# US 9,040,221 B2 · Radiation-sensitive resin composition, method for forming resist pattern, and polymer and compound

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- Number: US 9,040,221 B2
- Document ID: US9040221B2
- Status: Granted
- Kind: B2
- Application number: 13/699,007
- Filed: 2011-05-19
- Published: 2013-05-16
- Granted: 2015-05-26
- Earliest claimed: 2010-05-20
- Assignees: Jsr Corporation
- Applicants: Hitoshi Osaki; Yusuke Asano; Mitsuo Sato; Tomoki Nagai
- Inventors: Hitoshi Osaki; Yusuke Asano; Mitsuo Sato; Tomoki Nagai
- Web page: https://patentgrep.com/patent/US9040221B2

## CPC

- G03F 7/004: Photosensitive materials (G03F7/12, G03F7/14 take precedence)
- C07C 69/653: Acrylic acid esters; Methacrylic acid esters; Haloacrylic acid esters; Halomethacrylic acid esters
- C07C 69/753: of polycyclic acids
- C07D 307/93: condensed with a ring other than six-membered
- C08F 22/18: Esters containing halogen
- 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)
- C08F 220/26: Esters containing oxygen in addition to the carboxy oxygen
- G03F 7/0046: {with perfluoro compounds, e.g. for dry lithography (G03F7/0048 takes precedence)}
- G03F 7/0382: {the macromolecular compound being present in a chemically amplified negative photoresist composition}
- G03F 7/0392: {the macromolecular compound being present in a chemically amplified positive photoresist composition}
- G03F 7/2041: {in the presence of a fluid, e.g. immersion; using fluid cooling means}
- C08F 220/24: containing perhaloalkyl radicals
- 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)
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

A radiation-sensitive resin composition that provides a resist coating film in a liquid immersion lithography process is provided, the radiation-sensitive resin composition being capable of exhibiting a great dynamic contact angle during exposure, whereby the surface of the resist coating film can exhibit a superior water draining property, and the radiation-sensitive resin composition being capable of leading to a significant decrease in the dynamic contact angle during development, whereby generation of development defects can be inhibited, and further shortening of a time period required for change in a dynamic contact angle is enabled. A radiation-sensitive resin composition including (A) a fluorine-containing polymer having a structural unit (I) that includes a group represented by the following formula (1), and (B) a radiation-sensitive acid generator.

## Claims

### Claim 1

A radiation-sensitive resin composition comprising:
(A) a fluorine-containing polymer comprising a structural unit (I-3) represented by formula (1-3); and
(B) a radiation-sensitive acid generator:
wherein, in the formula (1-3), RL11 represents a single bond or a bivalent linking group; X represents a bivalent hydrocarbon group having 1 to 20 carbon atoms and having at least one fluorine atom; R0 represents a monovalent aromatic hydrocarbon group not having or optionally having a substituent; and R represents a hydrogen atom, a fluorine atom, a methyl group or a fluorinated methyl group.

### Claim 2 (depends on 1)

The radiation-sensitive resin composition according to claim 1, wherein the structural unit (I-3) is at least one structural unit selected from the group consisting of structural units represented by the following formulae (1-3a) to (1-3e), respectively:
wherein, in the formulae (1-3a) to (1-3e), R0, R and RL11 are as defined in the formula (1-3).

### Claim 3 (depends on 1)

The radiation-sensitive resin composition according to claim 1, wherein the R0 represents at least one selected from the set consisting of groups represented by (R0-a) and (R0-b):
wherein, in the formulae (R0-a) and (R0-b), R01 each independently represents a monovalent organic group having a fluorine atom; R02 each independently represents a substituent; nfl is each independently 0 or 1; and nfl1 is an integer of 1 to (5+2nfl); nfl2 is an integer of 0 to (5+2nfl), wherein an inequality of: (nfl1+nfl2)≦(5+2nfl) is satisfied; and nfl3 is an integer of 0 to (5+2nfl).

