Negative resist pattern-forming method, and composition for upper layer film formation

1. A negative resist pattern-forming method comprising:

applying a radiation-sensitive resin composition on a substrate to form a resist film, the radiation-sensitive resin composition comprising a first polymer component and a radiation-sensitive acid generator;

applying a composition for upper layer film formation on one surface of the resist film to form an upper layer film, the composition for upper layer film formation comprising a second polymer component and a solvent;

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

developing the resist film subjected to the liquid immersion lithography with a developer solution comprising an organic solvent,

wherein the second polymer component comprises:

a third polymer comprising no fluorine atom or silicone atom and comprising a first structural unit that comprises a polycyclic alicyclic structure and that is represented by formula (6-1) or formula (6-2); and

a fourth polymer comprising a second structural unit which comprises a group represented by formula (7), and a third structural unit which comprises a fluorinated alkyl group,

the polycyclic alicyclic structure in the first structural unit is a polycyclic hydrocarbon structure not comprising a hetero atom in the structure thereof, and

a percentage content of the fluorine atom in the second polymer component is no less than 2% by mass and no greater than 30% by mass:

wherein, in the formula (6-1),

R 21 represents a hydrogen atom, or a methyl group;

L represents a single bond or a divalent organic group having 1 to 20 carbon atoms; and

R 22 represents a substituted or unsubstituted monovalent polycyclic alicyclic hydrocarbon group having 3 to 20 ring atoms, and

in the formula (6-2),

R 21′ represents a hydrogen atom or a methyl group;

Y 1 , Y 2 and Y 3 each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms;

a is an integer of 1 to 4, wherein in a case where a is no less than 2, a plurality of Y 1 s are identical or different, and a plurality of Y 2 s are identical or different;

L′ represents a single bond or a divalent organic group having 1 to 20 carbon atoms; and

R 22′ represents a substituted or unsubstituted monovalent polycyclic alicyclic hydrocarbon group having 3 to 20 ring atoms,

wherein, in the formula (7),

R O represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms; and

R P and R Q each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 20 carbon atoms.

2. The negative resist pattern-forming method according to claim 1 , wherein the first polymer component comprises a first polymer that comprises a fluorine atom, and a second polymer that comprises an acid-labile group.

3. The negative resist pattern-forming method according to claim 2 , wherein the composition for upper layer film formation satisfies at least one selected from the group consisting of (i) and (ii):

(i) the composition for upper layer film formation further comprising an acid diffusion inhibiting compound; and

(ii) the second polymer component comprising a structural unit that comprises an acid diffusion-inhibiting group,

wherein the acid diffusion inhibiting compound comprises a compound represented by formula (1), a compound represented by formula (2), a compound represented by formula (3) or a combination thereof, and

wherein the acid diffusion-inhibiting group comprises a group represented by formula (1′), a group represented by formula (2′-1), a group represented by formula (2′-2), a group represented by formula (3′) or a combination thereof,

wherein, in the formula (1),

R A and R B each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, or R A and R B taken together represent an aliphatic heterocyclic structure having 3 to 20 ring atoms together with the nitrogen atom to which R A and R B bond; and

R 1 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, in the formula (2),

X + represents a monovalent onium cation; and

Y − represents a monovalent weak acid anion, in the formula (3),

R 18 , R 19 and R 20 each independently represent a hydrogen atom, or a substituted or unsubstituted linear or branched alkyl group, a substituted or unsubstituted monovalent saturated alicyclic hydrocarbon group, a substituted or unsubstituted monovalent aryl group or a monovalent aralkyl group,

in the formula (1′),

E represents a single bond or a divalent organic group having 1 to 20 carbon atoms;

R J represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms,

wherein R J and E optionally taken together represent an aliphatic heterocyclic structure having 3 to 20 ring atoms together with the nitrogen atom to which R J and E bond; and

R 1 ′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, in the formula (2′-1),

X′ + represents a monovalent group that comprises a monovalent onium cation; and

Y″ − represents a monovalent weak acid anion, in the formula (2′-2),

Y″ − represents a monovalent group that comprises a monovalent weak acid anion; and

X″ + represents a monovalent onium cation, and

in the formula (3′),

E′ represents a single bond or a divalent organic group having 1 to 20 carbon atoms; and

R 28 and R 29 each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms,

wherein any two of R 28 , R 29 and E′ optionally taken together represent an aliphatic heterocyclic structure having 3 to 20 ring atoms together with the nitrogen atom to which the any two of R 28 , R 29 and E′ bond.

4. The negative resist pattern-forming method according to claim 1 , wherein the proportion of the first structural unit with respect to total structural units constituting the second polymer component is no less than 30 mol %.

5. The negative resist pattern-forming method according to claim 4 , wherein the proportion of the first structural unit with respect to the total structural units constituting the second polymer component is no less than 35 mol %.

6. The negative resist pattern-forming method according to claim 1 , wherein a content of the fluorine atom in the composition for upper layer film formation in terms of solid content equivalent is no less than 5% by mass and no greater than 10% by mass.

7. The negative resist pattern-forming method according to claim 1 , wherein the solvent comprises an alcohol solvent, an ether solvent or a combination thereof.

8. The negative resist pattern-forming method according to claim 7 , wherein a total percentage content of the alcohol solvent and the ether solvent in the solvent is no less than 70% by mass.

