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 salt compound comprising: a nitrogen atom-containing cation having a structure in which a hydrogen atom of a carboxy group is substituted with a tertiary hydrocarbyl group having an androstane structure; and a non-nucleophilic counter anion of a weak acid.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] With the increasing integration and speed of LSIs, the miniaturization of pattern rules is progressing rapidly. This is because the proliferation of 5G high-speed communication and artificial intelligence (AI) necessitates high-performance devices to process them. As a cutting-edge miniaturization technology, mass production of 5nm node devices is underway using extreme ultraviolet (EUV) lithography with a wavelength of 13.5nm. Furthermore, research using EUV lithography is progressing for next-generation 3nm node and the following-generation 2nm node devices.

[0003] As miniaturization progresses and approaches the diffraction limit of light, the contrast of light decreases. This decrease in light contrast leads to a reduction in the resolution of hole and trench patterns, as well as a decrease in the focus margin, in positive-type resist films. To prevent the decrease in resolution of resist patterns due to the decrease in light contrast, attempts are being made to improve the dissolution contrast of the resist film.

[0004] For chemically amplified positive-type resist materials that undergo an acid-induced deprotection reaction by adding an acid generator and irradiating them with light or electron beam (EB), and for chemically amplified negative-type resist materials that undergo 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 1-3).

[0005] Patent Document 3 describes a resist material containing an amine compound having a tertiary ester-type acid-unstable group. By deprotecting the acid-unstable group, the alkali dissolution rate of not only the base polymer but also the amine quencher is improved, thereby improving the dissolution contrast.

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

[0007] [Patent Document 1] Japanese Patent Publication No. 2001-194776 [Patent Document 2] Japanese Patent Publication No. 2002-226470 [Patent Document 3] Japanese Patent Publication No. 2002-363148 [Overview of the project] [Problems that the invention aims to solve]

[0008] In acid-catalyzed chemically amplified resist materials, there is a need for the development of a quencher that can improve the LWR of line patterns and the CDU of hole patterns, while also improving sensitivity. This requires further reducing the diffusion distance of the acid while simultaneously improving contrast, thus improving both conflicting properties.

[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 it is positive or negative type, and a pattern formation method using the same. [Means for solving the problem]

[0010] As a result of diligent research to achieve the above objective, the present inventors have discovered that by adding a salt compound consisting of a nitrogen atom-containing cation having a structure in which the hydrogen atom of the carboxyl group is replaced by a tertiary hydrocarbyl group having an androstan structure, and a weak acid non-nucleophilic counter anion, as a quencher, to a chemically amplified resist material containing an acid generator, a resist film with improved LWR and CDU can be obtained, which has high acid diffusion control ability due to the acid-unstable group of the large androstan structure, improves dissolution contrast by deprotecting the acid-unstable group, prevents film thinning after development, and particularly improves the solubility of the exposed area in positive-type resists, thereby improving LWR and CDU, and thus completed the present invention.

[0011] In other words, the present invention provides the following chemically amplified resist material and pattern formation method. 1. A chemically amplified resist material comprising a quencher and an acid generator, wherein the quencher comprises a salt compound consisting of a nitrogen atom-containing cation having a structure in which the hydrogen atom of a carboxyl group is substituted with a tertiary hydrocarbyl group having an androstan structure, and a non-nucleophilic counter anion of a weak acid. 2. A chemically amplified resist material of type 1, wherein the salt compound is represented by the following formula (1). [ka] [In the formula, m is an integer between 1 and 3.] R 1 These are 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, there are two R 1 These two Rs may be identical or different from each other. 1may combine with each other to form a ring together with the nitrogen atom to which they are attached, and a part 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 selected from 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 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 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; R 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; R 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 2These may bond to each other to form a ring with the nitrogen atom to which they are bonded, and some of the hydrogen atoms of the ring may be substituted with halogen atoms, saturated hydrocarbyl groups having 1 to 6 carbon atoms which may be substituted with halogen atoms, or phenyl groups which may be substituted with halogen atoms, and the ring may contain at least one selected from ether bonds, ester bonds, sulfide bonds, sulfonyl groups and -N=, and the remaining R 1 The carbon atoms in the ring may bond with the carbon atoms in the ring to form a bridged ring. When m is 2 or 3, each R 2 They may be identical or different from one another. X 1 The bonds are single bonds, ether bonds, ester bonds, amide bonds, or thioester bonds. When m is 2 or 3, each X 1 They may be identical or different from one another. 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. When m is 2 or 3, each X 2 They may be identical or different from one another. R is a group containing the structure represented by the following formula (2). When m is 2 or 3, each R may be the same or different from one another. [ka] (In the formula, R 3 This is an aliphatic hydrocarbyl group having 1 to 6 carbon atoms, which may contain heteroatoms, or a phenyl group which may be substituted with a halogen atom. The ring in the formula may also contain a double bond. X -This is a non-nucleophilic counteranion of a weak acid, selected from carboxylic acid anions, sulfonamide anions, methidoic acid anions without a fluorine atom, phenoxide anions, halide anions, carbonate anions, 1,1,1,3,3,3-hexafluoro-2-propoxide anions, 1,3-diketone anions with a fluorine atom, β-ketoester anions with a fluorine atom, and imide anions with a fluorine atom. 3. A chemically amplified resist material of type 2, wherein R is a group represented by one of the following formulas (2)-1 to (2)-8. [ka] (In the formula, R 3 This is an aliphatic hydrocarbyl group having 1 to 6 carbon atoms, which may contain heteroatoms, or a phenyl group which may be substituted with a halogen atom. R 4 and R 5 Each of these is independently a hydrogen atom, a hydroxyl 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 These atoms may bond with each other to form a ring with the carbon atoms to which they are bonded, and this ring may contain an ether bond, -N(H)-, -N=, or a double bond. R 6 These are a hydrogen atom, a hydroxyl 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, and a saturated hydrocarbylsulfonyloxy group having 1 to 6 carbon atoms. R 7 This is either a methyl group or an ethyl group. n is either 1 or 2. The dashed lines represent connections. 4. A chemically amplified resist material of type 2 or 3, wherein the carboxylic acid anion is represented by the following formula (X)-1, the sulfonamide anion is represented by the following formula (X)-2, the methidoic acid anion without a fluorine atom is represented by the following formula (X)-3, the phenoxide anion is represented by the following formula (X)-4, the 1,1,1,3,3,3-hexafluoro-2-propoxide anion is represented by the following formula (X)-5, and the 1,3-diketone anion having a fluorine atom, the β-ketoester anion having a fluorine atom, or the imide anion having a fluorine atom is represented by the following formula (X)-6. [ka] (In the formula, R 11 This is a hydrocarbyl group having 1 to 24 carbon atoms, which may contain a hydrogen atom, a fluorine atom, or a heteroatom. R 12 This is a hydrocarbyl group having 1 to 20 carbon atoms, which may contain heteroatoms. R 13 This is a hydrocarbyl group having 1 to 20 carbon atoms, which may contain a hydrogen atom or a heteroatom. R 14 ~R 16 Each of these is independently a hydrocarbyl group having 1 to 10 carbon atoms, which may contain heteroatoms other than fluorine atoms. R 17 These are halogen atoms, hydroxyl groups, cyano groups, nitro groups, amino groups, C1-C10 alkylcarbonylamino groups, C1-C10 alkylsulfonylamino groups, C1-C10 alkylsulfonyloxy groups, C1-C10 alkyl groups, phenyl groups, C1-C10 alkoxy groups, C1-C10 alkylthio groups, alkoxycarbonyl groups, C1-C10 acyl groups, or C1-C10 acyloxy groups, and some or all of the hydrogen atoms bonded to these carbon atoms may be substituted with fluorine atoms. k is an integer between 0 and 5. R 18This is a trifluoromethyl group, a C2-C21 hydrocarbylcarbonyl group, or a C2-C21 hydrocarbyloxycarbonyl group, and the hydrocarbyl portion of the hydrocarbylcarbonyl group or hydrocarbyloxycarbonyl group may contain at least one selected from an ether bond, an ester bond, a sulfide bond, a cyano group, a nitro group, a hydroxyl group, a sultone ring, a sulfonic acid ester bond, an amide bond, and a halogen atom. R 19 and R 20 These are, independently, a C1-C16 hydrocarbyl group, a C1-C16 fluorinated hydrocarbyl group, a C1-C16 hydrocarbyloxy group, and a C1-C16 fluorinated hydrocarbyloxy group, but R 19 and R 20 At least one of these is a fluorinated hydrocarbyl group having 1 to 16 carbon atoms or a fluorinated hydrocarbyloxy group having 1 to 16 carbon atoms, and the hydrocarbyl group, fluorinated hydrocarbyl group, hydrocarbyloxy group and fluorinated hydrocarbyloxy group may contain at least one selected from an ether bond, an ester bond, a thiol group, a cyano group, a nitro group, a hydroxyl group, and a halogen atom other than a fluorine atom. X 3 (This is -C(H)= or -N=.) 5. A chemically amplified resist material according to any of 1 to 4, wherein the acid generating agent generates sulfonic acid, imido acid, or methidoic acid. 6. Furthermore, one of the chemically amplified resist materials 1 to 5, including a base polymer. 7. A chemically amplified resist material of 6, 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 Each of these is independently either a hydrogen atom or a methyl group. R 21 and R 22 These are, independently, acid-unstable groups. Y 1This is a linking group having 1 to 12 carbon atoms, containing at least one selected from a single bond, a phenylene group or a naphthylene group, or an ester bond and a lactone ring. Y 2 (These are single bonds or ester bonds.) 8. Chemically amplified positive resist material, which is chemically amplified resist material 7. 9. The chemically amplified resist material of 6, wherein the base polymer does not contain acid-unstable groups. 10. Chemically amplified negative resist material, which is a chemically amplified negative resist material. 11. A chemically amplified resist material according to any of 6 to 10, wherein the base polymer contains repeating units represented by any of the following formulas (f1) to (f3). [ka] (In the formula, R A Each of these is independently either a hydrogen atom or a methyl group. Z 1 This refers to 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 - is Z 11 This refers to 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 hydroxyl group. Z 2 This is a single bond, -Z 21 -C(=O)-O-, -Z 21 -O- or -Z 21 -OC(=O)- Z 21 This is a saturated hydrocarbylene group having 1 to 12 carbon atoms, and may contain a carbonyl group, an ester bond, or an ether bond. Z 3This includes single bonds, methylene groups, ethylene groups, phenylene groups, fluorinated phenylene groups, phenylene groups substituted with trifluoromethyl groups, -OZ 31 -, -C(=O)-OZ 31 -or -C(=O)-NH-Z 31 - is Z 31 This is a phenylene group substituted with an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a fluorinated phenylene group, or a trifluoromethyl group, and may contain a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. R 31 ~R 38 Each of these is independently a C1-C20 hydrocarbyl group which may contain a halogen atom or a heteroatom. 33 and R 34 or R 36 and R 37 However, they may bond with each other to form a ring with the sulfur atom to which they are bonded. R HF This is either a hydrogen atom or a trifluoromethyl group. M - (This is a non-nucleophilic counteranion.) 12. Furthermore, any of the chemically amplified resist materials 1 to 11 containing an organic solvent. 13. Furthermore, any of the chemically amplified resist materials 1 to 12 containing a surfactant. A pattern forming method comprising the steps of: forming a resist film on a substrate using any of the chemically amplified resist materials described in 14.1 to 13; exposing the resist film with high-energy rays; and developing the exposed resist film using a developer. 15. A pattern formation method for which the high-energy ray is an i-line with a wavelength of 365 nm, an ArF excimer laser light with a wavelength of 193 nm, a KrF excimer laser light with a wavelength of 248 nm, an EB, or an EUV with a wavelength of 3 to 15 nm. [Effects of the Invention]

[0012] The salt compound contained in the quencher has a nitrogen atom-containing cation in which the hydrogen atom of the carboxyl group is replaced by a tertiary hydrocarbyl group having an androstan structure. Therefore, it has a high effect of suppressing acid diffusion due to the acid-unstable group having a bulky androstan structure, and the dissolution contrast can be improved by the deprotection reaction of the acid-unstable group. As a result, low acid diffusion and It can achieve high contrast, and the developed pattern has the characteristics of low LWR and improved CDU. The quencher containing the salt compound is particularly effective in positive-type resist materials. [Modes for carrying out the invention]

[0013] [Chemically Amplified Resist Materials] The chemically amplified resist material of the present invention comprises a quencher containing a salt compound (hereinafter also referred to as salt compound A) consisting of a nitrogen atom-containing cation having a structure in which the hydrogen atom of a carboxyl group is replaced by a tertiary hydrocarbyl group having an androstan structure, and a non-nucleophilic counter anion of a weak acid, and an acid generator. A tertiary hydrocarbyl group refers to a group obtained by the removal of a hydrogen atom from a tertiary carbon atom of a hydrocarbon. Salt compound A neutralizes the acid generated from the acid generator and simultaneously generates a carboxylic acid through a deprotection reaction, thereby improving the alkali solubility of the exposed area. The acid-unstable group having an androstan structure has a high effect in suppressing acid diffusion and, furthermore, has a nitrogen atom in its molecule, can exhibit high acid diffusion control ability. This makes it possible to improve the dissolution contrast while reducing the diffusion distance of the acid, and to form a pattern with improved LWR and CDU after development.

