Stripping liquid composition

Abstract

The invention discloses a stripping liquid composition which is excellent in stripping performance of resist patterns and price competitiveness. According to one aspect, there is provided a stripper composition comprising: greater than 3% by weight and less than 20% by weight of an alkyl alcohol; more than 0.5 wt% and less than 25 wt% of an alkanolamine; hydroxide or acetate; and water; the weight ratio of the hydroxide to the alkanolamine or the weight ratio of the acetate to the alkanolamine is 1: 3 to 1: 400.

Description

Technical Field

[0001] This invention relates to a stripping liquid composition. Background Technology

[0002] The circuitry of an organic light-emitting diode (OLED) or liquid crystal display device has an extremely fine structure. This fine-structured circuitry can be formed by uniformly coating an insulating or metal film formed on a substrate with a composition for forming a resist, thereby forming a resist layer. The resist layer is then cured at an appropriate temperature, and a resist pattern with a predetermined pattern is formed by exposing and developing the resist layer.

[0003] At this point, the stripping solution composition used to remove the aforementioned resist patterns needs to possess excellent stripping properties against the resist patterns, while also ensuring that no undissolved resist material or particles 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 proportions of its components, this stripping solution composition exhibits significant variations in its resistance to resist materials, stripping performance, corrosion resistance to the metal film, process complexity, environmental stability, and workability. Therefore, research on the relevant compounds and proportions is ongoing. Summary of the Invention

[0004] Technical issues

[0005] According to one aspect of the present invention, a stripping liquid composition is provided, which has excellent stripping performance and cleaning ability against etchant patterns, effectively prevents corrosion of metal films, and can improve the initial solubility of etchant materials.

[0006] According to another aspect of the invention, a stripping liquid composition is provided that achieves stripping performance equivalent to or higher than that of existing organic stripping liquid compositions.

[0007] According to another aspect of the present invention, a stripping fluid composition with excellent price competitiveness is provided.

[0008] According to another aspect of the present invention, a method for removing resist patterns using the above-described stripping liquid composition is provided.

[0009] The objectives of this invention are not limited to those stated above. Other objectives and advantages of this invention not mentioned herein can be understood through the following description and through embodiments of the invention. Furthermore, it will be readily understood that the objectives and advantages of this invention can be achieved through the means and combinations thereof described in the specification.

[0010] Technical solution

[0011] According to a first aspect of the invention, a stripping liquid composition is provided, comprising: more than 3% by weight and less than 20% by weight of an alkyl alcohol; more than 0.5% by weight and less than 25% by weight of an alkanolamine; a hydroxide or an acetate; and water; wherein the weight ratio of the hydroxide to the alkanolamine or the weight ratio of the acetate to the alkanolamine is 1:3 to 1:400.

[0012] According to a second aspect of the invention, the alkyl alcohol may include a monohydric alcohol having at least one ether group.

[0013] According to a third aspect of the present invention, in the first or second aspect described above, the alkyl alcohol may include at least one selected from the group consisting of ethanol, 1-propanol, 1-butanol, 2-butanol, isopropanol, tetrahydrofurfuryl alcohol, propylene glycol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monobutyl ether, and glycerol.

[0014] According to a fourth aspect of the invention, in any of the first to third aspects described above, the content of the alkanolamine may be from 10% to 20% by weight, based on the total weight of the stripping liquid composition.

[0015] According to a fifth aspect of the invention, in any of the first to fourth aspects described above, the alkanolamine may include at least one hydroxyl group and a secondary amino group.

[0016] According to a sixth aspect of the present invention, in any one of the first to fifth aspects, the alkanolamine may include at least one selected from the group consisting of N-methylethanolamine, aminoethylethanolamine, monoethanolamine, monoisopropanolamine, 2-amino-2-methyl-1-propanol, 2-methylaminoethanol, 2-(2-aminoethylamino)ethanol and 3-aminopropanolamine.

[0017] According to a seventh aspect of the invention, in any of the first to sixth aspects described above, the content of the hydroxide or the acetate may be greater than 0.03% by weight and less than 7% by weight, based on the total weight of the stripping liquid composition.

[0018] According to an eighth aspect of the invention, in any of the first to seventh aspects described above, the hydroxide may include at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, and combinations thereof.

[0019] According to a ninth aspect of the present invention, in any one of the first to eighth aspects described above, the acetate may include at least one selected from the group consisting of sodium acetate, potassium acetate, magnesium acetate, and calcium acetate.

[0020] According to a tenth aspect of the invention, in any of the first to ninth aspects described above, the water content may be from 50% to 89% by weight, based on the total weight of the stripping liquid composition described above.

[0021] According to the eleventh aspect of the present invention, in any of the first to tenth aspects described above, the weight ratio of the hydroxide to the alkanolamine or the weight ratio of the acetate to the alkanolamine may be from 1:20 to 1:200.

[0022] According to a twelfth aspect of the present invention, in any of the first to eleventh aspects described above, a stripping liquid composition further comprising at least one additive selected from the group consisting of corrosion inhibitors, antioxidants, defoamers and stripping promoters can be provided.

