CN115151864A - Actinic-ray-sensitive or radiation-sensitive resin composition, actinic-ray-sensitive or radiation-sensitive film, pattern forming method, and method for manufacturing electronic device - Google Patents

Actinic-ray-sensitive or radiation-sensitive resin composition, actinic-ray-sensitive or radiation-sensitive film, pattern forming method, and method for manufacturing electronic device Download PDF

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CN115151864A
CN115151864A CN202180016486.6A CN202180016486A CN115151864A CN 115151864 A CN115151864 A CN 115151864A CN 202180016486 A CN202180016486 A CN 202180016486A CN 115151864 A CN115151864 A CN 115151864A
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radiation
actinic
sensitive
ray
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畠山直也
福崎英治
吉野文博
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Fujifilm Corp
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Fujifilm Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • 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
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/04—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing only one sulfo group
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    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
    • C07C309/08—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing hydroxy groups bound to the carbon skeleton
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    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
    • C07C309/12—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing esterified hydroxy groups bound to the carbon skeleton
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    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
    • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C309/17—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing carboxyl groups bound to the carbon skeleton
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    • C07C309/01—Sulfonic acids
    • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
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    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
    • C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
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    • C07C313/00—Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C313/02—Sulfinic acids; Derivatives thereof
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    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
    • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
    • C07D327/04—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
    • C07D327/06—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D327/10—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms two oxygen atoms and one sulfur atom, e.g. cyclic sulfates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
    • C07D339/08—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • 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
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • 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
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • 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
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • 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
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers

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Abstract

The invention provides an actinic-ray-or radiation-sensitive resin composition containing (A) a resin and (B) a compound represented by a specific general formula (1) that generates an acid upon irradiation with actinic rays or radiation, an actinic-ray-or radiation-sensitive film formed from the above-mentioned actinic-ray-or radiation-sensitive resin composition, a pattern forming method, and a method for producing an electronic device.

Description

Actinic-ray-sensitive or radiation-sensitive resin composition, actinic-ray-sensitive or radiation-sensitive film, pattern formation method, and method for producing electronic device
Technical Field
The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device.
Background
After the resist for KrF excimer laser light (248 nm), a pattern formation method using chemical amplification is used to compensate for the decrease in sensitivity due to light absorption. For example, in the positive chemical amplification method, first, a photoacid generator contained in an exposed portion is decomposed by light irradiation to generate an acid. Then, in a Post Exposure Bake (PEB) process or the like, an alkali-insoluble group contained in the photosensitive composition is changed to an alkali-soluble group by a catalytic action of the generated acid. Then, development is performed using, for example, an alkaline solution. Thereby, the exposed portion is removed to obtain a desired pattern.
In the above-mentioned method, various alkaline developers have been proposed as the alkaline developer. For example, an aqueous alkaline developer containing 2.38 mass% TMAH (tetramethylammonium hydroxide aqueous solution) is generally used as the alkaline developer.
In order to miniaturize semiconductor devices, the wavelength of an exposure light source has been shortened, and the numerical aperture (high NA) of a projection lens has been increased, and an exposure apparatus using an ArF excimer laser having a wavelength of 193nm as a light source has been developed. As a technique for further improving the analytical force, there is a method (that is, a liquid immersion method) in which a space between the projection lens and the sample is filled with a liquid having a high refractive index (hereinafter, also referred to as a "liquid immersion liquid").
As a conventional resist composition, a multi-layer composition is known, but for example, patent document 1 describes an actinic ray-sensitive or radiation-sensitive resin composition containing a compound represented by a specific general formula and generating an acid by irradiation with an actinic ray or radiation, and a resin.
Further, patent document 2 describes a positive resist material containing a photoacid generator of a compound represented by a specific general formula and a base resin in which a hydrogen atom of a carboxyl group or a hydrogen atom of a phenolic hydroxyl group is substituted with an acid labile group having an alkali dissolution controlling ability and the acid labile group is dissociated by the action of an acid generated by exposure to increase the solubility in an alkaline aqueous solution.
Prior art documents
Patent document
Patent document 1: japanese patent laid-open No. 2014-6491
Patent document 2: japanese patent laid-open publication No. 2003-321466
Disclosure of Invention
Technical problem to be solved by the invention
However, although a resist composition is usually left in a stored state for a predetermined period of time, the performance of the resist composition tends to deteriorate due to such storage over time, and therefore a resist composition capable of achieving more excellent stability over time is required (here, excellent stability over time means that, in the case of storing a resist composition before resist film formation over time, the pattern obtained using the composition after storage over time is less affected).
As a countermeasure, it is considered to change the composition of the resist composition to a composition capable of improving the stability with time, but it is not easy to actually find a composition capable of further improving the stability with time.
Accordingly, an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition which can realize extremely excellent stability over time.
It is another object of the present invention to provide an actinic ray-sensitive or radiation-sensitive film using the above actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method, and a method for manufacturing an electronic device.
Means for solving the technical problem
The present inventors have now made extensive studies on the structure of a sulfonium salt compound which is a compound generating an acid by irradiation with actinic rays or radiation (photoacid generator), and as a result, have found that the structure of a sulfonium ring having a heteroatom as a ring member or its vicinity is shielded by a substituent and the position of the substituent is precisely controlled, and although the detailed reasons are not clear, the present invention has surprisingly been found to be extremely excellent in stability over time, and thus have completed the present invention.
That is, the present invention has the following configuration, thereby solving the above-described problems of the present invention.
[1]
An actinic-ray-or radiation-sensitive resin composition comprising:
(A) A resin; and
(B) A compound represented by the following general formula (1) that generates an acid by irradiation with actinic rays or radiation.
[ chemical formula 1]
Figure BDA0003811393030000031
In the general formula (1) above,
W 1 representing a ring.
Q represents a constituent ring W 1 And 1 or more ring members of (a) are 2-valent linking groups of heteroatoms, carbonyl carbon atoms, or combinations thereof.
R 1A And R 1B Each independently represents a hydrogen atom, an organic group, a halogen atom or a cyano group. Wherein R is 1A And R 1B At least 1 of them represents an organic group, a halogen atom or a cyano group.
R 2A And R 2B Each independently represents a hydrogen atom, an organic group, a halogen atom or a cyano group. Wherein R is 2A And R 2B At least 1 of them represents an organic group, a halogen atom or a cyano group.
p represents 0 or 1,q represents 0 or 1.
Wherein p + q represents 1 or 2.
R 1 And R 2 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group. Wherein R is 1 And R 2 At least 1 of them represents an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
n represents 0 or 1.
R 3 And R 4 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
m represents 0 or an integer of 1 or more.
When m represents an integer of 1 or more, n represents 1.
L represents a carbonyl bond or an ester bond.
l represents 0 or 1.
In the case where l represents 1, n represents 1.
In the case where l represents 1, R 5 ～R 9 At least 2 of which may be connected to each other to form a ring.
In the case where l represents 0, m represents 0,n represents 0.
R 5 、R 6 、R 7 、R 8 And R 9 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkoxy group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, an alkenyl group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or a cycloalkylthio group.
Z-represents an anion.
[2]
The actinic-ray-or radiation-sensitive resin composition according to [1], wherein,
in the above general formula (1), the ring W 1 Is a 6-8 membered ring.
[3]
The actinic-ray-or radiation-sensitive resin composition according to any one of [1] and [2], wherein Z-in the general formula (1) is an anion represented by any one of the following general formulae (3) to (5).
[ chemical formula 2]
Figure BDA0003811393030000041
In the general formula (3), the compound (A),
each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
L 1 Represents a single bond or a divalent linking group. A represents a 1-valent organic group.
x represents an integer of 1 to 20.
[ chemical formula 3]
Figure BDA0003811393030000042
In the general formula (4), the compound (A),
Xf 1 each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. 2 Xf 1 May be connected to each other to form a ring structure.
[ chemical formula 4]
Figure BDA0003811393030000043
In the general formula (5), the metal salt,
Xf 2 each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. 2 Xf 2 May be connected to each other to form a ring structure.
[4]
The actinic-ray-or radiation-sensitive resin composition according to any one of [1] to [3], wherein,
in the general formula (1), Q is an arbitrary linking group selected from the following group.
[ chemical formula 5]
Figure BDA0003811393030000051
In the above-mentioned formula, the compound of formula,
R 11 represents a hydrogen atom or a substituent.
* Represents and forms W in the general formula (1) 1 A bond of adjacent groups to Q.
[5]
The actinic-ray-or radiation-sensitive resin composition according to any one of [1] to [4], wherein,
the compound represented by the above general formula (1) is a compound represented by the following general formula (2).
[ chemical formula 6]
Figure BDA0003811393030000052
In the general formula (2), in the formula,
ra to Rd each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
Wherein at least 1 of Ra to Rd represents an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
Q has the same meaning as that of Q in the above general formula (1).
R 1 、R 2 Has the same meaning as R in the above general formula (1) 1 、R 2 Have the same meaning.
R 5 、R 6 、R 7 、R 8 And R 9 Has the same meaning as R in the above general formula (1) 5 、R 6 、R 7 、R 8 And R 9 Have the same meaning.
R 5 ～R 9 At least 2 of which may be connected to each other to form a ring.
Z-has the same meaning as that of Z-in the above formula (1).
[6]
The actinic-ray-or radiation-sensitive resin composition according to any one of [1] to [5], wherein,
in the above general formula (1) or general formula (2), R 5 ～R 9 At least 1 of them represents an alkoxy group, a cycloalkoxy group, an alkylthio group or a cycloalkylthio group.
[7]
The actinic-ray-or radiation-sensitive resin composition according to any one of [1] to [6], wherein,
the solid content concentration of the composition is 10 mass% or more.
[8]
The actinic-ray-or radiation-sensitive resin composition according to any one of [1] to [7], wherein,
the resin (A) has a phenolic hydroxyl group.
[9]
The actinic-ray-or radiation-sensitive resin composition according to any one of [1] to [8], wherein,
the resin (A) has a carboxyl group.
[10]
An actinic-ray-or radiation-sensitive film formed by the actinic-ray-or radiation-sensitive resin composition according to any one of [1] to [9 ].
[11]
A pattern forming method, comprising:
exposing the actinic ray-sensitive or radiation-sensitive film according to [10 ]; and
and developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer.
[12]
A method of manufacturing an electronic device, comprising the pattern forming method of [11 ].
Effects of the invention
According to the present invention, an actinic ray-sensitive or radiation-sensitive resin composition which can realize extremely excellent stability over time can be provided.
According to the present invention, there can be further provided an actinic ray-sensitive or radiation-sensitive film using the above actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method, and a method for manufacturing an electronic device.
Detailed Description
In the following, the following description is given, the present invention will be described in detail.
The following description of the constituent elements is made in accordance with the exemplary embodiments of the present invention, but the present invention is not limited to such embodiments.
In the labeling of a group (atomic group) in the present specification, a label which is not described as substituted or unsubstituted includes a group having a substituent in addition to a group having no substituent. For example, "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Further, the "organic group" in the present specification means a group containing at least one carbon atom.
In the present specification, the kind of the substituent, the position of the substituent and the number of the substituents in the case of "optionally having a substituent" are not particularly limited. The number of the substituents may be, for example, 1,2, 3 or more. Examples of the substituent include a 1-valent nonmetal atomic group other than a hydrogen atom, and can be selected from the following substituents T.
(substituent T)
Examples of the substituent T include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl and phenoxycarbonyl; acyloxy groups such as acetoxy, propionyloxy, and benzoyloxy; acyl groups such as acetyl, benzoyl, isobutyryl, acryloyl, methacryloyl and methoxyacetyl; alkylsulfanyl groups such as methylsulfanyl and t-butylsulfanyl; phenylsulfanyl and p-tolyl radicals arylsulfanyl groups such as a sulfanyl group; an alkyl group; a cycloalkyl group; an aryl group; a heteroaryl group; a hydroxyl group; a carboxyl group; a formyl group; a sulfo group; a cyano group; an alkylaminocarbonyl group; an arylaminocarbonyl group; a sulfonamide group; a silyl group; an amino group; a monoalkylamino group; a dialkylamino group; arylamino, nitro; a formyl group; and combinations thereof.
The term "actinic rays" or "radiation" as used herein refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and Electron beams (EB Electron Beam). In the present specification, "light" unless otherwise specified, refers to actinic rays or radiation.
Unless otherwise stated, "exposure" in this specification includes not only exposure using a bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer laser, extreme ultraviolet rays, X-rays, EUV light, and the like, but also exposure using particle rays such as electron beams and ion beams.
In the present specification, "to" is used to indicate that numerical values described before and after the "to" are included as the lower limit value and the upper limit value.
In the present specification, (meth) acrylate means acrylate and methacrylate, and (meth) acrylic acid means acrylic acid and methacrylic acid.
In the present specification, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the degree of dispersion (also referred to as molecular weight distribution) (Mw/Mn) of the resin component are defined as polystyrene conversion values by GPC measurement using a GPC (Gel Permeation Chromatography) apparatus (HLC-8120 GPC manufactured by TOSOH CORPORATION) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10. Mu.L, column (column): TSK Gel Multipore HXL-M manufactured by TOSOH CORATION, column temperature: 40 ℃, flow rate: 1.0 mL/min, detector: differential Index Detector (Refractive Index Detector)).
In the present specification, when a plurality of substances corresponding to each component are present in a composition, the amount of each component in the composition means the total amount of the corresponding plurality of substances present in the composition unless otherwise specified.
In the present specification, the term "step" is not limited to an independent step, and is also included in the term as long as the expected date of the step can be achieved even when the term is not clearly distinguished from other steps.
In the present specification, "total solid content" means the total mass of components excluding the solvent from the entire composition of the composition. The term "solid component" refers to a component from which a solvent is removed as described above, and may be a solid or a liquid at 25 ℃.
In the present specification, "mass%" and "weight%" have the same meaning, and "parts by mass" and "parts by weight" have the same meaning.
In the present specification, a combination of two or more preferred embodiments is a more preferred embodiment.
(actinic ray-sensitive or radiation-sensitive resin composition)
An actinic-ray-or radiation-sensitive resin composition (hereinafter, also simply referred to as "composition") according to the present invention contains:
(A) A resin; and
(B) A compound represented by the following general formula (1) that generates an acid by irradiation with actinic rays or radiation.
[ chemical formula 7]
Figure BDA0003811393030000091
In the general formula (1) above,
W 1 representing a ring.
Q represents a constituent ring W 1 And 1 or more ring members of (a) are 2-valent linking groups of heteroatoms, carbonyl carbon atoms, or combinations thereof.
R 1A And R 1B Each independently represents a hydrogen atom, an organic group, a halogen atom or a cyano group. However, R 1A And R 1B At least 1 of them represents an organic group, a halogen atom or a cyano group.
R 2A And R 2B Each independently represents a hydrogen atom, an organic group, a halogen atom or a cyano group. However, R 2A And R 2B At least 1 of them represents an organic group, a halogen atom or a cyano group.
p represents 0 or 1,q represents 0 or 1.
However, p + q represents 1 or 2.
R 1 And R 2 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group. However, R 1 And R 2 At least 1 of them represents an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
n represents 0 or 1.
R 3 And R 4 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
m represents 0 or an integer of 1 or more.
When m represents an integer of 1 or more, n represents 1.
L represents a carbonyl bond or an ester bond.
l represents 0 or 1.
In the case where l represents 1, n represents 1.
In the case where l represents 1, R 5 ～R 9 At least 2 of which may be connected to each other to form a ring.
In the case where l represents 0, m represents 0,n represents 0.
R 5 、R 6 、R 7 、R 8 And R 9 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkoxy group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, an alkenyl group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or a cycloalkylthio group.
Z represents an anion.
The present invention can realize extremely excellent storage stability by adopting the above configuration.
The reason for this is not clear, but is presumed as follows.
First, the compound represented by the general formula (1) (photoacid generator) satisfies the expression "however, R 1A And R 1B At least 1 of them represents an organic group, a halogen atom or a cyano group. "," however, R 2A And R 2B At least 1 of (a) represents an organic group, a halogen atom or a cyano group. "and" p represents 0 or 1,q represents 0 or 1. However, p + q represents 1 or 2.", the matte ring has R which can function as a steric hindrance 1A 、R 1B 、R 2A And R 2B At least 1.
In addition, regarding the bond between the benzene ring and the sulfonium ring, when l = m = n =0, the benzene ring and the sulfonium ring are bonded by a single bond, the benzene ring can function as steric hindrance of the sulfonium ring, particularly from the sulfonium cation side, and when the relationship of l, m and n is other than the above, n =1 is set as R 1 And R 2 In (3), an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group in at least 1 of them are the same and can function as a steric hindrance of the sulfonium ring, particularly from the sulfonium cation side.
As described above, in the photoacid generator represented by the general formula (1), since a group capable of functioning as a steric hindrance is present on and in the vicinity of the sulfonium ring, the sulfonium ring (particularly, the ring member of the sulfonium ring) is less susceptible to attack by other components (e.g., nucleophilic attack) when the resist composition is stored over time, as compared with a photoacid generator that does not satisfy the general formula (1).
As a result, first, it is considered that the structure of the photoacid generator represented by the general formula (1) is easily maintained in the resist composition without being changed.
In addition, R which can function as a steric hindrance on the sulfonium ring is formed 1A 、R 1B 、R 2A And R 2B The configuration position of at least one of them is defined as the above general formula (1), and the unsubstituted carbon atom is adjacent to the sulfonium cation in the sulfonium ring, the present inventors have surprisingly found that the stability of a photoacid generator in a resist composition is greatly improved, although the detailed reasons and the like are not clear.
From this, it is estimated that the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is extremely excellent in stability with time.
The actinic-ray-or radiation-sensitive resin composition according to the present invention is preferably a so-called resist composition, and may be a positive resist composition or a negative resist composition. The resist composition may be an alkali-developable resist composition or an organic solvent-developable resist composition.
The composition of the present invention is typically preferably a chemically amplified resist composition.
Hereinafter, details of each component contained in the actinic ray-sensitive or radiation-sensitive resin composition (also simply referred to as "composition") according to the present invention will be described.
< Compound represented by the general formula (1) wherein an acid is generated by irradiation with actinic rays or radiation >
The composition of the present invention contains (B) a compound represented by the general formula (1) (hereinafter, also referred to as "photoacid generator (B)" or "compound (B)") that generates an acid upon irradiation with actinic rays or radiation.
In the above general formula (1), Q represents a constituent ring W 1 With 1 or more ring members being hetero atoms, carbonyl carbon atoms, or groups thereofA synthetic 2-valent linking group. In the 2-valent linking group as Q, a ring W is formed 1 And 1 or more ring members of (a) are a heteroatom, a carbonyl carbon atom, or a combination thereof.
The heteroatom is not particularly limited, and includes, for example, a nitrogen atom, an oxygen atom, and a sulfur atom.
The carbonyl carbon atom represents the carbon atom in the carbonyl bond.
Q is not particularly limited, and is preferably an arbitrary linking group selected from the following groups.
[ chemical formula 8]
Figure BDA0003811393030000111
In the above-mentioned group of methods,
R 11 represents a hydrogen atom or a substituent.
* Represents a group and forms a ring W in the general formula (1) 1 Q is a bond of adjacent groups.
As R 11 The substituent(s) is not particularly limited, and examples thereof include alkylsulfonyl, alkylcarbonyl, and alkyl.
The alkyl group in the alkylsulfonyl group may be linear or branched, and examples thereof include an alkyl group having 1 to 6 carbon atoms, and preferably an alkyl group having 1 to 4 carbon atoms.
The alkyl group in the alkylcarbonyl group may be linear or branched, and examples thereof include an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.
The alkyl group may be linear or branched, and examples thereof include an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.
The alkylsulfonyl group, the alkylcarbonyl group, and the alkyl group may further have a substituent.
* Represents a ring W formed by the bond of the general formula (1) 1 Q is a bond of adjacent groups.
In addition, the compound forms a ring W with the compound of the general formula (1) 1 Q is any of 2 groups adjacent to each otherOne bond is sufficient.
Q is preferably an arbitrary linking group selected from the following groups.
[ chemical formula 9]
Figure BDA0003811393030000121
In the above-mentioned formula, the compound of formula,
R 11 represents a hydrogen atom or a substituent.
* Represents a ring W formed by the bond of the general formula (1) 1 A bond of adjacent groups to Q.
R 11 And each as described above.
R 1A And R 1B Each independently represents a hydrogen atom, an organic group, a halogen atom or a cyano group.
R 2A And R 2B Each independently represents a hydrogen atom, an organic group, a halogen atom or a cyano group.
As R 1A 、R 2A 、R 1B And R 2B The organic group (b) is not particularly limited, and examples thereof include alkyl, cycloalkyl, alkoxy, cycloalkoxy, aryl, and alkylcarbonyl.
