Special auxiliary agent for segmented cleaning of quartz ring as well as preparation method and application of special auxiliary agent

Abstract

The invention discloses a special assistant for segmented cleaning of a quartz ring as well as a preparation method and application of the special assistant, a cleaning process in quartz ring production is divided into three segments, the special cleaning assistant is developed in each segment, and a first cleaning assistant comprises the following components in percentage by weight: 0.2-1% of an anionic surfactant, 0.1-0.5% of a nonionic surfactant and the balance of deionized water; the second cleaning aid comprises 0.2 to 1 percent of anionic surfactant, 0.1 to 0.5 percent of nonionic surfactant, 0.5 to 1.5 percent of chelating agent, 1 to 2 percent of oxidant, 0.3 to 1 percent of pH regulator and the balance of deionized water; and the third cleaning auxiliary agent comprises 0.1-0.3% of an anionic surfactant and the balance of deionized water. According to the prepared cleaning agent, efficient cleaning is achieved through a three-step synergistic process, in the first stage, coarse particles and organic matter are removed preferentially, adhesive wax is recycled, in the second stage, stubborn pollutants are removed through the synergistic effect of compound auxiliaries, and in the third stage, residues are removed through low-concentration cleaning.

Description

Technical Field

[0001] This invention belongs to the field of quartz ring cleaning technology, and in particular relates to a special additive for segmented cleaning of quartz rings, its preparation method and application. Background Technology

[0002] As a key component in semiconductor wafer etching processes, the surface cleanliness of the quartz ring directly determines the stability of the wafer manufacturing process and the product yield. In the high-temperature, high-vacuum etching chamber, the quartz ring must possess excellent physical sealing and chemical stability to support the wafer and isolate it from external contaminants. If contaminants such as organic matter, metal ions, or microparticles remain on its surface, they may be released into the chamber under extreme process conditions, leading to wafer surface defects (such as electrical failures, short circuits, or microstructural anomalies).

[0003] In the precision manufacturing process of quartz rings, key processes such as dewaxing, CNC cutting, and surface polishing can introduce multiple sources of contamination. The dewaxing process easily leaves behind alkane-based waxy organic matter; micron-sized silica particles generated during machining easily adhere to the surface; and the polishing process may introduce metal ions (such as Al). 3+ Ce 4+ These contaminants, or polishing fluid components, significantly degrade the dielectric properties and thermal stability of quartz substrates, making it difficult to meet the surface cleanliness requirements of semiconductor-grade products. Studies have confirmed that when particulate contaminants larger than 5 μm are present on the surface of a quartz ring, the probability of partial discharge during plasma etching increases by more than 30%, leading to micro-arc damage on the wafer surface.

[0004] Currently, cleaning agents used in the semiconductor manufacturing industry can be divided into two systems: solvent-based and water-based. Solvent-based cleaning agents have significant drawbacks. Their volatile organic compounds (VOCs) can easily pose safety risks and environmental pollution. They are not efficient at removing polar contaminants (such as metal ions), and high-viscosity solvents can easily form residual films on surfaces, causing secondary pollution. Wastewater treatment is also costly and complex. Water-based cleaning agents, primarily composed of deionized water, have advantages such as environmental safety, high material compatibility, and low cost. They can effectively remove metal ions and particulate contaminants. However, existing water-based cleaning agents cannot be effectively integrated with cleaning processes. They are not efficient at removing non-polar organic matter and submicron particles, are prone to particle redeposition due to surfactant charge mismatch, and have excessively high alkalinity, which can easily corrode materials.

[0005] Therefore, in the current field of quartz ring cleaning, there is an urgent need for a new type of cleaning agent that is green, efficient, safe, stable, does not damage quartz rings, is simple to prepare, and can promote the cleaning process. Summary of the Invention

[0006] The purpose of this invention is to address the problems of quartz ring cleaning agents failing to effectively integrate with the cleaning process, incomplete cleaning, and excessive alkali capacity by providing a special auxiliary agent for segmented cleaning of quartz rings, its preparation method, and its application, thereby overcoming the shortcomings and deficiencies of existing technologies.

