Les zéolithes sont largement utilisées en catalyse. Un enjeu majeur est d'obtenir des cristaux nanométriques qui offrent des perspectives prometteuses dans la conception de catalyseurs acides plus actifs et plus sélectifs, notamment pour les procédés de conversion des coupes lourdes pétrolières. L'obtention de ces nano-cristaux peut résulter de l'utilisation d'inhibiteurs de croissance. Cette thèse s'est attachée à identifier deux familles de composés organiques limitant la croissance des cristaux. Pour la première, l'inhibition est envisagée par adsorption de composés organiques (polycations, acides aminés...) sur la surface des cristaux en formation. Cette étude a été réalisée en suivant une méthodologie d'expérimentation à haut-débit et a conduit à des cristaux de zéolithe Y (FAU) de 300 nm par l'ajout de L-lysine. La seconde famille est dérivée de l’approche de l’équipe de Ryoo et consiste en l’utilisation de composés bifonctionnels comportant une fonction structurante et une fonction inhibitrice de croissance. Cette étude a démarré par la synthèse de zéolithe MFI. La modélisation moléculaire a permis d'identifier un mono-ammonium alkylé favorisant la formation de nanofeuillets de zéolithe ZSM-5 d'épaisseur voisine de 2 nm. L'étude cinétique a révélé par ailleurs que cette zéolithe est synthétisée à partir d’un polysilicate lamellaire formé in situ. Cette stratégie d'identification, couplée à une méthodologie d'expérimentation à haut débit, a alors été appliquée à la synthèse des zéolithes EMC-1 (FAU) et EMC-2 (EMT), et a conduit à l'élaboration de nouveaux agents structurants et composés bi-fonctionnels. / Zeolites are widely used in catalysis. One of today’s major challenges is to obtain nanometer-sized crystals, offering promising prospects for the design of more active and more selective acid catalysts, in particular for heavy oil conversion processes. Zeolite nanocrystals can be obtained by using growth inhibitors. This thesis focused on the identification of two families of organic compounds limiting the crystals growth. For the first one, the growth inhibition is favored by the adsorption of organic compounds (polycations, amino acids…) on the surface of growing crystals. This study was conducted using a high-throughput experiment methodology and led to zeolite Y (FAU) crystals of 300 nm by the addition of L-lysine. The second family is derived from Ryoo’s team approach and consists of the use of bifunctional compounds including one structure-directing function and one growth-inhibiting function. This study started with the synthesis of MFI zeolite. The molecular modelling allowed identifying an alkyl mono-ammonium directing the formation of 2 nm-thick nanosheets of zeolite ZSM-5. The kinetic study revealed that this zeolite is synthesized from a lamellar polysilicate formed in situ. This identification strategy, coupled to a high-troughput experiment methodology, was applied to the synthesis of zeolites EMC-1 (FAU) and EMC-2 (EMT) and conducted to the elaboration of new structure-directing agents and their bifunctional counterparts.

Quantum chemical calculations have been used to model dye-sensitized nanostructured titanium dioxide systems that can be used in solar cells for solar energy to electricity conversion. Structural, electronic and spectral properties of isolated dyes and both bare and dye-sensitized TiO2 have been calculated with density functional theory, providing detailed information about both the separate parts and the dye-TiO2 interface. The connection between the geometry, the ligand field splitting and the lifetime of the triplet metal-to-ligand charge transfer (MLCT) excited state has been explored for a series of ruthenium polypyridyl dyes. Moreover, the relative energetics of MLCT and metal centered triplet excited states have been studied for a number of such systems. It was found that small alterations of the polypyridyl ligands can result in significant changes in ligand field splitting and in the energetics of the triplet states. Attachment of the dyes to the TiO2 surface is achieved via anchor and spacer groups. The influence of such groups on various properties of the dye and their ability to act as mediators of photo-induced surface electron transfer has been studied. Delocalization of the lowest unoccupied dye orbital onto the spacer and/or anchor group indicates that certain unsaturated groups can mediate electron transfer. With a combination of methods that enables efficient computations and a scheme for construction of metal oxide clusters, chemical models for bare TiO2 nanocrystals in the 1-2 nm size range have been developed. The electronic structures show well-developed band structures with essentially no electronic band gap defect states. Atomistic models of the interface between TiO2 nanocrystals and Ru(II)-bis-terpyridine dyes, the so-called N3 dye as well as perylene dyes are reported. Electronic coupling strengths, which provide estimates for the electron injection times, are extracted from the interfacial electronic structure and the lowest electronic excitations are calculated.

