KR20160024574A - Resist stripper composition and a method of stripping resist using the same - Google Patents

Abstract

Provided is a resist stripper composition comprising: 5-50 wt% of an amide compound represented by chemical formula 1; less than 0.5-2 wt% of glycolamine represented by chemical formula 2; and a residual amount of glycol ether represented by chemical formula 3. The present invention further relates to a method for stripping resist using the same. According to the present invention, the stripping solution has high polarity, and thus shows superior capability of removing a resist pattern transformed after wet or dry etching.

Description

[0001] The present invention relates to a resist stripping liquid composition and a resist stripping method using the resist stripping composition.

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

In recent years, efforts have been made to increase the number of pixels per unit area as the demand for high-resolution implementation of flat panel displays increases. In accordance with this tendency, reduction of the wiring width is also required, and in order to cope with this, the dry etching process has been introduced, and the process conditions have become increasingly severe. In addition, due to the enlargement of the flat panel display device, an increase in the signal speed in the wiring is also required, and copper having a lower resistivity than aluminum is now being used as a wiring material. Accordingly, the required performance of the stripping solution used in the stripping process, which is a resist stripping process, is increasing. Specifically, a considerable level of exfoliation property with respect to the removal force of deformed resist generated after the dry etching process and the corrosion inhibiting ability against the metal wiring is required. In addition, in order to secure price competitiveness, it is required to improve the process speed, increase the number of storable days of the composition, and increase the number of processed substrates.

In response to the needs of such industries, new technologies are being disclosed, including:

Korean Patent No. 10-1304723 discloses an amide compound represented by the following general formula (1), a water-soluble organic amine compound, a hydroxylamine salt compound, a water-soluble polar aprotic solvent, an alkylene glycol alkyl ether compound, Roxy compounds, and deionized water.

[Chemical Formula 1]

(2)

Korean Patent Laid-Open No. 10-2003-0026822 discloses a process for the preparation of N-methyl-pyrrolidone (N-methyl-2-pyrrolidone), N, N-dimethyl-acetamide, dimethyl- Amide, and an amine compound capable of dissolving in water. The present invention also provides a resist stripper comprising a composition comprising a high-polarity solvent containing at least one member selected from the group consisting of amines,

The peeling liquids are characterized in that they contain an amide compound. However, considering the physical properties such as polarity, reactivity with amine, and boiling point of the amide compounds contained, It is thought that improvement is necessary.

Korean Patent No. 10-1304723 Korean Patent Publication No. 10-2003-0026822

SUMMARY OF THE INVENTION The present invention has been made to solve the problems of the prior art as described above, and it is an object of the present invention to provide a resist pattern forming method and a resist pattern forming method which are excellent in the ability to remove a resist pattern deformed after wet or dry etching, And a resist stripping method using the same.

According to the present invention,

A resist composition comprising 5 to 50% by weight of an amide compound represented by the following formula (1), less than 0.5 to 2% by weight of a glycolamine represented by the following formula (2), and a residual amount of a glycol ether represented by the following formula ≪ / RTI >

[Chemical Formula 1]

In the above formula

R1 is hydrogen or an ethyl group.

(2)

(3)

Wherein R2 is hydrogen or a C1 to C4 aliphatic hydrocarbon.

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

In addition,

(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 the exposed resist film to form a resist pattern;

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

(VI) a step of peeling the resist, which is denatured and cured by the resist pattern formation and etching after the etching process, from the substrate using the resist stripping liquid composition of the present invention.

In addition,

There is provided a method of manufacturing a flat panel display device and a method of manufacturing a flat panel display device, which comprises a step of peeling off a resist for a flat panel substrate using the resist stripping liquid composition of the present invention.

The resist stripper composition of the present invention is excellent in storage stability because the amide compound contained in the stripper solution has a high boiling point, minimizes the process loss, minimizes the reaction between the amide compound and the glycol amine, It provides excellent effects for removing patterns.

