TW202321837A - Stripper composition for removing photoresist and stripping method of photoresist using the same - Google Patents

Abstract

The present disclosure relates to a stripper composition for removing photoresists having improved photoresist solubility and inhibiting corrosion on a lower metal film during the stripping process while having excellent stripping force for photoresists, and a stripping method of photoresist using the same. The stripper composition for removing photoresists which includes: a primary or secondary chain amine compound; a cyclic amine compound; an amide compound having a boiling point of 180 DEG C or higher in which one or two linear or branched alkyl groups having 1 to 5 carbon atoms are substituted with nitrogen; a protic solvent; and a corrosion inhibitor.

Description

Stripper composition for removing photoresist and method for stripping photoresist using same

The present invention relates to a stripper composition for removing photoresist and a method of stripping photoresist using the same, and more particularly relates to a stripper composition for removing photoresist, which is used in the stripping process Inhibiting corrosion on a lower metal film while having excellent photoresist stripping ability, and having enhanced photoresist solubility, and a photoresist stripping method using the same.

The manufacturing process of microcircuits or semiconductor integrated circuits of liquid crystal display devices includes the following steps: forming various lower films on the substrate, such as conductive metal films made of aluminum, aluminum alloys, copper, copper alloys, molybdenum or molybdenum alloys, or an insulating film, such as a silicon oxide film, a silicon nitride film, or an acryl-based insulating film; uniformly coating a photoresist on such an underlying film; exposing and developing the coated photoresist as appropriate to form a photoresist pattern; and patterning the lower film using the photoresist pattern as a mask. After these patterning steps, a process of removing residual photoresist on the lower film is performed. For this purpose, a stripping composition for removing photoresist is used.

Heretofore, stripper compositions including amine compounds, polar protic solvents, polar aprotic solvents, and the like are well known and mainly used. These stripper compositions are known to exhibit some degree of photoresist removal and stripping capabilities.

However, these conventional stripper compositions promote the decomposition of amine compounds over time in the case of stripping a large amount of photoresist, and thus have a problem that the stripping and rinsing capabilities decrease over time. In particular, depending on the coating time of the stripper composition, these problems can be further contributed when a portion of the residual photoresist dissolves in the stripper composition.

In addition, when the photoresist modified by dry etching remains on the substrate, there is a problem that a film detachment phenomenon or a wiring disconnection phenomenon occurs during the progress of post-processing, which affects TFT yield.

Therefore, there is a need to develop a novel stripper composition that has excellent stripping ability even under harsh bake conditions, and has enhanced photoresist solubility before inhibiting corrosion on the underlying metal film.

[ Technical Problem ] The object of the present application is to provide a stripper composition for removing photoresist, which suppresses corrosion on the lower metal film during the stripping process, while having excellent photoresist stripping ability and having improved photoresist solubility; and a method of stripping photoresist using the same.

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

[ Technical solution ] This article provides a stripping agent composition for removing photoresist, which includes: a primary or secondary chain amine compound; a cyclic amine compound; one or both of which have a boiling point of 180° C. or higher Nitrogen-substituted amide compounds of linear or branched chain alkyl groups of 1 to 5 carbon atoms; protic solvents; and corrosion inhibitors, one or both of which have a boiling point of 180°C or higher and have 1 to 2 The content of the amide compound in which the linear or branched chain alkyl group of 5 carbon atoms is substituted by nitrogen is 60% by weight to 90% by weight relative to the total weight of the release agent composition, and wherein the primary or secondary The weight ratio of the chain amine compound to the cyclic amine compound is 100:1 to 1:1.

Also provided herein is a method for stripping a photoresist, which includes the step of stripping the photoresist using a photoresist-removing stripper composition.

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

Technical terms used herein are for the purpose of describing exemplary embodiments only, and are not intended to limit the scope of the present invention. The singular forms "a" and "the" are intended to include the plural forms as well, unless the context clearly dictates otherwise. It should be understood that the terms "comprise", "include", "have" and the like are used herein to designate the presence of stated features, integers, steps, components or combinations thereof, but do not The presence or addition of one or more other features, integers, steps, components or combinations thereof is excluded.

While the invention may have various forms and various modifications may be made thereto, specific embodiments will be illustrated and explained in detail. However, it is not intended to limit the present invention to the specific forms disclosed, and it should be understood that the present invention includes all modifications, equivalents, and substitutions within the idea and technical scope of the present invention.

According to an embodiment of the present invention, a stripping agent composition for removing photoresist can be provided, which includes: a primary or secondary chain amine compound; a cyclic amine compound; Two linear or branched chain alkyl nitrogen-substituted amide compounds having 1 to 5 carbon atoms; protic solvents; and corrosion inhibitors, one or both of which have a boiling point of 180°C or higher The content of the amide compound in which a linear or branched chain alkyl group of 1 to 5 carbon atoms is substituted by nitrogen is 60% by weight to 90% by weight relative to the total weight of the lifting release agent composition, and wherein the primary Or the weight ratio of the secondary chain amine compound to the cyclic amine compound is 100:1 to 1:1.

The present inventors conducted a lot of research on the stripper composition for removing photoresist, and found through experiments that the stripper composition for removing photoresist containing all the above-mentioned components is less effective during the stripping process. Suppressing the corrosion of the lower metal film while having excellent photoresist stripping ability and having improved photoresist solubility, thereby completing the present invention.

