JP2018025739A - Chemically amplified resist material and method for forming resist pattern - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a chemically amplified resist material that can exhibit excellent lithographic performance while maintaining good sensitivity.SOLUTION: The chemically amplified resist material of the present invention comprises (1) a polymer component that can be converted into soluble or insoluble with a developer by an action of an acid and (2) a component that generates a radiation-sensitive sensitizer and an acid by exposure. The (2) component comprises (a) a predetermined component, any two components in (a) to (c) components, or all of (a) to (c) components, in which the (a) component or the (c) component contains a radiation-sensitive first compound and a radiation-sensitive second compound. The first compound contains a first onium cation and a first anion; the second compound contains a second onium cation and a second anion different from the first anion; and when the first onium cation and the second onium cation are reduced into radicals, energy released by each onium cation is less than 5.0 eV.SELECTED DRAWING: None

Description

  The present invention relates to a chemically amplified resist material and a resist pattern forming method.

  As one of elemental technologies for manufacturing next-generation semiconductor devices, lithography using EUV (extreme ultraviolet) (hereinafter referred to as “EUV lithography”) has attracted attention. EUV lithography is a pattern formation technique that uses EUV having a wavelength of 13.5 nm as exposure light. According to EUV lithography, it has been demonstrated that an extremely fine pattern (for example, a line width of 20 nm or less) can be formed in an exposure step of a semiconductor device manufacturing process.

  However, since the EUV light source currently developed has a low output, it takes a long time for the exposure process. Therefore, EUV lithography has a disadvantage that it is not practical. In order to cope with this inconvenience, a technique for improving the sensitivity of a resist material that is a photosensitive resin has been developed (see JP 2002-174894 A).

  However, even the resist material in the above technique has insufficient sensitivity to EUV, and when the sensitivity to EUV is improved, there is a disadvantage that lithography performance such as nano edge roughness tends to be lowered. This inconvenience also exists when an electron beam or the like is used as irradiation light.

JP 2002-174894 A

  The present invention has been made on the basis of the above-mentioned circumstances, and the object thereof is non-ionizing having a wavelength of 250 nm or less such as ionizing radiation such as EUV, electron beam, ion beam, or KrF excimer laser and ArF excimer laser. Provided is a chemically amplified resist material capable of exhibiting excellent lithography performance while maintaining good sensitivity when ionizing radiation is used as pattern exposure light, and a resist pattern forming method using this chemically amplified resist material There is to do.

The invention made in order to solve the above problems includes (1) a polymer component that is soluble or insoluble in a developer by the action of an acid, and (2) a component that generates a radiation-sensitive sensitizer and an acid upon exposure. The component (2) contains the following (a) component, any two components in the following (a) to (c) components, or all of the following (a) to (c) components: The component (a) or the component (c) is a first compound having radiation sensitivity (hereinafter also referred to as “[C1] compound”) and a second compound having radiation sensitivity (hereinafter referred to as “[C2] compound”). The compound [C1] includes a first onium cation (hereinafter also referred to as “cation (I)”) and a first anion (hereinafter also referred to as “anion (I)”). The [C2] compound is converted to a second onium cation (hereinafter referred to as “cation (II)”). And a second anion different from the anion (I) (hereinafter also referred to as “anion (II)”), and the cation (I) and the cation (II) are reduced to radicals. It is a chemically amplified resist material that releases less than 5.0 eV.
(A) A radiation-sensitive sensitizer that absorbs the acid and the second radiation when the first radiation having a wavelength of 250 nm or less is irradiated and the second radiation having a wavelength exceeding 250 nm is not irradiated. Generation of a radiation-sensitive acid-sensitizer that does not substantially generate the acid and radiation-sensitive sensitizer when the first radiation is not irradiated and only the second radiation is irradiated. Agent (b) Generates a radiation-sensitive sensitizer that absorbs the second radiation when irradiated with the first radiation and does not emit the second radiation, and irradiates the first radiation Without radiating only the second radiation, the radiation-sensitive sensitizer generating agent that does not substantially generate the radiation-sensitive sensitizer (c) irradiating the first radiation, When no radiation is emitted, an acid is generated and the first radiation is Photoacid generator which does not substantially generate the acid when irradiated only the second radiation without morphism

  Another invention made in order to solve the above-described problems includes a film forming step of forming a resist material film on at least one surface of a substrate using the chemically amplified resist material, and a resist material film having a thickness of 250 nm or less. A pattern exposure step of irradiating radiation having a wavelength; a batch exposure step of irradiating the resist material film after the pattern exposure step with radiation having a wavelength exceeding 250 nm; and heating the resist material film after the batch exposure step. And a developing step of bringing the resist material film after the baking step into contact with a developer.

  Here, “when the first radiation is not irradiated and only the second radiation is irradiated, the acid and the radiation-sensitive sensitizer are not substantially generated”, “the first radiation is not irradiated and the second radiation is not irradiated. The radiation-sensitive sensitizer is not substantially generated when only the radiation is irradiated "and" the acid is not substantially generated when only the second radiation is irradiated without irradiating the first radiation ". "When an acid or radiation-sensitive sensitizer is not generated by irradiation with the second radiation, or even when an acid or radiation-sensitive sensitizer is generated by irradiation with the second radiation, The second radiation to such an extent that the difference in the concentration of the acid and the radiation-sensitive sensitizer between the exposed portion and the non-exposed portion in the pattern exposure for irradiating the first radiation can be maintained at a size that allows pattern formation. Increases the acid and radiation sensitivity of unexposed areas in the above pattern exposure by Means that the generation amount of acid or radiation-sensitive sensitizer is small enough to dissolve only the exposed or non-exposed portion in the pattern exposure after development in the developer. To do.

  The chemically amplified resist material of the present invention is used in the case where ionizing radiation such as EUV, electron beam, ion beam, or non-ionizing radiation having a wavelength of 250 nm or less such as KrF excimer laser and ArF excimer laser is used as pattern exposure light. It is possible to exhibit excellent lithography performance while maintaining good sensitivity. Further, the chemically amplified resist material can be suitably used for the resist pattern forming method.

It is process drawing which shows one Embodiment of the resist pattern formation method using the chemically amplified resist material which concerns on this invention. It is process drawing which shows an example of the resist pattern formation method using the conventional chemically amplified resist material. It is process drawing which shows another embodiment of the resist pattern formation method using the chemically amplified resist material which concerns on this invention. It is a conceptual diagram which shows the light absorbency of the pattern exposure part of a resist material film, and the light absorbency of an unexposed part as a graph. (A) is a conceptual diagram which shows the acid concentration distribution by the resist pattern formation method using the conventional chemically amplified resist material as a graph. (B) is a conceptual diagram showing the radiation-sensitive sensitizer concentration distribution and acid concentration distribution as a graph by the resist pattern forming method using the chemically amplified resist material according to the present embodiment. It is sectional drawing explaining an example of the manufacturing process of the semiconductor device which concerns on one Embodiment of this invention, (a) is sectional drawing which shows a resist pattern formation process, (b) is sectional drawing which shows an etching process. (C) is sectional drawing which shows a resist pattern removal process. It is a typical top view showing the nano edge roughness of a pattern. It is typical sectional drawing showing the nano edge roughness of a pattern.

  Hereinafter, embodiments of the present invention will be described in detail. In addition, this invention is not limited to the following embodiment.

<Chemically amplified resist material>
The chemically amplified resist material includes (1) a polymer component that becomes soluble or insoluble in a developer by the action of an acid, and (2) a component that generates a radiation-sensitive sensitizer and an acid upon exposure, The component (2) contains the following (a) component, any two components in the following (a) to (c) components, or all of the following (a) to (c) components.
(A) A radiation-sensitive sensitizer that absorbs the acid and the second radiation when the first radiation having a wavelength of 250 nm or less is irradiated and the second radiation having a wavelength exceeding 250 nm is not irradiated. And a radiation-sensitive acid-sensitizer generator that does not substantially generate the acid and radiation-sensitive sensitizer when the first radiation is not irradiated and only the second radiation is irradiated ( b) When the first radiation is irradiated and the second radiation is not emitted, a radiation-sensitive sensitizer that absorbs the second radiation is generated, and the first radiation is not irradiated. The radiation-sensitive sensitizer generating agent that does not substantially generate the radiation-sensitive sensitizer when irradiated only with the radiation (c) The first radiation is irradiated and the second radiation is not emitted In some cases, an acid is generated and the second radiation is not irradiated with the first radiation. Photoacid generator which does not substantially generate the acid when irradiated with only

  In addition to (1) the polymer component and (2) component, the chemical amplification resist material usually contains a solvent, and may further contain an acid diffusion control agent, a radical scavenger, a crosslinking agent, and other additives.

  Here, the component (2) may be incorporated in a part of the polymer constituting the (1) polymer component, or may be a component different from the (1) polymer component. In this case, even if a part of (2) component is a component different from (1) polymer component, all of (2) component may be a component different from (1) polymer component.

  The upper limit of the wavelength of the first radiation is preferably 250 nm, and more preferably 200 nm. On the other hand, the lower limit of the wavelength of the second radiation is preferably more than 250 nm, and more preferably 300 nm. The upper limit of the wavelength of the second radiation is preferably 500 nm, and more preferably 400 nm.

[(1) Polymer component]
(1) The polymer component is a component that becomes soluble or insoluble in the developer by the action of an acid. (1) The polymer component has, for example, a structural unit (hereinafter also referred to as “structural unit (I)”) containing a group that generates a polar group by the action of an acid (hereinafter also referred to as “acid-dissociable group”). Examples thereof include a first polymer (hereinafter also referred to as “[A] polymer”). (1) The polymer component may further include a second polymer that does not contain the structural unit (I) as long as it has the [A] polymer (hereinafter also referred to as “[B] polymer”).

  [A] polymer or [B] polymer is a structural unit containing a fluorine atom (hereinafter also referred to as “structural unit (II)”, a structural unit (III) containing a phenolic hydroxyl group, a lactone structure, a cyclic carbonate structure. And may further have a structural unit (IV) containing a sultone structure or a combination thereof, and may further have other structural units other than the structural unit (I) to the structural unit (IV).

[[A] polymer and [B] polymer]
[A] The polymer is a polymer having the structural unit (I). [A] The polymer may further have structural units (II) to (IV) or other structural units. [B] The polymer is a polymer different from the [A] polymer. [B] The polymer preferably has structural unit (II), and has structural unit (III) and structural unit (IV), and other structural units other than structural unit (III) to structural unit (IV). May be.

(Structural unit (I))
The structural unit (I) is a structural unit containing an acid dissociable group. [A] Since the polymer has the structural unit (I), the sensitivity and lithography performance of the chemically amplified resist material can be further improved. Examples of the structural unit (I) include a structural unit represented by the following formula (a-1) (hereinafter also referred to as “structural unit (I-1)”), and a structure represented by the following formula (a-2). A unit (hereinafter also referred to as “structural unit (I-2)”). In the following formulas (a-1) and (a-2), groups represented by —CR ^A2 R ^A3 R ^A4 and —CR ^A6 R ^A7 R ^A8 are acid dissociable groups.

In the above formula (a-1), R ^A1 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ^A2 is a monovalent hydrocarbon group having 1 to 20 carbon atoms. R ^A3 and R ^A4 are each independently a monovalent chain hydrocarbon group having 1 to 20 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or these groups are An alicyclic structure having 3 to 20 ring members composed of carbon atoms bonded to each other and bonded thereto is represented.
In the above formula (a-2), R ^A5 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ^A6 is a hydrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms, or a monovalent oxyhydrocarbon group having 1 to 20 carbon atoms. R ^A7 and R ^A8 are each independently a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent oxyhydrocarbon group having 1 to 20 carbon atoms. L ^A is a single bond, -O -, - COO- or -CONH-.

As a C1-C20 monovalent hydrocarbon group represented by said R ^{<A2 >} , R ^{< A6>} , R ^<A7> and R ^<A8 >, for example, a C1-C30 chain | strand-shaped hydrocarbon group, C3-C30 Examples thereof include alicyclic hydrocarbon groups and aromatic hydrocarbon groups having 6 to 30 carbon atoms.

Examples of the monovalent chain hydrocarbon group having 1 to 30 carbon atoms include alkyl groups such as a methyl group, an ethyl group, an n-propyl group, and an i-propyl group;
An alkenyl group such as an ethenyl group, a propenyl group, a butenyl group;
Examples thereof include alkynyl groups such as ethynyl group, propynyl group and butynyl group.

Examples of the monovalent alicyclic hydrocarbon group having 3 to 30 carbon atoms include a saturated simple group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentyl group, a cyclooctyl group, a cyclodecyl group, and a cyclododecyl group. A cyclic hydrocarbon group;
Unsaturated monocyclic hydrocarbon groups such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cyclooctenyl group, cyclodecenyl group;
Saturated polycyclic hydrocarbon groups such as bicyclo [2.2.1] heptanyl group, bicyclo [2.2.2] octanyl group, tricyclo [3.3.1.1 ^3,7 ] decanyl group;
And unsaturated polycyclic hydrocarbon groups such as a bicyclo [2.2.1] heptenyl group and a bicyclo [2.2.2] octenyl group.

Examples of the monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms include aryl groups such as phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methylnaphthyl group, anthryl group, and methylanthryl group;
Examples thereof include aralkyl groups such as benzyl group, phenethyl group, naphthylmethyl group and anthrylmethyl group.

R ^A2 is preferably a chain hydrocarbon group and a cycloalkyl group, more preferably an alkyl group and a cycloalkyl group, and a methyl group, an ethyl group, a propyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, and an adamantyl group. Further preferred.

Examples of the monovalent chain hydrocarbon group having 1 to 20 carbon atoms and the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by the above R ^{A3 and} R ^A4 include, for example, the above R ^A2 and R ^A6. , Groups similar to those exemplified for R ^A7 and R ^A8 .

Examples of the alicyclic structure having 3 to 20 ring members composed of the R ^A3 and R ^A4 groups together with the carbon atom to which they are bonded include a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclopentene structure, a cyclopentane structure, and the like. Monocyclic cycloalkane structures such as pentadiene structure, cyclohexane structure, cyclooctane structure, cyclodecane structure;
Examples thereof include polycyclic cycloalkane structures such as a norbornane structure, an adamantane structure, a tricyclodecane structure, and a tetracyclododecane structure.

R ^A3 and R ^A4 are preferably an alkyl group, a monocyclic cycloalkane structure, a norbornane structure, and an adamantane structure that are formed together with a carbon atom in which these groups are combined with each other, and are a methyl group, an ethyl group, A cyclopentane structure, a cyclohexane structure, and an adamantane structure are more preferable.

Examples of the monovalent oxyhydrocarbon group having 1 to 20 carbon atoms represented by R ^A6 , R ^A7 and R ^A8 include 1 to 20 carbon atoms of R ^A2 , R ^A6 , R ^A7 and R ^A8. Examples of the valent hydrocarbon group include a group containing an oxygen atom between carbon and carbon.

As said R ^<A6> , R ^<A7> and R ^<A8> , a chain hydrocarbon group and an alicyclic hydrocarbon group containing an oxygen atom are preferable.

As the ^{L A,} a single bond and -COO- is more preferably a single bond.

R ^A1 is preferably a hydrogen atom and a methyl group, more preferably a methyl group, from the viewpoint of copolymerization of the monomer that gives the structural unit (I).

R ^A5 is preferably a hydrogen atom and a methyl group, and more preferably a hydrogen atom, from the viewpoint of copolymerization of the monomer that gives the structural unit (I).

  Examples of the structural unit (I-1) include structural units represented by the following formulas (a-1-a) to (a-1-d) (hereinafter referred to as “structural units (I-1-a) to (I -1-d) ”) and the like. Examples of the structural unit (I-2) include a structural unit represented by the following formula (a-2-a) (hereinafter also referred to as “structural unit (I-2-a)”).

In the formulas (a-1-a) to (a-1-d), R ^{A1 to} R ^A4 have the same meanings as the formula (a-1). n _a is an integer of 1 to 4. In the above formula (a-2-a), R ^{A5 to} R ^A8 have the same ^meanings as the above formula (a-2).

The n _a, preferably 1, 2 and 4, more preferably 1.

  Examples of the structural units (I-1-a) to (I-1-d) include structural units represented by the following formulas.

In the above formula, R ^A1 has the same ^meaning as the above formula (a-1).

  Examples of the structural unit (I-2) include a structural unit represented by the following formula.

In the above formula, R ^A5 has the same ^{meaning as} in the above formula (a-2).

  As the structural unit (I), structural units (I-1-a) to (I-1-d) are preferable, and a structural unit derived from 2-methyl-2-adamantyl (meth) acrylate, 2-i-propyl- Structural unit derived from 2-adamantyl (meth) acrylate, structural unit derived from 1-methyl-1-cyclopentyl (meth) acrylate, structural unit derived from 1-ethyl-1-cyclohexyl (meth) acrylate, 1-i A structural unit derived from -propyl-1-cyclopentyl (meth) acrylate, a structural unit derived from 2-cyclohexylpropan-2-yl (meth) acrylate, and 2- (adamantan-1-yl) propan-2-yl ( A structural unit derived from (meth) acrylate is more preferred.

  [A] As a minimum of the content rate of structural unit (I) with respect to all the structural units which constitute a polymer, 10 mol% is preferred, 20 mol% is more preferred, 25 mol% is still more preferred, and 30 mol% is especially preferable. On the other hand, the upper limit of the content is preferably 80 mol%, more preferably 70 mol%, further preferably 65 mol%, particularly preferably 60 mol%. By setting the content ratio within the above range, it is possible to sufficiently ensure the dissolution contrast of the resist material film formed from the chemically amplified resist material with respect to the developer in the pattern exposed portion and the non-exposed portion, as a result. , Resolution and the like are improved.

(Structural unit (II))
The structural unit (II) is a structural unit containing a fluorine atom (except for those corresponding to the structural unit (I)). The structural unit (II) usually does not contain a salt structure. Examples of the structural unit (II) include structural units represented by the following formulas (f-1) to (f-4).

In said formula (f-1), R ^<F1> is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. L ^F1 is a single bond, an oxygen atom, a sulfur atom, —CO—O—, —SO ₂ —O—NH—, —CO—NH—, or —O—CO—NH—. R ^F2 is a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms.
In said formula (f-2), R ^<F3> is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. L ^F2 is a single bond, an oxygen atom, a sulfur atom, —CO—O—, —SO ₂ —O—NH—, —CO—NH—, or —O—CO—NH—. R ^F4 is a single bond, a (u + 1) -valent hydrocarbon group having 1 to 20 carbon atoms, or an oxygen atom, a sulfur atom, —NR ^FF1 —, a carbonyl group, —CO at the terminal of R ^F5 side of this hydrocarbon group. A structure in which —O— or —CO—NH— is bonded. R ^FF1 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. R ^F5 is a single bond or a divalent organic group having 1 to 20 carbon atoms. L ^F3 is a single bond or a divalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms. A ¹ is an oxygen atom, —NR ^FF2 —, —CO—O— *, or —SO ₂ —O— *. R ^FF2 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms. * Indicates a site that binds to R ^F6 . R ^F6 is a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms. u is an integer of 1 to 3. However, when u is 1, R ^F4 may be a single bond. When u is 2 or 3, a plurality of R ^F5 may be the same or different, a plurality of L ^F3 may be the same or different, a plurality of A ¹ may be the same or different, and a plurality of R ^F6 may be the same or different.
In formula (f-3), R ^F7 represents a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a monovalent carbonyloxy hydrocarbon group having 2 to 20 carbon atoms. L ^F4 is a single bond, an oxygen atom, a sulfur atom, —CO—O—, —SO ₂ —O—NH—, —CO—NH—, or —O—CO—NH—. R ^F8 is a single bond or a divalent organic group having 1 to 20 carbon atoms. R ^F9 and R ^F10 are each independently an alkyl group having 1 to 10 carbon atoms or a fluorinated alkyl group having 1 to 10 carbon atoms. However, one of R ^F9 and R ^F10 is a fluorinated alkyl group. v is an integer of 1 to 3. When v is 2 or 3, a plurality of R ^F9 may be the same or different, and a plurality of R ^F10 may be the same or different.
In said formula (f-4), R ^<F11> is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. R ^F12 and R ^F13 are each independently a hydrogen atom, a halogen atom, a hydroxy group, or a monovalent organic group having 1 to 20 carbon atoms. w is an integer of 1-4. When w is 2 or more, the plurality of R ^F12 may be the same or different, and the plurality of R ^F13 may be the same or different. Two or more of one or more of R ^F12 and one or more of R ^F13 form a ring structure having 3 to 20 ring members that is combined with a carbon atom or a carbon chain to which they are bonded together. Also good. R ^F14 and R ^F15 are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. However, at least one of R ^F14 and R ^F15 is a monovalent organic group having 1 to 20 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. R ^F14 and R ^F15 may be combined with each other to form a ring structure with 3 to 20 ring members that is configured together with the carbon atom to which they are bonded.

