Semiconductor-grade quartz ring cleaning agent and preparation method thereof

Abstract

The invention discloses a semiconductor grade quartz ring cleaning agent and a preparation method thereof, and relates to the technical field of quartz ring processing. The cleaning agent comprises the following components in percentage by weight: 0.2-1% of an anionic surfactant, 0.1-0.5% of a nonionic surfactant, 0.5-4% of a chelating agent, 1-5% of an organic solvent, 1-5% of a cleaning synergist, 0.1-1% of a pH regulator and the balance of deionized water. The prepared cleaning agent can efficiently remove pollutants such as residual organic matters, particulate matters and metal ions on the surface of the quartz ring, the surface of a device cannot be corroded, the organic pollutants can be clustered and gathered on the surface of the cleaning solution after cleaning, and the cleaning solution can be conveniently recycled and repeatedly utilized. Through the synergistic effect of anionic and nonionic surfactants on molecular structures, charge properties and interface behaviors, the cleaning efficiency can be remarkably improved, and the dosage of the cleaning agent is reduced. Compared with an existing semiconductor-grade cleaning agent, the cleaning agent has the advantages of being simple in preparation method, environmentally friendly and the like, and has a good application prospect.

Description

Technical Field

[0001] The invention belongs to the technical field of quartz ring processing, and in particular relates to a semiconductor-grade quartz ring cleaning agent and a preparation method thereof. Background Art

[0002] The surface cleanliness of wafers and related parts has an important impact on their quality and the yield rate of downstream processed devices. With the development of integrated circuits and the continuous reduction of key chip dimensions, the requirements for the cleanliness of semiconductor manufacturing processes are becoming increasingly higher. Quartz products are widely used in diffusion, oxidation, photolithography, etching, cleaning and other processes in semiconductor wafer manufacturing due to their high purity, excellent heat resistance, light transmittance, electrical insulation and chemical stability. Semiconductor quartz components account for about 70% of the quartz market and are the largest application area in the downstream market of quartz products. Therefore, the quality level of quartz components plays an important role in the stability of the production line of the semiconductor industry and the guarantee of product qualification rate. Quartz rings are mainly used in the etching process of semiconductor wafers and other products to achieve the bearing and airtight protection of the cavity to prevent external pollution. Therefore, whether the surface cleanliness of quartz ring products meets the standards will have a direct impact on the yield rate of semiconductor wafers. The manufacturing process of quartz rings involves processes such as dewaxing, machining, and polishing. During the processing, pollutants such as organic matter, particulate matter, and metal ions will remain on the surface and surrounding areas of the quartz rings, which cannot meet the requirements of semiconductor-grade quartz products. Therefore, it is necessary to use a cleaning agent to remove pollutants from the surface of the quartz rings. However, the commonly used glass cleaning agents on the market currently have problems such as insufficient cleaning power, excessive alkali capacity, low reuse rate, and unfriendly to the environment, and cannot meet the requirements of efficient cleaning of semiconductor-grade quartz rings.

[0003] Patent CN 112481042 A discloses a semiconductor chip adhesive wax cleaning agent and its preparation and use methods. The invention uses hydrocarbon solvents, alcohol ether solvents, cleaning synergists and odor regulators to prepare a solvent-based cleaning agent, which solves the problem of incomplete cleaning of adhesive wax on special structures of semiconductor chips to a certain extent. However, this method contains a large number of organic components, has great safety hazards, and is not environmentally friendly. Patent CN 118853313 A discloses a semiconductor chip deep cleaning agent, preparation method and application. The invention uses highly wettable esters as the main solvent, uses substances with low surface tension, has good penetration, and is used as a carrier to bring the substance that plays a degumming role into the gap, thereby effectively cleaning deep etching and complex structure chips. However, the auxiliary agents used in this method are flammable and explosive, have toxic effects on the human body, have high production costs, and are difficult to use in practice. Patent CN 116496851 A discloses a semiconductor chip cleaning agent and its preparation method. The invention uses sulfonic acid-type fluorinated surfactants, nonionic surfactants, ethanol, diethylene glycol monobutyl ether and complexing agents to prepare a water-based cleaning agent, which can effectively remove tin paste, solder paste, flux residues, etc. on semiconductor chips, and improves the cleaning efficiency of water-based cleaning agents to a certain extent. However, the preparation process of this method is complicated and the amount of surfactant used is large, which lacks economy. Patent CN 118853309 A discloses a highly adsorbable semiconductor chip cleaning agent and a preparation method. The invention uses short-chain hydrogen-containing linear siloxane and polyethylene glycol allyl methyl ether to synthesize an organosilicon surfactant, and prepares a water-based cleaning agent with high safety and environmental friendliness by compounding with anionic surfactants, ionic corrosion inhibitors, etc. However, the alkali capacity in the cleaning agent of this method is high, which will corrode the surface of the quartz ring, form defects, reduce product precision, and is not suitable for the cleaning requirements of semiconductor-grade quartz products.