As described above, the stripper composition for removing photoresist of the embodiment includes amide compounds having a boiling point (bp) of 180° C. or higher, one to two of which have 1 to 5 carbon atoms. Straight chain or branched chain alkyl groups substituted by nitrogen, wherein one to two straight chain or branched chain alkyl groups having 1 to 5 carbon atoms are substituted by nitrogen, acyl acids having a boiling point (bp) of 180°C or higher The content of the amine compound is 60% by weight to 90% by weight relative to the total weight of the release agent composition, and the weight ratio of the primary or secondary chain amine compound to the cyclic amine compound is 100:1 to 1:1, thus compared to According to the known situation, the stripping ability can be improved, and the solubility of the photoresist can be improved.

Amide compounds wherein one or two linear or branched chain alkyl groups having 1 to 5 carbon atoms are substituted with nitrogen and have a boiling point (bp) of 180°C or higher can be suitably dissolved in an aprotic polar organic solvent, The stripper composition for removing photoresist is allowed to effectively penetrate on the lower film, and may function in improving stripping ability, rinsing ability, and the like of the stripper composition.

In addition, amide compounds in which one or two linear or branched alkyl groups having 1 to 5 carbon atoms are nitrogen-substituted have some boiling point (bp): 180°C or more, or 182°C or more ℃, or 185°C or greater than 185°C, or 190°C or greater than 190°C, or 250°C or less than 250°C, or 210°C or less than 210°C, or 180°C to 250°C, or 180°C to 210°C, or 182°C °C to 250 °C, or 182 °C to 210 °C, or 185 °C to 250 °C, or 185 °C to 210 °C, or 190 °C to 250 °C, or 190 °C to 210 °C. When the photoresist is stripped using a stripping agent composition including an amide compound having a predetermined boiling point, the loss of the amide compound due to volatilization can be reduced, and it hardly causes decomposition of the amine compound over time, so that an embodiment The stripper composition can maintain physical properties such as excellent stripping and rinsing ability for a long time.

The boiling point is not limited to commonly known organic solvent measurement methods (eg, simple distillation equipment, etc.), and can be measured at normal temperature (temperature from 20°C to 30°C) and atmospheric pressure (pressure of 1 standard atmosphere) .

Simultaneously, when the boiling point (bp) of one or two straight-chain or branched-chain alkyl amide compounds substituted by nitrogen with 1 to 5 carbon atoms is too high, the subsequent distillation of the waste liquid can be carried out under reduced pressure. The recovery efficiency is lowered in the process, and therefore, it is preferable to have a boiling point of 250°C or less.

Meanwhile, with respect to the total weight of the release agent composition, more specifically, based on 100% by weight of the total weight of the release agent composition, wherein the boiling point (bp) is 180° C. or higher and one or both have 1 The content of the linear or branched chain alkylamide compound substituted by nitrogen to 5 carbon atoms may be 60% by weight or more, 65% by weight or more than 65% by weight, or 70% by weight or more than 70% by weight , and 90% by weight or less than 90% by weight, 85% by weight or less than 85% by weight, or 80% by weight or less than 80% by weight.

When the stripping agent composition for removing photoresist of an embodiment contains the above-mentioned content of one or both of them having a boiling point (bp) of 180° C. or higher When the linear or branched chain alkyl is nitrogen-substituted amide compound, the solubility of the photoresist is increased, which can ensure excellent stripping ability and the like, and can maintain the stripping and washing ability for a long time.

In addition, when the photoresist used remains on the substrate, a film detachment phenomenon or a wiring disconnection phenomenon occurs during the progress of post-processing, which affects process yield. Since one embodiment of the stripping agent composition for removing photoresist contains the above-mentioned content of one or both of the straight-chain or The amide compound in which the branched chain alkyl is substituted with nitrogen can increase the solubility of the photoresist, and reduce the probability of photoresist residue remaining on the substrate after the stripping process, thereby increasing the process economy and efficiency.

Meanwhile, when the content of one or both of the linear or branched chain alkyl groups having 1 to 5 carbon atoms substituted by nitrogen with a boiling point (bp) of 180°C or higher is contained in the release agent composition When the total weight of is less than 60% by weight, there may be a problem that the peeling ability is reduced and the photoresist remains on the substrate. When the content of the amide compound exceeds 90% by weight, there may be a problem that the peeling liquid remains on the surface without washing in the washing step.

其中，在化學式1中， R ₁為氫、甲基、乙基或丙基， R ₂為甲基或乙基， R ₃為氫或具有1個至5個碳原子的直鏈或分支鏈烷基，以及 R ₁及R ₃可彼此組合以形成環。 Specifically, nitrogen-substituted amide compounds in which one or two linear or branched chain alkyl groups having 1 to 5 carbon atoms having a boiling point (bp) of 180° C. or higher may have the following Chemical Formula 1 Structure: [Chemical Formula 1]

Wherein, in Chemical Formula 1, R ₁ is hydrogen, methyl, ethyl or propyl, R ₂ is methyl or ethyl, R ₃ is hydrogen or straight or branched chain alkane having 1 to 5 carbon atoms group, and R ₁ and R ₃ may combine with each other to form a ring.

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

The amide compound in which one or two linear or branched alkyl groups having 1 to 5 carbon atoms is substituted with nitrogen having a boiling point of 180° C. or higher may be in the group consisting of Select at least one of: N-Methylformamide (NMF), N-Ethylformamide (N-Ethylformamide, NEF), N-Methyl-2-pyrrolidone (N-Methyl-2- pyrrolidone, NMP) and N-ethyl-2-pyrrolidone (N-ethyl-2-pyrrolidone, NEP).

Meanwhile, the stripper composition for removing photoresist may include primary or secondary chain amine compounds and cyclic amine compounds.

