A resin, a composition, a film layer, an electronic device, and a method for manufacturing the same

Abstract

This application provides a resin, a composition, a film, an electronic device, and a method for preparing the same. The resin includes a first repeating unit and a second repeating unit, where R1 is selected from unsubstituted C1-C. 20 R2 is an alkyl group or a C1-C6 fluoroalkyl group; R2 is selected from a single bond or an unsubstituted C1-C6 fluoroalkyl group. 10 The resin, composition, and film are all alkylene groups; R3 is selected from, R5 and R6 are independently selected from substituted or unsubstituted alkyl groups, R4 is selected from H or substituted or unsubstituted alkyl groups, R6 and R4 can be linked to form a ring, at least one of R5, R6 and R4 contains a fluorine atom, and n is 1 or 2, indicating the linking site. This resin, composition, and film can be used simultaneously in both positive and negative developing processes, ensuring the anti-collapse ability of the formed patterned structure, improving pattern stability, which is beneficial for the fabrication of electronic devices and obtaining electronic devices with excellent overall performance.

Description

Technical Field

[0001] This application relates to the field of electronic device fabrication, specifically to a resin, composition, film, electronic device, and method for fabricating the same. Background Technology

[0002] With the widespread use of electronic devices (such as semiconductor devices), the industry has increasingly higher requirements for the precision of the patterning process involved in their fabrication. Related technologies introduce an intermediate layer between the photosensitive material film and the substrate to reduce the impact of reflected and diffracted light on the clarity and resolution of the patterned film. However, existing intermediate layers cannot be simultaneously applied to both positive and negative development processes, causing pattern collapse in the patterned photosensitive material film, reducing pattern resolution, and hindering the fabrication of electronic devices. Summary of the Invention

[0003] In view of this, this application provides a resin, a composition, a film, an electronic device, and a method for preparing the same. The resin changes from hydrophobic to hydrophilic after exposure, making it suitable for both positive and negative development processes. This ensures the anti-collapse ability of the patterned structure, improves pattern stability, and facilitates improved pattern resolution. Consequently, it is beneficial for the preparation of electronic devices, such as semiconductor devices, resulting in electronic devices with excellent overall performance.

[0004] In a first aspect, this application provides a resin comprising a first repeating unit and a second repeating unit, wherein the first repeating unit is shown in formula (I) and the second repeating unit is shown in formula (II).

[0005] Formula (I), Equation (II),

[0006] R1 is selected from unsubstituted C1-C. 20 R2 is an alkyl group, or a C1-C6 fluoroalkyl group; R2 is selected from single bonds or unsubstituted C1-C6 alkyl groups. 10 Alkylene;

[0007] R3 is selected from R5 and R6 are independently selected from substituted or unsubstituted alkyl groups, R4 is selected from H or a substituted or unsubstituted alkyl group, R6 and R4 may be linked together to form a ring, and at least one of R5, R6 and R4 contains a fluorine atom, and n is 1 or 2. Indicates the connection site.

[0008] In the resin provided in this application, the first repeating unit ensures the compatibility and reactivity between the resin and other components of the composition, and the second repeating unit can improve the ability of molecular chain segments to migrate and accumulate to the surface in the film layer, which is beneficial for their accumulation on the film layer surface; at the same time, R3 in the second repeating unit can improve the hydrophilicity after exposure, so that the composition and film layer containing the resin can be used for both positive and negative development processes, which is beneficial for its use in the preparation of electronic devices and improves the performance of the prepared electronic devices.

[0009] Optionally, the resin further includes a third repeating unit, as shown in formula (III).

[0010] Formula (III).

[0011] The third repeating unit in the resin provided in this application further improves the compatibility between the resin and other components of the composition, which is beneficial to further improving the stability of the composition.

[0012] Optionally, the molar fraction of the second repeating unit in the resin is 20%-80%, which is beneficial to further enhance the ability of resin molecular chain segments to migrate to the surface.

[0013] Optionally, the resin has a weight-average molecular weight of 600 g / mol to 6000 g / mol. A suitable weight-average molecular weight is advantageous for its use in the composition, facilitating migration and enrichment within the film layer.

[0014] Optionally, R1 is selected from the C1-C6 fluoroalkyl groups with a hydrogen atom substitution rate of less than or equal to 50%, which is beneficial to further improve the compatibility and reactivity of the resin.

[0015] Optionally, R2 is selected from single-bonded or unsubstituted C1-C4 alkylene groups.

[0016] Optionally, the ratio of the number of hydrogen atoms replaced by fluorine atoms to the total number of substituted hydrogen atoms in R5, R6 and R4 is less than or equal to 90%, which is beneficial to improving the migration ability of resin molecular chain segments.

[0017] Optionally, R6 and R4 are connected to form a ring C5-C6.

[0018] Optionally, R5, R6, and R4 are independently selected from substituted or unsubstituted C1-C4 alkyl groups.

[0019] In a second aspect, this application provides a composition comprising a resin component, an acid-generating agent, and a first solvent, wherein the resin component comprises the resin described in the first aspect and a silicone-containing resin.

[0020] The resin can migrate to the interface during coating and generate hydrophilic groups after being exposed to light, changing the polarity of the composition. This allows the composition to be used in both positive and negative development processes. Furthermore, the resin does not significantly affect the optical properties and etching rate of the film after coating, which is beneficial for the wide application of the composition.

[0021] Optionally, the resin content in the composition is 0.01%-0.5% by mass. A low resin content in the composition does not affect the optical properties and etching rate after film formation. Furthermore, a small amount of resin can still accumulate on the film surface after formation, allowing it to receive more light and react under illumination. This alters the film's polarity, especially its surface polarity, improving its compatibility with the patterned photosensitive material film and increasing the structural stability of the patterned photosensitive material film. This, in turn, facilitates subsequent processes and helps improve the performance of the resulting electronic devices.

[0022] Optionally, the mass content of the silicone resin in the composition is 0.1%-5%, which is beneficial to improving the mechanical properties of the formed film.

[0023] Optionally, the mass ratio of the resin to the silicone resin is 1:(4-65), which can balance the surface hydrophilicity of the composition after exposure with the etching rate and reflectivity of the solid molded product of the composition, which is beneficial to further improve the performance of the composition and its solid molded product.

[0024] Optionally, the mass content of the acid-generating agent in the composition is 0.005%-0.1%, which is beneficial to improving the performance of the film after film formation.

[0025] Optionally, the composition may further include an acidic substance, wherein the acidic substance comprises 0.001%-2% by mass in the composition, which is beneficial for controlling the pH value of the composition within a suitable range.

[0026] Optionally, the composition further includes a crosslinking catalyst, wherein the crosslinking catalyst has a mass content of 0.01%-0.1% in the composition, which is beneficial for the composition to cure into a film.

[0027] Optionally, the pH of the composition is 2-5. A suitable pH of the composition is beneficial for the mixing and dispersion of the components.

[0028] Optionally, the composition has a viscosity of 3.3 cps-3.9 cps at 25°C, which is beneficial for the leveling and film formation of the composition.

[0029] Optionally, the silicone-containing resin includes a fourth repeating unit and a fifth repeating unit, the fourth repeating unit being shown in formula (IV) and the fifth repeating unit being shown in formula (V).

[0030] Formula (IV), Equation (V),

[0031] R7 is selected from substituted or unsubstituted C1-C. 20 Hydrocarbon group.

[0032] Thirdly, this application provides a film layer comprising a solid molded article of the composition described in the second aspect. The resin molecular chain segments in the film layer can accumulate on the film surface, and the surface polarity of the film layer can be changed after illumination, making the film layer suitable for both positive and negative development processes. Furthermore, the refractive index, absorption coefficient, and dry etching rate of the film layer meet the application requirements, which is beneficial for its use in the fabrication of electronic devices.

[0033] Optionally, the thickness of the film layer is 10 nm to 1000 nm. A suitable film layer thickness is advantageous for its use in the fabrication of electronic devices.

[0034] Optionally, the refractive index of the film layer is 1.55-1.75. The film layer can better match the substrate and the photosensitive material film, reducing reflected light and exhibiting excellent anti-reflective properties, which is beneficial for improving the fabrication precision of electronic devices.

[0035] Optionally, the light absorption coefficient of the film layer is 0.17-0.27. The film layer can effectively absorb light, reduce reflected light, has excellent anti-reflection properties, and avoids the influence of interference light on the preparation process.

[0036] Optionally, the etching rate of the film is 800 Å / min-1200 Å / min, wherein the etching gas is a fluorine-containing gas. The film provided in this application has an excellent etching rate, ensuring rapid and efficient fabrication of patterned substrates and electronic devices.

[0037] Fourthly, this application provides a method for fabricating an electronic device, comprising:

[0038] The composition described in the second aspect is coated onto a substrate to form a film layer on the substrate;

[0039] A photosensitive material film is formed on the surface of the film layer;

[0040] A patterned photosensitive material film is formed by exposure and development using a photomask.

[0041] The film formed by the composition provided in this application can produce electronic devices with excellent overall performance.

[0042] Fifthly, this application provides an electronic device prepared by the preparation method described in the fourth aspect.

[0043] The electronic device provided in this application has high precision and excellent overall performance. Attached Figure Description

[0044] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0045] Figure 1 This is a schematic diagram of the patterning process provided in one embodiment of this application.

[0046] Figure 2 This is the CD-SEM image after negative development corresponding to Example 4.

[0047] Figure 3 This is the CD-SEM image after negative development corresponding to Comparative Example 1.

[0048] Figure 4 This is the CD-SEM image after negative development, corresponding to Comparative Example 2. Detailed Implementation

[0049] The technical solutions in the embodiments of this application will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments in this application, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of this application.

[0050] In the manufacturing of electronic devices (such as semiconductor devices), devices are constantly being miniaturized. To avoid pattern collapse / collapse during development due to excessive aspect ratio, the thickness of the patterning film is becoming increasingly thinner, and the feature size is continuously decreasing. During the patterning process, when the exposure light hits the substrate, some light is reflected. Since the reflected light has the same frequency as the exposure light, interference occurs between the two light rays in the photosensitive film, forming standing waves. This standing wave effect leads to uneven light intensity distribution in the photosensitive film, making overexposure more likely. This results in decreased stability of the patterning process and poor resolution of the produced pattern, with increased line width roughness. Related technologies address this by applying an anti-reflective film to the substrate surface to absorb reflected light from the bottom, thereby reducing the standing wave phenomenon in the photosensitive film. This allows for better control of the pattern's line width roughness and improves the pattern's resolution.

