Permanent magnets are used heavily for multiple applications in industry and current electronic technologies. However, the current permanent landscape is muddled by high cost of materials and insufficient magnetic or thermal properties. The primary focus of this dissertation work is the synthesis and optimization of a new permanent magnetic material, in the form of cobalt carbide nanomaterials. The optimization revolved around controlling the crystal phase and particle shape of synthesized cobalt carbide particles; these parameters have significant impact on the observed magnetic properties of magnetic nanoparticles. Co3C was identified to be the preferred crystal phase, leading to better magnetic properties. Cobalt Fumarate was found to be the ideal precursor to synthesize anisotropic Co3C particles and enhance magnetic properties of the synthesized cobalt carbide particles. Lastly, an ethanol based reduction system was employed to develop the greener synthesis of Co and Ni magnetic particles.

No description available.

L’étude et la réalisation de métamatériaux auto-assemblés possédant une réponse magnétique aux fréquences optiques font l’objet d’un champ de recherche très actif depuis plusieurs années. De nombreux calculs théoriques ont prédit qu’un arrangement dense de briques élémentaires plasmoniques, « les méta-atomes », conduirait à des matériaux à indice négatif actifs dans le domaine du visible. Il a été démontré qu’un nano-objet ayant un coeur de silice décoré de 12 nanoparticules d’or sphériques permettrait d’optimiser le phénomène de magnétisme optique. Ma thèse repose sur l’élaboration de ces objets à partir de particules colloïdales, parfaitement symétriques, constituées d’un coeur de silice et 12 nodules de polystyrène. Ces nodules de PS pouvant être éliminés ultérieurement par dissolution. Ces objets ont permis de fabriquer des particules de silices décorées d’un nombre précis de « patchs » ou de « fossettes ». Ces objets ont été formés en grande quantité. Nous sommes parvenus à rendre les cavités de surface des particules à fossettes collantes pour des germes d’or de 2-3 nm de diamètre et initier leur croissance. Les mesures de propriétés optiques de ces dodécapodes dorés ont reflété le couplage intense existant entre les nanoparticules plasmoniques autour du coeur diélectrique. La possibilité de faire croitre de l’argent à la surface des germes d’or permet de générer des nanorésonateurs avec des modes magnétiques optiques encore plus intenses que ceux observés pour les systèmes à base d’or. / Over the last decade, the field of self-assembled metamaterials exhibiting unusual properties such as a magnetic response in the visible range represents a challenging and attracting area. Many simulations reported that a dense arrangement of specific plasmonic sub-units called “meta-atoms”, may lead to a material with a negative refractive index. It was reported by computational modelling that a dodecapod clusters made of a central dielectric core and surrounded by a controlled number of satellites (12 satellites, here) with a specific size can exhibited some interesting properties. Here, the purpose was to fabricate such clusters from colloidal particles, which are perfectly symmetrical, made of a silica core and 12 polystyrene nodules. Subsequently, those polystyrene nodules can be dissolved to get silica particles with a specific number of “patches” or “dimples”. Those objects were synthesized in a large quantity. We were able to make those dimples sticky to tiny gold seed of 2-3 nm size and to grow then for a specific size. Optical measurements reported the strong magnetic coupling in-between the plasmonic nanoparticles around the dielectric core. We also reported that growing silver on tiny gold seeds generates stronger magnetic responses than those observed from gold clusters.

Synthesis of copper nanoparticles by a colloidal recipe in a two-phase liquid-liquid mixture (toluene/water) was investigated. The synthesis recipe used in this work was originally applied for the fabrication of alkylamine-capped gold nanoparticles. This method involves transferring metal cations from the aqueous layer to the organic one by the phase transfer reagent, tetraoctylammonium bromide, followed by reduction with sodium borohydride in the presence of oleylamine, which was used as the stabilising ligand. Several modifications were made to the original recipe to produce copper nanoparticles with high degrees of purity and stability. These particles are potentially applicable in various industries and are considered as an alternative for expensive metal nanoparticles, such as gold, silver, and platinum. Due to the high tendency of copper for oxidation, all of the synthesis experiments were carried out in a glove box under the flow of an inert gas (N2 or Ar). The concentration of Cl− was initially increased to form anionic complexes of copper that could later react with the cationic phase transfer reagent. This modification was followed to enhance the efficiency of the transferring step; however, the presence of anion, Cl−, at the surface of the synthesized particles was reported to change their properties; thus, increasing chloride concentration was eventually ignored. The decanting of two phases prior to the reduction step was also investigated to examine whether the site of the reduction reaction could be limited to cores of reverse micelles. The aggregated nanoparticles, which were fabricated by reducing the decanted organic phase, were heated after the synthesis at 150°C for 30 minutes to obtain a light green solution of nanoparticles. However, further characterization was not possible due to the hydrocarbon impurities. Dodecane, which was employed as the solvent for post-synthesis heating procedure, is believed to result in these impurities. Further investigation is required to explain the mechanism by which post-synthesis heating facilitates nanoparticle stabilization. Duplication of the original recipe for copper in an inert atmosphere resulted in a mixture of assembled layers of separated copper nanocrystals with an average size of ~ 5 nm and aggregated clusters of cubic copper (I) oxide nanoparticles. The possible mechanism for this division is believed to be the presence of the phase transfer reagent capped to the surface of a portion of synthesized particles leading to their metastability.