As said R ^{<F1 >} , R ^{< F3>} and R ^<F11> , a hydrogen atom and a methyl group are preferable and a methyl group is more preferable. As R ^F7 , a hydrogen atom, a methyl group, and a monovalent carbonyloxy hydrocarbon group are preferable, a methyl group and an alkoxycarbonyl group are more preferable, and a methyl group and an ethoxycarbonyl group are further preferable.

As said L ^<F1> , L ^<F2> and L ^<F4> , a single bond, an oxygen atom, and -CO-O- are preferable, and -CO-O- is more preferable.

The monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms represented by R ^F2, replacing part or all of the hydrogen atoms included in the monovalent hydrocarbon group having 1 to 20 carbon atoms with a fluorine atom The thing which was done is mentioned. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include groups similar to those exemplified for the above R ^A2 , R ^A6 , R ^A7 and R ^A8 .

As R ^F2 , a fluorinated chain hydrocarbon group is preferable, a fluorinated alkyl group is more preferable, and a fluorinated methyl group and a fluorinated ethyl group are further preferable.

Examples of the (u + 1) -valent hydrocarbon group having 1 to 20 carbon atoms represented by R ^F4 include monovalent carbon atoms having 1 to 20 carbon atoms exemplified by R ^A2 , R ^A6 , R ^A7 and R ^A8. Examples include those obtained by further removing u hydrogen atoms from a hydrogen group.

As said ^RFF1 , a hydrogen atom and a C1-C10 alkyl group are preferable, and a hydrogen atom, a methyl group, and an ethyl group are more preferable.

As R ^F4 , a single bond, a (u + 1) -valent chain hydrocarbon group having 1 to 20 carbon atoms, and an (u + 1) -valent aromatic hydrocarbon group having 6 to 20 carbon atoms are preferable. A (u + 1) -valent chain hydrocarbon group having 1 to 10 carbon atoms and a (u + 1) -valent aromatic hydrocarbon group having 6 to 10 carbon atoms are more preferable.

Examples of the divalent organic group having 1 to 20 carbon atoms represented by R ^F5 and R ^F8 include a divalent hydrocarbon group, divalent at the carbon-carbon end of the hydrocarbon group or at the terminal on the bond side. Groups containing a heteroatom-containing group, a group in which part or all of the hydrogen atoms of these groups are substituted with a substituent, and the like.

Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms include alkanediyl groups such as methanediyl group, ethanediyl group, propanediyl group, and butanediyl group;
Alkenediyl groups such as ethenediyl group, propenediyl group, butenediyl group;
Chain hydrocarbon groups such as alkynediyl groups such as ethynediyl, propynediyl, butynediyl;
Monocyclic cycloalkanediyl groups such as cyclopropanediyl group, cyclobutanediyl group, cyclopentanediyl group, cyclohexanediyl group;
Monocyclic cycloalkenediyl groups such as cyclopropenediyl group and cyclobutenediyl group;
A polycyclic cycloalkanediyl group such as a norbornanediyl group, an adamantanediyl group, a tricyclodecanediyl group, a tetracyclododecanediyl group;
An alicyclic hydrocarbon group such as a polycyclic cycloalkenediyl group such as a norbornenediyl group or a tricyclodecenediyl group;
Arenediyl groups such as benzenediyl group, toluenediyl group, xylenediyl group, naphthalenediyl group;
Aromatic hydrocarbon groups such as arenediyl (cyclo) alkanediyl groups such as benzenediylmethanediyl group and naphthalenediylcyclohexanediyl group.

  The hetero atom-containing group refers to a group having a divalent or higher valent hetero atom in the structure. The hetero atom-containing group may have one hetero atom or two or more hetero atoms. Here, the “hetero atom” refers to an atom other than a hydrogen atom and a carbon atom. The heteroatom-containing group may have only a heteroatom.

  The divalent or higher valent heteroatom of the heteroatom-containing group is not particularly limited as long as it is a diatomic or higher valent heteroatom. For example, an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, A boron atom etc. are mentioned.

Examples of the hetero atom-containing group include —O—, —S—, —NR ^HE —, —PR ^HE —, —SO—, —SO ₂ —, —SO ₂ O—, —OPO (OR ^HE ) O—. ^{_{, -PO 2 -, - PO 2}} O -, - CO -, - COO -, - COS -, - CONR HE -, - OCOO -, - OCOS -, - OCONR HE -, - SCONR HE -, - SCSNR HE -, -SCSS- group, etc. are mentioned. Here, R ^HE is a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms.

  Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, hydroxy group, carboxy group, nitro group and cyano group.

R ^F5 and R ^F8 are preferably a single bond, a divalent hydrocarbon group having 1 to 20 carbon atoms, and a group containing an oxygen atom between carbon-carbon atoms of the divalent hydrocarbon group. A divalent chain hydrocarbon group having 1 to 20 and a group containing an oxygen atom between carbon and carbon of the divalent chain hydrocarbon group and a divalent aromatic hydrocarbon group having 1 to 20 carbon atoms are more preferable. More preferred are a single bond, an alkanediyl group, an alkanediyloxyalkanediyl group and an arenediyl group.

Examples of the divalent fluorinated chain hydrocarbon group having 1 to 20 carbon atoms represented by L ^F3 include one of hydrogen atoms possessed by the divalent chain hydrocarbon group exemplified by the above R ^F5 and R ^F8. Examples include groups in which part or all are substituted with fluorine atoms.

As said ^LF3 , a single bond and a C1-C10 bivalent fluorinated chain hydrocarbon group are preferable, and a single bond and a C1-C10 fluorinated alkanediyl group are more preferable.

The above-mentioned ^{A 1,} oxygen atom and -CO-O- are preferable.

As said ^RFF2 , a hydrogen atom and a C1-C10 alkyl group are preferable, and a hydrogen atom, a methyl group, and an ethyl group are more preferable.

Examples of the monovalent organic group having 1 to 20 carbon atoms represented by R ^F6 , R ^F12 , R ^F13 , R ^F14, and R ^F15 include a monovalent hydrocarbon group and a carbon-carbon bond of the hydrocarbon group. Alternatively, a group containing a divalent heteroatom-containing group at the terminal on the bond side, a group in which part or all of the hydrogen atoms of these groups are substituted with a substituent, and the like can be given.

Examples of the monovalent hydrocarbon group include the same groups as those exemplified for R ^A2 , R ^A6 , R ^A7 and R ^A8 . Examples of the heteroatom-containing group and substituent include the same groups as those exemplified for R ^F5 and R ^F8 above.

As R ^F6 , a hydrogen atom and a monovalent chain hydrocarbon group having 1 to 30 carbon atoms are preferable, a hydrogen atom and an alkyl group having 1 to 30 carbon atoms are more preferable, and a hydrogen atom and an alkyl group having 1 to 10 carbon atoms are preferable. More preferred is an alkyl group. However, when L ^F3 is a single bond, R ^F6 preferably has a fluorine atom.

R ^F12 and R ^F13 are preferably a hydrogen atom and a monovalent hydrocarbon group having 1 to 12 carbon atoms, more preferably a monovalent hydrocarbon group having 1 to 12 carbon atoms, a phenyl group, a cycloalkyl group, And a fluorine atom-containing alkyl group substituted with a hydroxy group is more preferable.

R ^F14 and R ^F15 are preferably a hydrogen atom, a monovalent hydrocarbon group having 1 to 12 carbon atoms, and a monovalent hydroxy-substituted fluorinated hydrocarbon group having 3 to 12 carbon atoms. ˜12 alkyl groups and C 3-12 hydroxyfluorinated alkyl groups are more preferred, and hydrogen atom, methyl group, ethyl group and hydroxydi (trifluoromethyl) ethyl group are more preferred.

R ^F9 and R ^F10 are preferably a methyl group, an ethyl group, a propyl group, a fluorinated methyl group, a fluorinated ethyl group and a fluorinated propyl group, more preferably a fluorinated methyl group and a fluorinated ethyl group, and a fluorinated group. A methyl group is more preferable, and a trifluoromethyl group is particularly preferable.

  As said u, 1 and 2 are preferable and 1 is more preferable. As said v, 1 and 2 are preferable and 1 is more preferable. As said w, 1 and 2 are preferable and 1 is more preferable.

  As the structural unit (II), a structural unit represented by the following formula is preferred.

In the above formula, R ^F1 has the same ^meaning as the above formula (f-1). R ^F7 has the same ^{meaning as} in the above formula (f-3).

  [A] When the polymer has the structural unit (II), the lower limit of the content ratio of the structural unit (II) to all structural units constituting the [A] polymer is preferably 3 mol%, and 5 mol% More preferred is 10 mol%. On the other hand, as an upper limit of the said content rate, 40 mol% is preferable, 35 mol% is more preferable, and 30 mol% is further more preferable. By making the said content rate into the said range, the sensitivity in case EUV etc. are used as pattern exposure light can be improved more. On the other hand, when the said content rate exceeds the said upper limit, there exists a possibility that the rectangularity in the cross-sectional shape of a resist pattern may fall.

  (1) When the polymer component includes the [B] polymer and the [B] polymer has the structural unit (II), the lower limit of the structural unit (II) with respect to all the structural units constituting the [B] polymer Is preferably 3 mol%, more preferably 5 mol%, still more preferably 10 mol%. On the other hand, as an upper limit of the said content rate, 40 mol% is preferable, 35 mol% is more preferable, and 30 mol% is further more preferable. By making the said content rate into the said range, the sensitivity in case EUV etc. are used as pattern exposure light can be improved more. On the other hand, when the said content rate exceeds the said upper limit, there exists a possibility that the rectangularity in the cross-sectional shape of a resist pattern may fall.

(Structural unit (III))
The structural unit (III) is a structural unit containing a phenolic hydroxyl group (except for those corresponding to the structural unit (I) and the structural unit (II)). Since the [A] polymer or the [B] polymer has the structural unit (III), the sensitivity in the case of irradiation with KrF excimer laser light, EUV (extreme ultraviolet), electron beam or the like in the pattern exposure process described later is further increased. Can be improved.

Part or all of the hydrogen atoms of the aromatic ring containing the phenolic hydroxyl group may be substituted with a substituent. Examples of this substituent include the same groups as those exemplified for R ^F5 and R ^F8 above.

  Examples of the structural unit (III) include structural units represented by the following formulas (h-1) to (h-6) (hereinafter also referred to as “structural units (III-1) to (III-6)”). Can be mentioned.

In the above formulas (h-1) to (h-6), R ^AF1 is a hydrogen atom or a methyl group.

As said ^RAF1 , a hydrogen atom is preferable.

  As the structural unit (III), structural units (III-1) and (III-2) are preferable, and (III-1) is more preferable.

  [A] When the polymer has the structural unit (III), the lower limit of the content ratio of the structural unit (III) with respect to all the structural units constituting the [A] polymer is preferably 1 mol%, preferably 30 mol%. More preferred is 50 mol%. On the other hand, as an upper limit of the said content rate, 90 mol% is preferable, 80 mol% is more preferable, and 75 mol% is further more preferable. By making the content rate of structural unit (III) into the said range, the sensitivity of the said chemically amplified resist material can be improved more.

  (1) When the polymer component includes the [B] polymer and the [B] polymer has the structural unit (III), the content ratio of the structural unit (III) to all the structural units constituting the [B] polymer Is preferably 1 mol%, more preferably 30 mol%, and even more preferably 50 mol%. On the other hand, as an upper limit of the said content rate, 90 mol% is preferable, 80 mol% is more preferable, and 75 mol% is further more preferable. By making the content rate of structural unit (III) into the said range, the sensitivity of the said chemically amplified resist material can be improved more.

  The structural unit (III) was polymerized with a monomer obtained by substituting the hydrogen atom of the —OH group of the aromatic ring containing a phenolic hydroxyl group with an acetyl group, etc., and then the resulting polymer was hydrolyzed in the presence of an amine. A structure that can be formed by a decomposition reaction method or the like is also included.

(Structural unit (IV))
The structural unit (IV) is a structural unit containing a lactone structure, a cyclic carbonate structure, a sultone structure, or a combination thereof (except for those corresponding to the structural unit (I) to the structural unit (III)). [A] The polymer and the [B] polymer can further adjust the solubility in the developer by further including the structural unit (IV), and as a result, the chemically amplified resist The lithographic performance of the material can be further improved. Adhesion between the resist material film formed from the chemically amplified resist material and the substrate can be improved. Here, the lactone structure refers to a structure having one ring (lactone ring) including a group represented by —O—C (O) —. The cyclic carbonate structure refers to a structure having one ring (cyclic carbonate ring) including a group represented by —O—C (O) —O—. The sultone structure refers to a structure having one ring (sultone ring) including a group represented by —O—S (O) ₂ —. Examples of the structural unit (IV) include a structural unit represented by the following formula.

In the above formula, R ^AL is a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group.

As said ^RAL , a hydrogen atom and a methyl group are preferable from the viewpoint of the copolymerizability of the monomer which gives structural unit (IV), and a methyl group is more preferable.

  As the structural unit (IV), among these, a structural unit containing a norbornane lactone structure, a structural unit containing an oxanorbornane lactone structure, a structural unit containing a γ-butyrolactone structure, a structural unit containing an ethylene carbonate structure, and norbornane sultone A structural unit containing a structure is preferable, a structural unit derived from norbornanelactone-yl (meth) acrylate, a structural unit derived from oxanorbornanelactone-yl (meth) acrylate, and a cyano-substituted norbornanelactone-yl (meth) acrylate Structural unit, structural unit derived from norbornanelactone-yloxycarbonylmethyl (meth) acrylate, structural unit derived from butyrolactone-3-yl (meth) acrylate, butyrolactone-4-yl (meth) acrylate A structural unit derived from 3,5-dimethylbutyrolactone-3-yl (meth) acrylate, a structural unit derived from 4,5-dimethylbutyrolactone-4-yl (meth) acrylate, 1- (butyrolactone) -3-yl) cyclohexane-1-yl (meth) acrylate-derived structural unit, ethylene carbonate-ylmethyl (meth) acrylate-derived structural unit, cyclohexene carbonate-ylmethyl (meth) acrylate-derived structural unit, norbornane sultone -A structural unit derived from yl (meth) acrylate and a structural unit derived from norbornane sultone-yloxycarbonylmethyl (meth) acrylate are more preferred.

  [A] When the polymer has a structural unit (IV), the lower limit of the content ratio of the structural unit (IV) to all structural units constituting the [A] polymer is preferably 1 mol%, and 10 mol% More preferably, 20 mol% is more preferable, and 25 mol% is particularly preferable. On the other hand, the upper limit of the content is preferably 70 mol%, more preferably 65 mol%, still more preferably 60 mol%, and particularly preferably 55 mol%. By making the said content rate into the said range, the adhesiveness of the resist material film | membrane formed from the said chemically amplified resist material and a board | substrate can be improved more.

  (1) When the polymer component includes the [B] polymer, and the [B] polymer has the structural unit (IV), the content ratio of the structural unit (IV) with respect to all the structural units constituting the [B] polymer. Is preferably 1 mol%, more preferably 10 mol%, further preferably 20 mol%, particularly preferably 25 mol%. On the other hand, the upper limit of the content is preferably 70 mol%, more preferably 65 mol%, still more preferably 60 mol%, and particularly preferably 55 mol%. By making the said content rate into the said range, the adhesiveness of the resist material film | membrane formed from the said chemically amplified resist material and a board | substrate can be improved more.

[Other structural units]
The [A] polymer and the [B] polymer may have other structural units in addition to the structural units (I) to (IV). Examples of other structural units include a structural unit containing a polar group and a structural unit containing a non-dissociable hydrocarbon group. Examples of the polar group include an alcoholic hydroxyl group, a carboxy group, a cyano group, a nitro group, and a sulfonamide group. Examples of the non-dissociable hydrocarbon group include a linear alkyl group. [A] As an upper limit of the content rate of the said other structural unit with respect to all the structural units which comprise a polymer, 20 mol% is preferable and 10 mol% is more preferable. [B] The upper limit of the content ratio of the other structural units with respect to all the structural units constituting the polymer is preferably 20 mol%, and more preferably 10 mol%.

  The lower limit of the total content of the [A] polymer and the [B] polymer is preferably 70% by mass, more preferably 75% by mass, and more preferably 80% by mass in the total solid content of the chemically amplified resist material. preferable. Here, “total solid content” refers to components other than the solvent of the chemically amplified resist material.

  [A] The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer is not particularly limited, but the lower limit thereof is preferably 1,000, more preferably 2,000, and 3,000. Is more preferable, and 5,000 is particularly preferable. On the other hand, the upper limit of the Mw of the [A] polymer is preferably 50,000, more preferably 30,000, still more preferably 20,000, and particularly preferably 15,000. [A] By making Mw of a polymer into the said range, the applicability | paintability and development defect inhibitory property of the said chemically amplified resist material improve. [A] When Mw of the polymer is smaller than the lower limit, a resist material film having sufficient heat resistance may not be obtained. Conversely, when the Mw of the [A] polymer exceeds the above upper limit, the developability of the resist material film may be lowered.

  [A] The lower limit of the ratio (Mw / Mn) of Mw to the number average molecular weight (Mn) in terms of polystyrene by GPC of the polymer is usually 1. On the other hand, the upper limit of the ratio is usually 5, preferably 3 and more preferably 2.

  [B] The weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) of the polymer is not particularly limited, but the lower limit thereof is preferably 1,000, more preferably 2,000, and 2,500. Is more preferable, and 3,000 is particularly preferable. On the other hand, the upper limit of the Mw of the [B] polymer is preferably 50,000, more preferably 30,000, still more preferably 20,000, and particularly preferably 15,000. [B] By making Mw of a polymer into the said range, the applicability | paintability and development defect inhibitory property of the said chemically amplified resist material improve. [B] If the Mw of the polymer is smaller than the lower limit, a resist material film having sufficient heat resistance may not be obtained. Conversely, if the Mw of the [B] polymer exceeds the above upper limit, the developability of the resist material film may be reduced.

  [B] The lower limit of the ratio (Mw / Mn) of Mw to the number average molecular weight (Mn) in terms of polystyrene by GPC of the polymer is preferably 1. On the other hand, the upper limit of the ratio is preferably 5, more preferably 3, and even more preferably 2.

In addition, Mw and Mn of the polymer in this specification are values measured using gel permeation chromatography (GPC) under the following conditions.
GPC column: 2 G2000HXL, 1 G3000HXL, 1 G4000HXL (above, Tosoh Corporation)
Column temperature: 40 ° C
Elution solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene

  The [A] polymer and the [B] polymer may contain a low molecular weight component having a molecular weight of 1,000 or less. [A] The upper limit of the content of the low molecular weight component in the polymer is preferably 1.0% by mass, more preferably 0.5% by mass, and still more preferably 0.3% by mass. As a minimum of the above-mentioned content, it is 0.01 mass%, for example. [B] The upper limit of the content of the low molecular weight component in the polymer is preferably 1.0% by mass, more preferably 0.5% by mass, and still more preferably 0.3% by mass. As a minimum of the above-mentioned content, it is 0.01 mass%, for example. By setting the content of the low molecular weight component of the [A] polymer and the [B] polymer in the above range, the lithography performance of the chemically amplified resist material can be further improved.

In addition, the content of the low molecular weight component of the polymer in the present specification is a value measured using high performance liquid chromatography (HPLC) under the following conditions.
Column: GL Science's “Inertsil ODA-25 μm column” (4.6 mmφ × 250 mm)
Eluent: Acrylonitrile / 0.1% by mass phosphoric acid aqueous solution Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass
Sample injection volume: 100 μL
Detector: Differential refractometer

The lower limit of the fluorine atom content in the [A] polymer and the [B] polymer is preferably 1% by mass, more preferably 2% by mass, further preferably 4% by mass, and particularly preferably 7% by mass. On the other hand, as an upper limit of the said content rate, 60 mass% is preferable, 40 mass% is more preferable, and 30 mass% is further more preferable. Here, the fluorine atom content (% by mass) of the polymer can be calculated from the structure of the polymer determined by ¹³ C-NMR spectrum measurement.

  (1) The polymer component may have two or more polymers having different fluorine atom contents. Examples of such (1) polymer component include [A] polymer and [B] polymer, and [B] polymer having a higher fluorine atom content than [A] polymer, [A] ] Containing a polymer and [B] polymer, and [A] polymer having higher fluorine atom content than [B] polymer, or containing two or more [A] polymers having different fluorine atom contents And those containing two or more [B] polymers having different fluorine atom contents. As described above, (1) the polymer component has two or more polymers having different fluorine atom contents, so that a polymer having a high fluorine atom content is unevenly distributed in the resist material film surface layer, and a water-repellent polymer is added. It can function as an agent. As a result, elution of the component (2) and the like from the resist material film can be suppressed, the dynamic contact angle on the resist material film surface can be improved, and excellent drainage characteristics can be exhibited. This enables high-speed scan exposure when performing immersion exposure described later.

