Mask cleaning solution composition and preparation method thereof

Abstract

The invention relates to the technical field of cleaning solutions, in particular to a mask cleaning solution composition and a preparation method thereof. The mask cleaning solution composition is characterized by being prepared from the following raw materials in percentage by mass: 7 to 13 weight percent of inorganic alkali, 1 to 4 weight percent of organic alkali, 2 to 5 weight percent of an oxidizing agent, 0.2 to 0.8 weight percent of isethionic acid, 3 to 7 weight percent of a surfactant, 1 to 4 weight percent of a corrosion inhibitor, 3 to 8 weight percent of a cleaning auxiliary agent and the balance of water, the cleaning aid is a modified magnetic porous carbon material. The modified magnetic porous carbon material is adopted as a raw material of the mask cleaning solution composition, the usage amount of a chelating agent is reduced, meanwhile, the cleaning effect of energy consumption can be achieved without an adsorbent, photoresist residues, metal ions and other pollutants are more efficiently removed, secondary utilization can be achieved, the cleaning efficiency is improved, and the cost is reduced. And the cost is saved.

Description

Technical Field

[0001] The present invention relates to the technical field of cleaning fluids, and in particular to a mask cleaning fluid composition and a preparation method thereof. Background Art

[0002] In the semiconductor manufacturing process, the mask (also called a photomask or photolithography mask) is a key component used to transfer circuit patterns to silicon wafers. Minor contamination or defects on the mask may cause short circuits or open circuits in the circuit, thus affecting the performance and reliability of the entire chip. Therefore, mask cleaning is a crucial step in semiconductor manufacturing.

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

[0004] The preparation method of the mask cleaning fluid composition is also constantly innovating to meet the requirements of the mask cleaning fluid composition in terms of efficiency, environmental protection, safety, etc. Researchers are committed to developing new chemical formulas to optimize the performance of the cleaning fluid by precisely controlling the ratio and concentration of chemical components. In addition, the preparation method of the cleaning fluid also needs to consider its repeatability and ability to be mass-produced to meet the needs of industrial production.

[0005] Chinese invention patent CN 118639306 A discloses an electrolytic cleaning solution for OLED precision metal mask plates, the raw materials used and the proportion of each raw material are: inorganic base 5%-10%, chelating agent 3%-10%, surfactant 3%-10%, anti-corrosion agent 0.1%-1%, organic additive 8%-15%, and the balance is deionized water. Although the electrolytic cleaning solution prepared by the invention has a good cleaning effect and is easy to clean without residual corrosion. However, the cleaning solution of the invention cannot be reused, resulting in a large amount of waste of cleaning solution and increased costs. Summary of the invention

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

[0007] In order to solve the above technical problems, the technical solution adopted by the present invention is: A mask cleaning liquid composition is composed of the following raw materials in percentage by weight: 7-13wt% inorganic base, 1-4wt% organic base, 2-5wt% oxidant, 0.2-0.8wt% hydroxyethyl sulfonic acid, 3-7wt% surfactant, 1-4wt% corrosion inhibitor, 3-8wt% cleaning aid, and the balance is water; the cleaning aid is a modified magnetic porous carbon material.

[0008] The inorganic base is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate; Preferably, the inorganic base is a mixture of sodium hydroxide and sodium carbonate in a mass ratio of (3.5-5):1.

[0009] The organic base is at least one of tetramethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetraethylammonium hydroxide and benzyltrimethylammonium hydroxide.

[0010] The oxidant is at least one of hydrogen peroxide, urea peroxide, peracetic acid, permanganate, and ammonium periodate; preferably, the oxidant is a mixture of 30wt% hydrogen peroxide and ammonium periodate in a mass ratio of (2-4):1.

[0011] The surfactant is one or more of ethylenediaminetetraacetic acid, dimethyloctynediol, oleoyldiethanolamine, and coconut oleic acid diethanolamide polyoxyethylene ether.

[0012] The corrosion inhibitor is one or more of 2-mercaptobenzothiazole, 2-aminobenzimidazole, 3,5-dimethylpyrazole and 3-amino-1,2,4-triazole.

