A chip integrated circuit tetramethylammonium hydroxide developer and its preparation method

Abstract

The present invention relates to the technical field of developing solutions, and particularly relates to a tetramethylammonium hydroxide developing solution for chip integrated circuits and a preparation method thereof. The developing solution contains tetramethylammonium hydroxide and water, and also contains a composite surfactant and composite gel microspheres; the mass percentage of the composite gel microspheres in the developing solution is 0.3 - 0.6%; in the developing solution, the concentration of tetramethylammonium hydroxide is 2.1 - 2.8 wt%. The developing solution in the present invention has a relatively low surface tension. After developing the product, the developing solution hardly adheres to the surface of the product, thus facilitating subsequent rinsing with clean water, preventing spots from forming on the product, and improving the quality of the product; moreover, after use, the waste liquid generated by the developing solution can accelerate the enrichment of microorganisms during biochemical treatment, thereby improving the degradation efficiency and preventing the waste liquid of the developing solution from affecting the environment, meeting the environmental protection requirements.

Description

Technical Field

[0001] The present invention relates to the technical field of developing solutions, and particularly to a tetramethylammonium hydroxide developing solution for chip integrated circuits and a preparation method thereof. Background Art

[0002] TMAH, namely tetramethylammonium hydroxide, can be used as a developing solution in the lithography process. For large-sized products, it is necessary to first develop the products with a positive photoresist developing solution in an alkali washing tank, then take out the products and rinse them with clean water. At the same time, after the developing solution is used, the waste developing solution is usually treated by biochemical treatment as hazardous waste. Biochemical treatment means using microorganisms to degrade the tetramethylammonium hydroxide in the waste developing solution to meet the discharge requirements of the external drainage.

[0003] The invention patent with the publication number CN106842833A discloses a preparation method of a developing solution, including the following steps: (1) Stir and dissolve salicylate in benzyl alcohol to obtain solution a; (2) Heat solution a to 40 - 46°C, add a developing main agent composed of isopropylamine and triethylenetetramine, and stir at a stirring speed of 800 r / min for 18 - 25 min to obtain solution b; (3) Maintain the temperature of solution b at 40 - 46°C, sequentially add a wetting agent, polyoxyethylene glycerol ether, and 2-phosphonobutane-1,2,4-tricarboxylic acid, and stir at a stirring speed of 200 r / min for 8 - 13 min to obtain solution c; (4) Add deionized water and citrate to solution c, stir evenly, adjust and maintain the solution temperature within the range of 22 - 25°C, and finally obtain the developing solution; this developing solution has the advantages of good developing effect and not being prone to turbidity. However, after this developing solution is used to process the products, the developing solution remaining on the products after taking out the products from the alkali washing tank will be exposed to the air, and the TMAH remaining on the products will react with carbon dioxide in the air to form spots on the products, which are difficult to remove even after rinsing with clean water, affecting the product quality; moreover, when this developing solution is subjected to biochemical treatment after use, due to the relatively slow enrichment rate of microorganisms, the degradation efficiency of the developing solution is slow and the degradation cycle is long, resulting in the external drainage not being able to meet the discharge requirements in a short time.

[0004] Therefore, it is particularly important to seek a preparation method of a developing solution that produces a developing solution with low surface tension, meets environmental protection requirements, and can be quickly degraded. Summary of the Invention

[0005] In view of the problems existing in the prior art, the present invention provides a tetramethylammonium hydroxide developer for chip integrated circuits and a preparation method thereof. The produced developer has a low surface tension. After the product is developed, the developer hardly adheres to the surface of the product, thereby facilitating subsequent washing with clean water, so that no spots are formed on the product, and the quality of the product is improved; moreover, after the developer is used, the waste liquid generated can accelerate the enrichment of microorganisms during biochemical treatment, thereby improving the degradation efficiency, so that the developer waste liquid will not have an impact on the environment, and meets environmental protection requirements.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] A chip integrated circuit tetramethyl ammonium hydroxide developer comprises tetramethyl ammonium hydroxide and water, and further comprises a composite surfactant and composite gel microspheres.

