An organic antireflective coating composition, its preparation method and use

Abstract

The present application relates to the field of photoetching technology, and especially relates to an organic antireflection coating composition and a preparation method and application thereof. The coating composition comprises the following raw materials in parts by weight: matt resin 5-10 parts, crosslinking agent 1-5 parts, surfactant 0.2-1 part, and organic solvent 90-100 parts. The preparation process of the matt resin is as follows: methyl methacrylate, glycidyl methacrylate, methacrylic acid-9-anthracene methyl ester and acrylic ester monomer A are added into 1,4-dioxane, an initiator is added under the protection of inert gas, and the product is obtained after reaction and purification. The coating composition has excellent film thickness uniformity, corrosion resistance and antireflection performance.

Description

Technical Field

[0001] This invention relates to the field of photolithography, and more particularly to an organic antireflective coating composition, its preparation method, and its application. Background Technology

[0002] The silicon substrate reflects incident light, and the reflected light interferes with the incident light, creating a standing wave effect within the photoresist. This leads to decreased stability in critical dimension control and the formation of wavy or jagged defects on the photoresist sidewalls, severely impacting pattern resolution and sharpness. The bottom anti-reflective coating (BARC) absorbs reflected light from the substrate and reduces the reflectivity of the photoresist interface, thereby improving linewidth control and enhancing photoresist performance.

[0003] However, in actual film deposition processes, factors such as the leveling properties of the coating, drying shrinkage behavior, and interfacial interactions with the substrate can easily cause localized uneven film thickness. Once the deviation exceeds the process tolerance, it will not only cause fluctuations in reflectivity and affect exposure uniformity, but may also lead to critical dimension deviations or edge roughness deterioration due to film thickness variations, ultimately posing a significant threat to chip yield. Therefore, improving anti-reflective coating formulations to achieve excellent film thickness uniformity is of great practical significance. Summary of the Invention

[0004] In order to overcome the shortcomings of the prior art, one of the objectives of the present invention is to provide an organic anti-reflective coating composition with excellent film thickness uniformity, corrosion resistance and anti-reflective properties.

[0005] The second objective of this invention is to provide a simple method for preparing an organic antireflective coating composition.

[0006] The third objective of this invention is to provide an application of an organic antireflective coating composition, which has broad prospects.

[0007] One of the objectives of this invention is achieved through the following technical solution: An organic anti-reflective coating composition, by weight, comprises the following raw materials: 5-10 parts of matting resin, 1-5 parts of crosslinking agent, 0.2-1 parts of surfactant, and 90-100 parts of organic solvent; The preparation process of the matting resin is as follows: Methyl methacrylate, glycidyl methacrylate, methyl 9-anthracene methacrylate, and acrylate monomer A are added to 1,4-dioxane. Under inert gas protection, an initiator is added, and the reaction is purified to obtain the product. The structural formula of the acrylate monomer A is: .

[0008] This invention synthesizes a matting resin through the copolymerization reaction of methyl methacrylate, glycidyl methacrylate, methyl 9-anthracene methacrylate and acrylate monomer A.

[0009] Preferably, the molar ratio of methyl methacrylate, glycidyl methacrylate, methyl 9-anthracene methacrylate, and acrylate monomer A is 1:(3.5-4):(1.5-2):(0.5-0.8); the amount of initiator added is 0.2-0.5% of the total mass of the reactants; the initiator is azobisisobutyronitrile; the reaction temperature is 80-90℃, and the reaction time is 9-12h.

[0010] Preferably, the preparation process of the acrylate monomer A is as follows: (1) Under inert gas protection, biuret, 1 / 2-3 / 4 of 5,3'-diisocyanate-7,4'-dimethoxyflavone and dibutyltin dilaurate were added to tetrahydrofuran. After reflux reaction, the remaining 5,3'-diisocyanate-7,4'-dimethoxyflavone was added. After further reaction and purification, intermediate 1 was obtained. The structural formula of the 5,3'-diisocyanate-7,4'-dimethoxyflavonoid is: The structural formula of intermediate 1 is: (2) Under the protection of an inert gas, the intermediate 1 and dibutyltin dilaurate were added to dichloromethane, and then hydroxyethyl acrylate was added. After the reaction, the mixture was purified to obtain the acrylate monomer A.

