TW200401950A - Positive photo resist composition and method of forming resist pattern - Google Patents

Abstract

A material preferable for manufacture of a systematic LCD, having excellent linearity, and formable for fine resist patterns is provided. A positive photoresist for manufacture of a single substrate has 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; and 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

200401950 (1) 发明. 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 an integrated circuit and a liquid crystal display portion on a 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 maximum diameter of 8 inches (about 200mm) to 12 inches (about 300mm) is used. Conical silicon wafers, on the other hand, in the manufacture of liquid crystal display elements, the smallest use is a square glass substrate of about 3 60mm x 4 60mm. 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 JP-A-Hei 9-1 6023 1; JP-A-Hei 9-2 1 1 8 5 5; JP-A 2000-112120; JP-A 2000-1 Many reports such as 3 1 8 3, JP 2000- (2) (2) 200401950 18 1 05, and JP 200 1 _7 5272, etc. These materials are cheap, and for 3 6 0 mm X 460 mm The smaller substrate 'can form a photoresist pattern with excellent coatability, sensitivity, resolution, shape, and dimensional stability, so it is suitable for the purpose of manufacturing an LCD with only a 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 Development of high-performance LCD technology for 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 ~ 1 0 # m. In contrast, the pattern size in the integrated circuit part must be fine, for example, about 0.5 · 2 ~ 0 // m. Under the same exposure conditions, in the case where such integrated circuit parts and display parts are to be formed, linearity is desired [under the same exposure conditions (though the mask size on the reticle is different but the exposure amount is the same condition), and The characteristics of reproducing the mask size on the graticule at the time of exposure] are excellent. In addition, in order to form a fine pattern in an integrated circuit portion, it is necessary to increase a resolution that is not available in today's photoresist materials for the manufacture of liquid crystal display elements. In order to improve the resolution (resolution limit), the formula is as follows: R = k] χλ / NA (where R is the resolution limit and ki is the photoresist (3) (3) 200401950 and steps, like The proportionality constant determined by the formation method; I is the wavelength of the light used in the exposure step, and NA is the number of openings in the lens. As shown in the figure, a short-wavelength light source or a high NA exposure step must be used. Therefore, when forming a fine photoresist pattern of, for example, less than 2.0 // m as described above, it is effective to be exposed by the previous g-ray (4 3 6 nm), such as a shorter-wavelength i-ray (3 65 urn ) Light lithography technique for exposure. 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 not suitable for high NA lenses because the depth of focus is shallow, so it is difficult to localize. In the field of liquid crystal display device manufacturing, based on the above reasons, low NA conditions below 0.3 are generally preferred, but conventional photoresist materials used in the manufacture of liquid crystal display devices have difficulty forming good shapes under low NA conditions. The fine photoresist pattern of about 5 to 2 ^ / ζηι, 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, which is capable of forming a fine photoresist type and having excellent linearity even under a low NA condition, 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 that is suitable for manufacturing the LCD% system as described above. [Means to Solve the Problem] (4) 200401950 In order to solve the above-mentioned problems, as a result of intensive research, the inventors found that the positive photoresist composition containing a specific phenolic hydroxyl-containing compound, even under low NA conditions It can also form a fine photoresist pattern, and it is a photoresist material with excellent linearity. It is suitable for manufacturing LCD systems and completes the present invention. That is, the present invention contains (A) an alkali-soluble resin, (B) a naphthoquinonediazide esterified product, and (C) the following general formula (I)

[In the formula, 'R1 to R6 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 cyclohexyl group; Q is bound to or unconnected to the terminal of R7 Bonding; when Q is not bonded to the terminal of R7, R7 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Q is a residue represented by the following chemical formula (Π)

