Plasma etching temperature dependence

Poly (butene-1 sulfone (PBS) is a highly sensitive, high-resolution electron-beam resist (1-2) which is used primarily as a wet-etch mask in the fabrication of chrome photomasks. PBS has found little use as a dry-etch mask because of its lack of etch resistance in plasma environments (3-8). This primarily stems from the fact that PBS depolymerizes in such an environment which greatly enhances the rate of material loss from the film. Moreover, depolymerization is an activated process which causes the etching rate to be extremely temperature dependent. Previous work (3,7) has shown that the etch rate of PBS in fluorocarbon-based plasmas varies by orders of magnitude for temperature differentials of less than 30 C. 

These apparent contradictions can be rationalized in terms of a model which incorporates plasma-induced polymerization along with depolymerization. PBS has long been known to exhibit a marked temperature-dependent etch rate in a variety of plasmas. This is clearly seen in the previously published Arrhenius plots (3,7) for two different plasma conditions (Figure 1). This dependence is characteristic of an etch rate that is dominated by an activated material loss as would occur with polymer depolymerization. The latter also greatly accelerates the rate of material loss from the film. Bowmer et al. (10-13) have shown in fact that poly(butene-l sulfone) is thermally unstable and degrades by a depolymerization pathway. A similar mechanism had been proposed by Bowden and Thompson (1) to explain dry-development (also called vapor-development) under electron-beam irradiation. 

High etch rates and selectivity can be achieved by judicious selection of feed gases to a plasma reactor. The atomic and radical species formed by electron impact dissociation depend largely on feed gas composition, and the intrinsic etch rates measured in the absence of a plasma (i.e., downstream etching) provide a useful indicator of chemical selectivity in the presence of a plasma. For example, the ratio of (100) silicon (34) to thermal oxide (Si02) (37) etching by F atoms is 41 1 at room temperature. As etch rates generally follow an Arrhenius type dependence on substrate temperature. 

The results obtained on etching PBS in fluorine-based plasmas vary quite considerably depending on the temperature of the substrate. Below 15 C, both the resist and substrate are attacked (etched), by the etchant species while at an intermediate temperature (15-23 0, the phenomenon of reversal etching is observed (8) in which the exposed substrate is not etched at all, while the resist (and subsequently the substrate underneath the resist) is readily etched by the plasma thus giving rise to a negative-tone pattern. At higher temperatures, (>25 C), both the resist and substrate are etched by the plasma as in the low-temperature case, except that etching completely stops after several seconds. 

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