# US 9,519,213 B2 · Patterning process and resist composition

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- Number: US 9,519,213 B2
- Document ID: US9519213B2
- Status: Granted
- Kind: B2
- Application number: 14/182,682
- Filed: 2014-02-18
- Published: 2014-09-11
- Granted: 2016-12-13
- Earliest claimed: 2013-03-05
- Assignees: Shin-Etsu Chemical Co., Ltd.
- Applicants: Shin-Etsu Chemical Co., Ltd.
- Inventors: Tomohiro Kobayashi; Kazuhiro Katayama; Kentaro Kumaki; Chuanwen Lin; Masaki Ohashi; Masahiro Fukushima
- Web page: https://patentgrep.com/patent/US9519213B2

## CPC

- 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 7/0395: {the macromolecular compound having a backbone with alicyclic moieties}
- G03F 7/0397: {the macromolecular compound having an alicyclic moiety in a side chain}
- G03F 7/11: having cover layers or intermediate layers, e.g. subbing layers {(G03F7/091 - G03F7/093, B41N3/03 take precedence)}
- G03F 7/2041: {in the presence of a fluid, e.g. immersion; using fluid cooling means}
- G03F 7/325: {Non-aqueous 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
- 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 negative pattern is formed by coating a resist composition comprising (A) a polymer having an acid labile group, adapted to change its polarity under the action of acid, (B) a photoacid generator, and (C) an organic solvent onto a substrate, baking, exposing the resist film to high-energy radiation, PEB, and developing in an organic solvent-based developer to selectively dissolve the unexposed region of resist film. The photoacid generator has the formula: R1—COOC(CF3)2—CH2SO3−R2R3R4S+ wherein R1 is a monovalent hydrocarbon group, R2, R3 and R4 are an alkyl, alkenyl, oxoalkyl, aryl, aralkyl or aryloxoalkyl group, or may bond together to form a ring with the sulfur atom.

## Claims

### Claim 1

A process for forming a negative pattern, comprising the steps of coating a resist composition comprising (A) a polymer having an acid labile group, adapted to change its polarity under the action of acid, (B) a photoacid generator, and (C) an organic solvent onto a substrate, baking the coating to form a resist film, exposing the resist film to high-energy radiation to define exposed and unexposed regions, baking, and developing the resist film in a developer selected from the group consisting of ketones and esters to selectively dissolve the unexposed region of resist film,
said photoacid generator (B) having the general formula (1):
R1—COOC(CF3)2—CH2SO3−R2R3R4S+ (1)
wherein R1 is a straight, branched or cyclic, monovalent hydrocarbon group of 1 to 50 carbon atoms which may contain a heteroatom, R2, R3 and R4 are each independently a substituted or unsubstituted, straight or branched C1-C10 alkyl, alkenyl or oxoalkyl group or a substituted or unsubstituted C6-C18 aryl, aralkyl or aryloxoalkyl group, or at least two of R2, R3 and R4 may bond together to form a ring with the sulfur atom, and
said polymer (A) comprises recurring units having the general formula (2):
wherein R5 is hydrogen or methyl, R6 is a straight, branched or cyclic, divalent aliphatic hydrocarbon group of 2 to 16 carbon atoms which may contain an ether or ester bond, R7 is tert-pentyl or neopentyl, m is 0 or 1, and n is 1 or 2.

### Claim 2 (depends on 1)

The process of claim 1 wherein the polymer (A) further comprises recurring units having the general formula (3):
wherein R8 is hydrogen or methyl, R9 is a straight, branched or cyclic, divalent aliphatic hydrocarbon group of 2 to 16 carbon atoms which may contain an ether or ester bond, R10 is a cyclic hydrocarbon group of 4 to 15 carbon atoms having at least one partial structure selected from the group consisting of hydroxyl, ether, ketone, ester, carbonic acid ester, and sulfonic acid ester, and p is 0 or 1.

### Claim 3 (depends on 1)

The process of claim 1 wherein the developer comprises at least one organic solvent selected from the group consisting of 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, acetophenone, 2′-methylacetophenone, 4′-methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, butenyl acetate, propyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate, and 2-phenylethyl acetate,
the at least one organic solvent being present in a total amount of at least 60% by weight of the developer.

### Claim 4 (depends on 1)

The process of claim 1 wherein the step of exposing the resist film to high-energy radiation includes ArF excimer laser immersion lithography of wavelength 193 nm.