Semiconductor cleaning solution and manufacturing method thereof

Abstract

The invention relates to a semiconductor cleaning solution and a preparation method thereof. The semiconductor cleaning solution comprises the following components in percentage by mass: 40-60% of isopropanol, 1-2% of citric acid, 0.1-0.5% of a synergistic surfactant, 0.06-0.08% of high-dispersion nano silicon dioxide, 0.5-1% of a chelating agent, 0.3-0.5% of a corrosion inhibitor and the balance of water. The manufacturing method comprises the following steps: mixing isopropanol, citric acid, a synergistic surfactant, high-dispersion nano silicon dioxide, a chelating agent, a corrosion inhibitor and water according to the mass percentage, stirring, and homogenizing to obtain the semiconductor cleaning fluid. The semiconductor cleaning fluid has the effect of improving the cleaning performance of the semiconductor cleaning fluid, micro-size pollutants on the surface of a semiconductor can be effectively removed, the cleaning fluid is easy to clean and remove, and the residue-free effect can be achieved.

Description

Technical Field

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

[0002] The semiconductor cleaning process is an indispensable and important part of semiconductor manufacturing, which is directly related to the yield and performance of the chip. As semiconductor devices develop towards higher integration and smaller size, the requirements for cleaning fluids are getting higher and higher, requiring them to be able to efficiently remove impurities, dust and other pollutants to ensure the stability and reliability of semiconductor devices. Therefore, the development of efficient and low-toxic semiconductor cleaning fluids has become a research hotspot.

[0003] However, existing semiconductor cleaning fluids have poor cleaning ability and residue problems in practical applications. On the one hand, existing cleaning fluids cannot effectively remove some tiny-sized pollutants, such as nano-sized particles, metal atom clusters, etc., because these tiny pollutants have strong binding force with the wafer surface, and the traditional cleaning fluid has limited decontamination ability. On the other hand, there may be residues of cleaning fluid after cleaning, and some cleaning fluid components may be adsorbed on the wafer surface, affecting subsequent process and device performance. These problems seriously affect the performance and reliability of semiconductor devices and reduce the yield of semiconductor manufacturing. In order to improve the quality and performance of semiconductor devices, it is necessary to provide a semiconductor cleaning fluid that can effectively remove tiny pollutants without residue. Summary of the invention

[0004] In order to improve the cleaning performance of a semiconductor cleaning liquid, the present application provides a semiconductor cleaning liquid and a method for manufacturing the same.

[0005] The present application provides a semiconductor cleaning solution and a manufacturing method thereof using the following technical solutions: In the first aspect, the present application provides a semiconductor cleaning solution, which adopts the following technical solution: A semiconductor cleaning solution comprising the following components in percentage by weight: Isopropyl alcohol 40-60% Citric acid 1-2% Synergistic surfactant 0.1-0.5% Highly dispersed nano silicon dioxide 0.06-0.08% Chelating agent 0.5-1% Corrosion inhibitor 0.3-0.5% Make up the balance with water.

[0006] Isopropyl alcohol can effectively dissolve organic pollutants, and citric acid can react with metal oxides to remove metal impurities; synergistic surfactants reduce surface tension, allowing the cleaning solution to spread better on the semiconductor surface, increase the contact area with impurities on the semiconductor surface, better wrap impurities, make them easier to clean and remove, and improve cleaning performance; highly dispersed nano-silica has good dispersion properties, and its surface is rich in active groups such as hydroxyl groups, which can combine with pollutants through chemical adsorption. At the same time, the small particle size of highly dispersed nano-silica enables it to penetrate into tiny pores to adsorb and remove pollutants, thereby effectively improving the cleaning effect; chelating agents can combine with metal ions to prevent them from re-depositing on the semiconductor surface; corrosion inhibitors protect semiconductor materials from corrosion; the components in the cleaning solution work synergistically to effectively improve the cleaning performance, and the above components are easy to remove, which can reduce the residue of cleaning solution on the semiconductor surface.