[0011] Acrylate monomer A is prepared by reacting 5,3'-diisocyanate-7,4'-dimethoxyflavone with biuret to introduce a biuret structure to obtain intermediate 1, which is then further reacted with hydroxyethyl acrylate to obtain intermediate 1.

[0012] Preferably, in step (1), the molar ratio of biuret, 5,3'-diisocyanate-7,4'-dimethoxyflavone, and dibutyltin dilaurate is 1:(2.2-2.4):(0.005-0.006); the reflux reaction time is 5-8 h; the continued reaction time is 6-9 h; in step (2), the molar ratio of intermediate 1, hydroxyethyl acrylate, and dibutyltin dilaurate is 1:(1-1.04):(0.004-0.006); the reaction time is 5-8 h.

[0013] Preferably, the preparation process of the 5,3'-diisocyanate-7,4'-dimethoxyflavone is as follows: (a) 5,3'-dihydroxy-7,4'-dimethoxyflavone was added to N,N-dimethylformamide, a first portion of sodium hydroxide was added, and after stirring for 1-2 h, 2-bromo-2-methylpropionamide was added. After stirring for 12-14 h, a second portion of sodium hydroxide was added. After reacting at 50-55 °C for 5-6 h, water and a third portion of sodium hydroxide were added, and the mixture was refluxed. After purification, 5,3'-diamino-7,4'-dimethoxyflavone was obtained. The structural formula of the 5,3'-diamino-7,4'-dimethoxyflavonoid is: (b) The 5,3'-diamino-7,4'-dimethoxyflavone was added to acetonitrile, and then 4-dimethylaminopyridine and ditert-butyl dicarbonate were added in sequence. After the reaction, the mixture was purified to obtain the 5,3'-diisocyanate-7,4'-dimethoxyflavone.

[0014] The 5,3'-diisocyanate-7,4'-dimethoxyflavone of the present invention is prepared by using 5,3'-dihydroxy-7,4'-dimethoxyflavone as a raw material and converting the phenolic hydroxyl groups in the molecule into isocyanate groups through a two-step modification reaction.

[0015] Preferably, in step (a), the ratio of 5,3'-dihydroxy-7,4'-dimethoxyflavone, the first part of sodium hydroxide, 2-bromo-2-methylpropionamide, the second part of sodium hydroxide, the third part of sodium hydroxide, and water is 1 mmol: (3-4) mmol: (3-4) mmol: (9-10) mmol: (6-7) mmol: (1.5-2) mL; and the reflux reaction time is 1-2 h.

[0016] Preferably, the molar ratio of 5,3'-diamino-7,4'-dimethoxyflavonoid, 4-dimethylaminopyridine, and ditert-butyl dicarbonate in step (b) is 1:(0.1-0.15):(2.2-2.3); and the reaction time is 2-4 h.

[0017] Preferably, the crosslinking agent is 4,4'-diaminodicyclohexylmethane; the surfactant is BYK-388 or BYK-307; and the organic solvent is selected from propylene glycol methyl ether acetate, cyclohexanone, and propylene glycol monomethyl ether.

[0018] The second objective of this invention is achieved by the following technical solution: The preparation method of the above-mentioned organic antireflective coating composition includes the following steps: Add matting resin, crosslinking agent, and surfactant to an organic solvent and mix thoroughly to obtain the final product.

[0019] The third objective of this invention is achieved by the following technical solution: The above-mentioned organic anti-reflective coating composition is applied in the photolithography process.

[0020] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. This invention provides an organic anti-reflective coating composition comprising a matting resin, a crosslinking agent, a surfactant, and an organic solvent. This coating composition exhibits excellent film thickness uniformity, corrosion resistance, and anti-reflective properties.

[0021] 2. This invention uses 5,3'-dihydroxy-7,4'-dimethoxyflavonoid as a raw material, and obtains acrylate monomer A through a modification reaction. This monomer A is then copolymerized with methyl methacrylate, glycidyl methacrylate, and methyl 9-anthracene methacrylate to form a matting resin, thereby improving the film thickness uniformity and anti-reflective properties of the coating. The biuret structure in acrylate monomer A can enhance intermolecular forces through multiple hydrogen bonds, combining with the rigid skeleton of 5,3'-diisocyanate-7,4'-dimethoxyflavonoid to jointly inhibit the volume shrinkage of the polymer during curing, thus improving the film thickness uniformity of the coating. Simultaneously, the isocyanate groups retained in acrylate monomer A can participate in cross-linking and curing with the epoxy groups of glycidyl methacrylate in the matting resin, forming a film with good coating quality. Furthermore, its flavonoid skeleton has ultraviolet absorption capabilities, which helps to improve the anti-reflective properties of the coating.