This thesis presents an exploration of the photophysics of colloidal semiconductor nanocrystals using both linear and non-linear optical measurement techniques. These optical methodologies are used to follow population dynamics in both singly and multiply excited nanocrystal systems as well as determine material properties of the ensemble. Topics covered in the thesis include, the identification and characterization of bulk-like nanocrystals, study of the fine structure states of the lowest energy exciton, single and multiexciton population dynamics, acoustic phonon modes, elasticity and surface stress properties of a colloidal ensemble in solution.Through linear spectroscopy, the properties of both quantum confined and bulk-like colloidal semiconductor nanocrystals are compared. The identification of a model system of bulk-like nanocrystals with a non-standard absorption profile serves to resolve an ambiguity in literature concerning their characterization. The remainder of the thesis is focused on the size-dependent properties of quantum confined CdSe colloidal nanocrystals. The population dynamics and material properties of these systems are studied using a nonlinear optical technique called transient grating. A third order transient grating measurement with a cross-polarized configuration, which follows the relaxation within the fine structure levels of the lowest energy exciton state, is demonstrated and used to compare systems with different crystal field splittings. Transient grating experiments performed with specific polarization sequences allow for selective observation of the dynamics amongst nearly degenerate levels at room temperature. Cross-polarized transient grating is also used to observe a quantized acoustic phonon mode in a series of nanocrystal samples. The observation of this mode allows experimental determination of the elasticity and surface stress of the nanocrystal ensemble in solution. The anisotropic origin of the acoustic phonon is discussed using a combination of theoretical analysis, modelling and experimental data. In addition, third- and fifth-order transient grating experiments are used to study exciton and multiexciton population relaxation dynamics. The work presented here spans the optical and material properties of quantum confined and `bulk' nanocrystals. This thesis attempts to illustrate the broad scope of the observed behaviour of colloidal nanocrystal systems and to contribute to a greater understanding of their physical properties.

This thesis presents an exploration of the photophysics of colloidal semiconductor nanocrystals using both linear and non-linear optical measurement techniques. These optical methodologies are used to follow population dynamics in both singly and multiply excited nanocrystal systems as well as determine material properties of the ensemble. Topics covered in the thesis include, the identification and characterization of bulk-like nanocrystals, study of the fine structure states of the lowest energy exciton, single and multiexciton population dynamics, acoustic phonon modes, elasticity and surface stress properties of a colloidal ensemble in solution.Through linear spectroscopy, the properties of both quantum confined and bulk-like colloidal semiconductor nanocrystals are compared. The identification of a model system of bulk-like nanocrystals with a non-standard absorption profile serves to resolve an ambiguity in literature concerning their characterization. The remainder of the thesis is focused on the size-dependent properties of quantum confined CdSe colloidal nanocrystals. The population dynamics and material properties of these systems are studied using a nonlinear optical technique called transient grating. A third order transient grating measurement with a cross-polarized configuration, which follows the relaxation within the fine structure levels of the lowest energy exciton state, is demonstrated and used to compare systems with different crystal field splittings. Transient grating experiments performed with specific polarization sequences allow for selective observation of the dynamics amongst nearly degenerate levels at room temperature. Cross-polarized transient grating is also used to observe a quantized acoustic phonon mode in a series of nanocrystal samples. The observation of this mode allows experimental determination of the elasticity and surface stress of the nanocrystal ensemble in solution. The anisotropic origin of the acoustic phonon is discussed using a combination of theoretical analysis, modelling and experimental data. In addition, third- and fifth-order transient grating experiments are used to study exciton and multiexciton population relaxation dynamics. The work presented here spans the optical and material properties of quantum confined and `bulk' nanocrystals. This thesis attempts to illustrate the broad scope of the observed behaviour of colloidal nanocrystal systems and to contribute to a greater understanding of their physical properties.

