Optical study of oriented double-Se₈-ring clusters and luminescent Se₂⁻ anions in LTA at extremely high selenium loading density
Poborchii, Vladimir V.; Petranovskii, Vitalii P.; Glukhov, Igor A.; Fotiadi, Andrei A. (2022-12-07)
Vladimir V. Poborchii, Vitalii P. Petranovskii, Igor A. Glukhov, Andrei A. Fotiadi, Optical study of oriented double-Se8-ring clusters and luminescent Se2− anions in LTA at extremely high selenium loading density, Microporous and Mesoporous Materials, Volume 348, 2023, 112395, ISSN 1387-1811, https://doi.org/10.1016/j.micromeso.2022.112395
© 2023 The Authors. Published by Elsevier Inc. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
https://creativecommons.org/licenses/by/4.0/
https://urn.fi/URN:NBN:fi-fe2023020826356
Tiivistelmä
Abstract
Recently, LTA-Se(1–8) samples with 1–8 Se atoms per cavity (simplified unit cell, large cavity + sodalite cage) obtained via adsorption at the temperature of ∼450 °C were reported. It was shown that single Se8 or single Se₁₂ ring are formed in the large LTA cavities, Se₈/Se₁₂ ring concentration ratio decreasing with an increase in the Se loading density. Contrary, in the present work, using Se vapour adsorption at ∼550 °C, we succeeded in encapsulation of ∼17 Se atoms per cavity (LTA-Se(17)) with a significant increase in the Se₈/Se₁₂ concentration ratio manifesting double Se₈-ring cluster formation in the most of the LTA large cavities, which is a step towards cluster crystal fabrication. According to our polarization/orientation Raman spectroscopic study of LTA-Se(17) single crystals, the orientations of the Se₈ and Se₁₂ appeared to be similar to those in previously investigated LTA-Se(1–8). Importantly, luminescent Se₂⁻ anions, oriented along the LTA 4-fold axes and located in the sodalite cages, are detected via Raman polarization/orientation dependencies of LTA-Se(17). Bright Se₂⁻ light emission with a maximum at ∼1.56 eV and vibronic structure is observed in the 1.3–1.8 eV spectral range. We show that the anions experience a compression in LTA which is slightly relaxing with a decrease in temperature producing an anomalous Raman band downshift. The compression of Se₂⁻ in LTA is weaker/stronger than that in sodalite/cancrinite, luminescence band photon energy depending on its strength. High concentration of regularly arranged Se₂⁻ in LTA suggests considering LTA-Se(17) as an important novel light-emitting material.
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