Stripping liquid composition

Abstract

The invention discloses a stripping liquid composition which has excellent stripping performance and is environment-friendly. According to one aspect, there is provided a stripper composition comprising: two or more first solvents including at least one solvent having a pKa greater than or equal to 15; two or more second solvents including at least one solvent having a pKa of less than 15; and two or more amine compounds; the viscosity of the stripping liquid composition at 50 DEG C is less than 4.0 cP.

Description

Technical Field

[0001] The present invention relates to a stripping liquid composition. Background Art

[0002] The circuit of an organic light emitting diode or a liquid crystal display device has an extremely fine structure. Such a fine-structured circuit can be formed by the following method: a composition for forming a photoresist is uniformly coated on the surface of an insulating film or a metal film formed on a substrate to form a photoresist layer, and then, it is cured at an appropriate temperature, and by exposing and developing the photoresist layer, a photoresist pattern having a predetermined pattern is formed.

[0003] At this time, the stripping liquid composition for removing the above-mentioned photoresist pattern needs to have excellent stripping property for the photoresist pattern, and at the same time, no undissolved photoresist material or fine particles should remain on the substrate after stripping, and it also needs to have the property of not causing corrosion of the metal film. Depending on the compounds and the composition ratios of its components, the dissolution performance, stripping performance, corrosiveness of the metal film, process complexity, environmental stability, workability, etc. of this stripping liquid composition change significantly, and thus, research on the compounds and the composition ratios of the relevant components is ongoing. Summary of the Invention

[0004] Problems to be Solved by the Invention

[0005] According to one aspect of the present invention, there is provided a stripping liquid composition that excludes toxic solvents harmful to the human body and the environment.

[0006] According to another aspect of the present invention, there is provided a stripping liquid composition that can improve the stripping force, cleaning force, and persistence of stripping performance for a photoresist layer.

[0007] According to still another aspect of the present invention, there is provided a stripping liquid composition that can improve the yield and maintain the device reliability by effectively preventing corrosion of a metal substrate.

[0008] According to yet another aspect of the present invention, there is provided a stripping liquid composition that can improve the hydrophilicity even when a modified photoresist layer accumulates, thereby improving the efficiency of the rinsing process.

[0009] The object of the present invention is not limited to the above-mentioned objects, and other objects and advantages of the present invention not mentioned can be understood through the following description, and can be more clearly understood through the embodiments of the present invention. In addition, it can be easily understood that the objects and advantages of the present invention can be achieved by the means and combinations described in the specification.

[0010] Means for Solving the Problems

[0011] According to a first aspect of the present invention, there is provided a stripping liquid composition comprising: two or more first solvents including at least one solvent having a pK a greater than or equal to 15; two or more second solvents including at least one solvent having a pK a less than 15; and two or more amine compounds; the viscosity of the above stripping liquid composition at 50 °C is less than 4.0 cP.

[0012] According to a second aspect of the present invention, in the above first aspect, the number of carbon atoms of the solvent having a pK a greater than or equal to 15 may be 2 or more and 6 or less.

[0013] According to a third aspect of the present invention, in the above first or second aspect, at least one of the two or more first solvents contains one or more nitrogen atoms in the molecule. Specifically, the pK a of at least one of the two or more first solvents may be greater than or equal to 15.

[0014] According to a fourth aspect of the present invention, in any one of the above first to third aspects, the solvent having a pK a greater than or equal to 15 may include at least one selected from the group consisting of N-Ethylformamide, Dimethylsulfoxide, and Sulfolane.

[0015] According to a fifth aspect of the present invention, in any one of the above first to fourth aspects, the two or more first solvents may further include a solvent having a pK a less than 15.

[0016] According to a sixth aspect of the present invention, in any one of the above first to fifth aspects, based on the total weight of the stripping liquid composition, the content of the first solvent may be 30% by weight or more and 60% by weight or less.

[0017] According to a seventh aspect of the present invention, in any one of the above first to sixth aspects, the second solvent may include: a first secondary solvent having at least one ether group and one hydroxyl group; and a second secondary solvent having two or more hydroxyl groups in the molecule.

[0018] According to the eighth aspect of the present invention, in the above seventh aspect, the first co-solvent may include at least one selected from the group consisting of Diethylene glycol monomethylether, Diethyleneglycol monoethyl ether, Diethyleneglycol butylether, Diethyleneglycol propylether, Tri(propylene glycol)methylether, and Di(propylene glycol)methyl ether.

[0019] According to the ninth aspect of the present invention, in the above seventh or eighth aspect, the second co-solvent may include at least one selected from the group consisting of Diethylene Glycol, Ethylene glycol, Propyleneglycol, 1,3-Butylene glycol, Triethylene glycol, and Tetraethylene glycol.

[0020] According to the tenth aspect of the present invention, in any one of the above seventh to ninth aspects, based on the total weight of the stripping liquid composition, the content of the first co-solvent may be 25% by weight or more and 65% by weight or less, and the content of the second co-solvent may be 5% by weight or more and less than 45% by weight.

[0021] According to the eleventh aspect of the present invention, in any one of the above first to tenth aspects, based on the total weight of the stripping liquid composition, the content of the second solvent may be 35% by weight or more and 90% by weight or less.

[0022] According to the twelfth aspect of the present invention, in any one of the above first to eleventh aspects, the amine compound may include a chain amine and a cyclic amine.

[0023] According to a thirteenth aspect of the present invention, in the above twelfth aspect, the chain amine may include at least one selected from the group consisting of monoethanolamine, ethylenediamine, 2-(2-aminoethoxy)ethanol, 2-(2-aminoethylamino)ethanol, monoisopropanolamine, diethanolamine, 3,3'-iminodipropylamine, N-methylethanolamine, and triethanolamine.

