TW200416484A - Positive photoresist composition for producing LCD and process for forming resist pattern - Google Patents

Abstract

A positive photo resist material for producing an LCD, which makes it possible to form a resist pattern at a high resolution even under conditions of a low NA (numerical aperture of a lens), is provided. The resist material comprises (A) an alkaline soluble resin comprising a novolac resin having an alkaline solubility of 100 to 400 nm/sec., for aqueous 2.38 wt% tetramethyl ammonium hydroxide at 23 DEG C, (B) a compound which releases an acid by irradiation, and c a crosslinkable polyvinyl ether compound.

Description

200416484 (1) 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a method for forming a photoresist image using a positive photoresist for LCD manufacturing. [Prior technology] So far, in the manufacture of forming liquid crystal display elements (LCDs) on glass substrates, because they are inexpensive and can form a photoresist image with high resolution, most of them are made of lacquer tree for semiconductor manufacturing. An azide-based compound is a positive photoresist composition. However, in comparison with, for example, the manufacture of semiconductor devices using a disc type LCD with a maximum of 8 inches (about 200 mm) to 12 inches (about 300 mm) uses a substrate as small as 360 mm x 460 mm. In this way, in the manufacture of LCD, the material and shape of the photoresist material are different, and the size is much different from that used in semiconductor manufacturers. Therefore, in the manufacture of photoresist materials for LCDs, it is necessary to be able to form a photoresist with good characteristics such as shape and dimensional stability across the entire surface. In addition, the manufacture of LCDs consumes a lot of photoresist materials, and the photoresist materials used should be inexpensive except for the above characteristics. So far, 'the photoresist material for manufacturing LCD has been mentioned, for example,' the following patent documents 1 to 6). Patent documents 1 to 6 are excellent in the shape and shape of the liquid crystal display I-benzoquinone containing silicon wafers with large diameters up to silicon wafers, square glass substrates, and body components. The price of resist materials is low (2) (2) 200416484. For small substrates, such as 3 60 mm x 460 mm, it can form photoresist images with excellent coatability, sensitivity, resolution, shape and size stability. Therefore, it is suitable for the manufacture of a relatively small LCD. Patent Document 1 Japanese Patent Laid-Open No. 9-1 6023 Patent Document 2 Japanese Patent Laid-Open No. 9-2 1 1 85 Japanese Patent Publication No. 3 Japanese Patent Laid-Open No. 2000- 1 1 2 1 Patent Document No. 20 Patent Document 4 JP 2000- 1 3 1 835 Patent Document 5 Patent Publication JP 2000_ 1 8 1 05 No. 5 Patent φ Patent Document 6 Patent Publication JP 200 1 -7 5 272 The large-scale LCD display and the popularity of LCD TVs have a high demand for larger LCDs. In addition, due to the requirements of lower prices, there is a need to improve the efficiency of LCD manufacturing. Therefore, in the manufacturing of LCDs, the productivity (units) is increased. The amount of time to process), hope to increase as much as possible The exposure area is at least about 100 square millimeters. Moreover, because the unevenness of the glass substrate is larger than that of a silicon wafer, it is very difficult to maintain the planar uniformity of the photoresist film in a wide exposure range. It can expand the focus β depth, which is generally used in LCDs. In manufacturing, NA (the number of openings of the lens) is preferably an exposure process using a low NA condition such as 0.3 or less, especially 0.2 or less. However, when using an exposure process with a low NA condition, it is known to use a photoresist material for LCD manufacturing. Under low NA conditions such as 0.3 or less, it is difficult to form a photoresist image with excellent shape at high resolution. That is, the general resolution (analytic limit) is as the following Rayleigh equation: (3) (3) 200416484 R = k 1 χ λ / ΝΑ [where R is the analytical limit of the table, the k! Table depends on the proportional constants of the photoresist, process, and imaging method, the λ table is used for the light wavelength of the exposure process, and the number of openings in the NA table is used] 'use short wavelength The light source of Λ, the exposure process of high NA 'can improve the resolution even more. For example, instead of exposing the g-line (436 nm) used in LCD manufacturing, use the shorter I-line (3 65 nm). Light lithography The resolution can be further improved. However, as mentioned above, the high NA with a narrowed exposure area and a small depth of focus is not good, and it is possible to use a low NA exposure process. Therefore, high resolution is required. It is still difficult to obtain a high-resolution photoresist image, that is, a fine photoresist image. As the image size becomes finer, the focus depth wide characteristic tends to deteriorate significantly, making it difficult to focus well. It forms a fine photoresist image under the characteristics. Furthermore, it is currently popular as a next-generation LCD on a glass substrate to form an integrated circuit part such as an image processor, an image controller, a ram and the like at the same time as the display part. "System LCD" technology development of high-performance LCD (Semiconductor FPD World 2001.9, ρ · 50-67) ° At this time, because the integrated circuit part is formed in addition to the display part on the substrate, the substrate tends to be larger . Therefore, it is expected to be exposed at lower NA conditions than the conventional LC manufacturing. Again, in the “system B LCD”, for example, the image size of the display part is about 2 to 10 microns, and the integrated circuit part is formed with a fine size of about 0.5 to 20 microns (4) (4) 200416484. . Therefore, it is better to form display parts and integrated circuit parts of such different sizes at the same time under the same exposure conditions, and expect linearity [with the same exposure conditions (different mask sizes on the protective film and the same exposure amount) (Condition) When exposed, corresponding to different mask sizes on the protective film, the characteristics of high-precision reproduction are excellent, and photoresist materials with higher resolution than conventional photoresist materials for LCD manufacturing are highly anticipated. However, as mentioned above, the conventional photoresist materials used in the manufacture of LCDs are difficult to form images with high resolution under low NA conditions, and are therefore difficult to use in the manufacture of system LCDs. For example, under low NA conditions of 0.3 or less, it is difficult to form a photoresist image of, for example, 2.0 microns or less. The obtained photoresist image tends to be not rectangular but sloped, and the characteristics of wide depth of focus are also poor. Therefore, in the LCD process of the system, a photoresist material having good linearity and forming a fine photoresist image with excellent shape under low NA conditions such as 0.3 or less is expected. [Summary of the Invention] Φ That is, the problem of the present invention is to provide a photoresist that can display at least a part of the photoresist pattern at a high resolution under the conditions of lower NA than conventional photoresist