# US 7,741,007 B2 · Chemicallly amplified resist composition

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- Number: US 7,741,007 B2
- Document ID: US7741007B2
- Status: Granted
- Kind: B2
- Application number: 11/987,672
- Filed: 2007-12-03
- Published: 2008-09-04
- Granted: 2010-06-22
- Earliest claimed: 2006-12-06
- Assignees: Sumitomo Chemical Company, Limited
- Inventors: Satoshi Yamaguchi; Satoshi Yamamoto; Nobuo Ando
- Web page: https://patentgrep.com/patent/US7741007B2

## CPC

- G03F 7/0045: {with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors}
- G03F 7/0046: {with perfluoro compounds, e.g. for dry lithography (G03F7/0048 takes precedence)}
- G03F 7/0397: {the macromolecular compound having an alicyclic moiety in a side chain}
- Y10S 430/106: Binder containing
- Y10S 430/111: Polymer of unsaturated acid or ester
- Y10S 430/122: Sulfur compound containing
- Y10S 430/123: Sulfur in heterocyclic ring
- G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G)
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

## Abstract

The present invention provides a chemically amplified resist composition comprising: (A) a salt represented by the formula (1) wherein R21, Q1, Q2, and A+ defined in the specification; (B) a salt represented by the formula (II): wherein R22, Q3, Q4, and A′+ are defined in the specification; and (C) a resin which contains a structural unit having a structural unit having an acid-labile group and which itself is insoluble or poorly soluble in an aqueous alkali solution but becomes soluble in an aqueous alkali solution by the action of an acid.

## Claims

### Claim 1

A chemically amplified resist composition comprising:
(A) a salt represented by the formula (I):
wherein R21 represents a C1-C30 hydrocarbon group which may be substituted, and at least one —CH2— in the hydrocarbon group may be substituted by —CO— or —O—, Q1 and Q2 each independently represent a fluorine atom or a C1-C6 perfluoroalkyl group,
and A+ represents at least one organic cation selected from a cation represented by the formula (Ia):
wherein P1, P2 and P3 each independently represent a C1-C30 alkyl group which may be substituted with at least one selected from a hydroxyl group, a C3-C12 cyclic hydrocarbon group and a C1-C12 alkoxy group, or a C3-C30 cyclic hydrocarbon group which may be substituted with at least one selected from a hydroxyl group and a C1-C12 alkoxy group, a cation represented by the formula (Ib):
wherein P4 and P5 each independently represent a hydrogen atom, a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group, and a cation represented by the formula (Ic):
wherein P10, P11, P12, P13, P14, P15, P16, P17, P18, P19, P20 and P21 each independently represent a hydrogen atom, a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group, B represents a sulfur or oxygen atom and m represents 0 or 1,
(B) a salt represented by the formula (II):
wherein R22 represents a C1-C30 hydrocarbon group which may be substituted, and at least one —CH2— in the hydrocarbon group may be substituted by —CO— or —O—, Q3 and Q4 each independently represent a fluorine atom or a C1-C6 perfluoroalkyl group, and A′+ represents an organic cation represented by the formula (IIa):
wherein P6 and P7 each independently represent a C1-C12 alkyl group or a C3-C12 cycloalkyl group, or P6 and P7 are bonded to form a C3-C12 divalent acyclic hydrocarbon group which forms a ring together with the adjacent S+, and at least one —CH2— in the divalent acyclic hydrocarbon group may be substituted with —CO—, —O— or —S—,
P8 represents a hydrogen atom, P9 represents a C1-C12 alkyl group, a C3-C12 cycloalkyl group or an aromatic group which may be substituted, or P8 and P9 are bonded to form a divalent acyclic hydrocarbon group which forms a 2-oxocycloalkyl group together with the adjacent —CHCO—, and at least one —CH2— in the divalent acyclic hydrocarbon group may be replaced with —CO—, —O— or —S—; and
(C) a resin which contains a structural unit having an acid-labile group and which itself is insoluble or poorly soluble in an aqueous alkali solution but becomes soluble in an aqueous alkali solution by the action of an acid.

### Claim 2 (depends on 1)

The resist composition according to claim 1, wherein Q1, Q2, Q3 and Q4 each independently represent a fluorine atom or a trifluoromethyl group.

### Claim 3 (depends on 1)

The resist composition according to claim 1, wherein Q1, Q2, Q3 and Q4 represent fluorine atoms.

