TWI254191B - Resist pattern formation method - Google Patents

Abstract

A resist pattern formation method which is suitable for production of system LCDs, can reduce variation in resist pattern size. The method includes (1) a step for coating a positive photoresist composition on a substrate to form a coating, (2) a step for prebaking the substrate with the coating formed thereon, to form a resist coating film on the substrate, (3) a step for forming an antireflective film on the resist coating film, (4) subjecting the resist coating film to selective exposure by using a mask having both a mask pattern for formation of resist patterns of less than 2.0 mum and a mask pattern for formation of resist patterns of more than 2.0 mum, (5) a step of removing the antireflective film after selective exposure, and (6) a step of subjecting the resist coating film, after the selective exposure, to a developing treatment using an aqueous alkali solution.

Description

1254191 (1) Field of the Invention The present invention relates to a method for forming a resist pattern for forming an integrated circuit and a substrate of a liquid crystal display portion on the same substrate. [Prior Art] [Problems to be Solved by the Invention] At present, next-generation LCDs simultaneously form drivers, digital analog converters (DACs) on the same glass substrate, image processing devices, video controllers, and random access memories ( In the integrated circuit part and the display part of the RAM, etc., the development of the technology of the high-performance LCD of the so-called "system LCD" is prevailing (refer to Non-Patent Document 1 below). In the present specification, a substrate in which an integrated circuit and a liquid crystal display portion are formed on the same substrate is referred to as an expedient system L C D . In the system LCD, for example, the pattern size of the display portion is 2 to 1 0 /i ηι, and the integrated circuit portion is formed in a fine size of about 0.5 to 2.0 // m; therefore, the light used in the system LCD manufacturing In the resist composition, in addition to the ability (linear) to form a fine pattern and a rough pattern at a good shape at the same time, high resolution, high depth of focus (DOF) characteristics of the fine pattern, and the like are more strictly required. However, in the photoresist material in the field of manufacturing liquid crystal elements, the decrease in sensitivity causes a significant problem-solving ability to be lowered, which is extremely unsuitable; it is expected that the sensitivity is not lowered, and the above characteristics can be improved. In addition, especially in the field of LCDZ manufacturing, compared with tantalum wafers used in the manufacture of semiconductors (2) (2) 12541191, in addition to the increase in bending that often occurs in glass substrates of a very large area, in the photoresist film In the lower layer, there is a problem that the surface smoothness is also deteriorated. Therefore, the film thickness of the photoresist film is uneven, and the effect of the multi-interference is likely to be increased, and the effect on the body effect is increased (refer to Patent Document 1 below); Due to the difference in film thickness of the photoresist film, the dimensional change rate of the photoresist pattern is further enlarged, and there is a problem that the variation in the size of the photoresist pattern increases in the surface of the substrate. In particular, the substrate area of the system LCD has a tendency to expand, and the photoresist pattern is more refined, so that the problem will be more significant. [Non-Patent Document 1] Semiconductor FPD World, September 2001, pp. 50 to 67 [Patent Document 1] JP-A-6-2] 185. The present invention has been made in view of the above circumstances to provide a system suitable for use in the manufacture of a system LCD. A method of forming a photoresist pattern capable of suppressing variations in the size of a photoresist pattern is a problem. SUMMARY OF THE INVENTION [Means for Solving the Problem] The above-described problems are solved by the following means of the present invention. A method for forming a photoresist pattern according to the present invention, comprising: (1) applying a positive photoresist composition to a substrate to form a coating film, and (2) preheating the substrate on which the coating film is formed ( PB) a step of forming a photoresist film on the base, (3) a step of forming an anti-reflection film on the photoresist film, and (4) using a photoresist film of 2.0 m or less -6 - (3) a photoresist pattern for forming 1254191, a resist pattern of 2. Ο // m or more, a mask for drawing a mask pattern, a step of performing selective exposure, and (5) a selective exposure Thereafter, the step of removing the anti-reflection film and the step (6) of the photoresist film after the selective exposure are performed by performing an image forming process on the substrate, and forming an integrated circuit having a pattern size of 2.0 m or less. The step of the photoresist pattern and the photoresist pattern for the liquid crystal display portion of 2·0 // m or more. Further, the weight average molecular weight (M w ) of the photoresist composition in the present specification is measured by the following Gp C system. Device name: System 1 1 (product name, manufactured by Showa Denko Co., Ltd.) preparatory column: KF-G (product name, manufactured by Shodex Co., Ltd.) Column · KF — 8 05, KF — 803, KF — 802 (product name, Detector: UV 41 (product name, manufactured by Shodex Co., Ltd.) was measured at 280 nm for a solvent or the like: a flow rate of 1. 〇ml/min, and tetrahydrofuran was allowed to flow, and it was measured at 35 °C. The preparation method of the sample is as follows: the photoresist composition for measurement is adjusted to a solid concentration of about 3% by weight, and diluted to a solid concentration of 〇. 1% by weight, which is prepared for the measurement sample; The measurement sample was injected into the above device at 2 0 // 1, and the measurement was performed. [Embodiment of the Invention] <Composition of Antireflection Film, Material> -7- (4) 1254191 In the present invention, the antireflection film is provided as an upper layer of the photoresist film as long as it has an antireflection function. At the same time, the light (high energy line) used in the selective exposure step of the photoresist film can be penetrated, and the material is not particularly limited; there are various proposals for forming the composition of the anti-reflection film, for example, the special opening 200 Pp. 200019, JP-A-2002-174899, JP-A-6-4 1 7 6-8, JP-A-6-2 7 3 92 6 , and JP-A-6-2 8 962 0 7 - 1 8 1 6 8 5, JP-A-7-2 9 5 2 1 0, JP-A-8-9 5 2 5, and the like; in the present invention, such well-known formation prevention can be used. A composition for a reflective film. Especially after the exposure step, the antireflection film is preferably soluble in water or soluble in an aqueous alkaline solution. When the antireflection film is soluble in water or an alkaline aqueous solution, when the photoresist film after selective exposure is subjected to development processing by a developing liquid, the antireflection film can be simultaneously removed by the developing solution; in this case, in the light In addition to the development processing step of the resist film, it is not necessary to separately provide the removal step of the anti-reflection film, which is extremely suitable for engineering. In the material for forming the antireflection film in the present invention, for example, a polymer compound described in JP-A-2000-2000 can be used. That is, a polymer compound obtained by polymerizing a cyclic perfluoromonomer and a perfluorocarbon unit having a sulfonyl group in a branched chain can be used; such a polymer compound is represented by the following general formula (1) 'especially It is suitable for those shown in the general formula (2). 1254191 (5) R2 R3

Cf3 {〇CF2CF2)^S〇3M ...(1)

.CFf~h •·-(2) (ocf2 cf 〇cf2 cf2)^ so3m cf3 where R1 is a carbon atom in which a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom is a main chain or a branched chain. a linear or branched alkenyl group having a fluorination of ～2; in this case, R 1 is a ring of two carbon atoms bonded together with a total of 3 to 2 carbon atoms to form a ring of 3 to 8 The structure is more suitable; further, a part of the hydrogen atom of the fluorinated or alkenyl group may be substituted by a fluorine atom, and all of the hydrogen atoms may be substituted by a fluorine atom, and all of the hydrogen atoms of the alkenyl group may be fluorine. Replacement is better. Further, R2 to R5 are independently a fluorine atom or a fluorinated linear or branched alkyl group having 1 to 10' carbon atoms, particularly a carbon number of 1 to 3; It is better to use part or all of them.

a ~ d is, when b = l, 0 < a < 100, ISaSlO is better, 0 $ c < 2 〇, 〇 Sc <] 〇 is better, 0 $ d < 20, 0Sd < 10 is better, A; a 2, a 2 is, 0 S a 1 < 1 0 0, 0 0 a ] $ 1 0 is better, 0 Sa2<】〇〇, 〇$a2$l〇 is better, 0<al+a2<]. 00, preferably IS -9-(6) 1254191 a l+a2S 10; and η is an integer of 1 to 5, preferably an integer of 2 to 7. Μ is a hydrogen atom or an amine, and the amine component of hydrazine is preferably a water-soluble organic amine-based compound such as ammonia, tris(hydroxymethyl)aminomethane, pyridine, trimethylamine, triethylamine, tetramethylammonium hydride, Tetraethylammonium hydride, tetrapropylammonium hydride, tetrabutylammonium hydride, choline, 2,2 /,2 〃 mononitrotriethanol, monoethanolamine, diethanolamine, 1,4 -diindole bicyclic [2 _ 2 · 0] octane (DABCO), 1,5-dibicyclo[4.3.0]nonene-5 (DBN), 1,8-diguanidine (5.4.0) (Η-)ene-7 (DBU), 1-deoxy-1 mono(2-hydroxyethylamino)-D-semi-glucitol, 1-deoxy-indolyl (methylamino)-D-half-lactitol, etc. are exemplified; The refractive index may be a perfluoroorganoamine compound, a primary, tertiary or tertiary alkylamine compound having a carbon number of 1 to 20, or an alkanolamine compound; and specifically, perfluorotriethylamine and perfluoro Triethanolamine, perfluorotripropylamine, perfluorotributylamine, perfluoropentylamine, trifluoroethylamine, trifluoropropylamine, 4,4,4-trifluoro-DL-valine, 5,5,5-three Fluorine-DL- a water-soluble organic amine compound, a sulfonate group of the compound represented by the general formula (1) or (2), 1 mole, 〇. 〜 〇 耳, especially 〇. 1~5 Ear addition is more suitable. In the above formula (2), the following formula is used as the repeating unit, -10- 1254191