Synthesis of copper nanoparticles by a colloidal recipe in a two-phase liquid-liquid mixture (toluene/water) was investigated. The synthesis recipe used in this work was originally applied for the fabrication of alkylamine-capped gold nanoparticles. This method involves transferring metal cations from the aqueous layer to the organic one by the phase transfer reagent, tetraoctylammonium bromide, followed by reduction with sodium borohydride in the presence of oleylamine, which was used as the stabilising ligand. Several modifications were made to the original recipe to produce copper nanoparticles with high degrees of purity and stability. These particles are potentially applicable in various industries and are considered as an alternative for expensive metal nanoparticles, such as gold, silver, and platinum. Due to the high tendency of copper for oxidation, all of the synthesis experiments were carried out in a glove box under the flow of an inert gas (N2 or Ar). The concentration of Cl− was initially increased to form anionic complexes of copper that could later react with the cationic phase transfer reagent. This modification was followed to enhance the efficiency of the transferring step; however, the presence of anion, Cl−, at the surface of the synthesized particles was reported to change their properties; thus, increasing chloride concentration was eventually ignored. The decanting of two phases prior to the reduction step was also investigated to examine whether the site of the reduction reaction could be limited to cores of reverse micelles. The aggregated nanoparticles, which were fabricated by reducing the decanted organic phase, were heated after the synthesis at 150°C for 30 minutes to obtain a light green solution of nanoparticles. However, further characterization was not possible due to the hydrocarbon impurities. Dodecane, which was employed as the solvent for post-synthesis heating procedure, is believed to result in these impurities. Further investigation is required to explain the mechanism by which post-synthesis heating facilitates nanoparticle stabilization. Duplication of the original recipe for copper in an inert atmosphere resulted in a mixture of assembled layers of separated copper nanocrystals with an average size of ~ 5 nm and aggregated clusters of cubic copper (I) oxide nanoparticles. The possible mechanism for this division is believed to be the presence of the phase transfer reagent capped to the surface of a portion of synthesized particles leading to their metastability.

The work presented in this thesis reports the use of a series of novel thiobiuret metal complexes [M(SON(CNiPr2)2)n] (M = Cu, Ni, Fe, Zn, Cd or In; n = 2 or 3) for the first time as single source precursors for the colloidal synthesis of metal sulfide nanoparticles. Other single source precursor(s) were also used for the synthesis of CdSe, CdS, CdSe/CdS core/shell, CdSeS alloys and Cu2-xS nanoparticles in microfluidic reactors. Thermolysis experiments of [Cu(SON(CNiPr2)2)2] using only oleylamine produced Cu7S4 nanoparticles as a mixture of monoclinic and orthorhombic phases. Pure orthorhombic Cu7S4 nanoparticles were obtained when a solution of precursor in octadecene was injected into hot oleylamine whereas, Cu1.94S nanoparticles were obtained when a solution of the precursor in oleylamine was injected into hot dodecanethiol. The thermolysis of [Ni(SON(CNiPr2)2)2] gave Ni3S4 in all cases except when precursor solution in oleylamine was injected into hot octadecene which produced NiS nanoparticles. The thermolysis of [Fe(SON(CNiPr2)2)3] in oleylamine/oleylamine produced Fe7S8 nanoparticles but other combinations, in most cases, gave amorphous material. Thermolysis of [Zn(SON(CNiPr2)2)2] in oleylamine produced spherical ZnS nanoparticles. Particles with size smaller than 4.3 nm had a cubic phase, whereas the particles with size larger than 4.3 nm had a hexagonal crystal structure as suggested by the selected area electron diffraction. Powder X-Ray diffraction showed that the CdS nanoparticles obtained from the thermolysis of [Cd(SON(CNiPr2)2)2] in oleylamine were cubic under all reaction conditions except when dodecanethiol was used as an injection solvent which produced hexagonal CdS. β-In2S3 were synthesized from the thermolysis of [In(SON(CNiPr2)2)3]. Transmission electron microscopy showed that the copper, nickel and iron sulfide nanoparticles had various morphologies such as spherical, hexagonal disks, trigonal disks, rods or wires; depending on the reaction temperature, concentration of the precursor, the growth time and the solvent/capping agent combination. The zinc and cadmium sulfide nanoparticles were mostly spherical whereas the indium sulfide nanoparticles were produced in the form of ultra-thin (< 1.0 nm) nanorods or nanowires. ZnxCd1-xS and CuInS2 nanoparticles were synthesised from the 1,1,5,5-tetra-iso-propyl-4-thiobiureto complexes of Zn, Cd and Cu, In, respectively. Powder X-Ray diffraction showed that the obtained ZnxCd1-xS nanoparticles are cubic under all reaction conditions. The ZnxCd1-xS nanoparticles had an average diameter between 3.5 to 6.4 nm as shown by transmission electron microscopy. The optical properties of the ZnxCd1-xS nanoparticles were highly dependent on the ZnS to CdS precursor ratio and the solvents/capping agents. Chalcopyrite (tetragonal), wurtzite (hexagonal) or a mixture of both CuInS2 nanoparticles were obtained depending on the reaction conditions. TEM showed that the CuInS2 nanoparticles could be synthesised with different morphologies (spherical, hexagonal, trigonal or cone). Luminescent CuInS2 nanoparticles were obtained only in the absence of oleylamine. [Cd(S2CNMenHex)2], [Cd(Se2P(iPr)2)2] and [Cu(SON(CNiPr2)2)2] were used as single source precursor(s) for the synthesis of CdS, CdSe, CdSe/CdS core/shell, CdSeS alloys and Cu2-xS in microfludic reactor. The CdS nanoparticles were in size range of 5.0 to 8.0 nm whereas the CdSe nanoparticles were ultra small (ca. 2 nm) with blue luminescence. The CdSe/CdS core/shell and the CdSeS alloys were bluish green or green luminescent depending on their size. The copper sulfide nanoparticles were found to be monoclinic Cu7S4 or monoclinic Cu7S4 with minor impurities of rhombohedral Cu9S5 depending on the reaction conditions.

