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This thesis explores how the carrier dynamics within semiconductor nanocrystals can be directly engineered through specific core-shell design. Emphasis is placed on how material characteristics, such as strain or alloying at a core-shell interface, can influence the exciton energies and the recombination dynamics within semiconductor nanocrystals. This study synthesises type-II heterojunction ZnTe/ZnSe core-shell nanocrystals via a diethyl zinc-free synthesis method, producing small size distributions and quantum yields as high as 12%. It was found that the 7% lattice mismatch between the core and shell materials places limitations on the range of structures in which coherent growth is achieved. By developing compositional and strained atomistic core-shell models a variety of physical and optical properties could be simulated and has led to a clear picture of the core-shell architecture to be built. This characterisation provides evidence that the low bulk modulus ZnTe cores are compressed by the higher bulk modulus smaller lattice constant ZnSe shells. Further studies show how strain is manifested in structures with 'sharp' core-shell interfaces and how intentional alloying the interface can influence the growth and exciton energies. A (2-6)-band effective mass model was able to distinguish between the as-grown 'sharp' and 'alloyed' interfaces which indicated that strain accentuates the redshift of the excitonic state whilst reduced strain within an alloyed interface sees a reduced redshift. Single nanocrystal spectroscopy investigations of brightly emitting single graded alloyed nanocrystals and of a size series of commercially available CdSe/ZnS nanocrystals showed almost no fluorescence intermittency (nearly 'non-blinking'). These investigations also identified trion recombination as the main mechanism within the blinking 'off' state. Ultimately this thesis adds to the growing understanding of how specific core-shell architectures manipulate the electronic structure and develops techniques to identify specific material characteristics and how these characteristics influence the physical and optical properties within semiconductor nanocrystals.

Bringing together several materials into a single nanoparticle is an attractive way to design systems that exhibit diverse physical and chemical properties. Cobalt nanoparticles are extensively used in magnetic separation, ferrofluids, and magnetic storage media. The deposition of gold nanoparticles onto cobalt core significantly affects their optical properties due to the introduction of surface Plasmon. Here the synthesis of gold nanoparticles decorated cobalt-silica nanoparticles are reported for the first time. Their optical and magnetic properties and capacity as a surface enhanced Raman scattering (SERS) substrate were investigated. This nano-material is of particular interest as a dual agent allowing both magnetic separation and SERS detection. The synthesis involves three steps: i) synthesis of Co nanoparticles / ii) deposition of a silica shell around the Co core and introduction of amine functional groups on the surface / iii) decoration of the surface with gold nanoparticles. Co nanoparticles were prepared in an inert atmosphere in the presence of capping and reducing agents. Size of the cobalt nanoparticles was varied by changing the concentration of the capping agent. Since cobalt particles are easily oxidized, they were coated with silica shell both to prevent oxidation and allow further functionalization. Silica coating of the particles were performed in water/ethanolic solution of tetraethyl orthosilicate (TEOS). Thickness of silica coating was controlled by varying the concentrations of TEOS. Besides, by adding 3-aminopropyl-triethoxysilane (APTS) to the reaction medium, primarily amine groups were introduced on the silica surface. For further modifications citrate stabilized gold nanoparticles were appended onto the surface of amine modified core-shell cobalt-silica nanoparticles. Gold decorated magnetic core-shell structures were used as SERS substrate with Raman dyes / brilliant cresyl blue (BCB) and rhodamine 6G (R6G). They were also utilized for preconcentration and SERS detection of 4-mercapto benzoic acid (4-MBA). Gold nanoparticles on the silica and thiol group on the 4-MBA were very selective to each other, thus, 4-MBA could be attached on to gold surface and it could be easily separated magnetically from the reaction medium and identified by Raman spectroscopy. Characterization of the cobalt, cobalt-silica and gold modified cobalt-silica nanoparticles was done by Field Emission Scanning Electron Microscopy (FE-SEM), Scanning-Transmission Electron Microscopy (S-TEM), Energy-Dispersive X-ray Spectroscopy (EDX), UV-Vis spectrometry, and Raman microscope system.

