Micro Hall probe magnetometry has been used to investigate the magnetisation of various electrodeposited microcrystals. Superconducting tin crystals of almost perfect square cuboid shapes exhibit a strong size dependence of the supercooling of the superconducting state and, for the smallest accessible crystals, the crossover to the mesoscopic regime can be readily explored close to their critical temperatures. Experimental results are in good agreement with Ginzburg-Landau simulations using the exact experimental parameters. Electroplating of the tin cores with another material provides unique core-shell structures of either two superconductors (S-S’: tin-lead) or of a superconducting core, covered with a ferromagnetic shell (S-F: tin/lead-nickel). The critical parameters of the tin core in Sn-Pb core-shell crystals are considerably enhanced and superconductivity in the tin core is detected up to 1:16 TSn c . Little-Parks oscillations in the shell can be analysed to reveal the extent of the superconducting sheath and hence can be utilised to measure the range of the proximity effect close to the critical temperature of the shell. In S-F core-shell structures, field cancellation effects govern the overall behaviour. Under certain conditions it was possible to switch the overall magnetic response from para(ferro-)magnetic to diamagnetic and back at finite applied fields. Micromagnetic simulations qualitatively reproduce the experimentally observed effects. Applications for the core-shell structures include magnetic guidance or memory devices.

Nanoclusters a base de platina vêm sendo amplamente estudados devido à possibilidade de ajustar suas propriedades físicas e químicas através da manipulação de seu tamanho, forma e composição. No entanto, nossa compreensão em nível atomístico dos mecanismos que determinam a estabilidade desses sistemas está longe de ser ideal. Nesta dissertação de mestrado, utilizamos a teoria do funcional da densidade, empregando o método de projeção de onda aumentada com a aproximação do gradiente generalizado, para investigar as propriedades enérgicas, estruturais e eletrônicas de nanoligas PtnMT55-n (MT = Fe, Co, Ni, Cu, Zn). Usando uma energia relativa (energia excedente) para medir a estabilidade de uma nanoliga, sendo obtidas as seguintes composições de menor energia: Pt35Fe20, Pt42Co13, Pt28Ni27, Pt20Cu35 e Pt20Zn35. Com exceção da estrutura do tipo caroço-casca Pt42Co13 icosaedrica (ICO), os demais sistemas possuem ambos os átomos Pt e MT expostos diretamente à região de vácuo, o que é interessante para reações químicas. Das análises estruturais, obtivemos a relação entre tamanho, ordem de ligação e tendência de segregação. Para Zn55 e Pt55, as estruturas de caroço reduzido (RCORE) são preferidas, enquanto para MTs como Fe, Co, Ni e Cu que são menores do que a Pt em 10.6, 11.3, 11.3 e 8,5%, a geometria icosaedrica é favorecida. Portanto, a combinação de Pt com átomos de MT em uma nanoliga (PtMT) favorece a configuração ICO para átomos de MT pequenos (Fe, Co, Ni e Cu), devido a grande liberação de tensão. Já PtnZn55-n que apresentam pequena diferença de tamanho (Zn é menor do que a Pt em apenas 2,1%), consequentemente, a estabilização de estrutura ICO não é possível e uma estrutura RCORE é obtida para todas as composições analisadas. A posição do centro de gravidade dos estados-d ocupados em relação ao nível de Fermi pode ser ajustada em função da composição de Pt. Assim, a energia de adsorção do adsorbato para o nanoligas pode ser alterada, o que afeta a reatividade das nanoligas PtnMT55-n. / Platinum-based nanoclusters have been widely studied due to the possibility to tune their physical and chemical properties through size, shape, and composition. However, our atom-level understanding of the mechanisms that determines the stability of those systems is far from ideal. In this dissertation, we use the density functional theory, using the projected augmented wave method with the generalized gradient approximation, to investigate the energetic, structural, and electronic properties of the PtnTM55-n (TM = Fe, Co, Ni, Cu, Zn) nanoclusters. Using a relative energy (excess energy) to measure the stability of a nanoalloy, we have obtained the lowest energy compositions Pt20Fe35, Pt42Co13, Pt28Ni27, Pt20Cu35, and Pt20Zn35. Except for the core-shell Pt42Co13 icosahedron (ICO) structure, the other systems have both Pt and TM atoms exposed directly to the vacuum region, which is interesting for chemical reactions. From structural analyses we have obtained an interplay of size mismatch, bond-order parameter, and the segregation tendency. For Zn55 and Pt55, the reduced-core (RCORE) structures are preferred, while for small size TMs, like Fe, Co, Ni, and Cu that are smaller than Pt by 10.6, 11.3, 11.3, and 8.5%, the icosahedral geometry is stabilized. The combination of Pt with TM atoms in a nanoalloy (PtTM) favors the ICO configuration for small TM atoms (Fe, Co, Ni, and Cu), because of the larger release of the strain energy. PtnZn55-n presents a small size mismatch (Zn is smaller than Pt by only 2.1%), consequently, the ICO stabilization is not possible and RCORE structure is obtained for all compositions. The position of the center of the gravity of the occupied d -states in relation to the Fermi level can be tuned as a function of the Pt composition. Thus, the adsorption energy of adsorbate to the nanoalloys can be changed, which can affect the reactivity of the PtnTM55-n nanoclusters.