Doping in bulk semiconductors (e.g., n- or p- type doping in silicon) allows for precise control of their properties and forms the basis for the development of electronic and photovoltaic devices. Recently, there have been reports on the successful synthesis of doped semiconductor nanocrystals (or quantum dots) for potential applications in solar cells and spintronics. For example, nanocrystals of ZnSe (with zinc-blende lattice structure) and CdSe and ZnO (with wurtzite lattice structure) have been doped successfully with transition-metal (TM) elements (Mn, Co, or Ni). Despite the recent progress, however, the underlying mechanisms of doping in colloidal nanocrystals are not well understood. This thesis reports a comprehensive theoretical analysis toward a fundamental kinetic and thermodynamic understanding of doping in ZnO, CdSe, and ZnSe quantum dots based on first-principles density-functional theory (DFT) calculations. The theoretical predictions of this thesis are consistent with experimental measurements and provide fundamental interpretations for the experimental observations. The mechanisms of doping of colloidal ZnO nanocrystals with the TM elements Mn, Co, and Ni is investigated. The dopant atoms are found to have high binding energies for adsorption onto the Zn-vacancy site of the (0001) basal surface and the O-vacancy site of the (0001) basal surface of ZnO nanocrystals; therefore, these surface vacancies provide viable sites for substitutional doping, which is consistent with experimental measurements. However, the doping efficiencies are affected by the strong tendencies of the TM dopants to segregate at the nanocrystal surface facets, as indicated by the corresponding computed dopant surface segregation energy profiles. Furthermore, using the Mn doping of CdSe as a case study, the effect of nanocrystal size on doping efficiency is explored. It is shown that Mn adsorption onto small clusters of CdSe is characterized by high binding energies, which, in conjunction with the Mn surface segregation characteristics on CdSe nanocrystals, explains experimental reports of high doping efficiency for small-size CdSe clusters. In addition, this thesis presents a systematic analysis of TM doping in ZnSe nanocrystals. The analysis focuses on the adsorption and surface segregation of Mn dopants on ZnSe nanocrystal surface facets, as well as dopant-induced nanocrystal morphological transitions, and leads to a fundamental understanding of the underlying mechanisms of dopant incorporation into growing nanocrystals. Both surface kinetics (dopant adsorption onto the nanocrystal surface facets) and thermodynamics (dopant surface segregation) are found to have a significant effect on the doping efficiencies in ZnSe nanocrystals. The analysis also elucidates the important role in determining the doping efficiency of ZnSe nanocrystals played by the chemical potentials of the growth precursor species, which determine the surface structure and morphology of the nanocrystals.

No description available.

