Metal oxidation kinetics and the transition from thin to thick films
Literature Information
Zhijie Xu, Kevin M. Rosso, Stephen Bruemmer
We report an investigation of growth kinetics and transition from thin to thick films during metal oxidation. In the thin film limit (<20 nm), Cabrera and Mott's theory is usually adopted by explicitly considering ionic drift through the oxide in response to electric fields, where the growth kinetics follow an inverse logarithmic law log(dl/dt) ∝ 1/l. It is generally accepted that Wagner's theory, involving self-diffusion, is valid only in the limit of thick film regime (>1 μm) and leads to parabolic growth kinetics dl/dt ∝ 1/l, where l is the oxide film thickness. Theory presented here unifies the two models and provides a complete description of oxidation including the transition from thin to thick film. The range of validity of Cabrera and Mott's theory and Wagner's theory can be well defined in terms of the Debye–Hückel screening length. The transition from drift-dominated ionic transport for thin film to diffusion-dominated transport for thick film is found to strictly follow the direct logarithmic law log(dl/dt) ∝ −l that is frequently observed in many experiments.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.












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