KR20200112551A - Stripper composition for removing photoresist and stripping method of photoresist using the same - Google Patents

Abstract

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

Description

A stripper composition for removing photoresist, and a method of peeling photoresist using the same {STRIPPER COMPOSITION FOR REMOVING PHOTORESIST AND STRIPPING METHOD OF PHOTORESIST USING THE SAME}

The present invention relates to a stripper composition for removing a photoresist and a method for removing photoresist using the same, and more particularly, to suppress corrosion to a lower metal film during the peeling process while having excellent peeling power against the photoresist, and It relates to a photoresist stripper composition capable of removing effectively and a photoresist peeling method using the same.

The microcircuit process or semiconductor integrated circuit manufacturing process of a liquid crystal display device is performed on a substrate with an insulating film such as a conductive metal film such as aluminum, aluminum alloy, copper, copper alloy, molybdenum, molybdenum alloy, or silicon oxide film, silicon nitride film, fork acrylic insulating film, etc. Various processes of forming a photoresist pattern by forming the same various lower layers, uniformly coating a photoresist on the lower layers, and selectively performing exposure and development treatment to form a photoresist pattern, and then patterning the lower layers with a mask are included. After the patterning process, a photoresist remaining on the lower layer is removed, and a stripper composition for removing photoresist is used for this purpose.

Stripper compositions including an amine compound, a protic polar solvent, and an aprotic polar solvent have been widely known and mainly used. Such stripper compositions have been known to exhibit some degree of removal and peeling force for photoresists.

However, such a conventional stripper composition has a problem in that when a large amount of photoresist is peeled off, the decomposition of the amine compound is accelerated over time, so that the peeling force and the rinsing force are deteriorated over time. In particular, this problem may be further accelerated when a part of the residual photoresist is dissolved in the stripper composition depending on the number of times the stripper composition is used.

In addition, when a copper metal film is used as a lower film, stains and foreign substances due to corrosion are generated during the peeling process, making it difficult to use, and there are limitations such as not being able to effectively remove the copper oxide.

An object of the present invention is to provide a photoresist stripper composition capable of effectively removing oxides and inhibiting corrosion of a lower metal film during a peeling process while having excellent peeling power against a photoresist.

In addition, the present invention is to provide a photoresist stripping method using the photoresist stripper composition.

In the present specification, an amide compound in which a linear or branched alkyl group having 1 to 5 carbon atoms is substituted with 1 to 2 nitrogen; Amine compounds; Polar organic solvents; Methimazole; And a stripper composition for removing photoresist comprising a triazole-based compound is provided.

In the present specification, further, forming a photoresist pattern on the substrate on which the lower layer is formed; Patterning a lower layer with the photoresist pattern; And removing the photoresist using the photoresist stripper composition.

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

The terms used in the present specification are only used to describe exemplary embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present specification, terms such as "comprise", "include" or "have" are intended to designate the presence of implemented features, numbers, steps, components, or a combination thereof, and one or more other features or It is to be understood that the possibility of the presence or addition of numbers, steps, elements, or combinations thereof is not preliminarily excluded.

The present invention will be described in detail below and exemplify specific embodiments, as various changes can be made and various forms can be obtained. However, this is not intended to limit the present invention to a specific form disclosed, it is to be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

According to an embodiment of the present invention, an amide compound in which a linear or branched alkyl group having 1 to 5 carbon atoms is substituted with 1 to 2 nitrogen; Amine compounds; Polar organic solvents; Methimazole; And a stripper composition for removing photoresist comprising a triazole-based compound may be provided.

The present inventors conducted a study on a stripper composition for photoresist removal, and a stripper composition for photoresist removal containing the above-described components was It has been confirmed through experiments that it has excellent peeling power against the photoresist, suppresses corrosion to the lower metal film during the peeling process, and has characteristics that can effectively remove oxides, and the invention has been completed.

