JPH08231559A - Phenol compound containing silicon - Google Patents

Abstract

PURPOSE: To obtain the subject new compound, having a small absorption wavelength, capable of shortening the wavelength of an exposure light source, having a satisfactory definition of a resist in an i-line region and useful as a component of a chemical amplified positive type resist material suitable for a microlithographic technique. CONSTITUTION: This phenol compound containing silicon of formula I [(n) is 1 or 2; X is hydroxyl group, a 2-4C lower alkenyl, a 2-4C lower alkoxy, a 6-10C aryloxy or a group of formula II or III (Y is hydroxyl group, a 1-4C lower alkyl, a 2-4C lower alkenyl, etc.) when (n) is 1, and hydroxyl group, a 1-4C lower alkyl, a 6-10C aryl or a group of formula II or III, etc., when (n) is 2], e.g. a compound of formula IV. The compound of formula I is obtained by protecting a phenolic hydroxyl group in the corresponding halogenated phenol compound with a pyran compound, etc., then reacting the halogen site with metallic Mg, providing a Grignard reagent, reacting the resultant Grignard reagent with the corresponding chlorosilane compound, etc., and subsequently carrying out the deprotecting reaction of the pyranyl group under acidic conditions.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel silicon-containing phenol compound suitable as a component of a positive resist material suitable for fine processing technology.

[0002]

2. Description of the Related Art The basic constitution of a photoresist composition is disclosed in Japanese Examined Patent Publication No. 37-1801.
It has been publicly known since it was shown in Japanese Patent Publication No. 5 (1999) -58, and as a photosensitizer used for this photoresist composition, polyhydroxybenzophenone such as 1,2-naphthoquinone-2-di of 2,3,4-trihydroxybenzophenone has been used for a long time. Azidosulfonic acid esters have been used.

However, the conventional hydroxybenzophenone-based photosensitizers are no longer compatible with the increase in resolution of half micron or less and the shortening of the wavelength of the exposure light source, that is, the progress from g-line to i-line. This is because the absorption of carbonyl of benzophenone is i-line wavelength 3
It is speculated that it becomes larger at 65 nm, resulting in a decrease in efficiency.

As described above, tri- or tetrahydroxybenzophenone and further pentahydroxybenzophenone are known as ballast molecules, but the resolution of the resist film is limited in the i-line region, and the mother film having a smaller absorption wavelength is used. At present, the design of nuclear molecules is required.

The present invention has been made in view of the above circumstances.
It is an object of the present invention to provide a novel silicon-containing phenol compound which can cope with a shorter wavelength of an exposure light source and which is suitable as a component of a positive resist material suitable for a fine processing technique.

[0006]

Means and Actions for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the present inventor has found that the phenolic hydroxyl group of the corresponding halogenated phenol compound is protected with a pyran compound and the halogen site is metal magnesium. A Grignard reagent obtained by reacting with
A silicon-containing phenol compound represented by the following general formula (1), which can be synthesized by reacting a corresponding chlorosilane compound or alkoxysilane compound and then deprotecting a pyranyl group under acidic conditions, has an absorption wavelength Is a positive type suitable for microfabrication technology, which can sufficiently cope with the shortening of the wavelength of the exposure light source, that is, the progress from g-line to i-line, and has satisfactory resist resolution in the i-line region. The inventors have found that they can be effectively used as a component of a resist material, and have completed the present invention.

[0007]

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Therefore, the present invention provides a silicon-containing phenol compound represented by the above general formula (1).

The present invention will be described in more detail below. The silicon-containing phenol compound of the present invention is represented by the following general formula (1).

[0010]

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In the above general formula (1), each of the groups listed as X is specifically a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group or an iso-butyl group. , Sec-butyl group, tert-
A lower alkyl group having 1 to 4 carbon atoms such as butyl group, a vinyl group, an allyl group, a lower alkenyl group having 2 to 4 carbon atoms such as homoallyl group, ethoxy group, n-propoxy group, iso
-Lower alkoxy group having 2 to 4 carbon atoms such as propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, etc., phenyl group, tolyl group, tert-butylphenyl group, etc. 6-10
Aryl group, phenoxy group, triloxy group, tert.
Examples include aryloxy groups having 6 to 10 carbon atoms such as -butylphenoxy group and groups having the following structures.

[0012]

[Chemical 4]

Specific examples of Y include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group and ter.
lower alkyl group having 1 to 4 carbon atoms such as t-butyl group, lower alkenyl group having 2 to 4 carbon atoms such as vinyl group, allyl group and homoallyl group, ethoxy group, n-propoxy group, i
a lower alkoxy group having 2 to 4 carbon atoms such as so-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group and tert-butoxy group, carbon such as phenyl group, tolyl group and tert-butylphenyl group Number 6 to 1
0 aryl group, phenoxy group, triloxy group, ter
Examples thereof include aryloxy groups having 6 to 10 carbon atoms such as t-butylphenoxy group and hydroxyl groups.

Specific examples of the compound represented by the general formula (1) include compounds having the following structures.

[0015]

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[0016]

[Chemical 6]

The novel silicon-containing phenol compound represented by the above-mentioned general formula (1) is, for example, a phenolic hydroxyl group of a corresponding halogenated phenol compound is protected with a pyran compound or the like, and a halogen site is reacted with magnesium metal to grignard reagent. As a reaction product, a chlorosilane compound or an alkoxysilane compound corresponding thereto can be reacted, and then the pyranyl group can be deprotected under acidic conditions to easily synthesize the compound (JP-A-2-11).
7682).