The amine compound comprising primary or secondary chain amine compound and cyclic amine compound can allow the stripping agent composition for removing photoresist to have the ability to strip photoresist, and can play the role of dissolving photoresist and removing photoresist. Specifically, the primary or secondary chain amine compound may function in improving stripping ability, and the cyclic amine compound may function in improving stripping ability while minimizing damage to metal wiring.

Specifically, since the stripping agent composition for removing photoresist of the embodiment includes a primary or secondary chain amine compound and a cyclic amine compound, the removal rate of copper oxide will be improved, and in the conventional stripping The photoresist does not remain on the insulating film after the insulating film, it is easy to remove the metal oxide that may be generated on the lower metal film (for example, the lower Cu wiring), and when forming a transparent conductive film such as ITO, it is possible to prevent the insulating film The phenomenon of film detachment from the lower metal film.

Meanwhile, the weight ratio between the primary or secondary chain amine compound and the cyclic amine compound can be 100:1 to 1:1, or 80:1 to 1:1, or 50:1 to 1:1, or 10:1 to 1:1, or 100:1 to 1.5:1, or 80:1 to 1.5:1, or 50:1 to 1.5:1, or 10:1 to 1.5:1. Specifically, in the ratio formula, it means the weight ratio of primary or secondary chain amine compound:cyclic amine compound. For example, the weight ratio of the primary or secondary chain amine compound relative to 1 part by weight of the cyclic amine compound can be 1 part by weight to 100 parts by weight, or 1 part by weight to 80 parts by weight, or 1 part by weight to 50 parts by weight , or 1 to 10 parts by weight, or 1.5 to 100 parts by weight, or 1.5 to 80 parts by weight, or 1.5 to 50 parts by weight, or 1.5 to 10 parts by weight.

At this time, when the weight ratio of the primary or secondary chain amine compound to the cyclic amine compound exceeds 100:1, corrosion occurs on Cu or TFT metal, and may occur due to adhesion problems with the next insulating film or metal such as film problem of disengagement. When the weight ratio is less than 1:1, the decomposition ability of the photoresist decreases and remains on the substrate, which may cause a problem of foreign substances such as film detachment.

That is, the stripping agent composition for removing photoresist in the embodiment includes a primary or secondary chain amine compound and a cyclic amine compound, and the content of the cyclic amine compound is equal to or relatively less than the content of the primary or secondary chain amine compound , whereby the stripping ability and removal ability of the metal oxide of the metal-containing lower layer can be improved.

Meanwhile, relative to the total weight of the release agent composition, more specifically, based on 100% by weight of the total weight of the release agent composition, the total content of the primary or secondary chain amine compound and cyclic amine compound may be 1% by weight. or greater than 1 wt%, 3 wt% or greater than 3 wt%, or 5 wt% or greater than 5 wt%, 20 wt% or less than 20 wt%, 15 wt% or less than 15 wt%, or 10 wt% or less than 10 weight%.

Depending on the content range of the amine compound, the stripping agent composition of an embodiment can not only exhibit excellent stripping ability and the like, but also reduce the reduction of process economy and efficiency due to the excess amine, and reduce the generation of waste liquids and the like.

If excessive amounts of amine compounds are contained, this can lead to corrosion of the underlying film (eg, a copper-containing underlying film) and it may be necessary to use large amounts of corrosion inhibitor in order to inhibit corrosion. In this case, due to the large amount of corrosion inhibitor, a considerable amount of corrosion inhibitor may be absorbed and remain on the surface of the lower layer, thereby degrading the electrical characteristics of the copper-containing lower layer.

Specifically, if the total content of the primary or secondary chain amine compound and cyclic amine compound is less than 1% by weight relative to the total weight of the stripper composition, the stripping of the stripper composition for removing photoresist can be reduced. ability, and when the total content is more than 20% by weight relative to the total weight of the composition, the inclusion of excess amine compounds may lead to reduced process economy and efficiency.

In addition, within the content range of the amine compound, it can be used by adjusting the weight ratio between the above-mentioned primary or secondary chain amine compound and cyclic amine compound.

The primary or secondary chain amine compound may comprise at least one compound selected from the group consisting of: 2-(2-Aminoethoxy)ethanol, 1-Amino-2 - 1-Amino-2-Propanol, Monoethanolamine, Aminoethylethanolamine, N-methylethanolamine, and Diethanolamine, but not limited to.

Cyclic amine compounds may contain intramolecular tertiary amine structures. The tertiary amine means a structure in which three organic functional groups (except hydrogen) are bonded to one nitrogen atom, and the cyclic amine compound may contain at least one nitrogen atom of the tertiary amine. As a specific example, in the case of 1-imidazolidineethanol, the nitrogen atom in the ring bonded to the ethanol corresponds to the nitrogen atom of the tertiary amine.

In addition, the cyclic amine compound may be a saturated amine compound. The saturated amine compound means a compound composed of only a single bond and containing an unsaturated bond (double bond or triple bond) in the middle of the molecule.

The cyclic amine compound may comprise at least one compound selected from the group consisting of 1-imidazolidine ethanol, 1-(2-hydroxyethyl)piperazine (1-(2-Hydroxyethyl ) piperazine) and N-(2-aminoethyl) piperazine (N-(2-Amonoethyl) piperazine).

Meanwhile, the stripper composition for removing photoresist may contain a protic solvent. The protic solvent is a polar organic solvent that allows the stripper composition for removing the photoresist to penetrate better on the lower film, thereby assisting the stripping ability of the stripper composition for removing the photoresist, and can effectively Removal of stains on underlying films, such as copper-containing films, thereby improving the washability of stripper compositions used to remove photoresist.

