JP2021518922A - Stripper composition for removing photoresist and method for stripping photoresist using this - Google Patents

Abstract

The present invention uses a photoresist removing stripper composition capable of effectively removing oxides by suppressing corrosion on the lower metal film during the peeling process while having excellent peeling power against the photoresist. It relates to a method of peeling a photoresist.

Description

Mutual citation with related application

This application claims the benefit of priority under Korean Patent Application No. 10-2019-0033204 dated March 22, 2019, and all the contents disclosed in the document of the Korean patent application are a part of this specification. Included as.

The present invention relates to a stripper composition for removing a photoresist and a method for peeling a photoresist using the same. More specifically, the present invention has excellent peeling power for a photoresist and corrosion on a lower metal film during the peeling process. The present invention relates to a photoresist removing stripper composition capable of effectively removing oxides and a method for peeling a photoresist using the same.

In the microcircuit process of the liquid crystal display element or the semiconductor direct circuit manufacturing process, a conductive metal film such as aluminum, aluminum alloy, copper, copper alloy, molybdenum, molybdenum alloy or silicon oxide film, silicon nitride film, fork acrylic insulation is performed on the substrate. Various lower films such as an insulating film such as a film are formed, a photoresist is uniformly applied on such a lower film, and the photoresist pattern is selectively exposed and developed to form a photoresist pattern, and then this is masked. As a result, various steps of patterning the lower film will be included. After such a patterning step, a step of removing the photoresist remaining on the lower film is performed, and what is used for this is a stripper composition for removing the photoresist.

Stripper compositions containing amine compounds, protic and aprotic polar solvents, and the like have long been widely known and mainly used. Such stripper compositions have been known to exhibit some degree of removal and peeling power against photoresists.

However, such an existing stripper composition has a problem that when a large amount of photoresist is peeled off, the decomposition of the amine compound is promoted with time and the peeling force and the rinsing force are lowered with time. In particular, such a problem may be further accelerated if a part of the residual photoresist is dissolved in the stripper composition depending on the number of times the stripper composition is used.

Further, when a copper metal film is used as the lower film, stains and foreign substances due to corrosion are generated in the peeling process, which makes it difficult to use, and there is a limit that copper oxide cannot be effectively removed.

INDUSTRIAL APPLICABILITY The present invention provides a stripper composition for removing a photoresist, which has excellent peeling power against a photoresist, suppresses corrosion on the lower metal film during the peeling process, and can effectively remove oxides. It is a thing.

Further, the present invention is for providing a method for peeling a photoresist using the stripper composition for removing the photoresist.

The present specification includes an amide compound in which a linear or branched alkyl group having 1 to 5 carbon atoms is substituted 1-2 with nitrogen; an amine compound; a polar organic solvent; a methylazole; and a triazole-based compound. , A stripper composition for removing a photoresist is provided.

Also herein, a photoresist pattern is formed on a substrate on which a lower film is formed; a step of patterning the lower film with the photoresist pattern; and a photoresist removing stripper composition is used. A method for peeling a photoresist is provided, which comprises a step of peeling.

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

The terms used herein are used merely to illustrate exemplary examples and are not intended to limit the invention. A singular expression includes multiple expressions unless they have a distinctly different meaning in the context. As used herein, terms such as "contain", "provide" or "have" are intended to specify the existence of implemented features, numbers, stages, components or combinations thereof. It must be understood that the existence or addability of one or more other features, numbers, stages, components, or combinations thereof is not preliminarily excluded.

Since the present invention can be modified in various ways and can have various forms, specific examples will be illustrated below in detail. However, it should be understood that this does not attempt to limit the invention to any particular form of disclosure, but includes all modifications, equivalents to alternatives, contained within the ideas and technical scope.

According to one embodiment of the invention, an amide compound in which a linear or branched alkyl group having 1 to 5 carbon atoms is substituted with nitrogen by 1 to 2; an amine compound; a polar organic solvent; methimazole; and a triazole-based compound. A stripper composition for removing a photoresist can be provided.

The present inventors have conducted research on a stripper composition for removing a photoresist, and while the stripper composition for removing a photoresist containing the above-mentioned components has excellent peeling power for a photoresist, it is applied to a lower metal film in the peeling process. The invention was completed by confirming through experiments that it has the property of suppressing corrosion and effectively removing oxides.

