Chemically amplified resist material and pattern formation method

Abstract

To provide a chemically amplified resist material which has high sensitivity and improved LWR and CDU regardless of whether it is positive or negative, and a pattern forming method using the same.SOLUTION: The chemically amplified resist material contains a quencher and an acid generator. The quencher contains a compound in which a hydrogen atom of a carboxy group of a nitrogen atom-containing carboxylic acid is substituted with a tertiary hydrocarbyl group having an androstane structure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a chemically amplified resist material and a patterning method. [Background technology]

[0002] As LSIs become more highly integrated and faster, pattern rules are becoming increasingly miniaturized. In particular, the expansion of the logic memory market due to the spread of smartphones is driving this miniaturization. Cutting-edge miniaturization technologies include the mass production of 7nm node devices using double patterning with ArF immersion lithography, and the mass production of 5nm node devices using extreme ultraviolet (EUV) lithography.

[0003] As miniaturization progresses and approaches the diffraction limit of light, the optical contrast decreases. This decrease in optical contrast causes a decrease in the resolution of hole and trench patterns and a decrease in focus margin in positive resist films. To prevent this decrease in resist pattern resolution, attempts are being made to improve the dissolution contrast of resist films.

[0004] For chemically amplified positive resist materials, which contain an acid generator and generate acid upon irradiation with light or an electron beam (EB), causing an acid-induced deprotection reaction, and for chemically amplified negative resist materials, which cause an acid-induced polarity change reaction or crosslinking reaction, the addition of a quencher to control the diffusion of acid into unexposed areas and improve contrast has been very effective. For this reason, many amine quenchers have been proposed (Patent Documents 1 to 3).

[0005] Patent Document 3 describes a resist material containing an amine compound having a tertiary ester-type acid labile group. Deprotection of the acid labile group improves the alkaline dissolution rate of not only the base polymer but also the amine quencher, thereby improving dissolution contrast.

[0006] Resist materials for EB or EUV lithography, which require the formation of ultrafine patterns, require not only improved dissolution contrast but also unprecedented control of acid diffusion. The amine quenchers described in the aforementioned Patent Documents 1 to 3 lack the ability to control acid diffusion. There is a need for the development of new materials that can achieve low acid diffusion and high contrast. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2001-194776 [Patent Document 2] Japanese Patent Application Laid-Open No. 2002-226470 [Patent Document 3] Japanese Patent Application Laid-Open No. 2002-363148 Summary of the Invention [Problem to be solved by the invention]

[0008] For acid-catalyzed chemically amplified resist materials, the development of a quencher that can improve the LWR of line patterns and the CDU of hole patterns while also improving sensitivity is desired. To achieve this, it is necessary to further reduce the diffusion distance of the acid and simultaneously improve contrast, which are contradictory properties that must be improved.

[0009] The present invention has been made in view of the above circumstances, and aims to provide a chemically amplified resist material that is highly sensitive and has improved LWR and CDU, whether positive or negative, and a pattern formation method using the same. [Means for solving the problem]

[0010] As a result of extensive research into achieving the above-mentioned object, the present inventors have found that by adding a compound in which the hydrogen atom of the carboxy group of a nitrogen-containing carboxylic acid is substituted with a tertiary hydrocarbyl group having an androstane structure as a quencher to a chemically amplified resist material containing an acid generator, the resist film has high acid diffusion control ability due to the large acid labile group having an androstane structure, and the dissolution contrast is improved by deprotection of the acid labile group, thereby preventing film loss after development, and by improving the solubility of exposed areas, particularly in positive resists, it is possible to obtain a resist film with improved LWR and CDU, thereby completing the present invention.

[0011] That is, the present invention provides the following chemically amplified resist material and pattern forming method. 1. A chemically amplified resist material comprising a quencher and an acid generator, wherein the quencher comprises a compound in which the hydrogen atom of the carboxy group of a nitrogen-containing carboxylic acid is substituted with a tertiary hydrocarbyl group having an androstane structure. 2. The chemically amplified resist material of 1, wherein the compound in which the hydrogen atom of the carboxy group of the nitrogen-containing carboxylic acid is substituted with a tertiary hydrocarbyl group having an androstane structure is represented by the following formula (1): [ka] [In the formula, m is an integer of 1 to 3.] R 1 is a hydrogen atom, an aliphatic hydrocarbyl group having 1 to 14 carbon atoms, an aliphatic hydrocarbyloxycarbonyl group having 2 to 14 carbon atoms, an aliphatic hydrocarbylcarbonyl group having 2 to 10 carbon atoms, or an aralkyl group having 7 to 14 carbon atoms. When m is 1, two R 1 may be the same or different, and two R 1may be bonded to each other to form a ring together with the nitrogen atom to which they are bonded, and some of the hydrogen atoms in the ring may be substituted with a halogen atom, a saturated hydrocarbyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, or a phenyl group which may be substituted with a halogen atom, and the ring may contain an ether bond, an ester bond, a sulfide bond, a sulfonyl group, -N= and -N(R 1 )-. R 2 is a single bond or an aliphatic or aromatic hydrocarbylene group having 1 to 10 carbon atoms, and the aliphatic hydrocarbylene group may contain at least one bond selected from a halogen atom, an ether bond, an ester bond, and a sulfide bond, and the aromatic hydrocarbylene group may contain at least one bond selected from a halogen atom, —N(R 2A )(R 2B ), -N(R 2C )-C(=O)-R 2D and -N(R 2C )-C(=O)-OR 2D R 2A and R 2B are each independently a hydrogen atom or a saturated hydrocarbyl group having 1 to 6 carbon atoms. 2C is a hydrogen atom or a saturated hydrocarbyl group having 1 to 6 carbon atoms, and may contain a halogen atom, a hydroxy group, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, a saturated hydrocarbylcarbonyl group having 2 to 6 carbon atoms, or a saturated hydrocarbylcarbonyloxy group having 2 to 6 carbon atoms. 2D is an aliphatic hydrocarbyl group having 1 to 16 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 15 carbon atoms, and may contain a halogen atom, a hydroxy group, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, a saturated hydrocarbylcarbonyl group having 2 to 6 carbon atoms, or a saturated hydrocarbylcarbonyloxy group having 2 to 6 carbon atoms. When m is 1, R 1 and R 2and may be bonded to each other to form a ring together with the nitrogen atom to which they are bonded, and some of the hydrogen atoms of the ring may be substituted with a halogen atom, a saturated hydrocarbyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, or a phenyl group which may be substituted with a halogen atom, and the ring may contain at least one bond selected from an ether bond, an ester bond, a sulfide bond, a sulfonyl group, and -N=, and the remaining R 1 and a carbon atom contained in the ring may be bonded to form a bridged ring. 2 may be the same or different from each other. X 1 is a single bond, an ether bond, an ester bond, an amide bond, or a thioester bond. When m is 2 or 3, each X 1 may be the same or different from each other. X 2 is a single bond or a hydrocarbylene group having 1 to 12 carbon atoms, and the hydrocarbylene group may contain at least one bond selected from an ether bond, an ester bond, a sulfide bond, a cyano group, a nitro group, a sulfonyl group, a sultone ring, a lactone ring, and a halogen atom. 2 may be the same or different from each other. R is a group containing a structure represented by the following formula (2): When m is 2 or 3, each R may be the same or different. [ka] (In the formula, R 3 is an aliphatic hydrocarbyl group having 1 to 6 carbon atoms which may contain a heteroatom, or a phenyl group which may be substituted with a halogen atom. The ring in the formula may contain a double bond.) 3. The chemically amplified resist material of 2, wherein R is a group represented by any one of the following formulas (2)-1 to (2)-8: [ka] (In the formula, R 3is an aliphatic hydrocarbyl group having 1 to 6 carbon atoms which may contain a hetero atom, or a phenyl group which may be substituted with a halogen atom. R 4 and R 5 are each independently a hydrogen atom, a hydroxy group, a saturated hydrocarbyl group having 1 to 6 carbon atoms, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, a saturated hydrocarbylcarbonyloxy group having 2 to 6 carbon atoms, a saturated hydrocarbylsulfonyloxy group having 1 to 6 carbon atoms, an oxo group, or an amino group; R 4 and R 5 may be bonded to each other to form a ring together with the carbon atom to which they are attached, and the ring may contain an ether bond, -N(H)-, -N= or a double bond. R 6 represents a hydrogen atom, a hydroxy group, a saturated hydrocarbyl group having 1 to 6 carbon atoms, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, a saturated hydrocarbylcarbonyloxy group having 2 to 6 carbon atoms, or a saturated hydrocarbylsulfonyloxy group having 1 to 6 carbon atoms. R 7 is a methyl group or an ethyl group. n is 1 or 2. The dashed lines represent bonds.) 4. The chemically amplified resist material of any one of 1 to 3, wherein the acid generator generates a sulfonic acid, an imide acid, or a methide acid. 5. A chemically amplified resist material according to any one of 1 to 4, further comprising a base polymer. 6. The chemically amplified resist material according to 5, wherein the base polymer contains a repeating unit represented by the following formula (a1) or a repeating unit represented by the following formula (a2): [ka] (In the formula, R A are each independently a hydrogen atom or a methyl group. R 11 and R 12 are each independently an acid labile group. Y 1is a linking group having 1 to 12 carbon atoms and containing at least one selected from a single bond, a phenylene group, a naphthylene group, an ester bond, and a lactone ring. Y 2 is a single bond or an ester bond. 7. The chemically amplified resist material of 6, which is a chemically amplified positive resist material. 8. The chemically amplified resist material of 5, wherein the base polymer does not contain any acid labile groups. 9. The chemically amplified resist material of 8, which is a chemically amplified negative resist material. 10. The chemically amplified resist material of any one of 5 to 9, wherein the base polymer contains a repeating unit represented by any one of the following formulas (f1) to (f3): [ka] (In the formula, R A are each independently a hydrogen atom or a methyl group. Z 1 represents a single bond, an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a naphthylene group, or a group having 7 to 18 carbon atoms obtained by combining these, or -OZ 11 -, -C(=O)-OZ 11 - or -C(=O)-NH-Z 11 -It is. Z 11 represents an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a naphthylene group, or a group having 7 to 18 carbon atoms obtained by combining these, and may contain a carbonyl group, an ester bond, an ether bond, or a hydroxy group. Z 2 is a single bond, -Z 21 -C(=O)-O-, -Z 21 -O- or -Z 21 -OC(=O)-. Z 21 is a saturated hydrocarbylene group having 1 to 12 carbon atoms, which may contain a carbonyl group, an ester bond or an ether bond. Z 3represents a single bond, a methylene group, an ethylene group, a phenylene group, a fluorinated phenylene group, a phenylene group substituted with a trifluoromethyl group, -OZ 31 -, -C(=O)-OZ 31 - or -C(=O)-NH-Z 31 -It is. Z 31 represents an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a fluorinated phenylene group, or a phenylene group substituted with a trifluoromethyl group, and may contain a carbonyl group, an ester bond, an ether bond, or a hydroxy group. R 21 ~R 28 are each independently a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. 23 and R 24 or R 26 and R 27 may be bonded to each other to form a ring together with the sulfur atom to which they are attached. R HF is a hydrogen atom or a trifluoromethyl group. M - is a non-nucleophilic counterion. 11. The chemically amplified resist material of any one of 1 to 10, further comprising an organic solvent. 12. The chemically amplified resist material according to any one of 1 to 11, further comprising a surfactant. 13. A pattern forming method comprising the steps of forming a resist film on a substrate using a chemically amplified resist material according to any one of claims 1 to 12, exposing the resist film to high-energy radiation, and developing the exposed resist film using a developer. 14. The pattern formation method of 13, wherein the high-energy radiation is i-rays with a wavelength of 365 nm, ArF excimer laser light with a wavelength of 193 nm, KrF excimer laser light with a wavelength of 248 nm, EB, or EUV with a wavelength of 3 to 15 nm. [Effects of the Invention]

[0012] The compound contained in the quencher is a compound in which the hydrogen atom of the carboxy group of a nitrogen atom-containing carboxylic acid is substituted with a tertiary hydrocarbyl group having an androstane structure, and therefore has a high effect of suppressing acid diffusion due to the acid labile group having a bulky androstane structure, and the dissolution contrast can be improved by the deprotection reaction of the acid labile group. and The quencher containing the compound is particularly effective in positive resist materials, because it can achieve high contrast, and the developed pattern has small LWR and improved CDU. DETAILED DESCRIPTION OF THE INVENTION

[0013] [Chemically amplified resist materials] The chemically amplified resist material of the present invention comprises a quencher containing a compound (hereinafter also referred to as Compound A) in which the hydrogen atom of the carboxyl group of a nitrogen-containing carboxylic acid is substituted with a tertiary hydrocarbyl group having an androstane structure, and an acid generator. The tertiary hydrocarbyl group refers to a group obtained by eliminating a hydrogen atom from a tertiary carbon atom of a hydrocarbon. Compound A neutralizes the acid generated from the acid generator while simultaneously generating a carboxylic acid through a deprotection reaction, thereby improving the alkali solubility of the exposed area. The acid labile group having an androstane structure is highly effective in suppressing acid diffusion, and furthermore, the presence of a nitrogen atom in the molecule allows for high acid diffusion control. This reduces the acid diffusion distance while improving dissolution contrast, enabling the formation of patterns with improved LWR and CDU after development.

