Photoresist stripping liquid composition

Abstract

The invention discloses a photoresist stripping liquid composition which comprises the following components in percentage by weight: 58wt%-90wt% of a protonic solvent; 9 wt% to 45 wt% of an aprotic protonic solvent; 0.9 wt%-10 wt% of an organic base compound; 0.01 wt% to 1 wt% of an additive; 0.01 wt%-3 wt% of an auxiliary additive; and the balance of deionized water. When the photoresist stripping liquid is applied to a scene of large-thickness and large-coverage-area photoresist stripping, photoresist residues on a substrate cannot be caused, and the corrosion to copper, aluminum and the like is relatively small, so that the performance and the stability of a semiconductor component are favorably improved.

Description

Technical Field

[0001] The invention relates to the technical field of photoresist cleaning, in particular to a photoresist stripping liquid composition. Background Art

[0002] The display panel and semiconductor industries have experienced rapid growth in recent years. In the semiconductor component manufacturing process, photoresist is typically used as a mask. After three steps—exposure, development, and etching—a specific pattern is formed on the substrate. After the pattern is transferred, the photoresist, acting as the mask, must be removed before proceeding to the next step.

[0003] After development, photoresist undergoes various processes, such as wet etching, dry etching, and ion implantation, which can cause structural changes in the photoresist and make it difficult to remove. Therefore, a stripping solution with strong dissolving properties for the photoresist is required. During this process, a photoresist stripping solution is used to remove the photoresist adhered to the substrate. For conventional substrates, the thickness of the photoresist is generally ≤1.5μm, and the coverage area is less than 45%. However, a few film layers of photoresist can reach a thickness of 1.8μm or even 2.0μm, and cover a larger area. As the thickness and coverage area of the photoresist on the substrate increase, new challenges are posed to the stripping solution's removal capabilities.

[0004] Most existing photoresist stripping solutions are composed of organic solvents, amine compounds, and additives. When used to strip substrates with photoresist thickness greater than 1.8 μm and coverage greater than 45%, these stripping solutions can easily cause photoresist residue, which in turn causes the photoresist to stick back to the substrate, resulting in a decrease in the yield of panels or semiconductor components, ultimately affecting product quality.

[0005] In view of this, the present invention is proposed. Summary of the Invention

[0006] The purpose of the present invention is to provide a photoresist stripping solution composition to overcome the problem that the existing photoresist stripping solution composition is not suitable for the scenario of stripping photoresists with large thickness and large coverage area.

[0007] The present invention is achieved in that:

[0008] In a first aspect, the present invention provides a photoresist stripping solution composition, comprising:

[0009] Protic solvent 58wt%-90wt%;

[0010] 9 wt%-45 wt% of aprotic protic solvent;

[0011] 0.9wt%-10wt% of an organic base compound;

[0012] Additives 0.01wt%-1wt%;

[0013] Auxiliary additives 0.01wt%-3wt%;

[0014] The balance was deionized water.

[0015] In an optional embodiment, the mass fraction of the auxiliary additive is 0.02wt%-1wt%;

[0016] And / or, the auxiliary additive comprises at least one of the compounds represented by Formula I, Formula II and Formula III,

[0017]

[0018] In formula I, R2 and R3 are each independently selected from an alkyl group having 1 to 3 carbon atoms; R1 and R4 are each independently selected from an alkyl group having 2 to 10 carbon atoms;

[0019] In formula II, R1 and R3 are each independently selected from an alkyl group having 1 to 4 carbon atoms, and R2 is selected from an alkyl group having 3 to 11 carbon atoms;

[0020] In formula III, R1, R2 and R3 are each independently selected from an alkyl group having 2 to 10 carbon atoms.

[0021] In an optional embodiment, the compound of formula I is selected from at least one of dibutyl phthalate, dipropyl phthalate and dioctyl phthalate;

[0022] and / or, the compound of formula II is at least one selected from dimethyl succinate, dimethyl adipate, dimethyl sebacate, dibutyl succinate, dibutyl adipate and dibutyl sebacate;

[0023] And / or, the compound of formula III is at least one selected from glyceryl triacetate, glyceryl tripropionate and glyceryl tributyrate.

