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Title: Understanding the links between composition, polyhedral distortion, and luminescence properties in green-emitting β-Si 6–zAl zO zN 8–z:Eu 2+ phosphors

Abstract

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:Eu 2+ (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:Eu 2+. X-ray absorption near edge structure (XANES) is used to confirm that the majority of the activator Eu is in the Eu 2+ state, exhibiting the symmetry-allowed and efficient 4f 75d 0 → 4f 65d 1 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.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1];  [1];  [1];  [3]; ORCiD logo [1]
  1. Univ. of California, Santa Barbara, CA (United States)
  2. Bates College, Lewiston, ME (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC)
OSTI Identifier:
1399266
Grant/Contract Number:
AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. C
Additional Journal Information:
Journal Volume: 5; Journal Issue: 38; Journal ID: ISSN 2050-7526
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Cozzan, Clayton, Laurita, Geneva, Gaultois, Michael W., Cohen, Marcus, Mikhailovsky, Alexander A., Balasubramanian, Mahalingam, and Seshadri, Ram. Understanding the links between composition, polyhedral distortion, and luminescence properties in green-emitting β-Si6–zAlzOzN8–z:Eu2+ phosphors. United States: N. p., 2017. Web. doi:10.1039/C7TC03039H.
Cozzan, Clayton, Laurita, Geneva, Gaultois, Michael W., Cohen, Marcus, Mikhailovsky, Alexander A., Balasubramanian, Mahalingam, & Seshadri, Ram. Understanding the links between composition, polyhedral distortion, and luminescence properties in green-emitting β-Si6–zAlzOzN8–z:Eu2+ phosphors. United States. doi:10.1039/C7TC03039H.
Cozzan, Clayton, Laurita, Geneva, Gaultois, Michael W., Cohen, Marcus, Mikhailovsky, Alexander A., Balasubramanian, Mahalingam, and Seshadri, Ram. Thu . "Understanding the links between composition, polyhedral distortion, and luminescence properties in green-emitting β-Si6–zAlzOzN8–z:Eu2+ phosphors". United States. doi:10.1039/C7TC03039H.
@article{osti_1399266,
title = {Understanding the links between composition, polyhedral distortion, and luminescence properties in green-emitting β-Si6–zAlzOzN8–z:Eu2+ phosphors},
author = {Cozzan, Clayton and Laurita, Geneva and Gaultois, Michael W. and Cohen, Marcus and Mikhailovsky, Alexander A. and Balasubramanian, Mahalingam and Seshadri, Ram},
abstractNote = {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-Si6–zAlzOzN8–zEu0.009), 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.},
doi = {10.1039/C7TC03039H},
journal = {Journal of Materials Chemistry. C},
number = 38,
volume = 5,
place = {United States},
year = {Thu Sep 21 00:00:00 EDT 2017},
month = {Thu Sep 21 00:00:00 EDT 2017}
}

Journal Article:
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  • The crystal structure, electronic structure, and photoluminescence properties of Eu{sub x}Si{sub 6-z}Al{sub z-x}O{sub z+x}N{sub 8-z-x} (x=0-0.1, 0<z<1) and Eu{sub x}M{sub y}Si{sub 6-z}Al{sub z-x-y}O{sub z+x+y}N{sub 8-z-x-y} (M=2Li, Mg, Ca, Sr, Ba) have been studied. Single-phase Eu{sub x}Si{sub 6-z}Al{sub z-x}O{sub z+x}N{sub 8-z-x} can be obtained in very narrow ranges of x{<=}0.06 (z=0.15) and z<0.5 (x=0.3), indicating that limited Eu{sup 2+} ions can be incorporated into nitrogen-rich Si{sub 6-z}Al{sub z}O{sub z}N{sub 8-z}. The Eu{sup 2+} ion is found to occupy the 2b site in a hexagonal unit cell (P6{sub 3}/m) and directly connected by six adjacent nitrogen/oxygen atoms ranging 2.4850-2.5089 A. The calculatedmore » host band gaps by the relativistic DV-X{alpha} method are about 5.55 and 5.45 eV (without Eu{sup 2+} 