Makiko Irie

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.

Resist development to improve flare issue of EUV lithography

This report will introduce novel resist materials including specific photo acid generator (PAG) to improve flare issue from the resist standpoint. We have developed a method to control the acid diffusion length from the PAG. It previously reported that acid diffusion length can be altered by the PAG anion size. In this report, we focused on the effect of the Tg of a resist film. The thermal flow rate of a resist film can suggest the approximate resist Tg. Therefore, we measured the thermal flow rate of the resist. And we found out passivity of acid diffusion control by changing PAG species and volume. Moreover, newly designed PAG tested was confirmed to have uniform distribution in the resist film with no PAG clustering at the resist surface at compared to our conventional PAG. This new positive tone resist formulation shows good performance under flare condition. In addition, we focused on the pattern density variation as one of the key parameters for flare value. Low pattern density indicated less flare value. It is considered that negative tone resist to have advantage for isolated line type features. Novel positive and negative tone type resists were compared side-by-side and discussed for its advantages at varying pattern densities.

Effect of Molecular Structure on Depth Profile of Acid Generator Distribution in Chemically Amplified Resist Films

The acid generator distribution in resist films is an important issue for fine patterning based on chemical amplification. In particular, extreme ultraviolet (EUV) resists require a high acid generator concentration compared with conventional chemically amplified photoresists. In this study, the depth density profiles in partially protected poly(4-hydroxystyrene) films containing dispersed triphenylsulfonium salts were investigated by X-ray reflectivity measurements to clarify the depth profile of acid generator distribution. It was found that the depth profile depends on the molecular structure of acid generators. The hydrogen bonding between polymers and acid generators affected the depth profile of acid generator distribution.

Fundamental Studies on the Acid Generator to Improve the Resolution, Line Width Roughness, and Sensitivity Tradeoff under Ionizing Radiation

The effects of acid generation efficiency and other properties on the resolution, line width roughness (LWR), and sensitivity (RLS) tradeoff for extreme ultraviolet (EUV) photoresists were evaluated under electron beam (EB) exposure. The acid generators (AGs) introducing a trifluoromethyl group as an electron-withdrawing group on the sulfur atom had a much higher reduction potential than current AGs. We determined acid generation efficiency by the 13C-NMR method and standard titration. The dissolution inhibitory effect on the alkaline developer and the thermal property of the resist film using each AG were also evaluated. The RLS performance of resists containing AGs with a higher acid generation efficiency than conventional AGs was characterized using the relative Z-factor under EB exposure.