KR100596988B1 - Positive type photoresist composition and method of forming resist pattern - Google Patents

Abstract

(Problem) To provide a resist material with excellent linearity which can form a fine resist pattern of 2.0 micrometers or less even under the low NA conditions used suitably for manufacture of system LCD whose NA is 0.2 or less.

(Solution) A positive photoresist composition for use in the manufacture of an LCD in which an integrated circuit and a liquid crystal display portion are formed on one substrate, comprising: (A) an alkali-soluble resin, (B) a naphthoquinone diazide esterate, and (C) Formula 1

(Wherein R ¹ to R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; a and b each independently represent an integer of 1 to 3) and at least one phenolic hydroxyl group-containing compound selected from the group consisting of compounds represented by (D) and a positive type comprising the organic solvent Photoresist composition.

Description

Formation method of positive type photoresist composition and resist pattern {POSITIVE TYPE PHOTORESIST COMPOSITION AND METHOD OF FORMING RESIST PATTERN}

BRIEF DESCRIPTION OF THE DRAWINGS It is explanatory drawing of the process of apply | coating liquid to a developing solution from the board | substrate edge part X to Z. FIG.

The present invention relates to a positive type photoresist composition and a method of forming a resist pattern for use in manufacturing an LCD having an integrated circuit and a liquid crystal display portion formed on one substrate.

In manufacture of a semiconductor element, the positive type photoresist material which consists of a system which used novolak resin as a film formation component and the quinone diazide group containing compound as a photosensitive component is used a lot. The positive type photoresist material composed of the system of the novolak resin-quinonediazide group-containing compound is relatively inexpensive and can form a resist pattern excellent in sensitivity, resolution, and shape. It is also used for the manufacture of (liquid crystal display elements).                         

However, in the field of LCD manufacturing, the substrate to which the resist material is applied differs greatly from that used in the manufacture of semiconductor devices in terms of their material, shape, and size.

For example, as a board | substrate of a semiconductor element, the disk type silicon wafer of the maximum 8 inches (about 200 mm)-12 inches (about 300 mm) in diameter is used. In contrast, a rectangular glass substrate of at least 360 mm x 460 mm is used as the substrate of the LCD.

Therefore, it is required for the resist material for LCD manufacture to be able to form the resist pattern with favorable shape and dimensional stability with respect to the wide whole surface of a board | substrate. In addition, since a large amount of resist material is required for manufacturing the liquid crystal display element, it is also desired that the resist material be inexpensive.

On the other hand, as a next-generation LCD, a technology for a high-performance LCD called "System LCD" is formed on the board of a single board, which includes a display part, a driver, a digital-to-analog converter (DAC), an image processor, a video controller, and a RAM. Development is active (Semiconductor FPD World 2001.9, pp.50-67).

In this system LCD, the resist pattern dimension formed on the substrate is, for example, about 2 to 10 mu m in the display portion, whereas the integrated circuit portion is as fine as about 0.5 to 2.0 mu m.

In order to simultaneously form display portions and integrated circuit portions having different pattern dimensions, a resist material having excellent linearity under the same exposure conditions is desired. Linearity is a characteristic which reproduces the mask dimension on a reticle when it exposes on the same exposure conditions (conditions on which the mask dimension on a reticle is different but exposure amount is the same).

In addition, in order to form a fine pattern of the integrated circuit portion, it is necessary to use a resist material having a higher resolution than the conventional resist material for manufacturing a liquid crystal display element used to form a display portion having a relatively large pattern dimension.

The resolution (resolution limit) is a Rayleigh equation represented by the formula: R = k ₁ × λ / NA (where R is the resolution limit, k ₁ is the proportionality constant determined by the resist, process or phase formation method, λ) Is the wavelength of light used in the exposure process, NA represents the numerical aperture of the lens).

Therefore, in order to improve the resolution R, (1) it is necessary to use a light source with a short wavelength [lambda] or (2) use a high NA exposure process.

In the case of (1), photolithography using i-line (365 nm) exposure, which is a shorter wavelength, instead of g-ray (436 nm) exposure conventionally used when forming a fine resist pattern of 2.0 µm or less, for example. Using technology is one effective way.

On the other hand, in the case of (2), it can implement by using a lens with as high NA as possible.

By the way, in the field of LCD manufacture, it is desired to make an exposure area wide at least about 100 mm <2> from a viewpoint of throughput (processing amount per unit time) improvement. However, if the NA of the lens is made high, the depth of focus becomes shallow. Therefore, the wider the exposure area, the more difficult it is to maintain in-plane uniformity of the exposed portion.

