Sensitivity of sum frequency generation experimental conditions to thin film interference effects

Sum-frequency generation (SFG) spectroscopy has furthered our understanding of the chemical interfaces that guide key processes in biology, catalysis, environmental science, and energy conversion. However, interpreting SFG spectra of systems containing several internal interfaces, such as thin film electronics, electrochemical cells, and biofilms, is challenging as different interfaces within these structures can produce interfering SFG signals. One potential way to address this issue is to carefully select experimental conditions that amplify the SFG signal of an interface of interest over all others. In this report, we investigate a model two-interface system to assess our ability to isolate the SFG signal from each interface. For SFG experiments performed in a reflective geometry, we find that there are few experimental conditions under which the SFG signal originating from either interface can be amplified and isolated from the other. However, by performing several measurements under conditions that alter their interference, we find that we can reconstruct each signal even in cases where the SFG signal from one interface is more than an order of magnitude smaller than its counterpart. The number of spectra needed for this reconstruction varies depending on the signal-to-noise level of the SFG dataset and the degree to which different experiments in a dataset vary in their sensitivity to each interface. Taken together, our work provides general guidelines for designing experimental protocols that can isolate SFG signals stemming from a particular region of interest within complex samples.