A kind of regenerable photoresist stripping solution and preparation method thereof

Abstract

The invention relates to the field of stripping technology, and discloses a renewable photoresist stripping solution and a preparation method thereof. A photoresist stripping solution additive comprises the following raw materials in parts by weight: 35 to 45 parts of alcohol ether compounds; 35 to 45 parts of organic amine compounds; 10 to 15 parts of additives; the additives include corrosion inhibitors, surfactants and stripping rate promoters. The photoresist stripping solution additive provided by the invention has simple components, and the renewable photoresist stripping solution obtained by mixing with photoresist stripping solution waste liquid in a specific proportion has a stable degumming effect; the additive components can be flexibly adjusted, and the corrosion inhibitor, surfactant and stripping rate promoter are compounded and used in a specific proportion, which can quickly remove the glue and ensure that the substrate is not damaged. The preparation method of the renewable photoresist stripping solution is simple, and can realize the reuse of effective components in the photoresist stripping solution waste liquid, reduce the cost of the photoresist stripping solution, reduce resource waste and benefit environmental protection, and is suitable for industrial practical use.

Description

Technical Field

[0001] The invention relates to the technical field of stripping agents, and in particular to a regenerable photoresist stripping solution and a preparation method thereof. Background Art

[0002] Photoresist stripping liquid is widely used in semiconductor manufacturing, integrated circuit manufacturing and other fields. It can effectively remove the photoresist layer for subsequent etching, doping and other processes. With the continuous development of the electronics industry, the performance and demand for photoresist stripping liquid are also constantly improving to meet the requirements of higher integration and more sophisticated manufacturing processes.

[0003] As the demand for photoresist stripping liquid increases, the amount of waste photoresist stripping liquid generated also increases. Waste photoresist stripping liquid contains harmful chemicals, such as organic solvents, acids, alkalis, etc. If not properly handled, it will cause serious pollution to the environment. At the same time, waste photoresist stripping liquid still contains some valuable components, such as photoresist, solvents, etc. The existing technology can recover the effective components in waste photoresist stripping liquid by means of distillation, etc. If the recovered effective components can be reused, it can reduce the consumption of raw materials, reduce production costs, and reduce environmental impact. Summary of the invention

[0004] The present invention aims to solve at least one of the above-mentioned technical problems existing in the prior art. To this end, one of the purposes of the present invention is to provide a photoresist stripping solution additive; the second purpose of the present invention is to provide a regenerable photoresist stripping solution; the third purpose of the present invention is to provide a preparation method of the regenerable photoresist stripping solution.

[0005] In order to achieve the above purpose, the technical solution adopted by the present invention is:

[0006] The first aspect of the present invention provides a photoresist stripping solution additive, comprising the following raw materials in parts by weight:

[0007] 35-45 parts of alcohol ether compound;

[0008] 35-45 parts of organic amine compounds;

[0009] 10-15 parts of admixture;

[0010] The additives include corrosion inhibitors, surfactants and stripping rate accelerators.

[0011] Preferably, the mass ratio of the corrosion inhibitor, the surfactant and the stripping rate promoter is (1.5-2.5):(1.5-2.5):1; further preferably, the mass ratio of the corrosion inhibitor, the surfactant and the stripping rate promoter is (1.8-2.2):(1.8-2.2):1.

[0012] Preferably, the photoresist stripping solution additive is made of the following raw materials in parts by weight:

[0013]

[0014] Preferably, the corrosion inhibitor includes at least one of toluene triazole, benzotriazole, 5-aminotetrazolyl, and mercaptobenzotriazole.

[0015] Preferably, the surfactant includes at least one of 2,4-dihydroxypyrimidine and 4-hydroxybutyrolactone.

[0016] Preferably, the stripping rate accelerator includes at least one of ethylthiourea, n-butylthiourea, semicarbazide, ethylaminethiourea, dimethyl sulfoxide, dimethyl sulfone, diethyl sulfone, and sulfolane.

[0017] Preferably, the alcohol ether compound includes at least one of diethylene glycol butyl ether, diethylene glycol methyl ether, ethylene glycol methyl ether and ethylene glycol ethyl ether.

