TW201610144A - Stripper composition for removing photoresist and method for stripping photoresist using the same - Google Patents

Abstract

The present invention relates to a stripper composition for removing a photoresist which includes: at least one amine compound; an amide-based compound in which a linear or branched alkyl group having 1-5 carbon atoms is mono- or di-substituted with nitrogen; a polar organic solvent; a triazole-based compound; and a benzimidazole-based compound, and a method for stripping a photoresist using the same.

Description

Stripping composition for removing photoresist and photoresist peeling method using same

The present invention relates to a stripper composition for removing photoresist and a photoresist stripping method using the same. More specifically, the present invention relates to a stripper composition for removing photoresist which is capable of suppressing corrosion of a lower metal film and effectively removing oxide during a stripping process, while having excellent peeling and rinsing light. The ability to resist; and a method of resist stripping using it.

A manufacturing process of a microcircuit or a semiconductor integrated circuit of a liquid crystal display device includes the steps of forming a plurality of lower films on a substrate, such as a conductive metal film made of aluminum, aluminum alloy, copper, copper alloy, molybdenum or molybdenum alloy. Or an insulating film such as a hafnium oxide film, a tantalum nitride film or an acryl-based insulating film; uniformly coating a photoresist on the lower film; optionally exposing and developing the applied photoresist to form a photoresist a pattern; and the photoresist pattern is used as a mask to pattern the lower film.

After these patterning steps, a process of removing residual photoresist on the lower film is performed. For this purpose, a stripper composition for removing photoresist is used.

Previously, it has been known and generally used a stripper composition comprising an amine compound, a polar protic solvent, a polar aprotic solvent, and the like.

These stripper compositions are known to exhibit a degree of ability to remove and strip photoresist. However, in the case where a large amount of photoresist is peeled off, these conventional release agent compositions contribute to the decomposition of the amine compound over time, and thus there is a problem that the peeling and rinsing ability is lowered with time.

In particular, depending on the application time of the stripper composition, these problems may be further accelerated when a portion of the residual photoresist is dissolved in the stripper composition.

Further, in the case where a copper metal film is used as the lower film, stains and foreign matter appear due to corrosion during the peeling process, and thus there are difficulties in use thereof. In addition, there are limitations in that copper oxide cannot be effectively removed.

Therefore, there is a need to develop a new stripper composition which is capable of suppressing corrosion of the underlying metal film and effectively removing oxide while maintaining excellent peeling and rinsing ability over time.

It is an object of the present invention to provide a stripper composition for removing photoresist which is capable of suppressing corrosion of the underlying metal film and effectively removing oxide during the stripping process, while having excellent peeling and rinsing photoresist Ability.

Another object of the present invention is to provide a photoresist stripping method using the stripper composition described above for removing photoresist.

In order to achieve the above object, the present invention provides a release agent composition for removing a photoresist comprising: at least one amine compound; a guanamine compound having a linear or branched alkyl group having 1 to 5 carbon atoms Monosubstituted or disubstituted by nitrogen; polar organic solvent; a triazole-based compound; and a benzimidazole-based compound.

The present invention also provides a photoresist stripping method comprising the steps of: forming a photoresist pattern on a substrate on which a lower film is formed: patterning the lower film with a photoresist pattern; and using the above-mentioned stripper for removing photoresist The composition peels off the photoresist.

Hereinafter, a release agent composition for removing a photoresist and a photoresist peeling method using the same according to a specific embodiment of the present invention will be described in more detail below.

According to one embodiment, the present invention provides a stripper composition for removing a photoresist comprising: at least one amine compound; a guanamine compound having a linear or branched alkyl group having 1 to 5 carbon atoms Monosubstituted or disubstituted by nitrogen; polar organic solvent; triazole compound represented by Formula 1; and benzimidazole compound represented by Formula 2. [Formula 1]

Here, R1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R2 and R3 are the same or different from each other and are each independently a hydroxyalkyl group having 1 to 4 carbon atoms, and a is an integer of 1 to 4 , [Formula 2] Here, R4 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and b is an integer of 1 to 4.