The protic solvent may comprise alkylene glycol monoalkyl ether compounds. More specifically, the alkylene glycol monoalkyl ether may include diethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether , Diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, triethylene glycol Alcohol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether or a mixture of two or more of them.

Furthermore, considering the excellent wettability of the stripper composition for photoresist removal and especially resulting improved stripping ability and rinse ability, diethylene glycol monomethyl ether (MDG), diethylene glycol monomethyl ether Diethyl ether ((EDG), diethylene glycol monobutyl ether (BDG) or diethylene glycol monotertiary butyl ether (DGtB) and the like can be used as the alkylene glycol monoalkyl ether compound.

Relative to the total weight of the composition, except primary or secondary chain amine compounds, cyclic amine compounds, one or both of which have a boiling point (bp) of 180°C or higher, straight chain or In addition to branched chain alkyl nitrogen-substituted amide compounds, corrosion inhibitors, and the like, may contain residual levels of protic solvents.

For example, relative to the total weight of the composition, more specifically, based on 100% by weight of the total weight of the release agent composition, the content of the protic solvent may be 1% by weight to 50% by weight, or 5% by weight to 45% by weight, or 10% by weight to 40% by weight. By satisfying the content range, excellent stripping ability and the like of a stripper composition for removing photoresist can be secured, and stripping ability and rinse ability can be maintained for a long time.

In another aspect, a stripper composition for removing photoresist may include a corrosion inhibitor.

The above-mentioned corrosion inhibitor can suppress corrosion of a metal-containing lower film (for example, a copper-containing film) after removing a photoresist pattern using a stripper composition for removing photoresist.

As the corrosion inhibitor, at least one is selected from the group consisting of triazole compounds and imidazole compounds.

At this time, examples of the triazole compound are not particularly limited, but for example, it may be at least one selected from the group consisting of 2,2'[[(methyl-1H-benzotriazole -1-yl)methyl]imino]bisethanol and 4,5,6,7-tetrahydro-1H-benzotriazole.

In addition, examples of imidazole compounds are not particularly limited, and may be, for example, 2-Mercapto-1-methylimidazole (2-Mercapto-1-methylimidazole).

On the other hand, with respect to the total weight of the stripper composition, more specifically, based on 100% by weight of the total weight of the composition, the content of the corrosion inhibitor may be 0.01% by weight to 10% by weight, or 0.01% by weight % to 5.0 wt%, or 0.01 wt% to 1.0 wt%. When the content of the corrosion inhibitor is less than 0.01% by weight relative to the total weight of the composition, it may be difficult to effectively suppress corrosion of the lower layer. In addition, when the content of the corrosion inhibitor exceeds 10% by weight relative to the total weight of the composition, a large amount of the corrosion inhibitor may be absorbed and remain on the lower film, thereby reducing the copper-containing lower film, especially the copper/molybdenum metal film. electrical characteristics.

In addition, the stripper composition for removing photoresist may include a silicon-based nonionic surfactant in an amount relative to the total weight of the stripper composition, more specifically, based on 100% by weight of the total weight of the composition It is less than 0.001% by weight, or less than 0.0001% by weight. More preferably, the stripping agent composition for removing photoresist does not substantially contain silicon-based nonionic surfactant or may contain only a trace amount to almost no level.

When the content of the silicon-based nonionic surfactant increases to more than 0.001% by weight or more than 0.0001% by weight relative to the total weight of the composition, there may be a problem of metal contact resistance change.

Specifically, the silicon-based nonionic surfactant may include polysiloxane-based polymers. More specifically, examples of polysiloxane-based polymers are not particularly limited, but for example, polyether-modified acrylic functional polydimethylsiloxane, polyether-modified siloxane, polyether Modified polydimethylsiloxane, polyethylalkylsiloxane, aralkyl modified polymethylalkylsiloxane, polyether modified hydroxyl functional polydimethylcellulose, Polyether-modified dimethylpolysiloxanes, modified acrylic-functional polydimethylsiloxanes, or mixtures of two or more thereof, and the like.

The stripper composition for removing photoresist may further include known additives as needed, and the specific type or content of the additives is not particularly limited.

In addition, a stripper composition for removing photoresist may be prepared according to a general method of mixing the above-mentioned components. A specific method for preparing the stripper composition for removing photoresist is not particularly limited.

In another aspect, according to another embodiment of the present invention, a method for stripping a photoresist may be provided, which includes the step of stripping the photoresist using the stripper composition for removing the photoresist according to the above-mentioned one embodiment.

A method for stripping a photoresist according to an embodiment may include the steps of: forming a photoresist pattern on a substrate on which a lower film is formed; patterning the lower film with the photoresist pattern; The photoresist stripper composition strips the photoresist.

The description about the stripper composition for removing photoresist includes the detailed description about one embodiment above.

Specifically, the method for stripping the photoresist may include: a step of forming a photoresist pattern on the substrate forming the lower layer to be patterned through a photolithography process, and a step of patterning the lower film using the photoresist pattern as a mask , and a step of stripping the photoresist using the stripping agent composition mentioned above.

In the method for stripping the photoresist, the steps of forming the photoresist pattern and patterning the lower film can use a known device manufacturing method, and the specific manufacturing method is not particularly limited.

