Review of electric discharge microplasmas generated in highly fluctuating fluids: Characteristics and application to nanomaterials synthesis

Plasma-based fabrication of novel nanomaterials and nanostructures is indispensible for the development of next-generation electronic devices and for green energy applications. In particular, controlling the interactions between plasmas and materials interfaces, and the plasma fluctuations, is crucial for further development of plasma-based processes and bottom-up growth of nanomaterials. Electric discharge microplasmas generated in supercritical fluids represent a special class of high-pressure plasmas, where fluctuations on the molecular scale influence the discharge properties and the possible bottom-up growth of nanomaterials. This review discusses an anomaly observed for direct current microplasmas generated near the critical point, a local decrease in the breakdown voltage. This anomalous behavior is suggested to be caused by the concomitant decrease of the ionization potential due to the formation of clusters near the critical point, and the formation of extended electron mean free paths caused by the high-density fluctuation near the critical point. It is also shown that in the case of dielectric barrier microdischarges generated close to the critical point, the high-density fluctuation of the supercritical fluid persists. The final part of the review discusses the application of discharges generated in supercritical fluids to synthesis of nanomaterials, in particular, molecular diamond - so-called diamondoids - by microplasmas generated inside conventional batch-type and continuous flow microreactors.