From Octahedron Crystals to 2D Silicon Nanosheets: Facet‐Selective Cleavage and Biophotonic Applications

2D silicon nanosheets (SiNSs) are promising materials for biomedicine but facile synthesis of SiNSs remains a challenge. Herein, by means of a sulfur-iodine co-assisted chemical vapor transport method, octahedron silicon (oct-Si) crystals with fully exposed {111} planes are prepared as precursors for efficient synthesis of SiNSs by facet-selective exfoliation. The 13 nm thick SiNSs have good biocompatibility and the sharp Raman scattering signal facilitates intracellular Raman imaging upon exposure to a near-infrared (NIR) laser. Furthermore, the SiNSs have excellent NIR photothermal characteristics such as a large extinction coefficient of 11.3 L g^-1 cm^-1 and high photothermal conversion efficiency of 21.4% at 1064 nm. In vitro experiments demonstrate superior NIR-II photothermal therapeutic effects in killing cancer cells. Comparing to conventional methods, the novel facet-selective cleavage strategy is more controllable and environmentally friendly boding well for the fabrication of non-van der Waals 2D materials. The multimodal photonic behavior also suggests large potential of the SiNSs pertaining to integrated multi-NIR biophotonic techniques using single nanomaterials.