JP2011153087A - Precursor of acid-dissociative dissolution-inhibiting group, and cyclic compound having acid-dissociative dissolution-inhibiting group - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photoresist base material and a photoresist composition, having excellent coating solvent dissolvability, high transparency, high sensitivity, high microfabrication properties, high strength, and low outgas properties, and to provide a precursor of an acid-dissociative dissolution-inhibiting group constituting a part of a photoresist base material. <P>SOLUTION: The photoresist composition includes a compound represented by formula (1) (wherein, R is a group having a benzenecarboxylic acid ester site and an aliphatic condensed ring site; R<SP>1</SP>is a group such as hydroxy and alkoxy; and R<SP>2</SP>is hydrogen). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an acid dissociable, dissolution inhibiting group precursor and a cyclic compound having an acid dissociable, dissolution inhibiting group. More specifically, the present invention relates to a photoresist base material composed of the above cyclic compound used in the electrical / electronic field and optical field such as semiconductor, and more particularly to a photoresist base material for ultrafine processing.

  Lithography using extreme ultraviolet (EUV) or electron beam is useful as a high-productivity, high-resolution microfabrication method in the production of semiconductors, etc., and develops high-sensitivity, high-resolution photoresists for use in it. It is requested to do. It is indispensable to improve the sensitivity of the photoresist used in these lithography from the viewpoint of the productivity and resolution of the desired fine pattern.

  Examples of the photoresist used at the time of ultrafine processing using extreme ultraviolet light include chemically amplified polyhydroxystyrene-based photoresists used at the time of ultrafine processing using a known KrF laser. It is known that this resist can be finely processed up to about 50 nm. However, with this resist, the most important line edge roughness can be achieved even if high sensitivity and low resist outgas can be achieved to a certain extent by creating a pattern of 50 nm or less, which is the greatest merit of ultra-fine processing using extreme ultraviolet light. Since it cannot be reduced, it cannot be said that the original performance of extreme ultraviolet light has been sufficiently brought out. Against this background, it has been demanded to develop a higher performance photoresist.

  In response to this demand, for example, Patent Document 1 discloses a method using a chemically amplified positive photoresist having a higher concentration of photoacid generator as compared with other resist compounds. However, in this method, in the examples, a substrate comprising a terpolymer consisting of hydroxystyrene / styrene / t-butyl acrylate, at least about 5% by weight of di (t-butylphenyl) iodonium ortho-tri in total solids. Regarding the photoacid generator composed of fluoromethylsulfonate, the photoresist composed of tetrabutylammonium hydroxide lactate and ethyl lactate, specific results such as production line width when using extreme ultraviolet light were not exemplified . Therefore, for these results, it was considered that the processing up to 100 nm exemplified in the case of using an electron beam was the limit from the viewpoint of line edge roughness. It is presumed that the main cause of this is that the aggregate of the polymer compounds used as the base material or the three-dimensional shape of each polymer compound molecule is large and affects the production line width and the surface roughness.

  Patent Document 2 discloses a calix resorcinalene compound as a high-sensitivity, high-resolution photoresist material. However, a novel low molecular weight organic compound that is in an amorphous state at room temperature has been demanded. At this time, improvement in various performances such as improvement in etching resistance, which is a problem in the semiconductor manufacturing process, has been demanded in parallel. Moreover, since the photoresist base material is dissolved in a solvent in the current semiconductor manufacturing process and proceeds to a film forming process, high solubility in a coating solvent has been demanded.

Patent Document 3 discloses calix resorcinalene compounds, but these compounds are considered to have insufficient solubility and do not describe use as a photoresist base material.
Patent Document 4 discloses a specific low molecular weight compound with reduced basic impurities. However, there are problems such as insufficient solubility and contamination by outgas derived from an acid dissociable dissolution inhibiting group. It was.

JP 2002-055557 A JP 2004-191913 A US Pat. No. 6,093,517 Japanese Patent Laying-Open No. 2005-075757

An object of the present invention is to provide a photoresist base material and a photoresist composition that are excellent in coating solvent solubility, and have high transparency, high sensitivity, high fine workability, high strength, and low outgassing properties.
An object of the present invention is to provide an acid dissociable, dissolution inhibiting group precursor constituting a part of a photoresist base material.

According to the present invention, the following compounds and the like are provided.
1. A compound represented by the following formula (1).
(In formula, R is group represented by either of following formula (2)-(4).
R ¹ is a hydroxyl group, a substituted or unsubstituted linear alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted branched alkoxy group having 3 to 12 carbon atoms, or a substituted or unsubstituted cyclic group having 3 to 20 carbon atoms. An alkoxy group, a substituted or unsubstituted aryloxyl group having 6 to 10 carbon atoms, an alkoxyalkoxy group, a siloxy group, or a group in which these groups and a divalent group are bonded;
The divalent group includes a substituted or unsubstituted alkyleneoxy group, a substituted or unsubstituted aryleneoxy group, a substituted or unsubstituted silyleneoxy group, a group in which two or more of these groups are bonded, or a group thereof. A group having an ester bond, a carbonate ester bond or an ether bond.
R ² is a hydrogen atom, a group represented by R ¹ , a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, or a cyclic group having 3 to 20 carbon atoms. An aliphatic hydrocarbon group, an aromatic group having 6 to 10 carbon atoms, or a group containing an oxygen atom.
A plurality of R, R ¹ and R ² in the formula (1) may be the same or different.
(In the formula, Ar is selected from a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, a group in which two or more substituted or unsubstituted arylene groups having 6 to 10 carbon atoms are combined, or an alkylene group and an ether bond. A combination of one or more of the above and a substituted or unsubstituted arylene group having 6 to 10 carbon atoms,
In the case of having a substituent, the substituent is a bromine atom, a fluorine atom, a nitrile group, or an alkyl group having 1 to 10 carbon atoms.
R ³ is a group represented by the formula (5).
R ^{3 ′} -L—O— (5)
(L is one in which one or two or more selected from the groups represented by the following formulas (6) to (8) are linked, and takes any linkage order. Formulas (6) to ( When a plurality of groups represented by 8) are included, they may be the same or different.
(In the formula, each of R ^{4 ′ to} R ^{7 ′} is a hydrogen atom, an alkyl group or a heteroatom-containing alkyl group, and is bonded to an alicyclic structure-containing group represented by the following formula (i) to form a cyclic structure. Or a plurality of R ^{4 ′ to} R ^{7 ′} may be bonded to each other to form a cyclic structure.)
R ^{3 ′} is an alicyclic structure-containing group represented by the following formula (i).
(In the formula, Z represents an alicyclic structure having 5 to 20 carbon atoms which may have a hetero atom, and R ⁸ represents a substituted or unsubstituted carbon atom which may have a hetero atom or a cyclic structure. 10 is a divalent hydrocarbon group of 10 to 10, and R ⁹ is a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon A branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 15 carbon atoms, an alkoxy group, and an aryloxy group , Alkoxyalkyl groups, aryloxyalkyl groups, silyl groups, or these groups and divalent groups (substituted or unsubstituted alkylene groups, substituted or unsubstituted arylene groups, substituted or unsubstituted silylene groups, these groups Is 2 or more A group formed by combining these groups or a group formed by combining these groups with an ester group, a carbonate ester group or an ether group), and p and q are each independently an integer of 0 or more. a plurality of R ⁸ is also the same, or different, even more R ⁹ may be the same or different.)
R ⁴ and R ⁵ are each a hydrogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, and a substituted group. Alternatively, it is an unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a group obtained by combining two or more of these groups.
A ¹ is an alkylene group, an ether bond, a group in which two or more alkylene groups are combined, or a group in which one or more alkylene groups and one or more ether bonds are combined.
x is an integer of 1 to 5, y is 0 to 3, and z is an integer of 0 to 4.
A plurality of R ³ , R ⁴ , R ⁵ , Ar, A ¹ , L, x, y, and z may be the same or different. ))
2. A compound represented by R ¹⁰¹ -X,
R ¹⁰¹ is a group represented by the following formula (11),
A compound in which X is a halogen atom, a hydroxyl group, an aryloxy group, or a (meth) acrylic acid ester group represented by the following formula (15).
(In Formula (11),
n is an integer of 0 or 1, respectively.
R ^a is a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon number 3 A cyclic aliphatic hydrocarbon group of -20, or a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms.
R ^b is an alicyclic structure-containing group represented by the formula (i).
(In the formula, Z represents an alicyclic structure having 5 to 20 carbon atoms which may have a hetero atom, and R ⁸ represents a substituted or unsubstituted carbon atom which may have a hetero atom or a cyclic structure. 10 is a divalent hydrocarbon group of 10 to 10, and R ⁹ is a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon A branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 15 carbon atoms, an alkoxy group, and an aryloxy group , Alkoxyalkyl groups, aryloxyalkyl groups, silyl groups, or these groups and divalent groups (substituted or unsubstituted alkylene groups, substituted or unsubstituted arylene groups, substituted or unsubstituted silylene groups, these groups Is 2 or more A group formed by combining these groups or a group formed by combining these groups with an ester group, a carbonate ester group or an ether group), and p and q are each independently an integer of 0 or more. The plurality of R ⁸ may be the same or different, and the plurality of R ⁹ may be the same or different.)
R ^c is a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon number 3 A cyclic aliphatic hydrocarbon group of -20, or a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms.
(In the above formula (15), R ^d is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.)
3. 2. The compound according to 1, wherein Z has an adamantyl skeleton.
4). 4. The compound according to 1 or 3, wherein R ^{3 ′} is a group represented by formula (ii) or (iii).
(R ⁸ , R ⁹ , p and q are the same as in formula (i).)
5. 5. The compound according to 4, wherein R ⁹ is a group represented by formula (iv).
(R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hetero element-containing alkyl group, an aromatic group having 6 to 18 carbon atoms, or a hetero element-containing aromatic group, and a plurality of R ¹⁰ are the same or different. R ¹¹ is a carbon atom substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms, silicon, oxygen, sulfur, nitrogen or a halogen-containing group. An alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 18 carbon atoms substituted by a group containing silicon, oxygen, sulfur, nitrogen or halogen, and r is an integer of 1 to 4.
6). 4. The compound according to 1 or 3, wherein Z has a norbornyl skeleton.
7). 7. The compound according to 1 or 6, wherein R ^{3 ′} is a group represented by formula (v).
(R ⁸ , R ⁹ , p and q are the same as in formula (i).)
8). 8. The compound according to 7, wherein R ⁹ is a group represented by formula (iv).
(R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hetero element-containing alkyl group, an aromatic group having 6 to 18 carbon atoms, or a hetero element-containing aromatic group, and a plurality of R ¹⁰ are the same or different. R ¹¹ is a carbon atom substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms, silicon, oxygen, sulfur, nitrogen or a halogen-containing group. An alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 18 carbon atoms substituted by a group containing silicon, oxygen, sulfur, nitrogen or halogen, and r is an integer of 1 to 4.
The compound according to 9.1, wherein R is a group represented by the formula (11).
10. A photoresist composition comprising the compound according to any one of 10.1 and 3-9 and a solvent.
11. 11. The photoresist composition according to 10, containing a photoacid generator.
12 The photoresist composition according to 10 or 11, comprising a basic organic compound as a quencher.
A fine processing method using the photoresist composition according to any one of 13.10 to 12.
14. A semiconductor device manufactured by the microfabrication method described in 14.13.
A device comprising the semiconductor device according to 15.14.

  According to the present invention, a photoresist base material and a photoresist composition that are excellent in coating solvent solubility, high transparency, high sensitivity, high fine workability, high strength, and low outgassing properties, and a part of the photoresist base material The acid dissociable, dissolution inhibiting group precursor that constitutes can be provided.

2 is a ¹ H-NMR spectrum of a cyclic compound (A) produced in Synthesis Example 1. 1 is a ¹ H-NMR spectrum of a compound produced in Example 1. 2 is a ¹ H-NMR spectrum of a compound produced in Example 2. 2 is a ¹ H-NMR spectrum of a compound produced in Example 3. ¹ is a ¹ H-NMR spectrum of a compound produced in Example 4. ¹ is a ¹ H-NMR spectrum of a compound produced in Example 5. ¹ is a ¹ H-NMR spectrum of a compound produced in Example 6. ¹ is a ¹ H-NMR spectrum of a compound produced in Example 7. ¹ is a ¹ H-NMR spectrum of a compound produced in Example 8. ¹ is a ¹ H-NMR spectrum of a compound produced in Example 9. ¹ is a ¹ H-NMR spectrum of a compound produced in Example 10. ¹ is a ¹ H-NMR spectrum of a compound produced in Example 11. ¹ is a ¹ H-NMR spectrum of a compound produced in Example 12. 2 is a ¹ H-NMR spectrum of a compound produced in Example 33. ¹ is a ¹ H-NMR spectrum of a compound produced in Example 34.

