Fluorinated diesters were synthesized and evaluated as dissolution inhibitors (DIs) for 157 nm lithography. The results of dissolution rate measurements, exposure studies, and etching experiments on blends of fluorinated polymers containing these dissolution inhibitors are reported. It was shown that the DIs effectively slow the dissolution rate of the matrix polymer, poly(hexafluorohydroxyisopropyl styrene) (PHFHIPS). Etching studies show that they enhance the plasma etch resistance of poly(methyl methacrylate) using tetrafluoromethane plasma. Addition of the best performing dissolution inhibitor, cyclohexane-1,4-dicarboxylic acid bis-(1-cyclohexyl-2,2,2-trifluoro-1-methyl-ethyl) ester) (FCDE1) to candidate 157 nm photoresist polymers, Duvcor and poly(hexafluorohydroxyisopropyl styrene)-co-poly(t-butyl methacrylate) [pPHFHIPS-co-pt-BMA], improves the imaging behavior of these polymers. Our attempts to elucidate the mechanism of dissolution inhibition for this series of compounds will be discussed. Fourier Transform Infrared (FTIR) studies in conjunction with dissolution rate measurements performed on a series of DI analogues suggest a mechanism based on hydrogen bonding.
Fluorinated dissolution inhibitors (DIs) for 157 nm lithography were designed and synthesized as part of an ongoing study on the structure/property relationships of photoresist additives. The problem of volatilization of small DI candidates was observed from matrices such as poly(methyl methacrylate) (PMMA) and poly(hexafluorohydroxy-isopropyl styrene) (PHFHIPS) during post-apply bake cycles using Fourier Transform Infrared Spectroscopy (FT-IR). To avoid this problem, low volatility fluorinated inhibitors were designed and synthesized. Three fluorinated DIs, perfluorosuberic acid bis-(2,2,2,-trifluoro-1-phenyl-1-trifluoromethyl-ethyl) ester (PFSE1), perfluorosuberic acid bis-[1-(4-trifluoromethyl-phenyl)-ethyl] ester (PFSE2) and a fluorinated phenylmethanediol diester (FPMD1), largely remained in a PHFHIPS film during the post-apply bake. The dissolution behavior of the two fluorinated diesters was studied and found to slow down the dissolution rate of PHFHIPS with inhibition factors of 1.9 and 1.6, respectively. The absorbance of PHFHIPS films containing 10 wt% of the diester inhibitors is 3.6 AU/micron compared with an absorbance of 3.3 AU/micron for the polymer itself. The absorbance of 10% FPMD1 in PHFHIPS was measured as 3.5 AU/micron compared with an absorbance of 3.4 AU/micron for the polymer itself. Thus, the non-volatility and transparency of the fluorinated inhibitors at 157 nm as well as their ability to reduce the development rate of fluorinated polymers make them suitable for use in a 157 nm resist system.
Poly(vinyl alcohol-co-(alpha) -trifluoromethyl vinyl alcohol) (PVA-co-CF3PVA) protected with an acid cleavable group was prepared as a single-layer photoresist for use in 157 nm VUV lithography. It was found that the (alpha) -trifluoromethyl substituent renders PVA-co-CF3PVA readily soluble in 0.262 N TMAH. The protected polymer can be spin-coated from PGMEA and preliminary studies using 248 nm exposure showed a THP protected PVA-co-CF3PVA undergoes chemically amplified deprotection with a clearing dose of approximately 15 mJ/cm2. Using a VUV spectrometer, absorption coefficients of approximately 3 micrometer-1 were observed at 157 nm with PVA-co-CF3PVA and THP protected PVA-co-CF3PVA. Detailed lithographic evaluation of the polymer is underway and design strategies for 157 nm single-layer photoresists will be discussed.
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