Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: On the Mn4+ R-line emission intensity and its tunability in solids

Abstract

The spectroscopic properties of Mn4+ ions in solids are analyzed to establish key parameters that are responsible for the energy and the intensity of the 2Eg→4A2g zero-phonon emission transition (R-line). These two factors of the emission spectrum are critical in determining the phosphor luminosity or brightness. The emission energy is chiefly determined by the “Mn4+-ligand” bonding covalence. In fluorides, the Mn-F bonding covalence is weak, and the R-line occur at higher energy. In oxides, the stronger Mn-O bonding covalence reduces the energy of the 2Eg state. In oxides, the R-line shifts to higher energy with increasing local distortion of the MnO6 octahedral moiety. Those host crystals that locate the Mn4+ ion at a noncentrosymmetric site (absence of inversion symmetry) relax the parity section rule, which enhances the R-line intensity. Increased R-line intensity in the emission spectrum produces color changes that increases phosphor luminosity. The influence of second coordination sphere (next-nearest neighbors) on the R-line intensity is considered. This article establishes guidelines for the development of host crystals that meet the requirements of high luminosity phosphors for general illumination applications.

Authors:
 [1];  [2];  [2];  [3];  [3];  [4];  [5]
+ Show Author Affiliations
  1. Chongqing Univ. of Posts and Telecommunications (China); Univ. of Tartu (Estonia); Jan Dlugosz Univ., Czestochowa (Poland)
  2. Current Powered By GE, Cleveland, OH (United States). Current & Lighting
  3. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  4. Jan Dlugosz Univ., Czestochowa (Poland)
  5. GE Global Research. Niskayuna, NY (United States)
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States)
Sponsoring Org.:
National Recruitment Program of High-end Foreign Experts; Programme for the Foreign Experts; European Regional Development Fund (ERDF); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Advanced Manufacturing Office
OSTI Identifier:
1615572
Alternate Identifier(s):
OSTI ID: 1636666
Report Number(s):
LLNL-JRNL-808646
Journal ID: ISSN 0925-3467; 992284
Grant/Contract Number:  
AC52-07NA27344; GDT20185200479; GDW20145200225; W2017011; PUT PRG111; AC02-07CH11358
Resource Type:
Accepted Manuscript
Journal Name:
Optical Materials
Additional Journal Information:
Journal Volume: 91; Journal Issue: C; Journal ID: ISSN 0925-3467
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Mn4+; Luminescence; Red phosphors; R-line; White LED

Citation Formats

Brik, M. G., Beers, W. W., Cohen, W., Payne, S. A., Cherepy, N. J., Piasecki, M., and Srivastava, A. M. On the Mn4+ R-line emission intensity and its tunability in solids. United States: N. p., 2019. Web. doi:10.1016/j.optmat.2019.03.046.
Copy to clipboard
Brik, M. G., Beers, W. W., Cohen, W., Payne, S. A., Cherepy, N. J., Piasecki, M., & Srivastava, A. M. On the Mn4+ R-line emission intensity and its tunability in solids. United States. https://doi.org/10.1016/j.optmat.2019.03.046
Copy to clipboard
Brik, M. G., Beers, W. W., Cohen, W., Payne, S. A., Cherepy, N. J., Piasecki, M., and Srivastava, A. M. Mon . "On the Mn4+ R-line emission intensity and its tunability in solids". United States. https://doi.org/10.1016/j.optmat.2019.03.046. https://www.osti.gov/servlets/purl/1615572.
Copy to clipboard
@article{osti_1615572,
title = {On the Mn4+ R-line emission intensity and its tunability in solids},
author = {Brik, M. G. and Beers, W. W. and Cohen, W. and Payne, S. A. and Cherepy, N. J. and Piasecki, M. and Srivastava, A. M.},
abstractNote = {The spectroscopic properties of Mn4+ ions in solids are analyzed to establish key parameters that are responsible for the energy and the intensity of the 2Eg→4A2g zero-phonon emission transition (R-line). These two factors of the emission spectrum are critical in determining the phosphor luminosity or brightness. The emission energy is chiefly determined by the “Mn4+-ligand” bonding covalence. In fluorides, the Mn-F bonding covalence is weak, and the R-line occur at higher energy. In oxides, the stronger Mn-O bonding covalence reduces the energy of the 2Eg state. In oxides, the R-line shifts to higher energy with increasing local distortion of the MnO6 octahedral moiety. Those host crystals that locate the Mn4+ ion at a noncentrosymmetric site (absence of inversion symmetry) relax the parity section rule, which enhances the R-line intensity. Increased R-line intensity in the emission spectrum produces color changes that increases phosphor luminosity. The influence of second coordination sphere (next-nearest neighbors) on the R-line intensity is considered. This article establishes guidelines for the development of host crystals that meet the requirements of high luminosity phosphors for general illumination applications.},
doi = {10.1016/j.optmat.2019.03.046},
journal = {Optical Materials},
number = C,
volume = 91,
place = {United States},
year = {Mon Apr 01 00:00:00 EDT 2019},
month = {Mon Apr 01 00:00:00 EDT 2019}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1016/j.optmat.2019.03.046
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 40 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Energy-Efficient, High-Color-Rendering LED Lamps Using Oxyfluoride and Fluoride Phosphors
journal, July 2010