[0013] The present invention adopts porous carbon material as adsorbent and magnetic ferrosoferric oxide as adsorbent for 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 a multifunctional cleaning aid. The porous structure on the porous carbon material is an adsorbent, which provides storage space for ferroferric oxide and improves the adsorption capacity of the material. The nano ferroferric oxide magnetic material enters the pores of the porous carbon material through van der Waals force and is distributed on the surface of the material and the inner wall of the porous structure, which not only increases the roughness of the material but also improves the hydrophobicity of the material. A hyperbranched siloxane chelating agent is used as a modifier to hydrophobically modify the magnetic material to achieve hydrophobic properties. During the reaction, the ethyl group of the hyperbranched siloxane chelating agent is replaced by ferroferric oxide magnetic beads, so the hyperbranched siloxane chelating agent and the ferroferric oxide magnetic beads are combined together through a chemical reaction. It can be seen from the above that the ferroferric oxide magnetic beads are not only adsorbed on the surface of the porous carbon material, but also adsorbed inside the multi-hole channels. Therefore, the hyperbranched siloxane chelating agent exists on the surface of the porous carbon material and in the pores, which can form a multifunctional cleaning aid and improve the cleaning efficiency.

[0014] The preparation method of the modified magnetic porous carbon material is as follows: S1: Fe2(SO4)3·9H2O‌, sodium acetate and ethylene glycol are mixed and stirred, and subjected to hydrothermal reaction to obtain nano-iron tetroxide; porous carbon material and anhydrous ethanol are then added and ultrasonicated to obtain magnetic porous carbon material; S2: N-[β-(N,N-diacetoxy)aminoethyl]-γ-(N-acetoxy)aminopropyltrimethoxysilane, p-aminophenyltrimethoxysilane, methanol and tetrahydrofuran are mixed uniformly, heated with stirring, and distilled under reduced pressure to obtain a hyperbranched polysiloxane; ethanol aqueous solution is added to the obtained hyperbranched polysiloxane and stirred uniformly, the temperature is increased, glutaraldehyde and sodium borohydride are added, stirred, the temperature is lowered, carbon disulfide is added, and stirring is continued to obtain a chelating agent; S3: Mix the magnetic porous carbon material, the chelating agent and the ethanol aqueous solution, soak them in hot water with stirring, filter, wash and dry them to obtain a modified magnetic porous carbon material.

[0015] Specifically: The reaction mechanism is as follows: S1 uses ferrous sulfate, sodium acetate and ethylene glycol as reaction raw materials for mixing, ethylene glycol is used as a solvent and a reducing agent to participate in the reaction, a hydrothermal reaction occurs at 180-200°C, and ferrous sulfate is decomposed at high temperature to generate ferroferric oxide nanoparticles; mixed with porous carbon materials, anhydrous ethanol is added and then ultrasonically treated to disperse the ferroferric oxide nanoparticles and enhance their interaction with the porous carbon materials, and finally a magnetic porous carbon material is obtained; S2 uses N-[β-(N,N-diacetoxy)aminoethyl]-γ-(N-acetoxy)aminopropyltrimethoxysilane and p-aminophenyltrimethoxysilane as reaction The raw materials are heated in a mixed solvent of methanol and tetrahydrofuran to form a hyperbranched polysiloxane structure; glutaraldehyde is used as a crosslinking agent to react with the amino group on the polysiloxane, sodium borohydride is used as a reducing agent to react with the hyperbranched polysiloxane, and carbon disulfide is further used to modify the chelating agent to enhance the activity of its functional groups to form a chelating agent; S3 mixes the magnetic porous carbon material with the chelating agent, and soaks them in an ethanol aqueous solution to form a stable chelating effect between the functional groups of the chelating agent and the metal ions on the surface of the magnetic porous carbon material, and the ethyl group of the hyperbranched siloxane chelating agent is replaced by ferroferric oxide magnetic beads to finally obtain the product modified magnetic porous carbon material.

[0016] Preferably, the preparation method of the modified magnetic porous carbon material is as follows: S1: 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 are mixed, stirred at 400-1000 rpm for 20-50 min at room temperature, hydrothermally reacted at 180-200°C for 6-10 h, cooled, centrifuged, washed and dried to obtain nano-iron tetroxide; 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 a magnetic porous carbon material; S2: 1-3 parts by weight of N-[β-(N,N-diacetoxy)aminoethyl]-γ-(N-acetoxy)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 are uniformly mixed, stirred at 300-500 rpm and 50-70° C. for 15-30 min, the pH value is adjusted to 4.5-5.5, the reaction is continued with stirring for 2-5 h, and the pH value is adjusted to 6.5-7. .5, distill under reduced pressure to obtain a hyperbranched polysiloxane; add 50-120 parts by weight of a 50-70wt% ethanol aqueous solution to the obtained hyperbranched polysiloxane and stir evenly, heat to 50-70°C, add 0.1-0.5 parts by weight of glutaraldehyde and 0.2-0.6 parts by weight of sodium borohydride, stir at 400-800rpm for 2-5h, cool to room temperature, add 0.5-2 parts by weight of carbon disulfide, continue stirring for 20-50min, and distill under reduced pressure to obtain a chelating agent; S3: 4-8 parts by weight of the above-mentioned magnetic porous carbon material, 0.5-2 parts by weight of the above-mentioned chelating agent and 50-140 parts by weight of 60-85wt% ethanol aqueous solution are mixed, and the mixture is immersed in water at 50-70°C and 300-500rpm for 4-10h, filtered, washed and dried to obtain a modified magnetic porous carbon material.