([A] Polymer and [B] Polymer Synthesis Method)
The [A] polymer and the [B] polymer are obtained by polymerizing monomers corresponding to predetermined respective structural units in a suitable polymerization reaction solvent using a polymerization initiator such as a radical polymerization initiator. Can be manufactured. As a specific synthesis method, for example, a method of dropping a solution containing a monomer and a radical polymerization initiator into a polymerization reaction solvent or a solution containing a monomer to cause a polymerization reaction, a solution containing a monomer, , A method of dropping a solution containing a radical polymerization initiator separately into a polymerization reaction solvent or a solution containing a monomer to cause a polymerization reaction, a plurality of types of solutions containing each monomer, and initiation of radical polymerization Examples thereof include a method in which a solution containing an agent is dropped into a solution containing a polymerization reaction solvent or a monomer separately to cause a polymerization reaction.

  Examples of the radical polymerization initiator include azobisisobutyronitrile (AIBN), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2-cyclopropylpropylene). Pionitrile), azo radical initiators such as 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate; benzoyl peroxide, t-butyl hydroperoxide, And peroxide radical initiators such as cumene hydroperoxide. Among these, as the radical polymerization initiator, AIBN and dimethyl 2,2'-azobisisobutyrate are preferable, and AIBN is more preferable. These radical initiators can be used alone or in combination of two or more.

  As the solvent used for the polymerization, for example, the same solvent as that which may be contained in the chemical amplification resist material described later can be used.

  As a minimum of reaction temperature in the above-mentioned polymerization, 40 ° C is preferred and 50 ° C is more preferred. On the other hand, the upper limit of the reaction temperature is preferably 150 ° C, more preferably 120 ° C. The lower limit of the reaction time in the polymerization is preferably 1 hour. On the other hand, the upper limit of the reaction time is preferably 48 hours, more preferably 24 hours.

  [A] The polymer and [B] polymer are preferably recovered by a reprecipitation method. That is, after completion of the reaction, the target polymer is recovered as a powder by introducing the reaction solution into a reprecipitation solvent. As the reprecipitation solvent, alcohols, alkanes and the like can be used singly or in combination of two or more. In addition to the reprecipitation method, the polymer can be recovered by removing low molecular components such as monomers and oligomers by a liquid separation operation, a column operation, an ultrafiltration operation, or the like.

[(2) Component that generates radiation-sensitive sensitizer and acid upon exposure]
The component (2) is a component that generates a radiation-sensitive sensitizer and an acid upon exposure (radiation irradiation). The component (2) includes (a) a radiation-sensitive acid-sensitizer generator, (b) a radiation-sensitive sensitizer generator, and (c) a radiation-sensitive acid generator. It contains all of a) component, (a) component and (b) component, (a) component and (c) component, (b) component and (c) component, or (a)-(c) component.

  The (a) radiation-sensitive acid-sensitizer generator or the (c) radiation-sensitive acid generator includes a [C1] compound containing a cation (I) and an anion (I), and a cation (II) and an anion. And [C2] compound containing (II). Anion (II) is different from anion (I). That is, the (a) radiation-sensitive acid-sensitizer generator or the (c) radiation-sensitive acid generator has a cation (I) and a cation (II) as cations and an anion (I) as an anion. And having an anion (II). The cation (I) and the cation (II) are onium cations, and both release energy when reduced to radicals is less than 5.0 eV. The (a) radiation-sensitive acid-sensitizer generator or the (c) radiation-sensitive acid generator has one or more [C1] compounds and [C2] compounds, respectively. Also good.

  Of the compounds [C1] and [C2], the compound having the smaller logarithmic value (pKa) of the reciprocal of the acid dissociation constant of the acid generated is (1) the polymer component is soluble or insoluble in the developer. Functions as an acid generating compound. Further, the compound having the larger pKa of the other acid generated functions as an acid diffusion control agent.

(Cation)
The cation (I) and the cation (II) are onium cations, and both release energy when reduced to radicals is less than 5.0 eV.

  In the chemically amplified resist material, (a) a radiation-sensitive acid-sensitizer generator or (c) a radiation-sensitive acid generator has a [C1] compound and a [C2] compound. In the case where radiation having a wavelength of 250 nm or less, such as EUV, is used as pattern exposure light because the energy released when both cation (I) and cation (II) are reduced to radicals is less than 5.0 eV Excellent lithography performance can be exhibited while maintaining good sensitivity. Although the reason why the chemically amplified resist material has the above-described configuration provides the above-mentioned effect is not clear, it can be presumed as follows, for example. That is, both (a) the radiation-sensitive acid-sensitizer generating agent or (c) the energy released when the cation of the radiation-sensitive acid generator is reduced to radicals are both less than the specified value, When the photodegradability of the compound functioning as the acid diffusion control agent is controlled to be moderately low to suppress decomposition in the pattern unexposed area, and as a result, the lithography performance can be improved while maintaining good sensitivity. Conceivable.

  The upper limit of the energy released when reduced to the cation (I) and cation (II) radicals is preferably 4.9 eV, and more preferably 4.8 eV. As a minimum, 4.0 eV is preferred and 4.2 eV is more preferred.

  The lower limit of the reduction potential of the cation (I) and the cation (II) is preferably −3.0V, more preferably −2.5V, and further preferably −2.0V. On the other hand, the upper limit of the reduction potential is preferably -0.8V, more preferably -0.9V.

  The lower limit of the total content of the cation (I) and the cation (II) with respect to all onium cations in the chemically amplified resist material is preferably 80 mol%, more preferably 85 mol%, and even more preferably 90 mol%. preferable. By making the total content rate of the said cation (I) and the said cation (II) into the said range, the sensitivity and lithography performance of the said chemically amplified resist material can be improved more.

As the cation (I) and the cation (II), for example, a monovalent onium cation represented by X ⁺ is used. Examples of the monovalent onium cation represented by X ⁺ include cations represented by the following formulas (X-1) and (X-2) (hereinafter referred to as “cation (X-1)” and “cation (X -2) ").

X ⁺ is preferably a triphenylsulfonium cation.

(Anion)
Anion (I) and anion (II) are different anions.

  The upper limit of the pKa of the acid generated from at least one of the [C1] compound and the [C2] compound is preferably 0, more preferably -0.5. Moreover, as said minimum, -7 is preferable and -5 is more preferable. The upper limit of the pKa of the acid generated from the other compound is preferably 11.0, and more preferably 10.5. Moreover, as said minimum, 0 is preferable, 1 is more preferable, and 2 is further more preferable. By setting the pKa of the acid within the above range, more excellent lithography performance can be exhibited. The pKa is a calculated value obtained by ACD / ChemSketch (ACD / Labs 8.00 Release Product Version: 8.08).

  Examples of the anion (I) and the anion (II) include a sulfonate anion, a carboxylate anion, a bis (alkylsulfonyl) amide anion, and a tris (alkylsulfonyl) methide anion.

  Among the anions (I) and (II), an anion that has a small logarithmic value (pKa) of the reciprocal of the acid dissociation constant of the generated acid and functions as an anion of the acid generating compound includes the following general formulas (XX), ( An anion of an acid represented by XXI) and (XXII) is preferred, and an anion of an acid represented by the following general formula (XX) is more preferred.

In the general formulas (XX), (XXI), and (XXII), R ^{18 to} R ²¹ each independently represents an organic group. Examples of the organic group include an alkyl group, an aryl group, and a group in which a plurality of these groups are linked. The organic group is preferably an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, and a phenyl group substituted with a fluorine atom or a fluoroalkyl group. When the organic group has a fluorine atom or a fluoroalkyl group, the acidity of the acid generated by exposure increases, and the sensitivity tends to improve. However, the organic group preferably does not contain a fluorine atom as a substituent at the terminal.

  Among the compounds [C1] and [C2], the compound that has a small logarithmic value (pKa) of the reciprocal of the acid dissociation constant of the generated acid and functions as the acid generating compound is represented by the following formula (1). Those are preferred. That is, it is preferable that the acid anion of the compound functioning as the acid generating compound has a structure represented by the following formula (1).

In the above formula (1), R ^p1 is a monovalent group containing a ring structure having 6 or more ring members. R ^p2 is a divalent linking group. R ^p3 and R ^p4 are each independently a hydrogen atom, a fluorine atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms. R ^p5 and R ^p6 are each independently a fluorine atom or a monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms. n ^p1 is an integer of 0 to 10. n ^p2 is an integer of 0 to 10. n ^p3 is an integer of 1 to 10. When n ^p1 is 2 or more, the plurality of R ^p2 may be the same or different. When n ^p2 is 2 or more, the plurality of R ^p3 may be the same or different, and the plurality of R ^p4 may be the same or different. When n ^p3 is 2 or more, the plurality of R ^p5 may be the same or different, and the plurality of R ^p6 may be the same or different. X ⁺ is cation (I) and cation (II).

  Here, the “number of ring members” refers to the number of atoms constituting a ring of an aromatic ring structure, aromatic heterocyclic structure, alicyclic structure and aliphatic heterocyclic structure, and in the case of a polycyclic ring structure, The number of atoms that make up the ring. The “hydrocarbon group” includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The “hydrocarbon group” may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The “chain hydrocarbon group” refers to a hydrocarbon group that does not include a cyclic structure but includes only a chain structure, and includes both a linear hydrocarbon group and a branched hydrocarbon group. The term “alicyclic hydrocarbon group” refers to a hydrocarbon group that includes only an alicyclic structure as a ring structure and does not include an aromatic ring structure, and includes a monocyclic alicyclic hydrocarbon group and a polycyclic alicyclic group. Includes both hydrocarbon groups. However, it is not necessary to be composed only of the alicyclic structure, and a part thereof may include a chain structure. “Aromatic hydrocarbon group” refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be composed only of an aromatic ring structure, and a part thereof may include a chain structure or an alicyclic structure.

Examples of the monovalent group including a ring structure having 6 or more ring members represented by R ^p1 include a monovalent group including an alicyclic structure having 6 or more ring members and an aliphatic heterocyclic structure having 6 or more ring members. A monovalent group, a monovalent group containing an aromatic ring structure having 6 or more ring members, a monovalent group containing an aromatic heterocyclic structure having 6 or more ring members, and the like.

Examples of the alicyclic structure having 6 or more ring members include monocyclic cycloalkane structures such as a cyclohexane structure, a cycloheptane structure, a cyclooctane structure, a cyclononane structure, a cyclodecane structure, and a cyclododecane structure;
Monocyclic cycloalkene structures such as cyclohexene structure, cycloheptene structure, cyclooctene structure, cyclodecene structure;
Polycyclic cycloalkane structures such as norbornane structure, adamantane structure, tricyclodecane structure and tetracyclododecane structure;
Examples thereof include polycyclic cycloalkene structures such as a norbornene structure and a tricyclodecene structure.

Examples of the aliphatic heterocyclic structure having 6 or more ring members include lactone structures such as a hexanolactone structure and a norbornane lactone structure;
Sultone structures such as hexanosultone structure and norbornane sultone structure;
An oxygen atom-containing heterocyclic structure such as an oxacycloheptane structure or an oxanorbornane structure;
Nitrogen atom-containing heterocyclic structures such as azacyclohexane structure and diazabicyclooctane structure;
Examples thereof include a sulfur atom-containing heterocyclic structure having a thiacyclohexane structure and a thianorbornane structure.

Examples of the aromatic ring structure having 6 or more ring members include a benzene structure, a naphthalene structure, a phenanthrene structure, and an anthracene structure.

  Examples of the aromatic heterocyclic structure having 6 or more ring members include oxygen atom-containing heterocyclic structures such as pyran structures and benzopyran structures, and nitrogen atom-containing heterocyclic structures such as pyridine structures, pyrimidine structures, and indole structures.

The lower limit of the number of ring members of the ring structure of R ^p1 is preferably 7, more preferably 8, more preferably 9, and particularly preferably 10. On the other hand, the upper limit of the number of ring members is preferably 15, more preferably 14, still more preferably 13, and particularly preferably 12. By setting the number of ring members in the above range, the above acid diffusion length can be further appropriately shortened, and as a result, the LWR performance and the like of the resist material of this embodiment can be further improved.

A part or all of the hydrogen atoms ^{contained in} the ring structure of R ^p1 may be substituted with a substituent. Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, hydroxy group, carboxy group, cyano group, nitro group, alkoxy group, alkoxycarbonyl group, alkoxycarbonyloxy group, acyl group, Examples include an acyloxy group. Of these, a hydroxy group is preferred.

Among these, R ^p1 is preferably a monovalent group containing an alicyclic structure having 6 or more ring members and a monovalent group containing an aliphatic heterocyclic structure having 6 or more ring members, and an alicyclic group having 9 or more ring members. A monovalent group containing a ring structure and a monovalent group containing an aliphatic heterocyclic structure having 9 or more ring members are more preferred. An oxo-4-oxatricyclo [4.3.1.1 ^3,8 ] undecan-yl group is more preferred, and an adamantyl group is particularly preferred.

Examples of the divalent linking group represented by R ^p2 include a carbonyl group, an ether group, a carbonyloxy group, a sulfide group, a thiocarbonyl group, a sulfonyl group, and a divalent hydrocarbon group. The divalent linking group represented by R ^p2 is preferably a carbonyloxy group, a sulfonyl group, an alkanediyl group and a cycloalkanediyl group, more preferably a carbonyloxy group and a cycloalkanediyl group, a carbonyloxy group and a norbornanediyl group. A group is more preferred, and a carbonyloxy group is particularly preferred.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ^p3 and R ^p4 include an alkyl group having 1 to 20 carbon atoms. Examples of the monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms represented by R ^p3 and R ^p4 include a fluorinated alkyl group having 1 to 20 carbon atoms. R ^p3 and R ^p4 are preferably a hydrogen atom, a fluorine atom and a fluorinated alkyl group, more preferably a fluorine atom and a perfluoroalkyl group, and still more preferably a fluorine atom and a trifluoromethyl group.

Examples of the monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms represented by R ^p5 and R ^p6 include a fluorinated alkyl group having 1 to 20 carbon atoms. R ^p5 and R ^p6 are preferably a fluorine atom and a fluorinated alkyl group, more preferably a fluorine atom and a perfluoroalkyl group, still more preferably a fluorine atom and a trifluoromethyl group, and particularly preferably a fluorine atom.

The lower limit of n ^p1 is preferably 0. On the other hand, the upper limit of n ^p1 is preferably 5, more preferably 3, more preferably 2, and particularly preferably 1.

The lower limit of n ^p2 is preferably 0. On the other hand, the upper limit of n ^p2 is preferably 5, more preferably 2, and even more preferably 1.

The lower limit of n ^p3 is preferably 1. On the other hand, the upper limit of n ^p3 is preferably 5, more preferably 4, more preferably 3, and particularly preferably 2.

  Examples of the anion of the acid include, but are not limited to, an anion represented by the following formula.

  Examples of the anion described in the above formula (1) that is preferable as the acid anion of the compound that functions as the acid generating compound include the following.

  Examples of the [C1] compound and [C2] compound include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2-bicyclo [2]. 2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 6- (adamantan-1-ylcarboxyoxy) -1,1,2,2-tetrafluorohexane -1-sulfonate, triphenylsulfonium adamantane-1-yloxycarbonylcarboxylate, 4-methoxyphenyldiphenylsulfonium 1,2-di (cyclohexyloxycarbonyl) ethane-1-sulfonate Etc. The.

  Among the compounds [C1] and [C2], the lower limit of the content of the component (a) or the component (c) in 100 parts by mass of the compound having the smaller pKa of the generated acid is 50% by mass. Preferably, 60 mass% is more preferable. On the other hand, the upper limit of the content is preferably 90% by mass, and more preferably 80% by mass. Moreover, as a minimum of content with respect to 100 mass parts of the said (a) component or the said (c) component in a compound with larger pKa of the acid generated among [C1] compound and [C2] compound, 5 masses % Is preferable, and 10% by mass is more preferable. On the other hand, the upper limit of the content is preferably 50% by mass, and more preferably 40% by mass. By setting the contents of the compound having a smaller pKa of the generated acid and the compound having a larger pKa within the above range, the sensitivity and lithography performance of the chemically amplified resist material can be further improved.

((A) Radiation sensitive acid-sensitizer generator)
(A) The radiation-sensitive acid-sensitizer generating agent irradiates the first radiation having a wavelength of 250 nm or less and does not irradiate the second radiation having a wavelength exceeding 250 nm. 2 and a radiation-sensitive sensitizer that absorbs radiation, and when the first radiation is not irradiated and only the second radiation is irradiated, the acid and radiation-sensitive sensitizer are substantially Does not occur.

  Examples of the [C1] compound and the [C2] compound that serve as the radiation sensitive acid-sensitizer generator (a) include onium salt compounds among the above-mentioned [C1] compound and [C2] compound. It is done. Moreover, as an onium salt compound, a sulfonium salt compound, a tetrahydrothiophenium salt compound, etc. are mentioned, for example.

  Examples of the cation (I) and the cation (II) in the [C1] compound and the [C2] compound include triphenylsulfonium.

  (A) As a radiation sensitive acid-sensitizer generator, compounds other than the above [C1] compound and [C2] compound may also be included, and other onium salt compounds, diazomethane compounds, and sulfonimide compounds. Etc. As an onium salt compound, an iodonium salt compound etc. are mentioned, for example. As the (a) radiation-sensitive acid-sensitizer generator other than the [C1] compound and the [C2] compound, an iodonium salt compound is preferable.

  A sulfonium salt compound is a compound comprising a sulfonium cation and an anion of an acid. As the sulfonium salt compound, compounds represented by the following formulas (I) to (III) are preferable.

In the above formulas (I) to (III), R ¹ , R ² , R ¹ ′, R ² ′, R ¹ ″, R ² ″, R ³ and R ⁴ are each independently a hydrogen atom; Phenyl group; naphthyl group; anthracenyl group; phenoxy group; naphthoxy group; anthracenoxy group; amino group; amide group; halogen atom; straight chain, branched chain having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms), or A cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group); a phenoxy group substituted by an alkoxy group having 1 to 5 carbon atoms, a hydroxy group, an amino group, an amide group, or an alkyl group having 1 to 5 carbon atoms; C1-C30 (preferably C1-C5) linear, branched or cyclic saturated or unsaturated hydrocarbon group (preferably alkyl group), C1-C5 alkoxy group, amino group Amide group, Or a phenyl group substituted with a hydroxy group; an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, an amino group, an amide group, or a naphthoxy group substituted with a hydroxy group; An anthracenoxy group substituted with an alkoxy group, an alkyl group having 1 to 5 carbon atoms, an amino group, an amide group, or a hydroxy group; an alkoxy group having 1 to 5 carbon atoms, a phenoxy group, a naphthoxy group, an anthracenoxy group, an amino group, A linear, branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group) having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms) substituted with an amide group or a hydroxy group; Or the carbonyl group which the C1-C12 alkyl group couple | bonded is shown. In the above formulas (I) to (III), the hydrogen atom of the hydroxy group is a phenyl group; a halogen atom; a linear, branched or cyclic saturated group having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms). Or an unsaturated hydrocarbon group (preferably an alkyl group); or a linear, branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group) having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms). Group), an alkoxy group having 1 to 5 carbon atoms, or a phenyl group substituted with a hydroxy group. When the hydrogen atom of the hydroxy group is substituted, the sulfonium salt compound will contain a ketal compound group or an acetal compound group. In the formula (I), any two or more groups of R ¹ , R ² , R ³ , and R ⁴ may be a single bond or a double bond, or —CH ₂ —, —O—, —S—. _{, -SO 2 -, - SO 2} NH -, - C (= O) -, - C (= O) O -, - NHCO -, - NHC (= O) NH -, - CHR e -, - CR e _A ring structure may be formed by bonding to each other via a bond including _2- , -NH-, or -NR ^e- . In the formula (II), any two or more groups of R ¹ , R ² , R ¹ ′, R ² ′ and R ⁴ are each a single bond or a double bond, or —CH ₂ —, —O—. , —S—, —SO ₂ —, —SO ₂ NH—, —C (═O) —, —C (═O) O—, —NHCO—, —NHC (═O) NH—, —CHR ^e —. , -CR ^e _2- , -NH- or -NR ^e -may be bonded to each other to form a ring structure. In the formula (III), any two or more groups of R ¹ , R ² , R ¹ ′, R ² ′, R ¹ ″ and R ² ″ are each a single bond or a double bond, or − _{CH 2 -, - O -,} - S -, - SO 2 -, - SO 2 NH -, - C (= O) -, - C (= O) O -, - NHCO -, - NHC (= O) A ring structure may be formed by bonding to each other via a bond including NH—, —CHR ^e —, —CR ^e ₂ —, —NH—, or —NR ^e —. R ^e is a phenyl group; a phenoxy group; a halogen atom; a linear, branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group) having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms). ); A phenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, a hydroxy group, or an alkyl group having 1 to 5 carbon atoms; or a straight chain having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms), A phenyl group substituted with a branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group), an alkoxy group having 1 to 5 carbon atoms, or a hydroxy group is shown. R ¹ , R ² , R ¹ ′, R ² ′, R ¹ ″, R ² ″, R ³ and R ⁴ are preferably each independently a phenyl group; a phenoxy group; A phenoxy group substituted with an alkyl group; or a phenyl group substituted with an alkoxy group having 1 to 5 carbon atoms or a hydroxy group. In the formulas (I) to (III), X ⁻ represents an anion of an acid, preferably a strong acid, more preferably a super strong acid.

