Plasma etching of dielectric materials using inductively and capacitively coupled fluorocarbon discharges: mechanistic studies of the surface chemistry

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Fluorocarbon (FC) plasmas are commonly used for dielectric materials etching. Our initial work was performed using an inductively coupled plasma (ICP) system to produce FC discharges. We first examined the effect of CO addition to C4F8 or C4F8/Ar plasmas for selective etching of organosilicate glass (OSG), which is a typical low k (LK) material over etch stop layers. The chemical activity of CO when added to either C4F8 or C4F8/80%Ar can be understood in terms of the CO dissociation energy threshold relative to energies of inelastic electron collision processes of the dominant feedgas component. We also studied the plasma etching behavior of 193 nm and 248 nm photoresist in FC discharges used for dielectric etching. We showed that ion-enhanced selective volatilization of carbonyl groups of the 193 nm photoresist polymer backbone which is absent for the 248 nm material, along with modulation of the ion-interaction with the photoresist material by fluorocarbon surface passivation, may be responsible for the introduction of pronounced surface roughness of 193 nm photoresists.

Current industrial efforts are aimed primarily at capacitively coupled plasma (CCP) systems. A home-built dual frequency CCP reactor was used to investigate additional aspects of dielectric materials plasma etching. We designed a gap structure to simulate sidewall surface processes occurring during high aspect ratio trench etching. In particular, we showed that the FC film deposition rates measured using the gap structure qualitatively correlate with the trench sidewall angles produced in LK dielectrics in both C4F8/Ar and CF4/H2 based gas chemistries: The lower the FC deposition rate on the sidewall, the more vertical the trench sidewall. This approach was used to study surface chemistry aspects of FC film deposition with and without ion bombardment. For the gap structure film deposition takes place without ion bombardment and we observed a novel FC film growth phenomenon in pure C4F8 plasmas at high pressure: Two distinct chemical surface portions were shown to exist simultaneously, one consisting primarily of C-F2 and C-F3 bonding, and the other of C-C/C-H bonding. An explanation consistent with all of our data is localized CF2 attachment to growing FC chains.