KR102512488B1 - Photoresist stripper composition - Google Patents

Abstract

The present invention relates to a resist stripper composition, and more particularly, does not contain toxic substances harmful to the human body, minimizes process problems such as filter clogging due to excellent solvency of the stripped resist, and prevents corrosion of metal wiring. It relates to a stripper composition for photoresist removal that can be minimized.

Description

Stripper composition for photoresist removal {PHOTORESIST STRIPPER COMPOSITION}

The present invention relates to a resist stripper composition, and more particularly, does not contain toxic substances harmful to the human body, minimizes process problems such as filter clogging due to excellent solvency of the stripped resist, and prevents corrosion of metal wiring. It relates to a stripper composition for photoresist removal that can be minimized.

The photolithography process is a series of photo processes in which a pattern designed on a mask is transferred onto a substrate on which a thin film to be processed is formed.

More specifically, after forming a thin film on a substrate, uniformly applying a photoresist, which is a photosensitive material, on the thin film, placing a mask on the substrate coated with the photoresist and exposing the photoresist, is developed to form a photoresist pattern. The thin film is also referred to as a lower film, and may be, for example, a conductive metal film such as aluminum, aluminum alloy, copper, copper alloy, molybdenum and a molybdenum alloy, or an insulating film such as a silicon oxide film and a silicon nitride film.

A fine circuit pattern may be transferred and etched by wet or dry etching using the photoresist pattern as a mask. After this patterning process, a process of removing the photoresist remaining on the thin film is performed, and a stripper composition for removing the photoresist is used for this purpose.

Among them, the stripper for removing photoresist used in the process of forming electrode circuits for displays and semiconductors should be able to strip the photoresist in a short time at a low temperature, and should not leave photoresist residues on the substrate after rinsing. and at the same time have the ability to peel without damaging the organic insulating film and metal wiring.

Korean Patent Publication No. 10-2011-0124955, Korean Patent Publication No. 10-2014-0028962, and Korean Patent Publication No. 10-2015-0102354 are photoresist removal solutions that use amine compounds and alkylene glycol alkyl ether compounds. , aprotic polar solvents and organic compounds such as corrosion inhibitors were used, such as N-methylformamide (NMF) and N-methylpyrrolidone (NMP) with excellent double exfoliation and corrosion properties. The aprotic solvent of has been used as the main solvent. These solvents have the advantage of having excellent peeling power, but are toxic to reproduction, and have disadvantages that are harmful to the environment and human body, so their use is gradually being regulated. Therefore, the development of a stripper composition having excellent peeling power without using NMF and NMP is required, but a stripper composition exhibiting sufficient peeling and rinsing power has not yet been developed.

In addition, the stripper composition containing NMF and NMP has a problem in that the decomposition of the amine compound is accelerated over time, and thus the stripping power and rinsing power are deteriorated over time. This problem can be further accelerated when a part of the remaining photoresist is dissolved in the stripper composition according to the number of uses of the stripper composition.

Due to these problems, stripper compositions containing other polar aprotic solvents such as N,N'-dimethylcarboxamide (DMF) instead of NMF have been studied, but the DMF is also known to exhibit biotoxicity, and the need for regulation of use has emerged. It is becoming.

Therefore, a stripper composition that does not contain a solvent exhibiting biotoxicity and maintains excellent peeling and rinsing power over time has not yet been properly developed.

In view of this situation, conventionally, a method of including an excessive amount of an amine compound in the stripper composition was used to maintain excellent peeling and rinsing power over time, but in this case, the economics and efficiency of the process may be greatly reduced, and excessive Depending on the amine compound of the environmental or process problems may occur.

Republic of Korea Patent Publication No. 10-2011-0124955 Republic of Korea Patent Publication No. 10-2014-0028962 Republic of Korea Patent Publication No. 10-2015-0102354

In order to solve the above problems, an object of the present invention is to use a solvent that is not harmful to the environment and human body, and while using such a solvent, the photoresist can be peeled at a low temperature in a short time, so that the peeling speed can be further improved. It is an object of the present invention to provide a stripper composition for removing photoresist that is capable of stripping without leaving photoresist residues on a substrate after rinsing and without damaging an organic insulating film and metal wiring at the same time.

In addition, it is an object of the present invention to provide a stripper composition for removing a photoresist having excellent stability over time.

More specifically, a stripper composition for removing photoresist using N-ethylformamide (NEF) and a polar solvent containing hydrophobicity that is harmless to the environment and human body and can maximize the peeling force and the solvency of the peeled resist. intended to provide

In addition, it is an object of the present invention to provide a stripper composition for removing a photoresist having excellent water displacement and stability over time.

In addition, an object of the present invention is to provide a method for removing a photoresist using the above-described stripper composition for removing a photoresist.

In order to achieve the above object, the present invention relates to a stripper composition for removing a photoresist comprising N-ethylformamide, a first amine compound represented by the following Chemical Formula 1, and a first polar solvent represented by the following Chemical Formula 2.

[Formula 1]

In Formula 1, R ₁ is selected from hydrogen, straight or branched C ₁ to C ₅ alkylamine, and straight or branched C ₁ to C ₅ hydroxyalkyl.

[Formula 2]

In Formula 2, R ₂ is selected from hydrogen, linear or branched C ₁ to C ₅ alkyl, and n is a natural number selected from 1 to 3.

In one aspect of the present invention, the first amine compound represented by Formula 1 is 1-amino-2-propanol, 1-[(2-aminoethyl)amino]-2-propanol and 1,1-iminodi-2 -It may be any one or a mixture of two or more selected from propanol.

In one aspect of the present invention, the first polar solvent represented by Formula 2 is any one selected from dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether. Or it may be a mixture of two or more.

In one aspect of the present invention, the stripper composition may further include a second amine compound satisfying the following relational expression 1, a second polar solvent satisfying the following relational expression 2, and a mixture thereof.