The polymer compound has a weight average molecular weight of 1,00 0 to 1,000,000, particularly preferably 2,000 to 100,000. The antireflection film forming composition for forming an antireflection film is preferably one containing the polymer compound as a polymer component, and may be composed of only the polymer compound, and may be blended with various water-soluble polymers; for example; It can be blended with water-soluble polymers such as polyvinyl alcohol, polyacrylic acid, poly(meth)acrylic acid, polyvinylpyrrolidone, polyethylene oxide, amylose, dextran, cellulose, and osmanthus sugar. The film-forming property is improved, and the amount of the water-soluble polymerization % is preferably in the range of 〇 to 300 parts by weight based on 100 parts by weight of the polymer compound. -11 - (8) 1254191 In the composition for forming an antireflection film, a conventional surfactant may be added to improve the applicability, and the amount of the surfactant may be used in a range that does not impair the effects of the present invention. . Surfactants include perfluoroalkyl polyethylene oxide, fluorinated terephthalate, perfluoroalkylamine oxide, fluorine-containing organooxane compounds, etc.; for example, Flora "FC-430 "FC-431" (both Sumitomo 3M Co., Ltd.), Safron "S-141", "S-145", "3 - 3 8 1", "S-3 8 3" (all Asahi Glass Co., Ltd.), Unida because of "DS-401", "DS-403", "DS-451" (both made by Benz E-Industry Co., Ltd.), Megawah "F-8 1 5 1", "F-171", "F-172", "F-173", "F-177" (both manufactured by Dainippon Ink Co., Ltd.), "X-70-0 9 2", "X - 70 - 093" (both manufactured by Shin-Etsu Chemical Co., Ltd.), etc.; Flora "FC-430" and "X-70-093" are preferred. Further, a composition for forming a water-soluble antireflection film is likely to generate bubbles, and microscopic microbubbles called "microbubbles" may cause pattern defects; and microbubbles may be reduced to add an antifoaming agent. Effective; defoaming agent is preferably high in hydration, such as alcohols such as methanol, ethanol, isopropanol, n-butanol, n-hexanol, ethylene glycol, etc., and the following general formula (3), ( 4) An acetylene defoamer as shown. -12- (9)1254191 R11 R13

19 I I ^12—C —C —C—c —R14

AA 16 •••(3) 〇0 R17 R18—C—C—=C—R19 0 >20 (4) 0 The above-mentioned cyclic perfluoromonomer is polymerized with a perfluorocarbon monomer having a branched sulfonyl group. The polymer compound has a high transmittance and a low refractive index in a KrF laser (wavelength 24 8 nm) and an ArF laser (wavelength 1 93 nm), which are described in the above literature; the working colleagues of the present invention, In the method of exposing with an i-line (wavelength 3 6 5 nm) to form a photoresist pattern, it has been found that an antireflection film using the polymer compound is also extremely suitable. <Positive-type photoresist composition> The positive-type photoresist composition used in the present invention is not particularly limited as long as it is used by the conventional user, and may be used as a non-chemically enhanced type or as a chemically enhanced type. Good 'in terms of low cost of raw materials, non-chemically enhanced type is preferred; especially in LC〇|U Hao, ☆ late, so that 闬i line (3 6 ί ~ 13- (10) 1254191 nm) The phenolic-naphthoquinone-based photoresist composition is suitable. On the other hand, the chemically enhanced type has the advantages of large contrast, excellent resolution, and depth of focus (DOF) of the unexposed portion and the exposed portion. [Non-Chemically Enhanced Positive-Type Photoresist Composition] First, an example of a non-chemically-enhanced photoresist composition will be described below. The positive resist composition of this example contains (A) an alkali-soluble resin, (B) a naphthoquinone diazide compound, (C) a phenolic hydroxy compound having a molecular weight of 1 〇 〇 or less, and an organic solvent. (A) Ingredients: (A) The component is not particularly limited, and the positive-type photoresist composition may be used singly or in combination of one or more of those conventionally used as a film-forming substance. For example, naphthols (phenol, m-cresol, p-cresol, xylenol, trimethylphenol, etc.), and aldehydes (formaldehyde, formaldehyde precursor, propionaldehyde, 2-controlled benzophenone, 3 a phenolic resin obtained by condensation in the presence of an acidic catalyst, a phenolic ketone, a ketone (such as methyl ethyl ketone, etc.) and/or a ketone (methyl ethyl ketone, acetone, etc.); a copolymer of hydroxystyrene with another styrenic monomer, a hydroxystyrene resin such as a copolymer of hydroxystyrene with acrylic acid or (meth)propionic acid or a derivative thereof; a propionic acid or a methyl group An acrylic or (meth)acrylic resin or the like which is a copolymer of acrylic acid and its derivative. -14 - (11) (11) 1254191 Among them, a phenol resin or a hydroxystyrene resin is suitable. In particular, the condensation reaction is carried out by containing at least two kinds of phenols selected from the group consisting of m-cresol, p-cresol, 3,4-dimethylphenol and 2,3,trimethylphenol, and aldehydes containing formaldehyde. The phenolic resin is suitable for the adjustment of materials with high sensitivity and excellent resolution. (A) The ingredients can be made according to the usual method. The gel permeation chromatography method of the component (A) and the weight average molecular weight in terms of polystyrene vary depending on the type thereof, and are preferably 1005,000, more preferably 3,000 to 30,000, from the viewpoint of sensitivity and pattern formation. (B) Ingredients: (B) is not particularly limited as long as it is a product of a non-benzophenone-based phenolic hydroxyl group and an esterification reaction with a 1,2-naphthoquinonediazidesulfonic acid compound. In the general positive-type resist composition, those which are photosensitive components are not particularly limited, and one type or two or more types can be used arbitrarily. A compound containing a non-benzophenone-based phenolic hydroxyl group, particularly a phenol compound represented by the following general formula (i), and an esterified product with a 1,2-caioxadiazidesulfonic acid compound, is suitable for using an i-line The lithography, or a fine photoresist pattern of 2.0 // m or less suitable for forming a good shape under low NA conditions; that is, high resolution and linearity are good. -15 - (12)1254191

(i) Γ 4 rb, ~Rf, r5~r8 are respectively independent hydrogen atoms, [wherein κ

_ atom, an alkyl group having 1 to 6 carbon atoms, a oxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms; and R]] are independently hydrogen atoms or carbon atoms 1 to 6 of the hospital base; R9 is a hydrogen atom or a carbon number of 1 to 6 in the hospital, Q1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or the following formula (ii) The residue ' or Q 1 is linked to the end of R 9 'when' Q 1 舄 R9 and Q] and the carbon atom between R 9 is a cycloalkyl group having a carbon chain of 3 to 6; a, b is 1 to 3 An integer; d is an integer from 0 to 3; when a, b, or d is 3, there is no r3', R6, or R8, respectively; η is an integer of 0 to 3)

(wherein, Ri2lR]3 is 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; c is 1~3 of the whole)], 2-naphthoquinonediazidesulfonic acid compound, 1,2-naphthoquinone dimide gas - a 4-sulfonyl compound,], 2-naphthoquinone diazide Base one 5-sulfonate compound is more suitable. -16 - (13) (13)1254191 Further, when Q] is a cycloalkyl group in which a carbon atom between R9 5 and Q1 and R9 forms a carbon chain of 3 to 6, Q1 and R9 are bonded to each other to form a carbon atom number of 2 〜5的烯〇 In the general formula, the phenol compound is tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(4- Hydroxy- 2,3,5-trimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, double (4 Hydroxy-3,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)- 2-hydroxyphenylmethane, bis(4-hydroxyl) 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-dihydroxyphenyl Alkane, bis(4-hydroxy-2,5-dimethylphenyl)- 2,4-dihydroxyphenylmethane, bis(4-hydroxyphenyl)-3-methoxy-tetrahydroxyphenylmethane , bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-tetrahydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxybenzene Methane, bis(cyclohexyl-4-hydroxyl-2-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3,4 a tris(phenyl)phenol type compound such as dihydroxyphenylmethane. 2,4 a pair (3,5 - methyl - 4 - fluorenyl) - 5 - y phenol, 2,6 - bis (2,5 -diindolyl-4-hydroxybenzyl) - 4 a linear 3-nuclear phenol compound such as a methyl-1 - (14) 1254191 phenol; 1,1 bis[3 - (2-hydroxy-5-methylbenzyl)-4-hydroxy-5-cyclohexylbenzene 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-tetrahydroxybenzyl)-4-hydroxy-5-methylphenyl]methane, double [3 -(3,5-Dimethyl-4-hydroxybenzyl)-4-hydroxy-5-ethylphenyl]methane, bis[3-(3,5-diethyl-tetra-hydroxybenzyl) ) — 4-hydroxy-5-methylphenyl]methane, bis[3-(3,5-diethyl-4-hydroxybenzyl)-4-hydroxy-5-ethylphenyl]methane, double 2 One base 3 - (3 '5 - one methyl one 4 one base) one 5- Phenyl phenyl]methane, bis[2-hydroxy-3-(2-hydroxy-5-methylbenzyl)-5-methylphenyl]methane, bis[4-hydroxy-1,3-(2-hydroxy-5) —methylbenzyl)-5-methylphenyl]methane, bis[2,5-dimethyl-3-(2-hydroxy-5-methylbenzyl)-4-hydroxyphenyl]methane, etc. Linear 4-nuclear phenolic compound; 2,4 bis[2-hydroxy-3-(4-hydroxybenzyl)-5-methylbenzyl]-6-cyclohexylphenol, 2,4-bis[4-hydroxyl —3-(4-hydroxybenzyl)-5-methylbenzyl]-6-cyclohexylphenol '2,6-bis[2,5-dimethyl-3-(2-hydroxy-5-fluorenyl) a linear 5-nuclear phenol compound such as benzyl)-4-tetrahydroxybenzyl]-4-methylphenol, etc., a linear polyphenol compound; bis(2,3,4-trihydroxyphenyl)methane, bis (2) , 4 - dihydroxyphenyl) decane, 2,3,4-trihydroxyphenyl - 4 / hydroxyphenylmethane, 2-(2,3,4-trihydroxyphenyl)-2-(2^ ,3〆,4〆-18 - (15) 1254191 trishydroxyphenyl)propyl Alkyl '2-(2,4-dihydroxyphenyl)- 2-(2^,4〃-dihydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2(4-monophenylene)乙院, 2-(3- gas-tetra-phenylene)-2-(3〃-fluoro-4-cyanophenyl)propane, 2-(2,4-dihydroxyphenyl)-2-( 4/-hydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(4<-hydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl) a bis(phenyl)phenol type compound such as 2-(4-hydroxy-3,5〃-dimethylphenyl)propane; 1-[1(4-hydroxyphenyl)isopropyl]-4 —[1,1-bis(4-hydroxyphenyl)ethylbenzene, 1-[1-(3-methyl-4-hydroxyphenyl)isopropyl]-[1][1,1-double (3 —Methyl 4-pyridylphenyl)ethyl]benzene, etc., a multinuclear branched compound; 1,1 bis(4-hydroxyphenyl)cyclohexane or the like, a condensed phenol compound or the like. These may be used alone or in combination of two or more. These are mainly composed of a trisphenol type compound, and are particularly suitable from the viewpoint of high sensitivity and resolution, particularly bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)- 3,4-dihydroxyphenylmethane (hereinafter abbreviated as (B) / ), bis(4-hydroxy-2,3,5-trimethylphenyl)-2-hydroxyphenylmethane (hereinafter referred to as ( B 3 /) is most desirable; in addition, for the purpose of adjusting the photoresist composition excellent in resolution, sensitivity, heat resistance, depth of focus (DOF) characteristics, and linearity of photoresist characteristics such as linearity, The linear polyphenol compound, the bisphenol type compound 'multinuclear branched type compound, and the condensation type phenol compound are preferably used together with the above trisphenol type compound, particularly a bisphenol type compound, especially with a double (2' 4 one) -19- (16) (16)1254191 Per-phenyl)methane (hereinafter abbreviated as (B 2 / )) can be used to adjust the total and balance of the photoresist composition. The following are the following "B" / ), (B2 - ), and (B3 ^ ), respectively, and are referred to as (B 1 ), (B 2 ), (B3). When (B 1 ) and (B3 ) are used, the amount of the component (B) is 1% by weight or more, and more preferably B% by weight or more. Further, when all of '(B 1 ), (B 2 ) and (B 3 ) are used, the blending amount is (B1) 5 〇 to 90% by weight, preferably 60 to 80% by weight, from the viewpoint of effect. The blending amount of (B2) is 5 to 25% by weight, more preferably 1 to 15% by weight, and the amount of (B3) is 5 to 25% by weight, more preferably 1 to 15% by weight. The method of esterifying all or a part of the compound of the above formula (1) with a naphthoquinone diazide sulfonate can be carried out according to a usual method; for example, a chlorinated sulfonium chloride It can be obtained by condensation with a compound represented by the above general formula (i). Specifically, for example, the compound represented by the above general formula (i), and the naphthoquinone, a sulfonium chloride, are dissolved in dioxane according to the quantitative amount. An organic solvent such as n-methylpyrrolidone dimethylacetamide or tetrahydrofuran, wherein one or more basic catalysts such as triethylamine, diethanolamine, pyridine, carbonic acid base, and hydrogencarbonate are added to carry out the reaction. The material is washed and dried, and can be prepared. (B) a non-benzophenone-based phenolic hydroxy compound and an esterification reaction product with a 1 '2-naphthoquinonediazidesulfonic acid compound, also -20-(17) (17)1254191 Other naphthoquinone diazide ester compounds, such as polyhydroxybenzophenone, or a phenolic compound such as a gallic acid base, or an esterification reaction product with a diazide diacid acid compound may also be used. use. These other naphthoquinone diazide esters are used in an amount of 80% by weight or less, particularly 50% by weight or less, based on (B) the photosensitive component, and are more suitable for enhancing the effects of the present invention. The compounding amount of the component (B) in the resist composition is preferably 20 to 70% by weight, based on the total amount of the component (A) and the component (C), and is preferably 25 to 60% by weight. (B) When the amount of the component is at least the above lower limit ,, a faithful image can be obtained, and the copyability can be improved. When the upper limit is less than or equal to ,, the sensitivity can be prevented from being deteriorated, and the uniformity of the formed resist film can be obtained. Sexuality and the effect of improving resolution. (C) Ingredients: The (C) component is excellent in the effect of improving the sensitivity. In the i-line exposure process under low N A conditions, it also has high sensitivity and high resolution, and a material suitable for a system LCD with excellent linearity can be obtained. The molecular weight of the component (C) is 1; 〇〇〇 or less is preferably 7Q0 or less, substantially 200 or more, and preferably 300 or more, which is suitable from the above effects. (C) a component, generally used as a phenolic hydroxy compound for improving a sensitivity material or a sensitizer for a photoresist composition; as long as the above molecular weight conditions are satisfied, there is no particular limitation, and one or two types may be arbitrarily selected. It is used on -21 - (18) 1254191; and then, in particular, the phenol compound shown by the following general formula (i丨i) exhibits superior properties as described above, and is extremely suitable.

