Stripping solution and preparation method thereof

Abstract

A stripping solution and a preparation method thereof, belonging to the technical field of liquid crystal panel and semiconductor production. The stripping solution comprises a compound shown in formula I, a water-soluble organic solvent, an amine reagent, a corrosion inhibitor, a nonionic surfactant and water. The stripping solution is used for stripping photoresist, and the stripping solution has the advantages of good stripping effect, no photoresist residue after stripping, good corrosion resistance to metal, long service life, etc.

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 and a preparation method 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] 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.

[0004] 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

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

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

[0007] A stripping solution comprises a compound represented by Formula I, a water-soluble organic solvent, an amine reagent, a corrosion inhibitor, a nonionic surfactant and water; the compound represented by Formula I is as follows:

[0008]

[0009] The nonionic surfactant may include or be a compound represented by Formula II,

[0010]

[0011] Wherein, n is an integer from 10 to 20. In some embodiments, n is 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20.

[0012] 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 certain embodiments, the water-soluble organic solvent is at least one selected from ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol methyl ether, and diethylene glycol ethyl ether. In certain embodiments, the water-soluble organic solvent is diethylene glycol methyl ether.

[0013] The amine reagent may include at least one selected from cyclic amines and alkanolamines. In some embodiments, the amine reagent may include cyclic amines and alkanolamines.

[0014] The cyclic amine may include at least one selected from hydroxyethylpiperazine, piperazine, N-methyl-piperazine, and methyl-piperazine. In some embodiments, the cyclic amine is hydroxyethylpiperazine.

[0015] The alkanolamine may include at least one selected from monoethanolamine, diethanolamine, triethanolamine, 2-(2-aminoethoxy)ethanol, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dibutylethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, N-(2-aminoethyl)ethanolamine, and triisopropanolamine; preferably diethanolamine.

[0016] The corrosion inhibitor may include at least one selected from benzotriazole and sorbitol.

[0017] Based on the total weight of the stripping solution, the content of the compound of formula I may be 1 wt% to 5 wt%. In some embodiments, the content of the compound of formula I is 1 wt%, 2 wt%, 3 wt%, 4 wt% or 5 wt%.

[0018] Based on the total mass of the stripping solution, the content of the water-soluble organic solvent may be 38.4wt%-78.95wt%. In some embodiments, based on the total mass of the stripping solution, the content of the water-soluble organic solvent is 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt% or 75wt%.

[0019] Based on the total mass of the stripping solution, the content of the amine reagent can be 5wt%-15wt%. In some embodiments, based on the total mass of the stripping solution, the content of the amine reagent is 8wt%-12wt%. In some embodiments, based on the total mass of the stripping solution, the content of the amine reagent is 10wt%-15wt%. In some embodiments, based on the total mass of the stripping solution, the content of the amine reagent is 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt% or 15wt%.

[0020] Based on the total mass of the stripping solution, the content of the corrosion inhibitor may be 0.05wt%-1.5wt%. In some embodiments, based on the total mass of the stripping solution, the content of the corrosion inhibitor is 0.1wt%-1.0wt%. In some embodiments, based on the total mass of the stripping solution, the content of the corrosion inhibitor is 0.05wt%, 0.1wt%, 0.15wt%, 0.5wt%, 1.0wt% or 1.5wt%.

[0021] Based on the total mass of the stripping solution, the content of the nonionic surfactant can be 0-0.1wt%. In some embodiments, based on the total mass of the stripping solution, the content of the nonionic surfactant is 0.05wt%-0.1wt%. In some embodiments, based on the total mass of the stripping solution, the content of the nonionic surfactant is 0, 0.05wt% or 0.1wt%.

[0022] Based on the total mass of the stripping solution, the water content may be 15wt%-40wt%. In some embodiments, based on the total mass of the stripping solution, the water content is 20wt%-30wt%. In some embodiments, based on the total mass of the stripping solution, the water content is 15wt%, 20wt%, 25wt%, 30wt%, 35wt% or 40wt%.

[0023] Calculated based on the total mass of the stripping solution, the content of the water-soluble organic solvent may be the remaining content obtained by subtracting the sum of the contents of the compound represented by Formula I, the amine reagent, the corrosion inhibitor, the nonionic surfactant and water from 100 wt %.

[0024] Calculated based on the total mass of the stripping solution, the content of the compound represented by formula I is 1wt%-5wt%, the content of the amine reagent is 5wt%-15wt%, the content of the corrosion inhibitor is 0.05wt%-1.5wt%, the content of the non-ionic surfactant is 0-0.1wt%, the content of water is 15wt%-40wt%, and the balance is the water-soluble organic solvent.