[0014] The acid diffusion suppression effect, contrast improvement effect, and LWR and CDU reduction effect of Compound A are effective in both positive pattern formation and negative pattern formation by alkaline aqueous solution development and negative pattern formation by organic solvent development.

[0015] [Quencher] The quencher contained in the chemically amplified resist material of the present invention comprises a compound A in which the hydrogen atom of the carboxyl group of a nitrogen-containing carboxylic acid is substituted with a tertiary hydrocarbyl group having an androstane structure. Compound A is particularly preferably one represented by the following formula (1): [ka]

[0016] In formula (1), m is an integer of 1 to 3.

[0017] In formula (1), R 1 is a hydrogen atom, an aliphatic hydrocarbyl group having 1 to 14 carbon atoms, an aliphatic hydrocarbyloxycarbonyl group having 2 to 14 carbon atoms, an aliphatic hydrocarbylcarbonyl group having 2 to 10 carbon atoms, or an aralkyl group having 7 to 14 carbon atoms. When m is 1, two R 1 may be the same or different from each other.

[0018] R 1The aliphatic hydrocarbyl group having 1 to 14 carbon atoms represented by the following formula (I), the aliphatic hydrocarbyl moiety of the aliphatic hydrocarbyloxycarbonyl group and the aliphatic hydrocarbylcarbonyl group may be saturated or unsaturated, and may be linear, branched or cyclic. Specific examples thereof include alkyl groups having 1 to 14 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a tert-pentyl group, a neopentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, an n-decyl group, an undecyl group, a dodecyl group, a tridecyl group, and a tetradecyl group; a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a cyclopropylmethyl group, a cyclopropylethyl group, a cyclobutylmethyl group, a cyclobutylethyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, adamantylmethyl group, a norbornylmethyl group, and a methylcyclopropyl group. C cyclic saturated hydrocarbyl groups such as methylcyclobutyl, methylcyclopentyl, methylcyclohexyl, ethylcyclopropyl, ethylcyclobutyl, ethylcyclopentyl, and ethylcyclohexyl groups; C cyclic saturated hydrocarbyl groups such as vinyl, 1-propenyl, 2-propenyl, butenyl, pentenyl, hexenyl, heptenyl, nonenyl, and decenyl groups; C cyclic saturated hydrocarbyl groups such as ethynyl, propynyl, and methylcyclohexyl groups; Examples of such groups include alkynyl groups having 2 to 14 carbon atoms, such as cyclopentenyl, cyclohexenyl, methylcyclopentenyl, methylcyclohexenyl, ethylcyclopentenyl, ethylcyclohexenyl, and norbornenyl; and groups obtained by combining these groups.

[0019] R 1 Examples of the aralkyl group having 7 to 14 carbon atoms represented by the formula (I) include a benzyl group, a 1-phenylethyl group, and a 2-phenylethyl group.

[0020] In formula (1), R 2 is a single bond or an aliphatic or aromatic hydrocarbylene group having 1 to 10 carbon atoms, and the aliphatic hydrocarbylene group may contain at least one bond selected from a halogen atom, an ether bond, an ester bond, and a sulfide bond, and the aromatic hydrocarbylene group may contain at least one bond selected from a halogen atom, —N(R 2A )(R 2B ), -N(R 2C )-C(=O)-R 2D and -N(R 2C )-C(=O)-OR 2D R 2A and R 2B are each independently a hydrogen atom or a saturated hydrocarbyl group having 1 to 6 carbon atoms. 2C is a hydrogen atom or a saturated hydrocarbyl group having 1 to 6 carbon atoms, and may contain a halogen atom, a hydroxy group, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, a saturated hydrocarbylcarbonyl group having 2 to 6 carbon atoms, or a saturated hydrocarbylcarbonyloxy group having 2 to 6 carbon atoms. 2D is an aliphatic hydrocarbyl group having 1 to 16 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 15 carbon atoms, and may contain a halogen atom, a hydroxy group, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, a saturated hydrocarbylcarbonyl group having 2 to 6 carbon atoms, or a saturated hydrocarbylcarbonyloxy group having 2 to 6 carbon atoms. When m is 2 or 3, each R 2 may be the same or different from each other.

[0021] R 2The aliphatic or aromatic hydrocarbylene group represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkane diyl groups having 1 to 10 carbon atoms, such as methanediyl group, ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,1-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, propane-2,2-diyl group, butane-1,1-diyl group, butane-1,2-diyl group, butane-1,3-diyl group, butane-2,3-diyl group, butane-1,4-diyl group, 1,1-dimethylethane-1,2-diyl group, pentane-1,5-diyl group, 2-methylbutane-1,2-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, and decane-1,10-diyl group. cycloalkyl groups; saturated cyclic hydrocarbylene groups having 3 to 10 carbon atoms, such as a cyclopropanediyl group, a cyclobutanediyl group, a cyclopentanediyl group, a cyclohexanediyl group, an adamantanediyl group, or a norbornanediyl group; alkenediyl groups having 2 to 10 carbon atoms, such as a vinylene group, a propene-1,3-diyl group, or a butene-1,4-diyl group; alkynediyl groups having 2 to 10 carbon atoms, such as an ethyne-1,2-diyl group, a propyne-1,3-diyl group, or a butyne-1,4-diyl group; unsaturated cyclic aliphatic hydrocarbylene groups having 3 to 10 carbon atoms, such as a cyclopentenediyl group or a cyclohexenediyl group; arylene groups, such as a phenylene group or a naphthylene group; and groups obtained by combining these.

[0022] Also, when m is 1, two R 1 may be bonded to each other to form a ring together with the nitrogen atom to which they are bonded, and some of the hydrogen atoms in the ring may be substituted with a halogen atom, a saturated hydrocarbyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, or a phenyl group which may be substituted with a halogen atom, and the ring may contain an ether bond, an ester bond, a sulfide bond, a sulfonyl group, -N= and -N(R 1 When m is 1, R 1 and R 2and may be bonded to each other to form a ring together with the nitrogen atom to which they are bonded, and some of the hydrogen atoms of the ring may be substituted with a halogen atom, a saturated hydrocarbyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, or a phenyl group which may be substituted with a halogen atom, and the ring may contain at least one bond selected from an ether bond, an ester bond, a sulfide bond, a sulfonyl group, and -N=, and the remaining R 1 and a carbon atom contained in the ring may be bonded to form a bridged ring.

[0023] The nitrogen atom-containing ring is preferably a heterocyclic ring having 3 to 12 carbon atoms, which may be saturated or unsaturated, and may be a monocyclic or polycyclic ring. In the case of a polycyclic ring, a fused ring or a bridged ring is preferable. Specific examples of the heterocyclic ring include an aziridine ring, an azirine ring, an azetidine ring, an azeto ring, a pyrrolidine ring, a pyrroline ring, a pyrrole ring, a piperidine ring, a tetrahydropyridine ring, a pyridine ring, an azepane ring, an azocane ring, an azanorbornane ring, an azaadamantane ring, a tropane ring, a quinuclidine ring, an oxazolidine ring, a thiazolidine ring, a morpholine ring, a thiomorpholine ring, a pyrazolidine ring, an imidazolidine ring, a pyrazoline ring, an imidazoline ring, a pyrazole ring, an imidazole ring, Preferred are a triazole ring, a tetrazole ring, a pyrazine ring, a triazine ring, an indoline ring, an indole ring, an isoindole ring, a pyrimidine ring, an indolizine ring, a benzimidazole ring, an azaindole ring, an azaindazole ring, a purine ring, a tetrahydroquinoline ring, a tetrahydroisoquinoline ring, a decahydroquinoline ring, a decahydroisoquinoline ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, a phthalazine ring, a quinazoline ring, a cinnoline ring, a carbazole ring, and the like.

[0024] In formula (1), X 1 is a single bond, an ether bond, an ester bond, an amide bond, or a thioester bond. When m is 2 or 3, each X 1 may be the same or different from each other.

[0025] In formula (1), X 2is a single bond or a hydrocarbylene group having 1 to 12 carbon atoms, and the hydrocarbylene group may contain at least one bond selected from an ether bond, an ester bond, a sulfide bond, a cyano group, a nitro group, a sulfonyl group, a sultone ring, a lactone ring, and a halogen atom. 2 may be the same or different from each other.

[0026] X 2The hydrocarbylene group having 1 to 12 carbon atoms represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include a methanediyl group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, a propane-2,2-diyl group, a butane-1,1-diyl group, a butane-1,2-diyl group, a butane-1,3-diyl group, a butane-2,3-diyl group, a butane-1,4-diyl group, a 1,1-dimethylethane-1,2-diyl group, a pentane alkanediyl groups having 1 to 12 carbon atoms, such as 1,5-diyl, 2-methylbutane-1,2-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; cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, and cyclohexanediyl groups; cyclic saturated hydrocarbylene groups having 3 to 12 carbon atoms, such as vinylene, adamantanediyl, and norbornanediyl groups; alkenediyl groups having 2 to 12 carbon atoms, such as vinylene, propene-1,3-diyl, and butene-1,4-diyl groups; alkynediyl groups having 2 to 12 carbon atoms, such as ethyne-1,2-diyl, propyne-1,3-diyl, and butyne-1,4-diyl groups; cyclopentenediyl groups and cyclohexenediyl groups; Examples of the alkylene group include cyclic unsaturated aliphatic hydrocarbylene groups; arylene groups having 6 to 12 carbon atoms such as phenylene group, methylphenylene group, ethylphenylene group, n-propylphenylene group, isopropylphenylene group, n-butylphenylene group, isobutylphenylene group, sec-butylphenylene group, tert-butylphenylene group, naphthylene group, methylnaphthylene group, and ethylnaphthylene group; and groups obtained by combining these groups.

[0027] In formula (1), R is a group containing a structure represented by the following formula (2): When m is 2 or 3, each R may be the same or different. [ka]

[0028] In formula (2), R 3 is an aliphatic hydrocarbyl group having 1 to 6 carbon atoms which may contain a heteroatom, or a phenyl group which may be substituted with a halogen atom. The ring in the formula may contain a double bond. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0029] R 3 The aliphatic hydrocarbyl group having 1 to 6 carbon atoms represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include R 1 Among the examples of the aliphatic hydrocarbyl group represented by the following formula, those having 1 to 6 carbon atoms can be mentioned.

[0030] R is preferably a group represented by any one of the following formulas (2)-1 to (2)-8. [ka]

[0031] In formulas (2)-1 to (2)-8, R 3 R is an aliphatic hydrocarbyl group having 1 to 6 carbon atoms which may contain a heteroatom, or a phenyl group which may be substituted with a halogen atom. 4 and R 5 are each independently a hydrogen atom, a hydroxy group, a saturated hydrocarbyl group having 1 to 6 carbon atoms, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, a saturated hydrocarbylcarbonyloxy group having 2 to 6 carbon atoms, a saturated hydrocarbylsulfonyloxy group having 1 to 6 carbon atoms, an oxo group, or an amino group; R 4 and R 5 and may be bonded to each other to form a ring together with the carbon atoms to which they are attached, and the ring may contain an ether bond, -N(H)-, -N= or a double bond. 6R is a hydrogen atom, a hydroxy group, a saturated hydrocarbyl group having 1 to 6 carbon atoms, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, a saturated hydrocarbylcarbonyloxy group having 2 to 6 carbon atoms, or a saturated hydrocarbylsulfonyloxy group having 1 to 6 carbon atoms. 7 is a methyl group or an ethyl group. n is 1 or 2. The dashed line is a bond.

[0032] R 4 , R 5 and R 6 The saturated hydrocarbyl group represented by the formula (I) and the saturated hydrocarbyl moiety of the saturated hydrocarbyloxy group, saturated hydrocarbylcarbonyloxy group, and saturated hydrocarbylsulfonyloxy group may be linear, branched, or cyclic, and specific examples thereof include alkyl groups such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, and n-hexyl group; and cyclic saturated hydrocarbyl groups such as a cyclopentyl group and cyclohexyl group.

[0033] Examples of groups represented by R include, but are not limited to, the following: In the following formula, the dashed lines represent bonds. [ka]

[0034] [ka]

[0035] [ka]

[0036] [ka]

[0037] [ka]

[0038] [ka]

[0039] [ka]

[0040] [ka]

[0041] [ka]

[0042] [ka]

[0043] [ka]

[0044] [ka]

[0045] [ka]

[0046] [ka]

[0047] Compound A includes, but is not limited to, the following: In the following formula, R and R 1 is the same as above.

