TW200428151A - Chemical amplification type positive photoresist composition and resist pattern forming method using the same - Google Patents

Abstract

A photoresist composition has satisfactory heat resistance which is required for production of a system LCD which is formed by an integrated circuit and a portion of a liquid crystal display on a substrate, without decreasing sensitivity. A chemical amplification type positive photoresist composition for production of a system LCD comprising a novolak resin (A) which is hardly soluble or is insoluble in an alkali and which increases in the solubility in an alkali aqueous solution in the presence of an acid, and which is a reaction product of an alkaline soluble novolak resin (A1) with a compound represented by General Formula (I), a compound generating an acid component by irradiation with radiation (C) and solvents H2C=CH-O-R1-O-CH=CH2 …(I) wherein R1 represents an alkylene group having 1 to 10 carbons which may have a substituent, or a group represented by General Formula (II), wherein R4 represents an alkylene group having 1 to 10 carbons which may have a substituent, and m represents 0 or 1.

Description

200428151 (1) 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a chemically enhanced positive photoresist composition and a method for forming a photoresist pattern. [Prior technology] Photoresist materials in the field of manufacturing liquid crystal display elements using glass substrates so far are suitable for g-line, h-line, and i-line exposure, are relatively inexpensive, and can form photoresists with good sensitivity, resolution, and shape. Patterns, positive photoresist compositions using phenolic lacquer resins as alkali-soluble resins, and quinonediazide-containing compounds as photosensitive components are widely used, and see reports (Patent Documents 1 to 4 below) ). Regarding the chemically enhanced photoresist composition, the following Patent Document 5 describes that it contains a linear polymer having an acid component and a hydroxyl group, a photo acid generator (PAG), and a specific at least diene Alcohol-ether-based compound 'A composition in which the linear polymer and a specific compound are thermally crosslinked. The following Patent Document 6 describes a composition comprising a linear polymer having an acid group, PAG, and a specific compound having at least a dienol ether group, and a composition in which the linear polymer and the specific compound are thermally crosslinked. . Patent Document 1 Japanese Patent Laid-Open No. 2 0 0 0-1 3 1 8 3 Patent Literature 2 Japanese Patent Laid-Open No. 2001-75272 Patent Literature 3 Japanese Patent Laid-Open No. 2001-181055 Patent Literature 4 Japanese Patent Laid-Open No. 2 0 0 1- 1 1 2 1 2 0 (2) 200428151

Patent Document 5 JP 6- 1 4 8 8 8 9 Patent Document 6 JP 6-23 05 74 74 Now, a new-generation liquid crystal display (LCD) is provided on a glass substrate, and a driver and a DAC are formed at the same time. (Digital analog converters), image processors, video controllers, random access memory (RAM) and other integrated circuit parts and liquid crystal display parts, so-called "system LCD" high-performance LCD technology development is actively underway (Semiconductor FPD World 200 1 · 9, pp.5 0-67) ° In the following description, a substrate on which a integrated circuit and a liquid crystal display portion are formed on a substrate is conveniently referred to as a system LCD. In such a system LCD, the low-temperature polycrystalline silicon formed by a low-temperature process below 600 ° C, which replaces the amorphous silicon, is expected to be suitable because it has lower resistance and higher mobility than amorphous silicon. Therefore, development of a photoresist composition suitable for the manufacture of a system LCD using low-temperature polycrystalline silicon is expected, and so far, there have been no reports of photoresist materials for system LCDs. In the aforementioned Patent Documents 5 and 6 regarding chemically enhanced photoresist compositions, there is no record of a system LCD. In order to manufacture a TFT made of low-temperature polycrystalline silicon, after forming a polycrystalline silicon film on a glass substrate by a low-temperature process, the so-called "implantation step" in which the low-temperature polycrystalline silicon film is implanted with impurities (P, B, etc.) must be at a very high concentration. Impurities implanted. The implanting step is a state in which a photoresist pattern has been formed on a low-temperature polycrystalline silicon glass substrate on which a low-temperature polycrystalline silicon film is formed on a glass substrate. The photoresist pattern is performed under high vacuum conditions (3) 200428151. Due to the heating effect of the implantation of impurities, the substrate Once the above photoresist pattern is heated, there is a problem that the photoresist pattern changes in shape, and a certain component in the photoresist pattern vaporizes, which causes the vacuum in the processing chamber to decrease.

The method to solve this problem is that it is effective to perform a heat treatment step called "post-baking" before the planting step, but because the post-baking is at a temperature condition close to the temperature at which the plant is heated, such as 200 ° C The above-mentioned high temperature is performed, and it is necessary to form a highly heat-resistant photoresist pattern in which the pattern shape does not change during the heat treatment. Therefore, in order to make the system LCD practical, the photoresist composition used therein must have good heat resistance. In addition, in the field of manufacturing liquid crystal elements, the sensitivity of photoresist materials has decreased, which has led to a significant decrease in yield.