...(iii)

Wherein R21 to R28 are independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having a carbon number of 丨6, or a ring having a carbon number of 3 to 6 ; R3 (), is a separate hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R29 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; when Q2 is a hydrogen atom or a carbon atom; An alkyl group of 1 to 6 or a residue represented by the following chemical formula (iv), or a terminal of Q2 and R29, wherein Q2 is R29 and the carbon atom between Q 2 and R 2 9 is simultaneously a carbon chain 3 to 6 cycloalkyl; e, f is an integer from 1 to 3; h is an integer from 0 to 3; when e, f or h is 3, respectively

There is no R23, R26, or r28; n is an integer of 〇~3]

(0Η)〇• · · (iv) (wherein R.2 and R&quot;3' are independent hydrogenogens, ® atoms, and a number of carbon atoms of 1 to 6, and the number of carbon atoms is ~6 a oxy group, or a cycloalkyl group having 3 to 6 carbon atoms; g is an integer of 0 to 3) specific, for example, as exemplified in the above component (B), used in a naphthoquinone diazide compound of a phenol compound 'Besides the benzoic acid compound can be used to make (19) 1254191 a biguanide (methyl 3-methyl, 4, 4-hydroxyphenyl) group, a phenyl ketone, phenylmethane, bis (3 (2) -ethyl-a-4,5-di especially, bis- 4~-phenyl-phenyl)- 4-isopropylphenyl-phenyl, hydroxyphenyl)-phenylmethane, bis(2-methyl, benzene Methane, bis(3-methyl-2-hydroxyphenylbis(3,5-dimethyl-tetrahydroxyphenyl)-5-ethyl-4-hydroxyphenyl)-phenylmethane, bishydroxybenzene a trisphenol type compound such as monophenylmethane or bis(2-tert-butylphenyl)-phenylmethane; 4 2 methyl-tetrahydroxyphenyl)-phenylmethane, 1 [1] 4 — by its — 赛本 _) isopropyl 〕 4-1 [1,1-bis(4-hydroxyphenyl)ethyl] _ is most suitable for the compounding amount of () component, from the point of effect, the (A) component is 10~70 heavy / 恿%, preferably in the range of 20 to 60% by weight. In this case, the positive-opening u, W resist composition can be obtained by dissolving the components of (A) to (C) and the ingredients of the demand, and dissolving them in an organic solvent. Organic solvent: ¥ ί 容 容 ϋ ϋ 'The general use of the photoresist composition is not particularly limited. One or two or more types may be used; propylene glycol monoalkyl ether acetate, and/or Among the 2 - heptanone, the coating property is excellent, and the film thickness uniformity of the photoresist film on a large glass substrate is excellent, and it is especially suitable. Further, both propylene glycol monoalkyl ether acetate and 2-heptanone can be used; they can be used alone or in combination with other organic solvents. The film thickness uniformity when applied by a spin coating is excellent. The content of propylene glycol monoalkyl ether acetate in an organic solvent is suitably 5 〇 -23 - (20) 1254191 to 100% by weight. Propylene glycol monoalkyl ether acetate, for example, a linear or branched alkyl group having 1 to 3 carbon atoms, especially propylene glycol monomethyl ether acetate (hereinafter abbreviated as PG EA EA ), in a large glass The uniformity of the film thickness of the photoresist film on the substrate is particularly excellent. On the other hand, 2-heptanone is not particularly limited, and as described above, when (B) naphthoquinone diazide compound is combined with a non-benzophenone-based photosensitive component, it is a very suitable solvent. · 2 -Heptone is a solvent that is superior to P G Μ E A because it has excellent heat resistance and can reduce the scum of the photoresist composition. When 2-heptanone is used alone or in combination with other organic solvents, it is preferably contained in the total organic solvent in an amount of 50 to 100% by weight. Further, these suitable solvents can be used in combination with other solvents; for example, when blended with an alkyl lactate such as methyl lactate or ethyl lactate (preferably ethyl lactate), the film thickness of the photoresist film is uniform. Excellent in properties, it can form a beautifully shaped resist pattern, which is extremely suitable. When φ propylene glycol monoalkyl ether acetate is mixed with alkyl lactate, the weight ratio of propylene glycol monoalkyl ether acetate is preferably 〇·!~~〇, and it is preferably ～5 times 'Lactic acid based vinegar is more suitable; in addition, organic solvents such as γ-butyrolactone and propylene glycol monobutyl ether can also be used. When r-butyrolactone is used, the weight ratio of propylene glycol monoalkyl ether acetate is preferably in the range of 〇 〇 〇 1 〜 1 times 〇. 0 5 〇 〇 5 times. There are also other organic solvents which can be blended, and specific examples thereof are listed below. -24 - (21) 1254191 ie ketones such as acetone, methyl ethyl ketone, cyclohexanone and methyl isoamyl ketone; ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate, a divalent ethylene glycol monoacetate, or a polyvalent alcohol such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or monophenyl ether; and derivatives thereof; such as a ring of dioxane Ethers, and esters such as methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate. When such a solvent is used, it is preferable to contain 50% by weight or less in the organic solvent. The positive-type resist composition of this example may contain a compatible additive such as an additional resin or a plasticizer for improving the performance of the photoresist film, etc., insofar as the object of the present invention is not impaired. A stabilizer, a surfactant, a coloring material which makes the image of the image clearer, and a conventional additive such as a sensitizer for enhancing the sensitizing effect, a dye for preventing fading, and a tackifier. For the anti-corona dye, an ultraviolet absorbing agent or the like can be used (for example, 2, 2, 4, 4 / tetrahydroxybenzophenone, 4 - dimethylamine benzene - 2', 4 - dihydroxy diphenyl) Methyl ketone, 5-amino-3-methyl-l-phenyl- 4-(4-mono-phenylphenylazo) D is more than D, 4-dimethylamino- 4'-hydroxy azo Benzene, 4-diethylamino group - 4 - ethoxy azobenzene, 4-diethylamino azobenzene, curcumin, etc.). The surfactant is added, for example, to prevent streaks, and for example, Florado FC-430, FC-431 (trade name, manufactured by Sumitomo 3M Co., Ltd.), Yevpup EF] 22A, EF] 22B, EF can be used. ] 22C, EF126 (trade name, manufactured by Dekam Products Co., Ltd.) and other fluorine-based interface activities - 25 - (22) 1254191 agent; XR - 1 04, Megan library r - 〇 8 (trade name, Dainippon Ink Chemical Industry Co., Ltd.) and so on. Further, the amount of the organic solvent to be used is preferably such that the components (A) to (C) and other components which are required to be dissolved are dissolved, and a uniform positive resist composition can be obtained and appropriately adjusted; The concentration [(A) to (C) component and other components required for the demand] is 丨〇~5〇% by weight, more preferably 20~35 wt%. In the positive resist composition of this example, the Mw of the solid content contained in the photoresist composition is determined by the GPC method after the total component is mixed, and the weight of the polystyrene is converted. The average molecular weight (Μλν) (resistance molecular weight) is adjusted to a range of 5,000 to 30,000, and (Mw) is preferably 6,0 0 0 to 1 0 5 0 ;; the solid content of the photoresist composition When M is within the above range, a positive resist composition which is excellent in heat resistance and localized resolution, and which has excellent linearity and depth of focus (D 〇F ) characteristics, can be obtained without lowering the sensitivity; In the above range, the river of the solid content of the photoresist composition is superior in heat resistance, resolution, linearity, and DOF characteristics, and the coating property of the photoresist composition is also excellent. The method of modulating the M w to the above-mentioned suitable range is, for example, (1) the Mw after the total component is mixed up to the above range, and the history of the mixture (A) is separately operated, etc. '(A) component % w is pre-adjusted to the range of the appropriate S' (2) Preparation] The VU/different plural (a) component 'is appropriately blended to make the solid portion "to the above range, etc. According to the above-mentioned (2) modulation method, the adjustment of the molecular weight of the photoresist and the adjustment of the sensitivity of -26 ' (23) 1254191 are relatively easy, and it is very suitable. [Chemically enhanced positive photoresist composition] Next, it is suitable for the present invention. The three embodiments of the chemically amplified positive-type photoresist composition used are as follows. <First embodiment> The positive-type photoresist composition of this embodiment contains (A /) alkali-insoluble or The alkali is poorly soluble, and it becomes an alkali-soluble resin component by acid action, and (E) photoacid generator. • (A / ) component In this embodiment, (A / ) component uses (a 1 ) phenolic property. One of the total phenolic hydroxyl groups of the hydroxyl group-soluble resin component a partially insoluble or insoluble resin component which is protected by an acid dissociating dissolution inhibitor; this is (a 1 ) an alkali-soluble resin component which is insoluble or insoluble by alkali dissolving and inhibiting the base. (a 1 ) The component (alkali-soluble resin component) is not particularly limited, and may be arbitrarily selected from a user of a positive-type photoresist composition as a film-forming substance; more preferably, an aromatic hydroxy compound, and an aldehyde are preferable. a phenol resin obtained by a condensation reaction, a polyhydroxystyrene and a derivative thereof (hydroxystyrene resin), etc. The above aromatic hydroxy compound is, for example, phenol; m-cresol, p-cresol , phenols such as o-cresol; 2,3-xylenol, 2,5 - -27 - (24) 1254191 xylenol, 3,5-xylenol, 3,4-dimethylphenol, etc. Dimethylphenol; m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butyl Phenolic, 3-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl- 4 Alkylphenols such as monomethylphenol or 2-tert-butyl-5-methylphenol; p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol An alkoxyphenol such as p-propoxyphenol or m-propoxyphenol; o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, 2 Isopropenylphenols such as ethyl-4-isopropenylphenol; arylphenols such as phenylphenol; 4,4 / -dihydroxybiphenyl, bisphenol A, meta-benzenediol, p-benzene Polyphenols such as diphenols and benzenetriols; these may be used singly or in combination of two or more. The above aldehydes are, for example, formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde, acrolein, crotonaldehyde, cyclohexanal, furan aldehyde, furyl acrolein, benzene. Formaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropanal, yS-phenylpropanal, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde , m-methylbenzaldehyde, p-methylbenzaldehyde, o-chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, cinnamaldehyde, etc.; these may be used alone or in combination of two or more . Among these aldehydes, it is preferable to use formaldehyde, and in particular, it is preferable to use a combination of hydroxybenzaldehyde and formaldehyde to improve heat resistance. -28- (25) 1254191 The above ketones are, for example, acetone, methyl ethyl ketone, diethyl ketone, diphenyl copper, etc., and these may be used singly or in combination of two or more; It can also be mixed properly. The condensation reaction product of the above aromatic hydroxy compound with an aldehyde or a ketone can be produced by a known method in the presence of an acidic catalyst; the acidic catalyst at that time is hydrochloric acid, sulfuric acid, formic acid, oxalic acid, and Stupid sulfonic acid and the like can be used. The above polyhydroxystyrene and derivatives thereof include, for example, a gastric-only polymer of vinyl phenol, a copolymer of a comonomer obtained by copolymerization with a vinyl phenol, and the like; and the comonomer is, for example, an acrylic acid derivative. , acrylonitrile, (meth)acrylic acid derivatives, (meth)acrylonitrile, styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p-methoxystyrene , a styrene derivative such as p-chlorostyrene, and the like. Among them, particularly suitable as the (a 1 ) component are phenolic resin, polyhydroxystyrene, styrene-hydroxystyrene copolymer and the like. In this embodiment, the suitable average g of the weight average molecular weight (Mw) of the (a 1 ) alkali-soluble resin before the acid dissociable dissolution inhibitor is protected is from 5,000 to 200,000, preferably from 2,000 to 50,000, to 35. 〇〇q 〜 3 0 ; 0 0 0 is more preferable; when the M w of the component (a 1 ) is less than the above range, the resolution is lowered, and when it exceeds the above range, the coatability is deteriorated. In the present embodiment, at least a portion of the total phenolic hydroxyl group of the component (a 1 ) is decomposed into an alkali-soluble base by an acid catalyst reaction, and is protected by a so-called acid dissociable dissolution inhibiting group. Such an acid-dissociable dissolution inhibiting group is preferably an acid produced by (£) to - 29-(26) 1254191 parts described later, such as 1-ethoxymethyl, 1-ethoxyethyl. Alkoxyalkyl group such as 1-propoxymethyl, decyloxyethyl, 1-n-butoxymethyl,]-isobutoxymethyl ' 1 -tert-butoxymethyl; tert-butoxycarbon hydrazine Alkoxycarbenyl such as tert-butylcarbenylmethyl, tert-butoxycarboethyl; tetrahydrofuranyl; tetrahydropyranyl; linear or branched acetal; cyclic acetal Base; trimethylmethanyl, triethylformamidine, triphenylmethyl sylvestre base, etc. In particular, the monoethoxycarbon group represented by the following chemical formula (IV-1) and the tert-butoxycarbocarbyl group represented by the following chemical formula (IV-2) can provide a photoresist composition excellent in resolution. Suitable, especially 1-ethoxyethyl is most desirable. • · * (IV-1) -CH-0-C2H5

I ch3 .&quot;(IV - 2)

——C——0——C(CH3)3

(E) The component (E) component is not particularly limited, and a photoacid generator such as a sulfonyldiazepine methane generator, a gun salt system, which can be used as a material of the chemically enhanced positive photoresist composition in the early stage, can be used. An acid generator, an oxime sulfonate acid generator, and the like. Especially in the manufacture of LCDs, the g-line, h-line, and ray line coexistence of the ultraviolet side is used, and among them, a compound having high acid generation efficiency by ultraviolet irradiation is preferred; and, in order to improve the resolution, a shorter wavelength is used. The i-line is better than 30-(27) 1254191, especially for compounds with high acid production efficiency for i-line exposure.

The component (E) is preferably a compound having the following formula, and is preferably used for i-line exposure, and is preferably a compound represented by the following general formulas (II) and (III). (USP 6004724).

Ri one

ο MM S π ο R3, (II)

RiV R5 0

II ••(III) C = C C = N—0—S — R3

/ \ / II R2 A 〇 (where m / is 〇 or 1; x is 1 or 2; R) is 1 or more C! ~ C ! 2 alkyl substitution may also be phenyl, heteroaryl Or the like; or a C 2 to C 6 alkoxycarbenyl group, a phenoxycarbon group, a CN, etc. when m / is G; R 1 'is a C 2 -C 12 alkenyl group; R 2 is the same as Rdg; R 3 is ( ^~0:] 8 alkyl; R3 / is the same as R3, X 2, C2~C] 2 alkenyl, phenenyl; R4, R5 are independent hydrogen atoms 'halogen atom, G ～0:6 alkyl; A is S, 〇, and NR6; and R 6 is a hydrogen atom or a phenyl group.) Specifically, for example, a sulfenyl group-containing sulfonate represented by the following formula (π/) Etc. -31 - (28)1254191 C3H7 / calving Ο

CN

•••(II,) or a bis(trichloromethyl)triazine compound represented by the following formula (IV), or the compound (IV) and the bis(trichloromethyl group) represented by the following formula (V) A combination of a triazine compound (Japanese Unexamined Patent Publication No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei 6-2 8 9 6 4 , No. 3 4 4 1 2). m

R70 N 乂 Ν Ν==^ CC13 CC13 (wherein R6 and R7 are each an alkyl group having 1 to 3 carbon atoms).

