A Universal Atomic Substitution Conversion Strategy Towards Synthesis of Large-Size Ultrathin Nonlayered Two-Dimensional Materials

Nonlayered two-dimensional (2D) materials have attracted increasing attention, due to novel physical properties, unique surface structure, and high compatibility with microfabrication technique. However, owing to the inherent strong covalent bonds, the direct synthesis of 2D planar structure from nonlayered materials, especially for the realization of large-size ultrathin 2D nonlayered materials, is still a huge challenge. Here, a general atomic substitution conversion strategy is proposed to synthesize large-size, ultrathin nonlayered 2D materials. Taking nonlayered CdS as a typical example, large-size ultrathin nonlayered CdS single-crystalline flakes are successfully achieved via a facile low-temperature chemical sulfurization method, where pre-grown layered CdI(2) flakes are employed as the precursor via a simple hot plate assisted vertical vapor deposition method. The size and thickness of CdS flakes can be controlled by the CdI(2) precursor. The growth mechanism is ascribed to the chemical substitution reaction from I to S atoms between CdI(2) and CdS, which has been evidenced by experiments and theoretical calculations. The atomic substitution conversion strategy demonstrates that the existing 2D layered materials can serve as the precursor for difficult-to-synthesize nonlayered 2D materials, providing a bridge between layered and nonlayered materials, meanwhile realizing the fabrication of large-size ultrathin nonlayered 2D materials. [Image: see text] SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s40820-021-00692-6.