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Hidden gapless states during thermal transformations of preorganized zinc alkoxides to zinc oxide nanocrystals

Abstract

Zinc oxide (ZnO) is one of the most versatile semiconductor material with multifarious potential applications. Easily accessible alkylzinc alkoxides have been widely exploited as single-source precursors of ZnO-based nanomaterials but their multi-step decomposition pathways have not been understood in detail. The formation mechanism of ZnO nanocrystals via solid-state thermal decomposition of a model pre-organised alkylzinc alkoxide precursor, i.e. [tBuZn(μ3-OtBu)]4, is elucidated using in situ valence-to-core X-ray emission (v2c-XES) and high energy resolution off-resonant spectroscopy (HEROS) in conjunction with theoretical calculations. These results indicate that homolytic cleavage of the R-Zn bond leads to the formation of a transient radical [•Zn(μ3-OR)][RZn(μ3-OR)]3 species which is responsible for the initial decomposition process, while the ensuing multistep transformations involve the formation of intermediate radical zinc oxo-alkoxide clusters with gapless electronic states. Hitherto, the formation of clusters of this type has not been considered neither as intermediate structures en-route to a semiconductor ZnO phase nor as potential species accounting for various defect states of ZnO NCs, particularly the singly charged oxygen vacancy, Vo+.

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Publication details

The article was received on 25 Jan 2018, accepted on 13 Jul 2018 and first published on 13 Jul 2018


Article type: Communication
DOI: 10.1039/C8MH00106E
Citation: Mater. Horiz., 2018, Accepted Manuscript
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    Hidden gapless states during thermal transformations of preorganized zinc alkoxides to zinc oxide nanocrystals

    J. Szlachetko, A. Kubas, A. M. Cieślak, K. Sokołowski, L. Makolski, J. Czapla-Masztafiak, J. Sa and J. Lewinski, Mater. Horiz., 2018, Accepted Manuscript , DOI: 10.1039/C8MH00106E

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