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US 7,527,912 B2Granted
Photoacid generators, resist compositions, and patterning process
AssigneeShin-Etsu Chemical Co., Ltd.
InventorsYouichi Ohsawa, Takeru Watanabe, Koji Hasegawa, Masaki Ohashi
Life of this patent
Estimating the term…
Abstract
Photoacid generators generate sulfonic acids of formula (1a) upon exposure to high-energy radiation. RC(═O)R1—COOCH(CF3)CF2SO3−H+ (1a) R is hydroxyl, alkyl, aryl, hetero-aryl, alkoxy, aryloxy or hetero-aryloxy, R1 is a divalent organic group which may have a heteroatom (O, N or S) containing substituent, or R1 may form a cyclic structure with R. The photoacid generators are compatible with resins and can control acid diffusion and are thus suited for use in chemically amplified resist compositions.
Claims15
A photoacid generator for chemically amplified resist compositions which generates a sulfonic acid upon exposure to high-energy radiation selected from UV, deep-UV, EUV, electron beam, x-ray, excimer laser, gamma-ray and synchrotron radiation, said sulfonic acid having the general formula (1a):
- RC(═O)R1—COOCH(CF3)CF2SO3−H+ (1a)
- wherein R is selected from the group consisting of a hydroxyl group, a substituted or unsubstituted straight, branched or cyclic C1-C20 alkyl group, a substituted or unsubstituted C6-C15 aryl or C4-C15 hetero-aryl group, a substituted or unsubstituted straight, branched or cyclic C1-C20 alkoxy group, and a substituted or unsubstituted C6-C15 aryloxy or C4-C15 hetero-aryloxy group,
- R1 is a divalent C1-C20 organic group which may have a substituent group containing a heteroatom selected from oxygen, nitrogen and sulfur atoms, or R1 may form at least one cyclic structure with R.
A sulfonium salt having the general formula (2):
- RC(═O)—R1—COOCH(CF3)CF2SO3−R2R3R4S+ (2)
- wherein R is selected from the group consisting of a hydroxyl group, a substituted or unsubstituted straight, branched or cyclic C1-C20 alkyl group, a substituted or unsubstituted C6-C15 aryl or C4-C15 hetero-aryl group, a substituted or unsubstituted straight, branched or cyclic C1-C20 alkoxy group, and, a substituted or unsubstituted C6-C15 aryloxy or C4-C15 hetero-aryloxy group,
- R1 is a divalent C1-C20 organic group which may have a substituent group containing a heteroatom selected from oxygen, nitrogen and sulfur atoms, or R1 may form at least one cyclic structure with R,
- R2, R3 and R4 are each independently selected from the group consisting of substituted or unsubstituted straight, branched or cyclic C1-C20 alkyl, alkenyl and oxoalkyl groups, and substituted or unsubstituted C6-C18 aryl, aralkyl and aryloxoalkyl groups, or at least two of R2, R3 and R4 may bond together to form a ring with the sulfur atom.
1 more element
A sulfonium salt having the general formula (2a):
- RC(═O)—R1—COOCH(CF3)CF2SO3−(R5(O)n)mPh′S+Ph2 (2a)
- wherein R is selected from the group consisting of a hydroxyl group, a substituted or unsubstituted straight, branched or cyclic C1-C20 alkyl group, a substituted or unsubstituted C6-C15 aryl or C4-C15 hetero-aryl group, a substituted or unsubstituted straight, branched or cyclic C1-C20 alkoxy group, and a substituted or unsubstituted C6-C15 aryloxy or C4-C15 hetero-aryloxy group,
- R1 is a divalent C1-C20 organic group which may have a substituent group containing a heteroatom selected from oxygen, nitrogen and sulfur atoms, or R1 may form at least one cyclic structure with R,
- R5 is a substituted or unsubstituted straight, branched or cyclic C1-C20 alkyl or alkenyl group, or a substituted or unsubstituted C6-C14 aryl group,
- m is an integer of 1 to 5, n is 0 or 1, Ph is phenyl, and Ph′ is a phenyl group in which a number “m” of hydrogen atoms are substituted by R5(O)n— groups.
2 more elements
A iodonium salt having the general formula (2b):
- RC(═O)—R1—COOCH(CF3)CF2SO3−[(R5(O)n)mPh′]2I+ (2b)
- wherein R is selected from the group consisting of a hydroxyl group, a substituted or unsubstituted straight, branched or cyclic C1-C20 alkyl group, a substituted or unsubstituted C6-C15 aryl or C4-C15 hetero-aryl group, a substituted or unsubstituted straight, branched or cyclic C1-C20 alkoxy group, and a substituted or unsubstituted C6-C15 aryloxy or C4-C15 hetero-aryloxy group,
- R1 is a divalent C1-C20 organic group which may have a substituent group containing a heteroatom selected from oxygen, nitrogen and sulfur atoms, or R1 may form at least one cyclic structure with R,
- R5 is a substituted or unsubstituted straight, branched or cyclic C1-C20 alkyl or alkenyl group, or a substituted or unsubstituted C6-C14 aryl group,
- m is an integer of 1 to 5, n is 0 or 1, and Ph′ is a phenyl group in which a number “m” of hydrogen atoms are substituted by R5(O)n— groups.
2 more elements
A N-sulfonyloxyimide compound having the general formula (3a):
- wherein R is selected from the group consisting of a hydroxyl group, a substituted or unsubstituted straight, branched or cyclic C1-C20 alkyl group, a substituted or unsubstituted C6-C15 aryl or C4-C15 hetero-aryl group, a substituted or unsubstituted straight, branched or cyclic C1-C20 alkoxy group, and a substituted or unsubstituted C6-C15 aryloxy or C4-C15 hetero-aryloxy group,
- R1 is a divalent C1-C20 organic group which may have a substituent group containing a heteroatom selected from oxygen, nitrogen and sulfur atoms, or R1 may form at least one cyclic structure with R,
- X and Y are each independently hydrogen or a substituted or unsubstituted C1-C6 alkyl group, or X and Y may bond together to form a saturated or unsaturated C6-C12 ring with the carbon atoms to which they are attached, and
- Z is a single bond, double bond, methylene group or oxygen atom.
1 more element
An oxime sulfonate compound having the general formula (3b):
- wherein R is selected from the group consisting of a hydroxyl group, a substituted or unsubstituted straight, branched or cyclic C1-C20 alkyl group, a substituted or unsubstituted C6-C15 aryl or C4-C15 hetero-aryl group, a substituted or unsubstituted straight, branched or cyclic C1-C20 alkoxy group, and a substituted or unsubstituted C6-C15 aryloxy or C4-C15 hetero-aryloxy group,
- R1 is a divalent C1-C20 organic group which may have a substituent group containing a heteroatom selected from oxygen, nitrogen and sulfur atoms, or R1 may form at least one cyclic structure with R,
- q is 0 or 1,
- when q is 0, p is a substituted or unsubstituted C1-C20 alkyl group or a substituted or unsubstituted C6-C15 aryl group,
- when q is 1, p is a single bond, a substituted or unsubstituted C1-C20 alkylene group or a substituted or unsubstituted C6-C15 arylene group,
- EWG is a cyano, trifluoromethyl, perfluoroethyl, perfluoropropyl, 5H-perfluoropentyl, 6H-perfluorohexyl, nitro or methyl group, and when q is 1, two EWG's may bond together to form a ring of 6 carbon atoms with the carbon atoms to which they are attached.
3 more elements
Dependencies are inferred from the claim text.