# US 8,541,160 B2 · Actinic-ray- or radiation-sensitive resin composition and method of forming pattern using the same

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- Number: US 8,541,160 B2
- Document ID: US8541160B2
- Status: Granted
- Kind: B2
- Application number: 13/095,328
- Filed: 2011-04-27
- Published: 2011-11-03
- Granted: 2013-09-24
- Earliest claimed: 2010-04-28
- Assignees: FUJIFILM Corporation
- Applicants: Akinori Shibuya
- Inventors: Akinori Shibuya
- Web page: https://patentgrep.com/patent/US8541160B2

## CPC

- G03F 7/0397: {the macromolecular compound having an alicyclic moiety in a side chain}
- 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 7/2041: {in the presence of a fluid, e.g. immersion; using fluid cooling means}
- 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

Provided is an actinic-ray- or radiation-sensitive resin composition excelling in the LWR, pattern collapse performance and DOF, and a method of forming a pattern using the same. The composition according to the present invention contains (A) a resin containing a repeating unit with any of partial structures of general formula (I) below, (B) a compound (PA) as defined in the specification, and (C) a compound being configured to generate an acid when exposed to actinic rays or radiation, wherein the resin is contained in an amount of 50 mass % or more based on total solids of the composition.

## Claims

### Claim 1

An actinic-ray- or radiation-sensitive resin composition comprising:
(A) a resin containing a repeating unit with any of partial structures of general formula (I) below, the resin being configured to increase its rate of dissolution in an alkali developer when acted on by an acid;
(B) a compound (PA) containing a functional group with proton acceptor properties and being configured to decompose when exposed to actinic rays or radiation to thereby produce a compound exhibiting lower or no proton acceptor properties or a compound exhibiting acid properties instead of the proton acceptor properties; and
(C) a compound being configured to generate an acid when exposed to actinic rays or radiation;
wherein the resin is contained in an amount of 50 mass % or more based on total solids of the composition,
in which R13 represents a hydrogen atom, an alkyl group or a cycloalkyl group; and
wherein the composition further comprises a hydrophobic resin.

### Claim 2 (depends on 1)

The composition according to claim 1, wherein the repeating unit is represented by at least one selected from the group consisting of general formulae (I-1) to (I-3) below,
in which
each of R3, R11 and R14 independently represents a hydrogen atom, an alkyl group or a halogen atom;
each of X1, X3 and X4 independently represents any one of —C(═O)—, —C(═O)—O—, —C(═O)—O—R6—, —O—, —C(═O)—R6—C(═O)— and —C(═O)—O—R6—C(═O)—O—, in which R6 represents an alkylene group or a cycloalkylene group;
R1 represents a hydrogen atom, an alkyl group, a cycloalkyl group or a halogen atom, and R2 represents a hydrogen atom, an alkyl group or a cycloalkyl group, provided that R1 and R2 may be bonded to each other to thereby form a ring;
R12 represents a cycloalkylene group or a cycloalkanetriyl group, and R13 represents a hydrogen atom, an alkyl group or a cycloalkyl group, provided that in general formula (I-2), R12 and R13 may be bonded to each other to thereby form a ring; and
n1 is 1 or 2.

### Claim 3 (depends on 2)

The composition according to claim 2, wherein the repeating unit is represented by the general formula (I-1) or (I-3).

### Claim 4 (depends on 2)

The composition according to claim 2, wherein the repeating unit is represented by the general formula (I-2) in which n1 is 2.

### Claim 5 (depends on 1)

The composition according to claim 1, wherein the compound produced by the decomposition of the compound (PA) upon exposure to actinic rays or radiation is represented by general formula (PA-1) below:
Q-A-(X)n—B—R (PA-1)
in which
Q represents —SO3H, —CO2H or —W1NHW2Rf, in which Rf represents an alkyl group, a cycloalkyl group or an aryl group, and each of W1 and W2 independently represents —SO2— or —CO—;
A represents a single bond or a bivalent connecting group;
X represents —SO2— or —CO—;
n is 0 or 1;
B represents a single bond, an oxygen atom or —N(Rx)Ry—, in which Rx represents a hydrogen atom or a monovalent organic group, and Ry represents a single bond or a bivalent organic group, provided that Rx may be bonded to Ry to thereby form a ring or may be bonded to R to thereby form a ring; and
R represents a monovalent organic group containing the functional group with proton acceptor properties.