Au cours de ce travail de thèse, nous avons étudié la synthèse de particules de latex par polymérisation en miniémulsion, un procédé de polymérisation en milieu aqueux dispersé. Nous avons synthétisé avec succès et de manière contrôlée des particules de latex de polystyrène de masse molaire élevée (Mn > 30 000 g.mol-1) par polymérisation radicalaire contrôlée par les nitroxydes (NMP) en miniémulsion, en présence et en absence de tensio-actif moléculaire. Des latex stables présentant des diamètres de l’ordre de 150 – 200 nm ont été synthétisés. Une seconde partie de ce travail de thèse est dédié à la transposition de la polymérisation radicalaire contrôlée par les nitroxydes amorcée depuis la surface (« surface-initiated NMP ») d’un procédé en masse vers un procédé en milieu aqueux dispersé (miniémulsion) en vue de synthétiser des nanoparticules cœur@écorce de type silica@polystyrène. La dernière partie du travail de thèse est consacrée à la synthèse de stabilisants polymères et plus précisément à la synthèse de copolymères amphiphiles à base de dextrane ou de poly(acide acrylique) modifiés de manière hydrophobes par des terpènes. L’efficacité de stabilisation de tels copolymères synthétisés à partir de bio-resources a été étudiée au travers leur capacité à stabiliser la polymérisation en miniémulsion du styrène. Tout au long de ce travail, les caractéristiques macromoléculaires des polymères ainsi que la taille et la morphologie des particules ont été caractérisées respectivement par chromatographie d’exclusion stérique, diffusion dynamique de la lumière et microscopie (SEM, TEM, AFM). / During the work of this PhD, we investigated the synthesis of latex particles by miniemulsion, an aqueous dispersed medium process. We managed to synthesize in a controlled manner high molar mass (Mn > 30 000 g.mol-1) polystyrene latex particles via nitroxide mediated radical polymerization (NMP) in miniemulsion in both the presence and absence of molecular surfactant. Stable latex with final diameters within the range of 150-200 nm were synthesized. A second part of the PhD work was devoted to the transposition of surface-initiated NMP from bulk polymerization to polymerization in aqueous dispersed media (miniemulsion) in order to synthesize silica@polystyrene core@shell hybrid nanoparticles. The last part of the PhD work was dedicated to the synthesis of polymeric stabilizers, more precisely to the synthesis of amphiphilic copolymers based on dextran or poly(acrylic acid) polymers hydrophobically modified by terpenes. The stabilization efficiency of such copolymers synthesized from renewable resources to stabilize styrene miniemulsion polymerization was investigated. During this work, we characterized the macromolecular features of polymers along with the size and the morphology of the final particles by respectively size exclusion chromatography (SEC), dynamic light scattering (DLS) and microscopy (SEM, TEM, AFM).

