Fluorine-containing monomer and preparation method thereof

Abstract

The embodiment of the invention provides a fluorine-containing monomer and a preparation method thereof. The fluorine-containing monomer can be used for providing fluorine-containing resin, and the fluorine-containing resin has relatively high hydrophobic performance and relatively excellent alkali reactivity, so that the patterning effect of a resist under a specific production scene can be effectively improved, and preparation and development of a high-performance semiconductor device are facilitated.

Description

[0001] This application is a divisional application. The application number of the original application is CN202411194866.0, and the original application date is August 29, 2024. The entire contents of the original application are incorporated into this application by reference. Technical Field

[0002] The present application relates to the technical field of semiconductor device preparation, and in particular to fluorine-containing monomers and preparation methods thereof. Background Art

[0003] In the process of preparing semiconductor devices, it is often necessary to etch the substrate of the semiconductor device to form a certain pattern on the substrate, such as a patterned groove structure. Before etching, transferring the preset pattern to the substrate surface completely and accurately is also a key step in the process. Generally, a resist can be coated on the surface of the substrate to form a resist film layer, and then exposed through a mask; but in some production scenarios, in order to improve the resolution of exposure, the substrate with the resist film layer is immersed in liquids such as water, and the output end of the exposure light source is also immersed in the above liquid and then irradiated. In the above process, water forms watermark defects on the surface of the resist film layer, and even causes the film layer to swell. The above situations will seriously affect the patterning results; in addition, it may also cause the components in the resist film layer to contaminate the output end of the exposure light source and change the refractive index of the immersion liquid.

[0004] In order to solve the above technical problems, the industry often forms a barrier layer on the surface of the anti-etching film layer; however, the barrier layer used in the related art either has poor hydrophobic properties or is difficult to peel off after development, and the improvement of the patterning result is limited. Summary of the invention

[0005] In view of this, the embodiments of the present application provide fluorine-containing resins and preparation methods thereof, fluorine-containing monomers, resin compositions, functional films and functional parts, semiconductor devices and preparation methods thereof. The above-mentioned fluorine-containing resins have both high hydrophobicity and good alkali reactivity, which can effectively improve the patterning effect of the resist in specific production scenarios, and are conducive to the preparation and development of high-performance semiconductor devices, for example, the preparation and development of high-performance integrated circuits.

[0006] In a first aspect, an embodiment of the present application provides a fluorine-containing resin, comprising a first structural unit as shown in formula (I);

[0007]

[0008] Wherein, R1 is any one of a hydrogen atom, a fluorine atom, a methyl group or a methyl group substituted with a fluorine atom;

[0009] R 21 is a single bond, or, R 21 is an alkylene group; R 22is a cycloalkyl substituted with a substituent, wherein the substituent is The position marked with * is connected to the cycloalkyl group; R3 is a straight-chain fluorinated alkylene group, and R4 is an alkyl group or a fluorinated alkyl group.

[0010] The fluorine-containing resin provided in the embodiment of the present application has a first structural unit whose side group includes a cycloalkyl group substituted by a substituent, and the cycloalkyl group is beneficial to improving the hydrophobicity of the first structural unit; at the same time, R 22 The substituents in the above formula are specifically fluorine-substituted carboxylate linkage structures. It can simultaneously improve the hydrophobicity and alkaline reactivity of the first structural unit; more importantly, R 22 Only through the ester group -COO- or only through -COO-R 21 By connecting with the main chain of the fluorine-containing resin, the hydrophobicity of the fluorine-containing resin can be further improved; therefore, the fluorine-containing resin provided in the embodiment of the present application can have both high hydrophobicity and excellent alkali reactivity. During the immersion exposure process, the above-mentioned fluorine-containing resin can effectively reduce the risk of water leaving watermarks on the fluorine-containing resin film layer and effectively inhibit the diffusion of components in the anti-corrosion film layer into the water (i.e., immersion liquid), thereby facilitating the optimization of the patterning effect in the semiconductor device process and facilitating the preparation and application of high-performance semiconductor devices.

[0011] In some embodiments of the present application, the cycloalkyl group is a C4-C10 cubic cycloalkyl group; the C4-C10 cubic cycloalkyl group includes any one of formula (A) to formula (E):

[0012]

[0013] In some embodiments of the present application, the R 21 It is a C1-C5 straight chain alkylene group.

[0014] In some embodiments of the present application, the R 22 The number of the substituents is a positive integer of 1-3.

[0015] In some embodiments of the present application, the R3 is a C1-C5 straight-chain fluorinated alkylene group; and / or the number of carbon atoms of the R4 is 1-10.

[0016] In some embodiments of the present application, R3 is any one of -CHF-, -CF2-, -CHFCF2-, -CF2CF2-, -CF2CF2CF2-, -CHFCF2CF2-, -CF2CF2CHF-, -CF2CHFCF2-, -CF2CF2CF2CF2-, -CF2CF2CF2CF2-, -CF2CF2CF2CF2-.

[0017] In some embodiments of the present application, the first structural unit includes

[0018] and / or,

[0019] In some embodiments of the present application, the fluorine-containing resin further includes a second structural unit; the second structural unit includes one or more of formula (1) to formula (11):

[0020] Here, R is a hydrogen atom, a fluorine atom, a methyl group, or a methyl group substituted with a fluorine atom.

[0021] In some embodiments of the present application, the fluorine-containing resin includes one or more of formula (W) to formula (Z):

[0022] Wherein, a, b, and m are all independently positive integers.

[0023] In some embodiments of the present application, the molar proportion of the first structural unit in the fluorine-containing resin is ≥30%.

[0024] In some embodiments of the present application, the weight average molecular weight of the fluorine-containing resin is 3kDa-10kDa; and / or the molecular weight distribution index of the fluorine-containing resin is 1-2.

[0025] A second aspect of the present application provides a method for preparing a fluorine-containing resin, comprising:

[0026] The monomers are polymerized to obtain a fluorine-containing resin; wherein the monomers include R1 is any one of a hydrogen atom, a fluorine atom, a methyl group, or a methyl group substituted with a fluorine atom;

[0027] R 21 is a single bond, or, R 21 is an alkylene group; R 22 is a cycloalkyl substituted with a substituent, wherein the substituent is The position marked with * is connected to the cycloalkyl group; R3 is a straight-chain fluorinated alkylene group, and R4 is an alkyl group or a fluorinated alkyl group.

[0028] The above preparation method is suitable for large-scale industrial production.

[0029] The third aspect of the embodiment of the present application provides a fluorine-containing monomer, wherein the fluorine-containing monomer comprises a structure shown in formula (II):

[0030]

[0031] Wherein, R1 is any one of a hydrogen atom, a fluorine atom, a methyl group or a methyl group substituted with a fluorine atom;

[0032] R21 is a single bond, or, R 21 is an alkylene group; R 22 is a cycloalkyl substituted with a substituent, wherein the substituent is The position marked with * is connected to the cycloalkyl group; R3 is a straight-chain fluorinated alkylene group, and R4 is an alkyl group or a fluorinated alkyl group.

[0033] The above-mentioned fluorine-containing monomer can be used to provide the fluorine-containing resin provided in the first aspect of the embodiment of the present application.

