KR102228536B1 - Stripper composition for removing photoresist and stripping method of photoresist using the same - Google Patents

Abstract

The present invention is an aqueous stripper composition for removing photoresist that can exhibit excellent storage stability, peeling force and rinsing power equal to or higher than that of an organic stripper as an aqueous stripper containing water, and minimizing reproductive toxicity and metal corrosiveness, and It relates to a method for removing photoresist using the same.

Description

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

The present invention relates to a photoresist stripper composition and a photoresist stripping method using the same. More specifically, as an aqueous stripper containing water, a stripper composition for photoresist removal capable of exhibiting excellent peeling strength and rinsing power equal to or higher than that of an organic stripper, and minimizing reproductive toxicity and metal corrosiveness, and using the same It relates to a photoresist peeling method.

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 the same various lower layers, uniformly applying a photoresist on the lower layers, 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 polar protic solvent, and a polar aprotic solvent have been widely known from the past, and among them, particularly, as a polar aprotic solvent, including N-methyl form amide (NMF). Stripper compositions have been widely used. It is known that a stripper composition containing such NMF exhibits excellent peel strength.

However, this NMF is a Category 1B (GHS standard) substance that exhibits reproductive toxicity, and its use is gradually regulated. For this reason, various attempts have been made to develop a stripper composition exhibiting excellent peeling force and rinsing force without the use of the NMF, but a stripper composition showing sufficient peeling force and rinsing force has not been properly developed. to be.

In addition, the previous stripper composition containing the NMF has a problem in that 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 consideration of this situation, conventionally, a method of including an excessive amount of amine compound in the stripper composition was used to maintain excellent peeling force and rinsing force over time, but in this case, the economical efficiency and efficiency of the process may be greatly reduced. Environmental or process problems may occur depending on the amine compound of.

Accordingly, there is a need to develop a new stripper composition capable of maintaining excellent peeling force and rinsing force over time without containing a solvent exhibiting biotoxicity.

The present invention provides a stripper composition for photoresist removal capable of minimizing reproductive toxicity and metal corrosiveness as an aqueous stripper containing water, which can exhibit excellent storage stability, peeling force, and rinsing power equal to or higher than that of an organic stripper. It is to do.

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

In the present specification, an aqueous solvent; An amide compound in which a linear or branched alkyl group having 1 to 5 carbon atoms is 1 to 2 substituted with nitrogen; One or more amine compounds; And a protonic polar solvent, wherein a weight ratio of the amide compound is 10 to 90 parts by weight based on 100 parts by weight of the aqueous solvent, and a stripper composition for removing a photoresist 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 stripper composition.

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

In the present specification,'chain type' refers to a chemical structure in which carbon atoms are connected in a chain shape, and includes both a straight chain shape and a branched shape, and means a chemical structure in contrast to a cyclic structure.

In the present specification, the'alkyl group' is a monovalent functional group derived from alkane, for example, as a straight chain, branched or cyclic, methyl, ethyl, propyl, isobutyl, sec-butyl, tert -It can be butyl, pentyl, hexyl, etc. One or more hydrogen atoms included in the alkyl group may be substituted with other substituents, and examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, and 6 to carbon atoms. 12 aryl group, C2-C12 heteroaryl group, C6-C12 arylalkyl group, halogen atom, cyano group, amino group, amidino group, nitro group, amide group, carbonyl group, hydroxy group, sulfonyl group, carbamate Group, a C1-C10 alkoxy group, etc. are mentioned.

The term "substituted" means that other functional groups are bonded in place of a hydrogen atom in the compound, and the position to be substituted is not limited as long as the position at which the hydrogen atom is substituted, that is, the position where the substituent can be substituted. The substituents may be the same or different from each other.

In the present specification, the'alkylene group' is a divalent functional group derived from alkane, for example, as a straight chain, branched or cyclic, methylene group, ethylene group, propylene group, isobutylene group, It may be a sec-butylene group, a tert-butylene group, a pentylene group, a hexylene group, and the like. At least one hydrogen atom included in the alkylene group may be substituted with the same substituent as in the case of the alkyl group.

In the present specification,'*' means a bonding point of a functional group.

According to an embodiment of the invention, an aqueous solvent; An amide compound in which a linear or branched alkyl group having 1 to 5 carbon atoms is 1 to 2 substituted with nitrogen; One or more amine compounds; And a protonic polar solvent, wherein a weight ratio of the amide compound to 100 parts by weight of the aqueous solvent is 10 parts by weight to 90 parts by weight, and a stripper composition for removing a photoresist may be provided.

The present inventors use the stripper composition for photoresist removal of the above embodiment, even if an aqueous solvent is contained in an excessive amount, excellent peeling ability, stability over time, and corrosion protection for metals can be realized. It was confirmed through an experiment that the stripper could be substituted and the invention was completed.