As the number of high-resolution display models increases, copper wiring with low electrical resistance is used as the metal of the TFT. At this time, the copper wiring uses molybdenum (Mo) as the anti-diffusion film material (barrier metal) for the lower film. Therefore, it has a structure in which molybdenum with a low oxidation-reduction potential is corroded by the oxidation-reduction potential. However, as the stripping process, which is the process of removing the photoresist, progresses, quality problems occur while damage (damage) between copper and molybdenum occurs due to the stripper, and the stripper is prevented from corroding. Improvement of corrosion inhibitor is required.

As described above, in the stripper composition for removing the photoresist of the above embodiment, the amide compound, the amine compound, and the alkyl group of the linear or branched chain having 1 to 5 carbon atoms are substituted with nitrogen by 1-2. It contains a polar organic solvent, can maintain excellent peeling power over time and can effectively remove metal oxides, and also contains the methimazole and triazole compounds to suppress corrosion to the lower metal film. The effects that can be achieved can be realized together.

In particular, the stripper composition for removing a photoresist of the above-described embodiment contains both the methimazole and the triazole-based compound, and when removing the photoresist pattern, a copper-containing film, particularly a metal-containing lower film such as a copper / molybdenum metal film, is used. Corrosion can be prevented, and metal-containing lower parts can be used more efficiently at the same or lower amounts than when methimazole and triazole compounds are used, respectively, or when existing known corrosion inhibitors are used. Corrosion of the film can be suppressed.

Such an ascending action of the methimazole and the triazole-based compound has a role of the unshared electron pair of the Amino group (amino group) of the triazole-based compound binding to a metal of the lower membrane, for example, copper to prevent corrosion, and the triazole. It is considered that the unshared electron pair of Thiol group (thiol group) of methylazole, which has a smaller molecular weight than the system compound, binds to a metal other than the metal, for example, molybdenum (Mo) to protect the damage caused by stripper amine.

Further, the photoresist removing stripper composition of the above-described embodiment contains both methylazole and a triazole-based compound, and is removed in the DIW rinsing step immediately after the stripper step to improve the contact resistance between the metal-containing lower film and the substrate. For example, the contact resistance between Gate (Cu) and PXL (ITO) can be improved.

At this time, examples of the triazole-based compound are not largely limited, but for example, (2,2'[[(methyl-1H-benzotriazole-1-yl) methyl] imino] bisethanol, 4, 5 , 6,7-Tetrahydro-1H-benzotriazole, 1H-benzotriazole, 1H-1,2,3-triazole or methyl 1H-benzotriazole may be one or more selected from the group.

The methimazole is 0.001 to 0.5% by weight, or 0.001 to 0.3% by weight, or 0.001 to 0.1% by weight, or 0.005 to 0.07% by weight based on the total composition. It may be contained in% by weight, or 0.01 to 0.05% by weight. If the content of the methimazole is less than 0.001% by weight based on the total composition, it may be difficult to effectively suppress the corrosion on the lower membrane. If the content of methimazole exceeds 0.5% by weight based on the total composition, a considerable amount of corrosion inhibitor is adsorbed and remains on the lower film, and the copper-containing lower film, particularly the copper / molybdenum metal film. It may deteriorate the electrical properties such as, and adsorb to the photoresist to form a protective film, which may not be decomposed from the amine and may not be peeled off well, and foreign matter may be generated to cause a quality problem.

On the other hand, the methimazole can more efficiently prevent the corrosion of the metal-containing lower film even when the amount used is the same as or lower than that when the existing known corrosion inhibitor is used, and such an effect. Can be maximized when used in a specific content with a triazole-based compound described below.

The triazole-based compound is 0.01 to 5.0% by weight, or 0.02 to 2.0% by weight, or 0.05 to 1.0% by weight, or 0.07 to 0% by weight based on the total composition. It may be contained in an amount of 0.6% by weight, or 0.1 to 0.5% by weight. If the content of the triazole-based compound is less than 0.01% by weight based on the total composition, it may be difficult to effectively suppress corrosion on the lower membrane. If the content of the triazole compound exceeds 5.0% by weight with respect to the total composition, a considerable amount of the corrosion inhibitor is adsorbed and remains on the lower film, and the copper-containing lower film, particularly copper / molybdenum. It may reduce the electrical properties of metal films and the like.