[0014] The acid diffusion suppression effect, contrast enhancement effect, and LWR and CDU reduction effect of salt compound A are effective in both positive and negative pattern formation using alkaline aqueous solution development, as well as in negative pattern formation using organic solvent development.

[0015] [Quencher] The quencher contained in the chemically amplified resist material of the present invention contains salt compound A. Salt compound A is particularly preferably represented by the following formula (1). [ka]

[0016] In equation (1), m is an integer between 1 and 3.

[0017] In formula (1), R 1 These are 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, there are two R 1 They may be identical or different from one another.

[0018] R 1The aliphatic hydrocarbyl group, aliphatic hydrocarbyloxycarbonyl group, and the aliphatic hydrocarbyl moiety of the aliphatic hydrocarbylcarbonyl group, which are represented by a carbon-1 to carbon-14 aliphatic hydrocarbyl group, may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples include C1-C14 alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, 3-pentyl group, tert-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, cyclopropylmethyl group, cyclopropylethyl group, cyclobutylmethyl group, cyclobutylethyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclohexylmethyl group, cyclohexylethyl group, adamantylmethyl group, norbornylmethyl group, methylcyclopropyl Cyclic saturated hydrocarbyl groups with 3 to 14 carbon atoms, such as methylcyclobutyl group, methylcyclopentyl group, methylcyclohexyl group, ethylcyclopropyl group, ethylcyclobutyl group, ethylcyclopentyl group, and ethylcyclohexyl group; alkenyl groups with 2 to 14 carbon atoms, such as vinyl group, 1-propenyl group, 2-propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, nonenyl group, and decenyl group; ethynyl group, propinyl group Examples include alkynyl groups with 2 to 14 carbon atoms, such as yl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octinyl group, noninyl group, and desynyl group; cyclic unsaturated aliphatic hydrocarbyl groups with 3 to 14 carbon atoms, such as cyclopentenyl group, cyclohexenyl group, methylcyclopentenyl group, methylcyclohexenyl group, ethylcyclopentenyl group, ethylcyclohexenyl group, and norbornenyl group; and groups obtained by combining these.

[0019] R 1 Examples of aralkyl groups with 7 to 14 carbon atoms represented by this formula include the benzyl group, 1-phenylethyl group, and 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 selected from a halogen atom, an ether bond, an ester bond, and a sulfide bond. The aromatic hydrocarbylene group may contain at least one 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. R 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. R 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 as or different from each other.

[0021] R 2The aliphatic or aromatic hydrocarbylene group represented by may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples include C1-C10 alkaned groups 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, decane-1,10-diyl group, etc. Examples include yl groups; cyclic saturated hydrocarbylene groups having 3 to 10 carbon atoms, such as cyclopropanediyl, cyclobutanediyl, cyclopentanediyl, cyclohexanediyl, adamantanediyl, and norbornanediyl; alkenediyl groups having 2 to 10 carbon atoms, such as vinylene, propene-1,3-diyl, and butene-1,4-diyl; alkynediyl groups having 2 to 10 carbon atoms, such as ethyne-1,2-diyl, propyne-1,3-diyl, and butyne-1,4-diyl; cyclic unsaturated aliphatic hydrocarbylene groups having 3 to 10 carbon atoms, such as cyclopentenediyl and cyclohexenediyl; arylene groups such as phenylene and naphthylene; and groups obtained by combining these.

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

[0023] As the ring containing the nitrogen atom, a heterocyclic ring having 3 to 12 carbon atoms is preferable, and it may be saturated or unsaturated, and may be a monocyclic ring or a polycyclic ring. In the case of a polycyclic ring, a condensed ring or a bridged ring is preferable. Specific examples of the heterocyclic ring include an aziridine ring, an aziridine ring, an azetidine ring, an azet ring, a pyrrolidine ring, a pyrroline ring, a pyrrole ring, a piperidine ring, a tetrahydropyridine ring, a pyridine ring, an azepane ring, an azocan ring, an azanorborane ring, an azadamantane 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, 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, etc. are preferable.

[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 as or different from each other.

[0025] In formula (1), X [[ID=ST19]] 2is 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. When m is 2 or 3, each X 2 They may be identical or different from one another.

[0026] X 2The hydroxylene group, represented by , having 1 to 12 carbon atoms, may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples include 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, and pentane. Alkane diyl groups having 1 to 12 carbon atoms, such as -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, decane-1,10-diyl group, undecane-1,11-diyl group, dodecane-1,12-diyl group, etc.; cyclopropanediyl group, cyclobutanediyl group, cyclopentanediyl group, cyclohexanediyl Cyclocyclic saturated hydrocarbylene groups with 3 to 12 carbon atoms, such as the yl group, adamantanediyl group, norbornanediyl group; alkenediyl groups with 2 to 12 carbon atoms, such as the vinylene group, propene-1,3-diyl group, butene-1,4-diyl group; alkynediyl groups with 2 to 12 carbon atoms, such as the ethyne-1,2-diyl group, propyne-1,3-diyl group, butyne-1,4-diyl group; cyclopentenediyl group, cyclohexenediyl group, etc. Examples include cyclic unsaturated aliphatic hydrocarbylene groups; phenylene groups, methylphenylene groups, ethylphenylene groups, n-propylphenylene groups, isopropylphenylene groups, n-butylphenylene groups, isobutylphenylene groups, sec-butylphenylene groups, tert-butylphenylene groups, naphthylene groups, methylnaphthylene groups, ethylnaphthylene groups, and other arylene groups having 6 to 12 carbon atoms; and groups obtained by combining these.

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

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

[0029] R 3 The aliphatic hydrocarbyl group having 1 to 6 carbon atoms, represented by R, may be saturated or unsaturated, and may be linear, branched, or cyclic. A specific example is R 1 Examples of aliphatic hydrocarbyl groups represented by include those with 1 to 6 carbon atoms.

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

[0031] In formulas (2)-1 to (2)-8, R 3 This is an aliphatic hydrocarbyl group having 1 to 6 carbon atoms, which may contain heteroatoms, or a phenyl group which may be substituted with a halogen atom. 4 and R 5 Each of these is independently a hydrogen atom, a hydroxyl 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 These may bond to each other to form a ring with the carbon atoms to which they are bonded, and this ring may contain an ether bond, -N(H)-, -N=, or a double bond. 6These are a hydrogen atom, a hydroxyl 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, and 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 represents a bond.

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

[0033] The following are some examples of groups represented by R, but they are not limited to these. In the following formulas, 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] The cations of salt compound A include, but are not limited to, those listed below. In the following formulas, R and R 1 This is the same as described 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] In formula (1), X - This is a non-nucleophilic counteranion of a weak acid. In this invention, a weak acid is an acid having an acidity that does not allow for the deprotection of an acid-unstable group. Examples of the non-nucleophilic counteranion include carboxylic acid anions, sulfonamide anions, methidoates without a fluorine atom, phenoxide anions, halide anions, carbonate anions, 1,1,1,3,3,3-hexafluoro-2-propoxide anions, 1,3-diketone anions with a fluorine atom, β-ketoester anions with a fluorine atom, and imide anions with a fluorine atom.

[0076] The carboxylic acid anion is preferably represented by the following formula (X)-1. The sulfonamide anion is preferably represented by the following formula (X)-2. The methidoic acid anion without a fluorine atom is preferably represented by the following formula (X)-3. The phenoxide anion is preferably represented by the following formula (X)-4. The 1,1,1,3,3,3-hexafluoro-2-propoxide anion is preferably represented by the following formula (X)-5. The 1,3-diketone anion having a fluorine atom, the β-ketoester anion having a fluorine atom, and the imide anion having a fluorine atom are preferably represented by the following formula (X)-6. [ka]

[0077] In formula (X)-1, R 11 R is a C1-C24 hydrocarbyl group which may contain a hydrogen atom, a fluorine atom, or a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. A specific example is R in formula (3A') described later. 111 Examples of hydrocarbyl groups represented by the above are similar to those exemplified. Furthermore, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a group containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and some of the -CH2- of the hydrocarbyl group may be substituted with a group containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms, and as a result, it may contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, nitro groups, mercapto groups, carbonyl groups, ether bonds, ester bonds, sulfonic acid ester bonds, carbonate bonds, lactone rings, sultone rings, carboxylic acid anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0078] In formula (X)-2, R 12 R is a hydrocarbyl group having 1 to 20 carbon atoms, which may contain heteroatoms. 13R is 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. A specific example is R in formula (3A') described later. 111 Examples of hydrocarbyl groups represented by the above are similar to those exemplified. Furthermore, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a group containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and halogen atoms, and some of the -CH2- of the hydrocarbyl group may be substituted with a group containing heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms, and as a result, it may contain hydroxyl groups, fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, cyano groups, nitro groups, mercapto groups, carbonyl groups, ether bonds, ester bonds, sulfonic acid ester bonds, carbonate bonds, lactone rings, sultone rings, carboxylic acid anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0079] In formula (X)-3, R 14 ~R 16 Each of these is a hydrocarbyl group having 1 to 10 carbon atoms, which may contain heteroatoms other than fluorine atoms. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. A specific example is R in formula (3A') described later. 111 Examples of hydrocarbyl groups represented by include those with 1 to 10 carbon atoms. In addition, some or all of the hydrogen atoms of the hydrocarbyl group may be oxygen atoms, sulfur atoms, nitrogen atoms, Other than fluorine atoms The group may be substituted with a group containing a heteroatom such as a halogen atom, and a portion of the -CH2- of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, sulfur atom, or nitrogen atom, resulting in the hydroxyl group ,salt It may also contain elementary atoms, bromine atoms, iodine atoms, cyano groups, nitro groups, mercapto groups, carbonyl groups, ether bonds, ester bonds, sulfonic acid ester bonds, carbonate bonds, lactone rings, sultone rings, carboxylic acid anhydrides (-C(=O)-OC(=O)-), haloalkyl groups, etc.

[0080] In formula (X)-4, R 17 is a halogen atom, a hydroxy group, a cyano group, a nitro group, an amino group, an alkylcarbonylamino group having 1 to 10 carbon atoms, an alkylsulfonylamino group having 1 to 10 carbon atoms, an alkylsulfonyloxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, a phenyl group, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkoxycarbonyl group, an acyl group having 1 to 10 carbon atoms or an acyloxy group having 1 to 10 carbon atoms, and some or all of the hydrogen atoms bonded to these carbon atoms may be substituted with fluorine atoms. k is an integer of 0 to 5. When k is 2 or more, each R 17 may be the same as or different from each other.

[0081] In formula (X)-5, R 18 is a trifluoromethyl group, a hydrocarbylcarbonyl group having 2 to 21 carbon atoms or a hydrocarbyloxycarbonyl group having 2 to 21 carbon atoms. The hydrocarbyl moiety of the hydrocarbylcarbonyl group or hydrocarbyloxycarbonyl group may be saturated or unsaturated, and may be linear, branched or cyclic. Specific examples thereof include the same as those exemplified as the hydrocarbyl group represented by R 111 in formula (3A') described later. Further, the hydrocarbyl moiety of the hydrocarbylcarbonyl group or hydrocarbyloxycarbonyl group may contain at least one selected from an ether bond, an ester bond, a sulfide bond, a cyano group, a nitro group, a hydroxy group, a sultone ring, a sulfonic acid ester bond, an amide bond and a halogen atom.

