Atomic Scale Ordering of Sulfur Vacancies Enhances Charge Transport in Monolayer MoS$_2$

Abstract

Defect engineering in two-dimensional semiconductors has primarily focused on controlling the nature and concentration of atomic defects. Here, we show that the spatial arrangement of defects can be equally decisive in determining electronic transport. Using sulfur vacancies in monolayer MoS$_2$ as a model system, we investigate the impact of vacancy ordering through density functional theory, density functional tight-binding calculations, and quantum transport simulations. We demonstrate that a periodic vacancy arrangement at a concentration of 11.1% transforms isolated defect states into a narrow dispersive in-gap miniband, whereas randomly distributed vacancies generate only localized electronic states. This electronic transition fundamentally alters charge transport, enabling band-like propagation through the defect network rather than transport limited by disconnected localized states. A systematic analysis of the complete symmetry-reduced ensemble of 94 non-adjacent four-vacancy configurations shows that the ordered pattern lies within a broad low-energy manifold and is not energetically anomalous, although it is not the thermodynamic ground state. Device-level simulations of Au/MoS$_2$/Au junctions reveal efficient alignment of the metal Fermi level with vacancy-derived states, promoting charge injection into the defect miniband. As a result, ordered vacancy arrays exhibit electrical currents up to five orders of magnitude higher than statistically equivalent random distributions and can approach, or locally exceed, the transport performance of pristine MoS$_2$. These findings establish atomic-scale defect ordering as a powerful design principle for two-dimensional materials, demonstrating that the organization of defects, beyond their concentration alone, provides a route to simultaneously preserve functionality and high electrical conductivity in highly defective semiconductors.