KR20190116211A - A resist stripper composition for preventing unevenness - Google Patents

Abstract

The present invention relates to a resist stripper composition for preventing staining, comprising: (a) a glycol ether represented by chemical formula 1, R-(OCH_2CH_2)n-OH; (b) an alkaline compound; (c) a non-protic polar solvent; and (d) a corrosion inhibitor. In the chemical formula 1, R is a methyl group or an ethyl group, and n is an integer of 2 to 3.

Description

Resist stripper composition for preventing staining {A RESIST STRIPPER COMPOSITION FOR PREVENTING UNEVENNESS}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resist stripper composition having excellent cleaning ability in the manufacturing process of a flat panel display substrate and excellent in preventing stains generated in the stripping process.

Recently, as the demand for high-resolution implementation of flat panel displays increases, efforts have been made to increase the number of pixels per unit area. In accordance with this trend, a reduction in wiring width is required, and in order to cope with this, the process conditions are becoming more severe, such as the introduction of a dry etching process. In addition, due to the enlargement of the flat panel display device, an increase in signal speed in wiring is also required, and copper, which has a lower specific resistance than aluminum, has been put into practical use as a wiring material. In keeping with this, the required performance for the stripping solution used in the stripping step, which is a resist removal step, is also increasing. Specifically, a considerable level of peeling characteristics are required for the removal force on the etching residue and the corrosion inhibiting force on the metal wires generated after the dry etching process. In particular, not only aluminum but also corrosion inhibitors are required for copper, and economics such as increasing the number of substrates are required to secure price competitiveness. In response to the demands of the industry as described above, new technologies are being disclosed.

For example, Korean Patent Laid-Open Publication No. 2006-0028523 discloses a photoresist releasing agent that does not cause corrosion of metal wires, but by using a specific glycol ether having a high degree of stain generation, staining on a substrate after stripping in a process is performed. Problems that occur remain.

KR 10-2006-0028523 A

The present invention has been made to solve the above problems, in order to remove the resist applied to form a pattern of the metal film excellent in the residue removal ability of the resist by dry / wet etching during the manufacturing process of the flat panel display substrate It is an object of the present invention to provide a resist stripper composition which can prevent stains on a substrate caused by strippers and strippers in which resists are generated as the substrate passing the strip zone passes through the air curtain and the buffer zone in the strip process. .

In order to achieve the above object, the present invention provides a stain comprising (a) a glycol ether represented by the formula (1), (b) an alkaline compound, (c) a non-protonic polar solvent and (d) a corrosion inhibitor Provided is a resist peeling liquid composition for prevention of occurrence.

[Formula 1]

R- (OCH ₂ CH ₂ ) n-OH

In Formula 1, R is a methyl group or an ethyl group,

n is an integer of 2 to 3.

In addition, the present invention provides a method for manufacturing a flat panel display substrate comprising the step of cleaning the flat panel display substrate by using the resist stripper composition for preventing the occurrence of stain.

The resist stripper composition for preventing occurrence of stains according to the present invention is excellent in preventing stain generation by a stripper including a stripper and a resist in a resist stripping process of a flat panel display substrate by using a glycol ether represented by the formula (1). It has a washing ability and has an effect of improving the number of sheets processed.

In addition, when using the resist stripper composition for null display of the present invention, it is possible to reduce the failure rate of the flat panel display device to reduce the cost required for the overall manufacturing process.

Figure 1 shows the results observed using a halogen lamp according to Experimental Example 1 of the present invention, (a) is a Cu substrate using the resist stripper composition (photoresist content: 0.5%) of this Example 3 (B) shows the result of processing a Cu substrate using the resist stripper composition (photoresist content: 0.3%) of the comparative example 2. FIG.
Figure 2 shows the results observed with an optical microscope according to Experimental Example 1, (a) is the result of treating the Cu substrate using the resist stripper composition (photoresist content: 1%) of this Example 4, (b) shows the result of treating a Cu substrate using the resist stripper composition (photoresist content: 0.3%) of Comparative Example 5.