The present inventors have confirmed through extensive experiments that at least one amine compound, a guanamine compound (a linear chain having 1 to 5 carbon atoms therein) is used when the specific stripper composition for removing a photoresist described above is used. Or a branched alkyl group which is mono- or disubstituted with nitrogen) and a polar organic solvent which maintains excellent peeling ability over time and effectively removes metal oxides, and triazole compounds and benzimidazole compounds inhibit the lower portion Corrosion of metal film.

The release agent composition for removing the photoresist according to an embodiment of the present invention will be specifically described below.

The release agent composition for removing the photoresist may include a triazole compound represented by Formula 1 and a benzimidazole compound represented by Formula 2. [Formula 1] Here, R1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R2 and R3 are the same or different from each other and are each independently a hydroxyalkyl group having 1 to 4 carbon atoms, and a is an integer of 1 to 4 , [Formula 2] Here, R4 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and b is an integer of 1 to 4.

The triazole compound and the benzimidazole compound described above can inhibit the metal-containing lower film (such as a copper-containing film) after removing the photoresist pattern using the stripper composition for removing the photoresist as described above. ) Corrosion.

Examples of the triazole compound used herein may include, but are not particularly limited to, a compound of Formula 1, wherein R1 is a methyl group, each of R2 and R3 is a hydroxyethyl group, and a is 1.

Further, examples of the benzimidazole compound used herein may include, but are not particularly limited to, a compound of Formula 2, wherein R4 is hydrogen and b is 1.

The triazole compound may be contained in an amount of 0.1% by weight to 10% by weight, 0.15% by weight to 5% by weight, 0.2% by weight to 2% by weight or 0.25% by weight to 0.5% by weight based on the total weight of the composition.

If the content of the triazole compound is less than 0.1% by weight based on the total weight of the composition, it may be difficult to effectively suppress corrosion on the lower film.

Further, if the content of the triazole compound is more than 10% by weight based on the total weight of the composition, a large amount of the corrosion inhibitor may be absorbed and remain on the lower film, thereby lowering the electrical characteristics of the copper-containing lower film and the like.

0.1% by weight to 10% by weight, 0.15% by weight to 5% by weight, 0.17% by weight to 2% by weight, 0.18% by weight to 0.5% by weight, or 0.19% by weight to 0.25% by weight, based on the total weight of the composition. A quantity of benzimidazole compound.

If the content of the benzimidazole compound is less than 0.1% by weight based on the total weight of the composition, it may be difficult to effectively suppress corrosion on the lower film.

Further, if the content of the benzimidazole compound is more than 10% by weight based on the total weight of the composition, a large amount of the corrosion inhibitor may be absorbed and remain on the lower film, thereby lowering the electrical characteristics of the copper-containing lower film and the like film. .

The weight ratio between the triazole compound and the benzimidazole compound may be from 0.5:1 to 5:1, from 1:1 to 3:1 or from 1:2 to 2:1.

Since the triazole compound and the benzimidazole compound have the specific weight ratios mentioned above, the stripper composition for removing the photoresist can be maximized to prevent corrosion on the lower metal film. .

Additionally, the stripper composition for removing the photoresist may comprise at least one amine compound.

The above amine component is a component which exhibits peeling ability and can be used to dissolve the photoresist and remove it.

The at least one amine compound may be contained in an amount of from about 0.1% by weight to 10% by weight, from 0.5% by weight to 7% by weight, from 1% by weight to 5% by weight, or from 2% by weight to 4.6% by weight, based on the total weight of the composition. .

Depending on the content of the amine compound, the stripper composition according to one embodiment of the present invention exhibits excellent peeling ability due to excess amine, prevents economical efficiency and efficiency of the process, and further reduces waste liquid and the like. produce.

If an excess of the amine compound is contained, this may cause corrosion of the underlying film (for example, a copper-containing lower film), so it may be necessary to use a large amount of corrosion inhibitor to suppress corrosion.

In this case, a large amount of the corrosion inhibitor can be absorbed and remains on the surface of the lower film due to a large amount of the corrosion inhibitor, thereby lowering the electrical characteristics of the copper-containing lower film and the like.

In particular, the at least one amine compound may comprise a chain amine compound having a weight average molecular weight of greater than 95 grams per mole and a cylic amine compound.

A chain amine compound having a weight average molecular weight of more than 95 g/mole exhibits the ability to peel off the photoresist and also sufficiently remove the natural oxide film on the lower film (for example, a copper-containing film), thereby further improving the copper-containing film thereon The adhesion between the insulating film (for example, tantalum nitride film).

