Layered materials, represented by graphene and transition metal dichalcogenides, have aroused significant research interest with the intriguing physical phenomena behind and enormous nanoscale device applications. Here, we report two types of novel modulated Bi-based layered supercell (LSC) structures via combined experimental and first-principles investigation. These two types of oxide-based LSC structures are prepared through self-assembly fabrication from both BiMnO₃ and Bi₂NiMnO₆ by pulsed lased deposition under well-controlled growth conditions. Both LSC structures are composed of alternative layer stacking of two sublattices along the film growth direction, i.e. sublattice 1 of Mn–O or Ni–Mn–O octahedral slab and sublattice 2 of Bi₂O₂ or Bi₃O₃ slab, respectively. Moreover, these two LSC structures can be tuned by changing the compositions of Bi–O sublattice from Bi₂O₂ to Bi₃O₃ for the same material system by precise control of growth conditions. The experimental characterizations reveal that these new LSCs with modulated layer stacking sequence results in tunable physical properties including robust room-temperature ferromagnetism and unique optical properties, which is well consistent with our first-principles electronic structure calculations. This work demonstrates the possibility of tuning layered oxide stacking by self-assembly thin film growth for designed material functionalities. The Bi-based LSC can be epitaxially grown on flexible mica substrate which is of great significance toward future flexible layered oxide–based electronic applications such as magnetic data storage.

以石墨烯和过渡金属二氢二硫化物为代表的层状材料，由于其背后有趣的物理现象和巨大的纳米级器件应用，引起了人们极大的研究兴趣。在这里，我们通过结合实验和第一性原理研究报告了两种新型的基于Bi的调制双层超细胞（LSC）结构。这两种类型的基于氧化物的LSC结构是通过在良好控制的生长条件下通过脉冲激光沉积由BiMnO ₃和Bi ₂ NiMnO ₆进行自组装制造而制备的。两种LSC结构均由沿膜生长方向的两个亚晶格的交替层堆叠组成，即Mn-O或Ni-Mn-O八面体平板的亚晶格1和Bi _2的亚晶格₂O ₂或Bi ₃ O ₃平板。此外，可以通过将Bi–O子晶格的组成从Bi ₂ O ₂更改为Bi ₃ O ₃来调整这两个LSC结构。通过精确控制生长条件来实现相同的材料系统。实验特性表明，这些具有调制层堆叠顺序的新型LSC具有可调节的物理特性，包括强大的室温铁磁性和独特的光学特性，这与我们的第一性原理电子结构计算非常吻合。这项工作证明了通过自组装薄膜生长来调整层状氧化物堆叠以实现设计的材料功能的可能性。基于Bi的LSC可以外延生长在柔性云母衬底上，这对未来基于柔性分层氧化物的电子应用（如磁数据存储）具有重要意义。