[0082] In formula (X)-6, R 19 and R 20 are each independently a hydrocarbyl group having 1 to 16 carbon atoms, a fluorinated hydrocarbyl group having 1 to 16 carbon atoms, a hydrocarbyloxy group having 1 to 16 carbon atoms, a fluorinated hydrocarbyloxy group having 1 to 16 carbon atoms, but R 19 and R 20At least one of them is a fluorinated hydrocarbyl group having 1 to 16 carbon atoms or a fluorinated hydrocarbyloxy group having 1 to 16 carbon atoms. The hydrocarbyl moiety of the hydrocarbyl group and the hydrocarbyloxy group may be saturated or unsaturated, and may be linear, branched or cyclic. Specific examples thereof include R in the formula (3A') described later 111 Among the exemplified hydrocarbyl groups represented by, those having 1 to 16 carbon atoms are mentioned. The fluorinated hydrocarbyl moiety of the fluorinated hydrocarbyl group and the fluorinated hydrocarbyloxy group may be saturated or unsaturated, and may be linear, branched or cyclic. Specific examples thereof include monofluoromethyl group, difluoromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 1,1,2,2,2-pentafluoroethyl group, 1,1,1,3,3,3-hexafluoro-2-propyl group, 1,1,2,2,3,3,3-heptafluoropropyl group, 1,1,2,2,3,3,4,4,4-nonafluorobutyl group, 2-fluorophenyl group, 3-fluorophenyl group, 4-fluorophenyl group, 2,4-difluorophenyl group, 2,3-difluorophenyl group, 3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,4,5-trifluorophenyl group, 2,3,4-trifluorophenyl group, 2,3,4,5-tetrafluorophenyl group, 2,3,5,6-tetrafluorophenyl group, 2,3,4,5,6-pentafluorophenyl group, pentafluoromethylphenyl group, 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 2,4,5-trifluorophenyl group, etc. Further, the hydrocarbyl group, fluorinated hydrocarbyl group, hydrocarbyloxy group and fluorinated hydrocarbyloxy group may contain at least one selected from an ether bond, an ester bond, a thiol group, a cyano group, a nitro group, a hydroxy group and a halogen atom other than a fluorine atom. X 3 is -C(H)= or -N=.

[0083] Examples of the carboxylic acid anion include, but are not limited to, those shown below.

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[0084]

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[0085]

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[0086]

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[0087]

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[0088]

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[0089]

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[0090]

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[0091]

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[0092]

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[0093]

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[0094]

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[0095]

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[0096]

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[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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[0105] [ka]

[0106] [ka]

[0107] [ka]

[0108] [ka]

[0109] [ka]

[0110] Examples of sulfonamide anions include, but are not limited to, those listed below. [ka]

[0111] [ka]

[0112] [ka]

[0113] [ka]

[0114] [ka]

[0115]

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[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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[0125] [ka]

[0126] [ka]

[0127] [ka]

[0128] Examples of methidoates that do not have a fluorine atom include, but are not limited to, those listed below. [ka]

[0129] [ka]

[0130] [ka]

[0131] [ka]

[0132] Examples of the phenoxide anions mentioned above include, but are not limited to, those listed below. [ka]

[0133] [ka]

[0134] [ka]

[0135] [ka]

[0136] [ka]

[0137] [ka]

[0138] Examples of the 1,1,1,3,3,3-hexafluoro-2-propoxide anions mentioned above include, but are not limited to, those listed below. [ka]

[0139] [ka]

[0140] [ka]

[0141] [ka]

[0142] [ka]

[0143] [ka]

[0144] [ka]

[0145] [ka]

[0146] [ka]

[0147] [ka]

[0148] Examples of 1,3-diketone anions containing a fluorine atom, β-ketoester anions containing a fluorine atom, and imide anions containing a fluorine atom include, but are not limited to, those listed below. [ka]

[0149] [ka]

[0150] [ka]

[0151] [ka]

[0152] [ka]

[0153] Salt compound A is a salt compound consisting of a nitrogen atom-containing cation having a structure in which the hydrogen atom of the carboxyl group is replaced by a tertiary hydrocarbyl group having an androstan structure, and a non-nucleophilic counter anion of a weak acid. Therefore, it can achieve low acid diffusion and high contrast through the exchange reaction of strong acids generated from the acid generator, the acid diffusion control ability due to the bulky androstan structure, and the deprotection reaction of acid-unstable groups by the acid. This makes it possible to improve LWR or CDU.

[0154] Salt compound A can be obtained, for example, by a neutralization reaction of a compound obtained by the esterification reaction of a nitrogen atom-containing carboxylic acid compound with a tertiary alcohol having an androstan structure, with an acid.

[0155] In the chemically amplified resist material of the present invention, the content of the quencher consisting of salt compound A is preferably 0.001 to 50 parts by mass, and more preferably 0.01 to 20 parts by mass, relative to 100 parts by mass of the base polymer described later, from the viewpoint of sensitivity and acid diffusion suppression effect. Salt compound A may be used alone or in combination of two or more types.

[0156] The quencher may include quenchers other than salt compound A (hereinafter referred to as "other quenchers"). Examples of other quenchers include conventional basic compounds. Examples of conventional basic compounds include primary, secondary, or tertiary aliphatic amines, hybrid 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, carbamates, etc. In particular, primary, secondary, and tertiary amine compounds described in paragraphs

[0146] to

[0164] of Japanese Patent Publication No. 2008-111103, especially amine compounds having a hydroxyl group, ether bond, ester bond, lactone ring, cyano group, or sulfonic acid ester bond, or compounds having a carbamate group described in Japanese Patent Publication No. 3790649, etc. are preferred. By adding such basic compounds, it is possible to further suppress the diffusion rate of acids in the resist film or correct its shape, for example.

[0157] Other quenchers include the polymer-type quencher described in Japanese Patent Publication No. 2008-239918. This enhances the rectangularity of the resist pattern by oriented on the surface of the resist film. Polymer-type quenchers also have the effect of preventing film thinning of the pattern and rounding of the pattern top when a protective film for immersion lithography is applied.

[0158] In addition, ammonium salts, sulfonium salts, or iodonium salts may be added as other quenchers. In this case, suitable ammonium salts, sulfonium salts, or iodonium salts added as quenchers are salts of carboxylic acids, sulfonic acids, sulfonimides, or saccharins. The carboxylic acid in this case may or may not have fluorinated at the α-position.

[0159] Examples of such quenchers include compounds represented by the following formula (q1) (onium salts of sulfonic acids with the α-position not fluorinated), 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]

[0160] In formula (q1), R q1 This refers to 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 α-carbon atom of the sulfo group is substituted with a fluorine atom or a fluoroalkyl group.

[0161] R q1 The C1-C40 hydrocarbyl group represented by can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include C1-C40 alkyl groups 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 with 3 to 40 carbon atoms, such as decanyl group, adamantyl group, and adamantylmethyl group; alkenyl groups with 2 to 40 carbon atoms, such as vinyl group, allyl group, propenyl group, butenyl group, and hexenyl group; cyclic unsaturated aliphatic hydrocarbyl groups with 3 to 40 carbon atoms, such as cyclohexenyl group; phenyl group, naphthyl group, alkylphenyl group (2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl group, 4-methylmethylphenyl group, 4-methylphenyl group, methylphenyl group, methylphenyl group, 4-methylphenyl group, methylphenyl group, methylphenyl group, methylphenyl group, methylphenyl group, methylphenyl group, methylphenyl group, methylphenyl group, methylphenyl group, methylphenyl group, methylphenyl group, methylphenyl group, methylphenyl group, methylphenyl group, methylphenyl group, methylphenyl group, methylphenyl group, methylphenyl group, methylphenyl group, methylphenyl group, methylphenyl group, methylphenyl group, methylphenyl group, methylphenyl group, methylphenyl group, methylphenyl group, Examples include aryl groups with 6 to 40 carbon atoms, such as t-butylphenyl group, 4-n-butylphenyl group, dialkylphenyl group (2,4-dimethylphenyl group, 2,4,6-triisopropylphenyl group, etc.), alkylnaphthyl group (methylnaphthyl group, ethylnaphthyl group, etc.), and dialkylnaphthyl group (dimethylnaphthyl group, diethylnaphthyl group, etc.); and aralkyl groups with 7 to 40 carbon atoms, such as benzyl group, 1-phenylethyl group, and 2-phenylethyl group.

[0162] 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, sulfur atom, nitrogen atom, or halogen atom, and some of the -CH2- of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, sulfur atom, or nitrogen atom, and as a result, it may contain a hydroxyl group, a cyano group, a carbonyl group, an ether bond, an ester bond, a sulfonic acid ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic acid anhydride (-C(=O)-OC(=O)-), a haloalkyl group, etc. Examples of hydrocarbyl groups containing heteroatoms include heteroaryl groups such as thienyl groups; alkoxyphenyl groups such as 4-hydroxyphenyl, 4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl, 4-ethoxyphenyl, 4-tert-butoxyphenyl, and 3-tert-butoxyphenyl groups; alkoxynaphthyl groups such as methoxynaphthyl, ethoxynaphthyl, n-propoxynaphthyl, and n-butoxynaphthyl groups; dialkoxynaphthyl groups such as dimethoxynaphthyl and diethoxynaphthyl groups; and aryloxoalkyl groups such as 2-aryl-2-oxoethyl groups such as 2-phenyl-2-oxoethyl, 2-(1-naphthyl)-2-oxoethyl, and 2-(2-naphthyl)-2-oxoethyl groups.

[0163] In formula (q2), R q2 R is a hydrocarbyl group having 1 to 40 carbon atoms, which may contain heteroatoms. q2 The hydrocarbyl group represented by R is q1 Examples of hydrocarbyl groups represented by the same formulas as those exemplified above include the following. Other specific examples include fluorine-containing alkyl groups such as trifluoromethyl group, trifluoroethyl group, 2,2,2-trifluoro-1-methyl-1-hydroxyethyl group, and 2,2,2-trifluoro-1-(trifluoromethyl)-1-hydroxyethyl group; and fluorine-containing aryl groups such as pentafluorophenyl group and 4-trifluoromethylphenyl group.

[0164] In equation (q3), R q3This is a saturated hydrocarbyl group having 1 to 8 carbon atoms and having at least 3 fluorine atoms, or an aryl group having 6 to 10 carbon atoms and having at least 3 fluorine atoms, and the saturated hydrocarbyl group and aryl group may contain a nitro group.

[0165] In equations (q1), (q2), and (q3), MQ + This is an onium cation. The onium cation is preferably a sulfonium cation, iodonium cation, or ammonium cation, and more preferably a sulfonium cation. An example of a sulfonium cation is the sulfonium cation described in Japanese Patent Publication No. 2017-219836.

[0166] As a quencher, a sulfonium salt of an iodized benzene ring-containing carboxylic acid represented by the following formula (q4) can also be suitably used. [ka]

[0167] In formula (q4), R q11 This may be 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, or -N(R q11A )-C(=O)-R q11B Or -N(R q11A )-C(=O)-OR q11B That is. R q101A R is a hydrogen atom or a saturated hydrocarbyl group having 1 to 6 carbon atoms. q11B This is a saturated hydrocarbyl group having 1 to 6 carbon atoms or an unsaturated aliphatic hydrocarbyl group having 2 to 8 carbon atoms.

[0168] In equation (q4), x' is an integer between 1 and 5. y' is an integer between 0 and 3. z' is an integer between 1 and 3. LA This is a single bond or a (z'+1) valence linking group having 1 to 20 carbon atoms, and may contain at least one selected from an ether bond, carbonyl group, ester bond, amide bond, sultone ring, lactam ring, carbonate bond, halogen atom, hydroxyl group, and carboxyl 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 They may be the same or different from one another.

[0169] In formula (q4), R q12 , R q13 and R q14 Each of these is a hydrocarbyl group having 1 to 20 carbon atoms, which may independently contain a halogen atom or a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. A specific example is R in formula (3) described later. 101 ~R 103 Examples of hydrocarbyl groups represented by are similar to those exemplified. Furthermore, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a hydroxyl group, carboxyl group, halogen atom, oxo group, cyano group, nitro group, sultone ring, sulfo group, or sulfonium salt-containing group, and some of the -CH2- of the hydrocarbyl group may be substituted with an ether bond, ester bond, carbonyl group, amide bond, carbonate bond, or sulfonic acid ester bond. Also, R q12 and R q13 These may bond with each other to form a ring with the sulfur atom to which they are bonded.

[0170] Specific examples of compounds represented by formula (q4) include those described in Japanese Patent Publication No. 2017-219836 and Japanese Patent Publication No. 2021-91666.

