The crystal structure of graphene flakes is expected to significantly affect their sensing properties. Here we report an experimental investigation on the crystalline structure of graphene aimed at exploring the effects on the gas sensing properties. The morphology of graphene, prepared via Chemical Vapor Deposition (CVD), Liquid Phase Exfoliation (LPE) and Mechanical Exfoliation (ME), is inspected through Raman spectroscopy, Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM). CVD and LPE-graphene structures are found to be more defective with respect to ME-graphene. The defects are due to the jagged morphology of the films rather than originating from intrinsic disorder. The flatness of ME-graphene flakes, instead, explains the absence of defects. Chemiresistors based on the three different graphene preparation methods are subsequently exposed to NO2 in the concentration range 0.1–1.5 ppm (parts per million). The device performance is demonstrated to be strongly and unambiguously affected by the material structure: the less defective the material is, the higher the response rate is. In terms of signal variation, at 1.5 ppm, for instance, ME-graphene shows the highest value (5%) among the three materials. This study, comparing simultaneously graphene and sensors prepared via different routes, provides the first experimental evidence of the role played by the graphene level of defectiveness in the interaction with analytes. Moreover, these findings can pave the path for tailoring the sensor behavior as a function of graphene morphology.

The sp² carbon-based allotropes have been extensively exploited for the realization of gas sensors in the recent years because of their high conductivity and large specific surface area. A study on graphene that was synthetized by means of a novel transfer-free fabrication approach and is employed as sensing material is herein presented. Multilayer graphene was deposited by chemical vapour deposition (CVD) mediated by CMOS-compatible Mo. The utilized technique takes advantage of the absence of damage or contamination of the synthesized graphene, because there is no need for the transfer onto a substrate. Moreover, a proper pre-patterning of the Mo catalyst allows one to obtain graphene films with different shapes and dimensions. The sensing properties of the material have been investigated by exposing the devices to NO₂, NH₃ and CO, which have been selected because they are wellknown hazardous substances. The concentration ranges have been chosen according to the conventional monitoring of these gases. The measurements have been carried out in humid N₂ environment, setting the flow rate at 500 sccm, the temperature at 25 °C and the relative humidity (RH) at 50%. An increase of the conductance response has been recorded upon exposure towards NO₂, whereas a decrease of the signal has been detected towards NH₃. The material appears totally insensitive towards CO. Finally, the sensing selectivity has been proven by evaluating and comparing the degree of adsorption and the interaction energies for NO₂ and NH₃ on graphene. The direct-growth approach for the synthesis of graphene opens a promising path towards diverse applicative scenarios, including the straightforward integration in electronic devices.