JP3063177B2 - Radiation-sensitive resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation-sensitive resin composition containing an alkali-soluble resin, and more particularly to a radiation-sensitive resin composition suitable as a resist for producing highly integrated circuits.

[0002]

2. Description of the Related Art Positive resists are widely used in the manufacture of integrated circuits because they provide high-resolution resist patterns. However, with the recent increase in the degree of integration of integrated circuits, resists with higher resolution have been developed. A positive resist capable of forming a pattern is desired. That is, when a fine resist pattern is formed using a positive resist, when a latent image formed by exposure is developed with a developing solution composed of an alkaline aqueous solution, the exposed portion contacts the wafer (the bottom of the pattern). It needs to be developed quickly.

[0003]

However, in the case of the conventional positive type resist, when the distance between the resist patterns to be formed is 0.8 μm or less, development residue called scum tends to occur, and there is a problem in developability. .

Further, as the degree of integration of integrated circuits has been improved, the method of etching a wafer has shifted from conventional wet etching with large side etching to dry etching with small side etching. In this dry etching, it is necessary that the resist pattern does not change during the etching, so that good heat resistance is desired.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method which can effectively suppress the occurrence of scum and have excellent developability.
It is an object of the present invention to provide a radiation-sensitive resin composition which is suitable as a positive resist having high sensitivity and excellent in heat resistance, residual film ratio and the like.

That is, the present invention achieves the above object by providing (A) an alkali-soluble resin, and (B) a general formula (1):

Embedded image [Wherein, D represents a hydrogen atom or a 1,2-quinonediazide group-containing organic group, and R ¹ and R ² represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a carbon atom having 6 carbon atoms.
R ³ represents an OD group (where D is the same as described above) or the same group as R ¹ , X represents a hydrogen atom, an OD group (where D is the same as described above), or

Embedded image (Where D is the same as above, R ⁴ represents the same group as R ¹ , f represents an integer of 0 to 3 and g represents an integer of 0 to 2), and a and b represent 1 Represents an integer of ~ 3, c and d
And e show the integer of 0-2. (Hereinafter referred to as "compound (B)").

Alkali-soluble resin The alkali-soluble resin of the composition of the present invention (hereinafter referred to as “resin
Examples of (A) ") include novolak resins, resole resins, polyvinylphenol or derivatives thereof, styrene-maleic anhydride copolymers, polyvinylhydroxybenzoates, carboxylic acid-containing methacrylic resins, and the like. These can be used alone or in combination of two or more.

Of these, novolak resins are preferable, and among the novolak resins, the following general formula (2):

Embedded image (Wherein, n represents an integer of 1 to 3) is particularly preferably obtained by polycondensing a phenol and an aldehyde represented by the following formula:

Preferred phenols to be polycondensed are, for example, o-cresol, m-cresol and p-cresol.
Cresol, 2,3-xylenol, 2,4-xylenol, 2,
5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,4-trimethylphenol,
2,3,5-trimethylphenol and 3,4,5-trimethylphenol. Among them, particularly preferred are o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol and 2,3,5-trimethylphenol. These phenols are used alone or in combination of two or more.

Preferred aldehydes to be polycondensed with these phenols include, for example, formaldehyde, trioxane, paraformaldehyde, benzaldehyde, acetaldehyde, propylaldehyde, phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-
Chlorobenzaldehyde, o- nitrobenzaldehyde, m- nitrobenzaldehyde, p- nitrobenzaldehyde, o- methylbenzaldehyde, m- methylbenzaldehyde, p- methylbenzamide aldehyde arsenide de, p -n
-Butylbenzaldehyde, furfural and the like. Among them, particularly preferred is formaldehyde. These aldehydes can be used alone or in combination of two or more.

The use amount of these aldehydes is preferably 0.7 to 3 mol, more preferably 0.8 to 1.5 mol, per 1 mol of the phenol.

For the polycondensation of phenols and aldehydes, an acidic catalyst is usually used. Examples of the acidic catalyst include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, and organic acids such as formic acid, oxalic acid, and acetic acid. The use amount of these acidic catalysts is usually based on 1 mole of phenols.
1 × 10 ^{-5 to} 5 × 10 ^-1 mol, preferably 1 × 10 ^-4 to 1 × 10
^-1 mole.

In the polycondensation, water is usually used as a reaction medium. However, when the phenol used in the polycondensation does not dissolve in the aqueous solution of the aldehyde and becomes a heterogeneous system from the beginning of the reaction, it is used as the reaction medium. A hydrophilic solvent can be used in combination. Examples of these hydrophilic solvents include alcohols such as methanol, ethanol, propanol and butanol, and cyclic ethers such as tetrahydrofuran and dioxane. The amount of the reaction medium to be used is generally 20 to 1000 parts by weight, preferably 20 to 600 parts by weight, per 100 parts by weight of the total of phenols and aldehydes as the reaction raw materials.

The temperature of the polycondensation can be appropriately adjusted according to the reactivity of the reaction raw materials.
Preferably it is 70-130 ° C.

The polycondensation method includes, for example, a method in which phenols, aldehydes, acidic catalysts, etc. are charged all at once to a reaction vessel, and a method in which phenols, aldehydes, etc. are reacted with phenols, aldehydes, etc. in the presence of an acidic catalyst as the reaction proceeds. Can be adopted.