[0171] If the chemically amplified resist material of the present invention contains other quenchers, their content is preferably 0 to 5 parts by mass, and more preferably 0 to 4 parts by mass, per 100 parts by mass of the base polymer described later. The other quenchers may be used individually or in combination of two or more.

[0172] [Acid Generator] The chemically amplified resist material of the present invention includes an acid generator. The acid generator may be an additive-type acid generator different from the quencher and the components described later, and may also function as a base polymer as described later, in other words, a polymer-bound type acid generator that also functions as a base polymer.

[0173] As an additive-type acid generator, a compound that generates acid in response to active light or radiation (photoacid generator) is preferred. Any compound that generates acid upon irradiation with high-energy rays can be used as the photoacid generator, but those that generate sulfonic acid, imido acid, or methidic acid are preferred. Suitable photoacid generators include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxyimide, oxime-O-sulfonate type acid generators, etc. Specific examples of photoacid generators are those described in paragraphs

[0122] to

[0142] of Japanese Patent Publication No. 2008-111103.

[0174] Furthermore, a photoacid generator represented by the following formula (3) can also be suitably used. [ka]

[0175] In formula (3), R 101 ~R 103 Each of these is independently a C1-C20 hydrocarbyl group which may contain a halogen atom or a heteroatom.

[0176] Examples of the halogen atoms mentioned above include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0177] R 101 ~R 103 The hydrocarbyl group, represented by , having 1 to 20 carbon atoms, may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples include C1-C20 alkyl groups 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 eicosyl; C3-C20 cyclic saturated hydrocarbyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, 4-methylcyclohexyl, cyclohexylmethyl, norbornyl, and adamantyl; C2-C20 alkenyl groups such as vinyl, propenyl, butenyl, and hexenyl; and ethynyl groups. Examples include alkynyl groups with 2 to 20 carbon atoms, such as propynyl and butynyl groups; cyclic unsaturated aliphatic hydrocarbyl groups with 3 to 20 carbon atoms, such as cyclohexenyl and norbornenyl groups; aryl groups with 6 to 20 carbon atoms, such as phenyl, methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, sec-butylphenyl, tert-butylphenyl, naphthyl, methylnaphthyl, ethylnaphthyl, n-propylnaphthyl, isopropylnaphthyl, n-butylnaphthyl, isobutylnaphthyl, sec-butylnaphthyl, and tert-butylnaphthyl groups; aralkyl groups with 7 to 20 carbon atoms, such as benzyl and phenethyl groups; and groups obtained by combining these.

[0178] 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, sulfur atom, nitrogen atom, or halogen atom, and some of the -CH2- of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, sulfur atom, or nitrogen atom, and as a result, it may contain a hydroxyl 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 sulfonic acid ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic acid anhydride (-C(=O)-OC(=O)-), a haloalkyl group, etc.

[0179] Also, R 101 and R 102 However, they may bond with each other to form a ring with the sulfur atom to which they are bonded. In this case, the ring is preferably structured as shown below. [ka] (In the formula, the dashed line represents R 103 (This is a combination of the two.)

[0180] Examples of cations of the sulfonium salt represented by formula (3) include, but are not limited to, those listed below. [ka]

[0181] [ka]

[0182] [ka]

[0183] [ka]

[0184]

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[0185]

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[0186]

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[0187]

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[0188]

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[0189]

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[0190]

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[0191]

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[0192]

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[0193]

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[0194]

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[0195] [ka]

[0196] [ka]

[0197] [ka]

[0198] [ka]

[0199] [ka]

[0200] [ka]

[0201] [ka]

[0202] [ka]

[0203] [ka]

[0204] In equation (3), Xa - This is an anion selected from the following formulas (3A) to (3D). [ka]

[0205] In formula (3A), R fa R 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. A specific example is R in formula (3A') described later. 111 Examples of hydrocarbyl groups represented by the symbol shown are similar to those exemplified.

[0206] The anion represented by formula (3A) is preferably the one represented by formula (3A') below. [ka]

[0207] In formula (3A'), R HF R is a hydrogen atom or a trifluoromethyl group, preferably a trifluoromethyl group. 111 This is a hydrocarbyl group having 1 to 38 carbon atoms, which may contain heteroatoms. The heteroatoms are preferably oxygen atoms, nitrogen atoms, sulfur atoms, halogen atoms, etc., with oxygen atoms being more preferred. The hydrocarbyl group is particularly preferred to have 6 to 30 carbon atoms in order to obtain high resolution in fine pattern formation.

[0208] R 111The hydrocarbyl group represented by can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include C1-C38 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl, 2-ethylhexyl, nonyl, undecyl, tridecyl, pentadecyl, heptadecyl, and eicosyl; and cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-adamantylmethyl, and norbornyl groups. Examples include cyclic saturated hydrocarbyl groups with 3 to 38 carbon atoms, such as norbornylmethyl group, tricyclodecanyl group, tetracyclododecanyl group, tetracyclododecanylmethyl group, and dicyclohexylmethyl group; unsaturated aliphatic hydrocarbyl groups with 2 to 38 carbon atoms, such as allyl group and 3-cyclohexenyl group; aryl groups with 6 to 38 carbon atoms, such as phenyl group, 1-naphthyl group, and 2-naphthyl group; aralkyl groups with 7 to 38 carbon atoms, such as benzyl group and diphenylmethyl group; and groups obtained by combining these.

[0209] 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, sulfur atom, nitrogen atom, or halogen atom, and some of the -CH2- of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, sulfur atom, or nitrogen atom, and as a result, it may contain a hydroxyl 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 sulfonic acid ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic acid anhydride (-C(=O)-OC(=O)-), a haloalkyl group, etc. Examples of hydrocarbyl groups containing heteroatoms include tetrahydrofuryl group, methoxymethyl group, ethoxymethyl group, methylthiomethyl group, acetamidomethyl group, trifluoroethyl group, (2-methoxyethoxy)methyl group, acetoxymethyl group, 2-carboxy-1-cyclohexyl group, 2-oxopropyl group, 4-oxo-1-adamantyl group, and 3-oxocyclohexyl group.

[0210] For details on the synthesis of sulfonium salts containing the anion represented by formula (3A'), please refer to Japanese Patent Publication No. 2007-145797, Japanese Patent Publication No. 2008-106045, Japanese Patent Publication No. 2009-7327, Japanese Patent Publication No. 2009-258695, etc. Also, sulfonium salts described in Japanese Patent Publication No. 2010-215608, Japanese Patent Publication No. 2012-41320, Japanese Patent Publication No. 2012-106986, Japanese Patent Publication No. 2012-153644, etc., can be suitably used.

[0211] The anions represented by formula (3A) include, but are not limited to, those listed below. In the formula below, Ac represents an acetyl group. [ka]

[0212] [ka]

[0213] [ka]

[0214] [ka]

[0215] In formula (3B), R fb1 and R fb2 Each of these is a hydrocarbyl group having 1 to 40 carbon atoms, which may each contain a fluorine atom or a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. A specific example is R in formula (3A'). 111 Examples of hydrocarbyl groups represented by R include those similar to those exemplified. fb1 and R fb2 Preferably, R is a fluorine atom or a linear fluorinated alkyl group having 1 to 4 carbon atoms. fb1 and R fb2This refers to the groups that bond to each other (-CF2-SO2-N - It may form a ring with -SO2-CF2-), in which case R fb1 and R fb2 The group obtained by the bonding of these two elements is preferably a fluorinated ethylene group or a fluorinated propylene group.

[0216] In formula (3C), R fc1 , R fc2 and R fc3 Each of these is a hydrocarbyl group having 1 to 40 carbon atoms, which may each contain a fluorine atom or a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. A specific example is R in formula (3A'). 111 Examples of hydrocarbyl groups represented by R include those similar to those exemplified. fc1 , R fc2 and R fc3 Preferably, R is a fluorine atom or a linear fluorinated alkyl group having 1 to 4 carbon atoms. fc1 and R fc2 This refers to the groups that bond to each other (-CF2-SO2-C - It may form a ring with -SO2-CF2-), in which case R fc1 and R fc2 The group obtained by the bonding of these two elements is preferably a fluorinated ethylene group or a fluorinated propylene group.

[0217] In formula (3D), R fd R is a hydrocarbyl group having 1 to 40 carbon atoms, which may contain heteroatoms. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. A specific example is R in formula (3A'). 111 Examples of hydrocarbyl groups represented by the same formula as those exemplified above include those shown.

[0218] The synthesis of sulfonium salts containing the anion represented by formula (3D) is detailed in Japanese Patent Publication No. 2010-215608 and Japanese Patent Publication No. 2014-133723.

[0219] The anions represented by formula (3D) include, but are not limited to, those listed below. [ka]

[0220] [ka]

[0221] Furthermore, the photoacid generator containing the anion represented by formula (3D) does not have a fluorine atom at the α-position of the sulfo group, but has two trifluoromethyl groups at the β-position, which gives it sufficient acidity to cleave acid-unstable groups in the base polymer. Therefore, it can be used as a photoacid generator.

[0222] As a photoacid generator, one represented by the following formula (4) can also be suitably used. [ka]

[0223] In formula (4), R 201 and R 202 Each of these is independently a hydrocarbyl group having 1 to 30 carbon atoms, which may contain a halogen atom or a heteroatom. 203 This is a hydrocarbylene group having 1 to 30 carbon atoms, which may contain heteroatoms. Also, R 201 , R 202 and R 203 Any two of these may bond with each other to form a ring with the sulfur atom to which they are bonded. In this case, the ring is defined as R in the explanation of formula (3). 101 and R 102 Examples of rings that can be formed when these elements combine with the sulfur atom to which they are bonded are similar to those exemplified.

[0224] R 201 and R 202The hydrocarbyl group represented by can be saturated or unsaturated, and can be linear, branched, or cyclic. Specific examples include alkyl groups having 1 to 30 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, tert-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl; cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentylbutyl, cyclohexylmethyl, cyclohexylethyl, cyclohexylbutyl, norbornyl, oxanorbornyl, and tricyclo[5.2.1.0 2,6 Examples include cyclic saturated hydrocarbyl groups having 3 to 30 carbon atoms, such as decanyl and adamantyl groups; aryl groups having 6 to 30 carbon atoms, such as phenyl, methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isobutylphenyl, sec-butylphenyl, tert-butylphenyl, naphthyl, methylnaphthyl, ethylnaphthyl, n-propylnaphthyl, isopropylnaphthyl, n-butylnaphthyl, isobutylnaphthyl, sec-butylnaphthyl, tert-butylnaphthyl, and anthracenyl groups; 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, sulfur atom, nitrogen atom, or halogen atom, and some of the -CH2- of the hydrocarbyl group may be substituted with a group containing a heteroatom such as an oxygen atom, sulfur atom, or nitrogen atom, and as a result, it may contain a hydroxyl 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 sulfonic acid ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic acid anhydride (-C(=O)-OC(=O)-), a haloalkyl group, etc.

[0225] R 203The hydrocarbylene group represented by may be saturated or unsaturated, and may be linear, branched, or cyclic. Specific examples include alkane diyl groups with 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, heptadecane-1,17-diyl group, etc.; cyclopentanediyl group, cyclohex Examples include cyclic saturated hydrocarbylene groups having 3 to 30 carbon atoms, such as xanediyl, norbornanediyl, and adamantanediyl groups; 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. Furthermore, 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, sulfur atom, nitrogen atom, or halogen atom, and some of the -CH2- of the hydrocarbylene group may be substituted with a group containing a heteroatom such as an oxygen atom, sulfur atom, or nitrogen atom, and as a result, it may contain a hydroxyl 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 sulfonic acid ester bond, a carbonate bond, a lactone ring, a sultone ring, a carboxylic acid anhydride (-C(=O)-OC(=O)-), a haloalkyl group, etc. The heteroatom is preferably an oxygen atom.

[0226] In formula (4), L BThis is a 1-20 carbon atom hydrocarbylene group which may contain single bonds, ether bonds, or heteroatoms. The hydrocarbylene group may be saturated or unsaturated, and may be linear, branched, or cyclic. A specific example is R 203 Examples of hydrocarbylene groups represented by the same formula as those exemplified above include the same groups as those shown.

[0227] In formula (4), X A , X B , X C and X D Each of these is independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group. However, X A , X B , X C and X D At least one of these is a fluorine atom or a trifluoromethyl group.

[0228] In equation (4), c is an integer between 0 and 3.

