JPH07230165A - Positive type photoresist composition - Google Patents

Abstract

PURPOSE:To provide the positive type photoresist composition causing no striation and no inferior coat film and no poor development and superior in characteristics of deformability and wetability. CONSTITUTION:The positive type photoresist composition is formed by dissolving an alkali-soluble resin, a compound having a quinonediazido group, a compound of formula I (Rf is 6-10C fluoroalkyl; R<1> is H or 1-5 C alkyl; and R<2> is 2-5C alkyl having >=2 hydroxy), a compound of formula II (Rg is 4-20C perfluoroalkyl, and (m) is 1 or 2), or a nonionic fluorinated organopolysiloxane type compound only having perfluoroalkylated siloxane bonds and polyoxyethylene type polyether bonds in a solvent, such as alkyl-2-oxypropionate-alkyl-acetate or alkyl-2-oxypropionate-propylene-glycol-monoalkyl-ether-acetate.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel positive photoresist composition, and more specifically, it does not cause coating unevenness called striation, and is excellent in defoaming property and wetting property. The present invention relates to a positive photoresist composition that does not cause poor development.

[0002]

2. Description of the Related Art As a typical photoresist composition used for manufacturing a semiconductor integrated circuit, a composition containing an alkali-soluble novolac and a naphthoquinonediazide compound as main components is known. In such a photoresist composition, Has a drawback that it causes uneven coating called striation when the solution is applied to a substrate.

This striation, when visually observed, exhibits a radial striped pattern, and usually has a wavy undulation having a height difference of several hundred liters. When such striations occur, the linearity and reproducibility of the pattern deteriorate, and a fatal defect occurs in the semiconductor lithography technique that a desired resist pattern cannot be formed.

In order to improve such drawbacks, resist compositions containing various fluorine-containing surfactants have been proposed (JP-A-62-36657).

On the other hand, it has been proposed to add various fluorine-containing surfactants to the photosensitive composition used for the photosensitive printing plate in order to improve the printing characteristics (Japanese Patent Laid-Open No. 64-48849). Japanese Patent Publication No. 64-50040,
JP-A-4-9065, JP-A-4-212965, etc.).

As described above, it is a conventional practice to add a fluorine-containing surfactant to a resist composition or a photosensitive composition for a photosensitive printing plate. However, when the conventional fluorine-based surfactant is used, although the problem of striation is solved to some extent, bubbles are likely to occur in the resist solution, and such bubbles remain without disappearing. However, when the resist solution is applied onto the substrate, bubbles remain on the resist film to cause a defective coating film, which causes a problem that a desired resist pattern cannot be formed. Therefore, a resist composition having excellent defoaming properties is desired.

Further, in a conventional resist composition containing a fluorine-containing surfactant, the resist wettability is not sufficient during resist development, and when the resist solution on the substrate is coated with a developing solution, bubbles are formed on the resist surface. A resist composition having excellent wetting characteristics is desired, because development is defective due to the presence of the bubbles and the presence of the bubbles, and a desired resist pattern cannot be obtained.

[0008]

SUMMARY OF THE INVENTION The present invention, which is used in the manufacture of semiconductors, does not cause striation and has excellent defoaming properties and wetting characteristics. It was made for the purpose of providing a positive photoresist composition which does not have a positive photoresist.

[0009]

Means for Solving the Problems As a result of intensive studies to develop a positive photoresist composition having excellent defoaming and wetting properties, the present inventors have replaced conventional fluorine-based surfactants. Then, it was found that the purpose can be achieved by using a specific nonionic fluorine compound in combination with a specific organic solvent, and the present invention has been completed based on this finding.

That is, the present invention provides (A) an alkali-soluble resin, (B) a quinonediazide group-containing compound, and (C) a general formula (I).

