Layered group IV–VI compounds (i.e., SnSe, SnS, GeSe, and GeS) in the puckered structure resembling black‐phosphorene (BlackP) have attracted increasing interest because of their intriguing ferroic orders and outstanding thermoelectric properties. By invoking the guiding principles of isovalency and isomorphism for promoting van der Waals epitaxy, and based on comprehensive first‐principles calculations, here it is shown that the typically metastable BlackP‐like GeTe can be readily stabilized on the (001) surface of isostructural SnSe. Importantly, the ferroelectricity of such a BlackP‐like GeTe monolayer can be substantially enhanced compared to the freestanding state, due to the substrate enlarged in‐plane polar displacements. The GeTe/SnSe heterobilayer exhibits multiple ferroelectric/ferrielectric polarization states, which can be exploited for high‐density memory devices. These mutually switchable polarization states are also shown to be internally locked with the spin polarization of the valence/conduction bands with pronounced Rashba spin‐orbit splitting and Berry curvature dipole. These findings highlight the intuitive yet enabling power of van der Waals imprinting in growing novel 2D materials for enriched functionalities.

中文翻译：

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通过范德华压印稳定类磷烯 IV-VI 族化合物以实现多态铁电性和可调谐自旋输运

类似于黑磷烯 (BlackP) 的褶皱结构中的层状 IV-VI 族化合物（即 SnSe、SnS、GeSe 和 GeS）因其有趣的铁序和出色的热电性能而引起了越来越多的兴趣。通过引用等价性和同构性的指导原则来促进范德华外延，并基于全面的第一性原理计算，本文表明典型的亚稳态BlackP类GeTe可以很容易地稳定在同构SnSe的（001）表面上。重要的是，由于基底扩大了面内极位移，与独立状态相比，这种类 BlackP GeTe 单层的铁电性可以大大增强。 GeTe/SnSe 异质双层表现出多种铁电/亚铁电极化状态，可用于高密度存储器件。这些可相互切换的偏振态也被证明与价/导带的自旋偏振内部锁定，具有明显的拉什巴自旋轨道分裂和贝里曲率偶极子。这些发现凸显了范德华压印在开发新型二维材料以丰富功能方面所具有的直观而强大的力量。