NOVEL NAPHTHALIMIDE SULFONATE DERIVATIVE, AND PHOTOACID GENERATOR AND PHOTORESIST COMPOSITION EACH COMPRISING SAME

Abstract

The present invention relates to a naphthalimide sulfonate derivative, and a photoacid generator and a photoresist composition each comprising same and, more specifically, to a naphthalimide sulfonate derivative compound, and a photoacid generator and a photoresist composition each comprising same, wherein the compound has excellent absorbance for light of i-line (365 nm) wavelength, is greatly easy to prepare into a polymerizable composition due to very high solubility in an organic solvent, has good thermal stability, and shows a favorable acid generation rate.

Claims

1. A sulfonic acid derivative compound of naphthalimide represented by the following Formula I: ##STR00029## wherein R.sub.1 and R.sub.2 are each independently a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, or a substituted or unsubstituted alkylaryl group; and R.sub.3 is independently a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, a substituted or unsubstituted arylalkyl group, a substituted or unsubstituted alkylaryl group, or a group of formula R.sub.4O(CH.sub.2).sub.n, where n is an integer of 1 to 12 and R.sub.4 is a substituted or unsubstituted aliphatic hydrocarbon group.

2. The sulfonic acid derivative compound of naphthalimide according to claim 1, wherein R.sub.1 and R.sub.2 are each independently a substituted or unsubstituted, C.sub.1-C.sub.12 linear alkyl group or C.sub.3-C.sub.12 branched alkyl group; a substituted or unsubstituted C.sub.3-C.sub.12 alicyclic hydrocarbon group; a substituted or unsubstituted C.sub.6-C.sub.20 aryl group; a substituted or unsubstituted C.sub.7-C.sub.20 arylalkyl group; or a substituted or unsubstituted C.sub.7-C.sub.20 alkylaryl group; and R.sub.3 is a substituted or unsubstituted, C.sub.1-C.sub.12 linear alkyl group or C.sub.3-C.sub.12 branched alkyl group; a substituted or unsubstituted C.sub.3-C.sub.12 alicyclic hydrocarbon group; a substituted or unsubstituted C.sub.6-C.sub.20 aryl group; a substituted or unsubstituted C.sub.7-C.sub.20 arylalkyl group; a substituted or unsubstituted C.sub.7-C.sub.20 alkylaryl group; or a substituted or unsubstituted C.sub.1-C.sub.12 alkoxy-C.sub.1-C.sub.12 alkyl group.

3. The sulfonic acid derivative compound of naphthalimide according to claim 1, wherein R.sub.1 and R.sub.2 are each independently a C.sub.1-C.sub.12 linear alkyl group or C.sub.3-C.sub.12 branched alkyl group which is unsubstituted or substituted with one or more halogen atoms or alicyclic hydrocarbon groups; a C.sub.3-C.sub.12 alicyclic hydrocarbon group which is unsubstituted or substituted with one or more halogen atoms; a C.sub.6-C.sub.20 aryl group which is unsubstituted or substituted with one or more halogen atoms; a C.sub.7-C.sub.20 arylalkyl group which is unsubstituted or substituted with one or more halogen atoms or C.sub.1-C.sub.12 alkylthio groups; or a C.sub.7-C.sub.20 alkylaryl group which is unsubstituted or substituted with one or more halogen atoms; and R.sub.3 is a C.sub.1-C.sub.12 linear alkyl group or C.sub.3-C.sub.12 branched alkyl group which is unsubstituted or substituted with one or more halogen atoms or alicyclic hydrocarbon groups; a C.sub.3-C.sub.12 alicyclic hydrocarbon group which is unsubstituted or substituted with one or more halogen atoms; a C.sub.6-C.sub.20 aryl group which is unsubstituted or substituted with one or more halogen atoms; a C.sub.7-C.sub.20 arylalkyl group which is unsubstituted or substituted with one or more halogen atoms or C.sub.1-C.sub.12 alkylthio groups; a C.sub.7-C.sub.20 alkylaryl group which is unsubstituted or substituted with one or more halogen atoms; or a C.sub.1-C.sub.12 alkoxy-C.sub.1-C.sub.4 alkyl group which is unsubstituted or substituted with one or more halogen atoms.

