KR102223871B1 - Resist stripper composition and a method of stripping resist using the same - Google Patents

Abstract

The present invention is a resist stripper composition comprising at least one amide compound selected from compounds represented by Formula 1 and Formula 2, glycolamine represented by Formula 3, and glycol ether represented by Formula 4, and resist stripping using the same Provides a way.

Description

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

The present invention relates to a resist stripper composition and a resist stripping method using the same, and more particularly, a resist stripper composition capable of effectively removing a resist pattern deformed by etching during a manufacturing process of a flat panel display, and using the same. It relates to a method of peeling a resist.

In recent years, as the demand for high resolution implementation of flat panel displays increases, efforts to increase the number of pixels per unit area are continuing. In accordance with this trend, a reduction in wiring width is also required, and in order to cope with it, a dry etching process is introduced, and process conditions are becoming increasingly severe. In addition, due to the increase in the size of the flat panel display device, an increase in signal speed in the wiring is also required, and accordingly, copper, which has a lower specific resistance than aluminum, is being put into practical use as a wiring material. In line with this, the required performance for a stripper used in a stripping process, which is a resist removal process, is also increasing. Specifically, a considerable level of peeling characteristics is required for the removal power of the deformed resist and the corrosion inhibition power of the metal wiring generated after the dry etching process. In addition, in order to secure price competitiveness, economic feasibility such as an increase in process speed, an increase in the number of days for which the composition can be stored, and an increase in the number of substrates to be processed are also required.

In response to the demands of the industry, new technologies are being released, and representative ones are as follows:

Republic of Korea Patent Registration No. 10-1304723 is an amide compound represented by the following formula (1), a water-soluble organic amine compound, a hydroxyl amine salt compound, a water-soluble polar aprotic solvent, an alkylene glycol alkyl ether compound, a compound represented by the following formula (2), and an aromatic hydride. A photoresist stripper comprising a oxy compound and deionized water is disclosed:

[Formula 1]

[Formula 2]

Korean Patent Application Publication No. 10-2003-0026822 discloses N-methyl-pyrrolidone (N-methyl-2-pyrrolidone), N. N-dimethyl-acetamide, dimethyl-formamide, and N. N-methyl-form. Disclosed is a resist stripper comprising a composition comprising a highly polar solvent containing at least one selected from amides and an amine compound soluble in water.

The stripper is characterized by containing an amide compound, but in consideration of physical properties such as polarity, reactivity with amine, and boiling point of the included amide compounds, in order to sufficiently satisfy the requirements of this field, additional I think it needs improvement.

Korean Patent Registration No. 10-1304723 Republic of Korea Patent Publication No. 10-2003-0026822

The present invention is to solve the problems of the prior art as described above, and the polarity of the stripper is large, so that the removal ability of the resist pattern deformed after wet or dry etching is excellent, the storage stability is excellent, and the process loss is small. An object of the present invention is to provide a resist stripper composition and a resist stripping method using the same.

The present invention,

It provides a resist stripper composition comprising at least one amide compound selected from compounds represented by the following Formulas 1 and 2, a glycolamine represented by the following Formula 3, and a glycol ether represented by the following Formula 4:

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

In the above, R1 is hydrogen or C1-C4 aliphatic hydrocarbon.

In addition, the present invention

(I) depositing a conductive metal film on a flat panel display substrate,

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

(III) selectively exposing the resist film;

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

(V) etching the conductive metal layer using the resist pattern as a mask; And

(VI) After the etching process, a resist stripping method comprising the step of removing the resist modified and cured by forming and etching the resist pattern from the substrate using the resist stripper composition of the present invention is provided.

In addition, the present invention

A method of manufacturing a flat panel for a display device and a method of manufacturing a flat panel display device, comprising the step of removing a resist from a substrate for a flat panel using the resist stripper composition of the present invention.

The resist stripper composition of the present invention has a high boiling point of the amide compound contained in the stripper, thereby minimizing process loss, and has excellent storage stability due to its low reactivity with amines. Provides an excellent effect.