[0024] According to a fourteenth aspect of the present invention, in the above twelfth or thirteenth aspect, the cyclic amine may include at least one selected from the group consisting of 1-(2-hydroxyethyl)piperazine, 1-(2-aminoethyl)piperazine, 1-phenylpiperazine, N-(3-aminopropyl)morpholine, 2-methylpiperazine, 1-methylpiperazine, 1-amino-4-methylpiperazine, 1-(2-hydroxyethyl)-4-methylpiperazine, and 1-benzylpiperazine.

[0025] According to a fifteenth aspect of the present invention, in any one of the above first to fourteenth aspects, the amine compound may each independently contain one or more hydroxyl groups in the molecule.

[0026] According to a sixteenth aspect of the present invention, in any one of the above first to fifteenth aspects, based on the total weight of the stripping liquid composition, the content of the amine compound may be 2% by weight or more and 6% by weight or less.

[0027] According to a seventeenth aspect of the present invention, in any one of the above first to sixteenth aspects, a stripping liquid composition further including at least one additive selected from a preservative and a stripping accelerator may be provided.

[0028] The above technical solutions do not list all the features of the present invention. The various features of the present invention and the advantages and effects based on the features can be more detailedly understood by referring to the following specific illustrative examples.

[0029] Advantages of the Invention

[0030] According to one aspect of the present invention, the peeling force, cleaning force, and the persistence of the peeling performance of the photoresist layer can be improved.

[0031] According to another aspect of the present invention, the yield can be increased by effectively preventing the corrosion of the metal substrate, thereby maintaining the reliability of the device.

[0032] According to still another aspect of the present invention, even when the modified photoresist layer accumulates, the hydrophilicity can be improved, thereby improving the efficiency of the rinsing process.

[0033] In addition to the above effects, the specific effects of the present invention will be described while explaining the specific details of implementing the present invention. Further, the effects of the present invention are not limited to the above effects, and can be easily achieved by the means and combinations described in the specification. Detailed Embodiments

[0034] In this specification, unless explicitly distinguished and described otherwise, descriptions of the singular should be understood to include the plural.

[0035] As used herein, "comprising" and / or "including" mean the presence of the specific recited forms, steps, numbers, actions, components, elements, and / or groups thereof, and do not exclude the presence or addition of one or more other forms, steps, numbers, actions, components, elements, and / or groups.

[0036] In this specification, "at least one of a, b, and c" may include one or more selected from the group consisting of a, b, and c.

[0037] When describing multiple embodiments in this specification, unless explicitly stated to the contrary, each embodiment can be combined. At this time, the effects of the present invention can be defined to include the effects generated by each embodiment and the effects generated by organically combining each embodiment. For example, even if embodiments 1 and 2 are separately and independently described in this specification, unless the context clearly indicates otherwise, embodiments 1 and 2 can be organically combined with each other, and the effects of the present invention can include the effects generated by the combination of embodiments 1 and 2.

[0038] As used herein, the term "to" in a numerical range means a numerical range that includes the lower and upper limits respectively specified before or after that term. For example, when a to b is described in the specification, it can be understood that a or more and b or less (a to b) are described.

[0039] When multiple numerical values of the upper or lower limit of any numerical range are mentioned in this specification, the numerical range disclosed herein can be understood as any numerical range with any one of the multiple upper limit values mentioned as its upper limit value and any one of the multiple lower limit values as its lower limit value. For example, when a or more or b or more and c or less or d or less is described in the specification, it can be understood as a or more and c or less, a or more and d or less, b or more and c or less, or b or more and d or less.

[0040] In this specification, "layer" can include cases where the layer is formed only on a part of the relevant area, in addition to cases where the layer is formed over the entire relevant area when observing the area where the relevant layer exists. For example, the surface of the layer can be defined to include flat forms, non-flat forms, and combinations thereof, or continuous forms, discontinuous forms, and combinations thereof. For example, if another member forms a layer directly on top of a member, the coverage rate of the other member on the surface of the above-mentioned one member can be defined as 1% or more, 5% or more, 10% or more, 20% or more, 30% or more, 40% or more, 50% or more, 60% or more, 70% or more, 80% or more, 85% or more, 90% or more, 95% or more, or 99% or more.

[0041] Degree terms used herein, such as "about" and "substantially", mean a reasonable amount of deviation of the modified term such that the final result is not significantly changed. These terms can be interpreted to include a deviation of at least ±5% or at least ±10% provided that the deviation does not negate the meaning of the term it modifies.

[0042] In this specification, a "polar solvent" can be defined as a solvent having a dielectric constant of 5 or more, 6 or more, 7 or more, 8 or more, 9 or more, or 10 or more.

[0043] According to one aspect of the present invention, there is provided a stripping liquid composition, which includes: two or more first solvents, including at least one solvent with a pKa greater than or equal to 15; two or more second solvents, including at least one solvent with a pKa less than 15; and two or more amine compounds; and the viscosity of the above stripping liquid composition at 50 °C is less than 4.0 cP. According to one aspect of the present invention, when the combination relationship of two or more first solvents including at least one solvent with a pKa greater than or equal to 15, two or more second solvents including at least one solvent with a pKa less than 15, and two or more amine compounds and the viscosity of the above stripping liquid composition satisfy the above range, the stripping force, cleaning force, and persistence of the stripping performance for the photoresist layer can be improved. According to another aspect of the present invention, by satisfying the combination relationship of the above components, corrosion of the metal substrate can be effectively prevented, the yield can be increased, and thus the reliability of the device can be maintained.

[0044] Hereinafter, the constitution of the present invention will be described in more detail.

