Charging/discharging of Au (core)/silica (shell) nanoparticles as revealed by XPS

By recording XPS spectra while applying external voltage stress to the sample rod, we can control the extent of charging developed on core-shell-type gold nanoparticles deposited on a copper substrate, in both steady-state and time-resolved fashions. The charging manifests itself as a shift in the measured binding energy of the corresponding XPS peak. Whereas the bare gold nanoparticles exhibit no measurable binding energy shift in the Au 4f peaks, both the Au 4f and the Si 2p peaks exhibit significant and highly correlated (in time and magnitude) shifts in the case of gold (core)/silica (shell) nanoparticles. Using the shift in the Au 4f peaks, the capacitance of the 15-nm gold (core)/6-nm silica (shell) nanoparticle/nanocapacitor is estimated as 60 aF. It is further estimated that, in the fully charged situation, only 1 in 1000 silicon dioxide units in the shell carries a positive charge during our XPS analysis. Our simple method of controlling the charging, by application of an external voltage stress during XPS analysis, enables us to detect, locate, and quantify the charges developed on surface structures in a completely noncontact fashion.