JPH06130663A - Amorphous radiation-sensitive compound and radiation-sensitive resin composition using the same - Google Patents

Abstract

PURPOSE:To decrease the number of undissolved particles just after production or after stored for a long time and to increase the production yield of ICs by using a radiation-sensitive compd. having an amorphous halo form containing at least one max. in a specified range. CONSTITUTION:This radiation-sensitive compd. shows an amorphous halo form including at least one max. in 5 deg. to 35 deg. 2theta range in powder X-ray diffraction using Cu-Kalpha ray as the X-ray source. For example, 1,2-benzoquinone diazide-4- sulfonate, 1,2-naphthoquinone diazide-4-sulfonate, etc., is used. These quinonediazide sulfonate is obtd., for example, by the reaction of compd. having hydroxyl groups and quinonediazide sulfonic acid halide such as 1,2-benzoquinone diazide-4-sulfonic acid chloride in a hydrophilic org. solvent such as dioxane, acetone, and tetrahydrofuran in the presence of org. base such as triethylamine.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a radiation-sensitive compound which is sensitive to radiation such as ultraviolet rays, X-rays, electron beams, molecular beams, γ-rays, synchrotron radiation and proton beams, and radiation-sensitive compounds using the same. Resin composition.

[0002]

2. Description of the Related Art With the high integration of LSIs, the design rules of integrated circuits are becoming finer from around 1 μm to around 0.5 μm. The radiation-sensitive resin composition used for such fine processing is required to have good storage stability in addition to basic performance such as resolution, sensitivity, profile, coating property and depth of focus. That is, when there are many relatively large undissolved particles that cannot be visually observed in the radiation-sensitive resin composition, when the substrate is etched through the resist pattern formed from the composition, the substrate is often covered with the resist pattern. It is known that pinholes are generated in the substrate portion and the yield at the time of manufacturing an integrated circuit is deteriorated. The above-mentioned non-dissolved particles are mainly derived from the radiation-sensitive compound, and the number of non-dissolved particles in the radiation-sensitive resin composition is not so problematic immediately after the preparation of the composition,
It increases gradually and becomes abnormal level after long-term storage.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a radiation-sensitive compound having a small number of non-dissolved particles in a radiation-sensitive resin composition, and a small number of non-dissolved particles immediately after production and after long-term storage, which is an integrated circuit. Provided is a radiation-sensitive resin composition having a good yield during production.

[0004]

According to the present invention, in powder X-ray diffraction using Cu Kα ray as an X-ray source, the 2θ value is 5 ° to 5 °.
An amorphous radiation-sensitive compound characterized by having an amorphous halo diagram containing at least one maximum in the range of 35 °, and the amorphous radiation-sensitive compound, an alkali-soluble resin and a solvent. It is a radiation-sensitive resin composition formed by mixing.

Examples of the amorphous radiation-sensitive compound include 1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester and 1,2-naphthoquinonediazide-ester. Examples thereof include 5-sulfonic acid ester. These quinonediazide sulfonic acid esters include, for example, a compound having a hydroxyl group, 1,2-benzoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-4-sulfonic acid chloride or 1,2-naphthoquinonediazide-5. -A quinonediazide sulfonic acid halide such as sulfonic acid chloride can be obtained by reacting with a hydrophilic organic solvent such as dioxane, acetone, tetrahydrofuran, dimethylformamide or dimethylsulfoxide in the presence of an organic base such as triethylamine. The reaction temperature is preferably around room temperature or higher, and it is preferable to complete the reaction in a short time.
Immediately after the completion of the reaction, it is preferable to remove the salt of hydrogen halide such as hydrochloric acid and the organic base and the unreacted organic base from the reaction mixture. Examples of the removing means include a method of filtering a salt of hydrogen halide and an organic base in the reaction mixture, and then neutralizing the obtained filtrate with an aqueous organic acid solution such as acetic acid. Preferred amorphous radiation-sensitive compounds include those in which the amorphous halo figure contains two local maxima, more preferably one of the two local maxima is 2θ.
The value is in the range of 12 ° to 18 °.