4f5d levels) for x=0 and 0.013 in Eu{sub x}Si{sub 6-z}Al{sub z-x}O{sub z+x}N{sub 8-z-x} (z=0.15), in which the top of the 5d orbitals overlap with the Si-3s3p and N-2p orbitals within the bottom of the conduction band of the host. Eu{sub x}Si{sub 6-z}Al{sub z-x}O{sub z+x}N{sub 8-z-x} shows a strong green emission with a broad Eu{sup 2+} band centered at about 530 nm under UV to near-UV excitation range. The excitation and emission spectra are hardly modified by Eu concentration and dual-doping ions of Li and other alkaline-earth ions with Eu. Higher Eu concentrations can significantly quench the luminescence of Eu{sup 2+} and decrease the thermal quenching temperature. In addition, the emission spectrum can only be slightly tuned to the longer wavelengths ({approx}529-545 nm) by increasing z within the solid solution range of z<0.5. Furthermore, the luminescence intensity of Eu{sub x}Si{sub 6-z}Al{sub z-x}O{sub z+x}N{sub 8-z-x} can be improved by increasing z and the dual-doping of Li and Ba. - Graphical abstract: Excitation and emission spectra of Eu{sub x}Si{sub 6-z}Al{sub z-x}O{sub z+x}N{sub 8-z-x} with the project of a 2x2x2 supercell crystal structure viewed along (001), in which red spheres are the Eu atoms.« less
  • SiAlON ceramics, solid solutions based on the Si 3N 4 structure, are important, lightweight structural materials with intrinsically high strength, high hardness, and high thermal and chemical stability. Described by the chemical formula β-Si 6–zAl zO zN 8–z, from a compositional viewpoint, these materials can be regarded as solid solutions between Si 3N 4 and Al 3O 3N. A key aspect of the structural evolution with increasing Al and O (z in the formula) is to understand how these elements are distributed on the β-Si 3N 4 framework. The average and local structural evolution of highly phase-pure samples of β-Simore » 6–zAl zO zN 8–z with z = 0.050, 0.075, and 0.125 are studied here, using a combination of X-ray diffraction, NMR studies, and density functional theory calculations. Synchrotron X-ray diffraction establishes sample purity and indicates subtle changes in the average structure with increasing Al content in these compounds. Solid-state magic-angle-spinning 27Al NMR experiments, coupled with detailed ab initio calculations of NMR spectra of Al in different AlO qN 4–q tetrahedra (0 ≤ q ≤ 4), reveal a tendency of Al and O to cluster in these materials. Independently, the calculations suggest an energetic preference for Al–O bond formation, instead of a random distribution, in the β-SiAlON system.« less
  • The influence of the replacement of Sr by Ca on structural and luminescence properties of Eu{sup 2+}-doped Sr{sub 2}Si{sub 5}N{sub 8} is reported. The Rietveld refinement of the powder X-ray diffraction data shows that the Ca{sup 2+} ion preferentially occupies the larger Sr site in Sr{sub 2}Si{sub 5}N{sub 8}:Eu{sup 2+}. Although the excitation spectrum is hardly modified, the position of the emission band of Eu{sup 2+} can be tailored through partial replacement of Sr by Ca in Sr{sub 2}Si{sub 5}N{sub 8}:Eu{sup 2+}, resulting in red-emission shifting from 620 to 643 nm. Furthermore, (Sr, Ca){sub 2}Si{sub 5}N{sub 8}:Eu{sup 2+} shows highmore » potential as a conversion phosphor for white-light LED applications due to similar absorption, conversion efficiency and thermal quenching behaviour for 465 nm excitation after the introduction of the Ca ion. - Graphical abstract: The temperature dependence of the luminescence efficiency of M{sub 1.9}Eu{sub 0.1}Si{sub 5}N{sub 8} (M=Ca, Sr, Ba) and Sr{sub 1.3}Ca{sub 0.6}Eu{sub 0.1}Si{sub 5}N{sub 8} ({lambda}{sub exc}=465 nm)« less