[0034] The fourth aspect of the embodiment of the present application provides a resin composition, including the fluorine-containing resin and solvent provided in the first aspect of the embodiment of the present application; or, including the fluorine-containing resin prepared according to the preparation method of the fluorine-containing resin provided in the second aspect of the embodiment of the present application.

[0035] The resin composition can be used to provide a functional film having both excellent hydrophobicity and excellent alkali reaction performance.

[0036] The fifth aspect of the embodiments of the present application provides a functional film, comprising the fluorine-containing resin provided in the first aspect of the embodiments of the present application; or, comprising a fluorine-containing resin prepared according to the preparation method of the fluorine-containing resin provided in the second aspect of the embodiments of the present application; or, the functional film is formed by the resin composition provided in the fourth aspect of the embodiments of the present application.

[0037] The functional film has excellent hydrophobic properties, and the functional film can show excellent hydrophilicity after reacting with alkaline substances; the functional film can play a key role in the preparation process of high-performance semiconductor devices, improve the manufacturing accuracy and quality of semiconductor devices, and thus improve the performance of semiconductor components. Specifically, for example, the functional film can be set on the anti-etching film layer to prepare a patterned structure (for example, a patterned substrate), and then the patterned structure is etched to prepare a semiconductor device.

[0038] The sixth aspect of the embodiment of the present application provides a functional part, including a substrate and the functional film provided by the fifth aspect of the embodiment of the present application disposed on the substrate. The above-mentioned functional part can be used to prepare a semiconductor device. For example, the above-mentioned functional part can be used to provide a patterned structure, and then the patterned structure is etched and processed to prepare a semiconductor device.

[0039] The seventh aspect of the embodiment of the present application provides a semiconductor device, which is obtained by coating the fluorine-containing resin provided in the first aspect of the embodiment of the present application on a substrate, and then exposing and developing it, or the semiconductor device is obtained by coating the resin composition provided in the fourth aspect of the embodiment of the present application on a substrate, and then exposing and developing it, or the functional part provided in the sixth aspect of the embodiment of the present application is used to be exposed and developed. Specifically, the semiconductor device includes a structure obtained by etching a structure to be patterned (such as a substrate to be patterned), and the surface of the structure to be patterned has a film layer formed by the above-mentioned fluorine-containing resin or resin composition; or the structure to be patterned includes the above-mentioned functional part.

[0040] An eighth aspect of the embodiments of the present application provides a method for preparing a semiconductor device, comprising:

[0041] coating a resist on a substrate to form a resist film layer on the substrate;

[0042] Coating the fluorine-containing resin provided in the first aspect of the embodiment of the present application on the surface of the anti-corrosion film layer away from the substrate, or coating the resin composition provided in the fourth aspect of the embodiment of the present application on the surface of the anti-corrosion film layer away from the substrate, so as to form a functional layer on the surface of the anti-corrosion film layer;

[0043] The resist film layer is developed through a photomask and a developer to form a patterned film on a substrate. DETAILED DESCRIPTION

[0044] In the process of preparing semiconductor devices, it is often necessary to pattern the substrate of the semiconductor device, including: using a resist to form a resist film layer on the surface of the substrate, irradiating the resist film layer through a photomask, using a developer to treat the irradiated resist film layer to form a patterned film, and then etching the substrate with the patterned film to obtain a patterned substrate. The characteristic size of the patterned film will significantly affect the accuracy of the semiconductor device. At present, in order to further reduce the characteristic size of the patterned film, the industry will use immersion exposure. Immersion exposure requires immersing the substrate with the resist film layer in a liquid such as water, and immersing the output end of the light source (for example, the lens of the lens) in the above-mentioned immersion liquid for irradiation; after irradiation, it is successively developed and cleaned to obtain a patterned film. In order to prevent the immersion liquid from forming watermarks on the resist film layer, or from penetrating into the resist film layer and causing the resist film layer to swell; at the same time, some components in the resist film layer (for example, photoacid generators, photodecomposable bases, etc.) will also enter the immersion liquid and contaminate the lens, and change the refractive index of the immersion liquid, affecting exposure: for example, causing changes in the process window, damage to the characteristic size and morphology of the patterned film. In particular, in some production situations, for example, when the exposure process is irradiated with a laser light source excited by argon fluoride gas, the immersion liquid is preferably water.

[0045] In order to solve the above technical problems, the industry often forms a hydrophobic layer on the surface of the anti-etching film layer; it is understandable that in order to obtain a patterned film, the hydrophobic layer also needs to be removed during the above-mentioned development and cleaning process. Generally, a hydrophobic layer is formed by using a material with alkaline reactivity, so that the polarity of the hydrophobic layer after development can be reversed (specifically, from hydrophobic to hydrophilic), so that it can be smoothly peeled off. However, the comprehensive performance of the hydrophobic layer used in the related art is poor, and it is difficult to achieve better hydrophobic performance and higher alkaline reactivity at the same time, and the improvement of the patterning result of the resist is limited. Therefore, it is urgent to provide a hydrophobic layer resin with excellent comprehensive performance to enhance the patterning effect of immersion exposure. Generally, an alkaline developer can be used for the above-mentioned development treatment, so that the hydrophobic layer can react with the alkaline developer.

[0046] The embodiment of the present application provides a fluorine-containing resin, comprising a first structural unit as shown in formula (I);

[0047]

[0048] Wherein, R1 is any one of a hydrogen atom, a fluorine atom, a methyl group or a methyl group substituted with a fluorine atom. This is beneficial to improving the solubility of the fluorine-containing resin in the solvent, thereby facilitating the application of the fluorine-containing resin; and it is also beneficial to ensure that the alkali reactivity of the fluorine-containing resin is high.

[0049] R 21 is a single bond, or, R 21 is an alkylene group; R 22 is a cycloalkyl substituted with a substituent, wherein the substituent is The position marked with * is connected to the cycloalkyl group; R3 is a straight chain fluorinated alkylene group, and R4 is an alkyl group or a fluorinated alkyl group. The attachment position of may be any substitutable carbon atom on the cycloalkyl group.

[0050] In the embodiment of the present application, when the above R1 is a methyl group substituted by a fluorine atom, it can specifically be any one of -CH2F, -CHF2, and -CF3.

[0051] It can be understood that the fluorine-containing resin is a polymer. In the embodiment of the present application, the fluorine-containing resin may include only one first structural unit, that is, the fluorine-containing resin is a homopolymer, wherein the structures of R1 of the plurality of first structural units are the same, R 21 -R 22 The structures of the first structural units are the same; for example, R1 of the first structural units is methyl, R 21 -R 22 Both However, it is not limited thereto; it is also possible that the fluorine-containing resin includes a plurality of different first structural units: for example, R1 of a plurality of first structural units is the same, and R 21 -R 22 Selected from The first structural unit of the other part R 21 -R 22 Selected from But not limited thereto; or, R1 of the plurality of first structural units is different, wherein R1 of a portion of the first structural units is selected from methyl, R1 of a portion of the first structural units is selected from -CF3, and R1 of the plurality of first structural units is selected from 21 -R 22 or, there are some first structural units, among which R1 is different, R 21 -R 22 It is understandable that when the plurality of first structural units are different, the fluorine-containing resin can be a random copolymer or a block copolymer containing a plurality of different first structural units.

