Stabilization of Ca1-dFe2-xMnxO4 (0.44 lt x lt 2) with CaFe2O4-type Structure and Ca2plus Defects in 1D Channels
Solid solutions of Ca{sub 1-{delta}}Fe{sub 2-x}Mn{sub x}O{sub 4} (0.45 {<=} x {<=} 2) were synthesized from CaCl{sub 2} as flux at 850 C in air. The entire series, even with x = 2, crystallizes in the CaFe{sub 2}O{sub 4}-type structure (Pnma), rather than in the CaMn{sub 2}O{sub 4}-type structure (Pbcm). Rietveld refinements confirmed mixed-valency Mn{sup 3+}/Mn{sup 4+} and a substantial level of Ca{sup 2+} deficiency ({delta} {approx} 0.25) at high x. With increasing x, the unit-cell dimensions a and b decrease, while that of c increases. Detailed structural analyses, together with Mn K-edge X-ray absorption and {sup 57}Fe Moessbauer spectroscopy studies, revealed that the stabilization of CaFe{sub 2}O{sub 4}-type structure, even at high values of x, is due to the existence of non-Jahn-Teller active Mn{sup 4+} (and Fe{sup 3+}), which is compensated by the formation of the Ca{sup 2+} deficiencies in the one-dimensional (1D) channels of Ca{sub 1-{delta}}Fe{sub 2-x}Mn{sub x}O{sub 4} during the flux synthesis. Antiferromagnetic (AFM) long-range ordering is achieved for all compounds at low temperature, because of strong AFM interactions between Mn{sup 3+}/Mn{sup 4+} and Fe{sup 3+}. In addition, a spin (or cluster) glass component was also observed, as expected, because of the extensive Mn/Fe structural and Mn{sup 3+}/Mn{sup 4+} charge disordering.
- Research Organization:
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Sponsoring Organization:
- USDOE SC OFFICE OF SCIENCE (SC)
- DOE Contract Number:
- DE-AC02-98CH10886
- OSTI ID:
- 1041820
- Report Number(s):
- BNL-97498-2012-JA; CMATEX; TRN: US201212%%232
- Journal Information:
- Chemistry of Materials, Vol. 22; ISSN 0897-4756
- Country of Publication:
- United States
- Language:
- English
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