KR20150075521A - Photoresist stripper composition - Google Patents

Abstract

The present invention relates to a photoresist stripper composition including compounds represented by chemical formula 1, an alkali-based compound, and a water soluble organic solvent. The photoresist stripper composition of the present invention does not remain on surfaces of a substrate and shows corrosion resistance effects to copper metal, has not electrical problems after processes are completed, and can prevent stains.

Description

[0001] PHOTORESIST STRIPPER COMPOSITION [0002]

The present invention relates to a photoresist stripper composition in a manufacturing process for a flat panel display substrate.

Photoresist is a chemical film that can form a fine pattern pre-drawn on a photomask on a desired substrate by using photochemical reaction by light. It is used as a polymer material applied to exposure technology together with a photomask. Is directly recognized as a major factor in determining the ultimate resolution limit. In order to put the increasing degree of circuit integration into a semiconductor of limited size every year according to the so-called Moore's law (the theory that semiconductor density doubles every two years), the designed circuit must be patterned much smaller Increasing semiconductor density is inevitably demanding the development of new photoresists.

In order to produce a high-resolution flat panel display, a photolithography process for forming fine wiring on a substrate using such a photoresist is generally used. This is performed by applying a photoresist to a substrate using the thermal, mechanical, Followed by exposure to light of a certain wavelength and performing dry etching or wet etching.

In the fine patterning technique using a photoresist, a development that has been emphasized with respect to a new photoresist is a resist stripper (or a photoresist remover). After the photolithography process, the photoresist should be removed by a solvent called a stripper (or photoresist remover), which is used to remove unwanted photoresist layers after the etching process, and metal residues remaining on the substrate through the etching and / This is because deteriorated photoresist residues cause problems such as deterioration in the yield of semiconductor manufacturing.

Accordingly, there is a demand for a peeling liquid having an ability to remove etching residues generated after the etching process. In addition, there is a demand for an exfoliating liquid having an economical effect such as an increase in the number of processed substrates for copper, corrosion inhibition against copper, and cost competitiveness.

Generally, water-soluble organic amines such as monoethanolamine and monoisopropanolamine, organic solvents such as gamma-butyllactone and DMSO, and the like are used for removing the photoresist. In addition, various types of corrosion inhibitors such as catechol, resorcinol, and benzotriazole are generally used to inhibit metal corrosion caused by amines, and a photoresist stripper composition containing the same has been proposed.

However, conventional photoresist stripper liquid compositions are known to have problems such as corrosion performance, the number of treatments, stability in process or long-term storage, and the like. For example, Korean Patent Laid-Open No. 10-2002-0075471 discloses a detergent composition containing a compound similar to the compound of Formula 1 of the present invention and a surfactant as an active ingredient, but a compound similar to the compound of Formula 1 mainly performs a cleaning function And the surfactant should be used only to prevent the reattachment of the pollutant component, the surfactant temperature limitation problem and the foaming of the foam can reduce the effect of the cleaning solution. Korean Patent Laid-Open Publication No. 10-2012-00688818 discloses a cleaning solution containing fluoride, guanidine, a solvent and water. However, since fluoride is contained together, a problem of corrosion prevention may occur, and corrosion There is a problem in that after the process, electrical properties and the like may cause a problem.

Korean Patent Publication No. 10-2002-0075471 Korean Patent Publication No. 10-2012-0068818

In order to solve the problems of the prior art as described above, the present invention has been made to solve the above-mentioned problems of the prior art, and it is an object of the present invention to provide a method for preventing corrosion of a copper metal without remaining on the surface of the substrate, It is an object of the present invention to provide a photoresist stripping liquid composition.

(A) at least one compound represented by the formula (1);

(b) an alkaline compound; And

(c) a water-soluble organic solvent,

Wherein the compound represented by Formula 1 is contained in an amount of 0.01 to 5% by weight based on the total composition.

[Chemical Formula 1]

In the above formula (1), R is CH ₂ or NH.

One embodiment of the present invention is a compound represented by the following formula (3): (a) a compound represented by the following formula (2-imidazolidone) and a compound represented by the following formula

(2)

(3)

;

;

(b) an alkaline compound; And (c) a water-soluble organic solvent.

Another embodiment of the present invention is a composition comprising: (a) from 0.01 to 5% by weight of a compound of formula (I); (b) 1 to 35% by weight of an alkaline compound; And (c) 60 to 90% by weight of a water-soluble organic solvent.

