Fluorine-containing resin powder, photoresist composition containing fluorine-containing resin powder as well as preparation method and application of photoresist composition

Abstract

The invention provides a fluorine-containing resin powder and a photoresist composition containing the same. The powdery fluorine-containing resin is obtained through low-temperature sedimentation, sedimentation temperature control, sedimentation agent adding proportion control, sedimentation steps and the like, has the advantages of low residual monomer content, small solvent residual quantity and better storage stability, can prevent water from leaching effective components such as PAG and Quencher of a photoresist on the top layer in an immersed type ArF, and has the advantages of simple preparation process and low cost. The performance characterization analysis and the storage stability are obviously improved.

Description

Technical Field

[0001] The invention belongs to the technical field of photoresists, and particularly relates to fluorine-containing resin powder in photoresists, a preparation method and application thereof. Background Art

[0002] Photolithography is commonly used to manufacture fine structures in various electronic devices such as semiconductor devices and liquid crystal devices. In order to achieve such fine patterns, in addition to achieving high resolution and high sensitivity by adjusting the structure and composition of the resist, it can also be achieved by shortening the wavelength of the light source of the exposure device used, increasing the numerical aperture of the lens, etc. Immersion exposure, the part between the lens and the photoresist film on the wafer is filled with a solvent (liquid) with a refractive index greater than that of air. This immersion lithography can achieve the same high resolution as when using a light source with a shorter wavelength or using a high NA lens, even if a light source with the same exposure wavelength is used. At present, when preparing mid-to-high-end chips, light with a wavelength of about 193nm is used as the light source, and lithography is performed by immersion.

[0003] During immersion photolithography, the immersion medium contacts the resist film and lens during exposure. Substances contained in the resist leach into the immersion medium, degrading the resist film and reducing its performance. This can contaminate the lens surface and adversely affect lithographic properties. Current immersion photoresists incorporate fluororesins into their formulations. Due to the strong electronegativity and low polarizability of fluorine atoms, fluororesins for ArF photoresists are incorporated into immersion photoresist formulations as additives due to their low surface energy. These resins can self-segregate onto the top layer of the photoresist, preventing water from leaching active photoresist components such as PAG and Quencher.

[0004] However, fluororesins tend to form a gel-like substance during the preparation process, making them difficult to filter and dry, resulting in relatively large amounts of residual solvent and water. Furthermore, after drying, they tend to form lumps, forming films rather than powders, which severely impacts the storage and transportation of the fluororesins. Furthermore, their addition to photoresist compositions can significantly affect the performance of the resulting photoresists. Therefore, there is a need to provide a fluororesin powder and a preparation method that effectively prevents polymer agglomeration, improves its storage stability, and enhances its performance in photoresist applications. Summary of the Invention

[0005] Therefore, in order to solve the above problems, the present invention provides a fluorine-containing resin powder for immersion ArF photoresist in a first aspect, which is as follows:

[0006] The fluorine-containing resin is composed of a monomer M1, a monomer M2 and a monomer M3; the monomer M1 has a structure shown in formula I; the monomer M2 has a structure shown in formula II; the monomer M3 has a structure shown in formula III;

[0007] Formula I Formula II Formula III

[0008] wherein R5, R6, and R7 are each independently selected from one of H, methyl, ethyl, and isopropyl; R1, R2, and R4 are each independently selected from one of substituted or unsubstituted phenyl, adamantyl, norbornyl, and cycloalkyl; R3 is independently selected from one of substituted or unsubstituted methylene, ethylene, propylene, and phenylene; the substituted group is selected from at least one of H, methyl, ethyl, isopropyl, hydroxyl, carbonyl, and ester; and L is a methylene group in which at least one hydrogen atom is replaced by a fluorine atom.

[0009] The residual monomer content of the fluorine-containing resin powder is 200-1000 ppm; the residual solvent content of the fluorine-containing resin powder is 10-500 ppm; further, the residual monomer content of the fluorine-containing resin powder is 200-600 ppm; the residual solvent content of the fluorine-containing resin powder is 100-400 ppm.

