KR20170054297A - Chemically amplified resist material and process for forming resist pattern - Google Patents

Abstract

Provided is a chemically amplified resist material capable of showing excellent lithography performance while maintain good sensitivity. 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 a component (a), two random components among components (a)-(c), or all of the components (a)-(c). The component (a) or (c) includes a first compound having radiation sensitivity and a second compound having radiation sensitivity. The first compound includes a first onium cation and a first onium anion. The second compound includes a second onium cation and a second onium anion which is different from the first onium anion. Energy, emitted by the first and second onium cations when returned to a radical, is less than 5.0 eV.

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.

EUV (extreme ultraviolet light) lithography 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 light having a wavelength of 13.5 nm as exposure light. According to EUV lithography, it is demonstrated that a very fine pattern (for example, 20 nm or less) can be formed in an exposure process of a semiconductor device manufacturing process.

However, since the EUV light source developed at present is low in 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, even the resist material in the above-described technique has insufficient sensitivity to EUV light, and if the sensitivity to EUV light is improved, 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

SUMMARY OF THE INVENTION The present invention has been made based on the above-described circumstances, and its object is to provide a method of irradiating a non-ionizing radiation having a wavelength of 250 nm or less, such as ionizing radiation such as EUV light, electron beam, ion beam, or KrF excimer laser and ArF excimer laser, A chemically amplified resist material capable of exhibiting excellent lithography performance while maintaining good sensitivity when used as light, and a resist pattern forming method using the chemically amplified resist material.

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) comprises any one of the following components (a), (a) to (c), or both of the following components (a) to (c) (hereinafter also referred to as "[C2] compound") having a radiation-sensitive property, and the component (c) has a radiation-sensitive first compound (hereinafter also referred to as a " (C1) compound comprises a first onium cation (hereinafter also referred to as "cation (I)") and a first anion (hereinafter also referred to as "anion (I)") (Hereinafter also referred to as " anion (II) ") which is different from the anion (I) And the energy released when the cation (I) and the cation (II) are reduced to radicals is less than 5.0 eV.

(a) irradiating a first radiation, which is radiation having a wavelength of 250 nm or shorter, and not irradiating a second radiation, which is radiation having a wavelength exceeding 250 nm, Sensitizer generator which generates a sensitizer and does not substantially generate the acid and the radiation-sensitive sensitizer when only the second radiation is irradiated without irradiating the first radiation,

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

(c) generating an acid when irradiating the first radiation and not irradiating the second radiation, and substantially when the second radiation is irradiated without irradiating the first radiation, Non-sensitizing radiation-sensitive acid generator

According to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising the steps of: forming a resist material film on at least one surface of a substrate using the chemically amplified resist material; irradiating the resist material film with radiation having a wavelength of 250 nm or less A batch exposure step of irradiating the resist material film after the pattern exposure step with radiation having a wavelength exceeding 250 nm; a baking step of heating the resist material film after the batch exposure step; And a developing step of bringing the resist material film after the baking step into contact with a developing solution.

Here, "the acid and the radiation-sensitive sensitizer do not substantially occur when only the second radiation is irradiated without irradiating the first radiation", "when the second radiation alone is not irradiated with the first radiation, Quot; does not substantially cause the growth sensitizer " and " does not substantially generate the acid when only the second radiation is irradiated without irradiating the first radiation " means that the irradiation with the second radiation Even when an acid or a radiation-sensitive sensitizer is generated by irradiation of the second radiation, the acid or the radiation sensitivity change between the exposed portion and the non-exposed portion in the pattern exposure for irradiating the first radiation In the pattern exposure by the second radiation to such an extent that the difference in the concentration of the sieve The amount of the acid or the radiation-sensitive sensitizer generated in the exposed area is small, and as a result, the amount of the acid or the amount of the radiation-sensitive sensitizer in the developing solution after the development is such that only one of the exposed part and non- Means less.

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

1 is a process diagram showing an embodiment of a resist pattern forming method using a chemically amplified resist material according to the present invention.
2 is a process drawing showing an example of a resist pattern forming method using a conventional chemically amplified resist material.
3 is a process diagram showing another embodiment of the resist pattern forming method using the chemically amplified resist material according to the present invention.
4 is a conceptual diagram showing the absorbance of the pattern exposure unit and the absorbance of the unexposed portion of the resist material film in a graph.
FIG. 5A is a conceptual diagram showing a graph of an acid concentration distribution by a resist pattern forming method using a conventional chemically amplified resist material. FIG. (b) is a conceptual diagram showing, as a graph, a radiation-sensitive sensitizer concentration distribution and an acid concentration distribution by a resist pattern forming method using the chemically amplified resist material according to the present embodiment.
FIG. 6 is a cross-sectional view for explaining an example of a manufacturing process of a semiconductor device according to an embodiment of the present invention, wherein (a) is a cross-sectional view showing a resist pattern forming step, (b) (c) is a cross-sectional view showing a resist pattern removing step.
7 is a schematic plan view showing the nano-edge roughness of the pattern.
8 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 developing solution by the action of an acid, (2) a component that generates a radiation-sensitive sensitizer and an acid by exposure, (A), any two of the following components (a) to (c), or both of the following components (a) to (c).

(a) irradiating a first radiation, which is radiation having a wavelength of 250 nm or shorter, and not irradiating a second radiation, which is radiation having a wavelength exceeding 250 nm, Sensitizer generator which 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 irradiating the first radiation and not irradiating the second radiation, and wherein only the second radiation is irradiated without irradiating the first radiation (C) a radiation-sensitive sensitizer generator which does not substantially generate the radiation-sensitive sensitizer when irradiated with the first radiation, and generates an acid when the second radiation is not radiated, and A radiation-sensitive acid generator which does not substantially generate the acid when irradiating only the second radiation without irradiating the first radiation

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) incorporated into a part of the polymer 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.

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

[(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 includes a structural unit (hereinafter also referred to as " structural unit (I) ") containing a group capable of generating a polar group by the action of an acid (Hereinafter, also referred to as " [A] polymer "). (1) The polymer component may further comprise a second polymer (hereinafter also referred to as " [B] polymer ") that does not contain a structural unit (I) having a polymer [A].

(A) a polymer or a [B] polymer is a polymer comprising a structural unit (hereinafter also referred to as a "structural unit (II)") containing a fluorine atom, 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 units (II) to (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 may have other structural units other than the structural unit (III), the structural unit (IV), the structural unit (III) to the structural unit (IV).

(Structural unit (I))

The structural unit (I) is a structural unit containing 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 each of which is taken 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 of 1 to 20 carbon atoms represented by R ^A2 , R ^A6 , R ^A7 and R ^A8 A group containing an oxygen atom between the carbon-carbon atoms of the exemplified 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 (I-1-d) 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-propyl-1-cyclopentyl (meth) acrylate, a structural unit derived from 2-cyclohexylpropan-2- 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 of the polymer [A] is preferably 10 mol%, more preferably 20 mol%, still more preferably 25 mol%, and 30 mol% Particularly preferred. 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 material 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. The heteroatom-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, have.

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 containing the phenolic hydroxyl group 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 represented by the following formulas (h-1) to (h-6) (hereinafter also referred to as "structural units (III-1) to (III-6)") .

In the formulas (h-1) to (h-6), 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 30 mol% , And 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.

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) is formed by polymerizing a monomer in which a hydrogen atom of -OH group of an aromatic ring containing a phenolic hydroxyl group is substituted with an acetyl group, and then hydrolyzing the obtained polymer in the presence of an amine And the like.

(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 . It is possible to improve adhesion between the resist material film formed from the chemically amplified resist material and the substrate. Here, the lactone structure means a structure having one ring (lactone ring) including a group represented by -OC (O) -. 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 of the structural unit (IV) relative to the total structural units constituting the polymer [A] is preferably 1 mol%, more preferably 10 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, adhesion between the resist material 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 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, adhesion between the resist material 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 70% by mass, more preferably 75% by mass, and most preferably 80% by mass, based on the total solid content of the chemically amplified resist material. Here, the term " total solid content " means a component other than the solvent 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 material film having sufficient heat resistance may not be obtained. On the other hand, when the Mw of the [A] polymer exceeds the upper limit, there is a fear that the developability of the resist material film is 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. 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] is not particularly limited, but its lower limit is preferably 1,000, more preferably 2,000, still more preferably 2,500, Particularly preferred. 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 material film having sufficient heat resistance may not be obtained. Conversely, when the Mw of the [B] polymer exceeds the upper limit, there is a fear that the developability of the resist material 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, the polymer having a high fluorine atom content can be made to be uniform in the surface layer of the resist material film to function as a water repellent polymer additive. As a result, the elution of the component (2) and the like from the resist material film can be suppressed, and the dynamic contact angle of the surface of the resist material 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, 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 and the like 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.

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

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

The (C1) compound and the cation (II) and the anion (II), which contain the cation (I) and the anion (I) C2) < / RTI > The anion (II) differs from the anion (I). That is, the above-mentioned (a) radiation-sensitive acid-sensitizer generator or (c) the radiation-sensitive acid generator has cation (I) and cation (II) as cations and anions (II). Cation (I) and cation (II) are onium cations, and when released into the radicals, all of the energy released is less than 5.0 eV. The (a) radiation-sensitive acid-sensitizer generator or (c) the radiation-sensitive acid generator may have one or more than one of the [C1] compound and the [C2] compound.

The compound having a smaller logarithm value (pKa) of the inverse number of the acid dissociation constant of the generated acid among the [C1] compound and the [C2] compound is preferably (1) an acid generating compound which makes the polymer component soluble or insoluble in a developer Function. And the compound having the larger pKa of the acid generated on the other side functions as an acid diffusion control agent.

(Cation)

Cation (I) and cation (II) are onium cations, and when released into the radicals, all of the energy released is less than 5.0 eV.

