Aqueous stripping solution and use thereof

Abstract

The present invention provides a stripping solution and its application, belonging to the technical field of liquid crystal panel and semiconductor production. The stripping solution comprises a resist, an alkanolamine, a cyclic amine, an organic acid, a water-soluble organic solvent and water, and the resist comprises a compound shown in Formula I. The stripping solution has a good stripping effect and is less corrosive to metals, and can be used for photoresist stripping of high-precision liquid crystal panels and semiconductors.

Description

Technical Field

[0001] The invention belongs to the technical field of liquid crystal panel and semiconductor production, and in particular relates to a stripping liquid and a use thereof. Background Art

[0002] Photoresist, also known as photoresist, is mainly composed of three components: photosensitive resin, sensitizer and solvent. After being exposed to light, the photosensitive resin can quickly undergo a photocuring reaction in the exposed area, causing significant changes in the physical properties of this material, especially solubility and affinity. Through processes such as exposure, development, etching, diffusion, ion implantation, and metal deposition, the required fine pattern is transferred from the mask to the processed substrate, and finally the remaining photoresist in the unexposed part is cleaned by a degumming stripping solution, thus completing the entire pattern transfer process.

[0003] In the prior art, the stripping solution commonly used for positive photoresists and negative photoresists is mostly alkaline. The compatible stripping solution in the prior art, as described in CN106292209A, contains quaternary ammonium compounds, non-quaternary ammonium water-soluble solvents, metal protective agents, preservatives, surfactants, diol / ether organic compounds, and alkyl pyrrolidone. Among them, the main component organic amine is used to cut off long-chain insoluble substances such as photosensitive substances in the photoresist. The composition without adding metal protective agent has obvious corrosion effect on metal aluminum and copper, and the surface is metal surface discoloration and blackening. Commonly used metal protective agents include triazoles and sugar alcohols. The protective effect of metal protective agents is usually selective, and triazole compounds have good corrosion resistance effect on copper, low solubility in water, and the substrate after stripping treatment is rinsed with water, and the surface usually still has residues.

[0004] The main components of the existing water-based stripping solution are organic amine compounds, polar organic solvents and water. However, most of the existing water-based stripping solutions have problems such as corrosion of the metal layer, photoresist residue, short service life and poor stripping effect.

[0005] Therefore, there is still an urgent need for a stripping liquid that can prevent corrosion of the metal layer, has a good cleaning effect, good stripping performance, and a long service life. Summary of the invention

[0006] In order to solve the above problems, the present invention provides a stripping liquid and its use.

[0007] In a first aspect, a stripping solution is provided.

[0008] A stripping solution comprising an anti-corrosion agent, an alkanolamine, a cyclic amine, an organic acid, a water-soluble organic solvent and water, wherein the anti-corrosion agent comprises a compound shown in formula I,

[0009]

[0010] In some embodiments, the stripping solution can be used for photoresist stripping of substrates of copper, molybdenum, aluminum, copper-aluminum alloy, molybdenum-aluminum alloy or molybdenum-copper alloy. In some embodiments, the alkanolamine can include at least one selected from 2-aminoethanol, diethanolamine, N-ethylaminoethanol, N-methylaminoethanol, N-methyldiethanolamine, dimethylaminoethanol, 2-(2-aminoethoxy)ethanol, 1-amino-2-propanol and triethanolamine.

[0011] In some embodiments, the water-soluble organic solvent may include at least one selected from ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and tetraethylene glycol dimethyl ether compounds. In some embodiments, the water-soluble organic solvent is diethylene glycol methyl ether.

[0012] In some embodiments, the cyclic amine may include at least one selected from piperazine, imidazole, or piperidine.

[0013] In some embodiments, the organic acid may include at least one selected from malic acid, ascorbic acid, lactic acid, citric acid, and itaconic acid.

[0014] In some embodiments, the resist may further include a sugar alcohol-based resist.

[0015] In some embodiments, the sugar alcohol-based corrosion inhibitor may include glucose, sorbitol, xylitol, mannitol, and sorbitol.

[0016] In some embodiments, the content of the compound represented by Formula I can be 1.0wt%-10.0wt% based on the total mass of the stripping solution. In some embodiments, the content of the compound represented by Formula I is 1.0wt%, 2.0wt%, 3.0wt%, 4.0wt%, 5.0wt%, 6.0wt%, 7.0wt%, 8.0wt%, 9.0wt% or 10.0wt% based on the total mass of the stripping solution.

[0017] In some embodiments, the content of the alkanolamine can be 5.0wt%-15.0wt% based on the total mass of the stripping solution. In some embodiments, the content of the alkanolamine is 5.0wt%, 6.0wt%, 7.0wt%, 8.0wt%, 9.0wt%, 10.0wt%, 11.0wt%, 12.0wt%, 13.0wt%, 14.0wt% or 15.0wt% based on the total mass of the stripping solution.

