WO1998001791A1

WO1998001791A1 - Positive photoresist composition

Info

Publication number: WO1998001791A1
Application number: PCT/JP1997/002373
Authority: WO
Inventors: Shoji Kawata; Hirokazu Higashi; Masahiro Nakamura
Original assignee: Nippon Zeon Co., Ltd.
Priority date: 1996-07-10
Filing date: 1997-07-09
Publication date: 1998-01-15

Abstract

A positive resist composition comprising: (A) an alkali-soluble phenolic resin and (B) a photosensitive agent consisting of an ester of quinonediazidesulfonic acid with a phenol, characterized in that the component (B) contains an ester (B1) of 1,2-naphthoquinonediazide-6-sulfonic acid with a phenol wherein 10 to 70 % of the phenolic hydroxyl groups of the phenol are esterified with a photosensitive group of formula (1) resulting from 1,2-naphthoquinonediazide-6-sulfonic acid.

Description

Description Posi-type photo resist composition

Technical field

The present invention relates to a positive-type photoresist composition containing an alkali-soluble phenol resin and a quinonediazide sulfonate, and more particularly, to a semiconductor device and a magnetic bubble memory. Li—Positive photo resist composition for fine processing required for the manufacture of devices, integrated circuits, etc. Background art

In recent years, as a photoresist composition for forming a semiconductor device, a positive photoresist composition has become more prevalent than a negative photoresist composition. It has become. This is because the negative photoresist composition has high sensitivity, but uses an organic solvent for development, so that the resist pattern swells greatly and has a problem in resolution. It is caused. On the other hand, the photoresist type photoresist composition can be developed with an aqueous alkali solution, so that the resist pattern swells little, has excellent resolution, and has a high semiconductor performance. It is thought that it can sufficiently cope with integration.

Conventionally, a positive-type photoresist composition generally used in this field is composed of an alkali-soluble phenol resin such as a novolak resin and a quinonedia disulfonate compound. It is. Since this positive photoresist composition is developed with an aqueous alkali solution, it has a small swelling and is excellent in resolution. In addition, such positive type The resolution of the resist composition has been further improved by improving the performance of the resist composition itself and the sophistication of the exposure machine, and it is now possible to form fine patterns of 0.5 m or less. ing.

However, conventional positive photoresist compositions have not always yielded satisfactory results in terms of the balance of various properties such as sensitivity, residual film ratio, resolution, heat resistance, and storage stability. Therefore, further improvement in performance is desired. In particular, in the formation of a fine pattern of 0.5 m or less, it is necessary to more strictly control the resist size, and therefore, a positive photoresist composition having higher dimensional accuracy is required. Is becoming increasingly required.

Conventionally, in positive-type photoresist compositions, various phenols such as 1,2-quinonediazido-4-sulfonate ester or 1 , 2 — Quinone diazide-5-Sulfonate has been used (Japanese Patent Publication No. Hei 3-48896, Japanese Patent Publication No. Hei 4-5202519, Japanese Patent Application Laid-Open No. — 1667805, Japanese Patent Application Laid-Open No. Hei 6 — 148878, Japanese Patent Application Laid-Open No. 7-159589, Japanese Patent Application Laid-Open No. 7-168355, etc.) . Some of these photosensitizers provide good resist properties for g-line (433 nm) exposure. However, these sensitizers can exert their performance in i-line (365 nm) exposure at a resist film thickness of about l / t / m or less, but the performance exceeds this. With the film thickness of the resist, there is a problem that a practical pattern cannot be obtained because the exposure of the exposure light by the photosensitive agent is large.

In recent years, as a light source, the conventional mercury lamp g-line has been reduced to a shorter wavelength mercury lamp i-line, and a reduced projection exposure apparatus has been used. Is being developed. For example, as a means to obtain a practical pattern by i-ray exposure, 1,2—naphthoquinone (2) —di Azido 6 — Ester of sulfonic acid with alcohols or phenols, or 1,2 — naphthoquinone 1 (2) — Diazide 6 — Sulfo It has been proposed to use a sulfonamide of a phosphoric acid and an organic amine as a dissolution inhibitor (photosensitizer) in combination with an alkali-soluble resin (Japanese Patent Application Laid-Open No. HEI 4-151336). No. 56).

However, 1,2-naphthoquinone-1 (2) -diazido-6-sulfonate ester of phenol X-norls specifically shown in the examples of the publication is Of the hydroxyl groups esterified with 1,2-naphthoquinone (2) -diazido 6-sulfonate in the total hydroxyl groups of the phenols The so-called esterification rate) is relatively large, with a charge ratio of 75 to 83%.

1,2—Naphthoquinone— (2) —diazido 6—sulfonate, which has such a high esterification rate, has a large i-line absorption, Sensitivity tends to decrease. In addition, 1,2-naphthoquinone- (2) -diazide-16-sulfonate ester having a high esterification rate is a resist containing an alkali-soluble phenol resin. There is a problem that the solubility in a solvent is low, and the photoresist composition is precipitated when stored for a long period of time. Alkali-soluble phenol resins and photosensitizers are used after being uniformly dissolved in the solvent. The obtained solution is applied on a substrate to form a resist film. If the photosensitizer precipitates during storage of the solution, it will not be possible to form a resist film with the specified sensitivity, and the precipitate will remain on the resist film as foreign matter. become. Disclosure of the invention

It is an object of the present invention to provide a positive type photo diode with a highly balanced sensitivity, resolution, pattern shape, focus tolerance, dimensional accuracy, storage stability, and the like. An object of the present invention is to provide a resist composition.

It is another object of the present invention to provide a photoresist type photoresist capable of forming a practical pattern by i-line (365 nm) exposure. is there.

The present inventors have conducted intensive studies to solve the problems of the prior art, and as a result, as a photosensitive agent used in combination with an alcohol-soluble phenol resin, a specific esterification ratio of 1, 2 — Naphthoquinone diazide — 6 — sulfonate (ie, 1,2 — naphthoquinone mono (2) -diazido 6 — sulfonate) It is possible to obtain a photoresist composition with excellent storage stability, good pattern shape, and excellent focus tolerance, dimensional accuracy, sensitivity, and resolution. Was found.

As photosensitizers, 1,2-naphthoquinone diazide 6-sulfonate and 1,2-naphthoquinone diazide 5-snorrephonate And / or 1,2-Naphthoquinone diazide 4-sulfonate can be used to improve the effect of inhibiting the dissolution in an alkaline developer and improve the pattern. I found that it was possible to get By adding a phenol compound as a resist property improver, the pattern shape, heat resistance, sensitivity and the like can be further improved. The present invention has been completed based on these findings.

