Isolated oxygen vacancies in strontium titanate shine red: Optical identification of Ti3+ polarons

Crespillo, M. L.; Graham, J. T.; Agulló-López, F.; Zhang, Y.; Weber, W. J.

doi:10.1016/j.apmt.2018.04.006

Isolated oxygen vacancies in strontium titanate shine red: Optical identification of Ti³⁺ polarons

Journal Article · Thu Aug 30 00:00:00 EDT 2018 · Applied Materials Today

DOI:https://doi.org/10.1016/j.apmt.2018.04.006· OSTI ID:1468192

Crespillo, M. L. ^[1]; Graham, J. T. ^[2]; Agulló-López, F. ^[3]; Zhang, Y. ^[4]; ^[5]

Univ. of Tennessee, Knoxville, TN (United States). Dept. of Materials Science and Engineering
Missouri Univ. of Science and Technology, Rolla, MO (United States). Dept. of Mining and Nuclear Engineering; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Materials Science and Engineering
Autonomous Univ. of Madrid (Spain). Centre for the Micro Analysis of Materials (CMAM)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
Univ. of Tennessee, Knoxville, TN (United States). Dept. of Materials Science and Engineering; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division

Oxide perovskites exhibit fascinating physical properties that identify them as key materials for the next generation of oxide-based functional electronic devices, as well as for catalysis and photochemistry applications. In strontium titanate, substantial efforts have been devoted to elucidate the role of oxygen vacancies and localized electronic states, such as polarons, on those properties. In this paper, a new model is presented that assigns a definitive red luminescence signature at 2.0 eV to Ti³⁺ polarons trapped at isolated oxygen vacancies. This emission provides an unequivocal identification for the oxygen vacancies, which allows monitoring their creation and annealing by a variety of physio-chemical treatments. Ionoluminescence with energetic (MeV) ion beams enables such identification by combining the sensitivity and resolution of spectroscopic techniques with their in situ character, as well as controlled incorporation of point defects, such as oxygen vacancies. Alternative models assigning the blue luminescence emission at 2.8 eV to oxygen vacancies are not supported by the experimental results. Finally and therefore, oxygen vacancies shine red and not blue, as previously proposed.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Univ. of Tennessee (United States)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1468192

Alternate ID(s):: OSTI ID: 1698193

Journal Information:: Applied Materials Today, Journal Name: Applied Materials Today Vol. 12; ISSN 2352-9407

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (32)