The 1st compound of this invention is represented by Formula (1).
In the formula, R is a group represented by any of the following formulas (2) to (4).
R ¹ represents a hydroxyl group, a substituted or unsubstituted linear alkoxy group having 1 to 20 carbon atoms (preferably 1 to 6), a substituted or unsubstituted branched alkoxy group having 3 to 12 carbon atoms, a substituted or unsubstituted group. A cyclic alkoxy group having 3 to 20 carbon atoms, a substituted or unsubstituted aryloxyl group having 6 to 10 carbon atoms, an alkoxyalkoxy group, a siloxy group, or a group in which these groups are bonded to a divalent group.

  The divalent group includes a substituted or unsubstituted alkyleneoxy group, a substituted or unsubstituted aryleneoxy group, a substituted or unsubstituted silyleneoxy group, a group in which two or more of these groups are bonded, or a group thereof. A group having an ester bond, a carbonate ester bond or an ether bond.

R ² is a hydrogen atom, a group represented by R ¹ , a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, or a cyclic group having 3 to 20 carbon atoms. An aliphatic hydrocarbon group, an aromatic group having 6 to 10 carbon atoms, or a group containing an oxygen atom.
A plurality of R, R ¹ and R ² in the formula (1) may be the same or different.
In the formula, Ar is a substituted or unsubstituted arylene group having 6 to 10 carbon atoms (for example, a phenylene group), a group obtained by combining two or more substituted or unsubstituted arylene groups having 6 to 10 carbon atoms, or an alkylene group. And a combination of one or more selected from ether bonds and a substituted or unsubstituted arylene group having 6 to 10 carbon atoms,
In the case of having a substituent, the substituent is a bromine atom, a fluorine atom, a nitrile group, or an alkyl group having 1 to 10 carbon atoms.

R ³ is a group represented by the formula (5).
R ^{3 ′} -L—O— (5)
L is one to which one or two or more selected from groups represented by the following formulas (6) to (8) are connected, and takes an arbitrary connection order. When a plurality of groups represented by formulas (6) to (8) are included, they may be the same or different.
In the formula, each of R ^{4 ′ to} R ^{7 ′} is a hydrogen atom, an alkyl group, or a heteroatom-containing alkyl group, and is bonded to an alicyclic structure-containing group represented by the following formula (i) to form a cyclic structure. A plurality of R ^{4 ′ to} R ^{7 ′} may be bonded to each other to form a cyclic structure. Preferably, R ^{4 ′ to} R ^{7 ′} are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

R ^{3 ′} is an alicyclic structure-containing group represented by the following formula (i).
In formula, Z is a C5-C20 alicyclic structure which may have a hetero atom.
R ⁸ is a substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms which may have a hetero atom or a cyclic structure, and preferably an alkyl group having 1 to 6 carbon atoms.
R ⁹ represents a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, Substituted or unsubstituted C3-C20 cyclic aliphatic hydrocarbon group, substituted or unsubstituted C6-C15 aromatic group, alkoxy group, aryloxy group, alkoxyalkyl group, aryloxyalkyl group, silyl group Or these groups and a divalent group (a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted silylene group, a group formed by bonding two or more of these groups, or these And a group formed by bonding an ester group, a carbonic acid ester group, or an ether group).
p and q are each independently an integer of 0 or more, preferably 1 to 2, and more preferably 1.
A plurality of R ⁸ may be the same or different, and a plurality of R ⁹ may be the same or different.

R ³ may be R ¹⁰¹ —O— (R ¹⁰¹ is as described later).

R ⁴ and R ⁵ are each a hydrogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, and a substituted group. Alternatively, it is an unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a group obtained by combining two or more of these groups.

A ¹ is an alkylene group, an ether bond, a group in which two or more alkylene groups are combined, or a group in which one or more alkylene groups and one or more ether bonds are combined. x is an integer of 1 to 5, preferably 1. y is an integer of 0 to 3, preferably 1. z is an integer of 0 to 4, preferably 0.
A plurality of R ³ , R ⁴ , R ⁵ , Ar, A ¹ , L, x, y, and z may be the same or different.

As the linear aliphatic hydrocarbon (or alkyl) group having 1 to 20 carbon atoms, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and the like are preferable.
As the branched aliphatic hydrocarbon (or alkyl) group having 3 to 12 carbon atoms, a t-butyl group, an iso-propyl group, an iso-butyl group, a 2-ethylhexyl group, and the like are preferable.
As the cyclic aliphatic hydrocarbon (or alkyl) group having 3 to 20 carbon atoms, a cyclohexyl group, norbornyl group, adamantyl group, biadamantyl group, diadamantyl group and the like are preferable.
As the aromatic group having 6 to 10 carbon atoms, a phenyl group, a naphthyl group, and the like are preferable.
As the alkoxyalkyl group, a methoxymethyl group, an ethoxymethyl group, an adamantyloxymethyl group and the like are preferable.
As the silyl group, a trimethylsilyl group, a t-butyldimethylsilyl group and the like are preferable.

In addition, each of the above groups may have a substituent, specifically, an alkyl group such as a methyl group or an ethyl group, a ketone group, an ester bond, an alkoxy group, a nitrile group, a nitro group, or a hydroxyl group. Can be mentioned.
As a linear alkoxy group, a branched alkoxy group, a cyclic alkoxy group, an aryloxyl group, an alkoxyalkoxy group, a siloxy group, an alkyleneoxy group, an aryleneoxy group, and a silyleneoxy group, the above corresponding group is bonded to an oxygen atom. And a divalent group.
Examples of the arylene group and the alkylene group include the corresponding divalent groups.

Examples of the alicyclic structure having 5 to 20 carbon atoms that may have a hetero atom in the above formula (i) include a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, a cyclooctyl ring, a cyclononyl ring, a cyclodecanyl ring, and a decaryl ring. (Perhydronaphthalene ring), norbornyl ring, bornyl ring, isobornyl ring, adamantyl ring, bicyclo [2.2.1] heptane, tricyclo [5.2.1.0 ^2,6 ] decane ring, tetracyclo [4.4 0.1 ^{2, 5} . 17, ¹⁰ ] monocyclic or polycyclic structures such as dodecane ring, γ-butyrolactyl ring, 4-oxa-tricyclo [4.2.1.0 ^3,7 ] nonane-5-o, 4,8-dioxa- Monocyclic or polycyclic lactones such as tricyclo [4.2.1.0 ^3,7 ] nonane-5-one, 4-oxa-tricyclo [4.3.1.1 ^3,8 ] undecan-5-one , Tetrahydrofuran, tetrahydropyran, monocyclic or polycyclic ethers such as 1,4-dioxane, and perfluoro compounds thereof, and adamantyl ring, norbornyl ring, and bicyclo [2.2.1] heptane ring are preferable. .

Specific examples of the substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms which may have a heteroatom in the above formula (i) include straight chain such as methylene group, ethylene group and trimethylene group Or a branched alkylene group, those perfluoro forms, etc. are mentioned.
Specific examples of the substituted or unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms which may have a cyclic structure include monocyclic such as cyclopropane, cyclopentane and cyclohexane ring, adamantyl ring and damantyl ring , Norbornyl ring, bicyclo [2.2.1] heptane ring and the like, and perfluoro compounds thereof.

  The C5-C20 alicyclic structure which may have the said hetero atom, the C1-C10 substituted or unsubstituted bivalent hydrocarbon group which may have a hetero atom may have. Specific examples of the hetero atom include a nitrogen atom, a sulfur atom, and an oxygen atom.

For example, R ^{3 ′} is a group represented by (ii), (iii) or (v).
In the formula, R ⁸ , R ⁹ , p and q are the same as those in the formula (i), and preferable examples thereof include those mentioned in the formula (i).

For example, R ⁹ in formulas (ii), (iii), and (v) has a structure represented by the following formula (iv).
R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hetero element-containing alkyl group, an aromatic group having 6 to 18 carbon atoms, or a hetero element-containing aromatic group, and a plurality of R ¹⁰ are the same or different. May be. Preferably it is hydrogen.
R ¹¹ is substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms, silicon, oxygen, sulfur, nitrogen or a group containing halogen. Or an aromatic group having 6 to 18 carbon atoms substituted by a group containing 1 to 10 carbon atoms or a group containing silicon, oxygen, sulfur, nitrogen or halogen. Examples of the group containing silicon, oxygen, sulfur, nitrogen, or halogen include alkylcarbonyl, (alkoxyl group, aryloxy group), nitro, and alkyl halide. Examples of the aromatic group having 6 to 18 carbon atoms include phenyl, naphthyl (and their alkylcarbonyl, (alkoxyl group, aryloxy group), nitro, halide). Preferably carbon number of an alkyl group is 1-4. The halogen is preferably fluorine.
r is an integer of 1-4.

Specific examples of R ^{3 ′} include the following groups.
In the formula, the dotted line indicates the coupling position.

As described below, the first compound can be used not only as a photoresist base material but also for other applications.
As other applications, for example, another compound may be used as a photoresist base material, and the first compound may be used as an additive.

The second compound of the present invention is represented by R ¹⁰¹ -X. R ¹⁰¹ is a group represented by the following formula (11).
In formula (11), n is an integer of 0 or 1, respectively. R ^a is a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon number 3 A cyclic aliphatic hydrocarbon group of -20, or a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms. R ^a is preferably an alkyl group having 1 to 6 carbon atoms.

R ^b is an alicyclic structure-containing group represented by the above formula (i).
R ^c is a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon number 3 A cyclic aliphatic hydrocarbon group of -20, or a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms. R ^c is preferably an alkyl group having 1 to 6 carbon atoms.

X is a halogen atom, a hydroxyl group, an aryloxy group, or a (meth) acrylic acid ester group represented by the following formula (15).
In the above formula (15), R ^d is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.

  Preferable examples of each group include those listed above.

R ^b is represented by the formula (i), and the same examples as described above can be preferably mentioned. Specific examples of R ^b include the following groups.

As described below, the second compound can be used not only as a raw material for a photoresist base material but also for other uses.
As other applications, for example, it may be used as an additive for a photoresist composition.
Moreover, the compound manufactured using the second compound as described below can be used not only as a photoresist base material but also for other uses.
As other applications, for example, a compound produced using a second compound may be used as an additive using another compound as a photoresist base material.

  The third compound of the present invention is a compound in which only R in formula (1) is represented by formula (11).

  The second compound (acid dissociable, dissolution inhibiting group precursor) can be produced, for example, by the following production method 1 or production method 2.

Manufacturing method 1
The raw material alcohol R ^b —OH and, for example, bromoacetic acid (A1) are stirred in methylene chloride as a solvent in the presence of 4-dimethylaminopyridine, and dicyclohexylcarbodiimide as a dehydrating condensing agent is slowly added at 0 ° C. Then, it is made to react by stirring at 0 degreeC, cooling with an ice bath. The resulting white solid (urea of dicyclohexylcarbodiimide) is removed by filtration, followed by post-treatment and purification, and the second compound, bromoacetate ester (B), is obtained.
(In the formula, X is Br.)

Manufacturing method 2
The raw material alcohol R ^b —OH and, for example, bromoacetic acid bromide (A2) are cooled to 0 ° C. in dehydrated tetrahydrofuran, dehydrated pyridine is added dropwise, and the mixture is heated to room temperature and stirred to react. Post-treatment and purification are performed to obtain a bromoacetic acid ester (B) as the second compound.
(In the formula, X is Br.)

In the above production methods 1 and 2, tetrahydrofuran and methylene chloride are used as the solvent, respectively, but the present invention is not limited thereto, and other solvents may be used as long as the reactant and the raw material are dissolved.
Examples of other solvents include halogen-containing solvents and oxygen-containing solvents.

  In the above production methods 1 and 2, -dimethylaminopyridine and pyridine are used as the base of the reactant, respectively, but the present invention is not limited thereto, and other organic bases and inorganic bases may be used.

  In the above production method 1, dicyclohexylcarbodiimide is used as the dehydrating condensing agent, but the present invention is not limited to this, and other conventionally known condensing agents may be used.

  The reaction temperature is preferably −100 ° C. to 100 ° C., and particularly preferably −50 ° C. to 50 ° C.

  The first compound can be obtained by reacting the corresponding calix resorcinarene with one or more and five or less of the second compound (acid dissociable, dissolution inhibiting group precursor). The third compound is obtained by reacting one or more kinds of the second compound (acid dissociable, dissolution inhibiting group precursor) with a corresponding calixresorcinarene compound containing, for example, —COOH in R in the formula (1). Can be obtained.

  As described above, the first compound can be obtained by reacting the second compound with the corresponding calix resorcinarene compound, and the production method is specifically exemplified below.

Manufacturing method 1 '
Add corresponding calixresorcinarene compound, second compound, sodium carbonate, dimethylformamide as solvent, heat reaction at 80 ° C under nitrogen stream, and then filter the precipitate that is generated by adding the reaction solution to water Can be obtained by purification.

Manufacturing method 2 '
Corresponding calix resorcinarene compound, second compound, sodium hydride, tetrahydrofuran as a solvent is added and reacted at 0 ° C under nitrogen stream, then the reaction solution is poured into water and the resulting precipitate is filtered and purified Can be obtained.

