foi observado que não houve a incorporação dos íons Pr3+na matriz. Por outro lado, um aumento da fluorescência do íon Nd3+ foi observado, sugerindo uma incorporação parcial destes íons dentro da fase cristalina... / The present work deals with the study of new chalco-halide glass-ceramics doped with rare earth ions for visible luminescence. The effect of the addition of different alkali-halide into glasses belonging to the Ga2S3-GeS2 system has been studied with the aim to extend their transparency into the ultraviolet region. Glasses transparent over the visible range (400-750 nm) up to the mid infrared (11,5 μm) have been obtained in the Ga2S3-GeS2-CsCl system. Transparent and homogeneous glass-ceramics have been prepared from several base glasses varying the CsCl content in the Ga2S3-GeS2-CsCl system. Nanocrystals with homogeneous size and uniformly distributed in the amorphous matrix have been generated with reproducibility by appropriate heat-treatment. A structural study of the crystallization has been realized using X-ray diffraction and solid state nuclear magnetic resonance performed on the 71Ga and 133Cs nuclei. The nucleating agent character of gallium has been shown in the glassy matrix with the crystallization of the Ga2S3 phase. An improved mechanical behaviour has also been observed in the prepared composite materials. Rare-earth ion (praseodymium Pr3+ and neodymium Nd3+) doped glass-ceramics have been synthesized in the Ga2S3-GeS2-CsCl system. The visible luminescence from Pr3+ and Nd3+ ions has been studied as a function of heat-treatment conditions. It appeared from experiments that Pr3+ ions are not incorporated into the crystals contrary to the Nd3+ ions from which an enhanced luminescence was observed, suggesting their partial integration into the crystalline phase. Finally, silver and Pr3+ doped glasses have been synthesized in the Ga2S3-GeS2 system. Metallic silver nanoparticles were generated by heat-treatment at 370°C and characterized by transmission electronic microscopy. The influence of the NPs on the Pr3+ ions luminescence properties was studied by performing frequency... (Complete abstract click electronic access below)

The plasmonic properties of silver-based alloy thin films were studied. Silver-ytterbium (Ag-Yb) and silver-magnesium (Ag-Mg) prepared by thermal co-evaporation were investigated extensively for various thin film properties. The optical properties were intensively analyzed and discussed because the dielectric response of a material is particularly significant in terms of its plasmonic properties. The study of silver-based alloy thin films has been mostly about Ag alloying with other transition metals, but the results of Ag-Yb and Ag-Mg in this work showed that the intensity of plasma resonance is tunable, in which the idea may also apply to other silver-rich binary alloy thin films regardless of the kind of second metal components. In our research, the Ag plasma resonance was weakened with respect to the concentration of Yb and Mg in the alloy thin films. The change in the optical characteristics around Ag plasma resonance frequency was attributed to an increase in “resonance damping. This is confirmed from modeling using classical free-electron theory. The increase in the damping was experimentally corroborated by the concentration dependence of electrical conductivity and estimated average crystallite size of Ag-Yb and Ag-Mg thin films. The reduction in electrical conductivity was not only caused by introducing less conductive Yb or Mg but also through disturbing the Ag lattice structure to promote additional electron scattering at grain boundaries. The Ag-Yb and Ag-Mg alloys carried intermediate properties between their pure components despite the presence of Yb or Mg oxides. Besides optical and electrical properties, changes in the electronic work function were also assessed since it is also important in applications. Plasmonic nanostructures and transparent organic light-emitting diodes (OLEDs) were fabricated to demonstrate their potential applications. Two-dimensional disc-arrays nanostructures composed of pure Ag and Ag-Yb were implemented to evaluate the plasmonic properties. The damping loss in Ag-Yb caused weakened coupling of incident photons and surface plasmons when compared to pure Ag without altering the coupling wavelengths, suggesting potential plasmonic materials for tuning the coupling strength of surface plasmons by controlling the concentration of Yb which may also apply to Ag-Mg. Ultrathin Ag-Yb and Ag-Mg films were used as cathodes in transparent OLEDs for demonstration, which was beneficial by virtue of overall device transmittance though sacrificing electrical conduction leading to poor light emission unless inserting additional ultrathin lithium fluoride to modify the ultrathin cathodes.

