TW200402599A - 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

200402599 Π) Description of the invention [Technical field to which the invention belongs] The present invention relates to a positive type photoresist composition and a method for forming a photoresist pattern for manufacturing a substrate on which an integrated circuit and a liquid crystal display portion are formed on a single substrate. [Prior art] So far, for example, in the field of manufacturing a liquid crystal display element using a glass substrate, since it is relatively inexpensive and can form a photoresist pattern with excellent sensitivity, resolution, and shape, it is used in many semiconductor element manufacturing Positive photoresist material composed of phenolic lacquer resin-quinonediazide-based compound system. However, in the manufacture of semiconductor devices, a disc with a diameter of 8 inches (about 200 mm) to 12 inches (about 300 mm) can be used at the maximum. In contrast, in molding sand wafers, a square glass substrate of about 360 mm x 460 mm is used as a minimum in the manufacture of liquid crystal display elements. Thus, in the field of manufacturing liquid crystal display elements, the size is greatly different from that of semiconductor elements. Therefore, for a photoresist material for manufacturing a liquid crystal display element, a photoresist pattern capable of being formed on a wide substrate surface and having a good shape and size stability is required. Photoresist materials for the production of such liquid crystal display elements are known, for example, in Japanese Patent Application Laid-Open No. 9-1 6023 1; Japanese Patent Application Laid-Open No. 9- 2 1 1 8 5 5; Japanese Patent Application Laid-Open No. 2000-112120; Japanese Patent Application Laid-Open No. 2000-1 Many reports including 3 1 83 Publication No. 5, JP 2000--5- μ (2) (2) 200402599 1 8 1 0 5 5 and JP Publication No. 200 1 _75 272. These materials are inexpensive and can form photoresist patterns with excellent coatability, sensitivity, resolution, shape, and dimensional stability for smaller substrates of about 360 mm x 360 mm, so they are suitable for manufacturing. For the purpose of LCD with only display part. On the other hand, the second-generation LCD is now actively forming drivers, DACs (digital-to-analog converters), image processors, video controllers, RAM, etc. on a glass substrate to form integrated circuits and Technical development of the LCD in the display part (Semiconductor FPD World 200 1 · 9 'PP · 5 0-67). Hereinafter, in this specification, such a substrate forming an integrated circuit and a liquid crystal display portion on one substrate is referred to as an LCD system for convenience. However, the pattern size of such LCD systems in the display part is, for example, about 2 to 10 μm. In contrast, the pattern size of the integrated circuit part must be in a fine size of about 0.5 to 2.0 μm, so under the same exposure conditions In the case where such integrated circuit portions and display portions are to be formed, linearity is desired [under the same exposure conditions (conditions where the mask size on the reticle is different but the exposure amount is the same), and the light on the reticle is exposed during exposure. The characteristics of hood size reproduction] are excellent. In addition, in order to form a fine pattern of an integrated circuit portion, it is necessary to increase a resolution that is not available in a photoresist material used in the manufacture of liquid crystal display elements today. In order to improve the resolution (resolution limit), the formula is as follows: R = k] X person / ΝΑ (where R is the resolution limit, k) is determined by photoresist, steps, and image formation method Proportional constant, λ is -6-.31 ^ used in the exposure step (3) (3) 200402599 Light wavelength, NA is the number of openings of the lens) As shown, a short-wavelength light source or a high NA Exposure steps. Therefore, when forming a fine photoresist pattern of, for example, less than 2.0 μιη as described above, it is effective to expose by a previous g-ray (43 6nm), for example, a photomicrograph exposed using a shorter wavelength