# US 10,120,282 B2 · Chemically amplified resist material and resist pattern-forming method

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- Number: US 10,120,282 B2
- Document ID: US10120282B2
- Status: Granted
- Kind: B2
- Application number: 15/259,200
- Filed: 2016-09-08
- Published: 2017-03-16
- Granted: 2018-11-06
- Earliest claimed: 2015-09-10
- Assignees: Jsr Corporation
- Applicants: Jsr Corporation
- Inventors: Hisashi Nakagawa; Takehiko Naruoka; Tomoki Nagai
- Web page: https://patentgrep.com/patent/US10120282B2

## CPC

- G03F 7/0397: {the macromolecular compound having an alicyclic moiety in a side chain}
- 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 7/0392: {the macromolecular compound being present in a chemically amplified positive photoresist composition}
- G03F 7/203: {comprising an imagewise exposure to electromagnetic radiation or corpuscular radiation}
- G03F 7/322: {Aqueous alkaline compositions}
- G03F 7/38: Treatment before imagewise removal, e.g. prebaking {(G03F7/265 takes precedence)}
- C08F 220/24: containing perhaloalkyl radicals
- C08F 220/382: {and containing oxygen, e.g. 2-sulfoethyl (meth)acrylate}
- C08F 228/02: by a bond to sulfur
- 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

A chemically amplified resist material comprises: a polymer component that is capable of being made soluble or insoluble in a developer solution by an action of an acid; and a generative component that is capable of generating a radiation-sensitive sensitizer and an acid upon an exposure. The polymer component comprises: a first polymer comprising a first structural unit that comprises a fluorine atom and does not comprise a salt structure; or a second polymer comprising a second structural unit that comprises a fluorine atom and a salt structure. The generative component comprises: a radiation-sensitive acid-and-sensitizer generating agent; any two of the radiation-sensitive acid-and-sensitizer generating agent, a radiation-sensitive sensitizer generating agent and a radiation-sensitive acid generating agent; or the radiation-sensitive acid-and-sensitizer generating agent, the radiation-sensitive sensitizer generating agent and the radiation-sensitive acid generating agent.

## Claims

### Claim 1

A chemically amplified resist material comprising:
a polymer component that is capable of being made soluble or insoluble in a developer solution by an action of an acid; and
a generative component that is capable of generating a radiation-sensitive sensitizer and an acid upon an exposure,
wherein the polymer component comprises:
a first polymer comprising a first structural unit that comprises a fluorine atom and does not comprise a salt structure; or
a second polymer comprising a second structural unit that comprises a fluorine atom and a salt structure, and
wherein the generative component comprises:
a radiation-sensitive sensitizer generating agent; and a radiation-sensitive acid generating agent,
wherein
the radiation-sensitive sensitizer generating agent is capable of generating, upon the exposure to a first radioactive ray that is a radioactive ray having a wavelength of no greater than 250 nm, the radiation-sensitive sensitizer absorbing a second radioactive ray that is a radioactive ray having a wavelength of greater than 250 nm, does not generate an acid upon the exposure to the first radioactive ray, and substantially does not generate the radiation-sensitive sensitizer upon the exposure to the second radioactive ray without the exposure to the first radioactive ray, and
the radiation-sensitive acid generating agent is capable of generating an acid upon the exposure to the first radioactive ray, does not generate a radiation-sensitive sensitizer upon the exposure to the first radioactive ray, and substantially does not generate the acid upon the exposure to the second radioactive ray without the exposure to the first radioactive ray.

