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Light emission spectrum from a scanning tunnelling microscope (LESTM) isinvestigated as a function of relative humidity and shown to be a novel andsensitive means for probing the growth and properties of a water meniscus inthe nm-scale. An empirical model of the light emission process is formulatedand applied successfully to replicate the decay in light intensity and spectralchanges observed with increasing relative humidity. The modelling indicates aprogressive water filling of the tip-sample junction with increasing humidityor, more pertinently, of the volume of the localized surface plasmonsresponsible for light emission; it also accounts for the effect of asymmetry instructuring of the water molecules with respect to polarity of the appliedbias. This is juxtaposed with the case of a non-polar liquid in the tip-samplenano cavity where no polarity dependence of the light emission is observed. Incontrast to the discrete detection of the presence/absence of water bridge inother scanning probe experiments by measurement of the feedback parameter forinstrument control LESTM offers a means of continuously monitoring thedevelopment of the water bridge with sub-nm sensitivity. The results arerelevant to applications such as dip-pen nanolithography and electrochemicalscanning probe microscopy.

The tip-sample water bridge and light emission from scanning tunnelling microscopy