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

The present invention relates to a resist stripper composition which prevents spots from occurring on a flat panel display substrate.

(a) glycol ethers represented by Formula 1;

(b) alkali compounds;

(c) non-protonic polar solvents and

(d) It is related with the resist peeling liquid composition for preventing the generation | occurrence | production of a stain containing a corrosion inhibitor.

[Formula 1]

 R- (OCH ₂ CH ₂ n-OH

In Formula 1, R is a methyl group or an ethyl group,

n is an integer of 2 to 3.

In addition, the resist release liquid composition for preventing the occurrence of stains may further comprise (e) deionized water.

Each component is demonstrated concretely.

(a) Glycol ether represented by the formula (1)

Glycol ether represented by the following formula (1) included in the present invention has a stain preventing performance effect.

[Formula 1]

 R- (OCH ₂ CH ₂ n-OH

In Formula 1, R is a methyl group or an ethyl group,

n is an integer of 2 to 3.

Examples of the type of glycol ether represented by Formula 1 include diethylene glycol mono methyl ether, diethylene glycol ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and the like. Or two or more types can be mixed and used.

Other glycol ethers mainly used in TFT strippers include ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, polyethylene glycol, polyethylene glycol monomethyl ether, Polyethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, tetrahydrofurfuryl alcohol, and the like. Ether has no effect on the stain preventing performance of the resist stripper.

On the other hand, the glycol ether represented by Chemical Formula 1 included in the present invention has strippers, photoresists, and other organic substances remaining on the TFT substrate based on affinity with water in the stripper that serves to dissolve the photoresist. It washes well to prevent any contaminants remaining on the TFT substrate. In addition, the glycol ether satisfying Formula 1 has an effect of preventing the formation of stains on the TFT substrate, which can be classified through octanol / water partition coefficient.

In the glycol ether represented by Formula 1 included in the present invention, it is preferable that the octanol / water partition coefficient (Log P) calculated by Equation 1 below has a negative value.

 [Equation 1]

Kow = Co / Cw

(Co: concentration of solute in octanol, Cw: concentration of solute in water)

Log P (distribution factor) = Log (Kow)

(A) The glycol ether represented by the formula (1) is preferably included in 5 to 50% by weight, more preferably in 10 to 30% by weight relative to the total weight of the composition. When the content of the glycol ether represented by the formula (a) is less than 5% by weight, it is not effective in preventing the occurrence of stains, and when used in excess of 50% by weight, the cumulative number of release agents may be lowered. .

(b) alkali compounds

The alkali compounds strongly penetrate into the polymer matrix of the deteriorated or crosslinked resist under various process conditions such as dry or wet etching, ashing or ion implant processing, thereby allowing intramolecular or intermolecular molecules to penetrate. It acts to break existing bonds and creates a void in the structurally vulnerable part of the resist that remains on the substrate, transforming the resist into an amorphous polymer gel mass so that the resist attached to the substrate can be easily removed. To be.

The alkali compound included in the present invention is potassium hydroxide (KOH), sodium hydroxide (NaOH), tetramethyl ammonium hydroxide (TMAH), tetraethyl ammonium hydroxide (TEAH), It is preferable that it is 1 type, or 2 or more types chosen from the group which consists of carbonate, phosphate, ammonia, and amines.

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, etc. Amines; Tertiary amines such as diethyl hydroxyamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, dimethylethylamine, methyldiethylamine and methyldipropylamine; Choline, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, 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 Alkoxyamines; 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 having a ring such as-(2-hydroxyethyl) morpholine or N- (3-hydroxypropyl) morpholine.

The alkali-based compound preferably contains 5 to 30% by weight based on the total weight of the composition, and when included in less than 5% by weight, the peeling performance of the release agent is lowered, and when included in excess of 30% by weight of the metal film Can damage.

(c) non quantum polar solvent

The (c) non-protic polar solvent included in the present invention is also advantageous in the expression of the removal performance of the resist polymer deteriorated or crosslinked by etching or the like, and also advantageous in increasing the number of treatments. The non-protic polar solvent is preferably not too high or low in boiling point for proper peel force, it can be used mixed.