[0008] As a further preferred embodiment of the present invention, the mass percentage of the composite surfactant in the developer is 0.6-1.2%; the mass percentage of the composite gel microspheres in the developer is 0.3-0.6%; and the concentration of tetramethylammonium hydroxide in the developer is 2.1-2.8wt%.

[0009] As a further preferred embodiment of the present invention, the composite surfactant is composed of liquid A and liquid B, and the volume ratio of liquid A to liquid B is 1:(2-5).

[0010] Furthermore, the configuration method of the A liquid is as follows:

[0011] Prepare an aqueous solution of sodium dodecyl sulfate of appropriate concentration, then add zinc chloride and ferric chloride thereto in sequence, and stir thoroughly to obtain liquid A.

[0012] Furthermore, the concentration of the sodium dodecyl sulfate aqueous solution is 10-20 mmol / L;

[0013] In the liquid A, the zinc ion concentration is 20-60 mmol / L, and the iron ion concentration is 2.0-2.7 mmol / L.

[0014] Furthermore, the preparation method of the B solution is as follows:

[0015] Add appropriate amount of C 12-14 Fatty alcohol and pyridine are vacuum-sucked into the autoclave, heated to 80-86°C, low-boiling substances and water are vacuum-removed, and after nitrogen replacement 3-5 times, the temperature is raised to 175-178°C, and ethylene oxide is added to the autoclave in batches. After the feeding is completed, it is cooled to 80-85°C, aged to a constant pressure, and the ethylene oxide gas in the reaction system is vacuum-removed, and nitrogen is filled to discharge the material to obtain liquid B.

[0016] Furthermore, the C 12-14 The mass ratio of the fatty alcohol, pyridine, and ethylene oxide is (10 - 20):(0.8 - 1.5):(5 - 9);

[0017] The addition method of the ethylene oxide is as follows: First, add half of the ethylene oxide into the reaction kettle for reaction. When the pressure in the reaction kettle drops to 0.08 - 0.1 MPa, divide the remaining ethylene oxide into 3 - 5 portions and add them to the reaction kettle in batches. The addition timing is when the pressure in the reaction kettle drops to 0.1 - 0.12 MPa. Wait until all the ethylene oxide is added to the reaction kettle.

[0018] As a further preferred embodiment of the present invention, the preparation method of the composite gel microspheres is as follows:

[0019] (1) Add an appropriate amount of polyvinylpyrrolidone to deionized water. After stirring and mixing evenly, add sodium diethyldithiocarbamate trihydrate and molybdenum pentachloride in sequence. After mixing evenly, transfer to an autoclave and react at 230 - 240 °C for 23 - 26 h. After the reaction ends, cool to room temperature. Wash the product by centrifugation with distilled water and then dry it to obtain molybdenum disulfide nanosheets;

[0020] (2) Dissolve an appropriate amount of calcium chloride in deionized water. After fully stirring and dissolving, obtain an aqueous calcium chloride solution for standby. Then dissolve an appropriate amount of sodium alginate and wolfberry polysaccharide in deionized water. After fully dissolving, add molybdenum disulfide nanosheets and ultrasonically disperse for 10 - 30 min to obtain a mixed solution for standby;

[0021] (3) Pour the mixed solution into a syringe, connect a load voltage to the syringe needle part, with the needle as the positive electrode. Slowly push out the solution through a micro-injection pump at a speed of 10 - 30 μL / min and drop it into the aqueous calcium chloride solution. Gel for 30 - 50 min. Filter and separate the product, and freeze-dry to obtain the composite gel microspheres.

