# US 8,771,916 B2 · Actinic ray-sensitive or radiation-sensitive resin composition and pattern forming method using the same

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- Number: US 8,771,916 B2
- Document ID: US8771916B2
- Status: Granted
- Kind: B2
- Application number: 13/139,074
- Filed: 2009-12-11
- Published: 2011-09-29
- Granted: 2014-07-08
- Earliest claimed: 2008-12-12
- Assignees: FUJIFILM Corporation
- Applicants: Shuji Hirano; Kaoru Iwato; Hiroshi Saegusa; Yusuke Iizuka
- Inventors: Shuji Hirano; Kaoru Iwato; Hiroshi Saegusa; Yusuke Iizuka
- Web page: https://patentgrep.com/patent/US8771916B2

## CPC

- C07D 307/93: condensed with a ring other than six-membered
- C07D 407/12: linked by a chain containing hetero atoms as chain links
- C07D 493/08: Bridged systems
- C07D 493/18: Bridged systems
- C07D 495/18: Bridged systems
- C08F 24/00: Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a heterocyclic ring containing oxygen (cyclic esters of polyfunctional acids C08F18/00; cyclic anhydrides of unsaturated acids C08F20/00, C08F22/00)
- 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}
- G03F 7/2041: {in the presence of a fluid, e.g. immersion; using fluid cooling means}
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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)

## Abstract

An actinic ray-sensitive or radiation-sensitive resin composition, includes: (A) a resin capable of increasing the solubility of the resin (A) in an alkali developer by the action of an acid; and (C) a resin having at least either a fluorine atom or a silicon atom and containing (c) a repeating unit having at least two or more polarity conversion groups.

## Claims

### Claim 1

An actinic ray-sensitive or radiation-sensitive resin composition, comprising:
(A) a resin capable of increasing a solubility of the resin (A) in an alkali developer by an action of an acid; and
(C) a resin having at least either a fluorine atom or a silicon atom and containing (c) a repeating unit having at least two or more polarity conversion groups represented by —COO— in the structure represented by formula (KA-1) or (KB-1):
wherein Zka represents an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group or an electron-withdrawing group, and when a plurality of Zka's are present, the plurality of Zka's are the same or different;
each Zka may combine with every other Zka to form a ring;
nka represents an integer of 0 to 10;
each of Xkb1 and Xkb2 independently represents an electron-withdrawing group;
each of nkb and nkb′ independently represents 0 or 1; and
each of Rkb1 to Rkb4 independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an electron-withdrawing group, at least two members of Rkb1, Rkb2 and Xkb1 may combine with each other to form a ring, and at least two members of Rkb3, Rkb4 and Xkb2 may combine with each other to form a ring,
wherein:
the resin (A) contains no fluorine atom and no silicon atom;
the resin (A) includes a repeating unit represented by the following Formula (AI):
wherein in formula (AI), Xa1 represents a hydrogen atom, a methyl group which may have a substituent, or a group represented by —CH2—R9; R9 represents a hydroxyl group or a monovalent organic group;
T represents a single bond or a divalent linking group;
each of Rx1 to Rx3 independently represents a linear or branched alkyl group or a monocyclic or polycyclic cycloalkyl group; and
two members out of Rx1 to Rx3 may combine to form a monocyclic or polycyclic cycloalkyl group; and
the repeating unit (c) has a structure represented by the following formula (KY-2):
wherein each of Rky6 to Rky10 independently represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, an ether group, a hydroxyl group, a cyano group, an amide group or an aryl group;
two or more members of Rky6 to Rky10 may combine with each other to form a monocyclic or polycyclic structure;
Rky5 represents an electron-withdrawing group; and
Rkb1, Rkb2 and nkb have the same meanings as in formula (KB-1).

### Claim 2 (depends on 1)

The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1,
wherein the repeating unit (c) is (c′) a repeating unit having the at least two or more polarity conversion groups and at least either a fluorine atom or a silicon atom on one side chain.

### Claim 3 (depends on 1)

The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1,
wherein the repeating unit (c) is (c*) a repeating unit having the at least two or more polarity conversion groups and having neither a fluorine atom nor a silicon atom, and
the resin (C) further contains a repeating unit having at least either a fluorine atom or a silicon atom.

