Hole Transport in Exfoliated Monolayer MoS₂

Ideal monolayers of common semiconducting transition-metal dichalcogenides (TMDCs) such as MoS₂, WS₂, MoSe₂, and WSe₂ 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 WS₂, MoSe₂, and WSe₂, but not for MoS₂. Using ionic-liquid gated transistors, we show that, contrary to WS₂, MoSe₂, and WSe₂, hole transport in exfoliated MoS₂ 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 MoS₂ 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 ab initio calculations, the results of all these experiments are consistently explained in terms of defects associated with chalcogen vacancies that only in MoS₂ monolayers, but not in thicker MoS₂ 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.