TW200428141A - Positive photoresist composition for manufacturing system LCD, manufacturing method for the positive photoresist and formation method of resist pattern - Google Patents

Abstract

A positive photoresist composition is provided which has a high sensitivity and a high thermal resistance and is favorable for manufacturing LCD having integrated circuits and liquid crystal display portions on a substrate. The positive photoresist composition contains. (A) an alkali soluble resin, (B) a quinonediazido group-containing compound, wherein the (A) component is a novolak resin synthesized by a condensation reaction between a mixed phenol containing a phenol compound (a1) represented by the following general formula (I) and a phenol compound (a2) represented by the following general formula (II), and an aldehyde.

Description

200428141 (1) 发明. Description of the invention [Technical field to which the invention belongs] The present invention relates to a positive-type photoresist composition for system LCD manufacturing in which an integrated circuit and a liquid crystal part can be formed on one substrate, and a light forming method. [Prior art] Conventionally, in terms of photoresist materials used in the manufacture of thin-film transistor (TFT) and other liquid crystal display elements, it is suitable for ghi line (including all light of g-bound and i-line) exposure, because it is relatively cheap, and For high-sensitivity, lacquer-naphthoquinonediazide-based photoresist using phenolic lacquer resin as alkali-soluble resin and using naphthalene nitrogen-containing compound as photosensitive component (hereinafter referred to as PAC) is widely used (please refer to Exemplary Literature 1 ~ 4). This photoresist generally forms only a rough pattern (approximately 3 to 5 # m) in the pixel portion of the display. However, in recent years, as the next-generation LCD, the integrated circuit part of a glass' driver 'DAC (digital-analog converter), image processor controller' RAM, etc. can be integrated with the display part. For the so-called "system LCD" High-performance LCD technology is underway (for example, 'see Non-Patent Document 1). Hereinafter, in the book ', such an LCD that can form an integrated circuit and a liquid crystal display on one substrate is conveniently referred to as a system LC. In terms of the LCD substrate of such a system, recently, low-temperature polycrystalline display was unobstructed (LCD, h-line, quinone dipyramid, phenolic, such as on a very rough substrate, and the video was simultaneously developed in the original specifier. , -6- (2) (2) 200428141 Especially low temperature polysilicon formed by low temperature treatment below 6 0 ° C. Compared with amorphous polysilicon, the resistance is small and the mobility is appropriate. The development of a system LCD using low-temperature polysilicon as a substrate is highly anticipated. [Patent Document 1] Japanese Patent Laid-Open No. 2000- 1 3 1 83 5 [Patent Document 2] Japanese Patent Laid-Open No. 2001-75272 [Patent Document 3] Japanese Patent Publication No. 2000-181055 [Patent Literature 4] Japanese Patent Publication No. 2000-112120 [Non-Patent Literature 1]

Semiconductor FPD World 200 1. 9, ρρ · 50-67 In the system LCD manufacturing, the fine pattern in the photoresist material, integrated circuit part and the rough pattern in the liquid crystal display part can form a good shape at the same time ( The improvement of linearity, high resolution, and the improvement of the depth of focus (DOF) characteristics of fine patterns are strictly required. In addition, when manufacturing a TFT made of low-temperature polysilicon, a low-temperature polysilicon film is formed on the glass substrate by low-temperature processing, and then P or B is placed in the low-temperature polysilicon film, and the so-called "implantation" The improvement of the heat resistance of the step is also desired. In addition, in the manufacture of system LCDs, in order to form a fine pattern, instead of the conventional ghi-line exposure, it is expected that the i-line (3 6 5 nm) was exposed. -7- (3) (3) 200428141 Cheng Zhi Import. However, it is difficult to apply the material used for LCD manufacturing, such as a material using a diphenyl ketone PAC, to the i-line exposure process. Therefore, a material suitable for i-line exposure is expected. In terms of materials suitable for i-ray exposure, it is expected that the use of non-diphenylketone-based PAC materials is appropriate. However, the use of non-diphenylketone-based PAC materials has its difficulties in increasing sensitivity. The sensitivity of photoresistive materials is reduced, including system LCDs. In the field of LCD manufacturing, it is not good because it will cause a fatal decrease in productivity. In addition, in the heat treatment (post-exposure baking) step or injection step when forming a photoresist pattern, high-temperature treatment can be performed. Therefore, in such steps, the shape of the pattern is not deformed. Resistive materials and high heat resistance are also required. Therefore, in terms of photoresist materials for system LCD manufacturing, materials with high sensitivity and high heat resistance are desired. Regarding the technique of increasing the sensitivity of the photoresistive material, the type or mixing ratio of phenols, which is one of the raw materials of phenolic lacquer resin, can be considered. For example, in the case of phenols, when using cresol, the higher the ratio to cresol, the higher ortho phenolic varnish with excellent resolvability can be obtained, but the sensitivity of this resin tends to deteriorate significantly. . Therefore, if the ratio of cresols in phenols is increased, the sensitivity is increased. However, when using this phenolic varnish to modulate a photoresist material to form a photoresist pattern, there is a problem that the residual film property after development is lowered and the resolution is lowered. Furthermore, as the ratio β of cresols among phenols increases, the sensitivity also increases. However, when the photoresist material prepared by using this formaldehyde varnish is used to form a photoresist pattern, the edges of the photoresist pattern after development are rough -8- (4) 200428141 degrees, etc., there may be mask patterns. The problem of reduced faithful reproducibility. In addition, in terms of other techniques for high sensitivity, although the use of low molecular weight phenolic lacquer is considered, according to this method, the heat resistance of the photoresist pattern may be impaired. Therefore, these arbitrary techniques are practical Difficulties in applying. [Problems to be Solved by the Invention] In view of the completion of the above-mentioned problems, the present invention aims to provide a high-sensitivity and high heat-resistance, and is a suitable positive-type photoresist composition for system LCD manufacturing. [Means for Solving the Problem] The present invention provides a positive-type photoresist composition for LCD manufacturing, in which an integrated circuit and a liquid crystal display portion can be formed on one substrate, which is characterized by containing (A) an alkali-soluble resin and (B) containing A positive photoresist composition of a quinonediazide compound, wherein the component (A) contains the following general formula (I)

