In Situ Exfoliation Method of Large‐Area 2D Materials

2D materials provide a rich platform to study novel physical phenomena arising from quantum confinement of charge carriers. Many of these phenomena are discovered by surface sensitive techniques, such as photoemission spectroscopy, that work in ultra‐high vacuum (UHV). Success in experimental studies of 2D materials, however, inherently relies on producing adsorbate‐free, large‐area, high‐quality samples. The method that yields 2D materials of highest quality is mechanical exfoliation from bulk‐grown samples. However, as this technique is traditionally performed in a dedicated environment, the transfer of samples into vacuum requires surface cleaning that might diminish the quality of the samples. In this article, a simple method for in situ exfoliation directly in UHV is reported, which yields large‐area, single‐layered films. Multiple metallic and semiconducting transition metal dichalcogenides are exfoliated in situ onto Au, Ag, and Ge. The exfoliated flakes are found to be of sub‐millimeter size with excellent crystallinity and purity, as supported by angle‐resolved photoemission spectroscopy, atomic force microscopy, and low‐energy electron diffraction. The approach is well‐suited for air‐sensitive 2D materials, enabling the study of a new suite of electronic properties. In addition, the exfoliation of surface alloys and the possibility of controlling the substrate‐2D material twist angle is demonstrated.