Robust n-type doping of WSe₂ enabled by controllable proton irradiation

Two-dimensional (2D) transition metal dichalcogenides (TMDs) are considered to be promising building blocks for the next generation electronic and optoelectronic devices. Various doping schemes and work function engineering techniques have been explored to overcome the intrinsic performance limits of 2D TMDs. However, a reliable and long-time air stable doping scheme is still lacking in this field. In this work, we utilize keV ion beams of H₂⁺ to irradiate layered WSe₂ crystals and obtain efficient n-type doping effect for all irradiated crystals within a fluence of 1 × 10¹⁴ protons·cm⁻² (1e14). Moreover, the irradiated WSe₂ remains an n-type semiconductor even after it is exposed to ambient conditions for a year. Localized ion irradiation with a focused beam can directly pattern on the sample to make high performance homogenous p-n junction diodes. Raman and photoluminescence (PL) spectra demonstrate that the WSe₂ crystal lattice stays intact after irradiation within 1e14. We attribute the reliable electron-doping to the significant increase in Se vacancies after the proton irradiation, which is confirmed by our scanning transmission electron microscope (STEM) results. Our work demonstrates a reliable and long-term air stable n-type doping scheme to realize high-performance electronic TMD devices, which is also suitable for further integration with other 2D devices.