For this reason, high NA is difficult in the field of LCD manufacture, and it is generally considered that it is preferable to use the exposure process of the low NA conditions of 0.2 or less, for example.

However, the resist material for manufacturing a conventional LCD has poor linearity under low NA conditions, making it difficult to form a fine resist pattern on the order of 0.5 to 2.0 mu m in an excellent shape. Moreover, the cross-sectional shape of the resist pattern obtained using the conventional resist material for LCD manufacture also tended to have a taper shape instead of a rectangular shape.

For example, conventional resist materials for manufacturing liquid crystal display devices are disclosed in Japanese Patent Application Laid-Open Nos. Hei 9-160231, Hei 9-211855, Hei 2000-112120, Hei 2000-131835, Hei 2000-181055 and Hei. There are a number of reports, including 2001-75272.

The materials described in these are inexpensive, and when forming a relatively large pattern dimension, it is possible to form a resist pattern having good applicability, sensitivity and resolution, and excellent shape and dimensional stability. Therefore, these materials are suitable for the purpose of manufacturing LCDs (without integrated circuits) having only a display portion.

However, to be used in the manufacturing process of the system LCD as described above, it is necessary to improve linearity under low NA conditions.

That is, the present invention provides a resist material having improved linearity such that NA can form a fine resist pattern of 2.0 μm or less even under low NA conditions where NA is suitably used for manufacturing a system LCD such as 0.2 or less. It is a task to do.

Means to solve the problem

As a result of earnest research to solve the above problems, the present inventors found that a positive photoresist composition containing a specific trisphenyl-based sensitizer (phenolic hydroxyl group-containing compound) has excellent linearity under low NA conditions, and is integrated on one substrate. The present invention has been completed by finding that it is a resist material suitable for the manufacture of a resist LCD in which circuits and liquid crystal display portions are formed.

That is, the present invention is a positive type photoresist composition for LCD production, in which an integrated circuit and a liquid crystal display portion are formed on one substrate, including (A) an alkali-soluble resin, (B) a naphthoquinone diazide esterate, and (C)

[Formula 1]

(Wherein R ¹ to R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; a and b each independently represent an integer of 1 to 3) and at least one phenolic hydroxyl group-containing compound selected from the group consisting of compounds represented by (D) and a positive type comprising the organic solvent It relates to a photoresist composition.

Moreover, this invention is the process of (1) applying the said positive photoresist composition on a board | substrate, and forming a coating film, (2) heat-processing the board | substrate with the said coating film, and forming a resist film on a board | substrate, (3) said Performing a selective exposure to the resist film using a mask on which a resist pattern forming mask pattern of 2.0 µm or less and a resist pattern forming mask pattern of 2.0 µm or more are drawn; (4) the resist after the selective exposure; Developing a film using an aqueous alkali solution, and simultaneously forming a resist pattern for integrated circuits with a pattern dimension of 2.0 μm or less and a resist pattern for liquid crystal display portions larger than 2.0 μm on the substrate; and (5) the resist. Resist comprising a rinse step of washing off the developer remaining on the pattern surface It relates to a method for forming a turn.

Embodiment of the invention

In the present specification, the system LCD refers to an LCD in which an integrated circuit and a liquid crystal display portion are formed on one substrate as described above.

In the positive photoresist composition of the present invention, the component (A) is not particularly limited and may be arbitrarily selected from those which can be normally used as a film-forming substance in the positive photoresist composition.

As this alkali-soluble resin, For example, phenols, such as a phenol, m-cresol, p-cresol, xylenol, trimethylphenol, formaldehyde, a formaldehyde precursor, 2-hydroxybenzaldehyde, 3-hydroxy benzaldehyde, Novolak resins obtained by condensing aldehydes such as 4-hydroxybenzaldehyde and the like in the presence of an acidic catalyst; Hydroxystyrene resins such as homopolymers of hydroxystyrene, copolymers of hydroxystyrene and other styrene monomers, copolymers of hydroxystyrene and acrylic acid or methacrylic acid or derivatives thereof; Alkali-soluble resin, such as acrylic acid or methacrylic acid resin which is a copolymer of acrylic acid or methacrylic acid, and its derivative (s) is mentioned.

In particular, novolak resins obtained by condensation reaction of phenols containing m-cresol and 3,4-xylenol with aldehydes containing propionaldehyde and formaldehyde are suitable for preparing a resist material having high linearity with high sensitivity. .

