Sodium‐Mediated Epitaxial Growth of 2D Ultrathin Sb2Se3 Flakes for Broadband Photodetection

As an important member of group VA–VIA semiconductors, 2D Sb₂Se₃ has drawn widespread attention thanks to its outstanding optoelectronic properties as compared to the bulk material. However, due to the intrinsic chain‐like crystal structure, the controllable synthesis of ultrathin 2D planar Sb₂Se₃ nanostructures still remains a huge challenge. Herein, for the first time, the crystal structure limitation is overcome and the successful structural evolution of 2D ultrathin Sb₂Se₃ flakes (as thin as 1.3 nm), by introducing a sodium‐mediated chemical vapor deposition (CVD) growth method, is realized. The formation of 2D planar geometry is mainly attributed to the preferential growth of (010) plane with the lowest formation energy. The thickness‐dependent band structure of 2D Sb₂Se₃ flakes shows a wide absorption band from UV to NIR region (300–1000 nm), suggesting its potential application in broadband photodetection. Strikingly, the Sb₂Se₃ flakes–based photodetector demonstrates excellent performance such as broadband response varying from UV to NIR region, high responsivity of 4320 mA W^?1, fast response time (τ_rise ≈ 13.16 ms and τ_decay ≈ 9.61 ms), and strong anisotropic ratio of 2.5@ 532 nm, implying promising potential application in optoelectronics.