No abstract

Understanding submicrometer particle behavior in non-thermal capacitively coupled plasmas (CCPs) is important in the application of CCP reactors in thin-film vapor deposition; nucleated and resuspended particles can deposit on thin films, forming defects. Prior studies of supermicrometer particle behavior in CCP reactors have revealed that particles are trapped in the pre-sheath or sheath regions near electrodes, but have examined in detail neither the trapping of submicrometer particles, nor the influence of particle material properties on trapping. Using laser light scattering (LLS), we examined trapping of submicrometer metal oxide particles (radii in the 211 nm–565?nm range) of 6 distinct material compositions in the pre-sheath/sheath region of a CCP reactor operated at pressures in the 0.5–2.0 Torr range. We specifically focus on trapping near the upper electrode of a horizontally-oriented reactor. In this instance, trapping is brought about by a balance between electrostatic forces and gravitational forces driving particles away from the electrode, with ion drag forces driving particles toward the electrode. LLS measurements reveal that submicrometer particles are trapped near the upper electrode for all particle sizes, types, and operating pressures, with the trapping location at an increased distance away from the electrode with decreased CCP reactor pressure. Interestingly, we find the trapping location shifts slightly farther from the top electrode with increasing material dielectric constant. This suggests that the ion drag force is influenced by particle material properties, though in an unclarified manner. Measured trapping locations are also compared to model predictions where particle charge levels and the ion drag force are calculated using expressions based on ion trajectory calculations in a plasma sheath accounting for ion–neutral collisions. Predicted ion densities required for trapping are a factor of 6–16 higher than calculated at the observed particle trapping locations when applying a dissipative ion–particle encounter model, with more substantial disagreement found when considering a non-dissipative encounter model. In total, our results confirm that submicrometer particle trapping occurs at the upper electrode of CCP reactors, which must be facilitated by a balance largely between electrostatic and gravitational forces opposed by ion drag forces, but suggest future studies will be required to understand how particle material properties affect forces on particles on the plasma volume boundary, and how the ion drag force is sufficiently high to facilitate trapping.

Thin-film deposition from chemically reactive multi-component plasmas is complex, and the lack of electron collision cross sections for even the most common metalorganic precursors and their fragments complicates their modeling based on fundamental plasma physics. This study focuses on understanding the plasma physics and chemistry in argon (Ar) plasmas containing lithium bis (trimethylsilyl) amide used to deposit LixSiy thin films. These films are emerging as potential solid electrolytes for lithium-ion batteries, and the Li-to-Si ratio is a crucial parameter to enhance their ionic conductivity. We deposited LixSiy films in an axial flow-through plasma reactor and studied the factors that determine the variation of the Li-to-Si ratio in films deposited at various points on a substrate spanning the entire reactor axis. While the Li-to-Si ratio is 1:2 in the precursor, the Li-to-Si ratio is as high as 3:1 in films deposited near the plasma entrance and decreases to 1:1 for films deposited downstream. Optical emission from the plasma is dominated by Li emission near the entrance, but Li emission disappears downstream, which we attribute to the complete consumption of the precursor. We hypothesized that the axially decreasing precursor concentration affects the electron energy distribution function in a way that causes different dissociation efficiencies for the production of Li and Si. We used Li line intensities to estimate the local precursor concentration and Ar line ratios to estimate the local reduced electric field to test this hypothesis. This analysis suggests that the mean electron energy increases along the reactor axis with decreasing precursor concentration. The decreasing Li-to-Si ratio with axially decreasing precursor concentration may be explained by Li release from the precursor having lower threshold energy than Si release.