metal-oxide-semiconductor field-effect transistors (MOSFETs). As we continue to squeeze the last few drops from the lemon that is Moore's law, alternative channel materials other than silicon will be needed for future devices. [2] Likewise, replacement of traditional dielectrics, silicon oxide, with high-k dielectrics are being implemented for increased gate capacitance with low leakage currents. Currently, state-of-the-art MOSFETs manufactured by Intel utilizes a 2.6 nm thick high-k HfO 2 gate dielectric in their 14-nm FinFET structures. [3] For channel materials, promising candidates are 2D semiconductors such as transition metal dichalcogenides (TMDCs). [4][5][6][7][8][9][10] 2D TMDCs are an important class of atomically thin materials with novel properties such as tunable layer-dependent direct bandgaps, strong photoluminescence, large spin-orbit coupling, and unique spin-valley coupling. [11][12][13][14][15] These exceptional properties are attractive for applications in electronics, optoelectronic and quantum information processing. 2D TMDCs were first isolated with the "Scotch tape" technique, where adhesive tapes "peel" thin flakes from bulk crystals that are then repeatedly exfoliated to a single atomic layer. [16] Devices are fabricated through manual assembly and stacking of such semiconducting or insulating micron Temperature-dependent transport measurements are performed on the same set of chemical vapor deposition (CVD)-grown WS 2 single-and bilayer devices before and after atomic layer deposition (ALD) of HfO 2 . This isolates the influence of HfO 2 deposition on low-temperature carrier transport and shows that carrier mobility is not charge impurity limited as commonly thought, but due to another important but commonly overlooked factor: interface roughness. This finding is corroborated by circular dichroic photoluminescence spectroscopy, X-ray photoemission spectroscopy, cross-sectional scanning transmission electron microscopy, carrier-transport modeling, and density functional modeling. Finally, electrostatic gate-defined quantum confinement is demonstrated using a scalable approach of large-area CVD-grown bilayer WS 2 and ALD-grown HfO 2 . The high dielectric constant and low leakage current enabled by HfO 2 allows an estimated quantum dot size as small as 58 nm. The ability to lithographically define increasingly smaller devices is especially important for transition metal dichalcogenides due to their large effective masses, and should pave the way toward their use in quantum information processing applications.The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/adma.202103907.