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EuC(2)中的结构相变。

Structural phase transitions in EuC(2).

机构信息

Department of Chemistry, University of Cologne, Greinstrasse 6, D-50939 Cologne, Germany.

出版信息

Inorg Chem. 2010 Jan 4;49(1):312-8. doi: 10.1021/ic901979v.

DOI:10.1021/ic901979v
PMID:20000316
Abstract

Pure EuC(2), free of EuO impurities, was obtained by the reaction of elemental europium with graphite at 1673 K. By means of synchrotron powder diffraction experiments, the structural behavior was investigated in the temperature range from 10 to 1073 K. In contrast to former results, EuC(2) crystallizes in the ThC(2) type structure (C2/c, Z = 4) at room temperature. A tetragonal modification (I4/mmm, Z = 2) is only observed in a very small temperature range just below the transition to a cubic high-temperature modification (Fm3m, Z = 4) at 648 K. DTA/TG investigations confirm these results. According to Raman spectroscopy, EuC(2) contains C(2)(2-) ions (nu(C[triple bond]C) = 1837 cm(-1)). The divalent character of Eu is confirmed by the results of magnetic susceptibility measurements and (151)Eu Mossbauer spectroscopy. In these measurements a transition to a ferromagnetic state with T(C) = 15 K is observed, which is in reasonable agreement with literature data. Above T(C) EuC(2) is a semiconductor according to measurements of the electric resistivity vs temperature, again in contrast to former results. Around T(C) a sharp maximum of the electric resistivity vs temperature curve was observed, which collapses on applying external magnetic fields. The observed CMR effect (colossal magnetoresistance) is much stronger than that reported for other EuC(2) samples in the literature. These investigations explicitly show the influence of sample purity on the physical and even structural properties of EuC(2).

摘要

通过元素铕与石墨在 1673 K 下的反应,得到了纯净的 EuC(2),没有 EuO 杂质。通过同步辐射粉末衍射实验,在 10 至 1073 K 的温度范围内研究了其结构行为。与以前的结果相反,EuC(2)在室温下结晶为 ThC(2)型结构(C2/c,Z=4)。只有在非常小的温度范围内,即在 648 K 时向立方高温变体(Fm3m,Z=4)转变之前,才观察到四方变体(I4/mmm,Z=2)。DTA/TG 研究证实了这些结果。根据拉曼光谱,EuC(2)含有 C(2)(2-)离子(ν(C[triple bond]C)=1837 cm(-1))。磁导率测量和(151)Eu 穆斯堡尔光谱的结果证实了 Eu 的二价性质。在这些测量中,观察到一个从顺磁态到铁磁态的转变,T(C)=15 K,这与文献数据相当吻合。根据电阻率随温度的测量,在 T(C)以上,EuC(2)是半导体,这与以前的结果相反。在 T(C)附近,观察到电阻率随温度曲线的急剧最大值,施加外磁场后该最大值崩塌。观察到的 CMR 效应(巨磁电阻)比文献中报道的其他 EuC(2)样品要强得多。这些研究明确显示了样品纯度对 EuC(2)的物理甚至结构性质的影响。

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