KR20170054298A - Chemically amplified resist material and process for forming resist pattern - Google Patents

Abstract

Provided are a chemically amplified resist material and a resist pattern forming method, capable of making compatible sensitivity and lithography performance when using a radiation such as EUV, of which the wavelength is not more than 250nm, as light for pattern exposure. The chemically amplified resist material includes: a polymer component (1) becoming available or unavailable for a developer depending on the action of acid; and a component (2) generating a radiation sensitive variation body and acid through light exposure. The component (2) contains components (a)(b), components (b)(c), or components (a)(c), and the component (b) includes a compound indicated in a formula (B). RB3 and RB4 of the formula (B) indicate an organic group or ring structure. But at least one among RB3 and RB4 includes a nitro group and a sulfonyl group, or the ring structure is a spirocyclic structure, a condensation ring structure, or exchangeable structure. (a) radiation sensitive acid-variation body generator (b) radiation sensitive variation body generator (c) radiation sensitive acid generator.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a chemically amplified resist material,

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

Lithography (hereinafter referred to as " EUV lithography ") using EUV (Extreme Ultraviolet) has been attracting attention as one of the element technologies for manufacturing next-generation semiconductor devices. EUV lithography is a pattern formation technique using EUV having a wavelength of 13.5 nm as exposure light. According to the EUV lithography, it is demonstrated that a very fine pattern (for example, a line width of 20 nm or less) can be formed in the exposure process of the semiconductor device manufacturing process.

However, since the EUV source developed at present has a low output, a long time is required for the exposure processing. As a result, there is a problem that EUV lithography is not practical. To solve this problem, a technique for improving the sensitivity of a resist material as a photosensitive resin has been developed (see Japanese Patent Application Laid-Open No. 2002-174894).

However, the sensitivity to EUV is insufficient even for a resist material in the above-mentioned techniques, and further, when the sensitivity to EUV is improved, there is a problem that lithography performance such as nano-edge roughness tends to deteriorate. This problem also exists when the electron beam or the like is used as the irradiation light.

Japanese Patent Application Laid-Open No. 2002-174894

The present invention has been accomplished on the basis of the above-described circumstances, and its object is to provide a method of irradiating non-ionizing radiation having a wavelength of 250 nm or less, such as ionizing radiation such as EUV, electron beam, ion beam, or KrF excimer laser, ArF excimer laser, And a method of forming a resist pattern using the chemically amplified resist material, which is capable of achieving both high sensitivity and lithography performance when used as a resist pattern.

The present invention for solving the above problems is characterized in that (1) a polymer component which becomes soluble or insoluble in a developer by the action of an acid, (2) a component which generates a radiation- Wherein the component (2) contains both of the following components (a) and (b), the following components (b) and (c), or both of the following components (a) (Hereinafter also referred to as " compound (B) ").

(a) irradiating a first radiation having a wavelength of not more than 250 nm and not irradiating a second radiation having a wavelength of more than 250 nm, the radiation and the radiation-sensitive composition for absorbing only the second radiation Sensitizer generator that does not substantially generate the acid and the radiation-sensitive sensitizer when irradiated with only the second radiation without irradiating the first radiation,

(b) generating a radiation-sensitive sensitizer for absorbing the second radiation when the first radiation is not irradiated and the second radiation is not irradiated, and only the second radiation A radiation-sensitive sensitizer generator which does not substantially generate the radiation-sensitive sensitizer

(c) irradiating the first radiation and generating the acid when it does not emit the second radiation, and substantially not generating the acid when only the second radiation is irradiated without irradiating the first radiation A radiation-sensitive acid generator

(In the formula (B), R ^B1 and R ^B2 each independently represent a monovalent organic group bonded through a carbon atom to a hydrogen atom, a halogen atom, an amino group, or a carbon atom to which R ^B3 O and R ^B4 O are bonded, groups are combined to each other, it represents a ring structure of the reduced water from 3 to 30 that is configured with the carbon atoms to which they are attached. R ^B3 and R ^B4 each independently, or a monovalent organic group having 1 to 20 carbon atoms, or combined with each other, they are attached are At least one of R ^B3 and R ^B4 is a halogen atom, a nitro group, a cyano group, a formyl group, a carbonyl group, a carboxyl group, a sulfo group, a sulfonyl group or a , Or the ring structure of the reduced water 4 to 30 is a spiro ring structure, a condensed ring structure, or a branched (bridged) structure)

According to an aspect of the present invention, there is provided a lithographic projection apparatus comprising a coating step of coating a chemically amplified resist material on at least one surface of a substrate, and a step of irradiating the resist film obtained by the coating with radiation having a wavelength of 250 nm or less (Hereinafter also referred to as " first radiation ") to the resist film after the pattern exposure process (hereinafter also referred to as " second radiation " A baking step of heating the resist film after the batch exposure step; and a developing step of bringing the resist film after the baking step into contact with a developing solution.

Here, " the acid and the radiation-sensitive sensitizer are not substantially generated when only the second radiation is irradiated without irradiating the first radiation ", " when the second radiation alone is irradiated without irradiating the first radiation, Does not substantially generate a radiation-sensitive sensitizer "and" does not substantially generate the acid when irradiated with only the second radiation without irradiating the first radiation "means that the radiation is irradiated with the acid or the radiation- Even when a sensitizer does not occur or when an acid or a radiation-sensitive sensitizer is generated by the irradiation of the second radiation, the difference in the concentration of the acid or the sensitizing radiation sensitizer between the exposed portion and the non- Of the pattern unexposed portion by the second radiation to such an extent that the radiation can be maintained at a size enough to form a pattern, Less amount and, as a result, the development and the pattern after the exposed portion or unexposed pattern means the extent that only any one portion of it can dissolve in the developing solution that less amount of acid or sense radiation-sensitized material. The term "organic group" means a group containing at least one carbon atom. "Reduced water" means the number of atoms constituting a ring of a cyclic structure, and in the case of a polycyclic ring, it means the number of atoms constituting the polycyclic ring. The term " polymer " is a concept including an oligomer.

According to the chemically amplified resist material and the resist pattern forming method of the present invention, the sensitivity in the case of using radiation having a wavelength of 250 nm or less such as EUV, electron beam, KrF excimer laser beam, ArF excimer laser beam, And lithography performance at both high levels.

1 is a schematic plan view showing a nano-edge roughness of a pattern.
2 is a schematic cross-sectional view showing the nano-edge roughness of the pattern.

Hereinafter, embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments.

≪ Chemical amplification type resist material &

The chemical amplification type resist material comprises (1) a polymer component that becomes soluble or insoluble in a developer by the action of an acid, (2) a component that generates a radiation-sensitive sensitizer and an acid upon exposure, and (2) (A) and (b), the following components (b) and (c), or both of the following components (a) to (c).

(a) irradiating a first radiation having a wavelength of not more than 250 nm and not irradiating a second radiation having a wavelength of more than 250 nm, the radiation and the radiation-sensitive composition for absorbing only the second radiation Sensitizer generator that does not substantially generate the acid and the radiation-sensitive sensitizer when irradiated with only the second radiation without irradiating the first radiation,

(b) generating a radiation-sensitive sensitizer for absorbing the second radiation when the first radiation is not irradiated and the second radiation is not irradiated, and only the second radiation A radiation-sensitive sensitizer generator which does not substantially generate the radiation-sensitive sensitizer

(c) irradiating the first radiation and generating the acid when it does not emit the second radiation, and substantially not generating the acid when only the second radiation is irradiated without irradiating the first radiation A radiation-sensitive acid generator

The chemical amplification type resist material may further include a solvent in addition to (1) the polymer component and the component (2), and may further include an acid diffusion controlling agent, a radical scavenger, a crosslinking agent, and other additives.

Here, the component (2) may be (1) a polymer or a part of a low-molecular compound constituting the polymer component, or may be a component different from (1) the polymer component. In this case, a part of the component (2) may be a component different from (1) the polymer component, and all of the component (2) may be a component different from (1) the polymer component.

[(1) Polymer component]

(1) The polymer component is a component that becomes soluble or insoluble in the developer due to the action of an acid. (1) The polymer component is a structural unit (hereinafter, referred to as " polymer unit ") including a group generating a polar group by dissociation of an acid-dissociable group by the action of an acid (hereinafter also referred to as " polar group protected by an acid- (Hereinafter also referred to as a "[C] polymer") having a structural unit (I) (hereinafter also referred to as a "structural unit (I)") And the like. Further, (1) the polymer component may contain components other than the components that are soluble or insoluble in the developer by the action of the acid, as long as the polymer [A] or the polymer [C] is included. In an embodiment, the (1) polymer component may further include a second polymer not containing the structural unit (I) (hereinafter also referred to as "[B] polymer"). The term " calixarene " means a cyclic oligomer in which a plurality of aromatic rings through which a heteroaromatic ring to which an aromatic ring or a hydroxy group to which a hydroxy group is bonded is bonded through a hydrocarbon group.

(A) a polymer and a [B] polymer are a copolymer of a structural unit containing a fluorine atom (hereinafter also referred to as "structural unit (II)"), a structural unit (III) containing a phenolic hydroxyl group and a lactone structure, (IV) containing a carboxyl group, a carboxyl group, a carboxyl group, a carboxyl group, a carboxyl group, a carboxyl group, a carboxyl group, a carboxyl group, a nitrate structure, a sultone structure or a combination thereof.

[[A] Polymer and [B] Polymer]

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

(Structural unit (I))

The structural unit (I) is a structural unit containing a polar group protected by an acid dissociable group. By having the polymer [A] having the structural unit (I), the sensitivity and the lithographic performance of the chemically amplified resist material can be further improved. As the structural unit (I), for example, a structural unit represented by the following formula (a-1) (hereinafter also referred to as a "structural unit (I-1)"), a structural unit represented by the following formula (Hereinafter also referred to as " structural unit (I-2) "). The formula (a-1) and (a-2) a group of the acid-dissociable group represented by -CR ^A2 R ^A3 R ^A4 and R ^A6 -CR ^A7 R ^A8.

In the 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 of 1 to 20 carbon atoms. R ^A3 and R ^A4 are each independently a monovalent straight chain hydrocarbon group having 1 to 20 carbon atoms or a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms or a combination of these groups to form a reduced number of carbon atoms 3 to 20 alicyclic structures.

In the 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 each independently represent a monovalent hydrocarbon group of 1 to 20 carbon atoms or a monovalent oxyhydrocarbon group of 1 to 20 carbon atoms. L ^A is a single bond, -O-, -COO- or -CONH-.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ^A2 , R ^A6 , R ^A7 and R ^A8 include a linear hydrocarbon group having 1 to 30 carbon atoms, an alicyclic hydrocarbon group having 3 to 30 carbon atoms, And an aromatic hydrocarbon group of 1 to 30 carbon atoms.

As the monovalent straight chain hydrocarbon group having 1 to 30 carbon atoms, for example,

Alkyl groups such as methyl group, ethyl group, n-propyl group and i-propyl group;

Alkenyl groups such as an ethynyl group, a propenyl group, and a butenyl group;

An alkynyl group such as an ethynyl group, a propynyl group, and a butynyl group.

As the monovalent alicyclic hydrocarbon group having 3 to 30 carbon atoms, for example,

Saturated monocyclic hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclopentyl group, cyclooctyl group, cyclodecyl group and cyclododecyl group;

An unsaturated monocyclic hydrocarbon group such as a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cyclooctenyl group, and a cyclodecenyl group;

Bicyclo [2.2.1] hepta group, a bicyclo [2.2.2] octa group, a tricyclo [3.3.1.1 ^3, 7] a saturated polycyclic hydrocarbon group such as decamethylene group;

And an unsaturated polycyclic hydrocarbon group such as a bicyclo [2.2.1] heptenyl group and a bicyclo [2.2.2] octenyl group.

As the monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms, for example,

Aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthryl and methyl anthryl groups;

And aralkyl groups such as a benzyl group, a phenethyl group, a naphthylmethyl group, and an anthrylmethyl group.

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

Examples of the monovalent straight chain hydrocarbon group having 1 to 20 carbon atoms and the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by R ^A3 and R ^A4 include groups represented by R ^A2 , R ^A6 , R ^A7 and R ^A8 , And the like.

Examples of the alicyclic structure having 3 to 20 reduced groups formed by combining the groups R ^A3 and R ^A4 together with the carbon atoms to which they are bonded include,

Monocyclic cycloalkane structures such as a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclopentene structure, a cyclopentadiene structure, a cyclohexane structure, a cyclooctane structure, and a cyclodecane structure;

A cycloalkane structure such as a norbornane structure, an adamantane structure, a tricyclodecane structure, and a tetracyclododecane structure; and the like.

As R ^A3 and R ^A4 , an alkyl group, a monocyclic cycloalkane structure, a norbornane structure and an adamantane structure formed by combining these groups together with a carbon atom to which they are bonded are preferable, and 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 monovalent hydrocarbon groups having 1 to 20 carbon atoms as exemplified above for R ^A2 , R ^A6 , R ^A7 and R ^A8 A group containing an oxygen atom between the carbon-carbon of the group, and the like.

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

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

As R ^A1 , a hydrogen atom and a methyl group are preferable, and a methyl group is more preferable from the viewpoint of copolymerization of a monomer giving the structural unit (I).

As R ^A5 , a hydrogen atom and a methyl group are preferable, and a hydrogen atom is more preferable from the viewpoint of copolymerization of a monomer giving 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) "), 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)").

R ^A1 to R ^A4 in the above formulas (a-1-a) to (a-1-d) are synonymous with the above formula (a-1). n _a is an integer of 1 to 4; R ^A5 to R ^A8 in the formula (a-2-a) are the same as those in the formula (a-2).

As n _a, 1, 2 and 4 are preferable, and 1 is more preferable.

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

^Wherein R ^A1 is as defined in the above formula (a-1).

Examples of the structural unit (I-2) include structural units represented by the following formulas.

^Wherein R ^A5 is as defined in the above formula (a-2).

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

The lower limit of the content ratio of the structural unit (I) to the total structural units constituting the polymer [A] is preferably 10 mol%, more preferably 20 mol%, still more preferably 30 mol% Is particularly preferable. On the other hand, the upper limit of the content is preferably 80 mol%, more preferably 70 mol%, still more preferably 65 mol%, and particularly preferably 60 mol%.

By setting the content ratio within the above range, it is possible to sufficiently secure the dissolution contrast to the developing solution of the pattern exposure portion and the non-visible portion of the resist film formed from the chemically amplified resist material, and as a result, the resolution and the like are improved.

(Structural unit (II))

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

In the 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 the 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, oxygen, _{sulfur, -CO-O-, -SO 2 -O} -NH-, -CO-NH- or -O-CO-NH-. R ^F4 is a single bond, C 1 -C 20 (u + 1) valent hydrocarbon group, or an oxygen atom at the terminal of R ^F5 side of the hydrocarbon group, a sulfur atom, -NR ^FF1 -, carbonyl, -CO-O- or -CO-NH-. R ^FF1 is a hydrogen atom or a monovalent hydrocarbon group of 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 -, it is -CO-O- or * -SO ₂ -O- *. R ^FF2 is a hydrogen atom or a monovalent hydrocarbon group of 1 to 10 carbon atoms. * ^Represents a site bonding 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, plural R ^F5 may be the same or different, plural L ^F3 may be the same or different, plural A ¹ may be the same or different, The plurality of R ^F6 may be the same or different.

In the formula (f-3), R ^F7 is 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. Provided that any 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, plural R ^F9 may be the same or different, and plural R ^F10 may be the same or different.

In formula (f-4), R ^F11 is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. R ^F12 and R ^F13 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group or a monovalent organic group having 1 to 20 carbon atoms. w is an integer of 1 to 4; When w is 2 or more, a plurality of R ^F12 may be the same or different, and a plurality of R ^F13 may be the same or different. Two or more of one or more R ^F12 and one or more R ^F13 may combine with each other to form a ring structure of 3 to 20 reduced numbers constituted together with a carbon atom or a carbon chain to which they are bonded. R ^F14 and R ^F15 each independently represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. Provided that 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 combine with each other to form a ring structure having 3 to 20 reduced numbers formed together with the carbon atoms to which they are bonded.

As 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, and a methyl group and an alkoxycarbonyl group are more preferable, and a methyl group and an ethoxycarbonyl group are more preferable.

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

Examples of the monovalent fluorinated hydrocarbon group having 1 to 20 carbon atoms represented by R ^F2 include those obtained by substituting a part or all of hydrogen atoms contained in a monovalent hydrocarbon group having 1 to 20 carbon atoms with a fluorine atom. Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms include the same groups as exemplified above for R ^A2 , R ^A6 , R ^A7 and R ^A8 .