[0022] 3. This invention uses 4,4'-diaminodicyclohexylmethane as a crosslinking agent to improve the corrosion resistance of the coating. The active amino groups in 4,4'-diaminodicyclohexylmethane can react with the epoxy groups or isocyanate groups in the matte resin to form a crosslinking network. Simultaneously, the alicyclic skeleton of 4,4'-diaminodicyclohexylmethane has certain steric hindrance and hydrophobicity, which can reduce the medium permeability of the coating, thereby improving the corrosion resistance of the coating. Detailed Implementation

[0023] The present invention will now be further described in conjunction with specific embodiments. It should be noted that, without conflict, the various embodiments or technical features described below can be arbitrarily combined to form new embodiments. Specific conditions not specified in the embodiments shall be performed according to conventional conditions or conditions recommended by the manufacturer. Unless otherwise specified, all reagents or instruments used are conventional products obtained through commercial channels.

[0024] Preparation Example 1 A 5,3'-diisocyanate-7,4'-dimethoxyflavonoid is prepared as follows: (a) Using 5,3'-dihydroxy-7,4'-dimethoxyflavone, a first portion of sodium hydroxide, 2-bromo-2-methylpropionamide, a second portion of sodium hydroxide, a third portion of sodium hydroxide, water, and N,N-dimethylformamide in a ratio of 1 mmol:3.5 mmol:3.5 mmol:9.5 mmol:6.5 mmol:1.6 mL:3.5 mL, 5,3'-dihydroxy-7,4'-dimethoxyflavone was dissolved in N,N-dimethylformamide. Sodium hydroxide was added and the mixture was stirred at room temperature for 1.5 h. Then, 2-bromo-2-methylpropionamide was added and the mixture was stirred at room temperature for 13 h. Sodium hydroxide was then added, and the mixture was heated to 52 °C and reacted for 5.5 h. Deionized water and sodium hydroxide were added, and the mixture was reacted under reflux for 1.5 h. Finally, water was added to precipitate the product. The crude product was purified by column chromatography (V... 二氯甲烷 V 甲醇 V 三乙胺 =10:1:0.1), yielding 5,3'-diamino-7,4'-dimethoxyflavone; the NMR and mass spectrometry results of 5,3'-diamino-7,4'-dimethoxyflavone are as follows: 1 HNMR: (C 17 H 16 N2O4, 400MHz, DMSO- d6 ) δ: 3.78 (s, 3H), 3.90 (s, 3H), 5.40 (s, 2H), 6.28 (s, 1H), 6.35 (s, 2H), 6.73-6.87 (m, 4H), 7.03-7.10 (dd, 1H). MS (ESI) m / z=312.14[M].

[0025] (b) Using 5,3'-diamino-7,4'-dimethoxyflavone, 4-dimethylaminopyridine, di-tert-butyl dicarbonate, and acetonitrile in a ratio of 1 mmol:0.12 mmol:2.25 mmol:6 mL, the 5,3'-diamino-7,4'-dimethoxyflavone was dissolved in acetonitrile, followed by the sequential addition of 4-dimethylaminopyridine and di-tert-butyl dicarbonate. After reacting at room temperature for 3 h, the solvent was removed by rotary evaporation, and the residue was purified by column chromatography (V... 石油醚 V 乙酸乙酯 =2:1), yielding 5,3'-diisocyanate-7,4'-dimethoxyflavone; the NMR and mass spectrometry results of 5,3'-diisocyanate-7,4'-dimethoxyflavone are as follows: 1 HNMR: (C 19 H 12 N2O6, 400MHz, DMSO- d6) δ: 3.81 (s, 3H), 3.94 (s, 3H), 6.32 (s, 1H), 6.52 (s, 1H), 6.95-7.15 (m, 3H), 7.43-7.47 (dd, 1H). MS (ESI) m / z=364.09 [M].

