JiaranLi,#WenfaChen,*,#XiaoyueWu,*,#RuixinHuang,XinLiu, ShuiyanCao, andYanpengLiu*

ACS Appl. Mater. Interfaces（IF:8.5）Published December 2, 2025

Abstract

Defect chemistry critically shapes the optical response of atomically thin WQ2 (Q = S, Se), yet the interplay between ambient oxygen and ionizing radiation remains poorly quantified. Here, we map dose-resolved variations in monolayer and bilayer WQ2 exposed to in-air X-rays while tracking Raman and photoluminescence evolution. All four systems (monolayer/bilayer WQ2) show a nonmonotonic evolution: vibrational peaks blue-shift and intensities increase at low cumulative doses, then red-shift and weaken at higher doses; exciton and trion emissions follow the same rise-and-fall. The transition occurs at an X-ray dose of ∼120–150 Gy for WS2 and ∼60 Gy for WSe2, with bilayers requiring higher doses than monolayers, indicating chemistry-dependent and monolayer–bilayer thickness-dependent tolerance. Atomic force microscopy of these flakes reveals no intrinsic topographic change in this window. First-principles calculations rationalize these trends: chalcogen vacancies introduce midgap states that quench emission, whereas oxygen substitution removes subgap states and slightly narrows the band gap; binding-energy analysis identifies selenium in monolayers as the easiest to remove, while bilayers and oxygen-substituted sites are more robust. The combined experiment–theory framework establishes a practical strategy for enhancing optical emission through oxygen-assisted passivation without incurring irreversible radiation damage.

https://doi.org/10.1021/acsami.5c19570