GaN and its alloys with Al and In belong to the group III nitride semiconductors and are today the materials of choice for efficient white light emitting diodes (LEDs) enabling energy saving solid state lighting. Currently, there is a great interest in the development of novel inexpensive techniques to fabricate hybrid LEDs combining high quality III-N quantum well (QW) structures with inexpensive colloidal nanoparticles or conjugated polymers. Such hybrid devices are promising for future micro-light sources in full-color displays, sensors and imaging systems. Organics can be engineered to emit at different wavelengths or even white light based on functional groups or by blend of several polymers. This is especially important for the green region, where there is still a lack of efficient LEDs. Besides optoelectronics, other applications such as biochemical sensors or systems for water splitting can be realized using GaN-based nanostructures. Despite a significant progress in the field, there is still a need in fundamental understanding of many problems and phenomena in III-nitride based nanostructures and hybrids to fully utilize material properties on demand of specific applications. In this thesis, hybrid structures based on AlGaN/GaN QWs and colloidal ZnO nano-crystals have been fabricated for down conversion of the QW emission utilizing non-radiative (Förster) resonant energy transfer. Time-resolved photoluminescence (TRPL) was used to investigate the QW exciton dynamics depending on the cap layer thickness in the bare QW and in the hybrid samples. Although the surface potential influences the exciton dynamics, the maximum pumping efficiency assuming a non-radiative energy transfer mechanism was estimated to be ~40 % at 60 K in the structure with thin cap layer of 3 nm. Since bulk GaN of large area is difficult to synthesize, there is a lack of native substrates. Thus, GaN-based structures are usually grown on SiC or sapphire, which results in high threading dislocation density in the active layer of the device and can be the reason of efficiency droop in GaN based LED structures. Fabricating GaN nanorods (NR) can be a way to produce GaN with lower defect density since threading dislocations can be annihilated toward the NR wall during growth. Here, GaN(0001) NRs grown on Si(111) substrates by magnetron sputtering using a liquid Ga target have been investigated. A high quality of NRs have been confirmed by transmission electron microscopy (TEM) and TRPL. Two strong near band gap emission lines at ~3.42 eV and ~3.47 eV related to basal plane stacking faults (SF) and donor-bound exciton (DBE), respectively, have been observed at low temperatures. TRPL properties of the SF PL line suggest that SFs form a regular structure similar to a multiple QWs, which was confirmed by TEM. The SF related PL measured at 5 K for a single NR has a significantly different polarization response compared to the GaN exciton line and is much stronger polarized (> 40 %) in the direction perpendicular to the NR growth axis. Hybrids fabricated using GaN NRs and the green emitting polyfluorene (F8BT) have been studied using micro-TRPL. In contrast to the DBE emission, the recombination time of the SF-related emission was observed to decrease, which might be due to the Förster resonance energy transfer mechanism. Compared to chemical vapor deposition, sputtering allows synthesis at much lower temperatures. Here, sputtering was employed to grow InAlN/GaN heterostructures with an indium content targeted to ~18 %, which is lattice matched to GaN. This means that near strain-free GaN films can be synthesized. It was found that using a lower temperature (~25 C) while depositing the top InAlN results in an improved interface quality compared to deposition at 700 C. In latter case, regions of quaternary alloy of InAlGaN forming structural micro-defects have been observed at the top InAlN/GaN interface in addition to optically active flower-like defect formations.

Theoretical and experimental plasmonics is a growing field as a method to create near fields at sub-wavelength distances. In this thesis, a finite-difference time-domain method is used to simulate electromagnetic waves onto a thin film that present of nickel nanorods with sharp apexes. The absorbed, transmitted, and reflected fields were shown to depend linearly on silver film thickness and nanotip length. The electric field is visualized along the tip to show strong charge density along the base of the tip’s apex and how that density changes for wavelength, metal, and source tilt. Lastly, the study shows gold film on the nanotip apex provides the largest enhancement of the electric field for the wavelengths 532, 572, and 633 nm.

