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Sequential Thermal Decomposition of the Shell of Cubic ZnS/Zn(OH)2 Core–Shell Quantum Dots Observed With Mn2+ Probing Ions

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National Institute of Materials Physics, P.O. Box MG-7, Magurele-Ilfov, 077125 Romania
*Phone: 0040 213690185. Fax: 0040 213690177. E-mail: [email protected]
Cite this: J. Phys. Chem. C 2013, 117, 42, 22017–22028
Publication Date (Web):September 30, 2013
Copyright © 2013 American Chemical Society

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    Abstract Image

    Thermally induced changes in the structure and composition of the shell of tightly aggregated cubic ZnS/Zn(OH)2 core–shell quantum dots of 1.9 nm average core size were investigated by multifrequency electron paramagnetic resonance of Mn2+ probing ions. The observed three-steps temperature induced transformation of the Mn2+ surface centers in the 80–450 °C temperature range was attributed to the sequential decomposition by dehydration of the disordered ε-Zn(OH)2 shell into ZnO, with the formation of the Zn2O(OH)2 and Zn4O3(OH)2 intermediate nanocompounds. The presence of a 0.3 to 1.9 nm thick surface layer of disordered nanomaterial separating the cubic ZnS cores and its shrinking to a few atomic layers by mass loss after annealing up to 350 °C was observed by high resolution transmission electron microscopy. Unlike the single step dehydration around 120 °C of the bulk ε-Zn(OH)2, the complex decomposition of the ε-Zn(OH)2 shell is attributed to its nanosized, disordered structure.

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    Details of the sample preparations and pulse annealing procedure. Description of the spin Hamiltonian of the Mn2+ centers in cZnS QDs and of the EPR spectra analysis procedure. Sequences of EPR spectra of the cZnS:Mn2+ core QDs pulse annealed up to 500 °C in air and in vacuum. The XRD patterns of the cZnS/Zn(OH)2:Mn2+ core–shell and cZnS:Mn2+ core QDs, as-grown and pulse annealed at 500 °C in air and in vacuum. The results of the Rietveld analysis of the recorded XRD patterns. This material is available free of charge via the Internet at

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    Cited By

    This article is cited by 17 publications.

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    4. Ioana D. Vlaicu, Mariana Stefan, Cristian Radu, Daniela C. Culita, Dana Radu, Daniela Ghica. Atomic scale insight into the decomposition of nanocrystalline zinc hydroxynitrate toward ZnO using Mn2+ paramagnetic probes. Frontiers in Chemistry 2023, 11
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    8. Daniela Ghica, Ioana D. Vlaicu, Mariana Stefan, Valentin A. Maraloiu, Alexandra C. Joita, Corneliu Ghica. Tailoring the Dopant Distribution in ZnO:Mn Nanocrystals. Scientific Reports 2019, 9 (1)
    9. Mariana Stefan, Ioana Dorina Vlaicu, Leona Cristina Nistor, Daniela Ghica, Sergiu Vasile Nistor. Origin and chemical composition of the amorphous material from the intergrain pores of self-assembled cubic ZnS:Mn nanocrystals. Applied Surface Science 2017, 426 , 342-350.
    10. Mariana Stefan, Daniela Ghica, Sergiu V. Nistor, Adrian V. Maraloiu, Rodica Plugaru. Mn2+ ions distribution in doped sol–gel deposited ZnO films. Applied Surface Science 2017, 396 , 1880-1889.
    11. S.V. Nistor, M. Stefan, L.C. Nistor, D. Ghica, I.D. Vlaicu. Distribution and interaction of Mn2+ ions incorporated in cubic ZnS quantum dots over a broad concentration range. Journal of Alloys and Compounds 2016, 662 , 193-199.
    12. Daniela Ghica, Ioana D. Vlaicu, Mariana Stefan, Leona C. Nistor, Sergiu V. Nistor. On the agent role of Mn 2+ in redirecting the synthesis of Zn(OH) 2 towards nano-ZnO with variable morphology. RSC Advances 2016, 6 (108) , 106732-106741.
    13. Yiyu Li, Yiquan Wu. Spectroscopic characteristics of (Mn2+, Nd3+) co-doped zinc sulfide nanocrystals. Optical Materials 2015, 49 , 100-104.
    14. Guo-Liang Li, Shao-Yi Wu, Chang-Chun Ding, Xian-Fen Hu, Zhi-Hong Zhang. Studies on the spin Hamiltonian parameters for Mn 2+ in the ZnS nanocrystals and bulks. Molecular Physics 2014, 112 (24) , 3189-3194.
    15. S. V. Nistor, M. Stefan, D. Ghica. Pulse annealing electron paramagnetic resonance with probing transition ions. Journal of Thermal Analysis and Calorimetry 2014, 118 (2) , 1021-1031.
    16. Ekaterina A. Kozlova, Dina V. Markovskaya, Svetlana V. Cherepanova, Andrey A. Saraev, Eugeny Yu. Gerasimov, Timofey V. Perevalov, Vasily V. Kaichev, Valentin N. Parmon. Novel photocatalysts based on Cd1−Zn S/Zn(OH)2 for the hydrogen evolution from water solutions of ethanol. International Journal of Hydrogen Energy 2014, 39 (33) , 18758-18769.
    17. M. Stefan, S. V. Nistor, D. Ghica. ZnS and ZnO Semiconductor Nanoparticles Doped with Mn2+ Ions. Size Effects Investigated by EPR Spectroscopy. 2014, 3-27.

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