  Further, as described above, the third compound can be obtained by reacting the second compound with a calixresorcinarene compound containing, for example, —COOH in R in the formula (1). The manufacturing method is illustrated.

Manufacturing method 1 ''
After adding calixresorcinalene compound containing -COOH to R in formula (1), the second compound, N-methylpyrrolidone as solvent, adding triethylamine and DBU at room temperature under nitrogen flow, and reacting. The precipitate produced by introducing the reaction solution into water can be purified by filtration.

Manufacturing method 2 ''
In formula (1), calixresorcinalene compound containing -COOH in R, second compound, sodium hydrogen carbonate, N-methylpyrrolidone as a solvent was added and reacted at 50 degrees under a nitrogen stream, then reaction A precipitate formed by putting the solution into water can be purified by filtration.

In the above production methods 1 ′, 2 ′, 1 ′ ′, 2 ′ ′, dimethylformamide, tetrahydrofuran and N-methylpyrrolidone are used as the solvent, respectively, but the present invention is not limited thereto. A solvent may be used.
Examples of other solvents include halogen-containing solvents, oxygen-containing solvents, and aromatic solvents (toluene).

In the above production methods 1 ′, 2 ′, 1 ′ ′, 2 ′ ′, sodium carbonate, sodium hydrogen carbonate, sodium hydride, triethylamine, and DBU are used as the base of the reactant, but not limited thereto. An organic base or an inorganic base may be used.
The reaction temperature is preferably −100 ° C. to 100 ° C., particularly preferably −50 ° C. to 80 ° C.

The photoresist composition of the present invention contains the first compound and the second compound (photoresist substrate) of the present invention. The content of the photoresist base material is preferably 50 to 99.9% by weight, more preferably 75 to 95% by weight in the entire composition excluding the solvent.
When used as a photoresist substrate, the photoresist substrate of the present invention may be a single compound or a mixture of two or more.

  Examples of the solvent used in the photoresist composition of the present invention include ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like. Ethylene glycol monoalkyl ethers; propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate; propylene glycols such as propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether Monoalkyl ethers; methyl lactate, ethyl lactate (E Lactic acid esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate and ethyl propionate (PE); methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Other esters such as methyl ethoxypropionate and ethyl 3-ethoxypropionate; aromatic hydrocarbons such as toluene and xylene; ketones such as 2-heptanone, 3-heptanone, 4-heptanone and cyclohexanone; tetrahydrofuran, dioxane Examples thereof include cyclic ethers such as lactones and lactones such as γ-butyrolactone, but are not particularly limited. These solvents can be used alone or in combination of two or more.

  The components other than the solvent in the composition, that is, the amount of the photoresist solid content, is preferably set to an amount suitable for forming a desired film thickness of the photoresist layer. Specifically, it is generally 0.1 to 50% by weight of the total weight of the photoresist composition, but it can be defined according to the type of base material and solvent used, or the desired film thickness of the photoresist layer. . The solvent is preferably blended in an amount of 50 to 99.9% by weight in the entire composition.

  The photoresist composition of the present invention does not require an additive particularly when the substrate molecule contains a chromophore active against EUV and / or electron beam and exhibits the ability as a photoresist alone. When it is necessary to enhance the performance (sensitivity) as a photoresist, a photoacid generator (PAG) or the like is generally included as a chromophore as necessary.

The photoacid generator is not particularly limited, and those proposed as acid generators for chemically amplified resists can be used.
Examples of such acid generators include onium salt acid generators such as iodonium salts and sulfonium salts, oxime sulfonate acid generators, bisalkyl or bisarylsulfonyldiazomethanes, and diazomethanes such as poly (bissulfonyl) diazomethanes. There are various known acid generators, nitrobenzyl sulfonate acid generators, imino sulfonate acid generators, disulfone acid generators, and the like.

Examples of the onium salt acid generator include acid generators represented by the following formula (a-0).
[Wherein, R ⁵¹ represents a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group; R ⁵² represents a hydrogen atom, a hydroxyl group, a halogen atom, linear or A branched alkyl group, a linear or branched halogenated alkyl group, or a linear or branched alkoxy group; R ⁵³ is an optionally substituted aryl group; u '' Is an integer of 1 to 3. ]

In the formula (a-0), R ⁵¹ represents a linear, branched or cyclic alkyl group, or a linear, branched or cyclic fluorinated alkyl group.
The linear or branched alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.
The cyclic alkyl group preferably has 4 to 12 carbon atoms, more preferably 5 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms.
The fluorinated alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms. The fluorination rate of the fluorinated alkyl group (ratio of the number of substituted fluorine atoms to the total number of hydrogen atoms in the alkyl group) is preferably 10 to 100%, more preferably 50 to 100%, particularly hydrogen. Those in which all atoms are substituted with fluorine atoms are preferred because the strength of the acid is increased.
R ⁵¹ is most preferably a linear alkyl group or a fluorinated alkyl group.

R ⁵² represents a hydrogen atom, a hydroxyl group, a halogen atom, a linear, branched or cyclic alkyl group, a linear or branched halogenated alkyl group, or a linear or branched alkoxy group.
In R ⁵² , examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom, and a fluorine atom is preferable.
In ^R52 , the alkyl group is linear or branched, and the carbon number thereof is preferably 1 to 5, more preferably 1 to 4, and most preferably 1 to 3.
In R ⁵² , the halogenated alkyl group is a group in which part or all of the hydrogen atoms in the alkyl group are substituted with halogen atoms. Examples of the alkyl group herein are the same as the “alkyl group” in R ⁵² . Examples of the halogen atom to be substituted include the same as those described above for the “halogen atom”. In the halogenated alkyl group, it is desirable that 50 to 100% of the total number of hydrogen atoms are substituted with halogen atoms, and it is more preferable that all are substituted.
In R ⁵² , the alkoxy group is linear or branched, and the carbon number thereof is preferably 1 to 5, more preferably 1 to 4, and most preferably 1 to 3.
Of these, R ⁵² is preferably a hydrogen atom.

R ⁵³ is an aryl group which may have a substituent, and examples of the structure of the basic ring (matrix ring) excluding the substituent include a naphthyl group, a phenyl group, an anthracenyl group, and the like. From the viewpoint of absorption of exposure light such as ArF excimer laser, a phenyl group is desirable.
Examples of the substituent include a hydroxyl group and a lower alkyl group (straight or branched chain, preferably having 5 or less carbon atoms, particularly preferably a methyl group).
As the aryl group for R ⁵³ , those having no substituent are more preferable.

  u ″ is an integer of 1 to 3, preferably 2 or 3, and particularly preferably 3.

Preferable examples of the acid generator represented by the formula (a-0) include those represented by the following chemical formula.

The acid generator represented by the formula (a-0) can be used alone or in combination of two or more.
Examples of other onium salt-based acid generators represented by the formula (a-0) include compounds represented by the following formula (a-1) or (a-2).
[Wherein, R ¹ ″ to R ³ ″, R ⁵ ″, R ⁶ ″ each independently represents a substituted or unsubstituted aryl group or an alkyl group; R ⁴ ″ represents linear, branched or cyclic Represents an alkyl group or a fluorinated alkyl group; at least one of R ¹ ″ to R ³ ″ represents an aryl group, and at least one of R ⁵ ″ and R ⁶ ″ represents an aryl group.]

In formula (a-1), R ¹ ″ to R ³ ″ each independently represents a substituted or unsubstituted aryl group or alkyl group. At least one of R ¹ ″ to R ³ ″ represents a substituted or unsubstituted aryl group. Of R ¹ ″ to R ³ ″, two or more are preferably substituted or unsubstituted aryl groups, and most preferably all of R ¹ ″ to R ³ ″ are substituted or unsubstituted aryl groups.

The aryl group for R ¹ ″ to R ³ ″ is not particularly limited, and is, for example, an aryl group having 6 to 20 carbon atoms, in which part or all of the hydrogen atoms are alkyl or alkoxy. It may or may not be substituted with a group, a halogen atom or the like. The aryl group is preferably an aryl group having 6 to 10 carbon atoms because it can be synthesized at a low cost. Specific examples include a phenyl group and a naphthyl group.

The alkyl group that is a substituent of the aryl group is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group.
The alkoxy group that is a substituent of the aryl group is preferably an alkoxy group having 1 to 5 carbon atoms, and most preferably a methoxy group or an ethoxy group.
The halogen atom that is a substituent of the aryl group is preferably a fluorine atom.

The alkyl group for R 1 ^{"~R 3",} is not particularly limited, for example, a straight, include branched or cyclic alkyl group. It is preferable that it is C1-C5 from the point which is excellent in resolution. Specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an n-pentyl group, a cyclopentyl group, a hexyl group, a cyclohexyl group, a nonyl group, and a decanyl group. A methyl group is preferable because it is excellent in resolution and can be synthesized at low cost.
Among these, it is most preferable that all of R ¹ ″ to R ³ ″ are phenyl groups.

R ⁴ ″ represents a linear, branched or cyclic alkyl group or a fluorinated alkyl group.
The linear or branched alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms.
The cyclic alkyl group is a cyclic group as indicated by R ¹ ″ and preferably has 4 to 15 carbon atoms, more preferably 4 to 10 carbon atoms, and more preferably 6 carbon atoms. Most preferably, it is -10.
The fluorinated alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and most preferably 1 to 4 carbon atoms. Also. The fluorination rate of the fluorinated alkyl group (ratio of fluorine atoms in the alkyl group) is preferably 10 to 100%, more preferably 50 to 100%, and in particular, all hydrogen atoms are substituted with fluorine atoms. Since the strength of the acid is increased, it is preferable.
R ⁴ ″ is most preferably a linear or cyclic alkyl group or a fluorinated alkyl group.

In formula (a-2), R ⁵ ″ and R ⁶ ″ each independently represents a substituted or unsubstituted aryl group or alkyl group. At least one of R ⁵ ″ and R ⁶ ″ represents a substituted or unsubstituted aryl group. All of R ⁵ ″ and R ⁶ ″ are preferably substituted or unsubstituted aryl groups.
Examples of the substituted or unsubstituted aryl group for R ⁵ ″ to R ⁶ ″ include the same as the substituted or unsubstituted aryl group for R ¹ ″ to R ³ ″.
Examples of the alkyl group for R ⁵ ″ to R ⁶ ″ include the same as the alkyl group for R ¹ ″ to R ³ ″.
Among these, it is most preferable that all of R ⁵ ″ to R ⁶ ″ are phenyl groups.
"As ^{R 4} in the formula (a-1)" ^{R 4} in the formula (a-2) include the same as.

  Specific examples of the onium salt acid generators represented by formulas (a-1) and (a-2) include diphenyliodonium trifluoromethanesulfonate or nonafluorobutanesulfonate, bis (4-tert-butylphenyl) iodonium. Trifluoromethane sulfonate or nonafluorobutane sulfonate, triphenylsulfonium trifluoromethane sulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, tri (4-methylphenyl) sulfonium trifluoromethane sulfonate, its heptafluoropropane sulfonate or its Nonafluorobutanesulfonate, dimethyl (4-hydroxynaphthyl) sulfonium trifluoromethanesulfonate, its heptafluoropro Sulfonate or its nonafluorobutane sulfonate, monophenyldimethylsulfonium trifluoromethane sulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, diphenylmonomethylsulfonium trifluoromethane sulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, (4-methylphenyl) diphenylsulfonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, Bird (4 tert-butyl) phenylsulfonium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, diphenyl (1- (4-methoxy) naphthyl) sulfonium trifluoromethanesulfonate, its heptafluoropropanesulfonate or its nonafluorobutane Examples include sulfonates. In addition, onium salts in which the anion portion of these onium salts is replaced with methanesulfonate, n-propanesulfonate, n-butanesulfonate, or n-octanesulfonate can also be used.

Moreover, the onium salt type acid generator which replaced the anion part by the anion part represented by the following formula (a-3) or (a-4) in the said formula (a-1) or (a-2) is also used. (The cation moiety is the same as (a-1) or (a-2)).
[Wherein X ″ represents an alkylene group having 2 to 6 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom; Y ″ and Z ″ each independently represent at least one hydrogen atom as a fluorine atom; Represents an alkyl group having 1 to 10 carbon atoms and substituted with

X ″ is a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkylene group has 2 to 6 carbon atoms, preferably 3 to 5 carbon atoms, Preferably it is C3.
Y ″ and Z ″ are each independently a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkyl group has 1 to 10 carbon atoms, preferably It is C1-C7, More preferably, it is C1-C3.

  The carbon number of the alkylene group of X ″ or the carbon number of the alkyl group of Y ″ and Z ″ is preferably as small as possible within the range of the above carbon number for reasons such as good solubility in a resist solvent.

  In addition, in the alkylene group of X ″ or the alkyl group of Y ″ and Z ″, the strength of the acid increases as the number of hydrogen atoms substituted by fluorine atoms increases, and high-energy light or electron beam of 200 nm or less The ratio of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate is preferably 70 to 100%, more preferably 90 to 100%, and most preferably all. Are a perfluoroalkylene group or a perfluoroalkyl group in which a hydrogen atom is substituted with a fluorine atom.