[Relationship 1]

A1 _bp < A2 _bp

In Equation 1, A1 _bp is the boiling point temperature of the first amine compound, and A2 _bp is the boiling point temperature of the second amine compound.

[Relationship 2]

S1 _bp <S2 _bp

In Equation 2, S1 _bp is the boiling point temperature of the first polar solvent, and S2 _bp is the boiling point temperature of the second polar solvent.

In one aspect of the invention, the first amine compound is 1-amino-2-propanol or 1-[(2-aminoethyl)amino]-2-propanol, and the second amine compound is monoethanolamine, 2- (2-aminoethoxy) ethanol, diethanolamine, 3-amino-1-propanol and N- (2-aminoethyl) ethanolamine may be any one selected from, or a mixture of two or more.

In one aspect of the present invention, the first polar solvent is dipropylene glycol monomethyl ether, and the second polar solvent is diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene It may be any one or a mixture of two or more selected from glycol t-butyl ether, triethylene glycol t-butyl ether, diethylene glycol monohexyl ether, triethylene glycol monoethyl ether, triethylene glycol monomethyl ether, and polyethylene glycol. .

In one aspect of the present invention, the stripper composition may further include any one selected from a corrosion inhibitor and deionized water, or a mixture thereof.

In one aspect of the present invention, the corrosion inhibitor may be any one or a mixture of two or more selected from triazole-based compounds and gallate-based compounds.

In one aspect of the present invention, 10 to 90% by weight of the N-ethylformamide, more specifically 20 to 85% by weight, and 1 to 50% by weight of the first amine compound represented by Formula 1, based on the total weight of the stripper composition %, more specifically 3 to 30% by weight, 1 to 50% by weight of the first polar solvent represented by Formula 2, more specifically 5 to 40% by weight.

In one aspect of the present invention, of the total weight of the stripper composition, 1 to 20% by weight of a second amine compound satisfying the following relational expression 1, 1 to 30% by weight of a second polar solvent satisfying the following relational expression 2, and a mixture thereof It may further include.

[Relationship 1]

A1 _bp < A2 _bp

In Equation 1, A1 _bp is the boiling point temperature of the first amine compound, and A2 _bp is the boiling point temperature of the second amine compound.

[Relationship 2]

S1 _bp <S2 _bp

In Equation 2, S1 _bp is the boiling point temperature of the first polar solvent, and S2 _bp is the boiling point temperature of the second polar solvent.

In one aspect of the present invention, it may further include any one selected from 0.01 to 5% by weight of a corrosion inhibitor and 1 to 40% by weight of deionized water, or a mixture thereof, based on the total weight of the stripper composition.

In addition, the present invention comprises the steps of forming a photoresist pattern on the substrate on which the lower film is formed;

patterning a lower layer with the photoresist pattern; and

It relates to a photoresist stripping method comprising the step of stripping the photoresist using the stripper composition.

The stripper composition for photoresist removal of the present invention does not use N-methylformamide (NMF) and N-methylpyrrolidone (NMP), which are harmful to the environment and human body, as main solvents, The photoresist can be rapidly stripped. In addition, the stripper composition for removing photoresist according to the present invention can rapidly strip a modified photoresist even after dry or wet etching.

In addition, since the photoresist can be peeled off within a short time at a low temperature, the peeling speed can be further improved, leaving no photoresist residue on the substrate after rinsing, and at the same time without damaging the organic insulating film and metal wiring. It is possible to provide a stripper composition for removing a photoresist.

In addition, since the peeled photoresist has excellent solvency, it has the advantage of significantly increasing process efficiency by minimizing the defects of filter clogging in the process.

In addition, it is possible to provide a stripper composition for removing a photoresist having excellent stability over time.

Hereinafter, a stripper composition for removing a photoresist will be described in detail. The present invention relates to a stripper composition for removing photoresists used in display, OLED manufacturing and semiconductor manufacturing, and can be better understood by the following examples, which are for illustrative purposes of the present invention. However, it is not intended to limit the scope of protection defined by the appended claims.

The inventors of the present invention can improve the removal rate of photoresist without using N-methylformamide (NMF) and N-methylpyrrolidone (NMP), which are harmful to the human body, as main solvents. As a result of research to develop a stripper composition that can be used together with N-ethylformamide, a first amine compound represented by the following formula (1), and a first polar solvent represented by the following formula (2), it is consumed for photoresist removal. The present invention was completed by discovering that the time for processing can be shortened, the problem of filter clogging can be minimized in the process due to excellent solvency of the peeled photoresist, and the stability over time is excellent.

[Formula 1]

In Formula 1, R ₁ is selected from hydrogen, straight or branched C ₁ to C ₅ alkylamine, and straight or branched C ₁ to C ₅ hydroxyalkyl.

[Formula 2]

In Formula 2, R ₂ is selected from hydrogen, linear or branched C ₁ to C ₅ alkyl, and n is a natural number selected from 1 to 3.

Specifically, N-ethylformamide is used to solve environmental problems caused by the use of N-methylformamide (NMF) and N-methylpyrrolidone (NMP), and the above formula As shown in Formula 1 and Formula 2, by using a compound containing a hydrophobic isopropylene structure together with N-ethylformamide, the amine compound more easily breaks the crosslinked bonds of the photoresist by their synergistic action. The present invention was completed by discovering that the peeling time can be further shortened and a peeling speed equal to or superior to that of the existing composition using NMF and NMP can be achieved. In addition, the present invention was completed by finding that not only the peeling strength but also the solvency of the peeled resist was excellent, and the stability over time was excellent.

In addition, it was found that stability over time can be further improved by further including a second amine compound having a higher boiling point than the first amine compound in the composition, in addition to the first amine compound represented by Formula 1.

