Deprotection kinetics

Thermal and acid-catalyzed deprotection kinetics of PBOCST and PTBMA was monitored by UV and IR spectroscopy, respectively [515], and compared very favorably with models based on a stochastic kinetics simulator (CKS)... 

Kinetics, the branch of physical chemistry dealing with rates of chemical reactions, therefore had its origins in the above-mentioned works of Guldberg and Waage as well as van t Hoff. Today, the techniques developed hy these scientists are used to study rates of various reactions involved in lithographic patterning. A few examples include deprotection kinetics of chemical amplification resists, development kinetics of resists, kinetics of photolysis of photoacid generators in... 

Deprotection kinetics of representative resist polymer systems... 

Infrared spectroscopy provides a convenient method for studying the deprotection kinetics of resist polymers. For example, the deprotection kinetics of some alicyclic polymer resist systems comprising (i) poly(methylpropyl bicyclo[2.2.1]-hept-5-ene-2-carboxylate-co-bicyclo[2.2.1]hept-5-ene-2-carboxylic acid) (trivial name poly(carbo-t-butoxynorbomene-co-norbornene carboxylic acid) [poly(CBN-co-NBCA)] (I) and (ii) poly(methylpropyl bicyclo[2.2.1]hept-5-ene-2-carboxylate-co-maleic anhydride) (trivial name poly(carbo-t-butoxynorbomene-co-maleic anhydride) [poly(CBN-aZr-MAH)] (11) and containing triphenylsulfonium... 

The methodologies reported here follow from U. Okoroanyanwu, J.D. Byers, T. Cao, S.E. Webber, and C.G. Willson, Deprotection kinetics of alicyclic polymer resist systems designed for ArF (193 nm) lithography, in Polymers for Micro and Nano Patterning Science and Technology, H. Itoh, E. Reichmanis, O. Nalamasu, and T. Ueno, Eds., pp. 174 190, American Chemical Society, Washington, DC (1998). 

Deprotection Kinetics of Alicyclic Polymer Resist Systems Designed for ArF (193 nm) Lithography... 

The deprotection kinetics of alicyclic polymer resist systems designed for 193 nm lithography was examined using JR and fluorescence spectroscopic techniques. A kinetic model was developed that simulates the deprotection of the resists fairly well. A new, simple, and reliable method for monitoring photoinduced acid generation in polymer films and in solutions of the kind used in 193 nm and deep-UV lithography was developed. This technique could find application in the study of diffusional processes in thin polymer films. 

Infra-red spectroscopy and fluorescence spectroscopy provide convenient methods for studying these processes. Using FTIR, we investigated the deprotection kinetics of some of our alicyclic polymer resist systems (2,3) (containing triphenylsulfonium hexafluoroantimonate) that were exposed to 248 and 193 nm... 

IR Study of the Deprotection Kinetics of Radiation-Exposed Resist Films Upon exposure to UV-radiation, the PAG decomposes with a rate constant kc to produce the photoacid (designated as Acid), as illustrated in equation 1. Here hv represents photon energy, where h is the Planck s constant and v is the frequency of the radiation. 

A plot of In Ka versus 1/T gives a straight line, the slope of which is related to the activation energy, and the vertical intercept of which is related to the Arrhenius preexponential factor. Using numerical simulation of equations 3, 5, and 9, the deprotection kinetics can be modeled for various experimental conditions and values for ka obtained. 

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