[0045] 1. Stripping liquid composition

[0046] First solvent

[0047] The first solvent according to the present invention can improve the stripping force and solubility for the photoresist layer, and by excluding the use of chemicals harmful to humans and the environment, it can achieve the effects of environmental protection and harmlessness to humans.

[0048] The first solvent according to the present invention is a mixed solvent of two or more kinds, which includes at least one solvent with a pKa greater than or equal to 15. Specifically, if the above first solvent does not include at least one solvent with a pKa greater than or equal to 15, the stripping force for the photoresist layer will decrease, resulting in the residue of the photoresist layer, thus leading to problems such as a decrease in yield or a decrease in the reliability of the device.

[0049] In some embodiments of the present invention, the number of carbon atoms of the above solvent with a pKa greater than or equal to 15 can be 2 to 6, 2 to 5, or 2 to 4. Specifically, it can be 2, 3, or 4. According to some embodiments of the present invention, by making the number of carbon atoms of the above solvent with a pKa greater than or equal to 15 satisfy the above range, the boiling point of the above solvent with a pKa greater than or equal to 15 can be adjusted, thereby realizing a stripping liquid composition that will not volatilize at the stripping process temperature. In some examples, the temperature of the above stripping process can be 50 °C to 70 °C.

[0050] In some embodiments of the present invention, the boiling point of the solvent with a pKa greater than or equal to 15 may be above 170°C and below 290°C. Specifically, the boiling point of the solvent with a pKa greater than or equal to 15 may be above 170°C, above 175°C, above 180°C, above 185°C or above 189°C, and may be below 199°C, below 200°C, below 210°C, below 220°C, below 230°C, below 240°C, below 250°C, below 260°C, below 270°C, below 280°C, below 285°C or below 290°C. For example, the boiling point of the solvent with a pKa greater than or equal to 15 may be from 170°C to 290°C, specifically, from 175°C to 285°C. According to some embodiments of the present invention, by making the solvent with a pKa greater than or equal to 15 satisfy the above numerical range, a stripping liquid composition that does not volatilize at the stripping process temperature can be achieved, thereby achieving a stripping liquid composition with excellent stripping persistence.

[0051] In some examples, the solvent with a pKa greater than or equal to 15 is not particularly limited and may be a solvent capable of increasing the stripping force and solubility of the photoresist layer. Specifically, it may contain at least one selected from the group consisting of N-ethylformamide, dimethyl sulfoxide and sulfolane.

[0052] In some embodiments of the present invention, at least one of the two or more first solvents may contain one or more nitrogen atoms in the molecule. Specifically, at least one of the two or more first solvents may be a solvent with a pKa greater than or equal to 15. According to some embodiments of the present invention, by making at least one of the two or more first solvents have a pKa greater than or equal to 15 and contain one or more nitrogen atoms in the molecule, the viscosity of the stripping liquid composition can be further reduced, thereby effectively preventing an increase in the defect rate of the substrate due to the stripping liquid composition or the rinsing liquid (e.g., deionized water) on the substrate flowing to other areas when the substrate moves between the stripping area and the rinsing area.

[0053] In some embodiments of the present invention, the first solvent may further comprise a solvent having a pKa less than 15. For example, the solvent having a pKa less than 15 is not particularly limited and may specifically comprise at least one selected from the group consisting of N,N-diethylformamide, 1,2-dimethylimidazole, N,N-diethylacetamide, and γ-butyrolactone. According to some embodiments of the present invention, by further comprising a solvent having a pKa less than 15 in the first solvent, the viscosity and evaporation amount of the stripping liquid composition can be effectively controlled, and the dissolution power for the photoresist layer can be further improved.

[0054] In some embodiments of the present invention, based on the total weight of the stripping liquid composition, the content of the first solvent may be 30% by weight or more and 60% by weight or less. Specifically, based on the total weight of the stripping liquid composition, the content of the first solvent may be 30% by weight or more, 35% by weight or more, 40% by weight or more, 45% by weight or more, 50% by weight or more, or 55% by weight or more, or may be 35% by weight or less, 40% by weight or less, 45% by weight or less, 50% by weight or less, 55% by weight or less, or 60% by weight or less. Specifically, it may be any one or more of the above lower limits and any one or less of the above upper limits. For example, based on the total weight of the stripping liquid composition, the content of the first solvent may be 30% by weight to 60% by weight, specifically, it may be 30% by weight to 55% by weight, 35% by weight to 55% by weight. According to some embodiments of the present invention, by making the content of the first solvent satisfy the above range, the viscosity and evaporation amount of the stripping liquid composition can be effectively controlled, and the dissolution power for the photoresist layer can be further improved.

[0055] Second solvent

[0056] The second solvent according to the present invention can further improve the rinsing power, so that no residues or impurities are left during the process of cleaning with deionized water after the photoresist layer is stripped. Generally, when the photoresist layer accumulates, the hydrophilicity of the substrate surface will relatively decrease, resulting in the problem of residues or impurities remaining on the substrate surface. According to one aspect of the present invention, by including the second solvent in the stripping liquid composition, the hydrophilicity of the stripping liquid composition can be improved, so that even when the photoresist layer accumulates, the content of residues or impurities on the substrate surface can be minimized.

[0057] The second solvent according to the present invention is a mixed solvent of two or more kinds, which may include at least one solvent with a pKa less than 15. Specifically, two or more kinds may all include solvents with a pKa less than 15. Specifically, if the above-mentioned second solvent does not include at least one solvent with a pKa less than 15, the hydrophilicity of the substrate surface may be relatively reduced, resulting in problems such as residues or impurities remaining on the substrate surface. In addition, by making the above-mentioned second solvent include two or more solvents with a pKa less than 15, the hydrophilicity of the stripping liquid composition can be further improved, thereby further improving the rinsing force.