[0007] To achieve the above objectives, the present invention adopts the following technical solution: A special cleaning aid for segmented cleaning of quartz rings, its preparation method, and its application, wherein the aid comprises a first cleaning aid, a second cleaning aid, and a third cleaning aid, in weight percentages. The first cleaning aid consists of: 0.2-1% anionic surfactant, 0.1-0.5% nonionic surfactant, and the remainder is deionized water; The second cleaning aid includes: 0.2-1% anionic surfactant, 0.1-0.5% nonionic surfactant, 0.5-1.5% chelating agent, 1-2% oxidant, 0.3-1% pH adjuster, and the remainder is deionized water; The third cleaning aid includes: 0.1-0.3% anionic surfactant, with the remainder being deionized water; Furthermore, the anionic surfactant is one or more of sodium dodecylbenzene sulfonate, sodium secondary alkyl sulfonate, sodium α-alkenyl sulfonate, and fatty acid methyl ester sulfonate; Furthermore, the nonionic surfactant is one or more of fatty alcohol polyoxyethylene ether, cocamidopropylamine oxide, and fatty acid methyl ester ethoxylate.

[0008] Furthermore, the chelating agent is one or more of disodium ethylenediaminetetraacetate, sodium citrate, and sodium gluconate.

[0009] Furthermore, the oxidant is hydrogen peroxide, and the mass concentration of the hydrogen peroxide is 30%.

[0010] Furthermore, the pH adjuster is one of solid sodium hydroxide or sodium carbonate.

[0011] Furthermore, the pH range of the second cleaning aid is 10 to 12.

[0012] A method for preparing a special auxiliary agent for segmented cleaning of quartz rings, characterized by comprising the following steps: S1. Weigh each raw material component according to its weight percentage; S2. At room temperature, mix the weighed raw materials and the calculated amount of deionized water evenly and stir until the solution is uniform and transparent to obtain the first cleaning aid, the second cleaning aid and the third cleaning aid.

[0013] The application of a special additive for segmented cleaning of quartz rings is characterized by comprising the following steps: S3. Place the quartz ring material to be cleaned into the first cleaning aid and ultrasonically clean it at 70 ℃ for 8 to 12 minutes. After cleaning, remove the quartz ring material from the first cleaning aid and place it into the second cleaning aid. Ultrasonically clean it at 70 ℃ for 10 to 15 minutes. Then remove it and place it into the third cleaning aid. Ultrasonically clean it at room temperature for 3 to 6 minutes. S4. Spray the cleaned quartz ring material with deionized water for 2 to 3 minutes to remove residual cleaning agent on the surface, and then dry it in a nitrogen atmosphere.

[0014] The segmented cleaning agent prepared by this invention adopts a three-step synergistic process to achieve efficient cleaning. The first step prioritizes the removal of coarse particles and organic pollutants and realizes the recycling of adhesive wax. The second step utilizes the synergistic effect of compounded additives to remove stubborn pollutants. The third step uses low-concentration cleaning to eliminate residues, thus achieving an effective combination of cleaning agent and cleaning process.

[0015] Compared with the prior art, the beneficial effects of the present invention are: 1. The quartz ring segmented cleaning additive in this invention achieves effective integration with the cleaning process, and its gradient functional design enables precise adaptation to multi-stage cleaning procedures. The first cleaning additive preferentially removes physically adsorbed organic matter and large particulate pollutants through interfacial activation, inhibiting the emulsification process of the binding wax. This allows the peeled wax to accumulate in a non-emulsified state on the surface of the cleaning liquid, forming a solid-liquid interface phase separation, significantly reducing the difficulty of subsequent wastewater treatment. The second and third cleaning additives respectively target chemically adsorbed pollutants and submicron-sized residues for deep removal. While achieving tiered removal of pollutants, this invention also reduces energy consumption and avoids the load impact on the wastewater treatment system caused by emulsified oil in traditional composite cleaning agents.

