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Diluted ferromagnetic semiconductors (DMSs) have attracted widespread attention in last decades, owing to their potential applications in spintronic devices. But classical group-III-IV, and -V elements based DMS materials, such as (Ga,Mn)As which depend on heterovalent (Ga3+, Mn2+) doping, cannot separately control carrier and spin doping, and have seriously limited chemical solubilities, which are disadvantages for further improving the Curie temperatures. To overcome these difficulties, a new-generation DMS with independent spin and charge doping have been designed and synthesized. Their representatives are I-II-V based Li(Zn,Mn)As and II-II-V based (Ba,K)(Zn,Mn)2As2. In these new materials, doping isovalent Zn2+ and Mn2+ introduces only spins, while doping heterovalent non-magnetic elements introduces only charge. As a result, (Ba,K)(Zn,Mn)2As2 achieves Curie temperature of 230 K, a new record among DMS where ferromagnetic orderings are mediated by itinerate carriers. Herein, we summarize the recent advances in the new-generation DMS materials. The discovery and synthesis of several typical new-generation DMS materials are introduced. Physical properties are studied by using muon spin relaxation, angle-resolved photoemission spectroscopy and pair distribution function. The physical and chemical pressure effects on the title materials are demonstrated. The Andreev reflection junction based on single crystal and the measurement of spin polarization are exhibited. In the end, we demonstrate the potential multiple-parameter heterojunctions with DMSs superconductors and antiferromagnetic materials.
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Keywords:
- new generation diluted magnetic semiconductors /
- independent charge and spin doping /
- high Curie temperature /
- multiple-parameters heterojunctions
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图 1 (a) Li(Zn,Mn)As的晶体结构; (b) 不同Mn掺杂浓度的Li1.1(Zn1–xMnx)As磁矩-温度M(T)关系; (c) 不同Mn掺杂浓度的Li1.1(Zn1–xMnx)As的M(H)曲线[17]
Figure 1. (a) Crystal structure of Li(Zn,Mn)As; (b) temperature-dependent magnetization M(T) of Li1.1(Zn1–xMnx)As with different Mn doping concentrations; (c) field-dependent magnetization M(H) of Li1.1(Zn1–xMnx)As with different Mn doping concentrations[17]
图 2 (a) LiZnAs及其在Li过掺杂(y > 0)和欠掺杂(y < 0)条件下的电阻率-温度关系ρ(T); (b) 不同外磁场下Li1.1(Zn0.9Mn0.1)As的ρ(T)曲线, 反映了样品低温下负磁阻的特点; (c) 不同温度下Li1.1(Zn0.95Mn0.05)As的霍尔电阻率, 2 K下的图像表现出了低场下的反常霍尔效应, 同时说明了样品属于p型半导体[17]
Figure 2. (a) Temperature-dependent resistivity of LiZnAs with overdoped and underdoped Li+; (b) temperature-dependent resistivity of Li1.1(Zn0.9Mn0.1)As under varying fields; (c) Hall resistivity of Li1.1(Zn0.95Mn0.05)As at different temperatures, manifesting the anomalous Hall effect at 2 K and p-type semiconductor[17].
图 3 (a) (Ba,K)(Zn,Mn)2As2的晶体结构[18]; (b) 在FC和ZFC过程中不同K掺杂浓度下(Ba1–x, K)(Zn0.9Mn0.1)2As2的M(T)曲线[18]; (c) (Ba0.7K0.3)(Zn0.85Mn0.15)2As2的磁化率-温度变化关系, 样品具有230 K的TC, 插图对应2 K下M(H)曲线[19]; (d) 2 K时不同K掺杂浓度下(Ba1–xKx)(Zn0.9Mn0.1)2As2的M(H)曲线[18]
Figure 3. (a) Crystal structure of (Ba,K)(Zn,Mn)2As2[18]; (b) temperature-dependent magnetization of (Ba1–xK)(Zn0.9Mn0.1)2As2 for FC and ZFC process[18]; (c) temperature-dependent magnetization of (Ba0.7K0.3)(Zn0.85Mn0.15)2As2, the inset is field-dependent magnetization at 2 K[19]; (d) field-dependent magnetization of (Ba1–xKx)(Zn0.9Mn0.1)2As2 at 2 K with different K doping concentrations[18]
图 4 (a) 单晶(Ba0.904K0.096)(Zn0.805Mn0.195)2As2的XRD图谱, 插图为晶体结构和单晶照片; (b) 外场垂直和平行于该单晶ab面的M(T)曲线, 这说明了晶体c方向为易磁化轴; (c) 不同温度下该单晶的霍尔电阻, 外场方向垂直于ab面外[21]
Figure 4. (a) XRD pattern of single crystal (Ba0.904K0.096)(Zn0.805Mn0.195)2As2, and the illustrations are crystal structure and single crystal photos; (b) temperature-dependent magnetization of this single crystal with field vertical and parallel to ab-plane, indicating the easy axis is along c axis; (c) Hall resistance of this single crystal under varying temperature with field vertical to ab-plane[21].