i-ray (3 65 nm). Shadow technology. On the other hand, from the viewpoint of improving the throughput (the number of processes per unit time), it is desirable to make the exposure area in the liquid crystal field at least about 100 mm2. If the exposure area is widened, it will not only be difficult to maintain a uniform plane in this part. It is difficult to achieve high NA because the depth of focus is not suitable for high NA lenses. In the field of manufacturing liquid crystal display elements, based on the above reasons, low NA conditions of 0.3 or less are generally preferred, but conventional photoresist materials used in the manufacture of liquid crystal display elements have difficulty forming 0.5 to 2 with excellent shapes under low NA conditions. The fine photoresist pattern of about 0 μm, and the cross-sectional shape of the photoresist pattern is not rectangular, but tends to show a cone shape. Therefore, a photoresist material for manufacturing an LCD system that can form a fine photoresist pattern with excellent linearity even under low NA conditions is desired. [Problems to be Solved by the Invention] Therefore, in the present invention, it is an object of the present invention to provide a photoresist material having excellent linearity suitable for manufacturing an LCD system as described above. [Means for solving the problem] As a result of intensive research in order to solve the above-mentioned problems, the inventors of the present invention etc.-7- (4) 200402599 found that a positive-type photoresist composition containing a specific phenolic hydroxyl compound was found to be low. A fine photoresist pattern can also be formed under NA conditions, and it is a photoresist material with excellent linearity, and is suitable for manufacturing LCD systems, and has completed the present invention. That is, the present invention is a compound containing (A) an alkali-soluble resin, (B) a naphthoquinonediazide ester compound, and (C) a phenolic hydroxyl group-containing compound represented by the following general formula (I)

OH

And (D) an organic solvent having a positive-type photoresist composition for manufacturing a substrate on which an integrated circuit and a liquid crystal display portion are formed on a substrate. Furthermore, the present invention relates to (1) a step of applying the above-mentioned positive-type photoresist composition on a substrate and forming a coating film, and (2) heating the substrate formed on the above-mentioned coating film on the substrate. Steps of forming a photoresist film, (3) For the above photoresist film, use both a photomask pattern for forming an integrated circuit pattern and a photomask pattern for forming a photoresist pattern for a liquid crystal display portion. (4) The photoresist film after the selective exposure is subjected to a development process using an alkaline aqueous solution, and an integrated circuit for the integrated circuit is simultaneously formed on the substrate. (8) (5) (5) 200402599 Photoresist pattern and the steps of photoresist pattern used in liquid crystal display, (5) the washing step of washing the imaging solution remaining on the photoresist pattern surface as its characteristic photoresist pattern Formation method. [Embodiments of the invention] In the positive-type photoresist composition of the present invention, the alkali-soluble resin as the component (A) is not particularly limited, and it can be generally used as a film-forming substance from the positive-type photoresist composition. Select any. Examples of the alkali-soluble resin include phenols such as phenol, m-cresol, p-cresol, xylenol, and trimethylphenol, and formaldehyde, a precursor of formaldehyde, 2-hydroxybenzaldehyde, and 3-hydroxybenzene. Formaldehyde, 4-hydroxybenzaldehyde, and other aldehydes are condensed in the presence of acidic catalysts, phenolic resins, hydroxystyrene monopolymers, hydroxystyrene and other styrene-based monomer copolymers, hydroxyl groups A hydroxystyrene resin such as a copolymer of styrene and acrylic acid or methacrylic acid or a derivative thereof, and an alkali-soluble resin such as an acrylic acid or methacrylic resin of a copolymer of acrylic