In the above formulas (I) to (III), —C (—OH) R ¹ R ² , —C (—OH) R ¹ ′ R ² ′, and —C (—OH) R ¹ ″ R ² ″ Examples of the group represented by the above include groups represented by the following formulas. In addition, * in a formula shows the coupling | bond part with the sulfur ion in said formula (I)-(III). In the groups represented by —C (—OH) R ¹ R ² , —C (—OH) R ¹ ′ R ² ′, and —C (—OH) R ¹ ″ R ² ″, The carbon atom to which the hydroxy group is bonded becomes a carbonyl group by pattern exposure. Thus, in the compounds represented by the above formulas (I) to (III), —C (—OH) R ¹ R ² , —C (—OH) R ¹ 'R ² ', and —C (— OH) The group represented by R ¹ ″ R ² ″ is separated after pattern exposure to generate a radiation-sensitive sensitizer.

  The iodonium salt compound is a compound composed of an iodonium cation and an acid anion. As the iodonium salt compound, compounds represented by the following formulas (IV) to (V) are preferable.

In the above formulas (IV) to (V), R ⁵ , R ⁶ , R ⁵ ′, R ⁶ ′ and R ⁷ are each independently a hydrogen atom; a phenyl group; a naphthyl group; an anthracenyl group; a phenoxy group; Naphthoxy group; anthracenoxy group; amino group; amide group; halogen atom; linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms) (preferably Alkyl group); a phenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, a hydroxy group, an amino group, an amide group, or an alkyl group having 1 to 5 carbon atoms; 1 to 30 carbon atoms (preferably 1 to 1 carbon atoms) 5) a linear, branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group), an alkoxy group having 1 to 5 carbon atoms, an amino group, an amide group, or a hydroxy group. A phenyl group substituted with an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, an amino group, an amide group, or a hydroxy group; an alkoxy group having 1 to 5 carbon atoms and a carbon number An anthracenoxy group substituted with an alkyl group of 1 to 5, an amino group, an amide group, or a hydroxy group; an alkoxy group having 1 to 5 carbon atoms, a phenoxy group, a naphthoxy group, an anthracenoxy group, an amino group, an amide group, or a hydroxy group; A linear, branched, or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group) having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms) substituted with 1 or 12; A carbonyl group to which an alkyl group is bonded is shown. In the above formulas (IV) to (V), the hydrogen atom of the hydroxy group is a phenyl group; a halogen atom; a linear, branched or cyclic saturated group having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms). Or an unsaturated hydrocarbon group (preferably an alkyl group); or a linear, branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group) having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms). Group), an alkoxy group having 1 to 5 carbon atoms, or a phenyl group substituted with a hydroxy group. When the hydrogen atom of the hydroxy group is substituted, the iodonium salt compound will contain a ketal compound group or an acetal compound group. In the formula (IV), any two or more groups of R ⁵ , R ⁶ and R ⁷ are a single bond or a double bond, or —CH ₂ —, —O—, —S—, —SO _2. NH—, —C (═O) —, —C (═O) O—, —NHCO—, —NHC (═O) NH—, —CHR ^f —, —CR ^f ₂ —, —NH— or —NR ^A ring structure may be formed through a bond containing f-. In the formula (V), any two or more groups of R ⁵ , R ⁶ , R ⁵ ′ and R ⁶ ′ may be a single bond or a double bond, or —CH ₂ —, —O—, —S _{-, - SO 2 NH -,} - C (= O) -, - C (= O) O -, - NHCO -, - NHC (= O) NH -, - CHR f -, - CR f 2 -, - A ring structure may be formed through a bond containing NH— or —NR ^f —. R ^f represents a phenyl group; a phenoxy group; a halogen atom; a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms) (preferably an alkyl group). ); A phenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, a hydroxy group, or an alkyl group having 1 to 5 carbon atoms; or a straight chain having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms), A phenyl group substituted with a branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group), an alkoxy group having 1 to 5 carbon atoms, or a hydroxy group is shown. R ⁵ , R ⁶ , R ⁵ ′, R ⁶ ′ and R ⁷ are preferably each independently a phenyl group; a phenoxy group; an alkoxy group having 1 to 5 carbon atoms, a hydroxy group, or 1 to 5 carbon atoms. A phenoxy group substituted with an alkyl group, or a phenyl group substituted with an alkoxy group having 1 to 5 carbon atoms or a hydroxy group. In formulas (IV) to (V), Y ⁻ represents an anion of an acid, preferably a strong acid, more preferably a super strong acid.

In the above formulas (IV) to (V), examples of the groups represented by —C (—OH) R ⁵ R ⁶ and —C (—OH) R ⁵ 'R ⁶ ' include, for example, the above formulas (I) to ( A group represented by —C (—OH) R ¹ R ² , —C (—OH) R ¹ ′ R ² ′, —C (—OH) R ¹ ″ R ² ″ and the like exemplified in III) Similar groups are mentioned.

  (A) The radiation-sensitive acid-sensitizer generator may be a part of the polymer constituting (1) the polymer component. In this case, (a) the radiation-sensitive acid-sensitizer generator is present in a form in which a group obtained by removing one hydrogen atom from the above compound is bonded to the polymer.

  When (a) the radiation-sensitive acid-sensitizer generator is a component different from (1) the polymer component, (a) (a) radiation-sensitive acid-sensitizer generation with respect to 100 parts by mass of the polymer component As a minimum of the compounding quantity of an agent, 0.005 mass part is preferred and 0.1 mass part is more preferred. On the other hand, as an upper limit of the said compounding quantity, 50 mass parts is preferable and 30 mass parts is more preferable.

  (A) When the radiation-sensitive acid-sensitizer generator is a part of the polymer constituting the (1) polymer component, (a) (a) the radiation-sensitive acid with respect to 1 mol of the polymer component As a minimum of a content rate of a sensitizer generating agent, 0.001 mol is preferred, 0.002 mol is more preferred, and 0.01 mol is still more preferred. On the other hand, the upper limit of the content ratio is preferably 0.5 mol, more preferably 0.3 mol.

  If the blending amount or content ratio is smaller than the lower limit, the sensitivity may decrease. On the contrary, when the said compounding quantity or content rate exceeds the said upper limit, there exists a possibility that it may become difficult to form a resist material film, and there exists a possibility that the rectangularity in the cross-sectional shape of a resist pattern may fall.

((B) Radiation-sensitive sensitizer generating agent)
(B) The radiation-sensitive sensitizer generating agent generates a radiation-sensitive sensitizer that absorbs the second radiation when irradiated with the first radiation and does not emit the second radiation. And a component that does not substantially generate the radiation-sensitive sensitizer when only the second radiation is irradiated without irradiating the first radiation, and (a) the radiation-sensitive acid-sensitized sensitizer. It is different from the body generator.

  In the chemically amplified resist material, (b) the chemical structure of the radiation-sensitive sensitizer generating agent is converted by direct or indirect reaction upon irradiation with the first radiation, and acid is generated upon irradiation with the second radiation. Produce an auxiliary radiation-sensitive sensitizer. Since this radiation-sensitive sensitizer easily absorbs the second radiation as compared with the (b) radiation-sensitive sensitizer generating agent, the radiation-sensitive sensitization is performed when pattern exposure is performed with the first radiation. The absorption amount of the second radiation is greatly different between the exposed portion where the body is generated and the non-exposed portion where the radiation-sensitive sensitizer is not generated, and the contrast of the absorption amount is easily obtained.

  (B) The radiation-sensitive sensitizer generator is preferably a carbonyl compound having a carbonyl group that absorbs the second radiation when irradiated with the first radiation. Examples of the carbonyl compound include aldehyde, ketone, carboxylic acid, carboxylic acid ester and the like. The above reaction causes a shift in the peak of the absorption wavelength of radiation only in the (b) radiation-sensitive sensitizer generating agent in the pattern exposure portion. Therefore, if pattern exposure is performed with radiation having a wavelength that can be absorbed only by the pattern exposure portion after pattern exposure, only the pattern exposure portion can be selectively sensitized. (B) As the radiation-sensitive sensitizer generator, an alcohol compound represented by the following formula (VI) is more preferable, and a secondary alcohol compound may be used. In the present specification, the alcohol compound does not mean only a compound having an alcoholic hydroxyl group, but includes a ketal compound, an acetal compound, an orthoester compound, etc., in which a hydrogen atom of the alcoholic hydroxyl group is substituted. May be. (B) When the radiation-sensitive sensitizer generator is a ketal compound or an acetal compound, heating is performed after pattern exposure and before batch exposure in order to accelerate the hydrolysis reaction to the carbonyl compound by the acid catalyst generated by pattern exposure. May be.

式（ＶＩ）中、Ｒ^８、Ｒ^９及びＲ^１０は、それぞれ独立して、水素原子；フェニル基；ナフチル基；アントラセニル基；炭素数１〜５のアルコキシ基；炭素数１〜５のアルキルチオ基；フェノキシ基；ナフトキシ基；アントラセノキシ基；アミノ基；アミド基；ハロゲン原子；炭素数１〜３０（好ましくは炭素数１〜５）の直鎖状、分岐鎖状若しくは環状の飽和若しくは不飽和炭化水素基（好ましくはアルキル基）；炭素数１〜３０（好ましくは炭素数１〜５）の直鎖状、分岐鎖状若しくは環状の飽和若しくは不飽和炭化水素基（好ましくはアルキル基）、炭素数１〜５のアルコキシ基、アミノ基、アミド基、若しくはヒドロキシル基で置換された、炭素数１〜５のアルコキシ基；炭素数１〜３０（好ましくは炭素数１〜５）の直鎖状、分岐鎖状若しくは環状の飽和若しくは不飽和炭化水素基（好ましくはアルキル基）、炭素数１〜５のアルコキシ基、アミノ基、アミド基、若しくはヒドロキシル基で置換された、炭素数１〜５のアルキルチオ基；炭素数１〜５のアルコキシ基、ヒドロキシル基、アミノ基、アミド基、若しくは炭素数１〜５のアルキル基で置換されたフェノキシ基；炭素数１〜３０（好ましくは炭素数１〜５）の直鎖状、分岐鎖状若しくは環状の飽和若しくは不飽和炭化水素基（好ましくはアルキル基）、炭素数１〜５のアルコキシ基、アミノ基、アミド基、若しくはヒドロキシル基で置換されたフェニル基；炭素数１〜５のアルコキシ基、炭素数１〜５のアルキル基、アミノ基、アミド基、若しくはヒドロキシル基で置換されたナフトキシ基；炭素数１〜５のアルコキシ基、炭素数１〜５のアルキル基、アミノ基、アミド基、若しくはヒドロキシル基で置換されたアントラセノキシ基；炭素数１〜５のアルコキシ基、フェノキシ基、ナフトキシ基、アントラセノキシ基、アミノ基、アミド基、若しくはヒドロキシル基で置換された、炭素数１〜３０（好ましくは炭素数１〜５）の直鎖状、分岐鎖状若しくは環状の飽和若しくは不飽和炭化水素基（好ましくはアルキル基）；又は炭素数１〜１２のアルキル基が結合したカルボニル基を示す。アルコール化合物は、式（ＶＩ）中のアルコール性水酸基（ヒドロキシル基）がチオール基となったチオール化合物であってもよい。上記式（ＶＩ）中、ヒドロキシル基又はチオール基の水素原子は、フェニル基；ハロゲン原子；炭素数１〜３０（好ましくは炭素数１〜５）の直鎖状、分岐鎖状若しくは環状の飽和若しくは不飽和炭化水素基（好ましくはアルキル基）；又は炭素数１〜３０（好ましくは炭素数１〜５）の直鎖状、分岐鎖状若しくは環状の飽和若しくは不飽和炭化水素基（好ましくはアルキル基）、炭素数１〜５のアルコキシ基、若しくはヒドロキシル基で置換されたフェニル基で置換されていてもよい。式中、Ｒ^８、Ｒ^９及びＲ^１０のうち任意の２つ以上の基は、単結合若しくは二重結合により、又は−ＣＨ_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＳＯ_２ＮＨ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）Ｏ−、−ＮＨＣＯ−、−ＮＨＣ（＝Ｏ）ＮＨ−、−ＣＨＲ^ｇ−、−ＣＲ^ｇ _２−、−ＮＨ−若しくは−ＮＲ^ｇ−を含む結合を介して環構造を形成してもよい。Ｒ^ｇは、フェニル基；フェノキシ基；ハロゲン原子；炭素数１〜３０（好ましくは炭素数１〜５）の直鎖状、分岐鎖状若しくは環状の飽和若しくは不飽和炭化水素基（好ましくはアルキル基）；炭素数１〜５のアルコキシ基、ヒドロキシル基、若しくは炭素数１〜５のアルキル基で置換されたフェノキシ基；又は炭素数１〜３０（好ましくは炭素数１〜５）の直鎖状、分岐鎖状若しくは環状の飽和若しくは不飽和炭化水素基（好ましくはアルキル基）、炭素数１〜５のアルコキシ基、若しくはヒドロキシル基で置換されたフェニル基を示す。Ｒ^８、Ｒ^９及びＲ^１０は、それぞれ独立して、好ましくは水素原子；フェニル基；フェノキシ基；炭素数１〜５のアルコキシ基、ヒドロキシル基、若しくは炭素数１〜５のアルキル基で置換されたフェノキシ基；又は炭素数１〜５のアルコキシ基、若しくはヒドロキシル基で置換されたフェニル基を示す。

In formula (VI), R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom; a phenyl group; a naphthyl group; an anthracenyl group; an alkoxy group having 1 to 5 carbon atoms; an alkylthio group having 1 to 5 carbon atoms. A phenoxy group; a naphthoxy group; an anthracenoxy group; an amino group; an amide group; a halogen atom; a linear, branched or cyclic saturated or unsaturated hydrocarbon having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms); Group (preferably alkyl group); linear, branched or cyclic saturated or unsaturated hydrocarbon group (preferably alkyl group) having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms), preferably 1 carbon atom An alkoxy group having 1 to 5 carbon atoms, substituted with an alkoxy group having 5 to 5 alkoxy groups, an amino group, an amide group, or a hydroxyl group; a straight chain having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms); C1-C5 alkylthio substituted with branched or cyclic saturated or unsaturated hydrocarbon group (preferably alkyl group), C1-C5 alkoxy group, amino group, amide group, or hydroxyl group Group: a phenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, an amino group, an amide group, or an alkyl group having 1 to 5 carbon atoms; 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms) A phenyl group substituted with a linear, branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group), an alkoxy group having 1 to 5 carbon atoms, an amino group, an amide group, or a hydroxyl group; A naphthoxy group substituted by an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, an amino group, an amide group, or a hydroxyl group; An anthracenoxy group substituted with a alkoxy group, an alkyl group having 1 to 5 carbon atoms, an amino group, an amide group, or a hydroxyl group; an alkoxy group having 1 to 5 carbon atoms, a phenoxy group, a naphthoxy group, an anthracenoxy group, an amino group, an amide A linear, branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group) having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms) substituted with a group or a hydroxyl group; or A carbonyl group to which an alkyl group having 1 to 12 carbon atoms is bonded is shown. The alcohol compound may be a thiol compound in which the alcoholic hydroxyl group (hydroxyl group) in formula (VI) is a thiol group. In the formula (VI), the hydrogen atom of the hydroxyl group or thiol group is a phenyl group; a halogen atom; a linear, branched or cyclic saturated group having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms) or An unsaturated hydrocarbon group (preferably an alkyl group); or a linear, branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group) having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms). ), An alkoxy group having 1 to 5 carbon atoms, or a phenyl group substituted with a hydroxyl group. In the formula, any two or more groups of R ⁸ , R ⁹ and R ¹⁰ are each a single bond or a double bond, or —CH ₂ —, —O—, —S—, —SO ₂ —, — SO ₂ NH—, —C (═O) —, —C (═O) O—, —NHCO—, —NHC (═O) NH—, —CHR ^g —, —CR ^g ₂ —, —NH— or A ring structure may be formed through a bond containing —NR ^g —. R ^g is a phenyl group; a phenoxy group; a halogen atom; a linear, branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group) having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms). ); A phenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or an alkyl group having 1 to 5 carbon atoms; or a straight chain having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms), A phenyl group substituted with a branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group), an alkoxy group having 1 to 5 carbon atoms, or a hydroxyl group is shown. R ⁸ , R ⁹ and R ¹⁰ are preferably each independently substituted with a hydrogen atom; a phenyl group; a phenoxy group; an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or an alkyl group having 1 to 5 carbon atoms. Or a phenyl group substituted with an alkoxy group having 1 to 5 carbon atoms or a hydroxyl group.

In addition, as a ketal compound or acetal compound in which the hydrogen atom of the hydroxyl group in formula (VI) is substituted, a compound represented by the following formula (XXXVI) is preferable. That is, (b) the radiation-sensitive sensitizer generating agent may be a compound represented by the following formula (XXXVI). When either one of R ^{9 and} R ¹⁰ is a hydrogen atom, it can be said that the compound represented by the following formula (XXXVI) is an acetal compound.

式（ＸＸＸＶＩ）中、Ｒ^９及びＲ^１０は上記式（ＶＩ）中のＲ^９及びＲ^１０とそれぞれ同義である。Ｒ^９及びＲ^１０は、上記式（ＶＩ）中のＲ^９及びＲ^１０と同様に環構造を形成していてもよい。式（ＸＸＸＶＩ）中、Ｒ^２３及びＲ^２４は、それぞれ独立して、フェニル基；ハロゲン原子；炭素数１〜３０（好ましくは炭素数１〜５）の直鎖状、分岐鎖状若しくは環状の飽和若しくは不飽和炭化水素基（好ましくはアルキル基）；又は炭素数１〜３０（好ましくは炭素数１〜５）の直鎖状、分岐鎖状若しくは環状の飽和若しくは不飽和炭化水素基（好ましくはアルキル基）、炭素数１〜５のアルコキシ基、若しくはヒドロキシル基で置換されたフェニル基を示す。Ｒ^２３及びＲ^２４は、単結合、二重結合、−ＣＨ_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＳＯ_２ＮＨ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）Ｏ−、−ＮＨＣＯ−、ＮＨＣ（＝Ｏ）ＮＨ−、−ＣＨＲ^ｇ−、−ＣＲ^ｇ _２、−ＮＨ−又は−ＮＲ^ｇ−を含む結合を介して環構造を形成していてもよい。Ｒ^ｇは上記式（ＶＩ）中のＲ^ｇと同義である。ケタール化合物又はアセタール化合物は、式（ＸＸＸＶＩ）中のＲ^２３及び／又はＲ^２４と結合する酸素原子が硫黄に置き換えられたチオケタール化合物又はチオアセタール化合物であってもよい。

Wherein (XXXVI), ^{R 9} and ^{R 10} are the same meanings as ^{R 9} and ^{R 10} in formula (VI). R ⁹ and ^{R 10,} may form a similarly ring structure with ^{R 9} and ^{R 10} in formula (VI). In formula (XXXVI), R ²³ and R ²⁴ each independently represent a phenyl group; a halogen atom; a linear, branched or cyclic saturated group having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms). Or an unsaturated hydrocarbon group (preferably an alkyl group); or a linear, branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group) having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms). Group), an alkoxy group having 1 to 5 carbon atoms, or a phenyl group substituted with a hydroxyl group. R ²³ and R ²⁴ are a single bond, a double bond, —CH ₂ —, —O—, —S—, —SO ₂ —, —SO ₂ NH—, —C (═O) —, —C (= A ring structure may be formed through a bond containing O) O—, —NHCO—, NHC (═O) NH—, —CHR ^g —, —CR ^g ₂ , —NH— or —NR ^g —. . R ^g has the same meaning as ^{R g} in the formula (VI). The ketal compound or acetal compound may be a thioketal compound or a thioacetal compound in which the oxygen atom bonded to R ²³ and / or R ²⁴ in formula (XXXVI) is replaced with sulfur.