4. The sulfonic acid derivative compound of naphthalimide according to claim 1, wherein R.sub.1 is methyl group, ethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, nonafluorobutyl group or tosyl group; R.sub.2 is methyl group, ethyl group, propyl group, isopropyl group, butyl group or cyclohexyl group; and R.sub.3 is methyl group, ethyl group, propyl group, hexyl group, heptyl group, cyclohexyl group, methoxyethyl group or butoxyethyl group.

5. The sulfonic acid derivative compound of naphthalimide according to claim 1, which is selected from the following compounds: ##STR00030## ##STR00031## ##STR00032##

6. A photoacid generator comprising a sulfonic acid derivative compound of naphthalimide according to claim 1.

7. A photoresist composition comprising a sulfonic acid derivative compound of naphthalimide according to claim 1; and a binder resin.

8. A substrate coated with a photoresist composition according to claim 7.

9. A patterned substrate obtained by exposing and developing a coated substrate according to claim 8.

10. A display device comprising a patterned substrate according to claim 9.

11. A semiconductor device comprising a patterned substrate according to claim 9.

Description

EXAMPLES

Example 1: Preparation of 4-(1-ethoxybutyl)-naphthalimide trifluoromethane sulfonate (1)

Reaction 1. Synthesis of 5-butyryl acenaphthene

[0054] 21.43 g (139.0 mmol) of acenaphthene was added to dichloromethane, and cooled to 10 C. or lower. 19.46 g (145.9 mmol) of aluminum chloride was added thereto and stirred for 30 minutes, and then 14.81 g (139.0 mmol) of butyryl chloride was slowly added thereto, and the reaction mixture was stirred for 1 hour at 5 C. or lower. Next, distilled water was added to the reaction product, and after stirring for 30 minutes, the organic layer was separated. The separated organic layer was washed twice with distilled water, and the collected organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The concentrated residue was purified by silica gel column chromatography (developing solvent; ethyl acetate:n-heptane=1:4) to obtain 21.90 g (70.26%) of 5-butyryl acenaphthene.

[0055] .sup.1H NMR (.sub.ppm; CDCl.sub.3): 8.65-8.62 (dd, 1H), 8.05-8.02 (d, 1H), 7.66-7.55 (dd, 1H), 7.41-7.35 (d, 1H), 7.31-7.29 (dd, 1H), 3.43-3.38 (m, 4H), 3.05 (t, 2H), 1.87-1.77 (m, 2H), 1.04 (t, 3H)

[0056] MS(m/z): 224

Reaction 2. Synthesis of 5-(1-ethoxybutyl)acenaphthene

[0057] 10.60 g (47.3 mmol) of 5-butyryl acenaphthene was dissolved in ethanol and sodium borohydride was added thereto, the mixture was stirred at 60 C. and then cooled to 10 C. or lower, and 19.17 mL of 10% aqueous solution of hydrochloric acid was slowly added thereto and the mixture was stirred at 60 C. After the reaction was finished, distilled water was added to the reaction product and stirred for 30 minutes. Next, ethyl acetate was added thereto and the mixture was stirred, and then the organic layer was separated. The separated organic layer was washed with each of saturated aqueous solution of sodium bicarbonate and distilled water, and the collected organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The product obtained by distilling the organic layer under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate:n-heptane=1:10) to obtain 9.54 g (79.3%) of 5-(1-ethoxybutyl) acenaphthene.