La détection et la surveillance des gaz est un enjeu important tant pour la sécurité industrielle que pour la protection de l’environnement et des personnes. Le dihydrogène, prend une place de plus en plus importante en tant que combustible et vecteur énergétique mais il est extrêmement inflammable et explosif dans un large domaine de 4 à 75 % dans l’air. De même, l’ammoniac est très utilisé dans l’industrie comme gaz réfrigérant ou comme élément de base pour la production chimiques d’autres composés. Ce gaz présente des risques sur l’environnement et sur les êtres vivants et peut former des mélanges explosifs avec l’air dans les limites de 15 à 28 % en volume. Les capteurs de gaz permettant d’indiquer la présence et/ou la quantification de ces gaz prennent alors toute leur importance. Dans la continuité de nos nombreux travaux sur les capteurs résistifs à base d’assemblages discontinus de nano-objets, l’objet de ce travail de thèse a été de préparer des capteurs résistifs pour la détection de H2 et NH3. Ces capteurs sont à base d’assemblages 2D de nanoparticules de compositions complexes. Trois types de nanoparticules cœur-coquille ont été synthétisés : Au@ZnO, Au@SnO2 et Au@Ag. Différentes techniques physico-chimiques (UV-Visible/TEM / DRX etc) ont permis de caractériser les particules obtenues. L’étape suivante a consisté à les assembler en monocouches compactes. Les films ont été obtenus par la méthode d’assemblage de Langmuir-Blodgett. Après transfert à la surface d’un substrat en verre supportant des électrodes inter digitées, les performances de détection des capteurs résistifs fabriqués ont été alors évaluées. Les capteurs à base de Au@ZnO et Au@SnO2 ont été testés sous H2, tandis que les capteurs à base de Au@Ag l’ont été sous NH3. Les capteurs fabriqués ont montré des performances attractives de détection de H2 et NH3 dans des gammes de concentration étendues. Une autre contribution importante de ce travail concerne la compréhension des mécanismes de détection. Diverses techniques analytiques, tels que la TPD (Température désorption Programmed) et la TPR (Température de réduction programmée) ont été utilisés pour permettre la discussion des les mécanismes impliqués. / Gas sensing and monitoring are important issues for both industrial safety and protection of the environment and human beings. Dihydrogen, is increasingly used as fuel and energy carrier but it is extremely flammable and explosive in a wide range between 4 and 75% in air.Similarly, ammonia is widely used in industry as a cooling gas or as a reagent for the chemical production of other compounds.This gas presents risks to the environment and to living beings and can form explosive mixtures with air within 15 to 28% by volume.Gas sensors, indicating the presence and /or quantification of these gases, are very important.In continuation of our work on resistive sensors based on discontinuous assembly of nano-objects, the aim of this thesis was to prepare resistive sensors for the detection of H2 and NH3.These sensors are based on 2D assemblies of complex compositions of nanoparticles. Three types of core-shell nanoparticles were synthesized: Au@ZnO, Au@SnO2 and Au@Ag. Different physicochemical techniques (UV-Visible / TEM / DRX etc.) were used to characterize the particles. The next step was to assemble them in compact monolayers. The films were obtained by Langmuir-Blodgett assembling technique. Then, they were transferred to the surface of a glass slide supporting interdigitated electrodes. Sensing performances of the as-fabricated resistive sensor were evaluated.Sensors based on Au@ZnO and Au@SnO2 nanoparticles were tested towards H2, while Au@Ag based sensors were tested under NH3.The sensors showed attractive performances in H2 and NH3 detection within wide concentration ranges. Another important contribution of this work is the understanding of detection mechanisms. Various analytical techniques such as TPD (Temperature Programmed Desorption) and TPR (temperature programmed reduction) were used for the discussion of the mechanisms involved.