[0004] Therefore, in the current semiconductor-grade quartz ring cleaning field, there is an urgent need for a new type of cleaning agent that is green, efficient, safe, stable, harmless to quartz rings, and easy to prepare. Summary of the invention

[0005] The purpose of the present invention is to provide a semiconductor-grade quartz ring cleaning agent and a preparation method thereof to solve the shortcomings and deficiencies of the prior art, aiming at the problems of incomplete cleaning of semiconductor-grade quartz rings, excessive alkali capacity, complex process and environmental unfriendliness.

[0006] To achieve the above object, the present invention adopts the following technical solution: A semiconductor-grade quartz ring cleaning agent and a preparation method thereof, comprising the following components by weight percentage: 0.2-1% anionic surfactant, 0.1-0.5% nonionic surfactant, 0.5-4% chelating agent, 1-5% organic solvent, 1-5% cleaning synergist, 0.1-1% pH regulator, and the balance being deionized water.

[0007] Furthermore, the anionic surfactant is one or more of sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium lauryl alcohol polyoxyethylene ether sulfate, and sodium secondary alkyl sulfonate.

[0008] Furthermore, the nonionic surfactant is one or more of fatty alcohol polyoxyethylene ether, fatty acid methyl ester ethoxylate, and alkylphenol polyoxyethylene ether.

[0009] Furthermore, the chelating agent is one or more of disodium edetate, sodium citrate and sodium gluconate.

[0010] Furthermore, the organic solvent is one or more of isopropanol, ethylene glycol butyl ether, and propylene glycol methyl ether.

[0011] Furthermore, the cleaning synergist is triethanolamine.

[0012] Furthermore, the pH regulator is one of solid sodium hydroxide, sodium carbonate and citric acid.

[0013] Furthermore, the pH range of the semiconductor-grade quartz ring cleaning agent is 10-12.

[0014] A semiconductor-grade quartz ring cleaning agent and a preparation method thereof, comprising the following steps: S1. Weigh each raw material component according to weight percentage; S2, mixing anionic surfactant, nonionic surfactant and deionized water, stirring at a speed of 200 to 800 r / min for 8 to 12 min to obtain a mixed solution A; S3, adding the chelating agent to the mixed solution A, stirring at a rotation speed of 500 to 800 r / min for 10 to 15 minutes to obtain a mixed solution B; S4, adding the organic solvent and the cleaning synergist to the mixed solution B, stirring for 3 to 5 minutes at a rotation speed of 300 to 500 r / min to obtain a mixed solution C; S5. Add the pH adjuster into the mixed solution C, stir for 8 to 15 minutes at a rotation speed of 300 to 800 r / min, and adjust the pH to 10 to 12 to obtain the quartz ring cleaning agent.

[0015] The present invention utilizes the property of surfactants that can significantly reduce the surface tension of solutions. First, a mixed solution A is prepared using surfactants and deionized water to increase the stability of the cleaning agent and the dissolution rate of subsequent components. Since the time required for the dissolution of organic solvents and cleaning enhancers is relatively short and the organic solvent has a certain volatility, they are added after the chelating agent, and the pH adjuster is added last.

