KR102092919B1 - Resist stripper composition and a method of stripping resist using the same - Google Patents

Abstract

The present invention relates to a resist stripper composition comprising Hexahydropyrimidin-5-ol.

Description

Resist stripper composition and a method of stripping resist using the same}

The present invention relates to a resist stripper composition and a method for stripping a resist using the same.

Recently, as the demand for realization of high resolution of a flat panel display device increases, efforts to increase the number of pixels per unit area have been continued. According to this trend, a reduction in wiring width is also required, and in order to cope with this, process conditions such as the introduction of a dry etching process are becoming increasingly severe.

In addition, due to the increase in the size of a flat panel display device, an increase in signal speed in wiring is also required, and accordingly, copper having a lower specific resistance than aluminum is being used as a wiring material. In line with this, the required performance for the peeling liquid used in the peeling process, which is a resist removing process, is also increasing.

Specifically, a considerable level of peeling properties are required for the removal power for the etching residue generated after the dry etching process and the corrosion suppression power for the metal wiring, and the processing of the substrate to secure corrosion control power and price competitiveness for aluminum as well as copper A stripper having economical efficiency such as increased number of sheets is required.

In general, water-soluble organic amines such as monoethanolamine and monoisopropanolamine, and organic solvents such as gamma butyllactone and DMSO are used to remove the photoresist. In addition, various types of corrosion inhibitors such as catechol, lesocinol, and benzotriazole are generally used to suppress corrosion of metals generated by amines, and a photoresist stripper composition containing the same has been proposed.

In response to these demands, new technologies have been developed, and as one of them, a composition for exfoliation comprising an amide compound having a specific structural formula is proposed. However, the composition has a limitation that does not have a corrosion inhibitory effect on the copper wiring.

Republic of Korea Registered Patent No. 10-1213735

An object of the present invention is to provide a resist stripper composition that minimizes corrosion of metal wires containing copper or aluminum, and can quickly strip deteriorated or crosslinked resists in a small amount.

In order to achieve the above object,

A resist stripper composition comprising Hexahydropyrimidin-5-ol of Formula 1 below is provided.

[Formula 1]

In addition, the present invention (1) depositing a conductive metal film on a flat panel display substrate;

(2) forming a resist film on the conductive metal film;

(3) selectively exposing the resist film;

(4) developing a resist film after exposure to form a resist pattern;

(5) etching the conductive metal film using the resist pattern as a mask; And

(6) after the etching process, comprising the step of peeling the resist denatured and cured by forming and etching the resist pattern from the substrate using a resist stripper composition,

The resist stripper composition provides a method for stripping a resist, which is a resist stripper composition comprising Hexahydropyrimidin-5-ol of Formula 1 above.

In addition, the present invention provides a method for manufacturing a flat panel for a display device comprising the step of peeling the resist of the substrate for a flat panel using the resist stripper composition.

In addition, the present invention provides a method of manufacturing a flat panel display device comprising the step of peeling the resist of the substrate for a flat panel using the resist stripper composition.

In addition, the present invention provides a flat panel for a display device characterized in that it is manufactured according to the manufacturing method of the flat panel for a display device.

In addition, the present invention provides a flat panel display device characterized in that it is manufactured according to a method of manufacturing a flat panel display device.

The resist stripper composition of the present invention has the advantage of being able to quickly and effectively remove the resist attached to the top of the substrate, and to minimize corrosion of metal wiring including copper or aluminum.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a resist stripper composition comprising Hexahydropyrimidin-5-ol of Formula 1 below.

[Formula 1]

(a) Hexahydropyrimidine -5-ol

The hexahydropyrimidin-5-ol of Chemical Formula 1 strongly penetrates the polymer matrix of denatured or crosslinked resist under various process conditions such as dry etching, wet etching, ashing, or ion implant processing. By breaking the bonds present in the molecule or between the molecules, and forming an empty space in the structurally vulnerable portion in the resist to transform the resist into an amorphous polymer gel mass, it is easy to remove the resist attached to the top of the substrate. Plays a role.

