JP2001109144A - Positive photoresist composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an excellent coating property and a uniform photoresist film, because it does not cause drop mark unevenness or radial unevenness (striation), and is particularly useful for LCD and LSI manufacturing. A positive photoresist composition is provided. SOLUTION: With respect to a basic composition comprising an alkali-soluble novolak type resin and a quinonediazide group-containing compound,
A positive photoresist composition comprising a surfactant, wherein the surfactant comprises a specific nonionic surfactant and a fluorine-based surfactant.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive type photoresist composition, and more particularly, to a method in which no drop mark unevenness or radial unevenness (striation) occurs.
Excellent coatability, can form a uniform photoresist film,
In particular, the present invention relates to a positive photoresist composition useful for manufacturing LCDs and LSIs.

[0002]

2. Description of the Related Art A typical positive type photoresist used in the production of LCDs and LSIs has a basic composition of an alkali-soluble novolak type resin and a compound containing a quinonediazide group. Is used by applying a substance dissolved in an organic solvent onto a substrate surface having been subjected to an appropriate surface treatment and drying. However, when a photoresist solution is applied on a substrate and when the obtained photoresist film is dried, there is a problem that unevenness of application called radial unevenness (striation) occurs in the photoresist film. To solve this problem, for example, as described in JP-A-10-307385, radial unevenness (striation) is obtained by adding a fluorine-based surfactant to a positive photoresist composition. Prevention has been made. Also, in a photosensitive resin composition used for a photosensitive printing plate, it has been practiced to add a fluorine-based surfactant to prevent coating unevenness in a coating step and a drying step (Japanese Patent Application Laid-Open No. 3-172849). JP-A-3-219
248).

[0003]

As described above, by adding a fluorine-based surfactant to a photoresist composition, the problem of radial unevenness (striation) can be almost completely solved, but a problem arises in that the photoresist and the substrate are not covered. However, since the interfacial tension increases, the photoresist film formed on the substrate by the spin coating has a problem in that spots on the photoresist film become uneven. In particular, in the case of a photoresist for an LCD, unevenness of drop marks is likely to occur during the spin coating of a photoresist film, and the causes are as follows. That is, when a photoresist is spin-coated on a large substrate such as 360 × 465 mm, 550 × 650 mm, etc., 1) the rotation time is as short as ten and several seconds to improve the productivity, 2) the chamber size is large, and And 3) that the photoresist for LCD has a low viscosity, that is, a composition having a low solid content and a high solvent content. As described above, the application conditions of the photoresist used for manufacturing the LCD are very strict, and
CDs have been increased in screen size and definition, and demands for prevention of coating unevenness during coating and drying have become more severe.

That is, the present invention has solved the above-mentioned conventional problems, and has excellent coating properties and uniform photoresist film because it does not cause drop mark unevenness or radial unevenness (striation). Especially LC
The object of the present invention is to provide a positive photoresist composition useful for manufacturing D and LSI.

[0005]

SUMMARY OF THE INVENTION The present invention provides a positive photoresist composition containing a surfactant with respect to a basic composition comprising an alkali-soluble novolak resin and a compound containing a quinonediazide group. The present invention relates to a positive photoresist composition, wherein the agent contains a nonionic surfactant represented by the following formulas (A-1) to (H) and a fluorine-based surfactant. Formula (A-1):

[0006]

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Wherein A ¹ , A ² , A ³ and A ⁴ each represent a polypropylene oxide group, and B ¹ , B ² , B ³ and B ⁴ each represent a polyethylene oxide group. A compound having a molecular weight of 1,000 to 40,000 and containing 5 to 80% by weight of a polyethylene oxide group based on the average molecular weight, formula (A-2):

[0008]