The chemically amplified resist material is a resist composition comprising (a) a radiation-sensitive acid-sensitizer generator or (c) a radiation-sensitive acid generator having a [C1] compound and a [C2] (II) is reduced to radicals, all of the energy emitted is less than 5.0 eV. Thus, when radiation having a wavelength of 250 nm or less, such as EUV light, is used as pattern exposure light, excellent lithography performance Can be exercised. 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, by setting all of the energy (a) released when the cation of the radiation sensitive acid-sensitizer generator or (c) the cation of the radiation sensitive acid generator is reduced to less than the specific value, It is considered that the lithographic performance can be improved while maintaining a good sensitivity by suppressing the decomposition in the pattern unexposed portion by controlling the photodegradability of the functioning compound to be appropriately low.

The upper limit of the energy released when the radicals of the cation (I) and the cation (II) are reduced is preferably 4.9 eV, more preferably 4.8 eV. The lower limit is preferably 4.0 eV, more preferably 4.2 eV.

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

The lower limit of the total content of the cation (I) and the cation (II) relative to the total onium cation in the chemically amplified resist material is preferably 80 mol%, more preferably 85 mol%, still more preferably 90 mol% Do. By setting the total content of the cation (I) and the cation (II) in the above range, the sensitivity and lithography performance of the chemically amplified resist material can be further improved.

The cation (I) and the cation (II) are, for example, monovalent onium cations represented by X ^< ^{+ &} gt ;. Examples of the monovalent onium cation represented by X ^< ⁺ > include a cation represented by the following formulas (X-1) and (X- Quot;).

As X ^{< + &} gt ;, a triphenylsulfonium cation is preferable.

(Anion)

The anion (I) and the anion (II) are different anions.

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

Examples of the anion (I) and the anion (II) include a sulfonic acid anion, a carboxylic acid anion, a bis (alkylsulfonyl) amide anion, and a tris (alkylsulfonyl) methide anion.

Among the anion (I) and the anion (II), the aliphatic acid value (pKa) of the acid dissociation constant of the generated acid is small and the anion functioning as an anion of the acid generating compound includes the following general formulas (XX), An anion of an acid represented by the general formula (XXII) is preferable, and an anion of an acid represented by the following general formula (XX) is more preferable.

In the above 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.

The compound represented by the following formula (1) is preferred as the compound which functions as the acid generating compound, in which the logarithm value (pKa) of the inverse number of the acid dissociation constant of the generated acid among the [C1] compound and the [C2] . That is, it is preferable that the anion of an acid of a compound functioning as an acid generating compound has a structure described in the following formula (1).

In the formula (1), R ^p1 is a monovalent group containing a ring structure 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 cation (I) and a cation (II).

Here, the "reduced water" means the number of atoms constituting an aromatic ring structure, an aromatic heterocyclic structure, an alicyclic structure and an aliphatic heterocyclic ring structure, and in the case of a polycyclic ring structure, it means. The "hydrocarbon group" includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. This " hydrocarbon group " may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. The term " chain hydrocarbon group " means a hydrocarbon group that does not contain a cyclic structure but consists of only a chain structure, and includes both a straight chain hydrocarbon group and a branched hydrocarbon group. The "alicyclic hydrocarbon group" means a hydrocarbon group containing only an alicyclic structure and not containing an aromatic ring structure, and includes both monocyclic alicyclic hydrocarbon groups and polycyclic alicyclic hydrocarbon groups. However, it need not be constituted only of the alicyclic structure, and a part thereof may contain a chain structure. The "aromatic hydrocarbon group" means a hydrocarbon group having an aromatic ring structure as a ring structure. However, it need not be constituted only of an aromatic ring structure, and a part thereof may contain a chain structure or an alicyclic structure.

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

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.

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

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, it is possible to shorten the diffusion length of the acid more appropriately, and as a result, the LWR performance and the like in the resist material of the present embodiment can be further improved.

Some or all of the hydrogen atoms of the ring structure of R ^p1 may be substituted with substituents. 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.

R ^p1 is preferably a monovalent group containing an alicyclic structure containing 6 or more alicyclic groups and a monovalent group containing an aliphatic heterocyclic structure containing 6 or more alicyclic groups, A monovalent group including a recurring 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-yl group is more preferable, and adamantyl group is particularly preferable.

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

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

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

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

The anion described in the above formula (1), which is preferable as an anion of an acid of a compound functioning as an acid generating compound, includes, for example, the following.

Examples of the [C1] compound and the [C2] compound include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium perfluoro-n-octane Triphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 6- (adamantan- Ylcarboxyoxy) -1,1,2,2-tetrafluorohexane-1-sulfonate, triphenylsulfoniumadamantane-1-yloxycarbonyl carboxylate, 4-methoxyphenyldiphenylsulfonium 1 , 2-di (cyclohexyloxycarbonyl) ethane-1-sulfonate, and the like.

The lower limit of the content of the [C1] compound and the [C2] compound relative to 100 parts by mass of the component (a) or the component (c) in the compound having a smaller pKa of the generated acid is preferably 50% by mass By mass, and more preferably 60% by mass. On the other hand, the upper limit of the content is preferably 90% by mass, more preferably 80% by mass. The lower limit of the content of the [C1] compound and the [C2] compound relative to 100 parts by mass of the component (a) or the component (c) in the compound having a larger pKa of the generated acid is preferably 5% By mass, and more preferably 10% by mass. On the other hand, the upper limit of the content is preferably 50% by mass, more preferably 40% by mass. By setting the content of the compound having a smaller pKa of the generated acid and the compound having the larger pKa in the above range, the sensitivity and lithography performance of the chemically amplified resist material can be further improved.

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

(a) when the radiation-sensitive acid-sensitizer generator is irradiated with a first radiation which is radiation having a wavelength of 250 nm or less and not irradiated with a second radiation which is radiation with a wavelength exceeding 250 nm, The acid and the radiation-sensitive sensitizer for absorbing the second radiation are generated, and the acid and the radiation-sensitive sensitizer are not substantially generated when only the second radiation is irradiated without irradiating the first radiation.

Examples of the [C1] compound and the [C2] compound as the (a) radiation-sensitive acid-sensitizer generator include, for example, the onium salt compounds of the above-mentioned [C1] compounds and [C2] compounds. Examples of the onium salt compound include a sulfonium salt compound and a tetrahydrothiophenium salt compound.

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

(a) The radiation-sensitive acid-sensitizer generator may also contain compounds other than the [C1] compounds and [C2] compounds, and other onium salt compounds, diazomethane compounds and sulfonimide compounds . Examples of the onium salt compounds include iodonium salt compounds. As the (a) radiation-sensitive acid-sensitizer generator other than the [C1] compound and the [C2] compound, an iodonium salt compound is 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 .

(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 generator is a component different from (1) the polymer component, (1) the lower limit of the amount of the radiation-sensitive acid-sensitizer generator 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 blending amount 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 blending amount or content ratio is smaller than the above lower limit, the sensitivity may be lowered. On the other hand, if the blending amount or the content ratio exceeds the upper limit, the resist material 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 generating agent is irradiated with the first radiation and generates a radiation-sensitive sensitizer for absorbing the second radiation when the second radiation is not emitted, Sensitizer is substantially free of the radiation-sensitive sensitizer when irradiated with only the second radiation without irradiating the radiation, and is different from the (a) radiation-sensitive acid-sensitizer generator.

In the chemically amplified resist material, the chemical structure of the radiation-sensitive sensitizer generator (b) is directly or indirectly converted by the irradiation of the first radiation, and the chemical structure of the radiation- Thereby generating a radiation-sensitive 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.

It is preferable that (b) the radiation-sensitive sensitizer generating agent is a carbonyl compound having a carbonyl group absorbing the second radiation upon irradiation with the first radiation. Examples of the carbonyl compound include aldehydes, ketones, carboxylic acids, and carboxylic acid esters. By this reaction, the peak shift of the absorption wavelength of radiation occurs only in the (b) radiation-sensitive sensitizer generator of the pattern exposure unit. Therefore, if the batch exposure is performed with the radiation of the wavelength capable of absorbing only the pattern exposure portion after the pattern exposure, only the pattern exposure portion can be selectively increased or decreased. As the (b) sensitizing radiation sensitizer generating agent, an alcohol compound represented by the following formula (VI) is more preferable, and it may be a secondary alcohol compound. In the present specification, the alcohol compound does not only mean a compound having an alcoholic hydroxyl group but also may be a ketal compound in which a hydrogen atom of an alcoholic hydroxyl group is substituted, an acetal compound, an orthoester compound or the like. (b) When the radiation-sensitive sensitizer generating agent is a ketal compound or acetal compound, it may be heated before the pattern exposure and after the batch exposure in order to accelerate the hydrolysis reaction of the carbonyl compound by the acid catalyst generated by the pattern exposure.

R ⁸ , R ⁹ and R ¹⁰ in the formula (VI) each independently represent a hydrogen atom; A phenyl group; Naphthyl group; Anthracenyl group; An alkoxy group having 1 to 5 carbon atoms; An alkylthio group having 1 to 5 carbon atoms; 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); 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 hydrocarbyl group An alkoxy group having 1 to 5 carbon atoms substituted by an actual group; 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 hydrocarbyl group An alkylthio group having 1 to 5 carbon atoms substituted by an actual group; A phenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, an amino group, an amide group, or an alkyl group having 1 to 5 carbon atoms; 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 hydrocarbyl group A phenyl group substituted by an actual 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 hydroxyl 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 hydroxyl group; An alkoxy group having 1 to 5 carbon atoms, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms) substituted with a phenoxy group, a naphthoxy group, an anthracenoxy group, an amino group, an amide group or a hydroxyl group A saturated or 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. The alcohol compound may be a thiol compound in which the alcoholic hydroxyl group (hydroxyl group) in the formula (VI) is a thiol group. In the formula (VI), the hydrogen atom of the hydroxyl group or thiol 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); Or a linear, branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group) having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms), an alkoxy group having 1 to 5 carbon atoms, And may be substituted with a phenyl group. In the formula, any two or more groups of R ⁸ , R ⁹ and R ¹⁰ may be replaced by a single bond or a double bond, or -CH ₂ -, -O-, -S-, -SO ₂ -, -SO ₂ NH-, -C (= O) -, -C (= O) O-, -NHCO-, -NHC (= O) NH-, -CHR g -, -CR g 2 -, -NH- or -NR ^g - a To form a ring structure. R ^g 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 hydroxyl group, or an alkyl group having 1 to 5 carbon atoms; Or a linear, branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group) having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms), an alkoxy group having 1 to 5 carbon atoms, Phenyl group. R ⁸ , R ⁹ and R ¹⁰ are each independently preferably a hydrogen atom; A phenyl group; Phenoxy group; A phenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or an alkyl group having 1 to 5 carbon atoms; Or an alkoxy group having 1 to 5 carbon atoms, or a phenyl group substituted with a hydroxyl group.

