Composition, resist underlayer film, semiconductor device and preparation method thereof

Abstract

The invention provides a composition, a resist underlayer film, a semiconductor device and a preparation method thereof. The composition comprises a silicon-containing resin, a solvent and an acid, the silicon-containing resin has a high branching degree, a new branching degree DB of the silicon-containing resin is defined according to the branching degree contributed by a Q structural unit and a T structural unit in the silicon-containing resin and in combination with a 29Si nuclear magnetic resonance spectrogram, and the branching degree DB of the silicon-containing resin is controlled to be within a proper range. The silicon-containing resin is added into the composition, so that a resist underlayer film formed by the composition has relatively high anti-reflection performance and relatively high dry etching rate at the same time.

Description

Technical Field

[0001] The embodiments of the present application relate to the field of semiconductor preparation technology, and specifically to a composition, a resist underlayer film, a semiconductor device, and a preparation method thereof. Background Art

[0002] In the semiconductor device manufacturing process, a photoresist is typically used to form a film layer on a substrate. The pattern on the mask is then transferred to the substrate through processes such as exposure, development, and etching, forming a micro-pattern corresponding to the mask. With the advancement of integrated circuit and semiconductor technology, the light sources used and the corresponding photoresists have gradually evolved toward shorter wavelengths, and the industry's requirements for the precision of micro-patterns in integrated circuits and semiconductor devices have become increasingly demanding. As micro-patterns become more refined, the thickness of the photoresist film layer has gradually decreased to effectively prevent pattern collapse during development due to excessive aspect ratios. Furthermore, to accommodate shorter wavelength light sources and improve pattern resolution, the etching resistance of the photoresist has also gradually weakened.

[0003] Currently, to address the above-mentioned issues, a multilayer resist method is typically employed. Specifically, a hard mask layer with sufficient dry etching resistance is first formed on the substrate being processed, followed by a silicon-containing resist underlayer film, which is then subsequently formed as a conventional photoresist layer. The etching rate of a silicon-containing resist underlayer film is generally positively correlated with the silicon content. In other words, a higher silicon content results in a faster etching rate for the resist underlayer film by fluorine-based gases. However, excessive silicon content can reduce the antireflection performance of the resist underlayer film. Therefore, there is an urgent need to provide a resist underlayer film-forming composition that ensures good antireflection performance while also achieving a faster dry etching rate. Summary of the Invention

[0004] In view of this, the present application provides a composition, a resist underlayer film, a semiconductor device and a preparation method thereof. The composition comprises a silicone resin, a solvent and an acid, wherein the silicone resin has a high degree of branching. The present application provides a composition, a resist underlayer film, a semiconductor device and a preparation method thereof. The composition comprises a silicone resin, a solvent and an acid, wherein the silicone resin has a high degree of branching. 29 The Si nuclear magnetic resonance spectrum defines a new branching degree DB of the silicone-containing resin and controls the branching degree DB of the silicone-containing resin within an appropriate range. Adding the silicone-containing resin to the composition can ensure that the resist lower layer film formed by the composition has good anti-reflective properties while also having a faster dry etching rate.

[0005] In a first aspect, the present application provides a composition comprising a silicon-containing resin, a solvent, and an acid, wherein the silicon-containing resin comprises a Q structural unit and a T structural unit; the Q structural unit comprises a first silicon atom and four oxygen atoms bonded to the first silicon atom; the T structural unit comprises a second silicon atom and three oxygen atoms bonded to the second silicon atom;

[0006] Let Q n The silicone resin 29 The integrated area of ​​the nuclear magnetic peak corresponding to the Q structural unit obtained from the Si nuclear magnetic resonance spectrum, wherein n represents the number of oxygen atoms in the four oxygen atoms in any Q structural unit that are bonded to the silicon atoms in the adjacent structural unit; T m The silicone resin 29 The integrated area of ​​the nuclear magnetic peak corresponding to the T structural unit obtained from the Si nuclear magnetic resonance spectrum, wherein m represents the number of oxygen atoms in the three oxygen atoms in any T structural unit that are bonded to the silicon atoms in the adjacent structural unit;

[0007] The branching degree of the silicone resin is DB, and DB = (2Q4 + Q3 + T3) / [2Q 4+ 4 / 3(Q3+T3)+2 / 3(Q2+T2)], the DB satisfies: 0.75≤DB≤0.90. The composition provided by the present application includes a silicone resin, a solvent and an acid, wherein the silicone resin has a high degree of branching. The present application is based on the branching degree contributed by the Q structural unit and the T structural unit in the silicone resin and combined with 29 The Si nuclear magnetic resonance spectrum defines the branching degree DB of the new silicon-containing resin, and the branching degree DB of the silicon-containing resin is controlled within an appropriate range. Adding the silicon-containing resin to the composition can ensure that the resist lower layer film formed by the composition has good anti-reflective properties while improving its etching speed.

[0008] In the embodiment of the present application, the weight average molecular weight of the silicon-containing resin is 2000-15000. By controlling the molecular weight of the silicon-containing resin within a suitable range, the present application can facilitate the coating of the composition, thereby obtaining a resist underlayer film with more uniform thickness and pore distribution.

[0009] In an embodiment of the present application, in the silicon-containing resin, the molar ratio of the Q structural unit to the T structural unit is (1-9): 1. The present application can further control the branching degree of the silicon-containing resin by controlling the ratio of the Q structural unit to the T structural unit in the silicon-containing resin within an appropriate range.