As display high-resolution models increase, the metal of the TFT is used as a copper wiring with low electrical resistance. At this time, the copper wiring uses molybdenum (Mo) as a lower layer as a barrier metal, and due to the redox potential. It has a structure in which corrosion of molybdenum with a low redox potential occurs. However, during the strip process, which is a process of removing the photoresist, damage between copper and molybdenum occurs due to the stripper, resulting in a quality problem, and improvement of a corrosion inhibitor to prevent corrosion of the stripper is required. .

As described above, the stripper composition for photoresist removal of the embodiment includes an amide compound, an amine compound, and a polar organic solvent in which a linear or branched alkyl group having 1 to 5 carbon atoms is substituted with 1 to 2 nitrogen. It is possible to maintain excellent peeling force and effectively remove oxides of metals, and at the same time, the effect of suppressing corrosion to the lower metal film including the methimazole and triazole-based compounds may be realized.

In particular, the stripper composition for removing the photoresist of the embodiment includes the methimazole and the triazole-based compound together to prevent corrosion of a copper-containing film, particularly a metal-containing lower film such as a copper/molybdenum metal film, when removing the photoresist pattern. In addition, it is possible to more efficiently suppress the corrosion of the metal-containing lower film even with an equivalent amount or a lower amount compared to the case of using each of methimazole and a triazole-based compound or using a previously known corrosion inhibitor.

The synergistic action of the methimazole and the triazole-based compound is that the non-shared electron pair of the amino group (amino group) of the triazole-based compound binds to the metal of the lower layer, for example, copper to prevent corrosion. It seems that the unshared electron pair of the Thiol group (thiol group) of methymazole having a small molecular weight binds to a metal other than the metal, such as molybdenum (Mo), to protect the damage caused by the stripper amine.

In addition, the photoresist stripper composition for removing the photoresist of the above embodiment may include methimazole and a triazole-based compound together, and is removed in a DIW rinse process immediately after the stripper process to improve contact resistance between the metal-containing lower layer and the substrate. For example, it is possible to improve the contact resistance between the gate (Cu) and the PXL (ITO).

At this time, examples of the triazole-based compound are not largely limited, for example, (2,2'[[(methyl-1H-benzotriazol-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 consisting of.

The methimazole may be included in an amount of 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, or 0.01 to 0.05% by weight, based on the total composition. If the amount of methimazole is less than 0.001% by weight based on the total composition, it may be difficult to effectively suppress corrosion on the lower film. In addition, if the content of methymazole is more than 0.5% by weight of the total composition, a significant amount of corrosion inhibitor adsorbs and remains on the lower film, thereby deteriorating the electrical properties of the copper-containing lower film, especially the copper/molybdenum metal film. In addition, by adsorbing to the photoresist to form a protective film, it is not decomposed from amines, so that peeling is not performed properly and foreign matters are generated, which may cause quality problems.

On the other hand, the methymazole can more efficiently prevent corrosion of the metal-containing lower layer even with an equivalent amount or a lower amount compared to the case of using a previously known corrosion inhibitor, and such an effect can be achieved with a triazole-based compound to be described later. It can be maximized when used together in a specific amount.

The triazole-based compound may be included in an amount of 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 0.6% by weight, or 0.1 to 0.5% by weight, based on the total composition. When 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 film. In addition, if the content of the triazole-based compound is more than 5.0% by weight based on the total composition, a significant amount of corrosion inhibitor adsorbs and remains on the lower film, thereby reducing the electrical properties of the copper-containing lower film, especially the copper/molybdenum metal film. I can.

On the other hand, the triazole-based compound can more efficiently prevent corrosion of the metal-containing lower layer even with an equivalent amount or a lower amount compared to the case of using a previously known corrosion inhibitor, and such an effect can be achieved with the above-described methimazole. It can be maximized when used together in a specific amount.

Meanwhile, the weight ratio between the methimazole and the triazole-based compound may be 1:1 to 1:50, or 1:1 to 1:40, or 1:1.5 to 1:40, or 1:2 to 1:30. As the methimazole and triazole-based compounds have the specific weight ratio described above, the ability to prevent corrosion of the lower metal film of the photoresist stripper composition can be maximized, and methimazole and triazole-based compounds are used, respectively. Alternatively, when metimazole and triazole-based compounds are used together with different corrosion inhibitors, the lower metal film may have an excellent corrosion prevention effect.

