A fluorine-containing resin powder, a photoresist composition containing the same, and a method for preparing and using the same

Abstract

The application provides a fluorine-containing resin powder and a photoresist composition containing the same. The fluorine-containing resin powder is obtained by low-temperature settling, control of settling temperature and settling agent addition ratio, settling step method and the like, has the advantages of low residual monomer content, small solvent residual amount and better storage stability, can effectively prevent water from leaching out of effective components of the photoresist such as PAG and Quencher in the top layer in the ArF immersion mode, and has obvious improvement in performance characterization analysis and storage stability.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of photoresist, and particularly relates to a fluorine-containing resin powder in photoresist and a preparation method and application thereof. BACKGROUND

[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, 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. In immersion exposure, the part between the lens on the wafer and the photoresist film is filled with a solvent (liquid) with a refractive index greater than air, and this immersion lithography can achieve the same high resolution as using a light source with a shorter wavelength or using a high-NA lens, even if the same exposure wavelength is used. At present, when preparing medium and high-end chips, light with a wavelength of about 193 nm is used as the light source, and immersion lithography is used.

[0003] In immersion exposure, the immersion medium contacts the resist film and the lens during immersion exposure, and the substances contained in the resist dissolve into the immersion medium, the resist film deteriorates, the performance decreases, and the lens surface is contaminated, which has an adverse effect on the lithography characteristics. The current component of the immersion photoresist adds a fluorine-containing resin. Due to the strong electronegativity and low polarizability of fluorine atoms, the fluorine-containing resin in the ArF photoresist has the characteristics of low surface energy, and is added to the formula as an additive in the immersion photoresist, and can be self-condensed to the top layer of the photoresist to block the leaching of water to the effective components of the photoresist such as PAG, Quencher, etc.

[0004] However, the fluorine-containing resin is prone to form a gel-like substance during preparation, which is difficult to filter and dry, resulting in a relatively large amount of solvent and water residue; and after drying, it is easy to form a film instead of a powder, which seriously affects the storage and transportation of the fluorine-containing resin. Adding it to the photoresist composition will seriously affect the performance of the photoresist. Therefore, it is necessary to provide a fluorine-containing resin powder and a preparation method thereof, which can effectively avoid the occurrence of polymer agglomeration and improve the storage stability and performance in the application of photoresist. SUMMARY

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

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

[0007] Formula I Formula II Formula III

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

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

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

[0011] The second aspect of the present application provides a preparation method of the above-mentioned fluorine-containing resin powder, comprising a synthesis step of fluorine-containing resin and a purification step of fluorine-containing resin.

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

[0013] S1 temperature control of the reaction liquid after reaction and the settling agent;

[0014] S2 drop the reaction liquid after temperature control into the settling agent, and maintain stirring during the drop process, continue stirring after the drop is finished, and finally obtain the fluorine-containing resin powder product through solid-liquid separation by centrifugal filtration after the stirring is finished.

[0015] Further, the fluorine-containing resin is a polymethacrylate fluorine-containing resin.

[0016] Further, the temperature control range is-40℃-5℃, and the temperature difference between the reaction liquid and the settling agent is not higher than 10℃; preferably, the temperature control range is-40℃-0℃, and the temperature difference between the reaction liquid and the settling agent is not higher than 5℃.

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

[0018] Further, the dropping speed of the reaction solution is 100-500 mL / min; the stirring speed is 100-300 rpm; and the continued stirring time is 10-180 min.

[0019] Further, 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] Further, the preparation process of the fluorine-containing resin comprises the following steps:

[0021] (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;

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

[0023] (iii) under an inert environment, adding the solution obtained in step (ii) to the solution in step (i) in a dropping manner, maintaining the reaction temperature to perform ripening, and obtaining a reaction solution.

[0024] Further, in step (iii), the dropping time is 1-8 h; the ripening time is 0-6 h; and the reaction temperature is 75-90℃.

