Understanding the links between composition, polyhedral distortion, and luminescence properties in green-emitting β-Si6–zAlzOzN8–z:Eu2+ phosphors

Cozzan, Clayton; Laurita, Geneva; Gaultois, Michael W.; Cohen, Marcus; Mikhailovsky, Alexander A.; Balasubramanian, Mahalingam; Seshadri, Ram

doi:10.1039/C7TC03039H

Title: Understanding the links between composition, polyhedral distortion, and luminescence properties in green-emitting β-Si_6–zAl_zO_zN_8–z:Eu²⁺ phosphors

Journal Article · Thu Sep 21 00:00:00 EDT 2017 · Journal of Materials Chemistry C

DOI:https://doi.org/10.1039/C7TC03039H· OSTI ID:1399266

^[1];

^[2];

^[1]; Cohen, Marcus ^[1]; Mikhailovsky, Alexander A. ^[1]; Balasubramanian, Mahalingam ^[3];

^[1]

Univ. of California, Santa Barbara, CA (United States)
Bates College, Lewiston, ME (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

Inorganic phosphor materials play a crucial role in the creation of white light from blue and near-UV solid-state light-emitting diodes. Understanding the intricacies of the phosphor structure is key for setting the stage for improved, more efficient functionality. Average structure and coordination environment analysis of the robust and efficient green-emitting phosphor, β-SiAlON:Eu²⁺ (β-Si_6–zAl_zO_zN_8–zEu_0.009), is combined here with a range of property measurements to elucidate the role of Al content (z) in luminescence properties, including the red shift of emission and the thermal quenching of luminescence as a function of increasing Al content z. Average structure techniques reveal changes in polyhedral distortion with increasing z for the 9-coordinate Eu site in β-SiAlON:Eu²⁺. X-ray absorption near edge structure (XANES) is used to confirm that the majority of the activator Eu is in the Eu²⁺ state, exhibiting the symmetry-allowed and efficient 4f⁷5d⁰ → 4f⁶5d¹ transitions. As a result, room temperature and temperature-dependent luminescence indicate a curious increase in thermal stability with increasing z over a small range due to an increasing barrier for thermal ionization, which is correlated to an increase in the quantum yield of the phosphor.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1399266

Journal Information:: Journal of Materials Chemistry C, Vol. 5, Issue 38; ISSN 2050-7526

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 18 works

Citation information provided by
Web of Science

References (33)