[0010] Furthermore, the particle size distribution of the fluorine-containing resin powder is D10=0.1-10 μm, D50=0.1-50 μm, and D90=0.1-80 μm. Furthermore, the particle size distribution of the fluorine-containing resin powder is D10=1-10 μm, D50=5-20 μm, and D90=10-30 μm.

[0011] The second aspect of the present invention provides a method for preparing the above-mentioned fluorine-containing resin powder, comprising a fluorine-containing resin synthesis step and a fluorine-containing resin purification step;

[0012] Further, the purification step of the fluorine-containing resin comprises the following steps:

[0013] S1 controls the temperature of the reaction liquid and the precipitant after the reaction is completed;

[0014] S2: The temperature-controlled reaction solution is added dropwise to the sedimentation agent, and stirring is maintained during the addition process. Stirring is continued after the addition is completed. Solid-liquid separation is performed by centrifugal filtration, and finally drying is performed to obtain a fluorine-containing resin powder product.

[0015] Furthermore, the fluorine-containing resin is a polymethacrylate fluorine-containing resin;

[0016] Furthermore, the temperature control range is -40°C-5°C, and the temperature difference between the reaction liquid and the sedimentation agent is not higher than 10°C; preferably, the temperature control range is -40°C-0°C, and the temperature difference between the reaction liquid and the sedimentation agent is not higher than 5°C;

[0017] Furthermore, the volume ratio of the reaction solution to the sedimentation solvent is 1:(3-20); preferably 1:(5-10);

[0018] Furthermore, the reaction solution is added at a rate of 100-500 mL / min; the stirring speed is 100-300 rpm; and the stirring time is 10-180 min.

[0019] Furthermore, the sedimentation solvent is selected from at least one of pentane, cyclopentane, hexane, cyclohexane, heptane, petroleum ether, toluene, ethyl acetate, acetone, acetonitrile, dichloromethane, dichloroethane, methanol, ethanol, isopropanol, n-butanol, and water.

[0020] Furthermore, the preparation process of the fluorine-containing resin includes the following steps:

[0021] (i) dissolving a portion of the initiator and a portion of the monomers M1, M2, and M3 in a solvent and heating to a stable reflux state;

[0022] (ii) dissolving the remaining monomers M1, M2, M3 and the remaining initiator in a solvent to obtain a solution;

[0023] (iii) Under an inert environment, the solution obtained in step (ii) is added dropwise to the solution in step (i), and the mixture is aged while maintaining the reaction temperature to obtain a reaction solution.

[0024] Furthermore, in the step (iii), the dropwise addition time is 1-8 hours; the aging time is 0-6 hours; and the reaction temperature is 75-90°C.

[0025] Furthermore, the initiator is selected from at least one of an azo initiator and an organic peroxide initiator; the azo initiator is selected from at least one of azobisisobutyronitrile, azobisisoheptanenitrile, and dimethyl azobisisobutyrate; the organic peroxide initiator is selected from at least one of dibenzoyl peroxide, cyclohexanone peroxide, dodecyl peroxide, and tert-butyl peroxyvalerate;

[0026] A third aspect of the present invention provides use of the fluorine-containing resin powder in a photoresist composition.

[0027] A fourth aspect of the present invention provides a photoresist composition comprising (A) an alkali-soluble resin, (B) a photoacid generator, (C) an acid diffusion controller, (D) a fluorine-containing resin powder, and (E) a solvent;

[0028] Furthermore, the photoresist composition comprises, based on 100 parts by weight of (A) the alkali-soluble resin, 0.1 to 30 parts by weight of (B) a photoacid generator, 0.1 to 30 parts by weight of (C) an acid diffusion controller, and 0.5 to 30 parts by weight of (D) a fluorine-containing resin powder.

[0029] A fifth aspect of the present invention provides use of the above-mentioned photoresist composition in an immersion ArF reactor.

