Chemical optimization of resist/developer systems tuned for sub-0.4-μm process window expansion

Abstract

In order to perform 0.2 micrometer processes, one needs to study the diffusion of photoacid generators within the photoresist system, since diffusion during post exposure bake time has an influence on the critical dimension (CD). We have developed a new method to study the diffusion of photoacid generators within a polymer film. This new method is based on monitoring the change of the fluorescence intensity of a pH- sensitive fluorescent dye caused by the reaction with photoacid. A simplified version of this experiment has been conducted by introducing acid vapor to quench the fluorescence intensity of this pH sensor. A thin polymer film is spin cast onto the sensor to create a barrier to the acid diffusion process. During the acid diffusion process, the fluorescence intensity of this pH sensor is measured in situ, using excitation and emission wavelengths at 466 nm and 516 nm, respectively. Fluoresceinamine, the pH sensitive fluorescent dye, is covalently bonded onto the treated quartz substrate to form a single dye layer. Poly(hydroxystyrene) (M<SUB>n</SUB> equals 13k, T<SUB>g</SUB> equals 180 degrees Celsius) in PGMEA (5% - 18% by weight) is spin cast onto this quartz substrate to form films with varying thickness. The soft bake time is 60 seconds at 90 degrees Celsius and a typical film has a thickness of 1.4 micrometers. Trifluoroacetic acid is introduced into a small chamber while the fluorescence from this quartz window is observed. Our study focuses on finding the diffusion constant of the vaporized acid (trifluoroacetic acid) in the poly(hydroxystyrene) polymer film. By applying the Fick's second law, (I<SUB>t</SUB> - I<SUB>o</SUB>)/(I<SUB>(infinity</SUB> ) - I<SUB>o</SUB>) equals erfc [L/(Dt)<SUP>1/2</SUP>] is obtained. The change of fluorescence intensity with respect to the diffusion time is monitored. The above equation is used for the data analysis, where L represents the film thickness and t represents the average time for the acid to diffuse through the film. The diffusion constant is calculated to be at the order of 10<SUP>-10</SUP> cm<SUP>2</SUP>/s to 10<SUP>-12</SUP> cm<SUP>2</SUP>/s. All the experiments are conducted at room temperature and are valid only for acid vapor. With different film thickness, it was found that the acid diffuses through the film with a similar diffusion constant. The diffusion is faster with increased solvent residue in the film (controlled by spin coating speed). The theoretical computer modeling of the local acid concentration with respect to acid diffusion is also performed.