As the compound having a hydroxyl group,
For example, hydroquinone, resorcin, phloroglucin,
2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2 ', 3-trihydroxybenzophenone, 2,2', 4-trihydroxybenzophenone, 2,2 ', 5-trihydroxybenzophenone, 2,3,3'-trihydroxybenzophenone, 2,3,4'-trihydroxybenzophenone,
2,3 ', 4-trihydroxybenzophenone, 2,
3 ', 5-trihydroxybenzophenone, 2,4
4'-trihydroxybenzophenone, 2,4 ', 5-
Trihydroxybenzophenones such as trihydroxybenzophenone, 2 ', 3,4-trihydroxybenzophenone, 3,3', 4-trihydroxybenzophenone or 3,4,4'-trihydroxybenzophenone, 2,3,3 ', 4-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2', 3,4-tetrahydroxybenzophenone, 2,2 ' , 3,4'-Tetrahydroxybenzophenone, 2,2 ', 5,5'-Tetrahydroxybenzophenone, 2,3', 4 ', 5-Tetrahydroxybenzophenone or 2,3', 5,5'-Tetrahydroxy Tetrahydroxybenzophenones such as benzophenone, 2,2 ', 3,4,4'-pentahydro Shi benzophenone, 2,2 ', 3,4,5'- pentahydroxybenzophenone, 2,2', 3,3 ', 4-pentahydroxybenzophenone or 2,3,3', 4,
Pentahydroxybenzophenones such as 5′-pentahydroxybenzophenone, 2,3,3 ′, 4,4 ′,
5'-hexahydroxybenzophenone or 2,
Hexahydroxybenzophenones such as 2 ', 3,3', 4,5'-hexahydroxybenzophenone, alkyl esters of gallic acid, oxyflavans described by the general formula (I) in JP-A-2-84650, JP-A-2-
No. 269351, the phenol compound described by the general formula (I), JP-A-3-185447, the phenol compound described by the general formula (I), and Japanese Patent Application No. 4-134862.
And the compounds described in Formula (IV).

As the alkali-soluble resin, for example, polyhydroxystyrene or its derivative, styrene-maleic anhydride copolymer, polyvinyl hydroxybenzoate, methacrylic resin containing a carboxyl group,
Alternatively, novolac resin or the like may be used.

Examples of novolak resins include phenol, o-, m- or p-cresol, 2,5-xylenol, 3,5-xylenol or 3,4-xylenol, 2,3,5-trimethylphenol, 4- t
-Butylphenol, 2-t-butylphenol or 3-t-butylphenol, 3-ethylphenol,
2-ethylphenol or 4-ethylphenol,
A phenol such as 3-methyl-6-t-butylphenol or 4-methyl-2-t-butylphenol, 1,3-dihydroxynaphthalene, 1,7-dihydroxynaphthalene or 1,5-dihydroxynaphthalene, or 2-naphthol is used. Alone or in combination of two or more,
A resin condensed with an aldehyde by a conventional method can be used.

Examples of aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, p-hydroxybenzaldehyde, m-hydroxybenzaldehyde. , Glutaraldehyde, glyoxal, o-methylbenzaldehyde, p-methylbenzaldehyde and the like.

The ratio of the alkali-soluble resin to the amorphous radiation-sensitive compound is usually 5 to 100 parts by weight of the amorphous radiation-sensitive compound, preferably 10 parts by weight, relative to 100 parts by weight of the alkali-soluble resin. ~ 50 parts by weight.

Examples of the solvent include glycol ether esters such as ethyl cellosolve acetate or propylene glycol monomethyl ether acetate, the solvents described in JP-A-2-220056, amyl acetate,
Examples thereof include ethyl lactate, methyl pyruvate, methyl 2-methoxypropionate, 2-heptanone and γ-butyrolactone. These solvents may be used alone or in combination of two or more. The amount of solvent is usually adjusted to 50 to 97% by weight in the radiation sensitive resin composition.