In another embodiment of the present invention, the alkaline compound (b) is one selected from the group consisting of KOH, NaOH, Tetramethyl ammonium hydroxide (TMAH), Tetraethyl ammonium hydroxide (TEAH), carbonate, phosphate, ammonia and amines Or two or more.

In another embodiment of the present invention, (c) the water-soluble organic solvent may be a proton-polar solvent, an aprotic polar solvent or a mixture thereof.

Another embodiment of the present invention may be a photoresist stripper liquid composition further comprising deionized water.

The photoresist stripper solution composition of the present invention exhibits a corrosion inhibiting effect on the copper metal without remaining on the surface of the substrate due to the small amount of the compound represented by the general formula (1), the alkaline compound and the water-soluble organic solvent, There is no problem in characteristics, and there is an effect that a problem of stains can be prevented from occurring.

Hereinafter, the present invention will be described in detail.

(A) at least one compound represented by the formula (1);

(b) an alkaline compound; And

(c) a water-soluble organic solvent.

The present invention relates to a process for producing a copper alloy which does not remain on the surface of a substrate due to the inclusion of a compound represented by the general formula (1), an alkaline compound and a water-soluble organic solvent and exhibits corrosion resistance to copper metal, There is an effect that the occurrence can be prevented.

Hereinafter, each component will be described in detail.

(a) a compound represented by the formula (1)

The photoresist stripper composition of the present invention uses a compound represented by the following general formula (1).

[Chemical Formula 1]

In Formula 1, R in Formula 1 is CH ₂ or NH.

More specifically, the compound represented by Formula 1 may be a compound represented by Formula 2 or a compound represented by Formula 3 below.

(2)

(3)

The compound represented by Formula 1 may be contained in the composition in one or more kinds. For example, it may contain only the compound represented by the general formula (2) or may include only the compound represented by the general formula (3), and preferably includes the compound represented by the general formula (2) and the compound represented by the general formula can do.

The compound represented by the above formula (1) can act as a corrosion inhibitor in a small amount of time, peeling, and cleaning liquid.

For example, unlike the mercapto-series, benzotriazole series, and hydroquinone series which are used as corrosion inhibitors for preventing corrosion by adsorbing on the metal surface, the compound represented by the general formula (2) is not adsorbed physically and chemically on the surface, It does not remain after the rinse process and does not interfere with the flow of electrons. This can solve the off-current caused by the surface adsorption of the corrosion inhibitors in the conventional flat panel display manufacturing process, and prevent stains that may remain due to adhesion of the corrosion inhibitor. Also, it has a corrosion inhibiting effect on the surface of the metal pattern including the copper metal, so that corrosion to the metal film can be minimized and does not cause color change of the release liquid composition.

In addition, the compound represented by the general formula (3) adsorbs on the metal surface and does not fall off, so that unlike other anticorrosive agents which affect the current shift of the TFT array, the compound acts as a method in the peeling process and is not removed in the washing process.

The compound represented by Formula 1 is preferably contained in an amount of 0.01 to 5% by weight based on the total weight of the composition, and most preferably 0.01 to 1% by weight in order to maximize the effect of the present invention. If it exceeds 5% by weight, the effect of corrosion prevention is lost without protecting the metal surface from the alkali compound. If it is less than 0.01% by weight, the corrosion prevention effect may be insignificant.

(b) an alkaline compound

The alkali-based compound strongly penetrates into the polymer matrix of the photoresist, which is denatured or crosslinked under various process conditions such as dry or wet etching, ashing or ion implant processing, It is the role of breaking the bond that exists in. An empty space is formed in a structurally weak portion in the photoresist remaining on the substrate so that the photoresist adhered on the substrate can be easily removed by deforming the photoresist into an amorphous polymer gel lump state.

The alkaline compound is preferably selected from the group consisting of KOH, NaOH, Tetramethyl ammonium hydroxide (TMAH), Tetraethyl ammonium hydroxide (TEAH), carbonate, phosphate, ammonia and amines. Can be used.

