# US 9,519,217 B2 · Chemically amplified positive resist composition and patterning process

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 9,519,217 B2
- Document ID: US9519217B2
- Status: Granted
- Kind: B2
- Application number: 14/732,026
- Filed: 2015-06-05
- Published: 2015-12-10
- Granted: 2016-12-13
- Earliest claimed: 2014-06-09
- Assignees: Shin-Etsu Chemical Co., Ltd.
- Applicants: Shin-Etsu Chemical Co., Ltd.
- Inventors: Katsuya Takemura; Yoshinori Hirano
- Web page: https://patentgrep.com/patent/US9519217B2

## CPC

- G03F 7/0392: {the macromolecular compound being present in a chemically amplified positive photoresist composition}
- G03F 7/0397: {the macromolecular compound having an alicyclic moiety in a side chain}
- G03F 7/16: Coating processes; Apparatus therefor (applying coatings to base materials in general B05; applying photosensitive compositions to base for photographic purposes G03C1/74)
- G03F 7/20: Exposure; Apparatus therefor (photographic printing apparatus for making copies G03B27/00)
- G03F 7/38: Treatment before imagewise removal, e.g. prebaking {(G03F7/265 takes precedence)}
- G03F 7/427: {using plasma means only}
- 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 chemically amplified positive resist composition is provided comprising a substantially alkali-insoluble polymer having an acid labile group-protected acidic functional group, a poly(meth)acrylate polymer having Mw of 1,000-500,000, and an acid generator in a solvent. The composition forms on a substrate a resist film of 5-100 μm thick which can be briefly developed to form a pattern at a high sensitivity and a high degree of removal or dissolution to bottom.

## Claims

### Claim 1

A chemically amplified positive resist composition comprising (A) an organic solvent, (B) a base resin, and (C) an acid generator,
said base resin (B) comprising a first polymer comprising recurring units represented by the general formula (1) and having a weight average molecular weight of 1,000 to 500,000, and a second polymer comprising recurring units of acrylate or methacrylate represented by the general formula (2) and having a weight average molecular weight of 1,000 to 500,000,
wherein R1 is hydrogen, hydroxyl, straight alkyl, branched alkyl, halogen or trifluoromethyl, R2 is hydrogen, hydroxyl, halogen or trifluoromethyl, R3 is C4-C12 tertiary alkyl, R4 is hydrogen, an optionally substituted alkyl group, optionally substituted alkoxy group, —C(CF3)2—OH, trialkylsiloxy group in which each alkyl moiety has 1 to 6 carbon atoms, C4-C20 oxoalkoxy group, tetrahydropyranyloxy group, tetrahydrofuranyloxy group, or trialkylsiloxy group, R5 is hydrogen or methyl, R6 is hydrogen, methyl, alkoxycarbonyl, cyano, halogen or trifluoromethyl, R7 is C4-C30 alkyl, n is 0 or a positive integer of 1 to 4, m is 0 or a positive integer of 1 to 5, p and r each are 0 or a positive number, s is a positive number, q is a positive number, and p+q+r+s=1,
wherein R8 is hydrogen or methyl, and R9 is selected from the group consisting of a straight, branched or cyclic C2-C24 alkyl group, a C2-C12 alkoxyalkyl group, a C1-C12 hydroxyalkyl group, an organic group of the formula (3):
—(RO)n—R′ (3)
wherein R is C2-C4 alkylene, R′ is C1-C6 alkyl, and n is an integer of 1 to 6, and an organic group of the formula (4):
wherein R″ is a straight, branched or cyclic C1-C12 alkyl group, a C2-C12 alkoxyalkyl group, a C1-C12 hydroxyalkyl group, or a C3-C12 (poly)alkylene glycol alkyl group.

### Claim 2 (depends on 1)

The resist composition of claim 1 wherein R8 in formula (2) is hydrogen.

### Claim 3 (depends on 1)

The resist composition of claim 1 wherein the first polymer comprises recurring units of at least one type selected from the following formulae (6) and (7):
wherein R1, R2, R3, R5, R6, R7, m, and n are as defined for formula (1), p, q and s are positive numbers, p+q+s=1,
wherein R1, R2, R3, R4, R5, R6, R7, m, and n are as defined for formula (1), p, q, r and s are positive numbers, p+q+r+s=1.

