Article Cationic pair substitution in LaAlO3:Mn4+ for octahedral-tilting-dependent zero-phonon line

Siyuan Li ; Chenyu Zhang ; Qi Zhu ; Ji-Guang Li SAMURAI ORCID (National Institute for Materials ScienceROR)

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Siyuan Li, Chenyu Zhang, Qi Zhu, Ji-Guang Li. Cationic pair substitution in LaAlO3:Mn4+ for octahedral-tilting-dependent zero-phonon line. Inorganic Chemistry Frontiers. 2022, 10 (2), 638-650. https://doi.org/10.48505/nims.4340
SAMURAI

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(abstract)

Novel La1-xBaxAl1-xTixO3:0.001Mn4+ (LBAT:0.001Mn4+, x=0-0.2) and La1-yYyAl1-yGayO3:0.001Mn4+ (LYAG:0.001Mn4+, y=0-0.2) samples were successfully synthesized through a high-temperature solid-state reaction, and tunable ZPL of Mn4+ was found by cationic pair substitution of Ba2+-Ti4+ and Y3+-Ga3+ for
La3+-Al3+ in LaAlO3:Mn4+. The ZPL intensity is related to the local symmetry around Mn4+ and the ZPL energy corresponds to the Mn-O bond distance and the O-Mn-O bond distortion. Through co-doping Ba2+-Ti4+, the ZPL at 710 nm is enhanced and the intensity increases continuously with increasing the x value, due to the local symmetric degree of Mn4+ decreases slowly. However, the Y3+-Ga3+ co-doping induces linear and quick increase of the intensity of ZPL at 704 nm with increasing y value, due to the local symmetric degree of Mn4+ decreases quickly. The octahedral tilting distortion is very important for the local symmetry. Ba2+-Ti4+ co-doping reduces octahedral tilting distortion, but Y3+-Ga3+ co-doping induces a serious
octahedral tilting distortion. Consequently, the ZPL emission exhibits an octahedral-tilting dependent behavior. Mainly due to the larger distortion of O-Mn-O bond, the energy of ZPL for LYAG:0.001Mn4+ is higher than that for LBAT:0.001Mn4+. The outcomes of this work provide a promising way to regulate
the ZPL intensity and energy by tuning the local structure around Mn4+, and they may have wide implication for Mn4+-doped phosphors and solid state lighting.

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Keyword: LaAlO3, Mn4+ luminescence, Cation pair substitution, Zero phonon line

Date published: 2022-11-28

Publisher: Royal Society of Chemistry (RSC)

Journal:

  • Inorganic Chemistry Frontiers (ISSN: 20521553) vol. 10 issue. 2 p. 638-650

Funding:

Manuscript type: Author's version (Accepted manuscript)

MDR DOI: https://doi.org/10.48505/nims.4340

First published URL: https://doi.org/10.1039/d2qi01683d

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Updated at: 2024-01-15 13:34:38 +0900

Published on MDR: 2024-01-15 17:16:09 +0900

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