[0025] Further, the initiator is selected from at least one of azo initiators and organic peroxide initiators; the azo initiator is selected from at least one of azobisisobutyronitrile, azobisisoheptyl nitrile, and dimethyl azobis-2-methylpropionate; and the organic peroxide initiator is selected from at least one of dibenzoyl peroxide, cyclohexanone peroxide, dodecanoyl peroxide, and tert-butyl tert-amyl peroxide.

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

[0027] The fourth aspect of the present application provides a photoresist composition, which comprises (A) an alkali-soluble resin, (B) a photoacid generator, (C) an acid diffusion control agent, (D) a fluorine-containing resin powder, and (E) a solvent.

[0028] Further, the photoresist composition 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 control agent, and 0.5 to 30 parts by weight of (D) a fluorine-containing resin powder, based on 100 parts by weight of the (A) alkali-soluble resin.

[0029] The fifth aspect of the present application provides a use of the above photoresist composition in immersion ArF.

[0030] Advantages:

[0031] The present application provides a fluorine-containing resin powder and a preparation method thereof. The fluorine-containing resin reaction liquid at a certain temperature is added dropwise into a precipitant at a certain temperature. The precipitant system has good solubility to the initiator and residual monomer at the temperature system. The fluorine-containing resin polymer can form a powder product in the precipitating system, which significantly reduces the residual monomer and residual solvent, and can be applied in immersion photoresist to reduce the dissolution of effective components of the photoresist. DETAILED DESCRIPTION

[0032] Hereinafter, the specific embodiments of the present application will be described in detail, but the present application is not limited to the embodiments including the following examples, and various modifications can be made within the scope of the purpose of the application and without departing from the spirit of the application.

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

[0034] (A) Alkali-soluble resin

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

[0036] (B) Photoacid generator

[0037] The photoacid generator can generate acid under 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 present application, the photoacid generator includes at least one of iodonium salt and sulfonium salt. As an exemplary, the photoacid generator in the present application and the comparative examples is sulfonium salt, specifically The acid diffusion control agent is added in an amount of 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, relative to 100 parts by mass of the base-soluble resin (A). Specifically, the acid diffusion control agent can be added in an amount of 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 in a range between any two of these values.

[0038] (C) Acid diffusion control agent

[0039] The acid diffusion control agent 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 excess acid compounds generated by the PAG to prevent the denaturation of other areas of the base resin that are not exposed to light. As an example, the acid diffusion control agent in the examples and comparative examples of the present application is The acid diffusion control agent is added in an amount of 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, relative to 100 parts by mass of the base-soluble resin (A). Specifically, the acid diffusion control agent can be added in an amount of 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 in a range between any two of these values.

[0040] (D) Fluorine-containing resin powder

[0041] The fluorine-containing resin prepared in the present application is a powder solid, and the particle size distribution is D10 = 0.1-10 μm, D50 = 0.1-50 μm, and D90 = 0.1-80 μm. In the examples of the present application, the particle size distribution of the fluorine-containing resin 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 cumulative particle size distribution percentages of 10%, 50%, and 90% in the particle size distribution curve of the fluorine-containing resin powder.

[0042] In the present application, the residual monomer in the fluorine-containing resin powder is 200-1000 ppm, and the residual solvent in the fluorine-containing resin powder is 10-500 ppm. In the examples of the present application, the residual monomer in the fluorine-containing resin powder is 200-600 ppm, and the residual solvent in the fluorine-containing resin powder is 100-400 ppm. The smaller the residual monomer and residual solvent in the fluorine-containing resin powder, the more conducive to the storage and transportation of the product, and the more conducive to its application in photoresists, improving the performance of photolithography and reducing defects.

[0043] The fluorine-containing resin in the present application is a polymethacrylate fluorine-containing resin, which is applied in ArF immersion photoresist composition, added into the formula as an additive in the immersion photoresist composition, and can be self-condensed to the top layer of the photoresist composition to block the immersion of water to the effective components of the photoresist composition such as PAG, Quencher, etc.