In the positive photoresist composition of the present invention, the component (B) is not particularly limited, and any of naphthoquinone diazide esterified compounds conventionally used as the photosensitive component of the resist can be used. In particular, esterified compounds of the phenol compound and naphthoquinone diazide sulfonic acid compound represented by the following general formula (2) are suitable for photolithography using i line, and for example, to form a fine resist pattern of 2.0 µm or less in a good shape. Suitable for the occasion.                     

[In formula, R <^1> -R <^8> represents a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, or a C3-C6 cycloalkyl group each independently; R ⁹ to R ¹¹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Q is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may be bonded to the terminal of R ⁹ to form a cycloalkyl group having 3 to 6 carbon atoms, or the following general formula 3:

Wherein R ¹² and R ¹³ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms; And a, b each independently represent an integer of 1 to 3, d represents an integer of 0 to 3, and n represents an integer of 0 to 3.).

Further, if the Q taken together with the carbon atom between R ⁹ and, Q and R ⁹ form a cycloalkyl group having 3 to 6 carbon atoms, and combines the Q and R ⁹ constitute an alkylene group of a carbon number of 2-5.

As a phenolic compound corresponding to this formula (2),

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,

Bis (4-hydroxy-3,5-dimethylphenyl) -3-hydroxyphenylmethane,

Bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane,

Bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxyphenylmethane,

Bis (4-hydroxy-2,5-dimethylphenyl) -3-hydroxyphenylmethane,

Bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane,

Bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane,

Bis (4-hydroxy-2,5-dimethylphenyl) -3,4-dihydroxyphenylmethane,

Bis (4-hydroxy-2,5-dimethylphenyl) -2,4-dihydroxyphenylmethane,

Bis (4-hydroxyphenyl) -3-methoxy-4-hydroxyphenylmethane,

Bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenylmethane,

Bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane,                     

Bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -2-hydroxyphenylmethane,

Trisphenol type compounds such as bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane;

2,4-bis (3,5-dimethyl-4-hydroxybenzyl) -5-hydroxyphenol,

Linear trinuclear phenol compounds such as 2,6-bis (2,5-dimethyl-4-hydroxybenzyl) -4-methylphenol;

1,1-bis [3- (2-hydroxy-5-methylbenzyl) -4-hydroxy-5-cyclohexylphenyl] isopropane,

Bis [2,5-dimethyl-3- (4-hydroxy-5-methylbenzyl) -4-hydroxyphenyl] methane,

Bis [2,5-dimethyl-3- (4-hydroxybenzyl) -4-hydroxyphenyl] methane,

Bis [3- (3,5-dimethyl-4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane,

Bis [3- (3,5-dimethyl-4-hydroxybenzyl) -4-hydroxy-5-ethylphenyl] methane,

Bis [3- (3,5-diethyl-4-hydroxybenzyl) -4-hydroxy-5-methylphenyl] methane,

Bis [3- (3,5-diethyl-4-hydroxybenzyl) -4-hydroxy-5-ethylphenyl] methane,

Bis [2-hydroxy-3- (3,5-dimethyl-4-hydroxybenzyl) -5-methylphenyl] methane,

Bis [2-hydroxy-3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl] methane,

Bis [4-hydroxy-3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl] methane,

Linear tetranuclear phenol compounds such as bis [2,5-dimethyl-3- (2-hydroxy-5-methylbenzyl) -4-hydroxyphenyl] methane;

2,4-bis [2-hydroxy-3- (4-hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol,                     

2,4-bis [4-hydroxy-3- (4-hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol,

Linear poly, such as linear 5-nuclear body phenolic compounds, such as 2,6-bis [2,5-dimethyl-3- (2-hydroxy-5-methylbenzyl) -4-hydroxybenzyl] -4-methylphenol Phenolic compound;

Bis (2,3,4-trihydroxyphenyl) methane,

Bis (2,4-dihydroxyphenyl) methane,

2,3,4-trihydroxyphenyl-4'-hydroxyphenylmethane,

2- (2,3,4-trihydroxyphenyl) -2- (2 ', 3', 4'-trihydroxyphenyl) propane,

2- (2,4-dihydroxyphenyl) -2- (2 ', 4'-dihydroxyphenyl) propane,

2- (4-hydroxyphenyl) -2- (4'-hydroxyphenyl) propane,

2- (3-fluoro-4-hydroxyphenyl) -2- (3'-fluoro-4'-hydroxyphenyl) propane,

2- (2,4-dihydroxyphenyl) -2- (4'-hydroxyphenyl) propane,

2- (2,3,4-trihydroxyphenyl) -2- (4'-hydroxyphenyl) propane,

Bisphenol-type compounds such as 2- (2,3,4-trihydroxyphenyl) -2- (4'-hydroxy-3 ', 5'-dimethylphenyl) propane;