materials for LCD manufacturing. Materials and methods for forming photoresist images. The better one is to provide excellent linearity under low NA conditions. It can be used for high-resolution system LCD display parts and finer integrated circuit parts. It is suitable for manufacturing integrated circuits and liquid crystal displays on a substrate. Some LCD photoresist materials and methods for forming photoresist images are their subjects. In order to solve the above problems, the present inventors have found that compounds containing an alkali-soluble resin made of a lacquer resin having a specific alkali solubility of -8- (5) (5) 200416484, and a compound that generates an acid upon irradiation with radiation, The positive photoresist composition and cross-linkable polyvinyl ether are photoresist materials suitable for the exposure process in low NA conditions, and finally the present invention is completed. That is, the first aspect of the present invention relates to a positive type photoresist composition for manufacturing an LCD, which is characterized by containing the following components (A) to (C): (A) 2.38 mass to 23 ° C % Soluble tetramethylammonium hydroxide aqueous solution having alkali solubility ranging from 100 to 400 nanometers per second, alkali-soluble resin made of lacquer resin, (B) compounds that generate acid upon irradiation with radiation, and ( C) Crosslinkable polyvinyl ether compound. The second aspect of the present invention relates to a method for forming a photoresist image, which is characterized by: (1) coating a substrate with a positive photoresist composition in the first state as described above to form a coating film (2) The process of heating (pre-baking) the substrate on which the coating film is formed to form a photoresist film on the substrate. (3) For the photoresist film, a photoresist pattern below 2.0 microns is drawn. The process of selective exposure of both the mask image used for imaging and the mask image used to form a photoresist image over 2.0 microns, (4) the photoresist film after the selective exposure, The process of applying heat treatment (post-exposure baking), (5) subjecting the photoresist film after the heat treatment to an image development treatment with an alkaline aqueous solution, and simultaneously forming an image size of less than 2.0 microns on the substrate-9- (6) (6) 200416484 photoresist images for integrated circuits, and photoresist images for liquid crystal display parts larger than 2.0 microns, and (6) washing away the photoresist images remaining on the photoresist image surface Rinse process of imaging solution. [Embodiment] < (A) component > In the positive-type photoresist composition of the present invention, the (A) component is used for a 2.38 mass% tetramethylammonium hydroxide (hereinafter referred to as TMAH) aqueous solution at 23 ° C. Alkali soluble resin made from lacquer resin having alkali solubility in the range of 100 to 400 nm / s, preferably more than 100 to 400 nm, and more preferably 150 to 400 nm / s . Alkali solubility in the range of 100 to 400 nanometers / second, the sensitivity is high, the residue in the exposed part is small, the contrast is excellent, the resolution is high under low NA conditions, and the photoresist side has good verticality, so it is better. In this specification, the alkali solubility refers to a layer formed of an alkali-soluble resin having a specific film thickness (about 0.5 to 2.0 microns) on a substrate, and it is immersed in a 2.38% by mass aqueous solution of TMAA (about 23 t), and the value is determined. The time required for the film thickness to become 0 is calculated from the following formula: alkali solubility = film thickness / time required for the film thickness to become zero. The layer formed by the alkali-soluble resin can be, for example, a resin dissolved in PGMEA to a 20% by mass concentration solution, spin-coated on a 3 inch silicon wafer, and heat-treated on a hot plate set at 110 ° C. Formed in 90 seconds. (A) The component is not particularly limited if it has alkali solubility as defined above. -10- (7) (7) 200416484 For example, those conventionally used as a material for forming a film in a conventional positive type photoresist composition can be used. In particular, at least one aromatic hydroxy compound such as phenol, cresol, xylenol, tricresol, catechol, rasoxine, hydroquinone, etc., and at least one of formaldehyde, paraformaldehyde, propionaldehyde, salicylaldehyde, etc. A condensate of an aldehyde in the presence of an acidic catalyst is preferred because it is suitable for the modulation of photoresistive materials with high sensitivity and excellent linearity under low NA conditions. Specifically, there are: • Lacquer resins with a weight-average molecular weight of 2,000 to 3,000, m-cresol 100% condensed with formaldehyde under an acid catalyst, • m-cresol 30 to 80 mole%, better 40 to 70 mole% and o-cresol 70 to 20 mole%, preferably 60 to 30 mole% of mixed cresol, obtained by condensation with formaldehyde under an acid catalyst, weight average molecular weight 2 3,000 to 3,000 of lacquer resin. Acid catalysts include oxalic acid, p-toluenesulfonic acid, acetic acid, etc., and oxalic acid is preferred because it is cheap and easily available. Formaldehydes include formaldehyde, formaldehyde or trioxane dissolved in water, and formaldehyde is usually used. The alkali solubility of alkali-soluble resins varies with the types of raw materials (aromatic hydroxy compounds, aldehydes, etc.) used, blending ratio, weight average molecular weight (Mw), etc., and must be properly confirmed one by one. Specifically, for example, 'the alkali-soluble resin obtained from a specific raw material composition is plotted on the relationship between its Mw and the alkali solubility (ie, dissolution rate) obtained as described above, and the range of Mw is adjusted in advance from this map to the alkali solubility of 1 Within the range of 0 to 400 nanometers per second, an alkali-soluble resin having an alkali solubility in the range of 1000 to 400 nanometers per second can be prepared. (8) (8) 200416484 < (B) component > (A) and (C) components are thermally crosslinked during pre-baking 'to form an alkali-insoluble photoresist layer on the substrate. The component (B) may have an acid that is generated by the exposure of the exposed portion, and the acid decomposes the cross-linking to change the insoluble photoresist layer into an alkali-soluble function. A compound having such a function to generate an acid upon irradiation of radiation 'is a so-called acid generator for a chemically amplified photoresist, and various proposals have been made so far, which can be arbitrarily selected. The manufacturing of φ LCD uses ultraviolet rays coexisting with g-line, h-line, and i-line. Among them, compounds with high acid generation efficiency after irradiation with such ultraviolet rays are preferred. In addition, in order to improve the resolution, it is better to use a short-wavelength i-line, and in the manufacture of the system LCD, the i-line is mainly used, and especially the compound having a high efficiency in generating an acid exposed to the i-line is preferred. As mentioned above, the term “system LCD” in this specification refers to an LCD with integrated circuits and a liquid crystal display portion formed on a substrate. (B) As the component, the following compounds are used, for example, and the acid generation efficiency is high when exposed to i rays, so it is preferable. Φ