[0007] Preferably, the raw materials for preparing the synergistic surfactant include epoxy fatty acid methyl ester and sodium lignin sulfonate.

[0008] Epoxy fatty acid methyl ester has good lipophilicity and can interact with organic pollutants and impurities such as tiny metal atom clusters on the semiconductor surface, making them easily detached from the semiconductor surface; sodium lignin sulfonate has good hydrophilicity and can make the cleaning solution spread better on the semiconductor surface, increasing the contact area between the cleaning solution and impurities; the surfactant synthesized by using the two can, on the one hand, enhance the removal ability of tiny pollutants such as nano-particles and metal atom clusters, and remove these impurities from the semiconductor surface through encapsulation, suspension and other effects; on the other hand, it helps to reduce the residual organic matter in the cleaning solution and reduce the potential adverse effects on semiconductor performance after cleaning, providing efficient and reliable protection for semiconductor cleaning.

[0009] Preferably, the synergistic surfactant is prepared by the following steps: Epoxy fatty acid methyl ester, acetonitrile, sulfuric acid and deionized water are mixed and dispersed, and refluxed at a speed of 600 rpm for 2 hours to obtain a preliminary product. The preliminary product is separated and purified to obtain dihydroxy fatty acid methyl ester; dihydroxy fatty acid methyl ester and sodium lignin sulfonate are mixed and dispersed in toluene, sodium methoxide is added, heated and stirred to react, and the solvent is removed by rotary evaporation to obtain a synergistic surfactant.

[0010] The synergistic surfactant prepared according to the above steps has good cleaning effect and low residue.

[0011] Preferably, the raw materials for preparing the synergistic surfactant also include ethylene oxide.

[0012] Ethylene oxide introduces ethoxy groups into the molecules of surfactants, enhancing their hydrophilicity and solubility in water. When the cleaning fluid acts on the semiconductor surface, the surfactant molecules can interact with tiny pollutants through their lipophilic groups to wrap up nano-scale particles and metal atom clusters. At the same time, due to the better water solubility brought by the ethoxy group, the surfactant can more effectively suspend these tiny pollutants in the cleaning fluid and be carried away with the flow of the cleaning fluid, thereby improving the cleaning fluid's ability to remove tiny-sized pollutants.

[0013] Preferably, the mass ratio of the epoxy fatty acid methyl ester, sodium lignin sulfonate and ethylene oxide is 1:1.71:(0.28-0.7).

[0014] The synergistic surfactant prepared according to the above mass ratio has good performance, can effectively improve the cleaning effect of the cleaning solution, and reduce the residue of the cleaning solution.

[0015] Preferably, the raw materials for preparing the highly dispersed nano-silicon dioxide include silica sol and acrylic polymer.

[0016] By preparing highly dispersed nano-silica through silica sol and acrylic polymer, the surface of the nano-silica can be evenly coated with acrylic polymer, reducing the occurrence of agglomeration, improving the dispersibility of the nano-silica, making it evenly distributed in the cleaning solution, and better removing tiny-sized pollutants through physical friction and adsorption; at the same time, acrylic polymers can interact with organic pollutants on the surface of the semiconductor, promote the removal of organic pollutants, and reduce organic residues on the surface of the semiconductor.

[0017] Preferably, the silica sol is modified to obtain modified silica sol, and the raw materials for preparing the modified silica sol include ethyl orthosilicate and γ-aminopropyltriethoxysilane.

[0018] γ-Aminopropyltriethoxysilane introduces amino groups to the surface of nano-silica. Silica with amino groups can effectively capture nano-scale particles through electrostatic attraction and physical adsorption. At the same time, amino groups can form coordination bonds with metal ions, stably bind to metal atom clusters, and prevent them from redepositing on the semiconductor surface, thereby improving cleaning efficiency; amino groups can form amide bonds or other chemical bonds with carboxyl groups, ester groups, etc. in organic molecules, thereby changing the structure and properties of organic pollutants, making them easier to dissolve in the cleaning solution and be removed, reducing the organic residue in the cleaning solution.

