Anomalous tip-sample distance behavior on the tip-enhanced Raman spectroscopy of graphene in ambient conditions

Tip-enhanced Raman spectroscopy (TERS) combines Raman spectroscopy with scanning probe microscopy to overcome the spatial resolution limitation imposed by light diffraction, offering a primary optical technique for the comprehensive study of two-dimensional (2D) materials. In this work, we investigate an anomalous decay profile of the TERS intensity of the graphene 2D band as the tip-sample separation changes, observations enabled by high TERS efficiency and accuracy in tip-approach and tip-retract procedures. The anomalous results can be properly described by the addition of an ad hoc deformation to the effective tip-sample distance, rationalized here as due to the presence of a liquid meniscus formed via capillary forces.