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069] [ka]

[0070] [ka]

[0071] [ka]

[0072] [ka]

[0073] [ka]

[0074] [ka]

[0075] Compound A has a structure in which the hydrogen atom of the carboxyl group of a nitrogen-containing carboxylic acid is substituted with a tertiary hydrocarbyl group having an androstane structure. This allows for low acid diffusion and high contrast to be achieved through the acid trapping ability of the nitrogen atom through acid neutralization, the acid diffusion control ability of the bulky androstane structure, and the acid deprotection reaction of the acid-labile group with acid. This allows for improved LWR or CDU.

[0076] Compound A can be obtained, for example, by an esterification reaction between a nitrogen atom-containing carboxylic acid compound and a tertiary alcohol having an androstane structure.

[0077] The chemically amplified resist material of the present invention containing Compound A can be patterned even without a base polymer, but can also be blended with a base polymer. When the chemically amplified resist material of the present invention contains a base polymer, the content of the quencher composed of Compound A is preferably 0.001 to 50 parts by mass, more preferably 0.01 to 20 parts by mass, per 100 parts by mass of the base polymer described below, from the viewpoints of sensitivity and acid diffusion suppression effect. Compound A may be used alone or in combination of two or more types.

[0078] The quencher may include a quencher other than Compound A (hereinafter referred to as "other quenchers"). Examples of other quenchers include conventional basic compounds. Examples of conventional basic compounds include primary, secondary, and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amides, imides, and carbamates. In particular, the primary, secondary, and tertiary amine compounds described in paragraphs

[0146] to

[0164] of JP 2008-111103 A are preferred, including amine compounds having a hydroxyl group, an ether bond, an ester bond, a lactone ring, a cyano group, or a sulfonate ester bond, and compounds having a carbamate group described in Japanese Patent No. 3790649 A. By adding such a basic compound, for example, it is possible to further suppress the diffusion rate of the acid in the resist film and correct the shape.

[0079] Other examples of quenchers include the polymer-type quenchers described in JP 2008-239918 A. These quenchers enhance the rectangularity of resist patterns by orienting on the surface of the resist film. Polymer-type quenchers also have the effect of preventing pattern thinning and rounding of the pattern top when a protective film for immersion lithography is applied.

[0080] Alternatively, an ammonium salt, a sulfonium salt, or an iodonium salt may be added as a quencher. In this case, the ammonium salt, sulfonium salt, or iodonium salt added as a quencher is preferably a salt of a carboxylic acid, a sulfonic acid, a sulfonimide, or a saccharin. In this case, the carboxylic acid may or may not be fluorinated at the α-position.

[0081] Examples of such quenchers include compounds represented by the following formula (q1) (onium salts of sulfonic acids not fluorinated at the α-position), compounds represented by the following formula (q2) (onium salts of carboxylic acids), and compounds represented by the following formula (q3) (onium salts of alkoxides). [ka]

[0082] In formula (q1), R q1 represents a hydrocarbyl group having 1 to 40 carbon atoms which may contain a hydrogen atom or a heteroatom, but excludes those in which the hydrogen atom bonded to the carbon atom at the α-position of the sulfo group is substituted with a fluorine atom or a fluoroalkyl group.

[0083] R q1 The hydrocarbyl group having 1 to 40 carbon atoms represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 40 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, tert-pentyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, and tricyclo[5.2.1.0]. 2,6]Cyclic saturated hydrocarbyl groups having 3 to 40 carbon atoms such as decanyl group, adamantyl group, and adamantylmethyl group; C2 to 40 alkenyl groups such as vinyl group, allyl group, propenyl group, butenyl group, and hexenyl group; C3 to 40 unsaturated aliphatic hydrocarbyl groups such as cyclohexenyl group; phenyl group, naphthyl group, alkylphenyl group (2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-tert-butyl ... Examples of the alkyl groups include aryl groups having 6 to 40 carbon atoms, such as aryl groups (e.g., t-butylphenyl group, 4-n-butylphenyl group), dialkylphenyl groups (e.g., 2,4-dimethylphenyl group, 2,4,6-triisopropylphenyl group), alkylnaphthyl groups (e.g., methylnaphthyl group, ethylnaphthyl group), and dialkylnaphthyl groups (e.g., dimethylnaphthyl group, diethylnaphthyl group); and aralkyl groups having 7 to 40 carbon atoms, such as benzyl group, 1-phenylethyl group, and 2-phenylethyl group.

[0084] Furthermore, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom or a halogen atom, and some of the -CH- groups of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom, and as a result, the hydrocarbyl group may contain a hydroxy group, a cyano group, a carbonyl group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-OC(=O)-), a haloalkyl group, etc. Examples of the hydrocarbyl group containing a heteroatom include heteroaryl groups such as a thienyl group; alkoxyphenyl groups such as a 4-hydroxyphenyl group, a 4-methoxyphenyl group, a 3-methoxyphenyl group, a 2-methoxyphenyl group, a 4-ethoxyphenyl group, a 4-tert-butoxyphenyl group, and a 3-tert-butoxyphenyl group; alkoxynaphthyl groups such as a methoxynaphthyl group, an ethoxynaphthyl group, an n-propoxynaphthyl group, and an n-butoxynaphthyl group; dialkoxynaphthyl groups such as a dimethoxynaphthyl group and a diethoxynaphthyl group; and aryloxoalkyl groups such as a 2-aryl-2-oxoethyl group, a 2-(1-naphthyl)-2-oxoethyl group, and a 2-(2-naphthyl)-2-oxoethyl group.

[0085] In formula (q2), R q2 R is a hydrocarbyl group having 1 to 40 carbon atoms which may contain a heteroatom. q2 Examples of the hydrocarbyl group represented by R q1

[0039] Other specific examples include fluorine-containing alkyl groups such as a trifluoromethyl group, a trifluoroethyl group, a 2,2,2-trifluoro-1-methyl-1-hydroxyethyl group, and a 2,2,2-trifluoro-1-(trifluoromethyl)-1-hydroxyethyl group; and fluorine-containing aryl groups such as a pentafluorophenyl group and a 4-trifluoromethylphenyl group.

[0086] In formula (q3), R q3represents a saturated hydrocarbyl group having 1 to 8 carbon atoms and at least three fluorine atoms, or an aryl group having 6 to 10 carbon atoms and at least three fluorine atoms, and the saturated hydrocarbyl group and aryl group may contain a nitro group.

[0087] In formulas (q1), (q2) and (q3), Mq + is an onium cation. The onium cation is preferably a sulfonium cation, an iodonium cation, or an ammonium cation, and more preferably a sulfonium cation. Examples of the sulfonium cation include the sulfonium cations described in JP-A-2017-219836.

[0088] As the quencher, a sulfonium salt of an iodinated benzene ring-containing carboxylic acid represented by the following formula (q4) can also be suitably used. [ka]

[0089] In formula (q4), R q11 represents a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an amino group, a nitro group, a cyano group, or a saturated hydrocarbyl group having 1 to 6 carbon atoms, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, a saturated hydrocarbylcarbonyloxy group having 2 to 6 carbon atoms, or a saturated hydrocarbylsulfonyloxy group having 1 to 4 carbon atoms, in which some or all of the hydrogen atoms may be substituted with halogen atoms, or -N(R q11A )-C(=O)-R q11B or -N(R q11A )-C(=O)-OR q11B R q101A is a hydrogen atom or a saturated hydrocarbyl group having 1 to 6 carbon atoms. q11B is a saturated hydrocarbyl group having 1 to 6 carbon atoms or an unsaturated aliphatic hydrocarbyl group having 2 to 8 carbon atoms.

[0090] In formula (q4), x' is an integer of 1 to 5. y' is an integer of 0 to 3. z' is an integer of 1 to 3. LA is a single bond or a (z'+1)-valent linking group having 1 to 20 carbon atoms, and may contain at least one selected from an ether bond, a carbonyl group, an ester bond, an amide bond, a sultone ring, a lactam ring, a carbonate bond, a halogen atom, a hydroxy group, and a carboxy group. The saturated hydrocarbyl group, saturated hydrocarbyloxy group, saturated hydrocarbylcarbonyloxy group, and saturated hydrocarbylsulfonyloxy group may be linear, branched, or cyclic. When y' and / or z' is 2 or more, each R q11 may be the same or different from each other.

[0091] In formula (q4), R q12 , R q13 and R q14 are each independently a hydrocarbyl group having 1 to 20 carbon atoms which may contain a halogen atom or a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include R in formula (3) described below. 101 ~R 103 Examples of the hydrocarbyl group include the same as those exemplified above. In addition, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a hydroxy group, a carboxy group, a halogen atom, an oxo group, a cyano group, a nitro group, a sultone ring, a sulfo group, or a sulfonium salt-containing group, and some of the -CH2- groups of the hydrocarbyl group may be substituted with an ether bond, an ester bond, a carbonyl group, an amide bond, a carbonate bond, or a sulfonate ester bond. q12 and R q13 and may be bonded to each other to form a ring together with the sulfur atom to which they are attached.

[0092] Specific examples of the compound represented by formula (q4) include those described in JP 2017-219836 A and JP 2021-91666 A.

[0093] When the chemically amplified resist material of the present invention contains other quenchers, the content thereof is preferably 0 to 5 parts by mass, more preferably 0 to 4 parts by mass, relative to 100 parts by mass of the base polymer described below. The other quenchers may be used alone or in combination of two or more.

[0094] [Acid generator] The chemically amplified resist material of the present invention contains an acid generator. The acid generator may be an additive-type acid generator different from the quencher or each component described below, or may be one that also functions as a base polymer described below, in other words, a polymer-bound acid generator that also serves as a base polymer.

[0095] The additive-type acid generator is preferably a compound (photoacid generator) that generates an acid in response to actinic rays or radiation. The photoacid generator may be any compound that generates an acid upon exposure to high-energy rays, but is preferably one that generates a sulfonic acid, an imide acid, or a methide acid. Suitable photoacid generators include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxyimide, and oxime-O-sulfonate-type acid generators. Specific examples of photoacid generators include those described in paragraphs

[0122] to

[0142] of JP 2008-111103 A.

[0096] Furthermore, a photoacid generator represented by the following formula (3) can also be suitably used. [ka]

[0097] In formula (3), R 101 ~R 103 are each independently a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom.

[0098] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0099] R 101 ~R 103 The hydrocarbyl group having 1 to 20 carbon atoms represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl groups; cyclic saturated hydrocarbyl groups having 3 to 20 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl groups; alkenyl groups having 2 to 20 carbon atoms, such as vinyl, propenyl, butenyl, and hexenyl groups; and ethynyl groups. alkynyl groups having 2 to 20 carbon atoms such as a propynyl group or a butynyl group; cyclic unsaturated aliphatic hydrocarbyl groups having 3 to 20 carbon atoms such as a cyclohexenyl group or a norbornenyl group; aryl groups having 6 to 20 carbon atoms such as a phenyl group, a methylphenyl group, an ethylphenyl group, an n-propylphenyl group, an isopropylphenyl group, an n-butylphenyl group, an isobutylphenyl group, a sec-butylphenyl group, a tert-butylphenyl group, a naphthyl group, a methylnaphthyl group, an ethylnaphthyl group, an n-propylnaphthyl group, an isopropylnaphthyl group, an n-butylnaphthyl group, an isobutylnaphthyl group, a sec-butylnaphthyl group or a tert-butylnaphthyl group; aralkyl groups having 7 to 20 carbon atoms such as a benzyl group or a phenethyl group; and groups obtained by combining these.

[0100] Furthermore, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom or a halogen atom, and some of the -CH- groups of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom, and as a result, the hydrocarbyl group may contain a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a mercapto group, a carbonyl group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-OC(=O)-), a haloalkyl group, or the like.

[0101] Also, R 101 and R 102 However, they may be bonded to each other to form a ring together with the sulfur atom to which they are bonded. In this case, the ring preferably has the following structure: [ka] (In the formula, the dashed line indicates R 103 )

[0102] Examples of the cation of the sulfonium salt represented by formula (3) include, but are not limited to, those shown below. [ka]

[0103] [ka]

[0104] [ka]

[0105] [ka]

[0106]

change

[0107]

change

[0108]

change

[0109]

change

[0110]

change

[0111]

change

[0112]

change

[0113]

change

[0114]

change

[0115]

change

[0116]

change

[0117] [ka]

[0118] [ka]

[0119] [ka]

[0120] [ka]

[0121] [ka]

[0122] [ka]

[0123] [ka]

[0124] [ka]

[0125] [ka]

[0126] In formula (3), Xa - is an anion selected from the following formulae (3A) to (3D). [ka]

[0127] In formula (3A), R fa is a hydrocarbyl group having 1 to 40 carbon atoms which may contain a fluorine atom or a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include R in formula (3A') described below. 111 Examples of the hydrocarbyl group represented by the formula (I) include the same as those exemplified above.

[0128] The anion represented by formula (3A) is preferably one represented by the following formula (3A'). [ka]

[0129] In formula (3A'), R HF is a hydrogen atom or a trifluoromethyl group, preferably a trifluoromethyl group. 111 is a hydrocarbyl group having 1 to 38 carbon atoms which may contain a heteroatom. The heteroatom is preferably an oxygen atom, a nitrogen atom, a sulfur atom, a halogen atom, or the like, and more preferably an oxygen atom. In order to obtain high resolution in the formation of a fine pattern, the hydrocarbyl group is particularly preferably one having 6 to 30 carbon atoms.

