TWI263863B - Positive photo resist composition and method of forming resist pattern - Google Patents

Abstract

A material preferable for manufacture of systematic LCD, having excellent linearity, and formable for fine resist patterns is provided. A positive photoresist for manufacture of a single substrate having thereon an integrated circuit and a liquid crystal display part, comprising (A) alkali soluble resin, (B) naphthoquinone diazide-esterified material, (C) a specific phenolic hydroxyl group comprising compound, and (D) organic solvent. A resist pattern forming method comprises a step of forming a resist coat on a substrate by the use of the positive photoresist, a step of selectively exposing the coat to light via a mask provided with a mask pattern for forming a resist pattern of an integrated circuit and a mask pattern for forming a resist pattern of a liquid crystal display part, to form at the same time a resist pattern of an integrated circuit and a resist pattern of a liquid crystal display part.

Description

1263863 (1) Technical Field of the Invention The present invention relates to a method of forming a positive-type photoresist composition and a photoresist pattern for manufacturing a substrate on which an integrated circuit and a liquid crystal display portion are formed on one substrate. [Prior Art] In the field of manufacturing liquid crystal display elements using a glass substrate, for example, since it is relatively inexpensive and can form a photoresist pattern having excellent sensitivity, resolution, and shape, it is used in the manufacture of many semiconductor elements. A positive photoresist material composed of a phenolic enamel resin-yttrium diazide compound, but in the manufacture of a semiconductor device, a circle having a diameter of 8 吋 (about 200 mm) to 12 吋 (about 300 mm) is used at the maximum. In the case of a disk type wafer, in contrast to the manufacture of a liquid crystal display element, a square glass substrate of about 360 mm x 460 mm is used at a minimum. Thus, in the field of manufacturing liquid crystal display elements, the size is greatly different from that of semiconductor elements. Therefore, it is required to form a photoresist pattern having a good shape and dimensional stability on a wide substrate surface in a photoresist material for manufacturing a liquid crystal display. A photoresist material for the production of such a liquid crystal display element is disclosed in Japanese Laid-Open Patent Publication No. Hei 9-16023, No. Hei 9-2, No. 1 Many reports such as the bulletin 000- 1 3 1 8 3 5, JP-A-2000-5- 1263863 (2) 1 8 1 0 5 5, and JP-A-200 1 - 7 5 2 72. These materials are inexpensive, and for a small-sized substrate of about 360 mm X 4 60 mm, a photoresist pattern excellent in coatability, sensitivity, resolution, shape, and dimensional stability can be formed, so it is suitable for use. The purpose of manufacturing an LCD having only a display portion. On the other hand, the second-generation LCD is currently actively forming a driver, a DAC (digital-to-analog converter), an image processor, a video controller, a RAM, etc. on a single glass substrate to form an integrated circuit on a substrate. Display part of the high-performance LCD technology development (Semiconductor FPD World 200 1 · 9 ' pp. 5 0-67). Hereinafter, in the present specification, a substrate which forms an integrated circuit and a liquid crystal display portion on one substrate is referred to as an L C D system. However, the size of the display portion of such an LCD system is, for example, about 2 to 10 μm. In contrast, the pattern size of the integrated circuit portion must be formed to a fine size of, for example, about 〜5 to 2.0 μmτι. In the case of forming such an integrated circuit portion and a display portion under the same exposure conditions, linearity is desired [under the same exposure conditions (the conditions of the mask on the reticle are different but the exposure amount is the same), and at the time of exposure The characteristics of the reticle size reproduction on the reticle] are excellent. Further, in order to form a fine pattern of an integrated circuit portion, it is necessary to improve the resolution of a photoresist material for manufacturing a liquid crystal display element of the prior art. In order to improve the resolution (resolution boundary), the equation R = k]xA /ΝΑ (where R is the resolution limit, k) is the ratio determined by the photoresist and the step and image formation method. The constant, λ is the wavelength of -6-(3) 1263863 light used in the exposure step, ΝΑ is the number of openings of the lens, and it is necessary to use a short-wavelength light source' or an exposure step with a high να. Therefore, 'when forming a fine photoresist pattern such as 2 · Ο μηι below, 'is effectively exposed by the previous g-ray (4 3 6 nm), for example using a shorter wavelength i-ray (3 6 5 nm) ) Light lithography technology for exposure. On the other hand, 'from the viewpoint of increasing the throughput (the number of treatments per unit time), 'it is expected that the exposure area in the liquid crystal field is at least about 丨〇〇mm2'. If the exposure area is widened, it is not only difficult to maintain this part. The plane uniformity 'and because the depth of focus is shallow is not suitable for high NA lenses, so it is difficult to achieve high NA. In the manufacturing field in which the liquid is indispensable for the liquid, for the above reasons, it is generally preferable to have a low NA condition of 0.3 or less. However, the photoresist material for manufacturing a liquid crystal display element is difficult to form a shape excellent under low NA conditions. A fine photoresist pattern of about 0.5 to 2.0 μηι, and the cross-sectional shape of the photoresist pattern is not rectangular, but has a tendency to exhibit a taper. Therefore, it is desired to form a fine photoresist pattern even under low-lying conditions, and to manufacture a photoresist material for an L C D system which is excellent in linearity. [Problems to be Solved by the Invention] Therefore, in the present invention, it is an object of the invention to provide a photoresist material which is excellent in linearity for producing an LCD system as described above. [Means for Solving the Problems] In order to solve the above-mentioned problems, the inventors of the present invention found that 1263863 (4) found a positive resist composition containing a specific phenolic hydroxy compound, even under low NA conditions. It is also possible to form a fine photoresist pattern and is a linearly excellent photoresist material, and is suitable for manufacturing an LCD system, and has completed the present invention. That is, the present invention is a compound containing (A) an alkali-soluble resin, (B) a naphthoquinonediazide ester, and (C) a phenolic hydroxyl group represented by the following general formula (I).

