Efficient and reliable on-chip optical amplifiers and light sources would enable versatile integration of various active functionalities on the silicon platform. Although lasing on silicon has been demonstrated with semiconductors by using methods such as wafer bonding or molecular beam epitaxy, cost-effective mass production methods for CMOS-compatible active devices are still lacking. Here, we report ultra-high on-chip optical gain in erbium-based hybrid slot waveguides with a monolithic, CMOS-compatible and scalable atomic-layer deposition process. The unique layer-by-layer nature of atomic-layer deposition enables atomic scale engineering of the gain layer properties and straightforward integration with silicon integrated waveguides. We demonstrate up to 20.1 ± 7.31 dB/cm and at least 52.4 ± 13.8 dB/cm net modal and material gain per unit length, respectively, the highest performance achieved from erbium-based planar waveguides integrated on silicon. Our results show significant advances towards efficient on-chip amplification, opening a route to large-scale integration of various active functionalities on silicon.