[0130] R 111The hydrocarbyl group represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 38 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, a nonyl group, an undecyl group, a tridecyl group, a pentadecyl group, a heptadecyl group, and an icosyl group; a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, a 2-adamantyl group, a 1-adamantylmethyl group, and a norbornyl group. cyclic saturated hydrocarbyl groups having 3 to 38 carbon atoms such as a norbornylmethyl group, a tricyclodecanyl group, a tetracyclododecanyl group, a tetracyclododecanylmethyl group, or a dicyclohexylmethyl group; unsaturated aliphatic hydrocarbyl groups having 2 to 38 carbon atoms such as an allyl group or a 3-cyclohexenyl group; aryl groups having 6 to 38 carbon atoms such as a phenyl group, a 1-naphthyl group, or a 2-naphthyl group; aralkyl groups having 7 to 38 carbon atoms such as a benzyl group or a diphenylmethyl group; and groups obtained by combining these.

[0131] Furthermore, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom or a halogen atom, and some of the -CH- groups of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom, and as a result, the hydrocarbyl group may contain a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a carbonyl group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-OC(=O)-), a haloalkyl group, etc. Examples of hydrocarbyl groups containing hetero atoms include tetrahydrofuryl, methoxymethyl, ethoxymethyl, methylthiomethyl, acetamidomethyl, trifluoroethyl, (2-methoxyethoxy)methyl, acetoxymethyl, 2-carboxy-1-cyclohexyl, 2-oxopropyl, 4-oxo-1-adamantyl, and 3-oxocyclohexyl groups.

[0132] Synthesis of sulfonium salts containing anions represented by formula (3A') is described in detail in JP-A Nos. 2007-145797, 2008-106045, 2009-7327, and 2009-258695. Sulfonium salts described in JP-A Nos. 2010-215608, 2012-41320, 2012-106986, and 2012-153644 are also suitable.

[0133] Examples of the anion represented by formula (3A) include, but are not limited to, those shown below: In the following formula, Ac is an acetyl group. [ka]

[0134] [ka]

[0135] [ka]

[0136] [ka]

[0137] In formula (3B), R fb1 and R fb2 are each independently a hydrocarbyl group having 1 to 40 carbon atoms which may contain a fluorine atom or a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include R in formula (3A'). 111 Examples of the hydrocarbyl group represented by R include the same as those exemplified above. fb1 and R fb2 is preferably a fluorine atom or a linear fluorinated alkyl group having 1 to 4 carbon atoms. fb1 and R fb2means that the groups to which they are bonded (-CF2-SO2-N - -SO2-CF2-) together to form a ring, in which case, R fb1 and R fb2 The group obtained by bonding together is preferably a fluorinated ethylene group or a fluorinated propylene group.

[0138] In formula (3C), R fc1 , R fc2 and R fc3 are each independently a hydrocarbyl group having 1 to 40 carbon atoms which may contain a fluorine atom or a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include R in formula (3A'). 111 Examples of the hydrocarbyl group represented by R include the same as those exemplified above. fc1 , R fc2 and R fc3 is preferably a fluorine atom or a linear fluorinated alkyl group having 1 to 4 carbon atoms. fc1 and R fc2 are groups that are bonded together and bonded to each other (-CF2-SO2-C - -SO2-CF2-) together to form a ring, in which case, R fc1 and R fc2 The group obtained by bonding together is preferably a fluorinated ethylene group or a fluorinated propylene group.

[0139] In formula (3D), R fd is a hydrocarbyl group having 1 to 40 carbon atoms which may contain a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include R in formula (3A'). 111 Examples of the hydrocarbyl group represented by the formula (I) include the same as those exemplified above.

[0140] The synthesis of sulfonium salts containing anions represented by formula (3D) is described in detail in JP-A-2010-215608 and JP-A-2014-133723.

[0141] Examples of the anion represented by formula (3D) include, but are not limited to, those shown below. [ka]

[0142] [ka]

[0143] Although the photoacid generator containing the anion represented by formula (3D) does not have a fluorine atom at the α-position of the sulfo group, it has two trifluoromethyl groups at the β-position, and therefore has sufficient acidity to cleave the acid labile groups in the base polymer, making it suitable for use as a photoacid generator.

[0144] As the photoacid generator, a compound represented by the following formula (4) can also be suitably used. [ka]

[0145] In formula (4), R 201 and R 202 R are each independently a halogen atom or a hydrocarbyl group having 1 to 30 carbon atoms which may contain a heteroatom. 203 is a hydrocarbylene group having 1 to 30 carbon atoms which may contain a heteroatom. 201 , R 202 and R 203 Any two of these may be bonded to each other to form a ring together with the sulfur atom to which they are bonded. In this case, the ring may be any of the groups represented by R 101 and R 102 and the sulfur atom to which they are bonded to form a ring, the same rings as those exemplified above can be mentioned.

[0146] R 201 and R 202The hydrocarbyl group represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 30 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a tert-pentyl group, an n-hexyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, and an n-decyl group; a cyclopentyl group, a cyclohexyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclopentylbutyl group, a cyclohexylmethyl group, a cyclohexylethyl group, a cyclohexylbutyl group, a norbornyl group, an oxanorbornyl group, and a tricyclo[5.2.1.0] 2,6 cyclic saturated hydrocarbyl groups having 3 to 30 carbon atoms such as a phenyl group, a methylphenyl group, an ethylphenyl group, an n-propylphenyl group, an isopropylphenyl group, an n-butylphenyl group, an isobutylphenyl group, a sec-butylphenyl group, a tert-butylphenyl group, a naphthyl group, a methylnaphthyl group, an ethylnaphthyl group, an n-propylnaphthyl group, an isopropylnaphthyl group, an n-butylnaphthyl group, an isobutylnaphthyl group, a sec-butylnaphthyl group, a tert-butylnaphthyl group, an anthracenyl group, and the like; and groups obtained by combining these. Furthermore, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom or a halogen atom, and some of the -CH- groups of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom, and as a result, the hydrocarbyl group may contain a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a carbonyl group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-OC(=O)-), a haloalkyl group, etc.

[0147] R 203The hydrocarbylene group represented by the formula (I) may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkanediyl groups having 1 to 30 carbon atoms, such as methanediyl group, ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, tridecane-1,13-diyl group, tetradecane-1,14-diyl group, pentadecane-1,15-diyl group, hexadecane-1,16-diyl group, and heptadecane-1,17-diyl group; cyclopentanediyl group, cyclohexene-1,18-diyl group, and the like. Examples of the alkylene groups include cyclic saturated hydrocarbylene groups having 3 to 30 carbon atoms, such as xanediyl, norbornanediyl, and adamantanediyl; arylene groups having 6 to 30 carbon atoms, such as phenylene, methylphenylene, ethylphenylene, n-propylphenylene, isopropylphenylene, n-butylphenylene, isobutylphenylene, sec-butylphenylene, tert-butylphenylene, naphthylene, methylnaphthylene, ethylnaphthylene, n-propylnaphthylene, isopropylnaphthylene, n-butylnaphthylene, isobutylnaphthylene, sec-butylnaphthylene, and tert-butylnaphthylene; and groups obtained by combining these groups. In addition, some or all of the hydrogen atoms of the hydrocarbylene group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom, or a halogen atom, and some of the -CH- groups of the hydrocarbylene group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom, resulting in the hydrocarbylene group containing a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a carbonyl group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic anhydride (-C(=O)-OC(=O)-), a haloalkyl group, etc. As the heteroatom, an oxygen atom is preferred.

[0148] In formula (4), L Bis a single bond, an ether bond, or a hydrocarbylene group having 1 to 20 carbon atoms which may contain a heteroatom. The hydrocarbylene group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include R 203 Examples of the hydrocarbylene group represented by the formula (I) include the same as those exemplified above.

[0149] In formula (4), X A , X B , X C and X D are each independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, provided that X A , X B , X C and X D At least one of the groups is a fluorine atom or a trifluoromethyl group.

[0150] In formula (4), k is an integer of 0 to 3.

[0151] The photoacid generator represented by formula (4) is preferably one represented by the following formula (4'). [ka]

[0152] In formula (4'), L B is the same as above. R HF is a hydrogen atom or a trifluoromethyl group, preferably a trifluoromethyl group. 301 , R 302 and R 303 are each independently a hydrocarbyl group having 1 to 20 carbon atoms which may contain a hydrogen atom or a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include R in formula (3A'). 111 Examples of the hydrocarbyl group include the same as those exemplified above. Each of x and y is independently an integer of 0 to 5, and z is an integer of 0 to 4.

[0153] Examples of the photoacid generator represented by formula (4) include the same compounds as those exemplified as the photoacid generator represented by formula (2) in JP-A-2017-026980.

[0154] Among the photoacid generators, those containing an anion represented by formula (3A') or (3D) are particularly preferred because of their small acid diffusion and excellent solubility in solvents. Also, those represented by formula (4') are particularly preferred because of their extremely small acid diffusion.

[0155] The photoacid generator may also be a sulfonium salt or iodonium salt containing an anion having an aromatic ring substituted with an iodine atom or a bromine atom, such as those represented by the following formula (5-1) or (5-2): [ka]

[0156] In formulas (5-1) and (5-2), p is an integer that satisfies 1≦p≦3. q and r are integers that satisfy 1≦q≦5, 0≦r≦3, and 1≦q+r≦5. q is preferably an integer that satisfies 1≦q≦3, more preferably 2 or 3. r is preferably an integer that satisfies 0≦r≦2.

[0157] In formulas (5-1) and (5-2), X BI is an iodine atom or a bromine atom, and when p and / or q is 2 or more, they may be the same or different.

[0158] In formulas (5-1) and (5-2), L 1 is a single bond, an ether bond, an ester bond, or a saturated hydrocarbylene group having 1 to 6 carbon atoms which may contain an ether bond or an ester bond. The saturated hydrocarbylene group may be linear, branched, or cyclic.

[0159] In formulas (5-1) and (5-2), L 2represents a single bond or a divalent linking group having 1 to 20 carbon atoms when p is 1, and represents a (p+1)-valent linking group having 1 to 20 carbon atoms when p is 2 or 3, and the linking group may contain an oxygen atom, a sulfur atom, or a nitrogen atom.

[0160] In formulas (5-1) and (5-2), R 401 is a hydroxy group, a carboxy group, a fluorine atom, a chlorine atom, a bromine atom or an amino group, or a hydrocarbyl group having 1 to 20 carbon atoms, a hydrocarbyloxy group having 1 to 20 carbon atoms, a hydrocarbylcarbonyl group having 2 to 20 carbon atoms, a hydrocarbyloxycarbonyl group having 2 to 20 carbon atoms, a hydrocarbylcarbonyloxy group having 2 to 20 carbon atoms or a hydrocarbylsulfonyloxy group having 1 to 20 carbon atoms which may contain a fluorine atom, a chlorine atom, a bromine atom, a hydroxy group, an amino group or an ether bond, or 401A )(R 401B ), -N(R 401C )-C(=O)-R 401D or -N(R 401C )-C(=O)-OR 401D R 401A and R 401B are each independently a hydrogen atom or a saturated hydrocarbyl group having 1 to 6 carbon atoms. 401C is a hydrogen atom or a saturated hydrocarbyl group having 1 to 6 carbon atoms, and may contain a halogen atom, a hydroxy group, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, a saturated hydrocarbylcarbonyl group having 2 to 6 carbon atoms, or a saturated hydrocarbylcarbonyloxy group having 2 to 6 carbon atoms. 401Dis an aliphatic hydrocarbyl group having 1 to 16 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 15 carbon atoms, and may contain a halogen atom, a hydroxy group, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, a saturated hydrocarbylcarbonyl group having 2 to 6 carbon atoms, or a saturated hydrocarbylcarbonyloxy group having 2 to 6 carbon atoms. The aliphatic hydrocarbyl group may be saturated or unsaturated and may be linear, branched, or cyclic. The hydrocarbyl group, hydrocarbyloxy group, hydrocarbylcarbonyl group, hydrocarbyloxycarbonyl group, hydrocarbylcarbonyloxy group, and hydrocarbylsulfonyloxy group may be linear, branched, or cyclic. When p and / or r is 2 or more, each R 401 may be the same or different from each other.

[0161] Of these, R 401 Examples of the hydroxyl group include -N(R 401C )-C(=O)-R 401D , -N(R 401C )-C(=O)-OR 401D fluorine atom, chlorine atom, bromine atom, methyl group, methoxy group, etc. are preferred.

[0162] In formulas (5-1) and (5-2), Rf 1 ~Rf 4 are each independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, and at least one of them is a fluorine atom or a trifluoromethyl group. 1 and Rf 2 may combine to form a carbonyl group. 3 and Rf 4 are preferably both fluorine atoms.