Thus, according to the present invention, (A) an alkali-soluble phenol resin and (B) quinone diazide sulfonate of phenols are contained as photosensitizers. (B) quinonediazidosulfonate of phenols in the positive resist composition of the present invention contains 10 to 7 of all phenolic hydroxyl groups of the phenols. 0% is the formula (1)

1, 2 — naphthoquinone diazide 1 — 6 — 1,2 — naphthoquinone diazide 6 — esterified with a photosensitive group derived from sulfonate There is provided a positive photoresist composition comprising a sulfonate ester (B1). BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail.

(A) Alkali-soluble phenol resin

Examples of the alcohol-soluble phenol resin used in the present invention include, for example, a condensation reaction product of a phenol compound and an aldehyde, and a phenol compound and a ketone. Products of condensation reaction with phenols, vinylphenol-based polymers, isopropanol-based polymers, and hydrogenation reaction products of these phenolic resins I can do it. These soluble phenol resins can be used alone or in combination of two or more.

Examples of the phenol compound used herein include phenol, o—cresol, m—cresol, and p—cresol 2,3—dimethanol. Nore, 2, 5 — dimethyl phenol, 3 4 dimethyl phenol, 3, 5 — dimethyl phenol, 2 dimethyl, 2, 6 — Dimethylinophenol, 2, 3, 5 Trimethylphenol, 2, 3, 6 — Trimethylphenol, 2 t-butylinole, 3 — t-butylinole Knol, 4-t-butylphenol, 2 — Methyl benzo resin, 4 — Methyl benzo resin, 5 — Methyl benzo resin, 4 t-butyl catechol, 2 — Methoxy phenol Nor, 3—Methoxy phenol, 2—Propyl phenol, 3—Propyl phenol, 41 propyl phenol, 2—Iso propyl : L-north, 3—isopropylphenol, 4—isopropylphenol, 2—methoxy 1-5—methizolenophenol, 2—t-butyl-5—methyl Chinole Enole, Thymol, and Isotimol can be mentioned.

Among these phenolic compounds, 0-cresol, m-cresol, p-cresol, 2,3—dimethyl phenol, 3, 4 — Dimethyltinole, 3, 5 — Dimethylinole, 2, 5 — Dimethylinole, 2, 3, 5 — Trimethylinole, and 2, 3, 6 — Trimethylinophenol is particularly preferred. Each of these phenol compounds can be used alone or in combination of two or more.

Examples of the aldehydes include phormarin, paraform aldehyde, trioxane, acetate aldehyde, propyl aldehyde, benzaldehyde, and phenyl aldehyde. Aldehyde, a—vinylpropyl, / 3—vinylpropyl, o—hydroxybenzyl aldehyde, m—hydrobenzylaldehyde, p— Hydroxybenzaldehyde, 0 — Black Benzaldehyde, m — Black Benzaldehyde, p — Black Benzaldehyde, o — Nitrobenzaldehyde H, m — Two-Trobenzaldehid, p — Two-Trobenzaldehid, o — M チル t チル lbenzaldehid, m — M チル t チル lbenzaldehide, p — M チル t チル lbenz aldehide, p—Ethylbenzaldehyde, p—n—Butylbenzaldehyde, Telefta Noleanolede, etc. I can do it. Of these, honolemarin, parahonolemunoredaldehyde and hydroxybenzaldehydes are preferred. These aldehydes can be used alone or in combination of two or more.

Ketones include, for example, acetone, methylethylketone, jeethylketone, diphenylketone, and the like. These ketones can be used alone or in combination of two or more.

The condensation reaction product described above can be prepared by a conventional method, for example, by converting a phenol compound and an aldehyde or a phenol compound and a ketone in the presence of an acid catalyst. It can be obtained by reacting.

The vinylphenol-based polymer is selected from a homopolymer of vinylphenol and a copolymer of a component copolymerizable with vinylphenol. Isopropenylphenol-based polymers are selected from isopropanolphenol homopolymers and copolymers of isopropenylphenol with components that can be copolymerized with isopropenylphenol. It is something. Components that can be copolymerized with vinylphenol or isopro-vinylphenol include, for example, acrylic acid, methacrylic acid, styrene, maleic anhydride. Examples include monomers such as acid, maleic acid imide, vinyl acetate, acrylonitrile, and derivatives thereof. The copolymer can be obtained by copolymerizing each component by a well-known method.

The hydrogenation reaction product of the phenolic resin is obtained by dissolving the phenolic resin in an organic solvent and performing hydrogenation in the presence of a homogeneous or heterogeneous catalyst according to a conventional method. Obtainable.

Gel permeation chromatography (GPC) of the soluble phenolic resin used in the present invention using a UV254 nm detector The weight-average molecular weight in terms of polystyrene is usually from 2,000 to 2,500, preferably from 3,500 to 20,000. When the weight average molecular weight of the alkali-soluble phenolic resin is less than 3,500, the pattern shape, resolution, and developability tend to deteriorate, and when it is less than 2,000, it is not practical. It becomes bad. When the weight average molecular weight exceeds 200,000, the pattern shape, developability, and sensitivity deteriorate, and when the weight average molecular weight exceeds 25,000, it becomes impractical.

As the soluble phenol resin, a resin whose molecular weight and molecular weight distribution are controlled by known means can also be used. Methods for controlling the molecular weight and molecular weight distribution include, for example, (1) crushing the resin and performing solid-liquid extraction with an organic solvent having an appropriate solubility, or (2) dissolving the resin in a good solvent and adding a poor solvent. Or by dissolving the resin in a good solvent and dropping a poor solvent to perform solid-liquid or liquid-liquid extraction.

(B) Photosensitizer

The photosensitizer used in the present invention is a naphthoquinone diazide sulfonate of phenols, and particularly, in the total phenolic hydroxyl group of phenols, Ratio of 1,2-naphthoquinonediazido 6-sulfonate-derived phenolic hydroxyl group esterified by a photosensitive group derived from the above formula (1) (esterification ratio) 1,2—Naphthoquinone diazide 6—sulfonate (10-70%, preferably 20-70%, more preferably 25-65%) B 1). If the esterification rate of 1,2-naphthoquinonediazide 6—sulfonate (B 1) is too high, the storage stability of the positive-type photoresist composition decreases, Also, there is a tendency that a good pattern shape cannot be obtained, which is not preferable. In the present invention, when a compound having a photosensitive group represented by the following formula (2) or (3) is used in combination, the effect of inhibiting dissolution in an alkali developer is improved, It is preferable because a better pattern can be obtained.