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

[Chemical Formula 1]

In the above formula

R1 is hydrogen or an ethyl group.

(2)

(3)

Wherein R2 is hydrogen or a C1 to C4 aliphatic hydrocarbon.

The amide compound represented by the formula (1) has a high boiling point.

The amide compound may be contained in an amount of 5 to 50% by weight, more preferably 10 to 40% by weight, based on the total weight of the composition. When the amount of the amide compound represented by the general formula (1) is less than 5% by weight, the effect of increasing the peeling speed of the resist decreases. When the amount exceeds 50% by weight, Contamination problems can occur. Further, since the amide compound is relatively expensive, it is disadvantageous in terms of cost.

The glycol amine serves to decompose the resist crosslinked product into small structural units, which are deformed by the etching or not deformed.

Particularly, since the glycol amine contains a primary amino group and has a high decomposition reactivity to a denatured photoresist and has a low vapor pressure due to the presence of a hydroxyl group in the molecule, it is possible to suppress the process loss, Can be preferably used.

The glycol amine may be contained in an amount of 0.5 to less than 2 wt%, more preferably 1.0 to 1.5 wt%, based on the total weight of the composition. When the glycol amine compound is contained in an amount of less than 0.5% by weight, the peeling effect on the resist is insufficient. When the glycol amine compound is contained in an amount of 2% by weight or more, the reaction with the amide compound is increased, The corrosion rate for metal wiring can be increased.

When the glycol amine is contained in an amount of 1.0 to 1.5% by weight, it is more preferable that the peelability of the resist and the stability with time of the release liquid composition can be satisfied at the same time.

As described above, the decrease in the amine content with time increases with the increase in the content of glycolamine, because the glycolamine is a nucleophilic and simultaneously acts as a base. That is, it seems that when any glycol amine undergoes an amine substitution reaction with an amide compound by nucleophilic attack, the adjacent glycol amine functions as a base catalyst.

The glycol ether serves to dissolve the gelled resist polymer by assisting the amide compound, and facilitates the removal of the peeling liquid by water in the DI rinse process after peeling off the resist, thereby minimizing re-precipitation of the resist dissolved in the peeling liquid do. And acts to improve the performance of the glycol amine, thereby penetrating the modified or crosslinked resist and breaking the bonds existing in the molecule or between the molecules.

Particularly, since the glycol ether contains two or more ethylene glycol groups in the molecule and contains hydroxyl groups, it has a high breaking point to suppress the process loss. Further, the glycol ether contains not more than four ethylene glycol groups and thus increases the molecular weight and thereby the viscosity So that the peeling speed of the resist is not lowered. In addition, one end is alkylated with a lower hydrocarbon, so that the solubility of water is not lowered and the solubility of the resist is improved. In addition, it can be preferably used for the release liquid composition of the present invention in that it plays a role of suppressing the precipitation of the resist during the rinsing process.

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

In addition to the above components, the release liquid composition of the present invention may further contain components commonly used in the field such as surfactants, corrosion inhibitors, and water. When these components are further contained, the content of the polyethylene glycol is reduced in the above, and the above components can be added to the content of the polyethylene glycol.

Examples of the surfactant include anionic surfactants, cationic surfactants and nonionic surfactants. Of these, nonionic surfactants having excellent wettability and less bubble formation are preferably used.

Examples of the nonionic surfactant include polyoxyethylene alkyl ether type, polyoxyethylene alkyl phenyl ether type, polyoxyethylene polyoxypropylene alkyl ether type, polyoxyethylene polyoxybutylene alkyl ether type, polyoxyethylene alkylamino ether Polyoxyethylene alkylamido ether type, polyethylene glycol fatty acid ester type, sorbitan fatty acid ester type, glycerin fatty acid ester type, alkyrol amide type and glycerin ester type surfactants. These surfactants may be used singly or in combination of two or more. More than one species can be used together.