According to the present invention, a photoresist composition required for the manufacture of a system LCD with integrated circuits and liquid crystal display portions formed on a substrate, which can be achieved without a decrease in sensitivity, and the use of the photoresist composition Method of forming a photoresist pattern. [Summary of the Invention] Conventionally, a phenolic lacquer resin is used as an alkali-soluble resin, and a quinone-containing resin is used.

Achieving high heat resistance is generally a method using a high molecular weight alkali-soluble resin (phenol-formaldehyde lacquer resin), and a high sensitivity is generally used by a method using a low-molecular-weight alkali-soluble resin (phenol-formaldehyde lacquer resin). -8- (4) 200428151 In this way, it is difficult to achieve both high heat resistance and high sensitivity by conventional methods; the development of photoresist compositions for system LCDs with high heat resistance without causing a decrease in sensitivity is expected. The problem of the present invention is to provide the high heat resistance required for the manufacture of a system LCD that forms an integrated circuit and a liquid on a substrate, and can be used as a non-blocking composition. It is based on a chemical) alkali-soluble crystal display part. A photoresist composition achieved by a decrease in sensitivity and a method of forming a photoresist pattern using the light. The present inventors have carefully studied the results and found that the following problems can be solved and the present invention has been completed. That is, the substrate for forming an integrated circuit and a liquid crystal display portion on the substrate of the chemically-enhanced positive-type photoresist composition of the present invention is an enhanced positive-type photoresist composition, characterized in that it contains (A1 phenolic varnish resin) (B) A reaction product with the following compound of the general formula (I), which has the solubility property of an alkaline aqueous solution in the presence of an acid (A) Alkali-insoluble or insoluble phenolic lacquer resin, which produces acid components when irradiated Compounds, and (C)

(I

H2C = CH-0-R1 -0-CH = CH [wherein R1 represents an alkylene group having 1 to 10 carbon atoms which may have a substituent, or a general formula (II)

-9-(II) (5) (5) 200428151 (wherein R4 represents an alkylene group having 1 to 10 carbon atoms which may have a substituent, and m represents 0 or 1.). ] The method for forming a photoresist pattern of the present invention is characterized by comprising: (1) a step of forming a coating film by applying the chemically enhanced positive photoresist composition of the present invention on a substrate, and (2) forming The process of heating the substrate of the coating film (pre-baking) to form a photoresist film on the substrate. (3) For the photoresist film, use a photomask for forming a photoresist pattern of 2.0 / zm or less. And a photomask having a photoresist pattern formation pattern exceeding 2.0 // m, and performing a selective exposure step, (4) applying heat treatment to the photoresist film after the selective exposure described above. (Baking after exposure), and (5) the photoresist film after the heat treatment is subjected to a development treatment with an alkaline aqueous solution, and an integrated circuit having a pattern size of 2.0 / zm or less is formed on the substrate at the same time. Photoresistance pattern, and the step of photoresistance pattern for liquid crystal display parts exceeding 2.0 / zm. [Embodiment] The following describes suitable embodiments of the present invention, but the present invention is not limited to the following embodiments, for example, 'the constituent elements of the embodiments may be appropriately combined with each other [chemically enhanced positive photoresist composition for system LCD] • Component A-10- (6) 200428151 In the present invention, the reaction product of (A) an alkali-insoluble or insoluble phenolic system, (A 1) an alkali-soluble phenolic resin and (B) the compound of I) above, which It has the property that the solubility of a solution increases in the presence of an acid. The above (A 1) component can be used without particular limitation if it is a phenolic lacquer resin used in a photoresist composition. The alkali-soluble phenol-formaldehyde lacquer resin includes, for example, at least one hydroxy compound such as phenol, methylol, tricresol, catechol, resorcinol, hydroquinone, and aldehydes such as formaldehyde, polyformaldehyde, propionaldehyde, and salaldehyde Condensates in the presence of acidic catalysts. Examples of the acid catalyst include oxalic acid, p-toluenesulfonic acid, and acetic acid. However, it is preferable to use oxalic acid because of the availability. Among them, the aromatic hydroxy compound is preferably made of phenol and xylenol, or cresol (any of o-, m-, and p- or more). Formaldehyde is preferably used in formaldehyde, and Large-volume aldehyde synthesizers are preferred due to resistance and high sensitivity. Large-volume aldehydes include salaldehyde, propionaldehyde, etc. At this time, the ratio of formalin to large-scale aldehydes is improved by heat resistance, from 1 / 0.1 to 0.6. (Mole ratio), especially from 1 / 2.0 to 0 · ΐ). The above (Α1) component is subjected to gel permeation chromatography (GPC) to calculate a mass average molecular weight (Mw, hereinafter referred to as a mass average score of 1,000 to 50,000, more preferably about 1000 to 20,000. The characteristics are better. Less than the above range, there is analysis The degree of decline is low. The general formula of lacquer resin (in alkaline water-alkali soluble, xylenol type aromatic at least one kind is cheap, easy (any difference), any one of the thermal properties is improved, the crotonaldehyde effect is excellent (Mole ratio polymer The amount of ethylene exchanged) so that the sensitivity deteriorates beyond the above range of -11-(7) 200428151. (A1) One or two or more materials can be used as the component.

