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

Ji, Haipeng; Ueda, Jumpei; Brik, Mikhail G.; Du, Mao-Hua; Chen, Deliang; Tanabe, Setsuhisa

doi:10.1039/c9cp04007b

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

Journal Article · 22 October 2019 · Physical Chemistry Chemical Physics. PCCP

DOI: https://doi.org/10.1039/c9cp04007b · OSTI ID:1607041

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Zhengzhou Univ. (China); Kyoto Univ. (Japan)
Kyoto Univ. (Japan)
Chongqing Univ. of Posts and Telecommunications (China); Univ. of Tartu (Estonia)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Zhengzhou Univ. (China)

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 O^2- → Mn⁴⁺ charge transfer transition. The splitting of the ZPL of the Mn^{4+ 2}E_g → ⁴A_2g 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 Mn^{4+ 2}E_g → ⁴A_2g luminescence exhibited severe thermal quenching, which was explained by the low-lying ⁴T_2g level and charge-transfer state.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1607041

Alternate ID(s):: OSTI ID: 1573269

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Vol. 21, Issue 45; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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