[0052] In the embodiments of the present application, the presence of the first structural unit in the fluorine-containing resin can be determined by mass spectrometry, infrared, nuclear magnetic resonance or other testing methods.

[0053] The fluorine-containing resin provided in the embodiment of the present application has a first structural unit whose side group includes a cycloalkyl group substituted by a substituent, and the cycloalkyl group is beneficial to improving the hydrophobicity of the first structural unit; at the same time, R 22 The substituents in the above formula are specifically fluorine-substituted carboxylate linkage structures. It can simultaneously improve the hydrophobicity and alkaline reactivity of the first structural unit; more importantly, R 22 Only through the ester group -COO- or only through -COO-R 21 Connecting with the main chain of the fluorine-containing resin can further improve the hydrophobicity of the fluorine-containing resin; therefore, the fluorine-containing resin provided in the embodiment of the present application can have both high hydrophobicity and good alkaline reactivity. In the process of immersion exposure, the above-mentioned fluorine-containing resin can effectively reduce the risk of water leaving watermarks on the fluorine-containing resin film layer, effectively inhibit the diffusion of components in the anti-corrosion film layer into water (i.e., immersion liquid), thereby facilitating the optimization of the patterning effect in the semiconductor device process, and facilitating the preparation and application of high-performance semiconductor devices. Specifically, in the embodiment of the present application, the high hydrophobicity and alkaline reactivity of the fluorine-containing resin are specifically manifested as follows: compared with the related art, the film layer formed by the fluorine-containing resin provided in the embodiment of the present application shows a suitable forward contact angle and a suitable receding contact angle to water droplets, and can show a lower rolling angle; at the same time, the above-mentioned film layer shows a lower static contact angle to water droplets after exposure and development treatment, thereby facilitating the stripping of the fluorine-containing resin. The fluorine-containing resin provided in the embodiment of the present application is particularly suitable for use with a positive resist.

[0054] In some embodiments of the present application, the advancing contact angle (ACA) of the film layer including the above-mentioned fluorine-containing resin to water droplets is 90°-100°, and the receding contact angle (RCA) to water droplets is 75°-85°. It can be understood that the above-mentioned advancing contact angle and receding contact angle to water droplets are measured before exposure and development. Specifically, the ACA of the film layer including the above-mentioned fluorine-containing resin to water droplets can be, for example, 90°, 91°, 92°, 93°, 94°, 95°, 96°, 97°, 98°, 99°, 100°, etc. Specifically, the RCA of the film layer including the above-mentioned fluorine-containing resin to water droplets can be, for example, 75°, 76°, 77°, 78°, 79°, 80°, 81°, 82°, 83°, 84°, 85°, etc. In the embodiment of the present application, the advancing contact angle and the receding contact angle are tested by the tilted plate method; wherein, in the test process of the tilted plate method, the advancing contact angle refers to: when the surface is tilted to a certain angle, the droplet begins to slide, and the contact angle corresponding to the moment when the droplet slides below; the receding contact angle refers to: when the surface is tilted to a certain angle, the droplet begins to slide, and the contact angle corresponding to the moment when the droplet slides above. Specifically, the contact angle tester can be used to test the advancing contact angle and the receding contact angle; the amount of the droplet is 50μL.

[0055] In some embodiments of the present application, the rolling angle of the film layer comprising the above-mentioned fluorine-containing resin to water droplets is ≤20°. It will be understood that the above-mentioned rolling angle to water droplets is measured before exposure and development treatment. Specifically, the rolling angle of the film layer comprising the above-mentioned fluorine-containing resin to water droplets can be, for example, 7°, 8°, 9°, 10°, 11°, 12°, 13°, 14°, 15°, 16°, 17°, 18°, 19°, 20°, etc. In the embodiments of the present application, similarly, the tilted plate method is used to test the above-mentioned rolling angle. The rolling angle refers to the contact angle at which the droplet just starts to roll on the inclined surface.

[0056] In some embodiments of the present application, after development, the film layer comprising the above-mentioned fluorine-containing resin has a static contact angle of ≤65° to a water droplet, and a receding contact angle of ≤20° to a water droplet. Specifically, after development, the film layer comprising the above-mentioned fluorine-containing resin has a static contact angle (SCA) of 50°, 51°, 52°, 53°, 54°, 55°, 56°, 57°, 58°, 59°, 60°, 61°, 62°, 63°, 64°, 65°, etc. Specifically, after development, the film layer comprising the above-mentioned fluorine-containing resin has an RCA of 7°, 8°, 9°, 10°, 11°, 12°, 13°, 14°, 15°, 16°, 17°, 18°, 19°, 20°, etc. In the embodiment of the present application, the static contact angle can be tested according to a contact angle tester, and the droplet volume during the test is 50 μL. The receding contact angle is tested according to the relevant description in the previous text, which will not be repeated here. In the embodiment of the present application, the development can be: using an alkaline developer to contact the film layer including the fluorine-containing resin, and the contact time between the developer and the film layer can be 10s-120s. The alkaline developer can be, for example, a tetramethylammonium hydroxide (TMAH) aqueous solution with a mass fraction of 0.5-5%.

[0057] In some embodiments of the present application, the above-mentioned cycloalkyl group is a C4-C10 cubic cycloalkyl group; the C4-C10 cubic cycloalkyl group includes any one of formula (A) to formula (E): The steric hindrance of the cycloalkyl group is more appropriate and the hydrophobicity is better, which is beneficial to improving the comprehensive performance of the fluorine-containing resin.

[0058] In some embodiments of the present application, R 21 is a C1-C5 straight chain alkylene. Thus, in the fluorine-containing resin, R 22 By-COO-R 21 The alkylene group between the cycloalkyl group and the main chain is connected to the main chain, and the carbon number of the alkylene group between the cycloalkyl group and the main chain is controlled to be between 1 and 5 and is a straight chain alkylene group, which is conducive to maintaining the receding contact angle of water droplets on the surface of the film layer formed by the fluorine-containing resin within a more appropriate range, and is also more conducive to improving the developing performance of the fluorine-containing resin; specifically, the better the hydrophilicity of the fluorine-containing resin after the developing treatment, the better the developing performance of the fluorine-containing resin. In addition, it is also conducive to ensuring that the fluorine-containing resin has good solubility. Specifically, R 21 For example, it can be one or more of -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2-, and -CH2CH2CH2CH2CH2-. In some specific embodiments, the above R 22is a C4-C10 cycloalkyl substituted with a substituent. 22 The first structural unit has good hydrophobicity and is more conducive to the development performance of the fluorine-containing resin, thereby facilitating the smooth stripping of the film layer formed by the fluorine-containing resin in the semiconductor process. Specifically, the number of carbon atoms in the cycloalkyl group can be, for example, 4, 5, 6, 7, 8, 9, or 10.

