Les mésophases hexagonales sont des systèmes quaternaires formés de tensioactifs et co-tensioactifs, eau salée et huile. Ces mésophases sont utilisées comme moules « mous » pour la synthèse de différents nanomatériaux tels que des nanostructures métalliques poreuses, des nanostructures de polymères conjugués et des nanocomposites métalliques-polymères. Contrairement aux matrices (ou moules) durs, qui nécessitent des réactifs chimiques corrosifs pour extraire les nanomatériaux synthétisés in situ, le processus d'extraction des nanomatériaux synthétisés dans les mésophases hexagonales est simple : les nanomatériaux peuvent être extraits simplement par lavage avec de l'éthanol ou du 2-propanol. Un autre intérêt à utiliser ces mésophases comme matrice de synthèse est qu’elles peuvent être gonflées en contrôlant le rapport huile / eau. Cette thèse est divisée en trois parties: 1) La synthèse de nanostructures métalliques poreuses dans la phase aqueuse des mésophases hexagonales et leur application dans les piles à combustible (oxydation de l'éthanol), 2) La synthèse de nanostructures de polymères conjugués dans la phase huile des mésophases hexagonales pour des applications en photocatalyse et en particulier pour la dégradation de polluants, 3) La synthèse combinée dans les phases huile et eau des mésophases hexagonales de nanocomposites métal-polymère. Plusieurs nanostructures métalliques telles que des nanoballes PdPt de porosité et composition contrôlées, des nanostructures poreuses cœur-coquille AuPd et AuPt, bimetalliques PtNi et trimétalliques AuPdPt ont été synthétisées par radiolyse dans la phase aqueuse des mésophases hexagonales. Les nanoballes PdPt de porosité et composition contrôlées ont été utilisées comme électro-catalyseurs pour l'oxydation de l'éthanol. L'effet de la taille des pores sur la surface électro-active des nanostructures métalliques et leur activité électrocatalytique pour l'oxydation de l'éthanol a été étudié. Les nanostructures poreuses cœur-coquille bimétalliques AuPd et AuPt, et trimétalliques AuPdPt ont été utilisées pour l'oxydation de l'éthanol et du glucose. Les nanoballes poreuses PtNi ont été utilisées pour l'évolution de H2 et la réaction de réduction de l’oxygène. Des nanostructures de polymères conjugués (poly(3-hexylthiophène), P3HT) ont été synthétisées dans la phase huile des mésophases hexagonales. Ces nanostructures de polymères ont une activité photocatalytique élevée sous UV et lumière visible. Le phénol et la rhodamine B ont été utilisés comme polluants modèles. Ces photocatalyseurs sont très stables même après plusieurs cycles photocatalytiques. L'ajout de molécules capteurs et l’étude du mécanisme montrent que les radicaux O2.− sont les principaux radicaux responsables de la dégradation du phénol. De manière très intéressante, l'activité photocatalytique de ces nanostructures de P3HT est fortement augmentée lorsqu'elles sont supportées sur une surface solide. Ce résultat ouvre de nouvelles perspectives pour des applications dans des réacteurs photocatalytiques et des surfaces autonettoyantes. Des résultats préliminaires sur la synthèse des nanocomposites Pt-PDPB (polydiphenylbutadiyne) sont également présentés dans cette thèse. / Soft hexagonal mesophases, which consist of quaternary systems (surfactants, brine, oil, and co-surfactant) are used as templates for the synthesis of different nanomaterials such as metal nanostructures, conjugated polymer nanostructures, and metal-polymer nanocomposites. Unlike hard templates, which need a harsh chemical reagent to extract nanomaterials after the synthesis, in soft template hexagonal mesophases, the extraction process of nanomaterials is simple, only by washing with ethanol or 2-propanol. Another interesting property of this class of template lies on its ability to be swollen by controlling the ratio of oil to water.This thesis is divided into three parts: 1) Radiolytic synthesis of metal nanostructures in the aqueous phase of hexagonal mesophases and their application in fuel cells (ethanol oxidation), 2) Synthesis of conjugated polymer nanostructures in the oil phase of hexagonal mesophases for photocatalytic degradation of pollutants, 3) Combined synthesis in the oil and water phases of hexagonal mesophases of metal-polymer nanocomposites.Several metal nanostructures such as PdPt nanoballs with controlled composition and porosity, AuPd and AuPt core shell, bimetallic PtNi and trimetallic AuPdPt porous nanoballs were synthesized by radiolysis in the aqueous phase of hexagonal mesophases. PdPt nanoballs with controlled porosity and composition were used as electrocatalysts for ethanol oxidation. The effect of the pore size on their electro active surface and their electrocatalytic activity towards ethanol oxidation were studied. AuPd and AuPt core-shell, and trimetallic AuPdPt porous nanoballs were used for ethanol and glucose oxidation. PtNi porous nanoballs were used for H2 evolution and oxygen reduction reaction. Conjugated polymer nanostructures namely P3HT (poly(3-hexylthiophene)) were synthesized in the oil phase of hexagonal mesophases. These polymer nanostructures are highly active for photocatalysis under UV and visible light. Phenol and rhodamine B were used as model pollutants. These photocatalysts are very stable even after repeated cycling. Addition of scavengers and mechanistic studies show that O2.− is the main radical responsible for degradation of phenol. Most interestingly, the photocatalytic activity of these P3HT nanostructures is highly enhanced when they are supported on a solid surface opening new perspectives in photocatalytic reactors and self-cleaning surfaces. Premiminary results on the synthesis of Pt-PDPB (polydiphenylbutadiyne) nanocomposites are also presented in this thesis.

