WO2010067622A1

WO2010067622A1 - Stereoisomeric cyclic compounds, manufacturing method therefor, compositions comprising the stereoisomeric cyclic compounds and manufacturing method therefor

Info

Publication number: WO2010067622A1
Application number: PCT/JP2009/006810
Authority: WO
Inventors: 柏村孝; 蓬田知行; 大和田貴紀; 塩谷英昭; 石井宏寿
Original assignee: 出光興産株式会社
Priority date: 2008-12-11
Filing date: 2009-12-11
Publication date: 2010-06-17

Abstract

Disclosed are compounds of 90% or higher purity and that are represented by only one or the other of formula (1) or formula (2), and compositions comprising compound (1) and compound (2) wherein the molar ratio of compound (1):compound (2) = 15:85‑70:30.

Description

Stereoisomeric cyclic compound, production method thereof, composition containing stereoisomeric cyclic compound, and production method thereof

The present invention relates to a photoresist base material used in the electrical / electronic field such as a semiconductor, an optical field, etc., and particularly to a photoresist base material for ultrafine processing.

Lithography using extreme ultraviolet light (Extreme Ultra Violet Light: hereinafter referred to as EUVL) or electron beam is useful as a high-performance, high-resolution fine processing method in the manufacture of semiconductors and the like. There is a need for photoresists with high sensitivity and high resolution. It is indispensable to improve the sensitivity of the photoresist from the viewpoint of the productivity and resolution of the desired fine pattern.

As a photoresist used in the ultrafine processing by EUVL, for example, a method using a chemically amplified positive photoresist having a higher concentration of photoacid generator than other resist compounds has been proposed (for example, Patent Document 1). However, the photoresists of the examples are considered to be limited in processing up to 100 nm exemplified in the case of using an electron beam 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.

The present inventor has already proposed a calix resorcinarene compound as a photoresist material with high sensitivity and high resolution (see Patent Documents 2 and 3). Patent Document 4 discloses a calix resorcinarene compound.

JP 2002-055457 A JP 2004-191913 A JP-A-2005-075767 US Pat. No. 6,093,517

However, higher sensitivity and higher resolution are required as an ultrafine processing technique using EUVL. The photoresist materials disclosed in the above-mentioned Patent Documents 1 to 4 cannot sufficiently exhibit the required high sensitivity and high resolution.
The present inventor has found that it is necessary to control the ratio of stereoisomers in order to obtain high sensitivity and high resolution (Japanese Patent Application No. 2008-315972).
However, in the production methods described in Patent Documents 1 to 4, it is not easy to control the ratio of stereoisomers.
Therefore, the present inventors have invented a method for controlling the ratio of stereoisomers by mixing a single stereoisomer and a mixture of stereoisomers as a method for controlling the ratio of stereoisomers.
Therefore, an object of the present invention is to provide a method for extracting only a single stereoisomer of a calixresorcinarene compound used in the above method.
Furthermore, an object of the present invention is to provide a photoresist material with high sensitivity and high resolution.

According to the present invention, the following compounds and photoresist compositions are provided.
1. A compound represented by only one of the following formulas (1) and (2) having a purity of 90% or more.

[Wherein, R is a group represented by any of the following formulas (3) to (5).
R ¹ represents 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, a substituted or unsubstituted cyclic group having 3 to 20 carbon atoms. An alkoxy group, a substituted or unsubstituted aryloxy 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. It is a group to which an ester bond, a carbonate ester bond or an ether bond is bonded.
R ² is hydrogen, 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 fatty acid having 3 to 20 carbon atoms. A 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) and the formula (2) may be the same or different.

(In the formula, Ar represents a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, a group obtained by combining two or more substituted or unsubstituted arylene groups having 6 to 10 carbon atoms, or at least an alkylene group and an ether bond. A combination of one or more of them and a substituted or unsubstituted arylene group having 6 to 10 carbon atoms,
In the case of having a substituent, the substituent is bromine, fluorine, a nitrile group, or an alkyl group having 1 to 10 carbon atoms.
R ³ represents a hydroxyl 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, a substituted or unsubstituted carbon, A cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, an alkoxy group, an alkoxyalkyl group, a carboxy group, a silyl group, or these groups and a divalent group. A bonded group,
The divalent group includes a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted silylene group, a group in which two or more of these groups are bonded, or one or more of these groups and an ester. A group in which one or more groups selected from a bond, a carbonate ester bond and an ether bond are bonded.
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, A substituted or 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 combination of 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 , x, y, and z may be the same or different. ]]
2. 2. The compound according to 1, wherein R ³ is an acid dissociable, dissolution inhibiting group of any one of the following formulas (I) to (IV):

(In the formulas (I) to (IV),
α 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 to 20 cyclic aliphatic hydrocarbon groups, or substituted or unsubstituted aromatic groups having 6 to 10 carbon atoms.
β is an alkoxy group substituted with a group having a tertiary aliphatic structure, an aromatic structure, a monocyclic aliphatic structure or a bicyclic aliphatic structure.
γ represents an aromatic structure, an alkoxy group substituted by a group having a monocyclic aliphatic structure or a polycyclic aliphatic structure, or one or more structures of an aromatic structure, a monocyclic aliphatic structure, and a polycyclic aliphatic structure; And an alkoxy group substituted with a combination of linear aliphatic hydrocarbon groups having 1 to 10 carbon atoms.
δ 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 to 20 cyclic aliphatic hydrocarbon groups, or substituted or unsubstituted aromatic groups having 6 to 10 carbon atoms. )
3. R is a group represented by the following formula (6), and in formula (6), R ⁴ is a group selected from the following formulas (7) to (38);
R ² is hydrogen;
3. The compound according to 1 or 2, wherein ^one of two R ¹ existing on the same aromatic ring is a hydroxyl group and the other is a solubility adjusting group.

(Wherein r represents any of the substituents represented by the above formulas (7) to (35))
4.1 A process for producing the compound according to any one of 1 to 3,
The difference between the solubility of the compound of the formula (1) at 0 ° C. and the solubility of the compound of the formula (2) at 0 ° C. is in the range of −50 ° C. to 50 ° C. in a solvent of 1 gram / liter or more. From the mixture of the compound of the formula (1) and the compound of the formula (2), the compound of the formula (1) or the compound of the formula (2) is crystallized and isolated, and the formula (1) Or a method for producing the compound of the formula (2).
5). 5. The production method according to 4, wherein the temperature of the crystallization isolation step is −20 ° C. or higher and 20 ° C. or lower.
6). 6. The production method according to 4 or 5, wherein the solvent is at least one solvent selected from a halogen-containing organic solvent and an oxygen-containing organic solvent.
7.1 A thin film comprising the compound according to any one of 1 to 3.
8). A composition comprising the following compound (1) and the following compound (2), wherein the molar ratio is compound (1): compound (2) = 15: 85 to 70:30.

