Composition for forming underlayer and method for forming underlayer therewith
View Patent ↗[Problem] To provide a composition for an underlayer, which can form an underlayer having flattened surface. [Means for Solution] A composition for forming an underlayer, comprising a polymer having a repeating unit containing nitrogen and a solvent. An underlayer is formed by coating this composition on a substrate, preferably baking in an inert atmosphere, and then baking in the air containing oxygen.
1. A method for forming an underlayer, comprising:
a coating step, wherein a coating layer is formed by coating a substrate with a composition for forming an underlayer comprising:
a polymer having a repeating unit selected from the following formulae (1) to (4):
wherein
A1, A2 and A2′ are independently selected from the group consisting of phenylene group and naphthylene group,
A3 and A4 are independently an aromatic group, or a saturated or unsaturated aliphatic hydrocarbon group,
where said aromatic group or aliphatic hydrocarbon group may be substituted by a substituent selected from the group consisting of hydroxy group, alkyl group, aryl group, alkoxy group, nitro group, amide group, dialkylamino group, sulfonamide group, imide group, carboxy group, sulfonic acid ester group, alkylamino group and arylamino group,
L1, L2, L3 and L3′ are independently selected from the following formulae (a1) to (a3):
wherein
Z1 is selected from the group consisting of hydrogen, phenyl group and naphthyl group,
Z2 is selected from the group consisting of hydrogen, hydroxy group, alkyl group, aryl group, alkoxy group, nitro group, amide group, dialkylamino group, sulfonamide group, imide group, carboxy group, sulfonic acid ester group, alkylamino group and arylamino group,
L4 is selected from the group consisting of amino group and carbamoyl group, and substituted aromatic group and substituted aliphatic group having the amino group and carbamoyl group as substituent, and
a solvent, and wherein the content ratio of said polymer is 0.2 to 20 mass % based on the total weigh mass of said composition,
a pre-baking step in an inert gas atmosphere, and a baking step, wherein an underlayer is formed by baking said coating layer in the existence of oxygen,
and a surface layer removing step between said coating step and said baking step, wherein said coating layer is brought into contact with a solvent capable of solubilizing said polymer and the surface layer of the coating layer is dissolved and removed.
2. The method according to claim 1 , wherein heating temperature at said baking step is 200 to 800° C. and baking time is 0.3 to 120 minutes.
3. The method according to claim 1 , wherein the content ratio of oxygen in said inert gas atmosphere is 3 mol % or less.
4. The method according to claim 1 , wherein said A 4 is selected from the group consisting of saturated hydrocarbon group of 1 to 6 carbon atoms and unsaturated hydrocarbon group of 2 to 6 carbon atoms, and said L 4 is selected from the group consisting of substituted or unsubstituted amino group, and substituted or unsubstituted carbamoyl group.
5. The method according to claim 1 , wherein said A 3 is selected from the group consisting of saturated hydrocarbon group of 1 to 12 carbons and unsaturated hydrocarbon group of 2 to 12 carbons.
6. The method according to claim 1 , wherein said polymer has a mass-average molecular weight of 1,000 to 1,000,000.
7. A pattern formation method, comprising:
a coating step, wherein a coating layer is formed by coating a substrate with a composition for forming an underlayer comprising:
a polymer having a repeating unit selected from the following formulae (1) to (4):
wherein
A1, A2 and A2′ are independently selected from the group consisting of phenylene group and naphthylene group,
A3 and A4 are independently an aromatic group, or a saturated or unsaturated aliphatic hydrocarbon group,
where said aromatic group or aliphatic hydrocarbon group may be substituted by a substituent selected from the group consisting of hydroxy group, alkyl group, aryl group, alkoxy group, nitro group, amide group, dialkylamino group, sulfonamide group, imide group, carboxy group, sulfonic acid ester group, alkylamino group and arylamino group,
L1, L2, L3 and L3′ are independently selected from the following formulae (a1) to (a3):
wherein
Z1 is selected from the group consisting of hydrogen, phenyl group and naphthyl group,
Z2 is selected from the group consisting of hydrogen, hydroxy group, alkyl group, aryl group, alkoxy group, nitro group, amide group, dialkylamino group, sulfonamide group, imide group, carboxy group, sulfonic acid ester group, alkylamino group and arylamino group,
L4 is selected from the group consisting of amino group and carbamoyl group, and substituted aromatic group and substituted aliphatic group having the amino group and carbamoyl group as substituent, and
a solvent, and wherein the content ratio of said polymer is 0.2 to 20 mass % based on the total weigh mass of said composition,
a baking step, wherein an underlayer is formed by baking said coating layer in the existence of oxygen,
a resist layer forming step, wherein a photoresist layer is formed on said underlayer,
an exposure step, wherein said substrate coated with said underlayer and said photoresist layer is exposed, and
a developing step, wherein the exposed substrate is developed with a developing solution.
8. The method according to claim 7 , wherein said A 4 is selected from the group consisting of saturated hydrocarbon group of 1 to 6 carbon atoms and unsaturated hydrocarbon group of 2 to 6 carbon atoms, and said L 4 is selected from the group consisting of substituted or unsubstituted amino group, and substituted or unsubstituted carbamoyl group.
9. The method according to claim 7 , wherein said A 3 is selected from the group consisting of saturated hydrocarbon group of 1 to 12 carbons and unsaturated hydrocarbon group of 2 to 12 carbons.
10. The method according to claim 7 , wherein said polymer has a mass-average molecular weight of 1,000 to 1,000,000.
11. The method according to claim 7 , wherein said exposure is achieved by the ArF laser.
12. The method according to claim 7 , wherein said substrate has a groove with the width of 1 to 1,000 nm and the depth of 20 to 1,000 nm on the surface.
13. The method according to claim 7 , wherein heating temperature at said baking step is 200 to 800° C. and baking time is 0.3 to 120 minutes.
14. The method according to claim 7 , wherein the method comprises a pre-baking step in an inert gas atmosphere, and the content ratio of oxygen in said inert gas atmosphere is 3 mol % or less.