Luminescence of Mn4+ in the Orthorhombic Perovskites, ASnO3 (A=Ca, Sr)

Srivastava, A. M.; Brik, M. G.; Comanzo, H. A.; Beers, W. W.; Cohen, W.; Cherepy, N.; Payne, S. A.

doi:10.1149/2.0132001JSS

Title: Luminescence of Mn⁴⁺ in the Orthorhombic Perovskites, ASnO₃ (A=Ca, Sr)

Abstract

The aim of this paper is to provide a comparative study of the spectroscopic properties of Mn⁴⁺ (3d³) ion in the orthorhombic perovskites, ASnO₃ (A=Ca, Sr). The most significant parameter controlling the energy of the zero-phonon line (²E→⁴A₂ transition) is the deviation of the octahedral O-Mn-O bond angle from the ideal 90⁰ value. It is significant that despite the longer Sn⁴⁺-O^2- bond distance, the crystal field strength (10 Dq) in CaSnO₃ is higher than that of SrSnO₃. We discuss this result in relation to the perovskite crystal chemistry. Mulliken population analysis and bond order calculation are made to clarify the nature of chemical bonding in the stannate perovskites.

Authors:

; Brik, M. G.; Comanzo, H. A.; Beers, W. W.; Cohen, W.; Cherepy, N.; Payne, S. A.

Publication Date:: 2019-09-26

Research Org.:: Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Ames Lab., Ames, IA (United States)

Sponsoring Org.:: USDOE National Nuclear Security Administration (NNSA); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Advanced Manufacturing Office; National Recruitment Program of High-end Foreign Experts; Programme for the Foreign Experts; Chongqing University of Posts and Telecommunications (CQUPT); Estonian Research Council; European Regional Development Fund (ERDF)

OSTI Identifier:: 1566901

Alternate Identifier(s):: OSTI ID: 1635082

Report Number(s):: LLNL-JRNL-808457
Journal ID: ISSN 2162-8769; /jss/9/1/016009.atom

Grant/Contract Number:: AC52-07NA27344; AC02-07CH11358; GDT20185200479; GDW20145200225; W2017011; PUT PRG111

Resource Type:: Published Article

Journal Name:: ECS Journal of Solid State Science and Technology

Additional Journal Information:: Journal Name: ECS Journal of Solid State Science and Technology Journal Volume: 9 Journal Issue: 1; Journal ID: ISSN 2162-8769

Publisher:: Electrochemical Society

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE

Citation Formats


                    Srivastava, A. M., Brik, M. G., Comanzo, H. A., Beers, W. W., Cohen, W., Cherepy, N., and Payne, S. A. Luminescence of Mn4+ in the Orthorhombic Perovskites, ASnO3 (A=Ca, Sr).  United States: N. p., 2019. 
Web.  doi:10.1149/2.0132001JSS.

Copy to clipboard


                    Srivastava, A. M., Brik, M. G., Comanzo, H. A., Beers, W. W., Cohen, W., Cherepy, N., & Payne, S. A. Luminescence of Mn4+ in the Orthorhombic Perovskites, ASnO3 (A=Ca, Sr).  United States.  https://doi.org/10.1149/2.0132001JSS

Copy to clipboard


                    Srivastava, A. M., Brik, M. G., Comanzo, H. A., Beers, W. W., Cohen, W., Cherepy, N., and Payne, S. A. Thu .  
"Luminescence of Mn4+ in the Orthorhombic Perovskites, ASnO3 (A=Ca, Sr)".  United States.  https://doi.org/10.1149/2.0132001JSS.

Copy to clipboard


                    
@article{osti_1566901,

  title        = {Luminescence of Mn4+ in the Orthorhombic Perovskites, ASnO3 (A=Ca, Sr)},

  author       = {Srivastava, A. M. and Brik, M. G. and Comanzo, H. A. and Beers, W. W. and Cohen, W. and Cherepy, N. and Payne, S. A.},

  abstractNote = {The aim of this paper is to provide a comparative study of the spectroscopic properties of Mn4+ (3d3) ion in the orthorhombic perovskites, ASnO3 (A=Ca, Sr). The most significant parameter controlling the energy of the zero-phonon line (2E→4A2 transition) is the deviation of the octahedral O-Mn-O bond angle from the ideal 900 value. It is significant that despite the longer Sn4+-O2- bond distance, the crystal field strength (10 Dq) in CaSnO3 is higher than that of SrSnO3. We discuss this result in relation to the perovskite crystal chemistry. Mulliken population analysis and bond order calculation are made to clarify the nature of chemical bonding in the stannate perovskites.},

  doi          = {10.1149/2.0132001JSS},

  journal      = {ECS Journal of Solid State Science and Technology},

  number       = 1,

  volume       = 9,

  place        = {United States},

  year         = {2019},

  month        = {9}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Publisher's Version of Record
https://doi.org/10.1149/2.0132001JSS

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 1 work

Citation information provided by
Web of Science

Figures / Tables:

Figure 1: The low temperature (T = 15 K) excitation spectra of Mn⁴⁺ in CaSnO₃ (λ_em = 695 nm; dashed blue line) and SrSnO₃ (λ_em = 702 nm; solid red line).

