A photoresist stripping solution for delaying discoloration and preparation method thereof

Abstract

The present invention provides a photoresist stripping solution for delaying discoloration and a preparation method thereof, belonging to the technical field of photoresist stripping solutions. The present invention obtains a photoresist stripping solution by mixing an imidazoline surfactant with a sulfone organic solvent, a pyrrolidone solvent, an alcohol ether organic solvent, an alcohol amine solvent, and a dispersant. The photoresist stripping solution prepared by the method disclosed in the present invention is not easy to change color during production, storage, transportation and use, and is not easy to corrode the metal electrode on the surface of the chip during use. The process of the present invention is simple to operate, highly repeatable, and suitable for large-scale industrial production.

Description

Technical Field

[0001] The invention relates to the technical field of photoresist stripping liquid, and in particular to a photoresist stripping liquid that delays discoloration and a preparation method thereof. Background Art

[0002] Photoresist stripping solution, also known as degumming solution, is a chemical material commonly used in semiconductor manufacturing and the electronics industry. It is used to dissolve or strip the photoresist on the surface of the chip for subsequent process steps.

[0003] The existing degumming liquid is composed of N-methylpyrrolidone, sulfone organic solvents, alcohol ether organic solvents, amide solvents, etc. These raw materials are generally colorless and transparent liquids; but the alcohol amine solvents will absorb moisture in the air and react with carbon dioxide to form salts; as the water content increases, the sulfone organic solvents will be decomposed and slowly oxidized, turning into yellow and then brown. This change will be accelerated by heating and the presence of metals.

[0004] The color of the photoresist stripping solution can reflect its degree of aging. The photoresist stripping solution that is severely yellowed will significantly reduce its ability to dissolve and strip photoresist.

[0005] Therefore, alleviating the discoloration of photoresist stripping liquid during production, storage, transportation and use has become an urgent problem to be solved by technicians in this field. Summary of the invention

[0006] The object of the present invention is to provide a photoresist stripping solution with delayed discoloration and a preparation method thereof, so as to solve the technical problem of discoloration of the photoresist stripping solution during production, storage, transportation and use.

[0007] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0008] The present invention provides a photoresist stripping solution for delaying discoloration, which is composed of the following components in parts by mass:

[0009]

[0010] Furthermore, the imidazoline surfactant includes one or more of rosin-based imidazoline, 1-thioureaethyl-2-aryl-2-imidazoline and heptadecenyl hydroxyethyl imidazoline.

[0011] Furthermore, the pyrrolidone solvent comprises N-methylpyrrolidone.

[0012] Furthermore, the sulfone organic solvent comprises sulfolane and / or dimethyl sulfoxide.

[0013] Furthermore, the alcohol ether organic solvent includes one or more of ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether and ethylene glycol monobutyl ether.

[0014] Furthermore, the alcoholamine solvent comprises isopropanolamine and / or ethanolamine.

[0015] Furthermore, the dispersant comprises polyvinyl pyrrolidone.

[0016] The present invention also provides a method for preparing a photoresist stripping solution for delaying discoloration, comprising the following steps:

[0017] 1) mixing an imidazoline surfactant and a sulfone organic solvent to obtain a transparent mixture;

[0018] 2) Mixing pyrrolidone solvent, alcohol ether organic solvent, alcohol amine solvent, dispersant and transparent mixture to obtain a photoresist stripping solution that delays discoloration.

[0019] Furthermore, in the step 1), the mixing is carried out under stirring, the stirring speed is 100 to 300 r / min, and the stirring time is 30 to 120 min.

[0020] Furthermore, in the step 2), the mixing is carried out under stirring, the stirring speed is 100 to 300 r / min, and the stirring time is 10 to 30 min.