[0016] 2. The method in this invention is simple and easy to operate. Its approach of removing and recycling contaminants in stages can be used for cleaning most semiconductor devices and has universal applicability. Attached Figure Description

[0017] Figure 1 Metallographic micrographs of the wax-adhered and polished surfaces of the quartz ring material before cleaning; Figure 2 Metallographic micrographs of the wax-adhered and polished surfaces of the quartz ring material after cleaning with the first cleaning aid prepared in Example 3; Figure 3 Metallographic micrographs of the wax-adhered and polished surfaces of the quartz ring material after cleaning with the second cleaning aid prepared in Example 3; Figure 4Metallurgical microscope images of the wax-adhered surface and the polished surface of the quartz ring material after cleaning with the third cleaning aid prepared in Example 3. Detailed Implementation

[0018] To better illustrate the purpose, technical solution, and advantages of this invention, the following detailed description, in conjunction with specific embodiments, aims to help those skilled in the art to understand the invention more thoroughly and thus provide a clearer and more explicit definition of the scope of protection, rather than limiting the invention. All other embodiments obtained by those skilled in the art without inventive effort are within the scope of protection of this invention.

[0019] Example 1 A special cleaning aid for segmented cleaning of quartz rings, the components and their weight percentages of the first, second, and third cleaning aids are shown in Table 1: Table 1. Composition of the special additive for segmented cleaning of quartz rings in Example 1 The special auxiliary agent for segmented cleaning of quartz rings described in Example 1 of this invention is prepared by the following method: S1. Weigh each raw material component according to its weight percentage; S2. At room temperature, mix the weighed raw materials and the calculated amount of deionized water evenly and stir until the solution is uniform and transparent to obtain the first cleaning aid, the second cleaning aid and the third cleaning aid.

[0020] The application method of the special additive for segmented cleaning of quartz rings described in Example 1 of this invention is as follows: S3. Place the quartz ring material to be cleaned into the first cleaning aid and ultrasonically clean it at 70 ℃ for 10 min. After cleaning, remove the material from the first cleaning aid and place it into the second cleaning aid. Ultrasonically clean it at 70 ℃ for 15 min. Then remove it and place it into the third cleaning aid. Ultrasonically clean it at room temperature for 4 min.

[0021] S4. Spray the cleaned quartz ring material with deionized water for 3 minutes to remove residual cleaning agent on the surface, and then dry it in a nitrogen atmosphere.

[0022] Example 2 A special cleaning aid for segmented cleaning of quartz rings, the components and their weight percentages of the first, second, and third cleaning aids are shown in Table 2: Table 2. Composition of the special additive for segmented cleaning of quartz rings in Example 2 The special auxiliary agent for segmented cleaning of quartz rings described in Example 2 of this invention is prepared by the following method: S1. Weigh the raw material components of the first, second, and third cleaning aids according to their weight percentages; S2. At room temperature, mix the weighed raw materials and deionized water evenly and stir until the solution is uniform and transparent to obtain the first, second and third cleaning aids. The application method of the special auxiliary agent for segmented cleaning of quartz rings described in Embodiment 2 of the present invention is as follows: S3. Place the quartz ring material to be cleaned into the first cleaning aid and ultrasonically clean it at 70 ℃ for 8 min. After cleaning, remove the material from the first cleaning aid and place it into the second cleaning aid. Ultrasonically clean it at 70 ℃ for 12 min. Then remove it and place it into the third cleaning aid. Ultrasonically clean it at room temperature for 5 min.

[0023] S4. Spray the cleaned quartz ring material with deionized water for 3 minutes to remove residual cleaning agent on the surface, and then dry it in a nitrogen atmosphere.

[0024] Example 3 A special cleaning aid for segmented cleaning of quartz rings, the components and their weight percentages of the first, second, and third cleaning aids are shown in Table 3: Table 3. Composition of the special additive for segmented cleaning of quartz rings in Example 3 The special auxiliary agent for segmented cleaning of quartz rings described in Example 3 of this invention is prepared by the following method: S1. Weigh the raw material components of the first, second, and third cleaning aids according to their weight percentages; S2. At room temperature, mix the weighed raw materials and deionized water evenly and stir until the solution is uniform and transparent to obtain the first, second and third cleaning aids. The application method of the special additive for segmented cleaning of quartz rings described in Embodiment 3 of the present invention is as follows: S3. Place the quartz ring material to be cleaned into the first cleaning aid and ultrasonically clean it at 70 ℃ for 9 min. After cleaning, remove the material from the first cleaning aid and place it into the second cleaning aid. Ultrasonically clean it at 70 ℃ for 15 min. Then remove it and place it into the third cleaning aid. Ultrasonically clean it at room temperature for 4 min.

