Correlating Local Compositions and Structures with the Macroscopic Optical Properties of Ce3+-Doped CaSc2O4, an Efficient Green-Emitting Phosphor

George, Nathan C.; Brgoch, Jakoah; Pell, Andrew J.; Cozzan, Clayton; Jaffe, Adam; Dantelle, Géraldine; Llobet, Anna; Pintacuda, Guido; Seshadri, Ram; Chmelka, Bradley F.

doi:10.1021/acs.chemmater.6b05394

Correlating Local Compositions and Structures with the Macroscopic Optical Properties of Ce³⁺-Doped CaSc₂O₄, an Efficient Green-Emitting Phosphor

Journal Article · Tue Apr 11 00:00:00 EDT 2017 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.6b05394· OSTI ID:1368325

George, Nathan C. ^[1]; ^[1]; Pell, Andrew J. ^[2]; Cozzan, Clayton ^[1]; ^[1]; Dantelle, Géraldine ^[3]; Llobet, Anna ^[4]; Pintacuda, Guido ^[2]; ^[1]; ^[1]

Univ. of California, Santa Barbara, CA (United States)
Univ. of Lyon (France)
Centre National de la Recherche Scientifique (CNRS) (France)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

Calcium scandate (CaSc₂O₄) substituted with small amounts (<1%) of Ce³⁺ is a recently discovered bright-green-emitting phosphor with favorable light absorption and emission properties and robust temperature stability that make it well-suited for solid-state white-lighting applications. Combined analyses of scattering, solid-state nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR), and photoluminescence measurements establish the compositional and structural origins of the macroscopic optical properties of this phosphor material. Simultaneous refinements of synchrotron X-ray and neutron diffraction data of Ce³⁺-doped CaSc₂O₄ enable the average crystal structure to be determined, which is shown to correspond to an exceedingly rigid host structure, as corroborated by density functional theory (DFT) calculations. Such structural rigidity leads to high quantum efficiency, which is optimized by the substitution of as little as 0.5 mol % of Ce³⁺ for Ca²⁺ ions, with higher extents of Ce³⁺ substitution leading to decreased photoluminescent quantum yields. Solid-state ⁴³Ca and ⁴⁵Sc magic-angle spinning (MAS) NMR spectra are sensitive to the effects of the paramagnetic Ce³⁺ dopant ions on nearby atoms in the host structure and yield evidence for local structural distortions. EPR measurements provide direct insights on structures of the Ce³⁺ ions, as a function of Ce³⁺ substitution. The combined scattering and spectroscopic analyses yield detailed new understanding of the local and long-range structures of Ce³⁺-doped CaSc₂O₄, which account for the sensitive composition-dependent optical properties of this important phosphor material.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: AC52‐06NA25396; AC02‐06CH11357; (ANR‐11‐IDEX‐0007; ANR‐10‐LABX‐0064; NSF‐DGE 0801627; FP7‐PEOPLE‐2012‐ITN

OSTI ID:: 1368325

Journal Information:: Chemistry of Materials, Vol. 29, Issue 8; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: ENGLISH

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Cited by: 63 works

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Local coordination, electronic structure, and thermal quenching of Ce ³⁺ in isostructural Sr ₂ GdAlO ₅ and Sr ₃ AlO ₄ F phosphors Ji, Haipeng; Xu, Jian; Asami, Kazuki Journal of the American Ceramic Society, Vol. 102, Issue 3 https://doi.org/10.1111/jace.15985	journal	August 2018

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