There has been growing interest in developing colloidal metal and semiconductor nanocrystals as biomedical imaging contrast agents and therapeutics, since light excitation can cause the nanocrystals to fluoresce or heat up. Recent advances in synthetic chemistry produced fluorescent 2-4 nm diameter silicon and 1-2 nm diaemeter CuInSSe nanocrystals, as well as 16 nm diameter copper selenide (Cu₂₋[subscript x]Se) nanocrystals exhibiting strong absorbance of near infrared light suitable for biomedical applications. However, the syntheses yield nanocrystals that are stabilized by an adsorbed layer of hydrocarbons, making the nanocrystals hydrophobic and non-dispersible in aqueous solution. Encapsulating these nanocrystals in amphiphilic polymer micelles enables the nanocrystals to disperse in water. Subsequently, the Si nanocrystals were injected into tissue to demonstrate fluorescence imaging, the photothermal transduction efficiency of copper selenide nanocrystals was characterized in water, and the copper selenide nanocrystals were used enhance the photothermal destruction of cancer cells in vitro. The polymer-encapsulated copper selenide nanocrystals were found to have higher photothermal transduction efficiency than 140 nm diameter Au nanoshells, which have been widely investigated for photothermal therapy. Combining the optical properties of metal and semiconductor nanocrystals with the drug-carrying capability of lipid vesicles has received attention lately since it may create a nanomaterial capable of performing simultaneous drug delivery, optical contrast enhancement, and photo-induced therapy. Hydrophobic, dodecanethiol-coated Au nanocrystals were dispersed in water with phosphatidylcholine lipids and characterized using cryo transmission electron microscopy. 1.8 nm diameter Au nanocrystals completely load the bilayer of unsaturated lipid vesicles when the vesicles contain residual chloroform, and without chloroform the nanocrystals do not incorporate into the vesicle bilayer. 1.8 nm Au nanocrystals dispersed in water with saturated lipids to form lipid-coated nanocrystal agglomerates, which sometimes adhered to vesicles, and the shape of the agglomerates varied from linear nanocrystal chains, to flat sheets, to spherical clusters as the lipid fatty acid length was increased from 12 to 18 carbons. Including squalene formed lipid-stabilized emulsion droplets which were fully loaded with the Au nanocrystals. Results with 4.1 nm Au and 2-3 nm diameter Si nanocrystals were similar, but these nanocrystals could not completely load the bilayers of unsaturated lipids. / text

L’émergence de nouvelles souches bactériennes résistantes a signé la fin de l’« âge d’or » des antibiotiques. L’organisation mondiale de la santé a reconnu l’imminence des problèmes associés à ces nouvelles bactéries, qui engendrent de nouveau une mortalité en augmentation. Afin de palier à ce problème, de nouvelles alternatives aux antibiotiques sont envisagées par les chercheurs à travers le monde. La thérapie photodynamique antimicrobienne est l’une de ces alternatives. Elle a su se démarquer grâce à son incapacité à induire la résistance bactérienne. Alors que les résultats furent initialement très prometteurs contre les bactéries Gram positif, une moins bonne sensibilité fut rapidement observée de la part des bactéries Gram négatif. Afin d’augmenter le potentiel antibactérien de cette technique, diverses stratégies furent élaborées comme l’utilisation de photosensibilisateurs cationiques, l’ajout d’un agent de ciblage, ou la présence d’un agent de perméabilisation membranaire. L’un de ces agents est la polymyxine B, un peptide antimicrobien qui arbore une très bonne affinité avec les bactéries Gram négatif. Dans cette étude, nous avons voulu associer chimiquement différents photosensibilisateurs avec des dérivés de polymyxines B de façon covalente, par l’intermédiaire d’un bras « spacer » ou d’une plateforme. L’association de ces deux familles de molécules a permis d’élaborer de nouveaux composés qui ont démontré une activité photobactéricide accrue contre un large spectre de bactérie. De plus, ces composés ont montré une affinité augmentée pour les bactéries, ce qui permettra de réduire les effets secondaires sur les cellules humaines. Cette étude confirme l’importance d’utiliser des peptides antimicrobiens afin d’améliorer la thérapie photodynamique. Ces travaux seront approfondis afin de permettre la création de nouveaux traitements dermatologiques basées sur cette