[0051] Positive development is a process that combines a positive photosensitive film with an alkaline aqueous solution developer. In positive development, the hydrophilic exposed areas react with the alkaline developer to form water-soluble substances, which are then removed. The hydrophobic unexposed areas remain intact, resisting the erosion of the developer and thus preserved. With the miniaturization of electronic devices, light diffraction is approaching its physical limits, and the contrast of exposure used for pattern formation is gradually decreasing. This leads to a reduction in the dissolution contrast of the positive photosensitive film, resulting in a deterioration in the resolution and focal length latitude of hole and groove patterns after exposure and development. Therefore, to resolve the extremely fine hole patterns that cannot be achieved with positive exposure using negative exposure, negative patterns can be formed using organic solvent development with a high-resolution positive photoresist composition. This is called negative development, where the unexposed (hydrophobic) areas are dissolved by the organic solvent developer, while the exposed areas (which have become hydrophilic) remain undissolved and preserved. Because positive and negative development processes differ, for example, directly using an anti-reflective film from a positive development process in a negative development process can cause pattern collapse / collapse and affect the line width and roughness of the pattern. Furthermore, if different anti-reflective films are used in positive and negative development processes, different equipment must be used for control in electronic device manufacturing, increasing production costs and hindering cost reduction in electronic device manufacturing.

[0052] In view of this, this application provides a resin comprising a first repeating unit and a second repeating unit, wherein the first repeating unit is shown in formula (I) and the second repeating unit is shown in formula (II).

[0053] Formula (I), Equation (II),

[0054] R1 is selected from unsubstituted C1-C. 20 R2 is an alkyl group, or a C1-C6 fluoroalkyl group; R2 is selected from single bonds or unsubstituted C1-C6 alkyl groups. 10 Alkylene;

[0055] R3 is selected from R5 and R6 are independently selected from substituted or unsubstituted alkyl groups, R4 is selected from H or a substituted or unsubstituted alkyl group, R6 and R4 may be linked together to form a ring, and at least one of R5, R6 and R4 contains a fluorine atom, and n is 1 or 2. Indicates the connection site.

[0056] In the resin provided in this application, the first repeating unit ensures the compatibility and reactivity between the resin and other components of the composition, and the second repeating unit can improve the ability of molecular chain segments to migrate and accumulate to the surface in the film layer, which is beneficial for their accumulation on the film layer surface; at the same time, R3 in the second repeating unit can improve the hydrophilicity after exposure, so that the composition and film layer containing the resin can be used for both positive and negative development processes, which is beneficial for its use in the preparation of electronic devices and improves the performance of the prepared electronic devices.

[0057] In the positive development process, the exposed areas of the photosensitive material film change from a relatively hydrophobic state to a relatively hydrophilic state and are removed in the alkaline aqueous solution developer. The unexposed areas remain unchanged and are still hydrophobic, so they are not removed in the alkaline aqueous solution developer. Thus, a patterned photosensitive material film is obtained after development. At the same time, the molecular chain segments with the second repeating unit in the unexposed areas of the film layer do not change their properties because they are not exposed to light. They are both relatively hydrophobic and have similar polarities to the patterned photosensitive material film, which ensures the stability of the patterned photosensitive material film and is beneficial to the preparation process.

[0058] In the negative development process, the exposed areas of the photosensitive material film change from a relatively hydrophobic state to a relatively hydrophilic state, and are therefore not removed by the organic solvent developer. The unexposed areas remain unchanged, still hydrophobic, and are removed by the organic solvent developer, thus forming a patterned photosensitive material film after development. At the same time, resin accumulates on the film surface. The molecular chain segments with the second repeating unit in the exposed areas of the film become hydrophilic after the second repeating unit reacts due to light exposure, making the film surface change from hydrophobic to relatively hydrophilic. Both the film surface and the bottom layer of the patterned photosensitive material film are hydrophilic and have similar polarities, ensuring the stability of the patterned photosensitive material film and facilitating the preparation process.

[0059] In some embodiments of this application, the resin further includes a third repeating unit, which is shown in formula (III).

[0060] Formula (III).

[0061] The third repeating unit in the resin provided in this application further improves the compatibility between the resin and other components of the composition, which is beneficial to further improving the stability of the composition.

[0062] In this application, alkyl refers to an alkane molecule with one hydrogen atom removed, and substituted or unsubstituted alkyl groups can be straight-chain or branched. For example, the unsubstituted alkyl group may include, but is not limited to, at least one of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, heptyl, octyl, nonyl, and decyl. The substituents in the substituted alkyl group may include, but are not limited to, at least one selected from halogen atoms (F, Cl, Br, I, etc.), nitrogen atoms, oxygen atoms, sulfur atoms, hydroxyl groups, nitro groups, amino groups, mercapto groups, methoxy groups, and cyano groups. For example, the substituents in the substituted alkyl group may be fluorine atoms (F).

[0063] In this application, alkylene is an alkane molecule with two hydrogen atoms removed. Substituted or unsubstituted alkylene can be linear or branched. For example, unsubstituted alkylene may include, but is not limited to, at least one of methylene, ethylene, propylene, n-butylene, n-pentylene, and n-hexylene. Substituents in substituted alkylene may include, but are not limited to, at least one of halogen atoms (F, Cl, Br, I, etc.), nitrogen atoms, oxygen atoms, sulfur atoms, hydroxyl, nitro, amino, mercapto, methoxy, and cyano groups. For example, a substituent in a substituted alkylene may be F.

[0064] In this application, the first repeating unit ensures the compatibility of the resin in the composition. R1 is selected from unsubstituted C1-C. 20 The alkyl group, or C1-C6 fluoroalkyl group, i.e., the unsubstituted alkyl group has 1-20 carbon atoms, for example, the number of carbon atoms of the alkyl group can be, but is not limited to, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, etc.; the fluoroalkyl group has 1-6 carbon atoms, for example, the number of carbon atoms of the fluoroalkyl group can be, but is not limited to, 1, 2, 3, 4, 5 or 6, etc. In some embodiments of this application, R1 is selected from branched alkyl groups, which is beneficial to improving the compatibility and reactivity of the resin and ensuring the performance of the film layer before and after exposure. In some embodiments of this application, R1 is selected from C1-C6 fluoroalkyl groups with a hydrogen atom substitution rate of less than or equal to 50%. That is, the ratio of the number of hydrogen atoms replaced by fluorine atoms to the total number of hydrogen atoms in the unsubstituted C1-C6 alkyl group is less than or equal to 50%, for example, the general formula of C1-C6 fluoroalkyl groups is -C aF b H c 1≤a≤6, b+c=2a+1, b / (b+c)≤50%. For example, the hydrogen substitution rate of the C1-C6 fluoroalkyl group can be, but is not limited to, less than 50%, less than 45%, less than 40%, less than 35%, less than 30%, less than 25%, less than 20%, less than 15%, or less than 10%. In some embodiments, R1 is selected from C1-C6 fluoroalkyl groups with a hydrogen substitution rate less than or equal to 20%, which is beneficial for further improving the compatibility and reactivity of the resin. The selection of R1 in the multiple first repeating units of the resin can be the same or different.

[0065] In some embodiments of this application, the molar fraction of the first repeating unit in the resin is 20%-80%. This is advantageous in ensuring the compatibility and reactivity of the resin with silicone-containing resins. Exemplarily, the molar fraction of the first repeating unit in the resin can be, but is not limited to, 20%, 25%, 30%, 35%, 37%, 40%, 42%, 43%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, or 80%. In this application, the molar fraction of the repeating unit is obtained by detection using 1H NMR spectroscopy.

[0066] In some embodiments of this application, the first repeating unit is derived from the first monomer. That is, the first monomer reacts to form the first repeating unit in the resin. The first monomer can be a hydrolyzable silane monomer. In some embodiments of this application, the first monomer has the structural formula R1-Si(OR) 1 )3, where R1 is selected from unsubstituted C1-C 20 Alkyl groups, or C1-C6 fluoroalkyl groups, R 1 Selected from substituted or unsubstituted C1-C6 alkyl groups. Wherein, R... 1 The alkyl group is selected from substituted or unsubstituted C1-C6 alkyl groups, and the number of carbon atoms in the alkyl group may be, but is not limited to, 1, 2, 3, 4, 5, or 6. The first repeating unit in the resin may be derived from the same first monomer or from different first monomers.

[0067] In this application, the second repeating unit can not only ensure the migration ability of the resin, but also react under exposure to form hydrophilic hydroxyl groups, thereby changing the polarity of the film layer. This makes the composition and film layer suitable for both positive and negative development processes, improving the pattern's resistance to collapse.

[0068] The second repeating unit is generated under exposure. It changes from a hydrophobic group to a relatively hydrophilic group.

[0069] In the second repeating unit, R2 is selected from single bonds or unsubstituted C1-C bonds. 10 Alkylene, wherein C1-C10 The alkylene group is an unsubstituted alkylene group having 1-10 carbon atoms; for example, the number of carbon atoms in the alkylene group may be, but is not limited to, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10. In some embodiments of this application, R2 is selected from single-bonded or unsubstituted C1-C4 alkylene groups, which is beneficial for obtaining the second repeating unit.

[0070] In this application, R3 can react under light, changing the polarity of the molecular chain segment, which is beneficial for the use of the resin. R5 is selected from substituted or unsubstituted alkyl groups; for example, R5 is selected from substituted or unsubstituted C1-C4 alkyl groups, that is, the number of carbon atoms in the alkyl group can be, but is not limited to, 1, 2, 3, or 4. R6 is selected from substituted or unsubstituted alkyl groups; for example, R6 is selected from substituted or unsubstituted C1-C4 alkyl groups, that is, the number of carbon atoms in the alkyl group can be, but is not limited to, 1, 2, 3, or 4. R4 is selected from H or substituted or unsubstituted alkyl groups; for example, R4 is selected from H or substituted or unsubstituted C1-C4 alkyl groups, that is, the number of carbon atoms in the alkyl group can be, but is not limited to, 1, 2, 3, or 4. R6 and R4 in R3 can be linked to each other to form a ring; for example, R6 and R4 are linked to form a C5-C6 ring, that is, R6 and R4 are linked to form a carbon ring with 5 or 6 carbon atoms. Understandably, R6 and R4 in R3 are not connected and are independent groups, or R6 and R4 in R3 are connected to form a carbide ring. At least one of R5, R6, and R4 contains a fluorine atom, meaning at least one of R5, R6, and R4 is a fluoroalkyl group. This results in the resin molecular chain segment having a lower surface energy, enabling it to obtain the thermodynamic driving force for migration to the interface, while simultaneously reducing the intermolecular forces of the resin, thus giving the resin molecular chain segment the kinetic ability to migrate rapidly. This ensures the migration ability of the resin molecular chain segment. In some embodiments of this application, the ratio of the number of hydrogen atoms replaced by fluorine in R5, R6, and R4 to the total number of substituted hydrogen atoms is less than or equal to 90%. That is, the ratio of all hydrogen atoms replaced by fluorine atoms in the three groups of R5, R6, and R4 to the total number of hydrogen atoms in the unsubstituted groups is less than or equal to 90%, which is beneficial to improving the migration ability of the resin molecular chain segment. For example, the ratio of the number of hydrogen atoms replaced by fluorine atoms in R5, R6, and R4 to the total number of substituted hydrogen atoms can be, but is not limited to, less than 90%, less than 85%, less than 80%, less than 75%, less than 70%, less than 65%, less than 60%, less than 55%, less than 50%, less than 45%, less than 40%, etc. In some embodiments, the ratio of the total number of hydrogen atoms replaced by fluorine atoms in the three groups R5, R6, and R4 to the total number of hydrogen atoms in the unsubstituted groups can be 2%-90%.