As for the component (B), in the above general formula (I), R1 may have a substituent, a branched chain or linear alkylene group having 1 to 10 carbon atoms, or the general formula (Π) By. Moreover, these alkylene groups may also contain oxygen bonds (ether bonds) in the main chain. In the general formula (Π), R4 is also a branched, linear alkylene group which may have a substituent group of 1 to 10 carbon atoms, and the subgroup may also have an oxygen bond (ether bond) in the main chain. . R1 is preferably represented by -C4H8-, -c2H4oc2H4-, -C2H4OC2H4OC2H4-, and the general formula (Π). Among them, the general formula (Π) is preferable. The carbon number of R4 is 1 and m is 1 Is especially good. (B) The component may be used singly or as a mixture of two or more kinds.

When the component (A1) reacts with the component (B), a reaction product having a vinyl group having a single end of the component (B) and a structural unit of, for example, a hydroxyl group of a side chain bonded to the component (A1) is usually obtained. A specific example of this structural unit is a structural unit (al) of the following general formula (II). The reaction of the component (A1) with the component (B) can obtain a reaction product in which the vinyl group at the terminal end of the component (B) is bound to the component (A1), for example, a diphenolic hydroxyl group in a side chain is present. Specific examples of the structural unit include the intermolecular cross-linking moiety (a2) of general formula (IV). It usually means that there is only a combination of a single end of the (B) component _ especially (for example, (a 1)) and a part with both ends (for example, (a 2 • 12- (8) 200428151

R3 I C-

R1 represents an alkylene group having 1 to 10 carbon atoms which may have a substituent, or the above general formula (Π) (where R4 represents an alkylene group having 1 to 10 carbon atoms which may have a substituent, m is 0) Or 1.), R2 and R3 are based on -13- (9) 200428151 The phenolic lacquer resin described in the above description is derived from phenols, aldehydes, ketones and other groups. For example, R2 and R3 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an aryl group, and n represents an integer of 1 to 3. The component (A) in the present invention (insoluble or insoluble enamel resin) can be obtained by reacting the component (A1) with the component (B), preferably in the absence of an acid catalyst. .

The component (B) is previously combined with the hydroxyl group of the side chain of the alkali-soluble phenolic lacquer resin (A1), and thus becomes a photoresist material that suppresses the change of the photoresist coating liquid (composition) over time and has little change in sensitivity over time. When the photoresist material is coated on the substrate and heated, the unreacted phenolic hydroxyl group of the side chain of the (A 1) component reacts with the terminal vinyl group of the structural unit (al) to form a crosslinked structure. As a result, the photoresist film, that is, an alkaline aqueous solution such as an alkali developing solution used in the formation of the photoresist pattern becomes hardly soluble or insoluble.

The component (A) having the cross-linked structure is cleaved by the action of an acid generated from the (C) component due to exposure, and the solubility of the (A) component in an alkali-water-soluble solution increases. When the component (A1) and the component (B) are reacted, if an acid component is present in the reaction system, storage stability after photoresist modulation is not good. Therefore, it is better to strictly remove the acid component contained in the component (A 1) before reacting with the component (B). The acid component is, for example, an acid catalyst used in the synthesis of phenolic lacquer resin (A 1), and organic acids such as free acids present in the reaction solvent can be analyzed by gas chromatography or the like. There are known methods for removing the acid component. For example, methods such as use of an ion exchange resin, washing with pure water, and neutralization with an alkali can be used. -14 · (10) (10) 200428151 while reacting with the component (B), the concentration of the acid component in the lacquer resin (a 1) should be less than 0.1 ppm, especially 0 (n ppnl or less) The reaction between (A 1) and (B) components can be carried out without using an acid catalyst, and the use of an acid catalyst is not necessary, but based on the storage stability of a chemically enhanced positive photoresist composition, It is better not to use. Therefore, it is better that the acid catalyst does not substantially exist in the reaction solution, and zero is more preferable. (A1) The mass average molecular weight of component (a) obtained by reacting with component (B) is 10,000. It is more preferably 70,000, especially 20,000 to 50,000 in terms of heat resistance, etc. (B) The component system is used at a ratio of 1 to 15% by mass, and more preferably 4 to 8% by mass with respect to the component (a1). Less than 1 mass %, The film loss of the unexposed portion of the photoresist pattern will increase, and the contrast of the photoresist pattern will tend to decrease. If it exceeds 15% by mass, the solubility in the developing solution (aqueous alkaline solution) will tend to decrease significantly. The sensitivity is poor. There may be problems that the pattern cannot be imaged, etc. • (C) component (C) component is not particularly limited and can be used in known chemistry The materials of the reinforced positive photo I composition are known as photo-acid generators such as diazomethane-based acid generator, gun salt-based acid generator, oxime sulfonate-based acid generator, and the like. In the manufacture of LCD, there will be the use of ultraviolet rays with g-line, h-line, and i-line. (C) The component is preferably a compound with high acid production efficiency when exposed to such ultraviolet rays. In addition, in order to improve the resolution, The -15- (11) 200428151 length of the i-line is preferred, and in the manufacture of system LCDs, because the i-line tends to be mainly used, the (C) component is the compound that has a high acid production efficiency for i-line exposure. As the component (C), for example, the following compounds are used, and it is preferable because the acid generation efficiency for i-ray exposure is limited. Those represented by the following general formulae (V) and (VI). R1