Meanwhile, an example of the step of stripping the photoresist by using a stripper composition for removing the photoresist is not particularly limited, but for example, a step of applying a stripper composition for removing the photoresist to The substrate of the photoresist pattern remained and was washed with an alkali buffer solution, followed by washing with ultrapure water and drying. Since the above-mentioned stripper composition exhibits excellent stripping ability and rinsing ability to effectively remove stains on the lower film and ability to remove native oxide film, it can satisfactorily maintain the lower film surface condition while effectively removing residual photoresist film on the lower film. Thereby, subsequent steps can be appropriately performed on the patterned lower layer to form the device.

Specific examples of the lower layer formed on the substrate are not particularly limited, but may include aluminum or aluminum alloys, copper or copper alloys, molybdenum or molybdenum alloys, or mixtures thereof, composite alloys thereof, composite laminates thereof, and the like.

The type, composition or physical properties of the photoresist targeted by the lift-off method are also not particularly limited, and for example it may be a known photoresist to be used in an underlying film comprising aluminum or an aluminum alloy, copper or copper alloys, molybdenum or molybdenum alloys and the like. More specifically, the photoresist may include a photosensitive resin component such as a novolac resin, a resole resin, or an epoxy resin.

[ Advantageous Effect ] According to the present invention, it is possible to provide a stripper composition for removing photoresist, which suppresses corrosion on the lower metal film during the stripping process, and simultaneously has excellent photoresist stripping ability and has improved photoresist solubility resistance; and a stripping photoresist method using the same.

Hereinafter, the present invention will be described in detail with reference to the following examples. However, these examples are presented for illustrative purposes only, and the scope of the present invention is not limited thereto. < Example 1 to Example 16 : Preparation of stripper composition for removing photoresist >

According to the composition of Table 1 and Table 2 below, each component was mixed to prepare the stripping agent compositions for removing photoresist of Examples 1 to 16 respectively. The specific composition of the prepared stripper composition for removing photoresist is described in Table 1 and Table 2 below.

[ surface 1] category Instance (wt%) 1 2 3 4 5 6 7 8 AEE 7.9 5 7.9 5 7.9 5 7 6 MIPA - - - - - - - - MEAs - - - - - - - - AEEA - - - - - - - - N-MEA - - - - - - - - DEA - - - - - - - - IMEs 0.1 3 - - - - 1 2 HEP - - 0.1 3 - - - - AEP - - - - 0.1 3 - - NMF 75.00 75.00 75.00 75.00 75.00 70.00 60.00 80.00 NMP - - - - - - - - NEF - - - - - - - - DEF - - - - - - - - MDG - - 16.50 - 16.90 - - 11.60 EDG 16.60 - - - - 21.50 - - BDG - 16.99 - - - - 31.50 - BYZGR - - - 16.70 - - - - DIW - - - - - - - - Corrosion Inhibitor 1 0.40 - 0.50 0.30 0.10 - 0.50 0.40 Corrosion Inhibitor 2 - 0.01 - - - 0.50 - - Corrosion Inhibitor 3 - - - - - - - -

[ Table 2] category Instance (wt%) 9 10 11 12 13 14 15 16 AEE 6 6 7 - - - - - MIPA - - - 7 - - - - MEAs - - - - 7 - - - AEEA - - - - - 7 - - N-MEA - - - - - - 7 - DEA - - - - - - - 7 IMEs - - 1 1 - - - 1 HEP 2 - - - 1 - 1 - AEP - 2 - - - 1 - - NMF 75.00 75.00 75.00 - 70.00 - 70.00 - NMP - - - 65.00 - - - 70.00 NEF - - - - - 80.00 - - DEF - - - - - - - - MDG - - - - - - - - EDG 16.95 - - - 21.80 - BDG - 16.50 16.90 26.80 21.70 11.90 - - BYZGR - - - - - - - 21.90 DIW - - - - - - - - Corrosion Inhibitor 1 - 0.50 - - 0.30 - 0.20 - Corrosion Inhibitor 2 - - - 0.20 - 0.10 - 0.10 Corrosion Inhibitor 3 0.05 - 0.10 - - - - - AEE: 2-(2-aminoethoxy) ethanol (1-Amino-2-Propanol), CAS: 929-06-6 MIPA: 1-amino-2-propanol (1-Amino-2-Propanol ), CAS: 78-96-6 MEA: Monoethanolamine (Monoethanolamine), CAS: 141-43-5 AEEA: Aminoethylethanolamine (Aminoethylethanolamine), CAS: 111-41-1 N-MEA: N-methylethanolamine (N-methylethanolamine), CAS: 109-83-1 DEA: Diethanolamine, CAS: 150-59-9 IME: 1-Imidazolidine ethanol, CAS: 77215-47-5 HEP : Hydroxyethyl-piperazine (Hydroxyethyl-piperazine), CAS: 103-76-4 AEP: N-Aminoethylpiperazine (N-Aminoethylpiperazine), CAS: 140-31-8 NMF: N-methylformamide Amine (N-Methylformamide), CAS: 123-39-7, boiling point 182.5°C NMP: N-Methyl-2-pyrrolidone (N-Methyl-2-pyrrolidone), CAS: 872-50-4, boiling point 202°C NEF : N-Ethylformamide (N-Ethylformamide), CAS: 627-45-2, boiling point 202 to 204°C DEF: N, N-Diethylformamide (N,N-Diethylformamide), CAS: 617 -84-5, boiling point 178.3°C MDG: Diethylene glycol methyl ether, CAS: 111-77-3 EDG: Diethylene Glycol Monoethyl Ether, CAS: 111-90 -0 BDG: Diethylene Glycol Monobutyl Ether, CAS: 112-34-5 DGtB: Diethylene Glycol Mono-tert-butyl ether, CAS: 110 -09-8 DIW: deionized water corrosion inhibitor 1: 2,2'[[(methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol (2 ,2'[[(Methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol), CAS: 88477-37-6 Corrosion inhibitor 2: 4,5,6,7-tetrahydro-1H-benzo Triazole (4,5,6,7-tetrahydrotolytriazole), CAS: 6789-99-7 Corrosion inhibitor 3: 2-Mercapto-1-methylimidazole (2-Mercapto-1-methylimidazole), CAS: 60-56 -0 < Comparative Example 1 to Comparative Example 15 : Preparation of stripper composition for photoresist removal >

