In the 1950s and 1960s fundamental developments in electrochemical methods included voltammetry and low signal techniques. A generation later, the discovery of the unusual properties of ultramicroelectrodes has opened new possibilities of analyzing electrode processes. The changes in mass transport conditions bring about extremely high current densities at ultramicroelectrodes, whereas the currents themselves become very small. This little-noticed phenomenon allows for many electroanalytical applications that are not possible with conventional electrodes, especially experiments in solutions with very low electrolyte concentrations, in nonpolar solvents, in solids, and even in gases. In addition, two factors— changes in the experimental time scale at low scan rates because of the size of the electrode, and insignificant iR effects at very high scan rates—make it possible to study very fast homogeneous and heterogeneous electrode processes.

Ultramicroelectrodes in Electrochemistry

Des electrodes IDA avec differents parametres geometriques sont fabriques par lithographie et appliquees a des mesures de voltammerie cyclique et de chronoamperometrie d'especes redox

Electrochemical behavior of reversible redox species at interdigitated array electrodes with different geometries: consideration of redox cycling and collection efficiency

This review describes the theory of mass transport at ultramicroelectrodes that have broken through several experimental limitations of electrochemical measurements. On the basis of the mathematical miniaturization, the ultramicroelectrode can be classified into a point electrode, a line electrode, and a plane electrode. Electrochemical features of these electrodes are described from a viewpoint of the mass transport, especially due to diffusion. Theoretical difficulty in ultramicroelectrodes is mainly due to nonuniform current distribution on the electrode surface. The expression for the time-dependent diffusion-controlled current at any electrode geometry, which predicts the current responding to any potential variation, is presented. Conditions of the steady-state current are specified. The diffusional characteristic functions at a disk. a cylinder, and a band are presented, from which the theories of various electrochemical techniques can be derived analytically. Voltammetric peak currents at several ultramicroelectrodes are compared in light of the diffusional edge effect. The properties of the steady-state current are described at a disk, a band array, a ring, and a recess electrode. The theory is extended to the current-potential curves complicated by the heterogeneous kinetics at a disk, a cylinder, and a band-array electrode.

Theory of ultramicroelectrodes

Voltammetric electrodes of microscopic dimension, termed ultramicroelectrodes, can be used to make measurements that are difficult or impossible with conventional electrochemical techniques. Measurements of chemical concentration can be made with these electrodes on a microsecond time scale and with micrometer spatial resolution. In addition, measurements can be made in highly resistive solutions.

https://science.sciencemag.org/content/sci/240/4851/415.full.pdf

Voltammetry with microscopic electrodes in new domains.

Conducting polymer gas sensors part I: fabrication and characterization

Diffusion current at a band electrode by an integral equation method

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Diffusion current at a band electrode by an integral equation method