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Diffusion‐Mediated Growth and Size‐Dependent Nanoparticle Reactivity during Ruthenium Atomic Layer Deposition on Dielectric Substrates
Author(s) -
Soethoudt Job,
Grillo Fabio,
Marques Esteban A.,
Ommen J. Ruud,
Tomczak Yoann,
Nyns Laura,
Elshocht Sven,
Delabie Annelies
Publication year - 2018
Publication title -
advanced materials interfaces
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.671
H-Index - 65
ISSN - 2196-7350
DOI - 10.1002/admi.201800870
Subject(s) - nanoparticle , atomic layer deposition , materials science , dielectric , diffusion , surface diffusion , ruthenium , catalysis , chemical engineering , adsorption , deposition (geology) , thin film , reactivity (psychology) , substrate (aquarium) , surface modification , nanotechnology , chemistry , organic chemistry , alternative medicine , oceanography , pathology , engineering , biology , paleontology , thermodynamics , medicine , physics , optoelectronics , sediment , geology
Understanding the growth mechanisms during the early stages of atomic layer deposition (ALD) is of interest for several applications including thin film deposition, catalysis, and area‐selective deposition. The surface dependence and growth mechanism of (ethylbenzyl)(1‐ethyl‐1,4‐cyclohexadienyl)ruthenium and O 2 ALD at 325 °C on HfO 2 , Al 2 O 3 , OH, and SiOSi terminated SiO 2 , and organosilicate glass (OSG) are investigated. The experimental results show that precursor adsorption is strongly affected by the surface termination of the dielectric, and proceeds most rapidly on OH terminated dielectrics, followed by SiOSi and finally SiCH 3 terminated dielectrics. The initial stages of growth are characterized by the formation and growth of Ru nanoparticles, which is mediated by the diffusion of Ru species. Mean‐field and kinetic Monte Carlo modeling show that ALD on OSG is best described when accounting for (1) cyclic generation of new nanoparticles at the surface, (2) surface diffusion of both atomic species and nanoparticles, and (3) size‐dependent nanoparticle reactivity. In particular, the models indicate that precursor adsorption initially occurs only on the dielectric substrate, and occurs on the Ru nanoparticles only when these reach a critical size of about 0.85 nm. This phenomenon is attributed to the catalytic decomposition of oxygen requiring a minimum Ru nanoparticle size.