The chain amine compound having a weight average molecular weight of more than 95 g/mole may comprise (2-aminoethoxy)-1-ethanol (AEE), aminoethylethanolamine (aminoethyl) Ethanol amine;AEEA), methyl diethanolamine (MDEA), diethylene triamine (DETA), diethanolamine (DEA), diethylaminoethanol (DEEA), triethanolamine (triethanolamine; TEA), triethylene tetraamine (TETA), or a mixture of both or more.

The chain amine compound having a weight average molecular weight of more than 95 g/mole may be contained in an amount of from 0.1% by weight to 10% by weight or from 0.2% by weight to 8% by weight based on the total weight of the composition.

If the content of the chain amine compound having a weight average molecular weight of more than 95 g/mole is less than 0.1% by weight based on the total weight of the composition, the peeling ability of the release agent composition for removing the photoresist may be lowered.

Further, if the content of the chain amine compound having a weight average molecular weight of more than 95 g/mole is more than 10% by weight based on the total weight of the composition, this may cause corrosion of the copper-containing lower film and may require the use of a large amount of corrosion inhibitor To inhibit corrosion.

In this case, since a large amount of the corrosion inhibitor is used, a large amount of the corrosion inhibitor may be absorbed and remain on the surface of the lower film, thereby lowering the electrical characteristics of the copper-containing lower film and the like.

At the same time, the cyclic amine compound exhibits excellent ability to strip light and also dissolves the photoresist, thereby removing it.

Examples of the cyclic amine compound used herein may include, but are not particularly limited to, imidazolyl-4-ethanol (IME), hydroxyethyl piperazine (HEP), and the like.

The above cyclic amine compound may be contained in an amount of from 0.1% by weight to 10% by weight or from 0.2% by weight to 8% by weight based on the total weight of the composition.

If the content of the cyclic amine compound is less than 0.1% by weight based on the total weight of the composition, the peeling ability of the release agent composition for removing the photoresist may be lowered.

Further, if the content of the cyclic amine compound is more than 10% by weight based on the total weight of the composition, the economic efficiency and efficiency of the method may be lowered by including an excess of the cyclic amine compound.

The weight ratio between the chain amine compound having a weight average molecular weight of more than 95 g/mole and the cyclic amine compound may be from 1:2 to 1:10, 1:2.5 to 1:5 or 1:3 to 1:4.

Since the chain amine compound and the cyclic amine compound having a weight average molecular weight of more than 95 g/mole satisfy the specific weight ratio described above, the peeling ability of the release agent composition for removing the photoresist can be maximized.

Further, the above stripper composition for removing the photoresist may include a guanamine compound in which a linear or branched alkyl group having 1 to 5 carbon atoms is mono- or disubstituted with nitrogen.

The above guanamine compound in which a linear or branched alkyl group having 1 to 5 carbon atoms is mono- or disubstituted with nitrogen can advantageously dissolve an amine compound, and can also be used as a stripper composition for removing a photoresist. It is immersed in the lower film, thus improving the peeling and rinsing ability of the above-mentioned release agent composition.

Specifically, the guanamine compound in which a linear or branched alkyl group having 1 to 5 carbon atoms is mono- or disubstituted with nitrogen may include a guanamine compound in which a methyl group is mono- or disubstituted with nitrogen.

The guanamine compound in which the methyl group is mono- or disubstituted with nitrogen may have the structure of the following formula 11. [Formula 11]

Here, R ₁₁ is hydrogen, methyl, ethyl or propyl, and R ₁₂ and R ₁₃ are each independently hydrogen or a straight or branched alkyl group having 1 to 5 carbon atoms, and R ₁₂ and R ₁₃ At least one of them is a methyl group.

Examples of the linear or branched alkyl group having 1 to 5 carbon atoms used herein may include, but are not limited to, methyl, ethyl, propyl, butyl, isobutyl, pentyl, and the like. group.

Examples of the indoleamine compound in which the methyl group is mono- or disubstituted with nitrogen may include, but are not specifically limited to, a compound of the formula 11, wherein R ₁₂ is a methyl group, and R ₁₁ and R ₁₃ are Each of them is hydrogen.