In addition, corrosion of the metal wiring including copper or aluminum is low, and thus corrosion of the metal wiring can be minimized, and even a small amount of deteriorated or cross-linked resist can be quickly removed.

In addition, the resist stripper composition of the present invention may further include a polar organic solvent.

(b) Polar organic solvent

The polar organic solvent may be one or a mixture of two or more selected from quantum polar organic solvents and aprotic polar organic solvents. In addition, it is preferable to select and use one whose boiling point is not too high or low for proper peeling force.

The polar organic solvent serves to dissolve the resist that has become a gel mass by the hexahydropyrimidin-5-ol of Chemical Formula 1, and minimizes re-adsorption and / or re-adhesion of the dissolved resist. , After removing the resist, it is possible to effectively remove the peeling solution in the process of washing the substrate using deionized water.

The quantum polar organic solvent is specifically, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl Ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, polyethylene glycol, poly Alkylene glycol monoalkyl ethers such as propylene glycol, polyethylene glycol monomethyl ether, polyethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol monomethyl ether, propylene glycol monomethyl And the like Terre acetate and tetra-hydroperoxide furyl alcohol, and the compound can be mixed alone or in combination of two or more.

In addition, the aprotic polar organic solvent may include pyrrolidone compounds such as N-methylpyrrolidone (NMP) and N-ethylpyrrolidone; Imidazolidinone compounds such as 1,3-dimethyl-2-imidazolidinone and 1,3-dipropyl-2-imidazolidinone; lactone compounds such as γ-butyrolactone; Sulfoxide compounds such as dimethyl sulfoxide (DMSO) and sulfolane; Phosphate compounds such as triethyl phosphate and tributyl phosphate; Carbonate compounds such as dimethyl carbonate and ethylene carbonato, and formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, and N- (2 -Hydroxyethyl) acetamide, 3-methoxy-N, N-dimethylpropionamide, 3- (2-ethylhexyloxy) -N, N-dimethylpropionamide, 3-butoxy-N, N-dimethyl And amide compounds such as propionamide, and the compounds may be used alone or in combination of two or more.

When the resist stripper composition of the present invention includes the hexahydropyrimidin-5-ol of Formula 1 and a polar organic solvent, 0.1 to 30% by weight of hexahydropyrimidin-5-ol and a polar organic solvent based on the total weight of the composition 70 to 99,9% by weight.

If the content of the hexahydropyrimidin-5-ol is less than 0.1% by weight, the peeling power cannot be increased, and if it exceeds 30% by weight, the effect of increasing the peeling power due to the increase in content does not appear, so economic efficiency cannot be expected.

In addition, when the content of the polar organic solvent is less than 70% by weight, the solubility may be reduced, and the resist may be re-adsorbed and / or re-attached to the substrate in the washing process with deionized water. In addition, when the content exceeds 99.9% by weight, the content of hexahydropyrimidin-5-ol that may be included in the resist stripper composition may be reduced, and peeling power may be reduced.

In addition, the resist stripper composition comprising hexahydropyrimidin-5-ol of Formula 1 and a polar organic solvent may further include a basic compound.

(C) basic compound

The resist stripper composition of the present invention may further use a basic compound in addition to the oxazolidin-5-ylmethaneamine of Formula 1. The basic compound strongly penetrates the polymer matrix of the denatured or crosslinked resist, breaks the bonds present in the molecule or between the molecules, and forms an empty space in a structurally vulnerable part in the resist, thereby forming the resist into an amorphous polymer gel mass. It helps to easily remove the resist attached to the top of the substrate by deforming to.

The basic compound may be one or a mixture of two or more selected from organic basic compounds and inorganic basic compounds.

Specifically, as the basic compound, KOH, NaOH, TMAH (Tetramethyl ammonium hydroxide), TEAH (Tetraethyl ammonium hydroxide), carbonate, phosphate, ammonia, and amines may be used, and these may be used alone or in combination of two or more. have.