In addition, in addition to the first polar solvent represented by the above formula (2), it was found that the water exchangeability can be further improved by further including a second polar solvent having a higher boiling point and hydrophilicity than the first polar solvent in the composition.

Hereinafter, an embodiment of the present invention will be described in more detail.

A first aspect of the present invention is N-ethylformamide; A primary amine compound represented by Formula 1; and a first polar solvent represented by Formula 2.

A second aspect of the present invention is N-ethylformamide; A primary amine compound represented by Formula 1; A first polar solvent represented by Formula 2; and corrosion inhibitors.

A third aspect of the present invention is N-ethylformamide; A primary amine compound represented by Formula 1; A first polar solvent represented by Formula 2; and ultrapure or deionized water.

A fourth aspect of the present invention is N-ethylformamide; A primary amine compound represented by Formula 1; A first polar solvent represented by Formula 2; corrosion inhibitor; and ultrapure or deionized water.

A fifth aspect of the present invention is N-ethylformamide; A primary amine compound represented by Formula 1; A first polar solvent represented by Chemical Formula 2 and a second amine compound satisfying the following relational expression 1 are included.

[Relationship 1]

A1 _bp < A2 _bp

In Equation 1, A1 _bp is the boiling point temperature of the first amine compound, and A2 _bp is the boiling point temperature of the second amine compound.

A sixth aspect of the present invention is N-ethylformamide; A primary amine compound represented by Formula 1; It includes a first polar solvent represented by Chemical Formula 2 and a second polar solvent that satisfies the following relational expression 2.

[Relationship 2]

S1 _bp < S2 _bp

In Equation 2, S1 _bp is the boiling point temperature of the first polar solvent, and S2 _bp is the boiling point temperature of the second polar solvent.

A seventh aspect of the present invention is N-ethylformamide; A primary amine compound represented by Formula 1; It includes a first polar solvent represented by Chemical Formula 2, a second amine compound satisfying the above relational expression 1, and a second polar solvent satisfying the above relational expression 2.

An eighth aspect of the present invention is N-ethylformamide; A primary amine compound represented by Formula 1; A first polar solvent represented by Formula 2; A second amine compound that satisfies the above relational expression 1 and a corrosion inhibitor.

A ninth aspect of the present invention is N-ethylformamide; A primary amine compound represented by Formula 1; A first polar solvent represented by Formula 2; It includes a second polar solvent and a corrosion inhibitor that satisfies the relational expression 2 above.

A tenth aspect of the present invention is N-ethylformamide; A primary amine compound represented by Formula 1; A first polar solvent represented by Chemical Formula 2, a second amine compound satisfying the above relational expression 1; It includes a second polar solvent and a corrosion inhibitor that satisfies the relational expression 2 above.

The first to tenth aspects are only one aspect for specifically illustrating the present invention, but are not limited thereto. In addition, additives commonly used in the field may be further included as needed.

In one aspect of the present invention, the N-ethylformamide content is not limited, but may include 10 to 90% by weight of the total composition content. More preferably from 20 to 85% by weight, more preferably from 40 to 85% by weight. By improving the peeling force within the above range, the photoresist removal time can be remarkably shortened, and the corrosion of the lower film can be minimized.

In one aspect of the present invention, the first amine compound represented by Chemical Formula 1 may serve to facilitate penetration of solvent components by acting on a relatively weak portion of the surface of the modified photoresist. In addition, when used together with the N-ethylformamide and the first polar solvent represented by Formula 2, it serves to maximize the excellent peeling power and the peeled photoresist solvency without being harmful to the human body. In addition, there is an effect of improving stability over time.

The primary amine compound represented by Formula 1 is specifically, for example, 1-amino-2-propanol, 1-[(2-aminoethyl)amino]-2-propanol and 1,1-iminodi-2- It may be any one or a mixture of two or more selected from propanol, etc., but is not limited thereto.

The content of the first amine compound represented by Formula 1 may include 1 to 50% by weight based on the total weight of the stripper composition for removing photoresist. More preferably from 3 to 30% by weight, more preferably from 5 to 15% by weight. By being included in the above range, it is possible to significantly improve the peeling force for the modified photoresist.

In one aspect of the present invention, the first polar solvent represented by Formula 2 is a glycol compound containing isopropylene, which is a hydrophobic group, and has excellent wettability to the photoresist, so that not only the peeling force but also the solvency of the peeled photoresist is remarkably improved. can improve

The first polar solvent represented by Formula 2 is harmless to the human body by using the N-ethylformamide and the first amine compound represented by Formula 1, thereby maximizing excellent peeling power and peeling photoresist solvency. do In addition, there is an effect of improving stability over time.

The first polar solvent represented by Formula 2 is specifically, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene Any one selected from glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, and tripropylene glycol monobutyl ether. It may be one or a mixture of two or more.

More preferably, it may be any one selected from dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether, or a mixture of two or more.

The amount of the first polar solvent represented by Formula 2 may be 1 to 50% by weight based on the total weight of the stripper composition for removing photoresist. More preferably from 5 to 40% by weight, more preferably from 15 to 30% by weight. By being included within the above-described range, even when using an aprotic polar solvent that is not harmful to the human body, the peeling power of the photoresist and the solvency of the peeled photoresist can be significantly improved to increase process efficiency.

In one aspect of the present invention, the stripper composition for removing photoresist may further include an amine compound commonly used in the field in addition to the first amine compound represented by Chemical Formula 1.

More preferably, as shown in the following relational expression 1, by further including a second amine compound having a higher boiling point than the first amine compound, the volatilization degree may be further lowered, and stability over time may be further improved.

[Relationship 1]

A1 _bp < A2 _bp

In Equation 1, A1 _bp is the boiling point temperature of the first amine compound, and A2 _bp is the boiling point temperature of the second amine compound.