[0058] In some embodiments of the present invention, the above-mentioned second solvent may include a first co-solvent having one or more ether groups and one hydroxyl group and a second co-solvent containing two or more hydroxyl groups in the molecule. Specifically, one or more ether groups contained in the above-mentioned first co-solvent can improve the dissolving power for the photoresist material, and one hydroxyl group contained in the above-mentioned first co-solvent and two or more hydroxyl groups in the molecule contained in the above-mentioned second co-solvent can improve the hydrophilicity of the stripping liquid composition. Thus, even when the photoresist layer accumulates, the content of residues or impurities on the substrate surface can be minimized. According to some embodiments of the present invention, by making the above-mentioned second solvent include a first co-solvent having one or more ether groups and one hydroxyl group and a second co-solvent containing two or more hydroxyl groups in the molecule, while improving the stripping force, cleaning force, and persistence of the stripping performance for the photoresist layer, the efficiency of the rinsing process can be further improved.

[0059] In some examples, the above-mentioned first co-solvent is not particularly limited. Specifically, it may include at least one selected from the group consisting of diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol butyl ether, diethylene glycol propyl ether, tripropylene glycol methyl ether, and dipropylene glycol methyl ether.

[0060] In some examples, the above-mentioned second co-solvent is not particularly limited. Specifically, it may include at least one selected from the group consisting of diethylene glycol, ethylene glycol, propylene glycol, 1,3-butanediol, triethylene glycol, and tetraethylene glycol.

[0061] In some embodiments of the present invention, based on the total weight of the above-mentioned stripping liquid composition, the content of the above-mentioned first co-solvent may be 25% by weight to 65% by weight, and the content of the above-mentioned second co-solvent may be more than 5% by weight and less than 45% by weight.

[0062] Specifically, based on the total weight of the above-mentioned stripping liquid composition, the content of the above-mentioned first secondary solvent can be 25% by weight or more, 30% by weight or more, 35% by weight or more, 40% by weight or more, 45% by weight or more, 50% by weight or more, 55% by weight or more, or 60% by weight or more, or can be 30% by weight or less, 35% by weight or less, 40% by weight or less, 45% by weight or less, 50% by weight or less, 55% by weight or less, 60% by weight or less, or 65% by weight or less. Specifically, it can be any one or more of the above-mentioned multiple lower limits and any one or less of the above-mentioned multiple upper limits. For example, based on the total weight of the above-mentioned stripping liquid composition, the content of the above-mentioned first secondary solvent can be 25% to 55% by weight or 30% to 55% by weight.

[0063] Specifically, based on the total weight of the above-mentioned stripping liquid composition, the content of the above-mentioned second secondary solvent can be 5% by weight or more or 10% by weight or more, and can be 15% by weight or less, 20% by weight or less, 25% by weight or less, 30% by weight or less, 35% by weight or less, 40% by weight or less, or less than 45% by weight. For example, based on the total weight of the above-mentioned stripping liquid composition, the content of the above-mentioned second secondary solvent can be 5% to 30% by weight, 5% to 25% by weight, or 5% to 10% by weight.

[0064] According to some embodiments of the present invention, by making the contents of the above-mentioned first secondary solvent and the above-mentioned second secondary solvent satisfy the above numerical range based on the total weight of the above-mentioned stripping liquid composition, the stripping force, cleaning force, and persistence of the stripping performance on the photoresist layer can be improved, and at the same time, the efficiency of the rinsing process can be further increased.

[0065] In some embodiments of the present invention, based on the total weight of the above-mentioned stripping liquid composition, the content of the above-mentioned second solvent can be 35% by weight or more, 40% by weight or more, 45% by weight or more, 50% by weight or more, or 55% by weight or more, and can be 60% by weight or less, 65% by weight or less, 70% by weight or less, 75% by weight or less, 80% by weight or less, 85% by weight or less, or 90% by weight or less. Specifically, it can be 35% to 90% by weight, 35% to 70% by weight, or 38% to 68% by weight. According to some embodiments of the present invention, by making the content of the above-mentioned second solvent satisfy the above numerical range based on the total weight of the above-mentioned stripping liquid composition, the hydrophilicity and viscosity of the stripping liquid composition can be adjusted to an appropriate level, so that even when the photoresist layer accumulates, the content of residues or impurities on the substrate surface can be minimized.

[0066] Amine compound

[0067] The amine compound according to the present invention can decompose the bond of the polymer matrix contained in the modified photoresist layer modified by at least one of heat, exposure (light), development, and etching.

[0068] The amine compound according to the present invention contains two or more different amine compounds. If the above amine compound consists of only more than one kind, it may cause problems such as metal film corrosion, or a decrease in stability over time due to high reactivity, or a decrease in cleaning power due to high viscosity.

[0069] In some embodiments of the present invention, the above amine compound may contain a chain amine and a cyclic amine. Specifically, the above chain amine refers to a compound that does not contain a ring in the molecule and contains at least one primary amine, secondary amine, or tertiary amine group, and the above cyclic amine refers to a compound that contains at least one primary amine, secondary amine, or tertiary amine group inside and / or outside the ring. According to some embodiments of the present invention, by making two or more amine compounds contain a chain amine and a cyclic amine, even when the stripping liquid composition is recycled and used for a long time, the persistence and stability of the stripping performance of the stripping liquid composition can still be improved.

[0070] In some examples, the above chain amine is not particularly limited. Specifically, it may include at least one selected from the group consisting of monoethanolamine, ethylenediamine, 2-(2-aminoethoxy)ethanol, 2-(2-aminoethylamino)ethanol, monoisopropanolamine, diethanolamine, 3,3'-iminodipropylamine, N-methylethanolamine, and triethanolamine.

