TW201335724A - Photoresist stripper composition and application thereof - Google Patents

Abstract

A photosensitive stripper composition is provided, which comprises hydramine compound (A), diol and/or alcohol ether compound (B) and sulfone and/or sulfoxide organic solvent (C). The photosensitive stripper composition is beneficial for completely stripping the photoresist layer above the metallic circuits rather than corroding the underlying metallic circuits.

Description

Photoresist stripping liquid composition and application thereof

The present invention relates to a photoresist stripper composition, and more particularly to a photoresist stripper composition suitable for removing photoresist on formed metal wiring and avoiding corrosion of metal wiring.

Recently, with the evolution of the photolithography process, the layout of the circuit has become more and more fine. Therefore, in addition to the improvement of the exposure technology and the photoresist component, the technology of the photoresist stripping step is increasingly emphasized.

The photoresist stripping step has been widely used in the lithography process, and the photoresist on the formed metal wiring can be removed by using the photoresist stripping solution. The process of the semiconductor circuit of the liquid crystal panel and the electrode region thereof will be exemplified below, and the conventional photoresist stripping step will be outlined.

In general, a single or multiple layers of a metal film and an insulating film such as cerium oxide may be formed on a ruthenium or glass substrate by chemical vapor deposition (CVD) or sputtering, and the material suitable for the above metal film may be, for example, An aluminum alloy such as aluminum or aluminum-copper; titanium or titanium nitride; and a material suitable for the above-mentioned tantalum substrate may be, for example, amorphous germanium (a-Si), polycrystalline germanium (p-Si) or the like. Next, a photoresist layer is uniformly coated on the metal film and the insulating film, and after exposure and development processing, a photoresist pattern is formed. At this time, the above-mentioned insulating film and metal film are selectively etched by using a photoresist pattern as a mask. Thereafter, the photoresist pattern is removed using a photoresist stripper to form a plurality of metal wirings. However, when a plurality of layers of the multilayer metal wiring are formed, if necessary, the above-mentioned photoresist stripping liquid must be repeatedly treated a plurality of times to remove the photoresist pattern to form an electrode region. For the above-mentioned processes and materials, reference is made to Japanese Laid-Open Patent Publication No. 2005-70230, the Official Publication No. 2004-287288, and the like.

Although the above-mentioned photoresist stripping liquid used has a good photoresist peeling property, it is particularly susceptible to corrosion in metal wirings, particularly aluminum metal wiring.

In view of this, it is urgent to propose a photoresist stripping liquid composition in order to improve the disadvantages of the conventional photoresist stripping liquid which is likely to corrode the formed metal wiring.

Accordingly, an aspect of the present invention provides a photoresist stripping liquid composition comprising an alcohol amine compound (A), a glycol and/or an alcohol ether compound (B), and a hydrazine. Organic solvents (C) of the class and/or the amidoxime class.

Another aspect of the present invention provides a method for resisting peeling by using the above-described photoresist stripping liquid composition to peel off a photoresist layer on a glass substrate, thereby improving the formation of a conventional photoresist stripping liquid which is easily corroded. Disadvantages such as metal lines.

The photoresist stripping liquid composition of the present invention comprises an alcohol amine compound (A), a glycol and/or an alcohol ether compound (B), and an organic solvent (C) of an anthraquinone and/or an anthracene, as described below. It.

Alcohol amine compound (A)

The alcoholamine compound (A) of the present invention includes a primary aliphatic amine, a secondary aliphatic amine, and a tertiary aliphatic amine, and specific examples thereof include monoethanolamine, isopropanolamine, N-methylethanolamine, and N-ethyl. a primary aliphatic amine such as ethanolamine, 2-(2-aminomethoxy)ethanol, and 2-(2-aminoethoxy)ethanol; diethanolamine, N,N-dimethylethanolamine, N,N-diethyl a secondary aliphatic amine such as ethanolamine, 2-(2-aminoethylamino)ethanol or 2-methylaminoethanol; triethanolamine, triethylaminoethanol, etc. Tertiary aliphatic amine.

The above alcohol amine compound (A) is monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, N-methylethanolamine, N-ethylethanolamine, N,N-dimethylethanolamine, N,N. Ethylethanolamine, 2-(2-aminomethoxy)ethanol, 2-(2-aminoethoxy)ethanol or any combination of the above is preferred. The above-mentioned alcohol amine compound (A) can be used singly or in combination of plural kinds.