1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene,

Multinuclear branched compounds such as 1- [1- (3-methyl-4-hydroxyphenyl) isopropyl] -4- [1,1-bis (3-methyl-4-hydroxyphenyl) ethyl] benzene;

Condensation type phenol compounds, such as 1, 1-bis (4-hydroxyphenyl) cyclohexane, etc. are mentioned.

inter alia,                     

Bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) -3,4-dihydroxyphenylmethane,

Bis (2,4-dihydroxyphenyl) methane and

The photoresist composition containing a naphthoquinone diazide ester compound of three kinds of phenolic compounds of bis (2,3,5-trimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane has sensitivity, resolution, and resist properties. It is preferable at the point which is excellent in a pattern shape.

The naphthoquinone diazide sulfonic acid esterification method of all or part of the phenolic hydroxyl group of the compound represented by the said Formula (2) can be performed by a conventional method. For example, naphthoquinonediazide sulfonyl chloride is condensed with the compound represented by the above formula (2). Specifically, the compound represented by the formula (2), naphthoquinone-1,2-diazide-4-sulfonyl chloride or naphthoquinone-1,2-diazide-5-sulfonyl chloride, dioxane, A predetermined amount is dissolved in organic solvents such as n-methylpyrrolidone, dimethylacetamide and tetrahydrofuran, and basic catalysts such as triethylamine, triethanolamine, pyridine, alkali carbonate and alkali hydrogen carbonate are added and reacted. The product obtained is washed with water and dried.

As the component (B), other naphthoquinone diazide esterates can be used in addition to the above-mentioned naphthoquinone diazide ester compounds. For example, esterification reaction products of phenol compounds such as polyhydroxybenzophenone and alkyl gallate and naphthoquinone diazide sulfonic acid compounds can also be used. It is preferable that the usage-amount of the said other naphthoquinone diazide ester-ized thing is 80 mass% or less, especially 50 mass% or less in (B) component in the point which does not inhibit the effect of this invention.                     

In the positive photoresist composition of the present invention, the blending amount of the component (B) is 10 to 70% by mass, preferably 20 to 40% by mass relative to the total mass of the component (A) and the component (C) below. It is preferable to select from. When the compounding quantity of (B) component is less than the said range, the image faithful to a pattern may not be obtained and transferability may fall. On the other hand, when the compounding quantity of (B) component exceeds the said range, there exists a possibility of the resolution deterioration by the sensitivity deterioration and the homogeneity of the resist film formed.

In the positive photoresist composition of the present invention, at least one phenolic hydroxyl group-containing compound selected from the compounds represented by the general formula (1) as (C) component is blended. By mix | blending this (C) component, the positive type photoresist composition suitable for manufacture of the system LCD which can form the pattern excellent in linearity in low NA conditions is obtained. Furthermore, this positive photoresist composition is suitable for the i-ray exposure process, and hardly scum is found on the substrate after exposure and development.

Although it does not restrict | limit especially as a phenolic hydroxyl group containing compound represented by General formula (1), For example, the trisphenol type compound represented by following General formula (1a-1f) shows the said characteristic well, and is preferable.

The compound represented by this formula (1a) is preferable because of its good sensitivity.

The compound represented by the formula (1b) is preferable because the overall balance is good with respect to all of sensitivity, linearity and resolution.

The compound represented by this formula (1c) is preferable because linearity is particularly good.

The compound represented by the formula (1d) is preferable because of its good sensitivity and heat resistance.                     

The compound represented by the formula (1e) is preferable because of its relatively good heat resistance.

The compound represented by the general formula (1f) is preferable because it has very good sensitivity and heat resistance.

The compounding quantity of (C) component is 10-70 mass% with respect to alkali-soluble resin which is (A) component, Preferably it is selected in the range of 20-40 mass%. If the compounding quantity of (C) component is in the said range, the sensitivity in an i line | wire exposure process etc. will be favorable, and linearity will improve. Further, even under low NA conditions such as NA of 0.2 or less, a fine resist pattern of 2.0 µm or less can be formed.