-12- (9) 200416484

Ri ,,

απ) (where m is 0 or 1; X is 1 or 2; Ri is 1 or more of (^ to (: 12 alkyl substituted phenyl, heteroaryl, etc., or m is 0 to 0 at 0) C6 alkoxycarbonyl, aryloxycarbonyl, CN, etc .: ^^^^ to C12 aliphatic alkenyl, etc .; 112 is synonymous with 1; R; is 0: 1 to 0: 18 alkyl, etc .; R'3 is at X When = 1, it is synonymous with R3, and when X = 2, it is C2 to C12 aliphatic alkenyl, arylalkenyl, etc .; R4 and R5 are independently hydrogen atoms, halogens, alkyls, etc .; A is S, 0, NR6, etc .; R6 is a hydrogen atom, a phenyl group, and the like.) Compounds shown in the table (refer to USP 6004724). Specifically, there are, for example, sulfene-containing oxime sulfonates represented by the following formula.

13- (10) 200416484 R6〇

NN = ^ CC13 (IV) R7〇CCI3 (wherein R6 and R7 each represent an alkyl group having 1 to 3 carbon atoms.) A bis (trichloromethyl) triazine compound as shown in the table, or the compound (IV) and The following formula (V)

Z-f N CC13 (V)

CC13 (wherein z represents 4-alkoxyphenyl, etc.) Composition of the bis (trichloromethyl) triazine compound shown (Japanese Patent Application Laid-Open No. 6-2 896 1 4 and Japanese Patent Application Laid-Open No. 7-1 3 44 1 Bulletin 2). Specific examples of the triazine compound (IV) include 2- [2- (3,4-dimethoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine , 2- [2- (3-methoxy-4-ethoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2 -(3-methoxy-4-propoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2 · (3-ethyl Oxy-4-methoxyphenyl) vinyl] -4,6-bis (trichloromethyl) · 1,3,5 · triazine, 2- [2- (3,4-diethoxy Phenyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3-ethoxy-4-propoxyphenyl) vinyl ] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3-propoxy-4-methoxyphenyl) vinyl] -4,6 -Bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3-propoxy-4-ethoxyphenyl) • 14 · (11) (11) 200416484 vinyl ] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,4-dipropoxyphenyl) vinyl] -4,6-bis ( Trichloromethyl) -1,3,5-triazine and the like. These triazine compounds may be used alone or in combination of two or more kinds. On the other hand, the triazine compound (V) used in combination with the triazine compound (IV) as necessary includes, for example, 2- (4-methoxyphenyl) -4,6-bis (trifluoromethyl)- 1,3,5-diazine, ethoxyphenyl) -4,6-bis (trichloromethyl) -1,3 '5-triazine, 2- (4-propoxyphenyl) -4 , 6 · bis (trichloromethyl) -1,3,5-di-D-dioxine, 2- (4-butoxyphenyl) -4 '6-bis (trichloromethyl) -j, 3,5 -Triazine, 2- (4-methoxynaphthyl) -4,6 · bis (trichloromethyl) -1, 3,5 • triazine, 2- (4-ethoxynaphthyl) -4 '6-Bis (trichloromethyl) -1,3,5-triazine, 2- (4-propoxynaphthyl 6 · bis (trichloromethylbuthene 1,3') 5-tri-D Qin, 2 -(4-butoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-tri-D-phenylene, 2- (4-methoxy-6-carboxynaphthyl) -4 , 6-Bis (trichloromethyl) · 1,3,5 · Tri-D-Qin, 2- (4-methoxy-6-CycylCeichyl) · 4,6 · Bis (dichloromethyl)- 1, 3, 5-triazine, 2- [2- (2-furanyl) vinyl] -4 '6-bis (trichloromethyl) -1, 3,5-triazine, 2- [2 · (5 -Methyl-2-furyl) vinyl] -4,6 · bis (trichloromethyl) ) '-1' difluorene, 2- [2- (5-ethyl-2 -pyranyl) ethynyl] -4,6-bis (trichloromethyl) -1,3,5-triazine , 2- [2- (5-propyl-2-furanyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3 , 5-dimethoxyphenyl) vinyl] -4,6 · bis (trichloromethyl) -1,3,5-triazine, 3-methoxyethoxyphenyl) vinyl]- 4,6-bis (trichloromethyl, 3,5-triazine, 2- [2- (3-methoxy-5-propoxyphenyl) vinyl] -4,6-bis (trichloro (Methyl) -1'3,5-triazine, 2- [2- (3-ethoxy-5-methoxyphenyl) vinyl] -4 '6 · bis (trichloromethyl) -1, 3,5_triazine, 2_ [2_ (12) 200416484 (3 '5_-ethoxyphenyl) ethanyl] -4,6-bis (5j triazine, 2_ [2- (3-ethoxy _5_propoxyphenyl) vinyl] _4, 6-bis (dichloromethyl) -1,3, triazine, 2- [2- (3-propoxy_ethynyl) -4 '6 -Bis (trichloromethyl) -1,3,5-chloromethyl) methoxyphenyl) D_, 2-[2-(3-propoxy-5-ethoxyphenyl) vinyl] _4,6-bis (trichloropyridyl 1,3,5 · trifluorene, 2- [2- (3,5-dipropoxyphenyl) Anthroyl] _4 'bis (trichloromethylfluorene'3,5-triazine, 2_ (3,4-methylenedioxyphenyl η, 6bis (trichloromethyl) -1,3,5 -Triazine, 2- [2 · (3 '4-methylenedioxyphenyl) ethanoyl' 6 · bis (trichloromethyl η'3, Bu Sanqin, etc.). These three amidine compounds may be used singly or in combination of two or more kinds. Again ’

(In the formula, Ar is substituted or unsubstituted phenyl, naphthyl; "I". The alkyl group η is not an integer of 2 or 3. The compounds shown in the table. The compounds represented by this formula π) can be used alone 'It can also be used in combination of two or more types. The compounds shown in the following (VII) are especially preferred because of the high efficiency of the acid production of the thread. -16- (13) 200416484 〇C4H9, H / 〇II 〇