acid or methacrylic acid and a derivative thereof. In particular, a phenolic lacquer resin obtained by the condensation reaction of phenols containing m-cresol and 3,4-xylenol with propionaldehyde and methylbenzene is a photoresist material suitable for adjusting high sensitivity and excellent linearity. In the positive photoresist composition of the present invention, the naphthoquinonediazide acetate as the component (B) is not particularly limited, and the naphthoquinonediazide which has been previously used as the photosensitive component of the photoresist can be used. Any of the basic esters, in particular the following general formula (II) (6) 200402599

[Wherein R to R 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; R10 And R11 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; q is bonded or unbound to the terminal of R9; Q is not bonded to the terminal of R9, and R9 is a hydrogen atom or 1 to 6 carbon The alkyl group 'q is a hydrogen atom, an alkyl group having 6 to 6 carbon atoms, or a residue represented by the following chemical formula (ΠI)

R

(melon)

(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; c Is an integer from 1 to 3), when Q is bonded to the terminal of R9, Q and R9 are together with the carbon atoms between Q and R9 to form a cycloalkyl group of 3 to 6 carbon chains; a and b represent 1 An integer of ~ 3; d is an integer of 0 to 3; η is an integer of 0 to 3] The esterified product of a phenol compound and a naphthoquinonediazide sulfonic acid compound shown in FIG. 2 Shadowing is also suitable, for example, when a fine photoresist pattern of 2.0 μm or less is desired to form a good shape. In addition, when Q and R9 form a carbon chain together with a carbon atom between Q and R9-10- (7) (7) 200402599 3 to 6 alkyl groups, Q and R9 are bonded to form a carbon number of 2 to Five alkylene groups corresponding to this general formula include tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, and bis ( 4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, 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, bis (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-dihydroxyphenylmethane, 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-cyclo Hexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane, etc. Triphenol compounds; bis (2,3,4 · trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) methane, 2,3,4-trihydroxyphenyl-4'hydroxyphenyl Methane, 2,4-bis (3,5 · dimethyl-4-hydroxybenzyl) -5 · hydroxyphenol, 2,6-bis (2,5-dimethyl-4-hydroxybenzyl) -4 -Linear trinuclear phenol compounds such as methylphenol; 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-bis (8) (8) 200402599 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-methylbenzene ] Methane, bis [3- (3,5-diethyl-4-hydroxybenzyl) -4-hydroxy-5-ethylphenyl] methane, bis [2-hydroxy-3- (3,5-di Methyl-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-methylbenzyl) ) 5-methylphenyl] linear phenolic compounds such as methane; 2,4-bis [2-hydroxy-3- (4-hydroxybenzyl) -5-methylbenzyl] -6- Cyclohexylphenol, 2,4-bis [4-hydroxy-3- (4-hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,6-bis [2,5-dimethyl Linear polyphenol compounds such as linear pentanuclear phenol compounds such as 3- (2-hydroxy-5-methylbenzyl) -4-hydroxybenzyl] -4-methylphenol; 2. · (2,3 , 4-trihydroxyphenyl) -2- (2 ', 3', 4, trihydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) 2- (2 ', 4'-dihydroxy Phenyl) propane, 2- (4-hydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (3-fluoro-4-hydroxyphenyl) -2- (3f-fluoro-4 ' -Hydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl) 2- (4 '· hydroxyphenyl) propane , 2- (2,3,4 · trihydroxyphenyl) 2- (4'-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) 2- (4hydroxy-3 ', 5'-dimethylphenyl) propane and other bisphenol compounds; 1-Π, 1-bis (4-methylphenyl) ethyl] -4- [1- (4-hydroxyphenyl) isopropyl Yl] benzene, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [l, 1-bis (4-hydroxyphenyl) ethyl] benzene, 1- [1- (3-methyl Polynuclear branched compounds such as 4-hydroxyphenyl) isopropyl] -4- (1, 1-bis (3-methyl-4-hydroxyphenyl) ethyl) phenyl; 1,1-bis Condensed phenol compounds such as (4-hydroxyphenyl) cyclohexane. Among them, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxybenzene (9) (9) 200402599 methane, bis (4-hydroxy-2,3,5- Triphenol type compounds such as trimethylphenyl) -2-hydroxyphenylmethane, 1,1-bis [3- (2 · hydroxy-5-methylbenzyl) -4-hydroxy-5-cyclohexylbenzene A linear tetranuclear phenol compound such as propyl] isopropane is preferred in terms of sensitivity, resolvability, and formation of 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 general formula (11) with naphthoquinonediazidesulfonic acid can be performed according to a conventional method. For example, naphthoquinonediazidesulfonyl chloride and the above It can be obtained by condensing a compound represented by general formula (II). Specifically, the compound represented by the general formula (II) and naphthoquinone-1,2-diazidyl-4- (or 5) -sulfonyl chloride are dissolved in dioxane and n-methyl in a specified amount. In an organic solvent such as pyrrolidone, dimethylacetamide, tetrahydrofuran, etc., basic catalysts such as triethylamine, triethanolamine, pyridine, alkali metal carbonates, alkali metal carbonates, and the like are added and reacted. The product can be prepared by washing with water and drying. (B) In addition to the naphthoquinonediazide esterified product exemplified above, other naphthoquinonediazide esterified products can be used, such as phenol compounds such as polyhydroxybenzophenone and alkyl gallate, and An esterification reaction product of a naphthoquinonediazidesulfonic acid compound can also be used. The amount of the naphthoquinonediazidesulfonic acid compound is 80% by mass or less in the component (B), particularly 50% by mass or less, because the effect of the present invention is not impaired. Better. In the positive type photoresist composition of the present invention, the compounding amount of the component (B) is 20 to 70%, preferably 30 to 50%, relative to the total mass of the component (A) and the following component (c). It is better to choose in the quality range. (B) If the blending amount of the component is lower than the above range, a faithful image cannot be obtained, and the transferability may be reduced. -13- j I {(10) (10) 200402599 will be reduced. On the other hand, if the blending amount of the component (B) exceeds the above-mentioned range ', the sensitivity is deteriorated, the homogeneity of the formed photoresist film is reduced, and the resolvability may be deteriorated. In the positive-type photoresist composition of the present invention, the phenolic hydroxyl compound represented by the above formula (I) is blended as the component (C), which is a major feature. By blending such (C) ingredients. A positive photoresist composition with excellent linearity can be obtained. Specifically, for example, a positive-type photoresist composition suitable for a low NA condition (preferably 0.3 or less, more preferably 0.2 or less) and suitable for an i-ray exposure step having a shorter wavelength than a g-ray can be obtained. With these two effects, the resolution is greatly improved, and as a result, it is suitable as a photoresist composition for i-ray exposure steps for manufacturing LCD systems under low NA conditions. The compounding 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). Lcrn is selected. The composition of the present invention is preferably a solution type in which the components (A) to (C) and various additional components blended as necessary are dissolved in the following component (D) of an 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 has excellent photoresistance on a large glass substrate due to its excellent coating properties. The film thickness is excellent because it is excellent in uniformity. Among the propylene glycol monoalkyl ether acetates, propylene glycol monomethyl ether acetate (hereinafter, referred to as "PGMEA") is particularly preferable, and the uniformity of the thickness of the photoresist film on a large glass substrate is excellent. -14- (11) (11) 200402599 In addition, ethyl lactate is the best among alkyl lactates, but when using a large glass substrate of 500 mm x 60 mm or more, the coating tends to be uneven if used alone. Therefore, it