Chemically amplified positive resist composition

• US 5,876,900 A
• Filed: 04/01/1997
• Issued: 03/02/1999
• Est. Priority Date: 04/02/1996
• Status: Expired due to Term

• Current Assignee: Shin-Etsu Chemical Company Limited
• Original Assignee: Shin-Etsu Chemical Company Limited
• Inventors: Watanabe, Satoshi, Ishihara, Toshinobu, Yamaoka, Tsuguo, Nagura, Shigehiro
• Primary Examiner(s): CHU, JOHN S Y
• Application Number:
  US08/831,300
• Time in Patent Office: 700 Days
• Field of Search: 430/270.1, 430/288.1, 430/905
• US Class Current: 430/288.1
• CPC Class Codes: G03F 7/0045 with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
• CPC Class Codes: G03F 7/0392 the macromolecular compound being present in a chemically amplified positive photoresist composition
• CPC Class Codes: Y10S 430/106 Binder containing

Abstract

A chemically amplified positive resist composition contains (A) an organic solvent, (B) a base resin in the form of a polyhydroxystyrene having phenolic hydroxyl groups some of which are protected with alkoxyalkyl groups and having a weight-average molecular weight of 3,000-300,000 and a dispersity of 1.0 to 1.5, (C) a photoacid generator, and (D) a vinyl ether group-containing compound. The composition is sensitive to actinic radiation, especially KrF excimer laser beam, has high sensitivity and resolution, and forms a resist pattern having improved plasma etching resistance and heat resistance.

Claims

1. A chemically amplified positive resist composition comprising

(A) an organic solvent,

(B) a base resin in the form of a polymer having recurring units of the following general formula (1), and having a weight-average molecular weight of 3,000 to 300,000, ##STR10## wherein R¹ is a hydrogen atom or methyl group, R² is a group represented by the following general formula (2):

##STR11## wherein R⁴ and R⁵ are independently a hydrogen atom or a normal or branched alkyl group having 1 to 6 carbon atoms, R⁶ is a normal, branched or cyclic alkyl group having 1 to 10 carbon atoms, or R⁴ and R⁵, R⁴ and R⁶, or R⁵ and R⁶, taken together, may form a ring wherein R⁴, R⁵ and R⁶ are independently a normal or branched alkylene group having 1 to 6 carbon atoms,

R³ is an acid labile group different from R², and

letters x and y are 0 or a positive number, x and y are not equal to 0 at the same time, and z is a positive number, x, y and z satisfy 0≦

x/(x+y+z)≦

0.5, 0≦

y/(x+y+z)≦

0.5, 0.4≦

z/(x+y+z)≦

0.9, and x+y+z=1,

(C) a photoacid generator, and

(D) a compound having at least two vinyl ether groups in a molecule.

2. A chemically amplified positive resist composition comprising

(A) an organic solvent,

(B) a base resin in the form of a polymer of formula (1) as set forth in claim 1,

(C) a photoacid generator,

(D) a compound having at least two vinyl ether groups in a molecule, and

(E) a dissolution rate regulator.

3. The chemically amplified positive resist composition of claim 2 wherein said dissolution rate regulator (E) is a compound having a molecular weight of 100 to 1,000 and at least two phenolic hydroxyl groups in a molecule, the hydrogen atom of the phenolic hydroxyl group being replaced by an acid labile group in an average proportion of 10 to 100% of the entire phenolic hydroxyl groups.

4. The chemically amplified positive resist composition of claim 2 wherein said dissolution rate regulator (E) is a compound having a molecular weight of more than 1,000 to 3,000 and at least two phenolic hydroxyl groups in a molecule, the hydrogen atom of the phenolic hydroxyl group being partially replaced by an acid labile group in an average proportion of more than 0% to 60% of the entire phenolic hydroxyl groups.

5. The chemically amplified positive resist composition of claim 1 wherein said base resin (B) is a polymer having recurring units of the following general formula (3), and having a weight-average molecular weight of 3,000 to 300,000, ##STR12## wherein R¹, R², x, y, and z are as defined above.

6. The chemically amplified positive resist composition of claim 1 wherein the polymer as base resin (B) is a monodisperse polymer having a dispersity of 1.0 to 1.5.

