On chemical amplification

As discussed previously, an optional postexposure, predevelopment bake can reduce problems with the standing-wave effect in DNQ-novolac positive resists. However, such a postexposure bake step is indispensable in the image reversal of positive resists (37-41) and certain resists based on chemical amplification of a photogenerated catalyst (64-67, 77, 78). For both types of resists, the chemistry that differentiates between exposed and unexposed areas does not occur solely during irradiation. Instead, differentiation occurs predominantly during a subsequent bake. Therefore, to obtain acceptable CD control in these systems, the bake conditions must be carefully optimized and monitored. 

MacDonald, S.A. Schlosser, H. Ito, H. Clecak, N. Willson, C.G. Plasma developable photoresist systems based on chemical amplification. Chem. Mater. 1991, 3, 435-442. 

Fig. 182 Number of publications on chemical amplification resists (SciFinder)...

Kaimoto, K. Nozaki, S. Takechi, andN. Abe, Alicyclic polymer for ArF and KrF excimer resist based on chemical amplification, Proc. SPIE 1672, 66 (1992). 

How the balance between the above-named requirements are struck in each of the major advanced resist-processing schemes in use today is discussed below, along with the advantages and drawbacks of each technique. In particular, we discuss the material basis of the resolution limit issues of resists, especially as they concern those based on chemical amplification systems, since these constitute the majority of resists in use in advanced lithographic processing today. 

Advanced photoresists, such as 193 and 248 nm photoresists, are based on chemical amplification concept [7,8]. These chemically amplified photoresists generally consist of a base polymer, a photo-sensitive compound called photoacid generator (PAG), and sometimes a cross-linking... 

Major advances in radiation sensitivity have been achieved by applying the concept of chemical amplification to photolithography [252-254]. Chemical amplification is related to a cascade of chemical reactions that are initiated by a single photon. In fact, strategies based on chemical amplification have played a key role in the development of novel resist systems, as will be outlined in the following subsection. It is to be noted, that the chemical amplification concept has served the semiconductor industry as a workhorse for the past few decades. 

Dry-Film Resists Based on Radical Photopolymerization. Photoinitiated polymerization (PIP) is widely practiced ia bulk systems, but special measures must be taken to apply the chemistry ia Hthographic appHcations. The attractive aspect of PIP is that each initiator species produced by photolysis launches a cascade of chemical events, effectively forming multiple chemical bonds for each photon absorbed. The gain that results constitutes a form of "chemical amplification" analogous to that observed ia silver hahde photography, and illustrates a path for achieving very high photosensitivities. 

The detection of spectral sensitizing action often depends on amplification methods such as photographic or electrophotographic development or, alternatively, on chemical or biochemical detection of reaction products. Separation of the photosensitization reaction from the detection step or the chemical reaction allows selection of the most effective spectral sensitizers. Prime considerations for spectral sensitizing dyes include the range of wavelengths needed for sensitization and the absolute efficiency of the spectrally sensitized process. Because both sensitization wavelength and efficiency are important, optimum sensitizers vary considerably in their stmctures and properties. 

A number of new resist materials which provide very high sensitivities have been developed in recent years [1-3]. In general, these systems owe their high sensitivity to the achievement of chemical amplification, a process which ensures that each photoevent is used in a multiplicative fashion to generate a cascade of successive reactions. Examples of such systems include the electron-beam induced [4] ringopening polymerization of oxacyclobutanes, the acid-catalyzed thermolysis of polymer side-chains [5-6] or the acid-catalyzed thermolytic fragmentation of polymer main-chains [7], Other important examples of the chemical amplification process are found in resist systems based on the free-radical photocrosslinking of acrylated polyols [8]. 

The seminal work on deep-UV resist materials which incorporate chemical amplification was started at IBM San Jose s Research Laboratory in 1979 when FrSchet and Willson first prepared poly(4-t-butyloxycarbonyloxy styrene) and end-capped copolymers of o-phthalaldehyde and 3-nitro-l,2-phthalic dicarboxaldehyde. 

In this paper we report on the use of trifluoro-methanesulfonates (Table 1) of 4-N, N-dimethylamino-benzenediazonium (Dl) and 4-methoxybenzene-diazonium (D2) as CEL dyes, negative working sensitizers, and photoacid generators for chemical amplification resist systems(11). 

The latest addition to this list of dry developing resist materials is a contribution from IBM s San Jose Research Laboratory (66-67) that evolved from efforts to design positive-tone resist materials that incorporate chemical amplification. These efforts were stimulated by the fact that the quantum yield of typical diazoquinones of the sort used in the formulation of positive photoresists is 0.2 to 0.3 thus, three or four photons are required to transform a single molecule of sensitizer. This places a fundamental limit on the photo-sensitivity of such systems. 

Frechet, J. M. J. Ito, H. Willson, C. G. "Sensitive Deep UV Resist Incorporating Chemical Amplification," International Conference on Microlithography, Grenoble, France, Oct. 1982. 

M. Kopp et al. 1998. Chemical Amplification Continuous-Flow PCR on a Chip. Science 280 1046-1048. 

Chemical Amplification. The measurement of a small electrical signal is often accomplished by amplification to a larger, more easily measured one. This technique of amplification can also be applied to chemical systems. For peroxy radicals, Cantrell and Stedman (117) proposed, as a possible technique, the chemical conversion of peroxy radicals to N02 with amplification (i.e., more than one N02 per peroxy radical). This method has also been used for laboratory studies of H02 reactions on aqueous aerosols (21). The following chemical scheme was proposed as the basis of the instrument ... 

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