A degumming solution and its preparation method and application

Abstract

The present invention belongs to the field of semiconductor processing technology, and discloses a degumming solution and a preparation method and application thereof. The degumming solution of the present invention comprises the following components in parts by weight: 70 to 90 parts of a solvent, 1 to 5 parts of a complexing agent, 5 to 10 parts of a dehydrating agent, 5 to 10 parts of a stripping aid, and 1 to 3 parts of a cleaning aid. The degumming solution prepared by the present invention can fully spread and penetrate on the surface of a chip or a photoresist, and the synergistic effect of all components accelerates the degumming speed and enhances the degumming effect. The use of a complexing agent and a dehydrating agent can avoid the problem of metal corrosion.

Description

Technical Field

[0001] The present invention relates to the field of semiconductor processing technology, and in particular to a degumming solution and a preparation method and application thereof. Background Art

[0002] Photoresist is a key basic chemical material in the electronics industry. After exposure and development, the required fine pattern is transferred from the mask to the substrate to be processed, and then etching, diffusion, ion implantation and metallization are carried out to complete the production of functional chips. The above processes have been widely used in integrated circuits, discrete semiconductor devices, display screens and chip packaging.

[0003] When the etching or injection process is completed, the photoresist on the chip surface will be removed by a degumming liquid. At present, the existing degumming liquid is composed of organic alkali, NMP and sulfone organic solvents, metal corrosion inhibitors such as BTA, surfactants, alcohol ether organic solvents, carbonate solvents, amide solvents, etc. There are the following problems when removing the photoresist: First, the photoresist is designed and processed to be most suitable for adhering to the chip surface to meet the requirements of etching and ion implantation, and it is difficult to remove due to its strong adhesion. Second, the etching of fluorine-based or chlorine-based gases causes the photoresist to be denatured by excitation or carbonized by burning, becoming an insoluble solid contamination on the chip surface, making it difficult to remove. Third, since the chip contains a variety of metals and inorganic materials such as gold, nickel and titanium, during the cleaning process, the moisture and metal impurities in the degumming liquid will cause galvanic corrosion between metals and chip contamination; or the peeled photoresist debris will stick back to the chip surface, which will damage the chip and reduce the chip yield.

[0004] Therefore, how to provide a degumming solution that can avoid metal corrosion and has excellent degumming effect has become a problem that technical personnel in this field need to solve urgently. Summary of the invention

[0005] In view of this, the present invention provides a degumming solution and a preparation method and application thereof. The synergistic effect of all components in the present invention accelerates the degumming speed and enhances the degumming effect. The use of a complexing agent and a dehydrating agent can avoid the problem of metal corrosion.

[0006] In order to achieve the above object, the present invention adopts the following technical solution:

[0007] The present invention provides a degumming solution, comprising the following components in parts by weight:

[0008] 70-90 parts of solvent, 1-5 parts of complexing agent, 5-10 parts of dehydrating agent, 5-10 parts of stripping aid, 1-3 parts of cleaning aid.

[0009] Furthermore, the solvent is 2,2,4,6,6-pentamethylheptane, glycol ether or dichlorobenzene; the glycol ether is diethylene glycol tert-butyl ether and / or dipropylene glycol dimethyl ether; the dichlorobenzene is o-dichlorobenzene and / or m-dichlorobenzene.

[0010] Furthermore, the complexing agent is tetrahydroxyethylethylenediamine and / or dibutyl dithiophosphate.

[0011] Furthermore, the dehydrating agent is ka zeolite molecular sieve.

[0012] Furthermore, the stripping aid is N-octyl pyrrolidone and / or trifluoromethanesulfonimide.

[0013] Furthermore, the cleaning aid is hexadecyl mercaptan and / or octadecyl mercaptan.

[0014] The present invention provides a method for preparing the above-mentioned degumming solution, comprising the following steps:

[0015] S1, mixing the solvent, the complexing agent, the stripping agent and the cleaning agent, and filtering to obtain a mixed solution; soaking and drying the dehydrating agent in sequence;

[0016] S2. Mix the dried dehydrating agent and the mixed liquid to obtain a degumming liquid.

[0017] Furthermore, in step S1, the mixing is performed by stirring, the stirring speed is 100 to 300 r / min, and the stirring time is 30 to 60 min;

[0018] The filtration degree of the filtration is 0.1 to 0.2 μm;

[0019] The immersion is carried out in acetone, and the immersion time is 30 to 50 minutes.