[0071] In some examples, the above cyclic amine is not particularly limited. Specifically, it may include at least one selected from the group consisting of 1-(2-hydroxyethyl)piperazine, 1-(2-aminoethyl)piperazine, 1-phenylpiperazine, N-(3-aminopropyl)morpholine, 2-methylpiperazine, 1-methylpiperazine, 1-amino-4-methylpiperazine, 1-(2-hydroxyethyl)-4-methylpiperazine, and 1-benzylpiperazine.

[0072] In some embodiments of the present invention, the above amine compound may independently contain one or more hydroxyl groups in the molecule. According to some embodiments of the present invention, by making the above amine compound independently contain one or more hydroxyl groups in the molecule, the water solubility can be improved while reducing the corrosiveness, thereby further improving the efficiency of the rinsing process.

[0073] In some examples, the amine compound containing one or more hydroxyl groups in the molecule is not particularly limited. Specifically, it may include at least one selected from the group consisting of monoethanolamine, 2-(2-aminoethoxy)ethanol, 2-(2-aminoethylamino)ethanol, diethanolamine, N-methylethanolamine, triethanolamine, 1-(2-hydroxyethyl)piperazine, and 1-(2-hydroxyethyl)-4-methylpiperazine.

[0074] In some embodiments of the present invention, based on the total weight of the above-described stripping liquid composition, the content of the above amine compound may be 2 wt% or more, 3 wt% or more, 4 wt% or more, or 5 wt% or more, and may be 6 wt% or less. More specifically, it may be 2 wt% to 6 wt% or 2 wt% to 5 wt%. According to some embodiments of the present invention, by making the content of the above amine compound satisfy the above numerical range based on the total weight of the above stripping liquid composition, the corrosion of the metal wiring can be effectively inhibited while further improving the stripping performance of the photoresist layer.

[0075] In some embodiments of the present invention, based on the total weight of the above-described stripping liquid composition, the content of the above cyclic amine may be 1 wt% or more and 3 wt% or less, while the content of the above chain amine may be 1 wt% or more and 3 wt% or less, or 1 wt% or more and 2 wt% or less. In some embodiments of the present invention, by adjusting the contents of the above cyclic amine and chain amine to the above numerical ranges, the corrosion of the metal wiring can be effectively inhibited while further improving the stripping performance of the photoresist layer.

[0076] Other components

[0077] In some embodiments of the present invention, at least one additive selected from a preservative and a stripping promoter may be further included.

[0078] The preservative according to the present invention can effectively prevent the corrosion of the metal wiring. In some examples, the above preservative is not particularly limited. Specifically, it may include azole compounds such as benzotriazole, methyl gallate, methyl tolyltriazole, 2,2'-[[[benzotriazolyl]methyl]imino]diethanol, 2,2'-[[[methyl-1H-benzotriazol-1-yl]methyl]imino]dimethanol, 2,2'-[[[ethyl-1H-benzotriazol-1-yl]methyl]imino]diethanol, 2,2'-[[[methyl-1H-benzotriazol-1-yl]methyl]imino]dicarboxylic acid, 2,2'-[[[methyl-1H-benzotriazol-1-yl]methyl]imino]dimethylamine, 2,2'-[[[amine-1H-benzotriazol-1-yl]methyl]imino]diethanol, etc.

[0079] The stripping promoter according to the present invention can further improve the decomposition ability of the binding to the polymer matrix contained in the modified photoresist layer. In some examples, the above stripping promoter may include at least one selected from the group consisting of the compounds represented by the following Chemical Formula 1 and Chemical Formula 2.

[0080] [Chemical Formula 1]

[0081]

[0082] [Chemical Formula 2]

[0083]

[0084] In the above Chemical Formula 1, R may be an alkyl group having 1 to 4 carbon atoms, and R' may be a hydroxyalkyl group (alkan ol) having 1 to 10 carbon atoms. In Chemical Formula 2, R' may be an alkyl group or a hydroxyalkyl group (alkan ol) having 1 to 10 carbon atoms.

[0085] In some examples, the content of the above additive is not particularly limited and can be appropriately adjusted according to the purpose. Specifically, based on the total weight of the above stripping liquid composition, the content of the above additive may be 10 wt% or less, 9 wt% or less, 8 wt% or less, 7 wt% or less, 6 wt% or less, 5 wt% or less, 4 wt% or less, 3 wt% or less, 2 wt% or less, or 1 wt% or less.

[0086] Physical properties of the stripping liquid composition

[0087] In some embodiments of the present invention, the change rate of the contact angle of the above stripping liquid composition with respect to the IGZO substrate at 25°C may be 15% or less, specifically, it may be 10% or less, compared to the fresh liquid. The measurement method of the above contact angle change rate is as follows: a sample having a photoresist layer formed on one side of the IGZO substrate is immersed in the stripping liquid composition for 1 minute, then rinsed with ultrapure water sprayed for 30 seconds and dried. Ultrapure water is dropped on the surface of the sample after the above stripping process, and then the change rate of the contact angle compared to the fresh liquid is measured with a contact angle measuring instrument at 25°C, so as to be able to perform analysis. The above fresh liquid refers to the state before adding the photoresist material to the stripping liquid composition, that is, it may mean the stripping liquid composition without the photoresist material.

[0088] The viscosity of the stripping liquid composition according to the present invention at 50°C may be less than 4.0 cP, less than 3.0 cP, or 2.0 cP or less. Specifically, it may be 2.0 cP or more and less than 4.0 cP, or 2.0 cP or more and 3.0 cP or less. Specifically, when the viscosity of the above stripping liquid composition satisfies the above numerical range, it effectively prevents the increase in the defect rate of the substrate caused by the stripping liquid composition or the rinsing liquid (e.g., deionized water) on the substrate flowing to other areas when the substrate moves between the stripping area and the rinsing area.