CC13 • · · (V) CC13 (wherein Z is 4-alkoxyphenyl.) Triazine compound (1V), specifically, for example, 2 - [ 2 - ( 3, 4 - dimethoxyphenyl) Vinyl]-4,6-bis(trichloromethyl)-],3,3,5-triazine, 2-[2-(3-methoxy-4-ethoxyphenyl)vinyl] a 4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[-32-(29) 1254191 2-(3-methoxy-1,4-propoxyphenyl)vinyl group 〕 a 4,6-bis(trichloromethyl)-1,3,5-triazine '2-[2-(3-ethoxy-4-methoxyphenyl)vinyl]-4,6- Bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3,4-diethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1 , 3,5-triazine, 2 —[2-(3-ethoxy-4-cyclopropoxyphenyl)vinyl]- 4,6-bis(trichloromethyl)-1,3,5-three Oxazine, 2-(2-(3-propoxy-4-methoxyphenyl)ethyl]- 4,6-bis(dichloromethyl)-1,3,5-di-D-Qin, 2- 〔2—(3—C 4-yl-ethoxyphenyl)vinyl]- 4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3,4-dipropoxyphenyl) Vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine or the like; these triazine compounds may be used singly or in combination of two or more. On the other hand, the above triazine compound (V) which is used in combination with the above triazine compound (IV) according to the demand, for example, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl) a 1,3,5-triazine, 2-(4-ethoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-propoxybenzene) A) 4,6-bis(dichloromethyl)-1,3,5-triazine,2-(4-butoxyphenyl)-4,6-bis(trichloromethyl)-1,3 ,5-triazine, 2-(4-methoxynaphthalenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-ethoxynaphthyl)-4 ,6-bis(trichloromethyl)-],3,5-triazine, 2-(4-propoxynaphthalenyl)-4,6-bis(trichloromethyl)-1,3,5-three Oxazine, 2-(4-butoxynaphthyl)- 4,6-bis(trichloromethyl)-],3,5-triazine, 2 —( 4 -33 _ (30) 1254191-methoxy- 6-carboxyphenyl)- 4,6-bis(trichloromethyl)-1,3,5-diazine, 2-(4-methoxy-6-yl)- 4,6-double (trichloromethyl)—], 3 5-Triazine, 2-[2-(2-furyl)ethylidene]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2 — (5 — Methyl 2- 2 -D-fusyl) Ethyl] 4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(5-ethyl-2-furan) Vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine,2-[2-(5-propyl-2-furanyl)vinyl]-4,6 A pair of (trichloromethyl)-1,3,5-triazine, 2-[2-(3,5-dimethoxyphenyl)vinyl]- 4,6-bis(trichloromethyl)- 1,3,5-triazine, 2-(2-(3-methoxy-5-ethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5 — Triazine, 2-[2-(3-methoxy-5-propoxyphenyl)vinyl]- 4,6-bis(trichloromethyl)-1,3,5-triazine, 2-— 2-(3-ethoxy-5-methoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3,5 —diethoxyphenyl Vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3-ethoxy-5-propoxyphenyl)vinyl]-4, 6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3-propoxy-5-methoxyphenyl)vinyl]-4,6-bis(trichloro) Methyl)-1,3,5-triazine, 2-[2-(3-propoxy-5-ethoxyphenyl)ethyl]-4,6-bis(dichloromethyl)-1 , 3,5-triazine, 2-[2-(3,5-dipropoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2 — (3,4-monomethylenedioxyphenyl)- 4,6-bis(trichloromethyl)--3 core (31)1254191],3,5-triazine, 2-[2-(3, 4-methylenedioxyphenyl)ethenyl]- 4,6-bis(trichloromethyl)-], 3,5-triazine, etc.; these triazine compounds can be used alone or Use two or more combinations to make use

Factory A \\

There are two or four things in the CNIC. The use of the group VI is in the form of ο described / 〇 S = ο

R , π // single materialization , etc .

For ΓA-based Cai C is a substance or a P-form V is a suitable η 式 极 极 极 例 , , , , , , , , , , , , , , , , , , , , , , , , , , ,

9 Η 4 C

The amount of the ο ο (Ε) component is preferably from 1 to 30 parts by weight, particularly preferably from 1 to 20 parts by weight on the (a / ) component ι 〇 〇 by weight. In the chemically amplified positive resist composition of this example, in order to improve the stability of the immersion time, it is preferred to mix a basic compound (suitable as an amine) (hereinafter referred to as a (F) component). Such a basic compound as long as it is compatible with the photoresist composition

-35- (32) 1254191 is not particularly limited. For example, a compound described in JP-A-9-6-1A can be used. In particular, the addition of a specific specific basic compound (f 1 ) represented by the following general formula (V III ) not only has an effect of improving the stability of the above-mentioned placement, but also has a suppressing effect on the photoresist composition. The formation of acid over time and the effect of improving the storage stability of the photoresist solution; very suitable.

X

N——Y

I

Z In the general formula (VIII), one or more of X, Y, and Z (more preferably two or more, and most preferably three) are selected from the group consisting of the following (1) to (4). (1) an alkyl group having 4 or more carbon atoms; (2) a cycloalkyl group having 3 or more carbon atoms; (3) a phenyl group; and (4) an aralkyl group. Among the X, Y and Z, those other than the above (1) to (4) are selected from the group consisting of (1/) an alkyl group having 3 or less carbon atoms and a (2/) hydrogen atom group or an atom. X, Υ, Ζ may be the same or different, but when there are two or more of X, Υ, Ζ selected from the above (1) to (4), the base is the same, and the effect is the same. The stability is better. (1) Alkyl group having 4 or more carbon atoms In the case of the above (1), when the number of carbon atoms is less than 4, it is difficult to improve the stability over time; the number of carbon atoms is 5 or more, particularly preferably 8 or more; There is no particular limitation, and it is preferably 20 or less, particularly preferably 15 or less, from the confirmation of the stability effect over time or the commercial difficulty of -36 - (33) 1254191; The strength is weakened, and the effect of preserving stability is lowered. The alkyl group may be linear or branched. Specifically, for example, n-decyl, n-octyl, n-pentyl, and the like are more suitable. (2) A cycloalkyl group having 3 or more carbon atoms, which is commercially available in the ring base group, especially a ring having 4 to 8 carbon atoms, and is excellent in improving the stability over time, and is particularly suitable for carbon; The cycloalkyl group having an atomic number of 6 is most desirable. (4) an aralkyl aralkyl group which is represented by the general formula (a R/- Ρ); (R / is an alkenyl group, and an anthracene is an aromatic hydrocarbon group). ρ has, phenyl, naphthyl and the like; phenyl is more suitable. The number of carbon atoms of R / is preferably 1 or more, more preferably 1 to 3. An aralkyl group, for example, a benzyl group or a phenethyl group is preferred; and, among the ruthenium, osmium and iridium, those other than the above (1) to (4) are selected from the above (factory) and (2/). Base or atom. The alkyl group (]/) may be a straight chain or a branched chain; in particular, a methyl group or an ethyl group is preferred. (Π) The composition 'is preferably composed of a tertiary amine, and X, Υ, Ζ are not the above (]) to (4), and are preferably selected by (1 / ); for example, specifically, Tri-n-decylamine, methyl-di-n-octylamine, tri-n-pentyl-37-(34) 1254191-amine, N,N-dicyclohexylmethylamine 'tribenzylamine, and the like. Among them, one or more selected from the group consisting of tri-n-decylamine, methyl-di-n-octylamine and triamylamine are preferred, and tri-n-decylamine is particularly preferred. The basic compounds in the present embodiment may be used alone or in combination of two or more. The compounding weight of the test compound is ○ resin solid part 1 ο 〇 by weight, and is 0 · 0 1 to 5.0 parts by weight, and the range of 0.1 part by weight is particularly suitable. The positive resist composition of this example can be obtained by dissolving the above-mentioned materials and the like in an organic solvent. Organic solvent The organic solvent in the resist composition of the present embodiment is not particularly limited as long as it is used as a chemically amplified positive resist composition. For example, propylene glycol monoalkyl ether acetate (such as propylene glycol monomethyl ether acetate (PGMEA), etc.), lactate (such as ethyl lactate, etc.) ester solvent; acetone, methyl ethyl ketone, cyclohexanone, A a ketone of isoamyl ketone or 2-heptanone; a multivalent valence of ethylene glycol, propylene glycol, diethylene glycol, or its monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or monophenyl ether Alcohols and derivatives thereof; such as cyclic ethers of dioxane; non-ester solvents such as the like. Further, in the case of an ester-based solvent, the reaction product of an organic carboxylic acid and an alcohol is an organic residual acid containing a free acid; therefore, the photoresist composition of the above-mentioned (F) component or a storage stabilizer which will be described later is not provided. It is preferred to select a non-ester solvent which does not contain such a free acid, particularly a ketone (ketone-38-(35) 1254191 solvent); especially a 2-heptanone, a coating film It is most desirable for the solubility of the (E) component. Further, in the case where the ester solvent or the non-ester solvent is decomposed over time to form a by-produced acid, the decomposition reaction can be suppressed in the presence of the above-mentioned component (F) or a storage stabilizer described later; In the ester solvent, the effect is more remarkable. In the presence of the component (F) and the storage stabilizer, an ester solvent is preferred, and PGMEA is particularly preferred. Further, it is confirmed that formic acid, acetic acid, propionic acid or the like is produced by the above-mentioned decomposition of the by-produced acid component, for example, 2-heptanone. The organic solvent may be used alone or in combination of two or more. The chemically amplified positive-type photoresist composition of the present invention is suitable for use in combination with a storage stabilizer as follows. The storage stabilizer is not particularly limited as long as it has an action of inhibiting the decomposition reaction of the solvent. For example, the antioxidants described in JP-A-59-119 4 3 3 can be used; and the antioxidants include benzene. The acid-based compound and the amine-based compound are preferably a phenol-based compound, and particularly, a 2,6-di(tert-butyl)-p-cresol and a derivative thereof are highly deteriorated in an ester solvent or a ketone solvent. It is effective, commercially available, and inexpensive, and excellent in storage stability, and is extremely suitable; in particular, it is extremely excellent in preventing deterioration of propylene glycol monoalkyl ether acetate and 2-heptanone. The blending amount is preferably 0.01 to 3 parts by weight, particularly preferably 0.1 to 1 part by weight, based on 0 parts by weight of the resin solid portion. Further, in the photoresist composition of the present embodiment, the same as the non-chemically-enhanced positive-type photoresist composition, the range of -39 - (36) 1254191 should be required, without impairing the object of the present invention. With various additives; may contain compatible additives, such as additional resins, sensitizers, stabilizers, surfactants for improving the performance of the photoresist film, etc., in order to make the image of the image more clear, It is a conventional additive such as a sensitizer, an anti-corona dye, and an adhesion enhancer which enhances the sensitizing effect. Manufacture method of the composition The positive-type photoresist composition of the present embodiment dissolves the (A /) component, (E) component and other components required for the reaction in an organic solvent; and the photoresist composition is prepared according to the demand. The solid content contained in the solid content is measured by a gel permeation chromatography method, and the weight average molecular weight (Mw) of the converted polystyrene is 35,000 to 100,000, and is preferably produced in a range of 5,000 to 50,000. The amount of the organic solvent to be used is suitably adjusted to obtain a uniform positive resist composition when the (A / ) and (E) components and other components used in response to the demand are dissolved; suitable solid concentration It is preferably 10 to 50% by weight, more preferably 2 to 35% by weight; and the solid portion of the positive photoresist composition is equivalent to (A / ) and (E) components and used in response to demand. The sum of other ingredients. The step of adjusting the Mw of the positive resist composition to a suitable range is, for example, (1) separately performing the (A /) component before the mixing, performing the refining operation with the ion exchange resin, etc., /) The method of pre-adjusting the M w of the component to the appropriate range, (2) preparing a plurality of components (A) different in Mw, and appropriately fitting the Mw of the solid component to 1254191 (37) to the above range . Among these adjustment methods, in particular, the modulation method of the above (2), the adjustment of the molecular weight of the photoresist, and the sensitivity adjustment are relatively easy, and are extremely suitable. When M w is in the above range, heat resistance, resolution, linearity, and depth of focus (D Ο Ρ ) characteristics are further improved, and the coating properties of the photoresist composition are also excellent.

