KR102213779B1 - Resist stripper composition and a method of stripping resist using the same - Google Patents

Abstract

The present invention is a resist peeling comprising 5 to 50% by weight of the amide compound represented by Formula 1, 0.5 to less than 2% by weight of glycolamine represented by Formula 2, and the remaining amount of glycol ether represented by Formula 3 based on the total weight of the composition. It provides a liquid composition and a resist stripping method using the same.

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 resist stripping method.

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 this, 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 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 storage of the composition, 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:

Republic of Korea Patent Registration No. 10-1304723 is an amide compound of 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 of the following formula (2), and an aromatic hydrogen. A photoresist stripper comprising a oxy compound and deionized water is disclosed:

[Formula 1]

[Formula 2]

Republic of Korea Patent 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 type of amide and an amine compound soluble in water.

The stripper is characterized in that it contains 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, characterized in that the polarity of the stripper is large, so that the removal ability of the resist pattern deformed after wet or dry etching is excellent, storage stability is excellent, and 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,

Resist comprising 5 to 50% by weight of an amide compound represented by the following formula (1), less than 0.5 to less than 2% by weight of a glycolamine represented by the following formula (2), and the remaining amount of glycol ether represented by the following formula (3), based on the total weight of the composition Regarding the stripper composition:

[Formula 1]

In the above formula

R1 is hydrogen or ethyl group.

[Formula 2]

[Formula 3]

In the above, R2 is hydrogen or an aliphatic hydrocarbon of C1 to C4.

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

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 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, there is provided a method of removing a resist 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.

In addition, the present invention

A method for manufacturing a flat panel for a display device and a method for 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 since the reaction between the amide compound and glycolamine is minimized, it has excellent storage stability. Provides excellent effect on pattern removal.

The present invention, based on the total weight of the composition, 5 to 50% by weight of the amide compound represented by the following formula (1), 0.5 to less than 2% by weight of glycolamine represented by the following formula (2), and the remaining amount of glycol ether represented by the following formula (3) It relates to a resist stripper composition comprising:

[Formula 1]

In the above formula

R1 is hydrogen or ethyl group.

[Formula 2]

[Formula 3]

In the above, R2 is hydrogen or an aliphatic hydrocarbon of C1 to C4.

The amide compound represented by Formula 1 has a high boiling point.

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 reduced in the cleaning process after the resist stripping process. Pollution problems can arise. In addition, since amide compounds are relatively expensive, they are disadvantageous in terms of cost.

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 0.5 to less than 2% by weight, more preferably 1.0 to 1.5% by weight, based on the total weight of the composition. When the glycolamine compound is contained in an amount of less than 0.5% by weight, the peeling effect on the resist is insufficient, and when it is contained in an amount of 2% by weight or more, the reaction with the amide compound is increased and the aging stability of the peeling solution is lowered, Corrosion rates for metallization can increase.

When the glycol amine is contained in an amount of 1.0 to 1.5% by weight, the releasability of the resist and the aging stability of the stripping liquid composition can be simultaneously satisfied, which is more preferable.

As described above, the decrease in the content of amine with time increases as the content of glycolamine increases, which seems to be because glycolamine is a nucleophilic substance and acts as a base at the same time. That is, it seems that this is because the adjacent glycolamine acts as a base catalyst when any glycolamine undergoes an amine substitution reaction with an amide compound by nucleophilic attack.

The glycol ether serves to dissolve the gelled resist polymer by assisting the amide compound, and also minimizes re-precipitation of the dissolved resist in the stripping solution by facilitating the removal of the stripper by water during the DI rinse process after the resist stripping. do. In addition, it serves to improve the performance of the glycolamine, penetrates the denatured or crosslinked resist, and breaks the bonds existing in the molecule 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. 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 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.

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.

As the nonionic surfactant, polyoxyethylene alkyl ether type, polyoxyethylene alkylphenyl ether type, polyoxyethylene polyoxypropylene alkyl ether type, polyoxyethylene polyoxybutylene alkyl ether type, 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, and these may be used alone or in two More than one species can be used together.

It is preferable that the surfactant is included 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 in preventing the tendency to become difficult to handle due to severe foamability of the peeling solution.

The corrosion inhibitor is benzotriazole, methyl gallate, tolitrizol, methyl tolitrizol, 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]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] Azole compounds such as -benzotriazol-1-yl]methyl]imino]bisethanol, and these may be used singly 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 included 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 the 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 the 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 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.

Types of the resist include positive and negative g-ray, i-ray and deep ultraviolet (DUV) resists, electron beam resists, X-ray resists, and ion beam resists, and are not limited by their constituent components. , 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 contact with 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 easily modified by a person skilled in the art to suitable conditions. 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 a 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 peeling a resist from a substrate for a flat panel using the resist stripper composition of the present invention.

