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中国物理学会期刊

锌离子掺杂钴基金属有机材料(CH3)2NH2Co1–xZnx(HCOO)3中的低温反常磁现象

CSTR: 32037.14.aps.72.20221761

Abnormal magnetic phenomenon at low temperature in Zn doped \left(\mathbfC\mathbfH_3)_2\mathbfN\mathbfH_2\right\mathbfC\mathbfo_\mathitx\mathbfZ\mathbfn_1-\mathitx\left\mathbfH\mathbfC\mathbfO\mathbfO\right_3 frameworks

CSTR: 32037.14.aps.72.20221761
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  • 金属有机框架材料(MOFs)是一种有机配体桥接金属离子组成的新型无机-有机杂化多孔材料, 它具有功能可调、稳定性好以及多孔性等特点, 受到人们的广泛关注. 本文利用水热法制备了高质量的锌离子掺杂的钴基(CH3)2NH2Co1–xZnx(HCOO3)单晶样品 (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5). 单晶衍射、摇摆曲线、能量色散X射线光谱的实验结果表明, 锌离子均匀掺杂进了钴基金属有机框架材料中, 没有出现局部团簇等现象. 低温场冷曲线和比热曲线的测量结果表明, 非磁锌离子的掺杂减弱了Co基MOFs材料中Co离子之间的长程反铁磁相互作用, 使得Co-MOF的反铁磁相变温度由纯钴的15 K变为14.2 K (x = 0.1), 12.8 K (x = 0.2). 通过对掺锌样品低温下的磁滞回线的细致研究发现, 掺锌样品相对于纯钴样品在低温下具有更大的磁滞损耗和矫顽场. 相比于纯钴样品450 Oe (1 Oe = 103/(4π) A/m)的矫顽场, 掺锌样品的矫顽场最高达到3600 Oe, 并且磁滞面积也为纯钴样品的3倍以上. 另一方面, 在DMCo0.9Zn0.1F样品的磁滞回线上发现一系列台阶, 这一台阶现象随着温度升高而逐渐消失, 类似于单分子磁体的量子隧穿现象. 以往研究表明, 在这一类钙钛矿结构的金属有机骨架材料中, 存在长程磁相互作用和磁单离子行为的竞争. 我们认为非磁锌离子的掺杂减弱了Co离子之间的长程相互作用, 使得Co离子在低温下显示出量子隧穿引起的台阶效应.

     

    Metal-organic framework (MOF) is a new type of inorganic-organic hybrid porous material composed of organic ligands bridging metal ions, and it has the characteristics of tunable functions, good stability and porosity. In this study, Zn doped Co-based metal organic frame works single-crystal samples\left(\rmC\rmH_3)_2\rmN\rmH_2\right\rmC\rmo_1-x\rmZ\rmn_x \left\rmH\rmC\rmO\rmO\right_3are synthesized by the solvothermal method with normal ratio x = 0, 0.1, 0.2, 0.3, 0.4, 0.5. Single crystal diffraction, scanning electron microscope and energy dispersive X-ray spectroscopy results show that Zn ions are uniformly doped into Co-based MOFs crystals. The field cooling curves show that antiferromagnetic phase transition temperature of Co-based MOFs decreases from 15 K for pure Co-MOF x = 0 to 12.8 K for x = 0.2. Abnormal large magnetic hysteresis is obtained for Zn doped crystals with large coercive field 3600 Oe (x = 0.3) compared with 450 Oe coercive field for pure Co-MOF (x = 0), and the hysteresis area of Zinc-doped sample is more than 3 times that of pure cobalt sample. On the other hand, we find a series of steps on the hysteresis loop of DMCo0.9Zn0.1F sample, which gradually disappears with the increase of temperature, similar to the quantum tunneling phenomenon of a single molecule magnet. Previous studies have shown that the long range magnetic interaction and the magnetic single-ion behavior competition coexist in these systems. It is believed that the doping of non-magnetic zinc ions weakens the long-range interaction between Co ions and makes Co ions show the step effect caused by quantum tunneling at low temperature.

     

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