It is preferable that the composition of this invention dissolves the (A)-(C) component and the various additive components mix | blended as needed in the following (D) component which is an organic solvent, and uses it in the form of a solution.

Although there is no limitation in particular as (D) component, It is preferable at the point which contains propylene glycol monoalkyl ether acetate and / or alkyl lactic acid from the point which is excellent in applicability | paintability and excellent in film thickness uniformity on a large glass substrate. .

Among the propylene glycol monoalkyl ether acetates, propylene glycol monomethyl ether acetate (hereinafter referred to as "PGMEA") is particularly preferable, and the film thickness uniformity of the resist film on a large glass substrate is very excellent.

Among the alkyl lactates, ethyl lactate is most preferred. In the case of using a large glass substrate of 500 mm x 600 mm or more, since it tends to cause coating stains when used alone, it is preferable to use it in a mixed system with other solvents. Do.

In particular, the composition containing both of propylene glycol monoalkyl ether acetate and alkyl lactate has excellent film thickness uniformity of the resist film, can form a resist pattern with excellent shape, and also improves heat resistance and scum. ) Is also preferable in that the generation of

When using propylene glycol monoalkyl ether acetate and alkyl lactate, it is preferable to mix | blend 0.1-10 times, preferably 1-5 times the amount of alkyl lactate with respect to propylene glycol monoalkyl ether acetate.

In addition, in addition to the propylene glycol monoalkyl ether acetate and / or alkyl lactate, you may mix other organic solvents, such as (gamma) -butyrolactone and a propylene glycol monobutyl ether, to (D) component. When using gamma -butyrolactone, it is preferable to mix | blend in the range of the quantity of 0.01-1 time, Preferably it is 0.05-0.5 time with respect to propylene glycol mono alkyl ether acetate.

As other organic solvents other than γ-butyrolactone and propylene glycol monobutyl ether, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone and methyl isoamyl ketone; Ethylene glycol, propylene glycol, diethylene glycol, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate or polyhydric compounds such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether Alcohols and derivatives thereof; Cyclic ethers such as dioxane; And esters such as methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate.

When using other organic solvents other than these, it is preferable that they are 50 mass% or less with respect to propylene glycol monoalkyl ether acetate, alkyl lactate, or a mixture thereof.

As the component (D), when a nonbenzophenone photosensitive component is used as the naphthoquinone diazide esterified product (B), 2-heptanone (hereinafter referred to as "HE") can also be preferably used. HE is a very preferable solvent because it is excellent in heat resistance compared to PGMEA and gives a resist composition with reduced scum generation. HE may be used independently and may be used in mixture with the organic solvent mentioned above.

In this invention, various additives, such as surfactant, a ultraviolet absorber, a storage stabilizer, can be used in the range which does not impair the objective of this invention.                     

As surfactant, Floroid FC-430 and FC-431 (brand name, all are Sumitomo 3M company make); F-top EF122A, EF122B, EF122C, EF126 (brand name, all are manufactured by Tochem Products); Fluorine-type surfactant, such as Megapack R-08 (brand name, the Dai Nippon Inky Chemical company make) can be illustrated. As a ultraviolet absorber, 2,2 ', 4,4'- tetrahydroxy benzophenone, 4-dimethylamino-2', 4'- dihydroxy benzophenone, 5-amino-3-methyl-1- phenyl- 4- (4-hydroxyphenylazo) pyrazole, 4-dimethylamino-4'-hydroxyazobenzene, 4-diethylamino-4'-ethoxyazobenzene, 4-diethylaminoazobenzene, curcumin and the like will be exemplified. Can be.

Moreover, you may use the compound (E) which is not contained in the (C) component represented by the said General formula (1) as a phenolic hydroxyl group containing compound generally used as a sensitizer in a photoresist composition. When using this (E) component, the sum total of the compounding quantity of (C) component and (E) component is 10-70 mass% with respect to (A) component, Preferably it is within the range of 20-40 mass%. Moreover, it is preferable that (E) component is 50 mass% or less in the total amount of (C) component and (E) component to be used. As (E) component, the phenol compound represented by the said General formula (2) is mentioned. Among them, 1- [1,1-bis (4-hydroxyphenyl) ethyl] -4- [1- (4-hydroxyphenyl) isopropyl] benzene is preferred because of its excellent sensitivity enhancement effect.