9. The negative resist pattern-forming method according to claim 1 , wherein a mass ratio of the third polymer to the fourth polymer is no less than 10/90 and no greater than 95/5.

10. The negative resist pattern-forming method according to claim 1 , wherein a proportion of the first structural unit with respect to total structural units constituting the second polymer component is no less than 20 mol % and no greater than 95 mol %.

11. The negative resist pattern-forming method according to claim 1 , wherein the percentage content of the fluorine atom in the second polymer component is no less than 5% by mass and no greater than 10% by mass.

12. A composition for upper layer film formation, comprising:

a polymer component comprising:

a polymer comprising no fluorine atom or silicon atom and comprising a first structural unit that comprises a polycyclic alicyclic structure and that is represented by formula (6-1) or formula (6-2); and

a polymer comprising a second structural unit that comprises a group represented by formula (7), and a third structural unit that comprises a fluorinated alkyl group; and

a solvent,

wherein the polycyclic alicyclic structure is a polycyclic structure not comprising a hetero atom in the structure thereof, and a percentage content of the fluorine atom in the polymer component is no less than 2% by mass and no greater than 30% by mass:

wherein, in the formula (6-1),

R 21 represents a hydrogen atom, or a methyl group;

L represents a single bond or a divalent organic group having 1 to 20 carbon atoms; and

R 22 represents a substituted or unsubstituted monovalent polycyclic alicyclic hydrocarbon group having 3 to 20 ring atoms, and

in the formula (6-2),

R 21′ represents a hydrogen atom or a methyl group;

Y 1 , Y 2 and Y 3 each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms;

a is an integer of 1 to 4, wherein in a case where a is no less than 2, a plurality of Y 1 s are identical or different, and a plurality of Y 2 s are identical or different;

L′ represents a single bond or a divalent organic group having 1 to 20 carbon atoms; and

R 22′ represents a substituted or unsubstituted monovalent polycyclic alicyclic hydrocarbon group having 3 to 20 ring atoms,

wherein, in the formula (7),

R O represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms; and

R P and R Q each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 20 carbon atoms.

13. The composition for upper layer film formation according to claim 12 , wherein the percentage content of the fluorine atom in the polymer component is no less than 5% by mass and no greater than 10% by mass.

14. The composition for upper layer film formation according to claim 12 , wherein the composition for upper layer film formation satisfies at least one selected from the group consisting of (i′) and (ii′):

(i′) the composition for upper layer film formation further comprising an acid diffusion inhibiting compound; and

(ii′) the polymer component comprising a structural unit that comprises an acid diffusion-inhibiting group,

wherein the acid diffusion inhibiting compound comprises a compound represented by formula (1), a compound represented by formula (2), a compound represented by formula (3) or a combination thereof, and

wherein the acid diffusion-inhibiting group comprises a group represented by formula (1′), a group represented by formula (2′-1), a group represented by formula (2′-2), a group represented by formula (3′) or a combination thereof,

wherein, in the formula (1),

R A and R B each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, or R A and R B taken together represent an aliphatic heterocyclic structure having 3 to 20 ring atoms together with the nitrogen atom to which R A and R B bond; and

R 1 represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, in the formula (2),

X + represents a monovalent onium cation; and

Y − represents a monovalent weak acid anion,

in the formula (3),

R 18 , R 19 and R 20 each independently represent a hydrogen atom, or a substituted or unsubstituted linear or branched alkyl group, a monovalent saturated alicyclic hydrocarbon group, a monovalent aryl group or a monovalent aralkyl group,

in the formula (1′),

E represents a single bond or a divalent organic group having 1 to 20 carbon atoms;

R J represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms,

wherein R J and E optionally taken together represent an aliphatic heterocyclic structure having 3 to 20 ring atoms together with the nitrogen atom to which R J and E bond; and

R 1′ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, in the formula (2′-1),

X′ + represents a monovalent group that comprises a monovalent onium cation; and

Y″ − represents a monovalent weak acid anion, in the formula (2′-2),

Y″ − represents a monovalent group that comprises a monovalent weak acid anion; and

X″ + represents a monovalent onium cation, and

in the formula (3′),

E′ represents a single bond or a divalent organic group having 1 to 20 carbon atoms;

R 28 and R 29 each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms,

wherein any two of R 28 , R 29 and E′ optionally taken together represent an aliphatic heterocyclic structure having 3 to 20 ring atoms together with the nitrogen atom to which the any two of R 28 , R 29 and E′ bond.

15. The negative resist pattern-forming method according to claim 1 , wherein the second structural unit is represented by formula (7-a) or formula (7-b):

wherein in the above formula (7-a), R D represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; R E represents a divalent linking group; and R x represents the group represented by formula (7), and

in the above formula (7-b), R Y represents the group represented by formula (7); R F represents a single bond or a divalent linking group; and R G represents a hydrogen atom or a monovalent organic group.

16. The composition for upper layer film formation according to claim 12 , wherein the second structural unit is represented by formula (7-a) or formula (7-b):

wherein in the above formula (7-a), R D represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group; R E represents a divalent linking group; and R X represents the group represented by formula (7), and

in the above formula (7-b), R Y represents the group represented by formula (7); R F represents a single bond or a divalent linking group; and R G represents a hydrogen atom or a monovalent organic group.