Combining experiment and computation to elucidate the optical properties of Ce3+ in Ba5Si8O21

Zhong, Jiyou; Hariyani, Shruti; Zhuo, Ya; Zhao, Weiren; Liu, Xiang; Wen, Jun; Brgoch, Jakoah

doi:10.1039/c9cp05576b

Title: Combining experiment and computation to elucidate the optical properties of Ce³⁺ in Ba₅Si₈O₂₁

Journal Article · Mon Jan 06 00:00:00 EST 2020 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/c9cp05576b· OSTI ID:1600783

^[1];

^[2];

^[2]; Zhao, Weiren ^[1]; Liu, Xiang ^[1]; Wen, Jun ^[3];

^[2]

Guangdong Univ. of Technology, Guangzhou (China)
Univ. of Houston, TX (United States)
Anqing Normal Univ. (China)

Complex alkaline earth silicates have been extensively studied as rare-earth substituted phosphor hosts for use in solid-state lighting. One of the biggest challenges facing the development of new phosphors is understanding the relationship between the observed optical properties and the crystal structure. Fortunately, recent improvements in characterization techniques combined with advances in computational methodologies provide the research tools necessary to conduct a comprehensive analysis of these systems. Here, a new Ce³⁺ substituted phosphor is developed using Ba₅Si₈O₂₁ as the host crystal structure. The compound is evaluated using a combination of experimental and computational methods and shows Ba₅Si₈O₂₁:Ce³⁺ adopts a monoclinic crystal structure that was confirmed through Rietveld refinement of high-resolution synchrotron powder X-ray diffraction data. Photoluminescence spectroscopy reveals a broad-band blue emission centered at ~440 nm with an absolute quantum yield of ~45% under ultraviolet light excitation (λ_ex = 340 nm). This phosphor also shows a minimal chromaticity-drift but with moderate thermal quenching of the emission peak at elevated temperatures. The modest optical response of this phase is believed to stem from a combination of intrinsic structural complexity and the formation of defects because of the aliovalent rare-earth substitution. Finally, computational modeling provides essential insight into the site preference and energy level distribution of Ce³⁺ in this compound. These results highlight the importance of using experiment and computation in tandem to interpret the relationship between observed optical properties and the crystal structures of all rare-earth substituted complex phosphors.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: National Natural Science Foundation of China (NSFC); National Science Foundation (NSF); Welch Foundation; USDOE Office of Science (SC)

Grant/Contract Number:: 15-31814; AC02-06CH11357

OSTI ID:: 1600783

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Vol. 22, Issue 4; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

Citation Metrics:

Cited by: 7 works

Citation information provided by
Web of Science

References (63)

