JPH07316268A - Far-ultraviolet absorbent and method of forming pattern by using same - Google Patents

Abstract

PURPOSE:To obtain a far-ultraviolet absorbent useful in the formation of a resist pattern by far-ultraviolet lithography and capable of forming an antireflection film capable of being mass-produced by mixing a specified compound with a specified anthracene derivative and a solvent. CONSTITUTION:This absorbent comprises a compound having at least one glycidyl group in the molecule [e.g. poly(methyl methacrylate/glycidyl methacrylate/2,3-dihydroxypropyl methacrylate)], at least one anthracene derivative represented by formula I (wherein X is -O-SO2-,-O-CO- or -CO-; R<1> and R<2> are each H, alkyl, alkoxy, halogen or OH; R<3> to R<6> are each R<1> or a group of formula II and at least one of them is a group of formula II, provided that a compound of formula I (wherein the groups of formula II are simultaneously at the positions 1, 8 and 9 of the anthracene ring) is excluded) and a solvent therefor (e.g. tetraflufuryl alcohol and propylene glycol monomethyl ether acetate).

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for forming a resist pattern in the manufacture of semiconductor devices, etc., and particularly when a resist pattern is formed on a substrate such as a semiconductor by lithography using deep ultraviolet light. The present invention relates to a far-ultraviolet light absorbing material used for the purpose of suppressing the influence of the reflected light and a pattern forming method using the same.

[0002]

2. Description of the Related Art In recent years, with the high integration of semiconductor devices, the energy sources of exposure apparatuses used for microfabrication, especially photolithography, have become shorter and shorter in wavelength, and now far-ultraviolet light (300 nm or less) and KrF excimer are used. Laser light (24
8.4 nm), ArF excimer laser light (193 nm), electron beam,
Soft X-rays are being considered. For the use of these energy sources, high sensitivity and high resolution of the resist material are required, and for that purpose, a chemically amplified resist material using an acid generated by exposure as a medium has been proposed [H. Ito et al., Polym.
Eng. Sci., 23, 1012 (1983)]. After that, the chemical amplification type resist material has been studied and many reports have been issued. At present, a resist material having a resolution performance of 0.25 to 0.30 μm has been reported. Generally, when a chemically amplified resist material is used on a flat silicon substrate,
A good resist pattern having a rectangular cross section is obtained. However, since poly (hydroxystyrene), which is a base resin often used for chemically amplified resist materials, has high transparency to far-ultraviolet light such as KrF excimer laser light, excimer laser light from the underlying semiconductor substrate, etc. It is strongly affected by the multiple reflection in the film due to the reflection of far-ultraviolet light. Due to the influence of the multiple reflection in the film, the resist pattern size greatly changes due to the fluctuation of the resist film thickness. Especially when there is a step on the semiconductor substrate or a highly reflective substrate such as an aluminum substrate, the resist film thickness changes greatly, and the dimension of the resist pattern fluctuates significantly due to increased intra-film multiple reflection, There is a problem of breaking the wire.

Therefore, there is a method of using an organic antireflection film for the purpose of suppressing the influence of intra-film multiple reflection. The organic antireflection film is generally obtained by spin-coating a novolac resin-naphthoquinonediazide-based resist on a semiconductor substrate before applying the resist and heating it at a high temperature.

However, this method has a problem that the anti-reflection film effect cannot be provided because the light absorption of the novolak resin naphtoquinone diazide type resist is insufficient. Further, as a recent report, there is a method using an organic silane compound disclosed in, for example, JP-A-5-47656.

However, the method of using an organic silane compound as the antireflection film material has a problem that silicon oxide is generated by ashing and cannot be completely removed. In addition, JP-A-62-264051 and JP-A-59-9344.
When a polyamide or polyimide polymer or sulfone polymer disclosed in Japanese Patent Publication No. 8 etc. is used for the antireflection film, mixing may occur at the interface with the resist, or due to an acidic atmosphere or a basic atmosphere. However, there is a problem of defective shape such as pattern hem and undercut of the pattern.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above situation, and when forming a resist pattern by using deep ultraviolet lithography such as KrF excimer laser light, ArF excimer laser light, etc., a resist pattern from a semiconductor substrate is formed. A novel far-ultraviolet light absorbing material capable of forming an antireflection film which can be mass-produced on the surface of a semiconductor substrate and is used for the purpose of preventing the influence of multiple reflection in the film due to reflection, and a pattern forming method using this material The purpose is to provide.

[0007]

To achieve the above object, the present invention comprises the following configurations. “(1) One or more compounds having one or more glycidyl groups in the molecule, and the following general formula [1]

[0008]

[Chemical 3]

[In the formula, X is --O--SO _2- , --O--CO
- or represents a -CO-, R ¹ and R ² are independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or a hydroxyl ^{group, R 3, R 4, R} 5 and R ⁶ are independently a Hydrogen atom, alkyl group, alkoxy group, halogen atom or the following general formula [2]

[0010]

[Chemical 4]

(In the formula, R ¹ , R ² and X are the same as above.)
(Provided that at least one of R ^{3 to} R ⁶ represents a group represented by the general formula [2]. Further, the group represented by the general formula [2] simultaneously represents 1 of an anthracene ring. Rank,
The compounds introduced at the 8th and 9th positions are excluded. ). ] The far-ultraviolet light absorption material which consists of 1 or more types of anthracene derivatives shown by these, and the solvent which can melt | dissolve these.

(2) (i) a step of applying the far-ultraviolet light absorbing material described in (1) above on a semiconductor substrate and then subjecting it to a crosslinking reaction by heating to form a film; and (ii) obtained in (i) A step of applying a resist material on the far-ultraviolet light absorbing material film and then baking to form the resist material film; and (iii) KrF through a mask.
A pattern forming method comprising: a step of performing heat treatment after exposing to excimer laser light or far-ultraviolet light; and a step of developing with an (iV) alkali developing solution. ]

That is, the inventors of the present invention have made the resist film within the resist film due to the shortening of the wavelength of light and the high light transmittance of the base resin, which occurs when the resist pattern is formed by the deep ultraviolet photolithography such as KrF excimer laser light. As a result of intensive research on the antireflection film material formed on the surface of the semiconductor substrate for the purpose of preventing multiple reflections, it has excellent controllability of film formation by spin coating, excellent heat resistance, and a resist material at the interface with the resist material. The present invention has been completed by finding a far-ultraviolet light-absorbing material of the present invention that can satisfy all the conditions of not being mixed and having strong absorption at 300 nm or less, particularly around 248 nm.

As a constituent component of the antireflection film material according to the present invention, in addition to absorbing far-ultraviolet light, it contributes to the heat resistance of the antireflection film, and at the interface with the resist material applied on this film. It is a necessary condition to have the property of giving immiscible properties. As a compound satisfying these conditions, the present inventors have two or more phenolic hydroxyl groups in one molecule capable of undergoing a crosslinking reaction by heating with a resin having a glycidyl group, and in the vicinity of 220 to 300 nm. Focusing on a series of compounds having an anthracene skeleton having strong absorption in the molecule, in order to further facilitate the thermal crosslinking reaction, a carbonyl group, a carboxyl group or a sulfonyl group at the p-position or m-position of the phenolic hydroxyl group. The present invention has arrived at a compound represented by the above general formula [1] into which an electron withdrawing group such as

In the general formula [1], when the group represented by the general formula [2] is simultaneously introduced into the 1-position, 8-position and 9-position of the anthracene ring, a glycidyl group is added to the molecule. Since it is difficult for the crosslinking reaction with the resin contained therein to proceed, a desired antireflection film cannot be formed.

On the other hand, in the general formula [1], when one or more phenolic hydroxyl groups are at the p-position and / or the m-position with respect to X, a resin having a glycidyl group in the molecule is used. The crosslinking reaction is remarkably accelerated, and a preferable antireflection film can be obtained.

The compound represented by the general formula [1] can be easily synthesized by, for example, the following methods a), b) or c). a) Method-1 In the general formula [1], R ³ is a group represented by the general formula [2], and R ⁴ , R ⁵ and R ⁶ are a hydrogen atom, an alkyl group, a halogen atom or a general formula [ 2], wherein X is a carbonyloxy group or a sulfonyloxy group, can be easily synthesized, for example, according to the following Reaction Scheme 1.

[0018]

[Formula 1]

That is, first, an anthraquinone derivative having one or more hydroxyl groups is dissolved in 5 to 20 times by volume of acetic acid or propionic acid, etc., and excess concentrated hydrochloric acid and stannous chloride are added thereto to carry out a reduction reaction at 10 to 120 ° C. Then, the anthracentriol derivative can be easily obtained.

Next, the obtained anthracentriol derivative is used in an amount of 2 times or more moles (3 moles in the case of Scheme 1) of p-benzyloxybenzoyl chloride or
p-benzyloxybenzenesulfonyl chloride, etc.,
2 times or more moles (3 moles in the example of Scheme 1) of a base (eg, triethylamine, piperidine, NaOH,
In the presence of KOH, NaH, etc.), 1 to 20 volumes of a suitable organic solvent (eg, pyridine, methylene chloride, toluene,
0 to 150 in ethyl ether, tetrahydrofuran, etc.)
The hydroxyl group was protected by stirring for 30 minutes to 20 hours at ℃ (in the example of Scheme 1, protected by the benzyl group)
The target compound is obtained.

Then, this is placed in a suitable organic solvent (for example, methanol, ethanol, propanol, isopropanol, tetrahydrofuran, methylene chloride, chloroform, etc.) in a volume of 1 to 20 times, for example, Raney nickel,
When the hydrogenation reaction is carried out in the presence of a catalyst such as palladium carbon or the like at atmospheric pressure to 50 kg / cm ² (hydrogen initial pressure) at 0 to 50 ° C. for 1 to 10 hours, the desired compound represented by the general formula [1] is obtained. Easily obtained.

B) Method-2 In the general formula [1], R ³ is a hydrogen atom, and R ⁴ or R
^{When 6} is a group represented by the general formula [2], R ⁶ or R ⁴ and R ⁵ are a hydrogen atom, an alkyl group or a halogen atom, and X is a carbonyloxy group or a sulfonyloxy group, For example, it can be synthesized according to the following reaction scheme 2.

[0023]

[Formula 2]

That is, first, an anthraquinone derivative having two hydroxyl groups such as 2,6-dihydroxyanthraquinone is reacted with an alkylating agent such as dimethylsulfate in the presence of a deoxidizing agent such as anhydrous potassium carbonate to protect the hydroxyl groups. ,
Reduction with zinc / ammonia water gives, for example, 2,6-dimethoxyanthracene in which the 2,6-hydroxy group is protected. Then, the protecting group for the hydroxyl group is eliminated by reacting with, for example, boron tribromide to give 2,6-dihydroxyanthracene. In the following, according to the operation method after the esterification step in the method a), esterification with p-benzyloxybenzoic acid chloride, p-benzyloxybenzenesulfonyl chloride or the like is carried out, and then a hydroxyl-protecting group is formed by hydrogenation reaction. If the (benzyl group) is removed, the desired compound represented by the general formula [1] can be easily obtained.

C) Method-3 In the general formula [1], R ³ is a hydrogen atom, and R ⁴ and R
⁶ is a group represented by the general formula [2], R ⁵ is a hydrogen atom,
When the compound is an alkyl group, a halogen atom or a group represented by the general formula [2], and X is a carbonyloxy group or a sulfonyloxy group, for example, the following Reaction Scheme 3
Can be synthesized according to.