[0024] In an optional embodiment, the protic solvent is obtained by an addition reaction of a monohydric alcohol having 1 to 8 carbon atoms with at least one of ethylene oxide, propylene oxide, and butylene oxide;

[0025] And / or, the mass fraction of the protic solvent is 61wt%-81wt%;

[0026] In an optional embodiment, the aprotic protophilic solvent is selected from at least one of formamide and its derivatives, solvents containing sulfur-oxygen double bonds, and nitrogen-containing heterocyclic solvents;

[0027] and / or, the mass fraction of the aprotic protic solvent is 17 wt%-31 wt%;

[0028] In an optional embodiment, the organic base compound is selected from at least one of an alcoholamine compound, a polyamine compound and a fatty amine compound;

[0029] And / or, the mass fraction of the organic base compound is 1.5wt%-4.5wt%;

[0030] In an optional embodiment, the additive comprises at least one of a metal protective agent and a surfactant;

[0031] And / or, the mass fraction of the additive is 0.03wt%-0.8wt%;

[0032] In an optional embodiment, the protic solvent is obtained by an addition reaction of a monohydric alcohol having 1 to 5 carbon atoms with at least one of ethylene oxide, propylene oxide, and butylene oxide;

[0033] and / or the metal protective agent is selected from at least one of molybdic acid, citric acid, alanine, glycine, leucine, L-arginine, gallic acid, mercaptomethylimidazole, dimercaptobenzimidazole, dimercaptobenzothiazole, benzotriazole (BTA), methylbenzotriazole (TT), pentamethylbenzotriazole (TTA), 5-aminotetrazole (monohydrate), 5-aminotetrazole, methimazole, 2-aminothiazole, N-vinylimidazole, benzotriazole and benzimidazole;

[0034] and / or the surfactant is selected from at least one of 1-adamantane acrylate, 4-biphenylmethanol acrylate, 4-hydroxyphenyl methacrylate, N-(p-hydroxyphenyl) methacrylate, sodium dodecylbenzenesulfonate, acrylic acid copolymer, chloroethidium acetate, diphenylpolysiloxane, methylphenylpolysiloxane, organic modified siloxane, fluorinated siloxane, polyoxyethylene ethyl ether, isomeric decanol polyoxyethylene ether, and nonylphenol polyoxyethylene ether;

[0035] In an optional embodiment, the protic solvent is selected from at least one of diethylene glycol methyl ether, diethylene glycol butyl ether, dipropylene glycol methyl ether, ethylene glycol butyl ether and ethylene glycol dimethyl ether;

[0036] and / or, the aprotic protophilic solvent is selected from at least one of formamide, N-methylformamide, dimethylformamide, N,N-dimethylformamide (DMF), acetamide, dimethylacetamide, N-methylacetamide, N,N-dimethylacetamide, hexamethylphosphoramide, dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylimidazole and sulfolane;

[0037] And / or, the organic base compound is selected from at least one of N-hydroxyethylpiperazine (HEP), N-methylmonoethanolamine (MMEA), N-methyldiethanolamine (MDEA), N,N-dimethylethanolamine, triethanolamine, isopropanolamine, ethylenediamine, hydroxyethylethylenediamine (AEEA), diethylenetriamine, triethylenetetramine, tetraethylenepentamine, tris(2-aminoethyl)amine, polyethylenepolyamine and dibutylamine.

[0038] The present invention has the following beneficial effects:

[0039] The photoresist stripping liquid in this application can be used in scenarios where large-thickness, large-coverage-area photoresist stripping occurs without causing photoresist residue on the substrate, and has low corrosiveness to copper, aluminum, etc., thereby helping to improve the performance and stability of semiconductor components. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments. It should be understood that the following drawings only illustrate certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other relevant drawings can be obtained based on these drawings without paying any creative work.

[0041] Figure 1 The particle size distribution diagram obtained by testing the sol particle size of the photoresist stripping solution composition in Example 5;

[0042] Figure 2 The particle size distribution diagram obtained by testing the sol particle size of the photoresist stripping solution composition in Example 8;

[0043] Figure 3 The particle size distribution diagram obtained by testing the sol particle size of the photoresist stripping solution composition in Comparative Example 1;

[0044] Figure 4 This is a particle size distribution diagram obtained by testing the sol particle size of the photoresist stripping solution composition in Comparative Example 5. DETAILED DESCRIPTION

[0045] To make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention are described clearly and completely below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer are used. Where the manufacturer of the reagents or instruments is not specified, all are conventional products that can be purchased commercially.