0 II C R5

0 II -πι ’C = C C = N one 0 one S / \ / II R2 A 0

R5

/ 〇 C = N—0—S—R3 / II 0 (VI) 2

(Wherein m 'represents 0 or 1; X represents 1 or 2; R represents that there may be one or more of <^-(: 12 alkyl substituted phenyl, heterocyclic aryl, etc., or m, which is 0 More preferred are C2-C6 oxo-based, phenoxycarbonyl, CN, etc .; Ri 'indicates C2-C12 sub-radical, etc .; R2 indicates phenyl, heterocyclic aryl, etc., which may be substituted with one or more alkyl groups, or C2 -C6 alkoxycarbonyl, phenoxycarbonyl, CN, etc .; R3 shows C] -Ci8, etc .; R3 'is not Ci-Ci8, etc. at X = 1, and c2-c] 2 at X = 2. R4, R5 independently show hydrogen atom, halogen, CrG alkyl, etc .; A shows S, 0, NR6, etc .; R6 shows hydrogen atom, phenyl-16- (12) 200428151

Wait. ) (USP 6004 724). Specific examples include a thiolene-containing oxime sulfonate of the following formula (VD). C3H7 ^ / 0

I N… ⑽) CH3 έΝ Coexistence, the following formula (νιπ CC13 R &amp; 0

Threat CH = CH- ^ N R7〇 CC13

(Wherein R6 and R7 each represent an alkyl group having 1 to 3 carbon atoms.) A bis (trichloromethyl) -three farming compound, or the compound (WI) and the following formula (K

CC13 CC13 (where Z shows 4-alkoxyphenyl, etc.) bis (trichloromethyl) triphine compound combination (Japanese Patent Application Laid-Open No. 6-2 896 1 4 and Japanese Patent Application Laid-Open No. 7- 1 3 44 1 2 -17- (13) (13) 200428151). Specific examples of the trimorph compound () include 2- [2- (3,4-dimethoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-trioxine, 2- [2- (3-methoxy-4-ethoxyphenyl) vinyl] -4 · 6-bis (trichloromethyl) -1,3,5-trioxane, 2- [2- (3 -Methoxy-4-propoxyphenyl) vinyl] -4 · 6 · bis (trichloromethyl) -1,3,5-trioxane, 2- [2- (3-ethoxy-4-methyl Oxypropyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-trioxane, 2- [2- (3,4-diethoxyphenyl) vinyl] -4 , 6-bis (trichloromethyl) -1,3,5-Sanken, 2 · [2- (3 · ethoxy-4-propoxyphenyl) vinyl] -4,6-bis (trichloro Methyl) -1,3,5-Sanken, 2- [2- (3-propoxy-4-methoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -1,3 , 5-Sangen, 2- [2- (3-propoxy-4-ethoxyphenyl) vinyl] · 4,6 · bis (trichloromethyl) -1,3,5-trioxane, 2 -[2- (3,4-dipropoxyphenyl) vinyl] -4,6-bis (trichloromethyl)-1.3.5- Sangen, etc. These three compounds can be used alone or in combination of two or more kinds. The above three compounds (IX) used in combination with the above three compounds (IX) are, for example, 2- (4-methoxyphenyl) -4,6 · bis (trichloromethyl) -1,3,5 -Sangen, 2- (4-ethoxyphenyl) -4; 6-bis (trichloromethyl) · 1; 3,5-trioxane, 2- (4-propoxyphenyl) -4,6 -Bis (trichloromethyl) -1,3,5-triphine, 2- (4-butoxyphenyl) -4,6-bis (trichloromethyl) -1; 3,5-trioxine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl)-1.3.5- Sangen, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) Base) -1,3,5-Sanken, 2-([propoxynaphthyl) -4,6-bis (trichloromethyl) · 1,3,5 · Sankai, 2- (4-but Oxynaphthyl) -4,6-bis (trichloromethyl)--18- (14) 200428151 1,3,5-Sanken, 2- (4-methoxy-6-carboxynaphthyl) -4, 6-Bis (trichloromethyl) -1.3,5-Sanken, 2- (4-methoxy-6-hydroxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5 · Trioxane, 2- [2- (2-furanyl) vinyl] -4,6-bis (trichloromethyl) -1, 3,5-trigeno, 2-[2-(5 -methyl-2 -Furyl) vinyl]-

