Changes of chemical nature of photoresists induced by various plasma treatments and their impact on LWR

Changes in chemical nature of an ArF photoresist caused by various plasmas were analyzed, and it was found that the HBr plasma treatment induces a selective detachment of a heterocyclic unit of the photoresist, and the detached unit remains in the photoresist film. Thermomechanical analyses were performed, which showed that the softening temperature of the photoresist decreases by the HBr treatment, indicating that the detached heterocyclic unit acts as a plasticizer in the photoresist film. These results showed that the HBr treatment can be regarded as a softening process of the photoresist. This HBr treatment was applied to the fabrication of line patterns and it was shown that the treatment remarkably improves LWR (line width roughness) after etching. This improvement was more pronounced for the case of an isolated pattern than the case of a dense pattern. Further investigations on the HBr treatment were performed by changing the copolymerization ratio of a monomer containing the heterocyclic unit. It was shown that the reduction of LWR by the HBr treatment becomes more enhanced when the copolymerization ratio increases. However, an intensive HBr treatment was found to deteriorate LWR, showing that there is an optimum condition of the HBr treatment in terms of improving LWR.