[0058] .sup.1H NMR (.sub.ppm; CDCl.sub.3): 7.91 (d, 1H), 7.45 (dt, 2H), 7.31-7.25 (m, 2H), 4.86 (dd, 1H), 3.45-3.34 (m, 6H), 1.95 (m, 1H), 1.83 (m, 1H), 1.56-1.45 (m, 1H), 1.39-1.30 (m, 1H), 1.20 (t, 3H), 0.93 (t, 3H)

[0059] MS(m/z): 254

Reaction 3. Synthesis of 4-(1-ethoxybutyl)naphthalic anhydride

[0060] 7.24 g (28.4 mmol) of 5-(1-ethoxybutyl) acenaphthene was added to acetic acid, 42.41 g (142.3 mmol) of sodium dichromate dihydrate was added thereto, and the mixture was stirred at room temperature and heated to reflux. Then, after cooling to room temperature, the reaction mixture was poured into ice water, and ethyl acetate was added thereto and the mixture was stirred for 30 minutes. The organic layer was separated and washed with each of saturated aqueous solution of sodium bicarbonate and distilled water, and the collected organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The product obtained by distilling the organic layer under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate:n-heptane=1:10) to obtain 6.32 g (74.4%) of 4-(1-ethoxybutyl) naphthalic anhydride.

[0061] .sup.1H NMR (.sub.ppm; CDCl.sub.3): 8.73 (dd, 1H), 8.65 (dd, 1H), 8.62 (d, 1H), 7.87 (d, 1H), 7.83 (dd, 1H), 5.00 (dd, 1H), 3.46-3.38 (m, 2H), 1.99-1.87 (m, 1H), 1.84-1.73 (m, 1H), 1.61-1.56 (m, 1H), 1.54-1.35 (m, 1H), 1.23 (t, 3H), 0.95 (t, 3H)

[0062] MS(m/z): 298

Reaction 4. Synthesis of N-hydroxy-4-(1-ethoxybutyl)naphthalimide

[0063] 4.60 g (15.4 mmol) of 4-(1-ethoxybutyl) naphthalic anhydride was added to ethanol, 1.61 g (23.1 mmol) of hydroxylamine hydrochloride salt and 1.83 g (23.1 mmol) of pyridine were added thereto, and the mixture was heated to reflux. Ethanol was removed under reduced pressure to obtain 4.18 g (crude yield: 86.5%) of crude N-hydroxy-4-(1-ethoxybutyl) naphthalimide, which was used in the next reaction without further purification.

[0064] .sup.1H NMR (.sub.ppm; CDCl.sub.3): 8.71-8.64 (m, 4H), 7.86 (d, 1H), 7.81 (dd, 1H), 5.00 (dd, 1H), 3.46-3.38 (m, 2H), 2.02-1.87 (m, 1H), 1.85-1.73 (m, 1H), 1.62-1.50 (m, 1H), 1.46-1.36 (m, 1H), 1.23 (t, 3H), 0.95 (t, 3H)

[0065] MS(m/z): 313

Reaction 5. Synthesis of 4-(1-ethoxybutyl)naphthalimide trifluoromethane sulfonate

[0066] 4.08 g (13.2 mmol) of N-hydroxy-4-(1-ethoxybutyl) naphthalimide was added to dichloromethane, and 2.64 g (26.0 mmol) of triethylamine was added thereto, and the mixture was stirred for 30 minutes and cooled to 5 C. or lower. After adding 2.19 g (13.2 mmol) of trifluoromethane sulfonyl chloride, the mixture was stirred at room temperature. Then, after adding thereto distilled water and stirring, the organic layer was separated. The separated organic layer was washed twice with distilled water, and the collected organic layer was dried with anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The product obtained by distilling the organic layer under reduced pressure was purified by silica gel column chromatography (developing solvent: ethyl acetate:n-heptane=1:4) to obtain 4.12 g (71.7%) of 4-(1-ethoxybutyl) naphthalimide trifluoromethane sulfonate (1).