0H

And (D) an organic solvent which is a positive photoresist composition for substrate fabrication in which an integrated circuit and a liquid crystal display portion are formed on one substrate. Furthermore, the present invention relates to a step of (1) coating a positive-type photoresist composition on a substrate and forming a coating film, and (2) heat-treating the substrate formed on the coating film on the substrate. a step of forming a photoresist film, and (3) using a mask pattern for forming a photoresist pattern for forming an integrated circuit and a mask pattern for forming a liquid crystal display portion for the photoresist film; a step of selectively exposing the photomask, and (4) applying a development process using an alkaline aqueous solution to the photoresist film after the selective exposure, and forming an integrated circuit for the same on the substrate - 8 - 1263863 (5) The steps of the photoresist pattern and the photoresist pattern for the liquid crystal display portion, and (5) the photoreceptive liquid of the photoresist pattern surface is washed. Forming method. [Embodiment of the Invention] The _soluble resin as the component (A) in the positive resist composition of the present invention is not particularly limited, and can be generally used as a film forming material in a positive resist composition. Choose any one. Examples of the alkali-soluble resin include phenols such as phenol, m-toluene-p-cresol, xylenol, and trimethylphenol, and keke's formazan precursor, 2-hydroxybenzaldehyde, and 3_ a phenolic enamel resin obtained by condensing an aldehyde such as hydroxybenzaldehyde or 4-hydroxybenzaldehyde in the presence of an acidic catalyst; a monomer of hydroxystyrene; and a copolymer of hydroxystyrene and other styrene monomers; An alkali-soluble resin such as a hydroxystyrene resin such as a copolymer of hydroxystyrene and acrylic acid or methacrylic acid or a derivative thereof, or a copolymer of acrylic acid or methacrylic acid and a derivative thereof, such as acrylic acid or methacrylic resin. Particularly, a novolac resin obtained by condensation reaction of a phenol containing m-cresol and 3,4-xylenol with an aldehyde containing propionaldehyde and formaldehyde is a photoresist material suitable for adjusting high sensitivity and excellent linearity. In the positive-type resist composition of the present invention, the naphthoquinonediazide ester compound as the component (B) is not particularly limited, and the hydrazine diazide previously used as a photosensitive component of the photoresist can be used. Any of the base ester compounds, in particular, the following general formula (11) -9 - 1263863 (6)

[wherein R1 to R8 each independently represent a hydrogen atom, a halogen atom, a propylene group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms; RlG , Rl] independently represent the hydrogen atom or carbon number! ~6 alkyl groups; Q is terminated or unbound with R9; Q is not bonded to the end of R9, R9 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, q is a hydrogen atom, carbon number i~6 alkyl groups or residues represented by the following chemical formula (III)

