Herein, a high-quality gate stack (native HfO2 formed on 2D HfSe2) fabricated via plasma oxidation is reported, realizing an atomically sharp interface with a suppressed interface trap density (D-it approximate to 5 x 10(10) cm(-2) eV(-1)). The chemically converted HfO2 exhibits dielectric constant, kappa approximate to 23, resulting in low gate leakage current (approximate to 10(-3) A cm(-2)) at equivalent oxide thickness approximate to 0.5 nm. Density functional calculations indicate that the atomistic mechanism for achieving a high-quality interface is the possibility of O atoms replacing the Se atoms of the interfacial HfSe2 layer without a substitution energy barrier, allowing layer-by-layer oxidation to proceed. The field-effect-transistor-fabricated HfO2/HfSe2 gate stack demonstrates an almost ideal subthreshold slope (SS) of approximate to 61 mV dec(-1) (over four orders of I-DS) at room temperature (300 K), along with a high I-on/I-off ratio of approximate to 10(8) and a small hysteresis of approximate to 10 mV. Furthermore, by utilizing a device architecture with separately controlled HfO2/HfSe2 gate stack and channel structures, an impact ionization field-effect transistor is fabricated that exhibits n-type steep-switching characteristics with a SS value of 3.43 mV dec(-1) at room temperature, overcoming the Boltzmann limit. These results provide a significant step toward the realization of post-Si semiconducting devices for future energy-efficient data-centric computing electronics.