# US 8,771,922 B2 · Copolymer for resist comprising novel acryl based monomer and resin composition for resist comprising the same

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- Number: US 8,771,922 B2
- Document ID: US8771922B2
- Status: Granted
- Kind: B2
- Application number: 13/432,218
- Filed: 2012-03-28
- Published: 2012-10-04
- Granted: 2014-07-08
- Earliest claimed: 2011-03-30
- Assignees: Korea Kumho Petrochemical Co., Ltd.
- Applicants: Jin Bong Shin; Jin Ho Kim; Dae Hyeon Shin; Seung Jae Lee
- Inventors: Jin Bong Shin; Jin Ho Kim; Dae Hyeon Shin; Seung Jae Lee
- Web page: https://patentgrep.com/patent/US8771922B2

## CPC

- C08F 220/1818: {C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate}
- C08F 220/283: {and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate}
- C08F 220/40: Esters of unsaturated alcohols {, e.g. allyl (meth)acrylate}
- C08F 222/26: of unsaturated alcohols {(C08F222/1006 takes precedence)}
- C08F 232/08: having condensed rings (coumarone-indene polymers C08F244/00)
- 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}
- 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

A resist resin composition includes 100 parts by weight of a copolymer represented by Formula 3 below; 0.5 to 1.5 parts by weight of a photoacid generator and 700 to 1,500 parts by weight of a solvent: wherein R1, R2, and R3 are each independently a C1-30 alkyl group, a C3-30 cycloalkyl group, an ether group, an ester group, a carbonyl group, an acetal group, an epoxy group, a nitrile group, or an aldehyde group, R4, R5, and R6 are each independently hydrogen or a methyl group, and l, m, n, and o each independently refer to the number of repeating units in a main backbone and satisfy the conditions: l+m+n+o=1, 0≦l/(l+m+n+o)<0.4, 0<m/(l+m+n+o)<0.6, 0≦n/(l+m+n+o)<0.6, and 0<o/(l+m+n+o)<0.4.

## Claims

### Claim 1

A copolymer for a resist, comprising as repeating units a norbornene derivative and at least one of the acryl-based monomers represented by Formulae 1 and 2 below:

### Claim 2

A resist resin composition comprising:
100 parts by weight of a copolymer represented by Formula 3 below;
0.5 to 1.5 parts by weight of a photoacid generator and
700 to 1,500 parts by weight of a solvent:
wherein R1, R2, and R3 are each independently a C1-30 alkyl group, a C3-30 cycloalkyl group, an ether group, an ester group, a carbonyl group, an acetal group, an epoxy group, a nitrile group, or an aldehyde group, R4, R5, and R6 are each independently hydrogen or a methyl group, and l, m, n, and o each independently refer to the number of repeating units in a main backbone and satisfy the conditions: l+m+n+o=1, 0≦l/(l+m+n+o)<0.4, 0<m/(l+m+n+o)<0.6, 0≦n/(l+m+n+o)<0.6, and 0<o/(l+m+n+o)<0.4.

### Claim 3 (depends on 2)

The resist resin composition of claim 2, wherein a weight average molecular weight (Mw) of the copolymer with respect to polystyrene standard by gel permeation chromatography (GPC) is in a range of 2,000 to 1,000,000.

### Claim 4 (depends on 2)

The resist resin composition of claim 2, wherein a molecular weight distribution represented by weight average molecular weight/number average molecular weight of the copolymer is in a range of 1.0 to 5.0.

### Claim 5 (depends on 2)

The resist resin composition of claim 2, wherein repeating units “m” and “n” in Formula 3 comprise an acid-labile functional group.

### Claim 6 (depends on 2)

The resist resin composition of claim 2, wherein repeating units “m” and “n” in Formula 3 comprise a lactone-containing functional group.

