Ce travail de thèse a pour objectif la création d’indice optique local et contrôlé dans une matrice vitreuse à travers la mise au point et le développement de procédés de synthèse de nanoparticules (NPs) de sulfure de zinc (ZnS) dans un verre d’oxydes. Nous avons commencé par l’élaboration par voie de fusion d’un verre d’oxydes de composition initiale très simple. Nous avons ensuite examiné la problématique de la synthèse et du contrôle de croissance des NPs de ZnS dans nos échantillons dans trois matrices différentes et par trois traitements : recuit thermique, insolation UV ou par un traitement simultané (recuit thermique + insolation UV). Les propriétés optiques des verres dopés NPs ZnS fabriqués ont été caractérisées par diverses techniques (absorption UV visible, photoluminescence, FTIR, Raman, XPS, mesure d’indice). Il ressort de ces caractérisations que nous arrivons à fabriquer des NPs dans les trois matrices dont la taille peut aller de 1.8 à 7 nm. La dispersion sur les distributions de taille dépend de la matrice, du traitement post-fusion et de sa durée ainsi que de la concentration initiale en dopant. Nous avons également été amené à synthétiser et à étudier des nanopoudres de ZnS. Le procédé de sélection de taille révèle qu’il est possible d’obtenir au moins trois distributions étroites de tailles bien distinctes. Des filtres optiques UV à bande étroite peuvent ainsi être réalisés pour une longueur choisie en contrôlant la taille des NPs ZnS. Des applications prospectives des NPs ZnS pour le nano marquage et la photo dégradation de polluants modèles présents dans l’eau ont été illustrées / Our efforts have been devoted to the development of simple approach to synthesize ZnS nanoparticules (NPs) by melting process in a glassy matrix with the aim to create a controlled optical index variation. In this thesis, we present the formation of ZnS NPs in the glassy matrix and study of their optical properties. The nanocomposite incorporating ZnS in the host medium was prepared using the melting process from a mixture of the raw materials. We have prepared various glass samples with ZnS NPs size ranging from 1.8 à 7 nm. These samples were treated (heat treatment ± UV insulation with 244 nm laser) and characterized by UV-Vis absorption, FTIR, photoluminescence spectroscopy, Raman measurements and XPS. The refractive index measurements of these nanostructured composite glasses have been carried out and show an important increase with ZnS concentrations and treatments. We also present the elaboration of small and monodisperse ZnS nanopowder with size ranging from 3 to 100 nm by a simple, low-cost and mass production chemical method. The NPs were characterised by X-ray powder diffraction (XRD), UV-vis absorption and photoluminescence spectroscopy. The photocatalytic activity of ZnS nanopowders was investigated by using different colorant water dispersed. ZnS NPs appear to be a good candidate for potential environmental applications such as water purification. We also present application of fluorescent ZnS nanoparticles as cellular biomarkers. Fluorescent microscopy images of osteoblastic MC3T3-E1 cells revealed that the ZnS nanoparticles were biocompatible and were penetrated cells and nucleus regardless of their size. Hence, the ZnS NPs can be good candidates for drug delivery and bio-imaging applications

Nanomateriais apresentam propriedades ajustáveis pelo seu tamanho e forma, como o fenômeno de superparamagnetismo em nanopartículas magnéticas ou o confinamento quântico dos portadores de carga em pontos quânticos (quantum dots). Assim, a síntese de nanopartículas esféricas monodispersas torna-se um fator extremamente importante, haja visto que tais propriedades podem ser ajustáveis para diferentes aplicações na área de tecnologia e biomedicina. Nanopartículas magnéticas e quantum dots podem ser apontados como promissores materiais para diagnóstico e terapia de neoplasias (câncer), e o desenvolvimento desses sistemas busca, atualmente, intensificar a magnetização e a eficiência de emissão, respectivamente, relativo às propriedades magnéticas e ópticas, além de outros requisitos. Neste trabalho, nanopartículas esféricas de cobalto metálico foram sintetizadas com diâmetro médio de 5,3 nm e desvio padrão de 0,4 nm, distribuição de tamanhos lognormal. A equação de Langevin modificada pelo modelo de partículas interagentes foi utilizada no ajuste da curva de magnetização M(H) para obtenção do diâmetro magnético médio e desvio padrão, 4,7 nm e 1,0 nm, respectivamente. Comparando os dois diâmetros, encontra-se uma camada morta de magnetização de aproximadamente 3,0 Å a qual, praticamente, não contribui para a magnetização da amostra, sendo a magnetização de saturação de 125 emu g-1. Nanoestruturas core/shell de Co/Au apresentaram a propriedade de ressonância plamon de superfície, uma propriedade adicional também desejada para aplicações biomédicas, sendo este sistema denominado magnetoplasmônico. Quantum dots de CdSe foram sintetizados como elevado controle de tamanho e forma. Utilizando rotas de síntese diferentes dos clássicos procedimentos denominados TOP-TOPO, e dióxido de selênio como precursor, estudos mostraram que na presença de um agente redutor no meio de reação e do solvente 1-octadeceno, as amostras apresentaram melhores propriedades óticas. A estrutura cristalina das amostras de CdSe corresponde à formação da fase blenda de zinco, diferentemente das sínteses TOP-TOPO que levam à formação da fase hexagonal wurtzita. A cinética de crescimento dos quantum dots de CdSe também foram avaliadas através de alíquotas retiras com o tempo de reação mostrando um crescimento exponencial do diâmetro das partículas, como previsto pelas