[0229] As the photoacid generator represented by formula (4), the one represented by the following formula (4') is preferred. [ka]

[0230] In formula (4'), L B The same as above. R HF R is a hydrogen atom or a trifluoromethyl group, preferably a trifluoromethyl group. 301 , R 302 and R 303 Each of these is 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. A specific example is R in formula (3A'). 111 Examples of hydrocarbyl groups represented by the formula shown are similar to those exemplified. x and y are each independent integers from 0 to 5, and z is an integer from 0 to 4.

[0231] Examples of photoacid generators represented by formula (4) include those similar to those exemplified as photoacid generators represented by formula (2) in Japanese Patent Publication No. 2017-026980.

[0232] Among the photoacid generators, those containing an anion represented by formula (3A') or (3D) are particularly preferred because they exhibit low acid diffusion and excellent solubility in solvents. Furthermore, those represented by formula (4') are particularly preferred because they exhibit extremely low acid diffusion.

[0233] As the photoacid generator, a sulfonium salt or iodonium salt containing an anion having an aromatic ring substituted with an iodine or bromine atom can also be used. Examples of such salts are those represented by the following formulas (5-1) or (5-2). [ka]

[0234] In equations (5-1) and (5-2), p is an integer satisfying 1 ≤ p ≤ 3. q and r are integers satisfying 1 ≤ q ≤ 5, 0 ≤ r ≤ 3, and 1 ≤ q + r ≤ 5. q is preferably an integer satisfying 1 ≤ q ≤ 3, and more preferably 2 or 3. r is preferably an integer satisfying 0 ≤ r ≤ 2.

[0235] In equations (5-1) and (5-2), X BI These atoms are iodine atoms or bromine atoms, and when p and / or q are 2 or greater, they may be the same or different from each other.

[0236] In equations (5-1) and (5-2), L 1 This is a saturated hydrocarbylene group having 1 to 6 carbon atoms, which may contain a single bond, an ether bond, or an ester bond, or an ether bond or an ester bond. The saturated hydrocarbylene group may be linear, branched, or cyclic.

[0237] In equations (5-1) and (5-2), L 2When p is 1, it is a single bond or a divalent linking group having 1 to 20 carbon atoms, and when p is 2 or 3, it is a (p+1) valent linking group having 1 to 20 carbon atoms, and the linking group may contain an oxygen atom, a sulfur atom, or a nitrogen atom.

[0238] In equations (5-1) and (5-2), R 401 This may include a hydroxyl group, a carboxyl group, a fluorine atom, a chlorine atom, a bromine atom, or an amino group, or a fluorine atom, a chlorine atom, a bromine atom, a hydroxyl group, an amino group, or an ether bond, and may contain a C1-C20 hydrocarbyl group, a C1-C20 hydrocarbyloxy group, a C2-C20 hydrocarbylcarbonyl group, a C2-C20 hydrocarbyloxycarbonyl group, a C2-C20 hydrocarbylcarbonyloxy group, or a C1-C20 hydrocarbylsulfonyloxy group, or -N(R 401A )(R 401B ), -N(R 401C )-C(=O)-R 401D Or -N(R 401C )-C(=O)-OR 401D That is. R 401A and R 401B Each of these is independently a hydrogen atom or a saturated hydrocarbyl group having 1 to 6 carbon atoms. 401C R is a hydrogen atom or a saturated hydrocarbyl group having 1 to 6 carbon atoms, and may also contain a halogen atom, a hydroxyl 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. 401DThis 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 hydroxyl 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 They may be the same or different from one another.

[0239] Of these, R 401 Examples include hydroxyl groups, -N(R 401C )-C(=O)-R 401D , -N(R 401C )-C(=O)-OR 401D Fluorine atoms, chlorine atoms, bromine atoms, methyl groups, methoxy groups, etc. are preferred.

[0240] In equations (5-1) and (5-2), Rf 1 ~Rf 4 Each of these is independently a hydrogen atom, a fluorine atom, or a trifluoromethyl group, but at least one of these is either a fluorine atom or a trifluoromethyl group. Also, Rf 1 and Rf 2 These may combine to form a carbonyl group. In particular, Rf 3 and Rf 4 It is preferable that both are fluorine atoms.

[0241] In equations (5-1) and (5-2), R 402 ~R 406Each of these is a hydrocarbyl group having 1 to 20 carbon atoms, which may independently contain a halogen atom or a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. For example, in the explanation of formula (3), R 101 ~R 103 Examples of hydrocarbyl groups represented by the above are similar to those exemplified. Furthermore, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a hydroxyl group, carboxyl group, halogen atom, cyano group, nitro group, mercapto group, sultone ring, sulfo group, or sulfonium salt-containing group, and some of the -CH2- of the hydrocarbyl group may be substituted with an ether bond, ester bond, carbonyl group, amide bond, carbonate bond, or sulfonic acid ester bond. In addition, R 402 and R 403 However, they may bond with each other to form a ring with the sulfur atom to which they are bonded. In this case, the ring is R as described in the explanation of formula (3). 101 and R 102 Examples of rings that can be formed when these elements bond with each other, together with the sulfur atom to which they bond, are similar to those exemplified above.

[0242] Examples of cations for sulfonium salts represented by formula (5-1) are the same as those exemplified for sulfonium salts represented by formula (3). Examples of cations for iodonium salts represented by formula (5-2) are listed below, but are not limited to these. [ka]

[0243] [ka]

[0244] The anions of the onium salt represented by formula (5-1) or (5-2) include, but are not limited to, those listed below. Note that in the following formulas, X BI This is the same as above.

change

[0245]

change

[0246]

change

[0247]

change

[0248]

change

[0249]

change

[0250]

change

[0251]

change

[0252]

change

[0253]

change

[0254]

change

[0255]

change

[0256]

change

[0257]

change

[0258]

change

[0259]

change

[0260]

change

[0261]

change

[0262]

change

[0263]

change

[0264]

change

[0265] [ka]

[0266] [ka]

[0267] The content of the additive-type 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 later.

[0268] When the acid generator also serves as the base polymer described later, the acid generator is preferably a polymer containing repeating units derived from a compound that generates acid in response to active light or radiation. In this case, the acid generator is preferably a base polymer described later that contains repeating units f as essential units.

[0269] [Base polymer] The chemically amplified resist material of the present invention preferably includes a base polymer. In the case of a positive-type resist material, the base polymer includes repeating units containing acid-unstable groups. The repeating units containing acid-unstable groups are preferably the repeating units represented by the following formula (a1) (hereinafter also referred to as repeating unit a1) or the repeating units represented by the following formula (a2) (hereinafter also referred to as repeating unit a2). [ka]

[0270] In equations (a1) and (a2), R A Each of these is independently either a hydrogen atom or a methyl group. 21 and R 22 These are, independently, acid-unstable groups. Furthermore, if the base polymer contains both repeating unit a1 and repeating unit a2, R 21 and R 22 They may be the same or different from each other. 1This is a linking group having 1 to 12 carbon atoms, containing at least one selected from a single bond, a phenylene group or a naphthylene group, or an ester bond and a lactone ring. 2 These are single bonds or ester bonds.

[0271] Examples of monomers that give repeating unit a1 are listed below, but are not limited to these. Note that in the following formula, R A and R 21 This is the same as described above. [ka]

[0272] Examples of monomers that give repeating units a2 are listed below, but are not limited to these. Note that in the following formula, R A and R 22 This is the same as described above. [ka]

[0273] R 21 and R 22 Various acid-unstable groups can be selected, but examples include those represented by the following formulas (AL-1) to (AL-3). [ka] (In the equation, dashed lines represent connections.)

[0274] In equation (AL-1), a is an integer between 0 and 6. L1 This is a tertiary hydrocarbyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms; a trihydrocarbyl silyl group in which each hydrocarbyl group is a saturated hydrocarbyl group having 1 to 6 carbon atoms; a carbonyl group; a saturated hydrocarbyl group having 4 to 20 carbon atoms including an ether bond or an ester bond; or a group represented by formula (AL-3).

[0275] R L1The tertiary hydrocarbyl group represented by can be saturated or unsaturated, and can be branched or cyclic. Specific examples include tert-butyl group, tert-pentyl group, 1,1-diethylpropyl group, 1-ethylcyclopentyl group, 1-butylcyclopentyl group, 1-ethylcyclohexyl group, 1-butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group, 1-ethyl-2-cyclohexenyl group, and 2-methyl-2-adamantyl group. Examples of the trihydrocarbyl silyl group include trimethylsilyl group, triethylsilyl group, and dimethyl-tert-butylsilyl group. The saturated hydrocarbyl group containing the carbonyl group, ether bond, or ester bond may be linear, branched, or cyclic, but cyclic is preferred. Specific examples include 3-oxocyclohexyl group, 4-methyl-2-oxooxan-4-yl group, 5-methyl-2-oxooxolan-5-yl group, 2-tetrahydropyranyl group, and 2-tetrahydrofuranyl group.

[0276] Examples of acid-unstable groups represented by formula (AL-1) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-pentyloxycarbonyl group, tert-pentyloxycarbonylmethyl group, 1,1-diethylpropyloxycarbonyl group, 1,1-diethylpropyloxycarbonylmethyl group, 1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-2-cyclopentenyloxycarbonyl group, 1-ethyl-2-cyclopentenyloxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, and 2-tetrahydrofuranyloxycarbonylmethyl group.

[0277] Other acid-unstable groups represented by formula (AL-1) include those represented by the following formulas (AL-1)-1 to (AL-1)-10. [ka] (In the equation, dashed lines represent connections.)

[0278] In equations (AL-1)-1 to (AL-1)-10, a is the same as described above. L8 Each of these is independently a saturated hydrocarbyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms. L9 R is a hydrogen atom or a saturated hydrocarbyl group having 1 to 10 carbon atoms. L10 This 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.

[0279] In formula (AL-2), R L2 and R L3 Each of these is independently a hydrogen atom or a saturated hydrocarbyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. The saturated hydrocarbyl group may be linear, branched, or cyclic, and specific examples include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclopentyl group, cyclohexyl group, 2-ethylhexyl group, n-octyl group, and the like.

[0280] In formula (AL-2), R L4 This is a hydrocarbyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, which may contain heteroatoms. 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 these hydrogen atoms may be substituted with hydroxyl groups, alkoxy groups, oxo groups, amino groups, alkylamino groups, etc. Examples of such substituted saturated hydrocarbyl groups are shown below. [ka] (In the equation, dashed lines represent connections.)

[0281] R L2 and R L3 And, R L2 and R L4 or RL3 and R L4 These atoms may bond with each other to form a ring together with the carbon atoms to which they are bonded, or together with a carbon atom and an oxygen atom, and in this case, R involved in ring formation L2 and R L3 , R L2 and R L4 , or R L3 and R L4 Each of these is an alkanediyl group having 1 to 18 carbon atoms, preferably 1 to 10. The number of carbon atoms in the ring obtained by bonding these is preferably 3 to 10, more preferably 4 to 10.

[0282] Among the acid-unstable groups represented by formula (AL-2), those that are linear or branched include, but are not limited to, those represented by formulas (AL-2)-1 to (AL-2)-69 below. In the following formulas, dashed lines represent bonds. [ka]

[0283] [ka]

[0284] [ka]

[0285] [ka]

[0286] Among the acid-unstable groups represented by formula (AL-2), cyclic groups include tetrahydrofuran-2-yl group, 2-methyltetrahydrofuran-2-yl group, tetrahydropyran-2-yl group, and 2-methyltetrahydropyran-2-yl group.

[0287] Furthermore, examples of acid-unstable groups include groups represented by the following formulas (AL-2a) or (AL-2b). The base polymer may be intermolecularly or intramolecularly crosslinked by these acid-unstable groups. [ka] (In the equation, dashed lines represent connections.)

[0288] In formula (AL-2a) or (AL-2b), R L11 and R L12 Each of these is 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. Also, R L11 and R L12 These may bond with each other to form a ring with the carbon atoms to which they are bonded, in which case R L11 and R L12 These are, independently, alkanediyl groups having 1 to 8 carbon atoms. L13 Each of these is independently a saturated hydrocarbylene group having 1 to 10 carbon atoms. The saturated hydrocarbylene group may be linear, branched, or cyclic. Each of d and e is independently an integer from 0 to 10, preferably from 0 to 5, and f is an integer from 1 to 7, preferably from 1 to 3.