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

[0045] Formula I Formula II Formula III

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

[0047] In the present application, 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, and the fluorine-containing monomer M3 is preferably 40 mol%-80 mol% of the total monomer in the present application.

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

[0049] (i) in an inert gas environment, part of the initiator and part of the monomers M1, M2, M3 are dissolved with a solvent, and heated to a stable reflux state;

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

[0051] (iii) in an inert environment, the solution obtained in step (ii) is added to the solution of step (i) in the form of drops, the reaction temperature is maintained to mature, and a reaction liquid is obtained.

[0052] In step (i), a conventional solvent in the art for carrying out such a reaction can be selected, and acetonitrile is selected as the solvent in the present application; the amount of initiator and monomer can be determined according to the actual situation, and about 10% of the total amount is selected for reaction in the present application. The selected ratio is related to the capacity of the actual reaction and the total scale of the reaction, and is not fixed, and those skilled in the art can determine it according to the conventional technical means in the art.

[0053] In step (ii), the selected solvent is generally consistent with step (i); in step (iii), the dropping time is 1-8h; the maturation time is 0-6h; and the reaction temperature is 75-90℃.

[0054] The initiator in the preparation process is selected from at least one of azo initiators and organic peroxide initiators; the azo initiator is selected from at least one of azobisisobutyronitrile, azobisisoheptyl nitrile and dimethyl azobis isobutyrate; and the organic peroxide initiator is selected from at least one of dibenzoyl peroxide, cyclohexanone peroxide, dodecanoyl peroxide and tert-butyl tert-pentyl peroxide;

[0055] In the present application, in order to obtain a powdery fluorine-containing resin product, a post-treatment operation of purifying the synthesized fluorine-containing resin is required:

[0056] S1, the reaction liquid after the reaction and the settling agent are temperature controlled, the temperature control range is-40℃-5℃, and the temperature difference between the reaction liquid and the settling agent is not higher than 10℃;

[0057] S2, the reaction liquid after temperature control is added to the settling agent, the volume ratio of the reaction liquid to the settling solvent is 1: (3-20); and stirring is maintained during the dropping process, the dropping speed of the reaction liquid is 100-500mL / min; the stirring speed is 100-300rpm; after the dropping is completed, the stirring is continued, the continued stirring time is 10-180min; after the stirring is completed, solid-liquid separation is carried out by centrifugal filtration, and finally the fluorine-containing resin powdery product is obtained.

[0058] The settling solvent in the present application 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 content of the fluorine-containing resin powder (D) relative to 100 parts by mass of the (A) alkali-soluble resin is preferably 0.1 part by mass, further preferably 0.5 part by mass, more preferably 1 part by mass, and particularly preferably 2 parts by mass. The upper limit of the content of the fluorine-containing resin powder (D) is preferably 30 parts by mass, further preferably 20 parts by mass, more preferably 15 parts by mass, and particularly preferably 10 parts by mass. Specifically, the fluorine-containing resin powder (D) can 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, 10 parts by mass, or a range between any two of them, relative to 100 parts by mass of the (A) alkali-soluble resin.

[0060] (E) Solvent

[0061] In the resist composition, the organic solvent functions to dissolve the other components, and ensures uniformity of the components of the resist composition, so that a higher resolution pattern can be formed when applied. The organic solvent is not particularly limited as long as it can dissolve the other components. For example, the organic solvent can be a ketone solvent such as cyclohexanone, methyl-2-n-pentyl ketone, and the like; an alcohol solvent such as 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, and the like; 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, and the like; an ester solvent such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, and the like; a lactone solvent such as γ-butyrolactone; or a mixture of any one or more thereof. Of these organic solvents, in order to ensure good solubility, propylene glycol monomethyl ether acetate, cyclohexanone, γ-butyrolactone, and a mixture thereof are generally preferred. Specifically, in the present application, the organic solvent is propylene glycol monomethyl ether acetate.

