KR20000048001A - Positive-type photoresist coating liquid for producing liquid-crystal device and substrates using the same - Google Patents

Abstract

PURPOSE: A positive photoresist coating solution is provided, which is good at controlling striation, drying strain and dropping marks as well as obtains excellent resist pattern formation. CONSTITUTION: A positive photoresist coating solution comprises (i) alkali-soluble resin, (ii) quinone diazide group containing compounds, (iii) nonionic fluorine-silicon surfactant having 10-25 part by weight of fluorine and 3-10 part by weight of silicon, (iv) organic solvent to dissolve the above component.

Description

POSITIVE-TYPE PHOTORESIST COATING LIQUID FOR PRODUCING LIQUID-CRYSTAL DEVICE AND SUBSTRATES USING THE SAME}

The present invention relates to a photoresist coating liquid for producing a liquid crystal element and a substrate using the same. More specifically, the present invention relates to a positive type photoresist coating liquid and a substrate using the same, which control the striation, dry spots and traces of dripping even when applied to a liquid crystal element substrate having a large dimension.

As described in Japanese Laid-Open Patent Publication No. 7-230165, it has been conventionally added to add various surfactants to the positive photoresist to prevent streaks (radial streaks). However, when the substrate is replaced with glass substrates for liquid crystal device manufacture in large sizes such as 360 mm × 460 mm, 550 mm × 650 mm, and 600 mm × 720 mm in the silicon wafer for semiconductor device manufacturing, it becomes a problem with streaks (drying of resist film). There is a problem that spots appear everywhere. This dry unevenness causes a difference in the resist film thickness of several hundred angstroms, and the difference in the film thickness makes the obtained resist pattern dimensions different, which is a problem that cannot be ignored even in liquid crystal devices that have recently required miniaturization.

Such streaks and dry stains can be prevented to some extent by adding a fluorine-based surfactant having a fluorine alkyl group to the positive resist.

However, a new problem arises also with the positive resist coating liquid which added the fluorine-type surfactant. That is, when the positive resist coating liquid is dropped from the nozzle to the center of the glass substrate, and subsequently the resist film is formed by spin coating, the dropping trace is formed in a circular shape at the dropping portion, which causes a problem that it remains without being lost. The dropping trace is presumed to be due to the fluorine component remaining in the dropping portion of the active agent, and if the dropping trace is generated, a difference in resist film thickness occurs, and the obtained resist pattern dimensions are wrong, and the improvement is required.

Accordingly, the present invention provides a positive type photoresist coating liquid for producing a liquid crystal device and a base material using the same, which are excellent in resist pattern shape originally intended for a positive type photoresist composition, do not generate streaks and dry spots, and do not have traces of dripping. The purpose.

Means to solve the problem

That is, in this invention, the objective of this invention was achieved by adding the nonionic fluorine-silicone surfactant which has specific fluorine and silicon type content. Specifically, (a) alkali-soluble resin, (b) quinonediazide group-containing compound, and (c) nonionic fluorine-silicon interface having a fluorine content of 10 to 25% by weight and a silicon content of 3 to 10% by weight. The objective of this invention was achieved by providing the positive photoresist coating liquid for liquid crystal element manufacture which melt | dissolved the activator in (d) organic solvent.

Embodiment of the invention

Each component which comprises the positive photoresist coating liquid for liquid crystal element manufacture of this invention is demonstrated below.

(a) About component (alkali-soluble resin)

It will not specifically limit, if it is used by the conventional positive photoresist composition. Particularly preferred are weight average molecular weights obtained by reacting at least one phenol selected from p-cresol, m-cresol, xyleneol and trimethyl phenol with an acid catalyst and reacting with aldehydes such as formaldehyde in consideration of sensitivity, resolution and resist pattern shape. It is a cresol novolak resin of 3000-15000.

(b) Component (quinonediazide group-containing compound)

The quinonediazide group-containing compound is not particularly limited as long as it is a compound having a quinonediazide group known as a photosensitive component of a positive photoresist.

