JPH0782221A - New anthracene derivative - Google Patents

Abstract

PURPOSE:To provide the subject compound applicable as a semiconductor material, medicinal intermediate; dye intermediate or functional material such as optical recording material, esp. useful as a material for antireflection films in the semiconductor industry. CONSTITUTION:The objective compound of formula I [R<1> and R<2> are each H, alkyl, alkoxyl, halogen or OH; R<3>-R<6> are each H, alkyl, alkoxyl, halogen or group of formula II (where, at least one of R<3>-R<6> is of formula II and excepting the compounds where the groups of the formula II have been simultaneously introduced at the 1-, 8-and 9-sites of the anthracene ring)] e.g. 2,6,9-tris(4- hydroxybenzoyloxy)anthracene. The compound of the formula I, e.g. a compound of formula VII belonging thereto, can be obtained by a process wherein a compound of formula IV is formed from a compound of formula III, and a compound of formula V is then reacted with the compound of the formula IV to produce a compound of formula VI which leads to the aimed compound.

Description

Detailed Description of the Invention

INDUSTRIAL APPLICABILITY The present invention relates to a novel anthracene derivative which can be used as a functional material such as a semiconductor material, a pharmaceutical intermediate, a dye intermediate and an optical recording material, and is particularly useful as an antireflection film material in the semiconductor field. .

[0002]

BACKGROUND OF THE INVENTION In recent years, a chemically amplified resist material for deep ultraviolet light (300 nm or less) or KrF excimer laser light (248.4 nm) has been studied for the purpose of application to fine processing. However, when these resist materials are used for highly reflective substrates such as aluminum wiring, the effect of intra-film multiple reflection due to the reflection of exposure light from the semiconductor substrate is strong because the resist materials have high transparency to far-ultraviolet light and the like. receive. When the film thickness of the resist varies due to a step or the like due to the influence of the multiple reflection in the film, the dimension of the resist pattern greatly changes, resulting in a problem such as disconnection. A method of forming an antireflection film on a semiconductor substrate has been studied as one of the methods for suppressing the in-film multiple reflection. However, a suitable compound that can be used as an antireflection film material such as far ultraviolet light or KrF excimer laser light has not been found yet.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned situation, and it is an intra-film structure caused by reflection from a semiconductor substrate which occurs when a resist pattern is formed by using deep-UV lithography such as KrF excimer laser light. An object of the present invention is to provide a novel compound which is extremely useful as a material for an antireflection film formed on the surface of a semiconductor substrate in order to suppress the influence of multiple reflection.

[0004]

To achieve the above object, the present invention comprises the following configurations. [The following general formula [I]

[0005]

[Chemical 3]

[In the formula, 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 are independently hydrogen. Atom, alkyl group, alkoxy group, halogen atom or the following general formula [II]

[0007]

[Chemical 4]

(Wherein R ¹ and R ² 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 [II]). Further, the group represented by the general formula [II] is simultaneously at the 1-position of the anthracene ring, 8
Compounds introduced at positions 9 and 9 are excluded. ). ] The anthracene derivative shown by these. ]

That is, the present inventors use an antireflection film material for the purpose of suppressing the reflection of exposure light from the substrate when forming a resist pattern by using deep-UV lithography such as KrF excimer laser light. As a constituent component of, the compound of absorbing far-ultraviolet light, improving heat resistance of the antireflection film, and imparting a property of preventing the antireflection film from mixing with the resist material at the interface portion, has been earnestly studied. As a result, they have found an anthracene derivative represented by the above general formula [I], and completed the present invention.

The antireflective coating material according to the present invention has a component that absorbs far-ultraviolet light, contributes to the heat resistance of the antireflective coating, and forms an interface with the resist material applied on the antireflective coating. It is a necessary condition to have the property of giving immiscible properties. The present inventors have, as a compound satisfying these conditions, two or more phenolic hydroxyl groups in one molecule capable of undergoing a crosslinking reaction by heating with a resin having a glycidyl group (or an epoxy group), ~ 3
Focusing on a series of compounds having an anthracene skeleton having a strong absorption in the vicinity of 00 nm in the molecule, in order to further facilitate the thermal crosslinking reaction, the p-position of the phenolic hydroxyl group, or m-
The compound of the present invention in which an electron withdrawing group such as a carboxyl group is introduced into the position has arrived.