[Chemical 2] [Wherein R _f is a fluorinated alkyl group having 6 to 10 carbon atoms in which some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms, R ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
R ² is an alkyl group having 2 or more hydroxyl groups and having 2 to 5 carbon atoms, — (CH ₂ CH ₂ O) _n —R ³ (wherein R ³ is a hydrogen atom or a benzoyl group, and n is an integer of 1 to 10). Yes) or-
CH ₂ COOR ⁴ compound represented by (R ⁴ is an alkyl group having 1 to 5 carbon atoms) is, the general formula _{(II) R g - (CH} 2) m -OCH 2 CH (OH) -CH 2 OH (II) (wherein R _g is a perfluoroalkyl group having 4 to 20 carbon atoms, m is an integer of 1 or 2), a perfluoroalkyl group-containing siloxane bond and a polyoxyethylene type poly At least one nonionic fluorine-containing compound selected from nonionic fluorine-containing organosiloxane compounds having only an ether bond,
(D) Mixed solvent of 60 to 90% by weight of alkyl 2-oxypropionate and 40 to 10% by weight of alkyl acetate, 50 to 90% by weight of alkyl 2-oxypropionate and 50 to 1 of propylene glycol monoalkyl ether acetate
The present invention provides a positive photoresist composition which is dissolved in 0% by weight of a mixed solvent or propylene glycol monoalkyl ether acetate.

In the composition of the present invention, the alkali-soluble resin used as the component (A) is not particularly limited, and has a solubility in an alkaline solution which is conventionally used as a film forming resin in a positive photoresist composition. Any resin may be used. Examples of such a compound include a novolak resin obtained by condensing at least one selected from aromatic hydroxy compounds such as phenol, cresol, xylenol, and resorcinol with an aldehyde compound such as formaldehyde, acetaldehyde, and benzaldehyde. , Vinylphenol compounds such as p-vinylphenol, m-vinylphenol, o-vinylphenol and α-methylvinylphenol, and polymers or copolymers of these halogen-substituted compounds, acrylic acid, methacrylic acid, hydroxyethyl acrylate, Acrylic or methacrylic acid-based copolymers such as hydroxyethyl methacrylate, polyvinyl alcohol, and quinonediazide groups and naphthoquinonediazide groups are introduced through a part of the hydroxyl groups of each resin. And the like entering the modified resin. These alkali-soluble resins may be used alone or in combination of two or more.

Among these alkali-soluble resins, the weight average molecular weight of the low molecular weight region cut is 2000 to 2000.
A cresol novolac resin of 0, preferably 5000 to 15000 is suitable because it gives a photoresist composition having excellent heat resistance.

Examples of the quinonediazide group-containing compound as the component (B) used in the composition of the present invention include (i)
2,3,4-trihydroxybenzophenone, 2,4
4'-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone, 2,3,6-trihydroxybenzophenone, 2,3,4-trihydroxy-
2'-methylbenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3', 4,4 ',
6-pentahydroxybenzophenone, 2,2 ', 3,
4,4'-pentahydroxybenzophenone, 2,
2 ', 3,4,5'-pentahydroxybenzophenone, 2,3', 4,4 ', 5', 6-hexahydroxybenzophenone, 2,3,3 ', 4,4', 5'-hexahydroxy Polyhydroxybenzophenones such as benzophenone, (ro) bis (2,4-dihydroxyphenyl) methane, bis (2,3,4-trihydroxyphenyl) methane, 2- (4-hydroxyphenyl) -2-
(4'-hydroxyphenyl) propane, 2- (2,4
-Dihydroxyphenyl) -2- (2 ', 4'-dihydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (2', 3 ', 4'-trihydroxyphenyl) propane Bis [(poly) hydroxyphenyl] alkanes such as (ha) 1- [1- (4-
Hydroxyphenyl) isopropyl] -4- [1,1-
Bis (4-hydroxyphenyl) ethyl] benzene,
(D) Tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dimethylphenyl) -4-
Hydroxyphenylmethane, bis (4-hydroxy-
2,5-Dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2- Tris such as hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane (Hydroxyphenyl) methanes or their methyl-substituted products, (V) bis (3-cyclohexyl-4-hydroxyphenyl) -3-hydroxyphenylmethane, bis (3
-Cyclohexyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-
4-hydroxyphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2)
-Methylphenyl) -2-hydroxyphenylmethane,
Bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenylmethane, bis (3-
Cyclohexyl-2-hydroxyphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4)
-Hydroxy-3-methylphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-3-methyl) Phenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-2-hydroxyphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl) Bis (cyclohexylhydroxyphenyl) such as 2-hydroxy-4-methylphenyl) -2-hydroxyphenylmethane and bis (5-cyclohexyl-2-hydroxy-4-methylphenyl) -4-hydroxyphenylmethane
(Hydroxyphenyl) methanes or their methyl-substituted derivatives (f) phenol, p-methoxyphenol, dimethylphenol, hydroquinone, naphthol, pyrocatechol, pyrogallol, pyrogallol monomethyl ether,
Pyrogallol-1,3-dimethyl ether, gallic acid,
Esterified or etherified gallic acid leaving some hydroxyl groups, aniline, p-aminodiphenylamine, 4,
Compounds having a hydroxyl group or an amino group such as 4'-diaminobenzophenone, (to) novolac, pyrogallol-acetone resin, homopolymers of p-hydroxystyrene or copolymers with monomers copolymerizable therewith, and naphthoquinone-1. , 2-diazide-5-sulfonic acid or naphthoquinone-1,2-diazide-4-sulfonic acid, orthobenzoquinonediazidesulfonic acid, orthoanthraquinonediazidosulfonic acid, etc. , Amidated or partially amidated, and the like.