The linear or branched chain having 1 to 5 carbon atoms therein may be contained in an amount of 10% by weight to 80% by weight, 15% by weight to 70% by weight or 25% by weight to 60% by weight based on the total weight of the composition. A guanamine compound in which an alkyl group is mono- or disubstituted with nitrogen.

Depending on the content range, excellent stripping ability of the stripper composition for removing the photoresist can be ensured, and its peeling and rinsing ability can be maintained for a long period of time as time passes.

Further, the stripper composition for removing the photoresist may contain a polar organic solvent.

The above polar organic solvent may allow the stripper composition for removing the photoresist to be better immersed in the lower film, thus assisting the peeling ability of the stripper composition for removing the photoresist, and furthermore, it may be improved for shifting The release agent composition other than the photoresist effectively removes the rinsing ability of the stain on the lower film such as the copper-containing film.

The polar organic solvent may comprise an alkylene glycol monoalkyl ether, pyrrolidone, sulfone, sulfoxide or a mixture of both or more.

More specifically, the alkylene glycol monoalkyl ether may comprise diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether. , diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, triethylene glycol Alcohol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether Or a mixture of both or greater than the two.

In addition, the alkylene glycol monoalkyl ether used may comprise diethylene glycol alone in view of the excellent wetting ability of the stripper composition for removing the photoresist and thus the improved stripping and rinsing ability. Methyl ether (MDG), diethylene glycol monoethyl ether (EDG), diethylene glycol monobutyl ether (BDG), and the like.

Examples of the pyrrolidone used herein may include, but are not particularly limited to, N-methylpyrrolidone, pyrrolidone, N-ethyl-pyrrolidone, and the like.

Examples of hydrazines used herein may include, but are not specifically limited to, sulfolane.

Examples of the hydrazine used herein may include, but are not specific to, dimethyl hydrazine (DMSO), diethyl hydrazine, dipropylene hydrazine, and the like.

Further, the polar organic solvent may be contained in an amount of 10% by weight to 80% by weight, 20% by weight to 78% by weight or 40% by weight to 70% by weight based on the total weight of the composition.

When the polar organic solvent satisfies the content range described above, the excellent peeling ability of the stripper composition for removing the photoresist can be ensured, and the peeling and rinsing ability can be maintained over a long period of time over time. .

In addition, the stripper composition for removing the photoresist may further comprise an anthraquinone nonionic surfactant.

Since the quinone-based nonionic surfactant contains an amine compound or the like, it can be stably maintained without causing chemical changes, denaturation or even decomposition in a stripper composition having a high alkalinity. Additionally, anthraquinone nonionic surfactants can exhibit excellent compatibility with the aprotic polar solvents or protic organic solvents and the like described above.

Therefore, the quinone nonionic surfactant is well mixed with the other component, and thus it can lower the surface tension of the release agent composition and enable the release agent composition to exhibit the photoresist to be removed and the lower film thereof Good moisture and wetting ability.

Therefore, the bismuth-based nonionic surfactant-containing stripper composition according to one embodiment of the present invention can exhibit excellent photoresist peeling ability and excellent ability to rinse the lower film. Therefore, even after the release agent composition is treated, the stain or foreign matter does not substantially appear or remain in the lower film, and the stain or foreign matter can be effectively removed.

In addition, although a very small amount of anthraquinone nonionic surfactant is added, it can exhibit the effects described above and minimize the occurrence of by-products due to denaturation or decomposition thereof.

In particular, the anthraquinone nonionic surfactant may comprise a polyoxyalkylene polymer.

More specifically, examples of the polyoxyalkylene-based polymer used may include, but are not particularly limited to, a polyether-modified acrylic functional polydimethylsiloxane modified with a polyether. Polyether-modified siloxane, polyether-modified polydimethyl siloxane, polyethylalkyl siloxane An aralkyl-modified polymethylalkyl siloxane, a polyether-modified hydroxy functional polydimethyl siloxane, modified by a polyalkyl-modified polymethylalkyl siloxane, Polyether-modified dimethylpolysiloxane, modified acrylic functional polydimethylsiloxane, or a mixture of both or more Wait.

The quinone nonionic surfactant may be included in an amount of from 0.0005 wt% to 0.1 wt%, from 0.001 wt% to 0.09% wt%, or from 0.001 wt% to 0.01 wt%, based on the total weight of the composition.