[0017] The present invention adopts modified magnetic porous carbon material as chelating agent and adsorbent at the same time, which can be well compatible and dispersed with the mask cleaning liquid composition, has high dispersibility and adsorption in the system, and can be applied to the mask cleaning liquid composition to quickly penetrate into the micro cracks on the surface of the mask plate, forming a splitting effect, and uniformly forming a grinding surface on the surface of the mask plate. The modified magnetic porous carbon material has a high specific surface area and a porous structure, and can effectively adsorb organic pollutants and impurities in the mask cleaning liquid, such as photoresist residues, metal ions and other pollutants. This efficient 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, its selective adsorption capacity for specific pollutants can be enhanced. This selective removal capacity helps to improve the pertinence of the cleaning liquid and reduce the impact on other harmless components; because the modified magnetic porous carbon material can quickly adsorb and remove pollutants, the time and steps of the cleaning process can be significantly shortened, improving the overall production efficiency, and there is no residue in the subsequent cleaning process.

[0018] The present invention adopts the above-mentioned modified magnetic porous carbon material as the raw material of the mask cleaning liquid composition, which not only reduces the usage of the chelating agent, but also achieves the energy-saving cleaning effect without the adsorbent, and more efficiently removes photoresist residues, metal ions and other pollutants. Since the porous structure can be reused, the cleaning efficiency is improved.

[0019] The preparation method of the mask cleaning liquid composition comprises the following steps: weighing various raw materials by mass, first mixing water and inorganic base at room temperature and stirring them uniformly, then sequentially adding organic base, oxidant, hydroxyethyl sulfonic acid, surfactant, corrosion inhibitor and cleaning aid, and stirring at 100-300 rpm for 20-50 minutes to obtain the mask cleaning liquid composition.

[0020] Beneficial effects of the present invention: The present invention provides a mask cleaning liquid composition and a preparation method thereof. The present invention optimizes the raw materials and the reasonable distribution ratio of each raw material, and can effectively adsorb and chelate the cleaned metal ions and suspended particulate matter by adding a cleaning aid, and has good suspension, dispersion and ability to prevent solid dirt from re-precipitating and causing secondary pollution. At the same time, the modified magnetic porous carbon material added by the present invention can be reused and is environmentally friendly. The modification of the magnetic porous carbon material by a chelating agent can stabilize the cleaning liquid system and improve the cleaning effect. The present invention uses the above-mentioned modified magnetic porous carbon material as the raw material of the mask cleaning liquid composition, which not only reduces the use of the chelating agent, but also can achieve the energy-saving cleaning effect without an adsorbent, and more efficiently removes photoresist residues, metal ions and other pollutants, and can be reused, thereby improving the cleaning efficiency and saving costs. DETAILED DESCRIPTION

[0021] The above content of the present invention is further described in detail below in conjunction with specific implementation modes, but this should not be understood as the scope of the above subject matter of the present invention being limited to the following embodiments.

[0022] Introduction of some raw materials in this application: Coconut oleic acid diethanolamide polyoxyethylene ether was purchased from Hai'an Petrochemical Plant in Jiangsu Province, model POEA-15.

[0023] Example 1 A mask cleaning liquid composition is composed of the following raw materials in percentage by weight: 10wt% inorganic base, 2wt% organic base, 4wt% oxidant, 0.5wt% hydroxyethyl sulfonic acid, 6wt% surfactant, 2wt% corrosion inhibitor, 5wt% cleaning aid, and the balance is water.

[0024] The inorganic base is a mixture of sodium hydroxide and sodium carbonate in a mass ratio of 8:2.

[0025] The organic base is tetramethylammonium hydroxide.

[0026] The oxidant is a mixture of 30 wt % hydrogen peroxide and ammonium periodate in a mass ratio of 3:1.

[0027] The surfactant is coconut oil diethanolamide polyoxyethylene ether.

[0028] The corrosion inhibitor is 2-mercaptobenzothiazole.