&lt;Second Embodiment&gt; (A) Component The second embodiment of the chemically amplified positive resist composition of the present invention contains the component (A) (in this example, (a2) alkali-soluble resin And (D) (a3) a reaction product ((A') component) and (E) a photoacid generator represented by the following general formula (1). H2C=CH—-0——R1——0—CH=CH2 (1)

[In the formula, R 1 is an alkenyl group having a carbon atom number of 1 to 〇, which may have a substituent, or a group represented by the following general formula (2). 〕 - (2) (wherein, R is an alkyl group having a substituent or a carbon atom number), and is an an alkenyl group; m is ruthenium or 1. The component (a2) in the present embodiment is a photoresist composition. The test can be used without any particular limitation and can be used; it is suitable to have a suitable hydroxyl group from the reactivity with the component (D). - 41, 1254191 (38) • ( a2 ) The component (a 2 ) is suitable for use as an enumerator of the alkali-soluble resin component constituting the (a;[) component in the second embodiment. (a2) When the phenolic resin is used as a component, the Mw is 1,000 to 50,000. From the point of sensitivity characteristics, it is preferably 1 500 to 2 0 5 0 0, and 2,0 0 0 to 1 5,000. The Mw range is more suitable; when it is less than the above range, there is a fear that the resolution is lowered, and when it exceeds the above range, the coating property is not good. Further, when a phenol resin is used as the component (a2), it is preferable to use the above-mentioned component (F) and a storage stabilizer from the viewpoint of long-term storage stability of the photoresist composition. When the hydroxystyrene resin is used as the component (a2), the hydroxystyrene unit is at least 50 to 9 mol%, and from the viewpoint of reactivity with the (〇) component, it contains 70 to 90. Molar% is more suitable. In particular, the hydroxystyrene resin is a resin having almost no acidity compared with the phenol resin; the acidity of the component (A) affects the storage stability of the photoresist composition, and the storage stability is excellent. For the purpose of the photoresist composition, a hydroxystyrene resin is preferably selected; in particular, it is derived from a styrene constituent unit containing the above styrene and a styrene derivative, and an alkyl-substituted styrene constituent unit (hereinafter, two The hydroxystyrene resin which is nicknamed r styrene-based constituent unit is very suitable from the viewpoint of improving the sensitivity, heat resistance, and shape of the photoresist pattern of the photoresist composition. The content of the styrene-based constituent unit in the styrene-based resin is from 1 to 3 from the point of ensuring the reactivity with the component (D), improving the heat resistance, and improving the sensitivity of -42 to 1254191 (39). 〇Mer% is more suitable for '5 to 15% Mo.%. When the phenyl acetophenone resin is used as the (a 2 ) component, its M w is , 000 to 40,000, and it is preferable that it is heat-resistant, sensitized, and reacted with a crosslinking agent. In terms of point, 'especially 2,000~6,0 0 is the most ideal. The (a2) component may be used in one or two or more materials. • (D) Component: (D) The component is a compound represented by the above general formula (1) as a crosslinking agent. In the above general formula (1), R1 is a substituent or a carbon atom. a branched or linear alkenyl group of 1 to 10 or as shown in the following general formula (2); and the oxy group may have an oxygen bond (acid bond) on the primary bond, and the general formula ( In 2), R4 is also a branched or linear alkenyl group having 1 to 10 carbon atoms which may have a substituent, and the alkenyl group may have an oxygen bond (ether bond) in the main chain. It is suitable for -C4HU - , C2H4OC2H4 -, C2H4OC2H4OC2H4 -, or general formula (2), etc.; especially in the general formula (2); the number of carbon atoms of R4 is 1, m 1, special SU ideal. (D) The components may be used alone or in combination of two or more. • (a3) component (a3) component, (a2) component reacted with component (D) to form a reaction product, which is poorly soluble or insoluble in aqueous alkali solution, and has an acid-43- 1254191 (40) component. It acts as a soluble property; that is, the (A / ) component. When the component (a2) is reacted with the component (D), a reaction product of a vinyl group having a unilateral terminal of the component (D), for example, a constituent unit of a branched chain group bonded to the component (a2) is usually obtained. . Specific examples of such a constituent unit include a constituent unit represented by the following general formula (1A) or a constituent unit represented by the following general formula (2A). Further, when the component (a2) is reacted with the component (D), a vinyl group at both ends of the component (D) may be obtained, for example, a portion of two phenolic hydroxyl groups respectively bonded to the branch of the component (a2). The reaction product; a specific example of such a constituent unit is an intermolecular crosslinking moiety represented by the following general formula (1B) or an intermolecular crosslinking moiety represented by the following general formula (2B). _ stomach 5 can obtain only the constituent units of the unilateral end of the (D) component (for example, (]A), (2 a)], and the part combined with both (for example, &lt; 1 B ) ' ( 2B ) The reaction product (a3) is present in both. H3c—zl \ 0 ---(ΙΑ)

-44 - 1254191

- 45- 1254191 (42)