### Claim 4 (depends on 1)

The resist composition according to claim 1, wherein A+ is a cation represented by the formula (Id), (Ie) or (If):
wherein P28, P29 and P30 each independently represent a C1-C20 alkyl group or a C3-C30 cyclic hydrocarbon group except a phenyl group, and at least one hydrogen atom in the C1-C20 alkyl group may be substituted with a hydroxyl group, a C1-C12 alkoxy group or a C3-C12 cyclic hydrocarbon group and at least one hydrogen atom in the C3-C30 cyclic hydrocarbon group may be substituted with a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group, and
P31, P32, P33, P34, P35 and P36 each independently represent a hydroxyl group, a C1-C12 alkyl group, a C1-C12 alkoxy group or a C3-C12 cyclic hydrocarbon group, and l, k, j, i, h and g each independently represent an integer of 0 to 5.

### Claim 5 (depends on 1)

The resist composition according to claim 1, wherein A+ is a cation represented by the formula (Ig):
wherein P41, P42 and P43 each independently represent a hydrogen atom, a hydroxyl group, a C1-C12 alkyl group or a C1-C12 alkoxy group.

### Claim 6 (depends on 1)

The resist composition according to claim 1, wherein A+ is a cation represented by the formula (Ih):
wherein P22, P23 and P24 each independently represent a hydrogen atom or a C1-C4 alkyl group.

### Claim 7 (depends on 1)

The resist composition according to claim 1, wherein R21 represents a group represented by the formula:
wherein Z1 represents a single bond or —(CH2)f—, f represents an integer of 1 to 4, Y1 represents —CH2—, —CO— or —CH(OH)—; ring X1 represents a C3-C30 monocyclic or polycyclic hydrocarbon group in which a hydrogen atom is substituted with a hydroxyl group at Y1 position when Y1 is —CH(OH)— or in which two hydrogen atoms are substituted with ═O at Y1 position when Y1 is —CO—, and at least one hydrogen atom in the C3-C30 monocyclic or polycyclic hydrocarbon group may be substituted with a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, a hydroxyl group or a cyano group.

### Claim 8 (depends on 7)

The resist composition according to claim 7, wherein the group represented by the formula:
is a group represented by the formula (l), (m) or (n):

### Claim 9 (depends on 1)

The resist composition according to claim 1, wherein A+ is a cation represented by the formula (Ih):
wherein P22, P23 and P24 each independently represent a hydrogen atom or a C1-C4 alkyl group, and R21 represents a group represented by the formula:
wherein Z1 represents a single bond or —(CH2)f—, f represents an integer of 1 to 4, Y1 represents —CH2—, —CO— or —CH(OH)—; ring X1 represents a C3-C30 monocyclic or polycyclic hydrocarbon group in which a hydrogen atom is substituted with a hydroxyl group at Y1 position when Y1 is —CH(OH)— or in which two hydrogen atoms are substituted with ═O at Y1 position when Y is —CO—, and at least one hydrogen atom in the C3-C30 monocyclic or polycyclic hydrocarbon group may be substituted with a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, a hydroxyl group or a cyano group.

### Claim 10 (depends on 9)

The resist composition according to claim 9, wherein the group represented by the formula:
is a group represented by the formula (l), (m) or (n):

### Claim 11 (depends on 1)

The resist composition according to claim 1, wherein P6 and P7 are bonded to form a C3-C12 divalent acyclic hydrocarbon group which forms a ring together with the adjacent S+, P8 represents a hydrogen atom, P9 represents a C1-C12 alkyl group, a C3-C12 cycloalkyl group or an aromatic group which may be substituted with at least one selected from a C1-C6 alkoxy group, a C2-C20 acyl group and a nitro group.

### Claim 12 (depends on 1)

The resist composition according to claim 1, wherein R22 represents a group represented by the formula:
wherein Z2 represents a single bond or —(CH2)g, g represents an integer of 1 to 4, Y2 represents —CH2—, —CO— or —CH(OH)—; ring X2 represents a C3-C30 monocyclic or polycyclic hydrocarbon group in which a hydrogen atom is substituted with a hydroxyl group at Y2 position when Y2 is —CH(OH)— or in which two hydrogen atoms are substituted with ═O at Y2 position when Y2 is —CO—, and at least one hydrogen atom in the C3-C30 monocyclic or polycyclic hydrocarbon group may be substituted with a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, a hydroxyl group or a cyano group.