[0026] Preparation Example 2 A 5,3'-diisocyanate-7,4'-dimethoxyflavonoid is prepared as follows: (a) Using 5,3'-dihydroxy-7,4'-dimethoxyflavone, a first portion of sodium hydroxide, 2-bromo-2-methylpropionamide, a second portion of sodium hydroxide, a third portion of sodium hydroxide, water, and N,N-dimethylformamide in a ratio of 1 mmol:3 mmol:3 mmol:9 mmol:6 mmol:1.5 mL:3 mL, 5,3'-dihydroxy-7,4'-dimethoxyflavone was dissolved in N,N-dimethylformamide. Sodium hydroxide was added and the mixture was stirred at room temperature for 1 h. Then, 2-bromo-2-methylpropionamide was added and the mixture was stirred at room temperature for 12 h. Sodium hydroxide was then added, and the mixture was heated to 50 °C and reacted for 6 h. Deionized water and sodium hydroxide were added, and the mixture was reacted under reflux for 1 h. Finally, water was added to precipitate the product. The crude product was purified by column chromatography (V... 二氯甲烷 V 甲醇 V 三乙胺 =10:1:0.1), to obtain 5,3'-diamino-7,4'-dimethoxyflavone; the NMR and mass spectrometry results of 5,3'-diamino-7,4'-dimethoxyflavone were consistent with those of Preparation Example 1.

[0027] (b) Using 5,3'-diamino-7,4'-dimethoxyflavone, 4-dimethylaminopyridine, di-tert-butyl dicarbonate, and acetonitrile in a ratio of 1 mmol:0.1 mmol:2.2 mmol:5 mL, the 5,3'-diamino-7,4'-dimethoxyflavone was dissolved in acetonitrile, followed by the sequential addition of 4-dimethylaminopyridine and di-tert-butyl dicarbonate. After reacting at room temperature for 2 h, the solvent was removed by rotary evaporation, and the residue was purified by column chromatography (V... 石油醚 V 乙酸乙酯 =2:1), to obtain 5,3'-diisocyanate-7,4'-dimethoxyflavone; the NMR and mass spectrometry results of 5,3'-diisocyanate-7,4'-dimethoxyflavone were consistent with those of Preparation Example 1.

[0028] Preparation Example 3 A 5,3'-diisocyanate-7,4'-dimethoxyflavonoid is prepared as follows: (a) Using 5,3'-dihydroxy-7,4'-dimethoxyflavone, a first portion of sodium hydroxide, 2-bromo-2-methylpropionamide, a second portion of sodium hydroxide, a third portion of sodium hydroxide, water, and N,N-dimethylformamide in a ratio of 1 mmol:4 mmol:4 mmol:10 mmol:7 mmol:2 mL:4 mL, 5,3'-dihydroxy-7,4'-dimethoxyflavone was dissolved in N,N-dimethylformamide. Sodium hydroxide was added and the mixture was stirred at room temperature for 2 h. Then, 2-bromo-2-methylpropionamide was added and the mixture was stirred at room temperature for 14 h. Sodium hydroxide was then added, and the mixture was heated to 55 °C and reacted for 5 h. Deionized water and sodium hydroxide were added, and the mixture was reacted under reflux for 2 h. Finally, water was added to precipitate the product. The crude product was purified by column chromatography (V... 二氯甲烷 V 甲醇 V 三乙胺 =10:1:0.1), to obtain 5,3'-diamino-7,4'-dimethoxyflavone; the NMR and mass spectrometry results of 5,3'-diamino-7,4'-dimethoxyflavone were consistent with those of Preparation Example 1.

[0029] (b) Using 5,3'-diamino-7,4'-dimethoxyflavone, 4-dimethylaminopyridine, di-tert-butyl dicarbonate, and acetonitrile in a ratio of 1 mmol: 0.1-0.15 mmol: 2.2-2.3 mmol: 5-7 mL, the 5,3'-diamino-7,4'-dimethoxyflavone was dissolved in acetonitrile, and then 4-dimethylaminopyridine and di-tert-butyl dicarbonate were added sequentially. After reacting at room temperature for 4 h, the solvent was removed by rotary evaporation, and the residue was purified by column chromatography (V... 石油醚 V 乙酸乙酯 =2:1), to obtain 5,3'-diisocyanate-7,4'-dimethoxyflavone; the NMR and mass spectrometry results of 5,3'-diisocyanate-7,4'-dimethoxyflavone were consistent with those of Preparation Example 1.

