Detailed Structural Examinations of Covalently Immobilized Gold Nanoparticles onto Hydrogen‐Terminated Silicon Surfaces

The modification of flat semiconductor surfaces with nanoscale materials has been the subject of considerable interest. This paper provides detailed structural examinations of gold nanoparticles covalently immobilized onto hydrogen‐terminated silicon surfaces by a convenient thermal hydrosilylation to form Si? C bonds. Gold nanoparticles stabilized by ω‐alkene‐1‐thiols with different alkyl chain lengths (C₃, C₆, and C₁₁), with average diameters of 2–3 nm and a narrow size distribution were used. The thermal hydrosilylation reactions of these nanoparticles with hydrogen‐terminated Si(111) surfaces were carried out in toluene at various conditions under N₂. The obtained modified surfaces were observed by high‐resolution scanning electron microscopy (HR‐SEM). The obtained images indicate considerable changes in morphology with reaction time, reaction temperature, as well as the length of the stabilizing ω‐alkene‐1‐thiol molecules. These surfaces are stable and can be stored under ambient conditions for several weeks without measurable decomposition. It was also found that the aggregation of immobilized particles on a silicon surface occurred at high temperature (> 100 °C). Precise XPS measurements of modified surfaces were carried out by using a Au–S ligand‐exchange technique. The spectrum clearly showed the existence of Si? C bonds. Cross‐sectional HR‐TEM images also directly indicate that the particles were covalently attached to the silicon surface through Si? C bonds.