# US 2021/0278764 A1 · Fluorine-containing polymer, purification method, and radiation-sensitive resin composition

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- Number: US 2021/0278764 A1
- Document ID: US20210278764A1
- Status: Published application
- Kind: A1
- Application number: 17/320,640
- Filed: 2021-05-14
- Published: 2021-09-09
- Earliest claimed: 2006-03-31
- Assignees: Jsr Corporation
- Applicants: Jsr Corporation
- Inventors: Hiroki NAKAGAWA; Hiromitsu NAKASHIMA; Gouji WAKAMATSU; Kentarou GOTOU; Yukio NISHIMURA; Takeo SHIOYA
- Web page: https://patentgrep.com/patent/US20210278764A1

## CPC

- G03F 7/0046: {with perfluoro compounds, e.g. for dry lithography (G03F7/0048 takes precedence)}
- C08F 220/18: with acrylic or methacrylic acids
- C08F 220/1807: {C7-(meth)acrylate, e.g. heptyl (meth)acrylate or benzyl (meth)acrylate}
- C08F 220/24: containing perhaloalkyl radicals
- C08F 220/28: containing no aromatic rings in the alcohol moiety
- G03F 7/0045: {with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors}
- G03F 7/039: Macromolecular compounds which are photodegradable, e.g. positive electron resists (G03F7/075 takes precedence; macromolecular quinonediazides G03F7/023)
- G03F 7/0397: {the macromolecular compound having an alicyclic moiety in a side chain}
- G03F 7/162: {Coating on a rotating support, e.g. using a whirler or a spinner}
- G03F 7/168: {Finishing the coated layer, e.g. drying, baking, soaking}
- G03F 7/2006: {using coherent light; using polarised light}
- G03F 7/2041: {in the presence of a fluid, e.g. immersion; using fluid cooling means}
- G03F 7/322: {Aqueous alkaline compositions}
- G03F 7/38: Treatment before imagewise removal, e.g. prebaking {(G03F7/265 takes precedence)}
- G03F 7/40: Treatment after imagewise removal, e.g. baking
- C08F 220/283: {and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate}
- 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)
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

An object of the present invention is to provide a novel fluorine-containing polymer, a radiation-sensitive resin composition for liquid immersion lithography which contains the fluorine-containing polymer, which leads to a pattern having an excellent shape and excellent depth of focus, wherein the amount of an eluted component in a liquid for liquid immersion lithography such as water that comes in contact with the resist during exposure in liquid immersion lithography is little, and which provides a larger receding contact angle between the resist film and the liquid for liquid immersion lithography such as water, and a method for purifying the fluorine-containing polymer. The present resin composition comprises a novel fluorine-containing polymer (A) containing repeating units represented by the general formulae (1) and (2) and having Mw of 1,000-50,000, a resin (B) having an acid-unstable group, a radiation-sensitive acid generator (C), a nitrogen-containing compound (D) and a solvent (E).

## Claims

### Claim 1

A radiation-sensitive resin composition, comprising:
a fluorine-containing polymer including a repeating unit of formula (1) and a repeating unit of formula (2); and
an acid-unstable resin including a repeating unit of the formula (2),
wherein the formula (1) is
where R1 represents a hydrogen atom, a methyl group or a trifluoromethyl group,
A represents a single bond, an oxygen atom, a sulfur atom, a carbonyloxy group, an oxycarbonyl group, an amide group, a sulfonylamide group, or a urethane group, and
R2 represents a linear or branched, partially or fully fluorinated alkyl group having 1 to 6 carbon atoms or a monovalent partially or fully fluorinated alicyclic hydrocarbon group having 4 to 20 carbon atoms,
the formula (2) is
where R3 represents a hydrogen atom, a methyl group or a trifluoromethyl group, and
each R4 individually represents a monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or a linear or branched alkyl group having 1 to 4 carbon atoms, and
at least one of the fluorine-containing polymer and the acid-unstable resin includes the repeating unit of the formula (2) satisfying that two of R4s taken together represent an alicyclic hydrocarbon group derived from cyclopentane or cyclohexane, together with the carbon atom to which the two of R4s bond.

### Claim 2 (depends on 1)

The radiation-sensitive resin composition of claim 1, further comprising:
a radiation-sensitive acid generator;
a nitrogen-containing compound; and
a solvent.

### Claim 3 (depends on 1)

The radiation-sensitive resin composition of claim 1, wherein the fluorine-containing polymer includes the repeating unit of the formula (1) and the repeating unit of the formula (2) at a total content of 95 mol % or more based on 100 mol % of total repeating units in the fluorine-containing polymer, and
the acid-unstable resin includes the repeating unit of the formula (2) at a content of from 10 mol % to 70 mol % based on 100 mol % of total repeating units in the acid-unstable resin.

