A stripping solution with good stability, a preparation method and application thereof

Abstract

The application relates to a peeling solution with good stability and a preparation method and application thereof, and belongs to the technical field of liquid crystal panel and semiconductor production. The peeling solution comprises a solvent, a corrosion inhibitor and an amine reagent; the solvent comprises N, N-dimethylacetamide and diethylene glycol butyl ether; the corrosion inhibitor is 5-methylbenzotriazole; the amine reagent comprises cyclic amine and diethylene glycol amine, and the cyclic amine is a compound shown in formula A. The peeling solution has good lifetime stability, good solubility, good solubility stability, good corrosion stability and unexpected technical effects.

Description

Technical Field

[0001] The invention belongs to the technical field of liquid crystal panel and semiconductor production, and particularly relates to a stripping liquid with good stability and a preparation method thereof. Background Art

[0002] Photoresist, also known as photoresist, is primarily composed of three components: a photosensitive resin, a sensitizer, and a solvent. Upon exposure to light, the photosensitive resin rapidly undergoes a photocuring reaction in the exposed areas, significantly changing the material's physical properties, particularly its solubility and affinity. Through processes such as exposure, development, etching, diffusion, ion implantation, and metal deposition, the desired fine pattern is transferred from the mask to the substrate being processed. Finally, a stripping solution is used to remove the remaining photoresist from the unexposed areas, completing the pattern transfer process.

[0003] Existing stripping solutions usually use a system such as N-methylformamide + diethylene glycol butyl ether / diethylene glycol methyl ether. However, solvents such as N-methylformamide will hydrolyze in an alkaline environment, reducing the stripping ability and shortening the life of the stripping solution.

[0004] Therefore, there is still an urgent need for a stripping solution with good stability, long service life and good stripping effect. Summary of the Invention

[0005] In order to solve the above problems, the present invention provides a stripping liquid and a preparation method and application thereof.

[0006] In a first aspect, the present invention provides a stripping solution.

[0007] A stripping solution comprising a solvent, a corrosion inhibitor and an amine reagent; the solvent comprises N,N-dimethylacetamide and diethylene glycol butyl ether; the corrosion inhibitor is 5-methylbenzotriazole; the amine reagent comprises a cyclic amine and diglycolamine, and the cyclic amine is a compound represented by formula A.

[0008]

[0009] In some embodiments, the content of N,N-dimethylacetamide is 20.0 wt% to 40.0 wt% based on the total weight of the stripping solution. In some embodiments, the content of N,N-dimethylacetamide is 20.0 wt%, 25.0 wt%, 26.0 wt%, 27.0 wt%, 28.0 wt%, 29.0 wt%, 30.0 wt%, 31.0 wt%, 32.0 wt%, 33.0 wt%, 34.0 wt%, 35.0 wt%, 36.0 wt%, 37.0 wt%, 38.0 wt%, 39.0 wt%, or 40.0 wt% based on the total weight of the stripping solution.

[0010] In some embodiments, the content of butyl diglycol is 54.5 wt % to 77.9 wt % based on the total mass of the stripping solution. In some embodiments, the content of butyl diglycol is 54.5 wt %, 60.0 wt %, 65.0 wt %, 70.0 wt %, 75.0 wt % or 77.9 wt % based on the total mass of the stripping solution.

[0011] In some embodiments, the content of 5-methylbenzotriazole is 0.1 wt % to 0.5 wt % based on the total weight of the stripping solution. In some embodiments, the content of 5-methylbenzotriazole is 0.1 wt %, 0.2 wt %, 0.3 wt %, 0.4 wt % or 0.5 wt % based on the total weight of the stripping solution.

[0012] In some embodiments, the content of the compound represented by Formula A is 1.0 wt% to 2.0 wt% based on the total weight of the stripping solution. In some embodiments, the content of the compound represented by Formula A is 1.0 wt%, 1.5 wt% or 2.0 wt% based on the total weight of the stripping solution.

[0013] In some embodiments, the content of diglycolamine is 1.0 wt % to 2.0 wt % based on the total mass of the stripping solution. In some embodiments, the content of diglycolamine is 1.0 wt %, 1.5 wt % or 2.0 wt % based on the total mass of the stripping solution.

