Understanding the quenching nature of Mn4+ in wide band gap inorganic compounds: Design principles for Mn4+ phosphors with higher efficiency

Lei Wang, Zhaoxiang Dai, Rulong Zhou, Bingyan Qu, Xiao Cheng Zeng

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Mn4+ doped phosphors, as an alternative to rare-earth element doped phosphors, have attracted immense attention owing to their ultrahigh quantum efficiency of red emission for potential applications in high rendering white LEDs (light-emitting diodes). Their performance can be largely affected by quenching phenomena such as thermal quenching, concentration quenching and the quenching induced by some intrinsic/extrinsic defects. However, the quenching mechanisms due to the defect levels and host band are still incompletely understood. In this work, we carry out a comprehensive first-principles study on the underlying quenching mechanisms due to the defect levels of Mn4+ and other extrinsic/intrinsic defects, using the prototype oxide Y3Al5O12 (YAG), fluorides K2TiF6 (KTF) and ZnTiF6·6H2O (ZTF) as examples. From the comparison of the defect levels of Mn4+ with the host bands, we find that it is the very small energy difference between the defect levels of Mn4+ and the valence bands maximum (VBM) of YAG that causes the lower luminescence thermal stability of YAG:Mn4+, which we name as the hole-type thermal quenching mechanism. For the concentration quenching, it is nearly impossible for the Mn4+-Mn4+ pairs, previously considered as the main quenching centers, to appear in phosphors. A new quenching nature has been discussed. For the impurity ionic effects, the hole-type defects can largely stabilize the Mn ions in +4 states, thereby enhancing the emission intensity. These proposed mechanisms can offer deeper insights into the luminescence behavior of Mn4+ and a better practical understanding of the high photoluminescence quantum yield red phosphors by adjusting their chemical components.

Original languageEnglish (US)
Pages (from-to)16992-16999
Number of pages8
JournalPhysical Chemistry Chemical Physics
Volume20
Issue number25
DOIs
StatePublished - Jan 1 2018

Fingerprint

Inorganic compounds
inorganic compounds
Phosphors
phosphors
Quenching
Energy gap
quenching
broadband
Defects
defects
yttrium-aluminum garnet
Luminescence
luminescence
Quantum yield
Valence bands
Rare earth elements
Quantum efficiency
Fluorides
Oxides
Light emitting diodes

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Understanding the quenching nature of Mn4+ in wide band gap inorganic compounds : Design principles for Mn4+ phosphors with higher efficiency. / Wang, Lei; Dai, Zhaoxiang; Zhou, Rulong; Qu, Bingyan; Zeng, Xiao Cheng.

In: Physical Chemistry Chemical Physics, Vol. 20, No. 25, 01.01.2018, p. 16992-16999.

Research output: Contribution to journalArticle

@article{12c1d117ce904885bb38be12449e559d,
title = "Understanding the quenching nature of Mn4+ in wide band gap inorganic compounds: Design principles for Mn4+ phosphors with higher efficiency",
abstract = "Mn4+ doped phosphors, as an alternative to rare-earth element doped phosphors, have attracted immense attention owing to their ultrahigh quantum efficiency of red emission for potential applications in high rendering white LEDs (light-emitting diodes). Their performance can be largely affected by quenching phenomena such as thermal quenching, concentration quenching and the quenching induced by some intrinsic/extrinsic defects. However, the quenching mechanisms due to the defect levels and host band are still incompletely understood. In this work, we carry out a comprehensive first-principles study on the underlying quenching mechanisms due to the defect levels of Mn4+ and other extrinsic/intrinsic defects, using the prototype oxide Y3Al5O12 (YAG), fluorides K2TiF6 (KTF) and ZnTiF6·6H2O (ZTF) as examples. From the comparison of the defect levels of Mn4+ with the host bands, we find that it is the very small energy difference between the defect levels of Mn4+ and the valence bands maximum (VBM) of YAG that causes the lower luminescence thermal stability of YAG:Mn4+, which we name as the hole-type thermal quenching mechanism. For the concentration quenching, it is nearly impossible for the Mn4+-Mn4+ pairs, previously considered as the main quenching centers, to appear in phosphors. A new quenching nature has been discussed. For the impurity ionic effects, the hole-type defects can largely stabilize the Mn ions in +4 states, thereby enhancing the emission intensity. These proposed mechanisms can offer deeper insights into the luminescence behavior of Mn4+ and a better practical understanding of the high photoluminescence quantum yield red phosphors by adjusting their chemical components.",
author = "Lei Wang and Zhaoxiang Dai and Rulong Zhou and Bingyan Qu and Zeng, {Xiao Cheng}",
year = "2018",
month = "1",
day = "1",
doi = "10.1039/c8cp02569j",
language = "English (US)",
volume = "20",
pages = "16992--16999",
journal = "Physical Chemistry Chemical Physics",
issn = "1463-9076",
publisher = "Royal Society of Chemistry",
number = "25",