As nanopartículas de ouro (AuNPs), com formatos e distribuição de tamanhos definidos, têm atraído grande atenção devido às suas propriedades óticas e e catalíticas únicas, que dependem de da forma e tamanho de AuNPs e que são importantes para diversos aplicações. O desenvolvimento de métodos simples e ecológicamente seguros para a síntese de AuNPs de tamanho e forma controlados, empregando reagentes de baixo custo e de fácil manuseamento é, portanto, de grande importância. Considerando isto, realizou-se um estudo sistemático para preparar nanoparticlus de ouro (AuNPs) e prata (AgNPs) com um controle de forma e tamanho, empregando exclusivamente glicerol como um agente redutor flexivel, eco-friendly e de baixo custo. Em primeiro lugar, descrevemos um novo one-pot método para a preparação de nanorods ou nanobastões de ouro (AuNRs) monocristalinos com quase 100% de rendimento empragando o glicerol em meio alcalino como agente redutor e Brometo de hexadeciltrimetilamónio (CTAB) como agente controlador da forma de particulas. Podemos conseguir um controle da razões de aspecto (Aspect ratio do inglês, AR = 2 a 6), rendimento de AuNRs (27-99%) bem como da posicao de banda de absorção óticas de AuNRs (de 620 a 1200 nm) simplesmente variando as condições experimentais, principalmente o pH de meio reaccional (variou-se entre 12-13,5) e a concentração do AgNO3. Descobrimos que a formação de AuNRs é mais rápida a pH mais alto (> 11) e a maior temperatura (> 30 ° C), mas o rendimento de AuNRs é menor (< 70%). A análise de HRTEM mostrou que os AuNRs crescem na direcção [001] e têm uma estrutura do tipo fcc monocristalina, isenta de falhas estruturais ou deslocamentos. Em segundo lugar, realizamos com sucesso, pela primeira vez, a formação de nanoparticlulas esféricas de ouro (AuNPs), quase monodispersas de cerca de 8 nm, utilizando o glicerol bruto conhecido localmente como Glicerina Loíra (crude glycerol (CG) do inglê), tal como recebido, da planta de biodiesel pela. Não foi realizado nehum tratamento químico ou físico específico do CG, exceto filtração simples. Utilizaram-se duas amostras diferentes de CG com diferentes teores de glicerol (65% e 73%) e diferentes níveis de impurezas (baixo e alto) e tipos (orgânicos e inorgânicos) para preparar AuNPs, a fim de estudar o efeito de possíveis impurezas na formato e distribuição de tamanho de AuNPs. Para comparação, foram também preparadas AuNPs utilizando glicerol comercial puro (99,5%) em condições experimentais idênticas. Foram obtidos AuNPs com tamanho e formato semelhantes em ambos os casos (glicerol puro comercial e CG) indicando que o glicerol comercial pode ser substituído por CG na síntese de AuNPs e as impurezas orgânicas e inorgânicas não afectam significativamente a distribuição de tamanho de AuNPs preparadas . Este estudo abre novas possibilidades para um eco-friendly preparação de nanopartículas metálicas utilizando o CG com um agente redutor barato, não tóxico e biodegradável como. Em terceiro lugar, desenvolvemos um método de síntese de AuNPs do tipo Ligand-free (sem uso de agente establizante) empregando o glicerol tanto como agente redutor quanto com agente estabilizador. A ideia era evitar o uso de um agente estabilizante externo que muitas vezes diminui a actividade catalítica ou afeta adversamente a biocompatibilidade dos sistemas surfactante/AuNPs. Obtiveram-se AuNPs coloidais estáveis com uma distribuição de tamanho razoavelmente estreita (8 &plusmn; 3 nm) por este método e verificou-se que a estabilidade e distribuição de tamanho das partículas dependiam da razão água/glicerol, temperatura e pH dos meios reaccionais. Tais ligand-free AuNPs preparados utilizando glicerol podem ser utilizadas nas aplicações catáliticas e biomédicas. / Gold nanoparticles (AuNPs) especially with a control of size and shape have attracted great attention due to their shape-dependent optical properties that are important for many applications. The development of simpler and greener methods for the synthesis of size- and shape-controlled AuNPs employing low-cost and easily handled reagents is thus of great importance. Thus we have carried out a systematic study to prepare shape- and size-controlled AuNPs and AgNPs employing exclusively glycerol as an eco-friendly, low cost and pH-tunable reducing agent. Firstly, we report a new one-pot seedless method for the preparation of single-crystalline AuNRs in almost 100% yield based on the use of glycerol in alkaline medium as the reducing agent and hexadecyltrimethylammonium