Kinetic control for planar oxidation of MoS$_2$

TL;DR

This study investigates the atomic-scale mechanisms of MoS$_2$ oxidation, demonstrating how thermal and plasma processes influence oxide morphology and kinetics, with implications for TMD-based device fabrication.

Contribution

It provides a detailed analysis of MoS$_2$ oxidation pathways and introduces plasma-assisted methods to control oxide film quality and growth rate.

Findings

Thermal oxidation produces crystalline MoO$_3$ with sharp interfaces.

Plasma oxidation yields smooth, amorphous MoO$_3$ films.

Oxidation proceeds via vapor-phase mass transport and redeposition.

Abstract

Layered transition metal dichalcogenide (TMD) semiconductors oxidize readily in a variety of conditions, and a thorough understanding of this oxide formation is required for the advancement of TMD-based microelectronics. Here, we combine scanning transmission electron microscopy (STEM) with spectroscopic ellipsometry (SE) to investigate oxide formation at the atomic scale of the most widely-studied TMD, MoS$_2$. We find that aggressive thermal oxidation results in $\alpha$-phase plate-like crystalline MoO$_3$ with sharp interfaces, voids, and a textured alignment with the underlying MoS$_2$. Experiments with remote substrates and patterned MoS$_2$ prove that thermal oxidation proceeds via vapor-phase mass transport and redeposition - a challenge to forming thin, conformal planar oxide films. We accelerate the kinetics of oxidation relative to the kinetics of mass transport using a non-thermal oxygen plasma process, to form a smooth and conformal amorphous oxide. The resulting amorphous MoO$_3$ films can be grown several nanometers thick, and we calibrate the oxidation rate for varying plasma processing conditions. Our results illustrate how TMD semiconductor oxidation differs significantly from oxidation of legacy semiconductors, most notably silicon, and provide quantitative guidance for managing both the atomic scale structure and thin film morphology of oxides in the design and processing of MoS$_2$ semiconductor devices.