(In the formula, R8 and R9 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 cyclohexyl group; c is an integer representing 1 to 3) When Q is combined with the terminal of R7, Q and R7 are a cycloalkyl group having 3 to 6 carbon chains together with carbon atoms between Q and R7; a and b are integers representing 1 to 3) Among the compounds, at least one is selected. (5) (5) 200401950 A compound containing a phenolic hydroxyl group, and (D) an organic solvent, which is characterized in forming a substrate for forming an integrated circuit and a liquid crystal display portion on a substrate. Type photoresist composition. In addition, when Q and R7 are a cycloalkyl group having 3 to 6 carbon chains together with carbon atoms between Q and R7, Q and R7 are combined to form an alkylene group having 2 to 5 carbon atoms, and Q and R7 The carbon atoms in between are the carbon atoms of the two benzene rings represented by the formula (I). 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. The step of forming a photoresist film, (3) For the above photoresist coating, use a photoresist pattern for forming an integrated circuit and a photoresist pattern for forming a liquid crystal display part. (4) applying a development process using an alkaline aqueous solution to the photoresist film after the selective exposure, and simultaneously forming a photoresist pattern for integrated circuits on the substrate and The step of using a photoresist pattern for the liquid crystal display part, and (5) a washing step of washing the image developing solution remaining on the surface of the photoresist pattern, are its photoresist pattern forming methods. [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. -9- (6) (6) 200401950 Examples of the alkali-soluble resin include phenols such as phenol, m-cresol, p-cresol, xylenol, trimethylphenol, and formaldehyde, formaldehyde precursors, Phenolic lacquer resin obtained by condensing aldehydes such as 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, etc. in the presence of an acidic catalyst; monopolymers of hydroxystyrene, and hydroxystyrene and other benzenes Copolymers of vinyl monomers, hydroxystyrene resins such as copolymers of hydroxystyrene and acrylic acid or methacrylic acid or derivatives, acrylic or methacrylic resins of copolymers of acrylic acid or methacrylic acid and derivatives Alkali-soluble resins such as phenols are particularly suitable for the preparation of high-sensitivity phenolic lacquer resins obtained by the condensation reaction of phenols containing m-cresol and 3,4-xylenol with aldehydes containing propionaldehyde and formaldehyde. Photoresist material. In the positive photoresist composition of the present invention, the naphthoquinonediazide esterified product as the (B) component is not particularly limited, and naphthoquinonediazide which has been previously used as the photosensitive component of the photoresist can be used. Any of the basic esterified products, particularly the esterified product of a phenol compound and a naphthoquinonediazidesulfonic acid compound represented by the following general formula (III) is photolithography suitable for using i-rays, and, for example, It is suitable for the case where a fine photoresist pattern of 2.0 μm or less is to be formed in a good shape. (7) 200401950

[Wherein, R] i ~ Ri8 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 ; R2G and R21 each independently represent a hydrogen atom or an alkyl group of 1 to 6 carbon atoms; T is a terminal or unbound terminal of R19; T is a hydrogen atom or a carbon terminal of 1 to 19 when T is not bonded to the terminal of R19 6 alkyl groups, T is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a residue represented by the following chemical formula (IV)