[0046] An embodiment of the present invention provides a photoresist stripping solution composition, comprising:

[0047] Protic solvent 58wt%-90wt%;

[0048] 9 wt%-45 wt% of aprotic protic solvent;

[0049] 0.9wt%-10wt% of an organic base compound;

[0050] Additives 0.01wt%-1wt%;

[0051] Auxiliary additives 0.01wt%-3wt%;

[0052] The balance was deionized water.

[0053] The photoresist stripping liquid in this application can be used in scenarios where large-thickness, large-coverage-area photoresist stripping occurs without causing photoresist residue on the substrate, and has low corrosiveness to copper, aluminum, etc., thereby helping to improve the performance and stability of semiconductor components.

[0054] In an optional embodiment, the auxiliary additive comprises at least one of the compounds represented by Formula I, Formula II and Formula III,

[0055]

[0056] In Formula I, R2 and R3 are each independently selected from an alkyl group having 1 to 3 carbon atoms; R1 and R4 are each independently selected from an alkyl group having 2 to 10 carbon atoms; preferably, the compound of Formula I is selected from at least one of dibutyl phthalate, dipropyl phthalate and dioctyl phthalate;

[0057] In formula II, R1 and R3 are each independently selected from an alkyl group having 1 to 4 carbon atoms, and R2 is selected from an alkyl group having 3 to 11 carbon atoms; preferably, the compound of formula II is selected from at least one of dimethyl succinate, dimethyl adipate, dimethyl sebacate, dibutyl succinate, dibutyl adipate, and dibutyl sebacate;

[0058] In formula III, R1, R2 and R3 are each independently selected from an alkyl group having 2 to 10 carbon atoms. Preferably, the compound of formula III is selected from at least one of triacetin, tripropionin and tributyrin.

[0059] Auxiliary additives play the following main roles in the photoresist system:

[0060] 1. Improve solubility performance: During the stripping process, auxiliary additives can effectively enhance the stripping liquid's ability to dissolve photoresist, thereby significantly improving the removal efficiency of photoresist materials.

[0061] 2. Optimize compatibility: Auxiliary additives such as esters can achieve good synergy with other components in the photoresist system due to their excellent compatibility.

[0062] 3. Promote dispersion effect: The protic solvent, non-protonic protonic solvent and organic base compound in the stripping solution serve as dissolving media, and are combined with auxiliary additives to improve the uniformity of the distribution of the stripping solution on the photoresist surface, which is beneficial to improving the dispersion efficiency of the photoresist on the substrate. After the photoresist is dispersed, the contact area with the substrate is reduced, and the gaps between the photoresist particles become larger. At this time, the photoresist is easier to strip, which is beneficial to achieve the debonding effect.

[0063] In an optional embodiment, the mass fraction of the auxiliary additive is 0.01wt%-3wt%, such as 0.01%, 0.02%, 0.05%, 0.10%, 0.20%, 0.50%, 1.00%, 1.50%, 2.00%, 2.20%, 2.40%, 2.60%, 2.80%, 2.90%, 3.00%, preferably 0.02wt%-1wt%; when the addition ratio of the auxiliary additive is within this range, the photoresist on the glass substrate can be dispersed into smaller particles, and the smaller particles are easier to be cleaned, which can avoid the back-sticking caused by large particles of photoresist not being rinsed in time on the substrate. For example, the small particles of photoresist can be easily rinsed clean by using wind-powered spraying of deionized water from the stripping equipment. When the amount of auxiliary additives added is too low, the low amount makes its effect weak and cannot form a good synergistic effect with other components of the stripping solution. It is impossible to strip the photoresist with a large thickness and a large coverage area from the stripping substrate, which will cause photoresist residue on the substrate; when the amount of auxiliary additives added is too high, although the photoresist can be completely stripped from the sample substrate, it will cause damage to the glass substrate.

[0064] In an optional embodiment, the protic solvent is obtained by an addition reaction of a monohydric alcohol having 1 to 8 carbon atoms with at least one of ethylene oxide, propylene oxide, and butylene oxide; preferably, the protic solvent is obtained by an addition reaction of a monohydric alcohol having 1 to 5 carbon atoms with at least one of ethylene oxide, propylene oxide, and butylene oxide; more preferably, the protic solvent is selected from at least one of diethylene glycol methyl ether, diethylene glycol butyl ether, dipropylene glycol methyl ether, ethylene glycol butyl ether, and ethylene glycol dimethyl ether.

[0065] Protic solvents can provide hydrogen bonding and polar solubility, which is beneficial for dissolving polar components in photoresist.

