The preparation of thin mixed-metal alloy films by the chemical vapor deposition of heteronuclear organo-transition metal complexes; the development of chemical approaches to zinc-sulfide powders, gels, and fiber

The research in Part 1 of this study demonstrates the general utility of organo-transition metal complexes as precursors for chemical vapor deposition, CVD, processes. Uniform films of iron and cobalt alloys, FeCo$sb{rm x}$ where x = 1-3, transition metal complexes, HFeCo$sb3$(CO)$sb{12}$ and CpFeCo(CO)$sb6$, (Cp = cyclopentadienyl). These adherent thin films are amorphous or polycrystalline, with a smooth granular surface. The metal ratio of the films reflects the metal ratios in the starting organo-transition metal precursor complexes. Chemical analyses show that only trace impurities of carbon and oxygen are present in the films. Film thickness can be controlled as a function of deposition time, and reasonable film thicknesses on the order of 1.0 $mu$m can be obtained. The FeCo$sb3$ alloy films exhibit unusual ferromagnetic behavior such that $musb{rm s a t}$ = 4.26.;These FeCo$sb{rm x}$ alloy films can be oxidized to form FeCo$sb{rm x}$O$sb{rm y}$ films during deposition or post-treatment. These red-orange films are also uniform and adherent, with a metal ratio reflecting that of the organometallic precursor. Electron microprobe analysis indicates the presence of Fe$sp{+3}$ and Co$sp{+2}$ oxides.;The goal of the research in Part 2 of this study is to design solution chemistry routes to ZnS ceramic powders, gels, fibers, and whiskers. The results presented herein demonstrate that general chemistry routes for preparing ZnS ceramics based on the reactions of (EtZn(SBu$sp{rm t}$)) $sb5$ with H$sb2$S and ZnEt$sb2$ with (BzS)$sb2$S are possible. Powders derived from both routes have similar size distributions in the 0.0075-0.0600 $mu$m range, with an average particle size of 0.0150-0.0200 $mu$m.;The stoichiometric reaction of (EtZn(SBu$sp{rm t}$)) $sb5$ with H$sb2$S in toluene at 80$spcirc$C gives angstrom size fibers as well as powders. With excess H$sb2$S, there is some evidence for fiber formation, but powder morphologies predominate. When an excess of H$sb2$S reacts with (EtZn(SBu$sp{rm t}$)) $sb5$ in dichloromethane solution at room temperature, a powdered product is formed which is converted to single crystal whiskers during heat treatment with H$sb2$S. ZnEt$sb2$ reacts with a stoichiometric amount of (BzS)$sb2$S to give fine powders, but forms gels with an excess of (BzS)S. All products are characterized as ZnS based on transmission electron microscopy TEM, selected area diffraction SAD, electron diffraction, and x-ray powder diffraction XRD. The formation of these products is proposed to be related to the nature of the polymeric species actually found in solution.