nouvelle thérapie et efficaces contre un large spectre de souche bactérienne / Despite advances achieved over the last decade, infections caused by multi-drug resistant bacterial strains are increasingly important societal issues that need to be addressed. New approaches have already been developed in order to overcome this problem. Photodynamic antimicrobial chemotherapy (PACT) could provide an alternative to fight infectious bacteria. Interesting results have been obtained against Gram-positive bacteria, but it also appeared that Gram-negative strains were less sensitive to PACT. Enhanced efficacy against Gram-negative bacteria had been previously obtained following three differents strategies, which are respectively the use of cationic photosensitizers, photosensitizers bound to antimicrobial peptides, or a membrane disrupting agent. Polymyxin B is an antimicrobial peptide, known as the “last-line” treatment against Gram-negative resistant strains, which has already been used as a disrupting agent in order to improve PACT. In addition of this enhancement, this peptide is known for its strong interaction for Gram-negative bacteria. Thus, in this work, we designed differents coumpounds, consisting of a photosensitizer covalently attached to derivatives of polymyxin B, through a spacer or a chemical platform. These combinations have led to the creation of novel compounds which have shown highly photobactericidal activities against a wide spectrum of bacteria. Moreover, these compounds present enhanced affinity for bacteria, which should significantly reduce side effects on mammalian cells. This study confirmed the importance of using antimicrobial in order to target bacterial strains. Thus, such results may allow the creation of novels PACT-based dermatological treatments efficient against a wide spectrum of bacterial strains.

In recent years bismuth-based, layer-structured perovskites such as SrBi2Nb2O9 (SBN) and SrBi2Ta2O9 (SBT) have been investigated extensively, because of their potential use in ferroelectric random access memories (FeRAMs). In comparison with non-layered perovskite ferroelectrics such as Pb(Zr,Ti)O3 (PZT), these offer several advantages such as fatigue free, lead free, low operating voltages and most importantly their ferroelectric properties are independent of film thickness in the 90 to 500 nm range. For FeRAM device applications, large remnant polarization (Pr), low coercive field (Ec) accompanied by high Curie temperature (Tc) are required for better performance and reliable operation. Much effort has been made to improve the ferroelectric properties of SBN and SBT ceramics by doping on A or B sites. It was known in the literature that partial substitution of Sr2+ by Bi3+ ions in SBN and SBT would increase the Curie temperature and improve the dielectric properties. The focus of the investigations that were taken up was to improve the electrical, dielectric and ferroelectric characteristics of SrBi2Nb2O9 ceramics. It was reported that the ferroelectric and nonlinear optical properties of LiNbO3 and LiTaO3 could be improved when vanadium, the lightest element in group V of the periodic table is substituted for Nb or Ta along with Li and three oxygens. It is with this background the investigations have been taken up to see whether one can extend the same argument to the Aurivillius family of oxides. Therefore, the central theme of the present investigations aimed at substituting Nb5+ by a smaller cation V5+ in SBN and study its influence on the formation temperature, sinterability, structural and microstructural characteristics apart from its physical properties. Recently the optical properties of this material have been recognized to be important from the optical device point of view. Unfortunately single crystal growth of vanadium doped SBN was hampered because of the bismuth and vanadium loss (high volatility) observed in the process of growth. One of the routes that attracted our attention has been the glass-ceramic. It would be interesting to visualize the behavior of crystallites of nano/micrometer size embedded in a glass matrix as these crystals were known to give rise to exotic properties. One of the crucial steps in the process of fabrication of a glass nanocrystalcomposite system in which crystalline phases have symmetries that would eventually give rise to basic non - centrosymmetric properties such as piezoelectric, pyroelectric and Pockels effects, has been to choose a compatible matrix material associated