Siliconizing-Driven Layer-by-Layer Growth of 2D Tellurides with Controlled Crystallization

2D transition metal tellurides (TMTs) possess fascinating properties for applications in ferroelectrics and optoelectronics. Nevertheless, it is still challenging to grow high-quality 2D TMTs with the desired phase (especially high-temperature phase) because of the weak bonding between the transition metal and Te as compared to S and Se atoms. Here, a strategy of siliconizing-driven layer-by-layer growth is reported to synthesize 2D ZrTe₂ and ZrTe₃ crystals with high crystallinity and desired thickness. Both as-synthesized crystals exhibit large-area uniform phases and atomically precise layered stacking structures. 2D ZrTe₂ shows type-II Weyl semimetal characteristics with negative magnetoresistance, and 2D ZrTe₃ demonstrates the existence of charge density waves and intrinsic superconductivity. Theoretical study reveals that silicon atoms can infiltrate and isolate a single layer of zirconium atoms and allow them to be tellurized in a layer-by-layer manner. The work paves the way for the synthesis of layer-controlled 2D TMTs and lays a material foundation for their physical property research.