We report subnanometer modification enabled by an ultrafine helium ion beam. By adjusting ion dose and the beam profile, structural defects were controllably introduced in a few-layer molybdenum disulfide (MoS2) sample and its stoichiometry was modified by preferential sputtering of sulfur at a few-nanometer scale. Localized tuning of the resistivity of MoS2 was demonstrated and semiconducting, metallic-like, or insulating material was obtained by irradiation with different doses of He(+). Amorphous MoSx with metallic behavior has been demonstrated for the first time. Fabrication of MoS2 nanostructures with 7 nm dimensions and pristine crystal structure was also achieved. The damage at the edges of these nanostructures was typically confined to within 1 nm. Nanoribbons with widths as small as 1 nm were reproducibly fabricated. This nanoscale modification technique is a generalized approach that can be applied to various two-dimensional (2D) materials to produce a new range of 2D metamaterials.

Two-dimensional layered semiconductors have recently emerged as attractive building blocks for next-generation low-power non-volatile memories. However, Hongzhou Zhang: hozhang@tcd.ie 1 arXiv:1811.09545v1 [cond-mat.mtrl-sci] 23 Nov 2018 † J.J. and D.K. contributed equally to this project. D.K. performed electrical measurements on samples of different layer thickness and irradiation dose, as well as atomic force microscopy and scanning electron microscopy. CVD growth of MoS 2 monolayers was carried out by C.P.C. Mechanically-exfoliated devices were prepared by J.J. and D.K. Raman and PL spectroscopy was carried out by C.P.C. and analysed by P.M.. J.J and D.K. carried out EBL to fabricate the FET devices. H.S. assisted with fabrication and wirebonding of devices tested in Peking University (PKU). D.K., J.J. and P.M. carried out the HIM irradiations in Trinity College Dublin (TCD) while J.J and Y.Z. conducted the HIM exposures in PKU. J.J carried out the electrical tests (endurance and potentiation) with assistance from H.S and Y.Z in PKU. P.M. performed FIB processing of irradiated devices and carried out TEM of the cross-sectioned lamellae with assistance from C.D.. D.S.F. carried out helium exposures and TEM imaging of the plan-view irradiated devices after J.J. transferred the samples onto TEM grids. Z.L. oversaw the electrical characterisation work in PKU, while R.Z. and J.X. facilitated microscopy experiments in PKU. N.M and G.S.D. oversaw the material growth process and spectroscopic experiments in TCD. J.J.B. and H.Z. conceived the study and supervised the project. The manuscript was written by J.J., D.K. and P.M. All authors agreed with the final version of the paper.

A study to analyse beam damage, image quality and edge contrast in the helium ion microscope (HIM) has been undertaken. The sample investigated was graphene. Raman spectroscopy was used to quantify the disorder that can be introduced into the graphene as a function of helium ion dose. The effects of the dose on both freestanding and supported graphene were compared. These doses were then correlated directly to image quality by imaging graphene flakes at high magnification. It was found that a high magnification image with a good signal to noise ratio will introduce very significant sample damage. A safe imaging dose of the order of 10 13 He + cm −2 was established, with both graphene samples becoming highly defective at doses over 5 × 10 14 He + cm −2 . The edge contrast of a freestanding graphene flake imaged in the HIM was then compared with the contrast of the same flake observed in a scanning electron microscope and a transmission electron microscope. Very strong edge sensitivity was observed in the HIM. This enhanced edge sensitivity over the other techniques investigated makes the HIM a powerful nanoscale dimensional metrology tool, with the capability of both fabricating and imaging features with sub-nanometre resolution.

Time-controlled plasma treatment of MoS2 FETs improves carrier transport due to the presence of a two-dimensional oxide phase.