A Simple, Efficient Synthetic Route to Sr ₂ Si ₅ N ₈ :Eu ²⁺ -Based Red Phosphors for White Light-Emitting Diodes Xie, Rong-Jun; Hirosaki, Naoto; Suehiro, Takayuki Chemistry of Materials, Vol. 18, Issue 23 https://doi.org/10.1021/cm061010n	journal	November 2006
The a b i n i t i o model potential representation of the crystalline environment. Theoretical study of the local distortion on NaCl:Cu ⁺ Barandiarán, Zoila; Seijo, Luis The Journal of Chemical Physics, Vol. 89, Issue 9 https://doi.org/10.1063/1.455549	journal	November 1988
Nitride and oxynitride phosphors for white LEDs: Synthesis, new phosphor discovery, crystal structure Takeda, Takashi; Xie, Rong-Jun; Suehiro, Takayuki Progress in Solid State Chemistry, Vol. 51 https://doi.org/10.1016/j.progsolidstchem.2017.11.002	journal	September 2018
Achieving High Quantum Efficiency Narrow-Band β-Sialon:Eu ²⁺ Phosphors for High-Brightness LCD Backlights by Reducing the Eu ³⁺ Luminescence Killer Li, Shuxing; Wang, Le; Tang, Daiming Chemistry of Materials, Vol. 30, Issue 2 https://doi.org/10.1021/acs.chemmater.7b04605	journal	December 2017
Hybrid functionals based on a screened Coulomb potential Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias The Journal of Chemical Physics, Vol. 118, Issue 18 https://doi.org/10.1063/1.1564060	journal	May 2003
Luminescence enhancement of Eu2+, Ce3+ co-doped Ba3Si5O13−δNδ phosphors Zhang, Ruili; Maeda, Tomonori; Maruta, Ryosuke Journal of Solid State Chemistry, Vol. 183, Issue 3 https://doi.org/10.1016/j.jssc.2009.12.011	journal	March 2010
Luminescence properties of Eu ²⁺ -doped BaSi ₂ O ₅ as an efficient green phosphor for light-emitting devices and wide color gamut field emission displays Zhang, Qiang; Wang, Qian; Wang, Xicheng New Journal of Chemistry, Vol. 40, Issue 10 https://doi.org/10.1039/C6NJ01831A	journal	January 2016
Single-particle-diagnosis approach: An efficient strategy for discovering new nitride phosphors Wang, Xiaojun; Takeda, Takashi; Hirosaki, Naoto Journal of Rare Earths, Vol. 36, Issue 1 https://doi.org/10.1016/j.jre.2017.08.006	journal	January 2018
Understanding Thermal Quenching of Photoluminescence in Oxynitride Phosphors from First Principles Poncé, Samuel; Jia, Yongchao; Giantomassi, Matteo The Journal of Physical Chemistry C, Vol. 120, Issue 7 https://doi.org/10.1021/acs.jpcc.5b12361	journal	February 2016
Electronic Structures and Pr3+ Photoluminescence Characteristics in Fresnoite, Sr-Frenoite, and Ge-Frenoite: Electronic Structures and Pr3+ Photoluminescence Characteristics Li, Yanqin; Wang, Yuhua; Xu, Xuhui Journal of the American Ceramic Society, Vol. 94, Issue 2 https://doi.org/10.1111/j.1551-2916.2010.04108.x	journal	September 2010
Insights into Ba ₄ Si ₆ O ₁₆ structure and photoluminescence tuning of Ba ₄ Si ₆ O ₁₆ :Ce ³⁺ ,Eu ²⁺ phosphors Chen, Mingyue; Xia, Zhiguo; Molokeev, Maxim S. Journal of Materials Chemistry C, Vol. 3, Issue 48 https://doi.org/10.1039/C5TC03271G	journal	January 2015
Solid-State Light Sources Getting Smart Schubert, E. F. Science, Vol. 308, Issue 5726 https://doi.org/10.1126/science.1108712	journal	May 2005
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Novel zirconium silicate phosphor K ₂ ZrSi ₂ O ₇ :Eu ²⁺ for white light-emitting diodes and field emission displays Tang, Zuobin; Wang, Deyin; Khan, Waheed U. Journal of Materials Chemistry C, Vol. 4, Issue 23 https://doi.org/10.1039/C6TC01449F	journal	January 2016
Influence of Anion/Cation Substitution (Sr ²⁺ → Ba ²⁺ , Al ³⁺ → Si ⁴⁺ , N ^3– → O ^2– ) on Phase Transformation and Luminescence Properties of Ba ₃ Si ₆ O ₁₅ :Eu ²⁺ Phosphors Shang, Mengmeng; Liang, Sisi; Qu, Nianrui Chemistry of Materials, Vol. 29, Issue 4 https://doi.org/10.1021/acs.chemmater.6b05493	journal	February 2017