[0059] In some embodiments of the present application, R 21 is a single bond, R 22 is a C4-C10 cubic cycloalkyl group; the C4-C10 cubic cycloalkyl group includes any one of formula (A) to formula (E): In this way, the cubic cycloalkyl is connected to the main chain only through -COO-, which improves the receding contact angle of the fluorine-containing resin, which is not only more conducive to improving the hydrophobicity of the fluorine-containing resin, but also conducive to the dissolution of the fluorine-containing resin in the solvent, and more conducive to the coating of the fluorine-containing resin on the surface of the anti-etching film layer to form a uniform functional layer, and can also improve the anti-etching performance of the fluorine-containing resin, which is conducive to the final patterning effect. 21 -R 22 Can be selected from one or more of formula (F) to formula (K):

[0060] Wherein, n in the above formula (F)-formula (K) is a positive integer of 1-3; that is, the number of substituents on a single cycloalkyl group can be independently 1, 2, or 3. Controlling the number of substituents within the above range is, firstly, beneficial to control the steric hindrance of the first structural unit within an appropriate range, and secondly, beneficial to ensure that the hydrophobicity and alkaline reactivity of the fluorine-containing resin are high. In the embodiment of the present application, when a plurality of the above substituents are connected to a cycloalkyl group, the connection position of the substituent on the cycloalkyl group is not limited; for example, each of the multiple substituents is connected to a different carbon atom of the cycloalkyl group, and the relative positions of the substituents are not limited. It can be understood that the above substituents are connected to any substitutable carbon atom of the above cubic cycloalkyl group.

[0061] In the present application, the substituent R3 in is a straight-chain fluorinated alkylene group. R3 is straight-chain, which is beneficial to optimize the alkaline reactivity of the first structural unit. In the embodiment of the present application, R3 is a fluorinated alkylene group, specifically refers to a structure in which one or more hydrogen atoms in the alkylene group are replaced by fluorine atoms. When the above R3 contains multiple fluorine atoms, it includes but is not limited to the following three situations: (a) multiple hydrogen atoms connected to a carbon atom may be replaced by fluorine atoms; (b) there may be multiple carbon atoms, each of which has a hydrogen atom replaced by a fluorine atom; (c) it may also be a combination of the above two situations. When the fluorine atom content in R3 increases, it is beneficial to improve the alkaline reactivity and hydrophobicity of the first structural unit; when the fluorine atom content in R3 decreases, it is beneficial to optimize the solubility of the fluorine-containing resin after development.

[0062] In some embodiments of the present application, R3 is a C1-C5 straight chain fluorinated alkylene group. By controlling the number of carbon atoms of R3 within the above range, the substituent can be controlled. The steric hindrance between the two ester groups is small, which is conducive to the synergistic effect of the two, thereby facilitating the base reactivity of the fluorine-substituted carboxylic acid ester connection structure and improving the comprehensive performance of the fluorine-containing resin. Specifically, the carbon atoms of R3 can be 1, 2, 3, 4, or 5, for example; the above R3 can be, for example, -CHF-, -CF2-, -CHFCF2-, -CF2CF2-, -CF2CF2CF2-, -CHFCF2CF2-, -CF2CF2CHF-, -CF2CHFCF2-, -CF2CF2CF2CF2-, but is not limited thereto.

[0063] In the present application, the substituent R4 in the present invention is an alkyl group or a fluorinated alkyl group. In some embodiments of the present invention, the number of carbon atoms of R4 is 1-10. This is beneficial to the dissolution of the fluorinated resin in the solvent and to maintaining the alkaline reactivity of the fluorinated resin at a high level. Specifically, the number of carbon atoms of R4 can be, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0064] In some embodiments of the present application, R4 is a fluorinated alkyl group; the substitution of fluorine atoms is beneficial to improving the hydrophobicity and alkaline reactivity of the fluorinated resin. Similar to R3, R4 is a fluorinated alkyl group, specifically referring to a structure in which one or more hydrogen atoms in the alkyl group are replaced by fluorine atoms. In other embodiments of the present application, R4 is an alkyl group, which is beneficial to improving the wettability of the fluorinated resin to alkaline liquids, thereby facilitating the development process. Specifically, R4 can be linear, branched, or cyclic. In some embodiments, R4 is -CH3, -CH2CH3, or a branched alkyl group. In other embodiments, R4 is -CH3, -CH2CH3, or a branched alkyl group in which all or part of the hydrogen atoms are replaced by fluorine atoms. When the number of carbon atoms in R4 is constant, the higher the relative content of primary carbon atoms in R4, the more conducive to the polarity reversal reaction of the fluorinated resin. Specifically, R4 can be, for example, -CH3, -CH2CH3, -CH(CH3)2, -C(CH3)3, -C(CH3)2C(CH3)3, -C(CH3)2C(CH3)2C(CH3)3, but is not limited thereto; when R4 includes a fluorine-containing alkyl group, the fluorine-containing alkyl group can be a structure in which the hydrogen atoms in the above-mentioned alkyl groups are completely or partially substituted by fluorine atoms.

[0065] In some embodiments of the present application, the first structural unit includes and / or, In some specific embodiments, the first structural unit includes and / or, The first structural unit of the above structure has high hydrophobicity and alkali reaction, high solubility in solvents, and is easy to be coated on the surface of the anti-corrosion film layer; and the fluorine-containing resin including the first structural unit has excellent performance after exposure and development, which is conducive to the preparation of high-performance semiconductor devices. In addition, the fluorine-containing resin including the first structural unit of the above structure is easy to obtain in industry.

[0066] In the embodiments of the present application, the fluorine-containing resin may be composed of only the first structural unit, or may also include other structural units. In some cases, taking into account different specific production conditions, different stringency of process requirements, or considering production cost issues, in some embodiments of the present application, the fluorine-containing resin may also include a second structural unit; the second structural unit includes but is not limited to an organic structural unit having hydrophobic properties and / or alkaline reactivity, and the second structural unit is different from the first structural unit. In other words, the second structural unit can be selected from any structural unit known in the art that can be used to constitute a resin having hydrophobicity and / or alkaline reactivity. Specifically, the second structural unit may be, for example: But not limited to this; wherein the above R can be, for example, a hydrogen atom, a fluorine atom, a methyl group, or a methyl group substituted by a fluorine atom. The fluorine-containing resin may include one or more of the above-mentioned second structural units, and the present application is not limited to this. Specifically, a single molecular structure of the fluorine-containing resin may include multiple different second structural units, wherein the different second structural units may all conform to the structure shown in formula (1), but the R of the above-mentioned second structural units is different; or, there are some second structures that conform to the structure shown in formula (1), and other second structural units conform to the structure shown in formula (2). Of course, in the embodiments of the present application, the fluorine-containing resin may also include other structural units in addition to the aforementioned first structural unit and other structural units such as formula (1) to formula (11).

[0067] In some embodiments of the present application, when a single molecule of the fluorine-containing resin further includes the second structural unit, the fluorine-containing resin is a random copolymer, which is more conducive to the hydrophobicity, alkali reaction performance, exposure performance and performance after development of the fluorine-containing resin.