[0018] Preferably, the organic amine compound includes N-hydroxyethylpiperazine, or at least one of N-hydroxyethylpiperazine and diglycolamine and hydroxyethylethylenediamine.

[0019] Preferably, the photoresist stripping solution additive is prepared by a method comprising the following steps:

[0020] The prepared raw materials are mixed to obtain the photoresist stripping solution additive.

[0021] The second aspect of the present invention provides a regenerable photoresist stripping solution, comprising the photoresist stripping solution additive described in the first aspect of the present invention, and waste photoresist stripping solution.

[0022] The third aspect of the present invention provides a method for preparing the regenerable photoresist stripping solution according to the second aspect of the present invention, comprising the following steps:

[0023] 1) The photoresist stripping liquid waste is diluted, filtered and distilled to obtain a regenerated liquid;

[0024] 2) Adding a photoresist stripping solution additive into the regeneration solution to obtain the regenerable photoresist stripping solution.

[0025] Preferably, in the step 1), the dilution is to dilute the photoresist stripping liquid waste by adding purified water.

[0026] Preferably, in the step 1), the filtering is to filter the diluted solution of the photoresist stripping liquid waste through a 6-10 μm filter membrane.

[0027] Preferably, in step 1), the distillation temperature is 150-300°C; further preferably, the distillation temperature is 150-200°C.

[0028] Preferably, in step 1), the distillation pressure is 1.5-2 kPa.

[0029] Preferably, in the step 2), the mass ratio of the photoresist stripping solution additive to the regeneration solution is 1:(4-6); further preferably, the mass ratio of the photoresist stripping solution additive to the regeneration solution is 1:(4-5.5).

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] The photoresist stripping solution additive provided by the present invention has simple components, and the renewable photoresist stripping solution obtained by mixing with photoresist stripping solution waste liquid in a specific proportion has a stable adhesive removal effect; the additive components can be flexibly adjusted according to the effective ingredients in the photoresist stripping solution waste liquid, and the corrosion inhibitor, surfactant and stripping rate accelerator are compounded and used in a specific proportion, so that the substrate can be protected from damage while the adhesive is removed quickly.

[0032] The preparation method of the renewable photoresist stripping solution provided by the present invention is simple, can realize the reuse of effective components in waste photoresist stripping solution, reduce the cost of the photoresist stripping solution, reduce resource waste and is beneficial to environmental protection, and is suitable for industrial practical use. DETAILED DESCRIPTION

[0033] The present invention is further described in detail below by specific examples. Unless otherwise specified, the raw materials, reagents or devices used in the examples and comparative examples can be obtained from conventional commercial sources or can be obtained by prior art methods. Unless otherwise specified, the experiments or test methods are conventional methods in the art.

[0034] Example 1

[0035] The present embodiment provides a regenerable photoresist stripping solution, wherein the raw materials for preparation include waste photoresist stripping solution, the waste photoresist stripping solution is diluted with purified water, filtered through an 8 μm filter membrane, and distilled (150° C., 1.5 kPa) to obtain a regenerated solution, and the components of the regenerated solution are detected. The effective components include 58 parts by mass of N-methylformamide, 40 parts by mass of diethylene glycol butyl ether, and 2 parts by mass of N-hydroxyethylpiperazine. A photoresist stripping solution additive is prepared according to the components of the regenerated solution. The components of the photoresist stripping solution additive are shown in Table 1 below:

[0036] Table 1 Photoresist stripping solution additive components and contents in Example 1

[0037]

[0038] The components of the photoresist stripping solution additive in Table 1 are mixed to obtain a photoresist stripping solution additive, and then the photoresist stripping solution additive is mixed with a regeneration liquid at a mass ratio of 1:5 to obtain a regenerable photoresist stripping solution.

