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Structural, optical, and electronic properties of non-stoichiometric nano-ZnS1−x: Mnx

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Abstract

Non-stoichiometric ZnS1−x:Mnx nanomaterials were prepared using a thermolysis procedure by decreasing the stoichiometric amount of thiourea relative to the amount of zinc acetate as starting precursors: Zn(Ac)/(1−x) thiourea in the presence of (x) manganese acetate (x = 0, 0.01, 0.03, 0.05, and 0.1). Rietveld X-ray diffraction analysis was used to examine the structural modification in the ZnS lattice induced by sulfur deficiency and Mn2+ incorporation. The samples with x ≤ 0.01 exhibited a single ZnS zincblende phase, while other samples, x ≥ 0.02, have two phases ZnS and ZnO with different percentages. The lattice parameter of the system is governed by the Mn and S amounts in the matrix. A high-resolution transmission electron microscope established the quantum dot nature of the system. Fourier-transform infrared technique confirmed the presence of ZnS and ZnO phases in higher Mn-doped ZnS samples. The bandgap obtained from UV–vis analysis showed non-monotonic dependence on Mn content; it initially decreased and then increased to form a bandgap “bowing.” Photoluminescence analysis revealed that the emission colors depended on the amount of Mn doping in the matrix. The PL intensity raised for all Mn-doped samples as compared with the pristine sample reached its maximum value for the 3% and 5% Mn samples. The PL exhibited a red shift for the high dopant amount of Mn. Density function theory calculation was used to explore the electronic and optical characteristics of pure phases in ZnS1−xMnx system.

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Acknowledgements

The authors are grateful to the Deanship of Scientific Research, King Saud University for funding through Vice Deanship of Scientific Research Chairs.

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Authors and Affiliations

  1. Physics Department, Faculty of Science, Ain Shams University, Cairo, Egypt

    Zein K. Heiba, Mohamed Bakr Mohamed & S. I. Ahmed

  2. Physics Department, Faculty of Science, Taibah University, Al‑Madina al Munawarah, Saudi Arabia

    Mohamed Bakr Mohamed

  3. Physics Department, Faculty of Science, Taif University, Taif, 21974, Saudi Arabia

    S. I. Ahmed

  4. Research Chair of Exploitation of Renewable Energy Applications in Saudi Arabia, Physics and Astronomy Department, College of Science, King Saud University, P.O. Box 2455, Riyadh, 11451, Saudi Arabia

    A. A. Albassam

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  1. Zein K. Heiba
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  2. Mohamed Bakr Mohamed
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Heiba, Z.K., Mohamed, M.B., Ahmed, S.I. et al. Structural, optical, and electronic properties of non-stoichiometric nano-ZnS1−x: Mnx. J Mater Sci: Mater Electron 31, 13447–13459 (2020). https://doi.org/10.1007/s10854-020-03898-3

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