Among them, the amines include primary amines such as methylamine, ethylamine, monoisopropylamine, n-butylamine, sec-butylamine, isobutylamine, t-butylamine and pentylamine; Examples of the secondary amine such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, methylethylamine, methylpropylamine, methylisopropylamine, methylbutylamine and methylisobutylamine Amine; Tertiary amines such as diethylhydroxyamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, dimethylethylamine, methyldiethylamine and methyldipropylamine; But are not limited to, choline, monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, 2-aminoethanol, 2- (ethylamino) ethanol, 2- (methylamino) ethanol, Amino-2-propanol, 2-amino-1-propanol, 3-amino-1-propanol, Alkanolamines such as 4-amino-1-butanol, dibutanolamine and diglycolamine; (Methoxymethyl) dimethylamine, (methoxymethyl) dimethylamine, (butoxymethyl) dimethylamine, (isobutoxymethyl) dimethylamine, (methoxymethyl) diethanolamine (Methoxymethyl) aminoethanol, methyl (butoxymethyl) aminoethanol, 2- (2-aminoethoxy) ethanol and the like Alkoxyamine; 1- (2-hydroxyethyl) piperazine, 1- (2-aminoethyl) piperazine, 1- Methylpiperazine, 1-amino-4-methylpiperazine, 1-benzylpiperazine, 1-phenylpiperazine, N-methylmorpholine, 4-ethylmorpholine, N-formylmorpholine, N - (2-hydroxyethyl) morpholine, N- (3-hydroxypropyl) morpholine and the like.

The alkali-based compound is preferably contained in an amount of 1 to 35% by weight based on the total weight of the composition. If it is less than 1% by weight, the peeling force of the photoresist may be deteriorated. If it exceeds 35% by weight, the damage of the metal surface may be increased.

(c) a water-soluble organic solvent

The water-soluble organic solvent may be a protonic polar solvent, apolar polar solvent or a mixture thereof.

The protonic polar solvent is preferably selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol But are not limited to, monoisopropyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, polyethylene glycol monomethyl ether, polyethylene glycol mono Butyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether Ether compounds, such as, diethylene glycol methyl ethyl ether, diethylene glycol methyl ether, triethylene glycol methyl ether, propylene glycol monomethyl ether acetate; Alkyl glycols such as diethylene glycol, methyldiglycol, butyldiglycol, triethylene glycol and isopropylglycol; tetrahydroperfurfuryl alcohol, perfuryl alcohol; diacetone alcohol, ethylene glycol, glycerin and other alcohols; 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? -butyrolactone; Sulfoxide compounds such as dimethyl sulfoxide (DMSO) and sulfolane; Phosphate compounds such as triethyl phosphate, tributyl phosphate and the like; Carbonate compounds such as dimethyl carbonate, ethylene carbonate and the like; N, N-dimethylacetamide, N- (2-hydroxyethyl) acetamide, 3-methoxypyridine, N, N-dimethylformamide, Amide compounds such as N, N-dimethylpropionamide, 3- (2-ethylhexyloxy) -N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide and dimethyl lactamide These can be used alone or in admixture of two or more.

The protonic polar solvent further swells and further increases the dissolution rate of the photoresist dispersed by the exfoliation liquid, and helps to strengthen the rinse in the DI water rinse process used after the exfoliation liquid is cleaned. Since it helps to rinse the dispersed photoresist cleanly with deionized water after the peeling process, the DI rinse process time can be shortened, no foreign matters remain, and the yield can be improved. Also, one of the problems that may appear in metal film quality is that the problem related to staining can be solved because the deionized water rinse process is cleanly removed when the protonic polar solvent is added in relation to the stain.

The aprotic polar solvent is preferably a pyrrolidone compound such as N-methylpyrrolidone (NMP) or N-ethylpyrrolidone; Imidazolidinone compounds such as 1,3-dimethyl-2-imidazolidinone and 1,3-dipropyl-2-imidazolidinone; lactone compounds such as? -butyrolactone; Sulfoxide compounds such as dimethylsulfoxide (DMSO) and sulfolane; Phosphate compounds such as triethyl phosphate, tributyl phosphate and the like; Carbonate compounds such as dimethyl carbonate, ethylene carbonate, and the like; N, N-dimethylacetamide, N- (2-hydroxyethyl) acetamide, 3-methoxypyridine, N, N-dimethylformamide, Amide compounds such as N, N-dimethylpropionamide, 3- (2-ethylhexyloxy) -N, N-dimethylpropionamide and 3-butoxy-N, N-dimethylpropionamide, These can be used alone or in admixture of two or more.