[0066] In an optional embodiment, the mass fraction of the protic solvent is 58 wt%-90 wt%, such as 58%, 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, 78%, 80%, 85%, 88%, 90%, preferably 61 wt%-81 wt%;

[0067] When the amount of protic solvent added is within the above range, it is beneficial for the photoresist to be completely dissolved. If the amount of protic solvent added is too low, the photoresist will not be completely dissolved after stripping, and some photoresist will remain on the sample substrate. When the amount of protic solvent added is too high, the proportion of other components such as organic base compounds, additives, and auxiliary additives will be reduced, which is not conducive to the dispersion of the photoresist and, in turn, cannot completely strip the photoresist from the glass substrate. In addition, if the proportion of protic solvent in the stripping solution is too high, it will also increase the production cost of the product.

[0068] In an optional embodiment, the aprotic protophilic solvent is selected from at least one of formamide and its derivatives, solvents containing sulfur-oxygen double bonds, and nitrogen-containing heterocyclic solvents; preferably, the aprotic protophilic solvent is selected from at least one of formamide, N-methylformamide, dimethylformamide, N,N-dimethylformamide (DMF), acetamide, dimethylacetamide, N-methylacetamide, N,N-dimethylacetamide, hexamethylphosphoramide, dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylimidazole and sulfolane;

[0069] Aprotic protonic solvents can destroy the molecular structure of photoresist through dipole action and penetration ability, and can synergistically work with protic solvents to effectively increase the solubility of photoresist in the stripping solution, making the photoresist evenly and stably dispersed in the system.

[0070] In an optional embodiment, the mass fraction of the aprotic protic solvent is 9wt%-45wt%, such as 9%, 12%, 15%, 18%, 21%, 24%, 27%, 30%, 33%, 36%, 39%, 42%, 43%, 44%, 45%, preferably 17wt%-31wt%.

[0071] When the amount of non-protonic protonic solvent added is too low, the solubility of the stripping solution in the photoresist is low, which will cause stripping residue; when the amount of non-protonic protonic solvent added is too high, the proportion of other components such as protonic polar solvents, organic base compounds, additives and auxiliary additives will decrease accordingly, making it impossible to completely strip and dissolve the photoresist.

[0072] In an optional embodiment, the organic base compound is selected from at least one of an alcoholamine compound, a polyamine compound and a fatty amine compound; preferably, the organic base compound is selected from at least one of N-hydroxyethylpiperazine (HEP), N-methylmonoethanolamine (MMEA), N-methyldiethanolamine (MDEA), N,N-dimethylethanolamine, triethanolamine, isopropanolamine, ethylenediamine, hydroxyethylethylenediamine (AEEA), diethylenetriamine, triethylenetetramine, tetraethylenepentamine, tris(2-aminoethyl)amine, polyethylenepolyamine and dibutylamine.

[0073] Organic base compounds have excellent stripping and solubility properties. Due to steric hindrance, when the organic base compound concentration is within a reasonable range, the corrosion to metals such as copper and aluminum in the substrate is relatively low. For example, chain-like alkanolamine compounds, such as hydroxyethylethylenediamine, can penetrate between the photoresist and the substrate, continuously dissolving the photoresist resin, while fatty amine compounds can swell the photoresist resin, increasing the contact area between the organic base compound and the photoresist resin, thereby effectively improving the stripping efficiency of thick photoresist films with wide coverage areas.

[0074] It should be noted that MDEA in the organic base compound is a tertiary amine, with three hydrocarbon groups on the nitrogen atom, no NH bond, and no intermolecular hydrogen bond. The steric hindrance of the three hydrocarbon groups significantly improves the protective effect of the nitrogen atom, reduces the possibility of decomposition or oxidation reaction of the later stripping liquid waste during high-temperature distillation, and has better thermal stability. AEEA is a secondary amine, with two hydrocarbon groups and one hydrogen atom on the nitrogen atom, and the hydrogen bond effect is weakened. Due to the increase in substituents, the steric hindrance partially protects the nitrogen atom, making its thermal stability better than that of primary amines. Therefore, in some embodiments of the present application, a combination of N-methyldiethanolamine (MDEA) and hydroxyethylethylenediamine (AEEA) is used as an organic base compound. Considering the strong alkalinity of AEEA, in order to reduce the corrosion of metals such as copper and aluminum in the substrate, the mass ratio of the two is preferably 3:1, that is, when the amount of the organic base compound added is 2%, the amount of MDEA added is 1.5%, and the amount of AEEA added is 0.5%. At this time, the stripping solution has a better pH, and the appropriate pH value can promote the stripping of the photoresist by the stripping solution. It should be noted that the proportion of MDEA is higher than that of AEEA, and it can also minimize the decomposition and oxidation of amines during the waste liquid distillation recovery process, so that the amount of organic base in the components of the regenerated stripping liquid mixed with the semi-finished product after distillation changes little, and the stripping performance of the regenerated stripping liquid is equivalent to that of the new liquid.