Submitted by Luciana Ferreira (lucgeral@gmail.com) on 2014-08-19T14:30:36Z No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Dissertacao_Jose Carlos Campello Lopes Jr.pdf: 3551367 bytes, checksum: fc027437d4c362a01703752003b22515 (MD5) / Made available in DSpace on 2014-08-19T14:30:37Z (GMT). No. of bitstreams: 2 license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Dissertacao_Jose Carlos Campello Lopes Jr.pdf: 3551367 bytes, checksum: fc027437d4c362a01703752003b22515 (MD5) Previous issue date: 2010-05-17 / In this work we investigated, theoretically and experimentally, the magneto-optical properties of a magnetic fluid consisting of core-shell nanoparticles, where the core is made of magnetite, while the shell is silver. The theoretical model used was based on Mie s theory, under the electrostatic approximation, i.e. for nanoparticles with diameters much less than the incident wavelength (lambda). A Clausius-Mosotti for a core-shell system was used to calculate the electrical susceptibility of the core-shell nanoparticle for equals to 632 nm. The susceptibility was shown to be strongly dependent on the core diameter and the shell thickness. Nevertheless, a maximum value of 7.20 (greater than isolated nanoparticles of silver, which has 0 = 4.30, or magnetite with 0 = 1.47) was obtained for a fraction f, defined as f = (Dcore/Dcore−shell)3, equal to 0.36. This result suggest that there exist an ideal fraction f for nanocomposites with enhanced optical properties. In order to compare our theoretical results with experimental data a core-shell magnetic fluid was synthesized on the Institute of Chemistry of UFG by the group of Dr. Em´ılia Celma de Oliveira Lima. The nanoparticles were suspended in water at fisiological pH and recovered by a double layer of lauric acid (dodecanoic acid). The nanoparticles were characterized by X-ray diffraction, high resolution electron transmission, energy dispersive X-ray spectroscopy, and vibrating sample magnetometer. The Sturges method was used to obtain the nanoparticle diameter histogram. The data revealed the existence of a bimodal nanoparticle distribution. Both distributions were curve fitted using a lognormal function. The modal diameter of one of them was 9.24 ± 0.03 nm with a dispersity of 0.27 ± 0.02, while for the other one we found a modal diameter of 23.0 ± 0.2 nm with disperisty 0.2 ± 0.1. The energy dispersive X-ray spectroscopy confirmed the existence of magnetite and silver only for larger particle diameters, while the lower ones only magnetite was found. From the experimental analysis we confirmed the synthesis of a magnetic fluid containing 10% of core-shell nanoparticles. Magnetization data was used to estimate the magnetic particle volume fraction. The magneto-optical properties were obtained using a magnetotransmissivity technique, where the polarizer and analyser axis are positioned on the magnetic field direction. The sample containing 10% of core-shell nanoparticles, with a total particle volume fraction of 0.18%, had shown an extinction of light of 100% for a magnetic field of only 500 Oe, while a magnetic fluid with 100% of core nanoparticles, at a similar particle concentration (0.15%), had shown a 50% extinction of light at the same field range. The magnetotransmissivity data were curve fitted with a theoretical model containing only two parameters, one related to the electrical susceptibility and the other to the formation of self-organized nanostructures in the colloid. The mean agglomerate size (nanoparticles forming linear chains) had changed from 2.09 to 3.36 for a particle volume fraction increasing from 0.06% to 0.18%. Using the estimative of the double layer lenght of lauric acid, approximately 2 nm, and analyzing the magnetotransmissivity data for several particle concentrations, we were able to obtain the fraction f of core-shell nanoparticles of 0.17. This result, together with TEM data, allowed us to calculate the core diameter of the core-shell nanoparticle as 13 nm. Indeed such result suggest that in order to be suscessful in coating the nanoparticle with the shell element one might need monodisperse-like nanoparticle systems. / Neste trabalho