is desirable to use a mixed system with other solvents. In particular, a composition containing both propylene glycol monoalkyl ether acetate and alkyl lactate is preferable because the photoresist film has excellent film thickness uniformity and can form a photoresist pattern having an excellent shape. When a propylene glycol monoalkyl ether acetate and an alkyl lactate are mixed and used, it is desirable to mix the propylene glycol monoalkyl ether acetate with a mass ratio of 0.1 to 10 times the amount, preferably 1 to 5 times the amount of the alkyl lactate. In addition, other organic solvents such as r-butyrolactone and propylene glycol monobutyl ether can also be used. When 7-butyrolactone is used, it is preferable to use a mixture type with propylene glycol monoalkyl ether acetate, and In this case, it is desirable to make r-butyrolactone to propylene glycol monoalkyl ether acetate in a mass ratio of 0.01 to 1 times the amount, preferably 0.05 to 0.5 times the amount. In addition, organic solvents other than the above may be used. For example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isopentanone; ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoone Acetic acid esters, or their polyvalent alcohols such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether and derivatives thereof, cyclic ethers such as dioxane; and methyl acetate , Ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate and the like. When using these solvents such as acetone, it is preferable to use a mixture type of one or more mixtures selected from propylene glycol monoalkyl ether acetate, alkyl lactate, and 2-heptanone. In this case, the aforementioned acetone Solvents such as -15- (12) (12) 200402599 are selected from propylene glycol monoalkyl ether acetate, alkyl lactate, and 2-heptanone, or a mixture of two or more, preferably 50% by mass or less. . In the present invention, various additives such as a surfactant, a UV absorber, a storage stabilizer, and the like can be used within a range that does not impair the object of the present invention. Examples of the surfactant include Furorade FC-430 and Furorade FC-431 (trade names , Manufactured by Sumitomo 3M), Efutop EF122A, Efutop EF122B, Efutop EF122C, E fut op EF126 (trade name, manufactured by Tokem Products), Megafac R-08 (trade name, manufactured by Dainippon Ink Chemical Co., Ltd.) and other fluorine-based interfaces Active agent. Examples of the ultraviolet absorber include 2, 2 ', 4, 4f-tetrahydroxybenzophenone, 4-dimethylamino-2f, 4'-dihydroxybenzophenone, and 5-amino-3-methyl-1- Phenyl-4- (4-hydroxyphenylazo) pyrazole, 4-dimethylamino-4'-hydroxyazobenzene, 4-diethylamino-4'-ethoxyazobenzene, 4 -Diethylamino azobenzene, curcumin, etc. An example of a method for appropriately forming a photoresist pattern for manufacturing an LCD system using the composition of the present invention is shown. First, the component (A), the component (B) and the component (C), and various components added as necessary are dissolved in a solvent of the component (D), and applied to a substrate by a spin coater. The substrate is preferably a glass substrate. This glass substrate can use large substrates of 500mmx600mm or more, especially 550mmx650mm or more. Next, the substrate on which the coating film is formed is subjected to a heat treatment (pre-baking) at, for example, 100 to 140 ° C to remove the residual solvent to form a photoresist film. The pre-baking method is the closest proximity bake between the hot plate and the substrate. (13) (13) 200402599 Secondly, for the photoresist coating, for example, use a drawing of less than 2.0 μm (better A photoresist pattern for forming a photoresist pattern for an integrated circuit with a fine pattern size of 0.5 to 2.0 μιη, and a liquid crystal display having a pattern size of more than 2.0 μπι (preferably more than 2.0 μm and less than 10 μm) Part of the photomask used to form both the photoresist pattern pattern and the selective exposure using the desired light source. The light source used here is preferably an i-ray (3 65 nm) for forming a fine pattern, and the exposure step used for this exposure is preferably a step with a low NA condition where NA