### Claim 2 (depends on 1)

The chemically amplified resist material according to claim 1, wherein the first structural unit is a structural unit represented by formula (f-1), a structural unit represented by formula (f-2), a structural unit represented by formula (f-3), a structural unit represented by formula (f-4), or a combination thereof,
wherein, in the formula (f-1),
RF1 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group;
LF1 represents a single bond, an oxygen atom, a sulfur atom, —CO—O—, —SO2—O—NH—, —CO—NH— or —O—CO—NH—; and
RF2 represents a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms,
in the formula (f-2),
RF3 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group;
RF2 represents a single bond, an oxygen atom, a sulfur atom, —CO—O—, —SO2—O—NH—, —CO—NH— or —O—CO—NH—;
RF4 represents a single bond, a hydrocarbon group having 1 to 20 carbon atoms and having a valency of (u+1), or a structure obtained by incorporating an oxygen atom, a sulfur atom, —NRFF1—, a carbonyl group, —CO—O— or —CO—NH— into the end on the RF5 side of the hydrocarbon group having 1 to 20 carbon atoms and having a valency of (u+1), wherein RFF1 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms;
RF5 represents a single bond or a divalent organic group having 1 to 20 carbon atoms;
LF3 represents a single bond or a divalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms;
A1 represents an oxygen atom, —NRFF2—, —CO—O—* or —SO2—O—*, wherein RFF2 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and * denotes a binding site to RF6;
RF6 represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms; and
u is an integer of 1 to 3, wherein in a case where u is 1, RF4 optionally represent a single bond, and in a case where u is 2 or 3, a plurality of RF5s are identical or different, a plurality of LF3s are identical or different, and a plurality of A1s are identical or different, and a plurality of RF6s are identical or different,
in the formula (f-3),
RF7 represents a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group or a monovalent carbonyloxy hydrocarbon group having 2 to 20 carbon atoms;
LF4 represents a single bond, an oxygen atom, a sulfur atom, —CO—O—, —SO2—O—NH—, —CO—NH— or —O—CO—NH—;
RF8 represents a single bond or a divalent organic group having 1 to 20 carbon atoms;
RF9 and RF10 each independently represent an alkyl group having 1 to 10 carbon atoms or a fluorinated alkyl group having 1 to 10 carbon atoms, wherein either RF9 or RF10 represents the fluorinated alkyl group; and
v is an integer of 1 to 3, wherein in a case where v is 2 or 3, a plurality of RF9s are identical or different, and a plurality of RF10s are identical or different, and
in the formula (f-4),
RF11 represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group;
RF12 and RF13 each independently represent a hydrogen atom, a halogen atom, a hydroxy group or a monovalent organic group having 1 to 20 carbon atoms;
w is an integer of 1 to 4, wherein in a case where w is no less than 2, a plurality of RF12s are identical or different, a plurality of RF13s are identical or different, and at least two of one or more RF12s and one or more RF13s optionally taken together represent a ring structure having 3 to 20 ring atoms together with the carbon atom to which the at least two of one or more RF12s and one or more RF13s bond; and
RF14 and RF15 each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, wherein at least one of RF14 and RF15 represents a monovalent organic group having 1 to 20 carbon atoms and having at least one fluorine atom substituting for a hydrogen atom thereof, and wherein RF14 and RF15 optionally taken together represent a ring structure having 3 to 20 ring atoms together with the carbon atom to which RF14 and RF15 bond.

### Claim 3 (depends on 1)

The chemically amplified resist material according to claim 1, wherein
the first polymer or the second polymer comprises a structural unit that comprises a group that is capable of generating a polar group through dissociation of an acid-labile group by an action of an acid, or
the polymer component comprises a third polymer that is different from the first polymer and the second polymer, and the third polymer comprises a structural unit that comprises a group that is capable of generating a polar group through dissociation of an acid-labile group by an action of an acid.

### Claim 4 (depends on 1)

The chemically amplified resist material according to claim 1, wherein the polymer component further comprises a structural unit derived from p-hydroxystyrene.

### Claim 5 (depends on 1)

The chemically amplified resist material according to claim 1, wherein the polymer component comprises at least two polymers each having a different mass percentage content of fluorine atom.

### Claim 6 (depends on 1)

The chemically amplified resist material according to claim 1, wherein the second polymer further comprises the first structural unit.

### Claim 7 (depends on 1)

A resist pattern-forming method comprising:
applying the chemically amplified resist material according to claim 1 on a substrate to form a resist film;
patternwise exposing the resist film to a radioactive ray having a wavelength of no greater than 250 nm;
floodwise exposing to a radioactive ray having a wavelength of greater than 250 nm, the resist film patternwise exposed;
baking the resist film floodwise exposed; and
developing with a developer solution, the resist film baked.

### Claim 8 (depends on 1)

The chemically amplified resist material according to claim 1, wherein the radiation-sensitive sensitizer generating agent is represented by formula (VI):
wherein R8, R9 and R10 each independently represent: a hydrogen atom; a phenyl group; a naphthyl group; an anthracenyl group; an alkoxy group having 1 to 5 carbon atoms; an alkylthio group having 1 to 5 carbon atoms; a phenoxy group; a naphthoxy group; an anthracenoxy group; an amino group; an amide group; a halogen atom; a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms; an alkoxy group having 1 to 5 carbon atoms substituted with a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an amino group, an amide group, or a hydroxyl group; an alkylthio group having 1 to 5 carbon atoms substituted with a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an amino group, an amide group, or a hydroxyl group; a phenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, an amino group, an amide group, or an alkyl group having 1 to 5 carbon atoms; a phenyl group substituted with a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an amino group, an amide group, or a hydroxyl group; a naphthoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, an amino group, an amide group, or a hydroxyl group; an anthracenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, an amino group, an amide group, or a hydroxyl group; a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms substituted with an alkoxy group having 1 to 5 carbon atoms, a phenoxy group, a naphthoxy group, an anthracenoxy group, an amino group, an amide group, or a hydroxyl group; or a carbonyl group to which an alkyl group having 1 to 12 carbon atoms bonds, wherein at least two of the groups represented by R8, R9 and R10 optionally taken together represent a ring structure via a single bond or a double bond, or via a bond that includes —CH2—, —O—, —S—, —SO2—, —SO2NH—, —C(═O)—, —C(═O)O—, —NHCO—, —NHC(═O)NH—, —CHRg—, —CRg2—, —NH— or —NRg—, wherein Rg represents: a phenyl group; a phenoxy group; a halogen atom; a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms; a phenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or an alkyl group having 1 to 5 carbon atoms; or a phenyl group substituted with a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a hydroxyl group.

