On Relationships between Gas-Phase Chemistry and Reactive Ion Etching Kinetics for Silicon-Based Thin Films (SiC,SiO2 and SixNy) in Multi-Component Fluorocarbon Gas Mixtures

This work summarizes the results of our previous studies related to investigations of reactive ion etching kinetics and mechanisms for widely used silicon-based materials (SiC, SiO₂, and Si_xN_y) as well as for the silicon itself in multi-component fluorocarbon gas mixtures. The main subjects were the three-component systems composed either by one fluorocarbon component (CF₄, C₄F₈, CHF₃) with Ar and O₂ or by two fluorocarbon components with one additive gas. The investigation scheme included plasma diagnostics by Langmuir probes and model-based analysis of plasma chemistry and heterogeneous reaction kinetics. The combination of these methods allowed one (a) to figure out key processes which determine the steady-state plasma parameters and densities of active species; (b) to understand relationships between processing conditions and basic heterogeneous process kinetics; (c) to analyze etching mechanisms in terms of process-condition-dependent effective reaction probability and etching yield; and (d) to suggest the set gas-phase-related parameters (fluxes and flux-to-flux ratios) to control the thickness of the fluorocarbon polymer film and the change in the etching/polymerization balance. It was shown that non-monotonic etching rates as functions of gas mixing ratios may result from monotonic but opposite changes in F atoms flux and effective reaction probability. The latter depends either on the fluorocarbon film thickness (in high-polymerizing and oxygen-less gas systems) or on heterogeneous processes with a participation of O atoms (in oxygen-containing plasmas). It was suggested that an increase in O₂ fraction in a feed gas may suppress the effective reaction probability through decreasing amounts of free adsorption sites and oxidation of surface atoms.