Experimental investigation of liquidus and phase stability in the BaO–SiO 2 binary system Zhang, Rui; Taskinen, Pekka Journal of Alloys and Compounds, Vol. 657 https://doi.org/10.1016/j.jallcom.2015.10.165	journal	February 2016
The complete active space SCF (CASSCF) method in a Newton–Raphson formulation with application to the HNO molecule Siegbahn, Per E. M.; Almlöf, Jan; Heiberg, Anders The Journal of Chemical Physics, Vol. 74, Issue 4 https://doi.org/10.1063/1.441359	journal	February 1981
Thermally stable K _x Cs _1−x AlSi ₂ O ₆ :Eu ²⁺ phosphors and their photoluminescence tuning Zhang, Manli; Xia, Zhiguo; Liu, Qiulin Journal of Materials Chemistry C, Vol. 5, Issue 30 https://doi.org/10.1039/C7TC02539D	journal	January 2017
Synthesis, structure and luminescent properties of a new blue-green-emitting garnet phosphor Ca ₂ LuScZrAl ₂ GeO ₁₂ :Ce ³⁺ Zheng, Yaling; Zhuang, Weidong; Xing, Xianran RSC Advances, Vol. 6, Issue 73 https://doi.org/10.1039/C6RA11258G	journal	January 2016
Self-Consistent Equations Including Exchange and Correlation Effects Kohn, W.; Sham, L. J. Physical Review, Vol. 140, Issue 4A, p. A1133-A1138 https://doi.org/10.1103/PhysRev.140.A1133	journal	November 1965
Sunlight Activated Long-Lasting Luminescence from Ba ₅ Si ₈ O ₂₁ : Eu ²⁺ ,Dy ³⁺ Phosphor Wang, Pengjiu; Xu, Xuhui; Zhou, Dacheng Inorganic Chemistry, Vol. 54, Issue 4 https://doi.org/10.1021/ic5026312	journal	January 2015
Preparation, electronic structure, and photoluminescent properties of Eu ²⁺ activated BaSi ₂ O ₅ powder phosphors for solid-state lighting Cao, Donghua; Wang, Hui; Wei, Hongjun Journal of Semiconductors, Vol. 36, Issue 12 https://doi.org/10.1088/1674-4926/36/12/123008	journal	December 2015
A zero-thermal-quenching phosphor Kim, Yoon Hwa; Arunkumar, Paulraj; Kim, Bo Young Nature Materials, Vol. 16, Issue 5 https://doi.org/10.1038/nmat4843	journal	February 2017
Effects of Composition on the Long Phosphorescent SrAl[sub 2]O[sub 4]:Eu[sup 2+], Dy[sup 3+] Phosphor Crystals Katsumata, T. Journal of The Electrochemical Society, Vol. 144, Issue 9 https://doi.org/10.1149/1.1837931	journal	January 1997
A complete active space SCF method (CASSCF) using a density matrix formulated super-CI approach Roos, Björn O.; Taylor, Peter R.; Sigbahn, Per E. M. Chemical Physics, Vol. 48, Issue 2 https://doi.org/10.1016/0301-0104(80)80045-0	journal	May 1980
Up conversion luminescence of Yb3+–Er3+ codoped CeO2 nanocrystals with imaging applications Cho, Jung-Hyun; Bass, Michael; Babu, Suresh Journal of Luminescence, Vol. 132, Issue 3 https://doi.org/10.1016/j.jlumin.2011.11.011	journal	March 2012
Crystal chemistry of silica-rich Barium silicates Hesse, K. -F.; Liebau, F. Zeitschrift für Kristallographie - Crystalline Materials, Vol. 153, Issue 1-2 https://doi.org/10.1524/zkri.1980.0002	journal	January 1980
Phase Separation in the System BaO-SiO2 Seward, T. P.; Uhlmann, D. R.; Turnbull, David Journal of the American Ceramic Society, Vol. 51, Issue 5 https://doi.org/10.1111/j.1151-2916.1968.tb13858.x	journal	May 1968
Optical properties of Ba2SiO4:Eu2+ phosphor for green light-emitting diode (LED) Zhang, Mei; Wang, Jing; Zhang, Qiuhong Materials Research Bulletin, Vol. 42, Issue 1 https://doi.org/10.1016/j.materresbull.2006.05.011	journal	January 2007
EXPGUI , a graphical user interface for GSAS Toby, Brian H. Journal of Applied Crystallography, Vol. 34, Issue 2 https://doi.org/10.1107/S0021889801002242	journal	April 2001
MOLCAS: a program package for computational chemistry Karlström, Gunnar; Lindh, Roland; Malmqvist, Per-Åke Computational Materials Science, Vol. 28, Issue 2 https://doi.org/10.1016/S0927-0256(03)00109-5	journal	October 2003
Effect of RE3+ electronegativities on luminescence property of Ba5Si8O21:Eu2+ persistent phosphor Dong, Zhiliang; Qin, Yi; Yang, Yong Journal of Rare Earths, Vol. 34, Issue 5 https://doi.org/10.1016/S1002-0721(16)60048-0	journal	May 2016
