Aqueous stripping solution and method of preparation and use

Abstract

The application provides a water-based stripping solution, a preparation method and application, and particularly relates to the technical field of stripping solutions. The water-based stripping solution comprises a coupling agent, pure water, a polarity enhancer, an alcohol ether compound, an amine compound and a corrosion inhibitor. The water-based stripping solution provided by the application effectively reduces the volatilization of the polarity enhancer, the alcohol ether compound, the amine compound and the pure water by adding the coupling agent in the system, reduces the operation risk in the process, enhances the stability of the water-based stripping solution, maintains the original stripping effect, and increases the service life of the water-based stripping solution. After ensuring the stripping effect of the water-based stripping solution, the use amount of the water-based stripping solution in the photoresist removal process is reduced, the sewage discharge amount is also reduced, and the manufacturing cost and the sewage treatment cost are reduced in the whole.

Description

Technical Field

[0001] This invention relates to the field of stripping fluid technology, and in particular to an aqueous stripping fluid, its preparation method, and its application. Background Technology

[0002] Stripping solution, as one of the most widely used wet electronic chemicals in display panel manufacturing, plays a crucial role in the production of TP / TFT-LCD / OLED display panels and is extensively applied in photovoltaic solar energy, display panels, and semiconductor fields. Stripping solution is typically used after the etching process to remove photoresist and residual substances while preventing damage to the underlying substrate.

[0003] The stripping process involves a chemical reaction between the stripping solution and the photoresist, causing the photoresist to expand, soften, and dissolve. Existing stripping solutions mainly include aqueous and organic stripping solutions. Aqueous stripping solutions primarily consist of organic reagents and pure water; the proportion of pure water varies depending on the solution. During the reaction between the aqueous stripping solution and the photoresist, the process temperature is generally between 40 and 60 degrees Celsius. A significant amount of pure water and organic matter still evaporates during use, causing changes in the content of each component in the aqueous stripping solution and affecting the stripping effect. Furthermore, the generation of organic vapors can compromise operational safety.

[0004] In view of this, the present invention is hereby proposed. Summary of the Invention

[0005] One of the objectives of this invention is to provide an aqueous stripping fluid to alleviate the technical problems in the prior art where the unstable composition of the aqueous stripping fluid affects the stripping effect and the generation of organic vapor during use affects operational safety.

[0006] The second objective of this invention is to provide a method for preparing an aqueous stripping solution.

[0007] The third objective of this invention is to provide an application of aqueous stripping solution in removing photoresist during semiconductor manufacturing.

[0008] In order to achieve the above-mentioned objectives of the present invention, the following technical solution is adopted:

[0009] The first aspect of the present invention provides an aqueous stripping fluid, comprising a coupling agent, pure water, a polarity enhancer, an alcohol ether compound, an amine compound, and a corrosion inhibitor.

[0010] Further, by weight, it includes 0.2-0.45 parts coupling agent, 25-35 parts pure water, 25-35 parts polarity enhancer, 10-15 parts alcohol ether compound, 15-25 parts amine compound and 1-5 parts corrosion inhibitor.

[0011] Furthermore, the coupling agent comprises at least one of epoxytrimethoxysilane, 3-glycidyl etheroxypropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and vinyltriethoxysilane.

[0012] Furthermore, the polarity enhancer includes at least one of dimethylacetamide, 4-methyl-2-pentanone, dimethylformamide, dimethyl sulfoxide, and nitromethane.

[0013] Furthermore, the alcohol ether compound includes at least one of triethanolamine, dipropylene glycol methyl ether acetate, dipropylene glycol butyl ether, benzyl alcohol, and diethylene glycol butyl ether.

[0014] Furthermore, the amine compound includes at least one of diisopropylamine, triethylenediamine, phthalimide, 1,2-dimethylpropylamine, N,N-diisopropylethylamine, and isopropanolamine.

[0015] Furthermore, the corrosion inhibitor includes at least one of catechol, benzotriazole, mercaptobenzothiazole, imidazole, and phosphonic acid.

[0016] Furthermore, the coupling agent is epoxytrimethoxysilane and 3-glycidyl etheroxypropyltriethoxysilane.

[0017] A second aspect of the present invention provides a method for preparing the aqueous stripping fluid, wherein all raw materials are mixed evenly to obtain the aqueous stripping fluid.

[0018] A third aspect of the invention provides the application of the aqueous stripping solution in removing photoresist during semiconductor manufacturing.