### Claim 4 (depends on 1)

The resist composition of claim 1 wherein the optionally substituted alkoxy group of R4 is a group of the following formula (8), a group of the following formula (9), or a straight, branched or cyclic C4-C20 tertiary alkoxy group,
wherein R13, R14, R15, R16, and R17 are each independently hydrogen, or a straight or branched C1-C8 alkyl group, a pair of R13 and R14, R13 and R15, or R14 and R15 may bond together to form a ring with the carbon atom or the carbon and oxygen atoms to which they are attached, each of R13, R14, and R15 is a straight or branched C1-C18 alkylene group when they form a ring, R18 is a straight, branched or cyclic C4-C40 alkyl group, and a is 0 or an integer of 1 to 4.

### Claim 5 (depends on 1)

The resist composition of claim 1 wherein the first polymer comprises recurring units of the following formula (10):
wherein R7 is as defined for formula (1), p, q and s are positive numbers, p+q+s=1.

### Claim 6 (depends on 1)

The resist composition of claim 1, further comprising (D) a benzotriazole compound having the general formula (11) or (12):
wherein P is hydrogen, hydroxyl, an optionally substituted C1-C6 alkyl, optionally substituted phenyl, substituent group having sulfonic acid or derivative thereof, or —Z—Y, Z is a C2-C12 alkylene, cycloalkylene or alkylene ether group which may be substituted with carboxyl, Y is a hydroxyl, C1-C6 alkoxy group, carboxyl group or dialkylamino group in which each alkyl moiety has 1 to 6 carbon atoms, Q is hydrogen, halogen, hydroxyl, C1-C6 alkyl, C1-C6 alkoxy group or an organic group having the formula (13):
wherein R12 is hydrogen or C1-C12 alkyl, x is 0 or 1,
wherein T is hydrogen, hydroxyl, C1-C6 alkyl, or phenyl group, and W is hydrogen, halogen, hydroxyl, C1-C6 alkyl or C1-C6 alkoxy group.

### Claim 7 (depends on 1)

The resist composition of claim 1, further comprising (E) a dissolution inhibitor.

### Claim 8 (depends on 1)

The resist composition of claim 1, further comprising (F) a basic compound, with the proviso that the benzotriazole compound of the following formula (11) or (12) is excluded from the basic compound:
wherein P is hydrogen, hydroxyl, an optionally substituted C1-C6 alkyl, optionally substituted phenyl, substituent group having sulfonic acid or derivative thereof, or —Z—Y, Z is a C2-C12 alkylene, cycloalkylene or alkylene ether group which may be substituted with carboxyl, Y is a hydroxyl, C1-C6 alkoxy group, carboxyl group or dialkylamino group in which each alkyl moiety has 1 to 6 carbon atoms, Q is hydrogen, halogen, hydroxyl, C1-C6 alkyl, C1-C6 alkoxy group or an organic group having the formula (13):
wherein R12 is hydrogen or C1-C12 alkyl, x is 0 or 1,
wherein T is hydrogen, hydroxyl, C1-C6 alkyl, or phenyl group, and W is hydrogen, halogen, hydroxyl, C1-C6 alkyl or C1-C6 alkoxy group.

### Claim 9 (depends on 1)

A pattern forming process comprising the steps of:
(i) coating the resist composition of claim 1 onto a substrate and prebaking to form a resist film,
(ii) exposing the resist film to UV radiation having a wavelength of up to 500 nm through a photomask, and
(iii) optionally baking, and developing with a developer to form a resist pattern.

### Claim 10 (depends on 9)

The process of claim 9 wherein the substrate is a substrate having a conductive layer on its surface, and the process further comprises, after the developing step (iii),
(iv) subjecting the resist pattern-bearing substrate to ashing with an oxygen plasma for thereby removing any resist residue on the pattern and rendering the resist film surface hydrophilic,
(v) performing electroplating or electroless plating using the resist pattern as a mold, for thereby depositing a metal pattern on the conductive substrate to a predetermined thickness, and
(vi) removing the resist component which has served as the mold for depositing the metal pattern, from the substrate.

### Claim 11 (depends on 9)

The process of claim 9 wherein the resist film has a thickness of 5 to 100 μm.

### Claim 12 (depends on 1)

The resist composition of claim 1 wherein the second polymer consists of recurring units of acrylate or methacrylate represented by the general formula (2).