After the completion of the polycondensation, the temperature of the reaction system is generally increased to 130 to 230 ° C. to remove unreacted raw materials, acidic catalyst, reaction medium and the like present in the reaction system. For example, the volatile component is distilled off at about 20 to 50 mmHg, and the obtained resin (A) is recovered.

The weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) of the resin (A) used in the present invention is as follows:
Preferably 2,000 to 20,000, 3,000 to 15,000
Is more preferable. When Mw exceeds 20,000, it may be difficult to uniformly apply the composition of the present invention to a wafer, and furthermore, there is a tendency for developability and sensitivity to decrease. When Mw is less than 2,000, the heat resistance tends to decrease.

In order to obtain the resin (A) in which the content of the low molecular weight resin component is reduced, the resin (A) obtained above is used.
Is dissolved in a good solvent such as ethyl cellosolve acetate, dioxane, methanol and ethyl acetate, and then water, n-
A poor solvent such as hexane or n-heptane may be mixed, and then the separated resin solution layer may be separated, and the resulting resin (A) may be recovered.

Compound (B) The composition of the present invention contains at least one compound (B) represented by the general formula (1).

In the general formula (1), R ¹ , R ² and R ⁴ are each a methyl, ethyl, n-propyl, isopropyl, n-butyl or t-butyl group having 1 to ⁴ carbon atoms. An alkyl group, a methoxy group having 1 to 4 carbon atoms, an ethoxy group,
It represents an alkoxy group such as a propoxy group or a butoxy group, or an aryl group such as a phenyl group having 6 to 8 carbon atoms, a tolyl group, or a xylyl group. R ³ is an OD group (where D represents a hydrogen atom or an organic group containing a 1,2-quinonediazide group), and has 1 carbon atom
Alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group having 4 to 4 carbon atoms, methoxy group, ethoxy group, propoxy group, butoxy group, etc. Represents an aryl group such as an alkoxy group or a phenyl group having 6 to 8 carbon atoms, a tolyl group, a xylyl group,

Among these compounds (B), compounds represented by the following general formulas (3) and (4) are preferred.

General formula (3):

Embedded image [Wherein, a plurality of D may be the same or different and represent a hydrogen atom or a 1,2-quinonediazide group-containing organic group, a and b each represent an integer of 1 to 3, and h represents an integer of 0 to 3. Show. ]

General formula (4):

Embedded image [Wherein, a plurality of D may be the same or different and each represents a hydrogen atom or a 1,2-quinonediazide group-containing organic group, a and b each represent an integer of 1 to 3, and f represents an integer of 0 to 2. Show. ]

The compound (B) is a compound represented by the formula (1):
Is a hydrogen atom (that is, OD is a hydroxyl group) (hereinafter, referred to as “polyhydroxy compound (B ₁ )”), or at least a part of D 1 in the general formula (1) is 1,
Quinonediazide compound is a 2-quinonediazide group-containing organic group (hereinafter, "quinonediazide compound (B _2)" hereinafter) is, they may be used in combination.

Examples of the polyhydroxy compound (B ₁ ) include 1,4-bis (4-hydroxyphenoxy) benzene,
4-bis (3-hydroxyphenoxy) benzene, 1,3-bis (4-hydroxyphenoxy) benzene, 1,4-bis (3-methyl-4-hydroxyphenoxy) benzene, 1,4-bis (2-methyl -3-hydroxyphenoxy) benzene, 1,3-
Bis (3-methyl-4-hydroxyphenoxy) benzene,
1,3-bis (2-methyl-3-hydroxyphenoxy) benzene, 2,5-bis (4-hydroxyphenoxy) phenol,
2,5-bis (3-hydroxyphenoxy) phenol, 2,5-
Bis (3-methyl-4-hydroxyphenoxy) phenol, 2,5-bis (2-methyl-3-hydroxyphenoxy) phenol, 1,3-bis (3,4-dihydroxyphenoxy) benzene, 1,4-bis (3,5-dihydroxyphenoxy) benzene, 2,5-bis (3,5-dihydroxyphenoxy) phenol, 1,4-bis (3,4-dihydroxyphenoxy) benzene, 2,5-bis (3,4- Dihydroxyphenoxy) phenol, 1,4-bis (2,3-dihydroxyphenoxy) benzene, 2,5-bis (2,3-dihydroxyphenoxy) phenol, 1- (4-hydroxyphenoxy) -4- (3,5 -Dihydroxyphenoxy) benzene, 2- (4-hydroxyphenoxy) -5- (3,5-dihydroxyphenoxy) phenol, 2-
(3,5-dihydroxyphenoxy) -5- (4-hydroxyphenoxy) phenol, 1- (3-hydroxyphenoxy) -4-
(3,5-dihydroxyphenoxy) benzene, 2- (3-hydroxyphenoxy) -5- (3,5-dihydroxyphenoxy)
Phenol, 2- (3,5-dihydroxyphenoxy) -5- (3-
(Hydroxyphenoxy) phenol, 1- (4-hydroxyphenoxy) -4- (3,4-dihydroxyphenoxy) benzene, 2- (4-hydroxyphenoxy) -5- (3,4-dihydroxyphenoxy) phenol, 2- ( 3,4-dihydroxyphenoxy) -5- (4-hydroxyphenoxy) phenol, 1-
(4-hydroxyphenoxy) -4- (3-hydroxyphenoxy) benzene, 2- (4-hydroxyphenoxy) -5- (3-hydroxyphenoxy) phenol, 2- (3-hydroxyphenoxy) -5- (4- Hydroxyphenoxy) phenol,
1,3,5-tris (4-hydroxyphenoxy) benzene, 1,
3,5-tris (3-hydroxyphenoxy) benzene, 1,3,
5-tris (3,5-dihydroxyphenoxy) benzene, 1,
3,5-tris (3,4-dihydroxyphenoxy) benzene,
1,3,5-tris (2,3-dihydroxyphenoxy) benzene, 1,3,5-tris (3-methyl-4-hydroxyphenoxy) benzene, 1,3,5-tris (2-methyl-3- Hydroxyphenoxy) benzene, 1,3-bis (4-hydroxyphenoxy) -5- (3,5-dihydroxyphenoxy) benzene,
3-bis (3,5-dihydroxyphenoxy) -5- (4-hydroxyphenoxy) benzene, 1,3-bis (4-hydroxyphenoxy) -5- (3,4-dihydroxyphenoxy) benzene,
1,3-bis (3,4-dihydroxyphenoxy) -5- (4-hydroxyphenoxy) benzene, 1,3-bis (3-hydroxyphenoxy) -5- (3,5-dihydroxyphenoxy) benzene, 3-bis (3,5-dihydroxyphenoxy) -5- (3-hydroxyphenoxy) benzene, 1,3-bis (3-hydroxyphenoxy) -5- (3,4-dihydroxyphenoxy) benzene, 1,3- Bis (3,4-dihydroxyphenoxy) -5- (3-
Hydroxyphenoxy) benzene, 1,3-bis (4-hydroxyphenoxy) -5-phenoxybenzene, 1,4-bis (3-
Methoxy-4-hydroxyphenoxy) benzene, 1, 3,5
Tris (3-methoxy-4-hydroxyphenoxy) benzene and the like. These can be used alone or in combination of two or more.