This effect seems to be due to the mixing of water, which is an aqueous solvent, and a specific amide compound, and in particular, by mixing an excess of water compared to a specific amide compound, the amine compound and the amide compound contained in the photoresist stripper composition By effectively suppressing the decomposition reaction that occurs, the storage stability of the stripper composition can be improved.

In addition, the photoresist removal stripper composition of the embodiment further improves peeling power, rinsing power, and corrosion protection when mixing an amine compound, a proton organic solvent, and a corrosion inhibitor in a specific ratio on an aqueous solvent. It was confirmed that it can be done.

In particular, the aqueous solvent used in the photoresist stripper composition according to the embodiment may form hydrogen bonds with the amide compound, thereby minimizing a decomposition reaction between the amine and the amide compound in the composition. Accordingly, when mixed with an amide compound, an amine compound, a proton organic solvent, and a corrosion inhibitor, excellent physical properties as a stripper can be implemented, and superior storage stability can be secured compared to the conventional organic stripper.

Accordingly, the conventional organic stripper in which an aqueous solvent is not used and the aqueous stripper of the embodiment appear to correspond to completely different technical fields.

Specifically, the photoresist stripper composition for removing may include an aqueous solvent. An example of the aqueous solvent may be distilled water, and as the aqueous solvent is used, the amount of organic solvent used can be reduced, thereby improving the manufacturing efficiency of the semiconductor substrate, reducing the manufacturing cost, and improving productivity and stability. .

The aqueous solvent may be contained in an amount of 25 to 50 parts by weight based on 100 parts by weight of the total content of the photoresist stripper composition, and when the aqueous solvent is added in an excessive amount, peeling of the photoresist stripper composition The power may be reduced.

Meanwhile, the photoresist stripper composition may include an amide compound in which a linear or branched alkyl group having 1 to 5 carbon atoms is 1 to 2 substituted with nitrogen. The amide compound in which the linear or branched alkyl group having 1 to 5 carbon atoms is 1 to 2 substituted with nitrogen can dissolve the amine compound well in the stripper composition, and the stripper composition for removing the photoresist is effectively on the lower film. By soaking, peeling power and rinsing power of the stripper composition can be improved.

Specifically, the amide compound in which the linear or branched alkyl group having 1 to 5 carbon atoms is 1 to 2 substituted with nitrogen may include an amide compound in which a linear alkyl group having 2 to 4 carbon atoms is disubstituted with nitrogen. The amide compound in which the straight-chain alkyl group having 2 to 4 carbon atoms is disubstituted with nitrogen may have a structure represented by the following formula (11).

[Formula 11]

In Formula 11, R ₁ is hydrogen, a methyl group, an ethyl group, a propyl group,

R ₂ and R ₃ are each hydrogen or a straight-chain alkyl group having 2 to 4 carbon atoms, and at least one of R 2 and R 3 is an ethyl group.

Examples of the straight-chain alkyl group having 2 to 4 carbon atoms are not limited, but, for example, an ethyl group, a propyl group, or a butyl group may be used.

More specifically, the example of the amide compound in which the straight-chain alkyl group having 2 to 4 carbon atoms is disubstituted with nitrogen is not limited, but, for example, N,N'-diethylcarboxamide (DCA) may be used. . Unlike conventional methylformamide (NMF) or dimethylacetamide (DMAC), the N,N'-diethylcarboxamide (DCA) does not substantially exhibit reproductive or biotoxicity, and hardly decomposes amine compounds over time. It is not caused to cause the stripper composition of the embodiment to maintain excellent physical properties such as peeling force and rinsing force for a long period of time.

Examples of the N,N'-diethylcarboxamide (DCA) include diethylformamide, diethylacetamide, diethylpropionamide, and the like, preferably diethylformamide.

The diethylformamide (DEF) has two ethyl groups bonded to the nitrogen atom contained in the amide structure, and the steric hindrance effect around the nitrogen atom is relatively increased due to the molecular structural bulky ethyl group compared to the methyl group. , It has little reactivity to amine compounds. Accordingly, the amine compound can be stably and satisfactorily dissolved, and the stripper composition for removing the photoresist can effectively permeate the lower film, thereby improving peeling power and rinsing power of the stripper composition.

For reference, in the case of methylformamide (NMF), dimethylformamide (DMF), and dimethylacetamide (DMAC), their use is regulated during display or device processing due to reproductive or biotoxicity issues.In particular, DMF is reproductive toxicity. And as a specific target organ toxic substance, it has been identified as being related to leukemia and its use is regulated. In contrast, the N,N'-diethylcarboxamide (DCA) can achieve excellent physical properties such as excellent peeling force of the stripper composition without exhibiting such reproductive and biotoxicity.

The amide compound in which a linear or branched alkyl group having 1 to 5 carbon atoms is 1 to 2 substituted with nitrogen may be included in an amount of 10 to 30 parts by weight based on 100 parts by weight of the total content of the stripper composition for removing photoresist. Depending on the content range, 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.