[0030] Beneficial effects:

[0031] The present invention provides a fluorine-containing resin powder and a preparation method thereof. The fluorine-containing resin reaction liquid at a certain temperature is dropwise added to a precipitant at a certain temperature. Under the temperature system, the precipitant system has good solubility for the initiator and the residual monomer. Under the precipitation system, the fluorine-containing resin polymer can be formed into a powdery product. The residual monomer and residual solvent contained in the powdered product are significantly reduced. The powdered product can be used in an immersion photoresist to reduce the dissolution of the effective components of the photoresist. DETAILED DESCRIPTION

[0032] Specific embodiments of the present invention will be described in detail below, but the present invention is not limited to the embodiments including the following examples, and various modifications can be made within the scope that can achieve the object of the invention and does not depart from the gist of the invention.

[0033] In the present invention, the photoresist composition includes (A) an alkali-soluble resin, (B) a photoacid generator, (C) an acid diffusion controller, (D) a fluorine-containing resin powder, and (E) a solvent.

[0034] (A) Alkali-soluble resin

[0035] In the present invention, the alkali-soluble resin present as the main resin of the immersion photoresist is mainly a polyacrylate alkali-soluble resin. As an example, the polyacrylate alkali-soluble resin used in this application is In addition, you can also choose [PHS-MAdMA (60 / 40)], [NBHFA-MAdMA (40 / 15 / 45)], [NBHFA-MCpMA, (40 / 15 / 45)] and other commonly used polyacrylate alkali-soluble resins in this field.

[0036] (B) Photoacid generator

[0037] The photoacid generator generates acid when exposed to light, which can cause the side groups of the main resin and the fluorine-containing resin to fall off, thereby changing the solubility of the main resin and the fluorine-containing resin. In the embodiment of the present application, the photoacid generator includes at least one of an iodonium salt and a sulfonium salt. As an example, the photoacid generator in the embodiment of the present application and the comparative example is a sulfonium salt, specifically The amount of the acid diffusion controller of the present invention is 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, relative to 100 parts by mass of the alkali-soluble resin (A). Specifically, the amount can be within the range of 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 parts by mass, or any two thereof.

[0038] (C) Acid diffusion controller

[0039] The acid diffusion controller is also an ionic organic compound, and the acidity of the quencher is lower than that of the photoacid generator. In this way, the quencher can capture the excess acid compounds generated by the PAG to prevent other areas of the matrix resin that are not exposed to light from being denatured. As an example, the acid diffusion controller in the examples and comparative examples of the present application is The amount of the acid diffusion controller of the present invention added is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, relative to 100 parts by mass of the main resin (A). Specifically, it can be, for example, 0.1 to 30, preferably 0.5 to 20, and specifically can be 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 parts by mass or any two thereof.

[0040] (D) Fluorine-containing resin powder

[0041] The fluororesin prepared in the present invention is a powdered solid having a particle size distribution of D10 = 0.1-10 μm, D50 = 0.1-50 μm, and D90 = 0.1-80 μm. In embodiments of the present invention, the particle size distribution of the fluororesin is D10 = 1-10 μm, D50 = 5-20 μm, and D90 = 10-30 μm. D10, D50, and D90 represent the particle size values ​​corresponding to the 10%, 50%, and 90% cumulative particle size distribution percentages in the particle size distribution curve of the fluororesin powder.

[0042] In the present invention, the residual monomer content in the fluororesin powder is 200-1000 ppm, and the residual solvent content in the fluororesin powder is 10-500 ppm. In embodiments of the present invention, the residual monomer content in the fluororesin powder is 200-600 ppm, and the residual solvent content in the fluororesin powder is 100-400 ppm. The lower the residual monomer and residual solvent content in the fluororesin powder, the easier it is to store and transport the product, and the more advantageous it is for use in photoresists, improving lithographic performance and reducing defects.

[0043] The fluorine-containing resin in the present invention is a polymethacrylate fluorine-containing resin, which is used in an ArF immersion photoresist composition. It is added to the formulation of the immersion photoresist composition as an additive and can self-segregate to the top layer of the photoresist composition to prevent water from leaching effective components of the photoresist composition, such as PAG, Quencher, etc.