[0022] Furthermore, the dosage ratio of the polyvinylpyrrolidone, deionized water, sodium diethyldithiocarbamate trihydrate, and molybdenum pentachloride is (5 - 10) g:(400 - 1000) mL:(4.5 - 5.6) g:(2.5 - 3.6) g;

[0023] In the mixed solution, the dosage ratio of sodium alginate, wolfberry polysaccharide solution, deionized water, and molybdenum disulfide nanosheets is (1 - 5) g:(0.6 - 1.8) g:(30 - 50) mL:(0.1 - 0.3) g;

[0024] The volume ratio of the mixed solution to the aqueous calcium chloride solution is (30 - 50):(800 - 1000);

[0025] The concentration of the calcium chloride aqueous solution is 0.1-0.15 mol / L;

[0026] The particle size of the composite gel microsphere is 1-5 μm.

[0027] A method for preparing a tetramethylammonium hydroxide developer for a chip integrated circuit comprises the following steps: transporting tetramethylammonium hydroxide to a preparation tank, introducing water into the preparation tank to dilute the tetramethylammonium hydroxide, and then introducing a composite surfactant and composite gel microspheres into the preparation tank according to mass percentage, and mixing to obtain the tetramethylammonium hydroxide developer.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] Aiming at the defect that the developer in the prior art has high surface tension and will adhere to the product, after being exposed to the air, the residual tetramethylammonium hydroxide will react with the carbon dioxide in the air to form spots on the product, thus affecting the product quality, in the present invention, a composite surfactant is added to the developer, the composite surfactant is composed of liquid A and liquid B, wherein liquid A is composed of sodium dodecyl sulfate, zinc chloride and ferric chloride, by introducing divalent zinc ions and trivalent iron ions into the sodium dodecyl sulfate, utilizing the strong ability of zinc ions and iron ions to compress the double electric layer diffusion, making it easier for the sodium dodecyl sulfate molecules to aggregate and adsorb on the surface, thereby effectively reducing the electrostatic repulsion between the surface active ions and making the surface tension smaller; and by utilizing C in liquid B, the surface active agent is added to the developer, and ... 12-14 Fatty alcohol and ethylene oxide react under the action of catalyst pyridine to synthesize straight-chain alcohol ether. Since the straight-chain alcohol ether has a large average molecular area of ​​branched surfactant molecules and a small density of hydrophobic groups in the surface adsorption layer, it has a strong ability to reduce surface tension. The composite surfactant formed by mixing liquid A and liquid B has a very strong ability to reduce surface tension and can significantly reduce the surface tension of the developer, so that the developer will not adhere to the product after the product is taken out of the alkaline washing tank, thereby solving the problem of spots on the product.

[0030] Regarding the organic nitrogen compound tetramethylammonium hydroxide contained in the developer, which is strongly alkaline, corrosive and biologically toxic, it is necessary to remove the total nitrogen from the developer waste liquid. However, in the current biochemical treatment process, the enrichment rate of microorganisms is relatively slow, resulting in the defect of low degradation rate of the developer waste liquid. In the present invention, the electrostatic droplet method is used, and calcium chloride, sodium alginate and wolfberry polysaccharide are used as raw materials to prepare composite gel microspheres. The composite gel microspheres have good biodegradability and sustained-release effect, and can slowly release the loaded wolfberry polysaccharide. The wolfberry polysaccharide can provide nutrients for the growth of microorganisms as a carbon source, thereby promoting the enrichment of microorganisms in the degradation process of the developer waste liquid, so that the tetramethylammonium hydroxide in the developer waste liquid can be efficiently degraded, and the developer waste liquid will not affect the environment and meets the environmental protection requirements; moreover, in order to further improve the degradation effect and slow down the overflow of wolfberry polysaccharide, molybdenum disulfide nanosheets are added to the dissolution solution of sodium alginate and wolfberry polysaccharide in the present invention. The added molybdenum disulfide nanosheets can form a covering layer with a loose structure on the surface of the composite gel microspheres. On the one hand, it can play a role in delaying the overflow of wolfberry polysaccharide and avoid the phenomenon that the wolfberry polysaccharide loaded in the composite gel microspheres overflows too early and affects the microbial degradation. At the same time, the formation of the covering layer increases the surface roughness of the composite gel microspheres. The increase in surface roughness enhances the van der Waals adsorption force between the composite gel microspheres and microorganisms and the surface energy of the composite gel microspheres, thereby promoting the attachment and aggregation of microorganisms on the rough surface of the composite gel, further improving the enrichment effect of microorganisms, enhancing the reduction effect of the developer waste liquid, and making the developer in the present invention more compliant with environmental protection requirements and having the characteristics of rapid degradation.