The ketal compound or acetal compound in which the hydrogen atom of the hydroxyl group in the formula (VI) is substituted is preferably a compound represented by the following formula (XXXVI). That is, the (b) radiation-sensitive sensitizer generator may be a compound represented by the following formula (XXXVI). When either R ⁹ or R ¹⁰ is a hydrogen atom, the compound represented by the following formula (XXXVI) may be referred to as an acetal compound.

Formula R ⁹ and R ¹⁰ of (XXXVI) is R ⁹ and R ¹⁰ and accept, respectively in the above formula (VI). R ⁹ and R ¹⁰ may be to form a ring structure like the R ⁹ and R ¹⁰ in the formula (VI). In the formula (XXXVI), R ²³ and R ²⁴ each independently represent 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); Or a linear, branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group) having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms), an alkoxy group having 1 to 5 carbon atoms, Phenyl group. R ²³ and R ²⁴ are independently a single bond, a double bond, -CH ₂ -, -O-, -S-, -SO ₂ -, -SO ₂ NH-, -C (= O) O-, -NHCO-, NHC (= O ) NH-, -CHR g - there may be formed a ring structure via a coupling comprising a -, -CR ^g _2, -NH- or -NR ^g. R ^g is synonymous with R ^g in formula (VI) above. The ketal compound or acetal compound may be a thioketal compound or thioacetal compound in which an oxygen atom bonded to R ²³ and / or R ²⁴ in formula (XXXVI) is substituted with sulfur.

The ketal compound and the acetal compound can be obtained by reacting a carbonyl compound with an alcohol. The reaction may be a reaction for protecting a carbonyl group contributing to a radiation-sensitizing action, and R ²³ and R ²⁴ in the formula (XXXVI) may be a protecting group for a carbonyl group. In this case, the reaction in which the radiation-sensitive sensitizer generator (b) becomes a radiation-sensitive sensitizer by radiation or the like can be referred to as a deprotection reaction. An example of the reactivity of the protecting group (the tendency of the deprotection reaction to occur) is described below. The reactivity of the protecting group is higher toward the right side and lower toward the left side. For example, when a methoxy group is used as a protecting group for a carbonyl group, the reactivity of the deprotection reaction is high, and the deprotection reaction tends to proceed under acid catalysis even at room temperature. As such, the deprotection reaction proceeds at room temperature, which is advantageous in that image blur can be prevented. On the other hand, when the deprotection reaction occurs in the pattern unexposed portion at the time of pattern exposure to generate a radiation-sensitive sensitizer, the contrast of the resist may be deteriorated. A protecting group may be selected so as to increase the activation energy of the deprotection reaction (so as to lower the reactivity of the protecting group) in order to prevent the generation of the sensitizing radiation sensitizer in the pattern unexposed portion. From the viewpoint of decreasing the reactivity of the protecting group, a cyclic protecting group in which R ²³ and R ²⁴ in formula (XXXVI) are bonded to each other to form a ring structure is more preferable. Examples of the ring structure include a 6-membered ring and a 5-membered ring, and a 5-membered ring is preferred. When a protective group having low reactivity is used, the resist material preferably includes a first capturing agent described later, and it is preferable to bake the resist material film before the batch exposure after the pattern exposure. By performing the baking, the unnecessary acid of the pattern unexposed portion is neutralized by the capturing agent, and the contrast of the latent image can be improved. In addition, the baking can compensate for the lowering of the reactivity of the protecting group, and the roughness of the latent image of the acid in the resist material film can be reduced by the diffusion of the substance by baking.

(B) the radiation-sensitive sensitizer generator of the kettle type may be a compound represented by the following formulas (XXVII) to (XXX).

Wherein R ²³ and R ²⁴ (XXVII) through (XXX) is R ²³ and R ²⁴ each synonymous with the formula (XXXVI). 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 There may be. And R ²⁵ represents an alkyl group having 1 to 5 carbon atoms. (b) when the compounds represented by the above formulas (XXVII) to (XXX) are used as the radiation-sensitive sensitizer generating agent, (b) when the radiation-sensitive sensitizer is irradiated from the radiation- The shift of the wavelength is larger and it is possible to cause a more selective increase / decrease reaction in the pattern exposure portion.

The orthoester compound in which the hydrogen atom of the hydroxyl group in the formula (VI) is substituted is preferably a compound represented by the following formula (XLVI). That is, the (b) radiation-sensitive sensitizer generator may be a compound represented by the following formula (XLVI).

R ⁹ of the formula (XLVI) is synonymous with R ⁹ in the formula (VI). R ³⁸ to R ⁴⁰ in the formula (XLVI) each independently represent a phenyl group; A halogen atom; Linear, branched or cyclic saturated or unsaturated hydrocarbons (preferably alkyl groups) having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms); Or a linear, branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group) having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms), an alkoxy group having 1 to 5 carbon atoms, Phenyl group. R ³⁸ to R ⁴⁰ are independently selected from the group consisting of a single bond or a double bond or a group selected from the group consisting of -CH ₂ -, -O-, -S-, -SO ₂ -, -SO ₂ NH-, -C (= O) = O) O-, -NHCO-, -NHC (= O) NH-, -CHR g -, -CR g 2, -NH- or -NR ^g - might be to form a ring structure via a coupling that includes have. R ^g is synonymous with R ^g in formula (VI) above.

The orthoester compound is decomposed into a deprotection reaction in the pattern exposure to be, for example, a carboxylic acid ester containing a carbonyl group or a carboxylic acid. As the orthoester compound, the carboxyl group portion of the radiation-sensitive sensitizer having a carboxyl group is substituted with OBO (for example, 4-methyl 2,6,7-trioxabicyclo [2.2.2] octan-1-yl) ), The OBO ester compound represented by the following formula (XLVII) is preferable. The (b) radiation-sensitive sensitizer generator that protects the carboxyl group with OBO generates a carboxylic acid by an acid catalyst generated at the time of pattern exposure, shifts the absorption wavelength of the radiation, Lt; / RTI > (b) Since the carboxylic acid is generated from the radiation-sensitive sensitizer generator, the polarity of the resist in the pattern exposure section changes from non-polarity to polarity, for example. As a result, the orthoester compound also functions as a dissolution promoter in the development step, contributing to an improvement in resist contrast. (b) Since the radiation-sensitive sensitizer generating agent includes an OBO ester compound, it is also possible to simultaneously generate a radiation-sensitive sensitizer and a polarity-change reaction.

Formula (XLVII) of R ⁴¹ and R ⁴² 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 hydroxyl 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 hydrocarbyl group A phenyl group substituted by an actual group; An alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, or a naphthoxy group substituted with a hydroxyl 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 hydroxyl group; An alkoxy group having 1 to 5 carbon atoms, a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms) substituted with a phenoxy group, a naphthoxy group, an anthracenoxy group, an amino group, an amide group or a hydroxyl group A saturated or 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. R ⁴¹ and R ⁴² are each independently preferably a hydrogen atom; A phenyl group; Phenoxy group; A phenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or an alkyl group having 1 to 5 carbon atoms; Or an alkoxy group having 1 to 5 carbon atoms, or a phenyl group substituted with a hydroxyl group.

(b) As the radiation-sensitive sensitizer generating agent, for example, a compound represented by the following formula can be given. These compounds are alcohol compounds in which the hydrogen atom of the alcoholic hydroxyl group is not substituted and are changed into a ketone compound by the reaction at the time of pattern exposure.

The following compounds are examples of ketal compounds or acetal compounds that protect the carbonyl group of the radiation sensitive sensitizer. These compounds are sensitizing radiation sensitizers containing ketones in the pattern exposure part by catalysis by an acid generated by pattern exposure.

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

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

The following chemical formulas are derived from derivatives in which a carboxyl group portion of a radiation-sensitive sensitizer having a carboxyl group is protected with OBO (for example, 4-methyl-2,6,7-trioxabicyclo [2.2.2] octan-1-yl) Is an example of an OBO ester compound.