In the present invention, compounds represented by the following formulas (40) to (45) can also be used as a photoacid generator.

In formula (40), Q is an alkylene group, an arylene group or an alkoxylene group, and R ¹⁵ is an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group.

  The compound represented by the formula (40) includes N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoro Methylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) naphthylimide, N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide, N- ( 0-camphorsulfonyloxy) naphthylimide, N- (n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (n-octanesulfonyloxy) Naphthylimide, N- (p-toluenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (p-toluenesulfonyloxy) naphthylimide, N- (2 -Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (4 -Trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imido, N- (4-trifluoromethylbenzenesulfonyloxy) naphthylimide, N- (perfluorobenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (Perfluorobenzenesulfonyloxy) naphthylimide, N- (1-naphthalenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (1-naphthalenesulfonyloxy) Naphthylimide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) naphthylimide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept It is preferably at least one selected from the group consisting of to-5-ene-2,3-dicarboximide and N- (perfluoro-n-octanesulfonyloxy) naphthylimide.

In formula (41), R ¹⁶ may be the same or different and each independently represents an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, and optionally substituted. A heteroaryl group or an optionally substituted aralkyl group.

  The compound represented by the formula (41) includes diphenyl disulfone, di (4-methylphenyl) disulfone, dinaphthyl disulfone, di (4-tert-butylphenyl) disulfone, di (4-hydroxyphenyl) disulfone, di It must be at least one selected from the group consisting of (3-hydroxynaphthyl) disulfone, di (4-fluorophenyl) disulfone, di (2-fluorophenyl) disulfone and di (4-toluromethylphenyl) disulfone. preferable.

In formula (42), R ¹⁷ may be the same or different and each independently represents an optionally substituted linear, branched or cyclic alkyl group, an optionally substituted aryl group, and optionally substituted. A heteroaryl group or an optionally substituted aralkyl group.

  The compound represented by the formula (42) is α- (methylsulfonyloxyimino) -phenylacetonitrile, α- (methylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (trifluoromethylsulfonyloxyimino) -phenyl. Acetonitrile, α- (trifluoromethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (propylsulfonyloxyimino) -4-methylphenylacetonitrile and α It is preferably at least one selected from the group consisting of-(methylsulfonyloxyimino) -4-bromophenylacetonitrile.

In formula (43), R ¹⁸ may be the same or different and each independently represents a halogenated alkyl group having one or more chlorine atoms and one or more bromine atoms. The halogenated alkyl group preferably has 1 to 5 carbon atoms.

In formulas (44) and (45), R ¹⁹ and R ²⁰ are each independently an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group or an isopropyl group, a cyclopentyl group, or a cyclohexyl group. A cycloalkyl group such as methoxy group, ethoxy group, propoxy group or the like, or an aryl group such as phenyl group, toluyl group or naphthyl group, preferably 6 to 6 carbon atoms. 10 aryl groups.
L ¹⁹ and L ²⁰ are each independently an organic group having a 1,2-naphthoquinonediazide group. Specific examples of the organic group having a 1,2-naphthoquinonediazide group include a 1,2-naphthoquinonediazide-4-sulfonyl group, a 1,2-naphthoquinonediazide-5-sulfonyl group, and a 1,2-naphthoquinonediazide- A 1,2-quinonediazidosulfonyl group such as a 6-sulfonyl group can be mentioned as a preferable one. In particular, 1,2-naphthoquinonediazide-4-sulfonyl group and 1,2-naphthoquinonediazide-5-sulfonyl group are preferable.
p is an integer of 1 to 3, q is an integer of 0 to 4, and 1 ≦ p + q ≦ 5.
J ¹⁹ is a group having a single bond, a polymethylene group having 1 to 4 carbon atoms, a cycloalkylene group, a phenylene group, a group represented by the following formula (44a), a carbonyl bond, an ester bond, an amide bond or an ether bond.

Y ¹⁹ is each independently a hydrogen atom, an alkyl group or an aryl group, and X ²⁰ is each independently a group represented by the following formula (45a).
In the formula (45a), Z ²² each independently represents an alkyl group, a cycloalkyl group, or an aryl group, each R ²² independently represents an alkyl group, a cycloalkyl group, or an alkoxy group, and r is 0 to 3 It is an integer.

  Other acid generators include bis (p-toluenesulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) ) Diazomethane, bis (isopropylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, 1,3-bis (cyclohexylsulfonylazomethylsulfonyl) propane, 1,4 -Bis (phenylsulfonylazomethylsulfonyl) butane, 1,6-bis (phenylsulfonylazomethylsulfonyl) hexane, 1,10-bis (cyclohexylsulfo) Bissulfonyldiazomethanes such as (ruazomethylsulfonyl) decane, 2- (4-methoxyphenyl) -4,6- (bistrichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4 , 6- (bistrichloromethyl) -1,3,5-triazine, tris (2,3-dibromopropyl) -1,3,5-triazine, tris (2,3-dibromopropyl) isocyanurate And triazine derivatives.

  Of these photoacid generators, compounds that generate an organic sulfonic acid by the action of actinic rays or radiation are particularly preferred.

  The blending amount of PAG is 0 to 40% by weight, preferably 5 to 30% by weight, more preferably 5 to 20% by weight in the total composition excluding the solvent.

  In the present invention, an acid diffusion control agent (quencher) having an action of controlling an undesired chemical reaction in an unexposed region by controlling diffusion of an acid generated from an acid generator by irradiation in a resist film. May be blended in the photoresist composition. By using such an acid diffusion controller, the storage stability of the photoresist composition is improved. Further, the resolution is improved, and a change in the line width of the resist pattern due to fluctuations in the holding time before electron beam irradiation and the holding time after electron beam irradiation can be suppressed, and the process stability is extremely excellent.

  Examples of such acid diffusion control agents include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine; diethylamine, di-n-propylamine, di- -Dialkylamines such as n-heptylamine, di-n-octylamine, dicyclohexylamine; trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-hexylamine, tri-n-pentylamine , Tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decanylamine, tri-n-dodecylamine, and the like; diethanolamine, triethanolamine, diisopropanolamine, tri Isopropanol Alkyl alcohol amines such as min, di-n-octanolamine and tri-n-octanolamine; 1,4-diazabicyclo [2.2.2] octane, 1,5-diazabicyclo [4.3.0] -5 Electron beam decomposable basic compounds such as nitrogen atom-containing basic compounds such as cyclic amines such as nonene and 1,8-diazabicyclo [5.4.0] -7-undecene, basic sulfonium compounds and basic iodonium compounds Is mentioned. The acid diffusion controller can be used alone or in combination of two or more.

The blending amount of the quencher is 0 to 40% by weight, preferably 0.01 to 15% by weight in the total composition excluding the solvent.
In the present invention, if desired, further miscible additives, for example, additional resins for improving the performance of resist films, surfactants for improving coating properties, dissolution control agents, sensitizers, plasticizers. Stabilizers, colorants, antihalation agents, dyes, pigments, and the like can be appropriately added and contained.

  The dissolution control agent is a component having an action of reducing the solubility of the cyclic compound in an alkaline developer so as to moderate the dissolution rate during development.

  Examples of the dissolution control agent include aromatic hydrocarbons such as naphthalene, phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenylnaphthyl ketone; and sulfones such as methylphenylsulfone, diphenylsulfone, and dinaphthylsulfone. Can be mentioned. Furthermore, for example, bisphenols into which an acid dissociable functional group has been introduced, tris (hydroxyphenyl) methane into which a t-butylcarbonyl group has been introduced, and the like can also be mentioned. These dissolution control agents can be used alone or in combination of two or more. The blending amount of the dissolution control agent is appropriately adjusted according to the type of the cyclic compound to be used, but is preferably 0 to 50% by weight, more preferably 0 to 40% by weight, and more preferably 0 to 30% by weight based on the total weight of the solid component. Is more preferable.

  The sensitizer is a component that absorbs the energy of the irradiated radiation and transmits the energy to the acid generator, thereby increasing the amount of acid generated and improving the apparent sensitivity of the resist. is there. Examples of such sensitizers include, but are not limited to, benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes. These sensitizers can be used alone or in combination of two or more. The blending amount of the sensitizer is preferably 0 to 50% by weight, more preferably 0 to 20% by weight, even more preferably 0 to 10% by weight based on the total weight of the solid component.

  The surfactant is a component having an action of improving the coating property and striation of the photoresist composition of the present invention, the developing property as a resist, and the like. As such a surfactant, any of anionic, cationic, nonionic or amphoteric can be used. Of these, nonionic surfactants are preferred. Nonionic surfactants have better affinity with the solvent used in the photoresist composition and are more effective. Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, polyethylene glycol higher fatty acid diesters, and the following trade names: Ftop (manufactured by Gemco) , MegaFac (Dainippon Ink & Chemicals), Florard (Sumitomo 3M), Asahi Guard, Surflon (Asahi Glass), Pepol (Toho Chemical), KP (Shin-Etsu Chemical) The series products such as Polyflow (manufactured by Kyoeisha Yushi Chemical Co., Ltd.) and the like can be mentioned, but are not particularly limited. The blending amount of the surfactant is preferably 0 to 2% by weight, more preferably 0 to 1% by weight, and still more preferably 0 to 0.1% by weight based on the total weight of the solid components.

  Further, by blending a dye or a pigment, the latent image in the exposed area can be visualized, and the influence of halation during exposure can be reduced. Furthermore, the adhesiveness with a board | substrate can be improved by mix | blending an adhesion aid.

  An organic carboxylic acid or phosphorus oxo acid or a derivative thereof is added as an optional component for the purpose of preventing sensitivity deterioration when an acid diffusion control agent is added and improving the resist pattern shape, retention stability, etc. be able to. These compounds can be used in combination with an acid diffusion controller or may be used alone. As the organic carboxylic acid, for example, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like are suitable. Phosphorus oxo acids or derivatives thereof include phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid diphenyl ester and other phosphoric acid or derivatives thereof such as phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid di- Examples include phosphonic acids such as n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, and phosphonic acid dibenzyl ester or derivatives thereof, phosphinic acid such as phosphinic acid and phenylphosphinic acid, and derivatives such as esters thereof. Of these, phosphonic acid is particularly preferred.

  In order to form a resist pattern, first, the photoresist composition of the present invention is applied onto a substrate such as a silicon wafer, a gallium arsenide wafer, or a wafer coated with aluminum, by spin coating, cast coating, roll coating, or other coating means. Then, a resist film is formed by coating.

  If necessary, a surface treatment agent may be applied in advance on the substrate. Examples of the surface treatment agent include a silane coupling agent such as hexamethylene disilazane (hydrolyzable polymerizable silane coupling agent having a polymerizable group), an anchor coating agent or a base agent (polyvinyl acetal, acrylic resin, vinyl acetate). Based resins, epoxy resins, urethane resins, etc.), and coating agents obtained by mixing these base agents and inorganic fine particles.

  If necessary, a protective film may be formed on the resist film in order to prevent an amine or the like floating in the atmosphere from entering. By forming a protective film, the acid generated in the resist film due to radiation reacts with a compound that reacts with an acid such as amine floating as an impurity in the atmosphere and deactivates, and the resist image deteriorates and sensitivity. Can be prevented from decreasing. As the material for the protective film, a water-soluble and acidic polymer is preferable. Examples thereof include polyacrylic acid and polyvinyl sulfonic acid.

  In order to obtain a high-precision fine pattern and to reduce outgas during exposure, it is preferable to heat before irradiation (before exposure). The heating temperature varies depending on the composition of the photoresist composition, but is preferably 20 to 250 ° C, more preferably 40 to 150 ° C.

  Next, the resist film is exposed to a desired pattern by radiation such as KrF excimer laser, extreme ultraviolet light, electron beam or X-ray. The exposure conditions and the like are appropriately selected according to the composition of the photoresist composition. In the present invention, in order to stably form a high-precision fine pattern, it is preferable to heat after irradiation (after exposure). The post-exposure heating temperature (PEB) varies depending on the composition of the photoresist composition, but is preferably 20 to 250 ° C, more preferably 40 to 150 ° C.

  Next, a predetermined resist pattern can be formed by developing the exposed resist film with an alkaline developer. Examples of the alkaline developer include alkaline such as mono-, di- or trialkylamines, mono-, di- or trialkanolamines, heterocyclic amines, tetramethylammonium hydroxide (TMAH), choline and the like. An alkaline aqueous solution of preferably 1 to 10% by weight, more preferably 1 to 5% by weight, in which one or more compounds are dissolved is used. An appropriate amount of an alcohol such as methanol, ethanol, isopropyl alcohol, or the above-mentioned surfactant can be added to the alkaline developer. Of these, it is particularly preferable to add 10 to 30% by weight of isopropyl alcohol. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

  When a cyclic compound having an acid dissociable, dissolution inhibiting group is used as a photoresist base material, the resist film is exposed to a desired pattern with radiation such as KrF excimer laser, extreme ultraviolet light, electron beam, or X-ray, thereby generating an acid. When the dissociable dissolution inhibiting group is eliminated or the structure is changed, the dissociable dissolution inhibiting group is dissolved in the alkaline developer. On the other hand, it is preferable that the unexposed portion of the pattern is not dissolved in the alkaline developer.

