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Electron Transfer from a Diamond (100) Surface to an Atmospheric Water Adlayer: A Quantum Mechanical Study
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Materials Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Materials Chemistry.
2007 (English)In: The Journal of Physical Chemistry C, ISSN 1932-7447, E-ISSN 1932-7455, Vol. 111, no 37, 13804-13812 p.Article in journal (Refereed) Published
Abstract [en]

The possibility of electron transfer from a H-terminated diamond (100) surface to an electrochemically reducible wetting adlayer, including species normally found in the atmosphere, has been studied theoretically using first-principles DFT methods. This type of electron-transfer process is one commonly assumed to be a prerequisite for induced p-type conductivity within the diamond surface. A partial electron transfer from the (2 × 1) reconstructed, H-terminated (100) surface to a water adlayer, including oxonium ions and molecular oxygen (or ozone), was observed. Both atomic charge calculations and frontier orbital overlap analyses were used in estimating the degree of electron transfer, and a strong coupling was observed between these two observables. A diamond surface with a pure water adlayer did not show any observable electron transfer, whereas the presence of oxonium ions showed a slightly improved degree of electron transfer (0.16 e-). However, the presence of molecular oxygen, as well as ozone, was found to result in a much larger degree of electron transfer (0.32 vs 0.43 e-), and a combination of oxonium ion and oxygen (or ozone) resulted in further improvements (0.65 vs 0.68 e-). For these various chemical water adlayer compositions, sheet carrier densities of 1013 cm-2 were found, which are in line with experimental data reported in the literature.

Place, publisher, year, edition, pages
2007. Vol. 111, no 37, 13804-13812 p.
National Category
Chemical Sciences
URN: urn:nbn:se:uu:diva-96590DOI: 10.1021/jp070565iISI: 000249501800025OAI: oai:DiVA.org:uu-96590DiVA: diva2:171216
Available from: 2007-12-18 Created: 2007-12-18 Last updated: 2011-01-22Bibliographically 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.
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 380
Inorganic chemistry, DFT, Diamond, High surface conductivity, Surface reactivity, c-BN, Oorganisk kemi
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
Available from: 2007-12-18 Created: 2007-12-18Bibliographically approved

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