The alkyl group is not particularly limited, and may be linear or branched, and preferably includes an alkyl group having 1 to 20 carbon atoms.
The alkyl group is more preferably an alkyl group having 1 to 15 carbon atoms, and still more preferably an alkyl group having 1 to 10 carbon atoms.
The alkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T.
The cycloalkyl group is not particularly limited, and may be a monocyclic or polycyclic one, and is preferably a cycloalkyl group having 3 to 20 carbon atoms. Specific examples of the cycloalkyl group include cyclopentyl, cyclohexyl and decahydronaphthyl.
The cycloalkyl group is more preferably a cycloalkyl group having 3 to 15 carbon atoms, and still more preferably a cycloalkyl group having 3 to 10 carbon atoms.
The cycloalkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T.
The alkoxy group is not particularly limited, and is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 15 carbon atoms, and yet more preferably an alkoxy group having 1 to 10 carbon atoms.
The alkoxy group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T.
The cycloalkyl group in the cycloalkoxy group may be monocyclic or polycyclic, and is not particularly limited, and is preferably a cycloalkyl group having 3 to 20 carbon atoms. Specific examples of the cycloalkyl group include cyclopentyl, cyclohexyl, and decahydronaphthyl.
The cycloalkyl group in the cycloalkoxy group is more preferably a cycloalkyl group having 3 to 15 carbon atoms, and still more preferably a cycloalkyl group having 3 to 10 carbon atoms.
The cycloalkoxy group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T.
The aryl group is not particularly limited, and is preferably an aryl group having 6 to 20 carbon atoms, and specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a condensed tetraphenyl group, and a fluorenyl group.
The aryl group is more preferably an aryl group having 6 to 15 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms.
The aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T.
The alkyl group in the alkylcarbonyl group is not particularly limited, and may be a linear or branched alkyl group, and preferably includes an alkyl group having 1 to 20 carbon atoms.
The alkyl group in the alkylcarbonyl group is more preferably an alkyl group having 1 to 15 carbon atoms, and still more preferably an alkyl group having 1 to 10 carbon atoms.
The alkylcarbonyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
R 1A And R 1B Preferably represents a hydrogen atom, an organic group or a halogen atom, more preferably a hydrogen atom or an organic group.
R 2A And R 2B Preferably represents a hydrogen atom, an organic group or a halogen atom, more preferably a hydrogen atom or an organic group.
Wherein R is 1A And R 1B At least one of them represents an organic group, a halogen atom or a cyano group, R 2A And R 28 At least one of them represents an organic group, a halogen atom or a cyano group.
p represents 0 or 1,q represents 0 or 1.
However, p + q represents 1 or 2.
In the ring W 1 Wherein at least one carbon atom adjacent to Q has an organic group, a halogen atom or a cyano group as a substituent.
R 1A 、R 2A 、R 1B And R 2B Not all of them represents a hydrogen atom.
W 1 Representing a ring.
In the above general formula (1), W 1 Representing a ring. W is a group of 1 A ring having 5 or more members.
From W 1 The upper limit of the ring member of the ring is not particularly limited, and W 1 Preferably 10-membered rings or less.
W 1 Preferably a 6 to 8 membered ring, preferably a 6 or 7 membered ring, more preferably a 6 membered ring.
R 1 And R 2 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group. However, R 1 And R 2 At least 1 of them represents an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
As R 1 、R 2 The alkyl group (b) is not particularly limited, and may be linear or branched, and preferably includes an alkyl group having 1 to 20 carbon atoms.
The alkyl group is more preferably an alkyl group having 1 to 15 carbon atoms, and still more preferably an alkyl group having 1 to 10 carbon atoms.
The alkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.
As R 1 、R 2 The cycloalkyl group (b) is not particularly limited, and may be a monocyclic or polycyclic one, and is preferably a cycloalkyl group having 3 to 20 carbon atoms. Specific examples of the cycloalkyl group include cyclopentyl, cyclohexyl, and decahydronaphthyl.
The cycloalkyl group is more preferably a cycloalkyl group having 3 to 15 carbon atoms, and still more preferably a cycloalkyl group having 3 to 10 carbon atoms.
The cycloalkyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T.
As R 1 、R 2 The aryl group of (b) is not particularly limited, but is preferably an aryl group having 6 to 20 carbon atoms, and specific examples thereof include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a condensed tetraphenyl group, and a fluorenyl group.
The aryl group is more preferably an aryl group having 6 to 15 carbon atoms, and still more preferably an aryl group having 6 to 10 carbon atoms.
The aryl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T.
As R 1 、R 2 Examples of the halogen atom of (b) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
R 1 And R 2 Preferably a hydrogen atom, an alkyl group or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group. R 1 Represents a hydrogen atom, R 2 Further preferably represents an alkyl group.
R 3 And R 4 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
As R 3 、R 4 With the above-mentioned alkyl as R 1 、R 2 The alkyl groups are the same as those described.
As R 3 、R 4 And the cycloalkyl group as described above as R 1 、R 2 The cycloalkyl groups described are the same.
As R 3 、R 4 With aryl radicals as defined above for R 1 、R 2 The aryl groups described above are the same.
As R 3 、R 4 Examples of the halogen atom of (2) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
R 3 And R 4 Preferably a hydrogen atom, an alkyl group or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group. R 3 And R 4 Further preferably represents a hydrogen atom.
m represents 0 or an integer of 1 or more.
The upper limit of m is not particularly limited, and m is preferably an integer of 5 or less. m is preferably an integer of 0 to 3, more preferably 0 or 1.
When m represents an integer of 1 or more, n represents 1.
L represents a carbonyl bond or an ester bond. As L, a carbonyl bond is preferable.
In the case where l represents 1, n represents 1.
In the case where l represents 0, m represents 0,n represents 0.
R 5 、R 6 、R 7 、R 8 And R 9 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkoxy group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, an alkenyl group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or a cycloalkylthio group.
As R 5 、R 6 、R 7 、R 8 And R 9 With the above-mentioned alkyl as R 1A 、R 2A 、R 1B And R 2B The alkyl groups described are the same.
As R 5 、R 6 、R 7 、R 8 And R 9 With cycloalkyl radicals as defined above for R 1A 、R 2A 、R 1B And R 2B The cycloalkyl groups described are the same.
As R 5 、R 6 、R 7 、R 8 And R 9 And the above-mentioned aryl group as R 1A 、R 2A 、R 1B And R 2B Aryl ofThe same is true.
As R 5 、R 6 、R 7 、R 8 And R 9 With alkoxy radicals as defined above for R 1A 、R 2A 、R 1B And R 2B The alkoxy groups are the same as those described above.
As R 5 、R 6 、R 7 、R 8 And R 9 With cycloalkoxy radicals as defined above for R 1A 、R 2A 、R 1B And R 2B The cycloalkoxy groups are the same as those described.
As R 5 、R 6 、R 7 、R 8 And R 9 Alkoxy in alkoxycarbonyl of (a) with the above-mentioned as R 1A 、R 2A 、R 1B And R 2B The alkoxy groups are the same as those described above.
As R 5 、R 6 、R 7 、R 8 And R 9 Cycloalkyl in the cycloalkoxycarbonyl group of (a) with the above-mentioned as R 1A 、R 2A 、R 1B And R 2B The cycloalkyl groups described are the same.
As R 5 、R 6 、R 7 、R 8 And R 9 With the alkyl group in the alkylcarbonyloxy group mentioned above as R 1A 、R 2A 、R 1B And R 2B The alkyl groups are the same as those described.
As R 5 、R。、R 7 、R 8 And R 9 The cycloalkyl group in the cycloalkylcarbonyloxy group of (1) and the above-mentioned group as R 1A 、R 2A 、R 1B And R 2B The cycloalkyl groups described are the same.
As R 5 、R 6 、R 7 、R 8 And R 9 Alkyl in alkylthio of (2) with the above-mentioned as R 1A 、R 2A 、R 1B And R 2B The alkyl groups are the same as those described.
As R 5 、R 6 、R 7 、R 8 And R 9 Cycloalkyl in cycloalkylthio of (A) with the above as R 1A 、R 2A 、R 1B And R 2B The cycloalkyl groups described are the same.
As R 5 、R 6 、R 7 、R 8 And R 9 The alkenyl group (C) is not particularly limited, and may be linear or branched, preferably, an alkenyl group having 2 to 20 carbon atoms can be mentioned.
The alkenyl group is more preferably an alkenyl group having 2 to 15 carbon atoms, and still more preferably an alkenyl group having 2 to 10 carbon atoms.
The alkenyl group may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T.
As R 5 、R 6 、R 7 、R 8 And R 9 Examples of the halogen atom of (b) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
R 5 、R 6 、R 7 、R 8 And R 9 Preferably represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group or a cycloalkoxy group, more preferably represents a cycloalkyl group, an alkoxy group or a cycloalkoxy group, and still more preferably represents an alkoxy group or a cycloalkoxy group.
In the case where l represents 1, R 5 ～R 9 At least 2 of which may be connected to each other to form a ring.
As R 5 ～R 9 The ring formed by connecting at least 2 of them is not particularly limited, and examples thereof include an aromatic or non-aromatic (for example, aliphatic) hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, and a polycyclic condensed ring in which 2 or more of these rings are combined. Examples of the ring structure (in a polycyclic fused ring, a monocyclic ring structure constituting the fused ring structure) include a 3-to 10-membered ring, preferably a 4-to 8-membered ring, and more preferably a 5-or 6-membered ring.
Z - Represents an anion.
The anion of Z is not particularly limited, but is preferably a non-nucleophilic anion, and examples thereof include a sulfonic acid anion, a carboxylic acid anion, a sulfonyl imide anion, a bis (alkylsulfonyl) imide anion, a tris (alkylsulfonyl) methyl anion, and the like.
The non-nucleophilic anion is an anion having a remarkably low ability to cause nucleophilic reactions, and is an anion capable of inhibiting time-lapse decomposition caused by intramolecular nucleophilic reactions. Thereby improving the stability of the composition over time.
Examples of the sulfonic acid anion include an aliphatic sulfonic acid anion, an aromatic sulfonic acid anion, and a camphorsulfonic acid anion.
Examples of the carboxylic acid anion include an aliphatic carboxylic acid anion, an aromatic carboxylic acid anion, and an aralkyl carboxylic acid anion.
The aliphatic moiety in the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion may be an alkyl group, and may be a cycloalkyl group, and preferably an alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms, and the aromatic group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.
The alkyl group, cycloalkyl group and aryl group in the aliphatic sulfonic acid anion and the aromatic sulfonic acid anion may have a substituent.
As another non-nucleophilic anion, for example, fluorinated phosphor (e.g., PF) 6 - ) Boron fluoride (e.g., BF) 4 - ) Antimony fluoride, etc. (e.g., sbF) 6 - )。
The anion of Z is preferably an aliphatic sulfonic acid anion in which at least the α -position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonic acid anion in which a fluorine atom or a group having a fluorine atom is substituted, a bis (alkylsulfonyl) imide anion in which an alkyl group is substituted with a fluorine atom, or a tris (alkylsulfonyl) methide anion in which an alkyl group is substituted with a fluorine atom. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonic acid anion having 4 to 8 carbon atoms or a benzenesulfonic acid anion having a fluorine atom, and is still more preferably a nonafluorobutanesulfonic acid anion, a perfluorooctanesulfonic acid anion, a pentafluorobenzenesulfonic acid anion or a 3,5-bis (trifluoromethyl) benzenesulfonic acid anion.
In the general formula (1), Z is preferably an anion represented by any of the following general formulae (3) to (5).
[ chemical formula 10]
Figure BDA0003811393030000171
In the general formula (3), the compound (A),
xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
L 1 Represents a single bond or a divalent linking group.
A represents a 1-valent organic group.
x represents an integer of 1 to 20.
[ chemical formula 11]
Figure BDA0003811393030000181
In the general formula (4), in the formula,
Xf 1 each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. 2 Xf 1 May be connected to each other to form a ring structure.
[ chemical formula 12]
Figure BDA0003811393030000182
In the general formula (5), the metal salt,
Xf 2 each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. 2 Xf 2 May be connected to each other to form a ring structure.
The alkyl group in the alkyl group substituted with at least one fluorine atom as Xf preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. Also, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
The alkyl group substituted with at least one fluorine atom may have a substituent. The substituent is not particularly limited, and examples thereof include the substituent T described above.
As L 1 The 2-valent linking group of (a), for example, examples thereof include-COO- (= C (= O) -O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO 2 -, AAn alkyl group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and a 2-valent linking group formed by combining a plurality of these groups.
<xnotran> , , -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO </xnotran> 2 -、-SO 2 Alkylene-, -COO-alkylene-, -alkylene-COO-, -OCO-alkylene-, -alkylene-OCO-, -CONH-alkylene-or-NHCO-alkylene-, more preferably alkylene, -COO-, or-OCO-, -CONH-, -SO 2 -, -COO-alkylene-, -alkylene-COO-, -OCO-alkylene-or-alkylene-OCO-.
The alkylene group, cycloalkylene group and alkenylene group may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T, preferably a fluorine atom.
A represents an organic group.
The number of carbon atoms of the organic group is not particularly limited, but is generally 1 to 30, preferably 1 to 20.
The organic group is not particularly limited, and examples thereof include an alkyl group and an alkoxy group.
The alkyl group is not particularly limited, and may be linear or branched, and is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably an alkyl group having 1 to 4 carbon atoms.
The alkoxy group is not particularly limited, and is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 6 carbon atoms, and still more preferably an alkoxy group having 1 to 4 carbon atoms.
The alkyl group and the alkoxy group may have a substituent. May have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T, preferably a fluorine atom.
And, a may represent an organic group including a cyclic structure. Among them, a cyclic organic group is preferable.
Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.
The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl groups. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecyl, tetracyclo + dialkyl, and adamantyl. Among them, alicyclic groups having a bulky structure of 7 or more carbon atoms such as norbornyl, tricyclodecanyl, tetracyclodecyl, tetracyclododecyl, and adamantyl groups are preferable.
The aryl group may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
The heterocyclic group may be monocyclic or polycyclic. Polycyclic heterocyclic groups can further inhibit acid diffusion. The heterocyclic group may or may not have aromatic properties. Examples of the aromatic heterocyclic ring include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocyclic ring having no aromatic group include a tetrahydropyran ring, a lactone ring, a sultone ring and a decahydroisoquinoline ring. Examples of the lactone ring and the sultone ring include the lactone structure and the sultone structure exemplified in the above-mentioned resins. The heterocyclic ring in the heterocyclic group is particularly preferably a furan ring, a thiophene ring, a pyridine ring or a decahydroisoquinoline ring.
The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be a straight chain or branched chain, and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be a monocyclic group, a polycyclic group, or a spiro ring, and preferably has 3 to 20 carbon atoms), an aryl group (preferably has 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a carbamate group, a urea group, a thioether group, a sulfonamide group, and a sulfonate group. In addition, the carbon constituting the cyclic organic group (carbon contributing to the formation of a ring) may be a carbonyl carbon.
As Xf 1 The alkyl group substituted with at least one fluorine atom in (b) is the same as the alkyl group substituted with at least one fluorine atom described as Xf.
As Xf 2 The alkyl group substituted with at least one fluorine atom in (b) is the same as the alkyl group substituted with at least one fluorine atom described as Xf.
The compound represented by the above general formula (1) is preferably a compound represented by the following general formula (2).
[ chemical formula 13]
Figure BDA0003811393030000201
In the general formula (2), in the formula,
ra to Rd each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
However, at least 1 of Ra to Rd represents an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
Q has the same meaning as that of Q in the above general formula (1).
R 1 、R 2 Has the same meaning as R in the above general formula (1) 1 、R 2 Have the same meaning.
R 5 、R 6 、R 7 、R 8 And R 9 Has the same meaning as R in the above general formula (1) 5 、R 6 、R 7 、R 8 And R 9 Have the same meaning.
R 5 ～R 9 At least 2 of which may be connected to each other to form a ring.
Z has the same meaning as that of Z-in the above general formula (1).
Alkyl as Ra to Rd with the above-mentioned as R 1A 、R 2A 、R 1B And R 2B The alkyl groups are the same as those described.
Cycloalkyl as Ra-Rd with R as described above 1A 、R 2A 、R 1B And R 2B The cycloalkyl groups described are the same.
Aryl as Ra to Rd with the above-mentioned as R 1A 、R 2A 、R 1B And R 2B The aryl groups are the same as those described.
As halogen atoms of Ra to RdWith the above as R 1A 、R 2A 、R 1B And R 2B The halogen atoms mentioned are the same.
Ra to Rd preferably represent a hydrogen atom, an alkyl group, a cycloalkyl group or a halogen atom, and more preferably represent a hydrogen atom, an alkyl group or a cycloalkyl group.
R 5 ～R 9 At least 2 of which may be connected to each other to form a ring.
As R 5 ～R 9 The ring formed by connecting at least 2 of them is not particularly limited, and examples thereof include aromatic or non-aromatic (for example, aliphatic) hydrocarbon rings, aromatic or non-aromatic heterocyclic rings, and polycyclic condensed rings in which 2 or more of these rings are combined. Examples of the ring structure (in a polycyclic fused ring, a monocyclic ring structure constituting the fused ring structure) include a 3-to 10-membered ring, preferably a 4-to 8-membered ring, and more preferably a 5-or 6-membered ring.
As a preferred mode, in the general formula (1) or the general formula (2), R 5 ～R 9 At least one of (a) and (b) preferably represents an alkoxy group, a cycloalkoxy group, an alkylthio group, or a cycloalkylthio group, and more preferably represents an alkoxy group or a cycloalkoxy group.
Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited to these specific examples. t Bu represents a tert-butyl group, et represents an ethyl group, n bu represents n-butyl.
[ chemical formula 14]
Figure BDA0003811393030000221
[ chemical formula 15]
Figure BDA0003811393030000231
Other photoacid generators can be used in addition to the compound represented by the general formula (1) within a range not impairing the effects of the present invention.
The photoacid generator may be in the form of a low molecular weight compound or may be embedded in a part of a polymer. Further, the form of the low-molecular compound and the form of the low-molecular compound embedded in a part of the polymer may be used in combination.
The photoacid generator is preferably in the form of a low molecular weight compound.
When the photoacid generator is in the form of a low-molecular-weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and further preferably 1,000 or less.
When the photoacid generator is in a form of being embedded in a part of the polymer, it may be embedded in a part of the resin (a) described later, or may be embedded in a resin different from the resin (a).
The photoacid generator may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The content of the photoacid generator in the composition (the total amount thereof when a plurality of photoacid generators are present) is preferably 0.1 to 35% by mass, more preferably 0.5 to 25% by mass, even more preferably 1.0 to 20% by mass, and particularly preferably 1.0 to 20% by mass, based on the total solid content of the composition.
< (A) resin >
The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains a resin (a).
The resin (a) is typically a resin having an increased polarity by the action of an acid, and is preferably a resin having an increased polarity by the action of an acid and having a changed solubility in a developer.
The resin (a)) whose polarity is increased by the action of the acid is preferably a resin obtained by polymerizing at least an ethylenically unsaturated compound.
The above-mentioned ethylenically unsaturated compound preferably has 1 to 4 ethylenically unsaturated bonds, more preferably 1. The ethylenically unsaturated compound is preferably a monomer of a monomer.
The molecular weight of the ethylenically unsaturated compound is preferably from 28 to 1,000, more preferably from 50 to 800, and still more preferably from 100 to 600.
The resin having increased polarity by the action of an acid preferably has an acid-decomposable group, and more preferably a resin containing a structural unit having an acid-decomposable group.
In this case, in the pattern forming method according to the present invention to be described later, it is preferable to form a positive pattern when an alkaline developer is used as the developer, and to form a negative pattern when an organic developer is used as the developer.
[ structural Unit having acid-decomposable group ]
The resin (a) preferably contains a structural unit having an acid-decomposable group (also referred to as a "repeating unit").
As the resin (a), a known resin can be suitably used. For example, known resins disclosed in paragraphs 0055 to 0191 of U.S. patent application publication No. 2016/0274458, paragraphs 0035 to 0085 of U.S. patent application publication No. 2015/0004544, and paragraphs 0045 to 0090 of U.S. patent application publication No. 2016/0147150 can be preferably used as the resin (A).
The acid-decomposable group preferably has a structure in which a polar group is protected by a group (dissociative group) dissociated by the action of an acid.
Examples of the polar group include an acidic group (a group dissociated in a 2.38 mass% aqueous tetramethylammonium hydroxide solution) such as a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, an (alkylsulfonyl) (alkylcarbonyl) imide group, a bis (alkylcarbonyl) methylene group, a bis (alkylcarbonyl) imide group, a bis (alkylsulfonyl) methylene group, a bis (alkylsulfonyl) imide group, a tris (alkylcarbonyl) methylene group, a tris (alkylsulfonyl) methylene group, and an alcoholic hydroxyl group.