(In the formula, Ar represents a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, a group obtained by combining two or more substituted or unsubstituted arylene groups having 6 to 10 carbon atoms, or at least an alkylene group and an ether bond. A combination of one or more of them and a substituted or unsubstituted arylene group having 6 to 10 carbon atoms,
In the case of having a substituent, the substituent is bromine, fluorine, a nitrile group, or an alkyl group having 1 to 10 carbon atoms.
R ³ represents a hydroxyl 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, a substituted or unsubstituted carbon, A cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, an alkoxy group, an alkoxyalkyl group, a carboxy group, a silyl group, or these groups and a divalent group. A bonded group,
The divalent group includes a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted silylene group, a group in which two or more of these groups are bonded, or one or more of these groups and an ester. A group in which one or more groups selected from a bond, a carbonate ester bond and an ether bond are bonded.
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, a substituted 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 , x, y, and z may be the same or different. ]]
9. 9. The composition according to 8, wherein R ³ is any one of the following formulas (I) to (IV).

(In the formulas (I) to (IV),
α 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 to 20 cyclic aliphatic hydrocarbon groups, or substituted or unsubstituted aromatic groups having 6 to 10 carbon atoms.
β is an alkoxy group substituted with a group having a tertiary aliphatic structure, an aromatic structure, a monocyclic aliphatic structure or a bicyclic aliphatic structure.
γ represents an aromatic structure, an alkoxy group substituted by a group having a monocyclic aliphatic structure or a polycyclic aliphatic structure, or one or more structures of an aromatic structure, a monocyclic aliphatic structure, and a polycyclic aliphatic structure; And an alkoxy group substituted with a combination of linear aliphatic hydrocarbon groups having 1 to 10 carbon atoms.
δ 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 to 20 cyclic aliphatic hydrocarbon groups, or substituted or unsubstituted aromatic groups having 6 to 10 carbon atoms. )
10. R is a group represented by the following formula (6), and in formula (6), R ⁴ is a group selected from the following formulas (7) to (38);
R ² is hydrogen;
10. The composition according to 8 or 9, wherein ^one of two R ¹ existing on the same aromatic ring is a hydroxyl group and the other is a solubility adjusting group.

(Wherein r represents any of the substituents represented by the above formulas (7) to (35))
A method for producing the composition according to any one of 11.8 to 10, comprising:
The difference between the solubility of compound (1) at 0 ° C. and the solubility of compound (2) at 0 ° C. is 1 gram / liter or more under the condition of −50 ° C. or more and 50 ° C. or less under the condition of compound (1) And controlling the molar ratio of the compound (1) and the compound (2) in the mixture by crystallizing and isolating a predetermined amount of the compound (1) or the compound (2) from the mixture of the compound (2) A method for producing a composition.
A method for producing the composition according to any one of 12.8 to 10, comprising:
The difference between the solubility of compound (1) at 0 ° C. and the solubility of compound (2) at 0 ° C. is 1 gram / liter or more under the condition of −50 ° C. or more and 50 ° C. or less under the condition of compound (1) And a crystallization isolation step of crystallizing and isolating the compound (1) or the compound (2) from a mixture of the compound (2) and
The isolated compound (1) or compound (2) and a mixture of the compound (1) and the compound (2) are mixed at a predetermined ratio, and the molar ratio of the compound (1) and the compound (2) is determined. A mixing ratio control step to control;
The manufacturing method of the composition containing this.
A method for producing the composition according to any one of 13.8 to 10, comprising:
A mixture synthesis step of synthesizing a first mixture of compound (1) and compound (2) and a second mixture of compound (1) and compound (2);
The difference between the solubility of compound (1) at 0 ° C. and the solubility of compound (2) at 0 ° C. is 1 gram / liter or more under the condition of −50 ° C. or more and 50 ° C. or less under the conditions of the first A crystallization isolation step of crystallizing and isolating compound (1) or compound (2) from the mixture;
The first mixture after the compound (1) or the compound (2) is isolated by the crystallization isolation step and the second mixture are mixed at a predetermined ratio, and the compound (1) and the compound ( A mixing ratio control step for controlling the molar ratio of 2);
The manufacturing method of the composition containing this.
14 14. The production method according to any one of 11 to 13, wherein a temperature in the crystallization isolation step is −20 ° C. or higher and 20 ° C. or lower.
15. 15. The production method according to any one of 11 to 14, wherein the solvent is at least one solvent selected from a halogen-containing organic solvent and an oxygen-containing organic solvent.
16. A composition containing a compound according to any one of 1 to 3 and a solvent, or a photoresist composition containing the composition and a solvent according to any one of 8 to 10.
A thin film comprising the composition according to any one of 17.8 to 10.
A fine processing method using the photoresist composition according to 18.16.
A semiconductor device manufactured by the microfabrication method described in 19.18.

According to the present invention, only a single stereoisomer of the calix resorcinalene compound can be taken out. Stereoisomers can be used as raw materials for high-sensitivity, high-resolution photoresist materials.

According to the present invention, a photoresist material with high sensitivity and high resolution can be provided.
The composition of the present invention includes two types of stereoisomers that differ in a predetermined ratio. By including at a predetermined ratio, the performance is improved.

1 is a ¹ H-NMR spectrum of a compound (1b) synthesized in Example A-1 (Reference Example B-1). 1 is a ¹ H-NMR spectrum of a compound (2b) synthesized in Example A-1 (Reference Example B-1). 1 is a ¹ H-NMR spectrum of a compound (3b) synthesized in Example A-1 (Reference Example B-1). 1 is a ¹ H-NMR spectrum of a compound (1c) synthesized in Comparative Example A-1 (Comparative Example B-1). 1 is a ¹ H-NMR spectrum of a compound (2c) synthesized in Comparative Example A-1 (Comparative Example B-1). 1 is a ¹ H-NMR spectrum of a compound (3c) synthesized in Comparative Example A-1 (Comparative Example B-1). ¹ is a ¹ H-NMR spectrum of a mixture of compounds (1a) and (1b) synthesized in Example B-1. ¹ is a ¹ H-NMR spectrum of a mixture of compounds (2a) and (2b) synthesized in Example B-1. ¹ is a ¹ H-NMR spectrum of a mixture of compounds (3a) and (3b) synthesized in Example B-1. ¹ is a ¹ H-NMR spectrum of a mixture of compounds (4a) and (4b) synthesized in Example B-5. ¹ is a ¹ H-NMR spectrum of a mixture of compounds (5a) and (5b) synthesized in Example B-6. ¹ is a ¹ H-NMR spectrum of a mixture of compounds (2a) and (2b) synthesized in Example B-7. ¹ is a ¹ H-NMR spectrum of a mixture of compounds (4a) and (4b) synthesized in Example B-7. ¹ is a ¹ H-NMR spectrum of a mixture of compounds (5a) and (5b) synthesized in Example B-8.