In the composition of the present invention, as the component (B), the above-mentioned quinonediazide group-containing compound may be contained alone or in combination of two or more kinds.

The component (B) is added in an amount of 5 to 100 relative to 100 parts by weight of the alkali-soluble resin of the component (A).
It is desirable to blend in a range of 10 parts by weight, preferably 10 to 50 parts by weight. If the blending amount is less than 5 parts by weight, an image faithful to the pattern cannot be obtained, and the transferability is deteriorated.
If the amount is more than parts by weight, the homogeneity of the formed resist film is deteriorated and the resolution tends to be deteriorated.

In the composition of the present invention, as the nonionic fluorine-based compound as the component (C), each compound represented by the above general formulas (I) and (II), a perfluoroalkyl group-containing siloxane bond and polyoxyethylene. At least one selected from nonionic fluorine-containing organosiloxane compounds having only a type polyether bond is used.

As the nonionic fluorine-based compound represented by the general formula (I), R _f has a C ₇ F ₁₅ group or a C ₈ F ₁₇ group.
A group is preferable, and examples thereof include the groups shown below.

R _f -SO ₂ -N (C ₃ H ₇ )-(CH ₂ CH ₂ O) ₁₀ -H (when R _f is C ₈ F ₁₇ , trade name "EF-122B") R _f -SO _{2 -N (C 2 H 5)} - (CH 2 CH 2 O) 7 -H R f -SO 2 -N (C 3 H 7) - (CH 2 CH 2 O) 5 -H R f -SO 2 - _{N (C 3 H 7) -} ( when R _f is a C ₈ F _17, trade name _{"EF-122C") (CH 2 CH 2 O)} 3 -H R f -SO 2 -N (C 3 H 7) (if R _f is a C ₈ F _17, trade name _{"EF-121") -CH 2 CH 2 OH R f} -SO 2 -N (C 5 H 11) - (CH 2 CH 2 O) 10 -H R _{f -SO 2 -NH- (CH 2 CH} 2 O) 7 -H R f -SO 2 -N (C 4 H 9) - (CH 2 CH 2 O) 5 -H R f -SO 2 -N (C _{2 H 5) - (CH 2} CH 2 O) 3 -H R f -SO 2 -N (C 2 H 5) -CH 2 CH 2 OH

[Chemical 3] (When R _f is C ₈ F ₁₇ , product name “EF-126”)

[Chemical 4]

[Chemical 5]

[Chemical 6]

R _f --SO ₂ --N (C ₃ H ₇ )-CH ₂ CH (O
H) CH ₂ OH (when R _f is C ₈ F ₁₇ , product name “MF-110”) R _f —SO ₂ —NH—CH ₂ CH ₂ CH (OH) CH ₂ OH R _f —SO ₂ —N _{(C 4 H 9) -CH (} OH) CH 2 OH