All figures and tables (4 total)

Save / Share:

Export Metadata

Save to My Library

Works referenced in this record:

Structural and electronic relaxations around substitutional ${Cr}^{3 +}$ and ${Fe}^{3 +}$ ions in corundum
journal, March 2003

Gaudry, Emilie; Kiratisin, Amonmat; Sainctavit, Philippe
Physical Review B, Vol. 67, Issue 9
DOI: 10.1103/PhysRevB.67.094108

Mn4+ emission in pyrochlore oxides
journal, January 2015

Du, M. H.
Journal of Luminescence, Vol. 157
DOI: 10.1016/j.jlumin.2014.08.038

Zero-phonon transitions and the Stokes shift of ${Mn}^{2 +}$ -doped perovskites: Dependence on the metal-ligand distance
journal, August 1994

Marco de Lucas, M. C.; Rodríguez, F.; Moreno, M.
Physical Review B, Vol. 50, Issue 5
DOI: 10.1103/PhysRevB.50.2760

Revisiting the Spectroscopy of the Bi ³⁺ Ion in Oxide Compounds
journal, April 2013

Boutinaud, Philippe
Inorganic Chemistry, Vol. 52, Issue 10
DOI: 10.1021/ic400382k

Effects of Eu ³⁺ Sites on Photoluminescence in Ba ₂ Ln(BO ₃ ) ₂ Cl (Ln = Gd, Y) Hosts
journal, November 2012

Jing, Heng; Guo, Chongfeng; Zhang, Niumiao
ECS Journal of Solid State Science and Technology, Vol. 2, Issue 1
DOI: 10.1149/2.023301jss

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

Srivastava, A. M.; Comanzo, H. A.; Smith, D. J.
Journal of Luminescence, Vol. 206
DOI: 10.1016/j.jlumin.2018.10.090

The luminescence of tetravalent manganese in CaZrO3:Mn
journal, January 1981

Blasse, G.; de Korte, P. H. M.
Journal of Inorganic and Nuclear Chemistry, Vol. 43, Issue 7
DOI: 10.1016/0022-1902(81)80325-9

Crystal field studies of the Mn4+ energy levels in the perovskite, LaAlO3
journal, June 2013

Srivastava, A. M.; Brik, M. G.
Optical Materials, Vol. 35, Issue 8
DOI: 10.1016/j.optmat.2013.03.021

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

Preparation and characterization of BaMnO3 and SrMnO3 polytypes
journal, April 1970

Chamberland, B. L.; Sleight, A. W.; Weiher, J. F.
Journal of Solid State Chemistry, Vol. 1, Issue 3-4
DOI: 10.1016/0022-4596(70)90133-7

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

Srivastava, A. M.; Camardello, S. J.; Brik, M. G.
Journal of Luminescence, Vol. 183
DOI: 10.1016/j.jlumin.2016.11.015

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976

Shannon, R. D.
Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767
DOI: 10.1107/S0567739476001551

Pressure dependence of the ${}^{4}$ $T_{2}$ and ${}^{4}$ $T_{1}$ absorption bands of ruby to 35 GPa
journal, March 1990

Duclos, Steven J.; Vohra, Yogesh K.; Ruoff, Arthur L.
Physical Review B, Vol. 41, Issue 8
DOI: 10.1103/PhysRevB.41.5372

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

Beers, W. W.; Smith, D.; Cohen, W. E.
Optical Materials, Vol. 84
DOI: 10.1016/j.optmat.2018.07.050

On the Mn4+ R-line emission intensity and its tunability in solids
journal, May 2019

Brik, M. G.; Beers, W. W.; Cohen, W.
Optical Materials, Vol. 91
DOI: 10.1016/j.optmat.2019.03.046

Pressure and temperature dependence of chromium photoluminescence in $K_{2}$ ${NaGaF}_{6}$ : ${Cr}^{3 +}$
journal, May 1986

Dolan, J. F.; Kappers, L. A.; Bartram, R. H.
Physical Review B, Vol. 33, Issue 10
DOI: 10.1103/PhysRevB.33.7339

