KR100558121B1 - Positive photoresist composition for producing a liquid crystal display element and method for forming a resist pattern - Google Patents

Abstract

assignment

Providing a positive type photoresist composition and a method of forming a resist pattern which are excellent in linearity, suitable for the exposure process in low NA conditions, and suitable for i line | wire exposure preferable for manufacture of system LCD.

Resolution

(A) Alkali-soluble resin and (B) Formula 1

In the formula, D represents a hydrogen atom or a 1,2-naphthoquinone diazide-5-sulfonyl group. The quinone diazide ester compound represented by (D) was dissolved in an organic solvent.

Liquid Crystal Display Device, Positive Photoresist Composition, Resist Pattern

Description

POSITIVE PHOTORESIST COMPOSITION FOR PRODUCING A LIQUID CRYSTAL DISPLAY ELEMENT AND METHOD FOR FORMING A RESIST PATTERN}

1 is a plan view of a substrate for explaining the development treatment in Examples and Comparative Examples.

In particular, the present invention provides the use of an exposure process under low NA conditions of NA of 0.2 or less, and The positive photoresist composition suitable for manufacture of the liquid crystal display element using the large glass substrate mentioned above, and the positive photoresist composition suitable for manufacture of a system LCD (Liquid Crystal Display).

In the field of manufacturing liquid crystal display devices using glass substrates, novolak resin-quinonediazide has been used in the manufacture of semiconductor devices in that a resist pattern having a relatively low cost and excellent sensitivity, resolution, and shape can be formed. Many positive type photoresist materials which consist of a system of group containing compounds are used.

However, in the manufacture of a semiconductor device, although a disk-shaped silicon wafer having a maximum diameter of 8 inches (about 200 mm) to 12 inches (about 300 mm) is used, in the production of a liquid crystal display device, 50 × 6OO mm 2 is used. The above rectangular glass substrate is used. Thus, in the manufacturing field of a liquid crystal display element, it cannot be said that the board | substrate which apply | coats a resist composition differs in a material and a shape, but it differs greatly from a silicon wafer in the size. For this reason, the resist material for liquid crystal display element manufacture was requested | required to form the resist pattern with favorable shape and dimensional stability with respect to the wide whole surface of a board | substrate.

Moreover, since much resist material is consumed for manufacture of a liquid crystal display element, it was desired to be an inexpensive material in addition to these characteristics.

On the other hand, as a next-generation LCD, technology development for the high-performance LCD called "System LCD" is now actively progressing, in which integrated circuits such as a driver, a DAC, an image processor, a video controller, and a RAM are formed simultaneously with the display portion on one glass substrate. (Semiconductor FPD World 200l. 9, pp. 50-67).

However, while the pattern dimension of the display portion is about 2 to 10 μm, the pattern dimension of the integrated portion needs to be formed as fine as about 0.5 to 2.0 μm, so that these integrated portions and the display portion are formed under the same exposure conditions. In one case, it is desired that the linearity (the characteristic of reproducing the mask dimensions on the reticle when exposed under the same exposure conditions (the conditions of the mask on the reticle are different but the exposure dose is the same)) is desired.

To improve the resolution (resolution limit), Rayleigh's equation

R = k _l × λ / NA

(Where R is the resolution limit, k _l is the proportional constant determined by resist or process, image forming method, λ is the wavelength of light used in the exposure process, and NA is the numerical aperture of the lens)

As indicated by, it is necessary to use a short wavelength light source or to use a high NA exposure process. Therefore, when forming a fine resist pattern of 2.0 micrometers or less, it is effective to use the photolithography technique using i line | wire (365 nm) exposure which is shorter wavelength than conventional g line | wire (436 nm) exposure.

However, in view of throughput improvement, the exposure area in the liquid crystal field is at least 100 mm 2. It is desired to be about, which is why high NA is difficult.

In the liquid crystal display device manufacturing field, it is generally necessary to have a low NA condition of 0.2 or less for the above reason, but under low NA conditions, it is difficult to form a fine resist pattern having excellent shape, and the resist pattern is not rectangular but tapered. There was a tendency to show shape. Therefore, a resist material for liquid crystal display element manufacturing which can form the fine resist pattern of 2.0 micrometers or less which is excellent in shape also in the low NA conditions of NA or less 0.2 is desired.

There are many reports as a resist material for manufacturing a liquid crystal display element so far, for example, Japanese Patent Laid-Open No. 9-l60231, Japanese Patent Laid-Open No. 9-2ll855, Japanese Patent Laid-Open No. 2000-112l20, Japanese Patent Laid-Open No. 2000 -131835, Unexamined-Japanese-Patent No. 2000-181055, Unexamined-Japanese-Patent No. 2001-75272, etc. are mentioned.

