Substrate‐Free Hydrothermal Synthesis of Atomically Thin Tellurene with Enhanced Morphological Control and Device‐Ready Properties

2D nanomaterials with atomic‐scale thickness have attracted widespread attention due to their unique properties, including strong electrostatic gate control, excellent mechanical and thermal stability, and low power consumption. Among them, tellurene (2D Te), composed of helical chains of elemental tellurium, has emerged as a promising candidate for next‐generation semiconductor applications, owing to its outstanding environmental stability, superior flexibility, high carrier mobility, and tunable bandgap. However, conventional synthesis methods face notable limitations. Chemical vapor deposition requires precise atmospheric control and is highly substrate‐dependent, often resulting in poor uniformity and scalability. Alternatively, top‐down techniques such as liquid‐phase exfoliation offer large‐scale production but suffer from thickness nonuniformity, surface defects, and low yield of monolayer or few‐layer flakes, thereby limiting their practical applicability. In this study, a substrate‐free hydrothermal synthesis method is presented for producing high‐quality, large‐area 2D Te with controlled thickness and lateral dimensions. This solution‐based, low‐temperature approach enables facile fabrication without reliance on specific substrates and demonstrates excellent morphological control. The synthesized tellurene exhibits favorable characteristics suitable for integration into semiconductor devices and flexible electronics. The findings provide a practical and facile route for 2D Te fabrication and offer new opportunities for its implementation in future electronic and optoelectronic technologies.