Study of molecular trapping inside gold nanofinger arrays on surface-enhanced Raman substrates

The binding of trans-1,2-bis(4-pyridyl)-ethylene (BPE) molecules on substrates arrayed with flexible gold nanofingers has been studied by surface-enhanced Raman spectroscopy (SERS) and angle-resolved X-ray photoelectron spectroscopy (AR-XPS). On the basis of the SERS and XPS results, BPE molecules are found to interact with the gold nanofingers through the lone pair electrons of pyridyl nitrogens, not through delocalized π electrons. Furthermore, after comparing the AR-XPS spectra of finger arrays preclosed before exposure to BPE with the spectra of arrays that closed after exposure to BPE, we observed in the latter case, at grazing takeoff angles, an increase in the component of the nitrogen photoelectron peak associated with pyridyl nitrogen atoms residing on bridging sites. These results demonstrate that a small percentage of BPE molecules was trapped between the neighboring gold finger tips during the finger closing process. However, because these trapped BPE molecules coincidently resided in the hot spots formed among the touching finger tips, the substantial increase in the observed SERS signal was dominated by the contribution from this small minority of BPE molecules.