[0019] Preferably, the raw materials for preparing the acrylic ester polymer include hydroxyethyl acrylate, isobornyl acrylate and a quaternary ammonium salt modifier.

[0020] The combination of hydroxyethyl acrylate and isobornyl acrylate gives the polymer a good balance of hydrophilicity and hydrophobicity, enabling it to better interact with tiny pollutants on the semiconductor surface and remove them from the semiconductor surface by adsorption, encapsulation, etc.; the introduction of quaternary ammonium salt modifier enhances the cationic properties of the polymer, enabling it to generate stronger electrostatic attraction with negatively charged pollutants, further improving the removal effect of tiny pollutants; at the same time, acrylate polymers can also promote the dissolution and dispersion of organic pollutants during the cleaning process, reduce the residue of organic matter, and reduce the potential adverse effects on semiconductor performance.

[0021] Preferably, the mass ratio of hydroxyethyl acrylate, isobornyl acrylate and quaternary ammonium salt modifier is 1:1:(0.2-0.6).

[0022] The acrylic polymer prepared according to the above mass ratio has the characteristics of good cleaning performance and low residue.

[0023] In a second aspect, the present application provides a method for manufacturing a semiconductor cleaning solution, using the following technical solution: A method for manufacturing a semiconductor cleaning solution comprises the following steps: mixing isopropyl alcohol, citric acid, a synergistic surfactant, highly dispersed nano silicon dioxide, a chelating agent, a corrosion inhibitor and water according to the mass percentage, stirring and then homogenizing to obtain a semiconductor cleaning solution.

[0024] The semiconductor cleaning solution prepared according to the above steps has good cleaning performance, can effectively remove nanoparticles and metal clusters on the surface of the semiconductor, and reduce the residue of the cleaning solution.

[0025] In summary, the present application includes at least one of the following beneficial technical effects: 1. Isopropyl alcohol can effectively dissolve organic pollutants, and citric acid can react with metal oxides to remove metal impurities; synergistic surfactants reduce surface tension, allowing the cleaning solution to spread better on the semiconductor surface, increase the contact area with impurities on the semiconductor surface, better wrap impurities, make them easier to clean and remove, and improve cleaning performance; highly dispersed nano-silica has good dispersibility, and its surface is rich in active groups such as hydroxyl groups, which can combine with pollutants through chemical adsorption. At the same time, the small particle size of highly dispersed nano-silica enables it to penetrate into tiny pores to adsorb and remove pollutants, thereby effectively improving the cleaning effect; chelating agents can combine with metal ions to prevent them from re-depositing on the semiconductor surface; corrosion inhibitors protect semiconductor materials from corrosion; the components in the cleaning solution work synergistically to effectively improve the cleaning performance, and the above components are easy to remove, which can reduce the residue of the cleaning solution on the semiconductor surface.

[0026] 2. Epoxy fatty acid methyl ester has good lipophilicity and can interact with impurities such as organic pollutants and tiny metal atom clusters on the semiconductor surface, making them easy to detach from the semiconductor surface; sodium lignin sulfonate has good hydrophilicity, which can make the cleaning solution spread better on the semiconductor surface and increase the contact area between the cleaning solution and impurities; ethylene oxide introduces ethoxy groups into the surfactant molecules, enhancing its hydrophilicity and solubility in water; when the cleaning solution acts on the semiconductor surface, the surfactant molecules can interact with tiny pollutants through their lipophilic groups and wrap up nano-sized particles and metal atom clusters. At the same time, due to the better water solubility brought by the ethoxy group, the surfactant can more effectively suspend these tiny pollutants in the cleaning solution and be carried away with the flow of the cleaning solution, thereby improving the cleaning solution's ability to remove tiny pollutants.