If desired, the radiation-sensitive resin composition of the present invention may contain various additives commonly used in the art.

[0013]

The radiation-sensitive resin composition of the present invention has a small number of non-dissolved particles immediately after production and after long-term storage, and the use of the radiation-sensitive resin composition improves the yield in the production of integrated circuits. You can

[0014]

The present invention will be described in more detail with reference to examples. In the text, "part" means "part by weight" unless otherwise specified.

Example 1 12.31 g of 2,3,4,4'-tetrahydroxybenzophenone, 33.6 g of 1,2-naphthoquinonediazide sulfonic acid chloride and 280 g of dioxane were placed in a 500 ml four-necked flask.
Was charged and stirred at 20 to 30 ° C. for about 1 hour. Next, 13.3 g of triethylamine was added dropwise at 15 to 25 ° C. over about 1 hour, and after completion of the addition, the mixture was stirred at the same temperature for 1 hour. Immediately after completion of the reaction, the reaction mixture was filtered. Filter residue is dioxane
Washed with 34 g. The filtrate and the washing solution were combined, poured into a mixed solution of 930 g of pure water and 9.3 g of acetic acid at 30 ° C, and stirred at 28 to 32 ° C for 1 hour for crystallization. After filtration, the obtained crystals were thoroughly washed with pure water and then dried at 40 ° C. to obtain about 40 g of an amorphous radiation sensitive compound.

Example 2 172 parts of the amorphous radiation-sensitive compound obtained in Example 1,
Cresol novolac resin [m-cresol / p-cresol = 5/5, cresol / formalin = 1 / 0.75
Resin having a polystyrene-equivalent weight average molecular weight of 8000, condensed in the presence of an oxalic acid catalyst under the conditions of (both are molar ratios)] 800
And 2652 parts of ethyl cellosolve acetate were stirred and mixed under light-shielding conditions. Then, the mixture was filtered through a Teflon filter having a pore size of 0.1 μm and filled in a clean gallon bottle to obtain a radiation-sensitive resin composition. The number of non-dissolved particles in the composition immediately after production was measured by using an automatic particle counter (KL-20 type) manufactured by Rion Co., Ltd., and the following results were obtained. Number of particles of 0.25 μm or more 35 / ml Number of particles of 0.25 to 0.3 μm 18 / ml After storing the above composition in a clean room at 22 to 24 ° C for 1 month, measure the number of non-dissolved particles and obtain the following results. Obtained. The number of particles of 0.25 μm or more 47 particles / ml The number of particles of 0.25 to 0.3 μm 24 particles / ml As described above, the radiation-sensitive resin composition obtained in this example has a small number of non-dissolved particles. , 1 at 22-24 ℃
Even if an integrated circuit is manufactured after storage for a month, the yield is good.

[Brief description of drawings]

1 is an X-ray diffraction diagram of the amorphous radiation-sensitive compound obtained in Example 1. FIG.

Front page continuation (72) Inventor Sannori Kato 3-98 Kasugade, Konohana-ku, Osaka Sumitomo Chemical Co., Ltd.

Claims (4)

[Claims] 1. A powder X-ray diffraction using Cu Kα ray as an X-ray source, which has an amorphous halo pattern including at least one local maximum in a 2θ value range of 5 ° to 35 °. Amorphous radiation sensitive compound. 2. The radiation-sensitive compound according to claim 1, wherein the amorphous halo diagram includes two local maxima. 3. One of the two maxima is a 2θ value of 12 ° to 18 °.
The radiation-sensitive compound according to claim 2, which is within the range. 4. A radiation-sensitive resin composition obtained by mixing the radiation-sensitive compound according to claim 1, an alkali-soluble resin and a solvent.