The R ^F2 is preferably a fluorinated chain hydrocarbon group, more preferably a fluorinated alkyl group, more preferably a fluorinated methyl group and a fluorinated ethyl group.

Examples of the (u + 1) -valent hydrocarbon group having 1 to 20 carbon atoms represented by R ^F4 include monovalent hydrocarbon groups having 1 to 20 carbon atoms as exemplified above for R ^A2 , R ^A6 , R ^A7 and R ^A8 , And additionally u hydrogen atoms are excluded.

The R ^FF1 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom, a methyl group and an ethyl group.

The R ^{F4 is preferably a} single bond, a (u + 1) th chain hydrocarbon group having 1 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms and having a single bond, a (u + 1) -order chain hydrocarbon group and (u + 1) -order chain 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 divalent hydrocarbon groups, divalent hydrocarbon groups, carbon-carbon bonds in the hydrocarbon groups, or divalent heteroatom-containing groups A group in which a 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, for example,

Alkanediyl groups such as methanediyl, ethanediyl, propanediyl and butanediyl;

Alkenediyl groups such as an etendiyl group, a propenediyl group, and a butenediyl group;

Chain hydrocarbon groups such as an alkynediyl group such as an ethynyl group, an ethynyl group, an ethynyl group, an ethynyl group, an ethynyl group, an ethynyl group, a propynyl group,

Monocyclic cycloalkanediyl groups such as cyclopropanediyl, cyclobutanediyl, cyclobutanediyl, cyclopentanediyl, cycloheptanediyl and cyclohexanediyl;

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, and a tetracyclododecanediyl group;

Alicyclic hydrocarbon groups such as a norbornenediyl group and a polycyclic cycloalkenediyl group such as a tricyclodecenediyl group;

An alkylenediyl group such as a benzenediyl group, a benzenediyl group, a benzenediyl group, a toluenediaryl group, a benzenediyl group, a benzenediyl group, a benzenediyl group, a benzenediyl group, a benzenediyl group, a benzenediyl group,

(Cyclo) alkanediyl groups such as benzenediylmethanediyl, naphthalenediylcyclohexanediyl and the like, and the like.

The hetero atom-containing group means a group having two or more hetero atoms in the structure. The hetero atom-containing group may have one hetero atom or two or more hetero atoms. Here, the "hetero atom" means an atom other than a hydrogen atom and a carbon atom. In addition, the hetero atom-containing group may have only a hetero atom.

The heteroatom having two or more valencies of the heteroatom-containing group is not particularly limited as long as it is a heteroatom having a valence of 2 or more, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, .

As the group containing the hetero atom, such as ^{-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, and the like. Wherein R ^HE is a hydrogen atom or a monovalent hydrocarbon group of 1 to 20 carbon atoms.

Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a hydroxyl group, a carboxyl group, a nitro group, and a cyano group.

As R ^F5 and R ^F8 , a group containing an oxygen atom between a carbon atom and a carbon atom of a monovalent bond, a divalent hydrocarbon group of 1 to 20 carbon atoms, and a divalent hydrocarbon group is preferable, and a bond, a divalent straight chain More preferably a hydrocarbon group, a group containing an oxygen atom between the carbon-carbon atoms of the divalent chain hydrocarbon group and a divalent aromatic hydrocarbon group having 1 to 20 carbon atoms, and a single bond, an alkanediyl group, an alkanedioxyalkanediyl group, Di-yl group is more preferable.

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

The L ^F3 is preferably a single bond and a divalent fluorinated chain hydrocarbon group having 1 to 10 carbon atoms, more preferably a single bond and a fluorinated alkanediyl group having 1 to 10 carbon atoms.

The A ¹ is preferably an oxygen atom and -CO-O-.

The R ^FF2 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom, a methyl group and an ethyl group.

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 monovalent hydrocarbon groups, carbon-carbon bonds between the hydrocarbon groups, A group containing a divalent heteroatom-containing group, a group in which a part or all of the hydrogen atoms of these groups are substituted with a substituent, and the like.

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

The R ^F6 is preferably a hydrogen atom or a monovalent straight chain hydrocarbon group having 1 to 30 carbon atoms, more preferably a hydrogen atom and an alkyl group having 1 to 30 carbon atoms, further preferably a hydrogen atom and an alkyl group having 1 to 10 carbon atoms. However, when L ^F3 is a single bond, R ^F6 preferably has a fluorine atom.

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

As R ^F14 and R ^F15 , 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 are preferable, and a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, , More preferably a hydrogen atom, a methyl group, an ethyl group, and a hydroxydi (trifluoromethyl) ethyl group.

The R ^F9 and R ^F10 are preferably a methyl group, an ethyl group, a propyl group, a methyl fluoride group, an ethyl fluoride group and a fluorinated propyl group, more preferably a fluorinated methyl group and a fluorinated ethyl group, more preferably a fluorinated methyl group, and particularly preferably a trifluoromethyl group Do.

As u, 1 and 2 are preferable, and 1 is more preferable. The above v is preferably 1 and 2, more preferably 1. As 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 preferable.

^Wherein R ^F1 is synonymous with the formula (f-1). R ^F7 is synonymous with the formula (f-3).

When the polymer [A] has the structural unit (II), the lower limit of the content of the structural unit (II) relative to the total structural units constituting the polymer [A] is preferably 3 mol%, more preferably 5 mol% , And more preferably 10 mol%. On the other hand, the upper limit of the content is preferably 40 mol%, more preferably 35 mol%, still more preferably 30 mol%. By setting the content ratio within the above range, the sensitivity in the case of using EUV or the like as the pattern exposure light can be further improved. On the other hand, if the content ratio exceeds the upper limit, the rectangularity of the cross-sectional shape of the resist pattern may be deteriorated.

When the polymer component comprises the [B] polymer and the polymer [B] has the structural unit (II), the lower limit of the structural unit (II) relative to the total structural units constituting the [B] %, More preferably 5 mol%, and still more preferably 10 mol%. On the other hand, the upper limit of the content is preferably 40 mol%, more preferably 35 mol%, still more preferably 30 mol%. By setting the content ratio within the above range, the sensitivity in the case of using EUV or the like as the pattern exposure light can be further improved. On the other hand, if the content ratio exceeds the upper limit, the rectangularity of the cross-sectional shape of the resist pattern may be deteriorated.

(Structural unit (III))

The structural unit (III) is a structural unit containing a phenolic hydroxyl group (except for the structural unit (I) and structural unit (II)). When the polymer [A] or the polymer [B] has the structural unit (III), the sensitivity in the case of irradiating KrF excimer laser light, EUV (extreme ultraviolet) .

Some or all of the hydrogen atoms contained in the aromatic ring to which the phenolic hydroxyl group is bonded may be substituted by a substituent. Examples of the substituent include the same groups as those exemplified for R ^F5 and R ^F8 .

Examples of the structural unit (III) include structural units (hereinafter also referred to as "structural units (III-1) to (III-5)") represented by the following formulas (h-1) to have.

In the formulas (h-1) to (h-5), R ^AF1 is a hydrogen atom or a methyl group.

As R ^{AF1, 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.

When the polymer [A] has the structural unit (III), the lower limit of the content of the structural unit (III) relative to the total structural units constituting the polymer [A] is preferably 1 mol%, more preferably 20 mol% , More preferably 40 mol%. On the other hand, the upper limit of the content is preferably 90 mol%, more preferably 70 mol%, still more preferably 60 mol%. By setting the content ratio of the structural unit (III) within the above range, the sensitivity of the chemically amplified resist material can be further improved.

When the polymer component comprises the [B] polymer and the [B] polymer has the structural unit (III), the lower limit of the content ratio of the structural unit (III) to the total structural unit constituting [B] Is preferably 1 mol%, more preferably 30 mol%, still more preferably 50 mol%. On the other hand, the upper limit of the content is preferably 90 mol%, more preferably 80 mol%, and still more preferably 75 mol%. By setting the content ratio of the structural unit (III) within the above range, the sensitivity of the chemically amplified resist material can be further improved.

The structural unit (III) can be formed by, for example, a method of polymerizing a monomer in which a hydrogen atom of -OH group of hydroxystyrene is substituted with an acetyl group, and then subjecting the obtained polymer to a hydrolysis reaction in the presence of an amine.

(Structural unit (IV))

The structural unit (IV) is a structural unit comprising a lactone structure, a cyclic carbonate structure, a sultone structure, or a combination thereof (except for the structural units (I) to (III)). By further having the structural unit (IV) in the polymer [A] and the polymer [B], the solubility in the developer can be adjusted to a more appropriate value, and as a result, the lithographic performance of the chemically amplified resist material can be further improved . Further, the adhesion between the resist film formed from the chemically amplified resist material and the substrate can be improved. Here, the lactone structure means a structure having one ring (lactone ring) including a group represented by -OC (O) -. Further, the cyclic carbonate structure means a structure having one ring (cyclic carbonate ring) containing a group represented by -OC (O) -O-. The sultone structure means a structure having one ring (sultain ring) including a group represented by -OS (O) ₂ -. Examples of the structural unit (IV) include structural units represented by the following formulas.

Wherein R ^AL is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

As the R ^AL , a hydrogen atom and a methyl group are preferable, and a methyl group is more preferable from the viewpoint of copolymerization of a monomer giving the structural unit (IV).

Examples of the structural unit (IV) include a structural unit containing a norbornane lactone structure, a structural unit containing an oxanorbornane lactone structure, a structural unit containing a? -Butyrolactone structure, and an ethylene carbonate structure (Meth) acrylate, and a structural unit derived from norbornane lactone-yl (meth) acrylate are preferable, and structural units derived from norbornane lactone-yl (Meth) acrylate, a structural unit derived from norbornane lactone-yloxycarbonylmethyl (meth) acrylate, a structural unit derived from cyanogen-substituted norbornanactone- (Meth) acrylate, a structural unit derived from butyrolactone-4-yl (meth) acrylate, a structural unit derived from 3,5-dimethylbutyrolactone- (Meth) acrylate, a structural unit derived from 4,5-dimethylbutyrolactone-4-yl (meth) acrylate, a structural unit derived from 4- , Structural units derived from ethylene carbonate-methyl (meth) acrylate, structural units derived from cyclohexene carbonate-methyl (meth) acrylate, structural units derived from cyclohexanecarbonylmethyl (Meth) acrylate and a structural unit derived from norbornane sultone-yloxycarbonylmethyl (meth) acrylate are more preferable.

When the polymer [A] has the structural unit (IV), the lower limit of the content ratio of the structural unit (IV) to the total structural units constituting the polymer [A] is preferably 1 mol% , More preferably 20 mol%, and 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 setting the content ratio within the above range, the adhesion between the resist film formed from the chemically amplified resist material and the substrate can be further improved.

(B) the content of the structural unit (IV) relative to the total structural units constituting the polymer [B] when the polymer component comprises the [B] polymer and the polymer has the structural unit (IV) Is preferably 1 mol%, more preferably 10 mol%, still more preferably 30 mol%, and particularly preferably 40 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 setting the content ratio within the above range, the adhesion between the resist film formed from the chemically amplified resist material and the substrate can be further improved.

[Other structural units]

The polymer [A] and the polymer [B] may have other structural units in addition to the structural units (I) to (IV). Examples of the other structural unit include a structural unit including a polar group and a structural unit containing a non-reactive 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-reactive hydrocarbon group include linear alkyl groups and the like. The upper limit of the content ratio of the other structural units to the total structural units constituting the polymer [A] is preferably 20 mol%, more preferably 10 mol%. The upper limit of the content ratio of the other structural units to the total structural units constituting the [B] polymer is preferably 20 mol%, more preferably 10 mol%.

The lower limit of the total content of the polymer [A] and the polymer [B] is preferably 50% by mass, more preferably 60% by mass, and most preferably 70% by mass, based on the total solid content of the chemically amplified resist material. On the other hand, the upper limit of the total content is preferably 99% by mass, more preferably 90% by mass, and most preferably 80% by mass, based on the total solid content of the chemically amplified resist material.

The weight average molecular weight (Mw) of the polymer [A] in terms of polystyrene calculated by gel permeation chromatography (GPC) is not particularly limited, but the lower limit thereof is preferably 1,000, more preferably 2,000, still more preferably 3,000, Particularly preferred. On the other hand, the upper limit of the Mw of the [A] polymer is preferably 50,000, more preferably 30,000, even more preferably 20,000, and particularly preferably 15,000.

By setting the Mw of the polymer [A] within the above range, the coating property and the development defect inhibiting property of the chemically amplified resist material are improved. When the Mw of the polymer [A] is smaller than the above lower limit, there is a fear that a resist film having sufficient heat resistance may not be obtained. On the other hand, when the Mw of the polymer [A] exceeds the upper limit, the developability of the resist film may be lowered.

The lower limit of the ratio (Mw / Mn) of Mw to the polystyrene reduced number average molecular weight (Mn) of the polymer [A] is usually 1, and is preferably 1.3. On the other hand, the upper limit of the ratio is usually 5, preferably 3, and more preferably 2.

The polystyrene reduced weight average molecular weight (Mw) of the polymer [B] by polystyrene conversion is not particularly limited, but the lower limit thereof is preferably 1,000, more preferably 2,000, still more preferably 2,500, 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, even more preferably 20,000, and particularly preferably 15,000.

By setting the Mw of the [B] polymer within the above range, the coating property and the development defect inhibiting property of the chemically amplified resist material are improved. When the Mw of the [B] polymer is smaller than the above lower limit, there is a fear that a resist film having sufficient heat resistance may not be obtained. On the other hand, when the Mw of the [B] polymer exceeds the upper limit, there is a fear that the developability of the resist film is lowered.

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

Further, Mw and Mn of the polymer in the present specification are values measured by gel permeation chromatography (GPC) under the following conditions.

GPC column: 2 G2000HXL, 1 G3000HXL, 1 G4000HXL (above, Toso Co., Ltd.)

Column temperature: 40 DEG C

Elution solvent: tetrahydrofuran

Flow rate: 1.0 mL / min

Sample concentration: 1.0 mass%

Sample injection amount: 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. The upper limit of the content of the low molecular weight component in the polymer [A] is preferably 1.0% by mass, more preferably 0.5% by mass, and still more preferably 0.3% by mass. The lower limit of the content is, for example, 0.01% by mass. The upper limit of the content of the low molecular weight component in the [B] polymer is preferably 1.0% by mass, more preferably 0.5% by mass, still more preferably 0.3% by mass. The lower limit of the content is, for example, 0.01% by mass. By setting the content of the low molecular weight component of the polymer [A] and the polymer [B] within the above range, the lithographic performance of the chemically amplified resist material can be further improved.

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: " Inertsil ODA-25 占 퐉 column " (4.6 mm? X 250 mm)

Eluent: Acrylonitrile / 0.1% by mass aqueous solution of phosphoric acid

Flow rate: 1.0 mL / min

Sample concentration: 1.0 mass%

Sample injection amount: 100 μL

Detector: differential refractometer

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

(1) The polymer component may have two or more polymers having different fluorine atom content. Examples of the polymer component (1) include polymers [A] and polymers [B], and the polymer [B] has a higher fluorine atom content than the polymer [A] [A] polymer contains two or more [A] polymers having different fluorine content ratios, two or more [B] polymers having different fluorine atom ratios, and [B] And the like. As described above, (1) the polymer component has two or more polymers having different fluorine atom content ratios, whereby the polymer having a high fluorine atom content can be caused to shrink in the surface layer of the resist film to function as a water repellent polymer additive. As a result, elution of the component (2) and the like from the resist film can be suppressed, and the dynamic contact angle of the surface of the resist film can be improved to exhibit excellent water dropout characteristics. Thus, high-speed scanning exposure can be performed when liquid immersion exposure described later is performed.

(Method for synthesizing [A] polymer and [B] polymer)

The [A] polymer and the [B] polymer can be produced by, for example, polymerizing a monomer corresponding to a given structural unit by using a polymerization initiator such as a radical polymerization initiator in a suitable polymerization reaction solvent. Specific synthetic methods include, for example, a method in which a solution containing a monomer and a radical polymerization initiator is dropped into a polymerization reaction solvent or a solution containing a monomer to effect polymerization reaction, a method in which a solution containing a monomer and a solution containing a radical polymerization initiator A method comprising dropping them in a solution containing a polymerization reaction solvent or a monomer separately to carry out a polymerization reaction, a method comprising a step of separately adding a solution containing a monomer or a solution containing a monomer and a solution containing a radical polymerization initiator separately to a solution containing a polymerization reaction solvent or a monomer And a polymerization reaction is carried out.

