title: First preparation of nanocrystalline zinc silicate by chemical vapor synthesis using an organometallic single-source precursor.
abstract: A method is presented to prepare nanocrystalline alpha-Zn(2)SiO(4) with the smallest crystal size reported so far for this system. Our approach combines the advantages of organometallic single-source precursor routes with aerosol processing techniques. The chemical design of the precursor enables the preferential formation of pure zinc silicates. Since gas-phase synthesis reduces intermolecular processes, and keeps the particles small, zinc silicate was synthesized from the volatile organometallic precursor [[MeZnOSiMe(3)](4)], possessing a Zn-methyl- and O-silyl-substituted Zn(4)O(4)-heterocubane framework (cubane), under oxidizing conditions, using the chemical vapor synthesis (CVS) method. The products obtained under different process conditions and their structural evolution after sintering were investigated by using various analytical techniques (powder X-ray diffraction, transmission electron microscopy, EDX analysis, solid-state NMR, IR, Raman, and UV/Vis spectroscopy). The deposited aerosol obtained first (processing temperature 750 degrees C) was amorphous, and contained agglomerates with primary particles of 12 nm in size. These primary particles can be described by a [Zn-O-Si] phase without long-range order. The deposit obtained at 900 degrees C contained particles with embedded nanocrystallites (3-5 nm) of beta-Zn(2)SiO(4), Zn(1.7)SiO(4), and ZnO in an amorphous matrix. On further ageing, the as-deposited particles obtained at 900 degrees C form alpha-Zn(2)SiO(4) imbedded in amorphous SiO(2). The crystallite sizes and primary particle sizes in the formed alpha-Zn(2)SiO(4) were found to be below approximately 50 nm and mainly spherical in morphology. A gas-phase mechanism for the particle formation is proposed. In addition, the solid-state reactions of the same precursor were studied in detail to investigate the fundamental differences between a gas-phase and a solid-state synthesis route.
authors.affiliation: Process and Aerosol Measurement Technology, Department of Electrical Engineering and Information Technology, University Duisburg-Essen, 47057 Duisburg, Germany.
authors.forename: A
authors.initials: A
authors.lastname: Roy
authors.forename: S
authors.initials: S
authors.lastname: Polarz
authors.forename: S
authors.initials: S
authors.lastname: Rabe
authors.forename: B
authors.initials: B
authors.lastname: Rellinghaus
authors.forename: H
authors.initials: H
authors.lastname: Zähres
authors.forename: F E
authors.initials: FE
authors.lastname: Kruis
authors.forename: Matthias
authors.initials: M
authors.lastname: Driess
mesh_terms: D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010316:Particle Size; D017640:Silicates / Q000138:chemical synthesis*; D013696:Temperature; D017967:Zinc Compounds / Q000138:chemical synthesis*
chemical_list: D009942:Organometallic Compounds; D017640:Silicates; D017967:Zinc Compounds; C029500:zinc silicate