Specifically, the weight ratio of the amide compound to 100 parts by weight of the aqueous solvent may be 10 parts by weight to 90 parts by weight, or 30 parts by weight to 60 parts by weight. That is, the stripper composition for photoresist removal of the embodiment may have a characteristic of mixing an amide compound together with an aqueous solvent and mixing the aqueous solvent in an excessive amount compared to the amide compound.

When the weight ratio of the amide compound to 100 parts by weight of the aqueous solvent is excessively increased to more than 90 parts by weight, the decomposition reaction between the amine compound and the amide compound contained in the stripper composition for removing the photoresist of the embodiment proceeds excessively. Therefore, as the rate at which the content of the amine compound decreases during long-term storage increases, the lifespan of the stripper composition may decrease, and storage stability may decrease.

The photoresist stripper composition for removing may include one or more amine compounds. The amine compound is a component exhibiting detergency, and may serve to remove organic foreign substances by dissolving them. The at least one amine compound may include a chain amine compound, a cyclic amine compound, or a mixture thereof.

The chain amine compound is (2-aminoethoxy)-1-ethanol, aminoethylethanolamine, N-methylethanolamine, N-methyl diethanolamine, N-butyl diethanolamine, diethylene triamine, die Deolamine, diethylaminoethanol, triethanolamine, 1-aminoisopropanol, monomethanol amine, monoethanol amine, monoisopropanolamine, 2-methylaminoethanol, 3-aminopropanol, N-methylethylamine and triethylene tetraamine It may include one or more compounds selected from the group consisting of.

The cyclic amine compound is 1-imidazolidine ethanol (IME, LGA), amino ethyl piperazine (AEP), hydroxyl ethylpiperazine (HEP), or their It may contain a mixture of two or more.

The photoresist stripper composition may include the at least one amine compound in an amount of 1 to 10 parts by weight based on 100 parts by weight of the total photoresist stripper composition content. If the at least one amine compound is less than 1 part by weight relative to 100 parts by weight of the photoresist stripper composition, the peel strength of the photoresist stripper composition may decrease. In addition, if the amine compound is more than 10 parts by weight relative to 100 parts by weight of the total photoresist stripper composition, the corrosiveness to metal may increase, 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 substrate by a large amount of the corrosion inhibitor, thereby deteriorating electrical properties.

When the chain-type amine compound and the cyclic amine compound are mixed at the same time, the weight ratio of each is not significantly limited, for example, in a weight ratio of 1:10 to 10:1 or 1:5 to 5:1, respectively Can be mixed.

Specifically, the weight ratio of the amine compound to 100 parts by weight of the aqueous solvent may be 1 part by weight to 50 parts by weight, or 10 parts by weight to 20 parts by weight. That is, the stripper composition for photoresist removal of the embodiment may have a characteristic of mixing an amine compound together with an aqueous solvent and mixing the aqueous solvent in an excess amount compared to the amine compound.

Meanwhile, the photoresist stripper composition for removing may include a proton polar solvent. The proton polar solvent allows the photoresist stripper composition to more permeate onto the substrate, thereby assisting with excellent cleaning power, and effectively removes stains on the substrate to improve the rinsing power of the stripper composition for removing the photoresist. .

The protonic polar solvent may include alkylene glycol or alkylene glycol monoalkyl ether. 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 cleaning power and rinsing power, the alkylene glycol monoalkyl ethers include diethylene glycol monomethyl ether (MDG) and diethylene glycol monoethyl. Ether (EDG) or diethylene glycol monobutyl ether (BDG) may be used.

In addition, the proton polar solvent may be included in an amount of 20 parts by weight to 50 parts by weight based on 100 parts by weight of the total photoresist stripper composition. As the content range is satisfied, excellent cleaning power of the stripper composition for removing photoresist can be secured, and the cleaning power and rinsing power can be maintained for a long period of time.

Specifically, the weight ratio of the protonic polar solvent to 100 parts by weight of the aqueous solvent may be 100 parts by weight to 200 parts by weight, or 110 parts by weight to 140 parts by weight. That is, the photoresist removal stripper composition of the embodiment may have a characteristic of mixing a protic polar solvent together with an aqueous solvent and mixing the protic polar solvent in an excess amount compared to the aqueous solvent.

Meanwhile, the photoresist stripper composition may further include a corrosion inhibitor. Such a corrosion inhibitor may suppress corrosion of a metal-containing lower film such as a copper-containing film when removing a photoresist pattern using the photoresist stripper composition.

As the corrosion inhibitor, a benzimidazole-based compound, a triazole-based compound, a tetrazole-based compound, or a mixture of two or more thereof may be used.

The triazole-based compound may include a compound represented by Formula 1 or 2 below.

