Xu Kun, Zhang Luo, Godfrey Andy, Song Dongsheng, Si Wenlong, Zhao Yawen, Liu Yi, Rao Yiheng, Zhang Huaiwu, Zhou Heng-An, Jiang Wanjun, Wang Wenbin, Cheng Zhiying, Zhu Jing
National Center for Electron Microscopy in Beijing, School of Materials Science and Engineering, Tsinghua University, 100084 Beijing, People's Republic of China.
Central Nano and Micro Mechanism, Tsinghua University, 100084 Beijing, People's Republic of China.
Proc Natl Acad Sci U S A. 2021 May 18;118(20). doi: 10.1073/pnas.2101106118.
Bismuth and rare earth elements have been identified as effective substituent elements in the iron garnet structure, allowing an enhancement in magneto-optical response by several orders of magnitude in the visible and near-infrared region. Various mechanisms have been proposed to account for such enhancement, but testing of these ideas is hampered by a lack of suitable experimental data, where information is required not only regarding the lattice sites where substituent atoms are located but also how these atoms affect various order parameters. Here, we show for a Bi-substituted lutetium iron garnet how a suite of advanced electron microscopy techniques, combined with theoretical calculations, can be used to determine the interactions between a range of quantum-order parameters, including lattice, charge, spin, orbital, and crystal field splitting energy. In particular, we determine how the Bi distribution results in lattice distortions that are coupled with changes in electronic structure at certain lattice sites. These results reveal that these lattice distortions result in a decrease in the crystal-field splitting energies at Fe sites and in a lifted orbital degeneracy at octahedral sites, while the antiferromagnetic spin order remains preserved, thereby contributing to enhanced magneto-optical response in bismuth-substituted iron garnet. The combination of subangstrom imaging techniques and atomic-scale spectroscopy opens up possibilities for revealing insights into hidden coupling effects between multiple quantum-order parameters, thereby further guiding research and development for a wide range of complex functional materials.
铋和稀土元素已被确定为铁石榴石结构中的有效替代元素,可使可见和近红外区域的磁光响应增强几个数量级。人们提出了各种机制来解释这种增强现象,但由于缺乏合适的实验数据,这些观点的验证受到了阻碍,因为不仅需要有关替代原子所在晶格位置的信息,还需要了解这些原子如何影响各种有序参数。在此,我们展示了对于一种铋取代的镥铁石榴石,如何将一系列先进的电子显微镜技术与理论计算相结合,来确定包括晶格、电荷、自旋、轨道和晶体场分裂能在内的一系列量子有序参数之间的相互作用。特别是,我们确定了铋的分布如何导致晶格畸变,这些畸变与某些晶格位置处的电子结构变化相关联。这些结果表明,这些晶格畸变导致铁位点处的晶体场分裂能降低,八面体位点处的轨道简并性解除,而反铁磁自旋序得以保留,从而有助于增强铋取代铁石榴石的磁光响应。亚埃成像技术和原子尺度光谱学的结合为揭示多个量子有序参数之间隐藏的耦合效应提供了可能性,从而进一步指导广泛的复杂功能材料的研发。