Group- III nitride based semiconductors have emerged as the leading material for short wavelength optoelectronic devices. The InGaN alloy system forms a continuous and direct bandgap semiconductor spanning ultraviolet (UV) to blue/green wavelengths. An ideal and highly efficient light-emitting device can be designed by enhancing the spontaneous emission rate. This thesis deals with the design and fabrication of a visible light-emitting device using GaN/InGaN single quantum well (SQW) system with enhanced spontaneous emission. To increase the emission efficiency, layers of different metals, usually noble metals like silver, gold and aluminum are deposited on GaN/InGaN SQWs using metal evaporator. Surface characterization of metal-coated GaN/InGaN SQW samples was carried out using atomic force microscopy (AFM) and scanning electron microscopy (SEM). Photoluminescence is used as a tool for optical characterization to study the enhancement in the light emitting structures. This thesis also compares characteristics of different metals on GaN/InGaN SQW system thus allowing selection of the most appropriate material for a particular application. It was found out that photons from the light emitter couple more to the surface plasmons if the bandgap of former is close to the surface plasmon resonant energy of particular metal. Absorption of light due to gold reduces the effective mean path of light emitted from the light emitter and hence quenches the quantum well emission peak compared to the uncoated sample.

Upconverted light from nanostructured metal surfaces can be produced by harmonic generation and multi-photon luminescence; however, these are weak processes and require extremely high field intensities to produce a measurable signal. Here we report on bright emission, five orders of magnitude greater than harmonic generation, that can be seen from metal tunnel junctions due to light-induced inelastic tunneling. Like inelastic tunneling light emission, which was recently reported to have 2% conversion efficiency per tunneling event, the emission wavelength recorded varies with the local electric field applied; however, here the field is from a 1560 nm femtosecond pulsed laser source. Finite-difference time-domain simulations of the experimental conditions show the local field is sufficient to generate tunneling-based inelastic light emission in the visible regime. This phenomenon is promising for producing ultrafast upconverted light emission with higher efficiency than conventional nonlinear processes. / Graduate

The increasing prevalence of glass windows in modern buildings has raised the demand for solar control windows that possess climate-appropriate properties. Glass windows made of abundant and low-cost materials which can both decrease the heating energy consumption as well as enhance the light climate indoors would sufficiently meet the goals of economical yet uplifting buildings. The main objective of this thesis was to examine whether a plasmonic hybrid interface, comprising three layers of thin films (gold nanoparticles of approximately 10 nm, ZrO2 with a thickness range of 20-35 nm, and ZnO with a thickness of approximately 20 nm), could achieve the upconversion of infrared light to visible light through a multiphoton absorption process in the ZnO layer. If successful, this configuration, in conjunction with an established layer capable of downconverting ultraviolet light to visible light, would be applied to commercially available glass windows to enhance the solar utilization and improve indoor lighting conditions. ZnO was selected as the upconversion material due to its wide emission range in the visible spectrum, indicative of intermediate electron states between the valence and conduction bands suitable for excitation. The objective of the plasmonic material, the gold nanoparticles, was to increase the probability of the upconversion process by utilizing the enhanced electric field resulting from plasmons localized at the surface of the gold nanoparticles. ZrO2 served as a separator layer between the plasmonic material and the ZnO, to effectively preventing charge transfer and ensuring that any upconversion or other photoluminescence processes were purely photonic. Various optical experimental techniques were employed in this study to assess any upconversion, plasmon enhancement, and map the intermediate electron states of the ZnO. The ZrO2 layer successfully prevented charge transfer between the layers. However, the influence ofthe gold’s surface plasmons and it’s enhanced electric field on ZnO emission varied among the samples, likely due to the synthesis processes. Ultimately, the plasmonic hybrid interface investigated in this thesis did not exhibit detectable upconversion when illuminated with either 600 or 750 nm light. Further research is necessary to increase the density of intermediate electron states in ZnO, along with optimization of the thin film synthesis to enhance plasmon effects. These advancements would augment the probability of detectable upconversion.