[0039] Example 2

[0040] The present embodiment provides a regenerable photoresist stripping solution, wherein the raw materials for preparation include waste photoresist stripping solution, the waste photoresist stripping solution is diluted with purified water, filtered through an 8 μm filter membrane, and distilled (150° C., 1.5 kPa) to obtain a regenerated solution, and the components of the regenerated solution are detected. The effective components include 54 parts by mass of N',N-dimethylformamide, 43 parts by mass of ethylene glycol methyl ether, and 3 parts by mass of diglycolamine. A photoresist stripping solution additive is prepared according to the components of the regenerated solution. The components of the photoresist stripping solution additive are shown in Table 2 below:

[0041] Table 2 Components and contents of photoresist stripping solution additives in Example 2

[0042]

[0043] The components of the photoresist stripping solution additive in Table 2 are mixed to obtain a photoresist stripping solution additive, and then the photoresist stripping solution additive is mixed with a regeneration liquid at a mass ratio of 1:4 to obtain a regenerable photoresist stripping solution.

[0044] Example 3

[0045] The present embodiment provides a regenerable photoresist stripping solution, wherein the raw materials for preparation include waste photoresist stripping solution, the waste photoresist stripping solution is diluted with purified water, filtered through an 8 μm filter membrane, and distilled (150° C., 1.5 kPa) to obtain a regenerated solution, and the components of the regenerated solution are detected. The effective components include 55 parts by mass of N-methylformamide, 43 parts by mass of diethylene glycol butyl ether, and 2 parts by mass of hydroxyethylethylenediamine. A photoresist stripping solution additive is prepared according to the components of the regenerated solution. The components of the photoresist stripping solution additive are shown in Table 3 below:

[0046] Table 3 Components and contents of photoresist stripping solution additives in Example 3

[0047]

[0048] The components of the photoresist stripping solution additive in Table 3 are mixed to obtain a photoresist stripping solution additive, and then the photoresist stripping solution additive is mixed with a regeneration liquid at a mass ratio of 1:6 to obtain a regenerable photoresist stripping solution.

[0049] Comparative Example 1

[0050] The comparative example provides a regenerable photoresist stripping solution, wherein the raw materials for preparation include waste photoresist stripping solution, the waste photoresist stripping solution is diluted with purified water, filtered through an 8 μm filter membrane, and distilled (150° C., 1.5 kPa) to obtain a regenerated solution, and the components of the regenerated solution are detected. The effective components include 58 parts by mass of N-methylformamide, 40 parts by mass of diethylene glycol butyl ether, and 2 parts by mass of N-hydroxyethylpiperazine. A photoresist stripping solution additive is prepared according to the components of the regenerated solution. The components of the photoresist stripping solution additive are shown in Table 4 below:

[0051] Table 4 Components and contents of additives in photoresist stripping solution in Comparative Example 1

[0052]

[0053] The components of the photoresist stripping solution additive in Table 4 are mixed to obtain a photoresist stripping solution additive, and then the photoresist stripping solution additive is mixed with a regeneration liquid at a mass ratio of 1:5 to obtain a regenerable photoresist stripping solution.

[0054] Comparative Example 2

[0055] The comparative example provides a regenerable photoresist stripping solution, wherein the raw materials for preparation include waste photoresist stripping solution, the waste photoresist stripping solution is diluted with purified water, filtered through an 8 μm filter membrane, and distilled (150° C., 1.5 kPa) to obtain a regenerated solution, and the components of the regenerated solution are detected. The effective components include 58 parts by mass of N-methylformamide, 40 parts by mass of diethylene glycol butyl ether, and 2 parts by mass of N-hydroxyethylpiperazine. A photoresist stripping solution additive is prepared according to the components of the regenerated solution. The components of the photoresist stripping solution additive are shown in Table 5 below:

[0056] Table 5 Components and contents of additives for photoresist stripping solution in Comparative Example 2

[0057]

[0058]

[0059] The components of the photoresist stripping solution additive in Table 5 are mixed to obtain a photoresist stripping solution additive, and then the photoresist stripping solution additive is mixed with a regeneration liquid at a mass ratio of 1:5 to obtain a regenerable photoresist stripping solution.