[0016] Compared with the prior art, the present invention has the following beneficial effects: The semiconductor-grade quartz ring cleaning agent provided by the present invention can significantly improve the cleaning efficiency and reduce the amount of cleaning agent used through the synergistic effect of anionic and nonionic surfactants on molecular structure, charge properties and interface behavior. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 The following are scanning electron microscope photos of the machined surface and wax-bonded surface of the quartz ring before cleaning, where a) is the machined surface and b) is the wax-bonded surface. Figure 2 The present invention provides scanning electron microscope photos of the processed surface and the wax-adhered surface of a quartz ring after cleaning with the cleaning agent provided by the present invention, wherein: a) is the processed surface, and b) is the wax-adhered surface. DETAILED DESCRIPTION

[0018] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments, the purpose of which is to help those skilled in the art understand the content of the present invention in more detail, thereby making a clearer and more definite definition of the protection scope of the present invention, rather than limiting the present invention. All other embodiments obtained by ordinary technicians in this field without making creative work belong to the protection scope of the present invention.

[0019] Example 1 A semiconductor-grade quartz ring cleaning agent, the components and their corresponding weight percentages are shown in Table 1: Table 1 The composition of the quartz ring cleaning agent in Example 1 The semiconductor-grade quartz ring cleaning agent of Example 1 of the present invention is prepared by the following steps: S1. Weigh each raw material component according to weight percentage; S2, mixing sodium dodecylbenzene sulfonate, fatty alcohol polyoxyethylene ether and deionized water, and stirring at a speed of 300 r / min for 8 min to obtain a mixed solution A; S3, adding disodium ethylenediaminetetraacetate to the mixed solution A, stirring at a speed of 600 r / min for 10 min to obtain a mixed solution B; S4, adding isopropanol and triethanolamine to the mixed solution B, stirring at a speed of 300 r / min for 3 min to obtain a mixed solution C; S5. Add sodium carbonate into the mixed solution C, stir for 13 min at a speed of 500 r / min, and adjust the pH to 10.8 to obtain a quartz ring cleaning agent.

[0020] Example 2 A semiconductor-grade quartz ring cleaning agent, the components and their corresponding weight percentages are shown in Table 2: Table 2 The composition of the quartz ring cleaning agent in Example 2 The semiconductor-grade quartz ring cleaning agent of Example 2 of the present invention is prepared by the following steps: S1. Weigh each raw material component according to weight percentage; S2, mixing sodium lauryl sulfate, fatty alcohol polyoxyethylene ether and deionized water, stirring at a speed of 300 r / min for 8 min to obtain a mixed solution A; S3, adding sodium citrate to the mixed solution A, stirring at a speed of 500 r / min for 12 min to obtain a mixed solution B; S4, adding ethylene glycol butyl ether and triethanolamine to the mixed solution B, stirring at a speed of 400 r / min for 4 minutes to obtain a mixed solution C; S5. Add sodium hydroxide to the mixed solution C, stir for 10 min at a speed of 600 r / min, and adjust the pH to 11.9 to obtain a quartz ring cleaning agent.

[0021] Example 3 A semiconductor-grade quartz ring cleaning agent, the components and their corresponding weight percentages are shown in Table 3: Table 3 The composition of the quartz ring cleaning agent in Example 3 The semiconductor-grade quartz ring cleaning agent of Example 3 of the present invention is prepared by the following steps: S1. Weigh each raw material component according to weight percentage; S2, mixing sodium lauryl polyoxyethylene ether sulfate, fatty acid methyl ester ethoxylate and deionized water, and stirring at a rotation speed of 300 r / min for 9 min to obtain a mixed solution A; S3, adding sodium gluconate to the mixed solution A, stirring at a speed of 600 r / min for 12 min to obtain a mixed solution B; S4, adding propylene glycol methyl ether and triethanolamine to the mixed solution B, stirring at a speed of 400 r / min for 3 min to obtain a mixed solution C; S5. Add sodium carbonate into the mixed solution C, stir at a speed of 800 r / min for 8 min, and adjust the pH to 10.68 to obtain a quartz ring cleaning agent.