[0023] The solutions described above do not list all the features of the present invention and can be combined with some embodiments described in this specification. The various features of the present invention and the advantages and effects based on these features can be understood in more detail by referring to the specific examples described below.

[0024] Beneficial effects

[0025] According to one aspect of the present invention, a stripping liquid composition can be realized, which has excellent stripping performance and cleaning ability against etchant patterns, while effectively preventing corrosion of metal films and improving the solubility of etchant materials.

[0026] According to another aspect of the invention, a stripping liquid composition can be realized that achieves stripping performance equivalent to or higher than that of existing organic stripping liquid compositions.

[0027] In addition to the effects described above, specific effects of the invention will be described while explaining the specific details of implementing the invention. Furthermore, the effects of the invention are not limited to those described above, and can be readily achieved by the means and combinations thereof described in the specification. Detailed Implementation

[0028] In this specification, unless otherwise explicitly stated, any statement indicating a singular number should be understood to include plural numbers.

[0029] As used herein, “comprising” and / or “including” means the presence of a particular proposed form, step, number, action, component, element and / or group thereof, and does not exclude the presence or addition of more than one other form, step, number, action, component, element and / or group thereof.

[0030] In this specification, "at least one of a, b and c" may include a, b or c alone, or may include a combination of two or more selected from a, b and c.

[0031] When multiple embodiments are described in this specification, each embodiment may be combined unless explicitly stated otherwise. In this case, the effects of the invention can be defined as including the effects produced by each embodiment as well as the effects produced by organically combining each embodiment. For example, even though embodiments 1 and 2 are described independently in this specification, unless the context clearly indicates otherwise, embodiments 1 and 2 may be organically combined with each other, and the effects of the invention may include the effects produced by the combination of embodiments 1 and 2.

[0032] In this document, the term "to" refers to a range of values ​​that include the lower and upper limits specified before or after the term. When multiple values ​​are mentioned as the upper or lower limit of any range, the range described herein can be understood as a range with any one of the mentioned upper limits as its upper limit and any one of the mentioned lower limits as its lower limit. For example, when describing a to b or c to d in the specification, it can be understood as describing a above and below b, a above and below d, c above and below d, or c above and below b.

[0033] When this specification refers to multiple values ​​for the upper or lower limit of any numerical range, the numerical range disclosed herein can be understood as any numerical range with any one of the mentioned upper limit values ​​as its upper limit value and any one of the mentioned lower limit values ​​as its lower limit value. For example, when the specification describes a or above or b or below c or d, it can be understood as describing a or above c, a or above d, b or above c, or b or above d.

[0034] The degree terms used in this paper, such as “about” and “basically”, refer to a reasonable amount of deviation from the term they modify such that the final result is not significantly altered. These terms can be interpreted as including a deviation of at least ±5% or at least ±10%, provided that the deviation does not negate the meaning of the word they modify.

[0035] In this specification, the term "layer" or "film" can include cases where the layer or film forms over the entire area of ​​the observed region, or cases where the layer or film forms only over a portion of the area. For example, the surface of a layer or film can be defined as including flat, uneven, or combinations thereof, or continuous, discontinuous, or combinations thereof. For example, if another component directly above a component is formed of a layer or film, the coverage of the other component over the surface of the first component 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. For example, even if multiple particles form an aggregated structure, it can be defined as a "layer" or "film."

[0036] As used herein, "composition" can refer to a mixture of materials comprising the relevant composition, a reaction product formed from the materials of the composition, or a decomposition product. For example, the content of the materials in the above composition can be measured using gas chromatography. Specifically, the content of the above materials can be analyzed using an Agilent gas chromatograph (product name: Agilent 7890GC, column: HP-5, carrier gas: helium (flow rate: 2.4 mL / min), detector: FID, injection volume: 1 μL, initial temperature: 70 °C / 4.2 min, final temperature: 280 °C / 7.8 min, program rate: 15 °C / min).

[0037] According to one aspect of the present invention, a stripping liquid composition is provided, comprising: more than 3% by weight and less than 20% by weight of an alkyl alcohol; more than 0.5% by weight and less than 25% by weight of an alkanolamine; a hydroxide or an acetate; and water; wherein the weight ratio of the hydroxide to the alkanolamine or the acetate to the alkanolamine is 1:3 to 1:400. According to one aspect of the present invention, by satisfying the organic combination relationship of the above-mentioned components, a stripping force equivalent to or higher than that of conventional organic stripping liquid compositions on resist patterns can be achieved even without the use of organic solvents. According to another aspect of the present invention, by increasing the water content to increase the hydrophilicity of the substrate surface, the problem of resist material foreign matter remaining on the substrate surface after stripping can be easily solved, and a stripping liquid composition with excellent price competitiveness can be achieved.

[0038] The structure of the invention will be described in more detail below.

[0039] 1. Stripping fluid composition

[0040] Alkyl alcohols

[0041] In this specification, "alkyl alcohol" may be defined as a compound comprising a chain and / or cyclic alkyl group and having at least one hydroxyl group bonded to the aforementioned alkyl group. However, alkyl alcohols are defined herein as those without an amino group in order to distinguish them from alkanolamines, which will be described below.