Although these materials are inexpensive and can form resist patterns excellent in coating property, sensitivity, resolution, shape, and dimensional stability on relatively small substrates of about 360 x 460 mm2, for use in the manufacturing process of the system LCD, Further, it is required to further improve the linearity, to form a fine resist pattern even under a low NA condition of NA of 0.2 or less, and to make a material suitable for the i-ray exposure process.

In addition, although Japanese Unexamined Patent Publication No. 2000-29208 and Japanese Unexamined Patent Publication No. 2000-29209 describe a resist composition using a mixture of specific photosensitizers, the publication does not sufficiently describe a composition suitable for producing a liquid crystal display device. It does not describe at all about the manufacturing process of a liquid crystal display element.

An object of the present invention is a method of forming a positive photoresist composition and a resist pattern for producing a liquid crystal display device, which is excellent in linearity, suitable for an exposure process under low NA conditions, and suitable for i-ray exposure, which are preferable for the production of a system LCD. Is to provide.

As a result of earnestly researching in order to solve the said subject, the present inventors found that the positive type photoresist composition containing alkali-soluble resin, a specific quinonediazide ester compound, and a specific organic solvent is excellent in linearity, and is exposed in low NA conditions. A resist material suitable for the process and suitable for i-ray exposure was found to be suitable for the production of a system LCD, and the present invention has been achieved.

The invention according to claim 1 comprises (A) an alkali-soluble resin, (B) quinonediazide ester compound and (D) an organic solvent, wherein the component (B) is represented by the following general formula (1)

[Formula 1]

(Wherein D independently represents a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group, and at least one represents a 1,2-naphthoquinonediazide-5-sulfonyl group)

It is a positive photoresist composition for liquid crystal display element manufacture characterized by containing the quinonediazide ester compound which is represented by.

The invention according to claim 2, wherein the organic solvent contains at least propylene glycol monoalkyl ether acetate, and is a positive photoresist composition for producing a liquid crystal display device according to claim 1.

The invention according to claim 3, wherein the organic solvent contains at least alkyl lactate, characterized in that the positive type photoresist composition for producing a liquid crystal display device according to claim 1 or 2.

The invention according to claim 4, wherein the propylene glycol monoalkyl ether acetate is propylene glycol monomethyl ether acetate (PGMEA), wherein the positive type photoresist composition for producing a liquid crystal display device according to claim 2 is used.

The invention according to claim 5, wherein the alkyl lactate is ethyl lactate (EL), wherein the positive photoresist composition for producing a liquid crystal display device according to claim 3 is used.

The invention according to claim 6, wherein the alkali-soluble resin is a novolak resin obtained by condensation reaction of phenols and aldehydes containing m-cresol and 3,4-xylenol, wherein the liquid crystal display according to claim 1 It is a positive photoresist composition for device manufacture.

The invention according to claim 7, wherein the aldehydes comprise only propionaldehyde and formaldehyde, wherein the positive type photoresist composition for producing a liquid crystal display device according to claim 6 is used.

Invention of Claim 8 contains (C) sensitivity improving agent which consists of alkali-soluble low molecular weight compound which has phenolic hydroxyl group of molecular weight 1000 or less, The liquid crystal in any one of Claims 1-7 characterized by the above-mentioned. Positive type photoresist composition for display element manufacture.

The invention of claim 9 is used in a manufacturing process of a system LCD, wherein the positive type photoresist composition for producing a liquid crystal display device according to any one of claims 1 to 8.

The invention of claim 10 is used in a manufacturing process of an LCD using a large glass substrate of 50Ox60O 2 mm 2 or more, wherein the positive type photoresist composition for producing a liquid crystal display device according to any one of claims 1 to 9. .

The invention according to claim 11 uses an i line (365 nm) exposure process, wherein the positive type photoresist composition for producing a liquid crystal display device according to any one of claims 1 to 10 is used.

Invention of Claim 12 is NA used for the exposure process of 0.2 or less, The positive type photoresist composition for liquid crystal display element manufacture of any one of Claims 1-11 characterized by the above-mentioned.

The invention according to claim 13 is a step of (1) applying the positive photoresist composition according to any one of claims 1 to 8 on a large glass substrate of 50Ox60Omm 2 or more to form a coating film,

(2) heat-processing (prebaking) the glass substrate in which the said coating film was formed, and forming a resist film on a glass substrate,

(3) performing selective exposure to the resist film;

(4) process of developing the resist film after the selective exposure using an aqueous alkali solution to form a resist pattern on the glass substrate,

(5) A method of forming a resist pattern, comprising a rinsing step of washing the developer remaining on the resist pattern surface.

The process according to claim 14, wherein the step (3) of selective exposure is performed using a mask (reticle) on which a mask pattern for forming a resist pattern of 2.0 µm or less and a mask pattern for forming a resist pattern of more than 2.0 µm are simultaneously drawn. The resist pattern of Claim 13 which forms simultaneously the resist pattern of pattern size 2.0 micrometers or less, and the resist pattern larger than 2.0 micrometers on the said glass substrate.