teorias de nucleação e crescimento. Estudos por microscopia de fluorescência mostraram que os quantum dots apresentaram o comportamento de intermitência de fluorescência relatado na literatura como um dos fatores que levam a uma diminuição do rendimento quântico de fluorescência. Nanoestruturas core/shell de CdSe/ZnS foram obtidas com elevado controle da espessura da camada de recobrimento e a intensificação das propriedades de fotoluminescência foram mostradas. Os objetivos do trabalho foram alcançados com sucesso, onde foi possível observar a estabilização e a intensificação da magnetização da fase de cobalto metálico, pouco relatado na literatura. Ainda, foi possível conferir maior estabilidade química, versatilidade de funcionalização da superfície e uma segunda propriedade de ressonância plasmônica com o recobrimento com ouro, sem grande prejuízo da propriedade magnética. Em relação aos sistemas ópticos, os semicondutores de CdSe foram obtidos por nova rota de síntese com expressivo controle de tamanho e forma, recobertos com ZnS intensificando as propriedades ópticas do sistema.  / Nanomaterials properties are size- and shape-controlled, such as the superparamagnetism phenomenon of magnetic nanoparticles or the quantum confinement of charge carriers of quantum dots. Therefore, synthesis of monodisperse spherical nanoparticles became extremely important over the past few deacades, since nanoparticles can be used for plenty of applications in technology and biomedicine. Magnetic nanoparticles and quantum dots are promising materials for diagnosis and therapy of cancer. Spherical nanoparticles of metallic cobalt were synthesized with mean diameter of 5,3 nm and standard deviation of 0,4 nm, lognormal distribution. A modified Langevin equation using the interacting superparamagnetic model was used to fit magnetization curves obtaining the mean magnetic diameter and standard deviation, 4,7 nm and 1,0 nm, respectively. The difference between these two diameters was assigned to the magnetic dead layer (∼3.0 Å), which does not contribute to the sample magnetization, being the saturation magnetization of cobalt nanoparticles around 125 emu g-1. Co/Au core/shell nanostructures were synthesized and the surface plasmon ressonance property was observed, an additional property also desired for biomedical applications, being the Co/Au core/shell system called magnetoplasmonic. CdSe quantum dots were synthesized with high size- and shape-controlled. Using different synthetic routes from the classic TOP-TOPO synthesis, and selenium dioxide as a precursor, the results show that and reducing agent is necessary and 1-octadecene solvent leads to better optical properties. CdSe samples showed a zinc blend (cubic phase) crystal structure, different from TOP-TOPO syntheses that leads to wurtzite structure (hexagonal phase). The growth kinetics of CdSe particles were also evaluated through aliquots from reaction showing exponential growth of particles diameter, as predicted on the theory of nucleation and growth. Fluorescence microscopy studies showed that quantum dots exhibited fluorescence intermittence behavior already reported in the literature as one fo the reasons for the quantum yield decrease. CdSe/ZnS core/shell nanostructures were obtained with high control of the coating layer thickness and the increase of the photoluminescence properties were shown.

Ce travail de thèse a été consacré à la photostructuration d’une matrice polymère de type acrylate contenant des points quantiques CdSe/ZnS (QDs) par l’enregistrement de réseaux. La diffusion photoinduite des nanocristaux semi-conducteurs a tout d’abord été mise en évidence par l’utilisation d’un montage permettant d’irradier sur une seule ligne, et par l’émission de fluorescence des QDs utilisée ici comme sonde de déplacement. Ensuite, pour comprendre l’augmentation de la modulation d’indice de réfraction, et par conséquent du rendement de diffraction des réseaux enregistrés dans ces matériaux composites, nous avons mis en place une approche physico-chimique. Celle-ci nous a permis de corréler les modifications chimiques et les propriétés physiques du réseau. En effet, nous avons montré que l’ajout de points quantiques influence la cinétique de polymérisation ; la vitesse de consommation du photosensibilisateur et de conversion des monomères diminuent. Cette diminution permet une meilleure diffusion des espèces au sein de la matrice. Donc, le ralentissement de la cinétique de photopolymérisation et la répartition spatiale des QDs contribuent à un accroissement de la modulation d’indice de réfraction des réseaux enregistrés. / This work is devoted to the photostructuration of an acrylate polymer matrix with dispersed CdSe/ZnS quantum dots (QDs) upon grating exposure. The photo-induced diffusion of semiconductor nanocrystals is proved by the use of a "one line irradiation" set up and by the emission of the QDs fluorescence, used here as a probe of displacement. Then, in order to understand the increase of the refractive index modulation, and so, of the diffraction efficiency of the recorded patterns in the composite materials, we apply a physico-chemical approach. This one allows correlating the chemical modifications to the physical properties of the gratings. Indeed, we show that the addition of QDs influences the kinetics of polymerization ; the rate of the photo-initiator consumption, and that of the monomer conversion decrease. This decrease favors the diffusion ofthe species inside the matrix. Therefore, the slowing down of the kinetics of the photopolymerization and the spatial distribution of QDs contribute to the enhancement of the refractive index modulation of the recorded gratings.