[0067] .sup.1H NMR (.sub.ppm; CDCl.sub.3): 8.76 (dd, 1H), 8.71 (dd, 1H), 8.68 (d, 1H), 7.90 (d, 1H), 7.85 (dd, 1H), 5.01 (dd, 1H), 3.49-3.35 (m, 2H), 1.97-1.88 (m, 1H), 1.82-1.74 (m, 1H), 1.62-1.51 (m, 1H), 1.47-1.36 (m, 1H), 1.23 (t, 3H), 0.95 (t, 3H)

[0068] MS(m/z): 445

[0069] The following compounds were prepared in the same manner as in Example 1.

TABLE-US-00001 Com- pound MS No. Structure .sup.1H-NMR (m/z) 1 [00007] 8.76 (dd, 1H), 8.71 (dd, 1H), 8.68 (d, 1H), 7.90 (d, 1H), 7.85 (dd, 1H), 5.01 (dd, 1H), 3.49- 3.35 (m, 2H), 1.97-1.88 (m, 1H), 1.82-1.74 (m, 1H), 1.62-1.51 (m, 1H), 1.47-1.36 (m, 1H), 1.23 (t, 3H), 0.95 (t, 3H) 445 2 [00008] 8.77 (dd, 1H), 8.71 (dd, 1H), 8.68 (d, 1H), 7.94 (d, 1H), 7.85 (dd, 1H), 5.10 (dd, 1H), 3.50- 3.36 (m, 2H), 1.82-1.74 (m, 1H), 1.62-1.51 (m, 1H), 1.23 (t, 3H), 0.95 (t, 3H). 431 3 [00009] 8.76 (dd, 1H), 8.71 (dd, 1H), 8.68 (d, 1H), 7.90 (d, 1H), 7.85 (dd, 1H), 5.01 (dd, 1H), 3.49- 3.35 (m, 2H), 1.97-1.88 (m, 1H), 1.82-1.74 (m, 1H), 1.62-1.51 (m, 1H), 1.47-1.36 (m, 1H), 1.23 (t, 3H), 0.93-0.87 (m, 7H). 473 4 [00010] 8.76 (dd, 1H), 8.71 (dd, 1H), 8.68 (d, 1H), 7.90 (d, 1H), 7.85 (dd, 1H), 5.01 (dd, 1H), 3.49- 3.35 (m, 2H), 1.97-1.88 (m, 1H), 1.82-1.74 (m, 1H), 1.62-1.51 (m, 1H), 1.47-1.36 (m, 1H), 1.23 (t, 3H), 0.93-0.86 (m, 11H). 515 5 [00011] 8.76 (dd, 1H), 8.71 (dd, 1H), 8.68 (d, 1H), 7.90 (d, 1H), 7.85 (dd, 1H), 5.01 (dd, 1H), 3.49- 3.35 (m, 2H), 1.97-1.88 (m, 1H), 1.82-1.74 (m, 1H), 1.62-1.51 (m, 1H), 1.47-1.36 (m, 1H), 1.23 (t, 3H), 0.95 (t, 3H). 595 6 [00012] 8.76 (dd, 1H), 8.71 (dd, 1H), 8.68 (d, 1H), 7.89 (d, 1H), 7.84 (dd, 1H), 4.98 (dd, 1H), 3.39- 3.28 (m, 2H), 1.99-1.87 (m, 1H), 1.83-1.72 (m, 1H), 1.63-1.53 (m, 2H), 1.45-1.33 (m, 2H), 0.95 (t, 3H), 0.89 (t, 3H). 459 7 [00013] 8.76 (dd, 1H), 8.71 (dd, 1H), 8.68 (d, 1H), 7.89 (d, 1H), 7.84 (dd, 1H), 4.98 (dd, 1H), 3.39- 3.28 (m, 2H), 1.82-1.62 (m, 2H), 1.53-1.33 (m, 2H), 0.95 (t, 3H), 0.89 (t, 3H). 445 8 [00014] 8.76 (dd, 1H), 8.71 (dd, 1H), 8.68 (d, 1H), 7.89 (d, 1H), 7.84 (dd, 1H), 4.98 (dd, 1H), 3.39- 3.28 (m, 2H), 1.99-1.87 (m, 1H), 1.83-1.72 (m, 1H), 1.63-1.53 (m, 3H), 1.45-1.33 (m, 3H), 0.95 (t, 3H), 0.89 (t, 3H). 473 9 [00015] 8.76 (dd, 1H), 8.71 (dd, 1H), 8.68 (d, 1H), 7.89 (d, 1H), 7.84 (dd, 1H), 4.98 (dd, 1H), 3.39- 3.28 (m, 2H), 1.97-1.33 (m, 6H), 0.95 (t, 3H), 0.93-0.87 (m, 7H). 