On the other hand, the triazole-based compound can more efficiently prevent corrosion of the metal-containing lower film even when the amount used is the same as or lower than that when an existing known corrosion inhibitor is used. The effect can be maximized when used in a specific content with the aforementioned methimazole.

On the other hand, the weight ratio between the methimazole and the triazole-based compound is 1: 1 to 1:50, or 1: 1 to 1:40, or 1: 1.5 to 1:40, or 1: 2 to 1:30. It may be. When the methimazole and the triazole-based compound have the above-mentioned specific weight ratio, the corrosion prevention ability of the stripper composition for removing the photoresist with respect to the lower metal film is maximized, and the methimazole and the triazole-based compound are used, respectively. Methimazole and triazole compounds can each have a better anticorrosive effect on the lower metal film than when used in combination with other anticorrosive agents.

In addition, the photoresist removing stripper composition may contain an amine compound. The amine compound can make the photoresist removing stripper composition have a peeling force against the photoresist, and can specifically melt the photoresist and remove it.

The amine compound is contained in an amount of about 0.1 to 10% by weight, or 0.5 to 7% by weight, or 1 to 5% by weight, or 2 to 4.6% by weight based on the total composition. May be good. Depending on the content range of such an amine compound, the stripper composition of one embodiment can exhibit excellent peeling power and the like, but can reduce the decrease in efficiency and efficiency of the process due to an excessive amount of amine, and waste liquid. It is possible to reduce the occurrence of such things. If an excessively large content of amine compound is contained, this may result in corrosion of the lower membrane, for example, a copper-containing lower membrane, which may require the use of large amounts of corrosion inhibitors to control this. There is. In this case, a large amount of the corrosion inhibitor may adsorb and remain on the surface of the lower film to reduce the electrical properties of the copper-containing lower film and the like.

Specifically, if the amine compound is less than 0.1% by weight based on the total composition, the peeling force of the photoresist removing stripper composition may decrease, and 10% by weight based on the total composition. If it exceeds%, the economic efficiency and efficiency of the process may be reduced by containing an excessive amount of the amine compound.

Although the specific type of the amine compound is not largely limited, the amine compound can include at least one cyclic amine compound having a weight average molecular weight of 95 g / mol or more.

Examples of the cyclic amine compound are not broadly limited, but for example, 1-imidazolidine ethanol, 4-imidazolidine ethanol, hydroxyethylpiperazine (HEP), amino. Ethylpiperazine and the like can be used.

On the other hand, the amine compound may further contain a chain amine compound having a weight average molecular weight of 95 g / mol or more.

The chain amine compound having a weight average molecular weight of 95 g / mol or more appropriately removes a lower film, for example, a natural oxide film on a copper-containing film, together with a peeling force against a photoresist, to form a copper-containing film and an insulating film above the copper-containing film. For example, the intermembrane adhesive force with a silicon nitride film or the like can be further improved.

Examples of the chain amine compound having a weight average molecular weight of 95 g / mol or more are not largely limited, but for example, (2-aminoethoxy) -1-ethanol [(2-aminoethoxy) -1-ethanol; AEE]. , Aminoethyl ethanolamine (AEEA), methyldiethanolamine (MDEA), diethylenetriamine (DETA), diethanolamine (Diethanolamine; DEA), diethanolamine (DEA) TEA), Triethylene terraamine; TETA) or a mixture of two or more thereof can be included.

On the other hand, the total of the above-mentioned methimazole and triazole-based compounds can be contained in an amount of 1 to 30 parts by weight, 2 to 25 parts by weight, or 3 to 20 parts by weight with respect to 100 parts by weight of the amine compound.

As described above, the amine compound is a component exhibiting peeling power in the stripper composition for removing the photoresist, and plays a role of dissolving and removing the photoresist, and the methimazole and the triazole-based compound are the lower metal film. If the total amount is less than 1 part by weight of the methylazole and the triazole-based compound with respect to 100 parts by weight of the amine compound, it may be difficult to effectively suppress the corrosion on the lower film. Further, if the total amount of methimazole and the triazole-based compound exceeds 30 parts by weight with respect to 100 parts by weight of the amine compound, a considerable amount of the corrosion inhibitor is adsorbed and remains on the lower film, and the copper-containing lower film, particularly copper / It may reduce the electrical properties of molybdenum metal films and the like.