bromide (CTAB) as the shape-controlling agent. We could achieve a control of the aspect ratio (AR= 2 to 6), AuNRs yield (27-99%) as well the LSPR band of the AuNRs (620 to 1200 nm) by simply varying the experimental conditions, principally the pH of the reaction media (varied between 12-13.5 ) and the concentration of the AgNO3. We found that the formation of AuNRs is faster at higher pH (>11) and higher temperature (>30°C) but the AuNRs yield is smaller (< 70%). HRTEM analysis showed that the AuNRs grow in [001] direction and have a perfect single crystalline fcc structure, free from structural faults or dislocations. Secondly, we successfully carried out the formation of nearly monodisperse spherical AuNPs of around 8 nm using the as-received crude glycerol (CG) from the biodiesel plant for the first time. No special chemical or physical treatment of CG except simple filtration was carried out. Two different crude glycerol samples with different glycerol contents (65% and 73%) and different impurity levels (low and high) and types (organic and inorganic) were employed to prepare AuNPs so as to study the effect of possible impurities on the shape and size distribution of AuNPs. For comparison, AuNPs were also prepared using pure commercial (99.5 %) glycerol under identical experimental conditions. AuNPs with similar size and shape were obtained in both cases (commercial pure glycerol as well as CG) indicating that commercial glycerol can be replaced with CG in the AuNPs synthesis and the organic and inorganic impurities do not significantly affect the particle size distribution of prepared AuNPs. This study opens up new possibilities for the environment-friendly preparation of metallic nanoparticles using the low-cost, non-toxic and biodegradable CG as a reducing agent. Thirdly, we developed a ligand-free one-pot synthesis method of AuNPs employing the eco-friendly glycerol both as reducing agent and stabilizing agent. The idea was to avoid the use of an external stabilizing agent which often hinder the catalytic activity and adversely affect the biocompatibility of the surfactant/AuNP systems. Stable AuNPs with reasonably good size distribution (8 &plusmn; 3 nm) were obtained by this method and the stability and size distribution of the particles was found to be dependent on the water/glycerol ratio, temperature and pH of the reaction media. Such surfactant-free biocompatible AuNPs prepared using the eco-friendly glycerol may find useful applications in catalysis and biomedical applications.

Gallium nitride (GaN)-based light-emitting diodes (LEDs) with cylindrical nanostructures have been the subject of significant research interest in the past decade, due to the potential of such structures to increase light extraction efficiency and deliver highly directional light emission. Nanorod LEDs, where the light emission is within the nanocylinder, have the additional potential to increase internal quantum efficiency and emit in colours previously thought impractical with GaN-based LEDs. Optical modelling of nanostructured LEDs is usually carried out using finite-difference time-domain methods, which are computationally intensive and do not always provide sufficient insight into the physics underlying the simulation results. This thesis proposes an intuitive, quasi-analytic method based on modal expansion. It is found that it is possible to calculate the far field diffraction patterns of all guided modes supported by a single nanorod, with full consideration of Fabry-Perot effects, in minutes using a standard office desktop computer. Focus is placed on the case of a nanorod of radius 140 nm, for which angular photoluminescence measurements were available to provide a means of validating the model. Consideration of the guided modes alone provides a compelling explanation for gross features in the measured data where none previously existed. It is shown that, using a standard equation from a textbook, it is possible to calculate how much each of the guided and radiation modes of a single nanorod is excited by a Hertzian dipole of known position and orientation with respect to the nanorod geometry. When interference between these modes is considered, it is possible to calculate the total far field angular emission pattern due to that dipole. Comparing these patterns with photoluminescence measurements allows one to infer the locations and orientations of dipole current sources; the results are found to be consistent with those of cathodoluminescence studies.

