Photoacid generator, method for producing the same, and resist composition comprising the same
A photoacid generator represented by the following formula (1), a method for producing the photoacid generator, and a resist composition containing the photoacid generator are provided. wherein in the formula (1), Y 1 , Y 2 , X, R 1 , R 2 , n 1 , n 2 and A + have the same meanings as defined in the detailed description of the invention. The photoacid generator can maintain an appropriate contact angle at the time of ArF liquid immersion lithography, can reduce defects occurring during liquid immersion lithography, and has excellent solubility in resist solvents and excellent compatibility with resins. Furthermore, the photoacid generator can be produced by an efficient and simple method using an epoxy compound that is industrially easily available.
1. A photoacid generator represented by the following formula (1):
wherein in the formula (1),
Y 1 and Y 2 each independently represent any one selected from the group consisting of a cycloalkyl group, a heterocycloalkyl group, an aryl group and a heteroaryl group;
X represents any one selected from the group consisting of an alkanediyl, an alkenediyl, NR′, S, O, CO and combinations thereof, while R′ represents any one selected from the group consisting of a hydrogen atom and an alkyl group;
R 1 and R 2 each independently represent any one selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, a perfluoroalkyl group, a perfluoroalkoxy group, a halogen group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an amino group and a thio group;
n 1 represents an integer or 1 or 2;
n 2 represents an integer from 0 to 5; and
A + represents an organic counterion.
2. The photoacid generator according to claim 1 , wherein
Y 1 and Y 2 each independently represent any one selected from the group consisting of a cyclopentyl group, a cyclohexyl group, a decahydronaphthalene group, an octahydro-1H-indene group, an adamantyl group, a norbornyl group, a tetrahydrofuran group, a polycyclic cycloalkyl group containing a norbornyl group having 10 to 30 carbon atoms, a phenyl group, a naphthyl group, a biphenyl group, an anthryl group, a phenanthrene group, a fluorenyl group, a pyrene group, a phenalene group, an indene group, a biphenylene group, a tetrahydronaphthyl group, and a dihydroanthryl group.
3. The photoacid generator according to claim 1 , wherein
Y 1 and Y 2 each independently represents any one selected from the group consisting of groups represented by the following formulas (1-a) to (1-i) and formulas (2-a) to (2-h) and (2-j) to (2-l):
wherein in the formulas (1-a) to (1-i),
R 11 and R 12 each independently represent any one selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, a perfluoroalkyl group, a perfluoroalkoxy group, a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an amino group, a thio group, a methylthio group, a methoxy group, OR′, COR′, COOR′, O and S, while R′ represents any one selected from the group consisting of an alkyl group and an aryl group;
R 21 represents any one selected from the group consisting of CR 24 R 25 , O, CO, S and NR 23 ; R 23 to R 25 each independently represent any one selected from the group consisting of a hydrogen atom, an alkyl group and an aryl group;
a, c and d each independently represent an integer from 0 to 9; b represents an integer from 0 to 11; e represents an integer from 0 to 15; f represents an integer from 0 to 7; and 0≦c+d≦17, while 0≦c+f≦15;
wherein in the formulas (2-a) to (2-h) and (2-j) to (2-l),
R 11 , R 12 , R 13 and R 14 each independently represent any one selected from the group consisting of an alkyl group, an alkoxy group, a perfluoroalkyl group, a perfluoroalkoxy group, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group and a thio group;
R 21 and R 22 each independently represent any one selected from the group consisting of CR 24 R 25 , O, CO, S and NR 23 ; R 23 to R 25 each independently represent any one selected from the group consisting of a hydrogen atom, an alkyl group and an aryl group;
a, and h each independently represent an integer from 0 to 5; b represents an integer from 0 to 3; c and d each independently represent an integer from 0 to 4; e, f and g each independently represent an integer from 0 to 2; and 0≦c+d+e≦9.
4. The photoacid generator according to claim 1 , wherein the photoacid generator is any one selected from the group consisting of compounds represented by the following formulas (3-1), (3-2), (3-4) to (3-13):
5. A method for producing a photoacid generator, the method comprising:
a first step of allowing a hydroxysulfonic acid salt to react with oxirane, and thereby producing a hydroxyethoxysulfonic acid salt;
a second step of allowing the hydroxyethoxysulfonic acid salt produced above to react with a carbonyl halide and thereby producing an intermediate; and
a third step of subjecting the intermediate thus produced to a substitution reaction of the cation, and thereby producing a compound represented by the following formula (1):
wherein in the formula (1),
Y 1 and Y 2 each independently represent any one selected from the group consisting of a cycloalkyl group, a heterocycloalkyl group, an aryl group and a heteroaryl group;
X represents any one selected from the group consisting of an alkanediyl, an alkenediyl, NR′, S, O, CO and combinations thereof; R′ represents any one selected from the group consisting of a hydrogen atom and an alkyl group;
R 1 and R 2 each independently represent any one selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, a perfluoroalkyl group, a perfluoroalkoxy group, a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an amino group and a thio group;
n 1 represents an integer or 1 or 2;
n 2 represents an integer from 0 to 5; and
A + represents an organic counterion.
6. The method for producing a photoacid generator according to claim 5 , wherein
the hydroxysulfonic acid salt is represented by the following formula (6),
the oxirane is represented by the following formula (7),
the hydroxyethoxysulfonic acid salt is represented by the following formula (8)
the carboxyl halide is represented by the following formula (9), and
the intermediate is represented by the following formula (10):
wherein in the formulas (6) to (8),
Y 1 and Y 2 each independently represent any one selected from the group consisting of a cycloalkyl group, a heterocycloalkyl group, an aryl group and a heteroaryl group;
X represents any one selected from the group consisting of an alkanediyl, an alkenediyl, NR′, S, O, CO and combinations thereof; R′ represents any one selected from the group consisting of a hydrogen atom and an alkyl group;
R 1 and R 2 each independently represent any one selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, a perfluoroalkyl group, a perfluoroalkoxy group, a halogen atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an amino group and a thio group;
R x represents a halogen atom;
n 1 represents an integer of 1 or 2;
n 2 represents an integer from 0 to 5; and
M + represents an alkali metal ion.
7. The method for producing a photoacid generator according to claim 5 , wherein any one step selected from the group consisting of the first step, the second step and a combination thereof is carried out by allowing the reaction to occur in the presence of any one catalyst selected from the group consisting of an acidic catalyst and a basic catalyst.
8. The method for producing a photoacid generator according to claim 5 , wherein the second step is carried out by allowing the hydroxyethoxysulfonic acid salt and a carbonyl halide to react for 1 to 12 hours at a temperature of 20° C. to 100° C.
9. A resist composition comprising the photoacid generator according to claim 1 .