Anti-ferrodistortive-Like Oxygen-Octahedron Rotation Induced by the Oxygen Vacancy in Cubic SrTiO ₃ Choi, Minseok; Oba, Fumiyasu; Kumagai, Yu Advanced Materials, Vol. 25, Issue 1 https://doi.org/10.1002/adma.201203580	journal	October 2012
Room-temperature photoluminescence in amorphous SrTiO 3 - the influence of acceptor-type dopants Soledade, L. E. B.; Longo, E.; Leite, E. R. Applied Physics A: Materials Science & Processing, Vol. 75, Issue 5 https://doi.org/10.1007/s003390101140	journal	November 2002
In-situ luminescence monitoring of ion-induced damage evolution in SiO2 and Al2O3 Crespillo, M. L.; Graham, J. T.; Zhang, Y. Journal of Luminescence, Vol. 172 https://doi.org/10.1016/j.jlumin.2015.12.016	journal	April 2016
SRIM – The stopping and range of ions in matter (2010) Ziegler, James F.; Ziegler, M. D.; Biersack, J. P. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 268, Issue 11-12 https://doi.org/10.1016/j.nimb.2010.02.091	journal	June 2010
New ion beam materials laboratory for materials modification and irradiation effects research Zhang, Y.; Crespillo, M. L.; Xue, H. Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 338 https://doi.org/10.1016/j.nimb.2014.07.028	journal	November 2014
Tunable Electronic Structure and Surface Defects in Chromium-Doped Colloidal SrTiO _3−δ Nanocrystals Harrigan, William L.; Michaud, Samuel E.; Lehuta, Keith A. Chemistry of Materials, Vol. 28, Issue 2 https://doi.org/10.1021/acs.chemmater.6b00049	journal	January 2016
Correlation between Cr ³⁺ Luminescence and Oxygen Vacancy Disorder in Strontium Titanate under MeV Ion Irradiation Crespillo, M. L.; Graham, J. T.; Agulló-López, F. The Journal of Physical Chemistry C, Vol. 121, Issue 36 https://doi.org/10.1021/acs.jpcc.7b04352	journal	September 2017
Photophysical and Photocatalytic Properties of SrTiO ₃ Doped with Cr Cations on Different Sites Wang, Defa; Ye, Jinhua; Kako, Tetsuya The Journal of Physical Chemistry B, Vol. 110, Issue 32 https://doi.org/10.1021/jp062487p	journal	August 2006
Blue-light emission at room temperature from Ar+-irradiated SrTiO3 Kan, Daisuke; Terashima, Takahito; Kanda, Ryoko Nature Materials, Vol. 4, Issue 11 https://doi.org/10.1038/nmat1498	journal	October 2005
Oxygen vacancies shine blue Hwang, Harold Y. Nature Materials, Vol. 4, Issue 11 https://doi.org/10.1038/nmat1515	journal	November 2005
Magnetic effects at the interface between non-magnetic oxides Brinkman, A.; Huijben, M.; van Zalk, M. Nature Materials, Vol. 6, Issue 7, p. 493-496 https://doi.org/10.1038/nmat1931	journal	June 2007
Atomic-scale control of TiO6 octahedra through solution chemistry towards giant dielectric response Hu, Wanbiao; Li, Liping; Li, Guangshe Scientific Reports, Vol. 4, Issue 1 https://doi.org/10.1038/srep06582	journal	October 2014
X‐ray induced processes in SrTiO ₃ Aguilar, M.; Agulló‐López, F. Journal of Applied Physics, Vol. 53, Issue 12 https://doi.org/10.1063/1.330408	journal	December 1982
Temperature measurements during high flux ion beam irradiations Crespillo, M. L.; Graham, J. T.; Zhang, Y. Review of Scientific Instruments, Vol. 87, Issue 2 https://doi.org/10.1063/1.4941720	journal	February 2016
Role of oxygen vacancies on light emission mechanisms in SrTiO ₃ induced by high-energy particles Crespillo, M. L.; Graham, J. T.; Agulló-López, F. Journal of Physics D: Applied Physics, Vol. 50, Issue 15 https://doi.org/10.1088/1361-6463/aa627f	journal	March 2017
Model of ion-induced luminescence based on energy deposition by secondary electrons Michaelian, K.; Menchaca-Rocha, A. Physical Review B, Vol. 49, Issue 22 https://doi.org/10.1103/PhysRevB.49.15550	journal	June 1994
Symmetry-breaking Ta 4 + centers in KTaO 3 Laguta, V. V.; Zaritskii, M. I.; Glinchuk, M. D. Physical Review B, Vol. 58, Issue 1 https://doi.org/10.1103/PhysRevB.58.156	journal	July 1998
Electronic structure of a neutral oxygen vacancy in SrTiO 3 Ricci, Davide; Bano, Giuseppe; Pacchioni, Gianfranco Physical Review B, Vol. 68, Issue 22 https://doi.org/10.1103/PhysRevB.68.224105	journal	December 2003