[0031] The developer in the present invention has a low surface tension. After developing the product, the developer hardly adheres to the surface of the product, thus facilitating subsequent rinsing with clean water, preventing spots from forming on the product, and improving the quality of the product; moreover, after the developer is used, the waste liquid generated can accelerate the enrichment of microorganisms during biochemical treatment, thereby improving the degradation efficiency, making the developer waste liquid not affect the environment and meeting the environmental protection requirements. Detailed implementation mode

[0032] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0033] Example 1

[0034] A chip integrated circuit tetramethylammonium hydroxide developer, the developer comprising tetramethylammonium hydroxide and water, wherein the concentration of tetramethylammonium hydroxide in the developer is 2.38wt%;

[0035] The developer also contains a composite surfactant and gel composite microspheres;

[0036] The mass percentage of the composite surfactant in the developer is 0.6%, and the mass percentage of the gel composite microspheres in the developer is 0.3%.

[0037] The preparation method of the developer comprises the following steps: transporting tetramethylammonium hydroxide to a preparation tank, introducing water into the preparation tank to dilute the tetramethylammonium hydroxide, and then introducing a composite surfactant and composite gel microspheres into the preparation tank according to mass percentage, and mixing to obtain a tetramethylammonium hydroxide developer.

[0038] The composite surfactant is composed of liquid A and liquid B, and the volume ratio of liquid A to liquid B is 1:2;

[0039] The configuration method of liquid A is as follows:

[0040] Prepare a 10 mmol / L sodium dodecyl sulfate aqueous solution, then add zinc chloride and ferric chloride to the solution in sequence, stir thoroughly, control the zinc ion concentration to 20 mmol / L, and the iron ion concentration to 2.0 mmol / L, to obtain solution A;

[0041] The preparation method of liquid B is as follows:

[0042] 10gC 12-14 Fatty alcohol and 0.8g pyridine are vacuum-sucked into an autoclave, heated to 80°C, low-boiling substances and water are vacuum-removed, and after nitrogen replacement three times, the temperature is raised to 175°C, and 2.5g ethylene oxide is added for reaction. When the pressure in the reactor drops to 0.08MPa, the remaining ethylene oxide is divided into three equal parts and added to the reactor in batches. The addition time is when the pressure in the reactor drops to 0.1MPa. After all the ethylene oxide is added to the reactor, the feeding is stopped, the reactor is cooled to 80°C, aged until the pressure is constant, and the ethylene oxide gas in the reaction system is vacuum-removed. The system is filled with nitrogen and discharged to obtain liquid B.

[0043] The preparation method of the composite gel microspheres is as follows:

[0044] (1) Weigh 5 g of polyvinylpyrrolidone and add it to 400 mL of deionized water. After stirring and mixing evenly, add 4.5 g of sodium diethyldithiocarbamate trihydrate and 2.5 g of molybdenum pentachloride in sequence. After mixing evenly, transfer the mixture to an autoclave and react at 230 °C for 23 h. After the reaction is completed, cool it to room temperature. Wash the product by centrifugation with distilled water and then dry it to obtain molybdenum disulfide nanosheets;

[0045] (2) Weigh calcium chloride and dissolve it in deionized water. After fully stirring and dissolving, obtain a calcium chloride aqueous solution with a concentration of 0.1 mol / L for standby. Then weigh 1 g of sodium alginate and 0.6 g of wolfberry polysaccharide and dissolve them in 30 mL of deionized water. After fully dissolving, add 0.1 g of molybdenum disulfide nanosheets and ultrasonically disperse them for 10 min at 300 W to obtain a mixed solution for standby;

[0046] (3) Pour 30 mL of the mixed solution into a syringe, connect a load voltage to the needle part of the syringe, with the needle as the positive electrode. Slowly push out the solution drop by drop into 800 mL of the calcium chloride aqueous solution at a speed of 10 μL / min through a micro-injection pump, and gel for 30 min. Filter and separate the product, and freeze-dry it to obtain composite gel microspheres with a particle size of 1 μm.