1.1\xMagnetic nanoparticles (NPs) with sizes ranging from 2 to 20 nm in diameter represent an important class of artificial nanostructured materials, since the NP size is comparable to the size of a magnetic domain. They have potential applications in data storage, catalysis, permanent magnetic nanocomposites, and biomedicine.;1.2\xTo begin with, a brief overview on the background of Fe-based bimetallic NPs and their applications for data-storage and catalysis was presented in Chapter 1.;1.3\xIn Chapter 2, L10-ordered FePt NPs with high coercivity were directly prepared from a novel bimetallic acetylenic alternating copolymer P3 by a one-step pyrolysis method without post-thermal annealing. The chemical ordering, morphology and magnetic properties were studied. Magnetic measurements showed that a record coercivity of 3.6 T (1 T = 10 kOe) was obtained in FePt NPs. By comparison of the resultant FePt NPs synthesized under Ar and Ar/H2, the characterization proved that the incorporation of H2 would affect the nucleation and promote the growth of FePt NPs. The L10 FePt NPs were also successfully patterned on Si substrate by nanoimprinting lihthography (NIL). The highly ordered ferromagnetic arrays on a desired substrate for bit-patterned media (BPM) were studied and promised bright prospects for the progress of data-storage.;1.4\xFuthermore, we also reported a new FePt-containing metallopolymer P4 as the single-source precursor for metal alloy NPs synthesis, where the metal fractions were on the side chain and the ratio could be easily controlled. This polymer was synthesized from random copolymer poly(styrene-4-ethynylstyrene) PES-PS and bimetallic precursor TPy-FePt ([Pt(4-ferrocenyl-(NN̂N̂))Cl]Cl) by Sonogashira coupling reaction. After pyrolysis of P4, the stoichiometry of Fe and Pt atoms in the synthesized NPs (NPs) is nearly close to 1:1, which is more precise than using TPy-FePt as precursor. Polymer P4 was also more favorable for patterning by high throughout NIL as compared to TPy-FePt. Ferromagnetic nanolines, potentially as bit-patterned magnetic recording media, were successfully fabricated from P4 and fully characterized.;1.6\xBesides, a bimetallic complex TPy-FePd-2 was prepared and used as a single-source precursor to synthesize ferromagnetic FePd NPs by one-pot pyrolysis. The resultant FePd NPs have a mean size of 19.8 nm and show the coercivity of 1.02 kOe. In addition, the functional group (-NCMe) in TPy-FePd-2 was easily substituted by a pyridyl group. A random copolymer PS-P4VP was used to coordinate with TPy-FePd-2, and the as-synthesized polymer made the metal fraction disperse evenly along the flexible chain. Fabrication of FePd NPs from the polymers was also investigated, and the size could be easily controlled by tuning the metal fraction in polymer. FePd NPs with the mean size of 10.9, 14.2 and 17.9 nm were prepared from the metallopolymer with 5 wt%, 10 wt% and 20wt% of metal fractions, respectively.;1.7\xIn Chapter 4, molybdenum disulfide (MoS2) monolayers decorated with ferromagnetic FeCo NPs on the edges were synthesized through a one-step pyrolysis of precursor molecules in an argon atmosphere. The FeCo precursor was spin coated on the MoS2 monolayer grown on Si/SiO2 substrate. Highly-ordered body-centered cubic (bcc) FeCo NPs were revealed under optimized pyrolysis conditions, possessing coercivity up to 1000 Oe at room temperature. The FeCo NPs were well-positioned along the edge sites of MoS2 monolayers. The vibration modes of Mo and S atoms were confined after FeCo NPs decoration, as characterized by Raman shift spectroscopy. These MoS2 monolayers decorated with ferromagnetic FeCo NPs can be used for novel catalytic materials with magnetic recycling capabilities. The sizes of NPs grown on MoS2 monolayers are more uniform than from other preparation routines. Finally, the optimized pyrolysis temperature and conditions provide receipts for decorating related noble catalytic materials.;1.8\xFinally, Chapters 5 and 6 present the concluding remarks and the experimental details of the work described in Chapters 2-4.