[0289] In formula (AL-2a) or (AL-2b), L C This is an aliphatic saturated hydrocarbon group having 1 to 50 carbon atoms with (f+1) valency, an alicyclic saturated hydrocarbon group having 3 to 50 carbon atoms with (f+1) valency, an aromatic hydrocarbon group having 6 to 50 carbon atoms with (f+1) valency, or a heterocyclic group having 3 to 50 carbon atoms with (f+1) valency. Furthermore, some of the -CH2- groups of these groups may be substituted with a group containing a heteroatom, and some of the hydrogen atoms bonded to the carbon atoms of these groups may be substituted with a hydroxyl group, a carboxyl group, an acyl group, or a fluorine atom. C Preferred members include saturated hydrocarbon groups such as saturated hydrocarbylene groups, trivalent saturated hydrocarbon groups, and tetravalent saturated hydrocarbon groups having 1 to 20 carbon atoms, and arylene groups having 6 to 30 carbon atoms. The saturated hydrocarbon groups may be linear, branched, or cyclic.D These are -C(=O)-O-, -NH-C(=O)-O-, or -NH-C(=O)-NH-.

[0290] Examples of crosslinked acetal groups represented by formula (AL-2a) or (AL-2b) include groups represented by the following formulas (AL-2)-70 to (AL-2)-77. [ka] (In the equation, dashed lines represent connections.)

[0291] In formula (AL-3), R L5 , R L6 and R L7 Each of these is independently a hydrocarbyl group having 1 to 20 carbon atoms, and 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 include alkyl groups having 1 to 20 carbon atoms, cyclic saturated hydrocarbyl groups having 3 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, cyclic unsaturated aliphatic hydrocarbyl groups having 3 to 20 carbon atoms, and aryl groups having 6 to 10 carbon atoms. L5 and R L6 And, R L5 and R L7 or R L6 and R L7 These atoms may bond with each other to form an alicyclic ring with 3 to 20 carbon atoms.

[0292] Examples of groups represented by formula (AL-3) include tert-butyl group, 1,1-diethylpropyl group, 1-ethylnorbonyl group, 1-methylcyclopentyl group, 1-ethylcyclopentyl group, 1-isopropylcyclopentyl group, 1-methylcyclohexyl group, 2-(2-methyl)adamantyl group, 2-(2-ethyl)adamantyl group, and tert-pentyl group.

[0293] In addition, the groups represented by formula (AL-3) include those represented by the following formulas (AL-3)-1 to (AL-3)-19. [ka] (In the equation, dashed lines represent connections.)

[0294] In equations (AL-3)-1 to (AL-3)-19, R L14 Each of these is 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 Each of these is independently a hydrogen atom or a saturated hydrocarbyl group having 1 to 20 carbon atoms. L16 This is an aryl group having 6 to 20 carbon atoms. The saturated hydrocarbyl group may be linear, branched, or cyclic. Furthermore, a phenyl group is preferred as the aryl group. F g is a fluorine atom or a trifluoromethyl group. g is an integer from 1 to 5.

[0295] Furthermore, examples of acid-unstable groups include those represented by the following formulas (AL-3)-20 or (AL-3)-21. The base polymer may be intermolecularly or intramolecularly crosslinked by these acid-unstable groups. [ka] (In the equation, dashed lines represent connections.)

[0296] In equations (AL-3)-20 and (AL-3)-21, R L14 The same as above. R L18 h is a saturated hydrocarbylene group with 1 to 20 carbon atoms and a (h+1) valency, or an arylene group with 6 to 20 carbon atoms and a (h+1) valency, and may contain heteroatoms such as oxygen, sulfur, or nitrogen atoms. The saturated hydrocarbylene group may be linear, branched, or cyclic. h is an integer from 1 to 3.

[0297] R 21 and R 22Examples of acid-unstable groups represented by this include those described in Japanese Patent Publication No. 3832564, No. 5407892, No. 5407941, No. 5434983, No. 5463963, No. 5564293, No. 5565293, No. 5573595, No. 5655754, No. 5655755, and No. 5655756. In addition, acid-unstable groups containing aromatic groups or multiple bonds as described in Japanese Patent Publication No. 5772760, Japanese Unexamined Patent Publication No. 2007-279699, Japanese Unexamined Patent Publication No. 2018-172640, Japanese Unexamined Patent Publication No. 2019-214554, Japanese Unexamined Patent Publication No. 2021-50307 and Japanese Unexamined Patent Publication No. 2021-110922, as well as acid-unstable groups having a steroid structure as described in Japanese Patent Publication No. 6411967, can also be used.

[0298] The base polymer may contain repeating unit b having a phenolic hydroxyl group as an adhesion group. Examples of monomers that give repeating unit b are, but are not limited to, those listed below. In the following formula, R A This is the same as described above. [ka]

[0299] The base polymer may also contain repeating units c as other adhesive groups, including hydroxyl groups other than phenolic hydroxyl groups, lactone rings, sultone rings, ether bonds, ester bonds, sulfonic acid ester bonds, carbonyl groups, sulfonyl groups, cyano groups, or carboxyl groups. Examples of monomers that give repeating units c are, but are not limited to, those listed below. In the following formula, R A This is the same as described above. [ka]

[0300] [ka]

[0301] [ka]

[0302] [ka]

[0303] [ka]

[0304] [ka]

[0305] [ka]

[0306] [ka]

[0307] The base polymer may contain repeating units d derived from indene, benzofuran, benzothiophene, acenaphthylene, chromone, coumarin, norbornadiene, or derivatives thereof. Examples of monomers that give repeating units d are, but are not limited to, those listed below. [ka]

[0308] The base polymer may contain repeating units e derived from styrene, vinylnaphthalene, vinylanthracene, vinylpyrene, methyleneindan, vinylpyridine, or vinylcarbazole.

[0309] The base polymer may contain repeating units f derived from an onium salt containing polymerizable unsaturated bonds. Preferred repeating units f include the repeating unit represented by the following formula (f1) (hereinafter also referred to as repeating unit f1), the repeating unit represented by the following formula (f2) (hereinafter also referred to as repeating unit f2), and the repeating unit represented by the following formula (f3) (hereinafter also referred to as repeating unit f3). Repeating units f1 to f3 may be used individually or in combination of two or more types. [ka]

[0310] In formulas (f1) to (f3), R A Each of these is independently either a hydrogen atom or a methyl group. 1 This refers to 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 - is Z 11 This is an aliphatic hydrocarbylene group, phenylene group, naphthylene group having 1 to 6 carbon atoms, 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 hydroxyl group. 2 This is a single bond, -Z 21 -C(=O)-O-, -Z 21 -O- or -Z 21 -OC(=O)- Z 21 This is a saturated hydrocarbylene group having 1 to 12 carbon atoms, and may contain a carbonyl group, an ester bond, or an ether bond. 3 This includes single bonds, methylene groups, ethylene groups, phenylene groups, fluorinated phenylene groups, phenylene groups substituted with trifluoromethyl groups, -OZ 31 -, -C(=O)-OZ 31 -or -C(=O)-NH-Z 31 - is Z 31This is a phenylene group substituted with an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a fluorinated phenylene group, or a trifluoromethyl group, and may contain a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. 11 and Z 31 The aliphatic hydrocarbylene group represented by can be saturated or unsaturated, and can be linear, branched, or cyclic. 21 The saturated hydrocarbylene group represented by can be linear, branched, or cyclic.

[0311] In formulas (f1) to (f3), R 31 ~R 38 Each of these is a hydrocarbyl group having 1 to 20 carbon atoms, which may independently contain a halogen atom or a heteroatom. The hydrocarbyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. A specific example is R in formula (3). 101 ~R 103 Examples similar to those exemplified in the description can be given. Furthermore, some or all of the hydrogen atoms of the hydrocarbyl group may be substituted with a group containing heteroatoms such as oxygen, sulfur, nitrogen, or halogen atoms, and some of the -CH2- of the hydrocarbyl group may be substituted with a group containing heteroatoms such as oxygen, sulfur, or nitrogen atoms, and as a result, it may contain a hydroxyl group, fluorine atom, chlorine atom, bromine atom, iodine atom, cyano group, nitro group, mercapto group, carbonyl group, ether bond, ester bond, sulfonic acid ester bond, carbonate bond, lactone ring, sultone ring, carboxylic acid anhydride (-C(=O)-OC(=O)-), haloalkyl group, etc.

[0312] Also, R 33 and R 34 or R 36 and R 37 However, they may bond with each other to form a ring with the sulfur atom to which they are bonded. In this case, the ring is defined as R in the explanation of formula (3). 101 and R 102Examples of rings that can be formed when these elements combine with the sulfur atom to which they are bonded are similar to those exemplified.

[0313] In formula (f2), R HF This is either a hydrogen atom or a trifluoromethyl group.

[0314] In formula (f1), M - This is a non-nucleophilic counteranion. Examples of the non-nucleophilic counteranions include halide ions such as chloride ions and bromide ions; fluoroalkyl sulfonate ions such as triflate ions, 1,1,1-trifluoroethanesulfonate ions and nonafluorobutanesulfonate ions; aryl sulfonate ions such as tosylate ions, benzenesulfonate ions, 4-fluorobenzenesulfonate ions and 1,2,3,4,5-pentafluorobenzenesulfonate ions; alkyl sulfonate ions such as mesylate ions and butanesulfonate ions; imide ions such as bis(trifluoromethylsulfonyl)imide ions, bis(perfluoroethylsulfonyl)imide ions and bis(perfluorobutylsulfonyl)imide ions; and methide ions such as tris(trifluoromethylsulfonyl)methide ions and tris(perfluoroethylsulfonyl)methide ions.

[0315] Other examples of the aforementioned non-nucleophilic counteranions include a sulfonate ion in which the α-position is substituted with a fluorine atom, represented by the following formula (f1-1); a sulfonate ion in which the α-position is substituted with a fluorine atom and the β-position is substituted with a trifluoromethyl group, represented by the following formula (f1-2); and a sulfonate ion containing an iodine atom, represented by the aforementioned formula (5-1). [ka]

[0316] In formula (f1-1), R 41R 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. A specific example is R in formula (3A'). 111 Examples of hydrocarbyl groups represented by the same formula as those exemplified above include those shown.

[0317] In formula (f1-2), R 42 R is a hydrogen atom, a C1-C30 hydrocarbyl group, or a C2-C30 hydrocarbylcarbonyl group, and the hydrocarbyl group and hydrocarbylcarbonyl group may contain an ether bond, an ester bond, a carbonyl group, or a lactone ring. The hydrocarbyl portion of the hydrocarbyl group and hydrocarbylcarbonyl group may be saturated or unsaturated, and may be linear, branched, or cyclic. A specific example is R in formula (3A'). 111 Examples of hydrocarbyl groups represented by the same formula as those exemplified above include those shown.

[0318] Examples of monomer cations that give the repeating unit f1 are listed below, but are not limited to these. Note that in the following formula, R A This is the same as described above. [ka]

[0319] Examples of monomer cations that give repeating units f2 or f3 include those similar to those exemplified as cations of sulfonium salts represented by formula (3).

[0320] Examples of monomer anions that give the repeating unit f2 are listed below, but are not limited to these. Note that in the following formula, R A This is the same as described above. [ka]

[0321] [ka]

[0322] Examples of monomer anions that give the repeating unit f3 are listed below, but are not limited to these. Note that in the following formula, R A This is the same as described above. [ka]

[0323] [ka]

[0324] By binding an acid generator to the polymer backbone, acid diffusion can be reduced, preventing a decrease in resolution due to blurring caused by acid diffusion. Furthermore, the uniform dispersion of the acid generator improves LWR and CDU.

[0325] When repeating units f are included, the base polymer also functions as the acid generator described above. In this case, the base polymer is integrated with the acid generator (i.e., it is a polymer-bound type acid generator), so the chemically amplified resist material of the present invention may or may not contain an additive-type acid generator.

[0326] The base polymer for a chemically amplified positive resist material essentially contains 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 even 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 acid generator, the content ratio of the 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 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.

[0327] On the other hand, the base polymer for a chemically amplified negative resist material does not necessarily require an acid-labile group. Examples of such a base polymer include those containing the repeating unit b and optionally further containing the 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 the 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 the repeating unit f is at least one selected from the repeating units f1 to f3, f = f1 + f2 + f3. Also, b + c + d + e + f = 1.0.

[0328] To synthesize the aforementioned base polymer, for example, the monomer that provides the repeating units described above may be heated in an organic solvent with a radical polymerization initiator added, and polymerization may be carried out.

[0329] Organic solvents used during polymerization include toluene, benzene, tetrahydrofuran (THF), diethyl ether, and dioxane. Polymerization initiators include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2-azobis(2-methylpropionate), benzoyl peroxide, and lauroyl peroxide. The polymerization temperature is preferably 50 to 80°C. The reaction time is preferably 2 to 100 hours, more preferably 5 to 20 hours.