Structural and electronic properties of oxygen vacancies in cubic and antiferrodistortive phases of SrTiO 3 Buban, James P.; Iddir, Hakim; Öğüt, Serdar Physical Review B, Vol. 69, Issue 18 https://doi.org/10.1103/PhysRevB.69.180102	journal	May 2004
Structural and electronic properties of n -doped and p -doped Sr Ti O 3 Luo, Weidong; Duan, Wenhui; Louie, Steven G. Physical Review B, Vol. 70, Issue 21 https://doi.org/10.1103/PhysRevB.70.214109	journal	December 2004
Recombination kinetics of a dense electron-hole plasma in strontium titanate Rubano, A.; Paparo, D.; Miletto, F. Physical Review B, Vol. 76, Issue 12 https://doi.org/10.1103/PhysRevB.76.125115	journal	September 2007
Electronic structure of oxygen vacancies in SrTiO 3 and LaAlO 3 Mitra, C.; Lin, C.; Robertson, J. Physical Review B, Vol. 86, Issue 15 https://doi.org/10.1103/PhysRevB.86.155105	journal	October 2012
Hole localization, migration, and the formation of peroxide anion in perovskite Sr Ti O 3 Chen, Hungru; Umezawa, Naoto Physical Review B, Vol. 90, Issue 3 https://doi.org/10.1103/PhysRevB.90.035202	journal	July 2014
Vacancies and small polarons in SrTiO 3 Janotti, Anderson; Varley, Joel B.; Choi, Minseok Physical Review B, Vol. 90, Issue 8 https://doi.org/10.1103/PhysRevB.90.085202	journal	August 2014
Temperature Dependence of Photoluminescence Spectra of Nondoped and Electron-Doped SrTiO 3 : Crossover from Auger Recombination to Single-Carrier Trapping Yamada, Yasuhiro; Yasuda, Hideki; Tayagaki, Takeshi Physical Review Letters, Vol. 102, Issue 24 https://doi.org/10.1103/PhysRevLett.102.247401	journal	June 2009
Charge-Carrier Transport Phenomena in Amorphous Si O 2 : Direct Measurement of the Drift Mobility and Lifetime Hughes, R. C. Physical Review Letters, Vol. 30, Issue 26 https://doi.org/10.1103/PhysRevLett.30.1333	journal	June 1973
In-Gap States in Wide-Band-Gap SrTiO3 Analyzed by Cathodoluminescence: In-Gap States in Wide-Band-Gap SrTiO3 Yang, Kai-Hsun; Chen, Ting-Yu; Ho, New-Jin Journal of the American Ceramic Society, Vol. 94, Issue 6 https://doi.org/10.1111/j.1551-2916.2010.04324.x	journal	March 2011
Superconducting Interfaces Between Insulating Oxides Reyren, N.; Thiel, S.; Caviglia, A. D. Science, Vol. 317, Issue 5842 https://doi.org/10.1126/science.1146006	journal	August 2007
Semiconductor Radiation Detectors: Basic principles and some uses of a recent tool that has revolutionized nuclear physics are described Goulding, F. S.; Stone, Y. Science, Vol. 170, Issue 3955 https://doi.org/10.1126/science.170.3955.280	journal	October 1970
Spectra and color centers of strontium titanate crystals Kulagin, N. A.; Hieckmann, E. Optics and Spectroscopy, Vol. 112, Issue 1 https://doi.org/10.1134/S0030400X12010134	journal	January 2012
First-principles study of bulk and surface oxygen vacancies in SrTiO3 crystal Alexandrov, V. E.; Kotomin, E. A.; Maier, J. The European Physical Journal B, Vol. 72, Issue 1 https://doi.org/10.1140/epjb/e2009-00339-4	journal	October 2009
Defect States Induced by Oxygen Vacancies in Cubic SrTiO ₃ : First-Principles Calculations Hou, Zhufeng; Terakura, Kiyoyuki Journal of the Physical Society of Japan, Vol. 79, Issue 11 https://doi.org/10.1143/JPSJ.79.114704	journal	November 2010

Cited By (2)

The blue emission at 2.8 eV in strontium titanate: evidence for a radiative transition of self-trapped excitons from unbound states Crespillo, M. L.; Graham, J. T.; Agulló-López, F. Materials Research Letters, Vol. 7, Issue 7 https://doi.org/10.1080/21663831.2019.1604444	journal	April 2019
Resistance Switching Behavior in Rectangle-Nano-Pattern SrTiO3 Induced by Simple Annealing Liao, Xiaxia; Zhang, Yufeng; Wang, Jiaou Materials, Vol. 12, Issue 22 https://doi.org/10.3390/ma12223698	journal	November 2019

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Related Subjects

36 MATERIALS SCIENCE
defects
ionoluminescence
oxygen vacancies
polarons
strontium titanate