[0025] The amine reagent may include a cyclic amine and an alkanolamine; based on the total mass of the stripping solution, the content of the cyclic amine may be 0.5wt%-5wt%, and the content of the alkanolamine may be 5wt%-14.5wt%. In some embodiments, the amine reagent may include a cyclic amine and an alkanolamine; based on the total mass of the stripping solution, the content of the cyclic amine is 0.5wt%, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt%, 3.0wt%, 3.5wt%, 4.0wt%, 4.5wt% or 5wt%, and the content of the alkanolamine is 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 11wt%, 12wt%, 13wt%, 14wt% or 14.5wt%.

[0026] The corrosion inhibitor may include benzotriazole and sorbitol. Based on the total mass of the stripping solution, the content of the benzotriazole may be 0.05wt%-1.45wt%, and the content of the sorbitol may be 0.05wt%-1.45wt%. The corrosion inhibitor may include benzotriazole and sorbitol. Based on the total mass of the stripping solution, the content of benzotriazole is 0.05wt%, 0.10wt%, 0.20wt%, 0.50wt%, 0.95wt%, 1.0wt%, 1.10wt%, 1.15wt%, 1.20wt%, 1.25wt%, 1.30wt%, 1.35wt%, 1.40wt% or 1.45wt%, and the content of sorbitol is 0.05wt%, 0.10wt%, 0.20wt%, 0.50wt%, 0.95wt%, 1.0wt%, 1.10wt%, 1.15wt%, 1.20wt%, 1.25wt%, 1.30wt%, 1.35wt%, 1.40wt% or 1.45wt%.

[0027] In some embodiments of the present invention, a stripping solution includes a compound shown in formula I, a water-soluble organic solvent, an amine reagent, a corrosion inhibitor, a nonionic surfactant and water; the nonionic surfactant is a compound shown in formula II, the amine reagent includes a cyclic amine and an alkanolamine, the corrosion inhibitor includes benzotriazole and sorbitol, and based on the total mass of the stripping solution, the content of the compound shown in formula I is 1wt%-5wt%, the content of the cyclic amine is 0.5wt%-5wt%, the content of the alkanolamine is 5wt%-14.5wt%, the content of the benzotriazole is 0.05wt%-1.45wt%, the content of the sorbitol is 0.05wt%-1.45wt%, the content of the nonionic surfactant is 0-0.1wt%, the content of the water is 15wt%-40wt%, and the balance is the water-soluble organic solvent.

[0028] In a second aspect, the present invention provides a method for preparing the stripping solution described in the first aspect.

[0029] A method for preparing the stripping solution of the first aspect comprises mixing the compound represented by formula I, a water-soluble organic solvent, an amine reagent, a corrosion inhibitor, a nonionic surfactant and water.

[0030] Beneficial Effects

[0031] Compared with the prior art, the present invention has at least one of the following technical effects:

[0032] (1) Compared with other surfactants, the stripping solution obtained by adding the compound represented by formula II can reduce the corrosiveness of metal layers (for example, reducing the corrosiveness to copper-molybdenum metal layers such as molybdenum, aluminum, copper, titanium, molybdenum-aluminum, molybdenum-aluminum-molybdenum, copper-molybdenum, molybdenum-titanium, etc.), and can also extend the service life of the stripping solution, and has a good stripping effect without photoresist residue.

[0033] (2) Compared with other quaternary ammonium hydroxides, the stripping solution obtained by adding the compound shown in Formula I can reduce the corrosiveness of the metal layer (for example, reducing the corrosiveness to copper-molybdenum metal layers such as molybdenum, aluminum, copper, titanium, molybdenum-aluminum, molybdenum-aluminum-molybdenum, copper-molybdenum, molybdenum-titanium, etc.), and also has a good stripping effect without photoresist residue.

[0034] (3) The present invention uses benzotriazole and sorbitol as corrosion inhibitors, which can synergistically reduce the corrosion of the metal layer with the compound represented by Formula II.

[0035] (4) The reagent used in the present invention is a water-soluble reagent with good cleaning performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 Schematic diagram of corrosion height and corrosion depth in the corrosion of aluminum in the molybdenum-aluminum metal layer.

[0037] Definition of terms

[0038] Unless otherwise indicated, the following terms and phrases as used herein are intended to have the following meanings:

[0039] "V / V" means volume ratio. "wt%" means the mass percentage of the component to the total mass of the composition.

[0040] The terms "optional", "optional" or "optionally" mean that the subsequently described event or circumstance may but need not occur.

[0041] 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%.

[0042] 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.

[0043] 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

[0044] 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.

[0045] The reagents used in the present invention can be purchased from the market or prepared by the method described in the present invention.