4.6- Bis (trichloromethyl) -1; 3,5-tris, 2- [2- (5 · ethyl-2-furanyl) vinyl] · 4,6-bis (trichloromethyl)- 1,3,5-Sangen, 2- [2- (5-prop-2-furanyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-trimorphine, 2 -[2- (3,5-Dimethoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-trioxane, 2- [2- (3- -methoxy -5-ethoxyphenyl) vinyl]-4.6-bis (trichloromethyl) -1,3,5-Sanken, 2- [2- (3-methoxy-5-propoxyphenyl) ethylene Yl] -4,6-bis (trichloromethyl) -1,3,5-trioxo, 2- [2-

(3 -Ethoxy-5 · methoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-Sanken, 2- [2- (3,5-Diethyl Oxyphenyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5-Sanken, 2- [2- (3-ethoxy-5 · propoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -1,3,5 · Sangen, 2- [2- (3-propoxy-5-methoxyphenyl) vinyl] -4,6 · bis ( Trichloromethyl) -1,3,5-trigon, 2- [2- (3-propoxy-5-ethoxyphenyl) vinyl] -4,6-bis (trichloromethyl) trigon , 2- [2- (3,5-dipropoxyphenyl) vinyl] -4.6-bis (trichloromethyl) -1,3,5-trioxane, 2- (3,4-methylene di (Oxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-Sanken, 2- [2- (3,4-methylenedioxyphenyl) vinyl] -4,6 -Bis (trichloromethyl) -1,3,5-trioxine etc. These three compounds can be used singly or in combination of two or more kinds. In addition, there is the following formula (X) -19- &quot; • (X) (15) 200428151

\

(Where Ar is a substituted or unsubstituted phenyl group, naphthyl group; r is an alkyl group of Ci to c9; n is an integer of 2 or 3). These compounds may be used alone or in combination of two or more. Among the compounds exemplified above, a compound of the above formula (W) and a compound of the following formula (X1) are particularly preferably used because they are superior in the efficiency of acid generation to the i-line.