The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, and refers to a hydroxyl group other than a hydroxyl group (phenolic hydroxyl group) directly bonded to an aromatic ring, except for an aliphatic alcohol group (e.g., hexafluoroisopropanol group) substituted with an electron-withdrawing group such as a fluorine atom as the alpha-position of the hydroxyl group. The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less.
Preferred polar groups include a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group.
Preferred groups as the acid-decomposable groups are groups in which hydrogen atoms of these groups are substituted with groups (detaching groups) detached by the action of an acid.
Examples of the group (releasing group) released by the action of an acid include-C (R) 36 )(R 37 )(R 38 )、-C(R 36 )(R 37 )(OR 39 ) and-C (R) 01 )(R 02 )(OR 39 ) And the like.
In the formula, R 36 ～R 39 Each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R 36 And R 37 May be bonded to each other to form a ring.
R 01 And R 02 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.
R 36 ～R 39 、R 01 And R 02 The alkyl group (b) is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, and an octyl group.
R 36 ～R 39 、R 01 And R 02 The cycloalkyl group of (b) may be of a monocyclic type or of a polycyclic type. The monocyclic type is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl. The polycyclic type is preferably a cycloalkyl group having 6 to 20 carbon atoms, and examples thereof include an adamantyl group, a norbornyl group, an isobornyl group, a camphyl group, a dicyclopentanyl group, an α -pinenyl group, a tricyclodecanyl group, a tetracyclododecyl group, an androstanyl group and the like. In addition, at least one carbon atom in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.
R 36 ～R 39 、R 01 And R 02 The aryl group of (b) is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, an anthracenyl group and the like.
R 36 ～R 39 、R 01 And R 02 The aralkyl group of (2) is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group and the like.
R 36 ～R 39 、R 01 And R 02 The alkenyl group is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.
As R 36 And R 37 The ring formed by bonding to each other is preferably a cycloalkyl group (monocyclic or polycyclic). The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group, or an adamantyl group.
The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group or the like, and more preferably an acetal group or a tertiary alkyl ester group.
The resin (a) preferably has a structural unit represented by the following formula AI as a structural unit having an acid-decomposable group.
[ chemical formula 16]
Figure BDA0003811393030000261
In formula AI, xa 1 A halogen atom other than a hydrogen atom or a fluorine atom or a 1-valent organic group, T represents a single bond or a 2-valent linking group, rx 1 ～Rx 3 Each independently represents alkyl or cycloalkyl, rx 1 ～Rx 3 Any 2 of them may be bonded to form a ring structure, or may not form a ring structure.
As a linking group having a valence of 2 for T, examples thereof include alkylene, arylene, and the like-COO-Rt-and-O-Rt-, etc. In the formula, rt represents an alkylene group, a cycloalkylene group or an arylene group.
T is preferably a single bond or-COO-Rt-. Rt is preferably a chain alkylene group having 1 to 5 carbon atoms, more preferably-CH 2 -、-(CH 2 ) 2 -or- (CH) 2 ) 3 -. T is more preferably a single bond.
Xa 1 Preferably a hydrogen atom or an alkyl group.
Xa 1 The alkyl group of (2) may have a substituent, and examples of the substituent include a hydroxyl group and a fluorine atomA halogen atom other than the above.
Xa 1 The alkyl group (C) is preferably a C1-4 alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, and a hydroxymethyl group. Xa 1 The alkyl group of (b) is preferably a methyl group.
As Rx 1 、Rx 3 And Rx 3 The alkyl group (b) may be linear or branched, and preferably includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and the like. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.Rx 1 、Rx 2 And Rx 3 In the alkyl group of (3), a part of the bond between carbons may be a double bond.
As Rx 1 、Rx 2 And Rx 3 The cycloalkyl group of (3) is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group or an adamantyl group.
As Rx 1 、Rx 2 And Rx 3 The ring structure formed by bonding 2 of (a) is preferably a monocyclic cycloalkyl ring such as a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, or a cyclooctane ring, or a polycyclic cycloalkyl ring such as a norbornane ring, a tetracyclodecane ring, a tetracyclododecane ring, or an adamantane ring. More preferably a cyclopentyl ring, a cyclohexyl ring or an adamantane ring. As Rx 1 、Rx 2 And Rx 3 The ring structure formed by bonding 2 of (2) is also preferably the structure described below.
[ chemical formula 17]
Figure BDA0003811393030000271
Specific examples of monomers corresponding to the structural unit represented by formula AI are given below, but the present invention is not limited to these specific examples. The following specific examples correspond to Xa in the formula AI 1 In the case of methyl, xa 1 May be optionally substituted with a halogen atom other than a hydrogen atom or a fluorine atom or a 1-valent organic group.
[ chemical formula 18]
Figure BDA0003811393030000281
The resin (A) preferably has a structural unit described in paragraphs 0336 to 0369 of U.S. patent application laid-open No. 2016/0070167 as a structural unit having an acid-decomposable group.
The resin (a) may have, as a structural unit having an acid-decomposable group, a structural unit containing a group which is decomposed by the action of an acid to generate an alcoholic hydroxyl group, as described in paragraphs 0363 to 0364 of U.S. patent application laid-open No. 2016/0070167.
The resin (a) preferably contains, as the repeating unit having an acid-decomposable group, a repeating unit having a structure (acid-decomposable group) in which a phenolic hydroxyl group is protected by a leaving group decomposed by the action of an acid. In the present specification, the phenolic hydroxyl group is a group obtained by substituting a hydrogen atom of an aromatic hydrocarbon group with a hydroxyl group. The aromatic ring of the aromatic hydrocarbon group is a monocyclic or polycyclic aromatic ring, and examples thereof include a benzene ring and a naphthalene ring.
Examples of the leaving group which is decomposed and removed by the action of an acid include groups represented by formulas (Y1) to (Y4).
Formula (Y1): -C (Rx) 1 )(Rx 2 )(Rx 3 )
Formula (Y2): -C (= O) OC (Rx) 1 )(Rx 2 )(Rx 3 )
Formula (Y3): -C (R) 36 )(R 37 )(OR 38 )
Formula (Y4): -C (Rn) (H) (Ar)
In the formulae (Y1), (Y2), rx 1 ～Rx 3 Each independently represents an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). Wherein, when Rx is 1 ～Rx 3 When all are alkyl groups (linear or branched), rx is preferred 1 ～Rx 3 At least 2 of which are methyl groups.
Wherein, rx 1 ～Rx 3 Each independently of the other is more preferably a repeating unit representing a linear or branched alkyl group，Rx 1 ～Rx 3 Each independently is more preferably a repeating unit representing a linear alkyl group.
Rx 1 ～Rx 3 2 of these may also be bonded to form a single ring or multiple rings.
As Rx 1 ～Rx 3 The alkyl group of (2) is preferably an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group and the like.
As Rx 1 ～Rx 3 The cycloalkyl group of (3) is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group, or an adamantyl group.
As Rx 1 ～Rx 3 The cycloalkyl group in which 2 of these groups are bonded is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group, or an adamantyl group. Among these, monocyclic cycloalkyl groups having 5 to 6 carbon atoms are more preferable.
Rx 1 ～Rx 3 In the cycloalkyl group in which 2 of them are bonded, for example, 1 of methylene groups constituting the ring may be substituted with a group having a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group.
The groups represented by the formulae (Y1) and (Y2) are preferably, for example, rx 1 Is methyl or ethyl, and Rx 2 And Rx 3 And bonded to form the cycloalkyl group.
In the formula (Y3), R 36 ～R 38 Each independently represents a hydrogen atom or a 1-valent organic group. R 37 And R 38 May be bonded to each other to form a ring. Examples of the 1-valent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. R 36 Preferably a hydrogen atom.
In the formula (Y4), ar represents an aromatic hydrocarbon group. Rn represents an alkyl group, a cycloalkyl group or an aryl group. Rn and Ar may bond to each other to form a non-aromatic ring. Ar is more preferably an aryl group.
The repeating unit having a structure in which the phenolic hydroxyl group is protected by a leaving group which is decomposed by the action of an acid (acid-decomposable group) is preferably a repeating unit having a structure in which a hydrogen atom in the phenolic hydroxyl group is protected by a group represented by formulae (Y1) to (Y4).
The repeating unit having a structure in which a phenolic hydroxyl group is protected by a leaving group which is decomposed by the action of an acid (acid-decomposable group) is preferably a repeating unit represented by the following general formula (AII).
[ chemical formula 19]
Figure BDA0003811393030000301
In the general formula (AII),
R 61 、R 62 and R 63 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Wherein R is 62 May be reacted with Ar 6 Bonded to form a ring, in which case R 62 Represents a single bond or an alkylene group.
X 6 Represents a single bond, -COO-or-CONR 64 -。R 64 Represents a hydrogen atom or an alkyl group.
L 6 Represents a single bond or an alkylene group.
Ar 6 Represents an (n + 1) -valent aromatic hydrocarbon group when it is reacted with R 62 And (b) an aromatic hydrocarbon group having a valence of (n + 2) when bonded to form a ring.
In the case that n is not less than 2, Y 2 Each independently represents a hydrogen atom or a group released by the action of an acid. Wherein, Y 2 At least one of them represents a group which is detached by the action of an acid. As Y 2 The group to be eliminated by the action of the acid (2) is preferably represented by the formulae (Y1) to (Y4).
n represents an integer of 1 to 4.
Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms), and preferably a group having 8 or less carbon atoms.
[ chemical formula 20]
Figure BDA0003811393030000311
[ chemical formula 21]
Figure BDA0003811393030000321
The resin (a) may contain 1 kind of structural unit having an acid-decomposable group alone, or may contain 2 or more kinds.
The content of the structural unit having an acid-decomposable group contained in the resin (a) (the total of the structural units having an acid-decomposable group when a plurality of structural units are present) is preferably 5 to 90 mol%, more preferably 10 to 80 mol%, and still more preferably 15 to 70 mol% based on all the structural units of the resin (a).
In the present invention, when the content of the "structural unit" is defined in terms of a molar ratio, the "structural unit" and the "monomer unit" have the same meaning. In the present invention, the "monomer unit" may be modified by polymerization such as a polymer reaction. The same applies to the following.
[ having at least 1 structural unit selected from the group consisting of a lactone structure, a sultone structure and a carbonate structure ]
The resin (a) preferably contains a structural unit having at least 1 selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.
The lactone structure or the sultone structure may have any structure as long as it has a lactone structure or a sultone structure, and preferably has a 5-to 7-membered ring lactone structure or a 5-to 7-membered ring sultone structure, and more preferably has a structure in which another ring structure is fused with a 5-to 7-membered ring lactone structure to form a bicyclic structure or a spiro structure, or a structure in which another ring structure is fused with a 5-to 7-membered ring sultone structure to form a bicyclic structure or a spiro structure. Further, it preferably contains a structural unit having a lactone structure represented by any one of the following formulae LC1-1 to LC1-21 or a sultone structure represented by any one of the following formulae SL1-1 to SL 1-3. Also, the lactone structure or sultone structure may be directly bonded to the main chain. Preferred structures are LC1-1, LC1-4, LC1-5, LC1-8, LC1-16, LC1-21, SL1-1.
[ chemical formula 22]
Figure BDA0003811393030000331
The lactone moiety or the sultone moiety may have a substituent (Rb) 2 ) Or may have no substituent (Rb) 2 ). As preferred substituent (Rb) 2 ) Examples thereof include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom other than a fluorine atom, a hydroxyl group, a cyano group, and an acid-decomposable group. More preferably an alkyl group having 1 to 4 carbon atoms, a cyano group and an acid-decomposable group. n2 represents an integer of 0 to 4. When n2 is 2 or more, a plurality of substituents (Rb) are present 2 ) May be the same or different. And, there are a plurality of substituents (Rb) 2 ) May be bonded to each other to form a ring.
The structural unit having a lactone structure or a sultone structure is preferably a structural unit represented by the following formula III.
The resin containing a structural unit having an acid-decomposable group preferably contains a structural unit represented by the following formula III.
[ chemical formula 23]
Figure BDA0003811393030000341
In the above-mentioned formula III, the compound,
a represents an ester bond (a group represented by-COO-) or an amide bond (a group represented by-CONH-).
n is represented by-R 0 The number of repetitions of the structure represented by-Z-represents an integer of 0 to 5, preferably 0 or 1, more preferablyIs 0. In the case where n is 0, -R is absent 0 -Z-, A and R 8 By a single bond.
R 0 Represents alkylene, cycloalkylene, or a combination thereof. R 0 In the case where there are a plurality of such units, each independently represents alkylene, cycloalkylene, or a combination thereof.
Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond. When a plurality of Z s are present, each Z independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond, or a urea bond.
R 8 Represents a 1-valent organic group having a lactone structure or a sultone structure.
R 7 Represents a hydrogen atom, a halogen atom other than a fluorine atom, or a 1-valent organic group (preferably a methyl group).
R 0 The alkylene group or cycloalkylene group of (a) may have a substituent.
Z is preferably an ether bond or an ester bond, and more preferably an ester bond.
Specific examples of monomers corresponding to the structural unit represented by formula III and specific examples of monomers corresponding to the structural unit represented by formula A-1 described later are given below, but the present invention is not limited to these specific examples. The following specific examples correspond to R in formula III 7 And R in the formula A-1 described later A 1 In the case of methyl, however, R 7 And R A 1 Can be optionally substituted with a hydrogen atom, a halogen atom other than a fluorine atom, or a 1-valent organic group.
[ chemical formula 24]
Figure BDA0003811393030000351
In addition to the above monomers, the monomers shown below are also preferably used as the raw materials of the resin (a).
[ chemical formula 25]
Figure BDA0003811393030000352
The resin (a) may contain a structural unit having a carbonate structure. The carbonate structure is preferably a cyclic carbonate structure.
The structural unit having a cyclic carbonate structure is preferably a structural unit represented by the following formula A-1.
[ chemical formula 26]
Figure BDA0003811393030000361
In the formula A-1, R A 1 Represents a hydrogen atom, a halogen atom other than a fluorine atom or a 1-valent organic group (preferably methyl group), n represents an integer of 0 or more, R A 2 Represents a substituent. When n is 2 or more, R A 2 Each independently represents a substituent, a represents a single bond or a 2-valent linking group, and Z represents an atomic group that forms a monocyclic structure or a polycyclic structure together with a group represented by-O-C (= O) -O-in the formula.
The resin (a) preferably has a structural unit described in paragraphs 0370 to 0414 of U.S. patent application laid-open No. 2016/0070167 as a structural unit having at least 1 selected from the group consisting of a lactone structure, a sultone structure and a carbonate structure.
The resin (a) preferably has a structural unit (a) containing at least 2 lactone structures (hereinafter, also referred to as "structural unit (a)").
The at least 2 lactone structures may be, for example, a structure in which at least 2 lactone structures are condensed, and may also be a structure in which at least 2 lactone structures are connected by a single bond or a linking group.
The lactone structure of the structural unit (a) is not particularly limited, but a 5-to 7-membered ring lactone structure is preferable, and a structure in which other ring structures in the 5-to 7-membered ring lactone structure are condensed in the form of a bicyclic structure or a spiro structure is preferable.
The lactone structure is preferably represented by any one of LC1-1 to LC 1-21.
The structural unit having at least 2 lactone structures (hereinafter, also referred to as "structural unit (a)") is preferably a structural unit represented by the following formula L-1.
[ chemical formula 27]
Figure BDA0003811393030000362
In the formula L-1, ra represents a hydrogen atom or an alkyl group, and Rb represents a partial structure having 2 or more lactone structures.
The alkyl group in Ra is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. The alkyl group of Ra may be substituted. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, an alkoxy group such as a mercapto group, a hydroxyl group, a methoxy group, an ethoxy group, an isopropoxy group, a tert-butoxy group and a benzyloxy group, and an acetoxy group such as an acetyl group and a propionyl group. Ra is preferably a hydrogen atom, methyl group, trifluoromethyl group or hydroxymethyl group.
Examples of the lactone structure of the Rb part structure include the above lactone structures.
The partial structure of Rb having 2 or more lactone structures, for example, a structure in which at least 2 lactone structures are connected by a single bond or a linking group and at least 2 lactone structures are condensed.
The structural unit (a 1) having a structure in which at least 2 lactone structures are condensed and the structural unit (a 2) having a structure in which at least 2 lactone structures are connected by a single bond or a linking group will be described below.
Structural units (a 1) having a structure of at least 2 condensed rings of lactone structure
The structure of at least 2 lactone structure condensed rings is preferably a structure of 2 or 3 lactone structure condensed rings, and more preferably a structure of 2 lactone structure condensed rings.
Examples of the structural unit having a structure in which at least 2 lactone structures are condensed (hereinafter, also referred to as "structural unit (a 1)") include a structural unit represented by the following formula L-2.
[ chemical formula 28]
Figure BDA0003811393030000371
In the formula L-2, ra has the same meaning as Ra in the formula L-1, and Re 1 ～Re 8 Each independently represents a hydrogen atom or an alkyl group, me 1 Represents a single bond or a 2-valent linking group, me 2 And Me 3 Each independently represents a 2-valent linking group.
Re 1 ～Re 8 The alkyl group of (b) is, for example, preferably 5 or less carbon atoms, and more preferably 1 carbon atom.
Re 1 ～Re 8 Examples of the alkyl group having 5 or less carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, and a tert-pentyl group.
Wherein Re 1 ～Re 8 Preferably a hydrogen atom.
Me 1 Examples of the 2-valent linking group in (a) include an alkylene group, a cycloalkylene group, -O-, -CO-, -COO-, -OCO-and a combination of 2 or more of these groups.
Me 1 The alkylene group (b) is preferably a C1-10 alkylene group, for example. Further, the alkylene group having 1 or 2 carbon atoms is more preferable, and methylene or vinyl is preferable as the alkylene group having 1 or 2 carbon atoms.
Me 1 The alkylene group(s) may be linear or branched, and examples thereof include methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,3-diyl, propane-2,2-diyl, pentane-1,5-diyl and hexane-1,6-diyl.
Me 1 The cycloalkylene group of (b) is, for example, preferably 5 to 10 carbon atoms, and more preferably 5 or 6 carbon atoms.
Me 1 Examples of the cycloalkylene group in (b) include cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group, cyclodecylene group and the like.
As Me 1 The 2-valent linking group of (2), the group obtained by combining the above 2 or more groups, for example, a group obtained by combining an alkylene group with-COO-, is preferablyA group formed by combining-OCO-and alkylene. Further, the group in which 2 or more groups are combined is more preferably a group in which a methylene group and a-COO-group are combined and a group in which a-COO-group and a methylene group are combined.
Me 2 And Me 3 Examples of the linking group having a valence of 2 include alkylene and-O-. Me 2 And Me 3 The 2-valent linking group of (A) is preferably a methylene group, a vinyl group, -O-, and more preferably-O-.
The monomer corresponding to the structural unit (a 1) can be synthesized, for example, by the method described in japanese patent application laid-open No. 2015-160836.
A specific example of the structural unit (a 1) is shown below, but the present invention is not limited thereto. In the following formulae, R 9 Represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group, and represents a bonding position with other structural units.
[ chemical formula 29]
Figure BDA0003811393030000391
[ chemical formula 31]
Figure BDA0003811393030000401
At least 2 structural units (a 2) in which the lactone structures have a structure linked by a single bond or a linking group
The structure in which at least 2 lactone structures are connected by a single bond or a linking group is preferably a structure in which 2 to 4 lactone structures are connected by a single bond or a linking group, and more preferably a structure in which 2 lactone structures are connected by a single bond or a linking group.
Examples of the linking group include M in the formula L-3 described later 2 The linking group (C) is the same as the above-mentioned group.
Examples of the structural unit in which 2 or more lactone structures have a structure connected by a single bond or a linking group (hereinafter, also referred to as "structural unit (a 2)") include a structural unit represented by the following formula L-3.
[ chemical formula 32]
Figure BDA0003811393030000402
In the formula L-3, ra has the same meaning as Ra in the above formula L-1, and M 1 And M 2 Each independently of the other being a single bond or a linking group, lc 1 And Lc 2 Each independently represents a group having a lactone structure.
M 1 Examples of the linking group include alkylene, cycloalkylene, -O-, -CO-,; -COO-, -OCO-and a combination of 2 or more of these groups.
M 1 The alkylene group (b) is preferably a C1-10 alkylene group, for example.
M 1 The alkylene group(s) may be linear or branched, and examples thereof include methylene, ethane-1,1-diyl, ethane-1,2-diyl, propane-1,1-diyl, propane-1,3-diyl, propane-2,2-diyl, pentane-1,5-diyl and hexane-1,6-diyl.
M 1 The cycloalkylene group (b) is preferably a C5-10 group, for example.
M 1 Examples of the cycloalkylene group in (b) include cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclodecylene and the like.