>Magister Scientiae - MSc / TiO2 nanoparticle films are important electron transport layers (ETLs) in photovoltaics such as dye-sensitised, perovskite and polymer hetero-junction solar cells. These films, however, have significant electron trap-sites as a result of the large density of oxygen vacancies present in nanosized TiO2. These trap-sites cause electron-hole recombination and ultimately lower photon-tocurrent conversion efficiency of the underlying cell during operation. Doping the TiO2 lattice with low atomic number elements such as nitrogen is a proven method to overcoming the charge transport inefficiency of TiO2 ETLs; another is the use of one-dimensional (1D) nanowires (NWs), instead of nanoparticles. Modification of TiO2 with non-metals leads to optical bandgap narrowing, improvement in electron conductivity and increased electron lifetime in the ETL layer. However, a lot of scope exists in understanding and fully quantifying the relationship between optical property, for example light transmission and bandgap modification, versus the doping concentration and type. Most doping approaches are in-situ and involve the addition of a dopant precursor (usually a salt) during the synthesis of TiO2 nanostructures – this invariably leads to uncontrolled doping levels, anion contamination and poor-quality materials – a need thus exists to develop simple, controllable doping approaches. One such approach, which forms the basis of this study, is ex-situ doping by means of plasma generated species in a controlled environment. This field of study is fairly novel and not widely studied, requiring more research to understand the doping mechanisms and influence on the optical and electronic properties of the underlying nanomaterials. In particular, controlled doping of TiO2 with nitrogen using radio-frequency generated (RF) plasma requires vigorous experimentation and characterisation. Inaccuracy of the deposition parameters during exposure remains a common drawback for this approach in addition to a lack of understanding of the surface interaction between the N2 species and specimen during irradiation.

