Amphoteric Doping of Praseodymium Pr3+ in SrTiO3 Grain Boundaries

Yang, Hao; Lee, H. S.; Kotula, Paul G.; Sato, Yukio; Ikuhara, Yuichi; Browning, Nigel D.

doi:10.1063/1.4916223

Title: Amphoteric Doping of Praseodymium Pr3+ in SrTiO3 Grain Boundaries

Abstract

Charge Compensation in rare-earth Praseodymium (Pr³⁺) doped SrTiO₃ plays an important role in determining the overall photoluminescence properties of the system. Here, the Pr³⁺ doping behavior in SrTiO₃ grain boundaries (GBs) is analyzed using aberration corrected scanning transmission electron microscopy (STEM). The presence of Pr³⁺ induces structure variations and changes the statistical prevalence of GB structures. In contrast to the assumption that Pr³⁺ substitutes for A site as expected in the bulk, Pr³⁺ is found to substitute both Sr and Ti sites inside GBs with the highest concentration in the Ti sites. As a result, this amphoteric doping behavior in the boundary plane is further confirmed by first principles theoretical calculations.

Authors:: Yang, Hao; Lee, H. S.; Kotula, Paul G.; Sato, Yukio; Ikuhara, Yuichi; Browning, Nigel D.

Publication Date:: Mon Mar 23 00:00:00 EDT 2015

Research Org.:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Sponsoring Org.:: USDOE National Nuclear Security Administration (NNSA)

OSTI Identifier:: 1182940

Alternate Identifier(s):: OSTI ID: 1226726; OSTI ID: 1238591

Report Number(s):: PNNL-SA-108176; SAND-2015-8538J
47296

Grant/Contract Number:: AC05-76RL01830; FG02-03ER46057; AC04-94AL85000; FG02-03ER4605

Resource Type:: Journal Article: Accepted Manuscript

Journal Name:: Applied Physics Letters, 106(12):Article No. 121904

Additional Journal Information:: Journal Name: Applied Physics Letters, 106(12):Article No. 121904

Country of Publication:: United States

Language:: English

Subject:: Environmental Molecular Sciences Laboratory; 36 MATERIALS SCIENCE

Citation Formats


                    Yang, Hao, Lee, H. S., Kotula, Paul G., Sato, Yukio, Ikuhara, Yuichi, and Browning, Nigel D. Amphoteric Doping of Praseodymium Pr3+ in SrTiO3 Grain Boundaries.  United States: N. p., 2015. 
        Web.  doi:10.1063/1.4916223.

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                    Yang, Hao, Lee, H. S., Kotula, Paul G., Sato, Yukio, Ikuhara, Yuichi, & Browning, Nigel D. Amphoteric Doping of Praseodymium Pr3+ in SrTiO3 Grain Boundaries.  United States.  https://doi.org/10.1063/1.4916223

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                    Yang, Hao, Lee, H. S., Kotula, Paul G., Sato, Yukio, Ikuhara, Yuichi, and Browning, Nigel D. 2015.  
        "Amphoteric Doping of Praseodymium Pr3+ in SrTiO3 Grain Boundaries".  United States.  https://doi.org/10.1063/1.4916223.  https://www.osti.gov/servlets/purl/1182940.

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@article{osti_1182940,

  title        = {Amphoteric Doping of Praseodymium Pr3+ in SrTiO3 Grain Boundaries},

  author       = {Yang, Hao and Lee, H. S. and Kotula, Paul G. and Sato, Yukio and Ikuhara, Yuichi and Browning, Nigel D.},

  abstractNote = {Charge Compensation in rare-earth Praseodymium (Pr3+) doped SrTiO3 plays an important role in determining the overall photoluminescence properties of the system. Here, the Pr3+ doping behavior in SrTiO3 grain boundaries (GBs) is analyzed using aberration corrected scanning transmission electron microscopy (STEM). The presence of Pr3+ induces structure variations and changes the statistical prevalence of GB structures. In contrast to the assumption that Pr3+ substitutes for A site as expected in the bulk, Pr3+ is found to substitute both Sr and Ti sites inside GBs with the highest concentration in the Ti sites. As a result, this amphoteric doping behavior in the boundary plane is further confirmed by first principles theoretical calculations.},

  doi          = {10.1063/1.4916223},

  url          = {https://www.osti.gov/biblio/1182940},
  journal      = {Applied Physics Letters, 106(12):Article No. 121904},
number       = ,

  volume       = ,

  place        = {United States},

  year         = {Mon Mar 23 00:00:00 EDT 2015},

  month        = {Mon Mar 23 00:00:00 EDT 2015}

}

Copy to clipboard

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Works referenced in this record:

Photoluminescence Properties of Pr-Doped (Ca,Sr,Ba)TiO ₃
journal, June 2005

Kyômen, Tôru; Sakamoto, Riichiro; Sakamoto, Norihiko
Chemistry of Materials, Vol. 17, Issue 12
https://doi.org/10.1021/cm0403715

The influence of interface impurities on fracture energy of UHV diffusion bonded metal-ceramic bicrystals
journal, October 1994

Elssner, G.; Korn, D.; Rühle, M.
Scripta Metallurgica et Materialia, Vol. 31, Issue 8
https://doi.org/10.1016/0956-716X(94)90523-1

Current-Voltage Characteristics of Σ1 Boundaries with and without Cobalt Ions in Niobium-Doped SrTiO ₃ Bicrystals
journal, June 2000

Yamamoto, Takahisa; Hayashi, Katsuro; Ikuhara, Yuichi
Journal of the American Ceramic Society, Vol. 83, Issue 6
https://doi.org/10.1111/j.1151-2916.2000.tb01423.x

Local Structure and Energetics of Pr- and La-Doped SrTiO ₃ Grain Boundaries and the Influence on Core–Shell Structure Formation
journal, October 2014

Dawson, James A.; Tanaka, Isao
The Journal of Physical Chemistry C, Vol. 118, Issue 44
https://doi.org/10.1021/jp508444k

Emission from BaTiO3:Pr3+ controlled by ionic radius of added trivalent ion
journal, April 2002

Okamoto, Shinji; Yamamoto, Hajime
Journal of Applied Physics, Vol. 91, Issue 8
https://doi.org/10.1063/1.1458050

Atomic structure, electronic structure, and defect energetics in $[001] (310) Σ 5$ grain boundaries of ${SrTiO}_{3}$ and ${BaTiO}_{3}$
journal, December 2008

Imaeda, M.; Mizoguchi, T.; Sato, Y.
Physical Review B, Vol. 78, Issue 24
https://doi.org/10.1103/PhysRevB.78.245320

Enhanced red phosphorescence in nanosized CaTiO3:Pr3+ phosphors
journal, April 2007

Zhang, Xianmin; Zhang, Jiahua; Nie, Zhaogang
Applied Physics Letters, Vol. 90, Issue 15
https://doi.org/10.1063/1.2722205

Preparation and Al3+ enhanced photoluminescence properties of CaTiO3:Pr3+
journal, February 2006

Tang, Jinfeng; Yu, Xibin; Yang, Liangzhun
Materials Letters, Vol. 60, Issue 3
https://doi.org/10.1016/j.matlet.2005.08.047

Characteristic enhancement of emission from SrTiO3:Pr3+ by addition of group-III b ions
journal, January 2001

Okamoto, Shinji; Yamamoto, Hajime
Applied Physics Letters, Vol. 78, Issue 5
https://doi.org/10.1063/1.1343491

Luminescent properties of praseodymium-doped alkaline-earth titanates
journal, May 2003

Okamoto, Shinji; Yamamoto, Hajime
Journal of Luminescence, Vol. 102-103
https://doi.org/10.1016/S0022-2313(02)00591-4

Segregation of Mn ²⁺ Dopants as Interstitials in SrTiO ₃ Grain Boundaries
journal, October 2013

Yang, Hao; Kotula, Paul G.; Sato, Yukio
Materials Research Letters, Vol. 2, Issue 1
https://doi.org/10.1080/21663831.2013.856815

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

Kresse, G.; Furthmüller, J.
Physical Review B, Vol. 54, Issue 16, p. 11169-11186
https://doi.org/10.1103/PhysRevB.54.11169

Quantifying stoichiometry-induced variations in structure and energy of a SrTiO ₃ symmetric Σ13 {510}/<100 > grain boundary
journal, April 2013