[0163] In formulas (5-1) and (5-2), R 402 ~R 406are each independently a hydrocarbyl group having 1 to 20 carbon atoms which may contain a halogen atom or a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include R 101 ~R 103 Examples of the hydrocarbyl group include the same as those exemplified above. In addition, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a hydroxy group, a carboxy group, a halogen atom, a cyano group, a nitro group, a mercapto group, a sultone ring, a sulfo group, or a sulfonium salt-containing group, and some of the -CH2- groups of the hydrocarbyl group may be substituted with an ether bond, an ester bond, a carbonyl group, an amide bond, a carbonate bond, or a sulfonate ester bond. 402 and R 403 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded. In this case, the ring is the same as R 101 and R 102 and may be bonded to each other to form a ring together with the sulfur atom to which they are bonded, similar to the rings exemplified above.

[0164] Examples of the cation of the sulfonium salt represented by formula (5-1) include the same as those exemplified as the cation of the sulfonium salt represented by formula (3). Examples of the cation of the iodonium salt represented by formula (5-2) include, but are not limited to, the following: [ka]

[0165] [ka]

[0166] Examples of the anion of the onium salt represented by formula (5-1) or (5-2) include, but are not limited to, those shown below. BI is the same as above.

change

[0167]

change

[0168]

change

[0169]

change

[0170]

change

[0171]

change

[0172]

change

[0173]

change

[0174]

change

[0175]

change

[0176]

change

[0177]

change

[0178]

change

[0179]

change

[0180]

change

[0181]

change

[0182]

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[0183]

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[0184]

change

[0185]

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[0186]

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[0187] [ka]

[0188] [ka]

[0189] When the resist material of the present invention does not contain a base polymer, the content of the additive acid generator is preferably 0.1 to 50 parts by mass, and more preferably 1 to 40 parts by mass, per 100 parts by mass of compound A. When the resist material of the present invention contains a base polymer, the content of the additive acid generator is preferably 0.1 to 50 parts by mass, and more preferably 1 to 40 parts by mass, per 100 parts by mass of the base polymer described below.

[0190] When the acid generator also serves as a base polymer described below, the acid generator is preferably a polymer containing a repeating unit derived from a compound that generates an acid in response to actinic rays or radiation. In this case, the acid generator is preferably a base polymer described below containing the repeating unit f as an essential unit.

[0191] [Base polymer] The chemically amplified resist material of the present invention preferably contains a base polymer. In the case of a positive resist material, the base polymer contains a repeating unit containing an acid labile group. The repeating unit containing an acid labile group is preferably a repeating unit represented by the following formula (a1) (hereinafter also referred to as repeating unit a1) or a repeating unit represented by the following formula (a2) (hereinafter also referred to as repeating unit a2). [ka]

[0192] In formulas (a1) and (a2), R A are each independently a hydrogen atom or a methyl group. 11 and R 12are each independently an acid labile group. When the base polymer contains both the repeating unit a1 and the repeating unit a2, R 11 and R 12 may be the same or different. 1 Y is a linking group having 1 to 12 carbon atoms and containing at least one selected from a single bond, a phenylene group, a naphthylene group, an ester bond, and a lactone ring. 2 is a single bond or an ester bond.

[0193] Examples of monomers that provide the repeating unit a1 include, but are not limited to, the following: A and R 11 is the same as above. [ka]

[0194] Examples of the monomer that provides the repeating unit a2 include, but are not limited to, the following: A and R 12 is the same as above. [ka]

[0195] R 11 and R 12 The acid labile group represented by the formula (AL-1) may be selected from a variety of groups, and examples thereof include those represented by the following formulae (AL-1) to (AL-3). [ka] (In the formula, the dashed lines represent bonds.)

[0196] In formula (AL-1), a is an integer of 0 to 6. L1is a tertiary hydrocarbyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, a trihydrocarbylsilyl group in which each hydrocarbyl group is a saturated hydrocarbyl group having 1 to 6 carbon atoms, a carbonyl group, or a saturated hydrocarbyl group having 4 to 20 carbon atoms containing an ether bond or an ester bond, or a group represented by formula (AL-3).

[0197] R L1 The tertiary hydrocarbyl group represented by the formula (I) may be saturated or unsaturated, and may be branched or cyclic. Specific examples thereof include a tert-butyl group, a tert-pentyl group, a 1,1-diethylpropyl group, a 1-ethylcyclopentyl group, a 1-butylcyclopentyl group, a 1-ethylcyclohexyl group, a 1-butylcyclohexyl group, a 1-ethyl-2-cyclopentenyl group, a 1-ethyl-2-cyclohexenyl group, and a 2-methyl-2-adamantyl group. Examples of the trihydrocarbylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a dimethyl-tert-butylsilyl group. The saturated hydrocarbyl group containing a carbonyl group, an ether bond, or an ester bond may be linear, branched, or cyclic, but is preferably cyclic. Specific examples thereof include a 3-oxocyclohexyl group, a 4-methyl-2-oxooxan-4-yl group, a 5-methyl-2-oxoxolan-5-yl group, a 2-tetrahydropyranyl group, and a 2-tetrahydrofuranyl group.

[0198] Examples of the acid labile group represented by formula (AL-1) include a tert-butoxycarbonyl group, a tert-butoxycarbonylmethyl group, a tert-pentyloxycarbonyl group, a tert-pentyloxycarbonylmethyl group, a 1,1-diethylpropyloxycarbonyl group, a 1,1-diethylpropyloxycarbonylmethyl group, a 1-ethylcyclopentyloxycarbonyl group, a 1-ethylcyclopentyloxycarbonylmethyl group, a 1-ethyl-2-cyclopentenyloxycarbonyl group, a 1-ethyl-2-cyclopentenyloxycarbonylmethyl group, a 1-ethoxyethoxycarbonylmethyl group, a 2-tetrahydropyranyloxycarbonylmethyl group, and a 2-tetrahydrofuranyloxycarbonylmethyl group.

[0199] Examples of the acid labile group represented by formula (AL-1) also include groups represented by the following formulae (AL-1)-1 to (AL-1)-10. [ka] (In the formula, the dashed lines represent bonds.)

[0200] In formulae (AL-1)-1 to (AL-1)-10, a is the same as defined above. L8 are each independently a saturated hydrocarbyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms. L9 is a hydrogen atom or a saturated hydrocarbyl group having 1 to 10 carbon atoms. L10 is a saturated hydrocarbyl group having 2 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms. The saturated hydrocarbyl group may be linear, branched, or cyclic.

[0201] In formula (AL-2), R L2 and R L3are each independently a hydrogen atom or a saturated hydrocarbyl group having 1 to 18 carbon atoms, preferably 1 to 10. The saturated hydrocarbyl group may be linear, branched, or cyclic, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclopentyl group, a cyclohexyl group, a 2-ethylhexyl group, and an n-octyl group.

[0202] In formula (AL-2), R L4 is a hydrocarbyl group having 1 to 18 carbon atoms, preferably 1 to 10, which may contain a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Examples of the hydrocarbyl group include saturated hydrocarbyl groups having 1 to 18 carbon atoms, and some of the hydrogen atoms may be substituted with hydroxy groups, alkoxy groups, oxo groups, amino groups, alkylamino groups, etc. Examples of such substituted saturated hydrocarbyl groups include those shown below. [ka] (In the formula, the dashed lines represent bonds.)

[0203] R L2 and R L3 and R L2 and R L4 and, or R L3 and R L4 may be bonded to each other to form a ring together with the carbon atom to which they are bonded, or together with the carbon atom and oxygen atom, and in this case, R L2 and R L3 , R L2 and R L4 , or R L3 and R L4 are each independently an alkanediyl group having 1 to 18 carbon atoms, preferably 1 to 10. The ring obtained by combining these groups preferably has 3 to 10 carbon atoms, more preferably 4 to 10 carbon atoms.

[0204] Among the acid labile groups represented by formula (AL-2), linear or branched ones include, but are not limited to, those represented by the following formulae (AL-2)-1 to (AL-2)-69, in which the dashed lines represent bonds. [ka]

[0205] [ka]

[0206] [ka]

[0207] [ka]

[0208] Among the acid labile groups represented by formula (AL-2), examples of cyclic groups include tetrahydrofuran-2-yl, 2-methyltetrahydrofuran-2-yl, tetrahydropyran-2-yl, and 2-methyltetrahydropyran-2-yl groups.

[0209] Further, examples of the acid labile group include groups represented by the following formula (AL-2a) or (AL-2b): The base polymer may be inter- or intramolecularly crosslinked by the acid labile group. [ka] (In the formula, the dashed lines represent bonds.)

[0210] In formula (AL-2a) or (AL-2b), R L11 and R L12 are each independently a hydrogen atom or a saturated hydrocarbyl group having 1 to 8 carbon atoms. The saturated hydrocarbyl group may be linear, branched, or cyclic. L11 and R L12may be bonded to each other to form a ring together with the carbon atoms to which they are attached, in which case R L11 and R L12 are each independently an alkanediyl group having 1 to 8 carbon atoms. L13 are each independently a saturated hydrocarbylene group having 1 to 10 carbon atoms. The saturated hydrocarbylene group may be linear, branched, or cyclic. d and e are each independently an integer of 0 to 10, preferably an integer of 0 to 5, and f is an integer of 1 to 7, preferably an integer of 1 to 3.

[0211] In formula (AL-2a) or (AL-2b), L C is an (f+1)-valent aliphatic saturated hydrocarbon group having 1 to 50 carbon atoms, an (f+1)-valent alicyclic saturated hydrocarbon group having 3 to 50 carbon atoms, an (f+1)-valent aromatic hydrocarbon group having 6 to 50 carbon atoms, or an (f+1)-valent heterocyclic group having 3 to 50 carbon atoms. In addition, some of the -CH2- groups may be substituted with groups containing hetero atoms, and some of the hydrogen atoms bonded to carbon atoms in these groups may be substituted with hydroxy groups, carboxy groups, acyl groups, or fluorine atoms. C As L, saturated hydrocarbon groups such as saturated hydrocarbylene groups having 1 to 20 carbon atoms, trivalent saturated hydrocarbon groups, and tetravalent saturated hydrocarbon groups, and arylene groups having 6 to 30 carbon atoms are preferred. The saturated hydrocarbon groups may be linear, branched, or cyclic. D is -C(=O)-O-, -NH-C(=O)-O- or -NH-C(=O)-NH-.

[0212] Examples of the crosslinked acetal group represented by formula (AL-2a) or (AL-2b) include groups represented by the following formulae (AL-2)-70 to (AL-2)-77. [ka] (In the formula, the dashed lines represent bonds.)

[0213] In formula (AL-3), R L5 , R L6 and R L7are each independently a hydrocarbyl group having 1 to 20 carbon atoms, which may contain heteroatoms such as oxygen, sulfur, nitrogen, and fluorine atoms. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include alkyl groups having 1 to 20 carbon atoms, saturated cyclic hydrocarbyl groups having 3 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, unsaturated cyclic aliphatic hydrocarbyl groups having 3 to 20 carbon atoms, and aryl groups having 6 to 10 carbon atoms. In addition, R L5 and R L6 and R L5 and R L7 and, or R L6 and R L7 may be bonded to each other to form an alicyclic ring having 3 to 20 carbon atoms together with the carbon atom to which they are bonded.

[0214] Examples of the group represented by formula (AL-3) include a tert-butyl group, a 1,1-diethylpropyl group, a 1-ethylnorbornyl group, a 1-methylcyclopentyl group, a 1-ethylcyclopentyl group, a 1-isopropylcyclopentyl group, a 1-methylcyclohexyl group, a 2-(2-methyl)adamantyl group, a 2-(2-ethyl)adamantyl group, and a tert-pentyl group.

[0215] Further, examples of the group represented by formula (AL-3) include groups represented by the following formulae (AL-3)-1 to (AL-3)-19. [ka] (In the formula, the dashed lines represent bonds.)

[0216] In formulas (AL-3)-1 to (AL-3)-19, R L14 are each independently a saturated hydrocarbyl group having 1 to 8 carbon atoms or an aryl group having 6 to 20 carbon atoms. L15 and R L17 are each independently a hydrogen atom or a saturated hydrocarbyl group having 1 to 20 carbon atoms. L16is an aryl group having 6 to 20 carbon atoms. The saturated hydrocarbyl group may be linear, branched, or cyclic. The aryl group is preferably a phenyl group. R F is a fluorine atom or a trifluoromethyl group, and g is an integer of 1 to 5.

[0217] Further examples of the acid labile group include groups represented by the following formula (AL-3)-20 or (AL-3)-21: The base polymer may be inter- or intramolecularly crosslinked by the acid labile group. [ka] (In the formula, the dashed lines represent bonds.)

[0218] In formulas (AL-3)-20 and (AL-3)-21, R L14 is the same as above. R L18 is a (h+1)-valent saturated hydrocarbylene group having 1 to 20 carbon atoms or a (h+1)-valent arylene group having 6 to 20 carbon atoms, and may contain a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. The saturated hydrocarbylene group may be linear, branched, or cyclic. h is an integer of 1 to 3.