As the radical polymerization initiator, azobisisobutyronitrile (AIBN), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis Azo type radical initiators such as 2,2'-azobis (2,4-dimethylvaleronitrile) and dimethyl 2,2'-azobisisobutyrate; Peroxide radical initiators such as benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, and the like. As the radical polymerization initiator, AIBN and dimethyl 2,2'-azobisisobutyrate are preferable, and AIBN is more preferable. These radical initiators may be used alone or in combination of two or more.

As the solvent used in the polymerization, for example, the same solvent as that which the chemically amplified resist material to be described later may contain may be used.

The lower limit of the reaction temperature in the polymerization is preferably 40 占 폚, and more preferably 50 占 폚. On the other hand, the upper limit of the reaction temperature is preferably 150 ° C, and 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.

The polymer [A] and the polymer [B] are preferably recovered by the reprecipitation method. That is, after completion of the reaction, the reaction liquid is put in a re-precipitation solvent to recover the desired polymer as a powder. As the re-precipitation solvent, alcohols, alkanes, etc. may be used singly or in a mixture of two or more kinds. In addition to the reprecipitation method, the polymer may 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.

[[C] polymer]

The [C] polymer is a calixarene having a structural unit (I). The chemically amplified resist material of the present invention can further improve the nano-edge roughness performance by (1) the polymer component includes the [C] polymer. Examples of the structural unit (I) of the [C] polymer include a structural unit represented by the following formula (2-3) (hereinafter also referred to as "structural unit (I-3)"). The [C] polymer has a structure in which the structural unit (I) is linked with a chain hydrocarbon group.

In the formula (2-3), R ¹⁰ is a monovalent hydrocarbon group having 1 to 20 carbon atoms or a monovalent oxyhydrocarbon group having 1 to 20 carbon atoms. R ¹¹ is a single bond or a divalent hydrocarbon group of 1 to 10 carbon atoms. R ¹² is a monovalent hydrocarbon group of 1 to 20 carbon atoms. R ¹³ and R ¹⁴ each independently represent a monovalent hydrocarbon group having 1 to 20 carbon atoms or an alicyclic structure having 3 to 20 reduced numbers formed by combining these groups together with the carbon atoms to which they are bonded. a is an integer of 0 to 6; and b is an integer of 0 to 6. However, a + b is 5 or less. k is 0 or 1; When a is 2 or more, plural R < ¹⁰ > may be the same or different.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ¹⁰ include the same groups as those exemplified above for R ^A2 , R ^A6 , R ^A7 and R ^A8 . Examples of the monovalent oxyhydrocarbon group having 1 to 20 carbon atoms represented by R ¹⁰ include a carbon-carbon pair of the monovalent hydrocarbon group or an oxygen atom-containing group at the terminal of the univalent hydrocarbon group.

As R ¹⁰ , an oxyhydrocarbon group is preferable, an alkoxy group is more preferable, and a methoxy group is more preferable.

As the divalent hydrocarbon group having 1 to 10 carbon atoms represented by R ¹¹ , for example, a monovalent hydrocarbon group exemplified above for R ^A2 , R ^A6 , R ^A7 and R ^A8 , To 10, and the like.

As R ¹¹ , a single bond and an alkanediyl group are preferable, and a methanediyl group is more preferable.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms represented by R ¹² , R ¹³ and R ¹⁴ include groups similar to those exemplified above for R ^A2 , R ^A6 , R ^A7 and R ^A8 .

Examples of the alicyclic structure having 3 to 20 carbon atoms in which the groups R ¹³ and R ¹⁴ are joined together with the carbon atoms to which they are bonded include structures similar to those exemplified above for R ^A3 and R ^A4 .

As a, an integer of 0 to 2 is preferable, and 1 is more preferable. b is preferably an integer of 0 to 2, more preferably 1.

The [C] polymer may have other structural units besides the structural unit (I-3). Examples of other structural units include structural units containing a phenolic hydroxyl group.

The lower limit of the molecular weight of the [C] polymer is preferably 500, more preferably 1,000. The upper limit of the molecular weight is preferably 3,000, more preferably 2,500. By setting the molecular weight of the [C] polymer within the above range, the sensitivity of the chemically amplified resist material and the nano-edge roughness performance can be further improved.

The [C] polymer can be synthesized, for example, by the following method. First, a compound having a phenolic hydroxyl group represented by the following formula (a) and an aldehyde represented by the following formula (b) are allowed to react in the presence of an acid such as trifluoroacetic acid in a solvent such as chloroform. Subsequently, the obtained compound is reacted with a compound giving an acid-dissociable group such as 2-bromoacetyloxy-2-methyladamantane in a solvent such as N-methylpyrrolidone in the presence of a base such as potassium carbonate, [C] polymer can be synthesized.

In the above formula (a), R ^{10 '} is a hydrocarbon group having 1 to 20 carbon atoms. a 'is an integer of 0 to 7; b 'is an integer of 1 to 7; However, a '+ b' is 8 or less. k is 0 or 1; When a 'is 2 or more, a plurality of R ^10' may be the same or different.

In the above formula (b), Y is a substituted or unsubstituted hydrocarbon group of 1 to 30 carbon atoms or a hydrogen atom. j is 1 or 2;

As j, 2 is preferable. As Y, an unsubstituted divalent hydrocarbon group is preferable, an alkanediyl group is more preferable, and a propanediyl group is more preferable.

[(2) Components generating radiation-sensitive sensitizer and acid by exposure]

Component (2) is a component which generates sensitizing radiation sensitizer and acid by exposure (irradiation with radiation). (A) and (b) of the three components of (a) a radiation-sensitive acid-sensitizer generator, (b) a radiation-sensitive sensitizer generator, and (c) a radiation- (B) and (c), or both (a) to (c).

((a) a radiation-sensitive acid-sensitizer generator)

(a) a radiation-sensitive acid-sensitizer generator generates a radiation-sensitive sensitizer for absorbing an acid and a second radiation by irradiation of the first radiation, and generates only a second radiation The acid and the radiation-sensitive sensitizer do not substantially occur.

Examples of (a) radiation-sensitive acid-sensitizer generators include onium salt compounds, diazomethane compounds, and sulfonimide compounds. Examples of the onium salt compound include a sulfonium salt compound, a tetrahydrothiophenium salt compound, and an iodonium salt compound. As the (a) radiation-sensitive acid-sensitizer generating agent, a sulfonium salt compound and an iodonium salt compound are preferable from the viewpoint of a high reduction potential, and an iodonium salt compound is more preferable.

The sulfonium salt compound is a compound containing 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.

R ¹ , R ² , R ^{1 '} , R ^2' , R ^{1 "} , R ^2" , R ³ and R ⁴ in the formulas (I) to (III) are each independently a hydrogen atom; A phenyl group; Naphthyl group; Anthracenyl group; Phenoxy group; Naphthoxy group; Anthracene oxy group; An amino group; Amide 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, an amino group, an amide group, or an alkyl group having 1 to 5 carbon atoms; 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, an amino group, an amide group, or a hydroxy group A substituted phenyl 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 anthraceneoxy 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; Branched, or cyclic alkyl group having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms) substituted with 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 cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group); Or a carbonyl group to which an alkyl group having 1 to 12 carbon atoms is bonded. In the above formulas (I) to (III), the hydrogen atom of the hydroxyl group is preferably a phenyl 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); 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 hydroxy group Or may be substituted. When the hydrogen atom of the hydroxy group is substituted, the sulfonium salt compound includes a ketal compound group or an acetal compound group. In the formula (I), any two or more of R ¹ , R ² , R ³ and R ⁴ may be bonded to each other through 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 may combine with each other to form a ring structure through a bond including -NR ^e -. Any two or more groups of R ¹ , R ² , R ^{1 '} , R ^2' and R ⁴ in the formula (II) may be bonded to each other by a single bond or a double bond, or -CH ₂ -, -O-, _{-SO 2 -, -SO 2 NH-,} -C (= O) -, -C (= O) O-, -NHCO-, -NHC (= O) NH-, -CHR e -, -CR e 2 -, -NH-, or -NR ^e -, to form a ring structure. Any two or more groups of R ¹ , R ² , R ^{1 '} , R ^2' , R ^{1 "} and R ^2" in the formula (III) may be bonded to each other by a single bond or a double bond, or -CH ₂ - _{, -S-, -SO 2 -, -SO} 2 NH-, -C (= O) -, -C (= O) O-, -NHCO-, -NHC (= O) NH-, -CHR e - , -CR ^e ₂ -, -NH-, or -NR ^e - via a coupling comprising a may be bonded to each other to form a ring structure. R ^e is a phenyl group; 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; 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 hydroxy group, . R ¹ , R ² , R ^{1 '} , R ^2' , R ^{1 "} , R ^2" , R ³ and R ⁴ are each independently preferably a phenyl group; Phenoxy group; A phenoxy group substituted with an alkyl group having 1 to 5 carbon atoms; Or an alkoxy group having 1 to 5 carbon atoms, or a phenyl group substituted with a hydroxy group. Formula (I) to (Ⅲ) of the X ^- represents an acid, preferably a strong acid, more preferably an anion of a superacid.

In the formula (I) to (Ⅲ), a ^{-C (-OH) R 1 R 2} , -C (-OH) R 1 'R 2' , and ^{-C (-OH) R 1 "R} 2" , etc. As the group to be displayed, for example, a group represented by the following formula can be mentioned. In the formulas, * represents a bonding site with sulfur ions in the formulas (I) to (III). In the group represented by -C (-OH) R ¹ R ² , -C (-OH) R ^{1 '} R ^{2 '} and -C (-OH) R ^{1 "} R ^{2 "} , the carbon to which the hydroxy group and the The atom becomes a carbonyl group by pattern exposure. In this way, the formula (I) The compound represented by to (Ⅲ) -C (-OH) R 1 R 2, -C (-OH) R 1 'R 2' , and -C (-OH) R ^{1 The} group represented by ^" R ^{2 "} is separated after pattern exposure to generate a radiation-sensitive sensitizer.

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

In the formulas (IV) to (V), R ⁵ , R ⁶ , R ^{5 '} , R ^6' and R ⁷ are each independently a hydrogen atom; A phenyl group; Naphthyl group; Anthracenyl group; Phenoxy group; Naphthoxy group; Anthracene oxy group; An amino group; Amide 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, an amino group, an amide group, or an alkyl group having 1 to 5 carbon atoms; 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, an amino group, an amide group, or a hydroxy group A substituted phenyl 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 anthraceneoxy 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; Branched, or cyclic alkyl group having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms) substituted with 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 cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group); Or a carbonyl group to which an alkyl group having 1 to 12 carbon atoms is bonded. In the formulas (IV) to (V), the hydrogen atom of the hydroxy group is preferably a phenyl 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); 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 hydroxy group Or may be substituted. When the hydrogen atom of the hydroxy group is substituted, the iodonium salt compound includes a ketal compound group or an acetal compound group. Any two or more groups of R ⁵ , R ⁶ and R ⁷ in the formula (IV) may be bonded to each other by 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 ^f - And may form a ring structure through bonding. Formula (V) of the ^{R 5, R 6, R 5} ' and R ^6', -CH ₂ or by any of a single bond or a double bond, two or more groups of the -, -O-, -S-, -SO ₂ NH-, -C (= O) -, -C (= O) O-, -NHCO-, -NHC (= O) NH-, -CHR ^f -, -CR ^f ₂ -, -NH- or -NR and may form a cyclic structure through a bond including ^f -. R ^f is a phenyl group; 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; 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 hydroxy group, . R ⁵ , R ⁶ , R ^{5 '} , R ^6' and R ⁷ are each independently preferably a phenyl group; Phenoxy 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 an alkoxy group having 1 to 5 carbon atoms, or a phenyl group substituted with a hydroxy group. Y ^- in the formulas (IV) to (V) represents an acid, preferably a strong acid, more preferably an anion of super strong acid.

Examples of the group represented by -C (-OH) R ⁵ R ⁶ and -C (-OH) R ^{5 '} R ^{6 '} in the formulas (IV) to (V) (-OH) R ¹ R ² , -C (-OH) R ^{1 '} R ^2' , -C (-OH) R ^{1 "} R ^{2 "} and the like exemplified in .

Examples of the acid anion of the sulfonium salt compound and the iodonium salt compound include a sulfonic acid anion, a carboxylic acid anion, a bis (alkylsulfonyl) amide anion, and a tris (alkylsulfonyl) methide anion. The anion of the acid represented by the general formula (XX), (XXI) and (XXII) is preferable, and the anion of the acid represented by the following general formula (XX) is more preferable.

In the general formulas (XX), (XXI) and (XXII), R ¹⁸ to R ²¹ each independently represent 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 connected to each other. The organic group is preferably an alkyl group whose 1-position is substituted by a fluorine atom or a fluoroalkyl group, and a phenyl group substituted by 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 tends to increase and the sensitivity tends to be improved. It is preferable that the organic group does not contain a fluorine atom as a substituent at the terminal.

Examples of the anion of the acid include at least one anion group selected from the group consisting of a sulfonic acid anion, a carboxylic acid anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion and a tris (alkylsulfonyl) methide anion . Examples of the anion of the acid include a group represented by the general formula "R ²² -SO ₃ -" (wherein R ²² represents a linear, branched or cyclic alkyl group, halogenated alkyl group, aryl group or alkenyl group which may have a substituent) And anions to be displayed. The number of carbon atoms of the straight-chain or branched-chain alkyl group as R ²² is preferably 1 or more and 10 or less. For example, when R ²² is a linear, branched or cyclic alkyl group which may have a substituent, examples of the anion of the acid include methanesulfonate, n-propanesulfonate, n-butanesulfonate, Sulfonates such as sulfonate, and 1-adamantanesulfonate, 2-norbornanesulfonate, d-camphor-10-sulfonate and the like. The halogenated alkyl group as R ²² is a group in which a part or all of the hydrogen atoms in the alkyl group are substituted with halogen atoms. The number of carbon atoms of the alkyl group is preferably 1 or more and 10 or less, more preferably a linear or branched alkyl group, More preferred are methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, tert-pentyl and isopentyl. Examples of the halogen atom substituted by a hydrogen atom include a fluorine atom, a chlorine atom, an iodine atom and a bromine atom. In the halogenated alkyl group, it is preferable that 50% or more and 100% or less of the total number of hydrogen atoms of the alkyl group (alkyl group before halogenation) is substituted with a halogen atom, and more preferably all hydrogen atoms are substituted with a halogen atom. Here, as the halogenated alkyl group, a fluorinated alkyl group is preferable. The number of carbon atoms in the fluorinated alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 8 or less, and most preferably 1 or more and 4 or less. The fluorinated alkyl group preferably has a fluorine atom content of preferably 10% or more and 100% or less, more preferably 50% or more and 100% or less, particularly preferably all hydrogen atoms substituted with a fluorine atom, Do. Examples of such a preferable fluorinated alkyl group include a trifluoromethyl group, a heptafluoro-n-propyl group, and a nonafluoro-n-butyl group.

The R ²² may have a substituent. The substituent includes a divalent linking group containing an oxygen atom. Examples of the linking group include an oxygen atom (ether bond: -O-), an ester bond (-C (= O) -O-), an amide bond (-C (= O) -NH-), a carbonyl group (O) -), a sulfonyl group (-SO ₂ -), and a carbonate bond (-OC (= O) -O-).

The anion of an acid includes, for example, an anion represented by the following formula, but is not limited thereto.

(a) The radiation-sensitive acid-sensitizer generator may be part of (1) the polymer constituting the polymer component. In this case, (a) the radiation-sensitive acid-sensitizer generator is present in such a form that a group excluding one hydrogen atom from the compound binds to the polymer.

(a) when the radiation-sensitive acid-sensitizer generating agent is a component different from (1) the polymer component, (1) the lower limit of the content of the radiation-sensitive acid-sensitizer generating agent relative to 100 parts by mass of the polymer component Is preferably 0.005 part by mass, more preferably 0.1 part by mass. On the other hand, the upper limit of the content is preferably 50 parts by mass, more preferably 30 parts by mass.

(a) when the radiation-sensitive acid-sensitizer generator is part of the polymer constituting (1) the polymer component, (1) the content ratio of the (a) radiation-sensitive acid- Is preferably 0.001 mol, more preferably 0.002 mol, and still more preferably 0.01 mol. On the other hand, the upper limit of the content is preferably 0.5 mol, more preferably 0.3 mol.

If the content or the content is smaller than the above lower limit, the sensitivity may be lowered. On the contrary, when the content or the content exceeds the upper limit, the resist film tends to be difficult to form, and the rectangularity of the cross-sectional shape of the resist pattern may deteriorate.

