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锰亚晶格中等价取代对BiMnO₃:BiMn₁₋ₓMₓO₃(M = Al、Sc、Cr、Fe、Ga;0≤x≤0.2)的磁性、热学和结构性能的影响

Effects of isovalent substitution in the manganese sublattice on magnetic, thermal, and structural properties of BiMnO3: BiMn1-xMxO3 (M=Al, Sc, Cr, Fe, Ga; 0<or=x<or=0.2).

作者信息

Belik Alexei A, Takayama-Muromachi Eiji

机构信息

Advanced Nano Materials Laboratory (ANML), National Institute for Materials Science (NIMS), 1-1 Namiki, Tsukuba, Ibaraki 305-0044, Japan.

出版信息

Inorg Chem. 2007 Jul 9;46(14):5585-90. doi: 10.1021/ic0701615. Epub 2007 Jun 12.

Abstract

Solid solutions BiMn1-xMxO3 with M=Al, Sc, Cr, Fe, and Ga and 0<or=x<or=0.2 were prepared at a high pressure of 6 GPa and 1333-1453 K, and their magnetic, thermal, and structural properties were investigated. The orbital-ordered monoclinic phase of BiMnO3 (phase I) is destroyed by a small percentage of substitution. The M elements can be classified by their ability to destroy phase I in the sequence Ga (x approximately 0.08) approximately Fe (x approximately 0.08)<Cr (x approximately 0.04) approximately Al (x approximately 0.04)<Sc (x approximately 0.02), where phase I is most stable for Ga substitution (up to x approximately 0.08) and less stable for Sc substitution (up to x approximately 0.02). The orbital-disordered high-temperature monoclinic phase of BiMnO3 (phase II) is stabilized with larger x. In all cases, a compositional range was found where phases I and II coexist at room temperature. In phase I, the effect of substitution on the ferromagnetic transition temperature is weak (e.g., TC=102 K for BiMnO3 and TC=99 K for BiMn0.95Ga0.05O3), but there is a drastic effect on the orbital ordering temperature (e.g., TOO=474 K for BiMnO3 and TOO=412 K for BiMn0.95Ga0.05O3). Magnetic susceptibilities of phase I are typical for ferromagnets while, in phase II, ferromagnetic cluster-glass-like behavior is observed. The magnetic transition temperature of phase II (e.g., TC=70 K for BiMn0.8Ga0.2O3) exhibits a sudden drop compared with that of phase I. The effect of substitution on the structural monoclinic-to-orthorhombic transition is different depending on M (e.g., Tstr=768 K for BiMnO3, Tstr=800 K for BiMn0.95Ga0.05O3, and Tstr=738 K for BiMn0.85Cr0.15O3).

摘要

在6吉帕斯卡的高压和1333 - 1453开尔文的温度下制备了M = Al、Sc、Cr、Fe和Ga且0≤x≤0.2的固溶体BiMn₁₋ₓMₓO₃,并对其磁学、热学和结构性质进行了研究。BiMnO₃的轨道有序单斜相(相I)会因少量替代而被破坏。M元素可按其破坏相I的能力排序如下:Ga(x约为0.08)≈Fe(x约为0.08)<Cr(x约为0.04)≈Al(x约为0.04)<Sc(x约为0.02),其中相I对Ga替代最稳定(x高达约0.08),对Sc替代较不稳定(x高达约0.02)。BiMnO₃的轨道无序高温单斜相(相II)在x较大时更稳定。在所有情况下,都发现了一个成分范围,在室温下相I和相II共存。在相I中,替代对铁磁转变温度的影响较弱(例如,BiMnO₃的居里温度TC = 102 K,BiMn₀.₉₅Ga₀.₀₅O₃的居里温度TC = 99 K),但对轨道有序温度有显著影响(例如,BiMnO₃的轨道有序温度TOO = 474 K,BiMn₀.₉₅Ga₀.₀₅O₃的轨道有序温度TOO = 412 K)。相I的磁化率是铁磁体的典型特征,而在相II中,观察到类似铁磁团簇玻璃的行为。相II的磁转变温度(例如,BiMn₀.₈Ga₀.₂O₃的居里温度TC = 70 K)与相I相比有突然下降。替代对结构从单斜到正交转变的影响因M而异(例如,BiMnO₃的结构转变温度Tstr = 768 K,BiMn₀.₉₅Ga₀.₀₅O₃的结构转变温度Tstr = 800 K,BiMn₀.₈₅Cr₀.₁₅O₃的结构转变温度Tstr = 738 K)。

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