In addition, the photoresist removing stripper composition may contain an amide compound in which the alkyl group of a linear or branched chain having 1 to 5 carbon atoms is substituted with nitrogen by 1 to 2. The amide compound in which the alkyl group of the linear or branched chain having 1 to 5 carbon atoms is substituted with nitrogen by 1 to 2 can dissolve the amine compound well, and the stripper composition for removing the photoresist can be used. It is possible to improve the peeling force, the rinsing force, and the like of the stripper composition by effectively infiltrating the lower film.

Specifically, the amide-based compound in which the alkyl group of the linear or branched chain having 1 to 5 carbon atoms is 1-2 substituted with nitrogen includes an amide-based compound in which the methyl group is 1-2 substituted with nitrogen. Can be done. The amide compound in which the methyl group is substituted 1-2 with nitrogen can have the structure of the following chemical formula 1.

[Chemical formula 1]

In the above chemical formula 1, R ₁ is a hydrogen, a methyl group, an ethyl group, and a propyl group.
R ₂ and R ₃ are hydrogen or the linear or branched alkyl group having 1 to 5 carbon atoms, respectively, and _{at least one of R 2} and R ₃ is a methyl group.

Examples of the linear or branched alkyl group having 1 to 5 carbon atoms are not limited, but for example, a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group and the like are used. be able to.

Examples of amide compounds in which the methyl group is substituted 1-2 with nitrogen are not largely limited, but for example, in the chemical formula 1, R ₂ is a methyl group, and R ₁ and R ₃ are hydrogen, respectively. Compounds that are can be used.

The amide-based compound in which the alkyl group of the linear or branched chain having 1 to 5 carbon atoms is substituted with nitrogen by 1 to 2 is 10 to 80% by weight, or 15 to 70% by weight, or 15 to 70% by weight, based on the total composition. It may be contained in an amount of 25 to 60% by weight. Depending on the content range, excellent peeling force and the like of the photoresist removing stripper composition can be ensured, and the peeling force and rinsing force can be maintained for a long period of time.

In addition, the photoresist removing stripper composition may contain a polar organic solvent. The polar organic solvent can assist the excellent peeling force of the photoresist removing stripper composition by allowing the photoresist removing stripper composition to better penetrate onto the lower film, and can be applied to the lower film such as a copper-containing film. The stain can be effectively removed to improve the rinsing power of the photoresist removing stripper composition.

The polar organic solvent can contain an alkylene glycol monoalkyl ether, pyrrolidone, a sulfone, a sulfoxide, or a mixture of two or more thereof. More specifically, the alkylene glycol monoalkyl ether includes 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, and 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 monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol It can contain 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 two or more thereof.

Further, in consideration of the excellent wettability of the stripper composition for removing the photoresist, the improved peeling force due to the stripper composition, the rinsing force and the like, the alkylene glycol monoalkyl ethers include diethylene glycol monomethyl ether (MDG) and diethylene glycol monoethyl. Ether (EDG), diethylene glycol monobutyl ether (BDG), and the like can be used.

Examples of the pyrrolidone are not largely limited, but for example, N-methylpyrrolidone, pyrrolidone, N-ethylpyrrolidone and the like can be used. Examples of the sulfone are not broadly limited, but for example, sulfolane can be used. Examples of the sulfoxide are also not broadly limited, but for example, dimethyl sulfoxide (DMSO), diethyl sulfoxide, dipropyl sulfoxide and the like can be used.

Further, the polar organic solvent may be contained in an amount of 10 to 80% by weight, or 20 to 78% by weight, or 40 to 70% by weight based on the total composition. By satisfying the content range, excellent peeling force and the like of the photoresist removing stripper composition can be ensured, and the peeling force and rinsing force can be maintained for a long period of time.

On the other hand, the photoresist removing stripper composition may further contain a silicon-based nonionic surfactant. The silicon-based nonionic surfactant contains an amine compound and the like and is stably maintained without causing chemical change, modification or decomposition even in a strongly basic stripper composition, and the above-mentioned aprotic polar solvent or It may be shown that the compatibility with a protonic organic solvent or the like is excellent. Thereby, the silicon-based nonionic surfactant is well mixed with other components to reduce the surface tension of the stripper composition, which is more excellent for the photoresist and its lower film from which the stripper composition is removed. It can be made to show wettability and wettability. As a result, the stripper composition of one embodiment containing this can not only show better photoresist peeling power, but also show better rinsing power to the lower membrane, even after the stripper composition treatment. Almost no stain or foreign matter is generated and left on the film, and such stain or foreign matter can be effectively removed.