[0044] In the present invention, the polymethacrylate fluorine-containing resin is composed of a monomer M1, a monomer M2 and a monomer M3; the monomer M1 has a structure shown in formula I; the monomer M2 has a structure shown in formula II; the monomer M3 has a structure shown in formula III;

[0045] Formula I Formula II Formula III

[0046] wherein R5, R6, and R7 are each independently selected from one of H, methyl, ethyl, and isopropyl; R1, R2, and R4 are each independently selected from one of substituted or unsubstituted phenyl, adamantyl, norbornyl, and cycloalkyl; R3 is independently selected from one of substituted or unsubstituted methylene, ethylene, propylene, and phenylene; the substituted group is selected from at least one of H, methyl, ethyl, isopropyl, hydroxyl, carbonyl, and ester; and L is a methylene group in which at least one hydrogen atom is replaced by a fluorine atom.

[0047] In the present invention, the polymethacrylate fluorine-containing resin is composed of 0-50 mol% of monomer M1, 0-50 mol% of monomer M2 and 0-80 mol% of monomer M3. In the present invention, the molar ratio of the fluorine-containing monomer M3 to the total monomers is preferably 40 mol%-80 mol%.

[0048] In the present invention, the preparation of fluorine-containing resin powder includes a resin synthesis step and a resin purification step. The synthesis process of polymethacrylate fluorine-containing resin includes the following steps:

[0049] (i) in an inert gas environment, dissolving a portion of the initiator and a portion of the monomers M1, M2, and M3 in a solvent and heating to a stable reflux state;

[0050] (ii) dissolving the remaining monomers M1, M2, M3 and the remaining initiator in a solvent to obtain a solution;

[0051] (iii) Under an inert environment, the solution obtained in step (ii) is added dropwise to the solution in step (i), and the mixture is aged while maintaining the reaction temperature to obtain a reaction solution.

[0052] In step (i), a conventional solvent used in the art for such reactions can be selected. In the present invention, acetonitrile is selected as the solvent. The amounts of initiator and monomer used can be determined based on actual conditions. In the present invention, approximately 10% of the total amount is selected for the reaction. The selected ratio is related to the actual reaction volume and the total reaction scale and is not fixed. It can be determined by those skilled in the art using conventional techniques.

[0053] In step (ii), the solvent selected is generally the same as that in step (i); in step (iii), the dropwise addition time is 1-8 hours; the aging time is 0-6 hours; and the reaction temperature is 75-90°C.

[0054] In the preparation process, the initiator is selected from at least one of an azo initiator and an organic peroxide initiator; the azo initiator is selected from at least one of azobisisobutyronitrile, azobisisoheptanenitrile, and dimethyl azobisisobutyrate; the organic peroxide initiator is selected from at least one of dibenzoyl peroxide, cyclohexanone peroxide, dodecyl peroxide, and tert-butyl peroxyvalerate;

[0055] In the present invention, in order to obtain a powdered fluorine-containing resin product, the synthesized fluorine-containing resin needs to be purified by post-treatment operations:

[0056] S1: Control the temperature of the reaction liquid and the sedimentation agent after the reaction is completed. The temperature control range is -40°C to 5°C, and the temperature difference between the reaction liquid and the sedimentation agent is not higher than 10°C;

[0057] S2 adds the temperature-controlled reaction liquid dropwise to the sedimentation agent, with the volume ratio of the reaction liquid to the sedimentation solvent being 1:(3-20); and maintaining stirring during the dropwise addition process, with the dropwise addition rate of the reaction liquid being 100-500 mL / min; the stirring speed being 100-300 rpm; and continuing stirring after the dropwise addition is completed, with the continued stirring time being 10-180 min; after the stirring is completed, performing solid-liquid separation by centrifugal filtration, and finally drying to obtain a fluorine-containing resin powder product.

[0058] The sedimentation solvent in the present invention is selected from at least one of pentane, cyclopentane, hexane, cyclohexane, heptane, petroleum ether, toluene, ethyl acetate, acetone, acetonitrile, dichloromethane, dichloroethane, methanol, ethanol, isopropanol, n-butanol and water.