[0075] In an optional embodiment, the mass fraction of the organic base compound is 0.9wt%-10wt%, such as 0.9%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 4.0%, 5.0%, 6.0%, 7.0%, 8.0%, 9.0%, 9.5%, 9.8%, 10.0%, preferably 1.5wt%-4.5wt%.

[0076] When the addition ratio of the organic base compound is within this range, it is more conducive to the decomposition and stripping of the photoresist. When the addition amount of the organic base compound is too low, it is difficult to completely strip the photoresist, which may cause photoresist residue on the substrate. When the addition amount of the organic base compound is too high, although the photoresist resin can be completely stripped from the sample substrate, due to the alkaline nature of the organic base compound, some of which are even strongly alkaline, excessive addition can cause a certain degree of corrosion to the copper, aluminum and other metal circuits on the substrate, thereby affecting product yield.

[0077] In an optional embodiment, the additive comprises at least one of a metal protecting agent and a surfactant.

[0078] In an optional embodiment, the metal protective agent is selected from at least one of molybdic acid, citric acid, alanine, glycine, leucine, L-arginine, gallic acid, mercaptomethylimidazole, dimercaptobenzimidazole, dimercaptobenzothiazole, benzotriazole (BTA), methylbenzotriazole (TT), pentamethylbenzotriazole (TTA), 5-aminotetrazole (monohydrate), 5-aminotetrazole, methimazole, 2-aminothiazole, N-vinylimidazole, benzotriazole and benzimidazole.

[0079] In an optional embodiment, the surfactant is selected from at least one of 1-adamantane acrylate, 4-biphenylmethanol acrylate, 4-hydroxyphenyl methacrylate, N-(p-hydroxyphenyl) methacrylate, sodium dodecylbenzenesulfonate, acrylic acid copolymer, chloroethidium acetate, diphenyl polysiloxane, methylphenyl polysiloxane, organic modified siloxane, fluorinated siloxane, polyoxyethylene ethyl ether, isomeric decanol polyoxyethylene ether and nonylphenol polyoxyethylene ether.

[0080] The metal corrosion inhibitor undergoes physical or chemical adsorption with the metal wiring at the bottom of the glass substrate, thereby protecting the metal wiring from being corroded by the stripping liquid; the surfactant is used to reduce the surface tension and increase the wetting of the glass substrate by the stripping liquid to improve the photoresist stripping effect.

[0081] In an optional embodiment, the mass fraction of the additive is 0.01wt%-1wt%, such as 0.01%, 0.02%, 0.05%, 0.10%, 0.20%, 0.30%, 0.40%, 0.50%, 0.60%, 0.70%, 0.80%, 0.90%, 0.95%, 0.98%, 1.00%, preferably 0.03wt%-0.8wt%.

[0082] If the additive dosage is too low, as the contact time between the stripping substrate and the stripping solution increases, the additive will not be able to absorb enough metal wiring, causing the photoresist stripping solution to cause a certain degree of corrosion on the substrate's copper, aluminum, and other metal wiring. If the additive dosage is too high, the excessive amount of corrosion inhibitor and surfactant will affect the photoresist stripping and dissolving ability of the photoresist stripping solution. In some embodiments, the mass ratio of metal protective agent to surfactant is 1:1, which ensures both protection of the metal wiring and effective photoresist stripping.

[0083] The features and performance of the present invention are further described in detail below with reference to the embodiments.

[0084] The compositions of the photoresist stripping solution compositions provided in the examples and comparative examples of the present application are shown in Table 1.

[0085] Table 1

[0086]

[0087] Notes: 1. The preparation method of the photoresist stripping solution composition provided in each embodiment and comparative example includes: weighing the raw materials according to Table 1 and uniformly mixing them to obtain each photoresist stripping solution composition.

[0088] 2. In the example of Table 1: the protic polar solvent is diethylene glycol monomethyl ether; the aprotic protonic solvent is N-methylformamide; the organic base compound is MDEA:AEEA = 3:1 (mass ratio); the additive is 5-aminotetrazole:1-adamantane acrylate = 1:1 (mass ratio); and the auxiliary additive is dibutyl sebacate.