An example of the preferable formation method of the resist pattern for system LCD manufacture using the composition of this invention is shown.

First, (A) component, (B) component, (C) component, and the various components added as needed are dissolved in the solvent which is (D) component, and this is apply | coated to a board | substrate with a spinner etc. As the substrate, a glass substrate is preferable. As the glass substrate, a large substrate of 500 mm x 600 mm or more, particularly 550 mm x 650 mm or more can be used.

Subsequently, the remaining solvent is removed by heat-processing (prebaking) the board | substrate with which this coating film was formed, for example at 100-140 degreeC, and a resist film is formed. As the prebaking method, it is preferable to perform a proximity bake that makes a gap between the hot plate and the substrate.

Subsequently, for the resist film, for example, a mask pattern for forming a resist pattern for an integrated circuit having a pattern dimension of 2.0 μm or less (preferably 0.5 to 2.0 μm), and a pattern dimension exceeding 2.0 μm (preferably 2.0) More than 10 μm) The selective exposure is performed using a desired light source using a mask on which both of the mask patterns for forming a resist pattern for liquid crystal display portions are drawn.

As a light source used here, it is preferable to use i line (365 nm) in order to form a fine pattern. Moreover, it is preferable that the exposure process employ | adopted by this exposure is a process of low NA conditions whose NA is 0.2 or less, More preferably, it is 0.15 or less.

Subsequently, developing treatment using a developing solution, for example, an aqueous alkaline solution such as 1 to 10% by mass of tetramethylammonium hydroxide aqueous solution is performed on the resist film after selective exposure. As a result, the exposed portion is dissolved and removed, and the resist pattern for the integrated circuit and the resist pattern for the liquid crystal display portion are simultaneously formed on the substrate.

Subsequently, the resist pattern can be formed by rinsing the developer remaining on the surface of the resist pattern with a rinse solution such as pure water.

EXAMPLE

Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1

(A) Ingredients:

100 parts by mass of alkali-soluble resin (A1)

A1: m-cresol / 3,4-xylenol = 9/1 (molar ratio) mixed phenol and a condensation agent using a mixed aldehyde of propionaldehyde / formaldehyde = 1/3 (molar ratio) by a conventional method Synthesized Mw = 4750, Mw / Mn = 2.44, novolac resin

(B) Ingredients:

35 parts by mass of naphthoquinone diazide esterified product (a mixture of B1 / B2 / B3 = 6/1/1 (mass ratio))

B1: 1 mol of bis (2-methyl-4-hydroxy-5-cyclohexylphenyl) -3,4-dihydroxyphenylmethane and 1,2-naphthoquinonediazide-5-sulfonic acid chloride (hereinafter, 5-NQD ”) 2 mole esterification product

B2: esterification product of 1 mol of bis (2,4-dihydroxyphenyl) methane with 4 mol of 5-NQD

B3: esterification product of 1 mole of bis (2,3,5-trimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane with 2 moles of 5-NQD

(C) Ingredients:                     

25 mass parts of phenolic hydroxyl group containing compounds represented by following General formula (1a)

[Formula 1a]

PGMEA was used as a surfactant (trade name "R-08"; manufactured by Dainippon Inkki Co., Ltd.) in an amount equivalent to 350 ppm relative to the total mass of the components (A) to (C) and (A) to (C). It dissolved in ((D) component). The usage-amount of (D) component was adjusted so that solid content [the sum of (A)-(C) component] concentration might be 25-28 mass% concentration. This was filtered using a membrane filter having a pore diameter of 0.2 µm to prepare a positive photoresist composition.

Examples 2 to 9, Comparative Examples 1 and 2

As a component (A)-(E), the positive type photoresist composition was prepared like Example 1 except having used the thing of Table 1 as the compounding quantity (mass part) shown in Table 1. In addition, the usage-amount of (D) component was adjusted so that solid content [the sum of (A)-(C) and (E) component] concentration might be 25-28 mass% concentration.                     