(〇H) a… (.1) (R) b [wherein R represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group, allyl group, or aryl group having 1 to 3 carbon atoms; a represents An integer of 2 to 4; b represents an integer of 0 or i to 2], and the following general formula (-9-(5) 200428141 II) ο

OH… (π) [wherein R represents an alkyl group having 1 to 3 carbon atoms, alkoxy group having 1 to 3 carbon atoms, allyl group, or aryl group; and C represents an integer of 1 to 3] Phenolic lacquer resin synthesized by the condensation reaction of phenol compounds (a2) with phenols and aldehydes. The present invention further provides a photoresist pattern forming method, which is characterized by comprising the following steps: (1) coating a positive type photoresist composition according to any one of claims 1 to 5 on a substrate to form a coating; In the film step, (2) the step of heat-treating (pre-baking) the substrate with the coating film formed on the substrate to form a photoresist film on the substrate, and (3) using a photoresist of 2.0 # m or less relative to the photoresist film (4) Compared with the above-mentioned selective exposure, the steps of selective exposure for pattern formation mask pattern and masks described by both sides of the photoresist pattern formation mask mask pattern exceeding 2.0 // m are performed. The subsequent photoresist film is subjected to a heat treatment (post-exposure baking) step. (5) Compared with the photoresist film after the heat treatment, an alkaline aqueous solution is used for development processing. On the substrate, the pattern size is 2 The step of simultaneously forming a photoresist pattern for an integrated circuit below .0 m and a photoresist pattern for a liquid crystal display portion exceeding 2.0 / zm, which is constituted as follows [Content of the Invention] -10- (6) ( 6) 200428141 Hereinafter, the present invention will be described in detail. "Positive Photoresist Composition for System LCD Manufacturing" The positive photoresist composition of the present invention, (A), is an alkali-soluble formaldehyde varnish obtained by using a mixed phenol containing at least two types of phenol compounds Resin is its characteristic. < (A) component > (A) The component contains a mixed phenol compound of phenol compound (al) 'represented by general formula (I) and a phenol compound (A2) represented by general formula (Π) and aldehyde A kind of alkali-soluble phenolic lacquer resin synthesized by a condensation reaction of this kind. In the general formula (I), in terms of R, there are, for example, an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, propyl, etc .; an alkoxy group having 1 to 3 carbon atoms such as methoxy; Aryl and the like, in which an alkyl group having 1 to 3 carbon atoms is preferred. -As for the phenol compound (al) represented by the general formula (I), 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 1,2,3-tris Hydroxybenzene, 1,2,4-trihydroxybenzene, polyhydroxybenzene such as 1,3,5-trihydroxybenzene, etc., and R-substitutes in which a part of hydrogen atoms of the polyhydroxybenzene is replaced by R, and the like. Among them, 1,3-dihydroxybenzene is preferred because the reaction speed of the phenolic lacquer resin is high and the reactivity is good, so that the uniformity of the condensation reaction is not good because the unreacted monomer remains'. In the general formula (Π), the aspect of R is the same as the above. 'For example, there is an alkyl group having 1 to 3 carbon atoms; a oxy group having 1 to 3 carbon atoms; An alkyl group of 3 is preferred. -11-(7) (7) 200428141 As for the phenol compound (A2) represented by the general formula (II), there are cresols such as m-cresol, o-cresol, p-cresol and the like; Dimethylphenols such as phenol, 3,4-xylenol, etc .; Trialkylphenols such as 2,3,5-trimethylphenol, etc. The mixing ratio of the phenol compound (a 1) to the phenol compound (A2) is preferably 1:99 to 5 0:50 (molar ratio), and more preferably 5:95 to 30:70. When the phenol compound (a 1) is compounded with the phenol compound (a 1) and the phenol compound (a2) in a total amount of mol% or more, the effect of high sensitivity can be sufficiently obtained. On the one hand, it is 50 mol% or less In this case, the residual film property after the development process is excellent, and a photoresist pattern of high resolution can be formed. In terms of aldehydes, there is no particular limitation. The aldehydes used in the manufacture of conventional phenolic resins can be used. A mixture of formaldehyde (Π) and other aldehydes (f2) (mixed aldehydes) can be used. Furthermore, it is appropriate to prepare a photoresist material excellent in heat resistance. In terms of aldehydes (f2), there are no particular restrictions, but aldehydes having large substituents such as acetaldehyde, propionaldehyde, benzaldehyde, salaldehyde, vanillin, and the like are preferred. Among them, propionaldehyde and salaldehyde are preferred, and propionaldehyde is more preferred. By using these aldehydes and formaldehyde (f 1), the potential energy of the main chain and side chains of the phenolic lacquer resin can be increased by the steric obstacles in the molecule of the obtained phenolic lacquer resin. ), And suppresses free rotation, can exhibit the excellent effect of improving heat resistance. The mixing ratio of formaldehyde (f 1) and aldehydes (f2) in the mixed aldehydes is preferably 50: 50 to 95: 5 (molar ratio), and more preferably 60: 40 to 90: 10. In addition, aldehydes (f2) may be used alone or in combination of two or more. -12- (8) (8) 200428141. The mixing ratio of the mixed phenols and aldehydes is preferably 1: 0.5 to 1: 1 (molar ratio), and more preferably 1: 0.6 to 1: 0.95 in terms of excellent characteristics. The component (A) can be produced according to a conventional method, and can be synthesized by, for example, mixing phenols and aldehydes and performing a condensation reaction in the presence of an acidic catalyst. Polystyrene-equivalent mass average molecular weight (hereinafter, may be described as Mw only) due to gel permeation chromatography of component (A), may depend on the type, but in terms of sensitivity or pattern formation 2,000 to 100,000, and preferably 3,000 to 30,000 are appropriate. < (B) component > (B) component is a compound containing a quinonediazide group. Component (B) is generally used in a positive-type photoresist composition, and if it is used as a photosensitive component (P A C), the user is not particularly limited, and one or two or more types may be arbitrarily selected for use. Among them, 'non-diphenyl ketone-containing phenolic hydroxyl compound and 1,2-naphthoquinonediazidesulfonyl sulfonyl ester esterification reaction product (non-diphenyl ketone PAC)' is suitable for use I-line light lithography is preferred. Furthermore, it is excellent in resolvability even under a low NA condition, and it is appropriate to form a photoresist pattern with a desired shape. It is also preferable in terms of linearity or DOF. In the case of 1,2-naphthoquinonediazidesulfofluorenyl compounds, 1,2-naphthoquinonediazide-4 -sulfofluorenyl compound and / or 1,2-naphthoquinonediazide-5- Sulfo-13- (9) 200428141 is preferably a fluorenyl compound. In the case of non-diphenyl ketone-containing phenolic hydroxyl compounds, the following general formula (III)

