A mask cleaning solution composition and a method for preparing the same

Abstract

The present application relates to the technical field of cleaning solution, in particular to a mask cleaning solution composition and a preparation method thereof.The mask cleaning solution composition is characterized by being composed of the following raw materials in mass percentage: 7-13wt% of inorganic alkali, 1-4wt% of organic alkali, 2-5wt% of oxidizing agent, 0.2-0.8wt% of hydroxyethyl sulfonic acid, 3-7wt% of surfactant, 1-4wt% of corrosion inhibitor, 3-8wt% of cleaning aid, and the rest being water; the cleaning aid is modified magnetic porous carbon material.The present application uses the modified magnetic porous carbon material as the raw material of the mask cleaning solution composition, which not only reduces the amount of chelating agent used, but also achieves the cleaning effect of energy consumption without the need for adsorbent, more efficiently removes photoresist residues, metal ions and other pollutants, and can be reused, improving the cleaning efficiency and saving the cost.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of cleaning solutions, specifically to a mask cleaning solution composition and a preparation method thereof. BACKGROUND

[0002] In semiconductor manufacturing, masks (also known as photomasks or lithographic masks) are a critical component used to transfer circuit patterns onto silicon wafers. Even minor contamination or defects on the mask can cause short circuits or open circuits in the circuit, affecting the performance and reliability of the entire chip. Therefore, mask cleaning is a crucial step in semiconductor manufacturing.

[0003] Mask cleaning solution compositions are mainly used to remove organic and inorganic contaminants on the mask, including photoresist residues, metal ions, dust particles, etc. These contaminants may come from photoresist, developer, etchant or dust in the environment. Traditional cleaning methods may include the use of organic solvents, acidic or basic solutions, but these methods often have problems such as low efficiency, environmental pollution and operational safety.

[0004] The preparation method of mask cleaning solution composition is also constantly innovating to meet the requirements of high efficiency, environmental protection, safety, etc. of mask cleaning solution composition. Researchers are committed to developing new chemical formulations by precisely controlling the proportion and concentration of chemical components to optimize the performance of the cleaning solution. In addition, the preparation method of the cleaning solution also needs to consider its repeatability and the ability of large-scale production to meet the needs of industrial production.

[0005] Chinese invention patent CN 118639306 A discloses an electrolytic cleaning solution for OLED precision metal mask plate, which uses raw materials and their proportions: inorganic alkali 5%-10%, chelating agent 3%-10%, surfactant 3%-10%, corrosion inhibitor 0.1%-1%, organic auxiliary agent 8%-15%, and the rest is deionized water. Although the electrolytic cleaning solution prepared by this invention has good cleaning effect, is easy to clean and does not leave corrosion. However, the cleaning solution of this invention cannot be reused, resulting in a large amount of waste of cleaning solution and increased cost. SUMMARY

[0006] In view of the above-mentioned deficiencies in the prior art, the present application provides a mask cleaning solution composition and a preparation method thereof.

[0007] To solve the above technical problems, the technical solution adopted by the present application is:

[0008] A mask cleaning solution composition, which is composed of the following raw materials in mass percentage: 7-13wt% inorganic base, 1-4wt% organic base, 2-5wt% oxidizing agent, 0.2-0.8wt% isethionic acid, 3-7wt% surfactant, 1-4wt% corrosion inhibitor, 3-8wt% cleaning aid, and the rest is water; the cleaning aid is modified magnetic porous carbon material.

[0009] The inorganic base is one or more than two of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.

[0010] Preferably, the inorganic base is a mixture of sodium hydroxide and sodium carbonate in a mass ratio of (3.5-5):1.

[0011] The organic base is at least one of tetramethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetraethylammonium hydroxide, and benzyltrimethylammonium hydroxide.

[0012] The oxidizing agent is at least one of hydrogen peroxide, urea peroxide, peroxyacetic acid, permanganate, and ammonium periodate; preferably, the oxidizing agent is a mixture of hydrogen peroxide with a concentration of 30wt% and ammonium periodate in a mass ratio of (2-4):1.

[0013] The surfactant is one or more than two of ethylenediaminetetraacetic acid, dimethyl octyne glycol, oleoyl diethanolamine, and coconut oil acid diethanolamide polyoxyethylene ether.

[0014] The corrosion inhibitor is one or more than two of 2-mercaptobenzothiazole, 2-aminobenzimidazole, 3,5-dimethylpyrazole, and 3-amino-1,2,4-triazole.