7. The chemically amplified positive resist composition of claim 1 further comprising (F) a basic compound.

8. The chemically amplified positive resist composition of claim 1 wherein said photoacid generator (C) is an onium salt.

9. The chemically amplified positive resist composition of claim 2 wherein said base resin (B) is a polymer having recurring units of the following general formula (3), and having a weight-average molecular weight of 3,000 to 300,000, ##STR13## wherein R¹, R², x, y and z are as defined above.

10. The chemically amplified positive resist composition of claim 2 wherein the polymer as base resin (B) is a monodisperse polymer having a dispersity of 1.0 to 1.5.

11. The chemically amplified positive resist composition of claim 2 further comprising (F) a basic compound.

12. The chemically amplified positive resist composition of claim 2 wherein said photoacid generator (C) is an onium salt.

13. The chemically amplified positive resist composition of claim 1 wherein y is a positive number and R³ is tert-butyl, tert-butoxycarbonyl, tert-butoxycarbonylmethyl, or 3-oxycyclohexyl.

14. The chemically amplified positive resist composition of claim 2 wherein y is a positive number and R³ is tert-butyl, tert-butoxycarbonyl, tert-butoxycarbonylmethyl, or 3-oxycyclohexyl.

15. The chemically amplified positive resist composition of claim 1 wherein x is a positive number satisfying 0.1≦

x/(x+y+z)≦

0.4.

16. The chemically amplified positive resist composition of claim 2 wherein x is a positive number satisfying 0.1≦

x/(x+y+z)≦

0.4.

17. The chemically amplified positive resist composition of claim 1 wherein x is a positive number satisfying 0.1≦

x/(x+y+z)≦

0.4, and y is a positive number.

18. The chemically amplified positive resist composition of claim 2 wherein x is a positive number satisfying 0.1≦

x/(x+y+z)≦

0.4, and y is a positive number.

19. The chemically amplified positive resist composition of claim 17 wherein R³ is tert-butyl, tert-butoxycarbonyl, tert-butoxycarbonylmethyl, or 3-oxycyclohexyl.

20. The chemically amplified positive resist composition of claim 1, which contains about 150 to 700 parts by weight of the organic solvent, (A), 70 to 90 parts of the base resin, (B), 0.5 to 15 parts by weight of the photoacid generator, (C), and 0.5 to 24 parts by weight of the compound having at least two vinyl ether groups in a molecule, (D).

21. The chemically amplified positive resist composition of claim 2, which contains about 150 to 700 parts by weight of the organic solvent, (A), 70 to 90 parts of the base resin, (B), 0.5 to 15 parts by weight of the photoacid generator, (C), 0.5 to 24 parts by weight of the compound having at least two vinyl ether groups in a molecule, (D), and 6 to 30 parts by weight of the dissolution rate regulator, (E).

22. The chemically amplified positive resist composition of claim 1, wherein the organic solvent is 1-ethoxy-2-propanol, propylene glycol monomethyl ether acetate or a mixture thereof.

23. The chemically amplified positive resist composition of claim 1, wherein the organic solvent is 1-ethoxy-2-propanol, propylene glycol monomethyl ether acetate or a mixture thereof.

24. The chemically amplified positive resist composition of claim 1, wherein the polymer of formula (1) has a weight-average molecular weight of 5,000 to 30,000.

25. The chemically amplified positive resist composition of claim 2, wherein the polymer of formula (1) has a weight-average molecular weight of 5,000 to 30,000.

26. The chemically amplified positive resist composition of claim 1, wherein the compound having at least two vinyl ether groups in a molecule is a vinyl ether compound of one of the following formulae (I) and (II),

27. The chemically amplified positive resist composition of claim 2, wherein the compound having at least two vinyl ether groups in a molecule is a vinyl ether compound of one of the following formulae (I) and (II),

28. The chemically amplified positive resist composition of claim 1, wherein R³ is tert-butyl, tert-butoxycarbonyl, tert-butoxycarbonylmethyl, 3-oxycyclohexyl or a group of the formula (2), different from R² when present.

29. The chemically amplified positive resist composition of claim 2, wherein R³ is tert-butyl, tert-butoxycarbonyl, tert-butoxycarbonylmethyl, 3-oxycyclohexyl or a group of the formula (2), different from R² when present.