The amines include primary amines such as methylamine, ethylamine, monoisopropylamine, n-butylamine, sec-butylamine, isobutylamine, t-butylamine, and pentylamine; Secondary such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, methylethylamine, methylpropylamine, methylisopropylamine, methylbutylamine, methylisobutylamine Amine; Tertiary amines such as diethylhydroxyamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, dimethylethylamine, methyldiethylamine and methyldipropylamine; Choline, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, 2-aminoethanol, 2- (ethylamino) ethanol, 2- (methylamino) ethanol, N-methyl diethanolamine, N, N-dimethyl Ethanolamine, N, N-diethylaminoethanol, 2- (2-aminoethylamino) -1-ethanol, 1-amino-2-propanol, 2-amino-1-propanol, 3-amino-1-propanol, Alkanolamines such as 4-amino-1-butanol and dibutanolamine; (Butoxymethyl) diethylamine, (methoxymethyl) diethylamine, (methoxymethyl) dimethylamine, (butoxymethyl) dimethylamine, (isobutoxymethyl) dimethylamine, (methoxymethyl) diethanolamine , (Hydroxyethyloxymethyl) diethylamine, methyl (methoxymethyl) aminoethane, methyl (methoxymethyl) aminoethanol, methyl (butoxymethyl) aminoethanol, 2- (2-aminoethoxy) ethanol, etc. Alkoxyamine; 1- (2-hydroxyethyl) piperazine, 1- (2-aminoethyl) piperazine, 1- (2-hydroxyethyl) methylpiperazine, N- (3-aminopropyl) morpholine, 2-methyl Piperazine, 1-methylpiperazine, 1-amino-4-methylpiperazine, 1-benzyl piperazine, 1-phenyl piperazine, N-methylmorpholine, 4-ethylmorpholine, N-formylmorpholine, N And cyclic amines which form rings such as-(2-hydroxyethyl) morpholine and N- (3-hydroxypropyl) morpholine.

When the resist stripper composition of the present invention includes the hexahydropyrimidin-5-ol of Formula 1, a polar organic solvent and a basic compound, hexahydropyrimidin-5-ol of Formula 1 with respect to the total weight of the resist stripper composition 0.5 to 25% by weight, 70 to 94% by weight of a polar organic solvent and 0.1 to 20% by weight of a basic compound.

When the basic compound is contained in an amount of less than 0.1% by weight, the peel strength does not improve, and when it is included in an amount exceeding 20% by weight, corrosion strength of the metal wiring including copper or aluminum becomes strong.

In addition, the resist stripper composition comprising hexahydropyrimidin-5-ol of Formula 1, a polar organic solvent, and a basic compound may further include a corrosion inhibitor.

(D) Anti-corrosion agent

By further using a corrosion inhibitor in the resist stripper composition of the present invention, corrosion of aluminum or copper metal wiring can be prevented.

The corrosion inhibitor is specifically, for example, benzotriazole, tolytriazole, methyl tolytriazole, 2,2 '-[[[benzotriazole] methyl] imino] bisethanol, 2,2'- [[[Methyl-1 hydrogen-benzotriazol-1-yl] methyl] imino] bismethanol, 2,2 '-[[[ethyl-1hydrogen benzotriazol-1-yl] methyl] imino] bis Ethanol, 2,2 '-[[[methyl-1 hydrogen-benzotriazol-1-yl] methyl] imino] bisethanol, 2,2'-[[[methyl-1 hydrogen-benzotriazole-1- 1] methyl] imino] biscarboxylic acid, 2,2 '-[[[methyl-1hydrogen-benzotriazol-1-yl] methyl] imino] bismethylamine, 2,2'-[[[amine- Azole compounds such as monohydrogen-benzotriazol-1-yl] methyl] imino] bisethanol;

Quinone compounds such as 1,2-benzoquinone, 1,4-benzoquinone, 1,4-naphthoquinone and anthraquinone;

Alkyl gallates such as catechol, pyrogallol, methyl gallate, propyl gallate, dodecyl gallate, octyl gallate, and gallic acid; And

Succinic amide ester, maleic amide ester, maleic amide ester, fumaric amide ester, oxalic amide ester, malonic amide ester, glutaric amide ester, acetic amide ester, lactic amide ester, citric amide ester, tar Organic acid amide esters such as taric amide esters, glucolic amide esters, formic amide esters, and uric amide esters. The compounds may be used alone or in combination of two or more.