((b) a radiation-sensitive sensitizer generating agent)

(b) a radiation-sensitive sensitizer generator generates a radiation-sensitive sensitizer for absorbing the second radiation by irradiation with the first radiation, and when the second radiation alone is irradiated without irradiating the first radiation Sensitive sensitizer, and is different from the (a) radiation-sensitive acid-sensitizer generator.

((B) compound)

(b) the radiation-sensitive sensitizer generating agent includes the compound (B) represented by the following formula (B).

In the formula (B), R ^B1 and R ^B2 each independently represent a monovalent organic group which is bonded to a carbon atom to which a hydrogen atom, a halogen atom, an amino group, or R ^B3 O and R ^B4 O bond by a carbon atom, Together with a carbon atom to which they are bonded, form a cyclic structure of 3 to 30 carbon atoms. R ^B3 and R ^B4 are each independently a monovalent organic group of 1 to 20 carbon atoms or represent a ring structure of a reduced number of 4 to 30 constituted together with OCO to which they are bonded to form a ring. Provided that at least one of R ^B3 and R ^B4 contains a halogen atom, a nitro group, a cyano group, a formyl group, a carbonyl group, a carboxyl group, a sulfo group, a sulfonyl group or a combination thereof, A spirocyclic structure, a condensed ring structure, or a oil-exchange structure.

In the chemically amplified resist material of the present invention, the chemical structure of the radiation-sensitive sensitizer generating agent (b) is converted by direct or indirect reaction by irradiation of the first radiation to assist in the generation of acid Thereby generating a sensitizing radiation sensitizer. Since this radiation-sensitive sensitizer is easier to absorb the second radiation than (b) the radiation-sensitive sensitizer generator, it is preferable that, when the pattern exposure is performed by the first radiation, The amount of absorption of the second radiation between the pattern unexposed portion that does not generate the radiation sensitive property and the pattern unexposed portion greatly differs, and the contrast of the absorption amount tends to be obtained.

The chemically amplified type resist material comprises (b) a radiation-sensitive sensitizer generating agent (B), and the radiation having a wavelength of 250 nm or less, such as EUV, electron beam, KrF excimer laser beam, or ArF excimer laser beam, Both the sensitivity and the lithographic performance in the case of using as the pattern exposure light can be compatible at a high level. The reason why the chemically amplified resist material has the above-mentioned structure and exhibits the above effect is not clear, but can be estimated as follows, for example. That is, the compound (B) is a compound wherein R ^B3 and R ^B4 in the formula (B) are a halogen atom, a nitro group, a cyano group, a formyl group, a carbonyl group, a carboxyl group, a sulfo group, a sulfonyl group, An electron withdrawing group, or they form a spirocyclic structure, condensed ring structure, or oil-exchange structure, the activation energy necessary for cleavage of the acetal structure thereof is suitably high. Therefore, in the chemical amplification type resist material, the acid generated from the (a) radiation-sensitive acid-sensitizer generator and (c) the radiation-sensitive acid generator is transferred to the pattern non-exposure portion in the pattern exposure portion, Even when a small amount of acid is present, generation of the radiation-sensitive sensitizer in the pattern unexposed area can be suppressed. Specific electron-withdrawing groups such as a halogen atom which may be included in the R ^B3 and R ^B4 in the formula (B) are electron-withdrawing groups which are difficult to be hydrolyzed by an acid, unlike ester groups and the like. Therefore, even when R ^B3 and R ^B4 include the specific electron withdrawing group, the specific hydrolysis of the electron withdrawing group can be prevented from competing with the cleavage of the acetal structure.

As a result, it is considered that the chemically amplified resist material is excellent in sensitivity and lithography performance.

Examples of the halogen atom represented by R ^B1 and R ^B2 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the monovalent organic group represented by R ^B1 and R ^B2 include groups similar to those exemplified above for R ^F6 , R ^F12 , R ^F13 , R ^F14 and R ^F15 .

Examples of the ring structure having 3 to 30 carbon atoms which are combined with the carbon atoms to which the groups represented by R ^B1 and R ^B2 are bonded include an alicyclic structure having 3 to 20 carbon atoms and an aliphatic heterocyclic ring having 3 to 20 carbon atoms An aromatic ring structure having 6 to 20 reduced rings, and an aromatic heterocyclic ring structure having 5 to 20 reduced rings. These ring structures may be spiro ring structures, condensed ring structures or oil-exchange structures.

Examples of the alicyclic structures of the reduced numbers 3 to 20 include structures similar to those exemplified for R ^A3 and R ^A4 .

As the aliphatic heterocyclic structures of the reduced numbers 3 to 20, for example,

Lactone structures such as a hexanolactone structure and a norbornane lactone structure;

A sultone structure such as a hexanosultone structure and a norbornanesultone structure;

An oxocycloheptane structure, and an oxanorbornane structure;

A nitrogen atom-containing heterocyclic structure such as an azacyclohexane structure and a diazabicyclooctane structure;

A thiocyclohexane structure, and a thianorbornane structure, and the like.

Examples of the aromatic ring structures of the reduced numbers 6 to 20 include a benzene structure, a naphthalene structure, a phenanthrene structure, and an anthracene structure.

Examples of the aromatic heterocyclic structure of the reduced water 5 to 20 include an oxygen atom-containing heterocyclic structure such as a furan structure, a pyran structure, and a benzopyran structure, a nitrogen atom-containing heterocyclic structure such as a pyridine structure, a pyrimidine structure, And the like.

Examples of R ^B1 and R ^B2 include a hydrogen atom, a halogen atom, an amino group, 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 amide group, an unsaturated hydrocarbon group having 1 to 30 carbon atoms, or a carbonyl group bonded with an alkyl group having 1 to 12 carbon atoms, or the phenyl group, the naphthyl group, the anthracenyl group, the alkoxy group, the alkylthio group, Or a group in which at least a part of the hydrogen atoms of the naphthoxy group, the anthracenoxy group or the unsaturated hydrocarbon group is substituted, or a group in which these groups are -CH ₂ -, -O-, -S-, -SO ₂ -, - _{SO 2 NH-, -C (= O} ) -, -C (= O) O-, -NHCO-, -NHC (= O) NH-, -CHR g -, -CR g 2 -, -NH- , and -NR ^g - (Wherein R ^g represents a phenyl group, a phenoxy group, a halogen atom, a linear, branched or cyclic saturated or unsaturated hydrocarbon group of 1 to 30 carbon atoms, an alkoxy group of 1 to 5 carbon atoms, a hydroxy group or an alkyl group of 1 to 5 carbon atoms A linear or branched saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms, or a phenyl group substituted with an alkoxy group or a hydroxy group having 1 to 5 carbon atoms), a single bond or a double bond It is preferable that R < ^{B1 >} and R < ^B2 > form a ring structure together with the carbon atom to which they are bonded. Examples of the substituent include the same groups as those exemplified above for R ^F5 and R ^F8 .

As R ^B1 and R ^B2 , a phenyl group substituted with an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms is more preferable, and a phenyl group substituted with an alkoxy group having 1 to 3 carbon atoms is more preferable, Is particularly preferred. It is preferable that R ^B1 and R ^B2 are the same.

Examples of the monovalent organic group represented by R ^B3 and R ^B4 include groups similar to those exemplified above for R ^F6 , R ^F12 , R ^F13 , R ^F14 and R ^F15 .

Examples of the ring structure of the reduced number of 4 to 30 formed by combining R ^B3 and R ^B4 together with OCO to which they are bonded include 1,3-dioxolane structure, 1,3-dioxane structure, 1,3- Dioxepane structure and the like, and a polycyclic structure such as a spirocyclic structure, a condensed ring structure, and an oil-exchange structure which are composed of a ring structure different from the monocyclic structure.

The reduced water of the monocyclic structure is preferably 5 and 6, more preferably 5. As the ring structure, a 1,3-dioxolane structure and a 1,3-dioxane structure are preferable, and a 1,3-dioxolane structure is more preferable.

(B) is preferably composed of R ^B1 -CR ^B2 in the formula (B) and has a partial structure represented by the following formulas (XXVII) to (XXX).

* In the formulas (XXVII) to (XXX) represents a moiety bonded to OR ^B3 or OR ^B4 in the formula (B). The hydrogen atoms of the aromatic rings in the formulas (XXVII) to (XXX) 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 may be bonded to another aromatic ring to form a naphthalene ring or an anthracene ring It may be. And R ²⁵ represents an alkyl group having 1 to 5 carbon atoms.

(B) a compound having the partial structure represented by the above formulas (XXVII) to (XXX), (b) a radiation sensitive sensitizer generator and (b) a radiation sensitizer The shift of the absorption wavelength of the radiation between the color sensitizing bodies can be further increased, and as a result, the increase / decrease reaction can be caused more selectively in the pattern exposure section.

As the partial structure, a partial structure represented by the formula (XXVII) is preferable, and a partial structure represented by the following formula is more preferable.

At least one of R ^B3 and R ^B4 in the formula (B) is a halogen atom, a nitro group, a cyano group, a formyl group, a carbonyl group, a carboxyl group, a sulfo group, a sulfonyl group, (Hereinafter also referred to as " compound (B1) "). (B1) compound is believed to have an appropriately high activation energy required for cleavage by binding an organic group containing an electron-withdrawing group such as a halogen atom to at least one of the oxygen atoms constituting the acetal structure.

When R ^B3 and R ^B4 of the compound (B1) are combined with each other to form a ring structure, the ring structure is preferably a monocyclic structure.

As the group included in R ^B3 and R ^B4 , a nitro group and a sulfonyl group are preferable. Also, R ^B3 and R ^B4 are preferably the same.

As the compound (B1), for example, a compound represented by the following formula can be given.

^Wherein R ^B1 and R ^B2 are as defined in the above formula (B).

As the compound (B1), a compound represented by the following formula is preferable.

As the compound (B), a compound represented by the following formula (BI) or the formula (B-II) (hereinafter also referred to as a "(B2) (B2) represents a ring structure of a reduced number of 4 to 30 formed by combining R ^B3 and R ^B4 in the formula (B) together with OCO to which they are bonded, and the ring structure of the reduced number of 4 to 30 is Spirocyclic structure, condensed ring structure, or oil-exchange structure. (B2) compound, the OCO of the acetal structure together with R ^B3 and R ^B4 constitute a spirocyclic structure, condensed ring structure or oil-exchange structure, so that the activation energy required for cleavage is appropriately increased.

R ^B1 and R ^B2 in the formula (BI) and the formula (B-II) are the same as those in the formula (B).

In the formula (BI), R ^X1 is a group having a monocyclic structure having 4 to 20 reduced numbers. R ^X2 is a group having a ring structure of 3 to 20 in reduced number.

In the formula (B-II), R ^Y1 is a group having a monocyclic structure having a reduced number of 5 to 20. R ^Y2 is a group having a ring structure of 3 to 20 in reduced number. n is an integer of 0 to 3;

R ^X1 , R ^X2 , R ^Y1 and R ^Y2 may have one or more substituents. The substituent may be an electron withdrawing group or an electron donating group, and examples thereof include a hydrocarbon group having 1 to 10 carbon atoms, an oxyhydrocarbon group having 1 to 10 carbon atoms, a hydroxy group, an amino group, a carboxyl group, a nitro group, a cyano group, .

Examples of the monocyclic structure having 4 to 20 carbon atoms in the above R ^X1 include monocyclic aliphatic heterocyclic structures of 4 to 20 carbon atoms. Examples of the monocyclic aliphatic heterocyclic structure of the reduced water 4 to 20 include monocyclic structures of the aliphatic heterocyclic structures exemplified above for R ^B1 and R ^B2 . The reduced water of the monocyclic structure is preferably 5 and 6, more preferably 5. As the monocyclic structure, a 1,3-dioxolane structure and a 1,3-dioxane structure are preferable, and a 1,3-dioxolane structure is more preferable.

The ring structure having 3 to 20 reduced numbers of R ^X2 may be monocyclic or polycyclic. Examples of the ring structure of the R ^x2 having a reduced number of 3 to 20 include an alicyclic structure having a reduced number of 3 to 20 and an aliphatic heterocyclic structure having a reduced number of 3 to 20. Examples of the alicyclic structures of the reduced numbers 3 to 20 include structures similar to those exemplified for R ^A3 and R ^A4 . Examples of the aliphatic heterocyclic structures of the above-mentioned reduced numbers 3 to 20 include structures similar to those exemplified above for R ^B1 and R ^B2 . As the ring-structure reduced water of R ^X2 , 5 and 6 are preferable. The cyclic structure of R ^X2 is preferably an alicyclic structure, more preferably a cyclopentane structure and a cyclohexane structure, and more preferably a cyclopentane structure.

Examples of the monocyclic structure having 5 to 20 reduced numbers of R ^Y1 include monocyclic aliphatic heterocyclic structures having 5 to 20 reduced numbers. Examples of the monocyclic aliphatic heterocyclic structure of the above-mentioned reduced water 5 to 20 include monocyclic structures of the aliphatic heterocyclic structures exemplified above for R ^B1 and R ^B2 . The reduced water of the monocyclic structure of R ^Y1 is preferably 5 and 6, more preferably 5. The reduced water of the monocyclic structure of R ^Y1 is preferably a 1,3-dioxolane structure and a 1,3-dioxane structure, and more preferably a 1,3-dioxolane structure.

The ring structure of the reducing number 3 to 20 contained in R ^Y2 may be monocyclic or polycyclic. Examples of the ring structure of the reduced number 3 to 20 contained in the R ^Y2 include an alicyclic structure having a reduced number of 3 to 20, an aliphatic heterocyclic structure having a reduced number of 3 to 20, an aromatic ring structure having a reduced number of 6 to 20, And a heterocyclic structure. Examples of the alicyclic structures of the reduced numbers 3 to 20 include structures similar to those exemplified for R ^A3 and R ^A4 . Examples of the aliphatic heterocyclic structure of the reduced water 3 to 20, the aromatic ring structure of the reduced water 6 to 20, and the aromatic heterocyclic ring structure of the reduced water 5 to 20 include structures and the like as exemplified above for R ^B1 and R ^B2 . As the ring-structure reduced water of R ^Y2 , 5 and 6 are preferable. The ring structure of R ^Y2 is preferably an alicyclic structure, more preferably a cyclohexane structure and a norbornane structure.

As n, an integer of 0 to 2 is preferable, and 0 and 1 are preferable.

Among the compounds (B2), those represented by the above formula (B-I) include, for example, compounds represented by the following formulas.

^Wherein R ^B1 and R ^B2 are as defined in the above formula (B).

Examples of the compound represented by the formula (B-II) in the compound (B2) include compounds represented by the following formulas.

^Wherein R ^B1 and R ^B2 are as defined in the above formula (B).

As the compound (B-2), a compound represented by the following formula is preferable.

(b) The radiation-sensitive sensitizer generator may further comprise a known radiation-sensitive sensitizer generator in addition to the compound (B). In this case, the lower limit of the content of the (B) compound in the (b) radiation-sensitive sensitizer generator is preferably 60 mol%, more preferably 70 mol%. When the content ratio is smaller than the lower limit, the sensitivity of the chemically amplified resist material may not be sufficiently improved. The content may be 100 mol%.

Further, the (b) radiation-sensitive sensitizer generator may be a part of (1) the polymer constituting the polymer component. In this case, the (b) radiation-sensitive sensitizer generator is present in such a form that a group other than a hydrogen atom from the (B) compound or the like bonds to the polymer.

(b) when the radiation-sensitive sensitizer generator (b) is a component different from (1) the polymer component, the lower limit of the content of the radiation-sensitive sensitizer generator (b) relative to 100 parts by mass of the polymer component is 0.1 mass More preferably 1 part by mass, still more preferably 4 parts by mass. On the other hand, the upper limit of the content is preferably 50 parts by mass, more preferably 30 parts by mass, still more preferably 15 parts by mass.

(b) when the radiation-sensitive sensitizer generating agent (b) is a part of the polymer constituting (1) the polymer component, the lower limit of the content ratio of the radiation- 0.001 mol, more preferably 0.002 mol, and still more preferably 0.01 mol. On the other hand, the upper limit of the content is preferably 0.95 mol, more preferably 0.3 mol.

If the content or the content is less than the above lower limit, the sensitivity may be lowered. Conversely, if the content or the content exceeds the upper limit, the resist film tends to be difficult to form, and the rectangularity of the cross-sectional shape of the resist pattern may deteriorate.