[0060] Comparative Example 3

[0061] The comparative example provides a regenerable photoresist stripping solution, wherein the raw materials for preparation include waste photoresist stripping solution, the waste photoresist stripping solution is diluted with purified water, filtered through an 8 μm filter membrane, and distilled (150° C., 1.5 kPa) to obtain a regenerated solution, and the components of the regenerated solution are detected. The effective components include 58 parts by mass of N-methylformamide, 40 parts by mass of diethylene glycol butyl ether, and 2 parts by mass of N-hydroxyethylpiperazine. A photoresist stripping solution additive is prepared according to the components of the regenerated solution. The components of the photoresist stripping solution additive are shown in Table 6 below:

[0062] Table 6 Components and contents of additives in photoresist stripping solution in comparative example 3

[0063]

[0064] The components of the photoresist stripping solution additive in Table 6 are mixed to obtain a photoresist stripping solution additive, and then the photoresist stripping solution additive is mixed with a regeneration liquid at a mass ratio of 1:5 to obtain a regenerable photoresist stripping solution.

[0065] Comparative Example 4

[0066] The comparative example provides a regenerable photoresist stripping solution, wherein the raw materials for preparation include waste photoresist stripping solution, the waste photoresist stripping solution is diluted with purified water, filtered through an 8 μm filter membrane, and distilled (150° C., 1.5 kPa) to obtain a regenerated solution, and the components of the regenerated solution are detected. The effective components include 58 parts by mass of N-methylformamide, 40 parts by mass of diethylene glycol butyl ether, and 2 parts by mass of N-hydroxyethylpiperazine. A photoresist stripping solution additive is prepared according to the components of the regenerated solution. The components of the photoresist stripping solution additive are shown in Table 7 below:

[0067] Table 7 Components and contents of additives in photoresist stripping solution in Comparative Example 4

[0068]

[0069] The components of the photoresist stripping solution additive in Table 7 are mixed to obtain a photoresist stripping solution additive, and then the photoresist stripping solution additive is mixed with a regeneration liquid at a mass ratio of 1:5 to obtain a regenerable photoresist stripping solution.

[0070] Comparative Example 5

[0071] The comparative example provides a regenerable photoresist stripping solution, wherein the raw materials for preparation include waste photoresist stripping solution, the waste photoresist stripping solution is diluted with purified water, filtered through an 8 μm filter membrane, and distilled (150° C., 1.5 kPa) to obtain a regenerated solution, and the components of the regenerated solution are detected. The effective components include 58 parts by mass of N-methylformamide, 40 parts by mass of diethylene glycol butyl ether, and 2 parts by mass of N-hydroxyethylpiperazine. A photoresist stripping solution additive is prepared according to the components of the regenerated solution. The components of the photoresist stripping solution additive are shown in Table 8 below:

[0072] Table 8 Components and contents of photoresist stripping solution additives in Comparative Example 5

[0073]

[0074] The components of the photoresist stripping solution additive in Table 8 are mixed to obtain a photoresist stripping solution additive, and then the photoresist stripping solution additive is mixed with a regeneration liquid at a mass ratio of 1:8 to obtain a regenerable photoresist stripping solution.

[0075] Performance Testing

[0076] Use the renewable photoresist stripping solution in Examples 1-3 and Comparative Examples 1-5 to strip the photoresist. Take 100g of the renewable photoresist stripping solution in Examples 1-3 and Comparative Examples 1-5 respectively, heat in a 45°C water bath, immerse the ITO glass substrate (size 3cm×3cm×2mm) attached with photoresist in the stripping solution at 45°C, and corrode under static conditions. Start timing from when the glass substrate is placed in the stripping solution, record the time when the photoresist is completely stripped, and observe whether the substrate is damaged. After the test, the waste liquid can be collected and purified and used again as a regeneration liquid to participate in the preparation of the renewable photoresist stripping solution. The performance results of the renewable photoresist stripping solution in Examples 1-3 and Comparative Examples 1-5 are shown in Table 9 below:

[0077] Table 9 Performance test results of the regenerable photoresist stripping solution in Examples 1-3 and Comparative Examples 1-5

[0078]

[0079]

[0080] Table 9 shows the performance test results of the renewable photoresist stripping solution in Examples 1-3 and Comparative Examples 1-5. It can be seen from Table 9 that the renewable photoresist stripping solution in Examples 1-3, which is composed of a photoresist stripping solution purification solution and an additive in a mass ratio of (4 to 6): 1, can completely strip the photoresist within 2 to 3 minutes at 45°C, has a stable debonding effect, and will not cause damage to the substrate.