[0330] When copolymerizing monomers containing hydroxyl groups, the hydroxyl groups may be substituted with acetal groups that are easily deprotected by acids such as ethoxyethoxy groups during polymerization, and then deprotected with a weak acid and water after polymerization. Alternatively, they may be substituted with acetyl groups, formyl groups, pivaloyl groups, etc., and then subjected to alkaline hydrolysis after polymerization.

[0331] When copolymerizing hydroxystyrene or hydroxyvinylnaphthalene, acetoxystyrene or acetoxyvinylnaphthalene may be used instead of hydroxystyrene or hydroxyvinylnaphthalene, and the acetoxy group may be deprotected by alkaline hydrolysis after polymerization to obtain hydroxystyrene or hydroxyvinylnaphthalene.

[0332] Ammonia water, triethylamine, etc., can be used as the base during alkaline hydrolysis. 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.

[0333] The base polymer has a polystyrene-based weight-average molecular weight (Mw) of 1,000 to 500,000, more preferably 2,000 to 30,000, determined by gel permeation chromatography (GPC) using THF as a solvent. When Mw is within this range, the heat resistance and solubility in alkaline developers of the resist film are good.

[0334] Furthermore, if the molecular weight distribution (Mw / Mn) of the base polymer is broad, low molecular weight and high molecular weight polymers may be present, which may result in the appearance of foreign matter on the pattern or deterioration of the pattern shape after exposure. As the pattern rules become finer, the influence of Mw and Mw / Mn tends to increase. Therefore, in order to obtain a resist material suitable for fine pattern dimensions, it is preferable that the Mw / Mn of the base polymer be narrowly dispersed, between 1.0 and 2.0, and particularly between 1.0 and 1.5.

[0335] The base polymer may contain two or more polymers with different composition ratios, Mw, and Mw / Mn.

[0336] [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 the components described later. Examples of the organic solvent include ketones such as cyclohexanone, cyclopentanone, methyl-2-n-pentyl ketone, and 2-heptanone, as described in paragraphs

[0144] to

[0145] of Japanese Patent Application Publication No. 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 include ethers such as monoethyl ether, propylene glycol dimethyl ether, and diethylene glycol dimethyl ether; esters such as propylene glycol monomethyl 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, and propylene glycol monotert-butyl ether acetate; and lactones such as γ-butyrolactone.

[0337] In the chemically amplified resist material of the present invention, the content of the organic solvent is preferably 100 to 10,000 parts by mass, and more preferably 200 to 8,000 parts by mass, per 100 parts by mass of the base polymer. The organic solvent may be used alone or as a mixture of two or more types.

[0338] [Other ingredients] In addition to the components described above, the chemically amplified resist material of the present invention may also contain surfactants, dissolution inhibitors, crosslinking agents, water-repellency enhancers, acetylene alcohols, and the like.

[0339] Examples of the surfactants mentioned above include those described in paragraphs

[0165] to

[0166] of Japanese Patent Publication No. 2008-111103. By adding a surfactant, the coatability of the resist material can be further improved or controlled. When the chemically amplified resist material of the present invention contains the surfactant, its content is preferably 0.0001 to 10 parts by mass per 100 parts by mass of the base polymer. The surfactant may be used alone or in combination of two or more types.

[0340] When the chemically amplified resist material of the present invention is of the positive type, the difference in dissolution rate between the exposed and unexposed areas can be further increased by incorporating a dissolution inhibitor, thereby further improving the resolution. Examples of the dissolution inhibitor include compounds in which the hydrogen atoms of the phenolic hydroxyl groups of a compound having a molecular weight of preferably 100 to 1000, more preferably 150 to 800 and containing two or more phenolic hydroxyl groups in the molecule are substituted with an acid-unstable group in a total proportion of 0 to 100 mol%, or compounds in which the hydrogen atoms of the carboxyl group of a compound containing a carboxyl group in the molecule are substituted with an acid-unstable group in a total proportion of 50 to 100 mol%. Specifically, examples include compounds in which the hydrogen atoms of the hydroxyl group or carboxyl group of bisphenol A, trisphenol, phenolphthalein, cresol novolac, naphthalenecarboxylic acid, adamantanecarboxylic acid, and cholic acid are substituted with an acid-unstable group, as described, for example, in paragraphs

[0155] to

[0178] of Japanese Patent Application Publication No. 2008-122932.

[0341] When the chemically amplified resist material of the present invention is of the positive type and contains the dissolution inhibitor, the content thereof is preferably 0 to 50 parts by mass, and more preferably 5 to 40 parts by mass, per 100 parts by mass of the base polymer. The dissolution inhibitor may be used alone or in combination of two or more types.

[0342] On the other hand, if the chemically amplified resist material of the present invention is negative type, a negative type pattern can be obtained by adding a crosslinking agent to reduce the dissolution rate of the exposed area. Examples of the crosslinking agent include epoxy compounds, melamine compounds, guanamine compounds, glycoluryl compounds or urea compounds, isocyanate compounds, azide compounds, and compounds containing double bonds such as alkenyloxy groups, which are substituted with at least one group selected from methylol groups, alkoxymethyl groups, and acyloxymethyl groups. These may be used as additives or introduced as pendant groups in the polymer side chains. Compounds containing hydroxyl groups can also be used as crosslinking agents.

[0343] Examples of the epoxy compound include tris(2,3-epoxypropyl) isocyanurate, trimethylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, and triethylolethane triglycidyl ether.

[0344] Examples of the melamine compounds include hexamethylmelamine, hexamethoxymethylmelamine, compounds in which 1 to 6 methylol groups of hexamethylmelamine are methoxymethylated or mixtures thereof, hexamethoxyethylmelamine, hexaacyloxymethylmelamine, compounds in which 1 to 6 methylol groups of hexamethylmelamine are acyloxymethylated or mixtures thereof.

[0345] Examples of the guanamine compounds include tetramethylolguanamine, tetramethoxymethylguanamine, compounds in which 1 to 4 methylol groups of tetramethylolguanamine are methoxymethylated or mixtures thereof, tetramethoxyethylguanamine, tetraacyloxyguanamine, compounds in which 1 to 4 methylol groups of tetramethylolguanamine are acyloxymethylated or mixtures thereof.

[0346] Examples of glycoluryl compounds include tetramethylol glycoluryl, tetramethoxy glycoluryl, tetramethoxymethyl glycoluryl, compounds in which 1 to 4 methylol groups of tetramethylol glycoluryl are methoxymethylated or mixtures thereof, compounds in which 1 to 4 methylol groups of tetramethylol glycoluryl are acyloxymethylated or mixtures thereof. Examples of urea compounds include tetramethylolurea, tetramethoxymethylurea, compounds in which 1 to 4 methylol groups of tetramethylolurea are methoxymethylated or mixtures thereof, tetramethoxyethylurea, and the like.

[0347] Examples of the isocyanate compounds include tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, and cyclohexane diisocyanate.

[0348] Examples of the aforementioned azide compounds include 1,1'-biphenyl-4,4'-bisazide, 4,4'-methylidenebisazide, and 4,4'-oxybisazide.

[0349] Examples of compounds containing the aforementioned 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.

[0350] When the chemically amplified resist material of the present invention is of the negative type and contains the crosslinking agent, the content of the crosslinking agent 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. The crosslinking agent may be used alone or in combination of two or more types.

[0351] The water-repellent enhancer improves the water repellency of the resist film surface and can be used in immersion lithography without a topcoat. Preferred water-repellent enhancers include polymers containing alkyl fluoride, polymers containing 1,1,1,3,3,3-hexafluoro-2-propanol residues of a specific structure, and those exemplified in Japanese Patent Publication No. 2007-297590 and Japanese Patent Publication No. 2008-111103 are more preferred. The water-repellent enhancer needs to be soluble in an alkaline developer or an organic solvent developer. The aforementioned water-repellent enhancer having a specific 1,1,1,3,3,3-hexafluoro-2-propanol residue exhibits good solubility in the developer. As a water-repellent enhancer, polymers containing repeating units including amino groups or amine salts are highly effective in preventing acid evaporation during post-exposure baking (PEB) and thus preventing poor hole pattern opening after development. When the chemically amplified resist material of the present invention contains the water-repellency improving agent, its content is preferably 0 to 20 parts by mass, and more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the base polymer. The water-repellency improving agent may be used alone or in combination of two or more types.

[0352] Examples of the acetylene alcohols include those described in paragraphs

[0179] to

[0182] of Japanese Patent Publication No. 2008-122932. When the chemical amplification resist material of the present invention contains the acetylene alcohols, the content is preferably 0 to 5 parts by mass per 100 parts by mass of the base polymer. The acetylene alcohols may be used individually or in combination of two or more types.

[0353] [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 may include a step of forming a resist film on a substrate using the chemically amplified resist material described above, a step of exposing the resist film with high-energy rays, and a step of developing the exposed resist film using a developer.

[0354] 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 anti-reflective film, etc.) or a substrate for mask circuit manufacturing (Cr, CrO, CrON, MoSi2, SiO2, etc.) by a suitable coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, or doctor coating, so that the coating film thickness is 0.1 to 2 μm. This is then pre-baked 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.

[0355] Next, the resist film is exposed using high-energy rays. Examples of high-energy rays include ultraviolet rays, far-ultraviolet rays, EB rays, EUV rays with wavelengths of 3 to 15 nm, X-rays, soft X-rays, excimer laser light, gamma rays, and synchrotron radiation. When using ultraviolet rays, far-ultraviolet rays, EUV rays, X-rays, soft X-rays, excimer laser light, gamma rays, or synchrotron radiation as the high-energy rays, the exposure amount is preferably 1 to 200 mJ / cm², either directly or using a mask to form the desired pattern. 2 To the extent, more preferably 10 to 100 mJ / cm² 2 Irradiate to the extent of [a certain degree]. When using EB as the high-energy beam, the exposure dose is preferably 0.1 to 100 μC / cm². 2 To a degree, more preferably 0.5 to 50 μC / cm² 2The pattern is drawn either 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 rays, including i-rays with a wavelength of 365 nm, KrF excimer laser light, ArF excimer laser light, EB, EUV, X-rays, soft X-rays, gamma rays, and synchrotron radiation.

[0356] In addition to conventional exposure methods, immersion methods can also be used, in which a liquid with a refractive index of 1.0 or higher, such as water, is interposed between the resist film and the projection lens. In this case, a protective film insoluble in water can also be used.

[0357] After exposure, PEB may be performed on a hot plate or in an oven, preferably at 60-150°C for 10 seconds to 30 minutes, more preferably at 80-120°C for 30 seconds to 20 minutes.

[0358] After exposure or PEB, the exposed resist film is developed using a developer solution containing 0.1 to 10% by mass, preferably 2 to 5% by mass, of an alkaline aqueous solution 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 conventional methods such as the dip method, puddle method, or spray method, thereby forming the desired pattern. In the case of positive-type resist materials, the areas irradiated with light dissolve in the developer solution, while the unexposed areas do not dissolve, forming the desired positive-type pattern on the substrate. In the case of negative-type resist materials, the opposite is true: the areas irradiated with light become insoluble in the developer solution, while the unexposed areas dissolve.

[0359] Negative patterns can also be obtained by developing with organic solvents using positive-type resist materials containing a base polymer with acid-unstable groups. The developers used in this process include 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 crotate, ethyl crotate, Examples 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 phenyl acetate, and 2-phenylethyl acetate. These organic solvents may be used individually or in mixtures of two or more.

[0360] At the end of development, rinsing is performed. A solvent that mixes with the developer but does not dissolve the resist film is preferred as the rinsing solution. Preferred solvents include C3-C10 alcohols, C8-C12 ether compounds, C6-C12 alkanes, alkenes, alkynes, and aromatic solvents.

[0361] The C3-C10 alcohols 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 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.

[0362] Examples of the ether compounds 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.

[0363] Examples of C6-C12 alkanes include hexane, heptane, octane, nonane, decane, undecane, dodecane, methylcyclopentane, dimethylcyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, cycloheptane, cyclooctane, and cyclononane. Examples of C6-C12 alkenes include hexene, heptene, octene, cyclohexene, methylcyclohexene, dimethylcyclohexene, cycloheptene, and cyclooctene. Examples of C6-C12 alkynes include hexine, heptine, and octine.

