Resist pattern-forming method and photoresist composition

1. A resist pattern-forming method comprising:

forming a resist film which is made from a photoresist composition;

exposing the resist film; and

developing the exposed resist film using a developer which comprises an organic solvent to form a negative-tone resist pattern,

the photoresist composition comprising:

an acid generator capable of generating a protonic acid that generates a proton, upon application of exposure light;

a polymer which comprises structural unit comprising a cationic-group-forming group capable of forming a cationic group with the proton generated from the protonic acid; and

a solvent,

wherein the polymer substantially does not comprise a structural unit which comprises an acid-labile group,

the polymer does not comprise a fluorine atom or a silicon atom, and

a content of the structural unit comprising the cationic-group-forming group in the polymer is at least 15 mol % based on total structural units included in the polymer.

2. The resist pattern-forming method according to claim 1 , wherein the cationic-group-forming group comprises a nitrogen atom having an unshared electron pair, a phosphorus atom having an unshared electron pair, or both thereof.

3. The resist pattern-forming method according to claim 1 , wherein the cationic-group-forming group is at least one group selected from a group consisting of a group represented by formula (a-1), a group represented by formula (a-2), and a group represented by formula (a-3),

wherein

each Z is independently a nitrogen atom or a phosphorus atom;

R and R′ are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, or R and R′ taken together represent a cyclic structure together with Z to which R and R′ are bonded; and

R″ is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.

4. The resist pattern-forming method according to claim 3 , wherein the group represented by the formula (a-1) is at least one group selected from a group consisting of a group represented by formula (a-1-1), a group represented by formula (a-1-2), a group represented by formula (a-1-3), a group represented by formula (a-1-4), a group represented by formula (a-1-5), and a group represented by formula (a-1-6), and the group represented by the formula (a-2) is a group represented by formula (a-2-1),

wherein

each Z is independently a nitrogen atom or a phosphorus atom;

in the formula (a-1-1), R a and R β are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R α and R β taken together represent a cyclic structure together with an atom represented by Z;

in the formula (a-1-2), R α1 and R β are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R α1 and R β taken together represent a cyclic structure together with an atom represented by Z and —CH 2 —O—;

in the formula (a-1-3), R γ is a divalent hydrocarbon group having 1 to 20 carbon atoms or a divalent oxyhydrocarbon group having 1 to 20 carbon atoms;

in the formula (a-1-4), R β is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and R α2 and R α3 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R α2 and R α3 taken together represent a cyclic structure together with the carbon atom bonded to R α2 and R α3 ;

in the formula (a-1-5), R β is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and R δ is a group which forms a substituted or unsubstituted monovalent aromatic heterocyclic group having 3 to 20 carbon atoms together with an atom represented by Z;

in the formula (a-1-6), R β is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and R α4 is a monovalent hydrocarbon group having 1 to 20 carbon atoms;

in the formula (a-2-1), R ε is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.

5. The resist pattern-forming method according to claim 3 , wherein the group represented by the formula (a-1) is at least one group selected from a group consisting of a group represented by formula (a-1-1), a group represented by formula (a-1-2), a group represented by formula (a-1-4), a group represented by formula (a-1-5), and a group represented by formula (a-1-6), and the group represented by the formula (a-2) is a group represented by formula (a-2-1),

wherein

each Z is independently a nitrogen atom or a phosphorus atom;

in the formula (a-1-1), R α and R β are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R α and R β taken together represent a cyclic structure together with an atom represented by Z;

in the formula (a-1-2), R α1 and R β are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R α1 and R β taken together represent a cyclic structure together with an atom represented by Z and —CH 2 —O—;

in the formula (a-1-4), R β is independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and R α2 and R α3 are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R α2 and R α3 taken together represent a cyclic structure together with the carbon atom bonded to R α2 and R α3 ;

in the formula (a-1-5), R β is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and R δ is a group which forms a substituted or unsubstituted monovalent aromatic heterocyclic group having 3 to 20 carbon atoms together with an atom represented by Z;

in the formula (a-1-6), R β is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and R α4 is a monovalent hydrocarbon group having 1 to 20 carbon atoms;

in the formula (a-2-1), R ε is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.

6. The resist pattern-forming method according to claim 1 , wherein the structural unit comprising the cationic-group-forming group is represented by formula (1),

wherein

X 1 and X 2 are each independently a single bond, —O—, —C(O)—, —C(O)O—, —OC(O)O—, —C(O)OC(O)—, —C(O)NH—, —OC(O)NH—, or —SO 3 —;

Y 1 and Y 2 are each independently a single bond or an (n+1)-valent group represented by R C (R X )((L) p -*) n ,

wherein R C is an (n+2)-valent chain hydrocarbon group having 1 to 15 carbon atoms,

R X is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms,

L is —O—, —C(O)—, —C(O)O—, —OC(O)O—, —C(O)OC(O)—, —C(O)NH—, —OC(O)NH—, or —SO 3 —,

n is an integer from 1 to 3, and

p is 0 or 1, wherein a plurality of p are either identical or different when n is 2 or 3, and a plurality of L are either identical or different when a plurality of L are present;

* is a site bonded to R A or R B ; and

R A and R B are each independently a hydrogen atom or the cationic-group-forming group having valency of n, wherein a case where all of X 1 , Y 1 , X 2 , and Y 2 are a single bond is excluded, and at least one of R A or R B is the cationic-group-forming group having valency of n.

7. The resist pattern-forming method according to claim 6 , wherein the structural unit comprising the cationic-group-forming group is at least one structural unit selected from a group consisting of a structural unit represented by formula (1-1), a structural unit represented by formula (1-2), a structural unit represented by formula (1-3), and a structural unit represented by formula (1-4),

wherein

R α , R β , and R ε are each independently a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms;

R D is a hydrogen atom or a monovalent chain hydrocarbon group having 1 to 5 carbon atoms;

R E is a divalent chain hydrocarbon group having 1 to 10 carbon atoms;

R F1 to R F4 are each independently a hydrogen atom or a monovalent chain hydrocarbon group having 1 to 5 carbon atoms;

R G is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms;

R H is a single bond or a divalent chain hydrocarbon group having 1 to 10 carbon atoms; and

R 1 is a monovalent organic group having 1 to 20 carbon atoms.

8. The resist pattern-forming method according to claim 1 , wherein the polymer further comprises a structural unit represented by formula (2),

wherein

R 1 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms;

E is —O—, —C(O)—, —C(O)O—, —S—, —S(O)—, —S(O) 2 —, —C(O)S—, or —C(S)O—; and

R 2 is a non-acid-labile monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, wherein some or all of the hydrogen atoms included in the hydrocarbon group represented by R 1 and the alicyclic hydrocarbon group represented by R 2 are optionally substituted with a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, a carboxyl group, a nitro group, or an oxo group.

9. The resist pattern-forming method according to claim 1 , wherein the organic solvent is at least one organic solvent selected from a group consisting of an alcohol-based solvent, an ether-based solvent, a ketone-based solvent, an amide-based solvent, an ester-based solvent, and a hydrocarbon-based solvent.