(wherein R12 and R13 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms; In the case of an integer of 1 to 3, Q is bonded to the terminal of R9, and Q and R are ring-shaped groups of carbon atoms 3 to 6 together with carbon atoms between Q and R9; a and b are represented An integer of 1 to 3; d is an integer representing 0 to 3; n is an integer representing 0 to 3, and an esterified product of a phenol compound and a naphthoquinonediazidesulfonic acid compound is light suitable for using i-rays The lithography, for example, is applied in the case of a fine photoresist pattern below 2 Ο μηι. Also, Q and R 9 are formed together with carbon atoms between Q and R 9 . Carbon chain-10-(7) 1263863 3 to 6 of the alkyl group, Q and R9 are bonded to form a carbon number of 2 to 5 alkyl hydrazines. The phenol compound of the general formula is exemplified by three (4- Hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,3,5-trimethylphenyl)-2.hydroxybenzene Methane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxybenzene Methane, bis(4-hydroxy-3,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane , bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxyphenylmethane, double (4-hydroxy-2,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, Bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxy Phenylmethane, bis(4-hydroxy)-3-methoxy-4-hydroxyphenylmethane), bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane , bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxybenzene a trisphenol type compound such as methane or bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3,4-dihydroxyphenylmethane; bis(2,3,4-trihydroxyphenyl) Methane, bis(2,4-dihydroxyphenyl)methane, 2,3,4-trihydroxyphenyl hydroxyphenylmethane, 2,4-di ( Linear type 3 of 3,5-dimethyl-4-hydroxybenzyl)-5-hydroxyphenol or 2,6-bis(2,5-dimethyl-4-hydroxybenzyl)-4-methylphenol Nuclear phenolic compound; 1,1-bis[3-(2-hydroxy-5-methylbenzyl)-4-hydroxy-5-cyclohexylphenyl]isopropane, bis[2,5-dimethyl- 3-(4-hydroxy-5-methylbenzyl)-4-hydroxyphenyl]methane, bis[2,5-dimethyl-3-(4-hydroxybenzyl)-4-hydroxyphenyl]methane , bis[3-(3,5-di-11 - (8) 1263863 methyl-4-hydroxybenzyl)-4-hydroxy-5-methylphenyl]methane, bis[3-(3,5- Dimethyl-4-hydroxybenzyl)-4-hydroxy-5-ethylphenyl]methane, bis[3-(3,5-diethyl-4-hydroxybenzyl)-4-hydroxy-5- Methylphenyl]methane, bis[3-(3,5-diethyl-4-hydroxybenzyl)-4-hydroxy-5-ethylphenyl]methane, bis[2-hydroxy-3-(3) ,5-Dimethyl-4-hydroxybenzyl)-5-methylphenyl]methane, bis[2-hydroxy-3-(2-hydroxy-5-methylbenzyl)-5-methylphenyl Methane, bis[4-hydroxy-3-(2-hydroxy-5-methylbenzyl)-4-hydroxyphenyl]methane, bis[2,5-dimethyl-3-(2-hydroxy-5) Linear tetranuclear phenolic compound such as -methylbenzyl)-5-methylphenyl]methane; 2,4-bis[2 -hydroxy-3-(4-hydroxybenzyl)-5-methylbenzyl]-6-cyclohexylphenol, 2,4-bis[4-hydroxy-3-(4-hydroxybenzyl)-5- Benzyl]-6-cyclohexylphenol, 2,6-bis[2,5-dimethyl-3-(2-hydroxy-5-methylbenzyl)-4-hydroxybenzyl]-4- a linear polyphenol compound such as a linear penta-nuclear phenol compound such as phenol; 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4,trihydroxyphenyl)propane, 2-(2,4-Dihydroxyphenyl)2-(2',4^dihydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2 -(3-fluoro-4-hydroxyphenyl)-2-(3'-fluoro-4'-hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)2-(4'-hydroxybenzene Propane, 2-(2,3,4-trihydroxyphenyl)2-(4'-hydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)2-(4'- a bisphenol type compound such as hydroxy-3',5'-dimethylphenyl)propane; 1-[1,Bus(4-methylphenyl)ethyl]_4-[1-(4-hydroxybenzene) Isopropyl]benzene, 1-[1-(4-hydroxyphenyl)isopropyl]-4-[l,1-bis(4-hydroxyphenyl)ethyl]benzene, 1-[1- (3-methyl-4-hydroxyphenyl)isopropyl]-4-(1, bis(3-methyl-4-hydroxyphenyl)ethyl) A polynuclear branched compound such as a phenyl group; a condensed phenol compound such as 1,1-bis(4-hydroxyphenyl)cyclohexane; Among them, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3,4-dihydroxybenzene 1263863 (9) keel, bis(4-hydroxy-2,3,5-dimethyl Phenyl phenyl)-2 - a trisphenol type compound such as phenyl group, 丨'丨-bis[3-(2_transyl-5-methylbenzyl)-4-hydroxy-5-cyclohexylbenzene The linear tetranuclear phenol compound such as isopropane is preferable in terms of sensitivity and resolution, and can form a photoresist pattern having a good shape. The method of esterifying all or a part of the phenolic hydroxyl group of the compound represented by the above general formula (11) with naphthoquinonediazidesulfonate can be carried out according to a conventional method, for example, naphthoquinonediazidesulfonyl chloride and the above The compound represented by the general formula (II) can be obtained by condensation. Specifically, the compound represented by the above general formula (π) and naphthoquinone-1 'diazido-4' (or 5)-sulfonyl chloride are dissolved in dioxane, n-methylpyrrolidone in a specified amount, In an organic solvent such as dimethylacetamide or tetrahydrofuran, a basic catalyst such as triethylamine, triethanolamine, pyridine, an alkali metal carbonate or an alkali metal hydrogencarbonate is added thereto and reacted, and the obtained product is obtained. It can be prepared by washing with water and drying. (B) In addition to the naphthoquinonediazide esters exemplified above, other naphthoquinonediazide esters such as polyhydroxybenzophenone and phenyl compounds such as alkyl benzoate may be used. The esterification reaction product of the naphthoquinonediazidesulfonic acid compound or the like may be used, and the amount thereof to be used in the component (B) is 8 〇 by mass or less, particularly preferably 5% by mass or less, since the effect of the present invention is not impaired. Therefore, it is better. In the positive resist composition of the present invention, the compounding amount of the component (B) is 20 to 70%, preferably 30 to 50, based on the total mass of the component (A) and the component (C) below. The choice of % of the mass range is preferred. If the amount of the component (B) is too low, the image that is faithful to the pattern cannot be obtained, and the transfer property 1263863 (10) is lowered. On the other hand, when the amount of the component (B) exceeds the above range, the sensitivity is deteriorated, and the homogeneity of the formed photoresist film is lowered, and the resolution is likely to be deteriorated. In the positive resist composition of the present invention, the inclusive transbasic compound represented by the above formula (1) is a component of the component (C). By coordinating such (C') ingredients. Further, a positive-type resist composition having excellent linearity