Hexagonal boron nitride (h-BN) is believed to offer better passivation to metallic surfaces than graphene owing to its insulating nature, which facilitates blocking the flow of electrons, thereby preventing the occurrence of galvanic reactions. Nevertheless, this may not be the case when an h-BN-protected material is exposed to aqueous environments. In this work, we analyzed the stability of mono and multilayer h-BN stacks exposed to H₂O₂ and atmospheric conditions. Our experiments revealed that monolayer h-BN is as inefficient as graphene as a protective coating when exposed to H₂O₂. Multilayer h-BN offered a good degree of protection. Monolayer h-BN was found to be ineffective in an air atmosphere as well. Even a 10–15 layers-thick h-BN stack could not completely protect the surface of the metal under consideration. By combining Auger electron spectroscopy and secondary ion mass spectrometry techniques, we observed that oxygen could diffuse through the grain boundaries of the h-BN stack to reach the metallic substrate. Fortunately, because of the diffusive nature of the process, the oxidized area did not increase with time once a saturated state was reached. This makes multilayer (not monolayer) h-BN a suitable long-term oxidation barrier. Oxygen infiltration could not be observed by X-ray photoelectron spectroscopy. This technique cannot assess the chemical composition of the deeper layers of a material. Hence, the previous reports, which relied on XPS to analyze the passivating properties of h-BN and graphene, may have ignored some important subsurface phenomena. The results obtained in this study provide new insights into the passivating properties of mono and multilayer h-BN in aqueous media and the degradation kinetics of h-BN-coated metals exposed to an air environment.

The development of flexible transparent electrodes for next generation devices has been appointed as the major topic in carbon electronics research for the next five years. Among all candidate materials tested to date, graphene and graphene based nanocomposites have shown the highest performance. Although some incipient anti-oxidation tests have been reported, in-deep ageing studies to assess the reliability of carbon-based electrodes have never been performed before. In this work, we present a disruptive methodology to assess the ageing mechanisms of graphene electrodes, which is also extensible to other carbonbased and two-dimensional materials. After performing accelerated oxidative tests, we exhaustively analyze the yield of the electrodes combining nanoscale and device level experiments with Weibull probabilistic analyses and tunneling current simulation, based on the Fowler-Nordheim/Direct-Tunneling models. Our experiments and calculations reveal that an ultra-thin oxide layer can be formed on the pristine surface of graphene. We quantitatively analyze the consequences of this layer on the properties of the electrodes, and observed a change in the conduction mode at the interface (from Ohmic to Schottky), an effect that should be considered in the design of future graphene-based devices. Future mass production of carbon-based devices should include similar reliability studies, and the methodologies presented here (including the accelerated tests, characterization and modeling) may help other scientists to move from lab prototypes towards industrial device production.