[0029] The cleaning aid is a modified magnetic porous carbon material, and the preparation method of the modified magnetic porous carbon material is as follows: 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 were mixed, stirred at 800 rpm for 25 min at room temperature, hydrothermally reacted at 190°C for 8 h, cooled, centrifuged, washed and dried to obtain nano-iron tetroxide; then 8 parts by weight of porous carbon material and 400 parts by weight of anhydrous ethanol were added, ultrasonicated for 60 min, filtered, washed and dried to obtain a magnetic porous carbon material; S2: 2 parts by weight of N-[β-(N,N-diacetoxy)aminoethyl]-γ-(N-acetoxy)aminopropyltrimethoxysilane, 1 part by weight of p-aminophenyltrimethoxysilane, 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 stirring reaction is continued for 3 h, the pH value is adjusted to 7, and distilled under reduced pressure to obtain a hyperbranched polysiloxane; 80 parts by weight of 60wt% ethanol aqueous solution are added to the obtained hyperbranched polysiloxane and stirred uniformly, the temperature is raised to 60° C., 0.3 parts by weight of glutaraldehyde and 0.4 parts by weight of sodium borohydride are added, the mixture is stirred at 600 rpm for 3 h, the temperature is lowered to room temperature, 1 part by weight of carbon disulfide is added, the stirring is continued for 30 min, and distilled under reduced pressure to obtain a chelating agent; S3: Mix 6 parts by weight of the above-mentioned magnetic porous carbon material, 1 part by weight of the above-mentioned chelating agent and 80 parts by weight of 75wt% ethanol aqueous solution, soak at 60°C and 400rpm for 6h, filter, wash and dry to obtain a modified magnetic porous carbon material.

[0030] The preparation method of the mask cleaning liquid composition is as follows: weigh the raw materials according to mass, first mix water and inorganic base at room temperature and stir them evenly, then add organic base, oxidant, hydroxyethyl sulfonic acid, surfactant, corrosion inhibitor, and cleaning aid in sequence, and stir at 200 rpm for 30 minutes to obtain the mask cleaning liquid composition.

[0031] Example 2 A mask cleaning liquid composition is composed of the following raw materials in percentage by weight: 7wt% inorganic base, 1wt% organic base, 2wt% oxidant, 0.2wt% hydroxyethyl sulfonic acid, 3wt% surfactant, 1wt% corrosion inhibitor, 3wt% cleaning aid, and the balance is water.

[0032] The inorganic alkali is a mixture of sodium hydroxide and sodium carbonate in a mass ratio of 3.5:1.

[0033] The organic base is tetramethylammonium hydroxide.

[0034] The oxidant is a mixture of 30 wt % hydrogen peroxide and ammonium periodate in a mass ratio of 2:1.

[0035] The surfactant is coconut oil diethanolamide polyoxyethylene ether.

[0036] The corrosion inhibitor is 2-mercaptobenzothiazole.

[0037] The cleaning aid is a modified magnetic porous carbon material, and the preparation method of the modified magnetic porous carbon material is as follows: S1 Mix 6 parts by weight of Fe2(SO4)3·9H2O‌, 18 parts by weight of sodium acetate and 160 parts by weight of ethylene glycol, stir at 400 rpm for 20 min at room temperature, hydrothermally react at 180°C for 6 h, cool, centrifuge, wash and dry to obtain nano-iron tetroxide; then add 6 parts by weight of porous carbon material and 300 parts by weight of anhydrous ethanol, ultrasonicate for 50 min, filter, wash and dry to obtain magnetic porous carbon material; S2: 1 part by weight of N-[β-(N,N-diacetoxy)aminoethyl]-γ-(N-acetoxy)aminopropyltrimethoxysilane, 0.5 part by weight of p-aminophenyltrimethoxysilane, 70 parts by weight of methanol and 30 parts by weight of tetrahydrofuran were mixed uniformly, stirred at 300 rpm and 50° C. for 15 min, the pH value was adjusted to 4.5, the reaction was continued with stirring for 2 h, the pH value was adjusted to 6.5, and distilled under reduced pressure to obtain a hyperbranched polysiloxane; 50 parts by weight of a 50wt% ethanol aqueous solution were added to the obtained hyperbranched polysiloxane and stirred uniformly, the temperature was raised to 50° C., 0.1 parts by weight of glutaraldehyde and 0.2 parts by weight of sodium borohydride were added, the mixture was stirred at 400 rpm for 2 h, the temperature was lowered to room temperature, 0.5 parts by weight of carbon disulfide were added, the mixture was continued with stirring for 20 min, and distilled under reduced pressure to obtain a chelating agent; S3: Mix 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 a 60wt% ethanol aqueous solution, soak at 50°C and 300rpm for 4h, filter, wash and dry to obtain a modified magnetic porous carbon material.