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No. of bitstreams: 1 curcio_al_me_rcla.pdf: 1672370 bytes, checksum: fd59b862449a04ac385f3661da6430f3 (MD5) Previous issue date: 2016-02-29 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Nanocristais tem sido extensivamente investigados nos últimos anos devido à sua ampla gama de aplicações em vários dispositivos tais como sensores, células solares, lasers, fotocatalisadores, fotodetectores, detectores de infravermelhos, diodos emissores de luz, materiais eletroluminescentes e outros materiais emissores de luz. Semicondutores nanocristalinos apresentam propriedades eletrônicas intermediárias entre aqueles de estrutura molecular e sólidos macrocristalinos, proporcionando uma ampla gama de aplicações. Entre estes materiais, o sulfeto de zinco (ZnS) puro ou dopado tem recebido notável atenção por causa de suas propriedades estruturais ópticas, versatilidade e potencial para várias aplicações tecnológicas. O ZnS é um típico semicondutor II-VI, com um gap direto de 3,6 eV à temperatura ambiente e aproximadamente 40 meV de energia de gap, sendo um bom material luminescente utilizado em telas, sensores e lasers. Como material de gap largo, o ZnS pode facilmente hospedar diferentes metais de transição como centros luminescentes. Entre estes íons de metais de transição para estruturas dopadas, os íons Cu2+e Mn2+ são atraentes pelas emissões de luz características e por apresentarem propriedades eficientes para aplicações como luminóforos. A inserção desses íons na estrutura do ZnS proporcionam defeitos que resultam em emissão no verde para os íons Cu2+e emissão no laranja para os íons Mn2+. Neste estudo, as amostras de ZnS pura e dopadas com Cu2+ e Mn2+ foram preparados pelo método solvotermal, que demonstra ser um processo eficaz para preparar nanopartículas. Uma vez preparadas, as estruturas das amostras nanoestruturadas foram caracterizadas e correlacionada s com propriedades fotoluminescentes. Os resultados de difração de raios X mostram que as amostras de ZnS foram cristalizadas completamente sem a presença de fases secundárias e os difratogramas correspondem à estrutura blenda cúbica de zinco com grupo espacial F-43m. Os espectros de XANES (X-ray Absorption Near Edge Structure) teóricos e experimentais na borda K do Zn indicam que a incorporação de átomos de Mn na matriz ZnS causam a formação de vacâncias de Zn e S, a qual é confirmada por ajustes de espectros EXAFS (Extended X-ray Absorption Fine Structure). Estas vacâncias estão relacionadas com um desvio para o vermelho observado no pico do espectro de fotoluminescência devido a adição de Mn na estrutura do ZnS. Para o ZnS puro, o pico é centrado em ~ 504 nm, relativo as vacâncias de S na amostra nanoestruturada. À medida que se aumenta a porcentagem de Mn na matriz ZnS, uma emissão no amarelo-laranja centrada em ~ 590 nm pode ser observada, associada com a transição 4T1-6A1 no interior de níveis 3d de Mn2+. A adição de íons Cu2+ ao ZnS resulta em um alargamento no pico do espectro de fotoluminescência decorrente de emissão no azul-verde, que está relacionada a recombinação de elétrons de níveis de defeitos mais profundos dos estados t2 do Cu próximos da banda de valência. / Nanocrystals has been extensively investigated in recent years due to its wide range of applications in various devices light emitting materials such as sensors, solar cells, lasers, photocatalysts, photodetectors, IR detectors, light emitting diodes and others. Nanocrystalline Semiconductors have electronic properties between those intermediate molecular macrocristalinos and solid structure, providing a wide range of applications. Among these materials, zinc sulfide (ZnS) pure or doped has received considerable attention because of its optical structural properties, versatility and potential for several technological applications. The ZnS is a typical II-VI semiconductor with a direct band gap of 3.6 eV at room temperature and about 40 meV in energy gap, and a good luminescent material for constrution of displays, lasers and sensors. As wide band gap material, ZnS can easily host different transition metals as luminescent centers. Among these ions of transition metal doped structures, Cu2+ and Mn2+ ions are attractive for light emission characteristics and for having effective properties for applications such as phosphors. The addition of these ions in ZnS structure provide defects that result in emission in the green for the Cu2+ ions and emission in orange for the Mn2+ ions. In this study, samples of pure ZnS and doped with Cu2+ and Mn2+ ions were prepared by solvotermal method, which demonstrate to be an effective process for preparing nanoparticles. Once prepared, the structures of the nanostructured samples were characterized and correlated with photoluminescent properties. The results of X-ray diffraction showed that the ZnS samples were completely crystallized without the presence of secondary phases and XRD patterns correspond to the structure of zinc blende to cubic space group F-43m. spectra XANES (X-ray Absorption Near Edge Structure) theoretical and experimental in the Zn K edge indicates that the inclusion of Mn atoms in the ZnS matrix cause the formation of Zn and S vacancies, which is confirmed by spectral adjustments EXAFS (Extended X-ray Absorption Fine Structure). These vacancies are associated with a red shift observed in the photoluminescence spectrum peak due to the addition of Mn in ZnS structure. For pure ZnS, the peak is centered at ~ 504 nm concerning the vacancies in the S nanostructured sample. As it increases the percentage of Mn in the ZnS matrix, in yellow-orange emission centered at ~ 590 nm can be observed, associated with the transition 4 T1- 6A1 inside 3d levels of Mn2+. Adding Cu2+ to the ZnS results in a broadening of the peak of the photoluminescence spectrum due to emission in blue-green, which is related to recombination deeper defect levels of electrons of t2 Cu states near the valence band.