In the general formula [I], in the case where the group represented by the general formula [II] 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 [I], when one or more phenolic hydroxyl groups are in the p-position and / or m-position with respect to the carboxyl group, a resin having a glycidyl group in the molecule is used. The cross-linking reaction is remarkably accelerated and a preferable antireflection film can be obtained.

The compound of the present invention represented by the general formula [I] can be easily synthesized, for example, by the following method a), b) or c). a) Method-1 In the general formula [I], R ³ is a group represented by the general formula [II], and R ⁴ , R ⁵ and R ⁶ are a hydrogen atom, an alkyl group, a halogen atom or a general formula [ The compound of the present invention, which is the group represented by II], can be easily synthesized, for example, according to the following reaction scheme 1.

[0014]

[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 mixed with p-benzyloxybenzoic acid chloride in an amount of 2 times or more (3 mol in the case of the scheme 1) and the like, and 2 times or more moles thereof (the case of the scheme 1). 3 mol) of base (eg triethylamine, piperidine, NaO
H, KOH, NaH, etc.) in a suitable organic solvent (for example, pyridine, methylene chloride, toluene, ethyl ether, tetrahydrofuran, etc.) in an amount of 1 to 20 times,
When the reaction is carried out at 150 ° C. for 30 minutes to 20 hours with stirring, the target compound having a protected hydroxyl group (protected by a benzyl group in the example of Scheme 1) 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,
The desired compound of the present invention can be easily obtained by carrying out a hydrogenation reaction 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.

B) Method-2 In the general formula [I], R ³ is a hydrogen atom, and R ⁴ or R
^In the case of the compound of the present invention in which ⁶ is a group represented by the general formula [II], R ⁶ or R ⁴ and R ⁵ are a hydrogen atom, an alkyl group or a halogen atom, for example, the compound can be synthesized according to the following reaction scheme 2. Can be done.

[0019]

[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. According to the procedure after the esterification step in the above method a), esterification with p-benzyloxybenzoyl chloride or the like is carried out, and if the protecting group of the hydroxyl group (benzyl group) is removed by hydrogenation reaction, the purpose is The compound of the present invention can be easily obtained.

C) Method-3 In the general formula [I], R ³ is a hydrogen atom, and R ⁴ and R
⁶ is a group represented by the general formula [II], R ⁵ is a hydrogen atom,
The compound of the present invention, which is an alkyl group, a halogen atom or a group represented by the general formula [II], can be easily synthesized, for example, according to the following Reaction Scheme 3.

[0022]

[Formula 3]

That is, first, an anthraquinone derivative having three or more hydroxyl groups, for example, 6-methyl-1,3,8-trihydroxyanthraquinone, is used to alkyletherify the hydroxyl groups according to the operation method 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 the like and then the protective group of the hydroxyl group (benzyl group) is eliminated by catalytic reduction or the like to give the desired compound of the present invention.

Specific examples of the compound of the present invention represented by the general formula [I] include, for example, 2,6,9-tris (4-hydroxybenzoyloxy) anthracene and 2,6,9-tris (3,4-dihydroxy). Benzoyloxy) 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, 1,2-bis (4-hydroxybenzoyloxy) anthracene, 1,
2-bis (4-hydroxy-3-methoxybenzoyloxy)
Anthracene, 1,8-bis (4-hydroxybenzoyloxy) -3-methylanthracene, 6,7-dichloro-1,4-bis (4-hydroxybenzoyloxy) anthracene, 6-methyl-1,3,8- Tris (4-hydroxybenzoyloxy)
Anthracene, 1,4-bis (3,4-dihydroxybenzoyloxy) anthracene, 6-methyl-1,3,8,10-tetra (4-hydroxybenzoyloxy) anthracene, 1,10
-Bis (4-hydroxybenzoyloxy) -2-methoxyanthracene, 2,6-bis (4-hydroxybenzoyloxy) -9-methoxyanthracene, 2,3-dimethyl-1,4,9-
Tris (4-hydroxybenzoyloxy) anthracene, 1,4-bis (3,4-dihydroxybenzoyloxy)-
2,3-Dimethylanthracene, 1,2,5,8-Tetra (4-hydroxybenzoyloxy) anthracene, 5,8-Dichloro-
Examples thereof include 1,4,9-tris (4-hydroxybenzoyloxy) anthracene, but are not limited thereto.