On the other hand, when the resist stripper composition of the present invention includes a corrosion inhibitor, the resist stripper composition is preferably 1 to 20% by weight of the compound of Formula 1, and 70 to 70% polar organic solvent relative to the total weight of the resist stripper composition. 94% by weight, 1 to 15% by weight of the basic compound and 0.1 to 5% by weight of a corrosion inhibitor.

When the corrosion inhibitor is included in an amount exceeding 5% by weight, precipitation or peeling may be affected, and when the corrosion inhibitor is included in an amount of less than 0.1% by weight, the anti-corrosive power of the metal film is weak and thus it is not preferable. In addition, the corrosion inhibitor is more preferably included in 0.5% by weight to 1% by weight.

The resist stripper composition of the present invention can be prepared by advantageously mixing the above-mentioned compounds in a predetermined amount, and the mixing method is not particularly limited and various known methods can be applied without limitation.

In addition, the method for removing the resist of the present invention,

(1) depositing a conductive metal film on a flat panel display substrate;

(2) forming a resist film on the conductive metal film;

(3) selectively exposing the resist film;

(4) developing a resist film after exposure to form a resist pattern;

(5) etching the conductive metal film using the resist pattern as a mask; And

(6) after the etching process, characterized in that it comprises the step of peeling the resist denatured and cured by forming and etching the resist pattern from the substrate using the resist stripper composition of the present invention.

In addition, the peeling method of the present invention, without performing a resist pattern forming process using a mask, after performing a dry etching process such as an etchback (etchback) process or CMP (Chemical Mechanical Polishing) process, the exposed resist film It characterized in that it comprises the step of peeling using the resist stripper composition of the invention.

The process of forming, exposing, developing, etching, and ashing the resist film in the peeling method may be performed by methods commonly known in the art.

Types of the resist include positive and negative g-ray, i-ray and far ultraviolet (DUV) resists, electron beam resists, X-ray resists, ion beam resists, and the like, but are not limited by the components. , The resist to which the resist stripping composition of the present invention is applied particularly effectively is a photoresist film composed of a photoactive compound based on a novolac-based phenolic resin and diazonaptoquinone, and is also effective on a photoresist film composed of a mixture of these. .

As a method for removing resist, denatured or cured resist and dry etching residue on a flat panel display substrate using the resist stripper composition of the present invention, a method of depositing a substrate coated with a resist in the stripper or a stripper And a spraying method. Further, in this case, physical treatment such as irradiation of ultrasonic waves or contact of a brush that rotates or swings from side to side may be used in combination. After the peeling liquid treatment, the peeling liquid remaining on the substrate can be removed by a subsequent cleaning treatment. The washing process is the same as the peeling process except that water or isopropyl alcohol is used instead of the peeling solution.

As the peeling method, a immersion method, a spraying method or a immersion and spraying method can be used. When peeling by immersion, spraying or immersion and spraying, the temperature as the peeling condition is usually 15 to 100 ° C, preferably 30 to 70 ° C, and the immersion, spraying, or deposition and spraying time is usually 30 seconds to 40 minutes, It is preferably 1 minute to 20 minutes, but is not strictly applied in the present invention, and can be easily and appropriately modified by those skilled in the art. If the temperature of the release liquid composition applied on the substrate coated with the resist is less than 15 ° C, the time required to remove the denatured or cured resist film may be excessively long. In addition, when the temperature of the composition exceeds 100 ° C, damage to the lower film layer of the resist film is concerned, and handling of the peeling solution is difficult.

The resist stripper composition of the present invention and a stripping method using the same can be used not only for the removal of a general resist, but also for removal of a resist and an etch residue modified or cured by etching gas and high temperature. In addition, the resist stripper composition of the present invention and the stripping method using the same have the advantage of excellent corrosion protection against metal wiring containing aluminum or copper when used in the manufacture of flat panel displays.