More specifically, stability over time may be further improved by including, as the second amine compound, an amine compound having a boiling point higher than that of the first amine compound by 1° C. or more, more preferably by 10° C. or more.

Specific examples of the second amine compound are selected from monoethanolamine, 2-(2-aminoethoxy)ethanol, diethanolamine, 3-amino-1-propanol, and N-(2-aminoethyl)ethanolamine. It may be any one or a mixture of two or more, but is not limited thereto. More preferably, it may be 2-(2-aminoethoxy)ethanol and diethanolamine.

More specifically, for example, the first amine compound is 1-amino-2-propanol or 1-[(2-aminoethyl)amino]-2-propanol, and the second amine compound is monoethanolamine, 2-propanol, (2-aminoethoxy) ethanol, diethanolamine, 3-amino-1-propanol and N- (2-aminoethyl) ethanolamine may be any one selected from, or a mixture of two or more.

The content of the second amine compound may include 1 to 50% by weight based on the total weight of the stripper composition for removing photoresist. More preferably from 1 to 20% by weight, more preferably from 3 to 10% by weight. By being included within the above range, it is possible to further improve stability over time without impairing the peeling force and solvency.

In one aspect of the present invention, the stripper composition for removing photoresist may further include a polar solvent commonly used in the field in addition to the first polar solvent represented by Chemical Formula 2.

More preferably, as shown in the following relational expression 2, the water exchangeability may be further improved by further including a second polar solvent having a higher boiling point than the first polar solvent.

[Relationship 2]

S1 _bp < S2 _bp

In Equation 2, S1 _bp is the boiling point temperature of the first polar solvent, and S2 _bp is the boiling point temperature of the second polar solvent.

More specifically, for example, the water exchangeability may be further improved by including a polar solvent having a boiling point higher than that of the first polar solvent by 1 ° C. or more, more preferably by 10 ° C. or more, as the second polar solvent. More preferably, a polar solvent having a high boiling point and not containing an isopropylene structure may be used as shown in Equation 2 above.

Specific examples of the second polar solvent include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol t-butyl ether, triethylene glycol t-butyl ether, and diethylene. It may be any one or a mixture of two or more selected from glycol monohexyl ether, triethylene glycol monoethyl ether, triethylene glycol monomethyl ether, and polyethylene glycol, but is not limited thereto. More preferably, it may be diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monoethyl ether, triethylene glycol monomethyl ether and polyethylene glycol.

More specifically, for example, the first polar solvent is dipropylene glycol monomethyl ether, and the second polar solvent is diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene It may be any one or a mixture of two or more selected from glycol t-butyl ether, triethylene glycol t-butyl ether, diethylene glycol monohexyl ether, triethylene glycol monoethyl ether, triethylene glycol monomethyl ether, and polyethylene glycol. .

The content of the second polar solvent may include 1 to 50% by weight based on the total weight of the stripper composition for removing photoresist. More preferably 1 to 30% by weight, more preferably 10 to 20% by weight may be included. By being included within the above-described range, it is possible to further improve the water displacement without compromising peeling force and solvency.

In one aspect of the present invention, the stripper composition for removing the photoresist may include a corrosion inhibitor, and any corrosion inhibitor commonly used in the field may be used without limitation, specifically, for example, a triazole compound and It may be to use a gallate compound or the like. The corrosion inhibitor is easily soluble in the stripper and serves as an oxidizing agent and a complex compound during the DI rinse process, thereby suppressing the galvanic effect of organic amines to eliminate the corrosive effect on metal wiring.

The triazole compound is not limited as long as it is a compound known in the art, and specifically, for example, benzotriazole, o-tolyltriazole, m-tolyltriazole, p-tolyltriazole, carboxybenzotriazole Any one or a mixture of two or more selected from sol, 1-hydroxybenzotriazole, nitrobenzotriazole, dihydroxypropylbenzotriazole, tetrahydrotolyltriazole, etc. may be used, but is not limited thereto.

The gallate compound is not limited as long as it is a compound well known in the art, and specifically, for example, methyl gallate, ethyl gallate, propyl gallate, isopropyl gallate, butyl gallate, t-butyl gallate Any one or a mixture of two or more selected from late and octyl gallate may be used, but is not limited thereto.

In the photoresist stripper composition, the content of the corrosion inhibitor may be used within a range that does not impair the physical properties of the photoresist stripper composition, and is 0.01 to 5% by weight, more preferably 0.05 to 2% by weight, More preferably, it may include 0.1 to 0.5% by weight, but is not limited thereto.

In addition, the photoresist stripper composition of the present invention may be added without limitation if it is an additive that is usually added as needed in addition to the above components, and specifically, for example, a water replacement improver, a surfactant, an antifoaming agent, and One or more additives selected from the mixture may further be included.

That is, a surfactant may be further added to the composition according to the present invention to improve uniformity of cleaning, and an antifoaming agent may be used as an additive to suppress generation of bubbles that hinder cleaning. The amount of the additive is not limited, but may include the additive in an amount of 20 parts by weight or less, preferably 5 parts by weight or less, based on 100 parts by weight of the total weight of the stripper composition for removing the photoresist. no. On the other hand, examples of surfactants and antifoaming agents that can be used are commonly known in the art, and for example, amphoteric, cationic, anionic, nonionic or fluorine-based surfactants may be used as surfactants, and antifoaming agents include Silicone-based or non-silicone-based defoamers may be used.

In one aspect of the present invention, the stripper composition for removing the photoresist may be an aqueous or non-aqueous composition.

Deionized water may be further included to prepare the water-based composition. The deionized water may be used in the same sense as ultrapure water, purified water, etc., and may be used within a range that does not impair the physical properties of the stripper composition for removing photoresist, but is not limited to, more specifically, 1 to 40% by weight, more specifically It may contain 2 to 15% by weight.