[0030] Preparation Example 4 An acrylate monomer A is prepared as follows: (1) Biuret, 5,3'-diisocyanate-7,4'-dimethoxyflavone, dibutyltin dilaurate, and tetrahydrofuran were added to tetrahydrofuran in a ratio of 10 mmol: 23 mmol: 0.05 mmol: 85 mL under nitrogen protection. The mixture was reacted with 2 / 3 of the 5,3'-diisocyanate-7,4'-dimethoxyflavone and dibutyltin dilaurate from Preparation Example 1 into tetrahydrofuran. After reacting under reflux for 6 h, the remaining 5,3'-diisocyanate-7,4'-dimethoxyflavone was added, and the reaction was continued for another 8 h. The solvent was removed by rotary evaporation, and the residue was purified by column chromatography (V... 二氯甲烷 V 乙酸乙酯=3:1), resulting in intermediate 1; the NMR and mass spectrometry results of intermediate 1 are as follows: 1 HNMR: (C 40 H 29 N7O 14 400MHz, DMSO- d6 ) δ: 3.75 (s, 6H), 3.88 (s, 6H), 6.98 (s, 2H), 6.63 (s, 2H), 6.95-6.99 (d, 2H), 7.25 (s, 2H), 7.38-7.48 (m, 4H), 8.64 (s, 2H), 10.01 (s, 3H). MS (ESI) m / z=831.15 [M].

[0031] (2) With intermediate 1, hydroxyethyl acrylate, dibutyltin dilaurate, and dichloromethane in a ratio of 5 mmol:5.1 mmol:0.022 mmol:45 mL, under nitrogen protection, intermediate 1 and dibutyltin dilaurate were added to dichloromethane, followed by dropwise addition of hydroxyethyl acrylate. After reacting at room temperature for 7 h, the solvent was removed by rotary evaporation, and the residue was purified by column chromatography (V 二氯甲烷 V 乙酸乙酯 =2:1), yielding acrylate monomer A; the NMR and mass spectrometry results of acrylate monomer A are as follows: 1 HNMR: (C 45 H 37 N7O 17 400MHz, DMSO- d6 ) δ: 3.75 (s, 3H), 3.88 (s, 6H), 3.81 (s, 3H), 4.25-4.40 (m, 4H), 5.75-6.35 (m, 3H), 6.98 (s, 1H), 6.64 (s, 2H), 6.95-7.06 (m, 4H), 7.25 (s, 1H), 7.38-7.48 (m, 4H), 8.64 (s, 2H), 9.89 (s, 1H), 10.01 (s, 3H). MS (ESI) m / z=947.24[M].

[0032] Preparation Example 5 An acrylate monomer A is prepared as follows: (1) Biuret, 5,3'-diisocyanate-7,4'-dimethoxyflavone, dibutyltin dilaurate, and tetrahydrofuran were added to tetrahydrofuran in a ratio of 10 mmol: 22 mmol: 0.05 mmol: 80 mL under nitrogen protection. The mixture was reacted with biuret, 1 / 2 of the 5,3'-diisocyanate-7,4'-dimethoxyflavone from Preparation Example 2, and dibutyltin dilaurate. After reacting under reflux for 5 h, the remaining 5,3'-diisocyanate-7,4'-dimethoxyflavone was added, and the reaction was continued for 6 h. The solvent was removed by rotary evaporation, and the residue was purified by column chromatography (V... 二氯甲烷 V 乙酸乙酯 =3:1), to obtain intermediate 1; the NMR and mass spectrometry results of intermediate 1 are consistent with those of preparation example 4.

[0033] (2) With intermediate 1, hydroxyethyl acrylate, dibutyltin dilaurate, and dichloromethane in a ratio of 5 mmol: 5 mmol: 0.02 mmol: 40 mL, under nitrogen protection, intermediate 1 and dibutyltin dilaurate were added to dichloromethane, followed by dropwise addition of hydroxyethyl acrylate. After reacting at room temperature for 5 h, the solvent was removed by rotary evaporation, and the residue was purified by column chromatography (V 二氯甲烷 V 乙酸乙酯 =2:1), to obtain acrylate monomer A; the NMR and mass spectrometry results of acrylate monomer A are consistent with those of preparation example 4.

