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An ultra-narrow 40-nm slotted waveguide is fabricated to enable highly efficient, electro-optic polymer modulators. Our measurement results indicate thatV_πL’s below ∼ 1.19 V.mm are possible for the balanced Mach-Zehnder modulators using this ultra-narrow slotted waveguide on a hybrid silicon-organic hybrid platform. Our simulations suggest thatV_πL’s can be further reduced to ∼ 0.35 V.mm if appropriate doping is utilized. In addition to adapting standard recipes, we developed two novel fabrication processes to achieve miniaturized devices with high modulation sensitivity. To boost compactness and decrease the overall footprint, we use a fabrication approach based on air bridge interconnects on thick, thermally-reflowed, MaN 2410 E-beam resist protected by an alumina layer. To overcome the challenges of high currents and imperfect infiltration of polymers into ultra-narrow slots, we use a carefully designed, atomically-thin layer of TiO₂as a carrier barrier to enhance the efficiency of our electro-optic polymers. The anticipated increase in total capacitance due to the TiO₂layer is negligible. Applying our TiO₂surface treatment to the ultra-narrow slot allows us to obtain an improved index change efficiency (∂n/∂V) of ∼ 22% for a 5 nm TiO₂layer. Furthermore, compared to non-optimized cases, our peak measured current during poling is reduced by a factor of ∼ 3.