In addition, the photoresist stripper composition for removing may include an amine compound. The amine compound may allow the photoresist stripper composition to have a peeling force against the photoresist, and specifically, may serve to remove the photoresist by melting it.

The amine compound may be included 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. Depending on the content range of the amine compound, the stripper composition of one embodiment may exhibit excellent peeling force, etc., while reducing the economic efficiency and efficiency of the process due to an excess of amine, and reducing the generation of waste liquid. If an excessively large amount of the amine compound is included, corrosion of the lower film, for example, the copper-containing lower film may be caused by this, and it may be necessary to use a large amount of corrosion inhibitor to suppress this. In this case, a significant amount of the corrosion inhibitor adsorbs and remains on the surface of the lower film by a large amount of the corrosion inhibitor, thereby deteriorating the electrical properties of the copper-containing lower film.

Specifically, if the amine compound is less than 0.1% by weight of the total composition, the peel strength of the stripper composition for removing the photoresist may be reduced, and if it is more than 10% by weight of the total composition, the excess amine compound is included. Accordingly, the economic feasibility and efficiency of the process may decrease.

Although the specific type of the amine compound is not largely limited, the amine compound may 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 largely limited, but, for example, 1-imidazolidine ethanol, 4-imidazolidine ethanol, and hydroxyethylpiperazine (HEP), aminoethylpiperazine, and the like can be used.

Meanwhile, the amine compound may further include a chain-type amine compound having a weight average molecular weight of 95 g/mol or more.

The chain-type amine compound having a weight average molecular weight of 95 g/mol or more removes the natural oxide film on the lower film, for example, the copper-containing film, together with the peeling force on the photoresist, so that the containing film and the insulating film thereon, for example. For example, it is possible to further improve inter-film adhesion with a silicon nitride film or the like.

Examples of the chain-type amine compound having a weight average molecular weight of 95 g/mol or more are not greatly limited, for example, (2-aminoethoxy)-1-ethanol [(2-aminoethoxy)-1-ethanol; AEE], aminoethyl ethanol amine (AEEA), methyl diethanolamine (MDEA), diethylene triamine (DETA), diethanolamine (DEA), diethylaminoethanol (Diethylaminoethanol; DEEA), triethanolamine (TEA), triethylene tetraamine (TETA), or a mixture of two or more thereof.

Meanwhile, the total of the above-described methimazole and triazole-based compounds may be included in an amount of 1 to 30 parts by weight, 2 to 25 parts by weight, or 3 to 20 parts by weight based on 100 parts by weight of the amine compound.

As described above, in the stripper composition for removing photoresist, the amine compound is a component that exhibits peeling force, and serves to melt and remove the photoresist, and the methimazole and triazole-based compounds prevent corrosion of the lower metal film. It plays a role of suppressing, and if the total amount of methimazole and triazole-based compounds is less than 1 part by weight relative to 100 parts by weight of the amine compound, it may be difficult to effectively suppress corrosion on the lower film. In addition, if the total amount of methimazole and triazole-based compounds exceeds 30 parts by weight with respect to 100 parts by weight of the amine compound, a significant amount of corrosion inhibitor adsorbs and remains on the lower film, resulting in electrical properties such as copper-containing lower film, especially copper/molybdenum metal film. It can reduce the properties.

In addition, the photoresist stripper composition may include an amide-based compound in which a linear or branched alkyl group having 1 to 5 carbon atoms is substituted with 1 to 2 nitrogen. The amide-based compound in which the linear or branched alkyl group having 1 to 5 carbon atoms is substituted with 1 to 2 nitrogen can dissolve the amine compound satisfactorily, and the photoresist stripper composition for removing the photoresist effectively permeates the lower film. , It is possible to improve the peeling power and rinse power of the stripper composition.

Specifically, the amide-based compound in which the linear or branched alkyl group having 1 to 5 carbon atoms is substituted with 1 to 2 nitrogen may include an amide compound in which the methyl group is substituted with 1 to 2 nitrogen. The amide-based compound in which the methyl group is substituted with 1 to 2 nitrogen may have a structure represented by Formula 1 below.