The invention according to claim 15, wherein the step (3) of selective exposure is performed by an exposure process using i-line (365 nm) as a light source, wherein the resist pattern according to claim 13 or 14 is used. Formation method.

The invention according to claim 16 is characterized in that the step (3) of performing selective exposure is performed by an exposure process under a low NA condition of NA of 0.2 or less. It is a formation method of a resist pattern.

Embodiment of the invention

(A) component (alkali-soluble resin)

The alkali-soluble resin as the component (A) is not particularly limited, and can be arbitrarily selected from those which can be commonly used as a film forming material in the positive photoresist composition, and preferably an aromatic hydroxy compound, an aldehyde or a ketone And condensation reaction products, polyhydroxystyrenes and derivatives thereof.

As said aromatic hydroxy compound, For example, phenol, m-cresol, p-cresol, o-cresol, 2, 3- xylenol, 2, 5- xylenol, 3, 5- xylenol, 3, 4 -Xylenols such as xylenol; m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2- alkyl phenols such as tert-butylphenol, 2-tert-butyl-4-methylphenol and 2-tert-butyl-5-methylphenol; alkoxy phenols such as p-methoxyphenol, m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol and m-propoxyphenol; isopropenylphenols such as o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol and 2-ethyl-4-isopropenylphenol; Aryl phenols such as phenyl phenol; Polyhydroxyphenols, such as 4,4'- dihydroxy biphenyl, bisphenol A, resorcinol, hydroquinone, a pyrogallol, etc. are mentioned. These may be used independently and may be used in combination of 2 or more type.

As the aldehydes, for example, formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butylaldehyde, trimethylacetaldehyde, acrolein, crotonaldehyde, cyclohexanealdehyde, furfural, furyl aldehyde, benzaldehyde, benzoaldehyde Phenylacetaldehyde, α-phenylpropylaldehyde, β-phenylpropylaldehyde, o-hydroxybenzaldehyde, m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-methylbenzaldehyde, m-methylbenzaldehyde, p-methylbenzaldehyde, o -Chlorobenzaldehyde, m-chlorobenzaldehyde, p-chlorobenzaldehyde, cinnamic acid aldehyde and the like. These may be used independently and may be used in combination of 2 or more type.

Examples of the ketones include acetone, methyl ethyl ketone, diethyl ketone, diphenyl ketone and the like. These may be used independently and may be used in combination of 2 or more type. Moreover, you may use combining an aldehyde and ketones suitably.

The condensation reaction product of the aromatic hydroxy compound and aldehydes or ketones can be produced by a known method in the presence of an acidic catalyst. As the acidic catalyst at this time, hydrochloric acid, sulfuric acid, formic acid, oxalic acid, paratoluenesulfonic acid and the like can be used.

As said polyhydroxy styrene and its derivative (s), the homopolymer of vinylphenol, the copolymer of vinylphenol, and the comonomer which can be copolymerized with this, etc. are mentioned, for example. Examples of this comonomer include acrylic acid derivatives, acrylonitrile, methacrylic acid derivatives, methacrylonitrile, styrene, α-methylstyrene, p-methylstyrene, o-methylstyrene, p-methoxystyrene and p-chloro Styrene derivatives, such as styrene, are mentioned.

Especially, alkali-soluble resin as (A) component preferable in this invention has a weight average molecular weight (Mw) 2000-20000, Alkali-soluble novolak resin of 3000-12000 is especially preferable, Especially m-cresol and 3, The novolak resin obtained by condensation reaction of the phenols containing 4-xyleneol with the aldehydes containing propionaldehyde and formaldehyde is highly sensitive, and is suitable for the adjustment of the resist material excellent in linearity. Further, the aldehydes are more preferably composed of both propionaldehyde and formaldehyde.

(B) Component (Photosensitive Component: Quinonediazide Esterate)

By using the quinone diazide ester compound represented by the said Formula (1), it becomes the resist material excellent in linearity and suitable for i line | wire exposure.

Further, even under a low NA condition of NA of 0.2 or less, a rectangular and fine resist pattern having excellent shape can be formed without changing the prebaking condition, post-exposure heating (PEB) condition, developing sequence, and the like.

In addition, the average esterification rate of the esterified product is 20 to 80%, preferably 35 to 70%. If the average esterification rate is less than 20%, the residual film rate and resolution are lowered. It is not preferable because the developing residue (scum) is increased.

In addition to the said quinone diazide ester compound, (B) photosensitive component can also use other quinone diazide ester compound.