### Claim 13 (depends on 12)

The resist composition according to claim 12, wherein the group represented by the formula:
is a group represented by the formula (l), (m) or (n):

### Claim 14 (depends on 1)

The resist composition according to claim 1, wherein P6 and P7 are bonded to form a C3-C12 divalent acyclic hydrocarbon group which forms a ring together with the adjacent S+, P8 represents a hydrogen atom, P9 represents a C1-C12 alkyl group, a C3-C12 cycloalkyl group or an aromatic group which may be substituted with at least one selected from a C1-C6 alkoxy group, a C2-C20 acyl group and a nitro group; and
R22 represents a group represented by the formula:
wherein Z2 represents a single bond or —(CH2)g, g represents an integer of 1 to 4, Y2 represents —CH2—, —CO— or —CH(OH)—; ring X2 represents a C3-C30 monocyclic or polycyclic hydrocarbon group in which a hydrogen atom is substituted with a hydroxyl group at Y2 position when Y2 is —CH(OH)— or in which two hydrogen atoms are substituted with ═O at Y2 position when Y2 is —CO—, and at least one hydrogen atom in the C3-C30 monocyclic or polycyclic hydrocarbon group may be substituted with a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, a hydroxyl group or a cyano group.

### Claim 15 (depends on 14)

The resist composition according to claim 14, wherein the group represented by the formula:
is a group represented by the formula (l), (m) or (n):

### Claim 16 (depends on 1)

The resist composition according to claim 1, wherein A+ is a cation represented by the formula (Ih):
wherein P22, P23 and P24 each independently represent a hydrogen atom or a C1-C4 alkyl group,
R21 represents a group represented by the formula:
wherein Z1 represents a single bond or —(CH2)f—, f represents an integer of 1 to 4, Y1 represents —CH2—, —CO— or —CH(OH)—; ring X1 represents a C3-C30 monocyclic or polycyclic hydrocarbon group in which a hydrogen atom is substituted with a hydroxyl group at Y1 position when Y1 is —CH(OH)— or in which two hydrogen atoms are substituted with ═O at Y1 position when Y is —CO—, and at least one hydrogen atom in the C3-C30 monocyclic or polycyclic hydrocarbon group may be substituted with a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, a hydroxyl group or a cyano group, and
R22 represents a group represented by the formula:
wherein Z2 represents a single bond or —(CH2)g, g represents an integer of 1 to 4, Y2 represents —CH2—, —CO— or —CH(OH)—; ring X2 represents a C3-C30 monocyclic or polycyclic hydrocarbon group in which a hydrogen atom is substituted with a hydroxyl group at Y2 position when Y2 is —CH(OH)— or in which two hydrogen atoms are substituted with ═O at Y2 position when Y2 is —CO—, and at least one hydrogen atom in the C3-C30 monocyclic or polycyclic hydrocarbon group may be substituted with a C1-C6 alkyl group, a C1-C6 alkoxy group, a C1-C4 perfluoroalkyl group, a C1-C6 hydroxyalkyl group, a hydroxyl group or a cyano group.

### Claim 17 (depends on 16)

The resist composition according to claim 16, wherein
the group represented by the formula:
and the group represented by the formula:
each independently represent a group represented by the formula (l), (m) or (n):

### Claim 18 (depends on 1)

The resist composition according to claim 1, wherein the amount ratio of the salt represented by the formula (I) and the salt represented by the formula (II) is 9/1 to 1/9.

### Claim 19 (depends on 1)

The resist composition according to claim 1, wherein the resin contains a structural unit derived from a monomer having a bulky and acid-labile group.

### Claim 20 (depends on 19)

The resist composition according to claim 19, the bulky and acid-labile group is a 2-alkyl-2-adamantyl ester group or a 1-(1-adamantyl)-1-alkylalkyl ester group.

### Claim 21 (depends on 19)

The resist composition according to claim 19, the monomer having a bulky and acid-labile group is 2-alkyl-2-adamantyl acrylate, 2-alkyl-2-adamantyl methacrylate, 1-(1-adamantyl)-1-alkylalkyl acrylate, 1-(1-adamantyl)-1-alkylalkyl methacrylate, 2-alkyl-2-adamantyl 5-norbornene-2-carboxylate, 1-(1-adamantyl)-1-alkylalkyl 5-norbornene-2-carboxylate, 2-alkyl-2-adamantyl α-chloroacrylate or 1-(1-adamantyl)-1-alkylalkyl α-chloroacrylate.

### Claim 22 (depends on 1)

The resist composition according to claim 1, wherein the resist composition further comprises a basic compound.