Charge Redistribution Mechanisms in SnSe2Surfaces Exposed to Oxidative and Humid Environments and Their Related Influence on Chemical Sensing

Tin diselenide (SnSe2) is a van der Waals semiconductor, which spontaneously forms a subnanometric SnO2 skin once exposed to air. Here, by means of surface-science spectroscopies and density functional theory, we have investigated the charge redistribution at the SnO2-SnSe2 heterojunction in both oxidative and humid environments. Explicitly, we find that the work function of the pristine SnSe2 surface increases by 0.23 and 0.40 eV upon exposure to O2 and air, respectively, with a charge transfer reaching 0.56 e-/SnO2 between the underlying SnSe2 and the SnO2 skin. Remarkably, both pristine SnSe2 and defective SnSe2 display chemical inertness toward water, in contrast to other metal chalcogenides. Conversely, the SnO2-SnSe2 interface formed upon surface oxidation is highly reactive toward water, with subsequent implications for SnSe2-based devices working in ambient humidity, including chemical sensors. Our findings also imply that recent reports on humidity sensing with SnSe2 should be reinterpreted, considering the pivotal role of the oxide skin in the interaction with water molecules. ©PID2019-109525RB-I00; Horizon 2020 Framework Programme, H2020: 730872; Ministerio de Economía y Competitividad, MINECO: CEX2018-000805-M, E12H1800010001; Ministero dell’Istruzione, dell’Università e della Ricerca, MIUR; Ministry of Education and Science of the Russian Federation, Minobrnauka: FEUZ-2020-0060This work has been partially supported by the Spanish Ministerio de Ciencia e Innovación under Project PID2019-109525RB-I00. D.F. acknowledges financial support from the Spanish Ministry of Economy and Competitiveness, through the “María de Maeztu” Programme for Units of Excellence in R&D (CEX2018-000805-M). D.F. and A.A.T. acknowledge the project CALIPSOplus under Grant Agreement 730872 from the EU Framework Programme for Research and Innovation HORIZON 2020. A.P. and G.D. acknowledge the CERIC–ERIC Consortium for the access to the Nanospectroscopy facility and financial support. G.D. acknowledges funding of a Ph.D. fellowship from PON Ricerca e Innovazione 2014–2020 (Project E12H1800010001) by the Italian Ministry of University and Research (MIUR). D.W.B. acknowledges the support by the Ministry of Science and Higher Education of the Russian Federation (through the basic part of the government mandate, Project No. FEUZ-2020-0060)