Towards Improved Humidity Sensing Nanomaterials via Combined Electron and NH₃ Treatment of Carbon-Rich FEBID Deposits

Focused Electron Beam Induced Deposition (FEBID) is a unique tool to produce nanoscale materials. The resulting deposits can be used, for instance, as humidity or strain sensors. The humidity sensing concept relies on the fact that FEBID using organometallic precursors often yields deposits which consist of metal nanoparticles embedded in a carbonaceous matrix. The electrical conductivity of such materials is altered in the presence of polar molecules such as water. Herein, we provide evidence that the interaction with water can be enhanced by incorporating nitrogen in the deposit through post-deposition electron irradiation in presence of ammonia (NH₃). This opens the perspective to improve and tune the properties of humidity sensors fabricated by FEBID. As a proof-of-concept experiment, we have prepared carbonaceous deposits by electron irradiation of adsorbed layers of three different precursors, namely, the aliphatic hydrocarbon n-pentane, a simple alkene (2-methyl-2-butene), and the potential Ru FEBID precursor bis(ethylcyclopentadienyl)ruthenium(II). In a subsequent processing step, we incorporated C-N bonds in the deposit by electron irradiation of adsorbed NH₃. To test the resulting material with respect to its potential humidity sensing capabilities, we condensed sub-monolayer quantities of water (H₂O) on the deposit and evaluated their thermal desorption behavior. The results confirm that the desorption temperature of H₂O decisively depends on the degree of N incorporation into the carbonaceous residue which, in turn, depends on the chemical nature of the precursor used for deposition of the carbonaceous layer. We thus anticipate that the sensitivity of a FEBID-based humidity sensor can be tuned by a precisely timed post-deposition electron and NH₃ processing step.