As M 1 The linking group of (2) or more is preferably a group obtained by combining the above-mentioned groups, for example, a group obtained by combining an alkylene group with-COO-or a group obtained by combining-OCO-with an alkylene group. Further, the group in which 2 or more groups are combined is more preferably a group in which a methylene group and a-COO-group are combined and a group in which a-COO-group and a methylene group are combined.
M 2 Examples of the linking group include M 1 The same groups as those mentioned for the linking group of (2) are exemplified.
Lc 1 The lactone structure is preferably a 5-to 7-membered ring lactone structure, for example, and in the 5-to 7-membered ring lactone structure, the other ring structures are condensed in the form of a bicyclic structure or a spiro structure. The above lactoneThe structure is more preferably a lactone structure represented by any of the above LC1-1 to LC 1-21. Further preferable lactone structures include LC1-1, LC1-4, LC1-5, LC1-6, LC1-13, LC1-14 and LC1-17.
Lc 1 The lactone structure may have a substituent. Examples of the substituent that may be contained in the lactone structure of Lc1 include the same substituents as the substituent (Rb 2) of the lactone structure described above.
Lc 2 Examples of the lactone structure include Lc 1 Examples of the lactone structures include those having the same lactone structure.
The structural unit (a 2) represented by the formula L-3 is preferably a structural unit represented by the formula L-4.
[ chemical formula 33]
Figure BDA0003811393030000411
In the formula L-4, ra has the same meaning as Ra in the above formula L-1, mf 1 And Mf 2 Each independently represents a single bond or a linking group, rf 1 、Rf 2 And Rf 3 Each independently represents a hydrogen atom or an alkyl group, mf 1 And Rf 1 Can be bonded to each other to form a ring Mf 2 And Rf 2 Or Rf 3 May be bonded to each other to form a ring.
Mf 1 The meaning of the linking group of (A) is the same as that of M of the above formula L-3 1 The connecting groups of (A) have the same meaning.
Mf 2 The meaning of the linking group of (A) is the same as that of M of the above formula L-3 2 The connecting groups of (A) have the same meaning.
Rf 1 Examples of the alkyl group in (2) include alkyl groups having 1 to 4 carbon atoms. Rf 1 The alkyl group having 1 to 4 carbon atoms of (A) is preferably a methyl group or an ethyl group, and more preferably a methyl group. Rf 1 The alkyl group of (b) may have a substituent. Rf 1 Examples of the substituent which the alkyl group may have include an alkoxy group such as a hydroxyl group, a methoxy group and an ethoxy group, a cyano group, a halogen atom such as a fluorine atom, and the like.
Rf 2 And Rf 3 Meaning of alkyl of (A) and Rf 1 The alkyl groups of (a) have the same meaning.
Mf 1 And Rf 1 May be bonded to each other to form a ring. Examples of the structure in which Mf1 and Rf1 are bonded to each other to form a ring include lactone structures represented by the above-mentioned LC1-13, LC1-14 or LC1-17 among the above-mentioned lactone structures.
Mf 2 And Rf 2 Or Rf 3 May be bonded to each other to form a ring.
Examples of the structure in which Mf2 and Rf2 are bonded to each other to form a ring include lactone structures represented by the above-mentioned LC1-7, LC1-8 or LC1-15 among the above-mentioned lactone structures.
Mf 2 And Rf 3 Examples of the structure forming a ring by bonding to each other include lactone structures represented by any of the above LC1-3 to LC1-6 among the above lactone structures.
A specific example of the structural unit (a 2) is shown below, but the present invention is not limited thereto. * Indicating the bonding position with other structural units.
[ chemical formula 34]
Figure BDA0003811393030000431
The structural unit having at least 2 lactone structures usually has optical isomers, but any optical isomer may be used. Further, 1 kind of optical isomer may be used alone, or a plurality of kinds of optical isomers may be used in combination. When 1 optical isomer is mainly used, the optical purity (ee) is preferably 90% or more, more preferably 95% or more.
The content of the structural unit having at least 2 lactone structures is preferably 10 to 60 mol%, more preferably 20 to 50 mol%, and still more preferably 30 to 50 mol% based on the total structural units in the resin (a).
In order to improve the effect of the present invention, 2 or more kinds of structural units having at least 2 lactone structures may be used in combination. When 2 or more kinds of repeating units having at least 2 lactone structures are contained, the content ratio of the total of the structural units having at least 2 lactone structures is preferably within the above range.
The resin (a) may contain 1 kind of structural unit alone having at least 1 kind selected from a lactone structure, a sultone structure and a carbonate structure, or may contain 2 or more kinds in combination.
The content of the structural unit having at least 1 kind selected from the lactone structure, the sultone structure and the carbonate structure which are contained in the resin (a) is preferably 5 to 70 mol%, more preferably 10 to 65 mol%, and further preferably 20 to 60 mol% with respect to the total structural unit of the resin (a) (the total content thereof in the case where a plurality of structural units having at least 1 kind selected from the lactone structure, the sultone structure and the carbonate structure are present).
[ structural units having polar groups ]
The resin (a) preferably contains a structural unit having a polar group.
Examples of the polar group include a hydroxyl group, a cyano group, and a carboxyl group.
The structural unit having a polar group is preferably a structural unit having an alicyclic hydrocarbon structure substituted with a polar group. The structural unit having a polar group preferably does not have an acid-decomposable group. As the alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a polar group, an adamantyl group or a norbornyl group is preferable.
The resin (a) preferably has a carboxyl group.
Specific examples of the monomer corresponding to the structural unit having a polar group are given below, but the present invention is not limited to these specific examples. The following specific examples are described as methacrylate compounds, but may be acrylate compounds.
[ chemical formula 35]
Figure BDA0003811393030000441
Specific examples of the structural unit having a polar group include structural units disclosed in paragraphs 0415 to 0433 of U.S. patent application publication No. 2016/0070167.
The resin (a) may contain 1 kind of the structural unit having a polar group alone, or 2 or more kinds thereof in combination.
The content of the structural unit having a polar group is preferably 5 to 40 mol%, more preferably 5 to 30mol%, and still more preferably 10 to 25 mol% with respect to the structural unit in the resin (a).
[ structural units each having no acid-decomposable group or polar group ]
The resin (a) may further have a structural unit having neither the acid-decomposable group nor the polar group. The structural unit having neither the acid-decomposable group nor the polar group preferably has an alicyclic hydrocarbon structure. Examples of the structural unit having neither an acid-decomposable group nor a polar group include structural units described in paragraphs 0236 to 0237 of the specification of U.S. patent application laid-open No. 2016/0026083. Preferred examples of the monomer corresponding to the structural unit having neither the acid-decomposable group nor the polar group are shown below.
[ chemical formula 36]
Figure BDA0003811393030000451
Further, as a specific example of a structural unit having neither an acid-decomposable group nor a polar group, a structural unit disclosed in paragraph 0433 of the specification of U.S. patent application laid-open No. 2016/0070167 can be cited.
The resin (a) may contain 1 kind of the structural unit alone, which does not have any of the acid-decomposable group and the polar group, or 2 or more kinds of the structural units may be contained in combination.
The content of the structural unit having neither the acid-decomposable group nor the polar group is preferably 5 to 40 mol%, more preferably 5 to 30mol%, and still more preferably 5 to 25 mol% based on the total structural units in the resin (a).
(repeating unit (a 1))
The resin (a) may further have the following repeating unit (a 1).
The repeating unit (a 1) is a repeating unit derived from a monomer (also referred to as "monomer a 1") having a glass transition temperature of 50 ℃ or lower when prepared into a homopolymer.
The repeating unit (a 1) is a non-acid-decomposable repeating unit. Therefore, the repeating unit (a 1) does not have an acid-decomposable group.
(method of measuring glass transition temperature of homopolymer)
The glass transition temperature of the homopolymer is measured by Differential Scanning Calorimetry (DSC) in the presence of a reference value or a literature value and in the absence of a reference value or a literature value. The weight average molecular weight (Mw) of the homopolymer used for the measurement of Tg was 18000, and the dispersity (Mw/Mn) was 1.7. As the DSC apparatus, a thermal analysis DSC differential scanning calorimeter Q1000 type was used, and the temperature increase rate was measured at 10 ℃/min.
The homopolymer used for the measurement of Tg may be synthesized by a known method using a corresponding monomer, and can be synthesized by, for example, a general dropping polymerization method. An example is shown below.
54 parts by mass of Propylene Glycol Monomethyl Ether Acetate (PGMEA) were heated to 80 ℃ under a nitrogen stream. While the liquid was stirred, 125 parts by mass of a PGMEA solution containing 21% by mass of the corresponding monomer, 2,2' -azobisisobutyric acid dimethyl ester, 0.35% by mass, was added dropwise over 6 hours. After the end of the dropwise addition, the mixture was further stirred at 80 ℃ for 2 hours. The reaction solution was naturally cooled, reprecipitated with a large amount of methanol/water (mass ratio 9: 1), filtered, and the obtained solid was dried to obtain a homopolymer (Mw: 18000, mw/Mn: 1.7). The obtained homopolymer was used for DSC measurement. The DSC apparatus and the temperature increase rate were as described above.
The glass transition temperature (Tg) of the monomer a1 is not particularly limited as long as it is 50 ℃ or lower when it is a homopolymer, and the Tg of the monomer a1 is preferably 30 ℃ or lower when it is a homopolymer from the viewpoint of improving the resolution of the dot pattern and suppressing the roughness of the resist pattern side wall which may occur during etching. The lower limit of Tg when the monomer a1 is a homopolymer is not particularly limited, but it is preferably at least-80 ℃, more preferably at least-70 ℃, still more preferably at least-60 ℃, and particularly preferably at least-50 ℃. When the lower limit of Tg in the case of making the monomer a1 into a homopolymer is set to the above range, the fluidity of the pattern during heating can be suppressed, and the verticality of the dot pattern can be further improved, which is preferable.
The repeating unit (a 1) is preferably a repeating unit which may contain a heteroatom in the chain and has a non-acid-decomposable alkyl group having 2 or more carbon atoms, from the viewpoint of allowing the residual solvent to be more easily volatilized. In the present specification, "non-acid-decomposable" means having a property of not causing a dissociation/decomposition reaction by an acid generated from a photoacid generator.
More specifically, the "non-acid-decomposable alkyl group" includes an alkyl group which is not separated from the resin (a) by the action of an acid generated by the photoacid generator and an alkyl group which is not decomposed by the action of an acid generated by the photoacid generator.
The non-acid-decomposable alkyl group may be either linear or branched.
Hereinafter, a repeating unit having a non-acid-decomposable alkyl group having 2 or more carbon atoms, which may contain a hetero atom in the chain, will be described.
The non-acid-decomposable alkyl group which may contain a heteroatom in the chain and has 2 or more carbon atoms is not particularly limited, and examples thereof include alkyl groups having 2 to 20 carbon atoms and alkyl groups having 2 to 20 carbon atoms containing a heteroatom in the chain.
Examples of the alkyl group having 2 to 20 carbon atoms and containing a hetero atom in the chain include 1 or 2 or more-CH 2 is-O-) -S-) -CO-, -NR 6 Or an alkyl group substituted with an organic group having a valence of 2, which is a combination of 2 or more thereof. R is as defined above 6 Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
As the non-acid-decomposable alkyl group having 2 or more carbon atoms which may contain a hetero atom in the chain, specific examples thereof include methyl, ethyl, propyl, and the like,Butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, lauryl group, stearyl group, isobutyl group, sec-butyl group, 1-ethylpentyl group, and 2-ethylhexyl group, and 1 or 2 or more of these-CH groups 2 -alkyl substituted by-O-or-O-CO-for a valency 1.
The number of carbon atoms of the non-acid-decomposable alkyl group which may contain a heteroatom in the chain and has 2 or more carbon atoms is preferably 2 or more and 16 or less, more preferably 2 or more and 10 or less, and still more preferably 2 or more and 8 or less. The lower limit of the number of carbon atoms of the non-acid-decomposable alkyl group having 2 or more carbon atoms is preferably 4 or more.
The non-acid-decomposable alkyl group having 2 or more carbon atoms may have a substituent (e.g., substituent T).
The repeating unit (al) is preferably a repeating unit represented by the following general formula (1-2).
[ chemical formula 37]
Figure BDA0003811393030000471
In the general formula (1-2), R 1 Represents a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group. R 2 Represents a non-acid-decomposable alkyl group having 2 or more carbon atoms and optionally containing a heteroatom in the chain.
As a group consisting of R 1 The halogen atom is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
As a group consisting of R 1 The alkyl group is not particularly limited, and examples thereof include alkyl groups having 1 to 10 carbon atoms, specifically, methyl, ethyl, tert-butyl, and the like. Among them, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.
As a group consisting of R 1 The cycloalkyl group represented by the formula is not particularly limited, and examples thereof include a cycloalkyl group having 5 to 10 carbon atoms, and more specifically, a cyclohexyl group and the like.
As R 1 Among them, a hydrogen atom or a methyl group is preferable.
From R 2 Of a representationThe definition and preferred modes of the non-acid-decomposable alkyl group which may contain a heteroatom in the chain and has 2 or more carbon atoms are as described above.
In addition, the repeating unit (a 1) may be a repeating unit having a non-acid-decomposable alkyl group which may contain a heteroatom in the chain and has a carboxyl group or a hydroxyl group, or a non-acid-decomposable cycloalkyl group which may contain a heteroatom in the ring member and has a carboxyl group or a hydroxyl group, from the viewpoint of allowing the residual solvent to be more easily volatilized.
Hereinafter, a repeating unit having a non-acid-decomposable alkyl group which may contain a heteroatom in the chain and have a carboxyl group or a hydroxyl group, or a non-acid-decomposable cycloalkyl group which may contain a heteroatom in the ring member and have a carboxyl group or a hydroxyl group will be described.
The non-acid-decomposable alkyl group may be either linear or branched.
The number of carbon atoms of the non-acid-decomposable alkyl group is preferably 2 or more, and the upper limit of the number of carbon atoms of the non-acid-decomposable alkyl group is preferably 20 or less, for example, from the viewpoint that Tg of the homopolymer is 50 ℃ or less.
The non-acid-decomposable alkyl group which may contain a heteroatom in the chain is not particularly limited, and examples thereof include an alkyl group having 2 to 20 carbon atoms and an alkyl group having 2 to 20 carbon atoms which may contain a heteroatom in the chain. In addition, at least one of the hydrogen atoms in the alkyl group is substituted with a carboxyl group or a hydroxyl group.
Examples of the alkyl group having 2 to 20 carbon atoms and containing a hetero atom in the chain include 1 or 2 or more-CH 2 <xnotran> - -O-, -S-, -CO-, -NR </xnotran> 6 Or an alkyl group substituted with a 2-valent organic group obtained by combining 2 or more of these groups. R is as defined above 6 Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
The number of carbon atoms of the non-acid-decomposable alkyl group which may contain a heteroatom in the chain is preferably 2 to 16, more preferably 2 to 10, and even more preferably 2 to 8, from the viewpoint of further excellent crack resistance (less likely to cause cracking).
The non-acid-decomposable alkyl group may have a substituent (e.g., substituent T).
Specific examples of the repeating unit having a non-acid-decomposable alkyl group containing a heteroatom in the chain and having a carboxyl group include repeating units having the following structures.
[ chemical formula 38]
Figure BDA0003811393030000491
The number of carbon atoms of the non-acid-decomposable cycloalkyl group is preferably 5 or more, and from the viewpoint of the Tg of the homopolymer being 50 ℃ or less, the upper limit of the number of carbon atoms of the non-acid-decomposable cycloalkyl group is, for example, preferably 20 or less, more preferably 16 or less, and still more preferably 10 or less.
The non-acid-decomposable cycloalkyl group which may contain a heteroatom in a ring member is not particularly limited, and examples thereof include a cycloalkyl group having 5 to 20 carbon atoms (more specifically, a cyclohexyl group) and a cycloalkyl group having 5 to 20 carbon atoms which contains a heteroatom in a ring member. In addition, at least one of the hydrogen atoms in the cycloalkyl group is substituted with a carboxyl group or a hydroxyl group.
Examples of the cycloalkyl group having 5 to 20 carbon atoms and containing a heteroatom in a ring member include 1 or 2 or more of-CH 2 <xnotran> - -O-, -S-, -CO-, -NR </xnotran> 6 Or cycloalkyl substituted with 2-valent organic groups obtained by combining 2 or more of them. R is as defined above 6 Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
The non-acid-decomposable cycloalkyl group may have a substituent (e.g., substituent T).
Among them, a repeating unit represented by the following general formula (1-3) is preferable from the viewpoint of further excellent effects of the present invention as a repeating unit having a non-acid-decomposable alkyl group which may contain a heteroatom in the chain and has a carboxyl group or a hydroxyl group, or a non-acid-decomposable cycloalkyl group which may contain a heteroatom in the ring member and has a carboxyl group or a hydroxyl group.
[ chemical formula 39]
Figure BDA0003811393030000492
In the general formula (1-3), R 3 Represents a hydrogen atom, a halogen atom, an alkyl group or a cycloalkyl group. R 4 Represents a non-acid-decomposable alkyl group which may contain a heteroatom in the chain and have a carboxyl group or a hydroxyl group, or a non-acid-decomposable cycloalkyl group which may contain a heteroatom in a ring member and have a carboxyl group or a hydroxyl group.
In the general formula (1-3), R 3 And the above-mentioned R 1 The meaning is the same, and the preferred mode is the same.
From R 4 The definition and preferred modes of the non-acid-decomposable alkyl group which may contain a heteroatom in the chain and has a carboxyl group or a hydroxyl group, or the non-acid-decomposable cycloalkyl group which may contain a heteroatom in a ring member and has a carboxyl group or a hydroxyl group are as described above.
Wherein, as R 4 The non-acid-decomposable cycloalkyl group having a carboxyl group or a hydroxyl group, which may contain a heteroatom in the ring member, is preferable. Examples of such a mode include a repeating unit having the following structure.
[ chemical formula 40]
Figure BDA0003811393030000501
Examples of the monomer a1 include ethyl acrylate (-22 ℃), n-propyl acrylate (-37 ℃), isopropyl acrylate (-5 ℃), n-butyl acrylate (-55 ℃), n-butyl methacrylate (20 ℃), n-hexyl acrylate (-57 ℃), n-hexyl methacrylate (-5 ℃), n-octyl methacrylate (-20 ℃), 2-ethylhexyl acrylate (-70 ℃), isononyl acrylate (-82 ℃), lauryl methacrylate (-65 ℃), 2-hydroxyethyl acrylate (-15 ℃), 2-hydroxypropyl methacrylate (26 ℃), 1- [2- (methacryloyloxy) ethyl ] succinate (9 ℃), 2-ethylhexyl methacrylate (-10 ℃), sec-butyl acrylate (-26 ℃), methoxypolyethylene glycol monomethacrylate (n = 2) (-20 ℃), and hexadecyl acrylate (35 ℃). Further, the Tg (. Degree. C.) when the homopolymer is prepared is shown in parentheses.
In addition, methoxypolyethylene glycol monomethacrylate (n = 2) is a compound having the following structure.
[ chemical formula 41]
Figure BDA0003811393030000502
The monomer a1 is preferably n-butyl acrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl acrylate, lauryl methacrylate, cetyl acrylate, 2-hydroxyethyl acrylate and a compound represented by the following MA-5.
[ chemical formula 42]
Figure BDA0003811393030000511
The resin (a) may contain only 1 kind of repeating unit (a 1), or may contain 2 or more kinds.
In the resin (a), the content of the repeating unit (a 1) (the total of the plurality of repeating units (a 1) when present) is preferably 5 mol% or more, more preferably 10 mol% or more, preferably 50 mol% or less, more preferably 40 mol% or less, and further preferably 30mol% or less, with respect to all the repeating units of the resin (a). The content of the repeating unit (a 1) (the total of the plurality of repeating units (a 1) when present) in the resin (a) is preferably 5 to 50 mol%, more preferably 5 to 40 mol%, and still more preferably 5 to 30mol% based on all the repeating units in the resin (a).
(repeating unit (a 4) having a phenolic hydroxyl group) ]
The resin (a) may contain a repeating unit (a 4) having a phenolic hydroxyl group.
By containing the repeating unit (a 4), the resin (a) has a higher dissolution rate in alkali development and has excellent etching resistance.
The repeating unit having a phenolic hydroxyl group is not particularly limited, and examples thereof include a hydroxystyrene repeating unit and a hydroxystyrene (meth) acrylate repeating unit. The repeating unit having a phenolic hydroxyl group is preferably a repeating unit represented by the following general formula (I).
[ chemical formula 43]
Figure BDA0003811393030000512
In the formula (I), the compound is shown in the specification,
R 41 、R 42 and R 43 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Wherein R is 42 Can react with Ar 4 Bonded to form a ring, in which case R 42 Represents a single bond or an alkylene group.