<First aspect>
The compound of the present invention is represented by only one of the following formulas (1) and (2).

In the formula, R is a group represented by any of the following formulas (3) to (5).

R ¹ represents 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, a substituted or unsubstituted cyclic group having 3 to 20 carbon atoms. An alkoxy group, a substituted or unsubstituted aryloxy group having 6 to 10 carbon atoms, an alkoxyalkyloxy 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 in which an ester bond (—CO ₂ —), a carbonate ester bond (—CO ₃ —), or an ether bond (—O—) is bonded.

R ² is hydrogen, 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 fatty acid having 3 to 20 carbon atoms. A 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) and the formula (2) may be the same or different.

In the formula, Ar represents a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, a group obtained by combining two or more substituted or unsubstituted arylene groups having 6 to 10 carbon atoms, or at least one of an alkylene group and an ether bond. And a substituted or unsubstituted arylene group having 6 to 10 carbon atoms. In the case of having a substituent, the substituent is bromine, fluorine, a nitrile group, or an alkyl group having 1 to 10 carbon atoms.

R ³ represents a hydroxyl 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, a substituted or unsubstituted carbon, A cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, an alkoxy group, an alkoxyalkyl group, a carboxy group, a silyl group, or these groups and a divalent group. A divalent group is a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted silylene group, a group in which two or more of these groups are bonded, or a group thereof. It is a group in which one or more and one or more groups selected from an ester bond, a carbonate ester bond and an ether bond are bonded.

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, a substituted 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 from 1 to 5, y is from 0 to 3, and z is an integer from 0 to 4.

A plurality of R ³ , R ⁴ , R ⁵ , Ar, A ¹ , x, y, and z may be the same or different.

The compound of the present invention contains either stereoisomer of formula (1) or formula (2) at a purity of 90% or more. Preferably, it is a compound consisting essentially of a specific stereoisomer, and most preferably 100%.

In the formulas (1) and (2), R ³ is preferably an acid dissociable, dissolution inhibiting group.
An example of the acid dissociable, dissolution inhibiting group is a group having at least a carbon atom, a hydrogen atom, and an oxygen atom having a tertiary aliphatic structure, an aromatic structure, a monocyclic aliphatic structure, or a bicyclic aliphatic structure. An example of the tertiary aliphatic structure is a tert-butyl group. Examples of the aromatic structure include benzene and naphthalene. Examples of the monocyclic aliphatic structure include cyclohexane and cyclopentane. Examples of the bicyclic aliphatic structure include adamantane and norbornene.

Preferably, R ³ is represented by any of the following formulas (I) to (IV).

In the formulas (I) to (IV), α is a substituted or unsubstituted linear aliphatic hydrocarbon group having 1 to 10 carbon atoms or a substituted or unsubstituted branched aliphatic hydrocarbon group having 3 to 10 carbon atoms. A substituted or unsubstituted cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, or a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms.

Β is an alkoxy group substituted with a group having a tertiary aliphatic structure, an aromatic structure, a monocyclic aliphatic structure or a bicyclic aliphatic structure. Preferably, a tertiary carbon contained in a group having a tertiary aliphatic structure, an aromatic structure, a monocyclic aliphatic structure or a bicyclic aliphatic structure is bonded to an oxygen atom.

γ represents an aromatic structure, an alkoxy group substituted by a group having a monocyclic aliphatic structure or a polycyclic aliphatic structure, or one or more structures of an aromatic structure, a monocyclic aliphatic structure, and a polycyclic aliphatic structure; And an alkoxy group substituted with a combination of linear aliphatic hydrocarbon groups having 1 to 10 carbon atoms. The alkoxy group substituted by a group having an aromatic structure, a monocyclic aliphatic structure or a polycyclic aliphatic structure is preferably a tertiary aliphatic structure, an aromatic structure, a monocyclic aliphatic structure or a polycyclic aliphatic structure. The tertiary carbon contained in the group to be bonded to the oxygen atom.

δ 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 to 20 cyclic aliphatic hydrocarbon groups, or substituted or unsubstituted aromatic groups having 6 to 10 carbon atoms.

In formulas (1) and (2), R ² is preferably hydrogen.
Preferably, one of two R ¹ existing on the same aromatic ring is a hydroxyl group, and the other is a solubility adjusting group. Suitable solubility adjusting groups include alkoxy groups having 1 to 6 carbon atoms.

R is preferably a group represented by the following formula (6).
In the formula (6), R ⁴ is a group selected from the following formulas (7) to (38).

In the formula, r represents any of the substituents represented by the above formulas (7) to (35).

The compound of the present invention can be produced as follows.
First, a mixture of a compound having the structure of the above formula (1) (hereinafter also referred to as compound (1)) and a compound having the structure of the above formula (2) (hereinafter also referred to as compound (2)) is produced.
As described in Japanese Patent Application Laid-Open No. 2009-269901 (Japanese Patent Application No. 2008-158769), for example, in the presence of an acid catalyst, the mixture is a condensed cyclization of an aldehyde compound having a corresponding structure and a phenol derivative having a corresponding structure. A calix resorcinarene derivative (precursor) is synthesized by reaction, and a compound corresponding to a group such as R ³ can be synthesized by introducing it into the precursor by esterification reaction, etherification reaction, acetalization reaction, or the like.

Next, a difference Δd between the solubility of the compound (1) at 0 ° C. and the solubility of the compound (2) at 0 ° C. in a solvent having a concentration of 1 gram / liter or more is −50 ° C. or more and 50 ° C. or less, Only compound (1) or compound (2) is crystallized and isolated from the mixture.

In order to realize the present invention, it is necessary to use a solvent having a difference in solubility Δd at 0 ° C. between the stereoisomers of the compound (1) and the compound (2) of 1 gram / liter or more, and −50 A single compound having a lower solubility of the compound (1) and the compound (2) is precipitated as a solid under the conditions of -50 ° C. to 50 ° C., particularly preferably -20 ° C. to 20 ° C. Obtained.

Examples of applicable solvents include halogen-containing organic solvents and oxygen-containing organic solvents. Specific examples of the halogen-containing organic solvent include dichloromethane, chloroform, carbon tetrachloride, monochloroethane, dichloroethane, trichloroethane, tetrachloroethane, monochlorobenzene, dichlorobenzene, trichlorobenzene, trifluoroethanol, hexafluoroisopropanol, and the like. Examples of the oxygen-containing organic solvent include diethyl ether, tetrahydrofuran, 1,4-dioxane, propylene glycol methyl ether acetate, propylene glycol monomethyl ether, ethyl acetate, ethyl lactate, acetone, methyl ethyl ketone, and cyclohexanone.

The solvent used when producing the compound (1) and the compound (2) is preferably the same as the solvent used for separating the compound (1) and the compound (2).
If the solvents are the same, it is not necessary to wash the mixture of the compound (1) and the compound (2), and the purification step can be eliminated.

