Structural variation and near infrared luminescence in Mn5+-doped M2SiO4 (M = Ba, Sr, ca) phosphors by cation substitution

Zhang, Xiaowen; Nie, Jianmin; Liu, Shanshan; Qiu, Jianrong

doi:10.1007/s10854-018-8622-2

Cited by 10 publications

(5 citation statements)

References 30 publications

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“…However, at the D point chemical potential condition with lower μ D , higher μ C and higher μ A , and rich-O limit Δμ O = 0, the defect concentration of Mn tet 5+ can be high, just slightly lower than the dominant Mn oct 4+ in all of the three hosts (see the detailed Formation energy-versus-Fermi energy diagrams in Figure S2 of the Supporting Information). The emission of Mn tet 5+ is expected to be quite sharp at ∼1.1 eV, as reported in many other ternary oxides with high-valent cation sites and alkaline earth orthosilicates containing Mn 5+ …”

Section: Resultssupporting

confidence: 70%

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Elucidating the Multisite and Multivalence Nature of Mn Ions in Solids and Predicting Their Optical Transition Properties: A Case Study on a Series of Garnet Hosts

et al. 2022

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The abundant site occupancy and optical transitions of multivalence Mn dopants in luminescent materials have attracted much attention. Here, detailed first-principles calculations based on density functional theory have been carried out to clarify the multisite and multivalence nature of Mn ions in solids and predict their optical transition properties by using garnets as prototype systems. The formation energies of dodecahedral, octahedral, and tetrahedral coordinated Mn dopants are evaluated with chemical potential environments, and the preferable site occupancy and valence state of Mn ions in three garnet systems are clarified. The results show that even in a fixed atmosphere, taking Ca3Al2Ge3O12 in air as an example, not only can the preference of Mn ions switch between dodecahedral and octahedral sites, but also can the valence state change from Mn2+ to Mn3+ and Mn4+. Furthermore, for all of the three garnet systems, the calculation results of the energy-level structure and photoluminescence of Mn ions at different sites in the different valence states provide a reliable interpretation of the available spectroscopic data. The proposed first-principles scheme, with general applicability and encouraging predictive power, provides an effective approach for elucidating and characterizing the site occupancy, valence state, and optical transition of Mn activators in insulators, and will greatly benefit the design and optimization of related materials.

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Section: Resultssupporting

confidence: 70%

“…The emission of Mn tet 5+ is expected to be quite sharp at ∼1.1 eV, as reported in many other ternary oxides with high-valent cation sites and alkaline earth orthosilicates containing Mn 5+ . 46 3.2. Calibration of the Octahedral Mn 2+ Emissions.…”

Section: Formation Energies Of Mn Activators In Thementioning

confidence: 99%

Elucidating the Multisite and Multivalence Nature of Mn Ions in Solids and Predicting Their Optical Transition Properties: A Case Study on a Series of Garnet Hosts

et al. 2022

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“…17 Mn 3+ ions in solids show strong Jahn-Teller distortion and unique luminescence properties, such as temperature-dependent red to NIR luminescence and the quenching of photoluminescence. [18][19][20] Mn 4+ ions usually occupy octahedral coordinated sites and emit (deep) red light, 21,22 and Mn 5+ ions usually enter tetrahedral coordinated sites and emit NIR light, 23,24 while the luminescence from Mn 6+ has been rarely observed. [25][26][27] It is important to elucidate and regulate the site occupancy and valence states of Mn ions acting as important optical centers in solids and predict their optical transitions for the purpose of materials design and optimization.…”

Section: Introductionmentioning

confidence: 99%

“…17 Mn 3+ ions in solids show strong Jahn–Teller distortion and unique luminescence properties, such as temperature-dependent red to NIR luminescence and the quenching of photoluminescence. 18–20 Mn 4+ ions usually occupy octahedral coordinated sites and emit (deep) red light, 21,22 and Mn 5+ ions usually enter tetrahedral coordinated sites and emit NIR light, 23,24 while the luminescence from Mn 6+ has been rarely observed. 25–27…”

Section: Introductionmentioning

confidence: 99%

Mechanistic insights for regulating the site occupancy, valence states and optical transitions of Mn ions in yttrium–aluminum garnets via codoping

Chen¹,

Liu²,

Ma³

et al. 2023

Phys. Chem. Chem. Phys.

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“…Tetrahedrally coordinated Mn 5+ is known to produce a narrow emission spectrum of approximately 1000–1400 nm; however, its stabilization via solid-state reaction is challenging. The basic optical properties of Mn 5+ have all been studied for solid-state laser, luminescence thermometry, and bioimaging applications. − Unfortunately, detailed structural investigations of Mn 5+ luminescence are scarce, and the luminescence mechanism is not well understood. Liao et al studied room temperature (RT) photoluminescence (PL) in garnet-type structured Ca 14 Zn 6 Ga 10 O 35 exhibiting combined Mn 4+ and Mn 5+ emission, but without a detailed structure–property understanding.…”

mentioning

confidence: 99%

Pentavalent Manganese Luminescence: Designing Narrow-Band Near-Infrared Light-Emitting Diodes as Next-Generation Compact Light Sources

et al. 2022

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Manganese in the pentavalent state (Mn 5+ ) is both rare and central in materials exhibiting narrow-band nearinfrared (NIR) emission and is highly sought after for phosphorconverted light-emitting diodes as promising candidates for future miniature solid-state NIR light source. We develop the Ca 14 Zn 6 Ga 10−x Mn x O 35 (x = 0.3, 0.5, 1.0, 1.25, 1.5, and 3.0) series that exhibit simultaneous Mn 4+ (650−750 nm) and Mn 5+ (1100−1250 nm) luminescence. We reveal a preferential occupancy of Mn in regular octahedral and tetrahedral environments, with the short bond length between these responsible for luminescence. We present a theoretical spin− orbital interaction model in which breaking the spin selection rule permits the luminescence of Mn 4+ and Mn 5+ . A total photon flux of 87.5 mW under a 7 mA driving current demonstrates its potential for real-time application. This work pushes our understanding of achieving Mn 5+ luminescence and opens the way for the design of Mn 5+ -based narrow-band NIR phosphors.

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Structural variation and near infrared luminescence in Mn5+-doped M2SiO4 (M = Ba, Sr, ca) phosphors by cation substitution

Cited by 10 publications

References 30 publications

Elucidating the Multisite and Multivalence Nature of Mn Ions in Solids and Predicting Their Optical Transition Properties: A Case Study on a Series of Garnet Hosts

Elucidating the Multisite and Multivalence Nature of Mn Ions in Solids and Predicting Their Optical Transition Properties: A Case Study on a Series of Garnet Hosts

Mechanistic insights for regulating the site occupancy, valence states and optical transitions of Mn ions in yttrium–aluminum garnets via codoping

Pentavalent Manganese Luminescence: Designing Narrow-Band Near-Infrared Light-Emitting Diodes as Next-Generation Compact Light Sources

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