[Formula 1]

In Formula 1, R ₁ is hydrogen, a methyl group, an ethyl group, a propyl group,

R ₂ and R ₃ are each hydrogen or a linear or branched alkyl group having 1 to 5 carbon atoms, 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 may be used.

Examples of the amide-based compound in which the methyl group is substituted with 1 to 2 nitrogen are not limited, for example, in Formula 1, R ₂ is a methyl group, and R ₁ and R ₃ are each hydrogen.

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

In addition, the photoresist stripper composition for removing may contain a polar organic solvent. The polar organic solvent allows the photoresist stripper composition to permeate better on the lower layer, thereby assisting the excellent peeling force of the photoresist stripper composition, and effectively removes stains on the lower layer such as a copper-containing layer. It is possible to improve the rinse power of the stripper composition for removing photoresist.

The polar organic solvent may include alkylene glycol monoalkyl ether, pyrrolidone, sulfone, sulfoxide, or a mixture of two or more thereof. More specifically, the alkylene glycol monoalkyl ether is 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 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 mono It may contain butyl ether or a mixture of two or more thereof.

In addition, in consideration of the excellent wettability of the stripper composition for removing the photoresist and the resulting improved peeling force and rinsing force, the alkylene glycol monoalkyl ethers include diethylene glycol monomethyl ether (MDG), diethylene glycol mono Ethyl ether (EDG) or diethylene glycol monobutyl ether (BDG) may be used.

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

In addition, the polar organic solvent may be included 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. As the content range is satisfied, excellent peeling force of the stripper composition for removing the photoresist can be secured, and the peeling force and rinsing force may be maintained for a long period of time.

Meanwhile, the photoresist stripper composition may further include a silicone-based nonionic surfactant. The silicone-based nonionic surfactant contains an amine compound, so that it can be stably maintained without causing chemical changes, denaturation or decomposition even in a stripper composition having a strong basicity, and is compatible with the aprotic polar solvent or proton organic solvent described above. Can appear excellently. Accordingly, the silicone-based nonionic surfactant may be well mixed with other components to lower the surface tension of the stripper composition, and to exhibit more excellent wettability and wettability to the photoresist and the lower film from which the stripper composition is to be removed. As a result, the stripper composition of one embodiment including the same can not only exhibit better photoresist peeling power, but also exhibit excellent rinsing power to the lower film, so that even after treatment with the stripper composition, stains or foreign matters almost occur and remain Without doing so, such stains and foreign matter can be effectively removed.

In addition, the above-described effects can be exhibited even when the silicone-based nonionic surfactant is added in a very low content, and generation of by-products due to its denaturation or decomposition can be minimized.

Specifically, the silicone-based nonionic surfactant may include a polysiloxane-based polymer. More specifically, examples of the polysiloxane-based polymer are not greatly limited, for example, polyether-modified acrylic functional polydimethylsiloxane, polyether-modified siloxane, polyether-modified polydimethylsiloxane, polyethylalkylsiloxane, aralkyl-modified poly Methylalkylsiloxane, polyether-modified hydroxy-functional polydimethylsiloxane, polyether-modified dimethylpolysiloxane, modified acrylic-functional polydimethylsiloxane, or a mixture of two or more thereof may be used.

The silicone-based nonionic surfactant may be included in an amount of 0.0005 wt% to 0.1 wt %, or 0.001 wt% to 0.09 wt %, or 0.001 wt% to 0.01 wt %, based on the total composition. When the content of the silicone-based nonionic surfactant is less than 0.0005% by weight based on the total composition, the effect of improving the peel strength and rinsing power of the stripper composition according to the addition of the surfactant may not be sufficiently achieved. In addition, when the content of the silicone-based nonionic surfactant is more than 0.1% by weight of the total composition, bubbles are generated at high pressure during the peeling process using the stripper composition, causing stains on the lower film or malfunction of the equipment sensor. I can.