In addition, according to another embodiment of the present invention, it is possible to provide a photoresist stripping method of treating the stripper composition for removing the photoresist.

The method of removing the photoresist is to etch the substrate using a photoresist pattern formed on a substrate including an organic insulating film, a metal wiring, or a lower film such as a metal wiring and an inorganic material layer as a mask, and removing the photoresist. A step of stripping the photoresist with the composition may be included.

More specifically, forming a photoresist pattern on the substrate on which the lower film is formed; patterning a lower layer with the photoresist pattern; and stripping the photoresist using the stripper composition.

In this exfoliation method, first, a photoresist pattern may be formed on a substrate on which a lower film to be patterned is formed through a photolithography process. Thereafter, after patterning the lower film using the photoresist pattern as a mask, the photoresist may be stripped using the stripper composition or the like. In the process described above, since the formation of the photoresist pattern and the patterning process of the lower layer may follow a conventional device manufacturing process, further description thereof will be omitted.

On the other hand, in stripping the photoresist using the stripper composition, first, the stripper composition is treated on the substrate on which the photoresist pattern remains, washed with an alkali buffer solution, washed with ultrapure water, and dried. can proceed.

A method of stripping a photoresist from a substrate on which a microcircuit pattern is engraved using a photoresist stripping composition according to an embodiment of the present invention includes dipping several substrates to be stripped simultaneously in a large amount of stripping solution. Both a dip method and a sheet method in which photoresist is removed by spraying (spraying) a stripping solution on a substrate one by one may be used, but are not limited thereto.

Types of photoresists that can be stripped using the photoresist stripper composition of the present invention include, for example, positive photoresists, negative photoresists, and dual tone photoresists. can include In addition, although there are no limitations on its components, a photoresist that can be applied particularly effectively may be a photoresist composed of a photoactive compound including a novolac-based phenolic resin and diazonaphthoquinone.

A metal wiring to which the stripper composition for removing photoresist can be applied may include, for example, Al, Cu, Ag, Ti, and Mo as a lower layer, which may be used as a p-electrode and an n-electrode. , but is not limited thereto.

Hereinafter, a preferred embodiment of the stripper composition for removing a photoresist according to the present invention and a method for measuring performance thereof will be described in detail.

1) Evaluation of photoresist peeling force

In order to evaluate the photoresist stripping performance of the stripper composition for photoresist removal prepared as shown in Table 1 below, photoresist (AZEM, DTR-300) was coated on a glass substrate to a thickness of 1.5 μm and then heated at 160° C. and 170° C. Test specimens were prepared by hard bake (H/B) for 10 minutes each at °C. The time taken for the photoresist to be completely peeled off by the stripping solution was measured under a spray pressure condition of 0.4 kgf using a sheet spray type stripping equipment maintained at 60° C., and the evaluation results are shown in Table 2 below.

At this time, whether or not the photoresist was peeled off was confirmed by irradiating ultraviolet rays on the glass substrate to observe whether or not the photoresist remained.

2) Evaluation of solvency

In order to evaluate the photoresist solvency of the photoresist stripper composition prepared as shown in Table 1 below, photoresist powder was prepared by drying the photoresist (AZEM, DTR-300) on a hot plate at 150 ° C for 4 hours. did 2% by weight of the dried photoresist powder was added to the stripper composition at a constant temperature of 60 ° C under stirring conditions of 300 rpm, stirred for 20 minutes to dissolve, and then passed through a 10 micro filter (PTFE with 10 μm pores) to increase the solubility. evaluated. If 2% by weight of the photoresist is completely dissolved within 20 minutes and the residual amount is not measured after filtering, it is set to 100%, and the higher the value, the more photoresist can be dissolved, so the number of treatments is high. Solvent power can be calculated by the following formula.

Solvent power (%) = [(content of photoresist used for 2% by weight of solid content - content of photoresist remaining in the filter) / content of photoresist used for 2% by weight of solid content] × 100

3) Evaluation of lower film corrosion

Using a single-wafer spray type peeling equipment at a temperature of 60 ° C., the dried specimens were completely peeled with the stripping solution of Examples and Comparative Examples under spray pressure conditions of 0.4 kgf, and then dried specimens were subjected to an optical microscope at 200 magnification and FE at 10K to 50K magnification. - The degree of damage to the lower membrane was confirmed through SEM. The results are shown in Table 2 below.

◎: No corrosion.

○: Insignificant corrosion

△: corrosion occurs

X: Severely corroded

4) Evaluation of stability over time

(1) Evaluation of peel strength after change with time

In order to evaluate the stability over time, the peeling force after the change over time of the stripper composition was evaluated in the same manner as in 1) above. The results are shown in Table 2 below.

500 g of the stripper composition prepared in Examples and Comparative Examples was prepared, and photoresist (AZEM, DTR-300) was added in an amount of 2% by weight based on the total composition in a state where the temperature was raised to 60 ° C. and dissolved. The peeling solution was heated at 60° C. for 12 to 48 hours to cause aging under harsh conditions.

The stability of the peeling solution composition subjected to this change with time was evaluated by measuring the peel force in the same manner as in 1) above.

(2) Evaluation of solvency after change with time

Photoresist powder was prepared by drying the photoresist (AZEM, DTR-300) on a 150°C hot plate for 4 hours. 2% by weight of the dried photoresist powder was added to the stripper composition at a constant temperature of 60 ° C under a stirring condition of 300 rpm and dissolved by stirring for 20 minutes. The peeling solution was heated at 60° C. for 12 to 48 hours to cause aging under harsh conditions.

The stripper composition undergoing such change over time was passed through a 1 micro filter (PTFE having pores of 1 μm) as in 2) above, and the solvency was evaluated.