CN

CN 0

XT &gt; / 0 \ H / C4H9 (VI) II 〇 (B) The compounding amount of the component (B) is 100 parts by mass, (1) to 30 parts by mass, and particularly preferably 1 to 20 parts by mass. <(C) component> (C) Component The parent-linked polyethylene glycol compound and (a) component are crosslinked by heating during pre-baking to form an alkali-insoluble photoresist layer on the substrate. Then, due to the effect of the acid generated by the component (B), the cross-linking is decomposed, and the exposed portion becomes alkali-soluble, and the unexposed portion remains alkali-insoluble. Therefore, if the component (C) has the function of forming an alkali-insoluble photoresist layer on the substrate by heating and cross-linking together with the component (A) during pre-baking, the type is not particularly limited. Such polyvinyl ether compounds are listed in Japanese Patent Application Laid-open No. 6 1 48 8 8 9 and Japanese Patent Application Laid-Open No. 6-2 3 05 74, and can be selected arbitrarily. Especially considering the shape of the photoresist side, which depends on the thermal crosslinkability and acid decomposability, and the contrast characteristics of the exposed and unexposed areas during exposure under low NA conditions are good, and the resolution is excellent, the following is preferred General formula (1): R— (〇Η) η ⑴ [wherein R is an alkane having a linear group, branched group or cyclic group which can contain oxygen atoms, and a group of η hydrogen atoms is removed, η shows 2, 3 Or an integer of 4] -17- (14) (14) 200416484 As shown in the table, some or all of the hydroxyl groups of alcohols are vinyl etherified compounds. Examples of such compounds include ethylene glycol divinyl ether, triethylene glycol divinyl acid, 1,3-butanediol divinyl ether, tetramethylene glycol divinyl ether, neopentyl glycol divinyl ether, and triethylene glycol divinyl ether. Methylolpropane triethylene ether, trimethylolpropane triethylene ether, hexanediol divinyl ether, 1,4-cyclohexanediol divinyl ether, tetraethylene glycol divinyl ether, pentaerythritol divinyl ether, Pentaerythritol trivinyl ether, cyclohexanedimethanol divinyl ether, etc. Among them, a crosslinkable divinyl ether compound is more preferable, and cyclohexanedimethanol divinyl ether is particularly preferable. The compounding amount of the component (C) is 100 parts by mass, (0) to 50 parts by mass, and particularly preferably 5 to 25 parts by mass, with respect to the component (A). The positive-type photoresist composition of the present invention is more preferably a polymer amine ((D) component) from the viewpoints of preventing excessive diffusion of acid from the exposed portion and the stability of the photoresist image over time. (D) Ingredients include, for example, secondary or tertiary alcohol amines, diethylamine, such as diethanolamine, triethanolamine, tributanolamine, and triisopropanolamine, which are not easily volatile from the photoresist film due to heating during prebaking , Triethylamine, dibutylamine, tributylamine and other secondary or tertiary alkylamines. The compounding amount of the component (D) is 100 parts by mass of the component (A), preferably from 0.01 to 5 parts by mass, and more preferably from 0.1 to 1 part by mass. The positive type photoresist composition of the present invention may contain compatible additives such as additional resins, plasticizers, Common additives such as stabilizers, surfactants, colorants that make the developed image more visible, sensitizers that enhance the sensitization effect, anti-glow dyes, and adhesion improvers. (15) (15) 200416484 The positive photoresist composition of the present invention is preferably prepared by dissolving the (A) component, (B) component, (C) component and other components when necessary using an organic solvent. The organic solvents used in the present invention include, for example, acetone, methyl ethyl ketone, cyclohexanone, isobutyl methyl ketone, isoamyl methyl ketone, 1,1,1-trimethylacetone and other ketones; ethylene glycol, propylene glycol , Monoethylene glycol, diethylene glycol, ethylene glycol monoacetate or diethylene glycol monoacetate, monomethanol, monoethyl ether, monopropyl ether, monoisopropyl ether, monobutanol or monophenyl ether and other polyols and Derivatives; cyclic ethers such as dioxane; and methyl acetate, ethyl acetate, butyl acetate, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, 3 · ethoxypropyl Esters such as ethyl acetate. These can be used alone or in combination of two or more. The method for forming a photoresist image of the present invention is a method using the positive-type photoresist composition, and an example of a suitable method for forming a photoresist image when manufacturing an LCD is given below. First, the components (A), (B), and (C) and various components added as necessary are dissolved in a solvent, and they are applied to a substrate by a spin coater or the like to form a coating film. The substrate is preferably a glass substrate. The glass substrate can be a large substrate of more than 500 mm x 600 mm, especially a size of more than 500 mm x 65 mm. Next, the glass substrate on which the coating film is formed is subjected to a heat treatment (pre-baking) at, for example, 100 to 140 ° C to remove residual