Nanomateriais apresentam propriedades ajustáveis pelo seu tamanho e forma, como o fenômeno de superparamagnetismo em nanopartículas magnéticas ou o confinamento quântico dos portadores de carga em pontos quânticos (quantum dots). Assim, a síntese de nanopartículas esféricas monodispersas torna-se um fator extremamente importante, haja visto que tais propriedades podem ser ajustáveis para diferentes aplicações na área de tecnologia e biomedicina. Nanopartículas magnéticas e quantum dots podem ser apontados como promissores materiais para diagnóstico e terapia de neoplasias (câncer), e o desenvolvimento desses sistemas busca, atualmente, intensificar a magnetização e a eficiência de emissão, respectivamente, relativo às propriedades magnéticas e ópticas, além de outros requisitos. Neste trabalho, nanopartículas esféricas de cobalto metálico foram sintetizadas com diâmetro médio de 5,3 nm e desvio padrão de 0,4 nm, distribuição de tamanhos lognormal. A equação de Langevin modificada pelo modelo de partículas interagentes foi utilizada no ajuste da curva de magnetização M(H) para obtenção do diâmetro magnético médio e desvio padrão, 4,7 nm e 1,0 nm, respectivamente. Comparando os dois diâmetros, encontra-se uma camada morta de magnetização de aproximadamente 3,0 Å a qual, praticamente, não contribui para a magnetização da amostra, sendo a magnetização de saturação de 125 emu g-1. Nanoestruturas core/shell de Co/Au apresentaram a propriedade de ressonância plamon de superfície, uma propriedade adicional também desejada para aplicações biomédicas, sendo este sistema denominado magnetoplasmônico. Quantum dots de CdSe foram sintetizados como elevado controle de tamanho e forma. Utilizando rotas de síntese diferentes dos clássicos procedimentos denominados TOP-TOPO, e dióxido de selênio como precursor, estudos mostraram que na presença de um agente redutor no meio de reação e do solvente 1-octadeceno, as amostras apresentaram melhores propriedades óticas. A estrutura cristalina das amostras de CdSe corresponde à formação da fase blenda de zinco, diferentemente das sínteses TOP-TOPO que levam à formação da fase hexagonal wurtzita. A cinética de crescimento dos quantum dots de CdSe também foram avaliadas através de alíquotas retiras com o tempo de reação mostrando um crescimento exponencial do diâmetro das partículas, como previsto pelas teorias de nucleação e crescimento. Estudos por microscopia de fluorescência mostraram que os quantum dots apresentaram o comportamento de intermitência de fluorescência relatado na literatura como um dos fatores que levam a uma diminuição do rendimento quântico de fluorescência. Nanoestruturas core/shell de CdSe/ZnS foram obtidas com elevado controle da espessura da camada de recobrimento e a intensificação das propriedades de fotoluminescência foram mostradas. Os objetivos do trabalho foram alcançados com sucesso, onde foi possível observar a estabilização e a intensificação da magnetização da fase de cobalto metálico, pouco relatado na literatura. Ainda, foi possível conferir maior estabilidade química, versatilidade de funcionalização da superfície e uma segunda propriedade de ressonância plasmônica com o recobrimento com ouro, sem grande prejuízo da propriedade magnética. Em relação aos sistemas ópticos, os semicondutores de CdSe foram obtidos por nova rota de síntese com expressivo controle de tamanho e forma, recobertos com ZnS intensificando as propriedades ópticas do sistema.  / Nanomaterials properties are size- and shape-controlled, such as the superparamagnetism phenomenon of magnetic nanoparticles or the quantum confinement of charge carriers of quantum dots. Therefore, synthesis of monodisperse spherical nanoparticles became extremely important over the past few deacades, since nanoparticles can be used for plenty of applications in technology and biomedicine. Magnetic nanoparticles and quantum dots are promising materials for diagnosis and therapy of cancer. Spherical nanoparticles of metallic cobalt were synthesized with mean diameter of 5,3 nm and standard deviation of 0,4 nm, lognormal distribution. A modified Langevin equation using the interacting superparamagnetic model was used to fit magnetization curves obtaining the mean magnetic diameter and standard deviation, 4,7 nm and 1,0 nm, respectively. The difference between these two diameters was assigned to the magnetic dead layer (∼3.0 Å), which does not contribute to the sample magnetization, being the saturation magnetization of cobalt nanoparticles around 125 emu g-1. Co/Au core/shell nanostructures were synthesized and the surface plasmon ressonance property was observed, an additional property also desired for biomedical applications, being the Co/Au core/shell system called magnetoplasmonic. CdSe quantum dots were synthesized with high size- and shape-controlled. Using different synthetic routes from the classic TOP-TOPO synthesis, and selenium dioxide as a precursor, the results show that and reducing agent is necessary and 1-octadecene solvent leads to better optical properties. CdSe samples showed a zinc blend (cubic phase) crystal structure, different from TOP-TOPO syntheses that leads to wurtzite structure (hexagonal phase). The growth kinetics of CdSe particles were also evaluated through aliquots from reaction showing exponential growth of particles diameter, as predicted on the theory of nucleation and growth. Fluorescence microscopy studies showed that quantum dots exhibited fluorescence intermittence behavior already reported in the literature as one fo the reasons for the quantum yield decrease. CdSe/ZnS core/shell nanostructures were obtained with high control of the coating layer thickness and the increase of the photoluminescence properties were shown.

