Ab initio study of the atomic level structure of the rutile TiO2 (110) – titanium nitride (TiN) interface

dc.check.date2018-09-22
dc.check.infoAccess to this article is restricted until 12 months after publication by request of the publisher.en
dc.contributor.authorGutiérrez Moreno, José Julio
dc.contributor.authorNolan, Michael
dc.contributor.funderEnvironmental Protection Agencyen
dc.contributor.funderPartnership for Advanced Computing in Europe AISBLen
dc.contributor.funderScience Foundation Irelanden
dc.contributor.funderHigher Education Authorityen
dc.contributor.funderDepartment of Jobs, Enterprise and Innovationen
dc.contributor.funderDepartment of Education and Skillsen
dc.date.accessioned2017-09-25T09:09:39Z
dc.date.available2017-09-25T09:09:39Z
dc.date.issued2017-09-22
dc.date.updated2017-09-25T08:46:47Z
dc.description.abstractTitanium nitride (TiN) is widely used in industry as a protective coating due to its hardness and resistance to corrosion and can spontaneously form a thin oxide layer when it is exposed to air, which could modify the properties of the coating. With limited understanding of the TiO2 – TiN interfacial system at present, this work aims to describe the structural and electronic properties of oxidized TiN based on a density functional theory (DFT) study of the rutile TiO2 (110) – TiN (100) interface model system, also including Hubbard +U correction on Ti 3d states. The small lattice mismatch gives a good stability to the TiO2 – TiN interface after depositing the oxide onto TiN through the formation of interfacial Ti – O bonds. Our DFT+U study shows the presence of Ti3+ cations in the TiO2 region, which are preferentially located next to the interface region as well as the rotation of the rutile TiO2 octahedra in the interface structure. Although the vacancy formation energies for Ti in TiN (Evac (Ti) ≥ 4.03 eV) or O in the oxide (Evac (O) ≥ 3.40 eV) are quite high relative to perfect TiO2 – TiN, defects are known to form during the oxide growth and can therefore be present after TiO2 formation. Our results show that a structure with exchanged O and N can lie 0.82 eV higher in energy than the perfect system, suggesting the stability of structures with interdiffused O and N anions at ambient conditions. The presence of N in TiO2 introduces N 2p states localized between the top edge of the O 2p valence states and the mid-gap Ti3+ 3d states, thus reducing the bandgap in the TiO2 region for the exchanged O/N interface EDOS. The outcomes of these simulations give us a most comprehensive insight on the atomic level structure and the electronic properties of oxidised TiN surfaces.en
dc.description.sponsorshipEnvironmental Protection Agency (UisceSense project W-2015-MS-21);en
dc.description.statusPeer revieweden
dc.description.versionAccepted Versionen
dc.format.mimetypeapplication/pdfen
dc.identifier.citationGutiérrez Moreno, J. J. and Nolan, M. (2017) 'Ab initio study of the atomic level structure of the rutile TiO2 (110) – titanium nitride (TiN) interface', ACS Applied Materials and Interfaces, 2017(9), pp. 38089-38100. doi:10.1021/acsami.7b08840en
dc.identifier.doi10.1021/acsami.7b08840
dc.identifier.endpage38100
dc.identifier.issn1944-8244
dc.identifier.issued9
dc.identifier.journaltitleACS Applied Materials and Interfacesen
dc.identifier.startpage38089
dc.identifier.urihttps://hdl.handle.net/10468/4779
dc.identifier.volume2017
dc.language.isoenen
dc.publisherAmerican Chemical Societyen
dc.relation.projectinfo:eu-repo/grantAgreement/SFI/SFI Infrastructural Support/04/HEC/I584s4/IE/General Supplement to Irish Centre for High End Computing/en
dc.rights© 2017, American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Applied Materials and Interfaces, © 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/abs/10.1021/acsami.7b08840en
dc.subjectTiO2en
dc.subjectTiNen
dc.subjectInterfaceen
dc.subjectDefectsen
dc.subjectBiofoulingen
dc.titleAb initio study of the atomic level structure of the rutile TiO2 (110) – titanium nitride (TiN) interfaceen
dc.typeArticle (peer-reviewed)en
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