[0071] In some embodiments of this application, R3 is selected from at least one of the following groups, which may or may not have a fluorine atom substituted or unsubstituted:

[0072] , , , , , , .

[0073] The above-mentioned functional groups have simple structures and are easy to obtain, which is beneficial to the acquisition and use of resins.

[0074] In this application, when n is 1, the preparation difficulty of the resin can be reduced and the preparation cost can be reduced; when n is 2, the polarity difference of the second repeating unit and the resin before and after exposure can be further changed, which is beneficial for the use of the resin composition and film in the preparation of electronic devices, and further improves the performance of the prepared electronic devices.

[0075] In multiple second repeating units of the resin, the choices of R2 and R3 can be the same or different; when n is 2, the choices of R3 in the same second repeating unit can be the same or different.

[0076] In some embodiments of this application, the molar fraction of the second repeating unit in the resin is 20%-80%. This is beneficial for further enhancing the ability of resin molecular chain segments to migrate to the surface. Exemplarily, the molar fraction of the second repeating unit in the resin may be, but is not limited to, 20%, 25%, 30%, 35%, 37%, 40%, 42%, 43%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, or 80%.

[0077] In some embodiments of this application, the molar ratio of the first repeating unit and the second repeating unit in the resin is 2:8 to 8:2. This is beneficial for balancing the hydrophilicity after exposure with the compatibility and reactivity of the resin in the system. The molar ratio of the first repeating unit and the second repeating unit is calculated by detecting the molar fraction of the first repeating unit and the second repeating unit in the resin. Exemplarily, the molar ratio of the first repeating unit and the second repeating unit in the resin can be, but is not limited to, 2:8, 3:7, 4:6, 1:1, 6:4, 7:3, or 8:2, etc.

[0078] In some embodiments of this application, the second repeating unit is derived from the second monomer. That is, the second monomer reacts to form the second repeating unit in the resin. The first monomer and the second monomer can undergo hydrolytic condensation under acidic conditions to form the resin. The second monomer can be a hydrolyzable silane monomer. In some embodiments of this application, the structural formula of the second monomer is as follows: The choices of n and R3 are as described above, and R 2 Selected from substituted or unsubstituted C1-C4 alkyl groups. Wherein, R... 2The alkyl group is selected from substituted or unsubstituted C1-C4 alkyl groups, and the number of carbon atoms in the alkyl group may be, but is not limited to, 1, 2, 3, or 4. The second repeating unit in the resin may be derived from the same second monomer or from different second monomers.

[0079] In this application, n is 1 or 2. For example, when n is 1, R3 and R2 can be in an anti-parallel relationship; when n is 2, the two R3s and R2s can be in a meta-parallel relationship. It is understood that the positional relationship between R3 and R2 in the benzene ring is not limited to this and can be selected as needed.

[0080] In some embodiments of this application, the third repeating unit is derived from the third monomer. That is, the third repeating unit in the resin is formed after the third monomer reacts. The first monomer, the second monomer, and the third monomer can undergo hydrolysis-condensation under acidic conditions to form the resin. The third monomer can be a hydrolyzable silane monomer. In some embodiments of this application, the third monomer is selected from at least one of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, and tetran-butoxysilane. In some embodiments, the third monomer can be selected from at least one of tetramethoxysilane and tetraethoxysilane. The third repeating unit in the resin can be derived from the same third monomer or from different third monomers. The hydroxyl group attached to the silicon atom in the third repeating unit can be obtained by hydrolysis-condensation of the third monomer or by the removal of the alkyl protecting group from the third monomer under heat or acid. In some embodiments of this application, when the resin includes the first repeating unit, the second repeating unit, and the third repeating unit, the total molar fraction of the first repeating unit and the third repeating unit in the resin is less than or equal to 80%, which is beneficial to the function of the second repeating unit in the resin.

[0081] In some embodiments of this application, the weight-average molecular weight of the resin is 600 g / mol to 6000 g / mol. A suitable weight-average molecular weight of the resin is advantageous for its use in the composition, facilitating migration and enrichment within the film layer. Exemplarily, the weight-average molecular weight of the resin can be, but is not limited to, 600 g / mol, 800 g / mol, 1000 g / mol, 1300 g / mol, 1500 g / mol, 1900 g / mol, 2000 g / mol, 2500 g / mol, 2700 g / mol, 3000 g / mol, 3200 g / mol, 3500 g / mol, 3800 g / mol, 4000 g / mol, 4300 g / mol, 4500 g / mol, 4700 g / mol, 5000 g / mol, 5100 g / mol, 5500 g / mol, 5800 g / mol, or 6000 g / mol. In some embodiments, the weight-average molecular weight of the resin can be 800 g / mol to 4000 g / mol, which is beneficial for further migration and enrichment of the resin in the membrane layer, and further enhances the use of the membrane layer in different preparation processes. In this application, the weight-average molecular weight of the resin is obtained by gel permeation chromatography.

[0082] In this application, the two or three monomers described above can react under acidic conditions to form a resin. In some embodiments of this application, the first monomer and the second monomer undergo a first reaction under acidic conditions to form a resin, or the first monomer, the second monomer, and the third monomer undergo a first reaction under acidic conditions to form a resin. The acidic conditions refer to conditions containing an acidic solution, which may include at least one of inorganic and organic acids. The acidic solution used in the resin preparation process is referred to as the first acidic solution. Exemplarily, inorganic acids may include, but are not limited to, at least one of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, and hydrofluoric acid; organic acids may include, but are not limited to, at least one of methanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, benzoic acid, fumaric acid, maleic acid, citric acid, adipic acid, oxalic acid, formic acid, acetic acid, propionic acid, butyric acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, and phthalic acid. Specifically, the aforementioned two or three monomers are mixed with a first acid solution to form a first mixture, which is then hydrolyzed and condensed to form a resin-containing solution. Alternatively, multiple monomers can be gradually added dropwise to the first acid solution to form the first mixture for dehydration and condensation, or the first acid solution can be gradually added dropwise to a liquid containing multiple monomers to form the first mixture for dehydration and condensation. In some embodiments of this application, the mass content of the first acid solution in the first mixture is 0.001%-5%, which is beneficial for promoting the hydrolysis and condensation. For example, the mass content of the first acid solution in the first mixture can be, but is not limited to, 0.001%, 0.005%, 0.01%, 0.03%, 0.05%, 0.08%, 0.1%, 0.12%, 0.14%, 0.15%, 0.17%, 0.2%, 0.3%, 0.5%, 0.9%, 1%, 1.3%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5%. In some embodiments, the mass content of the first acid in the first mixture can be 0.01%-0.2%, which is beneficial to the hydrolysis and condensation process while avoiding the occurrence of side reactions.

[0083] In some embodiments of this application, the first mixture may further include a second solvent. The second solvent is used to dissolve and disperse the various monomers and the first acid solution, which is beneficial for the hydrolysis condensation. In some embodiments, the second solvent may be selected from at least one of water and water-soluble organic solvents. Exemplarily, water-soluble organic solvents may include, but are not limited to, alcohol solvents (such as methanol, ethanol, n-propanol, isopropanol, etc.), ether solvents (such as tetrahydrofuran, etc.), polyol ether solvents (such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, etc.), ketone solvents (such as acetone, etc.), and nitrile solvents (such as acetonitrile, etc.). The above-mentioned water-soluble organic solvents may be those that can or are easily removed by distillation or vacuum distillation, and the above-mentioned water-soluble organic solvents may be used as solvents in the composition. In some embodiments, the second solvent may be formed by mixing three or more solvents. The amount of the second solvent added to the first mixture is sufficient to meet the amount required for the dehydration condensation reaction of the monomers. The above-mentioned various monomers are hydrolyzable monomers with hydrolyzable groups. By controlling the content of the solvent, the reaction rate can be further improved and the reaction cost can be controlled, which is beneficial for the preparation of resins.

[0084] In some embodiments of this application, the mass content of all monomers in the first mixture is greater than or equal to 15%, which is beneficial for resin preparation. Exemplarily, the mass content of all monomers in the first mixture may be, but is not limited to, 15%, 18%, 20%, 23%, 25%, 27%, 30%, 32%, 35%, 36%, 38%, or 40%, etc.

[0085] In some embodiments of this application, the molar ratio of the second monomer to the total molar ratio of all monomers in the first mixture is 20%-80%. This is beneficial for increasing the content of the second monomer in the resin, which is advantageous for the use of the composition and the film in the fabrication of electronic devices. Specifically, the molar ratio of the second monomer to the total molar ratio of all monomers in the first mixture can be, but is not limited to, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, or 80%.

[0086] In the above reaction, at least 95 wt% of the hydrolyzable groups of all monomers are hydrolyzed into Si-OH or further condensed into Si-O-Si groups, which is beneficial for the preparation and use of the resin. In some embodiments of this application, the temperature of the first reaction can be 0℃-60℃, and the time of the first reaction can be 4h-48h. Exemplarily, the temperature of the first reaction can be, but is not limited to, 0℃, 5℃, 10℃, 15℃, 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, or 60℃, etc.; the time of the first reaction can be, but is not limited to, 4h, 5h, 8h, 10h, 12h, 14h, 15h, 17h, 20h, 24h, 25h, 30h, 33h, 35h, 36h, 38h, 40h, 45h, or 48h, etc. In some embodiments, the temperature of the first reaction can be 10℃-40℃, and the time of the first reaction can be 8h-24h.

[0087] Following the first reaction described above, solvent replacement can be performed through distillation or vacuum distillation, generating small-molecule alcohols, water, low-boiling-point water-soluble organic solvents, etc., thereby obtaining a resin-containing solution. In some embodiments of this application, the heating temperature for distillation or vacuum distillation is less than or equal to 60°C. Exemplarily, the heating temperature for distillation or vacuum distillation may be, but is not limited to, below 60°C, below 55°C, below 50°C, below 45°C, etc.