[0059] The lower limit of the amount of the fluororesin powder (D) relative to 100 parts by mass of the alkali-soluble resin (A) is preferably 0.1 parts by mass, more preferably 0.5 parts by mass, more preferably 1 part by mass, and particularly preferably 2 parts by mass. The upper limit of the amount of the fluororesin powder (D) is preferably 30 parts by mass, more preferably 20 parts by mass, more preferably 15 parts by mass, and particularly preferably 10 parts by mass. Specifically, for example, the amount of the fluororesin powder (D) relative to 100 parts by mass of the alkali-soluble resin (A) may be any of 1 part by mass, 2 parts by mass, 3 parts by mass, 4 parts by mass, 5 parts by mass, 6 parts by mass, 7 parts by mass, 8 parts by mass, 9 parts by mass, or 10 parts by mass, or within the range of any two of these.

[0060] (E) Solvent

[0061] In the resist composition, the organic solvent can dissolve other components and ensure that the components of the resist composition are uniform, so that a higher resolution photolithographic pattern can be formed when applied. As long as the organic solvent can dissolve other components, there is no specific limitation. For example, the organic solvent can be a ketone solvent such as cyclohexanone, methyl-2-n-amyl ketone; an alcohol solvent such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol; an ether solvent such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether; an ester solvent such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate; a lactone solvent such as γ-butyrolactone; or any one or more mixed solvents. Among these organic solvents, propylene glycol monomethyl ether acetate, cyclohexanone, γ-butyrolactone, and mixed solvents thereof are generally preferred to ensure good solubility. Specifically, in the embodiment of the present application, propylene glycol methyl ether acetate is used as the organic solvent.

[0062] Example

[0063] In the following examples, unless otherwise specified, the raw materials, reagents or processing techniques used are all commercially available raw materials or conventional processing techniques commonly used in the art.

[0064] The synthesis of the fluorine-containing resins in Examples 1-7 of the present invention and Comparative Examples 1-6 is as follows:

[0065] In a 5L four-necked reaction flask equipped with a thermometer, a reflux condenser, a mechanical stirrer, and nitrogen, 550 g of acetonitrile solvent, 9 g of 1-isopropylcyclopentyl methacrylate, 21.5 g of 2-methyl-2-methylacrylate adamantyl ester, 57.3 g of tert-butyl 2,2-difluoro-3-(methacryloyloxy) valerate, and 4 g of initiator V601 were first added. The mixture was mechanically stirred until it dissolved, then the temperature was raised to a stable reflux state. 1284 g of acetonitrile solvent, 80.9 g of 1-isopropylcyclopentyl methacrylate, 193.1 g of 2-methyl-2-methacrylate adamantyl ester, 515.8 g of tert-butyl 2,2-difluoro-3-(methacryloyloxy)valerate, and 35.6 g of initiator V601 were stirred until dissolved. The mixture was then added dropwise to a 5 L four-necked reaction flask under a nitrogen atmosphere for 6 hours. After the addition was complete, the mixture was matured at 81°C for 2 hours. The reaction solution was obtained and used for later use.

[0066] Example 1

[0067] The reaction solution obtained after the reaction was completed was cooled to -20°C, and 5 kg of the sedimentation solvent ethanol was also cooled to -20°C. 1 kg of the reaction solution was added dropwise to the sedimentation kettle at a rate of 175 mL / min with a stirring speed of 160 rpm. After the addition was completed, stirring was continued for 3 hours to precipitate. After filtration, washing, and drying, a powdered fluorine-containing resin was obtained.

[0068] Example 2

[0069] The reaction solution obtained after the reaction was completed was cooled to 0°C, and 7.5 kg of the sedimentation solvent n-heptane was also cooled to 0°C. 1 kg of the reaction solution was added dropwise to the sedimentation kettle at 475 mL / min with a stirring speed of 300 rpm. After the addition was completed, stirring was continued for 2 hours to precipitate. After filtration, washing and drying, a powdered fluorine-containing resin was obtained.