### Claim 4 (depends on 1)

The radiation-sensitive resin composition according to claim 1, wherein the content of the structural unit (I-3) in the polymer (A) is no less than 30 mol % and no greater than 100 mol %.

### Claim 5 (depends on 1)

The radiation-sensitive resin composition according to claim 1, wherein the polymer (A) further comprises at least one structural unit selected from the group consisting of a structural unit (II) represented by formula (2) and a structural unit (III) represented by (3):
wherein,
in the formulae (2) and (3), R is as defined in the above-formula (1-3),
in the formula (2), G represents a single bond, an oxygen atom, a sulfur atom, —CO—O—, —SO2—O—NH—, —CO—NH— or —O—CO—NH—; and R1 represents a monovalent chain hydrocarbon group having 1 to 6 carbon atoms and having at least one fluorine atom, or a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms and having at least one fluorine atom, and
in the formula (3), R2 represents a hydrocarbon group having a valency of (s+1) and having 1 to 20 carbon atoms, or a group which an oxygen atom, a sulfur atom, —NR′—, a carbonyl group, —CO—O— or —CO—NH— is bound to a hydrocarbon group having a valency of (s+1) and having 1 to 20 carbon atoms at an end of R3 side, wherein R′ represents a hydrogen atom or a monovalent organic group; R3 represents a single bond, a bivalent chain hydrocarbon group having 1 to 10 carbon atoms or a bivalent alicyclic hydrocarbon group having 4 to 20 carbon atoms; X2 represents a single bond, or a bivalent chain hydrocarbon group having 1 to 20 carbon atoms and having at least one fluorine atom; A represents an oxygen atom, —NR″—, —CO—O—* or —SO2—O—*, wherein R″ represents a hydrogen atom or a monovalent organic group and * denotes a site bound to R4; R4 represents a hydrogen atom or a monovalent organic group; and s is an integer of 1 to 3, wherein in a case where s is 2 or 3, a plurality of R3s, X2s, As and R4s are each independently defined as described above.

### Claim 6 (depends on 1)

The radiation-sensitive resin composition according to claim 1, further comprising (C) a polymer having an acid-dissociable group and having a content of fluorine atoms less than a content of fluorine atoms of the polymer (A).

### Claim 7 (depends on 6)

The radiation-sensitive resin composition according to claim 6, wherein the content of the polymer (A) is no less than 0.1 parts by mass and no greater than 10 parts by mass with respect to 100 parts by mass of the polymer (C).

### Claim 8 (depends on 1)

A method for forming a resist pattern comprising:
forming a photoresist film on a substrate using the radiation-sensitive resin composition according to claim 1;
subjecting the photoresist film to liquid immersion lithography; and
forming a resist pattern by developing the photoresist film subjected to the liquid immersion lithography.

### Claim 9

A compound represented by formula (i):
wherein, in the formula (i), R represents a hydrogen atom, a fluorine atom, a methyl group or a fluorinated methyl group; RL11 represents a single bond or a bivalent linking group; X represents a bivalent hydrocarbon group having 1 to 20 carbon atoms and having at least one fluorine atom; and Ro represents a monovalent aromatic hydrocarbon group not having or optionally having a substituent.

### Claim 10 (depends on 9)

The compound according to claim 9, wherein X represents —CF2—, —CHF—, —CF(CF3)—, —CH(CF3)—, or —C(CF3)2—.

### Claim 11 (depends on 9)

The compound according to claim 9, wherein the R0 represents at least one selected from the set consisting of groups represented by formulae (R0-a) and (R0-b):
wherein, in the formulae (R0-a) and (R0-b), R01 each independently represents a monovalent organic group having a fluorine atom; R02 each independently represents a substituent; nfl is each independently 0 or 1; and nfl1′ is an integer of 1 to (5+2nfl); nfl2 is an integer of 0 to (5+2nfl), wherein an inequality of: (nfl1+nfl2)≦(5+2nfl) is satisfied; and nfl3 is an integer of 0 to (5+2nfl).