[0021] Beneficial effects of the present invention:

[0022] The present invention adds an imidazoline surfactant to the existing photoresist stripping solution composition, which can effectively delay the discoloration of the photoresist stripping solution; at the same time, the imidazoline surfactant is a metal corrosion inhibitor, and its imidazoline ring can adhere to the metal surface, and its long carbon chain can isolate oxidizing substances, thereby slowing down the corrosion of the metal electrode on the surface of the LED chip caused by the photoresist stripping solution during the stripping process. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is a picture of the photoresist stripping solution prepared in Example 1 of the present invention after use;

[0024] Figure 2 This is a picture of the photoresist stripping solution prepared in Example 2 of the present invention after use;

[0025] Figure 3 This is a picture of the photoresist stripping solution prepared in Example 3 of the present invention after use;

[0026] Figure 4 This is a picture of the photoresist stripping solution prepared in Comparative Example 1 of the present invention after use;

[0027] Figure 5 This is a picture of the photoresist stripping solution prepared in Comparative Example 2 of the present invention after use. DETAILED DESCRIPTION

[0028] The present invention provides a photoresist stripping solution for delaying discoloration, which is composed of the following components in parts by mass:

[0029] 20-55 parts of pyrrolidone solvent;

[0030] 10-25 parts of sulfone organic solvent;

[0031] 0-35 parts of alcohol ether organic solvent;

[0032] 15-30 parts of alcoholamine solvent;

[0033] 0.5-2 parts of imidazoline surfactant;

[0034] Dispersant 0-0.7 parts.

[0035] In the present invention, the amount of the pyrrolidone solvent used is preferably 25 to 50 parts by mass, more preferably 30 to 45 parts, and even more preferably 35 to 40 parts.

[0036] In the present invention, the amount of the sulfone organic solvent used is preferably 12 to 22 parts by mass, more preferably 15 to 20 parts, and even more preferably 16 to 18 parts.

[0037] In the present invention, the amount of the alcohol ether organic solvent is preferably 5 to 30 parts by weight, more preferably 10 to 25 parts, and even more preferably 15 to 20 parts.

[0038] In the present invention, the amount of the alcoholamine solvent used is preferably 18 to 28 parts by mass, more preferably 20 to 25 parts, and even more preferably 22 to 24 parts.

[0039] In the present invention, the amount of the imidazoline surfactant used is preferably 0.8 to 1.8 parts by mass, more preferably 1.0 to 1.5 parts, and even more preferably 1.2 to 1.4 parts.

[0040] In the present invention, the dispersant is preferably present in an amount of 0.1 to 0.6 parts by mass, more preferably 0.2 to 0.5 parts by mass, and even more preferably 0.3 to 0.4 parts by mass.

[0041] In the present invention, the imidazoline surfactant comprises one or more of rosin-based imidazoline, 1-thioureaethyl-2-aryl-2-imidazoline and heptadecenyl hydroxyethyl imidazoline, preferably rosin-based imidazoline.

[0042] In the present invention, the imidazoline surfactant is an imidazoline surfactant that has been dried, and the specific steps are: placing an imidazoline surfactant sample in a vacuum drying oven, drying it at a temperature of 100-110° C. for 24 hours, and then recording the sample mass, and then recording the sample mass every half an hour until the mass of two consecutive samples is the same, and then using a Karl Fischer moisture meter to measure the moisture content to ensure that the moisture content of the imidazoline surfactant after the drying treatment is less than 0.1%.

[0043] In the present invention, the pyrrolidone solvent is preferably N-methylpyrrolidone.

[0044] In the present invention, the sulfone organic solvent comprises sulfolane and / or dimethyl sulfoxide, preferably dimethyl sulfoxide.

[0045] In the present invention, the alcohol ether organic solvent comprises one or more of ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether and ethylene glycol monobutyl ether, preferably ethylene glycol monoethyl ether.

[0046] In the present invention, the alcoholamine solvent comprises isopropanolamine and / or ethanolamine, preferably ethanolamine.

[0047] In the present invention, the dispersant is preferably polyvinyl pyrrolidone.

[0048] The present invention also provides a method for preparing a photoresist stripping solution for delaying discoloration, comprising the following steps:

[0049] 1) mixing an imidazoline surfactant and a sulfone organic solvent to obtain a transparent mixture;

[0050] 2) Mixing pyrrolidone solvent, alcohol ether organic solvent, alcohol amine solvent, dispersant and transparent mixture to obtain a photoresist stripping solution that delays discoloration.

[0051] In the present invention, in the step 1), the mixing is carried out under stirring, the stirring speed is 100 to 300 r / min, preferably 150 to 250 r / min, and more preferably 200 r / min; the stirring time is 30 to 120 min, preferably 50 to 100 min, and more preferably 60 to 80 min.

