Acid generating agent for chemically amplified resist compositions
An acid generating agent represented by the following formula (1) or (2) is provided, which is included in chemically amplified resist compositions: wherein in the formula (1) and (2), X represents an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms and selected from alkyl, haloalkyl and alkylsulfonyl, which may have at least one hydrogen atom substituted by an ether group, an ester group, a carbonyl group, an acetal group, a nitrile group, a cyano group, a hydroxyl group, a carboxyl group or an aldehyde group, or represents a perfluoroalkyl group having 1 to 4 carbon atoms; R 6 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a heteroatom selected from nitrogen, sulfur, fluorine and oxygen; m is an integer from 0 to 2; and A+ is an organic counterion.
1. An acid generating agent represented by the following formula (1):
wherein X represents an unsubstituted or substituted non-cyclic alkyl group having 1 to 20 carbon atoms and selected from alkyl, haloalkyl and alkylsulfonyl, which may have at least one hydrogen atom substituted by an ether group, an ester group, a carbonyl group, an acetal group, a nitrile group, a cyano group, a hydroxyl group, a carboxyl group or an aldehyde group, or represents a perfluoroalkyl group having 1 to 4 carbon atoms; R 6 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a heteroatom selected from nitrogen (N), sulfur (S), fluorine (F) and oxygen (O); m is an integer from 0 to 2; and A+ is an organic counterion.
2. The acid generating agent according to claim 1 , wherein A+ is at least one cation selected from the group consisting of cations represented by the following formulas 3a and 3b:
wherein in the formulas 3a and 3b, R 1 and R 2 each independently represent an alkyl group, a cycloalkyl group, an allyl group, a perfluoroalkyl group, a benzyl group or an aryl group, each having 1 to 20 carbon atoms; and R 3 , R 4 and R 5 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, an alkoxy group, an aryl group, a thiophenoxy group, a thioalkoxy group or an alkoxycarbonylmethoxy group.
3. The acid generating agent according to claim 1 , wherein A+ is at least one cation selected from the group consisting of cations represented by the following formulas 4a and 4b:
[Formula 4a]
wherein in the formulas (4a) and (4b), R 1 and R 4 each independently represent an alkyl group, a cycloalkyl group, an allyl group, a perfluoroalkyl group, a benzyl group or an aryl group; and R 2 and R 3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, an alkoxy group, an aryl group, a thiophenoxy group, a thioalkoxy group or an alkoxycarbonylmethoxy group.
4. The acid generating agent according to claim 1 , wherein the anion moiety of the acid generating agent is at least one selected from groups represented by the following formulas (1-i) to (1-viii)
5. The acid generating agent according to claim 1 , wherein the acid generating agent is produced by a reaction between a salt represented by the following formula (5) and a compound represented by the following formula (9):
wherein X represents an unsubstituted or substituted non-cyclic alkyl group having 1 to 20 carbon atoms and selected from alkyl, haloalkyl and alkylsulfonyl, which may have at least one hydrogen atom substituted by an ether group, an ester group, a carbonyl group, an acetal group, a nitrile group, a cyano group, a hydroxyl group, a carboxyl group or an aldehyde group, or represents a perfluoroalkyl group having 1 to 4 carbon atoms; R 6 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a heteroatom selected from N, S, F and O; m is an integer from 0 to 2; and M is lithium (Li), sodium (Na) or potassium (K);
A + +Z − [Formula 9]
wherein A+ is an organic counterion; and Z is OSO 2 CF 3 , OSO 2 C 4 F 9 , OSO 2 C 8 F 17 , N(CF 3 ) 2 , N(C 2 F 5 ) 2 , N(C 4 F 9 ) 2 , C(CF 3 ) 3 , C(C 2 F 5 ) 3 , C(C 4 F 9 ) 3 , F, Cl, Br, I, BF 4 , A S F 6 or PF 6 .
6. The acid generating agent according to claim 5 , wherein the salt of formula (5) is produced by a reaction between an alcohol compound represented by the following formula (7) and an acyl compound represented by the following formula (8):
wherein M is Li, Na or K;
wherein X represents an unsubstituted or substituted non-cyclic alkyl group having 1 to 20 carbon atoms and selected from alkyl, haloalkyl and alkylsulfonyl, which may have at least one hydrogen atom substituted by an ether group, an ester group, a carbonyl group, an acetal group, a nitrile group, a cyano group, a hydroxyl group, a carboxyl group or an aldehyde group, or represents a perfluoroalkyl group having 1 to 4 carbon atoms; R 6 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a heteroatom selected from N, S, F and O; and m is an integer from 0 to 2.
7. The acid generating agent according to claim 6 , wherein the alcohol compound of formula (7) is produced by a reduction reaction of an ester compound represented by the following formula (6):
wherein R 1 is hydrogen, methyl, trifluoromethyl, trichloromethyl, tribromomethyl or triiodomethyl; and M is Li, Na or K.
8. A chemically amplified resist composition comprising the acid generating agent of claim 1 and a copolymer.
9. The chemically amplified resist composition according to claim 8 , wherein the acid generating agent is contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the copolymer.