Acid generating agent for chemically amplified resist compositions
An acid generating agent used for chemically amplified resist compositions is provided, which agent is represented by the following formula (1): wherein X represents a monocyclic or polycyclic hydrocarbon group having 3 to 30 carbon atoms, and having at least one hydrogen atom on the ring substituted by an alkyl or alkoxy group which may be unsubstituted or substituted with a group selected from an ether group, an ester group, a carbonyl group, an acetal group, an epoxy group, a nitrile group and an aldehyde group, or by a perfluoroalkyl group, a hydroxyalkyl group, or a cyano group; R 6 is an alkyl group, an alkoxy group, or a heteroatom selected from the group consisting of N, S and F; 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 a monocyclic or polycyclic hydrocarbon group having 3 to 30 carbon atoms, and having at least one hydrogen atom substituted by an alkyl or alkoxy group which has 1 to 10 carbon atoms and may be unsubstituted or substituted with an ether group, an ester group, a carbonyl group, an acetal group, an epoxy group, a nitrile group or an aldehyde group, or by a perfluoroalkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms or a cyano group; 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 the group consisting of nitrogen (N) and sulfur (S); m is an integer from 1 to 2; and A+ is an organic counterion.
2. The acid generating agent according to claim 1 , wherein X represents an adamantyl group, a norbornyl group or a cycloalkyl group.
3. The acid generating agent according to claim 1 , wherein X is selected from the group consisting of the compounds of the following formulas (1-a) to (1-h):
4. The acid generating agent according to claim 1 , wherein A+ comprises a cation represented by the following formula (2a) or (2b):
wherein R 1 and R 2 each independently represent an alkyl group, an allyl group, a perfluoroalkyl group, a benzyl group or an aryl group; and R 3 , R 4 and R 5 each independently represent a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, an aryl group, a thiophenoxy group, a thioalkoxy group or an alkoxycarbonylmethoxy group.
5. The acid generating agent according to claim 1 , wherein A+ comprises a cation represented by the following formula (3a) or (3b):
wherein R 1 and R 4 each independently represent an alkyl 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 halogen group, an alkoxy group, an aryl group, a thiophenoxy group, a thioalkoxy group or an alkoxycarbonylmethoxy group.
6. The acid generating agent according to claim 4 , wherein the compound of the formula (2a) or (2b) is selected from the group consisting of the compounds of the following formulas (2-i) to (2-xx):
7. The acid generating agent according to claim 5 , wherein the compound of the formula (3a) or (3b) is selected from the group consisting of the compounds of the following formulas (3-i) to (3-ix):
8. The acid generating agent according to claim 1 , wherein the acid generating agent is a salt represented by the following formula (4a), (4b), (4c) or (4d):
wherein in the formulas (4a) and (4b), R 1 and R 2 each independently represent an alkyl group, an allyl group, a perfluoroalkyl group, a benzyl group or an aryl group; and R 3 , R 4 and R 5 each independently represent a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, an aryl group, a thiophenoxy group, a thioalkoxy group or an alkoxycarbonylmethoxy group; in the formulas (4c) and (4d), R 1 represents an alkyl group, an allyl group, a perfluoroalkyl group, a benzyl group or an aryl group; and R 2 , R 3 and R 4 each independently represent a hydrogen atom, an alkyl group, a halogen atom, an alkoxy group, an aryl group, a thiophenoxy group, a thioalkoxy group or an alkoxycarbonylmethoxy group; and in the above four formulas, B represents the anion moiety in the formula (1).
9. The acid generating agent according to claim 1 , wherein the acid generating agent of formula (1) is produced by reacting a salt represented by the following formula (8) with a compound represented by the following formula (12):
A + Z − [Formula 12]
wherein X represents a monocyclic or polycyclic hydrocarbon group having 3 to 30 carbon atoms, and having at least one hydrogen atom substituted by an alkyl or alkoxy group which has 1 to 10 carbon atoms and may be unsubstituted or substituted with an ether group, an ester group, a carbonyl group, an acetal group, an epoxy group, a nitrile group or an aldehyde group, or by a perfluoroalkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms or a cyano group; 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 the group consisting of N and S; m is an integer from 1 to 2; M is lithium (Li), sodium (Na) or potassium (K); 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 , fluorine (F), chlorine (Cl), bromine (Br), iodine (I), BF 4 , ASF 6 or PF 6 ; and A+ is an organic counterion.
10. The acid generating agent according to claim 9 , wherein the salt represented by the formula (8) is produced by reacting an alcohol compound represented by the following formula (10) with a compound represented by the following formula (11):
wherein in the formula (10), M is Li, Na or K; while in the formula (11), ring X represents a monocyclic or polycyclic hydrocarbon group having 3 to 30 carbon atoms, and having at least one hydrogen atom substituted by an alkyl or alkoxy group which has 1 to 10 carbon atoms and may be unsubstituted or substituted with an ether group, an ester group, a carbonyl group, an acetal group, an epoxy group, a nitrile group or an aldehyde group, or by a perfluoroalkyl group having 1 to 4 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms or a cyano group; 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 the group consisting of N and S; and m is an integer from 1 to 2.
11. The acid generating agent according to claim 10 , wherein the alcohol compound represented by the formula (10) is produced by dissolving an ester compound represented by the following formula (9) in an alcoholic solvent, and then adding a reducing agent dropwise to the solution:
wherein R 1 is selected from the group consisting of hydrogen, methyl, trifluoromethyl, trichloromethyl, tribromomethyl and triiodomethyl; and M is Li, Na or K.
12. The acid generating agent according to claim 11 , wherein the reducing agent is selected from sodium borohydride, lithium aluminum hydride (LiAlH 4 ), BH 3 -THF, NaBH 4 -AlCl 3 , NaBH 4 —LiCl, and LiAl(OMe) 3 .
13. A chemically amplified resist composition comprising the acid generating agent according to claim 1 .