R] is the same as above; R2 and r3 are the groups derived from phenols, aldehydes, ketones and the like which have been described in the above-mentioned phenol resin. In this case, the component (a3) may be obtained by reacting the above component (a2) with the above component (D) in the absence of a suitable acid catalyst. The component (D) is linked to the hydroxyl group branched by the (a2) alkali-soluble resin in advance, and the temporal change of the photoresist coating liquid (composition) can be suppressed, and the photoresist material having little change in sensitivity with time can be obtained. Then, the photoresist material is coated on the substrate, and when heated, the branched phenolic hydroxyl group of (a 2 ) reacts with the vinyl group at the terminal of the above constituent unit (1 A ) or (2 A ) to form a crosslink. In the structure, then, in the case of the alkali aqueous solution such as an alkali liquid used for forming the photoresist pattern, the barrier film becomes poorly soluble. -46- 1254191 (43) Therefore, when the acid produced by the component (E) in the component (a3) having the crosslinked structure acts, the solubility of the crosslinked structure is increased to the alkaline aqueous solution. Further, when the phenolic resin is selected as the component (a2) and the component (D) is reacted, the acid catalyst is not used, and it is not necessary to use an acid catalyst, and the acid component is stored, and the stability after storage is adjusted. In the case of (a2) component, it is necessary to strictly control the concentration of the acid component as the impurity is contained in the component (a2). Previously, it is preferred to carry out the operation of removing the component (a2) strictly; and, for example, the acid component used, for example, the acid catalyst used in the reaction solvent, can be analyzed by gas chromatography. The method for removing the acid component is a well-known method of washing with an ion exchange resin, washing with pure water, neutralizing with a base, etc., and then the concentration of (a2) before the reaction with the component (D) is 〇. 1 ppm or less, especially (a 3 ) average molecular weight obtained by reacting the most (a 2 ) and (D) components below ppm ppm, selecting phenolic resin as the (a2) component, 7〇, 〇〇〇, from heat resistance, etc. In the case of 20, 〇〇()~; when the hydroxystyrene resin is selected as the component (a2), 1 500, 00 0 'from the point of heat resistance, etc., After exposure by cracking, (a3) is formed, in (a2), the reaction can also enter into the reaction system; in addition, the choice: part and (D) are formed, the acid component is in this, and in (D) The acid contained in the phenolic resin is synthesized from an acid or the like, and the like, for example, the acid component of the method can be used. The weight of the component is equal to 1,0,0 0 〇~ 5 0, 00 0 is ideal. 3 0,0 〇〇~ , 1 0 0,0 0 0 Special 1254191 (44) Ideal. (D) Ingredients, when phenolic resin is selected as (a2) component, (a2) The content is 1 to 15% by weight, and is preferably used in a ratio of 4 to 8% by weight; when less than 1% by weight, the film reduction of the unexposed portion of the resist pattern is increased, and the contrast of the photoresist pattern is decreased. When the amount is more than 15% by weight, the solubility in the developing solution (aqueous alkali solution) tends to be remarkably deteriorated, and problems such as poor sensitivity and pattern resolution may occur. Further, the hydroxystyrene resin is selected. In the case of the component (a2), the component (D) has a component (a2) of 1 to 15% by weight, preferably 5 to 10% by weight. • (E) component (E) component has (, A2) cross-linking of the component and the component (D), and forming an alkali-insoluble photoresist layer on the substrate by heat during preheating, and decomposing the cross-linking by the acid generated by exposure at the exposure portion, thereby insolubilizing It is preferable that the photoresist layer is changed to an alkali-soluble function. Such a function is to irradiate a compound which generates an acid by radiation, that is, a so-called acid generator used in a chemically-enhanced photoresist, and there are many Proposal, which can be used arbitrarily. In this embodiment Specific examples of the suitability of the component (E) are the same as those in the first embodiment described above, etc. • (F) component In the present embodiment, the component (F) can be compared with the above-mentioned embodiment (F) The composition of the same composition; in particular, the use of the above (Π) -48 - 1254191 (45) as the component (F) in the present embodiment is most suitable. • The organic solvent is organic in this embodiment. The solvent ' can be the same as the organic solvent in the above first embodiment; from the point of storage stability, it is preferable that the photoresist component is absent from the acid component, so the above-mentioned non-vinegar system is selected. It is suitable to select an ester solvent on the premise of a solvent or a component containing the above (Η) or a storage stabilizer. In particular, when phenolic resin is used as the component (a2), the effect of acid on the change with time is remarkable. After the preparation, the viscosity of the photoresist composition (coating solution) increases, the film thickness changes, and the sensitivity changes. In case of problems, it is very suitable to mix the above (Π) ingredients and preservative stabilizers. The organic solvents may be used alone or in combination of two or more. The compounding amount of the organic solvent is not particularly limited, and the solid content concentration is from 20 to 50% by weight, and the compounding amount of up to 25 to 45% by weight is used, which is suitable from the viewpoint of coatability. • Other components The photoresist composition of the present embodiment may contain other components in the same manner as in the above-described third embodiment without departing from the object of the present invention. • Method for producing a composition The photoresist composition of the present embodiment can be produced by the same method as the first embodiment described in the above-mentioned -49-1254191 (46) using the component (a3). According to the photoresist composition of the present embodiment, in addition to the same effect as the above-described i-th application type, it is possible to obtain a light-resistance pattern excellent in heat resistance, especially when a cross-linked structure is formed during preheating. To prevent membrane loss. &lt;Third embodiment> • (A) and (D) components of the third embodiment, containing (A) component (referred to as (a2)_compatible resin in this example), and additionally The component (D) represented by the above general formula (.1). In the present embodiment, the (a2) component and the (D) component may be the same as the second embodiment of the above-described second embodiment; the present embodiment is in contrast to the second embodiment, in the (a2) component and (D) The component is in an unreactive state and is contained in (A) component. In the present embodiment, when the ratio of the component (D) is selected, when the phenol waking resin is selected as the component (a2), the ratio of (&amp; 2) component is 1 to 50% by weight, and the ratio is 5 to 35 weight%. Suitable; when less than 1% by weight, the film loss of the unexposed portion of the resist pattern increases, the contrast of the resist pattern decreases, and the solubility of the developing solution (aqueous alkali solution) when it exceeds 50% by weight 'There is a tendency to deteriorate significantly, and there may be problems such as poor sensitivity and pattern inconsistency. Also, when the hydroxystyrene resin is selected as the component (a2), the component (a2) is 1 to 50% by weight. The ratio of 5 to 40% by weight is preferably used. -50- 1254191 (47) • (E) component (E) component in this embodiment is the same as the above-mentioned second embodiment. 0 • (F) component (F) component in the present embodiment, and the above The second embodiment is the same. • Organic solvent The organic solvent in this embodiment is the same as the second embodiment described above. • Other components Further, the photoresist composition of the present embodiment may contain other components in the same manner as in the first embodiment described above without departing from the object of the present invention. I. Method of Producing Composition The photoresist composition of this embodiment can be produced in the same manner as in the first embodiment using the component (a2). In the photoresist composition of the present embodiment, in addition to the same effects as those in the above-described first embodiment, the photoresist is applied onto a substrate, and when heated, the crosslinking reaction as described above occurs. The heat resistance of the photoresist pattern formed by the photoresist composition can be improved, and the film can be prevented from being reduced. -51 - 1254191 (48) [Method of Forming Photoresist Pattern] An example of the method for forming a photoresist pattern of the present invention will be described below. First, a positive-type photoresist composition is applied onto a substrate by a spinner or the like to form a coating film. The substrate 'is composed of various substrates and various films formed on the substrate; the substrate is preferably a glass substrate; the glass substrate is usually made of amorphous cerium oxide, and the low temperature is used in the field of the system LCD. It is preferable that the glass substrate is 500 mm×600 mm or more, and in particular, a large substrate of 550 nimx 650 mm or more can be used. Then, the glass substrate on which the coating film is formed is subjected to a preliminary heat treatment to remove the residual solvent to form a photoresist film. In the preheating method, it is preferred to perform a very close heating in the gap between the heating plate and the substrate. The heating temperature in this step varies depending on the material, and is usually 80 to 1 20 ° C, preferably 90 to 1 l ° ° C; the heating time is usually 40 to 140 seconds, and 60 to 1 220 seconds. good. The thickness of the photoresist film is 〇 · 3~6.0 // ηι, to 〇. 5~5 // m is more suitable. Then, the antireflection film forming composition is applied onto the formed photoresist film by a spinner or the like, and heat treatment is performed to form an antireflection film, and an optical effect of the antireflection film is provided to obtain an antireflection film. In order to change the refractive index and the film thickness, it is preferable to set the film thickness of the antireflection film which can obtain an appropriate effect. For example, by providing an anti-reflection film on the photoresist film, it is possible to reduce the light incident on the substrate during the selective exposure, the reflection at the interface between the air and the anti-reflection film, and the anti-reflection. The reflection of the interface between the film and the photoresist film; thereby, the loss of the amount of incident light to the photoresist film can be reduced, and the utilization efficiency of the light can be improved; and a part of the light emitted from the substrate surface is respectively in the air The interface with the antireflection film and the surface of the antireflection film and the photoresist film reflect 'the thickness of the antireflection film, and the phase of the reflected light of the two can be reversed and controlled, thereby suppressing Multiple interference of light within the photoresist layer. Further, from the principle of preventing reflection, the wave light of the light for selective exposure is λ, and when the refractive index of the light and the photoresist film is η, the refractive index η / of the anti-reflection film is n, and the film thickness is λ. The approximation / of / 4η / odd multiples reduces the reflectivity and reduces the effects of standing waves. Next, the photoresist film is selectively exposed using a mask cover that depicts a mask pattern; the mask is formed using a photoresist pattern of a resist pattern of 2.0 // m or less, and more than 2.0//m It is suitable for the photomask cover which is drawn by both the photomask pattern of the photoresist pattern. Further, the light source is preferably an i-line (3 65 nm) for forming a fine pattern; further, the exposure process for the exposure is such that NA is 0.3 or less, more preferably 0.2 or less, and low NA of 0.15 or less. The conditional exposure process is ideal. Next, the photoresist film after selective exposure is subjected to heat treatment (p E B 'exposure heat treatment). When a chemically enhanced type is used as the positive resist composition, the acid formed by the (E) acid generating component in the selective exposure step and the (E) component are generated in the post-exposure heating (PEB) step. The acid acts as a catalyst 1504191 (50) to make the (A / ) resin component alkali-soluble; therefore, this case requires a