That is, in the present invention, (B) 1,2-naphthoquinone diazide 6-sulfonate is used as the quinone diazide sulfonate of phenols In cooperation with (B1), the phenolic hydroxyl group of the phenols is represented by the formula (2)

1,2 —Naphthoquinone diazide 5 —Sulfonate-derived 1,2 —Naphthoquinone diazide esterified with a photosensitive group derived from The acid ester (B2) and the phenolic hydroxyl group of phenols are represented by the formula (3)

1,2-Naphthoquinone diazide 4-ester esterified with a photosensitive group derived from 1,2-naphthoquinone diazide 4-sulfonate represented by At least one species selected from the group consisting of 3) can be used in combination. The esterification ratio of the compounds (B2 and B3) having a photosensitive group represented by the formulas (2) and (3) is not particularly limited, and can be arbitrarily set. The esterification ratio of these compounds is usually from 10 to 90%, preferably from 20 to 80%, more preferably from 30 to 70%.

1,2-Naphthoquinonediazido 6-sulfonate (B1) having a photosensitive group represented by the formula (1) is (A) an alkali-soluble phenolic resin having a weight of 100%. It is usually used in a proportion of 2 to 60 parts by weight, preferably 5 to 50 parts by weight, more preferably 5 to 30 parts by weight based on parts. 1,2—Naphthoquinone diazide 6—Sulfonate (B 1), if too small, the sensitivity, resolution, pattern, focus tolerance, and dimensional accuracy Are not improved, and it is difficult to form a more practical pattern by i-line exposure. 1, 2 — Naphthoquinone diazide 6 — Sulfonate (B 1) is preferred if the proportion is too large, because storage stability tends to decrease and pattern shape tends to deteriorate. Not good.

1,2-naphthoquinonediazide-6-sulfonate (B1) and 1,2-naphthoquinonediazido-5-sulfonate ester (B2 ) And 1,2—naphthoquinonediazide-14—sulfonate (B3), when used in combination with at least one member selected from the group consisting of: The ratio can be appropriately determined in consideration of the respective esterification rates, the type of phenols to be used, and the parameter A described later, and the weight ratio of the two is usually 1: It is desirable to be within the range of 99 to 99: 1, preferably 5:95 to 95: 5.

When both are used together, 1,2-naphthoquinonediazido 5-sulfonate (B2) and 1,2-naphthoquinonediazide " — 4 — At least one compounding ratio selected from the group consisting of the sulfonate esters (B3) is usually based on 100 parts by weight of (A) the alkali-soluble phenol resin. It is 2 to 60 parts by weight, preferably 5 to 50 parts by weight, and more preferably 5 to 40 parts by weight.

The photosensitive agent having a photosensitive group represented by the above formulas (1) to (3) is a 1,2-naphthoquinonediazidosulfonate of phenols. 1,2-Naphthoquinonediazidosulfonate can be converted to 1,2-naphthoquinonediazidosulfonate according to a conventional method. The compound can be synthesized by reacting a diazide sulfonate halide with a phenol in a solvent in the presence of a base. As the solvent, for example, acetone, dioxane, tetrahydrofuran or the like is used. Examples of the base include inorganic bases such as sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, and sodium hydroxide, or trimethylamine, Tritylamine, tripropylamine, diisopropylamine, tributynoleamine, pyrrolidine, pyridin, pyrazine, monolefolin, pirenazine Organic bases such as lysine and dicyclohexylamine are used.

The photosensitizer used in the present invention comprises 1,2-naphthoquinonediazidosulfonate halide represented by the formula (1) and phenols represented by the formula (2), based on phenols. And Z or 1,2-naphthoquinonediazidosulfonate halide, which gives a photosensitive group represented by the formula (3), simultaneously reacts with one molecule of X-nors. It is also possible to provide a plurality of types of photosensitive groups by using the above method. That is, 1,2-naphthoquinonediazide-16-sulfonate (B1) accounts for 10% to 70% of all phenolic hydroxyl groups of phenols. If the 1,2-naphthoquinonediazide 16- represented by the formula (1) is esterified with a photosensitive group derived from sulfonate, the remaining At least a part of the phenolic hydroxyl group is a photosensitive group derived from 1,2-naphthoquinonediazido-5-sulfonate represented by the formula (2) and the formula (3) )), A mixture esterified with at least one photosensitive group selected from the group consisting of 1,2-naphthoquinonediazide 4—sulfonic acid-derived photosensitive groups It may be an ester. The esterification ratio of this mixed ester is not particularly limited, but is at least 10%, preferably at least 20%, of all the phenolic hydroxyl groups of the phenols. Preferably, if at least 25% is esterified with a photosensitive group derived from 1,2-naphthoquinonediazido 6-sulfonate represented by the above formula (1), the entire mixed ester is obtained. The esterification ratio is usually 90% or less, preferably 80% or less, and more preferably 70% or less, from the viewpoint of the balance of the resist properties. New

The phenols used for the formation of the photosensitizer are preferably polyvalent phenols having three or more phenolic hydroxyl groups. Specific examples of phenols include 2,3,4 trihydroxybenzofenone, 2,4,4'-trihydroxybenzofenon, 2 , 3,4,4'-Tetrahydroxybenzofenon, 2,4,2 ', 4'-Tetrahydroxybenzofonone, 2,3,4,2 ', 4' — Polyhydroxybenzophenones such as hydroxybenzen hydrophenone; gallic acids such as methyl gallate, ethyl gallate and propyl gallate esters; 2, 2 - bis (4 one human b Doki sheet off d) yl Purono, ⁰ down, 2, 2 - bis (2, 4 - di arsenide mud key sheet off d sulfonyl) Po Li arsenide mud such as propane Xbis bisphenylalkanes; tris (4-hydroxyphenyl) methane, 1,1,1-tris (4-hydroxy3) Chil-Feninole) Ethane, 1,1,1—Tris (4-hydroxy 3) -Methynolephane Ethane, 1,1,1,1—Tris (4-h Droxy Hue Nyl) ethane, 1,1bis (4-hydroxy-13) -1-1 (4-hydroxyphenyl) ethane, bis (4-hydroxy) -3-methinoref ene) 1 2-Hydroxy 1 4-Polyhydroxytriphenylalkanes such as methoxyphenyl methane; 1, 1,