Gallium nitride (GaN) and its related semiconductor alloys are attracting tremendous interest for their wide range of applications in blue and green LEDs, diode lasers, high-temperature and high-power electronics. Nanomaterials such as InGaN/GaN core-shell three-dimensional nanostructures are seen as a breakthrough technology for future solid-state lighting and nano-electronics devices. In a core-shell LED, the active semiconductor layers grown around a GaN core enable control over a wide range of wavelengths and applications. In this thesis the capability for the heteroepitaxial growth of a proof-of-principle core-shell LED is advanced. A design that can be applied at the wafer scale using metalorganic vapor phase epitaxy (MOVPE) crystal growth on highly uniform GaN nanorod (NR) structures is proposed. This project demonstrates understanding over the growth constraints of active layers and dopant layers. The impact of reactor pressure and temperature on the morphology and on the incorporated InN mole fraction was studied for thick InGaN shells on the different GaN crystal facets. Mg doping and effectiveness of the p-n junction for a core-shell structure was studied by extensive growth experiments and characterization. Sapphire and Si substrates were used, and at all the stages of growth and fabrication. The structures were optimized to achieve geometry homogeneity, high-aspect-ratio, incorporation homogeneity for InN and Mg dopant. The three-dimensional nature of NRs and their light emission provided ample challenges which required adaptation of characterization and fabrication techniques for a core-shell device. Finally, an electrically contacted core-shell LED is demonstrated and characterized. Achieving a proof-of-principle core-shell device could be the starting point in the development of nanostructure-based devices and new physics, or in solving technical problems in planar LEDs, such as the polarization of emitted light, the quantum-confined Stark effect, efficiency droop, or the green gap.

As nanopartículas de ouro (AuNPs), com formatos e distribuição de tamanhos definidos, têm atraído grande atenção devido às suas propriedades óticas e e catalíticas únicas, que dependem de da forma e tamanho de AuNPs e que são importantes para diversos aplicações. O desenvolvimento de métodos simples e ecológicamente seguros para a síntese de AuNPs de tamanho e forma controlados, empregando reagentes de baixo custo e de fácil manuseamento é, portanto, de grande importância. Considerando isto, realizou-se um estudo sistemático para preparar nanoparticlus de ouro (AuNPs) e prata (AgNPs) com um controle de forma e tamanho, empregando exclusivamente glicerol como um agente redutor flexivel, eco-friendly e de baixo custo. Em primeiro lugar, descrevemos um novo one-pot método para a preparação de nanorods ou nanobastões de ouro (AuNRs) monocristalinos com quase 100% de rendimento empragando o glicerol em meio alcalino como agente redutor e Brometo de hexadeciltrimetilamónio (CTAB) como agente controlador da forma de particulas. Podemos conseguir um controle da razões de aspecto (Aspect ratio do inglês, AR = 2 a 6), rendimento de AuNRs (27-99%) bem como da posicao de banda de absorção óticas de AuNRs (de 620 a 1200 nm) simplesmente variando as condições experimentais, principalmente o pH de meio reaccional (variou-se entre 12-13,5) e a concentração do AgNO3. Descobrimos que a formação de AuNRs é mais rápida a pH mais alto (> 11) e a maior temperatura (> 30 ° C), mas o rendimento de AuNRs é menor (< 70%). A análise de HRTEM mostrou que os AuNRs crescem na direcção [001] e têm uma estrutura do tipo fcc monocristalina, isenta de falhas estruturais ou deslocamentos. Em segundo lugar, realizamos com sucesso, pela primeira vez, a formação de nanoparticlulas esféricas de ouro (AuNPs), quase monodispersas de cerca de 8 nm, utilizando o glicerol bruto conhecido localmente como Glicerina Loíra (crude glycerol (CG) do inglê), tal como recebido, da planta de biodiesel pela. Não foi realizado nehum tratamento químico ou físico específico do CG, exceto filtração simples. Utilizaram-se duas amostras diferentes de CG com diferentes teores de glicerol (65% e 73%) e diferentes níveis de impurezas (baixo e alto) e tipos (orgânicos e inorgânicos) para preparar AuNPs, a fim de estudar o efeito de possíveis impurezas na formato e distribuição de tamanho de AuNPs. Para comparação, foram também preparadas AuNPs utilizando glicerol comercial puro (99,5%) em condições experimentais idênticas. Foram obtidos