••• (XI) 0

C4H9. II

II 0 In this embodiment, the component (C) may be used singly or in combination of two or more. The amount of the component (c) is 1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, based on 100 parts by mass of the component (A). ° (D) Composition The chemically-enhanced positive photoresist composition of the present invention is used to improve the stability of a latent image formed on the photoresist layer after selective exposure, and is formulated with the (D) component, a basic compound (the preferred one) For amines). This compound has good compatibility with the photoresist composition, and is not particularly limited. It is produced by -20 · (16) (16) 200428151, and there is a compound described in, for example, Japanese Unexamined Patent Publication No. 9-600 1. Among them, tertiary amines are preferred, especially tri-n-pentylamine, methyl-di-n-octylamine, tri-n-decylamine, tritylamine, N, N-dicyclohexylmethylamine, etc. It not only has the effect of improving the stability of the above-mentioned latent image, but also suppresses the generation of acid in the photoresist composition over time, but also has the effect of improving the storage stability of the photoresist solution and is suitable. (D) A component can be used individually or in mixture of 2 or more types. (D) The component is preferably in an amount of 0.001 to 5.0 parts by mass relative to 100 parts by mass of the resin solid content, and more preferably in a range of 0.1 to 1.0 parts by mass. • Organic solvents Organic solvents can be used without special restrictions if they are used in chemically enhanced positive photoresist compositions. For example, ester solvents such as propylene glycol monoalkyl ether acetate (such as propylene glycol monomethyl ether acetate (PGMEA)), lactate (such as ethyl lactate, etc.), acetone, methyl ethyl ketone, and cyclohexanone , Ketones such as methyl isoamyl ketone, 2-heptanone; ethylene glycol, propylene glycol, diethylene glycol, or one of these methyl ether, monoethyl ether, monopropyl ether, monobutyl ether, or monophenyl ether, etc. Polyols and their derivatives; non-ester solvents such as cyclic ethers of dioxane. The ester solvent is a reaction product of an organic carboxylic acid and an alcohol, and contains a free acid and an organic carboxylic acid. Therefore, the photoresist composition without the above-mentioned (D) component or the photoresist composition without the stabilizing agent described later is preferably selected from non-ester solvents that do not contain these free acids. Ketones ( Ketone solvents) are particularly preferred. Among them, 2-heptanone is more suitable for coating properties and (C) component solubility. -21-(17) 200428151 Both ester-based and non-ester-based solvents decompose by-products over time. In the presence of the above-mentioned (D) component, or a storage stabilizer described later, the decomposition reaction is suppressed. The effect is that the ester solvent, especially the (D) component, is particularly suitable for dissolving PGMEA in the presence of a stabilizer. The acid component produced as a result of the above-mentioned decomposition is considered to produce formic acid, acetic acid, propionic acid, etc. in 2-heptane. The organic solvents may be used singly or in combination of two or more kinds. The blending amount of the organic solvent is not particularly limited, but if the solid content can be 20 to 50% by mass, the coating property is better; 25 to 4 5 is preferable. In the chemically-enhanced positive-type photoresist composition of the present invention, a stabilizing agent is stored as follows when necessary. If the storage stabilizer has a limitation to suppress the decomposition reaction of the solvent, for example, there is a chemical agent described in Japanese Patent Application Laid-Open No. 5 8-1 94 8 34. As antioxidants, phenolic compounds and amine compounds are known to be particularly preferable. Among them, 2,6-bis (tertiary butyl) p-cresol is effective due to deterioration of ester-based solvents and ketone-based solvents. It is cheap and has good storage stability. Particularly, the blending amount of the component (D), which is extremely excellent in preventing deterioration of alkyl ether acetate and 2-heptanone, is 0.01 to 3% by mass, and particularly 0.1 to 1.0% by mass relative to the solid content of the resin. In addition, acid is produced in the chemically-enhanced positive-type photoresist composition of the present invention, which is significant in the presence of it, and the agent is better, and the ketone has a strong body composition. The more preferred one is anti-oxidant which is not used in particular. It is better to use phenol and its derivative to obtain propylene glycol with a mass range of 100. The non-destructive -22- (18) (18) 200428151 is used in the present invention. Within the scope of the purpose, it may contain compatible additives such as additional resins, plasticizers, stabilizers, surfactants to improve the performance of the photoresist film, so as to make the developed image more Visible coloring agents, sensitizers to further enhance the sensitization effect, dyes for anti-halation, adhesives and other commonly used additives. [Formation method of photoresist pattern] The method of forming the photoresist pattern of the present invention is a method using the chemically-enhanced positive photoresist composition. The following describes a suitable method of forming the photoresist pattern in the manufacture of a system LCD. An example. First, the component (A), the component (C), and various components added as necessary are dissolved in a solvent, and then applied to a substrate by a spin coater or the like to form a coating film. The substrate is preferably a glass substrate. The substrate can be a large substrate having a size of 500 mm &gt; &lt; 600 mm or more, particularly 550 mm &gt; &lt; 650 mm or more. Next, the glass substrate on which the coating film is formed is subjected to a heat treatment (pre-baking) at, for example, 90 to 140 ° C to remove the residual solvent to form a photoresist film. The pre-baking method is preferably performed in the vicinity of baking with a gap between the hot plate and the substrate. Secondly, for the above photoresist film, selective exposure is performed using a photomask depicting both a% mask pattern for integrated circuits and a photoresist pattern for liquid crystal display portions. The light source used here is preferably an i-line (3 65 nm) to form a fine pattern. In addition, the exposure program used for this exposure is such that the NA is 0.3 or less, preferably 0.2 or less, and more preferably 0.1 5 or less, and the NA program is 23-23 (19) 200428151. . The use of the exposure program under low NA conditions enables a large area of exposure at one time, which improves the yield. Secondly, for the photoresist film after selective exposure, add (post-exposure baking: PEB) · PEB method: baking in the vicinity of the gap between the hot plate and the substrate, directly baking without leaving a gap; Yu Sheng warp, the diffusion effect is obtained by PEB, and it is better to directly bake in a neighboring baking line. The heating temperature is from 90 to 150 ° C, and preferably from 140 ° C. For the photoresist film after the above PEB, a developer, such as an aqueous solution such as a 10% by mass aqueous solution of tetramethylammonium hydroxide, is used to dissolve and remove the exposed portions, and simultaneously form an integrated photoresist on the substrate. Photoresist pattern for pattern and liquid crystal display. Next, the developing solution remaining on the surface of the photoresist pattern is washed away with pure water or the like to form a photoresist pattern. In the step of performing the above-mentioned selective exposure, the above-mentioned photomask uses both a photomask pattern for a photoresist pattern formation pattern below 2.0 vm and a photomask pattern for a photoresist pattern formation pattern exceeding the mask pattern, that is, In the same step as the above photoresist pattern, a photoresist pattern for an integrated circuit with a size of 2.0 // m or less and a photoresist pattern for a portion of more than 2.0 in a liquid crystal display can be simultaneously formed on the above substrate. . The positive-type photoresist composition of the present invention has excellent linearity, so that a coarse pattern and a fine pattern are formed on a substrate under the same exposure conditions. Therefore, the local resolution is the display part of the system L C D, so that the photoresistance pattern of the finer circuit part is suitable for the manufacture of the system LCD. It can be used to heat-treat the inter-board protective substrate after production, and enter 100 to: the eluent for the road 1 to the imaging site is depicted as 2.0 // m when it is formed on the pattern ruler // m, it can be used. Integral • 24-(20) (20) 200428151 And reach, the high sensitivity, high resolution, and excellent DOF characteristics that the conventional quinonediazide-phenolic lacquer resin photoresist composition cannot. In addition to obtaining high heat resistance and preventing film loss in unexposed areas, it is also suitable for the production of TFTs that include an implantation step. The photoresist pattern forming method of the present invention using the above-mentioned positive type photoresist composition with excellent sensitivity can improve the yield in LCD manufacturing. By using the photoresist pattern forming method of the present invention, a high-resolution photoresist pattern can be formed, especially because it can be formed on a substrate at the same time, such as a photoresist pattern for an integrated circuit with a pattern size below, and for example 2. 〇 # m of the liquid crystal display part of the photoresistive pattern, suitable for the system LCD manufacturing. Examples The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples. [Evaluation method of positive photoresist composition] The evaluation methods of the following physical properties (1) to (5) of the positive photoresist composition of the following examples or comparative examples are as follows. (1) Sensitivity evaluation: a positive photoresist composition was applied to a large-size substrate with a photoresist coating device (device name: TR3 6000 manufactured by Tokyo Chemical Industry Co., Ltd.), and coated on a glass substrate formed with a Ti film (5 50 mm x 65 0 mm), pre-bake under 1401 :, 90 seconds heating conditions, and adjacent baking with an interval of about 1 mm to form a film thickness of 1.5 / m. The photoresist is -25- ( 21) (21) 200428151 membrane. Secondly, through the test pattern of the photomask pattern depicting the photoresist pattern of 1 · 5 # m line and space width (L &amp; S) and the 3.0 / m L &amp; S photoresist pattern simultaneously Mask (reticle) 'Selective exposure was performed using a 1-line exposure device (device name: FX-702J, manufactured by NIKON Corporation; NA = 0.14) with an exposure amount (Eoρ exposure amount) that faithfully reproduces L &amp; S. Secondly, at 110 ° C and 90 seconds, PEB is performed in a neighboring baking with a 0.5 m m interval. Next, a 23 ° C, 2.38% by mass TMAH aqueous solution was used for 60 seconds for development processing, and then rinsed with pure water for 30 seconds, followed by spin drying. The index of sensitivity evaluation is used to faithfully reproduce the exposure of L &amp; S photoresist pattern of 1 · 5 # m (Εορ, unit: mJ). (2) Evaluation of D 〇 F characteristics · Under the above Ε p exposure, the focus is appropriately slid up and down, and the depth of focus of the L &amp; S dimensional change rate within the range of ± 10% can be obtained in a unit of // m (DOF) width. (3) Evaluation of heat resistance: Under the above exposure dose, the substrate on which 1.5 / im L &amp; S is drawn is left for 30 seconds on a hot plate set at 140 ° C, and the shape of the cross section is observed . The result is 1.5 // m L &amp; S dimensional change rate is within ± 1% as A, and between 1 and 3% or -1 to -3% is as B, exceeding ± 3. % Is represented by C. (4) Evaluation of resolution ... The limit resolution at the above-mentioned exposure dose of Eορ is obtained.