Preferred examples of the non-protic polar solvent include pyrrolidone compounds such as N-methyl pyrrolidone (NMP) and N-ethyl pyrrolidone; 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 carbonate; Formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N- (2-hydroxyethyl) acetamide, 3-methoxy Amide compounds such as -N, N-dimethylpropionamide, 3- (2-ethylhexyloxy) -N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, and the like. It can be used individually or in mixture of 2 or more types.

The non-protic polar solvent is preferably included in 20 to 70% by weight relative to the total weight of the composition, if less than 20% by weight, there is a risk of lowering the number of treatment due to the melting of the resist, 70% by weight If used in excess, it is not economical.

(d) corrosion inhibitors

(D) Corrosion inhibitor included in the present invention serves to suppress the corrosion of the metal wiring. In order to improve the corrosion protection performance of the metal, the (d) corrosion inhibitor is preferably a benzotriazole derivative represented by the formula (2).

[Formula 2]

R 2, R 3 and R 4 in Formula 2 are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an allyl group, an aryl group, an amino group, an alkylamino group, a nitro group, a cyano group, a mercapto group, an alkyl mercapto group, The monovalent group which has a hydroxyl group, a hydroxyalkyl group, a carboxyl group, a carboxyalkyl group, an acyl group, an alkoxy group, or a heterocycle is shown.

Specific examples of the benzotriazole derivatives include 2,2 '-[[[benzotriazole] methyl] imino] bisethanol, 2,2'-[[[methyl-1 hydrogen-benzotriazol-1-yl] Methyl] imino] bismethanol, 2,2 '-[[[ethyl-1 hydrogen-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-1 hydrogen-benzotriazol-1-yl] methyl] imino] bismethylamine, 2,2 '-[[[amine-1 hydrogen-benzotriazol-1-yl] methyl] imino ] Bisethanol etc. are mentioned.

The (d) corrosion inhibitor preferably contains 0.01 to 5% by weight relative to the total weight of the composition, when containing less than 0.01% by weight does not prevent the corrosion of the metal, when containing more than 5% by weight Not economical

(e) deionized water

The resist stripper composition of the present invention may further include (e) deionized water. The deionized water improves the activation rate of the alkali-based compound to increase the peeling rate, and compared with the composition not containing deionized water, it is possible to obtain an effect of improving the removal ability of the resist crosslinked or modified by a dry / wet etching process.

Mixed with the water-soluble polar solvent to remove the organic contaminants and the resist stripping solution remaining on the substrate in the rinsing process with deionized water can be quickly and completely, it is advantageous in cost down (Cost down).

The deionized water may or may not be included depending on the type of resist and the process of forming the metal pattern film. When the deionized water is included, it is preferable to include 10 to 40% by weight relative to the total weight of the composition, when used in excess of 40% by weight does not melt the resist well and may cause a decrease in the number of sheets.

Although a dipping method is common as a method of removing a resist using the resist stripping liquid composition of this invention, other methods, for example, the method by a spraying method, can also be used. As a washing | cleaning agent after processing with the composition by this invention, it is enough only to wash with water, without using an organic solvent like alcohol.

The resist stripper composition of the present invention can be usefully used in the process of removing the resist for semiconductor or electronic products, especially flat panel displays.

The present invention provides a method for producing a flat panel display substrate comprising a step of cleaning the flat panel display substrate using the resist stripper composition for preventing stain generation described above.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are intended to illustrate the present invention more specifically, but 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.

Reference Example 1. Glycol Ether Selection

The resist stripper composition of the present invention is excellent in the ability to prevent stain generation by a stripper including a stripper and a resist in a resist stripping process of a flat panel display substrate. This can be predicted by the octanol / water partition coefficient (Log P) and proved experimentally. At this time, the octanol / water partition coefficient is calculated by Equation 1 below.