is 0.3 or less. Secondly, the photoresist film after selective exposure is subjected to a development treatment using an alkaline aqueous solution, and a photoresist pattern for an integrated circuit and a photoresist pattern for a liquid crystal display portion are simultaneously formed on a substrate. Next, by immersing in a developing solution, such as an alkaline aqueous solution such as a 10 to 10% by mass tetramethylammonium hydroxide aqueous solution, the exposed portion can be dissolved and removed to obtain a faithful image of the mask pattern. Next, the developing solution remaining on the surface of the photoresist pattern is washed away with a washing solution such as pure water to form a photoresist pattern. [Examples] Hereinafter, the present invention will be described in more detail using examples. Each physical property of the positive-type photoresist composition of the Example or the comparative example mentioned later was calculated | required as follows. (1) Linear evaluation: After applying a sample to a glass substrate (550 mm x 650 mm) forming a Cl * film using a spin coater, the temperature of the hot plate was set to 13 (TC, and approximately 1 mm- 17- (14) (14) 200402599 Proximity baking at 60-second intervals, first drying for 60 seconds, secondly, set the temperature of the hot plate to 120 ° C, and apply proximate baking at 0.5mm intervals for 60 seconds. The second drying process forms a photoresist film with a thickness of 1.5 μm. Secondly, the photoresist patterns of 3.0 μm Line / Space (L & S) and 1.5 μm L & S are drawn simultaneously. Test Chart Mask (reticle) of each mask pattern reproduced by the model, and using an i-ray exposure device (device name: FX-7 02J, manufactured by Nikkon Corporation; NA = 0.14), faithful reproduction of 3.0 μm L & S The exposure amount (Eορ exposure amount) is subjected to selective exposure. Next, a developing device (device name ··) with a slit coating nozzle was used at a temperature of 2 ° C, 23.8% by mass of a tetramethylammonium hydroxide aqueous solution. TD-3 9000 model, manufactured by Tokyo Chemical Industry Co., Ltd., as shown in Figure 1, passes from the substrate end X to Y to Z, and lasts 10 seconds on the substrate After being filled with liquid and kept for 5 5 seconds, it was washed with water for 30 seconds and then dried by spin. After that, the cross-sectional shape of the obtained photoresist pattern was observed with a SEM (scanning electron microscope) photograph. Evaluation 1.5 Lm & The reproducibility of the photoresist pattern of S. The results are shown in Table 2. (2) Sensitivity evaluation: The above-mentioned exposure dose of Eορ was used as an index of sensitivity evaluation. The results are shown in Table 2. (3) Resolution Evaluation: The limit resolution in the above-mentioned Eορ exposure amount was obtained. The results are shown in Table 2. (15) (15) 200402599 (4) Scum evaluation: In the above-mentioned Eορ exposure amount, observed by SEM (scanning electron microscope) 1 5μιη L & S substrate surface, and investigate the presence of scum. Those who have not seen scum at all are shown by ◎, those who have almost no scum are seen by ◦, those who have seen a little are shown by △, a large amount The occurrence of scum is indicated by X. The results are shown in Table 2. (5) Shape evaluation: Observing the photoresistance pattern of 1.5 μm L & S with the SEM (scanning electron microscope) in the exposure amount of EO above. The shape of the cross section is indicated by ◎ if the cross section is approximately rectangular. A slight observation of the film thickness is indicated by 0, a cone shape is indicated by Δ ', a pattern is rolled into a filament, or a pattern whose most of the pattern is film thickness is indicated by χ. The results are shown in Table 2. & lt Example 1 > (A) component alkali-soluble resin (A1) A1: p-m-cresol / 3,4-xylenol == 9/1 (molar ratio) mixed phenol and condensation material using propionaldehyde / Formaldehyde = 1/3 (molar ratio) mixed aldehyde and Mw = 4750 and Mw / Mn = 2.44 phenolic resin based on conventional methods (B) Composition: 40 parts by mass of naphthoquinonediazide (Bl / B2 / = 1/1) B1 ·· Bis (2-methylhydroxy_5-cyclohexylphenyl) 3,4-dihydroxyphenylmethane 1 旲 and 1,2 naphthoquinone diazide 5 · sulfonyl chloride (hereinafter referred to as "5-nqd (16) (16) 200402599" (2 mole esterification reaction product B2: bis- (2,3,5-trimethyl-4-hydroxyphenyl Esterification reaction product (C) of 2-hydroxyphenylmethane 1 mole and 5-NQD2 mole: 25 parts by mass of phenolic hydroxyl-containing compound (C1)