solvents to form a photoresist film. The pre-baking method is preferably an adjacent baking in which a gap is maintained between the hot plate and the substrate. Next, for the above photoresist film, a mask on which both a mask pattern for integrated circuits and a mask image for a liquid crystal display portion are drawn is used for selective exposure. -19- (16) (16) 200416484 light. The light source used here is preferably an i-line (3,65 nanometers) to form a fine image. In addition, the NA used in the exposure is preferably 0.3 or less, more preferably 0.2 or less, and even more preferably 0.1 5 or less, and is preferably a low NA exposure process. Next, the photoresist film after selective exposure is heat-treated (baking after exposure: PEB). PEB is preferably baked in close proximity with a gap between the hot plate and the substrate. For the photoresist film after the above PEB, a developing solution, for example, 1 to 10 mass ° /. An alkali aqueous solution such as a tetramethylammonium hydroxide aqueous solution is subjected to a development treatment to dissolve and remove the exposed portions, and simultaneously form a photoresist image for the integrated circuit and a photoresist image for the liquid crystal display portion on the substrate. Next, the photoresist image can be formed by removing the developing solution remaining on the surface of the photoresist image with eluent such as pure water. During the above-mentioned selective exposure, the above-mentioned photomask is a photomask that depicts both a photomask image forming a photoresist image below 2.0 microns and a photomask image forming a photoresist image exceeding 2.0 microns, That is, in the above-mentioned process of simultaneously forming a photoresist image, a photoresist image for an integrated circuit having an image size of less than 2.0 microns and a photoresist for a liquid crystal display portion exceeding 2.0 microns are simultaneously formed on the above substrate. image. As described above, the positive photoresist composition of the present invention is suitable for the exposure process under low NA conditions. It is also suitable for i-line exposure. Therefore, in the manufacture of LCD, at least part of the photoresist image can be displayed at a high resolution. • 20- (17) (17) 200416484 In addition, the positive photoresist composition of the present invention is also excellent in linearity under low NA conditions, and can form coarser images and finer images on the same exposure conditions on a substrate. Therefore, the display portion of the system LCD can be obtained at high resolution under low NA conditions, so that the photoresistance pattern of the finer integrated circuit portion is suitable for manufacturing the system LCD. Furthermore, the method of forming a photoresist image of the present invention using the above-mentioned positive-type photoresist composition with excellent resolution under low NA conditions can improve the yield of LCD manufacturing. Furthermore, with the method for forming a photoresist image of the present invention, a high-resolution photoresist image can be formed in a low NA condition exposure process suitable for manufacturing an LCD. Ewing can simultaneously form, for example, photoresist images for integrated circuits with an image size of 2.0 micrometers or less, and photoresist images for liquid crystal display parts exceeding 2.0 micrometers, which are suitable for manufacturing system LCDs. Examples The present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples. Example 1 (A) The component was synthesized with m-cresol 1 mol using 0.8 mol formaldehyde in a general method, weight average molecular weight (Mw) = 2600, Mw / number average molecular weight (Μη) = 2.09, Alkali solubility = 3 3 0 nanometers / second of lacquer resin (resin 1). As for the alkali solubility of the component (A), as described above, an alkali-soluble resin layer having a specific film thickness is provided on the substrate, and it is immersed in 2.38% by weight TM A Η aqueous solution-21-(18) (18) 200416484 (2 3 ° C), and the time required for the film thickness to be 0 was measured and determined. (B) As the component, a compound of the above formula (VI) is used. (C) The component is a compound having the following structural formula. H2C = CH-0-CH2, di-CH2-O-CH = CH2 (D) Triethanolamine is used as the component. 100 parts by mass of the component (A), 5 parts by mass of the component (B), 15 parts by mass of the (C) component, 0.25 part by mass of the (D) component, and equivalent to 45 0 PPm of the total mass of the components (A) to (D) Surfactant (product name, R-〇8〃; manufactured by Dainippon Ink Chemical Industry Co., Ltd.), dissolved in propylene glycol monomethyl ether acetate ^ solid content [total of (A) to (C) components] concentration is 25% by mass ° Filtered by a 0.2 micron filter to prepare a positive photoresist composition. Examples 2 to 5 and Comparative Examples 1 and 2 (A) Instead of Resin 1, components other than Resins 2 to 7 of Table 1 were used as in Example 1 to modulate a positive-type photoresist composition. -22- (19) 200416484 Table 1 (A) Ingredients Example 1 Resin 1 Example 2 Resin 2 Example 3 Resin 3 Example 4 Resin 4 Example 5 Resin 5 Comparative Example 1 Resin 6 Comparative Example 2 Resin 7