[0052] In the present invention, in the step 2), the mixing is carried out under stirring, the stirring speed is 100 to 300 r / min, preferably 150 to 250 r / min, and more preferably 200 r / min; the stirring time is 10 to 30 min, preferably 15 to 25 min, and more preferably 20 min.

[0053] The technical solutions provided by the present invention are described in detail below in conjunction with the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0054] Example 1

[0055] The raw materials and dosages used in this embodiment are as follows:

[0056] Pyrrolidone solvent: 49 parts of N-methylpyrrolidone

[0057] Sulfone organic solvent: 25 parts dimethyl sulfoxide

[0058] Alcohol ether organic solvent: 10 parts of ethylene glycol monoethyl ether

[0059] Alcoholamine organic solvent: 15 parts of ethanolamine

[0060] Imidazoline surfactant: 1 part of rosin-based imidazoline.

[0061] The specific preparation steps are as follows:

[0062] In the ultra-clean purification room, the rosin-based imidazoline sample is placed in a clean watch glass, and the watch glass is placed in a vacuum drying oven. The sample mass is recorded after vacuum drying for 24 hours at a temperature of 105°C, and the sample mass is recorded every half an hour thereafter until the mass of two consecutive samples is the same. In a high-speed stirring kettle, the dried rosin-based imidazoline (the content of rosin-based imidazoline in this embodiment is based on the dried rosin-based imidazoline) is placed in a dimethyl sulfoxide solvent, and stirred continuously for 120 minutes at room temperature at a speed of 200r / min. Then N-methyl pyrrolidone, ethylene glycol monoethyl ether, and ethanolamine are added to the high-speed stirring kettle in sequence, and stirred continuously for 20 minutes at room temperature at a speed of 200r / min to obtain a photoresist stripping solution.

[0063] Example 2

[0064] The raw materials and dosages used in this embodiment are as follows:

[0065]

[0066] The specific preparation steps are as follows:

[0067] In the ultra-clean clean room, in a high-speed stirring kettle, the heptadecenyl hydroxyethyl imidazoline (the content of the heptadecenyl hydroxyethyl imidazoline in this embodiment is calculated based on the heptadecenyl hydroxyethyl imidazoline after drying, and the specific drying step is the same as in Example 1) is placed in dimethyl sulfoxide and cyclopentane sulfone solvents, and stirred at a speed of 200r / min at room temperature for 30min. Then N-methylpyrrolidone and isopropanolamine are added to the high-speed stirring kettle in sequence, and stirred at a speed of 200r / min at room temperature for 30min to obtain a photoresist stripping solution.

[0068] Example 3

[0069] The raw materials and dosages used in this embodiment are as follows:

[0070]

[0071] The specific preparation steps are as follows:

[0072] In a super clean room, in a high-speed stirring kettle, 1-thioureaethyl-2-aryl-2-imidazoline (the content of 1-thioureaethyl-2-aryl-2-imidazoline in this embodiment is based on the 1-thioureaethyl-2-aryl-2-imidazoline after drying, and the specific drying step is the same as in Example 1) is placed in dimethyl sulfoxide and cyclopentane sulfone solvents, and stirred at a speed of 200r / min at room temperature for 30min. Then, N-methylpyrrolidone is added to the high-speed stirring kettle, and stirred at a speed of 200r / min at room temperature for 30min to obtain a photoresist stripping solution.

[0073] Comparative Example 1

[0074] The raw materials and dosages used in this comparative example are as follows:

[0075]

[0076] The specific preparation steps are as follows:

[0077] In an ultra-clean purification room, dimethyl sulfoxide, N-methylpyrrolidone, ethylene glycol monoethyl ether and ethanolamine were added in sequence in a high-speed stirring kettle, and stirred continuously for 20 minutes at room temperature at a speed of 200 r / min to obtain a photoresist stripping solution.

[0078] Comparative Example 2

[0079] The raw materials and dosages used in this comparative example are as follows:

[0080]

[0081] The specific preparation steps are as follows:

[0082] In an ultra-clean purification room, dimethyl sulfoxide, cyclopentane sulfone, N-methylpyrrolidone, isopropanolamine and a dispersant are added in sequence to a high-speed stirring kettle, and the mixture is stirred continuously for 20 minutes at room temperature at a speed of 200 r / min to obtain a photoresist stripping solution.