[0020] The present invention also provides the application of the above-mentioned degumming liquid in integrated circuits, discrete semiconductor devices, display screens or chip packaging.

[0021] It can be seen from the above technical solution that compared with the prior art, the beneficial effects of the present invention are as follows:

[0022] The solvents used in the present invention all have rich branched chain structures and can fully spread and penetrate on the chip and photoresist surfaces; the stripping aid can promote the removal of denatured or carbonized photoresist from the chip surface and disperse in the degumming liquid, thereby enhancing the degumming effect; the cleaning aid can disperse the denatured or carbonized photoresist debris suspended in the degumming liquid to prevent it from re-adhering to the chip surface, thereby achieving a thorough cleaning effect; the dehydrating agent can absorb impure water; the complexing agent can prevent metal precipitation and deposition on the surface of heterogeneous metals, thereby causing internal short circuits or reduced reliability, as well as metal corrosion problems. The synergistic effect of all components accelerates the degumming speed and enhances the degumming effect. DETAILED DESCRIPTION

[0023] The present invention provides a degumming solution, comprising the following components in parts by weight:

[0024] 70-90 parts of solvent, 1-5 parts of complexing agent, 5-10 parts of dehydrating agent, 5-10 parts of stripping aid, 1-3 parts of cleaning aid.

[0025] In the present invention, the components in parts by weight are preferably: 75-85 parts of solvent, 2-4 parts of complexing agent, 6-8 parts of dehydrating agent, 6-8 parts of stripping aid, and 2-3 parts of cleaning aid.

[0026] In the present invention, the components in parts by weight are further preferably: 78-82 parts of solvent, 3 parts of complexing agent, 7 parts of dehydrating agent, 7 parts of stripping aid, and 3 parts of cleaning aid.

[0027] In the present invention, the solvent is 2,2,4,6,6-pentamethylheptane, glycol ether or dichlorobenzene;

[0028] The diol ether is diethylene glycol tert-butyl ether and / or dipropylene glycol dimethyl ether, preferably diethylene glycol tert-butyl ether;

[0029] The dichlorobenzene is o-dichlorobenzene and / or m-dichlorobenzene, preferably o-dichlorobenzene.

[0030] In the present invention, the complexing agent is tetrahydroxyethylethylenediamine and / or dibutyl dithiophosphate ammonium, preferably tetrahydroxyethylethylenediamine.

[0031] In the present invention, the dehydrating agent is ka zeolite molecular sieve.

[0032] In the present invention, the stripping aid is N-octyl pyrrolidone and / or trifluoromethanesulfonimide, preferably N-octyl pyrrolidone.

[0033] In the present invention, the cleaning aid is hexadecyl mercaptan and / or octadecyl mercaptan, preferably octadecyl mercaptan.

[0034] The present invention provides a method for preparing the above-mentioned degumming solution, comprising the following steps:

[0035] S1, mixing the solvent, the complexing agent, the stripping agent and the cleaning agent, and filtering to obtain a mixed solution; soaking and drying the dehydrating agent in sequence;

[0036] S2. Mix the dried dehydrating agent and the mixed liquid to obtain a degumming liquid.

[0037] In the present invention, in step S1, mixing is performed by stirring, the stirring speed is 100 to 300 r / min, preferably 120 to 280 r / min, more preferably 150 to 220 r / min; the stirring time is 30 to 60 min, preferably 35 to 55 min, more preferably 40 to 50 min;

[0038] The filtration degree of the filtration is 0.1-0.2 μm, preferably 0.1 μm.

[0039] In the present invention, the immersion is carried out in acetone, and the immersion time is 30 to 50 minutes, preferably 35 to 45 minutes, and more preferably 40 minutes.

[0040] In the present invention, the soaking and drying of the dehydrating agent are repeated 3 to 5 times, preferably 4 times.

[0041] In the present invention, the degumming liquid is preferably stored in a clean barrel, and the cover of the clean barrel includes an inner lining cover, a rotating cover with a threaded structure and a disposable anti-theft cover with an external buckle structure from the inside to the outside to ensure the sealing during product storage and transportation; the material of the clean barrel is preferably HDPE.

[0042] The present invention also provides the application of the above-mentioned degumming liquid in integrated circuits, discrete semiconductor devices, display screens or chip packaging.