[0019] Compared with the prior art, the present invention has at least the following beneficial effects:

[0020] The aqueous stripping solution provided by this invention incorporates a coupling agent, effectively reducing the volatilization of polar enhancers, alcohol ether compounds, amine compounds, and pure water, thus lowering operational risks during the manufacturing process. Simultaneously, the stability of the aqueous stripping solution is enhanced, maintaining the original stripping effect and increasing its service life. By ensuring the stripping effect of the aqueous stripping solution, the amount used in the photoresist removal process is reduced, and the amount of wastewater discharged is also decreased, resulting in an overall reduction in manufacturing costs and wastewater treatment costs.

[0021] The preparation method provided by this invention is simple, highly mechanized, and suitable for large-scale industrial production.

[0022] The aqueous stripping solution provided by this invention offers a better stripping solution for semiconductor manufacturing processes, enabling complete removal of photoresist with virtually no residue, improving the precision of semiconductor devices, and promoting the development of the semiconductor manufacturing industry and downstream industries. Attached Figure Description

[0023] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0024] Figure 1 SEM images of photoresist stripped from semiconductor devices using the aqueous stripping solution provided in Example 1;

[0025] Figure 2 SEM images of the photoresist stripped from a semiconductor device using the aqueous stripping solution provided in Comparative Example 1. Detailed Implementation

[0026] The embodiments and examples of the present invention will be described in detail below with reference to the implementation methods and examples. However, those skilled in the art will understand that the following implementation methods and examples are only for illustrating the present invention and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0027] According to a first aspect of the present invention, an aqueous stripping fluid is provided, comprising a coupling agent, pure water, a polarity enhancer, an alcohol ether compound, an amine compound, and a corrosion inhibitor.

[0028] The aqueous stripping solution provided by this invention incorporates a coupling agent, effectively reducing the volatilization of polar enhancers, alcohol ether compounds, amine compounds, and pure water, thus lowering operational risks during the manufacturing process. Simultaneously, the stability of the aqueous stripping solution is enhanced, maintaining the original stripping effect and increasing its service life. By ensuring the stripping effect of the aqueous stripping solution, the amount used in the photoresist removal process is reduced, and the amount of wastewater discharged is also decreased, resulting in an overall reduction in manufacturing costs and wastewater treatment costs.

[0029] In aqueous stripping solutions, pure water acts as a solvent to enhance the rinsing power of the stripping solution, making it easier to remove the photoresist. Coupling agents reduce the volatility of the aqueous stripping solution, maintaining its overall stability.

[0030] In aqueous stripping fluid systems, amine compounds exhibit better ionization polarity. When amine compounds and alcohol ether compounds are mixed with polarity enhancers, their polarity increases upon the addition of coupling agents. Some groups in the coupling agent form chemical bonds with water, while others form strong intermolecular interactions with amine compounds or alcohol ether compounds, thereby improving the connection between molecules in the system.

[0031] Alcohol ether compounds, amine compounds, and polarity enhancers are well soluble in water. Under the action of coupling agents, the amino functional groups in amine compounds form ammonium salts with the coupling agents. When alcohol ether compounds polymerize with coupling agents in water to form hydrogen bonds, the nitrogen atoms in the amino, imino, and subamino groups in the solution become lone pairs of electrons, giving the amines nucleophilicity. This forms a stable network structure with the alcohol ether compounds in the solution, making the molecules more tightly connected in the solution and less prone to changes with temperature fluctuations. This better maintains the overall stability of the aqueous stripping solution and achieves the purpose of reducing the volatilization of the aqueous stripping solution.

[0032] Further, by weight, it includes 0.2-0.45 parts coupling agent, 25-35 parts pure water, 25-35 parts polarity enhancer, 10-15 parts alcohol ether compound, 15-25 parts amine compound and 1-5 parts corrosion inhibitor.

[0033] In some embodiments of the present invention, the coupling agent in the aqueous stripping solution is typically, but not limited to, 0.2 parts, 0.3 parts, 0.4 parts, or 0.45 parts by weight.

[0034] In some embodiments of the present invention, the water-based stripping solution typically contains, but is not limited to, 25, 27, 29, 31, 33, or 35 parts by weight of pure water; the polarity enhancer typically contains, but is not limited to, 25, 27, 29, 31, 33, or 35 parts by weight of the polarity enhancer; the alcohol ether compound typically contains, but is not limited to, 10, 11, 12, 13, 14, or 15 parts by weight of the alcohol ether compound; the amine compound typically contains, but is not limited to, 15, 17, 19, 21, 23, or 25 parts by weight of the amine compound; and the corrosion inhibitor typically contains, but is not limited to, 1, 2, 3, 4, or 5 parts by weight of the corrosion inhibitor.