This thesis is devoted to the investigation of mechanical properties and self-assembly process of materials at the nanoscale. Various nanostructured materials such as nanoparticles, nanotubes, nanowires and thin films are used as constituent elements of nanodevices. Hence, knowledge of the mechanical properties of materials at the nanoscale is extremely important for understanding their functionality in nanodevices. Mechanical properties of nanostructured materials may significantly differ from those of their bulk counterparts due to the high surface to volume ratio in nanostruc-tures. We particularly focus on the role of the surface region on the stiffness of nanomaterials. We have shown that the stiffness of a nanomaterial can be tuned over a wide range by introducing appropriate coating on the nanostructure surface. We have also explored the effects of the surface region on the stability of various phases in a nanostructure. In the second part of this thesis, we have described the self-assembly process of nanostructures mediated by drendrimers. Self-assembly techniques are frequently used to decorate nanostructures into specific networks. The motivation of this study is to investigate the mechanisms which control the effective interaction and the inter-particle distance between nanoparticle-dendrimer compos-ites. Control over the inter-particle separation is very important since it has a strong influence on the electronic and optical properties of the nanostructures. In the following paragraphs, we sum-marize the results of our study. We start with a brief introduction to the mechanical properties and self-assembly process of nanostructures in the first chapter. A brief review of the work done on these topics in the recent past is presented in this chapter. We discuss the results and conclusions of various experimental and numerical studies on these topics. We also mention the motivation for the studies we have carried out. At the end, we briefly describe the numerical methods (molecular dynamics (MD) and density functional theory (DFT)) which have been used in our investigations. In the second chapter, we discuss the effects of the surface region on the mechanical properties of nanostructures. We have investigated the size and growth direction dependence of the mechanical properties of ZnS nanowires and thin films as a case study. We observe that the Young’s modulus of nanowires and thin films strongly depends on their size and growth direction. This size and growth direction dependence of the stiffness of nanostructured materials can be explained in terms of their surface modifications. Since the energy of the surface region is usually higher than that of the core region in a nanostructure, the surface atoms move their positions to minimize the surface energy. As a result, bond lengths at the surface region are usually different from their bulk values. We observe that in ZnS nanowires and thin films, the average bond length at the surface region is lower than that in the core region which remains unchanged from its bulk value. This decrease in the bond length (or equivalently increase in the bond energy) increases the effective stiffness of the entire nanostructure. As the size of the nanowire/thin film increases, the effect of the surface region gradually decreases and hence the Young’s modulus value converges to the bulk value. Since the surface region has a strong influence on the mechanical properties of nanostructures, the stiffness of a nanostructure can be tuned by modifying the surface region with other materials. In chapter three, we have shown that the stiffness of ZnS nanowires can be tuned by introducing a thin CdS shell on top of the ZnS surface. In general, the stiffness of a nanostructure can be increased (decreased) by coating the surface region with a stiffer (less stiff) material. However, the stiffness of the core/shell nanostructures strongly depends on the properties of the interface between the core and the shell. We observe that the binding energy between the core and shell regions is relatively low due to the lattice mismatch at the interface region of core/shell nanostructures. This lower binding energy strongly affects the stiffness of core/shell nanostructures. We have also shown that thermal properties such as thermal conductivity and melting temperature of core/shell structures can be tuned by changing the coating material. In chapter four, we discuss the effects of the surface region on the stability of various phases in a nanostructure. The surface atoms may stabilize a particular phase in a nanostructure which is not a stable phase in the bulk material. In this chapter, we investigate the stability of the h-MgO phase, an intermediate structure found during the wurtzite to rock salt transformation, in CdSe nanostructures. We observe that this five-fold coordinated phase is more stable at lower temperatures and smaller sizes of the nanowires. The appearance of this phase has not been observed till now in experiments. We show that this phase is not stable for larger CdSe nanocrystals on which the experiments have been done. In the