Such compounds include, for example, naphthoquinone-1,2-diazide- (4 or 5) sulfonyl halides, and 2,3,4-trihydroxybenzophenones, 2,3,4,4'-tetrahydroxy Polyhydroxy benzophenones such as benzophenone; Bis (4-hydroxy-3,5-dimethylphenol) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2-hydroxyphenylmethane, 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-methyl-5-cyclohexylphenyl) -3,4-hydroxyphenylmethane, bis (4-hydroxy- 2-methyl-5-cyclohexylphenyl) -4-hydroxyphenylmethane, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl ] Trisphenols, such as benzene, can be manufactured by condensation reaction and full esterification or partial esterification.

Particularly preferred is an ester obtained by reacting naphthoquinone-1,2-diazide-5-sulfonic acid chloride with 2.0 to 3.5 moles of 1,2,3,4,4'-tetrahydroxybenzophenone to 1 mole of resolution and pattern. It is preferable because it is excellent in shape characteristics.

The component (b) is preferably used in an amount of, for example, 10 to 50 parts by weight based on 100 parts by weight of the component (a).

(c) About component (nonionic surfactant)

The component (c) of the present invention needs to be a nonionic fluorine-silicone surfactant having a fluorine content of 10 to 25% by weight and a silicon content of 3 to 10% by weight. The fluorine content in the active agent is a value that can be obtained by ion chromatography after forming fluorine ions, and silicon content by inductively coupled plasma emission spectrometry (ICP).

More specifically, the fluorine content is quantified by ion chromatography after heating the sample in an electric furnace and burning carbon and hydrogen to generate fluorine ions. In addition, silicon content is quantified by ICP method by preparing a sample as a solid or a solution.

As described in the terms of the prior art, it is known to add various surfactants to the positive resist, but among them, it is preferably used.

Nonionic fluorine-based surfactants having perfluoroalkyl groups and alkyleneoxy groups such as trade names Prorad FC-430 and FC-431 (manufactured by Sumitomo Industries, Inc.);

Nonionic silicon-based surfactants in which an alkylsiloxane group and an alkyleneoxy group are bonded, such as the SI-10 series (manufactured by Tadamoto Motoshi Co., Ltd.) and Mega Pack Painted 31 (manufactured by Dainippon Ink & Chemical Co., Ltd.);

And nonionic fluorine-silicone surfactants in which a perfluoroalkyl ester group such as trade name Mega Pack R-08 and trade name XRB-4 (manufactured by Dainippon Ink, Inc.) is combined with an alkylsiloxane group and an alkyleneoxy group.

In addition, the fluorine content of the Megapack R-08 is 9.0% by weight, the silicon content is 3.0% by weight, and 5.0% by weight and 1.7% by weight for XRB-4, respectively.

However, if a nonionic fluorine-based surfactant is used, for example, a dripping trace is formed. In the case of the nonionic silicon-based surfactant, a portion (called an edge bead) in which the thickness of the resist film is raised near the end of the substrate is formed in the dropping trace. In addition, in the case of R-08 or XRB-4, dropping traces, streaks and dry stains are improved, but not satisfactory, compared to the fluorine-based surfactants or silicon-based surfactants. In addition, when the substrate size used is enlarged, improvement does not occur.

The more preferable fluorine content and silicon content which balances streaks, dry stains, and dripping traces of the component (c) of the present invention are 15 to 25% by weight and 5 to 10% by weight, respectively, and the fluorine content to the silicon content is 2 to 2%. 5 times is preferable. Although this invention (c) component will not be specifically limited if it is in the said range, As an example of a preferable thing, the following nonionic fluorine-silicone surfactant is mentioned.

A perfluoroalkyl group such as trade names X-70-090, X-70-091, X-70-092, and X-70-093 (all manufactured by Shin-Etsu Chemical Co., Ltd.), in which an alkylsiloxane group and an alkyleneoxy group are bonded. And nonionic fluorine and silicon surfactants. These fluorine contents are 21 wt% and the silicon content is 7 wt%.