(5) Linear evaluation: 3.0 // m L &amp; S (22) (22) 200428151 photoresistance cross-sectional shape obtained from the above exposure dose EO (scanning electron microscope) photo observation 'evaluation 3.0 / ^ m L &amp; Reproducibility of S photoresistance pattern. 3.0 // m L &amp; S

The dimensional change rate is within the range of ± 10/0 and A, and those exceeding ± 10% are represented by B. &amp; In the following examples, the component (A) uses the following. [Synthesis Example 1] (Synthesis of phenolic lacquer resin 1) Using m-methyl ester and formaldehyde, a phenolic lacquer resin 1 having M w = 82 00 and Mw / K8 was synthesized according to a general method. [Synthesis Example 2] (Synthesis of Phenolic Enamel Lacquer Resin 2) Use of mixed phenols of m-cresol / p-formaldehyde = 4/6 (molar ratio) and formaldehyde / salixal = 1 / 0.3 (molar ratio) Mixed aldehydes were synthesized according to the general method with Mw = 5462 and Mw / Mn = 10. [Synthesis Example 3] (Synthesis of component (A) 1) The concentration of methyl isobutyl ketone (MIBK) in the solvent was 30 mass. /. After dissolving the phenolic lacquer resin 1 with stirring so that the internal temperature reaches 100 to 110 ° C, the compound ((B) component) of the following formula (XΠ) is used to have a mass of 1000 relative to the solid content of the resin. A part is dripped only with respect to 8 mass parts. After 24 hours of reaction, the mixture was stirred at room temperature for 12 hours or more, and then substituted with a solvent of MIBK to 2-heptanone. The mass average molecular weight of the obtained (A) component (alkali poorly soluble phenolic varnish resin 1) was 5 0 0 0 0. (23) 200428151

CH? —0 —CH = CHg (XII) [Synthesis Example 4] ((A) Synthesis of Component 2)