[0062] Examples

[0063] In each of the following examples, unless otherwise specifically stated, the raw materials or processing techniques used are commercially available raw materials or conventional processing techniques that are common in the art.

[0064] The fluorine-containing resins in Examples 1 to 7 and Comparative Examples 1 to 6 of the present application were synthesized as follows:

[0065] In a 5L four-necked reaction flask equipped with a thermometer, a reflux condenser, a mechanical stirrer, and a nitrogen inlet, 550g of solvent acetonitrile, 9g of 1-isopropylcyclopentyl methacrylate, 21.5g of 2-methyl-2-adamantyl methacrylate, 57.3g of 2,2-difluoro-3-(methacryloyloxy)pentanoic acid tert-butyl ester, and 4g of initiator V601 were added. After the solution was stirred to be clear, the temperature was raised to a stable reflux state. After the solution was stirred to be clear, 1284g of solvent acetonitrile, 80.9g of 1-isopropylcyclopentyl methacrylate, 193.1g of 2-methyl-2-adamantyl methacrylate, 515.8g of 2,2-difluoro-3-(methacryloyloxy)pentanoic acid tert-butyl ester, and 35.6g of initiator V601 were added dropwise into the 5L four-necked reaction flask under a nitrogen atmosphere. The dropwise addition was performed for 6h, and after the dropwise addition was completed, the reaction was allowed to mature at 81°C for 2h. After the reaction was completed, the reaction solution was obtained for use.

[0066] Example 1

[0067] The reaction solution obtained after the reaction was completed was cooled to -20°C, 5kg of a settling solvent ethanol was also cooled to -20°C, 1kg of the reaction solution was added dropwise into the settling kettle at 175mL / min, the stirring speed was 160rpm, after the dropwise addition was completed, the precipitation was precipitated after stirring for 3h, and after filtration, washing, and drying, a fluorine-containing resin in powder form was obtained.

[0068] Example 2

[0069] The reaction solution obtained after the reaction was completed was cooled to 0°C, 7.5kg of a settling solvent n-heptane was also cooled to 0°C, 1kg of the reaction solution was added dropwise into the settling kettle at 475mL / min, the stirring speed was 300rpm, after the dropwise addition was completed, the precipitation was precipitated after stirring for 2h, and after filtration, washing, and drying, a fluorine-containing resin in powder form was obtained.

[0070] Example 3

[0071] The reaction solution obtained after the reaction was completed was cooled to -10°C, 5kg of a settling solvent dichloromethane was also cooled to -10°C, 0.5kg of the reaction solution was added dropwise into the settling kettle at 300mL / min, the stirring speed was 100rpm, after the dropwise addition was completed, the precipitation was precipitated after stirring for 3h, and after filtration, washing, and drying, a fluorine-containing resin in powder form was obtained.

[0072] Example 4

[0073] The reaction solution obtained after the reaction was cooled to -20°C, 5 kg of the settling solvent ethanol was also cooled to -25°C, 1 kg of the reaction solution was added dropwise to the settling tank at 175 mL / min, the stirring speed was 160 rpm, after the addition was completed, the stirring was continued for 3 h, then the precipitate was separated out, after filtration, washing and drying, the fluorine-containing resin in powder form was obtained.

[0074] Example 5

[0075] The reaction solution obtained after the reaction was cooled to -20°C, 3 kg of the settling solvent methanol: water = 2:8 v / v was also cooled to -20°C, 1 kg of the reaction solution was added dropwise to the settling tank at 175 mL / min, the stirring speed was 100 rpm, after the addition was completed, the stirring was continued for 3 h, then the precipitate was separated out, after filtration, washing and drying, the fluorine-containing resin in powder form was obtained

[0076] Example 6

[0077] The reaction solution obtained after the reaction was cooled to -40°C, 7.5 kg of the settling solvent toluene was also cooled to -40°C, 1 kg of the reaction solution was added dropwise to the settling tank at 475 mL / min, the stirring speed was 300 rpm, after the addition was completed, the stirring was continued for 2 h, then the precipitate was separated out, after filtration, washing and drying, the fluorine-containing resin in powder form was obtained.