[Formula 1]

In Formula 1, R ₄ is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is hydrogen or a functional group represented by the following Formula 1-1, and a is an integer of 1 to 4,

[Formula 1-1]

In Formula 1-1, R ₅ and R ₆ are the same as or different from each other and are a hydroxyalkyl group having 1 to 4 carbon atoms, Y is an alkylene group having 1 to 10 carbon atoms,

[Formula 2]

In Formula 2, R ₇ is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is hydrogen or a functional group represented by Formula 1-1, and b is an integer of 1 to 4.

Examples of such corrosion inhibitors are not largely limited, for example (1) R ₄ is a methyl group in Formula 1, a is 1, X is a functional group represented by Formula 1-1, and in Formula 1, Y is a methylene group, and R ₅ and R ₆ are each hydroxyethyl compound (2,2'[[(Methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol), or (2) Formula 1 In, R ₄ is a methyl group, a is 1, X is a hydrogen compound (tolyltriazole), or (3) In Formula 2, R ₇ is a methyl group, b is 1, and X is a hydrogen compound (4,5 ,6,7-tetrahydrotolyltriazole), and a tetrazole-based compound such as 5-aminotetrazole or a hydrate thereof. By using the corrosion inhibitor, it is possible to effectively suppress the corrosion of the metal-containing lower film, while excellently maintaining the peeling force of the stripper composition.

In addition, the corrosion inhibitor may be included in an amount of 0.01 parts by weight to 0.5 parts by weight, or 0.05 parts by weight to 0.3 parts by weight, or 0.2 parts by weight to 0.3 parts by weight, based on 100 parts by weight of the total composition. If the content of the corrosion inhibitor is less than 0.01 parts by weight based on 100 parts by weight of the total composition, it may be difficult to effectively suppress corrosion on the lower film. In addition, if the content of the corrosion inhibitor exceeds 0.5 parts by weight based on 100 parts by weight of the total composition, a significant amount of the corrosion inhibitor adsorbs and remains on the lower film, thereby deteriorating the electrical properties of the copper-containing lower film.

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 the protic polar solvent. This 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 for the lower film, so that even after treatment with the stripper composition, stains or foreign matters almost occur and remain on the lower film. 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.

The silicone-based nonionic surfactant may include a polysiloxane-based polymer. More specifically, examples of the polysiloxane-based polymer include polyether-modified acrylic functional polydimethylsiloxane, polyether-modified siloxane, polyether-modified polydimethylsiloxane, polyethylalkylsiloxane, aralkyl-modified polymethylalkylsiloxane, and polyether-modified hydroxide. And a oxy-functional polydimethylsiloxane, a polyether-modified dimethylpolysiloxane, a modified acrylic functional polydimethylsiloxane, or a mixture of two or more thereof.

The silicone-based nonionic surfactant may be included in an amount of 0.0005 parts by weight to 0.1 parts by weight, or 0.001 parts by weight to 0.09 parts by weight, or 0.001 parts by weight to 0.01 parts by weight based on 100 parts by weight of the total composition. When the content of the silicone-based nonionic surfactant is less than 0.0005 parts by weight based on 100 parts by weight of 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 parts by weight based on 100 parts 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 the equipment sensor It may cause malfunction.

The photoresist stripper composition for removing the photoresist may further include a conventional additive as necessary, 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 each component described above, and there is no particular limitation on a specific method of preparing the photoresist stripper composition. The stripper composition for removing the photoresist can exhibit excellent peeling strength and rinsing force without the use of reproductive toxic substances such as methylformamide (NMF) and dimethylacetamide (DMAC), and excellent peeling strength over time. By holding, it can be used to remove the residual photoresist pattern on the lower layer.

On the other hand, according to another embodiment of the invention, 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 stripper composition for removing the photoresist according to the embodiment.

The information on the stripper composition for removing the photoresist includes the above-described information with respect to 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 a 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 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.

According to the present invention, as an aqueous stripper containing water, a stripper composition for photoresist removal capable of exhibiting excellent storage stability, peeling force and rinsing power equal to or higher than that of an organic stripper, and minimizing reproductive toxicity and metal corrosiveness And a photoresist peeling method using the same may be provided.

