Interaction of black phosphorus with oxygen and water

Abstract

Black phosphorus (BP) has attracted significant interest as a monolayer or few-layer material with extraordinary electrical and optoelectronic properties. Chemical reactions with different ambient species, notably oxygen and water, are important as they govern key properties such as stability in air, electronic structure and charge transport, wetting by aqueous solutions, and so on. Here, we report experiments combined with ab initio calculations that address the effects of oxygen and water in contact with BP. Our results show that the reaction with oxygen is primarily responsible for changing properties of BP. Oxidation involving the dissociative chemisorption of O2 causes the decomposition of BP and continuously lowers the conductance of BP field-effect transistors (FETs). In contrast, BP is stable in contact with deaerated (i.e., O2 depleted) water and the carrier mobility in BP FETs gated by H2O increases significantly due to efficient dielectric screening of scattering centers by the high-k dielectric. Isotope labeling experiments, contact angle measurements, and calculations show that the pristine BP surface is hydrophobic but is turned progressively hydrophilic by oxidation. Our results open new avenues for exploring applications that require contact of BP with aqueous solutions including solution gating, electrochemistry, and solution-phase approaches for exfoliation, dispersion, and delivery of BP. © 2016 American Chemical Society