[0219] R 11 and R 12 Examples of acid labile groups represented by the formula (I) include those described in Japanese Patent No. 3832564, Japanese Patent No. 5407892, Japanese Patent No. 5407941, Japanese Patent No. 5434983, Japanese Patent No. 5463963, Japanese Patent No. 5564293, Japanese Patent No. 5565293, Japanese Patent No. 5573595, Japanese Patent No. 5655754, Japanese Patent No. 5655755, and Japanese Patent No. 5655756 Acid labile groups containing aromatic groups or multiple bonds described in Japanese Patent No. 5772760, Japanese Patent Application Laid-Open No. 2007-279699, Japanese Patent Application Laid-Open No. 2018-172640, Japanese Patent Application Laid-Open No. 2019-214554, Japanese Patent Application Laid-Open No. 2021-50307, ​​and Japanese Patent Application Laid-Open No. 2021-110922, and acid labile groups having a steroid structure described in Japanese Patent No. 6411967 can also be used.

[0220] The base polymer may contain a repeating unit b containing a phenolic hydroxy group as an adhesive group. Examples of monomers that provide the repeating unit b include, but are not limited to, the following. In the following formula, R A is the same as above. [ka]

[0221] The base polymer may contain a repeating unit c containing, as another adhesive group, a hydroxy group other than a phenolic hydroxy group, a lactone ring, a sultone ring, an ether bond, an ester bond, a sulfonate ester bond, a carbonyl group, a sulfonyl group, a cyano group, or a carboxy group. Examples of monomers that provide the repeating unit c include, but are not limited to, those shown below. In the following formula, R A is the same as above. [ka]

[0222] [ka]

[0223] [ka]

[0224] [ka]

[0225] [ka]

[0226] [ka]

[0227] [ka]

[0228] [ka]

[0229] The base polymer may contain repeating units d derived from indene, benzofuran, benzothiophene, acenaphthylene, chromone, coumarin, norbornadiene, or derivatives thereof. Monomers that provide repeating units d include, but are not limited to, the following: [ka]

[0230] The base polymer may include repeat units e derived from styrene, vinylnaphthalene, vinylanthracene, vinylpyrene, methyleneindane, vinylpyridine, or vinylcarbazole.

[0231] The base polymer may contain a repeating unit f derived from an onium salt containing a polymerizable unsaturated bond. Preferred repeating units f include a repeating unit represented by the following formula (f1) (hereinafter also referred to as repeating unit f1), a repeating unit represented by the following formula (f2) (hereinafter also referred to as repeating unit f2), and a repeating unit represented by the following formula (f3) (hereinafter also referred to as repeating unit f3). The repeating units f1 to f3 may be used alone or in combination of two or more. [ka]

[0232] In formulas (f1) to (f3), R A are each independently a hydrogen atom or a methyl group. 1represents a single bond, an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a naphthylene group, or a group having 7 to 18 carbon atoms obtained by combining these, or -OZ 11 -, -C(=O)-OZ 11 - or -C(=O)-NH-Z 11 -It is. Z 11 Z is an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a naphthylene group, or a group having 7 to 18 carbon atoms obtained by combining these, and may contain a carbonyl group, an ester bond, an ether bond, or a hydroxy group. 2 is a single bond, -Z 21 -C(=O)-O-, -Z 21 -O- or -Z 21 -OC(=O)-. Z 21 is a saturated hydrocarbylene group having 1 to 12 carbon atoms, which may contain a carbonyl group, an ester bond, or an ether bond. 3 represents a single bond, a methylene group, an ethylene group, a phenylene group, a fluorinated phenylene group, a phenylene group substituted with a trifluoromethyl group, -OZ 31 -, -C(=O)-OZ 31 - or -C(=O)-NH-Z 31 -It is. Z 31 is an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a fluorinated phenylene group, or a phenylene group substituted with a trifluoromethyl group, and may contain a carbonyl group, an ester bond, an ether bond, or a hydroxy group. 11 and Z 31 The aliphatic hydrocarbylene group represented by Z may be saturated or unsaturated, and may be linear, branched, or cyclic. 21 The saturated hydrocarbylene group represented by the formula (I) may be linear, branched or cyclic.

[0233] In formulas (f1) to (f3), R 21 ~R 28are each independently a hydrocarbyl group having 1 to 20 carbon atoms which may contain a halogen atom or a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include R in formula (3): 101 ~R 103 Examples include the same as those exemplified in the explanation of 1. In addition, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom, a nitrogen atom or a halogen atom, and some of the -CH2- groups of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom, and as a result, the hydrocarbyl group may contain a hydroxy group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, a nitro group, a mercapto group, a carbonyl group, an ether bond, an ester bond, a sulfonate ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic acid anhydride (-C(=O)-OC(=O)-), a haloalkyl group, etc.

[0234] Also, R 23 and R 24 or R 26 and R 27 may be bonded to each other to form a ring together with the sulfur atom to which they are bonded. In this case, the ring may be any of the groups represented by R 101 and R 102 and the sulfur atom to which they are bonded to form a ring, the same rings as those exemplified above can be mentioned.

[0235] In formula (f2), R HF is a hydrogen atom or a trifluoromethyl group.

[0236] In formula (f1), M -is a non-nucleophilic counter ion. Examples of the non-nucleophilic counter ion include halide ions such as chloride ion and bromide ion; fluoroalkylsulfonate ions such as triflate ion, 1,1,1-trifluoroethanesulfonate ion and nonafluorobutanesulfonate ion; arylsulfonate ions such as tosylate ion, benzenesulfonate ion, 4-fluorobenzenesulfonate ion and 1,2,3,4,5-pentafluorobenzenesulfonate ion; alkylsulfonate ions such as mesylate ion and butanesulfonate ion; imide ions such as bis(trifluoromethylsulfonyl)imide ion, bis(perfluoroethylsulfonyl)imide ion and bis(perfluorobutylsulfonyl)imide ion; and methide ions such as tris(trifluoromethylsulfonyl)methide ion and tris(perfluoroethylsulfonyl)methide ion.

[0237] Other examples of the non-nucleophilic counter ion include a sulfonate ion represented by the following formula (f1-1) in which the α-position is substituted with a fluorine atom, a sulfonate ion represented by the following formula (f1-2) in which the α-position is substituted with a fluorine atom and the β-position is substituted with a trifluoromethyl group, and a sulfonate ion containing an iodine atom represented by the above-mentioned formula (5-1). [ka]

[0238] In formula (f1-1), R 31 is a hydrogen atom or a hydrocarbyl group having 1 to 20 carbon atoms, and the hydrocarbyl group may contain an ether bond, an ester bond, a carbonyl group, a lactone ring, or a fluorine atom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include R in formula (3A'). 111 Examples of the hydrocarbyl group represented by the formula (I) include the same as those exemplified above.

[0239] In formula (f1-2), R 32is a hydrogen atom, a hydrocarbyl group having 1 to 30 carbon atoms, or a hydrocarbyl carbonyl group having 2 to 30 carbon atoms, and the hydrocarbyl group and hydrocarbyl carbonyl group may contain an ether bond, an ester bond, a carbonyl group, or a lactone ring. The hydrocarbyl moiety of the hydrocarbyl group and hydrocarbyl carbonyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples thereof include R in formula (3A'): 111 Examples of the hydrocarbyl group represented by the formula (I) include the same as those exemplified above.

[0240] Examples of the cation of the monomer that gives the repeating unit f1 include, but are not limited to, the following: A is the same as above. [ka]

[0241] Examples of the cation of the monomer that gives the repeating unit f2 or f3 include the same cations as those given as examples of the sulfonium salt represented by formula (3).

[0242] Examples of the anion of the monomer that gives the repeating unit f2 include, but are not limited to, those shown below. A is the same as above. [ka]

[0243] [ka]

[0244] Examples of the anion of the monomer that gives the repeating unit f3 include, but are not limited to, those shown below. A is the same as above. [ka]

[0245] [Chemical formula]

[0246] By bonding an acid generator to the polymer main chain, acid diffusion can be reduced, and a decrease in resolution due to blurring of acid diffusion can be prevented. Further, by uniformly dispersing the acid generator, LWR and CDU are improved.

[0247] When including the repeating unit f, the base polymer also functions as the aforementioned acid generator. In this case, since the base polymer is integrated with the acid generator (that is, it is a polymer-bound type acid generator), the chemically amplified resist material of the present invention may or may not contain an additive acid generator.

[0248] The base polymer for a chemically amplified positive resist material essentially requires a repeating unit a1 or a2 containing an acid-labile group. In this case, the content ratios of the repeating units a1, a2, b, c, d, e, and f are preferably 0 ≦ a1 < 1.0, 0 ≦ a2 < 1.0, 0 < a1 + a2 < 1.0, 0 ≦ b ≦ 0.9, 0 ≦ c ≦ 0.9, 0 ≦ d ≦ 0.8, 0 ≦ e ≦ 0.8, and 0 ≦ f ≦ 0.5, more preferably 0 ≦ a1 ≦ 0.9, 0 ≦ a2 ≦ 0.9, 0.1 ≦ a1 + a2 ≦ 0.9, 0 ≦ b ≦ 0.8, 0 ≦ c ≦ 0.8, 0 ≦ d ≦ 0.7, 0 ≦ e ≦ 0.7, and 0 ≦ f ≦ 0.4, and still more preferably 0 ≦ a1 ≦ 0.8, 0 ≦ a2 ≦ 0.8, 0.1 ≦ a1 + a2 ≦ 0.8, 0 ≦ b ≦ 0.75, 0 ≦ c ≦ 0.75, 0 ≦ d ≦ 0.6, 0 ≦ e ≦ 0.6, and 0 ≦ f ≦ 0.3. When the base polymer is a polymer-bound type acid generator, the content ratio of the repeating unit f is preferably 0 < f ≦ 0.5, more preferably 0.01 ≦ f ≦ 0.4, and still more preferably 0.02 ≦ f ≦ 0.3. In addition, when the repeating unit f is at least one selected from the repeating units f1 to f3, f = f1 + f2 + f3. Also, a1 + a2 + b + c + d + e + f = 1.0.

[0249] On the one hand, for the base polymer for chemically amplified negative resist materials, an acid-labile group is not necessarily required. Examples of such base polymers include those containing repeating unit b and optionally further containing repeating units c, d, e, and / or f. The content ratios of these repeating units are preferably 0 < b ≤ 1.0, 0 ≤ c ≤ 0.9, 0 ≤ d ≤ 0.8, 0 ≤ e ≤ 0.8, and 0 ≤ f ≤ 0.5, more preferably 0.2 ≤ b ≤ 1.0, 0 ≤ c ≤ 0.8, 0 ≤ d ≤ 0.7, 0 ≤ e ≤ 0.7, and 0 ≤ f ≤ 0.4, and even more preferably 0.3 ≤ b ≤ 1.0, 0 ≤ c ≤ 0.75, 0 ≤ d ≤ 0.6, 0 ≤ e ≤ 0.6, and 0 ≤ f ≤ 0.3. When the base polymer is a polymer-bound acid generator, the content ratio of repeating unit f is preferably 0 < f ≤ 0.5, more preferably 0.01 ≤ f ≤ 0.4, and even more preferably 0.02 ≤ f ≤ 0.3. When repeating unit f is at least one selected from repeating units f1 to f3, f = f1 + f2 + f3. Also, b + c + d + e + f = 1.0.

[0250] To synthesize the base polymer, for example, monomers that provide the aforementioned repeating units may be heated in an organic solvent with a radical polymerization initiator added thereto to perform polymerization.

[0251] Examples of the organic solvent used during polymerization include toluene, benzene, tetrahydrofuran (THF), diethyl ether, dioxane, etc. Examples of the polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2-azobis(2-methylpropionate), benzoyl peroxide, lauroyl peroxide, etc. The temperature during polymerization is preferably 50 to 80°C. The reaction time is preferably 2 to 100 hours, more preferably 5 to 20 hours.

[0252] When a monomer containing a hydroxy group is copolymerized, the hydroxy group may be substituted with an acetal group that is easily deprotected by an acid, such as an ethoxyethoxy group, during polymerization, and then deprotected with a weak acid and water after polymerization. Alternatively, the hydroxy group may be substituted with an acetyl group, a formyl group, a pivaloyl group, or the like, and then subjected to alkaline hydrolysis after polymerization.

[0253] When copolymerizing hydroxystyrene or hydroxyvinylnaphthalene, acetoxystyrene or acetoxyvinylnaphthalene may be used instead of hydroxystyrene or hydroxyvinylnaphthalene, and after polymerization, the acetoxy group may be deprotected by the alkaline hydrolysis to give hydroxystyrene or hydroxyvinylnaphthalene.

[0254] The base that can be used in alkaline hydrolysis includes aqueous ammonia, triethylamine, etc. The reaction temperature is preferably −20 to 100° C., more preferably 0 to 60° C. The reaction time is preferably 0.2 to 100 hours, more preferably 0.5 to 20 hours.

[0255] The base polymer preferably has a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) using THF as a solvent of 1,000 to 500,000, more preferably 2,000 to 30,000. When the Mw is within this range, the resist film has good heat resistance and solubility in an alkaline developer.