[0070] Example 3

[0071] The reaction solution obtained after the reaction was cooled to -10°C, and 5 kg of dichloromethane, a sedimentation solvent, was also cooled to -10°C. 0.5 kg of the reaction solution was added dropwise to the sedimentation kettle at a rate of 300 mL / min with a stirring speed of 100 rpm. After the addition was completed, stirring was continued for 3 hours to precipitate. After filtration, washing, and drying, a powdered fluorine-containing resin was obtained.

[0072] Example 4

[0073] The reaction solution obtained after the reaction was completed was cooled to -20°C, and 5 kg of the sedimentation solvent ethanol was also cooled to -25°C. 1 kg of the reaction solution was added dropwise to the sedimentation kettle at 175 mL / min with a stirring speed of 160 rpm. After the addition was completed, stirring was continued for 3 hours to precipitate. After filtration, washing, and drying, a powdered fluorine-containing resin was obtained.

[0074] Example 5

[0075] The reaction solution obtained after the reaction was cooled to -20 ° C, 3 kg of the sedimentation solvent methanol: water = 2:8 v / v was also cooled to -20 ° C, 1 kg of the reaction solution was added dropwise to the sedimentation kettle at 175 mL / min, and the stirring speed was 100 rpm. After the addition was completed, stirring was continued for 3 hours to precipitate. After filtration, washing and drying, a powdered fluorine-containing resin was obtained.

[0076] Example 6

[0077] The reaction solution obtained after the reaction was cooled to -40°C, and 7.5 kg of the sedimentation solvent toluene was also cooled to -40°C. 1 kg of the reaction solution was added dropwise to the sedimentation kettle at 475 mL / min with a stirring speed of 300 rpm. After the addition was completed, stirring was continued for 2 hours to precipitate. After filtration, washing and drying, a powdered fluorine-containing resin was obtained.

[0078] Example 7

[0079] The reaction solution obtained after the reaction was cooled to -15 ° C, and 5 kg of sedimentation solvent ethanol was also cooled to -10 ° C. 1 kg of the reaction solution was added dropwise to the sedimentation kettle at 175 mL / min with a stirring speed of 160 rpm. After the addition was completed, stirring was continued for 3 hours to precipitate. After filtration, washing and drying, a powdered fluorine-containing resin was obtained.

[0080] Comparative Example 1

[0081] The same as Example 1, except that after the reaction was completed, the reaction solution was cooled to 20° C. and the settling solvent was also cooled to 20° C. As a result, no powdery fluorine-containing resin was obtained, but it quickly agglomerated into a fluid colloid.

[0082] Comparative Example 2

[0083] The same as Example 1, except that after the reaction, the reaction solution was cooled to -20° C. and the precipitation solvent was cooled to 10° C. As a result, no powdery fluorine-containing resin was obtained, but it quickly agglomerated into a fluid colloid.

[0084] Comparative Example 3

[0085] The same as Example 1, except that after the reaction was completed, the reaction solution was cooled to 20° C. and the precipitation solvent was cooled to −20° C. As a result, no powdery fluorine-containing resin was obtained, but it quickly agglomerated into a fluid colloid.

[0086] Comparative Example 4

[0087] The same as Example 1, except that after the reaction was completed, the reaction solution was cooled to -20° C. and the precipitation solvent was cooled to 0° C. As a result, large lumps of sticky solids appeared, and no powdered fluorine-containing resin was obtained.

[0088] Comparative Example 5

[0089] The same as Example 1, except that the amount of the sedimentation agent used was 1.5 kg. As a result, no powdery fluorine-containing resin was obtained, but rather sticky large solid lumps appeared.

[0090] Comparative Example 6

[0091] The same as Example 1, except that 5 kg of sedimentation agent was added dropwise to the reaction solution at 175 mL / min. As a result, no powdery fluororesin was obtained, but the resin quickly agglomerated into a flowing colloid.

[0092] The fluorine-containing resin products obtained in Examples 1-7 and Comparative Examples 1-6 were tested:

[0093] <Particle size>

[0094] A powdered fluorine-containing resin sample is added to a Mastersizer laser particle size analyzer for testing to obtain the D50, D90 and D10 values ​​of the particles.