[0027] 3. By preparing highly dispersed nano-silica through silica sol and acrylic polymer, the surface of nano-silica can be evenly coated with acrylic polymer, reducing the occurrence of agglomeration, improving the dispersibility of nano-silica, making it evenly distributed in the cleaning solution, and better removing tiny-sized pollutants through physical friction and adsorption; at the same time, acrylic polymers can interact with organic pollutants on the surface of semiconductors, promote the removal of organic pollutants, and reduce organic residues on the surface of semiconductors. DETAILED DESCRIPTION

[0028] The present application discloses a semiconductor cleaning solution and a method for manufacturing the same. The raw materials used in the present application can be obtained from commercially available raw materials unless otherwise specified. The present application is further described in detail below in conjunction with the embodiments: Raw material description: The raw materials used in the preparation of this application are all electronically pure, with a purity of more than 99.9%, impurity content such as metal ions below ppm, and impurity content of 0.5μm particles is less than 10 / mL, epoxy fatty acid methyl ester (CAS No.: 6084-76-0), catalyst is titanium catalyst (CAS No.: 36673-16-2), sodium lignin sulfonate (CAS No.: 8061-51-6), sodium methoxide (CAS No.: 124-41-4), ethylene oxide (CAS No.: 124-41-4), S No.: 75-21-8), hydroxyethyl acrylate (CAS No.: 818-61-1), isobornyl acrylate (CAS No.: 5888-33-5), quaternary ammonium salt modifier is polymerizable quaternary ammonium salt R-303, tetraethyl orthosilicate (CAS No.: 78-10-4), γ-aminopropyltriethoxysilane (CAS No.: 919-30-2), azobisisobutyronitrile (CAS No.: 78-67-1), sodium dodecyl sulfonate (CAS No.: 2386-53-0).

[0029] Preparation Example 1 Preparation of synergistic surfactant 1 0.23 kg of epoxy fatty acid methyl ester, 30 g of acetonitrile, 3 g of sulfuric acid and 350 g of deionized water were mixed and dispersed, and the mixture was stirred and refluxed at a speed of 600 rpm for 2 h to obtain a preliminary product. The preliminary product was separated and purified to obtain dihydroxy fatty acid methyl ester; the dihydroxy fatty acid methyl ester prepared above and 0.77 kg of sodium lignin sulfonate were mixed and dispersed in 2 L of toluene, 1 g of sodium methoxide was added, and the mixture was stirred and reacted at a speed of 200 rpm at 80°C for 6 h. The solvent was removed by rotary evaporation to obtain a synergistic surfactant 1.

[0030] Preparation Example 2 Preparation of synergistic surfactant 2 0.33 kg of epoxy fatty acid methyl ester, 45 g of acetonitrile, 5 g of sulfuric acid and 530 g of deionized water were mixed and dispersed, and the mixture was stirred and refluxed at a speed of 600 rpm for 2 h to obtain a preliminary product. The preliminary product was separated and purified to obtain dihydroxy fatty acid methyl ester; the dihydroxy fatty acid methyl ester prepared above and 0.57 kg of sodium lignin sulfonate were mixed and dispersed in 2 L of toluene, 1 g of sodium methoxide was added, and the mixture was stirred and reacted at a speed of 200 rpm at 80°C for 6 h, and the solvent was removed by rotary evaporation to obtain a synergistic surfactant 1.

[0031] The above-prepared synergistic surfactant 1 and 1g of catalyst were mixed, the temperature was raised to 90°C and stirred at a speed of 600rpm, nitrogen was introduced to replace the air three times, the temperature was raised to 175°C, ethylene oxide was introduced to start the reaction, and when the pressure dropped to 0.1MPa, ethylene oxide was continuously introduced so that the total amount of ethylene oxide introduced was 0.1kg, and the reaction was continued to be stirred. When the temperature dropped to 80°C and the pressure reached 0.1MPa, the reaction was stopped and the material was discharged to obtain a synergistic surfactant.