[Equation 1]

Kow = Co / Cw

(Co: concentration of solute in octanol, Cw: concentration of solute in water)

Log P (distribution factor) = Log (Kow)

[Formula 1]

 R- (OCH ₂ CH ₂ n-OH

Glycol ether Octanol / water partition coefficient
(Log Kow) Diethylene glycol monomethyl ether -1.10 Diethylene glycol monoethyl ether -0.54 Triethylene Glycol Monomethyl Ether -0.70 Diethylene glycol monobutyl ether +0.15 Diethylene glycol monohexyl ether +1.70

As shown in Table 1, it was found that the glycol ether having an effect on stain prevention in the present invention has a negative octanol / water partition coefficient.

Example

Examples 1-7 and Comparative Examples 1-5: Preparation of Resist Stripping Liquid Composition

The components shown in Table 2 below were mixed at the corresponding composition ratios to prepare resist stripper compositions of Examples 1-7 and Comparative Examples 1-5.

(a)
Glycol ethers (b)
Alkaline compound (c)
Aprotic Polar Solvent (d)
Corrosion inhibitor (e)
DIW Kinds ingredient
(weight%) Kinds ingredient
(weight%) Kinds ingredient
(weight%) Kinds ingredient
(weight%) ingredient
(weight%) Example 1 MDG 20 MEA 10 NMF 69 d-1 1.0 - Example 2 EDG 20 MEA 10 NMF 69 d-1 1.0 - Example 3 MDG
EDG 10
10 MEA 10 NMF 69 d-1 1.0 -
- Example 4 MTG 20 MEA 10 NMF 69 d-1 1.0 - Example 5 ETG 20 MEA 10 NMF 69 d-1 1.0 - Example 6 EDG 20 MEA 10 NMF 39 d-1 1.0 30 Example 7 MTG 20 MEA 10 NMF 39 d-1 1.0 30 Comparative Example 1 - - MEA 10 NMF 89 d-1 1.0 - Comparative Example 2 BDG 20 MEA 10 NMF 69 d-1 1.0 - Comparative Example 3 BG 20 MEA 10 NMF 69 d-1 1.0 - Comparative Example 4 iPDG 20 MEA 10 NMF 69 d-1 1.0 - Comparative Example 5 BDG 20 MEA 10 NMF 39 d-1 1.0 30

MDG: Diethylene glycol monomethyl ether EDG: Diethylene glycol monoethyl ether

MTG: Triethylene Glycol Monomethyl Ether

ETG: Triethylene Glycol Monoethyl Ether

BDG: diethylene glycol monobutyl ether

BG: Ethylene Glycol Butyl Ether

iPDG: diethylene glycol monoisopropyl ether

MEA: monoethanol amine

NMF: N-methyl formamide

d-1: 2,2 '-[[[ethyl-1H-benzotriazol-1-yl] methyl] imino] bisethanol

Experimental Example 1. Evaluation of spot occurrence

In order to confirm the anti-staining effect of a resist stripping liquid composition, the board | substrate which formed the Cu layer using the thin-film sputtering method on the glass substrate was prepared in accordance with a conventional method. The resist needed for the experiment was prepared by baking DWG-520, our resist, at 115 ℃ for 3 days to remove all solvents and solidifying.

0.3%, 0.5%, and 1% of the resist prepared above was added to the resist stripper composition to sufficiently dissolve at room temperature, and then, the temperature of the stripper in which the resist was melted was maintained at 50 ° C. The target Cu substrate was immersed in the stripper where the temperature was constant for 2 minutes, and then removed, and the stripper and resist remaining on the substrate were removed to some extent by using nitrogen at a constant pressure, and then placed on a flat bottom. Drop 5 drops and let stand for 1 minute. After 1 minute, the substrate was rinsed with DIW for 1 minute, and then DIW remaining on the substrate was completely removed using nitrogen. In the experimental method described above, a halogen lamp, a digital camera, and an electron microscope were used to determine the degree of staining of the substrate in order to reproduce the actual TFT process. The results are shown in Table 3 and FIGS. (Circle), (good), (triangle | delta), and (triangle | delta), and the defect were represented by x.

division
Smear Cu substrate Photoresist content 0.3% 0.5% One% 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 3, the compositions of Examples 1 to 7, which are the resist stripper compositions of the present invention, were superior in preventing the occurrence of stains as compared to the compositions of Comparative Examples 1 to 5, and stains were generated even when the number of treatments was increased. It was confirmed that the prevention effect is much better.