[0015] The application adopts porous carbon material as adsorbent, magnetic ferroferric oxide as adsorbed metal impurities, both of which have certain adsorption capacity from different dimensions, and adopts hyperbranched siloxane as chelating agent to be used together, to realize multifunctional cleaning aid. The porous structure on the porous carbon material provides storage space for the adsorbent, ferroferric oxide, improves the adsorption capacity of the material, and the nano ferroferric oxide magnetic material enters the pore channel of the porous carbon material through van der waals force, is distributed on the surface and inner wall of the porous structure, increases the roughness of the material and improves the hydrophobicity of the material. The chelating agent of hyperbranched siloxane is used as a modifier for hydrophobic modification of the magnetic material, realizes the hydrophobic performance, and in the reaction process, the ethyl group of the chelating agent of hyperbranched siloxane is replaced by ferroferric oxide magnetic beads, so that the chelating agent of hyperbranched siloxane and ferroferric oxide magnetic beads are combined together through chemical reaction. As known from the above, the ferroferric oxide magnetic beads are not only adsorbed on the surface of the porous carbon material, but also adsorbed in the internal pore channel, so that the chelating agent of hyperbranched siloxane exists on the surface and in the pore channel of the porous carbon material, and a multifunctional cleaning aid can be formed to improve the cleaning efficiency.

[0016] The preparation method of the modified magnetic porous carbon material is as follows:

[0017] S1: Fe2(SO4)3·9H2O, sodium acetate and ethylene glycol are mixed and stirred, and a nano ferroferric oxide is obtained by hydrothermal reaction. Then, the porous carbon material and anhydrous ethanol are added and ultrasonicated to obtain a magnetic porous carbon material.

[0018] S2: N-[β-(N,N-diacetate) aminoethyl]-γ-(N-acetate) aminopropyl trimethoxysilane, p-aminophenyl trimethoxysilane, methanol and tetrahydrofuran are mixed uniformly, heated and stirred, and distilled under reduced pressure to obtain a hyperbranched polysiloxane. The obtained hyperbranched polysiloxane is added with an ethanol aqueous solution, stirred uniformly, heated, added with glutaraldehyde and a portion of sodium borohydride, stirred, cooled, added with carbon disulfide, and continuously stirred to obtain a chelating agent.

[0019] S3: The above magnetic porous carbon material, the above chelating agent and an ethanol aqueous solution are mixed, stirred and soaked in hot water, filtered, washed, dried, and a modified magnetic porous carbon material is obtained.

[0020] Specifically, the reaction mechanism is as follows: S1 mixes ferric sulfate, sodium acetate and ethylene glycol as reaction raw materials, ethylene glycol as solvent and reducing agent participates in the reaction, and hydrothermal reaction occurs at 180-200℃, ferric sulfate decomposes to generate magnetite nanoparticles at high temperature; mixed with porous carbon material, after adding anhydrous ethanol and ultrasonic treatment, the magnetite nanoparticles are dispersed and the interaction with the porous carbon material is enhanced, and finally the magnetic porous carbon material is obtained; S2 uses N-[β-(N,N-diacetylaminoethyl)-γ-(N-acetylamino) propyl trimethoxysilane and p-aminophenyl trimethoxysilane as reaction raw materials, and heats in a mixed solvent of methanol and tetrahydrofuran to form a hyperbranched polysiloxane structure; glutaraldehyde as a crosslinking agent reacts with the amino group on the polysiloxane, sodium borohydride as a reducing agent reacts with the hyperbranched polysiloxane, carbon disulfide further modifies the chelating agent to enhance the activity of its functional groups to form the chelating agent; S3 mixes the magnetic porous carbon material with the chelating agent, soaks in an ethanol aqueous solution, and makes the functional groups of the chelating agent form stable chelation with the metal ions on the surface of the magnetic porous carbon material, the ethyl group of the hyperbranched siloxane chelating agent is replaced by magnetite beads, and finally the modified magnetic porous carbon material product is obtained.

[0021] Preferably, the preparation method of the modified magnetic porous carbon material is as follows:

[0022] S1 mixes 6-10 parts by weight of Fe2(SO4)3·9H2O, 18-25 parts by weight of sodium acetate and 160-300 parts by weight of ethylene glycol, stirs at 400-1000 rpm at room temperature for 20-50 min, hydrothermal reaction at 180-200℃ for 6-10 h, cools, centrifuges, washes and dries to obtain nano-magnetite; then adds 6-10 parts by weight of porous carbon material and 300-700 parts by weight of anhydrous ethanol, ultrasonic treatment for 50-90 min, filters, washes and dries to obtain magnetic porous carbon material;

[0023] S2mix 1-3 parts by weight of N-[beta-(N,N-diacetate) aminoethyl]-gamma-(N-acetate) aminopropyl trimethoxysilane, 0.5-2 parts by weight of p-aminophenyl trimethoxysilane, 70-130 parts by weight of methanol and 30-50 parts by weight of tetrahydrofuran uniformly, stir at 300-500 rpm, 50-70 DEG C for 15-30 min, adjust the pH value to 4.5-5.5, continue to stir for 2-5 h, adjust the pH value to 6.5-7.5, distill under reduced pressure to obtain a hyperbranched polysiloxane; add 50-120 parts by weight of 50-70 wt% ethanol aqueous solution to the obtained hyperbranched polysiloxane and stir uniformly, heat to 50-70 DEG C, add 0.1-0.5 parts by weight of glutaraldehyde and 0.2-0.6 parts by weight of sodium borohydride, stir at 400-800 rpm for 2-5 h, cool to room temperature, add 0.5-2 parts by weight of carbon disulfide, continue to stir for 20-50 min, distill under reduced pressure to obtain a chelating agent;

[0024] S3mix 4-8 parts by weight of the above magnetic porous carbon material, 0.5-2 parts by weight of the above chelating agent and 50-140 parts by weight of 60-85 wt% ethanol aqueous solution, soak at 50-70 DEG C, 300-500 rpm for 4-10 h, filter, wash and dry to obtain a modified magnetic porous carbon material.

