Dissertation
Dissertation > Industrial Technology > Chemical Industry > Inorganic compounds, the chemical industry of the metal elements > Section II group metal elements of inorganic compounds > Inorganic compounds of elements of the alkaline earth metal (Ⅱ A family ) > Inorganic compounds of calcium

The Effects of Fe, Cr and Sc Doping on Ca3Co2O6

Author ChenJuan
Tutor OuYangZhongWen
School Huazhong University of Science and Technology
Course Materials Physics and Chemistry
Keywords Ca3(Co,T)2O6 doping FM interaction ESR spectra magnetic relaxation
CLC TQ132.32
Type Master's thesis
Year 2012
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The physical properties of transition metal oxide have been one of the hot topics inthe study of condensed matter physics. Quasi-one-dimensional spin system Ca3(Co,T)2O6(T=transition metal ions) have been attracting a lot of interests due to its thermoelectricproperties and rich magnetic behavior. In this paper, we performed our studies focus onthe synthesis, crystal structure and magnetic properties under low temperature of Fe-, Cr-and Sc-doped compounds. The main contents can be summarized as follows:(1)We have synthesized polycrystalline samples of Ca3Co2-xFexO6and singlecrystal of Ca3Co1.6Fe0.4O6by sol-gel reaction and flux method respectively. Themagnetization of Ca3Co2-xFexO6show that the high-temperature curve complies well withthe Curie-Weiss law, while the low-temperature part does not but exhibit an upturn due tothe presence of short-range ordering. This uptown becomes ambiguous as x increase andalmost disappears at x=0.7. Simultaneously, the value of pdecreases and eventuallyreaches zero because the intrachain FM coupling(J) is reduced. These results all showthat FM interactions decrease as x increase. The ESR spectra of polycrystalline samplex=0.4show that a resonance consisting of eight hyperfine-structure peaks starts to emergeas temperature is lowed to be50K. Such hyperfine peaks are due to the splitting producedby Co nuclei. The nuclear spin quantum number of59Co is I=7/2and a resonancesuperimposed with eight (2I+1) hyperfine splittings is expected. The corresponding gvalue is derived to be4.2, much larger than2.0. This again shows that observedresonance is due to Co ions with strong crystal-field effects of octahedra and trigonalprisms. The magnetization of single-crystal Ca3Co1.6Fe0.4O6show that the magneticanisotropy is much modified when the FM intrachain interaction is much suppressed byFe-doping.(2) Polycrystalline samples of Ca3Co2-xCrxO6have been prepared by sol-gel reaction.XRD patterns and lattice constant reveal that solid solubility of Cr in Ca3Co2O6is aboutx=0.4for rhombohedral phase. The magnetization of Ca3Co2-xCrxO6show that the valueof p, FM coupling(J) and saturation magnetization all decreased as x increased from x=0.0to x=0.4. These results all show that FM interactions decrease as x increase.(3) We studied the magnetic relaxation of Ca3(Co,T)2O6(T=Fe, Cr and Sc). We haveillustrated the presence of spin-glass-like freezing in these compounds. The magneticrelaxation of Ca3Co2-xFexO6are similar with that of Ca3Co2O6while the magnetizationsof Ca3Co2-xCrxO6and Ca3Co2-xScO6decay more slowly than x=0.0. So the relaxationcharacteristic time is significantly enhanced as compared to x=0.0. Different from thecases in x=0.0with strong spin frustration, the spin freezing in doped compounds isclosely associated with chemical disorder with randomness or imperfects.

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