Modification of the surface composition, stoichiometry, morphol., and structure of HfO2 ultra-thin layers upon exposure to at. hydrogen beams has been investigated by a combination of time-of-flight secondary ion mass spectrometry (ToF-SIMS) depth profile anal., angle-resolved XPS (ARXPS), at. force microscopy (AFM) imaging, and transmission electron microscopy (TEM).The etching reaction has been found to be thermally activated (Ea = 96 kJ/mol) and governed by the expression Retch(Å/h) = 3.03 x 108e-((1.15x104)/T) within the 350-400°C temperature range.The rate law determined exptl., i.e., Retch(Å/h) = 1.07 x 10-1[H2]1/2, is consistent with a reaction mechanism that involves the formation of a volatile hafnium dihydroxide, Hf(OH)2 in two successive elementary steps.Precise control of the etching conditions allows to reach atomically smooth HfO2 surfaces having r.m.s. roughness below 0.2 nm, with no evidence of Hf metal formation derived from the reaction with at. H.Elimination of C, Cl, F, and S contaminants from the HfO2 surface through the formation of the corresponding volatile hydrides has proved to be generally most effective at high temperatures and H2 flow rates.