### Claim 4 (depends on 1)

The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1,
wherein the repeating unit (c) is (c″) a repeating unit having the at least two or more polarity conversion groups on one side chain and at the same time, having at least either a fluorine atom or a silicon atom on a side chain different from said side chain in the same repeating unit.

### Claim 5 (depends on 1)

The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1,
wherein the resin (C) has at least one group represented by any one of formulae (F2) to (F4) and formulae (CS-1) to (CS-3):
wherein each of R57 to R68 independently represents a hydrogen atom, a fluorine atom, a linear or branched alkyl group or an aryl group, provided that at least one of R57 to R61, at least one of R62 to R64 and at least one of R65 to R68 each independently represent a fluorine atom or an alkyl group with at least one hydrogen atom being replaced by a fluorine atom, and R62 and R63 may combine with each other to form a ring:
wherein each of R12 to R26 independently represents a linear or branched alkyl group or a cycloalkyl group;
each of L3 to L5 represents a single bond or a divalent linking group; and
n represents an integer of 1 to 5.

### Claim 6 (depends on 5)

The actinic ray-sensitive or radiation-sensitive resin composition according to claim 5,
wherein the resin (C) contains at least one acrylate or methacrylate repeating unit having the group represented by any one of formulae (F2) to (F4) and formulae (CS-1) to (CS-3).

### Claim 7 (depends on 1)

The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1,
wherein the content of the resin (C) is from 0.01 to 10 mass % based on the entire solids content in the actinic ray-sensitive or radiation-sensitive resin composition.

### Claim 8 (depends on 7)

The actinic ray-sensitive or radiation-sensitive resin composition according to claim 7,
wherein the content of the resin (C) is 0.1 to 5 mass %, based on the entire solids content of the actinic ray-sensitive or radiation-sensitive resin composition.

### Claim 9 (depends on 1)

The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, which further comprises:
(B) a compound capable of generating an acid upon irradiation with an actinic ray or radiation.

### Claim 10 (depends on 9)

The actinic ray-sensitive or radiation-sensitive resin composition according to claim 9,
wherein the compound (B) is a compound capable of generating an acid represented by the following formula (1):
wherein in formula (1), each of R1 to R8 independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a hydroxyl group;
R9 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, —CORx or —SO2Rs;
A represents a heteroatom-containing divalent linking group or a single bond;
Rx represents an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group;
Rs represents an alkyl group, a cycloalkyl group or an aryl group;
each of m1 to m4 independently represents an integer of 0 to 12, provided that m3+m4≧1;
m5 represents an integer of 1 to 3; and
when any of m1 to m5 is an integer of 2 or more, a plurality of members for each of R1 to R8 and A may be the same or different.

### Claim 11 (depends on 9)

The actinic ray-sensitive or radiation-sensitive resin composition according to claim 9,
wherein the compound (B) is a compound represented by the following formula (I):
wherein in formula (I), X+represents an organic counter ion, and R represents a hydrogen atom or an organic group.

### Claim 12 (depends on 1)

The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1,
wherein the resin (A) contains a lactone structure-containing repeating unit.

### Claim 13 (depends on 1)

A resist film, which is formed from the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1.

### Claim 14 (depends on 13)

A pattern forming method, comprising:
immersion-exposing and developing the resist film according to claim 13.

### Claim 15 (depends on 1)

The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1,
wherein the resin (A) is a resin where all repeating units are (meth)acrylate-based repeating units.

### Claim 16 (depends on 1)

The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1,
wherein the resin (A) contains no aromatic group.

### Claim 17 (depends on 1)

The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1,
wherein the resin (A) contains at least two kinds of repeating units represented by the following formula (1):
wherein in formula (1), R1 represents a hydrogen atom, a methyl group which may have a substituent, or a group represented by —CH2—R9; R9 represents a hydroxyl group or a monovalent organic group;
R2 represents an alkyl group or a cycloalkyl group; and
R represents an atomic group necessary for forming an alicyclic structure together with the carbon atom.

### Claim 18 (depends on 1)

The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1,
wherein the actinic ray-sensitive or radiation-sensitive resin composition further contains a compound represented by the following Formula (A):
wherein in Formula (A), each of R200, R201 and R202 , which may be the same or different, represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and R201 and R202 may combine together to form a ring.

### Claim 19 (depends on 1)

The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1,
wherein the actinic ray-sensitive or radiation-sensitive resin composition further contains one, as a solvent, selected from the group consisting of cyclohexanone, ethyl lactate, γ-butyrolactone, and propylene carbonate.