AuNPs com tamanho e formato semelhantes em ambos os casos (glicerol puro comercial e CG) indicando que o glicerol comercial pode ser substituído por CG na síntese de AuNPs e as impurezas orgânicas e inorgânicas não afectam significativamente a distribuição de tamanho de AuNPs preparadas . Este estudo abre novas possibilidades para um eco-friendly preparação de nanopartículas metálicas utilizando o CG com um agente redutor barato, não tóxico e biodegradável como. Em terceiro lugar, desenvolvemos um método de síntese de AuNPs do tipo Ligand-free (sem uso de agente establizante) empregando o glicerol tanto como agente redutor quanto com agente estabilizador. A ideia era evitar o uso de um agente estabilizante externo que muitas vezes diminui a actividade catalítica ou afeta adversamente a biocompatibilidade dos sistemas surfactante/AuNPs. Obtiveram-se AuNPs coloidais estáveis com uma distribuição de tamanho razoavelmente estreita (8 &plusmn; 3 nm) por este método e verificou-se que a estabilidade e distribuição de tamanho das partículas dependiam da razão água/glicerol, temperatura e pH dos meios reaccionais. Tais ligand-free AuNPs preparados utilizando glicerol podem ser utilizadas nas aplicações catáliticas e biomédicas. / Gold nanoparticles (AuNPs) especially with a control of size and shape have attracted great attention due to their shape-dependent optical properties that are important for many applications. The development of simpler and greener methods for the synthesis of size- and shape-controlled AuNPs employing low-cost and easily handled reagents is thus of great importance. Thus we have carried out a systematic study to prepare shape- and size-controlled AuNPs and AgNPs employing exclusively glycerol as an eco-friendly, low cost and pH-tunable reducing agent. Firstly, we report a new one-pot seedless method for the preparation of single-crystalline AuNRs in almost 100% yield based on the use of glycerol in alkaline medium as the reducing agent and hexadecyltrimethylammonium bromide (CTAB) as the shape-controlling agent. We could achieve a control of the aspect ratio (AR= 2 to 6), AuNRs yield (27-99%) as well the LSPR band of the AuNRs (620 to 1200 nm) by simply varying the experimental conditions, principally the pH of the reaction media (varied between 12-13.5 ) and the concentration of the AgNO3. We found that the formation of AuNRs is faster at higher pH (>11) and higher temperature (>30°C) but the AuNRs yield is smaller (< 70%). HRTEM analysis showed that the AuNRs grow in [001] direction and have a perfect single crystalline fcc structure, free from structural faults or dislocations. Secondly, we successfully carried out the formation of nearly monodisperse spherical AuNPs of around 8 nm using the as-received crude glycerol (CG) from the biodiesel plant for the first time. No special chemical or physical treatment of CG except simple filtration was carried out. Two different crude glycerol samples with different glycerol contents (65% and 73%) and different impurity levels (low and high) and types (organic and inorganic) were employed to prepare AuNPs so as to study the effect of possible impurities on the shape and size distribution of AuNPs. For comparison, AuNPs were also prepared using pure commercial (99.5 %) glycerol under identical experimental conditions. AuNPs with similar size and shape were obtained in both cases (commercial pure glycerol as well as CG) indicating that commercial glycerol can be replaced with CG in the AuNPs synthesis and the organic and inorganic impurities do not significantly affect the particle size distribution of prepared AuNPs. This study opens up new possibilities for the environment-friendly preparation of metallic nanoparticles using the low-cost, non-toxic and biodegradable CG as a reducing agent. Thirdly, we developed a ligand-free one-pot synthesis method of AuNPs employing the eco-friendly glycerol both as reducing agent and stabilizing agent. The idea was to avoid the use of an external stabilizing agent which often hinder the catalytic activity and adversely affect the biocompatibility of the surfactant/AuNP systems. Stable AuNPs with reasonably good size distribution (8 &plusmn; 3 nm) were obtained by this method and the stability and size distribution of the particles was found to be dependent on the water/glycerol ratio, temperature and pH of the reaction media. Such surfactant-free biocompatible AuNPs prepared using the eco-friendly glycerol may find useful applications in catalysis and biomedical applications.