(IV) (In the formula, R22 and R23 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 cycloalkane having 3 to 6 carbon atoms. Group; f is an integer representing 1 to 3), when T is combined with the terminal of R19, T and R19 are together with the carbon atom between Q and R19 to form a carbon chain of 3 to 6 cycloalkyl groups; d, e Is an integer of 1 to 3; g is an integer of 0 to 3; η is an integer of 0 to 3] Examples of the phenol compound corresponding to the general formula (m) include tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane, bis (( 8) (8) 200401950 4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis ([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-dimethyl Radical) -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-cyclohexyl-4-hydroxy Triphenol type compounds such as 2-methylphenyl) -2-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane ; 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 [2- (3,5-dimethyl-4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane, bis [3- (3,5- Dimethyl-4-hydroxybenzyl Group) -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)-(9) (9) 200401950 5-methylphenyl] Methane, bis [4-hydroxy-3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl] methane, bis [2,5-dimethyl-3- (2-hydroxy-5 -Methylbenzyl) -4-hydroxyphenyl] methane and other linear tetranuclear phenol compounds; 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 Linear polyphenolic compounds such as dimethyl-3- (2-hydroxy-5-methylbenzyl) -4-hydroxybenzyl] -4-methylphenol and other linear pentanuclear phenol compounds; bis (2 , 3,4-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) methane, 2,3,4-trihydroxyphenyl-4, hydroxyphenylmethane, 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'-hydroxyphenyl) propane, 2- (2,3,4 · trihydroxyphenyl) 2- (4'-hydroxyphenyl) propane, 2- (2,3 , 4-trihydroxyphenyl) 2- (4'-hydroxy-3 ', 5'-dimethylphenyl) propane and other bisphenol-type compounds; 1- [1,1-bis (4-methylbenzene) (Yl) ethyl] -4- [1- (4-hydroxyphenyl) isopropyl] benzene, 1- [BU (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4 -Hydroxyphenyl) ethyl] benzene, 1- [BU (3-methyl-4-hydroxyphenyl) isopropyl] -4- (1, BU bis (3-methyl-4-hydroxyphenyl) Polynuclear branched compounds such as ethyl) phenyl; and condensation phenol compounds such as 1,4-bis (4-hydroxyphenyl) cyclohexane. Among them, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane and bis (4-hydroxy-2,3,5-trimethylphenyl)- 2-hydroxybenzene-13- (10) (10) 200401950 triphenol type compounds such as methane, 1,4-bis [3- (2-hydroxy-5 · methylbenzyl) -4-hydroxy-5-ring Linear tetranuclear phenol compounds such as hexylphenyl] isopropane are excellent in terms of sensitivity, resolvability, and can form photoresist patterns with good shapes. The method of esterifying all or a part of the phenolic hydroxyl group of the compound represented by the general formula (melon) with naphthoquinonediazidesulfonic acid can be performed according to a conventional method. For example, naphthoquinonediazidesulfonyl chloride and the It can be obtained by condensing a compound represented by the general formula (melon). Specifically, the compound represented by the general formula (m) and naphthoquinone d, 2-diazidyl-4- (or 5) -sulfonyl chloride are dissolved in a predetermined amount in dihumane and n-methylpyrrolidone. , Dimethylacetamide, tetrahydrofuran and other organic solvents, and added thereto basic catalysts such as triethylamine, triethanolamine, pyridine, alkali metal carbonates, alkali metal carbonates and the like, and the obtained The product can be prepared by washing with water and drying. (B) In addition to the naphthoquinonediazide esterified product exemplified above, other naphthoquinonediazide esterified product may be used. For example, an esterification reaction product of a phenol compound such as polyhydroxybenzophenone and alkyl gallate and a naphthoquinonediazidesulfonic acid compound can also be used. The amount used is (80) mass in the component (B). % Or less, particularly 50% by mass or less is preferable because the effect of the present invention is not impaired. In the positive-type photoresist composition of the present invention, the blending amount of the component (B) is 20 to 70%, and preferably 30 to 50, relative to the total mass of the component (A) and the following component (C). It is better to select from the mass range of%. (B) If the blending amount of the components is lower than the above range, an image faithful to the pattern cannot be obtained, and transferability may be reduced. On the other hand, if the blending amount of the component (B) is -14- (11) (11) 200401950, the sensitivity will deteriorate and the homogeneity of the formed photoresist film will decrease, and the resolution may deteriorate. In the positive-type photoresist composition of the present invention, the phenolic hydroxyl compound represented by the formula (I) is compounded as the (C) component, 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 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. These two effects and the resolution are greatly improved, and as a result, they are suitable as a photoresist composition for an i-ray exposure step for manufacturing an LCD system under low NA conditions. The phenolic hydroxyl-containing compound is not particularly limited, for example, 1,1-bis (4-hydroxyphenyl) cyclohexane, and bis (3,5-dimethyl-4-hydroxyphenyl) -2- Hydroxyphenylmethane, bis (3,5-dimethyl · 4 · hydroxyphenyl) -3,4-dihydroxyphenylmethane, bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxyphenyl) -4-hydroxyphenylmethane, bis (2,3 '5-trimethyl-4-hydroxyphenyl) -2-hydroxybenzene Triphenol-type compounds such as methylmethane are preferable because they exhibit the above-mentioned characteristics. The compounding amount of the component (C) is selected from a range of 5 to 50 parts by mass, and 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 additional components compounded 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 glycerin-15- (12) (12) 200401950 alcohol monoalkyl ether acetate, alkyl lactate, and 2-heptanone. It is excellent in cloth properties and excellent in film thickness uniformity of the photoresist film on a large glass substrate. 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. In addition, ethyl lactate is also the best among alkyl lactates. However, when a large glass substrate of 500 mm x 600 mm or more is used, the coating tends to be uneven if used alone. Therefore, it is desirable to use other solvents. In particular, a mixed system containing propylene glycol monoalkyl ether acetate and alkyl lactate is preferable because it has excellent uniformity of the thickness of the photoresist film and can form a photoresist pattern with excellent shape. When a propylene glycol monoalkyl ether acetate and an alkyl lactate are mixed and used, it is desirable that the mass ratio of the propylene glycol monoalkyl ether acetate to the propylene glycol monoalkyl ether acetate is 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 7-butyrolactone and propylene glycol monobutyl ether can also be used. When r-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 set r-butyrolactone to propylene glycol monoalkyl ether acetate in a mass ratio of 0. 1 to 1 times, and preferably in a range of 0.05 to 0.5 times. 