### Claim 20

An actinic ray-sensitive or radiation-sensitive resin composition, comprising:
(A) a resin capable of increasing a solubility of the resin (A) in an alkali developer by an action of an acid; and
(C) a resin having at least either a fluorine atom or a silicon atom and containing (c) a repeating unit having at least two or more polarity conversion groups represented by —COO— in the structure represented by formula (KA-1) or (KB-1):
wherein Zka represents an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group or an electron-withdrawing group, and when a plurality of Zka's are present, the plurality of Zka's are the same or different;
each Zka may combine with every other Zka to form a ring;
nka represents an integer of 0 to 10;
each of Xkb1 and Xkb2 independently represents an electron-withdrawing group;
each of nkb and nkb′ independently represents 0 or 1; and
each of Rkb1 to Rkb4 independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an electron-withdrawing group, at least two members of Rkb1, Rkb2 and Xkb1 may combine with each other to form a ring, and at least two members of Rkb3, Rkb4 and Xkb2 may combine with each other to form a ring,
wherein:
the resin (A) contains no fluorine atom and no silicon atom;
the resin (A) includes a repeating unit represented by the following Formula (AI):
wherein in formula (AI), Xa1 represents a hydrogen atom, a methyl group which may have a substituent, or a group represented by —CH2—R9; R9 represents a hydroxyl group or a monovalent organic group;
T represents a single bond or a divalent linking group;
each of Rx1 to Rx3 independently represents a linear or branched alkyl group or a monocyclic or polycyclic cycloalkyl group; and
two members out of Rx1 to Rx3 may combine to form a monocyclic or polycyclic cycloalkyl group;
and further wherein:
the repeating unit (c) is (c*) a repeating unit having the at least two or more polarity conversion groups and having neither a fluorine atom nor a silicon atom, and
the resin (C) further contains a repeating unit having at least either a fluorine atom or a silicon atom.

### Claim 21

An actinic ray-sensitive or radiation-sensitive resin composition, comprising:
(A) a resin capable of increasing a solubility of the resin (A) in an alkali developer by an action of an acid; and
(C) a resin having at least either a fluorine atom or a silicon atom and containing (c) a repeating unit having at least two or more polarity conversion groups represented by —COO— in the structure represented by formula (KA-1) or (KB-1):
wherein Zka represents an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group or an electron-withdrawing group, and when a plurality of Zka's are present, the plurality of Zka's are the same or different;
each Zka may combine with every other Zka to form a ring;
nka represents an integer of 0 to 10;
each of Xkb1 and Xkb2 independently represents an electron-withdrawing group;
each of nkb and nkb′ independently represents 0 or 1; and
each of Rkb1 to Rkb4 independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an electron-withdrawing group, at least two members of Rkb1, Rkb2 and Xkb1 may combine with each other to form a ring, and at least two members of Rkb3, Rkb4 and Xkb2 may combine with each other to form a ring,
wherein:
the resin (A) contains no fluorine atom and no silicon atom;
the resin (A) includes a repeating unit represented by the following Formula (AI):
wherein in formula (AI), Xa1 represents a hydrogen atom, a methyl group which may have a substituent, or a group represented by —CH2—R9; R9 represents a hydroxyl group or a monovalent organic group;
T represents a single bond or a divalent linking group;
each of Rx1 to Rx3 independently represents a linear or branched alkyl group or a monocyclic or polycyclic cycloalkyl group; and
two members out of Rx1 to Rx3 may combine to form a monocyclic or polycyclic cycloalkyl group; and
the repeating unit (c) has a structure represented by the following formula (KY-1):
wherein each of Rky1 and Rky4 independently represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a carbonyl group, a carbonyloxy group, an oxycarbonyl group, an ether group, a hydroxyl group, a cyano group, an amide group or an aryl group, Rky1 and Rky4 may be bonded to the same atom to form a double bond;
each of Rky2 and Rky3 independently represents an electron-withdrawing group, or R1 and Rky2 are combined to form a lactone ring and at the same time, Rky3 is an electron-withdrawing group;
at least two members of Rky1, Rky2 and Rky4 may combine with each other to form a monocyclic or polycyclic structure; and
Rkb1 to Rkb4, nkb and nkb′ have the same meanings as in formula (KB-1).