In this thesis, Density Functional Theory and Time-Dependent Density-Functional Theory approaches are applied to study the optical and magnetic properties of several types of nanostructures. In studies of the optical properties we mainly focused on the plasmonic and excitonic effects in pure and transition metal-doped noble metal nanochains and their conglomerates. In the case of pure noble metal chains, it was found that the (collective) plasmon mode is pronounceable when the number of atoms in the chain is larger than 5. The plasmon energy decreases with further with increasing number of atoms (N) and is almost N-independent when N is larger than 20. In the case of coupled pure chains it was found that the plasmon energy grows as square root of the number of chains, and reaches the visible light energy 1.8eV for the case of three parallel chains. Doping of pure Au chains with transition-metal atoms leads in many cases to formation of additional plasmon peaks close in energy to the undoped chain peak. This peak comes from the local charge oscillations around the potential minima created by the impurity atom. The effect is especially pronounced for Ni-doped chains. In the multiple-chain case, we find an unusual hybridization of the two different (local and collective) plasmon modes. Changing the chain size and chemical composition in the array can be used to tune the absorption properties of nanochains. The case of coupled finite (plasmonic) and infinite (semiconductor, excitonic) chains was also analyzed. We find that one can get significant exciton-plasmon coupling, including hybridized modes and energy transfer between these excitations, in the case of doped chains. The impurity atoms are found to work as attraction centers for excitons. This can be used to transform the exciton energy into local plasmon oscillations with consequent emission at desired point (at which the impurity is located). In a related study the optical properties of single layer MoS2 was analyzed with a focus on the possibility of ultrafast emission, In particular, it was found that the system can emit in femto-second regime under ultrafast laser pulse excitations. Finally, we have studied the magnetic properties of FeRh nanostructures to probe whether there is an antiferromagnetic to ferromagnetic transition as a function of the ratio of Fe and Rh atoms, as in the bulk alloy.. Surprisingly, the ferromagnetic phase is found to be much more stable for these nanostructures as compared to the bulk, which suggests that band-type effects may be responsible for this transition in the bulk, i.e. the transition cannot be described in terms of modification of the Heisenberg model parameters.

The current thrust towards developing silicon compatible integrated nanophotonic devices is driven by need to overcome critical challenges in electronic circuit technology related to information bandwidth and thermal management. Surface plasmon nanophotonics represents a hybrid technology at the interface of optics and electronics that could address several of the existing challenges. Surface plasmons are electronic charge density waves that can occur at a metal-dielectric interface at optical and infrared frequencies. Numerous plasmon based integrated optical devices such as waveguides, splitters, resonators and multimode interference devices have been developed, however no standard integrated device for coupling light into nanoscale optical circuits exists. In this thesis we experimentally and theoretically investigate the excitation of propagating surface plasmons via resonant metal nanoparticle arrays placed in close proximity to a metal surface. It is shown that this approach can lead to compact plasmon excitation devices. Full-field electromagnetic simulations of the optical illumination of metal nanoparticle arrays near a metal film reveal the presence of individual nanoparticle resonances and collective grating-like resonances related to propagating surface plasmons within the periodic array structure. Strong near-field coupling between the nanoparticle and grating resonances is observed, and is successfully described by a coupled oscillator model. Numerical simulations of the effect of nanoparticle size and shape on the excitation and dissipation of surface plasmons reveal that the optimum particle volume for efficient surface plasmon excitation depends sensitively on the particle shape. This observation is quantitatively explained in terms of the shape-dependent optical cross-section of the nanoparticles. iv Reflection measurements on nanoparticle arrays fabricated using electron-beam lithography confirm the predicted particle-grating interaction. An unexpected polarizationdependent splitting of the film-mediated collective resonance is successfully attributed to the existence of out-of plane polarization modes of the metal nanoparticles. In order to distinguish between the excitation of propagating surface plasmons and localized nanoparticle plasmons, spectrally resolved leakage radiation measurements are presented. Based on these measurements, a universally applicable method for measuring the wavelength dependent efficiency of coupling free-space radiation into guided surface plasmon modes on thin films is developed. Finally, it is shown that the resonantly enhanced near-field coupling the nanoparticles and the propagating surface plasmons can lead to optimized coupler device dimensions well below 10 m.

Metal nano particles are investigated as scattering centers on front surface of thin-film solar cells to improve efficiency. The principle is that scattering, which is enhanced near the plasmon resonance frequency of the particle and depends on particle size, increases the effective optical path length of incident light, leading to more light absorption in active layer of thin film solar cell. The particular types of particles investigated here are known as "metal-black", well known as an IR absorber for bolometric infrared detectors. Gold-black was deposited on commercial thin-film solar cells using a thermal evaporator in a nitrogen ambient at pressures of ~1 Torr. We suggest that the broad range of length scales for gold black particles, as quantified by scanning electron microscopy, gives rise to efficient scattering over a broad range of wavelengths across the solar spectrum. The solar cell efficiency was determined both as a function of wavelength and for a solar spectrum produced by a Xe lamp and appropriate filters. Up to 20% increase in short-circuit photocurrent, and a 7% increase in efficiency at the maximum power point, were observed.