[0025] The modified magnetic porous carbon material is used as a chelating agent and an adsorbent at the same time, can be well compatible and dispersed with the mask cleaning solution composition, has high dispersibility and adsorbability in the system, can quickly penetrate into the microcracks on the surface of the mask plate when applied in the mask cleaning solution composition, form a splitting effect, uniformly form a grinding surface on the surface of the mask plate, and has high specific surface area and porous structure, can effectively adsorb organic pollutants and impurities in the mask cleaning solution, such as photoresist residues, metal ions and other pollutants, and the high adsorption capacity can improve the cleaning effect and ensure the cleanliness of the mask. The surface of the modified magnetic porous carbon material is functionalized, the selective adsorption capacity of the modified magnetic porous carbon material to specific pollutants can be enhanced, and the selective removal capacity helps to improve the targeting of the cleaning solution and reduce the influence on other harmless ingredients; since the modified magnetic porous carbon material can quickly adsorb and remove pollutants, the time and steps of the cleaning process can be significantly shortened, the overall production efficiency is improved, and there is no residue in the subsequent cleaning process.

[0026] The modified magnetic porous carbon material is used as a raw material of the mask cleaning solution composition, the use amount of the chelating agent is reduced, the adsorbent is not needed, the energy consumption of the cleaning effect can be achieved, photoresist residues, metal ions and other pollutants can be removed more efficiently, and the porous structure can be reused, thereby improving the cleaning efficiency.

[0027] The preparation method of the mask cleaning solution composition comprises the following steps: weighing raw materials of each substance, mixing and stirring water and inorganic alkali uniformly at room temperature, adding organic alkali, oxidizing agent, hydroxyethyl sulfonic acid, surfactant, corrosion inhibitor and cleaning aid in sequence, and stirring for 20-50 min at 100-300 rpm to obtain the mask cleaning solution composition.

[0028] The present application provides a mask cleaning solution composition and a preparation method thereof. The present application uses the modified magnetic porous carbon material as the raw material of the mask cleaning solution composition, which not only reduces the amount of chelating agent used, but also achieves the cleaning effect of energy consumption without adsorbent, more efficiently removes photoresist residues, metal ions and other pollutants, and can be reused, improves the cleaning efficiency and saves the cost. DETAILED DESCRIPTION

[0029] The above summary of the application will be further described in detail in combination with the specific embodiments, but this should not be understood as limiting the scope of the above subject matter of the application to only the following examples.

[0030] Introduction of some raw materials in the present application:

[0031] Coconut oil acid diethanolamide polyoxyethylene ether is purchased from Haian Petroleum Chemical Plant in Jiangsu Province, model POEA-15.

[0032] Example 1

[0033] A mask cleaning solution composition is composed of the following mass percentage raw materials: 10wt% inorganic alkali, 2wt% organic alkali, 4wt% oxidizing agent, 0.5wt% hydroxyethyl sulfonic acid, 6wt% surfactant, 2wt% corrosion inhibitor, 5wt% cleaning aid, and the balance is water.

[0034] The inorganic alkali is a mixture of sodium hydroxide and sodium carbonate in a mass ratio of 8:2.

[0035] The organic alkali is tetramethylammonium hydroxide.

[0036] The oxidizing agent is a mixture of hydrogen peroxide with a concentration of 30wt% and ammonium periodate in a mass ratio of 3:1.

[0037] The surfactant is coconut oil acid diethanolamide polyoxyethylene ether.

[0038] The corrosion inhibitor is 2-mercaptobenzothiazole.

[0039] The cleaning aid is a modified magnetic porous carbon material, and the preparation method of the modified magnetic porous carbon material is as follows:

[0040] S1: 8 parts by weight of Fe2(SO4)3·9H2O, 20 parts by weight of sodium acetate, and 200 parts by weight of ethylene glycol are mixed, stirred at 800 rpm for 25 min at room temperature, and subjected to hydrothermal reaction at 190℃ for 8 h, and then cooled, centrifuged, washed, and dried to obtain nano-magnetic iron oxide; 8 parts by weight of a porous carbon material and 400 parts by weight of anhydrous ethanol are added, ultrasonically treated for 60 min, filtered, washed, and dried to obtain a magnetic porous carbon material;