[0038] The preparation method of the mask cleaning liquid composition is as follows: weigh the raw materials according to mass, first mix water and inorganic base at room temperature and stir them evenly, then add organic base, oxidant, hydroxyethyl sulfonic acid, surfactant, corrosion inhibitor, and cleaning aid in sequence, and stir at 100 rpm for 20 minutes to obtain the mask cleaning liquid composition.

[0039] Example 3 A mask cleaning liquid composition is composed of the following raw materials in percentage by weight: 10wt% inorganic base, 2wt% organic base, 4wt% oxidant, 0.5wt% hydroxyethyl sulfonic acid, 6wt% surfactant, 2wt% corrosion inhibitor, 5wt% cleaning aid, and the balance is water.

[0040] The inorganic base is a mixture of sodium hydroxide and sodium carbonate in a mass ratio of 8:2.

[0041] The organic base is tetramethylammonium hydroxide.

[0042] The oxidant is a mixture of 30 wt % hydrogen peroxide and ammonium periodate in a mass ratio of 3:1.

[0043] The surfactant is coconut oil diethanolamide polyoxyethylene ether.

[0044] The corrosion inhibitor is 2-mercaptobenzothiazole.

[0045] The cleaning aid is a modified magnetic porous carbon material, and the preparation method of the modified magnetic porous carbon material is as follows: 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 were mixed, stirred at 1000 rpm for 50 min at room temperature, hydrothermally reacted at 200°C for 10 h, cooled, centrifuged, washed and dried to obtain nano-iron tetroxide; 10 parts by weight of porous carbon material and 700 parts by weight of anhydrous ethanol were added, ultrasonicated for 90 min, filtered, washed and dried to obtain a magnetic porous carbon material; S2: 3 parts by weight of N-[β-(N,N-diacetoxy)aminoethyl]-γ-(N-acetoxy)aminopropyltrimethoxysilane, 2 parts by weight of p-aminophenyltrimethoxysilane, 130 parts by weight of methanol and 50 parts by weight of tetrahydrofuran were mixed uniformly, stirred at 500 rpm and 70° C. for 30 min, the pH value was adjusted to 5.5, the stirring reaction was continued for 5 h, the pH value was adjusted to 7.5, and the hyperbranched polysiloxane was obtained by distillation under reduced pressure; 120 parts by weight of 70wt% ethanol aqueous solution were added to the obtained hyperbranched polysiloxane and stirred uniformly, the temperature was raised to 70° C., 0.5 parts by weight of glutaraldehyde and 0.6 parts by weight of sodium borohydride were added, the mixture was stirred at 800 rpm for 5 h, the temperature was lowered to room temperature, 2 parts by weight of carbon disulfide were added, the stirring was continued for 50 min, and the mixture was distilled under reduced pressure to obtain a chelating agent; S3: Mix 8 parts by weight of the above-mentioned magnetic porous carbon material, 2 parts by weight of the above-mentioned chelating agent and 140 parts by weight of 85wt% ethanol aqueous solution, soak at 70°C and 500rpm for 10 hours, filter, wash and dry to obtain a modified magnetic porous carbon material.

[0046] The preparation method of the mask cleaning liquid composition is as follows: weigh the raw materials according to their mass, first mix water and inorganic base at room temperature and stir them evenly, then add organic base, oxidant, hydroxyethyl sulfonic acid, surfactant, corrosion inhibitor, and cleaning aid in sequence, and stir at 300 rpm for 50 minutes to obtain the mask cleaning liquid composition.

[0047] Comparative Example 1 A mask cleaning liquid composition is composed of the following raw materials in percentage by weight: 10 wt% of inorganic base, 2 wt% of organic base, 4 wt% of oxidant, 0.5 wt% of hydroxyethyl sulfonic acid, 6 wt% of surfactant, 2 wt% of corrosion inhibitor, and the balance is water.

[0048] The inorganic base is a mixture of sodium hydroxide and sodium carbonate in a mass ratio of 8:2.

[0049] The organic base is tetramethylammonium hydroxide.

[0050] The oxidant is a mixture of 30 wt % hydrogen peroxide and ammonium periodate in a mass ratio of 3:1.

[0051] The surfactant is coconut oil diethanolamide polyoxyethylene ether.

[0052] The corrosion inhibitor is 2-mercaptobenzothiazole.

[0053] The preparation method of the mask cleaning liquid composition is as follows: weigh the raw materials according to mass, first mix water and inorganic base at room temperature and stir them evenly, then add organic base, oxidant, hydroxyethyl sulfonic acid, surfactant and corrosion inhibitor in sequence, and stir at 200 rpm for 30 minutes to obtain the mask cleaning liquid composition.

