Pattern-forming method
A pattern-forming method includes applying a radiation-sensitive composition on a substrate to provide a film on the substrate. The film is exposed. The film exposed is developed. The radiation-sensitive composition includes a metal-containing component that is a metal compound having a hydrolyzable group, a hydrolysis product of the metal compound having a hydrolyzable group, a hydrolytic condensation product of the metal compound having a hydrolyzable group, or a combination thereof. A content of a transition metal atom in the metal-containing component with respect to total metal atoms in the metal-containing component is no less than 50 atomic %.
1. A pattern-forming method comprising:
applying a radiation-sensitive composition 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 radiation-sensitive composition comprises a metal-containing component that is a metal compound having a hydrolyzable group, a hydrolysis product of the metal compound having a hydrolyzable group, a hydrolytic condensation product of the metal compound having a hydrolyzable group, or a combination thereof;
a content of a transition metal atom in the metal-containing component with respect to total metal atoms in the metal-containing component is no less than 50 atomic %; and
the metal compound having a hydrolyzable group comprises a compound represented by formula (1):
L a MX b (1)
wherein in the formula (1),
M represents a transition metal atom,
L represents a ligand, and a is 1 or 2, wherein in a case where a is 2, a plurality of Ls are identical or different, and
X represents a hydrolyzable group selected from a halogen atom, an alkoxy group and a carboxylate group, and b is an integer of 2 to 6, wherein in a case where b is no less than 2, a plurality of Xs are identical or different, wherein the ligand represented by L does not fall under the definition of X.
2. The pattern-forming method according to claim 1 , wherein L represents a monocarboxylic acid having no less than 6 carbon atoms, a hydroxy acid ester, a β-diketone, a β-ketoester, a hydrocarbon having a π bond, a phosphine, or a combination thereof.
3. The pattern-forming method according to claim 1 , wherein the carboxylate group represented by X is a formate group or an alkylcarbonyloxy group having no greater than 5 carbon atoms.
4. 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.
5. 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.
6. The pattern-forming method according to claim 1 , wherein the transition metal atom represented by M is at least one atom selected from the group consisting of a Group 4 element, a Group 5 element, a Group 6 element, a Group 8 element, a Group 9 element, and a Group 10 element.
7. The pattern-forming method according to claim 1 , wherein the transition metal atom represented by M is at least one atom selected from the group consisting of zirconium, titanium, hafnium, tungsten, ruthenium and cobalt.
8. The pattern-forming method according to claim 1 , wherein the transition metal atom represented by M is at least one atom selected from the group consisting of zirconium and titanium.
9. The pattern-forming method according to claim 1 , wherein the ligand represented by L is at least one selected from the group consisting of a lactic acid ester, acetylacetone, an acetoacetic acid ester, a malonic acid diester, a cyclic diene, a phosphine, and a carboxylate anion.
10. The pattern-forming method according to claim 1 , wherein the ligand represented by L is acetylacetone.
11. The pattern-forming method according to claim 1 , wherein the hydrolyzable group represented by X is at least one selected from the group consisting of a chlorine atom, an isopropoxy group, a butoxy group, a formate group, an alkylcarbonyloxy group having no greater than 5 carbon atoms, and a (meth)acrylate group.
12. The pattern-forming method according to claim 1 , wherein b in the formula (1) is an integer of from 2 to 4.
13. The pattern-forming method according to claim 1 , wherein b in the formula (1) is an integer of 2 or 3.
14. The pattern-forming method according to claim 1 , wherein b in the formula (1) is an integer of 2.
15. The pattern-forming method according to claim 1 , wherein the metal compound having a hydrolyzable group comprises at least one selected from the group consisting of zirconium(IV) di-n-butoxide bis(2,4-pentanedionate), titanium(IV) tri-n-butoxide stearate, bis(cyclopentadienyl)hafnium(IV) dichloride, bis(2,4-pentanedionato)dimethacryloyloxyhafnium, bis(cyclopentadienyl)tungsten(IV) dichloride, diacetato[(S)-(−)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl]ruthenium(II), and dichloro[ethylenebis[diphenylphosphine]]cobalt.
16. A pattern-forming method comprising:
applying a radiation-sensitive composition 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 radiation-sensitive composition comprises a metal-containing component that is a metal compound having a hydrolyzable group, a hydrolysis product of the metal compound having a hydrolyzable group, a hydrolytic condensation product of the metal compound having a hydrolyzable group, or a combination thereof;
a content of a transition metal atom in the metal-containing component with respect to total metal atoms in the metal-containing component is no less than 50 atomic %; and
the exposing is carried out by irradiation with an extreme ultraviolet ray.
17. The pattern-forming method according to claim 16 , wherein the metal compound having a hydrolyzable group comprises a compound represented by formula (1):
L a MX b (1)
wherein in the formula (1),
M represents a transition metal atom,
L represents a ligand, and a is 1 or 2, wherein in a case where a is 2, a plurality of Ls are identical or different, and
X represents a hydrolyzable group selected from a halogen atom, an alkoxy group and a carboxylate group, and b is an integer of 2 to 6, wherein in a case where b is no less than 2, a plurality of Xs are identical or different, wherein
the ligand represented by L does not fall under the definition of X.
18. The pattern-forming method according to claim 17 , wherein L represents a monocarboxylic acid having no less than 6 carbon atoms, a hydroxy acid ester, a β-diketone, a β-ketoester, a hydrocarbon having a π bond, a phosphine, or a combination thereof.
19. The pattern-forming method according to claim 17 , wherein the carboxylate group represented by X is a formate group or an alkylcarbonyloxy group having no greater than 5 carbon atoms.
20. The pattern-forming method according to claim 16 , wherein the developing is carried out by using an alkaline solution to form a negative tone pattern.
21. The pattern-forming method according to claim 1 , wherein the metal compound consists of a hydrolytic condensation product of a transition metal compound.
22. The pattern-forming method according to claim 16 , wherein the metal compound consists of a hydrolytic condensation product of a transition metal compound.