A ketal compound and an acetal compound can be obtained by reacting a carbonyl compound with an alcohol. The above reaction can be referred to as a reaction for protecting a carbonyl group that contributes to radiosensitization, and R ²³ and R ²⁴ in the above formula (XXXVI) can be referred to as a protecting group for a carbonyl group. In this case, the reaction in which (b) the radiation-sensitive sensitizer generator becomes a radiation-sensitive sensitizer by radiation or the like can be referred to as a deprotection reaction. Examples of the reactivity of the protecting group (ease of deprotection reaction) are shown below. The reactivity of the protecting group increases as it goes to the right and decreases as it goes to the left. For example, when a methoxy group is used as a protecting group for a carbonyl group, the reactivity of the deprotection reaction is high, and the deprotection reaction tends to proceed under an acid catalyst even at room temperature. As described above, the deprotection reaction proceeds at room temperature, so that there is an advantage that blurring of the image can be prevented. On the other hand, if a deprotection reaction occurs in a pattern unexposed portion at the time of pattern exposure and a radiation-sensitive sensitizer is generated, the contrast of the resist may be deteriorated. In order to prevent the formation of a radiation-sensitive sensitizer in the pattern unexposed area, a protecting group can be selected so as to increase the activation energy of the deprotection reaction (decrease the reactivity of the protecting group). From the viewpoint of lowering the reactivity of the protecting group, a cyclic protecting group in which R ²³ and R ^{24 in} formula (XXXVI) are bonded to each other to form a ring structure is more preferable. Examples of the ring structure include a 6-membered ring and a 5-membered ring, and a 5-membered ring is preferable. When a protective group having low reactivity is used, the resist material preferably contains a first scavenger described later, and it is desirable to bake the resist material film after pattern exposure and before batch exposure. By performing baking, unnecessary acid in the unexposed portion of the pattern is neutralized by the capturing agent, and the contrast of the latent image can be improved. The baking can compensate for the decrease in the reactivity of the protecting group, and the roughness of the latent image of the acid in the resist material film can be reduced by the diffusion of the substance by baking.

  The ketal type (b) radiation-sensitive sensitizer generating agent may be compounds represented by the following formulas (XXVII) to (XXX).

Wherein ^{(XXVII) ~ (XXX),} R 23 and ^{R 24} are the same meanings as ^{R 23} and ^{R 24} in the formula (XXXVI). In formulas (XXVII) to (XXX), the hydrogen atom of the aromatic ring may be substituted with an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms, and the aromatic ring is bonded to another aromatic ring Thus, a naphthalene ring or an anthracene ring may be formed. R ²⁵ represents an alkyl group having 1 to 5 carbon atoms. (B) When the compounds represented by the above formulas (XXVII) to (XXX) are used as the radiation-sensitive sensitizer generating agent, (b) from the radiation-sensitive sensitizer generating agent to the radiation-sensitive sensitizer and The shift of the absorption wavelength of the radiation at that time is larger, and a more selective sensitization reaction can be caused in the pattern exposure part.

  In addition, as an orthoester compound by which the hydrogen atom of the hydroxyl group in Formula (VI) was substituted, the compound represented by a following formula (XLVI) is preferable. That is, (b) the radiation-sensitive sensitizer generating agent may be a compound represented by the following formula (XLVI).

式（ＸＬＶＩ）中、Ｒ^９は上記式（ＶＩ）中のＲ^９と同義である。式（ＸＬＶＩ）中、Ｒ^３８〜Ｒ^４０は、それぞれ独立して、フェニル基；ハロゲン原子；炭素数１〜３０（好ましくは炭素数１〜５）の直鎖状、分岐鎖状若しくは環状の飽和若しくは不飽和炭化水素（好ましくはアルキル基基）；又は炭素数１〜３０（好ましくは炭素数１〜５）の直鎖状、分岐鎖状若しくは環状の飽和若しくは不飽和炭化水素基（好ましくはアルキル基）、炭素数１〜５のアルコキシ基、若しくはヒドロキシル基で置換されたフェニル基を示す。Ｒ^３８〜Ｒ^４０は、単結合若しくは二重結合により、又は−ＣＨ_２−、−Ｏ−、−Ｓ−、−ＳＯ_２−、−ＳＯ_２ＮＨ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）Ｏ−、−ＮＨＣＯ−、−ＮＨＣ（＝Ｏ）ＮＨ−、−ＣＨＲ^ｇ−、−ＣＲ^ｇ _２、−ＮＨ−若しくは−ＮＲ^ｇ−を含む結合を介して環構造を形成していてもよい。Ｒ^ｇは上記式（ＶＩ）中のＲ^ｇと同義である。

Wherein (XLVI), ^{R 9} has the same meaning as ^{R 9} in the formula (VI). In formula (XLVI), R ^{38 to} R ⁴⁰ each independently represent a phenyl group; a halogen atom; a linear, branched or cyclic saturated group having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms). Or an unsaturated hydrocarbon (preferably an alkyl group); or a linear, branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group) having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms). Group), an alkoxy group having 1 to 5 carbon atoms, or a phenyl group substituted with a hydroxyl group. R ^{38 to} R ⁴⁰ are each a single bond or a double bond, or —CH ₂ —, —O—, —S—, —SO ₂ —, —SO ₂ NH—, —C (═O) —, —C A ring structure is formed through a bond containing (═O) O—, —NHCO—, —NHC (═O) NH—, —CHR ^g —, —CR ^g ₂ , —NH— or —NR ^g —. May be. R ^g has the same meaning as ^{R g} in the formula (VI).

  The ortho ester compound is decomposed by a deprotection reaction in pattern exposure to become, for example, a carboxylic acid ester or carboxylic acid containing a carbonyl group. As the ortho ester compound, the carboxyl group part of the radiation-sensitive sensitizer having a carboxyl group is OBO (for example, 4-methyl 2,6,7-trioxabicyclo [2.2.2] octane-1-yl). The OBO ester compound represented by the following formula (XLVII) substituted (protected) with is preferable. The (b) radiation-sensitive sensitizer generating agent having a carboxyl group protected with OBO generates carboxylic acid by an acid catalyst generated during pattern exposure, shifts the absorption wavelength of radiation, and radiation-sensitive sensitization during batch exposure. Work as a body. (B) Since the carboxylic acid is generated from the radiation-sensitive sensitizer generating agent, the polarity of the resist changes, for example, from nonpolar to polar in the pattern exposure portion. For this reason, the ortho ester compound also functions as a dissolution accelerator in the development process, and contributes to an improvement in resist contrast. (B) When the radiation-sensitive sensitizer generator contains an OBO ester compound, it is possible to simultaneously generate the radiation-sensitive sensitizer and cause a polarity change reaction.

式（ＸＬＶＩＩ）中、Ｒ^４１及びＲ^４２は、それぞれ独立して、水素原子；フェニル基；ナフチル基；アントラセニル基；フェノキシ基；ナフトキシ基；アントラセノキシ基；アミノ基；アミド基；ハロゲン原子；炭素数１〜３０（好ましくは炭素数１〜５）の直鎖状、分岐鎖状若しくは環状の飽和若しくは不飽和炭化水素基（好ましくはアルキル基）；炭素数１〜５のアルコキシ基、ヒドロキシル基、アミノ基、アミド基、若しくは炭素数１〜５のアルキル基で置換されたフェノキシ基；炭素数１〜３０（好ましくは炭素数１〜５）の直鎖状、分岐鎖状若しくは環状の飽和若しくは不飽和炭化水素基（好ましくはアルキル基）、炭素数１〜５のアルコキシ基、アミノ基、アミド基、若しくはヒドロキシル基で置換されたフェニル基；炭素数１〜５のアルコキシ基、炭素数１〜５のアルキル基、若しくはヒドロキシル基で置換されたナフトキシ基；炭素数１〜５のアルコキシ基、炭素数１〜５のアルキル基、アミノ基、アミド基、若しくはヒドロキシル基で置換されたアントラセノキシ基；炭素数１〜５のアルコキシ基、フェノキシ基、ナフトキシ基、アントラセノキシ基、アミノ基、アミド基、若しくはヒドロキシル基で置換された、炭素数１〜３０（好ましくは炭素数１〜５）の直鎖状、分岐鎖状若しくは環状の飽和若しくは不飽和炭化水素基（好ましくはアルキル基）；又は炭素数１〜１２のアルキル基が結合したカルボニル基を示す。Ｒ^４１及びＲ^４２は、それぞれ独立して、好ましくは水素原子；フェニル基；フェノキシ基；炭素数１〜５のアルコキシ基、ヒドロキシル基、若しくは炭素数１〜５のアルキル基で置換されたフェノキシ基；又は炭素数１〜５のアルコキシ基、若しくはヒドロキシル基で置換されたフェニル基を示す。

In formula (XLVII), R ⁴¹ and R ⁴² each independently represent a hydrogen atom; a phenyl group; a naphthyl group; an anthracenyl group; a phenoxy group; a naphthoxy group; an anthracenoxy group; an amino group; 1 to 30 (preferably 1 to 5 carbon atoms) linear, branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group); an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, amino Group, amide group, or phenoxy group substituted with an alkyl group having 1 to 5 carbon atoms; linear, branched or cyclic saturated or unsaturated having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms) A phenyl group substituted by a hydrocarbon group (preferably an alkyl group), an alkoxy group having 1 to 5 carbon atoms, an amino group, an amide group, or a hydroxyl group; carbon A naphthoxy group substituted by an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, or a hydroxyl group; an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, an amino group, an amide group, Or an anthracenoxy group substituted with a hydroxyl group; an alkoxy group having 1 to 5 carbon atoms, a phenoxy group, a naphthoxy group, an anthracenoxy group, an amino group, an amide group, or a hydroxyl group, substituted with 1 to 30 carbon atoms (preferably A linear, branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group) having 1 to 5 carbon atoms; or a carbonyl group to which an alkyl group having 1 to 12 carbon atoms is bonded. R ⁴¹ and R ⁴² are each independently preferably a hydrogen atom; a phenyl group; a phenoxy group; a phenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or an alkyl group having 1 to 5 carbon atoms. Or a phenyl group substituted with an alkoxy group having 1 to 5 carbon atoms or a hydroxyl group;

  (B) As a radiation sensitive sensitizer generating agent, the compound etc. which are represented by a following formula are mentioned, for example. These compounds are alcohol compounds in which the hydrogen atom of the alcoholic hydroxyl group is not substituted, and change into a ketone compound by a reaction during pattern exposure.

  The following compounds are examples of ketal compounds or acetal compounds in which the carbonyl group of the radiation-sensitive sensitizer is protected. These compounds become radiation-sensitive sensitizers containing ketones in the pattern exposure part by the catalytic action of the acid generated by pattern exposure.

  The following compounds are examples of orthoester compounds having carbon atoms substituted with three alkoxy groups.

  The ortho ester compound is deprotected by an acid catalyst generated during pattern exposure to produce an ester having a carbonyl group (methyl carboxylate in the following example).

  In the following chemical formula, the carboxyl group part of the radiation-sensitive sensitizer having a carboxyl group is represented by OBO (for example, 4-methyl-2,6,7-trioxabicyclo [2.2.2] octane-1-yl). It is an example of the OBO ester compound which is a protected derivative.

  The OBO ester compound generates the following carboxylic acid by an acid catalyst generated during pattern exposure.

  Examples of the radiation-sensitive sensitizer generated by exposure from the component (2) (that is, the (a) radiation-sensitive acid-sensitizer generator and (b) radiation-sensitive sensitizer generator) include, for example, Chalcone and its derivatives, 1,2-diketone and its derivatives, benzoin and its derivatives, benzophenone and its derivatives, fluorene and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, xanthene and its derivatives, thioxanthene and its derivatives, Xanthone and its derivatives, thioxanthone and its derivatives, cyanine and its derivatives, merocyanine and its derivatives, naphthalocyanine and its derivatives, subphthalocyanine and its derivatives, pyrylium and its derivatives, thiopyrylium and its derivatives, tetraphylline and its derivatives, annu And derivatives thereof, spiropyran and derivatives thereof, spirooxazine and derivatives thereof, thiospiropyran and derivatives thereof, oxole and derivatives thereof, azine and derivatives thereof, thiazine and derivatives thereof, oxazine and derivatives thereof, indoline and derivatives thereof, azulene and derivatives thereof Derivatives, azulenium and its derivatives, squarylium and its derivatives, porphyrin and its derivatives, porphyrazine and its derivatives, triarylmethane and its derivatives, phthalocyanine and its derivatives, acridone and its derivatives, coumarin and its derivatives, ketocoumarin and its derivatives, Quinolinone and its derivatives, benzoxazole and its derivatives, acridine and its derivatives, thiazine and its derivatives, benzothiazole and its derivatives, pheno Azine and derivatives thereof, benzotriazole and derivatives thereof, perylene and derivatives thereof, naphthalene and derivatives thereof, anthracene and derivatives thereof, phenanthrene and derivatives thereof, pyrene and derivatives thereof, naphthacene and derivatives thereof, pentacene and derivatives thereof, and coronene and derivatives thereof Derivatives and the like. Moreover, it is preferable that the said radiation sensitive sensitizer which generate | occur | produces from said (2) component by exposure contains a carbonyl compound. The carbonyl compound preferably contains ketone, aldehyde, carboxylic acid, ester, amide, enone, carboxylic acid chloride, carboxylic acid anhydride and the like as a carbonyl group. The carbonyl compound is preferably a compound that absorbs radiation on the longer wavelength side exceeding 250 nm from the viewpoint of increasing the contrast of the resist by sufficiently separating the wavelength of radiation at the time of batch exposure from the wavelength of radiation at the time of pattern exposure. Examples of the carbonyl compound include benzophenone derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, and acridone derivatives. The carbonyl compound may be a naphthalene derivative or an anthracene derivative, or an acridone derivative. In the radiation-sensitive sensitizer, the hydrogen of the aromatic ring is preferably substituted with an electron donating group. When the hydrogen in the aromatic ring of the radiation-sensitive sensitizer is replaced with an electron-donating group, the electron transfer efficiency due to the sensitization reaction during batch exposure is improved, and the resist sensitivity tends to be improved. In addition, (b) the difference between the radiation absorption wavelength of the radiation-sensitive sensitizer and the radiation absorption wavelength of the radiation-sensitive sensitizer can be increased, and the radiation sensitivity can be more selectively at the time of batch exposure. Since the sensitizer can be excited, the contrast of the latent image of the acid in the resist material tends to be improved. Examples of the electron donating group include a hydroxyl group, a methoxy group, an alkoxy group, an amino group, an alkylamino group, and an alkyl group.

  Examples of benzophenone and derivatives thereof include the following compounds.

  Examples of thioxanthone and derivatives thereof include the following compounds.

  Examples of xanthone and derivatives thereof include the following compounds.

  Examples of acridone and derivatives thereof include the following compounds.

  Examples of coumarin and its derivatives include the following compounds.

  The radiation-sensitive sensitizer may contain the following compound.

  Examples of the radiation-sensitive sensitizer include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 1,2-hydroxy-2-methyl-1-phenyl. Propan-1-one, α-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropanone, 2-hydroxy-2-methyl-1- (4-isopropylphenyl) propanone, 2-hydroxy-2 -Methyl-1- (4-dodecylphenyl) propanone, 2-hydroxy-2-methyl-1-[(2-hydroxyethoxy) phenyl] propanone, benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone 4-methoxybenzo Enone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, benzophenone tetracarboxylic acid or its tetramethyl ester, 4 , 4′-bis (dimethylamino) benzophenone, 4,4′-bis (dicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4- Methoxy-4′-dimethylaminobenzophenone, 4,4′-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-buty Luanthraquinone, 2-methylanthraquinone, phenanthraquinone, fluorenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2-[(4 -Methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-hydroxy 2-Methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin phenyl ether, benzyldimethyl ketal, acridone , Loroacridone, N-methylacridone, N-butylacridone, N-butyl-chloroacridone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyl Diphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, bis- (2, 6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,6-dichloroben Yl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2,6 -Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6-trimethylbenzoyl) Phenylphosphine oxide, (2,5,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichloro Thioxane , 1-chloro-4-propoxythioxanthone, benzoyldi- (2,6-dimethylphenyl) phosphonate, 1- [4- (phenylthio) phenyl] -1,2-octanedione-2- (O-benzoyloxime), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone-1- (O-acetyloxime), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropanone-1- (O-acetyloxime), 1- [4- (phenylthio) phenyl] -3-cyclopentylpropane-1,2-dione-2- ( O-benzoyloxime), 2,2-dimethoxy-1,2-diphenylethane-1-one, 1- [4- (2-hydroxyethoxy) -fur Nyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2- Methyl-propan-1-one, phenylglyoxylic acid methyl ester, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,1- [4- (phenylthio) phenyl] -1,2-octanedione 2- (O-benzoyloxime), 1- [9-ethyl-6- (2- Methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime) and the like.

  (B) The radiation-sensitive sensitizer generator may be (1) part of a polymer constituting the polymer component. In this case, (b) the radiation-sensitive sensitizer generator is present in a form in which a group obtained by removing one hydrogen atom from the above compound is bonded to the polymer.

  When the (b) radiation-sensitive sensitizer generator is a component different from the (1) polymer component, the blending amount of the (b) radiation-sensitive sensitizer generator with respect to 100 parts by mass of the polymer component (1) Is preferably 0.005 parts by mass, more preferably 0.1 parts by mass. On the other hand, as an upper limit of the said compounding quantity, 50 mass parts is preferable and 30 mass parts is more preferable.

  (B) When the radiation-sensitive sensitizer generator is a part of the polymer constituting the (1) polymer component, (b) generation of the radiation-sensitive sensitizer with respect to 1 mol of the polymer component As a minimum of a content rate of an agent, 0.001 mol is preferred, 0.002 mol is more preferred, and 0.01 mol is still more preferred. On the other hand, as an upper limit of the said content rate, 0.95 mol is preferable and 0.3 mol is more preferable.

  If the blending amount or content ratio is smaller than the lower limit, the sensitivity may decrease. On the contrary, when the said compounding quantity or content rate exceeds the said upper limit, there exists a possibility that it may become difficult to form a resist material film, and there exists a possibility that the rectangularity in the cross-sectional shape of a resist pattern may fall.

((C) Radiation sensitive acid generator)
(C) The radiation-sensitive acid generator generates an acid when the first radiation is irradiated and the second radiation is not emitted, and the second radiation is not irradiated with the first radiation. It is a component that does not substantially generate the acid when irradiated with only radiation, and is different from the above-mentioned (a) radiation-sensitive acid-sensitizer generating agent. (C) Since the radiation-sensitive acid generator has the above properties, it can generate an acid only at the pattern exposure portion of the resist material film by a radiation sensitization reaction during batch exposure.

Examples of the cation (I) and the cation (II) in the [C1] compound and the [C2] compound include a monovalent onium cation represented by X ⁺ as the cation (I) and the cation (II). Decomposes by exposure light exposure. In the exposed portion, sulfonic acid is generated from protons generated by the decomposition of the onium cation and the sulfonate anion. This cation does not generate a radiation-sensitive sensitizer.

Examples of the monovalent onium cation represented by X ⁺ include the cations represented by the above formulas (X-1) and (X-2).

Among these, triphenylsulfonium cation is preferable as X ⁺ .

  Examples of the anion (I) and the anion (II) in the [C1] compound and the [C2] compound include the same anions as those exemplified as the anion (I) and the anion (II).

  Examples of the [C1] compound and the [C2] compound that serve as the (c) radiation-sensitive acid generator include the sulfonium salt compounds that are the above-described onium salt compounds.

  Examples of the sulfonium salt compound include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, among the above-mentioned [C1] compound and [C2] compound, Triphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 6- (adamantan-1-ylcarboxyoxy) -1,1 , 2,2-tetrafluorohexane-1-sulfonate, triphenylsulfonium adamantane-1-yloxycarbonylcarboxylate, triphenylsulfonium 4-trifluoromethyl salicylate, 4-methoxyphenyl Sulfonyl diphenyl sulfonium 1,2-di (cyclohexyloxycarbonyl) ethane-1-sulfonate, and the like.

  (C) As a radiation sensitive acid generator, you may have compounds other than the said [C1] compound and a [C2] compound, (c) Radiation sensitive acid other than a [C1] compound and a [C2] compound Examples of the generator include other onium salt compounds, diazomethane compounds, and sulfonimide compounds. Examples of the onium salt compound include a tetrahydrothiophenium salt compound and an iodonium salt compound in addition to the sulfonium salt compound.