As described above, the compound of the present invention is isolated at −50 to 50 ° C., particularly preferably −20 to 20 ° C.
When the compound obtained at a temperature lower than −50 ° C. is used for a photoresist base material, the performance is inferior. For this reason, if it is isolated at less than −50 ° C., it is considered that not only the compound (1) and the compound (2) cannot be separated, but also the deterioration of performance due to the presence of impurities.

In addition, at a temperature exceeding 50 ° C., the solubility of both the compound (1) and the compound (2) increases, and the compound (1) and the compound (2) cannot be separated as a result. Moreover, although it depends on the type of solvent used, it becomes difficult to control the concentration due to boiling or diffusion of the solvent vapor, and there is a risk of ignition or explosion.

If all compounds with low solubility can be isolated, the other compound with high solubility can be isolated from the remaining solution. For example, it is isolated by precipitation at a lower temperature or by adding a poor solvent that does not dissolve the compound dissolved in the solution.

The cyclic compound which is a specific stereoisomer of the present invention can be used as a material for a photoresist substrate. A photoresist composition can be prepared from a photoresist substrate and a solvent. The photoresist composition can further contain a known photoacid generator, acid diffusion control agent, and the like, if necessary.

A thin film can be formed from a compound of the present invention on a substrate such as a silicon wafer by a known molding method.

Formation 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, the obtained thin film may be cured (cycloaddition reaction) with heat, ultraviolet light, deep ultraviolet light, vacuum ultraviolet light, extreme ultraviolet light, electron beam, plasma, X-ray or the like.

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.

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.

Thin films using the compounds of the present invention are used as photoresist thin films, optical thin films for various optical information processing devices such as optical lenses, optical fibers, optical waveguides, and photonic crystals, interlayer insulating films for semiconductors, and semiconductors. It is useful as a thin film for ULSI devices such as a protective film, a thin film for image display devices such as a liquid crystal display, a liquid crystal projector, a plasma display, an EL display, and an LED display, a thin film used for a CMOS image sensor, a CCD image sensor, and the like. Further, these thin films are provided for semiconductor devices such as CPUs, DRAMs, flash memories, etc., electronic circuit devices such as information processing small electronic circuit devices, 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.

<Second aspect>
The composition of the present invention comprises the following compound (1) and the following compound (2).
The molar ratio of compound (1) to compound (2) is 15:85 to 70:30.
If it is less than 15%, a part of the compound (2) does not dissolve but remains as an insoluble substance in a general solvent used for preparing a photoresist solution such as propylene glycol monomethyl ether, and a uniform photoresist solution When the amount exceeds 70%, a part of the compound (1) remains in an insoluble substance in a general solvent used in preparing a photoresist solution such as propylene glycol monomethyl ether, and remains homogeneous. A photoresist solution cannot be obtained.
Further, it is preferably 15:85 to 67:33.

The definition and preferred examples of substituents in the formula are the same as described in the first aspect, and are omitted here.

The composition of the present invention consists essentially of only two types of stereoisomers. Preferably, 90% or more are two types of stereoisomers.

The composition of the present invention can be produced by mixing the compound (1) and the compound (2) of the present invention in a predetermined molar ratio or as follows.
First, a mixture of a compound having the structure of the above formula (1) (hereinafter also referred to as compound (1)) and a compound having the structure of the above formula (2) (hereinafter also referred to as compound (2)) is produced.
As described in Japanese Patent Application No. 2008-158769, the mixture is prepared by, for example, a calixresorcinarene derivative ( And a compound corresponding to a group such as R ³ can be synthesized by introducing it into the precursor by an esterification reaction, an etherification reaction, an acetalization reaction, or the like.

Next, the ratio of the compound (1) and the compound (2) is adjusted.
For example, there are the following methods.
-A predetermined amount of compound (1) or compound (2) is removed from the above mixture, and the ratio in the mixture is adjusted.
-Isolate compound (1) or compound (2) from the above mixture. The isolated compound (1) or compound (2) and a mixture of the compound (1) and the compound (2) are mixed to adjust the ratio in the mixture. At this time, the mixture of the compound (1) and the compound (2) may be a mixture after isolating the compound (1) or the compound (2), or may be a separately prepared mixture.
-The mixture produced separately is mixed with the mixture except compound (1) or compound (2), and the ratio in a mixture is adjusted.
-Isolate compound (1) and compound (2) from the mixture. The isolated compound (1) and compound (2) are mixed in a desired ratio.
In the present invention, “mixing at a predetermined ratio” includes not only physical mixing but also mixing after dissolving the object to be mixed in a solvent.
For example, the compound (1) and the compound (2) may be physically mixed, or the compound (1) and the compound (2) may be mixed in a solvent in which each of them is dissolved. Since the solvent that can be used differs depending on the compound, it cannot be generally described, but a halogen-containing organic solvent or an oxygen-containing organic solvent can be preferably used.

If the mixture in which the above ratio is adjusted becomes uniform in the photoresist solution to be produced, it may not be mixed in advance.

The method for isolating the compound (1) or the compound (2) from the mixture is as described in the first embodiment, and is omitted here.

The photoresist composition of the present invention contains a composition and a solvent containing the cyclic compound of the above formula (1) or (2), or a composition of the cyclic compound of the above formulas (1) and (2) and a solvent. To do. The composition is used as a substrate.
The compounding amount of the cyclic compound composition is preferably 50 to 99.9% by weight, more preferably 75 to 95% by weight in the total composition excluding the solvent.

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 ( L) 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, Examples thereof include cyclic ethers such as dioxane 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 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 total 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%, and 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 alkyl halide 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 R ⁵² , 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 or the like, 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, an aryl group having no substituent is 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.
Examples of other onium salt 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 alkyl group; R ⁴ ″ represents a linear, branched or cyclic group; 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 groups, alkoxy groups 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 which 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 ″ to R ³ ″ is not particularly limited, and examples thereof include linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms. From the viewpoint of excellent resolution, the number of carbon atoms is preferably 1 to 5. Specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, nonyl group, decanyl group and the like. 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 represented by R ¹ ″, preferably having 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, those in which 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 those similar to the substituted or unsubstituted aryl group for R ¹ ″ to R ³ ″.
As the alkyl group for R ⁵ ″ to R ⁶ ″, the same as the alkyl groups for R ¹ ″ to R ³ ″ can be used.
Of 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 the formulas (a-1) and (a-2) include diphenyliodonium trifluoromethanesulfonate or nonafluorobutanesulfonate, bis (4-tert-butylphenyl) iodonium. Trifluoromethanesulfonate or nonafluorobutanesulfonate, triphenylsulfonium trifluoromethanesulfonate, heptafluoropropanesulfonate or nonafluorobutanesulfonate, tri (4-methylphenyl) sulfonium trifluoromethanesulfonate, heptafluoropropanesulfonate or the same Nonafluorobutanesulfonate, dimethyl (4-hydroxynaphthyl) sulfonium trifluoromethanesulfonate, its heptafluoropropyl Pansulfonate or its nonafluorobutanesulfonate, trifluoromethanesulfonate of monophenyldimethylsulfonium, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, trifluoromethanesulfonate of diphenylmonomethylsulfonium, its heptafluoropropanesulfonate or its nonafluorobutanesulfonate, (4-methylphenyl) diphenylsulfonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, bird( -Tert-butyl) phenylsulfonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluorobutane sulfonate, diphenyl (1- (4-methoxy) naphthyl) sulfonium trifluoromethanesulfonate, its heptafluoropropane sulfonate or its nonafluoro Examples include butane sulfonate. 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.