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Wherein A ⁵ , A ⁶ , A ⁷ and A ⁸ each represent a polypropylene oxide group, and B ⁵ , B ⁶ , B ⁷ and B ⁸ each represent a polyethylene oxide group. is 2,000 to 30,000, compound polyethylene oxide group is contained 5 to 80% by weight, based on the average molecular weight, the formula (B-1): HO- B 9 -A 9 -B 1 0 -OH (B -1) (wherein, a ⁹ represents a polypropylene oxide group, B ⁹ and B ^{1 0} is shown by representing the polyethylene oxide group),
Average molecular weight of 900～4,000, compound polyethylene oxide group is contained 5 to 55% by weight, based on the average molecular weight, the formula (B-2): HO- A 1 0 -B 1 1 -A 1 1 - OH (B-2) (wherein, a ^{1 0} and a ^{1 1} represents a polypropylene oxide group, B ^{1 1} represents a polyethylene oxide group) represented by the average molecular weight be 1,000 to 4,000 Having a polyethylene oxide group content of 5 to 55 based on the average molecular weight.
% By weight of the compound of formula (C):

[0010]

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Wherein R ¹ represents an alkyl group having 5 to 25 carbon atoms, EO represents an oxyethylene group, and a and b each represent an integer of 2 to 40. , Formula (D): R ² -O- (EO) _c -H (D) (wherein, R ² represents an alkyl group having 5 to 25 carbon atoms, EO represents an oxyethylene group, and c represents 2 A polyoxyethylene alkyl ether represented by the following formula (E): R ³ —COO— (EO) _d —H (E) (wherein R ³ is alkyl having 5 to 25 carbon atoms) EO represents an oxyethylene group, and d represents an integer of 2 to 40), a polyoxyethylene monofatty acid ester represented by the formula (F): R ⁴ —COO— (EO) _e —CO—R ⁵ (F) (wherein, R ⁴ and R ⁵ is an alkyl group having 5 to 25 carbon atoms Represents, EO represents an oxyethylene group, e is 2 to 40
A polyoxyethylene difatty acid ester represented by the formula (G):

[0012]

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Wherein R ⁶ represents an alkyl group having 5 to 25 carbon atoms, EO represents an oxyethylene group, and f represents 2
A polyoxyethylene alkylphenyl ether represented by the formula (H):

[0014]

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(Wherein EO represents an oxyethylene group;
g and h represent an integer of 2 to 40).

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The nonionic surfactant used in the present invention is at least one selected from the compounds represented by formulas (A-1) to (H).

The compound of the formula (A-1) used in the present invention is
To four active hydrogen ethylenediamine as the core, hydrophobic polypropylene oxide groups [-CH (CH ₃₎ CH ₂ O
Is a block copolymer obtained by polymerizing a polyoxyethylene group [a polymer group having —CH ₂ CH ₂ O— as a structural unit].

The compound of formula (A-1) has an average molecular weight of 1,
000 to 4,000, and the content of the polyethylene oxide group in the compound is 5 to 80% by weight based on the average molecular weight. Preferably, the compound of formula (A-1) has an average molecular weight of 2,500 to 12,000,
The content of polyethylene oxide groups in this compound is 10 to 70% by weight based on the average molecular weight. Most preferably, the compound of formula (A-1) has an average molecular weight of 2,500 to 7,000, and the content of polyethylene oxide groups in this compound is 10 to 40% by weight based on the average molecular weight. is there.

The compounds of the formula (A-1) used in the present invention include, for example, 304, 504, 701, 702, 704, 707 of the TETRONIC (registered trademark) series.
901, 904, 908, 1101, 1102, 110
4, 1107, 1301, 1302, 1304, 130
7, 1501, 1502, 1504, 1508 (or more,
BASF). Table 1 shows the average molecular weight and the content (% by weight) of the polyethylene oxide groups based on the average molecular weight.

[0020]

[Table 1]

The compound of the formula (A-2) used in the present invention is
A hydrophilic polyoxyethylene group [polymer group having —CH ₂ CH ₂ O— as a structural unit] is polymerized on four active hydrogens with ethylenediamine as a nucleus, and a hydrophobic polypropylene oxide group [—CH (CH ₃ ) Polymer group having CH ₂ O— as a constitutional unit].