[0026]

[Formula 3]

That is, first, an anthraquinone derivative having 3 or more hydroxyl groups, for example, 6-methyl-1,3,8-trihydroxyanthraquinone, is used to alkyl etherify the hydroxyl groups according to the procedure of the above method b). When reduced with zinc / ammonia water, the hydroxyl group at the 1,3,8-position is protected, for example, 6-methyl-1,3,8-trimethoxyanthracene is obtained. Then, the protecting group for the hydroxyl group is eliminated by reacting with, for example, boron tribromide to give 6-methyl-1,3,8-trihydroxyanthracene. This is further esterified with p-benzyloxybenzoic acid chloride or p-benzyloxybenzenesulfonyl chloride and the like, and then the protective group for the hydroxyl group (benzyl group) is eliminated by catalytic reduction or the like to obtain the desired general formula [1]. The compound represented by is easily obtained.

Specific examples of the compound represented by the general formula [1] (hereinafter sometimes referred to as the crosslinking agent according to the present invention) include, for example, 2,6,9-tris (4-hydroxybenzoyloxy). Anthracene, 2,6,9-Tris (3,4-dihydroxybenzoyloxy) anthracene, 2,6,9-Tris (3-
Hydroxybenzoyloxy) anthracene, 2,6,9-tris (4-hydroxy-3-methoxybenzoyloxy) anthracene, 2,6,9-tris (3-chloro-4-hydroxybenzoyloxy) anthracene, 2,6, 9-tris (3-hydroxy-4-methylbenzoyloxy) anthracene, 1,
2,10-Tris (4-hydroxybenzoyloxy) anthracene, 1,2,10-Tris (3-hydroxybenzoyloxy) anthracene, 1,2,10-Tris (3,4-dihydroxybenzoyloxy) anthracene, 1, 2,10-Tris (4-
Hydroxy-3-methoxybenzoyloxy) anthracene, 1,2,10-tris (3-hydroxy-4-methylbenzoyloxy) anthracene, 1,2,10-tris (3-chloro-
4-hydroxybenzoyloxy) anthracene, 1,5,9-
Tris (4-hydroxybenzoyloxy) anthracene, 1,5,9-Tris (3-hydroxybenzoyloxy) anthracene, 1,5,9-Tris (3,4-dihydroxybenzoyloxy) anthracene, 1,5,9- Tris (4-hydroxy-3-methoxybenzoyloxy) anthracene, 1,5,9-
Tris (3-hydroxy-4-methylbenzoyloxy) anthracene, 1,5,9-tris (3-chloro-4-hydroxybenzoyloxy) anthracene, 1,4,9-tris (4-hydroxybenzoyloxy) anthracene, 1,5-bis (4-
Hydroxybenzoyloxy) anthracene, 1,5-bis (3-hydroxybenzoyloxy) anthracene, 1,5-
Bis (3,4-dihydroxybenzoyloxy) anthracene, 1,5-bis (4-hydroxy-3-methoxybenzoyloxy) anthracene, 1,5-bis (3-chloro-4-hydroxybenzoyloxy) anthracene, 1, 5-bis (3-hydroxy-4-methylbenzoyloxy) anthracene, 2,
6-bis (4-hydroxybenzoyloxy) anthracene, 2,6-bis (3-hydroxybenzoyloxy) anthracene, 2,6-bis (3,4-dihydroxybenzoyloxy) anthracene, 2,6-bis (4- Hydroxy-3-methoxybenzoyloxy) anthracene, 2,6-bis (3-chloro-4-hydroxybenzoyloxy) anthracene, 2,
6-bis (3-hydroxy-4-methylbenzoyloxy) anthracene, 1,2-bis (4-hydroxybenzoyloxy) anthracene, 1,2-bis (4-hydroxy-3-methoxybenzoyloxy) anthracene, 1, 8-bis (4-hydroxybenzoyloxy) anthracene, 1,8-bis (4-
Hydroxy-3-methoxybenzoyloxy) anthracene, 1,8-bis (4-hydroxybenzoyloxy) -3-methylanthracene, 6,7-dichloro-1,4-bis (3,4-dihydroxybenzoyloxy) anthracene, 6-methyl-
1,3,8-Tris (4-hydroxybenzoyloxy) anthracene, 1,4-bis (4-hydroxybenzoyloxy) anthracene, 6-methyl-1,3,8,10-tetra (4-hydroxybenzoyloxy) Anthracene, 1,10-bis (4-hydroxybenzoyloxy) -2-methoxyanthracene, 2,3-dimethyl-1,4,9-tris (4-hydroxybenzoyloxy) anthracene, 1,4-bis (3, 4-dihydroxybenzoyloxy) anthracene, 1,2,5,8-tetra (4-hydroxybenzoyloxy) anthracene, 5,8-
Dichloro-1,4,9-tris (4-hydroxybenzoyloxy) anthracene, 2,6,9-Tris (4-hydroxybenzenesulfonyloxy) anthracene, 2,6,9-Tris (3-
Hydroxybenzenesulfonyloxy) anthracene,
2,6,9-Tris (3,4-dihydroxybenzenesulfonyloxy) anthracene, 2,6,9-Tris (4-hydroxy-3-
Methoxybenzenesulfonyloxy) anthracene, 2,
6,9-tris (3-chloro-4-hydroxybenzenesulfonyloxy) anthracene, 2,6,9-tris (3-hydroxy-4-methylbenzenesulfonyloxy) anthracene,
1,2,10-Tris (4-hydroxybenzenesulfonyloxy) anthracene, 1,2,10-Tris (3-hydroxybenzenesulfonyloxy) anthracene, 1,2,10-Tris (3,4-dihydroxybenzenesulfonyloxy) ) Anthracene, 1,2,10-tris (4-hydroxy-3-methoxybenzenesulfonyloxy) anthracene, 1,2,10-tris (3-chloro-4-hydroxybenzenesulfonyloxy) anthracene, 1,2,10 -Tris (3-hydroxy-4-
Methylbenzenesulfonyloxy) anthracene, 1,5,
9-Tris (4-hydroxybenzenesulfonyloxy) anthracene, 1,5,9-Tris (3-hydroxybenzenesulfonyloxy) anthracene, 1,5,9-Tris (3,4-dihydroxybenzenesulfonyloxy) anthracene, 1 ,
5,9-Tris (4-hydroxy-3-methoxybenzenesulfonyloxy) anthracene, 1,5,9-Tris (3-chloro-
4-hydroxybenzenesulfonyloxy) anthracene, 1,5,9-tris (3-hydroxy-4-methylbenzenesulfonyloxy) anthracene, 1,4,9-tris (4-hydroxybenzenesulfonyloxy) anthracene, 1,5 -
Bis (4-hydroxybenzenesulfonyloxy) anthracene, 1,5-bis (3-hydroxybenzenesulfonyloxy) anthracene, 1,5-bis (3,4-dihydroxybenzenesulfonyloxy) anthracene, 1,5-bis (4 -Hydroxy-3-methoxybenzenesulfonyloxy) anthracene, 1,5-bis (3-hydroxy-4-methylbenzenesulfonyloxy) anthracene, 1,5-bis (3-chloro-4-hydroxybenzenesulfonyloxy) anthracene, 2,6-bis (4-hydroxybenzenesulfonyloxy) anthracene, 2,6-bis (3-hydroxybenzenesulfonyloxy) anthracene, 2,6-bis (3,4-dihydroxybenzenesulfonyloxy) anthracene, 2,6 -
Bis (4-hydroxy-3-methoxybenzenesulfonyloxy) anthracene, 2,6-bis (3-hydroxy-4-methylbenzenesulfonyloxy) anthracene, 2,6-bis (3-chloro-4-hydroxybenzenesulfonyloxy) )
Anthracene, 2,6-bis (4-hydroxybenzenesulfonyloxy) -9-ethoxyanthracene, 2,6-bis (4-
Hydroxybenzoyloxy) -9- (4-hydroxybenzoyl) anthracene, 2,6-bis (4-hydroxybenzoyloxy) -9- (4-hydroxybenzenesulfonyl)
Anthracene, 1,2-bis (4-hydroxybenzenesulfonyloxy) anthracene, 1,8-bis (4-hydroxy-
3-methoxybenzenesulfonyloxy) anthracene,
Examples thereof include 1,4-bis (4-hydroxybenzenesulfonyloxy) anthracene, but are not limited thereto.

The far-ultraviolet light absorbing material of the present invention contains, as a constituent component, one or more compounds having a glycidyl group in the molecule, in addition to one or more crosslinking agents of the present invention.

The compound having a glycidyl group in the molecule used in the present invention has excellent film-forming properties and can be easily converted into a heat resistant resin by a crosslinking reaction with a coexisting crosslinking agent when heated. However, for example, the following general formula [3]

[0031]

[Chemical 5]

(Wherein R ⁷ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 13), or polyethylene glycol diglycidyl ether or polypropylene glycol diglycidyl ether, or the following general formula [4 ]

[0033]

[Chemical 6]

Sorbitol polyglycidyl ether represented by: or the following general formula [5]

[0035]

[Chemical 7]

(Wherein Z represents --NH-- or --COO--, and p represents an integer of 1 to 10) or a sorbitol polyglycidyl ether resin represented by the following general formula [6].

[0037]

[Chemical 8]

[In the formula, R ⁸ and R ¹⁰ each independently represent a hydrogen atom or a methyl group, and R ⁹ is a hydroxyl group or --COO.
R ¹² (R ¹² represents an alkyl group having 1 to 6 carbon atoms), R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (however, different from the alkyl group of R ¹² ) and norbornyl. Group, adamantyl group, 9-anthracenemethyl group, 2,3-
Represents a dihydroxypropyl group or a 2-hydroxyethyl group, k and r are integers of 1 or more (provided that r / k + r = 0.
It is 1 to 0.9. ), And m represents an integer of 0 or 1 or more (provided that m / k + r + m = 0 to 0.5). ] And the like are listed, but of course the present invention is not limited to these.

Among the compounds having a glycidyl group in the molecule, polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether and sorbitol polyglycidyl ether can be easily obtained as commercial products, and are represented by the general formula [5]. The resin shown can be easily obtained by heating and reacting sorbitol polyglycidyl ether with alkylenedicarboxylic acid or alkylenediamine as shown in the following formula 4.

[0040]

[Formula 4]

The resin represented by the general formula [6] can be easily obtained by, for example, the synthetic method represented by the following formula 5.

[0042]

[Formula 5]

In the method of synthesizing the resin represented by the above general formula [6] (polymerization method), two or more kinds of monomers (at least one kind is a monomer having a glycidyl group in the molecule) in an arbitrary ratio are used. To 1 to 10 times the volume of a suitable solvent (for example, toluene, 1,4-dioxane, tetrahydrofuran, 1,3-dioxolane, etc.), and 0.1 to 20% by weight of the monomer in a nitrogen stream. Polymerization initiator [eg,
Azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (methyl 2-methylpropionate), 2,2'-azobis (2-methylbutyro) Nitrile), benzoyl peroxide, lauroyl peroxide, etc.]
The reaction is carried out at 50 to 150 ° C. for 1 to 20 hours in the presence of, and after the reaction, each copolymer (resin) is obtained by post-treatment according to a conventional method for obtaining a polymer. Further, if necessary, the copolymer obtained under the above-mentioned polymerization conditions, a suitable solvent of 1 to 20 times the volume of the copolymer (for example, acetone, 1,4-dioxane, toluene, tetrahydrofuran, methanol, Dissolved in ethanol, isopropanol, etc.) and in the presence of 0.1 to 25% by weight of a suitable acid (for example, hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, etc.) with respect to the copolymer, at 20 to 150 ° C. After stirring and reacting for 1 to 20 hours, a resin having two or more hydroxyl groups in the molecule can be obtained by post-treatment according to a conventional method for obtaining a polymer.

