Self-Assembled SnO₂/SnSe₂ Heterostructures: A Suitable Platform for Ultrasensitive NO₂ and H₂ Sensing

By means of experiments and theory, the gas-sensing properties of tin diselenide (SnSe₂) were elucidated. We discover that, while the stoichiometric single crystal is chemically inert even in air, the nonstoichiometric sample assumes a subnanometric SnO₂ surface oxide layer once exposed to ambient atmosphere. The presence of Se vacancies induces the formation of a metastable SeO₂-like layer, which is finally transformed into a SnO₂ skin. Remarkably, the self-assembled SnO₂/SnSe_2-x heterostructure is particularly efficient in gas sensing, whereas the stoichiometric SnSe₂ sample does not show sensing properties. Congruently with the theoretical model, direct sensing tests carried out on SnO₂/SnSe_2- at an operational temperature of 150 °C provided sensitivities of (1.06 ± 0.03) and (0.43 ± 0.02) [ppm]^-1 for NO₂ and H₂, respectively, in dry air. The corresponding calculated limits of detection are (0.36 ± 0.01) and (3.6 ± 0.1) ppm for NO₂ and H₂, respectively. No detectable changes in gas-sensing performances are observed in a time period extended above six months. Our results pave the way for a novel generation of ambient-stable gas sensor based on self-assembled heterostructures formed taking advantage on the natural interaction of substoichiometric van der Waals semiconductors with air.