On Relationships between Gas-Phase Chemistry and Reactive Ion Etching Kinetics for Silicon-Based Thin Films (SiC, SiO(2) and Si(x)N(y)) 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, SiO(2), and Si(x)N(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 (CF(4), C(4)F(8), CHF(3)) with Ar and O(2) 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 O(2) fraction in a feed gas may suppress the effective reaction probability through decreasing amounts of free adsorption sites and oxidation of surface atoms.