[0025] S4. Spray the cleaned quartz ring material with deionized water for 2 minutes to remove residual cleaning agent on the surface, and then dry it in a nitrogen atmosphere.

[0026] Example 4 A special cleaning aid for segmented cleaning of quartz rings, the components and their weight percentages of the first, second, and third cleaning aids are shown in Table 4: Table 4. Composition of the special additive for segmented cleaning of quartz rings in Example 4 The special auxiliary agent for segmented cleaning of quartz rings described in Example 4 of this invention is prepared by the following method: S1. Weigh the raw material components of the first, second, and third cleaning aids according to their weight percentages; S2. At room temperature, mix the weighed raw materials and deionized water evenly and stir until the solution is uniform and transparent to obtain the first, second and third cleaning aids. The application method of the special auxiliary agent for segmented cleaning of quartz rings described in Example 4 of this invention is as follows: S3. Place the quartz ring material to be cleaned into the first cleaning aid and ultrasonically clean it at 70 ℃ for 10 min. After cleaning, remove the material from the first cleaning aid and place it into the second cleaning aid. Ultrasonically clean it at 70 ℃ for 13 min. Then remove it and place it into the third cleaning aid. Ultrasonically clean it at room temperature for 5 min.

[0027] S4. Spray the cleaned quartz ring material with deionized water for 3 minutes to remove residual cleaning agent on the surface, and then dry it in a nitrogen atmosphere.

[0028] Example 5 A special cleaning aid for segmented cleaning of quartz rings, the components and their weight percentages of the first, second, and third cleaning aids are shown in Table 5: Table 5. Composition of the special additive for segmented cleaning of quartz rings in Example 5 The special auxiliary agent for segmented cleaning of quartz rings described in Example 5 of this invention is prepared by the following method: S1. Weigh the raw material components of the first, second, and third cleaning aids according to their weight percentages; S2. At room temperature, mix the weighed raw materials and deionized water evenly and stir until the solution is uniform and transparent to obtain the first, second and third cleaning aids. The application method of the special additive for segmented cleaning of quartz rings described in Example 5 of this invention is as follows: S3. Place the quartz ring material to be cleaned into the first cleaning aid and ultrasonically clean it at 70 ℃ for 12 min. After cleaning, remove the material from the first cleaning aid and place it into the second cleaning aid. Ultrasonically clean it at 70 ℃ for 10 min. Then remove it and place it into the third cleaning aid. Ultrasonically clean it at room temperature for 4 min.

[0029] S4. Spray the cleaned quartz ring material with deionized water for 2 minutes to remove residual cleaning agent on the surface, and then dry it in a nitrogen atmosphere.

[0030] Example 6 A special cleaning aid for segmented cleaning of quartz rings, the components and their weight percentages of the first, second, and third cleaning aids are shown in Table 6: Table 6. Composition of the special additive for segmented cleaning of quartz rings in Example 6 The special auxiliary agent for segmented cleaning of quartz rings described in Example 6 of this invention is prepared by the following method: S1. Weigh the raw material components of the first, second, and third cleaning aids according to their weight percentages; S2. At room temperature, mix the weighed raw materials and deionized water evenly and stir until the solution is uniform and transparent to obtain the first, second and third cleaning aids. The application method of the special auxiliary agent for segmented cleaning of quartz rings described in Example 6 of this invention is as follows: S3. Place the quartz ring material to be cleaned into the first cleaning aid and ultrasonically clean it at 70 ℃ for 11 min. After cleaning, remove the material from the first cleaning aid and place it into the second cleaning aid. Ultrasonically clean it at 70 ℃ for 13 min. Then remove it and place it into the third cleaning aid. Ultrasonically clean it at room temperature for 5 min.

[0031] S4. Spray the cleaned quartz ring material with deionized water for 3 minutes to remove residual cleaning agent on the surface, and then dry it in a nitrogen atmosphere.