investigamos, teorica e experimentalmente, as propriedades magneto-´opticas de um fluido magn´etico constitu´ıdo de nanopart´ıculas core-shell (caro¸co-casca), em que o caro¸co ´e feito de magnetita e a casca de prata. O modelo te´orico utilizado baseou-se no modelo de Mie, dentro da aproxima¸c ao eletrost ´atica, que consiste no caso em que o di ametro das nanopart´ıculas ´e muito menor que o comprimento de onda da luz incidente ( ). Uma rela¸c ao de Claussius-Mossotti para o sistema core-shell foi utilizada para o c´alculo da susceptilidade el´etrica da nanopart´ıcula core-shell para lambda=632 nm. A susceptilidade el´etrica do nanocomposto foi fortemente dependente do di ametro do caro¸co e da espessura da casca. Entretanto atinge um valor m´aximo de 7,20 (maior que o de uma nanopart´ıcula de prata com 0 = 4, 30 ou de magnetita 0 = 1, 47) para uma fra¸c ao f, definida como f = (Dcore/Dcore−shell)3, igual a 0,36. Este resultado sugere que existe uma fra¸c ao ideal entre os materiais que proporciona ao nanocomposto resposta m´axima `as propriedades ´opticas. No intuito de comparar nossos resultados te´oricos com dados experimentais, um fluido magn´etico core-shell foi sintetizado no Instituto de Qu´ımica da UFG pelo grupo da Profa. Dra. Em´ılia Celma de Oliveira Lima. As nanopart´ıculas foram suspensas em ´agua em pH fisiol´ogico e recobertas por uma dupla camada de ´acido la´urico (´acido dodecan´oico). As nanopart´ıculas foram caracterizadas por difra¸c ao de raios-X (DRX), microscopia eletr onica de transmiss ao de alta resolu¸c ao (HR-TEM), espectrometria de energia dispersiva de raios-X (EDS) e magnetometria de amostra vibrante (VSM).O m´etodo de Sturges foi utilizado para montar o histograma dos di ametros das nanopart´ıculas. Os dados revelaram a exist encia de uma distribui¸c ao bimodal. Ambas distribui¸c oes foram ajustadas considerando uma distribui¸c ao do tipo lognormal. O di ametro modal de uma delas foi de 9.24 ± 0.03 nm com uma dispers ao de 0.27 ± 0.02, enquanto que para a outra distribui¸c ao foi encontrado um di ametro modal de 23.0 ± 0.2 nm e dispers ao 0.2 ± 0.1. A espectrometria de energia dispersiva confirmou a presen¸ca de magnetita e prata, em quantidades significativas, somente nas part´ıculas de maior di ametro, enquanto nas de menor di ametro foi confirmado a exist encia apenas de magnetita. A partir destas an´alises foi confirmada a s´ıntese de um fluido magn´etico contendo 10 % das nanopart´ıculas do tipo core-chell . Dados de magnetiza¸c ao foram obtidos para estimar a fra¸c ao volum´etrica de nanopart´ıculas magn´eticas. Medidas das propriedades magneto-´opticas foram feitas utilizando a t´ecnica de magnetotransmissividade com polarizador e analisador orientados na dire¸c ao do campo magn´etico aplicado. Amostra contendo10% de suas nanopart´ıculas do tipo core-shell , com uma fra¸c ao volum´etrica total de apenas 0,18%, apresentou uma extin¸c ao da luz de 100% a um campo de apenas 500 Oe, enquanto que uma amostra com 100% de nanopart´ıculas do tipo core , em concentra¸c ao semelhante (0,15%), apresentou uma extin¸c ao de 50% na mesma faixa de campo magn´etico. Os dados de magnetotransmissividade foram ajustados considerando um modelo contendo apenas 2 par ametros, estando um deles relacionado a susceptibilidade el´etrica e outro a forma¸c ao de estruturas auto-organizadas no col´oide. O tamanho m´edio de aglomerados (nanopart´ıculas formando uma cadeia linear) variou de 2.09 para 3.36 para uma fra¸c ao volum´etrica crescendo de 0,06% para 0,18%. Usando dados da literatura acerca da estimativa do comprimento da dupla camada de ´acido la´urico, como sendo de aproximadamente 2 nm, e analisando os dados de magnetotransmissividade para diversas concentra¸c oes de nanopart´ıculas, foi poss´ıvel obter a fra¸c ao f das nanopart´ıculas core-shell como sendo de 0,17. Este resultado, conjuntamente com os dados de TEM, permitiu concluir que o di ametro do caro¸co na nanopart´ıcula core-shell ´e de 13 nm. Este resultado ´e interessante tecnologicamente, pois sugere que, para se obter sucesso no recobrimento de nanopart´ıculas, seja necess´ario, ou ao menos importante, utilizar amostras com baixa dispers ao de di ametros.

