KR101319217B1 - Photoresist stripper composition, and a exfoliation method of photoresist using the same - Google Patents

Abstract

The present invention relates to a photoresist stripper composition comprising a compound of formula (1) (see Configuration of the Invention) and a method of stripping a photoresist using the same.

The present invention can easily peel off the cured or altered photoresist (polymer) generated during the wet or dry etching process in a low temperature or a short time by immersion, spraying, sheeting or air knife method, the metal wiring exposed to the peeling solution In particular, it has excellent anticorrosive properties for substrates on which metal layers and inorganic material layers having a multi-junction structure including copper are formed, and in subsequent rinsing processes, rinsing with water alone does not require the use of organic solvents such as isopropyl alcohol and dimethyl sulfoxide. It is possible to provide an environmentally friendly photoresist stripper composition which does not contain a benzotriazole compound which is poorly biodegradable, and a method of stripping a photoresist using the same.

Photoresist, stripping solution, corrosion inhibitor, curing, alteration

Description

Photoresist stripper composition and method of stripping photoresist using the same {PHOTORESIST STRIPPER COMPOSITION, AND A EXFOLIATION METHOD OF PHOTORESIST USING THE SAME}

The present invention relates to a photoresist stripper composition and a method of stripping a photoresist using the same. More specifically, the present invention relates to a peeling liquid composition of a photoresist film remaining after wet and dry etching in manufacturing processes of semiconductor devices and liquid crystal display devices, and a method of peeling a photoresist using the same.

In the manufacture of a semiconductor device or a liquid crystal display device, metal wiring is usually formed by forming a metal, inorganic material or metal oxide layer on a semiconductor substrate or a glass substrate, forming a photoresist layer, applying a mask pattern to the photoresist. It proceeds to the exposure process to transfer, the etching process to etch a film along a pattern, and the peeling process to remove a photoresist.

However, in recent years, the etching conditions of metals or oxide films have been severed due to the ultra-fine pattern of semiconductor devices and liquid crystal display devices, and thus the frequency of hardening and deterioration of photoresist by etching processes has increased.

Specific etching processes are classified into wet etching using an electrochemical reaction and dry etching using a radical reaction of a plasma-etched etching gas. The hardened and altered photoresist (polymer) generated after the etching process is difficult to remove even using a conventional photoresist stripper. If the cured and altered photoresist (polymer) is not completely removed, photoresist residues may cause disconnection and short circuit in subsequent processes, which may cause a decrease in yield in the production of semiconductor devices or liquid crystal display devices.

In addition, high integration of semiconductor elements and ultra miniaturization of patterns, as well as wiring delays due to the resistance (wiring resistance) and wiring capacitance of metals used in semiconductor elements, have become a problem. In order to improve the wiring resistance, it is proposed to use a metal having a lower resistance than aluminum (Al), for example, copper (Cu), which has been mainly used as a wiring material, and is in the stage of practical use.

As a solution for peeling the patterned photoresist layer, i.e., the release agent, an inorganic acid, an inorganic base, or an organic solvent, for example, a halogenated organic solvent, an alkylbenzene sulfonic acid, a mixture of an aromatic hydrocarbon solvent and an alkylbenzene sulfonic acid, and the like can be mentioned. . However, in the case of using an inorganic acid or an inorganic base as an active ingredient of the release agent, it is common to use organic solvents because of the difficulty in operating such as corrosion of the lower metal film or harmful to the human body. An amine release agent with an amine is used a lot.

The amine component in the amine-based releasing agent compositions has been found to be essential for effectively removing crosslinked resist films by calcination, plasma etching, implantation, or other LSI (LARGE SCALE I.C.) device fabrication processes. However, amine-based photoresist strippers sometimes cause serious problems of corrosion, especially when using aluminum and copper substrates.

This corrosion is known to proceed after the exfoliation step, with the residual exfoliation solution remaining on the substrate surface or on the substrate carrier, using water and then ionized with amines in the exfoliation cleaning step. In other words, the amine component of the release composition by itself does not corrode the substrate, but may also serve to trigger water to cause corrosion. In addition to this corrosion problem, due to the difference in the solubility of the foreign matter in the release agent and water, the material dissolved in the residual peeling solution may be precipitated when washed with water immediately after the peeling process.