[Wherein R1 to R8 are each independently hydrogen atom, halogen atom, alkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, or cycloalkyl group having 3 to 6 carbon atoms; R1G and R11 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R9 may be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. In this case, Q 1 is a hydrogen atom and 1 to 6 carbon atoms Alkyl group or the following formula (IV) R 12

... (IV)

(Wherein R12 and R13 are each independently 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; f represents an integer from 1 to 3), or Q1 is a bond to the terminal of R9. In this case, Q1 represents R9 and Q1 -14- (10) (10) 200428141 and the carbon atom between R9 At the same time, it represents a cycloalkyl group with a carbon chain of 3 to 6; d, e represents an integer of 1 to 3; g represents an integer of 0 to 3; when d, e, or g is 3, each is free of R3, R6, or R8 ; Η represents an integer from 0 to 3. 〕 Shown compounds. In addition, the carbon atoms between Q1 and R9 and Q1 and R9 all form a cycloalkyl group having a carbon chain of 3 to 6, and Q1 and R9 are bonded to form an olefin group having 2 to 5 carbon atoms. In terms of the phenol compound corresponding to the general formula (III), 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-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, bis ( 4-hydroxyphenyl) -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-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxy Triphenol type compounds such as phenylmethane; -15- (11) (11) 200428141 2,4-bis (3,5-dimethyl-4-hydroxybenzyl) -5-hydroxyphenyl, 2,6 -Linear 3-nuclear phenol compounds such as bis (2,5-dimethyl-4-hydroxybenzyl) -4-methylphenol; 1,2-bis [3- (2-hydroxy-5-methylbenzyl Group) -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-dimethyl-4-hydroxybenzyl) -4- Hydroxy-5-methylphenyl] methane, bis [3- (3,5-dimethyl-4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane, bis [3- (3 , 5-dimethyl-4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane, bis [3- (3,5-diethyl-4-hydroxybenzyl) -4-benzyl ) 5-methylphenyl] linear 4-nucleus of bis [2,5-dimethyl-3- (2-hydroxy-5-methylbenzyl) -4-hydroxyphenyl] methane, etc. Bulk phenol Compounds; 2,4-bis [2-hydroxy-3 (4-hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,4-bis [4-hydroxy-3-3- (4 -Hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,6-bis [2,5-dimethyl-3- (2-hydroxy-5-methylbenzyl) -4 -Hydroxybenzyl] -4-methylphenol and other linear polyphenol compounds such as linear nucleus phenol compounds; bis (2,3,4-trihydroxyphenyl) methane, bis (2,4 · bis Hydroxyphenyl) methane, 2,3,4-trihydroxyphenyl-4'-hydroxyphenylmethane, 2- (2,3,4-trihydroxyphenyl) -2- (2,34, -trihydroxy Phenyl) propane, 2- (2,4-Dimethynylphenyl) -2- (2-4 · '-Mondenylphenyl) propanyl ^ 2- (4-Methylphenyl) -2- ( 4'-hydroxyphenyl) propane, 2- (3-fluoro-4-hydroxyphenyl) -2- (3'-fluoro-4'-hydroxyphenyl) propane, 2- (2,4-dihydroxybenzene) ) -2- (4'-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (4 '· hydroxy-16- (12) (12) 200428141 phenyl ) Propane '2- (2,3,4-trihydroxyphenyl) -2- (4, -hydroxy-3', 5'-dimethylphenyl) propane and other bisphenol compounds; 1- 1- (4-hydroxyphenyl) isopropyl] _4- [1,1_bis (4-hydroxyphenyl) ethyl] benzene, methyl_4-hydroxyphenyl)) isopropyl) -4- Polynuclear branched polynuclear branched compounds such as [l, l-bis (3-methyl_4-hydroxyphenyl) ethyl] benzene; etc .; Condensed types of 1,4-bis (4-hydroxyphenyl) cyclohexane Phenol compounds, etc. These can be used in combination of one kind or two or more kinds. Among them, those containing a triphenol compound as the main component are preferred in terms of high sensitivity and resolution, especially bis (5-cyclohexyl-4_hydroxy-2_methylphenyl) -3, 4-Dihydroxyphenylmethane [hereinafter abbreviated (BΓ). ] '' (4-Hydroxy-2,3,5-trimethylphenyl) hydroxyphenylmethane [hereinafter referred to as (B3 '). ] Better. In order to adjust the resolution, sensitivity, heat resistance, DOF characteristics, linearity, etc., and the photoresist composition with excellent overall balance of photoresistance characteristics, the linear polyphenol compound and bisphenol type compound can be multi-cored. Chemical compounds, and condensed phenol compounds, etc., are preferably used in combination with the above-mentioned triphenylhydrazone-type compounds, especially bisphenol-type compounds. ). ] When used, the photoresist composition having excellent overall balance can be adjusted. In addition, hereinafter, each of the aforementioned (B1 ·), (B2,), (B3,) naphthoquinonediazide esterified products is abbreviated as (B1), (B2), (B3). When (B1) and (B3) are used, the blending amount 'in the (B) component is preferably 10% by mass or more, and more preferably 15% by mass or more. Furthermore, -17- (13) (13) 200428141 'may each be 90% by mass or less', and preferably 85% by mass or less. In the case where (B1) '(B2) and (B3) are completely used, the respective blending amounts (B1) are 50 to 90% by mass, and preferably 60 to 80% by mass. The blending amount of (B2) is 5 to 25 mass%, preferably 10 to 15 mass%, and the blending amount of (B3) is 5 to 25 mass%, preferably 10 to 15 mass%. The method of esterifying all or a part of the phenolic hydroxyl group of the compound represented by the general formula (III) with naphthoquinonediazidesulfonic acid can be carried out according to a conventional method. For example, it can be obtained by condensing a table-cum nitrogen-based donkey-based chloride with a compound represented by the general formula (111). Specifically, for example, the compound represented by the above general formula (III) and 'naphthoquinone-1, 2-diazido-4 (or 5) · sulfofluorenyl chloride, in epoxy hexane, n-formaldehyde Organic solvents such as pyrrolidone, dimethylacetamide, tetrahydrofuran, etc. are used to dissolve the quantitative amount. Here, one or more basic catalysts such as triethylamine, triethanolamine, pyridine, alkali carbonate, bicarbonate, etc. are added to dissolve the amount. In the reaction, the resulting product is washed with water and dried to prepare it. (B) In terms of components, as described above, in addition to the preferred naphthoquinonediazide esterified products described above, other naphthoquinonediazide esterified products can also be used. For example, polyhydroxydiphenyl can be used. An esterification reaction product of a phenylhydrazone compound such as a ketone or an alkyl gallate and a naphthoquinonediazidesulfonic acid compound. The use amount of these other naphthoquinonediazide esters in the photosensitive component (B) is 80% by mass or less, especially 50% by mass or less, and the effect of the present invention is better. -18- (14) (14) 200428141 The compounding amount of the (B) component in the photoresist composition is 20 to 70% by mass, preferably 25 to the total amount of the (A) component and the following (C) component ~ 60% by mass. When the blending amount of the component (B) is at least the above-mentioned lower limit, a faithful image of the pattern can be obtained, and the transferability can be improved. When it is equal to or less than the above upper limit, the deterioration of sensitivity can be prevented, and the effect of improving the homogeneity and resolution of the formed photoresist film can be obtained. < (C) component > The positive-type photoresist composition of the present invention, in addition to the above-mentioned components (A) and (B), further contains a (C) molecular weight of 10,000 or less in terms of a solubilizer. Phenolic hydroxy compounds are preferred. This (C) component has excellent sensitivity improvement effect, so by using the (C) component, during the i-line exposure process under low NA (numerical aperture) conditions, it has high sensitivity and high resolution, suitable for LCD The material manufactured can further be a material suitable for a system LCD with excellent linearity. The molecular weight of the component (C) is 1,000 or less, preferably 700 or less, substantially 200 or more, and preferably 300 or more, and the above-mentioned effects are preferable. (C) In terms of components, the sensitivity-improving material or the phenol-containing hydroxy compound generally used as a photoresist for the solubilizing composition. Among them, it is not particularly limited as long as it satisfies the above-mentioned molecular weight conditions. Anthracene can be used singly or in combination. In addition, the following general formula (V) -19- (15) 200428141