Composition of stripper composition for removing photoresist of Examples 1 to 8 division Example 1
(Part by weight) Example 2
(Part by weight) Example 3
(Part by weight) Example 4
(Part by weight) Example 5
(Part by weight) Example 6
(Part by weight) Example 7
(Part by weight) Example 8
(Part by weight) DIW 35 35 35 35 35 35 35 35 IME 3 - - - - - - - HEP - - 3 - - 4 - - AEP-HP - - - 3 - - 4 - MEA - - - - - - - - MIPA - - - - 4 - - - AEE One 4 One One - - - - AEEA - - - - - - - 4 N-MEA - - - - - - - - MDEA - - - - - - - - BDEA - - - - - - - - DEF 20 20 20 20 20 20 20 20 NMF - - - - - - - - DMSO - - - - - - - - DMAC - - - - - - - - BDG 40.7 - 40.7 - 40.8 - 40.7 - MDG - 40.8 - - - 40.7 - - EDG - - - 40.7 - - - 40.8 Corrosion inhibitor 1 0.3 - 0.3 0.3 - 0.3 0.3 - Corrosion inhibitor 2 - 0.2 - - 0.2 - - 0.2 Corrosion inhibitor 3 - - - - - - - -

* DIW: deionized water

* IME: 1-Imidazolidine ethanol

* HEP: 1-(2-Hydroxyethyl)piperazine)

* AEP-HP: Aminoethylpiperazine

* MEA: Monoethanolamine

* MIPA: Monoisopropanolamine

* AEE: (2-aminoethoxy)-1-ethanol ((2-aminoethoxy)-1-ethanol)

* AEEA: Aminoethylethanolamine

* N-MEA: N-methylethanolamine

* MDEA: N-methyldiethanolamine

* BDEA: N-butyldiethanolamine

* DEF: N,N'-diethylformamide

* NMF: N-methylformamide

* DMSO: Dimethylsulfoxide

* DMAC: Dimethylacetamide

* BDG: Diethyleneglycol monobutylether

* MDG: Diethyleneglycol monomethylether

* EDG: Diethyleneglycol monoethylether

* Corrosion inhibitor 1: 2,2'[[(Methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol

* Corrosion inhibitor 2: 4,5,6,7-tetrahydrotolyltriazole (4,5,6,7-tetrahydrotolyltriazole)

* Corrosion inhibitor 3: Tolyltriazole

Composition of stripper composition for removing photoresist of Examples 9 to 16 division Example 9
(Part by weight) Example 10
(Part by weight) Example 11
(Part by weight) Example 12
(Part by weight) Example 13
(Part by weight) Example 14
(Part by weight) Example 15
(Part by weight) Example 16
(Part by weight) DIW 35 35 35 35 35 35 35 35 IME One One One One One One One One HEP - - - - - - - - AEP-HP - - - - - - - - MEA - - - - - - - - MIPA - - - - - - - - AEE 3 3 3 3 3 - - - AEEA - - - - - - - - N-MEA - - - - - 3 - - MDEA - - - - - - 3 - BDEA - - - - - - - 3 DEF 14 14 14 14 14 14 14 14 NMF - - - - - - - - DMSO - - - - - - - - DMAC - - - - - - - - BDG 46.7 46.7 - - - - - - MDG - - 46.7 - 46.7 46.7 46.7 46.7 EDG - - - 46.7 - - - - Corrosion inhibitor 1 0.3 - - - - 0.3 0.3 0.3 Corrosion inhibitor 2 - - 0.3 - 0.3 - - - Corrosion inhibitor 3 - 0.3 - 0.3 - - - -

* DIW: deionized water

* IME: 1-Imidazolidine ethanol

* HEP: 1-(2-Hydroxyethyl)piperazine)

* AEP-HP: Aminoethylpiperazine

* MEA: Monoethanolamine

* MIPA: Monoisopropanolamine

* AEE: (2-aminoethoxy)-1-ethanol ((2-aminoethoxy)-1-ethanol)

* AEEA: Aminoethylethanolamine

* N-MEA: N-methylethanolamine

* MDEA: N-methyldiethanolamine

* BDEA: N-butyldiethanolamine

* DEF: N,N'-diethylformamide

* NMF: N-methylformamide

* DMSO: Dimethylsulfoxide

* DMAC: Dimethylacetamide

* BDG: Diethyleneglycol monobutylether

* MDG: Diethyleneglycol monomethylether

* EDG: Diethyleneglycol monoethylether

* Corrosion inhibitor 1: 2,2'[[(Methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol

* Corrosion inhibitor 2: 4,5,6,7-tetrahydrotolyltriazole (4,5,6,7-tetrahydrotolyltriazole)

* Corrosion inhibitor 3: Tolyltriazole

Composition of stripper compositions for photoresist removal of Comparative Examples 1 to 7 division Comparative Example 1
(Part by weight) Comparative Example 2
(Part by weight) Comparative Example 3
(Part by weight) Comparative Example 4
(Part by weight) Comparative Example 5
(Part by weight) Comparative Example 6
(Part by weight) Comparative Example 7
(Part by weight) DIW 20 - - - 35 - 20 IME - - - 3 3 - 3 HEP - - - - - 3 - AEP-HP - - - - - - - MEA - 30 70 - - - - MIPA - - - - - - - AEE - - - - - - One AEEA - - - - - One - N-MEA 10 - - - - - - MDEA - - - - - - - BDEA - - - - - - - DEF - - - - - - 35 NMF - - - 50 20 50 - DMSO - - 30 - - - - DMAC - - - - - - - BDG 70 70 - - - - 40.7 MDG - - - 46.8 41.8 45.8 - EDG - - - - - - - Corrosion inhibitor 1 - - - 0.2 0.2 0.2 0.3 Corrosion inhibitor 2 - - - - - - - Corrosion inhibitor 3 - - - - - - -