The aprotic polar solvent serves to dissolve the resist polymer gelled by the alkaline compound and smoothly disperses the photoresist to thereby cause salvation. As the organic solvent, which is very effective in dissolving the photoresist, Which accelerates the penetration of the organic amine compound into the solidified photoresist, thereby improving the peeling performance. In addition, it facilitates the removal of the stripping liquid by deionized water during the rinsing of the deionized water after the photoresist stripping, thereby minimizing the re-adsorption / re-adhesion of the stripping liquid and the dissolved photoresist. It is preferable that the water-soluble polar solvent is not too high or low in boiling point for proper peeling force, and may be mixed and used.

The water-soluble organic solvent is preferably contained in an amount of 60% by weight to 90% by weight based on the total weight of the composition. If it is less than 60% by weight, the ability to contain dissolved photoresist in the solution may deteriorate, and the water treatment ability may be deteriorated. If the amount exceeds 90% by weight, the content of other components may be decreased to affect metal corrosion and peeling force have.

(d) deionized water

The deionized water contained in the photoresist stripper solution composition of the present invention improves the activation of the alkaline compound to increase the removal rate of the photoresist. The deionized water is mixed with the water-soluble organic solvent and remains on the substrate during rinsing with deionized water The organic contaminants and the photoresist stripping liquid can be quickly and completely removed.

The deionized water is preferably contained in an amount of 1 wt% to 60 wt% based on the total weight of the composition. If the amount exceeds 60% by weight, the dissolution capacity of the photoresist is decreased to reduce the number of treatments, and corrosion of the metal wiring can be caused in the case of prolonged immersion of the substrate.

(e) Corrosion inhibitor

The release liquid composition of the present invention may further comprise a corrosion inhibitor.

Examples of the corrosion inhibitor include monocarboxylic acids such as formic acid, acetic acid and propionic acid, dicarboxylic acids such as malic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimetic acid, maleic acid, fumaric acid and glutaconic acid , Tricarboxylic acids such as trimellitic acid and tricarvaleric acid, and organic acids such as hydroxycarboxylic acid such as hydroxyacetic acid, lactic acid, salicylic acid, malic acid, tartaric acid, citric acid and gluconic acid; Maleic amide esters, maleic amide esters, maleic amide esters, fumaric amide esters, oxalic amide esters, malonic amide esters, glutaric amide esters, acetic amide esters, lactic amide esters, Organic acid amide esters such as tartaric amide esters, tartaric amide esters, tartaric amide esters, tartaric amide esters, tartaric amide esters, tartaric amide esters, tartaric amide esters, tartaric amide esters, 2,2 '- [[[[[benzotriazole] methyl] imino] bisethanol, 2,2' - [[[methyl-1-hydrogen-benzotriazole Yl] methyl] imino] bisethanol, 2,2 '- [[[ethyl-1-hydrogen-benzotriazol- Methyl-imino] biscarboxylic acid [methyl-1-hydrogen-benzotriazol-1-yl] methyl] imino] bisethanol and 2,2 '- [[ Benzimidazol-1-yl] methyl] imino] bismethylamine, 2,2 '- [[[ Yl] methyl] imino] bisethanol; Quinone compounds such as 1,2-benzoquinone, 1,4-benzoquinone, 1,4-naphthoquinone and anthraquinone, and quinone compounds such as catechol, pyrogallol, methyl gallate, propyl gallate, Alkyl gallate compounds such as tallylate, gallic acid, and the like, but are not limited thereto. These may be used alone or in combination of two or more.

The above compound serves as a corrosion inhibitor, but is excellent in solubility in water and a polar solvent and does not remain on the surface of the substrate. Therefore, the compound is excellent in corrosion resistance of metal wiring metallization including aluminum and / or copper, It does not cause color change.

The corrosion inhibitor is preferably contained in an amount of 0.001 to 3% by weight based on the total weight of the composition. If it is less than 0.001% by weight, corrosion may occur in the metal wiring made of aluminum or aluminum alloy and copper or copper alloy in the peeling or deionized water rinsing process, and if it exceeds 3% by weight, secondary contamination due to adsorption of metal wiring surface and Deterioration of peeling force may occur.

Hereinafter, the present invention will be described in more detail with reference to Examples, Comparative Examples and Experimental Examples. However, the following examples, comparative examples and experimental examples are for illustrating the present invention, and the present invention is not limited by the following examples, comparative examples and experimental examples, and can be variously modified and changed.