R 30 (H〇) h- j21

R22, r23 -c- R31 R2, 7

R28 (OH) k

(OH) i > 26 p25 (V) [wherein R21 to R28 are each independently 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; R30 and R31 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R29 may be a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. In this case, Q2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a residue R32 represented by the following chemical formula (VI)

(VI) (wherein R32 and R33 represent independent hydrogen atoms, halogen atoms' alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, or 3 to 6 carbon atoms Cycloalkyl; j is an integer from 0 to 3), 〇2 may be bonded to the end of 1129, in this case, Q2 represents r29 and, together with the carbon atom between 〇2 and R ", represents a carbon chain of 3 ~ 6 Cycloalkyl; h, i represents an integer of 1 to 3; k represents an integer of 0 to 3; when h, i or k is 3, 'there is no R23', R26 or R28; m represents an integer of 0 to 3] The phenol compound 'preferably exhibits the above-mentioned characteristics. -20- (16) (16) 200428141 Specifically, g' is exemplified in the above-mentioned component (B), other than the compound represented by the general formula (II), Appropriate use of bis (3-methyl · 4-merylphenyl) -4 -isopropylphenylmethane, bis (3-methyl-4-hydroxyphenyl) · phenylmethane'bis (2- Methyl-4-hydroxyphenyl) -phenylmethane, bis (3-methylhydroxyphenyl) -phenylmethane, bis (3,5_dimethyl · 4-hydroxyphenyl) -phenylmethane, bis (3-ethyl-4-hydroxyphenyl) -phenylmethane, bis (2-methyl-4-hydroxy Triphenyl compounds such as phenylphenyl) -phenylmethane, bis (2-tertiarybutyl-4,5-dihydroxyphenyl) -phenylmethane, etc. can be suitably used. Among them, bis (2 · methyl 4-hydroxyphenyl) -phenylmethane, preferably ΐ _ [: ι_ (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene (C) The compounding amount of the component is preferably in a range of 10 to 70% by mass, and more preferably 20 to 60% by mass with respect to the component (a). ≪ Organic solvent > The present invention The positive photoresist composition preferably further contains an organic solvent. The organic solvent is not particularly limited as long as it is a general photoresist composition, and one or two or more types can be selected for use, and it contains a propylene glycol monoalkyl group. Ether acetate and / or 2-heptanone are excellent in coating properties, and it is preferable that the uniformity of the thickness of the photoresist film on a large glass substrate is excellent. In addition, propylene glycol monoalkyl ether acetate and The two sides of 2-heptanone can be used separately or mixed with other organic solvents. It is better for the user to use the film thickness uniformity when applying by spin coating, etc. There are many cases -21-(17) (17) 200428141 Propylene glycol monoalkyl ether acetate is contained in an all-organic solvent, preferably 50 to 100% by mass. Propylene glycol monoalkyl ether acetate, for example, has a carbon number Among the linear or branched alkyl groups of 1 to 3, among them, propylene glycol monomethyl ether acetate (hereinafter referred to as PGMEA) and the photoresist film on a large glass substrate have excellent film thickness uniformity. On the one hand, 2-heptanone is not particularly limited, and the component (B) as described above is a suitable solvent when combined with a non-diphenyl ketone-based photosensitive component. 2-heptanone is excellent in heat resistance when compared with PGMEA, and has properties that can reduce the photoresist composition of dross and is a very good solvent. When 2-heptanone is used alone or mixed with other organic solvents, it is preferable to contain 50 to 100% by mass in all organic solvents. In addition, these preferred solvents can also be mixed with other solvents. For example, when mixed with alkyl lactate such as methyl lactate, ethyl lactate (preferably ethyl lactate), a photoresist film can be formed. Film thickness uniformity is excellent, and a photoresist pattern with excellent shape is preferred. When propylene glycol monoalkyl ether acetate is mixed with alkyl lactate, the mass ratio to propylene glycol monoalkyl ether acetate is 0.1 to 10 times the amount, preferably 1 to 5 times the amount of alkyl lactate The cooperation is expected. Organic solvents such as r-butyrolactone or propylene glycol monobutyl ether can also be used. In the case of using r-butyrolactone, the mass ratio of acetic acid to propylene glycol monoalkyl ether ethyl-22- (18) (18) 200428141 is 0.001 to 1 times, preferably 005 to 〇. A combination of 5 times the amount is expected. In addition, as for other organic solvents that can be blended, specifically, for example, the following may be mentioned. That is, ketones such as acetone 'methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, etc .; ethylene glycol' propylene glycol 'diethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate , Diethylene glycol monoacetate, or such monomethyl acid's monoethyl ether, monopropyl ether, monobutyl ether, or monophenyl ether, and their polyols and their derivatives; epoxy Hexane-like cyclic ethers; and methyl acetate, ethyl acetate, butyl acetate 'methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, etc. Class, etc. When these solvents are used, it is expected that the content will be 50% by mass or less in all organic solvents. < Other ingredients > The positive-type photoresist composition of the present invention may contain compatible additives as needed, such as improving the performance of the photoresist film, as long as the object of the present invention is not impaired. Additive resins, plasticizers, storage stabilizers, surfactants, colorants that make the developed image more visible, solubilizer or halation to improve the g-sensing effect, prevent the use of dyes, adhesion Enhancers, etc. are customary additives. As for the dye for preventing halo phenomenon, ultraviolet absorption can be used (for example, 2,2,4,4'-tetrahydroxydiphenyl ketone, 4-dimethylamino-2 ', 4, _- physyl Phenyl ketone, 5-amino-3-methyl-1-phenyl-4- (4-hydroxyphenyl dioxy-23- (19) (19) 200428141) pyrazole, 4-dimethylamino 4'-hydroxyazobenzene, 4-diethylamino-4'-ethoxyazobenzene, 4-diethylaminoazobenzene, curcumin, etc.). For example, a surfactant can be added to prevent stigma. For example, Furolite FC-43 0, FC4 3 1 (trade name: 'Sumitomo 3 M') can be used. ≫ EF-TOP EF 1 22Α 'EF 122B, EF 122C, EF 126 (trade name, manufactured by Tokem Products) and other fluorine-based surfactants;) ^ -104 'Megafuck R-08 (trade name, manufactured by Dainippon Ink Chemical Industry Co., Ltd.) and the like. < Modulation method of positive type photoresist > The positive type photoresist composition of the present invention, for example, (A) to (C) components and other components' is dissolved in an organic solvent and filtered to prepare it. In addition, the amount of the organic solvent used is preferably an amount obtained by appropriately dissolving the components (A) to (C) and other components to obtain a uniform positive-type photoresist composition. The concentration of the solid components [(A) to (C) component and other components] is preferably 10 to 50% by mass, and more preferably 20 to 35% by mass. The Mw (hereinafter referred to as "photoresist molecular weight") of the positive-type photoresist composition of the present invention contained in the solid content of the photoresist composition is preferably adjusted in the range of 5000 to 30,000, and more preferably Mw is 6000 ~ 10000. When the molecular weight of the photoresist is in the above range, high heat resistance and high resolution can be achieved without reducing sensitivity, and at the same time, a positive photoresist composition having excellent linearity and D o F characteristics can be obtained. -24- (20) (20) 200428141 The molecular weight of the photoresist is smaller than the above range, due to insufficient heat resistance, resolution, linearity, and DOF characteristics. If it exceeds the above range, the sensitivity will be significantly reduced, which will damage the The coating property of the positive photoresist composition may be in danger. Regarding the method of adjusting the molecular weight of the photoresist to the above-mentioned appropriate range, for example, separately operating the component (A) before mixing, etc., so that the Mw after mixing all the components becomes the above range, and the Mw of the (A) component is adjusted in advance to A suitable range method is a method of preparing a plurality of Mw-different (A) components to appropriately mix them, and adjusting the Mw of the solid component to the above-mentioned range. In addition, in this specification, the aspect of the molecular weight of the photoresist is measured by the following using a GPC system. Device name: SYSTEM 11 (product name, manufactured by Showa Denko Corporation)