Of these, preferred are 1,4-bis
(4-hydroxyphenoxy) benzene, 1,3-bis (4-hydroxyphenoxy) benzene, 2,5-bis (4-hydroxyphenoxy) phenol, 1,3-bis (3,4-dihydroxyphenoxy) benzene, 1 , 4-bis (3,5-dihydroxyphenoxy) benzene, 1,3,5-tris (4-hydroxyphenoxy) benzene and the like.

The above polyhydroxy compound (B ₁ ) is synthesized by various methods. For example, Ann. (1906), 350
Volume, p. 83, the condensation reaction of an alkoxy-substituted phenol and an aromatic bromide is carried out by utilizing the Ullmann reaction, and the alkoxyl group of the obtained alkoxy-substituted aromatic ether compound is converted to a hydroxyl group. It can be obtained by conversion.

The quinonediazide compound (B ₂ ) is a compound in which at least a part of D in the general formula (1) is a 1,2-quinonediazide group-containing organic group as described above. That is, it is a compound in which some or all of the hydrogen atoms of the hydroxyl groups in the above-mentioned polyhydroxy compound (B ₁ ) are substituted with the above-mentioned 1,2-quinonediazide group-containing organic group.

Examples of the above 1,2-quinonediazide group-containing organic group include 1,2-benzoquinonediazide-4-sulfonyl group, 1,2-naphthoquinonediazide-5-sulfonyl group,
2-naphthoquinonediazide-4-sulfonyl group, 2,1-naphthoquinonediazide-5-sulfonyl group, 2,1-naphthoquinonediazide-4-sulfonyl group and the like. Among them, preferred are a 1,2-naphthoquinonediazide-5-sulfonyl group and a 1,2-naphthoquinonediazide-4-sulfonyl group.

The quinonediazide compound (B ₂ ) is, for example,
It can be obtained by an esterification reaction between the above-mentioned polyhydroxy compound (B ₁ ) and 1,2-naphthoquinonediazide-4-sulfonyl chloride or 1,2-naphthoquinonediazide-5-sulfonyl chloride.

These can be used alone or in combination of two or more. Also, polyhydroxy compounds
(B ₁ ) and the quinonediazide compound (B ₂ ) can be used in combination.

The content of the compound (B) in the composition of the present invention is usually 0.5 to 90 parts by weight, preferably 2 to 50 parts by weight, per 100 parts by weight of the resin (A).

[0033] The compositions of other 1,2-quinonediazide compound present invention, resin (A), the and the other compound (B), quinonediazide compounds mentioned above (B ₂₎ other than the 1,2-quinonediazide compound ( Hereinafter, "quinonediazide compound
(D) "). Compound (B)
When only the polyhydroxy compound (B ₁ ) is used, the quinonediazide compound (D) is an essential component. Such quinonediazide compounds (D) include, for example, 1,
2-benzoquinonediazide-4-sulfonic acid ester, 1,2-
Examples include naphthoquinonediazide-4-sulfonic acid ester and 1,2-naphthoquinonediazide-5-sulfonic acid ester.

