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Evaluation of the Segregation of Paramagnetic Impurities at Grain Boundaries in Nanostructured ZnO Films

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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: ACS Appl. Mater. Interfaces 2014, 6, 16, 14231–14238
Publication Date (Web):August 4, 2014
Copyright © 2014 American Chemical Society

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    Abstract Image

    Magnetic and electrical properties of the nanostructured ZnO films are affected by the nonrandom distribution of impurities in the film due to segregation at grain boundaries (GBs) or extended defects. However, mapping the nature and distribution of the impurities in the film is not trivial. Here we demonstrate a simple, statistically relevant, and nondestructive procedure of quantitative determination of the paramagnetic impurities segregated at the GBs in nanostructured semiconducting and insulating films. From correlated electron paramagnetic resonance and transmission electron microscopy investigations, we determined the localization of trace amounts of Mn2+ ions, present as native impurities in a ZnO film deposited by magnetron sputtering at room temperature. In the as-deposited ZnO film, the Mn2+ ions were all localized in nanosized pockets of highly disordered ZnO dispersed between nanocrystalline columns. After the samples had been annealed in air at >400 °C, the size of the intercrystalline region decreased and the diffusion in GBs was activated, resulting in the localization of a portion of the Mn2+ ions in the peripheral atomic layers of the ZnO columns neighboring the GBs. The proportion of Mn2+ ions still localized at the GBs after annealing at 600 °C was 37%. The proposed method for the assessment of the presence and nature of impurities and the quantitative evaluation of their distribution in semiconducting and insulating nanostructures is expected to find direct applications in nanotechnology, in the synthesis and quality assurance of thin films for spintronics and opto- and nanoelectronics.

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    Details about the thin film deposition procedure and characterization methods, analysis of EPR spectra, and a table of EPR spectral parameters of the Mn centers in various ZnO structures. This material is available free of charge via the Internet at

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    Cited By

    This article is cited by 9 publications.

    1. Pushpendra Singh, Ranveer Kumar, Rajan Kumar Singh. Progress on Transition Metal-Doped ZnO Nanoparticles and Its Application. Industrial & Engineering Chemistry Research 2019, 58 (37) , 17130-17163.
    2. Chitra Bhukkal, Bindiya Goswami, Rachna Ahlawat. Identification of Different Phases and Thermal Analysis of Mn Doped Cadmium Oxide Nano-rods. 2022, 221-230.
    3. 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)
    4. Simona Somacescu, Corneliu Ghica, Cristian E. Simion, Andrei C. Kuncser, Aurel M. Vlaicu, Mariana Stefan, Daniela Ghica, Ovidiu G. Florea, Ionel F. Mercioniu, Adelina Stanoiu. Nanoclustered Pd decorated nanocrystalline Zn doped SnO2 for ppb NO2 detection at low temperature. Sensors and Actuators B: Chemical 2019, 294 , 148-156.
    5. I. Zgura, N. Preda, G. Socol, C. Ghica, D. Ghica, M. Enculescu, I. Negut, L. Nedelcu, L. Frunza, C.P. Ganea, S. Frunza. Wet chemical synthesis of ZnO-CdS composites and their photocatalytic activity. Materials Research Bulletin 2018, 99 , 174-181.
    6. 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.
    7. 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.
    8. Berat Yüksel Price, Gökhan Hardal, Muhammed Açıkgöz, Sergej Repp, Emre Erdem. Effects of MnO doping on the electronic properties of zinc oxide: 406 GHz electron paramagnetic resonance spectroscopy and Newman superposition model analysis. Journal of Applied Physics 2015, 118 (17)
    9. J. Perrière, C. Hebert, M. Nistor, E. Millon, J. J. Ganem, N. Jedrecy. Zn 1−x Fe x O films: from transparent Fe-diluted ZnO wurtzite to magnetic Zn-diluted Fe 3 O 4 spinel. Journal of Materials Chemistry C 2015, 3 (42) , 11239-11249.

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