The compound of formula (A-2) has an average molecular weight of 2,
2,000 to 21,000, and the content of the polyethylene oxide group in this compound is 5 to 80% by weight based on the average molecular weight. Preferably, the compound of formula (A-2) has an average molecular weight of 2,500 to 12,000, and the content of polyethylene oxide groups in the compound is 10 to 70% by weight based on the average molecular weight. . Most preferably, the compound of formula (A-2) has an average molecular weight of 3,000 to 6,000, and the content of polyethylene oxide groups in this compound is 10 to 40% by weight based on the average molecular weight. is there.

The compounds of the formula (A-2) used in the present invention include, for example, 50R1, 50R4, 50R8, 70R1, 70R of the TETRONIC (registered trademark) series.
2, 70R4, 90R1, 90R4, 90R8, 110
R1, 110R2, 110R7, 130R1, 130R
2, 150R1, 150R4, 150R8 (above, BA
SF Co., Ltd.). Table 2 shows the average molecular weight and the content (% by weight) of polyethylene oxide groups based on the average molecular weight.

[0024]

[Table 2]

The compound represented by the formula (B-1) used in the present invention has a hydrophobic polypropylene oxide group [—CH
(CH ₃ ) a polymer group having CH ₂ O— as a structural unit]
It is a block copolymer sanded with a hydrophilic polyethylene oxide group [polymer group having —CH ₂ CH ₂ O— as a structural unit].

The compound of the formula (B-1) has an average molecular weight of 90
0 to 4,000, and the content of the polyethylene oxide group in this compound is 5 to 5 based on the average molecular weight.
55% by weight. Preferably, the compound of formula (B-1) has an average molecular weight of from 900 to 2,200, and the content of polyethylene oxide groups in the compound is from 5 to 35% by weight based on the average molecular weight. More preferably, the compound of formula (B-1) has an average molecular weight of 900-2,
The content of the polyethylene oxide group in this compound is 5 to 15% by weight based on the average molecular weight. Most preferably, the compound of formula (B-1) has an average molecular weight of 900 to 1,200, and the content of polyethylene oxide groups in the compound is 5 to 15% by weight based on the average molecular weight.

The compound of the formula (B-1) used in the present invention includes, for example, L31, L35, L42, L43, L44, L61 of the PLURONIC (registered trademark) series.
L62, L63, L64, L72, L81, L92, L
101, P65 (all manufactured by BASF) and the like. Table 3 shows the average molecular weight and the content (% by weight) of polyethylene oxide groups based on the average molecular weight.

[0028]

[Table 3]

The compound of the formula (B-2) used in the present invention is
A hydrophilic polyethylene oxide group [polymer group having —CH ₂ CH ₂ O— as a structural unit] is replaced with a hydrophobic polypropylene oxide group [polymer group having —CH (CH ₃ ) CH ₂ O— as a structural unit]. It is a sandwiched block copolymer.

The compound of the formula (B-2) has an average molecular weight of 1,
000 to 4,000, and the content of the polyethylene oxide group in the compound is 5 to 55% by weight based on the average molecular weight. Preferably, the compound of formula (B-2) has an average molecular weight of 1,000 to 4,000, and the content of the polyethylene oxide group in the compound is 15 to 45% by weight based on the average molecular weight. . Preferably, the compound of formula (B-2) has an average molecular weight of 1,000 to 2,900, and the content of the polyethylene oxide group in the compound is 5 to 55% by weight based on the average molecular weight. It is. More preferably, the formula (B-
The compound (2) has an average molecular weight of 2,000 to 2,900, and the content of the polyethylene oxide group in the compound is 15 to 45% by weight based on the average molecular weight.

The compound of the formula (B-2) used in the present invention includes, for example, 10R5, 12R3, 17R1, 17R2, 17R of PLURONIC (registered trademark) R series.
4, 22R4, 25R1, 25R2, 25R4, 31R
1, 31R2 (all manufactured by BASF) and the like. Table 4 shows the average molecular weight and the content (% by weight) of polyethylene oxide groups based on the average molecular weight.

[0032]

[Table 4]

The “average molecular weight” in the formulas (A-1), (A-2), (B-1) and (B-2) is as follows.
It is calculated based on the hydroxyl value measured according to the following means (phthalation method).

