Metal-Insulator-Metal tunnel junctions (MIMTJ) are common throughout the microelectronics industry. The industry standard AlO x tunnel barrier, formed through oxygen diffusion into an Al wetting layer, is plagued by internal defects and pinholes which prevent the realization of atomically-thin barriers demanded for enhanced quantum coherence. In this work, we employed in situ scanning tunneling spectroscopy along with molecular dynamics simulations to understand and control the growth of atomically thin Al 2 O 3 tunnel barriers using atomic layer deposition (ALD). We found that a carefully tuned initial H 2 O pulse hydroxylated the Al surface and enabled the creation of an atomically-thin Al 2 O 3 tunnel barrier with a high quality M-I interface and a significantly enhanced barrier height compared to thermal AlO x . These properties, corroborated by fabricated Josephson Junctions, show that ALD Al 2 O 3 is a dense, leak-free tunnel barrier with a low defect density which can be a key component for the next-generation of MIMTJs.