When the content of the anthraquinone nonionic surfactant is less than 0.0005 wt% based on the total weight of the composition, the effect of improving the peeling and rinsing ability of the stripper composition may not be fully achieved by the addition of the surfactant.

In addition, if the content of the quinone-based nonionic surfactant is more than 0.1% by weight based on the total weight of the composition, bubbles may be generated under high pressure during the stripping process using the stripper composition, thereby causing stains to appear in the lower portion. On the membrane or causing equipment sensor failure.

The release agent composition for removing the photoresist may further contain a conventional additive as necessary. The specific type and amount of the additive are not specifically limited.

Further, the release agent composition for removing the photoresist can be prepared according to a general method of mixing the components described above. There is no particular limitation on the particular method of producing the stripper composition for removing the photoresist.

Meanwhile, according to another embodiment of the present invention, there may be provided a method of stripping photoresist comprising: forming a photoresist pattern on a substrate in which a lower film is formed; patterning a lower film with a photoresist pattern; and using the above one The stripper composition of the embodiment for removing the photoresist peels off the photoresist.

The description relating to the stripper composition for removing the photoresist includes a detailed description related to the above embodiment.

The photoresist stripping method may comprise the steps of: forming a photoresist pattern on a substrate on which a lower film to be patterned is formed by photolithography; patterning the lower film with a photoresist pattern as a mask; and by using the above The stripper composition described is stripped of the photoresist.

In the photoresist stripping method, the step of forming the photoresist pattern and patterning the lower film may use a manufacturing process of a conventional device, and a specific production method for this manufacturing process is not particularly limited.

Meanwhile, an example of the step of peeling off the photoresist by using the stripper composition for removing the photoresist is not particularly limited. For example, a stripper composition for removing a photoresist may be applied to a substrate in which a photoresist pattern is held and subjected to a step of rinsing with an alkaline buffer solution, followed by rinsing and drying with ultrapure water.

Since the release agent composition described above exhibits excellent peeling ability and the ability to effectively remove the stain on the lower film and the ability to remove the natural oxide film, it can satisfactorily maintain the surface state of the lower film. At the same time, the residual photoresist film on the lower film is effectively removed.

Accordingly, subsequent steps can be suitably performed on the patterned lower layer to form the device.

According to the present invention, it is possible to provide a release agent composition for removing photoresist which is capable of suppressing corrosion of a lower metal film during an exfoliation process and effectively removing oxide while having excellent peeling and rinsing photoresist resistance, and A peeling photoresist method using the same.

Hereinafter, the present invention will be explained in detail with reference to the following examples. However, these examples are merely illustrative of the concept of the invention, and the scope of the inventive concept is not limited thereto. < Example 1 to Example 5 : Preparation of a release agent composition for removing a photoresist >

Each of the components was mixed according to the composition shown in Table 1 below to prepare the stripper composition for removing the photoresist of Examples 1 to 5.

The specific composition ratio of the stripper composition for removing the photoresist thus prepared is summarized in Table 1 below. [Table 1] Composition ratio of the stripper composition for removing the photoresist * IME: imidazolyl-4-ethanol* AEE: (2-amino-ethoxy)-1-ethanol* NMF: N-methylformamide* BDG: diethylene glycol monobutyl ether Ether) * EDG: diethylene glycol monoethyl ether * MDG: diethylene glycol monomethyl ether * corrosion inhibitor 1: [[(methyl-1H-benzotriazol-1-yl)methyl]imino Diethanol ([[(methyl-1H-benzotriazole-1-yl)methyl]imino]bisethanol) *Corrosion inhibitor 2: benzimidazole* surfactant: polydimethyl methoxide modified by polyether <Comparative Example 1 to Comparative Example 7: preparation of release agent used to remove the photoresist composition>

Each of the components was mixed according to the composition shown in Table 2 below to prepare the release agent composition for removing the photoresist of Comparative Example 1 to Comparative Example 7.