Further, an onium salt acid generator in which the anion moiety is replaced by the anion moiety represented by the following formula (a-3) or (a-4) in the 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 has 1 to 7 carbon atoms, more preferably 1 to 3 carbon atoms.

The number of carbon atoms of the alkylene group of X ″ or the number of carbon atoms of the alkyl group of Y ″ and Z ″ is preferably as small as possible because the solubility in a resist solvent is good within the above-mentioned range of carbon numbers.

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- 10-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-dicarbo Siimide, 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, To N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] It is preferably at least one selected from the group consisting of pto-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 is 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 the 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, an isopropyl group, a cyclopentyl group, or a cyclohexyl group. A cycloalkyl group such as methoxy group, ethoxy group, propoxy group and the like, or an aryl group such as phenyl group, toluyl group and 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- Preferred examples include 1,2-quinonediazidosulfonyl groups such as a 6-sulfonyl group. In particular, 1,2-naphthoquinonediazido-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, R ²² each 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 (cyclohexylsulfur) Bissulfonyldiazomethanes such as nylazomethylsulfonyl) 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.

Among these photoacid generators, a compound that generates an organic sulfonic acid by the action of actinic rays or radiation is particularly preferable.

The blending amount of PAG is 0 to 40% by weight, preferably 5 to 30% by weight, and 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 Trialkylamines such as tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decanylamine, tri-n-dodecylamine; diethanolamine, triethanolamine, diisopropanolamine, Isopropano Alkyl alcohol amines such as amine, di-n-octanolamine, 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, basic iodonium compounds, etc. 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, based on 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 controlling 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 kind 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, and further 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 developability 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. The nonionic surfactant has a good affinity with the solvent used in the photoresist composition and is 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 compounding amount of the surfactant is preferably 0 to 2% by weight, more preferably 0 to 1% by weight, and further preferably 0 to 0.1% by weight based on the total weight of the solid components.

Also, by blending a dye or pigment, the latent image in the exposed area can be visualized and the influence of halation during exposure can be mitigated. 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 oxoacids or derivatives thereof include phosphoric acid, phosphoric acid di-n-butyl ester, phosphoric acid diphenyl ester and other phosphoric acid or derivatives thereof, 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 acids 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 on the substrate in advance. Examples of the surface treatment agent include silane coupling agents such as hexamethylene disilazane (hydrolyzable polymerizable silane coupling agent having a polymerizable group, etc.), anchor coating agents or base agents (polyvinyl acetal, acrylic resins, 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 invasion of amines floating in the atmosphere. 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 fine pattern with high accuracy 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.

Then, 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), and choline. 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 treatment may be performed after the alkali development, and 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 stripped with an aqueous solution 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. The wiring board on which the resist pattern is formed may be a multilayer wiring board or may have a small diameter through hole.

It is also possible to form a wiring board by a method of forming a resist pattern using the photoresist composition of the present invention, vacuum depositing a metal, and then eluting the resist pattern 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 composition of the cyclic 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 a known molding method.

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.

Moreover, a thin film is obtained by the above method using the composition of the cyclic compound of the present invention, and the obtained thin film is cured by heat, ultraviolet rays, deep ultraviolet rays, vacuum ultraviolet rays, extreme ultraviolet rays, electron beams, plasma, X-rays, etc. (Cycloaddition reaction) may be performed.

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

The concentration of the composition of the cyclic compound of the present invention in the paint may be appropriately adjusted in consideration of the viscosity of the paint, the thin film forming method, and the like.
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. Further, these thin films are provided for semiconductor devices such as CPUs, DRAMs, flash memories, etc., electronic circuit devices such as information processing small electronic circuit devices, 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.

<First aspect>
[Example A-1]
Under a nitrogen stream, 10.0 g (81 mmol) of 3-methoxyphenol, 13.2 g (80.6 mmol) of methyl 4-formylbenzoate, and 100 ml of dehydrated chloroform were added to a round bottom flask having a volume of 200 ml. Cooled to ° C. After 30.8 ml (250 mmol) of boron trifluoride ether adduct was added dropwise to the mixture, the mixture was warmed to room temperature and stirred for 20 hours, then heated to 50 ° C. and stirred for 14 hours. Continued. The reaction solution was cooled to 0 ° C. in an ice bath, and the precipitated solid was washed with ethanol to obtain a cyclic compound (1b) having the following structure in a yield of 25%. ^From the result of ¹ H-NMR measurement (FIG. 1), the structure of the cyclic compound (1b) was confirmed and confirmed to be a pure product by liquid chromatography.

Under a nitrogen stream, 0.8 g (0.74 mmol) of the obtained cyclic compound (1b), 0.74 g (18.5 mmol) of sodium hydroxide and 10 ml of water were added, and the mixture was heated and stirred at 90 ° C. for 5 hours. Then, it was allowed to cool. A dilute aqueous hydrochloric acid solution was added to acidify the reaction solution, and the precipitated white precipitate was collected by filtration and washed with water to obtain a cyclic compound (2b) with a yield of 89%. ^From the result of ¹ H-NMR measurement (FIG. 2), the structure of the cyclic compound (2b) was confirmed and confirmed to be pure by liquid chromatography.

Under a nitrogen stream, to a mixture of the obtained cyclic compound (2b) 5.03 g (4.88 mmol), sodium hydrogencarbonate 1.86 g (21.95 mmol), N-methyl-2-pyrrolidone 100 ml, After dropwise addition of 6.23 g (21.95 mmol) of 1-ethylcyclohexyl bromoacetate, the mixture was stirred with heating at 80 ° C. for 8 hours. The reaction mixture was allowed to cool and extracted with ethyl acetate / water. The organic layer was concentrated and reprecipitated with hexane, and the precipitated solid was filtered off to obtain a cyclic compound (3b) in a yield of 83%. ^From the result of ¹ H-NMR measurement (FIG. 3), the structure of the cyclic compound (3b) was confirmed and confirmed to be a pure product by liquid chromatography.