According to the composition of Table 3, Table 4 and Table 5, each component was mixed to prepare the stripping agent composition for removing photoresist of Comparative Example 1 to Comparative Example 15 respectively. The specific composition of the above-prepared stripping agent composition for removing photoresist is described in Table 3, Table 4 and Table 5 below.

[ surface 3] category Comparative example (weight%) 1 2 3 4 5 6 AEE 8 - - - - - MIPA - 8 - - - - MEAs - - 8 - - - AEEA - - - 8 - - N-MEA - - - - 8 - DEA - - - - - 8 IMEs - - - - - - HEP - - - - - - AEP - - - - - - NMF 75.00 75.00 75.00 75.00 75.00 75.00 NMP - - - - - - NEF - - - - - - DEF - - - - - - MDG - - 16.95 - 16.50 - EDG 16.50 - - 16.90 - - BDG - 16.90 - - - 16.50 BYZGR - - - - - - DIW - - - - - - Corrosion Inhibitor 1 0.50 - - - 0.50 0.50 Corrosion Inhibitor 2 - 0.10 - 0.10 - - Corrosion Inhibitor 3 - - 0.05 - - -

[ surface 4] category Comparative example (weight%) 7 8 9 10 11 12 13 14 AEE 7 - 7 - 7 - - 3 MIPA - 7 - 7 - - - - MEAs - - - - - 7 - - AEEA - - - - - - - - N-MEA - - - - - - 7 - DEA - - - - - - - - IMEs - - 1 - - 1 - 1 HEP 1 - - - - - 1 - AEP - 1 - 1 1 - - - NMF 55.00 - 91.90 - - - - - NMP - - - 91.90 - - - - NEF - - - - - - - - DEF - 55.00 - - 70.00 75.00 75.00 30.00 MDG - - - - - - 16.99 - EDG - - - - - 17.00 - - BDG - 36.50 - - 21.95 - - 35.50 BYZGR 36.50 - - - - - - - DIW - - - - - - - 30.00 Corrosion Inhibitor 1 0.50 0.50 - - 0.05 - - 0.50 Corrosion Inhibitor 2 - - 0.10 0.10 - 0.01 - - Corrosion Inhibitor 3 - - - - - - 0.01 -

[ surface 5] category Comparative example (weight%) 15 imidazolyl-4-ethanol 3.5 (2-aminoethoxy)-1-ethanol 1 N-Methylformamide 50 Diethylene glycol monobutyl ether 45 [[(Methyl-1H-benzotriazol-1-yl)methyl]imino]bisethanol 0.3 Benzimidazole 0.2 Polyether modified polydimethylsiloxane 0.035 < Experimental example : Measuring the Physical Properties of the Stripper Compositions for Removing Photoresist Obtained in Examples and Comparative Examples >

Prepare 300 g of each composition in Table 1 to Table 5 in a 500 ml beaker, stir it on a hot plate at 500 rpm, and heat to 60° C. to obtain a chemical solution (stripping agent composition).

The physical properties of the prepared chemical solutions were measured by the following methods, and the results are shown in the tables.

1 . Assess stripping capability

After photo-processing the a-Si, a substrate with photoresist patterning with a size of 3 cm x 3 cm was prepared and hard baked at 170° C. for 20 minutes.

The substrates were immersed in the chemical solution prepared at 60° C. at 30 second intervals, then removed and washed in tertiary deionized water for 30 seconds. Dry the deionized water using an air gun.

The prepared samples were analyzed via an optical microscope, and the time point at which the photoresist residue disappeared was evaluated as the peeling time.

The stripping abilities of the stripping agent compositions of Examples and Comparative Examples were evaluated in the same manner as above, and the results are shown in Table 6 and Table 7 below.

[ surface 6] category example 1 2 3 4 5 6 7 8 Stripping time (seconds) 30 30 30 30 30 30 30 30 category example 9 10 11 12 13 14 15 16 Stripping time (seconds) 30 30 30 30 30 30 30 30

[ surface 7] category comparative example 1 2 3 4 5 6 15 Stripping time (seconds) 90 120 60 90 90 90 60

As shown in Table 6 and Table 7, it can be confirmed that the release agent composition of the example contains a predetermined amount of a primary or secondary chain amine compound, a cyclic amine compound, and one or both of which have a boiling point of 180° C. or higher and have a 1 The nitrogen-substituted amide compound of a linear or branched chain alkyl group having 1 to 5 carbon atoms exhibits excellent stripping ability compared to the stripping agent composition of the comparative example.

In addition, from Table 7, it can be confirmed that the stripping agent compositions containing one type of primary or secondary chain amine compound or one type of cyclic amine compound of Comparative Examples 1 to 6 exhibited a significant reduction in stripping ability compared to Examples. Small, whereby there is a risk of post-processing defects in the photoresist residue.

In addition, the release agent composition of Comparative Example 15 containing an excess of imidazolyl-4-ethanol as a cyclic amine compared to (2-aminoethoxy)-1-ethanol as a chain amine showed Significant reduction in stripability, whereby there is a risk of post-processing defects in photoresist residues.

