Oxidation of Monolayer WS$_{2}$ in Ambient is a Photoinduced Process

TL;DR

This study reveals that monolayer WS2 undergoes photoinduced oxidation in ambient conditions, especially under light energies above the trion excitation threshold, impacting its stability and measurement in research and applications.

Contribution

It demonstrates that ambient oxidation of WS2 is driven by photo-oxidation linked to specific photon energies, with detailed analysis of the process and its dependence on illumination conditions.

Findings

Oxidation correlates with high-symmetry, sulfur-vacancy-rich areas.

Oxidation occurs rapidly under light above the trion energy.

Dark storage prevents oxidation for up to 10 months.

Abstract

We have studied the ambient air oxidation of chemical vapor deposition (CVD) grown monolayers of the semiconducting transition metal dichalcogenide (S-TMD) WS$_{2}$ using optical microscopy, laser scanning confocal microscopy (LSCM), photoluminescence (PL) spectroscopy, and atomic force microscopy (AFM). Monolayer WS$_{2}$ exposed to ambient conditions in the presence of light (typical laboratory ambient light for weeks, or typical PL spectroscopy map), exhibits damage due to oxidation which can be detected with the LSCM and AFM; though may not be evident in conventional optical microscopy due to poorer contrast and resolution. Additionally, this oxidation was not random, and correlated with 'high-symmetry' and red-shifted areas in the PL spectroscopy map - areas thought to contain a higher concentration of sulfur vacancies. In contrast, samples kept in ambient and darkness showed no signs of oxidation for up to 10 months. Low-irradiance/fluence experiments showed that samples subjected to excitation energies at or above the trion excitation energy (532 nm/2.33 eV and 660 nm/1.88 eV) oxidized in as little as 7 days, even for irradiances and fluences eight and four orders of magnitude lower (respectively) than previously reported. No significant oxidation was observed for 760 nm/1.63 eV light exposure, which lies below the trion excitation energy in WS$_{2}$. The strong wavelength dependence and apparent lack of irradiance dependence suggests that ambient oxidation of WS$_{2}$ is initiated by photon-mediated electronic band transitions, that is, photo-oxidation. These findings have important implications for prior, present and future studies concerning S-TMDs measured, stored or manipulated in ambient conditions.