Orientador: Ítalo Odone Mazali / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-19T10:30:04Z (GMT). No. of bitstreams: 1 Santos_EliasdeBarros_D.pdf: 21364667 bytes, checksum: 387f64757c1773196fb26d80d6304b52 (MD5) Previous issue date: 2011 / Resumo: Este trabalho de tese é referente à preparação e caracterização de sistemas nanoestruturados na forma de nanopartículas caroço-casca e filmes finos alternados dos óxidos semicondutores: TiO2, MoO3 e WO3. Para tal finalidade foram preparadas nanopartículas monocomponentes individuais dos três óxidos mencionados (PVG/TiO2, PVG/MoO3 e PVG/WO3) e nanopartículas caroço-casca bicomponentes (PVG/TiO2-MoO3, PVG/MoO3-TiO2 e PVG/TiO2-WO3), usando o vidro poroso Vycor® (PVG) como suporte. Também foram preparados filmes finos individuais e alternados de TiO2 e MoO3. Para a síntese das nanopartículas foram feitas impregnações do PVG com soluções precursoras dos compostos di-(propóxido)-di-(2-etilhexanoato) de titânio (IV) em hexano, 2-etilhexanoato de molibdênio (VI) em hexano e do composto di-[hexaquis(m-acetato)triacetato(m3-oxo)tritungstênio(III, III, IV) em água. Foi empregado o procedimento de ciclos de impregnação-decomposição sucessivos, que consiste em repetir, empregando o mesmo suporte poroso, o procedimento de impregnação do composto e sua posterior decomposição térmica. Com este método foi possível controlar o tamanho das nanopartículas, que seguido da alternância dos precursores envolvidos em cada ciclo levou a obtenção de nanopartículas compostas por bicamadas (caroço-casca). Os sistemas de nanopartículas foram caracterizados pelas técnicas de espectroscopia Raman, espectroscopia UV-Vis no modo de refletância difusa, difração de raios X usando radiação síncrotron e microscopia eletrônica de transmissão de alta resolução. As nanopartículas individuais PVG/TiO2, PVG/MoO3 e PVG/WO3 e as nanopartículas caroço-casca PVG/TiO2-MoO3, PVG/MoO3-TiO2 e PVG/TiO2-WO3 exibiram efeitos de confinamento quântico por tamanho. Os resultados de caracterização mostraram que a variação do número de ciclos de impregnação-decomposição permitiu controlar o diâmetro do caroço e a espessura da casca, evidenciando as potencialidades das técnicas de caracterização para tal finalidade. Este resultado mostrou que o método de decomposição de precursores metalorgânicos, aliado ao procedimento de ciclos de impregnação-decomposição, mostrou-se eficiente na obtenção de nanopartículas caroço-casca hierarquicamente organizadas. Os filmes finos de TiO2 e MoO3, individuais e alternados, foram depositados sobre substratos de quartzo a partir de ciclos sucessivos de deposição-decomposição alternados, empregando-se a técnica de dip coating. Os filmes finos foram caracterizados por perfilometria óptica, espectroscopia UV-Vis no modo de refletância difusa, espectroscopia Raman, microscopia Raman Confocal, microscopia de força atômica e microscopia eletrônica de varredura com análise espectroscópica de dispersão de energia. Os filmes finos alternados bicomponentes são formados por uma estrutura bicamada entre os dois óxidos componentes. Apesar da maior dimensão dos filmes finos, escala micrométrica, em comparação com as nanopartículas caroço-casca, escala nanométrica, foi possível identificar por espectroscopia Raman a presença dos dois óxidos mostrando que a camada do componente superior não suprime o sinal Raman do componente inferior / Abstract: This work reports the synthesis and characterization of nanostructured systems - core-shell nanoparticles and alternate thin films - based on the semiconductor oxides: TiO2, MoO3 and WO3. For this purpose, individual monocomponent nanoparticles (PVG/TiO2, PVG/MoO3 and PVG/WO3) and bicomponent core-shell nanoparticles (PVG/TiO2-MoO3, PVG/MoO3-TiO2 and PVG/TiO2-WO3) of the above mentioned oxides using porous Vycor® glass (PVG) as support were synthesized. Also, individual thin films and alternate thin films of TiO2 and MoO3 were prepared. For the nanoparticles synthesis, the procedure used was based on the impregnation of PVG pieces with titanium (IV) di-(n-propoxy)-di-(2-ethylhexanoate) in hexane, molybdenum (VI) 2-ethylhexanoate in hexane, or di-[hexakis(m-acetato)triacetate(m3-oxo)tritungstato of hexakis(m-acetate)triaquo(m3-oxo)tritungsten(III, III, IV) in water, followed by thermal decomposition. This procedure, successively repeated over the same PVG piece, was named impregnation-decomposition cycle. With this method it was possible to control the nanoparticles size, and by alternating the metallo-organic precursors used, it was possible to obtain nanoparticles with core-shell architecture. Nanoparticle-based systems were characterized by Raman and diffuse reflectance UV-Vis spectroscopies, powder X-ray diffraction using synchrotron radiation and high resolution transmission electron microscopy. Individual nanoparticles PVG/TiO2, PVG/MoO3 and PVG/WO3 and the core-shell nanoparticles PVG/TiO2-MoO3, PVG/MoO3-TiO2 and PVG/TiO2-WO3 are under quantum confinement regime. Characterization showed that the change in the impregnation-decomposition cycle number enables one to control the core size and shell thickness, showing the potential characterization for this purpose. This result showed that metallo-organic decomposition method and impregnation-decomposition cycle procedure is efficient to prepare organized hierarchically core-shell nanoparticle. Thin films of individual and alternated TiO2 and MoO3 were prepared by dip coating of the Ti(IV) and Mo(VI) metallo-organic precursors listed above over quartz slides, followed by thermal decomposition. This procedure, successively repeated over the same quartz slide, was named deposition-decomposition cycle. The thin films were characterized by optical profilometry, Raman and diffuse reflectance UV-Vis spectroscopies, confocal Raman microscopy, atomic force microscopy and scanning electron microscopy with energy dispersive spectroscopic analysis. The thin films formed by two-component show bilayered structure between the two oxide components. Despite the differences in dimension between thin films - in micrometer scale - and the supported core-shell nanoparticles - in nanometer scale - Raman spectroscopy was able to identify in both systems the presence of the two oxides, showing that the top layer component does not suppress the Raman signal of the lower component / Doutorado / Quimica Inorganica / Doutor em Ciências

