# US 8,541,159 B2 · Positive resist composition for immersion exposure and pattern forming method

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- Number: US 8,541,159 B2
- Document ID: US8541159B2
- Status: Granted
- Kind: B2
- Application number: 13/057,287
- Filed: 2009-09-25
- Published: 2011-06-16
- Granted: 2013-09-24
- Earliest claimed: 2008-09-26
- Assignees: FUJIFILM Corporation
- Applicants: Kei Yamamoto; Hiroshi Saegusa
- Inventors: Kei Yamamoto; Hiroshi Saegusa
- Web page: https://patentgrep.com/patent/US8541159B2

## CPC

- G03F 7/039: Macromolecular compounds which are photodegradable, e.g. positive electron resists (G03F7/075 takes precedence; macromolecular quinonediazides G03F7/023)
- C09D 133/16: Homopolymers or copolymers of esters containing halogen atoms
- C09D 133/26: Homopolymers or copolymers of acrylamide or methacrylamide
- C09D 143/04: Homopolymers or copolymers of monomers containing silicon
- 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 7/0048: {characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents}
- G03F 7/0397: {the macromolecular compound having an alicyclic moiety in a side chain}
- G03F 7/0758: {with silicon- containing groups in the side chains}
- G03F 7/2041: {in the presence of a fluid, e.g. immersion; using fluid cooling means}
- Y10S 430/122: Sulfur compound containing
- Y10S 430/126: Halogen compound containing
- 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)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

## Abstract

A positive resist composition for immersion exposure includes the following (A) to (D): (A) a resin capable of decomposing by an action of an acid to increase a solubility of the resin in an alkali developer; (B) a compound capable of generating an acid upon irradiation with an actinic ray or radiation; (C) a resin having at least either one of a fluorine atom and a silicon atom; and (D) a mixed solvent containing at least one kind of a solvent selected from the group consisting of solvents represented by any one of the following formulae (S1) to (S3) as defined in the specification, in which a total amount of the at least one kind of the solvent is from 3 to 20 mass % based on all solvents of the mixed solvent (D).

## Claims

### Claim 1

A positive resist composition for immersion exposure, comprising the following (A) to (D):
(A) a resin capable of decomposing by an action of an acid to increase a solubility of the resin in an alkali developer;
(B) a compound capable of generating an acid upon irradiation with an actinic ray or radiation;
(C) a resin having at least either one of a fluorine atom and a silicon atom; and
(D) a mixed solvent containing at least one kind of a solvent selected from the group consisting of solvents represented by any one of the following formulae (S1) to (S3), in which a total amount of the at least one kind of the solvent is from 3 to 20 mass % based on all solvents of the mixed solvent (D):
wherein each of R1 to R7 independently represents an alkyl group, a cycloalkyl group or an aryl group; and
R1 and R2, R3 and R4, and R6 and R7 may combine with each other to form a ring, respectively;
wherein the resin (C) contains at least one group selected from the following (x) to (z):
(x) an alkali-soluble group;
(y) a group capable of decomposing by the action of an alkali developer to increase the solubility in an alkali developer, and
(z) a group capable of decomposing by the action of an acid; and
the mixed solvent (D) is a mixed solvent containing only propylene glycol monomethyl ether acetate (PGMEA) and γ-butyrolactone.

### Claim 2 (depends on 1)

The positive resist composition for immersion exposure according to claim 1,
wherein the resin (C) has at least one group represented by any one of the following formulae (F2) to (F4) and (CS-1) to (CS-3):
wherein each of R57 to R68 independently represents a hydrogen atom, a fluorine atom, an alkyl group, a cycloalkyl 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 represent a fluorine atom or an alkyl, cycloalkyl or aryl group with at least one hydrogen atom being substituted 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 an alkyl group or a cycloalkyl group;
each of L3 to L5 independently represents a single bond or a divalent linking group; and
n represents an integer of 1 to 5.