can be obtained. Specifically, for example, a low NA condition (preferably 0.3 or less, more preferably 0.2 or less) can be obtained, and it is suitable for shorter wavelength than g-ray. The positive photoresist composition of the i-ray exposure step. With the effect of both of them, the resolution is greatly improved, and as a result, it is suitable as a photoresist composition for the i-ray exposure step for the L C D system for low-N A conditions. The amount of the component (C) is selected from the range of 5 to 50 parts by mass, preferably 10 to 30 parts by mass, based on 100 parts by mass of the alkali-soluble resin of the component (A). The composition of the present invention is preferably a solution type in which the components (A) to (C) and various additives to be added as needed are dissolved in the following component (D) of the organic solvent. The organic solvent used in the present invention is not particularly limited, but at least one selected from the group consisting of propylene glycol monoalkyl ether acetate, alkyl lactate, and 2-heptanone is excellent in coatability and is resistant to light on a large glass substrate. It is preferable that the film thickness of the film is excellent in uniformity. In the propylene glycol monoalkyl ether acetate, propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") is particularly preferable, and the film thickness uniformity of the photoresist film on a large glass substrate is extremely excellent. -14- 1263863 (11) In addition, ethyl lactate is also the most preferable, but when using a large glass substrate of 500 mm X 60 mm or more, if it is used alone, uneven coating may occur. There is a tendency to use a mixture with other solvents. In particular, the composition containing both propylene glycol monoalkyl ether acetate and alkyl lactate is excellent in film thickness uniformity of the photoresist film and can form a photoresist pattern having an excellent shape. When a propylene glycol monoalkyl ether acetate and an alkyl lactate are used in combination, it is desirable to blend the propylene glycol monoalkyl ether acetate in a mass ratio of 0.1 to 1 Torr, preferably 1 to 5 times the amount of the alkyl lactate. Further, other organic solvents such as r-butyrolactone and propylene glycol monobutyl ether may be used, and when r-butyrolactone is used, a mixture of propylene glycol monoalkyl ether acetate may be used, and In this case, the mass ratio of r-butyrolactone to propylene glycol monoalkyl ether acetate is desirably 0.01 to 1 times, preferably 0.05 to 0.5 times. Further, an organic solvent other than the above may also be used. For example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone; ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol Acetate, or monovalent ethers of monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether, derivatives thereof, cyclic ethers such as dioxane: and methyl acetate Ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxy propionate and the like. When a solvent such as acetone or the like is used, a mixture of one or more selected from the group consisting of propylene glycol monoalkyl ether acetate, alkyl lactate, and 2 · heptanone is preferred. In this case, the acetone is used. The solvent -15-1263863 (12) is preferably one or more of a mixture of propylene glycol monoalkyl ether acetate, alkyl lactate, and 2-heptanone, and preferably 50% by mass or less. In the present invention, various additives such as a surfactant, an ultraviolet absorber, a storage stabilizer, and the like can be used without departing from the object of the present invention. The surfactant can be exemplified as Furorade FC-430, Furorade FC-43 1 (Commodity Name, Sumitomo 3 Μ company system), Efutop EF 1 22 A ' Efutop EF122B, Efutop EF122C, Efutop EF126 (product name, Tokem Products Co., Ltd.), Mega fa c R-08 (trade name, manufactured by Dainippon Ink Chemical Co., Ltd.) A fluorine-based surfactant. The ultraviolet absorber can be exemplified by 2, 2', 4, 4'-tetrahydroxybenzophenone, 4 dimethylamino-2', 4'-dihydroxybenzophenone, 5-amino-3-methyl- Phenyl-4-(4-hydroxyphenylazo)pyrazole, 4-dimethylamino-4'-hydroxyazobenzene, 4-diethylamino-4'-ethoxy azobenzene, 4-diethylaminoazobenzene, curcumin, and the like. An example of a method of forming a photoresist pattern for an LCD system using the composition of the present invention is shown. First, the components (A), (B), and (C) and, if necessary, various components are dissolved in a solvent of the component (D), and applied to the substrate by a spin coater. The substrate is preferably a glass substrate. The glass substrate can be used as a large substrate of 50 〇 1 〇 1111 \ 60 〇 111111 or more, particularly 55 〇 111111 к 。 Next, the substrate on which the coating film is formed is subjected to heat treatment (prebaking) at 100 to 140 ° C to remove the residual solvent to form a photoresist film. The prebaking method is a proximity bake in which a gap is sandwiched between a hot plate and a substrate. 1263863 (13) Next, for the photoresist film, for example, a mask pattern for forming a resist pattern using an ultra-pattern size of 2.0 μΐΉ or less (preferably 0.5 to 2.0 μηι) is used, and more than 2 ·0μηι (preferably more than 2〇μηι£1〇μηιΗ下)) The liquid crystal display portion of the pattern size is used to form a photomask of the photoresist pattern type reticle pattern, using the desired light source to select Sexual exposure. The light source used herein is preferably an i-ray (3 6 5 n m) for forming a fine pattern, and the exposure step for the exposure is preferably a step of a low n A condition of N A . Next, a development process using an alkaline aqueous solution is applied to the photoresist film after selective exposure, and a photoresist pattern for an integrated circuit and a photoresist pattern for a liquid crystal display portion are simultaneously formed on a substrate. Then, if it is immersed in a developing solution, for example, an alkaline aqueous solution of a 1 to 10% by mass aqueous solution of tetramethylammonium hydroxide, the exposed portion can be dissolved and removed to obtain a faithful image of the mask pattern. Next, the photoresist which remains on the surface of the photoresist pattern is washed away with a washing liquid such as pure water to form a photoresist pattern. [Examples] Hereinafter, the present invention will be described in more detail by way of examples. The physical properties of the positive resist composition of the examples or comparative examples described later were determined by the following treatment. (1) Linear evaluation:

After applying the S material to the glass substrate (550×X 6 50 mm) on which the Cur film is formed using a spin coater, the temperature of the hot plate is 130 ° C, and about 1263386 (14) Next to the baking, the first drying is performed for 60 seconds, and then the temperature of the hot plate is 120 ° C, and the second baking is performed for 60 seconds at a spacing of 〇. 5 mm to form a film. A photoresist film with a thickness of 1.5 μm. Secondly, by simultaneously drawing the reticle pattern of the photoresist pattern of the 3.0 μm line/space (L i n e & S p a c e ' , L&S) and 1.5 μηι L&S

Chart Mask, and using an i-ray exposure apparatus (device name: FX-702J, manufactured by Nikkon Co., Ltd.; ΝΑ = 0·14), to faithfully reproduce the exposure amount of 3.0 μηι L & S (Εορ exposure amount) Selective exposure. Lu Qiji, using a developing device with a slit coating nozzle for a 2 3 t, 2 · 38 mass % tetramethylammonium hydroxide aqueous solution (device name: TD- 3 9000 machine, Tokyo Yinghua Industrial Co., Ltd.) As shown in Fig. 1, the substrate end portion X passes through Y to reach Z, and the substrate is filled with liquid for 10 seconds, and after holding for 5 5 seconds, it is washed with water for 30 seconds, and is spin-dried. Thereafter, the cross-sectional shape of the obtained resist pattern was observed by SEM (scanning electron microscope) photograph, and the reproducibility of the resist pattern of 1.5 μηι L & S was evaluated. The results are shown in Table 2. Spring (2) Sensitivity evaluation: Use the above Εορ exposure amount as an indicator of sensitivity evaluation. The results are shown in Table 2. (3) Resolution evaluation: The boundary resolution in the above Εορ exposure amount is obtained, and the results are shown in Table 2 -18- (15) 1263863 (4) Scum evaluation: In the above Ε ο P exposure amount, Ε Μ (Scanning Electron Microscope) The surface of the substrate depicted by 1.5 μηι L&S was observed and investigated for scum. Those who have not seen the scum at all are indicated by ◎, and those who have almost no scum at all are indicated by 〇, those who are slightly observed are indicated by △, and those who have a large amount of scum are indicated by X. The results are shown in Table 2. (5) Shape evaluation: In the above Εορ exposure amount, the resist pattern cross section of 1·5μηι L&S was observed by SEM (scanning electron microscope), and the cross-sectional shape was approximately rectangular, which was indicated by ◎, and the film was slightly observed. The thinner is represented by 〇, the shape of the cone is represented by △, the pattern is rolled into a filament, or the pattern is mostly thinned by X. The results are shown in Table 2. <Example 1 > (A) component alkali-soluble resin (A1) A1: mixed phenol and a condensing material using p-formaldehyde for m-cresol/3,4-xylenol = 9/1 (mole ratio) /Formaldehyde = 1/3 (mole ratio) mixed aldehyde and synthesized according to the conventional method Mw = 4 75 0, Mw / Mn = 2.44 phenolic enamel resin (B) Component: naphthoquinone diazide ester 40 parts by mass (B1/B2/-1/1)