2, 2 — Tetrakis (4-hydroxyphenyl) ethane, 1, 1, 1, 2, 2 — Tetrakis (3 — Methinole 4 — Hydroxyphenyl) ethane, 1 , 1,3,3—Polyhydroxyl trakisphenyls such as tetrakis (4-hydroxyphenyl) propane; a, a, a ', a'—Tetrakis (4-hydroxyphenyl) 1-3-xylene, a, a, a ', a'-tetrakis (4-hydroxyphenyl)-4-xylene, A, a, a ', a'-tetrakis (3—methinoleic 4-hydroxyphenyl) 13--polyhydroxy, such as xylene Rens; 2,6—bis (2,4—dihydroxybenzene), p—cresole, 2,6—bis (2,4—dihi) Droxi 1-3 — methylbenzil) 1 p — Cresol, 4, 6 — bis (4 1 hydroxybenzil) resorcin, 4, 6 — bis (4 — hydroquinone 1 3 — me Tilbenzil) Resorcinol, 4, 6—bis (4—hydroxybenzil) 1 2—methyl resonolecin, 4, 6—bis (4—hydroxy 3—methyl benzyl) 1 2 — Trimer by condensation reaction of phenolic compound such as methinoleresorcin and formalin, the following general formula (4)

(In the formula, R ¹ and R ² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ^{3 to} R ⁶ are each independently an alkyl group having 1 to 4 carbon atoms. Group. )

And the condensation reaction product of a phenolic compound such as a novolak resin with a formalin by a condensation reaction of a phenolic compound and formalin represented by Can be

Among these phenols, there are also polyhydroxytristriphenylalkanes, polyhydroxycitrates, traxphenylalkanes and polyphenols. Fluorine compounds such as triphenylbenzenes, trimethacrylates by condensation reaction of phenolic compounds with formalin, etc. When polyvalent phenols having 3 or 4 nuclei are used, particularly excellent resist characteristics tend to be obtained.

(C) Fluorine compound

In the present invention, a phenol compound can be added as an optional component in order to improve the resist properties such as pattern shape, heat resistance and sensitivity. Specific examples of the phenol compounds include monophenols such as p-phenylphenol, p-isopropanolphenol, and the like; biphenol , 4,4'-Hydroxy-hydrogen-no-tenor, 4,4'-Hydroxy-hydrogen-zonofen, Bis-funo-nore A (Honshu-Dogaku Kogyo Co., Ltd.) Bisphenol C (manufactured by Honshu Chemical Industry Co., Ltd.), bisphenol (manufactured by Honshu Chemical Industry Co., Ltd.), bisphenol F (manufactured by Honshu Chemical Industry Co., Ltd.), bisphenol Nor A (Honshu Chemical Industry Co., Ltd.), Bisphenol M (Mitsui Petrochemical Co., Ltd.), Bisphenol P (Mitsui Petrochemical Co., Ltd.), Bisphenol Le Z (manufactured by Honshu Chemical Industry Co., Ltd.), 1,1-bis (4—hydroxyphenyl) cyclopentane, 1,1-bis (4— (Doxy phenyl) cyclohexane, 9, 9-bis (4—hydroxy fluorinated) fluorene, 1, 1— bis (5—methyl 2-) (Hydroxyphenyl) methane, 3, 5 — dimethyl 4- ,

Fifteen

Bisphenols, such as 1,1,1,1 tris (4-hydroxyphenyl) methane, 1, 1, 1, 1—tris (4—hydr) 1,4-bis (3—methyl-14-hydroxyphenyl) 1-11,4- (4-hydroxyphenyl) meta 1, 1-bis (2,5—dimethyl 4-phenyl) 1 1— (2—hydroxy phenyl) methane, 1, 1—bis (3,5—dimethyloxy) -1 1— (2—hydroxyphenyl) methane, 2,6—vis (5—methyloxy2) — Hydroxybenzil) 1-4-Methylphenol, 2, 6-Bis (4-hydroxylbenzil)-4-1 Methylphenol, 2, 6-Bis ( 3 — Mechinore 4 — Hydroxybenzil) 1-4-methyl phenol, 2, 6-bis (3, 5-dimethyl-4-hydroxybenzene) 1-4-methyl phenol -Trisphenols such as Noren, Trisphenol (Honshu Chemical Industry Co., Ltd.) and Trisphenol-TC (Honshu Chemical Industry Co., Ltd.); 1, 1, 2, 2 — tetrax (4-hydroxyphenyl) ethane, 1, 1, 2, 2 — tetrax (3 — methyl 1-4-hide) Loxyphenyl) ethane, 1,1,3,3- (4-hydroxyphenyl) propane, 1,1,5,5—tetrakis (4-hydroxy) Phentan, a, a, a ', a' Tetrax (4—Hydroxyphenyl) 1-3 — Xylene, 《, a , a ', a' — Tetra kiss (4 -Hydroxyphenyl) 1-3-Xylene, α, a, a ', a'-Tetrakis (3-Methylenol 4-Hydroxyphenyl) 1 3 — Xylene, a, a, a ', a'-Tetrax (3 — Methyl-4-Hydroxifene) 1 4 — Quinlen, etc. Tetraphenols; and the like.

The phenolic compounds of the component (C) can be used alone or in combination of two or more. In particular, Alkali soluble When a resin having a low ratio containing a molecular weight of 10 nuclei or less is selected as a functional phenol resin, it is preferable to use such a phenol compound in combination. Results are often obtained.

The blending amount of the phenol compound can be arbitrarily selected, but usually 1 to 40 parts by weight, preferably 100 to 100 parts by weight of the alkali-soluble phenol resin. It is in the range of 3 to 30 parts by weight.

The positive resist composition of the present invention is usually used by dissolving it in a solvent in order to form a resist film by applying it to a substrate.

(Solvent)

Each component such as an alkali-soluble phenol resin, a photosensitizer, and a phenol compound is used after being dissolved in a sufficient amount of a solvent to uniformly dissolve these components.