Specific examples of the compound having a glycidyl group in the molecule used in the present invention (hereinafter also referred to as the resin according to the present invention) include, for example, poly (methyl methacrylate / glycidyl methacrylate). ), Poly (methyl methacrylate / glycidyl methacrylate / 2,3-dihydroxypropyl methacrylate), poly (cyclohexyl methacrylate / glycidyl methacrylate), poly (n-butyl methacrylate / glycidyl methacrylate), poly (methacrylic acid tert-butyl / glycidyl methacrylate), poly (methyl methacrylate / glycidyl methacrylate / tert-butyl methacrylate), poly (methyl methacrylate / glycidyl methacrylate / 2-hydroxyethyl methacrylate), poly (cyclohexyl methacrylate / Glycid methacrylate / Methacrylic acid
2,3-dihydroxypropyl), poly (methyl acrylate / glycidyl methacrylate), poly (methyl acrylate / glycidyl methacrylate), poly (methyl methacrylate / glycidyl methacrylate / norbornyl methacrylate), poly (methyl methacrylate) / Glycidyl methacrylate / adamantyl methacrylate), poly (methyl methacrylate / glycidyl methacrylate / methacrylic acid 9-
Anthracene methyl), poly (ethyl acrylate / glycidyl methacrylate), poly (methyl methacrylate / glycidyl methacrylate / n-butyl methacrylate), poly (2-hydroxyethyl methacrylate / glycidyl methacrylate), poly (methacrylic acid Examples thereof include, but are not limited to, methyl / glycidyl acrylate), poly (vinyl alcohol / glycidyl methacrylate / methyl methacrylate), and the like. Among these resins, poly (methyl methacrylate / glycidyl methacrylate / 9-anthracene methyl methacrylate) is particularly preferable because it absorbs light around 250 nm relatively well.

The solvent used in the far-ultraviolet light absorbing material of the present invention may be any solvent as long as it can dissolve both the crosslinking agent of the present invention and the compound having a glycidyl group in the molecule. Specifically, for example, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 2-heptanone, N-methylpyrrolidone, cyclohexanone, tetrahydrofurfuryl alcohol, tetrahydrofuran, 1,4-
Dioxane, 1,2-dimethoxyethane, butyl acetate, methyl ethyl ketone and the like can be mentioned.

To form a pattern using the far-ultraviolet light absorbing material of the present invention, for example, the following may be performed. That is, first, the far-ultraviolet light-absorbing material according to the present invention is used as an undercoating agent on a highly reflective substrate such as aluminum, polysilicon, or aluminum-silicon so that the thickness is about 50 to 500 nm, and this is applied in an oven. A far-ultraviolet light absorbing material film is obtained by heating at 150 to 230 ° C for 5 to 30 minutes or on a hot plate at 150 to 230 ° C for 1 to 2 minutes. Then, a chemical amplification type resist material (both positive type and negative type is possible) is applied on the far ultraviolet light absorbing material film to a thickness of about 0.5 to 2 μm, and this is applied in an oven at 70 to 130 ° C. , 10 ~ 3
0 minutes, or 70 ~ 130 ℃ on a hot plate, 1-2
Prebake for a minute. Next, a mask for forming a desired pattern is held over the resist film, and far-ultraviolet light of 300 nm or less is irradiated so that the exposure amount is about 1 to 100 mJ / cm ^2, and then 70 to 150 on a hot plate. Bake at 1-2 ° C for 1-2 minutes.

Further, using a developing solution such as an aqueous solution of 0.1 to 5% tetramethylammonium hydroxide (TMAH),
By developing for about 3 minutes by a conventional method such as a dipping method, a paddle method, or a spray method, a desired pattern is formed on the substrate.

In the far-ultraviolet light absorbing material of the present invention, the compounding ratio of the compound having a glycidyl group in the molecule and the crosslinking agent of the present invention is 1 weight (the two or more compounds having a glycidyl group are used. In the case of the total weight), the latter is about 0.1 to 1 weight, more preferably 0.15 to 0.7.
Approximately 5 weight (all of them are the total weight when two or more crosslinking agents according to the present invention are used). Further, as the amount of the solvent in the far-ultraviolet light absorbing material of the present invention, the far-ultraviolet light absorbing material obtained by dissolving the compound having a glycidyl group in the molecule and the crosslinking agent according to the present invention is applied onto the substrate. The amount is not particularly limited as long as it does not hinder the process, but is usually 1 weight of the compound having a glycidyl group (total weight when two or more compounds having a glycidyl group are used). 1 to 50% by weight, preferably 10 to 25% by weight (in the case of using two or more kinds of solvents, the total weight thereof).

The resist material used in the pattern forming method using the far-ultraviolet light absorbing material of the present invention as an undercoating agent may be either a positive acting chemically amplified resist material or a negatively acting chemically amplified resist material. However, either one is acceptable. The developer used in the pattern forming method using the far-ultraviolet light absorbing material of the present invention as an undercoat is, for example, in the case of a positive resist material, an alkaline developer of a resin component of the resist material used. Depending on the solubility of the alkali developing solution, an alkali developing solution having an appropriate concentration may be selected such that the unexposed area is hardly dissolved and the exposed area is dissolved, but it is usually selected from the range of 0.01 to 20%. The alkaline solution used is, for example, TMAH, choline,
Organic amines such as triethanolamine, for example NaOH,
Examples thereof include solutions containing inorganic alkalis such as KOH.

The far-ultraviolet light absorbing material of the present invention comprises a compound having a glycidyl group in the molecule, a cross-linking agent according to the present invention and a solvent as main constituents. A far ultraviolet light absorber that absorbs [eg, 9-anthracenemethanol, 9- (2-methoxyethoxy) methylanthracene, 9- (2-ethoxyethoxy) methylanthracene, 9-anthracenemethyl acetate, propionic acid
9-anthracene methyl, malonate di (9-anthracene methyl), terephthalate di (9-anthracene methyl),
1,2,10-triacetoxyanthracene, 1,5,9-triacetoxyanthracene, 2,6,9-triacetoxyanthracene, 1,5,9-tribenzoyloxyanthracene, 1,2,10
-Tribenzoyloxyanthracene, 2,6,9-tribenzoyloxyanthracene and the like can be mentioned. ], A commercially available surfactant that improves coating properties [for example, various nonionic or fluorine-containing nonionic surfactants and the like can be mentioned. ] And the like, it is possible to add one or more kinds as appropriate.

[0051]

[Operation] When the far-ultraviolet light absorbing material according to the present invention is spin-coated on a semiconductor substrate and heated to, for example, 150 ° C. or higher, a compound having a glycidyl group in the molecule according to the following formula 6 and a crosslinking agent according to the present invention are added. A cross-linking reaction occurs between them, resulting in an antireflection film having excellent heat resistance.

The cross-linking agent and the resin having a glycidyl group (epoxy group) in the molecule according to the present invention are both soluble in acetone and a resist solvent (for example, propylene glycol monomethyl ether acetate). 6
Accordingly, the antireflection film obtained as a result of the crosslinking reaction of these compounds is insoluble in these solvents.

[0053]

[Formula 6]

The heating conditions are not particularly limited as long as a crosslinking reaction occurs between the compound having a glycidyl group in the molecule and the crosslinking agent according to the present invention.

Then, a resist material for KrF excimer laser, for example, is spin-coated on the surface layer of the antireflection film and baked to form a resist film, which is then exposed to far ultraviolet light such as KrF excimer laser light to prevent reflection. Kr transmitted through the resist film due to the anthracene ring contained in the film
Far-ultraviolet light such as F excimer laser light is absorbed, and reflection from the semiconductor substrate is prevented. As a result, the influence of intra-film multiple reflection, which has been a problem in this field in the past, can be completely suppressed, and dimensional fluctuation due to the influence of reflection even when forming a resist pattern on a semiconductor substrate having a step with a difference in film thickness. Does not occur at all.

Further, since this antireflection film does not dissolve in the resist solvent, it does not mix at the interface with the resist and does not affect the resolution of the pattern.

As a compound similar to the cross-linking agent according to the present invention, a compound in which the group represented by the general formula [2] according to the present invention is simultaneously introduced into the 1-position, 8-position and 9-position of the anthracene ring, for example, 1,8,9-Tris (4-hydroxybenzoyloxy) anthracene, 1,8,9-Tris (2-hydroxybenzoyloxy) anthracene and the like are known (West German Published Patent No. 2,257,442). In the case of these compounds, the cross-linking reaction is difficult to proceed even when heated with a resin having the above-mentioned glycidyl group in the molecule due to steric hindrance or a strong intramolecular hydrogen bond, so that the solubility in acetone or the resist solvent is low. It is maintained as it is. Therefore, when this is used as an antireflection film, it mixes with the resist at the interface portion and cannot be used at all as an antireflection film.

The present invention will be described in more detail below with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited by these.

[0059]

【Example】

Synthesis Example 1 Synthesis of 2,6,9-tris (4-hydroxybenzoyloxy) anthracene (1) 190 g (1.5 mol) of benzyl chloride, 200 g (1.2 mol) of p-hydroxybenzoic acid and 165 g (1.2 mol) of potassium carbonate.
Mol) in 1200 ml of acetone and stirred for 12 hours,
The mixture was refluxed and reacted. After cooling, the precipitated crystals were filtered off and the filtrate was added to 400
The mixture was concentrated to 100 ml, water (1000 ml) was added, and the mixture was stirred, allowed to stand, and then separated. The organic layer is concentrated and the residue is sodium hydroxide 60 g
(1.5 mol), water (1000 ml) and ethanol (500 ml) were added and the solution was stirred for 4 hours to dissolve. Then, 200 ml of concentrated hydrochloric acid was injected to adjust the pH to 1, and the precipitated crystals were collected by filtration, washed with water, washed with ethanol and dried under reduced pressure to obtain 195 g of 4-benzyloxybenzoic acid as white crystals. mp. 191.2
~ 192.6 ° C. ¹ HNMR δ ppm (CDCl ₃ -DMSO-d ₆ ): 5.10 (2H, s, ArC H ₂ ), 6.9
2 (2H, d, J = 8Hz, Ar 3-H, 5-H), 7.13-7.51 (5H, m, aromatic ring hydrogen), 7.86 (2H, d, J = 8Hz, Ar 2-H, 6- H), 8.65 (1H, bs , O H). IR (KBr tablets) ν cm ^-1 : 1675 (COOH).

(2) 16 g (70 mmol) of 4-benzyloxybenzoic acid obtained in the above (1) was suspended in 50 ml of methylene chloride, and 20.6 g (173 mmol) of thionyl chloride was poured into the suspension. 45 by adding 2 drops of N-dimethylformamide
After stirring and reacting at 50 ° C. for 1 hour, the mixture was left at room temperature overnight.
After standing overnight, the solvent was distilled off to obtain 17.3 g of 4-benzyloxybenzoic acid chloride residue as white crystals.