For example, Formula 2

[Wherein, R ¹ to R ⁸ 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; R ⁹ to R ¹¹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Q is bonded to a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, R ⁹ , a cycloalkyl group having 3 to 6 carbon atoms, or a residue represented by the following 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; c represents an integer of 1 to 3); Each D independently represents a hydrogen atom and a 1,2-naphthoquinone diazide-5-sulfonyl group, and at least one represents a 1,2-naphthoquinone diazide-5-sulfonyl group; a and b represent the integer of 1-3; d represents an integer of 0 to 3; n represents an integer of 0 to 3]

And quinonediazide esters (except for the compounds represented by the formula (1)), specifically 2,4-bis (3,5-dimethyl-4-hydroxybenzyl) -5-hydroxy Linear trinuclear compounds such as phenol and 2,6-bis (2,5-dimethyl-4-hydroxybenzyl) -4-methylphenol; 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-hydroxy Benzyl) -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 Linear 4 nucleophile compounds such as) -5-methylphenyl] methane, 2,4-bis [2-hydroxy-3- (4-hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2, Linear 5 nucleophile compounds such as 4-bis [4-hydroxy-3- (4-hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol Linear Polyphenol Compound, Tris (4-hydroxyphenyl) methane, Bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, Bis (4-hydroxy-3,5-dimethyl Phenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxy 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-3,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, bis (4 -Hydroxyphenyl) -3-methoxy-4-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -3-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxy Phenyl) -2-hi Hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) -3-hydroxyphenylmethane, bis (3-cyclohexyl-4-hydroxy-6-methylphenyl) -4-hydroxyphenylmethane, bis (2 -Methyl-4-hydroxy-5-cyclohexyl) -3,4-dihydroxyphenylmethane, bis (3-cyclohexyl-6-hydroxyphenyl) -3-hydroxyphenylmethane, bis (3-cyclo Hexyl-6-hydroxyphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-6-hydroxyphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-6-hydroxy-4 -Methylphenyl) -2-hydroxyphenylmethane, bis (3-cyclohexyl-6-hydroxy-4-methylphenyl) -4-hydroxyphenylmethane, bis (3-cyclohexyl-6-hydroxy-4-methylphenyl ) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane, bis (4- Hydroxy-2,3,5-trimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-2,3,5-trimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy -2,3,5-trimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,3,5-trimethylphenyl) -4-hydroxy-3-methoxyphenylmethane and the like Quinone diazide ester compounds, such as the tris phenolic polyphenol compound, are mentioned.

However, the amount of the other quinonediazide esterified product is preferably 80% by weight or less, particularly 50% by weight or less, in the photosensitive component, in that it does not impair the effects of the present invention.

In the composition of the present invention, the blending amount of the component (B) is 20 to 70% by weight, preferably 40 to 40% by weight based on the total amount of the alkali-soluble resin which is the component (A) and the following (C) component added as desired. It is preferable to select in the range of 60% by weight. When the compounding quantity of (B) component is less than the said range, the image faithful to a pattern cannot be obtained and transferability will also fall. On the other hand, when the compounding quantity of (B) component exceeds the said range, deterioration of a sensitivity and the homogeneity of the resist film formed will fall and resolution will deteriorate.

(C) component (sensitivity enhancer)

In the composition of this invention, since a sensitivity improvement effect can be acquired by mix | blending an alkali-soluble low molecular compound (sensitivity improving agent) which has a phenolic hydroxyl group of molecular weight l000 or less as (C) component, it is preferable.

Although it does not restrict | limit especially as said low molecular weight compound, For example, the polyphenol compound represented by the said Formula (2 in which D is read as H) can be used, Specifically, 1- [1,1-bis (4 -Methylphenyl) ethyl] -4- [1- (4-hydroxyphenyl) isopropyl] benzene, bis (4-hydroxy-2,3,5-trimethylphenyl) -2-hydroxyphenylmethane, 1,4 -Bis [l- (3,5-dimethyl-4-hydroxyphenyl) isopropyl] benzene, 2,4-bis (3,5-dimethyl-4-hydroxyphenylmethyl) -6-methylphenol, bis ( 4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3 , 5-dimethylphenyl) -3,4-dihydroxyphenylmethane, l- [1- (3-methyl-4-hydroxyphenyl) isopropyl] -4- [1,1-bis (3-methyl- 4-hydroxyphenyl) ethyl] benzene, 2,6-bis [1- (2,4-dihydroxyphenyl) isopropyl] -4-methylphenol, 4,6-bis [1- (4-hydroxy Phenyl) isopropyl] rezo Cin, 4,6-bis (3,5-dimethoxy-4-hydroxyphenylmethyl) pyrogallol, 4,6-bis (3,5-dimethyl-4-hydroxyphenylmethyl) pyrogallol, 2,6 -Bis (3-methyl-4,6-dihydroxyphenylmethyl) -4-methylphenol, 2,6-bis (2,3,4-trihydroxyphenylmethyl) -4-methylphenol, 1,1 -Bis (4-hydroxyphenyl) cyclohexane etc. are mentioned as a preferable thing. Among them, 1- [1,1-bis (4-methylphenyl) ethyl] -4- [1- (4-hydroxyphenyl) isopropyl] benzene and bis (4-hydroxy-2,3,5-tri Methylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, 2,4-bis (3,5-dimethyl-4-hydrate Particular preference is given to hydroxyphenylmethyl) -6-methylphenol, 4,6-bis [1- (4-hydroxyphenyl) isopropyl] resorcin.