* DIW: deionized water

* IME: 1-Imidazolidine ethanol

* HEP: 1-(2-Hydroxyethyl)piperazine)

* AEP-HP: Aminoethylpiperazine

* MEA: Monoethanolamine

* MIPA: Monoisopropanolamine

* AEE: (2-aminoethoxy)-1-ethanol ((2-aminoethoxy)-1-ethanol)

* AEEA: Aminoethylethanolamine

* N-MEA: N-methylethanolamine

* MDEA: N-methyldiethanolamine

* BDEA: N-butyldiethanolamine

* DEF: N,N'-diethylformamide

* NMF: N-methylformamide

* DMSO: Dimethylsulfoxide

* DMAC: Dimethylacetamide

* BDG: Diethyleneglycol monobutylether

* MDG: Diethyleneglycol monomethylether

* EDG: Diethyleneglycol monoethylether

* Corrosion inhibitor 1: 2,2'[[(Methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol

* Corrosion inhibitor 2: 4,5,6,7-tetrahydrotolyltriazole (4,5,6,7-tetrahydrotolyltriazole)

* Corrosion inhibitor 3: Tolyltriazole

< Experimental example : Example And In Comparative Example Obtained Photoresist For removal Stripper Measurement of the physical properties of the composition>

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. Peeling force

1-1. Normal condition ( 140 ℃ 10 minutes at temperature Hard Bake In) New liquid Peeling force evaluation

300g of the stripper composition obtained in the above Examples and Comparative Examples was placed in a 500ml beaker and maintained at 40°C.

Thereafter, a positive photoresist was spin coated on a 100 mm x 100 mm molybdenum (Mo)/aluminum (Al)/molybdenum (Mo) pattern film using a spin coating device at a speed of 800 rpm, and then mounted on a hot plate, 140 A photoresist was formed by hard baking for 10 minutes at a temperature of °C. In addition, a specimen was prepared by cutting the pattern film on which the photoresist was formed into a size of 30 mm x 30 mm.

The specimen was immersed in the stripper compositions of Examples and Comparative Examples, washed with distilled water for 60 seconds, and dried in air for 30 seconds. The time when the photoresist was completely peeled and removed was measured to evaluate the peel strength of the new solution, and the results are shown in Table 4 below. At this time, whether or not the photoresist was peeled off was confirmed by observing the specimen with an optical microscope and whether or not the photoresist remained.

1-2. Normal condition ( 140 ℃ 10 minutes at temperature Hard Bake Neglect in) Peeling force evaluation

A sample for evaluating peel strength was prepared in the same manner as in Experimental Example 1-1, and 300g of the stripper composition obtained in Examples and Comparative Examples was placed in a 500ml beaker, and the photoresist powder was added to the total composition 100 in a state maintained at 40°C. After adding in an amount of 1 part by weight based on parts by weight, the mixture was stirred at 40° C. for 24 hours to cause a change over time.

The peeling force over time of the stripper composition was evaluated in the same manner as in Experimental Example 1-1, and the results are shown in Table 4 below.

Peeling force of stripper composition for photoresist removal under normal conditions Stripper composition New liquid peeling force (seconds) Peeling force over time (seconds) Example 1 10 10 Example 2 10 10 Example 3 10 10 Example 4 10 10 Example 5 10 10 Example 6 10 10 Example 7 10 10 Example 8 10 10 Example 9 10 10 Example 10 10 10 Example 11 10 10 Example 12 10 10 Example 13 10 10 Example 14 10 10 Example 15 10 10 Example 16 10 10 Comparative Example 1 30 30 Comparative Example 2 10 10 Comparative Example 3 10 30 Comparative Example 4 10 10 Comparative Example 5 10 10 Comparative Example 6 10 10

As shown in Table 4, it was confirmed that the stripper composition of the Example exhibits a photoresist peeling force (fast peeling time) comparable to or better than the stripper composition of Comparative Example.

1-3. Harsh conditions ( 150 ℃ At temperature for 20 minutes Hard Bake In) New liquid Peeling force evaluation

300g of the stripper composition obtained in Example 1, Comparative Example 4 and Comparative Example 6 was placed in a 500ml beaker and maintained at 40°C.

Thereafter, a positive photoresist was spin coated on a 100 mm x 100 mm molybdenum (Mo)/aluminum (Al)/molybdenum (Mo) pattern film using a spin coating device at a speed of 800 rpm, and then mounted on a hot plate. A photoresist was formed by hard baking for 20 minutes at a temperature of °C. In addition, a specimen was prepared by cutting the pattern film on which the photoresist was formed into a size of 30 mm x 30 mm.