[0068] In some embodiments of the present application, the molar proportion of the first structural unit in the fluorine-containing resin is ≥30%. In some specific embodiments, taking into account the cost and the comprehensive performance of the fluorine-containing resin, the molar proportion of the first structural unit in the fluorine-containing resin is 30%-70%. Specifically, the molar proportion of the first structural unit in the fluorine-containing resin can be, for example, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48%, 50%, 52%, 55%, 58%, 60%, 62%, 65%, 68%, 70%, 75%, 80%, etc. In the embodiment of the present application, gel chromatography (Gel Chromatography, GPC) can be used to test the molar proportion of the first structural unit in the fluorine-containing resin.

[0069] In some embodiments of the present application, the fluorine-containing resin includes one or more of formula (W) to formula (Z):

[0070]

[0071] Wherein, a, b, and m are all independently positive integers. In some specific embodiments, b / (a+b)≥30%. In some specific embodiments, 30%≤b / (a+b)≤70%.

[0072] In some embodiments of the present application, the weight average molecular weight of the fluorine-containing resin is 3kDa-10kDa. This is beneficial to the application and preparation of the fluorine-containing resin. In some specific embodiments, the weight average molecular weight of the fluorine-containing resin is 5kDa-6kDa. In the embodiments of the present application, the weight average molecular weight of the fluorine-containing resin can be tested by methods such as small-angle laser scattering.

[0073] In some embodiments of the present application, the molecular weight distribution index of the fluorine-containing resin is 1 to 2. In the embodiments of the present application, GPC can be used to test the molecular weight distribution index of the fluorine-containing resin.

[0074] The present application also provides a method for preparing a fluorine-containing resin, comprising:

[0075] The monomers are polymerized to obtain a fluorine-containing resin; wherein the monomers include R1 is any one of a hydrogen atom, a fluorine atom, a methyl group, or a methyl group substituted with a fluorine atom;

[0076] R 21 is a single bond, or, R 21 is an alkylene group; R 22 is a cycloalkyl substituted with a substituent, wherein the substituent is The position marked with * is connected to the cycloalkyl group; R3 is a straight chain fluorinated alkylene group, and R4 is an alkyl group or a fluorinated alkyl group. The above preparation method is suitable for large-scale industrial production.

[0077] In some embodiments of the present application, in the preparation process of the above fluorine-containing resin, the monomers may also include different For example, the other monomers may be compounds that can be derived from the second structural unit, but are not limited thereto.

[0078] In the embodiments of the present application, the fluorine-containing resin can be prepared by addition polymerization, but is not limited thereto. The preparation of the fluorine-containing resin can be carried out by any polymerization conditions known in the art, for example, by free radical polymerization. The following is a specific example to illustrate the polymerization of the fluorine-containing resin:

[0079] Among them, the above V601 is dimethyl azobisisobutyrate, and PGMEA is propylene glycol methyl ether acetate. The above is just an example polymerization route of one embodiment. The initiator, solvent and reaction temperature involved in the above polymerization reaction can be selected according to the actual fluorine-containing monomer used. This application does not limit this. The fluorine-containing resin can be obtained by polymerization.

[0080] The embodiment of the present application also provides a resin composition, including the fluorine-containing resin provided in the embodiment of the present application, and a solvent.

[0081] In the embodiments of the present application, the above-mentioned solvent can be selected from the solvents known in the art that can dissolve the fluorine-containing resin, and the solvent does not damage the anti-corrosion film layer; preferably, the above-mentioned solvent is easily volatile after drying. In some embodiments of the present application, the above-mentioned solvent includes but is not limited to one or more of propylene glycol methyl ether acetate (PGMA), γ-butyrolactone, and 2-hydroxyisobutyric acid methyl ester (HBM).

[0082] The resin composition formed by dissolving the fluorine-containing resin in a solvent is easier to apply and has better film-forming properties, for example, the uniformity of the film layer formed is high and the thickness is suitable. Understandably, in the process of semiconductor devices, the above-mentioned resin composition is coated on the anti-corrosion film layer, and the solvent can also be removed by treatments such as drying to obtain a functional layer. The functional layer formed by the above-mentioned resin composition can have both higher hydrophobicity and better alkali reactivity. During immersion exposure, the functional layer formed by the above-mentioned resin composition can effectively reduce the risk of watermarks on the fluorine-containing resin film layer, effectively suppress the components in the anti-corrosion film layer from diffusing into water (i.e., immersion liquid), thereby facilitating the patterning effect in the process of optimizing semiconductor devices, and facilitating the preparation and application of high-performance semiconductor devices.

[0083] In some embodiments of the present application, based on the total mass of the resin composition, the mass proportion of the fluorine-containing resin is 2%-10%. In this way, the film-forming performance of the resin composition is good, and the hydrophobic barrier performance of the functional layer formed after drying is better, which is more conducive to improving the patterning effect. Specifically, the mass proportion of the fluorine-containing resin can be, for example, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, etc. In the embodiments of the present application, the resin composition can be freeze-dried or the like to remove the solvent, and the solid substance obtained after freeze-drying is dissolved in a quantitative deuterated reagent and an internal standard and subjected to a nuclear magnetic resonance test, and the nuclear magnetic resonance test results are normalized, and then the content of the fluorine-containing resin in the resin composition is calculated and determined.

[0084] In some embodiments of the present application, the resin composition further comprises a photoacid generator and / or a photodecomposable base. A photoacid generator (PAG) refers to a compound that can react or dissociate to produce one or more acids (e.g., proton strong acid) under light conditions. A photodecomposable base (PDB) is a photosensitive alkaline material that is a thermodynamically stable compound that exhibits alkalinity when not irradiated and can be decomposed into a neutral compound or a weakly acidic compound after irradiation.

[0085] In the embodiments of the present application, the photoacid generator can be any known photoacid generator that can be used in the field of resist. Specifically, it includes an ionic photoacid generator, the cation of the ionic photoacid generator is selected from phenylsulfonium salts, for example, triphenylsulfonium salts; its anion includes an anion fragment containing fluorine element; in some specific embodiments, the cation in the above-mentioned photoacid generator is R s1 , R s2 , R s3 independently selected from H, substituted or unsubstituted alkyl, or substituted or unsubstituted cycloalkyl;

[0086] Anionic fragments include but are not limited to

[0087] Considering that the photodecomposable base itself is alkaline, in order to reduce the risk of the photodecomposable base affecting the polarity of the fluorine-containing resin, the photodecomposable base in the resin composition of the embodiment of the present application can be selected from PDB with weaker alkalinity, for example,

[0088] In some embodiments of the present application, the mass proportion of the photoacid generator in the resin composition is 3%-20%. In this way, it is beneficial to the application of the resin composition. In the embodiment of the present application, the resin composition can be subjected to freeze drying and other treatments to remove the solvent, and the solid material obtained after freeze drying is dissolved in a quantitative deuterated reagent and an internal standard and subjected to a nuclear magnetic resonance test, and the nuclear magnetic resonance test results are normalized, and then the content of the photoacid generator in the resin composition is calculated and determined. Specifically, the mass proportion of the photoacid generator in the resin composition can be, for example, 3%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, etc.