[0032] The final detergency performance of the quartz ring segmented cleaning agents prepared in Examples 1 to 6 of this invention was tested, and the results are shown in Table 7.

[0033] Table 7 Cleaning rate and quartz ring surface condition from Figure 1 It can be seen that the unwashed quartz ring material's wax-adhesive surface was completely covered by adhesive wax, and the polished surface retained a large amount of particles and cutting fluid. From Figure 2 It can be seen that the first cleaning agent can remove most of the adhesive wax and coarse particles from the surface of the quartz ring, leaving only a small amount of contaminants. From Figure 3 , 4 It can be seen that after cleaning with the second and third cleaning agents, no contaminants remained on the surface of the quartz ring, and a quartz ring sample with a high-quality surface was obtained.

[0034] The segmented cleaning agent prepared by this invention adopts a three-step synergistic process to achieve efficient cleaning. The first step prioritizes the removal of coarse particles and organic pollutants and realizes the recycling of adhesive wax. The second step utilizes the synergistic effect of compounded additives to remove stubborn pollutants. The third step uses low-concentration cleaning to eliminate residues, thus achieving an effective combination of cleaning agent and cleaning process.

[0035] The above description is only a preferred embodiment of the present invention. It should be noted that after reading this specification, those skilled in the art can make several improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A special cleaning aid for segmented cleaning of quartz rings, the aid comprising a first cleaning aid, a second cleaning aid, and a third cleaning aid, characterized in that, According to weight percentage, The first cleaning aid consists of: 0.2-1% anionic surfactant, 0.1-0.5% nonionic surfactant, and the remainder is deionized water; The second cleaning aid includes: 0.2-1% anionic surfactant, 0.1-0.5% nonionic surfactant, 0.5-1.5% chelating agent, 1-2% oxidant, 0.3-1% pH adjuster, and the remainder is deionized water; The third cleaning aid includes: 0.1-0.3% anionic surfactant, with the remainder being deionized water; The anionic surfactant is one or more of sodium dodecylbenzene sulfonate, sodium secondary alkyl sulfonate, sodium α-alkenyl sulfonate, and fatty acid methyl ester sulfonate. The nonionic surfactant is one or more of fatty alcohol polyoxyethylene ether, cocamidopropylamine oxide, and fatty acid methyl ester ethoxylate.

2. The special additive for segmented cleaning of quartz rings according to claim 1, characterized in that, The chelating agent is one or more of disodium ethylenediaminetetraacetate, sodium citrate, and sodium gluconate.

3. The special additive for segmented cleaning of quartz rings according to claim 1, characterized in that, The oxidant is hydrogen peroxide, and the mass concentration of the hydrogen peroxide is 30%.

4. The special additive for segmented cleaning of quartz rings according to claim 1, its preparation method and application, characterized in that, The pH adjuster is either solid sodium hydroxide or sodium carbonate.

5. The special additive for segmented cleaning of quartz rings according to claim 1, its preparation method and application, characterized in that, The pH range of the second cleaning aid is 10 to 12.

6. A method for preparing a special auxiliary agent for segmented cleaning of quartz rings according to any one of claims 1 to 5, characterized in that, Includes the following steps: S1. Weigh each raw material component according to its weight percentage; S2. At room temperature, mix the weighed raw materials and the calculated amount of deionized water evenly and stir until the solution is uniform and transparent to obtain the first cleaning aid, the second cleaning aid and the third cleaning aid.

7. The application of the special auxiliary agent for segmented cleaning of quartz rings according to any one of claims 1 to 5, characterized in that, Includes the following steps: S3. Place the quartz ring material to be cleaned into the first cleaning aid and ultrasonically clean it at 70 ℃ for 8 to 12 minutes. After cleaning, remove the quartz ring material from the first cleaning aid and place it into the second cleaning aid. Ultrasonically clean it at 70 ℃ for 10 to 15 minutes. Then remove it and place it into the third cleaning aid. Ultrasonically clean it at room temperature for 3 to 6 minutes. S4. Spray the cleaned quartz ring material with deionized water for 2 to 3 minutes to remove residual cleaning agent on the surface, and then dry it in a nitrogen atmosphere.

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