The surfactant is preferably contained in an amount of 0.001 to 1.0 wt% based on the total weight of the composition. When it is contained in the above-mentioned content range, it is advantageous to uniformly peel off the substrate, and at the same time, it is advantageous to prevent the tendency that handling of the peeling liquid becomes difficult due to severe foaming.

The corrosion inhibitor may be selected from the group consisting of benzotriazole, methyl gallate, tolythriazole, methyltolytriazole, 2,2 '- [[[benzotriazole] methyl] imino] bisethanol, 2,2' - [ Methyl] imino] bis-methanol, 2,2 '- [[[ethyl-1-hydrogen benzotriazol- Benzyltriazol-1-yl] methyl] imino] bisethanol, 2,2 '- [[[methyl- Methyl] imino] biscarboxylic acid, 2,2 '- [[[amine-1 < -Benzotriazol-1-yl] methyl] imino] bis-ethanol, which may be used alone or in combination of two or more.

The corrosion inhibitor is excellent in the corrosion inhibiting ability of a metal wiring including aluminum and / or a metal wiring including copper, and is particularly excellent in corrosion resistance against copper and a metal 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 the copper or the metal wiring including the copper or rhenium in the rinsing process by peeling or deionized water. When the corrosion inhibitor is added in an amount exceeding 5% by weight, The effect is not improved because it is no longer improved.

The resist stripping composition of the present invention can be prepared by mixing the above-mentioned compounds in an appropriate 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 by using the resist stripper composition of the present invention. The above-mentioned resist peeling method is a method for peeling a resist,

(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 the exposed resist film to form a resist pattern;

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

(VI) A step of peeling the resist, which has been modified and cured by the resist pattern formation and etching after the etching process, from the substrate using the resist stripping liquid composition of the present invention.

In addition, the removing method of the present invention may be carried out by performing a dry etching process such as an etchback process or a CMP (Chemical Mechanical Polishing) process without performing a resist pattern forming process using a mask, And a method of peeling off with the peeling liquid composition of the invention.

The resist film formation, exposure, development, etching, and ashing processes in the peeling method can be performed by a method commonly known in the art.

Examples of the types of the resist include positive and negative g-line, i-line and deep ultraviolet (DUV) resists, electron beam resists, X-ray resists, and ion beam resists. , The resist to which the resist stripping composition of the present invention is effectively applied is a photoresist film composed of a novolak-based phenol resin and a photoactive compound based on diazonaphthoquinone, and is also effective for a photoresist film composed of a mixture thereof .

As a method for removing the resist on the flat panel display substrate, the modified or cured resist, and the dry etching residue by using the resist stripping liquid composition of the present invention, a method of immersing the substrate coated with the resist in the stripping liquid, And a method of spraying onto a substrate. In this case, physical treatment such as irradiation of ultrasonic waves, rotation, or contact with a brush that rocks to the left and right may be used in combination. After the removing solution treatment, the removing solution remaining on the substrate can be removed by the subsequent cleaning treatment. The cleaning step is the same as the peeling step except that water or isopropyl alcohol is used in place of the peeling solution.

The peeling method may be a deposition method, a spraying method, or a deposition and spraying method. In the case of peeling by immersion, spraying or immersion and spraying, the temperature for peeling is usually from 15 to 100 캜, preferably from 30 to 70 캜, and the immersion, spraying or immersion and spraying time is usually from 30 seconds to 40 minutes, Preferably 1 minute to 20 minutes, but is not strictly applied in the present invention, and can be modified in a condition that is easy and suitable for a person skilled in the art. If the temperature of the release liquid composition applied on the substrate to which the resist is applied is less than 15 캜, the time required to remove the modified or cured resist film may become excessively long. If the temperature of the composition exceeds 100 占 폚, the lower film layer of the resist film may be damaged, resulting in difficulty in handling the exfoliation liquid.

The resist stripping composition of the present invention and the stripping method using the resist stripping composition of the present invention can be used not only for general resist removal but also for removal of resist and etching residue which are modified or cured by etching gas and high temperature.