[0010] In the embodiment of the present application, the pH value of the composition is 2 to 5. By controlling the pH value of the composition within a suitable range, the present application can provide a suitable acidic environment for the formation of the silicone resin and improve the stability of the composition.

[0011] In the embodiment of the present application, the mass percentage of the silicon-containing resin in the composition is 0.1%-5%. By controlling the content of the silicon-containing resin in the composition within the above range, the film-forming performance of the resist underlayer film can be further improved.

[0012] In the embodiment of the present application, the mass percentage of the solvent in the composition is 94.0%-99.8%. By controlling the solvent within the above range, the present application can ensure that the solvent fully dissolves and disperses each component while improving the coating ability and component uniformity of the composition.

[0013] In the embodiment of the present application, the mass percentage of the acid in the composition is 0.001%-5%. By controlling the acid content in the composition within a suitable range, the pH value of the composition can be controlled within a suitable range.

[0014] In an embodiment of the present application, the solvent includes an alcohol ether solvent, and the alcohol ether solvent includes one or more 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 butylene glycol methyl ether. The present application uses a suitable solvent to effectively dissolve and disperse the aforementioned silicone resin, acid, and other additives, thereby obtaining a composition with uniform components and high stability, and improving the coating and film-forming properties of the composition.

[0015] In an embodiment of the present application, the acid includes one or more of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, 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. By selecting a suitable acid, the present application can provide acidic conditions for the hydrolysis and condensation of the silicone-containing resin, thereby obtaining the silicone-containing resin.

[0016] In some embodiments of the present application, the solvent further comprises a non-alcoholic solvent, and the non-alcoholic solvent comprises one or more of toluene, cyclohexane, tetrahydrofuran, methyl tert-butyl ether, cyclopentyl methyl ether, acetone, cyclohexanone, methyl isobutyl ketone, methyl amyl 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 gamma-butyrolactone. The present application can further optimize the solvent system of the composition by using the above-mentioned solvents in combination with the alcohol-ether solvents described above, further improve the solubility and dispersibility of each component, and thereby improve the uniformity and stability of the composition.

[0017] In some embodiments of the present application, the mass of the alcohol ether solvent is greater than or equal to 60% of the total mass of the solvent. The present application can further optimize the mixed solvent system of the composition by further regulating the component ratio of the solvent, thereby further improving the solubility of the solvent and the stability of the composition.

[0018] In an embodiment of the present application, the Q structural unit of the silicone-containing resin is derived from a first monomer, and the first monomer includes one or more of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane and tetra-n-butoxysilane; the T structural unit of the silicone-containing resin is derived from a second monomer, and the second monomer includes a monomer with a structural formula of R1-Si(OR2)3, wherein R1 is a substituted or unsubstituted C1-C20 hydrocarbon group, and R2 is a C1-C6 alkyl group.

[0019] In the embodiment of the present application, R1 is selected from a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, or a substituted or unsubstituted C6-C20 aryl group; when R1 is a substituted C1-C20 alkyl group, a substituted C3-C20 cycloalkyl group, a substituted C2-C20 alkenyl group, a substituted C2-C20 alkynyl group, or a substituted C6-C20 aryl group, the substituent group is selected from at least one of a halogen atom, an epoxy group, an acryloyl group, a methacryloyl group, a thiol group, an amino group, a cyano group, -OR3, -SR4, -CONR5R6, an ester group, an isocyanurate group, and a lactone ring, wherein R3 is a hydrocarbon group, R4 is a hydrocarbon group, and R5 and R6 are independently selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group.

[0020] The second aspect of the present application provides a resist underlayer film, wherein the resist underlayer film is formed using the composition provided in the first aspect of the present application. The resist underlayer film provided in the present application has both good anti-reflection performance and a relatively fast etching rate.

[0021] The third aspect of the present application provides a semiconductor device, comprising a patterned substrate formed using the composition provided in the first aspect. Due to the use of the resist underlayer film provided above, the semiconductor device provided in the present application has good overall performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 The silicone resin in the composition provided in Example 1 of the present application 29 Si NMR spectrum. DETAILED DESCRIPTION

[0023] The present application is further described in detail below in conjunction with preferred embodiments, but the protection scope of the present application is not limited to the following specific embodiments.

[0024] In this application, all professional terms have the same meanings as those generally understood by those skilled in the art. The professional terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of this application.

[0025] In the semiconductor device manufacturing process, a photoresist is typically used to form a film layer on a substrate. The pattern on the mask is then transferred to the substrate through processes such as exposure, development, and etching, forming a micro-pattern corresponding to the mask. With the advancement of integrated circuit and semiconductor technology, the light sources used and the corresponding photoresists have gradually evolved toward shorter wavelengths, and the industry's requirements for the precision of micro-patterns in integrated circuits and semiconductor devices have become increasingly demanding. As micro-patterns become more refined, the thickness of the photoresist film layer has gradually decreased to effectively prevent pattern collapse during development due to excessive aspect ratios. Furthermore, to accommodate shorter wavelength light sources and improve pattern resolution, the etching resistance of the photoresist has also gradually weakened.