[0035] Furthermore, the coupling agent comprises at least one of epoxytrimethoxysilane, 3-glycidyl etheroxypropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and vinyltriethoxysilane.

[0036] Furthermore, the polarity enhancer includes at least one of dimethylacetamide, 4-methyl-2-pentanone, dimethylformamide, dimethyl sulfoxide, and nitromethane.

[0037] Furthermore, the alcohol ether compound includes at least one of triethanolamine, dipropylene glycol methyl ether acetate, dipropylene glycol butyl ether, benzyl alcohol, and diethylene glycol butyl ether.

[0038] Furthermore, the amine compound includes at least one of diisopropylamine, triethylenediamine, phthalimide, 1,2-dimethylpropylamine, N,N-diisopropylethylamine, and isopropanolamine.

[0039] Furthermore, the corrosion inhibitor includes at least one of catechol, benzotriazole, mercaptobenzothiazole, imidazole, and phosphonic acid.

[0040] Furthermore, the coupling agent is epoxytrimethoxysilane and 3-glycidyl etheroxypropyltriethoxysilane.

[0041] A second aspect of the present invention provides a method for preparing the aqueous stripping fluid, wherein all raw materials are mixed evenly to obtain the aqueous stripping fluid.

[0042] The preparation method provided by this invention is simple, highly mechanized, and suitable for large-scale industrial production.

[0043] A third aspect of the invention provides the application of the aqueous stripping solution in removing photoresist during semiconductor manufacturing.

[0044] The aqueous stripping solution provided by this invention offers a better stripping solution for semiconductor manufacturing processes, enabling complete removal of photoresist with virtually no residue, improving the precision of semiconductor devices, and promoting the development of the semiconductor manufacturing industry and downstream industries.

[0045] The present invention is further illustrated below with specific embodiments and comparative examples. However, it should be understood that these embodiments are merely for illustrative purposes and should not be construed as limiting the invention in any way. Unless otherwise specified, the raw materials used in the embodiments and comparative examples of the present invention were carried out under conventional conditions or conditions recommended by the manufacturer. Reagents or instruments used, unless otherwise specified, are all commercially available conventional products.

[0046] Example 1

[0047] This embodiment provides an aqueous stripping solution comprising 2g of epoxytrimethoxysilane, 2g of 3-glycidyl etheroxypropyltriethoxysilane, 330g of pure water, 340g of dimethylformamide, 120g of diethylene glycol butyl ether, 200g of N,N-diisopropylethylamine, and 30g of benzotriazole. The above substances are stirred evenly to obtain the aqueous stripping solution.

[0048] Example 2

[0049] This embodiment provides an aqueous stripping solution comprising 0.75g of epoxytrimethoxysilane, 0.75g of 3-glycidyl etheroxypropyltriethoxysilane, 330g of pure water, 340g of dimethylformamide, 120g of diethylene glycol butyl ether, 200g of N,N-diisopropylethylamine, and 30g of benzotriazole. The above substances are stirred evenly to obtain the aqueous stripping solution.

[0050] Example 3

[0051] This embodiment provides an aqueous stripping solution comprising 7.5g of epoxytrimethoxysilane, 7.5g of 3-glycidyl etheroxypropyltriethoxysilane, 330g of pure water, 340g of dimethylformamide, 120g of diethylene glycol butyl ether, 200g of N,N-diisopropylethylamine, and 30g of benzotriazole. The above substances are stirred evenly to obtain the aqueous stripping solution.

[0052] Example 4

[0053] This embodiment provides an aqueous stripping solution comprising 1g of epoxytrimethoxysilane, 1g of 3-glycidyl etheroxypropyltriethoxysilane, 330g of pure water, 340g of dimethylformamide, 120g of diethylene glycol butyl ether, 200g of N,N-diisopropylethylamine, and 30g of benzotriazole. The above substances are stirred evenly to obtain the aqueous stripping solution.

[0054] Example 5

[0055] This embodiment provides an aqueous stripping solution comprising 2.4g of epoxytrimethoxysilane, 2.4g of 3-glycidyl etheroxypropyltriethoxysilane, 330g of pure water, 340g of dimethylformamide, 120g of diethylene glycol butyl ether, 200g of N,N-diisopropylethylamine, and 30g of benzotriazole. The above substances are stirred evenly to obtain the aqueous stripping solution.