Au cours ce travail, nous nous sommes intéressés au design de particules plasmoniques pour le contrôle de l’absorption et de l’émission de lumière. Notre stratégie a été de synthétiser des nanoparticules de type cœur@écorce composées d’un cœur d’or et d’une écorce diélectrique de silice contenant des molécules organiques fluorescentes. Nous avons fait varier la distance entre ces dernières et le cœur afin de moduler l’intensité de leur couplage avec les plasmons du métal et d’ainsi contrôler les propriétés optiques des nanoparticules. Nous nous sommes aussi intéressés à l’assemblage de ces nanoparticules sous la forme de supra-particules ou de réseaux bidimensionnels organisés. L’étude des propriétés optiques de ces nouveaux matériaux a permis de mettre en évidence une forte exaltation de l’intensité de fluorescence des particules cœur@écorce quand celles-ci sont confinées entre deux nappes métalliques, ce qui correspond à un mode de cavité fort. Nous avons également travaillé sur la synthèse de particules composées d’un cœur de silice et soit d’une écorce d’or présentant des patchs « vierges », soit d’une écorce de dioxyde de titane comportant des patchs recouverts de nanoparticules d’or. / During this work, we were interested in the design of plasmonic particles for the control of the absorption and the emission of light. Our strategy was to synthesize core@shell nanoparticles made of a gold core and a silica shell containing fluorescent organic molecules. We have varied the distance between the emitters and the core in order to tune their coupling with the plasmons of gold. We thus tuned the optical properties of the particles. We were also interested in the assembly of these nanoparticles to get supra-particles or organized two-dimensional networks. The study of optical properties of these new materials showed that the exaltation of the fluorescence is maximal when the core@shell particles are confined between two gold boundaries, this situation corresponding to a strong cavity mode. We also worked on the synthesis of particles consisting of a silica core and either a gold shell with bare patches or a titanium dioxide shell with patches covered with gold nanoparticles.

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O objetivo do trabalho foi sintetizar e caracterizar nanopartículas de poliestireno e polimetacrilato de metila com morfologia núcleo-casca obtidas através da polimerização em emulsão sem emulsificante em dois estágios e através da fotopolimerização. Nos experimentos avaliou-se a influência de diferentes condições operacionais baseadas em fatores cinéticos sobre os dois estágios da polimerização. As condições avaliadas para o primeiro estágio de preparação de núcleos foram: a temperatura do processo, a concentração de iniciador e de monômero, e o efeito de agentes modificadores de superfície (sal, co-monômero e reticulante). Para o segundo estágio de formação da casca as condições avaliadas foram: a concentração e o regime de alimentação de monômero. Os resultados experimentais mostraram que uma relação de co-monômero e reticulante é a melhor alternativa para preparar núcleos estáveis e de diâmetros pequenos. Assim, o revestimento uniforme dos núcleos é obtido no segundo estágio e com isso a morfologia núcleo-casca em equilíbrio é alcançada. Dois sistemas experimentais (reator convencional e reator fotoquímico) foram propostos e avaliados na sua eficiência para obter partículas com este tipo de morfologia no segundo estágio (formação do revestimento). As diversas técnicas de caracterização indicaram a formação de morfologia núcleo-casca na maioria dos casos estudados para os dois sistemas propostos. Por sua vez, as técnicas espectroscópicas (NIR e Raman) permitiram o monitoramento do processo em tempo real e a elaboração de modelos de calibração que correlacionaram o crescimento do tamanho da partícula núcleo. Da mesma forma, os fatores termodinâmicos foram estudados para predizer a morfologia final esperada nos sistemas. Os resultados, experimental e predito são comparados e discutidos em termos de aspectos chave envolvidos no controle da morfologia da partícula. / This work aimed at studying the synthesis and characterization of core-shell nanoparticles of polystyrene and polymethylmethacrylate obtained in a two-stage emulsifier-free emulsion polymerization and photopolymerization. The influence of different operational conditions based on kinetic factors was experimentally evaluated. In the first stage (seed preparation) the process temperature, initiator and monomer concentrations and the effect of surface-modifier agents (acids, salts, co-monomers and crosslinker) were investigated; similarly in the second stage, the concentration and feeding regime of monomer were evaluated with respect to the shell formation. Experimental results showed that both, crosslinker and co-monomer are the best alternative to achieve a stable seed with small diameter; hence, with this core, uniform coating is obtained in the second stage and core-shell morphology is reached. In order to evaluate the efficiency of the preparation of core-shell particles, two experimental systems (conventional and photochemical reactor) were studied. Different characterization techniques indicated that in most of the cases studied particles with the desired core-shell morphology were formed. The use of spectroscopic techniques NIR and Raman were tested for the real-time monitoring of the process using adequate calibration models developed to correlate the average size of the growing core particle with the spectra. In the same way, thermodynamic factors were used to predict the expected final morphology of the particles. Experimental and predicted results were compared and discussed in terms of the key aspects involved in the control of the particle morphology.