[0034] Preparation Example 6 An acrylate monomer A is prepared as follows: (1) Biuret, 5,3'-diisocyanate-7,4'-dimethoxyflavone, dibutyltin dilaurate, and tetrahydrofuran were added to tetrahydrofuran in a ratio of 10 mmol: 24 mmol: 0.06 mmol: 90 mL under nitrogen protection. The mixture was reacted with 3 / 4 of the 5,3'-diisocyanate-7,4'-dimethoxyflavone and dibutyltin dilaurate from Preparation Example 3. After reacting under reflux for 8 h, the remaining 5,3'-diisocyanate-7,4'-dimethoxyflavone was added, and the reaction was continued for another 9 h. The solvent was removed by rotary evaporation, and the residue was purified by column chromatography (V... 二氯甲烷 V 乙酸乙酯 =3:1), to obtain intermediate 1; the NMR and mass spectrometry results of intermediate 1 are consistent with those of preparation example 4.

[0035] (2) With intermediate 1, hydroxyethyl acrylate, dibutyltin dilaurate, and dichloromethane in a ratio of 5 mmol:5.2 mmol:0.03 mmol:50 mL, under nitrogen protection, intermediate 1 and dibutyltin dilaurate were added to dichloromethane, followed by dropwise addition of hydroxyethyl acrylate. After reacting at room temperature for 8 h, the solvent was removed by rotary evaporation, and the residue was purified by column chromatography (V 二氯甲烷 V乙酸乙酯 =2:1), to obtain acrylate monomer A; the NMR and mass spectrometry results of acrylate monomer A are consistent with those of preparation example 4.

[0036] Preparation Example 7 A matting resin, prepared as follows: With a molar ratio of methyl methacrylate, glycidyl methacrylate, methyl 9-anthracene methacrylate, and acrylate monomer A of Preparation Example 4 of methyl methacrylate, glycidyl methacrylate, methyl 9-anthracene methacrylate, and acrylate monomer A of Preparation Example 4 dissolved in 1,4-dioxane; under nitrogen protection, 0.4% of the total mass of azobisisobutyronitrile (AIBN) of the total reactants was added, and the reaction was carried out at 85°C for 10 h. After cooling to room temperature, the reaction solution was poured into methanol to precipitate the product. The product was washed with methanol and dried under vacuum to obtain a matting resin (Mw=15678).

[0037] Preparation Example 8 A matting resin, prepared as follows: With a molar ratio of methyl methacrylate, glycidyl methacrylate, methyl 9-anthracene methacrylate, and acrylate monomer A of Preparation Example 5 of methyl methacrylate, glycidyl methacrylate, methyl 9-anthracene methacrylate, and acrylate monomer A of Preparation Example 5 dissolved in 1,4-dioxane; under nitrogen protection, 0.2% of the total mass of azobisisobutyronitrile (AIBN) of the total reactants was added, and the reaction was carried out at 80°C for 12 h. After cooling to room temperature, the reaction solution was poured into methanol to precipitate the product. The product was washed with methanol and dried under vacuum to obtain a matting resin (Mw=20946).

[0038] Preparation Example 9 A matting resin, prepared as follows: With a molar ratio of methyl methacrylate, glycidyl methacrylate, methyl 9-anthracene methacrylate, and acrylate monomer A of Preparation Example 6 of methyl methacrylate, glycidyl methacrylate, methyl 9-anthracene methacrylate, and acrylate monomer A of Preparation Example 6 dissolved in 1,4-dioxane; under nitrogen protection, 0.5% of the total mass of azobisisobutyronitrile (AIBN) of the total reactants was added, and the reaction was carried out at 90°C for 9 hours. After cooling to room temperature, the reaction solution was poured into methanol to precipitate the product. The product was washed with methanol and dried under vacuum to obtain a matting resin (Mw=24798).

[0039] Preparation Example 10 The difference between Preparation Example 10 and Preparation Example 7 is that hydroxyethyl acrylate was used to replace acrylate monomer A in Preparation Example 4, and the weight average molecular weight of the matting resin was 17650.

[0040] Example 1 An organic antireflective coating composition, by weight, comprises the following raw materials: 7 parts of the matting resin of Preparation Example 7, 4 parts of 4,4'-diaminodicyclohexylmethane, 0.6 parts of BYK-388, and 93 parts of propylene glycol methyl ether acetate.