[0078] Example 7

[0079] The reaction solution obtained after the reaction was cooled to -15°C, 5 kg of the settling solvent ethanol was also cooled to -10°C, 1 kg of the reaction solution was added dropwise to the settling tank at 175 mL / min, the stirring speed was 160 rpm, after the addition was completed, the stirring was continued for 3 h, then the precipitate was separated out, after filtration, washing and drying, the fluorine-containing resin in powder form 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, the fluorine-containing resin in powder form was not obtained, but it quickly agglomerated into a flowing colloidal substance.

[0082] Comparative Example 2

[0083] 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 cooled to 10°C. As a result, the fluorine-containing resin in powder form was not obtained, but it quickly agglomerated into a flowing colloidal substance.

[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 settling solvent was cooled to -20°C. As a result, a powder-like fluorine-containing resin was not obtained, but rather, it rapidly agglomerated into a flowing 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 settling solvent was cooled to 0°C. As a result, a powder-like fluorine-containing resin was not obtained, but rather, a large amount of a viscous solid was produced.

[0088] Comparative Example 5

[0089] The same as Example 1, except that the amount of the settling agent was 1.5 kg. As a result, a powder-like fluorine-containing resin was not obtained, but rather, a large amount of a viscous solid was produced.

[0090] Comparative Example 6

[0091] The same as Example 1, except that 5 kg of the settling agent was added dropwise to the reaction solution at 175 mL / min. As a result, a powder-like fluorine-containing resin was not obtained, but rather, it rapidly agglomerated into a flowing colloid.

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

[0093] <Particle Size>

[0094] A powder-like fluorine-containing resin sample was added to a Mastersizer laser particle size meter and tested, and the D50, D90, and D10 values of the particles were obtained.

[0095] <Residual Monomer>

[0096] The residual monomer content in the product was measured by high-performance liquid chromatography

[0097] <Residual Solvent>

[0098] The residual solvent content in a chemical sample was measured by gas chromatography.

[0099] Table 1

[0100] D10 (pm) D50 (pm) D90 (pm) 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 a photoresist composition composition:

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

[0104] The photoresist compositions for use in Examples 2 to 6 were prepared using Examples 2, 6 and Comparative Examples 1, 4, 6, as shown in Table 2.

[0105] <Dynamic contact angle test>

[0106] The photoresist compositions prepared above were spin-coated on the surface of a silicon wafer using a spin coater, and then the spin-coated photoresist was baked to be cured to a photoresist film of 110 nm. Thereafter, the dynamic water contact angle of the immersion-type photoresist prepared from each of the fluorine-containing resins of the examples and comparative examples was measured using a dynamic contact angle meter.

[0107] <Developing defect test>

[0108] After the measurement of the dynamic water contact angle, the immersion-type photoresist was exposed using an immersion ArF excimer laser scanner (Nikon NSR-S610C, NA = 1.30), and then developed using a developer (2.38 mass% aqueous TMAH solution) for 10 seconds, rinsed with pure water, and then formed into a resist pattern on a mask. Thereafter, the number of defects on the wafer surface was measured using a scanning electron microscope. When the total number of defects was less than 100 per wafer, it was evaluated as A (good), when the total number of defects was 100 to 500 per wafer, it was evaluated as B (fair), and when the total number of defects was more than 500 per wafer, it was evaluated as C (poor).

[0109] Table 2

[0110] Application Example Fluorine-containing resin Advancing water contact angle ° ]]> ​ Retreating water contact angle ° ]]> ​ 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 application, a powdered polymer can be easily and stably recovered, a resist polymer having a small amount of residual monomers and solvents in the polymer can be produced, and the polymer has a good hydrophobic property, which can well limit the dissolution of the effective components of the cured photoresist film into water when the polymer is used in an ArF immersion-type photoresist, and can reduce the number of defects on the wafer surface.