(3) 2,6-dihydroxy-9-anthrone 5
g (22 mmol) of pyridine (110 ml) and triethylamine
It was dissolved in 8.8 g of a mixed solution, and 17.0 g (69 mmol) of 4-benzyloxybenzoic acid chloride obtained in the above (2) was added little by little. Then, the mixture was reacted with stirring at 100 ° C. for 5 hours, cooled to room temperature, poured into 600 ml of 1N hydrochloric acid, and extracted with 250 ml of methylene chloride. The methylene chloride layer was washed once with 600 ml of 1N hydrochloric acid and three times with 500 ml of saturated saline, and then dried over anhydrous magnesium sulfate. After the desiccant was filtered off, the solvent was distilled off, and 26 g of the residual oily substance was crystallized from a mixed liquid of n-hexane / tetrahydrofuran (1/2 [V / V]), 2,
7.45 g of 6,9-tris (4-benzyloxybenzoyloxy) anthracene was obtained as yellow crystals. mp.219-22
1 ° C. ¹ HNMR δ ppm (CDCl ₃ ): 5.15 (2H, s, ArC H ₂ ), 5.17 (2H, s, A
rC H ₂ ), 5.20 (2H, s, ArC H ₂ ), 7.03 to 8.40 (34H, m, aromatic ring hydrogen). IR (KBr tablet) ν cm ^-1 : 1728 (COO-).

(4) 6.2 g of 2,6,9-tris (4-benzyloxybenzoyloxy) anthracene obtained in (3) above (7.
(3 mmol) was dissolved in 250 ml of tetrahydrofuran, 11.5 g of 5% palladium-carbon was added, and catalytic reduction was carried out at room temperature and atmospheric pressure. After reducing for 6 hours, the catalyst was filtered off, the filtrate was concentrated, and 4.2 g of the yellow crystals of the residue were recrystallized from a mixed solution of n-hexane / tetrahydrofuran (1/5 [V / V]) for 2,6,9. -
Tris (4-hydroxybenzoyloxy) anthracene
3.0 g was obtained as pale yellow crystals. mp. 238 ° C (decomposition). ¹ HNMR δppm (DMSO-d ₆ ): 6.90 ~ 7.04 (6H, m, (Ar 3'-H,
5'-H) × 3), 7.50-8.29 (12H, m, anthracene ring 1-H, 3-H,
4-H, 5-H, 7-H, 8-H and (Ar 2'-H, 6'-H) × 3), 8.67 (1H, s, anthracene ring 10-H), 10.60 (3H, bs , OH × 3). IR (KBr tablets) ν cm ⁻¹ : 3392 (OH), 1699 (COO-).

Synthesis Example 2 Synthesis of 2,6-bis (4-hydroxybenzoyloxy) anthracene (1) 2,6-dihydroxy-9,10-anthraquinone 3 g (12.
5 mmol) and 23 g of anhydrous potassium carbonate 400 g of acetone
20 g (158 mmol) of dimethylsulfate was added at room temperature, and the mixture was stirred, refluxed and reacted for 6 hours. After standing overnight at room temperature, the reaction solution was poured into 850 ml of cold water, and the precipitated crystals were collected by filtration and dried to obtain 3.1 g of crude crystals as dark brown crystals. Then, the crude crystals were recrystallized from benzene to obtain 2.7 g of 2,6-dimethoxy-9,10-anthraquinone as tan crystals. ¹ HNMR δ ppm (DMSO-d ₆ ): 3.97 (6H, s, C H ₃ O × 2), 7.43 (2H,
d, J = 8Hz, anthraquinone ring 3-H, 7-H), 7.61 (2H, s, anthraquinone ring 1-H, 5-H), 8.17 (2H, d, J = 8Hz, anthraquinone ring 4-H, 8-H). IR (KBr tablets) ν cm ^-1 : 1668 (C = O).

(2) 2,6-dimethoxy-9,10-obtained in (1) above
2.7 g (10 mmol) of anthraquinone was suspended in 92 ml of 25% aqueous ammonia, 10.2 g (156 mmol) of zinc powder and 130 mg of copper sulfate pentahydrate were added, and the mixture was stirred and reacted at 70 ° C for 7 hours. . After cooling, the reaction solution was neutralized with 1N sulfuric acid (40 ml), methylene chloride and water were added, the mixture was stirred, the insoluble material was filtered off, and the filtrate was separated to obtain an organic layer. The organic layer was washed with water and concentrated to obtain 2.2 g of crude crystals which were recrystallized from methanol to obtain 1.3 g of 2,6-dimethoxyanthracene as yellowish brown crystals. ¹ HNMR δ ppm (CDCl ₃ ): 3.80 (6H, s, C H ₃ O × 2), 6.51 to 8.2
0 (8H, m, anthracene ring hydrogen). IR (KBr tablet) ν cm ⁻¹ : 1613,1577.

(3) 1.22 g (5.1 mmol) of 2,6-dimethoxyanthracene obtained in (2) above was suspended in 30 ml of methylene chloride, and 3.2 g (12.8 mmol) of boron tribromide in methylene chloride (10 ml). The solution was added dropwise at -60 ° C. After dropping, the reaction solution was gradually returned to room temperature, left overnight, poured into 200 ml of cold water, and the precipitated crystal was collected by filtration, washed with water and dried to give 0.85 g of crude 2,6-dihydroxyanthracene as a tan crystal. Obtained. _{^{1 HNMR δppm (DMSO-d 6}} ): 6.07~8.15 (8H, m, anthracene ring hydrogen), 9.65 (2H, bs, O H × 2).

(4) 0.82 g (3.9 mmol) of 2,6-dihydroxyanthracene obtained in (3) above was dissolved in 15 ml of pyridine, and 4-benzyloxybenzoic acid obtained in (2) of Synthesis Example 1 was dissolved in this solution. After 2.12 g (8.58 mmol) of chloride was added, 1 g of triethylamine was added dropwise at 20 ° C. Then 9
After reacting at 0 to 95 ° C. for 8 hours and cooling, the reaction solution was poured into 400 ml of dilute hydrochloric acid and extracted with methylene chloride. After washing the organic layer with water, the solvent was distilled off, and the resulting crude oily substance was separated by column [filler: Wakogel C-200 (trade name of Wako Pure Chemical Industries, Ltd.); eluent: n-hexane / chloride Methylene = 7/1 → 2/1 →
1/1 → 1/2] to obtain 0.56 g of 2,6-bis (4-benzyloxybenzoyloxy) anthracene as yellow powdery crystals. ¹ HNMR δ ppm (CDCl ₃ ): 5.09 (2H, s, C H ₂ ), 5.17 (2H, s, C
_{H 2), 6.82~8.66 (26H,} m, aromatic hydrogen). IR (KBr tablet) ν cm ^-1 : 1732 (COO-).

(5) 0.56 g (0.88 g) of 2,6-bis (4-benzyloxybenzoyloxy) anthracene obtained in the above (4)
Was used to perform catalytic reduction and post-treatment in the same manner as in (4) of Synthesis Example 1 to obtain 0.36 g of 2,6-bis (4-hydroxybenzoyloxy) anthracene as pale yellow crystals. mp. 324 ° C (decomposition). _{^{1 HNMR δppm (DMSO-d 6}} ): 6.63~8.97 (16H, m, aromatic hydrogen), 10.48 (2H, bs, O H × 2). IR (KBr tablets) ν cm ^-1 : 3405 (OH), 1701 (COO-).

Synthesis Example 3 Synthesis of 1,5,9-tris (4-hydroxybenzoyloxy) anthracene (1) 10 g (41.6 mmol) of 1,5-dihydroxyanthraquinone and 45 g (237 mmol) of stannous chloride were added to 150 ml of acetic acid.
90 ml of concentrated hydrochloric acid was injected at 16 to 20 ° C., and the mixture was stirred, refluxed and reacted for 4 hours. After standing overnight at room temperature, it was cooled to 5 ° C, and the precipitated crystals were collected by filtration, washed with water and dried to give 1,5-
8.0 g of dihydroxy-9-anthrone was obtained as dark brown needle crystals. mp.231-233 ° C. ¹ HNMR δppm (DMSO-d ₆ ): 4.20 (2H, s, C H ₂ ), 6.87 (1H, d, J =
8Hz, anthracene ring 6-H), 7.09 (1H, d, J = 8Hz, anthracene ring 2-H), 7.19 (1H, d, J = 8Hz, anthracene ring 4-H), 7.35
(1H, t, J = 8Hz, anthracene ring 7-H), 7.57 (1H, t, J = 8Hz, anthracene ring 3-H), 7.69 (1H, d, J = 8Hz, anthracene ring 8
-H), 10.23 (1H, bs , 5-O H), 12.97 (1H, s, 1-O H). IR (KBr tablet) ν cm ⁻¹ : 3338 (OH), 1633 (C = O).

(2) 2.3 g (10 mmol) of 1,5-dihydroxy-9-anthrone obtained in the above (1) was dissolved in a mixed solution of 45 ml of pyridine and 3.6 g of triethylamine, and this was used in Synthesis Example 1
8 g of 4-benzyloxybenzoic acid chloride obtained in (2) above was added little by little, and the mixture was reacted at 90 ° C. for 5 hours with stirring. After standing overnight at room temperature, the reaction solution was poured into 300 ml of 1N hydrochloric acid and extracted with methylene chloride. The organic layer is washed with water, dried over anhydrous magnesium sulfate, the solvent is distilled off, and the residue is separated by column [filler: Wakogel C-200 (Wako Pure Chemical Industries, Ltd.).
Product name); Eluent: n-hexane / methylene chloride = 1/1 → 1 /
3] to obtain 2.0 g of 1,5,9-tris (4-benzyloxybenzoyloxy) anthracene as yellow crystals. mp. 240-242 ℃. ¹ HNMR δppm (CDCl ₃ ): 5.00 (2H, s, C H ₂ ), 5.03 (2H, s, C
H ₂ ), 5.23 (2H, s, C H ₂ ), 6.67 to 8.54 (34H, m, aromatic ring hydrogen). IR (KBr tablets) ν cm ^-1 : 1735 (COO-).

(3) 1 g (1.1 of 1,5,9-tris (4-benzyloxybenzoyloxy) anthracene obtained in the above (2)
(4 mmol) was used for catalytic reduction and post-treatment in the same manner as in (4) of Synthesis Example 1, and 0.7 g of the obtained crude crystal was recrystallized from a tetrahydrofuran / n-hexane mixed solution to give 1,5,9- Tris (4-hydroxybenzoyloxy) anthracene 0.
5 g was obtained as pale yellow crystals. mp. 326 ° C. ¹ HNMR δ ppm (DMSO-d ₆ ): 6.55 to 7.06 (6H, m, benzene ring
(3-H, 5-H) × 3), 7.32 to 8.23 (12H, m, anthracene ring 2-H,
3-H, 4-H, 6-H, 7-H, 8-H and benzene ring (2-H, 6-H) × 3), 8.
65 (1H, s, anthracene ring 10-H), 10.41 (3H , bs, O H × 3). IR (KBr tablets) ν cm ^-1 : 3408 (OH), 1702 (COO-).

Synthesis Example 4 Synthesis of 1,2,10-tris (4-hydroxybenzoyloxy) anthracene (1) 2.26 g of 1,2-dihydroxy-10-anthrone and 4 obtained in (2) of Synthesis Example 1 -Reaction and post-treatment were carried out in the same manner as in (3) of Synthesis Example 1 using 8 g of benzyloxybenzoic acid chloride, and 3.5 g of the obtained crude crystals were separated by column [filler: Wakogel C-200; eluent: n-hexane / methylene chloride = 4/1 → 2/1 → 1/1 (V / V)], and then 1,2,10-Tris (4
-Benzyloxybenzoyloxy) anthracene 1.6
g was obtained as yellow crystals. ¹ HNMR δ ppm (CDCl ₃ ): 5.09 (2H, s, C H ₂ ), 5.16 (2H, s, C
H ₂ ), 5.23 (2H, s, C H ₂ ), 6.91-8.44 (34H, m, anthracene ring hydrogen). IR (KBr tablet) ν cm ^-1 : 1740 (COO-).