To solve this problem, an intermediate cleaning step using an organic solvent has been introduced between the stripping step and the stripping step after using water. For example, isopropyl alcohol or dimethyl sulfoxide and the like are known to be useful for this purpose. As another method, an amine release composition has been proposed in which a corrosion inhibitor is added to alleviate the corrosion problem caused by residual amine in the post-peel step.

Examples of documents suggesting the above solution are as follows.

U.S. Patent No. 4,617,251 discloses certain amine compounds (eg, 2- (2-aminoethoxy) ethanol, 2- (2-aminoethylamino) ethanol, or mixtures thereof) and certain polar solvents (eg N -methyl 2-pyrrolidone, tetrahydrofurpryl alcohol, isophorone, dimethyl sulfoxide, dimethyl adipate, dimethyl glutarate, sulfolane, gamma-butyrolactone, N , N -dimethylacetamide and mixtures thereof) A positive photoresist stripping composition containing is disclosed.

U.S. Patent No. 4,786,578 proposes a cleaning solution for use after a photoresist stripper, wherein the cleaning solution described above comprises a nonionic surfactant (such as ethoxylated alkylphenol) and an organic base (such as parent-, di- or tree). Ethanolamine).

U.S. Pat. A cleaning solution after photoresist stripping is disclosed, wherein the cleaning solution described above is non-aqueous.

U.S. Patent No. 4,904,571 discloses solvents (eg, water, alcohols, ethers, ketones, etc.), alkaline compounds (eg, primary, secondary, tertiary amines, quaternary amines, cyclic amines, polyamines) dissolved in the solvent, Quaternary ammonium amine, sulfonium hydroxide, alkali hydroxide, etc.), and a printed circuit board containing borohydride compounds (eg, sodium borohydride, dimethyl amine boron, pyridine boron, etc.) dissolved in the solvent. Photoresist strippers are disclosed.

International Publication No. WO88 / 05813 proposes a positive or negative photoresist stripper containing butyrolactone or caprolactone, quaternary ammonium hydroxide compounds and any nonionic surfactant.

U.S. Patent 5,478,443 and U.S. Patent 5,320,709 disclose corrosion of metals using certain organic corrosion inhibitors (glycol and dimethyl sulfoxide) and fluorine-containing compounds (ammonium fluoride, hydrofluoric acid, perfluoric acid, etc.). It is proposed to solve the problem. However, in these compositions, a large amount of organic solvent is required, and thus, a large amount of waste has to be removed.

U.S. Patent No. 5,612,304 discloses a stripping solution comprising a polar solvent under certain conditions, a specific alkanolamine, an amino acid having a hydroxyl group, and a redox agent having a specific redox potential because it is not easy to remove the residue after etching. Is proposed. It is described in this document that amino acids with hydroxyl groups are used as corrosion inhibitors, and that organic or inorganic acids degrade the stripping power by lowering the basicity of the amine-containing stripper solution.

Korean Patent Laid-Open No. 2001-0018377 proposes a resist stripping agent containing an amine compound, a glycol solvent, and a perfluoroalkyl ethylene oxide.

Korean Patent Publication No. 2000-0016878 proposes a stripping solution composed of an alkoxy N -hydroxyalkylalkanamide and a polar substance having a dipole moment of 3 or more, a damage preventing agent and an alkanol amine.

Korean Patent Publication No. 2001-00440496 proposes a stripping solution applied to a positive type resist of a novolak resin / quinonediazide compound system using a pyriminone compound.

U.S. Patent No. 5,480,585 and Japanese Patent Application Laid-open No. Hei 5-281753 describe alkanols of the formula _3-n HN ((CH ₂ ) _m OH) _n (m is 2 or 3, n is 1, 2 or 3). An organic stripper for photoresists is proposed which comprises an amine, sulfone compound or sulfoxide compound and a hydroxy compound of the formula C ₆ H _{6 -n} (OH) _n (where n is 1, 2 or 3).