[0089] In some embodiments of the present invention, the evaporation amount of the above stripping liquid composition may be 10% or less, or 5% or less. The evaporation amount of the above stripping liquid composition refers to the weight change rate of the above stripping liquid composition before and after heating the above stripping liquid composition to 50 °C for 24 hours.

[0090] In some embodiments of the present invention, when the metal substrate is Cu / MoTi, the amount of metal ions dissolved after immersing the above metal substrate in the above stripping liquid composition may be 100 ppb or less, 90 ppb or less, 70 ppb or less, 50 ppb or less, 40 ppb or less, 30 ppb or less, or 20 ppb or less. Among them, the amount of dissolved metal ions may vary depending on the type of metal substrate.

[0091] Hereinafter, embodiments of the present invention will be described in more detail so that those skilled in the art can easily implement them, but this is only an example, and the scope of the present invention is not limited to the following content. Unless otherwise clearly stated to the contrary, the features described in one embodiment can be combined with other embodiments.

[0092] [Preparation Example: Preparation of Stripping Liquid Composition]

[0093] Prepare stripping liquid compositions having the compositions according to Tables 1 to 6 below, respectively. At this time, the unit of each composition in Tables 1 to 6 below is weight %.

[0094] In addition, the pKa values of the first solvent and the second solvent in Tables 1 to 6 below are the results measured using a pH meter under the analysis conditions at 25 °C.

[0095] Table 1

[0096]

[0097]

[0098] Table 2

[0099]

[0100] Table 3

[0101]

[0102]

[0103] Table 4

[0104]

[0105] Table 5

[0106]

[0107]

[0108] Table 6

[0109]

[0110]

[0111] [Experimental Example: Performance Evaluation of Stripping Liquid Composition]

[0112] The performance of the stripping liquid composition of the above Preparation Examples was evaluated by the following evaluation methods and criteria, and the results are listed in Tables 7 to 12 respectively.

[0113] 1) Measurement of Contact Angle Change Rate

[0114] Evaluation Method:

[0115] A sample with a photoresist layer formed on one side of an IGZO substrate was immersed in the stripping liquid composition (100 g) of the above Preparation Example for 1 minute. Subsequently, ultrapure water (2 μL) was dropped onto the surface of the sample after the above stripping process, and the contact angle change rate compared with the fresh liquid was measured at 25°C using a contact angle measuring instrument (DSA1005 of KRUSS company), and the evaluation was carried out according to the following criteria.

[0116] Specifically, in the following evaluation criteria, the fresh liquid refers to the state before adding the photoresist material to the stripping liquid composition, that is, the stripping liquid composition without the photoresist material, and the content of the photoresist material in the stripping liquid composition containing the photoresist material is adjusted to 0.5% by weight of the total weight of the stripping liquid composition. At this time, the lower the contact angle change rate of the stripping liquid composition containing the photoresist material compared with the fresh liquid, the relatively higher the degree of hydrophilicity retention on the sample surface and the more excellent the persistence of the stripping performance.

[0117] Evaluation Criteria:

[0118] ◎: When the contact angle change rate of the stripping liquid composition containing the photoresist material is less than or equal to 10% compared with the fresh liquid

[0119] ○: When the contact angle change rate of the stripping liquid composition containing the photoresist material is greater than 10% and less than or equal to 15% compared with the fresh liquid

[0120] △: When the contact angle change rate of the stripping liquid composition containing the photoresist material is greater than 15% and less than or equal to 20% compared with the fresh liquid

[0121] X: When the contact angle change rate of the stripping liquid composition containing the photoresist material is greater than 20% compared with the fresh liquid

[0122] 2) Viscosity of the stripping liquid composition

[0123] Evaluation method:

[0124] Measure the viscosity of the stripping liquid composition prepared in the above Preparation Example at 50 °C using a viscometer (Z439 Viscometer from Cannon).

[0125] Evaluation criteria:

[0126] ◎: When the viscosity of the stripping liquid composition at the process temperature (50 °C) is 2.0 cP or less

[0127] ○: When the viscosity of the stripping liquid composition at the process temperature (50 °C) is greater than 2.0 cP and less than or equal to 3.0 cP

[0128] △: When the viscosity of the stripping liquid composition at the process temperature (50 °C) is greater than 3.0 cP and less than 4.0 cP

[0129] X: When the viscosity of the stripping liquid composition at the process temperature (50 °C) is greater than or equal to 4.0 cP

[0130] 3) PR solubility

[0131] Evaluation method:

[0132] Add photoresist solid (10 g) to the stripping liquid composition (100 mL) prepared in the above Preparation Example heated to 50 °C. Here, the above photoresist solid is prepared by heating the photoresist-forming composition at 150 °C for 24 hours. Filter the stripping liquid composition added with the above photoresist solid using filter paper, and measure the filtration time until there is no liquid residue in the solution above the filter paper. At this time, the higher the solubility of the photoresist solid, the more excellent the persistence of the stripping performance of the stripping liquid composition.

[0133] Evaluation criteria:

[0134] ◎: When the filtration time is less than or equal to 30 seconds

[0135] ○: When the filtration time is greater than 30 seconds and less than or equal to 60 seconds

[0136] △: When the filtration time is greater than 60 seconds and less than or equal to 120 seconds

[0137] X: When the filtration time is greater than 120 seconds

[0138] 4) Volatile content

[0139] Evaluation method:

[0140] The stripping liquid composition of the above Preparation Example was heated at 50°C for 24 hours, and the evaporation amount of the stripping liquid composition was calculated by measuring the weight change rate of the stripping liquid composition before and after heating. The lower the evaporation amount of the stripping liquid composition, the more excellent its compositional stability over time.