with easy glass forming capability and the ability to evenly disperse dipolar defects within itself. Recent investigations into strontium borate SrB4O7 (SBO), lithium borate Li2B4O7 (LBO) glasses indicated that LBO by virtue of its favorable structure, thermal and optical properties would form a suitable host glass matrix for dispersing layer structured ferroelectric oxides belonging to the Aurivillius family of oxides. Since lithium borate has wide transmission window, it was worth making an attempt to fabricate optical composite of Li2B4O7 (LBO) and vanadium doped SrBi2Nb2O9 (SBVN) and to study its structural, dielectric, pyroelectric, ferroelectric and optical properties. Therefore the present thesis reports detailed investigations into the effect of vanadium doping on the structural and various physical properties of an n = 2 member of the Aurivillius family of oxides in the polycrystalline form and novel glass composites comprising nano/microcrystallites of this phase. Chapter 1 comprises a brief introduction to the dielectric, pyroelectric, ferroelectric and nonlinear optical properties of materials. In addition to the principles and phenomena, the material aspects of these important branches of physics are discussed. It also forms a preamble to the glasses, criteria for glass formation, glass – ceramics and subsequently ferroelectric and nonlinear optical effects that were observed in glasses and glass - ceramics. Chapter 2 describes the material fabrication techniques adopted to prepare polycrystalline and grain – oriented ceramics, glasses and glass nanocrystalcomposites. The details of various structural, dielectric, pyroelectric, ferroelectric and optical measurement techniques employed to characterize these materials are also included. Chapter 3 discloses the fabrication of strontium bismuth niobate ceramics and their characterization for dielectric and impedance properties. The dielectric properties of strontium bismuth niobate ceramics have been modeled based on Jonscher’s Universal formalism. The coefficients of the Jonscher’s expression, exponent n(T) undergoes a minimum and A(T) exhibits a peak at the Curie temperature, Tc (723K). A strong low frequency dielectric dispersion (LFDD) associated with an impedance relaxation has been found to exist in these ceramics in the temperature range 573 - 823K. The Z′′ of the AC complex impedance showed two distinct slopes in the frequency range 100Hz-1MHz suggesting the existence of two dispersion mechanisms. The exponents m and n were obtained from the curve fitting. The exponent n was found to exhibit a minimum at the Curie temperature, Tc (723K) whereas the m was temperature independent. Chapter 4 deals with the fabrication of vanadium doped SrBi2Nb2O9 ceramics and their characterization for microstructural, dielectric, pyroelectric and ferroelectric properties. The average grain size of the SrBi2Nb2O9 (SBN) ceramic containing V2O5 was found to increase with increase in V2O5 content. The dielectric constant (εr) as well as the dielectric loss (D) increased with increase in grain size (6µm-17µm). The pyroelectric coefficient was found to be positive at 300K and showed an increasing trend with increasing grain size. Interestingly, the SrBi2(Nb0.7V0.3)2O9-δ ceramics consisting of 17µm sized grains showed higher remnant polarization (Pr) and lower coercive field (Ec) than those with grains of 7µm. Chapter 5 deals with the dielectric properties which were studied in detail in the 100Hz to 1MHz frequency range at various temperatures (300 – 823 K) for undoped and vanadium (10 mol%) doped SrBi2Nb2O9 (SBVN10) ferroelectric ceramics. A strong low frequency dielectric dispersion was encountered in these ceramics in the 573 – 823 K temperature range. The dielectric constants measured in the wide frequency and temperature ranges for both the samples were found to fit well to the Jonscher’s dielectric dispersion relations. The dielectric behavior of SBN and SBVN10 ceramics was rationalized using the impedance and modulus data. The electrical conductivity studies of layered SrBi2(Nb1-xVx)2O9-δ ceramics with x lying in the range 0 to 0.3 (30 mol%) were centered in the 573 – 823K temperature range as the Curie temperature lies in this range. The concentration of mobile charge carriers (n), the diffusion constant (D0) and the mean free path (a) were calculated using Rice and Roth formalism. The conductivity parameters such as ion hopping rate (ωp) and the charge carrier concentration (K′) term have been