Theory of scanning electrochemical microscopy (SECM) as a probe of surface conductivity

Literature Information

Publication Date 2004-09-28
DOI 10.1039/B407397E
Impact Factor 3.676
Authors

Anna L. Whitworth, Daniel Mandler, Patrick R. Unwin


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Abstract

Scanning electrochemical microscopy (SECM) can be used in the feedback mode as a ‘contactless’ method for probing the conductivity of ultra-thin films. With this new technique a sample is bathed with one form of a reversible redox (Red/Ox) couple, e.g. Red, and an ultramicroelectrode (UME), located close to the film surface is used to locally convert Red to Ox by diffusion-limited oxidation. Ox diffuses from the UME to the film where it may undergo conversion back to Red. This process is driven by a potential gradient, which depends on the surface conductivity. A model is developed for the SECM feedback process from which the conductivity of the film can be extracted. Two routes arising from the model are considered: an approximate method which allows an order of magnitude estimate of the film conductivity and a more involved approach, which can be used with greater accuracy. The merits of the two approaches are assessed by analysing experimental data for the effect of surface pressure on the conductivity of a polyaniline monolayer at a water/air interface.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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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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