[0026] Currently, to address the above-mentioned issues, a multilayer resist method is typically employed. This involves first forming a hard mask layer with sufficient dry etch resistance on the substrate being processed, then forming a silicon-containing resist underlayer film thereon, and finally forming a conventional photoresist film thereon. By utilizing the fact that the resist underlayer has a faster etching rate than the photoresist film, the pattern of the photoresist film is transferred to the resist underlayer film, and then the pattern is transferred to the hard mask layer through etching selectivity. A slow etching rate can lead to defects caused by residual resist underlayer film, requiring a long etching time, and thus damaging the substrate. Therefore, to ensure the downward transfer of the pattern and the smooth removal of the resist underlayer film, the resist underlayer film needs to have a fast etching rate.

[0027] Because the etching rate of a silicon-containing resist underlayer film is positively correlated with the silicon content, i.e., the higher the silicon content, the faster the etching rate of the resist underlayer film by the fluorine-based gas. Therefore, increasing the silicon content in the resist underlayer film is often used to increase the etching rate. However, excessive silicon content can reduce the antireflection performance of the resist underlayer film. Therefore, there is an urgent need to provide a resist underlayer film-forming composition that ensures good antireflection performance while also achieving a fast etching rate.

[0028] In order to solve the above problems, the present application provides a composition, a resist underlayer film, a semiconductor device and a preparation method thereof. The composition comprises a silicone resin, a solvent and an acid, wherein the silicone resin has a high degree of branching. The present application is based on the degree of branching contributed by the Q structural unit and the T structural unit in the silicone resin and combined with 29 The Si nuclear magnetic resonance spectrum defines a new branching degree DB of the silicone-containing resin and controls the branching degree DB of the silicone-containing resin within an appropriate range. Adding the silicone-containing resin to the composition can ensure that the resist lower layer film formed by the composition has good anti-reflective properties while also having a faster dry etching rate.

[0029] An embodiment of the present application provides a composition comprising a silicone-containing resin, a solvent, and an acid. The silicone-containing resin comprises a Q structural unit and a T structural unit. In the embodiment of the present application, the Q structural unit comprises a first silicon atom and four oxygen atoms bonded to the first silicon atom, as shown in formula (I); the T structural unit comprises a second silicon atom and three oxygen atoms bonded to the second silicon atom, as shown in formula (II); in formula (I) and formula (II), * represents a site that can be connected to an adjacent structural unit;

[0030]

[0031] In the embodiment of the present application, let Q n Made of silicone resin 29 The integrated area of ​​the NMR peak corresponding to the Q structural unit obtained from the Si NMR spectrum, wherein n represents the number of oxygen atoms in any Q structural unit that are bonded to the silicon atoms in the adjacent structural unit, and n is an integer from 0 to 4, and n can be, for example, 0, 1, 2, 3, or 4; let T m Made of silicone resin 29 The integrated area of ​​the nuclear magnetic peak corresponding to the T structural unit obtained from the Si nuclear magnetic resonance spectrum, m represents the number of oxygen atoms in any T structural unit that are bonded to the silicon atom in the adjacent structural unit, m is an integer from 0 to 3, and m can be, for example, 0, 1, 2, or 3. In this application, the branching degree of the silicone resin is denoted as DB, and DB = (2Q4 + Q3 + T3) / [2Q 4+4 / 3(Q3+T3)+2 / 3(Q2+T2)]. In the embodiment of the present application, the degree of branching DB of the silicone-containing resin in the composition satisfies: 0.75≤DB≤0.90. In some specific embodiments, the degree of branching DB of the silicone-containing resin can be, for example, 0.75, 0.76, 0.77, 0.78, 0.80, 0.82, 0.83, 0.84, 0.85, 0.86, 0.87, 0.88, or 0.90. In the present application, the degree of branching DB of the silicone-containing resin is related to the actual specific selection of the raw material monomers, and the degree of branching DB in the present application is an approximate value obtained by calculation. The present application provides a novel method for defining the degree of branching to measure the degree of spatial branching of a special silicone-containing resin, and to control the degree of branching DB of the silicone-containing resin within an appropriate range. When the silicone-containing resin is added to a composition, on the one hand, its film-forming performance can be improved, and to a certain extent, the situation in which the composition is easy to gel due to excessively high degree of branching, resulting in difficulty in using the film; on the other hand, it can also be beneficial to the formation of a resist lower layer film with a larger porosity, increase the diffusion rate of the plasma etching gas in the resist lower layer film, and thus significantly improve the dry etching rate of the resist lower layer film without changing the silicon content, that is, without affecting the anti-reflective performance.

[0032] In some embodiments of the present application, the adjacent structural units of any Q structural unit and any T structural unit may be Q structural units and / or T structural units. In other embodiments of the present application, the adjacent structural units of any Q structural unit and any T structural unit may also be other structural units in addition to Q structural units and T structural units. In some embodiments of the present application, when the adjacent structural unit is a plurality of T structural units, the plurality of T structural units may be the same or different.

[0033] The composition provided by the present application includes a silicon-containing resin containing a Q structural unit and a T structural unit, and the present application is based on the contribution of the Q structural unit and the T structural unit in the silicon-containing resin to the branching degree and combined with 29 The Si nuclear magnetic resonance spectrum defines a new type of branching degree DB of the silicone-containing resin. Then, the branching degree DB of the silicone-containing resin is controlled within an appropriate range. The resulting resist underlayer film can have both good anti-reflection properties and a faster dry etching rate without changing the silicon content in the silicone-containing resin. This greatly reduces the impact of light source reflection while ensuring patterned downward transfer and smooth removal, resulting in a semiconductor device with higher precision and better performance.

