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.