[0083] Performance Testing

[0084] The photoresist stripping solutions prepared in Examples 1 to 3 of the present invention and Comparative Examples 1 to 2 were subjected to high temperature accelerated treatment to simulate the conditions of the photoresist stripping solutions at the end of their use, and then the chips containing the photoresist were treated respectively. The specific treatment process is as follows:

[0085] Pour the photoresist stripping solution into the cleaning tank, add 3 parts by mass of pure water and 3 parts by mass of photoresist to every 100 parts by mass of the photoresist stripping solution, and heat at 90°C for 36 hours; then keep the cleaning tank at 90°C, add the chip to the photoresist stripping solution, and ultrasonically treat it at a frequency of 40kHz for 1 hour, then rinse the chip with water twice, each time for 5 minutes; finally, blow dry with nitrogen at 70°C. Use a soptop brand MX8R model microscope to observe the metal corrosion. Take the cleaned tank liquid and place it in a colorless transparent glass bottle to observe the color of the photoresist stripping solution after use.

[0086] Table 1 Photoresist stripping liquid performance test results

[0087]

[0088] As can be seen from the above embodiments, the present invention provides a photoresist stripping solution that delays discoloration and a preparation method thereof. The photoresist stripping solution prepared by the method disclosed in the present invention is not easy to discolor during production, storage, transportation and use, and is not easy to corrode the metal electrodes on the surface of the chip during use. The process of the present invention is simple to operate, highly repeatable, and suitable for large-scale industrial production.

[0089] from Figures 1 to 5 It can be seen that the photoresist stripping solutions with delayed discoloration of Examples 1 to 3 prepared by the method disclosed in the present invention are not easy to discolor during use.

[0090] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A photoresist stripping solution for delaying discoloration, characterized in that: It is composed of the following components in parts by weight: 20-55 parts of pyrrolidone solvent; 10-25 parts of sulfone organic solvent; 0-35 parts of alcohol ether organic solvent; 15-30 parts of alcoholamine solvent; 0.5-2 parts of imidazoline surfactant; Dispersant 0-0.7 parts.

2. The photoresist stripping solution for delaying discoloration according to claim 1, characterized in that: The imidazoline surfactant includes one or more of rosin-based imidazoline, 1-thioureaethyl-2-aryl-2-imidazoline and heptadecenyl hydroxyethyl imidazoline.

3. The photoresist stripping solution for delaying discoloration according to claim 1 or 2, characterized in that: The pyrrolidone solvent includes N-methylpyrrolidone.

4. The photoresist stripping solution for delaying discoloration according to claim 3, characterized in that: The sulfone organic solvent comprises sulfolane and / or dimethyl sulfoxide.

5. The photoresist stripping solution for delaying discoloration according to claim 1, 2 or 4, characterized in that: The alcohol ether organic solvent includes one or more of ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether and ethylene glycol monobutyl ether.

6. The photoresist stripping solution for delaying discoloration according to claim 2, characterized in that: The alcoholamine solvent comprises isopropanolamine and / or ethanolamine.

7. The photoresist stripping solution for delaying discoloration according to claim 5, characterized in that: The dispersant comprises polyvinyl pyrrolidone.

8. The method for preparing the photoresist stripping solution for delaying discoloration according to any one of claims 1 to 7, characterized in that: The following steps are involved: 1) mixing an imidazoline surfactant and a sulfone organic solvent to obtain a transparent mixture; 2) Mixing pyrrolidone solvent, alcohol ether organic solvent, alcohol amine solvent, dispersant and transparent mixture to obtain a photoresist stripping solution that delays discoloration.

9. The preparation method according to claim 8, characterized in that: In the step 1), the mixing is performed under stirring, the stirring speed is 100 to 300 r / min, and the stirring time is 30 to 120 min.

10. The preparation method according to claim 8 or 9, characterized in that: In the step 2), the mixing is performed under stirring, the stirring speed is 100 to 300 r / min, and the stirring time is 10 to 30 min.

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