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

As the radiation-sensitive sensitizer generated from the component (2) (that is, the radiation-sensitive acid-sensitizer generator (a) and the radiation-sensitive sensitizer generator (b)) by exposure, And derivatives thereof, 1,2-diketone and derivatives thereof, benzoin and derivatives thereof, benzophenone and derivatives thereof, fluorene and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, xanthene and derivatives thereof , Thioxanthene and derivatives thereof, xanthone and derivatives thereof, thioxanthone and derivatives thereof, cyanine and derivatives thereof, merocyanine and derivatives thereof, naphthalocyanine and derivatives thereof, subphthalocyanine and derivatives thereof, pyrylium and derivatives thereof , Thiopyrilium and derivatives thereof, tetrapyrin and derivatives thereof, annulene and derivatives thereof, spiropyran and derivatives thereof, spirooxazine and derivatives thereof, thiosporopyran and its And derivatives thereof, oxazine and derivatives thereof, azine and derivatives thereof, thiazine and derivatives thereof, oxazine and derivatives thereof, indolin and derivatives thereof, azulene and derivatives thereof, azulenium and derivatives thereof, And derivatives thereof, porphyrin and derivatives thereof, triarylmethane and derivatives thereof, phthalocyanine and derivatives thereof, acridone and derivatives thereof, coumarin and derivatives thereof, ketokmarine and derivatives thereof, quinolinone and derivatives thereof, Solvates and derivatives thereof, acridine and derivatives thereof, thiazine and derivatives thereof, benzothiazole and derivatives thereof, 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, pentacene And the like derivatives thereof, and coronene and derivatives thereof. It is also preferable that the radiation-sensitive sensitizer generated from the component (2) by exposure contains 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 and a carboxylic acid anhydride as a carbonyl group. The carbonyl compound is preferably a compound that absorbs radiation on the long wavelength side exceeding 250 nm from the viewpoint of increasing the contrast of the resist by sufficiently separating the wavelength of the radiation during the single exposure from the wavelength of the radiation upon pattern exposure. Examples of the carbonyl compound include a benzophenone derivative, a xanthone derivative, a thioxanthone derivative, a coumarin derivative, an acridone derivative, and the like. The carbonyl compound may be a naphthalene derivative, an anthracene derivative, or an acridone derivative. In the sensitizing radiation sensitizer, it is preferable that hydrogen in the aromatic ring is substituted with an electron hole. Since the hydrogen of the aromatic ring of the sensitizing radiation sensitizer is substituted with an electron hole excitation, the electron transfer efficiency by the sensitization reaction during the batch exposure is improved, and the sensitivity of the resist tends to be improved. Furthermore, (b) the difference between the absorption wavelength of the radiation of the radiation sensitive sensitizer generator and the absorption wavelength of the radiation sensitizer can be increased, and the radiation sensitizer can be selectively The contrast of the latent image of the acid in the resist material tends to be improved. Examples of the electron-donating group include a hydroxyl group, a methoxy group, an alkoxy group, an amino group, an alkylamino group, and an alkyl group.

Examples of the benzophenone and derivatives thereof include the following compounds.

Examples of thioxanthone and derivatives thereof include the following compounds.

Examples of xanthones and derivatives thereof include the following compounds.

As the acridone and its derivatives, for example, the following compounds can be mentioned.

Examples of coumarin and its derivatives include the following compounds.

The radiation-sensitive sensitizer may include the following compounds.

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-1- (4-morpholinophenyl) - butanone-1 , 1,2-octanedione, 1- [4- (phenylthio) -, 2- (O-benzoyloxime)], ethanone, 1- [ Yl] -, 1- (O-acetyloxime), and the like.

(b) the radiation-sensitive sensitizer generator may be a part of (1) the polymer constituting the polymer component. In this case, (b) the radiation sensitive sensitizer generator is present in such a form that a group excluding one hydrogen atom from the compound binds 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 blending amount of the (b) radiation-sensitive sensitizer generator per 100 parts by mass of the polymer component is preferably 0.005 mass part And more preferably 0.1 part by mass. On the other hand, the upper limit of the blending amount is preferably 50 parts by mass, more preferably 30 parts by mass.

(b) the radiation-sensitive sensitizer generating agent is part of the polymer constituting the polymer component, (1) the lower limit of the content ratio of the (b) radiation-sensitive sensitizer generator per mole of the polymer component is 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 blending amount or content ratio is smaller than the above lower limit, the sensitivity may be lowered. On the other hand, if the blending amount or the content ratio exceeds the upper limit, the resist material film tends to be difficult to form, and the rectangularity of the cross-sectional shape of the resist pattern may deteriorate.

((c) a radiation-sensitive acid generator)

(c) a radiation-sensitive acid generator generates an acid when irradiating the first radiation and not irradiating the second radiation, and when irradiating only the second radiation without irradiating the first radiation Is a component which does not substantially generate the acid, and is different from the (a) radiation-sensitive acid-sensitizer generator. (c) Since the radiation-sensitive acid generator has the above properties, an acid can be generated only in the pattern exposure portion of the resist material film by the radiation sensitization reaction during the batch exposure.

Examples of the cation (I) and cation (II) in the [C1] compound and the [C2] compound include monovalent onium cations represented by X ⁺ as the cation (I) and the cation And decomposed by irradiation with exposure light. In the exposed part, protons generated by the decomposition of the onium cations and sulfonic acids are generated from the sulfonate anions. These cations do not generate sensitizing radiation sensitizers.

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

Among them, triphenylsulfonium cation is preferable as X ^{< + &} gt ;.

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

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

As the sulfonium salt compound, for example, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium purple in the [C1] compound and the [C2] Triphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 6- ( Adamantan-1-ylcarboxyoxy) -1,1,2,2-tetrafluorohexane-1-sulfonate, triphenylsulfoniumadamantane-1-yloxycarbonyl carboxylate, triphenylsulfonium 4-trifluoromethyl salicylate, 4-methoxyphenyldiphenylsulfonium 1,2-di (cyclohexyloxycarbonyl) ethane-1-sulfonate, and the like.

(c) The radiation-sensitive acid generator may also have a compound other than the [C1] compound and the [C2] compound, and the (c) radiation-sensitive acid generator other than the [C1] , For example, other onium salt compounds, diazomethane compounds, and sulfonimide compounds. Examples of the onium salt compound include a tetrahydrothiophenium salt compound and an iodonium salt compound in addition to the sulfonium salt compound.

As other sulfonium salt compounds, for example, 4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexylphenyl Octylsulfonate, 4-cyclohexylphenyldiphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethane Sulfonates such as 4-methanesulfonylphenyldiphenylsulfonium trifluoromethane sulfonate, 4-methanesulfonylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium Perfluoro-n-octanesulfonate, 4-methanesulfonylphenyldiphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, etc. .

Examples of the tetrahydrothiophenium salt compound include 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen- N-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- Tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium nonafluoro-n -Butane sulfonate, 1- (6-n-butoxynaphthalen-2-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- Tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethane sulphate (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonane N-butanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- Hydroxyphenyl) tetrahydrothiophenium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate.

Examples of the iodonium salt compounds include diphenyl iodonium trifluoromethanesulfonate, diphenyl iodonium nonafluoro-n-butanesulfonate, diphenyl iodonium perfluoro-n-octanesulfonate , Diphenyl iodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, bis (4-t- butylphenyl) iodonium trifluoro (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate.

Examples of the sulfone imide compound include N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (nonafluoro- (Perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- -2,3-dicarboxyimide, N- (2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) bicyclo [2.2. 1] hept-5-ene-2,3-dicarboxyimide.

Examples of the diazomethane compound include bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis Bis (cyclopentylsulfonyl) diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis Bis (p-tolylsulfonyl) diazomethane, bis (2,4-xylylsulfonyl) diazomethane, bis (4-isopropylphenylsulfonyl) diazomethane, bis Bis (naphthylsulfonyl) diazomethane, bis (anthracenylsulfonyl) diazomethane, and the like.

(c) The radiation-sensitive acid generator may be part of (1) a 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.

When the (c) radiation-sensitive acid generator is a component different from (1) the polymer component, the lower limit of the blending amount of (c) the radiation-sensitive acid generator relative to 100 parts by mass of the polymer component is preferably 0.1 part by mass , More preferably 1 part by mass. On the other hand, the upper limit of the blending amount 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 (1) the polymer component, (1) the lower limit of the content ratio of the (c) radiation-sensitive acid generator to 1 mole of the polymer component is preferably 0.01 , More preferably 0.02 mol, and still more preferably 0.1 mol. On the other hand, the upper limit of the content is preferably 0.5 mol, more preferably 0.3 mol.

If the blending amount or content ratio is smaller than the above lower limit, the sensitivity may be lowered. On the other hand, if the blending amount or the content ratio exceeds the upper limit, the resist material 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 10% by mass, more preferably 15% . On the other hand, the upper limit of the content is preferably 30% by mass, more preferably 25% 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, the "content of the component (2)" means the total content of the components different from the polymer component (1) in the component (2).

[Other acid diffusion control agent]

The chemical amplification type resist material may be mixed with an acid diffusion control agent other than the [C1] compound and the [C2] compound. Other acid diffusion control agents capture acid and cations and function as a quencher. The chemically amplified resist material contains other acid diffusion control agent so that the excess acid generated in the resist material 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 a radiation-sensitive property and a compound having no radiation-sensitive property.

As the compound having no radiation-sensitive properties, 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 hydroxyl group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen- , An amide compound, an imide compound, etc. Among them, a nitrogen-containing compound having a carbamate group is preferable.

