SrBi4Ti4O15的化学键性质和铁电性研究

通过原子环境计算方法分析了正交相SrBi₄Ti₄O₁₅晶体内的键络结构、各原子的空间配位数及局域团簇结构. 在此基础上, 结合晶体分解理论将SrBi₄Ti₄O₁₅晶体分解为多个二元赝晶体, 根据化学键介电理论计算得到各赝晶体所对应化学键的有效价电子密度、离子性等化学键性质. 通过键偶极矩建立了铁电体自发极化强度与化学键性质之间的关系, 求得正交相SrBi₄Ti₄O₁₅沿a轴方向的自发极化强度为28.03 μC/cm², 与实验结果和其他理论计算值符合较好.

The chemical bond properties and ferroelectricity studies of SrBi4Ti4O15

Spontaneous polarization as the most immediate parameter in ferroelectricity is always an emphasis in ferroelectric research. Some ferroelectric microscopic theory such as Berry-phase method and first principles calculation are used to study the spontaneous polarization of perovskite type ferroelectrics. SrBi₄Ti₄O₁₅ is a typical bismuth layered structure ferroelectric, the complexity of its crystal structure makes the ferroelectric research more difficult. This study, from the perspective of chemical bond, analyzes the relationship between the chemical bond properties and the spontaneous polarization, and further explores the atomic bonding state in ferroelectric crystal and its impact on ferroelectricity.By starting from the crystal structure data of SrBi₄Ti₄O₁₅, the atomic local cluster structure including bond length, atomic coordination situation and the number of atoms in a crystal structure unit are obtained by the atomic environment calculation (AEC). Calculation results show that there are 13 atomic local cluster structures in SrBi₄Ti₄O₁₅. Then combined with the crystal decomposition method, the SrBi₄Ti₄O₁₅crystal is decomposed into 38 pseudo-binary crystals, and each pseudo-binary crystal corresponds to a chemical bond. Accordding to the dielectric theory of chemical bond that used in binary crystal, chemical bond properties such as the number of effective valence electron, the effective valence electron density and the bond ionicity are calculated. Through improvement of the bond dipole moment model, the relationship among bond dipole moment, bond properties, and bond parameter is established, and the bond dipole moment of each bond in SrBi₄Ti₄O₁₅ is calculated.The spontaneous polarization of an ferroelectric can be approximated as the superposition of the spontaneous polarization of various chemical bonds in the crystal, where the spontaneous polarization of chemical bond is due to the bond dipole moment. Based on the traditional polarization theory, the spontaneous polarization can be expressed as the average bond dipole moment per unit volume, and considering the number of molecules in unit cell (Z) and the atomic site occupation factor (SOF), the correlation between bond dipole moment and spontaneous polarization of the bismuth layered ferroelectrics is established. On the basis of this, the calculated spontaneous polarization along a axis in the ferroelectric SrBi₄Ti₄O₁₅ is 28.03 μC/cm².This study simplifies the complex crystal research by AEC and crystal decomposition method, and studies the ferroelectricity of the bismuth layered ferroelectrics from the viewpoint of chemical bond. The bond dipole moment as the bridge in this study for connecting spontaneous polarization with chemical bond properties, which is a new micro study method in macro-properties of bismuth layered ferroelectrics. Based on this method, the spontaneous polarization of other relevant ferroelectrics such as orthogonal SrBi₂Ta₂O₉, orthogonal Bi₄Ti₃O₁₂, and tetragonal SrBi₄Ti₄O₁₅ are calculated, all the results are in good agreement with the experimental values and other theoretically calculated values.