Yang, H.; Lee, H. S.; Sarahan, M. C.
Philosophical Magazine, Vol. 93, Issue 10-12
https://doi.org/10.1080/14786435.2012.746479

A New Red-Emitting Phosphor, SrTiO ₃ :Pr ^{3 +} , for Low-Voltage Electron Excitation
journal, November 1999

Itoh, Shigeo; Toki, Hitoshi; Tamura, Kiyoshi
Japanese Journal of Applied Physics, Vol. 38, Issue Part 1, No. 11
https://doi.org/10.1143/JJAP.38.6387

Photoluminescence of Praseodymium-Doped Sr _{n +1} Ti _n O _{3 n +1} ( n =1, 2, ∞)
journal, January 2005

Inaguma, Yoshiyuki; Nagasawa, Daisuke; Katsumata, Tetsuhiro
Japanese Journal of Applied Physics, Vol. 44, Issue 1B
https://doi.org/10.1143/JJAP.44.761

The chemistry of the light rare‐earth elements as determined by electron energy loss spectroscopy
journal, June 1996

Fortner, J. A.; Buck, E. C.
Applied Physics Letters, Vol. 68, Issue 26
https://doi.org/10.1063/1.116627

Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation
journal, September 1992

Perdew, John P.; Chevary, J. A.; Vosko, S. H.
Physical Review B, Vol. 46, Issue 11
https://doi.org/10.1103/PhysRevB.46.6671

New electron excited light emitting materials∗
journal, March 1994

Vecht, A.
Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 12, Issue 2
https://doi.org/10.1116/1.587346

Defect energetics in SrTiO $_{3}$ symmetric tilt grain boundaries
journal, March 2011

Lee, H. -S.; Mizoguchi, T.; Mistui, J.
Physical Review B, Vol. 83, Issue 10
https://doi.org/10.1103/PhysRevB.83.104110

First-principles calculation of defect energetics in cubic-BaTiO3 and a comparison with SrTiO3
journal, November 2007

Lee, Hak-Sung; Mizoguchi, Teruyasu; Yamamoto, Takahisa
Acta Materialia, Vol. 55, Issue 19
https://doi.org/10.1016/j.actamat.2007.07.054

The application of a new potential model to the rare-earth doping of SrTiO3 and CaTiO3
journal, January 2013

Dawson, J. A.; Li, X.; Freeman, C. L.
Journal of Materials Chemistry C, Vol. 1, Issue 8
https://doi.org/10.1039/c2tc00475e

Automated Analysis of SEM X-Ray Spectral Images: A Powerful New Microanalysis Tool
journal, January 2003

Kotula, Paul G.; Keenan, Michael R.; Michael, Joseph R.
Microscopy and Microanalysis, Vol. 9, Issue 1
https://doi.org/10.1017/S1431927603030058

Improvement of the optical performances of Pr3+ in CaTiO3
journal, July 2001

Diallo, P. T.; Jeanlouis, K.; Boutinaud, P.
Journal of Alloys and Compounds, Vol. 323-324
https://doi.org/10.1016/S0925-8388(01)01115-X

Sr vacancy segregation by heat treatment at SrTiO3 grain boundary
journal, December 2005

Mizoguchi, Teruyasu; Sato, Yukio; Buban, James P.
Applied Physics Letters, Vol. 87, Issue 24
https://doi.org/10.1063/1.2146051

Red Luminescence in Pr3+-Doped Calcium Titanates
journal, March 1997

Diallo, P. T.; Boutinaud, P.; Mahiou, R.
physica status solidi (a), Vol. 160, Issue 1
https://doi.org/10.1002/1521-396X(199703)160:1<255::AID-PSSA255>3.0.CO;2-Y

Onset of spontaneous electrostrictive strain below 520 K in Pr-doped ${SrTiO}_{3}$
journal, September 2008

Ranjan, Rajeev; Garg, Rohini; Hackl, Rudi
Physical Review B, Vol. 78, Issue 9
https://doi.org/10.1103/PhysRevB.78.092102

Works referencing / citing this record:

Influence of Chemistry and Misfit Dislocation Structure on Dopant Segregation at Complex Oxide Heterointerfaces
journal, September 2018