1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([BMIM]Tf2N) was investigated as a multifunctional solvent, ligand, and reducing agent for platinum deposition onto well-defined CdSe@CdS nanorods. Platinum deposition was carried out thermally and photochemically using Pt(acac)2 as the metal precursor. Thermal deposition was investigated in [BMIM]Tf2N with and without addition of a sacrificial reducing agent, and product topology was compared with the products obtained from polyol reduction using 1,2-hexadecanediol, oleic acid, and oleylamine in diphenyl ether. Photochemically induced platinum deposition was carried out at room temperature in [BMIM]Tf2N, and product topology was compared with the photodeposition products obtained from a toluene dispersion. Thermal deposition of platinum in ionic liquid showed rods of broken morphology and small platinum nanoparticles speckled across the rods’ surface, while photodeposition of platinum exhibited particles decorated throughout the nanorod surface but larger in size than those exhibited by thermal means. Photocatalytic reduction of methylene blue was studied using these Pt-CdSe@CdS heterostructured nanoparticles, and catalytic performance was correlated with topology and synthetic history. Initial findings of catalytic performance suggest that there in an advantage of depositing platinum nanoparticles onto the CdSe@CdS in the ionic liquid system. Methylene blue dye was degraded using each system and the results show and there is an increased performance of the nanorods synthesized in the ionic system.

<p>The aims of this study are to first immobilize positively charged gold nanorods to negatively charged cell culture surfaces. Second, to use polyelectrolytes for controlling the distance between gold nanorods and fluorophores. This is used to optimally determine the distance, of which maximum fluorescence enhancement is achieved, between gold nanorods and fluorophores. In order to approach these aims, we use UV/VIS absorption spectroscopy, fluorescence spectroscopy, atomic force microscopy, and ellipsometry. The results show that we could control the immobilization of gold nanorods on plastic microwell plates and create reproducible polyelectrolyte layers, in order to control the distance between the gold nanorods and fluorophores. In addition, the localized surface plasmon resonance wavelength red shifted as the PELs increased. In conclusion, we found that the maximum fluorescence enhancement of the fluorophores (Cy7) is about 2.3 times at a fluorophores-nanoparticles separation of approximately 9-12 nm. This work contributes some research information towards the design of optical biochip platforms based on plasmon-enhanced fluorescence.</p>

The aims of this study are to first immobilize positively charged gold nanorods to negatively charged cell culture surfaces. Second, to use polyelectrolytes for controlling the distance between gold nanorods and fluorophores. This is used to optimally determine the distance, of which maximum fluorescence enhancement is achieved, between gold nanorods and fluorophores. In order to approach these aims, we use UV/VIS absorption spectroscopy, fluorescence spectroscopy, atomic force microscopy, and ellipsometry. The results show that we could control the immobilization of gold nanorods on plastic microwell plates and create reproducible polyelectrolyte layers, in order to control the distance between the gold nanorods and fluorophores. In addition, the localized surface plasmon resonance wavelength red shifted as the PELs increased. In conclusion, we found that the maximum fluorescence enhancement of the fluorophores (Cy7) is about 2.3 times at a fluorophores-nanoparticles separation of approximately 9-12 nm. This work contributes some research information towards the design of optical biochip platforms based on plasmon-enhanced fluorescence.

Tailoring the radiative properties of periodic micro/nanostructures can be used as an efficient way to create devices which have applications in energy harvesting, bioengineering and optical sensing. These structures are analyzed by a rigorous solution of the electromagnetic wave phenomena at the interfaces. The thesis explores the application of rigorous coupled-wave analysis (RCWA) method to study the optical responses of microstructure arrays. First section of the thesis elucidates the various mechanisms which are responsible for causing enhanced light absorption in inclined parallel plate grating arrays. Illustrative evidences of surface plasmon and magnetic resonances are provided by one and two-dimensional plots prepared by RCWA. Analytical agreement with visual data is obtained through use of LC circuit models. Finally, the effects of different geometric parameters on the resonance conditions are investigated. The second part of the thesis deals with application of RCWA to study the effect of light scattering on inclined silver nanorod (AgNR) arrays grown on compact disc (CD) gratings. Depending on the manner in which AgNRs are oriented with respect to CD gratings, they exhibit different optical behavior to incoming light. Effects of both incident light polarization and AgNR orientation with respect to the grating have been studied through the use of RCWA and effective medium theory. Calculated results are compared with experimental values and good agreements are observed for total reflection as well as trends of individual diffraction orders.