[0089] In some embodiments of the present application, the mass proportion of the photodecomposable base in the resin composition is ≤10%. In this way, it is beneficial to ensure the stability of the resin composition and the high hydrophobicity after film formation, which is beneficial to the final patterning effect. In the embodiment of the present application, the resin composition can be freeze-dried and other treatments to remove the solvent, and the solid material obtained after freeze-drying is dissolved in a quantitative deuterated reagent and an internal standard and subjected to a nuclear magnetic resonance test, and the nuclear magnetic resonance test results are normalized, and then the content of the photodecomposable base in the resin composition is calculated. Specifically, the mass proportion of the photodecomposable base in the resin composition can be, for example, 0.1%, 0.5%, 1%, 2%, 5%, 8%, 10%, etc.

[0090] In some embodiments of the present application, the functional layer formed after the above-mentioned resin composition is dried has an advancing contact angle (ACA) of 90°-100° to a water droplet, and a receding contact angle (RCA) of 75°-85° to a water droplet. It can be understood that the above-mentioned advancing contact angle and receding contact angle to a water droplet are measured before the development treatment.

[0091] In some embodiments of the present application, the functional layer formed after the resin composition is dried has a rolling angle of ≤20° to water droplets. It is understood that the rolling angle to water droplets is measured before exposure and development.

[0092] In some embodiments of the present application, the functional layer formed by drying the resin composition has a static contact angle of ≤65° to a water droplet and a receding contact angle of ≤20° to a water droplet after development.

[0093] The embodiment of the present application also provides a functional film, including the aforementioned fluorine-containing resin provided in the embodiment of the present application, or including the fluorine-containing resin prepared by the preparation method of the fluorine-containing resin provided in the embodiment of the present application, or the functional film is formed by the aforementioned resin composition provided in the embodiment of the present application. Of course, the functional film provided in the embodiment of the present application may also include other substances, for example, substances with chemical etching resistance, but it is not limited thereto.

[0094] The functional film has excellent hydrophobic properties, and the functional film can show excellent hydrophilicity after reacting with alkaline substances; the functional film can play a key role in the preparation process of high-performance semiconductor devices, improve the manufacturing accuracy and quality of semiconductor devices, and thus improve the performance of semiconductor components. Specifically, for example, the functional film can be arranged on the anti-etching film layer to prepare a patterned structure (for example, a patterned substrate), and then the patterned structure is etched to prepare a semiconductor device. In the embodiment of the present application, the thickness, shape and other parameters of the functional film are not limited.

[0095] The embodiment of the present application also provides a functional part, including a substrate and the aforementioned functional film disposed on the substrate. The functional part can be used to prepare a semiconductor device. For example, the aforementioned functional part can be used to provide a patterned structure, and then the patterned structure is etched and processed to prepare a semiconductor device.

[0096] In some embodiments of the present application, the functional component further comprises an anti-corrosion film layer, and the anti-corrosion film layer is disposed between the substrate and the functional film layer. Specifically, the anti-corrosion film layer comprises an anti-corrosion agent, for example, a chemical anti-corrosion agent.

[0097] The present application also provides a fluorine-containing monomer, which can be used to provide the aforementioned fluorine-containing resin provided in the present application; the fluorine-containing monomer includes a structure shown in formula (II):

[0098]

[0099] Wherein, R1 is any one of a hydrogen atom, a fluorine atom, a methyl group or a methyl group substituted with a fluorine atom;

[0100] R 21 is a single bond, or, R 21 is an alkylene group; R 22 is a cycloalkyl substituted with a substituent, wherein the substituent is The position marked with * is connected to the cycloalkyl group; R3 is a straight-chain fluorinated alkylene group, and R4 is an alkyl group or a fluorinated alkyl group.

[0101] It is understandable that the aforementioned fluorine-containing resin provided in the embodiment of the present application can be obtained by addition polymerization of the carbon-carbon double bond of the fluorine-containing monomer provided in the embodiment of the present application. Therefore, before and after polymerization, R1 in the fluorine-containing monomer, as well as -COO-R 21 -R 22 No chemical changes will occur. Therefore, R1 and R 21 , R 22 The relevant description and selection of can refer to the description of the relevant content of fluorine-containing resin in the previous text, which will not be repeated here.

[0102] In some embodiments of the present application, in the fluorinated monomer, R 21 is a C1-C5 straight chain alkylene group, R 22 is a C4-C10 cycloalkyl group substituted with a substituent. 21 The relevant description and selection of can refer to the description of the relevant content of fluorine-containing resin in the previous text, which will not be repeated here.

[0103] In some embodiments of the present application, in the fluorinated monomer, R 21 For a single key.

[0104] In some embodiments of the present application, in the fluorinated monomer, the cycloalkyl group is a C4-C10 cubic cycloalkyl group. In some specific embodiments, the C4-C10 cubic cycloalkyl group includes any one of formula (A) to formula (E):

[0105]

[0106] In some embodiments of the present application, in the fluorinated monomer, R 21 It is a C1-C5 straight chain alkylene group.

[0107] In some embodiments of the present application, in the fluorinated monomer, R 22 The number of substituents is a positive integer of 1 to 3. The description and selection of the above substituents can refer to the description of the fluorine-containing resin in the previous text, and will not be repeated here.

[0108] In some embodiments of the present application, in the fluorine-containing monomer, R3 is a C1-C5 straight-chain fluorine-containing alkylene group. The description and selection of R3 can refer to the description of the fluorine-containing resin in the above text, and will not be repeated here.

[0109] In some embodiments of the present application, in the fluorine-containing monomer, R3 is any one of -CHF-, -CF2-, -CHFCF2-, -CF2CF2-, -CF2CF2CF2-, -CHFCF2CF2-, -CF2CF2CHF-, -CF2CHFCF2-, -CF2CF2CF2CF2-, -CF2CF2CF2CF2-, -CF2CF2CF2CF2-.

[0110] In some embodiments of the present application, in the fluorine-containing monomer, the carbon number of R4 is 1 to 10. The description and selection of R4 can refer to the description of the fluorine-containing resin in the above text, and will not be repeated here.

[0111] In some embodiments of the present application, the fluorine-containing monomer includes:

[0112] and / or, In some specific embodiments, the fluorine-containing monomer includes and / or,

[0113] Accordingly, the present embodiment also provides a method for preparing the aforementioned fluorine-containing monomer, comprising:

[0114] S01, mix the first monomer and the second monomer A first reaction is performed to obtain a preform; R1 is any one of a hydrogen atom, a fluorine element, a methyl group, or a methyl group substituted with a fluorine atom; R 21 is a single bond, or, R 21 is an alkylene group; R 22 ' is a cycloalkyl group substituted with one or more hydroxyl groups; R3 is a straight-chain fluorinated alkylene group;

[0115] S02, mixing the preform and R4OH, and performing a second reaction to obtain the aforementioned fluorine-containing monomer; wherein R4 is an alkyl group or a fluorine-containing alkyl group. 22 The cycloalkyl group in ' can refer to the above R 22 The relevant description of the cycloalkyl in, for example, the cycloalkyl is a C4-C10 cubic cycloalkyl, is not repeated here.