Characterization and properties of green-emitting β-SiAlON:Eu2+ powder phosphors for white light-emitting diodes Hirosaki, Naoto; Xie, Rong-Jun; Kimoto, Koji Applied Physics Letters, Vol. 86, Issue 21 https://doi.org/10.1063/1.1935027	journal	May 2005
Direct observation of single dopant atom in light-emitting phosphor of β-SiAlON:Eu2+ Kimoto, Koji; Xie, Rong-Jun; Matsui, Yoshio Applied Physics Letters, Vol. 94, Issue 4 https://doi.org/10.1063/1.3076110	journal	January 2009
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT Ravel, B.; Newville, M. Journal of Synchrotron Radiation, Vol. 12, Issue 4 https://doi.org/10.1107/S0909049505012719	journal	June 2005
Preparation and Luminescence Spectra of Calcium- and Rare-Earth (R = Eu, Tb, and Pr)-Codoped α-SiAlON Ceramics Xie, Rong-Jun; Mitomo, Mamoru; Uheda, Kyota Journal of the American Ceramic Society, Vol. 85, Issue 5 https://doi.org/10.1111/j.1151-2916.2002.tb00250.x	journal	May 2002
Local structure and structural rigidity of the green phosphor β -SiAlON:Eu ²⁺ Brgoch, J.; Gaultois, M. W.; Balasubramanian, M. Applied Physics Letters, Vol. 105, Issue 18 https://doi.org/10.1063/1.4901104	journal	November 2014
Proxies from Ab Initio Calculations for Screening Efficient Ce ³⁺ Phosphor Hosts Brgoch, Jakoah; DenBaars, Steven P.; Seshadri, Ram The Journal of Physical Chemistry C, Vol. 117, Issue 35 https://doi.org/10.1021/jp405858e	journal	August 2013
β-Sialon:Eu phosphor-in-glass: a robust green color converter for high power blue laser lighting Zhu, Qiang-Qiang; Wang, Xiao-Jun; Wang, Le Journal of Materials Chemistry C, Vol. 3, Issue 41 https://doi.org/10.1039/C5TC02236C	journal	January 2015
Luminescence Properties of Terbium-, Cerium-, or Europium-Doped α-Sialon Materials van Krevel, J. W. H.; van Rutten, J. W. T.; Mandal, H. Journal of Solid State Chemistry, Vol. 165, Issue 1 https://doi.org/10.1006/jssc.2001.9484	journal	April 2002
Prospects for LED lighting Pimputkar, Siddha; Speck, James S.; DenBaars, Steven P. Nature Photonics, Vol. 3, Issue 4 https://doi.org/10.1038/nphoton.2009.32	journal	April 2009
Synthesis and Photoluminescence Properties of β-sialon:Eu[sup 2+] (Si[sub 6−z]Al[sub z]O[sub z]N[sub 8−z]:Eu[sup 2+]) Xie, R. -J.; Hirosaki, N.; Li, H. -L. Journal of The Electrochemical Society, Vol. 154, Issue 10 https://doi.org/10.1149/1.2768289	journal	January 2007
La1−x−0.025Ce0.025Sr2+xAl1−xSixO5 solid solutions as tunable yellow phosphors for solid state white lighting Im, Won Bin; Fellows, Natalie N.; DenBaars, Steven P. Journal of Materials Chemistry, Vol. 19, Issue 9 https://doi.org/10.1039/b818313a	journal	January 2009
Crystal field splitting of lanthanide 4f−15d-levels in inorganic compounds Dorenbos, P. Journal of Alloys and Compounds, Vol. 341, Issue 1-2 https://doi.org/10.1016/S0925-8388(02)00056-7	journal	July 2002
Temperature Quenching of Yellow Ce ³⁺ Luminescence in YAG:Ce Bachmann, Volker; Ronda, Cees; Meijerink, Andries Chemistry of Materials, Vol. 21, Issue 10 https://doi.org/10.1021/cm8030768	journal	May 2009
Luminescent Properties of Ca-α-SiAlON:Eu[sup 2+] Phosphors Synthesized by Gas-Pressured Sintering Ryu, Jeong Ho; Park, Youn-Gon; Won, Hyong Sik Journal of The Electrochemical Society, Vol. 155, Issue 4 https://doi.org/10.1149/1.2834453	journal	January 2008
Average and Local Structure, Debye Temperature, and Structural Rigidity in Some Oxide Compounds Related to Phosphor Hosts Denault, Kristin A.; Brgoch, Jakoah; Kloß, Simon D. ACS Applied Materials & Interfaces, Vol. 7, Issue 13 https://doi.org/10.1021/acsami.5b00445	journal	March 2015
Controlling of Structural Ordering and Rigidity of β-SiAlON:Eu through Chemical Cosubstitution to Approach Narrow-Band-Emission for Light-Emitting Diodes Application Zhang, Xuejie; Fang, Mu-Huai; Tsai, Yi-Ting Chemistry of Materials, Vol. 29, Issue 16 https://doi.org/10.1021/acs.chemmater.7b01697	journal	August 2017
Efficient and stable laser-driven white lighting Denault, Kristin A.; Cantore, Michael; Nakamura, Shuji AIP Advances, Vol. 3, Issue 7 https://doi.org/10.1063/1.4813837	journal	July 2013
Structural Evolution and Atom Clustering in β-SiAlON: β-Si _{6– z} Al _z O _z N _{8– z} Cozzan, Clayton; Griffith, Kent J.; Laurita, Geneva Inorganic Chemistry, Vol. 56, Issue 4 https://doi.org/10.1021/acs.inorgchem.6b02780	journal	February 2017
VESTA : a three-dimensional visualization system for electronic and structural analysis Momma, Koichi; Izumi, Fujio Journal of Applied Crystallography, Vol. 41, Issue 3 https://doi.org/10.1107/S0021889808012016	journal	May 2008
Temperature dependence of Ce:YAG single-crystal phosphors for high-brightness white LEDs/LDs Arjoca, Stelian; Víllora, Encarnación G.; Inomata, Daisuke Materials Research Express, Vol. 2, Issue 5 https://doi.org/10.1088/2053-1591/2/5/055503	journal	May 2015
White-light emission from near UV InGaN-GaN LED chip precoated with blue/green/red phosphors Sheu, J. K.; Chang, S. J.; Kuo, C. H. IEEE Photonics Technology Letters, Vol. 15, Issue 1 https://doi.org/10.1109/LPT.2002.805852	journal	January 2003
Recent Developments in the Methods and Applications of the Bond Valence Model Brown, Ian David Chemical Reviews, Vol. 109, Issue 12 https://doi.org/10.1021/cr900053k	journal	December 2009
Structure–property correlations in Ce-doped garnet phosphors for use in solid state lighting Wu, Jennifer L.; Gundiah, Gautam; Cheetham, A. K. Chemical Physics Letters, Vol. 441, Issue 4-6 https://doi.org/10.1016/j.cplett.2007.05.023	journal	June 2007
A green-yellow emitting oxyfluoride solid solution phosphor Sr2Ba(AlO4F)1−x(SiO5)x:Ce3+ for thermally stable, high color rendition solid state white lighting Denault, Kristin A.; George, Nathan C.; Paden, Sara R. Journal of Materials Chemistry, Vol. 22, Issue 35 https://doi.org/10.1039/c2jm33620k	journal	January 2012
Luminescence in Eu²⁺-doped Ba₂Si₅N₈: fluorescence, thermoluminescence, and upconversion Höppe, H. A.; Lutz, H.; Morys, P. Journal of Physics and Chemistry of Solids, Vol. 61, Issue 12, p. 2001-2006 https://doi.org/10.1016/S0022-3697(00)00194-3	journal	December 2000
Emission colour tuning through coupled N/La introduction in Sr ₂ SiO ₄ :Eu ²⁺ Black, Ashley P.; Denault, Kristin A.; Frontera, Carlos Journal of Materials Chemistry C, Vol. 3, Issue 43 https://doi.org/10.1039/C5TC02437D	journal	January 2015
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
The geometry of polyhedral distortions. Predictive relationships for the phosphate group Baur, W. H. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, Vol. 30, Issue 5 https://doi.org/10.1107/S0567740874004560	journal	May 1974
On the origin of fine structure in the photoluminescence spectra of the β-sialon:Eu ²⁺ green phosphor Takahashi, Kohsei; Yoshimura, Ken-ichi; Harada, Masamichi Science and Technology of Advanced Materials, Vol. 13, Issue 1 https://doi.org/10.1088/1468-6996/13/1/015004	journal	February 2012
Phosphors for Solid-State White Lighting George, Nathan C.; Denault, Kristin A.; Seshadri, Ram Annual Review of Materials Research, Vol. 43, Issue 1 https://doi.org/10.1146/annurev-matsci-073012-125702	journal	July 2013
Insight into the Thermal Quenching Mechanism for Y ₃ Al ₅ O ₁₂ :Ce ³⁺ through Thermoluminescence Excitation Spectroscopy Ueda, Jumpei; Dorenbos, Pieter; Bos, Adrie J. J. The Journal of Physical Chemistry C, Vol. 119, Issue 44 https://doi.org/10.1021/acs.jpcc.5b08828	journal	October 2015
Elucidating Structure–Composition–Property Relationships of the β-SiAlON:Eu ²⁺ Phosphor Wang, Zhenbin; Ye, Weike; Chu, Iek-Heng Chemistry of Materials, Vol. 28, Issue 23 https://doi.org/10.1021/acs.chemmater.6b03555	journal	November 2016
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