Die im Jahre 1963 von Robert Bruce Merrifield vorgestellte festphasengebundene Peptidsynthese beeinflusste in hohem Maße verschiedene Bereiche der Naturwissenschaften. Doch trotz zahlreicher neuer Entwicklungen hat sich in der das Prinzip der eingesetzten Trägermaterialien nicht grundlegend geändert. Geringfügig quervernetzte Polystyrol-Harze sind immer noch die meist verwendeten Trägermaterialien in der standardisierten Peptidsynthese. In dieser Arbeit wurden superparamagnetische Kern-Schale-Nanopartikel entwickelt und erstmals deren Einsatz als neues Trägermaterial für die Synthese von Peptiden, Peptid-Polymer-Konjugaten und Oligonucleotiden demonstriert. Unter Verwendung einer mikrowellenunterstützten Syntheseroute gelang es zunächst superparamagnetische Magnetitpartikel mit einem Durchmesser von durchschnittlich 6 nm darzustellen. Anschließend wurde ein neu entwickelter mikrowellenunterstützter Stöber-Prozess zur Herstellung von Magnetit-Silica-Kern-Schale-Nanopartikel angewendet, welche im dritten Schritt mit Aminopropyltrimethoxysilan funktionalisiert wurden. Es wurden hochpräzise, monodisperse Kern-Schale-Nanopartikel mit einem Durchmesser von durchschnittlich 69 nm und einem Beladungswert von 0.11 mmol/g erhalten, welche in durchgeführten Stabilitätstests hervorragende Ergebnisse zeigten und als neue Trägermaterialien für festphasengebundenen Synthesen getestet wurden. Die erforderliche Produktaufreinigung erfolgte durch ein externes Magnetfeld, durch welches die Partikel reversibel sedimentierbar sind. Erste Studien der Synthese einer 4-mer-Peptidsequenz zeigten Ausbeuten von über 70% und mit herausragender Reinheit von über 95%. Besonders eindrucksvolle Ergebnisse erzielten die Partikel bei der Synthese von Peptid-Polymer-Konjugaten, bei denen die Ligationsreaktionen mit vorher nicht dokumentierten Umsatzraten verliefen. Außerdem konnte die Anwendbarkeit bei der Synthese eines Trinucleotids nachgewiesen werden. / In 1963 Merrifield introduced the method of solid-phase supported synthesis and thus revolutionized peptide synthesis. In spite of several new developments, the main principle of established solid supports has not changed much. Still lightly cross linked poly(styrene) resins dominate the used supports. This work reports on surface amino functionalized, superparamagnetic nanoparticles with a protective silica shell to be applicable as colloidal supports for organic synthesis of peptides, peptide polymer conjugates and oligonucleotides. A microwave supported synthesis route lead to superparamagnetic magnetite particles with an average particle diameter of 6 nm. Subsequently a new developed microwave assisted Stöber process was used to build up magnetite-silica-core-shell-nanoparticles, which were functionalized in a third step with aminopropyltrimethoxysilane. Defined monodisperse core-shell nanoparticles were obtained with an average diameter of 69 nm and a concentration of free amino groups of 0.11 mmol/g, which showed excellent results in conducted stability tests and were used as new support materials for solid-supported syntheses. Convenient magnetic sedimentation proved to ensure ease of purification after each reaction step. Initial studies of a synthesis of a tetramer peptide sequence showed yields of more than 70% and an outstanding purity of more than 95%. The particles also showed impressive results in the synthesis of peptide-polymer conjugates, in which the ligation reactions proceeded conversion rates, which had not been published before. In addition, the applicability of the particles was demonstrated in the synthesis of a trinucleotide.