[0088] In some embodiments of this application, the solid content of the resin-containing solution is less than or equal to 20 wt%. Exemplarily, the solid content of the resin-containing solution may be, but is not limited to, less than 1 wt%, less than 2 wt%, less than 3 wt%, less than 4 wt%, less than 5 wt%, less than 6 wt%, less than 7 wt%, less than 8 wt%, less than 9 wt%, less than 10 wt%, less than 11 wt%, less than 12 wt%, less than 13 wt%, less than 14 wt%, less than 15 wt%, less than 16 wt%, less than 17 wt%, less than 18 wt%, less than 19 wt%, or less than 20 wt%. A diluent may be added to the resin-containing solution. The diluent may include, but is not limited to, alcohol solvents (such as methanol, ethanol, n-propanol, isopropanol, etc.), ether solvents (such as tetrahydrofuran, etc.), polyol ether solvents (such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, etc.), ketone solvents (such as acetone, etc.), and nitrile solvents (such as acetonitrile, etc.). Diluents can further reduce the solid content of resin-containing solutions, which helps improve the storage stability and storage period of the solution, and is beneficial to the use of the resin.

[0089] The resin also has end-capping groups, which may be, but are not limited to, at least one selected from trimethylsiloxy, hydroxy, vinyl, methoxy, ethoxy, etc.

[0090] This application provides a composition comprising a resin component, an acid-generating agent, and a first solvent. The resin component includes the resins described in any of the above embodiments and silicone-containing resins. The resin can migrate to the interface during coating and simultaneously generate hydrophilic groups upon exposure to light, altering the polarity of the composition. This allows the composition to be suitable for both positive and negative development processes. Furthermore, the resin does not significantly affect the optical properties (such as refractive index n and absorption coefficient k) and etching rate of the film formed by the composition, which is beneficial for the wide application of the composition.

[0091] The resin in the composition enables it to be used in both positive and negative developing processes without affecting the optical properties and etching rate of the film after formation. In some embodiments of this application, the resin content in the composition is 0.01%-0.5% by mass. The low resin content does not affect the optical properties and etching rate after film formation. Furthermore, the relatively low resin content allows it to accumulate on the film surface after formation, enabling it to receive more light and react under illumination. This alters the film polarity, particularly the surface polarity, thereby improving the compatibility with the patterned photosensitive material film and increasing its structural stability. This, in turn, facilitates subsequent processes (such as etching) and contributes to improving the performance of the resulting electronic device. For example, the mass content of resin in the composition may be, but is not limited to, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.4%, 0.45%, or 0.5%. In some embodiments, the mass content of resin in the composition may be 0.01%-0.09%.

[0092] The silicone resin in the composition exhibits good compatibility with other resins, ensuring the internal stability of the composition. Simultaneously, the silicone resin ensures the crosslinking degree and strength of the film layer after film formation, which is beneficial for the use of the film layer in the preparation process. In some embodiments of this application, the silicone resin includes a fourth repeating unit and a fifth repeating unit, the fourth repeating unit being shown in formula (IV) and the fifth repeating unit being shown in formula (V).

[0093] Formula (IV), Equation (V),

[0094] R7 is selected from substituted or unsubstituted C1-C. 20 Hydrocarbon group.

[0095] The composition contains a higher mass content of silicone resin than of resin, making silicone resin the main resin to ensure the mechanical properties of the film, while the resin is an auxiliary functional resin, enabling the film to be suitable for both positive and negative development processes.

[0096] In this application, R7 is selected from substituted or unsubstituted C1-C. 20 The hydrocarbon group, for example, R7 is selected from substituted or unsubstituted C6-C. 20 aryl, substituted or unsubstituted C1-C 20 Alkyl, substituted or unsubstituted C3-C 20 cycloalkyl, substituted or unsubstituted C2-C 20 alkenyl or substituted or unsubstituted C2-C 20 The alkynyl group. For example, R7 is selected from substituted or unsubstituted C6-C. 20 When the aryl group is aryl, the number of carbon atoms in the aryl group can be, but is not limited to, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; R7 is selected from substituted or unsubstituted C1-C groups. 20 When the alkyl group is alkyl, the number of carbon atoms in the alkyl group can be, but is not limited to, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; R7 is selected from substituted or unsubstituted C3-C atoms. 20 When the cycloalkyl group is substituted, the number of carbon atoms in the cycloalkyl group can be, but is not limited to, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; R7 is selected from substituted or unsubstituted C2-C groups. 20 When the alkenyl group is substituted, the number of carbon atoms in the alkenyl group can be, but is not limited to, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20; R7 is selected from substituted or unsubstituted C2-C groups. 20 When the alkynyl group is used, the number of carbon atoms in the alkynyl group can be, but is not limited to, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20. The choice of R7 in multiple fifth repeating units of silicone resin can be the same or different.

[0097] In this application, aryl groups may include, but are not limited to, at least one of phenyl, o-methylphenyl, m-methylphenyl, p-methylphenyl, dimethylphenyl, trimethylphenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-mercaptophenyl, o-methoxyphenyl, p-methoxyphenyl, dimethoxyphenyl, o-tert-butoxyphenyl, p-tert-butoxyphenyl, p-aminophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenyl, p-biphenyl, 1-anthrayl, 2-anthrayl, 9-anthrayl, 1-phenanthyl, 2-phenanthyl, 3-phenanthyl, 4-phenanthyl, 4-phenanthyl, 9-phenanthyl, benzyl, o-methoxybenzyl, p-methoxybenzyl, o-tert-butoxybenzyl, and p-tert-butoxybenzyl.

[0098] In this application, cycloalkyl groups may include, but are not limited to, at least one of cyclopropyl, cyclobutyl, 1-methyl-1-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, adamantyl, and norbornyl.

[0099] In this application, alkenyl groups may include, but are not limited to, straight-chain alkenyl groups and branched alkenyl groups. For example, alkenyl groups may include, but are not limited to, vinyl, 1-propenyl, 2-propenyl, 1-methyl-1-vinyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 1-ethylvinyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 1-n-propylvinyl, 1-methyl-1-butenyl, 1-methyl-2-butenyl, 2-ethyl-2-propenyl, 2-methyl-1-butenyl, and 2-methyl-2-butenyl. 1,2-dimethyl-1-butenyl, 1,1-dimethyl-2-propenyl, 1-isopropylvinyl, 1,2-dimethyl-1-propenyl, 1-cyclopentenyl, 2-cyclopentenyl, 3-cyclopentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 1-methyl-2-pentenyl, 1-methyl-3-pentenyl, 1-n-butylvinyl, 2-methyl-1-pentenyl, 2-methyl-2-pentenyl, 2-methyl-4-pentenyl, 2-n-propyl-2-propenyl, 3-methyl- 1-Pentenyl, 3-Methyl-2-pentenyl, 3-Methyl-3-pentenyl, 3-Ethyl-3-butenyl, 4-Methyl-1-pentenyl, 4-Methyl-2-pentenyl, 4-Methyl-3-pentenyl, 1,1-Dimethyl-2-butenyl, 1,1-Dimethyl-3-butenyl, 1,2-Dimethyl-3-butenyl, 1-Methyl-2-ethyl-2-propenyl, 1-sec-butylvinyl, 1,3-Dimethyl-1-butenyl, 2,3-Dimethyl-1-butenyl, 1-Ethyl-3-butenyl, 2-Isopropyl-2-propenyl, 3, At least one of 3-dimethyl-1-butenyl, 1-n-propyl-2-propenylhexyl, 2-ethyl-1-butenyl, 1-ethyl-2-methyl-1-propenyl, 1-methyl-2-cyclopentenyl, 1-methyl-3-cyclopentenyl, 2-methyl-1-cyclopentenyl, 2-methyl-2-cyclopentenyl, 2-methyl-3-cyclopentenyl, 3-methyl-1-cyclopentenyl, 3-methyl-2-cyclopentenyl, 3-methyl-3-cyclopentenyl, 1-cyclohexenyl, 2-cyclohexenyl, 3-cyclohexenyl, cyclopentadienylpropyl, dicycloheptenyl, and norbornenyl.

[0100] In this application, the alkynyl group may include, but is not limited to, straight-chain alkynyl and branched-chain alkynyl. For example, the alkynyl group may include, but is not limited to, at least one of ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, phenylethynyl, and 3-pentynyl.

[0101] In this application, R7 is selected from the substituted C6-C. 20 aryl, substituted C1-C 20 Alkyl, substituted C3-C20 cycloalkyl, substituted C2-C 20 alkenyl or substituted C2-C 20 When the alkynyl group is used, the substituent is selected from halogen atoms (such as F, Cl, Br, I, etc.), epoxy groups (such as epoxypropoxymethyl, epoxypropoxyethyl, epoxypropoxypropyl, epoxycyclohexylpropyl, etc.), acryloyl (-COCH=CH2), methacryloyl (-COCH=CH2CH3), mercapto (-SH), amino (-NH2), cyano (-CN), -OR 3 -SR 4 -CONR 5 R 6 Ester group, isocyanurate group (-N3C3O3), and lactone ring (-COO(CH2)). d At least one of R, where d is an integer greater than or equal to 2, and R 3 R 4 Independently selected from hydrocarbon groups, R 5 R 6 The lactone ring is independently selected from hydrogen atoms, or substituted or unsubstituted hydrocarbon groups. For example, the lactone ring can be a β-lactone ring (-COO(CH2)2), a γ-lactone ring (-COO(CH2)3), or a δ-lactone ring (-COO(CH2)4).

[0102] The fourth repeating unit in the silicone-containing resin ensures compatibility between the silicone-containing resin and the resin itself, and also ensures the silicon content after the composition is film-formed. In some embodiments of this application, the fourth repeating unit is derived from a fourth monomer. That is, the fourth monomer reacts to form the fourth repeating unit in the silicone-containing resin. The fourth monomer can be a hydrolyzable silane monomer. In some embodiments of this application, the fourth monomer is selected from at least one of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, and tetran-n-butoxysilane. In some embodiments, the fourth monomer can be selected from at least one of tetramethoxysilane and tetraethoxysilane. The fourth repeating unit in the silicone-containing resin can be derived from the same fourth monomer or from different fourth monomers; the third repeating unit of the resin and the fourth repeating unit in the silicone-containing resin can be the same or different.

