Nanoscale Raman Imaging with Nanogold-Topped AFM Probes Fabricated by Area-Selective Electroless Deposition

A single gold nanostructure is successfully deposited at the tip apex of a silicon probe for atomic force microscopes (AFM) in an electroless and area-selective manner. The tip apex of a commercially available silicon AFM probe is irradiated with a focused ion beam (FIB) to remove the native oxide layer, and then the probe was exposed to chloroauric acid (HAuCl4) aqueous solution containing sodium chloride (NaCl). A single gold nanostructure selectively grows at the FIB-irradiated apex as a consequence of electron transfer from silicon to the solution through the FIB-irradiated silicon surface. This electron transfer is driven by the difference in the electrochemical potential of electrons. NaCl, added to a pure HAuCl4 aqueous solution, improves the area-selectivity of gold growth and decreases the size of gold, resulting in desired geometry of gold as the tip apex for tip-enhanced Raman spectroscopy (TERS) in terms of the spatial resolution and the enhancement of the electric field. Our probes provide TERS imaging of a carbon nanotube with a spatial resolution of 10 nm, and enhancement factors up to 2.2 × 105 for an azobenzene thiol self-assembled monolayer in the gap-mode configuration with a side-illumination optical setup.