Pre-column: KF-G (product name, manufactured by Shodex) column: KF-8 05, KF-803, KF-802 (product name, manufactured by Shodex) Detector: UV41 (product name, manufactured by Shodex), Measured at 280 Nm. Solvent and the like: Tetrahydrofuran was passed through at a flow rate of 1.0 m 1 / min, and measured at 3 5 ° C. Measuring sample preparation method: The photoresist composition to be measured was adjusted to a solid content concentration of 30% by mass, and this was diluted with tetrahydrofuran to prepare a solid content concentration of 0.1% by mass of the measuring sample. 20 // L of this measurement sample was put into the above device for measurement. The positive photoresist composition of the present invention described above uses a specific mixed benzene -25- (21) (21) 200428141 phenolic lacquer resin obtained from phenols, which can improve heat resistance and sensitivity. Therefore, it is suitable for the manufacture of LCDs, which are systems that require high heat resistance and high sensitivity. In addition, it has excellent resolvability or residual film after development, and has excellent depth-of-focus (DOF) characteristics and linear photoresistance characteristics. It is a more suitable material for system LCD manufacturing. Among them, in the case of (B) component, in the case of using a non-diphenylketone PAC, the sensitivity can be improved, and the DOF characteristic with high resolution can also be made during exposure under low NA conditions, linearity, etc. The photoresistance characteristics are further improved. In the manufacture of system LCDs, as described above, it is expected that an i-line (3 65 nm) with a shorter wavelength than a user of a conventional LCD manufacturer may be used. In the positive photoresist composition of the present invention, in (B) In the case of the component, (C) component, when a non-diphenyl ketone compound represented by the general formulae (III) and (V) is used, absorption of the i-line of the component (B) and the component (C) can be suppressed. Therefore, it is a suitable material for the i-line exposure process, and thus can achieve high resolution. << Photoresist Pattern Forming Method >> Hereinafter, a suitable example of the photoresist pattern forming method of the present invention will be described. First, the above-mentioned positive photoresist composition of the present invention is coated on a substrate with a spinner or the like to form a coating film. . As the substrate, a glass substrate is preferable. In terms of glass substrates, in the field of system LCDs usually used for amorphous silica, glass substrates such as low temperature polysilicon layers -26- (22) (22) 200428141 are preferred. With regard to this glass substrate, the positive photoresist composition of the present invention has excellent resolvability under low NA conditions, and can use a large substrate of 500mmx600mm or more, especially a large substrate of 550mmx650mm or more. Next, the glass substrate on which the coating film is formed is subjected to a heating (pre-baking) treatment at, for example, 100 to 140 ° C to remove the remaining solvent to form a photoresist film. As for the pre-baking method, it is preferable to perform a close baking between the hot plate and the substrate to maintain the gap. In addition, the photoresist film is equivalent to a mask pattern for forming a photoresist pattern of 2 _ 0 // m or less in the integrated circuit portion and a photoresist pattern exceeding 2.0 / zm corresponding to a liquid crystal display portion. Masks drawn by both sides of the mask pattern for forming are used for selective exposure. In terms of light source, it is better to use an i-line (3 65Nm) to form a fine pattern. The exposure process used in this exposure is preferably an exposure process with a low NA condition of ≦ 0.3 or less, preferably 0.2 or less, more preferably 0.15 or less. Secondly, heat treatment is performed on the photoresist film after selective exposure (post-exposure baking: PEB). The PEB temperature is preferably 90 to 150. (:, More preferably 100 ~ 1 20 ° C ° In addition, in the PEB method, adjacent baking can be used to maintain a gap (gap) between the hot plate and the substrate, or between the hot plate and the substrate. Either of the two types of direct baking that maintains the gap, and in particular, it is better to use both of them. Among them, it is better to perform direct baking after proximity baking. More specifically (23) (23) 200428141 specifically 90 to 150 ° C, more preferably 100 to 120. (:, 5 to 100 seconds, more preferably 10 to 50 seconds, and a gap of 0.5 to 5 mm, and more preferably 0.1 ~ 1 mm after proximity baking, 90 ~ 150 ° C, more preferably 100 ~ 120 ° C, 5 ~ 200 seconds, more preferably 30 ~ 80 It is desirable to directly bake a gap of 0 mm in