Solvent power (%) = [(content of photoresist used for 2% by weight of solid content - content of photoresist remaining in the filter) / content of photoresist used for 2% by weight of solid content] × 100

5) Evaluation of degree of numerical substitution

In the photoresist stripping process, the last step includes washing with water. Therefore, the stripping solution containing the photoresist remaining on the substrate should have good water displacement with water, and an evaluation was conducted to confirm this.

The substrate immersed in the stripper for 1 minute is taken out and the stripper is overdried for 1 minute using an air knife. After rinsing the overdried substrate with water, the stainability of the substrate was visually confirmed. The more water-replaceable the composition, the weaker the stain strength, and the results are shown in Table 2 below.

◎: very good

○: good

△: spotting

X: Severe staining

6) Volatility

In order to check the volatility, 500 g of the composition was added to a 1L beaker and then placed in a thermostat at 60°C. Then, the weight after 24 hours was measured and the volatility was calculated according to the following formula.

Volatility = [(Weight of the original composition (g)) - 　 (Weight of the original composition after 24 hours (g))] / Weight of the original composition (g) × 100

[Examples and Comparative Examples]

A stripper composition for photoresist removal was prepared by mixing the components and compositions listed in Table 1 below. At this time, the mixing was carried out at room temperature, and after mixing for 1 hour or more so that the mixture was sufficiently dissolved, it was filtered through a Teflon filter (PTFE having pores of 1 μm) before use.

division menstruum primary amine compound Second amine compound 1st polar solvent 2nd polar solvent deionized water corrosion inhibitor type weight% type weight% type weight% type weight% type weight% weight% type weight% Example 1 NEF 70 MIPA 15 - - DPGME 15 - - - - - Example 2 NEF 75 MIPA 10 - - DPGME 15 - - - - - Example 3 NEF 80 MIPA 5 - - DPGME 15 - - - - - Example 4 NEF 75 HEA 10 - - DPGME 15 - - - - - Example 5 NEF 75 IDP 10 - - DPGME 15 - - - - - Example 6 NEF 60 MIPA 10 - - DPGME 30 - - - - - Example 7 NEF 85 MIPA 10 - - DPGME 5 - - - - - Example 8 NEF 75 MIPA 10 - - DPGEE 15 - - - - - Example 9 NEF 75 MIPA 10 - - DPGPE 15 - - - - - Example 10 NEF 75 MIPA 10 - - DPGBE 15 - - - - - Example 11 NEF 75 MIPA 10 - - TPGME 15 - - - - - Example 12 NEF 65 MIPA 10 - - DPGME 15 BDG 10 - - - Example 13 NEF 65 MIPA 10 - - DPGME 15 EDG 10 - - - Example 14 NEF 65 MIPA 10 - - DPGME 15 HDG 10 - - - Example 15 NEF 65 MIPA 10 - - DPGME 15 TEG 10 - - - Example 16 NEF 65 MIPA 10 - - DPGME 15 TMG 10 - - - Example 17 NEF 40 MIPA 15 - - DPGME 15 - - 30 - - Example 18 NEF 69.5 MIPA 15 - - DPGME 15 - - - H4TT 0.5 Example 19 NEF 69.5 MIPA 15 - - DPGME 15 - - - TT 0.5 Example 20 NEF 69.5 MIPA 15 - - DPGME 15 - - - MG 0.5 Example 21 NEF 70 MIPA 10 AEE 5 DPGME 15 - - - - - Example 22 NEF 70 MIPA 10 MEA 5 DPGME 15 - - - - - Example 23 NEF 69.5 MIPA 10 MEA 5 DPGME 15 - - TT 0.5 Example 24 NEF 59.5 MIPA 10 MEA 5 DPGME 15 BDG 10 - TT 0.5 Example 25 NEF 59.5 MIPA 10 MEA 5 DPGME 15 EDG 10 - TT 0.5 Example 26 NEF 59.5 MIPA 10 MEA 5 DPGME 15 EDG 10 - H4TT 0.5 Example 27 NEF 59.5 MIPA 10 MEA 5 DPGME 15 EDG 10 - MG 0.5 Example 28 NEF 59.5 MIPA 10 MEA 5 DPGME 15 EDG 10 - EG 0.5 Example 29 NEF 59.5 MIPA 10 MEA 5 DPGME 15 EDG 10 - PG 0.5 Example 30 NEF 59.5 MIPA 10 MEA 5 DPGME 15 EDG 10 - BG 0.5 Example 31 NEF 59.5 MIPA 10 MEA 5 DPGME 15 EDG 10 - OG 0.5 Comparative Example 1 NEF 75 MIPA 10 - - - - EDG 15 - - - Comparative Example 2 NEF 75 MIPA 10 - - - - MDG 15 - - - Comparative Example 3 NEF 75 MIPA 10 - - - - BDG 15 - - - Comparative Example 4 NEF 74.5 - - MEA 10 - - EDG 15 H4TT 0.5 Comparative Example 5 NEF 75 - - AEE 10 - - EDG 15 - - - Comparative Example 6 NEF 74.5 - - MEA 10 DPGME 15 - - - H4TT 0.5 Comparative Example 7 NEF 75 - - AEE 10 DPGME 15 - - - - - Comparative Example 8 NMP 75 - - MEA 10 DPGME 15 - - - - - Comparative Example 9 NMP 75 MIPA 10 - - DPGME 15 - - - - - Comparative Example 10 DMPA 70 - - MEA 15 - - EDG 15 - - - Comparative Example 11 NEF 40 MIPA 15 - - - - EDG 15 30 - -

