Structure Transformation and Cerium-Substituted Optical Response across the Carbonitridosilicate Solid Solution (LaδY1–δ)2Si4N6C(δ = 0–0.5)

Duke, Anna C.; Hermus, Martin; Brgoch, Jakoah

doi:10.1021/acs.inorgchem.7b02898

Title: Structure Transformation and Cerium-Substituted Optical Response across the Carbonitridosilicate Solid Solution (La_δY_1–δ)₂Si₄N₆C(δ = 0–0.5)

Journal Article · Wed Dec 20 00:00:00 EST 2017 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.7b02898· OSTI ID:1417391

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Univ. of Houston, TX (United States)

Following an investigation proving La₂Si₄N₆C crystallizes in a monoclinic space group, isostructural to Y₂Si₄N₆C, the reportedly hexagonal (La_0.5Y_0.5)₂Si₄N₆C was reinvestigated to examine the apparent crystal structure change across the solid solution. Initially, calculating the electronic structure and phonon density of states of (La_0.5Y_0.5)₂Si₄N₆C in the P6₃mc space group revealed an imaginary phonon mode, which is indicative of a structural instability. Displacing the atoms along the pathway of the imaginary vibration led to a previously unreported space group for carbonitridosilicates, trigonal P31c. The assignment of the trigonal space group was subsequently confirmed by synthesizing (La_0.5Y_0.5)₂Si₄N₆C using high-temperature, solid state synthesis and analyzing the crystal structure with high-resolution synchrotron X-ray powder diffraction. Preparing the solid solution, (La_δY_1–δ)_1.98Ce_0.02Si₄N₆C (δ = 0–0.5), showed that the crystal structure changes from the monoclinic to the trigonal space group at δ ≈ 0.25. Finally, substituting Ce³⁺ in the crystal structure to investigate the optical response via steady-state luminescent and photoluminescent quantum yield measurements reveals severe luminescent quenching with increasing La³⁺ content, due to a combination of absorption of luminescence by the host structure and thermal quenching. Here, these results display the virtue of combining computational and experimental techniques to solve inorganic crystal structures and assess potential phosphor hosts.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1417391

Journal Information:: Inorganic Chemistry, Vol. 57, Issue 1; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: ENGLISH

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
luminescence
solutions
crystal structure
space group
chemical structure

Title: Structure Transformation and Cerium-Substituted Optical Response across the Carbonitridosilicate Solid Solution (LaδY1–δ)2Si4N6C(δ = 0–0.5)

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Title: Structure Transformation and Cerium-Substituted Optical Response across the Carbonitridosilicate Solid Solution (La_δY_1–δ)₂Si₄N₆C(δ = 0–0.5)