[0056] Example 6

[0057] This embodiment provides an aqueous stripping solution comprising 2g of γ-methacryloxypropyltrimethoxysilane, 2g of vinyltriethoxysilane, 330g of pure water, 340g of dimethylformamide, 120g of diethylene glycol butyl ether, 200g of N,N-diisopropylethylamine, and 30g of benzotriazole. The above substances are stirred evenly to obtain the aqueous stripping solution.

[0058] Example 7

[0059] This embodiment provides an aqueous stripping solution comprising 1.5g of epoxytrimethoxysilane, 1.5g of 3-glycidyl etheroxypropyltriethoxysilane, 300g of pure water, 210g of dimethylformamide, 120g of diethylene glycol butyl ether, 200g of N,N-diisopropylethylamine, and 30g of benzotriazole. The above substances are stirred evenly to obtain the aqueous stripping solution.

[0060] Example 8

[0061] This embodiment provides an aqueous stripping solution comprising 1.5g of epoxytrimethoxysilane, 1.5g of 3-glycidyl etheroxypropyltriethoxysilane, 300g of pure water, 360g of dimethylformamide, 120g of diethylene glycol butyl ether, 200g of N,N-diisopropylethylamine, and 30g of benzotriazole. The above substances are stirred evenly to obtain the aqueous stripping solution.

[0062] Comparative Example 1

[0063] This comparative example provides an aqueous stripping solution comprising 330g of pure water, 340g of dimethylformamide, 120g of diethylene glycol butyl ether, 200g of N,N-diisopropylethylamine, and 30g of benzotriazole. The above substances are stirred evenly to obtain the aqueous stripping solution.

[0064] Comparative Example 2

[0065] This comparative example provides an aqueous stripping solution comprising 2g of epoxytrimethoxysilane, 2g of 3-glycidyl etheroxypropyltriethoxysilane, 330g of pure water, 120g of diethylene glycol butyl ether, 200g of N,N-diisopropylethylamine, and 30g of benzotriazole. The above substances are stirred evenly to obtain the aqueous stripping solution.

[0066] Comparative Example 3

[0067] This comparative example provides an aqueous stripping solution comprising 330g of pure water, 120g of diethylene glycol butyl ether, 200g of N,N-diisopropylethylamine, and 30g of benzotriazole. The above substances are stirred evenly to obtain the aqueous stripping solution.

[0068] Experimental Example 1

[0069] The stability of the aqueous stripping solutions provided in Examples 1-8 and Comparative Examples 1-3 was tested as follows: the aqueous stripping solutions were continuously stirred at 60°C, and the content of each component was measured every 12 hours.

[0070] Pure water testing: The testing instrument is a moisture analyzer; the testing method is the Karl Fischer volumetric method.

[0071] Coupling agent detection: The detection instrument is a gas chromatograph; the detector is a flame ionization detector.

[0072] Detection of polarity enhancers: The detection instrument is a gas chromatograph; the detector is a flame ionization detector.

[0073] Detection of alcohol and ether compounds: The detection instrument is a gas chromatograph; the detector is a flame ionization detector.

[0074] Detection of amine compounds: The detection instrument is a gas chromatograph; the detector is a flame ionization detector.

[0075] Corrosion inhibitor detection: The detection instrument is a high performance liquid chromatograph; the detector is a UV detector with a detection wavelength of 270 nm.

[0076] The detection results of Examples 1-8 and Comparative Examples 1-3 are shown in Tables 1-11 below.

[0077] Table 1. Detection data for Example 1

[0078]

[0079] Table 2 Detection data table for Example 2

[0080]

[0081]

[0082] Table 3. Detection data table for Example 3

[0083]

[0084] Table 4. Detection data from Example 4

[0085]

[0086]

[0087] Table 5. Detection data from Example 5

[0088]

[0089]

[0090] Table 6. Detection data from Example 6

[0091]

[0092] Table 7. Detection data from Example 7

[0093]

[0094]

[0095] Table 8. Detection data table for Example 8

[0096]

[0097] Table 9 shows the detection data for Comparative Example 1.

[0098]

[0099]

[0100] Table 10 shows the detection data for Comparative Example 2.