[0103] The fifth repeating unit of the silicone resin ensures the compatibility between the silicone resin and other components of the composition, and also ensures the refractive index and absorption coefficient of the composition after film formation. In some embodiments of this application, the fifth repeating unit is derived from the fifth monomer. That is, the fifth monomer reacts to form the fifth repeating unit in the silicone resin. The fourth and fifth monomers can undergo hydrolytic condensation under acidic conditions to form the silicone resin. The fifth monomer can be a hydrolyzable silane monomer. In some embodiments of this application, the fifth monomer has the structural formula R7-Si(OR) 2)3, wherein R7 is selected from substituted or unsubstituted C1-C 20 hydrocarbon group, R 2 Selected from substituted or unsubstituted C1-C6 alkyl groups. Wherein, R... 2 The alkyl group is selected from substituted or unsubstituted C1-C6 alkyl groups, and the number of carbon atoms in the alkyl group can be, but is not limited to, 1, 2, 3, 4, 5, or 6. The fifth repeating unit in the silicone resin can be derived from the same fifth monomer or from different fifth monomers.

[0104] In some embodiments of this application, the molar fraction of the fourth repeating unit in the silicone resin is greater than or equal to 60%. This is beneficial for further improving the efficacy of the resin. In some embodiments, the molar fraction of the fourth repeating unit in the silicone resin can be 60%-80%, which is beneficial for balancing the efficacy of the resin and the storage stability of the composition. Exemplarily, the molar fraction of the fourth repeating unit in the silicone resin can be, but is not limited to, 60%, 63%, 65%, 68%, 70%, 72%, 75%, 76%, 79%, or 80%, etc.

[0105] In some embodiments of this application, the weight-average molecular weight of the silicone resin is 1000 g / mol to 15000 g / mol. A suitable weight-average molecular weight of the silicone resin is beneficial for spin-coating and easy baking for crosslinking. Exemplarily, the weight-average molecular weight of the silicone resin can be, but is not limited to, 1000 g / mol, 2000 g / mol, 3000 g / mol, 4000 g / mol, 5000 g / mol, 6000 g / mol, 7000 g / mol, 8000 g / mol, 9000 g / mol, 10000 g / mol, 11000 g / mol, 12000 g / mol, 13000 g / mol, 14000 g / mol, or 15000 g / mol. In some embodiments, the weight-average molecular weight of the silicone resin can be 1500 g / mol to 8000 g / mol, which is beneficial for its compatibility with the system and easy baking for crosslinking after spin-coating.

[0106] In this application, the fourth and fifth monomers undergo a second reaction under acidic conditions to form a silicone-containing resin. The acidic conditions refer to conditions containing an acidic solution, which may include at least one of inorganic and organic acids. The acidic solution used in the preparation of the silicone-containing resin is referred to as the second acidic solution. Exemplarily, the inorganic acid may include, but is not limited to, at least one of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, and hydrofluoric acid; the organic acid may include, but is not limited to, at least one of methanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, benzoic acid, fumaric acid, maleic acid, citric acid, adipic acid, oxalic acid, formic acid, acetic acid, propionic acid, butyric acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, and phthalic acid. Specifically, the fourth and fifth monomers are mixed with the second acidic solution to form a second mixture, which undergoes hydrolysis and condensation to form a solution containing the silicone-containing resin. This can be achieved by gradually adding multiple monomers dropwise to the second acidic solution to form the second mixture for dehydration and condensation reactions, or by gradually adding the second acidic solution dropwise to a liquid containing multiple monomers to form the second mixture for dehydration and condensation reactions. In some embodiments of this application, the mass content of the second acid in the second mixture is 0.001%-5%, which is beneficial for promoting hydrolysis and condensation. For example, the mass content of the second acid in the second mixture may be, but is not limited to, 0.001%, 0.005%, 0.01%, 0.03%, 0.05%, 0.08%, 0.1%, 0.12%, 0.14%, 0.15%, 0.17%, 0.2%, 0.3%, 0.5%, 0.9%, 1%, 1.3%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5%. In some embodiments, the mass content of the second acid in the second mixture may be 0.01%-0.2%, which is beneficial for hydrolysis and condensation while avoiding side reactions.

[0107] In some embodiments of this application, the second mixture may further include a third solvent. The third solvent is used to dissolve and disperse various monomers and the second acid solution, which is beneficial for the hydrolysis condensation. In some embodiments, the third solvent may be selected from at least one of water and water-soluble organic solvents. Exemplarily, water-soluble organic solvents may include, but are not limited to, alcohol solvents (such as methanol, ethanol, n-propanol, isopropanol, etc.), ether solvents (such as tetrahydrofuran, etc.), polyol ether solvents (such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, etc.), ketone solvents (such as acetone, etc.), and nitrile solvents (such as acetonitrile, etc.). The aforementioned water-soluble organic solvents may be those that can or are easily removed by distillation or vacuum distillation, and may be used as solvents in the composition. The amount of the third solvent added to the second mixture is sufficient to meet the requirements of the monomer dehydration condensation reaction. The fourth and fifth monomers are hydrolyzable monomers with hydrolyzable groups. By controlling the content of the third solvent, the reaction rate can be further increased and the reaction cost controlled, which is beneficial for the preparation of silicone resins. In some embodiments, when the third solvent includes water, the molar ratio of the hydrolyzable substituents of the fourth and fifth monomers to water in the second mixture is 1:(2-20). Exemplarily, the molar ratio of the hydrolyzable substituents of the fourth and fifth monomers to water in the second mixture may be, but is not limited to, 1:2, 1:3, 1:5, 1:6, 1:8, 1:10, 1:12, 1:15, 1:16, 1:18, or 1:20, etc.

[0108] In some embodiments of this application, the mass content of all monomers in the second mixture is greater than or equal to 30%, which is beneficial for the preparation of silicone resins. Exemplarily, the mass content of all monomers in the second mixture may be, but is not limited to, 30%, 35%, 38%, 40%, 42%, 45%, 46%, 49%, or 50%, etc.

[0109] In the above reaction, at least 95 wt% of the hydrolyzable groups of all monomers are hydrolyzed into Si-OH or further condensed into Si-O-Si groups, which is beneficial for the preparation and use of silicone-containing resins. In some embodiments of this application, the temperature of the second reaction can be 0℃-60℃, and the time of the second reaction can be 4h-48h. Exemplarily, the temperature of the second reaction can be, but is not limited to, 0℃, 5℃, 10℃, 15℃, 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, or 60℃, etc.; the time of the second reaction can be, but is not limited to, 4h, 5h, 8h, 10h, 12h, 14h, 15h, 17h, 20h, 24h, 25h, 30h, 33h, 35h, 36h, 38h, 40h, 45h, or 48h, etc. In some embodiments, the temperature of the second reaction can be 10℃-40℃, and the time of the second reaction can be 8h-24h.

[0110] Following the second reaction described above, solvent displacement can be achieved through distillation or vacuum distillation, producing small-molecule alcohols, water, low-boiling-point water-soluble organic solvents, etc., thereby obtaining a solution containing silicone resin. In some embodiments of this application, the heating temperature for distillation or vacuum distillation is less than or equal to 60°C. Exemplarily, the heating temperature for distillation or vacuum distillation may be, but is not limited to, below 60°C, below 55°C, below 50°C, below 45°C, etc.

[0111] In some embodiments of this application, the solid content of the solution containing silicone resin is less than or equal to 20 wt%. Exemplarily, the solid content of the solution containing silicone resin may be, but is not limited to, less than 1 wt%, less than 2 wt%, less than 3 wt%, less than 4 wt%, less than 5 wt%, less than 6 wt%, less than 7 wt%, less than 8 wt%, less than 9 wt%, less than 10 wt%, less than 11 wt%, less than 12 wt%, less than 13 wt%, less than 14 wt%, less than 15 wt%, less than 16 wt%, less than 17 wt%, less than 18 wt%, less than 19 wt%, or less than 20 wt%. A diluent can be added to the solution containing silicone resin to further reduce the solid content, which is beneficial for improving the storage stability and shelf life of the solution and for the use of the silicone resin.

[0112] Silicone-containing resins also have end-capping groups, which may be, but are not limited to, at least one selected from trimethylsiloxy, hydroxyl, vinyl, methoxy, ethoxy, etc.

[0113] In some embodiments of this application, the mass content of silicone resin in the composition is 0.1%-5%, which is beneficial for improving the mechanical properties of the formed film. Exemplarily, the mass content of silicone resin in the composition may be, but is not limited to, 0.1%, 0.11%, 0.12%, 0.15%, 0.2%, 0.25%, 0.3%, 0.35%, 0.5%, 0.75%, 0.9%, 1%, 1.2%, 1.5%, 1.7%, 2%, 2.3%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 3.7%, 4%, 4.1%, 4.5%, 4.6%, 4.9%, or 5%. In some embodiments, the mass content of silicone resin in the composition may be 0.1%-2%, which is beneficial for further controlling the film thickness and reflectivity of the formed film.

[0114] In some embodiments of this application, the mass ratio of resin to silicone resin is 1:(4-65), which can balance the surface hydrophilicity of the composition after exposure with the etching rate and reflectivity of the solid molded product of the composition, which is beneficial to further improve the performance of the composition and its solid molded product. For example, the mass ratio of resin to silicone resin can be, but is not limited to, 1:4, 1:5, 1:8, 1:10, 1:12, 1:15, 1:17, 1:20, 1:23, 1:25, 1:29, 1:30, 1:33, 1:35, 1:37, 1:40, 1:42, 1:45, 1:48, 1:49, 1:50, 1:51, 1:52, 1:53, 1:54, 1:55, 1:56, 1:57, 1:58, 1:59, 1:60, 1:61, 1:62, 1:63, 1:64, or 1:65.

[0115] The composition includes a first solvent capable of dissolving and dispersing the components in the composition, which is beneficial for improving the uniformity and stability of the composition dispersion, and also beneficial for coating and film formation. In some embodiments, the first solvent includes at least one of water and an alcohol ether solvent, which may include, but is not limited to, at least one of ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, and butanediol methyl ether. For example, the first solvent may be propylene glycol ethyl ether. In other embodiments, the first solvent may further include a non-alcoholic solvent, which may include, but is not limited to, at least one of toluene, cyclohexane, tetrahydrofuran, methyl tert-butyl ether, cyclopentyl methyl ether, acetone, cyclohexanone, methyl isobutyl ketone, methyl pentyl ketone, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol tert-butyl ether acetate, propylene glycol dimethyl ether, diethylene glycol methyl ether, ethyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, and γ-butyrolactone. The combination of alcohol ether solvents and non-alcoholic solvents further enhances the solubility and dispersibility of the components in the composition, and further improves the homogeneity and stability of the composition. In some embodiments, the first solvent includes both alcohol ether solvents and non-alcoholic solvents, and the mass content of the alcohol ether solvent in the first solvent is greater than or equal to 60%, further optimizing the solvent system of the composition and improving the dissolution and dispersion performance and the dispersion stability of each component. In some embodiments of this application, the mass content of the first solvent in the composition is 95%-99.9%. This facilitates the full dissolution and dispersion of each component, while ensuring the stability of the composition system and improving the coating ability and component uniformity of the composition. For example, the mass content of the first solvent in the composition may be, but is not limited to, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, 99%, 99.5%, or 99.9%.