Japanese Patent Application Laid-open No. Hei 4-124668 discloses 20 to 90% by weight of organic amine, 0.1 to 20% by weight of phosphate ester surfactant, 0.1 to 20% by weight of 2-butyne-1,4-diol and the balance of glycol monoalkyl ether and A release agent composition for photoresists comprising an aprotic polar solvent is proposed. Glycol monoalkyl ethers include ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and the like, and aprotic polar solvents include dimethyl sulfoxide, N, N -dimethylacetamide, and the like. Used. 2-butyne-1,4-diol and phosphate ester surfactants are added here to prevent corrosion of metal layers such as aluminum and copper by organic amines absorbed in the photoresist, as long as the peeling properties are not deteriorated. .

Japanese Patent Application Laid-Open No. 64-42653 includes at least 50% by weight of dimethyl sulfoxide, particularly preferably at least 70% by weight, and includes diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, gamma-butyrolactone and 1 1 to 50% by weight of at least one solvent selected from, 3-dimethyl-2-imidazolidinone and 0.1 to 5% by weight of a nitrogen-containing organic hydroxyl compound such as monoethanolamine Proposed. When the dimethyl sulfoxide is less than 50% by weight, the peelability is remarkably lowered, and when the nitrogen-containing organic hydroxyl compound solvent exceeds 5% by weight, it is described that metal layers such as aluminum corrode.

Korean Patent Laid-Open Publication No. 1999-0062480 proposes a stripping liquid comprising an organic amine compound, a protic glycol ether compound, an aprotic multipolar compound, and an alkylpyrrolidone compound.

Korean Patent Laid-Open Publication No. 2000-0008103 discloses a stripper composition for photoresist comprising 5 to 15% by weight of alkanolamine, 35 to 55% by weight of sulfoxide or sulfone compound, 35 to 55% by weight of glycol ether and surfactant Is proposed. It is described here that when the alkanolamine is more than 15% by weight and the sulfoxide or sulfone compound is less than 35% by weight, the water absorption with the LCD front film becomes small, the contact angle is increased, and the peeling performance by the air knife is lowered.

U.S. Patent No. 5,174,816 discloses 0.01 to 15% by weight quaternary ammonium hydroxides such as trimethyl (2-hydroxyethyl) ammonium hydroxide, and 0.1 to 20% by weight sugar or sugar alcohols such as xylitol, mannose, glucose, etc. Disclosed is a composition for removing chlorine remaining on the surface of an aluminum line pattern substrate after dry etching, including an aqueous solution containing a solution.

Japanese Patent Laid-Open No. 07-028254 discloses a non-corrosive resist removal liquid comprising sugar alcohol, alcohol amine, water and quaternary ammonium hydroxide.

Japanese Patent Laid-Open No. 07-247498 discloses a cleaning liquid containing a quaternary ammonium hydroxide, a sugar or a sugar alcohol, and a urea compound.

Korean Patent Publication No. 2001-0106537 discloses 3 to 10% by weight of an organic amine compound, N, N -dimethylacetamide (DMAc), N, N -dimethylformamide (DMF), 1,3-dimethyl-2-imide 30 to 60% by weight of solvents such as dazolidinone (DMI), N -methyl-2-pyrrolidone (NMP), 30 to 60% by weight of water, 1 to 10% by weight of catechol, resorcin or mixtures thereof A resist stripper composition containing 1 to 10% by weight of a straight chain polyhydric alcohol having 4 to 6 carbon atoms is disclosed.

Korean Patent Publication No. 2001-0062828 discloses nitrogen-containing organic hydroxylamines, water-soluble organic solvents (eg, N -methyl-2-pyrrolidone (NMP) and dimethyl sulfoxide), water, and certain benzotriazole-based compounds. A peeling solution for photoresists comprising a compound is disclosed.

However, the organic solvent stripping agent proposed in the prior art used an environmentally harmful alkylpyrrolidone compound and sulfone compound or sulfoxide compound as an organic solvent, the peeling ability to the photoresist and residue is not sufficient, Insufficient dissolving power in the polymer material constituting the photoresist may cause a problem that the exfoliated photoresist residue is reattached to a semiconductor substrate or a glass substrate or generates additional solvent by-products. In addition, the process conditions are high temperature, which is not advantageous in terms of environmental aspects and processing costs, there is a limit to cleaning the residues, there is a problem that the use of organic solvents such as isopropyl alcohol, dimethyl sulfoxide in the subsequent rinsing process . In addition, in the case of the copper resist photoresist stripping solution, the corrosion was prevented by using an azole additive, but in the case of the azole compound, especially 1,2,3-benzotriazole, there was a problem in that a separate waste liquid treatment was required.