[0041] S2: 2 parts by weight of N-[β-(N,N-diacetylaminoethyl]-γ-(N-acetylamino) propyl trimethoxysilane, 1 part by weight of p-aminophenyl trimethoxysilane, 100 parts by weight of methanol, and 40 parts by weight of tetrahydrofuran are uniformly mixed, stirred at 400 rpm for 20 min at 60℃, the pH value is adjusted to 5, and the stirring is continued for 3 h, the pH value is adjusted to 7, and then distilled under reduced pressure to obtain a hyperbranched polysiloxane; 80 parts by weight of 60wt% ethanol aqueous solution is added to the obtained hyperbranched polysiloxane and uniformly stirred, heated to 60℃, 0.3 parts by weight of glutaraldehyde and 0.4 parts by weight of sodium borohydride are added, and stirred at 600 rpm for 3 h, and then cooled to room temperature, 1 part by weight of carbon disulfide is added, and the stirring is continued for 30 min, and then distilled under reduced pressure to obtain a chelating agent;

[0042] S3: 6 parts by weight of the above magnetic porous carbon material, 1 part by weight of the above chelating agent, and 80 parts by weight of 75wt% ethanol aqueous solution are mixed, soaked at 60℃ for 6 h at 400 rpm, filtered, washed, and dried to obtain a modified magnetic porous carbon material.

[0043] The preparation method of the mask cleaning solution composition is as follows: the raw materials are weighed by mass, and the water and inorganic base are first mixed and stirred uniformly at room temperature, and then the organic base, oxidizing agent, isethionic acid, surfactant, corrosion inhibitor, and cleaning aid are sequentially added, and stirred at 200 rpm for 30 min to obtain the mask cleaning solution composition.

[0044] Example 2

[0045] A mask cleaning solution composition is composed of the following raw materials by mass percentage: 7wt% inorganic base, 1wt% organic base, 2wt% oxidizing agent, 0.2wt% isethionic acid, 3wt% surfactant, 1wt% corrosion inhibitor, 3wt% cleaning aid, and the balance is water.

[0046] The inorganic base is a mixture of sodium hydroxide and sodium carbonate in a mass ratio of 3.5:1.

[0047] The organic base is tetramethylammonium hydroxide.

[0048] The oxidizing agent is a mixture of hydrogen peroxide with a concentration of 30wt% and ammonium periodate in a mass ratio of 2:1.

[0049] The surfactant is coconut oil acid diethanolamide polyoxyethylene ether.

[0050] The corrosion inhibitor is 2-mercaptobenzothiazole.

[0051] The cleaning aid is a modified magnetic porous carbon material, and the preparation method of the modified magnetic porous carbon material is as follows:

[0052] S1: 6 parts by weight of Fe2(SO4)3·9H2O, 18 parts by weight of sodium acetate and 160 parts by weight of ethylene glycol are mixed, stirred at 400 rpm at room temperature for 20 min, hydrothermally reacted at 180℃ for 6 h, cooled, centrifuged, washed and dried to obtain nano-magnetic iron oxide; then 6 parts by weight of porous carbon material and 300 parts by weight of anhydrous ethanol are added, ultrasonically treated for 50 min, filtered, washed and dried to obtain the magnetic porous carbon material;

[0053] S2: 1 part by weight of N-[β-(N,N-diacetylaminoethyl)-γ-(N-acetylamino) propyl trimethoxysilane, 0.5 parts by weight of p-aminophenyl trimethoxysilane, 70 parts by weight of methanol and 30 parts by weight of tetrahydrofuran are uniformly mixed, stirred at 300 rpm and 50℃ for 15 min, the pH value is adjusted to 4.5, and the stirring reaction is continued for 2 h, the pH value is adjusted to 6.5, and vacuum distillation is performed to obtain hyperbranched polysiloxane; 50 parts by weight of 50wt% ethanol aqueous solution is added to the obtained hyperbranched polysiloxane and uniformly stirred, heated to 50℃, 0.1 parts by weight of glutaraldehyde and 0.2 parts by weight of sodium borohydride are added, stirred at 400 rpm for 2 h, cooled to room temperature, 0.5 parts by weight of carbon disulfide is added, and stirring is continued for 20 min, and vacuum distillation is performed to obtain a chelating agent;

[0054] S3: 4 parts by weight of the above-mentioned magnetic porous carbon material, 0.5 parts by weight of the above-mentioned chelating agent and 50 parts by weight of 60wt% ethanol aqueous solution are mixed, soaked at 50℃ and 300 rpm for 4 h, filtered, washed and dried to obtain a modified magnetic porous carbon material.

[0055] The preparation method of the mask cleaning solution composition is as follows: the raw materials of each substance are weighed by mass, water and inorganic base are mixed and stirred uniformly at room temperature, the organic base, oxidizing agent, isethionic acid, surfactant, corrosion inhibitor and cleaning aid are added in sequence, and stirring is carried out at 100 rpm for 20 min to obtain the mask cleaning solution composition.