Specifically, for example, 1,2-benzoquinonediazide-4 of (poly) hydroxybenzene such as p-cresol, resorcinol, pyrogallol, phloroglicinol, etc.
-Sulfonic acid ester, 1,2-naphthoquinonediazide-4-
Sulfonate or 1,2-naphthoquinonediazide-5
-Sulfonic acid esters; 2,4-dihydroxyphenylpropyl ketone, 2,4-dihydroxyphenyl-n-hexyl ketone, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxyphenyl-n-hexyl ketone, 3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone,
2,2 ', 3,4-tetrahydroxybenzophenone, 3'-methoxy-2,3,4,4'-tetrahydroxybenzophenone, 2,
2 ', 4,4'-tetrahydroxybenzophenone, 2,2', 3,4,
6'-pentahydroxybenzophenone, 2,3,3 ', 4,4', 5'-
Hexahydroxybenzophenone, 2,3 ', 4,4', 5 ', 6'-
1,2-benzoquinonediazide-4- of (poly) hydroxyphenyl alkyl ketone such as hexahydroxybenzophenone or (poly) hydroxyphenyl aryl ketone
Sulfonate, 1,2-naphthoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-5-
Sulfonates: bis (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane 1,2-benzo (2,2-bis (2,4-dihydroxyphenyl) propane, 2,2-bis (2,3,4-trihydroxyphenyl) propane) Quinonediazide
-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4
-Sulfonate or 1,2-naphthoquinonediazide
-5-sulfonic acid ester; lauryl 3,5-dihydroxybenzoate, phenyl 2,3,4-trihydroxybenzoate, 3,4,
Alkyl (poly) hydroxybenzoate or aryl (poly) hydroxybenzoate such as lauryl 5-trihydroxybenzoate, propyl 3,4,5-trihydroxybenzoate, phenyl 3,4,5-trihydroxybenzoate 1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester of bis (2,5-dihydroxybenzoyl) methane , Bis (2,3,4-trihydroxybenzoyl) methane, bis (2,
4,6-trihydroxybenzoyl) methane, p-bis (2,
5-dihydroxybenzoyl) benzene, p-bis (2,3,
4-trihydroxybenzoyl) benzene, p-bis (2,
Bis such as 4,6-trihydroxybenzoyl) benzene
1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester of 1,2-naphtho [(poly) hydroxybenzoyl) alkane or bis [(poly) hydroxybenzoyl) benzene Quinonediazide-5-sulfonic acid ester; ethylene glycol-di (3,5-dihydroxybenzoate), polyethylene glycol-di (3,5-dihydroxybenzoate), polyethylene glycol-di (3,4,5-trihydroxybenzoate), etc. Polyethylene glycol di
1,2-benzoquinonediazide-4-sulfonic acid ester, 1,2-naphthoquinonediazide-4-sulfonic acid ester or 1,2-naphthoquinonediazide-5-sulfonic acid ester of [(poly) hydroxybenzoate];
1,2-benzoquinonediazide-4-sulfonic acid ester, 1,
2-naphthoquinonediazide-4-sulfonic acid ester or
1,2-naphthoquinonediazide-5-sulfonic acid ester and the like.

Of the quinonediazide compounds (D), particularly preferred are 2,3,4-trihydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester and 2,3,4-trihydroxybenzophenone- 1,2-naphthoquinonediazide-5-sulfonic acid ester, 2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-sulfonic acid ester, 2,3,4,4'-tetrahydroxy Benzophenone-1,2-naphthoquinonediazide-5-sulfonate, 3'-methoxy-2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide-4-
Sulfonate, 3'-methoxy-2,3,4,4'-tetrahydroxybenzophenone-1,2-naphthoquinonediazide
Polyhydroxybenzophenone-1,2-naphthoquinonediazidosulfonic acid ester such as -5-sulfonic acid ester,
And an alkali-soluble novolak resin or an alkali-soluble resole resin (hereinafter referred to as “resin (C)”), for example, by adding 20 to 10 hydrogen atoms per hydrogen atom.
1,2-naphthoquinonediazido-4-sulfonyl group, 1,2-naphthoquinonediazide-5-sulfonyl group and other 1,2-quinonediazidosulfonyl groups such as 1,2-naphthoquinonediazido-4-sulfonyl group at 0 mol%, preferably 40 to 100%. 2-quinonediazidesulfonic acid ester.

The resin (C) is obtained by condensation of a phenol and an aldehyde. Examples of the phenol include those exemplified as the phenol used in the synthesis of the resin (A), and phenol and 1-phenol. Naphthol, 2-naphthol and the like can be used. As the aldehydes, those used in the synthesis of the resin (A) can be used. The amount of the aldehyde used is preferably 0.1 to 3 mol, more preferably 0.2 to 1.5 mol, per 1 mol of the phenol. In this condensation, an alkaline catalyst can be used in addition to the acidic catalyst exemplified in the synthesis of the resin (A).