Dependence of the optical spectrum of MnF ⁴⁻ ₆ on the Mn ² ⁺ –F ⁻ distance
journal, January 1986

Rodríguez, Fernando; Moreno, Miguel
The Journal of Chemical Physics, Vol. 84, Issue 2
DOI: 10.1063/1.450565

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

Srivastava, A. M.; Brik, M. G.
Optical Materials, Vol. 63
DOI: 10.1016/j.optmat.2016.06.032

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

Luminescence of Mn[sup 4+] in the Distorted Perovskite Gd[sub 2]MgTiO[sub 6]
journal, January 1996

Srivastava, A. M.
Journal of The Electrochemical Society, Vol. 143, Issue 9
DOI: 10.1149/1.1837087

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

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

Brik, M. G.; Srivastava, A. M.
Journal of Luminescence, Vol. 133
DOI: 10.1016/j.jlumin.2011.08.047

Figures / Tables found in this record:

Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.

Similar Records in DOE PAGES and OSTI.GOV collections:

Spectroscopy of Mn⁴⁺ in orthorhombic perovskite, LaInO₃

Journal Article Srivastava, A. M. ; Comanzo, H. A. ; Smith, D. J. ; ... - Journal of Luminescence

The low temperature spectroscopic properties of Mn⁴⁺ (3d³) in the orthorhombic perovskite, LaInO₃, is examined in this work. The exchange charge model of crystal-field theory is used to calculate the Mn⁴⁺ energy levels. The spectra can be fitted by the parameters Dq = 1776 cm^–1, B = 700 cm^–1 and C = 3189 cm^–1, with C/B = 4.5. Discussions pertaining to the low luminescence efficiency of LaInO₃:Mn⁴⁺ are presented. A comparative study of the variations in the energy of the ²E_g → ⁴A_2g emission transition in a series of materials with the perovskite structure is presented. Here, the data suggestmore »« less
Cited by 11
https://doi.org/10.1016/j.jlumin.2018.10.090

Full Text Available
On the Mn⁴⁺ R-line emission intensity and its tunability in solids

Journal Article Brik, M. G. ; Beers, W. W. ; Cohen, W. ; ... - Optical Materials

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 ²E_g→⁴A_2g 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 ²E_g state. In oxides, the R-line shifts to higher energy with increasing local distortion of themore »« less
Cited by 15
https://doi.org/10.1016/j.optmat.2019.03.046

Full Text Available
Optical spectrum of Mn⁴⁺ in Y₂Ti_2-xSn_xO₇ pyrochlore solid solution: R-line energy and intensity

Journal Article Srivastava, A. M. ; Brik, M. G. ; Comanzo, H. A. ; ... - Optical Materials

We report we investigated the luminescence of the Mn⁴⁺ ions in Y₂Ti_2-xSn_xO₇ (x = 0, 0.5, 1.0, 2.0) pyrochlore solid solutions and compared the results with the spectroscopic data of the two end members. The emission spectra in the mixed pyrochlore solid solutions are broadened relative to the end members due to long range disorder between the Sn⁴⁺ and Ti⁴⁺ ions. The R-line intensity is particularly weak in both Y₂Sn₂O₇ and Y₂Ti₂O₇. The increase in R-line intensity in the mixed pyrochlore solid solutions is attributed to the random distribution of Sn⁴⁺ and Ti⁴⁺ ions in the second coordination sphere (nextmore »« less
Cited by 1
https://doi.org/10.1016/j.optmat.2019.109196

Full Text Available
CaSn(OH){sub 6} hydroxides, CaSnO{sub 3} oxides and CaSnF{sub 6} fluorides: Synthesis and structural filiation. Cationic environment impact on Pr{sup 3+} doped compounds luminescence

Journal Article Gaudon, Manuel ; Salek, Guillaume ; Kande, Malang ; ... - Journal of Solid State Chemistry (Print)

Highlights: • Structural filiation of stannates compounds. • {sup 119}Sn Mossbauer analysis of Sn-X chemical bonding (X = OH, O, F). • Nephelauxetic effect observed in the luminescence of Pr{sup 3+} doped stannate compounds. - Abstract: CaSn(OH){sub 6}, CaSnO{sub 3} and CaSnF{sub 6} compounds were elaborated from a “one-batch” synthesis route: the coprecipitation of the pure double hydroxide leads to pure double oxide or fluoride after annealing treatments under air or HF as anhydrous gas, respectively. Structural and morphological features of the three matrices were carefully investigated by X Ray Diffraction analysis and Scanning Electron Microscopy, respectively. In addition, themore »« less
https://doi.org/10.1016/J.JSSC.2018.06.017
Structural, optoelectronic, infrared and Raman spectra of orthorhombic SrSnO{sub 3} from DFT calculations