[0047] Example 2

[0048] A chip integrated circuit tetramethylammonium hydroxide developer, the developer contains tetramethylammonium hydroxide and water. In this developer, the concentration of tetramethylammonium hydroxide is 2.5 wt%;

[0049] The developer also contains a composite surfactant and gel composite microspheres;

[0050] Among them, the mass percentage of the composite surfactant in the developer is 1%, and the mass percentage of the gel composite microspheres in the developer is 0.3%;

[0051] The preparation method of the developer includes the following steps: Transport tetramethylammonium hydroxide to a preparation tank, introduce water into the preparation tank to dilute the tetramethylammonium hydroxide, and then introduce the composite surfactant and composite gel microspheres into the preparation tank according to the mass percentage. After mixing evenly, the tetramethylammonium hydroxide developer can be obtained.

[0052] Among them, the composite surfactant is composed of liquid A and liquid B, and the volume ratio of liquid A to liquid B is 1:3;

[0053] The preparation method of liquid A is as follows:

[0054] Prepare a 15 mmol / L sodium dodecyl sulfate aqueous solution, then add zinc chloride and ferric chloride to the solution in sequence, stir thoroughly, control the zinc ion concentration to 35 mmol / L, and the iron ion concentration to 2.4 mmol / L, to obtain solution A;

[0055] The preparation method of liquid B is as follows:

[0056] 15gC 12-14 Fatty alcohol and 1.3 g of pyridine were vacuum-sucked into the autoclave, and the temperature was raised to 85°C. Low-boiling substances and water were removed in vacuo. After nitrogen replacement for 4 times, the temperature was raised to 176°C, and 3.5 g of ethylene oxide was added for reaction. When the pressure in the reactor dropped to 0.1 MPa, the remaining ethylene oxide was divided into 4 equal parts and added to the reactor in batches. The addition time was when the pressure in the reactor dropped to 0.12 MPa. After all the ethylene oxide was added to the reactor, the feeding was stopped, the reactor was cooled to 82°C, aged until the pressure was constant, and the ethylene oxide gas in the reaction system was vacuum-removed. The system was filled with nitrogen and discharged to obtain liquid B.

[0057] The preparation method of the composite gel microspheres is as follows:

[0058] (1) Weigh 7 g of polyvinyl pyrrolidone and add it to 800 mL of deionized water, stir and mix, then add 5.2 g of sodium diethyldithiocarbamate trihydrate and 3.1 g of molybdenum pentachloride in sequence, mix well and transfer to an autoclave, react at 235° C. for 25 h, after the reaction is completed, cool to room temperature, wash the product with distilled water by centrifugation and dry it to obtain molybdenum disulfide nanosheets;

[0059] (2) Weigh calcium chloride and dissolve it in deionized water. After fully stirring and dissolving, obtain a 0.12 mol / L calcium chloride aqueous solution, which is set aside. Then weigh 3 g of sodium alginate and 1.3 g of wolfberry polysaccharide and dissolve them in 40 mL of deionized water. After fully dissolving, add 0.2 g of molybdenum disulfide nanosheets and disperse them ultrasonically at 400 W for 20 min to obtain a mixed solution, which is set aside.

[0060] (3) Pour 40 mL of the mixed solution into a syringe, connect a load voltage to the needle of the syringe, with the needle as the positive electrode, and slowly push the solution out at a rate of 20 μL / min through a microinjection pump and drop it into 900 mL of a calcium chloride aqueous solution. Gelation takes 40 minutes, and the product is filtered and separated, and freeze-dried to obtain composite gel microspheres with a particle size of 3 μm.