[0043] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0044] Example 1

[0045] The raw materials and dosages used in this embodiment are as follows:

[0046] Solvent: 50 parts of 2,2,4,6,6-pentamethylheptane, 20 parts of o-dichlorobenzene;

[0047] Complexing agent: 2 parts of tetrahydroxyethylethylenediamine, 2 parts of dibutyl dithiophosphate ammonium;

[0048] Dehydrating agent: 5 parts of Ka zeolite molecular sieve;

[0049] Stripping aid: 5 parts of N-octyl pyrrolidone, 0.5 parts of trifluoromethanesulfonimide;

[0050] Cleaning aid: 3 parts of hexadecyl mercaptan.

[0051] The specific preparation steps are as follows:

[0052] In the ultra-clean room, in a high-speed stirring kettle, the complexing agent, stripping aid and cleaning aid are dissolved in the solvent, stirred at a speed of 150r / min for 30 minutes, and then filtered with a filtration accuracy of 0.1μm to obtain a mixed solution, which is then placed in a clean bucket made of HDPE material. At room temperature, the dehydrating agent is soaked in acetone for 30 minutes, dried at 70℃ for 20 minutes, and the soaking and drying process is repeated three times; then the mixed solution and the dehydrating agent are mixed to obtain a degumming solution.

[0053] Example 2

[0054] The raw materials and dosages used in this embodiment are as follows:

[0055] Solvent: 50 parts of 2,2,4,6,6-pentamethylheptane, 10 parts of diethylene glycol tert-butyl ether, 10 parts of dipropylene glycol dimethyl ether;

[0056] Complexing agent: 1 part of tetrahydroxyethylethylenediamine;

[0057] Dehydrating agent: 7 parts of Ka zeolite molecular sieve;

[0058] Stripping aid: 6 parts of N-octyl pyrrolidone;

[0059] Cleaning aid: 1 part hexadecyl mercaptan, 1 part octadecyl mercaptan.

[0060] The specific preparation steps are as follows:

[0061] In the ultra-clean room, in a high-speed stirring kettle, the complexing agent, stripping aid and cleaning aid are dissolved in the solvent, stirred at a speed of 200r / min for 40 minutes, and then filtered with a filtration accuracy of 0.1μm to obtain a mixed solution, which is then placed in a clean bucket made of HDPE material. At room temperature, the dehydrating agent is soaked in acetone for 40 minutes, dried at 70℃ for 20 minutes, and the soaking and drying process is repeated four times; then the mixed solution and the dehydrating agent are mixed to obtain a degumming solution.

[0062] Example 3

[0063] The raw materials and dosages used in this embodiment are as follows:

[0064] Solvent: 20 parts of 2,2,4,6,6-pentamethylheptane, 10 parts of dipropylene glycol dimethyl ether, 50 parts of o-dichlorobenzene;

[0065] Complexing agent: 3 parts of tetrahydroxyethylethylenediamine, 1 part of dibutyl dithiophosphoric acid;

[0066] Dehydrating agent: 8 parts of Ka zeolite molecular sieve;

[0067] Stripping aid: 8 parts of N-octyl pyrrolidone;

[0068] Cleaning aid: 1 part of octadecyl mercaptan.

[0069] The specific preparation steps are as follows:

[0070] In the ultra-clean room, in a high-speed stirring kettle, the complexing agent, stripping agent and cleaning agent are dissolved in the solvent, stirred at a speed of 220r / min for 35 minutes, and then filtered with a filtration accuracy of 0.1μm to obtain a mixed solution, which is then placed in a clean bucket made of HDPE material. At room temperature, the dehydrating agent is soaked in acetone for 35 minutes, dried at 70℃ for 20 minutes, and the soaking and drying process is repeated five times; then the mixed solution and the dehydrating agent are mixed to obtain a degumming solution.

[0071] Example 4

[0072] The raw materials and dosages used in this embodiment are as follows:

[0073] Solvent: 30 parts of 2,2,4,6,6-pentamethylheptane, 30 parts of diethylene glycol tert-butyl ether, 10 parts of o-dichlorobenzene;

[0074] Complexing agent: 2 parts of tetrahydroxyethylethylenediamine;

[0075] Dehydrating agent: ka zeolite molecular sieve 9 parts;

[0076] Stripping aid: 7 parts of N-octyl pyrrolidone;

[0077] Cleaning aid: 1 part of octadecyl mercaptan.