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-16 -(13) (13) 200401950 Alcohol monoacetate, or their monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether, and their polyvalent alcohols and their derivatives, dioxane, etc. Cyclic ethers; and esters of methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate and the like. When using these solvents, 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 solvent is relative to One or more kinds of propylene glycol monoalkyl ether acetate, alkyl lactate, and 2-heptanone are selected, and 50% by mass or less is preferable. In the present invention, various additives such as a surfactant, an ultraviolet 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, Efutop EF126 (trade name, manufactured by Tokem Products), Megafac R-08 (trade name, manufactured by Daikumoto Ink Chemical Co., Ltd.), etc. Agent. Examples of the ultraviolet absorber include 2,2 ^ 4,4, tetrahydroxybenzophenone, 4-dimethylamino-2, V-dihydroxybenzophenone, 5-amino-3-methyl-1-benzene 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 LC system using the composition of the present invention is shown. First, (A) component, (B) component and (C) component, and various components added as needed are dissolved in a solvent of (d) to 17- (14) (14) 200401950, and spin-coated The device is applied to the substrate. The substrate is preferably a glass substrate. This glass substrate can use a large substrate of more than 500 mm x 60 mm, especially a size of 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 a proximity bake that sandwiches the gap between the hot plate and the substrate ° Secondly, for the photoresist film, for example, a fineness of less than 2.0 μιη (preferably 0.5 to 2.0 μηι) is used. Photomasks for photoresist patterns for pattern size ICs and photoresist patterns for liquid crystal display parts with pattern sizes exceeding 0 μm (preferably more than 2.0 μm and less than 10 μm) Photomask with both photomask patterns. Selective exposure using the desired light source. The light source used here is preferably an i-ray (36 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 process 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, if the developer is immersed in a developing solution, for example, an alkaline aqueous solution such as a 10 to 10% by mass aqueous solution of tetramethylammonium hydroxide, the exposed portion can be dissolved and removed, and an image faithful to the mask pattern can be obtained. Secondly, the developing solution remaining on the surface of the photoresist pattern is washed away with a washing liquid such as pure water to form a photoresist pattern. [Examples] -18- (15) (15) 200401950 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) where a Cr film was formed using a spin coater, the temperature of the hot plate was set to 130 ° C, and the temperature was about 1 mm. Adjacent baking at intervals, first drying for 60 seconds, followed by setting the temperature of the hot plate to 120 ° C, and applying second drying for 60 seconds at adjacent baking at 0.5mm intervals to form a film Photoresist film with a thickness of 1.5 μm. Secondly, by simultaneously plotting the test chart masks that reproduce the photoresist patterns of 3.0 μm line / space (Line & Space, L & S) and 1.5 μm L & S, Furthermore, an i-ray exposure device (device name: FX-702J, manufactured by Nikkon Corporation; NA = 0.14) was used for selective exposure at an exposure amount (Eoρ exposure amount) that faithfully reproduces 3.0 μL & S. Next, a 23 ° C, 2.38 mass% tetramethylammonium hydroxide aqueous solution was used with a developing device with a slit coating nozzle (device name: TD-3 900 type machine, manufactured by Tokyo Chemical Industry Co., Ltd.), such as As shown in FIG. 1, the substrate end portion X passes through Y to reach Z. After 10 seconds, the substrate is filled with liquid and held for 5 5 seconds, then washed with water for 30 seconds, and spin-dried. Then, the cross-sectional shape of the obtained photoresist pattern was observed with a SEM (scanning electron microscope) photograph, and the reproducibility of the photoresist pattern of 1.5 μm L & S was evaluated. The results are shown in Table 2. -19- (16) 200401950 (2) Sensitivity evaluation: Use the above E0P exposure as the index of sensitivity evaluation. The results are shown in Table 2 °. (3) Resolution evaluation: The limit resolution in the above-mentioned Eορ exposure was obtained, and the results are shown in Table (4) Scum evaluation: In the above Eορ exposure, the SEM (scanning) Type electron microscope) Observe the surface of the substrate depicted by 1.5 μm L & S, and investigate the presence or absence of scum. Those who did not see scum at all were indicated by ◎, those who had almost no scum observation were indicated by 0, those who slightly observed were indicated by △, and those who had occurred a large amount of scum were indicated by X. The results are shown in Table 2. $ (5) Shape evaluation: Observe 1.5 μm L & S photoresistive cross-section with SEM (scanning electron microscope) in the above exposure amount, and indicate the shape of the rectangle with ◎, and slightly observe the film The thinner is indicated by 0, the cone shape is indicated by △, the pattern is rolled into a filament, or the pattern is mostly film thinned by X. The results are shown in Table 2. -20- (17) (17) 200401950 < Example 1 > (A) Alkali-soluble resin (A1) A1: p-cresol / 3,4-xylenol = 9/1 (Molar ratio ) Mixed phenol and condensed materials use propaldehyde / formaldehyde = 1/3 (mole ratio) mixed aldehyde and Mw = 4 75 0 and Mw / Mn = 2.44 synthesized phenolic resin (B) Ingredients: 40 parts by mass of naphthoquinonediazide ester (Bl / B2 / = 1/1) B1: bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) -3,4-dihydroxy Esterification reaction product of phenylmethane 1 mol and 1,2-naphthoquinonediazide-5-sulfonyl chloride (hereinafter referred to as "5-NQD") 2 mol B2: bis- (2,3, Esterification reaction product of 5-trimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane and 5-NQD2 mole (C) Component: Compound (C 1) containing phenolic hydroxyl group 2 5 Mass part C1: 1- [1,1-bis (4-hydroxyphenyl) cyclohexane is equivalent to 3 of the above components (A) to (C) and the total mass of the components (A) to (C) 5 Ορρηι amount of surfactant Megafac R-08 (trade name, manufactured by Dainippon Ink Co., Ltd.) is dissolved in PGMEA and adjusted to a solid content [(A) ~ (C) of component Total] The concentration is 25 to 28% by mass, and it is filtered with a membrane filter having a pore size of 0.2 μm to adjust a positive photoresist composition. -21-(18) (18) 200401950 < Examples 2 to 1 〇 >, < Comparative Examples 1 to 4 > Except using the substances described in Table 1 at the same mixing ratio as in Example 1 as (A ) To (D) except for the components, the same Example 1 was used to prepare a positive type photoresist composition. Their evaluation results are shown in Table 2. In addition, none of the positive-type photoresist compositions of Comparative Examples 1 to 4 were drawn with an L & S pattern of 1.5 μm, so no linear evaluation was performed. In addition, the positive-type light composition of Comparative Examples 1 to 2 had a pattern in which only 3 μm was drawn, and the resolvability evaluation could not be performed.