[0061] Example 3

[0062] A tetramethylammonium hydroxide developer for chip integrated circuits, the developer comprising tetramethylammonium hydroxide and water, wherein the concentration of tetramethylammonium hydroxide in the developer is 2.8 wt %;

[0063] The developer also contains a composite surfactant and gel composite microspheres;

[0064] The mass percentage of the composite surfactant in the developer is 1%, and the mass percentage of the gel composite microspheres in the developer is 0.6%.

[0065] The preparation method of the developer comprises the following steps: transporting tetramethylammonium hydroxide to a preparation tank, introducing water into the preparation tank to dilute the tetramethylammonium hydroxide, and then introducing a composite surfactant and composite gel microspheres into the preparation tank according to mass percentage, and mixing to obtain a tetramethylammonium hydroxide developer.

[0066] The composite surfactant is composed of liquid A and liquid B, and the volume ratio of liquid A to liquid B is 1:5;

[0067] The configuration method of liquid A is as follows:

[0068] Prepare a 20 mmol / L sodium dodecyl sulfate aqueous solution, then add zinc chloride and ferric chloride to the solution in sequence, stir thoroughly, control the zinc ion concentration to 60 mmol / L, and the iron ion concentration to 2.7 mmol / L, to obtain solution A;

[0069] The preparation method of liquid B is as follows:

[0070] 20gC 12-14 Fatty alcohol and 1.5g pyridine were vacuum-sucked into the autoclave, and the temperature was raised to 86°C. Low-boiling substances and water were removed in vacuo. After nitrogen replacement for 5 times, the temperature was raised to 178°C, and 4.5g ethylene oxide was added for reaction. When the pressure in the reactor dropped to 0.12MPa, the remaining ethylene oxide was divided into 5 equal parts and added to the reactor in batches. The addition time was when the pressure in the reactor dropped to 0.15MPa. After all the ethylene oxide was added to the reactor, the feeding was stopped, the reactor was cooled to 85°C, aged until the pressure was constant, and the ethylene oxide gas in the reaction system was vacuum-removed. The reaction system was filled with nitrogen and discharged to obtain liquid B.

[0071] The preparation method of the composite gel microspheres is as follows:

[0072] (1) Weigh 10 g of polyvinyl pyrrolidone and add it to 1000 mL of deionized water, stir and mix, then add 5.6 g of sodium diethyldithiocarbamate trihydrate and 3.6 g of molybdenum pentachloride in sequence, mix well and transfer to an autoclave, react at 240° C. for 26 h, after the reaction is completed, cool to room temperature, wash the product with distilled water by centrifugation and dry it to obtain molybdenum disulfide nanosheets;

[0073] (2) Weigh calcium chloride and dissolve it in deionized water. After stirring well until it is completely dissolved, obtain an aqueous calcium chloride solution with a concentration of 0.15 mol / L for standby. Then, weigh 5 g of sodium alginate and 1.8 g of wolfberry polysaccharide, dissolve them in 50 mL of deionized water. After complete dissolution, add 0.3 g of molybdenum disulfide nanosheets, and ultrasonically disperse for 30 min at 500 W to obtain a mixed solution for standby;

[0074] (3) Pour 50 mL of the mixed solution into a syringe, connect a load voltage to the needle part of the syringe, with the needle as the positive electrode. Slowly push out the solution dropwise into 1000 mL of the aqueous calcium chloride solution at a speed of 30 μL / min through a micro-injection pump, and gel for 50 min. Filter and separate the product, and freeze-dry to obtain composite gel microspheres with a particle size of 5 μm.

[0075] Comparative Example 1: This comparative example is basically the same as Example 1, except that it does not contain a composite surfactant.

[0076] Comparative Example 2: This comparative example is basically the same as Example 1, except that the composite surfactant does not contain liquid A.

[0077] Comparative Example 3: This comparative example is basically the same as Example 1, except that the composite surfactant does not contain liquid B.