The basic compounds include 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) - -) - 2- (tert-butoxycarbonylamino) -3-cyclohexyl-1-propanol, (R) Butanol, (R) - (+) - 2- (tert-butoxycarbonylamino) -3-phenylpropanol, (S) Propanol, (R) - (+) - 2- (tert-butoxycarbonylamino) -3-phenyl-1-propanol, (R) - (+) - 2- (tert-butoxycarbonylamino) -1-propanol, Benzyl-L-threonine, N- (tert-butoxycarbonyl) -L-aspartic acid 4-benzyl ester, N- (tert-butoxycarbonyl) Methyl-4-imidazolidinone, (S) - (-) - 1- (tert-butoxycarbonyl) -2-tert- Methyl-4-imidazolidinone, N- (tert-butoxycarbonyl) -3-cyclohexyl-L-alanine methyl ester, N- (tert- N- (tert-butoxycarbonyl) -D-glucosamine, N- (tert-butoxycarbonyl) ethylamine, N- Butoxycarbonyl) -L-isoleucine, N- (tert-butoxycarbonyl) -L-glutamine, 1- (tert-butoxycarbonyl) imidazole, N- (Tert-butoxycarbonyl) -L-lysine, N- (tert-butoxycarbonyl) -L-lysine, N- (tert-butoxycarbonyl) ) -L-methionine, N- (tert-butoxycarbonyl) -3- (2-naphthyl) -L- alanine, N- (tert- (Tert-butoxycarbonyl) -L-proline, N- (tert-butoxycarbonyl) -L-phenylalanine methyl ester, N- Propoxycarbonyl) -L-prol (S) - (-) - l- (tert-butoxy) -N'-methoxy-N'-methyl amide, N- (tert-butoxycarbonyl) (R) - (+) - 1- (tert-butoxycarbonyl) -2-pyrrolidinemethanol and 1- (tert-butoxycarbonyl) N- (tert-butoxycarbonyl) -L-serine methyl ester, N- (tert-butoxycarbonyl) (tert-butoxycarbonyl) -L-threonine, N- (tert-butoxycarbonyl) -p-toluenesulfonamide, 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, Butyl-4-benzyl-1-piperazinecarboxylate, tert-butyl (1S, 4S) - ((tert-butylcarbamoylcarbamoyl) -) - 2,5-diazabicyclo [2.2.1] heptane-2-carboxylate, tert-butyl N- (2,3- dihydroxypropyl) carbamate, tert- (R *, S *)] - N- [2-hydroxy-2- ( 1-methylethyl] carbamate, tert-butyl-4-oxo-1-piperidinecarboxylate, tert-butyl- Pyrrolidinecarboxylate, 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.

The compound having a radiation-sensitive property is divided into a compound (radiation-decomposable compound) which is decomposed by radiation and loses acid diffusion control ability and a compound which is produced by radiation and obtains acid diffusion control ability (radiation-generating compound).

The radiation-decomposable compound is decomposed only in the pattern exposure portion in the pattern exposure process, 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 unexposed portion can be improved.

As the radiation-decomposable compound, sulfonic acid salts and carboxylic acid salts of a radiation-decomposable cation other than the [C1] compound and the [C2] compound are preferable. The sulfonic acid in the sulfonic acid salt is preferably a weak acid, more preferably a hydrocarbon group having 1 to 10 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 iodonium cation and the like.

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 the batch exposure process. In this case, in the exposure unit of the pattern exposure process, the radiation-sensitive sensitizer can be efficiently generated, and the unnecessary acid and cation 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-cationic complex), a compound containing 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 radiation-sensitive base generator is preferably a compound having a cyclic 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-dimethyl- 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. Thus, from the viewpoint of obtaining the acid diffusion control ability in the baking step, it is preferable that the heating temperature in the baking step described later 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 (1) the acid diffusion control agent relative to 100 parts by mass of the polymer component is preferably 0.001 part by mass, more preferably 0.01 part by mass. 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 crosslinking agent is to cause a crosslinking reaction between polymer components by an acid catalysis reaction in a baking step after collective exposure to increase the molecular weight of the polymer component and insolubilize with the developing solution. It is different. Since the resist material contains a cross-linking agent, the polarity portion becomes non-polar at the same time as the cross-linking, and is insoluble in the developer, so that a negative resist material can be provided.

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

[Other additives]

Examples of other additives include a surfactant, an antioxidant, a dissolution inhibitor, a plasticizer, a stabilizer, a colorant, a halation inhibitor, and a dye. Known materials can be selected for the surfactant, the antioxidant, the dissolution inhibitor, the plasticizer, the stabilizer, the colorant, the halation inhibitor and the dye. As the surfactant, for example, ionic or nonionic fluoric surfactants, silicone surfactants and the like can be used. Examples of the antioxidant include phenolic antioxidants, antioxidants containing organic acid derivatives, sulfur-containing antioxidants, phosphorus-based antioxidants, amine-based antioxidants, antioxidants containing amine-aldehyde condensates, amine-ketone condensates An antioxidant and the like.

[menstruum]

The solvent is intended to dissolve the composition of the resist material to facilitate the formation of the resist material film by the applicator in the spin coating method or the like. In addition, the compound contained in the above-mentioned (b) radiation-sensitive sensitizer generators and the like is excluded from the solvent. As the solvent, for example, ketones such as cyclohexanone and methyl-2-amyl ketone; Alcohols such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol and 1-ethoxy-2-propanol; Ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether and diethylene glycol dimethyl ether; And propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, tert- butyl acetate, And esters such as glycol monomethyl ether, propylene glycol mono-tert-butyl ether acetate and the like.

[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% by mass, preferably 30% by mass, and more preferably 20% by mass.

<Method of Forming Resist Pattern>

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

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

As shown in Fig. 1, the lithography process according to the present embodiment includes the following steps.

Step S1: Step of preparing a substrate to be processed

Step S2: a step of forming a lower layer film and a resist material film (film forming step)

Step S3: A step of generating an acid in the exposure part by pattern exposure (pattern exposure step)

Step S4: a step of growing the acid only in the pattern exposure part by the batch exposure (batch exposure step)

Step S5: A step of generating a polarity change reaction by the acid catalyst on the pattern exposure part by baking after exposure (baking step)

Step S6: a step of forming a resist pattern by a developing process (developing step)

Step S7: a step of transferring the pattern by etching (etching step)

(Step S1)

The substrate (the processed substrate) to be processed in the following steps may be a semiconductor wafer such as a silicon substrate, a silicon dioxide substrate, a glass substrate, and an ITO substrate, or may be an insulating film layer formed on the semiconductor wafer.

(Step S2: film forming step)

The resist material film is formed using the resist material of the present embodiment. Examples of the method for forming the resist material film include a method of applying a liquid resist material by spin coating or the like, a method of adhering a resist material in the form of a film (solid phase), and the like. When a liquid resist material is applied, it may be heated (pre-baked) after application to volatilize the solvent in the resist material. The conditions for forming the resist material film are appropriately selected according to properties of the resist material and the thickness of the obtained resist material film. The average thickness of the resist material film is preferably 1 nm or more and 5,000 nm or less, more preferably 10 nm or more and 1,000 nm or less, and still more preferably 30 nm or more and 200 nm or less.

Prior to forming the resist material film on the substrate, a lower layer film (a film for improving the adhesion of the resist, a film for improving the resist shape, etc.) may be formed on the substrate. By forming the antireflection 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. By forming a film for improving resist adhesion, adhesion between the substrate and the resist material film can be improved. By forming a film for improving the shape of the resist, the shape of the resist after development can be further improved. That is, the footing shape or constricted shape of the resist can be reduced. On the other hand, in order to prevent the degradation of the resist shape due to the generation of the standing wave of the radiation of the batch exposure, it is preferable that the thickness of the lower layer film is designed so as to suppress the reflection of the radiation of the batch exposure. The lower layer film is preferably a film that does not absorb the radiation of the batch exposure. For example, when the lower layer film absorbs the radiation of the batch exposure, the radiation increase / decrease reaction occurs in the resist material film due to the energy transfer or the electron transfer from the lower layer film, thereby causing a risk of acid generation in the pattern unexposed portion. As a result, a buffer layer that does not carry out the radiation sensitization reaction can be disposed between the resist material film and the lower layer film to prevent the lower layer film from absorbing radiation.

A protective film may be further formed on the resist material film. By forming a protective film, it is possible to suppress the deactivation of the radiation-sensitive sensitizer, the acid, and the reaction intermediate thereof, which are generated in the pattern exposure step S3, and the process stability can be improved. In order to prevent the acid generation reaction in the unexposed portion in the batch exposure step, the protective film may be formed so that at least a part of the wavelength of the non-ionizing radiation directly absorbed by the component (a) or (c) Absorbing film. It is possible to suppress the entry of the out-of-band light (OOB light), which is the radiation of the ultraviolet region generated during the EUV exposure, into the resist material film and to prevent the outgoing radiation of the radiation- It is possible to prevent the decomposition of the generator. When the absorber film is directly formed on the resist material film, in order to suppress the generation of acid in the resist material film due to the radiation sensitization reaction in the pattern unexposed portion, the wavelength of the second radiation beam in the collective exposure step Of the radiation-sensitive reaction. Further, a buffer layer may be disposed between the resist material film and the protective film so as to prevent the sensitizing radiation absorbing film in the resist material film from increasing or decreasing from the absorbing film that absorbs the radiation, It is possible. After the pattern exposure step S3, the absorbing film is formed on the resist material film before the batch exposure step S4. By the irradiation of the second radiation in the batch exposure step S4, It is possible to further suppress the generation of acid directly from the radiation-sensitive acid generator or the radiation-sensitive acid generator.

(Step S3: pattern exposure process)

In the pattern exposure step S3, a light shielding mask of a predetermined pattern is arranged on the resist material film formed in the film forming step S2. Thereafter, the resist film is irradiated (pattern exposed) with the first radiation through the mask from an exposure apparatus (radiation irradiation module) having a projection lens, an electro-optical system mirror, or a reflection mirror.

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

Further, ionizing radiation is radiation having sufficient energy to ionize atoms or molecules. Non-ionizing radiation, on the other hand, is radiation that does not have enough energy to ionize atoms or molecules. Examples of the ionizing radiation include gamma ray, x-ray, alpha ray, intrapersonal ray, quantum ray, beta ray, ion beam, electron beam and EUV. As the ionizing radiation used for pattern exposure, electron beams, EUV and ion beams are preferable, and electron beams and EUV are more preferable. Examples of non-ionizing radiation include non-ionizing radiation having a wavelength of 250 nm or less such as KrF excimer laser light and ArF excimer laser light.

EUV having a wavelength of 13.5 nm, excimer laser beam (ArF excimer laser beam) having a wavelength of 193 nm, and excimer laser beam (KrF excimer laser beam) having a wavelength of 248 nm are used as the light for pattern exposure, for example, . The amount of exposure in the pattern exposure is preferably less than that in the case of using the chemically amplified resist of the present embodiment for batch exposure. By the pattern exposure, the groups represented by the components (a) to (c) in the resist material film are decomposed to generate a radiation-sensitive sensitizer for absorbing the acid and the second radiation.