seconds. Compared with the photoresist film after PEB, the developing solution is, for example, an imaging solution using an alkaline aqueous solution such as a tetramethylammonium hydroxide aqueous solution of i to 10% by mass. The exposed part is dissolved and removed, and a photoresist pattern for an integrated circuit and a photoresist pattern for a liquid crystal display can be formed on the substrate at the same time. Furthermore, the photoresist pattern will remain in the photoresist pattern. The developing solution on the surface is washed away with a washing solution such as pure water, and can be formed on the substrate at the same time, and a photoresist pattern for integrated circuits with a pattern size of 2.0 # m or less and a liquid crystal display of more than 2.0 // m Partially used photoresist pattern. [Embodiment] The following "The present invention is shown in the examples and explained in detail. (Synthesis Example 1) 1L with a cooling tube, a Teflon (registered trademark) stirring blade, and a thermometer" dripping funnel The separable flask has a composition (a molar ratio) of 1,3-dihydroxybenzene (ai) / -m-cresol (a2) / 3,4--cresol (a2) / 2,3, 5-trimethylphenol (a 2) = 15/68 / 8.5 / 8 · 5 mixed with 1 mol of phenols and 0.01 mol of p-toluenesulfonic acid dihydrate as an acid catalyst, and butyrolactone added Stir the total monomers (total concentration of mixed benzene to 40% by mass). -28- (24) (24) 3,4-XY: 2,3,5-TMP FA: Formaldehyde PA: C Aldehyde SA: Salixaldehyde 200428141 Secondly, the temperature of the oil bath was set to 100 ° c. Secondly, a 37.5% by weight aqueous formaldehyde solution (formaldehyde content of 0.005 mol) was added to the oil bath. •• Propionaldehyde (F 2) = 8 3.5: 1 6 _ 5 (The Morrbi dropping funnel was dripped slowly over 30 minutes. After that, the mixture was stirred for 12 hours at i0 (rC), and then cooled to room temperature ( 2 5 It was added with butyl acetate and washed with water, and the upper layer was concentrated by an evaporator to obtain a non-resin solution. The resin solution and methanol were added in a separatory funnel, and the n-heptane was stirred and then 'stand still' to peel off the lower layer and added PGMEA to obtain To IJ refined resin solution (A 1). The polystyrene mass average molecular weight (Mw) of the obtained resin was 10,500. (Synthesis Examples 2 to 6) In Synthesis Example 1, the composition of phenols, aldehydes (f 2) and aldehydes (Π) / (f2) were changed as described in Table 1, and others were the same as those in Synthesis Example 1. Similarly, resin solutions (A2) to () are obtained. In Table 1, the Mw of each resin is noted. In addition, the values in Table 丨 have the following meanings. 1 + DHB: 1,3-dihydroxybenzene mC: m Cresol xylenol 2,3,5-trimethylphenol propionaldehyde 76 Mo) At temperature), refined alkanes are converted to concentrated species, A6) Rule -29- (25) (25) 200428141 [Table 1 ] Composition of mixed phenylhydrazones (Molar ratio) (al / a2) Aldehydes (fl / f2) Mw Synthesis Example 1 1,3-DHB / mC / 3,4-XY / 2,3,5-TMP ( 15/68 / 8.5 / 8.5) 15/85 FA / PA (83.5 / 16.5) 10500 Synthesis Example 2 Same as above FA / SA (83.5 / 16.5) 10000 Synthesis Example 3 1,3-DHB / mC / 3,4-XY (l 5/68/17) Ibid. FA / PA (83.5 / 16.5) 10500 Synthesis Example 4 l, 3-DHB / mC / 3,4-XY / 2,3,5-TMP (15/68 / 8.5 / 8.5 ) Ibid. FA 10000 Synthesis example 5 mC / 3,4-XY / 2,3,5 -IMP (68 / 8.5 / 8.5)-/ 100 FA / PA (83.5 / 16.5) 11000 Synthesis example 6 Ibid. FA 11000 (Implementation Examples 1 to 4, Comparative Examples 1 to 2) Relative to the above Synthesis Example 1~6 The resulting resin solution (A 1) ~ (A6) of solid parts, (C) component based complex bis (2-methyl-4-hydroxyphenyl) - phenylmethane 35% by mass. Secondly, in the component (B), the mixed mass of "(B1) / (B2) / (B3) = 6/1/1 (mass ratio)" is compared with the total mass of the solid content of the resin and the (C) component. The blending amount is 30% by mass. Next, PGMEA was added to adjust the concentration of the solid component to 25% by mass to obtain a photoresist composition. The photoresist composition -30- (26) 200428141 was filtered with a filter of 0 2 / m to adjust the photoresist coating liquid. Table 2 shows the types and the photoresist molecular weight of each photoresist coating solution used. In addition, the above (B1) to (B3) are as follows. (B1) Bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane (B1 ') 丨 Mole and 1,2-naphthoquinonediazide- 5-sulfofluorenyl chloride [hereinafter, abbreviated as (5-NQD). 〔2 Molar esterification reaction product (B2) bis (2, kernel dihydroxyphenyl) methane (B2 ·) 1 Molar esterification reaction product (B3) bis (kernel hydroxyl group) -2,3,5_trimethylphenyl) _2_hydroxyphenylmethane (B3 ') 1 mol and 5_NQD 2 mol esterification reaction product [Table 2]