In general, the above-mentioned alcohol amine compound (A) can form a void between the photoresist and the substrate to which it adheres by breaking the attraction force between molecules or molecules, thereby increasing the swelling effect of the photoresist stripping liquid as a whole, thereby improving light. Stripping resistance and operating temperature dependence, and reducing residue.

When the organic amine compound (A) is not used in the composition of the photoresist stripping liquid of the present invention, the resulting photoresist peeling liquid may have problems such as photoresist residue and poor operation temperature dependency.

Glycols and/or alcohol ethers (B)

The above-mentioned diol and/or alcohol ether compound (B), for example, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol single Dibutyl ether, diethylene glycol monopentyl ether, diethylene glycol monohexyl ether, diethylene glycol monophenyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl Ethylene glycol and/or glycol ethers such as phenyl ether; propylene glycol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, etc., dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol single Propylene glycol and/or propylene glycol ethers such as methyl ether; and 1,3-butanediol.

The above-mentioned diols and/or alcohol ether compounds (B) are ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether. Acetate, ethylene glycol monoethyl ether acetate, diethylene glycol ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether or the above Any combination is preferred. The above-mentioned diols and/or alcohol ether compounds (B) can be used singly or in combination of plural kinds.

In general, the amount of the above-mentioned glycol and/or alcohol ether compound (B) is from 20 parts by weight to 200 parts by weight based on 100 parts by weight of the alcohol amine compound (A), and is 30. It is preferably from 180 parts by weight, more preferably from 50 parts by weight to 150 parts by weight.

When the diol and/or the alcohol ether compound (B) is not used in the composition of the photoresist stripping liquid of the present invention, the swelling effect of the entire stripping liquid obtained is too high, and the aluminum metal is too corrosive and the operating temperature is dependent. Poor sexual problem.

Organic solvents of terpenoids and/or hydrazines (C)

The organic solvent (C) of the anthraquinone and/or the anthracene of the present invention can dissolve the alcohol amine compound (A) and the glycol and/or the alcohol ether compound (B), and does not react with the above components. It is preferred to have a suitable volatility, such as dimethyl hydrazine, diethyl hydrazine, bis(2-hydroxyethyl) fluorene, tetramethylene sulfone (tetramethylene sulfone) or the like. Class; dimethyl azine, tetramethyl sulfoxide.

The organic solvents (C) of the above-mentioned hydrazines and/or hydrazines are dimethyl hydrazine, diethyl hydrazine and bis(2-hydroxyethyl) hydrazine and/or dimethyl fluorene and The amidoxime class of tetramethylphosphonium is preferred. The above organic solvents (C) of the anthraquinones and/or the anthracene may be used singly or in combination of plural kinds.

In general, the amount of the organic solvent (C) of the above terpenoids and/or anthraquinones is from 200 parts by weight to 1000 parts by weight based on 100 parts by weight of the alcohol amine compound (A). More preferably, from 250 parts by weight to 900 parts by weight, still more preferably from 300 parts by weight to 800 parts by weight.

When the organic solvent (C) of an anthracene and/or an anthracene is used in the composition of the photoresist stripper of the present invention, the resulting photoresist stripper may have problems such as photoresist residue and poor operation temperature dependency.

Amidoxime organic solvent (D)

In the present invention, the organic solvent (D) of the guanamine can dissolve the alcohol amine compound (A) and the diol and/or the alcohol ether compound (B), and the organic matter of the quinone and/or the fluorene. The solvent (C) is mutually soluble, does not react with the above components, and has a suitable volatility, and specific examples thereof include: meglumine, acetamide, N-methylformamide, N-methylacetamide, N-ethylformamide, N-ethylacetamide, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N , N-diethylacetamide, N,N-dimethylimidazole and other guanamines; N-methyl-2-pyrrolidone (NMP), N-ethyl-2- Indoleamines such as pyrrolidone.

The above organic solvents (D) of guanamines are N-methyl-2-pyrrolidone, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-ethylethyl Indoleamine, N,N-diethylacetamide, formamide, N-methylformamide, N,N-dimethylformamide, N-ethylformamide, N,N-di Ethylformamide or any combination of the above is preferred. The organic solvent (D) of the above guanamines may be used singly or in combination of plural kinds.

In general, the organic solvent (D) of the above guanamine is used in an amount of 50 parts by weight to 500 parts by weight, based on 100 parts by weight of the alcohol amine compound (A), and then 50 parts by weight to 450 parts by weight. The parts by weight are more preferably from 100 parts by weight to 400 parts by weight.

