Influence of oxygen exposure on the nucleation of platinum atomic layer deposition : consequences for film growth, nanopatterning, and nanoparticle synthesis

Control of the nucleation behavior during atomic layer deposition (ALD) of metals is of great importance for the deposition of metallic thin films and nanoparticles, and for nanopatterning applications. In this work it is established for Pt ALD, that the exposure to O2 during the O2 pulse of the ALD process is the key parameter controlling the nucleation behavior. The O2 dependence of the Pt nucleation is explained by the enhanced diffusion of Pt species in the presence of oxygen, and the resulting faster aggregation of Pt atoms in metal clusters that catalyze the surface reactions of ALD growth. Moreover, it is demonstrated that the O2 exposure can be used as the parameter to tune the nucleation to enable (i) deposition of ultrathin films with minimal nucleation delay, (ii) preparation of single element or core/shell nanoparticles, and (iii) nanopatterning of metallic structures based on area-selective deposition

In situ spectroscopic ellipsometry during atomic layer deposition of Pt, Ru and Pd

The preparation of ultra-thin platinum-group metal films, such as Pt, Ru and Pd, by atomic layer deposition (ALD) was monitored in situ using spectroscopic ellipsometry in the photon energy range of 0.75–5 eV. The metals' dielectric function was parametrized using a 'flexible' Kramers–Kronig consistent dielectric function because it was able to provide accurate curve shape control over the optical response of the metals. From this dielectric function, it was possible to extract the film thickness values during the ALD process. The important ALD process parameters, such as the nucleation period and growth per cycle of Pt, Ru and Pd could be determined from the thickness evolution. In addition to process parameters, the film resistivity in particular could be extracted from the modeled dielectric function. Spectroscopic ellipsometry thereby revealed itself as a feasible and valuable technique to be used in research and development applications, as well as for process monitoring during ALD

Atomic layer deposition of Ru from CpRu(CO2)Et using O2 gas and O2 plasma

The metalorganic precursor cyclopentadienylethyl(dicarbonyl)ruthenium (CpRu(CO)2Et) was used to develop an atomic layer deposition (ALD) process for ruthenium. O2 gas and O2 plasma were employed as reactants. For both processes, thermal and plasma-assisted ALD, a relatively high growth-per-cycle of - 1 Å was obtained. The Ru films were dense and polycrystalline, regardless of the reactant, yielding a resistivity of - 16 µO¿cm. The O2 plasma not only enhanced the Ru nucleation on the TiN substrates but also led to an increased roughness compared to thermal ALD

Catalytic combustion and dehydrogenation reactions during atomic layer deposition of platinum

Atomic layer deposition (ALD) processes of noble metals are gaining increasing interest for applications in catalysis and microelectronics. Platinum ALD from (methylcyclopentadienyl)trimethylplatinum (MeCpPtMe3) and O2 gas has been considered as a model system for noble metal ALD. However, many questions about the underlying reaction mechanisms remain. In this work, the insight into the Pt ALD reaction mechanisms is extended by considering the catalytic nature of the Pt film. It is evaluated which surface reactions are likely to take place during Pt ALD on the basis of surface science results on the interaction of the Pt surface with O2 and hydrocarbon species, combined with previously reported Pt ALD mechanistic studies. In analogy to the reactions of hydrocarbon species on catalytic Pt, it is proposed that, in addition to combustion-like reactions, dehydrogenation of precursor ligands plays a role in the mechanism. The formation of CH4 during the MeCpPtMe3 exposure pulse is explained by hydrogenation of methyl species by hydrogen atoms released from dehydrogenation reactions. The implications of the surface reactions on the self-limiting behavior, the growth rate, and the temperature dependence of the process are discussed. Moreover, this work demonstrates that surface science studies are of great use in obtaining more understanding of metal ALD processes