[0042] The alkyl alcohols according to the present invention can improve the peeling performance of the resist material while simultaneously improving the wettability of the stripping fluid composition. Furthermore, the alkyl alcohols according to the present invention can further improve the rinsing ability of the resist material.

[0043] In some embodiments of the present invention, based on the total weight of the stripping liquid composition, the content of the alkyl alcohol can be greater than 3% by weight and less than 20% by weight, 5% to 15% by weight, 7% to 15% by weight, or 10% to 15% by weight. Specifically, it can be 10% to 13% by weight or 13% to 15% by weight. According to some embodiments of the present invention, when the content of the alkyl alcohol is lower than or does not exceed the above-mentioned numerical range, it may lead to a decrease in the stripping performance of the resist pattern and the solubility of the resist solid, while when the content is equal to or higher than the above-mentioned numerical range, corrosion or damage to the metal film may occur.

[0044] In some examples, based on the total weight of the stripping liquid composition, the content of the alkyl alcohol may be 5% or more by weight, 7% or more by weight, or 10% or more by weight, and may be less than 13% by weight, less than 15% by weight, less than 17% by weight, or less than 19% by weight.

[0045] In some embodiments of the present invention, the alkyl alcohol may comprise a monohydric alcohol having one or more ether groups, specifically, a monohydric alcohol having two ether groups. The ether group may be contained in at least one of the chains and / or rings. Specifically, the one or more ether groups can increase the hydrophilicity of the stripping liquid composition, thereby reducing the content of residues and impurities on the substrate surface when resist accumulates, and the monohydric alcohol can further improve the wettability of the stripping liquid composition. According to some embodiments of the present invention, by including a monohydric alcohol having two ether groups in the stripping liquid composition, the solubility of the resist solid and the stripping performance of the resist pattern can be further improved within the limits of preventing metal film corrosion.

[0046] In some embodiments of the present invention, the number of carbon atoms in the alkyl alcohol can be 1 or more and 5 or less; specifically, it can be 2 or more and 5 or less, 3 or more and 5 or less, or 4 or more and 5 or less. According to some embodiments of the present invention, when the number of carbon atoms in the alkyl alcohol meets the above-mentioned numerical range, the solubility of the solid resist and the stripping performance of the resist pattern can be further improved within the limit of preventing metal film corrosion. In some non-limiting examples, the number of carbon atoms in the alkyl alcohol can refer to the number of carbon atoms in chain-like and / or cyclic alkyl groups.

[0047] In some embodiments of the present invention, the molecular weight (molecular weight / carbon number) of the alkyl alcohol relative to the number of carbon atoms can be 20 g / (mol·carbon number) or more, specifically, it can be 20 g / (mol·carbon number) to 31 g / (mol·carbon number), 23 g / (mol·carbon number) to 27 g / (mol·carbon number), 23 g / (mol·carbon number) to 25 g / (mol·carbon number), or 24 g / (mol·carbon number) to 25 g / (mol·carbon number). According to some embodiments of the present invention, when the molecular weight (molecular weight / carbon number) of the alkyl alcohol relative to the number of carbon atoms meets the above-mentioned numerical range, its solubility in water may be increased, thereby further improving the stripping performance of the resist pattern. Alternatively, the molecular weight of the alkyl alcohol can be molar mass.

[0048] In some embodiments of the present invention, the monohydric alcohol having one or more ether groups may comprise a compound represented by the following general formula 1. According to some embodiments of the present invention, the solubility of the resist solid and the stripping performance of the resist pattern can be further improved by the compound represented by the following general formula 1, within the limits of preventing metal film corrosion.

[0049] [General Formula 1]

[0050] HO-R a -OR a -OR b

[0051] In the above general formula 1, R a Each is independently an alkylene group having 1 to 3 carbon atoms, R b It is an alkyl group having 1 to 3 carbon atoms. Here, the two R... a and R b The total number of carbon atoms can be more than 3 and less than 5.

[0052] In some examples, the monohydric alcohol having one or more ether groups is not particularly limited, but specifically, it may include at least one selected from the group consisting of tetrahydrofurfuryl alcohol, diethylene glycol monomethyl ether and diethylene glycol monobutyl ether.

[0053] In some instances, the alkyl alcohols mentioned above are not particularly limited, but specifically, they may include at least one selected from the group consisting of ethanol, 1-propanol, 1-butanol, 2-butanol, isopropanol, tetrahydrofurfuryl alcohol, propylene glycol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monobutyl ether, and glycerol.

[0054] Alkylamine

[0055] In this specification, "alkanolamine" can be defined as a compound containing hydroxyl and amine groups within its molecule.

[0056] The alkanolamines according to the present invention can penetrate into the polymer matrix contained in the resist material, thereby breaking down intramolecular or intermolecular bonds.

