Nonthermal plasmas have emerged as a viable synthesis technique for nanocrystal materials. Inherently solvent and ligand-free, nonthermal plasmas offer the ability to synthesize high purity nanocrystals of materials that require high synthesis temperatures. The nonequilibrium environment in nonthermal plasmas has a number of attractive attributes: energetic surface reactions selectively heat the nanoparticles to temperatures that can strongly exceed the gas temperature; charging of nanoparticles through plasma electrons reduces or eliminates nanoparticle agglomeration; and the large difference between the chemical potentials of the gaseous growth species and the species bound to the nanoparticle surfaces facilitates nanocrystal doping. This paper reviews the state of the art in nonthermal plasma synthesis of nanocrystals. It discusses the fundamentals of nanocrystal formation in plasmas, reviews practical implementations of plasma reactors, surveys the materials that have been produced with nonthermal plasmas and surface chemistries that have been developed, and provides an overview of applications of plasma-synthesized nanocrystals.

The ‘‘kinetic theory’’ of homogeneous nucleation developed by Katz and Wiedersich is extended to derive a new expression for the rate of nucleation from an ideal supersaturated vapor. Compared to the classical expression for the nucleation rate, the new expression has a slightly different dependence on supersaturation, and a substantially different dependence on temperature. A comparison of the new expression with experimental data on nucleation rates of several organic liquids indicates that in some but not all cases the new expression gives much closer agreement with the data than does the classical expression. Discrepancies between the theory and the data are ascribed mainly to the physical assumptions of the theory presented, which are the same as in the classical theory—particularly, that the physical properties of microscopic clusters are the same as those of the bulk liquid.

Product contamination by particles nucleated within the processing environment often limits the deposition rate during chemical vapor deposition processes. A fundamental understanding of how these particles nucleate could allow higher growth rates while minimizing particle contamination. Here we present an extensive chemical kinetic mechanism for silicon hydride cluster formation during silane pyrolysis. This mechanism includes detailed chemical information about the relative stability and reactivity of different possible silicon hydride clusters. It provides a means of calculating a particle nucleation rate that can be used as the nucleation source term in aerosol dynamics models that predict particle formation, growth, and transport. A group additivity method was developed to estimate thermochemical properties of the silicon hydride clusters. Reactivity rules for the silicon hydride clusters were proposed based on the group additivity estimates for the reaction thermochemistry and the analogous reactions of smaller silicon hydrides. These rules were used to generate a reaction mechanism consisting of reversible reactions among silicon hydrides containing up to 10 silicon atoms and irreversible formation of silicon hydrides containing 11-20 silicon atoms. The resulting mechanism was used in kinetic simulations of clustering during silane pyrolysis in the absence of any surface reactions. Results of those simulations are presented, along with reaction path analyses in which key reaction paths and rate-limiting steps are identified and discussed.

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A new silicon hydride clustering model was developed to study the nucleation of particles in a low-temperature silane plasma. The model contains neutral silanes, silylenes, silenes and silyl radicals as well as silyl and silylene anions. Reaction rates were estimated from available data. Simulations were carried out for typical discharge parameters in a capacitive plasma. It was shown that the main pathway leading to silicon hydride clustering was governed by anion-neutral reactions. SiH 2 radical insertion was found to be important only in the initial stages of clustering, whereas electron-induced dissociations were seen to lead to dehydrogenation. Increased ion density (radiofrequency power density) leads to faster clustering due to increased formation of reactive radicals.