-22- (19) 200401950 [Table 1] (A) (B) (Mixing ratio) (C) (Mixing ratio) (〇) 1 A 1 B1 / B2 (1/1) C 1 PGMEA 2 Same as above C2 Same as above 3 Same as above C3 Same as above 4 Same as above C4 Same as 5 Same as above C5 Same as above 6 Same as above C6 Same as above 7 Same as above C2 / C5 (1/1) Same as 8 Same as above C 1 HE 9 A2 Same as above PGMEA 10 A1 B1 / B3 (1/1) Ibid. Ibid. 1 Ibid. B 1 / B2 (1/1) C7 Ibid. 2 Ibid. Ibid. C8 Ibid. 3 Ibid. C9. Ibid. 4 Ibid. Ibid. C10 Ibid.

In Table 1, each symbol has the following meanings. A2: p-m-cresol / p-cresol / 2,3,5-trimethylphenol-23- (20) (20) 200401950 = 9 / 0.5 / 0.5 (molar ratio) mixed phenol and condensation material Phenolic lacquer resin B3 using formaldehyde / crotonaldehyde = 2/1 (molar ratio) mixed aldehyde and Mw = 7 0 0 0, Mw / Mn = 3.05 synthesized according to a conventional method: 1 gallate of methyl gallate Product of esterification reaction of ear with 5-NQD3 Mol: C2: bis (3,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane C3: bis (3,5-dimethyl-4 -Hydroxyphenyl) -3,4-dihydroxyphenylmethane C4: bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) -3,4-dihydroxyphenylmethane C5: bis (4 -Hydroxyphenyl) -4-hydroxyphenylmethane C6: bis (2,3,5-trimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane C7: 2,3,4,4 '- Tetrahydroxytriphenone C8: bis [2-hydroxy-3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl] methane C9: bis [3- (3,5-dimethyl 4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane C 1 0: methyl gallate PGMEA: propylene glycol monomethyl ether acetate HE: 2-heptanone-24- (21) 200401950 [Table 2]