B1: bis(2-methyl-4-hydroxy-5-cyclohexylphenyl)_3,4-dihydroxyphenylmethane 1 与 and 1,2-naphthoquinonediazide-5-sulfonyl chloride ( Hereinafter referred to as "5 - NQD 1263863 (16)" (2 moles of esterification reaction product B2: bis-(2,3,5-trimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane 1 Molar and 5 - NQD 2 molar esterification reaction product (C) component: phenolic hydroxyl group-containing compound (c 1 ) 2 5 parts by mass C1 : 1-[1, bus(4-hydroxyphenyl) 4-[l-(4-hydroxyphenyl)isopropyl]benzene The above-mentioned (A) to (C) components and the total mass of the components (A) to (C) are equivalent to 350 ppm. The amount of the surfactant, Megafac R-08 (trade name, manufactured by Dainippon Ink Co., Ltd.), was dissolved in PGMEA, adjusted to a concentration of the solid component [total of (A) to (C) components] of 25 to 28% by mass, and This was filtered using a membrane filter having a pore size of 0.2 μm to prepare a positive resist composition. <Examples 2 to 9>, &lt;Comparative Examples 1 to 4&gt; In addition to the ratios shown in Table 1, the compositions described in Table 1 were used. Using the composition of (Α) to (D), the composition of the positive resist is processed in the same manner as in the first embodiment. The results of their evaluation are shown in Table 2. Also, the positive resist composition of Comparative Example 4 did not depict the L &amp; S pattern of 1.5 μm, so no linear evaluation was performed. 1263863 (17 ) [Table 1] (A) (B) (mixing ratio) (C) (mixing ratio) (D) 1 A 1 B 1 /B2 C1 PGMEA (1/1) (25 parts by mass) 2 A1 B3/B4 C1 PGMEA Real (1/1) (25 parts by mass) 3 A1 B 1 /B5 C1 PGMEA Application (1/1) (25 parts by mass) 4 A2 B1/B2 C1 PGMEA Example (1/1) (25 parts by mass) 5 A3 B1/B2 C1 PGMEA (1/1) (25 parts by mass) 6 A1 B1/B2 C1 NS (1/1) (25 parts by mass) 7 A1 B1/B2 C1 HE (1/1) (25 parts by mass) 8 A1 B 1 /B2 C1 PGMEA (1/1) (20 parts by mass) 9 A1 B 1 /B2 C1 PGMEA (1/1) (30 parts by mass) than 1 A1 B 1 /B2 C2 PGMEA (1/1 (25 parts by mass) Example 2 A1 B 1 /B2 C3 PGMEA (1/1) (25 parts by mass) 3 A1 B 1 /B2 C4 PGMEA (1/1) (25 parts by mass) 4 A1 B 1 /B2 C5 PGMEA (1/1) (25 parts by mass) 1263863 (18) In Table 1, each symbol indicates the following meaning A2: p-toluene oxime/p-toluic acid/2,5·xylene oxime Bu 4/2/4 (Morbi) mixed phenol and condensate material using formaldehyde and synthesized according to the conventional method Mw = 500 00, Mw / Mn = 28 phenolic enamel resin, 3,5 _ three The phenolic mixture is a mixture of formaldehyde/croton A3: p-cresol/p-cresol/2 = 9/0.5/0.5 (mole ratio) mixed phenol and acetal = 2/1 (mole ratio). Aldehyde and synthesized according to the usual method (10)