  The non-solubility in the alkali developer cannot be generally defined because the preferred non-solubility differs depending on the development conditions such as the size of the pattern to be formed and the type of the alkali developer to be used. When an aqueous methylammonium hydroxide solution is used as an alkaline developer, the insolubility expressed by the developer dissolution rate of a thin film made of a photoresist substrate is preferably less than 1 nanometer / second, preferably 0.5 nanometer / second. Less than a second is particularly preferred.

  In some cases, post-baking may be performed after the alkali development, or an organic or inorganic antireflection film may be provided between the resist film and the substrate.

  After forming the resist pattern, the pattern wiring board is obtained by etching. Etching can be performed by a known method such as dry etching using plasma gas, wet etching using an alkali solution, a cupric chloride solution, a ferric chloride solution, or the like. After the resist pattern is formed, a plating process such as copper plating, solder plating, nickel plating, or gold plating can be performed.

  The residual resist pattern after etching can be peeled off with an aqueous solution that is stronger than an organic solvent or an alkaline developer. Examples of the organic solvent include PGMEA, PGME, EL, acetone, tetrahydrofuran, and the like. Examples of the strong alkaline aqueous solution include 1 to 20% by weight sodium hydroxide aqueous solution and 1 to 20% by weight potassium hydroxide aqueous solution. Is mentioned. Examples of the peeling method include a dipping method and a spray method. Further, the wiring board on which the resist pattern is formed may be a multilayer wiring board or may have a small diameter through hole.

  After forming a resist pattern using the photoresist composition of the present invention, a wiring substrate can be formed by a method in which a metal is vacuum-deposited and then the resist pattern is eluted with a solution, that is, a lift-off method.

  A semiconductor device can be produced by a microfabrication method using the photoresist composition of the present invention. This semiconductor device can be provided in various devices such as an electric product (electronic device) such as a television receiver, a mobile phone, and a computer, a display, and a car controlled by a computer.

  The compound of the present invention can produce various molded products (thin films, films, thin plates, fibers, etc. formed on a substrate such as a silicon wafer) by known molding methods.

  Molding methods include injection molding, injection compression molding, extrusion molding, blow molding, pressure molding, transfer molding, spin coating, spray coating, casting, vapor deposition, thermal CVD, plasma Examples thereof include a CVD method and a plasma polymerization method, and these molding methods can be appropriately selected according to the form and performance of a desired product.

  Further, a thin film is obtained by the above method using the compound of the present invention, and the obtained thin film is cured by heat, ultraviolet light, deep ultraviolet light, vacuum ultraviolet light, extreme ultraviolet light, electron beam, plasma, X-ray, etc. (cyclization addition) Reaction).

  When the compound of the present invention is formed into a thin film by a spin coating method or the like, the compound of the present invention can be dissolved in an organic solvent and used as a paint.

  Examples of organic solvents include chloroform, dichloromethane, 1,1,2,2-tetrachloroethane, dichloroethane, dichlorobenzene, trichlorobenzene, tetrachlorobenzene, dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethylacetamide, dimethyl sulfoxide. (DMSO), anisole, acetophenone, benzonitrile, nitrobenzene, propylene glycol methyl ether acetate, propylene glycol monomethyl ether, tetrahydrofuran (THF), cyclohexanone, methyl ethyl ketone, acetone and the like.

The concentration of the compound of the present invention in the paint may be appropriately adjusted in consideration of the viscosity of the paint and the thin film forming method.
The thickness of the thin film is not particularly limited, but generally a thickness of about 10 nm to 10 μm is preferably used. The film thickness of the thin film can be measured with an ellipsometer, a reflective optical film thickness meter, or the like, or with a stylus film thickness meter or AFM.

  The thin film of the present invention is used as a photoresist thin film, optical thin films for various optical information processing devices such as optical lenses, optical fibers, optical waveguides, photonic crystals, interlayer insulating films for semiconductors, protective films for semiconductors, etc. It is useful as a thin film for ULSI devices, a liquid crystal display, a liquid crystal projector, a plasma display, an EL display, an LED display and other thin film for image display devices, a CMOS image sensor, a CCD image sensor, and the like. Furthermore, these thin films are provided for semiconductor devices such as CPU, DRAM, flash memory, electronic circuit devices for information processing, electronic circuit devices such as high-frequency communication electronic circuit devices, image display devices, optical information processing devices, and optical communication devices. It can also be used in a member such as a surface protective film and a heat-resistant film.

Synthesis example 1
Under a nitrogen stream, in a round bottom flask with a capacity of 200 ml, 50.0 g (402.8 mmol) of 3-methoxyphenol (Tokyo Chemical Industry Co., Ltd.), 4-formylbenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 60. 5 g (402.8 mmol) and 500 ml of dehydrated dichloromethane were added and immersed in an ice-water bath and cooled to 5 ° C. or lower. To this mixture, 60.8 ml (483.6 mmol) of boron trifluoride ether adduct (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise so that the internal temperature did not exceed 15 ° C., and then the temperature was raised to room temperature. Warmed and continued stirring for 8 hours. The reaction solution was cooled in an ice water bath, quenched slowly by dropwise addition of water, and the precipitated solid was filtered off. Further, the precipitate separated by filtration is washed with water until it becomes neutral, then dissolved in N-methyl-2-pyrrolidone, reprecipitated with ethyl acetate, and the precipitated solid is separated by filtration to obtain a cyclic compound (A (Yield 94.4 g).
The result of ¹ H-NMR measurement is shown in FIG. ^{From the 1} H-NMR spectrum, it was confirmed that the obtained compound had the structure of the following formula (1).

Example 1
Synthesis of 2-adamantan-1-yl-propan-2-oxy-carbonylmethyl bromide
Under a nitrogen stream, 100 g (0.555 mol) of 1-adamantanecarboxylic acid was sealed in a 1 L round bottom flask equipped with a Jimroth condenser and a dropping funnel, and 250 ml of methanol was added. Concentrated sulfuric acid (2.5 ml, 0.047 mol) was gradually dropped from the dropping funnel and heated to reflux for 4 hours. The mixture was allowed to cool to room temperature, cooled to 0 ° C., and saturated brine was added to stop the reaction. Subsequently, the reaction solution was extracted with an ether solvent, and the obtained organic layer was washed with saturated brine until the solution became neutral. After drying and adding anhydrous sodium sulfate to the separated organic layer, the solvent was distilled off under reduced pressure to obtain methyl 1-adamantanecarboxylate (yield 105 g).

  Under a nitrogen stream, 8.07 g (0.0415 mol) of methyl 1-adamantanecarboxylate and 83.0 ml of tetrahydrofuran were added to a 300 ml round bottom flask and stirred. After cooling to 0 ° C., 100.0 ml of methylmagnesium bromide (1.0 M THF solution, 0.10 mol) was added, and the mixture was warmed to room temperature and stirred for 11 hours. The reaction was stopped with a saturated aqueous ammonium chloride solution, the reaction solution was extracted with an ethyl acetate solvent, and the resulting solution was washed with saturated brine. After adding anhydrous sodium sulfate to the separated organic layer and drying, the solvent was distilled off under reduced pressure to obtain 2-adamantan-1-yl-propan-2-ol (yield 7.95 g).

Under a nitrogen stream, 8.0 g (0.041 mol) of 2-adamantan-1-yl-propan-2-ol and 50.0 ml of dichloromethane were added to a 200 ml round bottom flask and stirred, followed by 5.0 ml of pyridine (0. 062 mol) was added. After cooling to 0 ° C., 7.1 ml (0.082 mol) of bromoacetic acid bromide was added, and the mixture was warmed to room temperature and stirred for 20 hours. The reaction was stopped with saturated aqueous sodium hydrogen carbonate solution, the reaction solution was extracted with ethyl acetate solvent, and the resulting solution was washed with saturated brine. The separated organic layer was dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified with a neutral silica gel column (developing solvent: hexane / ethyl acetate = 9/1) to give 2-adamantan-1-yl-propane-2-oxy-carbonylmethyl bromide as a colorless oil (yield 4 .5g).
The result of ¹ H-NMR measurement is shown in FIG. ^{From the 1} H-NMR spectrum, it was confirmed that the obtained compound was 2-adamantan-1-yl-propan-2-oxy-carbonylmethyl bromide.

Example 2
Under a nitrogen stream, 0.812 g (7.92 mmol) of calix resorcinalene compound obtained in Synthesis Example 1 and 26.0 ml of N-methyl-2-pyrrolidone were sealed in a 100 ml round bottom flask and heated to 40 ° C. Dissolved. The mixture was allowed to cool to room temperature, cooled to 0 ° C., added with 0.99 ml (7.10 mmol) of triethylamine, stirred for 10 minutes, and 2-adamantan-1-yl-propane-2-oxy-carbonylmethyl obtained in Example 2 2.27 g (7.20 mmol) of bromide was added. After warming to room temperature and stirring for 20 hours, the reaction was stopped by adding a saturated ammonium chloride solution. Subsequently, the reaction solution was extracted with ethyl acetate and washed with pure water and saturated brine. The resulting solution was concentrated and reprecipitated with a mixed solvent of ethyl acetate and hexane to obtain the desired product (yield 1.14 g). The result of ¹ H-NMR measurement is shown in FIG. ^{From the 1} H-NMR spectrum, it was confirmed that the obtained compound had the structure of the following formula (2).

Example 3
Synthesis of 3-adamantan-1-yl-2-methyl-propane-2-oxy-carbonylmethyl bromide
Under a nitrogen stream, 13.5 g (0.0695 mol) of 1-adamantaneacetic acid was sealed in a 1 L round bottom flask equipped with a Mr. Jimroth condenser and a dropping funnel, and 31.0 ml of methanol was added. Concentrated sulfuric acid 0.31 ml (0.00583 mol) was gradually dropped from the dropping funnel and heated to reflux for 4 hours. The mixture was allowed to cool to room temperature, cooled to 0 ° C., and saturated brine was added to stop the reaction. Subsequently, the reaction solution was extracted with an ether solvent, and the obtained organic layer was washed with saturated brine until the solution became neutral. After drying and adding anhydrous sodium sulfate to the separated organic layer, the solvent was distilled off under reduced pressure to obtain methyl 1-adamantane acetate (yield 14 g).

  Under a nitrogen stream, 7.0 g (0.034 mol) of methyl 1-adamantane acetate and 68.0 ml of tetrahydrofuran (THF) were added to a 500 ml round bottom flask and stirred. After cooling to 0 ° C., 81.0 ml of methylmagnesium bromide (1.0 M THF solution, 0.081 mol) was added, and the mixture was warmed to room temperature and stirred for 7 hours. The reaction was stopped with a saturated aqueous ammonium chloride solution, the reaction solution was extracted with an ethyl acetate solvent, and the resulting solution was washed with saturated brine. After adding anhydrous sodium sulfate to the separated organic layer and drying, the solvent was distilled off under reduced pressure to obtain 3-adamantyl-2-methyl-propan-2-ol (yield 6.7 g).

Under a nitrogen stream, 1.0 g (4.8 mmol) of 3-adamantyl-2-methyl-propan-2-ol and 10.0 ml of tetrahydrofuran were added to a 100 ml round bottom flask and stirred, and then 0.6 ml of pyridine (7. 4 mmol) was added. After cooling to 0 ° C., 0.84 ml (9.6 mmol) of bromoacetic acid bromide was added, and the mixture was warmed to room temperature and stirred for 20 hours. The reaction was stopped with saturated aqueous sodium hydrogen carbonate solution, the reaction solution was extracted with ethyl acetate solvent, and the resulting solution was washed with saturated brine. The separated organic layer was dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The residue is purified by a neutral silica gel column (developing solvent: hexane / ethyl acetate = 9/1) to give 3-adamantan-1-yl-2-methyl-propane-2-oxy-carbonylmethyl bromide as a colorless oil. (Yield 1.3 g). The results of ¹ H-NMR measurement are shown in FIG.
^{From the 1} H-NMR spectrum, it was confirmed that the obtained compound was 3-adamantan-1-yl-2-methyl-propane-2-oxy-carbonylmethyl bromide.

Example 4
Under a nitrogen stream, 0.96 g (0.94 mmol) of the calix resorcinalene compound obtained in Synthesis Example 1 and 31.0 ml of N-methyl-2-pyrrolidone were sealed in a 100 ml round bottom flask and heated to 40 ° C. Dissolved. The mixture was allowed to cool to room temperature and then cooled to 0 ° C., 1.0 ml (7.2 mmol) of triethylamine was added and stirred for 10 minutes, and 3-adamantan-1-yl-2-methyl-propane-2 obtained in Example 3 was added. -2.3 g (7.1 mmol) of oxy-carbonylmethyl bromide was added. After warming to room temperature and stirring for 20 hours, the reaction was stopped by adding a saturated ammonium chloride solution. Subsequently, the reaction solution was extracted with ethyl acetate and washed with pure water and saturated brine. The obtained solution was concentrated and reprecipitated with a mixed solvent of ethyl acetate and hexane to obtain the cyclic compound shown above (yield 1.13 g). The result of ¹ H-NMR measurement is shown in FIG. ^{From the 1} H-NMR spectrum, it was confirmed that the obtained compound had the structure of the following formula (3).