X 4 Represents a single bond, -COO-or-CONR 64 -，R 64 Represents a hydrogen atom or an alkyl group.
L 4 Represents a single bond or a 2-valent linking group.
Ar 4 Represents an (n + 1) -valent aromatic hydrocarbon group when it is reacted with R 42 And (b) an aromatic hydrocarbon group having a valence of (n + 2) when bonded to form a ring.
n represents an integer of 1 to 5.
In order to make the repeating unit represented by the general formula (I) highly polar, it is also preferable that n is an integer of 2 or more or X 4 is-COO-or-CONR 64 -。
As a radical R in the general formula (I) 41 、R 42 And R 43 The alkyl group represented by (a) is preferably an alkyl group having not more than 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, which may have a substituent(s), more preferably an alkyl group having not more than 8 carbon atoms, and still more preferably an alkyl group having not more than 3 carbon atoms.
As in formula (I) by R 41 、R 42 And R 43 The cycloalkyl group may be monocyclic or polycyclic. Preferred is an optionally substituted monocyclic cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl or cyclohexyl.
As in formula (I) by R 41 、R 42 And R 43 A halogen atom ofExamples thereof include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
As a radical R in the general formula (I) 41 、R 42 And R 43 The alkyl group contained in the alkoxycarbonyl group is preferably the same as R 41 、R 42 And R 43 The alkyl in (1) is the same alkyl.
Preferred substituents in the above groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, urea groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, acyl groups, acyloxy groups, alkoxycarbonyl groups, cyano groups, nitro groups, and the like, and the number of carbon atoms in the substituent is preferably 8 or less.
Ar 4 Represents an (n + 1) -valent aromatic hydrocarbon group. The aromatic hydrocarbon group having a valence of 2 in the case where n is 1 may have a substituent, and is preferably an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group (tolylene group), a naphthylene group, or an anthracenylene group, or an aromatic hydrocarbon group containing a heterocycle such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, or thiazole.
Specific examples of the (n + 1) -valent aromatic hydrocarbon group in which n is an integer of 2 or more include groups obtained by removing (n-1) arbitrary hydrogen atoms from the specific examples of the 2-valent aromatic hydrocarbon group.
The (n + 1) -valent aromatic hydrocarbon group may further have a substituent.
Examples of the substituent which the alkyl group, the cycloalkyl group, the alkoxycarbonyl group and the (n + 1) -valent aromatic hydrocarbon group may have include R in the general formula (I) 41 、R 42 And R 43 The alkyl groups mentioned in (1); alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy; aryl groups such as phenyl; and the like.
As a result of X 4 Represented by-CONR 64 -(R 64 Represents a hydrogen atom or an alkyl group) 64 The alkyl group of (a) is, preferred examples thereof are an optionally substituted methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group,An alkyl group having 20 or less carbon atoms such as a hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group, and an alkyl group having 8 or less carbon atoms is more preferable.
As X 4 Preferably a single bond, -COO-or-CONH-, more preferably a single bond or-COO-.
As L 4 The 2-valent linking group in (1) is preferably an alkylene group, and the alkylene group is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, a vinyl group, a propylene group, a butylene group, a hexylene group, and an octylene group, which may have a substituent.
As Ar 4 The aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent is preferable, and a benzene ring group, a naphthalene ring group or a biphenylene ring group is more preferable. Among them, the repeating unit represented by the general formula (I) is preferably a repeating unit derived from hydroxystyrene. Namely, ar 4 Preferably a benzene ring group.
Specific examples of the repeating unit having a phenolic hydroxyl group are shown below, but the present invention is not limited thereto. Wherein a represents 1 or 2.
[ chemical formula 44]
Figure BDA0003811393030000541
The resin (a) preferably has a phenolic hydroxyl group.
The resin (a) may have 1 kind of repeating unit (a 4) alone, or may have 2 or more kinds in combination.
In the resin (a), the content of the repeating unit (a 4) is preferably 40 mol% or more, more preferably 50 mol% or more, and further preferably 60 mol% or more, based on all repeating units in the resin (a). The content of the repeating unit (a 4) is preferably 85 mol% or less, and more preferably 80 mol% or less, based on all the repeating units in the resin (a).
The resin (a) may have various structural units for the purpose of adjusting dry etching resistance, adaptability to standard developer, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc., which are generally required characteristics of a resist, in addition to the above structural units. Examples of such a structural unit include structural units corresponding to other monomers, but are not limited thereto.
Examples of the other monomer include compounds having one addition polymerizable unsaturated bond selected from acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like.
In addition to these, an addition polymerizable unsaturated compound copolymerizable with the monomers corresponding to the various structural units may be copolymerized.
In the resin (a), the contained molar ratio of each structural unit is appropriately set for adjusting various performances.
When the actinic-ray-or radiation-sensitive resin composition according to the present invention is for exposure to a fluorine argon (ArF) laser, it is preferable that the resin (a) has substantially no aromatic group from the viewpoint of ArF light transmittance. More specifically, among all the structural units of the resin (a), the structural unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, and further preferably 0mol%, that is, the structural unit having an aromatic group is not contained. Further, the resin (a) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.
The resin (a) preferably has all the structural units composed of (meth) acrylate-based structural units. In this case, any of a resin having all of the structural units as methacrylate structural units, a resin having all of the structural units as acrylate structural units, and a resin having all of the structural units formed of methacrylate structural units and acrylate structural units can be used, but the acrylate structural units are preferably 50 mol% or less with respect to all of the structural units of the resin (a).
When the actinic-ray-or radiation-sensitive resin composition according to the present invention is used for krypton fluoride (KrF) exposure, electron Beam (EB) exposure, or Extreme Ultraviolet (EUV) exposure, the resin (a) preferably contains a structural unit having an aromatic hydrocarbon group. The resin (a) more preferably contains a structural unit having a phenolic hydroxyl group.
Examples of the structural unit having a phenolic hydroxyl group include the above-mentioned repeating unit (a 4).
When the actinic-ray-or radiation-sensitive resin composition according to the present invention is for KrF exposure, EB exposure or EUV exposure, the resin (a) preferably has a structure in which a hydrogen atom of a phenolic hydroxyl group is protected by a group (a leaving group) that is decomposed and removed by the action of an acid.
The content of the structural unit having an aromatic hydrocarbon group contained in the resin (a) is preferably 30 to 100 mol%, more preferably 40 to 100 mol%, and still more preferably 50 to 100 mol% based on all the structural units in the resin (a).
The weight average molecular weight of the resin (a) is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, still more preferably 3,000 to 15,000, and particularly preferably 3,000 to 11,000.
The dispersity (Mw/Mn) is preferably 1.0 to 3.0, more preferably 1.0 to 2.6, still more preferably 1.0 to 2.0, and particularly preferably 1.1 to 2.0.
Specific examples of the resin (A) include, but are not limited to, the resins A-1 to A-12 used in the examples.
The resin (A) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The content of the resin (a) is preferably 20 mass% or more, more preferably 40 mass% or more, further preferably 60 mass% or more, and particularly preferably 80 mass% or more, based on the total solid content of the actinic-ray-sensitive or radiation-sensitive resin composition according to the present invention. The upper limit is not particularly limited, but is preferably 99.5% by mass or less, more preferably 99% by mass or less, and still more preferably 97% by mass or less.
[ hydrophobic resin ]
The actinic-ray-or radiation-sensitive resin composition according to the present invention preferably contains a hydrophobic resin (also referred to as "hydrophobic resin (E)").
The actinic-ray-or radiation-sensitive resin composition according to the present invention preferably contains at least a hydrophobic resin (E) other than the resin whose polarity is increased by the action of an acid and a resin whose polarity is increased by the action of an acid.
Since the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains the hydrophobic resin (E), the static/dynamic contact angle in the surface of the actinic ray-sensitive or radiation-sensitive film can be controlled. This makes it possible to improve the development characteristics, suppress degassing, improve the liquid immersion liquid following property in liquid immersion exposure, reduce liquid immersion defects, and the like.
The hydrophobic resin (E) is preferably designed to be biased to the surface of the resist film, but unlike the surfactant, does not necessarily need to have a hydrophilic group in the molecule, and may not contribute to uniform mixing of polar/non-polar substances.
In the present invention, the resin having a fluorine atom is treated as a hydrophobic resin and a fluorine-containing resin described later. The resin containing a structural unit having the acid-decomposable group preferably does not contain a fluorine atom.
From the viewpoint of being biased toward the film surface layer, the hydrophobic resin (E) preferably contains a group having a CH contained in a side chain moiety selected from the group consisting of a "fluorine atom", a "silicon atom" and a "resin 3 A resin of a structural unit of at least 1 kind in the partial structure ".
When the hydrophobic resin (E) contains a fluorine atom or a silicon atom, the fluorine atom or the silicon atom in the hydrophobic resin (E) may be contained in the main chain of the resin or may be contained in the side chain.
The hydrophobic resin (E) preferably has at least 1 group selected from the following groups (x) to (z).
(x) Acid radical
(y) a group which is decomposed by the action of an alkaline developer to increase the solubility in the alkaline developer (hereinafter, also referred to as a polarity converting group.)
(z) groups which are decomposed by the action of an acid
Examples of the acid group (x) include a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonimide group, an (alkylsulfonyl) (alkylcarbonyl) methylene group, an (alkylsulfonyl) (alkylcarbonyl) imide group, a bis (alkylcarbonyl) methylene group, a bis (alkylcarbonyl) imide group, a bis (alkylsulfonyl) methylene group, a bis (alkylsulfonyl) imide group, a tris (alkylcarbonyl) methylene group, a tris (alkylsulfonyl) methylene group, and a tris (alkylsulfonyl) methylene group.
As the acid group, a fluorinated alcohol group (preferably hexafluoroisopropanol group), a sulfonylimino group, or a bis (alkylcarbonyl) methylene group is preferable.
As the group (y) which is decomposed by the action of the alkaline developer to increase the solubility in the alkaline developer, examples thereof include a lactone group, a carboxylate group (-COO-), an acid anhydride group (-C (O) OC (O) -), and the like acid imide group (-NHCONH-), carboxylic thioester group (-COS-), carbonate group (-OC (O) O-), sulfate group (-OSO) 2 O-) and sulfonic ester group (-SO) 2 O-), etc., preferably a lactone group or a carboxylate group (-COO-).
The structural unit containing these groups is a structural unit in which these groups are directly bonded to the main chain of the resin, and examples thereof include structural units based on acrylate and methacrylate. The structural unit may bond these groups on the main chain of the resin via a linking group. Alternatively, the structural unit may be used in polymerization of a polymerization initiator or a chain transfer agent having these groups and introduced into the end of the resin.
Examples of the structural unit having a lactone group include the same repeating units as those having a lactone structure described in the above item of the resin (a).
The content of the structural unit having the group (y) which is decomposed by the action of the alkaline developer to increase the solubility in the alkaline developer is preferably 1 to 100 mol%, more preferably 3 to 98 mol%, and further preferably 5 to 95 mol% based on all the structural units in the hydrophobic resin (E).
The structural unit having a group (z) which is decomposed by the action of an acid in the hydrophobic resin (E) includes the same repeating unit as the structural unit having an acid-decomposable group in the resin (a). The structural unit having the group (z) decomposed by the action of an acid may have at least one of a fluorine atom and a silicon atom. The content of the structural unit having a group (z) decomposed by the action of an acid is preferably 1 to 80 mol%, more preferably 10 to 80 mol%, and still more preferably 20 to 60 mol% based on all the structural units in the resin (E).
The hydrophobic resin (E) may have a structural unit different from the above structural unit.
The fluorine atom-containing structural unit is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, based on all the structural units contained in the hydrophobic resin (E). The structural unit containing a silicon atom is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, based on all the structural units contained in the hydrophobic resin (E).
On the other hand, particularly in the hydrophobic resin (E), CH is contained in a side chain moiety 3 In the case of a partial structure, the hydrophobic resin (E) is also preferably in a form substantially free of fluorine atoms and silicon atoms. The hydrophobic resin (E) is preferably substantially composed of only structural units composed of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms, and sulfur atoms.
The hydrophobic resin (E) preferably has a weight average molecular weight of 1,000 to 100,000 in terms of standard polystyrene, more preferably 1,000 to 50,000.
The total content of the residual monomer and oligomer components contained in the hydrophobic resin (E) is preferably 0.01 to 5% by mass, and more preferably 0.01 to 3% by mass. The dispersity (Mw/Mn) is preferably in the range of 1 to 5, more preferably in the range of 1 to 3.
As the hydrophobic resin (E), known resins can be appropriately selected and used alone or as a mixture thereof. For example, known resins disclosed in paragraphs 0451 to 0704 of U.S. patent application laid-open No. 2015/0168830 and 0340 to 0356 of U.S. patent application laid-open No. 2016/0274458 can be preferably used as the hydrophobic resin (E). Also, the structural units disclosed in paragraphs 0177 to 0258 of U.S. patent application publication No. 2016/0237190 are also preferable as the structural units constituting the hydrophobic resin (E).
Fluorine-containing resins
The hydrophobic resin (E) is preferably a resin containing a fluorine atom (also referred to as "fluorine-containing resin").
When the hydrophobic resin (E) contains a fluorine atom, as a partial structure having a fluorine atom, a resin containing an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom is preferable.
The alkyl group having a fluorine atom is a linear or branched alkyl group in which at least one hydrogen atom is substituted by a fluorine atom, and preferably has 1 to 10 carbon atoms, and more preferably has 1 to 4 carbon atoms.
The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
Examples of the aryl group having a fluorine atom include aryl groups such as phenyl and naphthyl groups in which at least one hydrogen atom is substituted with a fluorine atom.
The alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, and the aryl group having a fluorine atom are preferably groups represented by formulae F2 to F4.
[ chemistry formula 45)
Figure BDA0003811393030000591
In the formulae F2 to F4,
R 57 ～R 68 each independently represents a hydrogen atom, a fluorine atom or an alkyl group (linear or branched). Wherein R is 57 ～R 61 At least one of R 62 ～R 64 And R 65 ～R 68 At least one of (a) and (b) each independently represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
R 57 ～R 61 And R 65 ～R 67 Preferably all fluorine atoms. R 62 、R 63 And R 68 An alkyl group in which at least one hydrogen atom is substituted with a fluorine atom (preferably a C1-4 alkyl group), and a C1-4 perfluoroalkyl group is more preferable. R is 62 And R 63 May be bonded to each other to form a ring.
Among them, the fluorine-containing resin preferably has an alkali decomposability from the viewpoint of further improving the effect of the present invention.
The term "the fluorine-containing resin has alkaline decomposability" means that 100mg of the fluorine-containing resin is added to a mixture of 2mL of a buffer solution having a pH of 10 and 8mL of THF, and the mixture is allowed to stand at 40 ℃ for 10 minutes to hydrolyze 30mol% or more of the total amount of decomposable groups in the fluorine-containing resin. The decomposition rate can be calculated from the ratio of the raw material and the decomposed product obtained by NMR analysis.
The fluorine-containing resin preferably has a structural unit represented by formula X from the viewpoints of tolerance of depth of focus, pattern linearity, improvement of developing characteristics, suppression of outgassing, improvement of liquid immersion liquid following property in liquid immersion exposure, and reduction of liquid immersion defects.
In addition, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention preferably further contains a fluorine-containing resin having a structural unit represented by formula X from the viewpoints of tolerance of depth of focus, pattern linearity, improvement of development characteristics, suppression of outgassing, improvement of liquid immersion liquid followability in liquid immersion exposure, and reduction of liquid immersion defects.
[ chemical formula 46]
Figure BDA0003811393030000601
In the formula X, Z represents a halogen atom, represented by R 11 OCH 2 A group represented by-or R 12 OC(＝0)CH 2 A group represented by R 11 And R 12 Each independently represents a substituent, and X represents an oxygen atom or a sulfur atom. L represents an (n + 1) -valent linking group, R 10 A group having a group which is decomposed by the action of an aqueous alkaline solution to increase the solubility of the fluorine-containing resin in the aqueous alkaline solution, n is a positive integer, and when n is 2 or more, a plurality of R' s 10 May be the same as or different from each other.
Examples of the halogen atom of Z include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.
As R 11 And R 12 Examples of the substituent(s) include an alkyl group (preferably having 1 to 4 carbon atoms), a cycloalkyl group (preferably having 6 to 10 carbon atoms) and an aryl group (preferably having 6 to 10 carbon atoms). And as R 11 And R 12 The substituent(s) may further have a substituent, and examples of such further substituent include an alkyl group (preferably having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (preferably having 1 to 4 carbon atoms), and a carboxyl group.
The linking group as L is preferably a linking group having a valence of 2 or 3 (in other words, n is preferably 1 or 2), more preferably a linking group having a valence of 2 (in other words, n is preferably 1). The linking group as L is preferably a linking group selected from the group consisting of an aliphatic group, an aromatic group, and a combination thereof.
For example, when n is 1 and the linking group of L is a linking group having a valence of 2, examples of the aliphatic group having a valence of 2 include an alkylene group, an alkenylene group, an alkynylene group, and a polyalkyleneoxy group. Among them, an alkylene group or an alkenylene group is preferable, and an alkylene group is more preferable.
The 2-valent aliphatic group may have a chain structure or a ring structure, but is preferably a chain structure as compared with the ring structure, and is preferably a linear structure as compared with a chain structure having branches. The aliphatic group having a valence of 2 may have a substituent, and examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a hydroxyl group, a carboxyl group, an amino group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, an arylamino group, and a diarylamino group.
The aromatic group having a valence of 2 may be an arylene group. Among them, phenylene and naphthylene are preferable.
The aromatic group having a valence of 2 may have a substituent, and examples of the substituent in the aliphatic group having a valence of 2 include an alkyl group.
Further, L may be a 2-valent group obtained by removing 2 hydrogen atoms at arbitrary positions from the structure represented by the above formulae LC1-1 to LC1-21 or formulae SL1-1 to SL-3.
When n is 2 or more, specific examples of the (n + 1) -valent linking group include groups obtained by removing arbitrary (n-1) hydrogen atoms from the specific examples of the 2-valent linking group.
Specific examples of L include the following linking groups.
[ chemical formula 47]
-CH 2 - -CH 2 CH 2 - -CH 2 cH 2 cH 2 - -cH 2 CH 2 CH 2 CH 2 -
-CH 2 CH 2 CH 2 CH 2 CH 2 - -CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 -
Figure BDA0003811393030000611
These linking groups may further have a substituent as described above.
As R 10 The group represented by the following formula W is preferable.
-Y-R 20 Formula W
In the formula W, Y represents a group which is decomposed by the action of an alkaline aqueous solution to increase the solubility in the alkaline aqueous solution. R 20 Represents an electron withdrawing group.
<xnotran> Y, (-COO- OCO-), (-C (O) OC (O) -), (-NHCONH-), (-COS-), (-OC (O) O-), (-OSO </xnotran> 2 O-) and sulfonate (-SO) 2 O-), preferably a carboxylate group.
The electron-withdrawing group is preferably a partial structure represented by the following formula EW. In formula EW denotes a bond directly bonded to the group Y in formula W.
[ chemical formula 48]
Figure BDA0003811393030000621
In the formula EW, the compound represented by the formula EW,
n ew is represented by-C (R) ew1 )(R ew2 ) The number of repetitions of the linker represented by (A) represents an integer of 0 or 1. When n is ew When 0, represents a single bond, represents Y ew1 And (4) direct bonding.
Y ew1 Examples thereof include a halogen atom, a cyano group, a nitro group, a group represented by the following formula-C (R) f1 )(R f2 )-R f3 Halo (cyclo) alkyl, halo aryl, oxy, carbonyl, sulfonyl, sulfinyl and combinations thereof. (wherein, when Y is ew1 When it is a halogen atom, cyano group or nitro group, n ew Is 1. )
R ew1 And R ew2 Each independently represents an arbitrary group, for example, a hydrogen atom, an alkyl group (preferably having 1 to 8 carbon atoms), a cycloalkyl group (preferably having 3 to 10 carbon atoms), or an aryl group (preferably having 6 to 10 carbon atoms).
R ew1 、R ew2 And Y ew1 At least 2 of which may be connected to each other to form a ring.
Further, "halo (cyclo) alkyl" represents an alkyl group and a cycloalkyl group which are at least partially halogenated, and "haloaryl" represents an aryl group which is at least partially halogenated.
As Y ew1 Preferably a halogen atom, of the formula-C (R) f1 )(R f2 )-R f3 A halo (cyclo) alkyl group or a halo aryl group.
R f1 Represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group or a perhaloaryl group, preferably a fluorine atom, a perfluoroalkyl group or a perfluorocycloalkyl group, more preferably a fluorine atom or a trifluoromethyl group.