Híbridos poliuretano-acrílicos foram sintetizados via polimerização em emulsão, utilizando uma dispersão de poliuretano base poliol poliéster como semente para a polimerização dos monômeros acrílicos, no caso, acrilato de butila e ácido metacrílico. As propriedades das dispersões híbridas resultantes foram avaliadas por espalhamento dinâmico de luz, teor de sólidos, pH e potencial Zeta. Os polímeros resultantes da secagem das dispersões aquosas foram caracterizados por cromatografia por exclusão de tamanho, calorimetria exploratória de varredura, análise dinâmico-mecânica, dureza, microscopia ótica do processo de cristalização, microscopia de força atômica, microscopia eletrônica de transmissão. A influência do método de síntese na morfologia dos híbridos foi avaliada. / PU-acrylic hybrids were prepared via emulsion polymerization, using an aqueous polyurethane dispersion as a seed for the acrylic monomers polymerization. Different quantities of acrylic monomers (butyl acrylate and methacrylic acid) were polymerized. The properties of the resulting hybrid dispersions were evaluated through dynamic light scattering, solid content, pH and Zeta potential. The resulting polymers obtained from dried dispersions were characterized via size exclusion chromatography, differential scanning calorimetry, dynamic mechanical analysis, optical microscopy of the crystallization process, atom force microscopy and transmission electron microscopy. The influence of the synthetic method on the morphology of the hybrids was evaluated.

Nos últimos anos novas propriedades magnéticas, eletrônicas e ópticas, têm sido observadas em sistemas de nanopartículas (NPs) feitas de diferentes tipos de materiais. Em nanoestruturas do tipo núcleo@casca, a composição de um núcleo magnético com uma casca plasmônica apresenta características que lhe conferem promissor potencial para aplicações em áreas como eletrônica, biomédica, farmacêutica, óptica e catálise. Este trabalho apresenta uma nova abordagem para a produção de nanopartículas metálicas do tipo núcleo@casca pela combinação de técnicas físicas, o método de agregação gasosa e fontes de magnetron sputtering planar/radial. As NPs produzidas foram analisadas magneticamente por VSM e SQUID, sua morfologia por HRTEM, a sua composição por RBS e EDS, a sua estrutura cristalina por XRD e as propriedades ópticas por espectrofotometria de UV-Visível. Os resultados experimentais serão apresentados para o sistema Co@Cu, mas a técnica pode ser utilizada para produzir NPs compostas de outros elementos químicos. Em paralelo a produção de nanopartículas, o gerador de NPs foi totalmente reestruturado. Foram testadas diferentes aberturas de saída das nanopartículas, viabilizando uma deposição do material de forma homogênea em áreas maiores. As novas aberturas possuem formato cônico, plano e de grades (600 furos com diâmetros entre 50 µm e 224 µm). Através destas grades foi possível obter uma distribuição espacial homogênea de nanopartículas. A entrada de gás no gerador também foi modificada, a fim de otimizar a deposição dos aglomerados e obter uma reprodutibilidade na operação do equipamento. Foram testados diversos modos de entrada do gás: na lateral do copo, no centro em diferentes distâncias do alvo e por último na região em torno do alvo, sendo a última a melhor configuração obtida. / In recent years new magnetic, electronic and optical properties have been observed in nanoparticles (NPs) made of different conjugation of materials. In magnetic nanostructures of the core@shell type, the compound of a magnetic core and a plasmonic shell, provides many features with potential for applications in areas such as electronics, biomedical, pharmaceutical, optical and catalysis. This work presents a new approach to the production of metallic core@shell nanoparticles by the combination of physical techniques, the gas aggregation method and planar/radial magnetron sputtering sources. The produced NPs were magnetically analyzed by VSM e SQUID, the morphology by SEM and HRTEM, the stoichiometry by RBS and EDS, the crystal structure by XRD and UV-Visible spectrophotometry. The experimental results will be presented for the system Co@Cu but the technique can be used to produce NPs composed of other chemical elements. In parallel to the production of nanoparticles, the NPs generator has been completely redesigned. Different apertures were tested enabling deposition of homogeneous material in large areas. The nanoparticles are now spread on the substrate using the frontal apertures shaped as conical, plane and grids (600 holes ranging from 50 µm to 224 µm diameters). Through these grids we have obtained a homogeneous spatial distribution of NPs. The gas inlet in the NP generator was modified, in order to optimize the deposition of NPs and to obtain reproducibility in the operation of the equipment. Several gas injection modes were explored, as p.e. lateral; frontal to the center of the target at different distances; and finally through the gap of the sputtering gun, in parallel to the target surface. The last option was the best configuration.

