Relationship between deprotection and film thickness loss during plasma etching of positive tone chemically amplified resists

Abstract

Positive tone chemically amplified (CA) resists have demonstrated the sensitivity, contrast, and resolution necessary to print state-of-the-art subwavelength features using 248 nm and more recently 193 nm lithography. These materials are also being considered for printing sub-100 nm features with 157 nm and next-generation lithography technologies such as extreme ultraviolet and electron beam projection lithography. The basis for solubility differential and image formation in these resists is the acid catalyzed deprotection of labile protecting groups of an inherently base soluble polymer. The deprotection is effected by the photochemical generation of strong acid during the exposure process. Such acid-catalyzed deprotection reactions can also occur in unexposed resist areas when etched in a plasma. This can be due to UV exposure, high-energy ion bombardment, elevated substrate temperatures, or interaction of the resist surface with plasma species to form acidic moieties. Deprotection has been associated with resist mass loss and film shrinkage during plasma etching, leaving inadequate masking material for the entire etch step. In this article, we report the film thickness loss of several unexposed CA resists as a function of etch time in a variety of plasmas and correlate these data with film composition, monitored by Fourier transform infrared spectroscopy. These results are compared with theoretical predictions based on generally accepted deprotection mechanisms. Our findings indicate that the “acidic” nature of certain plasmas such as Cl2/O2 can result in deprotection in the resist film, even in the absence of a photoacid generator. Additionally, the data suggest that the nature of the resist polymer and, in turn, the identity of the deprotection products directly influence resist mass loss and etch rate linearity, both of which can be controlled by careful selection of resist materials.