[0116] In the above preparation method, R 22 The hydroxyl group on the cycloalkyl of ' reacts with the second monomer, specifically, a second monomer is ring-opened and reacts with a hydroxyl group to obtain a preform with an active site, and the active site of the preform then reacts with the hydroxyl group in R4OH to obtain a fluorine-containing monomer. The following is an example of a synthetic route of a specific embodiment for explanation:

[0117]

[0118] Wherein, Pyridine is azaphenylpyridine, MeCN is acetonitrile, EDCI is 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, DMAP is 4-dimethylaminopyridine, and DCM is dichloromethane. The above is only an exemplary synthesis route of one embodiment. The reagents involved in the above reaction can be selected according to the first monomer and the second monomer actually used. This application is not limited to this, and the fluorine-containing monomer can be synthesized.

[0119] The present application also provides a method for preparing a semiconductor device, comprising:

[0120] S11, coating the resist on the substrate to form an anti-corrosion film layer on the substrate;

[0121] S12, coating the fluorine-containing resin provided in the embodiment of the present application, or the aforementioned resin composition provided in the embodiment of the present application on the surface of the anti-corrosion film layer facing away from the substrate to form a functional layer;

[0122] S13, immersing the substrate with the functional layer and the anti-corrosion film layer completely or partially in an immersion liquid (e.g., water), and exposing the substrate to an exposure light source through a photomask;

[0123] S14, developing the exposed resist film layer with a developer to form a patterned film on the substrate.

[0124] In the embodiment of the present application, the semiconductor device may be an integrated circuit device including a chip. In the process of preparing the semiconductor device, after completing the above-mentioned processes S11-S14, the substrate with the patterned film is also etched, and further, other structures may be prepared after etching. Specifically, the above-mentioned other structures may be any structure applicable to semiconductor devices, such as metal wiring, active devices, passive devices, etc.

[0125] In the embodiment of the present application, the substrate can be selected according to specific needs, and can be a silicon wafer, or a silicon wafer covered by other coatings, and other coatings can be anti-reflective coatings, anti-etching coatings, epitaxial layers, metal layers, dielectric layers, modified layers or supporting layers. Usually, other coatings can be obtained by pre-treating the substrate, and the pre-treatment method can be: the silicon wafer substrate is subjected to O2 plasma surface hydrophilic activation; or it is cleaned in Piranha solution (H2O: 30% ammonia: 30% H2O2 = 5: 1: 1) for 15mins-20mins, and then washed with deionized water and isopropanol to complete the hydrophilic treatment; or hexamethyldisilazane (Hexamethyldisilazane, HMDS) is covered on the substrate by evaporation or spin coating to perform surface hydrophobic treatment on the substrate; the hydrophobic treatment can be after the hydrophilic treatment; or a bottom antireflection layer (Bbottomantireflection coating, BARC), a bottom carbon-containing coating (Spin on carbon, SOC), and a bottom silicon-containing coating (Spin on glass, SOG) are added.

[0126] In the embodiment of the present application, after the resist is coated on the substrate, the solvent remaining in the resist coating can be selectively removed by a baking process to obtain a resist film layer. The baking temperature can be between 60° C. and 200° C., and the time can be between 20s and 120s.

[0127] S12. Coat the fluorine-containing resin provided in the embodiment of the present application, or the fluorine-containing resin prepared according to the preparation method of the fluorine-containing resin provided in the embodiment of the present application, or the aforementioned resin composition provided in the embodiment of the present application on the surface of the anti-corrosion film layer facing away from the substrate to form a functional layer.

[0128] In the embodiment of the present application, the coating method in S12 includes but is not limited to spin coating, etc. In the embodiment of the present application, after the resin composition provided in the embodiment of the present application is coated on the surface of the anti-corrosion film layer, the solvent remaining in the resin composition coating can be selectively removed by a baking process to obtain a functional layer. The baking temperature can be between 80°C and 140°C, and the time can be between 20s and 120s.

[0129] S13, immersing the substrate with the functional layer and the anti-corrosion film layer completely or partially in an immersion liquid (e.g., water), and exposing the substrate to an exposure light source through a photomask;

[0130] Specifically, the exposure light source may be a light source with multiple wavelengths, for example, a light source with a wavelength of 150 nm to 350 nm.

[0131] S14, developing the exposed resist film layer with a developer to form a patterned film on the substrate.

[0132] The irradiated film layer (including the anti-corrosion film layer and the functional layer) is cleaned by a developer, and the cleaning time ranges from 10s to 300s, and can be single-step cleaning or multi-step cleaning.

[0133] The development process can select a suitable developer according to the properties of the anti-etching film layer and the fluorine-containing resin; for example, an alkaline developer. In some embodiments of the present application, the developer includes a tetramethylammonium hydroxide (TMAH) aqueous solution with a mass fraction of 0.5-5%. The developer is in contact with the exposed film layer for a development time of 10s-120s. After development, a water rinsing process can be selectively added, and the rinsing time can be 20s-120s. Rinsing can make the film layer cleaner; a baking process can also be selectively added, and the baking temperature can be between 80℃-140℃, and the time can be between 20s-120s; baking can make the pattern structure more stable and not easy to collapse.

[0134] The patterned film formed in step S14 selectively protects the underlying substrate material in the etching step. After etching under certain conditions, the patterned film and the unprotected substrate material are etched, but the etching speed of the protected part is slower than that of the unprotected part, and finally a pattern is formed on the substrate material, that is, the pattern is transferred to the substrate to obtain a patterned substrate. The etching process can specifically transfer the pattern to the substrate through HF etching, ion etching or ion implantation process.

[0135] The present application also provides a semiconductor device, which is obtained by coating the fluorine-containing resin provided in the present application on a substrate, and then exposing and developing it, or the semiconductor device is obtained by coating the resin composition provided in the present application on a substrate, and then exposing and developing it, or the semiconductor device is obtained by exposing and developing the aforementioned functional parts provided in the present application. Since the semiconductor device provided in the present application is made of the fluorine-containing resin or resin composition or functional parts provided in the present application, the semiconductor device provided in the present application has high precision.

[0136] In the embodiments of the present application, there is no special limitation on the structure of the semiconductor device. Those skilled in the art can design it based on the actual application needs, and prepare it based on the fluorine-containing resin or resin composition provided in the embodiments of the present application. Specifically, the semiconductor device includes a structure obtained by etching the structure to be patterned (such as a substrate to be patterned), and the surface of the structure to be patterned has a film layer formed by the above-mentioned fluorine-containing resin or resin composition; or, the structure to be patterned includes the above-mentioned functional parts. In the embodiments of the present application, semiconductor devices include but are not limited to integrated circuit devices such as chips. It can be understood that the semiconductor device provided in the embodiments of the present application also includes other structures, and the other structures can be applied to any structure in the semiconductor device, for example, metal wiring, active devices, passive devices, etc.

[0137] In some embodiments of the present application, the semiconductor device is manufactured by coating the fluorine-containing resin on a substrate with an anti-etching layer, followed by exposure, development, and etching.

[0138] In some embodiments of the present application, the semiconductor device is prepared by coating the resin composition on a substrate with an anti-etching layer, followed by exposure, development, and etching.

[0139] In some further implementations of the present application, the semiconductor device is manufactured by exposing, developing, and etching the functional parts.