Depuis la démonstration de l’extrême sensibilité de la spectroscopie Raman exaltée de surface (acronyme SERS en anglais) à la fin des années 90, un des défis actuels consiste à élaborer des substrats SERS actifs composés de nanoparticules ayant des formes anisotropes avec des pointes prononcées ou des nanoparticules couplées de manière contrôlée et reproductible. De tels systèmes génèrent en effet une forte exaltation du champ électromagnétique, respectivement sur les régions à fort rayon de courbure et au sein de l’interstice. Ce fort confinement du champ, on parlera de point chaud, est essentiel dans le but de détecter de très faibles quantités de molécules. L’objectif principal de ma thèse est de développer et de caractériser finement de nouveaux substrats SERS obtenus par des méthodes d’élaboration chimiques (fonctionnalisation de surface) de substrats à points chauds contrôlés. La réalisation de tels substrats vise également une meilleure compréhension des mécanismes d’exaltation électromagnétique à l’origine de l’effet SERS. / The design of novel plasmonic platforms for Surface Enhanced Raman Spectroscopy (SERS) constitutes a very active field of research in nanosciences. Such platforms can be used for the detection and identification of various analytes at very low concentration, through a huge amplification of the Raman signal, resulting from the excitation of localized surface plasmon resonances. The main objective of my phd is to develop and to characterize new SERS substrates obtained by chemical assembly (surface functionalization) of nanoparticles with controlled hot spots. Design of such substrates contributes to a better understanding of the mechanisms of electromagnetic enhancement considered at the origin of the SERS effect.

Les recherches sur les nanocristaux semiconducteur (NCs) ont conduit à des résultats scientifiques fascinants, spécialement pour l'application en dispositifs optoelectroniques. Afin de répondre à certaines exigences comme des coûts mineurs, des gains d'efficacité, des composants respectueux de l'environnement, etc., des nouvelles méthodes sont explorées: dans les procédés en solution, dans l'ingénierie de bande et des niveaux d'énergie. En particulier, la méthode de synthèse peut influencer les propriétés optoélectroniques. Par conséquent, une meilleure compréhension des facteurs complexes pendant la synthèse entraînera une amélioration des performances.La microscopie électronique avancée fournit un moyen précis de recueillir des informations sur la morphologie, la structure cristalline et la composition chimique des matériaux avec une résolution spatiale au niveau atomique. La première partie de cette thèse traite de la synthèse et de la préparation des échantillons pour la microscopie électronique à transmission en haute résolution (HRTEM).La deuxième partie traite du mécanisme de croissance des NCs Cu2ZnSnS4 synthétisés par une méthode colloïdale. La morphologie et la stoechiométrie des intermédiaires de réaction extraits après différents intervalles de temps sont déterminés par HRTEM et analyse dispersive en énergie (EDS).Deux méthodes complémentaires, la diffraction par nanofaisceau d’électrons en précession (NPED) et la microscope électronique en transmission par balayage à haute résolution avec imagerie en champ sombre avec détecteur annulaire à grand angle (HRSTEM-HAADF) permettent une profonde caractérisation de la structure cristalline.En outre, la structure cristalline de NCs CsPbBr3 est résolue avec simulations de STEM-HAADF. Cet approche peut différencier entre structures cristallines cubiques et orthorhombiques, impossible avec techniques de diffraction traditionnelles. Enfin, l'influence des méthodes de synthèse sur la morphologie et sur la structure cristalline de NCs CuFeS2 pour applications dans le domaine de la thermoélectricité est analysée par HRTEM. / The investigations of semiconductor nanocrystals (NCs) led to fascinating scientific results in optoelectronic devices. In order to fulfill certain requirements, i.e. cheaper costs, higher efficiencies, environmental friendly components etc., new methods are explored in solution-processing, band gap and energy level engineering. Particularly, the method of synthesis can alter the optoelectronic properties. Therefore, a better understanding of the intricate factors during synthesis will lead to improved performances. Advanced electron microscopy provides a precise way to gather information about morphology, crystal structure and chemical composition of materials with a spatial resolution down to the atomic level. The first part of this thesis deals with the optimization of the synthesis and sample preparation for high resolution transmission electron microscopy (HRTEM).The second part deals with the growth mechanism of Cu2ZnSnS4 NCs synthesized by a colloidal method. The morphology and stoichiometry of the samples extracted after different time intervals are characterized by HRTEM and electron dispersion spectroscopy (EDS). Two complementary methods, Nanobeam Precession Electron Diffraction (NPED) and High Resolution Scanning Transmission Electron Microscopy by High Angle Annular Dark-Field Imaging (HRSTEM-HAADF), provide an in-depth crystal structure characterization.Moreover, the crystal structure of CsPbBr3 NCs is solved by probing STEM-HAADF simulations. This approach is able to differentiate cubic and orthorhombic crystal structures, which is otherwise impossible by diffraction techniques. Finally, the influence of synthesis methods on the morphology and crystal structure of CuFeS2 NCs is investigated by HRTEM for thermoelectric applications.