2. Evaluate Ti/Al/Ti cross section damage

After the optical treatment of Ti/Al/Ti, a substrate with photoresist patterning with a size of 3 cm×3 cm was prepared, and the substrate was immersed in the chemical solution prepared at 60° C. for 120 seconds. The substrate was removed and washed in tertiary deionized water for 30 seconds, and the deionized water was dried using an air gun.

After repeating the above treatment three times, the Ti/Al/Ti cross-sectional damage was analyzed via FE-SEM.

The presence or absence of cross-sectional damage was evaluated as having cross-sectional damage when the Al layer had damage compared to the sample not subjected to chemical treatment.

The Ti/Al/Ti cross-sectional damage of the stripper compositions of Examples and Comparative Examples was evaluated in the same manner as above, and the results are shown in Table 8, Table 9 and FIG. 1 below.

[ surface 8] category example 1 2 3 4 5 6 9 11 Ti/Al/Ti cross section no damage no damage no damage no damage no damage no damage no damage no damage

[ surface 9] category comparative example 1 2 3 Ti/Al/Ti cross section damage damage damage

As shown in Table 8, Table 9, and Figure 1, no Ti/Al/Ti cross-sectional damage was observed in the examples of the present invention, but Ti/Al/Ti cross-sectional damage was observed in Comparative Examples 1 to 3 damage. Thus, it can be confirmed that a predetermined amount of a primary or secondary chain amine compound, a cyclic amine compound, and one or both of them having a boiling point (bp) of 180°C or higher and having 1 to 5 carbon atoms are contained or The stripper composition of the present invention of branched chain alkyl nitrogen substituted amide compounds minimizes damage to metals.

3. Evaluate Cu surface damage

A substrate having a size of 3 cm × 3 cm with Cu deposited on the front surface was prepared, and then the substrate was immersed in a chemical solution prepared at 60 °C for 120 seconds, and the substrate was taken out and washed in tertiary deionized water for 30 seconds . Dry the deionized water using an air gun.

After repeating the above treatment 3 times, Cu surface damage was analyzed via FE-SEM.

The presence or absence of surface damage was assessed as having surface damage when there was a change in morphology compared to chemically untreated specimens.

The Cu surface damage of the stripper compositions of Examples and Comparative Examples was evaluated in the same manner as above, and the results are shown in Table 10, Table 11 and FIG. 2 below.

[ surface 10] category example 1 2 3 4 5 6 9 11 Cu surface no damage no damage no damage no damage no damage no damage no damage no damage

[ surface 11] category comparative example 1 2 3 Cu surface damage damage damage

As shown in Table 10, Table 11, and FIG. 2 , Cu surface damage was not observed in Examples of the present invention, but Cu surface damage was observed in Comparative Examples 1 to 3. Thus, it can be confirmed that a predetermined amount of a primary or secondary chain amine compound, a cyclic amine compound, and one or both of them having a boiling point (bp) of 180°C or higher and having 1 to 5 carbon atoms are contained or The stripper composition of the present invention of branched chain alkyl nitrogen substituted amide compounds minimizes damage to metals.

4. Assessing photoresist solubility

The photoresist stock solution (CT-3813, produced by COTEM) was oven baked at 150°C for 4 hours to prepare 3% photoresist powder.

The PR powder was dissolved in the chemical solution prepared at 60°C for 1 hour, and then the dissolved chemical solution was vacuum filtered through a filter with a pore size of 1 micron and a diameter of 90 mm.

After drying in an oven at 100°C for 1 hour, the weight of the filter was measured and compared to the weight before filtration to calculate the PR solubility, and the results are shown in Table 12 below.

PR solubility = (filter weight before filtration/filter weight after drying) × 100%)

[ surface 12] category Example 7 Example 11 Example 12 Example 14 Comparative Example 7 Comparative Example 8 Comparative Example 15 Solubility of PR 96.76% 98.85% 98.54% 98.47% 92.37% 91.89% 94.08%

As shown in Table 12, the inventive examples all exhibit solubility of 95% or greater, but the comparative examples exhibit solubility of less than 95%.

The higher the solubility of the photoresist, the lower the probability that photoresist residue will remain on the substrate after the stripping process. Therefore, containing a predetermined content of primary or secondary chain amine compounds, cyclic amine compounds, and one or two of them having a boiling point (bp) of 180°C or higher, linear or branched chain alkanes having 1 to 5 carbon atoms Compared with the comparative example, the stripping agent composition of the present invention based on the nitrogen-substituted amide compound has lower cost and higher efficiency.

5. Evaluate contact angle

A substrate having a size of 3 cm × 3 cm with Cu deposited on the front surface was prepared, and then the substrate was immersed in a chemical solution prepared at 60 °C for 120 seconds, and the substrate was taken out and washed in tertiary deionized water for 30 seconds . Dry the deionized water using an air gun.

3 μl of deionized water (DIW) was dropped on the prepared sample, and then the angle between the sample and the DIW was measured. The left and right angles of the sample were measured and their average value was calculated, and the equipment used was DSA100 from KRUSE. The degree of surface hydrophilization was evaluated by the average value of the contact angle, and it means that the lower the value of the contact angle, the stronger the degree of hydrophilization, thereby evaluating the degree of residual organic matter on the surface.

The contact angles of the release agent compositions of Examples and Comparative Examples were evaluated in the same manner as above, and the results are shown in Table 13 below.