[0140] The technical solution of the present application is described in detail below in multiple embodiments.

[0141] Example 1

[0142] A fluorine-containing resin, the structural units of which are The weight average molecular weight Mw of the fluorine-containing resin was 5.0 KDa, and the molecular weight distribution index was 1.4.

[0143] Example 2

[0144] A fluorine-containing resin, the structural units of which are The weight average molecular weight Mw of the fluorine-containing resin was 6.0 KDa, and the molecular weight distribution index was 1.4.

[0145] Example 3

[0146] A fluorine-containing resin, which is a random copolymer composed of a first structural unit and a second structural unit, wherein the first structural unit is The second structural unit is Moreover, in the fluorine-containing resin, the molar proportion of the first structural unit is 50%; the weight average molecular weight Mw of the fluorine-containing resin is 4.8 KDa, and the molecular weight distribution index is 1.2.

[0147] Example 4

[0148] A fluorine-containing resin, which is a random copolymer composed of a first structural unit and a second structural unit, wherein the first structural unit is The second structural unit is Moreover, in the fluorine-containing resin, the molar proportion of the first structural unit is 50%; the weight average molecular weight Mw of the fluorine-containing resin is 5.8 KDa, and the molecular weight distribution index is 1.35.

[0149] Comparative Example 1

[0150] A fluorine-containing resin, the structural units of which are The weight average molecular weight Mw of the fluorine-containing resin is 4.8 KDa, and the molecular weight distribution index is 1.2.

[0151] Comparative Example 2

[0152] A fluorine-containing resin, the structural units of which are The weight average molecular weight Mw of the fluorine-containing resin was 5.0 KDa, and the molecular weight distribution index was 1.4.

[0153] Comparative Example 3

[0154] A fluorine-containing resin, the structural units of which are The weight average molecular weight Mw of the fluorine-containing resin is 5.0 KDa, and the molecular weight distribution index is 1.2.

[0155] Comparative Example 4

[0156] A fluorine-containing resin, the structural units of which are The weight average molecular weight Mw of the fluorine-containing resin is 4.8 KDa, and the molecular weight distribution index is 1.22.

[0157] Comparative Example 5

[0158] A fluorine-containing resin, the structural units of which are The weight average molecular weight Mw of the fluorine-containing resin was 5.0 KDa, and the molecular weight distribution index was 1.4.

[0159] Performance Testing

[0160] (1) An equal amount of the fluorine-containing resins of the above-mentioned embodiments and comparative examples were dissolved in an equal amount of solvent to obtain a resin composition, and a plurality of hydrophobic barrier films having equal surface roughness and thickness were obtained by using the resin composition. Under the same test conditions, the static contact angle (θ) of a water drop on the hydrophobic barrier films of the embodiments and comparative examples was tested. SCA ), advancing contact angle (θ ACA ), receding contact angle (θ RCA ) and the roll angle (θ TA ), the results are summarized in Table 1. Among them, the advancing contact angle (θ ACA ), receding contact angle (θ RCA ) and the roll angle (θ TA ) were measured using the tilted plate method, and the volume of the water droplet was 50 μL.

[0161] (2) The hydrophobic barrier films of the above-prepared embodiments and comparative examples were subjected to the same development treatment (the developer used a TMAH aqueous solution with a mass fraction of 2.38%), and then the static contact angle test was performed on each hydrophobic barrier film after the development treatment. The test liquid was water, and the volume of the water droplet was 50 μL. When testing each sample, the test steps were the same; the test results are summarized in Table 2; wherein ND means complete wetting and the contact angle cannot be measured.

[0162] Table 1

[0163] Case <![CDATA[θ SCA / °]]> <![CDATA[θ ACA / °]]> <![CDATA[θ RCA / °]]> <![CDATA[θ TA / °]]> Example 1 91 89 81 8 Example 2 94 95 86 8 Example 3 88 91 78 12 Example 4 91 92 82 9 Comparative Example 1 91 96 83 13 Comparative Example 2 84 93 64 29 Comparative Example 3 86 94 78 17 Comparative Example 4 83 97 68 26 Comparative Example 5 86 90 68 21

[0164] Table 2

[0165]

[0166]

[0167] Combined with the data in Table 1, it can be seen that the fluorine-containing resin provided in the embodiment of the present application has excellent hydrophobicity, and after exposure and development treatment, it has good hydrophilicity. The above fully illustrates that the fluorine-containing resin provided in the embodiment of the present application has both high hydrophobicity and excellent alkali reactivity.

[0168] The above is an exemplary embodiment of the present application. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made thereto without departing from the principles of the present application. These improvements and modifications are also considered to be within the scope of protection of the present application.

Claims

1. A fluorine-containing monomer, characterized in that The fluorine-containing monomer includes a structure shown in formula (II): Wherein, R1 is any one of a hydrogen atom, a fluorine atom, a methyl group or a methyl group substituted with a fluorine atom; R 21 is a single bond, or, R 21 is an alkylene group; R 22 is a cycloalkyl substituted with a substituent, wherein the substituent is The position marked with * is connected to the cycloalkyl group; R3 is a straight-chain fluorinated alkylene group, and R4 is a C1-C10 alkyl group or a C1-C10 fluorinated alkyl group.

2. The fluorinated monomer according to claim 1, characterized in that The cycloalkyl group is a C4-C10 cubic cycloalkyl group.

3. The fluorinated monomer according to claim 2, characterized in that The C4-C10 cubic cycloalkyl group includes any one of formula (A) to formula (E):

4. The fluorinated monomer according to any one of claims 1 to 3, characterized in that The R 21 It is a C1-C5 straight chain alkylene group.

5. The fluorinated monomer according to any one of claims 1 to 4, characterized in that The R 22 In the formula (a), the number of the substituents is a positive integer of 1-3.

6. The fluorinated monomer according to any one of claims 1 to 5, characterized in that The R3 is a C1-C5 straight-chain fluorinated alkylene group.

7. The fluorine-containing monomer according to claim 6, characterized in that The R3 is any one of -CHF-, -CF2-, -CHFCF2-, -CF2CF2-, -CF2CF2CF2-, -CHFCF2CF2-, -CF2CF2CHF-, -CF2CHFCF2-, -CF2CF2CF2CF2-, -CF2CF2CF2CF2-.

8. The fluorinated monomer according to any one of claims 1 to 7, characterized in that The fluorine-containing monomers include: and / or, 9. The fluorinated monomer according to claim 8, characterized in that The fluorinated monomers include: and / or, 10. A method for preparing a fluorine-containing monomer according to any one of claims 1 to 9, characterized in that: include: Mix the first monomer and the second monomer A first reaction is performed to obtain a preform; R1 is any one of a hydrogen atom, a fluorine element, a methyl group, or a methyl group substituted with a fluorine atom; R 21 is a single bond, or, R 21 is an alkylene group; R 22 ' is a cycloalkyl group substituted with one or more hydroxyl groups; R3 is a straight-chain fluorinated alkylene group; The preform and R4OH are mixed and subjected to a second reaction to obtain the aforementioned fluorine-containing monomer; wherein R4 is a C1-C10 alkyl group or a C1-C10 fluorine-containing alkyl group.

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