}

TY - JOUR

T1 - Understanding the quenching nature of Mn4+ in wide band gap inorganic compounds

T2 - Design principles for Mn4+ phosphors with higher efficiency

AU - Wang, Lei

AU - Dai, Zhaoxiang

AU - Zhou, Rulong

AU - Qu, Bingyan

AU - Zeng, Xiao Cheng

PY - 2018/1/1

Y1 - 2018/1/1

N2 - Mn4+ doped phosphors, as an alternative to rare-earth element doped phosphors, have attracted immense attention owing to their ultrahigh quantum efficiency of red emission for potential applications in high rendering white LEDs (light-emitting diodes). Their performance can be largely affected by quenching phenomena such as thermal quenching, concentration quenching and the quenching induced by some intrinsic/extrinsic defects. However, the quenching mechanisms due to the defect levels and host band are still incompletely understood. In this work, we carry out a comprehensive first-principles study on the underlying quenching mechanisms due to the defect levels of Mn4+ and other extrinsic/intrinsic defects, using the prototype oxide Y3Al5O12 (YAG), fluorides K2TiF6 (KTF) and ZnTiF6·6H2O (ZTF) as examples. From the comparison of the defect levels of Mn4+ with the host bands, we find that it is the very small energy difference between the defect levels of Mn4+ and the valence bands maximum (VBM) of YAG that causes the lower luminescence thermal stability of YAG:Mn4+, which we name as the hole-type thermal quenching mechanism. For the concentration quenching, it is nearly impossible for the Mn4+-Mn4+ pairs, previously considered as the main quenching centers, to appear in phosphors. A new quenching nature has been discussed. For the impurity ionic effects, the hole-type defects can largely stabilize the Mn ions in +4 states, thereby enhancing the emission intensity. These proposed mechanisms can offer deeper insights into the luminescence behavior of Mn4+ and a better practical understanding of the high photoluminescence quantum yield red phosphors by adjusting their chemical components.

AB - Mn4+ doped phosphors, as an alternative to rare-earth element doped phosphors, have attracted immense attention owing to their ultrahigh quantum efficiency of red emission for potential applications in high rendering white LEDs (light-emitting diodes). Their performance can be largely affected by quenching phenomena such as thermal quenching, concentration quenching and the quenching induced by some intrinsic/extrinsic defects. However, the quenching mechanisms due to the defect levels and host band are still incompletely understood. In this work, we carry out a comprehensive first-principles study on the underlying quenching mechanisms due to the defect levels of Mn4+ and other extrinsic/intrinsic defects, using the prototype oxide Y3Al5O12 (YAG), fluorides K2TiF6 (KTF) and ZnTiF6·6H2O (ZTF) as examples. From the comparison of the defect levels of Mn4+ with the host bands, we find that it is the very small energy difference between the defect levels of Mn4+ and the valence bands maximum (VBM) of YAG that causes the lower luminescence thermal stability of YAG:Mn4+, which we name as the hole-type thermal quenching mechanism. For the concentration quenching, it is nearly impossible for the Mn4+-Mn4+ pairs, previously considered as the main quenching centers, to appear in phosphors. A new quenching nature has been discussed. For the impurity ionic effects, the hole-type defects can largely stabilize the Mn ions in +4 states, thereby enhancing the emission intensity. These proposed mechanisms can offer deeper insights into the luminescence behavior of Mn4+ and a better practical understanding of the high photoluminescence quantum yield red phosphors by adjusting their chemical components.

UR - http://www.scopus.com/inward/record.url?scp=85049170630&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85049170630&partnerID=8YFLogxK

U2 - 10.1039/c8cp02569j

DO - 10.1039/c8cp02569j

M3 - Article

C2 - 29900444

AN - SCOPUS:85049170630

VL - 20

SP - 16992

EP - 16999

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 25

ER -