### Claim 6 (depends on 5)

The composition according to claim 5, wherein Q represents —SO3H or —CO2H.

### Claim 7 (depends on 1)

The composition according to claim 1, wherein the compound (PA) is represented by general formula (7) below,
in which
A represents a sulfur atom or an iodine atom;
m is 1 or 2 and n is 1 or 2, provided that m+n=3 when A is a sulfur atom and that m+n=2 when A is an iodine atom;
R represents an aryl group;
RN represents an aryl group substituted with the functional group with proton acceptor properties; and
X− represents a counter anion.

### Claim 8 (depends on 1)

The composition according to claim 1, wherein the resin further contains any of repeating units of general formula (II-1) below:
in which
R represents a hydrogen atom, an alkyl group or a halogen atom;
A represents —COO— or —CONH—;
R0, when n≧2 each independently, represents an alkylene group, a cycloalkylene group or a combination thereof;
Z, when n≧2 each independently, represents an ether bond, an ester bond, an amido bond, a urethane bond or a urea bond;
L represents a substituent with a lactone structure; and
n is an integer of 1 to 5.

### Claim 9 (depends on 1)

The composition according to claim 1, the hydrophobic resin comprising at least one of a fluorine atom and a silicone atom.

### Claim 10 (depends on 1)

The composition according to claim 1, the hydrophobic resin comprising at least one group selected from among the following groups (x), (y) and (z):
(x) an alkali-soluble group;
(y) a group that is decomposed by the action of an alkali developer, resulting in an increase of solubility in the alkali developer; and
(z) a group that is decomposed by the action of an acid.

### Claim 11 (depends on 1)

The composition according to claim 1, wherein a content of the hydrophobic resin in the composition based on the total solids thereof is in the range of 0.01 to 20 mass %.

### Claim 12 (depends on 1)

A resist film formed from the composition according to claim 1.

### Claim 13 (depends on 1)

A method of forming a pattern, comprising:
forming the composition according to claim 1 into a film,
exposing the film, and
developing the exposed film.

### Claim 14 (depends on 13)

The method according to claim 13, wherein the exposure is performed through an immersion liquid.

### Claim 15

An actinic-ray- or radiation-sensitive resin composition comprising:
(A) a resin containing a repeating unit with any of partial structures of general formula (I) below, the resin being configured to increase its rate of dissolution in an alkali developer when acted on by an acid;
(B) a compound (PA) containing a functional group with proton acceptor properties and being configured to decompose when exposed to actinic rays or radiation to thereby produce a compound exhibiting lower or no proton acceptor properties or a compound exhibiting acid properties instead of the proton acceptor properties; and
(C) a compound being configured to generate an acid when exposed to actinic rays or radiation;
wherein the resin is contained in an amount of 50 mass % or more based on total solids of the composition,
in which R13 represents a hydrogen atom, an alkyl group or a cycloalkyl group and
wherein the acid generator (C) is limited to a compound represented by general formula (ZI) or (ZII)
wherein in general formula (ZI),
each of R201, R202 and R203 independently represents an organic group, and
Z− represents an sulfonate anion configured to generate the acid represented by general formula (I) below:
wherein in general formula (ZII),
each of R204 and R205 independently represents an aryl group, an alkyl group or a cycloalkyl group, and
Z− represents an sulfonate anion configured to generate the acid represented by general formula (I) below:
wherein in general formula (I),
each of Xfs independently represents a fluorine atom or an alkyl group having at least one hydrogen atom thereof substituted with one or more fluorine atoms,
each of R1 and R2 represents a hydrogen atom,
L, when z≧2 each independently, represents a bivalent connecting group,
A represents an organic group with a cyclic structure,
x is 1 or 2,
y is an integer of 0 to 10, and
z is an integer of 0 to 10.

