Structure sensitive in situ Raman study of iron passive films using SERS-active Fe ∕ Au ( 111 ) substrates
Abstract
This work describes the preparation of well-defined Fe∕Au(111)/mica substrates for in situ Raman studies of the iron passive film with surface-enhanced Raman scattering (SERS). It is a two-step technique in which a SERS active (111) epitaxial gold substrate is prepared by resistive evaporation on mica. An epitaxial Fe(110) film is then electrodeposited to serve as iron electrode. It is shown that the SERS enhancement factor depends primarily on the good matching between the gold film plasmon resonance wavelength λP and the excitation wavelength. The iron thickness is the second main parameter controlling the SERS enhancement factor with a maximum found for a thickness of 20 monolayers. Under optimized conditions an amplification factor of 5×104 is demonstrated with respect to the case of a bulk polycrystalline iron substrate. This technique allows the recording of Raman spectra of nm-thick passive films within a few seconds only, which opens up to nearly real-time bias-dependent investigations of the chemistry at the electrochemical interface. In addition, taking advantage of the well-defined structure of the Fe(110)∕Au(111)∕mica substrates, we present a preliminary structure-sensitive in situ Raman study of the iron passive film formed in a borate solution of pH 8.4. It is thought that this simple approach of promoting SERS should find more general interest for the electrochemistry community.