Dholabhai, Pratik P.; Martinez, Enrique; Uberuaga, Blas P.
Advanced Theory and Simulations, Vol. 2, Issue 1
https://doi.org/10.1002/adts.201800095

A sub-sampled approach to extremely low-dose STEM
journal, January 2018

Stevens, A.; Luzi, L.; Yang, H.
Applied Physics Letters, Vol. 112, Issue 4
https://doi.org/10.1063/1.5016192

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Similar Records

Title: Amphoteric Doping of Praseodymium Pr3+ in SrTiO3 Grain Boundaries

Abstract

Citation Formats

Photoluminescence Properties of Pr-Doped (Ca,Sr,Ba)TiO 3 journal, June 2005

The influence of interface impurities on fracture energy of UHV diffusion bonded metal-ceramic bicrystals journal, October 1994

Current-Voltage Characteristics of Σ1 Boundaries with and without Cobalt Ions in Niobium-Doped SrTiO 3 Bicrystals journal, June 2000

Local Structure and Energetics of Pr- and La-Doped SrTiO 3 Grain Boundaries and the Influence on Core–Shell Structure Formation journal, October 2014

Emission from BaTiO3:Pr3+ controlled by ionic radius of added trivalent ion journal, April 2002

Atomic structure, electronic structure, and defect energetics in [ 001 ] ( 310 ) Σ 5 grain boundaries of SrTiO 3 and BaTiO 3 journal, December 2008

Enhanced red phosphorescence in nanosized CaTiO3:Pr3+ phosphors journal, April 2007

Preparation and Al3+ enhanced photoluminescence properties of CaTiO3:Pr3+ journal, February 2006

Characteristic enhancement of emission from SrTiO3:Pr3+ by addition of group-III b ions journal, January 2001

Luminescent properties of praseodymium-doped alkaline-earth titanates journal, May 2003

Segregation of Mn 2+ Dopants as Interstitials in SrTiO 3 Grain Boundaries journal, October 2013

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal, October 1996

Quantifying stoichiometry-induced variations in structure and energy of a SrTiO 3 symmetric Σ13 {510}/<100 > grain boundary journal, April 2013

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Photoluminescence of Praseodymium-Doped Sr n +1 Ti n O 3 n +1 ( n =1, 2, ∞) journal, January 2005

The chemistry of the light rare‐earth elements as determined by electron energy loss spectroscopy journal, June 1996

Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation journal, September 1992

New electron excited light emitting materials∗ journal, March 1994

Defect energetics in SrTiO 3 symmetric tilt grain boundaries journal, March 2011

First-principles calculation of defect energetics in cubic-BaTiO3 and a comparison with SrTiO3 journal, November 2007

The application of a new potential model to the rare-earth doping of SrTiO3 and CaTiO3 journal, January 2013

Automated Analysis of SEM X-Ray Spectral Images: A Powerful New Microanalysis Tool journal, January 2003

Improvement of the optical performances of Pr3+ in CaTiO3 journal, July 2001

Sr vacancy segregation by heat treatment at SrTiO3 grain boundary journal, December 2005

Red Luminescence in Pr3+-Doped Calcium Titanates journal, March 1997

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Influence of Chemistry and Misfit Dislocation Structure on Dopant Segregation at Complex Oxide Heterointerfaces journal, September 2018

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Photoluminescence Properties of Pr-Doped (Ca,Sr,Ba)TiO ₃
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The influence of interface impurities on fracture energy of UHV diffusion bonded metal-ceramic bicrystals
journal, October 1994

Current-Voltage Characteristics of Σ1 Boundaries with and without Cobalt Ions in Niobium-Doped SrTiO ₃ Bicrystals
journal, June 2000

Local Structure and Energetics of Pr- and La-Doped SrTiO ₃ Grain Boundaries and the Influence on Core–Shell Structure Formation
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Emission from BaTiO3:Pr3+ controlled by ionic radius of added trivalent ion
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Atomic structure, electronic structure, and defect energetics in $[001] (310) Σ 5$ grain boundaries of ${SrTiO}_{3}$ and ${BaTiO}_{3}$
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Enhanced red phosphorescence in nanosized CaTiO3:Pr3+ phosphors
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journal, October 1996

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