The photoresist stripper composition for removing the photoresist may further include conventional additives as needed, and there is no particular limitation on the specific type or content of the additive.

In addition, the photoresist stripper composition may be prepared according to a general method of mixing the above-described components, and there is no particular limitation on a specific method of preparing the photoresist stripper composition.

Meanwhile, according to another embodiment of the present invention, a method of removing a photoresist including the step of removing the photoresist using the stripper composition for removing the photoresist of the embodiment may be provided.

The information on the stripper composition for removing the photoresist includes the above-described information regarding the embodiment.

The photoresist peeling method includes first forming a photoresist pattern on a substrate on which a lower film to be patterned is formed through a photolithography process, and then patterning the lower film using the photoresist pattern as a mask, and the above-described stripper composition It may include the step of peeling the photoresist using.

In the photoresist peeling method, the forming step of the photoresist pattern and the patterning step of the lower layer may use a conventional device manufacturing process, and there is no particular limitation on a specific manufacturing method thereof.

On the other hand, the example of the step of peeling the photoresist using the photoresist stripper composition is not largely limited, for example, by treating the photoresist stripper composition on the substrate on which the photoresist pattern remains, and alkali A method of washing with a buffer solution, washing with ultrapure water, and drying may be used. As the stripper composition exhibits excellent peeling power, rinsing power to effectively remove stains on the lower film, and ability to remove natural oxide films, it is possible to maintain a good surface condition of the lower film while effectively removing the photoresist pattern remaining on the lower film. have. Accordingly, a device may be formed by appropriately performing a subsequent process on the patterned lower layer.

Although a specific example of the lower layer formed on the substrate is not largely limited, it may include aluminum or aluminum alloy, copper or copper alloy, molybdenum or molybdenum alloy, or mixtures thereof, composite alloys thereof, and composite laminates thereof. .

The type, component, or physical property of the photoresist subject to the peeling method is also not limited, and is known to be used for a lower film including, for example, aluminum or aluminum alloy, copper or copper alloy, molybdenum or molybdenum alloy, etc. It may be a resist. More specifically, the photoresist may include a photosensitive resin component such as a novolac resin, a resol resin, or an epoxy resin.

According to the present invention, a photoresist removal stripper composition capable of effectively removing oxides and suppressing corrosion of a lower metal film during a peeling process while having excellent peeling power against a photoresist, and a photoresist peeling method using the same Can be provided.

The invention will be described in more detail in the following examples. However, the following examples are merely illustrative of the present invention, and the contents of the present invention are not limited by the following examples.

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

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

Composition of stripper composition for photoresist removal division Example 1
(wt%) Example 2
(wt%) Example 3
(wt%) Example 4
(wt%) Example 5
(wt%) LGA 3.5 3.5 3.5 3.5 3.5 NMF 55.0 55.0 55.0 55.0 55.0 EDG 0 0 40.97 0 0 MDG 0 40.97 0 0 0 BDG 40.97 0 0 41.19 41.35 Corrosion inhibitor 1 0.03 0.03 0.03 0.01 0.05 Corrosion inhibitor 2 0.5 0.5 0.5 0.3 0.1 Corrosion inhibitor 3 0 0 0 0 0 Corrosion inhibitor 4 0 0 0 0 0 Corrosion inhibitor 5 0 0 0 0 0 Corrosion inhibitor 6 0 0 0 0 0 Total 100.00 100.00 100.00 100.00 100.00

* LGA: 1-imidazolidine ethanol

* NMF: N-methylformamide

* EDG: Diethylene glycol monoethyl ether

* MDG: Diethylene glycol monomethyl ether

* BDG: Diethylene glycol monobutyl ether

* Corrosion inhibitor 1: Methimazole

*Anti-corrosion agent 2: (2,2'[[(methyl-1H-benzotriazol-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: Preparation of a stripper composition for photoresist removal>