Atomic/plasma polymerization technology is widely used in various technical fields. This work is focused to use the PE-CVD technology in the field of formation of interphase and adhesive layers, which are developed into layered nanostructures. To ensure reproducible chemical and physical properties of the materials, the deposition process was monitored by mass spectrometry. Vapours of the pure tetravinylsilane, or a mixture of these vapours with oxygen, was used as a precursor for atomic polymerization, which results in the thin films with a large variability of properties. Physical and chemical properties were varied by the effective power delivered to the plasma discharge. The deposited films were analyzed from different perspectives using several methods (in situ spectroscopic ellipsometry, FTIR, nanoindentation, AFM). The removal of hydrogen atoms from the carbon-silicon network results in increased crosslinking of the material, which controls the mechanical and optical properties of the deposited layers. From the precisely defined a-CSi:H and a-CSiO:H materials, layered nanostructures composed of 3 and 7 individual layers was subsequently constructed. These nanostructures were analyzed by XPS and RBS to determine the atomic concentrations of carbon, silicon, oxygen and their binding states.

Orientador: Olivia Maria Berengue / Banca: Eduardo Gonçalves Ciapina / Banca: Erica Freire Antunes / Resumo: Neste trabalho foram desenvolvidas rotas de crescimento de micro- e nanoestruturas de Sb2O3 e Sb2O4 através de métodos de deposição de fase vapor. Para análise das amostras obtidas foram utilizadas técnicas de difratometria de raios-X, microscopia eletrônica de varredura e espectroscopia Raman. A análise dos resultados obtidos permitiu identificar corretamente as algumas das características estruturais e morfológicas das amostras bem como definir uma rota de crescimento de qualidade e reprodutibilidade. Após a produção e caracterização das amostras dos óxidos de antimônio foi feita a funcionalização e decoração superficial das nanoestruturas de Sb2O3 com nanopartículas de paládio. As nanoestruturas funcionalizadas foram devidamente caracterizadas pelas mesmas técnicas aplicadas as amostras puras dos óxidos, com isso foi possível verificar a eficácia do processo de decoração superficial bem como obter informações sobre a estrutura do produto final desse processo. A síntese de Sb2O3 gerou amostras com 3 tipos de morfologias diferentes, a primeira possui fase cristalina ortorrômbica e consiste de micro e nanofitas ramificadas, as outras duas morfologias são constituídas por seguimentos de micro octaedros empilhados e aglomerados de micrestruturas octaédricas e microesferas, ambas apresentam fase cristalina cúbica. O processo de decoração superficial das amostras de Sb2O3 com nanopartículas de paládio se mostrou eficaz, porém levou a uma grande alteração na morfologia das amostra... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: In this work, Sb2O3 and Sb2O4 micro- and nanostructures were synthesized by a vapor phase deposition method. Aiming to provide data on the structure of these samples, Xray diffraction, scanning electron microscopy and Raman spectroscopy techniques were used. The data analysis allowed to correctly identify the characteristics of the samples as well as to define a good and reproductible growth process. The as-grown Sb2O3 was submitted to palladium nanoparticles functionalization and superficial decoration process. The functionalized nanostructures were duly characterized by the same techniques applied to the pure oxide samples, with the purpose of verifying the effectiveness of the surface decoration process as well as obtaining information on the structure. The Sb2O3 synthesis provide 3 types of different morphologies, the first one has an orthorhombic crystalline phase and consists of branched micro and nanobelts, the other two morphologies are followed by stacked micro octahedron and agglomerate of octahedrons and sphere microstructures, both morphologies have orthorhombic crystalline phase. The palladium nanoparticles functionalization and superficial decoration process proved to be effective, but led to a great morphology change of the Sb2O3 samples. The as-grown Sb2O4 are mainly composed by micro- and nanowires mixed with branched micro-belts structures, both morphologies have orthorhombic crystalline phase / Mestre

