After γ-ray irradiation treatment, a monolayer tungsten diselenide could be transitioned into an n-doped semiconductor due to the anion vacancies created by the radiation. Transmission electron microscope studies showed clear chemical modulation with atomically sharp interface. Change in the lattice vibrational modes induced by passivation of oxygen is captured by Raman spectroscopy. The frequency shifts in both in-plane and out-of-plane modes are dependent linearly on the oxidation content. We observe a negative trion, which is a neutral exciton bound with an electron, in the photoluminescence spectra. The binding energy of this trion is estimated to be ∼90 meV, making it a tightly bound exciton. The first-principles calculation suggests that an increase in the anion vacancy population is generally accompanied by a transition from a direct gap material to an indirect one. This opens up a new venue to engineer the electronic properties of transition metal dichalcogenides by using irradiation.
Our work showed a new defect inducing technique to engineer the bandgap and control the optical, frictional and electrostatic properties of atomically thin WSe2.
The nanoscale characteristics of semiconducting transition metal dichalcogenides (TMDCs) are largely determined by their photonic, mechanical, magnetic, thermal, and electronic properties, which can be modulated by adjusting thickness and radiation treatments. In this paper, gamma-rays were applied to irradiate the materials with one to six layers, based on which a comparison was drawn of the frictional and electrical properties before and after irradiation. The changes on a few-layer WSe2 were investigated using Raman spectroscopy, photoluminescence spectroscopy, scanning electron microscopy, transmission electron microscopy, force friction microscopy, and Kelvin probe force microscopy. Under the context of irradiation, there was a phenomenon found different than previously reported. The friction force of WSe2 nano-flakes increased from monolayer to bilayer, decreased at tri-layer, and then increased on a continued basis with thickness. It is suggested that the gamma-ray irradiation treatment could be effective in improving frictional and electronic properties. The range of change to the surface contact potential difference (CPD) was narrowed, and the stability of the device surface potential was enhanced. The continuum mechanics theory was applied to explore the friction force variation between different thickness layers. Based on the puckering effect of tip-flake adhesion, the friction force was determined by bending stiffness. The thermal treatment of WSe2 nanoflakes had a significant impact on the CPD between the sample and the test tip. After thermal treatment, the surface potential increased from one to five layers with thickness. These phenomena were explained in detail. The research contributes to enriching nanotribology and electrical theory in addition to promoting the use of semiconducting TMDCs for nano-components’ design.
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