Mw/MhU5 phenolic enamel resin B3 based. 1,1-bis[3-(2-hydroxy-5-methylbenzyli-4-hydroxy-5-cyclohexylbenzene)isopropane 1 molar and 5-NQD2 Molar esterification reaction product Β 4 ·· 2,3,4,4 Esterification reaction product-tetrahydroxybenzophenone 1 molar and 5-NQD2.34 molar Β5: methyl gallate i Esterification reaction product of ear with 5_NQD3 mole C2: bis(3,5-dimethyl-4-hydroxyphenyl)-3,4-dihydroxyphenylmethane C3: bis(4-hydroxyphenyl)_4_ Hydroxyphenylmethane

C4: bis(2,3,5-trimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane C5: bis[3-(3,5-dimethyl-4-hydroxybenzyl)-4 -hydroxy-5-methylphenyl]methane PGMEA: propylene glycol monomethyl ether acetate NS: 9/1 (mole ratio) mixture of ethyl lactate and butyl acetate HE: 2-heptanone-22- (19 ) 1263863

[Table 2] ------ Linear evaluation sensitivity evaluation Image scum evaluation shape evaluation (μηι) Price evaluation price - -.. (m J ) (μ m ) 1 - 45 1 .3 ◎ ◎ 2 —__1^60 50 1 .3 〇◎ Real 3 --LJ2 60 1 .3 Δ 〇4 ——~i_62 43 1.3 5 5 __Ll5 7 45 1 .3 Δ 〇6 —~ϋ9 60 1.3 Example 7 ___Κ65 68 1.3 〇〇8 53 1 .3 〇Δ 9 -__^4 30 1.3 Δ Δ ratio 1 — 4 5 1 .4 Δ • Δ · Compared with 2 __J^8 5 35 1 .4 Δ Δ Example 3 __1^9 1 70 1.4 〇Δ 4 - 60 1 .7 x X

