Synthesis and characterization of cyclotriphosphazenes containing silicon as single solid-state precursors for the formation of silicon/phosphorus nanostructured materials

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Inorg.Chem-revised.pdf(1.86 MB)
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Date
2008-11-01
Authors
Díaz, Carlos
Valenzuela, María Luisa
Bravo, Daniel
Lavayen, Vladimir
O'Dwyer, Colm
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American Chemical Society
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Abstract
The synthesis and characterization of new organosilicon derivatives of N3P3Cl6, N3P3[NH(CH2)3Si(OEt)3]6 (1), N3P3[NH(CH2)3Si(OEt)3]3[NCH3(CH2)3CN]3 (2), and N3P3[NH(CH2)3Si(OEt)3]3[HOC6H4(CH2)CN]3 (3) are reported. Pyrolysis of 1, 2, and 3 in air and at several temperatures results in nanostructured materials whose composition and morphology depend on the temperature of pyrolysis and the substituents of the phosphazenes ring. The products stem from the reaction of SiO2 with P2O5, leading to either crystalline Si5(PO4)6O, SiP2O7 or an amorphous phase as the glass Si5(PO4)6O/3SiO2·2P2O5, depending on the temperature and nature of the trimer precursors. From 1 at 800 °C, core−shell microspheres of SiO2 coated with Si5(PO4)6O are obtained, while in other cases, mesoporous or dense structures are observed. Atomic force microscopy examination after deposition of the materials on monocrystalline silicon wafers evidences morphology strongly dependent on the precursors. Isolated islands of size ∼9 nm are observed from 1, whereas dense nanostructures with a mean height of 13 nm are formed from 3. Brunauer−Emmett−Teller measurements show mesoporous materials with low surface areas. The proposed growth mechanism involves the formation of cross-linking structures and of vacancies by carbonization of the organic matter, where the silicon compounds nucleate. Thus, for the first time, unique silicon nanostructured materials are obtained from cyclic phosphazenes containing silicon.
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Phosphazene-organosilicon polymers , Structural characterization , Organometallic derivatives , Mesoporous silica , Nanoparticles
Citation
Diaz, C., Valenzuela, M. L., Bravo, D., Lavayen, V and O'Dwyer, C.(2008) 'Synthesis and characterization of cyclotriphosphazenes containing silicon as single solid-state precursors for the formation of silicon/phosphorus nanostructured materials', Inorganic Chemistry, 47(24), pp. 11561–11569. http://dx.doi.org/10.1021/ic8009805
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© 2008 American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/pdf/10.1021/ic8009805