The substrate used in the present invention is a glass angle substrate for producing a liquid crystal element, specifically, 360 × 460 mm to 550 mm × 650 mm, and also 600 mm × 720 mm, etc. are used, but it continues to be enlarged in the future. The silicon wafers in the manufacture of such large glass substrates and semiconductor devices have different substrate sizes, but the chromium film, molybdenum film, molybdenum alloy film, tantar film, tantar alloy film, silicon nitride film, amorphous silicon film and tin oxide on the substrate. Since the state of the surface of the substrate is different, for example, various films such as an indium oxide (ITO) film and a tin oxide film doped with each other, the positive photoresist for semiconductor device manufacture and the positive photoresist for liquid crystal device manufacture are technically different.

The blending amount of component (c) is in the range of 0.2 to 1% by weight, preferably 0.2 to 0.5% by weight, based on solutes other than component (c) of the coating liquid, such as (a) and (b) and other additives described later. It is preferred to add at. In particular, in the case of semiconductor device manufacturing, the amount needs to be used in a small amount of about 0.025% by weight in order to improve the leakage property to the developing solution. In order to use it, it is preferable to use in the said range.

(d) Component (Organic Solvent)

If it is proposed as an organic solvent of a positive photoresist until now, it will not specifically limit.

Specific examples thereof include polyhydric alcohol derivatives such as ethylene glycol, propylene glycol, ethylene glycol monoacetate, and monomethyl, monoethyl, monopropyl and monobutyl ether of propylene glycol monoacetate;

Alkyl acetates such as methyl acetate, ethyl acetate and butyl acetate;

Ketones such as acetone, methyl ethyl ketone, cyclohexanone and 2-heptanone;

Monooxycarboxylic acid alkyl, such as methyl lactate, ethyl lactate, methyl methoxy dipropionate, and ethyl ethoxy dipropionate, or its derivative (s) is mentioned.

You may mix and use 2 or more types as needed. Especially, the propylene glycol monomethyl ether acetate single solvent, the mixed solvent of ethyl lactate and butyl acetate, and the mixed solvent of ethyl lactate and propylene glycol monomethyl ether acetate are preferable. The mixing ratio of the former is 70 to 90 wt% of ethyl lactate, 30 to 10 wt% of butyl acetate, and the mixing ratio of the latter is 60 to 90 wt% of ethyl lactate and 10 to 40 wt% of propylene glycol monomethyl ether acetate.

Moreover, when 2-40 weight% of (gamma) -butylactone is mixed with the said solvent as needed, the storage stability of a positive resist solution improves and it is further more preferable.

It is preferable that 200-1000 weight part of (d) component is used with respect to a total of 100 weight part of (a) component and (b) component.

OTHER ADDITIVES

Other low-molecular-weight phenols having a weight average molecular weight of about 200 to 600, such as trisphenols used in the component (b) for improving the sensitivity, or hydroxyalkyl-containing such as 2-hydroxyethylpyridine as an adhesion improving agent. You may mix | blend additional components, such as a nitrogen heterocyclic compound and the antihalation agent which has the ability to absorb exposure light further as needed.

Example

Hereinafter, the present invention has been described in detail by way of examples, but is not limited thereto.

In addition, all the physical properties of the obtained positive photoresist coating liquid are evaluated by the following method.

(1) stripes:

The prepared positive photoresist coating liquid was spinner-coated so as to have a film thickness of 1.5 mu m on a 360 mm x 460 mm glass substrate having a Cr film formed thereon, thereby forming a resist coating film. Subsequently, the hot plate temperature is set at 130 ° C. and the first drying is performed for 60 seconds at intervals of about 1 mm, and then the second drying is performed at 110 ° C. for 60 seconds on the hot plate to obtain a resist film. The board | substrate with which this resist film was formed is visually observed, and 0 where the stripe does not generate | occur | produce, 0 where the stripe generation is severe, and set it as (triangle | delta).

(2) dry stains:

In the same manner as in (1), the resist film was visually observed, and 0 where no dry spots were generated, 0 with high occurrence, and Δ with a slight one.

(3) dripping traces

The resist film is visually observed in the same manner as in (1), and 0 for no trace of dropping remains and x for remaining.