[0256] Furthermore, if the base polymer has a broad molecular weight distribution (Mw / Mn), the presence of low-molecular-weight and high-molecular-weight polymers may result in the appearance of foreign matter on the pattern after exposure, or the pattern shape may be deteriorated. As the pattern rule becomes finer, the effects of Mw and Mw / Mn tend to become greater. Therefore, in order to obtain a resist material that is suitable for use with fine pattern dimensions, it is preferable that the Mw / Mn of the base polymer has a narrow distribution of 1.0 to 2.0, particularly 1.0 to 1.5.

[0257] The base polymer may contain two or more polymers with different composition ratios, Mw, and Mw / Mn.

[0258] [Organic solvents] The chemically amplified resist material of the present invention may contain an organic solvent. The organic solvent is not particularly limited as long as it can dissolve the components described above and below. Examples of the organic solvent include ketones such as cyclohexanone, cyclopentanone, methyl-2-n-pentyl ketone, and 2-heptanone, as described in paragraphs

[0144] and

[0145] of JP-A-2008-111103; alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, and diacetone alcohol; propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, and ethylene glycol. Examples of the esters include propylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono-tert-butyl ether acetate, and lactones such as γ-butyrolactone.

[0259] When the chemically amplified resist material of the present invention does not contain a base polymer, the content of the organic solvent is preferably 100 to 10,000 parts by mass, more preferably 200 to 8,000 parts by mass, per 100 parts by mass of compound A. When the chemically amplified resist material of the present invention contains a base polymer, the content of the organic solvent is preferably 100 to 10,000 parts by mass, more preferably 200 to 8,000 parts by mass, per 100 parts by mass of base polymer. The organic solvents may be used alone or in combination of two or more.

[0260] [Other ingredients] The chemically amplified resist material of the present invention may contain, in addition to the above-mentioned components, surfactants, dissolution inhibitors, crosslinking agents, water repellency improvers, acetylene alcohols, and the like.

[0261] Examples of the surfactant include those described in paragraphs

[0165] and

[0166] of JP 2008-111103 A. The addition of a surfactant can further improve or control the coatability of the resist material. When the chemically amplified resist material of the present invention contains the surfactant, the content is preferably 0.0001 to 10 parts by mass per 100 parts by mass of Compound A if the chemically amplified resist material of the present invention does not contain a base polymer. When the chemically amplified resist material of the present invention contains a base polymer, the content is preferably 0.0001 to 10 parts by mass per 100 parts by mass of base polymer. The surfactant may be used alone or in combination of two or more types.

[0262] When the chemically amplified resist material of the present invention is a positive-tone resist, the incorporation of a dissolution inhibitor can further increase the difference in dissolution rate between exposed and unexposed areas, thereby further improving resolution. Examples of dissolution inhibitors include compounds having a molecular weight of preferably 100 to 1,000, more preferably 150 to 800, containing two or more phenolic hydroxy groups in the molecule, in which the hydrogen atoms of the phenolic hydroxy groups have been substituted with acid-labile groups at a rate of 0 to 100 mol % overall, and compounds containing carboxy groups in the molecule, in which the hydrogen atoms of the carboxy groups have been substituted with acid-labile groups at an average rate of 50 to 100 mol % overall. Specific examples include compounds in which the hydrogen atoms of the hydroxyl groups or carboxyl groups of bisphenol A, trisphenol, phenolphthalein, cresol novolak, naphthalenecarboxylic acid, adamantanecarboxylic acid, and cholic acid have been substituted with acid-labile groups. These compounds are described, for example, in paragraphs

[0155] to

[0178] of JP 2008-122932 A.

[0263] When the chemically amplified resist material of the present invention is a positive-working material and contains the dissolution inhibitor, the content thereof is preferably 0 to 50 parts by mass, more preferably 5 to 40 parts by mass, per 100 parts by mass of Compound A when the chemically amplified resist material of the present invention does not contain a base polymer, and when the chemically amplified resist material of the present invention contains a base polymer, the content thereof is preferably 0 to 50 parts by mass, more preferably 5 to 40 parts by mass, per 100 parts by mass of base polymer. The dissolution inhibitors may be used alone or in combination of two or more.

[0264] On the other hand, when the chemically amplified resist material of the present invention is negative, a negative pattern can be obtained by adding a crosslinking agent to reduce the dissolution rate of the exposed area. Examples of crosslinking agents include epoxy compounds, melamine compounds, guanamine compounds, glycoluril compounds or urea compounds, isocyanate compounds, azide compounds, and compounds containing double bonds, such as alkenyloxy groups, all substituted with at least one group selected from methylol groups, alkoxymethyl groups, and acyloxymethyl groups. These may be used as additives or may be introduced as pendant groups into polymer side chains. Hydroxy-containing compounds may also be used as crosslinking agents.

[0265] Examples of the epoxy compound include tris(2,3-epoxypropyl)isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, and triethylolethane triglycidyl ether.

[0266] Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine are methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, a compound in which 1 to 6 methylol groups of hexamethylol melamine are acyloxymethylated, or a mixture thereof.

[0267] Examples of the guanamine compound include tetramethylolguanamine, tetramethoxymethylguanamine, a compound of tetramethylolguanamine in which 1 to 4 methylol groups are methoxymethylated, or a mixture thereof; tetramethoxyethylguanamine, tetraacyloxyguanamine, a compound of tetramethylolguanamine in which 1 to 4 methylol groups are acyloxymethylated, or a mixture thereof; and the like.

[0268] Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxy glycoluril, tetramethoxymethyl glycoluril, a compound in which 1 to 4 methylol groups of tetramethylol glycoluril are methoxymethylated or a mixture thereof, a compound in which 1 to 4 methylol groups of tetramethylol glycoluril are acyloxymethylated or a mixture thereof, etc. Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound in which 1 to 4 methylol groups of tetramethylol urea are methoxymethylated or a mixture thereof, tetramethoxyethyl urea, etc.

[0269] Examples of the isocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate.

[0270] Examples of the azide compound include 1,1'-biphenyl-4,4'-bisazide, 4,4'-methylidenebisazide, and 4,4'-oxybisazide.

[0271] Examples of the compound containing an alkenyloxy group include ethylene glycol divinyl ether, triethylene glycol divinyl ether, 1,2-propanediol divinyl ether, 1,4-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane trivinyl ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, pentaerythritol trivinyl ether, pentaerythritol tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, and trimethylolpropane trivinyl ether.

[0272] When the chemically amplified resist material of the present invention is a negative-working material and contains the crosslinking agent, the content of the crosslinking agent is preferably 0.1 to 50 parts by mass, more preferably 1 to 40 parts by mass, per 100 parts by mass of Compound A when the chemically amplified resist material of the present invention does not contain a base polymer, and when the chemically amplified resist material of the present invention contains a base polymer, the content of the crosslinking agent is preferably 0.1 to 50 parts by mass, more preferably 1 to 40 parts by mass, per 100 parts by mass of base polymer. The crosslinking agents may be used alone or in combination of two or more.

[0273] The water repellency improver improves the water repellency of the resist film surface and can be used in immersion lithography without a top coat. Preferred examples of the water repellency improver include polymers containing fluorinated alkyl groups and polymers containing a specific 1,1,1,3,3,3-hexafluoro-2-propanol residue, with those exemplified in JP-A Nos. 2007-297590 and 2008-111103 being more preferred. The water repellency improver must be soluble in an alkaline developer or an organic solvent developer. The water repellency improver having the specific 1,1,1,3,3,3-hexafluoro-2-propanol residue described above has good solubility in the developer. As a water repellency improver, polymers containing repeating units containing an amino group or an amine salt are highly effective in preventing acid evaporation during post-exposure baking (PEB) and preventing poor hole pattern opening after development. When the chemically amplified resist material of the present invention contains the water repellency improver, the content thereof is preferably 0 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of Compound A when the chemically amplified resist material of the present invention does not contain a base polymer, and when the chemically amplified resist material of the present invention contains a base polymer, the content thereof is preferably 0 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of base polymer. The water repellency improvers may be used alone or in combination of two or more.

[0274] Examples of the acetylene alcohols include those described in paragraphs

[0179] to

[0182] of JP 2008-122932 A. When the chemically amplified resist material of the present invention contains the acetylene alcohols, the content thereof is preferably 0 to 5 parts by mass per 100 parts by mass of Compound A when the chemically amplified resist material of the present invention does not contain a base polymer, and preferably 0 to 5 parts by mass per 100 parts by mass of base polymer when the chemically amplified resist material of the present invention contains a base polymer. The acetylene alcohols may be used alone or in combination of two or more.

[0275] [Pattern formation method] When the chemically amplified resist material of the present invention is used in the manufacture of various integrated circuits, known lithography techniques can be applied. For example, a pattern formation method can include a method comprising the steps of forming a resist film on a substrate using the above-mentioned chemically amplified resist material, exposing the resist film to high-energy radiation, and developing the exposed resist film using a developer.

[0276] First, the chemically amplified resist material of the present invention is applied to a substrate for integrated circuit manufacturing (Si, SiO2, SiN, SiON, TiN, WSi, BPSG, SOG, organic antireflective coating, etc.) or a substrate for mask circuit manufacturing (Cr, CrO, CrON, MoSi2, SiO2, etc.) by an appropriate coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc., to a coating thickness of 0.1 to 2 μm. This is then prebaked on a hot plate, preferably at 60 to 150°C for 10 seconds to 30 minutes, more preferably at 80 to 120°C for 30 seconds to 20 minutes, to form a resist film.

[0277] Next, the resist film is exposed to high-energy radiation. Examples of the high-energy radiation include ultraviolet radiation, far ultraviolet radiation, EB, EUV radiation with a wavelength of 3 to 15 nm, X-rays, soft X-rays, excimer laser light, gamma rays, and synchrotron radiation. When ultraviolet radiation, far ultraviolet radiation, EUV radiation, X-rays, soft X-rays, excimer laser light, gamma rays, and synchrotron radiation are used as the high-energy radiation, the exposure dose is preferably 1 to 200 mJ / cm, either directly or using a mask for forming a desired pattern. 2 approximately, more preferably 10 to 100 mJ / cm 2 When EB is used as the high energy beam, the exposure dose is preferably 0.1 to 100 μC / cm 2 approximately, more preferably 0.5 to 50 μC / cm 2The resist is patterned directly or using a mask to form the desired pattern. The chemically amplified resist material of the present invention is particularly suitable for fine patterning using high-energy radiation, such as i-rays with a wavelength of 365 nm, KrF excimer laser light, ArF excimer laser light, EB, EUV, X-rays, soft X-rays, γ-rays, and synchrotron radiation.

[0278] In addition to the usual exposure method, the immersion method can be used, in which a liquid with a refractive index of 1.0 or higher, such as water, is placed between the resist film and the projection lens. In this case, a water-insoluble protective film can also be used.

[0279] After the exposure, PEB may be performed on a hot plate or in an oven, preferably at 60 to 150° C. for 10 seconds to 30 minutes, more preferably at 80 to 120° C. for 30 seconds to 20 minutes.

[0280] After exposure or PEB, the exposed resist film is developed using a developer of an alkaline aqueous solution of 0.1 to 10% by weight, preferably 2 to 5% by weight, such as tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, or tetrabutylammonium hydroxide, for 3 seconds to 3 minutes, preferably 5 seconds to 2 minutes, by a conventional method such as dipping, puddling, or spraying, to form the desired pattern. In the case of a positive resist material, the irradiated portion dissolves in the developer, while the unexposed portion remains insoluble, forming the desired positive pattern on the substrate. In the case of a negative resist material, the opposite occurs: the irradiated portion becomes insoluble in the developer, while the unexposed portion dissolves.

[0281] A negative pattern can also be obtained by organic solvent development using a positive resist material containing a base polymer containing an acid labile group. The developer used in this case includes 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methylacetophenone, propyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, butenyl acetate, isopentyl acetate, propyl formate, butyl formate, isobutyl formate, pentyl formate, isopentyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, Examples of the organic solvent include methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, isopentyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate, 2-phenylethyl acetate, etc. These organic solvents may be used alone or in combination of two or more.

[0282] After the development is completed, the resist film is rinsed. A solvent that is miscible with the developer but does not dissolve the resist film is preferred as the rinse solution. Preferred examples of such solvents include alcohols having 3 to 10 carbon atoms, ether compounds having 8 to 12 carbon atoms, alkanes, alkenes, alkynes, and aromatic solvents having 6 to 12 carbon atoms.

[0283] Examples of the alcohol having 3 to 10 carbon atoms include n-propyl alcohol, isopropyl alcohol, 1-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, tert-pentyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, Examples of such an alcohol include 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol, and 1-octanol.

[0284] Examples of the ether compound having 8 to 12 carbon atoms include di-n-butyl ether, diisobutyl ether, di-sec-butyl ether, di-n-pentyl ether, diisopentyl ether, di-sec-pentyl ether, di-tert-pentyl ether, and di-n-hexyl ether.