  Examples of other sulfonium salt compounds include 4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4 -Cyclohexylphenyldiphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methanesulfonylphenyl Diphenylsulfonium nonafluoro-n-butanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium perf Oro -n- octane sulfonate, 4-methanesulfonyl-phenyl diphenyl sulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethane ethanesulfonate.

  Examples of the tetrahydrothiophenium salt compound include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium. Nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothio Phenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium trifluoro Lomethanesulfonate, 1- (6-n-butoxynaphthalene) 2-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (6-n- Butoxynaphthalen-2-yl) tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (3,5-dimethyl-4 -Hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (3,5-dimethyl-4-hydroxy Phenyl) tetrahydrothiophenium perfluoro-n-oct Sulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, etc. Is mentioned.

  Examples of the iodonium salt compound include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl. -1,1,2,2-tetrafluoroethanesulfonate, bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4- t-butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2- Tiger fluoro ethanesulfonate.

  Examples of the sulfonimide compound include N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [ 2.2.1] Hept-5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3- Dicarboximide, N- (2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene -2,3-dicarboximide and the like.

  Examples of the diazomethane compound include bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (tert-butylsulfonium) diazomethane, bis (cyclopentylsulfonyl) diazomethane, and bis (cyclo Hexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (4-chlorophenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, bis (2,4-xylylsulfonyl) diazomethane, bis (4-isopropylphenylsulfonyl) ) Diazomethane, bis (4-tert-butylphenylsulfonyl) diazomethane, bis (naphthylsulfonyl) diazomethane, bis (anthracenylsulfur) ) Diazomethane.

  (C) The radiation sensitive acid generator may be a part of the polymer constituting (1) the polymer component. In this case, (c) the radiation sensitive acid generator is present in a form in which a group obtained by removing one hydrogen atom from the above compound is bonded to the polymer.

  When (c) the radiation-sensitive acid generator is a component different from (1) the polymer component, (1) the lower limit of the blending amount of the (c) radiation-sensitive acid generator with respect to 100 parts by mass of the polymer component 0.1 part by mass is preferable, and 1 part by mass is more preferable. On the other hand, as an upper limit of the said compounding quantity, 50 mass parts is preferable and 30 mass parts is more preferable.

  When the (c) radiation sensitive acid generator is part of the polymer constituting the (1) polymer component, the content ratio of the (c) radiation sensitive acid generator with respect to 1 mole of the polymer component (1) Is preferably 0.01 mol, more preferably 0.02 mol, and even more preferably 0.1 mol. On the other hand, the upper limit of the content ratio is preferably 0.5 mol, more preferably 0.3 mol.

  If the blending amount or content ratio is smaller than the lower limit, the sensitivity may decrease. On the contrary, when the said compounding quantity or content rate exceeds the said upper limit, there exists a possibility that it may become difficult to form a resist material film, and there exists a possibility that the rectangularity in the cross-sectional shape of a resist pattern may fall.

  When the component (2) is a component different from the (1) polymer component, the lower limit of the content of the component (2) with respect to the total solid content of the chemically amplified resist material is preferably 10% by mass, and 15% by mass. % Is more preferable. On the other hand, the upper limit of the content is preferably 30% by mass, and more preferably 25% by mass. (2) By making content of a component into the said range, the sensitivity and lithography performance of the said chemically amplified resist material can be improved more. Here, “content of (2) component” means the total content of components different from (1) the polymer component among (2) components.

[Other acid diffusion control agents]
The chemically amplified resist material may contain an acid diffusion controller other than the [C1] compound and the [C2] compound. Other acid diffusion control agents capture acids and cations and function as quenchers. The chemical amplification resist material contains another acid diffusion control agent, so that the excess acid generated in the resist material film is neutralized, and an acid latent image between the pattern exposed portion and the pattern non-exposed portion is obtained. Can increase the chemical contrast.

  The acid diffusion controller is classified into a compound having radiation sensitivity and a compound having no radiation sensitivity.

  As the compound having no radiation sensitivity, a basic compound is preferable. Examples of the basic compound include a hydroxide compound, a carboxylate compound, an amine compound, an imine compound, an amide compound, and more specifically, primary to tertiary aliphatic amines, aromatic amines, Heterocyclic amine, nitrogen-containing compound having carboxyl group, nitrogen-containing compound having sulfonyl group, nitrogen-containing compound having hydroxyl group, nitrogen-containing compound having hydroxyphenyl group, alcoholic nitrogen-containing compound, nitrogen-containing compound having carbamate group , Amide compounds, imide compounds, and the like. Among these, nitrogen-containing compounds having a carbamate group are preferred.

  The basic compounds include: Troger's base; hindered amines such as diazabicycloundecene (DBU) and diazabicyclononene (DBM); tetrabutylammonium hydroxide (TBAH) and tetrabutylammonium lactate It may be an ionic quencher.

  Examples of the primary aliphatic amine include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-amylamine, and cyclopentylamine. Hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine and the like.

  Examples of the secondary aliphatic amine include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, and dihexylamine. , Dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepentamine and the like.

  Examples of the tertiary aliphatic amine include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine, tricyclopentylamine, Trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ′, N′-tetramethylmethylenediamine, N, N , N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyltetraethylenepentamine and the like.

  Examples of the aromatic amine and heterocyclic amine include aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, and 4-methylaniline. , Ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N, N- Aniline derivatives such as dimethyltoluidine; diphenyl (p-tolyl) amine; methyldiphenylamine; triphenylamine; phenylenediamine; naphthylamine; diaminonaphthalene; pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2, 5-dimethylpi And pyrrole derivatives such as N-methylpyrrole; oxazole derivatives such as oxazole and isoxazole; thiazole derivatives such as thiazole and isothiazole; imidazole derivatives such as imidazole, 4-methylimidazole and 4-methyl-2-phenylimidazole; Pyrazole derivatives; furazane derivatives; pyrroline derivatives such as pyrroline and 2-methyl-1-pyrroline; pyrrolidine derivatives such as pyrrolidine, N-methylpyrrolidine, pyrrolidinone and N-methylpyrrolidone; imidazoline derivatives; imidazolidine derivatives; pyridine, methylpyridine, Ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl- -Phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 4-pyrrolidinopyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc. Pyridine derivatives; pyrimidine derivatives; pyrazoline derivatives; pyrazolidine derivatives; piperidine derivatives; piperazine derivatives; morpholine derivatives; indole derivatives; isoindole derivatives; 1H-indazole derivatives; indoline derivatives; quinoline, 3-quinolinecarbonitrile, etc. Quinoline derivatives; isoquinoline derivatives; cinnoline derivatives; quinazoline derivatives; quinoxaline derivatives; phthalazine derivatives; purine derivatives; Conductors; carbazole derivatives; phenanthridine derivatives; acridine derivatives; phenazine derivatives; 1,10-phenanthroline derivatives; adenine derivatives; adenosine derivatives; guanine derivatives;

  Examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid; indolecarboxylic acid; nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine, threonine, Examples include amino acid derivatives such as lysine, 3-aminopyrazine-2-carboxylic acid, and methoxyalanine.

  Examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid and pyridinium p-toluenesulfonate.

  Examples of the nitrogen-containing compound having a hydroxyl group, the nitrogen-containing compound having a hydroxyphenyl group, and the alcoholic nitrogen-containing compound include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indolemethanol hydrate, Monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2′-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol, 4- Amino-1-butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) ethyl] piperazi Piperidine ethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propanediol, 8 -Hydroxyurolidine, 3-cuincridinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotine Examples include amides.

  Examples of the nitrogen-containing compound having a carbamate group include N- (tert-butoxycarbonyl) -L-alanine, N- (tert-butoxycarbonyl) -L-alanine methyl ester, (S)-(−)-2- ( tert-butoxycarbonylamino) -3-cyclohexyl-1-propanol, (R)-(+)-2- (tert-butoxycarbonylamino) -3-methyl-1-butanol, (R)-(+)-2 -(Tert-butoxycarbonylamino) -3-phenylpropanol, (S)-(-)-2- (tert-butoxycarbonylamino) -3-phenylpropanol, (R)-(+)-2- (tert- Butoxycarbonylamino) -3-phenyl-1-propanol, (S)-(−)-2- (tert-butoxycarbonyl) Amino) -3-phenyl-1-propanol, (R)-(+)-2- (tert-butoxycarbonylamino) -1-propanol, (S)-(−)-2- (tert-butoxycarbonylamino) -1-propanol, N- (tert-butoxycarbonyl) -L-aspartic acid 4-benzyl ester, N- (tert-butoxycarbonyl) -O-benzyl-L-threonine, (R)-(+)-1- (Tert-Butoxycarbonyl) -2-tert-butyl-3-methyl-4-imidazolidinone, (S)-(−)-1- (tert-butoxycarbonyl) -2-tert-butyl-3-methyl- 4-imidazolidinone, N- (tert-butoxycarbonyl) -3-cyclohexyl-L-alanine methyl ester, N- (tert Butoxycarbonyl) -L-cysteine methyl ester, N- (tert-butoxycarbonyl) ethanolamine, N- (tert-butoxycarbonylethylenediamine), N- (tert-butoxycarbonyl) -D-glucosamine, Nα- (tert-butoxy) Carbonyl) -L-glutamine, 1- (tert-butoxycarbonyl) imidazole, N- (tert-butoxycarbonyl) -L-isoleucine, N- (tert-butoxycarbonyl) -L-isoleucine methyl ester, N- (tert- Butoxycarbonyl) -L-leucinol, Nα- (tert-butoxycarbonyl) -L-lysine, N- (tert-butoxycarbonyl) -L-methionine, N- (tert-butoxycarbonyl) -3- (2-naphthy) ) -L-alanine, N- (tert-butoxycarbonyl) -L-phenylalanine, N- (tert-butoxycarbonyl) -L-phenylalanine methyl ester, N- (tert-butoxycarbonyl) -D-prolinal, N- ( tert-butoxycarbonyl) -L-proline, N- (tert-butoxycarbonyl) -L-proline-N′-methoxy-N′-methylamide, N- (tert-butoxycarbonyl) -1H-pyrazole-1-carboxyami Zin, (S)-(−)-1- (tert-butoxycarbonyl) -2-pyrrolidinemethanol, (R)-(+)-1- (tert-butoxycarbonyl) -2-pyrrolidinemethanol, 1- (tert -Butoxycarbonyl) 3- [4- (1-pyrrolyl) phenyl] -L-a Lanine, N- (tert-butoxycarbonyl) -L-serine, N- (tert-butoxycarbonyl) -L-serine methyl ester, N- (tert-butoxycarbonyl) -L-threonine, N- (tert-butoxycarbonyl) ) -P-toluenesulfonamide, N- (tert-butoxycarbonyl) -S-trityl-L-cysteine, Nα- (tert-butoxycarbonyl) -L-tryptophan, N- (tert-butoxycarbonyl) -L-tyrosine N- (tert-butoxycarbonyl) -L-tyrosine methyl ester, N- (tert-butoxycarbonyl) -L-valine, N- (tert-butoxycarbonyl) -L-valine methyl ester, N- (tert-butoxy Carbonyl) -L-valinol, tert- Tyl N- (3-hydroxypropyl) carbamate, tert-butyl N- (6-aminohexyl) carbamate, tert-butylcarbamate, tert-butylcarbazate, tert-butyl-N- (benzyloxy) carbamate, tert- Butyl-4-benzyl-1-piperazinecarboxylate, tert-butyl (1S, 4S)-(−)-2,5-diazabicyclo [2.2.1] heptane-2-carboxylate, tert-butyl-N -(2,3-dihydroxypropyl) carbamate, tert-butyl (S)-(-)-4-formyl-2,2-dimethyl-3-oxazolidinecarboxylate, tert-butyl [R- (R *, S * )]-N- [2-hydroxy-2- (3-hydroxyphenyl) -1-methylethyl ] Carbamate, tert-butyl-4-oxo-1-piperidinecarboxylate, tert-butyl-1-pyrrolecarboxylate, tert-butyl-1-pyrrolidinecarboxylate, tert-butyl (tetrahydro-2-oxo-3-furanyl) ) Carbamate and the like.

  Examples of the amide compound include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, 1-cyclohexylpyrrolidone and the like.

  Examples of the imide compound include phthalimide, succinimide, maleimide and the like.

  The compound having radiation sensitivity is classified into a compound that is decomposed by radiation and loses acid diffusion control ability (radiolysis type compound) and a compound that is generated by radiation and obtains acid diffusion control ability (radiation generation compound).

  The radiation-decomposable compound is decomposed only in the pattern exposure part in the pattern exposure step, so that the action of capturing the acid and cation is reduced in the pattern exposure part, and the action of capturing the acid and cation is maintained in the pattern non-exposed part. The For this reason, the chemical contrast of the latent image of the acid between the exposed part and the non-exposed part can be improved.

  As the radiolytic compound, sulfonates and carboxylates of radiolytic cation other than the [C1] compound and the [C2] compound are preferable. The sulfonic acid in the sulfonate is preferably a weak acid, more preferably a hydrocarbon group having 1 to 10 carbon atoms, and the hydrocarbon group not containing fluorine. Examples of such sulfonic acid include sulfonic acids such as alkyl sulfonic acid, benzene sulfonic acid, and 10-camphor sulfonic acid. The carboxylic acid in the carboxylate is preferably a weak acid, more preferably a carboxylic acid having 1 to 20 carbon atoms. Examples of such carboxylic acids include carboxylic acids such as formic acid, acetic acid, propionic acid, tartaric acid, succinic acid, cyclohexyl carboxylic acid, benzoic acid, and salicylic acid. The radiolytic cation in the carboxylate of the radiolytic cation is preferably an onium cation, and examples of the onium cation include an iodonium cation.

  Since the radiation generating compound is generated only in the pattern exposure part in the pattern exposure step, an action of capturing an acid and a cation occurs in the pattern exposure part and does not occur in the pattern non-exposure part.

  The radiation generating compound may be generated in the batch exposure process without being generated in the pattern exposure process. In this case, a radiation-sensitive sensitizer can be efficiently generated in the exposed portion of the pattern exposure step, and unnecessary acids and cations can be captured in the non-exposed portion of the batch exposure step.

  As the radiation-generating compound, a compound that generates a base upon exposure (a radiation-sensitive base generator) is preferable, and a nitrogen-containing organic compound that generates an amino group is more preferable.

  Examples of the radiation sensitive base generator include, for example, JP-A-4-151156, JP-A-4-162040, JP-A-5-197148, JP-A-5-5995, JP-A-6-194634, JP-A-8-146608, and JP-A-10. -83079, and the compound as described in European Patent 622682.

  Examples of the radiation sensitive base generator include a compound containing a carbamate group (urethane bond), a compound containing an acyloxyimino group, an ionic compound (anion-cation complex), a compound containing a carbamoyloxyimino group, and the like. And a compound containing a carbamate group (urethane bond), a compound containing an acyloxyimino group, and an ionic compound (anion-cation complex) are preferable.

  Furthermore, as the radiation sensitive base generator, a compound having a ring structure in the molecule is preferable. Examples of the ring structure include a benzene ring structure, a naphthalene ring structure, an anthracene ring structure, a xanthone ring structure, a thioxanthone ring structure, an anthraquinone ring structure, and a fluorene ring structure.

  Examples of the radiation sensitive base generator include 2-nitrobenzyl carbamate, 2,5-dinitrobenzyl cyclohexyl carbamate, N-cyclohexyl-4-methylphenylsulfonamide, 1,1-dimethyl-2-phenylethyl. -N-isopropyl carbamate and the like.

  The acid diffusion control agent may be a compound (heat generation compound) that is generated by a thermal reaction and obtains acid diffusion control ability. In this case, it is desirable to generate in the baking process after the batch exposure process. Thus, it is preferable that the heating temperature in the baking process mentioned later is higher than the heating temperature in another process from a viewpoint that an acid diffusion control agent acquires acid diffusion control ability in a baking process.

  When the chemically amplified resist material contains the acid diffusion controller, (1) the lower limit of the content of the acid diffusion controller relative to 100 parts by mass of the polymer component is preferably 0.001 part by mass, Part by mass is more preferable. On the other hand, as an upper limit of the said content, 20 mass parts is preferable and 10 mass parts is more preferable. When the said content is smaller than the said minimum, there exists a possibility that the said acid diffusion control agent cannot fully capture | acquire an acid and a cation. On the contrary, when the content exceeds the upper limit, the sensitivity may be excessively lowered.

[Radical scavenger]
The radical scavenger traps free radicals. When the chemically amplified resist material contains the radical scavenger, the generation of radiation-sensitive sensitizers via reaction by radicals in the pattern non-exposed portion is reduced, and the pattern exposed portion after the batch exposure step described later and The contrast of the acid concentration with the non-exposed part can be further improved. Examples of the radical scavenger include compounds such as phenolic compounds, quinone compounds, and amine compounds, and natural antioxidants such as rubber.

[Crosslinking agent]
The cross-linking agent is used to cause a cross-linking reaction between polymer components by an acid catalyst reaction in a baking step after collective exposure, to increase the molecular weight of the polymer component, and to insolubilize in the developer. 1) It is different from the polymer component. Since the resist material contains a cross-linking agent, the polar part becomes nonpolar at the same time as the cross-linking and becomes insoluble in the developer, so that a negative resist material can be provided.

  The crosslinking agent is a compound having two or more functional groups. The functional group is preferably at least one selected from the group consisting of a (meth) acryloyl group, a hydroxymethyl group, an alkoxymethyl group, an epoxy group, and a vinyl ether group.

[Other additives]
Examples of other additives include surfactants, antioxidants, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents, and dyes. Known materials can be selected for the surfactant, antioxidant, dissolution inhibitor, plasticizer, stabilizer, colorant, antihalation agent, and dye. As the surfactant, for example, an ionic or nonionic fluorine-based surfactant, a silicon-based surfactant, or the like can be used. Examples of the antioxidant include a phenolic antioxidant, an antioxidant made of an organic acid derivative, a sulfur-containing antioxidant, a phosphorus antioxidant, an amine antioxidant, and an antioxidant made of an amine-aldehyde condensate. And an antioxidant comprising an amine-ketone condensate.

[solvent]
The solvent is for dissolving the composition of the resist material and facilitating the formation of the resist material film by a coating machine using a spin coating method or the like. In addition, the compound included in said (b) radiation sensitive sensitizer generator etc. shall be remove | excluded from a solvent. Examples of the solvent include ketones such as cyclohexanone and methyl-2-amyl ketone; 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol and the like. Alcohols; ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether; and propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, 3-ethoxypropionic acid Chill acetate tert- butyl, tert- butyl propionate, propylene glycol monomethyl ether acetate, and esters such as propylene glycol monobutyl tert- butyl ether acetate.

[Method of preparing chemically amplified resist material]
The chemically amplified resist material can be prepared, for example, by mixing (1) a polymer component, (2) component, and other optional components as necessary at a predetermined ratio. The chemically amplified resist material is preferably filtered after mixing with, for example, a filter having a pore diameter of about 0.2 μm. The lower limit of the total solid content concentration of the chemically amplified resist material is usually 0.1% by mass, preferably 0.5% by mass, and more preferably 1% by mass. On the other hand, the upper limit of the total solid content is usually 50% by mass, preferably 30% by mass, and more preferably 20% by mass.

<Resist pattern formation method>
The resist material is preferably used in a two-step exposure lithography process. That is, the lithography process (including the resist pattern forming method) according to the present embodiment includes a film forming process for forming a resist material film formed using the resist material on a substrate, and a mask for the resist material film. A pattern exposure step of irradiating the first radiation through, a batch exposure step of irradiating the resist material film after the pattern exposure step with a second radiation, and a baking step of heating the resist material film after the batch exposure step And a step of bringing the resist material film after the baking step into contact with a developer.

  FIG. 1 is a process diagram showing a lithography process according to this embodiment. FIG. 2 is a process diagram showing an example of a resist pattern forming method using a conventional chemically amplified resist material.

As shown in FIG. 1, the lithography process according to this embodiment includes the following steps.
Step S1: Step of preparing a substrate to be processed Step S2: Step of forming a lower layer film and a resist material film (film formation step)
Step S3: A step of generating an acid in the exposed portion by pattern exposure (pattern exposure step)
Step S4: a step of multiplying acid only in the pattern exposure portion by batch exposure (collective exposure step)
Step S5: A step of causing a polarity change reaction by an acid catalyst in the pattern exposed portion by baking after exposure (baking step).
Step S6: Step of forming a resist pattern by development processing (development step)
Step S7: Step of transferring pattern by etching (etching step)

(Process S1)
The substrate to be processed (substrate to be processed) in the following steps may be composed of a semiconductor wafer such as a silicon substrate, a silicon dioxide substrate, a glass substrate, and an ITO substrate, and is insulated on the semiconductor wafer. A film layer may be formed.