[ surface 13] category Example 2 Example 3 Example 4 Example 8 Example 9 Example 10 Example 16 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 15 DIW contact angle (°) 55.2 54.7 54.4 53.8 54.1 55.4 54.2 62.1 61.8 63.5 62.6 42

As shown in Table 13, it was confirmed that the release agent compositions of the examples of the present invention exhibited a contact angle distribution of 54°±2°, and the comparative examples exhibited values significantly deviated from 54°. From this, it can be confirmed that the degree of surface hydrophilization is greatly influenced by the content of the amide compound in the release agent composition.

Specifically, in the case of Comparative Example 15, the hydrophilic surfactant remained in the release agent composition, and the contact angle was greatly reduced to 42°, which may cause a problem of variation in metal contact resistance.

none

1 is a scanning electron microscope (FE-SEM) photograph showing the evaluation of Ti/Al/Ti by stripper compositions for removing photoresist according to Examples 1 to 6, Example 9 and Example 11 of the present invention the result of cross-sectional damage; and 2 is a scanning electron microscope (FE-SEM) photograph showing the results of evaluating Cu surface damage by the stripper compositions for removing photoresist according to Examples 1 to 6, Example 9 and Example 11 of the present invention .

Claims (16)

A stripper composition for removing photoresist, comprising: Primary or secondary chain amine compounds; Cyclic amine compounds; Amide compounds in which one or two linear or branched chain alkyl groups having 1 to 5 carbon atoms are nitrogen-substituted, having a boiling point of 180°C or higher; protic solvents; and corrosion inhibitors, The content of the amide compound wherein one or two of the linear or branched alkyl groups having 1 to 5 carbon atoms or more having a boiling point of 180° C. or higher is nitrogen-substituted relative to the stripping The total weight of the agent composition is 60% to 90% by weight, and Wherein the weight ratio of the primary or secondary chain amine compound to the cyclic amine compound is 100:1 to 1:1. The stripping agent composition for removing photoresist as described in Claim 1, wherein: one or both of them have a linear or branched chain alkane having 1 to 5 carbon atoms having a boiling point of 180° C. or higher The amide compound whose group is substituted by nitrogen comprises a compound of the following chemical formula 1: [chemical formula 1]

Wherein, in Chemical Formula 1, R ₁ is hydrogen, methyl, ethyl or propyl, R ₂ is methyl or ethyl, R ₃ is hydrogen or straight or branched chain alkane having 1 to 5 carbon atoms group, and R ₁ and R ₃ are optionally combined with each other to form a ring. The stripping agent composition for removing photoresist as described in Claim 1, wherein: Said amide compound having a boiling point of 180° C. or higher in which one or two linear or branched chain alkyl groups having 1 to 5 carbon atoms is substituted with nitrogen is selected from the group consisting of At least one of: N-methylformamide, N-ethylformamide, N-methyl-2-pyrrolidine, and N-ethyl-2-pyrrolidine. The stripping agent composition for removing photoresist as described in Claim 1, wherein: The weight ratio of the primary or secondary chain amine compound to the cyclic amine compound is 80:1 to 1.5:1. The stripping agent composition for removing photoresist as described in Claim 1, wherein: The total content of the primary or secondary chain amine compound and the cyclic amine compound is contained in an amount of 1% by weight to 20% by weight relative to the total weight of the release agent composition. The stripping agent composition for removing photoresist as described in Claim 1, wherein: The primary or secondary chain amine compound comprises at least one selected from the group consisting of: 2-(2-aminoethoxy)ethanol, 1-amino-2-propanol, monoethanolamine , amine ethylethanolamine, N-methylethanolamine and diethanolamine. The stripping agent composition for removing photoresist as described in Claim 1, wherein: The cyclic amine compound contains an intramolecular tertiary amine structure. The stripping agent composition for removing photoresist as described in Claim 1, wherein: The cyclic amine compound is a saturated amine compound. The stripping agent composition for removing photoresist as described in Claim 1, wherein: The cyclic amine compound comprises at least one selected from the group consisting of: 1-imidazolidineethanol, 1-(2-hydroxyethyl)piperazine, and N-(2-aminoethyl)piperazine . The stripping agent composition for removing photoresist as described in Claim 1, wherein: The protic solvent comprises alkylene glycol monoalkyl ether compounds. The stripping agent composition for removing photoresist as described in Claim 1, wherein: The corrosion inhibitor includes at least one selected from the group consisting of triazole compounds and imidazole compounds. The stripping agent composition for removing photoresist as described in Claim 11, wherein: The triazole compound comprises at least one selected from the group consisting of: 2,2'[[(methyl-1H-benzotriazol-1-yl)methyl]imino] Diethanol and 4,5,6,7-tetrahydro-1H-benzotriazole. The stripping agent composition for removing photoresist as described in Claim 11, wherein: The imidazole compounds include 2-mercapto-1-methylimidazole. The stripper composition for removing photoresist as described in Claim 1, comprising: 1% to 20% by weight of primary or secondary chain amine compounds and cyclic amine compounds, 60% to 90% by weight of nitrogen-substituted amide compounds having a boiling point of 180°C or higher in which one or two linear or branched chain alkyl groups having 1 to 5 carbon atoms, 0.01% to 10% by weight of a corrosion inhibitor, and Residual amount of protic solvent. The stripping agent composition for removing photoresist as described in Claim 1, wherein: The release agent composition contains silicon-based nonionic surfactant in an amount of less than 0.001% by weight based on the total weight of the composition. A method for stripping photoresist comprising the steps of: forming a photoresist pattern on the substrate forming the lower film; patterning the lower film with the photoresist pattern; and The photoresist is stripped using the stripper composition for removing photoresist as described in Claim 1.

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