Reagent to be used : phthalic anhydride in pyridine solution: 42 g of phthalic anhydride is completely dissolved in 300 ml of pyridine and aged at 70 ° C. for 2 hours or at room temperature overnight. In addition, this reagent is stored in a colored bottle, renewed within 8 days, and the colored reagent is not used. Pyridine 0.5N sodium hydroxide solution Phenolphthalein pyridine solution (1W / V%)

Procedure Properly weigh a specified amount of sample into a 300 ml flask [S (g)]. In the case collection amount is less than 1g 10 ^{- 1}
If the amount is 1 g or more, weigh in mg order. Add exactly 25 ml of a pyridine solution of phthalic anhydride with a whole pipette, seal the cochlear with pyridine and heat on a boiling water bath for 2 hours (shake every 15 minutes). After heating, remove from the water bath and cool to room temperature. Rinse off the coincens with pyridine (the wash is dropped into the flask) and add exactly 0.5N sodium hydroxide solution with a 50 ml whole pipette. 1 indicator (phenolphthalein solution in pyridine)
Add 0 drops. Titrate with 0.5N sodium hydroxide solution [A (m
l)]. The point that remains red for at least 15 seconds is the end point. In this test, a blank test is performed under the same conditions. [B (m
l)].

Calculation of average molecular weight Calculation of hydroxyl value OHV = [28.05 × (BA) × f] / S In the formula, OHV is (mgKOH / g) of hydroxyl value, and B is titration in blank test. Required amount of 0.5N sodium hydroxide solution (m
l), A indicates the amount (ml) of 0.5N sodium hydroxide solution required for titration of the sample, f indicates the factor of the 0.5N sodium hydroxide solution, and S indicates the amount of sample (g). When the sample contains a free acid, it is corrected by the following equation. Correction value = hydroxyl value + acid value Calculation of average molecular weight Average molecular weight = (56.1 × 2 × 1000) / OHV In the formula, 56.1 is a formula weight of KOH, and 2 is a functional group (OH group).
Is the number of

In the polyoxyethylene alkylamine represented by the formula (C) used in the present invention, R ¹ is an alkyl group having 5 to 25 carbon atoms, and a and b are integers of 2 to 40. Preferably, R ¹ is an alkyl group having 10 to 20 carbon atoms, and a and b are integers of 5 to 20.

The polyoxyethylene alkylamine represented by the formula (C) used in the present invention includes, for example, D-3110 and D-110 of the Pionin series manufactured by Takemoto Yushi Co., Ltd.
3120, D-3412, D-3440, D-351
0, D-3605 and the like.

In the polyoxyethylene alkyl ether represented by the formula (D) used in the present invention, R ² is an alkyl group having 5 to 25 carbon atoms, and c is an integer of 2 to 40. Preferably, R ² is an alkyl group having 10 to 20 carbon atoms, and c is an integer of 5 to 20.

The polyoxyethylene alkyl ether represented by the formula (D) used in the present invention includes, for example, D-1305 and D-1305 of the Pionin series manufactured by Takemoto Yushi Co., Ltd.
-1315, D-1405, D-1420, D-150
4, D-1508, D-1518 and the like.

In the polyoxyethylene monofatty acid ester represented by the formula (E) used in the present invention, R ³ is an alkyl group having 5 to 25 carbon atoms, and d is an integer of 2 to 40. Preferably, R ³ is an alkyl group having 10 to 20 carbon atoms, and d is an integer of 5 to 20.

Examples of the polyoxyethylene monofatty acid ester represented by the formula (E) used in the present invention include, for example, D-2112- of Pionin series manufactured by Takemoto Yushi Co., Ltd.
A, D-2112-C, D-2123-C and the like.

In the polyoxyethylene difatty acid ester represented by the formula (F) used in the present invention, R ³ and R ⁴ are an alkyl group having 5 to 25 carbon atoms, and e is an integer of 2 to 40. Preferably R ³ and R ⁴ are 10 to 20 carbon atoms
And e is an integer of 5 to 20.

The polyoxyethylene difatty acid ester represented by the formula (F) used in the present invention includes, for example, D-2405-Pionin series manufactured by Takemoto Yushi Co., Ltd.
A, D-2410-D and D-2110-D.

