Water-soluble negative photoresist polymer and composition containing the same

• US 7,399,570 B2
• Filed: 03/31/2005
• Issued: 07/15/2008
• Est. Priority Date: 06/18/2004
• Status: Expired due to Fees

• Current Assignee: Hynix Semiconductor Incorporated (SK Hynix Inc.)
• Original Assignee: Hynix Semiconductor Incorporated (SK Hynix Inc.)
• Inventors: Lee, Geun Su
• Primary Examiner(s): WALKE, AMANDA C
• Application Number:
  US10/999,416
• Publication Number:
  US 20050282080A1
• Time in Patent Office: 1,202 Days
• Field of Search: None
• US Class Current: 430/270.1
• CPC Class Codes: C08F 8/44 Preparation of metal salts or ammonium salts
• CPC Class Codes: G03F 7/0382 the macromolecular compound being present in a chemically amplified negative photoresist composition

Abstract

Photoresist patterns are formed using a photoresist composition, which includes water, a negative photoresist polymer having a salt-type repeating unit, and a photoacid generator, so that a developing process can be performed not by using conventional TMAH solution but by using water. Additionally, because the main solvent of the composition is water, the disclosed photoresist composition is environment-friendly, and has a low light absorbance at 193 nm and 248 nm, which is useful in a photolithography process using a light source in a far ultraviolet region when high-integrated fine circuits of semiconductor device are manufactured.

Claims

1. A photoresist composition comprising a basic compound, water, and a photoacid generator, and a polymer having a repeating unit represented by Formula (IV):

2. The photoresist composition of claim 1, wherein the repeating unit of Formula (IV) is selected from the group consisting of Formulas (IVa) to (IVd):

3. The photoresist composition of claim 1, further comprising a C₁-C₁₀ alcohol.

4. The photoresist composition of claim 3, wherein the C₁-C₁₀ alcohol is selected from the group consisting of 2-propanol, butyl alcohol, 2-methyl-2-butanol, 2-pentanol, 3-pentanol, 1-hexanol, 1-heptanol, and mixtures thereof.

5. The photoresist composition of claim 3, wherein the C₁-C₁₀ alcohol is present in an amount ranging from 1 wt. % to 50 wt. %, based on the weight of water present in the composition.

6. The photoresist composition of claim 1, wherein the photoresist polymer is present in an amount ranging from 2 wt. % to 30 wt. %, based on the weight of water present in the composition.

7. The photoresist composition of claim 1, wherein the basic compound is an amine or ammonium hydroxide.

8. The photoresist composition of claim 1, wherein the basic compound is present in an amount ranging from 0.001 wt. % to 0.1 wt. %, based on the weight of water present in the composition.

9. The photoresist composition of claim 1, wherein the photoacid generator is one or more compounds selected from the group consisting of diphenyl iodide hexafluorophosphate, diphenyl iodide hexafluoroarsenate, diphenyl iodide hexafluoroantimonate, diphenyl p-methoxyphenylsulfonium triflate, diphenyl p-toluenylsulfonium triflate, diphenyl p-isobutylphenylsulfonium triflate, diphenyl p-t-butylphenylsulfonium triflate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium triflate, dibutylnaphthylsulfonium triflate, phthalimidotrifluoromethane sulfonate, dinitrobenzyltosylate, n-decyl disulfone, and naphthylimido trifluoromethane sulfonate.

10. The photoresist composition of claim 1, wherein the photoacid generator is present in an amount ranging from 0,5 wt. % to 10 wt. %, based on the weight of photoresist polymer present in the composition.

11. The photoresist composition of claim 1, wherein the polymer of Formula (IV) is reacted with the basic compound to form a polymer of Formula (I);

23. A method of forming a photoresist pattern, the method comprising:

(a) coating the photoresist composition of claim 1 on an underlying layer of a semiconductor substrate to form a photoresist film;

(b) exposing the photoresist film to light; and

,

(c) developing the exposed photoresist film to obtain a photoresist pattern.

24. The method of claim 23, further comprising baking the photoresist film either before or after the exposing step (b).

25. The method of claim 24, wherein the baking is performed at a temperature ranging from 70°

C. to 200°

C.

26. The method of claim 23, wherein the light is selected from the group consisting of F₂(157 nm), ArF (193 nm), KrF (248 nm), E-beam, EUV (13 nm), and ion beam.

27. The method of claim 23, wherein the exposing step (b) is performed at an exposure energy ranging from 0.1 mJ/cm² to 100 mJ/cm².

12. A photoresist composition comprising a basic compound, water, a photoacid generator, and a polymer having a repeating unit represented by Formula (V):

13. The photoresist composition of claim 12, wherein the repeating unit of Formula (V) is selected from the group consisting of Formulas (Va) to (Vd):

14. The photoresist composition of claim 12, further comprising a C₁-₁₀ alcohol.

15. The photoresist composition of claim 14, wherein the C₁-C₁₀ alcohol is selected from the group consisting of 2-propanol, butyl alcohol, 2-methyl-2-butanol, 2-pentanol, 3-pentanol, 1-hexanol, 1-heptanol, and mixtures thereof.

16. The photoresist composition of claim 14, wherein the C₁-C₁₀ alcohol is present in an amount ranging from 1 wt. % to 50 wt. %, based on the weight of water present in the composition.

17. The photoresist composition of claim 12, wherein the photoresist polymer is present in an amount ranging from 2 wt. % to 30 wt. %, based on the weight of water present in the composition.

18. The photoresist composition of claim 12, wherein the basic compound is an amine or ammonium hydroxide.

19. The photoresist composition of claim 12, wherein the basic compound is present in an amount ranging from 0.001 wt. % to 0.1 wt. %, based on the weight of water present in the composition.

20. The photoresist composition of claim 12, wherein the photoacid generator is one or more compounds selected from the group consisting of diphenyl iodide hexafluorophosphate, diphenyl iodide hexafluoroarsenate, diphenyl iodide hexafluoroantimonate, diphenyl p-methoxyphenylsulfonium triflate, diphenyl p-toluenylsulfonium triflate, diphenyl p-isobutylphenylsulfonium triflate, diphenyl p-t-butylphenylsulfonium triflate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium triflate, dibutylnaphthylsulfonium triflate, phthalimidotrifluoromethane sulfonate, dinitrobenzyltosylate, n-decyl disulfone, and naphthylimido trifluoromethane sulfonate.

21. The photoresist composition of claim 12, wherein the photoacid generator is present in an amount ranging from 0.5 wt. % to 10 wt. %, based on the weight of photoresist polymer present in the composition.

22. The photoresist composition of claim 12, wherein the polymer of Formula (V) is reacted with the basic compound to form a polymer of Formula (III);

28. A method of forming a photoresist pattern, the method comprising:

(a) coating the photoresist composition of claim 12 on an underlying layer of a semiconductor substrate to form a photoresist film;

(b) exposing the photoresist film to light; and

,

(c) developing the exposed photoresist film to obtain a photoresist pattern.

29. The method of claim 28, further comprising baking the photoresist film either before or after the exposing step (b).

30. The method of claim 29, wherein the baking is performed at a temperature ranging from 70°

C. to 200°

C.

31. The method of claim 28, wherein the light is selected from the group consisting of F₂ (157 nm), ArF (193 nm), KrF (248 nm), E-beam, EUV (13 nm), and ion beam.

32. The method of claim 28, wherein the exposing step (b) is performed at an exposure energy ranging from 0.1 mJ/cm² to 100 mJ/cm².