[0018] In some embodiments, the content of the cyclic amine can be 1.0wt%-5.0wt% based on the total mass of the stripping solution. In some embodiments, the content of the cyclic amine is 1.0wt%, 2.0wt%, 3.0wt%, 4.0wt% or 5.0wt% based on the total mass of the stripping solution.

[0019] In some embodiments, the content of the organic acid can be 0.2wt%-0.5wt% based on the total mass of the stripping solution. In some embodiments, the content of the organic acid is 0.2wt%, 0.3wt%, 0.4wt% or 0.5wt% based on the total mass of the stripping solution. The addition of the organic acid is beneficial to improving the solubility of the alkanolamine and the stripping speed of the stripping solution.

[0020] In some embodiments, the content of the water-soluble organic solvent can be 25.5wt%-76.8wt% based on the total mass of the stripping solution. In some embodiments, the content of the water-soluble organic solvent is 43.5wt%-76.8wt% based on the total mass of the stripping solution. In some embodiments, the content of the water-soluble organic solvent is 30.0wt%-60.0wt% based on the total mass of the stripping solution. In some embodiments, the content of the water-soluble organic solvent is 40.0wt%-50.0wt% based on the total mass of the stripping solution. In some embodiments, the content of the water-soluble organic solvent is 40.0wt%-50.0wt% based on the total mass of the stripping solution. In some embodiments, based on the total mass of the stripping solution, the content of the water-soluble organic solvent is 25.5wt%, 30.0wt%, 35.0wt%, 40.0wt%, 43.5wt%, 45.0wt%, 50.0wt%, 55.0wt%, 60.0wt%, 65.0wt%, 70.0wt% or 76.8wt%.

[0021] In some embodiments, the water content can be 15.0wt%-40.0wt% based on the total mass of the stripping solution. In some embodiments, the water content is 20.0wt%-30.0wt% based on the total mass of the stripping solution. In some embodiments, the water content is 15.0wt%, 20.0wt%, 25.0wt%, 30.0wt%, 35.0wt% or 40.0wt% based on the total mass of the stripping solution.

[0022] In some embodiments, the content of the sugar alcohol resist can be 1.0wt%-4.0wt% based on the total mass of the stripping solution. In some embodiments, the content of the sugar alcohol resist is 1.0wt%, 2.0wt%, 3.0wt% or 4.0wt% based on the total mass of the stripping solution.

[0023] In some embodiments, a stripping solution includes a resist, an alkanolamine, a cyclic amine, an organic acid, a water-soluble organic solvent and water, wherein the resist includes a compound shown in Formula I and a sugar alcohol resist.

[0024] In some embodiments, a stripping solution includes an anti-corrosion agent, an alkanolamine, a cyclic amine, an organic acid, a water-soluble organic solvent and water, wherein the anti-corrosion agent includes a compound represented by formula I and a sugar alcohol anti-corrosion agent, and calculated based on the total mass of the stripping solution, the content of the compound represented by formula I is 1.0wt%-10.0wt%, the content of the alkanolamine is 5.0wt%-15.0wt%, the content of the water-soluble organic solvent is 25.5wt%-76.8wt%, the content of the sugar alcohol anti-corrosion agent is 1.0wt%-4.0wt%, the content of the cyclic amine is 1.0wt%-5.0wt%, the content of the organic acid is 0.2wt%-0.5wt%, and the balance is water.

[0025] In some embodiments, a stripping solution includes an anti-corrosion agent, an alkanolamine, a cyclic amine, an organic acid, a water-soluble organic solvent and water, wherein the anti-corrosion agent includes a compound represented by formula I and a sugar alcohol anti-corrosion agent, and calculated based on the total mass of the stripping solution, the content of the compound represented by formula I is 1.0wt%-10.0wt%, the content of the alkanolamine is 5.0wt%-15.0wt%, the content of the water-soluble organic solvent is 43.5wt%-76.8wt%, the content of the sugar alcohol anti-corrosion agent is 1.0wt%-4.0wt%, the content of the cyclic amine is 1.0wt%-5.0wt%, the content of the organic acid is 0.2wt%-0.5wt%, and the balance is water.

[0026] In some embodiments, a stripping solution includes an anti-corrosion agent, an alkanolamine, a cyclic amine, an organic acid, a water-soluble organic solvent and water, wherein the anti-corrosion agent includes a compound represented by formula I and a sugar alcohol anti-corrosion agent, and calculated based on the total mass of the stripping solution, the content of the compound represented by formula I is 1.0wt%-10.0wt%, the content of the alkanolamine is 5.0wt%-15.0wt%, the content of the water is 15.0wt%-40.0wt%, the content of the sugar alcohol anti-corrosion agent is 1.0wt%-4.0wt%, the content of the cyclic amine is 1.0wt%-5.0wt%, the content of the organic acid is 0.2wt%-0.5wt%, and the balance is a water-soluble organic solvent.