In the polyoxyethylene alkylphenyl ether represented by the formula (G) used in the present invention, R ⁶
Is an alkyl group having 5 to 25 carbon atoms, and f is an integer of 2 to 40. Preferably, R ⁶ is an alkyl group having 10 to 20 carbon atoms, and f is an integer of 5 to 20.

The polyoxyethylene alkylphenyl ether represented by the formula (G) used in the present invention includes, for example, D-40 of the Pionin series manufactured by Takemoto Yushi Co., Ltd.
6, D-410, D-414, D-418 and the like.

In the polyoxyethylene tetramethyldecyne diol diether represented by the formula (H) used in the present invention, g and h are integers of 2 to 40. Preferably, g and h are integers of 5 to 20, more preferably g and h are integers of 10 to 20.

The polyoxyethylene tetramethyl decyne diol diether represented by the formula (H) used in the present invention includes, for example, 104S, 420, 440 and 465 of Surfynol series manufactured by Nissin Chemical Industry Co., Ltd. 48
5 and the like.

The nonionic surfactants used in the present invention may be used alone or in combination of two or more.

The amount of the nonionic surfactant used in the present invention is preferably 0.01 to 25 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble novolak resin described below and the quinonediazide group-containing compound described later. Is 0.1
10 to 10 parts by weight, more preferably 0.5 to 5 parts by weight.

The fluorosurfactant used in the present invention is not particularly limited, and various known ones can be used. Examples thereof include FC-430 and FC-431 of the Florad series manufactured by Sumitomo 3M Limited. 17 of Megafac (registered trademark) series manufactured by Dainippon Ink and Chemicals, Inc.
1, 172, 173, 178K, 178A, R08, S-381, S-3 of Surflon series manufactured by Asahi Glass Co., Ltd.
83, S-393, SC-101, SC-105,
FT250, FT251, DFX18 of the Neogent (registered trademark) series manufactured by Neos Co., Ltd., E of the F-top (registered trademark) series manufactured by Tochem Products Co., Ltd.
F351, EF352, EF122A, EF122B,
EF122C, Unidyne (registered trademark) series DS-401, DS-403, DS manufactured by Daikin Industries, Ltd.
-451 and the like.

The fluorosurfactants used in the present invention may be used alone or in combination of two or more.

The amount of the fluorine-based surfactant used in the present invention is 0.001 to 0.5 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble novolak resin described below and the quinonediazide group-containing compound described later. , Preferably 0.0
5 to 0.1 parts by weight.

The alkali-soluble novolak resin as a film-forming substance used in the present invention includes a resin obtained by condensing a phenol and an aldehyde in a bulk or in a solvent in the presence of an acid catalyst. Phenols include phenol, o-, m- or p-cresol, 2,
5-xylenol, 3,6-xylenol, 3,4-xylenol, 2,3,5-trimethylphenol, 4-
t-butylphenol, 2-t-butylphenol, 3
-T-butylphenol, 2-ethylphenol, 3-
Ethylphenol, 4-ethylphenol, 3-methyl-6-t-butylphenol, 4-methyl-2-t-butylphenol, 2-naphthol, 1,3-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,
And aromatic hydroxy compounds such as 7-dihydroquinaphthalene. Aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propylaldehyde, benzaldehyde, phenylaldehyde and the like. Examples of the catalyst include organic acids (formic acid, oxalic acid, p-toluenesulfonic acid, trichloroacetic acid, etc.), inorganic acids (phosphoric acid, hydrochloric acid, sulfuric acid, perchloric acid, etc.),
Valent metal salts (such as zinc acetate and magnesium acetate). These alkali-soluble novolak resins may be used alone or in combination of two or more.

