• Journal of the Korean Magnetics Society
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• v.24 no.2
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• pp.46-50
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• 2014

The crystallographic properties and cationic distribution of $M_{0.2}Fe_{2.8}O_4$ (M =Mn, Ni, Cu) and $Fe_3O_4$ thin films prepared by sol-gel method have been investigated by X-ray diffraction (XRD) and conversion electron M$\ddot{o}$ssbauer spectroscopy (CEMS). The ionic valence, preferred site, and hyperfine field of Fe ions of the ferrites could be obtained by analyzing the CEMS spectra. The $M_{0.2}Fe_{2.8}O_4$ films were found to maintain cubic spinel structure as in $Fe_3O_4$ with the lattice constant slightly decreased for Ni substitution and increased for Mn and Cu substitution from that of $Fe_3O_4$. Analyses on the CEMS data indicate that $Mn^{2+}$ and $Ni^{2+}$ ions substitute octahedral $Fe^{2+}$ sites mostly, while $Cu^{2+}$ ions substitute both the octahedral and tetrahedral sites. The observed intensity ratio $A_B/A_A$ of the CEMS subspectra of the samples exhibited difference from the theoretical value. It is interpreted as due to the effect of the M substitution for A and B on the Debye temperature of the site. The relative line-broadening of the B-site CEMS subspectra can be explained by the dispersion of magnetic hyperfine fields due to random distribution of M cations in the B sites.

• Journal of the Korean Magnetics Society
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• v.15 no.2
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• pp.109-112
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• 2005

Electronic and magnetic properties of $Ti_{1-x}M_xO_{2-\delta}$ (M=Co and Fe) thin films grown by sol-gel method have been investigated. Anatase and rutile $Ti_{1-x}Co_xO_{2-\delta}$ films were successfully grown on $Al_2O_3$ (0001) substrates and exhibited p-type electrical conductivity while the undoped films n-type conductivity. Room temperature vibrating sample magnetometry measurements on the anatase and rutile $Ti_{1-x}Co_xO_{2-\delta}$ films with same x ($=4.8 at.{\%}$) showed quite similar magnetic hysteresis curves with the saturation magnetic moment of $\~4 {\mu}_B$ per Co ion despite their differences in structural and electronic properties. Such giant magnetic moment is attributable to the unquenched orbital moment of the $Co^{2+}$ ions substituting the octahedral $Ti^{4+}$ sites. Similar ferromagnetic behavior was observed for $Ti_{1-x}Fe_xO_{2-\delta}$ films that are highly resistive compared to the Co doped samples. Saturation magnetic moment was found to decrease for higher x, i.e., $\~2$ and $\~1.5 {\mu}_B$ per Fe ion for x=2.4 and 5.8 at. $\%$, respectively. Conversion electron $M\ddot{o}ssbauer$ spectroscopy measurements predicted the coexistence of $Fe^{2+}$ and $Fe^{3+}$ ions at the octahedral sites of $Ti_{1-x}Fe_xO_{2-\delta}$.

• Journal of Magnetics
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• v.11 no.1
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• pp.51-54
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• 2006

Variation of magnetic properties through Cr substitution for Co in inverse-spinel $CoFe_2O_4$ has been investigated by vibrating-sample magnetometry (VSM) and conversion electron $M\ddot{o}ssbauer$ spectroscopy (CEMS). $Cr_{x}Co_{1-x}Fe_2O_4$ samples were prepared as thin films by a sol-gel method. The lattice constant of the $Cr_{x}Co_{1-x}Fe_2O_4$ samples was found to remain unchanged, explainable in terms of a reduction of tetrahedral $Fe^{3+}$ ion to $Fe^{2+}$ due to substitution of $Cr^{3+}$ ion into octahedral $Co^{2+}$ site. The existence of the tetrahedral $Fe^{2+}$ ions in $Cr_{x}Co_{1-x}Fe_2O_4$ was confirmed by CEMS analysis. Room-temperature magnetic hysteresis curves for the $Cr_{x}Co_{1-x}Fe_2O_4$ films measured by VSM revealed that the saturation magnetization $M_s$ increases by Cr doping. The $M_s$ is maximized when x = 0.1 and decreases for higher x but is still bigger than that of $CoFe_2O_4$. The increase of $M_s$ can be explained partly by the reduction of the tetrahedral $Fe^{3+}$ ion to $Fe^{2+}$.

• Journal of the Korean Magnetics Society
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• v.15 no.2
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• pp.96-99
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• 2005

Phase transition from normal- to inverse-spinel structure has been observed for $Fe_xCo_{3-x}O_4$ thin films as the Fe composition (x) increases from 0 to 2. The samples were fabricated as thin films by sol-gel method on Si(100) substrates. X-ray diffraction measurements revealed a coexistence of two phases, normal and inverse spinel, for $0.76{\le}x{\le}0.93$. The normal-spinel phase is dominant for $x{\le}0.55$ while the inverse-spinel phase for $x{\ge}l.22$. The cubic lattice constant of the inverse-spinel phase is larger than that of the normal-spinel phase. For both phases the lattice constant increases with increasing x. X-ray photoelectron spectroscopy measurements revealed that both $Fe^{2+}$ and $Fe^{3+}$ ions exist with similar strength in the x=0.93 sample. Conversion electron $M\ddot{o}ssbauer$ spectra measured on the same sample showed that $Fe^{2+}$ ions prefer the octahedral $Co^{3+}$ sites, indicating the formation of the inverse-spinel phase. Analysis on the measured optical absorption spectra for the samples by spectroscopic ellipsometry indicates the dominance of the normal spinel phase for low x in which $Fe^{3+}$ ions tend to substitute the octahedral sites.