Improving Quantum Efficiency and Thermal Stability in Blue-Emitting Ba 2– x Sr x SiO 4 :Ce 3+ Phosphor via Solid Solution Ji, Xiaoyu; Zhang, Jilin; Li, Ying Chemistry of Materials, Vol. 30, Issue 15 https://doi.org/10.1021/acs.chemmater.8b01652	journal	July 2018
Bluish-green color emitting Ba2Si3O8:Eu2+ ceramic phosphors for white light-emitting diodes Xiao, F.; Xue, Y. N.; Zhang, Q. Y. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, Vol. 74, Issue 3 https://doi.org/10.1016/j.saa.2009.08.011	journal	October 2009
Tunable Blue-Green Color Emission and Energy Transfer of Ca ₂ Al ₃ O ₆ F:Ce ³⁺ ,Tb ³⁺ Phosphors for Near-UV White LEDs Xia, Zhiguo; Liu, Ru-Shi The Journal of Physical Chemistry C, Vol. 116, Issue 29 https://doi.org/10.1021/jp304722z	journal	July 2012
Ce ³⁺ -Doped garnet phosphors: composition modification, luminescence properties and applications Xia, Zhiguo; Meijerink, Andries Chemical Society Reviews, Vol. 46, Issue 1 https://doi.org/10.1039/C6CS00551A	journal	January 2017
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Luminescence Properties of a Red Phosphor, CaAlSiN[sub 3]:Eu[sup 2+], for White Light-Emitting Diodes Uheda, Kyota; Hirosaki, Naoto; Yamamoto, Yoshinobu Electrochemical and Solid-State Letters, Vol. 9, Issue 4 https://doi.org/10.1149/1.2173192	journal	January 2006
The multi-state CASPT2 method Finley, James; Malmqvist, Per-Åke; Roos, Björn O. Chemical Physics Letters, Vol. 288, Issue 2-4 https://doi.org/10.1016/S0009-2614(98)00252-8	journal	May 1998
Synthesis, electronic structures, and photoluminescence properties of an efficient and thermally stable red-emitting phosphor Ca ₃ ZrSi ₂ O ₉ :Eu ³⁺ ,Bi ³⁺ for deep UV-LEDs Zhong, Jiyou; Zhao, Weiren; Yang, Lunwei RSC Advances, Vol. 8, Issue 24 https://doi.org/10.1039/C8RA00844B	journal	January 2018
Identifying the Emission Centers and Probing the Mechanism for Highly Efficient and Thermally Stable Luminescence in the La ₃ Si ₆ N ₁₁ :Ce ³⁺ Phosphor Zhong, Jiyou; Zhao, Weiren; Du, Fu The Journal of Physical Chemistry C, Vol. 122, Issue 14 https://doi.org/10.1021/acs.jpcc.8b00683	journal	March 2018
Inhomogeneous Electron Gas Hohenberg, P.; Kohn, W. Physical Review, Vol. 136, Issue 3B, p. B864-B871 https://doi.org/10.1103/PhysRev.136.B864	journal	November 1964
Chemical Unit Cosubstitution and Tuning of Photoluminescence in the Ca ₂ (Al _{1– x} Mg _x )(Al _{1– x} Si _{1+ x} )O ₇ :Eu ²⁺ Phosphor Xia, Zhiguo; Ma, Chonggeng; Molokeev, Maxim S. Journal of the American Chemical Society, Vol. 137, Issue 39 https://doi.org/10.1021/jacs.5b08315	journal	September 2015
Luminescence characteristics of yellow emitting Ba3SiO5:Eu2+ phosphor Park, Joung Kyu; Lim, Mi Ae; Choi, Kyoung Jae Journal of Materials Science, Vol. 40, Issue 8 https://doi.org/10.1007/s10853-005-1237-z	journal	April 2005
Red phosphor converts white LEDs Huang, Xiaoyong Nature Photonics, Vol. 8, Issue 10 https://doi.org/10.1038/nphoton.2014.221	journal	October 2014
Candela‐class high‐brightness InGaN/AlGaN double‐heterostructure blue‐light‐emitting diodes Nakamura, Shuji; Mukai, Takashi; Senoh, Masayuki Applied Physics Letters, Vol. 64, Issue 13, p. 1687-1689 https://doi.org/10.1063/1.111832	journal	March 1994
Preparation and Luminescence Properties of Ba5Si8O21 Long Persistent Phosphors Doped with Rare-Earth Elements Silvestri, Andrea; Ligabue, Maria Laura; Malavasi, Gianluca Materials, Vol. 12, Issue 1 https://doi.org/10.3390/ma12010183	journal	January 2019
The ternary system BaSiO3-SrSiO3-SiO3 Huntelaar, M. E.; Cordfunke, E. H. P. Journal of Nuclear Materials, Vol. 201 https://doi.org/10.1016/0022-3115(93)90180-7	journal	May 1993