(2) 1.54 g of 1,2,10-tris (4-benzyloxybenzoyloxy) anthracene obtained in the above (1)
(1.8 mmol) was subjected to catalytic reduction and post-treatment in the same manner as in (4) of Synthesis Example 1, and 0.92 g of the crude crystal obtained was recrystallized from a tetrahydrofuran / n-hexane mixed solution,
0.5 g of 1,2,10-tris (4-hydroxybenzoyloxy) anthracene was obtained as pale yellow crystals. ¹ HNMR δ ppm (DMSO-d ₆ ): 6.79 to 7.08 (6H, m, benzene ring
(3-H, 5-H) × 3), 7.49-8.29 (12H, m, benzene ring (2-H, 6-H)
× 3 and anthracene ring 3-H, 4-H, 5-H, 6-H, 7-H, 8-H), 8.
59 (1H, s, anthracene ring 9-H), 10.59 (3H , bs, O H × 3). IR (KBr tablets) νcm-1: 3413 (OH), 1706 (COO-).

Synthesis Example 5 2,6,9-Tris (4-hydroxy-
Synthesis of 3-methoxybenzoyloxy) anthracene (1) 4-Hydroxy-3-methoxybenzoic acid 25 g (0.15 mol) was suspended in 150 ml of ethanol, and 74.3 g (0.15 mol) of 2N sodium hydroxide aqueous solution and benzyl chloride were suspended in this suspension.
After adding 56.5 g (0.45 mol) and stirring and refluxing for 1 hour,
150 ml of a 5N sodium hydroxide aqueous solution was added dropwise with stirring under reflux, and after the addition, the mixture was further stirred under reflux for 1 hour. After the reaction, the solvent was distilled off, 300 ml of water was poured into the residue, and the pH was adjusted to 1 with concentrated hydrochloric acid. The precipitated crystals were collected by filtration, washed with water and dried to give 22.1 g of 4-benzyloxy-3-methoxybenzoic acid. Obtained as yellow crystals. mp. 171-12.5 ° C. ¹ HNMR δppm (DMSO-d ₆ ): 3.81 (3H, s, C H ₃ O), 5.16 (2H,
s, C H ₂ ), 7.13 (1H, d, J = 8Hz, Ar 5-H), 7.33〜7.44 (5H, m, aromatic ring hydrogen), 7.47 (1H, d, J = 2Hz, Ar 2-H ), 7.54 (1H, dd, J = 2Hz
And 8 Hz, Ar 6-H). IR (KBr tablet) ν cm _-1 : 1676 (COOH).

(2) 4-benzyloxy-3-obtained in (1) above
A suspension consisting of 22.3 g (86.3 mmol) of methoxybenzoic acid and 30.8 g (0.26 mol) of thionyl chloride was gradually warmed and reacted with stirring at 60 to 65 ° C for 2 hours. After the reaction, the reaction solution was concentrated to obtain 23.4 g of 4-benzyloxy-3-methoxybenzoic acid chloride as pale yellow flaky crystals. mp.63 ~ 65
° C.

(3) 4-benzyloxy-3-obtained in (2) above
Methoxybenzoyl chloride 10.1g (36.4mmol)
And 2,6-dihydroxy-9-anthrone (2.2 g, 11 mmol) were used to carry out a reaction and a post-treatment in the same manner as in (3) of Synthesis Example 1 to give 2,6,9-tris (4-benzyloxy). 7.8 g of (3-methoxybenzoyloxy) anthracene was obtained as pale yellow crystals. mp.186-189 ° C. ¹ HNMR δ ppm (CDCl ₃ ): 3.96 (3H, s, C H ₃ O), 3.99 (3H, s, C
H ₃ O), 4.00 (3H, s, C H ₃ O), 5.25 (2H, s, Ar-C H ₂ ), 5.27 (2H,
s, Ar-C H ₂ ), 5.29 (2H, s, Ar-C H ₂ ), 6.93 ~ 8.09 (30H, m,
Benzene ring hydrogen), 8.39 (1H, s, anthracene ring 10-H). IR (KBr tablets) νcm-1: 1736 (COO-).

(4) Using 2.4 g (2.52 mmol) of 2,6,9-tris (4-benzyloxy-3-methoxybenzoyloxy) anthracene obtained in (3) above, the same procedure as in (4) of Synthesis Example 1 was performed. Crude crystals obtained by catalytic reduction and post-treatment in the same manner
Recrystallization of 1.6 g from a mixed solution of terahydrofuran / n-hexane gave 0.9 g of 2,6,9-tris (4-hydroxy-3-methoxybenzoyloxy) anthracene as pale yellow crystals. mp. 206 ° C (decomposition). ¹ HNMR δppm (DMSO-d ₆ ): 3.94 (3H, s, C H ₃ O), 3.97 (3H,
s, C H ₃ O), 3.98 (3H, s, C H ₃ O), 7.01〜8.39 (15H, m, benzene ring hydrogen), 8.78 (1H, s, anthracene ring 10-H), 10.33 (3H,
. bs, O H × 3) IR (KBr ^{tablet) νcm -1: 3374 (OH)} , 1728 (COO-).

Synthesis Example 6 Synthesis of 1,2,10-tris (4-hydroxybenzenesulfonyloxy) anthracene (1) 9.61 g (0.24 mol) of sodium hydroxide was dissolved in 55 ml of water, and p-hydroxybenzenesulfone was added thereto. 40 g (0.17 mol) of sodium acid was suspended. Then, a solution of 27.6 g (0.22 mol) of benzyl chloride in ethanol (35 ml) was added dropwise, and the mixture was refluxed with stirring for 5 hours. After standing at room temperature overnight, the precipitated crystals were collected by filtration, washed with water and dried to obtain 35.2 g of sodium 4-benzyloxybenzenesulfonate as white crystals.

(2) 30 g (105 mmol) of sodium 4-benzyloxybenzenesulfonate obtained in (1) above was gradually added to 46 g (387 mmol) of thionyl chloride at 45 ° C. or lower, and N, N was added thereto. -After injecting 0.5 g of dimethylformamide, the mixture was stirred and refluxed at 50 to 60 ° C for 3.5 hours and then for 4 hours. After standing at room temperature overnight, the solvent was distilled off to obtain 29.1 g of residual 4-benzyloxybenzenesulfonyl chloride as white crystals. mp.95-97.5 ° C. ¹ HNMR δppm (DMSO-d ₆ ): 5.10 (2H, s, Ar-C H ₂ ), 6.95 (2H,
d, J = 8.8Hz, aromatic ring 2-H, 6-H), 7.29 to 7.43 (5H, m, aromatic ring hydrogen), 7.54 (2H, d, J = 8.8Hz, aromatic ring 3-H, 5- H). IR (KBr tablet) ν cm ⁻¹ : 1370,1190,1170.

(3) 1,2-dihydroxy-10-anthrone 4
g (17.7 mmol) in 100 ml of methylene chloride,
To this, 6.2 g (61 mmol) of triethylamine was injected, and 15.8 g (58 mmol) of 4-benzyloxybenzenesulfonyl chloride obtained in the above (2) was added to this at 5 to 10 ° C.
Was added little by little, and the mixture was stirred and reacted at 18 to 23 ° C. for 5 hours, and then left overnight at room temperature. The reaction solution was extracted with 50 ml of methylene chloride, and the methylene chloride layer was washed once with 70 ml of 0.1N hydrochloric acid, once with 70 ml of a saturated aqueous sodium hydrogen carbonate solution, once with 70 ml of water, and then dried over anhydrous magnesium sulfate. After filtering off the desiccant,
The solvent was distilled off, and 18 g of the resulting residual oily substance was separated by column [filler: Wakogel C-200 (trade name of Wako Pure Chemical Industries, Ltd.); eluent: n-hexane / methylene chloride = 4/1 → 3 / 1 →
2/1 (V / V)] to obtain 5.75 g of 1,2,10-tris (4-benzyloxybenzenesulfonyloxy) anthracene as yellow crystals. ¹ HNMR δ ppm (CDCl ₃ ): 5.07 (2H, s, ArC H ₂ ), 5.18 (4H, s, Ar
C H ₂ × 2), 6.82 to 8.05 (33 H , m, aromatic ring hydrogen, except aromatic ring H-10), 8.49 (1 H, s, aromatic ring H-10). IR (KBr tablet) ν cm ^-1 : 1370,1195,1170.

(4) 1,2,10-Tris (4-benzyloxybenzenesulfonyloxy) anthracene obtained in (3) above
3.8 g (4 mmol) was dissolved in 80 ml of tetrahydrofuran, 10 g of 5% palladium-carbon was added, and catalytic reduction was carried out at room temperature under normal pressure. After reduction for 5 hours, the catalyst was filtered off and the filtrate was concentrated to give 1.7 g of an orange oily residue which was separated by column [filler: Wakogel C-200; eluent: methylene chloride / methanol = 20/1 (V / V)] to obtain 0.85 g of 1,2,10-tris (4-hydroxybenzenesulfonyloxy) anthracene as yellow crystals. ¹ HNMR δ
ppm (acetone-d ₆ ): 6.89 to 8.14 (18H, m, aromatic ring hydrogen, except aromatic ring H-10), 8.44 (1H, s, aromatic ring H-10), 9.74 (1H, b
s, O H ). IR (KBr tablet) ν cm ⁻¹ : 3440 (OH), 1370, 1190, 1167.

Synthesis Example 7 Synthesis of 1,5,9-tris (4-hydroxybenzenesulfonyloxy) anthracene (1) 1.5 g of 1,5-dihydroxy-9-anthrone obtained in (1) of Synthesis Example 3 (6.6 (3 mmol) in 40 ml of methylene chloride and 2.33 g (23 mmol) of triethylamine was added at 10 ° C or lower, and then 5.9 g (20.8 g of 2-benzyloxybenzenesulfonyl chloride obtained in (2) of Synthesis Example 6).
Mmol) was added little by little at 8 to 12 ° C.
Reaction and post-treatment were carried out in the same manner as in (3), and 5.2 g of the obtained crude oily substance was separated by column [filler: Wakogel C-200
(Wako Pure Chemical Industries, Ltd. product name); Eluent: n-hexane / methylene chloride = 8/1 → 4/1 → 1/1 → 1/2 (V / V)] and 1,5,9 1.8 g of -tris (4-benzyloxybenzenesulfonyloxy) anthracene was obtained as orange-yellow crystals. ¹ HNMR δ ppm (CDCl ₃ ): 4.85 (2H, s, ArC H ₂ ), 5.02 (2H, s, Ar
C H ₂ ), 5.11 (2H, s, ArC H ₂ ), 6.69,6.88,6.95 (each 2H, each d, each J =
8.6Hz (benzene ring 3-H, 5-H) x 3), 7.02 to 7.87 (27H, m, (benzene ring 2-H, 6-H) x 3), ArC H ₂ x 3 and anthracene ring
2-H, 3-H, 4-H, 6-H, 7-H, 8-H), 8.38 (1H, s, anthracene ring
10-H). IR (KBr tablet) ν cm ^-1 : 1378,1192,1170.