[0054] Comparative Example 2 A mask cleaning liquid composition is composed of the following raw materials in percentage by weight: 10wt% inorganic base, 2wt% organic base, 4wt% oxidant, 0.5wt% hydroxyethyl sulfonic acid, 6wt% surfactant, 2wt% corrosion inhibitor, 5wt% cleaning aid, and the balance is water.

[0055] The inorganic base is a mixture of sodium hydroxide and sodium carbonate in a mass ratio of 8:2.

[0056] The organic base is tetramethylammonium hydroxide.

[0057] The oxidant is a mixture of 30 wt % hydrogen peroxide and ammonium periodate in a mass ratio of 3:1.

[0058] The surfactant is coconut oil diethanolamide polyoxyethylene ether.

[0059] The corrosion inhibitor is 2-mercaptobenzothiazole.

[0060] The cleaning aid is a magnetic porous carbon material, and the preparation method of the magnetic porous carbon material is as follows: 8 parts by weight of Fe2(SO4)3·9H2O‌, 20 parts by weight of sodium acetate and 200 parts by weight of ethylene glycol were mixed, stirred at 800 rpm for 25 min at room temperature, hydrothermally reacted at 190°C for 8 h, cooled, centrifuged, washed and dried to obtain nano-iron tetroxide; then 8 parts by weight of porous carbon material and 400 parts by weight of anhydrous ethanol were added, ultrasonicated for 60 min, filtered, washed and dried to obtain a magnetic porous carbon material.

[0061] The preparation method of the mask cleaning liquid composition is as follows: weigh the raw materials according to mass, first mix water and inorganic base at room temperature and stir them evenly, then add organic base, oxidant, hydroxyethyl sulfonic acid, surfactant, corrosion inhibitor, and cleaning aid in sequence, and stir at 200 rpm for 30 minutes to obtain the mask cleaning liquid composition.

[0062] Comparative Example 3 A mask cleaning liquid composition is composed of the following raw materials in percentage by weight: 10wt% inorganic base, 2wt% organic base, 4wt% oxidant, 0.5wt% hydroxyethyl sulfonic acid, 6wt% surfactant, 2wt% corrosion inhibitor, 5wt% cleaning aid, and the balance is water.

[0063] The inorganic base is a mixture of sodium hydroxide and sodium carbonate in a mass ratio of 8:2.

[0064] The organic base is tetramethylammonium hydroxide.

[0065] The oxidant is a mixture of 30 wt % hydrogen peroxide and ammonium periodate in a mass ratio of 3:1.

[0066] The surfactant is coconut oil diethanolamide polyoxyethylene ether.

[0067] The corrosion inhibitor is 2-mercaptobenzothiazole.

[0068] The cleaning aid is a chelating agent, and the preparation method of the chelating agent is as follows: 2 parts by weight of N-[β-(N,N-diacetoxy)aminoethyl]-γ-(N-acetoxy)aminopropyltrimethoxysilane, 1 part by weight of p-aminophenyltrimethoxysilane, 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 stirring reaction is continued for 3 h, the pH value is adjusted to 7, and distillation is performed under reduced pressure to obtain a hyperbranched polysiloxane; 80 parts by weight of a 60wt% ethanol aqueous solution are added to the obtained hyperbranched polysiloxane and stirred uniformly, the temperature is raised to 60° C., 0.3 parts by weight of glutaraldehyde and 0.4 parts by weight of sodium borohydride are added, the mixture is stirred at 600 rpm for 3 h, the temperature is lowered to room temperature, 1 part by weight of carbon disulfide is added, the stirring is continued for 30 min, and distillation is performed under reduced pressure to obtain a chelating agent.

[0069] The preparation method of the mask cleaning liquid composition is as follows: weigh the raw materials according to mass, first mix water and inorganic base at room temperature and stir them evenly, then add organic base, oxidant, hydroxyethyl sulfonic acid, surfactant, corrosion inhibitor, and cleaning aid in sequence, and stir at 200 rpm for 30 minutes to obtain the mask cleaning liquid composition.

[0070] Comparative Example 4 A mask cleaning liquid composition is composed of the following raw materials in percentage by weight: 10wt% inorganic base, 2wt% organic base, 4wt% oxidant, 0.5wt% hydroxyethyl sulfonic acid, 6wt% surfactant, 2wt% corrosion inhibitor, 5wt% cleaning aid, and the balance is water.

[0071] The inorganic base is a mixture of sodium hydroxide and sodium carbonate in a mass ratio of 8:2.

[0072] The organic base is tetramethylammonium hydroxide.

[0073] The oxidant is a mixture of 30 wt % hydrogen peroxide and ammonium periodate in a mass ratio of 3:1.

[0074] The surfactant is coconut oil diethanolamide polyoxyethylene ether.