post-exposure heating (PEB) step; the PEB method is used between the heating plate and the substrate. The gap is preferably very close to heating. The heating temperature and heating time in this step are from 90 to 160 ° C, preferably from 1 1 0 to 1 50 t: from the point of controlling the diffusion of the acid component; 4 0 to 1 4 0 seconds, preferably 6 0 to 1 2 0 seconds. On the other hand, when a non-chemically enhanced type is used as the positive resist composition, the PEB step is not necessary, and in order to obtain a shape improving effect, it is preferred to carry out the PEB step. That is, after the exposure step, the (B) component contained in the positive-type photoresist composition in the photoresist portion of the exposed portion, for example, the solubilized hydrazine carboxylic acid derived from the quinonediazide-based compound; By the step of P EB, the ruthenium carboxylic acid is uniformly diffused uniformly into the photoresist film or the fine portion; as a result, the shape of the photoresist pattern is improved and the effect of high resolution is obtained. Further, 'particularly, the specific example of the non-chemically-enhanced positive-type photoresist composition' is formed in an angular shape by heating at the top of the photoresist pattern (the upper portion of the unexposed portion of the photoresist film). When the photoresist pattern having a good rectangular shape is formed, the step of performing the PEB can effectively improve the shape of the photoresist pattern. In this case, the PEB temperature is preferably 90 to 15 (rc is preferred; [〇〇~M (rc is more suitable; when the PEB temperature is in the above range, the surface insolubilized layer is easily formed, and the PEB method is used in the heating plate). The direct heating between the gap between the substrate and the substrate, or the direct heating between the heating plate and the substrate, is -54 - 1254191 (51), especially in the case of using both. Direct heating is more suitable; specifically, at 90~150 °C, more suitable for heating 〇〇~140 °C for 5~]0 0 seconds' to 1 0~] 5 0 seconds better , the gap is 〇. 〇5~mm, to 〇. 1 ~ 1 mm is very close to the heating, then apply 9 0~1 5 0 °C, to more suitable 1 0 0~〗 4 0 °C heating 5 to 200 seconds, preferably 30 to 80 seconds, and direct heating with a gap of 0 mm is suitable. The initial application of the near-heating can suppress the back-up phenomenon of the substrate due to heat; By performing direct heating followed by the above effect of diffusing the acid component by heat, the exposed portion of the photoresist film can be sufficiently imparted. The PEB step for the purpose of improving the shape can be applied to the chemically-enhanced positive-type photoresist composition, and the same effect can be obtained. Next, the anti-reflection film is removed; when the anti-reflection film is water-soluble, it is easily removed by washing with water. When the antireflection film is soluble in an aqueous alkali solution, the antireflection film can be simultaneously removed and developed in the development step described later, and the antireflection film removing step and the development processing step are performed in the same step. Then, after performing the development treatment on the photoresist film after the PEB using an aqueous alkali solution, the exposed portion is dissolved and removed, and a photoresist pattern for the integrated circuit is simultaneously formed on the substrate, and the liquid crystal display portion is used. This developing treatment is performed, for example, using a 2.38% by weight aqueous solution of tetramethylammonium hydroxide for 60 seconds. Moreover, the developing liquid remaining on the surface of the resist pattern is pure water or the like.淸- 55- 1254191 (52) The washing liquid is washed away to form a photoresist pattern. Thereafter, the photoresist pattern formed thereon is preferably subjected to heat treatment (post-heating). Thereafter, heating is performed to In the step of reducing the amount of outgas by the photoresist pattern, the heat treatment is performed at a temperature close to the heating temperature at the time of injection; specifically, it is performed at a heating temperature of 100 to 200 ° C, The heating time is preferably 60 to 240 seconds. Further, in the above example, after the PEB step, the anti-reflection film is removed, and the anti-reflection film is present in the photoresist film when performing selective exposure. Above, and in the developing process step, it is preferable that the anti-reflection film does not hinder the contact of the photoresist film with the developing liquid; for example, when the anti-reflection film is water-soluble, after performing selective exposure, washing with water The anti-reflection film is removed, and then the PEB step described above may be performed. Further, when a non-chemically-enhanced photoresist composition is used and a PEB step is not performed, after performing selective exposure, the anti-reflection film is removed by washing with water, and then development processing may be performed; the anti-reflection film is soluble in an aqueous alkali solution. The development processing step and the anti-reflection film removal step can be performed in the same step. According to the present invention, it is possible to prevent variations in size by providing an anti-reflection film on the photoresist film formed of the photoresist composition. In particular, the specific examples of the non-chemically-enhanced positive-type photoresist composition and the first to third embodiments of the chemically-enhanced positive-type photoresist composition are linear, sensitive, and deep in focus. Point, resolution, etc., the characteristics required in the manufacture of system LCDs are extremely excellent, and a photoresist pattern that faithfully reproduces the fine pattern of the mask pattern can be obtained; therefore, at the same time -56-1254191 (53) In the step of forming the photoresist pattern, a photoresist pattern for an integrated circuit having a pattern size of 2.0 or less and a photoresist pattern for a liquid crystal display portion exceeding 2.0 m can be simultaneously formed on the substrate. [Embodiment] [Examples] The present invention will be described in detail by way of examples. (1) Linear evaluation Using a photoresist coating apparatus for a large substrate (device name: TR 3 6000, manufactured by Tokyo Ohka Kogyo Co., Ltd.), a positive photoresist composition was applied to a glass substrate on which a Ti film was formed ( After 5 5 0 mm X 6 5 0 mm ), the temperature of the hot plate is adjusted to 100 ° C, and the first drying of 9 〇 seconds is performed by the interval of about 1 mm, and then the temperature of the heating plate is adjusted. A photoresist film of 1 · 4 8 // m is formed at intervals of 90 ° C and 0.5 mm. Next, the composition for forming an antireflection film was applied onto a resist film, and then subjected to heat treatment at 90 ° C for 90 seconds to form an antireflection film. Next, a reticle pattern that reproduces the photoresist pattern of the line & space (L &amp; S) of 3 · 0 // m and L &amp; S of 1.5 m and a test chart mask simultaneously depicted (Scale line) intervened, using i-line exposure device (device name: FX-702 J, manufactured by Nikon Corporation, NA=0.14), so that 1·5 // m L &amp; S faithfully reproduces the exposure The amount (Εορ exposure) is subjected to selective exposure. Then, the temperature of the heating plate is adjusted to 12 (TC, 0.5 mm interval, by -57- 1254191 (54) by the close heating, performing heat treatment for 30 seconds; then, without interval at the same temperature, performing 60 seconds Direct heat treatment. Next, a developing device having a slit coating nozzle (device name: TD - 3 9 000, manufactured by Tokyo Ohka Kogyo Co., Ltd.), at 23 ° C, 2.38% by weight Aqueous ammonium hydroxide aqueous solution, as shown in the figure, is sprayed from γ to Z from the end portion X of the substrate, sprayed for 1 〇 second, the substrate is filled with the solution, and after 5 5 seconds, it is washed for 30 seconds. Rotary drying; thereby removing the anti-reflection film; the symbol 1 in the figure is a substrate (carrier). Thereafter, the cross-sectional shape of the obtained photoresist pattern is observed by a scanning electron microscope (s E Μ ), and evaluation is performed 3.0. // Reproducibility of the photoresist pattern of m L &amp; s. 3.0// m L· &amp; S The dimensional change rate of S is within ± 1 〇%, and X is greater than ±10%. The sensitivity evaluation is expressed by the exposure amount (mJ) which can faithfully reproduce the photoresist pattern of 1 · 5 // m L &amp; S. (3) Deep focus (D 0 F ) Characteristic evaluation In the above exposure amount (Ε ο p ), the focus is appropriately moved up and down, and the resulting focus is within the range of the size change rate of 1 · 5 // ill L &amp; S ± 10 % The range of depth is the D Ο F characteristic, and the unit is &quot;m ° (4) resolution evaluation ^ 58 - 1254191 (55) In the above Ε ο p exposure, the critical resolution is obtained. (5) Photoresist The dimension deviation evaluation is shown in Fig. 1 by the symbols a to i of the carrier, respectively, indicating 9 dots, and detecting the size of the formed photoresist pattern; among the 9 dots, the size of the photoresist pattern is 5 &quot;m ± 10 0 % When the number of the following points is 8 or 9, it is represented by ;; when it is 7 or less, it is represented by X. [Example 1] Using TSP-7C (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) It is a composition (X 1 ) for forming an antireflection film, and the composition (X 1 ) for forming an antireflection film contains a polyvinylpyrrolidone/polyacrylic acid copolymer. On the other hand, it is prepared into a non-chemically enhanced type. Positive-type photoresist composition; The following components are mixed and mixed with the following, and the aperture 〇.2 # m is used. The membrane filter is filtered to prepare a photoresist composition; the weight average molecular weight (Mw) of the obtained photoresist 0 composition is 9000. (A) Alkali-soluble resin: m-cresol/3,4-xylene = 8 / 2 (Morbi) mixed phenol oxime, with formaldehyde 〇. 8 丨 5 mol, synthesized according to the usual method, and obtained M w = 1 9 5 0 0, M w / Μ η = 5 · The amount of the resin of I 5 is 1 part by weight. (Β) naphthoquinone diazide compound: [Β 1 / Β 2 / Β 3 = 6 : 1 : 1 (by weight) mixture] 3 8 parts by weight, Β1: bis(5-cyclohexyl- 4-hydroxyl 2- 2-methylphenyl-3,4-59- 1254191 (56) mono-dihydroxyphenylmethane (ie B 1 / ) 1 molar, with 2-naphthoquinonediazide-5-sulfonyl chloride a compound (hereinafter abbreviated as (5 - NQD)) 2 molar synthesis product. B2: bis(2,4-dihydroxyphenyl)methane (ie, B2 -); [mole, and 5-NQD 2 Mol's esterification reaction product B3: bis(4-hydroxy-2,3,5-trimethylphenyl)-2 phenyl group (ie B3) 1 旲' and 5 - NQD 2 (C) a compound containing a phenolic hydroxyl group: bis(2-methyl-4-isophenyl)-phenylmethane 25 parts by weight, organic solvent: PGMEA-464 parts by weight The antireflection film-shaped composition (X)) and the obtained positive-type photoresist composition were evaluated for each of the above items (1) to (5); the results are shown in Table 1. Further, the anti-reflection film was used. The film thickness is 〇.65 # ηΊ. [Example 2] TS Ρ 9 9 Α (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) is used as an antireflection film forming composition (Χ2), and the antireflection film forming composition (Χ2) is 'containing polyvinylpyrrolidone On the other hand, 'modulating into a chemically-enhanced positive-type photoresist composition; that is, the following components' are mixed and mixed as described below, and then filtered using a membrane filter having a pore diameter of 〇 2 μ m to prepare a photoresist. The composition; the weight average molecular weight (Mw) of the obtained photoresist composition is 4 Å - 60 - 1254191 (57) (eight / ) : Mw = 4500 polyhydroxystyrene 100 parts by weight (D ): ring Hexane dimethanol divinyl ether 1 part by weight (E ): compound of the above formula (VII) 2 parts by weight (F): tri-n-decylamine hydrazine · 3 parts by weight of organic solvent: 2 - heptanone 2 6 2 weight The anti-reflection film-forming composition (X 2 ) and the obtained positive-type photoresist composition' were evaluated for each of the above items (1) to (5), and the results are shown in Table 1. The film thickness of the film was 〇·6 5 // m. [Comparative Example 1] A substrate on which an antireflection film was not formed was used, and the other Each of the above items (1) to (5) was evaluated in the same manner as in Example 1. The results are shown in Table 1. [Comparative Example 2] A substrate on which an antireflection film was not formed was used, and the other was carried out. In the same manner as in Example 2, each of the above ()) to (5) was evaluated, and the results are shown in Table 1. In the embodiment of the present invention, the deviation of the size can be suppressed _; y^ @, solution Image, linearity, and depth of focus are excellent. -61 - 1254191 (58) Table 1