The Mw of the resin (C) is usually preferably 10,000 or less, more preferably 200 to 2,000, in view of the ease of the esterification reaction and the solubility in a solvent. Particularly preferred Mw is 300-1,000. Examples of the 1,2-quinonediazidesulfonic acid ester of the resin (C) include phenol / formaldehyde condensed novolak resin-1,2-naphthoquinonediazide-4-sulfonic acid ester and phenol / formaldehyde condensed novolak resin-1,2- Naphthoquinonediazide-5-sulfonic acid ester, m-cresol / formaldehyde condensed novolak resin-1,2-naphthoquinonediazide-4-sulfonic acid ester, m-cresol / formaldehyde condensed novolak resin-1,2-naphthoquinonediazide-5-sulfone Acid ester, p-cresol / formaldehyde condensed novolak resin-1,2-naphthoquinonediazide-4-sulfonic acid ester, p-cresol / formaldehyde condensed novolak resin-1,2-naphthoquinonediazide-5-sulfonic acid ester, o-cresol / Holmardich Condensed novolak resin-1,2-naphthoquinonediazide-4-sulfonic acid ester, o-cresol / formaldehyde condensed novolak resin-1,2-naphthoquinonediazide-5-sulfonic acid ester, m-cresol / p-cresol / formaldehyde condensed novolak Resin-1,2-naphthoquinonediazide-4-
Sulfonate, m-cresol / p-cresol / formaldehyde condensed novolak resin-1,2-naphthoquinonediazide-5-sulfonate and the like.

In the composition of the present invention, the amount of the quinonediazide compound (D) is usually 0 to 100 parts by weight, preferably 5 to 50 parts by weight, per 100 parts by weight of the resin (A).
However, the total amount of 1,2-quinonediazidosulfonyl groups in the composition is usually adjusted to 5 to 25% by weight, preferably 10 to 20% by weight.

Various Compounding Agents In the composition of the present invention, various compounding agents such as sensitizers and surfactants can be compounded, if necessary.

The sensitizer is compounded to improve the sensitivity of the composition.
For example, 2H-pyrido- (3,2-b) -1,4-oxazine-3 (4H) -ones, 10H-pyrido- (3,2-b)-(1,4) -oxazine-3 (4H )-
Examples include benzothiazines, urazoles, hydantoins, parbituric acids, glycine anhydrides, 1-hydroxybenzotriazoles, alloxanes, and maleimides. These can be used alone or in combination of two or more.

The amount of these sensitizers is 100
The amount is usually 50 parts by weight or less, preferably 30 parts by weight or less based on parts by weight.

The surfactant is compounded for improving the coating property and the developability of the composition. Examples of such a surfactant include polyoxyethylene lauryl ether and polyoxyethylene stearyl ether. ,
Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, and polyethylene glycol distearate;
EF301, EF301, EF352 (trade name, manufactured by Shin-Akita Kasei), Megafax F171, F172, F173 (trade name, manufactured by Dainippon Ink), Florad FC430, FC431 (trade name, manufactured by Sumitomo 3M) Asahi Guard AG710 , Surflon S-382, SC
-101, SC-102, SC-103, SC-104, SC-105, SC-106 (trade name, manufactured by Asahi Glass Co., Ltd.), etc., organosiloxane polymer KP341 (trade name, Shin-Etsu Chemical Co., Ltd.) No. 75, No. 95 (trade name, manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.). These can be used alone or in combination of two or more.

The amount of these surfactants is usually 2 parts by weight or less, preferably 0.001 to 1 part by weight, per 100 parts by weight of the solid content of the composition.

Further, the composition of the present invention can contain a dye or a pigment for visualizing the latent image of the irradiated portion and reducing the influence of halation upon irradiation, and can improve the adhesiveness. In order to do so, an adhesion aid may be added. Further, if necessary, a storage stabilizer, an antifoaming agent and the like can be added.

Preparation of Composition and Pattern Formation The composition of the present invention is prepared by mixing the above-mentioned resin (A), compound (B) and the above-mentioned various compounding agents with a solid content of 10%.
It is prepared by dissolving in a solvent so as to have a concentration of about 50% by weight, preferably 20 to 40% by weight, and filtering through a filter having a pore size of about 0.2 μm.

Examples of the solvent used in this case include glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether;
Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; diethylene glycols such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; toluene , Aromatic hydrocarbons such as xylene, ketones such as methyl ethyl ketone and cyclohexanone, 2-
Ethyl hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Esters such as ethyl ethoxypropionate, ethyl acetate and butyl acetate can be used. These organic solvents are used alone or in combination of two or more. Further N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone, Isophorone, caproic acid, caprylic acid, 1-octanol,
High boiling solvents such as 1-naphthol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate can also be added.

The composition of the present invention is applied to a silicon wafer or a wafer coated with aluminum or the like by spin coating, flow coating, roll coating or the like to form a photosensitive layer, and a predetermined mask pattern is formed. The pattern is formed by irradiating the photosensitive layer with radiation and developing with a developer.

When the composition of the present invention is used as a positive resist, the composition is coated on a wafer or the like, prebaked and exposed, and then heated at 70 to 140 ° C. Then, by performing development, the effect of the present invention can be further improved.

Developer The developer of the composition of the present invention includes, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di- n-
Propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- (5,4,0) -7-undecene An alkaline aqueous solution obtained by dissolving an alkaline compound such as 1,5-diazabicyclo- (4,3,0) -5-nonane in a concentration of usually 1 to 10% by weight is used.

The developer may be used after adding an appropriate amount of a water-soluble organic solvent, for example, an alcohol such as methanol or ethanol, or a surfactant.

When development is performed using a developing solution composed of such an alkaline aqueous solution, rinsing is generally continued with water.

[0052]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited by these examples.

The measurement of Mw and the evaluation of the resist in the examples were performed by the following methods.

[0054] Mw: Toyo Soda Co. gel permeation chromatography (hereinafter, referred to as "GPC") column (G2000H ₆ 2 present, G3
000H ₆ 1 bottle, G4000H ₆ 1 bottle) at a flow rate of 1.5 ml / min.
It was measured by a GPC method using monodisperse polystyrene as a standard under the analysis conditions of an elution solvent of tetrahydrofuran and a column temperature of 40 ° C.