Specific examples of the solvent used in the present invention include ketones such as acetone, methylethylenoketone, cyclopentanone, cyclohexanonone; Non-reactive compounds such as pyranol, isopropyl alcohol, n-butyl alcohol, and hexagonal hexanol; ethylene glycol, etc .; ethylene glycol Ethers such as ethylene glycol, polyethylene glycol, dioxane, etc .; ethylene glycol methanol, etc .; ethylene glycol, ethylene glycol, etc. Alcohols such as propyl formate, butyl formate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl dextranate, ethyl butyl butyrate, lactic acid Esters such as chill and ethyl lactate; cellosolve acetate, such as cellosolve acetate, methyl acetate solvent acetate, ethylcellosolone acetate, propylcellosolve acetate, and butylcelle solvent acetate Propylene glycol, propylene glycol monomethyl ether acetate, propylene glycol Propylene glycols such as luminoethyl acetate, propylene glycol, and butyl alcohol, etc .; diethyl glycol monomethyl alcohol, diethyl alcohol, etc. Diethylene glycols such as ethyl glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, etc .; halogenates such as trichloroethylene Aromatic hydrocarbons such as toluene and xylene; polar solvents such as dimethyl acetate, dimethylformamide, and N-methylacetamide; and the like. No. These solvents can be used alone or in combination of two or more.

(Other ingredients)

The poly-type photoresist composition of the present invention may contain, for example, styrene and acrylic resin, if necessary, in order to improve developability, storage stability, heat resistance and the like. Acid, copolymer of methacrylic acid or maleic anhydride, copolymer of argenine and maleic anhydride, polyvinyl alcohol, polyvinyl pyrrolidone, Addition of rosin, silver, etc. can be added. The amount of such a polymer to be added is generally 0 to 50 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the alkali-soluble phenol resin. Is within the range.

The photoresist composition of the present invention may contain, if necessary, a phase such as a surfactant, a storage stabilizer, a sensitizer, a striation inhibitor, and a plasticizer. Soluble additives can be included.

Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; Oxyethylene phenyl ether, polyoxyethylene Polyoxyethylene phenol ethers such as nonyl phenol ethers; polyethylene glycols such as polyethylene glycol, polyester glycolate stearate, etc. Glycol dialkyl esters; trade name EF TOP 31, EF 303, EF 352 (manufactured by Shin-Akita Kasei Co., Ltd.), trade names Megafax F171, F17 2, F177, F177 (manufactured by Dainippon Ink Inc.), trade name Florad FC430, FC4311

(Manufactured by Sumitomo SL), trade name Asahigad AG710, trade name Safron S — 382, SC — 101, SC — 102, SC — 10 3, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.) and other fluorine-based surfactants; Organosiloxane polymer KP 341

(Manufactured by Shin-Etsu Chemical Co., Ltd.); acrylic acid or methacrylic acid (co) polymer polyflow No. 75, No. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo) Is mentioned. The amount of these surfactants is 100 parts by weight of the solid content of the positive photoresist composition, usually 2 parts by weight or less, and preferably 1 part by weight or less.

(Developer)

The positive photoresist composition of the present invention can use an aqueous alkaline solution as a developing solution in the developing step. Examples of aqueous solutions of sodium hydroxide include aqueous solutions of inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium gayate, and ammonia; ethylamine, propylamine Aqueous solutions of primary amines such as acetylamine, dipropylamine, etc. Aqueous solutions of secondary amines such as getylamine, dipropylamine, etc .; Aqueous solutions of tertiary amines such as trimethylamine, triethylamine, etc. Aqueous solutions of alcohol amines such as ethetylethanolamine, triethanolamine, etc .; tetramethylammonium hydroxide, tetrahydroammonium hydroxide, triglyceride Methinole Hydrochloride Chillammonium Hydro An aqueous solution of a quaternary ammonium hydroxide such as xide, triethylenoxy hydroxymethyl methinoammonium hydroxide, trimethyl ethyl hydroxy shetyl ammonium hydroxide or the like; And so on.

In addition, the aqueous alkali solution may contain, as necessary, a water-soluble organic solvent such as methanol, ethanol, propanol, and ethylene glycol, a surfactant, and a resin dissolution inhibitor. Etc. can be added.

(No, ° lame evening A)

The positive photoresist composition of the present invention has the formula (I)

A = — ^ n [T _(max) Τ, ο)] (

Tr

[T r is the resist film thickness (im), T _(max) is the transmittance (%) of the resist after exposure, and T (.) Is the resist thickness before exposure. The transmittance (%). )

Is usually 0.30-1.50, preferably 0.33--; 1.35, more preferably 0.4 It is desirable to be within the range of 0 to 1.25.

The transmittances T ( _max ) and T (.) Are the transmittance (T _(max) ) when the resist composition is applied to a glass substrate to a thickness of 1 m, respectively. This is the transmittance (T (.)) When fully bleached using PLA-501F (manufactured by Canon Inc.) after the cloth is measured using a UV spectrophotometer. You.

Parameter Α is the parameter that is most affected by the sensitizer component, and the photo resist composition whose parameter A value falls within the above range is unbalanced by i-line exposure. It is particularly preferable because it gives good register characteristics.

(Posi-type photoresist composition) The positive photoresist composition of the present invention contains an alkaline soluble phenolic resin, quinone diazide sulfonate, and other optional components. Is used and stored as a resist solution uniformly dissolved in a solvent.

The resist solution can be applied to a substrate such as a silicon wafer by a conventional method, and then a solvent can be dried and removed to form a resist film. As a coating method at this time, spin coating is particularly preferable.

Exposure sources used in the exposure process for forming a notch on the resist film thus obtained include ultraviolet light, far ultraviolet light, and KrF excimer laser light. Electron sources such as X-rays, X-rays, and electron beams.

Heat treatment (post-exposure bake) after exposure is preferred because sensitivity, residual film ratio, resolution, and heat resistance can be improved.

Example

Hereinafter, the present invention will be described more specifically with reference to Synthesis Examples, Examples, and Comparative Examples. Parts and percentages in each example are by weight unless otherwise specified.

The weight-average molecular weight of the novolak resin in the following synthesis examples was calculated in terms of polystyrene in the pattern obtained by gel permeation chromatography (GPC) using a UV 254 nm detector. It is the weight average molecular weight (Mw).

[Synthesis example 1] Synthesis of novolak resin (A-1)

To a 2-liter flask equipped with a cooling tube and stirrer, 350 g of m-cresol, 350 g of p-cresol, 367 g of 37% formalin , And 2.45 g of oxalic acid dihydrate were added, and the mixture was reacted for 2 hours while maintaining the temperature at 95 to 100 ° C. Thereafter, water was distilled off at 200 ° C. to 105 ° C. for 2 hours. Furthermore, the pressure was reduced to 10 mmHg while the temperature was raised to 180 ° C to remove unreacted monomers and water, and the temperature was returned to room temperature to collect the produced resin. — L) 5 85 g were obtained. The Mw of this novolak resin (A-1) was 5,000.