The present invention relates to a resist stripper composition comprising at least one amide compound selected from compounds represented by the following formulas (1) and (2), a glycolamine represented by the following formula (3), and a glycol ether represented by the following formula (4) will be:

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

In the above, R1 is hydrogen or C1-C4 aliphatic hydrocarbon.

Examples of the C1 to C4 aliphatic hydrocarbons include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, and t-butyl.

Since the compound of Formula 1 has a higher molecular weight compared to other amide compounds, the breaking point is high, and the compound of Formula 2 has a cyclic structure and thus has a high polarity, and a high boiling point because hydrogen bonds can be strongly formed between molecules. Therefore, the compounds of Formulas 1 and 2 can minimize the amount of evaporation loss of the stripper.

In addition, the compound of Formula 1 causes a steric hindrance to the ethyl group bonded to the carbonyl group to reduce reactivity with an amine. Since the compound of Formula 2 also has a ring structure, it has low reactivity with an amine. Accordingly, the compounds of Formulas 1 and 2 have characteristics of minimizing changes in the composition of the stripper over time and the change in properties of the stripper due to the reaction of an amine and an amide.

The amide compound may be included in 5 to 50% by weight, more preferably 10 to 40% by weight, based on the total weight of the composition. When the amide compound of Formula 1 is contained in an amount of less than 5% by weight, the effect of increasing the peeling rate on the resist decreases, and when it exceeds 50% by weight, the metal surface due to reprecipitation of the dissolved resist is Contamination problems can arise. In addition, since amide compounds are relatively expensive, they are disadvantageous in terms of cost as well.

The glycolamine serves to decompose a resist crosslinked product that is deformed or not deformed by etching into small structural units.

In particular, the glycolamine contains a primary amino group and has a high decomposition reactivity to the modified photoresist, and it contains a hydroxyl group in the molecule and has a low vapor pressure, so that process loss can be suppressed. It can be preferably used.

The glycolamine may be included in an amount of 2 to 25% by weight, more preferably 3 to 10% by weight, based on the total weight of the composition. When the organic amine compound is contained in an amount of less than 2% by weight, the peeling effect on the resist is insufficient, and when it exceeds 25% by weight, the corrosion rate for the metal wiring may increase.

The glycol ether assists the amide compound to dissolve the gelled resist polymer, and also minimizes re-precipitation of the dissolved resist in the stripping solution by facilitating the removal of the stripping solution by water during the DI rinsing process after the resist stripping. do. In addition, it serves to improve the performance of the glycolamine, penetrates into the deteriorated or crosslinked resist, and breaks the bonds existing within or between molecules.

In particular, the glycol ether contains two or more ethylene glycol groups in the molecule and contains a hydroxy group, so it has a high boiling point and plays a role of suppressing process loss. Also, since it contains four or less ethylene glycol groups, the molecular weight increases and the viscosity increases accordingly. It does not cause a decrease in the peeling rate of the resist due to. In addition, since one end is alkylated with a lower hydrocarbon, the solubility in water does not decrease and the solubility of the resist is improved. In addition, it can be preferably used in the stripper composition of the present invention in that it serves to suppress the precipitation of the resist during the rinsing process.

The glycol ether may be included in a residual amount such that the total weight of the composition is 100% by weight.

The stripper composition of the present invention may include 5 to 50% by weight of an amide compound, 2 to 25% by weight of glycolamine, and a remaining amount of glycol ether based on the total weight of the composition.

In addition to the above components, the stripper composition of the present invention may further include components generally used in this field, such as surfactants, corrosion inhibitors, and water. When these components are further included, the content of polyethylene glycol is reduced in the above, and the components may be added in a range of the content.