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

Composition of stripper composition for photoresist removal division Comparative Example 1
(wt%) Comparative Example 2
(wt%) Comparative Example 3
(wt%) Comparative Example 4
(wt%) Comparative Example 5
(wt%) Comparative Example 6
(wt%) Comparative Example 7
(wt%) LGA 3.5 3.5 3.5 3.5 3.5 3.5 3.5 NMF 55.0 55.0 55.0 55.0 55.0 55.0 55.0 EDG 0 0 0 0 0 0 0 MDG 0 0 0 0 0 0 0 BDG 40.9 41.0 41.0 41.0 41.0 41.0 40.9 Corrosion inhibitor 1 0 0 0 0 0 0.5 0 Corrosion inhibitor 2 0.5 0 0 0 0 0 0.5 Corrosion inhibitor 3 0.1 0 0 0 0.5 0 0 Corrosion inhibitor 4 0 0.5 0 0 0 0 Corrosion inhibitor 5 0 0 0.5 0 0 0 0 Corrosion inhibitor 6 0 0 0 0.5 0 0 0 Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0

* LGA: 1-imidazolidine ethanol

* NMF: N-methylformamide

* EDG: Diethylene glycol monoethyl ether

* MDG: Diethylene glycol monomethyl ether

* BDG: Diethylene glycol monobutyl ether

* Corrosion inhibitor 1: Methimazole

*Anti-corrosion agent 2: (2,2'[[(methyl-1H-benzotriazol-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 stripper compositions for photoresist removal obtained in Examples and Comparative Examples>

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

1. Peel force evaluation

First, 3.5 ml of a photoresist composition (trade name: JC-800) was added dropwise to a 100 mm x 100 mm glass substrate, and the photoresist composition was applied for 10 seconds at a speed of 400 rpm in a spin coating apparatus. The glass substrate was mounted on a hot plate and hard-baked at 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 x 30 mm to prepare a sample for evaluating a new solution 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 a photoresist on a glass substrate was treated with a stripper composition while the temperature was raised to 50°C. The time for completely peeling and removing the photoresist was measured to evaluate the peel strength of the new solution. At this time, whether the photoresist was peeled off was confirmed by observing whether the photoresist remained by irradiating ultraviolet rays on the glass substrate.

The peel strength of the stripper compositions of Examples 1 to 5 and Comparative Examples 1 to 4, 6 and 7 was evaluated in the same manner as described above, and are shown in Tables 3 and 4 below.

division Example 1 Example 2 Example 3 Example 4 Example 5 Peeling time 240 seconds 240 seconds 240 seconds 240 seconds 240 seconds

division Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 6 Comparative Example 7 Peeling time 240 seconds 240 seconds 240 seconds 240 seconds 360 seconds 240 seconds

As shown in Tables 3 and 4, it was confirmed that the stripper compositions of Examples 1 to 5 exhibited equal or superior peel strength compared to the stripper compositions of Comparative Examples 1 to 4, 6, and 7.

2. Corrosion evaluation of copper (Cu) metal

3.5 ml of a photoresist composition (trade name: JC-800) was added dropwise to a 100 mm x 100 mm glass substrate on which a thin film containing copper was formed, and the photoresist composition was applied for 10 seconds at a speed of 400 rpm in a spin coating apparatus. The glass substrate was mounted on a hot plate and hard-baked at 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 x 30 mm to prepare a sample for evaluating corrosion.

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 sample for evaluating corrosion was immersed in the stripper composition at a temperature of 50°C for 10 minutes, and then ultrapure water Washed with. The corrosiveness of the copper metal was evaluated by measuring the surface corrosion state of the cleaned sample through SEM, and it is shown in Tables 5 and 6 below.

A film formed on a glass substrate Example 1 Example 3 Example 4 Example 5 Cu film No change No change No change No change

A film formed on a glass substrate Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Cu film Corrosion occurs Corrosion occurs Corrosion occurs Corrosion occurs

As shown in Tables 5 and 6, since the stripper compositions of Examples 1, 3, 4, and 5 contain both methimazole and triazole-based compounds, corrosion resistance to copper metal compared to the stripper compositions of Comparative Examples 2 to 5 It was found to decrease.

From these results, it can be seen that the methymazole and triazole-based compounds included in the stripper composition of the examples have excellent ability to prevent corrosion of copper metal.

