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Title: Optical properties of Eu{sup 2+}/Eu{sup 3+} mixed valence, silicon nitride based materials

Eu{sub 2}SiN{sub 3}, a mixed valence europium nitridosilicate, has been prepared via solid-state reaction synthesis and its oxidation behavior and optical properties have been determined. Furthermore, the stability of several isostructural compounds of the type M{sup 2+}L{sup 3+}SiN{sub 3} has been predicted by using the density functional theory calculations, and verified by the actual synthesis of CaLaSiN{sub 3}, CaEuSiN{sub 3} and EuLaSiN{sub 3}. The band gap of CaLaSiN{sub 3} was found around 3.2 eV giving the material its yellow color. Eu{sub 2}SiN{sub 3} on the other hand is black due to a combination of the 4f–5d absorption band of Eu{sup 2+} and the charge transfer band of Eu{sup 3+}. Thermogravimetric analysis and Raman spectroscopic study of Eu{sub 2}SiN{sub 3} revealed that oxidation of this compound in dry air takes place via a nitrogen retention complex. - Graphical abstract: Energy level scheme of Eu{sub 2}SiN{sub 3} showing the occupied N{sup 3−} 2p band (blue rectangle), unoccupied Eu{sup 2+} 5d band (white rectangle), occupied Eu{sup 2+} 4f ground states (filled red circles) and unoccupied Eu{sup 2+} ground states (open red circles). - Highlights: • Density functional theory calculations on the stability of M{sup 2+}L{sup 3+}SiN{sub 3} compounds. • Solid-state reaction synthesis ofmore » Eu{sub 2}SiN{sub 3}, CaLaSiN{sub 3}, EuLaSiN{sub 3} and CaEuSiN{sub 3}. • Determination of the Eu{sup 2+} 4f–5d and Eu{sup 3+} CT transitions in M{sup 2+}L{sup 3+}SiN{sub 3} compounds. • Oxidation of Eu{sub 2}SiN{sub 3} in dry air takes place via a nitrogen retention complex.« less
Authors:
 [1] ;  [2] ;  [1] ;  [3] ; ;  [1]
  1. Chemical Engineering and Chemistry, Eindhoven University of Technology, Den Dolech 2, 5600 MB Eindhoven (Netherlands)
  2. (Netherlands)
  3. Fundamental Aspects of Materials and Energy, Delft University of Technology, Mekelweg 15, 2629 JB Delft (Netherlands)
Publication Date:
OSTI Identifier:
22334210
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 213; Other Information: Copyright (c) 2014 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION; DENSITY FUNCTIONAL METHOD; EUROPIUM IONS; GROUND STATES; NITROGEN; OXIDATION; SILICON NITRIDES; SOLIDS; SYNTHESIS; THERMAL GRAVIMETRIC ANALYSIS