CN110716390A - Resist composition and resist pattern forming method - Google Patents

Resist composition and resist pattern forming method Download PDF

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Publication number
CN110716390A
CN110716390A CN201910574756.XA CN201910574756A CN110716390A CN 110716390 A CN110716390 A CN 110716390A CN 201910574756 A CN201910574756 A CN 201910574756A CN 110716390 A CN110716390 A CN 110716390A
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group
substituent
component
atom
carbon atoms
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砂道智成
河野绅一
大野庆晃
白木雄哲
齐藤彩
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Tokyo Ohka Kogyo Co Ltd
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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
    • 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
    • G03F7/0035—Multiple processes, e.g. applying a further resist layer on an already in a previously step, processed pattern or textured surface
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • 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

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)

Abstract

Provided are a resist composition capable of forming a thick resist film having a film thickness of 5 [ mu ] m or more, maintaining high sensitivity, and forming a pattern having a good shape, and a method for forming a resist pattern using the same. The resist composition generates acid by exposure and the solubility of the resist composition to a developer is changed by the action of the acid, and the resist composition contains: a base component (A) whose solubility in a developer changes due to the action of an acid; a tertiary monoamine compound (D0) represented by the following general formula (D0), wherein the concentration of the base component (A) is 20% by mass or more, and the content of the compound (D0) is 0.01 to 0.05 parts by mass relative to 100 parts by mass of the base component (A)Parts by mass, Rx1～Rx3Each independently represents a hydrocarbon group which may have a substituent, Rx1～Rx3Or 2 or more of them may be bonded to each other to form a ring structure.

Description

Resist composition and resist pattern forming method
Technical Field
The invention relates to a resist composition and a resist pattern forming method.
Background
In the photolithography technique, for example, the following steps are performed: a resist film made of a resist material is formed on a substrate, and the resist film is selectively exposed to light and subjected to a development process, thereby forming a resist pattern having a predetermined shape on the resist film. A resist material in which an exposed portion of the resist film is changed to a property of dissolving in a developer is called a positive type, and a resist material in which an exposed portion of the resist film is changed to a property of not dissolving in a developer is called a negative type.
In recent years, in the manufacture of semiconductor devices and liquid crystal display devices, the miniaturization of patterns has been rapidly advanced due to the progress of photolithography. As a method for miniaturization, generally, the exposure light source is shortened in wavelength (increased in energy). Specifically, although ultraviolet rays typified by g-rays and i-rays have been used conventionally, semiconductor devices are now mass-produced using KrF excimer laser light or ArF excimer laser light. Further, studies have been conducted on EUV (extreme ultraviolet), EB (electron beam), X-ray, and the like, which have a shorter wavelength (higher energy) than these excimer lasers.
The resist material is required to have lithographic characteristics such as sensitivity to these exposure light sources and resolution with which a pattern having a fine size can be reproduced.
As a resist material satisfying such a demand, a chemically amplified resist composition containing a base component whose solubility in a developer changes by the action of an acid and an acid generator component which generates an acid upon exposure has been conventionally used.
For example, when the developer is an alkaline developer (alkaline developing process), a composition containing a resin component (base resin) whose solubility in the alkaline developer is increased by the action of an acid and an acid generator component is generally used as a positive chemically amplified resist composition. In a resist film formed using the resist composition, if selective exposure is performed during formation of a resist pattern, an acid is generated from an acid generator component in an exposed portion, the polarity of a matrix resin is increased by the action of the acid, and the exposed portion of the resist film becomes soluble in an alkaline developer. Therefore, by performing the alkali development, a positive pattern in which an unexposed portion of the resist film remains as a pattern is formed.
On the other hand, when such a chemically amplified resist composition is applied to a solvent development process using a developer containing an organic solvent (organic developer), the solubility in the organic developer is relatively lowered when the polarity of the base resin is increased, and thus the unexposed portions of the resist film are dissolved and removed by the organic developer to form a negative resist pattern in which the exposed portions of the resist film remain as a pattern. The solvent development process for forming the negative resist pattern in this way is also sometimes referred to as a negative development process.
Generally, a matrix resin used in a chemically amplified resist composition has a plurality of structural units in order to improve lithographic characteristics and the like.
For example, in the case of a resin component whose solubility in an alkaline developer is increased by the action of an acid, a structural unit containing an acid-decomposable group whose polarity is increased by decomposition by the action of an acid generated from an acid generator or the like is used in combination with a structural unit containing a lactone ring group, a structural unit containing a polar group such as a hydroxyl group, or the like.
In addition, in the formation of a resist pattern, the behavior of acid generated from an acid generator component by exposure is a factor that greatly affects the lithographic characteristics.
In view of the above, a chemically amplified resist composition has been proposed which combines an acid generator and an acid diffusion controller for controlling the diffusion of an acid generated from the acid generator component by exposure.
For example, patent document 1 discloses a chemically amplified resist material containing: a specific solvent, a base polymer containing a fluorine atom, a crosslinking agent, an acid generator, and a basic compound as an acid diffusion controller. Further, for example, patent document 2 discloses a chemically amplified positive resist composition containing: an alkali-soluble resin, a specific crosslinking agent, and an amine compound having a specific structure as an acid diffusion controlling agent.
However, with the high integration of LSIs and the high speed of communications, the increase in memory capacity is required, and the further miniaturization of patterns is rapidly progressing. However, although lithography using electron beam or EUV aims to form a fine pattern of several tens of nanometers, it has many technical problems such as low productivity, and there are limitations in the technique of microfabrication.
In addition to miniaturization, development of a three-dimensional device in which a memory is increased in capacity by stacking cells and stacking the cells has been advanced.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2001-174997
Patent document 2: japanese patent laid-open publication No. 2004-347852
Disclosure of Invention
Technical problem to be solved by the invention
The manufacturing of the three-dimensional structure device includes the following steps: a thick resist film having a film thickness of, for example, 5 μm or more, which is higher than that of the conventional one, is formed on the surface of a work, and a resist pattern is formed and etched. In the case of using the chemically amplified resist composition, it is more difficult to maintain the sensitivity at the time of exposure as the thickness of the resist film becomes thicker. In addition, in the thick film resist film, resolution against development is lowered, and it is difficult to obtain a desired resist pattern.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a resist composition capable of forming a thick resist film having a thickness of 5 μm or more, and forming a pattern having a good shape while maintaining high sensitivity, and a method for forming a resist pattern using the same.
Solution for solving the above technical problem
In order to solve the above-described problems, the present invention adopts the following configuration.
That is, the invention according to claim 1 is a resist composition which generates an acid upon exposure and whose solubility in a developer is changed by the action of the acid, comprising: a base component (A) whose solubility in a developer changes due to the action of an acid; a tertiary monoamine compound (D0) represented by the following general formula (D0), wherein the concentration of the base component (A) is 20% by mass or more, and the content of the compound (D0) is 0.01 to 0.05 parts by mass relative to 100 parts by mass of the base component (A).
[ CHEM 1 ]
Figure BDA0002111803720000031
[ wherein Rx is1～Rx3Each independently represents a hydrocarbon group which may have a substituent. Rx1～Rx3The ring structure may be formed by bonding 2 or more members to each other.]
The invention according to claim 2 is a resist pattern forming method including: a step (i) of forming a resist film on a support using the resist composition; a step (ii) of exposing the resist film; and (iii) developing the exposed resist film to form a resist pattern.
Effects of the invention
According to the present invention, a resist composition and a method for forming a resist pattern using the same are provided, which can form a thick resist film having a thickness of 5 μm or more, and can form a pattern having a good shape while maintaining high sensitivity.
Detailed Description
In the present specification and claims, "aliphatic" is a relative concept with respect to aromatic, and is defined to mean a group, a compound, or the like that has no aromatic character.
Unless otherwise specified, "alkyl" includes straight-chain, branched-chain and cyclic 1-valent saturated hydrocarbon groups. The same applies to the alkyl group in the alkoxy group.
Unless otherwise specified, "alkylene" includes linear, branched and cyclic 2-valent saturated hydrocarbon groups.
The "haloalkyl group" is a group in which a part or all of hydrogen atoms of an alkyl group are substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
"fluoroalkyl" or "fluoroalkylene" refers to a group in which a part or all of the hydrogen atoms of an alkyl group or alkylene group are replaced with fluorine atoms.
The "structural unit" refers to a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
When "may have a substituent" or "may have a substituent" is described, the case where a hydrogen atom (-H) is substituted with a group having a valence of 1 and the case where a methylene group (-CH) is substituted are included2-) two cases substituted with a 2-valent group.
"exposure" refers to a concept including irradiation of all radiation.
The "structural unit derived from an acrylate" refers to a structural unit formed by cleavage of an ethylenic double bond of an acrylate.
"acrylate" is acrylic acid (CH)2CH — COOH) in which a hydrogen atom at the carboxyl terminal is substituted with an organic group.
The hydrogen atom bonded to the carbon atom in the α -position of the acrylate may be substituted with a substituent. A substituent (R) for substituting the hydrogen atom bonded to the carbon atom at the alpha positionα0) Examples of the atom or group other than hydrogen atom include alkyl groups having 1 to 5 carbon atoms and halogenated alkyl groups having 1 to 5 carbon atoms. In addition, the compound also comprises a substituent (R)α0) Itaconate diester substituted with a substituent comprising an ester bond, substituent (R)α0) An alpha hydroxy acrylate substituted with a hydroxyalkyl group or a group modifying the hydroxyl group thereof. Unless otherwise specified, the carbon atom at the α -position of the acrylate refers to a carbon atom to which a carbonyl group of acrylic acid is bonded.
Hereinafter, an acrylate in which a hydrogen atom bonded to an α -position carbon atom is substituted with a substituent may be referred to as an α -substituted acrylate. Further, the acrylate and the α -substituted acrylate are also collectively referred to as "(α -substituted) acrylate".
The "structural unit derived from acrylamide" refers to a structural unit formed by cleavage of an ethylenic double bond of acrylamide.
The acrylamide may be obtained by substituting a substituent for a hydrogen atom bonded to a carbon atom in the α -position, or by substituting a substituent for one or both of hydrogen atoms of an amino group of the acrylamide. Unless otherwise specified, the carbon atom at the α -position of acrylamide refers to a carbon atom to which the carbonyl group of acrylamide is bonded.
Examples of the substituent for substituting the hydrogen atom bonded to the carbon atom at the α -position of acrylamide include the groups (substituents (R) listed as the α -position substituents in the above-mentioned α -substituted acrylic acid esterα0) ) the same group.
The "structural unit derived from hydroxystyrene" means a structural unit in which an olefinic double bond of hydroxystyrene is cleaved. The "structural unit derived from a hydroxystyrene derivative" means a structural unit in which an olefinic double bond of the hydroxystyrene derivative is cleaved.
The term "hydroxystyrene derivative" is intended to encompass compounds in which the hydrogen atom at the α -position of hydroxystyrene is substituted with another substituent such as an alkyl group or a haloalkyl group, and derivatives thereof. Examples of the derivatives include compounds in which the hydrogen atom at the α -position is substituted with a substituent, and the hydrogen atom of the hydroxyl group of hydroxystyrene is substituted with an organic group; and a compound in which a substituent other than a hydroxyl group is bonded to a benzene ring of hydroxystyrene in which a hydrogen atom at the α -position may be substituted with a substituent. In addition, the α -position (carbon atom at α -position) means a carbon atom to which a benzene ring is bonded unless otherwise specified.
Examples of the substituent for substituting the hydrogen atom at the α -position of hydroxystyrene include the same groups as those listed as the substituent at the α -position in the above α -substituted acrylate.
The "structural unit derived from vinylbenzoic acid or a vinylbenzoic acid derivative" refers to a structural unit in which an ethylenic double bond of vinylbenzoic acid or a vinylbenzoic acid derivative is cleaved.
The term "vinylbenzoic acid derivative" is a concept including compounds in which the hydrogen atom at the α -position of vinylbenzoic acid is substituted with another substituent such as an alkyl group or a haloalkyl group, and derivatives thereof. Examples of the derivatives include compounds in which a hydrogen atom at the α -position is substituted with a substituent, and a hydrogen atom of a carboxyl group of vinylbenzoic acid is substituted with an organic group; and a compound in which a substituent other than a hydroxyl group and a carboxyl group is bonded to a benzene ring of vinylbenzoic acid in which a hydrogen atom at the α -position may be substituted with a substituent. In addition, the α -position (carbon atom at α -position) means a carbon atom to which a benzene ring is bonded unless otherwise specified.
The term "styrene derivative" is intended to include compounds in which the hydrogen atom at the α -position of styrene is substituted with another substituent such as an alkyl group or a haloalkyl group, and derivatives thereof. Examples of the derivatives include compounds obtained by bonding a substituent to the benzene ring of hydroxystyrene in which the hydrogen atom at the α -position may be substituted with a substituent. In addition, the α -position (carbon atom at α -position) means a carbon atom to which a benzene ring is bonded unless otherwise specified.
The "structural unit derived from styrene" and the "structural unit derived from a styrene derivative" mean a structural unit in which an ethylenic double bond of styrene or a styrene derivative is cleaved.
The alkyl group as the substituent at the α -position is preferably a linear or branched alkyl group, and specifically, an alkyl group having 1 to 5 carbon atoms (methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl) and the like are mentioned.
The haloalkyl group as the substituent at the α -position may specifically be a group obtained by substituting a part or all of hydrogen atoms of the above-mentioned "alkyl group as the substituent at the α -position" with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is particularly preferable.
Specific examples of the hydroxyalkyl group as the substituent at the α -position include those obtained by substituting a part or all of the hydrogen atoms of the above-mentioned "alkyl group as a substituent at the α -position" with a hydroxyl group. The number of hydroxyl groups in the hydroxyalkyl group is preferably 1 to 5, most preferably 1.
In the present description and in the claims, depending on the structure shown in the formula, asymmetric carbons exist and the structure of enantiomers (enantiomers) or diastereomers (diastereomers) may exist. In this case, these isomers are representatively shown in a chemical formula. These isomers may be used alone or as a mixture.
(resist composition)
The resist composition according to claim 1 of the present invention is a resist composition which generates an acid upon exposure and in which the solubility in a developer changes due to the action of the acid, and comprises a base component (a) (hereinafter referred to as component (a)) whose solubility in a developer changes due to the action of the acid and a tertiary monoamine compound (D0) (hereinafter referred to as component (D0)) represented by the general formula (D0). The content of the base component (A) is 20% by mass or more, and the content of the compound (D0) is 0.01 to 0.05 parts by mass per 100 parts by mass of the base component (A).
When a resist film is formed using the resist composition, a resist film having a thickness of 5 μm or more can be formed.
When a resist film is formed using the resist composition and the resist film is selectively exposed to light, an acid is generated in an exposed portion of the resist film, and the solubility of the component (a) in a developer changes due to the action of the acid, while the solubility of the component (a) in a developer does not change in an unexposed portion of the resist film, so that a difference in solubility in the developer occurs between the exposed portion and the unexposed portion. Therefore, when the resist film is developed, in the case where the resist composition is a positive type, exposed portions of the resist film are dissolved and removed to form a positive type resist pattern, and in the case where the resist composition is a negative type, unexposed portions of the resist film are dissolved and removed to form a negative type resist pattern.
In this specification, a resist composition in which exposed portions of a resist film are dissolved and removed to form a positive resist pattern is referred to as a positive resist composition, and a resist composition in which unexposed portions of a resist film are dissolved and removed to form a negative resist pattern is referred to as a negative resist composition.
The resist composition of the present embodiment may be a positive resist composition or a negative resist composition.
The resist composition of the present embodiment is applicable to an alkaline development process using an alkaline developer in a development process in forming a resist pattern, and also applicable to a solvent development process using a developer containing an organic solvent (organic developer) in the development process.
The resist composition of the present embodiment has an acid generating ability to generate an acid upon exposure, and the component (a) may generate an acid upon exposure, or an additive component other than the component (a) may generate an acid upon exposure.
Specifically, the resist composition of the present embodiment (1) may contain an acid generator component (B) that generates an acid upon exposure (hereinafter referred to as "component (B"); (2) the (a) component may be a component that generates an acid by exposure; (3) the component (A) is a component which generates an acid upon exposure to light, and may further contain a component (B).
That is, in the cases (2) and (3), the component (a) is a "base material component which generates an acid upon exposure and changes solubility in a developer by the action of the acid". When the component (a) is a base component which generates an acid by exposure and the solubility in a developer is changed by the action of the acid, the component (a1) described later is preferably a polymer compound which generates an acid by exposure and the solubility in a developer is changed by the action of the acid. As such a polymer compound, a resin having a structural unit that generates an acid by exposure may be used. As the structural unit of the structural unit which generates an acid by exposure, a known structural unit can be used.
The resist composition is particularly preferably the resist composition in the case of the above (1), that is, an embodiment containing the component (a), the component (D0), and further containing the component (B).
< ingredient (A) >
In the resist composition of the present embodiment, the component (a) is a base material component whose solubility in a developer changes by the action of an acid.
In the present invention, the "base material component" is an organic compound having a film-forming ability, and an organic compound having a molecular weight of 500 or more is preferably used. When the molecular weight of the organic compound is 500 or more, film formation ability is improved, and a resist pattern of a nanometer order is easily formed.
Organic compounds used as a component of the substrate are broadly classified into non-polymers and polymers.
As the non-polymer, a non-polymer having a molecular weight of 500 or more and less than 4000 is generally used. Hereinafter, in the case where "low molecular compound" is mentioned, it means a non-polymer having a molecular weight of 500 or more and less than 4000.
As the polymer, a polymer having a molecular weight of 1000 or more is generally used. Hereinafter, when "resin", "high molecular compound" or "polymer" is referred to, it means a polymer having a molecular weight of 1000 or more.
As the molecular weight of the polymer, a mass average molecular weight in terms of polystyrene based on GPC (gel permeation chromatography) was used.
In the case where the resist composition of the present embodiment is a "negative resist composition for an alkaline development process" in which a negative resist pattern is formed in an alkaline development process, or a "positive resist composition for a solvent development process" in which a positive resist pattern is formed in a solvent development process, it is preferable to use a base material component (a-2) (hereinafter referred to as "a-2 component") soluble in an alkaline developer, and further blend a crosslinking agent component as the (a) component. When an acid is generated from the component (B) by exposure, for example, the acid acts to crosslink the component (a-2) with the crosslinking agent component, and as a result, the solubility in an alkaline developer decreases (the solubility in an organic developer increases). Therefore, in the formation of a resist pattern, when a resist film obtained by applying the resist composition to a support is selectively exposed, the exposed portion of the resist film is rendered insoluble to an alkaline developer (soluble to an organic developer), while the unexposed portion of the resist film is not rendered soluble to an alkaline developer (insoluble to an organic developer), and therefore, a negative resist pattern can be formed by development with an alkaline developer. In addition, at this time, a positive resist pattern can be formed by development with an organic developer.
As the component (A-2), a resin soluble in an alkaline developer (hereinafter referred to as "alkali-soluble resin") can be used preferably
Examples of the alkali-soluble resin include: a resin having a structural unit derived from at least one member selected from the group consisting of α - (hydroxyalkyl) acrylic acid and alkyl esters of α - (hydroxyalkyl) acrylic acid (preferably alkyl esters having 1 to 5 carbon atoms), disclosed in Japanese unexamined patent publication No. 2000-206694; an acrylic resin or a polycycloolefin resin having a sulfonamide group, in which a hydrogen atom bonded to a carbon atom at the α -position may be substituted with a substituent, as disclosed in U.S. Pat. No. 6949325; acrylic resins containing a fluorinated alcohol and having a hydrogen atom bonded to a carbon atom at the α -position substituted with a substituent, as disclosed in U.S. Pat. No. 6949325, JP 2005-336452 and JP 2006-317803; the alkali-soluble resins disclosed in Japanese patent application laid-open No. 2006-259582, such as the polycycloolefin resins having a fluorinated alcohol, are preferable because they can form a good resist pattern with less swelling.
The α - (hydroxyalkyl) acrylic acid represents one or two of acrylic acid in which a hydrogen atom bonded to a carbon atom at the α -position is optionally substituted with a substituent, acrylic acid in which a hydrogen atom is bonded to a carbon atom at the α -position bonded to a carboxyl group, and α -hydroxyalkyl acrylic acid in which a hydroxyalkyl group (preferably a hydroxyalkyl group having 1 to 5 carbon atoms) is bonded to a carbon atom at the α -position.
As the crosslinking agent component, an amino crosslinking agent such as glycoluril having a methylol group or an alkoxymethyl group, or a melamine crosslinking agent is preferably used because a good resist pattern having a small swelling is easily formed. The blending amount of the crosslinking agent component is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the alkali-soluble resin.
In the case where the resist composition of the present embodiment is a "positive resist composition for an alkaline development process" in which a positive resist pattern is formed in an alkaline development process or a "negative resist composition for a solvent development process" in which a negative resist pattern is formed in a solvent development process, it is preferable to use, as the component (a), a base component (a-1) (hereinafter referred to as "component (a-1)") whose polarity is increased by the action of an acid. By using the (A-1) component, since the polarity of the base material component changes before and after exposure, a good development contrast can be obtained not only in the alkali development process but also in the solvent development process.
In the case of applying an alkaline developing process, the component (a-1) is hardly soluble in an alkaline developer before exposure, and for example, when an acid is generated from the component (B) by exposure, the polarity thereof increases by the action of the acid, and the solubility in the alkaline developer increases. Therefore, in the formation of a resist pattern, when a resist film obtained by applying the resist composition to a support is selectively exposed, the solubility of the exposed portion of the resist film in an alkaline developer is changed from poorly soluble to soluble, while the alkali solubility of the unexposed portion of the resist film is not changed as it is, so that a positive resist pattern can be formed by performing alkaline development.
On the other hand, in the case of applying a solvent development process, the solubility of the component (a-1) in an organic developer before exposure is high, and when an acid is generated from the component (B) by exposure, the polarity thereof increases by the action of the acid, and the solubility in the organic developer decreases. Therefore, in the formation of a resist pattern, when a resist film obtained by applying the resist composition to a support is selectively exposed, the solubility of the exposed portion of the resist film in an organic developer changes from soluble to poorly soluble, while the unexposed portion of the resist film remains soluble and does not change, so that development with an organic developer can produce a contrast between the exposed portion and the unexposed portion, thereby forming a negative resist pattern.
In the resist composition of the present embodiment, 1 kind of the component (a) may be used alone, or 2 or more kinds may be used in combination.