[0057] In some embodiments of the present invention, based on the total weight of the stripping liquid composition, the content of the alkanolamine can be greater than 0.5% by weight and less than 25% by weight, 1% to 20% by weight, 3% to 20% by weight, 5% to 20% by weight, 7% to 20% by weight, 10% to 20% by weight, and specifically, 10% to 15% by weight or 15% to 20% by weight. According to some embodiments of the present invention, when the content of the alkanolamine is below or does not exceed the above-mentioned numerical range, problems may arise regarding the stripping performance of the resist pattern and the initial solubility of the resist material; while when the content is equal to or higher than the above-mentioned numerical range, damage or corrosion of the metal film may occur.

[0058] In some examples, based on the total weight of the stripping liquid composition, the content of the alkanolamine can be 1% or more by weight, 3% or more by weight, 5% or more by weight, 7% or more by weight, 10% or more by weight, or 15% or more by weight, and can be less than 17% by weight or less than 20% by weight.

[0059] In some embodiments of the present invention, the alkanolamine may contain one or more hydroxyl groups and secondary amine groups. Specifically, the one or more hydroxyl groups can improve the wettability of the stripping fluid composition, while the secondary amine groups can adjust the reactivity of the alkanolamine to an appropriate level, thereby not only effectively preventing corrosion of the metal film but also achieving long-term stability. Long-term stability here refers to the stability of the performance of the stripping fluid composition during use.

[0060] In some examples, the alkanolamines containing one or more hydroxyl and secondary amino groups are not particularly limited, but specifically, they may include at least one selected from the group consisting of N-methylethanolamine, aminoethylethanolamine, 2-methylaminoethanol and 2-(2-aminoethylamino)ethanol.

[0061] In some examples, the alkanolamines mentioned above are not particularly limited, but specifically, they may include at least one selected from the group consisting of N-methylethanolamine, aminoethylethanolamine, monoethanolamine, monoisopropanolamine, 2-amino-2-methyl-1-propanol, 2-methylaminoethanol, 2-(2-aminoethylamino)ethanol and 3-aminopropanolamine.

[0062] hydroxides or acetates

[0063] In this specification, hydroxides can be defined as salts of hydroxide ions combined with metal cations, and acetates can be defined as salts of acetic acid combined with metal cations. However, the solubility of hydroxides and acetates in water at 20°C can each independently be 1 g / L or more, 10 g / L or more, 100 g / L or more, or 1000 g / L or more. In some non-limiting examples, the aforementioned metal cations can be alkali metal ions or alkaline earth metal ions.

[0064] According to the present invention, the aforementioned hydroxide or acetate can be included in the stripping solution composition, thereby improving the solubility of the resist solid and the stripping performance of the resist pattern.

[0065] In some embodiments of the present invention, based on the total weight of the stripping liquid composition, the content of the hydroxide or acetate can be greater than 0.03% by weight and less than 7% by weight, specifically, it can be from 0.05% by weight to 5% by weight, 0.1% by weight to 5% by weight, 0.1% by weight to 3% by weight, and more specifically, it can be from 0.1% by weight to 1% by weight or 0.2% by weight to 1% by weight. According to some embodiments of the present invention, when the content of the hydroxide or acetate meets the above-mentioned numerical range, the solubility of the resist solid and the stripping performance of the resist pattern can be further improved within the limit of preventing metal film corrosion.

[0066] In some examples, based on the total weight of the stripping liquid composition, the content of the hydroxide can be 0.05% by weight or more, 0.2% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 0.7% by weight or more, or 1% by weight or more, and can be less than 3% by weight, less than 5% by weight, or less than 6% by weight.

[0067] In some examples, based on the total weight of the stripping liquid composition, the content of the acetate can be 0.05% by weight or more, 0.1% by weight or more, or 0.5% by weight or more, and can be less than 1% by weight, less than 3% by weight, or less than 5% by weight.

[0068] In some examples, the aforementioned hydroxide may contain at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, and combinations thereof.

[0069] In some examples, the above-mentioned acetate may include at least one selected from the group consisting of sodium acetate, potassium acetate, magnesium acetate, and calcium acetate.

[0070] water

[0071] The stripping fluid composition according to the invention includes water as a solvent or dispersion medium for dissolving or dispersing the aforementioned components. Furthermore, the water according to the invention is not limited to its role as a solvent or dispersion medium, but can also be a factor in adjusting the stripping performance against corrosion patterns. Moreover, with prolonged use of the water-containing stripping fluid composition, water may be lost through evaporation, resulting in changes in the anti-corrosion performance of the metal film due to variations in the water content of the stripping fluid composition.

[0072] In some embodiments of the present invention, based on the total weight of the stripping liquid composition, the water content can be 50% to 89% by weight, 64% to 89% by weight, 64% to 89% by weight, 64% to 89% by weight, 64% to 88% by weight, 64% to 87% by weight, 64% to 86% by weight, 64% to 85% by weight, 64% to 84% by weight, 64% to 83% by weight, 64% to 82% by weight, 64% to 81% by weight, 64% to 80% by weight, or 64% to 79.9% by weight. According to some embodiments of the present invention, when the water content meets the above-mentioned numerical ranges, even with long-term use, corrosion of the metal film can be effectively prevented, and excellent stripping performance against the resist pattern can be better achieved, while further improving the initial solubility of the resist solid.