[0089] 3. In the comparative example in Table 1: the protic polar solvent is ethylene glycol monomethyl ether; the aprotic protonic solvent is N-methylpyrrolidone (NMP); the organic base compound is isopropanolamine; the additives are acrylic acid copolymer and sodium citrate, and the mass ratio of acrylic acid copolymer to sodium citrate is 1:1; and the auxiliary additive is triacetin.

[0090] Example 11

[0091] The only difference from Example 5 is that the organic base compound is replaced by MDEA.

[0092] Example 12

[0093] The only difference from Example 5 is that the organic base compound is replaced by AEEA.

[0094] Example 13

[0095] The only difference from Example 5 is that the organic base compound is replaced by MDEA:triethanolamine=3:1 (mass ratio).

[0096] Example 14

[0097] The only difference from Example 5 is that the auxiliary additive is replaced by triacetin.

[0098] Comparative Example 6

[0099] The only difference from Example 8 is that the protic solvent is replaced by cyclohexanone.

[0100] Comparative Example 7

[0101] The only difference from Example 8 is that the aprotic protophilic solvent is replaced by dimethyl sulfoxide.

[0102] Comparative Example 8

[0103] The only difference from Example 8 is that the organic base compound is replaced by diethylamine.

[0104] Comparative Example 9

[0105] The only difference from Example 8 is that the additives are replaced by sodium citrate and organosilicon-modified siloxane, and the mass ratio of sodium citrate to organosilicon-modified siloxane is 1:1.

[0106] Comparative Example 10

[0107] The only difference from Example 8 is that the auxiliary additive is replaced by dibutyl phthalate.

[0108] The photoresist stripping solution compositions prepared in the examples and comparative examples were subjected to stripping performance test experiments, stability tests and sol particle size tests.

[0109] The specific experimental operations are as follows:

[0110] (1) Stripping performance test experiment: 100 ml of each of the photoresist stripping solution compositions of the above-mentioned embodiment and comparative example were respectively placed in a 50°C water bath and heated. A glass substrate with a size of 3 cm*3 cm and a Cu film layer with a photoresist thickness of 2 μm and a photoresist coverage area of 90% and a glass substrate with a size of 3 cm*3 cm and an Al film layer with a photoresist thickness of 1.8 μm and a photoresist coverage area of 50% was placed in the photoresist stripping solution composition and immersed for 90 seconds. The stripping residue and copper and aluminum circuit corrosion of the glass substrate by the photoresist stripping solution composition were tested.

[0111] (2) Stability test: 100 ml of each of the photoresist stripping solution compositions of the above-mentioned embodiment and comparative example were taken, and the stripping solution was tested for crystallization of the solid additive after being exposed to volatilization at 50° C. for 1 hour and 24 hours;

[0112] (3) Detection of sol particle size: 100 ml of each of the photoresist stripping solution compositions of the above-mentioned embodiment and comparative example were taken, 10 g of photoresist powder was added to dissolve to obtain a dissolving solution, the dissolving solution was mixed with n-hexane in a volume ratio of 1:1, and then ultrasonically treated for 2 minutes to obtain a test solution, and then the sol particle size in the test solution was detected using a laser particle size analyzer.

[0113] Evaluation method:

[0114] (1) Use an optical microscope (OM) to observe whether there is any photoresist residue on the glass substrate after immersion stripping, and record the results in the following Table 2; the OM evaluation rules are as follows: √ (no residue on the glass substrate surface), × (residue on the glass substrate surface).

[0115] The concentrations of copper ions and aluminum ions in the stripping solution in which the photoresist was immersed were measured using inductively coupled plasma mass spectrometry (ICP MS), and the results are recorded in Table 2 below.

[0116] (2) The crystals precipitated in the stripping solution were observed and the results were recorded in Table 3 below. In the examples, the precipitated crystals were mainly 5-aminotetrazole.

[0117] (3) Comparison of the median diameter, volume average diameter D(4,3) (large particle size) and area average diameter D(3,2) (actual particle size) of the sol in the test solution is shown in Table 4.

