Atomic layer deposition (ALD) of platinum (Pt) has gained significant interest in the recent years due to its capability of depositing various Pt nanostructures for applications in different fields, such as Pt nanoparticles (NPs) for catalytic reactions and energy devices and Pt thin films for microelectronic technology. Among various developed processes, Pt ALD using MeCpPtMe₃as the precursor has been most popularly employed owing to the high reactivity, volatility, and thermal stability of the precursor, which enable controlled deposition of Pt nanostructures in a broad range of temperatures. Typical MeCpPtMe₃-based Pt ALD processes use O₂and H₂as the coreactants. In this study, we explore atomic hydrogen as an alternative and reveal its exceptional reactivity that outperforms H₂and O₂. Specifically, atomic hydrogen enables the deposition of highly dispersed Pt NPs with narrow particle size distributions (i.e., standard deviation <0.3 nm) on various oxide surfaces, including TiO₂, SiO₂, CeO₂and V₂O₅, which is unattainable with H₂under identical experimental conditions. In addition, it facilitates the deposition of Pt NPs with improved size uniformity and accelerates the closure of Pt films compared to ALD processes using O₂as the coreactant. The results demonstrate a significant potential of atomic hydrogen as a highly effective coreactant for ALD of Pt NPs and thin films.

A fundamental understanding of the interplay between ligand-removal kinetics and metal aggregation during the formation of platinum nanoparticles (NPs) in atomic layer deposition of Pt on TiO₂ nanopowder using trimethyl(methylcyclo-pentadienyl)platinum(IV) as the precursor and O₂ as the coreactant is presented. The growth follows a pathway from single atoms to NPs as a function of the oxygen exposure (P_O2 × time). The growth kinetics is modeled by accounting for the autocatalytic combustion of the precursor ligands via a variant of the Finke–Watzky two-step model. Even at relatively high oxygen exposures (<120 mbar s) little to no Pt is deposited after the first cycle and most of the Pt is atomically dispersed. Increasing the oxygen exposure above 120 mbar s results in a rapid increase in the Pt loading, which saturates at exposures >> 120 mbar s. The deposition of more Pt leads to the formation of NPs that can be as large as 6 nm. Crucially, high P_O2 (≥5 mbar) hinders metal aggregation, thus leading to narrow particle size distributions. The results show that ALD of Pt NPs is reproducible across small and large surface areas if the precursor ligands are removed at high P_O2.