Sensitivity: The exposure time is changed using a Nikon NSR-1505G4D reduction projection exposure machine (lens numerical aperture; 0.45), and exposure is performed using g-line having a wavelength of 436 nm, or Nikon Corporation. Exposure was performed using i-line with a wavelength of 365 nm by changing the exposure time with an NSR-1505i6A reduction projection exposure machine (numerical aperture of the lens; 0.45), and then a 2.4 wt% aqueous solution of tetramethylammonium hydroxide was developed. Used as a liquid, developed at 25 ° C for 60 seconds, rinsed with water and dried to form a resist pattern on the wafer, forming a 0.6 μm line-and-space pattern (1 LIS) with a 1: 1 width Exposure time (hereinafter,
"Optimal exposure time").

Resolution: The minimum dimension of the resist pattern that could be resolved when exposed for the optimal exposure time was measured.

Remaining film ratio: The thickness of the pattern after development at the optimum exposure time was divided by the thickness of the resist film before development, and this value was multiplied by 100 to give a unit of%.

Developability: The degree of scum and residual development was examined.

Heat resistance: The wafer on which the resist pattern was formed was placed in a clean oven, and the temperature was raised (temperature rising rate 5-10 ° C. /
Min), the temperature at which the pattern began to collapse was measured.

Pattern shape: Using a scanning electron microscope, the lower and upper sides A and B of a rectangular cross section of a 0.6 μm resist pattern after development were measured.
When ≦ B / A ≦ 1, the pattern shape was determined to be good. However, the pattern shape is pulling the hem,
In the case of a reverse taper shape, it was not determined that B / A was good even when B / A was within the above range.

<Synthesis of Resin (A)> Synthesis Example 1 In a flask equipped with a stirrer, a cooling pipe and a thermometer, m
-Cresol 67.6 g (0.63 mol), 2,3,5-trimethylphenol 10.0 g (0.073 mol), p-cresol 31.8 g
(0.29 mol), 37% by weight aqueous formaldehyde solution 107.1
g (formaldehyde: 1.32 mol) and oxalic acid dihydrate 1.33 g (1.26 × 10 ^-2 mol) were charged, the flask was immersed in an oil bath, and polycondensation was carried out for 30 minutes while stirring while maintaining the internal temperature at 100 ° C. After that, 17.5 g (0.16 mol) of m-cresol and 40.0 g (0.29 mol) of 2,3,5-trimethylphenol were added, and polycondensation was further performed for 40 minutes.

Next, the temperature of the oil bath was raised to 180 ° C., and simultaneously the pressure in the flask was lowered to 30 to 50 mmHg.
Oxalic acid, unreacted formaldehyde, m-cresol, p-cresol and 2,3,5-trimethylphenol were removed.

Next, the molten resin was returned to room temperature and collected. This resin is referred to as resin (A1).

Synthesis Example 2 Resin (A1) was dissolved in ethyl cellosolve acetate so as to have a solid content of 20% by weight, and then added to methanol and an equal amount of water twice as much as the weight of the resin solution, followed by stirring. And left. After being separated into two layers by standing, the resin solution layer (lower layer) is taken out, concentrated, dehydrated,
After drying, the resin was recovered. This resin is referred to as resin (A2).

Synthesis Example 3 In an autoclave, 69.2 g (0.64 mol) of m-cresol, 21.8 g (0.16 mol) of 2,3,5-trimethylphenol, 61.0 g of a 37% by weight aqueous formaldehyde solution (formaldehyde: 0.75 mol), oxalic acid 6.3 g of dihydrate (0.
05 mol), 52.6 g of water and 182 g of dioxane.
The autoclave was immersed in an oil bath, polycondensation was carried out for 6 hours while stirring at an internal temperature of 130 ° C., and after the reaction, the content was returned to room temperature and the contents were taken out into a beaker. After separating into two layers in this beaker, the lower layer was taken out, concentrated, dehydrated, and dried to collect the resin. This resin is referred to as resin (A3).

Synthesis Example 4 In the same flask as used in Synthesis Example 1, 13.0 g (0.12 mol) of m-cresol, 32.4 g (0.3 mol) of p-cresol, 39.0 g (0.32 mol) of 3,5-xylenol , 37% by weight
56.9 g of formaldehyde aqueous solution (formaldehyde: 0.
70 mol) and oxalic acid dihydrate 0.083 g (6.59 × 10 ⁻⁴⁾
Mol), and the flask is immersed in an oil bath.
After performing polycondensation for 30 minutes while stirring, 51.9 g (0.48 mol) of m-cresol and 9.77 g (0.08 mol) of 3,5-dimethylphenol were continuously added to the flask as the reaction progressed. Charged and polycondensed for 45 minutes.

Thereafter, the resin was recovered in the same manner as in Synthesis Example 1. This resin is referred to as resin (A4).

Synthesis Example 5 In an autoclave, 69.2 g (0.64 mol) of m-cresol, 19.5 g (0.16 mol) of 3,5-xylenol, 37% by weight
58.4 g of formaldehyde aqueous solution (formaldehyde: 0.
72 mol), 0.90 g (7.14 × 10 ⁻³ mol) of oxalic acid dihydrate, 54.4 g of water and 228 g of dioxane were charged, polycondensed for 10 hours, and the resin was recovered in the same manner as in Synthesis Example 3. This resin is referred to as resin (A5).