When the organic solvent (D) of the guanamine is used as the composition of the photoresist stripping liquid of the present invention, it is helpful to infiltrate the alcohol amine compound (A) into the interior of the photoresist to improve the photoresist stripping ability. If used in combination with an organic solvent (C) of anthraquinones and/or anthraquinones, the photoresist stripping ability can be improved.

Photoresist stripping liquid composition for liquid crystal panel process

The photoresist stripping liquid composition of the present invention generally comprises the above alcohol amine compound (A), a glycol and/or an alcohol ether compound (B), and an organic solvent of a terpenoid and/or an anthraquinone (C). The mixture is placed in a stirrer to be stirred and uniformly mixed into a solution state to prepare a photoresist stripping liquid composition in a solution state.

The amount of the diol and/or the alcohol ether compound (B) to be used is 20 parts by weight to 200 parts by weight, based on the amount of the alcohol amine compound (A), and the hydrazines and/or the hydrazines. The organic solvent (C) is used in an amount of from 200 parts by weight to 1000 parts by weight, and then from 30 parts by weight to 180 parts by weight of the diol and/or the alcohol ether compound (B) and from 250 parts by weight to 900 parts by weight The organic solvent (C) of an anthraquinone and/or an anthracene is preferably 50 parts by weight to 150 parts by weight of the diol and/or the alcohol ether compound (B) and 300 parts by weight to 800 parts by weight. The organic solvent (C) of anthraquinone and/or anthraquinone is more preferred.

Further, the above-mentioned photoresist stripping liquid composition may further optionally contain an organic solvent (D) of a guanamine, wherein the organic amine solvent (D) is used in an amount of 100 parts by weight based on the alcohol amine compound (A). The amount used is from 50 parts by weight to 500 parts by weight, more preferably from 50 parts by weight to 450 parts by weight, still more preferably from 100 parts by weight to 400 parts by weight.

Secondly, the method for preparing the photoresist stripping liquid composition of the present invention is not particularly limited. For example, the alcohol amine compound (A), the glycol and/or the alcohol ether compound (B) can be directly added to the anthraquinone and / or dispersed in an organic solvent (C) of an anthraquinone type, or a part of the anthraquinone compound (A), a glycol, and/or an alcohol ether compound (B) dispersed in a part of the anthraquinone and / or the medium of the organic solvent (C) of the hydrazine group, and then add the remaining part of the alcohol amine compound (A), the diol and/or the alcohol ether compound (B), and the hydrazine and/or sub It is prepared from an organic solvent (C) of anthraquinone.

The photoresist stripper composition of the present invention can be applied to remove the photoresist layer above the formed metal line, especially the photoresist layer on the formed aluminum metal line, completely removing the photoresist layer and avoiding corrosion underneath it. Metal lines.

Method of photoresist stripping

The method of photoresist stripping of the present invention can be carried out by the following exemplified methods.

First, a single or a plurality of aluminum-containing metal films are formed on a glass substrate by chemical vapor deposition (CVD) or sputtering, wherein the substrate is specifically, for example, an alkali-free glass or sodium used for a liquid crystal display device or the like. Calcium glass, hard glass (Pyrus glass), quartz glass, and a transparent conductive film attached to the glass; or a photoelectric conversion device substrate (such as a germanium substrate) used in a solid-state imaging device or the like.

Next, after uniformly coating the photoresist layer on the aluminum-containing metal film, most of the solvent is removed by drying under reduced pressure, and then the solvent is removed by pre-bake to form a pre-baked coating film. . Among them, the conditions of drying under reduced pressure and pre-baking vary depending on the type of each component and the blending ratio. Usually, the drying under reduced pressure is carried out at a pressure of 0 mmHg to 200 mmHg for 1 second to 60 seconds, and the pre-bake is at 70. It is carried out at a temperature of from ° C to 110 ° C for 1 minute to 15 minutes. After pre-baking, the pre-baked film is exposed between the specified masks, immersed in the developer at a temperature of 23±2° C. for 15 seconds to 5 minutes for development, and is not partially removed to form a resist pattern. . For the light used for exposure, ultraviolet rays such as g-line, h-line, and i-line are preferable, and the ultraviolet device may be a (super) high-pressure mercury lamp and a metal halide lamp.