(Process S2: Film formation process)
The resist material film is formed using the resist material of this embodiment. Examples of the method for forming the resist material film include a method of applying a liquid resist material by spin coating or the like, a method of attaching a film-like (solid) resist material, and the like. When applying a liquid resist material, the solvent in the resist material may be volatilized by heating (pre-baking) after application. The formation conditions of the resist material film are appropriately selected according to the properties of the resist material and the thickness of the resist material film to be obtained. The average thickness of the resist material film is preferably 1 nm to 5,000 nm, more preferably 10 nm to 1,000 nm, and even more preferably 30 nm to 200 nm.

  Prior to forming the resist material film on the substrate, a lower layer film (an antireflection film, a film for improving resist adhesion, a film for improving resist shape, etc.) may be formed on the substrate. By forming the antireflection film, it is possible to suppress the occurrence of standing waves due to radiation reflected by the substrate or the like in the pattern exposure step. By forming a film for improving the resist adhesion, the adhesion between the substrate and the resist material film can be improved. By forming a film for improving the resist shape, the resist shape after development can be further improved. That is, it is possible to reduce the skirt shape or constriction shape of the resist. On the other hand, in order to prevent resist shape deterioration due to the generation of standing wave of batch exposure radiation, it is desirable to design the thickness of the lower layer film so that reflection of radiation of batch exposure can also be suppressed. The lower layer film is desirably a film that does not absorb the radiation for batch exposure. If the lower layer film absorbs the radiation of the batch exposure, a radiation sensitization reaction may occur in the resist material film due to energy transfer or electron transfer from the lower layer film, which may generate acid in the pattern unexposed area. . For this reason, a buffer layer that does not propagate the radiation sensitization reaction may be disposed between the resist material film and the lower layer film to prevent sensitization from the lower layer film that has absorbed the radiation.

  A protective film may be further formed on the resist material film. By forming the protective film, it is possible to suppress the deactivation of the radiation-sensitive sensitizer, acid, and these reaction intermediates generated in the pattern exposure step S3, thereby improving the process stability. The protective film has at least one wavelength of non-ionizing radiation that is directly absorbed by the component (a) or (c) (radiation sensitive acid generator) in order to prevent an acid generation reaction in an unexposed portion in the batch exposure process. An absorption film that absorbs the portion may be used. By using the above absorption film, the out-of-band light (OOB light), which is ultraviolet radiation generated when exposed to EUV, is suppressed from entering the resist material film, and radiation sensitive acid is generated in the pattern unexposed area. The decomposition of the agent or the radiation-sensitive acid generating group can also be prevented. Furthermore, when the absorption film is formed directly on the resist material film, the wavelength of the second radiation in the batch exposure process is used to suppress acid generation in the resist material film due to the radiation sensitization reaction in the pattern unexposed area. It is preferable that it does not induce a radiosensitization reaction from the protective film. In addition, a buffer layer is disposed between the resist material film and the protective film to absorb the radiation so that the radiation-sensitive sensitizer in the resist material film is not sensitized by energy transfer or electron transfer from the protective film. Sensitization from the absorbing film may be prevented. By forming the absorption film on the resist material film after the pattern exposure step S3 and before the batch exposure step S4, the resist material film after the pattern exposure step S3 is formed by irradiation with the second radiation in the batch exposure step S4. Direct generation of acid from the remaining radiation-sensitive acid generator or radiation-sensitive acid-generating group can be further suppressed.

(Process S3: Pattern exposure process)
In the pattern exposure step S3, a light shielding mask having a predetermined pattern is arranged on the resist material film formed in the film formation step S2. Thereafter, the resist material film is irradiated with a first radiation (pattern exposure) through the mask from an exposure apparatus (radiation irradiation module) having a projection lens, an electron optical system mirror, or a reflection mirror.

  The first radiation used for pattern exposure is ionizing radiation or non-ionizing radiation having a wavelength of 250 nm or less. The upper limit of the wavelength of the non-ionizing radiation is 250 nm, and preferably 200 nm. On the other hand, the lower limit of the wavelength of the non-ionizing radiation is preferably 150 nm, and more preferably 190 nm.

  Note that ionizing radiation is radiation having sufficient energy to ionize atoms or molecules. In contrast, non-ionizing radiation is radiation that does not have sufficient energy to ionize atoms or molecules. Examples of the ionizing radiation include gamma rays, X-rays, alpha rays, heavy particle rays, proton rays, beta rays, ion beams, electron beams, EUV, and the like. The ionizing radiation used for pattern exposure is preferably an electron beam, EUV or ion beam, more preferably an electron beam or EUV. Non-ionizing radiation includes non-ionizing radiation having a wavelength of 250 nm or less, such as KrF excimer laser light and ArF excimer laser light.

  As pattern exposure light, for example, an electron beam of 1 keV to 200 keV, EUV having a wavelength of 13.5 nm, excimer laser light of 193 nm (ArF excimer laser light), and excimer laser light of 248 nm (KrF excimer laser light) are used. There are many cases. The exposure amount in pattern exposure may be smaller than in the case of batch exposure using the chemically amplified resist of the present embodiment. By the pattern exposure, groups represented by the components (a) to (c) in the resist material film are decomposed to generate an acid and a radiation-sensitive sensitizer that absorbs the second radiation.

  For exposure, a step-and-scan type exposure apparatus called a “scanner” is widely used. In this method, a pattern for each shot is formed by performing scanning exposure while synchronizing the mask and the substrate. By this exposure, a selective reaction occurs at the exposed portion in the resist.

  Prior to performing the following batch exposure step S4, the radiation-sensitive acid generator in the component (a) or (c) is directly absorbed on the resist material film in the post-pattern exposure step S3. An absorption film that absorbs at least a part of the wavelength of the ionizing radiation may be formed. By forming the absorption film, from the radiation sensitive acid generator or the radiation sensitive acid generating group remaining in the resist material film after the pattern exposure step S3 by irradiation with the second radiation in the following batch exposure step S4. The direct acid generation of can be further suppressed.

  In the case of using (b) a radiation-sensitive sensitizer generator having an alcoholic hydroxyl group in which hydrogen atoms are not substituted, the resist material film is formed until the following batch exposure step S4 is performed after the pattern exposure step S3. It is preferable to place in a reduced-pressure atmosphere or an inert atmosphere containing nitrogen or argon. By placing the resist material film in the above atmosphere, the exposure of the resist material film to oxygen during exposure and the termination of radical reaction by this oxygen can be suppressed, and the acid quenching by a small amount of basic compound can be suppressed. Since the chin can be suppressed, the process tends to be further stabilized. The upper limit of the time (storage time) until the collective exposure step S4 is performed after the pattern exposure step S3 is preferably 30 minutes, and more preferably 10 minutes. There exists a tendency which can suppress the fall of a sensitivity because storage time is 30 minutes or less. On the other hand, when (b) a radiation-sensitive sensitizer generating agent (that is, a ketal compound, an acetal compound or an orthoester compound) having an alcoholic hydroxyl group substituted with a hydrogen atom is used, after the pattern exposure step S3, the following Until the collective exposure step S4 is performed, it is preferable that the atmosphere in which the resist material film exists is in the atmosphere cleaned with an amine removal filter. When the above-mentioned (b) radiation-sensitive sensitizer generating agent is used, it may be treated in the atmosphere cleaned with an amine removing filter because it is not easily affected by oxygen as described above. By placing the resist material film in the above atmosphere, acid quenching by a small amount of a basic compound can be suppressed, so that the process tends to be further stabilized. The upper limit of the time (storage time) until the collective exposure step S4 is performed after the pattern exposure step S3 is preferably 30 minutes, and more preferably 10 minutes. There exists a tendency which can suppress the fall of a sensitivity because storage time is 30 minutes or less.

  In the resist pattern forming method of this embodiment, after the pattern exposure step S3 and before the following batch exposure step S4, the substrate is transferred from the exposure apparatus that performs the pattern exposure step S3 to the exposure device that performs the batch exposure step S4. You may further provide the process. Further, the batch exposure may be performed in a coating and developing apparatus connected inline or in a module corresponding to an interface with the exposure machine. When the component (2) includes a ketal compound, an acetal compound or an orthoester compound, the resist pattern forming method of this embodiment is performed after the pattern exposure step S3 and before the following batch exposure step S4, followed by a baking step S3a (post Pattern exposure bake (also referred to as PPEB or PEB)) (see FIG. 3). The heating temperature in the baking step is preferably 30 ° C. or higher and 150 ° C. or lower, more preferably 50 ° C. or higher and 120 ° C. or lower, and further preferably 60 ° C. or higher and 100 ° C. or lower. The heating time is preferably 5 seconds to 3 minutes, more preferably 10 seconds to 60 seconds. Moreover, it is preferable to perform the said baking in the environment which controlled humidity. This is because when the hydrolysis reaction is used as the deprotection reaction for generating the radiation-sensitive sensitizer, the humidity affects the reaction rate. When the resist pattern forming method includes the baking step S3a, it is possible to accelerate the generation of a radiation-sensitive sensitizer due to a hydrolysis reaction from an acetal compound, an ortho ester compound, a ketal compound or the like to a carbonyl compound.

(Process S4: Batch exposure process)
In the batch exposure step S4, a high-sensitivity module (exposure device or light source) having a projection lens (or light source) on the entire resist material film after the pattern exposure step S3 (the entire surface including the pattern exposed portion and the pattern unexposed portion). The second radiation is irradiated (collective exposure) from a radiation irradiation module. As this collective exposure, the entire wafer surface may be exposed at one time, a combination of local exposures, or overlapping exposure. As a light source for batch exposure, a general light source can be used. In addition to ultraviolet rays from mercury lamps and xenon lamps controlled to a desired wavelength by passing through a band-pass filter or a cut-off filter, LEDs are used. Narrow-band ultraviolet light from a light source, laser diode, laser light source, or the like may be used. In the collective exposure, only the radiation-sensitive sensitizer generated at the pattern exposure portion in the resist material film absorbs radiation. For this reason, in the batch exposure, radiation is selectively absorbed in the pattern exposure portion. Therefore, during the batch exposure, the acid can be continuously generated only in the pattern exposure part, and the sensitivity can be greatly improved. On the other hand, since no acid is generated in the pattern unexposed area, the sensitivity can be improved while maintaining the chemical contrast in the resist material film.

  Said 2nd radiation used for collective exposure is a non-ionizing radiation which has a wavelength longer than the wavelength of the non-ionizing radiation in said 1st radiation, and has a wavelength exceeding 250 nm, near ultraviolet rays (wavelength 250-450 nm) ) Is preferred.

  In the collective exposure step S4, in order to suppress the acid generation reaction in the pattern unexposed area, (1) from the wavelength of radiation that can be absorbed by the polymer component, the radiation sensitive acid generator, and the radiation sensitive sensitizer generator. It is necessary to expose with radiation having a long wavelength. Considering these, the lower limit of the wavelength of non-ionizing radiation in the batch exposure is preferably 280 nm, and more preferably 320 nm. When generating a radiation-sensitive sensitizer capable of absorbing longer wavelength radiation, the wavelength of the non-ionizing radiation may be 350 nm or more. However, if the wavelength of the non-ionizing radiation is too long, the efficiency of the radiation sensitization reaction is reduced, so the wavelength of radiation that can be absorbed by the polymer component, the radiation sensitive acid generator, and the radiation sensitive sensitizer generator. It is desirable to use non-ionizing radiation having a wavelength as short as possible that can be absorbed by the radiation-sensitive sensitizer. From such a viewpoint, the upper limit of the wavelength of the non-ionizing radiation is preferably 450 nm, and more preferably 400 nm.

  The pattern exposure step S3 and / or the collective exposure step S4 may be performed by immersion lithography (immersion exposure) or may be performed by dry lithography (dry exposure). Immersion lithography refers to exposure performed with a liquid interposed between a resist material film and a projection lens. On the other hand, dry lithography refers to exposure performed in a state where a gas is interposed between a resist material film and a projection lens, under reduced pressure, or in vacuum.

  In the immersion lithography in the pattern exposure step S3 and / or the batch exposure step S4, a liquid having a refractive index of 1.0 or more is applied between the resist material film or protective film formed in the film formation step S2 and the projection lens. You may carry out in the state interposed. The protective film is preferably for preventing reflection or improving reaction stability. The protective film preferably prevents liquid penetration, enhances water repellency on the film surface, and prevents defects due to liquid in immersion exposure.

  In the immersion lithography in the collective exposure step S4, the liquid absorbs at least a part of the wavelength of the second radiation directly absorbed by the component (a) or (c) (radiation sensitive acid generator). There may be. By using the liquid in the immersion lithography, the radiation-sensitive acid generator or the radiation-sensitive acid remaining in the resist material film after the pattern exposure step S4 by irradiation with the second radiation in the batch exposure step S4. Direct acid generation from the generating group can be further suppressed.

  When the pattern exposure step S3 and / or the batch exposure step S4 is performed by dry lithography, the pattern exposure step S3 and / or the batch exposure step S4 can be performed in the air, in a reduced pressure atmosphere, or in an inert atmosphere, but include a reduced pressure atmosphere or nitrogen or argon. It is preferable to carry out in an inert atmosphere. Furthermore, the upper limit of the concentration of the basic compound in the atmosphere during the implementation is preferably 20 ppb, more preferably 5 ppb, and even more preferably 1 ppb.

(Process S5: Baking process)
In the baking step S5, the resist material film after the batch exposure step S4 is heated (hereinafter also referred to as “post-flood exposure baking (PFEB)” or “post-exposure baking (PEB)”). When the resist pattern forming method of the present embodiment includes the baking step S3a after the pattern exposure step S3 and before the batch exposure step S4, the baking step S3a is referred to as a 1st PEB step, and the baking step S5 is referred to as a 2nd PEB step. Yes (see FIG. 3). The heating condition can be, for example, 50 ° C. or higher and 200 ° C. or lower and 10 seconds or longer and 300 seconds or shorter in an atmosphere of an inert gas such as nitrogen or argon. By setting the heating condition within the above range, acid diffusion can be controlled, and the processing speed of the semiconductor wafer tends to be ensured. In the baking step S5, the acid generated in the pattern exposure step S3 and the batch exposure step S4 causes (1) a polarity change reaction such as a deprotection reaction of the polymer component and a crosslinking reaction. Further, although the resist side wall may be wavy due to the influence of the standing wave of radiation in the resist material film, the waviness can be reduced by diffusion of reactants in the baking step S5.

(Step S6: Development step)
In the developing step S6, the resist material film after the baking step S5 is brought into contact with a developer. Development is performed by utilizing the fact that the solubility in the developer is selectively changed in the pattern exposure portion by the reaction in the resist material film in the baking step S5, thereby forming a resist pattern. The developer can be divided into a positive developer and a negative developer.

  As the positive developer, an alkali developer is preferable. The alkaline developer selectively dissolves the highly polar part of the resist material film after exposure. Examples of the alkaline developer include alkaline such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines (ethanolamine, etc.), tetraalkylammonium hydroxide (TAAH), etc. Examples include an alkaline aqueous solution in which at least one compound is dissolved. The alkaline developer is preferably an alkaline aqueous solution in which TAAH is dissolved. As TAAH, for example, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltriethylammonium hydroxide, trimethylethylammonium hydroxide, dimethyldiethylammonium hydroxide, water Trimethyl (2-hydroxyethyl) ammonium oxide (ie, choline), triethyl (2-hydroxyethyl) ammonium hydroxide, dimethyldi (2-hydroxyethyl) ammonium hydroxide, diethyldi (2-hydroxyethyl) ammonium hydroxide, hydroxylated Methyl tri (2-hydroxyethyl) ammonium, ethyl tri (2-hydroxyethyl) ammonium hydroxide, tetra (2-hydroxyethyl) ammonium hydroxide, etc. It is below.

  A 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) is widely used as a positive developer.

  In alkali development, a pattern is formed by utilizing a phenomenon in which carboxylic acid or hydroxyl group generated in a resist material film after exposure is ionized and dissolved in an alkali developer. After the development, in order to remove the developer remaining on the substrate, a water washing process called rinsing is performed.

  An organic developer is preferred as the negative developer. The organic developer selectively dissolves the low polarity portion of the resist material film after exposure. The organic developer is used to improve the resolution performance and the process window by removing patterns such as holes and trenches. In this case, the dissolution contrast between the pattern exposed portion and the pattern unexposed portion is obtained by the difference in affinity between the solvent in the resist material film and the organic developer. The portion with high polarity has low solubility in an organic developer, and remains as a resist pattern. Examples of the organic developer include 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone, methylcyclohexanone, acetophenone, methyl acetophenone, propyl acetate, acetic acid. Butyl, isobutyl acetate, amyl acetate, butenyl acetate, isoamyl acetate, propyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl valerate, methyl pentenoate, methyl crotonic acid, ethyl crotonic acid, methyl propionate, propionate Ethyl acetate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, Examples include methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate, and 2-phenylethyl acetate. .

  The resist pattern after the development step S6 (including rinse treatment) may be heated (sometimes referred to as post-baking). The post-baking can vaporize and remove the rinsing liquid remaining after the rinsing process, and can cure the resist pattern.

(Process S7: Etching process)
In step S7, a pattern is formed by etching or ion implantation of the underlying substrate using the resist pattern after the developing step S6 as a mask. The etching may be dry etching under an atmosphere such as plasma excitation, or may be wet etching immersed in a chemical solution. After the pattern is formed on the substrate by etching, the resist pattern is removed.

  The resist pattern forming method of the present embodiment includes the pattern exposure step S3 and the batch exposure step S4, so that the acid generated after exposure can be greatly increased only in the pattern exposed portion.

  FIG. 4 is a graph showing the absorbance at the pattern exposed portion and the absorbance at the unexposed portion of the resist material film during batch exposure. The portion of the resist material film that is not subjected to pattern exposure (pattern unexposed portion) absorbs ultraviolet rays having a relatively short wavelength, but does not absorb ultraviolet rays having a long wavelength. On the other hand, as described above, an acid and a radiation-sensitive sensitizer are generated in the pattern-exposed portion (pattern exposed portion) of the resist material film. The generated radiation-sensitive sensitizer absorbs non-ionizing radiation having a wavelength exceeding 250 nm, and absorbs ultraviolet rays having a relatively long wavelength. In batch exposure, radiation is irradiated to the entire surface of the resist material film without using a mask as in pattern exposure. However, in the pattern unexposed portion, absorption of the second radiation in the batch exposure step S4 is small. Accordingly, in the collective exposure step S4, an acid generation mechanism mainly occurs by the radiation sensitive sensitizer in the pattern exposure portion. For this reason, an acid can be continuously generated only in the pattern exposure part during the batch exposure, and the sensitivity can be improved while maintaining the lithography characteristics.

  FIG. 5A is a conceptual diagram showing, as a graph, an acid concentration distribution by a resist pattern forming method using a conventional chemically amplified resist material. When only pattern exposure is performed by EUV or the like as shown in FIG. 2, sufficient acid cannot be generated and sensitivity is lowered. When the exposure amount is increased in order to improve the sensitivity, the latent image of the resist pattern is deteriorated (lithography characteristics are lowered), so that it is difficult to achieve both sensitivity and lithography characteristics. FIG. 5B is a conceptual diagram showing, as a graph, the radiation-sensitive sensitizer concentration distribution and the acid concentration distribution obtained by the resist pattern forming method using the chemically amplified resist material according to the present embodiment. In pattern exposure, although a resist pattern latent image is excellent, sufficient acid is not generated. However, after batch exposure, the amount of acid can be increased only in the pattern exposure area by the radiation-sensitive sensitizer generated by pattern exposure, and sensitivity can be reduced with low exposure while maintaining an excellent latent image of the resist pattern. Can be improved. Since the acid generation mechanism by the radiation-sensitive sensitizer at the time of batch exposure occurs at room temperature, there is little bleeding of the latent image at the time of acid generation, and it is possible to greatly increase the sensitivity while maintaining the resolution.

<Semiconductor devices>
The semiconductor device according to the present embodiment is manufactured using the resist pattern formed by the above method. FIG. 6 is a cross-sectional view showing an example of the manufacturing process of the semiconductor device of this embodiment.