R _f —SO ₂ —N (C ₃ H ₇ ) —CH ₂ COOC ₂ H ₅ (when R _f is C ₈ F ₁₇ , trade name “EF-127”) R _f —SO ₂ —N ( _{C 5 H 11) -CH 2 COOC} 4 H 9 R f -SO 2 -NH-CH 2 COOC 3 H 7 R f -SO 2 -N (C 2 H 5) -CH 2 COOCH 3

As the nonionic fluorine-based compound represented by the general formula (II), R _g has a C ₄ F ₉ group and a C ₆ group.
It is preferably an F ₁₃ group or a C ₈ F ₁₇ group, and examples of such a group include those shown below. For _{R g -CH 2 -OCH 2 CH (} OH) -CH 2 OH R g -CH 2 CH 2 -OCH 2 CH (OH) -CH 2 OH (R g is C ₆ F _13, trade name "MF- 100 ")

Commercially available products can be used as these nonionic fluorine-based compounds, and examples of the commercially available products include the above-mentioned EFTOP "EF-121" and "EF-12".
2B "," EF-122C "," EF-126 "," E
F-127 "," MF-110 "," MF-100 "
(All are manufactured by Tochem Products) and the like. Among these, "EF-122B" is the most preferable.

Further, the above-mentioned nonionic fluorine-containing organosiloxane compound having only a perfluoroalkyl group-containing siloxane bond and a polyoxyethylene type polyether bond is a siloxane group having a perfluoroalkyl group and a polyoxyethylene type compound. A compound having a polyether group bonded, and examples of commercially available products include X-70.
-090, X-70-091, X-70-092, X-
70-093 (all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like, among which X-70-092 and X-70-09.
3 is the most preferable.

In the composition of the present invention, the nonionic fluorine-based compound as the component (C) may be used alone or in combination of two or more.
It is usually 100 to 10 relative to the solid content of the photoresist composition.
000 ppm, preferably in the range of 1000 to 6000 ppm. If the blending amount is less than 100 ppm, the object of the present invention is not sufficiently achieved, and 10,000 ppm is not achieved.
If it exceeds, the softening temperature of the photoresist composition decreases, which is not preferable. In particular, when the content of the nonionic fluorine-based compound in the resist composition increases, problems such as a decrease in sensitivity and a narrow focal depth range occur. Those that exhibit the effects of foaming property and wetting property are preferable.

In the composition of the present invention, the above (A),
Components (B) and (C) are composed of 60 to 90% by weight of alkyl 2-oxypropionate and 40 to 10% by weight of alkyl acetate.
Mixed solvent of alkyl 2-oxypropionate 50-9
It is necessary to dissolve it in a mixed solvent of 0% by weight and 50 to 10% by weight of propylene glycol monoalkyl ether acetate or propylene glycol monoalkyl ether acetate. Examples of the alkyl 2-oxypropionate include methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate, and ethyl 2-oxypropionate is most preferable. Alkyl acetate includes methyl acetate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate and the like, with butyl acetate being most preferred. Examples of the alkyl group of propylene glycol monoalkyl ether acetate include a methyl group, an ethyl group, a propyl group, and the like, and a methyl group is most preferable.

Conventionally, ethylene glycol monoethyl ether acetate has been widely used as a solvent for a positive photoresist composition and has been used as a practical solvent. However, at present, its toxicity poses a problem and its environmental concentration is low. Since it is regulated and cannot be used, highly safe ethyl lactate, propylene glycol monomethyl ether acetate, etc. have been proposed as alternative solvents, and are used as resist solvents. However, the ethyl lactate alone solvent has a problem that when the resist layer is provided on the substrate, the dispersion of the film thickness on the substrate surface is large and the in-plane uniformity is poor when the ethyl lactate alone solvent is used. Further, with respect to such a solvent, the conventional fluorine-based activators that have been used so far have insufficient defoaming properties and wetting properties, which causes problems such as poor coating film and poor development.

