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First Preparation of Nanocrystalline Zinc Silicate by Chemical Vapor Synthesis Using an Organometallic Single‐Source Precursor
Author(s) -
Roy A.,
Polarz S.,
Rabe S.,
Rellinghaus B.,
Zähres H.,
Kruis F. E.,
Driess Matthias
Publication year - 2004
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200305397
Subject(s) - nanocrystalline material , amorphous solid , materials science , zinc , raman spectroscopy , crystallite , chemical engineering , crystallography , analytical chemistry (journal) , chemistry , nanotechnology , organic chemistry , metallurgy , physics , engineering , optics
A method is presented to prepare nanocrystalline α‐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 °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 °C contained particles with embedded nanocrystallites (3–5 nm) of β‐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 °C form α‐Zn 2 SiO 4 imbedded in amorphous SiO 2 . The crystallite sizes and primary particle sizes in the formed α‐Zn 2 SiO 4 were found to be below ∼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.