화학공학소재연구정보센터
Journal of the American Chemical Society, Vol.134, No.6, 3215-3227, 2012
Systematic Study of Compositional and Synthetic Control of Vacancy and Magnetic Ordering in Oxygen-Deficient Perovskites Ca2Fe2-xMnxO5+y and CaSrFe2-xMnxO5+y (x=1/2, 2/3, and 1; y=0-1/2)
Ten compounds belonging to the series of oxygen-deficient perovskite oxides Ca2Fe2-xMnxO5 and CaSrFe2-xMnxO5+y, where x = 1/2, 2/3, and 1 and y approximate to 0-0.5, were synthesized and investigated with respect to the ordering of oxygen vacancies on both local and long-range length scales and the effect on crystal structure and magnetic properties. For the set with y approximate to 0 the oxygen vacancies always order in the long-range sense to form the brownmillerite structure containing alternating layers of octahedrally and tetrahedrally coordinated cations. However, there is a change in symmetry from Pnma to Icmm upon substitution of Sr for one Ca for all x, indicating local T-d chain (vacancy) disorder. In the special case of CaSrFeMnO5 the neutron diffraction peaks broaden, indicating only short-range structural order on a length scale of similar to 160 angstrom. This reveals a systematic progression from Ca2FeMnO5 (Pnma, well-ordered tetrahedral chains) to CaSrFeMnO5 (Icmm, disordered tetrahedral chains, overall short-range order) to Sr2FeMnO5 (Pm (3) over barm, destruction of tetrahedral chains in a long-range sense). Systematic changes occur in the magnetic properties as well. While long-range antiferromagnetic order is preserved, the magnetic transition temperature, T-c, decreases for the same x when Sr substitutes for one Ca. A review of the changes in T-c, for the series Ca2Fe2-xMxO5, taking into account the tetrahedral/octahedral site preferences for the various M3+ ions, leads to a partial understanding of the origin of magnetic order in these materials in terms of a layered antiferromagnetic model. While in all cases the preferred magnetic moment direction is (010) at low temperatures, there is a cross over for x = 0.5 to (100) with increasing temperature for both the Ca2Fe2-xMnxO5 and the CaSrFe2-xMnxO5 series. For the y > 0 phases, while a brownmillerite ordering of oxygen vacancies is preserved for the Ca-2 phases, a disordered Pm (3) over barm cubic perovskite structure is always found when Sr is substituted for one Ca. Long-range magnetic order is also lost, giving way to spin glass or cluster-glass-like behavior below similar to 50 K. For the x = 0.5 phase, neutron pair distribution function (NPDF) studies show a local structure related to brownmillerite ordering of oxygen vacancies. Neutron diffraction data at 3.8 K show a broad magnetic feature, incommensurate with any multiple of the chemical lattice, and with a correlation length (magnetic domain) of 6.7(4) angstrom.