On the other hand, in the positive photoresist composition of the present invention, a mixed solvent of alkyl 2-oxypropionate and alkyl acetate in a predetermined ratio, a predetermined ratio of alkyl 2-oxypropionate and propylene glycol monoalkyl ether acetate. By combining the mixed solvent or the propylene glycol monoalkyl ether acetate single solvent with the predetermined (C) component, the safety is high, the occurrence of striation can be suppressed, and the defoaming property and the wetting property are excellent. It is possible to form a desired pattern without causing problems such as poor coating film and poor development.

In the composition of the present invention, the polyhydroxybenzophenones and the bis [(poly) hydroxyphenyl] are optionally used as sensitizers in order to further enhance the sensitivity within the range where the object of the present invention is not impaired. ] Alkanes, said 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene, or said tris (hydroxyphenyl) methanes or its methyl substitution The body and the like can be used in combination. The compound used in combination can provide a practical photoresist composition having excellent sensitizing effect, high sensitivity, and a small amount of dimensional change with respect to the exposure amount.

If desired, other sensitizers such as mercaptooxazole, mercaptobenzoxazole, mercaptooxazoline, mercaptobenzothiazole, benzoxazoline, benzothiazolone, mercaptobenzimidazole, Urazol, thiouracil, mercaptopyrimidine, imidazolone and their derivatives can be used in combination.

One of these sensitizers may be used,
Two or more kinds may be used in combination, and the mixing ratio thereof is usually 0.1% with respect to 100 parts by weight of the alkali-soluble resin.
It is selected in the range of 1 to 40 parts by weight, preferably 0.5 to 35 parts by weight. If this amount is less than 0.1 parts by weight, the sensitizing effect will not be sufficiently exerted, and if it exceeds 40 parts by weight, the sensitizing effect will not be obtained for the amount and is rather uneconomical. The optimum amount thereof is appropriately selected depending on the kind of the photosensitive component.

Further, in the composition of the present invention, resolution,
An isocyanurate compound may be added as an auxiliary agent for improving the residual film rate. Examples of this isocyanurate compound include 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl) -3-hydroxy-2,6-
Examples thereof include diethylbenzyl) isocyanurate and 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate. These may be used alone or in combination of two or more, and the mixing ratio thereof is usually 0.5 to 15 parts by weight with respect to 100 parts by weight of the alkali-soluble resin,
It is preferably selected in the range of 1.0 to 10 parts by weight.

In the composition of the present invention, in order to suppress the effect of standing waves, benzyl 2-hydroxybenzoate, 4
-Benzyl hydroxybenzoate, ethyl 2-hydroxybenzoate, hexyl 2-hydroxybenzoate and other hydroxybenzoic acid esters, 2-tert-butyl-4
Tert-Butyl-methylphenols such as -methylphenol, 2-tert-butyl-6-methylphenol, 4-tert-butyl-2-methylphenol and the like can be included. The blending amount of these is usually 1 to 10 parts by weight with respect to 100 parts by weight of the alkali-soluble resin,
It is preferably selected in the range of 2 to 5 parts by weight.

[0033]

The positive photoresist composition of the present invention comprises
(1) Since striation does not occur, excellent coatability can be formed and a uniform resist film can be formed. (2) Since defoaming property is excellent, even when the resist solution is applied onto the substrate. A desired resist pattern can be obtained without causing defective development of the resist film due to bubbles and development failure. (3) Since the wettability is excellent, bubbles adhere to the resist film during resist development. In addition, it is possible to obtain a desired pattern without causing development failure, the developing solution spreads quickly, the amount of the developing solution used is small, and the developing solution easily spreads uniformly on the resist film, It has features such as.

[0034]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Various physical properties of the composition were determined as follows. (1) Striation The sample was spin-coated on a 6-inch silicon wafer at 4000 rpm for 20 seconds using a spinner, and the surface of the resist film was visually observed to examine the occurrence of striation. The case where no striation was observed was evaluated as ◯, and the case where it was recognized was evaluated as x.

(2) Defoaming property The sample was spin-coated on a 6-inch silicon wafer in the same manner as in (1) above, and the surface of the resist film was visually observed to examine the occurrence of coating film defects due to bubbles. It was ○: No film defects due to bubbles were observed, ×:
Evaluated as.