Line Sensitivity (mJ) Depth of Focus (U m ) Resolution (β m ) Deviation of Photoresist Size Example 1 〇 50 20 1.3 〇 Example 2 〇 50 30 1 .3 〇 Comparative Example 1 〇 60 20 1 . 3 X Comparative Example 2 〇 60 30 1.3 X [Effect of the Invention] As described above, the method for forming a photoresist pattern according to the present invention can be suitably used for the manufacture of a system LCD, and the variation in the size of the resist pattern can be suppressed. [Simple description of the drawing] Figure 1: In order to evaluate the linearity, the positive photoresist composition is applied to the glass substrate. After heating and drying, the pattern is exposed, and the device with the slit coating nozzle is used to display the developing liquid from the substrate end. Description of the X to z spray-coated substrate filled solution. Main g component comparison table 1 substrate -62 -

Claims (1)

1254191 (1) Pickup, Patent Application No. 1 A method for forming a photoresist pattern, comprising: (1) a step of applying a positive photoresist composition onto a substrate to form a coating film, and (2) a substrate on which a coating film is formed, a heating (preheating, PB) treatment, a step of forming a photoresist film on the substrate, (3) a step of forming an antireflection film on the photoresist film, and (4) using the light a resist pattern of 2.0 // m or less of the resist film is formed, and a resist pattern of 2.0 // m or more is formed, and the mask for the mask pattern is subjected to selective exposure, and (5) After the selective exposure is performed, the step of removing the anti-reflection film, and (6) performing the development process on the resist film after the selective exposure is performed with an aqueous alkali solution, and simultaneously forming a pattern size of 2.0 // m or less on the substrate. The step of forming a photoresist pattern for an integrated circuit and a photoresist pattern for a liquid crystal display portion exceeding 2.0 // m. 2. The method for forming a photoresist pattern according to claim 1, wherein between the above (4) and (6), the photoresist film after the selective exposure is subjected to heat treatment (heating after exposure) , PEB) steps. 3. The method for forming a photoresist pattern according to claim 1 or 2, wherein after the step (6), the photoresist pattern is subjected to heat treatment (post-heating, p 〇S t - bake ) step. 4. The method for forming a photoresist pattern according to claim 1, wherein the positive photoresist composition is phenolic ruthenium-63- 1254191 (2) lacquer-naphthoquinone used for i-line (3 6 5 nm) The photoresist material. 5. The method of forming a photoresist pattern according to claim 1, wherein the step (4) of performing the selective exposure is performed by using an i-line as a light source and by an exposure process under a low NA condition where the NA is 0.3 or less. Implementation. -64-