Claims

1. A process for producing a fluorine-containing resin powder, characterized by, The synthesis step of the fluorine-containing resin and the purification step of the fluorine-containing resin are included. The purification of the fluorine-containing resin specifically includes the following steps: S1: temperature control of the reaction solution after the reaction and the settling agent, the temperature control range is -40℃-0℃, the temperature difference between the reaction solution and the settling agent is not higher than 5℃; S2: drop the reaction solution after temperature control into the settling agent, the volume ratio of the reaction solution to the settling agent is 1:(3-20), stirring is maintained during the drop, after the drop, the stirring is continued, after the stirring, solid-liquid separation is carried out by centrifugal filtration, and finally the fluorine-containing resin powder product is obtained by drying; The fluorine-containing resin is obtained by reaction of monomer M1, monomer M2 and monomer M3; the monomer M1 has the structure shown in formula I; the monomer M2 has the structure shown in formula II; and the monomer M3 has the structure shown in formula III; Formula I Formula II Formula III Wherein, R5, R6, R7 are each independently selected from one of H, methyl, ethyl, isopropyl; R1, R2, R4 are each independently selected from one of substituted or unsubstituted adamantyl, norbornyl, cycloalkyl; R3 is independently selected from one of substituted or unsubstituted methylene, ethylene, propylene, phenylene; the substituted group is selected from H, methyl, ethyl or isopropyl; L is at least one hydrogen atom replaced by a fluorine atom.

2. The production method according to claim 1, characterized by, The settling agent 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, water.

3. The preparation method according to claim 1, characterized in that, The drop speed of the reaction solution is 100-500mL / min; and / or, the stirring speed is 100-300rpm; and / or, the continued stirring time is 10-180 min.

4. The method of claim 1, wherein, The volume ratio of the reaction solution to the settling agent is 1:(5-10).

5. The preparation method according to claim 1, characterized in that, The synthesis step of the fluorine-containing resin of the polymethacrylate type includes: (i) partially dissolved initiator and partially dissolved monomers M1, M2, M3 with solvent, heated to stable reflux state; (ii) the remaining monomers M1, M2, M3 and the remaining initiator are dissolved with solvent to obtain a solution; (iii) under inert environment, the solution obtained in step (ii) is added to the solution of step (i) in the form of drop, the reaction temperature is maintained for maturation, and the reaction liquid is obtained.

6. The production method according to claim 5, wherein The initiator is selected from at least one of azo initiator and organic peroxide initiator; the azo initiator is selected from at least one of azobisisobutyronitrile, azobisisoheptyl nitrile, dimethyl azobis isobutyrate; the organic peroxide initiator is selected from at least one of dibenzoyl peroxide, cyclohexanone peroxide, dodecanoyl peroxide, tert-butyl tert-amyl peroxide; and / or, in step (iii), the drop time is 1-8h; the maturation time is 0-6h; and the reaction temperature is 75-90℃.

7. The fluorine-containing resin powder produced by the production method according to any one of claims 1 to 6, wherein the fluorine-containing resin powder has a content of residual monomer of 200 to 1000 ppm, a content of residual solvent of 10 to 500 ppm, and a particle size distribution of D10 = 0.1 to 10 μm, D50 = 0.1 to 50 μm, and D90 = 0.1 to 80 μm.

8. A photoresist composition characterized by comprising: The photoresist composition comprises (A) an alkali-soluble resin, (B) a photoacid generator, (C) an acid diffusion control agent, (D) the fluorine-containing resin powder of claim 7, and (E) a solvent.

9. The photoresist composition of claim 8, wherein The photoresist comprises 0.1 to 30 parts by weight of (B) the photoacid generator, 0.1 to 30 parts by weight of (C) the acid diffusion control agent, and 0.5 to 30 parts by weight of (D) the fluorine-containing resin powder, per 100 parts by weight of (A) the alkali-soluble resin.

10. Use of the resist composition according to claim 8 or 9 or the fluorine-containing resin powder according to claim 7 in ArF immersion.

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