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Title: Intense deep-red zero phonon line emission of Mn4+ in double perovskite La4Ti3O12

Abstract

Phosphors that emit in the deep-red spectral region are critical for plant cultivation light-emitting diodes. In this work, ultrabroadband deep-red luminescence of Mn4+ in La4Ti3O12 was studied, which showed intense zero phonon line emission. The double-perovskite structural La4Ti3O12 simultaneously contains two Ti4+ sites forming slightly- and highly-distorted TiO6 octahedra, respectively. The influence of octahedral distortion on the Mn4+ emission energy in the two distinct Ti4+ sites was studied both experimentally and theoretically. The spectral measurements indicated that Mn4+ in La4Ti3O12 showed intense zero phonon line emission (ZPL) at deep-red 710–740 nm under excitation of 400 nm charging the O2- → Mn4+ charge transfer transition. The splitting of the ZPL of the Mn4+ 2Eg4A2g transition as well as the intensity of ZPL relative to the vibronic phonon sideband emissions were found to be greatly influenced by the degree of octahedral distortion. The crystal-field strength and Racah parameters of Mn4+ in each Ti4+ site were also estimated. The Mn4+ 2Eg4A2g luminescence exhibited severe thermal quenching, which was explained by the low-lying 4T2g level and charge-transfer state.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [2]
  1. Zhengzhou Univ. (China); Kyoto Univ. (Japan)
  2. Kyoto Univ. (Japan)
  3. Chongqing Univ. of Posts and Telecommunications (China); Univ. of Tartu (Estonia)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  5. Zhengzhou Univ. (China)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1607041
Alternate Identifier(s):
OSTI ID: 1573269
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 21; Journal Issue: 45; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Mn4+; luminescence; double perovskite; titanate

Citation Formats

Ji, Haipeng, Ueda, Jumpei, Brik, Mikhail G., Du, Mao-Hua, Chen, Deliang, and Tanabe, Setsuhisa. Intense deep-red zero phonon line emission of Mn4+ in double perovskite La4Ti3O12. United States: N. p., 2019. Web. https://doi.org/10.1039/c9cp04007b.
Ji, Haipeng, Ueda, Jumpei, Brik, Mikhail G., Du, Mao-Hua, Chen, Deliang, & Tanabe, Setsuhisa. Intense deep-red zero phonon line emission of Mn4+ in double perovskite La4Ti3O12. United States. https://doi.org/10.1039/c9cp04007b
Ji, Haipeng, Ueda, Jumpei, Brik, Mikhail G., Du, Mao-Hua, Chen, Deliang, and Tanabe, Setsuhisa. Tue . "Intense deep-red zero phonon line emission of Mn4+ in double perovskite La4Ti3O12". United States. https://doi.org/10.1039/c9cp04007b. https://www.osti.gov/servlets/purl/1607041.
@article{osti_1607041,
title = {Intense deep-red zero phonon line emission of Mn4+ in double perovskite La4Ti3O12},
author = {Ji, Haipeng and Ueda, Jumpei and Brik, Mikhail G. and Du, Mao-Hua and Chen, Deliang and Tanabe, Setsuhisa},
abstractNote = {Phosphors that emit in the deep-red spectral region are critical for plant cultivation light-emitting diodes. In this work, ultrabroadband deep-red luminescence of Mn4+ in La4Ti3O12 was studied, which showed intense zero phonon line emission. The double-perovskite structural La4Ti3O12 simultaneously contains two Ti4+ sites forming slightly- and highly-distorted TiO6 octahedra, respectively. The influence of octahedral distortion on the Mn4+ emission energy in the two distinct Ti4+ sites was studied both experimentally and theoretically. The spectral measurements indicated that Mn4+ in La4Ti3O12 showed intense zero phonon line emission (ZPL) at deep-red 710–740 nm under excitation of 400 nm charging the O2- → Mn4+ charge transfer transition. The splitting of the ZPL of the Mn4+ 2Eg → 4A2g transition as well as the intensity of ZPL relative to the vibronic phonon sideband emissions were found to be greatly influenced by the degree of octahedral distortion. The crystal-field strength and Racah parameters of Mn4+ in each Ti4+ site were also estimated. The Mn4+ 2Eg → 4A2g luminescence exhibited severe thermal quenching, which was explained by the low-lying 4T2g level and charge-transfer state.},
doi = {10.1039/c9cp04007b},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 45,
volume = 21,
place = {United States},
year = {2019},
month = {10}
}

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Figures / Tables:

Figure 1 Figure 1: XRD pattern of the as-prepared La4(Ti2.998Mn0.002)O12 (the insert shows digital image of the sample). The reference pattern (No. 01-074-2661) of La4Ti3O12 was also given.

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