| Advances in microfabrication technology to construct smaller and faster integrated circuits depend on improving resolution capabilities of patterning thin films of photoresist materials by photolithographic imaging. Positive-tone, chemically amplified photoresists represent one of the most important classes of photoresist materials. These materials function by the generation of a photoacid catalyst from the decomposition of a photoacid generator with exposure that catalyzes chemical reactions that alter the development rate of the exposed resist. Chemical amplification is derived from the fact that a single molecule of photogenerated catalyst may participate in numerous reactions. Photoacid catalyzes the cleavage of acid-labile protecting groups from the backbone of the resin polymer, increasing the dissolution rate of the resist in aqueous base. A pattern is formed in the photoresist film from the difference between dissolution rates of the exposed and unexposed material.; The continual improvement of the resolution of chemically amplified resists depends on understanding, controlling, and optimizing the chemical processes that govern pattern formation, namely photoacid generation, resin deprotection, and resist dissolution. To elucidate how the formulation of the resist affects these processes, a systematic methodology was designed, validated and implemented to analyze the materials and processing of chemically amplified photoresist systems. The efficiency of photoacid generation and the concentration of photoacid produced upon exposure were determined for a wide range of resist formulations, processing conditions, and exposure technologies. The chemical structure of photoacid generators and base quenchers were found to affect the processes of acid-base neutralization, resin deprotection, and resist development. The reaction-diffusion process of photoacid to deprotect the resin was identified to depend on the concentration of the photoacid generator. A much greater concentration of photoacid was required to render development for ultra-thin films of chemically amplified photoresist less than 150nm thick than for thicker resist films. These investigations identified that the action of photoacid within the resist film is more complex than previously thought, and provided insight for the design and optimization of photoresist materials and processes. |