Defect-Induced Luminescence Quenching vs. Charge Carrier Generation of Phosphorus Incorporated in Silicon Nanocrystals as Function of Size Hiller, Daniel; López-Vidrier, Julian; Gutsch, Sebastian Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/s41598-017-01001-1	journal	April 2017
Second-order perturbation theory with a CASSCF reference function Andersson, Kerstin.; Malmqvist, Per Aake.; Roos, Bjoern O. The Journal of Physical Chemistry, Vol. 94, Issue 14 https://doi.org/10.1021/j100377a012	journal	July 1990
Combinatorial Approach to the Development of a Single Mass YVO ₄ :Bi ³⁺ ,Eu ³⁺ Phosphor with Red and Green Dual Colors for High Color Rendering White Light-Emitting Diodes Chen, Lei; Chen, Kuo-Ju; Lin, Chun-Che Journal of Combinatorial Chemistry, Vol. 12, Issue 4 https://doi.org/10.1021/cc100063x	journal	July 2010
Ba ₃ Y ₂ B ₆ O ₁₅ :Ce ³⁺ —A High Symmetry, Narrow-Emitting Blue Phosphor for Wide-Gamut White Lighting Duke, Anna C.; Hariyani, Shruti; Brgoch, Jakoah Chemistry of Materials, Vol. 30, Issue 8 https://doi.org/10.1021/acs.chemmater.8b00111	journal	March 2018
Advances in Phosphors for Light-emitting Diodes Lin, Chun Che; Liu, Ru-Shi The Journal of Physical Chemistry Letters, Vol. 2, Issue 11 https://doi.org/10.1021/jz2002452	journal	May 2011
Properties of a novel Ba 5 Si 8 O 21 :Eu 2+ , Nd 3+ phosphor: Bulk and 1D nanostructure with PVP synthesized by sol-gel and electrospinning Yao, Yuanlin; Zhou, Zhufa; Ye, Feng Journal of Alloys and Compounds, Vol. 712 https://doi.org/10.1016/j.jallcom.2017.04.102	journal	July 2017
Recent progress in luminescence tuning of Ce ³⁺ and Eu ²⁺ -activated phosphors for pc-WLEDs Li, Guogang; Tian, Ying; Zhao, Yun Chemical Society Reviews, Vol. 44, Issue 23 https://doi.org/10.1039/C4CS00446A	journal	January 2015
Insights into the discrepant luminescence for BaSiO ₃ :Eu ²⁺ phosphors prepared by solid-state reaction and precipitation reaction methods Xu, Jiao; Zhao, Yang; Chen, Jingjing Luminescence, Vol. 32, Issue 6 https://doi.org/10.1002/bio.3277	journal	February 2017
An improved experimental determination of external photoluminescence quantum efficiency de Mello, John C.; Wittmann, H. Felix; Friend, Richard H. Advanced Materials, Vol. 9, Issue 3 https://doi.org/10.1002/adma.19970090308	journal	March 1997
Consequences of Optimal Bond Valence on Structural Rigidity and Improved Luminescence Properties in Sr _x Ba _{2– x} SiO ₄ :Eu ²⁺ Orthosilicate Phosphors Denault, Kristin A.; Brgoch, Jakoah; Gaultois, Michael W. Chemistry of Materials, Vol. 26, Issue 7 https://doi.org/10.1021/cm500116u	journal	March 2014
Blue-shift of spectrum and enhanced luminescent properties of YAG: Ce3+ phosphor induced by small amount of La3+ incorporation Zhong, Jiyou; Zhuang, Weidong; Xing, Xianran Journal of Alloys and Compounds, Vol. 674 https://doi.org/10.1016/j.jallcom.2016.03.011	journal	July 2016
Crystal chemistry of silica-rich barium silicates Czank, Michael; Buseck, Peter R. Zeitschrift für Kristallographie - Crystalline Materials, Vol. 153, Issue 1-4 https://doi.org/10.1524/zkri.1980.153.14.19	journal	January 1980
Singlet exciton fission in a modified acene with improved stability and high photoluminescence yield. Budden, Peter; Weiss, Leah R.; Müller, Matthias Apollo - University of Cambridge Repository https://doi.org/10.17863/cam.64548	text	January 2021
Crystal chemistry of silica-rich Barium silicates: I: Refinement of the crystal structures of Ba ₄ [Si ₆ O ₁₆ ], Ba ₅ [Si ₈ O ₂₁ ] and Ba ₆ [Si ₁₀ O ₂₆ ], silicates with triple, quadruple and quintuple chains Hesse, K. -F.; Liebau, F. Zeitschrift für Kristallographie - Crystalline Materials, Vol. 153, Issue 1-4 https://doi.org/10.1524/zkri.1980.153.14.3	journal	December 1980
Luminescent Materials Leverenz, Humboldt W.; Seitz, Frederick Journal of Applied Physics, Vol. 10, Issue 7 https://doi.org/10.1063/1.1707331	journal	July 1939