Linear evaluation Sensitivity evaluation Resolution evaluation Scum shape (μτη) (mJ) (μηι) Evaluation evaluation 1 1.50 50 1 .3 〇〇2 1.50 55 1 .3 〇 ◎ Real 3 2.02 _ 4 5 1.4 Δ Δ 4 1.50 70 1.3 〇 ◎ Shi 5 1.85 35 1.4 Δ Δ 6 1.91 70 1.4 〇Δ Example 7 1.60 60 1.3 .3 〇08 1.90 68 1.4 〇1.70 50 1.4 〇09 1.54 1 70 1.4 〇Δ is more than 1 _ 100 XX More than 2 1 0 0 XX Example 3 • 60 1 .7 XX 4-No residual film No residual film XX

As can be seen from Table 2, none of the positive-type photoresist compositions of the comparative examples could draw a pattern of 1.5 μm, and linearity could not be evaluated. In addition, the resolution is also smaller than 3. 0 μηι, so it cannot be evaluated, and it is as low as 1.7 μιη. In addition, a large amount of scum occurred, and the shape evaluation was also X. In contrast, the linear evaluation of the pattern of the positive photoresist composition in the example of the sun and moon is I 9 1 μm, and a pattern with excellent linearity can be obtained. Moreover, the resolution was also (22) (22) 200401950 1 · 4 μm or less, which showed better resolution than that of the comparative example. In addition, it was found 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, Obtain a pattern with excellent linearity, and provide an excellent positive photoresist composition for the manufacture of a substrate (LCD system) that forms integrated circuits and liquid crystal display parts on a substrate. In addition, according to the positive-type photoresist composition 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. -26-

Claims (1)