### Claim 3 (depends on 2)

The positive resist composition for immersion exposure according to claim 2,
wherein the resin (C) contains at least one repeating unit derived from an acrylate or methacrylate having a group represented by any one of formulae (F2) to (F4) and (CS-1) to (CS-3).

### Claim 4 (depends on 1)

The positive resist composition for immersion exposure according to claim 1,
wherein the total amount of the at least one kind of the solvent selected from the group consisting of solvents represented by any one of formulae (S1) to (S3) is from 3 to 10 mass % based on all solvents of the mixed solvent (D).

### Claim 5 (depends on 1)

A pattern forming method, comprising:
forming a resist film from the positive resist composition for immersion exposure according to claim 1;
exposing the resist film through an immersion liquid so as to form an exposed resist film; and
developing the exposed resist film.

### Claim 6 (depends on 1)

The positive resist composition for immersion exposure according to claim 1,
wherein the amount of the resin (C) is from 0.01 to 10 mass % based on the entire solid content of the positive resist composition.

### Claim 7 (depends on 1)

A resist film, which is formed from the positive resist composition for immersion exposure according to claim 1.

### Claim 8

A positive resist composition for immersion exposure, comprising the following (A) to (D):
(A) a resin capable of decomposing by an action of an acid to increase a solubility of the resin in an alkali developer;
(B) a compound capable of generating an acid upon irradiation with an actinic ray or radiation;
(C) a resin having at least either one of a fluorine atom and a silicon atom; and
(D) a mixed solvent containing at least one kind of a solvent selected from the group consisting of solvents represented by any one of the following formulae (S1) to (S3), in which a total amount of the at least one kind of the solvent is from 3 to 20 mass % based on all solvents of the mixed solvent (D):
wherein each of R1 to R7 independently represents an alkyl group, a cycloalkyl group or an aryl group; and
R1 and R2, R3 and R4, and R6 and R7 may combine with each other to form a ring, respectively;
wherein the resin (C) contains at least one group selected from the following (x) to (z):
(x) an alkali-soluble group;
(y) a group capable of decomposing by the action of an alkali developer to increase the solubility in an alkali developer, and
(z) a group capable of decomposing by the action of an acid; and
the mixed solvent (D) is a mixed solvent containing only propylene glycol monomethyl ether acetate (PGMEA) and propylene carbonate.

### Claim 9 (depends on 8)

The positive resist composition for immersion exposure according to claim 8,
wherein the resin (C) has at least one group represented by any one of the following formulae (F2) to (F4) and (CS-1) to (CS-3):
wherein each of R57 to R68 independently represents a hydrogen atom, a fluorine atom, an alkyl group, a cycloalkyl 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 represent a fluorine atom or an alkyl, cycloalkyl or aryl group with at least one hydrogen atom being substituted 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 an alkyl group or a cycloalkyl group;
each of L3 to L5 independently represents a single bond or a divalent linking group; and
n represents an integer of 1 to 5.

### Claim 10 (depends on 9)

The positive resist composition for immersion exposure according to claim 9,
wherein the resin (C) contains at least one repeating unit derived from an acrylate or methacrylate having a group represented by any one of formulae (F2) to (F4) and (CS-1) to (CS-3).

### Claim 11 (depends on 8)

The positive resist composition for immersion exposure according to claim 8,
wherein the total amount of the at least one kind of the solvent selected from the group consisting of solvents represented by any one of formulae (S1) to (S3) is from 3 to 10 mass % based on all solvents of the mixed solvent (D).

### Claim 12 (depends on 8)

A pattern forming method, comprising:
forming a resist film from the positive resist composition for immersion exposure according to claim 8;
exposing the resist film through an immersion liquid so as to form an exposed resist film; and
developing the exposed resist film.

### Claim 13 (depends on 8)

The positive resist composition for immersion exposure according to claim 8,
wherein the amount of the resin (C) is from 0.01 to 10 mass % based on the entire solid content of the positive resist composition.

### Claim 14 (depends on 8)

A resist film, which is formed from the positive resist composition for immersion exposure according to claim 8.