[0116] The acid-generating agent in the composition is beneficial for improving the performance of the film after formation. The acid-generating agent can be a photoacid-generating agent, which generates acid through a photochemical reaction. In some embodiments of this application, the mass content of the acid-generating agent in the composition is 0.005%-0.1%, which is beneficial for cross-linking catalysis. Exemplarily, the mass content of the acid-generating agent in the composition can be, but is not limited to, 0.005%, 0.007%, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, or 0.1%. The acid-generating agent can be selected from at least one of onium salt compounds, sulfonylimide compounds, and disulfonylimide compounds.

[0117] In some embodiments of this application, the composition may further include a crosslinking catalyst. The crosslinking catalyst promotes the curing and crosslinking reaction of the composition to form a film, and also enhances the mechanical strength, thermal stability, and chemical stability of the film. In some embodiments, the mass content of the crosslinking catalyst in the composition is 0.01%-0.1%, which is beneficial for the composition to cure into a film. Exemplarily, the mass content of the crosslinking catalyst in the composition may be, but is not limited to, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, or 0.1%. The crosslinking catalyst may be selected from at least one of triphenylsulfonium salts having a carboxyl group, diphenyliodosulfonium salts having a carboxyl group, tetraphenyl quaternary phosphonium salts having a carboxyl group, and tetraalkyl quaternary ammonium salts having a carboxyl group, wherein the above organic salts may be monocarboxylic acid salts or polycarboxylic acid salts. Exemplarily, the crosslinking catalyst may be triphenylsulfonium nitrate. Alternatively, one or more of sulfonium salts, iodonium salts, quaternary phosphonium salts, and quaternary ammonium salts can be added to the aforementioned silicone resin as part of a hydrolyzable silane compound through co-hydrolysis and condensation. In other words, the silicone resin can have cross-linking catalytic groups and play a cross-linking catalytic role.

[0118] In some embodiments of this application, the composition may further include an acidic substance. The acidic substance can adjust the pH value of the composition, providing a suitable acidic environment for the resin components and improving the stability of the composition. In some embodiments, the mass content of the acidic substance in the composition is 0.001%-2%, which is beneficial for controlling the pH value of the composition within a suitable range. Exemplarily, the mass content of the acidic substance in the composition may be, but is not limited to, 0.001%, 0.005%, 0.008%, 0.01%, 0.05%, 0.07%, 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.1%, 1.3%, 1.5%, 1.6%, 1.8%, or 2%, etc. The acidic substance may include inorganic acids and / or organic acids; for example, inorganic acids may include, but are not limited to, at least one of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, and hydrofluoric acid, and organic acids may include, but are not limited to, at least one of methanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, benzoic acid, fumaric acid, maleic acid, citric acid, adipic acid, oxalic acid, formic acid, acetic acid, propionic acid, butyric acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, and phthalic acid. In some embodiments, the acidic substance may be nitric acid.

[0119] In some embodiments of this application, the composition may further include a surfactant. Surfactants can effectively improve the coating performance and film uniformity of the composition. In some embodiments, the mass content of the surfactant in the composition is 0.001%-0.1%. Exemplarily, the mass content of the surfactant in the composition may be, but is not limited to, 0.001%, 0.005%, 0.008%, 0.01%, 0.05%, 0.07%, 0.1%, 0.2%, 0.3%, 0.5%, 0.6%, 0.8%, or 1%. The surfactant may be selected from at least one of nonionic surfactants and fluorinated surfactants. Nonionic surfactants may include polyoxyethylene ethers, long-chain carboxylic acid esters of sorbitol, etc.

[0120] The composition may also contain other additives, such as rheology modifiers and binders, to further improve the performance of the composition. All of the above additives can be added according to actual usage requirements.

[0121] In some embodiments of this application, the pH value of the composition is 2-5. A suitable pH value facilitates the mixing and dispersion of the components. Exemplarily, the pH value of the composition may be, but is not limited to, 2, 3, 4, or 5. In some embodiments, the pH value of the composition may be 2-4. The pH value of the composition in this application may be obtained from the contribution of acidic substances, or it may be obtained by subsequently adding an acid, base, or other buffering agent to adjust the pH value. The method for testing the pH value of the composition in this application may be, but is not limited to, mixing the composition with an equal mass of water and then measuring it at room temperature (25±1°C) using a pH agent.

[0122] In some embodiments of this application, the viscosity of the composition at 25°C is 3.3 cps-3.9 cps, which is beneficial for the leveling and film formation of the composition. Exemplarily, the viscosity of the composition may be, but is not limited to, 3.3 cps, 3.4 cps, 3.5 cps, 3.6 cps, 3.7 cps, 3.8 cps, or 3.9 cps. In this application, the viscosity of the composition at 25°C is measured using a viscometer (such as an Anton Paar SVM3001).

[0123] In this application, a composition can be obtained by mixing a resin, a silicone resin, an acid-generating agent, and a solvent. It is understood that when the composition also contains a crosslinking catalyst, an acidic substance, a surfactant, or other additives, the composition can be obtained by mixing the resin, the silicone resin, the acid-generating agent, the solvent, and at least one of the crosslinking catalyst, the acidic substance, the surfactant, and other additives. Alternatively, the composition can be obtained by filtering after mixing.

[0124] This application provides the use of the resin in the film layer in any of the above embodiments.

[0125] This application provides the use of the compositions in any of the above embodiments in film layers.

[0126] This application provides a film layer comprising a solid molded article of the composition in any of the above embodiments. The resin molecular chain segments in the film layer can accumulate on the film surface, and the surface polarity of the film layer can be changed after light irradiation, making the film layer suitable for both positive and negative development processes. Furthermore, the refractive index, absorption coefficient, and dry etching rate of the film layer meet the application requirements, which is beneficial for its use in the fabrication of electronic devices.

[0127] In some embodiments of this application, the thickness of the film layer is 10 nm to 1000 nm. A suitable film layer thickness is advantageous for its use in the fabrication of electronic devices. Exemplarily, the film layer thickness can be, but is not limited to, 10 nm, 25 nm, 50 nm, 75 nm, 80 nm, 100 nm, 120 nm, 150 nm, 175 nm, 200 nm, 250 nm, 300 nm, 350 nm, 400 nm, 450 nm, 500 nm, 550 nm, 600 nm, 650 nm, 700 nm, 750 nm, 800 nm, 850 nm, 900 nm, 950 nm, or 1000 nm. In some embodiments, the film layer thickness can be 10 nm to 100 nm.

[0128] In this application, an ellipsometer is used to test the refractive index (n) and absorption coefficient (k) of the film layer at a wavelength of 193 nm. In some embodiments of this application, the refractive index (n) of the film layer is 1.55-1.75, which allows the film layer to better match the substrate and the photosensitive material film, reduce reflected light, and has excellent anti-reflection properties, which is beneficial to improving the fabrication precision of electronic devices. For example, the refractive index of the film layer may be, but is not limited to, 1.55, 1.57, 1.59, 1.60, 1.61, 1.62, 1.63, 1.64, 1.65, 1.66, 1.67, 1.68, 1.69, 1.70, 1.71, 1.72, 1.73, 1.74, or 1.75. In some embodiments of this application, the absorption coefficient (k) of the film layer is 0.17-0.27, which allows the film layer to effectively absorb light, reduce reflected light, has excellent anti-reflection properties, and avoids the influence of interference light on the fabrication process. For example, the light absorption coefficient of the film layer may be, but is not limited to, 0.17, 0.18, 0.19, 0.20, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26 or 0.27.

[0129] In some embodiments of this application, the etching rate of the film is 800 Å / min-1200 Å / min, wherein the etching gas is a fluorine-containing gas. The fluorine-containing gas composition is CF4 and CHF3, wherein the volume ratio of CF4 to CHF3 is 50%:50%. The etching rate affects the patterning rate and effect. The film provided in this application has an excellent etching rate, ensuring the rapid and efficient fabrication of patterned substrates and electronic devices.

[0130] In this application, a coating composition is baked to obtain a film layer. That is, the composition solidifies to form a solid molded article during the baking process. The coating can be performed using common coating methods in the art, such as spin coating. In some embodiments of this application, the baking temperature is 80℃-300℃ and the baking time is 10s-3000s, which is conducive to the full cross-linking and curing process and ensures the performance of the formed film layer. For example, the baking temperature may be, but is not limited to, 80℃, 100℃, 120℃, 130℃, 150℃, 175℃, 190℃, 200℃, 225℃, 250℃, 270℃, 280℃, or 300℃; the baking time may be, but is not limited to, 10s, 30s, 50s, 75s, 100s, 120s, 150s, 175s, 200s, 400s, 500s, 700s, 1000s, 1200s, 1500s, 1800s, 2000s, 2200s, 2500s, 2800s, or 3000s. In some embodiments, the baking temperature may be 150℃-250℃, and the baking time may be 30s-200s.

[0131] In some embodiments of this application, the composition can be coated onto the surface of a substrate and baked to obtain a film layer. The substrate can be selected according to actual needs; for example, the substrate can be a layer structure used in electronic device fabrication methods. For example, the substrate can be a substrate to be patterned, or the substrate can be a substrate to be patterned and a hard mask disposed on the surface of the substrate to be patterned. Exemplarily, the substrate to be patterned can be, but is not limited to, at least one of a silicon wafer substrate, a silicon nitride substrate, and a glass substrate; the hard mask can be, but is not limited to, a high-carbon content organic hard mask, etc. In other embodiments of this application, after cleaning the substrate, the composition is coated onto the surface of the substrate and baked to obtain a film layer. Cleaning can remove impurities and dust from the surface of the substrate, which is beneficial for the coating and film formation of the composition. The cleaning method can be, but is not limited to, using solvents, acids, ultrasonic cleaning, or jet cleaning, etc.; for example, ultrasonic cleaning can be used in one embodiment.

[0132] Figure 1 The schematic diagram of a patterning process provided in one embodiment of this application includes: coating a substrate 10 with the composition described in any of the above embodiments to form a film layer 20 on the substrate 10; forming a photosensitive material film 30 on the surface of the film layer 20; and exposing and developing the film using a photomask to form a patterned photosensitive material film 31. This development process can be either a positive or negative development process, increasing the diversity of process options for patterning. Simultaneously, the similarity in performance between the patterned photosensitive material film and the film layer ensures the structural stability of the pattern, especially preventing the collapse of patterns with large aspect ratios, which is beneficial for the use of the patterned photosensitive material film.