[0034] In the embodiment of the present application, Q n for the reason 29The integrated area of ​​the nuclear magnetic peak corresponding to the Q structural unit measured by the Si nuclear magnetic resonance spectrum, n represents the number of oxygen atoms in any Q structural unit that are bonded to the silicon atoms in the adjacent structural unit among the four oxygen atoms, n is an integer from 0 to 4, and n can be, for example, 2, 3, or 4. In some specific embodiments of the present application, n=2, that is, two of the four oxygen atoms in the Q structural unit are bonded to the silicon atoms in the adjacent structural unit, and Q2 represents that the Q structural unit consists of 29 In some specific embodiments of the present application, n=3, that is, 3 of the 4 oxygen atoms in the Q structural unit are bonded to the silicon atoms in the adjacent structural unit, and Q3 indicates that the Q structural unit consists of 29 In some specific embodiments of the present application, n=4, that is, 4 of the 4 oxygen atoms in the Q structural unit are bonded to the silicon atoms in the adjacent structural unit. Q4 means that the Q structural unit consists of 29 The integrated area of ​​the nuclear magnetic peak obtained from the Si nuclear magnetic resonance spectrum. In the embodiment of the present application, Q n The specific testing method can be, but is not limited to, freeze-drying the composition to remove the original solvent and dissolving it in chloroform. 29 Si NMR test, NMR peak integral area Q n The integration region is from -70 ppm to -130 ppm.

[0035] In an embodiment of the present application, the Q structural unit of the silicone-containing resin is derived from a first monomer, and the first monomer is a hydrolyzable silane monomer, including one or more of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane and tetra-n-butoxysilane. In some specific embodiments, the Q structural unit of the silicone-containing resin can be derived from, for example, tetramethoxysilane or tetraethoxysilane. In an embodiment of the present application, the Q structural unit of the silicone-containing resin in the composition can be derived from the same first monomer or from different first monomers.

[0036] In the embodiment of the present application, T m for the reason 29 The integrated area of ​​the nuclear magnetic peak corresponding to the T structural unit measured by the Si nuclear magnetic resonance spectrum, m represents the number of oxygen atoms in any T structural unit that are bonded to the silicon atoms in the adjacent structural unit among the three oxygen atoms, m is an integer from 0 to 3, and m can be, for example, 2 or 3. In some specific embodiments of the present application, m=2, that is, two of the three oxygen atoms in the T structural unit are bonded to the silicon atoms in the adjacent structural unit, and T2 represents that the T structural unit consists of 29In some specific embodiments of the present application, m=3, that is, 3 of the 3 oxygen atoms in the T structural unit are bonded to the silicon atoms in the adjacent structural unit, and T3 indicates that the T structural unit consists of 29 The integrated area of ​​the nuclear magnetic peak obtained from the Si nuclear magnetic resonance spectrum. In the embodiment of the present application, T m The specific testing method can be, but is not limited to, freeze-drying the composition to remove the original solvent and dissolving it in chloroform. 29 Si NMR test, NMR peak integral area T m The integration region is from -35 ppm to -85 ppm.

[0037] In an embodiment of the present application, the molar ratio of the Q structural unit to the T structural unit in the silicon-containing resin is (1-9): 1. In some embodiments of the present application, the molar ratio of the Q structural unit to the T structural unit in the silicon-containing resin can be, for example, 1: 1, 2: 1, 3: 1, 4: 1, 5: 1, 6: 1, 7: 1, 8: 1, or 9: 1. The present application can further control the degree of branching of the silicon-containing resin by controlling the ratio of the Q structural unit to the T structural unit in the silicon-containing resin within an appropriate range.

[0038] In an embodiment of the present application, the T structural unit of the silicone-containing resin is derived from a second monomer, and the second monomer is a hydrolyzable silane monomer with the structural formula R1-Si(OR2)3, wherein R1 is a substituted or unsubstituted C1-C20 hydrocarbon group, and R2 is a C1-C6 alkyl group. In an embodiment of the present application, the C1-C20 hydrocarbon group can be a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group or a C6-C20 aryl group. In an embodiment of the present application, the selection of R2 in each second monomer can be the same or different. In an embodiment of the present application, the T structural unit of the silicone-containing resin in the composition can be derived from the same second monomer or from different second monomers. That is, in an embodiment of the present application, the silicone-containing resin can contain one T structural unit or multiple T structural units.

[0039] In the embodiment of the present application, the alkyl group may include a straight-chain alkyl group and a branched-chain alkyl group. In some specific embodiments, the alkyl group may include, but is not limited to, at least one of a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, a n-hexyl group, a 1-methyl-n-pentyl group, a 2-methyl-n-pentyl group, a 1,1-dimethyl-n-butyl group, a 1,3-dimethyl-n-butyl group, a 2,2-dimethyl-n-butyl group, a 3,3-dimethyl-n-butyl group, a 1-ethyl-n-butyl group, a 1,1,2-trimethyl-n-propyl group, a 1-ethyl-1-methyl-n-propyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. In the embodiment of the present application, the number of carbon atoms in the alkyl group is 1 to 20. In some specific embodiments, the number of carbon atoms in the alkyl group can be, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.

[0040] In the embodiment of the present application, the cycloalkyl group may include, but is 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. In the embodiment of the present application, the number of carbon atoms in the cycloalkyl group is 3 to 20. In some specific embodiments, the number of carbon atoms in the cycloalkyl group can be 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.