3. Corrosion evaluation of copper (Cu)/molybdenum (Mo) metal lower film

Using a transmission electron microscope (Helios NanoLab650), the cross-sections of the samples for corrosion evaluation obtained in Examples 1 to 5 and Comparative Examples 1, 3, 4, 6, and 7 were observed. Specifically, a thin piece of a sample for corrosive evaluation was produced using a FIB (Focused Ion Beam), and then observed with an acceleration voltage of 2 kV, and the sample surface (Cu layer) was used to prevent surface damage due to ion beams during the specimen production ), a Pt (platinum) protection layer was formed, and then TEM flakes were fabricated.

division Example 1 Example 2 Example 3 Example 4 Example 5 Size(nm) <10nm <10nm <10nm <10nm <10nm

division Comparative Example 1 Comparative Example 3 Comparative Example 4 Comparative Example 7 Size(nm) 137nm 292nm 251nm 283nm

As shown in Tables 7 and 8, since the stripper compositions of Examples 1 to 5 contain both metimazole and triazole-based compounds, Comparative Example 1 including methimazole and benzimidazole and one type of corrosion inhibitor Compared to the stripper compositions of Comparative Examples 3, 4 and 7, it was confirmed that the corrosiveness of the lower layer of copper (Cu)/molybdenum (Mo) metal was decreased.

From these results, it can be confirmed that the methymazole and triazole-based compounds included in the stripper composition of the embodiment have excellent ability to prevent corrosion of the copper (Cu)/molybdenum (Mo) metal lower layer.

Claims (10)

An amide compound in which a linear or branched alkyl group having 1 to 5 carbon atoms is substituted with 1 to 2 nitrogen;
Amine compounds;
Polar organic solvents;
Methimazole; And
Triazole-based compound; containing, a photoresist stripper composition for removing.
The method of claim 1,
The weight ratio between the methimazole and the triazole-based compound is 1:1 to 1:50, a stripper composition for removing photoresist.
The method of claim 1,
A stripper composition for removing a photoresist comprising 1 to 30 parts by weight of a total of methimazole and triazole-based compounds based on 100 parts by weight of the amine compound.
The method of claim 1,
The triazole-based compound is (2,2'[[(methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol, 4,5,6,7-tetrahydro-1H-benzotriazole, 1H-benzotriazole, 1H-1,2,3-triazole or methyl 1H- comprising at least one compound selected from the group consisting of benzotriazole, stripper composition for removing photoresist.
The method of claim 1,
The amine compound comprises a cyclic amine compound having a weight average molecular weight of 95 g/mol or more, a photoresist stripper composition.
The method of claim 5,
The amine compound further comprises a chain-type amine compound having a weight average molecular weight of 95 g/mol or more, a stripper composition for removing a photoresist.
The method of claim 1,
The amide-based compound in which a linear or branched alkyl group having 1 to 5 carbon atoms is substituted with 1 to 2 nitrogen is a stripper composition for removing a photoresist comprising a compound of the following formula (1):
[Formula 1]

In Formula 1, R ₁ is hydrogen, a methyl group, an ethyl group, a propyl group,
R ₂ and R ₃ are each hydrogen or a linear or branched alkyl group having 1 to 5 carbon atoms, and at least one of R ₂ and R ₃ is a methyl group.
The method of claim 1,
The polar organic solvent comprises at least one selected from the group consisting of alkylene glycol monoalkyl ether, pyrrolidone, sulfone and sulfoxide, a stripper composition for photoresist removal.
The method of claim 1,
10 to 80% by weight of an amide compound in which a straight or branched alkyl group having 1 to 5 carbon atoms is substituted with 1 to 2 nitrogen;
0.1 to 10% by weight of an amine compound;
10 to 80% by weight of a polar organic solvent;
0.001 to 0.5% by weight of methimazole; And
0.01 to 5.0% by weight of a triazole-based compound; Containing, a photoresist stripper composition for removal.
A method of removing a photoresist comprising the step of removing the photoresist using the stripper composition for removing the photoresist of claim 1.