[0032] Preparation Example 3 Preparation Example 3 is based on Preparation Example 2. The only difference between Preparation Example 3 and Preparation Example 2 is that in Preparation Example 3, the amount of epoxy fatty acid methyl ester used is 0.29 kg, the amount of sodium lignin sulfonate used is 0.5 kg, and the amount of ethylene oxide used is 0.21 kg.

[0033] Preparation Example 4 Preparation Example 4 is based on Preparation Example 2. The only difference between Preparation Example 4 and Preparation Example 2 is that in Preparation Example 4, the amount of epoxy fatty acid methyl ester used is 0.31 kg, the amount of sodium lignin sulfonate used is 0.53 kg, and the amount of ethylene oxide used is 0.16 kg.

[0034] Preparation Example 5 Preparation Example 5 is based on Preparation Example 2. The only difference between Preparation Example 5 and Preparation Example 2 is that in Preparation Example 5, the amount of epoxy fatty acid methyl ester used is 0.36 kg, the amount of sodium lignin sulfonate used is 0.61 kg, and the amount of ethylene oxide used is 0.03 kg.

[0035] Preparation Example 6 Preparation Example 6 is based on Preparation Example 2. The only difference between Preparation Example 6 and Preparation Example 2 is that in Preparation Example 6, the amount of epoxy fatty acid methyl ester used is 0.28 kg, the amount of sodium lignin sulfonate used is 0.47 kg, and the amount of ethylene oxide used is 0.25 kg.

[0036] Preparation Example 7 Preparation of Highly Dispersed Nanosilicon Dioxide 90.91 g of hydroxyethyl acrylate, 90.91 g of isobornyl acrylate and 18.18 g of quaternary ammonium salt modifier were mixed and dispersed in 500 mL of a mixed solvent of toluene and ethyl acetate in a volume ratio of 1:1, 0.5 g of azobisisobutyronitrile was added, the temperature was raised to 100° C. and the reaction was carried out for 10 hours, and the solvent was removed by rotary evaporation to obtain an acrylic ester polymer.

[0037] 2.5 kg of tetraethyl orthosilicate was dispersed in 5 L of anhydrous ethanol, and the mixture was stirred and dispersed at a speed of 200 rpm for 30 min to obtain a tetraethyl orthosilicate solution. 0.5 L of deionized water was added to the tetraethyl orthosilicate solution, and the temperature was raised to 60° C., and the pH was adjusted to 4 using concentrated hydrochloric acid. 0.5 kg of γ-aminopropyltriethoxysilane was added to the solution after the pH was adjusted, and the mixture was stirred and reacted at a speed of 200 rpm at 60° C. for 4 h, and the solvent was removed by rotary evaporation to obtain a modified silica sol. The modified silica sol prepared above and the acrylic ester polymer prepared above were mixed and dispersed in 2 L of anhydrous ethanol, 1 g of azobisisobutyronitrile was added, and the mixture was stirred and reacted at a speed of 200 rpm at 60° C. for 6 h, and the solvent was removed by rotary evaporation. The mixture was dried in an oven at 80° C. and then ground to obtain highly dispersed nano-silica.

[0038] Preparation Example 8 Preparation Example 8 is based on Preparation Example 7. The only difference between Preparation Example 8 and Preparation Example 7 is that in Preparation Example 8, the amount of hydroxyethyl acrylate used is 76.92 g, the amount of isobornyl acrylate used is 76.92 g, and the amount of quaternary ammonium salt modifier used is 46.16 g.

[0039] Preparation Example 9 Preparation Example 9 is based on Preparation Example 7. The only difference between Preparation Example 9 and Preparation Example 7 is that in Preparation Example 9, the amount of hydroxyethyl acrylate used is 83.33 g, the amount of isobornyl acrylate used is 83.33 g, and the amount of quaternary ammonium salt modifier used is 33.34 g.

