Silicon nanomaterials are encouraging candidates for application to photonic, electronic, or biosensing devices, due to their size-quantization effects. Two-dimensional silicon nanosheets could help to realize a widespread quantum field, because of their nanoscale thickness and microscale area. However, there has been no example of a successful synthesis of two-dimensional silicon nanomaterials with large lateral size and oxygen-free surfaces. Here we report that oxygen-free silicon nanosheets covered with organic groups can be obtained by exfoliation of layered polysilane as a result of reaction with n-decylamine and dissolution in an organic solvent. The amine residues are covalently bound to the Si(111) planes. It is estimated that there is ca. 0.7 mol of residue per mole of Si atoms in the reaction product. The amine-modified layered polysilane can dissolve in chloroform and exfoliate into nanosheets that are 1-2 microm wide in the lateral direction and with thicknesses on the order of nanometers. The nanosheets have very flat and smooth surfaces due to dense coverage of n-decylamine, and they are easily self-assembled in a concentrated state to form a regularly stacked structure. The nanosheets could be useful as building blocks to create various composite materials.

The synthesis of silicon nanosheets for fabricating electronic devices, without using conventional vacuum processes and vapor deposition, is challenging and is anticipated to receive significant attention for a wide range of applications. Here, we report the synthesis of oxygen-free, phenyl-modified organosilicon nanosheets with atomic thickness. In organic solvents, a consequence of this new silicon structure is its uniform dispersion and the possibility of exfoliation into unilamellar nanosheets. Light-induced photocurrent in [Si(6)H(4)Ph(2)] was observed, leading to the possibility of various organosilicon nonamaterials with useful properties.

Transparent Si nanosheets with a thickness of 0.37 nm are produced by chemically exfoliating calcium disilicide with propylamine hydrochloride (PA⋅HCl; see picture, Ca white, Si red). The nanosheets have a two‐dimensional silicon backbone and are an order of magnitude thinner than previously reported silicon nanostructures.