Crystalline structure of 0.65BiFeO3–0.35Ba1-xSrxTiO3 solid solutions in the vicinity of the morphotropic phase boundary

M. Silibin, P. Sklyar, Vadim D. Zhivulko, S. I. Latushko, D. V. Zheludkevich, Dmitry V. Karpinsky
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Abstract

Complex transition metal oxides are distinguished for a close interrelation between their type of crystal structure and electrical and magnetic properties, thus determining their practical importance. Bismuth ferrite based solid solutions contain simultaneously both dipole electric and magnetic ordering thus expanding their potential applications as external impact sensors. The sensitivity of these compositions to external fields is largely dependent on their structural state. 0.65BiFeO3–0.35Ba1-xSrxTiO3 solid solutions (0 ≤ x ≤ 1) the compositions of which are close to the rhombohedral/cubic morphotropic phase boundary have metastable structures and are therefore promising functional materials. The crystal structure and morphology of 0.65BiFeO3–0.35Ba1-xSrxTiO3 solid solutions has been studied using X-ray diffraction, scanning electron microscopy, Raman spectroscopy and energy dispersive X-ray spectroscopy. The chemical substitution of barium ions for strontium ones has been found to reduce the magnitude of rhombohedral distortions and decrease the unit cell parameters for all the substituted compounds. Solid solutions with x ≥ 0,25 have single-phase structure and cubic unit cells, their grain size decreasing with an increase in the concentration of the substituting ions. The results of structural studies obtained using Raman spectroscopy suggest the presence of rhombohedral distortions in the structures of all the compositions studied. The results of structural studies have allowed identifying the sequence of changes in the phase state and lattice parameter of the compounds in the vicinity of the rhombohedral/cubic morphotropic phase boundary. The concentration ranges in which the compounds have single-phase and two-phase structures have been found. The concentration stability range of the polar rhombohedral phase has been corrected on the basis of the structural data obtained using local and microscopic methods.
各向形态相边界附近 0.65BiFeO3-0.35Ba1-xSrxTiO3 固溶体的晶体结构
复杂的过渡金属氧化物因其晶体结构类型与电学和磁学特性之间的密切联系而与众不同,从而决定了它们的实际重要性。以铋铁氧体为基础的固溶体同时包含偶极电性和磁性排序,从而扩大了其作为外部冲击传感器的潜在应用范围。这些成分对外部场的敏感性在很大程度上取决于它们的结构状态。0.65BiFeO3-0.35Ba1-xSrxTiO3 固溶体(0 ≤ x ≤ 1)的成分接近斜方体/立方体形态相边界,具有可迁移结构,因此是很有前途的功能材料。利用 X 射线衍射、扫描电子显微镜、拉曼光谱和能量色散 X 射线光谱研究了 0.65BiFeO3-0.35Ba1-xSrxTiO3 固溶体的晶体结构和形态。研究发现,钡离子对锶离子的化学取代降低了所有取代化合物的斜方体畸变程度,并降低了单胞参数。x ≥ 0.25 的固溶体具有单相结构和立方晶胞,其晶粒尺寸随着替代离子浓度的增加而减小。利用拉曼光谱进行的结构研究结果表明,所有研究成分的结构都存在斜方体畸变。根据结构研究的结果,可以确定化合物在斜方体/立方体形态相边界附近的相态和晶格参数的变化顺序。发现了化合物具有单相和两相结构的浓度范围。根据使用局部和微观方法获得的结构数据,修正了极性斜方体相的浓度稳定范围。
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