The groundbreaking discovery of graphene by top-down exfoliation of bulk graphite using Scotch tape led to the foundation of 2D material research. Since then, this technique has been one of the most successful and widely utilized techniques to produce monolayer materials. However, the materials produced by this technique are unpractically small in size and often appear together with a very high ratio of bulk layers. Moreover, the involved viscoelastic stamps in this process release chemical fingerprints on the materials, altering the intrinsic nature of the produced atom-thin layers. The exfoliation of 2D materials under ambient conditions has been a major shortcoming for direct probing of electronic states, as those measurement techniques require extremely clean materials, which has been achieved by post-preparation cleaning processes. Moreover, because of their high reactivity toward oxygen and water, several key materials, such as high-temperature magnets based on transition metal halides, oxyhalides, and tellurides, could not be exfoliated even inside the controlled atmosphere of a glove box, which greatly hampered the experimental progress of the field. Several bottom-up techniques to synthesize large-area monolayers have been developed over the last two decades. Great progress has been made in chemical vapor deposition (CVD), attaining large-area synthesis of layers. However, CVD requires rigorous optimization to obtain monolayers of unconventional materials and even more for scalable synthesis. Similar challenges were also encountered by the molecular beam epitaxy (MBE) technique. The materials produced by atomic layer deposition (ALD) are generally amorphous in nature. Mechanical exfoliation of crystals with the assistance of gold tape has provided ultra-large area monolayers. This technique primarily relies on the dispersive interaction between metals and the topmost layer of the bulk crystal, where the interaction potential can be higher than the interlayer interaction potential of the bulk crystals. For the exfoliation, gold was directly deposited on the bulk crystals and cleaved using adhesive tape. However, the direct deposition of metals often causes substitution doping of Au atoms in the 2D layers, which could be eventually avoided by Au-film-assisted exfoliation by placing bulk crystals on a pre-deposited metal layer. However, taking advantage of the high dispersive interaction potential of this process is challenging because of the aging of the Au films. The fresh Au surface tends to interact with the environment and quickly saturates with chemical impurities, which prevents efficient exfoliation. For other noble metals such as Ag, the interaction with the surrounding impurities is even stronger and hence surface passivation is faster, resulting in no possibility of exfoliation under ambient conditions or in a glove box, where the remnant oxygen and water are sufficient to saturate the surface of the fresh Ag film. Ultra-high vacuum (UHV) conditions could substantially extend the lifetime of the fresh metal films. Hence, single and polycrystalline metal films cleaned under UHV conditions have been recently utilized for the exfoliation of 2D materials, and monolayer 2D materials sized in the hundreds of microns have been obtained. However, a thorough cleaning of the surface by plasma etching or ion bombardment is challenging. On the other hand, the metal films prepared directly under UHV conditions offer a chemically unperturbed surface and can lead to better exfoliation results.