Further, specific examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, sodium citrate, sodium methyl citrate, aqueous ammonia, ethylamine, diethylamine, and Basicity of methylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-(5,4,0)-7-undecene Compound. The concentration of the developer is generally from 0.001% by weight (% by weight) to 10% by weight, preferably from 0.005% by weight to 5% by weight, more preferably from 0.01% by weight to 1% by weight. When such a developer is used, it is usually washed with water after development. Next, the pattern is air-dried with compressed air or compressed nitrogen, and then post-baked by a heating device such as a hot plate or an oven. The post-baking temperature is usually from 150 to 250 ° C, wherein the heating time using the hot plate is from 5 minutes to 60 minutes, and the heating time in the oven is from 15 minutes to 150 minutes.

After pre-baking, exposure, development, and post-baking, a photoresist pattern film is formed. At this time, the photoresist film which is not protected by the photoresist film is selectively etched by using an etching solution such as phosphoric acid, acetic acid or nitric acid as a mask. Thereafter, the glass substrate is immersed in the above-mentioned photoresist stripping solution, immersed at a temperature of 24 ° C to 100 ° C for 30 seconds to 30 minutes, or immersed for 1 minute to 20 minutes, after peeling off the photoresist pattern on the glass substrate, A plurality of metal wirings and electrode regions are formed. Thereafter, the glass substrate forming the metal wiring is sequentially subjected to a cleaning step and a drying step.

The following embodiments are used to illustrate the application of the present invention, and are not intended to limit the present invention. Those skilled in the art can make various changes without departing from the spirit and scope of the present invention. Retouching.

Hereinafter, the photoresist stripping liquid compositions of Examples 1 to 10 and Comparative Examples 1 to 3 were prepared according to the first table, and the photoresist stripping liquid composition was evaluated by the following evaluation method.

[Evaluation method] Example 1

The positive photosensitive resin composition of the novolak resin was placed in a coater (Model MS-A150; purchased from Shinko Trading, Taiwan) and coated by spin coating at 2吋×2吋. The glass substrate containing the aluminum metal film was dried under reduced pressure at 100 mmHg for 5 seconds, and then prebaked in an oven at 110 ° C for 1.5 minutes to form a prebaked coating film having a film thickness of 3.5 μm. The prebaked coating film was placed between the designated masks, irradiated with a light amount of 20 mJ/cm ² by a stepping machine (Nikon 1755G7A), and then subjected to a 0.84% potassium hydroxide aqueous solution at 23 ° C. The film was developed for 1 minute, and the coating film on the exposed portion of the substrate was removed, and then washed with pure water. Then, after baking at 170 ° C for 15 minutes in an oven, a photoresist film having a thickness of 3.0 μm was formed on the glass substrate containing the aluminum metal film.

The glass substrate containing the photoresist line film is etched with an etching solution such as phosphoric acid, acetic acid or nitric acid to etch an aluminum-containing metal film not protected by the photoresist film. After completion, it is washed with deionized water and dried to obtain a glass substrate containing a photoresist line film.

The glass substrate containing the photoresist line film was immersed in the photoresist stripping liquid composition of Example 1 shown in Table 1 at 50 ° C for 20 minutes. Next, the glass substrate was washed with deionized water and dried, and then the photoresist film peelability, the corrosion resistance of the aluminum-containing metal line, and the operation temperature dependence were observed by a scanning electron microscope (SEM), and the results were as follows. Table 1 shows.

Examples 2 to 9 and Comparative Examples 1 to 3

Examples 2 to 9 and Comparative Examples 1 to 3 used the same operation method as in Example 1, except that the types and mixing amounts of the photoresist stripping liquid composition were changed, and the details and subsequent evaluation results are shown in the first section. 1 table.

1. Photoresist stripping:

The above-mentioned glass substrate having an aluminum-containing metal wiring was observed by SEM to observe the photoresist residue, and evaluated according to the following criteria:

◎: no photoresist residue

○: a little photoresist residue

╳: A large amount of photoresist residue

2. Corrosion resistance of aluminum-containing metal lines:

The above-mentioned glass substrate having an aluminum-containing metal wiring was observed by SEM to observe the surface of the aluminum-containing metal wiring, and evaluated according to the following criteria:

○: There is no corrosion on the surface of the aluminum-containing metal line

╳: Honeycomb-like defects appear on the surface of aluminum-containing metal lines

3. Operating temperature dependence:

The etched photoresist film and the aluminum substrate-containing glass substrate were respectively immersed in the photoresist stripping liquid compositions of the examples and the comparative examples at 90 ° C, 70 ° C, and 50 ° C for 10 minutes, followed by After washing with ionized water, the residual photoresist was observed by SEM and evaluated according to the following criteria:

○: No photoresist remains at 90 ° C, 70 ° C and 50 ° C.