rest of the thesis, we have presented the results of our studies of self-assembly of nanostructures mediated by DNAs and dendrimers. First we describe in chapter five the nature of the effective interaction between two PAMAM dendrimers. Dendrimers are frequently used to coat surfaces of nanoparticles to prevent the nanoparticles from aggregation. The interaction between such nanoparticle-dendrimer composites depends strongly on the nature of the effective interac-tion between dendrimers. We have used fully atomistic MD simulations to calculate the potential of mean force (PMF) between two PAMAM dendrimers. We show that the effective interaction strongly depends on the size (generation) and protonation level of the dendrimers. The PMF profiles of nonprotonated dendrimers show a global minimum which represents the attractive nature of the interaction between the dendrimers up to a certain center-to-center distance. On the other hand, the interaction between protonated dendrimers is repulsive throughout their interaction re-gion. The PMF profiles are fitted very well by a sum of an exponential and a Gaussian function. This observation is in contradiction with some of the results of existing coarse-grained simulations which predicted the effective interaction between dendrimers to be Gaussian. Our atomistic simulation which includes all the local fluctuations is expected to give more accurate results. Information about the effective interaction between two dendrimers helps in understanding how dendrimer molecules can be used to control the interaction strength and the preferred inter-particle distance between two nanostructures. In chapter six, we discuss the effective interaction between two dendrimer grafted gold nanoparticles. We observe that dendrimer molecules can get adsorbed spontaneously on the surface of a gold nanoparticle. These grafted dendrimers significantly alter the interaction between the gold nanoparticles. We have explored the effects of proto-nation level and the density of the grafted dendrimers on the effective interaction between two gold nanoparticle-dendrimer composites. We observe that these nanoparticle-dendrimer composites at-tract each other at low grafting density. However, the interaction strength and the inter-particle distance at the minimum of the potential are much lower and higher, respectively than those between two bare gold nanoparticles. Interestingly at higher grafting density, the nature of the interaction between the nanocomposites depends on the protonation level of the grafted dendrimers. Nanoparticles grafted with nonprotonated dendrimers still attract each other but with lower inter-action strength and higher inter-particle distance compared to the values for low grafting density. On the other hand, nanocomposites grafted with protonated dendrimers repel each other at high grafting density. Thus we show that the effective interaction and the optimal inter-particle distance between the nanostructures can be tuned over a wide range by using a suitable grafting density and protonation level of the dendrimers. In the seventh chapter, we describe a strategy to assemble dendrimers with the help of sin-gle stranded DNA (ssDNA). We attach an ssDNA to one dendrimer and a complementary ssDNA to a second dendrimer. These two complementary ssDNAs bind with each other through base pair formation to assemble the dendrimers into a single structure. The complementary ssDNAs form a dsDNA which is rigid enough to maintain the inter-dendrimer distance almost the same as the length of the DNA. The inter-dendrimer distance can be tuned by changing the DNA length. However, this method strongly depends on the protonation level of the dendrimers. It works well only for nonprotonated dendrimers. Since the protonated dendrimers are positively charged, they strongly interact with the negatively charged ssDNAs through electrostatic interaction. As a result, ssDNAs wrap the dendrimer surface and hence the inter-dendrimer distance can not be controlled. We have also verified that this method works for multiple nonprotonated dendrimers as well. In the final chapter of this thesis, we summarize the main results and conclude with a brief discussion of future directions of research on the problems considered in the thesis.

QDs haben aufgrund ihrer einzigartigen optischen und elektronischen Eigenschaften erhebliche Aufmerksamkeit erregt und sind vielseitige Materialien für verschiedene Anwendungen. T-QDs, wie AIS/ZnS, haben aufgrund ihrer geringeren Toxizität, Umweltverträglichkeit und einstellbaren optischen Eigenschaften an Bedeutung gewonnen. Diese Arbeit konzentriert sich auf die MW-Synthese von AIS/ZnS-QDs und untersucht den Einfluss von Syntheseparametern auf ihre optischen Eigenschaften sowie deren nachfolgende Anwendung in LSCs. Die Synthese kombiniert einen zweistufigen Erhitzungsansatz mit MW, was eine präzise Kontrolle über die QD-Zusammensetzung, Liganden und die chemische Zerfallsreihenfolge ermöglicht. Die Studie untersucht die Variation der Ag:In:S:Zn-Verhältnisse und den Einfluss von vier verschiedenen Liganden auf die optischen