[0014] In some embodiments, calculated based on the total mass of the stripping solution, the content of N,N-dimethylacetamide is 27.0wt%-35.0wt%, the content of diethylene glycol butyl ether is 60.2wt%-70.7wt%, the content of 5-methylbenzotriazole is 0.3wt%-0.8wt%, the content of the compound represented by formula A is 1.0wt%-2.0wt%; and the content of diglycolamine is 1.0wt%-2.0wt%.

[0015] In some embodiments, based on the total mass of the stripping solution, the content of N,N-dimethylacetamide is 27.0wt%-35.0wt%, the content of 5-methylbenzotriazole is 0.3wt%-0.8wt%, the content of the compound represented by formula A is 1.0wt%-2.0wt%; the content of diglycolamine is 1.0wt%-2.0wt%, and the balance is diethylene glycol butyl ether.

[0016] In some embodiments, based on the total mass of the stripping solution, the content of N,N-dimethylacetamide is 27.0 wt%, the content of diethylene glycol butyl ether is 70.7 wt%, the content of 5-methylbenzotriazole is 0.3 wt%, the content of the compound represented by formula A is 1.0 wt%, and the content of diglycolamine is 1.0 wt%.

[0017] In some embodiments, the content of N,N-dimethylacetamide is 31.0 wt%, the content of diethylene glycol butyl ether is 65.5 wt%, the content of 5-methylbenzotriazole is 0.5 wt%, the content of the compound represented by formula A is 1.5 wt%, and the content of diglycolamine is 1.5 wt%.

[0018] In some embodiments, the content of N,N-dimethylacetamide is 35.0 wt %, the content of diethylene glycol butyl ether is 60.2 wt %, the content of 5-methylbenzotriazole is 0.8 wt %, the content of the compound represented by formula A is 2.0 wt %, and the content of diglycolamine is 2.0 wt %.

[0019] In a second aspect, the present invention provides a method for preparing the stripping solution described in the first aspect.

[0020] A method for preparing the stripping solution of the first aspect comprises: mixing a corrosion inhibitor and an amine reagent with a solvent to obtain the stripping solution.

[0021] In a third aspect, the present invention provides an application of the stripping solution described in the first aspect or the stripping solution prepared by the preparation method described in the second aspect.

[0022] A use of the stripping solution described in the first aspect or the stripping solution prepared by the preparation method described in the second aspect in the preparation of liquid crystal panels or semiconductors.

[0023] In some embodiments, a stripping solution described in the first aspect or a stripping solution prepared by the preparation method described in the second aspect is used in stripping or cleaning photoresist and / or its residues in preparing liquid crystal panels or semiconductors.

[0024] In some embodiments, the photoresist is a positive photoresist.

[0025] Beneficial effects

[0026] Compared with the prior art, the present invention has at least one of the following technical effects:

[0027] (1) Compared with other solvents, the use of N,N-dimethylacetamide and diethylene glycol butyl ether within the content range provided by the present invention as solvents is beneficial to significantly improve the lifetime stability of the obtained stripping solution, which has unexpected technical effects.

[0028] (2) Compared with other amine reagents, the use of the compound represented by formula A and diethyleneglycol amine in the content range provided by the present application as amine reagents is conducive to significantly improving the lifetime stability of the obtained stripping solution, and has unexpected technical effects.

[0029] (3) Compared with other amine reagents, such as any one of N-aminoethylpiperazine, aminoethylmorpholine, the compound represented by formula B or ethanolamine in combination with diethyleneglycol amine, the use of the compound represented by formula A and diethyleneglycol amine provided by the present application as amine reagents is more conducive to obtaining a stripping solution with good dissolution effect, and has unexpected technical effects.

[0030] (4) Compared with the use of other solvents, such as the combination of one of N-methylformamide, N,N-diethylformamide, N-ethylformamide, dimethylformamide and diethylene glycol butyl ether, the present application uses the combination of N,N-diethylacetamide and diethylene glycol butyl ether, which is more conducive to improving the dissolution stability of the obtained stripping solution, and has unexpected technical effects.

[0031] (5) Compared with other corrosion inhibitors, the use of 5-methylbenzotriazole as a corrosion inhibitor in the present application is more conducive to improving the corrosion stability of the obtained stripping solution, and has unexpected technical effects.

