Quantification and Healing of Defects in Atomically Thin Molybdenum Disulfide: Beyond the Controlled Creation of Atomic Defects

Atomically thin 2D materials provide an opportunity to investigate the atomic-scale details of defects introduced by particle irradiation. Once the atomic configuration of defects and their spatial distribution are revealed, the details of the mesoscopic phenomena can be unveiled. In this work, we created atomically small defects by controlled irradiation of gallium ions with doses ranging from 4.94 × 1012 to 4.00 × 1014 ions/cm2 on monolayer molybdenum disulfide (MoS2) crystals. The optical signatures of defects, such as the evolution of defect-activated LA-bands and a broadening of the first-order (E′ and A′1) modes, can be studied by Raman spectroscopy. High-resolution scanning transmission electron microscopy (HR-STEM) analysis revealed that most defects are vacancies of few-molybdenum atoms with surrounding sulfur atoms (V xMo+yS) at a low ion dose. When increasing the ion dose, the atomic vacancies merge and form nanometer-sized holes. Utilizing HR-STEM and image analysis, we propose the estimation of the finite crystal length (L fc) via the careful quantification of 0D defects in 2D systems through the formula L fc = 4.41/ η ion , where ηion corresponds to the ion dose. Combining HR-STEM and Raman spectroscopy, the formula to calculate L fc from Raman features, I(LA)/I(A′1) = 5.09/L fc 2, is obtained. We have also demonstrated an effective route to healing the ion irradiation-induced atomic vacancies by annealing defective MoS2 in a hydrogen disulfide (H2S) atmosphere. The H2S annealing improved the crystal quality of MoS2 with L fc greater than the calculated size of the A exciton wave function, which leads to a partial recovery of the photoluminescence signal after its quenching by ion irradiation.