In addition,

There is provided a method of manufacturing a flat panel for a display device, which comprises a step of peeling off a resist for a flat panel substrate using the resist stripping liquid composition of the present invention.

In addition,

There is provided a method of manufacturing a flat panel display device, which comprises a step of peeling off a resist for a flat panel substrate using the resist stripping liquid composition of the present invention.

The flat panel and the flat panel display device for a display device manufactured by the above manufacturing method are excellent in the removal of the resist in the manufacturing process and the corrosion of the metal wiring including aluminum and / Respectively.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, 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 to 6: Resist Peeling liquid  Preparation of composition

The components and contents described in Table 1 below were mixed to prepare a resist stripper composition.

division Amide compound
[weight%] Glycol amine
[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 6 10 DGA 1.2 EDG 88.8 Comparative Example 6 Formula 4 10 DGA 1.2 DEGDME 88.8

week)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical 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  Removal performance evaluation

In order to confirm 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 탆, (Hard-bake) for 10 minutes to prepare a substrate coated with a resist under a severe condition. The substrate was cut into 1.5 cm (width) .times.1.5 cm (length), immersed in the stock solution of resist stripper composition at 50.degree. C., washed and dried to remove the resist completely, The time not observed was measured. The resist stripping time was measured five times for each of the prepared stripping liquid compositions, and the range of time for complete stripping is shown in Table 2 below.

division Resist stripping 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 the above Table 2, the resist stripping liquid compositions of Examples 1 to 9 exhibited resist stripping rates to the same degree as those of the resist stripping solutions of Comparative Examples 1 and 6.

Test Example  2: Evaluation of storage stability (storage property)

Changes in the content of the organic amine compound were measured using gas chromatography (GC) while the peeling liquid compositions of Examples 1 to 9 and Comparative Examples 1 to 6 were stored at 70 占 폚 for 96 hours. The results are shown in Table 3 below Respectively.

division Changes in content of amine compounds 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 peeling liquid compositions of Examples 1 to 9 of the present invention showed excellent storage stability as compared with the peeling liquid compositions of Comparative Examples 1 to 6.

Test Example  3: Evaluation of weight change by evaporation loss

The peeled-off liquid compositions of Examples 1 to 9 and Comparative Examples 1 to 6 were put in each container, and the change in weight due to evaporation loss was measured while being stored under the temperature condition of 70 ° C, and it is 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 peeling liquid compositions of Examples 1 to 9 of the present invention exhibited equal or less evaporation loss as compared with the peeling liquid compositions of Comparative Examples 1 to 6.

Claims (6)

A resist peeling method comprising 5 to 50% by weight of an amide compound represented by the following formula (1), 0.5 to 2% by weight of a glycolamine represented by the following formula (2), and a residual amount of a glycol ether represented by the following formula Liquid composition:
[Chemical Formula 1]

In the above formula
R1 is hydrogen or an ethyl group.
(2)

(3)

Wherein R2 is hydrogen or a C1 to C4 aliphatic hydrocarbon. The method according to claim 1,
Wherein the glycol amine 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 may further comprise at least one selected from the group consisting of a surfactant, a corrosion inhibitor, and water Wherein the resist stripper composition is a resist stripper composition. (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 the exposed resist film to form a resist pattern;
(V) etching the conductive metal film using the resist pattern as a mask; And
(VI) A method of peeling off a resist, comprising the step of peeling the resist, which has been modified and cured by the resist pattern formation and etching after the etching process, using the resist stripping solution composition of any one of claims 1 to 3. A method for manufacturing a flat panel for a display device, which comprises a step of peeling a resist for a flat panel substrate using the resist stripping liquid composition according to any one of claims 1 to 3. A method for manufacturing a flat panel display device, which comprises a step of peeling off a resist for a flat panel substrate using the resist stripping liquid composition according to any one of claims 1 to 3.