Examples of the surfactants include anionic surfactants, cationic surfactants, and nonionic surfactants. Among these, it is preferable to use a nonionic surfactant having excellent wettability and less generation of bubbles.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether type, polyoxyethylene alkylphenyl ether type, polyoxyethylene polyoxypropylene alkyl ether type, polyoxyethylene polyoxybutylene alkyl ether type, and polyoxyethylene alkylamino ether. Type, polyoxyethylene alkylamido ether type, polyethylene glycol fatty acid ester type, sorbitan fatty acid ester type, glycerin fatty acid ester type, alkyrolamide type and glycerin ester type surfactant. More than one species can be used together.

The surfactant is preferably contained in an amount of 0.001 to 1.0% by weight based on the total weight of the composition. When included in the content range as described above, it is advantageous for uniform peeling of the substrate, and at the same time, it is advantageous to prevent the tendency to be difficult to handle due to severe foamability of the peeling solution.

The corrosion inhibitors are benzotriazole, methyl gallate, tolitrizol, methyl tolitrizol, 2,2'-[[[benzotriazole]methyl]imino]bisethanol, 2,2'-[[ [Methyl-1hydrogen-benzotriazol-1-yl]methyl]imino]bismethanol, 2,2'-[[[ethyl-1hydrogen benzotriazol-1-yl]methyl]imino]bisethanol, 2,2'-[[[methyl-1 hydrogen-benzotriazol-1-yl]methyl]imino]bisethanol, 2,2'-[[[methyl-1 hydrogen-benzotriazol-1-yl] Methyl]imino]biscarboxylic acid, 2,2'-[[[methyl-1hydrogen-benzotriazol-1-yl]methyl]imino]bismethylamine, 2,2'-[[[amine-1hydrogen] And azole compounds such as -benzotriazol-1-yl]methyl]imino]bisethanol, and these may be used alone or in combination of two or more.

The corrosion inhibitor has excellent anti-corrosion ability of metal wires containing aluminum and/or metal wires containing copper, and particularly has excellent anti-corrosion power for copper and metals containing the same.

The corrosion inhibitor is preferably contained in an amount of 0.01% to 5% by weight based on the total weight of the composition. If the content of the corrosion inhibitor is less than 0.01% by weight, corrosion may occur in copper or metal wiring containing the same in the peeling or rinsing process with deionized water, and if it exceeds 5% by weight, corrosion prevention due to an increase in the content of the corrosion inhibitor It is not desirable because the effect is no longer improved.

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

The present invention also provides a resist stripping method, characterized in that the resist stripping liquid composition of the present invention is used. The above resist peeling method,

(I) depositing a conductive metal film on a flat panel display substrate,

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

(III) selectively exposing the resist film;

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

(V) etching the conductive metal layer using the resist pattern as a mask; And

(VI) After the etching process, the resist pattern is formed and the resist modified and cured by etching is removed from the substrate using the resist stripper composition of the present invention.

In addition, in the exfoliation method of the present invention, a dry etching process such as an etchback process or a chemical mechanical polishing (CMP) process is performed, and then the exposed resist film is viewed without performing a resist pattern formation process using a mask. It includes a method of peeling with the peeling liquid composition of the invention.

Among the stripping methods, the resist film formation, exposure, development, etching, and ashing processes may be performed by methods commonly known in the art.

Examples of the resist types include positive and negative g-ray, i-ray and deep ultraviolet (DUV) resists, electron beam resists, X-ray resists, ion beam resists, etc., and are not limited to their constituents. , The resist to which the composition for resist stripping of the present invention is particularly effectively applied is a photoresist film composed of a photoactive compound based on a novolac-based phenol resin and diazonaphthoquinone, and is also effective in a photoresist film composed of a mixture thereof. .

As a method of removing the resist, the modified or cured resist, and the dry etching residue on the flat panel display substrate by using the resist stripper composition of the present invention, a method of depositing a resist coated substrate in a stripper or a stripper is applicable. And a method of spraying onto the substrate. Further, in this case, a physical treatment such as irradiation of ultrasonic waves or contacting a brush that rotates or swings left and right may be used in combination. After the stripping solution treatment, the stripping solution remaining on the substrate can be removed by 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.

