Mn和Fe掺杂对尖晶石氧化物Co2MnO4结构和磁性的影响

doi:10.15541/jim20160518

摘要/Abstract

摘要：

以金属盐及柠檬酸为原料, 采用溶胶-凝胶法制备了尖晶石氧化物Co_2-_xMn₁₊_xO₄和Co_2-_xFe_xMnO₄系列, 通过XRD、FT-IR及PPMS等手段研究了Co₂MnO₄及系列掺杂样品的成相、结构、磁性等特征。结果表明, Co_2-_xMn₁₊_xO₄系列在x<0.6时, 呈单相立方结构, 晶格常数和磁性随着Mn掺杂量的增加而增大, x≥0.6时逐渐向四方结构转化, 磁性下降, 并呈现磁化强度不易饱和的特征; Co_2-_xFe_xMnO₄系列样品在x<1.75成分范围内均可保持立方结构, 且晶格常数和磁性都随着x增大而提高。这些变化主要是由于掺杂原子尺度及磁矩均大于原有元素, 掺杂后样品内部的磁性相互作用有所增强。

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关键词: 尖晶石氧化物, 晶体结构, 磁性耦合

Abstract:

Spinel solid solution Co_2-_xMn₁₊_xO₄ and Co_2-_xFe_xMnO₄ were synthesized by Sol-Gel method using metal nitrates and citric acid as the starting materials. Crystalline phases, structure and magnetic properties of the Co₂MnO₄doped with different concentrations of Fe and Mn were investigated by XRD、FT-IR and PPMS, respectively. Results show that Co_2-_xMn₁₊_xO₄ series are single-phase cubic spinel structure at x<0.6, the lattice parameter as well as the saturation magnetization are found to be increasing with the Mn content increasing. Co_2-_xMn₁₊_xO₄ series transform to tetragonal structure gradually at x≥0.6, which result in the decline of magnetic properties and difficulty of reaching saturation. Co_2-_xFe_xMnO₄ samples have cubic spinel structure at x<1.75, the lattice parameter and magnetic increase with the increase of Fe-substitution. When the Fe content increases to 1.75, Fe₂O₃phase is formed in the sample. The changes of performance are mainly due to the larger atom radius of the doping atoms (Fe or Mn) as compared to that of Co. And magnetic moment is another important factor to the performance change. The first-principles calculation results show that the magnetic moments of Fe and Mn are larger than that of Co. As a result, the interatomic magnetic interaction is enhanced by doping.

Key words: spinel-type oxide, crystal structure, magnetic coupling

中图分类号:

TQ174

孟凡斌, 马晓帆, 张炜, 吴光恒, 张玉洁. Mn和Fe掺杂对尖晶石氧化物Co₂MnO₄结构和磁性的影响[J]. 无机材料学报, 2017, 32(6): 609-614.

MENG Fan-Bin, MA Xiao-Fan, ZHANG Wei, WU Guang-Heng, ZHANG Yu-Jie. Structure and Magnetic Property of Fe and Mn Doped Spinel Co₂MnO₄[J]. Journal of Inorganic Materials, 2017, 32(6): 609-614.

图/表 7

图1 (a) Co2-xMn1+xO4 (x= 0, 0.5, 0.6, 1)的XRD 图谱; (b) Co2-xFexMnO4 (x= 0.25, 0.75, 1.50, 1.75)的XRD 图谱, 星号标出杂相; (c) Co2-xFexMnO4 系列x= 0.25, 0.75, 1.50三个成分的(311)衍射峰, 插图为随着Fe含量增加晶格常数a的变化

Fig. 1 XRD patterns for Co2-xMn1+xO4 (x= 0, 0.5, 0.6, 1) (a); XRD patterns for Co2-xFexMnO4 (x= 0.25, 0.75, 1.50, 1.75), the impure phase peaks are marked with asterisks; (b) Detailed XRD patterns for Co2-xFexMnO4 (x= 0.25, 0.75, 1.50) showing the peak of (311) reflection (c). Inset shows the lattice parameter as a function of Fe content

图2 Co2MnO4、Co1.7 Fe0.3MnO4和CoMn2O4在400~950 cm-1范围的红外光谱图

Fig. 2 FT-IR spectra of Co2MnO4, Co1.7Fe0.3MnO4 and CoMn2O4 samples tested in 400-950 cm-1 Inset shows the testing range of 400-4000 cm-1

图3 (a)Co2-xMn1+xO4 (x=0, 0.5, 1.0)于5 K温度下的磁滞回线, 插图为室温测量曲线; (b)Co2-xFexMnO4(x=0.25, 0.75, 1.50)于5 K温度下磁滞回线, 插图为同成分室温结果

Fig. 3 Hysteresis loop for Co2-xMn1+xO4 (x=0, 0.5, 1.0) (a) and Co2-xFexMnO4 (x=0.25, 0.75, 1.50) (b) at the temperature of 5 K. Inset of them are the loops tested at room temperature

表1 5 K时Co2-xMn1+xO4和Co2-xFexMnO4系列磁性能参数

Table 1 Magnetic parameters for Co2-xMn1+xO4 and Co2-xFexMnO4 tested at 5 K

Co_2-_xMn₁₊_xO₄	M_S/(A∙m²∙kg^-1)	M_r/(A∙m²∙kg^-1)	H_C/T
x = 0	13.23	7.32	0.5421
x = 0.5	22.41	12.16	0.5427
Co_2-_xFe_xMnO₄	M_s/(A∙m²∙kg^-1)	M_r/(A∙m²∙kg^-1)	H_C/T
x = 0	13.23	7.32	0.5421
x = 0.25	41.61	19.91	0.2763
x = 0.75	66.78	37.36	0.2507
x = 1.50	77.97	64.83	0.7118

图4 (a)Co2MnO4成分氧四面体及八面体内局部磁结构示意图; (b)Co2-xMn1+xO4中掺杂的Mn原子附近磁结构; (c) Co2-xFexMnO4中掺杂的Fe原子附近磁结构

Fig. 4 Schematic of magnetic structure for Co2MnO4 (a); magnetic structure near the doped atoms for Co2-xMn1+xO4 (b) and Co2-xFexMnO4 (c)

图5 Co2-xMn1+xO4 (x = 0, 0.5, 1.0)磁性随温度的变化, 测试场强为0.1 T

Fig. 5 Temperature dependence of magnetization for Co2-xMn1+xO4 (x = 0, 0.5, 1.0) with the field of 0.1 T

图6 Co2-xFexMnO4样品中晶格常数(Lattice parameter)和室温饱和磁化强度(MS)随x值的变化

Fig. 6 Lattice parameter and MS as a function of composition

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Mn和Fe掺杂对尖晶石氧化物Co₂MnO₄结构和磁性的影响

Structure and Magnetic Property of Fe and Mn Doped Spinel Co₂MnO₄

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