[0022] Example 4 A semiconductor-grade quartz ring cleaning agent, the components and their corresponding weight percentages are shown in Table 4: Table 4 The composition of the quartz ring cleaning agent in Example 4 The semiconductor-grade quartz ring cleaning agent of Example 4 of the present invention is prepared by the following steps: S1. Weigh each raw material component according to weight percentage; S2, mixing sodium dodecylbenzene sulfonate, sodium secondary alkyl sulfonate, alkylphenol polyoxyethylene ether and deionized water, and stirring at a speed of 500 r / min for 8 min to obtain a mixed solution A; S3, adding disodium ethylenediaminetetraacetate and sodium citrate to the mixed solution A, stirring at a speed of 800 r / min for 10 min to obtain a mixed solution B; S4, adding isopropanol and triethanolamine to the mixed solution B, stirring at a speed of 300 to 500 r / min for 3 to 5 min to obtain a mixed solution C; S5. Add sodium carbonate to the mixed solution C, stir for 15 min at a speed of 300 r / min, and adjust the pH to 10.6 to obtain a quartz ring cleaning agent.

[0023] Example 5 A semiconductor-grade quartz ring cleaning agent, the components and their corresponding weight percentages are shown in Table 5: Table 5 The composition of the quartz ring cleaning agent in Example 5 The semiconductor-grade quartz ring cleaning agent of Example 5 of the present invention is prepared by the following steps: S1. Weigh each raw material component according to weight percentage; S2, mixing sodium dodecylbenzene sulfonate, sodium lauryl alcohol polyoxyethylene ether sulfate, fatty alcohol polyoxyethylene ether, fatty acid methyl ester ethoxylate and deionized water, and stirring at a speed of 600 r / min for 9 min to obtain a mixed solution A; S3, adding disodium ethylenediaminetetraacetate to the mixed solution A, stirring at a speed of 600 r / min for 15 min to obtain a mixed solution B; S4, adding isopropanol, propylene glycol methyl ether and triethanolamine to the mixed solution B, stirring at a speed of 500 r / min for 4 min to obtain a mixed solution C; S5. Add sodium carbonate into the mixed solution C, stir for 10 min at a speed of 500 r / min, and adjust the pH to 10.89 to obtain a quartz ring cleaning agent.

[0024] Example 6 A semiconductor-grade quartz ring cleaning agent, the components and their corresponding weight percentages are shown in Table 6: Table 6 Quartz ring cleaning agent formula composition in Example 6 The semiconductor-grade quartz ring cleaning agent of Example 6 of the present invention is prepared by the following steps: S1. Weigh each raw material component according to weight percentage; S2, mixing sodium lauryl polyoxyethylene ether sulfate, sodium secondary alkyl sulfonate, fatty acid methyl ester ethoxylate and deionized water, and stirring at a rotation speed of 600 r / min for 10 min to obtain a mixed solution A; S3, adding sodium citrate and sodium gluconate to the mixed solution A, stirring at a speed of 800 r / min for 14 min to obtain a mixed solution B; S4, adding isopropanol and triethanolamine to the mixed solution B, stirring at a speed of 300 r / min for 4 min to obtain a mixed solution C; S5. Add citric acid to the mixed solution C, stir at a speed of 600 r / min for 8 min, and adjust the pH to 10.07 to obtain a quartz ring cleaning agent.

[0025] Example 7 A semiconductor-grade quartz ring cleaning agent, the components and their corresponding weight percentages are shown in Table 7: Table 7 The composition of the quartz ring cleaning agent in Example 7 The semiconductor-grade quartz ring cleaning agent of Example 7 of the present invention is prepared by the following steps: S1. Weigh each raw material component according to weight percentage; S2, mixing sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium lauryl alcohol polyoxyethylene ether sulfate, fatty alcohol polyoxyethylene ether, fatty acid methyl ester ethoxylate, alkylphenol polyoxyethylene ether and deionized water, and stirring at a speed of 500 r / min for 12 min to obtain a mixed solution A; S3, adding disodium ethylenediaminetetraacetate and sodium gluconate to the mixed solution A, stirring at a speed of 800 r / min for 15 min to obtain a mixed solution B; S4, adding ethylene glycol butyl ether, propylene glycol methyl ether and triethanolamine to the mixed solution B, stirring at a speed of 500 r / min for 5 min to obtain a mixed solution C; S5. Add sodium carbonate into the mixed solution C, stir at a speed of 800 r / min for 8 min, and adjust the pH to 10.64 to obtain a quartz ring cleaning agent.