[0095] <Residual Monomers>

[0096] Measure the residual monomer content in the product by high performance liquid chromatography

[0097] <Residual Solvents>

[0098] Determine the amount of residual solvents in chemical samples using gas chromatography.

[0099] Table 1

[0100] D10 (μm) D50 (μm) D90 (μm) Residual monomer ppm Residual solvent ppm Example 1 4.639 10.24 17.27 247 143 Example 2 6.072 12.91 19.78 294 169 Example 3 9.173 16.94 27.61 218 126 Example 4 5.189 17.08 29.49 395 307 Example 5 4.113 11.69 21.97 498 281 Example 6 4.185 9.77 17.81 301 138 Example 7 6.172 14.79 23.43 591 392 Comparative Example 1 / / / 13785 6427 Comparative Example 2 / / / 6738 3941 Comparative Example 3 / / / 6861 4376 Comparative Example 4 / / / 3413 1076 Comparative Example 5 / / / 3069 938 Comparative Example 6 / / / 5973 4901

[0101] Application Example 1

[0102] The fluorine-containing resin of Example 1 was added as an additive to the photoresist composition:

[0103] 100 parts by mass of the photoresist composition resin polymer , 14.0 parts by mass of an acid generator , 2.3 parts by mass of acid diffusion controller , 3.0 parts by mass (solid content) of the fluorine-containing resins of Examples 1-7 and Comparative Examples 1-6, and 3,230 parts by mass of propylene glycol monomethyl ether acetate as a solvent were mixed, and then the mixture was filtered through a membrane filter with a pore size of 0.2 μm to prepare a photoresist composition 1.

[0104] The photoresist compositions of Application Examples 2-6 were prepared using Examples 2 and 6 and Comparative Examples 1, 4, and 6, as shown in Table 2.

[0105] <Dynamic contact angle test>

[0106] The prepared photoresist composition was spin-coated onto a silicon wafer using a spin coater. The immersion photoresist was then dried and cured to form a 110 nm photoresist film. The dynamic water contact angles of the immersion photoresists prepared with the fluorine-containing resins of each example and comparative example were then measured using a dynamic contact angle meter.

[0107] <Development Defect Test>

[0108] After measuring the dynamic water contact angle, an immersion ArF excimer laser scanner (Nikon NSR-S610C, NA = 1.30) was used to expose the immersion photoresist, and then a developer (2.38% by mass of TMAH aqueous solution) was used to develop for 10 seconds, and then rinsed with pure water to form a resist pattern on the mask. The number of defects on the wafer surface was then detected using a scanning electron microscope. When the total number of defects was less than 100 / wafer, it was evaluated as A (good), when the total number of defects was 100-500 / wafer, it was evaluated as B (general), and when the total number of defects was greater than 500 / wafer, it was evaluated as C (poor).

[0109] Table 2

[0110] Application Examples Fluorine-containing resin <![CDATA[ Advancing water contact angle° ]]> <![CDATA[ Receding water contact angle° ]]> <![CDATA[ Wafer defect evaluation ]]> 1 Example 1 88 79 A 2 Example 2 85 74 A 3 Example 6 89 77 A 4 Comparative Example 1 97 68 C 5 Comparative Example 4 92 65 B 6 Comparative Example 6 93 70 C

[0111] According to the present invention, powdered polymers can be easily and stably recovered, and resist polymers with low residual monomers and solvent content can be manufactured. These polymers have good hydrophobic properties and, when used in ArF immersion photoresists, can effectively limit the dissolution of effective components of the cured photoresist film in water, thereby reducing the number of defects on the wafer surface.