### Claim 16 (depends on 15)

The composition according to claim 15, wherein the compound produced by the decomposition of the compound (PA) upon exposure to actinic rays or radiation is represented by general formula (PA-1) below:
Q-A-(X)n—B—R (PA-1)
in which
Q represents —SO3H, —CO2H or —W1NHW2Rf, in which Rf represents an alkyl group, a cycloalkyl group or an aryl group, and each of W1 and W2 independently represents —SO2—or —CO—;
A represents a single bond or a bivalent connecting group;
X represents —SO2— or —CO—;
n is 0 or 1;
B represents a single bond, an oxygen atom or —N(Rx)Ry—, in which Rx represents a hydrogen atom or a monovalent organic group, and Ry represents a single bond or a bivalent organic group, provided that Rx may be bonded to Ry to thereby form a ring or may be bonded to R to thereby form a ring; and
R represents a monovalent organic group containing the functional group with proton acceptor properties.

### Claim 17 (depends on 16)

The composition according to claim 16, wherein Q represents —SO3H or —CO2H.

### Claim 18 (depends on 15)

The composition according to claim 15, wherein the compound (PA) is represented by general formula (7) below,
in which
A represents a sulfur atom or an iodine atom;
m is 1 or 2 and n is 1 or 2, provided that m+n=3 when A is a sulfur atom and that m+n=2 when A is an iodine atom;
R represents an aryl group;
RN represents an aryl group substituted with the functional group with proton acceptor properties; and
X− represents a counter anion.

### Claim 19

An actinic-ray- or radiation-sensitive resin composition comprising:
(A) a resin containing a repeating unit with any of partial structures of general formula (I) below, the resin being configured to increase its rate of dissolution in an alkali developer when acted on by an acid;
(B) a compound (PA) containing a functional group with proton acceptor properties and being configured to decompose when exposed to actinic rays or radiation to thereby produce a compound exhibiting lower or no proton acceptor properties or a compound exhibiting acid properties instead of the proton acceptor properties; and
(C) a compound being configured to generate an acid when exposed to actinic rays or radiation;
wherein the resin is contained in an amount of 50 mass % or more based on total solids of the composition,
in which R13 represents a hydrogen atom, an alkyl group or a cycloalkyl group, and
wherein the resin (A) further contains at least two kinds of repeating unit represented by general formula (1) below:
wherein in general formula (I),
R1 represents a hydrogen atom, a methyl group or any of the groups of the formula —CH2—R9, in which R9 represents a monovalent organic group,
R2 represents an alkyl group or a cycloalkyl group and
R represents an atomic group required for forming an alicyclic structure in cooperation with a carbon atom.

### Claim 20 (depends on 19)

The composition according to claim 19, wherein the compound produced by the decomposition of the compound (PA) upon exposure to actinic rays or radiation is represented by general formula (PA-1) below:
Q-A-(X)n—B—R (PA-1)
in which
Q represents —SO3H, —CO2H or —W1NHW2Rf, in which Rf represents an alkyl group, a cycloalkyl group or an aryl group, and each of W1 and W2 independently represents —SO2— or —CO—;
A represents a single bond or a bivalent connecting group;
X represents —SO2—or —CO—;
n is 0 or 1;
B represents a single bond, an oxygen atom or —N(Rx)Ry—, in which Rx represents a hydrogen atom or a monovalent organic group, and Ry represents a single bond or a bivalent organic group, provided that Rx may be bonded to Ry to thereby form a ring or may be bonded to R to thereby form a ring; and
R represents a monovalent organic group containing the functional group with proton acceptor properties.

### Claim 21 (depends on 20)

The composition according to claim 20, wherein Q represents —SO3H or —CO2H.

### Claim 22 (depends on 19)

The composition according to claim 19, wherein the compound (PA) is represented by general formula (7) below,
in which
A represents a sulfur atom or an iodine atom;
m is 1 or 2 and n is 1 or 2, provided that m+n=3 when A is a sulfur atom and that m+n=2 when A is an iodine atom;
R represents an aryl group;
RN represents an aryl group substituted with the functional group with proton acceptor properties; and
X− represents a counter anion.

### Claim 23 (depends on 19)

The composition according to claim 19, wherein the alicyclic structure formed by R included in at least one kind of repeating unit represented by general formula (1) is an alicyclic structure of a single ring.