(Sensitizing radiation sensitizer)

The sensitizing radiation sensitizer is generated from (a) a radiation-sensitive acid-sensitizer generator and (b) a radiation-sensitive sensitizer generator by irradiation of a first radiation, and absorbs the second radiation and (c ) Photoacid generator (for example, photoacid generator: PAG).

Examples of the radiation sensitive sensitizer include 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, xanthine 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 , Thiopyrilium and derivatives thereof, tetrapyrin and derivatives thereof, annulene and derivatives thereof, spiropyran and derivatives thereof, spirooxazine and derivatives thereof, thiosporopyran and its derivatives, thiopyrimidine and derivatives thereof, Oxazine and derivatives thereof, azine and derivatives thereof, thiazine and derivatives thereof, oxazine and derivatives thereof, indolin and its derivatives, Derivatives, azulene and derivatives thereof, azulenium and derivatives thereof, squarylium and derivatives thereof, porphyrin and derivatives thereof, porphyrazine and derivatives thereof, triarylmethane and derivatives thereof, phthalocyanine and derivatives thereof, acridones and derivatives thereof , Coumarin and its derivatives, ketocoumarin and its derivatives, quinolinone and its derivatives, benzooxazole and its derivatives, acridine and its derivatives, thiazine and its derivatives, benzothiazole and its derivatives, phenothiazine 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, Coronene and derivatives thereof, and the like.

It is also preferable that the radiation sensitive sensitizer includes a carbonyl compound. The carbonyl compound preferably includes a ketone, an aldehyde, a carboxylic acid, an ester, an amide, an enone, a carboxylic acid chloride, or a carboxylic acid anhydride as a carbonyl group. Examples of the carbonyl compound include benzophenone derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, acridone derivatives, and the like. In addition, the carbonyl compound may be a naphthalene derivative, an anthracene derivative, or an acridone derivative.

Further, it is preferable that at least one hydrogen atom in the aromatic ring of the radiation sensitive sensitizer is substituted by an electron hole. Since the hydrogen atoms are substituted by electron holes, the electron transfer efficiency by the sensitization reaction in the later-described batch exposure step is improved, and the sensitivity of the chemically amplified resist material tends to be improved. The difference between the absorption wavelength of the radiation absorbable by (a) the radiation-sensitive acid-sensitizer generator and (b) the radiation-sensitive sensitizer generator and the absorption wavelength of the radiation absorbable by the radiation- So that the radiation-sensitive sensitizer can be excited more selectively in the batch exposure process. As a result, the contrast of the latent image of the acid in the chemically amplified resist material is further improved. Examples of the electron donor include a hydroxyl group, a methoxy group, an alkoxy group, an amino group, an alkylamino group, and an alkyl group.

Examples of the radiation sensitive sensitizer include acetophenone, 2,2-dimethoxy-2-phenylacetophenone, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 1,2- Methyl-1-phenylpropan-1-one, -hydroxycyclohexyl phenyl ketone, 2-hydroxy-2- 2-methyl-1 - [(2-hydroxyethoxy) phenyl] propanone, 2-hydroxy- Benzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, Benzoyl-4'-methyldiphenylsulfide, benzophenonetetracarboxylic acid or its tetramethyl ester, 4,4'-bis (dimethylamino) benzoate, Phenone, 4,4'-bis (dicyclohexylamino) benzophenone, 4,4'- (Diethylamino) benzophenone, 4,4'-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 4,4'-dimethoxybenzophenone, 4- Benzyl anthraquinone, 2-t-butyl anthraquinone, 2-methylanthraquinone, phenanthraquinone, fluorenone, 2-benzyl-2-dimethylamino-1- ( (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2 - [ Methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-hydroxy- , Benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin phenyl ether, benzyl dimethyl ketal, acridone, chloroacridone, N Methyl acridone, N-butyl acridone, N-butyl-chloroacridone, 2,4,6- Dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, 2 < RTI ID = 0.0 > Tetramethylbenzoyldiphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2, 3-dichlorobenzoyl) phenylphosphine oxide, 4,6-trimethylbenzoylethoxyphenylphosphine oxide, Bis (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphtho Bis (2,6-dimethoxybenzoyl) phenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- Dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4,6-trimethylbenzoyl) phenylphosphine oxide, (2,5,6-trimethylbenzoyl) -2,4,4 - trimethylpentylphosphinoxa 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- propanedioxanthone, benzoyl 2- (O-benzoyloxime), 1- [9-ethyl-6 (phenylthio) phenyl] -9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] (O-acetyloxime), 1- [4- (phenylthio) phenyl] -3-cyclopentylpropane- Benzoyloxime), 2,2-dimethoxy-1,2-diphenylethan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy- 2-methyl-propan-1-one, phenyl (2-hydroxy-2-methyl-propionyl) (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino- )-part (O-benzoyloxime), 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbaldehyde 3-yl] ethanone 1- (O-acetyloxime) and the like.

((c) a radiation-sensitive acid generator)

(c) a radiation-sensitive acid generator is a component which generates an acid upon irradiation of a first radiation and which does not substantially generate the acid when only the second radiation is irradiated without irradiating the first radiation, (a) Sensitive radiation-sensitive acid-sensitizer generators.

(c) Examples of the radiation-sensitive acid generator include an onium salt compound, an N-sulfonyloxyimide compound, a sulfonimide compound, a halogen-containing compound, and a diazoketone compound.

Examples of the onium salt compound include a sulfonium salt, a tetrahydrothiophenium salt, an iodonium salt, a phosphonium salt, a diazonium salt, and a pyridinium salt.

(c) Specific examples of the radiation-sensitive acid generator include, for example, compounds described in paragraphs [0080] to [0113] of JP-A No. 2009-134088.

As the (c) radiation-sensitive acid generator, an acid generator represented by the following formula (c) is preferable. (c) The radiation-sensitive acid generator has the following structure, whereby the acid resist film (hereinafter referred to as " resist film " It is considered that the diffusion length in the chemically amplified resist material is more appropriately shortened. As a result, the performance such as the depth of focus of the chemically amplified resist material is improved.

In the formula (c), R ^p1 is a monovalent group containing a ring structure having a reducing number of 6 or more. R ^p2 is a divalent linking group. R ^p3 and R ^p4 each independently represent 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 of 1 to 20 carbon atoms. n ^p1 is an integer of 0 to 10; n ^p2 is an integer of 0 to 10; and n ^p3 is an integer of 1 to 10. When n ^p1 is 2 or more, plural R ^p2 may be the same or different. When n ^p2 is 2 or more, a plurality of R ^p3 may be the same or different, and a plurality of R ^p4 may be the same or different. When n ^p3 is 2 or more, a plurality of R ^p5 may be the same or different, and a plurality of R ^p6 may be the same or different. X ^{< + &} gt ^; is a monovalent, radiosensitive onium cation.

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

As the alicyclic structure of the reduced water 6 or more, for example,

A monocyclic cycloalkane structure 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 a cyclohexene structure, a cycloheptene structure, a cyclooctene structure, and a cyclodecene structure;

A polycyclic cycloalkane structure such as a norbornane structure, an adamantane structure, a tricyclodecane structure, and a tetracyclododecane structure;

A cycloalkene structure of a polycyclic structure such as a norbornene structure and a tricyclodecene structure, and the like.

As the aliphatic heterocyclic structure of the reduced water 6 or more, for example,

Lactone structures such as a hexanolactone structure and a norbornane lactone structure;

A sultone structure such as a hexanosultone structure and a norbornanesultone structure;

An oxocycloheptane structure, and an oxanorbornane structure;

A nitrogen atom-containing heterocyclic structure such as an azacyclohexane structure and a diazabicyclooctane structure; A thiocyclohexane structure, and a thionorbornane structure, and the like.

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

Examples of the aromatic heterocyclic structure of the above-mentioned reduced water 6 include an oxygen atom-containing heterocyclic structure such as a pyran structure and a benzopyran structure, a nitrogen atom-containing heterocyclic structure such as a pyridine structure, a pyrimidine structure, and an indole structure .

The lower limit of the reduced water of the cyclic structure of R ^p1 is preferably 7, more preferably 8, further preferably 9, and particularly preferably 10. On the other hand, the upper limit of the reduced water is preferably 15, more preferably 14, even more preferably 13, and particularly preferably 12. By setting the reduced water to the above range, the above-described acid diffusion length can be appropriately shortened, and as a result, various performances of the chemically amplified resist material can be further improved.

Some or all of the hydrogen atoms of the cyclic structure of R ^p1 may be substituted with a substituent. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxycarbonyl group, an alkoxycarbonyloxy group, Time and so on. Among them, a hydroxy group is preferable.

The R ^p1 is preferably a monovalent group containing an alicyclic structure having 6 or more alicyclic structures and a monovalent group containing an aliphatic heterocyclic structure having 6 or more alicyclic groups, A monovalent group containing a heterocyclic structure is more preferable, and an adamantyl group, a hydroxyadamantyl group, a norbornanactone-yl group, a norbornane sultone-yl group and 5-oxo-4-oxatricyclo [4.3.1.1 ^{3, 8]} undecane-group and the more preferred, and 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, and a carbonyloxy group and a norborn A norbornyl group is more preferable, and a carbonyloxy group is particularly preferable.

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. As R ^p3 and R ^p4 , a hydrogen atom, a fluorine atom and a fluorinated alkyl group are preferable, a fluorine atom and a perfluoroalkyl group are more preferable, and a fluorine atom and a trifluoromethyl group are more preferable.

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, more preferably a fluorine atom and a trifluoromethyl group, and particularly preferably a fluorine atom.

The n ^p1 is preferably an integer of 0 to 5, more preferably an integer of 0 to 3, still more preferably an integer of 0 to 2, and particularly preferably 0 and 1.

The n ^p2 is preferably an integer of 0 to 5, more preferably an integer of 0 to 2, more preferably 0 and 1, and particularly preferably 0.

As n ^p3 , an integer of 1 to 5 is preferable, an integer of 1 to 4 is more preferable, an integer of 1 to 3 is more preferable, and 1 and 2 are particularly preferable.

The monovalent radiation-sensitive onium cation represented by X ^< ⁺ > is a cation which is decomposed by irradiation with exposure light. In the exposure part, a proton produced by the decomposition of the photodegradable onium cation and a sulfonic acid are generated from the sulfonate anion. Examples of the monovalent radiation sensitive onium cation represented by X ^< ⁺ > include a cation represented by the following formula (ca) (hereinafter also referred to as a " cation (ca) (Hereinafter also referred to as " cation (cb) "), and a cation represented by the following formula (cc)

In the formula (ca), R ^C3 , R ^C4 and R ^C5 each independently represent a substituted or unsubstituted, linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms , -OSO ₂ -R ^CC1, or -SO ₂ -R ^CC2 , or a ring structure formed by combining two or more of these groups. R ^CC1 and R ^CC2 each independently represent a substituted or unsubstituted straight or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted alicyclic hydrocarbon group having 5 to 25 carbon atoms, or a substituted or unsubstituted carbon group having 6 or more carbon atoms To 12 aromatic hydrocarbon groups. c1, c2 and c3 are each independently an integer of 0 to 5; When a plurality of R ^C3 to R ^C5 and R ^CC1 and R ^CC2 are respectively plural, plural R ^C3 to R ^C5 and R ^CC1 and R ^CC2 may be the same or different.

In the formula (cb), R ^C6 is a substituted or unsubstituted linear or branched alkyl group having 1 to 8 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 8 carbon atoms. and c4 is an integer of 0 to 7. When there are a plurality of R ^C6 , a plurality of R ^C6 may be the same or different, and a plurality of R ^C6 may represent a cyclic structure formed by being joined together. R ^C7 is a substituted or unsubstituted, linear or branched alkyl group having 1 to 7 carbon atoms or a substituted or unsubstituted aromatic hydrocarbon group having 6 or 7 carbon atoms. c5 is an integer of 0 to 6; When R ^C7 is plural, plural R ^C7 may be the same or different, and plural R ^C7 may represent a ring structure constituted by mutually joining together. n _c2 is an integer of 0 to 3; R ^C8 is a single bond or a divalent organic group having 1 to 20 carbon atoms. n _c1 is an integer of 0 to 2;

In the formula (cc), R ^C9 and R ^C10 each independently represent a substituted or unsubstituted, linear or branched alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 12 carbon atoms, -OSO _2- R ^CC3 or -SO ₂ -R ^CC4 , or a cyclic structure in which two or more of these groups are joined together. R ^CC3 and R ^CC4 each independently represent a substituted or unsubstituted, linear or branched alkyl group of 1 to 12 carbon atoms, a substituted or unsubstituted alicyclic hydrocarbon group of 5 to 25 carbon atoms, or a substituted or unsubstituted carbon group of 6 To 12 aromatic hydrocarbon groups. c6 and c7 are each independently an integer of 0 to 5; R ^C9 , R ^C10 , R ^CC3 and R ^CC4 may be the same or different when a plurality of R ^C9 , R ^C10 , R ^CC3 and R ^CC4 are respectively plural.

Examples of the unsubstituted straight-chain alkyl group represented by R ^C3 , R ^C4 , R ^C5 , R ^C6 , R ^C7 , R ^C9 and R ^C10 include methyl, ethyl, n-propyl, .

Examples of the unsubstituted branched alkyl group represented by R ^C3 , R ^C4 , R ^C5 , R ^C6 , R ^C7 , R ^C9 and R ^C10 include i-propyl group, i-butyl group, sec- butyl group and the like.

As the unsubstituted aromatic hydrocarbon group represented by R ^C3 , R ^C4 , R ^C5 , R ^C9 and R ^C10 , for example,

An aryl group such as a phenyl group, a tolyl group, a xylyl group, a mesityl group, or a naphthyl group;

And aralkyl groups such as a benzyl group and a phenethyl group.

Examples of the unsubstituted aromatic hydrocarbon group represented by R ^C6 and R ^C7 include a phenyl group, a tolyl group and a benzyl group.

Examples of the divalent organic group represented by R ^C8 include groups similar to those exemplified as a divalent organic group having 1 to 20 carbon atoms represented by R ^F5 and R ^F8 in the formula (f-2) .

Examples of the substituent which may replace the hydrogen atom of the alkyl group and the aromatic hydrocarbon group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, A carbonyl group, an alkoxycarbonyloxy group, an acyl group, an acyloxy group and the like. Of these, a halogen atom is preferable, and a fluorine atom is more preferable.

Wherein ^{R C3, R C4, R C5} , R C6, R C7, R C9 and R ^C10 as, unsubstituted linear or branched alkyl group, a fluorinated alkyl group, an unsubstituted monovalent aromatic hydrocarbon ring group, -OSO ₂ - R ^BB5 and -SO ₂ -R ^BB5 are preferable, a fluorinated alkyl group and an unsubstituted monovalent aromatic hydrocarbon group are more preferable, and a fluorinated alkyl group is more preferable. R ^BB5 is an unsubstituted monovalent alicyclic hydrocarbon group or an unsubstituted monovalent aromatic hydrocarbon group.

As c1, c2 and c3 in the formula (ca), an integer of 0 to 2 is preferable, and 0 and 1 are more preferable, and 0 is more preferable. The c4 in the formula (cb) is preferably an integer of 0 to 2, more preferably 0 and 1, and even more preferably 1. As c5, an integer of 0 to 2 is preferable, 0 and 1 are more preferable, and 0 is more preferable. As n _c2, 2 and 3 are preferable, and _d is more preferable. As n _c1, 0 and 1 are preferable, and 0 is more preferable. As c6 and c7 in the formula (cc), an integer of 0 to 2 is preferable, 0 and 1 are more preferable, and 0 is more preferable.

Examples of the X ^+, in these cations (ca) and cationic (cb) is preferable, and diphenyl iodonium cation, a triphenylsulfonium cation, a 1- [2- (4-cyclohexyl-phenyl-carbonyl) -2 propane -Tetrahydrothiophenium cation and 4-cyclohexylsulfonylphenyldiphenylsulfonium cation are more preferable.

Examples of the acid generator represented by the above formula (c) include compounds represented by the following formulas (c1) to (c17) (hereinafter also referred to as "compounds (c1) to (c17)") .

In the formulas (c1) to (c17), X < ^{+ &} gt ^; is a monovalent radiation sensitive onium cation.

(c5), (c14), (c15), (c16) and (c17) are preferably used as the acid- Is more preferable.

Further, (c) the radiation-sensitive acid generator may be a part of (1) the polymer constituting the polymer component. In this case, (c) the radiation-sensitive acid generator is present in such a form that a group excluding one hydrogen atom from the compound bonds to the polymer.

