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Molecular electronics is a fascinating area of research with the ability totune device properties by a chemical tailoring of organic molecules. However,molecular electronics devices often suffer from dispersion and lack ofreproducibility of their electrical performances. Here, we show that watermolecules introduced during the fabrication process or coming from theenvironment can strongly modify the electrical transport properties ofmolecular junctions made on hydrogen-terminated silicon. We report an increasein conductance by up to three orders of magnitude, as well as an inducedasymmetry in the current-voltage curves. These observations are correlated witha specific signature of the dielectric response of the monolayer at lowfrequency. In addition, a random telegraph signal is observed for thesejunctions with macroscopic area. Electrochemical charge transfer reactionbetween the semiconductor channel and H+/H2 redox couple is proposed as theunderlying phenomenon. Annealing the samples at 150{\deg}C is an efficient wayto suppress these water-related effects. This study paves the way to a bettercontrol of molecular devices and has potential implications when thesemonolayers are used as hydrophobic layers or incorporated in chemical sensors.

Role of Hydration on the Electronic Transport through Molecular Junctions on Silicon