On the other hand, in the conventional peeling liquid composition, the corrosion prevention of the metal wiring, in particular, the substrate on which the multi-junction metal wiring including copper is formed, or the substrate on which the metal wiring and the inorganic material are formed, and the peelability of the photoresist film and the photoresist modified film We did not achieve a balance together.

In particular, due to the recent increase in the size and mass production of semiconductor devices and liquid crystal display devices, a single wafer system or an air knife method to be treated by spraying or sheeting, rather than dipping, which is a conventional method of using a stripping agent. Since the photoresist stripping method using is widely used, it is suitable for such a spraying method, a single sheet method, and an air knife method, and is an environmentally friendly release agent composition which can be peeled off without causing corrosion to both metal wirings, particularly copper wirings and inorganic material layers. Development is required.

Therefore, the present invention can easily peel off the cured or altered photoresist (polymer) generated during the wet or dry etching process in a low temperature, a short time by immersion, spraying, sheeting or air knife method, and is exposed to the peeling solution Excellent corrosion resistance for metal interconnects, in particular metal substrates with a multi-junction structure containing copper, and substrates with inorganic material layers, and in subsequent rinsing processes without the need for the use of organic solvents such as isopropyl alcohol and dimethyl sulfoxide. An object of the present invention is to provide an environmentally friendly photoresist stripping solution that is rinsable and does not contain a benzotriazole compound that is poorly biodegradable.

Another object of the present invention is to provide a method of peeling a photoresist film using the above peeling solution.

In order to achieve the above technical problem, the present invention provides a photoresist stripper composition comprising a compound of formula (1).

[Formula 1]

Wherein R 1 and R 2 are each independently a hydrogen atom, C 1 -C 10 alkyl, C 1 -C 10 hydroxyalkyl, C 1 -C 10 alkylamino, C 1 -C 10 aminoalkyl, C 6 -C 10 aryl, or C 7- An aralkyl group of C 15, wherein R 1 or R 2 bonded to one N may form a ring together with R 1 or R 2 bonded to the other N.)

In addition, the present invention is a compound of Formula 1 0.01 to 5% by weight, 1 to 10% by weight of ammonium hydroxide compound, 1 to 30% by weight glycol ether compound, 1 to 30% by weight of a water-soluble organic solvent, and the remaining amount Provided is a photoresist stripper composition comprising deionized water.

This invention also provides the peeling method of the photoresist using said peeling liquid composition.

In the stripper composition of the present invention, the compound of formula 1 is used as a corrosion inhibitor, and specific examples thereof include N, N, N'N'-tetrakis (2-hydroxypropyl) ethylenediamine (quadrol, manufactured by BASF), N , N'-dialkylethylenediamine, N, N'-Bis- (2-aminoethyl) ethane-1,2-diamine, N, N'-dimethyl piperazine, N, N, N'N'-tetraethyl -1,2-ethanediamine, N, N'- diethanol piperazine, or a mixture thereof.

Benzotriazole, which is conventionally used for corrosion protection of copper wiring, shows a slanted bond structure due to coordination bonding of nitrogen-dense parts on the copper surface, whereas the compound of Formula 1 of the present invention bonds in parallel with the copper surface. Since it has a more stable bond structure, the equivalent effect can be acquired with a smaller addition amount. In addition, the benzotriazole compound has an environmental problem that is not biodegradable by microorganisms, but the compound of Compound 1 has the advantage of being biodegradable.

In the stripper composition of the present invention, the content of the corrosion inhibitor compound of Formula 1 is preferably 0.01 to 5% by weight. When used in less than 0.01% by weight, the effect of preventing corrosion is reduced, when used in excess of 5% by weight, but the effect of the method, the problem that the removal force of the photoresist is lowered.

In the peeling liquid composition of this invention, as an ammonium hydroxide compound, tetramethylammonium hydroxide, tetraethylammonium hydroxide, or a mixture thereof is preferable.