[0101]

[0102] Table 11 Detection data of Comparative Example 3

[0103]

[0104]

[0105] As can be seen from Tables 1-11, in Comparative Example 1, without the addition of a coupling agent, the components in the sample under specified conditions underwent significant changes after 12 hours. In Example 1, with the addition of the coupling agent provided by this invention, the volatilization of each component in the sample was significantly reduced compared to Comparative Example 1. In Example 2, with the addition of a small amount of coupling agent, the volatilization of each component was reduced compared to Comparative Example 1, but the volatilization of each component was increased compared to Example 1. When the amount of coupling agent added is insufficient, the stability of the component content cannot be well maintained. In Example 3, with the addition of a relatively large amount of coupling agent, the volatilization of each component was reduced compared to Comparative Example 1, but the volatilization of each component was increased compared to Example 1. The stripping effect was better than Comparative Example 1, but not as good as Example 1. When the addition of coupling agent is outside the scope of this invention, it is not conducive to the stability of the component content.

[0106] Experimental Example 2

[0107] The peeling ability of the aqueous peeling solutions provided in Examples 1-8 and Comparative Examples 1-3 was tested. The specific test steps are as follows: After the samples were peeled in the aqueous peeling solution, they were cleaned with deionized water and dried with nitrogen gas; the peeling effect was observed using a scanning electron microscope.

[0108] The results are shown in Tables 12 and 13 below.

[0109] Table 12 Results of Peeling Ability Test

[0110]

[0111]

[0112] Table 13 Results of Peeling Ability Test

[0113]

[0114]

[0115] As can be seen from Tables 12 and 13, in Comparative Example 1, without the addition of a coupling agent, the components in the sample under specified conditions underwent significant changes after 12 hours, resulting in a mediocre peeling effect. In Example 1, with the addition of an appropriate amount of the coupling agent of this invention, the content of each component in the sample was significantly reduced compared to Comparative Example 1, and the peeling performance remained completely achieved after 96 hours, indicating a substantial improvement in peeling performance after the addition of the coupling agent. In Example 2, with the addition of a slightly smaller amount of coupling agent, the peeling effect was better than Comparative Example 1 but not as good as Example 1. In Example 3, with the addition of an excessive amount of coupling agent, the peeling effect was better than Comparative Example 1 but not as good as Example 1; when an excessive amount of coupling agent is added, it is detrimental to the stability of the content of each component.

[0116] Experimental Example 3

[0117] The aqueous stripping solution provided in Example 1 and Comparative Example 1 was used to strip the photoresist after stirring and storing for 96 hours.

[0118] The p-Si substrate after peeling was photographed using SEM, and the results are as follows: Figure 1 and Figure 2 As shown. From Figure 1 and Figure 2 As can be seen, in Example 1, after adding the coupling agent aqueous stripping solution and letting it stand for 96 hours, the photoresist was completely stripped; in Comparative Example 1, after adding the coupling agent aqueous stripping solution and letting it stand for 96 hours, the photoresist was not stripped.

[0119] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A water-based stripping solution, characterized in that, By weight, it includes 0.2-0.45 parts coupling agent, 25-35 parts pure water, 25-35 parts polarity enhancer, 10-15 parts alcohol ether compound, 15-25 parts amine compound and 1-5 parts corrosion inhibitor.

2. The aqueous stripping solution according to claim 1, characterized in that, The coupling agent includes at least one of epoxytrimethoxysilane, 3-glycidyl etheroxypropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, and vinyltriethoxysilane.

3. The aqueous stripping solution according to claim 1, characterized in that, The polarity enhancer includes at least one of dimethylacetamide, 4-methyl-2-pentanone, dimethylformamide, dimethyl sulfoxide, and nitromethane.

4. The aqueous stripping solution according to claim 1, characterized in that, The alcohol ether compound includes at least one of triethanolamine, dipropylene glycol methyl ether acetate, dipropylene glycol butyl ether, benzyl alcohol, and diethylene glycol butyl ether.

5. The aqueous stripping solution according to claim 1, characterized in that, The amine compounds include at least one of diisopropylamine, triethylenediamine, phthalimide, 1,2-dimethylpropylamine, N,N-diisopropylethylamine, and isopropanolamine.

6. The aqueous stripping solution according to claim 1, characterized in that, The corrosion inhibitor includes at least one of catechol, benzotriazole, mercaptobenzothiazole, imidazole, and phosphonic acid.

7. The aqueous stripping solution according to claim 2, characterized in that, The coupling agents are epoxytrimethoxysilane and 3-glycidyl etheroxypropyltriethoxysilane.

8. A method for preparing the aqueous stripping solution according to any one of claims 1-7, characterized in that, All raw materials are mixed evenly to obtain the aqueous stripping solution.

9. The use of the aqueous stripping solution according to any one of claims 1-7 in removing photoresist during semiconductor manufacturing.

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