Similar Records

Structure and photoluminescence properties of Ce{sup 3+}-doped novel silicon-oxynitride Ba{sub 4-z}M{sub z}Si{sub 8}O{sub 20-3x}N{sub 2x} (M=Mg, Ca, Sr)

Journal Article · Wed Jun 15 00:00:00 EDT 2011 · Journal of Solid State Chemistry · OSTI ID:1600783

Fang, Y; Xie, R J; Hirosaki, N; +3 more

The optical spectroscopic properties of rare earth-activated barium orthophosphate in VUV-Vis range

Journal Article · Wed Apr 30 00:00:00 EDT 2003 · Materials Research Bulletin · OSTI ID:1600783

Hongbin, Liang; Ye, Tao; Qinghua, Zeng; +5 more

The effect of rare-earth substitution on the Debye temperature of inorganic phosphors

Journal Article · Mon Feb 03 00:00:00 EST 2020 · Applied Physics Letters · OSTI ID:1600783

Hariyani, Shruti; Duke, Anna C.; Krauskopf, Thorben; +2 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Combining experiment and computation to elucidate the optical properties of Ce3+ in Ba5Si8O21

Citation Formats

References (63)

Similar Records

Related Subjects

Title: Combining experiment and computation to elucidate the optical properties of Ce³⁺ in Ba₅Si₈O₂₁