[Synthesis Example 2] Acquisition of Novolak resin (A-2)

To 350 g of the novolak resin (A-1) obtained in Synthesis Example 1, 350 g of ethyl acetate solupucetate was added and dissolved. In a flask equipped with a dropping funnel, with the temperature of the solution controlled at 80 to 85, 3450 g of toluene was added dropwise from the dropping funnel, and then at 80 for 1 hour. Heated. After slowly cooling to room temperature, it was left still for 1 hour. The supernatant of the precipitated resin was removed by decantation, and 570 g of ethyl lactate was added.The residue was heated to 100 ° C at 100 mm Hg to remain. The toluene was removed to obtain an ethyl acetate lactate solution of the novolak resin (A-2). The Mw of this novolak resin (A-2) was 9,200.

[Synthesis Example 3] Synthesis of novolak resin (A-3)

A 2-liter flask equipped with a condenser and a stirrer was charged with m-cresol 280 g, p-cresol 42 1 g, 37% formalin 343 g, And 2.45 g of oxalic acid dihydrate were added, and the mixture was reacted for 2 hours while maintaining a temperature of 95 to 100 ° C. After this, 100 to 105. Water was distilled off with C over 2 hours. Further, the pressure was reduced to 10 mmHg while the temperature was raised to 180 ° C. After removing unreacted monomers and water, the temperature was returned to room temperature, and the generated resin was recovered. 3) 473 g was obtained. The Mw of this novolak resin (A-3) was 6,000.

[Synthesis Example 4] Acquisition of Novolak resin (A-4) To 180 g of the novolak resin (A-3) obtained in Synthesis Example 3, 350 g of ethyl acetate mouth sorp acetate was added and dissolved. In a flask equipped with a dropping funnel, with the temperature of the solution being controlled at 80 to 85 ° C, 345 g of toluene was dropped from the dropping funnel, and then added. Heated at 0 ° C for 1 hour. After slowly cooling to room temperature, it was left still for 1 hour. After removing the supernatant liquid of the precipitated resin by decantation, 570 g of ethyl lactate was added, and the mixture was adjusted to 100 OmmHg to 100 g. The residue was heated to C to remove residual toluene, and an ethyl lactate solution of the novolak resin (A-4) was obtained. The Mw of this novolak resin (A-4) was 9,900.

[Synthesis Example 5] Synthesis of Novolak resin (A-5)

Two liter flasks equipped with a cooling pipe and a stirrer were fitted with m—cresole 255 g, p—cresole 32 g, 2, 3, 5— Trimethylaminophenol 160 g, 92%. 14.6 g of laformaldehyde and 2.45 g of oxalic acid dihydrate were added, and the mixture was reacted for 2 hours while maintaining the temperature at 95 to 100 ° C. Thereafter, water was distilled off at 100 to 105 ° C over 2 hours. Furthermore, the pressure was reduced to 10 mmHg while the temperature was raised to 180 ° C to remove unreacted monomers and water, and the temperature was returned to room temperature to recover the generated resin. 63 g of resin (A-5) was obtained. The Mw of this novolak resin (A-5) was 4,800.

[Synthesis example 6] Acquisition of novolak resin (A-6)

To 380 g of the novolak resin (A-5) obtained in Synthesis Example 5, 380 g of toluene was added and dissolved. After heating the solution at 80 ° C for 1 hour, it was gradually cooled to room temperature, and left still for 1 hour. After removing the supernatant of the precipitated resin by decantation, 570 g of ethyl lactate was added, and the mixture was heated to 100 ° C with 100 mm Hg to remove residual toluene. Then, an ethyl lactate solution of the novolak resin (A-6) was obtained. This nobo The Mw of the lacquer resin (A-6) was 8,000.

[Synthesis Example 7] Synthesis of Novolak resin (A-7)

Two liter flasks equipped with a cooling pipe and a stirrer were fitted with m—cresole 291,1 g, 3,5—xylone 1 110 g, 2,3,5 — Add 122 g of trimethyl phenol, 346 g of 92% paraformaldehyde, and 1.70 g of oxalic acid dihydrate, and raise the temperature to 95 to 100 °. The reaction was carried out for 2 hours while maintaining at C. Thereafter, water was distilled off at 100 to 105 ° C for 2 hours. Further, the pressure was reduced to 10 mmHg while the temperature was raised to 180 ° C to remove unreacted monomers and water, and the temperature was returned to room temperature to collect the generated resin. — 7) 560 g were obtained. The Mw of this novolak resin (A-7) was 2,400.

[Synthesis Example 8] Acquisition of novolak resin (A-8)

To 140 g of the novolak resin (A-7) obtained in Synthesis Example 1 was added and dissolved 14 g of ethyl acetate sorp acetate. In a flask equipped with a dropping funnel, while the temperature of the solution is controlled at 80 to 85 ° C, 210 g of toluene is added dropwise, and further at 80 ° C for 1 hour. Heated. After slowly cooling to room temperature, it was left still for 1 hour. The supernatant of the precipitated resin was removed by decantation, 50 g of ethyl lactate was added, and the mixture was heated to 100 with 100 mm Hg to remove residual toluene. Then, an ethyl lactate solution of the novolac resin (A-8) was obtained. The Mw of this novolak resin (A-8) was 4,000.

[Synthesis examples 9 to 12] Synthesis of photosensitizers (B-1) to (B-4)

As the phenols, each of the novolak resins obtained in Synthesis Examples 1, 3, 5, and 7 was used, and 1,2-naphthoquinonediazide 16-sulfonate was used with each of these resins. And (B-1), (B-2), (B-3) and (B-4) with the esterification rates shown in Table 1 Was synthesized.

More specifically, novolak resin and 1,2-naphthoquinonediazide-6-sulfonic acid chloride (the amount corresponds to the esterification ratio in Table 1) (Moles) was dissolved in acetone to give a 10% concentration solution. While controlling the temperature of the solution within the range of 20 to 25 ° C, 1.2 equivalents of 1,2-naphthoquinonediazide-6-sulfonyl chloride Triethylamine was added dropwise over 30 minutes, and the temperature was kept at this temperature for 2 hours to complete the reaction. After the precipitated salt was separated by filtration, the solution was poured into a 10-fold amount of a 0.2% aqueous solution of oxalic acid of the reaction solution. The precipitated solid was filtered, washed with ion-exchanged water, and dried under vacuum to obtain 1,2-naphthoquinonediazide-6-sulfonate (photosensitizer). In this way, four types of photosensitizers (B-1), (B-2), (B-3) and (B-4) shown in Table 1 were obtained.

