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Nitrides with Inverse K 2 [NiF 4 ] Structure: ( R 1– x Ca 3+ x N 1– x /3 )Bi 2 with R = Rare‐Earth Metal
Author(s) -
Gäbler Frank,
Bräunling Daniel,
Senyshyn Anatoliy,
Schnelle Walter,
Niewa Rainer
Publication year - 2010
Publication title -
zeitschrift für anorganische und allgemeine chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.354
H-Index - 66
eISSN - 1521-3749
pISSN - 0044-2313
DOI - 10.1002/zaac.200900573
Subject(s) - crystallography , x ray crystallography , crystal structure , analytical chemistry (journal) , electrical resistivity and conductivity , neutron diffraction , nitride , materials science , chemistry , diffraction , physics , chromatography , layer (electronics) , optics , quantum mechanics , composite material
Abstract The novel nitrides ( R 1– x Ca 3+ x N 1– x /3 )Bi 2 (with R = La, Ce, Pr) crystallize in the K 2 [NiF 4 ] structure type ( I 4/ mmm , No. 139, Z = 2). Samples (La 1– x Ca 3+ x N 1– x /3 )Bi 2 with x = 0.10, 0.05, 0.00, (Ce 1– x Ca 3+ x N 1– x /3 )Bi 2 with x = 0.30, and (PrCa 3 N)Bi 2 were obtained as single phase microcrystalline powders according to X‐ray diffraction and the crystal structure details were derived from Rietveld refinements based on X‐ray and neutron diffraction powder patterns. A partial order of R 3+ /Ca 2+ on two crystallographic sites is governed by different ionic radii and charges. (La 1– x Ca 3+ x N 1– x /3 )Bi 2 and (Ce 1– x Ca 3+ x N 1– x /3 )Bi 2 exhibit small homogeneity ranges and typically a nitrogen deficiency. In contrast, for (PrCa 3 N)Bi 2 no indications for a significant homogeneity range or deficiency of nitrogen was observed. (La 1– x Ca 3+ x N 1– x /3 )Bi 2 with x = 0.05 is a diamagnet. X‐ray absorption spectroscopy at the Ce L 3 ‐edge as well as magnetic susceptibility measurements evidence that (Ce 1– x Ca 3+ x N 1– x /3 )Bi 2 with x = 0.30 contains Ce 3+ in the 4 f 1 configuration. According to electrical resistivity data, samples from all three systems are heavily doped semiconductors.