[0056] Embodiment 3

[0057] A mask cleaning solution composition, which is composed of the following raw materials in mass percentage: 10wt% inorganic base, 2wt% organic base, 4wt% oxidizing agent, 0.5wt% isethionic acid, 6wt% surfactant, 2wt% corrosion inhibitor, 5wt% cleaning aid, and the rest is water.

[0058] The inorganic base is a mixture of sodium hydroxide and sodium carbonate in a mass ratio of 8:2.

[0059] The organic base is tetramethylammonium hydroxide.

[0060] The oxidizing agent is a mixture of hydrogen peroxide with a concentration of 30wt% and ammonium periodate in a mass ratio of 3:1.

[0061] The surfactant is coconut oil acid diethanolamide polyoxyethylene ether.

[0062] The corrosion inhibitor is 2-mercaptobenzothiazole.

[0063] The cleaning aid is a modified magnetic porous carbon material, and the preparation method of the modified magnetic porous carbon material is as follows:

[0064] S1: 10 parts by weight of Fe2(SO4)3·9H2O, 25 parts by weight of sodium acetate, and 300 parts by weight of ethylene glycol are mixed, stirred at 1000 rpm at room temperature for 50 min, and subjected to hydrothermal reaction at 200℃ for 10 h, cooled, centrifuged, washed, and dried to obtain nano-magnetic iron oxide; then 10 parts by weight of porous carbon material and 700 parts by weight of anhydrous ethanol are added, ultrasonically treated for 90 min, filtered, washed, and dried to obtain the magnetic porous carbon material;

[0065] S2: 3 parts by weight of N-[β-(N,N-diacetate)aminoethyl]-γ-(N-acetate)aminopropyl trimethoxysilane, 2 parts by weight of p-aminophenyl trimethoxysilane, 130 parts by weight of methanol, and 50 parts by weight of tetrahydrofuran are uniformly mixed, stirred at 500 rpm and 70℃ for 30 min, the pH value is adjusted to 5.5, and the stirring reaction is continued for 5 h, the pH value is adjusted to 7.5, and vacuum distillation is performed to obtain hyperbranched polysiloxane; 120 parts by weight of 70wt% ethanol aqueous solution is added to the obtained hyperbranched polysiloxane and uniformly stirred, heated to 70℃, 0.5 parts by weight of glutaraldehyde and 0.6 parts by weight of sodium borohydride are added, stirred at 800 rpm for 5 h, cooled to room temperature, 2 parts by weight of carbon disulfide is added, and the stirring is continued for 50 min, and vacuum distillation is performed to obtain the chelating agent;

[0066] S3 mixed 8 parts by weight of the above magnetic porous carbon material, 2 parts by weight of the above chelating agent, and 140 parts by weight of an 85 wt% ethanol aqueous solution, soaked at 70°C for 10h under 500rpm, filtered, washed, and dried to obtain a modified magnetic porous carbon material.

[0067] The preparation method of the mask cleaning solution composition is as follows: the raw materials are weighed by mass, and water and inorganic base are mixed and stirred uniformly at room temperature, and then organic base, oxidizing agent, isethionic acid, surfactant, corrosion inhibitor, and cleaning aid are added in sequence, and stirred at 300rpm for 50min to obtain the mask cleaning solution composition.

[0068] Comparative Example 1

[0069] A mask cleaning solution composition is composed of the following raw materials by mass percentage: 10wt% inorganic base, 2wt% organic base, 4wt% oxidizing agent, 0.5wt% isethionic acid, 6wt% surfactant, 2wt% corrosion inhibitor, and the balance is water.

[0070] The inorganic base is a mixture of sodium hydroxide and sodium carbonate in a mass ratio of 8:2.

[0071] The organic base is tetramethylammonium hydroxide.

[0072] The oxidizing agent is a mixture of hydrogen peroxide with a concentration of 30wt% and ammonium periodate in a mass ratio of 3:1.

[0073] The surfactant is coconut oil acid diethanolamide polyoxyethylene ether.

[0074] The corrosion inhibitor is 2-mercaptobenzothiazole.

[0075] The preparation method of the mask cleaning solution composition is as follows: the raw materials are weighed by mass, and water and inorganic base are mixed and stirred uniformly at room temperature, and then organic base, oxidizing agent, isethionic acid, surfactant, and corrosion inhibitor are added in sequence, and stirred at 200rpm for 30min to obtain the mask cleaning solution composition.

[0076] Comparative Example 2

[0077] A mask cleaning solution composition is composed of the following raw materials by mass percentage: 10wt% inorganic base, 2wt% organic base, 4wt% oxidizing agent, 0.5wt% isethionic acid, 6wt% surfactant, 2wt% corrosion inhibitor, 5wt% cleaning aid, and the balance is water.

[0078] The inorganic base is a mixture of sodium hydroxide and sodium carbonate in a mass ratio of 8:2.

[0079] The organic base is tetramethylammonium hydroxide.