In Table 1, resins 1 to 7 are as follows. The purpose of the tree month 1: as the above resin 2: m-cresol / o-cresol = 6: 4 (molar ratio) 1 mol, compared with 0.8 mol formaldehyde synthesis in a general method, Mw = 25 00, Mw / Mn = 4.32, solubility test = 310 nanometers per second of lacquer resin resin 3: phenol 1 mol, which is synthesized by a general method relative to 0.8 mol formaldehyde, Mw = 2090, Mw / Mn = 4.32, alkali solubility = 3 3 0 nanometer / second lacquer resin resin 4: razoxin / m-cresol / 3,4-xylenol = 15: 77: 8 (molar ratio) 1 mole, relative to formaldehyde 0 · 8 mol is synthesized by the general method, Mn = 2500, Mw / Mn = 4.2, alkali solubility = 300 nanometers per second of lacquer resin resin 5: m-cresol / 3, 4-xylenol = 90: 10 (Mole ratio) mixture of 1 mole, relative to salicylaldehyde 0.2 mole, formaldehyde 0.6 mole in general formula -23- (20) 200416484 lacquer synthesis lacquer synthesis Comparative preparation of quinone 20%, Mw = 2 500, Mw / Mn = 4.2, alkali solubility = 3 00 m / s resin resin 6: m-cresol / o-cresol / 2,3,5-tricresol = 40 : 3 5: 2 ratio) of the mixture 1 mole, relative to the use of formaldehyde 0.8 mole in a general method , Mw = 2450, Mw / Mn = 4.40, Resin resin with solubility = 80 nm / sec. Resin 7: m-cresol 1 mol, compared with 0.5 mol formaldehyde in a general formula, Mw = 1000, Mw / Mn = 1.5, solubility test = 1 000 nm / sec. Lacquer resin Example 3 In Example 1, the components of (A) to (C) were changed to the following except that the positive photoresist composition of Example 1 was used. (A) component: 100 parts by mass of the above resin 1, (X) component: an ester obtained by reacting 1 mole of a compound of the following structural formula with 1,2-naphthalene azide-2-sulfonic acid chloride 2 mole 27 parts by mass of chemical products