In the resist composition of the present embodiment, the component (a) is preferably the component (a-1). That is, the resist composition of the present embodiment is preferably a "positive resist composition for an alkaline development process" in which a positive resist pattern is formed in an alkaline development process, or a "negative resist composition for a solvent development process" in which a negative resist pattern is formed in a solvent development process. At least one of a high molecular compound and a low molecular compound can be used as the component (a).
When the component (A) is the component (A-1), the component (A-1) is preferably a compound containing the resin component (A1) (hereinafter referred to as the "component (A1)").
With respect to the (A1) component
(A1) Component (b) is a resin component, and preferably contains a polymer compound having a structural unit (a1) containing an acid-decomposable group whose polarity is increased by the action of an acid.
The component (a1) preferably has a structural unit (a10) having a hydroxystyrene skeleton in addition to the structural unit (a 1).
Further, it is preferable that the component (a1) has a structural unit (st) derived from styrene or a styrene derivative in addition to the structural unit (a 1).
The component (A1) may have a structural unit other than the structural unit (a1), the structural unit (a10) and the structural unit (st).
Structural unit (a1)
The structural unit (a1) is a structural unit containing an acid-decomposable group whose polarity is increased by the action of an acid.
The "acid-decomposable group" is an acid-decomposable group having a structure in which at least a part of the bonds in the structure of the acid-decomposable group can be cleaved by the action of an acid.
Examples of the acid-decomposable group whose polarity is increased by the action of an acid include groups which are decomposed by the action of an acid to generate a polar group.
Examples of the polar group include a carboxyl group, a hydroxyl group, an amino group, and a sulfonic acid group (-SO)3H) And the like. Among these, a polar group containing-OH in the structure (hereinafter also referred to as "OH-containing polar group") is preferable, a carboxyl group or a hydroxyl group is more preferable, and a carboxyl group is particularly preferable.
More specifically, the acid-decomposable group includes a group in which the polar group is protected by an acid-dissociable group (for example, a group in which a hydrogen atom of an OH-containing polar group is protected by an acid-dissociable group).
The "acid-dissociable group" herein means both of the following: (i) an acid-dissociable group having a bond between the acid-dissociable group and an atom adjacent to the acid-dissociable group that can be cleaved by the action of an acid; or (ii) a group in which a part of the bond is cleaved by the action of an acid and then decarboxylation is further caused, whereby the bond between the acid-dissociable group and the atom adjacent to the acid-dissociable group can be cleaved.
The acid-dissociable group constituting the acid-dissociable group must be a group having a polarity lower than that of a polar group generated by dissociation of the acid-dissociable group, and thus when the acid-dissociable group dissociates by the action of an acid, a polar group having a polarity higher than that of the acid-dissociable group is generated and the polarity increases. As a result, the polarity of the entire component (a1) increases. The increase in polarity changes the solubility in the developer, and the solubility increases when the developer is an alkaline developer, and decreases when the developer is an organic developer.
Examples of the acid-dissociable group include those proposed as acid-dissociable groups of matrix resins for chemically amplified resists.
Specific examples of the group proposed as the acid-dissociable group of the base resin for a chemically amplified resist include "acetal acid-dissociable group", "tert-alkyl ester acid-dissociable group", and "tert-alkoxycarbonyl acid-dissociable group" described below.
Acetal type acid-dissociable group:
examples of the acid-dissociable group that protects the carboxyl group or the hydroxyl group of the polar group include acid-dissociable groups represented by the following general formula (a1-r-1) (hereinafter also referred to as "acetal-type acid-dissociable groups").
[ CHEM 2]
[ wherein, Ra'1、Ra’2Is a hydrogen atom or an alkyl group. Ra'3Is hydrocarbyl, Ra'3May be substituted with Ra'1、Ra’2Any of which is bonded to form a ring.]
In the formula (a1-r-1), Ra 'is preferred'1And Ra'2At least one of them is a hydrogen atom, and more preferably both are hydrogen atoms.
In Ra'1Or Ra'2In the case of an alkyl group, the alkyl group may be the same as the alkyl group exemplified as the substituent which may be bonded to the carbon atom at the α -position in the above description of the α -substituted acrylate, and is preferably an alkyl group having 1 to 5 carbon atoms. Specifically, a linear or branched alkyl group is preferable. More specifically, it includes methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl and the like, more preferably methyl or ethyl, and particularly preferably methyl.
In the formula (a1-r-1), as Ra'3Examples of the hydrocarbon group of (3) include a linear or branched alkyl group and a cyclic hydrocarbon group.
The number of carbon atoms of the linear alkyl group is preferably 1 to 5, more preferably 1 to 4, and further preferably 1 or 2. Specific examples thereof include methyl group, ethyl group, n-propyl group, n-butyl group, and n-pentyl group. Among these, methyl, ethyl or n-butyl is preferable, and methyl or ethyl is more preferable.
The branched alkyl group preferably has 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms. Specific examples thereof include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1-diethylpropyl group, and 2, 2-dimethylbutyl group, with isopropyl group being preferred.
In Ra'3When the hydrocarbon group is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, or may be a polycyclic group or a monocyclic group.
The alicyclic hydrocarbon group as a monocyclic group is preferably a group obtained by removing 1 hydrogen atom from a monocyclic hydrocarbon. The monocyclic hydrocarbon is preferably a monocyclic hydrocarbon having 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
The aliphatic hydrocarbon group of the polycyclic group is preferably a group obtained by removing 1 hydrogen atom from a polycycloalkane, and the polycycloalkane is preferably a C7-12 polycycloalkane, and specifically includes adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like.
In Ra'3When the cyclic hydrocarbon group of (2) is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least 1 aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n +2 pi electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, still more preferably 6 to 15, and particularly preferably 6 to 12.
Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and the like; and an aromatic heterocyclic ring in which a part of carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring.
As Ra'3Specific examples of the aromatic hydrocarbon group in (1) include a group (aryl group or heteroaryl group) obtained by removing 1 hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring; from containing more than 2 aromatic ringsA group obtained by removing 1 hydrogen atom from an aromatic compound (e.g., biphenyl, fluorene, etc.); and those in which 1 hydrogen atom of the aromatic hydrocarbon ring or aromatic heterocyclic ring is substituted with an alkylene group (for example, arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl and 2-naphthylethyl). The number of carbon atoms of the alkylene group bonded to the aromatic hydrocarbon ring or the aromatic heterocyclic ring is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.
Ra’3The cyclic hydrocarbon group in (1) may have a substituent. Examples of the substituent include-RP1、-RP2-O-RP1、-RP2-CO-RP1、-RP2-CO-ORP1、-RP2-O-CO-RP1、-RP2-OH、-RP2-CN or-RP2-COOH (hereinafter, these substituents are collectively referred to as "Ra05") and the like.
Herein, R isp1Is a C1-valent chain saturated hydrocarbon group having 1 to 10 carbon atoms, a C3-20 1-valent aliphatic cyclic saturated hydrocarbon group, or a C6-30 1-valent aromatic hydrocarbon group. Furthermore, Rp2Is a single bond, a C1-10 chain saturated hydrocarbon group having a valence of 2, a C3-20 aliphatic cyclic saturated hydrocarbon group having a valence of 2, or a C6-30 aromatic hydrocarbon group having a valence of 2. Wherein R isp1And Rp2A part or all of hydrogen atoms of the chain saturated hydrocarbon group, the aliphatic cyclic saturated hydrocarbon group and the aromatic hydrocarbon group of (2) may be substituted with fluorine atoms. The aliphatic cyclic hydrocarbon group may have 1 or more of the substituents described above, alone, or may have a plurality of the substituents described above, each of which is 1 or more.
Examples of the 1-valent chain saturated hydrocarbon group having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, and the like.
Examples of the 1-valent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl; polycyclic aliphatic saturated hydrocarbon groups such as bicyclo [2.2.2] octane group, tricyclo [5.2.1.02, 6] decane group, tricyclo [3.3.1.13, 7] decane group, tetracyclo [6.2.1.13, 6.02, 7] dodecane group, adamantyl group and the like.
Examples of the 1-valent aromatic hydrocarbon group having 6 to 30 carbon atoms include those obtained by removing 1 hydrogen atom from an aromatic hydrocarbon ring such as benzene, biphenyl, fluorene, naphthalene, anthracene, phenanthrene, and the like.
Ra’3And Ra'1、Ra’2In the case where any one of these groups is bonded to form a ring, the cyclic group is preferably a four-to seven-membered ring, and more preferably a four-to six-membered ring. Specific examples of the cyclic group include tetrahydropyranyl group and tetrahydrofuranyl group.
Tertiary alkyl ester type acid-dissociable group:
examples of the acid-dissociable group that protects the carboxyl group of the polar group include acid-dissociable groups represented by the following general formula (a 1-r-2).
For convenience of explanation, a group composed of an alkyl group in the acid-dissociable group represented by the following formula (a1-r-2) will be referred to as a "tertiary alkyl ester-type acid-dissociable group" hereinafter.
[ CHEM 3 ]
Figure BDA0002111803720000141
[ wherein, Ra'4～Ra’6Are each hydrocarbyl, Ra'5、Ra’6May be bonded to each other to form a ring.]
As Ra'4Examples of the hydrocarbon group of (3) include a linear or branched alkyl group, a linear or cyclic alkenyl group, and a cyclic hydrocarbon group.
Ra’4Examples of the linear or branched alkyl group and the cyclic hydrocarbon group (aliphatic hydrocarbon group as monocyclic group, aliphatic hydrocarbon group as polycyclic group, and aromatic hydrocarbon group) in (1) include the groups mentioned above and Ra'3The same groups.
Ra’4The linear or cyclic alkenyl group in (1) is preferably an alkenyl group having 2 to 10 carbon atoms.
As Ra'5、Ra’6The hydrocarbon group of (2) may be represented by the above Ra'3The same hydrocarbon group.
In Ra'5And Ra'6When they are bonded to each other to form a ring, preferred examples thereof include a group represented by the following general formula (a1-r2-1), a group represented by the following general formula (a1-r2-2), and a group represented by the following general formula (a1-r 2-3).
On the other hand, in Ra'4～Ra’6When the hydrocarbon groups are independent of each other, preferred examples thereof include those represented by the following general formulae (a1-r 2-4).
[ CHEM 4 ]
Figure BDA0002111803720000151
[ Ra 'of formula (a1-r 2-1)'10Represents an alkyl group having 1 to 10 carbon atoms or a group represented by the following general formula (a1-r2-r 1). Ra'11Is represented by and Ra'10The bonded carbon atoms together form the radical of an alicyclic group. In the formula (a1-r2-2), Ya is a carbon atom. Xa is a group which forms a cyclic hydrocarbon group together with Ya. Part or all of the hydrogen atoms of the cyclic hydrocarbon group may be substituted. Ra01～Ra03Each independently represents a hydrogen atom, a C1-valent chain-like saturated hydrocarbon group having 1 to 10 carbon atoms or a C3-20 1-valent aliphatic cyclic saturated hydrocarbon group. Some or all of the hydrogen atoms of the chain-like saturated hydrocarbon group and the aliphatic cyclic saturated hydrocarbon group may be substituted. Ra01～Ra032 or more of them may be bonded to each other to form a ring structure. In the formula (a1-r2-3), Yaa is a carbon atom. Xaa is a group which together with Yaa forms an aliphatic cyclic group. Ra04Is an aromatic hydrocarbon group which may have a substituent. In the formula (a1-r2-4), Ra'12And Ra'13Each independently is a C1-10 chain-like saturated hydrocarbon group or a hydrogen atom. Some or all of the hydrogen atoms of the chain-like saturated hydrocarbon group may be substituted. Ra'14Is a hydrocarbon group which may have a substituent. Indicates a key (the same way below)]
[ CHEM 5 ]
[ in the formula, Ya0Is a quaternary carbon atom. Ra031、Ra032And Ra033Each independently is a hydrocarbon group which may have a substituent. Wherein, Ra031、Ra032And Ra033At least one of them is a hydrocarbon group having at least one polar group.]
Ra 'in the above formula (a1-r 2-1)'10The alkyl group having 1 to 10 carbon atoms of (a) is preferably Ra 'in the formula (a 1-r-1)'3The straight-chain or branched-chain alkyl group of (4). Ra'10Preferably an alkyl group having 1 to 5 carbon atoms.
In the formula (a1-r2-r1), Ya0Is a quaternary carbon atom. I.e. with Ya0(carbon atom) bonded adjacent carbon atoms are 4.
In the formula (a1-r2-r1), Ra031、Ra032And Ra033Each independently is a hydrocarbon group which may have a substituent. As Ra031、Ra032And Ra033Examples of the hydrocarbon group in (1) include a linear or branched alkyl group, a linear or cyclic alkenyl group and a cyclic hydrocarbon group.
Ra031、Ra032And Ra033The number of carbons in the linear alkyl group is preferably 1 to 5, more preferably 1 to 4, and still more preferably 1 or 2. Specific examples thereof include methyl, ethyl, n-propyl, n-butyl, and n-pentyl. Among them, methyl, ethyl or n-butyl is preferable, and methyl or ethyl is more preferable.
Ra031、Ra032And Ra033The number of carbons in the branched alkyl group is preferably 3 to 10, more preferably 3 to 5. Specific examples thereof include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1-diethylpropyl group, and 2, 2-dimethylbutyl group, with isopropyl group being preferred.
Ra031、Ra032And Ra033In the above formula, the chain or cyclic alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms.
Ra031、Ra032And Ra033In the above-mentioned embodiments, the cyclic hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a monocyclic group or a polycyclic group.
The monocyclic aliphatic hydrocarbon group is preferably a group obtained by removing 1 hydrogen atom from a monocyclic hydrocarbon. The monocyclic hydrocarbon is preferably a monocyclic hydrocarbon having 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
The polycyclic aliphatic hydrocarbon group is preferably a group obtained by removing 1 hydrogen atom from a cycloalkane. The polycyclic alkane is preferably a polycyclic alkane having 7 to 12 carbon atoms, and specifically includes adamantane, norbornane, isoborane, tricyclodecane, tetracyclododecane, and the like.
Ra031、Ra032And Ra033The aromatic hydrocarbon group in (1) is a hydrocarbon group having at least 1 aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n +2 pi electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, still more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and the like; and an aromatic heterocyclic ring in which a part of carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring. Specific examples of the aromatic hydrocarbon group include a group (aryl group or heteroaryl group) obtained by removing 1 hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring; a group obtained by removing 1 hydrogen atom from an aromatic compound (for example, biphenyl, fluorene, or the like) having 2 or more aromatic rings; and those in which 1 hydrogen atom of the aromatic hydrocarbon ring or aromatic heterocyclic ring is substituted with an alkylene group (for example, arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl and 2-naphthylethyl). The number of carbons of the alkylene group bonded to the aromatic hydrocarbon ring or the aromatic heterocyclic ring is preferablyIs selected from 1 to 4, more preferably 1 to 2, and particularly preferably 1.
In the above Ra031、Ra032And Ra033When the hydrocarbon group represented by (a) is substituted, examples of the substituent include a hydroxyl group, a carboxyl group, a halogen atom (e.g., a fluorine atom, a chlorine atom, and a bromine atom), an alkoxy group (e.g., a methoxy group, an ethoxy group, a propoxy group, and a butoxy group), and an alkoxycarbonyl group.
Wherein, Ra031、Ra032And Ra033The hydrocarbon group which may have a substituent(s) in (1) is preferably a linear or branched alkyl group which may have a substituent(s), and more preferably a linear alkyl group.
Wherein, Ra031、Ra032And Ra0331 or more of (A) are hydrocarbon groups having at least a polar group.
"hydrocarbyl group having a polar group" means a methylene group (-CH) constituting a hydrocarbyl group substituted with a polar group2-) or a group in which at least one hydrogen atom constituting the hydrocarbon group is substituted with a polar group.
The "hydrocarbon group having a polar group" is preferably a functional group represented by the following general formula (a1-p 1).
[ CHEM 6]
[ wherein Ra07Represents a C2-12 hydrocarbon group having a valence of 2. R08Represents a heteroatom-containing 2-valent linking group. Ra06Represents a C1-12 hydrocarbon group having a valence of 1. n isP0Is an integer of 1 to 6.]
Ra in the formula (a1-p1)07Represents a C2-12 hydrocarbon group having a valence of 2.
Ra07The carbon number of (A) is 2 to 12, preferably 2 to 8, more preferably 2 to 6, further preferably 2 to 4, particularly preferably 2.
Ra07The hydrocarbon group in (2) is preferably a chain or cyclic aliphatic hydrocarbon group, and more preferably a chain hydrocarbon group.
As Ra07Examples thereof include linear alkanediyl groups such as ethylene, propane-1, 3-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl, heptane-1, 7-diyl, octane-1, 8-diyl, nonane-1, 9-diyl, decane-1, 10-diyl, undecane-1, 11-diyl and dodecane-1, 12-diyl; branched alkanediyl groups such as propane-1, 2-diyl group, 1-methylbutane-1, 3-diyl group, 2-methylpropane-1, 3-diyl group, pentane-1, 4-diyl group and 2-methylbutane-1, 4-diyl group; cycloalkanediyl groups such as cyclobutane-1, 3-diyl, cyclopentane-1, 3-diyl, cyclohexane-1, 4-diyl and cyclooctane-1, 5-diyl; and polycyclic, 2-valent alicyclic hydrocarbon groups such as norbornane-1, 4-diyl, norbornane-2, 5-diyl, adamantane-1, 5-diyl, and adamantane-2, 6-diyl.
Among the above, alkanediyl groups are preferred, and linear alkanediyl groups are more preferred.
In the formula (a1-p1), Ra08Represents a heteroatom-containing 2-valent linking group.
As Ra08Examples thereof include-O-, -C (. quadrature.O) -, -O-C (. quadrature.O) -O-, -C (. quadrature.O) -NH-, -NH-C (. quadrature.NH) - (H may be substituted by a substituent such as an alkyl group or an acyl group), -S-, -S (. quadrature.O)2-、-S(＝O)2-O-, etc.
Among these, from the viewpoint of solubility in the developer, preferred are — O-, -C (═ O) -, -O-C (═ O) -O-, and particularly preferred are-O-, -C (═ O) -.
In the formula (a1-p1), Ra06Represents a C1-12 hydrocarbon group having a valence of 1.
Ra06The carbon number of (b) is 1 to 12, and from the viewpoint of solubility in a developer, the carbon number is preferably 1 to 8, more preferably 1 to 5, further preferably 1 to 3, particularly preferably 1 or 2, and most preferably 1.
Ra06Examples of the hydrocarbon group in (3) include a chain hydrocarbon group, a cyclic hydrocarbon group, and a combination of a chain hydrocarbon group and a cyclic hydrocarbon group.
Examples of the chain hydrocarbon group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, a 2-ethylhexyl group, a n-octyl group, a n-nonyl group, a n-decyl group, a n-undecyl group, and a n-dodecyl group.
The cyclic hydrocarbon group may be an alicyclic hydrocarbon group or an aromatic hydrocarbon group.
The alicyclic hydrocarbon group may be any of monocyclic and polycyclic, and examples of the monocyclic alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl, cycloheptyl, and cyclodecyl. Examples of the polycyclic alicyclic hydrocarbon group include decahydronaphthyl, adamantyl, 2-alkyladamantan-2-yl, 1- (adamantan-1-yl) alk-1-yl, norbornyl, methylnorbornyl and isobornyl.
Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a p-methylphenyl group, a p-tert-butylphenyl group, a p-adamantylphenyl group, a tolyl group, a xylyl group, a cumylphenyl group, a mesitylenyl group, a biphenyl group, a phenanthryl group, a2, 6-diethylphenyl group, and a 2-methyl-6-ethylphenyl group.
As Ra06From the viewpoint of solubility in the developer, a chain hydrocarbon group is preferable, an alkyl group is more preferable, and a linear alkyl group is further preferable.
In the above formula (a1-p1), np0Is an integer of 1 to 6, preferably an integer of 1 to 3, more preferably 1 or 2, and further preferably 1.
Specific examples of the hydrocarbon group having at least a polar group are shown below.
In the following formula, is a group bonded to a quaternary carbon atom (Ya)0) A bonded bond.
[ CHEM 7]
Figure BDA0002111803720000191
In the formula (a1-r2-r1), Ra031、Ra032And Ra033Among them, the number of the hydrocarbon groups having at least a polar group is 1 or more, and may be appropriately determined in consideration of solubility in a developer at the time of forming a resist pattern, and for example, Ra is preferable031、Ra032And Ra033Wherein 1 or 2 hydrocarbon groups have at least a polar group, and particularly preferably 1 hydrocarbon group has at least a polar group.
The hydrocarbon group having at least a polar group may have a substituent other than a polar group. Examples of the substituent include a halogen atom (e.g., a fluorine atom, a chlorine atom, and a bromine atom) and a haloalkyl group having 1 to 5 carbon atoms.
Ra 'of the formula (a1-r 2-1)'11(and Ra'10Aliphatic cyclic group formed together with bonded carbon atoms) is preferably Ra 'in the formula (a 1-r-1)'3The monocyclic group or polycyclic group of the aliphatic hydrocarbon group are exemplified.
In the formula (a1-r2-2), as the cyclic hydrocarbon group formed by Xa and Ya, Ra 'in the formula (a1-r-1) is mentioned'3Wherein 1 or more hydrogen atoms are further removed from the cyclic 1-valent hydrocarbon group (aliphatic hydrocarbon group) in (1).
The cyclic hydrocarbon group formed by Xa together with Ya may have a substituent. The substituent is preferably Ra'3The cyclic hydrocarbon group in (1) may have the same substituent.
In the formula (a1-r2-2), as Ra01～Ra03Examples of the 1-valent chain saturated hydrocarbon group having 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, and the like.
As Ra01～Ra03The (1) -valent aliphatic cyclic saturated hydrocarbon group having 3 to 20 carbon atoms in the (a) may include, for example, monocyclic aliphatic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl and cyclododecyl; bicyclo [2.2.2]Octyl radical, tricyclo [5.2.1.02, 6]]Decyl, tricyclo [3.3.1.13, 7]Decyl, tetracyclic [6.2.1.13, 6.02, 7]And polycyclic aliphatic saturated hydrocarbon groups such as dodecyl and adamantyl.
Among them, Ra is Ra from the viewpoint of easy synthesis of the monomer compound from which the structural unit (a1) is derived01～Ra03Preferably a hydrogen atom or a C1-valent chain saturated hydrocarbon group of 1 to 10, more preferablyThe hydrogen atom, methyl group and ethyl group are selected, and the hydrogen atom is particularly preferable.