Eigenschaften. Die Ergebnisse bestätigen die Vielseitigkeit dieser QDs bei der Herstellung wasserlöslicher, hochphotolumineszierender Materialien. Die AIS/ZnS-QDs werden weiterhin als Materialien für LSCs genutzt, um erneuerbare Energie in BIPV-Systemen zu nutzen. Die Studie erforscht die Integration dieser QDs in eine Polymermatrix für LSCs und betont die Effizienz der Synthese. Zwei Syntheseansätze, ein zweistufiges Erhitzungsverfahren und die MW-Synthese mit Thiol-Liganden, erzeugen QDs, die in Toluol dispergierbar sind. Die resultierenden lumineszierenden Platten, integriert in LSC-Geräte, zeigen eine hohe PL QY (>60%). Die optischen Verluste werden für verschiedene Ligandenkombinationen verglichen, wobei überlegene Ergebnisse für MPA-OLA/OA-capped QDs beobachtet werden. Die LSC-Geräte, gekoppelt mit Si-Solarzellen unter einem Sonnensimulator, zeigen OPE-Werte von 3,8 ± 0,2% und 3,5 ± 0,2% für GSH-OLA/OA bzw. MPA-OLA/OA AIS/ZnS-QDs, und QOE-Werte von 24,1 ± 0,4% und 27,4 ± 0,4%. Die erreichte Leistung, gepaart mit der einfachen, wasserbasierten Synthese und den guten optischen Eigenschaften, unterstreicht das Potenzial von AIS/ZnS-QDs als LSCs. / QDs gained significant attention for their unique optical and electronic properties, making them versatile materials for various applications. t-QDs, such as AIS/ZnS, gained prominence due to their lower toxicity, eco-friendly nature, and tunable optical characteristics. This thesis focuses on the MW-assisted synthesis of AIS/ZnS QDs, exploring the impact of synthesis parameters on their optical properties and subsequent application as LSCs. The synthesis methodology combines a two-step heating approach with MW assistance, allowing for precise control over QD composition, ligands, and chemical decomposition order. The study investigates the variation of Ag:In:S:Zn ratios and the influence of four different ligands on optical properties. The results confirm the versatility of these QDs in producing water-soluble, highly photoluminescent materials with PL QY of 60-65% and long PL decay. The synthesized AIS/ZnS QDs are further utilized as materials for LSCs, aiming to harness renewable energy in building-integrated photovoltaic systems. The study explores the integration of these QDs into a polymer matrix for LSCs, emphasizing the efficiency of the synthesis method. Two synthesis approaches, a two-step heating method and MW-assisted synthesis with thiol ligands, yield QDs dispersible in organic solvents. The resulting luminescent slabs, integrated into LSC devices, exhibit high PLQY (>60%). Optical losses due to reabsorption and matrix effects are compared for different ligand combinations, with superior results observed for MPA-OLA/OA-capped QDs. The LSC devices coupled with Si-solar cells under a solar simulator demonstrate OPE values of 3.8 ± 0.2% and 3.5 ± 0.2% for GSH-OLA/OA and MPA-OLA/OA AIS/ZnS QDs, respectively, and QOE values of 24.1 ± 0.4% and 27.4 ± 0.4%. The achieved device performance, among the highest reported, coupled with the simplicity of the water-based synthesis and the excellent optical properties, underscores the potential of AIS/ZnS QDs as LSCs.

Described herein are two projects focusing on developing and investigating two types of nanoparticles (NPs) grown by the seeded growth method from a conducting metallopolymer for photovoltaic (PV) applications. Core/shell CdS/ZnS NPs are proven to resist the photo-oxidation of PV devices, while CuInxGa(1-x)Se2 (CIGS) NPs are expected to optimize the efficiency of PV devices. / text

Στην παρούσα Ειδική Ερευνητική Εργασία ερευνώνται οι οπτικές ιδιότητες των νανοκρυσταλλικών κβαντικών τελειών CuInS2/ZnS, γνωστές ως CIS/ZnS QDs, τόσο με τη χρήση φασματοσκοπίας σταθερής κατάστασης όσο και με τη χρήση φασματοσκοπίας χρονικής ανάλυσης με την τεχνική Time Correlated Single Photon Counting. Ειδικότερα, διερευνώνται οι μηχανισμοί που εμπλέκονται στη διαδικασία της εκπομπής φωτός, η επίδραση που έχει η πολικότητα του διαλύτη και η συγκέντρωση των κβαντικών τελειών, όταν είναι διαλυμένες εντός διαλύματος, καθώς και η αλληλεπίδραση μεταξύ των κβαντικών τελειών όταν είναι εναποτιθέμενες σε υμένια, είτε με την τεχνική drop-casting είτε με spin-coating. Τόσο η αύξηση της συγκέντρωσης των κβαντικών τελειών όσο και η αύξηση της πολικότητας του διαλύτη προκάλεσε τη μετατόπιση του εξιτονικού ώμου και του μήκους κύματος μέγιστης εκπομπής προς το ερυθρό, στα φάσματα σταθερής κατάστασης. Επίσης η μετατόπιση της φωτοφωταύγειας των CIS/ZnS QDs προς το ερυθρό ήταν μεγαλύτερη στα υμένια που είχαν παρασκευασθεί με την τεχνική drop-casting από τα υμένια με το ίδιο υπόστρωμα που είχαν παρασκευασθεί με την τεχνική spin-coating. Με χρήση φασματοσκοπίας χρονικής ανάλυσης, ανιχνεύθηκε η ύπαρξη τριών μηχανισμών στα διαλύματα με χρόνους ζωής 1-3, 20-40 και 200-300 ns, ενώ στα υμένια προστέθηκε ένας επιπλέον μηχανισμός με χρόνο ζωής από μερικές εκατοντάδες ps έως 4 ns. Ο χαρακτήρας της αποδιέγερσης των QDs στα υμένια κυμαίνεται μεταξύ διεκθετικού και τετραεκθετικού ανάλογα με το δείγμα και το μήκος κύματος ανίχνευσης. Το περίεργο χαρακτηριστικό του νέου μηχανισμού που ανιχνεύθηκε στα υμένια είναι