Claims (10)

(a) glycol ethers represented by Formula 1;
(b) alkali compounds;
(c) non-protic polar solvents; And
(d) a resist stripping liquid composition for preventing staining, comprising a corrosion inhibitor:
[Formula 1]
R- (OCH ₂ CH ₂ ) n-OH
In Formula 1, R is a methyl group or an ethyl group,
n is an integer of 2 to 3. The resist stripper composition according to claim 1, wherein the resist stripper composition further comprises (e) deionized water. The method according to claim 1, wherein the total weight of the composition
(A) 5 to 50% by weight of a glycol ether (Glycol ether) represented by Formula 1;
(b) 5 to 30% by weight of the alkaline compound;
(c) 20 to 70% by weight of a non-protic polar solvent; And
(d) 0.01 to 5% by weight of a corrosion inhibitor, stain removal prevention composition for preventing occurrence of stains. The method according to claim 2, wherein (e) deionized water is characterized in that it comprises 10 to 40% by weight based on the total weight of the composition, the resist stripping liquid composition for preventing the occurrence of stain. The method according to claim 1 or claim 3, (a) Glycol ether (Glycol ether) represented by the formula (1) that octanol / water partition coefficient (Log P) calculated by the following formula (1) has a negative value (-) A resist peeling liquid composition for preventing the occurrence of stains.
[Equation 1]
Kow = Co / Cw
(Co: concentration of solute in octanol, Cw: concentration of solute in water)
Log P (distribution factor) = Log (Kow) The glycol ether having a negative value of octanol / water partition coefficient (Log P) calculated by Equation 1 is diethylene glycol mono methyl ether, diethylene glycol ethyl ether. And 1 or 2 or more types selected from the group consisting of triethylene glycol monomethyl ether and triethylene glycol monoethyl ether. The method of claim 1, wherein the (b) alkali compound is potassium hydroxide (KOH), sodium hydroxide (NaOH), tetramethyl ammonium hydroxide (TMAH), tetraethyl ammonium hydroxide (Tetraethyl ammonium hydroxide, TEAH), carbonate, phosphate, ammonia, and amines, characterized in that the one or two or more selected from the group consisting of, resist removal liquid composition for preventing the occurrence of stain. The method according to claim 1, wherein the (c) non-protic polar solvent is a pyrrolidone compound comprising N-methyl pyrrolidone (NMP) and N-ethyl pyrrolidone; Imidazolidinone compounds including 1,3-dimethyl-2-imidazolidinone and 1,3-dipropyl-2-imidazolidinone; lactone compounds including γ-butyrolactone; Sulfoxide compounds including dimethyl sulfoxide (DMSO) and sulfolane; Phosphate compounds including triethylphosphate and tributylphosphate; Carbonate compounds including dimethyl carbonate and ethylene carbonate; Formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N- (2-hydroxyethyl) acetamide, 3-methoxy An amide compound comprising -N, N-dimethylpropionamide, 3- (2-ethylhexyloxy) -N, N-dimethylpropionamide and 3-butoxy-N, N-dimethylpropionamide It is 1 type (s) or 2 or more types to which it becomes, The resist peeling liquid composition for preventing a stain generation. The method according to claim 1, wherein (d) the corrosion inhibitor is a benzotriazole derivative represented by the formula (2), characterized in that the stain release liquid resist stripping composition:
[Formula 2]

In Formula 2, R2, R3 and R4 are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an allyl group, an aryl group, an amino group, an alkylamino group, a nitro group, a cyano group, a mercapto group, an alkyl mercapto group And a monovalent group having a hydroxyl group, a hydroxyalkyl group, a carboxyl group, a carboxyalkyl group, an acyl group, an alkoxy group or a heterocycle. The manufacturing method of the flat panel display board | substrate including the process of washing a flat panel display board | substrate using the resist peeling liquid composition for preventing the generation | occurrence | production of any one of Claims 1-9.