[0080] The oxidizing agent is a mixture of hydrogen peroxide with a concentration of 30wt% and ammonium periodate in a mass ratio of 3:1.

[0081] The surfactant is coconut oil acid diethanolamide polyoxyethylene ether.

[0082] The corrosion inhibitor is 2-mercaptobenzothiazole.

[0083] The cleaning aid is a magnetic porous carbon material, and the preparation method of the magnetic porous carbon material is as follows:

[0084] 8 parts by weight of Fe2(SO4)3·9H2O, 20 parts by weight of sodium acetate, and 200 parts by weight of ethylene glycol are mixed, stirred at 800 rpm at room temperature for 25 min, and subjected to hydrothermal reaction at 190℃ for 8 h, cooled, centrifuged, washed, and dried to obtain nano-magnetic iron oxide; then 8 parts by weight of a porous carbon material and 400 parts by weight of anhydrous ethanol are added, ultrasonically treated for 60 min, filtered, washed, and dried to obtain the magnetic porous carbon material.

[0085] The preparation method of the mask cleaning solution composition is as follows: the raw materials are weighed by mass, and the water and inorganic base are mixed and stirred uniformly at room temperature, and then the organic base, oxidizing agent, isethionic acid, surfactant, corrosion inhibitor, and cleaning aid are added in sequence, and stirred at 200 rpm for 30 min to obtain the mask cleaning solution composition.

[0086] Comparative Example 3

[0087] A mask cleaning solution composition is prepared from the following raw materials by mass percentage: 10wt% inorganic base, 2wt% organic base, 4wt% oxidizing agent, 0.5wt% isethionic acid, 6wt% surfactant, 2wt% corrosion inhibitor, 5wt% cleaning aid, and the balance being water.

[0088] The inorganic base is a mixture of sodium hydroxide and sodium carbonate in a mass ratio of 8:2.

[0089] The organic base is tetramethylammonium hydroxide.

[0090] The oxidizing agent is a mixture of hydrogen peroxide with a concentration of 30wt% and ammonium periodate in a mass ratio of 3:1.

[0091] The surfactant is coconut oil acid diethanolamide polyoxyethylene ether.

[0092] The corrosion inhibitor is 2-mercaptobenzothiazole.

[0093] The cleaning aid is a chelating agent, and the preparation method of the chelating agent is as follows:

[0094] 2 parts by weight of N-[β-(N,N-diacetylaminoethyl]-γ-(N-acetylamino)propyl trimethoxysilane, 1 part by weight of p-aminophenyl trimethoxysilane, 100 parts by weight of methanol and 40 parts by weight of tetrahydrofuran are mixed uniformly, stirred at 400 rpm and 60°C for 20 min, the pH value is adjusted to 5, the reaction is continued to stir for 3 h, the pH value is adjusted to 7, and then distilled under reduced pressure to obtain a hyperbranched polysiloxane; 80 parts by weight of 60 wt% ethanol aqueous solution is added to the obtained hyperbranched polysiloxane and stirred uniformly, heated to 60°C, 0.3 parts by weight of glutaraldehyde and 0.4 parts by weight of sodium borohydride are added, stirred at 600 rpm for 3 h, cooled to room temperature, 1 part by weight of carbon disulfide is added, and then stirred for 30 min, and then distilled under reduced pressure to obtain a chelating agent.

[0095] The preparation method of the mask cleaning solution composition is as follows: the raw materials are weighed by mass, water and inorganic base are mixed and stirred uniformly at room temperature, the organic base, oxidizing agent, isethionic acid, surfactant, corrosion inhibitor and cleaning aid are sequentially added, and stirred at 200 rpm for 30 min to obtain the mask cleaning solution composition.

[0096] Comparative Example 4

[0097] A mask cleaning solution composition is composed of the following raw materials by mass percentage: 10 wt% inorganic base, 2 wt% organic base, 4 wt% oxidizing agent, 0.5 wt% isethionic acid, 6 wt% surfactant, 2 wt% corrosion inhibitor, 5 wt% cleaning aid, and the balance is water.

[0098] The inorganic base is a mixture of sodium hydroxide and sodium carbonate in a mass ratio of 8:2.

[0099] The organic base is tetramethylammonium hydroxide.

[0100] The oxidizing agent is a mixture of hydrogen peroxide with a concentration of 30 wt% and ammonium periodate in a mass ratio of 3:1.

[0101] The surfactant is coconut oil acid diethanolamide polyoxyethylene ether.

[0102] The corrosion inhibitor is 2-mercaptobenzothiazole.