Example  1 to 5 and Comparative Example  1 to 5: Photoresist Peeling liquid  Preparation of composition

The photoresist stripping solution composition was prepared by mixing the ingredients and the contents shown in the following Table 1, and the content of the components listed in Table 1 is expressed as% by weight with respect to the total composition.

division (2)
(weight%) (3)
(weight%) Alkali-based compound (% by weight) Quantum-polar polar organic solvent (wt.%) Aprotic polar organic solvent (wt.%) Additional additives (% by weight) Example 1 0.5 DGA 3 EDG 60 NMP 36.5 Example 2 0.8 TEA 3 MDG 50 DMSO 46.2 Example 3 0.2 0.7 MDEA 5 BDG 30 NMP 64.1 Example 4 0.5 0.4 DEA 4 TEG 40 NMF 55.1 Example 5 0.6 0.3 DGA 3 IPG 35 NMP 51.1 DIW 10 Comparative Example 1 MEA 5 EDG 60 NMP 35 Comparative Example 2 20 DEA 5 BDG 45 NMP 30 Comparative Example 3 30 DEA 5 MDG 20 NMP 35 Comparative Example 4 5 25 DGA 3 IPG 40 NMP 27 Comparative Example 5 DGA 3 MDG 70 NMP 20 DMI 7

Note) DGA: diglycolamine

TEA: triethanolamine

MDEA: methyl diethanolamine

DEA: diethanolamine

MEA: Monoethanolamine

EDG: diethylene glycol

MDG: methyl diglycol

BDG: butyl diglycol

TEG: triethylene glycol

IPG: isopropyl glycol

NMP: N-methylpyrrolidone

DMSO: dimethylsulfoxide

NMF: N-methylformamide

DIW: Deionized water

DMI: 1,3-dimethyl-2-imidazolidone

< Experimental Example > Metal wiring Revolution  evaluation

The photoresist stripper compositions of Examples 1 to 5 and Comparative Examples 1 to 5 were maintained at a constant temperature of 50 캜 and then Cu / Ti ( X) wirings were immersed for 15 minutes and 30 minutes, respectively. After washing and drying, the corrosion force was confirmed and the corrosion rate was measured using a scanning electron microscope (SEM, Hitach S-4700) The results are shown in Table 2, and the results are shown as &quot; good &quot;, &quot; good &quot;, &quot; good &quot;

division 15 min deposition 30 minute deposition Corrosion rate
(Å / min) Also, Corrosion rate
(Å / min) Also, Example 1 0.62 ◎ 1.0 ◎ Example 2 0.53 ◎ 0.88 ◎ Example 3 0.18 ◎ 0.34 ◎ Example 4 0.13 ◎ 0.27 ◎ Example 5 0.11 ◎ 0.20 ◎ Comparative Example 1 -
(Peeling) × -
(Peeling) × Comparative Example 2 1200 △ -
(Peeling) × Comparative Example 3 533 △ -
(Peeling) × Comparative Example 4 -
(Peeling) × -
(Peeling) × Comparative Example 5 -
(Peeling) × -
(Peeling) ×

From the results shown in Table 2, the photoresist stripping solution compositions of Examples 1 to 5 of the present invention exhibited excellent corrosion resistance along with a corrosion rate of 0.1 A / min or less.

However, Comparative Examples 1 to 5, which did not contain the compound of the formula (2) or (3) or had the high content of the compound of the formula (2) or (3), showed poor corrosion performance and a rapid corrosion rate as compared with the compositions of Examples 1 to 5.

Claims (6)

(a) at least one compound represented by the following formula (1);
(b) an alkaline compound; And
(c) a water-soluble organic solvent,
Wherein the compound represented by Formula 1 is contained in an amount of 0.01 to 5% by weight based on the total composition.
[Chemical Formula 1]

In the above formula (1), R is CH ₂ or NH. The method according to claim 1,
(a) a compound represented by the following formula (2) and a compound represented by the following formula (3)
(2)

(3)

(b) an alkaline compound; And
(c) a water-soluble organic solvent. The method according to claim 1,
(A) from 0.01 to 5% by weight of a compound of formula (I); (b) 1 to 35% by weight of an alkaline compound; And (c) 60 to 90% by weight of a water-soluble organic solvent. The method according to claim 1,
The alkaline compound (b) is one or more selected from the group consisting of KOH, NaOH, Tetramethyl ammonium hydroxide (TMAH), Tetraethyl ammonium hydroxide (TEAH), carbonate, phosphate, ammonia and amines. Resist stripper composition. The method according to claim 1,
(C) the water-soluble organic solvent is a protonic polar solvent, an aprotic polar solvent or a mixture thereof. The method according to claim 1,
(d) 1 to 20% by weight of deionized water.