### Claim 9 (depends on 1)

The chemically amplified resist material according to claim 1, wherein the radiation-sensitive sensitizer generating agent is represented by formula (XXXVI):
wherein
R9 and R10 each independently represent: a hydrogen atom; a phenyl group; a naphthyl group; an anthracenyl group; an alkoxy group having 1 to 5 carbon atoms; an alkylthio group having 1 to 5 carbon atoms; a phenoxy group; a naphthoxy group; an anthracenoxy group; an amino group; an amide group; a halogen atom; a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms; an alkoxy group having 1 to 5 carbon atoms substituted with a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an amino group, an amide group, or a hydroxyl group; an alkylthio group having 1 to 5 carbon atoms substituted with a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an amino group, an amide group, or a hydroxyl group; a phenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, an amino group, an amide group, or an alkyl group having 1 to 5 carbon atoms; a phenyl group substituted with a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an amino group, an amide group, or a hydroxyl group; a naphthoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, an amino group, an amide group, or a hydroxyl group; an anthracenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, an amino group, an amide group, or a hydroxyl group; a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms substituted with an alkoxy group having 1 to 5 carbon atoms, a phenoxy group, a naphthoxy group, an anthracenoxy group, an amino group, an amide group, or a hydroxyl group; or a carbonyl group to which an alkyl group having 1 to 12 carbon atoms bonds, wherein R9 and R10 optionally taken together represent a ring structure via a single bond or a double bond, or via a bond that includes —CH2—, —O—, —S—, —SO2—, —SO2NH—, —C(═O)—, —C(═O)O—, —NHCO—, —NHC(═O)NH—, —CHRg—, —CRg2—, —NH— or —NRg—, wherein Rg represents: a phenyl group; a phenoxy group; a halogen atom; a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms; a phenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or an alkyl group having 1 to 5 carbon atoms; or a phenyl group substituted with a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a hydroxyl group,
R23 and R24 each independently represent: a phenyl group; a halogen atom; a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms; or a phenyl group substituted with a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a hydroxyl group, wherein R23 and R24 optionally taken together represent a ring structure via a single bond or a double bond, or via a bond that comprises —CH2—, —O—, —S—, —SO2—, —SO2NH—, —C(═O)—, —C(═O)O—, —NHCO—, NHC(═O)NH—, —CHRg—, —CRg2, —NH— or —NRg—, wherein Rg represents: a phenyl group; a phenoxy group; a halogen atom; a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms; a phenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or an alkyl group having 1 to 5 carbon atoms; or a phenyl group substituted with a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a hydroxyl group.

### Claim 10 (depends on 9)

The chemically amplified resist material according to claim 9, wherein the radiation-sensitive sensitizer generating agent is represented by at least one of formulae (XXVII) to (XXX):
wherein
R23 and R24 are as defined in the formula (XXXVI), respectively;
at least one hydrogen atom of an aromatic ring is optionally substituted with an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms, and the aromatic ring is optionally fused with other aromatic ring to form a naphthalene ring or an anthracene ring; and
R25 represents an alkyl group having 1 to 5 carbon atoms.

### Claim 11 (depends on 1)

The chemically amplified resist material according to claim 1, wherein the radiation-sensitive sensitizer generating agent is represented by formula (XLVI):
wherein
R9 represents: a hydrogen atom; a phenyl group; a naphthyl group; an anthracenyl group; an alkoxy group having 1 to 5 carbon atoms; an alkylthio group having 1 to 5 carbon atoms; a phenoxy group; a naphthoxy group; an anthracenoxy group; an amino group; an amide group; a halogen atom; a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms; an alkoxy group having 1 to 5 carbon atoms substituted with a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an amino group, an amide group, or a hydroxyl group; an alkylthio group having 1 to 5 carbon atoms substituted with a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an amino group, an amide group, or a hydroxyl group; a phenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, an amino group, an amide group, or an alkyl group having 1 to 5 carbon atoms; a phenyl group substituted with a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an amino group, an amide group, or a hydroxyl group; a naphthoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, an amino group, an amide group, or a hydroxyl group; an anthracenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, an amino group, an amide group, or a hydroxyl group; a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms substituted with an alkoxy group having 1 to 5 carbon atoms, a phenoxy group, a naphthoxy group, an anthracenoxy group, an amino group, an amide group, or a hydroxyl group; or a carbonyl group to which an alkyl group having 1 to 12 carbon atoms bonds, and
R38, R39, and R40 each independently represent: a phenyl group; a halogen atom; a saturated or unsaturated linear, branched or cyclic hydrocarbon having 1 to 30 carbon atoms; or a phenyl group substituted with a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a hydroxyl group, wherein at least two of the groups represented by R38, R39, and R40 optionally taken together represent a ring structure via a single bond or a double bond, or via a bond that includes —CH2—, —O—, —S—, —SO2—, —SO2NH—, —C(═O)—, —C(═O)O—, —NHCO—, —NHC(═O)NH—, —CHRg—, —CRg2, —NH— or —NRg—, wherein Rg represents: a phenyl group; a phenoxy group; a halogen atom; a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms; a phenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or an alkyl group having 1 to 5 carbon atoms; or a phenyl group substituted with a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a hydroxyl group.