[0025]

[Operation] The compound according to the present invention and a resin having a glycidyl group (epoxy group) in the molecule, for example, glycidyl methacrylate homopolymer or copolymer are dissolved in a suitable solvent, and then spin-coated on a semiconductor substrate. Then, when heated to 150 ° C. or higher, for example, a crosslinking reaction occurs between the glycidyl group of the resin and the compound according to the present invention according to the following formula 4,
It becomes an antireflection film with 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). Four
Accordingly, the antireflection film obtained as a result of the crosslinking reaction of these compounds is insoluble in these solvents.

[0027]

[Formula 4]

Then, for example, a resist material for KrF excimer laser light is spin-coated on the upper layer of the antireflection film,
After the resist film is baked to form a resist film, it is exposed to far ultraviolet light such as KrF excimer laser light or the like, and K which has passed through the resist film due to the anthracene ring contained in the antireflection film is exposed.
Far-ultraviolet light such as rF excimer laser light is absorbed, and reflection from the semiconductor substrate is prevented. As a result, it is possible to completely suppress the influence of in-film multiple reflection, which has been a problem in this field in the past, and no dimensional variation occurs even when a resist pattern is formed on a highly reflective substrate such as aluminum wiring or a stepped substrate.

Further, since the antireflection film formed from the material containing the compound according to the present invention as a constituent component does not dissolve in the resist solvent, it does not mix at the interface with the resist. As a result, the dimensional variation of the resist pattern does not occur.

As a compound similar to the cross-linking agent according to the present invention, a compound having the group represented by the general formula [II] according to the present invention simultaneously introduced into the 1-position, 8-position and 9-position of the anthracene ring, for example, 1,8,9-Tris (4-hydroxybenzoyloxy) anthracene and 1,8,9-Tris (2-hydroxybenzoyloxy) anthracene are known (West German Patent No. 2,257,442), but these compounds In the case of, due to steric hindrance and strong intramolecular hydrogen bond, the crosslinking reaction is difficult to proceed even when heated with a resin having the above-mentioned glycidyl group in the molecule, and therefore the solubility in acetone or the resist solvent is maintained as it is. It 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.

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

[0032]

【Example】

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 of potassium carbonate (1.2 mol)
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 ~ 1
92.6 ° C. ¹ HNMR δppm (CDCl ₃ -DMSO-d ₆ ): 5.10 (2H, s, ArC
H ₂ ), 6.92 (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,
ArC 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 (7. 6,9-tris (4-benzyloxybenzoyloxy) anthracene obtained in (3) above.
(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, O H × 3) IR (KBr tablet) ν cm ^-1 : 3392 (OH), 1699 (COO-).

Example 2 Synthesis of 2,6-bis (4-hydroxybenzoyloxy) anthracene (1) 3,6-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 δppm (DMSO-d ₆ ): 3.97 (6H, s, C H ₃ O × 2), 7.43 (2
H, 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 tablet) 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 Example 1 was added to the 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 (4) above
Was used to perform catalytic reduction and post-treatment in the same manner as in (4) of 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-).

