Plasma-liquid interactions represent a growing interdisciplinary area of research involving plasma science, fluid dynamics, heat and mass transfer, photolysis, multiphase chemistry and aerosol science. This review provides an assessment of the state-of-the-art of this multidisciplinary area and identifies the key research challenges. The developments in diagnostics, modeling and further extensions of cross section and reaction rate databases that are necessary to address these challenges are discussed. The review focusses on nonequilibrium plasmas.

Microplasmas have attracted a tremendous amount of interest from the plasma community because of their small physical size, stable operation at atmospheric pressure, non-thermal characteristics, high electron densities and non-Maxwellian electron energy distributions. These properties make microplasmas suitable for a wide range of materials applications, including the synthesis of nanomaterials. Research has shown that vapour-phase precursors can be injected into a microplasma to homogeneously nucleate nanoparticles in the gas phase. Alternatively, microplasmas have been used to evaporate solid electrodes and form metal or metal-oxide nanostructures of various composition and morphology. Microplasmas have also been coupled with liquids to directly reduce aqueous metal salts and produce colloidal dispersions of nanoparticles. This topical review discusses the unique features of microplasmas that make them advantageous for nanomaterials synthesis, gives an overview of the diverse approaches previously reported in the literature and looks ahead to the potential for scale-up of current microplasma-based processes.

Plasma‐induced non‐equilibrium liquid chemistry (PiLC) offers enhanced opportunities over solution chemistry for developing new nanomaterials and tailoring their functional properties. Recent advances in the design and scientific understanding of microplasma devices operating at atmospheric pressure offer simple and effective routes to non‐equilibrium chemistry for both scientific study and future nanomanufacturing. This paper presents a short review of our recent work on atmospheric pressure plasma–liquid interactions used in the fabrication and functionalization of nanoparticles. A brief discussion of possible electron‐liquid reactions highlights outstanding scientific and engineering questions.

Plasma-induced non-equilibrium liquid chemistry is used to synthesize gold nanoparticles (AuNPs) without using any reducing or capping agents. The morphology and optical properties of the synthesized AuNPs are characterized by transmission electron microscopy (TEM) and ultraviolet-visible spectroscopy. Plasma processing parameters affect the particle shape and size and the rate of the AuNP synthesis process. Particles of different shapes (e.g. spherical, triangular, hexagonal, pentagonal, etc) are synthesized in aqueous solutions. In particular, the size of the AuNPs can be tuned from 5 nm to several hundred nanometres by varying the initial gold precursor (HAuCl4) concentration from 2.5 μM to 1 mM. In order to reveal details of the basic plasma-liquid interactions that lead to AuNP synthesis, we have measured the solution pH, conductivity and hydrogen peroxide (H2O2) concentration of the liquid after plasma processing, and conclude that H2O2 plays the role of the reducing agent which converts Au(+3) ions to Au(0) atoms, leading to nucleation growth of the AuNPs.

Surface engineering of silicon nanocrystals directly in water or ethanol by atmospheric‐pressure dc microplasma is reported. In both liquids, microplasma processing stabilizes the optoelectronic properties of silicon nanocrystals. The microplasma treatment induces non‐equilibrium liquid chemistry that passivates the silicon nanocrystals surface with oxygen‐/organic‐based terminations. In particular, the microplasma treatment in ethanol drastically enhances the silicon nanocrystals photoluminescence intensity and causes a clear red‐shift (≈80 nm) of the photoluminescence maximum. The photoluminescence properties are stable after several days of storage in either ethanol or water. The surface chemistry induced by the microplasma treatment is analyzed and discussed.