(Example 1)

m-cresol and p-cresol are mixed in a weight ratio of 60:40, and formalin is added thereto, and condensed by a conventional method using an oxalic acid catalyst to give 100 parts by weight of cresol novolak resin (weight average molecular weight 10000), 2, 27 parts by weight of an esterification reaction of 1 mole of 3,4,4'-tetrahydroxybenzophenone and 2.2 moles of naphthoquinone-1,2-diazide-5-sulfonyl chloride and a nonionic fluorine and silicon-containing surfactant 0.38 parts by weight (0.3% by weight) of phosphorus X-70-093 was dissolved in a mixture of 324 parts by weight of propylene glycol monomethyl ether acetate and 36 parts by weight of γ-butyrolactone (weight ratio 9: 1), and the pore diameter A positive photoresist coating liquid was prepared by filtration using a 0.2 μm membrane filter. About this, the evaluation test of said (1)-(3) is performed. The results are shown in Table 1.

(Examples 2-5, Comparative Examples 1-5)

A positive photoresist coating liquid was prepared in the same manner as in Example 1 except that the active agent type and amount or solvent was replaced with those shown in Table 1. About this, Table 1 shows the evaluation results of said (1)-(3).

Example or Comparative Example Active agent (% by weight) Solvent (weight ratio) stripe Dry stains No trace Example 1 X-70-093 (0.3) PGMEA: γ-B (9: 1) 0 0 0 Example 2 X-70-093 (0.3) PGMEA 0 0 0 Example 3 X-70-093 (0.3) PGMEA: EL (3/7) 0 0 0 Example 4 X-70-093 (0.1) PGMEA 0 △ 0 Example 5 X-70-093 (0.2) PGMEA 0 0 0 Comparative Example 1 FC-430 (0.05) PGMEA 0 × × Comparative Example 2 SI-10 (0.05) PGMEA 0 × × Comparative Example 3 Painted 31 (0.05) PGMEA 0 × × Comparative Example 4 R-08 (0.05) PGMEA 0 × × Comparative Example 5 XRB-4 (0.05) PGMEA 0 × × PGMEA: Propylene glycol monomethyl ether acetate EL: Ethyl lactate γ-B: γ-butyrolactone

Since the present invention is configured as described above, even when applied to a large substrate, such as a glass angle substrate for manufacturing a liquid crystal device, it is possible to provide a positive photoresist coating liquid that balances streaks, dry stains and traces of dripping.

Claims (8)

(a) alkali-soluble resin, (b) quinonediazide group-containing compound, and (c) nonionic fluorine-silicone surfactant having 10 to 25 wt% of fluorine content and 3 to 10 wt% silicon content ( d) Positive type photoresist coating liquid for liquid crystal element manufacture which melt | dissolves in the organic solvent. The positive type photoresist coating liquid for producing a liquid crystal device according to claim 1, wherein the component (c) is a nonionic fluorine-silicone surfactant in which a perfluoroalkyl group, an alkylsiloxane group, and an alkyleneoxy group are bonded. The nonionic fluorine-silicone surfactant according to claim 1, wherein the component (c) has a fluorine content of 15 to 25% by weight, a silicon content of 5 to 10% by weight, and a fluorine content of 2 to 5 times the silicon content. Positive type photoresist coating liquid for liquid crystal element manufacture which uses the following. The positive type photoresist coating liquid for producing a liquid crystal element according to claim 1, wherein (c) component is blended in an amount of 0.2 to 1% by weight based on solutes other than the component (c) of the coating liquid. The liquid crystal device according to claim 1, wherein (d) the organic solvent is a propylene glycol monomethyl ether acetate alone solvent, a mixed solvent of ethyl lactate and butyl acetate, and a mixed solvent of ethyl lactate and propylene glycol monomethyl ether acetate. Positive photoresist coating liquid. A substrate in which the positive photoresist coating liquid for liquid crystal device production according to any one of claims 1 to 4 is applied onto a glass substrate and dried to form a resist film. The positive type photoresist coating liquid for liquid crystal element manufacture of Claim 1 which mix | blended 10-50 weight part of (b) component with respect to 100 weight part of (a) component. The positive type photoresist coating liquid for liquid crystal element manufacture of Claim 1 which mix | blends (d) component with 200-1000 weight part with respect to a total of 100 weight part of (a) component and (b) component.