As is clear from Table 2, the positive resist composition of the comparative example was not subjected to linear evaluation because the pattern was not drawn, and the linear evaluation result of the obtained pattern was 1. 8 5 μηι or more. The shape is also Δ~X, and the resolution is also 丨.4 μηι or more. In contrast, the positive resistive composition of the present invention has a linear evaluation of the pattern of 1. 6 8 μπι and is close to 1.5 Ο μιιι, and it can be seen that a linearly excellent pattern can be obtained. Further, the resolution was also 1.3 μm and showed better resolution than the comparative example. -23- (20) 1263863 In addition, it was found that all of the sensitivity, resolution, scum evaluation, and shape evaluation including linearity were good, and a good balance was obtained in all evaluation items [effect of the invention] As described above, in the present invention, a pattern having excellent linearity is obtained, and an excellent positive resist composition for manufacturing a substrate (LCD system) for forming an integrated circuit and a liquid crystal display portion on one substrate can be provided. Further, according to the photoresist pattern forming method of the present invention, it is possible to form a fine photoresist pattern which is excellent in linearity and which is suitable for manufacturing an L C D system. [Simplified illustration of the drawing] [Fig. 1] For linear evaluation, a positive photoresist composition is applied to a glass substrate 'and baked and dried, and the pattern is exposed, followed by a developing device having a slit coater An explanatory view in which the developing liquid is filled with liquid from the end portion X of the substrate toward z. -twenty four-

Claims (1)

1263863 (1) Picking up, applying for patent coverage No. 9 2 1 1 8 2 3 Patent application No. 3 Revision of the Chinese patent application scope Amendment dated December 29, 1993]. A positive-type photoresist composition manufactured on a substrate A positive-type photoresist composition for forming a substrate on an integrated circuit and a liquid crystal display portion, characterized in that it contains a (Α) alkali-soluble resin, and the total amount of the (Α) component and the (C) component is 20 to 70% by mass. (Β) naphthoquinone diazide ester compound, 5 to 50 parts by mass based on 100 parts by mass of the (Α) component (C) phenolic hydroxy compound represented by the following general formula (1) OH OH and (D) organic solvents. The positive-type resist composition of the first aspect of the invention, wherein the component (D) is one or more selected from the group consisting of propylene glycol monoalkyl ether acetate, alkyl lactate and 2-hexanone. 3. A positive-type photoresist composition as claimed in claim 1, wherein the positive-type photoresist composition is used for an i-ray (3 65 nm) exposure step. 4. The positive-type photoresist composition according to the scope of the patent application, wherein the positive (2) 1263863 type photoresist composition is used for an exposure step of NA 〇. 3 or less. And a method for forming a film comprising the method of applying a positive photoresist of any one of the first to fourth aspects of the patent application to the substrate to form a coating film (2) a step of forming a resist film on the substrate by heat-treating the substrate on which the coating film is formed, and (3) using the photoresist pattern for forming the integrated circuit for forming the integrated circuit and forming a liquid crystal. Part of the photoresist pattern used in the photomask of the reticle pattern has a selective exposure step' (4) For the above-mentioned selective exposure of the photoresist film, an imaging treatment using an alkaline aqueous solution is applied' a step of simultaneously forming a photoresist pattern for an integrated circuit and a photoresist pattern for a liquid crystal display portion on the substrate. (5) a washing step of washing the developer liquid remaining on the surface of the photoresist pattern. 6. The method of forming a photoresist pattern according to claim 5, wherein the step of performing the above (3) selective exposure is performed by an exposure step of using a light source using an i-ray (365 nm). 7. The method of forming a photoresist pattern according to claim 5 or 6, wherein the step of performing the (3) selective exposure is carried out by an exposure step at a low NA condition of NA of 0.3 or less. 8 The method for forming a photoresist pattern according to claim 5, wherein the photoresist pattern for the integrated circuit in the above step (4) is a photoresist pattern having a line width of 2.0 Å or less. 9 . The method for forming a photoresist pattern according to item 5 of the patent application scope, wherein the photoresist pattern for the liquid crystal display portion in the above step (4) in the step -4 is to exceed 2 . The photoresist pattern of μ m. -3-