The content of the ammonium hydroxide compound in the stripper composition of the present invention is preferably 1 to 10% by weight. When used in less than 1% by weight, the peeling effect of the photoresist film, that is, the oil and inorganic polymer, is reduced after dry etching, ashing, and ion implantation processes. Corrosion to the metal film will appear.

In general, glycol ether derivatives are biodegradable, environmentally friendly organic solvents, and have a wide range of applications as very good solvents that share ether and hydroxyl groups in a molecule and are well mixed with water. The addition of these glycol ethers acts as a kind of surfactant to lower the surface tension of the solution and improve the penetration, thereby enhancing the peeling ability of the peeling solution at a relatively low temperature.

The glycol ether compounds used in the present invention are generally alkylene glycol mono alkyl ethers. Specific examples may include the following compounds.

CH ₃ CH ₂ CH ₂ CH ₂ —OCH ₂ CH ₂ —OH;

CH ₃ CH ₂ CH ₂ CH ₂ —OCH ₂ CH ₂ —OCH ₂ CH ₂ —OH;

CH ₃ CH ₂ CH ₂ CH ₂ —OCH ₂ CH ₂ —OCH ₂ CH ₂ —OCH ₂ CH ₂ —OH;

CH ₃ CH ₂ CH ₂ CH ₂ —OCH ₂ CH ₂ —OCH ₂ CH ₂ —OCH ₂ CH ₂ —OCH ₂ CH ₂ —OH;

CH ₃ -OCH ₂ CH ₂ -OH;

CH ₃ -OCH ₂ CH ₂ -OCH ₂ CH ₂ -OH;

CH ₃ -OCH ₂ CH ₂ -OCH ₂ CH ₂ -OCH ₂ CH ₂ -OH;

CH ₃ -OCH ₂ CH ₂ -OCH ₂ CH ₂ -OCH ₂ CH ₂ -OCH ₂ CH ₂ -OH;

CH ₃ -OCH ₂ CH ₂ CH ₂ -OH;

CH ₃ -OCH ₂ CH ₂ CH ₂ -OCH ₂ CH ₂ CH ₂ -OH;

CH ₃ -OCH ₂ CH ₂ CH ₂ -OCH ₂ CH ₂ CH ₂ -OCH ₂ CH ₂ CH ₂ -OH; And

CH ₃ -OCH ₂ CH ₂ CH ₂ -OCH ₂ CH ₂ CH ₂ -OCH ₂ CH ₂ CH ₂ -OCH ₂ CH ₂ CH ₂ -OH

In particular, preferred glycol ether compounds are ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether or mixtures thereof.

 The content of the glycol ether compound in the stripping solution is preferably 1 to 30% by weight. More preferably, it is 10-25 weight%. At this time, when used at less than 1% by weight, the peeling ability at low temperatures of the photoresist and polymer is lowered, and when used at more than 30% by weight, the compound relatively decomposes the photoresist film, oil and inorganic polymer. The lower the content of the cause of the peeling effect is lowered.

As a water-soluble organic solvent used in the peeling liquid composition of this invention, it is a solvent which is very excellent in the solubility to a polymer resin, N-methylpyrrolidone (NMP), 1, 3- dimethyl- 2-imidazolidinone (DMI) , Dimethyl sulfoxide (DMSO), dimethyl acetamide (DMAc), dimethyl formamide (DMF), tetrahydrofurfuryl alcohol, isophorone, diethyl adipate, dimethyl glutarate, sulfolane, gamma-butyllactone (GBL) Polar solvents such as And mono-, di- or tri-ethanolamine, mono-, di- or tri-propanolamine, mono-, di- or tri-isopropanolamine, butanolamine, butylmonoethanolamine, ethyldiethanolamine, N -methyl One or two or more mixtures selected from the group consisting of aminoalkanol compounds such as aminoethanol are preferable, and 1,3-dimethyl-2-imidazolidinone (DMI) and N-methylpyrrolidone (NMP) , Dimethyl sulfoxide (DMSO), gamma-butyllactone (GBL), mono-, di- or tri-ethanolamine, N -methylaminoethanol, mono-, di- or tri-isopropanolamine One or more mixtures are more preferred.