[0073] Relationship between components

[0074] In the stripping solution composition according to the present invention, the weight ratio of the hydroxide to the alkanolamine (hydroxide:alkanolamine) or the weight ratio of the acetate to the alkanolamine (acetate:alkanolamine) can be from 1:3 to 1:400, specifically from 1:20 to 1:200. Specifically, when the weight ratio of the hydroxide to the alkanolamine (hydroxide:alkanolamine) or the weight ratio of the acetate to the alkanolamine (acetate:alkanolamine) is below the above-mentioned range, corrosion of the metal film may occur; and when it exceeds the above-mentioned range, the stripping performance and initial dissolution performance against the resist pattern may be reduced.

[0075] Other components

[0076] In some embodiments of the present invention, the above-mentioned stripping fluid composition may further include at least one additive selected from the group consisting of corrosion inhibitors, antioxidants, defoamers and stripping promoters.

[0077] The corrosion inhibitors according to the present invention can effectively prevent corrosion of metal films. In some examples, the corrosion inhibitors may include benzotriazole, methyl gallate, methylbenzotriazole, methyltoluenetriazole, 2,2'-[[[benzotriazole]methyl]imino]diethanol, 2,2'-[[[methyl-1-hydro-benzotriazole-1-yl]methyl]imino]diethanol, 2,2'-[[[ethyl-1-hydro-benzotriazole-1-yl]methyl]imino]diethanol, 2,2'-[[[ [Methyl-1-hydro-benzotriazol-1-yl]methyl]imino]diethanol, 2,2'-[[[methyl-1-hydro-benzotriazol-1-yl]methyl]imino]dicarboxylic acid, 2,2'-[[[methyl-1-hydro-benzotriazol-1-yl]methyl]imino]dimethylamine, 2-mercapto-1-methylimidazolium or 2,2'-[[[amine-1-hydro-benzotriazol-1-yl]methyl]imino]diethanol, etc.

[0078] The antioxidants according to the present invention can effectively prevent the oxidation of metal films. In some examples, the antioxidants are not particularly limited, and specifically may include at least one selected from the group consisting of phenolic antioxidants, amine antioxidants, thiol antioxidants, and phosphine antioxidants.

[0079] The defoamer according to the present invention can remove air bubbles contained in the stripping liquid composition. In some examples, the defoamer is not particularly limited, and specifically, it may include silicone-based defoamers. For example, the silicone-based defoamer may be in the form of a solution, emulsion, self-emulsifying, or solid.

[0080] The release accelerator according to the invention can further enhance the ability to break down the bonding force of the polymer matrix contained in the modified resist pattern. In some examples, the release accelerator may comprise at least one compound selected from the group consisting of compounds represented by the following chemical formulas 1 and 2.

[0081] [Chemical Formula 1]

[0082]

[0083] [Chemical Formula 2]

[0084]

[0085] In the above chemical formula 1, R is 1 to 4 substituents, each independently being a straight-chain or branched alkyl group having 1 to 4 carbon atoms, and R' is independently a hydroxyalkyl (alkyl alcohol) having 1 to 10 carbon atoms. In the above chemical formula 2, R' is independently a straight-chain or branched alkyl group having 1 to 10 carbon atoms, or a hydroxyalkyl (alkyl alcohol) having 1 to 10 carbon atoms.

[0086] In some examples, the content of the above-mentioned additives is not particularly limited and can be appropriately adjusted according to the purpose. Specifically, the content of the above-mentioned additives, based on the total weight of the above-mentioned stripping liquid composition, can be less than 10% by weight, less than 9% by weight, less than 8% by weight, less than 7% by weight, less than 6% by weight, less than 5% by weight, less than 4% by weight, less than 3% by weight, less than 2% by weight, or less than 1% by weight, and can be more than 0.01% by weight and less than any of the above-mentioned upper limits, specifically, it can be more than 0.01% by weight and less than 0.05% by weight, or more than 0.03% by weight and less than 0.04% by weight.

[0087] Physical properties

[0088] In some embodiments of the present invention, 1% by weight of the photoresist solid is added to a stripping liquid composition heated to 50°C, and the mixture is stirred at 600 rpm for 30 minutes. The initial solubility of the photoresist solid relative to the stripping liquid composition is then measured to be 95% by weight or more, 96% by weight or more, 97% by weight or more, 98% by weight or more, or 99% by weight or more. This initial solubility can be a parameter used to determine the stripping efficiency of the photoresist pattern, compared to methods involving stirring for a relatively longer period than 30 minutes. In other words, a higher initial solubility indicates a higher stripping efficiency of the photoresist pattern. According to some embodiments of the present invention, since the initial solubility of the stripping liquid composition meets the above-mentioned numerical range, a stripping liquid composition with higher stripping efficiency can be achieved.

[0089] 2. Method for peeling off resist patterns

[0090] According to some embodiments of the present invention, a method for removing a resist pattern is provided, the method comprising: step (S1), preparing a metal film to be formed on a substrate; step (S2), forming a resist pattern on the metal film; step (S3), removing the resist pattern using a stripping liquid composition according to some embodiments; and step (S4), cleaning the residue of the stripped resist pattern.