The specific composition ratio of the stripper composition for removing the photoresist thus prepared is summarized in Table 2 below. [Table 2] Composition ratio of the stripper composition for removing the photoresist * IME: imidazolyl-4-ethanol* AEE: (2-amino-ethoxy)-1-ethanol* MEA: methylethylamine* HEP: hydroxyethylpiperazine* AEEA: aminoethylethanolamine* NMF: N-dimethylformamide * BDG: diethylene glycol monobutyl ether * EDG: diethylene glycol monoethyl ether * MDG: diethylene glycol monomethyl ether * first corrosion inhibitor: [[(A -1H-benzotriazol-1-yl)methyl)]imino]diethanol*2nd corrosion inhibitor: benzimidazole* surfactant: polydimethylene oxime modified by polyether Alkane < Experimental Example : Physical properties of the stripper composition for removing photoresist obtained in the examples and comparative examples >

The physical properties of the stripper composition for removing the photoresist obtained in the examples and the comparative examples were measured by the following methods, and the results are shown in the following table. 1. Peeling ability 1-1. Evaluating the peeling ability of the new liquid of the stripper

First, a 3.5 ml photoresist composition (trademark: JC-800) was dropwise added to a 100 mm × 100 mm glass substrate, and the photoresist composition was applied by a spin coating apparatus at a speed of 400 rpm for 10 seconds.

The glass substrate was equipped with a hot plate and baked hard at a temperature of 150 ° C or 140 ° C for 20 minutes to form a photoresist.

The glass substrate on which the photoresist was formed was air-cooled at room temperature, and then cut into a size of 30 μm × 30 μm to prepare a sample for evaluating the peeling ability of the new stripper liquid.

500 g of the release agent composition obtained in Examples 1 to 5 and Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 7 were prepared. The photoresist on the glass substrate was treated with a stripper composition in a state in which the temperature was raised to 50 °C.

The time to completely strip and remove the photoresist was measured to evaluate the peeling ability of the stripper new liquid.

At this time, the peeling ability of the photoresist was confirmed by observing whether or not the photoresist remained after the ultraviolet light was emitted on the glass substrate.

In the above methods, the new liquid peeling ability of the release agent compositions of Examples 1 to 5 and Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 7 was evaluated, and the results are shown in Table 3 below. [Table 3] New liquid peeling ability of the stripper composition for removing photoresist

As shown in Table 3 above, it has been confirmed that the release agent compositions of Examples 1 to 5 exhibit a photoresist peeling ability (rapid peeling time) equal to or greater than: N-methylformaldehyde (NMF)-free Comparative Example 1 and Comparative Example 2, a release agent composition, a release agent composition of Comparative Example 3 containing no diethylene glycol monobutyl ether (BDG), and a release agent composition of Comparative Example 7 containing only one type of amine.

From these results, it was confirmed that the release agent composition of the above examples exhibited and maintained excellent peeling ability by containing two types of amines, N-methylformaldehyde (NMF) and diethylene glycol monobutyl ether (BDG). 1-2. Stripping ability over time

A sample for evaluating the peeling ability was prepared in the same manner as Experimental Example 1-1. 500 g of the release agent composition obtained in Examples 1 to 5 and Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 7 were prepared. The photoresist composition was dissolved in an amount of 3% by weight based on the entire composition, in which the temperature was raised to 50 °C.

The stripper composition was heated for 48 hours to cause a change over time under harsh conditions.

The peeling ability of the release agent compositions of Examples 1 to 5 and Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 7 over time was evaluated in the same manner as Experimental Example 1-1. The results are shown in Table 4 below. [Table 4] The peeling ability of the stripper composition for removing the photoresist over time

As shown in Table 4 above, the release agent compositions of Examples 1 to 5 exhibited a photoresist peeling ability (rapid peeling time) equal to or greater than: Comparative Example 1 and Comparative Example without N-methylformaldehyde (NMF) 2 A release agent composition, a release agent composition of Comparative Example 3 containing no diethylene glycol monobutyl ether (BDG), and a release agent composition of Comparative Example 7 containing only one type of amine.

From these results, it was confirmed that the release agent composition of the above examples exhibited and maintained excellent peeling ability by containing two types of amines, N-methylformaldehyde (NMF) and diethylene glycol monobutyl ether (BDG). 2. Evaluate flushing capacity

The 500 gram stripper composition of Example 1 and Comparative Example 5 was heated to a temperature of 50 °C. The glass substrate was treated with a release agent composition using a glass substrate on which a film containing copper was formed.

