Hole Transport in Exfoliated Monolayer MoS$_2$

TL;DR

This study reveals that monolayer MoS$_2$ exhibits anomalous hole transport due to chalcogen vacancy defects creating in-gap states, unlike other TMDC monolayers, highlighting the importance of defect control in 2D semiconductors.

Contribution

It provides a detailed experimental analysis showing how chalcogen vacancies uniquely affect hole transport in MoS$_2$ monolayers compared to other TMDCs.

Findings

Hole transport in MoS$_2$ monolayers is anomalous with a conductivity maximum at negative gate voltage.

Chalcogen vacancies create in-gap states near the valence band top in MoS$_2$ monolayers.

Defect-related in-gap states strongly trap holes, affecting transport properties.

Abstract

Ideal monolayers of common semiconducting transition metal dichalcogenides (TMDCs) such as MoS$_2$, WS$_2$, MoSe$_2$, and WSe$_2$ possess many similar electronic properties. As it is the case for all semiconductors, however, the physical response of these systems is strongly determined by defects in a way specific to each individual compound. Here we investigate the ability of exfoliated monolayers of these TMDCs to support high-quality, well-balanced ambipolar conduction, which has been demonstrated for WS$_2$, MoSe$_2$, and WSe$_2$, but not for MoS$_2$. Using ionic-liquid gated transistors we show that, contrary to WS$_2$, MoSe$_2$, and WSe$_2$, hole transport in exfoliated MoS$_2$ monolayers is systematically anomalous, exhibiting a maximum in conductivity at negative gate voltage (V$_G$) followed by a suppression of up to 100 times upon further increasing V$_G$. To understand the origin of this difference we have performed a series of experiments including the comparison of hole transport in MoS$_2$ monolayers and thicker multilayers, in exfoliated and CVD-grown monolayers, as well as gate-dependent optical measurements (Raman and photoluminescence) and scanning tunneling imaging and spectroscopy. In agreement with existing {\it ab-initio} calculations, the results of all these experiments are consistently explained in terms of defects associated to chalcogen vacancies that only in MoS$_2$ monolayers -- but not in thicker MoS$_2$ multilayers nor in monolayers of the other common semiconducting TMDCs -- create in-gap states near the top of the valence band that act as strong hole traps. Our results demonstrate the importance of studying systematically how defects determine the properties of 2D semiconducting materials and of developing methods to control them.