[0091] In some examples, the substrate is not particularly limited; specifically, it can be a glass substrate.

[0092] In some examples, the metal film described above can be a single-layer film or a multi-layer film, specifically, it can include at least one selected from the group consisting of Cu, Mo, Al and Ti.

[0093] In some examples, to achieve step (S2) above, a patterning method commonly used in the relevant technical field can be used. For example, step (S2) above may include conventional steps such as coating a composition for forming a resist onto the surface of the metal film, and performing curing, etching, developing, and exposure.

[0094] In some examples, step (S3) above may include immersing the product of step (S2) above in the stripper composition or applying the stripper composition of some embodiments to the resist pattern by spraying.

[0095] When using the stripping liquid composition according to some embodiments of the present invention, the hydrophilicity of the substrate surface can be increased, thereby further improving the process efficiency of cleaning the residue of the stripped resist pattern.

[0096] Example

[0097] Embodiments of the invention will be described in more detail below so that those skilled in the art can readily implement them, but this is merely an example and the scope of the invention is not limited to the following.

[0098] In this specification, the values ​​for the compositions listed in Tables 1 to 3 below are all based on the total weight of the stripping fluid composition. In this case, all the above values ​​are in weight percent.

[0099] [Preparation Example 1: Preparation of the Stripping Liquid Composition]

[0100] Stripping fluid compositions as shown in Table 1 below were prepared. Table 1 below can be divided into Examples 1 to 8 for adjusting hydroxide content, Examples 9 to 13 for adjusting alkyl alcohol content, and Examples 14 to 20 for adjusting alkanolamine content.

[0101] Table 1

[0102]

[0103]

[0104] [Preparation Example 2: Preparation of a stripping liquid composition with a different compound than that in Preparation Example 1]

[0105] Except for changing the hydroxide or alkanolamine to the composition according to Table 2 below, the stripping liquid composition was prepared in the same manner as in Preparation Example 1.

[0106] Table 2

[0107]

[0108]

[0109] [Preparation Example 3: Preparation of a stripping liquid composition with adjusted moisture content]

[0110] The stripping fluid composition was prepared by adjusting the water content according to the composition in Table 3 below. In this case, the composition in Table 3 below is the same as the composition in Table 1 above.

[0111] Table 3

[0112]

[0113]

[0114] [Preparation Example 4: Using acetate instead of hydroxide]

[0115] A stripping liquid composition having the composition according to Table 4 below was prepared.

[0116] Table 4

[0117]

[0118]

[0119] [Experimental Example: Performance Evaluation of Stripping Fluid Composition]

[0120] The performance of each stripping fluid composition having the compositions shown in Tables 1 to 4 above was evaluated according to the following evaluation methods and evaluation criteria.

[0121] On the other hand, in the experiments described below, the composition used to form the resist can be a composition commonly used in the art, including phenolic resin and diazonoquinone.

[0122] 1) Peeling performance of resist patterns

[0123] Evaluation methods :

[0124] In the stripping liquid composition (100g) of the above-mentioned preparation example, heated to 50°C, a sample with a resist pattern (thickness: about 1μm) formed by curing one side of a glass substrate (thickness: 0.5cm) at 150°C for 10 minutes was immersed, and the time required for the resist pattern to be completely peeled off and removed was measured.

[0125] Evaluation criteria :

[0126] ◎: Cases where the resist pattern removal time is less than 10 seconds.

[0127] ○: Cases where the removal time of the resist pattern exceeds 10 seconds but is less than 30 seconds.

[0128] △: Cases where the removal time of the resist pattern exceeds 30 seconds but is less than 90 seconds.

[0129] X: Resist pattern removal time exceeds 90 seconds.

[0130] 2) Contact angle measurement for evaluating cleaning ability

[0131] Evaluation methods :

[0132] A solution was prepared by dissolving 1% by weight of the solid resist in the stripping solution composition (100g) of the above preparation example. A glass substrate (2cm × 3cm) was immersed in the above solution, then rinsed with ultrapure water and dried with air to prepare a sample. At 25°C, 2μL of ultrapure water was dropped onto the surface of the sample, and the contact angle of the water droplet was measured using a contact angle meter (KRUSS DSA1005).

[0133] Evaluation criteria :

[0134] ◎: Cases where the contact angle of the water droplet is less than 40°

[0135] ○: Cases where the contact angle of the water droplet is greater than 40° and less than or equal to 50°

[0136] △: When the contact angle of the water droplet is greater than 50° and less than or equal to 60°

[0137] X: Cases where the contact angle of the water droplet is greater than 60°.

[0138] 3) Corrosion stability of metal films

[0139] Evaluation methods :

[0140] The Cu / MoTi metal film with the resist pattern was immersed in a mixture prepared by mixing the stripping solution composition of the above preparation example with deionized water at a weight ratio of 1:9. After holding for 1 minute, it was rinsed with ultrapure water and dried with air. The critical size loss (CD-Loss) of the metal film contained in the product obtained by the above drying was measured using scanning electron microscopy (SEM). The lower the CD-Loss of the metal film, the better the corrosion stability of the metal film and the better the device performance.