The quinonediazide group-containing compound as a photosensitive component used in the present invention includes, for example, 2,3,4
-Trihydroxybenzophenone, 2,3,4,4'-
Polyhydroxybenzophenone such as tetrahydroxybenzophenone and naphthoquinone-1,2-diazide 5-
Sulfonic acid or naphthoquinone-1,2-diazide-4-
Examples thereof include a complete ester compound and a partial ester compound with sulfonic acid. In addition, other quinonediazide compounds, for example, ortho-benzoquinonediazide, orthonaphthoquinonediazide, orthoanthraminonediazide or orthonaphthoquinonediazidesulfonic acid esters and other nuclear-substituted derivatives, and further have orthonaphthoquinonesulfonyl chloride and a hydroxyl group or an amino group. Compounds such as phenol, p-methoxyphenol, dimethylphenol, hydroquinone, bisphenol A, naphthol, carbinol, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3
Dimethyl ether, gallic acid, gallic acid esterified or etherified leaving some of the hydroxyl groups, aniline, p
Reaction products with -aminodiphenylamine and the like can also be used. These may be used alone or in combination of two or more. These quinonediazide group-containing compounds include, for example, polyhydroxybenzophenone and naphthoquinone-1,2-diazide-4-sulfonyl chloride in a suitable solvent such as dioxane, triethanolamine, alkali carbonate, alkali hydrogen carbonate, etc. It can be produced by condensation in the presence of an alkali and complete or partial esterification.

The quinonediazide group-containing compound was used in an amount of 100 parts by weight of the alkali-soluble novolak resin.
5 to 30 parts by weight, preferably 10 to 20 parts by weight are blended.

The positive photoresist composition of the present invention comprises
Further compatible additives as needed, for example, a resin for improving the performance of the photoresist film, a plasticizer,
Conventional components such as a stabilizer, a dye for improving the visibility of the resist pattern after development, and a sensitizer for improving the sensitizing effect can be contained.

The positive photoresist composition of the present invention comprises
The alkali-soluble novolak resin, the quinonediazide group-containing compound, the fluorinated surfactant, the nonionic surfactant, and various additives used as necessary are dissolved in an appropriate solvent to form a solution.

As the solvent, 2-heptane, acetone,
Ketones such as methyl ethyl ketone and 1,1,1-trimethylacetone; ethylene glycol monoacetate;
Derivatives of polyhydric alcohols such as propylene glycol monoacetate, diethylene glycol or diethylene glycol monoacetate, such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether; cyclic ethers such as dioxane; ethyl lactate, methyl acetate Esters such as ethyl acetate, butyl acetate, methyl propionate, ethyl pyruvate, methyl 3-methoxypropionate and methyl 3-ethoxypropionate. These solvents may be used alone or in combination of two or more. The amount of the solvent used is usually 50 to 90 with respect to the positive photoresist composition of the present invention.
It is prepared so as to be% by weight.

In the method of using the positive photoresist composition of the present invention, a positive photoresist containing each of the above components is applied to a substrate by spin coating or slot coating, and dried to form a photoresist layer. I do. This is exposed to ultraviolet rays through a predetermined mask pattern using a low-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, arc lamp, xenon lamp, or the like. Next, this is added to a developing solution, for example, 1
When immersed in a weakly alkaline aqueous solution such as a 10% by weight aqueous solution of tetramethylammonium hydroxide, the exposed portions are selectively dissolved and removed, and a resist pattern faithful to the mask pattern can be formed on the substrate. Next, the exposed substrate is etched by a known method using the obtained resist pattern as a mask, and then the resist pattern is peeled off to form a circuit pattern on the substrate.

[0061]

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

Examples 1 to 13 m-cresol and p-cresol were mixed at a weight ratio of 6: 4, and 22.5 g of a cresol novolak resin (average molecular weight: 5,000) produced by a conventional method, and 2,3,4 , 4 '
-Naphthoquinone of tetrahydroxybenzophenone-
2.5 g of 1,2-diazide-5-sulfonic acid ester was dissolved in 75 g of propylene glycol monomethyl ether acetate. To the resulting solution A, 0.02 g of each of the fluorine-based surfactant and the nonionic surfactant shown in Table 5 was added to obtain a positive photoresist solution.

The obtained positive photoresist solution was spin-coated on a glass substrate having a surface coated with molybdenum so as to have a thickness of 1.5 μm.
The application state of the photoresist on the substrate surface was irradiated with a high-intensity sodium lamp, and visually observed for dripping trace unevenness and radial unevenness. Table 5 shows the results.