As with the above Ra01～Ra03Examples of the substituent of the chain-like saturated hydrocarbon group or the aliphatic cyclic saturated hydrocarbon group include the same as Ra05The same groups.
Ra01～Ra03The group containing a carbon-carbon double bond is produced by bonding at least 2 of them to each other to form a cyclic structure, and examples of the group containing a carbon-carbon double bond include cyclopentenyl group, cyclohexenyl group, methylcyclopentenyl group, methylcyclohexenyl group, cyclopentylidenevinyl group, cyclohexylidene vinyl group and the like. Among them, cyclopentenyl, cyclohexenyl and cyclopentylidenevinyl are preferable from the viewpoint of easy synthesis of the monomer compound from which the structural unit (a1) is derived.
In formula (a1-r2-3), the aliphatic cyclic group formed by Xaa together with Yaa is preferably Ra 'in formula (a 1-r-1)'3The monocyclic group or polycyclic group of the aliphatic hydrocarbon group are exemplified.
In the formula (a1-r2-3), Ra is04The aromatic hydrocarbon group in (1) may be a group obtained by removing 1 or more hydrogen atoms from an aromatic hydrocarbon ring having 5 to 30 carbon atoms. Wherein, Ra04Preferably, the aromatic hydrocarbon ring having 6 to 15 carbon atoms is one obtained by removing 1 or more hydrogen atoms, more preferably one obtained by removing 1 or more hydrogen atoms from benzene, naphthalene, anthracene or phenanthrene, still more preferably one obtained by removing 1 or more hydrogen atoms from benzene, naphthalene or anthracene, particularly preferably one obtained by removing 1 or more hydrogen atoms from benzene or naphthalene, and most preferably one obtained by removing 1 or more hydrogen atoms from benzene.
As Ra in the formula (a1-r2-3)04Examples of the substituent which may be present include a methyl group, an ethyl group, a propyl group, a hydroxyl group, a carboxyl group, a halogen atom (e.g., a fluorine atom, a chlorine atom, and a bromine atom), an alkoxy group (e.g., a methoxy group, an ethoxy group, a propoxy group, and a butoxy group), and an alkoxycarbonyl group.
In the formula (a1-r2-4), Ra'12And Ra'13Each independently is a C1-10 chain-form saturated hydrocarbon group or a hydrogen atom. As Ra'12And Ra'13In the above-mentioned group, the 1-valent chain-like saturated hydrocarbon group having 1 to 10 carbon atoms includes the group represented by Ra01～Ra03Wherein the C1-10 chain saturated hydrocarbon groups have the same valence as each other. Some or all of the hydrogen atoms of the chain-like saturated hydrocarbon group may be substituted.
Ra’12And Ra'13Among them, a hydrogen atom and an alkyl group having 1 to 5 carbon atoms are preferable, an alkyl group having 1 to 5 carbon atoms is more preferable, a methyl group and an ethyl group are further preferable, and a methyl group is particularly preferable.
In the above Ra'12And Ra'13When the chain saturated hydrocarbon group represented by (A) is substituted, examples of the substituent include Ra05The same groups.
In the formula (a1-r2-4), Ra'14Is a hydrocarbon group which may have a substituent. As Ra'14Examples of the hydrocarbon group in (1) include a linear or branched alkyl group and a cyclic hydrocarbon group.
Ra’14The number of carbon atoms of the linear alkyl group in (1) is preferably 1 to 5, more preferably 1 to 4, and further preferably 1 or 2. Specific examples thereof include methyl, ethyl, n-propyl, n-butyl, and n-pentyl. Among them, methyl, ethyl or n-butyl is preferable, and methyl or ethyl is more preferable.
Ra’14The number of carbon atoms in the branched alkyl group in (1) is preferably 3 to 10, more preferably 3 to 5. Specific examples thereof include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1-diethylpropyl group, and 2, 2-dimethylbutyl group, with isopropyl group being preferred.
In Ra'14When the hydrocarbon group is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a polycyclic group, or a monocyclic group.
The monocyclic aliphatic hydrocarbon group is preferably a group obtained by removing 1 hydrogen atom from a monocyclic hydrocarbon. The monocycloparaffins are preferably monocycloparaffins having 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane.
The aliphatic hydrocarbon group of the polycyclic group is preferably a group obtained by removing 1 hydrogen atom from a polycycloalkane, and the polycycloalkane is preferably a C7-12 polycycloalkane, specifically, adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, or the like.
As Ra'14The aromatic hydrocarbon group in (1) may be represented by Ra04The aromatic hydrocarbon group in (1) is the same as that in (2). Wherein, Ra'14Preferably, the aromatic hydrocarbon ring having 6 to 15 carbon atoms is one obtained by removing 1 or more hydrogen atoms, more preferably one obtained by removing 1 or more hydrogen atoms from benzene, naphthalene, anthracene or phenanthrene, still more preferably one obtained by removing 1 or more hydrogen atoms from benzene, naphthalene or anthracene, particularly preferably one obtained by removing 1 or more hydrogen atoms from naphthalene or anthracene, and most preferably one obtained by removing 1 or more hydrogen atoms from naphthalene.
As Ra'14Examples of the substituent which may be present include Ra04The same substituents as those that may be present.
Ra 'in formula (a1-r 2-4)'14In the case of a naphthyl group, the position bonded to the tertiary carbon atom in the formula (a1-r2-4) may be either the 1-position or the 2-position of the naphthyl group.
Ra 'in formula (a1-r 2-4)'14In the case of an anthracene group, the position bonded to the tertiary carbon atom in the formula (a1-r2-4) may be any of the 1-, 2-or 9-positions of the anthracene group.
Specific examples of the group represented by the above formula (a1-r2-1) are shown below.
[ CHEM 8 ]
Figure BDA0002111803720000221
[ CHEM 9 ]
Figure BDA0002111803720000231
[ CHEM 10 ]
Specific examples of the group represented by the above formula (a1-r2-2) are listed below.
[ CHEM 11 ]
Figure BDA0002111803720000233
Figure BDA0002111803720000241
[ CHEM 12 ]
Figure BDA0002111803720000242
[ CHEM 13 ]
Figure BDA0002111803720000243
Figure BDA0002111803720000251
Specific examples of the group represented by the above formula (a1-r2-3) are listed below.
[ CHEM 14 ]
Figure BDA0002111803720000252
Specific examples of the group represented by the above formula (a1-r2-4) are listed below.
[ CHEM 15 ]
Tertiary alkoxycarbonyl acid-dissociable group:
examples of the acid-dissociable group that protects the hydroxyl group of the polar group include an acid-dissociable group represented by the following general formula (a1-r-3) (hereinafter, also referred to as a "tertiary alkoxycarbonyl acid-dissociable group" for convenience of description).
[ CHEM 16 ]
Figure BDA0002111803720000261
[ wherein, Ra'7～Ra’9Are each an alkyl group.]
In the formula (a1-r-3), Ra'7～Ra’9Each preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.
The total number of carbon atoms of each alkyl group is preferably 3 to 7, more preferably 3 to 5, and most preferably 3 to 4.
Examples of the structural unit (a1) include a structural unit derived from an acrylate ester in which a hydrogen atom bonded to a carbon atom at the α -position is substituted with a substituent, a structural unit derived from acrylamide, a structural unit in which at least a part of a hydrogen atom in a hydroxyl group of a structural unit derived from hydroxystyrene or a hydroxystyrene derivative is protected with a substituent containing the acid-decomposable group, and a structural unit in which at least a part of a hydrogen atom in-C (═ O) -OH of a structural unit derived from vinylbenzoic acid or a vinylbenzoic acid derivative is protected with a substituent containing the acid-decomposable group.
Among the above, as the structural unit (a1), a structural unit derived from an acrylate in which a hydrogen atom bonded to a carbon atom at the α -position may be substituted with a substituent is preferable.
As a preferred specific example of the above-mentioned structural unit (a1), a structural unit represented by the following general formula (a1-1) or (a1-2) can be mentioned.
[ CHEM 17 ]
Figure BDA0002111803720000271
[ wherein R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a haloalkyl group having 1 to 5 carbon atoms. Va (Va)1Is a 2-valent hydrocarbon group which may have an ether bond, na1Is an integer of 0 to 2. Ra1Is represented by the above general formula (a1-r-1) or (a1-r-2)An acid-dissociable group. Wa1Is na2A hydrocarbon radical having a valence of +1, na2Is an integer of 1 to 3, Ra2Is an acid-dissociable group represented by the general formula (a1-r-1) or (a 1-r-3).]
In the above formula (a1-1), the alkyl group having 1 to 5 carbon atoms in R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically, it includes methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl and the like. The C1-5 haloalkyl is a group in which a part or all of the hydrogen atoms of the C1-5 alkyl are substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is particularly preferable.
R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluoroalkyl group having 1 to 5 carbon atoms, and most preferably a hydrogen atom or a methyl group, from the viewpoint of easy industrial availability.
In the formula (a1-1), Va1The 2-valent hydrocarbon group in (b) may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
As Va1The aliphatic hydrocarbon group of the 2-valent hydrocarbon group in (b) may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, and a saturated aliphatic hydrocarbon group is generally preferred.
More specifically, the aliphatic hydrocarbon group includes a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group having a ring in the structure, and the like.
The straight-chain aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms.
The linear aliphatic hydrocarbon group is preferably a linear alkylene group, and specifically includes methylene [ -CH ]2-]Ethylene [ - (CH)2)2-]Propylene [ - (CH)2)3-]Butylene [ - (CH)2)4-]- (CH) pentylene [ - (CH)2)5-]And the like.
The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, still more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.
The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specifically includes-CH (CH)3)-、-CH(CH2CH3)-、-C(CH3)2-、-C(CH3)(CH2CH3)-、-C(CH3)(CH2CH2CH3)-、-C(CH2CH3)2-isoalkylmethylene; -CH (CH)3)CH2-、-CH(CH3)CH(CH3)-、-C(CH3)2CH2-、-CH(CH2CH3)CH2-、-C(CH2CH3)2-CH2-isoalkylethylene; -CH (CH)3)CH2CH2-、-CH2CH(CH3)CH2-isoalkylpropylene; -CH (CH)3)CH2CH2CH2-、-CH2CH(CH3)CH2CH2An alkylalkylene group such as an alkylbutylene group, etc. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.
Examples of the aliphatic hydrocarbon group having a ring in the above structure include an alicyclic hydrocarbon group (a group obtained by removing 2 hydrogen atoms from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, and a group in which an alicyclic hydrocarbon group is interposed between linear or branched aliphatic hydrocarbon groups. Examples of the linear or branched aliphatic hydrocarbon group include the same groups as those of the linear aliphatic hydrocarbon group and the branched aliphatic hydrocarbon group.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing 2 hydrogen atoms from a monocyclic hydrocarbon. The monocyclic hydrocarbon is preferably a monocyclic hydrocarbon having 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing 2 hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably a C7-12 polycycloalkane, and specifically includes adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like.
As Va1The aromatic hydrocarbon group of the 2-valent hydrocarbon group in (1) is a hydrocarbon group having an aromatic ring.
The number of carbon atoms of the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, further preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. Wherein the number of carbons does not include the number of carbons in the substituent.
Specific examples of the aromatic ring included in the aromatic hydrocarbon group include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, phenanthrene, and the like; and an aromatic heterocyclic ring in which a part of carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom.
Specific examples of the aromatic hydrocarbon group include a group (arylene group) obtained by removing 2 hydrogen atoms from the aromatic hydrocarbon ring; a group (aryl group) obtained by removing 1 hydrogen atom from the aromatic hydrocarbon ring, wherein 1 hydrogen atom is substituted with an alkylene group (for example, a group obtained by removing 1 hydrogen atom from an aryl group in an arylalkyl group such as a benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc.). The number of carbon atoms of the alkylene group (alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.
In the formula (a1-1), Ra1Is an acid-dissociable group represented by the formula (a1-r-1) or (a 1-r-2).
In the formula (a1-2), Wa1N in (1)a2The +1 valent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group is a hydrocarbon group having no aromatic character, and may be saturated or unsaturated, and is preferably saturated in general. Examples of the aliphatic hydrocarbon group include a straight-chain or branched-chain aliphatic hydrocarbon group, an aliphatic hydrocarbon group having a ring in the structure, or a combination of a straight-chain or branched-chain aliphatic hydrocarbon group and an aliphatic hydrocarbon group having a ring in the structureA group.
N isa2The +1 valence is preferably 2 to 4 valence, more preferably 2 or 3 valence.
In the formula (a1-2), Ra2Is an acid-dissociable group represented by the general formula (a1-r-1) or (a 1-r-3).
Specific examples of the structural unit represented by the above formula (a1-1) are shown below. In the following formulae, RαRepresents a hydrogen atom, a methyl group or a trifluoromethyl group.
[ CHEM 18 ]
Figure BDA0002111803720000291
Figure BDA0002111803720000301
[ CHEM 19 ]
Figure BDA0002111803720000302
[ CHEM 20 ]
Figure BDA0002111803720000303
Figure BDA0002111803720000311
[ CHEM 21 ]
Figure BDA0002111803720000312
[ CHEM 22 ]
[ CHEM 23 ]
[ CHEM 24 ]
Figure BDA0002111803720000323
Figure BDA0002111803720000331
[ CHEM 25 ]
[ CHEM 26 ]
Figure BDA0002111803720000333
Figure BDA0002111803720000341
[ CHEM 27 ]
Figure BDA0002111803720000342
[ CHEM 28 ]
Specific examples of the structural unit represented by the above formula (a1-2) are shown below.
[ CHEM 29 ]
Figure BDA0002111803720000351
(A1) The constituent unit (a1) of component (a) may be 1 or 2 or more.
The structural unit (a1) is more preferably represented by the above formula (a1-1) because the characteristics (sensitivity, CDU, shape, etc.) in KrF lithography can be more easily improved.
Among these, the structural unit (a1) is particularly preferably the structural unit (a1) containing a structural unit represented by the following general formula (a 1-1-1).
[ CHEM 30 ]
Figure BDA0002111803720000352
[ wherein Ra1”Is an acid-dissociable group represented by the general formula (a1-r2-1), (a1-r2-3) or (a1-r 2-4).]
In the formula (a1-1-1), R, Va1And na1And R, Va in the formula (a1-1)1And na1The same is true.
The acid-dissociable group represented by the general formula (a1-r2-1), (a1-r2-3), or (a1-r2-4) is described above.
(A1) The proportion of the structural unit (a1) in the component (a1) is preferably 1 to 80 mol%, more preferably 5 to 70 mol%, and still more preferably 10 to 60 mol% based on the total (100 mol%) of all the structural units constituting the component (a 1).
By setting the ratio of the structural unit (a1) to the lower limit or more, the lithographic characteristics such as sensitivity, resolution, and roughness improvement are improved. Further, when the ratio of the structural unit (a1) is not more than the upper limit, balance with other structural units can be obtained, and various lithographic characteristics can be improved.
Structural Unit (a10) containing hydroxystyrene skeleton
(A1) Component (b) is preferably a component (a10) having a hydroxystyrene skeleton-containing structural unit in addition to the structural unit (a 1).
Examples of the structural unit (a10) include a structural unit represented by the following general formula (a 10-1).
[ CHEM 31 ]
Figure BDA0002111803720000361
[ wherein R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a haloalkyl group having 1 to 5 carbon atoms. YaX1Is a single bond or a 2-valent linking group. WaX1Is (n)ax1+1) a valent aromatic hydrocarbon radical. n isax1Is an integer of 1 to 3.]
In the formula (a10-1), R is hydrogen atom, alkyl group with 1-5 carbon atoms or halogenated alkyl group with 1-5 carbon atoms.
The alkyl group having 1 to 5 carbon atoms in R is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically, it is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, or the like. The haloalkyl group having 1 to 5 carbon atoms as R is a group in which a part or all of hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is particularly preferable.
R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluoroalkyl group having 1 to 5 carbon atoms, and most preferably a hydrogen atom or a methyl group from the viewpoint of easy industrial availability.
In said formula (a10-1), Yax1Is a single bond or a 2-valent linking group.
As Yax1The 2-valent linking group in (2) includes, for example, a 2-valent hydrocarbon group which may have a substituent, and a 2-valent linking group containing a hetero atom as a preferable group.
A 2-valent hydrocarbon group which may have a substituent:
at Yax1When the hydrocarbon group is a 2-valent hydrocarbon group which may have a substituent, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
··Yax1Aliphatic hydrocarbon group of (1)
The aliphatic hydrocarbon group means a hydrocarbon group having no aromatic character. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, and is preferably a saturated aliphatic hydrocarbon group.
Examples of the aliphatic hydrocarbon group include a straight-chain or branched-chain aliphatic hydrocarbon group, an aliphatic hydrocarbon group having a ring in the structure, and the like.
Linear or branched aliphatic hydrocarbon radical
The number of carbon atoms of the straight chain aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, and most preferably 1 to 3.
The linear aliphatic hydrocarbon group is preferably a linear alkylene group, and specifically, a methylene group [ -CH ] may be mentioned2-]Ethylene [ - (CH)2)2-]Propylene [ - (CH)2)3-]Butylene [ - (CH)2)4-]- (CH) pentylene [ - (CH)2)5-]And the like.
The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, still more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.
The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specific examples thereof include-CH (CH)3)-、-CH(CH2CH3)-、-C(CH3)2-、-C(CH3)(CH2CH3)-、-C(CH3)(CH2CH2CH3)-、-C(CH2CH3)2-and the like alkylmethylene; -CH (CH)3)CH2-、-CH(CH3)CH(CH3)-、-C(CH3)2CH2-、-CH(CH2CH3)CH2-、-C(CH2CH3)2-CH2-and the like, an alkyl ethylene group; -CH (CH)3)CH2CH2-、-CH2CH(CH3)CH2-and the like, alkyl propylene; -CH (CH)3)CH2CH2CH2-、-CH2CH(CH3)CH2CH2An alkylalkylene group such as an alkylbutylene group. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.
The linear or branched aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluoroalkyl group having 5 or more carbon atoms and being substituted with a fluorine atom, and a carbonyl group.
Aliphatic hydrocarbon groups containing rings in the structure
Examples of the aliphatic hydrocarbon group having a ring in the structure include a cyclic aliphatic hydrocarbon group (a group obtained by removing 2 hydrogen atoms from an aliphatic hydrocarbon ring) having a hetero atom in the ring structure and optionally having a substituent, a group obtained by bonding the cyclic aliphatic hydrocarbon group to an end of a linear or branched aliphatic hydrocarbon group, and a group in which the cyclic aliphatic hydrocarbon group is interposed between linear or branched aliphatic hydrocarbon groups. Examples of the linear or branched aliphatic hydrocarbon group include the same aliphatic hydrocarbon groups as described above.
The number of carbon atoms of the cyclic aliphatic hydrocarbon group is preferably 3 to 20, more preferably 3 to 12.
The cyclic aliphatic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing 2 hydrogen atoms from a monocycloparaffin. The monocycloalkane is preferably a monocycloalkane having 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing 2 hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably a C7-12 polycycloalkane, and specifically includes adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like.
The cyclic aliphatic hydrocarbon group may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, and a carbonyl group.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a tert-butoxy group, and most preferably a methoxy group or an ethoxy group.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
Examples of the haloalkyl group as the substituent include groups in which a part or all of hydrogen atoms of the alkyl group are substituted with the halogen atom.
The cyclic aliphatic hydrocarbon group may be partially substituted with a heteroatom-containing substituent. The heteroatom-containing substituent is preferably-O-, -C (═ O) -O-, -S-, -S (═ O)2-、-S(＝O)2-O-。
··Yax1Aromatic hydrocarbon radical in (1)
The aromatic hydrocarbon group is a hydrocarbon group having at least 1 aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n +2 pi electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, still more preferably 6 to 15, and particularly preferably 6 to 12. Wherein the number of carbons does not include the number of carbons in the substituent. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and the like; and an aromatic heterocyclic ring in which a part of carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring.
Specific examples of the aromatic hydrocarbon group include a group (arylene group or heteroarylene group) obtained by removing 2 hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocyclic ring; a group obtained by removing 2 hydrogen atoms from an aromatic compound (for example, biphenyl, fluorene, or the like) having 2 or more aromatic rings; and a group (aryl or heteroaryl) obtained by removing 1 hydrogen atom from the aromatic hydrocarbon ring or the aromatic heterocyclic ring, wherein 1 hydrogen atom is substituted with an alkylene group (for example, a group obtained by removing 1 hydrogen atom from an aryl group in an arylalkyl group such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.), and the like. The number of carbon atoms of the alkylene group bonded to the aryl or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.
In the aromatic hydrocarbon group, a hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, and a hydroxyl group.
The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
Examples of the alkoxy group, the halogen atom, and the haloalkyl group as the substituent include those exemplified as the substituent for substituting the hydrogen atom of the cyclic aliphatic hydrocarbon group.
Heteroatom-containing 2-valent linking groups:
at Yax1In the case of a heteroatom-containing 2-valent linking group, preferable examples of the linking group include-O-, -C (═ O) -, -O-C (═ O) -O-, -C (═ O) -NH-, -NH-C (═ NH) - (H may be substituted by a substituent such as an alkyl group or an acyl group), -S-, -S (═ O)2-、-S(＝O)2-O-, of the formula-Y21-O-Y22-、-Y21-O-、-Y21-C(＝O)-O-、-C(＝O)-O-Y21-、-[Y21-C(＝O)-O]m”-Y22-、-Y21-O-C(＝O)-Y22-or-Y21-S(＝O)2-O-Y22A group represented by (wherein Y is)21And Y22Each independently is a 2-valent hydrocarbon group which may have a substituent, O is an oxygen atom, and m' is an integer of 0 to 3]And the like.
In the case where the heteroatom-containing 2-valent linking group is — C (═ O) -NH-, -C (═ O) -NH-C (═ O) -, -NH-C (═ NH) -, H thereof may be substituted with a substituent such as an alkyl group or an acyl group. The number of carbon atoms of the substituent (such as alkyl group or acyl group) is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5.
General formula-Y21-O-Y22-、-Y21-O-、-Y21-C(＝O)-O-、-C(＝O)-O-Y21-、-[Y21-C(＝O)-O]m”-Y22-、-Y21-O-C(＝O)-Y22-or-Y21-S(＝O)2-O-Y22In (Y)21And Y22Each independently is a 2-valent hydrocarbon group which may have a substituent. The 2-valent hydrocarbon group may be the same group as (a 2-valent hydrocarbon group which may have a substituent) listed in the description of the 2-valent linking group.
As Y21The aliphatic hydrocarbon group is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, still more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group or an ethylene group.
As Y22The aliphatic hydrocarbon group is preferably a linear or branched aliphatic hydrocarbon group, and more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group.
Is represented by the formula- [ Y ]21-C(＝O)-O]m”-Y22In the group represented by (A), m' is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, as represented by the formula- [ Y ]21-C(＝O)-O]m”-Y22A group represented by the formula-Y is particularly preferred21-C(＝O)-O-Y22-a group represented by (a). Among them, the formula- (CH) is preferred2)a’-C(＝O)-O-(CH2)b’-a group represented by (a). In the formula, a' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, further preferably 1 or 2, and most preferably 1. b' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, still more preferably 1 or 2, and most preferably 1.
As Yax1Preferably a single bond, an ester bond [ -C (═ O) -O-]An ether bond (-O-) -, -C- (═ O) -NH-, a linear or branched alkylene group, or a combination thereof, and among them, a single bond is particularly preferable.
In the formula (a10-1), Wax1Is (n)ax1+1) a valent aromatic hydrocarbon radical.
As Wax1The aromatic hydrocarbon group in (1) includes those removed from aromatic ring (n)ax1+1) hydrogen atoms. The aromatic ring is not particularly limited if it is a cyclic conjugated system having 4n +2 pi electronsThe compound may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, still more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and an aromatic heterocyclic ring in which a part of carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring.
In the formula (a10-1), nax1Is an integer of 1 to 3, preferably 1 or 2, more preferably 1.
Specific examples of the structural unit represented by the above formula (a10-1) are shown below.
In the formula, RαRepresents a hydrogen atom, a methyl group or a trifluoromethyl group.
[ CHEM 32 ]
(A1) The constituent unit (a10) of component (a) may be 1 or 2 or more.
(A1) The proportion of the structural unit (a10) in component (a) is, for example, 1 to 90 mol%, preferably 10 to 85 mol%, more preferably 20 to 80 mol%, and particularly preferably 30 to 75 mol%, based on the total (100 mol%) of all structural units constituting component (a 1).
By setting the ratio of the structural unit (a10) to be equal to or higher than the lower limit of the preferable range, the lithographic characteristics such as sensitivity, resolution, and roughness improvement are further improved. Further, by setting the upper limit value or less of the preferable range, balance with other constituent units can be easily obtained, and various lithographic characteristics can be improved.
Structural unit (a2)
(A1) Component (a) may have a lactone ring-containing group or an-SO-containing group in addition to the structural unit (a1)2-structural units (a2) containing cyclic groups or carbonate cyclic groups (but not limited thereto)Not including the structural element belonging to structural element (a 1).
Lactone ring type group-containing, -SO-containing structural unit (a2)2When the component (a1) is used for forming a resist film, a cyclic group or a cyclic group containing carbonate is effective in improving adhesion of the resist film to a substrate. Further, by having the structural unit (a2), the lithographic characteristics become favorable by effects such as, for example, appropriately adjusting the acid diffusion length, improving the adhesion of the resist film to the substrate, appropriately adjusting the solubility at the time of development, and improving the etching resistance.
The "lactone ring-containing group" refers to a cyclic group containing a ring (lactone ring) containing — O — C (═ O) -, in the ring skeleton thereof. The lactone ring is referred to as the first ring, and when the lactone ring is present alone, the lactone ring is referred to as a monocyclic group, and when the lactone ring has another ring structure, the lactone ring is referred to as a polycyclic group regardless of the structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group.
The lactone ring-containing group in the structural unit (a2) is not particularly limited, and any lactone ring-containing group can be used. Specifically, there may be mentioned groups represented by the following general formulae (a2-r-1) to (a 2-r-7).
[ CHEM 33 ]
Figure BDA0002111803720000421
[ wherein, Ra'21Each independently is a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, -COOR ", -OC (═ O) R", a hydroxyalkyl group or a cyano group; r' is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a-SO-containing group2-a cyclic group. A' is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom (-O-) or a sulfur atom (-S-), an oxygen atom or a sulfur atom. n 'is an integer of 0 to 2, and m' is 0 or 1.]
In the general formulae (a2-r-1) to (a2-r-7) as Ra'21The alkyl group in (1) is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. Specific examples thereof include methyl, ethyl, propyl, isopropyl, and isopropyl,N-butyl, isobutyl, t-butyl, pentyl, isopentyl, neopentyl, hexyl and the like. Among these, methyl or ethyl is preferable, and methyl is particularly preferable.
As Ra'21The alkoxy group in (1) is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably linear or branched. Specifically, the Ra 'may be mentioned'21Examples of the alkyl group in (1) include those in which an alkyl group is bonded to an oxygen atom (-O-).
As Ra'21Examples of the halogen atom in (b) include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
As Ra'21Examples of the haloalkyl group in (1) include the above Ra'21Wherein a part or all of hydrogen atoms of the alkyl group in (1) are substituted by the halogen atom. The haloalkyl group is preferably a fluoroalkyl group, and particularly preferably a perfluoroalkyl group.
Ra’21In the group-COOR ", -OC (. ═ O) R", R "is each a hydrogen atom, an alkyl group, a lactone ring-containing group, a carbonate ring-containing group, or a group containing-SO2-a cyclic group.
The alkyl group in R' may be linear, branched or cyclic, and the number of carbon atoms is preferably 1 to 15.
When R' is a linear or branched alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, and particularly preferably a methyl group or an ethyl group.
When R' is a cyclic alkyl group, the number of carbon atoms is preferably 3 to 15, more preferably 4 to 12, and most preferably 5 to 10. Specifically, there can be exemplified a group obtained by removing 1 or more hydrogen atoms from a monocycloparaffin which may be substituted or unsubstituted with a fluorine atom or a fluoroalkyl group; and groups obtained by removing 1 or more hydrogen atoms from a multicycloparaffin such as bicycloalkane, tricycloalkane or tetracycloalkane. More specifically, there may be mentioned a group obtained by removing 1 or more hydrogen atoms from a monocycloparaffin such as cyclopentane or cyclohexane; and groups obtained by removing 1 or more hydrogen atoms from a polycyclic alkane such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, or the like.
Examples of the lactone ring-containing group in R' include the same groups as those represented by the above general formulae (a2-R-1) to (a 2-R-7).
As the carbonate-containing cyclic group in R', there may be mentioned, in the same manner as the carbonate-containing cyclic group described later, specifically, groups represented by general formulae (ax3-R-1) to (ax3-R-3), respectively.
As containing-SO in R2A cyclic group with-SO-containing as described later2As the cyclic group, there may be mentioned those represented by the general formulae (a5-r-1) to (a 5-r-4).
As Ra'21The hydroxyalkyl group in (1) is preferably a hydroxyalkyl group having 1 to 6 carbon atoms, and concretely, the above Ra'21Wherein at least 1 of the hydrogen atoms of the alkyl group in (1) is substituted with a hydroxyl group.
In the general formulae (a2-r-2), (a2-r-3) and (a2-r-5), the alkylene group having 1 to 5 carbon atoms in A' is preferably a linear or branched alkylene group, and examples thereof include a methylene group, an ethylene group, an n-propylene group and an isopropylene group. When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include a group having-O-or-S-interposed between the terminal or carbon atom of the alkylene group, and examples thereof include-O-CH2-、-CH2-O-CH2-、-S-CH2-、-CH2-S-CH2-and the like. A' is preferably an alkylene group having 1 to 5 carbon atoms or-O-, more preferably an alkylene group having 1 to 5 carbon atoms, and most preferably a methylene group.
Specific examples of the groups represented by the general formulae (a2-r-1) to (a2-r-7) are shown below.
[ CHEM 34 ]
Figure BDA0002111803720000441
Figure BDA0002111803720000451
[ CHEM 35 ]
Figure BDA0002111803720000452
"contains-SO2The term "cyclic group" means a group containing-SO in its ring skeleton2The cyclic group of the ring of (A) is, in particular, -SO2The sulfur atom (S) in (E) forms a cyclic group which is part of the ring skeleton of the cyclic group. The ring skeleton of the catalyst contains-SO2The ring of (E) is referred to as a first ring, and is referred to as a monocyclic group when only the ring is present, and is referred to as a polycyclic group when the ring has other ring structures. containing-SO2The cyclic group may be a monocyclic group or a polycyclic group.
containing-SO2The cyclic group is particularly preferably one having-O-SO in the ring skeleton2A cyclic radical, i.e. containing-O-SO2-O-S-in (a) -forms the cyclic group of the sultone ring forming part of the ring backbone.
As containing-SO2More specifically, examples of the cyclic group include groups represented by the following general formulae (a5-r-1) to (a 5-r-4).
[ CHEM 36 ]
Figure BDA0002111803720000461
[ wherein, Ra'51Each independently is a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, -COOR ", -OC (═ O) R", a hydroxyalkyl group or a cyano group; r' is a hydrogen atom, an alkyl group, a lactone-containing cyclic group, a carbonate-containing cyclic group, or a-SO-containing group2-a cyclic group; a 'is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, and n' is an integer of 0 to 2.]
In the general formulae (a5-r-1) to (a5-r-2), A 'is the same as A' in the general formulae (a2-r-2), (a2-r-3) and (a 2-r-5).
As Ra'51Examples of the alkyl group, alkoxy group, halogen atom, haloalkyl group, -COOR ', -OC (═ O) R ', hydroxyalkyl group in (a2-R-1) to (a2-R-7) include Ra '21Are recited in the descriptionThe same groups.
Specific examples of the groups represented by the general formulae (a5-r-1) to (a5-r-4) are shown below. "Ac" in the formula represents an acetyl group.
[ CHEM 37 ]
Figure BDA0002111803720000462
[ CHEM 38 ]
Figure BDA0002111803720000472
[ CHEM 39 ]
Figure BDA0002111803720000473
The "carbonate-containing cyclic group" refers to a cyclic group containing a ring (carbonate ring) having a ring skeleton containing — O — C (═ O) -O-. The carbonate ring is referred to as the first ring, and when only the carbonate ring is present, the carbonate ring is referred to as a monocyclic group, and when the carbonate ring has another ring structure, the carbonate ring is referred to as a cyclic group regardless of the structure. The cyclic group containing carbonate may be a monocyclic group or a polycyclic group.
The cyclic group containing a carbonic ester is not particularly limited, and any cyclic group containing a carbonic ester can be used. Specifically, there can be mentioned groups represented by the following general formulae (ax3-r-1) to (ax 3-r-3).
[ CHEM 40 ]
Figure BDA0002111803720000481
[ wherein, Ra'x31Each independently is a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, -COOR ", -OC (═ O) R", a hydroxyalkyl group or a cyano group; r' is hydrogen atom, alkyl, or alkylEster ring group, carbonate ring group-containing group, or group containing-SO2-a cyclic group; a ' is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, p ' is an integer of 0 to 3, and q ' is 0 or 1.]
In the general formulae (ax3-r-2) to (ax3-r-3), A 'is the same as A' in the general formulae (a2-r-2), (a2-r-3) and (a 2-r-5).
As Ra'31Examples of the alkyl group, alkoxy group, halogen atom, haloalkyl group, -COOR ', -OC (═ O) R ', hydroxyalkyl group in (a2-R-1) to (a2-R-7) include Ra '21The same groups as those listed in the description of (1).
Specific examples of the groups represented by the general formulae (ax3-r-1) to (ax3-r-3) are shown below.
[ CHEM 41 ]
As the structural unit (a2), among them, a structural unit derived from an acrylate in which a hydrogen atom bonded to a carbon atom at the α -position may be substituted with a substituent is preferable.
The structural unit (a2) is preferably a structural unit represented by the following general formula (a 2-1).
[ CHEM 42 ]
Figure BDA0002111803720000491
[ wherein R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a haloalkyl group having 1 to 5 carbon atoms. Ya21Is a single bond or a 2-valent linking group. La21is-O-, -COO-, -CON (R ') -, -OCO-, -CONHCO-or-CONHCS-, and R' represents a hydrogen atom or a methyl group. Wherein, in La21In the case of-O-, Ya21Will not be-CO-. Ra21Is a lactone ring group-containing, carbonate ring group-containing or-SO-containing group2-a cyclic group.]
In the formula (a2-1), R is the same as described above. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluoroalkyl group having 1 to 5 carbon atoms, and particularly preferably a hydrogen atom or a methyl group, from the viewpoint of easy industrial availability.
In the formula (a2-1), as Ya21The 2-valent linking group in (2) is not particularly limited, and a 2-valent hydrocarbon group which may have a substituent, a 2-valent heteroatom-containing linking group, and the like are exemplified as preferable linking groups. About Ya21The description of the substituent-optionally substituted 2-valent hydrocarbon group and the heteroatom-containing 2-valent linking group in (a) are the same as those described for Ya in the above-mentioned general formula (a10-1)x1The same applies to the description of the substituent-optionally substituted 2-valent hydrocarbon group and the heteroatom-containing 2-valent linking group.
As Ya21Preferably a single bond, an ester bond [ -C (═ O) -O-]An ether bond (-O-), a linear or branched alkylene group, or a combination thereof.
In the formula (a2-1), Ra21Is a lactone ring group-containing, SO-containing2-a cyclic group or a carbonate-containing cyclic group.
As Ra21In (1), the lactone ring-type group-containing compound contains-SO2The cyclic group and the carbonate-containing cyclic group preferably include groups represented by the above general formulae (a2-r-1) to (a2-r-7), groups represented by the general formulae (a5-r-1) to (a5-r-4), and groups represented by the general formulae (ax3-r-1) to (ax 3-r-3).
Among them, preferred is a lactone ring group-containing or-SO-containing group2A cyclic group, more preferably a group represented by the general formula (a2-r-1), (a2-r-2), (a2-r-6) or (a5-r-1), respectively. More specifically, any of the above-mentioned chemical formulae (r-lc-1-1) to (r-lc-1-7), (r-lc-2-1) to (r-lc-2-18), (r-lc-6-1), (r-sl-1-1), and (r-sl-1-18) is more preferable.
(A1) The constituent unit (a2) of component (a) may be 1 or 2 or more.
When the component (a1) has the structural unit (a2), the proportion of the structural unit (a2) is preferably 0 to 50 mol%, more preferably 5 to 45 mol%, further preferably 10 to 40 mol%, and particularly preferably 10 to 30 mol% based on the total (100 mol%) of all the structural units constituting the component (a 1).
When the ratio of the structural unit (a2) is equal to or higher than a preferable lower limit, the effect of including the structural unit (a2) can be sufficiently obtained, and when the ratio is equal to or lower than an upper limit, balance with other structural units can be obtained, and various lithographic characteristics can be improved.
Structural unit (a3)
The component (a1) may further have a structural unit (A3) containing a polar group-containing aliphatic hydrocarbon group in addition to the structural unit (a1) (except for units belonging to the structural unit (a1) and the structural unit (a 2)). By providing the component (a1) with the structural unit (a3), the effects of, for example, appropriately adjusting the acid diffusion length, improving the adhesion of the resist film to the substrate, appropriately adjusting the solubility during development, improving the etching resistance, and the like are achieved, whereby the lithographic characteristics and the like become good.
Examples of the polar group include a hydroxyl group, a cyano group, a carboxyl group, and a hydroxyalkyl group in which a part of hydrogen atoms of an alkyl group is substituted with a fluorine atom, and a hydroxyl group is particularly preferable.
Examples of the aliphatic hydrocarbon group include a linear or branched hydrocarbon group (preferably an alkylene group) having 1 to 10 carbon atoms, and a cyclic aliphatic hydrocarbon group (a cyclic group). The cyclic group may be a monocyclic group or a polycyclic group, and may be appropriately selected from cyclic groups which have been mentioned many times in the resin for a resist composition for ArF excimer laser light, for example. The cyclic group is preferably a polycyclic group, and more preferably has 7 to 30 carbon atoms.
Among these, a structural unit derived from an acrylic ester containing an aliphatic polycyclic group having a hydroxyalkyl group in which a part of hydrogen atoms of a hydroxyl group, a cyano group, a carboxyl group, or an alkyl group is substituted with a fluorine atom is more preferable. Examples of the polycyclic group include groups obtained by removing 2 or more hydrogen atoms from a bicycloalkane, tricycloalkane, tetracycloalkane, or the like. Specifically, there may be mentioned groups obtained by removing 2 or more hydrogen atoms from a polycyclic alkane such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. Among these polycyclic groups, industrially preferred are groups obtained by removing 2 or more hydrogen atoms from adamantane, groups obtained by removing 2 or more hydrogen atoms from norbornane, and groups obtained by removing 2 or more hydrogen atoms from tetracyclododecane.
The structural unit (a3) is not particularly limited as long as it contains a polar group-containing aliphatic hydrocarbon group, and any structural unit can be used.
As the structural unit (a3), a structural unit derived from an acrylate in which a hydrogen atom bonded to a carbon atom at the α -position may be substituted with a substituent and containing a polar group-containing aliphatic hydrocarbon group is preferable.
When the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, the structural unit (a3) is preferably a structural unit derived from hydroxyethyl acrylate.
When the hydrocarbon group in the polar group-containing aliphatic hydrocarbon group is a polycyclic group, preferable examples of the structural unit (a3) include a structural unit represented by the following formula (a3-1), a structural unit represented by the following formula (a3-2), and a structural unit represented by the following formula (a 3-3).
[ CHEM 43 ]
Figure BDA0002111803720000511
[ wherein R is the same as above, j is an integer of 1 to 3, k is an integer of 1 to 3, t' is an integer of 1 to 3, l is an integer of 1 to 5, and s is an integer of 1 to 3. ]
In the formula (a3-1), j is preferably 1 or 2, and more preferably 1. In the case where j is 2, it is preferable that hydroxyl groups are bonded to the 3-and 5-positions of the adamantyl group. When j is 1, a hydroxyl group is preferably bonded to the 3-position of the adamantyl group.
j is preferably 1, and particularly preferably a hydroxyl group is bonded to the 3-position of the adamantyl group.
In the formula (a3-2), k is preferably 1. The cyano group is preferably bonded to the 5-or 6-position of the norbornyl group.
In the formula (a3-3), t' is preferably 1. l is preferably 1. s is preferably 1. They are preferably bonded with 2-norbornyl or 3-norbornyl at the terminal of the carboxyl group of acrylic acid. The fluoroalkyl alcohol is preferably bonded to the 5 or 6 position of the norbornyl group.
(A1) The constituent unit (a3) of component (a) may be 1 or 2 or more.
When the component (a1) has the structural unit (A3), the proportion of the structural unit (A3) is preferably 1 to 40 mol%, more preferably 2 to 30 mol%, further preferably 5 to 25 mol%, and particularly preferably 5 to 20 mol% based on the total of all the structural units constituting the component (a 1).
By setting the ratio of the structural unit (a3) to a preferred lower limit or more, the effect of including the structural unit (a3) can be sufficiently obtained, and when the ratio is a preferred upper limit or less, balance with other structural units is easily obtained, and various lithographic characteristics are improved.
Structural unit (st)
(A1) Component (b) may have, in addition to the structural unit (a1), a structural unit (st) derived from styrene or a derivative thereof. "styrene" is a concept including styrene and a concept in which a hydrogen atom at the α -position of styrene is substituted with a substituent such as an alkyl group or a haloalkyl group. Examples of the alkyl group as the substituent include alkyl groups having 1 to 5 carbon atoms, and examples of the haloalkyl group as the substituent include haloalkyl groups having 1 to 5 carbon atoms.
Examples of the "styrene derivative" include styrene derivatives in which a substituent is bonded to the benzene ring of styrene in which the hydrogen atom at the α -position may be substituted with a substituent.
The α -position (carbon atom at α -position) refers to a carbon atom to which a benzene ring is bonded unless otherwise specified.
The "structural unit derived from styrene" and the "structural unit derived from a styrene derivative" mean a structural unit in which an ethylenic double bond of styrene or a styrene derivative is cleaved.
(A1) The constituent (st) of the component (A) may be 1 or 2 or more.
When the component (a1) has the structural unit (st), the proportion of the structural unit (st) is preferably 1 to 50 mol%, more preferably 3 to 40 mol%, based on the total (100 mol%) of all the structural units constituting the component (a 1).
Other structural units
(A1) The component (c) may have other structural units in addition to the structural unit (a1), the structural unit (a10), the structural unit (a2), the structural unit (a3) and the structural unit (st).
Examples of the other structural unit include a structural unit (a9) represented by the general formula (a9-1) described later, a structural unit derived from styrene, a structural unit derived from a styrene derivative (excluding the structural unit belonging to the structural unit (a 10)), and a structural unit containing an acid-non-dissociable alicyclic group.
Structural unit (a 9):
the structural unit (a9) is a structural unit represented by the following general formula (a 9-1).
[ CHEM 44 ]
Figure BDA0002111803720000531
[ wherein R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a haloalkyl group having 1 to 5 carbon atoms. Ya91Is a single bond or a 2-valent linking group. Ya92Is a 2-valent linking group. R91Is a hydrocarbon group which may have a substituent.]
In the formula (a9-1), R is the same as defined above.
R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a fluoroalkyl group having 1 to 5 carbon atoms, and particularly preferably a hydrogen atom or a methyl group, from the viewpoint of easy industrial availability.
In the formula (a9-1), as Ya91The linking group having a valence of 2 in (a) is exemplified by the linking group to Ya in the above general formula (a10-1)x1The 2-valent linking group in (1) is the same linking group. Wherein, as Ya91Preferably a single bond.
In the formula (a9-1), as Ya92The linking group having a valence of 2 in (a) is exemplified by the linking group to Ya in the above general formula (a10-1)x1And (3) a linking group which is the same as the linking group of the 2-valent linking group of (1).
At Ya92In the 2-valent linking group of (1), the substituent may beThe 2-valent hydrocarbon group of the group is preferably a linear or branched aliphatic hydrocarbon group.
Furthermore, in Ya92Among the 2-valent linking groups in (a), examples of the heteroatom-containing 2-valent linking group include-O-, -C (═ O) -, -O-C (═ O) -O-, -C (═ O) -NH-, -NH-C (═ NH) - (H may be substituted by a substituent such as an alkyl group or an acyl group), -S-, -S (═ O)2-、-S(＝O)2-O-, -C (═ S) -, of formula-Y21-O-Y22-、-Y21-O-、-Y21-C(＝O)-O-、-C(＝O)-O--Y21、[Y21-C(＝O)-O]m’-Y22-or-Y21-O-C(＝O)-Y22A group represented by (wherein Y is)21And Y22Each independently represents a 2-valent hydrocarbon group which may have a substituent, O represents an oxygen atom, and m' represents an integer of 0 to 3.]And the like. Among them, preferred are-C (═ O) -, -C (═ S) -.
In the formula (a9-1), R is91Examples of the hydrocarbon group in (1) include an alkyl group, a 1-valent alicyclic hydrocarbon group, an aryl group, and an aralkyl group.
R91The alkyl group in (1) is preferably a C1-8, more preferably a C1-6, and still more preferably a C1-4, and may be linear or branched. Specifically, methyl, ethyl, propyl, butyl, hexyl, octyl and the like are preferably cited.
R91The alicyclic hydrocarbon group having a valence of 1 in (A) is preferably a C3-20, more preferably a C3-12, and may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing 1 or more hydrogen atoms from a monocyclic hydrocarbon. The monocycloalkane is preferably a monocycloalkane having 3 to 6 carbon atoms, and specific examples thereof include cyclobutane, cyclopentane, cyclohexane, and the like. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing 1 or more hydrogen atoms from a cycloalkane, and the polycycloalkane is preferably a group having 7 to 12 carbon atoms, and specifically, adamantane or norbornane is preferable. Isobornane, tricyclodecane, tetracyclododecane, and the like.
R91The aryl group in (1) is preferably an aryl group having 6 to 18 carbon atoms, more preferably an aryl group having 6 to 18 carbon atomsAryl having 6 to 10 carbon atoms is preferable, and particularly, phenyl is preferable.
As R91The aralkyl group in (1) is preferably an alkylene group having 1 to 8 carbon atoms and the above-mentioned "R91The aralkyl group in which the aryl group in (1) is bonded is more preferably an alkylene group having 1 to 6 carbon atoms and the above-mentioned "R91The aralkyl group in which the aryl group in (1) is bonded is particularly preferably an alkylene group having 1 to 4 carbon atoms and the above-mentioned "R91An aralkyl group in which the aryl group in (1) is bonded.
R91In the hydrocarbon group (b), a part or all of hydrogen atoms of the hydrocarbon group are preferably substituted by fluorine atoms, and more preferably 30 to 100% of hydrogen atoms of the hydrocarbon group are substituted by fluorine atoms. Among these, a perfluoroalkyl group in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms is particularly preferable.
R91The hydrocarbon group in (1) may have a substituent. Examples of the substituent include a halogen atom, an oxo group (═ O), a hydroxyl group (— OH), and an amino group (— NH)2)、-SO2-NH2And the like. Further, a part of the carbon atoms constituting the hydrocarbon group may be substituted with a substituent containing a hetero atom. Examples of the heteroatom-containing substituent include-O-, -NH-, -N ═ C (═ O) -O-, -S-, -S (═ O)2-、-S(＝O)2-O-。
At R91In the above-mentioned examples of the substituted hydrocarbon group, lactone ring-containing groups represented by the general formulae (a2-r-1) to (a2-r-7) are mentioned.
In addition, in R91In the above-mentioned examples, the substituted hydrocarbon group may include-SO-containing groups represented by the general formulae (a5-r-1) to (a5-r-4)2-a cyclic group; substituted aryl groups represented by the following chemical formula, 1-valent heterocyclic groups, and the like.
[ CHEM 45 ]
Figure BDA0002111803720000551
Among the structural units (a9), the structural unit represented by the following general formula (a9-1-1) is preferred.
[ CHEM 46 ]
Figure BDA0002111803720000552
[ wherein R is the same as above, Ya91Is a single bond or a 2-valent linking group, R91Is a hydrocarbon group which may have a substituent, R92Is an oxygen atom or a sulfur atom.]
In the general formula (a9-1-1), Ya is concerned91、R91And R is as defined above. Furthermore, R92Is an oxygen atom or a sulfur atom.
Specific examples of the structural unit represented by the above formula (a9-1) or general formula (a9-1-1) are shown below. In the following formula, RαRepresents a hydrogen atom, a methyl group or a trifluoromethyl group.
[ CHEM 47 ]
[ CHEM 48 ]
Figure BDA0002111803720000562
[ CHEM 49 ]
Figure BDA0002111803720000563
(A1) The constituent unit (a9) contained in component (a) may be 1 or 2 or more.
When the component (a1) has the structural unit (a9), the proportion of the structural unit (a9) is preferably 1 to 40 mol%, more preferably 3 to 30 mol%, further preferably 5 to 25 mol%, and particularly preferably 10 to 20 mol% based on the total (100 mol%) of all the structural units constituting the component (a 1).
By setting the ratio of the structural unit (a9) to the lower limit or more, effects such as an appropriate adjustment of the acid diffusion length, an improvement in the adhesion of the resist film to the substrate, an appropriate adjustment of the solubility during development, an improvement in the resist resistance, and the like can be obtained, and when the ratio is not more than the upper limit, a balance with other structural units can be obtained, and various lithographic characteristics can be improved.
Structural unit (a 4):
the structural unit (a4) is a structural unit containing an acid-non-dissociable alicyclic group. The (a1) component may have the structural unit (a4) in addition to the structural unit (a 1).
When the component (a1) has the structural unit (a4), the resist pattern formed has improved dry etching resistance. The hydrophobicity of the component (A) is improved. The improvement in hydrophobicity is considered to contribute to improvement in resolution, resist pattern shape, and the like, particularly in the case of a solvent development process.
The "acid-non-dissociable cyclic group" in the structural unit (a4) is a cyclic group that does not dissociate even by the action of an acid generated in the resist composition by exposure (for example, when an acid is generated from the component (B) described later), and remains as it is in the structural unit.
As the structural unit (a4), for example, a structural unit derived from an acrylate containing an acid-non-dissociable alicyclic group is preferable. As the cyclic group, a large number of groups known in the art as groups to be used in resin components of resist compositions for ArF excimer lasers, KrF excimer lasers (preferably for ArF excimer lasers), and the like can be used.
Particularly, at least 1 kind selected from the group consisting of tricyclodecyl group, adamantyl group, tetracyclododecyl group, isobornyl group and norbornyl group is preferable from the viewpoint of easy industrial availability. These polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.
As the structural unit (a4), specific examples thereof include structural units represented by the following general formulae (a4-1) to (a 4-7).
[ CHEM 50 ]
Figure BDA0002111803720000581
[ in the formula, RαAs before.]
(A1) The constituent unit (a4) of component (a) may be 1 or 2 or more.
When the component (a1) has the structural unit (a4), the proportion of the structural unit (a4) is preferably 1 to 30 mol%, more preferably 3 to 20 mol%, based on the total of all the structural units constituting the component (a 1).
When the proportion of the structural unit (a4) is equal to or higher than a preferable lower limit, the effect of including the structural unit (a4) can be sufficiently obtained, and when the proportion is equal to or lower than a preferable upper limit, balance with other structural units can be easily obtained.
The component (a1) contained in the resist composition may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
(A1) The component (A) is preferably a component containing a polymer compound (A1-1) (hereinafter referred to as "component A1-1") having a structural unit (a 1).
Examples of the preferable component (a1-1) include a polymer compound having a repeating structure of the structural unit (a1) and the structural unit (a10), a polymer compound having a repeating structure of the structural unit (a1) and the structural unit (st), and the like.
In addition to the combination of the 2 constituent elements described above, the constituent elements described above may be appropriately combined as the 3 rd or 3 or more constituent elements in accordance with the desired effect. Examples of the combination of 3 or more structural units include the structural unit (a1), the combination of the structural unit (a10) and the structural unit (st), and the like.
The above-mentioned (a1) component can be produced by: the monomer from which each structural unit is derived is dissolved in a polymerization solvent, and polymerization can be carried out by adding a radical polymerization initiator such as Azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (e.g., V-601). Alternatively, the component (a1) can be produced by: the monomer from which the structural unit (a1) is derived and, if necessary, a precursor of the monomer from which the structural unit other than the structural unit (a1) is derived (monomer in which the functional group of the monomer is protected) are dissolved in a polymerization solvent, polymerized by adding the radical polymerization initiator as described above, and deprotectedAnd (4) reacting. In addition, in the polymerization, HS-CH may be used in combination, for example2-CH2-CH2-C(CF3)2Chain transfer agent such as-OH to introduce-C (CF) at the end3)2-OH groups. The hydroxyalkyl group-containing copolymer in which a part of the hydrogen atoms of the alkyl group is substituted with fluorine atoms as described above is effective in reducing development defects and lowering LER (line edge roughness: uneven unevenness of line side walls).
(A1) The mass average molecular weight (Mw) of the component (B) is not particularly limited, but is preferably about 1000 to 50000, more preferably 2000 to 30000, and further preferably 3000 to 20000 (in terms of polystyrene based on Gel Permeation Chromatography (GPC)).
If the Mw of the component (a1) is not more than the preferable upper limit of the range, the solubility in a resist solvent is sufficient for use as a resist, and if the Mw of the component is not less than the preferable lower limit of the range, the dry etching resistance and the cross-sectional shape of a resist pattern are good.
(A1) The molecular weight distribution (Mw/Mn) of the component (B) is not particularly limited, but is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and particularly preferably 1.1 to 2.0. In addition, Mn represents a number average molecular weight.
With respect to the (A2) component
The resist composition of the present embodiment may use, as the component (a), a base material component (hereinafter referred to as a "component (a 2)") which is not the component (a1) and whose solubility in a developer changes due to the action of an acid.
The component (a2) is not particularly limited, and may be used by arbitrarily selecting from a large number of components conventionally known as base components for chemically amplified resist compositions.
(A2) The component (A) may be 1 kind of high molecular compound or low molecular compound, or 2 or more kinds thereof may be used in combination.
(A) The proportion of the component (a1) in the component (a) is preferably 25% by mass or more, more preferably 50% by mass or more, further preferably 75% by mass or more, and may be 100% by mass, based on the total mass of the component (a). When the ratio is 25% by mass or more, a resist pattern having excellent lithographic characteristics such as high sensitivity, resolution, and roughness can be easily formed.
In the resist composition of the present embodiment, the content of the component (a) is 20% by mass or more. When the content of the component (a) is 20% by mass or more, a thick resist film having a film thickness of 5 μm or more can be formed when the resist composition is applied to a substrate. (A) The content of the component (b) is preferably 25% by mass or more, more preferably 30% by mass or more. By increasing the content of the component (a) in the resist composition, a resist composition capable of forming a resist film having a higher thickness (for example, 8 μm or more) can be obtained.
(A) The upper limit of the content of the component is not particularly limited as long as the resist film can be formed at a high concentration, and can be, for example, 50 mass% or less. (A) The content of the component (b) may be, for example, 20 to 50% by mass, preferably 25 to 45% by mass, and more preferably 30 to 40% by mass. The thickness of the resist film to be formed may be adjusted.
< ingredient (D0) >
(D0) The component (B) is a tertiary monoamine compound represented by the following general formula (d 0). (D0) The component (A) is a substance which acts as a quencher for capturing an acid generated by exposure in the resist composition. The resist composition of the present embodiment contains 0.01 to 0.05 parts by mass of the component (D0) per 100 parts by mass of the component (a), and thus has good sensitivity, good lithographic characteristics such as CDU, and a resist pattern having a good shape can be formed.
[ CHEM 51 ]
[ wherein Rx is1～Rx3Each independently represents a hydrocarbon group which may have a substituent. Rx1～Rx3More than 2 can be bonded to each other to form a ring structure.]
In the formula (d0), Rx1、Rx2、Rx3Each independently is a hydrocarbon group which may have a substituent.
Rx1、Rx2And Rx3The hydrocarbon group in (2) may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
As Rx1、Rx2And Rx3Examples of the aliphatic hydrocarbon group in the hydrocarbon group in (1) include a linear or branched alkyl group and a cyclic aliphatic hydrocarbon group.
The straight-chain alkyl group preferably has 1 to 15 carbon atoms, more preferably 2 to 15 carbon atoms, still more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 10 carbon atoms. Specific examples thereof include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, and n-dodecyl group.
The branched alkyl group preferably has 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, and still more preferably 3 to 10 carbon atoms. Specific examples thereof include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1-diethylpropyl group, and 2, 2-dimethylbutyl group.
The Rx is1、Rx2And Rx3The linear or branched alkyl group in (1) may have a substituent or may have no substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (═ O), an ester bond [ -C (═ O) -O-]And an ether bond (-O-), etc. The ester bond and the ether bond as the substituents are groups substituting methylene groups constituting the alkyl group. In addition, Rx1、Rx2And Rx3The linear or branched alkyl group in (1) has no amino group as a substituent.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
Among these substituents, a hydroxyl group is preferable.
Rx1、Rx2And Rx3The cyclic aliphatic hydrocarbon group in (2) may be a polycyclic group or a monocyclic group. The monocyclic aliphatic hydrocarbon group is preferably a group obtained by removing 1 hydrogen atom from a monocyclic hydrocarbon. The monocycloparaffins are preferably monocycloparaffins having 3 to 6 carbon atoms, and specifically, cyclopentane, cyclohexane and the like are exemplified, and cyclopentane is particularly preferable. As multiple ring systemsThe aliphatic hydrocarbon group is preferably a group obtained by removing 1 hydrogen atom from a polycycloalkane, and the polycycloalkane is preferably a C7-12 polycycloalkane, and specifically, adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like are exemplified.
Rx as described above1、Rx2And Rx3The cyclic aliphatic hydrocarbon group in (1) may have a substituent or may have no substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (═ O), an alkyl group, an ester bond [ -C (═ O) -O-]And an ether bond (-O-), etc. The ester bond and the ether bond as the substituents are groups substituting methylene groups constituting the cyclic aliphatic hydrocarbon group. In addition, Rx1、Rx2And Rx3The cyclic aliphatic hydrocarbon group in (1) has no amino group as a substituent.
Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.
The alkyl group as the substituent is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. Specific examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, and hexyl. Among them, methyl or ethyl is preferable.
Among these, a hydroxyl group or an alkyl group is preferable as the substituent.
Rx1、Rx2And Rx3The aromatic hydrocarbon group as the hydrocarbon group in (1) is a hydrocarbon group having at least 1 aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n +2 pi electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, still more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and the like; and an aromatic heterocycle in which a part of carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom (excluding a nitrogen atom). Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom and a sulfur atom. Specific examples of the aromatic heterocyclic ring include furan rings and thiophene rings.
As Rx1、Rx2And Rx3Specific examples of the aromatic hydrocarbon group in (1) include a group (aryl group or heteroaryl group) obtained by removing 1 hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring; a group obtained by removing 1 hydrogen atom from an aromatic compound (for example, biphenyl, fluorene, or the like) having 2 or more aromatic rings; and a group in which 1 hydrogen atom of the aromatic hydrocarbon ring or aromatic heterocyclic ring is substituted with an alkylene group (for example, an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group). The number of carbon atoms of the alkylene group bonded to the aromatic hydrocarbon ring or the aromatic heterocyclic ring is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.
The Rx is1、Rx2And Rx3The aromatic hydrocarbon group in (1) may or may not have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (═ O), an alkyl group, and the like. Examples of the halogen atom and the alkyl group as the substituent include the same groups as those listed as the substituents of the above-mentioned cyclic aliphatic hydrocarbon group.
Among these substituents, a hydroxyl group or an alkyl group is preferable.
At Rx1、Rx2And Rx3In (b), 2 or more of them may be bonded to form a ring. The Rx is1、Rx2And Rx3The ring structure formed by 2 or more of (a) and the nitrogen atom in the formula (d0) form a ring structure. The ring structure may be an aliphatic heterocyclic ring containing a nitrogen atom in the ring structure, or may be an aromatic heterocyclic ring. The ring structure may be a polycyclic structure made of other ring structures.
Rx1、Rx2And Rx3The aliphatic heterocyclic ring formed by 2 or more of (A) may be polycyclic or monocyclic. The aliphatic heterocyclic ring is preferably an aliphatic heterocyclic ring having 3 to 6 carbon atoms, and specific examples thereof include aziridine, azetidine, pyrrolidine, piperidine, and the like.
Rx1、Rx2And Rx3The aromatic heterocyclic ring formed by 2 or more of (A) may be polycyclic or monocyclic. The aromatic heterocyclic ring is preferably an aromatic heterocyclic ring having 3 to 12 carbon atoms, and specific examples thereof include aziridine, azetidine (Azete), pyrrole, pyridine, and azepine.
Rx1、Rx2And Rx3The ring structure formed by bonding at least 2 of the above groups may have a substituent or may have no substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxo group (═ O), an alkyl group, and the like. Examples of the halogen atom and the alkyl group as the substituent include the same groups as those listed as the substituents of the above-mentioned cyclic aliphatic hydrocarbon group.
As Rx1、Rx2And Rx3Among the substituents in the ring structure formed by bonding 2 or more, an alkyl group is preferable.
Rx1、Rx2And Rx3The ring structure formed by bonding 2 or more of (a) preferably has a substituent, and more preferably has a substituent at a carbon atom adjacent to a nitrogen atom in the general formula (d 0).
Preferable examples of the component (D0) include compounds represented by the following general formula (D0-1) or (D0-2).
[ CHEM 52 ]
Figure BDA0002111803720000631
[ formula (d0-1), Rx11～Rx13Each independently represents a linear or branched alkyl group or an aromatic hydrocarbon group which may have a substituent. However, Rx11～Rx13Not all are aromatic hydrocarbon groups. In the formula (d0-2), Ry1～Ry3Represents a linear or branched alkyl group which may have a substituent. ny1 represents an integer of 0 to 3.]
A compound represented by the general formula (d0-1)
In the general formula (d0-1), Rx11～Rx13Each independently may have an access toA linear or branched alkyl group or an aromatic hydrocarbon group as a substituent. Wherein, Rx11～Rx13Not all are aromatic hydrocarbon groups.
Rx11、Rx12And Rx13The straight-chain alkyl group in (1) is preferably a C1-15, more preferably a C2-15, still more preferably a C2-12, and particularly preferably a C2-10. Specific examples thereof include Rx in the above formula (d0)1、Rx2And Rx3The hydrocarbon group in (1) is the same as the above-mentioned linear alkyl group.
Rx11、Rx12And Rx13The branched alkyl group in (1) is preferably a C3-15, more preferably a C3-12, and still more preferably a C3-10. Specific examples thereof include Rx in the above formula (d0)1、Rx2And Rx3The branched alkyl group of the hydrocarbon group in (1) is the same as the above-mentioned groups.
Rx as described above11、Rx12And Rx13The linear or branched alkyl group in (1) may have a substituent or may have no substituent. As such a substituent, Rx in the formula (d0) is mentioned1、Rx2And Rx3The substituents for the linear or branched alkyl group in (1) are the same as those listed above. Among these substituents, a hydroxyl group is preferable.
Rx11、Rx12And Rx13The aromatic hydrocarbon group in (b) may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, still more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples thereof include Rx in the above formula (d0)1、Rx2And Rx3The same groups as those listed for the aromatic hydrocarbon group of the hydrocarbon group in (1).
The Rx is11、Rx12And Rx13The aromatic hydrocarbon group in (1) may or may not have a substituent. As such a substituent, Rx in the formula (d0) is mentioned1、Rx2And Rx3Of (5)The substituents of the hydrocarbon group are the same as those listed above. Among these, an alkyl group is preferable as the substituent.
Rx11、Rx12And Rx13Not all are aromatic hydrocarbon groups. At Rx11、Rx12And Rx13When any of them is an aromatic hydrocarbon group, 1 of them is preferably an aromatic hydrocarbon group.
Preferable examples of the compound represented by the general formula (d0-1) include compounds represented by the following general formula (d0-1-1) or (d 0-1-2).
[ CHEM 53 ]
Figure BDA0002111803720000641
[ formula (d0-1-1) ], Rx111～Rx113Each independently represents a linear or branched alkyl group which may have a substituent. In the formula (d0-1-2), Rx121～Rx123Each independently represents a linear or branched alkyl group which may have a substituent. nx1 represents an integer of 0 to 5.]
In the general formula (d0-1-1), Rx111～Rx113Each independently represents a linear or branched alkyl group which may have a substituent. As Rx111、Rx112And Rx113Examples of the linear or branched alkyl group in (1) include those mentioned above for Rx in the general formula (d0)1、Rx2And Rx3The linear or branched alkyl group in (1) is the same as the alkyl group.
Rx111、Rx112And Rx113The linear or branched alkyl group in (1) may have a substituent or may have no substituent. As such a substituent, Rx in the formula (d0) is mentioned1、Rx2And Rx3The substituents for the linear or branched alkyl group in (1) are the same as those listed above. Among these substituents, a hydroxyl group is preferable.
Rx111～Rx113Preferably all are the same group.
General formula (VII)(d0-1-2) wherein Rx is121、Rx122And Rx123Each independently represents a linear or branched alkyl group which may have a substituent.
As Rx121And Rx122Examples of the linear or branched alkyl group in (b) include the same as Rx in the general formula (d0)1、Rx2And Rx3The linear or branched alkyl groups in (1) are the same.
Rx121And Rx122The linear or branched alkyl group in (1) may have a substituent or may have no substituent. Examples of the substituent include Rx in the above-mentioned formula (d0)1、Rx2And Rx3The substituents for the linear or branched alkyl group in (1) are the same as those listed above. Among these substituents, a hydroxyl group is preferable.
Rx121And Rx122The same groups as each other are preferred.
Rx123The straight-chain alkyl group in (1) is preferably a C1-10, more preferably a C1-6, still more preferably a C1-3, and particularly preferably a C1 or C2. As a specific example, Rx in the formula (d0)1、Rx2And Rx3Among them, methyl or ethyl is preferable.
Rx123The branched alkyl group in (1) is preferably a C3-10, more preferably a C3-6, and further preferably a C3-or C4. As a specific example, Rx in the above formula (d0) may be mentioned1、Rx2And Rx3Specific examples of the branched alkyl group in (1) include the following groups. Among them, isopropyl, isobutyl or tert-butyl is preferable.
Rx123The linear or branched alkyl group in (1) may have a substituent or may have no substituent. As such a substituent, Rx in the formula (d0) is mentioned1、Rx2And Rx3The same groups as those mentioned as examples of the substituent of the linear or branched alkyl group in (1).
In the general formula (d0-1-2), nx1 represents an integer of 0 to 5. nx1 is preferably 0 to 3, more preferably 0 to 2, and further preferably 0 or 1.
Specific examples of the compound represented by the general formula (d0-1) are shown below.
[ CHEM 54 ]
Figure BDA0002111803720000651
Figure BDA0002111803720000661
Specific examples of the compound represented by the general formula (d0-1) include trialkylamines such as trimethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-nonylamine and tri-n-dodecylamine; trialkyl alcohol amines such as tri-n-octylalcohol amine; tris (2-methoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl } amine, tris {2- (1-ethoxyethoxy) ethyl } amine, tris {2- (1-ethoxypropoxy) ethyl } amine, tris [2- {2- (2-hydroxyethoxy) ethoxy } ethyl ] amine, triethanolamine triacetate, and the like.
A compound represented by the general formula (d0-2)
In the general formula (d0-2), Ry1、Ry2And Ry3Each independently represents a linear or branched alkyl group which may have a substituent.
Ry1And Ry2The straight-chain alkyl group in (1) is preferably a C1-10, more preferably a C2-6, and further preferably a C2-4. As a specific example, Rx in the above formula (d0) may be mentioned1、Rx2And Rx3Examples of the linear alkyl group in (3) include the groups listed below.
Ry1And Ry2The branched alkyl group in (1) is preferably a C3-10, more preferably a C3-6, and further preferably a C3-or C4. Specific examples thereof include Rx in the above formula (d0)1、Rx2And Rx3Examples of the branched alkyl group in (1) include the groups listed below. Among them, isopropyl, isobutyl or tert-butyl is preferable.
Ry1And Ry2The linear or branched alkyl group in (1) may have a substituent or may have no substituent. As such a substituent, Rx in the formula (d0) is mentioned1、Rx2And Rx3The substituents for the linear or branched alkyl group in (1) are the same as those listed above.
Wherein Ry1And Ry2A branched alkyl group is preferred, a branched alkyl group having no substituent is more preferred, and an isopropyl group, an isobutyl group, or a tert-butyl group is further preferred. Ry1And Ry2Preferably identical to each other
Ry3The linear alkyl group in (1) preferably has 1 to 10 carbon atoms, more preferably has 2 to 6 carbon atoms, and still more preferably has 2 to 4 carbon atoms. Specific examples thereof include Rx in the above formula (d0)1、Rx2And Rx3Examples of the linear alkyl group in (3) include the groups listed below.
Rx123The branched alkyl group in (1) is preferably a C3-10, more preferably a C3-6, and further preferably a C3-or C4. Specific examples thereof include Rx in the above formula (d0)1、Rx2And Rx3Examples of the branched alkyl group in (1) include the groups listed below.
Ry1And Ry2The linear or branched alkyl group in (1) may have a substituent or may have no substituent. As such a substituent, Rx in the formula (d0) is mentioned1、Rx2And Rx3The substituents for the linear or branched alkyl group in (1) are the same as those listed above.
In the general formula (d0-2), ny1 is an integer of 0 to 3. ny1 is preferably 0 to 2, more preferably 0 or 1, and further preferably 0.
Specific examples of the compound represented by the general formula (d0-2) are shown below.
[ CHEM 55 ]
Figure BDA0002111803720000671
(D0) The component (A) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
The content of the component (D0) in the resist composition of the present embodiment is 0.01 to 0.05 parts by mass per 100 parts by mass of the component (a). When the content of the component (D0) is in the above range, it is possible to improve CDU while maintaining high sensitivity and to obtain a resist pattern having a good shape when a thick resist film having a film thickness of 5 μm or more is formed. (D0) The content of the component (A) is preferably 0.02 to 0.05 parts by mass, more preferably 0.02 to 0.04 parts by mass, per 100 parts by mass of the component (A).
< optional Components >
Component (B): acid generator component(s)
The resist composition of the present embodiment preferably contains an acid generator component (B) that generates an acid upon exposure in addition to the components (a) and (D0).
The component (B) is not particularly limited, and any acid generator heretofore proposed as an acid generator for a chemically amplified resist can be used.
Examples of such an acid generator include onium salt type acid generators such as iodonium salts and sulfonium salts, oxime sulfonate type acid generators; diazomethane acid generators such as dialkyl or bisarylsulfonyl diazomethane and poly (bissulfo) diazomethane; a plurality of acid generators such as nitrobenzyl sulfonate acid generators, imino sulfonate acid generators, disulfone acid generators and the like.
As the onium salt-type acid generator, for example, a compound represented by the following general formula (b-1) (hereinafter also referred to as "component (b-1)"), a compound represented by the following general formula (b-2) (hereinafter also referred to as "component (b-2)") or a compound represented by the following general formula (b-3) (hereinafter also referred to as "component (b-3)") can be used.
[ CHEM 56 ]
[ in the formula, R101、R104～R108Each independently represents a cyclic group which may have a substituent, a linear alkyl group which may have a substituent, or a linear alkenyl group which may have a substituent. R104、R105May be bonded to each other to form a ring. R102Is a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms. Y is101Is a single bond or a 2-valent linking group comprising an oxygen atom. V101～V103Each independently a single bond, alkylene, or fluoroalkylene. L is101～L102Each independently a single bond or an oxygen atom. L is103～L105Each independently of the other being a single bond, -CO-or-SO2-. M is an integer of 1 or more, M'm+Is an onium cation having a valence of m.]
{ anion portion }
The anion part of component (b-1)
In the formula (b-1), R101The alkyl group may be a cyclic group which may have a substituent, a linear alkyl group which may have a substituent, or a linear alkenyl group which may have a substituent.
A cyclic group which may have a substituent:
the cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group having no aromatic character. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, and a saturated aliphatic hydrocarbon group is generally preferred.
R101The aromatic hydrocarbon group in (1) is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, still more preferably 5 to 20 carbon atoms, particularly preferably 6 to 15 carbon atoms, and most preferably 6 to 10 carbon atoms. Wherein the number of carbons does not include the number of carbons in the substituent.
As R101The aromatic ring of the aromatic hydrocarbon group in (3) includes, specifically, benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, an aromatic heterocyclic ring in which a part of carbon atoms constituting the aromatic ring is substituted with a hetero atom, and the like. As the hetero atom in the aromatic heterocyclic ring, there may be mentionedExamples of the nitrogen atom include an oxygen atom, a sulfur atom and a nitrogen atom.
As R101Specific examples of the aromatic hydrocarbon group in (1) include a group obtained by removing 1 hydrogen atom from the aromatic ring (an aryl group: for example, phenyl, naphthyl, etc.), a group obtained by substituting 1 hydrogen atom of the aromatic ring with an alkylene group (for example, an arylalkyl group such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.), and the like. The alkylene group (alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably has 1 to 2 carbon atoms, and particularly preferably has 1 carbon atom.
R101The cyclic aliphatic hydrocarbon group in (2) includes an aliphatic hydrocarbon group having a ring in the structure.
Examples of the aliphatic hydrocarbon group having a ring in its structure include an alicyclic hydrocarbon group (a group obtained by removing 1 hydrogen atom from an aliphatic hydrocarbon ring), a group obtained by bonding an alicyclic hydrocarbon group to the end of a linear or branched aliphatic hydrocarbon group, and a group in which an alicyclic hydrocarbon group is interposed between linear or branched aliphatic hydrocarbon groups.
The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.
The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing 1 or more hydrogen atoms from a monocyclic hydrocarbon. The monocyclic hydrocarbon is preferably a monocyclic hydrocarbon having 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing 1 or more hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably a C7-30 polycycloalkane. Among these, as the polycyclic alkane, polycyclic alkanes having a polycyclic skeleton with a crosslinked ring, such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane, are more preferable; polycyclic alkanes having a polycyclic skeleton of condensed rings, such as cyclic groups having a steroid skeleton.
Wherein, as R101The cyclic aliphatic hydrocarbon group in (1) is preferably a group obtained by removing 1 or more hydrogen atoms from a monocycloparaffin or polycycloalkane, and more preferably a group obtained by removing 1 or more hydrogen atoms from a polycycloalkaneThe group obtained by removing 1 hydrogen atom from cycloalkane is particularly preferably an adamantyl group, a norbornyl group, or a cyclic group having a steroid skeleton, and most preferably an adamantyl group or a cyclic group having a steroid skeleton.
The straight or branched aliphatic hydrocarbon group which may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms.
The linear aliphatic hydrocarbon group is preferably a linear alkylene group, and specifically includes methylene [ -CH ]2-]Ethylene [ - (CH)2)2-]Propylene [ - (CH)2)3-]Butylene [ - (CH)2)4-]- (CH) pentylene [ - (CH)2)5-]And the like.
The branched aliphatic hydrocarbon group is preferably a branched alkylene group, and specifically includes-CH (CH)3)-、-CH(CH2CH3)-、-C(CH3)2-、-C(CH3)(CH2CH3)-、-C(CH3)(CH2CH2CH3)-、-C(CH2CH3)2-isoalkylmethylene; -CH (CH)3)CH2-、-CH(CH3)CH(CH3)-、-C(CH3)2CH2-、-CH(CH2CH3)CH2-、-C(CH2CH3)2-CH2-isoalkylethylene; -CH (CH)3)CH2CH2-、-CH2CH(CH3)CH2-isoalkylpropylene; -CH (CH)3)CH2CH2CH2-、-CH2CH(CH3)CH2CH2An alkylalkylene group such as an alkylbutylene group, etc. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.
Furthermore, R101The cyclic hydrocarbon group in (2) may contain a hetero atom like a heterocycle and the like. Specifically, there may be mentioned lactone ring-containing groups represented by the general formulae (a2-r-1) to (a2-r-7) and-SO-containing groups represented by the general formulae (a5-r-1) to (a5-r-4)2-a cyclic radicalAnd other heterocyclic groups represented by the following chemical formulae (r-hr-1) to (r-hr-16).
[ CHEM 57 ]
Figure BDA0002111803720000701
As R101Examples of the substituent in the cyclic group in (b) include an alkyl group, an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, a carbonyl group, and a nitro group.
The alkyl group as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
The alkoxy group as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a tert-butoxy group, and most preferably a methoxy group or an ethoxy group.
Examples of the halogen atom as a substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.
Examples of the haloalkyl group as a substituent include alkyl groups having 1 to 5 carbon atoms, for example, groups in which some or all of hydrogen atoms of methyl group, ethyl group, propyl group, n-butyl group, tert-butyl group, and the like are substituted with the above-mentioned halogen atom.
The carbonyl group as the substituent is a methylene group (-CH) substituted for the cyclic hydrocarbon group2-) of (a) a group of (b).
Chain alkyl group which may have a substituent:
as R101The chain alkyl group of (b) may be either linear or branched.
The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. Specific examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, and docosyl.
The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specific examples thereof include 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl and 4-methylpentyl.
Chain alkenyl group which may have a substituent:
as R101The chain alkenyl group (b) may be either straight-chain or branched, and the number of carbon atoms is preferably 2 to 10, more preferably 2 to 5, still more preferably 2 to 4, and particularly preferably 3. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), and a butenyl group. Examples of the branched alkenyl group include a 1-methylethenyl group, a 2-methylethenyl group, a 1-methylpropenyl group, and a 2-methylpropenyl group.
Among the above, the linear alkenyl group is preferably a linear alkenyl group, more preferably a vinyl group or a propenyl group, and particularly preferably a vinyl group.
As R101Examples of the substituent in the chain alkyl group or the chain alkenyl group include an alkoxy group, a halogen atom, a haloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, and the above-mentioned R101Cyclic group in (1), and the like.
Wherein R is101The cyclic group may have a substituent, and more preferably a cyclic hydrocarbon group may have a substituent. More specifically, for example, a group obtained by removing 1 or more hydrogen atoms from a phenyl group, a naphthyl group, or a polycycloalkane; lactone ring-containing groups represented by the general formulae (a2-r-1), (a2-r-3) to (a2-r-7), respectively; containing-SO represented by the general formulae (a5-r-1) to (a5-r-4) respectively2-cyclic groups, etc.
In the formula (b-1), Y101Is a single bond or a 2-valent linking group comprising an oxygen atom.
At Y101In the case of a 2-valent linking group containing an oxygen atom, Y101Atoms other than oxygen atoms may be contained. Examples of the atom other than the oxygen atom include carbon atom,Hydrogen atom, sulfur atom, nitrogen atom, etc.
Examples of the linking group having a valence of 2 and containing an oxygen atom include linking groups represented by the following general formulae (y-al-1) to (y-al-8).
As Y101The linking group having a valence of 2 and containing an ester bond or the linking group having a valence of 2 and containing an ether bond are preferable, and the linking groups represented by the general formulae (y-al-1) to (y-al-5) are more preferable.
In the formula (b-1), V101Is a single bond, alkylene or fluoroalkylene. V101The alkylene group and fluoroalkylene group in (1) are preferably C1-C4. As V101In (3), the fluoroalkylene group includes V101A group in which a part or all of hydrogen atoms of the alkylene group in (1) is substituted by fluorine atoms. Wherein, V101Preferably a single bond or a C1-4 fluoroalkylene group.
In the formula (b1-1), R102Is a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms. R102Preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom.
Specific examples of the anion portion of the component (b-1) include, for example, those in Y101When the anion is a single bond, there may be mentioned fluoroalkylsulfonate anions such as trifluoromethanesulfonate anion and perfluorobutanesulfonate anion; at Y101In the case of a linking group having a valence of 2 and containing an oxygen atom, an anion represented by any one of the following general formulae (an-1) to (an-3) can be mentioned.
[ CHEM 58 ]
Figure BDA0002111803720000721
Figure BDA0002111803720000731
[ in the formula, R "101Is an alicyclic ring group which may have a substituent, a 1-valent heterocyclic group represented by the formulae (r-hr-1) to (r-hr-6), or a chain alkyl group which may have a substituent. R'102Is an aliphatic cyclic group which may have a substituent, a lactone-containing cyclic group represented by the general formulae (a2-r-1), (a2-r-3) to (a2-r-7), or an-SO-containing cyclic group represented by the general formulae (a5-r-1) to (a5-r-4)2-a cyclic group. R'103The group is an aromatic cyclic group which may have a substituent, an aliphatic cyclic group which may have a substituent, or a chain alkenyl group which may have a substituent. V'101Is a single bond, an alkylene group having 1 to 4 carbon atoms or a fluoroalkylene group having 1 to 4 carbon atoms. R102Is a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms. v ' is an independent integer of 0-3, q ' is an independent integer of 1-20, and n ' is 0 or 1.]
R”101、R”102And R "103The alicyclic group which may have a substituent(s) is preferably as the R101The cyclic aliphatic hydrocarbon group in (1) is exemplified. As the substituent, there may be mentioned optionally substituted R101The cyclic aliphatic hydrocarbon group in (1) has the same substituent.
R”103The aromatic cyclic group which may have a substituent(s) in (1) is preferably the R101Examples of the aromatic hydrocarbon group in the cyclic hydrocarbon group in (1) are given. As the substituent, there may be mentioned optionally substituted R101The aromatic hydrocarbon group in (1) has the same substituent.
R”101The chain alkyl group which may have a substituent(s) in (1) is preferably the R group101The chain alkyl group in (1) above. R'104The optionally substituted chain alkenyl group in (1) is preferably the R group101The chain alkenyl group in (1) is exemplified.
V”101Preferably a single bond or a fluoroalkylene group, and more preferably a single bond or a fluoroalkylene group having 1 to 3 carbon atoms. At V'101In the case of fluoroalkylene radicals, -V "101-C(F)(R”102)-SO3 -V in (1) "101preferably-CF2-、-CHF-、-CF2CF2-、-CHFCF2-、-CF(CF3)CF2-、-CH(CF3)CF2-, more preferably-CF2-、-CHF-。
R102Is a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms. R102Preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom.
v' is an integer of 0 to 3, preferably 0 or 1. q' is an integer of 1 to 20, preferably an integer of 1 to 10, more preferably an integer of 1 to 5, further preferably 1, 2 or 3, and particularly preferably 1 or 2. n "is 0 or 1.
Anion part of component (b-2)
In the formula (b-2), R104、R105Each independently represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and R in the formula (b-1)101The same groups. Wherein R is104、R105May be bonded to each other to form a ring.
R104、R105The alkyl group is preferably a chain alkyl group which may have a substituent, more preferably a linear or branched alkyl group or a linear or branched fluoroalkyl group.
The chain alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms, and still more preferably 1 to 3 carbon atoms. R is also good in solubility in a solvent for a resist, and the like104、R105The number of carbons of the chain alkyl group(s) is preferably as small as possible within the above-mentioned range of carbon numbers. Furthermore, R104、R105The higher the number of hydrogen atoms substituted with fluorine atoms in the chain alkyl group (2), the stronger the acid strength is, and thus the more preferable. The proportion of fluorine atoms in the chain alkyl group, that is, the fluorination rate, is preferably 70 to 100%, more preferably 90 to 100%, and most preferably a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.
In the formula (b-2), V102、V103Each independently represents a single bond, an alkylene group or a fluoroalkylene group, and each of these groups is represented by formula (b-1) and V101The same groups.
In the formula (b-2), L101、L102Each independently a single bond or an oxygen atom.
The anion part of component (b-3)
In the formula (b-3), R106～R108Each independently represents a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and R in the formula (b-1)101The same groups.
L103～L105Each independently of the other being a single bond, -CO-or-SO2-。
{ cation portion }
In the formulae (b-1), (b-2) and (b-3), M is an integer of 1 or more, M'm+As the onium cation having a valence of m, sulfonium cation and iodonium cation can be preferably mentioned, and organic cations represented by the following general formulae (ca-1) to (ca-4) can be mentioned, respectively.
[ CHEMICAL 59 ]
Figure BDA0002111803720000751
[ in the formula, R201～R207And R211～R212Each independently represents an aryl group which may have a substituent, an alkyl group which may have a substituent, or an alkenyl group which may have a substituent, R201～R203、R206～R207、R211～R212May be bonded to each other to form a ring together with the sulfur atom in the formula. R208～R209Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, or may be bonded to each other to form a ring together with the sulfur atom in the formula. R210Is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a-SO-containing group which may have a substituent2-a cyclic group. L is201represents-C (═ O) -or-C (═ O) -O-. Plural of Y201Each independently represents an arylene group, an alkylene group or an alkenylene group. x is 1 or 2. W201Represents a (x +1) -valent linking group.]
As R201～R207And R211～R212Examples of the aryl group in (1) include unsubstituted aryl groups having 6 to 20 carbon atoms, and preferably phenyl and naphthyl groups.
As R201～R207And R211～R212The alkyl group in (2) is a chain or cyclic alkyl group, preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.
As R201～R207And R211～R212The number of carbon atoms in the alkenyl group is preferably 2 to 10.
As R201～R207And R211～R212Examples of the substituent which may be present include an alkyl group, a halogen atom, a haloalkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and groups represented by the following formulae (ca-r-1) to (ca-r-7).
[ CHEM 60 ]
Figure BDA0002111803720000752
[ wherein R'201Each independently represents a hydrogen atom, a cyclic group which may have a substituent, a linear alkyl group which may have a substituent, or a linear alkenyl group which may have a substituent.]
R’201Examples of the cyclic group which may have a substituent, the chain alkyl group which may have a substituent, or the chain alkenyl group which may have a substituent include R in the formula (b-1) described later101Examples of the same group other than the above-mentioned groups include the same group as the acid-dissociable group represented by the above-mentioned formula (a1-r-2) as a cyclic group which may have a substituent or a chain alkyl group which may have a substituent.
At R201～R203、R206～R207、R211～R212When they are bonded to each other to form a ring together with the sulfur atom in the formula, they may be bonded to each other via a heteroatom such as a sulfur atom, an oxygen atom, a nitrogen atom or the like, a carbonyl group, -SO-, -SO2-、-SO3-, -COO-, -CONH-or-N (R)N) - (the R)NIs C1-5 alkyl) And the like. The ring to be formed is preferably a three-to ten-membered ring in which 1 ring including the sulfur atom in the formula in the ring skeleton includes a sulfur atom, and particularly preferably a five-to seven-membered ring. Specific examples of the ring to be formed include a thiophene ring, a thiazole ring, a benzothiophene ring, a thianthrene ring, a benzothiophene ring, a dibenzothiophene ring, a 9H-thioxanthene ring, a thianthrene ring, a phenoxathiin ring, a tetrahydrothiophenium ring, and a tetrahydrothiopyranium ring.
R208～R209Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, in R208～R209In the case of an alkyl group, they may be bonded to each other to form a ring.
R210Is an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a-SO-containing group which may have a substituent2-a cyclic group.
As R210Examples of the aryl group in (1) include unsubstituted aryl groups having 6 to 20 carbon atoms, and preferably phenyl and naphthyl groups.
As R210The alkyl group in (1) is a chain or cyclic alkyl group, preferably an alkyl group having 1 to 30 carbon atoms.
As R210The alkenyl group in (1) preferably has 2 to 10 carbon atoms.
As R210Wherein the-SO-containing group may have a substituent2-cyclic radicals, preferably "containing-SO2A polycyclic group ", more preferably a group represented by the above general formula (a 5-r-1).
Y201Each independently represents an arylene group, an alkylene group or an alkenylene group.
Y201The arylene group in (b) may be exemplified by the group represented by R in the formula (b-1)101The aromatic hydrocarbon group in (1) is a group obtained by removing 1 hydrogen atom from an aromatic group.
Y201Examples of the alkylene group and alkenylene group in (a) include those derived from R in the formula (b-1)101The group represented by the chain alkyl group or the chain alkenyl group in (1) is a group obtained by removing 1 hydrogen atom.
In the formula (ca-4), x is 1 or 2.
W201Is a linking group having a valence of (x +1), i.e., 2 or 3.
As W201The 2-valent linking group in (a) is preferably a 2-valent hydrocarbon group which may have a substituent(s), and may be exemplified by the group corresponding to Ya in the above-mentioned general formula (a2-1)21The same 2-valent hydrocarbon group which may have a substituent. W201The 2-valent linking group in (b) may be linear, branched or cyclic, and is preferably cyclic. Among these, a group in which 2 carbonyl groups are combined at both ends of an arylene group is preferable. The arylene group includes phenylene and naphthylene, and phenylene is particularly preferable.
As W201The linking group having a valence of 3 in (1) may be exemplified by those derived from the above-mentioned group W201Wherein the 2-valent linking group is a group obtained by removing 1 hydrogen atom from the 2-valent linking group, a group obtained by bonding the 2-valent linking group to the 2-valent linking group, or the like. As W201The linking group having a valence of 3 in (1) is preferably a group in which 2 carbonyl groups are bonded to an arylene group.
Specific examples of the preferable cation represented by the formula (ca-1) include cations represented by the following formulae (ca-1-1) to (ca-1-78) and (ca-1-101) to (ca-1-149).
In the following chemical formula, g1 represents the number of repetitions, and g1 is an integer of 1 to 5. g2 represents the number of repetitions, and g2 is an integer of 0 to 20. g3 represents the number of repetitions, and g3 is an integer of 0 to 20.
[ CHEM 61 ]
Figure BDA0002111803720000771
Figure BDA0002111803720000781
[ CHEM 62 ]
Figure BDA0002111803720000782
[ CHEM 63 ]
Figure BDA0002111803720000791
[ CHEM 64 ]
Figure BDA0002111803720000792
Figure BDA0002111803720000801
[ CHEM 65 ]
Figure BDA0002111803720000802
[ CHEM 66 ]
[ CHEM 67 ]
Figure BDA0002111803720000812
Figure BDA0002111803720000821
[ CHEM 68 ]
Figure BDA0002111803720000822
[ CHEM 69 ]
Figure BDA0002111803720000831
[ CHEM 70 ]
Figure BDA0002111803720000832
Figure BDA0002111803720000841
[ in the formula, R "201Is a hydrogen atom or a substituent, and the substituent is exemplified by the above-mentioned R201～R207And R210～R212Examples of the substituent which may be contained include an alkyl group, a halogen atom, a haloalkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, and groups represented by the general formulae (ca-r-1) to (ca-r-7).]
Specific examples of the preferable cation represented by the formula (ca-2) include cations represented by the following formulae (ca-2-1) to (ca-2-3), a diphenyliodonium cation, and a bis (4-tert-butylphenyl) iodonium cation.
[ CHEM 71 ]
Figure BDA0002111803720000842
As the preferable cation represented by the above formula (ca-3), specifically, cations represented by the following formulae (ca-3-1) to (ca-3-7) are listed.
[ CHEM 72 ]
Figure BDA0002111803720000851
As the preferable cation represented by the above formula (ca-4), specifically, cations represented by the following formulae (ca-4-1) to (ca-4-2) are listed.
[ CHEM 73 ]
Figure BDA0002111803720000852
Of the above, the cation portion [ (M'm+)1/m]Cations represented by the general formula (ca-1) or (ca-2) are preferred, and cations represented by the general formula (ca-1) or (ca-2) are more preferred to be converted separatelyCations represented by chemical formulas (ca-1-1) to (ca-1-78), (ca-1-101) to (ca-1-149), and chemical formulas (ca-2-1) to (ca-2-3).
In the resist composition of the present embodiment, 1 kind of the component (B) may be used alone, or 2 or more kinds may be used in combination.
When the resist composition contains the component (B), the content of the component (B) in the resist composition is preferably 50 parts by mass or less, more preferably 1 to 40 parts by mass, further preferably 1 to 30 parts by mass, and particularly preferably 1 to 20 parts by mass, relative to 100 parts by mass of the component (a).
By setting the content of the component (B) within the above range, the pattern formation can be sufficiently performed.
When the resist composition contains the component (B), the molar ratio of the component (B) to the component (D0) is preferably 0.01 to 0.09 for the component (D0)/component (B), more preferably 0.02 to 0.09 for the component (D0)/component (B), and still more preferably 0.02 to 0.05 for the component (D0)/component (B). By setting the above molar ratio, when an acid is generated from the component (B) by exposure in forming a thick resist film having a thickness of 5 μm or more, the equilibrium of the trapped acid is improved by the component (D0), and CDU can be improved while maintaining high sensitivity.
Component (D): ingredients of acid diffusion controlling agent
(D) The component (a) is a substance that functions as a quencher (acid diffusion controller) for trapping an acid generated by exposure in the resist composition. The resist composition of the present embodiment may further contain an acid diffusion controller component other than the above-mentioned component (D0) as the component (D) within a range not to impair the effects of the present invention.
Examples of the (D) component other than the (D0) component include a photodegradable base (D1) (hereinafter referred to as a "D1) component") which loses its acid diffusion controllability by decomposition by exposure, and a nitrogen-containing organic compound (D2) (hereinafter referred to as a "D2") which does not belong to the (D1) component and the (D0) component.
With respect to the (D1) component
The component (D1) is not particularly limited as long as it is a component which loses acid diffusion controllability by decomposition by exposure to light, and is preferably 1 or more compounds selected from the group consisting of a compound represented by the following general formula (D1-1) (hereinafter referred to as a "D1-1 component"), a compound represented by the following general formula (D1-2) (hereinafter referred to as a "D1-2 component"), and a compound represented by the following general formula (D1-3) (hereinafter referred to as a "D1-3 component").
The components (d1-1) to (d1-3) decompose in the exposed portion of the resist film and lose the acid diffusion controllability (basicity), and thus cannot function as a quencher, but function as a quencher in the unexposed portion.
[ CHEM 74 ]
Figure BDA0002111803720000861
[ in the formula, Rd1～Rd4The alkyl group may be a cyclic group which may have a substituent, a linear alkyl group which may have a substituent, or a linear alkenyl group which may have a substituent. Wherein Rd in the general formula (d1-2)2To the carbon atom adjacent to the S atom in (1) is not bonded with a fluorine atom. Yd1Is a single bond or a 2-valent linking group. M is an integer of 1 or more, Mm+Each independently an m-valent onium cation.]
{ (d1-1) composition }
Anion part
In the formula (d1-1), Rd1Examples of the substituent(s) include a cyclic group which may have a substituent(s), a chain alkyl group which may have a substituent(s), and a chain alkenyl group which may have a substituent(s), and Rx in the formula (b1)1～Rx4And the like.
Among these, as Rd1Preferred is an aromatic hydrocarbon group which may have a substituent, an alicyclic group which may have a substituent, or a chain alkyl group which may have a substituent. Examples of the substituent which these groups may have include a hydroxyl group, an oxo group, an alkyl group, an aryl group, a fluorine atom, a fluoroalkyl group, lactone ring-containing groups represented by the general formulae (a2-r-1) to (a2-r-7), ether bonds, ester bonds, and combinations thereof. In the case of containing ether bond or ester bond as a substituent, may be through alkylene, as the substituent in this case, preferably respectively in the above formula (y-al-1) E(y-al-5) is a linking group.
As the aromatic hydrocarbon group, a polycyclic structure containing a phenyl group, a naphthyl group or a bicyclooctane skeleton (for example, a polycyclic structure composed of a ring structure of a bicyclooctane skeleton and other ring structures) is preferably exemplified.
The alicyclic group is more preferably a group obtained by removing 1 or more hydrogen atoms from a polycyclic alkane such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, or the like.
The chain alkyl group preferably has 1 to 10 carbon atoms, and specifically includes a linear alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group; branched alkyl groups such as 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl and 4-methylpentyl.
When the chain alkyl group is a fluoroalkyl group having a fluorine atom or a fluoroalkyl group as a substituent, the number of carbon atoms in the fluoroalkyl group is preferably 1 to 11, more preferably 1 to 8, and still more preferably 1 to 4. The fluoroalkyl group may contain an atom other than a fluorine atom. Examples of the atom other than the fluorine atom include an oxygen atom, a sulfur atom, and a nitrogen atom.
As Rd1The fluoroalkyl group is preferably a fluoroalkyl group in which a part or all of the hydrogen atoms constituting the linear alkyl group are substituted with fluorine atoms, and particularly preferably a fluoroalkyl group (linear perfluoroalkyl group) in which all of the hydrogen atoms constituting the linear alkyl group are substituted with fluorine atoms.
Preferred specific examples of the anion portion of the component (d1-1) are shown below.
[ CHEM 75 ]
Figure BDA0002111803720000881
Cationic moiety
M 'of formula (d 1-1)'m+Is an onium cation having a valence of m.
As M'm+The onium cation(s) of (b) may preferably be the same cations as those represented by the general formulae (ca-1) to (ca-4), more preferably is represented by the general formula (ca-1), and still more preferably is represented by the formulae (ca-1-1) to (ca-1-78) and (ca-1-101) to (ca-1-149).
The component (d1-1) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
{ (d1-2) composition }
Anion part
In the formula (d1-2), Rd2Examples of the substituent(s) include a cyclic group which may have a substituent(s), a chain alkyl group which may have a substituent(s), and a chain alkenyl group which may have a substituent(s), and Rx in the above formula (b1)1～Rx4The same groups.
Wherein, Rd2The carbon atom adjacent to the S atom in (1) is not bonded with a fluorine atom (fluorine-free substitution). Thus, the anion of the component (D1-2) becomes a moderately weak acid anion, and the quenching ability as the component (D1) is improved.
As Rd2Preferred is a chain alkyl group which may have a substituent, or an alicyclic group which may have a substituent. The chain alkyl group preferably has 1 to 10 carbon atoms, more preferably 3 to 10 carbon atoms. More preferred examples of the alicyclic group include groups (which may have a substituent) obtained by removing 1 or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like; groups obtained by removing 1 or more hydrogen atoms from camphor and the like.
Rd2The hydrocarbon group (C) may have a substituent, and examples of the substituent include Rd of the formula (d1-1)1The hydrocarbon group (aromatic hydrocarbon group, alicyclic group, or chain alkyl group) in (1) may have the same substituent.
Preferred specific examples of the anion portion of the component (d1-2) are shown below.
[ CHEM 76 ]
Figure BDA0002111803720000891
Cationic moiety
M 'of formula (d 1-2)'m+Is an M-valent onium cation, with M 'in the formula (d 1-1)'m+The same is true.
The component (d1-2) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.
{ (d1-3) composition }
An anionic moiety
In the formula (d1-3), Rd3Examples of the substituent(s) include a cyclic group which may have a substituent(s), a linear alkyl group which may have a substituent(s), and a linear alkenyl group which may have a substituent(s), and Rx in the formula (b1)1～Rx4The same group is preferably a cyclic group, a linear alkyl group or a linear alkenyl group containing a fluorine atom. Among them, fluoroalkyl group is preferable, and Rd is more preferable1The fluoroalkyl group of (a) is the same as the fluoroalkyl group.
In the formula (d1-3), Rd4Is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent, and Rx in the above formula (b1) is exemplified1～Rx4And the like.
Among them, preferred are alkyl groups, alkoxy groups, alkenyl groups, and cyclic groups which may have a substituent.
Rd4The alkyl group in (1) is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specifically preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, or the like. Rd4A part of the hydrogen atoms of the alkyl group in (b) may be substituted by a hydroxyl group, a cyano group or the like.
Rd4The alkoxy group in (1) is preferably an alkoxy group having 1 to 5 carbon atoms, and specific examples of the alkoxy group having 1 to 5 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a tert-butoxy group. Among them, methoxy group and ethoxy group are preferable.
Rd4The alkenyl group in (b) may be exemplified by the same as Rx in the formula (b1)1～Rx4And the like, preferably vinyl, propenyl (allyl), 1-methylpropenyl and 2-methylpropenyl. These groups may further have an alkyl group having 1 to 5 carbon atoms or a haloalkyl group having 1 to 5 carbon atoms as a substituent.
Rd4Examples of the cyclic group in (b) include those mentioned above in connection with Rx in the formula (b1)1～Rx4The same groups are preferably alicyclic groups obtained by removing 1 or more hydrogen atoms from cycloalkanes such as cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane, or aromatic groups such as phenyl and naphthyl. At Rd4In the case of an alicyclic group, the resist composition is well dissolved in an organic solvent, and thus the lithographic characteristics are improved.
In the formula (d1-3), Yd1Is a single bond or a 2-valent linking group.
As Yd1The 2-valent linking group in (2) is not particularly limited, but examples thereof include a 2-valent hydrocarbon group (aliphatic hydrocarbon group, aromatic hydrocarbon group) which may have a substituent, a 2-valent linking group containing a hetero atom, and the like. These include Ya in the above formula (a10-1)x1The 2-valent hydrocarbon group which may have a substituent and the same group as the 2-valent linking group containing a hetero atom are listed in the description of the 2-valent linking group in (1).
As Yd1Preferably a carbonyl group, ester linkage, amide linkage, alkylene group, or a combination thereof. The alkylene group is more preferably a linear or branched alkylene group, and still more preferably a methylene group or a vinyl group.
Preferred specific examples of the anion portion of the component (d1-3) are shown below.
[ CHEM 77 ]
Figure BDA0002111803720000921
[ CHEM 78 ]
Figure BDA0002111803720000922
Figure BDA0002111803720000931
Cationic moiety
M 'of formula (d 1-3)'m+Is an M-valent onium cation, with M 'in the formula (d 1-1)'m+The same is true.
The component (d1-3) may be used alone in 1 kind, or 2 or more kinds may be used in combination.
(D1) The component (C) may be any of the above-mentioned components (d1-1) to (d1-3), or 2 or more thereof may be used in combination.
When the resist composition contains the component (D1), the content of the component (D1) in the resist composition is preferably 0.5 to 35 parts by mass, more preferably 1 to 25 parts by mass, still more preferably 2 to 20 parts by mass, and particularly preferably 3 to 15 parts by mass, relative to 100 parts by mass of the component (A).
When the content of the (D1) component is equal to or more than the preferable lower limit, particularly good lithographic characteristics and resist pattern shape can be easily obtained. On the other hand, if the upper limit value is less than or equal to the upper limit value, balance with other components can be obtained, and various lithographic characteristics become good.
(D1) The method for producing the component (A):
the method for producing the component (d1-1) or the component (d1-2) is not particularly limited, and the component (d1-1) or the component (d1-2) can be produced by a known method.
The method for producing the component (d1-3) is not particularly limited, and the component (d1-3) can be produced, for example, in the same manner as the method described in U.S. Pat. No. 2012-0149916.
With respect to the (D2) component
(D2) The component (b) is an alkali component, and is a nitrogen-containing organic compound component which functions as an acid diffusion controller in the resist composition (excluding the components belonging to the above-mentioned components (D0) and (D1)).
The component (D2) is not particularly limited as long as it functions as an acid diffusion controller and does not belong to the components (D0) and (D1), and examples thereof include compounds composed of an anion portion and a cation portion, aliphatic secondary amines, and aliphatic tertiary amines.
As the compound composed of an anion portion and a cation portion in the component (D2), compounds in which the cation portion in the above-mentioned components (D1-1) to (D1-3) is an ammonium cation can be cited. As the ammonium cation herein, NH4 is exemplified+Or a cation (a 1-4-stage ammonium cation) in which H bonded to the nitrogen atom is substituted with a hydrocarbon group which may have a hetero atom, or a cyclic cation which forms a ring together with the nitrogen atom.
The aliphatic amine is an amine having 1 or more aliphatic groups, and the aliphatic group preferably has 1 to 12 carbon atoms.
As the aliphatic amine, ammonia NH may be mentioned3An amine (alkylamine or alkylol amine) or a cyclic amine obtained by substituting 1 or 2 of the hydrogen atoms in (a) with an alkyl group or a hydroxyalkyl group having 12 or less carbon atoms.
Specific examples of the alkylamine and the alkylol amine include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylamine; and alkylol amines such as diethanolamine, diisopropanolamine, triisopropanolamine and di-n-octanolamine.
Examples of the cyclic amine include heterocyclic compounds containing a nitrogen atom as a hetero atom. The heterocyclic compound may be a monocyclic compound (aliphatic monocyclic amine) or a polycyclic compound (aliphatic polycyclic amine).
Specific examples of the alicyclic monocyclic amine include piperidine and piperazine.
The aliphatic polycyclic amine preferably has 6 to 10 carbon atoms, and specifically includes 1, 5-diazabicyclo [4.3.0] -5-nonene, 1, 8-diazabicyclo [5.4.0] -7-undecene, hexamethylenetetramine, 1, 4-diazabicyclo [2.2.2] octane and the like.
As the component (D2), an aromatic amine can be used.
Examples of the aromatic amine include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, and 2, 6-diisopropylaniline.
(D2) The components may be used alone or in combination of 2 or more.
When the resist composition contains the component (D2), the component (D2) is usually used in an amount of 0.01 to 5 parts by mass per 100 parts by mass of the component (a) in the resist composition. By setting the above range, balance with other components and various lithographic characteristics can be obtained.
The resist composition of the present embodiment preferably does not contain the component (D1) and the component (D2).
(E) component: at least 1 compound selected from oxyacids of organic carboxylic acids and phosphorus and derivatives thereof
In the resist composition of the present embodiment, the resist composition may contain at least 1 compound (E) (hereinafter referred to as "component (E)") selected from the group consisting of organic carboxylic acids, oxyacids of phosphorus and derivatives thereof as an arbitrary component for the purpose of preventing sensitivity deterioration, improving resist pattern shape, stability with time after leaving, and the like.
As the organic carboxylic acid, for example, acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, and the like are preferable.
The oxyacid of phosphorus includes phosphoric acid, phosphonic acid, phosphinic acid, and the like, and among these, phosphonic acid is particularly preferable.
Examples of the derivative of an oxyacid of phosphorus include esters obtained by substituting a hydrogen atom of the oxyacid with a hydrocarbon group, and examples of the hydrocarbon group include an alkyl group having 1 to 5 carbon atoms and an aryl group having 6 to 15 carbon atoms.
Examples of the phosphoric acid derivative include phosphoric acid esters such as di-n-butyl phosphate and diphenyl phosphate.
Examples of the derivative of phosphonic acid include phosphonic acid esters such as dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, and dibenzyl phosphonate.
The phosphinic acid derivative includes phosphinic acid esters and phenylphosphinic acid.
In the resist composition of the present embodiment, 1 kind of the component (E) may be used alone, or 2 or more kinds may be used in combination.
When the resist composition contains the component (E), the content of the component (E) is usually 0.01 to 5 parts by mass per 100 parts by mass of the component (a).
Component (F): fluorine additive ingredient
The resist composition of the present embodiment may contain a fluorine additive component (hereinafter referred to as "component (F)") in order to impart water repellency to the resist film or to improve the lithographic characteristics.
As the component (F), for example, fluorine-containing polymer compounds described in Japanese patent application laid-open Nos. 2010-002870, 2010-032994, 2010-277043, 2011-13569 and 2011-128226 can be used.
More specifically, the component (F) is a polymer having a structural unit (F1) represented by the following formula (F1-1). As the polymer, a polymer (homopolymer) composed only of a structural unit (f1) represented by the following formula (f1-1) is preferable; a copolymer of the structural unit (f1) and the structural unit (a 1); the structural unit (f1), a structural unit derived from acrylic acid or methacrylic acid, and a copolymer of the structural unit (a 1). Preferable examples of the structural unit (a1) copolymerized with the structural unit (f1) include a structural unit derived from 1-ethyl-1-cyclooctyl (meth) acrylate and a structural unit derived from 1-methyl-1-adamantyl (meth) acrylate.
[ CHEM 79 ]
Figure BDA0002111803720000961
[ wherein R is the same as above, Rf102And Rf103Each independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms or a haloalkyl group having 1 to 5 carbon atoms, Rf102And Rf103May be the same or different. nf1Is an integer of 1 to 5, Rf101Is an organic group containing a fluorine atom.]
In the formula (f1-1), R bonded to the carbon atom at the α -position is the same as described above. As R, a hydrogen atom or a methyl group is preferable.
In the formula (f1-1), as Rf102And Rf103Examples of the halogen atom of (b) include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is particularly preferable. As Rf102And Rf103Examples of the alkyl group having 1 to 5 carbon atoms in (b) include the same ones as those of the alkyl group having 1 to 5 carbon atoms in R, and a methyl group or an ethyl group is preferable. As Rf102And Rf103The halogenated alkyl group having 1 to 5 carbon atoms in (b) includes, specifically, a group in which hydrogen atoms of an alkyl group having 1 to 5 carbon atoms are partially or entirely substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is particularly preferable. Wherein as Rf102And Rf103The alkyl group is preferably a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms, and is preferably a hydrogen atom, a fluorine atom, a methyl group or an ethyl group.
In the formula (f1-1), nf1Is an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2.
In the formula (f1-1), Rf101Is an organic group containing a fluorine atom, preferably a hydrocarbon group containing a fluorine atom.
The hydrocarbon group containing a fluorine atom may be any of linear, branched or cyclic, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 15, and particularly preferably 1 to 10.
The hydrocarbon group containing a fluorine atom is preferably fluorinated in an amount of 25% or more, more preferably 50% or more, of the hydrogen atoms in the hydrocarbon group, and is particularly preferably fluorinated in an amount of 60% or more, since the hydrophobicity of the resist film at the time of immersion exposure can be improved.
Wherein, as Rf101More preferred is a C1-6 fluorinated hydrocarbon group, and particularly preferred is a trifluoromethyl group, -CH2-CF3、-CH2-CF2-CF3、-CH(CF3)2、-CH2-CH2-CF3、-CH2-CH2-CF2-CF2-CF2-CF3。
(F) The mass average molecular weight (Mw) of the component (B) is preferably 1000 to 50000, more preferably 5000 to 40000, and most preferably 10000 to 30000 (in terms of polystyrene based on gel permeation chromatography). If the amount is less than the upper limit of the range, the solubility to a resist solvent sufficient for use as a resist is obtained, and if the amount is more than the lower limit of the range, the dry etching resistance and the cross-sectional shape of the resist pattern are good.
(F) The molecular weight distribution (Mw/Mn) of the component (B) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, most preferably 1.2 to 2.5.
In the resist composition of the present embodiment, 1 kind of the component (F) may be used alone, or 2 or more kinds may be used in combination.
When the resist composition contains the component (F), the content of the component (F) is usually 0.5 to 10 parts by mass per 100 parts by mass of the component (a).
(S) component: organic solvent composition
The resist composition of the present embodiment can be produced by dissolving a resist material in an organic solvent component (hereinafter also referred to as "S component").
The component (S) is not particularly limited as long as it can dissolve each component used to form a uniform solution, and any component may be appropriately selected from those conventionally known as solvents for chemically amplified resist compositions.