The silicon-based nonionic surfactant can exhibit the above-mentioned effect even when added at a very low content, and the generation of by-products due to its modification or decomposition can be minimized.

Specifically, the silicon-based nonionic surfactant may contain a polysiloxane-based polymer. More specifically, examples of the polysiloxane-based polymer are not largely limited, but for example, polyether-modified acrylic functional polydimethylsiloxane, polyether-modified siloxane, polyether-modified polydimethylsiloxane, and polyethylalkyl. Siloxane, aralkyl-modified polymethylalkylsiloxane, polyether-modified hydroxyfunctional polydimethylsiloxane, polyether-modified dimethylpolysiloxane, modified acrylic-functional polydimethylsiloxane, or a mixture of two or more thereof can be used.

The silicon-based nonionic surfactant is 0.0005% by weight to 0.1% by weight, or 0.001% by weight to 0.09% by weight, or 0.001% by weight to 0% by weight based on the total composition. It may be contained in a content of 0.01% by weight. When the content of the silicon-based nonionic surfactant is less than 0.0005% by weight with respect to the total composition, the effect of improving the peeling force and rinsing force of the stripper composition by adding the surfactant should not be sufficiently increased. There is. Further, when the content of the silicon-based nonionic surfactant exceeds 0.1% by weight with respect to the total composition, bubbles are generated at high pressure during the peeling step using the stripper composition, and the lower part is formed. The membrane may stain or the equipment sensor may malfunction.

The photoresist removing stripper composition may additionally contain a usual additive, if necessary, and there is no particular limitation on the specific type and content of the additive.

Further, the photoresist removing stripper composition can be produced by a general method of mixing the above-mentioned components, and there are no particular restrictions on the specific production method of the photoresist removing stripper composition.

On the other hand, according to another embodiment of the invention, it is possible to provide a method for peeling a photoresist, which comprises a step of stripping the photoresist using the stripper composition for removing the photoresist of the above embodiment.

The content relating to the photoresist removing stripper composition includes the content detailed with respect to the embodiment.

The method for peeling the photoresist is as follows: first, a photoresist pattern is formed on a substrate on which a lower film to be patterned is formed through a photolithography step, and then the lower film is patterned using the photoresist pattern as a mask. , The step of stripping the photoresist using the stripper composition described above can be included.

In the photoresist peeling method, a normal element manufacturing process can be used for the photoresist pattern forming step and the lower film patterning step, and there are no particular restrictions on the specific manufacturing method.

On the other hand, the example of the step of peeling the photoresist using the photoresist removing stripper composition is not largely limited, but for example, the photoresist removing stripper composition is placed on a substrate on which the photoresist pattern remains. Can be used by treating, washing with an alkali buffering solution, washing with ultrapure water, and drying. The stripper composition exhibits excellent peeling power, rinsing power for effectively removing stains on the lower film, and ability to remove the natural oxide film, thereby effectively removing the photoresist pattern remaining on the lower film. , The surface condition of the lower film can be maintained well. As a result, the element can be formed on the patterned lower film by appropriately performing the subsequent steps.

Specific examples of the lower film formed on the substrate are not largely limited, but are aluminum or aluminum alloys, copper or copper alloys, molybdenum or molybdenum alloys, or mixtures thereof, composite alloys thereof, these. It can include a composite laminate and the like.

The type, composition or physical properties of the photoresist to be the subject of the peeling method are not largely limited, and when used for a lower film containing, for example, aluminum or aluminum alloy, copper or copper alloy, molybdenum or molybdenum alloy, etc. It may be a known photoresist. More specifically, the photoresist can contain a photosensitive resin component such as a novolak resin, a resole resin, or an epoxy resin.

According to the present invention, a stripper composition for removing a photoresist, which has excellent peeling power against a photoresist, suppresses corrosion on the lower metal film in the peeling process, and can effectively remove oxides, and a stripper composition for removing the photoresist. A method for peeling off the photoresist used can be provided.

The invention will be described in more detail with reference to the following examples. However, the following examples merely exemplify the present invention, and the content of the present invention is not limited to the following examples.