  FIG. 6A is a cross-sectional view showing a resist pattern forming step. The semiconductor wafer 1, the film to be etched 3 formed on the semiconductor wafer 1, and the film to be etched 3 by the resist pattern forming method are shown. It is sectional drawing with the formed resist pattern 2 (equivalent after completion | finish of image development process S6). Examples of the film to be etched include an active layer, a lower insulating film, a gate electrode film, and an upper insulating film. Between the etching target film 3 and the resist pattern 2, an antireflection film, a lower layer film for improving resist adhesion, and a lower layer film for improving the resist shape may be provided. A multilayer mask structure may be adopted. FIG. 6B is a cross-sectional view showing the etching process, and is a cross-sectional view of the semiconductor wafer 1, the resist pattern 2, and the etching target film 3 etched using the resist pattern 2 as a mask. The etched film 3 is etched along the shape of the opening of the resist pattern 2. FIG. 6C is a cross-sectional view of the pattern substrate 10 including the semiconductor wafer 1 and the pattern of the etched film 3 that has been etched after the resist pattern 2 is removed.

  A semiconductor device can be formed using a substrate having the pattern of the film 3 to be etched. As this formation method, for example, a method of embedding wiring between the patterns of the film to be etched 3 from which the resist pattern 2 has been removed and further laminating device elements on the substrate can be cited.

<Lithography mask>
The lithography mask according to this embodiment is manufactured by processing a substrate using the resist pattern formed by the above method. As this manufacturing method, the method of etching the hard mask formed in the glass substrate surface or the glass substrate surface, for example using a resist pattern is mentioned. Here, the lithography mask includes a transmissive mask using ultraviolet rays or an electron beam, a reflective mask using EUV, and the like. When the lithography mask is a transmissive mask, it can be manufactured by masking the light shielding portion or the phase shift portion with a resist pattern and processing by etching. Further, when the lithography mask is a reflective mask, it can be manufactured by processing the light absorber by etching using the resist pattern as a mask.

<Template for nanoimprint>
The nanoimprint template according to the present embodiment can also be manufactured using the resist pattern formed by the above method. Examples of the manufacturing method include a method of forming a resist pattern on a glass substrate surface or a hard mask surface formed on the glass substrate surface, and processing by etching.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. The measuring method of the physical property value in a present Example is shown below.

[Weight average molecular weight (Mw) and number average molecular weight (Mn)]
Mw and Mn of the polymer are GPC columns (2 G2000HXL, 1 G3000HXL, 1 G4000HXL, Tosoh Corporation), flow rate 1.0 mL / min, elution solvent tetrahydrofuran, sample concentration 1.0 mass%, sample Measurement was performed by gel permeation chromatography (GPC) using monodisperse polystyrene as a standard, using a differential refractometer as a detector under the analysis conditions of an injection amount of 100 μL and a column temperature of 40 ° C.

[ ¹³ C-NMR analysis]
The ¹³ C-NMR analysis for determining the content of the structural unit of the polymer uses a nuclear magnetic resonance apparatus (“JNM-ECX400” manufactured by JEOL Ltd.), uses CDCl ₃ as a measurement solvent, and uses tetramethylsilane ( TMS) was performed as an internal standard.

<[A] Synthesis of polymer>
(1) The monomer used for the synthesis of [A] polymer is shown below.

  The compound (M-1) is the structural unit (I), the compound (M-2) is the structural unit (IV), the compound (M-3) is the structural unit (III), and the compound (M-4). ) Gives structural unit (II), respectively.

[Synthesis Example 1] (Synthesis of polymer (A-1))
After dissolving 55 g (50 mol%) of the compound (M-2), 45 g (50 mol%) of the compound (M-1) and 3 g of azobisisobutyronitrile (AIBN) in 300 g of methyl ethyl ketone, The polymerization was carried out for 6 hours while maintaining the reaction temperature at 78 ° C. After the polymerization, the reaction solution was dropped into 2,000 g of methanol to solidify the polymer. Next, this polymer was washed twice with 300 g of methanol, and the resulting white powder was filtered and dried at 50 ° C. under reduced pressure overnight. [A] Polymer (A-1) as a polymer was obtained. Obtained. The polymer (A-1) had Mw of 7,000 and Mw / Mn of 2.10. As a result of ¹³ C-NMR analysis, the content ratios of the structural units derived from the compound (M-1) and the compound (M-2) were 52 mol% and 48 mol%, respectively.

[Synthesis Example 2] (Synthesis of polymer (A-2))
After dissolving 55 g (58 mol%) of the compound (M-3), 45 g (42 mol%) of the compound (M-1), 3 g of AIBN and 1 g of t-dodecyl mercaptan in 150 g of propylene glycol monomethyl ether, The polymerization was carried out for 16 hours while maintaining the reaction temperature at 70 ° C. After the polymerization, the reaction solution was dropped into 1,000 g of n-hexane to solidify and purify the polymer. Next, 150 g of propylene glycol monomethyl ether was added to the polymer again, and then 150 g of methanol, 37 g of triethylamine and 7 g of water were further added, and a hydrolysis reaction was performed for 8 hours while refluxing at the boiling point. The structural unit derived from -3) was deacetylated. After the reaction, the solvent and triethylamine were distilled off under reduced pressure, and the obtained polymer was dissolved in 150 g of acetone, then dropped into 2,000 g of water to solidify, and the resulting white powder was filtered and filtered at 50 ° C. under reduced pressure. And dried overnight to obtain a polymer (A-2) as a polymer [A]. The polymer (A-2) had Mw of 6,000 and Mw / Mn of 1.90. In addition, as a result of ¹³ C-NMR analysis, the p-hydroxystyrene structural unit obtained by deacetylation of the structural unit derived from the compound (M-3) and the inclusion of the structural unit derived from the compound (M-1) The proportions were 50 mol% and 50 mol%, respectively.

[Synthesis Example 3] (Synthesis of Polymer (A-3))
Compound (M-1) 6.99 g (40 mol%), compound (M-3) 6.22 g (40 mol%) and compound (M-4) 6.79 g (20 mol%) were added to propylene glycol monomethyl ether 40 g. A monomer solution was prepared by dissolving 0.79 g of AIBN (5 mol% based on the total number of moles of the compound) as a radical polymerization initiator. After putting 20 g of propylene glycol monomethyl ether into a 100 mL three-necked flask and purging with nitrogen for 30 minutes, the reaction kettle was heated to 80 ° C. with stirring. Thereto, the monomer solution prepared above was dropped over 3 hours, and further aged for 3 hours. After completion of the polymerization, the polymerization reaction liquid was cooled with water and cooled to 30 ° C. or lower. This polymerization reaction liquid was put into 400 g of hexane, and the precipitated solid content was separated by filtration. The solid content after filtration was washed twice with 80 g of hexane, further filtered, and dried at 50 ° C. for 17 hours. This solid content was put into a 100 mL eggplant flask containing 20 g of propylene glycol monomethyl ether and dissolved. Further, 3.49 g of triethylamine and 0.56 g of pure water were added, heated to 80 ° C., and reacted for 6 hours for hydrolysis. After completion of hydrolysis, the reaction solution was cooled with water and cooled to 30 ° C. or lower. This reaction solution was put into 400 g of hexane, and the precipitated solid content was separated by filtration. The filtered solid content was washed twice with 80 g of hexane, further filtered and dried at 50 ° C. for 17 hours to obtain 12.2 g (yield 61%) of the polymer (A-3). Mw of the polymer (A-3) was 7,500, and Mw / Mn was 1.52. As a result of ¹³ C-NMR analysis, the structural unit derived from (M-1), the p-hydroxystyrene structural unit obtained by deacetylation of the structural unit derived from (M-3), and (M-4) The content ratio of each structural unit derived from was 40 mol%, 40 mol%, and 20 mol%, respectively. In Table 1, it shows about Mw, Mw / Mn, and each structural unit content rate of the obtained polymers (A-1)-(A-3).

＊表中のＭ−３の構造単位含有割合は、Ｍ−３に由来する構造単位を脱アセチル化することにより得られたｐ−ヒドロキシスチレン構造単位としての含有割合を示す。

* The structural unit content ratio of M-3 in the table indicates the content ratio as a p-hydroxystyrene structural unit obtained by deacetylating the structural unit derived from M-3.

<(2) Component that generates radiation-sensitive sensitizer and acid by exposure>
[(B) Radiation-sensitive sensitizer generating agent]
(B) The following compounds were used as the radiation-sensitive sensitizer generating agent.
B-1: Compound represented by the following formula (B-1) B-2: Compound represented by the following formula (B-2)

[Absorbance measurement of component (b)]
Table 2 shows the component (b) and the sensitizer derived from the component (b). Moreover, the sensitizer derived from these (b) component and (b) component was prepared so that it might become a 0.0001 mass% cyclohexane solution, respectively. About this preparation solution, the light absorbency was measured using the spectrophotometer ("V-670" of JASCO Corporation) using cyclohexane as a reference solvent.

  The absorbance was determined by subtracting the absorbance of the reference solvent from the absorbance of the measurement solution at each wavelength of 250 nm to 600 nm. When the measured value of the absorbance in the entire wavelength region of the wavelength of 300 nm or more and 450 nm or less is less than 0.01, it is evaluated as “transparent”, and the wavelength at which the absorbance is 0.01 or more in the entire wavelength region is small Was evaluated as “absorbed”. The evaluation results are shown in Table 3 below. In addition, it confirmed that the transmittance | permeability of the cyclohexane which is a solvent used for the measurement of absorption spectrometry was 95% or more in all the wavelength ranges of wavelength 250 nm or more and 600 nm or less.

[(C) Radiation sensitive acid generator]
(C) The following [C1] compound (first compound) and [C2] compound (second compound) were used as the radiation-sensitive acid generator.
(Acid generating compound)
In this example, [C1] compound (first compound) and [C2] compound (second compound), the following [C1] compound, which is the compound with the smaller pKa of the generated acid, is generated. Used as a compound.
C-1-1: Compound represented by the following formula (C-1-1) C-1-2: Compound represented by the following formula (C-1-2) C-1-3: The following formula (C -1-3) Compound C-1-4: Compound represented by the following Formula (C-1-4)

(PKa of acid generated from acid generating compound ([C1] compound))
About the said compounds (C-1-1)-(C-1-4), it shows in Table 4 about the pKa (logarithm value of the reciprocal number of the acid dissociation constant of an acid) of the acid which generate | occur | produced from these compounds.

(Energy generating compound ([C1] compound) energy released when a cation is reduced to a radical)
Table 4 shows the calculation results of the energy released when the cations of these compounds (C-1-1) to (C-1-4) are reduced to radicals in these compounds. Here, the energy was calculated from the energy difference between the cation and the radical after the structure optimization of each cation and the radical was performed, the energy level of each substance was determined by the B3LYP / LANL2DZ method.

(Acid diffusion control agent)
In the present example, among the [C1] compound (first compound) and the [C2] compound (second compound), the following [C2] compound (C-2), which is the compound having the larger pKa of the generated acid -1 and C-2-4) were used as acid diffusion control agents. Moreover, C-2-1 to C-2-5 was used as an acid diffusion controller in the comparative example.
C-2-1: Compound represented by the following formula (C-2-1) (having radiation sensitivity)
C-2-2: Compound represented by the following formula (C-2-2) (does not have radiation sensitivity)
C-2-3: Compound represented by the following formula (C-2-3) (having radiation sensitivity)
C-2-4: Compound represented by the following formula (C-2-4) (having radiation sensitivity)
C-2-5: Compound represented by the following formula (C-2-5) (having radiation sensitivity)

(PKa of acid generated from acid diffusion controller ([C2] compound))
The acid diffusion controller having radiation sensitivity of the above compounds (C-2-1), (C-2-3), (C-2-4) and (C-2-5) is generated from these compounds. Table 5 shows the pKa (logarithm of the reciprocal of the acid dissociation constant of the acid) of the acid (anion portion).

(Energy released when cations in acid diffusion controller ([C2] compound) are reduced to radicals)
Further, the acid diffusion controller having radiation sensitivity of the above compounds (the above compounds (C-2-1), (C-2-3), (C-2-4) and (C-2-5)) Table 5 shows the calculation results of the energy released when cations in these compounds are reduced to radicals. Here, the energy was calculated from the energy difference between the cation and the radical after the structure optimization of each cation and the radical was performed, the energy level of each substance was determined by the B3LYP / LANL2DZ method.

(solvent)
G-1: Propylene glycol monomethyl ether acetate G-2: Ethyl lactate

[Example 1]
[A] 100 parts by mass of polymer (A-1), (b) 5 parts by mass of radiation-sensitive sensitizer generator (B-1), (c) [C1] compound (C -1-1) Mixing 15 parts by mass and 5.0 parts by mass of [C2] compound (C-2-1) and 4,300 parts by mass of solvent (G-1) and 1,900 parts by mass of (G-2) did. Next, the obtained mixed liquid was filtered through a membrane filter having a pore size of 0.20 μm to prepare a chemically amplified resist material (R-1).

[Examples 2-3 and Comparative Examples 1-10]
Chemically amplified resist materials (R-2) to (R-13) were prepared in the same manner as in Example 1 except that the components of the types and blending amounts shown in Table 6 were used. “-” In the table indicates that the corresponding component was not added.

<Formation of resist pattern>
In the “Clean Track ACT-8” of Tokyo Electron Co., after spin-coating the above-mentioned chemically amplified resist material on a silicon wafer, PB is performed at 110 ° C. for 60 seconds, and a resist material having an average thickness of 50 nm. A film was formed. Next, the resist material film is irradiated with an electron beam using a simple electron beam lithography apparatus (“HL800D” manufactured by Hitachi, Ltd., output 50 KeV, current density 5.0 A / cm ² ). Patterning was performed. For this patterning, a mask was used, and a line-and-space pattern (1L1S) composed of a line portion having a line width of 150 nm and a space portion having a spacing of 150 nm formed by adjacent line portions was used. After the electron beam irradiation, the following operations (1) to (3) were evaluated.

(Operation (1): No batch exposure)
After the electron beam irradiation, PEB is performed in the clean track ACT-8 at 110 ° C. for 60 seconds, and then in the clean track ACT-8, 2.38 mass% tetramethylammonium hydroxide (TMAH). Development was performed by the paddle method at 23 ° C. for 1 minute using an aqueous solution. After development, a positive resist pattern was formed by washing with pure water and drying.

(Operation (2): With batch exposure (10 minutes))
After the electron beam irradiation, the entire surface of the resist material film was collectively exposed for 10 minutes using a black light (Toshiba, wavelength 320 nm). Next, PEB was performed in the clean track ACT-8 under the conditions of 110 ° C. and 60 seconds. Thereafter, development, washing and drying were carried out in the same manner as in the above operation (1) to form a positive resist pattern.
(Operation (3): With batch exposure (30 minutes))
After the electron beam irradiation, the entire surface of the resist material film was collectively exposed for 30 minutes using a black light (Toshiba, wavelength 320 nm). Next, PEB was performed in the clean track ACT-8 under the conditions of 110 ° C. and 60 seconds. Thereafter, development, washing and drying were carried out in the same manner as in the above operation (1) to form a positive resist pattern.

<Evaluation>
The positive resist pattern thus formed was evaluated for sensitivity and nanoedge roughness according to the following procedure.

[sensitivity]
Optimum exposure dose is used to form a line-and-space pattern (1L1S) having a line width of 150 nm and a space portion having a spacing of 150 nm formed by adjacent line portions with a one-to-one line width. This optimum exposure amount was used as an index of sensitivity. When the optimum exposure amount was 50 μC / cm ² or less, it was judged as “A (good)”, and when it exceeded 50 μC / cm ² , it was judged as “B (defective)”. Table 7 shows the measurement values of the optimum exposure amount and the evaluation results of the sensitivity.

[Nano edge roughness]
The line pattern of the line and space pattern (1L1S) was observed using a high-resolution FEB length measuring device (“S-9220” from Hitachi, Ltd.). The shape is observed at 20 arbitrary points of the line pattern, and as shown in FIGS. 7 and 8 for each point, along the lateral side surface 12a of the line part 12 in the pattern formed on the base material (silicon wafer) 11. The difference “ΔCD” between the line width at the place where the generated unevenness was most remarkable and the design line width of 150 nm was measured. The average value of ΔCD of 20 points was used as an index of nano edge roughness. When the average value (nm) of ΔCD is 12.0 nm or less, “AA (very good)”, when it is more than 12.0 nm and 15.0 nm or less, “A (good)”, and when it is more than 15.0 nm It was judged as “B (defect)”. In addition, the unevenness | corrugation shown in FIG.7 and FIG.8 is exaggerated rather than actually. Table 7 shows the average value of ΔCD and the evaluation results of the nano edge roughness.

  As shown in Table 7, the radiation-sensitive [C1] compound and [C2] compound containing both onium cations whose energy released when reduced to radicals is less than 5.0 eV are used as the radiation sensitive component (c). In the examples contained as the acidic acid generator, it was confirmed that good sensitivity could be obtained without deteriorating the nano edge roughness even when the UV batch exposure amount was large. On the other hand, in the comparative example in which the energy released upon reduction to the onium cation radical of either the [C1] compound or the [C2] compound is 5.0 eV or more, the nano edge roughness is low when the UV batch exposure amount is small. Although the sensitivity increased without deteriorating, nano edge roughness was deteriorated when the exposure amount exceeded a certain value such as an exposure time of 30 minutes. In addition, in the case of the comparative example in which a compound having no radiation sensitivity was used as the acid diffusion control agent instead of the radiation sensitive [C2] compound, it was confirmed that the sensitivity enhancement in UV batch exposure was suppressed.

  As described above, according to the chemically amplified resist material and the resist pattern formation method, ionizing radiation such as EUV, electron beam, ion beam, or a wavelength of 250 nm or less such as KrF excimer laser and ArF excimer laser. When non-ionizing radiation is used as pattern exposure light, it is possible to exhibit excellent lithography performance while maintaining good sensitivity. Further, the chemically amplified resist material can be suitably used for the resist pattern forming method.

DESCRIPTION OF SYMBOLS 1 Semiconductor wafer 2, 12 Resist pattern 3 Etching film 10 Pattern board | substrate 11 Base material 12a Lateral side surface of resist pattern

Claims (8)

(1) a polymer component that becomes soluble or insoluble in a developer by the action of an acid;
(2) including a radiation-sensitive sensitizer and an acid-generating component upon exposure;
The component (2) contains the following (a) component, any two components in the following (a) to (c) components, or all of the following (a) to (c) components:
The component (a) or the component (c) has a first compound having radiation sensitivity and a second compound having radiation sensitivity,
The first compound includes a first onium cation and a first anion, and the second compound includes a second onium cation and a second anion different from the first anion,
A chemically amplified resist material, wherein the energy released when the first onium cation and the second onium cation are reduced to radicals is less than 5.0 eV.
(A) A radiation-sensitive sensitizer that absorbs the acid and the second radiation when the first radiation having a wavelength of 250 nm or less is irradiated and the second radiation having a wavelength exceeding 250 nm is not irradiated. Generation of a radiation-sensitive acid-sensitizer that does not substantially generate the acid and radiation-sensitive sensitizer when the first radiation is not irradiated and only the second radiation is irradiated. Agent (b) Generates a radiation-sensitive sensitizer that absorbs the second radiation when irradiated with the first radiation and does not emit the second radiation, and irradiates the first radiation Without radiating only the second radiation, the radiation-sensitive sensitizer generating agent that does not substantially generate the radiation-sensitive sensitizer (c) irradiating the first radiation, When no radiation is emitted, an acid is generated and the first radiation is Photoacid generator which does not substantially generate the acid when irradiated only the second radiation without morphism   The chemically amplified resist material according to claim 1, wherein a total content of the first onium cation and the second onium cation with respect to all onium cations in the chemically amplified resist material is 80 mol% or more.   The chemically amplified resist material according to claim 1 or 2, wherein a logarithmic value of the reciprocal of an acid dissociation constant of an acid generated from at least one of the first compound and the second compound is 0 or less.   The chemically amplified resist material according to claim 1, 2 or 3, wherein the polymer component (1) comprises a first polymer having a structural unit containing a group that generates a polar group by the action of an acid.   The first polymer has a structural unit containing a fluorine atom, or the (1) polymer component contains a second polymer different from the first polymer, and the second polymer contains a fluorine atom. The chemically amplified resist material according to claim 4, comprising a structural unit.   The chemically amplified resist material according to any one of claims 1 to 5, wherein the component (2) is a component different from the polymer component (1).   The chemically amplified resist material according to claim 6, wherein the content of the component (2) with respect to the total solid content is 10% by mass or more and 30% by mass or less. A film forming step of forming a resist material film on at least one surface of the substrate using the chemically amplified resist material according to any one of claims 1 to 7;
A pattern exposure step of irradiating the resist material film with radiation having a wavelength of 250 nm or less;
A batch exposure step of irradiating the resist material film after the pattern exposure step with radiation having a wavelength of more than 250 nm;
A baking step of heating the resist material film after the batch exposure step;
A resist pattern forming method comprising: a developing step of bringing the resist material film after the baking step into contact with a developer.

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