In this work, we evaluate the dependence of tip-enhanced Raman (TER) spectra of a monolayer of thiophenol at a Au(111) electrode on the scanning tunneling microscope's tunneling current set-point and bias voltage parameters. We find an increase of the TER intensity upon set-point increase or bias decrease as expected from a gap-distance reduction. The relations obtained follow a theoretical model considering a simple gap-distance change when tuning the mentioned parameters. We find that the value of the bias voltage affects the TER intensity to a larger extent than the current set-point. Therefore it is advisable to work in a low-bias regime when aiming for ultrasensitive TER measurements.

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Effective defect passivation of semiconductor surfaces and interfaces is indispensable for the development of high efficiency solar cells. In this study we systematically investigated the surface and grain boundary properties of CuInSe 2 (CISe) with scanning tunneling microscopy (STM) and spectroscopy (STS) after different surface treatments such as potassium cyanide (KCN) etching, pre-electrolyte treatment with cadmium ions, and annealing in ultrahigh vacuum (UHV). We show that air exposed samples with a subsequent KCN etching step exhibits a highly defective surface. However, a Cd pre-electrolyte treatment passivates most of these defects, which manifests itself by a reduction of the high conductance in the STS measurements at positive sample biases. The origin of the improvement can be traced back to an increase in surface band bending, which leads to a type inversion, induced by a change in the concentration of Cu vacancies. We observe a defect passivation at the CISe surface and at the grain boundaries. Our results give a direct explanation of why the CdS buffer layer in CISe thin film solar cells is of utmost importance for high efficiency devices.