The specimens were immersed in the stripper compositions of Examples 1, 4 and 6, washed with distilled water for 60 seconds, and dried in air for 30 seconds. The time when the photoresist was completely peeled and removed was measured to evaluate the peel strength of the new solution, and the results are shown in Table 5 below. At this time, whether or not the photoresist was peeled off was confirmed by observing the specimen with an optical microscope and whether or not the photoresist remained.

Peeling force of stripper composition for photoresist removal under harsh conditions Hard bake conditions New liquid peeling force (seconds) Temperature(℃) Time(min) Example 1 Comparative Example 6 150 20 40 90

As shown in Table 5, it was confirmed that the stripper composition of Example 1 exhibits superior photoresist peeling force (faster peeling time) than the stripper composition of Comparative Example 6.

2. Metal corrosion protection evaluation

2-1. Copper (Cu) corrosion protection

300g of the stripper composition obtained in the above Examples and Comparative Examples was placed in a 500ml beaker and maintained at 40°C.

Thereafter, the metal wire on which copper (Cu) was deposited was cut into a size of 30 mm x 30 mm to prepare a specimen.

The specimens were immersed in the stripper compositions of Examples 1, 9, 10, 11 and Comparative Examples 1, 2, and 3 for 10 minutes, washed with distilled water for 60 seconds, and dried in air for 30 seconds. Then, the immersed specimen was observed with an optical microscope to evaluate the corrosion protection under the following criteria, and the results are shown in Table 6 below.

OK: No copper corrosion is observed

NG: Corrosion occurs on copper

2-2. Molybdenum (Mo)/aluminum (Al) corrosion protection

300g of the stripper composition obtained in the above Examples and Comparative Examples was placed in a 500ml beaker and maintained at 40°C.

Thereafter, a metal wire on which molybdenum (Mo)/aluminum (Al) was deposited was cut into a size of 30 mm x 30 mm to prepare a specimen.

The specimens were immersed in the stripper compositions of Examples 1, 9, 10, 11 and Comparative Examples 1, 2, and 3 for 10 minutes, washed with distilled water for 60 seconds, and dried in air for 30 seconds. Then, the immersed specimen was observed with an optical microscope to evaluate the corrosion protection under the following criteria, and the results are shown in Table 6 below.

OK: No corrosion of molybdenum (Mo)/aluminum (Al) was observed

NG: Corrosion occurs in molybdenum (Mo)/aluminum (Al)

Metal corrosion protection of photoresist stripper composition metal Example 1 Example 9 Example 10 Example 11 Comparative Example 1 Comparative Example 2 Comparative Example 3 Cu OK OK OK OK NG NG NG Mo/Al OK OK OK OK OK OK OK

As shown in Table 6, it was confirmed that the stripper composition of the Example exhibits superior metal corrosion protection than the stripper compositions of Comparative Examples 1 to 3. From these results, it can be seen that the corrosion inhibitor included in the stripper composition of the embodiment can implement excellent corrosion protection, and can be applied to all TFT metals such as copper and aluminum through this.

3. Rinse power evaluation

300g of the stripper compositions obtained in Examples 1, 10, 11, 12 and Comparative Examples 1 and 4 were placed in a 500ml beaker and maintained at 40°C.

Thereafter, a positive photoresist was spin coated on a 100 mm x 100 mm molybdenum (Mo)/aluminum (Al)/molybdenum (Mo) pattern film using a spin coating device at a speed of 800 rpm, and then mounted on a hot plate, 140 A photoresist was formed by hard baking for 10 minutes at a temperature of °C. In addition, a specimen was prepared by cutting the pattern film on which the photoresist was formed into a size of 30 mm x 30 mm.

The specimen was immersed in the stripper compositions of Examples 1, 10, 11, 12 and Comparative Examples 1 and 4 for 1 minute, and after passing through an air curtain 50kpa, 1 μm drop of ultrapure water was added dropwise and waited for 30 seconds. After washing with ultrapure water for 60 seconds, drying in air for 30 seconds, the specimen was observed with an optical microscope to evaluate the rinse power under the following criteria, and the results are shown in Table 7 below.

OK: No stain or foreign matter was observed on the specimen;

NG: A stain or foreign matter was observed on the specimen.

Rinse power of stripper composition for photoresist removal Example 1 Example 9 Example 10 Example 11 Comparative Example 1 Comparative Example 4 OK OK OK OK NG NG

As shown in Table 7 above, it was confirmed that the stripper composition of the Example has improved rinsing power compared to the Comparative Example. From these results, it can be confirmed that the solvent such as DEF contained in the stripper composition of the Example expresses and maintains excellent rinsing power.