Název práce: Optické vlastnosti křemíkových nanostruktur pro fotovoltaiku Autor: Bc. Jan Salava Katedra: Katedra chemické fyziky a optiky Vedoucí diplomové práce: doc. RNDr. František Trojánek, Ph.D., katedra chemické fyziky a optiky Abstrakt: V předložené práci jsou studovány křemíkové nanokrystaly umístěné v SiC matrici - jednotlivé vzorky se odlišují přidáním dopantu (boru) do příslušné vrstvy struktury během depozice metodou PECVD a pasivací vodíkem. Křemíkové nanokrystaly jsou významné zejména tím, že oproti své objemové verzi vykazují účinnou fotoluminiscenci a absorpci ve viditelné oblasti spektra. Změnami parametr· při přípravě lze ladit jejich vlastnosti s ohledem na konkrétní aplikaci. Základní myšlenka integrace křemíkových nanostruktur do solárních článk· spočívá ve zvýšení účinnosti konverze slunečního spektra kombinací několika tenkých vrstev s nanokrystaly a objemového Si článku tak, aby každá vrstva sluneční cely absorbo- vala určitou část spektra. Procesy, které se v těchto strukturách dějí krátce po excitaci nosič· náboje, však stále nejsou zcela popsány. Cílem práce je charakterizace těchto jev· metodami ča- sově rozlišené spektroskopie. Dalším úkolem je popsat vliv dopování jednotlivých částí materiálu a jeho pasivace ve vodíkové atmosféře na chování fotoexcitovaných nosič· a intenzitu...

In this work we investigate changes in dynamics of CdSe nanocrystalline films caused by different annealing temperatures and different conditions during films growth. We use methods of time-resolved laser spectroscopy like time-resolved pump and probe and streak camera to study these dynamics. We also measured linear absorption and luminiscence. Our goal is to match measured dynamics with dynamics of other samples with different annealing temperatures and discuss the microscopic origin of these dynamics. Powered by TCPDF (www.tcpdf.org)

Nanostructured thin films deposited by magnetron sputtering and gas aggregation sources of nanoparticles are studied especially with regards to their use in biomedical applications. The possibility of using plasma polymers for the preparation of antibacterial coatings is tested first. It is presented that sputtered nylon 6,6 films may be impregnated by antibiotics. The subsequent release of antibiotics from such prepared reservoirs may be tuned by their thickness, chemical composition, or by an additional barrier layer. The second studied type of antibacterial coatings is based on metallic nanoparticles overcoated with sputtered PTFE. It is shown that by a proper choice of the number of nanoparticles and thickness of fluorocarbon overlayer, a significant antibacterial effect can be achieved while maintaining the biocompatibility of produced nanocomposite coatings. The possibility to enhance the antibacterial effect by impregnation of plasma polymer/nanoparticle nanocomposites by antibiotics is also verified. Nanoparticle sources are used to study two-component films with 2D gradient character, too. A simple analytical model is developed allowing description and design of such nanomaterials. Its suitability is experimentally verified on 2D gradients combining Ag and Cu nanoparticles. Finally, an original...

>Magister Scientiae - MSc / The industrial safety requirements and environmental pollution have created a high demand to develop gas sensors to monitor combustible and toxic gases. As per specifications of World Health Organization (WHO) and Occupational Safety and Health Administration (OSHA), lengthy exposure to these gases lead to death which can be avoided with early detection. Semiconductor metal oxide (SMO) has been utilized as sensor for several decades. In recent years, there have been extensive investigations of nanoscale semiconductor gas sensor.

>Magister Scientiae - MSc / TiO2 nanoparticle films are important electron transport layers (ETLs) in photovoltaics such as dye-sensitised, perovskite and polymer hetero-junction solar cells. These films, however, have significant electron trap-sites as a result of the large density of oxygen vacancies present in nano-sized TiO2. These trap-sites cause electron-hole recombination and ultimately lower photon-to-current conversion efficiency of the underlying cell during operation. Doping the TiO2 lattice with low atomic number elements such as nitrogen is a proven method to overcoming the charge transport inefficiency of TiO2 ETLs; another is the use of one-dimensional (1D) nanowires (NWs), instead of nanoparticles.