For the peeling method, an immersion method, a spray method, or an immersion and spray method may be used. In the case of peeling by dipping, spraying or dipping and spraying, the temperature as the peeling condition is usually 15 to 100°C, preferably 30 to 70°C, and the dipping, spraying, or dipping and spraying time is usually 30 seconds to 40 minutes, It is preferably 1 minute to 20 minutes, but it is not strictly applied in the present invention, and can be modified in easy and suitable conditions by a person skilled in the art. If the temperature of the stripper composition applied on the substrate on which the resist is applied is less than 15° C., the time required to remove the modified or cured resist film may be too long. In addition, when the temperature of the composition exceeds 100°C, there is a concern about damage to the lower film layer of the resist film, and it is difficult to handle the stripper.

The resist stripper composition of the present invention and a stripping method using the same can be used not only to remove a general resist, but also to remove a resist modified or cured by an etching gas and high temperature, and an etching residue.

In addition, the present invention

It provides a method for manufacturing a flat panel for a display device, comprising the step of removing the resist from a substrate for a flat panel by using the resist stripper composition of the present invention.

In addition, the present invention

A method for manufacturing a flat panel display device is provided, comprising the step of removing the resist from a substrate for a flat panel by using the resist stripper composition of the present invention.

Flat panels and flat panel display devices for display devices manufactured by the above manufacturing method are of excellent quality because the resist is completely removed during the manufacturing process, and corrosion of metal wiring including aluminum and/or copper is hardly caused. Has.

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are for explaining the present invention in more detail, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

Example 1 to 9 and Comparative example 1-5: Resist Stripper Preparation of the composition

A resist stripper composition was prepared by mixing the components and contents shown in Table 1 below.

division Amide compounds
[weight%] Glycolamine
[weight%] Glycol ether
[weight%] Example 1 Formula 1 10 DGA 5 DEGEE 85 Example 2 Formula 2 10 DGA 5 DEGEE 85 Example 3 Formula 1 5 DGA 5 DEGEE 85 Formula 2 5 Example 4 Formula 1 20 DGA 5 DEGEE 75 Example 5 Formula 1 40 DGA 5 DEGEE 55 Example 6 Formula 2 20 DGA 5 DEGEE 75 Example 7 Formula 2 40 DGA 5 DEGEE 55 Example 8 Formula 1 10 DGA 5 TEGME 85 Example 9 Formula 1 10 DGA 5 TEG 85 Comparative Example 1 Formula 5 10 DGA 5 DEGEE 85 Comparative Example 2 Formula 1 10 DGA 5 DEGDME 85 Comparative Example 3 Formula 2 10 DGA 5 DEGDME 85 Comparative Example 4 Formula 1 10 DEA 5 DEGEE 85 Comparative Example 5 Formula 2 10 DEA 5 DEGEE 85

week)

[Formula 1]

[Formula 2]

[Formula 5]

DGA: 2-(2-aminoethoxy)ethanol

DEA: diethanolamine

DEGEE: Diethylene glycol monoethyl ether

TEGME: triethylene glycol monomethyl ether

TEG: triethylene glycol

DEGDME : Diethylene glycol dimethyl ether

Test example One: Resist Evaluating removal performance

In order to check the peeling effect of the resist stripping composition prepared in Examples 1 to 9 and Comparative Examples 1 to 5, a photoresist was applied to a 4 inch bare glass substrate to a thickness of about 2 μm, and then at 170°C. Hard-bake was carried out for 10 minutes at, to prepare a substrate coated with a resist under harsh conditions. In addition, the substrate was cut into 1.5 cm (horizontal) x 1.5 cm (vertical), and then immersed in the resist stripper composition stock solution at 50°C, followed by washing and drying to completely remove the resist to remove residual resist visually The time not observed was measured. The measurement of the resist peeling time was performed five times for each prepared peeling solution composition, and the range of the complete peeling time is shown in Table 2 below.