[0046] Example 1: Preparation of nonionic surfactant

[0047]

[0048] 1.35g of the compound represented by formula B (5mmol) and 2.00g of the compound represented by formula III (5mmol) were dissolved in a mixed solution of 200mL tetrahydrofuran and methanol (tetrahydrofuran: methanol = 1: 1 (V / V)), and then 2.06g of dicyclohexylcarbodiimide (10mmol) was added, and the mixture was reacted at 50°C for 12 hours, and the solvent was removed by rotary evaporation, and the mixture was purified by column chromatography (eluent: chloroform: methanol = 4: 1 (V / V)), and dried to obtain 2.07g of the compound represented by formula A (white solid, yield 64%). The obtained compound represented by formula A was tested for mass spectrum and hydrogen spectrum, and the results were as follows:

[0049] HRMS[M+H] + :Molecular formula: C 29 H 49 NO 15 , theoretical value: 651.3102; measured value: 651.3099.

[0050] Hydrogen spectrum: 1 H NMR (400MHz, Chloroform-d) δ5.37 (d, J=7.0Hz, 1H), 5.16 (d, J=7.0Hz, 1H), 4.39-4.33 (m , 2H), 3.98-3.71 (m, 5H), 3.64 (q, J=6.9Hz, 1H), 3.61-3.50 (m, 3H), 3.47 (dt, J=8.8, 7.0H z, 1H), 3.35 (q, J=7.1Hz, 1H), 2.90 (p, J=7.0Hz, 1H), 2.672.57 (m, 2H), 1.57 (qd, J=7.1, 1 .6Hz, 2H), 1.48-1.34(m, 2H), 1.33-1.26(m, 2H), 1.29-1.18(m, 14H), 0.93-0.80(m, 3H).

[0051] Example 2: Preparation of nonionic surfactant

[0052]

[0053] 2.05 g of the compound represented by formula D (5 mmol) and 2.00 g of the compound represented by formula III (5 mmol) were dissolved in a mixed solution of 300 mL of tetrahydrofuran and methanol (tetrahydrofuran: methanol = 1: 1 (V / V)), and then 1.03 g of dicyclohexylcarbodiimide (5 mmol) was added, and the mixture was reacted at 40°C for 18 hours, and the solvent was removed by rotary evaporation, and the mixture was purified by column chromatography (eluent: chloroform: methanol = 4: 1 (V / V)), and dried to obtain 2.36 g of the compound represented by formula A (white solid, yield 60%). The obtained compound represented by formula C was tested for mass spectrum, and the results were as follows:

[0054] HRMS[M+H] + :Molecular formula: C 39 H 69 NO 15 , theoretical value: 791.4667; measured value: 791.4650.

[0055] Hydrogen spectrum: 1 H NMR (400MHz, Chloroform-d) δ5.34 (d, J=7.0Hz, 1H), 5.14 (d, J=6.8Hz, 1H), 4.40-4.31 (m, 2H), 4.30 (d, J=12.3Hz, 1H), 3.91-3.83 (m, 4H), 3.63 (q, J=6.9H z, 1H), 3.61-3.44 (m, 5H), 3.423.34 (m, 1H), 2.92 (p, J=7.0Hz, 1H), 2.672.56 (m, 2H), 1.54 (qd, J=7.1, 1.6Hz, 2H), 1.47-1.13 (m, 38H), 0.95-0.80 (m, 3H).

[0056] Example 3: Preparation of stripping solution

[0057] Prescription: As shown in Table 1.

[0058] Table 1: Peeling solution formulation

[0059]

[0060] Preparation method: The compound shown in formula I, a water-soluble organic solvent, a cyclic amine, an alkanolamine, a corrosion inhibitor, a nonionic surfactant and water are mixed according to the prescribed amount to obtain a stripping solution.

[0061] Example 4: Preparation of stripping solution

[0062] Prescription: As shown in Table 2.

[0063] Table 2: Peeling fluid formulations

[0064]

[0065]

[0066] Preparation method: The compound shown in formula I, a water-soluble organic solvent, a cyclic amine, an alkanolamine, a corrosion inhibitor, a nonionic surfactant and water are mixed according to the prescribed amount to obtain a stripping solution.

[0067] Comparative Examples 1 to 4: Investigation of Different Types of Quaternary Ammonium Hydroxides

[0068] The compound represented by formula D:

[0069]

[0070] Compound represented by formula E:

[0071]

[0072] Prescription: As shown in Table 3.

[0073] Table 3: Peeling fluid prescription

[0074]

[0075]

[0076] Preparation method: Mix quaternary ammonium hydroxide, water-soluble organic solvent, cyclic amine, alkanolamine, corrosion inhibitor, nonionic surfactant and water according to the prescribed amount to obtain a stripping solution.