### Claim 7 (depends on 2)

The resist resin composition of claim 2, wherein the photoacid generator is a salt compound represented by Formula 19 or 20 below:
wherein R1 and R2 are each independently an alkyl group, an allyl group, a perfluoroalkyl group, a benzyl group, or an aryl group, R3, R4, and R5 are each independently hydrogen, an alkyl group, a halogen group, a alkoxy group, an aryl group, a thiophenoxy group, a thioalkoxy group, or an alkoxycarbonylmethoxy group, and “A” that denotes an anion is OSO2CF3, OSO2C4F9, OSO2C5F17, N(CF3)2, N(C2F5)2, N(C4F9)2, C(CF3)3, C(C2F5)3, C(C4F9)3, or a compound represented by Formula 21 below:
wherein X refers to a monocyclic or polycyclic C3-C30 hydrocarbon group, a benzyl group, or an aryl group; a C1-C20 alkyl group, an allyl group, a perfluoroalkyl group, alkyl, haloalkyl, or an alkylsulfonyl group, wherein the alkyl group is substituted with a hydrogen group, an ether group, an ester group, a carbonyl group, an acetal group, a nitrile group, a cyano group, a hydroxy group, a carboxyl group, or an aldehyde group; or C1-C4 perfluoroalkyl group, R is a C1-C10 alkyl group, a C1-C10 alkoxy group, or a hetero atom selected from N, S, F, and O, and m is an integer of 0 to 2.

### Claim 8 (depends on 2)

A photoresist film formed by coating and curing the resist resin composition of claim 2.

### Claim 9 (depends on 8)

The photoresist film of claim 8, wherein a developing process is performed using an aqueous solution containing tetramethyl ammonium hydroxide.

### Claim 10 (depends on 2)

The resist resin composition of claim 2, wherein the solvent is selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl isopropyl ketone, cyclohexanone, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-heptanone, ethyl lactate, γ-butyrolactone, and combinations thereof.

### Claim 11

A resist resin composition comprising:
100 parts by weight of a copolymer selected from the group consisting of Formula 6, Formula 7, Formula 9, Formula 12, and Formula 13 as shown below;
0.5 to 1.5 parts by weight of a photoacid generator and
700 to 1,500 parts by weight of a solvent:

### Claim 12 (depends on 11)

The resist resin of claim 11, wherein the solvent is selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methyl isopropyl ketone, cyclohexanone, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, 2-heptanone, ethyl lactate, γ-butyrolactone, and combinations thereof.

### Claim 13 (depends on 11)

The resist resin composition of claim 11, wherein the photoacid generator is a salt compound represented by Formula 19 or 20 below:
wherein R1 and R2 are each independently an alkyl group, an allyl group, a perfluoroalkyl group, a benzyl group, or an aryl group, R3, R4, and R5 are each independently hydrogen, an alkyl group, a halogen group, a alkoxy group, an aryl group, a thiophenoxy group, a thioalkoxy group, or an alkoxycarbonylmethoxy group, and “A” that denotes an anion is OSO2CF3, OSO2C4F9, OSO2C8F17, N(CF3)2, N(C2F5)2, N(C4F9)2, C(CF3)3, C(C2F5)3, C(C4F9)3, or a compound represented by Formula 21 below:
wherein X refers to a monocyclic or polycyclic C3-C30 hydrocarbon group, a benzyl group, or an aryl group; a C1-C20 alkyl group, an allyl group, a perfluoroalkyl group, alkyl, haloalkyl, or an alkylsulfonyl group, wherein the alkyl group is substituted with a hydrogen group, an ether group, an ester group, a carbonyl group, an acetal group, a nitrile group, a cyano group, a hydroxy group, a carboxyl group, or an aldehyde group; or C1-C4 perfluoroalkyl group, R is a C1-C10 alkyl group, a C1-C10 alkoxy group, or a hetero atom selected from N, S, F, and O, and m is an integer of 0 to 2.

### Claim 14 (depends on 11)

The resist resin composition of claim 11, wherein the copolymer is represented by Formula 6.

### Claim 15 (depends on 11)

The resist resin composition of claim 11, wherein the copolymer is represented by Formula 7.

### Claim 16 (depends on 11)

The resist resin composition of claim 11, wherein the copolymer is represented by Formula 9.

### Claim 17 (depends on 11)

The resist resin composition of claim 11, wherein the copolymer is represented by Formula 12.

### Claim 18 (depends on 11)

The resist resin composition of claim 11, wherein the copolymer is represented by Formula 13.