[Comparative Example A-1]
Under a nitrogen stream, 10.0 g (81 mmol) of 3-methoxyphenol, 13.2 g (80.6 mmol) of methyl 4-formylbenzoate, and 100 ml of dehydrated dichloromethane were added to a round bottom flask having a capacity of 200 ml, and -78 Cooled to ° C. To this mixture, 30.8 ml (250 mmol) of boron trifluoride ether adduct was dropped, and then the temperature was raised to room temperature and stirring was continued for 8 hours. The reaction solution was cooled to −78 ° C., and the precipitated solid was washed with 80 ml of dichloromethane, 200 ml of water and ethanol to obtain the following cyclic compound (1c) which is a mixture of the cyclic compound (1a) and the cyclic compound (1b). Obtained in 20.5 g (94% yield). As a result of ¹ H-NMR measurement (FIG. 4), the following structure was confirmed.

A cyclic compound (2c), which is a mixture of the following cyclic compound (2a) and cyclic compound (2b), was obtained in the same manner as in Example A-1 except that the cyclic compound (1c) was used as a starting material. (Yield 90%). As a result of ¹ H-NMR measurement (FIG. 5), the following structure was confirmed.

A cyclic compound (3c), which is a mixture of the following cyclic compound (3a) and cyclic compound (3b), was obtained in the same manner as in Example A-1, except that the cyclic compound (2c) was used as a starting material. (Yield 69%). As a result of ¹ H-NMR measurement (FIG. 6), the following structure was confirmed.
In the cyclic compound (3c) obtained in this comparative example, the stereoisomer mixture ratio of the benzoate structure bonded to the cyclic structure was determined by ¹ H-NMR and liquid chromatography. The molar ratio of the following cyclic compounds (3a) and (3b) was 2: 3. However, even if the same production method is repeatedly carried out, including by-products of unknown structure that cannot be separated, the molar ratios of the cyclic compounds (3a) and (3b) are different each time, and further, by-products of unknown structure. Product formation could not be suppressed.

<Second aspect>
[Example B-1]
Under a nitrogen stream, 10.0 g (81 mmol) of 3-methoxyphenol, 13.2 g (80.6 mmol) of methyl 4-formylbenzoate, and 100 ml of dehydrated dichloromethane were added to a round bottom flask having a capacity of 200 ml, and -78 Cooled to ° C. To this mixture, 30.8 ml (250 mmol) of boron trifluoride ether adduct was dropped, and then the temperature was raised to room temperature and stirring was continued for 8 hours. The reaction solution is cooled to 0 ° C. in an ice bath, the precipitated solid (cyclic compound (1b)) is removed by filtration, and the obtained solid solution is poured into n-hexane to collect the precipitated solid by filtration. , A mixture of cyclic compounds (1a) and (1b) [(1a) :( 1b) = 2: 1 (molar ratio)] was obtained in a yield of 60%. As a result of ¹ H-NMR measurement (FIG. 7), the following structure and the above composition were confirmed.

Under a nitrogen stream, 0.8 g (0.74 mmol) of a mixture of the obtained cyclic compounds (1a) and (1b), 0.74 g (18.5 mmol) of sodium hydroxide and 10 ml of water were added, The mixture was heated and stirred for 5 hours and then allowed to cool. The reaction solution is acidified by adding a dilute hydrochloric acid solution, and the precipitated white precipitate is filtered and washed with water, whereby a mixture of cyclic compounds (2a) and (2b) [(2a) :( 2b) = 2: 1 (molar ratio)] In a yield of 85%. As a result of ¹ H-NMR measurement (FIG. 8), it was confirmed that the following structure and the above composition were obtained.

Under a nitrogen stream, 5.03 g (4.88 mmol) of a mixture of the obtained cyclic compounds (2a) and (2b), 1.86 g (21.95 mmol) of sodium bicarbonate, 100 ml of N-methyl-2-pyrrolidone To the mixture, 6.23 g (21.95 mmol) of 1-ethylcyclohexyl 2-bromoacetate was added dropwise, followed by stirring with heating at 80 ° C. for 8 hours. The reaction mixture was allowed to cool and extracted with ethyl acetate / water. The organic layer is concentrated and reprecipitated with hexane, and the precipitated solid is separated by filtration. As a final product, a mixture of cyclic compounds (3a) and (3b) [(3a) :( 3b) = 2: 1 (molar ratio)] was obtained in a yield of 80%. As a result of ¹ H-NMR measurement (FIG. 9), the following structure and the above composition were confirmed.

[Reference Example B-1]
Example A-1 in the first aspect was designated as Reference Example B-1 in the second aspect.

[Examples B-2 to B-4]
A mixture of the cyclic compounds (3a) and (3b) obtained in Example B-1 (2: 1 (molar ratio)) and a pure product of the cyclic compound (3b) obtained in Reference Example B-1 were respectively obtained. By mixing at a ratio shown in Table 1, a mixture containing the cyclic compounds (3a) and (3b) at a ratio shown in Table 1 was created. Thus, a mixture of the cyclic compounds (3a) and (3b) mixed at a desired ratio can be obtained accurately.

[Comparative Example B-1]
Comparative Example A-1 in the first aspect was designated as Comparative Example B-1 in the second aspect.
In the cyclic compound (3c) obtained in Comparative Example B-1, the stereoisomer mixture ratio of the benzoate structure bonded to the cyclic structure was determined by ¹ H-NMR and liquid chromatography. The molar ratio of the following cyclic compounds (3a) and (3b) was 2: 3. However, even if the same production method is repeatedly carried out, including by-products of unknown structure that cannot be separated, the molar ratios of the cyclic compounds (3a) and (3b) are different each time, and further, by-products of unknown structure. Product formation could not be suppressed.

[Evaluation Example 1]
A photoresist solution composed of a substrate, PAG, quencher, and solvent was prepared, and a pattern was formed on a silicon wafer using an electron beam.
As the substrate, 77 parts by weight of the mixture obtained in Examples B-1 to B-4 and Comparative Example B-1 and the compound obtained in Reference Example B-1 were used, respectively, and triphenylsulfonium nonafluorobutane as PAG 20 parts by weight of sulfonate and 3 parts by weight of 1,4-diazabicyclo (2,2,2) octane were used as a quencher. These solid components were dissolved in propylene glycol monomethyl ether so as to have a concentration of 2.5% by weight.

When the cyclic compound of Reference Example B-1 was used, an insoluble substance remained in propylene glycol monomethyl ether, so that a uniform photoresist solution could not be produced.

A photoresist solution containing a mixture of Examples B-1 to B-4 and Comparative Example B-1 was spin-coated on a silicon wafer subjected to hexamethyldisilazane (HMDS) treatment at 100 ° C. A thin film was formed by heating for 180 seconds. Next, the substrate having this thin film was drawn using an electron beam drawing apparatus (acceleration voltage 50 kV), baked at 100 ° C. for 60 seconds, and then added with an aqueous tetrabutylammonium hydroxide solution having a concentration of 2.38 wt%. The film was developed for 2 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.