The content of the water-soluble organic solvent in the stripping solution is preferably 1 to 30% by weight. More preferably, it is 10 to 25% by weight, and when used in less than 1% by weight, the dissolving ability of the photoresist and polymer of the stripping solution is lowered and they are reattached, and when used in excess of 30% by weight It is disadvantageous in terms of both aspects and processing costs, and corrosion occurs.

The stripper composition of the present invention may include a surfactant, an antifoaming agent or a mixture thereof as an additive commonly used in the stripper.

Surfactant may be added to improve the uniformity of the peeling, the addition amount is not limited, but is preferably added in 0.01 to 10% by weight, preferably 0.01 to 5% by weight based on the total stripping liquid composition.

The stripper composition of the present invention is effective for stripping a cured or altered photoresist (polymer) generated during the wet or dry etching process of a substrate formed of a metal wiring and an inorganic material layer. In particular, in semiconductor manufacturing processes such as LSI devices, liquid crystal panels, etc., very low corrosiveness to materials such as oxide films, copper, aluminum, tungsten, molybdenum, chromium, titanium, and indium tin oxide (ITO) metal films constituting the semiconductor. It is especially suitable for metal film of single or multiple junction structure containing copper.

The above-described compounds may be advantageously mixed in a predetermined amount to prepare the release composition of the present invention, and the mixing method is not particularly limited and various known methods may be applied.

The peeling method using the above-mentioned peeling liquid composition which is another aspect of this invention relates to the method of removing the hardened | cured or altered photoresist (polymer) which arises in a wet and dry etching process.

The peeling method may be performed by a peeling method commonly known in the art, and a good result may be obtained if the peeling solution and the substrate on which the photoresist film including the cured or altered photoresist (polymer) is formed can contact each other. Can be obtained.

The peeling method of the present invention may be applied by a method using a deposition, spraying, sheet and air knife method. In the case of peeling by immersion, spraying, sheeting and air knife method, as the peeling condition, the temperature is usually 10 to 100 ° C, preferably 20 to 80 ° C, and the deposition and spraying time is usually 5 seconds to 30 minutes, preferably Although 10 seconds to 10 minutes, the present invention is not limited to this range, it can be easily adapted by those skilled in the art.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the scope of the present invention is not limited to the following examples and the like.

Example  1 to 7 and Comparative Example  1 to 4: Photoresist Peeling liquid  Preparation of the composition

To the compositions and contents as shown in Tables 1 and 2 were prepared to prepare the peeling liquid compositions of Examples 1 to 7 and Comparative Examples 1 to 4.

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 TMAH 2 2 3 3 One 1.5 2 MEA - - - - 5 BDG 20 20 20 20 15 MDG - 20 - - - 20 N, N-dialkylethylenediamine 0.5 Trientin One 0.5 2 2 One 3 DMI 20 20 20 NMP - 20 - - - DMSO - - 20 - 10 GBL 20 10 H ₂ O 57 56.5 53 53 53 58 60

(Unit: wt%)

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 TMAH 10 10 5 10 MEA - - 15 BDG 20 - 30 20 MDG - 25 BTA One 5 5 NMP 20 15 20 Trientin - 7 GBL 20 H ₂ O 49 40 30 40

(Unit: wt%)

TMAH: Tetramethylammonium Hydroxide

MEA: Monoethanolamine

NMP: N-methylpyrrolidone

DMSO: dimethylsulfoxide

GBL: gamma-butyllactone

BDG: diethylene glycol monobutyl ether

MDG: diethylene glycol monomethyl ether

DMI: 1,3-dimethyl-2-imidazolidinone

Trientine: N, N'-Bis- (2-aminoethyl) ethane-1,2-diamine

BTA: 1,2,3 benzotriazole

Test Example : Peel Ability and Corrosion Test

Peeling ability test

After etching, the specimen with the remaining photoresist film was immersed in a stripping solution having a temperature of 65 ^° C. for 10 minutes, and the specimen was removed from the stripping solution, rinsed with ultrapure water for 1 minute, and dried using nitrogen gas. Then, the removal property of the photoresist film was evaluated using a scanning electron microscope, and the results are shown in Tables 3 and 4 below.