(3) Wetting characteristics Pure water was dropped on the resist film, and the surface contact angle of the resist film with respect to pure water was measured using a goniometer.
In this case, if the value of the surface contact angle is less than 68 °, ○, 6
Those having an angle of 8 ° or more were evaluated as x. It should be noted that the smaller the value of the surface contact angle, the better the wettability of the resist film, and at 68 ° or more, the developing solution is repelled, resulting in poor development and formation of a desired pattern.

(4) Pattern shape The sample was spin-coated on a 6-inch silicon wafer at 4000 rpm for 20 seconds using a spinner and dried on a hot plate at 90 ° C. for 90 seconds to give a film thickness of 1.05 μm.
m resist film was obtained. A reduction projection exposure apparatus NSR-1755i7A (manufactured by Nikon Corporation, NA = 0.
50) was used for exposure at intervals of 0.1 to 0.01 seconds, and then paddle development was performed at 23 ° C. for 1 minute using a 2.38 wt% tetramethylammonium hydroxide aqueous solution. Then, it was washed with water for 30 seconds and dried to obtain a resist pattern.

At that time, the cross-sectional shape of the obtained resist pattern having a line and space width of 0.40 μm was taken by SEM.
(Scanning electron microscope) Observed by a photograph, the one that faithfully reproduces the mask pattern is ○, defective development occurs,
Those in which the mask pattern was not reproduced were evaluated as x.

Example 1 m-cresol and p-cresol in a weight ratio of 40:60
The mixture was mixed at a ratio of 1., formalin was added thereto, and the mixture was condensed by an ordinary method using an oxalic acid catalyst to obtain cresol novolac. 100 parts by weight of cresol novolac having a weight average molecular weight of 6000 obtained by subjecting this resin to a fractionation treatment and cutting the low-molecular region, 1 mol of 2,3,4,4'-tetrahydroxybenzophenone and naphthoquinone-1,
25 parts by weight of esterification reaction product with 4.0 mol of 2-diazide-5-sulfonyl chloride, 25 parts by weight of bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane and nonionic fluorine -Based compound EF-121 (manufactured by Tochem Products) 5000
After dissolving ppm in a mixed solvent of 360 parts by weight of ethyl 2-oxypropionate and 40 parts by weight of butyl acetate, this was filtered using a membrane filter having a pore size of 0.2 μm to prepare a positive photoresist composition. For this, striation, defoaming property, wetting property and pattern shape were determined. The results are shown in Table 1.

Examples 2 to 7 and Comparative Examples 1 to 3 Positive type was carried out in the same manner as in Example 1 except that the kind and amount of the nonionic fluorine-based compound were changed as shown in Table 1. A photoresist composition was prepared. For this, striation, defoaming property, wetting property and pattern shape were determined. The results are shown in Table 1.

Example 8 MF-1 was used in place of the nonionic fluorine-based compound of Example 1.
00 was used and a positive photoresist composition was prepared in the same manner as in Example 1 except that the compounding amount was changed to 300 ppm. About this thing, striation, defoaming,
Wetting characteristics and pattern shape were determined. The results are shown in Table 1.

Example 9 X-70 was used in place of the nonionic fluorine compound of Example 1.
A bodi type photoresist composition was obtained in the same manner as in Example 1 except that -092 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd., nonionic fluorine-containing organosiloxane compound) was used and the compounding amount was 250 ppm. For this, striation, defoaming property, wetting property and pattern shape were determined. The results are shown in Table 1.