(2) 1,5,9-Tris (4-benzyloxybenzenesulfonyloxy) anthracene obtained in the above (1)
Catalytic reduction and post-treatment were carried out in the same manner as in (4) of Synthesis Example 6 using 0.5 g (0.5 mmol) to obtain 0.18 g of 1,5,9-tris (4-hydroxybenzenesulfonyloxy) anthracene as a concentrated residue. Obtained as pale yellow crystals. ¹ HNMR δ ppm (acetone-d ₆ ): 6.55, 6.72, 6.77 (each 2H, each d, each J
= 8.6Hz, (benzene ring 3-H, 5-H) × 3), 7.09 ~ 7.89 (12H, m,
Anthracene ring 2-H, 3-H, 4-H, 6-H, 7-H, 8-H and benzene ring (2-H, 6-H) × 3), 8.28 (1H, s, anthracene ring 10 -H),
9.62 (3H, s, O H × 3) IR (KBr ^{tablet) νcm -1:. 3418 (OH} ), 1367,1192,1167.

Synthesis Example 8 Synthesis of 2,6,9-tris (4-hydroxybenzenesulfonyloxy) anthracene (1) 1 g (4.4 mmol) of 2,6-dihydroxy-9-anthrone was dissolved in 20 ml of pyridine and 27 ml of methylene chloride. After dissolving and adding 1.56 g of triethylamine at 10 ° C or lower, 3.94 g (13.9 mmol) of 4-benzyloxybenzenesulfonyl chloride obtained in (2) of Synthesis Example 6 was added at 8-12 ° C.
Was added in small amounts, and the reaction and post-treatment were carried out in the same manner as in (3) of Synthesis Example 6, and 3.3 g of the crude crystals obtained were separated by column [filler: Wakogel C-200]; eluent: n-hexane. /
Methylene chloride = 8/1 → 2/1 → 1/1 (V / V)] and then recrystallized from n-hexane / ethyl acetate to give 2,6,9-tris (4-benzyloxybenzenesulfonyloxy) Anthracene
1.2 g was obtained as pale yellow crystals. mp. 163.5-165.5 ° C. ¹ HNMR δ ppm (CDCl ₃ ): 5.07 (2H, s, ArC H ₂ ), 5.11 (2H, s, A
rC H ₂ ), 5.18 (2H, s, ArC H ₂ ), 6.99 ~ 7.09 (7H, m, (benzene ring 3-H, 5-H) × 3 and anthracene ring 7-H), 7.17 (1H, dd ,
J = 2.2Hz and J = 9.5Hz, anthracene ring 3-H), 7.28 to 7.4
6 (15H, m, aromatic ring × 3), 7.49 (1H, d, J = 2.2Hz, anthracene ring 1-H), 7.61 (1H, d, J = 2.2Hz, anthracene ring 5-H), 7.75
~ 7.84 (6H, m, (benzene ring 2-H, 6-H) × 3), 7.87 (1H, d, J =
9.5Hz, anthracene ring 8-H), 7.96 (1H, d, J = 9.5Hz, anthracene ring 4-H), 8.24 (1H, s, anthracene ring 10-H). IR (KBr tablet) ν cm ₋₁ : 1371, 1192, 1170.

(2) 2,6,9-tris (4-benzyloxybenzenesulfonyloxy) anthracene obtained in the above (1)
Using 1.05 g (1.1 mmol), catalytic reduction and post-treatment were carried out in the same manner as in (4) of Synthesis Example 6, the concentrated residue was crystallized from methylene chloride, collected by filtration and dried to give 2,6,9- Tris (4-
Hydroxybenzenesulfonyloxy) anthracene
0.4 g was obtained as pale yellow crystals. mp. 192-1945 ° C (decomposition). ¹ HNMR δ ppm (CDCl ₃ ): 6.91 to 7.01 (6H, m, (benzene ring
3-H, 5-H) × 3), 7.20 to 7.27 (2H, m, anthracene ring 3-H, 7-
H), 7.39 (1H, d, J = 1.8Hz, anthracene ring 1-H), 7.63-7.7
4 (6H, m, (benzene ring 2-H, 6-H) × 3), 7.79 (1H, d, J = 1.8Hz,
Anthracene ring 5-H), 7.93 (1H, d, J = 9.5Hz, Anthracene ring 8-H), 8.15 (1H, d, J = 9.5Hz, Anthracene ring 4-H), 8.66
(1H, s, anthracene ring 10-H), 10.88 (1H, s, -O H ), 10.91 (1
H, s, -O H), 11.05 (1H, s, -O H). IR (KBr tablet) ν cm ⁻¹ : 3401 (OH), 1363, 1188, 1167.

Synthesis Example 9 Synthesis of 2,6,9-tris (3,4-dihydroxybenzoyloxy) anthracene (1) Suspension of 25.4 g (0.17 mol) of 3,4-dihydroxybenzoic acid in ethanol (250 ml) Then, 270 ml of 5N aqueous sodium hydroxide solution and 102 g (0.81 mol) of benzyl chloride were added thereto, and the mixture was stirred and refluxed for 6 hours. After the reaction, the mixture was cooled to room temperature and left overnight, then 40 ml of concentrated hydrochloric acid was injected and the precipitated crystals were collected by filtration, washed with hot ethanol and dried under reduced pressure to give 38.2 g of 3,4-dibenzyloxybenzoic acid as pale yellow crystals. Obtained. mp.
184-186 ° C. ¹ HNMR δ ppm (DMSO-d ₆ ): 3.38 (1H, bs, -O H ), 5.18 (2H, s, A
rC H _2- ), 5.22 (2H, s, ArC H _2- ), 7.16 (1H, d, J = 8.8Hz, benzene ring 5-H), 7.30 to 7.57 (12H, m, benzene ring hydrogen). IR (KBr tablet) ν cm ^-1 : 1679 (C = O).

(2) 10 g (30 mmol) of 3,4-dibenzyloxybenzoic acid obtained in (1) above and 10.7 g of thionyl chloride
The suspension consisting of (90 mmol) was gradually heated and reacted at 85 ° C for 1 hour, and then the reaction solution was concentrated to dryness to obtain 10.3 g of 3,4-dibenzyloxybenzoic acid chloride as white crystals. It was mp. 92.5-94.5 ° C.

(3) Synthesis Example 1 using 5.2 g (14.6 mmol) of 3,4-dibenzyloxybenzoic acid chloride obtained in (2) above and 1 g (4.4 mmol) of 2,6-dihydroxy-9-anthrone. Reaction and post-treatment were carried out in the same manner as in (3) above, and 5.4 g of the crude crystals obtained were recrystallized from a mixed solution of methylene chloride / ethyl acetate (1/4 [V / V]) for 2,6, 9-Tris (3,4-dibenzyloxybenzoyloxy) anthracene 3.4g
Was obtained as yellow crystals. mp.189-191 ° C. ¹ HNMR δ ppm (CDCl ₃ ): 5.20 ~ 5.31 (12 H, m, ArC H ₂ × 6),
7.14 ~ 8.05 (44H, m, benzene ring hydrogen), 8.21 (1H, d, J = 9.2H
z, anthracene ring 4-H), 8.58 (1H, s, anthracene ring 10-
H). IR (KBr tablet) ν cm ^-1 : 1733 (COO-).

(4) 2 g of 2,6,9-tris (3,4-dibenzyloxybenzoyloxy) anthracene obtained in the above (3)
(1.7 mmol) was subjected to catalytic reduction and post-treatment in the same manner as in (4) of Synthesis Example 1, and 1.8 g of the obtained crude crystal was extracted from a tetrahydrofuran / n-hexane mixed solution (5/7 [V / V]). Recrystallization was performed to obtain 1.2 g of 2,6,9-tris (3,4-dihydroxybenzoyloxy) anthracene as pale yellow crystals. m
p. 233 ° C (decomposition). ¹ HNMR δ ppm (DMSO-d ₆ ): 6.87 to 8.08 ( ¹⁴ H, m, aromatic ring), 8.
27 (1H, d, J = 9.2Hz, anthracene ring 4-H), 8.67 (1H, s, anthracene ring 10-H), 9.77 (6H, bs, OH × 6). IR (KBr tablets) ν cm ⁻¹ : 3365 (OH), 1701 (COO-).

Synthesis Example 10 1,2,10-Tris (3-chloro-4-
Synthesis of hydroxybenzoyloxy) anthracene (1) 25 g of 3-chloro-4-hydroxybenzoic acid hemihydrate
(0.14 mol) and 52.3 g (0.41 mol) of benzyl chloride were reacted and post-treated in the same manner as in (1) of Synthesis Example 1 to give 20.4 g of 4-benzyloxy-3-chlorobenzoic acid as white crystals. Obtained. mp.211-213 ° C. ¹ HNMR δ ppm (DMSO-d ₆ ): 5.30 (2H, s, ArC H ₂ O-), 7.34 (1
H, d, J = 8.4Hz, aromatic ring 5-H), 7.37 to 7.49 (5H, m, aromatic ring hydrogen), 7.88 (1H, dd, J = 1.8Hz and J = 8.4Hz, aromatic ring 6-H) ), 7.93
(1H, d, J = 1.8Hz, aromatic ring 2-H), 11.15 (1H, bs, -COO H ). IR (KBr tablet) ν cm ^-1 : 1683 (COOH).

(2) 4-benzyloxy-3-obtained in the above (1)
The reaction and post-treatment were carried out in the same manner as in (2) of Synthesis Example 1 using 2.0 g (7.6 mmol) of chlorobenzoic acid to obtain 2.1 g of 4-benzyloxy-3-chlorobenzoic acid chloride as light brown crystals. . mp. 78-80 ° C. IR (KBr tablet) ν cm ^-1 : 1751 (C = O).

(3) 4-benzyloxy-3-obtained in (2) above
Chlorinated benzoic acid chloride 1.6 g (5.7 mmol) and 1,2
The reaction and post-treatment were carried out in the same manner as in (3) of Synthesis Example 1 using 0.4 g (1.7 mmol) of -dihydroxy-10-anthrone, and 1.1 g of the obtained crude crystals were separated by column [filler: Wakogel C- 200 (trade name of Wako Pure Chemical Industries, Ltd.); Eluent: n-
Hexane / methylene chloride = 4/1 → 3/1 → 1/1 (V / V)]
0.65 g of 2,10-tris (4-benzyloxy-3-chlorobenzoyloxy) anthracene was obtained as pale yellow crystals. mp.106-109 ° C. ¹ HNMR δ ppm (CDCl ₃ ): 5.18 (2H, s, ArC H ₂ O-), 5.25 (2H,
s, ArC H ₂ O-), 5.33 (2H, s, ArC H ₂ O-), 6.91 ~ 8.46 (30H, m,
Benzene ring hydrogen), 8.49 (1H, s, anthracene ring 9-H). IR (KBr tablet) ν cm ⁻¹ : 1743 (COO-).

(4) As in (4) of Synthesis Example 1, using 280 mg (0.4 mmol) of 1,2,10-tris (4-benzyloxy-3-chlorobenzoyloxy) anthracene obtained in (3) above. Catalytic reduction and post-treatment are carried out, and 1,2,10-tris (3
0.2 g of -chloro-4-hydroxybenzoyloxy) anthracene was obtained as white crystals. mp. 238 ° C. ¹ HNMR δ ppm (acetone-d ₆ ): 6.98 to 8.41 (15H, m, aromatic ring hydrogen), 8.52 (1H, s, anthracene ring 9-H), 10.41 (3H, bs, -O)
H ). IR (KBr tablets) ν cm ^-1 : 3382 (OH), 1747 (COO-).