  • Two isostructural europium(II) quaternary chalcogenides, Na{sub 8}Eu{sub 2}(Si{sub 2}S{sub 6}){sub 2}, 1, and Na{sub 8}Eu{sub 2}(Ge{sub 2}S{sub 6}){sub 2}, 2, containing an ethane-like (Si{sub 2}S{sub 6}){sup 6−} or (Ge{sub 2}S{sub 6}){sup 6−} moiety have been synthesized by employing the polychalcogenide molten flux method. Single-crystal X-ray diffraction reveals that both compounds crystallize in the C2/m space group, and their structures contain layers of ([Na{sub 2}Eu{sub 2}(Si{sub 2}S{sub 6}){sub 2}]{sup 6−}){sub ∞} or ([Na{sub 2}Eu{sub 2}(Ge{sub 2}S{sub 6}){sub 2}]{sup 6−}){sub ∞} anions held together by six interlayer sodium cations to yield (Na{sub 6}[Na{sub 2}Eu{sub 2}(Si{sub 2}S{sub 6}){sub 2}]){sub ∞} and (Na{sub 6}[Na{submore » 2}Eu{sub 2}(Ge{sub 2}S{sub 6}){sub 2}]){sub ∞}. Compound 2 is a semiconductor with an optical band gap of 2.15(2) eV. The temperature dependence of the magnetic susceptibility indicates that compounds 1 and 2 are paramagnetic with μ{sub eff}=7.794(1) μ{sub B} per Eu and g=1.964(1) for 1 and μ{sub eff}=8.016(1) μ{sub B} per Eu and g=2.020(1) for 2, moments that are in good agreement with the europium(II) spin-only moment of 7.94 μ{sub B}. The europium-151 Mössbauer isomer shift of 2 confirms the presence of europium(II) cations with an electronic configuration between [Xe]4f{sup 6.81} and 4f{sup 7}6s{sup 0.32}. - Graphical abstract: TOC figure caption: structure of Na{sub 8}Eu{sub 2}(Si{sub 2}S{sub 6}){sub 2} viewed along the a-axis showing the filling of A–B and B–A types of anion layers with two different types of cations. - Highlights: • Synthesis of quaternary europium chalcogenides containing ethane-like dimer. • Structural characterization employing single-crystal X-ray diffraction. • Mössbauer spectroscopy and magnetic measurements confirm presence of Eu(II)« less
  • Graphical abstract: The phosphor has two separated emission centers with the dependent emission intensity on Eu{sup 2+} doping. There is a red-shift in the emission due to energy transfer with increasing the Eu{sup 2+}-doping. - Highlights: • Green-origin-emitting phosphors of Eu{sup 2+}-doped Ca{sub 7}Si{sub 2}P{sub 2}O{sub 16} were firstly prepared by chemical sol–gel method. • The tunable luminescence color was realized by the changing Eu{sup 2+}-doping in Ca{sub 7}Si{sub 2}P{sub 2}O{sub 16}. • Ca{sub 7}Si{sub 2}P{sub 2}O{sub 16}:Eu{sup 2+} displays two typical luminescence centers with the emission depending on Eu{sup 2+} doping. • Eu{sup 2+}-doped Ca{sub 7}Si{sub 2}P{sub 2}O{sub 16}more » phosphor has an excellent thermal stability on the temperature quenching. - Abstract: Color tunable green-origin-emitting phosphor of Eu{sup 2+}-doped phosphate-silicate Ca{sub 7}Si{sub 2}P{sub 2}O{sub 16} was prepared by chemical sol–gel method. The X-ray powder diffraction, the photoluminescence excitation and emission spectra, time resolved spectra, and thermal stability were measured. The excitation spectra can well match with the emission light of near UV-LED chips (360–400 nm). The tunable luminescence was realized by changing Eu{sup 2+}-doping concentration. Ca{sub 7}Si{sub 2}P{sub 2}O{sub 16}:Eu{sup 2+} displays two typical luminescence centers, which were suggested to originate from two Ca{sup 2+} sites in the host. With increasing Eu{sup 2+} doping concentrations, the green emission band shifts to long wavelength. Energy transfer between the two different Eu{sup 2+} ions is discussed by analyzing the photoluminescence excitation and emission spectra, concentration-dependent luminescence intensity, and lifetimes. The dependence of the luminescence intensity of Ca{sub 7}Si{sub 2}P{sub 2}O{sub 16}:Eu{sup 2+} on temperatures was measured. The activation energy (ΔE) for thermal quenching was reported.« less