[0141] Evaluation criteria :

[0142] ◎: The case where the CD-Loss of the metal film is 0

[0143] ○: Cases where the CD-Loss of the metal film is below 0.01 μm.

[0144] △: Case where the CD-Loss of the metal film is greater than 0.01 μm and less than or equal to 0.10 μm.

[0145] X: Case where the CD-Loss of the metal film is greater than 0.10 μm.

[0146] 4) Initial solubility of PR

[0147] Evaluation methods :

[0148] In the stripping liquid composition (100g) of the above-mentioned preparation example, heated to 50°C, 1g of solid resist was added. After stirring at 600 rpm for 30 minutes, the initial solubility of the solid resist in the stripping liquid composition was measured. The solid resist was prepared by heating the liquid resist forming composition at 150°C for 8 hours. Higher solubility of the solid resist indicates better persistence of the stripping performance of the stripping liquid composition.

[0149] Evaluation criteria :

[0150] ◎: When the initial solubility of the solid resist is 99% by weight or higher.

[0151] ○: The initial solubility of the solid resist is 95% by weight or more but less than 99% by weight.

[0152] △: The initial solubility of the solid resist is 90% by weight or more but less than 95% by weight.

[0153] X: Case where the initial solubility of the solid resist is less than 90% by weight.

[0154] Table 5

[0155]

[0156]

[0157]

[0158] Table 6

[0159] Classification Peeling performance Cleaning ability Corrosion stability PR initial solubility Example 21 ○ ◎ ◎ ○ Example 22 ○ ◎ ◎ ○ Example 23 ◎ ◎ ◎ ◎ Example 24 ◎ ◎ ○ ◎ Example 25 ◎ ◎ ◎ ○ Example 26 ◎ ◎ ◎ ○ Example 27 ◎ ◎ ○ ◎ Example 28 ○ ◎ ◎ ○ Example 29 ○ ◎ ◎ ○ Example 30 ○ ○ ○ ○ Example 31 ◎ ○ ○ ○ Example 32 ○ ◎ ○ ○ Example 33 ○ ◎ ○ ○ Example 34 ○ ◎ ○ ○

[0160] Table 7

[0161] Classification Peeling performance Cleaning ability Corrosion stability PR initial solubility Comparative Example 16 ◎ X X ◎ Comparative Example 17 ◎ X X ◎ Comparative Example 18 ◎ X X ◎ Comparative Example 19 ◎ X X ◎ Comparative Example 20 ◎ X X ◎ Comparative Example 21 ◎ X X ◎ Comparative Example 22 ◎ △ X ◎ Comparative Example 23 ◎ △ X ◎ Comparative Example 24 ◎ △ X ◎ Comparative Example 25 ◎ △ X ◎ Comparative Example 26 ◎ △ X ◎ Comparative Example 27 ◎ △ X ◎ Comparative Example 28 X ◎ ◎ X Comparative Example 29 X ◎ ◎ X Comparative Example 30 X ◎ △ X Comparative Example 31 X ◎ X X Comparative Example 32 X ◎ ◎ X Comparative Example 33 X ◎ ◎ X

[0162] Table 8

[0163]

[0164]

[0165] When Comparative Examples 8 and 9, with different alkyl alcohol contents, were compared with Examples 9 to 13 and 20, Comparative Examples 8 and 9, whose alkyl alcohol contents did not meet the range of greater than 3% by weight and less than 20% by weight, exhibited problems with peel performance, corrosion of the metal film, or reduced solubility of the solid resist. Specifically, Comparative Example 8, with an alkyl alcohol content of less than 3% by weight, had problems with reduced peel performance and reduced solubility of the solid resist. Comparative Example 9, with an alkyl alcohol content of 20% by weight or more, experienced metal film corrosion. On the other hand, Examples 9 to 13 and 20, with alkyl alcohol contents meeting the range of greater than 3% by weight and less than 20% by weight, exhibited excellent peel performance, cleaning ability, corrosion resistance of the metal film, and solubility of the solid resist.

[0166] When comparing Comparative Examples 12 to 15 with different alkanolamine contents with Examples 9 to 13 and 20, it was found that when the alkanolamine content was 0.5% by weight or less, the peeling performance and the initial solubility of the resist material decreased, while when the alkanolamine content was 25% by weight or more, metal film corrosion occurred. On the other hand, Examples 9 to 13 and 20, with an alkanolamine content in the range of greater than 0.5% by weight and less than 25% by weight, exhibited excellent peeling performance, cleaning ability, metal film corrosion, and solubility of the resist solid.

[0167] When comparing Comparative Examples 1 to 6 with different weight ratios of hydroxide to alkanolamine with Examples 1 to 8, 11, 14 to 20, Comparative Examples 3 to 6, with a hydroxide to alkanolamine weight ratio of less than 1:3, exhibited problems with metal film corrosion, while Comparative Examples 1 and 2, with a hydroxide to alkanolamine weight ratio greater than 1:400, showed poor peeling performance and initial dissolution performance. On the other hand, the hydroxide to alkanolamine weight ratios of Examples 1 to 8, 11, 14 to 20 met the requirements of 1:3 to 1:400, thereby exhibiting excellent peeling performance, cleaning ability, metal film corrosion, and dissolution performance of the resist solid.

