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We present a first principles based investigation into the nucleation and growth of metal-rich precipitates in substoichiometric hafnium dioxide with relevance to applications in resistive switching memories. We identify an optimal HfOx stoichiometry, with x in the range 1.50–1.75, for efficient nucleation and growth of stable Hf-rich clusters which may serve as precursors for the growth of conductive filaments during forming. We also show that filaments with sub-nm diameter posses remarkably metallic character. These results provide invaluable atomistic insight into forming in resistive switching films and demonstrate that precise regulation of stoichiometry is essential in order to ensure uniformity in the nucleation and subsequent growth of a conductive filament during the forming process. [ABSTRACT FROM AUTHOR]