Subsequently, the glass substrate was removed by liquid and a few drops of ultrapure water were added dropwise thereto for 50 seconds.

The substrate was washed again with ultrapure water, and stains and foreign matter on the glass substrate were observed with an optical microscope to evaluate the rinsing ability under the following criteria. OK: no stain or foreign matter on the glass substrate was observed; and NG: stains or foreign matter on the glass substrate were observed on the glass substrate.

The rinsing ability of the release agent compositions of Example 1 and Comparative Example 5 over time was evaluated in the method as described above and the results are shown in Table 5 below.

These results are demonstrated by separately evaluating the rinsing capacity over time under different conditions. [Table 5] Flushing ability of the stripper composition for removing the photoresist

As shown in Table 5 above, in view of the change in appearance over time, it has been confirmed that even under the severe conditions of prolonging the heating of the photoresist composition, since the release agent composition of Example 1 contains a surfactant, it exhibits and maintains the rinsing ability. For a long time.

In contrast, it has been confirmed that since the release agent composition of Comparative Example 5 does not contain a surfactant, it exhibits a reduced flushing ability of the film formed on the glass substrate.

From these results, it was confirmed that the surfactant contained in the release agent composition of the example exhibited and maintained excellent rinsing ability. 3. Evaluate the removal efficiency of copper oxide

The 500 gram stripper compositions of Example 2 and Comparative Example 3 and Comparative Example 6 were heated to a temperature of 50 ° C, and copper (Cu) metal was immersed in the stripper composition for 1 minute, and then washed with ultrapure water for 1 minute. .

The ratio of oxygen element to copper element in the washed copper metal was measured using X-ray photoelectron spectroscopy (XPS) to evaluate the removal efficiency of copper oxide. The results are shown in Table 6 below. [Table 6] Removal efficiency of copper oxide in the stripper composition for removing photoresist

As shown in Table 6 above, it has been confirmed that the Example 2 release agent composition is compared to the Comparative Example 3 and the Comparative Example 6 release agent composition without (2-aminoethoxy)-1-ethanol (AEE). Shows increased copper oxide removal efficiency.

Based on these results, it has been confirmed that the (2-aminoethoxy)-1-ethanol (AEE) contained in the release agent composition of the example has an excellent ability to remove the oxide film of the copper wire. 4. Evaluation of Corrosion 4-1. Evaluation of Corrosion of Copper (Cu) Metals

A 3.5 ml photoresist composition (trademark: JC-800) was added dropwise to a 100 mm x 100 mm glass substrate on which a copper-containing film was formed. The photoresist composition was applied in a spin coating apparatus at a speed of 400 rpm for 10 seconds.

The glass substrate was equipped with a hot plate and baked hard at a temperature of 150 ° C or 140 ° C for 20 minutes to form a photoresist.

The glass substrate on which the photoresist was formed was air-cooled at room temperature, and then cut into a size of 30 mm × 30 mm to prepare a sample for evaluation.

The 500 gram stripper composition obtained in Example 3 and Comparative Example 4 was heated to a temperature of 50 °C. The sample for evaluation of corrosivity was immersed in the stripper composition for 10 minutes at a temperature of 50 ° C, and then washed with ultrapure water.

The surface corrosion of the washed samples was measured by SEM to evaluate the corrosivity of the copper metal, and the results are shown in Table 7 below. [Table 7] Corrosion of the release agent composition for removing the photoresist

As shown in Table 7 above, it has been confirmed that since the stripper composition of Example 3 contains two types of corrosion inhibitors (first inhibitor and second inhibitor), it contains a type of corrosion inhibitor (second inhibition). The comparative example 4 of the agent) exhibited reduced copper metal corrosion compared to the stripper composition.

Based on these results, it was confirmed that the two types of corrosion inhibitors (first inhibitor and second inhibitor) contained in the stripper composition of the example exhibited excellent ability to prevent corrosion of copper metal. 4-2. Evaluating the corrosivity of molybdenum ( Mo )

A sample for evaluating corrosivity was prepared in the same manner as Experimental Example 1-1, except that a molybdenum-containing film was formed instead of the copper-containing film.

The 500 gram stripper composition of Example 4 and Comparative Example 6 was heated to a temperature of 50 ° C, and the sample for evaluation of corrosivity was immersed in the stripper composition for 10 minutes at a temperature of 50 ° C, and then super Wash with pure water.