[0026] Example 8 A semiconductor-grade quartz ring cleaning agent, the components and their corresponding weight percentages are shown in Table 8: Table 8 The composition of the quartz ring cleaning agent in Example 8 The semiconductor-grade quartz ring cleaning agent of Example 8 of the present invention is prepared by the following steps: S1. Weigh each raw material component according to weight percentage; S2, mixing sodium dodecyl sulfate, sodium lauryl alcohol polyoxyethylene ether sulfate, sodium secondary alkyl sulfonate, fatty alcohol polyoxyethylene ether and deionized water, and stirring at a speed of 500 r / min for 10 min to obtain a mixed solution A; S3, adding sodium gluconate to the mixed solution A, stirring at a rotation speed of 700 r / min for 12 min to obtain a mixed solution B; S4, adding isopropanol and triethanolamine to the mixed solution B, stirring at a speed of 300 r / min for 3 min to obtain a mixed solution C; S5. Add sodium hydroxide to the mixed solution C, stir at a speed of 300 r / min for 9 min, and adjust the pH to 11.16 to obtain a quartz ring cleaning agent.

[0027] Performance testing The performance of the semiconductor-grade quartz ring cleaning agent prepared in Examples 1 to 8 of the present invention was tested. The contaminated quartz ring was placed in a container, and the cleaning liquid was poured in to cover the quartz ring. After ultrasonic treatment at 70°C for 20 min, the quartz ring was taken out and rinsed with deionized water. The cleaning effect was observed, and the cleaning rate and the surface condition of the quartz ring were measured. The results are shown in Table 9.

[0028] Table 9 Cleaning rate and quartz ring surface condition Figure 1 The following are scanning electron microscope photos of the machined surface and wax-bonded surface of the quartz ring before cleaning, where a) is the machined surface and b) is the wax-bonded surface. Figure 2 The following are scanning electron microscope photos of the machined surface and the wax-adhered surface of the quartz ring after cleaning with the cleaning agent prepared in Example 1, a) is the machined surface, and b) is the wax-adhered surface. Figure 1 It can be seen that a large amount of particles and organic contaminants remain on the uncleaned quartz ring surface, and the wax-bonded surface is completely covered with bonding wax. Figure 2 It can be seen that the cleaning agent prepared in Example 1 can effectively remove residual pollutants on the surface of the quartz ring.

[0029] The anionic surfactant in the present invention has the advantages of strong decontamination ability and low cost, can significantly reduce the surface tension of the aqueous solution, form a micelle structure in water, and strip pollutants from the surface of the quartz ring through emulsification and dispersion. It can also ionize anions, increase the electrostatic repulsion between the particle pollutants and the surface of the quartz ring, and prevent redeposition while desorbing the particles. Nonionic surfactants have good emulsification and dispersion properties, good stability and biocompatibility, and are not easily affected by factors such as water hardness, pH value and electrolyte concentration. The use of anionic surfactants and nonionic surfactants in combination can further improve the emulsification and dispersion ability and the ability to reduce the surface tension of the solution, enhance the dissolution and stripping effect of micelles on pollutants, and improve the performance of the cleaning agent.

[0030] For metal ion pollutants, the present invention uses disodium ethylenediaminetetraacetic acid, sodium citrate and sodium gluconate as chelating agents, and utilizes the carboxyl and hydroxyl groups contained in their molecular structures to form stable chelates with metal ions, thereby separating the metal ion pollutants cleaned from the surface of the quartz ring, preventing the reaction of metal ions with other substances, and eliminating the influence of metal ions on anionic surfactants. Finally, an organic solvent is added to increase the dissolving ability of the cleaning agent for organic matter; a cleaning synergist is added to increase the emulsification and penetration ability of the cleaning agent; and a pH regulator is added to maintain the cleaning agent in the pH range with the best decontamination ability.