Synthesis Example 6 26.0 g (0.24 mol) of m-cresol and 78.2 g (0.64 mol) of 3,5-xylenol were placed in the same flask as used in Synthesis Example 1.
Mol), 14.6 g of a 37% by weight aqueous solution of formaldehyde (formaldehyde: 1.80 mol) and oxalic acid dihydrate 0.1
64 g (1.30 × 10 ⁻³ mol) was charged, the flask was immersed in an oil bath, polycondensation was carried out for 30 minutes while maintaining the internal temperature at 100 ° C., and then 104 g (0.96 mol) of m-cresol and 20.0 g (0.16 mol) of 3,5-xylenol was added, and polycondensation was further performed for 70 minutes.

Next, the temperature of the oil bath was raised to 180 ° C., and at the same time, the pressure in the flask was lowered to 30 to 40 mmHg.
Oxalic acid, unreacted formaldehyde, m-cresol and 3,5-xylenol were removed. Next, Synthesis Example 1
The resin was recovered in the same manner as described above. This resin is referred to as resin (A6).

Synthesis Example 7 In the same flask as used in Synthesis Example 1, 95.2 g (0.88 mol) of m-cresol, 2,3,5-trimethylphenol 2
4.4 g (0.18 mol), 37% by weight formaldehyde aqueous solution
154 g (formaldehyde: 1.90 mol) and oxalic acid dihydrate 1.82 g (0.014 mol) were charged, the flask was immersed in an oil bath, polycondensed for 90 minutes while stirring while maintaining the internal temperature at 100 ° C. 23.8 g of m-cresol (0.22 g
Mol) and 97.6 g of 2,3,5-trimethylphenol (0.72
Mol) was added and polycondensation was carried out for an additional 60 minutes.

Next, the oil bath temperature was raised to 180 ° C., and at the same time, the pressure in the flask was lowered to 30 to 40 mmHg.
Oxalic acid, unreacted formaldehyde, m-cresol and 2,3,5-trimethylphenol were removed. Next, the resin was recovered in the same manner as in Synthesis Example 1. This resin is referred to as resin (A7).

<Synthesis of Resin (C)> Synthesis Example 8 In a flask similar to that used in Synthesis Example 1, 108.0 g (1.00 mol) of m-cresol, 24.3 g of a 37% by weight aqueous solution of formaldehyde (formaldehyde: 0.30 mol) Then, 0.30 g (2.40 × 10 ⁻³ mol) of oxalic acid dihydrate was charged, the flask was immersed in an oil bath, and polycondensation was performed for 40 minutes while maintaining the internal temperature at 100 ° C. Next, the resin was recovered in the same manner as in Synthesis Example 1. This resin is referred to as resin (C1).

Synthesis Example 9 A flask similar to that used in Synthesis Example 1 was charged with 64.9 g (0.60 mol) of m-cresol, 43.3 g (0.40 mol) of p-cresol, and 20.3 g of a 37% by weight aqueous formaldehyde solution (formaldehyde: 0.25 mol). Mol) and oxalic acid dihydrate 0.30 g
(2.40 × 10 ^-3 mol), immerse the flask in an oil bath,
Polycondensation was performed for 30 minutes while maintaining the internal temperature at 100 ° C. Next, the resin was recovered in the same manner as in Synthesis Example 1. This resin is referred to as resin (C2).

<Abbreviated name of polyhydroxy compound (B ₁ )> In the following, the polyhydroxy compound (B ₁ ) of 1,3-
Bis (3,4-dihydroxyphenoxy) benzene compound
(B ₁ 1), 1,4-bis (3,5-dihydroxy aminophenoxy) benzene Compound (B ₁ 2), 1,3,5-tris (4-hydroxyphenoxy) benzene Compound (B ₁ 3), 1,4-bis (4-hydroxyphenoxy) benzene compound (B ₁ 4), 1,3-bis (4-dihydroxy aminophenoxy) benzene compound (B
₁ 5), abbreviated 2,4-bis (4-dihydroxy-phenoxy) phenol compound (B ₁ 6).

[0076] In Synthesis Example 10 shielding <quinonediazide compound (B ₂₎ Synthesis of> stirrer, a flask equipped with a dropping funnel and a thermometer, the compound _{(B 1 1) 32.6 g (} 0.10 mol), 1,2 Naphthoquinonediazide-4-sulfonic acid chloride 80.6g
(0.30 mol) and 100 g of dioxane were charged and dissolved with stirring.

Then, the flask was immersed in a water bath controlled at 30 ° C., and when the internal temperature became constant at 30 ° C., 33.3 g (0.33 mol) of triethylamine was added to the solution, and the internal temperature was kept at 35 ° C. Was slowly dropped using a dropping funnel.

Thereafter, the precipitated triethylamine hydrochloride was removed by filtration, and the filtrate was poured into a large amount of dilute hydrochloric acid to cause precipitation. Then, the precipitate was filtered, and dried overnight with a heating vacuum dryer controlled at 40 ° C. To give the compound. The resulting compound, referred to as the compound (B ₂ 1).