[0041] In the embodiment of the present application, alkenyl may include straight-chain alkenyl and branched alkenyl. In some specific embodiments, alkenyl may include but is 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, 2-methyl-2 -butenyl, 3-methyl-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-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-methyl-2-propenyl , 3-dimethyl-1-butenyl, 1-n-propyl-2-propenyl, 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, bicycloheptenyl and norbornenyl. In the embodiment of the present application, the number of carbon atoms of the alkenyl group is 2-20. In some specific embodiments, the number of carbon atoms in the alkenyl group can be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.

[0042] In the embodiment of the present application, the alkynyl group may include a straight chain alkynyl group and a branched chain alkynyl group. In some specific embodiments, 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. In the embodiment of the present application, the number of carbon atoms of the alkynyl group is 2-20. In some specific embodiments, the number of carbon atoms of the alkynyl group may be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.

[0043] In the embodiment of the present application, aryl can include but is not limited to 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-anthryl, 2-anthryl, 9-anthryl, 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl, 4-phenanthrenyl, 9-phenanthrenyl, benzyl, o-methoxybenzyl, p-methoxybenzyl, o-tert-butoxybenzyl and p-tert-butoxybenzyl at least one. In the embodiment of the present application, phenyl has 6-20 carbon atoms. In some specific embodiments, the number of carbon atoms in the phenyl group can be 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.

[0044] In the embodiment of the present application, when R1 is a substituted C1-C20 alkyl group, a substituted C3-C20 cycloalkyl group, a substituted C2-C20 alkenyl group, a substituted C2-C20 alkynyl group or a substituted C6-C20 aryl group, the substituent group is selected from a halogen atom, an epoxy group, an acryloyl group (-COCH=CH2), a methacryloyl group (-COCH=CH2CH3), a thiol group (-SH), an amino group (-NH2), a cyano group (-CN), -OR3, -SR4, -CONR5R6, an ester group, an isocyanurate group (-N3C3O3) and a lactone ring (-COO(CH2) n , n is an integer greater than or equal to 2), wherein R3 is a hydrocarbon group, R4 is a hydrocarbon group, and R5 and R6 are independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group. In the embodiment of the present application, the halogen atom includes but is not limited to a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. In the embodiment of the present application, the epoxy group includes but is not limited to a glycidoxymethyl group, a glycidoxyethyl group, a glycidoxypropyl group or a glycidoxycyclohexylpropyl group. In the embodiment of the present application, the lactone ring includes but is not limited to a β-lactone (-COO(CH2)2), a γ-lactone (-COO(CH2)3) or a δ-lactone (-COO(CH2)4).

[0045] In an embodiment of the present application, the silicon-containing resin includes Q structural units and T structural units, wherein the Q structural units are derived from the first monomer described above, and the T structural units are derived from the second monomer described above. In some specific embodiments, the silicon-containing resin can be obtained by hydrolyzing and condensing these hydrolyzable silane monomers under acidic conditions to obtain a silicon-containing resin solution precursor, and then aging or aging under heating conditions to obtain a silicon-containing resin solution with a significantly increased degree of branching.

[0046] In some embodiments of the present application, the method for preparing the solution containing the above-mentioned silicone resin may include:

[0047] S101, mixing a first monomer, a second monomer, and an acid to obtain a silicon resin solution precursor;

[0048] S102, heating the silicon-containing resin solution precursor to obtain a silicon-containing resin solution.

[0049] In step S101, the first monomer and the second monomer are the first monomer and the second monomer provided above. In an embodiment of the present application, the acid includes an inorganic acid and / or an organic acid, wherein the inorganic acid can be, for example, one or more of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, and hydrofluoric acid; the organic acid can be, for example, one or more 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 the present application, the first monomer and the second monomer are hydrolyzed and condensed under acidic conditions to obtain a silicone resin solution precursor.

[0050] In an embodiment of the present application, when mixing the first monomer, the second monomer and the acid, the amount of acid added can be 0.001%-5% of the total mass of the mixed solution. In some specific embodiments, the amount of acid added can be, for example, 0.001%, 0.005%, 0.01%, 0.02%, 0.03%, 0.05%, 0.08%, 0.1%, 0.2%, 0.5%, 0.6%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5% of the total mass of the mixed solution. By controlling the acid content in the composition within a suitable range, the acidic conditions of the first monomer and the second monomer during the dehydration condensation reaction can be further optimized, thereby further promoting the hydrolysis condensation reaction.

[0051] In some embodiments of the present application, a solvent may be added when mixing the first monomer, the second monomer, and the acid. The solvent may include water and / or a water-soluble organic solvent. Specifically, the water-soluble organic solvent includes, but is not limited to, alcohol solvents, polyol ether solvents, acetone, tetrahydrofuran, and acetonitrile. In some specific embodiments, the alcohol solvent may be, for example, methanol, ethanol, n-propanol, or isopropanol, and the polyol ether solvent may be, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, or propylene glycol monopropyl ether. In some embodiments of the present application, the water-soluble organic solvent is one that is easily removed by distillation or vacuum distillation or that can be used as a component in the final composition. In some embodiments of the present application, the amount of solvent added is sufficient to meet the amount required for the dehydration condensation reaction of the first monomer and the second monomer. In some embodiments, the amount of solvent added is such that the mass percentage of the first monomer and the second monomer in the mixed solution is greater than or equal to 30%. In some embodiments of the present application, both the first monomer and the second monomer are hydrolyzable monomers containing hydrolyzable substituents. By controlling the amount of solvent added within an appropriate range, the reaction rate can be further increased and the reaction cost can be reasonably controlled. In some embodiments, the molar ratio of the hydrolyzable substituent in the first monomer and the second monomer to the water added during mixing is 1:(2-20). In some specific embodiments, the molar ratio of the hydrolyzable substituent in the first monomer and the second monomer to the water added during mixing can be, for example, 1:2, 1:3, 1:5, 1:6, 1:8, 1:10, 1:12, 1:15, 1:16, 1:18, or 1:20.

