Contaminants, chemically amplified systems

From these highly idealized reactions, one can gain an understanding of some potential diffculties and process related concerns. For this system to work satisfactorily, it would be necessary for the radiation generated acid concentration, [H+], to remain constant. However, in most chemically amplified systems, undesired side reactions occur that prematurely destroy the acid, i.e., reactions with contaminants such as water, oxygen, ions or reactive sites on the polymer (reactions 2 and 3). 

The rates of these reactions depend upon the contaminant concentration and the inherent rate constants of the reactions. While the exact nature of these reactions differ for each type of chemically amplified system and are not fully understood, this generalized discussion is sufficient to understand many of the process issues. 

Recently, nonionic acid precursors based on nitrobenzyl ester photochemistry have been developed for chemically amplified resist processes (78-80). These ester based materials (Figure 8) exhibit a number of advantages over the onium salt systems. Specifically, the esters are easily synthesized, are soluble in a variety organic solvents, are nonionic in character, and contain no potential device contaminants such as arsenic or antimony. In addition, their absorption characteristics are well suited for deep-UV exposure. 

Chemically amplified resist system is a promising technology to attain hi resolution and high sensitivity for sub-quarter micron device fabrication. However, air-borne contamination (1-3), such as ammonia mainly generated from conventional adhesion promoter, hexamethyldisilazane (HMDS), severely affects this kind of resist. It causes surface insoluble layer of resist patterns, which results in failure of the pattern fabrication. 

As with all chemically amplified resists, a major concern is, however, the latent image stabflity and the susceptibility to environmental conditions. With t-BOC deprotecdon systems, the influence of airborne nudeophilic contaminants has been recently demonstrated (23) the observadon of surface residues in a number of such materials (23, 24) may be traced back to the presence of ppb amounts of volatile bases. In the case of the acetal systems (19-21), the influence of trace bases is less pronounced, as even amine hydrochlorides are sdll sufficiendy addic to have some catatydc activity. Linewidth dianges with the interval between exposure and post exposure bake have been observed for both the t-BOC and the acetal systems. In the case of the t-BOC tystems, long intervals (several hoius) between exposure and post-e]q)osure bake will lead to a decrease of apparent sensidvity, which manifests itself as a linewidth inCTease, or, in extreme cases, as faUure to open the imaged areas. These effects are normally due to contaminadon by base traces, or, in cases where the presence of even ppb amounts of bases can be excluded, may be assumed to be the result of the same, unspecified chain terminadon (add annihilation) mechanism which is responsible for the containment of the calalytic reacdon to the immediate vicinity of the imaged resist. 

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