R f2 And R f3 Each independently represents a hydrogen atom, a halogen atom or an organic group, R f2 And R f3 May be joined to form a ring. Examples of the organic group include an alkyl group, a cycloalkyl group and an alkoxy group, which may be substituted with a halogen atom (preferably a fluorine atom). R is f2 And R f3 Preferably (halo) alkyl or (halo) cycloalkyl. R is f2 More preferably with R f1 The same group as R, or f3 Joined to form a ring.
As R f2 And R f3 Examples of the ring formed by linkage include a (halo) cycloalkyl ring.
As R f1 ～R f3 The (halo) alkyl group in (b) may be either linear or branched, and the linear (halo) alkyl group is preferably a group having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms.
As R f1 ～R f3 Or R in f2 And R f3 The (halo) cycloalkyl group in the ring formed by the linkage may be of a monocyclic type or of a polycyclic type. In the case of polycyclic types, (halo) cycloalkyl groups may be bridged. That is, in this case, the (halo) cycloalkyl group may have a bridging structure.
Examples of the (halo) cycloalkyl group include a group represented by the following formula and a halogenated group thereof. In addition, a part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.
[ chemical formula 49]
Figure BDA0003811393030000631
As R f2 And R f3 Or R is f2 And R f3 (halo) cycloalkyl in the ring formed by the linkage, preferably of formula-C (n) F (2n-2) And H represents a fluorocycloalkyl group. Here, the number of carbon atoms n is not particularly limited, but is preferably 5 to 13, and more preferably 6.
Y ew1 Or R is f1 The (per) haloaryl group in (1) may be exemplified by a group represented by the formula-C (n) F (n-1) The perfluoroaryl group is represented. Here, the number of carbon atoms n is not particularly limited, but is preferably 5 to 13, and more preferably 6.
As R ew1 、R ew2 And Y ew1 At least 2 of which may be linked to each other to form a ring, preferably a cycloalkyl group or a heterocyclic group.
Each group and each ring constituting the partial structure represented by the formula EW may further have a substituent.
In the above formula W, R 20 Preferably an alkyl group substituted by 1 or more selected from the group consisting of a halogen atom, a cyano group and a nitro group, more preferably an alkyl group (haloalkyl group) substituted by a halogen atom, and further preferably a fluoroalkyl group. The number of carbon atoms of the alkyl group substituted by 1 or more selected from the group consisting of a halogen atom, a cyano group and a nitro group is preferably 1 to 10, more preferably 1 to 5.
More specifically, R 20 Preferably is composed of-C (R' 1 )(R’ f1 )(R’ f2 ) or-C (R' 1 )(R’ 2 )(R’ f1 ) The atomic group shown. R' 1 And R' 2 Each independently represents a hydrogen atom or a (preferably unsubstituted) alkyl group which is unsubstituted by an electron withdrawing group. R' f1 And R' f2 Each independently represents a halogen atom, a cyano group, a nitro group or a perfluoroalkyl group.
As R' 1 And R' 2 The alkyl group (b) may be linear or branched, and preferably has 1 to 6 carbon atoms.
As R' f1 And R' f2 The perfluoroalkyl group (b) may be linear or branched, and preferably has 1 to 6 carbon atoms.
As R 20 As a preferred specific example thereof, may be mentioned-CF 3 、-C 2 F 5 、-C 3 F 7 、-C 4 F 9 、-CF(CF 3 ) 2 、-CF(CF 3 )C 2 F 5 、-CF 2 CF(CF 3 ) 2 、-C(CF 3 ) 3 、-C 5 F 11 、-C 6 F 13 、-C 7 F 15 、-C 8 F 17 、-CH 2 CF 3 、-CH 2 C 2 F 5 、-CH 2 C 3 F 7 、-CH(CF 3 ) 2 、-CH(CF 3 )C 2 F 5 、-CH 2 CF(CF 3 ) 2 and-CH 2 And (C) CN. Among them, preferred is-CF 3 、-C 2 F 5 、-C 3 F 7 、-C 4 F 9 、-CH 2 CF 3 、-CH 2 C 2 F 5 、-CH 2 C 3 F 7 、-CH(CF 3 ) 2 or-CH 2 CN, more preferably-CH 2 CF 3 、-CH 2 C 2 F 5 、-CH 2 C 3 F 7 、-CH(CF 3 ) 2 or-CH 2 CN, more preferably-CH 2 C 2 F 5 、-CH(CF 3 ) 2 or-CH 2 CN, particularly preferably-CH 2 C 2 F 5 or-CH (CF) 3 ) 2 。
As the structural unit represented by the formula X, a structural unit represented by the following formula X-1 or formula X-2 is preferable, and a structural unit represented by the formula X-1 is more preferable.
[ chemical formula 50]
Figure BDA0003811393030000651
In the formula X-1, R 20 Represents an electron withdrawing group, L 2 Denotes a 2-valent linking group, X 2 Represents an oxygen atom or a sulfur atom, Z 2 Represents a halogen atom.
In the formula X-2, R 20 Represents an electron withdrawing group, L 3 Denotes a 2-valent linking group, X 3 Represents an oxygen atom or a sulfur atom, Z 3 Represents a halogen atom.
As L 2 And L 3 Specific examples and preferable examples of the 2-valent linking group of (3) are the same as those described for L as the 2-valent linking group of the formula X.
As R 2 And R 3 The electron-withdrawing group(s) of (a) is preferably a partial structure represented by the formula EW described above, and specific examples and preferred examples are also as described above, and a halo (cyclo) alkyl group is more preferred.
In the above formula X-1, L 2 And R 2 Form a ring without bonding to each other, and in the above formula X-2, L 3 And R 3 Form a ring without bonding to each other.
As X 2 And X 3 Preferably an oxygen atom.
As Z 2 And Z 3 Preferably, it is a fluorine atom or a chlorine atom, and more preferably a fluorine atom.
Further, as the structural unit represented by the formula X, a structural unit represented by the formula X-3 is also preferable.
[ chemical formula 51]
Figure BDA0003811393030000652
In the formula X-3, R 20 Represents an electron withdrawing group, R 21 Represents a hydrogen atom, an alkyl group or an aryl group, L 4 Denotes a 2-valent linking group, X 4 Represents an oxygen atom or a sulfur atom, and m represents 0 or 1.
As L 4 Specific examples and preferable examples of the 2-valent linking group in (2) are the same as those described for L as the 2-valent linking group in the formula X.
As R 4 The electron-withdrawing group (b) is preferably a partial structure represented by the formula EW, and specific examples and preferred examples are also as described above, and more preferably a halo (cyclo) alkyl group.
Further, in the above formula X-3, L 4 And R 4 Form a ring without bonding to each other.
As X 4 Preferably an oxygen atom.
Further, the structural unit represented by the formula X is also preferably a structural unit represented by the formula Y-1 or a structural unit represented by the formula Y-2.
[ chemical formula 52]
Figure BDA0003811393030000661
In the formulae Y-1 and Y-2, Z represents a halogen atom, R 11 OCH 2 A group represented by-or by R 12 OC(＝O)CH 2 A group represented by R 11 And R 12 Each independently represents a substituent, R 20 Indicating suckerAn electron group.
As R 20 The electron-withdrawing group(s) of (a) is preferably a partial structure represented by the formula EW described above, and specific examples and preferred examples are also as described above, and a halo (cyclo) alkyl group is more preferred.
As Z, a halogen atom, represented by R 11 OCH 2 A group represented by and R 12 OC(＝O)CH 2 Specific examples and preferred examples of the group represented by the formula-are the same as those described in the above formula 1.
The content of the structural unit represented by the formula X is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, and still more preferably 30 to 100 mol% based on all the structural units of the fluorine-containing resin.
Preferred examples of the structural unit constituting the hydrophobic resin (E) are shown below.
The hydrophobic resin (E) is preferably a resin obtained by arbitrarily combining these constituent units, but is not limited thereto.
[ chemical formula 53]
Figure BDA0003811393030000671
[ chemical formula 54]
Figure BDA0003811393030000681
The hydrophobic resin (E) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
From the viewpoint of achieving both liquid immersion liquid following properties and developing properties in liquid immersion exposure, it is preferable to use 2 or more kinds of hydrophobic resins (E) having different surface energies.
The content of the hydrophobic resin (E) in the composition is preferably 0.01 to 10% by mass, and more preferably 0.05 to 8% by mass, based on the total solid content of the actinic-ray-or radiation-sensitive resin composition according to the present invention.
[ acid diffusion controller ]
The actinic-ray-or radiation-sensitive resin composition according to the present invention contains an acid diffusion controller (also referred to as "acid diffusion controller (D)").
In a preferred embodiment, the acid diffusion controller (D) is preferably an amine compound.
The acid diffusion controller (D) traps acid generated from an acid generator or the like at the time of exposure, and functions as a quencher that suppresses a reaction of the acid-decomposable resin in the unexposed portion due to the excessively generated acid. For example, a basic compound (DA), a basic compound (DB) in which the basicity is reduced or eliminated by irradiation with actinic rays or radiation, an onium salt (DC) which is a relatively weak acid with respect to an acid generator, a low-molecular compound (DD) having a nitrogen atom and having a group which is detached by the action of an acid, an onium salt compound (DE) having a nitrogen atom in a cation portion, or the like can be used as the acid diffusion controller (D).
Among them, the actinic-ray-or radiation-sensitive resin composition according to the present invention preferably contains a nitrogen-containing compound, and more preferably contains a nitrogen-containing basic compound, as the acid diffusion controller (D), from the viewpoint of linearity of a pattern obtained over time.
In the actinic ray-or radiation-sensitive resin composition according to the present invention, a known acid diffusion controller can be suitably used. For example, known compounds disclosed in paragraphs 0627 to 0664 of U.S. patent application publication No. 2016/0070167, paragraphs 0095 to 0187 of U.S. patent application publication No. 2015/0004544, paragraphs 0403 to 0423 of U.S. patent application publication No. 2016/0237190, and paragraphs 0259 to 0328 of U.S. patent application publication No. 2016/0274458 can be preferably used as the acid diffusion control agent (D).
[ basic Compound (DA) ]
As the basic compound (DA), compounds having structures represented by the following formulae a to E can be preferably cited.
[ chemical formula 55]
Figure BDA0003811393030000691
In the formula A and the formula E,
R 200 、R 201 and R 202 May be the same or different and each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl group (preferably having 6 to 20 carbon atoms). R 201 And R 202 May be bonded to each other to form a ring.
R 203 、R 204 、R 205 And R 206 May be the same or different and each independently represents an alkyl group having 1 to 20 carbon atoms.
The alkyl group in the formula a and the formula E may have a substituent or may be unsubstituted.
The alkyl group is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms or a cyanoalkyl group having 1 to 20 carbon atoms.
More preferably, the alkyl groups in formula a and formula E are unsubstituted.
The basic compound (DA) is preferably guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine or the like, and more preferably a compound having an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and/or an ether bond, an aniline derivative having a hydroxyl group and/or an ether bond, or the like.
[ basic Compound (DB) in which basicity is reduced or eliminated by irradiation with actinic rays or radiation ]
A basic compound (DB) (hereinafter, also referred to as "compound (DB)") having a proton acceptor functional group and being decomposed by irradiation with actinic rays or radiation to reduce or eliminate the proton acceptor or to change the proton acceptor from the proton acceptor to acidic is a compound having a proton acceptor functional group.
The proton acceptor functional group is a functional group having a group or an electron capable of electrostatic interaction with a proton, and represents, for example, a functional group having a macrocyclic compound structure such as a cyclic polyether, or a functional group having a nitrogen atom with an unshared electron pair not contributing to pi conjugation. The nitrogen atom having an unshared electron pair not contributing to pi conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.
[ chemical formula 56]
Figure BDA0003811393030000701
Unshared electron pair
Examples of the preferable partial structure of the proton acceptor functional group include crown ethers, azacrown ethers, primary to tertiary amines, pyridine, imidazole, pyrazine, and the like.
The compound (DB) is decomposed by irradiation with actinic rays or radiation to reduce or eliminate the proton acceptor property or to change the proton acceptor property to acidic. Here, the decrease or disappearance of the proton acceptor or the change from the proton acceptor to acidity is a change in the proton acceptor property due to addition of a proton to the proton acceptor functional group, and specifically, indicates that when a proton adduct is generated from a compound (DB) having the proton acceptor functional group and a proton, the equilibrium constant in the chemical equilibrium is decreased.
Proton acceptor can be confirmed by pH measurement.
The acid dissociation constant pKa of the compound produced by the decomposition of the compound (DB) by irradiation with actinic rays or radiation preferably satisfies pKa < -1, more preferably-13 < pKa < -1, and still more preferably-13 < pKa < -3.
The acid dissociation constant pKa represents the acid dissociation constant in an aqueous solution, and is defined, for example, as chemical toilet (II) (revision 4, 1993, edited by japan chemical society, MARUZEN co., ltd.). The lower the value representing the acid dissociation constant pKa, the greater the acid strength. Specifically, the acid dissociation constant pKa in the aqueous solution can be actually measured by measuring the acid dissociation constant at 25 ℃. Alternatively, the number of substituents of Hammett and a value based on a known literature value database can be obtained by calculation using the following software package 1. The pKa values described in the present specification all represent values obtained by calculation using the software package.
Software package 1: advanced Chemistry Development (ACD/Labs) Software V8.14for Solaris (1994-2007 ACD/Labs).
Onium salt (DC) which is weak acid to photoacid generator
In the actinic-ray-or radiation-sensitive resin composition according to the present invention, an onium salt (DC) which is weak with respect to the photoacid generator can be used as the acid diffusion controller (D).
When an onium salt that will generate an acid that is a relatively weak acid with respect to an acid generated from a photoacid generator is used in admixture, if an acid generated from the photoacid generator by irradiation of actinic rays or radiation collides with an onium salt having an unreacted weak acid anion, the weak acid is released by salt exchange and an onium salt having a strong acid anion is generated. In this process, the strong acid is exchanged for a weak acid having a lower catalytic ability, and thus the acid is deactivated from the surface to enable control of acid diffusion.
From the viewpoint of the depth of focus tolerance and pattern linearity, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention preferably further comprises at least 1 compound selected from the group consisting of compounds represented by the formulae d1-1 to d 1-3.
[ chemical formula 57]
Figure BDA0003811393030000711
In the formulae d1-1 to d1-3, R 51 Represents a hydrocarbon group which may have a substituent, Z 2c Represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, provided that a fluorine atom is not bonded to a carbon atom adjacent to the S atom, and R 52 Represents an organic group, Y 3 Represents a linear, branched or cyclic alkylene or arylene group, rf represents a hydrocarbon group containing a fluorine atom, M + Each independently represents an ammonium cation, a sulfonium cation or an iodonium cationAnd (4) adding the active ingredients.
As with M + Preferred examples of the sulfonium cation and the iodonium cation include sulfonium cations represented by the formula ZI and iodonium cations represented by the formula ZII.
The onium salt (DC) which becomes a weak acid relative to the photoacid generator may be a compound having a cationic site and an anionic site in the same molecule, and the cationic site and the anionic site are linked by a covalent bond (hereinafter, also referred to as "compound (DCA)").
The compound (DCA) is preferably a compound represented by any one of the following formulas C-1 to C-3.
[ chemical formula 58]
Figure BDA0003811393030000721
In the formulae C-1 to C-3, R 1 、R 2 And R 3 Each independently represents a substituent having 1 or more carbon atoms.
L 1 Represents a 2-valent linking group or a single bond linking the cationic site and the anionic site.
-X - Represents a group selected from-COO - 、-SO 3 - 、-SO 2 - and-N - -R 4 The anionic site in (a). R is 4 Represents a structure having a carbonyl group (- = O) -), a sulfonyl group (- = S (= O) at a linking site to an adjacent N atom 2 -) and a sulfinyl group (-S (= O) -) each having at least 1 substituent having a valence of 1.
R 1 、R 2 、R 3 、R 4 And L 1 May be bonded to each other to form a ring structure. And, in the formula C-3, R is 1 ～R 3 2 of these substituents together represent 1 substituent having a valence of 2, and may be bonded to the N atom via a double bond.
As R 1 ～R 3 Examples of the substituent having 1 or more carbon atoms in (A) include alkyl, cycloalkyl, aryl, alkoxycarbonyl, cycloalkoxycarbonyl, aryloxycarbonyl, alkylaminocarbonyl, cycloalkylaminocarbonyl and arylaminoAlkylcarbonyl, and the like. Preferably an alkyl, cycloalkyl or aryl group.
L as a 2-valent linking group 1 Examples thereof include a straight-chain or branched alkylene group, a cycloalkylene group, an arylene group, a carbonyl group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, and a combination of 2 or more of these. L is 1 Preferably an alkylene group, an arylene group, an ether bond, an ester bond or a combination of 2 or more of these.
[ Low-molecular-weight Compound (DD) having a Nitrogen atom and a group which is eliminated by the action of an acid ]
The low-molecular compound (DD) (hereinafter, also referred to as "compound (DD)") having a nitrogen atom and having a group released by the action of an acid is preferably an amine derivative having a group released by the action of an acid on a nitrogen atom.
The group to be eliminated by the action of an acid is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, and more preferably a carbamate group or a hemiaminal ether group.
The molecular weight of the compound (DD) is preferably 100 to 1000, more preferably 100 to 700, and further preferably 100 to 500.
The compound (DD) may have a carbamate group having a protective group on a nitrogen atom. The protecting group constituting the carbamate group can be represented by the following formula d-1.
[ chemical formula 59]
Figure BDA0003811393030000731
In the formula d-1, the metal oxide,
R b each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), an aralkyl group (preferably having 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably having 1 to 10 carbon atoms). R is b May be connected to each other to form a ring.
R b Is shown inThe alkyl group, the cycloalkyl group, the aryl group and the aralkyl group may be independently substituted with a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group or an oxo group, an alkoxy group or a halogen atom. For R b The alkoxyalkyl groups represented are also the same.
As R b The alkyl group is preferably a linear or branched alkyl group, cycloalkyl group or aryl group, and more preferably a linear or branched alkyl group or cycloalkyl group.
As 2R b Examples of the rings formed by the mutual connection include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, and derivatives thereof.
Specific examples of the structure of the group represented by the formula d-1 include, but are not limited to, the structures disclosed in paragraph 0466 in the specification of U.S. patent application publication No. 2012/0135348.
The compound (DD) is preferably a compound having a structure represented by formula 6 below.
[ chemical formula 60]
Figure BDA0003811393030000741
In the case of the formula 6, the compound,
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and l + m =3 is satisfied.
R a Represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, 2R a May be the same or different, 2R a Or may be linked to each other to form a heterocyclic ring together with the nitrogen atom in the formula. The heterocyclic ring may contain a hetero atom other than the nitrogen atom in the formula.
R b With R in the above formula d-1 b Similarly, the preferred embodiments are also the same.
In formula 6, as R a The alkyl group, the cycloalkyl group, the aryl group and the aralkyl group of (A) may be independently substituted with the same groups as those mentioned above as the groups which may be substituted as R b Alkyl, cycloalkyl, aryl and aralkyl groups.
As the above-mentioned R a Specific examples of the alkyl group, cycloalkyl group, aryl group and aralkyl group (these groups may be substituted with the above-mentioned groups) of (A) include b The same as in the above-mentioned specific examples.
Specific examples of the compound (DD) particularly preferable in the present invention include, but are not limited to, the compounds disclosed in paragraph 0475 in the specification of U.S. patent application publication No. 2012/0135348.
The onium salt compound (DE) (hereinafter, also referred to as "compound (DE)") having a nitrogen atom in the cation portion is preferably a compound having a basic site containing a nitrogen atom in the cation portion. The basic site is preferably an amino group, and more preferably an aliphatic amino group. Further preferably, all atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. From the viewpoint of improving the basicity, it is preferable that the electron-withdrawing functional group (such as a carbonyl group, a sulfonyl group, a cyano group, and a halogen atom) is not directly bonded to a nitrogen atom.
Preferred specific structures of the compound (DE) include, but are not limited to, those disclosed in paragraph 0203 in the specification of U.S. patent application laid-open No. 2015/0309408.
Preferred examples of the acid diffusion controller (D) are shown below, but the present invention is not limited thereto.
[ chemical formula 61]
Figure BDA0003811393030000751
[ chemical formula 62]
Figure BDA0003811393030000761
[ chemical formula 63]
Figure BDA0003811393030000762
[ chemical formula 64]
Figure BDA0003811393030000771
[ chemical formula 65]
Figure BDA0003811393030000772
[ chemical formula 66]
Figure BDA0003811393030000773
In the actinic-ray-or radiation-sensitive resin composition of the present invention, 1 or more acid diffusion controllers (D) may be used alone or in combination.
The content of the acid diffusion-controlling agent (D) in the composition (when a plurality of them are present, the total content thereof) is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass, based on the total solid content of the composition.
< solvent >
The actinic-ray-or radiation-sensitive resin composition according to the present invention preferably contains a solvent (also referred to as "solvent (F)"), more preferably an organic solvent.