<Solvent>

NEF: N-ethylformamide

NMP: N-methylpyrrolidone

<Primary amine compound>

MIPA: 1-amino-2-propanol

HEA: 1-[(2-aminoethyl)amino]-2-propanol

IDP: 1,1-iminodi-2-propanol

<Second amine compound>

MEA: Monoethanolamine

AEE: 2-(2-aminoethoxy)ethanol

DEA: Diethanolamine

3-AP: 3-amino-1-propanol

AEEA: N-(2-aminoethyl)ethanolamine

<First Polar Solvent>

DPGME: dipropylene glycol monomethyl ether

DPGEE: dipropylene glycol monoethyl ether

DPEPE: dipropylene glycol monopropyl ether

DPEBE: dipropylene glycol monobutyl ether

<Second Polar Solvent>

MDG: diethylene glycol monomethyl ether

BDG: diethylene glycol monobutyl ether

EDG: diethylene glycol monoethyl ether

TGTB: triethylene glycol t-butyl ether

DGTB: diethylene glycol t-butyl ether

HDG: diethylene glycol monohexyl ether

TEG: triethylene glycol monoethyl ether

TMG: triethylene glycol monomethyl ether

<Corrosion inhibitor>

H4TT: tetrahydrotolyltriazole

TT: tolyltriazole

MG: methyl gallate

EG: ethyl gallate

PG: propyl gallate

BG: butyl gallate

OG: Octyl Gallate

In Table 2 below, Δ12 refers to physical properties measured after change over time for 12 hours, and Δ48 refers to physical properties measured after change over time for 48 hours.

division Peel force
(sec) solvency(%) lower membrane
corrosion degree of numerical substitution Volatility 160°C
H/B 170°C
H/B Early △12 △48 60℃, △24 Early △12 △48 Early △12 △48 Example 1 10 10 10 20 20 20 100 100 100 ○ ○ 10% Example 2 10 10 10 20 20 20 100 100 100 ○ ○ 10% Example 3 10 10 10 20 20 20 100 100 100 ○ ○ 8% Example 4 10 10 10 20 20 20 100 100 100 ○ ○ 7% Example 5 10 10 10 20 20 20 100 100 100 ○ ○ 12% Example 6 10 10 10 20 20 20 100 100 100 ○ ○ 9% Example 7 10 10 10 20 20 20 100 100 100 ○ ○ 10% Example 8 10 10 10 20 20 20 100 100 100 ○ ○ 8% Example 9 10 10 10 20 20 20 100 100 100 ○ ○ 8% Example 10 10 10 10 20 20 20 100 100 100 ○ ○ 7% Example 11 10 10 10 20 20 20 100 100 100 ○ ○ 7% Example 12 10 10 10 20 20 20 100 100 100 ○ ◎ 7% Example 13 10 10 10 20 20 20 100 100 100 ○ ◎ 7% Example 14 10 10 10 20 20 20 100 100 100 ○ ◎ 7% Example 15 10 10 10 20 20 20 100 100 100 ○ ◎ 7% Example 16 10 10 10 20 20 20 100 100 100 ○ ◎ 7% Example 17 30 30 30 50 50 50 95.2 95.4 95.8 ○ ○ 24% Example 18 10 10 10 20 20 20 100 100 100 ◎ ○ 10% Example 19 10 10 10 20 20 20 100 100 100 ◎ ○ 10% Example 20 10 10 10 20 20 20 100 100 100 ◎ ○ 8% Example 21 10 10 10 20 20 20 100 100 100 ○ ○ 8% Example 22 10 10 10 20 20 20 100 100 100 ○ ○ 8% Example 23 10 10 10 20 20 20 100 100 100 ◎ ○ 8% Example 24 10 10 10 20 20 20 100 100 100 ◎ ◎ 6% Example 25 10 10 10 20 20 20 100 100 100 ◎ ◎ 6% Example 26 10 10 10 20 20 20 100 100 100 ◎ ◎ 6% Example 27 10 10 10 20 20 20 100 100 100 ◎ ◎ 6% Example 28 10 10 10 20 20 20 100 100 100 ◎ ◎ 6% Example 29 10 10 10 20 20 20 100 100 100 ◎ ◎ 6% Example 30 10 10 10 20 20 20 100 100 100 ◎ ◎ 6% Example 31 10 10 10 20 20 20 100 100 100 ◎ ◎ 6% Comparative Example 1 30 30 35 80 80 80 50.5 50.6 50.8 X ◎ 8% Comparative Example 2 30 35 50 80 90 120 40 38 35 X ◎ 8% Comparative Example 3 30 30 30 80 80 80 50.7 50.8 50.7 X ◎ 8% Comparative Example 4 30 30 30 80 80 80 80 80 80 ○ ◎ 9% Comparative Example 5 30 30 30 80 80 80 80 80 80 △ ◎ 8% Comparative Example 6 30 30 30 80 80 80 80 80 80 ○ ○ 10% Comparative Example 7 35 35 35 90 90 90 70 70 70 △ ○ 10% Comparative Example 8 40 40 40 120 120 120 40 40 40 X ○ 10% Comparative Example 9 10 10 10 20 20 20 60 60 60 X ○ 10% Comparative Example 10 40 40 40 120 120 120 40 40 40 X ○ 10% Comparative Example 11 50 50 50 120 120 120 35 32 30 X ◎ 9%

As shown in Table 2, it was confirmed that the stripper composition for removing photoresist according to the present invention was remarkably excellent in both removal rate and solvency as well as lower film corrosion. In addition, it was found that the stability over time was excellent.

As can be seen in Examples 1 to 11, when NEF, the first amine compound represented by Chemical Formula 1, and the first polar solvent represented by Chemical Formula 2 were used in combination, it was confirmed that the peel strength and solvency were the most excellent.

In addition, as shown in Examples 12 to 16, even when the second polar solvent was further included, it was found that there was no change in peel strength and solvency, and it was confirmed that the water exchangeability was further improved.

In addition, as shown in Example 17, when deionized water was added, the peel strength and solvency were lowered compared to other examples, but it was found that the peel strength and solvency were excellent compared to the comparative examples.

In addition, as shown in Examples 18-20, it was confirmed that corrosion of the lower film was further reduced by including the corrosion inhibitor.