[0364] Examples of the aforementioned aromatic solvents include toluene, xylene, ethylbenzene, isopropylbenzene, tert-butylbenzene, and mesitylene.

[0365] Rinsing can reduce the occurrence of deformation and defects in the resist pattern. However, rinsing is not always necessary, and omitting it can reduce the amount of solvent used.

[0366] The developed hole patterns and trench patterns can also be shrunk using thermal flow, RELACS, or DSA techniques. A shrinking agent is applied to the hole pattern, and crosslinking of the shrinking agent occurs on the surface of the resist film due to the diffusion of an acid catalyst from the resist film during baking, causing the shrinking agent to adhere to the side walls 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, during which excess shrinking agent is removed and the hole pattern is reduced in size. [Examples]

[0367] The present invention will be specifically described below with reference to synthesis examples, examples, and comparative examples, but the present invention is not limited to the following examples.

[0368] The structures of the quenchers Q-1 to Q-30 used in the chemically amplified resist material are shown below. [ka]

[0369] [ka]

[0370] [ka]

[0371] [ka]

[0372] [ka]

[0373] [ka]

[0374] [ka]

[0375] [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 added to methanol, and the precipitated solid was washed with hexane, then isolated and dried to obtain base polymers (polymers P-1 to P-3) with the following compositions. The compositions of the obtained base polymers are: 1 Mw and Mw / Mn were confirmed by H-NMR using GPC (solvent: THF, standard: polystyrene). [ka]

[0376] [Examples 1-31, Comparative Examples 1-3] Preparation and Evaluation of Chemically Amplified Resist Materials (1) Preparation of resist material Solutions containing each component, as shown in Tables 1-3, were filtered through a 0.2 μm filter to prepare chemically amplified positive resist materials.

[0377] In Tables 1-3, the components are as follows: • Organic solvent: PGMEA (propylene glycol monomethyl ether acetate) DAA (Diacetone Alcohol) EL (L-ethyl lactate)

[0378] • Acid generators: PAG-1~PAG-3 [ka]

[0379] • Comparative Quenchers: cQ-1 to cQ-3 [ka]

[0380] • Blend Quencher: bQ-1~bQ-4 [ka]

[0381] (2) EUV lithography evaluation Each resist material shown in Tables 1-3 was spin-coated onto a Si substrate on which a silicon-containing spin-on hard mask SHB-A940 (silicon content 43 mass%) manufactured by Shin-Etsu Chemical Co., Ltd. had been formed to a thickness of 20 nm. A resist film with a thickness of 50 nm was fabricated by pre-baking at 100°C for 60 seconds using a hot plate. The resist film was exposed using an ASML EUV scanner NXE3400 (NA 0.33, σ 0.9 / 0.6, quadruple pole illumination, wafer-mounted dimensions of a 44 nm pitch hole pattern mask with a +20% bias). PEB was performed on a hot plate at the temperatures listed in Tables 1-3 for 60 seconds, and development was performed with a 2.38 mass% TMAH aqueous solution for 30 seconds to form a hole pattern with dimensions of 22 nm. Using a length-measuring SEM (CG6300) manufactured by Hitachi High-Tech Corporation, the exposure amount when a hole with a dimension of 22 nm was formed was measured and defined as the sensitivity. The dimensions of 50 holes at this point were also measured, and the dimensional variation (CDU) was defined as three times the standard deviation (σ) calculated from these results (3σ). The results are shown in Tables 1-3.

[0382] [Table 1]

[0383] [Table 2]

[0384] [Table 3]

[0385] The results shown in Tables 1-3 indicate that the chemically amplified resist material of the present invention containing salt compound A showed improved CDU.

Claims

1. A chemically amplified resist material comprising a quencher and an acid generator, wherein the quencher comprises a salt compound represented by the following formula (1). 【Chemistry 1】 [In the formula, m is an integer between 1 and 3.] R1 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, the two R1s may be the same or different from each other, and the two R1s may bond to each other to form a ring 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 at least one selected from an ether bond, an ester bond, a sulfide bond, a sulfonyl group, -N=, and -N(R1)-. R2 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 selected from a halogen atom, an ether bond, an ester bond, and a sulfide bond. The aromatic hydrocarbylene group may contain at least one selected from a halogen atom, -N(R2A)(R2B), -N(R2C)-C(=O)-R2D, and -N(R2C)-C(=O)-O-R2D. R2A and R2B are each independently a hydrogen atom or a saturated hydrocarbyl group having 1 to 6 carbon atoms. R 2C is a hydrogen atom or a saturated hydrocarbyl group having 1 to 6 carbon atoms, and may contain a halogen atom, a hydroxyl 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. R 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 hydroxyl 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, R1 and R2 may bond to each other and form a ring with the nitrogen atom to which they are bonded, and some of the hydrogen atoms of the ring may be substituted with halogen atoms, saturated hydrocarbyl groups having 1 to 6 carbon atoms which may be substituted with halogen atoms, or phenyl groups which may be substituted with halogen atoms, and the ring may contain at least one selected from ether bonds, ester bonds, sulfide bonds, sulfonyl groups and -N=, and the remaining R1 may bond to the carbon atoms contained in the ring to form a bridged ring. When m is 2 or 3, each R2 may be the same or different from each other. X1 is a single bond, ether bond, ester bond, amide bond, or thioester bond. When m is 2 or 3, each X1 may be the same or different from the others. X2 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. When m is 2 or 3, each X2 may be the same or different from the others. R is a group containing the structure represented by the following formula (2). When m is 2 or 3, each R may be the same or different from one another. 【Chemistry 2】 (In the formula, R3 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 also contain a double bond.) X- is a non-nucleophilic counteranion of a weak acid, selected from carboxylic acid anions, sulfonamide anions, methidoic acid anions without a fluorine atom, phenoxide anions, halide anions, carbonate anions, 1,1,1,3,3,3-hexafluoro-2-propoxide anions, 1,3-diketone anions with a fluorine atom, β-ketoester anions with a fluorine atom, and imide anions with a fluorine atom.

2. The chemically amplified resist material according to claim 1, wherein R is a group represented by any of the following formulas (2)-1 to (2)-8. 【Transformation 3】 (In the formula, R 3 This is an aliphatic hydrocarbyl group having 1 to 6 carbon atoms, which may contain heteroatoms, or a phenyl group which may be substituted with a halogen atom. R 4 and R 5 Each of these is independently a hydrogen atom, a hydroxyl 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 These atoms may bond with each other to form a ring with the carbon atoms to which they are bonded, and this ring may contain an ether bond, -N(H)-, -N=, or a double bond. R 6 These are a hydrogen atom, a hydroxyl 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, and a saturated hydrocarbylsulfonyloxy group having 1 to 6 carbon atoms. R 7 This is either a methyl group or an ethyl group. n is either 1 or 2. The dashed lines represent connecting moves.

3. The chemically amplified resist material according to claim 1, wherein the carboxylic acid anion is represented by the following formula (X)-1, the sulfonamide anion is represented by the following formula (X)-2, the methidoic acid anion without a fluorine atom is represented by the following formula (X)-3, the phenoxide anion is represented by the following formula (X)-4, the 1,1,1,3,3,3-hexafluoro-2-propoxide anion is represented by the following formula (X)-5, and the 1,3-diketone anion having a fluorine atom, the β-ketoester anion having a fluorine atom, or the imide anion having a fluorine atom is represented by the following formula (X)-6. 【Chemistry 4】 (In the formula, R 11 This is a hydrocarbyl group having 1 to 24 carbon atoms, which may contain a hydrogen atom, a fluorine atom, or a heteroatom. R 12 is a hydrocarbyl group having 1 to 20 carbon atoms which may contain heteroatoms. R 13 This is a hydrocarbyl group having 1 to 20 carbon atoms, which may contain a hydrogen atom or a heteroatom. R 14 ~R 16 Each of these is independently a C1-C10 hydrocarbyl group which may contain heteroatoms other than fluorine atoms. R 17 These are halogen atoms, hydroxyl groups, cyano groups, nitro groups, amino groups, C1-C10 alkylcarbonylamino groups, C1-C10 alkylsulfonylamino groups, C1-C10 alkylsulfonyloxy groups, C1-C10 alkyl groups, phenyl groups, C1-C10 alkoxy groups, C1-C10 alkylthio groups, alkoxycarbonyl groups, C1-C10 acyl groups, or C1-C10 acyloxy groups, and some or all of the hydrogen atoms bonded to these carbon atoms may be substituted with fluorine atoms. k is an integer between 0 and 5. R 18 This is a trifluoromethyl group, a C2-C21 hydrocarbylcarbonyl group, or a C2-C21 hydrocarbyloxycarbonyl group, and the hydrocarbyl portion of the hydrocarbylcarbonyl group or hydrocarbyloxycarbonyl group may contain at least one selected from an ether bond, an ester bond, a sulfide bond, a cyano group, a nitro group, a hydroxyl group, a sultone ring, a sulfonic acid ester bond, an amide bond, and a halogen atom. R 19 and R 20 These are, independently, a C1-C16 hydrocarbyl group, a C1-C16 fluorinated hydrocarbyl group, a C1-C16 hydrocarbyloxy group, and a C1-C16 fluorinated hydrocarbyloxy group, but R 19 and R 20 At least one of the groups is a fluorinated hydrocarbyl group having 1 to 16 carbon atoms or a fluorinated hydrocarbyloxy group having 1 to 16 carbon atoms, and the hydrocarbyl group, fluorinated hydrocarbyl group, hydrocarbyloxy group and fluorinated hydrocarbyloxy group may contain at least one selected from an ether bond, an ester bond, a thiol group, a cyano group, a nitro group, a hydroxyl group, and a halogen atom other than a fluorine atom. X 3 (This is -C(H) = or -N =.)

4. The chemically amplified resist material according to claim 1, wherein the acid generating agent generates sulfonic acid, imido acid, or methido acid.

5. Furthermore, the chemically amplified resist material according to claim 1, further comprising a base polymer.

6. The chemically amplified resist material according to claim 5, wherein the base polymer comprises a repeating unit represented by the following formula (a1) or a repeating unit represented by the following formula (a2). 【Transformation 5】 (In the formula, R A Each of these is independently either a hydrogen atom or a methyl group. R 21 and R 22 These are, independently, acid-unstable groups. Y 1 This is a linking group having 1 to 12 carbon atoms, containing at least one selected from a single bond, a phenylene group or a naphthylene group, or an ester bond and a lactone ring. Y 2 (These are single bonds or ester bonds.)

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

8. The chemically amplified resist material according to claim 5, wherein the base polymer does not contain acid-unstable groups.

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

10. The chemically amplified resist material according to claim 5, wherein the base polymer includes a repeating unit represented by any of the following formulas (f1) to (f3). 【Transformation 6】 (In the formula, R A Each of these is independently either a hydrogen atom or a methyl group. Z 1 This includes single bonds, aliphatic hydrocarbylene groups having 1 to 6 carbon atoms, phenylene groups, naphthylene groups, or groups 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 This refers to 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 hydroxyl group. Z 2 This is a single bond, -Z 21 -C(=O)-O-, -Z 21 -O- or -Z 21 -O-C(=O)-. Z 21 This is a saturated hydrocarbylene group having 1 to 12 carbon atoms, and may contain a carbonyl group, an ester bond, or an ether bond. Z 3 This includes single bonds, methylene groups, ethylene groups, phenylene groups, fluorinated phenylene groups, trifluoromethyl groups, and -O-Z. 31 -, -C(=O)-O-Z 31 - or -C(=O)-NH-Z 31 - is Z 31 This is a phenylene group substituted with an aliphatic hydrocarbylene group having 1 to 6 carbon atoms, a phenylene group, a fluorinated phenylene group, or a trifluoromethyl group, and may contain a carbonyl group, an ester bond, an ether bond, or a hydroxyl group. R 31 ~R 38 Each of these is independently a C1-C20 hydrocarbyl group which may contain a halogen atom or a heteroatom. 33 and R 34 or R 36 and R 37 However, they may bond with each other to form a ring with the sulfur atom to which they are bonded. R HF This is either a hydrogen atom or a trifluoromethyl group. M - (This is a non-nucleophilic counteranion.)

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

12. Furthermore, 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 a chemically amplified resist material according to any one of claims 1 to 12; exposing the resist film with a high-energy beam; and developing the exposed resist film using a developer.

14. The pattern forming method according to claim 13, wherein the high-energy ray is an i-ray 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, an electron beam, or extreme ultraviolet light with a wavelength of 3 to 15 nm.

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