[0041] The preparation method of the above-mentioned organic antireflective coating composition includes the following steps: Add matting resin, 4,4'-diaminodicyclohexylmethane, and BYK-388 to propylene glycol methyl ether acetate, mix well, and filter through a 0.45 μm filter membrane to obtain the final product.

[0042] Example 2 An organic antireflective coating composition, by weight, comprises the following raw materials: 5 parts of the matting resin of Preparation Example 8, 1 part of 4,4'-diaminodicyclohexylmethane, 0.2 parts of BYK-307, and 90 parts of cyclohexanone.

[0043] The preparation method of the above-mentioned organic antireflective coating composition includes the following steps: Add matting resin, 4,4'-diaminodicyclohexylmethane, and BYK-307 to cyclohexanone, mix well, and filter through a 0.45μm filter membrane to obtain the final product.

[0044] Example 3 An organic antireflective coating composition, by weight, comprises the following raw materials: 10 parts of the matting resin of Preparation Example 9, 5 parts of 4,4'-diaminodicyclohexylmethane, 1 part of BYK-388, and 100 parts of propylene glycol monomethyl ether.

[0045] The preparation method of the above-mentioned organic antireflective coating composition includes the following steps: Add matting resin, 4,4'-diaminodicyclohexylmethane, and BYK-388 to propylene glycol monomethyl ether, mix well, and filter through a 0.45μm filter membrane to obtain the final product.

[0046] Comparative Example 1 The difference between Comparative Example 1 and Example 1 is that the matting resin of Preparation Example 10 was used instead of the matting resin of Preparation Example 7.

[0047] Comparative Example 2 The difference between Comparative Example 2 and Example 1 is that 1,5-diaminopentane is used instead of 4,4'-diaminodicyclohexylmethane.

[0048] Experimental Example 1 Film thickness uniformity: The organic anti-reflective coating prepared in the examples or comparative examples was spin-coated onto the surface of the silicon wafer, and then baked at 160°C for 120s. After crosslinking, 100 points were taken to measure the film thickness uniformity of the coating surface. Film thickness uniformity = (maximum film thickness - minimum film thickness) / (maximum film thickness + minimum film thickness) × 100%. The test results are shown in Table 1.

[0049] Corrosion resistance: Refer to GB / T 10125-2021 "Artificial Atmosphere Corrosion Test - Salt Spray Test" to test the resistance of each sample to neutral salt spray, and record the time when the coating blistering or cracking occurs. The test results are shown in Table 1.

[0050] Anti-reflection performance: The organic anti-reflection coatings of the examples or comparative examples were spin-coated onto the wafer at a speed of 1500 rpm, and then baked at 150°C for 60 s to form a bottom anti-reflection coating (BARC coating) with a thickness of 800 Å. The refractive index n of each BARC coating was then measured at a wavelength of 193 nm using a spectroelastic elliptic analyzer. The results are shown in Table 1.

[0051] Table 1 The experimental results in Table 1 show that the organic antireflective coatings prepared in Examples 1-3 of this invention exhibit excellent film thickness uniformity, salt spray resistance, and antireflective properties. In Comparative Example 1, the use of hydroxyethyl acrylate instead of acrylate monomer A resulted in a significant decrease in film thickness uniformity and antireflective properties. In Comparative Example 2, the use of 1,5'-diaminopentane instead of the crosslinking agent of this invention significantly reduced salt spray resistance. In summary, acrylate monomer A is crucial for ensuring high film thickness uniformity and a suitable refractive index, while 4,4'-diaminodicyclohexylmethane plays an irreplaceable role in improving salt spray resistance.

[0052] The above embodiments are merely preferred embodiments of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-substantial changes and substitutions made by those skilled in the art based on the present invention shall fall within the scope of protection claimed by the present invention.