In the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention, a known resist solvent can be suitably used. For example, known solvents disclosed in paragraphs 0665 to 0670 of U.S. patent application publication No. 2016/0070167, paragraphs 0210 to 0235 of U.S. patent application publication No. 2015/0004544, paragraphs 0424 to 0426 of U.S. patent application publication No. 2016/0237190, and paragraphs 0357 to 0366 of U.S. patent application publication No. 2016/0274458 can be preferably used.
Examples of the solvent that can be used in the preparation of the composition include organic solvents such as alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), monoketone compound (preferably having 4 to 10 carbon atoms) which may have a ring, alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.
As the organic solvent, a mixed solvent in which a solvent containing a hydroxyl group in the structure and a solvent containing no hydroxyl group are mixed can be used.
The above exemplified compounds can be appropriately selected as the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, but the solvent containing a hydroxyl group is preferably an alkylene glycol monoalkyl ether or an alkyl lactate, and more preferably propylene glycol monomethyl ether (PGME: 1-methoxy-2-propanol), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate or ethyl lactate. The solvent containing no hydroxyl group is preferably alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, a monoketone compound which may contain a ring, a cyclic lactone, an alkyl acetate, or the like, more preferably propylene glycol monomethyl ether acetate (PGMEA: 1-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone, γ -butyrolactone, cyclohexanone, cyclopentanone, or butyl acetate, and still more preferably propylene glycol monomethyl ether acetate, γ -butyrolactone, ethyl ethoxypropionate, cyclohexanone, cyclopentanone, or 2-heptanone. As the solvent containing no hydroxyl group, propionate carbonate is also preferable. Among them, the solvent particularly preferably contains γ -butyrolactone from the viewpoint of uniformity of the formed layer.
The mixing ratio (mass ratio) of the solvent containing a hydroxyl group to the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. From the viewpoint of coating uniformity, a mixed solvent containing 50 mass% or more of a solvent containing no hydroxyl group is preferred.
The solvent preferably contains propylene glycol monomethyl ether acetate, and may be propylene glycol monomethyl ether acetate single solvent, or may be a mixed solvent of 2 or more kinds containing propylene glycol monomethyl ether acetate.
The solid content concentration of the actinic ray-or radiation-sensitive resin composition according to the present invention is not particularly limited, but is preferably 0.5 to 50 mass%, more preferably 1.0 to 45 mass%, and still more preferably 1.0 to 40 mass%.
In a preferred embodiment, the actinic ray-or radiation-sensitive resin composition has a solid content concentration of preferably 10% by mass or more, preferably 15% by mass or more, and preferably 20% by mass or more.
The solid component concentration is a mass percentage of the mass of the resist components other than the solvent with respect to the total mass of the composition.
< surfactant (H) >
The actinic-ray-or radiation-sensitive resin composition according to the present invention may or may not contain a surfactant (also referred to as "surfactant (H)").
In a preferred embodiment, the actinic ray-or radiation-sensitive resin composition according to the present invention further contains a surfactant (H). When the surfactant is contained, it is preferable to contain at least one of a fluorine-based surfactant and a silicon-based surfactant (specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both a fluorine atom and a silicon atom).
By containing the surfactant in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, a resist pattern having good sensitivity and resolution and reduced in adhesion and development defects can be obtained when an exposure light source having a wavelength of 250nm or less, particularly 220nm or less is used.
Examples of the fluorine-based or silicon-based surfactant include the surfactants described in section 0276 of U.S. patent application publication No. 2008/0248425.
In addition, surfactants other than fluorine-based or silicon-based surfactants described in paragraph 0280 of specification of U.S. patent application publication No. 2008/0248425 can be used.
These surfactants may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
When the actinic ray-or radiation-sensitive resin composition according to the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, based on the total solid content of the composition.
On the other hand, when the content of the surfactant is 0.0001% by mass or more based on the total solid content of the composition, the surface distribution unevenness of the hydrophobic resin increases. This makes the surface of the actinic ray-sensitive or radiation-sensitive film more hydrophobic, and improves the water-following property during immersion exposure.
< other additives >
The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may further contain other known additives.
Examples of the other additives include acid proliferators, dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors, and dissolution promoters.
The actinic-ray-or radiation-sensitive resin composition according to the present invention is preferably used by dissolving the above components in a predetermined organic solvent, preferably the above mixed solvent, filtering the solution with a filter, and then, for example, coating the filtered solution on a predetermined support (substrate).
The pore size (pore diameter) of the filter used for filter filtration is preferably 0.2 μm or less, more preferably 0.05 μm or less, and further preferably 0.03 μm or less.
In addition, when the concentration of the solid content of the actinic ray-or radiation-sensitive resin composition is high (for example, 25 mass% or more), the pore size of the filter used for filter filtration is preferably 3 μm or less, more preferably 0.5 μm or less, and still more preferably 0.3 μm or less.
The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. In the filter filtration, for example, as disclosed in japanese patent application laid-open No. 2002-62667, circulation filtration may be performed, or filtration may be performed by connecting a plurality of filters in series or in parallel. Further, the composition may be filtered several times. Further, the composition may be subjected to degassing treatment before or after filtration by a filter.
< use >
The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is an actinic ray-sensitive or radiation-sensitive resin composition of which properties are changed by an irradiation reaction of light. More specifically, the actinic ray-or radiation-sensitive resin composition according to the present invention relates to an actinic ray-or radiation-sensitive resin composition used for a resist composition for use in a semiconductor production process such as an IC (Integrated Circuit), a production process of a Circuit board such as a liquid crystal or a thermal head, a production process of a mold structure for imprinting, another photolithography process, a production process of a lithographic printing plate, or an acid-curable composition. The resist pattern formed from the actinic ray-or radiation-sensitive resin composition according to the present invention can be used in an etching step, an ion implantation step, a bump electrode formation step, a rewiring step, MEMS (Micro Electro Mechanical Systems) and the like.
(actinic ray-sensitive or radiation-sensitive film)
The actinic ray-sensitive or radiation-sensitive film (preferably, resist film) according to the present invention is a film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention. The actinic ray-sensitive or radiation-sensitive film according to the present invention is a cured product of the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention.
The cured product in the present invention may be a cured product obtained by removing at least a part of the solvent from the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention.
Specifically, the actinic-ray-or radiation-sensitive film according to the present invention is obtained by coating the actinic-ray-or radiation-sensitive resin composition according to the present invention on a support such as a substrate, and then drying the coating.
The drying means removing at least a part of the solvent contained in the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention.
The drying method is not particularly limited, and a known method can be used, and examples thereof include drying by heating (for example, 70 to 130 ℃ for 30 to 300 seconds).
The heating method is not particularly limited, and known heating means may be used, and examples thereof include a heater, an oven, a hot plate, an infrared lamp, and an infrared laser.
The components contained in the actinic-ray-sensitive or radiation-sensitive film according to the present invention are the same as the components contained in the actinic-ray-sensitive or radiation-sensitive resin composition according to the present invention, except for the solvent, and the preferred embodiment is the same.
The content of each component contained in the actinic-ray-or radiation-sensitive film according to the present invention corresponds to the description of "total solid content" in the description of the content of each component other than the solvent of the actinic-ray-or radiation-sensitive resin composition according to the present invention, which is replaced with "total mass of the actinic-ray-or radiation-sensitive film".
The thickness of the actinic ray-sensitive or radiation-sensitive film according to the present invention is not particularly limited, but is preferably 50nm to 3000nm, more preferably 80nm to 2500nm.
When a thick actinic ray-sensitive or radiation-sensitive film is to be formed in accordance with the three-dimensional formation of the memory device, the thickness is, for example, preferably 2 μm or more, more preferably 2 μm or more and 50 μm or less, and still more preferably 2 μm or more and 20 μm or less.
In general, in order to form a thick actinic ray-sensitive or radiation-sensitive film, the concentration of solid components in the actinic ray-sensitive or radiation-sensitive composition tends to be increased. In such a composition, since a large amount of components such as a resin and a photoacid generator can be contained, more excellent stability over time tends to be required.
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention is excellent in stability with time, and therefore can be preferably used for forming an actinic ray-sensitive or radiation-sensitive film having such a thick film.
(Pattern Forming method)
The pattern forming method according to the present invention includes:
a step of exposing the actinic ray-sensitive or radiation-sensitive film (preferably, resist film) according to the present invention with actinic rays or radiation (exposure step); and
and a step (developing step) of developing the actinic ray-sensitive or radiation-sensitive film after the exposure step with a developer.
The pattern forming method according to the present invention may include:
a step (film-forming step) of forming an actinic ray-sensitive or radiation-sensitive film on a support by the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention;
a step of exposing the actinic ray-sensitive or radiation-sensitive film to actinic rays or radiation (exposure step); and
and a step (developing step) of developing the actinic ray-sensitive or radiation-sensitive film after the exposure step with a developer.
< film Forming Process >
The pattern forming method according to the present invention may include a film forming step. As a method for forming an actinic ray-sensitive or radiation-sensitive film in the film formation step, for example, a method for forming an actinic ray-sensitive or radiation-sensitive film by using drying described in the above-mentioned item of the actinic ray-sensitive or radiation-sensitive film can be cited.
[ support body ]
The support is not particularly limited, and a substrate generally used in a photolithography process for other photo-etching processes can be used in addition to a process for manufacturing a semiconductor such as an IC or a process for manufacturing a circuit board such as a liquid crystal or a thermal head. Specific examples of the support include silicon and SiO 2 And inorganic substrates such as SiN.
< Exposure Process >
The exposure step is a step of exposing the actinic ray-sensitive or radiation-sensitive film with light.
The exposure method may be immersion exposure.
The pattern forming method according to the present invention may include a multiple exposure step.
The kind of light (actinic ray or radiation) used for the exposure may be selected in consideration of the characteristics of the photoacid generator, the shape of a pattern to be obtained, and the like, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-ray, electron beam, and the like, and far ultraviolet light is preferable.
For example, actinic rays having a wavelength of 250nm or less are preferred, 220nm or less is more preferred, and 1 to 200nm is even more preferred.
The light used is specifically KrF excimer laser (248 nm), arF excimer laser (193 nm), or F 2 Excimer laser (157 nm), X-ray, EUV (13 nm), electron beam, or the like, preferably ArF excimer laser, EUV, or electron beam.
Among them, the exposure in the exposure step is preferably performed by liquid immersion exposure using an ArF excimer laser.
The exposure amount is preferably 5mJ/cm 2 ～200mJ/cm 2 More preferably 10mJ/cm 2 ～100mJ/cm 2 。
< developing step >
The developer used in the developing step may be an alkaline developer, or may be a developer containing an organic solvent (hereinafter, also referred to as an organic developer), and is preferably an alkaline aqueous solution.
[ alkaline developer ]
As the alkaline developer, quaternary ammonium salts represented by tetramethylammonium hydroxide are preferably used, and in addition to these, alkaline aqueous solutions such as inorganic bases, primary to tertiary amines, alkanolamines, and cyclic amines can be used.
The alkaline developer may contain an appropriate amount of at least one of an alcohol and a surfactant. The alkali concentration of the alkali developer is preferably 0.1 to 20% by mass. The pH of the alkaline developer is preferably 10 to 15.
The time for development with the alkaline developer is preferably 10 seconds to 300 seconds.
The alkali concentration, pH and developing time of the alkali developer can be appropriately adjusted according to the pattern to be formed.
[ organic developer ]
The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.
Ketone solvents
Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone (ionone), diacetonealcohol, acetyl alcohol, acetophenone, methylnaphthyl ketone, isophorone, and propylene carbonate.
Ester solvents
Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butyrate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.
Other solvents-
As the alcohol solvent, the amide solvent, the ether solvent and the hydrocarbon solvent, the solvents disclosed in paragraphs 0715 to 0718 of U.S. patent application laid-open No. 2016/0070167 can be used.
A plurality of the above solvents may be mixed, or a solvent other than the above solvents or water may be mixed. The water content of the entire developer is preferably less than 50% by mass, more preferably less than 20% by mass, still more preferably less than 10% by mass, and particularly preferably substantially no water.
The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, further preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, with respect to the total amount of the developer.
Surfactants-
The organic developer may contain an appropriate amount of a known surfactant as needed.
The content of the surfactant is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, and still more preferably 0.01 to 0.5% by mass, based on the total mass of the developer.
Acid diffusion controllers
The organic developer may contain the above-mentioned acid diffusion controller.
[ developing method ]
As the developing method, for example, the following can be applied: a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dip method); a method of depositing a developing solution on the surface of a substrate by surface tension and allowing the substrate to stand for a certain period of time (a spin immersion method); a method of spraying a developing solution on the surface of a substrate (spray method); or a method of continuously discharging the developer while scanning a developer discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispensing method).
A step of performing development with an alkaline aqueous solution (alkaline development step) and a step of performing development with a developer containing an organic solvent (organic solvent development step) may be combined. This makes it possible to form a pattern without dissolving only the region of the intermediate exposure intensity, and thus a finer pattern can be formed.
< preheating step and post-exposure heating step >
The pattern forming method according to the present invention preferably includes a preliminary heating (PB: preBake) step before the exposure step.
The pattern forming method according to the present invention may include a plurality of preheating processes.
The pattern forming method according to the present invention preferably includes a Post Exposure heating (PEB) step after the Exposure step and before the development step.
The pattern forming method according to the present invention may include a multiple post-exposure heating step.
The heating temperature is preferably 70 to 130 ℃, more preferably 80 to 120 ℃ in both the preliminary heating step and the post-exposure heating step.
The heating time is preferably 30 seconds to 300 seconds, more preferably 30 seconds to 180 seconds, and even more preferably 30 seconds to 90 seconds in both the preliminary heating step and the post-exposure heating step.
The heating may be performed by a mechanism provided in the exposure device and the developing device, or may be performed using a hot plate or the like.
< resist underlayer film Forming step >
The pattern forming method according to the present invention may further include a step of forming a resist underlayer film (resist underlayer film forming step) before the film forming step.
The resist underlayer film forming step is a step of forming a resist underlayer film (for example, SOG (Spin On Glass), SOC (Spin On Carbon), antireflection film, or the like) between the resist film and the support. As the resist underlayer film, a known organic or inorganic material can be suitably used.
< protective film Forming step >
The pattern forming method according to the present invention may further include a step of forming a protective film (protective film forming step) before the developing step.
The protective film forming step is a step of forming a protective film (topcoat layer) on the resist film. As the protective film, a known material can be suitably used. For example, the composition for forming a protective film disclosed in U.S. patent application publication No. 2007/0178407, U.S. patent application publication No. 2008/0085466, U.S. patent application publication No. 2007/0275326, U.S. patent application publication No. 2016/0299432, U.S. patent application publication No. 2013/0244438, and international publication No. 2016/157988 can be preferably used. The composition for forming a protective film preferably contains the above-mentioned acid diffusion controller.
A protective film may be formed on the resist film containing the hydrophobic resin.
< washing step >
The pattern forming method according to the present invention preferably includes a step of cleaning with a rinse solution (rinsing step) after the developing step.
[ case of developing step using alkaline developer ]
The rinse liquid used in the rinsing step after the developing step using the alkaline developer can be, for example, pure water. The pure water may contain an appropriate amount of a surfactant. In this case, after the developing step or the rinsing step, a process of removing the developing solution or the rinsing solution adhering to the pattern with the supercritical fluid may be added. Further, after the rinsing process or the process using the supercritical fluid, a heating process may be performed to remove moisture remaining in the pattern.
[ case of developing step Using organic developer ]
The rinse liquid used in the rinse step after the development step using the developer containing an organic solvent is not particularly limited as long as it does not dissolve the resist pattern, and a solution containing a general organic solvent can be used. As the rinse liquid, a rinse liquid containing at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent is preferably used.
Specific examples of the hydrocarbon solvent, ketone solvent, ester solvent, alcohol solvent, amide solvent and ether solvent include the same solvents as those described in the description of the developing solution containing an organic solvent.
The rinsing liquid used in the rinsing step at this time is more preferably a rinsing liquid containing monohydric alcohol.
Examples of the monohydric alcohol used in the rinsing step include linear, branched, or cyclic monohydric alcohols. Specific examples thereof include 1-butanol, 2-butanol, 3-methyl-1-butanol, t-butanol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and methyl isobutyl carbinol. Examples of the monohydric alcohol having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and methyl isobutyl carbinol.
The components may be mixed in plural, or may be mixed with an organic solvent other than the above.
The water content for the rinse solution is preferably 10 mass% or less, more preferably 5 mass% or less, and further preferably 3 mass% or less. By setting the water content to 10 mass% or less, good development characteristics can be obtained.
The rinse solution may contain an appropriate amount of a surfactant.
In the rinsing step, a substrate developed with an organic developer is cleaned with a rinsing liquid containing an organic solvent. The method of the cleaning treatment is not particularly limited, and for example, a method of continuously discharging a rinse liquid onto a substrate rotating at a constant speed (spin coating method), a method of immersing the substrate for a constant time in a tank filled with the rinse liquid (immersion method), a method of spraying the rinse liquid onto the surface of the substrate (spray method), or the like can be applied. Among them, it is preferable to perform a cleaning treatment by a spin coating method, and after the cleaning, the rinse liquid is removed from the substrate by rotating the substrate at a rotation speed of 2,000 rpm to 4,000 rpm (spin/minute). Further, it is also preferable to include a heating step (Post Bake) after the rinsing step. The heating step can remove the developer and rinse solution remaining between and inside the patterns. In the heating step after the rinsing step, the heating temperature is preferably 40 to 160 ℃, and more preferably 70 to 95 ℃. The heating time is preferably 10 seconds to 3 minutes, more preferably 30 seconds to 90 seconds.
< improvement of surface roughness >
A method of improving the surface roughness of a pattern formed by the pattern forming method according to the present invention can also be applied. As a method of improving the surface roughness of a pattern, for example, a method of treating a resist pattern with plasma of a hydrogen-containing gas as disclosed in U.S. patent application publication No. 2015/0104957 can be cited. In addition, known methods such as those described in Japanese patent application laid-open No. 2004-235468, U.S. patent application publication No. 2010/0020297, and Proc.of SPIE Vol.832883280N-1 for EUV resistance Technique for LWR Reduction and Etch Selectivity Enhancement can be applied.
The resist pattern formed by the above method can be used as a Core material (Core) of the spacer process disclosed in, for example, japanese patent application laid-open No. h 3-270227 and U.S. patent application publication No. 2013/0209941.
(method of manufacturing electronic device)
The method for manufacturing an electronic device according to the present invention includes the pattern forming method according to the present invention. The electronic component manufactured by the method for manufacturing an electronic component according to the present invention can be preferably mounted in electric and electronic devices (for example, home appliances, OA (Office Automation) related devices, media related devices, optical devices, communication devices, and the like).
Examples
Hereinafter, embodiments of the present invention will be described in detail with reference to examples. The materials, the amounts used, the ratios, the contents of the processes, the processing steps, and the like shown in the following examples can be appropriately modified within the scope not departing from the gist of the embodiments of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "part" and "%" are based on mass.
< resin (A) >
The structures of the resins (A-1 to A-12) used are shown below.
The weight average molecular weight (Mw), number average molecular weight (Mn), and the molecular weight of the resinThe dispersion (Mw/Mn) was measured by GPC (carrier: tetrahydrofuran (THF)) as described above (in terms of polystyrene). And the composition ratio (molar ratio) of the resin is determined by 13 C-NMR (Nuclear Magnetic Resonance).
[ chemical formula 67]
Figure BDA0003811393030000881
[ chemical formula 68]
Figure BDA0003811393030000891
[ chemical formula 69]
Figure BDA0003811393030000901
The unit of the content ratio of each repeating unit in the resin is mol%. t Bu represents a tert-butyl group, et represents an ethyl group, n bu represents n-butyl.
The value of the glass transition temperature (Tg) of the monomer a1 when produced into a homopolymer can be referred to the description of PCT/JP2018/018239, and the monomer a1 corresponds to the repeating unit (a 1) derived from the monomer (monomer a 1) having a glass transition temperature (Tg) of 50 ℃ or lower when produced into a homopolymer in the present specification and examples.
< photoacid Generator (B) >
The structures of the photoacid generators (B-1 to B-16) used are shown below. n Bu represents an n-butyl group, and tBu represents a tert-butyl group.
The photoacid generator (BX-1-BX-3) is not the photoacid generator (B), but is described below for convenience.
[ chemical formula 70]
Figure BDA0003811393030000911
[ chemical formula 71]
Figure BDA0003811393030000921
< acid diffusion-controlling agent (D) >
The structure of the acid diffusion controller (D) used is shown below.
[ chemical formula 72]
Figure BDA0003811393030000931
The surfactants used are shown below.