Examples of the component (S) include lactones such as γ -butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-amyl ketone, methyl isoamyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; derivatives of polyhydric alcohols such as compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, and compounds having an ether bond such as monomethyl ethers, monoethyl ethers, monopropyl ethers, monobutyl ethers, and the like of the polyhydric alcohols or the compounds having an ester bond [ among these, Propylene Glycol Monomethyl Ether Acetate (PGMEA), Propylene Glycol Monomethyl Ether (PGME) ]; cyclic ethers such as dioxane, esters such as methyl lactate, Ethyl Lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; aromatic organic solvents such as anisole, ethylbenzyl ether, methyltolyl ether, diphenyl ether, dibenzyl ether, phenetole, butylphenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, isopropyltoluene, mesitylene, and the like; dimethylsulfoxide (DMSO), and the like.
In the resist composition of the present embodiment, the component (S) may be used alone or in the form of a mixed solvent of 2 or more.
Among them, PGMEA, PGME, gamma-butyrolactone, EL, and cyclohexanone are preferable.
In addition, a mixed solvent obtained by mixing PGMEA with a polar solvent is also preferable. The blending ratio (mass ratio) thereof may be appropriately determined in consideration of compatibility of PGMEA with a polar solvent, and the like, and is preferably 1: 9-9: 1, more preferably 2: 8-8: 2, or a salt thereof.
More specifically, in the case of blending EL or cyclohexanone as a polar solvent, PGMEA: the mass ratio of EL or cyclohexanone is preferably 1: 9-9: 1, more preferably 2: 8-8: 2. further, in the case of blending PGME as a polar solvent, PGMEA: the mass ratio of PGME is preferably 1: 9-9: 1, more preferably 2: 8-8: 2, more preferably 3: 7-7: 3. in addition, a mixed solvent of PGMEA and PGME with cyclohexanone is also preferable.
In addition to the (S) component, a mixed solvent of γ -butyrolactone and at least 1 selected from PGMEA and EL is also preferable. In this case, the mixing ratio of the former to the latter is preferably 70: 30-95: 5.
since the concentration of the component (a) in the resist composition of the present embodiment is 20% by mass or more, the component (S) is used in an amount such that the concentration of the component (a) in the resist composition is 20% by mass or more.
The resist composition of the present embodiment may further contain additives having miscibility, for example, an additional resin for improving the performance of a resist film, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, an antihalation agent, a dye, and the like, as desired.
The resist composition of the present embodiment described above contains the component (a) and the tertiary monoamine compound (D0) represented by the general formula (D0). The content of the component (a) in the resist composition of the present embodiment is 20% by mass or more, and the content of the compound (D0) is 0.01 to 0.05 parts by mass with respect to 100 parts by mass of the component (a).
In the resist composition of the present embodiment, since the content of the component (a) is 20% by mass or more, a thick resist film having a film thickness of 5 μm or more can be formed when the resist film is formed by applying the composition to a substrate. In such a thick resist film, light hardly reaches the bottom during exposure, and sensitivity tends to be lowered. On the other hand, when the amount of the acid diffusion controller is reduced to maintain sensitivity, the in-plane uniformity (CDU) of the pattern size is deteriorated, and it is difficult to improve CDU while maintaining good sensitivity. In addition, in the thick film resist film, since light hardly reaches the bottom, it is difficult to form a resist pattern having a good shape.
The compound (D0) has a specific structure (tertiary monoamine represented by the general formula (D0)) and therefore has an appropriate acid diffusion controllability when applied to a resist composition for forming a thick resist film. This is presumably because nucleophilicity can be moderately hindered by steric hindrance caused by the arrangement of atoms around a nitrogen atom. It is presumed that the resist composition of the present embodiment can improve CDU at a small content within a specific range by using the compound (D0) having the above structure as an acid diffusion controller. Further, it is presumed that since the content is small in the specific range, deterioration of sensitivity can be suppressed.
It is also presumed that by using the compound (D0) in the specific range, the controllability of acid diffusion in the downward direction in the thick film resist film can be appropriately controlled at the time of exposure, and a resist pattern having a good shape can be formed.
By the above-described action, it is presumed that when a thick resist film having a film thickness of 5 μm or more is formed in the resist composition of the present embodiment, a resist pattern having a good shape can be formed by improving the lithographic characteristics such as CDU while maintaining good sensitivity.
(resist Pattern Forming method)
The invention of claim 2 is a resist pattern forming method, comprising: a step (i) of forming a resist film on a support using the resist composition of the above embodiment; a step (ii) of exposing the resist film; and (iii) developing the exposed resist film to form a resist pattern.
As an embodiment of the above-described resist pattern forming method, for example, a resist pattern forming method performed as described below can be exemplified.
Step (i):
first, the resist composition of the above embodiment is applied to a support by a spin coater or the like, and baked (pre-bake (PAB)) at a temperature of 80 to 150 ℃ for 40 to 120 seconds, preferably 60 to 90 seconds, to form a resist film.
Step (ii):
next, the resist film is selectively exposed to light through a mask (mask pattern) having a predetermined pattern formed thereon by using an exposure apparatus such as a KrF exposure apparatus, and then baked (post exposure bake (PEB)) at a temperature of 80 to 150 ℃ for 40 to 120 seconds, preferably 60 to 90 seconds.
Step (iii):
next, the exposed resist film is subjected to a development treatment. The development treatment is performed using an alkaline developer in the case of an alkaline development process, and is performed using an organic solvent-containing developer (organic developer) in the case of a solvent development process.
After the development treatment, a cleaning treatment is preferably performed. The cleaning treatment is preferably water cleaning using pure water in the case of an alkaline development process, and is preferably cleaning liquid containing an organic solvent in the case of a solvent development process.
In the case of the solvent development process, after the development treatment or the cleaning treatment, a treatment of removing the developing solution or the cleaning solution attached to the pattern by the supercritical fluid may be performed.
Drying is performed after the development treatment or after the cleaning treatment. In addition, a baking process (post-baking) may be performed after the above-described developing process according to circumstances.
As described above, a resist pattern can be formed.
The resist pattern forming method of the present embodiment will be described in detail below.
The support is not particularly limited, and conventionally known supports can be used, and examples thereof include a substrate for electronic components, a support having a predetermined wiring pattern formed thereon, and the like. More specifically, silicon wafers, substrates made of metal such as copper, chromium, iron, and aluminum, glass substrates, and the like can be cited. As a material of the wiring pattern, for example, copper, aluminum, nickel, gold, or the like can be used.
Further, as the support, an inorganic and/or organic film may be provided on the substrate as described above. As the inorganic film, an inorganic anti-reflection film (inorganic BARC) can be cited. Examples of the organic film include organic films such as an organic anti-reflection film (organic BARC) and an underlying organic film in a multilayer resist method.
Here, the multilayer resist method is a method in which at least one organic film (lower organic film) and at least one resist film (upper resist film) are provided on a substrate, and patterning of the lower organic film is performed using a resist pattern formed on the upper resist film as a mask, and it is considered that a pattern with a high aspect ratio can be formed. That is, according to the multilayer resist method, a desired thickness can be secured by the lower organic film, and therefore, the resist film can be thinned, and a fine pattern with a high aspect ratio can be formed.
Among the multilayer resist methods, there are basically classified into a method (2-layer resist method) using a two-layer structure of an upper resist film and a lower organic film; and a method (3-layer resist method) of a multilayer structure of three or more layers in which one or more intermediate layers (metal thin films and the like) are provided between an upper resist film and a lower organic film.
In the resist pattern forming method of the present embodiment, since the resist film is formed using the resist composition of the above-described embodiment, the film thickness of the resist film formed in the step (i) is 5 μm or more. The thickness of the resist film formed in step (i) is preferably 7 μm or more. The upper limit of the film thickness of the resist film is substantially 30 μm or less. The thickness of the resist film formed in the step (i) is, for example, in the range of 5 to 30 μm, preferably 7 to 20 μm, more preferably 7 to 15 μm, and still more preferably 8 to 10 μm.
The film thickness of the resist film can be adjusted according to the content of the component (a) in the resist composition used in the step (i). That is, a resist film having a higher thickness can be formed as the content of the component (a) in the resist composition is higher.
The wavelength used for the exposure is not particularly limited, and ArF excimer laser, KrF excimer laser, F excimer laser, and the like can be used2Excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, soft X-ray, and the like. The resist composition is highly useful for KrF excimer laser, ArF excimer laser, EB or EUV, is highly useful for KrF excimer laser, ArF excimer laser, and is particularly useful for KrF excimer laser. That is, the method for forming a resist pattern according to the present embodiment is particularly useful when the step of exposing the resist film includes an operation of exposing the resist film to KrF excimer laser light.
The resist film may be exposed to normal light in an inert gas such as air or nitrogen (dry exposure) or may be subjected to Liquid Immersion exposure (Liquid Immersion Lithography).
The liquid immersion exposure is an exposure method in which a space between a resist film and a lens at the lowermost position of an exposure apparatus is filled with a solvent (liquid immersion medium) having a refractive index larger than that of air in advance, and exposure is performed in this state (immersion exposure).
The immersion medium is preferably a solvent having a refractive index higher than that of air and lower than that of the resist film to be exposed. The refractive index of the solvent is not particularly limited within the above range.
Examples of the solvent having a refractive index higher than that of air and lower than that of the resist film include water, a fluorine-based inert liquid, a silicon-based solvent, and a hydrocarbon-based solvent.
Specific examples of the fluorine-based inert liquid include C3HCl2F5、C4F9OCH3、C4F9OC2H5、C5H3F7And liquids containing a fluorine-based compound as a main component, preferably a liquid having a boiling point of 70 to 180 ℃, more preferably a liquid having a boiling point of 80 to 160 ℃. When the fluorine-based inert liquid has a boiling point in the above range, it is preferable because the medium used in the immersion liquid can be removed by a simple method after the end of exposure.
As the fluorine-based inert liquid, a perfluoroalkyl compound in which all hydrogen atoms of the alkyl group are substituted by fluorine atoms is particularly preferable. Specific examples of the perfluoroalkyl compound include perfluoroalkyl ether compounds and perfluoroalkyl amine compounds.
More specifically, the perfluoroalkyl ether compound may be perfluoro (2-butyl-tetrahydrofuran) (boiling point: 102 ℃ C.), and the perfluoroalkyl amine compound may be perfluorotributylamine (boiling point: 174 ℃ C.).
As the immersion medium, water is preferably used from the viewpoints of cost, safety, environmental problems, versatility, and the like.
The alkaline developer used for the development treatment in the alkaline development process may be, for example, a 0.1 to 10 mass% aqueous tetramethylammonium hydroxide (TMAH) solution.
The organic solvent contained in the organic developer used for the development treatment in the solvent development process may be selected from known organic solvents as long as it is an organic solvent capable of dissolving the component (a) (component (a) before exposure). Specific examples thereof include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, and hydrocarbon solvents.
The ketone solvent is an organic solvent containing C — C (═ O) -C in the structure. The ester solvent is an organic solvent containing C — C (═ O) -O — C in the structure. The alcohol solvent is an organic solvent containing alcoholic hydroxyl groups in the structure. "Alcoholic hydroxyl group" means a hydroxyl group bonded to a carbon atom of an aliphatic hydrocarbon group. Nitrile solvents are organic solvents that contain nitrile groups in the structure. The amide-based solvent is an organic solvent containing an amide group in the structure. The ether solvent is an organic solvent containing C-O-C in the structure.
Among the organic solvents, there are also organic solvents having a structure containing a plurality of functional groups that are characteristic of the respective solvents, and in this case, the organic solvents are classified into all kinds of solvents having the functional groups at the same time. For example, diethylene glycol monomethyl ether also belongs to any of the alcohol-type organic solvents and ether-type organic solvents in the above classification.
The hydrocarbon solvent is a hydrocarbon solvent composed of a halogenated hydrocarbon and having no substituent other than a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a fluorine atom is preferable.
Among the above, the organic solvent contained in the organic developer is preferably a polar solvent, and preferably a ketone solvent, an ester solvent, a nitrile solvent, or the like.
Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethyl ketone, methylisobutyl ketone, acetylacetone, diacetone, ionone, diacetone alcohol, acetyl methanol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, γ -butyrolactone, and methyl amyl ketone (2-heptanone). Among these, methyl amyl ketone (2-heptanone) is preferred as the ketone solvent.
Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl, Propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4-methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl carbonate, butyl carbonate, methyl pyruvate, methyl acetate, ethyl formate, butyl formate, ethyl lactate, butyl acetate, ethyl formate, butyl formate, methyl pyruvate, ethyl, Ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, and the like. Among these, butyl acetate is preferable as the ester solvent.
Examples of the nitrile solvent include acetonitrile, propionitrile, valeronitrile, and butyronitrile.
The organic developer may be blended with known additives as needed. Examples of the additive include surfactants. The surfactant is not particularly limited, and for example, an ionic or nonionic fluorine-based and/or silicon-based surfactant can be used. The surfactant is preferably a nonionic surfactant, more preferably a nonionic fluorine-based surfactant or a nonionic silicon-based surfactant.
When the surfactant is blended, the blending amount thereof is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass, based on the total amount of the organic developer.
The developing treatment can be carried out by a known developing method, and examples thereof include a method of immersing the support in a developer for a certain period of time (immersion method), a method of supporting the developer on the surface of the support by surface tension and standing for a certain period of time (stirring (paddle) method), a method of spraying the developer on the surface of the support (spray method), and a method of continuously applying the developer to the support rotating at a certain speed while scanning a developer discharge nozzle at a certain speed (dynamic dispensing method).
As the organic solvent contained in the cleaning liquid used for the cleaning treatment after the development treatment in the solvent development process, for example, an organic solvent which is less likely to dissolve the resist pattern among the organic solvents listed as the organic solvents used for the organic developer can be appropriately selected and used. At least 1 solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is generally used. Among these, at least 1 kind selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, and amide solvents is preferable, at least 1 kind selected from alcohol solvents and ester solvents is more preferable, and alcohol solvents are particularly preferable.
The alcohol solvent used in the cleaning solution is preferably a monohydric alcohol having 6 to 8 carbon atoms, and the monohydric alcohol may be linear, branched or cyclic. Specific examples thereof include 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and benzyl alcohol. Among these, 1-hexanol, 2-heptanol, and 2-hexanol are preferred, and 1-hexanol and 2-hexanol are more preferred.
These organic solvents may be used alone, or 2 or more kinds may be used in combination. Further, the solvent may be used in combination with an organic solvent or water other than those mentioned above. However, in consideration of the developing property, the amount of water to be mixed in the cleaning liquid is preferably 30% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, and particularly preferably 3% by mass or less, based on the total amount of the cleaning liquid.
The cleaning liquid may contain known additives as needed. Examples of the additive include surfactants. Examples of the surfactant include the same surfactants as described above, preferably nonionic surfactants, more preferably nonionic fluorine surfactants, or nonionic silicon surfactants.
When the surfactant is blended, the blending amount thereof is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass, based on the total amount of the cleaning liquid.
The cleaning treatment (cleaning treatment) using the cleaning liquid can be performed by a known cleaning method. Examples of the method of the cleaning treatment include a method of continuously discharging a cleaning liquid onto a support rotating at a constant speed (spin coating method), a method of immersing the support in a cleaning liquid for a constant period of time (immersion method), and a method of spraying a cleaning liquid onto the surface of the support (spray method).
In the resist pattern forming method of the present embodiment described above, since the resist composition according to claim 1 is used, a resist pattern having more excellent lithographic characteristics (e.g., an improved CDU) can be formed with higher sensitivity when forming a resist pattern. Further, according to the resist pattern forming method, a resist pattern having a good shape can be formed.
The above-described resist pattern forming method is useful for manufacturing a three-dimensional structure device, and is a method preferable for use in processing a multi-level stepped structure (stacking, etc.). By applying the resist pattern forming method of the present invention, lamination of memory films can be realized with high accuracy (manufacturing of a three-dimensional, large-capacity memory).
[ examples ] A method for producing a compound
The present invention will be described in further detail with reference to examples below, but the present invention is not limited to these examples.
< preparation of resist composition >
The components shown in table 1 were mixed and dissolved to prepare resist compositions of respective examples (the content of the component (a): 35 mass%).
[ TABLE 1 ]
Figure BDA0002111803720001051
Figure BDA0002111803720001061
In table 1, the abbreviations have the following meanings. [] The numerical values in (b) are amounts (parts by mass) to be blended.
(A) -1: a polymer compound represented by the following chemical formula (A1-1). The polymer compound (A) -1 is obtained by radical polymerization of a monomer from which a structural unit constituting the polymer compound is derived at a predetermined molar ratio. The polymer compound (A) -1 had a mass average molecular weight (Mw) of 10000 and a molecular weight distribution (Mw/Mn) of about 2.0 in terms of polystyrene standards, which were determined by GPC measurement. By passing13The copolymerization composition ratio (the ratio of the respective structural units in the structural formula (molar ratio)) determined by C-NMR was 1/0.6/0.4.
[ CHEM 80 ]
Figure BDA0002111803720001071
(B) -1: an acid generator comprising the following compound (B-1).
(B) -2: an acid generator comprising the following compound (B-2).
[ CHEMICAL 81 ]
Figure BDA0002111803720001072
(D0) -1: an acid diffusion controlling agent comprising a compound represented by the following chemical formula (D0-1).
(D0) -2: an acid diffusion controlling agent comprising a compound represented by the following chemical formula (D0-2).
[ CHEM 82 ]
Figure BDA0002111803720001073
(D) -1: an acid diffusion controlling agent comprising a compound represented by the following chemical formula (D2-1).
(D) -2: an acid diffusion controlling agent comprising a compound represented by the following chemical formula (D2-2).
[ CHEM 83 ]
(S) -1: propylene glycol monomethyl ether/propylene glycol monomethyl ether acetate (mass ratio 80/20).
< method for Forming resist Pattern >
Step (i):
the resist compositions of the examples were applied to 8-inch silicon wafers by using a spin coater, and then Prebaked (PAB) treatment was performed on a hot plate at 140 ℃ for 120 seconds, followed by drying, thereby forming resist films having a thickness of 8 μm.
Step (ii):
next, the resist film was selectively irradiated with KrF excimer laser light (248nm) through a mask pattern (6% halftone) by a KrF exposure apparatus NSR-S203C (manufactured by nikon, inc.; NA (numerical aperture): 0.60, σ ═ 0.68).
Then, a post-exposure heating (PEB) treatment was performed at 110 ℃ for 90 seconds.
Step (iii):
next, alkaline development was carried out at 23 ℃ for 60 seconds using 2.38 mass% aqueous tetramethylammonium hydroxide (TMAH) solution "NMD-3" (trade name, manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a developer.
Then, the sheet was washed with water for 30 seconds using pure water, and then dried by spin drying.
As a result, an isolated line pattern (hereinafter referred to as "IS pattern") having a pitch width of 3 μm and a pitch of 15 μm was formed.
[ sensitivity ]
In the resist pattern forming method, the optimum exposure dose Eop (mJ/cm) for forming a target resist pattern is determined2) As the sensitivity. This was regarded as "sensitivity (mJ/cm)2) "is shown in Table 2.
[ uniformity of dimension (CDU) within the surface of the wafer (Shot) ]
The IS pattern (7X 15shot) formed by the resist pattern formation method was observed from above using a length measuring SEM (scanning Electron microscope, accelerated Voltage 300V, trade name: S-9380, manufactured by Hitachi high and New technology Co., Ltd.), and the interval width (38 dots in the shot) in the IS pattern was measured. A value (3 sigma) 3 times the standard deviation (sigma) calculated from the measurement result is obtained. The smaller the value of 3 σ thus obtained, the higher the uniformity of the dimension (CD) of the space width formed in the resist film. The results are shown in Table 2 as "CDU (nm)".
[ shape of resist Pattern ]
The shape of the IS pattern formed by the resist pattern formation method described above was observed by a length measuring SEM (scanning Electron microscope, accelerated Voltage 800V, trade name: SU-8000, manufactured by Hitachi high tech Co., Ltd.), and the evaluation results are shown in Table 2 as "shape" according to the following evaluation criteria.
Evaluation criteria
○ side walls of the pattern slope linearly
△ there is a protrusion in the slope of the pattern side wall
X: top-round shape, pattern sidewall recess, etc
[ TABLE 2]
Sensitivity (mJ/cm)2) CDU(nm) Shape of
Example 1 30 18 △
Example 2 45 10 ○
Example 3 65 12 ○
Example 4 32 19 △
Example 5 46 12 ○
Example 6 67 14 ○
Example 7 42 13 ○
Comparative example 1 7 37 ×
Comparative example 2 108 12 △
Comparative example 3 72 33 ×
Comparative example 4 79 31 ×
From the results shown in table 2, it was confirmed that the resist compositions of examples 1 to 7 to which the present invention was applied exhibited higher sensitivity and improved CDU performance as compared with the resist compositions of comparative examples 1 to 4. In examples 1 to 7, the resist pattern shape was also better than in comparative examples 1 to 4.

Claims (5)

1. A resist composition which generates an acid upon exposure and whose solubility in a developer changes by the action of the acid, characterized by comprising:
a base component (A) whose solubility in a developer changes due to the action of an acid;
a tertiary monoamine compound (D0) represented by the following general formula (D0),
the content of the base component (A) is 20% by mass or more,
the content of the compound (D0) is 0.01 to 0.05 parts by mass per 100 parts by mass of the base component (A),
[ CHEM 1 ]
Figure FDA0002111803710000011
In the formula, Rx1～Rx3Each independently represents a hydrocarbon group which may have a substituent; rx1～Rx3Or 2 or more of them may be bonded to each other to form a ring structure.
2. The resist composition according to claim 1, wherein the compound (D0) is a compound represented by the following general formula (D0-1) or (D0-2),
[ CHEM 2]
Figure FDA0002111803710000012
In the formula (d0-1), Rx11～Rx13Each independently represents a linear or branched alkyl group or an aromatic hydrocarbon group which may have a substituent, wherein Rx is11～Rx13Not all of which are aromatic hydrocarbon groups, in the formula (d0-2), Ry1～Ry3Represents a linear or branched alkyl group which may have a substituent, and nx1 represents an integer of 0 to 3.
3. The resist composition according to claim 1 or claim 2, further comprising an acid generator component (B) which generates an acid upon exposure.
4. A method of forming a resist pattern, comprising:
a step (i) of forming a resist film on a support by using the resist composition according to any one of claims 1 to 3;
a step (ii) of exposing the resist film;
and (iii) developing the exposed resist film to form a resist pattern.
5. The method of forming a resist pattern according to claim 4, wherein the resist film formed in the step (i) has a film thickness of 5 μm or more.
CN201910574756.XA 2018-07-11 2019-06-28 Resist composition and resist pattern forming method Pending CN110716390A (en)

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