Cl: 1- [1,1-bis (4-hydroxyphenyl) ethyl] -4- [l- (4-hydroxyphenyl) isopropyl] benzene will be the components (A) to (C) above, and The surfactant M egafac R-〇8 (trade name, manufactured by Dainippon Ink Co., Ltd.) equivalent to 350 ppm parts relative to the total mass of the components (A) to (C) is dissolved in PGMEA and adjusted to a solid content [ (Total of (A) to (C) components] The concentration is 25 to 28% by mass, and it is filtered using a membrane filter having a pore size of 0. 2 μm to prepare a positive photoresist composition. < Examples 2 to 9 >, < Comparative Examples 1 to 4 > The same as Example 1 except that the substances described in Table 1 were used at the compounding ratios described in Table 1 as the components (A) to (D). Processes modulated positive photoresist composition. Their evaluation results are shown in Table 2. In addition, the positive photoresist composition of Comparative Example 4 did not draw an L & S pattern of 1.5 μm, so no linear evaluation was performed. (17) 200402599 [Table 1] (A) (B) (Mixing ratio) (C) (Mixing ratio) (D) 1 A1 B 1 / B2 C1 PGMEA (1/1) (25 parts by mass) 2 A1 B3 / B4 C1 PGMEA (1/1) (25 parts by mass) 3 A1 B 1 / B5 C1 PGMEA (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) Parts) 8 A1 B1 / B2 C1 PGMEA (1/1) (20 parts by mass) 9 A1 B1 / B2 C1 PGMEA (1/1) (30 parts by mass) is better than 1 A1 B 1 / B2 C2 PGMEA (1/1 ) (25 parts by mass) Example 2 A1 B1 / B2 C3 PGMEA (1/1) (25 parts by mass) 3 A1 B1 / B2 C4 PGMEA (1/1) (25 parts by mass) 4 A1 B1 / B2 C5 PGMEA (1 / 1) (25 parts by mass) (18) (18) 200402599 In Table 1, 'each I number' means the following meaning. A2: p-m-cresol / p-cresol / 2,5-xylenol = 4/2/4 (molar ratio) mixed phenol and condensation materials using formaldehyde and Mw synthesized by conventional methods = 5,000 Phenolic lacquer resin A3 with Mw / Mn = 2.8: p-cresol / p-cresol / 2,3,5 · trimethylphenol = 9/0 · 5 / 0.5 (molar ratio) mixed phenol Formaldehyde / croton 2/1 (ear ratio) mixed aldehyde and a phenolic lacquer resin B3 with mw = 7〇q〇 and Mw / Mh = 3.05 synthesized according to a conventional method with a condensation material B3: 1 '1 -Esterification reaction product of bis [3- (2-hydroxy-5-methylbenzyl) -4-hydroxy-5-cyclohexylphenyl] isopropane and 5-NqD2 mole B4: 2,3 Esterification reaction product of 4,4, tetrahydroxybenzophenone 1 mole and 5-NQD2.34 mole. B5: esterification reaction product of methyl gallate 1 mole and 5-NQD3 mole. C2: Bis (3,5-dimethyl-4-hydroxyphenyl) -3,4-dihydroxyphenylmethane C3: bis (4-hydroxyphenylhydroxyphenylmethane C4: bis (2,3,5-tris Methyl-4-hydroxyphenyl) -2-hydroxyphenylmethane C5: bis [3_ (3,5-dimethyl-4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane PGMEA : Propylene glycol monomethyl ether acetate NS: Milk Ethyl and butyl acetate 9/1 (mole ratio) mixed HE: 2- heptanone

.-V

MO -22- (19) 200402599

[Table 2] Linear evaluation, sensitivity evaluation, scum evaluation, shape evaluation (μηι), evaluation value (111 J) (μm) 1 1.50 45 1.3 ◎ 2 1.60 50 1.3 〇 〇 3 1.52 60 1.3 Δ 〇 4 1.62 43 1 .3 〇〇5 5 1.57 45 1.3 Δ 〇6 1.49 60 1.3 〇Example 7 1.65 68 1.3 〇8 1.68 53 1.3 〇 △ 9 1.4 30 1.3 △ △ ratio 1 2.02 4 5 1.4 △ • Δ 2 1.85 35 1.4 Δ Δ Example 3 1.91 70 1.4 〇Δ 4 • 60 1.7 XX