[0027] In a second aspect, a use of the aforementioned stripping solution is provided.

[0028] A use of the above-mentioned stripping solution for stripping photoresist on copper, molybdenum, aluminum, copper-aluminum alloy, molybdenum-aluminum alloy or molybdenum-copper alloy.

[0029] Beneficial Effects

[0030] Compared with the prior art, an embodiment of the present invention has at least one of the following technical effects:

[0031] (1) Compared with other resists, the present invention uses the compound shown in Formula I as the resist or uses the compound shown in Formula I or the compound shown in Formula I and a sugar alcohol resist as the resist, which can greatly reduce the corrosion of the stripping solution on copper, molybdenum or aluminum or alloys of any two metals thereof, and can be used for photoresist stripping of high-precision liquid crystal panels and semiconductors.

[0032] (2) Compared with other resists, the present invention simultaneously uses the compound shown in Formula I and the sugar alcohol resist as the resist of the stripping solution described in the present invention. The compound shown in Formula I and the sugar alcohol resist have a synergistic effect, which is beneficial to reduce the corrosion of copper, molybdenum or aluminum, and can be used for photoresist stripping of high-precision liquid crystal panels and semiconductors.

[0033] (3) The combined use of cyclic amines and alkanolamines is beneficial to increasing the stripping speed of photoresists and reducing photoresist residues.

[0034] (4) Organic acid is helpful to improve the solubility of alkanolamine and the stripping speed of the stripping solution.

[0035] Definition of terms

[0036] Unless otherwise indicated, the following terms and phrases as used herein are intended to have the following meanings:

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

[0038] The term "and / or" should be understood to mean any one of the optional items or a combination of any two or more of the optional items.

[0039] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means 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 may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction. DETAILED DESCRIPTION

[0040] In order to enable those skilled in the art to better understand the technical solution 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] Example 1-Example 5: Preparation of stripping solution

[0043] Prescription: as shown in Table 1.

[0044] Table 1: Peeling solution formulation

[0045]

[0046] Preparation method: Mix the components of the prescription according to the prescribed amount to obtain the stripping solution.

[0047] Comparative Examples 1-6: Preparation of Stripping Solution

[0048] Prescription: as shown in Table 2.

[0049] Table 2: Peeling fluid formulations

[0050]

[0051] Preparation method: Mix the components of the prescription according to the prescribed amount to obtain the stripping solution.

[0052] Compound of formula II:

[0053] Example 5: Peeling effect test

[0054] Test of stripping effect: prepare a glass substrate with a copper-molybdenum metal layer wiring film on the surface after wet etching, cut it into small pieces of 1cm×1cm, soak it in the stripping solution of the above-mentioned Example 1-Example 4 respectively, soak it at 35°C for 60 seconds respectively, take it out and wash it with ultrapure water, dry it with nitrogen, and observe the photoresist residue. The results are shown in Table 3.

[0055] Table 3: Peeling effect test results

[0056]

[0057]

[0058] Example 6: Anti-corrosion effect test

[0059] Test the anti-corrosion effect of the stripping solution as follows:

[0060] Copper wire pretreatment: 2 g of commercially available copper wire was immersed in a 1.0 wt % sodium hydroxide aqueous solution at 50° C. for 1 minute and a 1.0 wt % sulfuric acid aqueous solution at 50° C., then washed with ultrapure water, dried, and weighed.

[0061] Corrosion test: The pre-treated copper wire was immersed in the stripping solution of Example 1 to Example 4 and Comparative Example 1 to Comparative Example 6 at 70°C, respectively. After stirring for 1 hour, the copper wire was removed, the copper ion concentration in the stripping solution was detected, and the corrosion value was calculated according to the following formula. The results are shown in Table 4.

[0062] Corrosion value (ppb / mg) = copper ion concentration in stripping solution (ppb) / weight of copper wire before corrosion test (mg)

[0063] Table 4: Anti-corrosion effect test results

[0064] Stripping fluid Corrosiveness value (ppb / mg) Example 1 9.8 Example 2 5.2 Example 3 2.6 Example 4 4.9 Example 5 1.5 Comparative Example 1 20.4 Comparative Example 2 16.2 Comparative Example 3 30.8 Comparative Example 4 28.9 Comparative Example 5 155.6 Comparative Example 6 985.4

[0065] Conclusion: From the above results, it can be seen that the stripping solution provided by the present invention has a good stripping effect and has little corrosion to metals. Compared with other resists, the use of the compound shown in formula I as a resist can greatly reduce the corrosion of the stripping solution to metals. In addition, compared with other resists, the present invention simultaneously uses the compound shown in formula I and the sugar alcohol resist as the resist of the stripping solution of the present invention. There is a synergistic effect between the compound shown in formula I and the sugar alcohol resist, which is beneficial to reduce the corrosion to metals.