[0168] Furthermore, in Comparative Examples 13 to 15, even though the weight ratio of hydroxide to alkanolamine ranged from 1:3 to 1:400, the content of alkanolamine exceeded the range of greater than 0.5% by weight and less than 25% by weight. Therefore, they exhibited poor results in terms of peeling performance, corrosion of metal films, or initial solubility of solid resist. It can be inferred that the performance of the peeling solution composition can be improved by the organic combination of the weight ratio of hydroxide to alkanolamine and the content of alkanolamine.

[0169] Furthermore, in Comparative Examples 8 and 9, even though the weight ratio of hydroxide to alkanolamine ranged from 1:3 to 1:400, the alkyl alcohol content did not meet the range of greater than 3% by weight and less than 20% by weight. Therefore, these examples exhibited problems with peeling performance, corrosion of the metal film, or reduced solubility of the solid resist. It can be inferred that all properties can be improved through the organic combination of the weight ratio of hydroxide to alkanolamine and the content of alkyl alcohol.

[0170] Taking into account the above experimental results, it can be confirmed that in order to exhibit excellent performance in all evaluated performances, the following conditions need to be met: the alkyl alcohol content is greater than 3% by weight and less than 20% by weight; the alkanolamine content is greater than 0.5% by weight and less than 25% by weight; it contains hydroxide and water, and the weight ratio of the hydroxide to the alkanolamine is 1:3 to 1:400.

[0171] Referring to Table 8 above, when the alkyl alcohol content is greater than 3% by weight and less than 20% by weight, the alkanolamine content is greater than 0.5% by weight and less than 20% by weight, and the product contains hydroxide and water with a weight ratio of hydroxide to alkanolamine ranging from 1:3 to 1:400, it exhibits excellent performance in resist pattern removal, cleaning ability, metal film corrosion, and resist solid dissolution. Specifically, Comparative Examples 34 and 35, where the weight ratio of acetate to alkanolamine does not meet the 1:3 to 1:400 range, show a decrease in at least one of the following properties: resist pattern removal, metal film corrosion protection, and initial resist solid dissolution.

[0172] Unless explicitly stated otherwise, the features described in the above embodiments may be combined with other embodiments. Furthermore, while preferred embodiments of the present invention have been described in detail above, the scope of the invention is not limited thereto. Various modifications and alterations made by those skilled in the art utilizing the basic concepts of the invention as defined in the appended claims are also within the scope of the invention.

Claims

1. A stripping liquid composition, characterized in that, include: Alkyl alcohols greater than 3% by weight and less than 20% by weight; Alkylamines greater than 0.5% by weight and less than 25% by weight; hydroxides or acetates; and water; The weight ratio of the hydroxide to the alkanolamine or the weight ratio of the acetate to the alkanolamine is 1:3 to 1:

400.

2. The stripping fluid composition according to claim 1, characterized in that, The alkyl alcohols include monohydric alcohols having at least one ether group.

3. The stripping fluid composition according to claim 1, characterized in that, The alkyl alcohol includes at least one selected from the group consisting of ethanol, 1-propanol, 1-butanol, 2-butanol, isopropanol, tetrahydrofurfuryl alcohol, propylene glycol, ethylene glycol, diethylene glycol, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monobutyl ether, and glycerol.

4. The stripping fluid composition according to claim 1, characterized in that, Based on the total weight of the stripping fluid composition, the content of the alkanolamine is from 10% to 20% by weight.

5. The stripping fluid composition according to claim 1, characterized in that, The alkanolamine includes at least one hydroxyl group and a secondary amino group.

6. The stripping fluid composition according to claim 1, characterized in that, The alkanolamine includes at least one selected from the group consisting of N-methylethanolamine, aminoethylethanolamine, monoethanolamine, monoisopropanolamine, 2-amino-2-methyl-1-propanol, 2-methylaminoethanol, 2-(2-aminoethylamino)ethanol, and 3-aminopropanolamine.

7. The stripping fluid composition according to claim 1, characterized in that, Based on the total weight of the stripping fluid composition, the content of the hydroxide or the acetate is greater than 0.03% by weight and less than 7% by weight.

8. The stripping fluid composition according to claim 1, characterized in that, The hydroxide includes at least one selected from the group consisting of potassium hydroxide, sodium hydroxide, and combinations thereof.

9. The stripping fluid composition according to claim 1, characterized in that, The acetate includes at least one selected from the group consisting of sodium acetate, potassium acetate, magnesium acetate, and calcium acetate.

10. The stripping fluid composition according to claim 1, characterized in that, The water content is from 50% to 89% by weight, based on the total weight of the stripping fluid composition.

11. The stripping fluid composition according to claim 1, characterized in that, The weight ratio of the hydroxide to the alkanolamine or the weight ratio of the acetate to the alkanolamine is 1:20 to 1:

200.

12. The stripping fluid composition according to claim 1, characterized in that, It also includes at least one additive selected from the group consisting of corrosion inhibitors, antioxidants, defoamers and stripping promoters.

Images