[0081] The only difference between Comparative Example 1 and Example 1 is that the additive does not contain surfactant and stripping rate accelerator. It can be seen that although the regenerable photoresist stripping liquid in Comparative Example 1 will not damage the substrate, the degumming rate is significantly slowed down, and the photoresist complete stripping time is twice that of Example 1.

[0082] The only difference between Comparative Example 2 and Example 1 is that the additive does not contain a corrosion inhibitor and a stripping rate accelerator. It can be seen that the photoresist stripping solution easily causes damage to the substrate and the debonding rate is significantly slowed down.

[0083] The only difference between Comparative Example 3 and Example 1 is that the additive does not contain a corrosion inhibitor and a surfactant, and the photoresist stripping solution has an accelerated photoresist removal speed, but will cause damage to the substrate.

[0084] The difference between Comparative Example 4 and Example 1 is that the corrosion inhibitor, surfactant and stripping rate accelerator are not mixed in a specific proportion. Therefore, although the components contain corrosion inhibitor, surfactant and stripping rate accelerator, the substrate is slightly damaged and the time for complete stripping of the photoresist is longer than that in Example 1.

[0085] The difference between Comparative Example 5 and Example 1 is that the photoresist stripping liquid additive and the regeneration liquid are not mixed in a specific ratio, resulting in a problem of less amount of photoresist stripping liquid additive, which causes damage to the substrate and significantly slows down the photoresist stripping rate, resulting in poor degumming effect.

[0086] It can be seen that the photoresist stripping liquid additive provided by the present invention can flexibly adjust the components according to the composition of the photoresist stripping liquid waste liquid purification regeneration liquid, and then after mixing with the regeneration liquid in a specific ratio, a better degumming effect can be achieved. Too much photoresist stripping liquid additive is used, which is easy to cause waste of raw materials and is not conducive to cost saving. Too little photoresist stripping liquid additive cannot achieve a good degumming effect. The regenerable photoresist stripping liquid formed by the photoresist stripping liquid additive and the photoresist stripping liquid waste liquid can be purified again to form a regeneration liquid after the degumming is completed, and can be regenerated and used after compounding with the additive.

Claims

1. A photoresist stripping solution additive, characterized in that: The preparation method is composed of the following raw materials in parts by weight: 43 parts of dibutyl glycol butyl ether; 45 parts of N-hydroxyethyl piperazine; an admixture, the admixture comprising a corrosion inhibitor, a surfactant and a stripping rate accelerator; The corrosion inhibitor is 5 parts of 5-aminotetrazolyl; the surfactant is 5 parts of 4-hydroxybutyrolactone; The stripping rate accelerator is 2 parts of n-butylthiourea.

2. A regenerable photoresist stripping solution, characterized in that: The preparation method comprises the following raw materials: the photoresist stripping liquid additive according to any one of claims 1, and waste liquid of the photoresist stripping liquid; The effective components of the photoresist stripping liquid waste liquid include 55 parts by mass of N-methylformamide, 43 parts by mass of diethylene glycol butyl ether and 2 parts by mass of hydroxyethylethylenediamine.

3. The method for preparing the regenerable photoresist stripping solution according to claim 2, characterized in that: The following steps are involved: 1) The photoresist stripping liquid waste is filtered, diluted and distilled to obtain a regenerated liquid; 2) Adding a photoresist stripping solution additive into the regeneration solution to obtain the regenerable photoresist stripping solution.

4. The preparation method according to claim 3, characterized in that: In the step 1), the distillation temperature is 150-300°C; And / or, in the step 2), the mass ratio of the photoresist stripping solution additive to the regeneration solution is 1:(4-6).

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