图 5 (a) ZF模式下Li1.1(Zn0.95Mn0.05)As样品的μSR谱[17]; (b) ZF与WTF模式下拟合得到的Li1.1(Zn0.95Mn0.05)As样品中铁磁相体积分数[17]; (c) ZF模式下(Ba0.8K0.2)(Zn0.85Mn0.15)2As2样品的μSR谱[18]; (d) ZF与WTF模式下拟合得到的(Ba0.8K0.2)(Zn0.85Mn0.15)2As2样品中铁磁相体积分数, 插图为5 Oe外场下样品M/MS(T)图像[18]
Figure 5. (a) μSR spectra of Li1.1(Zn0.95Mn0.05)As in ZF process[17]; (b) the volume fraction of ferromagnetic region in Li1.1(Zn0.95Mn0.05)As derived from ZF and WTF process[17]; (c) μSR spectra of (Ba0.8K0.2)(Zn0.85Mn0.15)2As2 in ZF process[18]; (d) the volume fraction of ferromagnetic region in (Ba0.8K0.2)(Zn0.85Mn0.15)2As2 derived from ZF and WTF process, and the illustration is a M/MS(T) image of a sample under 5 Oe field[18].
图 6 (a) (Ba0.7K0.3)(Zn0.85Mn0.15)2As2, Mn单质以及其他含Mn化合物的Mn L2,3边的XAS图像[42]; (b) (Ba0.904K0.096)(Zn0.805Mn0.195)2As2在非共振和共振能光子条件下获得的ARPES谱图以及对应的能量二阶导的谱图[43]
Figure 6. (a) Mn L2,3-edge XAS spectra of (Ba0.7K0.3)(Zn0.85Mn0.15)2As2, Mn and other compounds containing Mn ions[42]; (b) ARPES spectra and corresponding second derivative spectra of (Ba0.904K0.096)(Zn0.805Mn0.195)2As2 taken with on- and off-resonance[43].
图 7 (a) (Ba,K)(Zn0.85Mn0.15)2As2畸变量随温度的变化曲线; (b)含有以及未含有K掺杂情况下的(Ba1–xKx)(Zn0.85Mn0.15)2As2样品中子全散射的PDF拟合结果与实验结果的残差(垂直虚线代表最近邻Mn—Mn间距); (c) 2 K和300 K下(Ba0.7K0.3)(Zn0.85Mn0.15)2As2样品磁性PDF图像(垂线代表Mn—Mn键长); (d) 长程铁磁模型和最近邻模型拟合下磁性PDF的比例系数与温度的关系[44]
Figure 7. (a) Temperature-dependent structure distortion of (Ba,K)(Zn0.85Mn0.15)2As2; (b) nuclear PDF fit residuals for (Ba1–xKx)(Zn0.85Mn0.15)2As2 (vertical dashed line represents the nearest neighbor Mn—Mn distance); (c) magnetic PDF patterns for (Ba0.7K0.3)(Zn0.85Mn0.15)2As2 at 2 K and 300 K (vertical line represents the Mn—Mn bond length); (d) magnetic PDF scale factors from LRO model and NN model at varying temperatures [44].
图 8 (Ba0.8K0.2)(Zn0.95Mn0.05)2As2在压力作用下晶格常数的变化. 左下插图为层间As—As间距随压力的变化, 右上插图为As—Zn—As夹角随压力的变化[49]
Figure 8. Pressure-dependent lattice parameters of (Ba0.8K0.2)(Zn0.95Mn0.05)2As2. Lower-left inset is the pressure-dependent inter-layered As—As distance and upper-right inset is the pressure-dependent As—Zn—As bond angle[49].
图 9 (a) (Ca,Na)(Cd,Mn)2As2晶体结构; (b) 在(Sr,Na)(Cd,Mn)2As2和(Ca,Na)(Cd,Mn)2As2中的CdAs四面体Cd—As键长与As—Cd—As键角的对比; (c) (Sr,Na)(Cd,Mn)2As2样品的M(T)曲线; (d) (Ca,Na)(Cd,Mn)2As2样品的M(T)曲线, 插图为磁化率倒数-温度关系[20,52]
Figure 9. (a) Crystal structure of (Ca,Na)(Cd,Mn)2As2; (b) comparison of Cd—As distance and As—Cd—As bond angle between (Sr,Na)(Cd,Mn)2As2 and (Ca,Na)(Cd,Mn)2As2; (c) temperature-dependent magnetization of (Sr,Na)(Cd,Mn)2As2; (d) temperature-dependent magnetization of (Ca,Na)(Cd,Mn)2As2, the inset is the Curie-Wiess fitting [20,52].
图 10 (a) 零偏压下归一化G/G0随温度的变化关系, 插图为Pb/(Ba,K)(Zn,Mn)2As2安德烈夫反射结示意图; (b)不同温度下Pb/(Ba,K)(Zn,Mn)2As2安德烈夫反射谱以及在修正BTK理论模型下拟合的结果[21]
Figure 10. (a) Temperature-dependent normalized G/G0 and the sketch of the Pb/(Ba,K)(Zn,Mn)2As2 Andreev reflection junction; (b) Andreev reflection spectra of Pb/(Ba,K)(Zn,Mn)2As2 junction and the modified BTK fit at different temperature[21].
图 11 (a) Li(Zn,Mn)As, LiMnAs和LiFeAs的晶体结构和晶胞参数的对比; (b) (Ba,K)Fe2As2, (Ba,K)(Zn,Mn)2As2和BaMn2As2的晶体结构和晶胞参数的对比[17]
Figure 11. (a) Comparison of crystal structure and lattice parameter among Li(Zn,Mn)As, LiMnAs and LiFeAs; (b) comparison of crystal structure and lattice parameter among (Ba,K)Fe2As2, (Ba,K)(Zn,Mn)2As2 and BaMn2As2[17].
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Google Scholar
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Google Scholar
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Google Scholar
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Google Scholar
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Google Scholar
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