[0118] Among them, if the particle diameter of each particle size interval in the particle group is d i , the corresponding number of particles is n i , then the calculation formula of D(4,3) is: The calculation formula for D(3,2) is:

[0119] Table 2: Sample peeling residue and corrosion

[0120]

[0121]

[0122] Table 3: Stability test

[0123]

[0124]

[0125] Table 4: Sol particle size detection

[0126] Median diameter (D50) μm Volume average diameter D(4,3)μm Area average diameter D(3,2)μm Example 1 19.31 23.18 20.25 Example 2 19.27 25.46 22.75 Example 3 17.36 20.34 17.94 Example 4 15.46 16.38 15.51 Example 5 8.21 16.71 14.97 Example 6 7.35 15.49 13.62 Example 7 10.69 18.48 16.42 Example 8 4.55 7.19 5.59 Example 9 5.31 8.25 6.48 Example 10 17.52 29.35 27.34 Example 11 16.39 27.62 21.72 Example 12 18.31 30.02 28.60 Example 13 19.37 24.58 21.92 Example 14 20.31 25.02 23.12 Comparative Example 1 25.37 68.28 45.64 Comparative Example 2 32.38 69.83 55.28 Comparative Example 3 45 59.21 52.26 Comparative Example 4 39.12 51.21 49.31 Comparative Example 5 40.19 82.34 75.28 Comparative Example 6 47.82 84.92 77.49 Comparative Example 7 39.67 72.59 64.15 Comparative Example 8 26.72 62.27 42.41 Comparative Example 9 36.61 68.36 60.24 Comparative Example 10 24.84 57.62 42.6

[0127] The experimental data results in the above table are analyzed as follows:

[0128] 1. The variables in Examples 1 to 3 are protic polar solvents and non-protic protophilic solvents. When the solvent dosage is within the scope of this application, the obtained photoresist stripping solution compositions all have good effects; organic base compounds are corrosive, and additives can inhibit the corrosion of copper and aluminum by the photoresist stripping solution. In Examples 4-6, the dosage and relative amounts of organic base compounds and additives were studied, and it was found that the photoresist stripping solution composition in Example 5 can reduce the corrosion of copper and aluminum while avoiding residue. At the same time, with the increase of the concentration of the two, the sol particle size is reduced during the sol particle size detection; It can be seen from the comparison of Examples 7-10 that with the increase of the dosage of additives and auxiliary additives, the corrosion of copper and aluminum and the sol particle size first decrease and then increase. Therefore, the dosage of additives and auxiliary additives needs to be within a reasonable range. Examples 7 and 8 have good effects.

[0129] Comparing Example 5 with Examples 11-13, it can be seen that compared with single MDEA or AEEA or other mixed amines as organic base compounds, the selection of a mixture of MDEA and AEEA as the organic base compound can better reduce the corrosion of the metal film layer, and at the same time can reduce the volume average diameter D(4,3) (particle size of large particles) and the area average diameter D(3,2) (actual particle size of particles).

[0130] Comparing Example 5 with Example 14, it can be seen that the auxiliary additive of dibutyl sebacate can better reduce the corrosion of the metal film layer, and at the same time can reduce the volume average diameter D(4,3) (particle size of large particles) and the area average diameter D(3,2) (actual particle size of particles).

[0131] Comparison of Examples 1-10 and Comparative Examples 1-5 shows that the photoresist stripping solution composition has a better effect when the components are within the preferred range. Figure 1-4 It can also be seen that the sol particle size in the detection solution of Example 5 and Example 8 is smaller than that of Comparative Example 1 and Comparative Example 5.

[0132] From the comparison of Example 8 with Comparative Examples 6-10, it can be seen that the use of the protonic polar solvent, aprotic protonic solvent, organic base compound, additive and auxiliary additive defined in the present application can reduce the photoresist residue and corrosion to the metal film layer, avoid the crystallization of solid additives, and at the same time reduce the volume average diameter D(4,3) (particle size of large particles) and the area average diameter D(3,2) (actual particle size of particles) compared with other reagents.

[0133] The foregoing description is merely a preferred embodiment of the present invention and is not intended to limit the present invention. Those skilled in the art will readily appreciate that various modifications and variations of the present invention are possible. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present invention are intended to be within the scope of protection of the present invention.

Claims

1. A photoresist stripping solution composition, characterized in that include: Protic solvent 58wt%-90wt%; 9 wt%-45 wt% of aprotic protic solvent; 0.9wt%-10wt% of an organic base compound; Additives 0.01wt%-1wt%; Auxiliary additives 0.01wt%-3wt%; The balance was deionized water.