Comparative Examples 1-2 Using the solution A obtained in Examples 1-13 and the photoresist solution obtained by adding 0.02 g of the fluorinated surfactant shown in Table 5 to Solution A, Example 1 was used. In the same manner as in Examples 13 to 13, the presence or absence of dripping trace unevenness and radial unevenness (striation) was visually observed. Table 5 shows the results.

[0065]

[Table 5]

[0066]

The positive type photoresist composition of the present invention has excellent coatability and can form a uniform photoresist film because it does not cause dripping trace unevenness or radial unevenness (striation). And LSI manufacturing.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yoshitaka Kamada 300 Kanayahara, Sakura-mura, Oga-machi, Kitakanbara-gun, Niigata Pref. Ninja Kanayahara 300 Shipley Far East Co., Ltd. Sasami Plant F-term (reference) 2H025 AA00 AA02 AB16 AC01 AD03 BE01 BE10 CB29 CB53 CC04 EA05

Claims (1)

[Claims] Claims: 1. A basic composition comprising an alkali-soluble novolak resin and a quinonediazide group-containing compound,
In a positive photoresist composition containing a surfactant, the surfactant contains a nonionic surfactant represented by the following formulas (A-1) to (H) and a fluorine-based surfactant. A positive photoresist composition comprising: Formula (A-1): Wherein A ¹ , A ² , A ³ and A ⁴ represent a polypropylene oxide group, and B ¹ , B ² , B ³ and B ⁴ represent a polyethylene oxide group, and have an average molecular weight of 1,000. ~
A compound having a polyethylene oxide group content of 5 to 80% by weight, based on the average molecular weight, formula (A-2): Wherein A ⁵ , A ⁶ , A ⁷ and A ⁸ each represent a polypropylene oxide group, and B ⁵ , B ⁶ , B ⁷ and B ⁸ each represent a polyethylene oxide group, and have an average molecular weight of 2,000. ~
Is 30,000, compound polyethylene oxide group is contained 5 to 80% by weight, based on the average molecular weight, the formula (B-1): HO- B 9 -A 9 -B 1 0 -OH (B-1) ( wherein, a ⁹ represents a polypropylene oxide group, B ⁹ and B ^{1 0} is shown by representing the polyethylene oxide group),
Average molecular weight of 900～4,000, compound polyethylene oxide group is contained 5 to 55% by weight, based on the average molecular weight, the formula (B-2): HO- A 1 0 -B 1 1 -A 1 1 - OH (B-2) (wherein, a ^{1 0} and a ^{1 1} represents a polypropylene oxide group, B ^{1 1} represents a polyethylene oxide group) represented by the average molecular weight be 1,000 to 4,000 Having a polyethylene oxide group content of 5 to 55 based on the average molecular weight.
% By weight of a compound represented by the formula (C): (Wherein, R ¹ represents an alkyl group having 5 to 25 carbon atoms, EO represents an oxyethylene group, and a and b represent 2 to 4
A polyoxyethylene alkylamine represented by the formula (D): R ² —O— (EO) _c —H (D) wherein R ² is an alkyl group having 5 to 25 carbon atoms And EO represents an oxyethylene group, and c represents an integer of 2 to 40), a polyoxyethylene alkyl ether represented by the formula (E): R ³ —COO— (EO) _d —H (E) ( In the formula, R ³ represents an alkyl group having 5 to 25 carbon atoms, EO represents an oxyethylene group, and d represents an integer of 2 to 40), a polyoxyethylene monofatty acid ester represented by the formula (F): R ⁴ —COO— (EO) _e —CO—R ⁵ (F) (wherein, R ⁴ and R ⁵ represent an alkyl group having 5 to 25 carbon atoms, EO represents an oxyethylene group, and e represents 2-40
A polyoxyethylene difatty acid ester represented by the formula (G): (Wherein, R ⁶ represents an alkyl group having 5 to 25 carbon atoms, EO represents an oxyethylene group, f represents an integer of 2 to 40), and a formula ( H): (Wherein EO represents an oxyethylene group, and g and h are 2
A polyoxyethylene tetramethyldecinediol diether represented by the following formula: