Laser-Assisted Synthesis of Monolayer 2D MoSe₂Crystals with Tunable Vacancy Concentrations: Implications for Gas and Biosensing

Tuning the structural and electronic properties of atomically thin two-dimensional (2D) materials via defect and vacancy engineering is the key to enabling their potential use in various applications, including electronics, energy, and sensing devices. Vacancies are, for instance, becoming highly promising for the enhanced interaction of gases and biomolecules with 2D materials in energy and sensing applications. However, the deterministic generation of desirable vacancies with tunable concentrations remains a challenge in 2D materials due to the limitations in the current growth methods, such as the complex reaction chemistries and gas flow dynamics. Therefore, engineering defects and vacancies in 2D materials have been mainly limited to destructive top-down processes such as heating, ion bombardments, and laser postprocessing. Here, we introduce a single-step bottom-up synthesis approach for the growth of monolayer MoSe₂crystals with tunable vacancy concentrations. This method utilizes the spatiotemporal properties and adjustable power densities of the lasers to control the vaporization dynamics of the stoichiometric MoSe₂powders. Such a mechanism in the vaporization allows us to grow tunable stoichiometry monolayer MoSe_2-xcrystals on the substrates. The localized and time-controlled (250 ms to 2 s) vaporization of the MoSe₂powder by a CO₂laser enables the formation of monolayer crystals with controlled vacancy concentrations ranging from ∼1 to 20%. The effects of laser power, laser irradiation time, and background pressure on the tuning range and subsequent properties of the crystals are investigated and quantified using Raman and photoluminescence spectroscopy, scanning transmission electron microscopy (STEM), and time-correlated single-photon counting (TCSPC). This bottom-up synthesis is a promising approach that allows the deterministic vacancy tuning for future electronics and, in particular, gas and biosensing applications without the need for further postprocessing and potential structural disruption of the crystals.