When mix | blending (C) component with the composition of this invention, the content is chosen in the range of 5-70 weight% with respect to alkali-soluble resin which is (A) component, Preferably it is 20-60 weight%.

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

(D) Component (Organic Solvent)

The organic solvent used in the present invention is preferably containing propylene glycol monoalkyl ether acetate or alkyl lactate in view of excellent coating properties and excellent film thickness uniformity of the resist film on a large glass substrate.

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

Moreover, although ethyl lactate is the most preferable among alkyl lactates, since the coating nonuniformity tends to arise when using a large glass substrate of 500x600 mm <2> or more, it is preferable to use it by mixing systems with another solvent.

In particular, the composition containing both propylene glycol monoalkyl ether acetate and alkyl lactate is preferable because it is excellent in the film thickness uniformity of a resist film and can form the resist pattern which is excellent in a shape.

When using a mixture of 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.

Moreover, other organic solvents, such as (gamma) -butyrolactone and a propylene glycol monobutyl ether, can also be used, and when using (gamma) -butyrolactone, it is 0.01-1 times by weight ratio with respect to propylene glycol monoalkyl ether acetate, It is preferable. Preferably it is mix | blended in the range of 0.05-0.5 times.

Moreover, ketones, such as an organic solvent of that excepting the above, specifically acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone; Polyhydric alcohols and derivatives thereof such as ethylene glycol, diethylene glycol, ethylene glycol monoacetate, diethylene glycol monoacetate, monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether 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 may also be used, but these may be used for propylene glycol monoalkyl ether acetate, alkyl lactate and mixtures thereof. It is preferable that it is 50 weight% or less.

The composition of the present invention may also contain, if necessary, compatible additives, ultraviolet absorbers for preventing halation, such as 2,2 ', 4,4'-tetrahydroxybenzophenone, 4-dimethylamino-2', 4'-dihydroxybenzophenone, 5-amino-3-methyl-1-phenyl-4- (4-hydroxyphenylazo) pyrazole, 4-dimethylamino-4'-hydroxyazobenzene, 4-diethyl Amino-4'-ethoxy azobenzene, 4-diethylamino azobenzene, curcumin, etc. may be added.

In order to further improve the in-plane uniformity of the resist coating film, the fluorine-based or silicon-based or fluorine-silicone-based surfactant is preferably 0.01 to 0.5% by weight, more preferably 0.02 to 0.4, based on the solid content in the composition. It is advantageous to contain it in the ratio of weight%. The fluorine-based surfactant is not particularly limited and conventionally known ones can be used. Examples of the fluorine-based surfactant include linear nonionic fluorine-based surfactants having a fluorinated alkyl group or a perfluoroalkyl group such as the brand names Florade FC-430 and FC-431 (manufactured by Sumitomo 3M Corporation). There is no restriction | limiting in particular as a silicon type surfactant, A conventionally well-known thing can be used. Examples of this silicon-based surfactant include B, in which an alkylsiloxane group such as the trade name SI-l0 series (manufactured by Takemoto Yushi Co., Ltd.) and mega pack paint 3l (manufactured by Dainippon Ink & Chemical Co., Ltd.) is combined with an ethyleneoxy group and a propyleneoxy group. A warm silicon type surfactant is mentioned. Moreover, it does not restrict | limit especially as a fluorine-silicone surfactant, A conventionally well-known thing can be used. Examples of this fluorine-silicone surfactant include nonionic fluorine-containing a perfluoroalkyl ester group such as the trade name Megapak R-08 (manufactured by Dainippon Ink & Chemicals Co., Ltd.), an alkylsiloxane group, an ethyleneoxy group, and a propyleneoxy group. Silicon-based surfactant, siloxane having a perfluoroalkyl group such as X-70-090, X-70-09l, X-70-092, X-70-093 (manufactured by Shin-Etsu Chemical Co., Ltd.) and a polyether group are bonded. Nonionic fluorine-silicon-based surfactants may be mentioned. These surfactants may be used alone or in combination of two or more thereof.