(c) When the radiation-sensitive acid generator is a component different from (1) the polymer component, the lower limit of the content of (c) the radiation-sensitive acid generator relative to 100 parts by mass of the polymer component is preferably 0.1 part by mass By mass, more preferably 1 part by mass, still more preferably 5 parts by mass, and particularly preferably 15 parts by mass. On the other hand, the upper limit of the content is preferably 50 parts by mass, more preferably 30 parts by mass.

(c) when the radiation-sensitive acid generator is part of the polymer constituting the polymer component, (1) the lower limit of the content ratio of the (c) radiation-sensitive acid generator to one mole of the polymer component is 0.001 More preferably 0.002 mol, and still more preferably 0.01 mol. On the other hand, the upper limit of the content is preferably 0.5 mol, more preferably 0.3 mol.

If the content or the content is smaller than the above lower limit, the sensitivity may be lowered. On the contrary, when the content or the content exceeds the upper limit, the resist film tends to be difficult to form, and the rectangularity of the cross-sectional shape of the resist pattern may deteriorate.

When the component (2) is a component different from (1) the polymer component, the lower limit of the content of the component (2) relative to the solid content of the chemically amplified resist material is preferably 5% by mass, more preferably 10% By mass, more preferably 15% by mass. On the other hand, the upper limit of the content is preferably 40% by mass, more preferably 30% by mass. By setting the content of the component (2) within the above range, the sensitivity and lithography performance of the chemically amplified resist material can be further improved. Here, "solid content" means a component other than the solvent of the chemically amplified resist material. The "content of component (2)" means the total content of components different from (1) the polymer component in component (2).

[Acid diffusion control agent]

An acid diffusion control agent, which is an optional component of the chemically amplified resist material, is a compound that captures acid and cation and functions as a quencher. The chemically amplified resist material contains the acid diffusion control agent, so that the excess acid generated in the resist film is neutralized, and the chemical contrast of the latent image of the acid between the pattern exposure portion and the pattern unexposed portion can be increased.

The acid diffusion control agent is divided into a compound having radiation reactivity and a compound having no radiation reactivity.

As the compound having no radiation reactivity, a basic compound is preferable. Examples of the basic compound include a hydroxide compound, a carboxylate compound, an amine compound, an imine compound, and an amide compound, and more specifically, a primary, secondary or tertiary aliphatic amine, an aromatic amine, A nitrogen-containing compound having a carboxyl group, a nitrogen-containing compound having a sulfonyl group, a nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen- Compounds, and imide compounds. Of these, nitrogen-containing compounds having a carbamate group are preferable.

In addition, the basic compound may be selected from the group consisting of Troger's base; Hindered amines such as diazabicyclo undecene (DBU) and diazabicyclononene (DBM); Tetrabutylammonium hydroxide (TBAH), tetrabutylammonium lactate, and the like.

Examples of the primary aliphatic amine include aliphatic amines such as ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, there may be mentioned tertiary amines such as tert-amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine and tetraethylenepentamine .

Examples of the secondary aliphatic amine include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di- N, N-dimethylmethylenediamine, N, N-dimethylmethylenediamine, N, N-dimethylmethylenediamine, N, N-dimethylmethylenediamine, 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- N, N ', N', N'-tetramethylethylenediamine, triethylamine, tricyclohexylamine, trihexylamine, trioctylamine, trinonylamine, tridecylamine, 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-ethyl aniline, N-propylaniline, N, N-dimethylaniline, 2-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N , Aniline derivatives such as N-dimethyltoluidine; Diphenyl (p-tolyl) amine; Methyl diphenylamine; Triphenylamine; Phenylenediamine; Naphthylamine; Diaminonaphthalene; Pyrrole derivatives such as pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole and 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; Furazan derivatives; Pyrrole derivatives such as pyrrole, 2-methyl-1-pyrene and the like; Pyrrolidine derivatives such as pyrrolidine, N-methylpyrrolidine, pyrrolidinone, and N-methylpyrrolidone; Imidazoline derivatives; Imidazolidine derivatives; (1-butylphenyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, Pyridine derivatives such as butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 4-pyrrolidinopyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine; Pyridazine derivatives; Pyrimidine derivatives; Pyrazine derivatives; Pyrazoline derivatives; Pyrazolidine derivatives; Piperidine derivatives; Piperazine derivatives; Morpholine derivatives; Indole derivatives; Isoindole derivatives; 1H-indazole derivatives; Indolin derivatives; Quinoline derivatives such as quinoline and 3-quinolinecarbonitrile; Isoquinoline derivatives; Cinnoline derivative; Quinazoline derivatives; Quinoxaline derivatives; Phthalazine derivatives; Purine derivatives; Pyridine derivatives; Carbazole derivatives; Phenanthridine derivatives; Acridine derivatives; Phenazine derivatives; 1,10-phenanthroline derivatives; Adenine derivatives; Adenosine derivatives; Guanine derivatives; Guanosine derivatives; Uracil derivatives; Pyridine derivatives and the like.

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

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

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, , Monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 1-butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethoxy) ethyl] piperazine, piperidine ethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- 2-propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxydilolidine, 3-quinuclidinol, 3- Pyrrolidine ethanol, 1-aziridine Ethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide and the like.

Examples of the nitrogen-containing compound having a carbamate group include N- (tert-butoxycarbonyl) -L-alanine, N- (tert-butoxycarbonyl) -L-alanine methyl ester, (S) (R) - (+) - 2- (tert-butoxycarbonylamino) -3-methyl-1-propanol Butanol, (R) - (+) - 2- (tert-butoxycarbonylamino) -3-phenylpropanol, (S) Phenylpropanol, (S) - (-) - 2- (tert-butoxycarbonylamino) -3-phenyl- Propanol, (R) - (+) - 2- (tert-butoxycarbonylamino) (Tert-butoxycarbonyl) -L-aspartic acid 4-benzyl ester, N- (tert-butoxycarbonyl) -O-benzyl-L- threonine, (S) - (-) - l- (tert-butoxycarbonyl) -2-tert- butyl-3-methyl-4-imidazolidinone, Methyl-4-imidazolidinone, N- (tert-butoxycarbonyl) -3-cyclohexyl-L-alanine methyl ester, N- (tert- Carbonyl) -L-cysteine methyl ester, N- (tert-butoxycarbonyl) ethanolamine, N- (tert-butoxycarbonylethylenediamine) N- (tert- butoxycarbonyl) -D-glucosamine , N- (tert-butoxycarbonyl) -L-glutamine, 1- (tert-butoxycarbonyl) imidazole, N- Isoxycarbonyl) -L-isoleucine methyl ester, N- (tert-butoxycarbonyl) -L-leucinol, N? - (tert-butoxycarbonyl) (Tert-butoxycarbonyl) -L-alanine, N- (tert-butoxycarbonyl) -L-phenylalanine, N- (tert (Tert-butoxycarbonyl) -L-proline, N- (tert-butoxycarbonyl) -L-phenylalanine methyl ester, N- Butoxycarbonyl) -L (S) - (-) - 1- (tert-butoxycarbonyl) -1H-pyrazole-1-carboxamidine, N- (R) - (+) - 1- (tert-butoxycarbonyl) -2-pyrrolidinemethanol, 1- (tert-butoxycarbonyl) -L-serine, N- (tert-butoxycarbonyl) -L-serine methyl ester, N (tert-butoxycarbonyl) (tert-butoxycarbonyl) -L-threonine, N- (tert-butoxycarbonyl) -p-toluenesulfonamide, N- , N- (tert-butoxycarbonyl) -L-tryptophan, N- (tert-butoxycarbonyl) -L-tyrosine, N- (tert-butoxycarbonyl) -L-valine, N- (tert-butoxycarbonyl) -L-valine methyl ester, N- - (3-hydroxypropyl) carbamate, tert-butyl N- (6-aminohexyl) carbamate, tert- Butyl-4-benzyl-1-piperazinecarboxylate, tert-butyl (1S, 4S) - (tert-butylcarbamate) (S) -2-thiabicyclo [2.2.1] heptane-2-carboxylate, tert-butyl N- (2,3- dihydroxypropyl) carbamate, - (-) - 4-formyl-2,2-dimethyl-3-oxazolidinecarboxylate, tert- butyl [R- (R * (3-hydroxyphenyl) -1-methylethyl] carbamate, tert-butyl-4-oxo-1-piperidinecarboxylate, tert- Pyrrolidine carboxylate, and tert-butyl (tetrahydro-2-oxo-3-pranyl) carbamate.

Examples of the amide compound include amides such as formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, Cyclohexylpyrrolidone, and the like.

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

In addition, the above-mentioned radiation-reactive compound is divided into a compound (radiation decomposition type compound) which is decomposed by radiation and loses acid diffusion control ability and a compound which is produced by radiation and obtains an acid diffusion control ability (radiation generation type compound).

The radiation-decomposable compound is decomposed only in the pattern exposure portion in the pattern exposure process described later, so that the action of capturing the acid and the cation is deteriorated in the pattern exposure portion, and the action of capturing the acid and the cation is retained in the pattern non-exposure portion. As a result, the chemical contrast of the latent image of the acid between the exposed portion and the non-exposed portion can be improved.

The radiation-decomposable compound is preferably a sulfonate or a carboxylate of a radiation-decomposable cation. The sulfonic acid in the sulfonic acid salt is preferably a weak acid, more preferably a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group does not contain fluorine. Examples of such sulfonic acids include sulfonic acids such as alkylsulfonic acid, benzenesulfonic acid, and 10-camphorsulfonic acid. The carboxylic acid in the carboxylic acid salt is preferably a weak acid, and 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, cyclohexylcarboxylic acid, benzoic acid and salicylic acid. The radiation-decomposable cation in the carboxylate of the radiation-decomposable cation is preferably an onium cation, and examples of the onium cation include an iodonium cation and a sulfonium cation.

The radiation-generating compound is generated only in the pattern exposure portion in the pattern exposure process, so that the action of capturing the acid and the cation occurs in the pattern exposure portion and does not occur in the pattern non-exposure portion.

The radiation-generating compound may not be generated in the pattern exposure process, but may be generated in a later-described batch exposure process. In this case, in the exposure unit of the pattern exposure process, the radiation-sensitive sensitizer can be efficiently generated, and unnecessary acids and cations in the unexposed area of the batch exposure process can be captured.

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

Examples of the radiation-sensitive base generator include those disclosed in JP-A Nos. 4-151156, 4-162040, 5-197148, 5-5995, 6-194834, 8- 146608, 10-83079 and European Patent 622682, all of which are incorporated herein by reference.

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 carbamoyloxyimino group , And a compound containing a carbamate group (urethane bond), a compound containing an acyloxyimino group, and an ionic compound (anion-cation complex) are preferable.

The above-described radiation-sensitive base generator is preferably a compound having a ring structure in the molecule. Examples of the ring structure include a benzene structure, a naphthalene structure, an anthracene structure, a xanthone structure, a thioxanthone structure, an anthraquinone structure, and a fluorene structure.

Examples of the radiation-sensitive base generator include 2-nitrobenzylcarbamate, 2,5-dinitrobenzylcyclohexylcarbamate, N-cyclohexyl-4-methylphenylsulfonamide, 1,1- 2-phenylethyl-N-isopropylcarbamate, and the like.

The acid diffusion control agent may be a compound (heat generation type compound) which is produced by a thermal reaction and obtains acid diffusion control ability. In this case, it is preferable to be generated in the baking step after the batch exposure step described later. Thus, from the viewpoint of obtaining the acid diffusion control ability of the acid diffusion control agent in the baking step, it is preferable that the heating temperature in the baking step is higher than the heating temperature in the other steps.

When the chemical amplification type resist material contains the acid diffusion control agent, the lower limit of the content of the acid diffusion controller in (1) the 100 parts by mass of the polymer component is preferably 0.1 part by mass, more preferably 1 part by mass, 4 parts by mass is more preferable. On the other hand, the upper limit of the content is preferably 20 parts by mass, more preferably 10 parts by mass. When the content is smaller than the lower limit, there is a fear that the acid diffusion control agent can not sufficiently capture acid and cation. Conversely, when the content exceeds the upper limit, the sensitivity may be excessively lowered.

[Radical Picking Agent]

The radical scavenger is to capture free radicals. Since the chemically amplified resist material contains the radical scavenger, generation of the radiation-sensitive sensitizer through the radical-induced reaction in the pattern unexposed area is reduced, and the pattern exposure unit and the non- The contrast of the acid concentration can be further improved. Examples of the radical scavenger include compounds such as phenol compounds, quinone compounds, and amine compounds, and antioxidants derived from natural materials such as rubber.

[Crosslinking agent]

The cross-linking agent is a compound having two or more functional groups. In the baking step after the batch exposure step described later, the acid catalyst reaction causes (1) a cross-linking reaction in the polymer component to (1) increase the molecular weight of the polymer component , And the solubility of the pattern exposure unit in a developing solution is lowered. Examples of the functional group include a (meth) acryloyl group, a hydroxymethyl group, an alkoxymethyl group, an epoxy group, and a vinyl ether group.

[Other additives]

Examples of the other additives include surfactants, antioxidants, dissolution inhibitors, plasticizers, stabilizers, colorants, antireflection agents, and dyes. As these additives, known ones can be used.

[menstruum]

Examples of the solvent include an alcohol-based solvent, an ether-based solvent, a ketone-based solvent, an amide-based solvent, an ester-based solvent and a hydrocarbon-based solvent.

Examples of the alcohol solvent include alcohols such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, sec-butanol, Butanol, sec-pentanol, tert-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, Octanol, sec-octanol, n-nonyl alcohol, 2,6-dimethyl-4-heptanol, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl Monoalcohol solvents such as alcohol, sec-heptadecyl alcohol, furfuryl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol and diacetone alcohol;

Propylene glycol, 1,3-butylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,5-hexanediol, 2,4- Polyhydric alcohol solvents such as 2-ethyl-1,3-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol and tripropylene glycol;

Ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol monophenyl ether, ethylene glycol mono-2-ethylbutyl ether, diethylene glycol mono Methyl ethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene Glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monopropyl ether; and the like.

Examples of the ether solvent include dialkyl ether solvents such as diethyl ether, dipropyl ether and dibutyl ether;

Cyclic ether solvents such as tetrahydrofuran and tetrahydropyran;

Containing ether solvents such as diphenyl ether and anisole, and the like.

Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl iso butyl ketone, Chain ketone solvents such as ketone, methyl-n-hexyl ketone, di-iso-butyl ketone, and trimethyl nonanone;

Cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone and methylcyclohexanone;

2,4-pentanedione, acetonyl acetone, acetophenone, and the like.

Examples of the amide solvent include cyclic amide solvents such as N, N'-dimethylimidazolidinone and N-methylpyrrolidone;

A chain amide type such as N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, Solvents, and the like.

Examples of the ester solvents include methyl acetate, ethyl acetate, n-propyl acetate, isopropyl propyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, n-pentyl acetate, Propyl acetate, sec-pentyl acetate, 3-methylbutyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, Acetic acid ester solvents such as acetone and the like;

Ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, Polyhydric alcohol partial ether acetate type solvents such as monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate and dipropylene glycol monoethyl ether acetate;

lactone type solvents such as? -butyrolactone and valerolactone;

Carbonate solvents such as diethyl carbonate, ethylene carbonate and propylene carbonate;

Butyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl lactate, ethyl lactate, n-butyl lactate, n-butyl acetate, n-butyl acetate, isoamyl propionate, diethyl oxalate, -Butyl, n-amyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate.

Examples of the hydrocarbon solvent include hydrocarbon solvents such as n-pentane, iso-pentane, n-hexane, isohexane, n-heptane, iso-heptane, 2,2,4-trimethylpentane, Aliphatic hydrocarbon solvents such as cyclohexane and methylcyclohexane;

Benzene, toluene, xylene, mesitylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, di- And aromatic hydrocarbon solvents such as amylnaphthalene.

Among them, ester solvents and ketone solvents are preferable, and polyhydric alcohol partial ether acetate solvents, lactone solvents, cyclic ketone solvents, ethyl lactate and partial polyether alcohol ether acetates solvents are more preferable, and propylene Glycol monomethyl ether acetate,? -Butyrolactone, cyclohexanone, ethyl lactate and propylene glycol monomethyl ether acetate are more preferable. The chemical amplification type resist material may contain the above solvents in a single kind or in a mixture of two or more kinds.

[Method of producing chemically amplified resist material]

Such a chemically amplified resist material can be produced, for example, by mixing (1) a polymer component, (2) component and optionally other optional components in a predetermined ratio. After mixing, the chemically amplified resist material is preferably filtered, for example, with a filter having a pore diameter of about 0.2 탆. The lower limit of the solid 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 solid content concentration is usually 50 mass%, preferably 20 mass%, more preferably 5 mass%.