[0133] In this application, the substrate may be, but is not limited to, at least one of silicon wafer substrate, silicon nitride substrate, and glass substrate.

[0134] In some embodiments of this application, the patterning process may further include: setting a hard mask on a substrate surface; coating a composition on the surface of the hard mask to form a film layer on the substrate; forming a photosensitive material film on the surface of the film layer; and exposing and developing the film through a photomask to form a patterned photosensitive material film. The hard mask may be, but is not limited to, a high-carbon-content organic hard mask. The raw material for the photosensitive material film is a photosensitive material composition, which may include, for example, polyacrylate resins, photoacid-generating agents, and solvents. The photosensitive material composition also includes photodegrading alkalis and / or acid quenchers, the acid quenchers being used to capture acids. The photosensitive material composition is coated onto the film layer surface and then dried to remove the solvent from the coating, thus forming the photosensitive material film.

[0135] The exposure and development of a photosensitive material film using a photomask can involve exposing the photosensitive material film to an exposure light source through a photomask, causing a change in the solubility of the photosensitive material film, followed by development to transfer a pattern or its complementary pattern from the photomask to the photosensitive material film. The wavelength of the exposure light source can be 150nm-350nm. The development process can involve using a developer to develop the exposed photosensitive material film to form a patterned photosensitive material film. The developer can be, for example, one that alters the chemical properties of the exposed portion of the photosensitive material film, changing its solubility; the predetermined pattern can be obtained by cleaning the irradiated structure with a developing solution. In some embodiments, the positive developing solution can be an alkaline solution. For example, the developing solution can be a 0.5%-5% aqueous solution of tetramethylammonium hydroxide (TMAH). In some embodiments, the negative developing solution can be an organic solvent. For example, the organic solvent can be at least one of butyl acetate or similar ester solvents. The developing solution can be a mixture of one or more of the above solvents. Development can be achieved by immersion or coating (e.g., spin coating). The developing time between the developer and the exposed structure can be 10s-120s. A water rinsing process can be optionally added after development, with a rinsing time of 20s-120s, to further clean the structure. A drying process can be optionally added after exposure and before development; a drying process can also be optionally added after development.

[0136] In some embodiments of this application, the patterning process may further include: using a patterned photosensitive material film as a mask, etching the film layer under an etching gas (such as a fluorine-containing gas) to make the film layer a patterned film layer; this is beneficial for the fabrication of electronic devices.

[0137] This application provides a patterned substrate, which is fabricated using the patterning process described in any of the above embodiments. The patterned substrate has excellent resolution and clarity, which is beneficial for its use.

[0138] This application provides an electronic device including the patterned substrate described in any of the above embodiments. This is beneficial for improving the performance of the electronic device.

[0139] In some embodiments of this application, the electronic device further includes a functional layer disposed on a patterned substrate.

[0140] This application provides a method for fabricating an electronic device, comprising: coating the composition of any of the above embodiments onto a substrate to form a film layer on the substrate; forming a photosensitive material film on the surface of the film layer; and exposing and developing the photosensitive material film using a photomask to form a patterned photosensitive material film. This film layer provides excellent support for the patterned photosensitive material film, ensuring the stability of the pattern and preventing collapse, which is beneficial for the fabrication of electronic devices and allows for the production of electronic devices with excellent overall performance.

[0141] In this application, the substrate may be, but is not limited to, at least one of silicon wafer substrate, silicon nitride substrate, and glass substrate.

[0142] In some embodiments of this application, the method for fabricating an electronic device further includes: setting a hard mask on a substrate surface; coating a composition onto the surface of the hard mask to form a film layer on the hard mask; forming a photosensitive material film on the surface of the film layer; and exposing and developing the photosensitive material film through a photomask to form a patterned photosensitive material film. The hard mask may be, but is not limited to, a high-carbon-content organic hard mask, etc.

[0143] In some embodiments of this application, the method for fabricating an electronic device further includes: obtaining a patterned substrate by etching, fabricating a functional layer on the patterned substrate, and obtaining the electronic device.

[0144] Exposure and development are described above and will not be repeated here. The patterned photosensitive material film provides selective protection to the substrate during etching. Under certain etching conditions, portions of the patterned photosensitive material film and the unprotected film layers are etched, forming a patterned film layer. When a hard mask is present, portions of the patterned film layer and the unprotected hard mask layer are etched, forming a patterned hard mask. The patterned film layer or patterned hard mask provides selective protection to the substrate during etching. While portions of the patterned film and the unprotected substrate are etched, the etch depth in the protected areas is slower than in the unprotected areas, ultimately forming a pattern on the substrate. This pattern transfer to the substrate results in a patterned substrate. The etching process can specifically involve HF etching, fluorine-containing gas etching, ion etching, or ion implantation to transfer the pattern to the substrate.

[0145] This application provides an electronic device prepared by the above-described method. This electronic device exhibits high precision and excellent overall performance, which is beneficial for its application.

[0146] In this application, the electronic device may be, but is not limited to, a semiconductor device, which may include integrated circuit devices such as chips; the functional layer may include any structure that can be applied to the electronic device, such as metal wiring, active devices, passive devices, etc.

[0147] This application also provides a self-cleaning material, including the resin in any of the above embodiments. Specifically, the application of resin in the self-cleaning material utilizes the difference in polarity of the resin before and after light exposure to alter the hydrophilicity / hydrophobicity of the self-cleaning material's surface, thereby achieving a self-cleaning function.

[0148] The technical solution of this application will be further explained through specific experiments below.

[0149] The resin preparation experiment is as follows:

[0150] Experiment 1-1

[0151] 18g of (2,2,2-trifluoro-1,1-dimethyl-ethoxy)-phenyltrimethoxysilane and 17g of ethyltrimethoxysilane were mixed thoroughly and then added dropwise to a mixed solution of 35g methanol and 30g water. The mixture was reacted at room temperature for 15 hours after addition. Then, 100g of propylene glycol ethyl ether was added, and the water and byproduct alcohols were removed by vacuum distillation to obtain a resin solution. Propylene glycol ethyl ether was added to the resin solution and the mixture was cooled and diluted to obtain a resin solution with a solid content of 10wt%. The weight-average molecular weight of the prepared resin was determined to be 2200 g / mol by GPC. The structural formula of (2,2,2-trifluoro-1,1-dimethyl-ethoxy)-phenyltrimethoxysilane is as follows:

[0152] .

[0153] Experiment 1-2

[0154] 25g of (2,2,2-trifluoro-1,1-dimethyl-ethoxy)-phenyltrimethoxysilane, 5g of ethyltrimethoxysilane, and 5g of tetraethoxysilane were mixed thoroughly and then added dropwise to a mixed solution of 35g of methanol and 30g of water. The mixture was reacted at room temperature for 15 hours after the addition. Then, 100g of propylene glycol ethyl ether was added, and the water and byproduct alcohols were removed by vacuum distillation to obtain a resin solution. Propylene glycol ethyl ether was added to the resin solution, and the mixture was diluted with cooling to obtain a resin solution with a solid content of 10wt%. The weight-average molecular weight of the prepared resin was determined to be 2000 g / mol by GPC.

[0155] Experiments 1-3

[0156] 25g of bis(2,2,2-trifluoro-1,1-dimethyl-ethoxy)-phenyltrimethoxysilane, 5g of ethyltrimethoxysilane, and 5g of tetraethoxysilane were mixed thoroughly and then added dropwise to a mixed solution of 35g methanol, 10g propylene glycol ethyl ether, and 20g water. The mixture was reacted at room temperature for 15 hours after the addition. Then, 100g of propylene glycol ethyl ether was added, and the water and byproduct alcohols were removed by vacuum distillation to obtain a resin solution. Propylene glycol ethyl ether was added to the resin solution, and the mixture was diluted with cooling to obtain a resin solution with a solid content of 10wt%. The weight-average molecular weight of the prepared resin was determined to be 1800g / mol by GPC. The structural formula of bis(2,2,2-trifluoro-1,1-dimethyl-ethoxy)-phenyltrimethoxysilane is as follows:

[0157] .

[0158] Experiments 1-4

[0159] 25g of tert-butoxyphenyltrimethoxysilane, 5g of ethyltrimethoxysilane, and 5g of tetraethoxysilane were mixed thoroughly and then added dropwise to a mixed solution of 35g of methanol and 30g of water. The mixture was reacted at room temperature for 15 hours after addition. Then, 100g of propylene glycol ethyl ether was added, and the water and byproduct alcohols were removed by vacuum distillation to obtain a resin solution. Propylene glycol ethyl ether was added to the resin solution, and the mixture was diluted with cooling to obtain a resin solution with a solid content of 10wt%. The weight-average molecular weight of the prepared resin was determined to be 2500 g / mol by GPC.

[0160] The preparation experiment of silicone resin is as follows:

[0161] Experiment 2-1

[0162] 6.9 g of phenyltrimethoxysilane, 18.4 g of methyltrimethoxysilane, and 50 g of tetramethoxysilane were mixed thoroughly and then gradually added dropwise to a mixed solution of 0.25 g of 68% nitric acid, 48.2 g of methanol, and 45.1 g of water. The mixture was reacted at room temperature for 15 hours after the addition. Then, 200 g of propylene glycol ethyl ether was added, and the water and byproduct alcohols were removed by vacuum distillation to obtain a resin solution. Propylene glycol ethyl ether was added to the resin solution, and the mixture was diluted with cooling to obtain a solution containing silicone resin with a solid content of 10 wt%. The weight-average molecular weight of the prepared silicone resin was determined to be 2000 g / mol by GPC.

[0163] Experiment 2-2

[0164] 6.9 g of phenyltrimethoxysilane, 23.4 g of methyltrimethoxysilane, and 45 g of tetramethoxysilane were mixed thoroughly and then gradually added dropwise to a mixed solution of 0.25 g of 68% nitric acid, 48.2 g of methanol, and 45.1 g of water. The mixture was allowed to react at room temperature for 15 hours after the addition. Then, 200 g of propylene glycol ethyl ether was added, and the water and byproduct alcohols were removed by vacuum distillation to obtain a resin solution. Propylene glycol ethyl ether was added to the resin solution, and the mixture was diluted with cooling to obtain a solution containing silicone resin with a solid content of 10 wt%. The weight-average molecular weight of the prepared silicone resin was determined to be 2000 g / mol by GPC.