[0052] In some embodiments of the present application, mixing the first monomer, the second monomer, and the acid may be performed by gradually dropping the mixed solution of the first monomer and the second monomer into a solvent containing the acid to carry out a dehydration condensation reaction. In other embodiments of the present application, mixing the first monomer, the second monomer, and the acid may be performed by gradually dropping the solution containing the acid into the mixed solution containing the first monomer and the second monomer.

[0053] In an embodiment of the present application, when the first monomer, the second monomer, and the acid are mixed, the reaction temperature is 0°C-60°C, and the reaction time is the time required for at least 95% or more of the hydrolyzable groups in the first monomer and the second monomer to be hydrolyzed into Si-OH groups or further condensed into Si-O-Si groups. In some specific embodiments of the present application, the reaction temperature can be, for example, 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, or 60°C.

[0054] In some embodiments of the present application, after mixing the first monomer, the second monomer, and the acid, distillation or reduced pressure distillation is further performed to perform solvent replacement, thereby reacting the generated small molecule alcohols, water, and a low-boiling point water-soluble organic solvent to obtain a silicon-containing resin solution precursor with a low degree of branching. In some embodiments of the present application, the heating temperature for distillation or reduced pressure distillation is less than or equal to 60° C., and the solid content of the silicon-containing resin solution precursor after solvent replacement is less than or equal to 20 wt %.

[0055] In step S102, the heating temperature is 60°C-150°C. In some embodiments, the heating temperature can be 80°C-130°C. In some specific embodiments, the heating temperature can be, for example, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, or 150°C. In the embodiment of the present application, the heating temperature is lower than the boiling point of the water-soluble organic solvent mentioned above, thereby effectively avoiding the occurrence of gelation due to uncontrolled aging. The present application can mature or age the silicone resin solution precursor with a low degree of branching by controlling the heating temperature within a suitable range, thereby significantly improving the degree of branching of the silicone resin while reducing the preparation cost.

[0056] In some embodiments of the present application, after heating, a solvent is further added to further dilute the silicone resin solution and cool it for storage, so that the storage period of the stability of the silicone resin solution can be further improved, which is convenient for subsequent addition to the composition. In some embodiments of the present application, the solid content of the silicone resin solution is less than or equal to 15wt%. In some embodiments of the present application, the solid content of the silicone resin solution can be less than or equal to 10wt%. In some specific embodiments, the solid content of the silicone resin solution can be, for example, 3wt%, 5wt%, 8wt%, 10wt%, 12wt%, 14wt%, or 15wt%. The storage stability of the silicone resin solution containing a high degree of branching can be further improved by controlling the solid content within a suitable range.

[0057] In the present application embodiment, the weight average molecular weight of silicone-containing resin is 2000-15000. In some specific embodiments, the weight average molecular weight of silicone-containing resin can be, for example, 2000, 2500, 3000, 3200, 3400, 3500, 4000, 4500, 4600, 4700, 5000, 5500, 6000, 6100, 6500, 7000, 7200, 7500, 8000, 8500, 9000, 9500, 10000, 11000, 12000, 13000, 14000, 15000. In some embodiments of the present application, the weight average molecular weight of silicone-containing resin can be 3000-8000. The present application can be more conducive to the coating of composition by controlling the molecular weight of silicone-containing resin in a suitable range, and then obtain the resist lower layer film with thickness and pore distribution being more uniform. In the present application, the weight average molecular weight of the silicone-containing resin can be measured by, but is not limited to, GPC (Gel Permeation Chromatography).

[0058] In an embodiment of the present application, the mass percentage of the silicone resin in the composition is 0.1%-5.0%. In some embodiments of the present application, the mass percentage of the silicone resin in the composition can be 1.0%-2.0%. In some specific embodiments, the mass percentage of the silicone resin in the composition can be, for example, 0.1%, 0.2%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5%. By controlling the content of the silicone resin in the composition within the above range, the film-forming performance of the resist lower layer film can be further improved.

[0059] In the embodiment of the present application, the acid in the composition includes an inorganic acid and / or an organic acid, wherein the inorganic acid can be, for example, one or more of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid and hydrofluoric acid, and the organic acid can be, for example, one or more 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 specific implementations, the acid can be, for example, nitric acid. The present application can provide acidic conditions for the hydrolysis condensation of the silicone resin by selecting suitable acid, and then obtain the silicone resin.

[0060] In an embodiment of the present application, the weight percentage of the acid in the composition is 0.001%-5%. In some specific embodiments, the weight percentage of the acid in the composition can be, for example, 0.001%, 0.005%, 0.01%, 0.02%, 0.03%, 0.05%, 0.08%, 0.1%, 0.2%, 0.5%, 0.6%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, or 5%. By controlling the acid content in the composition within a suitable range, the pH value of the composition can be further controlled within a suitable range.