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

It is also preferable that at least the wavelength of the non-ionizing radiation absorbed directly by the radiation-sensitive acid generator in the component (a) or the component (c) is applied onto the resist material film in the post- It is also possible to form an absorbing film which absorbs a part. By forming the absorbing film, the second radiation in the following batch exposure step S4 is irradiated with the radiation of the radiation-sensitive acid generator or the direct acid from the radiation-sensitive acid generator remaining in the resist material film after the pattern exposure step S3 Occurrence can be further suppressed.

(B) a radiation-sensitive sensitizer generator having an alcoholic hydroxyl group that is not substituted with a hydrogen atom is used, the resist material film is exposed to a reduced pressure atmosphere It is preferable to place it in an inert atmosphere containing nitrogen or argon. By placing the resist material film in the above-described atmosphere, it is possible to suppress the exposure of the resist material film to exposure to oxygen during the exposure and the stop of the radical reaction by the oxygen, and to suppress the quenching of the acid by the trace amount of the basic compound The process tends to be more stable. The upper limit of the time (storage time) from the pattern exposure step S3 to the execution of the batch exposure step S4 is preferably 30 minutes, more preferably 10 minutes. When the storage time is 30 minutes or less, a decrease in sensitivity tends to be suppressed. On the other hand, when the (b) radiation-sensitive sensitizer generator having an alcoholic hydroxyl group substituted with a hydrogen atom (i.e., a ketal compound, an acetal compound or an orthoester compound) is used, after the pattern exposure step S3, It is preferable that the atmosphere in which the resist material film is present is made into the air that has been cleaned with an amine removing filter. When the above-mentioned (b) radiation-sensitive sensitizer generator is used, since it is difficult to receive the influence of oxygen as described above, it can be treated in an air cleaned with an amine removing filter. By placing the resist material film in the above-described atmosphere, the quenching of the acid by the trace amount of the basic compound can be suppressed, and the process tends to be further stabilized. The upper limit of the time (storage time) from the pattern exposure step S3 to the execution of the batch exposure step S4 is preferably 30 minutes, more preferably 10 minutes. When the storage time is 30 minutes or less, a decrease in sensitivity tends to be suppressed.

In the resist pattern forming method of the present embodiment, after the pattern exposure step S3, before the following batch exposure step S4, the step of carrying the substrate from the exposure apparatus that performs the pattern exposure step S3 to the exposure apparatus that performs the batch exposure step S4 It may be further equipped. Further, the batch exposure may be performed in a module corresponding to an interface with an exposure device in an inline-connected coating and developing device. When the component (2) comprises a ketal compound, an acetal compound or an orthoester compound, the resist pattern forming method of the present embodiment is characterized in that after the pattern exposure step S 3, before the following batch exposure step S 4, the baking step S 3 a (Sometimes referred to as an exposure bake (PPEB or PEB)) (see Fig. 3). The heating temperature in the baking step is preferably 30 占 폚 to 150 占 폚, more preferably 50 占 폚 to 120 占 폚, and still more preferably 60 占 폚 to 100 占 폚. The heating time is preferably 5 seconds or more and 3 minutes or less, more preferably 10 seconds or more and 60 seconds or less. It is also preferable that the baking is performed under an environment in which humidity is controlled. This is because when the hydrolysis reaction is used as the deprotection reaction to generate the sensitizing radiation sensitizer, the humidity affects the reaction rate. The resist pattern forming method can accelerate the generation of the radiation-sensitive sensitizer due to the hydrolysis reaction of the acetyl compound, the ortho ester compound, the ketal compound and the like to the carbonyl compound by including the baking step S3a.

(Step S4: batch exposure process)

In the batch exposure step S4, a high-sensitivity module (including an exposure apparatus or a radiation irradiation module) having a projection lens (or a light source) is formed on the entire surface of the resist material film after the pattern exposure step S3 The second radiation is irradiated (collectively exposed). As the batch exposure, the entire surface of the wafer may be exposed at one time, or may be combined with local exposure, or may be overlaid and exposed. A general light source can be used for the light source for collective exposure. By passing through a band-pass filter or a cut-off filter, ultraviolet rays from a mercury lamp and a xenon lamp controlled at a desired wavelength, This may be a narrow ultraviolet ray. In the above-mentioned batch exposure, only the radiation-sensitive sensitizer generated in the pattern exposure portion of the resist material film absorbs the radiation. As a result, in the batch exposure, the radiation is selectively absorbed in the pattern exposure unit. Therefore, during the batch exposure, the acid can be continuously generated only in the pattern exposure section, and the sensitivity can be greatly improved. On the other hand, since no acid is generated in the pattern unexposed portion, the sensitivity can be improved while maintaining the chemical contrast in the resist material film.

The second radiation used for the batch exposure has a wavelength longer than the wavelength of the non-ionizing radiation in the first radiation and is a non-ionizing radiation having a wavelength exceeding 250 nm, and the near ultraviolet (wavelength: 250 to 450 nm) .

In the batch exposure step S4, in order to suppress the acid generation reaction in the pattern unexposed portion, the polymer component, the radiation-sensitive acid generator, and the radiation-sensitive sensitizer generator are irradiated with radiation having a wavelength longer than that of the radiation capable of absorbing It is necessary to expose it. Taking these into consideration, the lower limit of the wavelength of the non-ionizing radiation in the batch exposure is preferably 280 nm, more preferably 320 nm. In the case of generating a radiation-sensitive sensitizer capable of absorbing radiation of a longer wavelength, the wavelength of the non-ionizing radiation may be 350 nm or more. However, when the wavelength of the non-ionizing radiation is excessively long, the efficiency of the radiation sensitization reaction is lowered, so that the polymer component, the radiation-sensitive acid generator, and the radiation- It is preferable to use non-ionizing radiation having as short a wavelength as possible that can absorb the radiation-sensitive sensitizer. From this viewpoint, the upper limit of the wavelength of the non-ionizing radiation is preferably 450 nm, more preferably 400 nm.

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

The immersion lithography in the pattern exposure step S3 and / or the batch exposure step S4 is performed in a state in which a resist material film formed in the film formation step S2 or a liquid having a refractive index of 1.0 or more is interposed between the protective film and the projection lens It is possible. The protective film is preferably for preventing reflection or improving the reaction stability. Further, it is preferable that the protective film prevents penetration of liquid, thereby enhancing water repellency on the surface of the film, and preventing defects due to liquid in immersion exposure.

In the immersion lithography in the batch exposure step S4, the liquid may absorb at least part of the wavelength of the second radiation directly absorbed by the component (a) or (c) (radiation-sensitive acid generator). By using the liquid for the immersion lithography, by irradiation of the second radiation in the batch exposure step S4, the radiation-sensitive acid generator or the radiation-sensitive acid generator remaining in the resist material film after the pattern exposure step S4 It is possible to further suppress the direct acid generation from the catalyst.

In the case where the pattern exposure step S3 and / or the batch exposure step S4 are carried out by dry lithography, it can be carried out under any atmospheric pressure reduced atmosphere or under an inert atmosphere, but in an atmosphere of reduced pressure or an inert atmosphere containing nitrogen or argon , And the upper limit of the basic compound concentration in the atmosphere in the practice is preferably 20 ppb, more preferably 5 ppb, and further preferably 1 ppb.

(Process S5: bake process)

In the baking step S5, the resist material film after the batch exposure step S4 is heated (hereinafter also referred to as "post flat exposing bake (PFEB)" or "post exposing bake (PEB)"). When the resist pattern forming method of the present embodiment includes the baking step S3a after the pattern exposure step S3 and before the collective exposure step S4, the baking step S3a is referred to as a first PEB step, the baking step S5 is referred to as a second PEB (See Fig. 3). As the heating conditions, for example, the temperature can be set to 50 ° C or more and 200 ° C or less and 10 seconds or more and 300 seconds or less in an atmosphere of inert gas such as nitrogen or argon in the air. By setting the heating conditions within the above ranges, it is possible to control the diffusion of the acid and also to ensure the processing speed of the semiconductor wafer. In the baking step S5, the acid generated in the pattern exposure step S3 and the batch exposure step S4 causes (1) a polarity change reaction such as a deprotection reaction of a polymer component, a crosslinking reaction, and the like. In addition, wave wrinkles may occur on the sidewall of the resist due to the influence of the standing wave of radiation in the resist material film. In the baking step S5, the wrinkles on the surface can be reduced by diffusion of the reactant.

(Step S6: development step)

In the developing step S6, the resist material film after the baking step S5 is brought into contact with the developing solution. By the reaction in the resist material film in the baking step S5, the resist pattern is formed by using the fact that the solubility in the developing solution is selectively changed in the pattern exposure part. The developer can be divided into a positive developer and a negative developer.

The positive developer is preferably an alkaline developer. The alkali developing solution selectively melts the portion of the resist film after exposure with high polarity. Examples of the alkali developing solution include a solution obtained by dissolving at least one kind of alkaline compound such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines (ethanolamine etc.), tetraalkylammonium hydroxide Alkaline aqueous solution and the like. As the alkaline developer, an alkaline aqueous solution in which TAAH is dissolved is preferable. As TAAH, for example, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltriethylammonium hydroxide, trimethylethylammonium hydroxide, dimethyldiethylammonium hydroxide, trimethylhydroxide (2-hydroxyethyl) ammonium, hydroxylated (2-hydroxyethyl) ammonium, (i.e., choline), triethyl (2-hydroxyethyl) (2-hydroxyethyl) ammonium hydroxide, ethyl tri (2-hydroxyethyl) ammonium hydroxide, and tetra (2-hydroxyethyl) ammonium hydroxide.