<Examples 1 to 5: Production of stripper composition for photoresist removal>

According to the composition shown in Table 1 below, each component was mixed to prepare a photoresist removing stripper composition of Examples 1 to 5, respectively. The specific composition of the produced photoresist removing stripper composition is as shown in Table 1 below.

[Table 1]
Composition of Stripper Composition for photoresist Removal

* LGA: 1-imidazolidine ethanol
* NMF: N-methylformamide * EDG: Diethylene glycol monoethyl ether * MDG: Diethylene glycol monomethyl ether * BDG: Diethylene glycol monobutyl ether * Anticorrosion agent 1: Thiamazole
* Corrosion inhibitor 2: (2,2'[[(methyl-1H-benzotriazole-1-yl) methyl] imino] bisethanol * Corrosion inhibitor 3: benzimidazole * Corrosion inhibitor 4: imidazole * Corrosion inhibitor 5: 2-Methylimidazole * Corrosion inhibitor 6: 2-Mercaptobenzimidazole

<Comparative Examples 1 to 5: Production of Stripper Composition for Removing photoresist>

According to the composition shown in Table 2 below, each component was mixed to prepare a stripper composition for removing photoresist of Comparative Examples 1 to 5, respectively. The specific composition of the produced photoresist removing stripper composition is as shown in Table 2 below.

[Table 2]
Composition of Stripper Composition for photoresist Removal

* LGA: 1-imidazolidine ethanol
* NMF: N-methylformamide * EDG: Diethylene glycol monoethyl ether * MDG: Diethylene glycol monomethyl ether * BDG: Diethylene glycol monobutyl ether * Anticorrosion agent 1: Thiamazole
* Corrosion inhibitor 2: (2,2'[[(methyl-1H-benzotriazole-1-yl) methyl] imino] bisethanol * Corrosion inhibitor 3: benzimidazole * Corrosion inhibitor 4: imidazole * Corrosion inhibitor 5: 2-Methylimidazole * Corrosion inhibitor 6: 2-Mercaptobenzimidazole

<Experimental example: Measurement of physical properties of the photoresist removing stripper composition obtained in Examples and Comparative Examples>

The physical characteristics of the stripper compositions obtained in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in the table.

1. 1. Peeling force evaluation

First, 3.5 ml of a photoresist composition (trade name: JC-800) was added dropwise to a 100 mm × 100 mm glass substrate, and the photoresist composition was applied at a speed of 400 rpm for 10 seconds using a spin coating apparatus. Such a glass substrate was mounted on a hot plate and hard baked 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 evaluating the new liquid peeling force.

500 g of the stripper compositions obtained in Examples 1 to 5 and Comparative Examples 1 to 4, 6 and 7 were prepared, and the photoresist on the glass substrate was treated with the stripper composition in a state where the temperature was raised to 50 ° C. .. The new liquid peeling force was evaluated by measuring the time during which the photoresist was completely peeled off and removed. At this time, the presence or absence of peeling of the photoresist was confirmed by irradiating the glass substrate with ultraviolet rays and observing whether or not the photoresist remained.

The stripping force of the stripper compositions of Examples 1 to 5 and Comparative Examples 1 to 4, 6 and 7 was evaluated by the above method and shown in Tables 3 and 4 below.

As shown in Tables 3 and 4 above, the stripper compositions of Examples 1 to 5 show the same or superior level of peeling power as the stripper compositions of Comparative Examples 1 to 4, 6 and 7. It was confirmed that.

2. Evaluation of corrosiveness of copper (Cu) metal

3.5 ml of the photoresist composition (trade name: JC-800) was dropped onto a 100 mm × 100 mm glass substrate on which a thin film containing copper was formed, and the photoresist composition was applied at a speed of 400 rpm for 10 seconds with a spin coating device. did. Such a glass substrate was mounted on a hot plate and hard baked 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 corrosion evaluation.

500 g of the stripper compositions of Examples 1, 3, 4, 5 and Comparative Examples 1 to 7 were heated to a temperature of 50 ° C., and the corrosiveness evaluation sample was immersed in the stripper composition at a temperature of 50 ° C. for 10 minutes. After that, it was washed with ultrapure water. The corrosive state of the washed sample was measured through SEM to evaluate the corrosiveness of the copper metal, which are shown in Tables 5 and 6 below.