Resin solution Photoresistance Molecular weight Linearity Sensitivity (mJ) DOF (μιη) Resolution (μπι) Heat resistance Example 1 (A1) 5700 A 47.5 20 1.2 A Example 2 (A2) 5500 A 20 10 1.5 A Example 3 (A3) 5700 A 42.5 20 1.2 B Example 4 (A4) 5500 A 35 15 1.4 B Comparative Example 1 (A5) 6000 A 150 20 1.4 C Comparative Example 2 (A6) 6000 A 120 20 1.4 C About Examples 1 to 4. The photoresist coating liquids obtained in Comparative Examples 1 to 2, and -31-(27) (27) 200428141 each evaluated linearity, sensitivity, DOF, resolution, and heat resistance in the following order. The results are shown in Table 2. (Linear evaluation) A photoresist coating device for large substrates (device name: TR 3 6000, manufactured by Tokyo Yingka Kogyo Co., Ltd.) was used to apply a photoresist coating solution to a glass substrate (550 mm × 650 mm) formed by a T i film, and then The temperature of the hot plate is 100 ° C, and the first drying is performed for 90 seconds by opening the adjacent baking at an interval of about 1mm, and the temperature of the hot plate is 90 ° C by opening the interval of 0.5mm. The second drying was carried out for 90 seconds in the vicinity of baking to form a photoresist film with a film thickness of 1.48 # m. Secondly, the test pattern mask (marked line) of 3.0 # m L &amp; S and l.5 &quot; m L &amp; S photoresistive pattern reproducible mask pattern can be drawn at the same time, use i line The exposure device (device name: FX-702 J, manufactured by Nikon Corporation; NA = 0.14) performs selective exposure at an exposure amount (Eoρ exposure amount) that enables faithful reproduction of 1.5 / zm L &amp; S. Secondly, the temperature of the hot plate was set to 120 ° C, and the interval was opened by 0.5 mm, followed by baking for 30 seconds, followed by heating at the same temperature for 60 seconds without opening the interval. Heat treatment. Secondly, using a developing device with a gap coater nozzle (device name: TD-39000 display machine, manufactured by Tokyo Yinghua Chemical Industry Co., Ltd.), a 23 ° C, 2.38% by mass TMAH aqueous solution (product name "NMD-3 『Made by Tokyo Yinghua Chemical Industry Co., Ltd.】, from the end of the substrate X to Z (refer to the figure i), -32- (28) (28) 200428141 10 seconds after the liquid is loaded on the substrate 'hold for 5 5 seconds , Wash with water for 30 seconds for spin drying. The cross-sectional shape of the obtained photoresist pattern was observed with a SEM (scanning electron microscope) photograph to evaluate the reproducibility of the photoresist pattern of L &amp; S. The dimensional change rate of ± 10% or less is represented by A, the value exceeding 10% to 15% is represented by B, and the value exceeding 15% is represented by C. (Sensitivity evaluation) The photoresist pattern of 1.5 m L &amp; S is represented by an exposure amount (Eop) (mJ / cm2) that can be faithfully reproduced. (DOF evaluation) In the above exposure amount (Eop), the DOF can be moved up and down by 1.5 # m L &amp; S within the range of the dimensional change rate of ± 10% (total depth width) with // It is expressed in m units. (Resolution Evaluation) The exposure amount (Eop) is expressed by a limited resolution. (Evaluation of heat resistance) In the above-mentioned Eop exposure, the substrate depicted by '3_0 // m L &amp; S was set, and the hot plate at 140 ° C was allowed to stand for 300 seconds, and the cross-sectional shape was observed. As a result, if the dimensional change rate of 3.0 L &amp; S is less than ± 3%, it is A, if it is within the range of 3 to 4% or -3 to -4%, it is B, and if it exceeds ± 4%, it is C. -33- (29) 200428141 Photoresist composition containing phenol-formaldehyde lacquer resin, which is synthesized using the specific mixed phenols of Examples 1 to 4, and also has the characteristics of heat resistance and linearity, DOF, and resolvability. Excellent, self-explanatory material used in Portuguese. In addition, compared with Example 4 used in the phenolic lacquer resin synthesized by using aldehydes in aldehydes, the use of mixed aldehydes can obtain a photoresist composition having a high degree of rain. On the other hand, the composition of the comparative example which does not use mixed phenols has poor heat resistance and sensitivity. [Effects of the Invention] As described above, the positive-type photoresist composition of the present invention is extremely suitable for system LCD manufacturing. [Brief description of the figure] [Figure 1] The linear photoresist composition is coated on a glass substrate and baked and dried under low NA conditions. Z is an illustration of the purpose of filling the liquid. The present invention provides a positive photoresist composition made of LCD with high sensitivity and high heat resistance, forming an integrated circuit and a liquid crystal display portion. This positive-type photoresist composition contains a resin and (B) a quinonediazide-based compound, and the former: is composed of a phenol compound represented by the following general formula (I) and represented by the following general formula (II) Phenol compound (A2)-: excellent. Also, £ LCD manufacturing 丨 a specific mixture of 1 ~ 3, and the actual [heat resistance and further increase the photoresistance of 1,2 high sensitivity and high valence, the positive end of the substrate pattern exposed X-substrate can be i It is suitable for the (A) alkali soluble ® (A) component (a 1), and: a phenolic lacquer resin synthesized by the condensation reaction of phenols-34- (30) 200428141 and aldehydes.

