Negative resist composition, method of forming resist pattern and complex
A negative resist composition including a complex represented by the general formula (1); and a polymerization initiator, in which M represents hafnium (Hf) or zirconium (Zr), X represents a ligand comprising a conjugate base of an acid which has an acid dissociation constant (pKa) of 3.8 or less and has a polymerizable group, Y represents a ligand having no polymerizable group, and n represents an integer of 1 to 4. [MX n Y 4-n ] (1)
1. A complex which is represented by the following general formula (1):
[MX n Y 4-n ] (1)
wherein M represents hafnium or zirconium, X represents a ligand comprising a conjugate base of an acid which has an acid dissociation constant pKa of 3.8 or less and has a polymerizable group, Y represents a ligand having no polymerizable group, and n represents an integer of 1 to 4.
2. The complex according to claim 1 , wherein the acid dissociation constant pKa of the acid is 2.8 or less.
3. The complex according to claim 1 , wherein X in the formula (1) is a ligand comprising a conjugate base represented by general formula (2) shown below:
R 1 —Y 1 —SO 3 ⊖ (2)
wherein R 1 represents a polymerizable group having a group selected from groups (X-01) to (X-07) shown below, and Y 1 represents a divalent linking group or a single bond;
wherein R represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms, Ar represents an aromatic hydrocarbon group, n represents an integer of 0 to 2, and * represents a valence bond.
4. The complex according to claim 1 , wherein X in the formula (1) is a ligand comprising a conjugate base selected from the group consisting of a conjugate base of 3-(methacryloyloxy)-1-propanesulfonic acid, a conjugate base of 3-(acryloyloxy)-1-propanesulfonic acid, a conjugated base of vinylsulfonic acid, and a conjugated base of styrenesulfonic acid.
5. The complex according to claim 1 , wherein X in the formula (1) is a ligand comprising a conjugate base represented by general formula (3) shown below:
R 2 —Y 2 —COO ⊖ (3)
wherein, in formula (3), R 2 represents a polymerizable group having a group selected from (X-01) to (X-07) shown below, and Y 2 represents a divalent linking group or a single bond:
wherein R represents a hydrogen atom, an alkyl group of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms, Ar represents an aromatic hydrocarbon group, n represents an integer of 0 to 2, and * represents a valence bond.
6. The complex according to claim 1 , wherein X in the formula (1) is a ligand comprising a conjugate base selected from the group consisting of a conjugate base of carboxymethyl methacrylate, and a conjugate base of carboxymethyl acrylate.
7. The complex according to claim 1 , wherein M represents hafnium.
8. The complex according to claim 2 , wherein M represents hafnium.
9. The complex according to claim 3 , wherein M represents hafnium.
10. The complex according to claim 4 , wherein M represents hafnium.
11. The complex according to claim 5 , wherein M represents hafnium.
12. The complex according to claim 6 , wherein M represents hafnium.
13. The complex according to claim 1 , wherein M represents zirconium.
14. The complex according to claim 2 , wherein M represents zirconium.
15. The complex according to claim 3 , wherein M represents zirconium.
16. The complex according to claim 4 , wherein M represents zirconium.
17. The complex according to claim 5 , wherein M represents zirconium.
18. The complex according to claim 6 , wherein M represents zirconium.
19. The complex according to claim 4 , wherein X in the formula (1) is a ligand comprising a conjugate base of 3-(methacryloyloxy)-1-propanesulfonic acid, and M represents hafnium.
20. The complex according to claim 6 , wherein X in the formula (1) is a ligand comprising a conjugate base of carboxymethyl methacrylate, and M represents hafnium.