Removability  How to Display Evaluation Results

O: good

△: Normal

X: Bad

Corrosion Test

The copper film was deposited on a bare silicon film in a stripping solution having a temperature of 65 ^° C. for 20 minutes, and then the specimen was removed from the stripping solution, rinsed with ultrapure water for 1 minute, and dried using nitrogen gas. And the degree of corrosion was evaluated using a scanning electron microscope and a 4-point probe, the results are shown in Table 3 and Table 4 below.

How to Display Corrosion Evaluation Results

O: good

△: Normal

X: bad

Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Peelability O O O O O O O causticity O O O O O O O

Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Peelability O X X △ causticity △ O O O

As can be seen in Table 4, the stripping solution composition containing the 1,2,3 benzotriazole compound (Comparative Examples 1 to 3), or the stripping solution composition (Comparative Example 4) outside the content range of the present invention has a removability property. Corrosiveness was poor. However, as can be seen from Table 3, it was confirmed that the peeling liquid composition (Examples 1 to 7) according to the present invention was also excellent in removal and corrosion.

 The present invention can easily peel off the cured or altered photoresist (polymer) generated during the wet or dry etching process in a low temperature or a short time by immersion, spraying, sheeting or air knife method, the metal wiring exposed to the peeling solution In particular, it has excellent anticorrosive properties for substrates on which metal layers and inorganic material layers having a multi-junction structure including copper are formed. It is possible to provide an environmentally friendly photoresist stripper without adding a benzotriazole compound which is poorly biodegradable, and a method of stripping a photoresist using the same.

Claims (9)

delete 0.01 to 5% by weight of the compound of Formula 1, 1 to 10% by weight of ammonium hydroxide compound, 1 to 30% by weight of glycol ether compound, 1 to 30% by weight of water-soluble organic solvent, and the balance of deionized water Photoresist stripping liquid composition:

(One) Wherein R 1 and R 2 are each independently a hydrogen atom, C 1 -C 10 alkyl, C 1 -C 10 hydroxyalkyl, C 1 -C 10 alkylamino, C 1 -C 10 aminoalkyl, C 6 -C 10 aryl, or C 7 -C 15 Is an aralkyl group, and R 1 or R 2 bonded to one N may form a ring together with R 1 or R 2 bonded to the other N. The compound of formula 1 is N, N, N'N'-tetrakis (2-hydroxypropyl) ethylenediamine (quadrol, manufactured by BASF), N, N'-dialkylethylenediamine, N , N'-Bis- (2-aminoethyl) ethane-1,2-diamine, N, N'-dimethyl piperazine, N, N, N'N'-tetraethyl-1,2-ethanediamine, N, N'- diethanol piperazine, or a mixture thereof. The photoresist stripper composition according to claim 2, wherein the ammonium hydroxide compound is tetramethylammonium hydroxide, tetraethylammonium hydroxide or a mixture thereof. The method of claim 2, wherein the glycol ether compound is ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, tri Ethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tetrapropylene glycol monobutyl ether, or a mixture thereof Resist stripper composition. The method of claim 2, wherein the water-soluble organic solvent is N-methylpyrrolidone (NMP), 1,3-dimethyl-2-imidazolidinone (DMI), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc), dimethyl Formamide (DMF), tetrahydrofurfuryl alcohol, isophorone, diethyl adipate, dimethylglutarate, sulfolane, gamma-butyllactone (GBL), mono-, di- or tri-ethanolamine, mono-, One or two or more selected from the group consisting of di- or tri-propanolamine, mono-, di- or tri-isopropanolamine, butanolamine, butyl monoethanolamine, ethyl diethanolamine, and N -methylaminoethanol A photoresist stripper composition, characterized in that the mixture. The photoresist stripper composition according to claim 2, which is used to peel a cured or altered photoresist (polymer) generated during a wet or dry etching process of a substrate formed of a metal wiring and an inorganic material layer. 8. The photoresist stripper composition according to claim 7, wherein the metal wiring is a metal wiring of a single or multiple junction structure containing copper. The photoresist stripping method of claim 2, wherein the photoresist (polymer) cured or deteriorated by the deposition, spraying, sheeting or air knife method is stripped using the stripper composition of claim 2.