The use of combinatorial chemical vapor deposition in the synthesis of Ti3-δO4N with 0.06 < δ < 0.25: A titanium oxynitride phase isostructural to anosovite

Hyett, G. and Green, M.A. and Parkin, I.P. (2007) The use of combinatorial chemical vapor deposition in the synthesis of Ti3-δO4N with 0.06 < δ < 0.25: A titanium oxynitride phase isostructural to anosovite. Journal of the American Chemical Society, 129 (50). pp. 15541-15548. ISSN 0002-7863. (doi:https://doi.org/10.1021/ja073355s) (The full text of this publication is not currently available from this repository. You may be able to access a copy if URLs are provided)

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Official URL
http://dx.doi.org/10.1021/ja073355s

Abstract

We employ, for the first time, a unique combinatorial chemical vapor deposition (CVD) technique to isolate a previously unreported transition-metal mixed-anion phase. The new oxynitride phase, Ti3-δO 4N (where 0.06 &lt; δ &lt; 0.25), is the first example of a complex titanium oxynitride and was synthesized within composition graduated films formed from atmospheric pressure CVD of TiCl4, NH3, and ethyl acetate. Characterization was performed by X-ray diffraction, X-ray photoelectron spectroscopy, UV-visible spectra, and SQUID magnetometry. The material crystallizes in the Cmcm space group, with the ordered nitrogen ions stabilizing the orthorhombic analogue of the monoclinic anosovite structure, β-Ti3O5. The lattice parameters are sensitive to composition, but were determined to be a = 3.8040(1) �, b = 9.6486(6) �, and c = 9.8688(5) � for Ti2.85(2)O4N. Powder samples were prepared through delamination of the thin films for synchrotron X-ray diffraction and magnetic measurements. It is the first example of a new phase to be synthesized using such a combinatorial CVD approach and clearly demonstrates how such techniques can provide access to new materials. This metastable phase with unusual nitrogen geometry has proved to be elusive to conventional solid-state chemistry techniques and highlights the value of the surface growth mechanism present in CVD. Furthermore, the ease and speed of the synthesis technique, combined with rapid routes to characterization, allow for large areas of phase space to be probed effectively. These results may have major implications in the search for new complex mixed-anion phases in the future. © 2007 American Chemical Society.

Item Type: Article
Additional information: Unmapped bibliographic data: LA - English [Field not mapped to EPrints] J2 - J. Am. Chem. Soc. [Field not mapped to EPrints] AD - Christopher Ingold Laboratory, University College London, 20 Gordon Street, London, WC1H 0AJ, United Kingdom [Field not mapped to EPrints] AD - NIST Center for Neutron Research, National Institute of Standards and Technology, 100 Bureau Drive, Gaithersburg, MD 20899-8563, United States [Field not mapped to EPrints] DB - Scopus [Field not mapped to EPrints]
Uncontrolled keywords: Ethyl acetate, Solid-state chemistry, Surface growth, Titanium oxynitride, Chemical vapor deposition, Metastable phases, SQUIDs, Synthesis (chemical), X ray diffraction, X ray photoelectron spectroscopy, Titanium compounds, anion, anosovite, metal complex, nitrogen derivative, oxygen derivative, titanium derivative, unclassified drug, article, atmospheric pressure, chemical composition, chemical structure, combinatorial chemistry, complex formation, crystallization, film, growth, magnetism, measurement, parameter, solid state, synchrotron, synthesis, technique, ultraviolet spectroscopy, vapor, X ray diffraction, X ray photoelectron spectroscopy
Subjects: Q Science > QC Physics > QC173.45 Condensed Matter
Q Science > QD Chemistry > QD478 Solid State Chemistry
Divisions: Faculties > Sciences > School of Physical Sciences > Functional Materials Group
Depositing User: Giles Tarver
Date Deposited: 15 Oct 2015 11:06 UTC
Last Modified: 16 Oct 2015 10:58 UTC
Resource URI: https://kar.kent.ac.uk/id/eprint/51017 (The current URI for this page, for reference purposes)
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