[0103] The cleaning aid is a modified magnetic porous carbon material, and the preparation method of the modified magnetic porous carbon material is as follows:

[0104] S1 mixed 8 parts by weight of Fe2(SO4)3·9H2O, 20 parts by weight of sodium acetate and 200 parts by weight of ethylene glycol, stirred at 800 rpm for 25 min at room temperature, hydrothermally reacted at 190℃ for 8 h, cooled, centrifuged, washed, and dried to obtain nano-magnetic iron oxide; then added 8 parts by weight of porous carbon material and 400 parts by weight of anhydrous ethanol, ultrasonically treated for 60 min, filtered, washed, and dried to obtain magnetic porous carbon material;

[0105] S2 mixed 6 parts by weight of the above magnetic porous carbon material, 1 part by weight of N-[β-(N,N-diacetylaminoethyl)-γ-(N-acetylamino)propyl]trimethoxysilane and 80 parts by weight of 75wt% aqueous ethanol solution, soaked at 60℃ for 6 h under stirring at 400 rpm, filtered, washed, and dried to obtain modified magnetic porous carbon material.

[0106] The preparation method of the mask cleaning solution composition is as follows: the raw materials are weighed by mass, and the water and inorganic alkali are first mixed and stirred uniformly at room temperature, and then the organic alkali, oxidizing agent, isethionic acid, surfactant, corrosion inhibitor and cleaning aid are added in sequence, and stirred at 200 rpm for 30 min to obtain the mask cleaning solution composition.

[0107] Test Example 1

[0108] A semiconductor wafer (containing a pattern) containing a negative acrylate photoresist (about 60 microns thick and subjected to exposure and etching) was immersed in the mask cleaning solution compositions prepared in Examples 1-3 and Comparative Examples 1-4, and oscillated at 55℃ for 20 min using a constant temperature oscillator, then washed with deionized water and dried with high-purity nitrogen, and the cleaning effect of the photoresist and the cleaning and corrosion of the wafer pattern by the cleaning agent composition were observed, and the mask cleaning solution composition after adsorption was placed for one month and then cleaned again, and the results are shown in Table 1.

[0109] Table 1 Cleaning effect test of mask cleaning solution composition

[0110]

[0111] Test Example 2

[0112] Etching rate test method: the mask cleaning solution composition was heated in a water bath, and when the cleaning solution reached 40℃, a 2*2 cm titanium nitride sheet was put into the cleaning solution and the timing started, and when the titanium nitride etching was completely finished, the actual titanium nitride etching rate was calculated by the known film thickness and the etching time required, and the corrosion rate=(thickness before cleaning-thickness after cleaning) / cleaning time, and the results are shown in Table 2.

[0113] Table 2 Etching effect test of mask cleaning solution composition

[0114]

[0115] From the above results, the mask cleaning solution composition prepared by the application has good cleaning effect on photoresist and titanium nitride. As can be seen from comparative example 1 and comparative examples 1-3, the application uses porous carbon material as adsorbent, and magnetic magnetite as adsorbed metal impurities, both of which have certain adsorption capacity from different dimensions, and uses hyperbranched siloxane as chelating agent together, realizing multifunctional cleaning aid. The porous structure on the porous carbon material provides storage space for the adsorbent, i.e. magnetite, improves the adsorption capacity of the material, and the nano-magnetite magnetic material enters the pore channel of the porous carbon material through van der waals force, which is distributed on the surface of the material and the inner wall of the porous structure, not only increasing the roughness of the material but also improving the hydrophobicity of the material. The chelating agent of hyperbranched siloxane is used as a modifier to modify the magnetic material, realize the hydrophobic performance, and the ethyl group of the chelating agent of hyperbranched siloxane is replaced by the magnetite magnetic bead in the reaction process, so the chelating agent of hyperbranched siloxane and the magnetite magnetic bead are combined together through chemical reaction. As can be seen from the above, the magnetite magnetic bead is not only adsorbed on the surface of the porous carbon material, but also adsorbed in the internal pore channel, so the chelating agent of hyperbranched siloxane exists in the surface and pore channel of the porous carbon material, and a multifunctional cleaning aid can be formed to improve the cleaning efficiency.

[0116] The modified magnetic porous carbon material used as chelating agent and adsorbent can be well compatible and dispersed with the mask cleaning solution composition, has high dispersibility and adsorbability in the system, can quickly penetrate into the microcracks on the surface of the mask plate to form a splitting effect, and form a grinding surface on the surface of the mask plate. The modified magnetic porous carbon material has high specific surface area and porous structure, can effectively adsorb organic pollutants and impurities in the mask cleaning solution, such as photoresist residues, metal ions and other pollutants, and this high adsorption capacity can improve the cleaning effect and ensure the cleanliness of the mask. By functionalizing the surface of the modified magnetic porous carbon material, the selective adsorption capacity of the material to specific pollutants can be enhanced, and this selective removal capacity can help to improve the specificity of the cleaning solution and reduce the impact on other harmless ingredients. Since the modified magnetic porous carbon material can quickly adsorb and remove pollutants, the time and steps of the cleaning process can be significantly shortened, the overall production efficiency can be improved, and there is no residual in the subsequent cleaning process.