[0077] Comparative Examples 5 and 6: Investigation of Surfactants

[0078] The compound represented by formula F:

[0079]

[0080] Prescription: As shown in Table 4.

[0081] Table 4: Peeling fluid formulation

[0082]

[0083]

[0084] Preparation method: Mix the ingredients according to the prescription amount shown in Table 4 to obtain the stripping solution.

[0085] Comparative Example 7-Comparative Example 8: Investigation of Corrosion Inhibitors

[0086] Prescription: As shown in Table 5.

[0087] Table 5: Peeling fluid formulation

[0088]

[0089] Preparation method: Mix the ingredients according to the prescribed amount as shown in Table 5 to obtain the stripping solution.

[0090] Example 5: Testing of peeling effect and corrosion

[0091] Preparation of test piece: In order to evaluate the stripping performance of the photoresist stripping liquid composition on the photoresist, the test piece used is a 2μm photoresist film spin-coated on the substrate. The specific treatment is as follows: first, the glass substrate is cleaned with a special cleaning agent, then washed with ultrapure water and dried. Then, a layer of 2μm thick photoresist film is spin-coated on the substrate at 800-1000rpm by a spin coater, and then cured in an oven at a temperature of 150°C to obtain a test piece for testing the stripping performance of the photoresist stripping liquid composition on the photoresist.

[0092] Stripping effect and corrosion test: The substrate test piece with a copper-molybdenum metal layer or a molybdenum-aluminum metal layer formed on the glass surface was cut into small pieces of 1 cm×1 cm, and immersed in the stripping solution of the above-mentioned Example 3-Example 4 or Comparative Example 1-Comparative Example 9, respectively, at 35°C for 120 seconds, and then taken out and washed with ultrapure water, dried with nitrogen, and the corrosion conditions of the surface and cross-section of the test piece were observed under a microscope. The results are shown in Table 6.

[0093] Table 6: Test results of peeling effect and corrosion

[0094]

[0095]

[0096] Corrosion depth: The width of the corrosion hole at the edge of the molybdenum-aluminum metal layer in the side cross section of the molybdenum-aluminum metal layer, such as Figure 1 The position shown in A.

[0097] Corrosion height: The height of the corrosion hole at the edge of the molybdenum-aluminum metal layer in the side cross section of the molybdenum-aluminum metal layer, such as Figure 1 The position shown in B.

[0098] Results analysis: From Table 6, we can see that:

[0099] (1) Compared with other surfactants, the stripping solution obtained by adding the compound represented by formula II in the present invention can reduce the corrosiveness of the metal layer and also has a good stripping effect without photoresist residue.

[0100] (2) Compared with other quaternary ammonium hydroxides, the stripping solution obtained by adding the compound represented by formula I in the present invention reduces the corrosiveness of the metal layer and also has a good stripping effect without photoresist residue.

[0101] (3) The present invention uses benzotriazole and sorbitol as corrosion inhibitors, which can synergistically reduce the corrosion of the metal layer with the compound represented by Formula II.

[0102] 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 photoresist stripping solution, characterized in that: It includes a compound represented by formula I, a water-soluble organic solvent, an amine reagent, a corrosion inhibitor, a nonionic surfactant and water; the compound represented by formula I is as follows: ； The nonionic surfactant is a compound represented by formula II, ； Wherein, in formula II, n is an integer of 10-20; The water-soluble organic solvent comprises at least one 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 compounds; The amine reagent includes cyclic amine and alkanolamine, the corrosion inhibitor includes benzotriazole and sorbitol, and based on the total mass of the stripping solution, the content of the compound represented by formula I is 1wt%-5wt%, the content of the cyclic amine is 0.5wt%-5wt%, the content of the alkanolamine is 5wt%-14.5wt%, the content of the benzotriazole is 0.05wt%-1.45wt%, the content of the sorbitol is 0.05wt%-1.45wt%, the content of the nonionic surfactant is 0.05-0.1wt%, the content of water is 15wt%-40wt%, and the balance is the water-soluble organic solvent.

2. The photoresist stripping solution according to claim 1, characterized in that The cyclic amine includes at least one of hydroxyethylpiperazine, piperazine, N-methyl-piperazine, and methyl-piperazine; the alkanolamine includes at least one of monoethanolamine, diethanolamine, triethanolamine, 2-(2-aminoethoxy)ethanol, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dibutylethanolamine, N-methylethanolamine, N-(2-aminoethyl)ethanolamine, N-ethylethanolamine, N-butylethanolamine, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine.

3. A method for preparing a photoresist stripping solution according to any one of claims 1 to 2, characterized in that: The method comprises mixing a compound shown in formula I, a water-soluble organic solvent, an amine reagent, a corrosion inhibitor, a nonionic surfactant and water.

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