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

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

As the negative developer, an organic developer is preferable. The organic developer selectively melts the low polarity portion of the resist film after exposure. The organic developer is used to improve the resolution performance and process window by removing patterns such as holes and trenches (grooves). In this case, the dissolution contrast between the pattern exposure portion and the pattern unexposed portion is obtained due to the difference in affinity between the solvent in the resist material film and the organic developer. The high polarity portion has low solubility in the organic developer and remains as a resist pattern. Examples of the organic developer include organic solvents such as 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutylketone, methylcyclohexa Acetic acid isoamyl acetate, isoamyl acetate, propyl formate, propyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, valeryl formate, valerol acetate, isobutyl acetate, Wherein the lactic acid is selected from the group consisting of methyl lactate, methyl lactate, methyl propionate, methyl crotonate, ethyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, Methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenylethyl formate, 3-phenylpropionic acid Propionate, benzyl, phenyl ethyl, and the like can be mentioned acetic acid 2-phenylethyl.

The resist pattern after the developing step S6 (including the rinsing treatment) is heated (sometimes referred to as post-baking). By the post-baking, the rinsing liquid remaining after the rinsing process can be vaporized and removed, and the resist pattern can be hardened.

(Step S7)

In step S7, the base substrate is etched or ion-implanted using the resist pattern after the development step S6 as a mask to form a pattern. The etching may be dry etching in an atmosphere of plasma excitation or the like, or may be wet etching to be immersed in a chemical solution. After the pattern is formed on the substrate by etching, the resist pattern is removed.

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

4 is a graph showing the absorbance of the pattern exposure unit and the absorbance of the unexposed portion of the resist material film at the time of batch exposure. In the pattern unexposed portion (pattern unexposed portion) of the resist material film, absorption is exhibited in ultraviolet rays having a relatively short wavelength but not in ultraviolet rays having a long wavelength. On the other hand, in the pattern exposed portion (pattern exposure portion) of the resist material film, an acid and a radiation-sensitive sensitizer are generated as described above. The generated radiation-sensitive sensitizer absorbs non-ionizing radiation having a wavelength exceeding 250 nm and shows absorption by ultraviolet rays having a relatively long wavelength. In the batch exposure, the entire surface of the resist material film is irradiated with radiation without using a mask like the pattern exposure. In the pattern unexposed portion, the absorption of the second radiation in the batch exposure step S4 is small. Therefore, in the batch exposure step S4, a mechanism for generating acid mainly by the radiation sensitive property adjuster occurs in the pattern exposure part. Therefore, the acid can be continuously generated only in the pattern exposure portion during the batch exposure, and the sensitivity can be improved while maintaining the lithography characteristics.

FIG. 5A is a conceptual diagram showing a graph of an acid concentration distribution by a resist pattern forming method using a conventional chemically amplified resist material. FIG. As shown in Fig. 2, when only pattern exposure is performed with EUV or the like, sufficient acid can not be generated and sensitivity is lowered. When the exposure dose is increased to improve the sensitivity, the latent image of the resist pattern is deteriorated (the lithography characteristic is lowered), making it difficult to achieve both sensitivity and lithography characteristics. FIG. 5B is a conceptual diagram showing a radiation-sensitive sensitizer concentration distribution and an acid concentration distribution by a resist pattern forming method using the chemically amplified resist material according to the present embodiment as a graph. FIG. As the pattern exposure, the latent image of the resist pattern is excellent, but sufficient acid is not generated. However, after the batch exposure, the amount of the acid can be increased only in the pattern exposure portion by the radiation-sensitive sensitizer generated by the pattern exposure, and the sensitivity can be improved with a small exposure amount while maintaining a good latent image of the resist pattern. Since the acid generating mechanism by the sensitizing radiation sensitizer at the time of batch exposure occurs at room temperature, the blurring of the latent image at the time of acid generation is small, and the sensitivity can be remarkably increased while maintaining the resolution.

<Semiconductor device>

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

6A is a cross-sectional view showing the step of forming a resist pattern, and FIG. 6A is a cross-sectional view of a semiconductor wafer 1, an etched film 3 formed on the semiconductor wafer 1, Sectional view of the resist pattern 2 formed on the film 3 (equivalent to the end of the developing step S6). Examples of the etched film include an active layer, a lower insulating film, a gate electrode film, and an upper insulating film. Between the etched film 3 and the resist pattern 2, an antireflection film, a lower layer film for improving resist adhesion, and a lower layer film for improving the resist shape may be formed. Further, a multilayer mask structure may be employed. 6B is a cross-sectional view showing an etching process and is a sectional view of a semiconductor wafer 1, a resist pattern 2 and an etched film 3 etched using the resist pattern 2 as a mask. The etched film 3 is etched along the shape of the opening of the resist pattern 2. [ 6C is a cross-sectional view of a patterned substrate 10 having a pattern of a semiconductor wafer 1 and an etched film 3 etched after the resist pattern 2 is removed.

A semiconductor device can be formed using a substrate having the pattern of the etched film 3. As the forming method, for example, a method of embedding wiring between patterns of the etched film 3 from which the resist pattern 2 is removed and laminating a device element on the substrate can be given.

&Lt; Mask for lithography >

The lithography mask according to the present embodiment is manufactured by processing a substrate using a resist pattern formed by the above method. Examples of the manufacturing method include a method of etching a hard mask formed on the surface of a glass substrate or a surface of a glass substrate using a resist pattern. Here, the lithography mask includes a transmissive mask using ultraviolet rays or electron beams, a reflective mask using EUV light, and the like. When the mask for lithography is a transmissive mask, it can be manufactured by masking the light shielding portion or the phase shift portion with a resist pattern and etching the mask. When the lithography mask is a reflection type mask, it can be produced by processing the light absorbing body by etching using the resist pattern as a mask.

<Template for Nanoimprint>

A template for a nanoimprint according to the present embodiment can also be produced using a resist pattern formed by the above method. Examples of the manufacturing method include a method in which a resist pattern is formed on the surface of a hard mask formed on the surface of a glass substrate or a surface of a glass substrate and then processed by etching.

<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 will be described below.

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

The Mw and Mn of the polymer were determined by using a GPC column (G2000HXL, G3000HXL, G4000HXL, G4000HXL, and one or more resins) at a flow rate of 1.0 mL / min, an eluting solvent of tetrahydrofuran, a sample concentration of 1.0% , And a column temperature of 40 占 폚, using a differential refractometer as a detector, by gel permeation chromatography (GPC) using monodispersed polystyrene as a standard.

[ ¹³ C-NMR analysis]

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

<Synthesis of [A] Polymer>

(1) Monomers used for synthesis of [A] polymer are shown below.

(M-2), (M-3), (M-4) and (M-4) (II), respectively.

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

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

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

After dissolving 55 g (58 mol%) of the compound (M-3), 45 g (42 mol%) of the compound (M-1), 3 g of AIBN and 1 g of t-dodecylmercaptan in 150 g of propylene glycol monomethyl ether, Under the atmosphere, the reaction temperature was maintained at 70 占 폚 and polymerization was carried out for 16 hours. After the polymerization, the reaction solution was added dropwise to 1,000 g of n-hexane to coagulate and purify the polymer. 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 further added, and hydrolysis was carried out for 8 hours while refluxing from the boiling point to obtain (M- 3) was deacetylated. After the reaction, the solvent and triethylamine were distilled off under reduced pressure, and the obtained polymer was dissolved in 150 g of acetone. The resulting polymer was 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 thereby obtain a polymer (A-2) as the polymer [A]. The polymer (A-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 the p-hydroxystyrene structural unit and the compound (M-1) obtained by deacetylation of the structural unit derived from (M-3) 50 mol% and 50 mol%, respectively.

[Synthesis Example 3] (Synthesis of polymer (A-3)

6.79 g (20 mol%) of compound (M-1) were dissolved in 40 g of propylene glycol monomethyl ether, 6.99 g (40 mol%) of compound (M- And 0.79 g (5 mol% based on the total molar amount of the compound) of AIBN as a radical polymerization initiator was dissolved to prepare a monomer solution. 20 g of propylene glycol monomethyl ether was added to a 100 mL three-necked flask, and the mixture was purged with nitrogen for 30 minutes, and then the reaction flask was heated to 80 DEG C with stirring. The resulting monomer solution was added dropwise over 3 hours and aged for 3 hours. After completion of the polymerization, the polymerization reaction solution was cooled to 30 캜 or lower by water-cooling. This polymerization reaction solution was poured into 400 g of hexane, and the precipitated solid was separated by filtration. The solid matter separated by filtration was washed twice with 80 g of hexane, filtered again, and dried at 50 DEG C for 17 hours. This solid component was added to a 100 mL branched flask containing 20 g of propylene glycol monomethyl ether and dissolved. Further, 3.49 g of triethylamine and 0.56 g of pure water were added, and the mixture was heated to 80 DEG C and reacted for 6 hours to hydrolyze. After completion of the hydrolysis, the reaction solution was cooled with water to 30 캜 or lower. The reaction solution was poured into 400 g of hexane, and the precipitated solid was separated by filtration. The solid matter separated by filtration was washed twice with 80 g of hexane, filtered again, and dried at 50 캜 for 17 hours to obtain 12.2 g (61%) of polymer (A-3). The polymer (A-3) had an Mw of 7,500 and an Mw / Mn of 1.52. ¹³ C-NMR results of the analysis, in the (M-1) structural unit, (M-3) p- hydroxystyrene structural unit, and (M-4) obtained by the deacetylation of the structural unit derived from derived from The content ratio of each structural unit derived was 40 mol%, 40 mol% and 20 mol%, respectively. Table 1 shows the Mw, Mw / Mn and ratio of each structural unit in the obtained polymers (A-1) to (A-3).

* 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.

&Lt; (2) Components generating radiation-sensitive sensitizer and acid by exposure >

[(b) Radiation-sensitive sensitizer generating agent]

(b) The following compounds were used as the sensitizing radiation sensitizer generating agent.