(1) 200401950 Patent application scope 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, is characterized by containing (A ) Alkali-soluble resin, (B) naphthoquinonediazide esterified product, (C) the following general formula () [) [In the formula, 'R1 to R6 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having i to 6 carbon atoms, or a cyclohexyl group; q is bonded to or unconnected to the terminal of R7 Bonding; when Q is not bonded to the terminal of R7, R7 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Q is a residue represented by the following chemical formula (Π) (Π) (In the formula, R8 and R9 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 cyclohexyl group; c is an integer representing 1 to 3) When Q is combined with the terminal of R7, Q and R7 are a cycloalkyl group having 3 to 6 carbon chains together with carbon atoms between Q and R7; a and b are integers representing 1 to 3) Among the compounds, at least one kind of a phenolic hydroxyl group-containing compound and (D) an organic solvent are selected. 2. The positive photoresist composition according to item 1 of the application, wherein the -27- (2) (2) 200401950 (C) component is 1,1-bis (4-hydroxyphenyl) cyclohexane. 3. The positive photoresist composition as described in the scope of the patent application, wherein the component (C) is bis (3,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane. 4 For example, the positive photoresist composition in the scope of the patent application, wherein the component (C) is bis (3,5 · dimethyl-4-hydroxyphenyl) -3,4-dihydroxyphenylmethane. 5. The positive photoresist composition according to item 1 of the patent application, wherein the component (C) is bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) -3,4-di Hydroxyphenylmethane. 6. The positive photoresist composition according to item 1 of the scope of the application, wherein the component (C) is bis (4-hydroxyphenyl) · 4-hydroxyphenyl formaldehyde. 7. The positive photoresist composition according to item 1 of the application, wherein the component (C) is bis (2,3,5-trimethyl · 4-hydroxyphenyl) -2-hydroxyphenylmethane. 8. The positive photoresist composition according to item 1 of the patent application range, wherein the component (D) is propylene glycol monoalkyl acetate. 9. The positive photoresist composition according to item 1 of the application, wherein the component (D) contains an alkyl lactate. 10 · The positive photoresist composition according to item 1 of the patent application range, wherein the (D) component contains 2-heptanone. 1 1. The positive type photoresist composition according to any one of items 1 to 10 of the scope of application for a patent, wherein the positive type photoresist composition is an i-ray (36.5 nm) exposure step. -28-(3) (3) 200401950 1 2. The positive photoresist composition according to any one of items 1 to 10 of the scope of application for a patent, wherein the positive photoresist composition is one having a NA of 0.3 or less For exposure steps. 13. A method for forming a photoresist pattern, comprising: (1) coating a positive photoresist composition as described in any one of claims 1 to 10 on a substrate to form a coating film In the step, (2) the step of heating the substrate on which the coating film is formed to form a photoresist film on the substrate, and (3) using the photoresist pattern photomask for forming an integrated circuit for the photoresist film The step of performing selective exposure with a photomask having both a pattern and a photoresist pattern for forming a liquid crystal display portion, (4) applying a photoresist film using an alkaline aqueous solution to the photoresist film after the selective exposure. Step of developing processing, forming a photoresist pattern of an integrated circuit and a photoresist pattern for a liquid crystal display part on the substrate at the same time, (5) washing away the developing solution remaining on the surface of the photoresist pattern step. 14. The method for forming a photoresist pattern according to item 13 of the scope of patent application, wherein the step of performing the above (3) selective exposure is performed by using an i-ray (3 65 nm) exposure step with a light source. 15 · The method for forming a photoresist pattern according to item 13 of the scope of the patent application, wherein the step of performing the above-mentioned (3) selective exposure is performed by an exposure step under a low NA condition with NA of 0.3 or less. 1 6 · The method for forming a photoresist pattern according to item 13 of the scope of patent application, wherein the photoresist pattern of the integrated circuit in step (4) above is a light having a line width of 2.00μηι -29- (4) below 200401950 Resistive pattern. 17. The method for forming a photoresist pattern according to any one of items 13 to 16 of the scope of application for a patent, wherein the photoresist pattern for the liquid crystal display portion in the step (4) above is a photoresist having a line width exceeding 2.0 μηι Pattern. -30-