487 10 [00016] 8.76 (dd, 1H), 8.71 (dd, 1H), 8.68 (d, 1H), 7.89 (d, 1H), 7.84 (dd, 1H), 4.98 (dd, 1H), 3.39- 3.28 (m, 2H), 1.97-1.33 (m, 6H), 0.95 (t, 3H), 0.93-0.86 (m, 11H). 530 11 [00017] 8.76 (dd, 1H), 8.71 (dd, 1H), 8.68 (d, 1H), 7.90 (d, 1H), 7.85 (dd, 1H), 5.01 (dd, 1H), 3.31(s, 3H), 1.97-1.88 (m, 1H), 1.82- 1.74 (m, 1H), 1.62-1.51 (m, 1H), 1.47-1.36 (m, 1H), 0.95 (t, 3H). 431 12 [00018] 8.77 (dd, 1H), 8.71 (dd, 1H), 8.68 (d, 1H), 7.94 (d, 1H), 7.85 (dd, 1H), 5.10 (dd, 1H), 3.53- 3.46 (m, 1H), 1.94-1.83 (m, 1H), 1.79-1.68 (m, 1H), 1.65-1.55 (m, 1H), 1.48-1.37 (m, 1H), 1.23 (d, 3H), 1.09 (d, 3H), 0.96 (t, 3H). 609 13 [00019] 8.76 (dd, 1H), 8.71 (dd, 1H), 8.68 (d, 1H), 7.90 (d, 1H), 7.85 (dd, 1H), 5.01 (dd, 1H), 3.53- 3.46 (m, 1H), 1.97-1.88 (m, 1H), 1.82-1.74 (m, 1H), 1.62-1.51 (m, 1H), 1.47-1.36 (m, 1H), 1.23 (d, 3H), 1.09 (d, 3H), 0.93-0.87 (m, 7H). 638 14 [00020] 8.77 (dd, 1H), 8.71 (dd, 1H), 8.68 (d, 1H), 7.94 (d, 1H), 7.85 (dd, 1H), 5.10 (dd, 1H), 3.53- 3.46 (m, 1H), 1.94-1.83 (m, 1H), 1.79-1.68 (m, 1H), 1.23 (d, 3H), 1.09 (d, 3H), 0.96 (t, 3H). 445 15 [00021] 8.77 (dd, 1H), 8.71 (dd, 1H), 8.68 (d, 1H), 7.94 (d, 1H), 7.85 (dd, 1H), 5.10 (dd, 1H), 3.53- 3.46 (m, 1H), 1.94-1.83 (m, 1H), 1.79-1.68 (m, 1H), 1.65-1.55 (m, 1H), 1.48-1.37 (m, 1H), 1.23 (d, 3H), 1.09 (d, 3H), 0.96 (t, 3H). 459 16 [00022] 8.76 (dd, 1H), 8.71 (dd, 1H), 8.68 (d, 1H), 7.89 (d, 1H), 7.84 (dd, 1H), 4.98 (dd, 1H), 3.39- 3.28 (m, 2H), 1.63-1.53 (m, 2H), 1.45-1.33 (m, 2H), 1.29(d, 3H), 0.95 (t, 3H). 445 17 [00023] 8.76 (dd, 1H), 8.71 (dd, 1H), 8.68 (d, 1H), 7.89 (d, 1H), 7.84 (dd, 1H), 4.98 (dd, 1H), 3.39- 3.28 (m, 2H), 1.63-1.53 (m, 2H), 1.45-1.33 (m, 2H), 1.29(d, 3H), 0.95 (t, 3H). 595 18 [00024] 8.76 (dd, 1H), 8.71 (dd, 1H), 8.68 (d, 1H), 7.90 (d, 1H), 7.85 (dd, 1H), 5.01 (dd, 1H), 3.49- 3.35 (m, 2H), 1.75-1.60(m, 6H), 1.23 (t, 3H), 1.21-1.18(m, 5H) 485 19 [00025] 8.76 (dd, 1H), 8.71 (dd, 1H), 8.68 (d, 1H), 7.90 (d, 1H), 7.85 (dd, 1H), 5.01 (dd, 1H), 3.60- 3.52 (m, 4H), 3.36 (s, 3H), 1.97- 1.88 (m, 1H), 1.82-1.74 (m, 1H), 1.62-1.51 (m, 1H), 1.47-1.36 (m, 1H), 0.95 (t, 3H). 475 20 [00026] 8.76 (dd, 1H), 8.71 (dd, 1H), 8.68 (d, 1H), 7.90 (d, 1H), 7.85 (dd, 1H), 5.01 (dd, 1H), 3.60- 3.52 (m, 4H), 3.43-3.39 (m, 2H), 1.97-1.88 (m, 1H), 1.82-1.74 (m, 1H), 1.62-1.51 (m, 1H), 1.55- 1.49(m, 2H), 1.47-1.36 (m, 1H), 1.38-1.30(m, 2H), 0.95 (t, 3H), 0.91(t, 3H). 517

