Tuning Electronic Structure of Single Layer MoS₂ through Defect and Interface Engineering

Transition-metal dichalcogenides (TMDs) have emerged in recent years as a special group of two-dimensional materials and have attracted tremendous attention. Among these TMD materials, molybdenum disulfide (MoS2) has shown promising applications in electronics, photonics, energy, and electrochemistry. In particular, the defects in MoS2 play an essential role in altering the electronic, magnetic, optical, and catalytic properties of MoS2, presenting a useful way to engineer the performance of MoS2. The mechanisms by which lattice defects affect the MoS2 properties are unsettled. In this work, we reveal systematically how lattice defects and substrate interface affect MoS2 electronic structure. We fabricated single-layer MoS2 by chemical vapor deposition and then transferred onto Au, single-layer graphene, hexagonal boron nitride, and CeO2 as substrates and created defects in MoS2 by ion irradiation. We assessed how these defects and substrates affect the electronic structure of MoS2 by performing X-ray photoelectron spectroscopy, Raman and photoluminescence spectroscopies, and scanning tunneling microscopy/spectroscopy measurements. Molecular dynamics and first-principles based simulations allowed us to conclude the predominant lattice defects upon ion irradiation and associate those with the experimentally obtained electronic structure. We found that the substrates can tune the electronic energy levels in MoS2 due to charge transfer at the interface. Furthermore, the reduction state of CeO2 as an oxide substrate affects the interface charge transfer with MoS2. The irradiated MoS2 had a faster hydrogen evolution kinetics compared to the as-prepared MoS2, demonstrating the concept of defect controlled reactivity in this phase. Our findings provide effective probes for energy band and defects in MoS2 and show the importance of defect engineering in tuning the functionalities of MoS2 and other TMDs in electronics, optoelectronics, and electrochemistry.