That is, the silicon-containing phenol compound of the formula (1) can be produced according to the following reaction formula (A) or reaction formula (B).

[0019]

[Chemical 7]

[0020]

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In this case, the Grignard reagent of the formula (5) can be obtained by reacting with magnesium metal in a nitrogen atmosphere at room temperature or 70 ° C. or lower according to a conventional method. Usually, this Grignard reaction is carried out by dissolving it in a solvent such as anhydrous THF or diethyl ether.
The use of HF is effective because it contributes to the improvement of the solubility of the reaction raw material and the reaction product.

The reaction of the silane of formula (4) or formula (4 ') with the Grignard reagent of formula (5) is carried out at room temperature or 70 ° C.
Perform under the following conditions.

The deprotection reaction of the pyranyl group is carried out with methanol,
A small amount of acid is added in ethanol, THF or a mixed solvent thereof at room temperature or at 50 ° C. or lower.

In this way, a silicon-containing phenol compound free of a pyranyl group can be obtained.

[0025]

INDUSTRIAL APPLICABILITY The novel silicon-containing phenol compound of the present invention has a small absorption wavelength and shortens the wavelength of the exposure light source, that is, g
To be able to sufficiently cope with the progress from the i-line to the i-line, have a satisfactory resist resolution in the i-line region, and be suitably used as a component of a chemically amplified positive resist material suitable for microfabrication technology. You can

[0026]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to the following examples.

Example 1 Magnesium powder 10.94 g (0.45 mol) and anhydrous tetrahydrofuran (THF) 50 ml were charged into a 1 liter four-necked flask equipped with a stirrer, a condenser and a thermometer, and p was charged therein.
-Bromophenylpyranyl ether 76.8 g (0.3
mol) and 300 ml of anhydrous THF under a nitrogen stream,
The solution was added dropwise over about 90 minutes to prepare a Grignard reagent.

Next, 14.3 g (0.0) of methyltrichlorosilane was placed in a 1-liter four-necked flask which had been purged with nitrogen.
96 mol) and 50 ml of anhydrous THF were charged, and the Grignard reagent solution was added thereto at 35 ° C.
The mixture was added dropwise over 0 minutes and then stirred at room temperature for 18 hours.

Next, the above solution was poured into 100 ml of water to terminate the reaction, extracted with ethyl acetate, washed with water, and the solvent was distilled off under reduced pressure to precipitate a part of white crystals. The crystals were filtered off and recrystallized from ethanol to give tris- (p-pyranyloxyphenyl) methylsilane 7.
2 g (yield 13%) was obtained. On the other hand, the viscous filtrate phase was washed with hexane to obtain 23.1 g (yield 58%) of bis- (p-pyranyloxyphenyl) methylsilanol.

Next, 1.5 g (2.61 g) of tris- (p-pyranyloxyphenyl) methylsilane obtained above.
mmol) was dissolved in a mixed solution of 20 ml of ethanol and 10 ml of THF, 0.08 ml of 1% hydrochloric acid was added, and the mixture was stirred at room temperature for 20 hours. Then, the mixture was extracted with ethyl acetate, washed with water, and the solvent was distilled off under reduced pressure.
(P-Hydroxyphenyl) methylsilane 0.77 g
(Yield 91%) was obtained.

Nuclear magnetic resonance spectrum (NMR) of the obtained tris- (p-hydroxyphenyl) methylsilane,
The infrared spectrum (IR) results were as follows.

[0032]

[Chemical 9]

Example 2 8.2 g (19.8 mmol) of bis- (p-pyranyloxyphenyl) methylsilanol obtained from the viscous filtrate phase in the same manner as in Example 1 above.
Was dissolved in 50 ml of ethanol, 0.5 ml of 1% hydrochloric acid was added, and the mixture was stirred at room temperature for 20 hours. Then, after extraction with ethyl acetate and washing with water, the solvent was distilled off under reduced pressure to obtain a viscous substance. This viscous substance was extracted by heating with petroleum ether and the residual solvent was distilled off under reduced pressure from the residual precipitate to obtain 1.22 g (yield 25%) of bis- (p-hydroxyphenyl) methylsilanol. It was

Obtained bis (p-hydroxyphenyl)
Nuclear magnetic resonance spectrum (NMR) of methylsilanol,
The infrared spectrum (IR) results were as follows.

[0035]

[Chemical 10]

Example 3 8.2 g (19.8 mmol) of bis- (p-pyranyloxyphenyl) methylsilanol obtained from the viscous filtrate phase in the same manner as in Example 1 above.
Was dissolved in 50 ml of ethanol, 0.5 ml of 1% hydrochloric acid was added, and the mixture was stirred at room temperature for 20 hours. Then, the mixture was extracted with ethyl acetate, washed with water, and the solvent was distilled off under reduced pressure to obtain a viscous substance. The viscous substance was heated and extracted with petroleum ether, and the solvent was distilled off from the petroleum ether phase under reduced pressure to give 1,1,3,3-tetrakis- (p-hydroxyphenyl) -1,3-dimethyl. Disiloxane 3.05g
(Yield 65%) was obtained. Obtained 1,1,3,3-
Nuclear magnetic resonance spectrum of tetrakis- (p-hydroxyphenyl) -1,3-dimethyldisiloxane (NM
The results of R) and infrared spectrum (IR) are as follows.

[0037]

[Chemical 11]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mitsuo Umemura 1 Hitomi, Oita, Matsuida-cho, Usui-gun, Gunma 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory

Claims (1)

[Claims] 1. A silicon-containing phenol compound represented by the following general formula (1). Embedded image