Nonstoichiometry, point defects and magnetic properties in Sr{sub 2}FeMoO{sub 6-{delta}} double perovskites

Journal Article · Sun Jan 15 00:00:00 EST 2012 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2011.10.043· OSTI ID:21612853

Kircheisen, R ^[1]; Toepfer, J ^[1]

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1. University of Applied Sciences Jena, Dept. SciTec, Carl-Zeiss-Promenade 2, 07745 Jena (Germany)

The phase stability, nonstoichiometry and point defect chemistry of polycrystalline Sr{sub 2}FeMoO{sub 6-{delta}} (SFMO) was studied by thermogravimety at 1000, 1100, and 1200 Degree-Sign C. Single-phase SFMO exists between -10.2{<=}log pO{sub 2}{<=}-13.7 at 1200 Degree-Sign C. At lower oxygen partial pressure a mass loss signals reductive decomposition. At higher pO{sub 2} a mass gain indicates oxidative decomposition into SrMoO{sub 4} and SrFeO{sub 3-x}. The nonstoichiometry {delta} at 1000, 1100, and 1200 Degree-Sign C was determined as function of pO{sub 2}. SFMO is almost stoichiometric at the upper phase boundary (e.g. {delta}=0.006 at 1200 Degree-Sign C and log pO{sub 2}=-10.2) and becomes more defective with decreasing oxygen partial pressure (e.g. {delta}=0.085 at 1200 Degree-Sign C and log pO{sub 2}=-13.5). Oxygen vacancies are shown to represent majority defects. From the temperature dependence of the oxygen vacancy concentration the defect formation enthalpy was estimated ({Delta}H{sub OV}=253{+-}8 kJ/mol). Samples of different nonstoichiometry {delta} were prepared by quenching from 1200 Degree-Sign C at various pO{sub 2}. An increase of the unit cell volume with increasing defect concentration {delta} was found. The saturation magnetization is reduced with increasing nonstoichiometry {delta}. This demonstrates that in addition to Fe/Mo site disorder, oxygen nonstoichiometry is another source of reduced magnetization values. - Graphical abstract: Nonstoichiometry {delta} of Sr{sub 2}FeMoO{sub 6-{delta}} as function of oxygen partial pressure at 1000, 1100, and 1200 Degree-Sign C. Highlights: Black-Right-Pointing-Pointer Sr{sub 2}FeMoO{sub 6-{delta}} is stable at T=1200 Degree-Sign C at low pO{sub 2} only. Black-Right-Pointing-Pointer Nonstoichiometry {delta} measured at 1200, 1100, and 1000 Degree-Sign C. Black-Right-Pointing-Pointer Increase of oxygen vacancy concentration with lower pO{sub 2}. Black-Right-Pointing-Pointer Reduction of magnetization with increasing nonstoichiometry {delta}.

• OSTI ID: 21612853
• Journal Information: Journal of Solid State Chemistry, Vol. 185; Other Information: DOI: 10.1016/j.jssc.2011.10.043; PII: S0022-4596(11)00585-8; Copyright (c) 2011 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
DECOMPOSITION
DEFECTS
MAGNETIC PROPERTIES
MAGNETIZATION
OXIDATION
OXYGEN
PARTIAL PRESSURE
PEROVSKITES
PHASE STABILITY
POLYCRYSTALS
SATURATION
TEMPERATURE DEPENDENCE
VACANCIES
CHEMICAL REACTIONS
CRYSTAL DEFECTS
CRYSTAL STRUCTURE
CRYSTALS
ELEMENTS
MINERALS
NONMETALS
PHYSICAL PROPERTIES
POINT DEFECTS
STABILITY
THERMODYNAMIC PROPERTIES