[0031] The semiconductor-grade quartz ring cleaning agent prepared by the present invention can efficiently remove pollutants such as residual organic matter, particulate matter and metal ions on the surface of the quartz ring, will not corrode the surface of the device, and has a good cleaning effect. After cleaning, the organic pollutants will be clustered on the surface of the cleaning liquid, which is convenient for recycling and multiple utilization of the cleaning liquid, thereby reducing pollution to the environment. The cleaning agent has the advantages of high cleaning efficiency, simple preparation method, easy availability of raw materials, environmental friendliness, etc., and has good application prospects.

[0032] In summary, the cleaning agent prepared by the present invention can efficiently remove pollutants such as residual organic matter, particulate matter and metal ions on the surface of the quartz ring, will not corrode the surface of the device, and the organic pollutants will be aggregated on the surface of the cleaning liquid after cleaning, which is convenient for recycling and multiple utilization of the cleaning liquid, reducing pollution to the environment. Compared with the existing semiconductor-grade cleaning agent, the present invention has the advantages of high cleaning efficiency, simple preparation method, easy to obtain raw materials, and environmental friendliness.

[0033] The above description is only a preferred embodiment of the present invention. It should be pointed out that after reading this specification, those skilled in the art may make several improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be regarded as the protection scope of the present invention.

Claims

1. A semiconductor-grade quartz ring cleaning agent, characterized in that: The composition comprises the following components by weight percentage: 0.2-1% anionic surfactant, 0.1-0.5% nonionic surfactant, 0.5-4% chelating agent, 1-5% organic solvent, 1-5% cleaning enhancer, 0.1-1% pH adjuster, and the balance is deionized water.

2. A semiconductor-grade quartz ring cleaning agent according to claim 1, characterized in that: The anionic surfactant is one or more of sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium lauryl alcohol polyoxyethylene ether sulfate, and sodium secondary alkyl sulfonate.

3. A semiconductor-grade quartz ring cleaning agent according to claim 1, characterized in that: The nonionic surfactant is one or more of fatty alcohol polyoxyethylene ether, fatty acid methyl ester ethoxylate, and alkylphenol polyoxyethylene ether.

4. A semiconductor-grade quartz ring cleaning agent according to claim 1, characterized in that: The chelating agent is one or more of disodium edetate, sodium citrate and sodium gluconate.

5. The semiconductor-grade quartz ring cleaning agent according to claim 1, characterized in that: The organic solvent is one or more of isopropyl alcohol, ethylene glycol butyl ether and propylene glycol methyl ether.

6. The semiconductor-grade quartz ring cleaning agent according to claim 1, characterized in that: The synergist is triethanolamine.

7. The semiconductor-grade quartz ring cleaning agent according to claim 1, characterized in that: The pH regulator is one of solid sodium hydroxide, sodium carbonate and citric acid.

8. The semiconductor-grade quartz ring cleaning agent according to claim 1, characterized in that: The pH range of the semiconductor-grade quartz ring cleaning agent is 10-12.

9. A method for preparing a semiconductor-grade quartz ring cleaning agent according to any one of claims 1 to 8, characterized in that: The following steps are involved: S1. Weigh each raw material component according to weight percentage; S2, mixing anionic surfactant, nonionic surfactant and deionized water, stirring at a speed of 200 to 800 r / min for 8 to 12 min to obtain a mixed solution A; S3, adding the chelating agent to the mixed solution A, stirring at a speed of 500-800 r / min for 10-15 min to obtain a mixed solution B; S4, adding the organic solvent and the cleaning synergist to the mixed solution B, stirring at a speed of 300 to 500 r / min for 3 to 5 min to obtain a mixed solution C; S5. Add the pH adjuster into the mixed solution C, stir for 8 to 15 minutes at a rotation speed of 300 to 800 r / min, and adjust the pH to 10 to 12 to obtain the quartz ring cleaning agent.

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