Preparation of Binder Resin

a) Preparation of Binder Resin 1

[0070] 200 ml of propylene glycol monomethyl ether acetate (PGMEA) and 1.5 g of azobisisobutyronitrile (AIBN) were added in a 500 ml polymerization vessel, and acetoxy styrene, styrene, and t-butoxymethacrylate were added with a molar ratio of 50:25:25, respectively, so that the solid content might be 40% by weight, and then polymerized with stirring at 70 C. for 5 hours under nitrogen atmosphere to prepare binder resin 1. It was confirmed that the weight average molecular weight of the copolymer prepared as such was 25,000, and the degree of dispersion thereof was 2.0.

b) Preparation of Binder Resin 2

[0071] 200 ml of PGMEA and 1.5 g of AIBN were added in a 500 ml polymerization vessel, and acetoxy styrene, styrene, t-butoxymethacrylate and methyl methacrylate were added with a molar ratio of 40:25:25:10, respectively, so that the solid content might be 40% by weight, and then polymerized with stirring at 70 C. for 5 hours under nitrogen atmosphere to synthesize a copolymer. After adding 0.3 g of N,N-dimethylaniline and 20 molar ratio of glycidyl methacrylate to the reactor, the mixture was stirred at 100 C. for 10 hours to prepare binder resin 2, which was an acrylic polymer having an acrylic unsaturated bond in the side chain. It was confirmed that the weight average molecular weight of the copolymer prepared as such was 20,000, and the degree of dispersion thereof was 2.1.

Measurement of Solubility

[0072] In preparing a photoresist composition, solubility of a photoacid generator is very important. Hence, the solubility in propylene glycol monomethyl ether (PGMEA) and cyclohexane, which are solvents mainly used in photoresist compositions, were compared with those of the compound of the following Formula II, and are shown in Table 1 below.