〇H CHa CHa 0H

(Y) Ingredient: 15 parts by mass for the compound of the following structural formula -24- (21) 200416484

OH CHs φ k φ

OH test example 1

The positive photoresist compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 3 were evaluated for the following physical properties (1) to (5). (1) Linearity evaluation: A photoresist coating device for a large-size substrate with a positive type photoresist composition (device name: TR36000; manufactured by Tokyo Chemical Industry Co., Ltd.) coated on a glass substrate with a Cr film (550 mm) X 6 5 0 mm) after the first 'drying at a hot plate temperature of 130 ° C, adjacent baking at about 1 mm intervals for 60 seconds' second, followed by a hot plate temperature of 14 0 ° C, 0. The adjacent baking at 5 mm intervals was subjected to a second drying for 60 seconds to form a photoresist film with a thickness of 1.5 micrometers. Secondly, lines and gaps (L &amp; S) were reproduced to simultaneously reproduce the 3.0 micrometers. And a test chart of a photomask image of a 1.5 micron L &amp; S photoresist image using a i-ray exposure device (device name: FX-702J, manufactured by Nikon Corporation; NA = 0.14), Selective exposure was performed with faithful reproduction of 3.0 micron L &amp; S exposure (Eορ exposure). Second, adjacent baking at a hot plate temperature of 140 ° C and 0.5 mm intervals was applied for 60 seconds. -25 · (22) (22) 200416484 Second, 23t, 2.38% by mass of Ding "human 11 aqueous solution with a gap coating nozzle development device (equipment Name: TD-3 9000 display machine, manufactured by Tokyo Chemical Industry Co., Ltd., as shown in the first figure, from the substrate end X diameter Y to Z, the liquid is poured on the substrate for 10 seconds, and kept for 55 seconds and then washed for 30 seconds Then, spin-dry. Then observe the cross-sectional shape of the obtained photoresist image with a SEM (scanning electron microscope) photograph, and evaluate the reproducibility of the photoresist image of 1.5 micron L & S. The results are shown in Table 2 (2) ) Sensitivity evaluation: Use the above exposure amount of E ο p as the sensitivity evaluation index. The results are listed in Table 2. (3) Resolution evaluation: Determine the limit resolution under the exposure amount of E ο p. The results are listed in Table 2 〇 ( 4) Evaluation of DOF characteristics: Under the above Εορ exposure, slide the focus appropriately up and down to find the width of the depth of focus (DO F) obtained by the L &amp; S of 1.5 micrometers within a range of ± 10% dimensional change rate in micrometer units. The results are shown in Table 2. (5) Residue evaluation: Observed by SEM, the substrate surface of 1.5 micrometers L &amp; S was traced under the above exposure dose, and the presence or absence of residue was examined. The results are shown in Table 2. -26 · (23 200416484 Table 2 Linear Evaluation Sensitivity Evaluation Resolution Evaluation DOF Evaluation Residue (Microns) (millijoules) Estimate (microns) (microns) Evaluation Example 1 1. 4 30 0.9 30 4πτ Πιΐ: y \ Example 2 1.6 80 1.1 30 Γ. Nrt J \ W Example 3 1.4 40 1.3 10 M Example 4 1.4 80 1. 1 30 J \ W Example 5 1.4 70 1. 1 30 M Comparative Example 1 1.6 120 1. 5 10 There are Comparative Examples 2 • 30 3 0 &gt; 1, Comparative Examples 3-150 2 0 Yes