division Resist peeling time (sec) Example 1 80 Example 2 50 Example 3 60 Example 4 70 Example 5 55 Example 6 40 Example 7 35 Example 8 70 Example 9 90 Comparative Example 1 70 Comparative Example 2 50 Comparative Example 3 40 Comparative Example 4 150 Comparative Example 5 140

As can be seen in Table 2, the resist stripper compositions of Examples 1 to 9 exhibited a stripping speed equal to or higher than that of the resist stripping solution compositions of Comparative Examples 1 and 5.

Test example 2: Evaluation of storage stability (storage characteristics)

While storing the stripper compositions of Examples 1 to 9 and Comparative Examples 1 to 5 at 70° C. for 96 hours, gas chromatography (GC) was used to measure the change in the content of the organic amine compound, and the results are shown in Table 3 below. Indicated.

division Changes in the content of amine compounds Example 1 25% Example 2 3% Example 3 18% Example 4 35% Example 5 39% Example 6 5% Example 7 7% Example 8 27% Example 9 12% Comparative Example 1 57% Comparative Example 2 78% Comparative Example 3 65% Comparative Example 4 22% Comparative Example 5 3%

As shown in Table 3, the stripper compositions of Examples 1 to 9 of the present invention exhibited excellent storage stability with the stripper compositions of Comparative Examples 1 to 5. In the stripper compositions of Comparative Examples 4 and 5, a secondary amine having a low reactivity was used, so that the change in the content of the amine compound was small.

Test example 3: Evaluation of weight change due to evaporation loss

After putting the stripper compositions of Examples 1 to 9 and Comparative Examples 1 to 5 in each container, the weight change due to evaporation loss was measured while being stored under a temperature condition of 70°C, and is shown in Table 4 below.

Weight change due to evaporation loss (g) Elapsed time (hr) 24 Example 1 -3 Example 2 0 Example 3 -2 Example 4 -4 Example 5 -5 Example 6 0 Example 7 0 Example 8 -3 Example 9 -2 Comparative Example 1 -8 Comparative Example 2 -18 Comparative Example 3 -16 Comparative Example 4 -3 Comparative Example 5 0

As shown in Table 4, the stripper compositions of Examples 1 to 9 of the present invention exhibited evaporation loss equal to or higher than those of the stripper compositions of Comparative Examples 1 to 5.

Claims (6)

An amide compound represented by the following formula (1),
Glycolamine represented by the following Chemical Formula 3, and
Resist stripper composition comprising a glycol ether represented by the following formula (4):
[Formula 1]

[Formula 3]

In Chemical Formula 3, n=2~3.
[Formula 4]

In Chemical Formula 4, R ₁ is hydrogen or C1-C4 aliphatic hydrocarbon. The method according to claim 1,
A resist stripper composition comprising 5 to 50% by weight of an amide compound, 2 to 25% by weight of glycolamine, and a remaining amount of glycol ether based on the total weight of the composition. The method according to claim 1,
The resist stripper composition further comprises at least one selected from the group consisting of a surfactant, a corrosion inhibitor, and water. Resist stripper composition, characterized in that. (I) depositing a conductive metal film on a flat panel display substrate,
(II) forming a resist film on the conductive metal film;
(III) selectively exposing the resist film;
(IV) developing a resist film after the exposure to form a resist pattern;
(V) etching the conductive metal layer using the resist pattern as a mask; And
(VI) After the etching step, a resist stripping method comprising the step of removing the resist modified and cured by forming and etching the resist pattern using the resist stripper composition of any one of claims 1 to 3. A method of manufacturing a flat panel for a display device, comprising a step of removing the resist from a substrate for a flat panel using the resist stripper composition according to any one of claims 1 to 3. A method of manufacturing a flat panel display device, comprising a step of removing the resist from a substrate for a flat panel using the resist stripper composition according to any one of claims 1 to 3.