[0032] (6) Compared with the stripping solution of the prior art, the stripping solution provided by the present application has more stable corrosion stability and lifetime stability, and has unexpected technical effects.

[0033] Definitions of terms

[0034] Unless otherwise indicated, the following terms and phrases as used herein are intended to have the following meanings:

[0035] “V / V” means volume ratio. “wt%” means the mass percentage of the component mass to the total mass of the composition.

[0036] The term “optional”, “optionally”, or “may” means that the subsequently described event or circumstance can but need not occur.

[0037] The term “weight percent” or “percent by weight” or “wt%” is defined as the weight of a particular component in a composition divided by the total weight of all components in the composition and multiplied by 100%.

[0038] The term “and / or” should be understood to mean either one of the items or any combination of the items in the alternatives.

[0039] In the description of this specification, the reference terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" mean that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in this specification and features of different embodiments or examples without contradiction. DETAILED DESCRIPTION

[0040] In order to enable those skilled in the art to better understand the technical solutions of the present invention, some non-limiting embodiments are further disclosed below to further illustrate the present invention in detail.

[0041] The reagents used in the present invention can be purchased from the market or prepared by the method described in the present invention.

[0042] The structure of the compound represented by formula A described in this application is:

[0043]

[0044] The structure of the compound represented by formula B described in this application is:

[0045]

[0046] Example 1-Example 3: Preparation of stripping solution

[0047] Recipe: See Table 1.

[0048] Table 1: Stripping solution formulation

[0049]

[0050] Preparation method: An amine reagent, a corrosion inhibitor, and a solvent are mixed to obtain the stripping solution. Comparative Examples 1-4: Investigation of Solvents Formula: A single factor investigation was conducted based on the formula of Example 2. The formula is shown in Table 2.

[0051] Table 2: Investigation of solvents

[0052]

[0053]

[0054] Preparation method: An amine reagent, a corrosion inhibitor, and a solvent are mixed to obtain the stripping solution. Comparative Examples 5-9: Solvent Investigation Formulation: A single factor investigation was conducted based on the formulation of Example 2. The formulation is shown in Table 3.

[0055] Table 3: Investigation of solvents

[0056]

[0057]

[0058] Preparation method: An amine reagent, a corrosion inhibitor and a solvent are mixed to obtain the stripping solution. Comparative Examples 10-15: Corrosion Inhibitor Investigation Formulation: A single factor investigation was conducted based on the formulation of Example 2. The formulation is shown in Table 4.

[0059] Table 4: Investigation of corrosion inhibitors

[0060]

[0061]

[0062] Preparation method: An amine reagent, a corrosion inhibitor, and a solvent are mixed to obtain the stripping solution. Comparative Examples 16-20: Investigation of Amine Reagents Formula: A single factor investigation was conducted based on the formula of Example 2. The formula is shown in Table 5.

[0063] Table 5: Investigation of amine reagents

[0064]

[0065]

[0066] Preparation method: An amine reagent, a corrosion inhibitor and a solvent are mixed to obtain the stripping solution.

[0067] Comparative Example 21: Stripping solution of prior art (CN111458990A)

[0068] The stripping solution was prepared with reference to the second formula of CN111458990A (see paragraph 0030 of the specification of CN111458990A), as follows:

[0069] The following components in parts by weight were mixed to obtain a stripping solution of Comparative Example 21:

[0070] N-methylformamide (NMF): 54.2 parts by weight;

[0071] 40.0 parts by weight of diethylene glycol butyl ether (BDG);

[0072] AMP-95 (2-aminomethyl-1-propanol containing 5% water): 3.0 parts by weight;

[0073] Aminoethylpiperazine: 2.0 parts by weight;

[0074] Tolyltriazole: 0.5 parts by weight;

[0075] Benzotriazole: 0.1 parts by weight;

[0076] Polyethylene glycol: 0.2 parts by weight.

[0077] Test Example 1: Testing the Photoresist Dissolving Ability Experimental Procedure: 1 gram of positive photoresist (10 μm thick) was placed on a watch glass, baked at 140°C for 180 seconds, and then placed in 100 g of the stripping solution to be tested at 50°C. The dissolution time was recorded. The results are shown in Table 6.