Synthesis Example 11 Synthesis of 1,2,10-tris (3-hydroxy-4-methylbenzoyloxy) anthracene (1) 3-hydroxy-4-methylbenzoic acid 20.3 g (0.13 mol) and benzyl chloride 50.8 g (0.40 mol) was used for the reaction and post-treatment in the same manner as in (1) of Synthesis Example 1, and the obtained crude crystals were recrystallized from ethanol to give 3-benzyloxy-
15.0 g of 4-methylbenzoic acid was obtained as white crystals. mp. 15
9-161 ° C. ¹ HNMR δ ppm (DMSO-d ₆ ): 2.26 (3H, s, C H ₃ ), 5.18 (2H, s, Ar
C H ₂ O-), 7.27 to 7.43 (6H, m, benzene ring and aromatic ring 5-H),
7.47 (1H, s, aromatic ring 2-H), 7.51 (1H, d, J = 7.7Hz, aromatic ring 6-
H), 12.81 (1H, bs, COO H ). IR (KBr tablets) ν cm ^-1 : 1690 (COOH).

(2) 3-benzyloxy-4-obtained in the above (1)
The reaction and post-treatment were carried out in the same manner as in (2) of Synthesis Example 1 using 3.0 g (12.4 mmol) of methylbenzoic acid to obtain 3.12 g of 3-benzyloxy-4-methylbenzoic acid chloride as pale yellow crystals. . mp. 49-51 ° C. IR (KBr tablet) ν cm ⁻¹ : 1741 (C = O).

(3) 3-benzyloxy-4-obtained in the above (2)
2.85 g (10.9 mmol) of methylbenzoic acid chloride
The reaction and post-treatment were carried out in the same manner as in (3) of Synthesis Example 1 using 0.75 g (3.3 mmol) of 1,2-dihydroxy-10-anthrone, and the obtained crude crystals were separated by column [filler: Wakogel C -200 ； Eluent: methylene chloride] and 1,2,10-tris (3-benzyloxy-4-methylbenzoyloxy)
160 mg of anthracene was obtained as yellow crystals. mp.132 ~ 13
5 ° C. ¹ HNMR δ ppm (CDCl ₃ ): 2.17 (3H, s, C H ₃ ), 2.27 (3H, s, C
H ₃ ), 2.31 (3H, s, C H ₃ ), 5.03 (2H, s, ArC H ₂ O-), 5.15 (2H, s, A
rC H ₂ O-), 5.24 (2H, s, ArC H ₂ O-), 7.15 to 8.07 (30H, m, aromatic ring hydrogen), 8.45 (1H, s, anthracene ring 9-H). IR (KBr tablet) ν cm ^-1 : 1737 (COO-).

(4) Similar to (4) of Synthesis Example 1 using 150 mg (0.17 mmol) of 1,2,10-tris (3-benzyloxy-4-methylbenzoyloxy) anthracene obtained in (3) above. Reduced and post-treated to give 1,2,10-tris (3-hydroxy-4-methylbenzoyloxy) anthracene 80m
g was obtained as white crystals. mp.251 ° C (decomposition). ¹ HNMR δppm (Acetone-d ₆ ): 2.22 (3H, s, C H ₃ ), 2.25 (3H,
s, C H ₃ ), 2.27 (3H, s, C H ₃ ), 6.95-8.26 (15H, m, aromatic ring hydrogen), 8.56 (1H, s, anthracene ring 9-H), 10.11 (3H, bs, OH × 3). IR (KBr tablets) ν cm ^-1 : 3409 (OH), 1716 (COO-).

Synthesis Example 12 Synthesis of poly (methyl methacrylate / glycidyl methacrylate / 2,3-dihydroxypropyl methacrylate) (1) 50.1 g (0.5 mol) of methyl methacrylate and 28.4 g (0.2 mol) of glycidyl methacrylate were added. It was dissolved in 240 ml of toluene, 0.8 g of 2,2′-azobis (methyl 2-methylpropionate) was added thereto, and the mixture was stirred and reacted at 80 ° C. for 7 hours under a nitrogen stream. The reaction solution was poured into 200 ml of methanol to cause precipitation, and the precipitated crystals were collected by filtration and dried under reduced pressure to obtain 77 g of poly (methyl methacrylate / glycidyl methacrylate) as white powder crystals. In the obtained copolymer, the composition ratio of the methyl methacrylate unit and the glycidyl methacrylate unit was ¹ HNMR.
It was about 5: 2 from the measurement. The weight average molecular weight (Mw) of the copolymer was about 35,800 and the number average molecular weight (Mn) was about 19,200 by GPC measurement using polystyrene as a standard.

(2) 5 g of the poly (methyl methacrylate / glycidyl methacrylate) obtained in the above (1) was dissolved in 50 ml of tetrahydrofuran at 40 ° C., 10 ml of 1N sulfuric acid was added thereto, and the mixture was stirred and reacted at 40 ° C. for 1 hour. It was After cooling the reaction solution to 10 ℃, pour it into 500 ml of water, collect the precipitated crystals by filtration, wash with water, and dry under reduced pressure to obtain poly (methyl methacrylate / glycidyl methacrylate / 2,3-dihydroxypropyl methacrylate) 2.5.
g was obtained as a white powder crystal. The composition ratio of the methyl methacrylate unit, the glycidyl methacrylate unit and the 2,3-dihydroxypropyl methacrylate unit of the obtained copolymer was
It was about 5: 1: 1 from ¹ H NMR measurement. The weight average molecular weight is about 36300 from GPC measurement (polystyrene standard).
The number average molecular weight was about 20,200.

Synthesis Example 13 Synthesis of sorbitol polyglycidyl ether / ethylenediamine resin 9.1 g of sorbitol polyglycidyl ether and 0.2 g of ethylenediamine were dissolved in 15 ml of 1,4-dioxane, and 10
The mixture was reacted at 0 ° C. for 3 hours with stirring. After cooling, add 150m
After being washed twice with 1, the mixture was concentrated under reduced pressure to obtain 2.3 g of sorbitol polyglycidyl ether / ethylenediamine resin as a colorless viscous oil.

Synthesis Example 14 Synthesis of sorbitol polyglycidyl ether / glutaric acid resin 9.1 g of sorbitol polyglycidyl ether, 0.8 g of glutaric acid and 30 mg of benzyltriethylammonium chloride were suspended and reacted with stirring at 80 ° C. for 4 hours. After cooling, pour 60 ml of methylene chloride into the reaction mixture and dilute it with water.
The extract was washed 3 times with ml and concentrated under reduced pressure to obtain 9.4 g of sorbitol polyglycidyl ether / glutaric acid resin as a slightly yellow viscous oil.

Synthesis Example 15 Synthesis of poly (methyl methacrylate / glycidyl methacrylate / tert-butyl methacrylate) Methyl methacrylate 40.0 g (0.4 mol) and glycidyl methacrylate 28.4 g (0.2 mol) and tert-methacrylate.
The reaction and post-treatment were carried out in the same manner as in (1) of Synthesis Example 12 using 14.2 g (0.1 mol) of butyl, and the precipitated crystals were collected by filtration and dried under reduced pressure to give poly (methyl methacrylate / glycidyl methacrylate / methacrylic acid). (tert-butyl) 78.5 g was obtained as white powder crystals. Methyl methacrylate unit and glycidyl methacrylate unit of the obtained copolymer and t
Composition ratio of ert-butyl unit: Approximately 4: 2: 1 from ¹ H NMR measurement
Met. The weight average molecular weight of the copolymer was about 35,000 and the number average molecular weight was about 19,000 according to GPC measurement using polystyrene as a standard.

Synthesis Example 16 Synthesis of poly (methyl methacrylate / glycidyl methacrylate / 2-hydroxyethyl methacrylate) 35.0 g (0.35 mol) of methyl methacrylate, 28.4 g (0.2 mol) of glycidyl methacrylate and 2-methacrylate
Synthesis Example 12 using 13.0 g (0.1 mol) of hydroxyethyl
Reaction and post-treatment are carried out in the same manner as in (1) above, and the precipitated crystals are collected by filtration and dried under reduced pressure to give poly (methyl methacrylate / glycidyl methacrylate / 2-hydroxyethyl methacrylate).
70.3 g was obtained as white powder crystals. The obtained copolymer had a weight average molecular weight of about 35,000 and a number average molecular weight of about 19,200 according to GPC measurement using polystyrene as a standard.

Synthesis Example 17 Synthesis of poly (methyl methacrylate / glycidyl methacrylate / n-butyl methacrylate) Methyl methacrylate 20.0 g (0.2 mol) and glycidyl methacrylate 14.2 g (0.1 mol) and n-butyl methacrylate 7.1 g (0.05 mol) was used for the reaction and post-treatment in the same manner as in Synthesis Example 12 (1), and the precipitated crystals were collected by filtration and dried under reduced pressure to give poly (methyl methacrylate / glycidyl methacrylate / methacrylic acid n- Butyl) (31.7 g) was obtained as white powder crystals. The composition ratio of the methyl methacrylate unit, the glycidyl methacrylate unit, and the n-butyl methacrylate unit of the obtained copolymer was about 4: 2: 1 by ¹ HNMR measurement. The weight average molecular weight was about 35,000 and the number average molecular weight was about 19,200 according to GPC measurement (polystyrene standard).

Synthesis Example 18 Synthesis of poly (methyl methacrylate / glycidyl methacrylate / 9-anthracene methyl methacrylate) (1) 50 g (0.24 mol) of 9-anthracenemethanol, 50.6 g (0.5 mol) of triethylamine and 750 ml of benzene
A suspension of 52.3 g (0.5 mol) of methacrylic acid chloride in benzene (50 ml) was added dropwise thereto at 10 ° C. or lower, and the mixture was reacted with stirring at 20 ° C. for 1 hour. After standing overnight at room temperature,
The reaction solution was poured into 150 ml of ethyl acetate and 800 ml of water, and the organic layer was once treated with 700 ml of 1.4% sodium carbonate aqueous solution and water 10 ml.
After washing 4 times with 00 ml, it was concentrated under reduced pressure. The residual oily substance was crystallized from cyclohexane, collected by filtration and dried under reduced pressure to obtain 74.0 g of methyl 9-anthracenemethyl methacrylate as yellow crystals. mp. 83-84 ° C. ¹ HNMR δ ppm (CDCl ₃ ): 1.90 (3H, s, C H ₃ ), 5.48 (1H, s, C = C H
₂ ), 6.04 (1H, s, C = C H ₂ ), 6.19 (2H, s, ArC H ₂ O-), 7.43 ~ 8.3
9 (8H, m, anthracene ring hydrogen), 8.46 (1H, s, anthracene ring 10-H). IR (KBr tablet) ν cm ^-1 : 1722 (COO-).

(2) 20.0 g (0.20 mol) of methyl methacrylate, 14.2 g (0.10 mol) of glycidyl methacrylate and 9-anthracenemethyl methacrylate obtained in (1) above.
Reaction and post-treatment were carried out in the same manner as in (1) of Synthesis Example 12 using 8.3 g (0.03 mol), and the precipitated crystals were collected by filtration and dried under reduced pressure to give poly (methyl methacrylate / glycidyl methacrylate /
30.8 g of 9-anthracenemethyl methacrylate) was obtained as pale yellow powder crystals. The composition ratio of the methyl methacrylate unit, the glycidyl methacrylate unit and the 9-anthracene methyl methacrylate unit of the obtained copolymer was about 20: 10: 3 by ¹ H NMR measurement. The weight average molecular weight was about 37500 and the number average molecular weight was about 19,000 according to GPC measurement (polystyrene standard).