(A) (parts by mass) (B) (mass ratio) (mass part) (C) (parts by mass) (D) (E) (parts by mass) Example 1 A1 (100) B1 / B2 / B3 (6/1/1) (35) Compound of formula (1a) (25) PGMEA Example 2 A1 (100) B1 / B2 / B3 (6/1/1) (35) Compound of formula (1b) (25) PGMEA Example 3 A1 (100) B1 / B2 / B3 (6/1/1) (35) Compound of formula (1c) (25) PGMEA Example 4 A1 (100) B1 / B2 / B3 (6/1/1) (3/5) Compound of formula (1d) (25) PGMEA Example 5 A1 (100) B1 / B2 / B3 (6/1/1) (35) Compound of formula (1e) (25) PGMEA Example 6 A1 (100) B1 / B2 / B3 (6/1/1) (35) Compound of formula (1f) (25) PGMEA Example 7 A1 (100) B1 / B2 / B3 (6/1/1) (35) Compound of Formula (1b) (12.5) PGMEA E1 (12.5) Example 8 A1 (100) B1 / B2 / B3 (6/1/1) (35) Compound of formula (1b) (25) HE Example 9 A2 (100) B1 / B2 / B3 (6/1/1) (35) Compound of formula (1b) (25) PGMEA Example 10 A1 (100) B1 / B4 (1/1) (35) Compound of formula (1b) (25) PGMEA Comparative Example 1 A1 (100) B1 / B2 / B3 (6/1/1) (35)  - PGMEA E2 (25) Comparative Example 2 A1 (100) B1 / B2 / B3 (6/1/1) (35)  - PGMEA E3 (25)

In Table 1, each symbol shows the following meanings.

A2: m-cresol / p-cresol / 2,3,5-trimethylphenol = 9 / 0.5 / 0.5 (molar ratio) As a mixed phenol and a condensing agent, using formaldehyde / crotonaldehyde = 2/1 (molar ratio) normally Compounded Mw = 7000, Mw / Mn = 3.05, Novolak Resin                     

B4: esterification product of 1 mol of methyl gallate and 3 mol of 5-NQD

E1: 1- [1,1-bis (4-hydroxyphenyl) ethyl] -4- [1- (4-hydroxyphenyl) isopropyl] benzene

E2: 2,3,4,4'-tetrahydroxybenzophenone

E3: bis [2-hydroxy-3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl] methane

PGMEA: Propylene Glycol Monomethyl Ether Acetate

HE: 2-heptanone

Test Example 1

The positive type photoresist compositions obtained in Examples 1 to 9 and Comparative Examples 1 and 2 were evaluated for the following physical properties (1) to (3). These evaluation results are shown in Table 2.

(1) Linearity evaluation:

A positive photoresist composition was applied onto a glass substrate (550 mm x 650 mm) on which a Cr film was formed using a spinner. Thereafter, the first drying was performed for 60 seconds by a proximity bake with an interval of about 1 mm on a hot plate set at 130 ° C. Subsequently, the temperature of the hot plate was set to 120 ° C., and second drying was performed for 60 seconds by a proximity bake with an interval of 0.5 mm to form a resist film having a thickness of 1.5 μm.

Subsequently, the i-line exposure apparatus (device name: through a test chart mask (reticle) on which both a mask pattern for forming a line and space (L & S) of 3.0 mu m and a mask pattern for forming a resist pattern of 1.5 mu m L & S was drawn. Selective exposure was performed using FX-702J, manufactured by Nikon Corporation; NA = 0.14). The exposure amount was made into the exposure amount (Eop exposure amount) which can faithfully reproduce 3.0 micrometers L & S.

Subsequently, a tetramethylammonium hydroxide (TMAH) aqueous solution having a concentration of 2.38% by mass at 23 ° C. was used on a substrate using a developing apparatus having a slit coater nozzle (device name: TD-39000 Demonstrator, manufactured by Tokyo Oka Industry Co., Ltd.). The solution was applied. At this time, as shown in FIG. 1, the liquid was apply | coated on the board | substrate for 10 second from one terminal part X to Y through the other terminal part Z of a board | substrate. After holding for 55 seconds, water was washed for 30 seconds and spin-dried.

Then, the cross-sectional shape of the obtained resist pattern was observed by SEM (scanning electron microscope) photograph, and the reproducibility of the resist pattern of 1.5 micrometer L & S was evaluated.

(2) sensitivity evaluation:

The Eop exposure amount was used as an index of sensitivity evaluation.

(3) Resolution Evaluation:

The limit resolution in the said Eop exposure amount was calculated | required.                     

Example Linearity Evaluation (μm) Sensitivity rating (mJ) Resolution Evaluation (μm) One 1.55 60 1.3 2 1.52 50 1.3 3 1.50 85 1.3 4 1.55 65 1.3 5 1.55 80 1.3 6 1.58 42.5 1.4 7 1.51 47.5 1.3 8 1.55 70 1.3 9 1.70 50 1.4 10 1.55 70 1.4 Comparative Example 1 - More than 100 - 2 - More than 100 -

In the positive resist compositions of Comparative Examples 1 and 2, the 1.5 µm L & S pattern could not be drawn, so the linearity evaluation could not be performed.

