Gas-Phase Synthesis of Gold- and Silica-Coated Nanoparticles

Composite nanoparticles consisting of separate core-shell materials are of interest for a variety of biomedical and industrial applications. By combining different materials at the nanoscale, particles can exhibit enhanced or multi-functional behavior such as plasmon resonance combined with superparamagnetism. Gas-phase nanoparticle synthesis processes are promising because they can continuously produce particles with high mass-yield rates. In this dissertation, new methods are investigated for producing gas-phase coatings of nanoparticles in an "assembly-line" fashion. Separate processes are developed to create coatings from silica and gold that can be used with a variety of core-particle chemistries. A photoinduced chemical vapor deposition (photo-CVD) method is used to produce silica coatings from tetraethyl orthosilicate (TEOS) on the surface of nanoparticles (diameter ∼5--70 nm). Tandem differential mobility analysis (TDMA) of the process demonstrates that particle coatings can be produced with controllable thicknesses (∼1--10 nm) by varying system parameters such as precursor flow rate. Electron microscopy and infrared spectroscopy confirm that the photo-CVD films uniformly coat the particles and that the coatings are silica. In order to describe the coating process a chemical mechanism is proposed that includes gas-phase, surface and photochemical reactions. A chemical kinetics model of the mechanism indicates that photo-CVD coating proceeds primarily through the photodecomposition of TEOS which removes ethyl groups, thus creating activated TEOS species. The activated TEOS then adsorbs onto the surface of the particle where a series of subsequent reactions remove the remaining ethyl groups to produce a silica film with an open site for further attachment. The model results show good agreement with the experimentally measured coating trends, where increased TEOS flow increases coating thickness and increased nitrogen flow decreases coating thickness.;Gold decoration of nanoparticles is accomplished by evaporation of solid gold in the presence of an aerosol flow. A hot-wire generation method is developed where gold particles are produced from a composite gold-platinum wire. Investigations of the hot-wire generator show that it can produce particles with a range of sizes and that more uniform, non-agglomerated particles are produced when using smaller diameter tubes where gas velocities across the wire are higher and recirculation zones are diminished. When gold is evaporated in the presence of silica nanoparticles, the silica aerosol is decorated by gold through either homogeneous gold nucleation and subsequent scavenging by the silica nanoparticles, or by heterogeneous nucleation on the silica surface in which the gold "balls up" due to the high surface tension of gold on silica. In both cases the resulting particles exhibit a plasmon absorbance resonance typical of gold nanoparticles (lambda∼550 nm). Finally, the silica coating and gold decoration processes are combined with a thermal plasma technique for synthesizing iron-oxide to produce tri-layer nanoparticles.