Example 3 Synthesis of 1,5,9-tris (4-hydroxybenzoyloxy) anthracene (1) 1,5-dihydroxyanthraquinone 10 g (41.6 mmol) and stannous chloride 45 g (237 mmol) were added to acetic acid 150 ml. 90 ml of concentrated hydrochloric acid was injected at 16 to 20 ° C., and the mixture was stirred and refluxed for 4 hours. After leaving it at room temperature overnight, it was cooled to 5 ° C., and the precipitated crystals were collected by filtration, washed with water and dried to obtain 8.0 g of 1,5-dihydroxy-9-anthrone 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-dihydroxyanthrone obtained in the above (1) was dissolved in a mixed solution of 45 ml of pyridine and 3.6 g of triethylamine, and the solution of Example 1 was added thereto.
4-benzyloxybenzoic acid chloride obtained in (2)
8 g 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 was washed with water, dried over anhydrous magnesium sulfate, the solvent was distilled off, and the residue was separated by column [filler: Wakogel C-200 (trade name of Wako Pure Chemical Industries, Ltd.); eluent: n-hexane / Methylene chloride = 1/1 → 1/3
] To give 2.0 g of 1,5,9-tris (4-benzyloxybenzoyloxy) anthracene as yellow crystals. mp. 240-242 ℃. ¹ HNMR δ ppm (CDCl ₃ ): 5.00 (2H, s, C H ₂ ), 5.03 (2H, s, C H ₂
), 5.23 (2H, s, C H ₂ ), 6.67〜8.54 (34H, m, aromatic ring hydrogen). IR (KBr tablets) νcm ⁻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 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, benzen 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 tablet) ν cm ^-1 : 3408 (OH), 1702 (COO-).

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 Example 1 -Reaction and post-treatment were carried out in the same manner as in (3) of 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 1.6g
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 tablets) 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 used for catalytic reduction and post-treatment in the same manner as in (4) of Example 1, and 0.92 g of the obtained crude crystal was recrystallized from a tetrahydrofuran / n-hexane mixed solution to give 1,2.
0.5 g of 2,10-tris (4-hydroxybenzoyloxy) anthracene was obtained as pale yellow crystals. ¹ HNMR δ ppm (DMSO-d ₆ ): 6.79 to 7.08 (6 H, m, benzen ring (3-
H, 5-H) × 3), 7.49-8.29 (12H, m, Benzen ring (2-H, 6-H) × 3
And anthracene ring 3H, 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 tablet) ν cm ^-1 : 3413 (OH), 1706 (COO-).

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 δ ppm (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 8Hz, Ar 6-H). IR (KBr tablets) νcm-1: 1676 (COOH).

(2) 4-benzyloxy-3-obtained in the above (1)
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 scaly crystals. mp. 63 ~ 6
5 ° 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 for the reaction and post-treatment in the same manner as in (3) of 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, aromatic ring hydrogen), 8.39 (1H, s, anthracene ring 10-H). IR (KBr tablets) ν cm ^-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 procedure of (4) of Example 1 was repeated. 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 to 8.39 (15H, m, aromatic ring hydrogen), 8.78 (1H, s, anthracene ring 10-H), 10.33 (3H, bs, O H ×
3). IR (KBr tablets) ν cm ⁻¹ : 3374 (OH), 1728 (COO-).

Example 6 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 250 ml of ethanol. 270ml of 5N aqueous sodium hydroxide solution and benzyl chloride 102g (0.81mol)
Was injected and the mixture was stirred and refluxed for 6 hours. After the reaction, the mixture was cooled to room temperature, left overnight, poured with 40 ml of concentrated hydrochloric acid, 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. 1
84-186 ℃. ¹ HNMR δ ppm (DMSO-d ₆ ): 3.38 (1H, bs, -O
H ), 5.18 (2H, s, ArC H _2- ), 5.22 (2H, s, ArC H _2- ), 7.16 (1H,
d, J = 8.8 Hz, benzene ring 5-H), 7.30 to 7.57 (12 H, m, aromatic 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) 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 crystal obtained was recrystallized from a mixed solution of methylene chloride / ethyl acetate (1/4 [V / V]) to give 2,6,9- 3.4 g of tris (3,4-dibenzyloxybenzoyloxy) anthracene 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 to 8.05 (44H, m, aromatic ring hydrogen), 8.21 (1H, d, J = 9.2Hz, 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 Example 1, and 1.8 g of the obtained crude crystal was mixed with tetrahydrofuran / n-hexane (5/7 [V / V]). The crystals were recrystallized from 1.2 g of 2,6,9-tris (3,4-dihydroxybenzoyloxy) anthracene as pale yellow crystals.
mp. 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 1
0-H), 9.77 (6H , bs, O H × 6). IR (KBr tablets) ν cm ^-1 : 3365 (OH), 1701 (COO-).