Especially the composition of this invention can be used suitably for manufacture of a liquid crystal display element and a system LCD. When an example is shown about the preferable use method of the composition of this invention, first, (A)-(C) component and the additive component used as needed are dissolved in the (D) organic solvent, and it is made into the solution, and this is 500 A coating film was formed by applying a spinner or the like on a large glass substrate having a size of 600 mm 2 or more, and the glass substrate on which the coating film was formed was subjected to heat treatment (prebaking) to form a resist film on the glass substrate, and then a light source, For example, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a xenon lamp, and the like are selectively exposed through a desired mask pattern, followed by an alkaline aqueous solution such as, for example, an aqueous solution of 1-10 wt% tetramethylammonium hydroxide (TMAH). The developer is spread over the entire surface of the substrate to be developed to form a resist pattern on the glass substrate. By cleaning the developer remaining on the surface pattern, a resist pattern can be formed with a desired shape. Moreover, you may postbake as needed.

According to the composition of the present invention, even if a selective exposure is performed using a mask (reticle) on which a mask pattern for forming a resist pattern of 2.0 µm or less and a mask pattern for forming a resist pattern of 2.0 µm or more are drawn at the same time, the pattern dimensions on the glass substrate It is possible to simultaneously form a resist pattern of 2.0 μm or less and a resist pattern of 2.0 μm or more in an excellent shape. Moreover, the exposure process which used i line | wire (365 nm) for the light source can be employ | adopted for selective exposure. This can achieve high resolution. Moreover, selective exposure by the exposure process in low NA conditions whose NA is 0.2 or less is also possible. Even under such low NA conditions, the composition of the present invention can form a fine resist pattern of 2.0 μm or less having an excellent shape.

Example

Below, an Example and a comparative example are given and this invention is further demonstrated.

Synthesis Example l (Synthesis of Novolak Resin 1)

(l order reaction)

In a 1-liter four-necked flask, equipped with a mechanical stirrer, a cooler, a 300 ml dropping funnel, a nitrogen gas introduction tube, 86.4 g (0.8 mole) of m-cresol, 2.0 g of p-toluenesulfonic acid and 86.4 g of γ-butyrolactone Was added, and the reaction solution concentration was adjusted to 50% by weight.

Subsequently, while heating with a magnetic stirrer while flowing nitrogen gas, it heated in the oil bath, and when the internal temperature of the reaction solution reached 100 degreeC, 12.22g of 95 weight% propionaldehyde aqueous solution 12 minutes from the dropping funnel over 30 minutes. The dropping was slowly performed, and the reaction was carried out for 4 hours after the dropping.

As a result of sampling the obtained reactant, Mw was 250 and Mw / Mn was 1.65.

(Secondary reaction)

Next, a solution obtained by dissolving 24.4 g (0.2 mol) of 3,4-xylenol in 24.4 g of γ-butyrolactone was placed in the reaction solution after the first reaction, followed by 52.7 g of 37 wt% aqueous formaldehyde solution. Was added dropwise slowly over 30 minutes, and the reaction was carried out for 10 hours after the addition.

After the reaction was completed, the reaction vessel was sufficiently cooled to room temperature, and then the reaction solution was adjusted to a solution having a concentration of 20% by weight using MAK (methyl amyl ketone), washed three times with water using a 3 liter separatory funnel, and concentrated with an evaporator. It was.

Then, it diluted with MAK and methanol, and adjusted to the solution of 15 weight% MAK / methanol = 4/1 (weight ratio).

The solution was placed in a 3-liter separatory funnel, n-heptane was added thereto to remove the low molecular weight containing the monomer, thereby obtaining the desired novolak resin 1 (Mw = 4000).

Synthesis Example 2 (Synthesis of Novolak Resin 2)

(First-order reaction)

In (l-order reaction) of Synthesis Example 1, 86.4 g (0.8 mol) of m-cresol was changed to 97.2 g (0.9 mol) of m-cresol, and 86.4 g of γ-butyrolactone was changed to 97.2 g. Reacted in the same manner as in Synthesis example 1 to obtain a reaction product of Mw = 210 and Mw / Mn = 1.84.

(Secondary reaction)

In (Secondary reaction) of Synthesis Example 1, 24.4 g (0.2 mol) of 3,4-xylenol was changed to 12.2 g (0.l mol) of 3,4-xylenol, and γ-butyrolactone The reaction was carried out in the same manner as in Synthesis Example 1 except that 24.4 g was changed to l2.2 g to obtain a novolak resin 2 having Mw = 6000.

Synthesis Example 3 (Synthesis of Novolak Resin 3)

(First-order reaction)

In (Primary reaction) of Synthesis Example 1, 86.4 g (0.8 mol) of m-cresol was changed to 97.2 g (0.9 mol) of m-cresol, 86.4 g of γ-butyrolactone was changed to 97.2 g, and propion The reaction was carried out in the same manner as in Synthesis Example 1 except that the aldehyde l2.22 g was changed to 9.15 g to obtain a reactant having Mw = l80 and Mw / Mn = 1.72.