##STR00027##

TABLE-US-00002 TABLE 1 Solubility of photoacid generators Solubility (w/v %) Compound No. PGMEA Cyclohexane 8 50.0 62.3 12 9.2 25.2 19 60.0 64.1 20 45.0 54.1 Formula II 1.7 5.8

Measurement of Thermal Stability

[0073] If a photoacid generator is thermally stable in a photoresist preparation process, a very good effect in terms of stability can be expected. Hence, the temperature at which 5% weight loss occurred was measured by using a thermogravimetric analyzer to compare with the compound of Formula II.

TABLE-US-00003 TABLE 2 Thermal stability of photoacid generators Compound No. Temperature at which 5% weight loss occurred ( C.) 8 232 11 230 19 234 20 235 Formula V 223

Preparation of Photoresist Compositions of Examples

[0074] In a reaction mixing bath equipped with an ultraviolet blocking film and an agitator, according to the components and contents shown in Table 3 below, binder resin 1 or 2; compound 8, 11, 19 or 20 as photoacid generator; and FC-430 (a leveling agent of 3M, 0.02 weight %) were sequentially added, and the mixture was stirred at room temperature, and then PGMEA as a solvent was added to make 100% by weight, to prepare a photoresist composition.

TABLE-US-00004 TABLE 3 Preparation of photoresist composition Composition Binder resin Photoacid generator Additive No. (parts by weight) (parts by weight) (parts by weight) 1 1 (97) Compound 8 (0.4) FC-430 (0.1) 2 1 (97) Compound 11 (0.4) FC-430 (0.1) 3 1 (97) Compound 19 (0.4) FC-430 (0.1) 4 1 (97) Compound 20 (0.4) FC-430 (0.1) 5 2 (97) Compound 8 (0.4) FC-430 (0.1) 6 2 (97) Compound 11 (0.4) FC-430 (0.1) 7 2 (97) Compound 19 (0.4) FC-430 (0.1) 8 2 (97) Compound 20 (0.4) FC-430 (0.1) 9 1 (60) + 2 (37) Compound 8 (0.4) FC-430 (0.1) 10 1 (37) + 2 (60) Compound 8 (0.4) FC-430 (0.1)

Preparation of Photoresist Composition of Comparative Example

[0075] A photoresist composition was prepared in the same manner as in the preparation of Composition 3, except that the photoacid generator of Formula II was used instead of Compound 19 as the photoacid generator.

##STR00028##

Evaluation of Photoresist Composition

[0076] Evaluation of the photoresist compositions of Examples and Comparative Example was performed on a glass substrate, and pattern stability and taper angle of the photoresist composition were measured, and the evaluation results are shown in Table 4 below.

1) Pattern Stability

[0077] The photoresist was spin-coated on a silicon wafer substrate, dried on a hot plate at 90 C. for 1 minute, exposed with using a line-space (10 m-10 m) step mask, subjected to a post-exposure bake process, and then developed in 2.384% aqueous solution of trimethylammonium hydroxide (TMAH). The width of the pattern in the space portion after the development was measured.

2) Taper Angle

[0078] The photoresist was spin-coated on a silicon wafer substrate, dried on a hot plate at 90 C. for 1 minute, exposed with using a line-space (10 m-10 m) step mask, subjected to a post-exposure bake process, and then developed in 2.384% aqueous solution of TMAH. The taper angle of the space portion after the development was measured, and it was determined as good in case of 85 to 90, and poor in case of less than 85 or greater than 91.

TABLE-US-00005 TABLE 4 Size of space Value compared CD pattern with Comparative Condition of Composition No. (m) Example taper angle 1 12.3 1.06 Good 2 12.1 1.04 Good 3 12.2 1.05 Good 4 12.1 1.04 Good 5 12.0 1.03 Good 6 12.2 1.05 Good 7 12.1 1.04 Good 8 12.0 1.03 Good 9 12.2 1.05 Good 10 12.0 1.03 Good Comparative Example 11.6 1.00 Poor