The above phenolic lacquer resin 1 was changed to other than phenolic lacquer resin 2 'as in Synthesis Example 3 to obtain the component (A) (alkali-insoluble phenolic lacquer resin 2). The mass average molecular weight is 25,000. [Example 1] (A) Component [Alkali-insoluble phenolic lacquer resin 1 synthesized as described above]: 1000 parts by mass (C) component [Compound of the above formula (XI)]: 5 parts by mass (D) component [Tri-n-octylamine]: 0.28 parts by mass of each component dissolved in 2-heptanone, adjusted to 35% by mass, and added with 7-butyrolactone 0.5 parts by mass, the pore diameter is 0.2. // m The filter membrane filters and modulates the photoresist composition. The obtained photoresist composition was evaluated for the physical properties (1) to (5) above. The results are shown in Table 1 below. [Example 2] In Example 1, except that the component (A) was replaced with the base poorly soluble phenolic lacquer resin 2 which was used in the above synthesis example, the photoresist was prepared in the same manner as in Example 1 -28- (24) 200428151. The obtained photoresist composition was evaluated for physical properties (1) to (5) above. The results are shown in Table 1 below. [Comparative Example 1] As a comparative example, a conventional quinonediazide novolak varnish-based photoresist composition (product name "THMR-iP 5 700"; manufactured by Tokyo Chemical Industry Co., Ltd.) was used.

The obtained photoresist composition was evaluated for physical properties (1) to (5) above. The results are shown in Table 1 below.

Table 1

Sensitivity DOF Heat resistance resolution linear (m J) (// m) (β ηι) Example 1 65 30 B 1 .3 A Example 2 65 30 A 1 .2 A Comparative Example 1 90 15 C 1 .2 A -29-

Claims (1)

200428151 Π) Pick up and apply for patent scope 1 · A chemically enhanced positive type photoresist composition is a chemically enhanced positive type photoresist composition for the manufacture of a substrate on which a integrated circuit and a liquid crystal display portion are formed on a substrate, It is characterized by containing the reaction product of (A 1) alkali-soluble phenolic lacquer resin and (B) a compound of the following general formula (I), which has the property of increasing solubility in an alkaline aqueous solution in the presence of an acid ( A) Alkali-insoluble or insoluble _ awakening lacquer resin, and (C) Compounds that produce acid components by radiation irradiation, and organic solvents. H2C = CH-0-R1-0-CH = CH2… (I) [wherein R1 represents an alkylene group having 1 to 10 carbon atoms which may have a substituent 'or the following general formula (11) (Wherein R4 represents an alkylene group having 1 to 10 carbon atoms which may have a substituent, m is 0 or 1), any of the subunits in the main chain may contain an oxygen bond (ether bond) P 2 .For example, the chemically enhanced positive photoresist composition in the first patent application range, wherein the (A) component has the following general formula (melon) • 30- (2) 200428151 [Wherein R1 represents an alkylene group having 1 to 10 carbon atoms which may have a substituent, or the following general formula (Π) (where R4 represents an alkylene group having 1 to 10 carbon atoms which may have a substituent, m is any one of the groups of 0 or 1), these alkylene groups may also contain oxygen bonds (ether bonds) in the main chain, and R2 and R3 are independent of each other, showing a hydrogen atom and an alkyl group having 1 to 3 carbon atoms , Or aryl, n represents an integer of 1 to 3] structural unit (al). 3. The chemically-enhanced positive photoresist composition according to item 2 of the scope of patent application, wherein the component (A) has the following general formula (IV) -31-(3) (3) 200428151 (Wherein R1 represents an alkylene group having 1 to 10 carbon atoms which may have a substituent, or the following general formula (Π) (where R4 represents an alkylene group having 1 to 10 carbon atoms which may have a substituent, m is any one of the groups of 0 or 1), R2 and R3 are each independently, and represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an aryl group, and η represents an integer of 1 to 3, and these alkylene groups are also It may contain an intermolecular cross-linking moiety (a2) of an oxygen bond (ether bond)) in the main chain. 4. The chemically-enhanced positive-type photoresist composition according to item 1 of the patent application range, wherein the (C) component is a compound that generates an acid component by irradiation with i-rays (36.5 nm). 5. The chemically-enhanced positive-type photoresist composition 'according to item 丨 of the patent application scope, which further contains (D) a basic compound. 6. A method for forming a photoresist pattern, characterized in that it includes (1) a chemically-enhanced positive light such as item 1 of the scope of the patent application • 32- (4) 200428151 a resist composition is coated on the substrate 'Step of forming a coating film' (2) The step of forming a photoresist film on the substrate by heating (pre-baking) the substrate for forming the coating film '(3) For the above photoresist film, use 2.0 V Steps of selective exposure of a mask pattern for forming a photoresist pattern of m and a mask pattern for forming a photoresist pattern of more than 2.0 // m, (4) applying heat treatment (post-exposure bake) to the photoresist film after selective exposure, (5) applying image development treatment using alkaline aqueous solution to the photoresist film after heat treatment, The photoresist pattern for integrated circuits with a pattern size of 2.0 // m or less and the photoresist pattern for liquid crystal display portions exceeding 2.0 / im are simultaneously formed on the above substrate. 7 · The method of forming a photoresist pattern according to item 6 of the patent application range, wherein the step of selective exposure (3) above uses an i-ray light source and is performed according to an exposure procedure under a low NA condition of NA below 0.3. . -33- 200428151 柒, (1), the designated representative of this case is: None (二), the component representative symbol of this representative is simply explained: None 捌 If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: Formula IV -5-