4. Change in amine content

100 ml of the photoresist stripper composition for removing photoresist of Example 1 and Comparative Example 7 was sealed in a 250 ml bottle and stored in an oven at 40°C, while changes in amine (IME and AEE) content relative to 100 parts by weight of the total composition were observed for each storage date. Analysis and evaluation by gas chromatography (GC) are shown in Table 8 below.

Changes in amine content over time in stripper composition for photoresist removal Elapsed days Amine content of Example 1 (parts by weight) Amine content of Comparative Example 7 (parts by weight) 0 4.00 4.00 10 3.98 3.70 30 3.97 3.50

As shown in Table 8, the amine content of the stripper composition of Example 1 was reduced by 0.03 parts by weight even when stored for a long time for 30 days under severe conditions over time, whereas the composition of Comparative Example 7 had an amine content when stored for 30 days. It was confirmed that it was reduced by 0.5 parts by weight.

Accordingly, as in Comparative Example 7, when the weight ratio of DEF to 100 parts by weight of DIW is contained in an excessive amount exceeding 100 parts by weight, the degree of decomposition of the amine compound is relatively increased, so that the stripper composition for photoresist removal is stored. It can be seen that the stability decreases.

Claims (14)

Aqueous solvent;
An amide compound in which a linear or branched alkyl group having 1 to 5 carbon atoms is 1 to 2 substituted with nitrogen;
One or more amine compounds; And
Containing a protic polar solvent,
The weight ratio of the amide compound to 100 parts by weight of the aqueous solvent is 10 parts by weight to 90 parts by weight,
Including the aqueous solvent in an amount of 25 parts by weight to 50 parts by weight based on 100 parts by weight of the total content of the stripper composition for removing photoresist,
The weight ratio of the amine compound to 100 parts by weight of the aqueous solvent is 1 part by weight to 50 parts by weight,
A stripper composition for removing a photoresist comprising the amine compound in an amount of 3 to 10 parts by weight based on 100 parts by weight of the total photoresist removal stripper composition.
The method of claim 1,
The amide compound includes an amide compound in which a linear alkyl group having 2 to 4 carbon atoms is disubstituted with nitrogen, a stripper composition for photoresist removal.
The method of claim 1,
The amide compound comprises diethyl formamide, a photoresist stripper composition for removing.
The method of claim 1,
The amine compound is a photoresist stripper composition comprising at least one selected from the group consisting of a chain amine compound and a cyclic amine compound.
The method of claim 4,
The chain amine compound is (2-aminoethoxy)-1-ethanol, aminoethylethanolamine, N-methylethanolamine, N-methyl diethanolamine, N-butyl diethanolamine, diethylene triamine, die Deolamine, diethylaminoethanol, triethanolamine, 1-aminoisopropanol, monomethanol amine, monoethanol amine, monoisopropanolamine, 2-methylaminoethanol, 3-aminopropanol, N-methylethylamine and triethylene tetraamine A photoresist stripper composition comprising at least one compound selected from the group consisting of.
The method of claim 4,
The cyclic amine compound comprises at least one compound selected from the group consisting of 1-imidazolidine ethanol, amino ethyl piperazine, and hydroxyethyl piperazine, a stripper composition for photoresist removal.
delete The method of claim 1,
The protonic polar solvent comprises an alkylene glycol or an alkylene glycol monoalkyl ether, a stripper composition for removing a photoresist.
The method of claim 8,
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, and tripropylene glycol monobutyl ether A photoresist stripper composition comprising at least one selected from the group consisting of.
The method of claim 1,
A photoresist stripper composition in which the weight ratio of the proton polar solvent is 100 parts by weight to 200 parts by weight based on 100 parts by weight of the aqueous solvent.
The method of claim 1,
A stripper composition for removing photoresist further comprising a corrosion inhibitor.
The method of claim 11,
The corrosion inhibitor comprises at least one selected from the group consisting of a benzimidazole-based compound, a triazole-based compound, and a tetrazole-based compound, a stripper composition for photoresist removal.
The method of claim 12,
The triazole-based compound comprises a compound of the following formula 1 or 2, a photoresist stripper composition for removing:
[Formula 1]

In Formula 1, R ₄ is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is hydrogen or a functional group represented by the following Formula 1-1, and a is an integer of 1 to 4,
[Formula 1-1]

In Formula 1-1, R ₅ and R ₆ are the same as or different from each other and are a hydroxyalkyl group having 1 to 4 carbon atoms, Y is an alkylene group having 1 to 10 carbon atoms,
[Formula 2]

In Formula 2, R ₇ is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is hydrogen or a functional group represented by Formula 1-1, and b is an integer of 1 to 4.
Forming a photoresist pattern on the substrate on which the lower layer is formed;
Patterning a lower layer with the photoresist pattern; And
A method of removing a photoresist comprising the step of removing the photoresist using the stripper composition for removing the photoresist of claim 1.