As can be seen from Table 2, since the positive type photoresist composition of the comparative example has no drawing pattern, no linear evaluation is performed, and the linear evaluation result of the obtained pattern is 1.85 μηι or more. The shape is also △ ~ X, and the resolution is 1.4 μηι or more. In contrast, the linear evaluation of the pattern of the positive-type photoresist composition of the present invention is 1.68 μηι and is close to 1.50 μm, and it can be seen that a pattern with excellent linearity can be obtained. In addition, the resolvability was also 1 · 3 μηι, and the resolvability was better than that of the comparative example. -23- (20) (20) 200402599 In addition, I learned that all of the linear sensitivity, resolution, scum evaluation, and shape evaluation were good, and a good balance was achieved in all the evaluation items [Effect of the invention] As described above, in the present invention, a pattern having excellent linearity is obtained, and an excellent positive type photoresist composition for manufacturing a substrate (LCD system) for forming an integrated circuit and a liquid crystal display portion on one substrate can be provided. In addition, according to the photoresist pattern forming method of the present invention, a fine photoresist pattern having excellent linearity and suitable for manufacturing an LCD system can be formed. [Schematic description] [Figure 1] In order to perform linear evaluation, a positive photoresist composition is coated on a glass substrate, and baked and dried. After the pattern is exposed, a developing device having a slit coater is used. An explanatory view of filling the developing liquid with the liquid from the substrate end X toward Z. -twenty four-

Claims (1)

(1) 200402599 Scope of patent application 1. A positive type photoresist composition, which is a positive type photoresist composition for a substrate formed on a substrate to form an integrated circuit and a liquid crystal display portion, which is characterized by containing (A ) Alkali-soluble resin, (B) naphthoquinonediazide esterified product, (C) phenolic hydroxyl-containing compound OH represented by the following general formula (I) And (D) an organic solvent. 2. The positive photoresist composition according to item 1 of the application, wherein the component (D) is selected from the group consisting of propylene glycol monoalkyl ether acetate, alkyl lactate, and 2-heptanone. _ 3 • The positive photoresist composition according to item 1 of the scope of patent application, wherein the positive photoresist composition is used for the i-ray (365nm) exposure step. 4. The positive-type photoresist composition according to item 1 of the patent application scope, wherein the positive-type photoresist composition is used for an exposure step with NA of 0.3 or less. 5 · —A method for forming a photoresist pattern, comprising: (1) coating a positive photoresist composition 9 as described in any one of claims 1 to 4 on a substrate to form a coating film In the steps, (2) heating the substrate on which the coating film is formed to form -25- on the substrate (2) 200402599 photoresist coating step, (3) for the above photoresist coating film, forming an integrated circuit for drawing A step of performing selective exposure using both a photoresist pattern for a photoresist pattern and a photoresist pattern for forming a liquid crystal display portion, (4) applying an alkali solution to the photoresist film after the selective exposure. In the development process, a step of simultaneously forming a pattern for an integrated circuit and a photoresist pattern for a liquid crystal display portion on the substrate, (5) a step of washing away the developing solution remaining on the surface of the photoresist pattern. 6. According to the method of forming the photoresist pattern in item 5 of the patent application, the step of performing the selective exposure (3) above is performed using an exposure step using a light source (365 nm). 7. The formation of the photoresist pattern according to item 5 or 6 of the scope of the patent application, wherein the step of performing the above (3) selective exposure is performed by an exposure step with NA of 0.3 and NA. 8 · If the photoresist pattern is formed in the patent application No.5, the photoresist pattern for the integrated circuit in step (4) above is the photoresist pattern at line width 2. 9. If the photoresist pattern is formed by the scope of the patent application No. 5: The photoresist pattern for the liquid crystal display part in step (4) above is the photoresist pattern of line 2.0 μm. Photoresist Photomask Photoresist Water-soluble photoresist Washing method, its i-ray method, lower method, its .0 μιη method, its width exceeds