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首页> 外文期刊>Crystallography reports >Structural Mechanisms of Superionic Conductivity in M_(1–x)R_xF_(2+x） Single Crystals
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Structural Mechanisms of Superionic Conductivity in M_(1–x)R_xF_(2+x） Single Crystals

机译：M_（1–x）R_xF_（2 + x）单晶中超离子电导的结构机理

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摘要

The relationship between the superionic transport in fluorite phases M＿（1 – x）R＿xF＿（2 + x） (M = Ca, Sr, or Ba; R are rare earth elements) and their defect structure has been analyzed. The superionic conductivity of M＿（1 – x）R＿xF＿（2 + x） crystals is provided by the high concentration of charge carriers. However, the carrier concentration is several tens of times lower than the concentration of anionic defects, which is explained by the presence of defect regions (DRs), which partially block carriers. The dependence of the superionic conductivity of M＿（1 – x）R＿xF＿（2 + x） phases on the RF_3(x) content has a percolation nature. Crystals of these phases are divided into two groups with respect to the percolation threshold: x_(p, 1) = 2–3 mol % RF_3 and xp, 2 = 7–8 mol % RF_3. The corresponding DR volumes are 3000–4000 ?～3 (x_(p, 1)) and 500–700 ?～3 (xp, 2). The x_(p, 1), and xp, 2 values correlate, respectively, with the octahedral cubic {M_(14 – p)R_pF_(68 – 69)} and tetrahedral {M＿（4 – p）R_pF_(26)} clusters, which are DR cores. The DR model and cluster structure are indicative of the heterogeneity of nonstoichiometric M＿（1 – x）R＿xF＿（2 + x） crystals at the nanoscale level with respect to the chemical composition and the electrical and crystallochemical (coordinations of M and R) characteristics.
机译：分析了萤石相M＿（1 – x）R＿xF＿（2 + x）（M = Ca，Sr或Ba; R为稀土元素）中超离子迁移与它们的缺陷结构之间的关系。高浓度的电荷载流子提供了M＿（1 – x）R＿xF＿（2 + x）晶体的超离子电导率。但是，载流子浓度比阴离子缺陷的浓度低几十倍，这可以通过缺陷区域（DR）的存在来解释，该缺陷区域会部分阻塞载流子。 M＿（1 – x）R＿xF＿（2 + x）相的超离子电导率对RF_3（x）含量的依赖性具有渗滤性质。就渗透阈而言，这些相的晶体分为两组：x_（p，1）= 2–3 mol％RF_3和xp，2 = 7–8 mol％RF_3。相应的DR量为3000–4000？〜3（x_（p，1））和500–700？〜3（xp，2）。 x_（p，1）和xp，2值分别与八面体立方{M_（14 – p）R_pF_（68 – 69）}和四面体{M＿（4 – p）R_pF_（26）}簇相关，它们是灾难恢复核心。 DR模型和簇结构指示了非化学计量的M＿（1 – x）R＿xF＿（2 + x）晶体在纳米级的化学组成以及电和晶体化学（M和R的配位）特性的异质性。

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