The University of Southampton
University of Southampton Institutional Repository

The use of combinatorial chemical vapor deposition in the synthesis of Ti3-?O4N with 0.06 <? <0.25: a titanium oxynitride phase isostructural to anosovite

The use of combinatorial chemical vapor deposition in the synthesis of Ti3-?O4N with 0.06 <? <0.25: a titanium oxynitride phase isostructural to anosovite
The use of combinatorial chemical vapor deposition in the synthesis of Ti3-?O4N with 0.06 <? <0.25: a titanium oxynitride phase isostructural to anosovite
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, Ti(3-delta)O(4)N (where 0.06 < delta < 0.25), is the first example of a complex titanium oxynitride and was synthesized within composition graduated films formed from atmospheric pressure CVD of TiCl(4), NH(3), 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, beta-Ti(3)O(5). The lattice parameters are sensitive to composition, but were determined to be a = 3.8040(1) angstrom, b = 9.6486(6) angstrom, and c = 9.8688(5) angstrom for Ti(2.85(2))O(4)N. 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.
0002-7863
15541-15548
Hyett, Geoffrey
4f292fc9-2198-4b18-99b9-3c74e7dfed8d
Green, Mark A.
82f1a0d9-e9b2-4557-9259-98ab93471721
Parkin, Ivan P.
7f95b9c4-1f9d-441c-8d43-ac8ea2554b85
Hyett, Geoffrey
4f292fc9-2198-4b18-99b9-3c74e7dfed8d
Green, Mark A.
82f1a0d9-e9b2-4557-9259-98ab93471721
Parkin, Ivan P.
7f95b9c4-1f9d-441c-8d43-ac8ea2554b85

Hyett, Geoffrey, Green, Mark A. and Parkin, Ivan P. (2007) The use of combinatorial chemical vapor deposition in the synthesis of Ti3-?O4N with 0.06 <? <0.25: a titanium oxynitride phase isostructural to anosovite. Journal of the American Chemical Society, 129 (50), 15541-15548. (doi:10.1021/ja073355s).

Record type: Article

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, Ti(3-delta)O(4)N (where 0.06 < delta < 0.25), is the first example of a complex titanium oxynitride and was synthesized within composition graduated films formed from atmospheric pressure CVD of TiCl(4), NH(3), 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, beta-Ti(3)O(5). The lattice parameters are sensitive to composition, but were determined to be a = 3.8040(1) angstrom, b = 9.6486(6) angstrom, and c = 9.8688(5) angstrom for Ti(2.85(2))O(4)N. 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.

Full text not available from this repository.

More information

Published date: 19 December 2007
Organisations: Organic Chemistry: Synthesis, Catalysis and Flow, Chemistry, Faculty of Natural and Environmental Sciences

Identifiers

Local EPrints ID: 346971
URI: http://eprints.soton.ac.uk/id/eprint/346971
ISSN: 0002-7863
PURE UUID: 50215538-cb2d-4e6b-8ed1-601cd5171a54
ORCID for Geoffrey Hyett: ORCID iD orcid.org/0000-0001-9302-9723

Catalogue record

Date deposited: 12 Feb 2013 17:01
Last modified: 10 Dec 2019 01:36

Export record

Altmetrics

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton: eprints@soton.ac.uk

ePrints Soton supports OAI 2.0 with a base URL of http://eprints.soton.ac.uk/cgi/oai2

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.

×