In addition, the present invention provides a method for manufacturing a flat panel for a display device comprising the step of peeling the resist of the substrate for a flat panel using the resist stripper composition of the present invention.

In addition, the present invention provides a method of manufacturing a flat panel display device comprising the step of peeling the resist of the substrate for a flat panel using the resist stripper composition of the present invention.

The flat panel and flat panel display device for a display device manufactured by the above-described manufacturing method are excellent in quality because the resist is completely removed in the manufacturing process and corrosion of the metal wiring containing aluminum and / or copper hardly occurs. Have

In addition, the present invention provides a flat panel and a flat panel display device for a display device characterized in that it is manufactured using the resist stripper composition.

Hereinafter, the present invention will be described in more detail using Examples and Comparative Examples. However, the following examples and comparative examples are intended to illustrate the present invention, and the present invention is not limited to the following and may be variously modified and changed.

Example  1 to 7 and Comparative example  1 to 5. Resist Peeling solution  Preparation of the composition

By mixing the components and contents shown in Table 1 below, a resist stripper composition was prepared.

(Unit:% by weight) division (A) Hexahydropyrimidin-5-ol (B)
Polar organic solvent (C)
Basic compound (D)
Corrosion inhibitor Example 1 5 NMP 95 - - - - Example 2 5 NMF 95 - - - - Example 3 10 NMP
EDG 60
30 - - - - Example 4 10 NMP
EDG 50
30 MDEA 10 - - Example 5 10 NMP
BDG 54.5
30 AEE 5 BTA 0.5 Example 6 10 NMP
EDG 54
30 MEA 5 BTA
MG 0.5
0.5 Example 7 10 NMP
EDG 44.5
40 HEM 5 BTA 0.5 Comparative Example 1 - NMF
EDG 60
40 - - - Comparative Example 2 - NMP
EDG 50
40 AEE 10 - - Comparative Example 3 - NMP
EDG 50
40 MEA 10 - - Comparative Example 4 - NMP
EDG 50
40 HEM 10 - - Comparative Example 5 - NMP
EDG 65
30 MDEA 5 - -

NMP: N-methylpyrrolidone

NMF: N-methylformamide

BDG: Diethylene glycol monobutyl ether

EDG: diethylene glycol monoethyl ether

MDEA: N-methyldiethanolamine

AEE: 2- (2-iminoethoxy) -1-ethanol

MEA: monoethanolamine

HEM: N-hydroxyethylmorpholine

BTA: benzotriazole

MG: methyl gallate

Experimental example  One. Resist Peeling solution  Composition Peeling force  evaluation

In order to confirm the peel strength of the resist stripper compositions of Examples 1 to 7 and Comparative Examples 1 to 5, a Mo / Al and Cu / Ti layer was formed on a glass substrate using a thin film sputtering method according to a conventional method. Thereafter, a substrate in which a metal film was etched by wet etching and dry etching by preparing a photoresist pattern was prepared.

After the resist stripper composition was kept constant at a temperature of 50 ° C., the substrate was immersed for 1 minute to evaluate the peel force.

Thereafter, the substrate was washed with pure water for 1 minute to remove the stripping liquid remaining on the substrate, and the substrate was completely dried using nitrogen to remove the pure water remaining on the substrate after washing. The performance of removing the modified or cured resist and dry etching residue of the substrate was confirmed using a scanning electron microscope (SEM, Hitach S-4700), and the results are shown in Table 2 below.

The criteria for evaluating residue removal are as follows.

◎: Very good

○: Good

△: Normal

×: bad

Experimental example  2. Resist Peeling solution  Composition Anticorrosive  evaluation

The anticorrosive power of the resist stripper compositions of Examples 1 to 7 and Comparative Examples 1 to 5 was evaluated.

The anti-corrosion force evaluation was carried out in the same manner as the peel force evaluation of Experimental Example 1, except that the time for immersing the substrate in the resist stripper composition was 30 minutes.

