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Origin of the reactivity on the nonterminated (100), (110), and (111) diamond surfaces: An electronic structure DFT study
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Materials Chemistry, Inorganic Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Materials Chemistry, Inorganic Chemistry.
2008 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, Vol. 112, no 37, 14367-14376 p.Article in journal (Refereed) Published
Abstract [en]

The reactivity of nonterminated diamond low-index surfaces has been evaluated using density functional theory (DFT). The intrinsic electronic structures of the topmost carbon atoms of diamond (100)-1 x 1, (100)-2 x 1, (110)-1 x 1, (111)-1 x 1, and (111)-2 x 1 surfaces have been calculated and analyzed using highly accurate numerical basis set first-principle techniques. The following reactivity indicators have been utilized: Fukui functions, electrostatic potential, and Kohn-Sham orbitals (highest occupied and lowest unoccupied). Their spatial representations have been mapped onto a charge density isosurface whereby plausible reactive sites were identified and related. Specifically, the change in chemically reactivity induced by a I x I to 2 x I surface reconstruction has been discussed. In addition, density of states and the deformation density of the topmost carbon atoms have been included. Most often the sites of electrophilically susceptible areas correspond to the mapping of f(-) function, electrostatic potential, and highest occupied molecular orbital. Conversely, nucleciphilic sites correspond to the f(+)-function and the lowest unoccupied molecular orbital. However, some discrepancies are found, and it seems that the Fukui functions yield more accurate results due to orbital relaxation effects taken into account. The results herein were furthermore compared to adsorption Studies of H-, O-, and OH-terminated diamond (100) and (I 11) surfaces, respectively. It was concluded that the reactivity of diamond surfaces can be evaluated by using DFT techniques, which will thereby make it possible to increase the knowledge about thin film growth mechanisms, Surface functionalization, and reconstructions.

Place, publisher, year, edition, pages
2008. Vol. 112, no 37, 14367-14376 p.
National Category
Inorganic Chemistry
Research subject
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-96591DOI: 10.1021/jp711190rISI: 000259140700026OAI: oai:DiVA.org:uu-96591DiVA: diva2:171217
Available from: 2007-12-18 Created: 2007-12-18 Last updated: 2009-08-31Bibliographically approved
In thesis
1. Surface Stabilization and Electrochemical Properties from a Theoretical Perspective
Open this publication in new window or tab >>Surface Stabilization and Electrochemical Properties from a Theoretical Perspective
2007 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Diamond and cubic boron nitride surfaces have extreme properties that can be exploited in novel tribological, electrochemical and electronic applications. Normally insulating diamond surfaces can exhibit high surface conductivities due to hydrogen termination and the nature of the surrounding atmosphere. Successful growth of cubic boron nitride thin films is hindered when harsh synthesis methods are used.

Three significant surface-related properties are addressed in this thesis using computational methods: (1) the structure, energy stability and reactivity of clean and differently terminated diamond surfaces, (2) the high surface conductivity of diamond, and (3) the adsorption-induced stability, reactivity and reconstruction of the cubic boron nitride (100) surface. Density Functional Theory (DFT) has been used at the GGA level under periodic boundary conditions to simulate the diamond and cubic boron nitride surfaces.

The diamond surface structures are shown to be insensitive to hydrogen desorption. Oxygen atoms bind in different positions and with different bond strengths. Hydroxyl groups experience both attractive hydrogen bonding and steric repulsions within the adsorbed species. The reconstruction of diamond (111)-1x1 is strongly dependent on the species adsorbed onto the surface. Electron transfer was observed from a diamond surface into a water-based adlayer, yielding a p-type doped surface, depending on the nature of the surface and the adlayer. The cubic boron nitride (100)-1x1 surface was shown to reconstruct into a 2x1 configuration on both the boron- and nitrogen-rich side through the formation of B-B bonds, as well as N–N dimer-induced surface relaxation. Hydrogen stabilized the (100)-1x1 surface, but the partial removal of hydrogen yielded non-reactive dimer formation on the surface.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2007. 71 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 380
Keyword
Inorganic chemistry, DFT, Diamond, High surface conductivity, Surface reactivity, c-BN, Oorganisk kemi
Identifiers
urn:nbn:se:uu:diva-8372 (URN)978-91-554-7059-3 (ISBN)
Public defence
2008-01-18, Häggsalen, Ångström Laboratory, Lägerhyddsvägen 1, 75121, Uppsala, 14:00
Opponent
Supervisors
Available from: 2007-12-18 Created: 2007-12-18Bibliographically approved

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