[0079] Except for using Synthesis Example 11 Compound _{(B 1 1) 32.6 g (} 0.10 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride 80.6 g (0.30 mol) and triethylamine 33.3 g (0.33 mol) are in the same manner as in example 10 to give compound (B _{2 2).}

[0080] Except for using Synthesis Example 12 Compound _{(B 1 2) 32.6 g (} 0.10 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride 80.6 g (0.30 mol) and triethylamine 33.3 g (0.33 mol) are in the same manner as in example 10 to give compound (B ₂ 3).

[0081] Except for using Synthesis Example 13 Compound _{(B 1 3) 40.2 g (} 0.10 mol) of 1,2-naphthoquinonediazide-5-sulfonic acid chloride 53.7 g (0.20 mol) and triethylamine 22.3 g (0.22 mol) are in the same manner as in example 10 to give compound (B ₂ 4).

<Synthesis of quinonediazide compound (D)> Synthesis Example 14 10.0 g of resin (C1) 1,3.9 g of 1,2-naphthoquinonediazide-4-sulfonic acid chloride and 5.75 g of triethylamine
A quinonediazide compound (D1) was obtained in the same manner as in Synthesis Example 10 except that was used.

Synthesis Example 15 10.0 g of resin (C2) 16.6 g of 1,2-naphthoquinonediazide-4-sulfonic acid chloride and 6.86 g of triethylamine
A quinonediazide compound (D2) was obtained in the same manner as in Synthesis Example 10 except that was used.

[0084] Examples 1 to 11 and Comparative Examples 1 to 3 resin (A), the quinonediazide compound (D), polyhydroxy compound (B ₁₎ or quinonediazide compound (B ₂₎ and a solvent were mixed, after a uniform solution The mixture was filtered through a membrane filter having a pore size of 0.2 μm to prepare a composition of the present invention. The obtained composition was pre-baked on a silicon wafer having a silicon oxide film at 90 ° C. for 2 minutes to a thickness of 1.2.
After forming a resist film having a thickness of μm, and exposing using a g-line having a wavelength of 436 nm or an i-ray having a wavelength of 365 nm through a reticle as described above, developing, rinsing and drying, the sensitivity of the resist film is determined. , Resolution, residual film ratio, developability, heat resistance and pattern shape were evaluated. The results are shown in Table 1 together with the used resins and the like.

Examples 1 to 9 and Comparative Examples 1 and 2
Irradiated g-rays, and Examples 10 and 11 and Comparative Example 3
The line was irradiated.

[0086]

[Table 1]

Note: Each amount added is shown in parts by weight. Note: (D3) to (D6) in the quinonediazide compound (D)
Is: (D3); 1 mol of 2,3,4-trihydroxybenzoquinone and 1,
Condensate with 3.0 mol of 2-naphthoquinonediazide-5-sulfonic acid chloride. (D4); 1 mol of 2,3,4,4'-tetrahydroxybenzoquinone and 1,2-naphthoquinonediazide-5-sulfonic acid chloride
Condensate with 3.6 moles. (D5); 1 mol of 2,3,4,4'-tetrahydroxybenzoquinone and 1,2-naphthoquinonediazide-5-sulfonic acid chloride
Condensate with 4.0 moles. (D6); 1 mol of 2,3,4,4'-tetrahydroxybenzoquinone and 1,2-naphthoquinonediazide-4-sulfonic acid chloride
Condensate with 4.0 moles. Note: The types of solvents are as follows. α: ethyl cellosolve acetate. β; ethyl 2-hydroxypropionate. Note: Compound (E); m-cresol 108.0 g (1.00 mol), 37% by weight formaldehyde aqueous solution 20.3 g (formaldehyde: 0.25 mol) and oxalic acid dihydrate 0.30 g
(2.40 × 10 ^-3 mol), and maintain the internal temperature at 100 ° C.
An alkali-soluble novolak resin (Mw = 520) synthesized in the same manner as in Synthesis Example 1 except that condensation was performed for 30 minutes.

[0088]

According to the radiation-sensitive resin composition of the present invention, a positive resist which is excellent in developing property by effectively suppressing the occurrence of scum, has high sensitivity, and is excellent in heat resistance, residual film property and the like. Can be suitably used.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Takao Miura 2--11-24 Tsukiji, Chuo-ku, Tokyo Japan Synthetic Rubber Co., Ltd. (56) References JP-A-2-296248 (JP, A) JP-A Sho 57-135947 (JP, A) JP-A-57-63526 (JP, A) JP-A-2-197844 (JP, A) JP-A-2-254451 (JP, A) JP-A-1-289946 (JP, A A) JP-A-2-2560 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G03F ^7/ 00-7/42

Claims (1)

(57) [Claims] (A) an alkali-soluble resin, and (B) a general formula (1): [Wherein, D represents a hydrogen atom or a 1,2-quinonediazide group-containing organic group, and R ¹ and R ² represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a carbon atom having 6 carbon atoms.
R ³ represents an OD group (where D is the same as described above) or the same group as R ¹ , X represents a hydrogen atom, an OD group (where D is the same as described above), or Embedded image (Where D is the same as above, R ⁴ represents the same group as R ¹ , f represents an integer of 0 to 3 and g represents an integer of 0 to 2), and a and b represent 1 Represents an integer of ~ 3, c and d
And e show the integer of 0-2. ] The radiation-sensitive resin composition containing the compound represented by these.