[0141] Evaluation criteria:

[0142] ◎: The evaporation amount is less than or equal to 5%

[0143] ○: The evaporation amount is greater than 5% and less than or equal to 10%

[0144] △: The evaporation amount is greater than 10% and less than or equal to 20%

[0145] X: The evaporation amount is greater than 20%

[0146] 5) PR stripping force and modified PR stripping force

[0147] Evaluation method:

[0148] A substrate having an unmodified photoresist layer (thickness: 1 μm) or a photoresist layer (thickness: 1 μm) modified by a heat treatment process at 180°C formed on one surface of a glass substrate (thickness: 0.5 cm) was immersed in the stripping liquid composition (100 g) of the above Preparation Example heated to 50°C, and then the time required for complete stripping and removal of the above unmodified or modified photoresist layer was measured.

[0149] Evaluation criteria:

[0150] ◎: When the time for complete removal of the unmodified or modified photoresist layer and foreign matter is less than or equal to 60 seconds

[0151] ○: When the time for complete removal of the unmodified or modified photoresist layer and foreign matter is greater than 60 seconds and less than or equal to 90 seconds

[0152] △: When the time for complete removal of the unmodified or modified photoresist layer and foreign matter is greater than 90 seconds and less than or equal to 120 seconds

[0153] X: When the time for complete removal of the unmodified or modified photoresist layer and foreign matter is greater than 120 seconds

[0154] 6) Metal corrosion

[0155] Evaluation method:

[0156] After immersing a Cu / MoTi metal substrate in a mixture prepared by mixing the stripping liquid composition of the above Preparation Example and deionized water at a weight ratio of 1:9 for 1 minute, the dissolution amount of metal ions contained in the above stripping liquid composition was measured by Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). The lower the dissolution amount of metal ions, it can mean that the metal substrate is not damaged and the device performance is more excellent. The dissolution amount of metal ions described here is the total dissolution amount of the contents of copper ions, molybdenum ions and titanium ions.

[0157] Evaluation criteria:

[0158] ◎: When the dissolution amount of metal ions is less than or equal to 20 ppb

[0159] ○: When the dissolution amount of metal ions is greater than 20 ppb and less than or equal to 50 ppb

[0160] △: When the dissolution amount of metal ions is greater than 50 ppb and less than or equal to 100 ppb X: When the dissolution amount of metal ions is greater than 100 ppb

[0161] Table 7

[0162] Classification Contact angle change Viscosity PR solubility Volatilization amount PR stripping force Modified PR stripping force Metal corrosion Example 1 ◎ ◎ ◎ ◎ ◎ ◎ ○ Example 2 ◎ ◎ ◎ ◎ ◎ ◎ ○ Example 3 ◎ ◎ ◎ ◎ ◎ ◎ ○ Example 4 ◎ ○ ◎ ◎ ◎ ◎ ○ Example 5 ◎ ◎ ◎ ◎ ◎ ◎ ○ Example 6 ◎ ◎ ◎ ◎ ◎ ◎ ○ Example 7 ◎ ◎ ◎ ◎ ◎ ◎ ○ Example 8 ◎ ◎ ◎ ◎ ◎ ◎ ○ Example 9 ◎ ◎ ◎ ◎ ◎ ◎ ○ Example 10 ◎ ○ ◎ ◎ ◎ ◎ ○ Example 11 ◎ ◎ ◎ ◎ ◎ ◎ ○ Example 12 ○ ○ ◎ ◎ ◎ ◎ ○ Example 13 ◎ ◎ ◎ ◎ ◎ ◎ ○ Example 14 ◎ ◎ ◎ ◎ ◎ ◎ ○ Example 15 ◎ ◎ ◎ ◎ ◎ ◎ ○ Example 16 ◎ ○ ◎ ◎ ◎ ◎ ○ Example 17 ◎ ◎ ◎ ◎ ◎ ◎ ○ Example 18 ◎ ○ ◎ ◎ ◎ ◎ ○ Example 19 ◎ ◎ ◎ ◎ ◎ ◎ ○ Example 20 ◎ ◎ ◎ ◎ ◎ ◎ ○ Example 21 ◎ ◎ ◎ ◎ ◎ ◎ ○ Example 22 ◎ ○ ◎ ◎ ◎ ◎ ○ Example 23 ◎ ◎ ◎ ◎ ◎ ◎ ○ Example 24 ○ ○ ◎ ◎ ◎ ◎ ○ Example 25 △ ◎ ◎ ◎ ◎ ◎ ○ Example 26 ◎ △ ◎ ◎ ◎ ◎ ○ Example 27 △ ◎ ◎ ◎ ◎ ◎ ○ Example 28 △ ◎ ◎ ◎ ◎ ◎ ○ Example 29 △ ◎ ◎ ◎ ◎ ◎ ○ Example 30 ◎ △ ◎ ◎ ◎ ◎ ○

[0163] Table 8

[0164]

[0165]

[0166] Table 9

[0167] Classification Contact angle change Viscosity PR solubility Volatilization amount PR stripping force Modified PR stripping force Metal corrosion Example 31 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 32 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 33 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 34 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 35 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 36 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 37 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 38 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Example 39 ◎ ○ ◎ ◎ ◎ ◎ ◎ Example 40 ◎ ○ ◎ ◎ ◎ ◎ ◎ Example 41 ◎ ○ ◎ ◎ ◎ ◎ ◎ Example 42 ◎ △ ◎ ◎ ◎ ◎ ◎