[0078] The specific preparation steps are as follows:

[0079] In the ultra-clean room, in a high-speed stirring kettle, the complexing agent, stripping aid and cleaning aid are dissolved in the solvent, stirred at a speed of 300r / min for 30 minutes, and then filtered with a filtration accuracy of 0.2μm to obtain a mixed solution, which is then placed in a clean bucket made of HDPE material. At room temperature, the dehydrating agent is soaked in acetone for 50 minutes, dried at 70℃ for 20 minutes, and the soaking and drying process is repeated three times; then the mixed solution and the dehydrating agent are mixed to obtain a degumming solution.

[0080] Example 5

[0081] The raw materials and dosages used in this embodiment are as follows:

[0082] Solvent: 60 parts of diethylene glycol tert-butyl ether, 30 parts of o-dichlorobenzene;

[0083] Complexing agent: 5 parts of tetrahydroxyethylethylenediamine;

[0084] Dehydrating agent: 10 parts of ka zeolite molecular sieve;

[0085] Stripping aid: 10 parts of N-octyl pyrrolidone;

[0086] Cleaning aid: 1 part of octadecyl mercaptan.

[0087] The specific preparation steps are as follows:

[0088] In the ultra-clean room, in a high-speed stirring kettle, the complexing agent, stripping aid and cleaning aid are dissolved in the solvent, stirred at a speed of 250r / min for 60 minutes, and then filtered with a filtration accuracy of 0.1μm to obtain a mixed solution, which is then placed in a clean bucket made of HDPE material. At room temperature, the dehydrating agent is soaked in acetone for 45 minutes, dried at 70℃ for 20 minutes, and the soaking and drying process is repeated three times; then the mixed solution and the dehydrating agent are mixed to obtain a degumming solution.

[0089] Performance Testing

[0090] The degumming solutions prepared in Examples 1 to 5 of the present invention and the commercially available VS1016 degumming solution were used to treat the chip containing the photoresist, and the specific treatment process was as follows:

[0091] In the cleaning tank, at 80°C, the chip was added to the degumming solution and ultrasonically treated at a frequency of 40kHz for 10 minutes, repeated twice; then the chip was added to the acetone solution and soaked at room temperature for 10 minutes; then the chip was rinsed with water twice, each time for 10 minutes; finally, it was blown dry with nitrogen at 70°C. A soptop brand MX8R model microscope was used to observe the metal corrosion and cleaning effect, and the test results are shown in Table 1.

[0092] Table 1 Performance test results of degumming liquid

[0093]

[0094] In Table 1, VS1016 is a degumming liquid product sold by Sandaoke Chemical Co., Ltd., and its main raw materials are NMP, sulfones and organic bases. As shown in Table 1, the degumming liquid prepared by the present invention has a better degumming effect and less damage to the chip than the prior art.

[0095] The various embodiments in this specification are described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the various embodiments can be referenced to each other.

[0096] The above description of the disclosed embodiments enables one skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to one skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A degumming solution, characterized in that: The composition comprises the following components in parts by weight: 70-90 parts of solvent, 1-5 parts of complexing agent, 5-10 parts of dehydrating agent, 5-10 parts of stripping agent, 1-3 parts of cleaning agent; The solvent is 2,2,4,6,6-pentamethylheptane, glycol ether or dichlorobenzene; The diol ether is diethylene glycol tert-butyl ether and / or dipropylene glycol dimethyl ether; The dichlorobenzene is o-dichlorobenzene and / or m-dichlorobenzene; The complexing agent is tetrahydroxyethylethylenediamine and / or dibutyl dithiophosphate; The stripping aid is N-octyl pyrrolidone and / or trifluoromethanesulfonimide; The cleaning aid is hexadecyl mercaptan and / or octadecyl mercaptan.

2. The degumming solution according to claim 1, characterized in that: The dehydrating agent is ka zeolite molecular sieve.

3. The method for preparing the degumming solution according to claim 1 or 2, characterized in that: The following steps are involved: S1, mixing the solvent, the complexing agent, the stripping agent and the cleaning agent, and filtering to obtain a mixed solution; soaking and drying the dehydrating agent in sequence; S2. Mix the dried dehydrating agent and the mixed liquid to obtain a degumming liquid.

4. The preparation method according to claim 3, characterized in that: In step S1, mixing is performed by stirring at a speed of 100 to 300 r / min and a stirring time of 30 to 60 min; The filtration degree of the filtration is 0.1 to 0.2 μm; The immersion is carried out in acetone, and the immersion time is 30 to 50 minutes.

5. Use of the degumming solution according to claim 1 or 2 in integrated circuits, discrete semiconductor devices, display screens or chip packaging.

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