[0040] Preparation Example 10 Preparation Example 10 is based on Preparation Example 7. The only difference between Preparation Example 10 and Preparation Example 7 is that in Preparation Example 10, the amount of hydroxyethyl acrylate used is 95.24 g, the amount of isobornyl acrylate used is 95.24 g, and the amount of quaternary ammonium salt modifier used is 9.52 g.

[0041] Preparation Example 11 Preparation Example 11 is based on Preparation Example 7. The only difference between Preparation Example 11 and Preparation Example 7 is that in Preparation Example 11, the amount of hydroxyethyl acrylate used is 71.43 g, the amount of isobornyl acrylate used is 71.43 g, and the amount of quaternary ammonium salt modifier used is 57.14 g.

[0042] Preparation Example 12 Preparation Example 12 is based on Preparation Example 7. The only difference between Preparation Example 12 and Preparation Example 7 is that in Preparation Example 12, γ-aminopropyltriethoxysilane is not used to modify the silica sol.

[0043] Example 1 Mix 40% of isopropanol, 1% of citric acid, 0.5% of the synergistic surfactant 1 prepared in Preparation Example 1, 0.08% of the highly dispersed nano-silicon dioxide prepared in Preparation Example 7, 1% of the chelating agent and 0.5% of the corrosion inhibitor, make up the balance to 100% with water, stir at a speed of 200 rpm for 1 hour, and perform homogenization treatment for 1 hour to obtain a semiconductor cleaning solution.

[0044] Example 2 Mix 60% of isopropanol, 2% of citric acid, 0.1% of the synergistic surfactant 1 prepared in Preparation Example 1, 0.06% of the highly dispersed nano-silicon dioxide prepared in Preparation Example 8, 0.5% of the chelating agent and 0.3% of the corrosion inhibitor, make up the balance to 100% with water, stir at a speed of 200 rpm for 1 hour, and perform homogenization treatment for 1 hour to obtain a semiconductor cleaning solution.

[0045] Example 3 Mix 50% of isopropanol, 1.5% of citric acid, 0.3% of the synergistic surfactant 1 prepared in Preparation Example 1, 0.07% of the highly dispersed nano-silicon dioxide prepared in Preparation Example 9, 0.75% of the chelating agent and 0.4% of the corrosion inhibitor, make up the balance to 100% with water, stir at a speed of 200 rpm for 1 hour, and perform homogenization treatment for 1 hour to obtain a semiconductor cleaning solution.

[0046] Example 4 Example 4 is based on Example 3. The only difference between Example 4 and Example 3 is that in Example 4, the synergistic surfactant 1 prepared in Preparation Example 1 is replaced by the synergistic surfactant 2 prepared in Preparation Example 2.

[0047] Example 5 Example 5 is based on Example 3. The only difference between Example 5 and Example 3 is that in Example 5, the synergistic surfactant 1 prepared in Preparation Example 1 is replaced by the synergistic surfactant 2 prepared in Preparation Example 3.

[0048] Example 6 Example 6 is based on Example 3. The only difference between Example 6 and Example 3 is that in Example 6, the synergistic surfactant 1 prepared in Preparation Example 1 is replaced by the synergistic surfactant 2 prepared in Preparation Example 4.

[0049] Example 7 Example 7 is based on Example 3. The only difference between Example 7 and Example 3 is that in Example 7, the synergistic surfactant 1 prepared in Preparation Example 1 is replaced by the synergistic surfactant 2 prepared in Preparation Example 5.

[0050] Example 8 Example 8 is based on Example 3. The only difference between Example 8 and Example 3 is that in Example 8, the synergistic surfactant 1 prepared in Preparation Example 1 is replaced by the synergistic surfactant 2 prepared in Preparation Example 6.

[0051] Example 9 Example 9 is based on Example 3. The only difference between Example 9 and Example 3 is that in Example 9, the highly dispersed nano-silicon dioxide prepared in Preparation Example 9 is replaced by the highly dispersed nano-silicon dioxide prepared in Preparation Example 10.