[0078] Table 6: Test results of photoresist dissolving ability

[0079]

[0080]

[0081] Conclusion: Compared with other amine reagents, such as N-aminoethylpiperazine, aminoethylmorpholine, the compound represented by formula B, or any combination of ethanolamine and diglycolamine, the combination of the compound represented by formula A provided by the present invention and diglycolamine as an amine reagent is more conducive to obtaining a stripping solution with good dissolving effect, and has unexpected technical effects.

[0082] Test Example 2: Investigation of the Stability of Photoresist Dissolving Ability Operation: After the stripping solutions of the embodiments and comparative examples were prepared, they were placed in black light-proof bottles and placed at 30°C. Samples were taken at 0, 7 days, 15 days, 1 month, and 2 months to test their photoresist dissolving ability (the operation was the same as in Test Example 1). The results are shown in Table 7.

[0083] Table 7: Stability Study

[0084]

[0085]

[0086]

[0087] Note: “s” in the table stands for seconds.

[0088] Conclusion: Compared with the use of other solvents, such as a combination of one of N-methylformamide, N,N-diethylformamide, N-ethylformamide, and dimethylformamide with diethylene glycol butyl ether, the combination of N,N-diethylacetamide and diethylene glycol butyl ether used in the present invention is more conducive to improving the solubility stability of the obtained stripping solution, and has unexpected technical effects.

[0089] Test Example 3: Investigation of the Corrosion of Copper by Stripping Solution

[0090] Investigation of copper corrosion: The copper-plated sheet was immersed in the stripping solution at 50°C for 30 minutes, rinsed with pure water, and dried with nitrogen.

[0091] The film thickness was measured using a scanning electron microscope (SEM).

[0092] Study on copper corrosion stability: After the stripping solutions of the examples and comparative examples were prepared, they were placed in black, light-proof bottles and stored at 30°C. Samples were taken at 0, 7 days, 15 days, 1 month, and 2 months to test their copper corrosion resistance. The results are shown in Table 8.

[0093] Table 8: Investigation of the corrosion of copper by different stripping solutions

[0094]

[0095]

[0096] in conclusion:

[0097] (1) Compared with other corrosion inhibitors, the present invention uses 5-methylbenzotriazole as a corrosion inhibitor, which is more conducive to improving the corrosion stability of the obtained stripping solution and has unexpected technical effects.

[0098] (2) Compared with the stripping solution of the prior art, the stripping solution provided by the present invention has more stable corrosiveness and has unexpected technical effects.

[0099] Test Example 4: Lifetime test

[0100] After the stripping solutions of the examples and comparative examples were prepared, they were placed in black, light-proof bottles and stored at 30°C. Samples were taken at 0, 7 days, 15 days, 1 month, and 2 months to test their lifetimes. The results are shown in Table 9.

[0101] Lifetime test operation: Place positive photoresist (3cm×3cm, 8μm thick) on a watch glass, bake at 140℃ for 110 seconds, and then place them in 100g of 50℃ stripping solution to be tested. Record the time required for complete stripping. The stripping solution to be tested is continuously kept at 50℃ for lifetime test. During the test, the positive photoresist is stripped once according to the above operation at a frequency of once every 24 hours from 0h to 72h, and once according to the above operation at a frequency of once every 6 hours from 72h to 168h. After 168h, the positive photoresist is stripped once according to the above operation at a frequency of once every 6 hours until the time required for complete stripping of the positive photoresist is greater than 60 seconds. The holding time when the time required for complete stripping of the positive photoresist exceeds 60s is recorded from the time when the positive photoresist is first stripped, which is the lifetime of the stripping solution to be tested. The results are shown in Table 9.

[0102] Table 9: Lifetime results of the stripping solutions of various examples and comparative examples

[0103]

[0104]

[0105] Note: “h” in the table stands for hour.

[0106] in conclusion:

[0107] (1) Compared with other solvents, the use of N,N-dimethylacetamide and diethylene glycol butyl ether within the content range provided by the present invention as solvents is beneficial to significantly improve the lifetime stability of the obtained stripping solution, which has unexpected technical effects.

