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Renaud A, Cario L, Rocquelfelte X, et al. Unravelling the origin of the giant Zn deficiency in wurtzite type ZnO nanoparticles. Sci Rep. 2015;5:12914doi: 10.1038/srep12914.
Renaud, A., Cario, L., Rocquelfelte, X., Deniard, P., Gautron, E., Faulques, E., Das, T., Cheviré, F., Tessier, F., & Jobic, S. (2015). Unravelling the origin of the giant Zn deficiency in wurtzite type ZnO nanoparticles. Scientific reports, 512914. https://doi.org/10.1038/srep12914
Renaud, Adèle, et al. "Unravelling the origin of the giant Zn deficiency in wurtzite type ZnO nanoparticles." Scientific reports vol. 5 (2015): 12914. doi: https://doi.org/10.1038/srep12914
Renaud A, Cario L, Rocquelfelte X, Deniard P, Gautron E, Faulques E, Das T, Cheviré F, Tessier F, Jobic S. Unravelling the origin of the giant Zn deficiency in wurtzite type ZnO nanoparticles. Sci Rep. 2015 Sep 03;5:12914. doi: 10.1038/srep12914. PMID: 26333510; PMCID: PMC4558607.
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Sci Rep. 2015 Sep 03;5:12914. doi: 10.1038/srep12914.

Unravelling the origin of the giant Zn deficiency in wurtzite type ZnO nanoparticles.

Scientific reports

Adèle Renaud, Laurent Cario, Xavier Rocquelfelte, Philippe Deniard, Eric Gautron, Eric Faulques, Tilak Das, François Cheviré, Franck Tessier, Stéphane Jobic

Affiliations

  1. Institut des Matériaux Jean Rouxel, Université de Nantes, CNRS, 2 rue de la Houssinière, 44322 Nantes cedex 3, France.
  2. Institut des Sciences Chimiques de Rennes, Université de Rennes 1, CNRS, 263 Avenue du General Leclerc, 35042 Rennes cedex, France.

PMID: 26333510 PMCID: PMC4558607 DOI: 10.1038/srep12914

Abstract

Owing to its high technological importance for optoelectronics, zinc oxide received much attention. In particular, the role of defects on its physical properties has been extensively studied as well as their thermodynamical stability. In particular, a large concentration of Zn vacancies in ZnO bulk materials is so far considered highly unstable. Here we report that the thermal decomposition of zinc peroxide produces wurtzite-type ZnO nanoparticles with an extraordinary large amount of zinc vacancies (>15%). These Zn vacancies segregate at the surface of the nanoparticles, as confirmed by ab initio calculations, to form a pseudo core-shell structure made of a dense ZnO sphere coated by a Zn free oxo-hydroxide mono layer. In others terms, oxygen terminated surfaces are privileged over zinc-terminated surfaces for passivation reasons what accounts for the Zn off-stoichiometry observed in ultra-fine powdered samples. Such Zn-deficient Zn1-xO nanoparticles exhibit an unprecedented photoluminescence signature suggesting that the core-shell-like edifice drastically influences the electronic structure of ZnO. This nanostructuration could be at the origin of the recent stabilisation of p-type charge carriers in nitrogen-doped ZnO nanoparticles.

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