[0075] The corrosion inhibitor is 2-mercaptobenzothiazole.

[0076] The cleaning aid is a modified magnetic porous carbon material, and the preparation method of the modified magnetic porous carbon material is as follows: 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 were mixed, stirred at 800 rpm for 25 min at room temperature, hydrothermally reacted at 190°C for 8 h, cooled, centrifuged, washed and dried to obtain nano-iron tetroxide; then 8 parts by weight of porous carbon material and 400 parts by weight of anhydrous ethanol were added, ultrasonicated for 60 min, filtered, washed and dried to obtain a magnetic porous carbon material; S2: Mix 6 parts by weight of the above-mentioned magnetic porous carbon material, 1 part by weight of N-[β-(N,N-diacetoxy)aminoethyl]-γ-(N-acetoxy)aminopropyltrimethoxysilane and 80 parts by weight of 75wt% ethanol aqueous solution, soak at 60°C and 400rpm for 6 hours, filter, wash and dry to obtain a modified magnetic porous carbon material.

[0077] The preparation method of the mask cleaning liquid composition is as follows: weigh the raw materials according to mass, first mix water and inorganic base at room temperature and stir them evenly, then add organic base, oxidant, hydroxyethyl sulfonic acid, surfactant, corrosion inhibitor, and cleaning aid in sequence, and stir at 200 rpm for 30 minutes to obtain the mask cleaning liquid composition.

[0078] Test Example 1 A semiconductor wafer (containing a pattern) containing a negative acrylic photoresist (having a thickness of about 60 microns and having been exposed and etched) was immersed in the mask cleaning solution composition prepared in Examples 1-3 and Comparative Examples 1-4, and oscillated at 55°C using a constant temperature oscillator for 20 minutes, then washed with deionized water and dried with high-purity nitrogen. The cleaning effect of the photoresist and the cleaning and corrosion conditions of the cleaning agent composition on the wafer pattern were evaluated. The mask cleaning solution composition after adsorption was placed for one month and then cleaned again. The results are shown in Table 1.

[0079] Table 1 Cleaning effect test of mask cleaning liquid composition Test Example 2 Etching rate test method: Heat the mask cleaning liquid composition in a water bath. When the cleaning liquid reaches 40°C, add a 2*2cm titanium nitride sheet into the cleaning liquid and start timing. When the titanium nitride etching is completely finished, the timing is stopped. The actual titanium nitride etching rate is calculated based on the known film thickness and the etching time. Corrosion rate = (thickness before cleaning - thickness after cleaning) / cleaning time. The results are shown in Table 2.

[0080] Table 2 Etching effect test of mask cleaning solution composition From the above results, it can be seen that the mask cleaning liquid composition prepared by the present invention has a good cleaning effect on both photoresist and titanium nitride. Comparison of Example 1 and Comparative Examples 1-3 shows that the present invention uses porous carbon materials as adsorbents and magnetic ferroferric oxide as adsorbents for metal impurities, both of which have certain adsorption capacity from different dimensions, and uses hyperbranched siloxanes as chelating agents to combine and use, thereby realizing a multifunctional cleaning aid. The porous structure on the porous carbon material is an adsorbent, which provides storage space for ferroferric oxide and improves the adsorption capacity of the material. The nano ferroferric oxide magnetic material enters the pores of the porous carbon material through van der Waals force and is distributed on the surface of the material and the inner wall of the porous structure, which not only increases the roughness of the material but also improves the hydrophobicity of the material. A hyperbranched siloxane chelating agent is used as a modifier to hydrophobically modify the magnetic material to achieve hydrophobic properties. During the reaction, the ethyl group of the hyperbranched siloxane chelating agent is replaced by ferroferric oxide magnetic beads, so the hyperbranched siloxane chelating agent and the ferroferric oxide magnetic beads are combined together through a chemical reaction. It can be seen from the above that the ferroferric oxide magnetic beads are not only adsorbed on the surface of the porous carbon material, but also adsorbed inside the multi-hole channels. Therefore, the hyperbranched siloxane chelating agent exists on the surface of the porous carbon material and in the pores, which can form a multifunctional cleaning aid and improve the cleaning efficiency.

[0081] The present invention adopts modified magnetic porous carbon material as chelating agent and adsorbent at the same time, which can be well compatible and dispersed with the mask cleaning liquid composition, has high dispersibility and adsorption in the system, and can be applied to the mask cleaning liquid composition to quickly penetrate into the micro cracks on the surface of the mask plate, forming a splitting effect, and uniformly forming a grinding surface on the surface of the mask plate. The modified magnetic porous carbon material has a high specific surface area and a porous structure, and can effectively adsorb organic pollutants and impurities in the mask cleaning liquid, such as photoresist residues, metal ions and other pollutants. This efficient 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, its selective adsorption capacity for specific pollutants can be enhanced. This selective removal capacity helps to improve the pertinence of the cleaning liquid and reduce the impact on other harmless components; because the modified magnetic porous carbon material can quickly adsorb and remove pollutants, the time and steps of the cleaning process can be significantly shortened, improving the overall production efficiency, and there is no residue in the subsequent cleaning process.