[ chemical formula 73]
Figure BDA0003811393030000932
E-2: megaface R-41 (DIC Corporation)
E-3: KF-53 (Shin-Etsu Chemical Co., ltd., manufactured by Ltd.)
E-4: megaface F176 (DIC Corporation)
E-5: megaface R08 (DIC Corporation)
The additives used are shown below.
[ chemical formula 74]
Figure BDA0003811393030000941
The solvents used are shown below.
S-1: propylene Glycol Monomethyl Ether Acetate (PGMEA)
S-2: propylene Glycol Monomethyl Ether (PGME)
S-3: lactic acid ethyl ester
S-4: 3-Ethoxypropionic acid ethyl ester
S-5: 2-heptanone
S-6: 3-Methoxypropionic acid methyl ester
S-7: 3-Methoxyacetic acid butyl ester
S-8: acetic acid butyl ester
(examples 1 to 35 and comparative examples 1 to 3)
< preparation of actinic-ray-or radiation-sensitive resin composition > (KrF Exposure)
(examples 1 to 7, 10 to 16, 19 to 31 and 35 and comparative examples 1 to 3)
Each component shown in table 1 was mixed at the content (mass%) shown in table 1 to obtain a solution having the solid content concentration (mass%) shown in table 1. Next, the obtained solution was filtered using a polyethylene filter having a pore size of 3 μm, thereby preparing an actinic ray-or radiation-sensitive resin composition (resist composition).
In the resist composition, the solid component means all components except the solvent. The resulting resist compositions were used in examples and comparative examples.
In addition, in Table 1, the content (% by mass) of each component other than the solvent means a content ratio with respect to the total solid content. The amount (parts by mass) of the solvent used is shown in the table.
< method for forming pattern (1): krF Exposure and alkaline aqueous solution development >
The resist composition prepared above was applied to a Si substrate (hereinafter, also referred to as "substrate") subjected to hexamethyldisilazane treatment without providing an antireflection layer thereon using a spin coater "ACT-8" manufactured by Tokyo Electron ltd, and subjected to heat drying (PB) at 150 ℃ for 60 seconds, thereby forming a resist film having a thickness of 5 μm.
The resist film was pattern-exposed through a mask having a line and a space pattern with a space pattern of 250nm and a pitch of 1000nm after reduction projection exposure and positive development, using a KrF excimer laser scanner (PAS 5500/850C, manufactured by ASML, wavelength 248 nm) under exposure conditions of NA =0.68 and o = 0.60. After irradiation, baking (PEB) was performed at 130 ℃ for 60 seconds, and after dipping for 60 seconds using a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution, rinsing was performed for 30 seconds with water, and drying was performed, thereby forming a line-and-space pattern having a space size of 250nm and a pitch of 1000 nm.
Exposing through the mask to form a line and space pattern with a space size of 250nm and a pitch of 1000nm as an optimum exposure, and setting the optimum exposure as a sensitivity (mJ/cm) 2 ). The width of the spatial pattern was measured using a Scanning Electron Microscope (SEM) (9380 II, hitachi High-Technologies Corporation).
Through the above steps, a pattern wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.
< evaluation of Properties >
[ stability over time ]
After the resist composition was stored at 40 ℃ for 4 weeks, a line and space pattern was formed in the same manner as described above. The sensitivity of the obtained pattern was determined in the same manner as described above, and the difference between the sensitivity of the pattern formed using the resist composition before the storage with time and the sensitivity of the pattern formed using the resist composition after the storage with time (4 weeks at 40 ℃), that is, the degree of sensitivity fluctuation was evaluated based on the following criteria.
(criteria for determination)
A: the observed sensitivity variation is less than 1mJ/cm 2
B: the observed sensitivity variation was 1mJ/cm 2 More than and less than 2mJ/cm 2
C: the observed sensitivity variation was 2mJ/cm 2 Above and less than 3mJ/cm 2
D: the observed sensitivity variation was 3mJ/cm 2 More than and less than 4mJ/cm 2
E: the observed sensitivity variation was 4mJ/cm 2 The above
< preparation of actinic-ray-or radiation-sensitive resin composition > (ArF Exposure)
(examples 8 to 9, 17 to 18, and 32)
Each component shown in table 1 was mixed at the content (mass%) shown in table 1, and a solution having the solid content concentration (mass%) shown in table 1 was obtained. Next, the obtained solution was filtered using a polyethylene filter having a pore size of 0.1 μm, thereby preparing an actinic ray-sensitive or radiation-sensitive resin composition (resist composition). In the resist composition, the solid component means all components except the solvent. The resulting resist compositions were used in the examples.
In table 1, the content (mass%) of each component other than the solvent refers to the content ratio with respect to the total solid content. The amount (parts by mass) of the solvent used is shown in table 1.
< method for forming pattern (2): arF Exposure and alkaline aqueous solution development (Positive) >
The resist composition prepared above was applied to a Si substrate (manufactured by Advanced Materials Technology) subjected to hexamethyldisilazane treatment without providing an antireflection layer at a rotation speed to a target film thickness, and baked at a temperature of 120 ℃ for 60 seconds to form an actinic ray-sensitive or radiation-sensitive film (resist film) having a film thickness of 700 nm.
The wafer on which the resist film was formed was pattern-exposed through an exposure mask using an ArF excimer laser scanner (PAS 5500/1500, wavelength 193nm, NA0.50, manufactured by ASML). Then, the plate was baked at 115 ℃ for 60 seconds, developed with a 2.38 mass% aqueous tetramethylammonium hydroxide solution (TMAHaq) for 30 seconds, rinsed with plain water, and spin-dried. Thus, a line and space pattern with a space size of 250nm and a pitch of 1500nm was obtained.
The exposure dose with the space size of 250nm and the pitch of 1500nm of the formed line and space pattern was set as the optimum exposure dose, and the optimum exposure dose was set as the sensitivity (mJ/cm) 2 ). The width of the space pattern was measured using a Scanning Electron Microscope (SEM: scanning Electron Microscope) (9380 II, hitachi High-Technologies Corporation).
Through the above steps, a pattern wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.
< method for forming pattern (3): arF Exposure, organic solvent development (negative) >
The same operation as in the above pattern formation method (2) was performed except that an exposure mask in which the light-transmitting portion and the light-shielding portion of the exposure mask used in the above pattern formation method (2) (forward development) were inverted was used, butyl acetate (organic developer) was used instead of 2.38 mass% tetramethylammonium hydroxide aqueous solution (TMAHaq), and methyl isobutyl carbinol (MIBC) was used instead of pure water, thereby obtaining a line-and-space pattern having a space size of 250nm and a pitch of 1500 nm.
The exposure dose with the space size of 250nm and the pitch of 1500nm of the formed line and space pattern was set as the optimum exposure dose, and the optimum exposure dose was set as the sensitivity (mJ/cm) 2 ). The width of the spatial pattern was measured using a Scanning Electron Microscope (SEM) (9380 II, hitachi High-Technologies Corporation).
< evaluation of Properties >
[ stability over time ]
After the resist composition was stored at 40 ℃ for 4 weeks, a line and space pattern was formed in the same manner as described above. The sensitivity of the obtained pattern was determined in the same manner as described above, and the difference between the sensitivity of the pattern formed using the resist composition before the storage with time and the sensitivity of the pattern formed using the resist composition after the storage with time (4 weeks at 40 ℃), that is, the degree of sensitivity fluctuation was evaluated based on the following criteria.
(criteria for determination)
A: the observed sensitivity variation is less than 1mJ/cm 2
B: the observed sensitivity variation was 1mJ/cm 2 More than and less than 2mJ/cm 2
C: the observed sensitivity variation was 2mJ/cm 2 More than and less than 3mJ/cm 2
D: the observed sensitivity variation was 3mJ/cm 2 Above and less than 4mJ/cm 2
E: the observed sensitivity variation was 4mJ/cm 2 The above
< preparation of actinic-ray-or radiation-sensitive resin composition > (EUV exposure)
(example 34)
Each component shown in table 1 was mixed at the content (mass%) shown in table 1, and a solution having the solid content concentration (mass%) shown in table 1 was obtained. Then, the obtained solution was filtered in the order of a polyethylene filter having a pore size of 50nm, a nylon filter having a pore size of 10nm, and a polyethylene filter having a pore size of 5nm to prepare an actinic ray-sensitive or radiation-sensitive resin composition (resist composition).
In the resist composition, the solid component means all components except the solvent. The resulting resist compositions were used in the examples.
In table 1, the content (mass%) of each component other than the solvent means a content ratio with respect to the total solid content. The amount (parts by mass) of the solvent used is shown in table 1.
< method for forming pattern (4): EUV Exposure, alkali development (Positive) >
ALA12 (manufactured by Brewer Science) was applied onto a silicon wafer, and the silicon wafer was baked at 205 ℃ for 60 seconds to form an underlayer film having a film thickness of 30 nm. The resist compositions shown in the table were applied thereon, and baked (PB) at 120 ℃ for 60 seconds, thereby forming a positive resist film having a film thickness of 30 nm.
The resist film was pattern-irradiated using an EUV Exposure apparatus (manufactured by Exitech Corporation, micro Exposure Tool, nao.3, quadrupol, outer sigma 0.68, inner sigma 0.36). As a reticle (reticle), a mask having a line size =40nm and a line: space = 1: 1 was used.
The resist film after exposure was baked (PEB) at 120 ℃ for 60 seconds, developed with an aqueous tetramethylammonium hydroxide solution (TMAH, 2.38 mass%) for 30 seconds, and then rinsed with pure water for 30 seconds. A silicon wafer was rotated at 4000rpm for 30 seconds and then baked at 90 ℃ for 60 seconds, thereby obtaining a line and space pattern having a pitch of 80nm and a line width of 40nm (space width of 40 nm).
In addition, the optimum exposure amount (sensitivity) (mJ/cm) for forming a line-and-space (LS) pattern with a pitch of 80nm and a line width of 40nm is set 2 ). In the determination of the above sensitivity, a Scanning Electron Microscope (SEM) (9380 II, manufactured by Hitachi High-Technologies Corporation) was used for the determination of the spatial width of the pattern.
Through the above steps, a pattern wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.
< evaluation of Properties >
[ stability over time ]
After the resist composition was stored at 40 ℃ for 4 weeks, a line and space pattern was formed in the same manner as described above. The sensitivity of the obtained pattern was determined in the same manner as described above, and the difference between the sensitivity of the pattern formed using the resist composition before the storage with time and the sensitivity of the pattern formed using the resist composition after the storage with time (4 weeks at 40 ℃), that is, the degree of sensitivity fluctuation was evaluated based on the following criteria.
(criteria for determination)
A: the observed sensitivity variation is less than 1mJ/cm 2
B: the observed sensitivity variation was 1mJ/cm 2 More than and less than 2mJ/cm 2
C: the observed sensitivity variation was 2mJ/cm 2 Above and less than 3mJ/cm 2
D: the observed sensitivity variation was 3mJ/cm 2 Above and less than 4mJ/cm 2
E: the observed sensitivity variation was 4mJ/cm 2 Above
< preparation of actinic ray-sensitive or radiation-sensitive resin composition > (EB Exposure)
(example 33)
Each component shown in table 1 was mixed, and the mixture was mixed so as to have a solid content concentration (mass%) shown in table 1, to obtain a solution. The obtained liquid was filtered with a polytetrafluoroethylene filter having a pore size of 0.03 μm, thereby obtaining an actinic ray-sensitive or radiation-sensitive resin composition (resist composition).
In the resist composition, the solid component means all components except the solvent. The resulting resist compositions were used in the examples.
In table 1, the content (mass%) of each component other than the solvent means a content ratio with respect to the total solid content. The amount (parts by mass) of the solvent used is shown in table 1.
< method of forming pattern (5): EB Exposure and alkali development (Positive) >
The resist composition shown in Table 1 was applied to a 6-inch wafer using a Tokyo Electron Ltd. Spin coater Mark8, and baked (PB) on a hot plate at 110 ℃ for 90 seconds, thereby obtaining a resist film having a film thickness of 80 nm.
The resist film was subjected to pattern irradiation using an electron beam writing apparatus (manufactured by ELIONIX INC., inc.; ELS-7500, acceleration voltage 50 KeV). As a reticle (reticle), a mask having a line size =100nm and a line: space = 1: 1 was used. After the irradiation, the substrate was baked on a hot Plate (PEB) at 110 ℃ for 90 seconds, immersed in an aqueous solution of 2.38 mass% tetramethylammonium hydroxide as a developing solution for 60 seconds, and then rinsed with pure water for 30 seconds to dry, thereby obtaining a line-and-space pattern having a pitch of 200nm and a line width of 100nm (a space width of 100 nm).
In addition, the optimum exposure (sensitivity) (μ C/cm) for forming a Line and Space (LS) pattern with a pitch of 200nm and a line width of 100nm is set 2 ). In the determination of the above sensitivity, a Scanning Electron Microscope (SEM) (9380 II, manufactured by Hitachi High-Technologies Corporation) was used for the determination of the spatial width of the pattern.
Through the above steps, a pattern wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.
< evaluation of Properties >
[ stability over time ]
After the resist composition was stored at 40 ℃ for 4 weeks, a line and space pattern was formed in the same manner as described above. The sensitivity of the obtained pattern was determined in the same manner as described above, and the difference between the sensitivity of the pattern formed using the resist composition before the storage with time and the sensitivity of the pattern formed using the resist composition after the storage with time (4 weeks at 40 ℃), that is, the degree of sensitivity fluctuation was evaluated based on the following criteria.
(criteria for determination)
A: the observed sensitivity variation is less than 1 μ C/cm 2
B: the observed sensitivity variation was 1. Mu.C/cm 2 Above and less than 2 mu C/cm 2
C: the observed sensitivity variation was 2. Mu.C/cm 2 Above and less than 3 mu C/cm 2
D: the observed sensitivity variation was 3. Mu.C/cm 2 Above and less than 4 mu C/cm 2
E: the observed sensitivity variation was 4. Mu.C/cm 2 The above
The evaluation results obtained are shown in table 2 below.
Figure BDA0003811393030001011
Figure BDA0003811393030001021
[ Table 3]
TABLE 2
Pattern forming method Stability over time
Example 1 KrF C
Example 2 KrF D
Example 3 KrF B
Example 4 KrF C
Example 5 KrF A
Example 6 KrF A
Example 7 KrF B
Example 8 ArF-positive A
Example 9 ArF-normal B
Example 10 KrF C
Example 11 KrF B
Example 12 KrF C
Example 13 KrF C
Example 14 KrF D
Example 15 KrF B
Example 16 KrF C
Example 17 ArF-positive A
Example 18 ArF-normal A
Example 19 KrF B
Example 20 KrF A
Example 21 KrF B
Example 22 KrF C
Example 23 KrF B
Example 24 KrF C
Example 25 KrF A
Example 26 KrF A
Example 27 KrF A
Example 28 KrF D
Example 29 KrF D
Example 30 KrF D
Example 31 KrF C
Example 32 ArF-organic solvent development C
Example 33 EB C
Example 34 EUV C
Example 35 KrF A
Comparative example 1 KrF E
Comparative example 2 KrF E
Comparative example 3 KrF E
From the results in table 2, it is understood that the composition of the present invention is excellent in stability with time.
Industrial applicability
According to the present invention, an actinic ray-sensitive or radiation-sensitive resin composition which can realize extremely excellent stability over time can be provided.
According to the present invention, there can be further provided an actinic ray-sensitive or radiation-sensitive film using the above actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method, and a method for manufacturing an electronic device.
While the present invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be added thereto without departing from the spirit and scope thereof.
In addition, the present application is based on Japanese patent application (Japanese patent application No. 2020-32446) filed on 27/2/2020, the contents of which are incorporated herein by reference.

Claims (12)

1. An actinic-ray-or radiation-sensitive resin composition comprising:
(A) A resin; and
(B) A compound represented by the following general formula (1) which generates an acid by irradiation with actinic rays or radiation,
Figure FDA0003811393020000011
in the general formula (1) above,
W 1 the representation of a ring is shown,
q represents a constituent ring W 1 1 or more ring members of (a) are 2-valent linking groups of heteroatoms, carbonyl carbon atoms, or combinations thereof,
R 1A and R 1B Each independently represents a hydrogen atom, an organic group, a halogen atom or a cyano group,R 1A and R 1B At least 1 of which represents an organic group, a halogen atom or a cyano group,
R 2A and R 2B Each independently represents a hydrogen atom, an organic group, a halogen atom or a cyano group, wherein R 2A And R 2B At least 1 of which represents an organic group, a halogen atom or a cyano group,
p represents 0 or 1,q represents 0 or 1,
wherein p + q represents 1 or 2,
R 1 and R 2 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group, wherein R 1 And R 2 At least 1 of which represents an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group,
n represents a number of 0 or 1,
R 3 and R 4 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group,
m represents an integer of 0 or 1 or more,
in the case where m represents an integer of 1 or more, n represents 1,
l represents a carbonyl bond or an ester bond,
l represents a number of 0 or 1,
in the case where l represents 1, n represents 1,
in the case where l represents 1, R 5 ～R 9 At least 2 of which are optionally linked to each other to form a ring,
in the case where l represents 0, m represents 0,n represents 0,
R 5 、R 6 、R 7 、R 8 and R 9 Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkoxy group, an alkoxycarbonyl group, a cycloalkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, an alkenyl group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or a cycloalkylthio group,
z represents an anion.
2. The actinic-ray-or radiation-sensitive resin composition according to claim 1, wherein,
in the general formula (1), ring W 1 Is a 6-8 membered ring.
3. The actinic-ray-or radiation-sensitive resin composition according to claim 1 or 2, wherein,
in the general formula (1), Z - Is an anion represented by any of the following general formulae (3) to (5),
Figure FDA0003811393020000021
in the general formula (3), in the formula,
xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom,
L 1 represents a single bond or a divalent linking group,
a represents an organic group having a valence of 1,
x represents an integer of 1 to 20,
Figure FDA0003811393020000022
in the general formula (4), the compound (A),
Xf 1 each independently represents a fluorine atom or an alkyl group substituted by at least one fluorine atom, 2 Xf 1 Optionally linked to each other to form a ring structure,
Figure FDA0003811393020000031
in the general formula (5), the compound (A),
Xf 2 each independently represents a fluorine atom or an alkyl group substituted by at least one fluorine atom, 2 Xf 2 Optionally linked to each other to form a ring structure.
4. The actinic-ray-or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein,
in the general formula (1), Q is an arbitrary linking group selected from the following groups,
Figure FDA0003811393020000032
in the above-mentioned formula, the compound of formula,
R 11 represents a hydrogen atom or a substituent group,
* Represents and forms W in the general formula (1) 1 A bond of adjacent groups to Q.
5. The actinic-ray-or radiation-sensitive resin composition according to any one of claims 1 to 4, wherein,
the compound represented by the general formula (1) is a compound represented by the following general formula (2),
Figure FDA0003811393020000033
in the general formula (2), in the formula,
ra to Rd each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group,
wherein at least 1 of Ra to Rd represents an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group,
q has the same meaning as that of Q in the above general formula (1),
R 1 、R 2 has the same meaning as R in the above general formula (1) 1 、R 2 The meaning of (A) is the same as that of (B),
R 5 、R 6 、R 7 、R 8 and R 9 Has the same meaning as R in the above general formula (1) 5 、R 6 、R 7 、R 8 And R 9 The meaning of (A) is the same as that of (B),
R 5 ～R 9 at least 2 of which are optionally linked to each other to form a ring,
Z - has the same meaning as that of Z-in the above general formula (1).
6. The actinic-ray-or radiation-sensitive resin composition according to any one of claims 1 to 5, wherein,
in the general formula (1) or the general formula (2), R 5 ～R 9 At least 1 of (a) represents an alkoxy group, a cycloalkoxy group, an alkylthio group, or a cycloalkylthio group.
7. The actinic-ray-or radiation-sensitive resin composition according to any one of claims 1 to 6, wherein,
the solid content concentration of the composition is 10 mass% or more.
8. The actinic-ray-or radiation-sensitive resin composition according to any one of claims 1 to 7, wherein,
the resin (A) has a phenolic hydroxyl group.
9. The actinic-ray-or radiation-sensitive resin composition according to any one of claims 1 to 8, wherein,
the resin (A) has a carboxyl group.
10. An actinic-ray-or radiation-sensitive film formed by the actinic-ray-or radiation-sensitive resin composition according to any one of claims 1 to 9.
11. A pattern forming method, comprising:
exposing the actinic-ray-or radiation-sensitive film according to claim 10; and
and developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer.
12. A method of manufacturing an electronic device, comprising the pattern forming method of claim 11.
CN202180016486.6A 2020-02-27 2021-02-16 Actinic-ray-sensitive or radiation-sensitive resin composition, actinic-ray-sensitive or radiation-sensitive film, pattern forming method, and method for manufacturing electronic device Pending CN115151864A (en)

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