Synthesis Example 19 Synthesis of poly (methyl acrylate / glycidyl methacrylate) Synthesis Example 12 was prepared using 21.5 g (0.25 mol) of methyl acrylate and 14.2 g (0.10 mol) of glycidyl methacrylate.
Reaction and post-treatment were carried out in the same manner as in (1), and the precipitated crystals were collected by filtration and dried under reduced pressure to obtain 21.0 g of poly (methyl acrylate / glycidyl methacrylate) as a colorless viscous oil.
The composition ratio of the methyl acrylate unit and the glycidyl methacrylate unit of the obtained copolymer was about 5: 2. or,
From the GPC measurement (polystyrene standard), the weight average molecular weight was about 35,000 and the number average molecular weight was about 18,000.

Example 1 A far-ultraviolet light absorbing material having the following composition was prepared. Poly (methyl methacrylate / glycidyl methacrylate / 2,3-dihydroxypropyl methacrylate) (resin of Synthesis Example 12) 4.0 g 2,6,9-tris (4-hydroxybenzoyloxy) anthracene (Compound of Synthesis Example 1) 1.0 g Tetrahydrofurfuryl alcohol 45.0 g Propylene glycol monomethyl ether acetate 50.0 g The above composition was spin coated on a substrate (quartz wafer),
It was baked on a hot plate at 200 ° C. for 90 seconds to obtain a far-ultraviolet light absorbing material film having a film thickness of 100 nm. Then U of this material film
V measurement was performed. This UV spectrum is shown in FIG. From the results shown in FIG. 1, it can be seen that this material film has absorption around 250 nm. It was also confirmed that this material film did not elute in acetone at all, and a crosslinking reaction had occurred.

Example 2 A far-ultraviolet light absorbing material having the following composition was prepared. Poly (methyl methacrylate / glycidyl methacrylate / 2,3-dihydroxypropyl methacrylate) (resin of Synthesis Example 12) 4.0 g 1,2,10-tris (4-hydroxybenzenesulfonyloxy) anthracene (Compound of Synthesis Example 6 ) 1.0 g tetrahydrofurfuryl alcohol 45.0 g propylene glycol monomethyl ether acetate 50.0 g The above composition is spin-coated on a substrate (quartz wafer),
The film was baked on a hot plate at 180 ° C for 90 seconds to obtain a far-ultraviolet light absorbing material film having a film thickness of 100 nm. Then U of this material film
V measurement was performed. This UV spectrum is shown in FIG. From the results of FIG. 2, it can be seen that this material film has absorption around 250 nm. It was also confirmed that this material film did not elute in acetone at all, and a crosslinking reaction had occurred.

Example 3 A chemically amplified positive resist material having the following composition was prepared. Poly [p- (1-ethoxyethoxy) styrene / p-hydroxystyrene] 2.50g 2-Cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane 0.13g Propylene glycol monomethyl ether acetate 7.37g As a far-ultraviolet light absorbing material Using the composition described in Example 1 and using a resist material having the above composition as a chemically amplified positive resist material, pattern formation was performed on a highly reflective substrate having steps. The results will be described with reference to FIG.

A far-ultraviolet light absorbing material 2 having the composition described in Example 1 was spin-coated on a highly reflective aluminum step substrate 1 obtained by subjecting a silicon substrate to photolithography, etching and aluminum sputtering.
The film was baked on a hot plate at 00 ° C for 90 seconds to obtain a far-ultraviolet light absorbing material film of 100 nm (Fig. 3a). Then, a chemically amplified positive resist material 3 having the above composition was spin-coated on this absorbing material film and prebaked at 90 ° C. for 90 seconds on a hot plate to obtain a resist material film having a thickness of 1.0 μm (FIG. 3).
b). Next, a 248.4 nm KrF excimer laser beam 4 was selectively exposed through a mask 5 (FIG. 3c). And 1
After post-baking on a hot plate at 00 ° C for 90 seconds, it is developed with an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution) for 60 seconds to dissolve and remove only the exposed portion of the resist material 3 to form a positive pattern 3a. Obtained (Fig. 3d). The obtained positive type pattern resolved a 0.25 μm line and space and had a good pattern shape (rectangle). The exposure dose at this time was about 30 mJ / cm ² . After that, the far ultraviolet light absorbing material film 2 and the aluminum substrate 1 according to the present invention were sequentially etched with oxygen gas and chlorine-based gas using the pattern 3a as a mask (FIG. 3e). The formed etching pattern 1a is a resist pattern 3
The pattern was a good pattern with no dimensional variation from that of a.

Examples 4 to 25 Far ultraviolet light absorbing materials having the compositions shown in Tables 1 to 7 below were prepared.

[0112]

[Table 1]

[0113]

[Table 2]

[0114]

[Table 3]

[0115]

[Table 4]

[0116]

[Table 5]

[0117]

[Table 6]

[0118]

[Table 7]

Using each of the far-ultraviolet light absorbing materials having the compositions shown in Tables 1 to 7 above, an absorbing material film was formed in the same manner as in Example 3, and the chemistry described in Example 3 was formed on this film. Pattern formation was performed in the same manner as in Example 3 using the amplification type positive resist material. The results are shown in Tables 8 and 9 below.

[0120]

[Table 8]

[0121]

[Table 9]

It should be noted that none of the material films of Examples 4 to 25 eluted at all in acetone, indicating that the crosslinking reaction proceeded.

Comparative Example 1 A chemically amplified positive resist material having the composition described in Example 3 was used without using the far-ultraviolet light absorbing material according to the present invention. Pattern formation was performed in the same manner. As a result, as shown in FIG. 4a, the pattern 3b was a defective pattern affected by reflection. After that, an attempt was made to etch the base substrate, but the etching pattern 1b was a defective pattern in which the dimension variation was larger than the original resist pattern width due to a defective resist pattern (FIG. 4b).

Comparative Examples 2 to 5 Materials having a far-ultraviolet light absorber having the respective compositions shown in Table 10 below were prepared.

[0125]

[Table 10]

Using the materials having the compositions shown in Table 10 in place of the far-ultraviolet light absorbing material according to the present invention, material films were formed in the same manner as in Example 3, and Example 3 was formed on this film. Pattern formation was performed in the same manner as in Example 3 using the chemically amplified positive resist material having the composition described in 1. As a result, both mix with the resist material at the interface,
As shown in FIG. 5, the pattern shape was extremely poor.

It was confirmed that the addition of the resin component or the far-ultraviolet light absorber to the resin component had no effect, and the far-ultraviolet light absorber capable of undergoing the crosslinking reaction according to the present invention was an essential component.

Comparative Example 6 A film material having the following composition was prepared. Poly (methyl methacrylate / glycidyl methacrylate / 2,3-dihydroxypropyl methacrylate) [Resin of Synthesis Example 12] 4.0 g 1,8,9-Tris (4-hydroxybenzoyloxy) anthracene 1.0 g Tetrahydrofurfuryl alcohol 45.0 g Propylene glycol monomethyl ether acetate 50.0 g The above composition was spin coated on a substrate (quartz wafer),
Baking was performed on a hot plate at 200 ° C. for 90 seconds to obtain a material film having a film thickness of 100 nm. Next, when this material film was immersed in acetone, it was easily eluted. In this way, when 1,8,9-tris (4-hydroxybenzoyloxy) anthracene is used, the crosslinking reaction does not proceed and it cannot be used for the far-ultraviolet absorbing material film (antireflection film) utilizing the crosslinking reaction. I knew that.

[0129]

As is apparent from the above description, the far-ultraviolet light absorbing material according to the present invention is used for far-ultraviolet light (300 nm or less) or K.
High reflectance of aluminum, aluminum-silicon, aluminum-silicon-copper, polysilicon, copper or silver as an undercoat material for exposure resist materials such as rF excimer laser light (248.4 nm) and ArF excimer laser light (193 nm) When used as a substrate or a stepped substrate, a good quarter-micron pattern shape can be obtained while maintaining high resolution performance and high sensitivity without causing notching or halation which is a problem such as disconnection in these substrates. Therefore, the present invention has great value for the formation of ultrafine patterns in the semiconductor industry and the like.

[0130]

[Brief description of drawings]

FIG. 1 shows an ultraviolet spectrum curve diagram of a far-ultraviolet light absorbing material film obtained in Example 1.

FIG. 2 shows an ultraviolet spectrum curve diagram of the far-ultraviolet light absorbing material film obtained in Example 2.

FIG. 3 is a process cross-sectional view of a pattern forming method when the far ultraviolet light absorbing material of the present invention in Example 3 is used as an undercoating agent.

FIG. 4 is a cross-sectional view of a pattern that cannot be formed, which is observed when pattern formation is attempted without using the far-ultraviolet light absorbing material of the present invention in Comparative Example 1.

FIG. 5 is a cross-sectional view of a pattern formation failure observed when pattern formation was attempted by using each material shown in Comparative Examples 2 to 5 as an undercoating agent.

[0131]

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... High reflective substrate, 2 ... Far-ultraviolet light absorption material, 3 ... Chemical amplification type positive resist material, 4 ... KrF excimer laser light, 5 ... Mask, 3a ... Resist pattern 1a ...
Etching pattern 3b ... Resist pattern 1b.
..Etching pattern, 3 '... Mixing of resist material and undercoat of comparative example, 3c ... Resist pattern, 6 ...
Undercoat for comparative examples.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location H01L 21/027 (72) Inventor Hiroshi Matsuda 1633 Matoba, Kawagoe City, Saitama Wako Pure Chemical Industries, Ltd. (72) Inventor Masataka Endo 1006 Kadoma, Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd. (72) Satoshi Kobayashi 1006, Kadoma, Kadoma City, Osaka Matsushita Electric Industrial Co., Ltd.

Claims (5)

[Claims] 1. One or more compounds having at least one glycidyl group in the molecule and the following general formula [1]: [Wherein, X is _{-O-SO 2 -, - O} -CO- or -CO
Represents a hydrogen atom, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or a hydroxyl group, and R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group. Group, alkoxy group, halogen atom or the following general formula [2] (Wherein R ¹ , R ² and X are the same as defined above) (provided that at least one of R ^{3 to} R ⁶ is a group represented by the general formula [2]). In addition, a compound in which the group represented by the general formula [2] is simultaneously introduced into the 1-position, 8-position and 9-position of the anthracene ring is excluded. ] The far-ultraviolet light absorption material which consists of 1 or more types of anthracene derivatives shown by these, and the solvent which can melt | dissolve these. 2. X in the compound represented by the general formula [1] is-
The far ultraviolet light absorbing material according to claim 1, which is O-CO-. 3. X in the compound represented by the general formula [1] is-
The far ultraviolet light absorbing material according to claim 1, which is O—SO ₂ —. 4. In the general formula [I] and the general formula [II],
The far ultraviolet light absorbing material according to claim 1, wherein the one or more phenolic hydroxyl groups are in the p-position and / or the m-position with respect to X. 5. (i) a step of applying the far-ultraviolet light absorbing material according to claim 1 on a semiconductor substrate and then subjecting it to a cross-linking reaction by heating to form a film; After applying a resist material on the ultraviolet light absorbing material film, baking to form a resist material film, and (iii) a step of performing heat treatment after exposing KrF excimer laser light or far ultraviolet light through a mask And a step of developing with (iV) an alkali developing solution. [0001]