The surface corrosion of the washed samples was evaluated via SEM, and the results are shown in Table 8 below. [Table 8] Corrosion of the release agent composition for removing the photoresist

As shown in Table 8 above, it has been confirmed that since the stripper composition of Example 4 contains two types of corrosion inhibitors (first inhibitor and second inhibitor), it contains a type of corrosion inhibitor (first inhibition). The comparative example 6 of the agent) exhibited reduced molybdenum metal corrosion resistance compared to the stripper composition.

Based on these results, it was confirmed that the two types of corrosion inhibitors (first inhibitor and second inhibitor) contained in the example stripper composition exhibited excellent ability to prevent corrosion of molybdenum metal.

no.

Claims (12)

A stripper composition for removing photoresist, comprising: at least one amine compound; a guanamine compound, wherein a linear or branched alkyl group having 1 to 5 carbon atoms is mono- or disubstituted with nitrogen; a polar organic solvent; a triazole compound represented by Formula 1; and a benzimidazole compound represented by Formula 2: [Formula 1] Wherein R 1 is hydrogen or an alkyl group having 1 to 4 carbon atoms, R 2 and R 3 are the same or different from each other and are each independently a hydroxyalkyl group having 1 to 4 carbon atoms, and a is an integer of 1 to 4, [Formula 2] Wherein R4 is hydrogen or an alkyl group having 1 to 4 carbon atoms, and b is an integer of 1 to 4. A stripper composition for removing a photoresist according to claim 1, wherein a weight ratio between the triazole compound and the benzimidazole compound is from 0.5:1 to 5:1. Within the scope. The stripper composition for removing photoresist as described in claim 1, wherein the at least one amine compound comprises a chain amine compound having a weight average molecular weight of more than 95 g/mole and a cyclic amine compound. A release agent composition for removing a photoresist according to claim 3, wherein a weight ratio of the chain amine compound to the cyclic amine compound having a weight average molecular weight of more than 95 g/mole is used. It is 1:2 to 1:10. A stripper composition for removing a photoresist according to the above-mentioned claim 1, wherein the linear or branched alkyl group having 1 to 5 carbon atoms is mono- or disubstituted by nitrogen The guanamine compound includes a guanamine compound in which a methyl group is mono- or disubstituted with nitrogen. The stripper composition for removing a photoresist according to claim 1, wherein the polar organic solvent comprises an alkylene glycol monoalkyl ether, pyrrolidone, anthracene, and anthracene. One or more of the ethnic groups selected. The stripper composition for removing photoresist as described in claim 1, comprising: 0.1% by weight to 10% by weight, based on the total weight of the stripper composition, of the at least one amine a compound; 10% by weight to 80% by weight of the guanamine compound in which a linear or branched alkyl group having 1 to 5 carbon atoms is mono- or disubstituted with nitrogen; 10% by weight to 80% by weight a polar organic solvent; 0.1% by weight to 10% by weight of the triazole compound; and 0.1% by weight to 10% by weight of the benzimidazole compound. The stripper composition for removing photoresist as described in claim 1, which further comprises an anthraquinone nonionic surfactant. The stripper composition for removing photoresist as described in claim 8, wherein the anthraquinone nonionic surfactant comprises a polyoxyalkylene polymer. The release agent composition for removing a photoresist according to claim 9, wherein the polyoxyalkylene-based polymer comprises one or more selected from the group consisting of: Polyether modified acrylic functional polydimethyl siloxane, polyether modified siloxane, polyether modified polydimethyl siloxane, polyethyl alkyl decane, Aralkyl modified polymethylalkyl siloxane, polyether modified hydroxy functional polydimethyl siloxane, polyether modified dimethyl polyoxy siloxane, and modified Acrylic functional polydimethyl siloxane. The stripper composition for removing photoresist as described in claim 8, wherein the anthraquinone nonionic surfactant is 0.0005 wt% to 0.1 based on the total weight of the stripper composition. The amount by weight is contained therein. A photoresist stripping method comprising the steps of: forming a photoresist pattern on a substrate on which a lower film is formed; patterning the lower film with the photoresist pattern; and using the method as recited in claim 1 The stripper composition for removing the photoresist peels off the photoresist.