Claims

1. A photoresist composition, characterized in that The photoresist composition comprises (A) an alkali-soluble resin, (B) a photoacid generator, (C) an acid diffusion controller, (D) a fluorine-containing resin powder, and (E) a solvent. The fluorine-containing resin powder (D) has a residual monomer content of 200-1000 ppm and a residual solvent content of 10-500 ppm. The fluorine-containing resin powder has the following particle size distribution: D10 = 0.1-10 μm, D50 = 0.1-50 μm, and D90 = 0.1-80 μm. The resin in the fluorine-containing resin powder is obtained by reacting monomer M1, monomer M2, and monomer M3. The monomer M1 has a structure shown in formula I; the monomer M2 has a structure shown in formula II; and the monomer M3 has a structure shown in formula III. Formula I Formula II Formula III Wherein, R5, R6, and R7 are each independently selected from one of H, methyl, ethyl, and isopropyl; R1, R2, and R4 are each independently selected from one of substituted or unsubstituted phenyl, adamantyl, norbornyl, and cycloalkyl; R3 is independently selected from one of substituted or unsubstituted methylene, ethylene, propylene, and phenylene; the substituted group is selected from at least one of H, methyl, ethyl, isopropyl, hydroxyl, carbonyl, and ester; and L is a methylene group in which at least one hydrogen atom is replaced by a fluorine atom.

2. The photoresist composition according to claim 1, wherein Based on 100 parts by weight of (A) the alkali-soluble resin, the photoresist includes 0.1 to 30 parts by weight of (B) a photoacid generator, 0.1 to 30 parts by weight of (C) an acid diffusion controller, and 0.5 to 30 parts by weight of (D) a fluorine-containing resin powder.

3. A method for preparing fluorine-containing resin powder as claimed in claim 1 or 2, characterized in that: The method comprises a fluorine-containing resin synthesis step and a fluorine-containing resin purification step; The purification of the fluorine-containing resin specifically comprises the following steps: S1: Controlling the temperature of the reaction liquid and the sedimentation agent after the reaction is completed, wherein the temperature control range is -40°C to 5°C, and the temperature difference between the reaction liquid and the sedimentation agent is not higher than 10°C; S2: The reaction liquid after controlling the temperature is added dropwise to the sedimentation agent, the volume ratio of the reaction liquid to the sedimentation solvent is 1: (3-20), and stirring is maintained during the addition process. After the addition is completed, stirring is continued. After the stirring is completed, solid-liquid separation is performed by centrifugal filtration, and finally drying is performed to obtain a fluorine-containing resin powder product.

4. The preparation method according to claim 3, characterized in that The sedimentation solvent is selected from at least one of pentane, cyclopentane, hexane, cyclohexane, heptane, petroleum ether, toluene, ethyl acetate, acetone, acetonitrile, dichloromethane, dichloroethane, methanol, ethanol, isopropanol, n-butanol, and water.

5. The preparation method according to claim 3, characterized in that The reaction solution is added at a rate of 100-500 mL / min; and / or the stirring rate is 100-300 rpm; and / or the stirring time is 10-180 min.

6. The preparation method according to claim 3, characterized in that The volume ratio of the reaction solution to the sedimentation solvent is 1:(5-10).

7. The preparation method according to claim 3, characterized in that The synthesis steps of the fluorine-containing resin include: (i) dissolving part of the initiator and part of the monomers M1, M2, and M3 in a solvent and heating to a stable reflux state; (ii) dissolving the remaining monomers M1, M2, M3 and the remaining initiator in a solvent to obtain a solution; (iii) Under an inert environment, the solution obtained in step (ii) is added dropwise to the solution in step (i), and the mixture is aged while maintaining the reaction temperature to obtain a reaction solution.

8. The preparation method according to claim 7, characterized in that The initiator is selected from at least one of an azo initiator and an organic peroxide initiator; the azo initiator is selected from at least one of azobisisobutyronitrile, azobisisoheptanenitrile, and dimethyl azobisisobutyrate; the organic peroxide initiator is selected from at least one of dibenzoyl peroxide, cyclohexanone peroxide, dodecyl peroxide, and tert-butyl peroxyvalerate; and / or, in step (iii), the dropwise addition time is 1-8 hours; the aging time is 0-6 hours; and the reaction temperature is 75-90°C.

9. Fluorine-containing resin powder prepared by the preparation method according to any one of claims 3 to 8.

10. Use of the resist composition according to claim 1 or 2 or the fluorine-containing resin powder according to claim 9 in an immersion ArF reactor.

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