### Claim 4 (depends on 1)

The radiation-sensitive resin composition of claim 1, wherein the repeating unit of the formula (2) in the fluorine-containing polymer and the acid-unstable resin is derived from one of the monomers of formulas (M-1), (M-2), (M-9) and (M-12):

### Claim 5 (depends on 1)

The radiation-sensitive resin composition of claim 1, wherein the acid-unstable resin includes the repeating unit of the formula (2) satisfying that two of R4s taken together represent an alicyclic hydrocarbon group derived from cyclopentane or cyclohexane, together with the carbon atom to which the two of R4s bond.

### Claim 6 (depends on 1)

The radiation-sensitive resin composition of claim 1, wherein the acid-unstable resin further includes a repeating unit comprising a lactone structure, and
a monomer that leads to the repeating unit comprising the lactone structure is one of compounds of formulas (3-1) to (3-6):
where R5 represents hydrogen atom or methyl group, R6 represents an alkyl group having 1 to 4 carbon atoms, that may be substituted, R7 represents hydrogen atom or methoxy group, A represents a single bond or methylene group, B represents oxygen atom or methylene group, 1 is an integer of 1 to 3, and m is 0 or 1.

### Claim 7 (depends on 2)

The radiation-sensitive resin composition of claim 2, wherein the radiation-sensitive acid generator includes an onium ion that includes
a cation, and
an anion represented by R17CnF2SO3−, an anion represented by R7SO3−, or both thereof,
where R17 represents a fluorine atom, a cycloalkyl group, or a bridge alicyclic hydrocarbon group, the cycloalkyl group and the bridge alicyclic hydrocarbon group having no more than 12 carbon atoms and optionally being substituted, and n is an integer of 1 to 10.

### Claim 8 (depends on 7)

The radiation-sensitive resin composition of claim 7, wherein the anion is represented by R17CnF2nSO3−.

### Claim 9 (depends on 7)

The radiation-sensitive resin composition of claim 7, wherein R17 is the bridge alicyclic hydrocarbon group.

### Claim 10 (depends on 7)

The radiation-sensitive resin composition of claim 7, wherein the cation is represented by formula (7-1),
where R14 represents a hydrogen atom, a fluorine atom, a hydroxyl group, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxyl group having 1 to 10 carbon atoms, or a linear or branched alkoxycarbonyl group having 2 to 11 carbon atoms,
R15 represents a linear or branched alkyl group having 1 to 10 carbon atoms, or an alkoxyl group,
R16 individually represents a linear or branched alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted phenyl group, or a substituted or unsubstituted naphthyl group, or two R16s taken together represent a substituted or unsubstituted divalent group which comprises 2 to 10 carbon atoms,
k is an integer of 0 to 2, and
r is an integer of 0 to 10.

### Claim 11 (depends on 7)

The radiation-sensitive resin composition of claim 7, wherein R16 individually represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group.

### Claim 12 (depends on 2)

The radiation-sensitive resin composition of claim 2, wherein the radiation-sensitive acid generator is included in an amount of from 0.5 to 10 parts by weight based on 100 parts by weight of a total of the fluorine-containing polymer and the acid-unstable resin.

### Claim 13 (depends on 2)

The radiation-sensitive resin composition of claim 2, wherein the radiation-sensitive acid generator is included in an amount of from 7 to 9.5 parts by weight based on 100 parts by weight of the acid-unstable resin.

### Claim 14 (depends on 2)

The radiation-sensitive resin composition of claim 2, wherein the nitrogen-containing compound comprises at least one of an amine compound, an amide group-containing compound, a urea compound, or a nitrogen-containing heterocyclic compound.

### Claim 15 (depends on 1)

The radiation-sensitive resin composition of claim 1, wherein the fluorine-containing polymer is included in an amount of 0.1% or more by weight based on 100% by weight of the radiation-sensitive resin composition.

### Claim 16 (depends on 1)

The radiation-sensitive resin composition of claim 1, wherein the fluorine-containing polymer is included in an amount of from 0.5% to 35% by weight based on 100% by weight of the radiation-sensitive resin composition.

### Claim 17 (depends on 1)

The radiation-sensitive resin composition of claim 1, wherein the fluorine-containing polymer has a weight average molecular weight determined by gel permeation chromatography in a range from 1,000 to 50,000.

### Claim 18 (depends on 1)

The radiation-sensitive resin composition of claim 1, wherein the fluorine-containing polymer further includes a repeating unit comprising a lactone structure.

### Claim 19 (depends on 18)

The radiation-sensitive resin composition of claim 18, wherein a monomer that leads to the repeating unit comprising the lactone structure in the fluorine-containing polymer is one of compounds of formulas (3-1) to (3-6):
where R5 represents hydrogen atom or methyl group, R6 represents an alkyl group having 1 to 4 carbon atoms, that may be substituted, R7 represents hydrogen atom or methoxy group, A represents a single bond or methylene group, B represents oxygen atom or methylene group, 1 is an integer of 1 to 3, and m is 0 or 1.

### Claim 20 (depends on 1)

The radiation-sensitive resin composition of claim 1, wherein R1 in the formula (1) represents a trifluoromethyl group, and R3 in the formula (2) represents a trifluoromethyl group.