[0052] Example 10 Example 10 is based on Example 3. The only difference between Example 10 and Example 3 is that in Example 10, the highly dispersed nano-silicon dioxide prepared in Preparation Example 9 is replaced by the highly dispersed nano-silicon dioxide prepared in Preparation Example 11.

[0053] Embodiment 11 Example 11 is based on Example 3. The only difference between Example 11 and Example 3 is that in Example 11, the highly dispersed nano-silicon dioxide prepared in Preparation Example 9 is replaced by the highly dispersed nano-silicon dioxide prepared in Preparation Example 12.

[0054] Comparative Example 1 Comparative Example 1 is based on Example 3, and the only difference between Comparative Example 1 and Example 3 is that the highly dispersed nano-silicon dioxide is replaced by nano-silicon dioxide in Comparative Example 1.

[0055] Comparative Example 2 Comparative Example 2 is based on Example 3, and the only difference between Comparative Example 2 and Example 3 is that in Comparative Example 2, the synergistic surfactant is replaced by sodium dodecyl sulfate.

[0056] Performance testing (1) Cleaning performance test: The semiconductor product to be cleaned was immersed in a cleaning solution diluted 10 times and ultrasonically cleaned for 60 minutes. It was then cleaned with ultrapure water and dried with nitrogen. The number of defects on the semiconductor surface before and after cleaning was observed under a long reflection scanning electron microscope. The defect removal rate was calculated and the results are recorded in Table 1.

[0057] (2) Metal cluster cleaning performance test: The semiconductor product to be cleaned was immersed in a 10-fold diluted cleaning solution for ultrasonic cleaning for 60 min, then cleaned with ultrapure water and dried with nitrogen. The metal ion concentration on the surface of the semiconductor product before and after cleaning was detected using inductively coupled plasma mass spectrometry, and the removal rate was calculated. The results are recorded in Table 1. (3) Table 1 Test results of cleaning performance of semiconductor cleaning fluid Test results Defect count before cleaning Defects after cleaning Removal rate (%) Example 1 35164 1878 94.66 Example 2 43260 2111 95.12 Example 3 21897 1044 95.23 Example 4 33147 514 98.45 Example 5 46389 682 98.53 Example 6 36753 481 98.69 Example 7 41164 1671 95.94 Example 8 52178 1998 96.17 Example 9 37841 2392 93.68 Example 10 26993 1779 93.41 Embodiment 11 32014 2481 92.25 Comparative Example 1 47324 5859 87.62 Comparative Example 2 35577 5219 85.33 It can be seen from Table 1 that the removal rates of Examples 1-3 are greater than 96.66%, which shows that the semiconductor cleaning solution prepared in the present application has good cleaning performance.

[0059] It can be seen from Table 1 that the only difference between Example 4-8 and Example 3 is that when preparing the synergistic surfactant in Example 4-8, ethylene oxide is added and ethoxy group is introduced. Compared with Example 3, the cleaning performance of Example 4-8 is improved; the synergistic surfactant prepared according to the mass ratio of Example 4-6 has good emulsification and dispersion properties and cleaning performance, while Examples 7 and 8 destroy the limited range and affect the stability of the surfactant, and the cleaning effect is reduced compared with Example 4-6.

[0060] As can be seen from Table 1, the only difference between Examples 9-11 and Example 3 is that the mass ratio of the highly dispersed silica synthesis components in Examples 9-10 is not within the specified range, and the highly dispersed nano-silica in Example 11 is not subjected to amino-modification treatment. Compared with Example 3, the cleaning performance of Examples 9-11 is reduced; this is because the destruction of the specified ratio will affect the stability of the acrylic polymer, thereby affecting the dispersibility of the highly dispersed silica, thereby reducing the cleaning performance; and the lack of the introduction of amino groups will reduce the adsorption performance of the highly dispersed nano-silica, thereby reducing the cleaning performance.