[0165] Experiment 2-3

[0166] 6.9 g of phenyltrimethoxysilane, 12.9 g of 3-glycidyl etheroxypropyltrimethoxysilane, 16.4 g of methyltrimethoxysilane, and 40 g of tetramethoxysilane were mixed thoroughly and then gradually added dropwise to a mixed solution of 0.25 g of 68% nitric acid, 48.2 g of methanol, and 45.1 g of water. The mixture was reacted at room temperature for 15 h after the addition. Then, 200 g of propylene glycol ethyl ether was added, and the water and byproduct alcohols were removed by vacuum distillation to obtain a resin solution. Propylene glycol ethyl ether was added to the resin solution, and the mixture was diluted with cooling to obtain a solution containing silicone resin with a solid content of 10 wt%. The weight-average molecular weight of the prepared silicone resin was determined to be 2000 g / mol by GPC.

[0167] The preparation experiments of the composition are as follows:

[0168] The above-mentioned resin solution, the solution containing silicone resin, the acid-generating agent (triphenyl sulfonium perfluorobutyl sulfonate TPS-Nf), the crosslinking catalyst (triphenyl sulfonium maleate, TPSMA), water, and propylene glycol ethyl ether were mixed, and the pH value was adjusted to the range of 2-5. After filtration through a 0.2 μm fluororesin filter, the composition was obtained. The mass content of the resin solution and the solution containing silicone resin in the composition is shown in Table 1. "Experiment" indicates the type of resin used, such as the resin solution obtained in Experiment 1-1 and the solution containing silicone resin obtained in Experiment 2-1 in Example 1; " / " indicates no addition; the mass content of the acid-generating agent in the composition is 0.03%, the mass content of the crosslinking catalyst is 0.02%, the mass content of water is 15%, and the balance is propylene glycol ethyl ether.

[0169] Table 1. Mass content of resin in the composition

[0170]

[0171] Performance testing

[0172] The compositions obtained in the above examples and comparative examples were spin-coated onto a silicon wafer substrate to form a thin film, and then baked at 220°C for 60 seconds to obtain the corresponding film layers.

[0173] The refractive index n and absorption coefficient k of these films at a wavelength of 193 nm were measured using an ellipsometer, and the results are shown in Table 2.

[0174] These films were plasma etched with fluorine-containing gas (composition: CF4:CHF3, volume ratio: 50%:50%) to obtain the fluorine-based gas dry etching rate (i.e., etching rate, unit: Å / min), and the results are shown in Table 2.

[0175] A carbon-containing layer (SOC layer) is spin-coated onto a silicon wafer and baked to form a film. The above composition is then spin-coated onto the carbon-containing layer and baked at 220°C for 60 seconds to form a film layer. A negative-developing photosensitive material (Shin-Etsu X219) is then spin-coated onto the film layer, and pre-baking (PAB), exposure, post-baking (PEB), and development are performed under recommended conditions, wherein a photoresist pattern of L38P84 is obtained using a suitable photomask.

[0176] A carbon-containing layer (SOC layer) is spin-coated onto a silicon wafer and baked to form a film. The above composition is then spin-coated onto the carbon-containing layer and baked at 220°C for 60 seconds to form a film layer. A positively developed photosensitive material (Shin-Etsu X222) is then spin-coated onto the film layer, and pre-baking (PAB), exposure, post-baking (PEB), and development are performed under recommended conditions, wherein a photoresist pattern of L43P124 is obtained using a suitable mask.

[0177] The presence of pattern collapse at different linewidths in patterns obtained by positive and negative development processes was observed using CD-SEM (scanning electron microscope for feature size measurement). Result 1 shows whether pattern collapse exists in patterns obtained by positive development process at linewidths of 32nm-35nm; Result 2 shows whether pattern collapse exists in patterns obtained by negative development process at linewidths of 32nm-35nm (excluding 32nm); and Result 3 shows whether pattern collapse exists in patterns obtained by negative development process at linewidths of 29nm-32nm. The results are shown in Table 2.

[0178] The accompanying drawings of this application show partial test result diagrams, in which... Figure 2 , Figure 3 , Figure 4 These are CD-SEM images of Example 4, Comparative Example 1, and Comparative Example 2 after negative development. The values ​​in the images are linewidth values ​​in nm. "Indicates pattern collapse, specific line width value cannot be measured; in Example 4, the negative development pattern did not collapse when the line width was above 29nm; in Comparative Example 1, the negative development pattern did not collapse when the line width was above 32nm, but collapsed when the line width was below 32nm; in Comparative Example 2, the negative development pattern collapsed when the line width was below 35nm."

[0179] Table 2 Performance Test Results

[0180]

[0181] It can be seen that the silicone resin used in Comparative Example 2 can be used in the positive development process but cannot be used in the negative development process simultaneously. Pattern collapse occurs in the negative development process. Although the addition of resin in Comparative Example 1 improves the support for patterns with larger linewidths in the negative development process, patterns with smaller linewidths still collapse. The silicone resin used in Comparative Example 3 can be used in the negative development process but cannot be used in the positive development process simultaneously. Pattern collapse occurs in the positive development process, and patterns with smaller linewidths still collapse in the negative development process, resulting in a low dry etching rate for the film layer. The film layer formed by the resin composition provided in this application has better optical properties and a better dry etching rate. Furthermore, it can improve the pattern collapse problem in both positive and negative development processes, achieving pattern structure stability and facilitating the continued progress of the preparation process. Compared with Example 5, Example 3 still showed no pattern collapse in the negative development pattern with a line width of 27nm-29nm (excluding 29nm), while Example 5 showed pattern collapse. This indicates that the molar fraction of the fourth repeating unit (above 60%) in the silicone resin used in Example 3 is more suitable, which is beneficial to the separation and migration of silicone resin and resin, further improving the anti-collapse ability. Therefore, it can be applied to more stringent positive and negative development processes, which is more conducive to the preparation of precision and fine devices. In the examples, the film layer of Example 4 has excellent optical properties and dry etching rate, and better overall performance, which is more conducive to its use in electronic devices and to the preparation of high-performance electronic devices.

[0182] It should be understood that the terms "first," "second," "third," "fourth," "fifth," and various numerical designations used herein are merely for descriptive convenience and are not intended to limit the scope of this application.

[0183] In this application, "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone, where A and B can be singular or plural. The character " / " generally indicates that the related objects before and after it are in an "or" relationship.

[0184] In this application, "at least one" means one or more. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be a single or multiple.

[0185] In this application, "-" indicates a range value, including the endpoint values. For example, the value of 'a' can be 0.5-15, meaning that the value of 'a' can be between 0.5 and 15, including the endpoint values ​​of 0.5 and 15. In this application, "below" includes endpoint values. For example, the value of 'a' can be below 10, meaning that the value of 'a' can be less than or equal to 10.

[0186] The above description is an exemplary embodiment of this application, but it should not be construed as limiting the scope of this application. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of this application, and these improvements and modifications are also considered to be within the scope of protection of this application.

Claims

1. A resin, characterized in that, It includes a first repeating unit and a second repeating unit, wherein the first repeating unit is R1SiO 3 / 2 The second repeating unit is , R1 is selected from unsubstituted C1-C. 20 R2 is an alkyl group, or a C1-C6 fluoroalkyl group; R2 is selected from single bonds or unsubstituted C1-C6 alkyl groups. 10 Alkylene; R3 is selected from R5 and R6 are independently selected from substituted or unsubstituted alkyl groups, R4 is selected from H or a substituted or unsubstituted alkyl group, R6 and R4 may be linked together to form a ring, and at least one of R5, R6 and R4 contains a fluorine atom, and n is 1 or 2. Indicates the connection site.

2. The resin according to claim 1, characterized in that, The resin further includes a third repeating unit derived from a third monomer selected from at least one of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, and tetran-n-butoxysilane.

3. The resin as described in claim 1 or 2, characterized in that, The molar fraction of the second repeating unit in the resin is 20%-80%; and / or The weight-average molecular weight of the resin is 600 g / mol to 6000 g / mol; and / or The R1 is selected from the C1-C6 fluoroalkyl groups with a hydrogen atom substitution rate of less than or equal to 50%; and / or The R2 is selected from single-bonded or unsubstituted C1-C4 alkylene groups; and / or The ratio of the number of hydrogen atoms replaced by F in R5, R6, and R4 to the total number of substituted hydrogen atoms is less than or equal to 90%; and / or R6 and R4 are connected to form a loop C5-C6; and / or R5, R6, and R4 are independently selected from substituted or unsubstituted C1-C4 alkyl groups.

4. A composition, characterized in that, It includes a resin component, an acid-generating agent, and a first solvent, wherein the resin component includes the resin according to any one of claims 1-3 and a silicone-containing resin.

5. The composition according to claim 4, characterized in that, The resin in the composition has a mass content of 0.01%-0.5%; and / or The composition contains 0.1%-5% by mass of the silicone resin; and / or The mass ratio of the resin to the silicone-containing resin is 1:(4-65); and / or The mass content of the acid-producing agent in the composition is 0.005%-0.1%.

6. The composition according to claim 4 or 5, characterized in that, The composition further includes an acidic substance, wherein the acidic substance comprises 0.001%-2% by mass in the composition; and / or The composition further includes a crosslinking catalyst, wherein the crosslinking catalyst comprises 0.01%-0.1% by mass in the composition; and / or The pH value of the composition is 2-5; and / or The composition has a viscosity of 3.3 cps-3.9 cps at 25°C.

7. The composition according to claim 4, characterized in that, The silicone-containing resin comprises a fourth repeating unit derived from a fourth monomer and a fifth repeating unit derived from a fifth monomer, wherein the fourth monomer is selected from at least one of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, and tetran-n-butoxysilane, and the fifth repeating unit is R7SiO 3 / 2 R7 is selected from substituted or unsubstituted C1-C. 20 Hydrocarbon group.

8. A film layer, characterized in that, The film layer comprises a solid molded product of the composition according to any one of claims 4-7.

9. The film layer as described in claim 8, characterized in that, The thickness of the film layer is 10nm-1000nm; and / or The refractive index of the film is 1.55-1.75; and / or The light absorption coefficient of the film layer is 0.17-0.27; and / or The etching rate of the film is 800 Å / min-1200 Å / min, and the etching gas is a fluorine-containing gas.

10. A method for fabricating an electronic device, characterized in that, include: The composition according to any one of claims 4-7 is coated onto a substrate to form a film layer on the substrate; A photosensitive material film is formed on the surface of the film layer; A patterned photosensitive material film is formed by exposure and development using a photomask.

11. An electronic device, characterized in that, It is prepared by the preparation method described in claim 10.

12. The electronic device as claimed in claim 11, characterized in that, The electronic devices include semiconductor devices.

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