In addition, the present invention

There is provided a method for manufacturing a flat panel display device comprising the step of removing the resist from a substrate for a flat panel 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 more specifically, 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 1-6: 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 4 10 DGA 1.2 DEGEE 88.8 Example 2 Formula 5 10 DGA 1.2 DEGEE 88.8 Example 3 Formula 4 20 DGA 1.0 DEGEE 79 Example 4 Formula 4 40 DGA 1.0 DEGEE 59 Example 5 Formula 5 20 DGA 1.5 DEGEE 78.5 Example 6 Formula 5 40 DGA 1.5 DEGEE 58.5 Example 7 Formula 4 10 TGA 1.2 DEGEE 88.8 Example 8 Formula 4 10 DGA 1.2 TEGME 88.8 Example 9 Formula 4 10 DGA 1.2 TEG 88.8 Comparative Example 1 Formula 4 10 DGA 2 DEGEE 88.0 Comparative Example 2 Formula 5 10 DGA 2 DEGEE 88.0 Comparative Example 3 Formula 4 10 DGA 5 DEGEE 85 Comparative Example 4 Formula 5 10 DGA 5 DEGEE 85 Comparative Example 5 Formula 6 10 DGA 1.2 EDG 88.8 Comparative Example 6 Formula 4 10 DGA 1.2 DEGDME 88.8

week)

[Formula 4]

[Formula 5]

[Formula 6]

DGA: 2-(2-aminoethoxy)ethanol

)TGA: diethylene glycol aminoethyl ether (

)

DEGEE: Diethylene glycol monoethyl ether

TEGME: triethylene glycol monomethyl ether

DEGDME : Diethylene glycol dimethyl ether

Test example One: Resist Evaluating removal performance

To check the peeling effect of the resist stripping composition prepared in Examples 1 to 9 and Comparative Examples 1 to 6, a photoresist was applied to a 4 inch bare glass substrate to a thickness of about 2 μm, and then 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 with the naked eye. 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 90 Example 2 90 Example 3 75 Example 4 60 Example 5 75 Example 6 60 Example 7 95 Example 8 85 Example 9 100 Comparative Example 1 90 Comparative Example 2 90 Comparative Example 3 80 Comparative Example 4 80 Comparative Example 5 80 Comparative Example 6 60

As can be seen from Table 2 above, the resist stripping liquid compositions of Examples 1 to 9 exhibited a resist stripping speed equivalent to that of the resist stripping solutions of Comparative Examples 1 and 6.

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

While storing the stripper compositions of Examples 1 to 9 and Comparative Examples 1 to 6 at 70° C. for 96 hours, the change in the content of the organic amine compound was measured using gas chromatography (GC), and the results are shown in Table 3 below. Indicated.

division Change of amine compound content Example 1 30% Example 2 25% Example 3 25% Example 4 20% Example 5 35% Example 6 30% Example 7 35% Example 8 35% Example 9 15% Comparative Example 1 60% Comparative Example 2 50% Comparative Example 3 75% Comparative Example 4 65% Comparative Example 5 50% Comparative Example 6 60%

As shown in Table 3, the stripper compositions of Examples 1 to 9 of the present invention exhibited excellent storage stability compared to the stripper compositions of Comparative Examples 1 to 6.

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 6 in each container, the weight change due to evaporation loss was measured while being stored under a temperature condition of 70° C. and shown in Table 4 below.

Weight change due to evaporation loss (g) Elapsed time (hr) Example 1 0 Example 2 -One Example 3 0 Example 4 -One Example 5 -2 Example 6 -2 Example 7 0 Example 8 0 Example 9 0 Comparative Example 1 0 Comparative Example 2 -One Comparative Example 3 0 Comparative Example 4 -One Comparative Example 5 -5 Comparative Example 6 -21

As shown in Table 4, the stripper compositions of Examples 1 to 9 of the present invention exhibited equal or less evaporation loss compared to the stripper compositions of Comparative Examples 1 to 6.

Claims (6)

Resist peeling comprising 5 to 50% by weight of an amide compound represented by the following Formula 1, 0.5 to less than 2% by weight of a glycolamine represented by the following Formula 2, and the remaining amount of glycol ether represented by the following Formula 3 based on the total weight of the composition Liquid composition:
[Formula 1]

In Formula 1, R ₁ is hydrogen or an ethyl group.
[Formula 2]

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

In Chemical Formula 3, R ₂ is hydrogen or C1-C4 aliphatic hydrocarbon. The method according to claim 1,
Resist stripper composition, characterized in that the glycolamine is contained in an amount of 1.0 to 1.5% by weight 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 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 stripping 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 of any one of claims 1 to 3. A method of manufacturing a flat panel display device, comprising the step of removing the resist from the substrate for a flat panel using the resist stripper composition according to any one of claims 1 to 3.