Example 7 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 worked up in the same manner as in (1) of Example 1 to give 2-benzyloxy-3-chlorobenzoic acid (20.4 g) as white crystals. Obtained. mp. 211-213 ° C. ¹ HNM R δppm (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 (1) above
The reaction and post-treatment were carried out in the same manner as in (2) of 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 Example 1 using 0.4 g (1.7 mmol) of -dihydroxy-10-anthrone, and 1.1 g of the obtained crude crystal 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 → 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,
Aromatic ring hydrogen), 8.49 (1H, s, anthracene ring 9-H). IR (KBr tablet) ν cm ⁻¹ : 1743 (COO-).

(4) Same as (4) of Example 1 using 280 mg (0.4 mmol) of 1,2,10-tris (4-benzyloxy-3-chlorobenzoyloxy) anthracene obtained in the above (3). 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 (15 H, m, aromatic ring hydrogen), 8.52 (1 H, s, anthracene ring 9-H), 10.41 (3 H, bs, -OH). IR (KBr tablets) ν cm ⁻¹ : 3382 (OH), 1747 (COO-).

Example 8 Synthesis of 1,2,10-tris (3-hydroxy-4-methylbenzoyloxy) anthracene (1) 20.3 g (0.13 mol) of 3-hydroxy-4-methylbenzoic acid and 50.8 g of benzyl chloride (0.40 mol) was used for the reaction and post-treatment in the same manner as in (1) of Example 1, and the obtained crude crystals were recrystallized from ethanol to give 3-benzyloxy-4-.
15.0 g of methylbenzoic acid was obtained as white crystals. mp. 159
~ 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, benzen 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 tablet) 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 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 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 ~ 1
35 ° 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, ArCH 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 tablets) ν cm ^-1 : 1737 (COO-).

(4) Same as (4) of Example 1 using 150 mg (0.17 mmol) of 1,2,10-tris (3-benzyloxy-4-methylbenzoyloxy) anthracene obtained in (3) above. After reduction and post-treatment, 1,2,10-tris (3-hydroxy-4-methylbenzoyloxy) anthracene 8
0 mg 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, CH 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, O H × 3). IR (KBr tablets) ν cm ^-1 : 3409 (OH), 1716 (COO-).

Reference Example 1 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. 240 ml of toluene
, 2,2'-azobis (methyl 2-methylpropionate) (0.8 g) was added, 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. The resulting copolymer had a composition ratio of methyl methacrylate units and glycidyl methacrylate units of ¹ HNM.
It was about 5: 2 from the R measurement. In addition, the weight average molecular weight (Mw) of the copolymer was determined by GPC measurement using polystyrene as the standard.
Was about 35,800 and the number average molecular weight (Mn) was about 19,200.

(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.

Reference Example 2 An antireflection film material having the following composition was prepared. Poly (methyl methacrylate / glycidyl methacrylate / 2,3-dihydroxypropyl methacrylate) (resin of Reference Example 1) 4.0 g 2,6,9-tris (4-hydroxybenzoyloxy) anthracene (Compound of 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.