[0285] Examples of the alkanes having 6 to 12 carbon atoms include hexane, heptane, octane, nonane, decane, undecane, dodecane, methylcyclopentane, dimethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cycloheptane, cyclooctane, and cyclononane. Examples of the alkenes having 6 to 12 carbon atoms include hexene, heptene, octene, cyclohexene, methylcyclohexene, dimethylcyclohexene, cycloheptene, and cyclooctene. Examples of the alkynes having 6 to 12 carbon atoms include hexyne, heptine, and octyne.

[0286] Examples of the aromatic solvent include toluene, xylene, ethylbenzene, isopropylbenzene, tert-butylbenzene, and mesitylene.

[0287] Rinsing can reduce the occurrence of resist pattern collapse and defects. Rinsing is not always necessary, and not performing rinsing can reduce the amount of solvent used.

[0288] The developed hole or trench pattern can also be shrunk using thermal flow, RELACS, or DSA. A shrink agent is applied to the hole pattern, and the diffusion of an acid catalyst from the resist film during baking causes crosslinking of the shrink agent on the surface of the resist film, resulting in adhesion of the shrink agent to the sidewalls of the hole pattern. The baking temperature is preferably 70 to 180°C, more preferably 80 to 170°C, and the baking time is preferably 10 to 300 seconds. Excess shrink agent is removed, and the hole pattern is shrunk. [Example]

[0289] The present invention will be specifically explained below by showing synthesis examples, examples and comparative examples, but the present invention is not limited to the following examples.

[0290] The structures of quenchers Q-1 to Q-32 used in the chemically amplified resist material are shown below. [ka]

[0291] [ka]

[0292] [ka]

[0293] [ka]

[0294] [ka]

[0295] [ka]

[0296] [ka]

[0297] [Synthesis Example] Synthesis of base polymers (polymers P-1 to P-3) Each monomer was combined and copolymerized in THF, a solvent. The reaction solution was poured into methanol, and the precipitated solid was washed with hexane, isolated, and dried to obtain the base polymers (polymers P-1 to P-3) with the following compositions. The resulting base polymers were 1 Mw and Mw / Mn were confirmed by H-NMR and GPC (solvent: THF, standard: polystyrene). [ka]

[0298] [Examples 1 to 33, Comparative Examples 1 to 3] Preparation and Evaluation of Chemically Amplified Resist Materials (1) Preparation of resist material Solutions in which the components were dissolved according to the compositions shown in Tables 1 to 3 were filtered through a 0.2 μm filter to prepare chemically amplified positive resist materials.

[0299] In Tables 1 to 3, the components are as follows. Organic solvent: PGMEA (propylene glycol monomethyl ether acetate) DAA (diacetone alcohol) EL (L-ethyl lactate)

[0300] Acid generator: PAG-1 to PAG-4 [ka]

[0301] Comparison quenchers: cQ-1 to cQ-3 [ka]

[0302] Blend Quencher: bQ-1~bQ-4 [ka]

[0303] (2) EUV lithography evaluation Each resist material listed in Tables 1-3 was spin-coated onto a Si substrate with a 20 nm thick silicon-containing spin-on hard mask (SHB-A940, manufactured by Shin-Etsu Chemical Co., Ltd.) (43% silicon by weight) and pre-baked at 100°C for 60 seconds to produce a 50 nm thick resist film. The resist film was exposed to light using an ASML EUV scanner NXE3400 (NA 0.33, σ 0.9 / 0.6, quadruple-pole illumination, 44 nm pitch on the wafer, +20% bias hole pattern mask), and then subjected to PEB for 60 seconds on a hot plate at the temperatures listed in Tables 1-3. Development was then performed for 30 seconds in a 2.38% by weight TMAH aqueous solution to form a 22 nm hole pattern. Using a critical dimension SEM (CG6300) manufactured by Hitachi High-Tech Corporation, the exposure dose when a hole dimension of 22 nm was formed was measured and used as the sensitivity. The dimensions of 50 holes were also measured, and the standard deviation (σ) calculated from the results was tripled (3σ) to give the dimensional variation (CDU). The results are shown in Tables 1 to 3.

[0304] [Table 1]

[0305] [Table 2]

[0306] [Table 3]

[0307] The results shown in Tables 1 to 3 demonstrate that the chemically amplified resist material of the present invention, which contains as a quencher a compound in which the hydrogen atom of the carboxy group of a nitrogen-containing carboxylic acid is substituted with a tertiary hydrocarbyl group having an androstane structure, exhibits improved CDU.

Claims

1. A chemically amplified resist material comprising a quencher and an acid generator, wherein the quencher comprises a compound in which a hydrogen atom of a carboxy group of a nitrogen-containing carboxylic acid is substituted with a tertiary hydrocarbyl group having an androstane structure.

2. 2. The chemically amplified resist material according to claim 1, wherein the compound in which the hydrogen atom of the carboxy group of the nitrogen-containing carboxylic acid is substituted with a tertiary hydrocarbyl group having an androstane structure is represented by the following formula (1): 【Chemistry 1】 [In the formula, m is an integer of 1 to 3. R 1 is a hydrogen atom, an aliphatic hydrocarbyl group having 1 to 14 carbon atoms, an aliphatic hydrocarbyloxycarbonyl group having 2 to 14 carbon atoms, an aliphatic hydrocarbylcarbonyl group having 2 to 10 carbon atoms, or an aralkyl group having 7 to 14 carbon atoms. When m is 1, two R 1 may be the same or different, and two R 1 may be bonded to each other to form a ring together with the nitrogen atom to which they are bonded, and some of the hydrogen atoms of the ring may be substituted with a halogen atom, a saturated hydrocarbyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, or a phenyl group which may be substituted with a halogen atom, and the ring may contain an ether bond, an ester bond, a sulfide bond, a sulfonyl group, -N= and -N(R 1 )- may contain at least one selected from R 2 is a single bond or an aliphatic or aromatic hydrocarbylene group having 1 to 10 carbon atoms, the aliphatic hydrocarbylene group may contain at least one bond selected from a halogen atom, an ether bond, an ester bond and a sulfide bond, and the aromatic hydrocarbylene group may contain at least one bond selected from a halogen atom, —N(R 2A )(R 2B ), -N(R 2C )-C(=O)-R 2D and -N(R 2C )-C(=O)-O-R 2D R 2A and R 2B are each independently a hydrogen atom or a saturated hydrocarbyl group having 1 to 6 carbon atoms. 2C is a hydrogen atom or a saturated hydrocarbyl group having 1 to 6 carbon atoms, and may contain a halogen atom, a hydroxy group, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, a saturated hydrocarbylcarbonyl group having 2 to 6 carbon atoms, or a saturated hydrocarbylcarbonyloxy group having 2 to 6 carbon atoms. 2D is an aliphatic hydrocarbyl group having 1 to 16 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an aralkyl group having 7 to 15 carbon atoms, and may contain a halogen atom, a hydroxy group, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, a saturated hydrocarbylcarbonyl group having 2 to 6 carbon atoms, or a saturated hydrocarbylcarbonyloxy group having 2 to 6 carbon atoms. When m is 1, R 1 and R 2 and may be bonded to each other to form a ring together with the nitrogen atom to which they are bonded, and some of the hydrogen atoms of the ring may be substituted with a halogen atom, a saturated hydrocarbyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, or a phenyl group which may be substituted with a halogen atom, and the ring may contain at least one bond selected from an ether bond, an ester bond, a sulfide bond, a sulfonyl group, and -N=, and the remaining R 1 and a carbon atom contained in the ring may be bonded to form a bridged ring. 2 may be the same or different from each other. X 1 is a single bond, an ether bond, an ester bond, an amide bond, or a thioester bond. When m is 2 or 3, each X 1 may be the same or different from each other. X 2 is a single bond or a hydrocarbylene group having 1 to 12 carbon atoms, and the hydrocarbylene group may contain at least one selected from an ether bond, an ester bond, a sulfide bond, a cyano group, a nitro group, a sulfonyl group, a sultone ring, a lactone ring, and a halogen atom. 2 may be the same or different from each other. R is a group containing a structure represented by the following formula (2): When m is 2 or 3, each R may be the same or different. 【Chemistry 2】 (In the formula, R 3 is an aliphatic hydrocarbyl group having 1 to 6 carbon atoms which may contain a heteroatom, or a phenyl group which may be substituted with a halogen atom. In addition, the ring in the formula may contain a double bond.)

3. 3. The chemically amplified resist material according to claim 2, wherein R is a group represented by any one of the following formulas (2)-1 to (2)-8: 【Transformation 3】 (In the formula, R 3 is an aliphatic hydrocarbyl group having 1 to 6 carbon atoms which may contain a heteroatom, or a phenyl group which may be substituted with a halogen atom. R 4 and R 5 are each independently a hydrogen atom, a hydroxy group, a saturated hydrocarbyl group having 1 to 6 carbon atoms, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, a saturated hydrocarbylcarbonyloxy group having 2 to 6 carbon atoms, a saturated hydrocarbylsulfonyloxy group having 1 to 6 carbon atoms, an oxo group, or an amino group; R 4 and R 5 may be bonded to each other to form a ring together with the carbon atom to which they are attached, and the ring may contain an ether bond, -N(H)-, -N= or a double bond. R 6 represents a hydrogen atom, a hydroxy group, a saturated hydrocarbyl group having 1 to 6 carbon atoms, a saturated hydrocarbyloxy group having 1 to 6 carbon atoms, a saturated hydrocarbylcarbonyloxy group having 2 to 6 carbon atoms, or a saturated hydrocarbylsulfonyloxy group having 1 to 6 carbon atoms. R 7 is a methyl group or an ethyl group. n is 1 or 2. The dashed lines represent bonds.)

4. 2. The chemically amplified resist material according to claim 1, wherein the acid generator generates a sulfonic acid, an imide acid, or a methide acid.

5. The chemically amplified resist material of claim 1, further comprising a base polymer.

6. 6. The chemically amplified resist material according to claim 5, wherein the base polymer contains a repeating unit represented by the following formula (a1) or a repeating unit represented by the following formula (a2): 【Chemistry 4】 (In the formula, R A are each independently a hydrogen atom or a methyl group. R 11 and R 12 are each independently an acid labile group. Y 1 is a linking group having 1 to 12 carbon atoms and containing at least one selected from a single bond, a phenylene group, a naphthylene group, an ester bond, and a lactone ring. Y 2 is a single bond or an ester bond.

7. 7. The chemically amplified resist material according to claim 6, which is a chemically amplified positive resist material.

8. 6. The chemically amplified resist material of claim 5, wherein the base polymer does not contain any acid labile groups.

9. 9. The chemically amplified resist material according to claim 8, which is a chemically amplified negative resist material.

10. 6. The chemically amplified resist material according to claim 5, wherein the base polymer contains a repeating unit represented by any one of the following formulas (f1) to (f3): 【Transformation 5】 (In the formula, R A are each independently a hydrogen atom or a methyl group. Z 1 represents a single bond, an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a naphthylene group, or a group having 7 to 18 carbon atoms obtained by combining these, or -O-Z 11 -, -C(=O)-O-Z 11 - or -C(=O)-NH-Z 11 - is. Z 11 represents an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a naphthylene group, or a group having 7 to 18 carbon atoms obtained by combining these, and may contain a carbonyl group, an ester bond, an ether bond, or a hydroxy group. Z 2 is a single bond, -Z 21 -C(=O)-O-, -Z 21 -O- or -Z 21 -O-C(=O)-. Z 21 is a saturated hydrocarbylene group having 1 to 12 carbon atoms, which may contain a carbonyl group, an ester bond, or an ether bond. Z 3 represents a single bond, a methylene group, an ethylene group, a phenylene group, a fluorinated phenylene group, a phenylene group substituted with a trifluoromethyl group, -O-Z 31 -, -C(=O)-O-Z 31 - or -C(=O)-NH-Z 31 - is. Z 31 represents an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a fluorinated phenylene group, or a phenylene group substituted with a trifluoromethyl group, and may contain a carbonyl group, an ester bond, an ether bond, or a hydroxy group. R 21 ~R 28 are each independently a halogen atom or a hydrocarbyl group having 1 to 20 carbon atoms which may contain a heteroatom. 23 and R 24 or R 26 and R 27 may be bonded to each other to form a ring together with the sulfur atom to which they are attached. R HF is a hydrogen atom or a trifluoromethyl group. M - is a non-nucleophilic counterion.)

11. 2. The chemically amplified resist material according to claim 1, further comprising an organic solvent.

12. 2. The chemically amplified resist material according to claim 1, further comprising a surfactant.

13. A pattern forming method comprising the steps of: forming a resist film on a substrate using the chemically amplified resist material according to any one of claims 1 to 12; exposing the resist film to high-energy rays; and developing the exposed resist film using a developer.

14. 14. The pattern forming method according to claim 13, wherein the high-energy beam is i-line having a wavelength of 365 nm, ArF excimer laser light having a wavelength of 193 nm, KrF excimer laser light having a wavelength of 248 nm, an electron beam, or extreme ultraviolet light having a wavelength of 3 to 15 nm.

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