In addition, as shown in Examples 21-23, even when the second amine compound was further included, it was found that there was no change in peel strength and solvency, and the volatility was lower than in Example 1, so the stability over time was further improved. confirmed.

In addition, as shown in Examples 24-31, even when the second polar solvent and the second amine compound are further included, there is no change in peeling power and solvency, and the stability over time is further improved due to low volatility, and hydrolysis It was found that the degree of improvement was further improved.

As shown in Comparative Examples 1 to 7, it was confirmed that physical properties deteriorated when any one component was excluded from the composition of the present invention. This is because the first polar solvent represented by Chemical Formula 2 has a strong affinity for the photoresist, which is the target to be removed, and is rapidly wetting. At this time, the first polar solvent represented by Chemical Formula 2 is a first amine compound represented by Chemical Formula 1 having a similar structure It can be seen that faster photoresist peeling and dissolution while dragging to the photoresist surface at the same time.

In addition, as shown in Comparative Examples 8 to 10, it was confirmed that the solvency was lowered when other amide solvents such as NMP were used instead of NEF.

Therefore, according to the peeling solution composition for removing photoresist according to the present invention, it contains a solvent that is not harmful to the human body, an amine compound, and a polar solvent containing a hydrophobic group, and has excellent peeling power, solvency, and stability over time, thereby increasing process efficiency. It was confirmed that it is possible to provide a stripper composition capable of increasing the.

Although the preferred embodiments of the present invention have been described above, it is clear that the present invention can use various changes and equivalents, and can be equally applied by appropriately modifying the above embodiments. Accordingly, the above description is not intended to limit the scope of the present invention, which is defined by the limitations of the following claims.

Claims (14)

N-ethylformamide; A first amine compound represented by Formula 1 below; and a first polar solvent including any one or a mixture of two or more selected from dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, and dipropylene glycol monobutyl ether. As a stripper composition for removal,
The N-ethylformamide is included in 40 to 90% by weight of the total content of the composition, the first amine compound is included in 1 to 50% by weight, and the first polar solvent is included in 1 to 40% by weight, photo A stripper composition for resist removal.
[Formula 1]

In Formula 1, R ₁ is selected from hydrogen, straight or branched C ₁ to C ₅ alkylamine, and straight or branched C ₁ to C ₅ hydroxyalkyl. According to claim 1,
The first amine compound represented by Formula 1 is any one selected from 1-amino-2-propanol, 1-[(2-aminoethyl)amino]-2-propanol and 1,1-iminodi-2-propanol Or a stripper composition for removing photoresist that is a mixture of two or more. delete According to claim 1,
The stripper composition further comprises a second amine compound satisfying the following relational expression 1, a second polar solvent satisfying the following relational expression 2, and a mixture thereof.
[Relationship 1]
A1 _bp < A2 _bp
In Equation 1, A1 _bp is the boiling point temperature of the first amine compound, and A2 _bp is the boiling point temperature of the second amine compound.
[Relationship 2]
S1 _bp <S2 _bp
In Equation 2, S1 _bp is the boiling point temperature of the first polar solvent, and S2 _bp is the boiling point temperature of the second polar solvent. According to claim 4,
The first amine compound is 1-amino-2-propanol or 1-[(2-aminoethyl)amino]-2-propanol, and the second amine compound is monoethanolamine, 2-(2-aminoethoxy) A stripper composition for removing photoresist, which is any one selected from ethanol, diethanolamine, 3-amino-1-propanol, and N-(2-aminoethyl)ethanolamine, or a mixture of two or more. According to claim 4,
The first polar solvent is dipropylene glycol monomethyl ether, and the second polar solvent is diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol t-butyl ether, tri A stripper composition for removing photoresist comprising any one or a mixture of two or more selected from ethylene glycol t-butyl ether, diethylene glycol monohexyl ether, triethylene glycol monoethyl ether, triethylene glycol monomethyl ether and polyethylene glycol. According to claim 1 or 4,
The stripper composition for removing a photoresist further comprising any one selected from a corrosion inhibitor and deionized water, or a mixture thereof. According to claim 7,
The corrosion inhibitor is any one selected from a triazole-based compound and a gallate-based compound, or a mixture of two or more photoresist stripper compositions. delete According to claim 1,
A stripper composition for removing photoresist comprising 40 to 85% by weight of the N-ethylformamide, 3 to 30% by weight of the first amine compound represented by Formula 1, and 5 to 40% by weight of the first polar solvent. According to claim 10,
Of the total weight of the stripper composition, 1 to 20% by weight of a second amine compound satisfying the following relational expression 1, 1 to 30% by weight of a second polar solvent satisfying the following relational expression 2, and a mixture thereof Photoresist removal stripper composition.
[Relationship 1]
A1 _bp < A2 _bp
In Equation 1, A1 _bp is the boiling point temperature of the first amine compound, and A2 _bp is the boiling point temperature of the second amine compound.
[Relationship 2]
S1 _bp < S2 _bp
In Equation 2, S1 _bp is the boiling point temperature of the first polar solvent, and S2 _bp is the boiling point temperature of the second polar solvent. According to claim 11,
A stripper composition for removing photoresist further comprising any one selected from 0.01 to 5% by weight of a corrosion inhibitor and 1 to 40% by weight of deionized water, or a mixture thereof, based on the total weight of the stripper composition. forming a photoresist pattern on the substrate on which the lower film is formed;
patterning a lower layer with the photoresist pattern; and
A photoresist stripping method comprising the step of stripping the photoresist using the stripper composition according to any one of claims 1, 2, and 4 to 6. forming a photoresist pattern on the substrate on which the lower film is formed;
patterning a lower layer with the photoresist pattern; and
A photoresist stripping method comprising the step of stripping the photoresist using the stripper composition according to claim 7 .