After the anti-corrosion force evaluation, the Mo / Al and Cu / Ti layers were checked using a scanning electron microscope (SEM, Hitach S-4700), and the results are shown in Table 2 below.

The anticorrosive power evaluation criteria are as follows.

◎: No corrosion

○: almost no corrosion

△: Some corrosion, surface roughness change

×: Etching occurred

division
Peeling force
Anticorrosive Al Cu Example 1 ◎ ◎ ◎ Example 2 ◎ ◎ ◎ Example 3 ◎ ◎ ◎ Example 4 ○ ◎ ◎ Example 5 ◎ ◎ ◎ Example 6 ◎ ◎ ◎ Example 7 ○ ◎ ◎ Comparative Example 1 × ◎ ◎ Comparative Example 2 ◎ × × Comparative Example 3 ◎ × × Comparative Example 4 × ◎ ◎ Comparative Example 5 × ◎ ◎

As shown in Table 2, in the case of Examples 1 to 7 of the resist stripper composition of the present invention, it was confirmed that it has excellent peel strength as well as excellent corrosion resistance to Al and Cu. On the other hand, the resist stripper compositions of Comparative Examples 1 to 5, which do not contain hexahydropyrimidin-5-ol, which is Formula 1 of the present application, showed excellent results only in one of the peel strength and the anticorrosive strength.

From the results of the experiment, it was confirmed that when the hexahydropyrimidin-5-ol of Chemical Formula 1 of the present invention is used in a resist stripper composition, the peel strength is excellent and the anticorrosive power for Al and Cu is maximized.

Claims (14)

A resist stripper composition comprising hexahydropyrimidin-5-ol of Formula 1 below.
[Formula 1]

The method according to claim 1, wherein the resist stripping liquid composition further comprises a polar organic solvent. The method according to claim 2, wherein the polar organic solvent is a resist stripper composition, characterized in that one or a mixture of two or more selected from quantum polar organic solvent and aprotic polar organic solvent. The method according to claim 2, wherein the resist stripper composition comprises 0.1 to 30% by weight of the compound of Formula 1 and 70 to 99.9% by weight of the polar organic solvent relative to the total weight of the resist stripper composition. The resist stripper composition according to claim 2, further comprising a basic compound. The method according to claim 5, wherein the basic compound is a resist stripper composition, characterized in that one or a mixture of two or more selected from organic basic compounds and inorganic basic compounds. The method according to claim 5, wherein the resist stripping solution is characterized in that it comprises 0.5 to 25% by weight of the compound of Formula 1, 70 to 94% by weight of a polar organic solvent and 0.1 to 20% by weight of a basic compound relative to the total weight of the resist stripping agent composition. Composition. The resist stripper composition according to claim 5, further comprising a corrosion inhibitor. The method according to claim 8, wherein 1 to 20% by weight of the compound of Formula 1, 70 to 94% by weight of a polar organic solvent, 1 to 15% by weight of a basic compound, and 0.1 to 5% by weight of a corrosion inhibitor based on the total weight of the resist stripper composition Resist stripper composition comprising a. (1) depositing a conductive metal film on the flat panel display substrate;
(2) forming a resist film on the conductive metal film;
(3) selectively exposing the resist film;
(4) developing a resist film after exposure to form a resist pattern;
(5) etching the conductive metal film using the resist pattern as a mask; And
(6) after the etching step, comprising the step of peeling the resist denatured and cured by forming and etching the resist pattern from the substrate using a resist stripper composition,
The resist stripping solution composition is a stripping method of the resist, characterized in that the resist stripping composition of claim 1. A method for manufacturing a flat panel for a display device comprising the step of peeling the resist of the substrate for a flat panel using the resist stripper composition of claim 1. A method of manufacturing a flat panel display device comprising the step of peeling the resist of the flat panel substrate using the resist stripper composition of claim 1. Flat panel for a display device characterized in that it is manufactured according to claim 11. A flat panel display device manufactured according to claim 12.