╳: At 90 ° C, 70 ° C and 50 ° C, there are photoresist residues.

From the results of Example 1 to Example 9 of Table 1, it is understood that the alcohol amine compound (A), the glycol and/or the alcohol ether compound (B), and the anthraquinones and the like are controlled by the composition of the resist stripper. / or the use amount of the organic solvent (C) of the anthraquinone type, has better photoresist peeling resistance and corrosion resistance of the aluminum-containing metal line and operating temperature dependence, and an organic solvent of anthraquinone and/or anthraquinone When (C) is used in combination with the organic solvent (D) of the guanamine, the photoresist is more excellent in peeling resistance, so that the object of the present invention can be attained. In contrast, after the photoresist stripping liquid composition of Comparative Example 1 to Comparative Example 3 of the first table was subjected to photoresist peeling, the photoresist peeling resistance and the corrosion resistance of the aluminum-containing metal wiring were less desirable, and the operation was performed. Temperature dependence is poor.

It should be noted that, although the present invention is exemplified by specific compounds, compositions, reaction conditions, processes, analytical methods or specific instruments, the composition of the photoresist stripper of the present invention and its application, but any of the technical fields of the present invention It is to be understood by those skilled in the art that the present invention is not limited thereto, and other compounds, compositions, reaction conditions, processes, analytical methods or methods may be used for the photoresist stripper composition of the present invention without departing from the spirit and scope of the present invention. The instrument is carried out and applied in other technical fields.

The present invention has been disclosed in the above embodiments, but it is not intended to limit the invention, and any one of ordinary skill in the art to which the present invention pertains can be modified and retouched without departing from the spirit and scope of the invention. Therefore, the scope of the invention is defined by the scope of the appended claims.

Claims (9)

A photoresist stripping liquid composition comprising: an alcohol amine compound (A); a glycol and/or an alcohol ether compound (B); and an organic solvent (C) of an anthraquinone and/or an anthracene. The photoresist stripping liquid composition according to claim 1, wherein the diol and/or the alcohol ether compound (B) is used based on 100 parts by weight of the alcohol amine compound (A). The amount used is from 20 parts by weight to 200 parts by weight, and the organic solvent (C) of the hydrazine and/or the fluorene is used in an amount of from 200 parts by weight to 1000 parts by weight. The photoresist stripping liquid composition according to claim 1, further comprising at least an organic solvent (D) of a guanamine. The photoresist stripping liquid composition according to claim 1, wherein the organic amine solvent (D) is used in an amount of 100 parts by weight based on the amount of the alcohol amine compound (A). 50 parts by weight to 500 parts by weight. The photoresist stripping liquid composition according to claim 1, wherein the alcohol amine compound (A) is selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, and N-methylethanolamine. , N-ethylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, 2-(2-aminomethoxy)ethanol and 2-(2-aminoethoxy)ethanol At least one of a group. The photoresist stripping liquid composition according to claim 1, wherein the glycol and/or the alcohol ether compound (B) is selected from the group consisting of ethylene glycol and propylene glycol. Or ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol ether, diethylene glycol monomethyl At least one of a group consisting of ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, and diethylene glycol monobutyl ether. The photoresist stripping liquid composition according to claim 1, wherein the organic solvent (C) of the anthraquinone and/or the anthracene is selected from the group consisting of dimethyl hydrazine and diethyl hydrazine. At least one of the group consisting of the quinone and/or dimethyl hydrazine of bis(2-hydroxyethyl) hydrazine and the hydrazine of the tetramethyl fluorene. The photoresist stripping liquid composition according to claim 4, wherein the organic solvent (D) of the guanamine is selected from the group consisting of N-methyl-2-pyrrolidone, acetamide, N-A Ethylamine, N,N-dimethylacetamide, N-ethylacetamide, N,N-diethylacetamide, formamide, N-methylformamide, N,N At least one of a group consisting of dimethylformamide, N-ethylformamide, and N,N-diethylformamide. A method for resisting peeling, comprising: peeling off a photoresist layer on a glass substrate using the photoresist stripping liquid composition according to any one of claims 1 to 8; and the glass substrate A washing step and a drying step are sequentially applied.