Airborne base contamination

The impact on negative-CA resists of airborne base contamination differs qualitatively from their positive tone counterparts. Suppression of acid-catalyzed chemistry at the surface of a negative resist results in some film erosion at the top of the exposed fields and in some cases an apparent loss of photosensitivity, but in general the reUef images formed exhibit the expected cross-sectional profile. This is in sharp contrast with the typical behavior seen with positive-tone CA resists, where suppression of acid-catalyzed chemistry at the surface causes an insoluble surface skin. 

The human health risk assessment was conducted based on exposure estimates from two most relevant exposure pathways, namely dietary intake of POPs from food consumption and inhalation intake of airborne POPs contaminants. The potential intake of POPs from drinking water (considered to be a relatively minor exposure pathway) was not taken into account due to lack of relevant local data necessary for their estimation. 

Application of a protective overcoat to seal off airborne contaminants was also a popular approach initially. Although many polymers, lipophilic and hydrophilic, have been evaluated as a topcoat, water-soluble poly[ (meth)acryhc acid] is most commonly employed, which can be cast from a water solution without interfacial mixing with the resist layer and can be removed during aqueous base development. However, it has been reported that a poly(acrylic acid) overcoat allows diffusion of water, which reportedly contaminates a chemical amplification resist [211]. Poly(cx-methylstyrene) has been recommended as a good barrier against both airborne base and water [211]. 

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. 

The TLVs, as recommended and published by the ACGIH, refer to concentrations of airborne contaminants or levels of physical agents, and represent the conditions to which it is believed nearly all workers may be repeatedly exposed day after day without adverse effects. TLVs are based on the results of animal experiments, limited human experiments, some industrial experience and, when possible, a combination of all three. 

The TLVs for airborne contaminants are based on the premise that although all chemical substances are toxic at some concentration for some period of time, a concentration exists for all substances from which no toxicity may be expected no matter how often the exposure is repeated. A similar premise holds for substances producing irritation, discomfort and nuisance. In using these limits, items such as excursion factors, ceiling values, "skin" notations, mixtures of substances, and inert material should be considered. These factors are discussed below. 

Filter samples can be prepared to airborne workplace concentrations by spiking each filter with aqueous solution containing elements with concentrations gravimetrically traceable to ultrapure metals or stoidiiometricaUy well defined oxides. The amormts correspond for some of the materials to current threshold limit values of contaminants in workroom atmospheres provided that the simulated filter has been exposed to one cubic meter of air. The certified values are based on a gravimetric procedure, i.e. weight per volume composition of the primary reference material dissolved in high purity sub-dis-tiUed acids. The National Institute of Occupational Health in Oslo, Norway, has produced several batches of such materials certified for 20 elements. Additionally, information values are reported for four other elements see Table 6.2. 

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