2. The photoresist stripping liquid composition according to claim 1, wherein The mass fraction of the auxiliary additive is 0.02wt%-1wt%; And / or, the auxiliary additive comprises at least one of the compounds represented by Formula I, Formula II and Formula III, In formula I, R2 and R3 are each independently selected from an alkyl group having 1 to 3 carbon atoms; R1 and R4 are each independently selected from an alkyl group having 2 to 10 carbon atoms; In formula II, R1 and R3 are each independently selected from an alkyl group having 1 to 4 carbon atoms, and R2 is selected from an alkyl group having 3 to 11 carbon atoms; In formula III, R1, R2 and R3 are each independently selected from an alkyl group having 2 to 10 carbon atoms.

3. The photoresist stripping solution composition according to claim 2, characterized in that The compound of formula I is selected from at least one of dibutyl phthalate, dipropyl phthalate and dioctyl phthalate; and / or, the compound of formula II is at least one selected from dimethyl succinate, dimethyl adipate, dimethyl sebacate, dibutyl succinate, dibutyl adipate and dibutyl sebacate; And / or, the compound of formula III is at least one selected from glyceryl triacetate, glyceryl tripropionate and glyceryl tributyrate.

4. The photoresist stripping solution composition according to claim 1, characterized in that The protic solvent is obtained by an addition reaction between a monohydric alcohol having 1 to 8 carbon atoms and at least one of ethylene oxide, propylene oxide, and butylene oxide; And / or, the mass fraction of the protic solvent is 61 wt%-81 wt%.

5. The photoresist stripping solution composition according to claim 1, characterized in that The aprotic protophilic solvent is selected from at least one of formamide and its derivatives, solvents containing sulfur-oxygen double bonds, and nitrogen-containing heterocyclic solvents; And / or, the mass fraction of the aprotic protic solvent is 17 wt%-31 wt%.

6. The photoresist stripping solution composition according to claim 1, characterized in that The organic base compound is selected from at least one of an alcoholamine compound, a polyamine compound and a fatty amine compound; And / or, the mass fraction of the organic base compound is 1.5 wt%-4.5 wt%.

7. The photoresist stripping solution composition according to claim 1, characterized in that The additive comprises at least one of a metal protecting agent and a surfactant; And / or, the mass fraction of the additive is 0.03wt%-0.8wt%.

8. The photoresist stripping solution composition according to claim 1, wherein The protic solvent is obtained by an addition reaction between a monohydric alcohol having 1 to 5 carbon atoms and at least one of ethylene oxide, propylene oxide, and butylene oxide; and / or the metal protective agent is at least one selected from molybdic acid, citric acid, alanine, glycine, leucine, L-arginine, gallic acid, mercaptomethylimidazole, dimercaptobenzimidazole, dimercaptobenzothiazole, benzotriazole, methylbenzotriazole, pentamethylbenzotriazole, 5-aminotetrazole, 5-aminotetrazole, methimazole, 2-aminothiazole, N-vinylimidazole, benzotriazole and benzimidazole; And / or, the surfactant is selected from at least one of 1-adamantane acrylate, 4-biphenylmethanol acrylate, 4-hydroxyphenyl methacrylate, N-(p-hydroxyphenyl) methacrylate, sodium dodecylbenzenesulfonate, acrylic acid copolymer, chloroethidium acetate, diphenylpolysiloxane, methylphenylpolysiloxane, organic modified siloxane, fluorinated siloxane, polyoxyethylene ethyl ether, isomeric decanol polyoxyethylene ether and nonylphenol polyoxyethylene ether.

9. The photoresist stripping solution composition according to claim 1, characterized in that The protic solvent is selected from at least one of diethylene glycol methyl ether, diethylene glycol butyl ether, dipropylene glycol methyl ether, ethylene glycol butyl ether and ethylene glycol dimethyl ether.

10. The photoresist stripping liquid composition according to claim 1, characterized in that The aprotic protophilic solvent is selected from at least one of formamide, N-methylformamide, dimethylformamide, N,N-dimethylformamide, acetamide, dimethylacetamide, N-methylacetamide, N,N-dimethylacetamide, hexamethylphosphoramide, dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylimidazole and sulfolane; And / or, the organic base compound is selected from at least one of N-hydroxyethylpiperazine (HEP), N-methylmonoethanolamine, N-methyldiethanolamine, N,N-dimethylethanolamine, triethanolamine, isopropanolamine, ethylenediamine, hydroxyethylethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, tris(2-aminoethyl)amine, polyethylenepolyamine and dibutylamine.

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