Abstract
Doping and alloying are effective ways to engineer the band structure and modulate the optoelectronic functionality of monolayer transition metal dichalcogenides (TMDs). In this work, we explore the synthesis and electronic properties of monolayer Mo1-xWxSe2 (0<x<0.18) alloys with almost 100% alloying degree. The isoelectronic substitutional doping of tungsten for molybdenum in the monolayer MoSe2 is shown to suppress its intrinsically n-type conduction behavior, with p-type conduction gradually emerging to become dominant with increasing W concentration in the alloys. Atomic resolution Z-contrast electron microscopy show that W is shown to substitute directly for Mo without the introduction of noticeable vacancy or interstitial defects, however with randomly-distributed ‘W-rich’ regions ~2 nm in diameter. Scanning tunneling microscopy/spectroscopy measurements reveal that these W-rich regions exhibit a local band structure with the valence band maximum (VBM) closer to the Fermi level as compared with the ‘Mo-rich’ regions in the monolayer Mo1-xWxSe2 crystal. These localized upshifts of the VBM in the local band structure appear responsible for the overall p-type behavior observed for the monolayer Mo1-xWxSe2 crystals. Stacked monolayers of n-type MoSe2 and p-type Mo1-xWxSe2 were demonstrated to form atomically thin, vertically stacked p−n homojunctions with gate-tunable characteristics, which appear useful for future optoelectronic applications. These results indicate that alloying with isoelectronic dopant atoms appears to be an effective and advantageous alternate strategy to doping or alloying with electron donors or acceptors in two-dimensional TMDs.