<Method of Forming Resist Pattern>

The resist pattern forming method includes: a coating step of coating the chemically amplified resist material on at least one surface of a substrate; a pattern exposure step of irradiating the resist film obtained by the coating with the first radiation; A baking step of heating the resist film after the batch exposure step; and a developing step of bringing the resist film after the baking step into contact with a developing solution.

The resist pattern forming method may further include a step of forming an organic underlayer film on a surface side of coating the chemically amplified resist material on the substrate before the coating step. The organic underlayer film forming step and the coating step A step of forming a silicon-containing film on the side of coating the chemically amplified resist material of the organic underlayer film.

The resist pattern forming method may further include a step of baking the resist film after the pattern exposure step (hereinafter also referred to as "pre-exposure baking step") before the batch exposure step.

Usually, a step of forming a pattern on the substrate is performed using the resist pattern formed by the resist pattern forming method as a mask after the above-described development step.

[Organic underlayer film forming process]

In the organic lower layer film formation step, an organic underlayer film is formed on the substrate. Here, the &quot; organic undercoat film &quot; means a film containing an organic substance as a main component.

Examples of the substrate include silicon wafers, silicon dioxide, wafers coated with aluminum, glass substrates, and ITO substrates.

Examples of the organic material include phenol resin, acenaphthylene resin, and the like. Herein, the term "acenaphthylene resin" means a resin having a structural unit derived from a compound containing an acenaphthylene skeleton.

Examples of the organic underlying film include a film for improving the adhesion between the resist film and the substrate, a film for improving the shape of the resist pattern, and an antireflection film for reducing the reflection of the radiation by the substrate. According to the anti-reflection film, it is possible to suppress the generation of standing waves due to the reflection of the radiation on the substrate or the like in the pattern exposure process. As the antireflection film, a known antireflection film can be used.

Further, it is preferable that the organic underlying film does not absorb the second radiation in the batch exposure process. In the case where the organic underlayer film absorbs the second radiation in the batch exposure process, there is a fear that a radiation increase / decrease reaction occurs in the resist film due to energy transfer or electron transfer from the organic underlayer film, and acid is generated in the pattern unexposed area. Therefore, it is preferable to form a buffer layer between the resist film and the organic under layer film so as not to carry out the radiation sensitization reaction, thereby preventing the increase or decrease of the radiation absorbing underlayer film. The buffer layer may be, for example, a transparent film that does not absorb the second radiation.

[Silicon-containing film forming process]

The silicon-containing film forming process further forms a silicon-containing film between the organic underlayer film and the resist film. Examples of the silicon-containing film include SOG (spin on glass) films used in a multilayer resist process. As the composition for forming the SOG film, known ones can be used. In addition, well known ones can be suitably applied to the conditions for forming the SOG film.

[Coating process]

In the coating step, the chemically amplified resist material is coated on at least one surface of the substrate to form a resist film. This resist film is directly formed on the surface of the substrate in the case where the organic under layer film forming step and the silicon containing film forming step are not performed and is formed on the surface of the silicon containing film in the case of performing the organic under layer film forming step and the silicon containing film forming step do.

Examples of the coating method of the chemically amplified resist material include spin coating (spin coating), flex coating, roll coating and the like.

After the chemical amplification type resist material is coated on the substrate, it may be subjected to prebaking (PB) for volatilizing the solvent in the coating film, if necessary. The lower limit of the PB temperature is usually 60 占 폚, preferably 80 占 폚. On the other hand, the upper limit of the PB temperature is usually 140 占 폚, preferably 120 占 폚. The lower limit of the PB time is usually 5 seconds, preferably 10 seconds. On the other hand, the upper limit of the PB time is usually 600 seconds, preferably 300 seconds.

The lower limit of the average thickness of the formed resist film is preferably 10 nm. On the other hand, the upper limit of the average thickness is preferably 1,000 nm, more preferably 500 nm.

Further, a protective film may be further formed on the resist film. By forming a protective film, it is possible to suppress the deactivation of the radiation-sensitive sensitizer, the acid, and the reaction intermediate produced in the pattern exposure process, thereby improving the process stability.

When the chemically amplified resist material does not contain a water repellent polymer additive such as a polymer having a high content of fluorine atoms and is subjected to liquid immersion lithography in a pattern exposure process to be described later in order to avoid direct contact between the immersion liquid and the resist film, A protective film for immersion immersion insoluble in the immersion liquid may be formed on the resist film. Examples of the protective film for immersion include a solvent peelable protective film (see, for example, Japanese Unexamined Patent Publication (Kokai) No. 2006-227632) which is peeled off by a solvent, a developer peelable protective film WO2005-069076 and WO2006-035790). From the viewpoint of throughput, a protective film for liquid immersion immersion is preferable.

[Pattern exposure process]

In the pattern exposure step, at least a part of the resist film obtained by coating is irradiated with the first radiation. Specifically, a light shielding mask of a predetermined pattern is disposed on the resist film obtained by the coating process. Thereafter, the resist film is irradiated with the first radiation through the mask using a projection lens, an electro-optical system mirror, or an exposure apparatus (radiation irradiation module) having a reflection mirror. As a result, a radiation-sensitive sensitizer and an acid are generated from the components (a) to (c) in the pattern exposure portion.

The first radiation to be irradiated in this process is radiation having a wavelength of 250 nm or less. Examples of such radiation include a gamma ray, an X-ray, an alpha ray, an intraviolet ray, a quantum ray, a beta ray, an ion beam, an electron beam, an EUV (extreme ultraviolet ray), an ArF excimer laser light (wavelength: 193 nm), a KrF excimer laser light And the like. Of these, electron beam, EUV, ArF excimer laser and KrF excimer laser are preferable, and electron beam and EUV are more preferable.

The pattern exposure process and / or the batch exposure process to be described later may be performed by liquid immersion lithography or dry lithography. In the case of performing the pattern exposure process and / or the batch exposure process by immersion exposure, examples of the immersion liquid to be used include water, fluorine-based inactive liquid, and the like. The liquid immersion liquid is transparent to the exposure wavelength and is preferably a liquid as small as possible of the temperature coefficient of refraction so as to minimize the distortion of the optical image projected onto the film. In particular, the exposure light source is ArF excimer laser light (wavelength 193 nm) In addition to the above-mentioned points, it is preferable to use water in terms of ease of acquisition and ease of handling. In the case of using water, it is possible to add additives for increasing the surface activity, in addition to decreasing the surface tension of water, in a small proportion. The additive preferably does not dissolve the resist film on the wafer and can neglect the influence of the lower surface of the lens on the optical coating. As the water, distilled water is preferable.

On the other hand, in the case of performing the pattern exposure process and / or the batch exposure process by dry lithography, the operation atmosphere may be any of an atmospheric pressure, a reduced pressure atmosphere, and an inert atmosphere, but may be a reduced pressure atmosphere, an inert atmosphere containing nitrogen, An inert atmosphere is preferred. The upper limit of the concentration of the basic compound inevitably incorporated in the atmosphere is preferably 20 ppb, more preferably 5 ppb, and further preferably 1 ppb.

Further, an absorbing film may be formed on the resist film after the pattern exposure process so as to absorb at least a part of the radiation of the wavelength capable of directly absorbing the radiation-sensitive acid generator in the component (a) or the component (c). By forming such an absorbing film, it is possible to further suppress the direct acid generation from the radiation-sensitive acid generator in the pattern unexposed area caused by the irradiation of the second radiation in the batch exposure step.

When the (b) radiation-sensitive sensitizer generator has an alcoholic hydroxyl group that is not substituted with a hydrogen atom, the resist film is exposed under a reduced pressure atmosphere in an inert atmosphere containing nitrogen during the period from the pattern exposure process to the batch exposure process It is preferable to store the solution in any one of an inert atmosphere containing argon. By placing the resist film under the atmosphere, exposure of oxygen to the resist film and stop of the radical reaction by the oxygen can be suppressed, and quenching of the acid by the trace amount of the basic compound can be suppressed. As a result, the process tends to be more stabilized. The upper limit of the storage time is preferably 30 minutes, more preferably 10 minutes. By reducing the storage time to the upper limit or lower, there is a tendency that the lowering of the sensitivity can be further suppressed.

On the other hand, when the (b) radiation-sensitive sensitizer generator has an alcoholic hydroxyl group substituted with a hydrogen atom, it is preferable that the resist film is stored in an air cleaned with an amine removal filter after the pattern exposure process to the batch exposure process. By placing the resist film under the above atmosphere, quenching of the acid by the trace amount of the basic compound can be suppressed, so that the process tends to be more stabilized. The upper limit of the storage time is preferably 30 minutes, more preferably 10 minutes. By reducing the storage time to the upper limit or lower, there is a tendency that the lowering of the sensitivity can be further suppressed.

[Bake process before collective exposure]

In the pre-exposure bake step, the resist film is heated after the pattern exposure step and before the batch exposure step. Thus, the generation of the radiation-sensitive sensitizer by the hydrolysis reaction of the (b) radiation-sensitive sensitizer generator and the like in the resist film can be promoted.

The lower limit of the heating temperature is preferably 30 占 폚, more preferably 50 占 폚, and further preferably 60 占 폚. On the other hand, the upper limit of the heating temperature is preferably 150 占 폚, more preferably 120 占 폚, and further preferably 100 占 폚. The lower limit of the heating time is preferably 5 seconds, more preferably 10 seconds. On the other hand, the upper limit of the heating time is preferably 3 minutes, more preferably 60 seconds. It is preferable that the heating is performed under an environment in which humidity is controlled. By heating under such an environment, (b) the hydrolysis reaction of moisture in the air when a hydrolysis reaction is used as a deprotection reaction for generating a radiation-sensitive sensitizer from a radiation-sensitive sensitizer generator, etc. Can be reduced.

[Bulk exposure process]

In the batch exposure step, a second radiation is applied to the entire surface of the resist film (the entire surface including the pattern exposure portion and the pattern unexposed portion) after the pattern exposure process. The second radiation may be irradiated onto the entire surface of the wafer at one time, or may be combined or overlapped with a plurality of localized irradiation.

In this step, only the radiation-sensitive sensitizer generated by the first radiation in the pattern exposure section in the resist film absorbs the second radiation, so that the second radiation is selectively absorbed in the pattern exposure section. Therefore, the acid can be continuously generated only in the pattern exposure section, and the sensitivity can be greatly improved. On the other hand, since the acid is not substantially generated in the pattern unexposed portion, the sensitivity can be improved while maintaining the chemical contrast in the resist film.

As the light source of the second radiation in this step, a general light source can be used. Examples of the second radiation include ultraviolet rays such as a mercury lamp or a xenon lamp having a desired wavelength by a band-pass filter or a cutoff filter, ultraviolet rays having a narrow band by an LED light source, a laser diode, or a laser light source.

The wavelength of the second radiation is more than 250 nm. The lower limit of the wavelength of the second radiation is preferably 280 nm, more preferably 300 nm. On the other hand, the upper limit of the wavelength is preferably 450 nm, and more preferably 400 nm. When the wavelength is smaller than the lower limit, there is a possibility that the amount of the acid or the radiation-sensitive sensitizer in the pattern unexposed portion due to the second radiation is increased. Conversely, when the wavelength exceeds the upper limit, the efficiency of the sensitization reaction by the second radiation may be lowered.

[Bake process]

In the baking step, the resist film after the batch exposure step is heated (post exposure bake (PEB)). As a result, dissociation of the acid-dissociable group of the [A] polymer or the like is accelerated by the acid generated from (c) a radiation-sensitive acid generator in the pattern exposure section. Further, when the chemically amplified resist material contains a cross-linking agent or the like, a cross-linking reaction occurs in the pattern exposure portion. As a result, a difference occurs in the solubility of the developer in the exposed portion and the non-exposed portion. In addition, there is a case where wave wrinkles occur on the sidewall of the resist due to the influence of the standing wave of the radiation in the resist film. However, the diffusion of the reactant in the resist film can be promoted by the PEB, It is possible to reduce wrinkles in the wrinkles.

The PEB atmosphere includes, for example, an inert atmosphere containing nitrogen, an inert atmosphere containing argon, and the like. The lower limit of the PEB temperature is usually 50 占 폚 and preferably 80 占 폚. On the other hand, the upper limit of the PEB time is usually 180 ° C and preferably 130 ° C. The lower limit of the PEB time is usually 5 seconds, preferably 10 seconds.

On the other hand, the upper limit of the PEB time is usually 600 seconds, preferably 300 seconds.

[Development process]

In the developing step, the resist film after the baking step is brought into contact with the developing solution. Thereby, the pattern exposure portion or the non-exposure portion is removed by the developer, and a predetermined resist pattern is formed. In the case of the alkali development, the pattern exposure portion is removed in the developing step, and a positive resist pattern is formed. On the other hand, in the case of organic solvent development, the pattern unexposed portion is developed in the developing process, and a negative resist pattern is formed. The negative resist pattern after development is generally washed with a rinsing liquid such as water or alcohol, and dried.

In the case of an alkali development, examples of the developing solution used in the above-mentioned development include, but are not limited to, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, Diazabicyclo- [5.4.0] - (2,2,2-trifluoroethyl) amine, triethylamine, methyldiethylamine, ethyldimethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), pyrrole, piperidine, Undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene, and the like can be given as an aqueous solution of an alkali in which at least one kind of alkaline compound is dissolved. Among them, a TMAH aqueous solution is preferable, a 2% by mass to 3% by mass aqueous solution of TMAH is more preferable, and a 2.38% by mass aqueous solution of TMAH is more preferable.

In the case of organic solvent development, the developing solution used in the above-mentioned development may be, for example, an organic solvent such as a hydrocarbon solvent, an ether solvent, an ester solvent, a ketone solvent or an alcohol solvent or a solvent containing an organic solvent . As the organic solvent, for example, solvents listed in the chemical amplification type resist material may be used singly or in combination of two or more kinds. Of these, ester-based solvents and ketone-based solvents are preferred. As the ester-based solvent, acetic ester-based solvents are preferable, and n-butyl acetate is more preferable. As the ketone solvent, a chain ketone is preferable, and 2-heptanone is more preferable. The lower limit of the content of the organic solvent in the developing solution is preferably 80% by mass, more preferably 90% by mass, still more preferably 95% by mass, and particularly preferably 99% by mass. Examples of components other than the organic solvent in the developer include water and silicone oil.

[Substrate Pattern Forming Step]

In the substrate pattern forming step, a pattern is formed on the substrate by using the resist pattern formed by the developing step as a mask and etching the substrate. This etching may be a dry etching in an atmosphere of a plasma excitation or the like, or a wet etching in which a substrate is immersed in a chemical liquid. After the pattern is formed on the substrate, the resist pattern is generally removed.

<Examples>

Hereinafter, the present invention will be described concretely with reference to examples, but the present invention is not limited to these examples. A method of measuring the physical property values in this embodiment is described below.

[Weight average molecular weight (Mw) and number average molecular weight (Mn)] [

The Mw and Mn of the polymer were measured by gel permeation chromatography (GPC). The measurement was carried out using a GPC column (two G2000HXL, one G3000HXL and one G4000HXL, one or more, manufactured by Sekisui Chemical Co., Ltd.) at a flow rate of 1.0 mL / min, a dissolution solvent tetrahydrofuran, a sample concentration of 1.0 mass%, a sample injection amount of 100 μL, ° C, a differential refractometer was used as a detector, and monodisperse polystyrene was used as a standard material.

[ ¹³ C-NMR analysis]

¹³ C-NMR analysis for determining the content of the structural unit of the polymer is a nuclear magnetic resonance apparatus (Nippon Den "JNM-ECX400" topical) use, and, using CDCl ₃ as a measuring solvent with tetramethylsilane (TMS) an As an internal standard.

&Lt; (1) Synthesis of polymer component >

(1) Monomers used in the synthesis of the polymer component are shown below.

[Synthesis Example 1] (Synthesis of polymer (S-1)

45 g (50 mol%) of the compound (M-1), 55 g (50 mol%) of the compound (M-2) and 3 g (3 mol% based on the total amount of the monomers) of azobisisobutyronitrile After dissolving in 300 g of ethyl ketone, the reaction temperature was maintained at 78 캜 under a nitrogen atmosphere and polymerization was carried out for 6 hours. After the polymerization, the reaction solution was added dropwise to 2,000 g of methanol, and the polymer was solidified. Subsequently, this polymer was washed twice with 300 g of methanol, and the resulting white powder was filtered and dried overnight at 50 캜 under reduced pressure to obtain a polymer (S-1) as a polymer component. The polymer (S-1) had Mw of 7,000 and Mw / Mn of 2.10. As a result of ¹³ C-NMR analysis, the content ratio of the respective structural units derived from the compound (M-1) and the compound (M-2) was 52 mol% and 48 mol%, respectively.

