Issue 5, 2019

Graphene and novel graphitic ZnO and ZnS nanofilms: the energy landscape, non-stoichiometry and water dissociation

Abstract

The energy landscapes of ultra-thin nanofilms of ZnO and ZnS are examined in detail using periodic hybrid density functional calculations. We predict new staggered graphitic forms, which are stable only for the thinnest films and are of particular interest as the electronic structure shows a spontaneous symmetry breaking across the film and consequently a marked decrease in band gap with thickness. The relative energies of the various forms, their structural and electronic properties and their variation with film thickness are discussed. Possible kinetic pathways for transitions from the graphitic forms are examined by explicit evaluation of transition state energies. For polar surfaces, such as (0001) würtzite and (111) zinc blende, many different mechanisms operate to remove or reduce the surface dipole depending on the number of layers in the nanofilm. The polar ZnS nanofilms, but not the polar ZnO analogues or any non-polar film, are predicted to spontaneously become non-stoichiometric by loss of zinc atoms from the surface. The behaviour of adsorbed water on the ultra-thin films is also examined. There is no dissociation on any ZnS film. For ZnO, dissociation into OH and H+ takes place not only on (10[1 with combining macron]0) würtzite, but also on (110) zinc blende. This result that does not appear to have been reported previously and deserves future experimental study. While we concentrate on ZnO and ZnS, similar energy landscapes are expected for any oxide or sulphide which adopts the würtzite or zinc blende structure in the bulk.

Graphical abstract: Graphene and novel graphitic ZnO and ZnS nanofilms: the energy landscape, non-stoichiometry and water dissociation

Supplementary files

Article information

Article type
Paper
Submitted
20 авг 2018
Accepted
22 мар 2019
First published
01 апр 2019
This article is Open Access
Creative Commons BY license

Nanoscale Adv., 2019,1, 1924-1935

Graphene and novel graphitic ZnO and ZnS nanofilms: the energy landscape, non-stoichiometry and water dissociation

S. Conejeros, N. L. Allan, F. Claeyssens and J. N. Hart, Nanoscale Adv., 2019, 1, 1924 DOI: 10.1039/C8NA00155C

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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