calculated using Almond and West formalism. The afore mentioned microscopic parameters were found to be V2O5 content dependent in SrBi2(Nb1-xVx)2O9-δceramics. Chapter 6 describes the fabrication of partially grain – oriented SrBi2(Nb1-xVx)2O9-δ (0 ≤x≤3.0 in molar ratio) ceramics and characterization for their structural, microstructural, dielectric, pyroelectric and ferroelectric properties. The grain – orientation factor and the microstructural features were studied by XRD and scanning electron microscopy as a fuction of sintering temperature and V2O5 content. The dielectric constant measured along the direction parallel and perpendicular to the pressing axis has shown a significant anisotropy. The pyroelectric and ferroelectric properties were superior in the direction perpendicular to the pressing axis (polar) to that in the parallel direction. The fabrication and characterization details of (100 – x) (Li2B4O7) – x (SrO - Bi2O3 - 0.7 Nb2O5 – 0.3 V2O5) (10 ≤ x ≤ 60, in molar ratio) glasses and glass nanocrystal composites are dealt within Chapter 7. The nanocrystallization of strontium bismuth niobate doped with vanadium (SrBi2(Nb0.7V0.3)2O9-δ(SBVN)) has been demonstrated in Li2B4O7 glasses. The glassy nature of the as – quenched samples was established by differential thermal analyses (DTA). The amorphous nature of the as – quenched glasses and crystallinity of glass nanocrystal composites were confirmed by X – ray powder diffraction studies. High resolution transmission electron microscopy (HRTEM) of the glass nanocrystal composites (heat – treated at 783K/6h) confirm the presence of nano rods of SBVN embedded in Li2B4O7 glass matrix. Chapter 8 presents the physical properties of the glasses and glass nanocrystal composites. Dielectric constant of both the as – quenched and glass nanocrystal composites was found to increase with increase in the composition, whereas the loss was observed to decrease with increasing SBVN composition. Different dielectric mixture formulae were employed to analyze the dielectric properties of the glass nanocrystal composite. The electrical behaviour of the glasses and glass nanocrystal composites was rationalized using impedance spectroscopy. The observed pyroelectric response and ferroelectric hysteresis of these composites confirmed the polar nature. Various optical parameters such as optical band gap (Eopt), Urbach energy (∆E), refractive index (n), optical dielectric constant (ε′∞) and ratio of carrier concentration to the effective mass (N/m*) were determined. The effects of composition of the glasses and glass nanocrystal composites on these parameters were studied. Transparent glasses embedded with nanocrystallites of SBVN exhibited intense second harmonic signals in transmission mode when exposed to IR laser light at λ = 1064 nm. The thesis ends with a summary of the important findings and conclusions.

No description available.

We proposed and demonstrated the first account of large-area, semi-transparent, tandem photosensitive nanocrystal skins (PNSs) constructed on flexible substrates operating on the principle of photogenerated potential buildup, which avoid the need for applying an external bias and circumvent the currentmatching limitation between junctions. We successfully fabricated and operated the tandem PNSs composed of single monolayers of colloidal water-soluble CdTe and CdHgTe nanocrystals (NCs) in adjacent junctions on a Kapton polymer tape. Owing to the usage of a single NC layer in each junction, noise generation was significantly reduced while keeping the resulting PNS films considerably transparent. In each junction, photogenerated excitons are dissociated at the interface of the semi-transparent Al electrode and the NC layer, with holes migrating to the contact electrode and electrons trapped in the NCs. As a result, the tandem PNSs lead to an open-circuit photovoltage buildup equal to the sum of those of the two single junctions, exhibiting a total voltage buildup of 128.4 mV at an excitation intensity of 75.8 μW cm⁻² at 350 nm. Furthermore, we showed that these flexible PNSs could be bent over 3.5 mm radius of curvature and cut out in arbitrary shapes without damaging the operation of individual parts and without introducing any significant loss in the total sensitivity. These findings indicate that the NC skins are promising as building blocks to make low-cost, flexible, large-area UV/visible sensing platforms with highly efficient full-spectrum conversion.

No description available.