[0061] As can be seen from Table 1, the only difference between Comparative Examples 1 and 2 and Example 3 is that in Comparative Example 1, the highly dispersed nano-silicon dioxide is replaced by nano-silicon dioxide, and in Comparative Example 2, the synergistic surfactant is replaced by sodium dodecyl sulfate. Compared with Example 3, the cleaning performance of Comparative Examples 1 and 2 is significantly reduced; this is because the nano-silicon dioxide lacks modification treatment, the dispersion performance is reduced, and the lack of synergistic effect of the acrylic polymer causes the adsorption performance to decrease, thereby greatly reducing the cleaning performance; and when the synergistic surfactant is replaced by sodium dodecyl sulfate, the emulsification and dispersion effect achieved by the single sulfonic acid functional group is limited, the solubility of pollutants is reduced, and the cleaning ability is significantly reduced.

[0062] This specific embodiment is only an explanation of the present application, and it is not a limitation of the present application. Through the above description, relevant staff can make various changes and modifications without deviating from the technical idea of ​​the present application. The technical scope of the present application is not limited to the content in the specification, and its technical scope must be determined according to the scope of the claims.

Claims

1. A semiconductor cleaning solution, characterized in that: Includes the following components in percentage by mass: Isopropyl alcohol 40-60% Citric acid 1-2% Synergistic surfactant 0.1-0.5% Highly dispersed nano silicon dioxide 0.06-0.08% Chelating agent 0.5-1% Corrosion inhibitor 0.3-0.5% Make up the balance with water.

2. A semiconductor cleaning solution according to claim 1, characterized in that: The raw materials for preparing the synergistic surfactant include epoxy fatty acid methyl ester and sodium lignin sulfonate.

3. A semiconductor cleaning solution according to claim 2, characterized in that: The synergistic surfactant is prepared by the following steps: Epoxy fatty acid methyl ester, acetonitrile, sulfuric acid and deionized water are mixed and dispersed, and refluxed at a speed of 600 rpm for 2 hours to obtain a preliminary product. The preliminary product is separated and purified to obtain dihydroxy fatty acid methyl ester; dihydroxy fatty acid methyl ester and sodium lignin sulfonate are mixed and dispersed in toluene, sodium methoxide is added, heated and stirred to react, and the solvent is removed by rotary evaporation to obtain a synergistic surfactant.

4. A semiconductor cleaning solution according to claim 3, characterized in that: The raw materials for preparing the synergistic surfactant also include ethylene oxide.

5. A semiconductor cleaning solution according to claim 4, characterized in that: The mass ratio of the epoxy fatty acid methyl ester, sodium lignin sulfonate and ethylene oxide is 1:1.71:(0.28-0.7).

6. A semiconductor cleaning solution according to claim 1, characterized in that: The raw materials for preparing the highly dispersed nano-silicon dioxide include silica sol and acrylic polymer.

7. A semiconductor cleaning solution according to claim 6, characterized in that: The silica sol is subjected to modification treatment to obtain modified silica sol, and the raw materials for preparing the modified silica sol include ethyl orthosilicate and gamma-aminopropyltriethoxysilane.

8. A semiconductor cleaning solution according to claim 7, characterized in that: The raw materials for preparing the acrylic ester polymer include hydroxyethyl acrylate, isobornyl acrylate and a quaternary ammonium salt modifier.

9. A semiconductor cleaning solution according to claim 8, characterized in that: The mass ratio of the hydroxyethyl acrylate, isobornyl acrylate and quaternary ammonium salt modifier is 1:1:(0.2-0.6).

10. A method for manufacturing a semiconductor cleaning solution as claimed in any one of claims 1 to 9, characterized in that: The method comprises the following steps: mixing isopropyl alcohol, citric acid, a synergistic surfactant, highly dispersed nano silicon dioxide, a chelating agent, a corrosion inhibitor and water according to the mass percentage, stirring and then homogenizing to obtain a semiconductor cleaning solution.