ότι γίνεται πιο γρήγορος και πιο αποδοτικός καθώς το μήκος κύματος ανίχνευσης αυξάνει. Ένας παρόμοιος μηχανισμός δεν έχει αναφερθεί σε άλλες εργασίες με CIS/ZnS QDs, ενώ έχει αναφερθεί σε παλιότερες εργασίες με PbS QDs τόσο σε διαλύματα όσο και σε στερεά υμένια. Η μετατόπιση των πυκνών υμενίων προς το ερυθρό σε σχέση με τα αραιά αποτελεί ένδειξη της ύπαρξης μεταφοράς ενέργειας μεταξύ QDs διαφορετικών μεγεθών. / In this Master Thesis, the optical properties of CuInS2/ZnS nanocrystal quantum dots are investigated. For this purpose both steady state and time resolved spectroscopy, specifically the Time Correlated Single Photon Counting technique, were used. The photoluminescence properties of CuInS2/ZnS quantum dots, commonly known as CIS/ZnS QDs, either dissolved in solutions of different concentrations and solvent polarities or deposited on films made by spin-coating or drop-casting are studied. Either in the absorption and the photoluminescence steady state spectra, a red-shift both in the excitonic transition and the wavelength of the maximum intensity was observed as the concentration of the CIS/ZnS QDs or the polarity of the solvent increased. In films, a red-shifted photoluminescence spectrum is observed for films made by drop-casting compared to those prepared by spin-coating, having the same substrate material. By using time-resolved photoluminescence spectroscopy a three-exponential decay was observed in solutions, with time constants 1-3, 20-40 and 200-300 ns, while decays in films, apart from the three mechanisms also observed in solutions, also exhibit a fast decay component with a lifetime varying from some hundreds of ps until 4 ns. The attitude of the decay in films varies from two-exponential to four-exponential and it depends on the samples and the detection wavelength. The strange characteristic of the new mechanism which was detected in films is that its lifetime becomes shorter and its pre-exponential factor increases with the detection wavelength. To the best of our knowledge, such a faster decay as the emission wavelength increases has never been reported for CIS/ZnS QDs, but it has been reported for PbS QDs either diluted in solution or deposited in polymeric matrices. The time resolved photoluminescence spectra in the drop-casted films experience a larger transient red-shift than the spin-coated ones, indicative of a possible energy transfer among adjacent QDs with different diameters.

Submitted by Alice Araujo (alice.caraujo@ufpe.br) on 2018-06-05T21:43:58Z No. of bitstreams: 1 DISSERTAÇÃO Roberta Cristina da Silva.pdf: 1891274 bytes, checksum: cd1ace9dd4f9811ce8ec0408c798b709 (MD5) / Made available in DSpace on 2018-06-05T21:43:58Z (GMT). No. of bitstreams: 1 DISSERTAÇÃO Roberta Cristina da Silva.pdf: 1891274 bytes, checksum: cd1ace9dd4f9811ce8ec0408c798b709 (MD5) Previous issue date: 2016-12-21 / O sulfeto de zinco (ZnS) é um excelente semicondutor, com aplicações interessantes nos campos da ótica e da elétrica, mas outras propriedades como a ação como aditivo em matrizes poliméricas ainda não são muito claras em estudos anteriores. Neste trabalho, o ZnS foi sintetizado pela rota sonoquímica e nanopartículas com diâmetros de aproximadamente 2 nm foram obtidas. O ZnS produzido foi adicionado à matriz de Poli(cloreto de vinila) nas concentrações de 0,10; 0,30; 0,50; 0,70 e 1,00% (m/m). As amostras foram irradiadas com fonte de radiação gama (60Co) na dose de 25 kGy à temperatura ambiente e no ar. Análises viscosimétricas mostram decréscimo na massa molar viscosimétrica (Mv) das amostras de PVC e PVC com ZnS (PVC/ZnS). Contudo, somente as amostras de PVC com a concentração de 0,7% de ZnS mostraram proteção molecular à matriz polimérica. As interações entre o ZnS e o PVC, constatadas por espectros de FT-IR, favoreceram a ação do ZnS como agente proteto radiolítico do PVC. Estes resultados sugerem o uso de nanopartículas de ZnS, sintetizadas pela rota sonoquímica, como um novo aditivo na matriz de PVC para aplicações de resistência à irradiação gama. / Zinc sulfide (ZnS) is an excellent semiconductor, with interesting applications in the optical and electrical fields, but other properties, such as the action as additive in polymer matrices, are still not very evident in previous studies. In this work, the ZnS was synthesized by sonochemical method and nanoparticles with diameters around 2 nm were obtained. The ZnS produced was added to the Poly (vinyl chloride) matrix at concentrations of 0.10; 0.30; 0.50; 0.70 and 1.00% (m/m). The samples were irradiated with gamma radiation (60Co) at dose of 25 kGy in air at room temperature. Viscosimetric analysis show a decrease in viscosity-average molar mass (Mv) of PVC and PVC with ZnS (PVC/ZnS) samples. However, only the PVC/ZnS samples with 0.7% concentration of ZnS showed molecular protection to the polymer matrix. The interactions between ZnS and PVC, verified by FT-IR spectra, favored the action of ZnS as a radiolytic protective agent of PVC. These results suggest the use of sonochemically synthesized ZnS nanoparticles as a new additive in the PVC matrix for gamma irradiation resistance applications.