Cited By (3)

Novel polygonal structure Mn ⁴⁺ activated In ³⁺ -based Elpasolite-type hexafluorides red phosphor for warm white light-emitting diodes (WLEDs) Hong, Feng; Cheng, Haiming; Song, Chao Dalton Transactions, Vol. 48, Issue 4 https://doi.org/10.1039/c8dt04690e	journal	January 2019
Mn ⁴⁺ nonequivalent-doped Al ³⁺ -based cryolite high-performance warm WLED red phosphors Hong, Feng; Xu, Haiping; Yang, Liu New Journal of Chemistry, Vol. 43, Issue 37 https://doi.org/10.1039/c9nj03607e	journal	January 2019
Insight into a novel rare‐earth‐free red‐emitting phosphor Li ₃ Mg ₂ NbO ₆ :Mn ⁴⁺ : Structure and luminescence properties Wang, Xicheng; Zhou, Xiaopeng; Cao, Yaxin Journal of the American Ceramic Society, Vol. 102, Issue 11 https://doi.org/10.1111/jace.16527	journal	May 2019

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:1399266

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

Luminescence properties of Eu-activated alkaline and alkaline-earth silicate Na{sub 2}Ca{sub 3}Si{sub 6}O{sub 16}

Journal Article · Tue Jul 01 00:00:00 EDT 2014 · Materials Research Bulletin · OSTI ID:1399266

Wang, Jing; Huang, Yanlin; Wang, Xigang; +1 more

Temperature dependence of the luminescence of calcium-magnesium phosphate Ca{sub 3}Mg{sub 3}(PO{sub 4}){sub 4}:Eu{sup 2+}, a blue-emitting material for white light-emitting diodes

Journal Article · Sat Mar 01 00:00:00 EST 2014 · Materials Research Bulletin · OSTI ID:1399266

Zhang, Xinmin; Pan, Qi; Kim, Sun Il; +1 more

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Understanding the links between composition, polyhedral distortion, and luminescence properties in green-emitting β-Si6–zAlzOzN8–z:Eu2+ phosphors

Citation Formats

References (33)

Cited By (3)

Similar Records

Related Subjects

Title: Understanding the links between composition, polyhedral distortion, and luminescence properties in green-emitting β-Si_6–zAl_zO_zN_8–z:Eu²⁺ phosphors