[0066] Example 7: Anti-corrosion effect test

[0067] Corrosion test: A glass substrate having a molybdenum-aluminum-molybdenum metal layer wiring film on its surface was wet-etched, cut into small pieces of 1 cm×1 cm, and immersed in diethylene glycol methyl ether at 40°C for 60 seconds to remove the surface photoresist.

[0068] The stripping solutions of Examples 1 to 5 and Comparative Examples 1 to 6 were respectively prepared into 2% aqueous stripping solution solutions (2 g stripping solution + 98 g pure water), and the wafers from which the photoresist was removed were immersed in the 2% aqueous stripping solution solutions of Examples 1 to 5 and Comparative Examples 1 to 6 at 40° C. for 10 min. The aluminum corrosion was observed by SEM. The results are shown in Table 5.

[0069] Table 5: Anti-corrosion effect test results

[0070] Stripping fluid Aluminum etching depth (nm) Example 1 0.02 Example 2 0.01 Example 3 0.01 Example 4 0.01 Example 5 0.01 Comparative Example 1 2.0 Comparative Example 2 1.3 Comparative Example 3 1.8 Comparative Example 4 1.7 Comparative Example 5 2.5 Comparative Example 6 4.3

[0071] Conclusion: From the results in Table 5, it can be seen that using the compound represented by Formula I or the compound represented by Formula I and a sugar alcohol resist as an anti-corrosion agent can greatly reduce the corrosion of the stripping solution to the metal.

[0072] Example 8: Testing of peeling effect

[0073] Test of stripping effect: prepare a glass substrate with a molybdenum-aluminum-molybdenum metal layer wiring film on the surface by wet etching, cut it into small pieces of 1cm×1cm, soak them in the stripping solutions of the above-mentioned Examples 1-5, respectively, and soak them at 40°C for 60 seconds. After taking them out, wash them with ultrapure water, dry them with nitrogen, and observe the photoresist residues. The results are shown in Table 6.

[0074] Table 6: Peeling effect test results

[0075] Stripping fluid Photoresist residue Example 1 No residue Example 2 No residue Example 3 No residue Example 4 No residue Example 5 No residue

[0076] Conclusion: When the stripping solution provided by the present invention is used, no residue is left when stripping the photoresist.

[0077] The method of the present invention has been described through preferred embodiments, and relevant personnel can obviously modify or appropriately change and combine the methods and applications described herein within the content, spirit and scope of the present invention to implement and apply the technology of the present invention. Those skilled in the art can refer to the content of this article and appropriately improve the process parameters. It is particularly important to point out that all similar replacements and modifications are obvious to those skilled in the art, and they are all considered to be included in the present invention.

Claims

1. A stripping solution comprising a resist, an alkanolamine, a cyclic amine, an organic acid, a water-soluble organic solvent and water, wherein the resist comprises a compound represented by formula I, (Formula I); The resist comprises a sugar alcohol resist; The organic acid comprises at least one selected from malic acid, ascorbic acid, lactic acid, citric acid and itaconic acid.

2. The stripping solution according to claim 1, wherein the alkanolamine comprises at least one selected from the group consisting of 2-aminoethanol, diethanolamine, N-ethylaminoethanol, N-methylaminoethanol, N-methyldiethanolamine, dimethylaminoethanol, 2-(2-aminoethoxy)ethanol, 1-amino-2-propanol and triethanolamine; The cyclic amine includes at least one selected from piperazine, imidazole or piperidine.

3. The stripping solution according to claim 1, wherein the water-soluble organic solvent comprises at least one selected from the group consisting of ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, triethylene glycol monomethyl ether, triethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, and tetraethylene glycol dimethyl ether. 4 . The stripping solution according to claim 1 , wherein the content of the compound represented by formula I is 1.0 wt % to 10.0 wt % based on the total mass of the stripping solution.

5. The stripping solution according to claim 1, wherein the content of the alkanolamine is 5.0 wt% to 15.0 wt% based on the total mass of the stripping solution; and / or The content of the cyclic amine is 1.0 wt% to 5.0 wt% based on the total mass of the stripping solution; and / or Calculated based on the total mass of the stripping solution, the content of the organic acid is 0.2wt%-0.5wt%. 6 . The stripping solution according to claim 1 , wherein the content of the water-soluble organic solvent is 25.5 wt % to 76.8 wt % based on the total mass of the stripping solution. 7 . The stripping solution according to claim 1 , wherein the content of water is 15.0 wt % to 40.0 wt % based on the total mass of the stripping solution. 8 . The stripping solution according to claim 1 , wherein the content of the sugar alcohol resist is 1.0 wt % to 4.0 wt % based on the total mass of the stripping solution.

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