Pattern-forming method
A pattern-forming method includes applying a radiation-sensitive composition comprising a complex on a substrate to provide a film on the substrate. The film is exposed. The film exposed is developed. The complex includes: a metal-containing component that is a transition metal compound having a hydrolyzable group, a hydrolysis product of the transition metal compound having a hydrolyzable group, a hydrolytic condensation product of the transition metal compound having a hydrolyzable group, or a combination thereof; and an organic compound represented by formula (1). In the formula (1), R 1 represents an organic group having a valency of n, n being an integer of 1 to 4. In a case where n is 1, X represents —COOH. In a case where n is 2 to 4, X represents —OH, —COOH, —NCO, —NHR a , —COOR A or —CO—C(R L ) 2 —CO—R A . R 1 X) n (1)
1. A pattern-forming method comprising:
applying a radiation-sensitive composition comprising a complex on a substrate to provide a film on the substrate;
exposing the film via a mask which has a predetermined pattern; and
developing the film exposed to form a pattern in the film,
wherein the complex is a reaction product from a mixture of:
a metal-containing component that is a transition metal compound having a hydrolyzable group, a hydrolysis product of the transition metal compound having a hydrolyzable group, a hydrolytic condensation product of the transition metal compound having a hydrolyzable group, or a combination thereof, wherein the transition metal compound is represented by formula (2-1); and
an organic compound represented by formula (1):
R 1 X) n (1)
MY b (2-1)
wherein in the formula (1), R 1 represents an alkyl group, an alkanediyl group, an alkanetriyl group, or an alkanetetrayl group,
wherein the alkyl group, the alkanediyl group, the alkanetriyl group, or the alkanetetrayl group represented by R 1 is optionally substituted with a halogen atom, an alkoxy group, an alkoxycarbonyl group, an acyl group, a cyano group or a nitro group,
wherein:
in a case where n is 1, X represents —COOH;
in a case where n is 2 to 4, X represents —COOH, —NCO, —COOR A or —CO—C(R L ) 2 —CO—R A ,
R A each independently representing a monovalent organic group, and
R L each independently representing a hydrogen atom or a monovalent organic group; and
in a case where n is no less than 2, a plurality of Xs are identical or different, and
wherein in the formula (2-1): M represents a transition metal atom; Y represents the hydrolyzable group selected from the group consisting of a halogen atom, an alkoxy group and a carboxylate group; and b is an integer of 2 to 6, wherein a plurality of Ys are identical or different.
2. The pattern-forming method according to claim 1 , wherein the metal-containing component is a metal alkoxide that is neither hydrolyzed nor hydrolytically condensed.
3. The pattern-forming method according to claim 1 , wherein in the formula (1), X represents —COOH, and n is 1.
4. The pattern-forming method according to claim 1 , wherein the radiation-sensitive composition further comprises a radiation-sensitive acid generating agent.
5. The pattern-forming method according to claim 1 , wherein the developing is carried out by using an alkaline solution to form a negative tone pattern.
6. The pattern-forming method according to claim 1 , wherein the developing is carried out by using an organic solvent to form a negative tone pattern.
7. The pattern-forming method according to claim 1 , wherein the exposing is carried out by irradiation with an extreme ultraviolet ray or an electron beam.
8. The pattern-forming method according to claim 1 , wherein the transition metal compound comprises at least one transition metal selected from the groups 4 to 6 and 8 in the periodic table.
9. The pattern-forming method according to claim 1 , wherein the transition metal compound comprises at least one transition metal selected from titanium, zirconium, hafnium, tantalum, tungsten and iron.
10. The pattern-forming method according to claim 1 , wherein the transition metal compound comprises at least one transition metal selected from titanium, zirconium, hafnium and iron.
11. The pattern-forming method according to claim 1 , wherein an amount of the organic compound with respect to 1 mol of a transition metal in the metal-containing compound is from 0.01 to 30 mol %.
12. The pattern-forming method according to claim 1 , wherein an amount of the organic compound with respect to 1 mol of a transition metal in the metal-containing compound is from 0.1 to 20 mol %.
13. The pattern-forming method according to claim 1 , wherein an amount of the organic compound with respect to 1 mol of a transition metal in the metal-containing compound is from 0.1 to 15 mol %.
14. The pattern-forming method according to claim 1 , wherein the radiation-sensitive composition further comprises a solvent.
15. The pattern-forming method according to claim 1 , wherein the radiation-sensitive composition further comprises a surfactant.
16. The pattern-forming method according to claim 1 , wherein a solid content of the radiation-sensitive composition is from 0.1 to 50 mass %.
17. The pattern-forming method according to claim 1 , wherein a solid content of the radiation-sensitive composition is from 0.5 to 30 mass %.
18. The pattern-forming method according to claim 1 , wherein a solid content of the radiation-sensitive composition is from 1 to 20 mass %.
19. The pattern-forming method according to claim 1 , wherein a solid content of the radiation-sensitive composition is from 1.5 to 10 mass %.
20. The pattern-forming method according to claim 1 , wherein in the formula (1), in a case where n is 2, at least one X represents NCO, —COOR A or —CO—C(R L ) 2 —CO—R A .