[Synthesis Example 2] (Synthesis of polymer (S-2)

(4 mol% based on the total amount of the monomers) and 1 g of t-dodecylmercaptan (the amount of the monomer (M-1)), 55 g (58 mol%) of the compound 1 mol% based on the total amount) was dissolved in 150 g of propylene glycol monomethyl ether, and polymerization was carried out for 16 hours while maintaining the reaction temperature at 70 캜 in a nitrogen atmosphere. After the polymerization, the reaction solution was added dropwise to 1,000 g of n-hexane, and the polymer was coagulated and purified. Subsequently, 150 g of propylene glycol monomethyl ether was further added to the polymer, and then 150 g of methanol, 37 g of triethylamine and 7 g of water were added, and hydrolysis was carried out for 8 hours while refluxing at the boiling point to obtain the compound (M -3) was deacetylated. After the reaction, the solvent and triethylamine were distilled off under reduced pressure, and the resulting polymer was dissolved in 150 g of acetone and then added dropwise to 2,000 g of water and solidified. The resulting white powder was filtered and dried overnight at 50 캜 under reduced pressure to obtain (1) a polymer (S-2) as a polymer component. This polymer (S-2) had Mw of 6,000 and Mw / Mn of 1.90. As a result of ¹³ C-NMR analysis, the content ratio of the structural unit derived from p-hydroxystyrene and the structural unit derived from the compound (M-1) was 50 mol% and 50 mol%, respectively.

[Synthesis Examples 3 and 4] (Synthesis of Polymers (S-3) and (S-4)

Polymers (S-3) and (S-4) as polymer components (1) were synthesized in the same manner as in Synthesis Example 2 except that monomers of the kind and amount shown in Table 1 were used. In Table 1, Mw, Mw / Mn and the content ratio of each structural unit determined by ¹³ C-NMR analysis are shown together.

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

[Synthesis Example 5] (Synthesis of compound (S-5)

10 g of glutaraldehyde (50 mass% aqueous solution), 24.8 g of 3-methoxyphenol and 37.5 g of trifluoroacetic acid were dissolved in 50 mL of chloroform and refluxed for 48 hours. This solution was added to methanol, and the precipitated precipitate was dried in vacuo to obtain 11.3 g of a monomolecular compound (M-8) represented by the following formula protected with a methoxy group. Then, 8.0 g of this compound (M-8), 8.2 g of potassium carbonate and 0.064 g of tetrabutylammonium bromide were dissolved in 95 mL of N-methylpyrrolidone (NMP) and stirred at 60 DEG C for 3 hours. To this reaction solution, a mixed solution of 4.3 g of 2-bromoacetyloxy-2-methyladamantane and 5 mL of NMP was added and stirred again at 60 DEG C for 48 hours. The reaction solution was poured into chloroform, washed with 0.1 M oxalic acid solution, dried over magnesium sulfate, filtered through celite, and the filtrate was concentrated under reduced pressure. (S-5) in which 18% of the hydroxyl groups of the compound (M-8) are protected with 2-acetyloxy-2-methyladamantane groups can be obtained by precipitating a solid by adding the concentrated solution to methanol, . This compound (S-5) corresponds to (1) a polymer component.

&Lt; Component (2) >

[(b) Synthesis of radiation-sensitive sensitizer generator]

[Synthesis Example 6] (Synthesis of compound (B-1)

2.4 g of 4,4'-dimethoxybenzophenone and 11.6 g of cis-1,2-cyclohexanediol were dissolved in 100 ml of toluene, 0.1 g of p-toluenesulfonic acid was added thereto, and the reaction solution was heated to 130 ° C The mixture was refluxed and reacted for 48 hours while removing by-product water by the Dean-Stark method. Subsequently, the reaction solution was concentrated under reduced pressure to remove toluene, and then, the compound (B-1) represented by the following formula was obtained in a yield of 50% by column chromatography using alumina gel.

[Synthesis Examples 7 to 11] (Synthesis of compounds (B-2) to (B-7)

(B-2) to (B-7) were synthesized in the same manner as in Synthesis Example 6 except that cis-1,2-cyclohexanediol was changed to the alcohol compound shown in Table 2.

[Synthesis Example 13] (Synthesis of Compound B-8)

2.4 g of 4,4'-dimethoxybenzophenone and 20 g of trimethyl orthoformate were dissolved in 100 ml of nitromethane, 0.1 g of p-toluenesulfonic acid was added thereto, and the reaction solution was reacted at 100 ° C for 12 hours. Subsequently, the reaction solution was concentrated under reduced pressure to remove the nitromethane, and then, by column chromatography using alumina gel, the compound (B-8) represented by the following formula was obtained in a yield of 72%.

[(b) Measurement of absorbance of the radiation-sensitive sensitizer generator]

(b) 4,4'-dimethoxybenzophenone, which is a sensitizer derived from the sensitizing radiation sensitizer generator and (b) the radiation sensitive sensitizer generator, were each prepared to be a cyclohexane solution of 0.0001% by mass. The absorbance of this production solution was measured using a spectrophotometer ("V-670" manufactured by Nihon Bunko Co., Ltd.) using cyclohexane as a reference solvent.

The absorbance was obtained by subtracting the absorbance of the reference solvent from the absorbance of the measurement solution at each wavelength of 250 nm to 600 nm. The measurement result of the absorbance is evaluated as &quot; transparent &quot; when the measured value of the absorbance is less than 0.01 in the whole wavelength range of the wavelength of 250 nm or more and 450 nm or less, and even if the wavelength at which the absorbance is 0.01 or more The case was evaluated as &quot; having absorbed &quot;. The evaluation results are shown in Table 3 below. Also, it was confirmed that the transmittance of cyclohexane, which is a solvent used for the measurement of the absorption analysis, was 95% or more in all wavelength regions of 250 nm to 600 nm.

((c) a radiation-sensitive acid generator)

As the (c) radiation-sensitive acid generator, a compound represented by the following formula (C-1) was used.

&Lt; Preparation of chemically amplified resist material >

The components other than the polymer component (1) and the component (2) used in the production of the chemically amplified resist material are described below.

(Acid diffusion control agent)

E-1: Triphenylsulfonium salicylate (compound represented by the following formula (E-1)):

E-2: 2,4,5-triphenylimidazole (compound represented by the following formula (E-2)

(solvent)

G-1: Propylene glycol monomethyl ether acetate

G-2: Ethyl lactate

G-3: Cyclohexanone

[Example 1] (Production of chemically amplified resist material (R-1)) [

(C-1) as a radiation-sensitive acid generator, (b) 100 parts by mass of (S-1) as a polymer component, , 2.5 parts by mass of (E-1) as an acid diffusion control agent, 4,300 parts by mass of (G-1) as a solvent and 1,900 parts by mass of (G-2) were mixed. The obtained mixed solution was filtered with a membrane filter having a pore diameter of 0.20 占 퐉 to prepare a chemically amplified resist material (R-1).

[Examples 2 to 5 and Comparative Examples 1 to 8] (Production of chemically amplified resist materials (R-2) to (R-13)

Each of the chemically amplified resist materials was produced in the same manner as in Example 1 except that each component of the kind and content shown in Table 4 was used. In addition, "-" in Table 4 indicates that the component is not added.

<Evaluation>

Resist patterns were formed on the chemically amplified resist materials of the Examples and Comparative Examples according to the procedures described below, and sensitivity and nano-edge roughness were evaluated.

[Formation of resist pattern]

The chemically amplified resist material (R-1) of Example 1 was spin-coated on a silicon wafer in "Clean Track ACT-8" manufactured by Tokyo Electron Co., Nm resist film was formed. Subsequently, the resist material film was irradiated with an electron beam using a simple electron beam drawing apparatus (&quot; HL800D &quot;, output: 50 KeV, current density 5.0 amperes / cm 2) manufactured by Hitachi Seisakusho Co., Ltd., and patterning was performed. In this patterning, a line-and-space pattern 1L1S including a line portion having a line width of 150 nm and a space portion having an interval of 150 nm formed by adjacent line portions was formed by using a mask. After the irradiation of the electron beam, the following operations (a) and (b) were carried out.

(Operation (a): No batch exposure)

After the irradiation of the electron beam, PEB was performed in the clean track ACT-8 under conditions of 110 DEG C and 60 seconds. Subsequently, the resist film was developed by a puddle method at 23 占 폚 for 1 minute using a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) in the clean track ACT-8. After development, a positive resist pattern was formed by washing with pure water and drying.

(Operation (b): with a batch exposure)

After the irradiation of the electron beam, the whole surface of the resist film was subjected to batch exposure for 30 minutes by using black light (Urban bar, wavelength: 320 nm). Subsequently, PEB was performed in the clean track ACT-8 under conditions of 110 DEG C and 60 seconds. Thereafter, development, washing with water and drying were carried out in the same manner as in the above operation (a) to form a positive resist pattern.

[Sensitivity]

An exposure amount for forming a line-and-space pattern 1L1S including a line portion having a line width of 150 nm and a space portion having an interval of 150 nm formed by adjacent line portions with a line width of 1: And the optimum exposure amount was used as an index of sensitivity. A (good) "when the optimum exposure amount was 35 μC / cm 2 or less, and" B (poor) "when the optimum exposure amount was 35 μC / Table 5 shows the measured 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 measuring apparatus ("S-9220" manufactured by Hitachi, Ltd.). The shape is observed at arbitrary 20 points of the line pattern, and the line portion 2 in the pattern formed on the base material (silicon wafer) 1, as shown in Figs. 1 and 2, Quot; CD &quot; between the line width at a portion where the concavities and convexities are most conspicuous along the lateral side 2a of the printed wiring board and the designed line width of 150 nm. The average value of ΔCD of 20 points was used as an index of nano edge roughness. A (good) "when the average value of ΔCD is 12.0 nm or less," AA (very good) ", 12.0 nm or more and 14.0 nm or less and" B (bad) "when the average value . The irregularities shown in Figs. 1 and 2 are exaggerated in actuality. The average value of? CD and the evaluation results of nano edge roughness are shown in Table 5.

As shown in Table 5, in the chemically amplified resist materials of Examples, both of the operation (a) as the conventional pattern formation method for performing only the pattern exposure and the operation (b) as the pattern formation method for further performing the batch exposure, The edge roughness was excellent. In the chemically amplified resist material of the embodiment, the sensitivity in the operation (b) is improved to a greater extent than the sensitivity in the operation (a), and the resist pattern can be suitably used for a pattern forming method for pattern exposure and batch exposure It was clear.

On the other hand, in the case of the chemically amplified resist materials of the comparative examples, (b) the sensitivity of the nano-edge roughness and the operation (a) were equivalent to those of the examples, the sensitivity in operation (b) was equivalent to the sensitivity in operation (a), and a significant improvement in sensitivity in operation (b) was not confirmed. The fact that the acetal protecting group does not satisfy the constitution of the present invention even when the chemical amplification type resist material of the comparative example contains (b) the radiation-sensitive sensitizer generating agent, indicates that the good sensitizing action itself in the operation (b) However, it has been found that the nano edge roughness deteriorates, or the effect of the increase and decrease in the operation (b) is limited.

As described above, according to the chemically amplified resist material and the resist pattern forming method of the present invention, radiation having a wavelength of 250 nm or less, such as EUV, electron beam, ion beam, KrF excimer laser beam, or ArF excimer laser beam, Both sensitivity and lithography performance in the case of using can be compatible at a high level. As a result, the chemically amplified resist material and the resist pattern forming method can be suitably used in a photoresist process in which the micropatterning is further advanced.

1: substrate
2: Resist pattern
2a: lateral side of the resist pattern

Claims (8)

(1) a polymer component which becomes soluble or insoluble in a developer by the action of an acid,
(2) a component that generates a sensitizing radiation sensitizer and an acid by exposure
/ RTI &gt;
Wherein the component (2) contains both of the following components (a) and (b), (b) and (c)
Wherein the component (b) comprises a compound represented by the following formula (B).
(a) irradiating a first radiation having a wavelength of not more than 250 nm and not irradiating a second radiation having a wavelength of more than 250 nm, the radiation and the radiation-sensitive composition for absorbing only the second radiation Sensitizer generator that does not substantially generate the acid and the radiation-sensitive sensitizer when irradiated with only the second radiation without irradiating the first radiation,
(b) generating a radiation-sensitive sensitizer for absorbing the second radiation when the first radiation is not irradiated and the second radiation is not irradiated, and only the second radiation A radiation-sensitive sensitizer generator which does not substantially generate the radiation-sensitive sensitizer
(c) irradiating the first radiation and generating the acid when it does not emit the second radiation, and substantially not generating the acid when only the second radiation is irradiated without irradiating the first radiation A radiation-sensitive acid generator

(In the formula (B), R ^B1 and R ^B2 each independently represent a monovalent organic group bonded through a carbon atom to a hydrogen atom, a halogen atom, an amino group, or a carbon atom to which R ^B3 O and R ^B4 O are bonded, groups are combined to each other, it represents a ring structure of the reduced water from 3 to 30 that is configured with the carbon atoms to which they are attached. R ^B3 and R ^B4 each independently, or a monovalent organic group having 1 to 20 carbon atoms, or combined with each other, they are attached are At least one of R ^B3 and R ^B4 is a halogen atom, a nitro group, a cyano group, a formyl group, a carbonyl group, a carboxyl group, a sulfo group, a sulfonyl group or a , Or the ring structure of the reduced water 4 to 30 is a spiro ring structure, a condensed ring structure, or a branched (bridged) structure) The compound according to claim 1, wherein R in the formula (B)^B1 And R^B2Each independently represent a hydrogen atom, a halogen atom, an amino group, 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 amide group, an unsaturated hydrocarbon group having 1 to 30 carbon atoms, or a carbonyl group bonded with an alkyl group having 1 to 12 carbon atoms, or the phenyl group, the naphthyl group, the anthracenyl group, the alkoxy group, the alkylthio group, A naphthoxy group, an anthracene oxy group, or a group in which at least a part of the hydrogen atoms of the unsaturated hydrocarbon group is substituted,₂-, -O-, -S-, -SO₂-, -SO₂NH-, -C (= O) -, -C (= O) O-, -NHCO-, -NHC^g-, -CR^g ₂-, -NH- and -NR^g- &Lt; / RTI &gt;^gIs a phenyl group; Phenoxy group; A halogen atom; A linear, branched or cyclic saturated or unsaturated hydrocarbon group of 1 to 30 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, branched or cyclic saturated or unsaturated hydrocarbon group of 1 to 30 carbon atoms, an alkoxy group of 1 to 5 carbon atoms or a phenyl group substituted by a hydroxy group), R^B1 And R^B2Form a cyclic structure together with the carbon atoms to which the carbon atom is bonded. The chemically amplified resist composition according to claim 1 or 2, wherein the compound represented by the formula (B) is represented by the following formula (BI) or (B-II).

(R ^B1 and R ^B2 in the formula (BI) and the formula (B-II) are the same as those in the formula (B).
In the formula (BI), R ^X1 is a group having a monocyclic structure having 4 to 20 reduced numbers. R ^X2 is a group having a ring structure of 3 to 20 in reduced number.
In the formula (B-II), R ^Y1 is a group having a monocyclic structure having a reduced number of 5 to 20. R ^Y2 is a group having a ring structure of 3 to 20 in reduced number. and n is an integer of 0 to 3) The method according to any one of claims 1 to 3, wherein the (1) polymer component comprises a first polymer having a structural unit comprising a group which generates a polar group by dissociation of an acid-dissociable group by the action of an acid Wherein the resist pattern is a resist pattern. The method of any one of claims 1 to 4, wherein the first polymer has a structural unit comprising a fluorine atom, or (1) the polymer component comprises a second polymer different from the first polymer And the second polymer has a structural unit containing a fluorine atom. 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 composition according to claim 6, wherein the content of the component (2) relative to the total solid content is 5% by mass or more and 40% by mass or less. A coating step of coating the chemically amplified resist material according to any one of claims 1 to 7 on at least one side of the substrate,
A pattern exposure step of irradiating the resist film obtained by the coating with the radiation having a wavelength of 250 nm or less,
A batch exposure step of irradiating the resist film after the pattern exposure step with radiation having a wavelength exceeding 250 nm;
A baking step of heating the resist film after the batch exposure step,
A developing step of bringing the resist film after the baking step into contact with a developing solution
To form a resist pattern.

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