Doctor of Philosophy / Department of Chemistry / Viktor Chikan / This dissertation reports the colloidal synthesis of iron silicide, hafnium oxide core-gold shell and water soluble iron-gold alloy for the first time. As the first part of the experimentation, plasmonic and superparamagnetic nanoparticles of gold and iron are synthesized in the form of core-shell and alloy. The purpose of making these nanoparticles is that the core-shell and alloy nanoparticles exhibit enhanced properties and new functionality due to close proximity of two functionally different components. The synthesis of core-shell and alloy nanoparticles is of special interest for possible application towards magnetic hyperthermia, catalysis and drug delivery. The iron-gold core-shell nanoparticles prepared in the reverse micelles reflux in high boiling point solvent (diphenyl ether) in presence of oleic acid and oleyl amine results in the formation of monodisperse core-shell nanoparticles. The second part of the experimentation includes the preparation of water soluble iron-gold alloy nanoparticles. The alloy nanoparticles are prepared for the first time at relatively low temperature (110 oC). The use of hydrophilic ligand 3-mercapto-1-propane sulphonic acid ensures the aqueous solubility of the alloy nanoparticles. Next, hafnium oxide core-gold shell nanoparticles are prepared for the first time using high temperature reduction method. These nanoparticles are potentially important as a high κ material in semiconductor industry. Fourth, a new type of material called iron silicide is prepared in solution phase. The material has been prepared before but not in a colloidal solution. The Fe3Si obtained is superparamagnetic. Another phase β-FeSi2 is a low band gap (0.85 eV) semiconductor and is sustainable and environmentally friendly. At last, the iron monosilicide (FeSi) and β-FeSi2 are also prepared by heating iron-gold core-shell and alloy nanoparticles on silicon (111) substrate. The nucleation of gaseous silicon precursor on the melted nanoparticles results the formation of nanodomains of FeSi and β-FeSi2. A practical application of these nanoparticles is an important next step of this research. Further improvement in the synthesis of β-FeSi2 nanoparticles by colloidal synthetic approach and its application in solar cell is a future goal.

Le domaine des nanotechnologies représente la thématique de recherche la plus importante de ce début de 21ème siècle. L’enjeu, bien que apparemment simple est de taille : réaliser des objets ou des structures fonctionnelles, les plus petits possibles et ce de manière reproductible, i.e. en maîtrisant leur taille, leur position. S’inscrivant dans cette problématique, ce travail de thèse porte sur le développement d’une technique originale d’assemblage dirigé de nanostructures à partir de particules d’or et d’argent sous forme de nanofils, nanocristaux, nanoanneaux et nanodisques sur des substrats rigides. Cette technique s’appuie sur une méthode purement chimique reconnue et basée sur la réduction colloïdale in situ de sels métalliques sur une surface. L’organisation bi ou tridimensionnelle de ces nanoparticules métalliques est, de plus, induite par une préstructuration du substrat réalisée par le dépôt d’un film mince de copolymères diblocs. En effet, l’auto-assemblage de films minces de copolymère permet de réaliser, par micro-séparation de phase à la paroi, un réseau bidimensionnel hexagonal de cylindres verticaux. La suppression d’une des phases du système permet de générer alors un film organique nanoporeux organisé sur le substrat qui va servir de masque et permettre d’assembler des nanoparticules métalliques lors d’une seconde étape. L’initiation du dépôt de nanoparticules métalliques dans les pores du masque a été réalisée sous ultravide en épitaxie par jets moléculaires ou par voie colloïdale en solution. La croissance finale (complète) des cristaux métalliques d’argent a été poursuivie enfin par voie colloïdale en solution. Les propriétés spectroscopiques, de mouillage et électrochimiques des structures nanoparticulaires étudiées dans ce travail ont été directement corrélées aux morphologies cristallines de surface. Une des perspectives de ce travail préliminaire est el développement d’une plateforme MEMS générique pour la détection de traces de plusieurs types de molécules (volatiles et réfractaires) par voie électrochimique. / Nanotechnology became one of the most important research field of the 21st century. Though seemingly simple, the challenge is huge: achieving the formation of the smallest objects or functional structures (in a reproducible manner) and being able to control acurately their sizes and positions, as well. Answering these demands, this thesis deals with the development of a novel technique focusing on the directed growth and assembly of metallic nanostructures onto rigid substrates. First, the combination of phase separation of a block copolymer leading to the formation of nanopores, and gold nanocolloids synthesis confined in the nanoholes, has allowed the facile fabrication of hexagonally arranged gold nanoparticles onto silicon wafer. Then, the in situ reduction of colloidal silver salts has lead to the selective growth of metallic crystals onto the rigid prepatterned substrate. The control of both the physical parameters of the patterning and the chemical synthesis ones has induced the formation of various microstructures metallic morphologies ranging from nanowires, nanocrystals, nanorings and nanodisks. Spectroscopic properties, wetting and electrochemical these nanoparticles structures were finally investigated and directly correlated with crystal surface morphologies. One of the perspectives of this preliminary work is the development of a MEMS generic platform allowing the electrochemical detection of trace of molecules (volatile or refractory).