[0078] Comparative Example 4: This comparative example is basically the same as Example 1, except that it does not contain composite gel microspheres.

[0079] Comparative Example 5: This comparative example is basically the same as Example 1, except that the composite gel microspheres do not contain molybdenum disulfide nanosheets.

[0080] Control group: The developer provided in Example 1 of the invention patent with the publication number of CN106842833A.

[0081] Test Experiment 1:

[0082] Adopt the Wilhelmy plate method to conduct surface tension tests on the developer samples in Examples 1 - 3, Comparative Examples 1 - 5, and the control group. Hang a cover glass with a smooth and uniform surface on a torsion balance, and then vertically insert it into the liquid so that the bottom edge parallel plane just contacts the liquid surface, and measure the force received during the wetting process. The test results are shown in Table 1.

[0083] Table 1

[0084]

[0085]

[0086] As can be seen from the results in Table 1, the developer in the present invention has a low surface tension. After developing the product, the developer hardly adheres to the surface of the product, facilitating subsequent rinsing with clean water, preventing the formation of spots on the product, and improving the quality of the product.

[0087] Test Experiment 2:

[0088] Use the developer samples in Examples 1 - 3, Comparative Examples 1 - 5, and the control group to develop the product (in the developer samples, the initial concentration of tetramethylammonium hydroxide is controlled at 2.38 wt%). Subject the generated developer waste liquid to biochemical treatment (for the specific treatment method, refer to the method disclosed in the invention patent with the publication number CN111268863A). Stop the treatment when the concentration of tetramethylammonium hydroxide in the waste liquid drops to 0.3 mg / L. Record the treatment time of each developer waste liquid, and take the treatment time of the developer waste liquid in the control group as the standard. Compare the treatment times in Examples 1 - 3 and Comparative Examples 1 - 5 with that of the control group. The results are shown in Table 2.

[0089] Table 2

[0090] Example 1 Example 2 Example 3 Reduction in processing time / % 28.5 30.6 29.7 Comparative Example 1 Comparative Example 2 Comparative Example 3 Reduction in processing time / % 27.9 27.3 27.6 Comparative Example 4 Comparative Example 5 Control group Reduction in processing time / % 1.2 17.8 0

[0091] As can be seen from the results in Table 2, for the developer in the present invention, the waste liquid generated after use can accelerate the enrichment of microorganisms during biochemical treatment, thereby improving the degradation efficiency and shortening the time of biochemical treatment, so that the developer waste liquid will not affect the environment and meets the environmental protection requirements.

[0092] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific embodiments described. Obviously, many modifications and variations can be made according to the content of this specification. These embodiments are selected and specifically described in this specification to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and utilize the present invention well. The present invention is only limited by the claims and their full scope and equivalents.

Claims

1. A chip integrated circuit tetramethylammonium hydroxide developer, the developer comprising tetramethylammonium hydroxide and water, characterized in that, The developer also contains a composite surfactant and composite gel microspheres; The composite surfactant is composed of liquid A and liquid B, and the volume ratio of liquid A to liquid B is 1:(2 - 5); The preparation method of the liquid A is as follows: Prepare an aqueous solution of sodium dodecyl sulfate with an appropriate concentration, and then add zinc chloride and ferric chloride thereto in sequence. After sufficient stirring, the liquid A can be obtained; The preparation method of the liquid B is as follows: Add an appropriate amount of C 12-14 Vacuum suck the fatty alcohol and pyridine into the autoclave, heat up to 80 - 86 °C, and vacuum remove the low-boiling substances and water. After purging with nitrogen for 3 - 5 times, heat up to 175 - 178 °C, and add ethylene oxide to the autoclave in batches. After the feeding is completed, cool down to 80 - 85 °C, age until the pressure is constant, vacuum remove the ethylene oxide gas in the reaction system, fill with nitrogen and discharge, then liquid B can be obtained.