Example 5
Synthesis of adamantyl- (chloromethoxy) methane
Under a nitrogen stream, 10.0 g (0.0601 mol) of 1-hydroxymethyladamantane, 2.32 g (0.0773 mol) of paraformaldehyde, 10.9 g (0.0906 mol) of anhydrous magnesium sulfate, 100. 0 ml was sealed and stirred at 0 ° C. Separately, a 100 ml three-necked flask equipped with a dropping funnel was prepared and connected to the aforementioned two-necked flask with a Teflon (registered trademark) tube and a glass tube. 19.8 g (0.339 mol) of sodium chloride was added to the flask, and 12.0 ml (0.221 mol) of concentrated sulfuric acid was added to the dropping funnel, which was gradually added dropwise. The generated hydrochloric acid gas was hubbed in the reaction solution under a nitrogen stream and stirred at 0 ° C. for 6 hours. The anhydrous magnesium sulfate was removed by filtration, and the solvent in the filtrate was distilled off under reduced pressure. The residue was distilled under reduced pressure to obtain adamantyl- (chloromethoxy) methane as a colorless oil (yield 5.52 g).
The result of ¹ H-NMR measurement is shown in FIG. ^{From the 1} H-NMR spectrum, it was confirmed that the obtained compound was adamantyl- (chloromethoxy) methane.

Example 6
By enclosing 2.0 g (2.0 mmol) of calix resorcinalene compound obtained in Synthesis Example 1 and 32.0 ml of N-methyl-2-pyrrolidone in a 100 ml round bottom flask under a nitrogen stream and heating to 40 ° C. Dissolved. After allowing to cool to room temperature, it was cooled to 0 ° C., 2.7 ml (19.4 mmol) of triethylamine was added and stirred for 10 minutes, and 2.0 g (8.7 mmol) of adamantyl- (chloromethoxy) methane obtained in Example 5 was added. added. After warming to room temperature and stirring for 20 hours, the reaction was stopped by adding a saturated ammonium chloride solution. Subsequently, the reaction solution was extracted with ethyl acetate and washed with pure water and saturated brine. The resulting solution was concentrated and reprecipitated with a mixed solvent of ethyl acetate and hexane to obtain the desired product (yield 2.7 g). The result of ¹ H-NMR measurement is shown in FIG. ^{From the 1} H-NMR spectrum, it was confirmed that the obtained compound had the structure of the following formula (4).

Example 7
Synthesis of adamantyl- (chloromethoxy) ethane
Adamantyl- (chloromethoxy) ethane was obtained as a colorless oil in the same procedure as in Example 5 except that 5.67 g of 1-adamantaneethanol was used instead of 1-hydroxymethyladamantane of Example 5 (yield 2. 97 g). The results of ¹ H-NMR measurement are shown in FIG. ^{From the 1} H-NMR spectrum, it was confirmed that the obtained compound was adamantyl- (chloromethoxy) ethane.

Example 8
The target compound was obtained as a white solid in the same procedure as in Example 6 except that adamantyl- (chloromethoxy) ethane obtained in Example 7 was used instead of adamantyl- (chloromethoxy) methane in Example 6. Yield 2.7 g). The results of ¹ H-NMR measurement are shown in FIG. ^{From the 1} H-NMR spectrum, it was confirmed that the obtained compound had the structure of the following formula (5).

Example 9
Synthesis of 2- (chloromethoxy) bicyclo [2.2.1] heptane
2- (Chloromethoxy) bicyclo [2.2.1] was prepared in the same manner as in Example 5 except that 7.7 g of norborneneol obtained in Example 9 was used instead of 1-hydroxymethyladamantane in Example 5. ] Heptane was obtained as a colorless oil (yield 6.8 g). The result of ¹ H-NMR measurement is shown in FIG. ^{From the 1} H-NMR spectrum, it was confirmed that the obtained compound was 2- (chloromethoxy) bicyclo [2.2.1] heptane.

Example 10
The target compound was prepared in the same manner as in Example 6 except that 1.4 g of 2- (chloromethoxy) bicyclo [2.2.1] heptane was used instead of adamantyl- (chloromethoxy) methane of Example 6. Obtained as a white solid (yield 2.4 g). The results of ¹ H-NMR measurement are shown in FIG. ^{From the 1} H-NMR spectrum, it was confirmed that the obtained compound had the structure of the following formula (6).

Example 11
Synthesis of 2- (chloromethoxy) -1,7,7 trimethylbicyclo [2.2.1] heptane
2- (Chloromethoxy) -1,7,7 trimethylbicyclo [2.2.1] heptane was prepared in the same procedure as in Example 5 except that 15 g of borneol was used instead of 1-hydroxymethyladamantane in Example 5. Obtained as a colorless oil (yield 11.1 g). The results of ¹ H-NMR measurement are shown in FIG. ^{From the 1} H-NMR spectrum, it was confirmed that the obtained compound was 2- (chloromethoxy) -1,7,7 trimethylbicyclo [2.2.1] heptane.

Example 12
Except for using 2.1 g of 2- (chloromethoxy) -1,7,7 trimethylbicyclo [2.2.1] heptane obtained in Example 11 instead of adamantyl- (chloromethoxy) methane of Example 6. The target compound was obtained as a white solid by the same method as in Example 6 (yield 3.8 g). The result of ¹ H-NMR measurement is shown in FIG. ^{From the 1} H-NMR spectrum, it was confirmed that the obtained compound had the structure of the following formula (7).

Example 13
Synthesis of 2- (2-phenoxyethyl) adamantyl bromoacetate
Under a nitrogen stream, 100 ml (100 mmol) of a tetrahydrofuran solution (1 mol / l) of lithium bistrimethylsilyllithium was added to a 300 ml round bottom flask, cooled to −78 ° C., and 9.7 ml (99.3 mmol) of dehydrated ethyl acetate was added for 30 minutes. Stirring was performed. To this was added 14 g (93.2 mmol) of 2-adamantanone, and then the mixture was warmed to room temperature and stirred for 8 hours. The reaction solution was poured into ice water, extracted with ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain methyl 1-hydroxy-1- (2-adamantyl) acetate (yield 20.0 g). (89.2 mmol)).

  11.4 g (47.16 mmol) of the obtained compound was dissolved in tetrahydrofuran under a nitrogen stream and cooled to −78 ° C., and 167.8 ml (174.5 mmol) of diisobutylaluminum hydride 1.04 mo / l hexane solution was added. It was dripped. The temperature was raised to room temperature and stirring was performed for 8 hours. The reaction solution was poured into ice water and extracted by adding dilute hydrochloric acid and ethyl acetate to obtain 2- (1-hydroxyethyl) adamantanol (yield 8.6 g (43.8 mmol)).

  5.78 g (29.47 mmol) of the obtained compound and 9.82 g (29.47 mmol) of triphenylphosphine were dissolved in 175 ml of dichloromethane and dissolved in ice. To this solution, 6.30 g (29.47 mmol) of N-bromosuccinimide was gradually added, and the mixture was allowed to warm to room temperature and stirred for 8 hours. The reaction solution was evaporated under reduced pressure, and the residue was purified by silica gel chromatography (developing solvent: ethyl acetate / hexane = 5/95) to obtain 2- (2-bromoethyl) adamantanol (yield 5.81 g (22 .41 mmol)).

  Under a nitrogen stream, 5.3 g (20.59 mmol) of the obtained bromide, 13.42 g (20.59 mmol) of cesium carbonate, 2.33 g (20.59 mmol) of phenol and 100 ml of dehydrated dimethylformamide were added and heated at 50 ° C. for 3 hours. Stir. After allowing to cool, ethyl acetate and a saturated aqueous sodium hydrogen carbonate solution were added for liquid separation, the organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain 2- (2-phenoxyethyl) adamantanol ( Yield 5.5 g (20.3 mmol)).

Under a nitrogen stream, 5.1 g (18.8 mmol) of 2- (2-phenoxyethyl) adamantanol obtained, 0.23 g (1.88 mmol) of N, N-dimethyl-4-aminopyridine (DMAP), 100 ml of toluene Then, 2.87 ml (22.6 mmol) of dimethylaniline was added and ice-cooled. Bromoacetic acid bromide (3.28 ml, 37.64 mmol) was added dropwise, and the mixture was warmed to room temperature and stirred for 24 hours. Extraction was performed by adding ethyl acetate and a saturated aqueous sodium hydrogen carbonate solution, and the organic layer was dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography (developing solvent: ethyl acetate / hexane = 2/8) to obtain 2- (2-phenoxyethyl) adamantyl bromoacetate (yield 4.0 g (10.34 mmol)).
^{(1 H-NMR: 1.5-2.1 (} 12H), 2.49 (2H), 2.73 (t, 2H), 3.81 (s, 2H), 4.07 (t, 2H) 6.8-7.0 (m, 3H) 7.28 (m, 2H) (CDCl3))

Example 14
Synthesis of 2- (2- (p-methoxyphenoxy) ethyl) adamantyl bromoacetate
Synthesis was carried out in the same manner as in Example 13 except that the phenol in Example 13 was replaced with p-methoxyphenol to obtain 2- (2- (p-methoxyphenoxy) ethyl) adamantyl bromoacetate.
^{(1 H-NMR: 1.55-2.15 (} 12H), 2.49 (2H), 2.68 (t, 2H), 3.77 (s, 3H), 3.90 (s, 2H) , 3.99 (t, 2H), 6.81 (m, 4H) (CDCl3))

Example 15
Synthesis of 2- (2- (p-fluorophenoxy) ethyl) adamantyl bromoacetate
Synthesis was performed in the same manner as in Example 13 except that the phenol in Example 13 was replaced with p-fluorophenol to obtain 2- (2- (p-fluorophenoxy) ethyl) adamantyl bromoacetate.
^{(1 H-NMR: 1.6-2.15 (} 12H), 2.49 (2H), 2.68 (t, 2H), 3.80 (s, 2H), 4.00 (t, 2H) 6.8 (m, 2H), 6.98 (m, 2H) (CDCl3))

Example 16
Synthesis of 2- (2- (p-nitrophenoxy) ethyl) adamantyl bromoacetate
Synthesis was performed in the same manner as in Example 13 except that the phenol in Example 13 was replaced with p-nitrophenol to obtain 2- (2- (p-nitrophenoxy) ethyl) adamantyl bromoacetate.
^{(1 H-NMR: 1.6-2.15 (} 12H), 2.49 (m, 2H), 2.78 (t, 2H), 3.82 (s, 2H), 4.17 (t, 2H), 6.93 (m, 2H), 8.21 (m, 2H) (CDCl3))

Example 17
Synthesis of 2- (2- (1-naphthoxy) ethyl) adamantyl bromoacetate
Synthesis was carried out in the same manner as in Example 13 except that the phenol in Example 13 was replaced with α-naphthol to obtain 2- (2- (1-naphthoxy) ethyl) adamantyl bromoacetate.
^{(1 H-NMR: 1.6-2.15 (} 12H), 2.6 (2H), 2.89 (t, 2H), 3.79 (s, 2H), 4.25 (t, 2H) , 7.81 (m, 1H), 7.35-7.52 (m, 4H), 7.77 (m, 1H), 8.2 (m, 1H) (CDCl3))

Example 18
Synthesis of 2-methoxymethyladamantyl bromoacetate
Under a nitrogen stream, 4 g (24.35 mmol) of 2-adamantyloxirane and 1.58 g (29.22 mmol) of sodium methoxide were heated and stirred at 50 ° C. and 120 ° C. for 5 hours. After cooling, ethyl acetate and water were added for extraction, the organic layer was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was dissolved in toluene and recrystallized to obtain 2-methoxymethyl-2-adamantanol (yield 3.0 g (15.4 mmol)).
Under a nitrogen stream, 3.0 g (15.4 mmol) of 2-methoxymethyl-2-adamantanol and 0.19 g (1.5 mmol) of DMAP were dissolved in toluene and cooled with ice. 2.34 ml (18.49 mmol) of N, N-dimethylaniline was added, and 2.68 ml (30.8 mmol) of bromoacetic acid bromide was gradually added dropwise. The mixture was warmed to room temperature and stirred as it was for 24 hours. The reaction solution was extracted with ethyl acetate and a saturated aqueous sodium hydrogen carbonate solution, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography (developing solvent: ethyl acetate / hexane = 3/97) to obtain 2-methoxymethyladamantyl bromoacetate (yield 3.3 g (10.62 mmol)).
^{(1 H-NMR: 1.57-2.15 (} 12H), 2.5 (2H), 3.35 (s, 3H), 3.85 (s, 2H), 4.00 (s, 2H) (CDCl3))

Example 19
Synthesis of 2-isopropyladamantyl bromoacetate
Under a nitrogen stream, 8.76 g (58.33 mmol) of 2-adamantanone was dissolved in 500 ml of dehydrated tetrahydrofuran and cooled to -78 ° C. To this was added 100 ml of a 1.07 mol / l pentane solution of 2-propyllithium, and then the mixture was warmed to room temperature and further stirred for 8 hours. The reaction solution was poured into ice-cold water and extracted with ethyl acetate. The residue was recrystallized using toluene to give 2-isopropyladamantanol (yield 9.8 g (50.43 mmol)).
Under a nitrogen stream, 9.8 g (50.43 mmol) of 2-isopropyladamantanol, 0.62 g (5.04 mmol) of DMAP and 250 ml of dehydrated toluene were added and ice-cooled. 7.67 ml (60.52 mmol) of N, N-dimethylaniline was added, and 8.79 ml (100.9 mmol) of bromoacetic acid bromide was gradually added dropwise. After completion of dropping, the mixture was stirred for 48 hours. Ethyl acetate and a saturated aqueous carbonate solution were added to the reaction solution, the organic layer was separated, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography (developing solvent: ethyl acetate / hexane = 2/98) to give 2-isopropyladamantyl bromoacetate (yield 5.28 g (16.8 mmol)).
^{(1 H-NMR: 0.98 (} d, 6H), 1.6-2.0 (12H), 2.48 (1H), 2.63 (2H), 3.85 (s, 2H) (CDCl3 ))

Example 20
Synthesis of 2-phenethyladamantyl bromoacetate
Under a nitrogen stream, 2.08 g (15.2 mmol) of zinc chloride, 8.5 g (200.6 mmol) of lithium chloride and 230 ml of dehydrated tetrahydrofuran were added, and the mixture was stirred on ice. To this, 200 ml of a 1.0 mol / l tetrahydrofuran solution of phenethylmagnesium chloride was added dropwise, and further 23 g (153.1 mmol) of 2-adamantanone in tetrahydrofuran was added and stirred as it was for 8 hours. The reaction solution was poured into ice-cold water, extracted with ethyl acetate, and the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography (developing solution: ethyl acetate / hexane = 2/8) to obtain 2-phenethyladamantanol (yield 4.1 g (16.01 mmol)).
Under a nitrogen stream, 4.1 g (16.01 mmol) of 2-phenethyladamantanol, 0.20 g (1.6 mmol) of DMAP, and 100 ml of toluene were added and ice-cooled. After adding 2.44 ml (19.2 mmol) of N, N-dimethylaniline, 2.78 ml (32.0 mmol) of bromoacetic acid bromide was gradually added, followed by stirring for 24 hours while raising the temperature to room temperature. The reaction solution was extracted with ethyl acetate and a saturated aqueous sodium hydrogen carbonate solution, and the organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. The residue was purified by silica gel chromatography (developing solution: ethyl acetate / hexane = 1/9) to obtain 2-phenethyladamantyl bromoacetate (yield 4.15 g (11.0 mmol)).
^{(1 H-NMR: 1.6-2.1 (} 12H), 2.5 (4H), 2.6 (2H), 3.73 (s, 2H), 7.18 (m, 3H), 7 .25 (m, 2H) (CDCl3))

Example 21
Synthesis of 2-methylnorbornyl bromoacetate
Under a nitrogen stream, 9.73 g (88.33 mmol) of 2-norbornanone was dissolved in 100 ml of dehydrated tetrahydrofuran and cooled to -78 ° C. To this solution was added 1.06 mmol / ml tetrahydrofuran solution of methylmagnesium bromide, and the mixture was warmed to room temperature and stirred for 8 hours. The reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and the solvent was distilled off under reduced pressure. The residue was distilled under reduced pressure to give 2-methylnorborneol (yield 5.74 g (45.51 mmol)).
Under a nitrogen stream, 5.74 g (45.51 mmol) of 2-methylnorborneol was dissolved in 230 ml of toluene and cooled with ice. After adding 4.42 ml (54.6 mmol) of pyridine, 5.95 ml (68.2 mmol) of bromoacetic acid bromide was added dropwise, and the mixture was warmed to room temperature and stirred for 24 hours. Ethyl acetate and saturated aqueous sodium hydrogen carbonate solution were added for extraction, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel chromatography (developing solution: ethyl acetate / hexane = 5/95) to obtain 2-methylnorbornyl bromoacetate (yield 8.9 g (36.0 mmol)).
^{(1 H-NMR: 1.2-1.8 (} 11H), 2.21 (1H), 2.60 (1H), 3.89 (s, 2H), 7.18 (m, 3H), ( CDCl3))

Example 22
Synthesis of 2-ethylnorbornyl bromoacetate
Synthesis was performed in the same manner as in Example 21 except that an ethylmagnesium bromide tetrahydrofuran solution was used instead of the methylmagnesium bromide tetrahydrofuran solution to obtain 2-ethylnorbornyl bromoacetate.
^{(1 H-NMR: 0.835 (} t, 3H), 1.2-1.8 (10H), 2.22 (1H), 2.66 (1H), 3.78 (s, 2H) (CDCl3 ))

Example 23
The same method as in Example 2 except that 2- (2-phenoxyethyl) adamantyl bromoacetate obtained in Example 13 was used instead of 2-adamantan-1-yl-propane-2-oxy-carbonylmethyl bromide. Gave the desired compound (8).
^{(1 H-NMR: 1.5-2.1 (} m, 48H), 2.35 (8H), 2.57 (8H), 3.4-3.7 (12H), 4.04 (8H) 4.85 (m, 8H), 5.1-5.25, 5.51-5.71, 6.15-6.4, 6.5 (12H), 6.6-6.8 (8H) ), 6.9 (12H), 7.25 (8H), 7.4-7.7 (8H), 8.9-9.1, 9.1-9.2 (4H) ((CD ₃ ) ₂ SO))

Example 24
Example except that 2- (2- (p-methoxyphenoxy) ethyl) adamantyl bromoacetate obtained in Example 14 was used instead of 2-adamantan-1-yl-propan-2-oxy-carbonylmethyl bromide The target compound (9) was obtained by the same method as 2.
^{(1 H-NMR: 1.4-2.1 (} m, 48H), 2.38 (8H), 2.57 (8H), 3.4-3.7 (24H), 4.00 (8H) 4.84 (m, 8H), 5.1-5.25, 5.51-5.71, 6.15-6.4, 6.49 (12H), 6.6-6.8 (8H) ), 6.84 (16H), 6.9 (12H), 7.4-7.6 (8H), 8.9-9.1, 9.1-9.2 (4H) ((CD ₃ ) ₂ SO))

Example 25
Example except that 2- (2- (p-fluorophenoxy) ethyl) adamantyl bromoacetate obtained in Example 15 was used instead of 2-adamantan-1-yl-propan-2-oxy-carbonylmethyl bromide The target compound (10) was obtained by the same method as 2.
^{(1 H-NMR: 1.4-2.1 (} m, 48H), 2.34 (8H), 2.56 (8H), 3.4-3.65 (24H), 4.02 (8H) 4.85 (m, 8H), 5.1-5.25, 5.51-5.71, 6.15-6.4, 6.50 (12H), 6.6-6.8 (8H) ), 6.93 (8H), 7.10 (8H), 6.9 (12H), 7.4-7.6 (8H), 8.9-9.1, 9.1-9.2 ( 4H) ((CD ₃ ) ₂ SO))

Example 26
Example except that 2- (2- (p-nitrophenoxy) ethyl) adamantyl bromoacetate obtained in Example 16 was used instead of 2-adamantan-1-yl-propan-2-oxy-carbonylmethyl bromide A photoresist base material (11) was obtained by the same method as 2.
^{(1 H-NMR: 1.4-2.1 (} m, 48H), 2.33 (8H), 2.62 (8H), 3.4-3.65 (24H), 4.21 (8H) 4.86 (m, 8H), 5.1-5.25, 5.51-5.71, 6.15-6.4, 6.50 (12H), 6.6-6.8 (8H) ), 6.93 (8H), 7.12 (8H), 7.4-7.6 (8H), 8.19 (8H), 8.9-9.1, 9.1-9.2 ( 4H) ((CD ₃ ) ₂ SO))

Example 27
Example 2 except that 2- (2- (1-naphthoxy) ethyl) adamantyl bromoacetate obtained in Example 17 was used instead of 2-adamantan-1-yl-propan-2-oxy-carbonylmethyl bromide The target compound (12) was obtained by the same method as described above.
^{(1 H-NMR: 1.4-2.1 (} m, 48H), 2.36 (8H), 2.71 (8H), 3.4-3.65 (24H), 4.21 (8H) , 4.79 (m, 8H), 5.1-5.25, 5.51-5.71, 6.15-6.4, 6.50 (12H), 6.6-6.8 (8H ), 6.96 (4H), 7.3-7.6 (24H), 7.81 (4H), 8.08 (4H), 8.9-9.1, 9.1-9.2 ( 4H) ((CD ₃ ) ₂ SO))

Example 28
The target compound was prepared in the same manner as in Example 2 except that 2-methoxymethyladamantyl bromoacetate obtained in Example 18 was used instead of 2-adamantan-1-yl-propane-2-oxy-carbonylmethyl bromide. (13) was obtained.
^{(1 H-NMR: 1.5-2.1 (} m, 48H), 2.36 (8H), 2.57 (8H), 3.28 (s, 3H), 3.4-3.7 ( 12H), 3.94 (8H), 4.81 (8H), 5.1-5.25, 5.51-5.71, 6.15-6.4, 6.51 (12H), 6. 6-6.8 (8H), 7.4-7.7 (8H), 8.9-9.1, 9.1-9.2 (4H) ((CD ₃ ) ₂ SO))

Example 29
The target compound (2) was prepared in the same manner as in Example 2 except that 2-isopropyladamantyl bromoacetate obtained in Example 19 was used instead of 2-adamantan-1-yl-propane-2-oxy-carbonylmethyl bromide. 14) was obtained.
^{(1 H-NMR: 0.92 (} 24H), 1.5-2.1 (m, 48H), 2.42 (4H), 2.49 (8H), 3.4-3.7 (12H) 4.82 (8H), 5.1-5.25, 5.51-5.71, 6.15-6.4, 6.49 (12H), 6.6-6.8 (8H), 7.4-7.6 (8H), 8.9-9.1, 9.1-9.2 (4H) ((CD ₃ ) ₂ SO))

Example 30
The target compound (2) was prepared in the same manner as in Example 2 except that 2-phenethyladamantyl bromoacetate obtained in Example 20 was used instead of 2-adamantan-1-yl-propane-2-oxy-carbonylmethyl bromide. 15) was obtained.
^{(1 H-NMR: 1.5-2.1 (} m, 48H), 2.33 (4H), 2.56 (8H), 3.4-3.7 (12H), 4.87 (8H) , 5.1-5.25, 5.51-5.71, 6.15-6.4, 6.50 (12H), 7.1-7.35 (m, 20H), 7.5-7 .7 (8H), 8.9-9.1, 9.1-9.2 (4H) ((CD ₃ ) ₂ SO))

Example 31
The target was prepared in the same manner as in Example 2 except that 2-methylnorbornyl bromoacetate obtained in Example 21 was used instead of 2-adamantan-1-yl-propane-2-oxy-carbonylmethyl bromide. Compound (16) was obtained.
( ¹ H-NMR: 1.1-1.4, 1.45, 1.58-1.7 (m, 48H), 2.17 (4H), 3.4-3.7 (12H), 4 79 (8H), 5.1-5.25, 5.51-5.71, 6.15-6.4, 6.50 (12H), 6.6-6.8 (8H), 7. 4-7.6 (8H), 8.9-9.1,9.1-9.2 (4H ) ((CD 3) 2 SO))

Example 32
The target was prepared in the same manner as in Example 2 except that 2-ethylnorbornyl bromoacetate obtained in Example 22 was used instead of 2-adamantan-1-yl-propan-2-oxy-carbonylmethyl bromide. Compound (17) was obtained.
^{(1 H-NMR: 0.81 (} t, 12H), 1.1-1.8,1.9-2.1 (m, 44H), 2.17 (4H), 3.4-3.7 (12H), 4.82 (8H), 5.1-5.25, 5.51-5.71, 6.15-6.4, 6.50 (12H), 6.6-6.8 ( 8H), 7.4-7.6 (8H), 8.9-9.1, 9.1-9.2 (4H) ((CD ₃ ) ₂ SO))

Example 33
Under a nitrogen stream, 1.96 g (0.082 mol) of sodium hydride was sealed in a 200 ml round bottom flask and washed with hexane. Subsequently, after adding 40.0 ml of dimethyl sulfoxide and cooling to 0 ° C., 10.0 ml of a dimethyl sulfoxide solution of 7.0 g (0.042 mol) of 5-hydroxy-2-adamantanone was added. After warming to room temperature and stirring for 8 hours, the reaction was stopped by cooling to 0 ° C. and adding pure water, and the reaction solution was extracted with a methylene chloride solvent. The obtained organic layer was washed with pure water and saturated brine, dried sodium sulfate was added to the separated organic layer, and the solvent was evaporated under reduced pressure. The obtained residue was purified with a neutral silica gel column (developing solvent: hexane / ethyl acetate = 5/1) to give 5-methoxy-2-adamantanone as a colorless oil (yield 5.8 g, yield 77). %).

  Under a nitrogen stream, 3.76 g (0.021 mol) of 5-methoxy-2-adamantanone, 15.6 g (0.063 mol) of cerium trichloride and 60.0 ml of diethyl ether were added to a 200 ml round bottom flask and stirred. After cooling to −78 ° C., 100.0 ml of ethyl lithium (0.5 M benzene / cyclohexane = 9/1 solution, 0.050 mol) was added and stirred for 3 hours, and then the temperature was raised to room temperature and stirred for 2 hours. The reaction was stopped by adding a saturated aqueous ammonium chloride solution, the reaction solution was extracted with an ethyl acetate solvent, and the resulting solution was washed with saturated brine. After the anhydrous organic sulfate was added to the separated organic layer and dried, the solvent was distilled off under reduced pressure to obtain 2-ethyl-5-methoxy-2-adamantanol as a colorless oil (yield 3.74 g, yield). 85%).

  Under a nitrogen stream, 3.47 g (0.017 mol) of 2-ethyl-5-methoxy-2-adamantanol and 32.0 ml of toluene were added to a 200 ml round bottom flask and stirred, followed by 3.2 ml (0.040 mol) of pyridine. ) Was added. After cooling to 0 ° C., 5.9 ml (0.068 mol) of bromoacetic acid bromide was added, and the mixture was warmed to room temperature and stirred for 24 hours. The reaction was stopped by adding a saturated aqueous sodium hydrogen carbonate solution, and the solution obtained by extracting the reaction solution with an ethyl acetate solvent was washed with saturated brine. After drying by adding anhydrous sodium sulfate to the separated organic layer, the solvent was distilled off under reduced pressure. The residue was purified with a neutral silica gel column (developing solvent: hexane / ethyl acetate = 10/1) to give 2-ethyl-5-methoxy-2-adamantyloxycarbonylmethyl bromide as a colorless oil (yield 3.24 g). Yield 59%).

Example 34
Under a nitrogen stream, 1.55 g (1.52 mmol) of calixresorcinarene compound and 30.0 ml of N-methyl-2-pyrrolidone were sealed in a 100 ml round bottom flask and dissolved by heating to 40 ° C. The mixture was allowed to cool to room temperature, cooled to 0 ° C., added with 1.05 ml (7.53 mmol) of triethylamine, stirred for 10 minutes, and 2.51 g of 2-ethyl-5-methoxy-2-adamantyloxycarbonylmethyl bromide (7. 58 mmol) of an N-methyl-2-pyrrolidone solution, followed by 0.33 ml (2.30 mmol) of 1,8-diazabicyclo [5.4.0] -7-undecene, and the mixture was warmed to room temperature. Stir for 8 hours. The reaction was stopped by adding a saturated ammonium chloride solution, the reaction solution was extracted with ethyl acetate, and washed with pure water and saturated brine. The obtained solution was concentrated and then reprecipitated with a mixed solvent of ethyl acetate and hexane to obtain the target compound (18) as a white solid (yield 2.18 g, yield 71%).

Evaluation Example A photoresist solution composed of a substrate, PAG (photoacid generator), quencher and solvent was prepared, and a pattern was formed on a silicon wafer using an electron beam.
As the substrate, compounds (2) to (18) obtained in Examples, triphenylsulfonium nonafluorobutanesulfonate as PAG, and 1,4-diazabicyclo (2,2,2) octane as the quencher are shown in Table 1. Used as street. A photoresist solution was prepared by dissolving in propylene glycol monomethyl ether so that the concentration of these solid components was 2% by weight.
Each of these photoresist solutions was spin-coated on a silicon wafer subjected to hexamethyldisilazane (HMDS) treatment, and pre-baked (baked before exposure) (PB) at the temperatures shown in Table 1 to form thin films. Next, the substrate having this thin film was drawn using an electron beam drawing apparatus (acceleration voltage 50 kV), and after exposure bake (PEB) as shown in Table 2, the concentration was 2.38 wt% tetrabutylammonium hydroxy. The film was developed with an aqueous solution for 60 seconds, washed with pure water for 60 seconds, and then dried with a nitrogen stream. Table 2 shows the results of resolution (half pitch) and sensitivity (necessary electron beam dose) when a line / space pattern having a size of 1/1 was obtained from the observation results obtained with a scanning electron microscope. The results were the same even when tri-n-octylamine was used in place of 1,4-diazabicyclo (2,2,2) octane as the quencher.

The mass% of the base material / PAG / quencher is a ratio (total 100%) to the total solid content.

  The substrate having the photoresist thin film was irradiated with EUV light (wavelength: 13.5 nm) using an EUV exposure apparatus instead of the electron beam drawing apparatus. Then, it baked at 100 degreeC for 90 second, and formed the pattern by rinsing with 2.38 weight% tetramethylammonium hydroxide aqueous solution for 30 second and ion-exchange water for 30 second. When observed with a scanning electron microscope, it was observed that the resolution was the same as that of the electron beam drawing apparatus.

  The compound of the present invention can be suitably used for a photoresist substrate or composition, particularly a photoresist substrate or composition for extreme ultraviolet light or an electron beam. The photoresist and the photoresist composition of the present invention are suitably used in the electric / electronic field and the optical field such as semiconductor devices.

Claims (15)

A compound represented by the following formula (1).
(In formula, R is group represented by either of following formula (2)-(4).
R ¹ is a hydroxyl group, a substituted or unsubstituted linear alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted branched alkoxy group having 3 to 12 carbon atoms, or a substituted or unsubstituted cyclic group having 3 to 20 carbon atoms. An alkoxy group, a substituted or unsubstituted aryloxyl group having 6 to 10 carbon atoms, an alkoxyalkoxy group, a siloxy group, or a group in which these groups and a divalent group are bonded;
The divalent group includes a substituted or unsubstituted alkyleneoxy group, a substituted or unsubstituted aryleneoxy group, a substituted or unsubstituted silyleneoxy group, a group in which two or more of these groups are bonded, or a group thereof. A group having an ester bond, a carbonate ester bond or an ether bond.
R ² is a hydrogen atom, a group represented by R ¹ , a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, or a cyclic group having 3 to 20 carbon atoms. An aliphatic hydrocarbon group, an aromatic group having 6 to 10 carbon atoms, or a group containing an oxygen atom.
A plurality of R, R ¹ and R ² in the formula (1) may be the same or different.
(In the formula, Ar is selected from a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, a group in which two or more substituted or unsubstituted arylene groups having 6 to 10 carbon atoms are combined, or an alkylene group and an ether bond. A combination of one or more of the above and a substituted or unsubstituted arylene group having 6 to 10 carbon atoms,
In the case of having a substituent, the substituent is a bromine atom, a fluorine atom, a nitrile group, or an alkyl group having 1 to 10 carbon atoms.
R ³ is a group represented by the formula (5).
R ^{3 ′} -L—O— (5)
(L is one in which one or two or more selected from the groups represented by the following formulas (6) to (8) are linked, and takes any linkage order. Formulas (6) to ( When a plurality of groups represented by 8) are included, they may be the same or different.
(In the formula, each of R ^{4 ′ to} R ^{7 ′} is a hydrogen atom, an alkyl group or a heteroatom-containing alkyl group, and is bonded to an alicyclic structure-containing group represented by the following formula (i) to form a cyclic structure. Or a plurality of R ^{4 ′ to} R ^{7 ′} may be bonded to each other to form a cyclic structure.)
R ^{3 ′} is an alicyclic structure-containing group represented by the following formula (i).
(In the formula, Z represents an alicyclic structure having 5 to 20 carbon atoms which may have a hetero atom, and R ⁸ represents a substituted or unsubstituted carbon atom which may have a hetero atom or a cyclic structure. 10 is a divalent hydrocarbon group of 10 to 10, and R ⁹ is a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon A branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 15 carbon atoms, an alkoxy group, and an aryloxy group , Alkoxyalkyl groups, aryloxyalkyl groups, silyl groups, or these groups and divalent groups (substituted or unsubstituted alkylene groups, substituted or unsubstituted arylene groups, substituted or unsubstituted silylene groups, these groups Is 2 or more A group formed by combining these groups or a group formed by combining these groups with an ester group, a carbonate ester group or an ether group), and p and q are each independently an integer of 0 or more. The plurality of R ⁸ may be the same or different, and the plurality of R ⁹ may be the same or different.)
R ⁴ and R ⁵ are each a hydrogen atom, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, and a substituted group. Alternatively, it is an unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 12 carbon atoms, or a group obtained by combining two or more of these groups.
A ¹ is an alkylene group, an ether bond, a group in which two or more alkylene groups are combined, or a group in which one or more alkylene groups and one or more ether bonds are combined.
x is an integer of 1 to 5, y is 0 to 3, and z is an integer of 0 to 4.
A plurality of R ³ , R ⁴ , R ⁵ , Ar, A ¹ , L, x, y, and z may be the same or different. )) A compound represented by R ¹⁰¹ -X,
R ¹⁰¹ is a group represented by the following formula (11),
A compound in which X is a halogen atom, a hydroxyl group, an aryloxy group, or a (meth) acrylic acid ester group represented by the following formula (15).
(In Formula (11),
n is an integer of 0 or 1, respectively.
R ^a is a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon number 3 A cyclic aliphatic hydrocarbon group of -20, or a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms.
R ^b is an alicyclic structure-containing group represented by the formula (i).
(In the formula, Z represents an alicyclic structure having 5 to 20 carbon atoms which may have a hetero atom, and R ⁸ represents a substituted or unsubstituted carbon atom which may have a hetero atom or a cyclic structure. 10 is a divalent hydrocarbon group of 10 to 10, and R ⁹ is a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon A branched aliphatic hydrocarbon group having 3 to 12 carbon atoms, a substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 15 carbon atoms, an alkoxy group, and an aryloxy group , Alkoxyalkyl groups, aryloxyalkyl groups, silyl groups, or these groups and divalent groups (substituted or unsubstituted alkylene groups, substituted or unsubstituted arylene groups, substituted or unsubstituted silylene groups, these groups Is 2 or more A group formed by combining these groups or a group formed by combining these groups with an ester group, a carbonate ester group or an ether group), and p and q are each independently an integer of 0 or more. The plurality of R ⁸ may be the same or different, and the plurality of R ⁹ may be the same or different.)
R ^c is a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms, a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 10 carbon atoms, a substituted or unsubstituted carbon number 3 A cyclic aliphatic hydrocarbon group of -20, or a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms.
(In the above formula (15), R ^d is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.)   The compound according to claim 1, wherein Z has an adamantyl skeleton. The compound according to claim 1 or 3, wherein R ^{3 '} is a group represented by formula (ii) or (iii).
(R ⁸ , R ⁹ , p and q are the same as in formula (i).) The compound according to claim 4, wherein R ⁹ is a group represented by formula (iv).
(R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hetero element-containing alkyl group, an aromatic group having 6 to 18 carbon atoms, or a hetero element-containing aromatic group, and a plurality of R ¹⁰ are the same or different. R ¹¹ is a carbon atom substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms, silicon, oxygen, sulfur, nitrogen or a halogen-containing group. An alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 18 carbon atoms substituted by a group containing silicon, oxygen, sulfur, nitrogen or halogen, and r is an integer of 1 to 4.   The compound according to claim 1, wherein Z has a norbornyl skeleton. The compound according to claim 1 or 6, wherein R ^{3 '} is a group represented by formula (v).
(R ⁸ , R ⁹ , p and q are the same as in formula (i).) The compound according to claim 7, wherein R ⁹ is a group represented by formula (iv).
(R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a hetero element-containing alkyl group, an aromatic group having 6 to 18 carbon atoms, or a hetero element-containing aromatic group, and a plurality of R ¹⁰ are the same or different. R ¹¹ is a carbon atom substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 18 carbon atoms, silicon, oxygen, sulfur, nitrogen or a halogen-containing group. An alkyl group having 1 to 10 carbon atoms or an aromatic group having 6 to 18 carbon atoms substituted by a group containing silicon, oxygen, sulfur, nitrogen or halogen, and r is an integer of 1 to 4.   The compound according to claim 1, wherein R is a group represented by the formula (11).   The photoresist composition containing the compound and solvent of any one of Claim 1 and 3-9.   The photoresist composition of Claim 10 containing a photo-acid generator.   The photoresist composition of Claim 10 or 11 which contains a basic organic compound as a quencher.   The fine processing method using the photoresist composition of any one of Claims 10-12.   A semiconductor device manufactured by the microfabrication method according to claim 13.   An apparatus comprising the semiconductor device according to claim 14.