Claims

1. A mask cleaning liquid composition, characterized in that: The invention is composed of the following raw materials in percentage by weight: 7-13wt% inorganic base, 1-4wt% organic base, 2-5wt% oxidant, 0.2-0.8wt% hydroxyethyl sulfonic acid, 3-7wt% surfactant, 1-4wt% corrosion inhibitor, 3-8wt% cleaning aid, and the balance is water; the cleaning aid is a modified magnetic porous carbon material.

2. The mask cleaning liquid composition according to 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 liquid composition according to 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 liquid composition according to 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 liquid composition according to claim 1, characterized in that: The surfactant is one or more of ethylenediaminetetraacetic acid, dimethyloctynediol, oleoyldiethanolamine, and coconut oleic acid diethanolamide polyoxyethylene ether.

6. The mask cleaning liquid composition according to 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 liquid composition according to claim 1, characterized in that: The preparation method of the modified magnetic porous carbon material is as follows: S1: Fe2(SO4)3·9H2O‌, sodium acetate and ethylene glycol are mixed and stirred, and subjected to hydrothermal reaction to obtain nano-iron tetroxide; porous carbon material and anhydrous ethanol are then added and ultrasonicated to obtain magnetic porous carbon material; S2: N-[β-(N,N-diacetoxy)aminoethyl]-γ-(N-acetoxy)aminopropyltrimethoxysilane, p-aminophenyltrimethoxysilane, methanol and tetrahydrofuran are mixed uniformly, heated with stirring, and distilled under reduced pressure to obtain a hyperbranched polysiloxane; ethanol aqueous solution is added to the obtained hyperbranched polysiloxane and stirred uniformly, the temperature is increased, glutaraldehyde and sodium borohydride are added, stirred, the temperature is lowered, carbon disulfide is added, and stirring is continued to obtain a chelating agent; S3: Mix the magnetic porous carbon material, the chelating agent and the ethanol aqueous solution, soak them in hot water with stirring, filter, wash and dry them to obtain a modified magnetic porous carbon material.

8. The mask cleaning liquid composition according to claim 7, characterized in that: The preparation method of the modified magnetic porous carbon material is as follows: S1: 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 are mixed, stirred at 400-1000 rpm for 20-50 min at room temperature, hydrothermally reacted at 180-200°C for 6-10 h, cooled, centrifuged, washed and dried to obtain nano-iron tetroxide; 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 a magnetic porous carbon material; S2: 1-3 parts by weight of N-[β-(N,N-diacetoxy)aminoethyl]-γ-(N-acetoxy)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 are uniformly mixed, stirred at 300-500 rpm and 50-70° C. for 15-30 min, the pH value is adjusted to 4.5-5.5, the reaction is continued with stirring for 2-5 h, and the pH value is adjusted to 6.5-7. .5, distill under reduced pressure to obtain a hyperbranched polysiloxane; add 50-120 parts by weight of a 50-70wt% ethanol aqueous solution to the obtained hyperbranched polysiloxane and stir evenly, heat to 50-70°C, add 0.1-0.5 parts by weight of glutaraldehyde and 0.2-0.6 parts by weight of sodium borohydride, stir at 400-800rpm for 2-5h, cool to room temperature, add 0.5-2 parts by weight of carbon disulfide, continue stirring for 20-50min, and distill under reduced pressure to obtain a chelating agent; S3: 4-8 parts by weight of the above-mentioned magnetic porous carbon material, 0.5-2 parts by weight of the above-mentioned chelating agent and 50-140 parts by weight of 60-85wt% ethanol aqueous solution are mixed, and the mixture is immersed in water at 50-70°C and 300-500rpm for 4-10h, filtered, washed and dried to obtain a modified magnetic porous carbon material.

9. The method for preparing the mask cleaning liquid composition according to any one of claims 1 to 8, characterized in that: The method comprises the following steps: weighing various raw materials by mass, mixing water and inorganic base at room temperature and stirring evenly, adding organic base, oxidant, hydroxyethyl sulfonic acid, surfactant, corrosion inhibitor and cleaning aid in sequence, stirring at 100-300 rpm for 20-50 minutes, and obtaining a mask cleaning liquid composition.

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