  • Setlur, Anant A.; Radkov, Emil V.; Henderson, Claire S.
  • Chemistry of Materials, Vol. 22, Issue 13
  • DOI: 10.1021/cm100960g

K_2SiF_6:Mn^4+ as a red phosphor for displays and warm-white LEDs: a review of properties and perspectives
journal, January 2017

  • Sijbom, Heleen F.; Verstraete, Reinert; Joos, Jonas J.
  • Optical Materials Express, Vol. 7, Issue 9
  • DOI: 10.1364/OME.7.003332

Temperature dependence (13–600 K) of Mn4+ lifetime in commercial Mg28Ge7.55O32F15.04 and K2SiF6 phosphors
journal, October 2018

Concentration Quenching in K 2 SiF 6 :Mn 4+ Phosphors
journal, July 2017

  • Garcia-Santamaria, F.; Murphy, J. E.; Setlur, A. A.
  • ECS Journal of Solid State Science and Technology, Vol. 7, Issue 1
  • DOI: 10.1149/2.0081801jss

Properties of Mn[sup 4+]-Activated Hexafluorotitanate Phosphors
journal, January 2011

  • Xu, Yan Kai; Adachi, Sadao
  • Journal of The Electrochemical Society, Vol. 158, Issue 3
  • DOI: 10.1149/1.3530793

Photoluminescent properties of K2GeF6:Mn4+ red phosphor synthesized from aqueous HF/KMnO4 solution
journal, July 2009

  • Adachi, Sadao; Takahashi, Toru
  • Journal of Applied Physics, Vol. 106, Issue 1
  • DOI: 10.1063/1.3160303

Control of Luminescence by Tuning of Crystal Symmetry and Local Structure in Mn 4+ -Activated Narrow Band Fluoride Phosphors
journal, January 2018

  • Fang, Mu-Huai; Wu, Wei-Lun; Jin, Ye
  • Angewandte Chemie International Edition, Vol. 57, Issue 7
  • DOI: 10.1002/anie.201708814

Synthesis and Properties of Hetero-Dialkaline Hexafluorosilicate Red Phosphor KNaSiF 6 :Mn 4+
journal, January 2011

  • Adachi, Sadao; Abe, Hiroki; Kasa, Ryota
  • Journal of The Electrochemical Society, Vol. 159, Issue 2
  • DOI: 10.1149/2.064202jes

First-principles and crystal-field calculations of the electronic and optical properties of two novel red phosphors Rb 2 HfF 6 :Mn 4+ and Cs 2 HfF 6 :Mn 4+
journal, January 2018

  • Liu, Dong-Xu; Ma, Chong-Geng; Hu, Pei-Wen
  • Journal of the American Ceramic Society, Vol. 101, Issue 6
  • DOI: 10.1111/jace.15406

Synthesis and narrow red luminescence of Cs2HfF6:Mn4+, a new phosphor for warm white LEDs
journal, February 2018

Comparative ab initio study of electronic, optical and chemical bonding properties of pyrochlores, Y2B2O7 (B=Ti4+, Sn4+)
journal, December 2010

Comparative analysis of crystal field effects and energy level scheme of six-fold coordinated Cr4+ ion in the pyrochlores, Y2B2O7 (B=Ti4+, Sn4+)
journal, January 2011

Comparative analysis of crystal field effects and optical spectroscopy of six-coordinated Mn4+ ion in the Y2Ti2O7 and Y2Sn2O7 pyrochlores
journal, September 2011

On the optical properties of the Mn4+ ion in solids
journal, January 2013

Influence of Covalency on the Mn 4+ 2 E g → 4 A 2g Emission Energy in Crystals
journal, December 2014

  • Brik, M. G.; Camardello, S. J.; Srivastava, A. M.
  • ECS Journal of Solid State Science and Technology, Vol. 4, Issue 3
  • DOI: 10.1149/2.0031503jss

Spin-Forbidden Transitions in the Spectra of Transition Metal Ions and Nephelauxetic Effect
journal, September 2015

  • Brik, M. G.; Camardello, S. J.; Srivastava, A. M.
  • ECS Journal of Solid State Science and Technology, Vol. 5, Issue 1
  • DOI: 10.1149/2.0091601jss

Spectroscopy of Mn 4+ in Double Perovskites, La 2 LiSbO 6 and La 2 MgTiO 6 : Deep Red Photon Generators for Agriculture LEDs
journal, July 2017

