Beyond the energy gap law: the influence of selection rules and bost compound effects on nonradiative transition rates in Boltzmann thermometers

  • Apart from the energy gap law, control parameters over nonradiative transitions are so far only scarcely regarded. In this work, the impact of both covalence of the lanthanoid–ligand bond and varying bond distance on the magnitude of the intrinsic nonradiative decay rate between the excited 6P5/2 and 6P7/2 spin–orbit levels of Gd3+ is investigated in the chemically related compounds Y2[B2(SO4)6] and LaBO3. Analysis of the temperature-dependent luminescence spectra reveals that the intrinsic nonradiative transition rates between the excited 6PJ (  J = 5/2, 7/2) levels are of the order of only 10 ms−1 (Y2[B2(SO4)6]:Gd3+: 8.9 ms−1; LaBO3:Gd3+: 10.5 ms−1) and differ due to the different degree of covalence of the GdO bonds in the two compounds. Comparison to the established luminescent Boltzmann thermometer Er3+ reveals, however, that the nonradiative transition rates between the excited levels of Gd3+ are over three orders of magnitude slower despite a similar energy gap and the presenceApart from the energy gap law, control parameters over nonradiative transitions are so far only scarcely regarded. In this work, the impact of both covalence of the lanthanoid–ligand bond and varying bond distance on the magnitude of the intrinsic nonradiative decay rate between the excited 6P5/2 and 6P7/2 spin–orbit levels of Gd3+ is investigated in the chemically related compounds Y2[B2(SO4)6] and LaBO3. Analysis of the temperature-dependent luminescence spectra reveals that the intrinsic nonradiative transition rates between the excited 6PJ (  J = 5/2, 7/2) levels are of the order of only 10 ms−1 (Y2[B2(SO4)6]:Gd3+: 8.9 ms−1; LaBO3:Gd3+: 10.5 ms−1) and differ due to the different degree of covalence of the GdO bonds in the two compounds. Comparison to the established luminescent Boltzmann thermometer Er3+ reveals, however, that the nonradiative transition rates between the excited levels of Gd3+ are over three orders of magnitude slower despite a similar energy gap and the presence of a single resonant phonon mode. This hints to a fundamental magnetic dipolar character of the nonradiative coupling in Gd3+. These findings can pave a way to control nonradiative transition rates and how to tune the dynamic range of luminescent Boltzmann thermometers.show moreshow less

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Metadaten
Author:Philip Netzsch, Matthias HämmerORCiD, Erich Turgunbajew, Thomas P. van Swieten, Andries Meijerink, Henning A. HöppeORCiDGND, Markus Suta
URN:urn:nbn:de:bvb:384-opus4-947414
Frontdoor URLhttps://opus.bibliothek.uni-augsburg.de/opus4/94741
ISSN:2195-1071OPAC
Parent Title (English):Advanced Optical Materials
Publisher:Wiley
Place of publication:Weinheim
Type:Article
Language:English
Year of first Publication:2022
Publishing Institution:Universität Augsburg
Release Date:2022/04/26
Tag:Atomic and Molecular Physics, and Optics; Electronic, Optical and Magnetic Materials
Volume:10
Issue:11
First Page:2200059
DOI:https://doi.org/10.1002/adom.202200059
Institutes:Mathematisch-Naturwissenschaftlich-Technische Fakultät
Mathematisch-Naturwissenschaftlich-Technische Fakultät / Institut für Physik
Mathematisch-Naturwissenschaftlich-Technische Fakultät / Institut für Physik / Lehrstuhl für Festkörperchemie
Dewey Decimal Classification:5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften
Licence (German):CC-BY-NC-ND 4.0: Creative Commons: Namensnennung - Nicht kommerziell - Keine Bearbeitung (mit Print on Demand)