Reference Example 3 A chemically amplified positive resist material having the following composition was prepared. Poly [p- (ethoxyethoxy) styrene / p-hydroxystyrene] 2.50 g 2-Cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane 0.13 g Propylene glycol monomethyl ether acetate 7.37 g In Reference Example 2 above as an antireflection film material. Using the composition described above, a resist material having the above composition was used as a chemically amplified positive resist material to form a pattern on a highly reflective substrate having steps. The results will be described with reference to FIG. An antireflection coating material 2 having the composition described in Reference Example 2 was spin-coated on a highly reflective aluminum step substrate 1 obtained by performing photolithography, etching, and aluminum sputtering on a silicon substrate, and the temperature was 200 ° C. for 90 seconds. Baking on a hot plate gave a 100 nm antireflective coating (Fig. 2a). Then, a chemically amplified positive resist material 3 having the above composition is spin-coated on the antireflection film, and the temperature is kept at 90 ° C.
Prebaking was performed on a hot plate for a second to obtain a resist material film having a thickness of 1.0 μm (FIG. 2b). Next, 248.4 nm KrF
The excimer laser light 4 of 1. was selectively exposed through the mask 5 (FIG. 2c). Then, after post-baking on a hot plate at 100 ° 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. Was obtained (Fig. 2d). 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 this, pattern 3
The far-ultraviolet light absorbing material film 2 according to the present invention and the aluminum substrate 1 were sequentially etched with oxygen gas and chlorine-based gas using a as a mask (FIG. 2e). The formed etching pattern 1a was a good pattern without any dimensional variation with the resist pattern 3a.

Reference Examples 4 to 10 Antireflection film materials having the compositions shown in Tables 1 and 2 below were prepared.

[0067]

[Table 1]

[0068]

[Table 2]

Using the antireflection film materials having the compositions shown in Tables 1 and 2 above, an antireflection film was formed on a high-reflectance aluminum step substrate in the same manner as in Reference Example 3, respectively. Pattern formation was performed on the film in the same manner as in Reference Example 3 using the chemically amplified positive resist material having the composition described in Reference Example 3. The results are shown in Table 3 below.

[0070]

[Table 3]

None of the material films of Reference Examples 4 to 10 eluted at all in acetone, and it was confirmed that the crosslinking reaction proceeded.

Reference Example 11 A film material having the following composition was prepared. Poly (methyl methacrylate / glycidyl methacrylate / 2,3-dihydroxypropyl methacrylate) [Resin of Reference Example 1] 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.

[0073]

As is clear from the above description, the film material containing the compound of the present invention is used as the undercoating material for the resist material for exposure to far-ultraviolet light (300 nm or less) or KrF excimer laser light (248.4 nm). As a result, when used for a highly reflective substrate such as aluminum, aluminum-silicon or polysilicon, or a stepped substrate, notching or halation that causes problems such as disconnection in these substrates while maintaining high resolution performance and high sensitivity is performed. A good pattern shape of quarter micron can be obtained without generating. Therefore, the present invention has great value for the formation of ultrafine patterns in the semiconductor industry and the like.

[0074]

[Brief description of drawings]

FIG. 1 shows an ultraviolet spectrum curve diagram of an antireflection film obtained in Reference Example 2.

FIG. 2 is a process cross-sectional view of a pattern forming method when an antireflection film material using the anthracene derivative of the present invention is used as an undercoating agent.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Highly reflective substrate, 2 ... Antireflection film material, 3 ... Chemically amplified positive resist material, 4 ... KrF excimer laser light, 5 ... Mask, 3a ... Resist pattern, 1a ...
Etching pattern.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area H01L 21/027

Claims (4)

[Claims] 1. The following general formula [I]: [Wherein R ¹ and R ² each independently represent 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 each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or the following general formula [I
I] [Chemical 2] (In the formula, R ¹ and R ² 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 [II]. Compounds in which the group represented by the general formula [II] is simultaneously introduced into the 1-position, 8-position and 9-position of the anthracene ring are excluded. ] The anthracene derivative shown by these. 2. R ^{3 of the} compound represented by the general formula [I]
The anthracene derivative according to claim 1, wherein one of R ⁶ is a group represented by the general formula [II]. 3. R ^{3 of the} compound represented by the general formula [I]
The anthracene derivative according to claim 1, wherein two of R ⁶ are groups represented by the general formula [II]. 4. In the general formula [I] and the general formula [II],
One or more phenolic hydroxyl groups to carboxyl group
The anthracene derivative according to claim 1, which is in the p-position and / or the m-position. [0001]