Journal Article Moreira, E ; Henriques, J M ; Azevedo, D L ; ... - Journal of Solid State Chemistry

Orthorhombic SrSnO{sub 3} was investigated using density functional theory (DFT) considering both the local density and generalized gradient approximations, LDA and GGA, respectively. The electronic band structure, density of states, complex dielectric function, optical absorption, and the infrared and Raman spectra were computed. Calculated lattice parameters are close to the experimental measurements, and an indirect band gap E(S{yields}{Gamma})=1.97eV (2.27 eV) was obtained within the GGA (LDA) level of calculation. Effective masses for holes and electrons were estimated, being very anisotropic in comparison with similar results for orthorhombic CaSnO{sub 3}. The complex dielectric function and the optical absorption of SrSnO{sub 3}more »« less
https://doi.org/10.1016/j.jssc.2011.02.009

Similar Records

Title: Luminescence of Mn4+ in the Orthorhombic Perovskites, ASnO3 (A=Ca, Sr)

Abstract

Citation Formats

Figures / Tables:

Structural and electronic relaxations around substitutional Cr 3 + and Fe 3 + ions in corundum journal, March 2003

Mn4+ emission in pyrochlore oxides journal, January 2015

Zero-phonon transitions and the Stokes shift of Mn 2 + -doped perovskites: Dependence on the metal-ligand distance journal, August 1994

Revisiting the Spectroscopy of the Bi 3+ Ion in Oxide Compounds journal, April 2013

Effects of Eu 3+ Sites on Photoluminescence in Ba 2 Ln(BO 3 ) 2 Cl (Ln = Gd, Y) Hosts journal, November 2012

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

The luminescence of tetravalent manganese in CaZrO3:Mn journal, January 1981

Crystal field studies of the Mn4+ energy levels in the perovskite, LaAlO3 journal, June 2013

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

Preparation and characterization of BaMnO3 and SrMnO3 polytypes journal, April 1970

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

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides journal, September 1976

Pressure dependence of the 4 T 2 and 4 T 1 absorption bands of ruby to 35 GPa journal, March 1990

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

On the Mn4+ R-line emission intensity and its tunability in solids journal, May 2019

Pressure and temperature dependence of chromium photoluminescence in K 2 NaGaF 6 : Cr 3 + journal, May 1986

Dependence of the optical spectrum of MnF 4− 6 on the Mn 2 + –F − distance journal, January 1986

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

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

Luminescence of Mn[sup 4+] in the Distorted Perovskite Gd[sub 2]MgTiO[sub 6] journal, January 1996

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

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

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

Title: Luminescence of Mn⁴⁺ in the Orthorhombic Perovskites, ASnO₃ (A=Ca, Sr)

Structural and electronic relaxations around substitutional ${Cr}^{3 +}$ and ${Fe}^{3 +}$ ions in corundum
journal, March 2003

Mn4+ emission in pyrochlore oxides
journal, January 2015

Zero-phonon transitions and the Stokes shift of ${Mn}^{2 +}$ -doped perovskites: Dependence on the metal-ligand distance
journal, August 1994

Revisiting the Spectroscopy of the Bi ³⁺ Ion in Oxide Compounds
journal, April 2013

Effects of Eu ³⁺ Sites on Photoluminescence in Ba ₂ Ln(BO ₃ ) ₂ Cl (Ln = Gd, Y) Hosts
journal, November 2012

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

The luminescence of tetravalent manganese in CaZrO3:Mn
journal, January 1981

Crystal field studies of the Mn4+ energy levels in the perovskite, LaAlO3
journal, June 2013

Influence of Covalency on the Mn ^{4+ 2} E _g → ⁴ A _2g Emission Energy in Crystals
journal, December 2014

Preparation and characterization of BaMnO3 and SrMnO3 polytypes
journal, April 1970

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

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976

Pressure dependence of the ${}^{4}$ $T_{2}$ and ${}^{4}$ $T_{1}$ absorption bands of ruby to 35 GPa
journal, March 1990

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

On the Mn4+ R-line emission intensity and its tunability in solids
journal, May 2019

Pressure and temperature dependence of chromium photoluminescence in $K_{2}$ ${NaGaF}_{6}$ : ${Cr}^{3 +}$
journal, May 1986

Dependence of the optical spectrum of MnF ⁴⁻ ₆ on the Mn ² ⁺ –F ⁻ distance
journal, January 1986

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

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

Luminescence of Mn[sup 4+] in the Distorted Perovskite Gd[sub 2]MgTiO[sub 6]
journal, January 1996

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

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

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