The positive photoresist composition of Examples 1 to 5 of the present invention has good resolution under low NA conditions (NA = 0.14). In addition, all evaluation items including resolution are well balanced. On the other hand, the positive type photoresist composition of Comparative Example 1 had poor sensitivity and left a residue. In addition, the positive-type photoresist compositions of Comparative Examples 2 and 3 were unable to draw a separated image and could not be evaluated linearly. The resolution, D0F and other characteristics are also not good. Under the condition of low NA, the positive photoresist composition of the present invention can obtain at least a portion of a photoresist image at a higher resolution than that of a conventional photoresist material for manufacturing an LCD. In addition, the production of LCD can be improved. Furthermore, the positive photoresist composition of the present invention is also excellent in wire generation under low NA conditions, and can form integrated circuits and liquid crystal displays on a substrate at high resolution-27- (24) (24) 200416484 Display part of the system LCD display part, so that the photoresistance image of the finer integrated circuit part is suitable for manufacturing system LCD. With the method of forming a photoresist image of the present invention using a positive-type photoresist composition as described above, a high-resolution photoresist image can also be formed during an exposure process suitable for manufacturing low-NA conditions of an LCD, especially Suitable for manufacturing system LCD. [Brief description of the figure] Figure 1 is used to evaluate the linearity under low NA conditions. A positive photoresist composition is coated on a glass substrate. After baking and image exposure, the image will be developed by a developing device with a gap coater. An illustration of the liquid injection from the substrate end X to the zeta.

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Claims (1)

(1) 200416484 Patent application scope 1. A positive photoresist composition for manufacturing LCD, which is characterized by containing the following components (A) to (C): (A) 2 to 3 3 ° C 2 · 3 8 Alkali-soluble resins made from lacquer resins with an alkali solubility of 100% by mass of tetramethylammonium hydroxide aqueous solution in the range of 100 to 400 nanometers / second, (B) compounds that generate acids upon irradiation with radiation, (C) crosslinkable polymers Vinyl ether compounds. 2. The positive photoresist composition according to item 1 of the application, wherein the component (B) above is a compound that generates an acid upon i-ray irradiation. 3. The positive photoresist composition according to item 1 of the patent application scope, wherein the component (B) is represented by the formula: Compounds shown. 4 · The positive photoresist composition according to item 1 of the patent application range, wherein the component (C) is the following general formula (I): R- (〇H) n (I) [where R is self-contained A linear, branched, or cyclic alkyl group of an oxygen atom removes a group of η hydrogen atoms, η represents an integer of 2, 3, or 4] Compounds in which some or all of the hydroxyl groups of the alcohols shown in the table are vinyl etherified . -29- (2) (2) 200416484 5 · The positive photoresist composition of item 1 in the scope of the patent application of S 靑, where the (C) component formula is: H2C = CHUH2-(^)-C; H2- 0-CH = CH2 Compounds shown. 6 · The positive photoresist composition according to item 1 of the patent application scope, which further contains amines as the (D) component. 7. The positive photoresist composition according to item 6 of the patent application, wherein the component (D) is triethanolamine. 8 · The positive photoresist composition according to any one of claims 1 to 7, which is used in the i-line exposure process. 9 · The positive photoresist composition according to any one of claims 1 to 7 in the scope of patent application, which is used in the exposure process with NA below 0.3. 1 〇 If the positive photoresist composition of any of claims 1 to 7 of the scope of application for a patent is used, it is used for manufacturing an LCD in which a integrated circuit and a liquid crystal display portion are formed on a substrate. 11. · A method for forming a photoresist image, comprising: (1) coating a substrate with a positive photoresist composition according to any one of claims 1 to 7 to form a coating film, (2) The process of baking the above-formed substrate to form a photoresist film on the substrate, (3) For the above photoresist film, use a photoresist pattern with a size of less than 2.0 microns (3) (3) 200416484 The process of selective exposure of a mask with a mask image and a mask image with a size of more than 2.0 micron for photoresist image formation. (4) Applying the above-mentioned photoresist film after selective exposure. In the process of post-exposure baking, (5) applying a developing treatment to the photoresist film after the heat treatment with an alkaline aqueous solution, and simultaneously forming a photoresist pattern for integrated circuits with an image size of 2.0 microns or less on the above substrate. Image, and the process of using the photoresist image on the liquid crystal display portion exceeding 2.0 microns, and the rinsing process of φ (6) washing away the developing solution remaining on the surface of the photoresist image. 1 2 · The method for forming a photoresist image according to item 1 丨 in the scope of patent application, wherein (3) the selective exposure process described above uses a line as a light source. 1 3. The method for forming a photoresist image according to item 丨 丨 in the scope of the patent application, wherein the above (3) selective exposure process is an exposure process under να as low as 0.3 or less) ^ 8. -31-