Claims

1. An organic antireflective coating composition, characterized in that, By weight, it includes the following raw materials: 5-10 parts of matting resin, 1-5 parts of crosslinking agent, 0.2-1 parts of surfactant, and 90-100 parts of organic solvent; The preparation process of the matting resin is as follows: Methyl methacrylate, glycidyl methacrylate, methyl 9-anthracene methacrylate, and acrylate monomer A are added to 1,4-dioxane. Under inert gas protection, an initiator is added, and the reaction is purified to obtain the product. The structural formula of the acrylate monomer A is: ； The preparation process of the acrylate monomer A is as follows: (1) Under inert gas protection, biuret, 1 / 2-3 / 4 of 5,3'-diisocyanate-7,4'-dimethoxyflavone and dibutyltin dilaurate were added to tetrahydrofuran. After reflux reaction, the remaining 5,3'-diisocyanate-7,4'-dimethoxyflavone was added. After further reaction and purification, intermediate 1 was obtained. The structural formula of the 5,3'-diisocyanate-7,4'-dimethoxyflavonoid is: The structural formula of intermediate 1 is: (2) Under the protection of an inert gas, the intermediate 1 and dibutyltin dilaurate were added to dichloromethane, and then hydroxyethyl acrylate was added. After the reaction, the mixture was purified to obtain the acrylate monomer A. The crosslinking agent is 4,4'-diaminodicyclohexylmethane.

2. The organic antireflective coating composition according to claim 1, characterized in that, The molar ratio of methyl methacrylate, glycidyl methacrylate, methyl 9-anthracene methacrylate, and acrylate monomer A is 1:(3.5-4):(1.5-2):(0.5-0.8); the amount of initiator added is 0.2-0.5% of the total mass of the reactants; the initiator is azobisisobutyronitrile; the reaction temperature is 80-90℃, and the reaction time is 9-12h.

3. The organic antireflective coating composition according to claim 1, characterized in that, In step (1), the molar ratio of biuret, 5,3'-diisocyanate-7,4'-dimethoxyflavone, and dibutyltin dilaurate is 1:(2.2-2.4):(0.005-0.006); the reflux reaction time is 5-8 h; the reaction time is 6-9 h; in step (2), the molar ratio of intermediate 1, hydroxyethyl acrylate, and dibutyltin dilaurate is 1:(1-1.04):(0.004-0.006); the reaction time is 5-8 h.

4. The organic antireflective coating composition according to claim 3, characterized in that, The preparation process of the 5,3'-diisocyanate-7,4'-dimethoxyflavone is as follows: (a) 5,3'-dihydroxy-7,4'-dimethoxyflavone was added to N,N-dimethylformamide, a first portion of sodium hydroxide was added, and after stirring for 1-2 h, 2-bromo-2-methylpropionamide was added. After stirring for 12-14 h, a second portion of sodium hydroxide was added. After reacting at 50-55 °C for 5-6 h, water and a third portion of sodium hydroxide were added, and the mixture was refluxed. After purification, 5,3'-diamino-7,4'-dimethoxyflavone was obtained. The structural formula of the 5,3'-diamino-7,4'-dimethoxyflavonoid is: (b) The 5,3'-diamino-7,4'-dimethoxyflavone was added to acetonitrile, and then 4-dimethylaminopyridine and ditert-butyl dicarbonate were added in sequence. After the reaction, the mixture was purified to obtain the 5,3'-diisocyanate-7,4'-dimethoxyflavone.

5. The organic antireflective coating composition according to claim 4, characterized in that, The ratio of 5,3'-dihydroxy-7,4'-dimethoxyflavone, the first part of sodium hydroxide, 2-bromo-2-methylpropionamide, the second part of sodium hydroxide, the third part of sodium hydroxide, and water in step (a) is 1 mmol: (3-4) mmol: (3-4) mmol: (9-10) mmol: (6-7) mmol: (1.5-2) mL; the reflux reaction time is 1-2 h.

6. The organic antireflective coating composition according to claim 4, characterized in that, The molar ratio of 5,3'-diamino-7,4'-dimethoxyflavone, 4-dimethylaminopyridine, and ditert-butyl dicarbonate in step (b) is 1:(0.1-0.15):(2.2-2.3); the reaction time is 2-4 h.

7. The organic antireflective coating composition according to claim 1, characterized in that, The surfactant is BYK-388 or BYK-307; the organic solvent is selected from propylene glycol methyl ether acetate, cyclohexanone, and propylene glycol monomethyl ether.

8. A method for preparing the organic antireflective coating composition according to any one of claims 1-7, characterized in that, Includes the following steps: Add matting resin, crosslinking agent, and surfactant to an organic solvent and mix thoroughly to obtain the final product.

9. The application of an organic antireflective coating composition according to any one of claims 1-7, characterized in that, It is used in photolithography processes.

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