In contrast, the positive photoresist compositions of the present invention all exhibited good linearity. Moreover, both the sensitivity and the resolution were good, and a good balance was achieved in all evaluation items including linearity.

As described above, the positive photoresist composition of the present invention is excellent in linearity under low NA conditions. Therefore, since the rough pattern and the fine pattern can be formed on one substrate under the same exposure conditions, they are suitable as a positive photoresist composition for manufacturing LCDs (system LCDs) in which integrated circuits and liquid crystal display portions are formed on one substrate. .

Further, according to the method of forming a resist pattern of the present invention using the positive photoresist composition excellent in linearity under low NA conditions, a fine resist pattern suitable for the manufacture of a system LCD can be formed.

Claims (13)

A positive type photoresist composition for manufacturing an LCD in which an integrated circuit and a liquid crystal display portion are formed on one substrate, (A) alkali-soluble resin, (B) naphthoquinone diazide esterified product, (C) following General formula (1) [Formula 1]

(Wherein R ¹ to R ⁶ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms; R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; a and b each independently represent an integer of 1 to 3) and at least one phenolic hydroxyl group-containing compound selected from the group consisting of compounds represented by (D) and a positive type comprising the organic solvent Photoresist composition. The method of claim 1, wherein the component (C) is represented by the formula [Formula 1a]

A positive type photoresist composition for manufacturing an LCD having an integrated circuit and a liquid crystal display portion formed on one substrate, which is a compound represented by. The method according to claim 1, wherein the component (C) is represented by the formula (1b): [Formula 1b]

A positive type photoresist composition for manufacturing an LCD having an integrated circuit and a liquid crystal display portion formed on one substrate, which is a compound represented by. The method of claim 1, wherein the component (C) is represented by the formula (1c): [Formula 1c]

A positive type photoresist composition for manufacturing an LCD having an integrated circuit and a liquid crystal display portion formed on one substrate, which is a compound represented by. According to claim 1, wherein the component (C) is represented by the formula [Formula 1d]

A positive type photoresist composition for manufacturing an LCD having an integrated circuit and a liquid crystal display portion formed on one substrate, which is a compound represented by. According to claim 1, wherein the component (C) is represented by the formula [Formula 1e]

A positive type photoresist composition for manufacturing an LCD in which an integrated circuit and a liquid crystal display portion are formed in the same process on one substrate which is a compound represented by. The method according to claim 1, wherein the component (C) is represented by the general formula 1f: [Formula 1f]

A positive type photoresist composition for manufacturing an LCD having an integrated circuit and a liquid crystal display portion formed on one substrate, which is a compound represented by. The positive type photoresist composition for manufacturing an LCD according to claim 1, wherein the component (D) has an integrated circuit and a liquid crystal display portion formed on a substrate containing propylene glycol monoalkyl ether acetate. The positive type photoresist composition for manufacturing an LCD according to claim 1, wherein an integrated circuit and a liquid crystal display portion are formed on one substrate for an i line (365 nm) exposure process. The positive type photoresist composition for manufacturing an LCD according to claim 1, wherein an integrated circuit and a liquid crystal display portion are formed on one substrate for an exposure process having an NA of 0.2 or less. (1) A process of forming a coating film by applying a positive photoresist composition for manufacturing an LCD having an integrated circuit and a liquid crystal display portion formed thereon on one substrate according to any one of claims 1 to 10, (2) Heat-treating the substrate on which the coating film is formed, and forming a resist film on the substrate; A process of performing selective exposure using a mask on which both sides are drawn; (4) a development process using an aqueous alkali solution is performed on the resist film after the selective exposure, and an integrated circuit resist pattern having a pattern dimension of 2.0 μm or less is formed on the substrate. Simultaneously forming a resist pattern for liquid crystal display portions larger than 2.0 µm; The method of forming a resist pattern, comprising a step of including a rinsing step for rinsing the developing solution remaining on the host surface pattern. The formation method of the resist pattern of Claim 11 which performs the said (3) process of performing selective exposure by the exposure process which used i line (365 nm) for the light source. The method of forming a resist pattern according to claim 11, wherein the step (3) of performing selective exposure is performed by an exposure process under a low NA condition where NA is 0.2 or less.

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