[0108] (2) Compared with other amine reagents, the use of the compound represented by formula A and diglycolamine within the content range provided by the present invention as amine reagents is beneficial to significantly improve the lifetime stability of the obtained stripping solution, which has unexpected technical effects.

[0109] (3) Compared with the stripping solution of the prior art, the stripping solution provided by the present invention has more stable lifetime stability and has unexpected technical effects.

[0110] The methods of the present invention have been described through preferred embodiments. It is apparent that those skilled in the art will be able to modify or appropriately alter and combine the methods and applications described herein within the scope, spirit, and spirit of the present invention to implement and apply the technology of the present invention. Those skilled in the art may refer to the disclosure herein and appropriately modify the process parameters to achieve the desired effect. It is particularly important to note that all similar substitutions and modifications apparent to those skilled in the art are considered encompassed by the present invention.

Claims

1. A stripping solution, characterized in that: The invention comprises a solvent, a corrosion inhibitor and an amine reagent; the solvent comprises N,N-dimethylacetamide and diethylene glycol butyl ether; the corrosion inhibitor is 5-methylbenzotriazole; the amine reagent comprises a cyclic amine and diglycolamine, and the cyclic amine is a compound represented by formula A. ； Calculated based on the total mass of the stripping solution, the content of N,N-dimethylacetamide is 20.0 wt%-40.0 wt%; Calculated based on the total mass of the stripping solution, the content of diethylene glycol butyl ether is 54.5 wt%-77.9 wt%; Calculated based on the total mass of the stripping solution, the content of 5-methylbenzotriazole is 0.1wt%-0.5wt%; Calculated based on the total mass of the stripping solution, the content of the compound represented by formula A is 1.0 wt%-2.0 wt%; Calculated based on the total mass of the stripping solution, the content of the diglycolamine is 1.0 wt % to 2.0 wt %.

2. The stripping solution according to claim 1, wherein, calculated based on the total mass of the stripping solution, the content of N,N-dimethylacetamide is 27.0 wt%-35.0 wt%, the content of diethylene glycol butyl ether is 60.2 wt%-70.7 wt%, the content of 5-methylbenzotriazole is 0.3 wt%-0.8 wt%, the content of the compound represented by formula A is 1.0 wt%-2.0 wt%; and the content of diglycolamine is 1.0 wt%-2.0 wt%.

3. The stripping solution according to claim 1, wherein, calculated based on the total mass of the stripping solution, the content of N,N-dimethylacetamide is 27.0 wt%-35.0 wt%; the content of 5-methylbenzotriazole is 0.3 wt%-0.8 wt%; the content of the compound represented by Formula A is 1.0 wt%-2.0 wt%; the content of diglycolamine is 1.0 wt%-2.0 wt%; and the balance is diethylene glycol butyl ether.

4. The stripping solution according to claim 1, wherein, based on the total mass of the stripping solution, the content of N,N-dimethylacetamide is 27.0 wt %, the content of diethylene glycol butyl ether is 70.7 wt %, the content of 5-methylbenzotriazole is 0.3 wt %, the content of the compound represented by formula A is 1.0 wt %, and the content of diglycolamine is 1.0 wt %; or The content of N,N-dimethylacetamide is 31.0 wt %, the content of diethylene glycol butyl ether is 65.5 wt %, the content of 5-methylbenzotriazole is 0.5 wt %, the content of the compound represented by formula A is 1.5 wt %, and the content of diglycolamine is 1.5 wt %; or The content of N,N-dimethylacetamide is 35.0 wt %, the content of diethylene glycol butyl ether is 60.2 wt %, the content of 5-methylbenzotriazole is 0.8 wt %, the content of the compound represented by formula A is 2.0 wt %, and the content of diglycolamine is 2.0 wt %.

5. A method for preparing the stripping solution according to any one of claims 1 to 4, comprising: The corrosion inhibitor and the amine reagent are mixed with a solvent to obtain the stripping solution.

6. Use of the stripping solution according to any one of claims 1 to 4 or the stripping solution prepared by the preparation method according to claim 5 in the preparation of liquid crystal panels or semiconductors.

7. Use of the stripping solution according to any one of claims 1 to 4 or the stripping solution prepared by the preparation method according to claim 5 in stripping or cleaning photoresist and / or its residues in the preparation of liquid crystal panels or semiconductors.

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