[0044]

[Table 1]

[Note] 1) FC-430: Fluorochemical-Fluorosurfactant Fluorard "FC-430" manufactured by Sumitomo 3M 2) S-382: Fluorosurfactant Surflon "S- manufactured by Asahi Glass Co., Ltd." 382 "3) EF-122A: JEMCO Inc. fluorosurfactants EFTOP" EF-122A ", structural _{formula; C 8 F 17 SO 2 (} C 3 H 7) (C 2 H 4 O) 20 H 4) α: a mixed solvent of 90% by weight of ethyl 2-oxypropionate and 10% by weight of butyl acetate

Examples 10 to 15 and Comparative Examples 4 to 5 In Example 1, the solvent mixture shown in Table 2 was used instead of the mixed solvent.
Further, a bodi type photoresist composition was obtained in the same manner as in Example 1 except that the kind and amount of the nonionic fluorine-based compound were changed as shown in Table 2. For this, striation, defoaming property, wetting property and pattern shape were determined.
The results are shown in Table 2.

[0047]

[Table 2]

[Note] 1) 70% by weight of β: ethyl 2-oxypropionate and 30% of propylene glycol monomethyl ether acetate
Wt% mixed solvent 2) γ: propylene glycol monomethyl ether acetate

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Koichi Takahashi, 150 Nakamaruko, Nakahara-ku, Kawasaki-shi, Kanagawa Tokyo Ohka Kogyo Co., Ltd. (72) Hidekatsu Ohara 150, Nakamaruko, Nakahara-ku, Kawasaki, Kanagawa Higashi Kyoka Industrial Co., Ltd. (72) Inventor Hisasa Nakayama 150 Nakamaruko, Nakahara-ku, Kawasaki, Kanagawa Tokyo Ohka Kogyo Co., Ltd. (72) Inventor Hiroki Yamamoto 150 Nakamaruko, Nakahara-ku, Kawasaki, Kanagawa Tokyo Ohka Kogyo (72) Inventor Ikuo Akutsu 150 Nakamaruko, Nakahara-ku, Kawasaki, Kanagawa Tokyo Ohka Kogyo Co., Ltd. (72) Inventor Nobuo Tokutake 150 Nakamaruko, Nakahara-ku, Kawasaki, Kanagawa Tokyokyoka Kogyo Co., Ltd.

Claims (5)

[Claims] 1. An (A) alkali-soluble resin, (B) a quinonediazide group-containing compound, and (C) a general formula: [Wherein R _f is a fluorinated alkyl group having 6 to 10 carbon atoms in which some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms, R ¹ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
R ² is an alkyl group having 2 or more hydroxyl groups and having 2 to 5 carbon atoms, — (CH ₂ CH ₂ O) _n —R ³ (wherein R ³ is a hydrogen atom or a benzoyl group, and n is an integer of 1 to 10). Yes) or-
CH ₂ COOR ⁴ (R ⁴ is an alkyl group having 1 to 5 carbon atoms) The compound represented by which] the general formula _{R g - (CH 2) m} -OCH 2 CH (OH) -CH 2 OH ( formula Wherein R _g is a compound represented by a perfluoroalkyl group having 4 to 20 carbon atoms, m is an integer of 1 or 2, and a nonionic compound having only a perfluoroalkyl group-containing siloxane bond and a polyoxyethylene type polyether bond. At least one nonionic fluorine-based compound selected from the organic fluorine-containing organosiloxane compounds,
(D) Mixed solvent of 60 to 90% by weight of alkyl 2-oxypropionate and 40 to 10% by weight of alkyl acetate, 50 to 90% by weight of alkyl 2-oxypropionate and 50 to 1 of propylene glycol monoalkyl ether acetate
A positive photoresist composition obtained by dissolving 0% by weight of a mixed solvent or propylene glycol monoalkyl ether acetate. 2. The content of the nonionic fluorine-based compound as the component (C) is 100 to 10,000 with respect to the solid content of the composition.
The positive photoresist composition according to claim 1, which is in ppm. 3. The positive photoresist composition according to claim 1, wherein the group represented by R _f of the nonionic fluorine-based compound as the component (C) is a C ₇ F ₁₅ group or a C ₈ F ₁₇ group. 4. The group represented by R _g of the nonionic fluorine-based compound of the component (C) is a C ₄ F ₉ group, a C ₆ F ₁₃ group or a C ₈ F ₁₇ group.
The positive photoresist composition according to claim 1, which is a group. 5. The positive photoresist composition according to claim 1, wherein the subscript m of the nonionic fluorine-based compound as the component (C) is 2.