[0061] In the embodiment of the present application, the pH value of the composition is 2-5. In some embodiments, the pH value of the composition is 2-4. In some specific embodiments of the application, the pH value of the composition can be, for example, 2, 2.5, 3, 3.5, 4, 4.5, or 5. The present application selects a suitable acid to be added to the composition, and controls its content within a suitable range, so as to further adjust the pH value of the composition within a suitable range, thereby providing a suitable acidic environment for the formation of the silicone resin and improving the stability of the composition. In the present application, the method for testing the pH value of the composition can 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. In the present application, the pH value of the composition can be obtained by the acid contribution described above, or it can be obtained by subsequently adding an acid, base or other buffering agent for adjusting the pH value.

[0062] In the embodiment of the present application, the solvent includes an alcohol ether solvent, and the alcohol ether solvent includes one or more 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 butylene glycol methyl ether. In some specific embodiments, the solvent can be, for example, propylene glycol ethyl ether. The present application can preferably dissolve and disperse the aforementioned components such as silicone resin and acid and other additives by selecting a suitable solvent, which is conducive to obtaining a composition with uniform components and high stability, and is conducive to improving the coating performance and film-forming performance of the composition.

[0063] In some embodiments of the present application, the solvent also includes a non-alcohol solvent, such as toluene, cyclohexane, tetrahydrofuran, methyl tert-butyl ether, cyclopentyl methyl ether, acetone, cyclohexanone, methyl isobutyl ketone, methyl amyl 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 one or more of gamma-butyrolactone. The present application can further optimize the solvent system of the composition by using the above-mentioned solvents in combination with the alcohol ether solvents described above, further improve the solubility and dispersibility of each component, and then improve the uniformity and stability of the composition. In some embodiments of the present application, when the solvent includes both alcohol ether solvents and non-alcohol solvents, the mass of the alcohol ether solvent is greater than or equal to 60% of the total mass of the solvent. In some specific embodiments, the mass of the alcohol ether solvent can be, for example, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95% of the total mass of the solvent. The present application can further optimize the mixed solvent system of the composition by further regulating the proportion of the solvent components, thereby further improving the solubility of the solvent and the stability of the composition.

[0064] In the embodiments of the present application, the mass percentage of the solvent in the composition is 94.0%-99.8%. In some specific embodiments, the mass percentage of the solvent in the composition can be, for example, 94%, 95%, 96%, 97%, 98%, 98.5%, 99%, 99.5%, or 99.8%. By controlling the solvent within the above range, the present application can ensure that it fully dissolves and disperses the various components while improving the coating ability and component uniformity of the composition.

[0065] In some embodiments of the present application, in order to improve the overall performance, the composition may further include other additives. In some embodiments of the present application, additives include but are not limited to one or more of a cross-linking catalyst, a photoacid generator, a surfactant and other auxiliary agents. In some embodiments of the present application, the composition also includes a cross-linking catalyst. By selecting a suitable cross-linking catalyst, the curing cross-linking reaction in the resist lower film can be promoted, thereby enhancing the mechanical strength, thermal stability and chemical stability of the resist lower film. In some specific embodiments, the cross-linking catalyst can be selected from one or more of triphenylsulfonium salts, diphenyliodonium salts, tetraphenyl quaternary phosphonium salts and tetraalkyl quaternary ammonium salts of monocarboxylic acid or polycarboxylic acid. In other specific embodiments, the cross-linking catalyst can also be one or more of sulfonium salts, iodonium salts, quaternary phosphonium salts and quaternary ammonium salts as part of a hydrolyzable silane compound, added to the silicon-containing resin described above by co-hydrolysis condensation. In some specific embodiments of the present application, the cross-linking catalyst can be, for example, triphenylsulfonium nitrate or benzyltriethylammonium chloride. In some embodiments of the present application, the composition also includes a photoacid generator, which can generate acid through a photochemical reaction and then catalyze a cross-linking reaction. In some specific embodiments, the photoacid generator can be, for example, one or more of an onium salt compound, a sulfonimide compound, and a disulfonimide compound. In some embodiments of the present application, the composition also includes a surfactant, and the addition of a suitable surfactant can effectively improve the coating performance of the composition and the film uniformity of the resist lower layer. In some specific embodiments, the surfactant can be, but is not limited to, non-ionic surfactants such as polyoxyethylene ether and long-chain carboxylic acid esters of anhydrous sorbitol, and fluorine-containing surfactants. In some embodiments of the present application, the composition also includes other additives, such as rheology regulating additives, bonding additives, etc. The above additives can be added according to actual use requirements.

[0066] The composition provided by the present application includes a silicone resin, a solvent and an acid, wherein the silicone resin has a high degree of branching. The present application is based on the degree of branching contributed by the Q structural unit and the T structural unit in the silicone resin and combined with 29 The Si nuclear magnetic resonance spectrum defines the branching degree DB of the silicone resin. The present application selects a silicone resin with a branching degree DB within a suitable range, thereby ensuring that the resist underlayer film formed by the composition has good anti-reflective properties while also having a faster dry etching rate.

[0067] The present application also provides a method for preparing the composition described above, comprising:

[0068] A silicon-containing resin solution, an acid and a solvent are mixed to obtain a composition, wherein the silicon-containing resin solution includes the silicon-containing resin described above.

