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Resolving Composition and Structure of RE –Sb–O–C Natural Superlattice Phases ( RE = La, Ho)
Author(s) -
Wang Peng,
Forbes Scott,
Svitlyk Volodymyr,
Aushana Ashur,
Mozharivskyj Yurij
Publication year - 2011
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201100313
Subject(s) - antimonide , chemistry , crystallography , superlattice , antimony , melting point , oxide , composition (language) , phase (matter) , materials science , inorganic chemistry , organic chemistry , linguistics , philosophy , optoelectronics
A family of rare earth antimonide oxycarbides have been prepared and structurally characterized. These superlattice phases are constructed from NaCl‐type RE Sb slabs sandwiched between RE –O–C layers. Depending on the carbon content and synthetic conditions, three different RE –Sb–O–C structures can be obtained. At lower temperatures, RE 9– δ Sb 5 (O,C) 5 phases are obtained for RE = La, Ho. These phases adopt a stuffed Sc 2 Sb‐type structure with P 4/ nmm symmetry. An O/C mixture, in which the O/C ratio is larger than 4:1, is randomly distributed within the RE –O–C layers. The RE atoms are highly disordered within the oxide layer. At temperatures above the melting point of the samples, RE 9 Sb 5 O 4 C phases with P 4/ n symmetry are produced. The RE –O–C layers in RE 9 Sb 5 O 4 are fully ordered; the RE sites are well defined, and the O and C atoms occupy the tetrahedral and square‐pyramidal voids, respectively. At high temperatures, a new ordered La 14 Sb 8 O 7 C structure with P 4 bm symmetry was discovered. The La 14 Sb 8 O 7 C phase is structurally similar to RE 9 Sb 5 O 4 C and features orderedarrangements of La and O/C atoms in the La–O–C layer. The RE 9– δ Sb 5 (O,C) 5 , RE 9 Sb 5 O 4 C and La 14 Sb 8 O 7 C phases appear to be charge‐balanced, and their compositions and structures are controlled by the O/C ratio. Parallel preparative experiments revealed the importance of carbon in the formation of these layered phases. In addition, it has been established that the purity of the rare earth metals influences the compositions and structures of the products.