B-1: a compound represented by the following formula (B-1)

B-2: A compound represented by the following formula (B-2)

[Absorbance measurement of component (b)] [

In Table 2, the component (b) and the sensitizer derived from the component (b) are shown together. Further, the sensitizer derived from the component (b) and the component (b) was prepared so as to be a cyclohexane solution of 0.0001 mass%, respectively. 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. When the measured value of the absorbance in the entire wavelength range of 300 nm or more and 450 nm or less is less than 0.01, it is evaluated as &quot; transparent &quot;, and when there is a slight difference in the wavelength in which the absorbance is 0.01 or more in the whole wavelength range, " 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) Radiation-sensitive acid generator]

(c) the following [C1] compound (first compound) and [C2] compound (second compound) were used as the radiation-sensitive acid generator.

(Acid generating compound)

In the present embodiment, the following [C1] compound, which is a compound having a smaller pKa of an acid generated in the [C1] compound (the first compound) and the [C2] compound (the second compound), was used as the acid generating compound.

C-1-1: A compound represented by the following formula (C-1-1)

C-1-2: A compound represented by the following formula (C-1-2)

C-1-3: A compound represented by the following formula (C-1-3)

C-1-4: A compound represented by the following formula (C-1-4)

(PKa of an acid generated from an acid generating compound ([C1] compound)

Table 4 shows the pKa (the logarithm value of the reciprocal of the acid dissociation constant of the acid) of the acid generated from these compounds with respect to the compounds (C-1-1) to (C-1-4).

(The energy that the acid generating compound ([C1] compound) releases when the cation is reduced to a radical)

Table 4 shows calculation results of the energy released when the cations in the compounds are reduced to radicals with respect to the compounds (C-1-1) to (C-1-4). Here, the energy was calculated from the energy difference between the positive ion and the radical, by calculating the energy level of each material by the B3LYP / LANL2DZ method after optimizing the structure of each cation and the radical.

(Acid diffusion control agent)

As the present embodiment, the following [C2] compounds (C-2-1 and C-2) which are compounds having a higher pKa of the acid generated in the [C1] compound (first compound) and the [C2] -4) was used as an acid diffusion controlling agent. C-2-1 to C-2-5 were used as the acid diffusion control agent of the comparative example.

C-2-1: A compound represented by the following formula (C-2-1) (having a radiation-sensitive property)

C-2-2: A compound represented by the following formula (C-2-2) (having no radiation-sensitive property)

C-2-3: A compound represented by the following formula (C-2-3) (having a radiation-sensitive property)

C-2-4: A compound represented by the following formula (C-2-4) (having a radiation-sensitive property)

C-2-5: A compound represented by the following formula (C-2-5) (having a radiation-sensitive property)

(PKa of the acid generated from the acid diffusion control agent ([C2] compound)

(C-2-1), (C-2-3), (C-2-4) and (C-2-5) The pKa (the logarithm value of the reciprocal of the acid dissociation constant of the acid) of the acid (anion moiety) is shown in Table 5.

(The energy released when the cation in the acid diffusion control agent ([C2] compound) is reduced to a radical)

The acid diffusion control agent having the radiation-sensitive properties of the above-mentioned compounds (C-2-1), (C-2-3), (C- 2-4) Table 5 shows the results of calculation of the energy released when the cation in the sample is reduced to the radical. Here, the energy was calculated from the energy difference between the positive ion and the radical, by calculating the energy level of each material by the B3LYP / LANL2DZ method after optimizing the structure of each cation and the radical.

(menstruum)

G-1: Propylene glycol monomethyl ether acetate

G-2: Ethyl lactate

[Example 1]

(C1) compound (C-1) as a radiation-sensitive acid generator, 100 parts by mass of the polymer (A-1), (b) 5 parts by mass of the radiation- -1) and 5.0 parts by mass of the [C2] compound (C-2-1), 4,300 parts by mass of the solvent (G-1) and 1,900 parts by mass of the (G-2) were mixed. Subsequently, the obtained mixed solution was filtered with a membrane filter having a pore diameter of 0.20 mu m to prepare a chemically amplified resist material (R-1).

[Examples 2 to 3 and Comparative Examples 1 to 10]

Chemically amplified resist materials (R-2) to (R-13) were produced in the same manner as in Example 1 except that each component of the type and compounding amount shown in Table 6 was used. "-" in the table indicates that the corresponding component is not added.

&Lt; Formation of resist pattern &

The adjusted chemically amplified resist material was spin-coated on a silicon wafer in "Clean Track ACT-8" manufactured by Tokyo Electron Co., Ltd. Then, PB was performed under the conditions of 110 ° C. for 60 seconds to form a resist material film having an average thickness of 50 nm did. 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 A / cm 2) manufactured by Hitachi Seisakusho Co., Ltd., and patterning was performed. As the patterning, a mask was used to form 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. After the irradiation of the electron beam, the following operations (1) to (3) were successively evaluated.

(Operation (1): no batch exposure)

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

(Operation (2): with a batch exposure (10 minutes))

After the irradiation of the electron beam, the whole surface of the resist material film was subjected to a batch exposure for 10 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-mentioned operation (1) to form a positive resist pattern.

(Operation (3): with a batch exposure (30 minutes))

After the irradiation of the electron beam, the entire surface of the resist material film was subjected to a batch exposure for 30 minutes 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-mentioned operation (1) to form a positive resist pattern.

<Evaluation>

The positive resist pattern thus formed was evaluated for sensitivity and nano-edge roughness according to the procedure described below.

[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 50 袖 C / cm 2 or less, and" B (poor) "when the optimum exposure amount was 50 袖 C / cm 2 or more. Table 7 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 of the line pattern is observed at arbitrary 20 points and the line portion 12 in the pattern formed on the base material (silicon wafer) 11, as shown in Figs. 7 and 8, &Quot; CD &quot; between the line width at the portion where the concavities and convexities most prominent along the transverse side face 12a of the front side face 12a and the design line width 150 nm were measured. 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 and" AA (very good) "when it is 12.0 nm or more and 15.0 nm or less and" B (bad) "when the average value I decided. The irregularities shown in Figs. 7 and 8 are exaggerated in actuality. The average value of? CD and the evaluation results of nano edge roughness are shown in Table 7.

As shown in Table 7, the radiation-sensitive [C1] compound and the [C2] compound containing both of the onium cations having an energy of emission of less than 5.0 eV when reduced to radicals were used as the radiation- It was confirmed that good sensitivity can be obtained without deterioration of the nano edge roughness even in the case where the UV total exposure amount is large. On the other hand, in the case of the comparative example in which the energy released when the compound is reduced to a radical of an onium cation of the [C1] compound or the [C2] compound is 5.0 eV or more, when the UV cumulative exposure dose is small, the deterioration of the nano- Although the sensitivity is increased, the nano edge roughness is deteriorated when the exposure amount is equal to or more than a constant exposure time such as 30 minutes of exposure time. Further, in the case of the comparative example using a compound having no radiation-sensitive properties as the acid diffusion control agent in place of the [C2] compound as the radiation-sensitive compound, it was confirmed that the degree of increase and decrease in the UV batch exposure was suppressed.

As described above, according to the chemically amplified resist material and the method for forming a resist pattern of the present invention, ionizing radiation such as EUV light, electron beam, and ion beam, or KrF excimer laser and ArF excimer laser, It is possible to exhibit excellent lithography performance while maintaining good sensitivity when radiation is used as pattern exposure light. The chemically amplified resist material can be suitably used for the resist pattern forming method.

1: semiconductor wafer
2, 12: resist pattern
3: Etching film
10: pattern substrate
11: substrate
12a: 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 any of the following components (a), (a) to (c), or both of the following components (a)
Wherein the component (a) or the component (c) comprises a first compound having a radiation-sensitive property and a second compound having a radiation-
Wherein the first compound comprises a first onium cation and a first anion and the second compound comprises a second onium cation and a second anion different from the first anion,
Wherein the first onium cation and the second onium cation each have an energy of less than 5.0 eV when they are reduced to a radical.
(a) irradiating a first radiation, which is radiation having a wavelength of 250 nm or shorter, and not irradiating a second radiation, which is radiation having a wavelength exceeding 250 nm, Sensitizer generator which generates a sensitizer and does not substantially generate the acid and the radiation-sensitive sensitizer when only the second radiation is irradiated without irradiating the first radiation,
(b) irradiates the first radiation and generates a radiation-sensitive sensitizer for absorbing the second radiation when the second radiation is not emitted, A radiation-sensitive sensitizer generator which does not substantially generate the radiation-sensitive sensitizer when irradiated only with radiation
(c) generating an acid when irradiating the first radiation and not irradiating the second radiation, and substantially when the second radiation is irradiated without irradiating the first radiation, Non-sensitizing radiation-sensitive acid generator The chemically amplified resist composition according to claim 1, wherein the total content of the first onium cation and the second onium cation to the total onium cation in the chemically amplified resist material is 80 mol% or more. 3. The chemically amplified resist composition according to claim 1 or 2, wherein the logarithm of the inverse number of the acid dissociation constant of the acid generated from at least one of the first compound and the second compound is 0 or less. The chemical amplification type resist composition according to any one of claims 1 to 3, wherein the (1) polymer component comprises a first polymer having a structural unit containing a group capable of generating a polar group by the action of an acid material. 5. The method of claim 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 a structural unit containing an 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 10% by mass or more and 30% by mass or less. A film forming step of forming a resist material film by using 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 material film with radiation having a wavelength of 250 nm or less,
A batch exposure step of irradiating the resist material film after the pattern exposure process with radiation having a wavelength exceeding 250 nm;
A baking step of heating the resist material film after the batch exposure step,
A developing step of bringing the resist material film after the baking step into contact with a developing solution
To form a resist pattern.

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