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Claims (1)

(1) 200428141 Patent application scope i A positive photoresist composition for LCD manufacturing, which can form integrated circuits and liquid crystal display parts on a substrate, which is characterized by (a) alkali soluble resin and (B) containing A positive type photoresist composition of a quinonediazide compound, wherein the component (A) contains the following general formula (I) ~ \ — (〇H) a --- (1) (R) b [wherein R represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, dilute propyl 'or aromatic Group; a represents an integer of 2 to 4; b represents an integer of 0 or 1 to 2], a phenol compound (al) represented by the following general formula (π OH --- (11) (R) c [wherein R represents an alkyl group having 1 to 3 carbon atoms, and alkoxy, allyl, or aryl group having 1 to 3 carbon atoms; C represents 1 to 3 Integer] is a phenolic lacquer resin synthesized by the condensation reaction of a mixed phenol compound (A2) with phenols and aldehydes. 2. The positive photoresist composition according to item 1 of the scope of application, wherein the compounding ratio of the aforementioned phenol compound (a 1) and the aforementioned phenol compound (A2) is -36- (2) (2) 200428141 is 1:99 ~ 50: 50 (Morle ratio). 3. The positive photoresist composition according to item 1 or 2 of the scope of patent application, wherein the aforementioned aldehydes are a mixture of formaldehyde and propionaldehyde. 4 · The positive photoresist composition according to item 1 of the patent application scope, wherein the aforementioned (B) component system contains a non-diphenyl ketone-containing phenolic hydroxyl compound and 1,2-naphthoquinonediazide group. Product of esterification reaction of sulfonyl compound. 5. The positive photoresist composition according to item 1 of the patent application scope, which further contains (C) a phenol-containing hydroxy compound having a molecular weight of 1,000 or less. 6. —A photoresist pattern forming method, comprising the following steps: (1) coating a positive photoresist composition according to any one of claims 1 to 5 on a substrate to form a coating The film step is (2) a step of forming a photoresist film on the substrate by heating (pre-baking) the substrate with the above-mentioned coating film formed, and (3) using a photoresist of 2.0 / zm or less relative to the above photoresist film The mask pattern for pattern formation and the mask described by both sides of the mask pattern for the photoresist pattern formation of more than 2.0 // m are used for selective exposure. (4) After the above selective exposure, The photoresist film is subjected to a heat treatment (post-exposure baking) step. (5) The photoresist film after the heat treatment is subjected to development processing using an alkaline aqueous solution. On the substrate, the pattern size is 2.0 / zm. The following steps are used to form a photoresist pattern for an integrated circuit and a photoresist pattern for a liquid crystal display portion exceeding 2.0 / zm at the same time. 7. The method for forming a photoresist pattern as described in item 6 of the scope of the patent application, wherein the step of (3) selective exposure is performed at light source -37- (3) 200428141 using i-line 'and NA at The exposure process is performed under low NA conditions below 0 · 3. -38-