[Synthesis Examples 13 to 15] Synthesis of Photosensitizers (B-5) to (B-7)

As phenols, the following formula (b-1)

This compound is reacted with 1,2-naphthoquinonediazido 6-sulfonyl chloride to give a sensitizer (B — 5), (B-6) and (B-7) were synthesized. The synthesis method was the same as in Synthesis Examples 9 to 12, and Table 1 shows the amount of 1,2-naphthoquinone diazide-6-sulfonyl chloride used. The number of moles was equivalent to the esterification ratio of each photosensitive agent.

[Synthesis examples 16 to 17] Synthesis of photosensitizers (B-8) to (B-9) As phenols, the following formula (b-2)

This compound is reacted with 1,2-naphthoquinone diazide 6-sulfonyl chloride to give a sensitizer with an esterification rate as shown in Table 1. (B-8) and (B-9) were synthesized. The synthesis method was the same as in Synthesis Examples 9 to 12, and the amount of 1,2-naphthoquinonediazide-6-sulfonyl chloride used was as shown in Table 1 for each photosensitizer. The number of moles was equivalent to the esterification rate of

[Synthesis Examples 18 to 19] As the phenols for synthesizing the photosensitizers (B-10) to (B-11), the respective volatile resins obtained in Synthesis Examples 3 and 7 were used. Each of these was reacted with 1,2-naphthoquinonediazide 5—sulfonate chloride to obtain a photosensitizer (B- 10) and (B-11) were synthesized. The synthesis method was the same as in Synthesis Examples 9 to 12, and the amount of 1,2-naphthoquinonediazide-5-sulfonyl chloride used was as shown in Table 1. The number of moles was equivalent to the esterification ratio of the photosensitizer.

[Synthesis Examples 20 to 21] The above compounds (b-1) or (b-2) were used as phenols for synthesizing photosensitizers (B12) to (B-13). Each of these was reacted with 1,2-naphthoquinonediazide 5—sulfonyl chloride to obtain a photosensitizer (B— 12) and (B-13) were synthesized. The synthesis method was the same as in Synthesis Examples 9 to 12, except that 1,2—naphthoquinonediazide-1-5 The amount of sulfonic acid chloride used was a molar number corresponding to the esterification ratio of each photosensitizer shown in Table 1.

[Examples 1 to 15, Comparative Examples 1 to 5]

Using the following components, each positive photoresist composition (resist solution) shown in Table 1 was prepared.

(1) As alkaline soluble phenolic resin (A), novolak resins (A-2), (A-4), (A-6) and

(A-8) was used.

(2) As photosensitizers 1, 2 — naphthoquinone diazide 6 — sulfonate ester (B 1), the photosensitizers (B_ 1) to

(B-9) was used.

(3) Photosensitizers 1,2-Naphthoquinone diazide 5—Sulfonate ester (B1), and the photosensitizers (B-10) obtained in the above synthesis examples (B-10) B—13) was used.

As the phenol compounds, the phenol compounds represented by the following formulas (C-11), (C-12) and (C-13) were used.

(C-1)

(4) Ethyl 2-hydroxypropionate (D-) or 3-ethyl methoxypropionate (D-2) was used as the solvent.

Using the above components, resist compositions 1 to 20 shown in Table 1 (resist solution; solid concentration: 23%) were prepared.

table 1

Various characteristics were evaluated using the resist solutions 1 to 20 shown in Table 1. Specifically, a resist solution was applied on a silicon wafer with a spinner, and then pre-baked at 90 ° C for 60 seconds to obtain a film thickness of 1.0 μm and 1 μm. A 30 ^ m resist film was formed.

On the resist film formed on the silicon wafer, i-line status, ⁰ — NSR 205 i10D (Nikon; NA = 0.57) and test Exposure was performed using a reticle while changing the exposure time, and a post exposure bake (Post Exposure Baking) was performed at 110 and 60 seconds. Next, a positive type pattern was formed by developing with a 2.38% aqueous solution of tetramethylammonium hydroxyride by a paddle method at 23 ° C for 1 minute. .

The silicon wafer on which the resist pattern is formed is taken out, observed with an electron microscope, and the sensitivity, resolution, pattern shape, focus tolerance, and dimensional change Was evaluated. Parameter A value was measured by the measurement method described above. In addition, the storage stability of each resist solution was evaluated. Each evaluation method is as follows.

(1) Sensitivity

The exposure energy (unit: msec), which represents the amount of exposure energy that can form 1: 1 lines and spaces of 0.6111, according to design dimensions, was expressed. (2) Resolution

The minimum pattern size (m) resolved when exposed for the above exposure time was expressed.

(3) Pattern shape

The silicon wafer on which the resist pattern was formed was cut from the vertical direction of the line-turning pattern, observed with an electron microscope from the cross-sectional direction of the pattern, and evaluated according to the following criteria.

〇: The film thickness is not reduced, and the pattern sidewall is at 80 degrees to the substrate. It stands up at the above angle.

Δ: The film was not reduced, and the pattern sidewall was rising at an angle of 70 ° or more and less than 80 ° with respect to the substrate.

: There is film loss, and the side wall rises at an angle of less than 70 degrees to the substrate.

(4) Force tolerance

0.35 111 1: 1 line & space is within ± 10% of the mask's design dimension, and the remaining film ratio [resist pattern is formed on the silicon wafer When the ratio (% :) of the resist film thickness before and after the development of the unexposed portion is 90% or more, the focus tolerance is determined according to the following criteria depending on the fluctuation width of the focus. The sex was evaluated.

〇: The focus swing is 1.2 m or more.

X: The focus deflection force is less than 1.2 m.

(5) Dimensional change

An exposure dose that reproduces the mask dimensions of 0.35 / m 1: 1 line & space at a resist film thickness of 1.07 m, and a resist film of 1.30 / m The thick resist film was exposed, and the obtained resist pattern was observed and evaluated according to the following criteria in comparison with a resist pattern of 1.07 m.

：: The dimensional change rate of the resist pattern is 10% or less.

△: The dimensional change rate of the resist pattern is 11 to 15%.