  • Srivastava, A. M.; Brik, M. G.; Comanzo, H. A.
  • ECS Journal of Solid State Science and Technology, Vol. 7, Issue 1
  • DOI: 10.1149/2.0191801jss

Electronic Energy Levels of the Mn 4+ Ion in the Perovskite, CaZrO 3
journal, January 2013

  • Brik, Mikhail G.; Srivastava, Alok M.
  • ECS Journal of Solid State Science and Technology, Vol. 2, Issue 7
  • DOI: 10.1149/2.020307jss

Luminescence of Mn 4+ in the orthorhombic perovskite, LaGaO 3
journal, March 2017

The nature of Mn 4+ luminescence in the orthorhombic perovskite, GdAlO 3
journal, January 2017

Luminescence of Mn 4+ ions in CaTiO 3 and MgTiO 3 perovskites: Relationship of experimental spectroscopic data and crystal field calculations
journal, December 2017

Spectroscopy of Mn4+ in orthorhombic perovskite, LaInO3
journal, February 2019

Photoluminescence and Raman Scattering Spectra in (NH 4 ) 2 XF 6 :Mn 4+ (X = Si, Ge, Sn, and Ti) Red Phosphors
journal, January 2011

  • Xu, Yan Kai; Adachi, Sadao
  • Journal of The Electrochemical Society, Vol. 159, Issue 1
  • DOI: 10.1149/2.026201jes

Photoluminescent Properties of K[sub 2]SnF[sub 6]⋅H[sub 2]O:Mn[sup 4+] Hydrate Phosphor
journal, January 2011

  • Arai, Yusuke; Adachi, Sadao
  • Journal of The Electrochemical Society, Vol. 158, Issue 3
  • DOI: 10.1149/1.3532784

Optical Transitions and Internal Vibronic Frequencies of MnF[sub 6][sup 2-] Ions in Cs2SiF6 and Cs2GeF6 Red Phosphors
journal, January 2011

  • Arai, Yusuke; Adachi, Sadao
  • Journal of The Electrochemical Society, Vol. 158, Issue 6
  • DOI: 10.1149/1.3576124

Synthesis and Optical Properties of BaTiF 6 :Mn 4+ Red Phosphor
journal, January 2014

  • Sekiguchi, Daisuke; Adachi, Sadao
  • ECS Journal of Solid State Science and Technology, Vol. 3, Issue 4
  • DOI: 10.1149/2.025404jss

Editors' Choice—Rb 2 SiF 6 :Mn 4+ and Rb 2 TiF 6 :Mn 4+ Red-Emitting Phosphors
journal, January 2016

  • Sakurai, Shono; Nakamura, Toshihiro; Adachi, Sadao
  • ECS Journal of Solid State Science and Technology, Vol. 5, Issue 12
  • DOI: 10.1149/2.0171612jss

Light-Induced Degradation in Red-Emitting ZnSiF 6 ·6H 2 O:Mn 4+ Hydrate Phosphor
journal, January 2014

  • Hoshino, Ryosuke; Adachi, Sadao
  • ECS Journal of Solid State Science and Technology, Vol. 3, Issue 8
  • DOI: 10.1149/2.0031408jss

VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011

Mn 2+ and Mn 4+ red phosphors: synthesis, luminescence and applications in WLEDs. A review
journal, January 2018

  • Zhou, Qiang; Dolgov, Leonid; Srivastava, Alok M.
  • Journal of Materials Chemistry C, Vol. 6, Issue 11
  • DOI: 10.1039/C8TC00251G
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Photoluminescence Spectroscopy and Crystal-Field Parameters of Cr 3+ Ion in Red and Deep Red-Emitting Phosphors
    journal, January 2019

    • Adachi, Sadao
    • ECS Journal of Solid State Science and Technology, Vol. 8, Issue 12
    • DOI: 10.1149/2.0061912jss

    Luminescence of Mn 4+ in the Orthorhombic Perovskites, ASnO 3 (A=Ca, Sr)
    journal, September 2019

    • Srivastava, A. M.; Brik, M. G.; Comanzo, H. A.
    • ECS Journal of Solid State Science and Technology, Vol. 9, Issue 1
    • DOI: 10.1149/2.0132001jss

    Review—Tanabe−Sugano Energy-Level Diagram and Racah Parameters in Mn 4+ -Activated Red and Deep Red-Emitting Phosphors
    journal, January 2019

    • Adachi, Sadao
    • ECS Journal of Solid State Science and Technology, Vol. 8, Issue 12
    • DOI: 10.1149/2.0281912jss

    Intense deep-red zero phonon line emission of Mn 4+ in double perovskite La 4 Ti 3 O 12
    journal, January 2019

    • Ji, Haipeng; Ueda, Jumpei; Brik, Mikhail G.
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 45
    • DOI: 10.1039/c9cp04007b
      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: