Production method of composition for resist top coat layer, method of forming resist pattern, production method of fluorine-containing resin, and method of improving water repellency of resist top coat layer

1. A method for producing a composition for resist top coat layer, comprising:

polymerizing a monomer solution comprising a fluorine-containing monomer in a presence of a polymerization initiator that cleaves to generate an active species having 7 or more carbon atoms in total to obtain a fluorine-containing resin A; and

mixing the fluorine-containing resin A, a resin B having a fluorine atom mass content lower than a fluorine atom mass content of the fluorine-containing resin A, and a solvent,

wherein the polymerization initiator has an alicyclic structure having 3 to 12 carbon atoms, and

wherein the monomer solution comprises:

a first fluorine-containing monomer represented by formula (2-a); and

a second fluorine-containing monomer having a partial structure represented by formula (3) and having a fluorine atom mass content higher than a fluorine atom mass content of the first fluorine-containing monomer:

wherein in the formula (2-a), R Y is a partial structure represented by formula (2), R FA is a single bond or a divalent linking group, and R G is a hydrogen atom or a monovalent organic group,

in the formula (3), R f is a fluorine atom or a fluoroalkyl group having 1 to 3 carbon atoms R 2 and R 3 are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, or a fluoroalkyl group having 1 to 3 carbon atoms, and * is a binding site for another portion,

wherein R f is as defined in the formula (3), R 1 is a hydrogen atom, a fluorine atom, an alkyl group having 1 to 3 carbon atoms, or a fluoroalkyl group having 1 to 3 carbon atoms, and * is a binding site for R FA .

2. The method for producing a composition for resist top coat layer according to claim 1 , wherein the alicyclic structure is represented by formula (1):

wherein R X is a cyano group or an alkoxycarbonyl group having 2 to 8 carbon atoms, n is an integer of 0 to 8, δ is an integer of 0 to (2n+5), * is a binding site for another portion, and when two or more R X s are present, the R X s are the same or different from each other.

3. The method for producing a composition for resist top coat layer according to claim 1 , wherein the alicyclic structure is represented by formula (1-1):

wherein R x is a cyano group or an alkoxycarbonyl group having 2 to 8 carbon atoms, n is an integer of 2 to 6, and * is a binding site for another portion.

4. The method for producing a composition for resist top coat layer according to claim 1 , wherein the polymerization initiator is at least one selected from the group consisting of an azo compound and an organic peroxide.

5. The method for producing a composition for resist top coat layer according to claim 1 , wherein when the fluorine-containing resin A, the resin B, and the solvent are mixed, a resin C is further added, the resin C being different from the fluorine-containing resin A and the resin B and comprising at least one selected from the group consisting of a sulfo group and a carboxyl group.

6. The method for producing a composition for resist top coat layer according to claim 1 , wherein the solvent is at least one selected from the group consisting of a monovalent aliphatic alcohol having 3 to 8 carbon atoms, a dialkyl ether having 6 to 12 carbon atoms, a monoalkyl ether of a monoalkylene glycol having 2 to 4 carbon atoms, a monoalkyl ether monocarboxylate of a monoalkylene glycol having 2 to 4 carbon atoms, a monoalkyl ether of a dialkylene glycol having 4 to 8 carbon atoms, and a monoalkyl ether monocarboxylate of a dialkylene glycol having 4 to 8 carbon atoms.

7. The method for producing a composition for resist top coat layer according to claim 6 , wherein the solvent comprises:

at least one selected from the group consisting of a monovalent aliphatic alcohol having 3 to 8 carbon atoms and a dialkyl ether having 6 to 12 carbon atoms; and

at least one selected from the group consisting of a monoalkyl ether of a monoalkylene glycol having 2 to 4 carbon atoms and a monoalkyl ether of a dialkylene glycol having 4 to 8 carbon atoms.

8. A method for forming a resist pattern comprising:

applying a composition for resist top coat layer onto a resist film to form a liquid immersion top coat layer;

subjecting the resist film having the liquid immersion top coat layer formed thereon to liquid immersion lithography; and

developing the resist film subjected to liquid immersion lithography,

wherein the composition for resist top coat layer is produced by the method for producing a composition for resist top coat layer according to claim 1 .

9. The method for forming a resist pattern according to claim 8 , wherein the alicyclic structure is represented by formula (1):

wherein R X is a cyano group or an alkoxycarbonyl group having 2 to 8 carbon atoms, n is an integer of 0 to 8, δ is an integer of 0 to (2n+5), * is a binding site for another portion, and when two or more R X s are present, the R X s are the same or different from each other.

10. The method for forming a resist pattern according to claim 8 , wherein the alicyclic structure is represented by formula (1-1):

wherein R x is a cyano group or an alkoxycarbonyl group having 2 to 8 carbon atoms, n is an integer of 2 to 6, and * is a binding site for another portion.

11. The method for forming a resist pattern according to claim 8 , wherein when the fluorine-containing resin A, the resin B, and the solvent are mixed, a resin C is further added, the resin C being different from the fluorine-containing resin A and the resin B and comprising at least one selected from the group consisting of a sulfo group and a carboxyl group.

12. A method for improving water-repellency of a resist top coat layer, comprising:

applying a composition for resist top coat layer onto a resist film to form a liquid immersion top coat layer,

wherein the composition for resist top coat layer is produced by the method for producing a composition for resist top coat layer according to claim 1 .

13. The method for improving water-repellency of a resist top coat layer according to claim 12 , wherein a dynamic receding contact angle of water on the liquid immersion top coat layer is 82° or more.

14. The method for improving water-repellency of a resist top coat layer according to claim 12 , wherein the alicyclic structure is represented by formula (1):

wherein R X is a cyano group or an alkoxycarbonyl group having 2 to 8 carbon atoms, n is an integer of 0 to 8, δ is an integer of 0 to (2n+5), * is a binding site for another portion, and when two or more R X s are present, the R X s are the same or different from each other.

15. The method for improving water-repellency of a resist top coat layer according to claim 12 , wherein the alicyclic structure is represented by formula (1-1):

wherein R x is a cyano group or an alkoxycarbonyl group having 2 to 8 carbon atoms, n is an integer of 2 to 6, and * is a binding site for another portion.

16. The method for improving water-repellency of a resist top coat layer according to claim 12 , wherein when the fluorine-containing resin A, the resin B, and the solvent are mixed, a resin C is further added, the resin C being different from the fluorine-containing resin A and the resin B and comprising at least one selected from the group consisting of a sulfo group and a carboxyl group.