To investigate the interaction between nanoparticles and electromagnetic waves, a numerical simulation model based on FEM was built in this thesis. Numerical simulation is an important auxiliary research method besides experiments. The optical properties of nanoparticles consist of scattering, absorption, and extinction, and in the case of nanoparticle suspension, the transmission is also involved. This thesis addressed two typical applications based on the established model, one was regarding the nanofluids for solar energy harvesting, and the other was regarding the optical properties of atmospheric soot. In the case of the nanofluids solar energy harvesting, the established model provided a convenient and rapid screening of potential nanoparticles and nanofluids candidates for solar energy harvesting. A core-shell structure nanoparticle, using Cu as the core material in a diameter of 90 nm coated with 5 nm thickness graphene, exhibited a better photothermal property under the solar radiation. In the second case regarding atmospheric soot, the established model provided an efficient method for understandings on the optical properties and warming effects of realistic soot particles. It was found that the sizes and material characteristics of soot, would greatly affect their scattering and absorption of light. Moreover, two submodels were introduced and integrated, which can better predict behaviors of real atmospheric soot involving their core-shell structures (moisture or organic condensates) and their fractal agglomerate structures. In conclusion, the established model helps to understand the interaction between nanoparticles and electromagnetic waves, which shows great potentials of wide applications.

L’objectif de cette thèse était d’étudier les mécanismes responsables de la luminescence des ions lanthanides dans des polymères de coordination. Pour cela, des séries d’alliages moléculaires à base d’acide 4 carboxyphénylboronique ont été synthétisées, en faisant varier les proportions relatives des ions lanthanides. Les produits synthétisés ont été étudiés dans la perspective de leur application dans les domaines de la lutte anti-contrefaçon et des thermomètres moléculaires. D’autre part, de nouveaux systèmes utilisant d’autres dérivés d’acide boronique ont été synthétisés. Une nouvelle structure cristalline a été obtenue à base de l’acide 2-carboxyphénylboronique. La seconde partie de cette thèse a porté sur la synthèse et la caractérisation de poudres microcristallines de type coeur-coquille. Il s’agit de la première micro-structuration de polymères de coordination réalisée à l’échelle micrométrique. Les poudres synthétisées ont été caractérisées par microscopies électroniques à balayage, à transmission et par analyses EDS. Leurs propriétés optiques ont été comparées avec celles des alliages moléculaires. Les résultats obtenus ont mis en évidence l'intérêt de la micro-structuration de ces poudres concernant les transferts d'énergie intermétalliques. Cette technique de synthèse basée sur la croissance épitaxiale, est rendue possible par les propriétés chimiques similaires des terres rares. Nos travaux ont montré que lorsque les constantes thermodynamiques et\ou cinétiques le permettent, la phase cristalline de la coquille présente la structure cristalline du cœur même lorsque le composé constituant la coquille cristallise dans une autre phase lorsqu'il est synthétisé seul. / The aim of this thesis was to study the luminescence mechanisms of lanthanide ions in coordination polymers. Series of molecular alloys (hetero-lanthanide compounds in which lanthanide ions are randomly distributed) based on 4-carboxyphenylboronic acid were synthesized, by varying the relative contents of the lanthanide ions. The synthesized products have been studied from the perspective of their application in the fields of anti-counterfeiting and molecular thermometers. On the other hand, new systems using other boronic acid derivatives have been synthesized. A new crystal structure was obtained based on 2-carboxyphenylboronic acid. The second part of this thesis focused on the synthesis and characterization of core-shell microcrystalline powders. This is the first time that micro-structuration of a coordination polymer is achieved at the micrometric scale. The synthesized powders were characterized by scanning electron microscopy, transmission electron microscopy and EDS analyses. Their optical properties have been compared with those of the corresponding molecular alloys. The obtained results highlighted the interest of the micro-structuration concerning intermetallic energy transfers. This strategy of synthesis based on epitaxial growth, is possible because of lanthanide similar chemical properties. This work demonstrates that in the case where the thermodynamic and\or kinetic constants allow it, the shell crystallizes according to the same crystal structure than the core even if its crystal structure is different when it is synthesized alone.