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Study of Mn ion charge state in Zn2TiO4 and its impact on the photoluminescence and optical absorption spectra

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Abstract

The Zn2TiO4 ceramics doped with manganese of nominal content from 0.0016 to 1.6 mol% were produced by a solid-state reaction and investigated by the X-ray diffraction, photoluminescence (PL), diffuse reflectance spectroscopy and electron paramagnetic resonance (EPR) methods. The influence of sintering conditions (annealing temperature in the range of 800–1200 °C and atmosphere, Mn concentration) on Mn charge state and red PL has been studied. All samples contained a spinel Zn2TiO4 crystal phase with a minor amount of ZnO. The ceramics showed a PL band peaked at 680 nm, which was ascribed to 2Eg → 4A2g transition of Mn4+Ti in the Zn2TiO4. The PL intensity increased with annealing temperature and Mn concentration. The highest PL intensity was found in the samples with 0.1 mol% Mn sintered at 1100 °C. In the EPR spectra, the signals ascribed to residual Cr3+ in the Zn2TiO4, Mn2+ in the ZnO (g = 2.0014, A = 74.1 × 10−4 cm−1, b20  = 235 × 10−4 сm−1) and Mn2+ in the Zn2TiO4 (g = 1.987, A = 74.510 × 10−4 сm−1, b20 = 45 × 10−4 сm−1) were detected. The intensity of EPR signal due to Mn2+ in the Zn2TiO4 increased noticeably in the samples with 1.0 mol% Mn and in those sintered at 1200 °C. This was accompanied by the decrease of Mn4+ PL intensity. It is concluded that manganese dopes the Zn2TiO4 as both Mn4+ and Mn2+, the Mn2+ incorporation is strongly promoted by high annealing temperature (> 1100 °C) and high Mn concentration (~ 1 mol%). It is proposed that optical absorption of Mn-doped Zn2TiO ceramics in the visible spectral range is determined by spin allowed transition of Mn4+Ti and Mn2+/3+ donor-type photoionization transition in the Zn2TiO4.

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Data availability

The datasets generated and analyzed during the current study are available from the corresponding author on reasonable request.

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Acknowledgements

The authors thank prof. J.-L. Doualan for the help in study of PL relaxation. The authors also thank all brave defenders of Ukraine who made finalizing this work possible.

Funding

This work was partly supported via bilateral program DNIPRO (project M/34-2020 in Ukraine and #42549TM in France) funded by the Ministry of Education and Research of Ukraine, the French Ministry of Higher Education, Research and Innovation and the Ministry for Europe and Foreign Affairs (MESRI-DAEI/MEAE).

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Authors and Affiliations

  1. V. Lashkaryov Institute of Semiconductor Physics of NASU, Pr. Nauky 41, Kyiv, 03028, Ukraine

    L. Borkovska, T. Stara, O. Gudymenko, K. Kozoriz, I. Vorona & V. Nosenko

  2. CIMAP, Normandie Univ, ENSICAEN, UNICAEN, CEA, CNRS, 6 Blvd. Maréchal Juin, 14050, Caen, France

    C. Labbe & J. Cardin

  3. Instituto Politécnico Nacional – ESFM, Av. IPN, Ed.9 U.P.A.L.M, 07738, Mexico City, Mexico

    T. Kryshtab

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  1. L. Borkovska
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Contributions

All authors contributed to the study conception and design. Synthesis of ceramic samples was performed by TS. Data collection and analysis of structural characteristics by X-ray diffraction were performed by OG and TK. Photoluminescence study of ceramic samples was carried out by TS, KK, CL and JC. EPR study of ceramic samples was performed by IV and the modeling of experimental EPR curves was carried out by VN. Diffuse reflectance study of ceramic samples was performed by KK. Analysis of the experimental results was carried out by LB, IV, VN, CL and JC. The first draft of the manuscript was written by LB and TK, all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.

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Correspondence to T. Kryshtab.

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The authors Lyudmyla Borkovska, Christophe Labbe and Julien Cardin have conducted their research under the French—Ukrainian Program PHC DNIPRO funded by French Ministry of Higher Education, Research and Innovation and the Ministry for Europe and Foreign Affairs (MESRI-DAEI/MEAE), Ministry of Education and Science of Ukraine.

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Borkovska, L., Stara, T., Gudymenko, O. et al. Study of Mn ion charge state in Zn2TiO4 and its impact on the photoluminescence and optical absorption spectra. J Mater Sci: Mater Electron 34, 999 (2023). https://doi.org/10.1007/s10854-023-10380-3

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