2. The tetramethylammonium hydroxide developer for a chip integrated circuit according to claim 1, characterized in that, The mass percentage of the composite surfactant in the developer is 0.6 - 1.2%; the mass percentage of the composite gel microspheres in the developer is 0.3 - 0.6%; in the developer, the concentration of tetramethylammonium hydroxide is 2.1 - 2.8 wt%.

3. A tetramethylammonium hydroxide developer for a chip integrated circuit according to claim 1, characterized in that The concentration of the aqueous solution of sodium dodecyl sulfate is 10 - 20 mmol / L; In the liquid A, the concentration of zinc ions is 20 - 60 mmol / L, and the concentration of ferric ions is 2.0 - 2.7 mmol / L.

4. A tetramethylammonium hydroxide developer for a chip integrated circuit according to claim 1, characterized in that, The said C 12-14 The mass ratio of fatty alcohol, pyridine and ethylene oxide is (10 - 20):(0.8 - 1.5):(5 - 9); The addition method of ethylene oxide is as follows: First, add half of the amount of ethylene oxide to the reaction kettle for reaction. When the pressure in the reaction kettle drops to 0.08 - 0.1 MPa, divide the remaining ethylene oxide into 3 - 5 portions and add them to the reaction kettle in batches. The addition timing is when the pressure in the reaction kettle drops to 0.1 - 0.12 MPa. Wait until all the ethylene oxide is added to the reaction kettle.

5. A tetramethylammonium hydroxide developer for a chip integrated circuit according to claim 1, wherein The preparation method of the composite gel microspheres is as follows: (1) Add an appropriate amount of polyvinylpyrrolidone to deionized water, stir and mix evenly, then add sodium diethyldithiocarbamate trihydrate and molybdenum pentachloride in sequence. After mixing evenly, transfer it to an autoclave and react at 230 - 240 °C for 23 - 26 h. After the reaction is completed, cool to room temperature, wash the product with distilled water by centrifugation and then dry it to obtain molybdenum disulfide nanosheets; (2) Dissolve an appropriate amount of calcium chloride in deionized water, stir and dissolve it fully to obtain an aqueous solution of calcium chloride for standby. Then dissolve an appropriate amount of sodium alginate and wolfberry polysaccharide in deionized water, dissolve them fully, add the molybdenum disulfide nanosheets, and perform ultrasonic dispersion for 10 - 30 min to obtain a mixed solution for standby; (3) Pour the mixed solution into a syringe, connect a load voltage to the syringe needle part, the needle is the positive electrode, and slowly push out the solution through a micro-injection pump at a speed of 10 - 30 μL / min and drop it into the aqueous solution of calcium chloride. Gelatinize for 30 - 50 min, filter and separate the product, and freeze-dry it to obtain the composite gel microspheres.

6. The tetramethylammonium hydroxide developing solution for a chip integrated circuit according to claim 5, wherein, The dosage ratio of polyvinylpyrrolidone, deionized water, sodium diethyldithiocarbamate trihydrate and molybdenum pentachloride is (5 - 10) g:(400 - 1000) mL:(4.5 - 5.6) g:(2.5 - 3.6) g; In the mixed solution, the dosage ratio of sodium alginate, wolfberry polysaccharide solution, deionized water and molybdenum disulfide nanosheets is (1 - 5) g:(0.6 - 1.8) g:(30 - 50) mL:(0.1 - 0.3) g; The volume ratio of the mixed solution to the aqueous solution of calcium chloride is (30 - 50):(800 - 1000); The concentration of the aqueous solution of calcium chloride is 0.1 - 0.15 mol / L; The particle size of the composite gel microspheres is 1 - 5 μm.

7. A method for preparing a tetramethylammonium hydroxide developer for a chip integrated circuit according to any one of claims 1-6, characterized in that, It includes the following steps: Transport tetramethylammonium hydroxide to a preparation tank, introduce water into the preparation tank to dilute the tetramethylammonium hydroxide, and then introduce a composite surfactant and composite gel microspheres into the preparation tank according to mass percentage. After mixing evenly, a tetramethylammonium hydroxide developer can be obtained.

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