(Secondary reaction)

In (Secondary reaction) of Synthesis Example 1, 24.4 g (0.2 mol) of 3,4-xylenol was changed to 12.2 g (0.1 mol) of 3,4-xylenol, and 24.4 g of γ-butyrolactone The reaction was carried out in the same manner as in Synthesis Example 1 except that l was changed to l2.2 g to obtain a novolak resin 3 having Mw = 6000.

Example 1

(A) Ingredients:

100 parts by weight of alkali-soluble resin

(Novolak Resin l Obtained in Synthesis Example l)

(B) Ingredients:

38 parts by weight of a mixture of Bl / B2 = l: l (weight ratio)

(B1: 1 mole of phenolic compound of Formula 1 and 2 moles of 5-NQD (1,2-naphthoquinone diazide-5-sulfonic acid chloride), B2: 1 mole of bis (2-methyl 4-hydroxy-5-cyclohexylphenyl) -3,4-dihydroxyphenylmethane and 2 moles of 5-NQD esterified product)

(C) Ingredients:

25 parts by weight of sensitivity enhancer

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

Surfactant (product name "R-08"; manufactured by Dainippon Ink, Inc.) in an amount equivalent to 350 ppm relative to the total weight of the components (A) to (C) and (A) to (C) Dissolved in PGMEA, adjusted so that the solid content [total of (A) to (C) components] concentration was 25 to 28% by weight, which was filtered using a membrane filter having a pore diameter of 0.2 µm, and a positive photoresist composition. Was prepared.

[Examples 2 to 5] and [Comparative Examples 1 to 4]

A positive photoresist composition was produced in the same manner as in Example 1 except that the components (A), (B) and (D) were changed to those shown in Table 1 below.

The following physical properties were examined about the positive photoresist composition obtained by each said Example and the comparative example. The results are shown in Table 2.

(1) linearity evaluation:

After the sample was applied onto the glass substrate (550 x 650 mm 2) on which the Cr film was formed using a spinner, the temperature of the hot plate was set to 130 ° C. and the first time for 60 seconds by proximity bake with an interval of about 1 mm. Second drying was performed, and then the temperature of the hot plate was set to 120 ° C., and the 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, an i-line exposure apparatus (device name: FX-702J, manufactured by Nikon Corporation; NA = 0.14) was used through a test chart mask (reticle) in which a mask pattern for reproducing a resist pattern of 3.0 µm L & S and 1.5 µm L & S was simultaneously drawn. And selective exposure was performed with the exposure amount (Eop exposure amount) which can reproduce 3.0 micrometers L & S faithfully.

Subsequently, using a developing apparatus (apparatus name: TD-39000 Demonstrator, manufactured by Toyo Kogyo Co., Ltd.) having a slit coater nozzle at 23 ° C. and a 2.38% by weight TMAH aqueous solution, the substrate was extended from one end to the other end. The liquid was placed on the substrate for seconds, held for 55 seconds, washed with water for 30 seconds, and spin dried. 1 is a plan view of a substrate for explaining this development process in the present example and the comparative example. The liquid was contained from the one end X through Y to the other end Z.

Then, the cross-sectional shape of the obtained resist pattern was observed with the SEM (scanning electron microscope) photograph, and the reproducibility of the resist pattern of 0.5 micrometer L & S was evaluated. The results are shown in Table 2.

(2) sensitivity evaluation:

Table 2 shows the result of the Eop exposure amount.

(3) Resolution Evaluation:

The limit resolution in the said Eop exposure amount was calculated | required, and the result was shown in Table 2.

(4) DOF characteristic evaluation:

In the above Eop exposure amount, the focal point was properly shifted up and down, the width of the depth of focus obtained in the range of ± 10% dimensional change rate in 1.5 μm L & S was determined in μm units, and the results are shown in Table 2.

(5) Scum evaluation:

In the said Eop exposure amount, the surface of the board | substrate in which 1.5 micrometer L & S was drawn was observed with SEM (scanning electron microscope), the presence or absence of scum was investigated, and the result was shown in Table 2.