: The dimensional change rate of the resist pattern is 16% or more.

(6) Storage stability

The prepared positive photoresist solution was allowed to stand at 23 ° C., and a precipitate in the solution after three months was observed, and evaluated according to the following criteria.

〇: No precipitate was observed. X: precipitate was observed

Table 2 shows the evaluation results.

From the results shown in Table 2, it can be seen that the positive photoresist composition of the present invention (Examples 1 to 15) has a sensitivity and a resolution in forming a pattern on a relatively thick resist film. , Pattern shape and focus tolerance Industrial applicability that has been shown to improve

The photoresist composition of the present invention has excellent sensitivity, resolution, pattern shape, and focus tolerance, and is excellent in dimensional accuracy. In addition, the resist characteristics are highly balanced even under thick film conditions, such as excellent storage stability. Therefore, the positive photoresist composition of the present invention is extremely useful for the production of integrated circuits and the like, for which higher integration is expected to further advance in the future.

Claims

The scope of the claims

1. Posi-type resist composition containing (A) an alkali-soluble phenolic resin and (B) quinonediazidosulfonate of a phenol as a photosensitizer. In (B), the quinone diazide sulfonate of phenols represents 10 to 70% of the total phenolic hydroxyl groups of the phenols of the formula (1) )

1, 2 — naphthoquinone diazide 6 — sulfonate esterified with a sulfonate-derived photosensitive group represented by 1,2 — naphthoquinone diazide 6 (sulfonate) A positive resist composition characterized by containing B1).

2. (B) The quinone diazide sulfonate of phenols is a quinone diazide sulfonate of polyhydric phenols having at least three hydroxyl groups. 2. The photoresist composition according to claim 1, wherein the composition is:

3. Polyhydric phenols are polyhydroxybenzophenones, gallic esters, polyhydroxybisbisphenylalkanes, polyhydroxytris It does not consist of phenylalkanes, polyhydroxyltraxenyl phenylalkanes, polyhydroxyltraxyl phenyloxylens, and the condensation reaction products of phenolic compounds with formalin. 3. The photoresist composition of claim 2, wherein the composition is at least one selected from the group consisting of:

4. (A) 1,2-Naphthoquinonediazide 6-sulfonate (B1) in a proportion of 2 to 60 parts by weight based on 100 parts by weight of the alkali-soluble phenol resin. 4. The photoresist composition according to any one of claims 1 to 3, which contains the composition.

5. (B) The quinonediazidosulfonate ester of phenols is obtained by adding 1,2-naphthoquinonediazide 6-sulfonate ester (B1) to phenol. Phenolic hydroxyl groups of formula (2)

1,2-Naphthoquinone diazide 5 —sulfonate esterified with a photosensitive group derived from 1,2-naphthoquinone diazide 5-sulfonate represented by B 2), and the phenolic hydroxyl group of phenols is represented by the formula (3)

1,2-Naphthoquinone diazide derived from 4-sulfonate It further contains at least one member selected from the group consisting of 1,2-naphthoquinonediazide-14-sulfonate (B3) esterified by a photosensitive group. 5. The positive photoresist composition according to claim 1, wherein the composition is a positive photoresist composition.

6. 1, 2-naphthoquinone diazide 6-sulfonate (B1) and 1, 2-naphthoquinone diazide 5-sulfonate ester (B2) And 1,2—naphthoquinonediazido 4—snorrephonate (B 3) having a weight ratio of at least one selected from the group consisting of 1:99 to 99: 1. 6. The positive photoresist composition according to claim 5, which is within the range.

7. 2 to 60 parts by weight of 1,2-naphthoquinonediazido 6-esterenolate sulfonate (B1) and 100 parts by weight of (A) the alkali-soluble phenol resin , 2 — naphthoquinone diazide 5 — sulfonate (B 2) and 1, 2 — naphthoquinone diazide 4-sulfonate (B 3) 7. The positive photoresist composition according to claim 5, which contains at least one member selected from the group in an amount of 2 to 60 parts by weight.

8. 1, 2 — Naphthoquinone diazide 6 — Sulfonate (B 1) accounts for 10 to 70% of all phenolic hydroxyl groups in phenols. 1,2-Naphthoquinone diazide 6 represented by the formula (1) is esterified with a photosensitive group derived from sulfonate, and has a small amount of residual phenolic hydroxyl group. And a photosensitive group derived from 1,2-naphthoquinonediazido 5—sulfonate, a part of which is represented by the formula (2); A mixed ester esterified with at least one kind of photosensitive group selected from the group consisting of photosensitive groups derived from 1,2-naphthoquinonediazido-4-sulfonic acid represented by the following formula: The positive photoresist composition according to any one of the above.

9. The photoresist composition according to any one of claims 1 to 8, further comprising (C) a phenol compound.

10. The method according to claim 9, wherein the (C) phenol compound is contained in a proportion of 1 to 40 parts by weight based on 100 parts by weight of the (A) alkali soluble phenol resin. Positive photoresist composition.

1 1. The (C) phenolic compound is a monophenol, a bisphenol, a trisphenol, or a tetraxphenol. 10. The photoresist composition of claim 9 or 10, wherein the composition is at least one member selected from the group consisting of:

12. The positive electrode according to any one of claims 1 to 11, wherein (A) the alkali-soluble resin has a weight average molecular weight in the range of 3,500 to 20,000. Type photo resist composition.

13. The positive photoresist composition according to claim 1, further comprising a solvent in an amount sufficient to uniformly dissolve each component.

1 4. (A) Alkali-soluble phenol resin 100 parts by weight Then, 1,2-naphthoquinonediazido 6-sulfonate (Bl) 2 to 60 parts by weight, 1,2-naphthoquinonediazido 5—sulfonate (B2) and At least one selected from the group consisting of 1,2-naphthoquinonediazido-4-snolephonate (B3); 2 to 60 parts by weight; and (C) funolol 10. The positive photoresist composition according to claim 10, comprising 1 to 40 parts by weight of the compound.

15. The positive photoresist composition according to claim 14, further comprising a solvent in an amount sufficient to uniformly dissolve each component.

1 6. Equation (I)

A = ^-£ n [T _(max , / T ₍₀ )] (I)

Ί r

[Τr is the resist film thickness (m), T ( _max > is the transmittance (%) of the resist after exposure, and T <.) Is the resist thickness before exposure. The transmittance (%). )

The positive type photo resist according to any one of claims 1 to 15, wherein the parameter A calculated on the basis of Composition.