From Table 2, it was confirmed that Examples B-1 to B-4, ie, (3a) :( 3b), had a preferable performance as a photoresist in the range of 15:85 to 67:33. On the other hand, from Table 2, when Reference Example B-1, that is, only compound (3b) and (3a) :( 3b) are outside the above preferred range, as described above, under the conditions of this evaluation example, No uniform photoresist solution was obtained, and Comparative Example B-1, that is, (3a) :( 3b) was within the above-mentioned preferred range, but the purification of the present invention was not carried out and the structure was unknown. When the product was included, it was confirmed that the performance decreased in terms of resolution. The results were the same even when tri-n-octylamine was used as the quencher instead of 1,4-diazabicyclo (2,2,2) octane.

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.

[Example B-5]
Under a nitrogen stream, 5.03 g (4.88 mmol) of a mixture of the cyclic compounds (2a) and (2b) obtained in Example B-1; 1.86 g (21.95 mmol) of sodium bicarbonate; N— To a mixture of 100 ml of methyl-2-pyrrolidone, 6.59 g (21.95 mmol) of ethyl adamantyl bromoacetate was added dropwise, followed by heating and stirring at 80 ° C. for 8 hours. The reaction mixture was allowed to cool and extracted with ethyl acetate / water. The organic layer is concentrated and reprecipitated with hexane, and the precipitated solid is filtered off to obtain a mixture of cyclic compounds (4a) and (4b) [(4a) :( 4b) = 2: 1 (molar ratio)] was obtained in a yield of 82%. As a result of ¹ H-NMR measurement (FIG. 10), the following structure and the above composition were confirmed.

[Example B-6]
Under a nitrogen stream, 5.03 g (4.88 mmol) of a mixture of the cyclic compounds (2a) and (2b) obtained in Example B-1; 1.86 g (21.95 mmol) of sodium bicarbonate; N— To a mixture of 100 ml of methyl-2-pyrrolidone, 6.14 g (21.95 mmol) of methyl adamantyl bromoacetate was added dropwise, followed by heating and stirring at 80 ° C. for 8 hours. The reaction mixture was allowed to cool and extracted with ethyl acetate / water. The organic layer is concentrated and reprecipitated with hexane, and the precipitated solid is filtered off to obtain a mixture of cyclic compounds (5a) and (5b) [(5a) :( 5b) = 2: 1 (molar ratio)] was obtained in a yield of 83%. As a result of ¹ H-NMR measurement (FIG. 11), the following structure and the above composition were confirmed.

[Example B-7]
Under a nitrogen stream, 50.0 g (402.8 mmol) of 3-methoxyphenol, 60.5 g (402.8 mmol) of 4-formylbenzoic acid, and 500 ml of dehydrated dichloromethane were added to a round bottom flask having a capacity of 200 ml. It was 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 diethyl ether adduct was added dropwise so that the internal temperature did not exceed 15 ° C., then the mixture was warmed to room temperature and stirred 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. The precipitate separated by filtration is washed with water until neutral, then dissolved in N-methyl-2-pyrrolidone, reprecipitated with ethyl acetate, and the precipitated solid is separated by filtration, whereby the cyclic compound (2a), ( A mixture of 2b) [(2a) :( 2b) = 1: 2 (molar ratio)] was obtained in a yield of 93%. As a result of ¹ H-NMR measurement (FIG. 12), the following structure and the above composition were confirmed.

Under a nitrogen stream, 5.03 g (4.88 mmol) of the mixture of the cyclic compounds (2a) and (2b) obtained above, 1.86 g (21.95 mmol) of sodium bicarbonate, N-methyl-2-pyrrolidone To 100 ml of the mixture, 6.59 g (21.95 mmol) of ethyl adamantyl bromoacetate was added dropwise, followed by heating and stirring at 80 ° C. for 8 hours. The reaction mixture was allowed to cool and extracted with ethyl acetate / water. The organic layer is concentrated and reprecipitated with hexane, and the precipitated solid is filtered off to obtain a mixture of cyclic compounds (4a) and (4b) [(4a) :( 4b) = 1: 3 (molar ratio)] was obtained in a yield of 75%. As a result of ¹ H-NMR measurement (FIG. 13), the following structure and the above composition were confirmed.

[Example B-8]
Under a nitrogen stream, 5.03 g (4.88 mmol) of a mixture of the cyclic compounds (2a) and (2b) obtained in Example B-7, 1.86 g (21.95 mmol) of sodium bicarbonate, N— To a mixture of 100 ml of methyl-2-pyrrolidone, 6.14 g (21.95 mmol) of methyl adamantyl bromoacetate was added dropwise, followed by heating and stirring at 80 ° C. for 8 hours. The reaction mixture was allowed to cool and extracted with ethyl acetate / water. The organic layer is concentrated and reprecipitated with hexane, and the precipitated solid is filtered off to obtain a mixture of cyclic compounds (5a) and (5b) [(5a) :( 5b) = 1: 3.5 (molar ratio)] was obtained in a yield of 72%. As a result of ¹ H-NMR measurement (FIG. 14), it was confirmed that the following structure and the above composition were obtained.

[Evaluation Example 2]
A photoresist solution composed of a substrate, PAG, quencher, and solvent was prepared, and a pattern was formed on a silicon wafer using an electron beam.
As a substrate, 77 parts by weight of each of the mixtures obtained in Examples B-7 and B-8 were used, 20 parts by weight of triphenylsulfonium nonafluorobutanesulfonate as a PAG, and 1,4-diazabicyclo (2,2 as a quencher) 2,2) 3 parts by weight of octane was used. These solid components were dissolved in propylene glycol monomethyl ether so as to have a concentration of 2.5% by weight.

A photoresist solution containing the mixture of Examples B-7 and B-8 was spin-coated on a silicon wafer subjected to hexamethyldisilazane (HMDS) treatment and heated at 100 ° C. for 180 seconds to form a thin film. Formed. Next, the substrate having this thin film was drawn using an electron beam drawing apparatus (acceleration voltage 50 kV), baked at 100 ° C. for 60 seconds, and then added with an aqueous tetrabutylammonium hydroxide solution having a concentration of 2.38 wt%. The film was developed for 2 seconds, washed with pure water for 60 seconds, and then dried with a nitrogen stream. Table 3 shows the results of resolution (half pitch) and sensitivity (necessary electron beam dose) obtained when a line / space pattern having a size of 1/1 was obtained from the results of observation 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 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 was baked at 100 ° C. for 90 seconds and rinsed with 2.38 wt% tetramethylammonium hydroxide aqueous solution for 30 seconds and ion-exchanged water for 30 seconds to form a pattern. 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 cyclic compound of the present invention can be used as a material for a photoresist substrate. A photoresist composition containing a photoresist base material is suitably used in the electric / electronic field, optical field, and the like of semiconductor devices.

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

Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will appreciate that these exemplary embodiments and / or embodiments are substantially without departing from the novel teachings and advantages of the present invention. It is easy to make many changes to the embodiment. Accordingly, many of these modifications are within the scope of the present invention.
The entire contents of the documents described in this specification are incorporated herein by reference.

Claims

A compound represented by only one of the following formulas (1) and (2) having a purity of 90% or more.

[Wherein, R is a group represented by any of the following formulas (3) to (5).
R 1 represents 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, a substituted or unsubstituted cyclic group having 3 to 20 carbon atoms. An alkoxy group, a substituted or unsubstituted aryloxy 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. It is a group to which an ester bond, a carbonate ester bond or an ether bond is bonded.
R 2 is hydrogen, 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 fatty acid having 3 to 20 carbon atoms. A 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) and the formula (2) may be the same or different.

(In the formula, Ar represents a substituted or unsubstituted arylene group having 6 to 10 carbon atoms, a group obtained by combining two or more substituted or unsubstituted arylene groups having 6 to 10 carbon atoms, or at least an alkylene group and an ether bond. A group in which one or more of them are combined with a substituted or unsubstituted arylene group having 6 to 10 carbon atoms,
In the case of having a substituent, the substituent is bromine, fluorine, a nitrile group, or an alkyl group having 1 to 10 carbon atoms.
R 3 represents a hydroxyl 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, a substituted or unsubstituted carbon, A cyclic aliphatic hydrocarbon group having 3 to 20 carbon atoms, a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, an alkoxy group, an alkoxyalkyl group, a carboxy group, a silyl group, or these groups and a divalent group. A bonded group,
The divalent group includes a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted silylene group, a group in which two or more of these groups are bonded, or one or more of these groups and an ester. A group in which one or more groups selected from a bond, a carbonate ester bond and an ether bond are bonded.
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, a substituted 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.
The plurality of R 3 , R 4 , R 5 , Ar, A 1 , x, y, and z may be the same or different. ]]
The compound according to claim 1, wherein R 3 is an acid dissociable, dissolution inhibiting group of any one of the following formulas (I) to (IV).

(In the formulas (I) to (IV),
α 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 to 20 cyclic aliphatic hydrocarbon groups, or substituted or unsubstituted aromatic groups having 6 to 10 carbon atoms.
β is an alkoxy group substituted with a group having a tertiary aliphatic structure, an aromatic structure, a monocyclic aliphatic structure or a bicyclic aliphatic structure.
γ represents an aromatic structure, an alkoxy group substituted by a group having a monocyclic aliphatic structure or a polycyclic aliphatic structure, or one or more structures of an aromatic structure, a monocyclic aliphatic structure, and a polycyclic aliphatic structure; And an alkoxy group substituted with a combination of linear aliphatic hydrocarbon groups having 1 to 10 carbon atoms.
δ 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 to 20 cyclic aliphatic hydrocarbon groups, or substituted or unsubstituted aromatic groups having 6 to 10 carbon atoms. )
R is a group represented by the following formula (6), and in formula (6), R 4 is a group selected from the following formulas (7) to (38);
R 2 is hydrogen;
Of the two R 1 that are present on the same aromatic ring, one is a hydroxyl group, a compound of claim 1 or 2, wherein the other is soluble adjustment group.

(Wherein r represents any of the substituents represented by the above formulas (7) to (35))
A method for producing the compound according to any one of claims 1 to 3,
The difference between the solubility of the compound of the formula (1) at 0 ° C. and the solubility of the compound of the formula (2) at 0 ° C. is in the range of −50 ° C. to 50 ° C. in a solvent of 1 gram / liter or more. From the mixture of the compound of the formula (1) and the compound of the formula (2), the compound of the formula (1) or the compound of the formula (2) is crystallized and isolated, and the formula (1) Or a method for producing the compound of the formula (2).
The production method according to claim 4, wherein the temperature of the crystallization isolation step is -20 ° C or higher and 20 ° C or lower.
6. The method according to claim 4, wherein the solvent is at least one solvent selected from a halogen-containing organic solvent and an oxygen-containing organic solvent.
A thin film comprising the compound according to any one of claims 1 to 3.
A compound represented by the formula (1) according to any one of claims 1 to 3 and a compound represented by the formula (2) according to any one of claims 1 to 3, which are represented by the formula (1) A composition in which the molar ratio of the compound to the compound represented by formula (2) is 15:85 to 70:30.
A method for producing the composition of claim 8, comprising:
The difference between the solubility of compound (1) at 0 ° C. and the solubility of compound (2) at 0 ° C. is 1 gram / liter or more under the condition of −50 ° C. or more and 50 ° C. or less under the condition of compound (1) And controlling the molar ratio of the compound (1) and the compound (2) in the mixture by crystallizing and isolating a predetermined amount of the compound (1) or the compound (2) from the mixture of the compound (2) A method for producing a composition.
A method for producing the composition of claim 8, comprising:
The difference between the solubility of compound (1) at 0 ° C. and the solubility of compound (2) at 0 ° C. is 1 gram / liter or more under the condition of −50 ° C. or more and 50 ° C. or less under the condition of compound (1) And a crystallization isolation step of crystallizing and isolating the compound (1) or the compound (2) from a mixture of the compound (2) and
The isolated compound (1) or compound (2) and a mixture of the compound (1) and the compound (2) are mixed at a predetermined ratio, and the molar ratio of the compound (1) and the compound (2) is determined. A mixing ratio control step to control;
The manufacturing method of the composition containing this.
A method for producing the composition of claim 8, comprising:
A mixture synthesis step of synthesizing a first mixture of compound (1) and compound (2) and a second mixture of compound (1) and compound (2);
The difference between the solubility of compound (1) at 0 ° C. and the solubility of compound (2) at 0 ° C. is 1 gram / liter or more under the condition of −50 ° C. or more and 50 ° C. or less under the conditions of the first A crystallization isolation step of crystallizing and isolating compound (1) or compound (2) from the mixture;
The first mixture after the compound (1) or the compound (2) is isolated by the crystallization isolation step and the second mixture are mixed at a predetermined ratio, and the compound (1) and the compound ( A mixing ratio control step for controlling the molar ratio of 2);
The manufacturing method of the composition containing this.
The method according to any one of claims 9 to 11, wherein a temperature in the crystallization isolation step is -20 ° C or higher and 20 ° C or lower.
The production method according to any one of claims 9 to 12, wherein the solvent is at least one solvent selected from a halogen-containing organic solvent and an oxygen-containing organic solvent.
A composition containing the compound according to any one of claims 1 to 3 and a solvent, or a photoresist composition containing the composition according to claim 8 and a solvent.
A thin film comprising the composition according to claim 8.
A fine processing method using the photoresist composition according to claim 14.
A semiconductor device manufactured by the microfabrication method according to claim 16.