Example (A) (B) (mixed weight ratio) (C) (mixed weight ratio) One Novolak Resin 1 B1 / B2 = 1/1 PGMEA 2 Novolak Resin 1 B1 / B3 = 1/1 PGMEA 3 Novolak Resin 1 B1 / B2 = 1/1 PGMEA / EL = 3/7 4 Novolak Resin 2 B1 / B2 = 1/1 PGMEA 5 Novolak Resin 3 B1 / B2 = 1/1 PGMEA Comparative Example 1 Novolak Resin 1 B4 / B2 = 1/1 PGMEA 2 Novolak Resin 1 B4 / B3 = 1/1 PGMEA 3 Novolak Resin 1 B5 / B2 = 1/1 PGMEA 4 Novolak Resin 1 B5 / B3 = 1/1 PGMEA

B3: 1 mole of 2,3,4,4'-tetrahydroxybenzophenone and 2.34 moles of 5-NQD

B4: esterified of 1 mole of bis [2-hydroxy-3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl] methane with 2 moles of 5-NQD

B5: esterified of 1 mole of bis [4-hydroxy-3- (2-hydroxy-5-methylbenzyl) -5-methylphenyl] methane with 2 moles of 5-NQD

Example Linearity Evaluation (μm) Sensitivity rating (mJ) Resolution Evaluation (μm) DOF evaluation (μm) Scum Reviews One 1.515 40 1.2 20 none 2 1.525 45 1.2 20 none 3 1.515 35 1.2 20 none 4 1.515 40 1.2 20 none 5 1.515 35 1.2 20 none Comparative Example 1 1.700 40 1.4 10 has exist 2 1.750 45 1.4 10 has exist 3 1.850 30 1.5 10 has exist 4 1.800 35 1.4 10 has exist

According to the present invention, a positive photoresist composition and a method of forming a resist pattern for producing a liquid crystal display element, which are excellent in linearity, suitable for an exposure process under low NA conditions, and suitable for i-line exposure, which are preferable for the production of system LCDs. This is provided.

Claims (16)

As a positive photoresist composition for liquid crystal display element manufacture used for the manufacturing process of a system LCD, or at least one side of the manufacturing process of LCD using a large glass substrate of 50Ox60Omm <2> or more, (A) Alkali-soluble novolak resin obtained by condensation reaction of phenols and aldehydes containing m-cresol and 3,4- xylenol, (B) quinone diazide ester compound, and (D) organic solvent (B) component is made of the following Chemical Formula 1 [Formula 1]

(Wherein D independently represents a hydrogen atom or 1,2-naphthoquinonediazide-5-sulfonyl group, and at least one represents a 1,2-naphthoquinonediazide-5-sulfonyl group) The quinone diazide ester compound which is represented by is contained, The positive type photoresist composition for liquid crystal display element manufacture characterized by the above-mentioned. The positive type photoresist composition for manufacturing a liquid crystal display device according to claim 1, wherein the organic solvent contains at least propylene glycol monoalkyl ether acetate. The positive type photoresist composition for producing a liquid crystal display device according to claim 1 or 2, wherein the organic solvent contains at least alkyl lactate. The positive type photoresist composition for manufacturing a liquid crystal display device according to claim 2, wherein the propylene glycol monoalkyl ether acetate is propylene glycol monomethyl ether acetate (PGMEA). 4. The positive type photoresist composition for manufacturing a liquid crystal display device according to claim 3, wherein the alkyl lactate is ethyl lactate (EL). delete The positive type photoresist composition for producing a liquid crystal display device according to claim 1, wherein the aldehydes consist only of propionaldehyde and formaldehyde. (C) A sensitivity improving agent as described in any one of Claims 1, 2, 4 or 7 which consists of alkali-soluble low molecular weight compound which has a phenolic hydroxyl group of 1000 or less molecular weight. Positive photoresist composition for liquid crystal display element manufacture which is used. delete delete The positive photoresist composition for producing a liquid crystal display device according to any one of claims 1, 2, 4 or 7, wherein an i-line (365 nm) exposure process is used. The positive type photoresist composition for manufacturing a liquid crystal display device according to claim 1, wherein NA is used in an exposure process of 0.2 or less. (1) Process of apply | coating positive type photoresist composition in any one of Claim 1, 2, 4 or 7 on 50-60 * mm <2> or more large glass substrates, and forming a coating film, (2) heat-processing (prebaking) the glass substrate in which the said coating film was formed, and forming a resist film on a glass substrate, (3) performing selective exposure to the resist film; (4) process of developing the resist film after the selective exposure using an aqueous alkali solution to form a resist pattern on the glass substrate, (5) A method of forming a resist pattern, comprising a rinsing step of washing the developer remaining on the resist pattern surface. The process for performing selective exposure according to claim 13, wherein the step of performing selective exposure is performed by using a mask (reticle) on which a mask pattern for forming a resist pattern of 2.0 µm or less and a mask pattern for forming a resist pattern of more than 2.0 µm are simultaneously drawn. And forming a resist pattern having a pattern dimension of 2.0 μm or less and a resist pattern of more than 2.0 μm simultaneously on the glass substrate. The method of forming a resist pattern according to claim 13, wherein the step (3) of performing selective exposure is performed by an exposure process using i line (365 nm) as a light source. The method of forming a resist pattern according to claim 13, wherein the step (3) of performing selective exposure is performed by an exposure process under low NA conditions of NA of 0.2 or less.

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