Claims

1. A mask cleaning solution composition, characterized in that, The raw materials are composed of the following components by weight percentage: 7-13 wt% inorganic alkali, 1-4 wt% organic alkali, 2-5 wt% oxidant, 0.2-0.8 wt% hydroxyethyl sulfonic acid, 3-7 wt% surfactant, 1-4 wt% corrosion inhibitor, 3-8 wt% cleaning aid, and the balance being water; the cleaning aid is a modified magnetic porous carbon material; the preparation method of the modified magnetic porous carbon material is as follows: S1 mixes and stirs Fe2(SO4)3·9H2O, sodium acetate and ethylene glycol, and performs a hydrothermal reaction to obtain nano-iron oxide; then, porous carbon material and anhydrous ethanol are added and ultrasonicated to obtain magnetic porous carbon material. S2 mixes N-[β-(N,N-diacetyl)aminoethyl]-γ-(N-acetyl)aminopropyltrimethoxysilane, p-aminophenyltrimethoxysilane, methanol, and tetrahydrofuran until homogeneous, heats and stirs, and distills under reduced pressure to obtain hyperbranched polysiloxane; adds an aqueous ethanol solution to the obtained hyperbranched polysiloxane and stirs until homogeneous, heats up, adds glutaraldehyde and sodium borohydride and stirs, cools down, adds carbon disulfide and continues stirring to obtain a chelating agent; S3 mixes the above-mentioned magnetic porous carbon material, the above-mentioned chelating agent and ethanol aqueous solution, stirs and soaks in hot water, filters, washes and dries to obtain modified magnetic porous carbon material.

2. The mask cleaning solution composition as described in claim 1, characterized in that, The inorganic base is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.

3. The mask cleaning solution composition as described in claim 1, characterized in that, The organic base is at least one of tetramethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetraethylammonium hydroxide, and benzyltrimethylammonium hydroxide.

4. The mask cleaning solution composition as described in claim 1, characterized in that, The oxidant is at least one of hydrogen peroxide, urea peroxide, peracetic acid, permanganate, and ammonium periodate.

5. The mask cleaning solution composition as described in claim 1, characterized in that, The surfactant is one or more of ethylenediaminetetraacetic acid, dimethyloctynediol, oleoyldiethanolamine, and coconut oil diethanolamide polyoxyethylene ether.

6. The mask cleaning solution composition as described in claim 1, characterized in that, The corrosion inhibitor is one or more of 2-mercaptobenzothiazole, 2-aminobenzimidazole, 3,5-dimethylpyrazole, and 3-amino-1,2,4-triazole.

7. The mask cleaning solution composition as described in claim 1, characterized in that, The preparation method of the modified magnetic porous carbon material is as follows: S1 mixes 6-10 parts by weight of Fe2(SO4)3·9H2O, 18-25 parts by weight of sodium acetate, and 160-300 parts by weight of ethylene glycol, stirs at 400-1000 rpm for 20-50 min at room temperature, and hydrothermally reacts at 180-200℃ for 6-10 h. After cooling, centrifugation, washing, and drying, nano-Fe3O4 is obtained. Then, 6-10 parts by weight of porous carbon material and 300-700 parts by weight of anhydrous ethanol are added, ultrasonicated for 50-90 min, filtered, washed, and dried to obtain magnetic porous carbon material. S2: Mix 1-3 parts by weight of N-[β-(N,N-diacetyl)aminoethyl]-γ-(N-acetyl)aminopropyltrimethoxysilane, 0.5-2 parts by weight of p-aminophenyltrimethoxysilane, 70-130 parts by weight of methanol, and 30-50 parts by weight of tetrahydrofuran until homogeneous. Stir at 300-500 rpm and 50-70°C for 15-30 min, adjust the pH to 4.5-5.5, and continue stirring for 2-5 h, adjusting the pH to 6.5-7.

5. Vacuum distillation to obtain hyperbranched polysiloxane; add 50-120 parts by weight of 50-70 wt% ethanol aqueous solution to the obtained hyperbranched polysiloxane and stir evenly, heat to 50-70℃, add 0.1-0.5 parts by weight of glutaraldehyde and 0.2-0.6 parts by weight of sodium borohydride, stir at 400-800 rpm for 2-5 h, cool to room temperature, add 0.5-2 parts by weight of carbon disulfide, continue stirring for 20-50 min, vacuum distillation to obtain chelating agent; S3 mixes 4-8 parts by weight of the above magnetic porous carbon material, 0.5-2 parts by weight of the above chelating agent and 50-140 parts by weight of 60-85wt% ethanol aqueous solution, soaks in the solution at 50-70℃ and 300-500rpm for 4-10h, filters, washes and dries to obtain the modified magnetic porous carbon material.

8. The method for preparing the mask cleaning solution composition according to any one of claims 1-7, characterized in that, The process includes the following steps: Weigh each raw material by weight, mix water and inorganic alkali evenly at room temperature, then add organic alkali, oxidant, hydroxyethyl sulfonic acid, surfactant, corrosion inhibitor, and cleaning aid in sequence, and stir at 100-300 rpm for 20-50 minutes to obtain the mask cleaning solution composition.

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