[0168] Table 10

[0169] Classification Contact angle change Viscosity PR solubility Volatilization amount PR stripping force Modified PR stripping force Metal corrosion Comparative Example 15 ◎ ◎ X △ X X ◎ Comparative Example 16 ◎ ◎ △ △ △ X ◎ Comparative Example 17 ◎ ◎ X △ X X ◎ Comparative Example 18 ◎ ◎ △ △ △ X ◎ Comparative Example 19 ◎ ◎ X △ X X ◎ Comparative Example 20 ◎ ◎ △ △ △ X ◎ Comparative Example 21 ◎ ◎ X △ X X ◎ Comparative Example 22 ◎ ◎ △ △ △ X ◎ Comparative Example 23 ◎ ◎ X △ X X ◎ Comparative Example 24 ◎ ◎ △ △ △ X ◎ Comparative Example 25 ◎ ○ X △ X X ◎ Comparative Example 26 ◎ ○ △ △ △ X ◎ Comparative Example 27 ◎ ○ X △ X X ◎ Comparative Example 28 ◎ ○ △ △ △ X ◎

[0170] Table 11

[0171]

[0172]

[0173] Table 12

[0174] Classification Contact angle change Viscosity PR solubility Volatilization amount PR stripping force Modified PR stripping force Metal corrosion Comparative Example 29 ◎ ◎ ◎ ◎ ○ X ◎ Comparative Example 30 ◎ ◎ ◎ ◎ ◎ △ ◎ Example 59 ◎ ◎ ◎ ◎ ◎ ◎ △ Example 60 ◎ ◎ ◎ ◎ ◎ ◎ △ Example 61 ◎ ◎ ◎ ◎ ◎ ◎ △ Example 62 ◎ ◎ ◎ ◎ ◎ ◎ △ Example 63 ◎ ◎ ◎ ◎ ◎ ◎ △ Example 64 ◎ ◎ ◎ ◎ ◎ ◎ △ Example 65 ◎ ◎ ◎ ◎ ◎ ◎ △ Example 66 ◎ ◎ ◎ ◎ ◎ ◎ △

Claims

1. A stripping liquid composition, characterized in that, Comprising: Two or more first solvents, including at least one solvent having a pK a greater than or equal to 15, Two or more second solvents, including at least one solvent having a pK a less than 15, and Two or more amine compounds; The viscosity of the above-mentioned stripping liquid composition at 50 °C is less than 4.0 cP.

2. The stripping liquid composition according to claim 1, characterized in that The above pK a The number of carbon atoms of the solvent that is greater than or equal to 15 is 2 or more and 6 or less.

3. The stripping liquid composition according to claim 1, characterized in that At least one of the above two or more first solvents contains one or more nitrogen atoms in the molecule.

4. The stripping liquid composition according to claim 1, characterized in that The above pK a Solvents having a pK greater than or equal to 15 include at least one selected from the group consisting of N-ethylformamide, dimethyl sulfoxide, and sulfolane.

5. The stripping liquid composition according to claim 1, characterized in that The above two or more first solvents further include a solvent having a pK a less than 15.

6. The stripping liquid composition according to claim 1, characterized in that Based on the total weight of the above-mentioned stripping liquid composition, the content of the above-mentioned first solvent is 30% by weight or more and 60% by weight or less.

7. The stripping liquid composition according to claim 1, characterized in that The above-mentioned second solvent includes: A first co-solvent having at least one ether group and one hydroxyl group; and A second co-solvent having two or more hydroxyl groups in the molecule.

8. The stripping liquid composition according to claim 7, characterized in that The above-mentioned first co-solvent includes at least one selected from the group consisting of diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol butyl ether, diethylene glycol propyl ether, tripropylene glycol methyl ether, and dipropylene glycol methyl ether.

9. The stripping liquid composition according to claim 7, characterized in that The above-mentioned second co-solvent includes at least one selected from the group consisting of diethylene glycol, ethylene glycol, propylene glycol, 1,3-butanediol, triethylene glycol, and tetraethylene glycol.

10. The stripping liquid composition according to claim 7, characterized in that Based on the total weight of the above-mentioned stripping liquid composition, the content of the above-mentioned first co-solvent is 25% by weight or more and 65% by weight or less, Based on the total weight of the above-mentioned stripping liquid composition, the content of the above-mentioned second co-solvent is 5% by weight or more and less than 45% by weight.

11. The stripping liquid composition according to claim 1, characterized in that Based on the total weight of the above-mentioned stripping liquid composition, the content of the above-mentioned second solvent is 35% by weight or more and 90% by weight or less.

12. The stripping liquid composition according to claim 1, characterized in that The above-mentioned amine compound includes aliphatic amine and cyclic amine.

13. The stripping liquid composition according to claim 12, characterized in that The above-mentioned aliphatic amine includes at least one selected from the group consisting of monoethanolamine, ethylenediamine, 2-(2-aminoethoxy)ethanol, 2-(2-aminoethylamino)ethanol, monoisopropanolamine, diethanolamine, 3,3'-iminodipropylamine, N-methylethanolamine, and triethanolamine.

14. The stripping liquid composition according to claim 12, characterized in that The above-mentioned cyclic amine includes at least one selected from the group consisting of 1-(2-hydroxyethyl)piperazine, 1-(2-aminoethyl)piperazine, 1-phenylpiperazine, N-(3-aminopropyl)morpholine, 2-methylpiperazine, 1-methylpiperazine, 1-amino-4-methylpiperazine, 1-(2-hydroxyethyl)-4-methylpiperazine, and 1-benzylpiperazine.

15. The stripping liquid composition according to claim 1, characterized in that Each of the above amine compounds independently contains one or more hydroxyl groups in the molecule.

16. The stripping liquid composition according to claim 1, characterized in that Based on the total weight of the above stripping liquid composition, the content of the above amine compound is 2% by weight or more and 6% by weight or less.

17. The stripping liquid composition according to claim 1, characterized in that The stripping liquid composition further comprises at least one additive selected from a preservative and a stripping promoter.

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