As shown in Tables 5 and 6 above, the stripper compositions of Examples 1, 3, 4, and 5 are compared with the stripper compositions of Comparative Examples 2 to 5 by containing all of methimazole and triazole-based compounds. It was confirmed that the corrosiveness to copper metal was reduced.

From such a result, it can be confirmed that the methimazole and the triazole-based compound contained in the stripper composition of the example are excellent in the ability to prevent the corrosion of the copper metal.

3. 3. Evaluation of corrosiveness of copper (Cu) / molybdenum (Mo) metal undercoat

A cross section of the corrosiveness evaluation sample obtained in Examples 1 to 5 and Comparative Examples 1, 3, 4, 6 and 7 was observed using a transmission electron microscope (Helios NanoLab 650). Specifically, after producing a piece of a sample for corrosiveness evaluation using FIB (Focused Ion Beam), observe it at an acceleration voltage of 2 kV, and the sample is to prevent surface damage due to ion beam during the sample production process. After forming a Pt (platinum) corrosion layer on the sample surface (Cu layer), TEM flakes were produced.

As shown in Tables 7 and 8 above, the stripper compositions of Examples 1 to 5 contain all of the methimazole and triazole compounds to prevent corrosion of Comparative Examples 1 and 1 containing methimazole and benzimidazole. It was confirmed that the corrosiveness of the copper (Cu) / molybdenum (Mo) metal lower film was reduced as compared with the stripper compositions of Comparative Examples 3, 4 and 7 containing the agent.

From these results, it is confirmed that the methimazole and triazole-based compounds contained in the stripper composition of the example have an excellent ability to prevent corrosion of the copper (Cu) / molybdenum (Mo) metal undercoat. be able to.

Claims (10)

An amide compound in which the alkyl group of a linear or branched chain having 1 to 5 carbon atoms is substituted with nitrogen by 1 to 2;
Amine compound;
Polar organic solvent;
Methimazole; and triazole compounds;
including,
Stripper composition for photoresist removal. The weight ratio between the methimazole and the triazole-based compound is 1: 1 to 1:50.
The stripper composition for removing a photoresist according to claim 1. A total of 1 to 30 parts by weight of methimazole and a triazole-based compound is contained with respect to 100 parts by weight of the amine compound.
The stripper composition for removing a photoresist according to claim 1 or 2. The triazole compounds are (2,2'[[(methyl-1H-benzotriazole-1-yl) methyl] imino] bisethanol, 4,5,6,7-tetrahydro-1H-benzotriazole, 1H-benzo. Includes one or more compounds selected from the group consisting of triazole, 1H-1,2,3-triazole or methyl1H-benzotriazole.
The stripper composition for removing a photoresist according to any one of claims 1 to 3. The amine compound contains a cyclic amine compound having a weight average molecular weight of 95 g / mol or more.
The stripper composition for removing a photoresist according to any one of claims 1 to 4. The amine compound further contains a chain amine compound having a weight average molecular weight of 95 g / mol or more.
The stripper composition for removing a photoresist according to claim 5. The amide compound in which the alkyl group of the linear or branched chain having 1 to 5 carbon atoms is substituted with nitrogen by 1 to 2 includes the compound of the following chemical formula 1.
The photoresist removing stripper composition according to any one of claims 1 to 6.
[Chemical formula 1]

In the above chemical formula 1, R ₁ is a hydrogen, a methyl group, an ethyl group, and a propyl group.
R ₂ and R ₃ are hydrogen or the above-mentioned linear or branched alkyl group having 1 to 5 carbon atoms, respectively.
At _{least one of R 2} and R ₃ is a methyl group. The polar organic solvent comprises one or more selected from the group consisting of alkylene glycol monoalkyl ethers, pyrrolidones, sulfones and sulfoxides.
The stripper composition for removing a photoresist according to any one of claims 1 to 7. 10-80% by weight of an amide compound in which the alkyl group of a linear or branched chain having 1 to 5 carbon atoms is substituted with nitrogen by 1 to 2;
Amine compound 0.1-10% by weight;
Polar organic solvent 10-80% by weight;
Methimazole 0.001 to 0.5% by weight; and triazole compounds 0.01 to 5.0% by weight;
include,
The stripper composition for removing a photoresist according to any one of claims 1 to 8. A step of peeling a photoresist using the photoresist removing stripper composition according to any one of claims 1 to 9.
Photoresist peeling method.