[0069] In some embodiments of the present application, the mixing of the silicone resin solution, the acid and the solvent further includes filtering, and the filtration may be performed using a 0.02 μm fluororesin filter, for example.

[0070] The preparation method of the composition provided in the present application is simple, the preparation cost is low, the raw materials are simple and easily available, and the prepared composition has high stability and good film-forming properties.

[0071] The present application also provides a resist underlayer film formed using the composition provided above. The resist underlayer film provided herein exhibits both excellent antireflection properties and a relatively fast dry etching rate, significantly reducing the effects of light source reflection while ensuring patterned downward transfer and smooth removal, thereby yielding a semiconductor device with high precision and superior performance.

[0072] In an embodiment of the present application, the method for preparing the resist lower film may be, for example, coating the composition on a substrate and then baking it to form a film. In an embodiment of the present application, the coating method may be a common coating method in the field, for example, coating may be performed using a spin coater. In some embodiments of the present application, the substrate may be cleaned before coating to remove impurities and dust on the surface of the substrate. Specifically, the cleaning method may be, but is not limited to, the use of a solvent, acid, ultrasonic or spray cleaning, etc. In some embodiments of the present application, the cleaning method may be ultrasonic cleaning.

[0073] In the embodiment of the present application, the substrate can be selected according to actual needs. In some embodiments, the substrate may include a substrate to be patterned and a hard mask covering the surface of the substrate to be patterned. Specifically, the substrate to be patterned may be, but is not limited to, a silicon wafer substrate, a silicon nitride substrate, or a glass substrate; the hard mask may be, but is not limited to, an organic hard mask with a high carbon content, etc. In the embodiment of the present application, the thickness of the resist lower film is 10nm-1000nm. In some specific embodiments, the thickness of the resist lower film may be, for example, 10nm, 20nm, 30nm, 50nm, 60nm, 80nm, 100nm, 150nm, 200nm, 250nm, 300nm, 500nm, 600nm, 800nm, or 1000nm.

[0074] In the embodiment of the present application, the baking temperature is 80°C-300°C, and the baking time is 10s-3000s. In some embodiments, the baking temperature can be 150°C-250°C, and the baking time can be 30s-200s. In some specific embodiments, the baking temperature can be, for example, 80°C, 100°C, 120°C, 150°C, 180°C, 200°C, 220°C, 250°C, 280°C, 300°C, and the baking time can be, for example, 10s, 50s, 100s, 200s, 300s, 500s, 600s, 800s, 1000s, 1500s, 2000s, 2500s, 3000s.

[0075] The present application also provides a semiconductor device, which includes a patterned substrate, and the patterned substrate is formed using the composition described above. Due to the use of the resist lower layer film provided above, the semiconductor device provided by the present application has good comprehensive performance. In the present application, there is no restriction on the specific type of semiconductor device. In one embodiment of the present application, the semiconductor device may be an integrated circuit device including a chip. In the preparation process of the chip, other functional layers can be prepared after completing the aforementioned patterning process. In some embodiments of the present application, the semiconductor device may include a substrate, a hard mask, a silicon-containing resist lower layer film, and a photoresist film that are stacked in sequence during the patterning process. Among them, the substrate can be, but is not limited to, a silicon wafer substrate, a silicon nitride substrate, and a glass substrate; the hard mask can be, for example, an organic hard mask with a high carbon content, etc.

[0076] In the embodiments of the present application, there is no special limitation on the structure of the semiconductor device. Those skilled in the art can design it based on actual application needs and prepare it based on the resist underlayer film provided in the embodiments of the present application.

[0077] In the embodiments of the present application, there is no limitation on the specific type of semiconductor device. In some embodiments of the present application, the semiconductor device may be an integrated circuit device including a chip.

[0078] In some specific embodiments of the present application, a method for preparing a semiconductor device may include: performing a patterning process on a substrate to be patterned to obtain a patterned substrate. Specifically, for example, the method may include:

[0079] S201, sequentially preparing a hard mask, a resist underlayer film, and a photoresist film on a substrate to be patterned;

[0080] S202, using a mask, exposing and developing the photoresist film to pattern the photoresist film to obtain a patterned photoresist film;

[0081] S203, using the patterned photoresist film as a mask, patterning the resist lower layer film to obtain a patterned resist lower layer film;

[0082] S204, using the patterned resist lower layer film as a mask, patterning the hard mask to obtain a patterned hard mask;

[0083] S205 , using the patterned hard mask as a mask, etching the substrate to be patterned to obtain a patterned substrate.

[0084] In step S201, a resist underlayer film is coated on a substrate using the composition provided above, and baked to obtain the resist underlayer film. The patterning process in steps S203 and S204 can be, for example, dry etching using plasma.

[0085] The technical solution of this application is described in detail below with multiple embodiments.

[0086] Example 1

[0087] After 6.9g of phenyltrimethoxysilane, 20.4g of methyltrimethoxysilane and 48.9g of tetramethoxysilane are mixed evenly, they are gradually added dropwise to a mixed solution of 0.25g of 68% nitric acid, 48.2g of methanol and 45.1g of water. After the addition, the mixture is reacted at room temperature (25°C) for 4h, and then 200g of propylene glycol ethyl ether is added. Then, the mixture is distilled under reduced pressure to remove water and by-product alcohol, etc. to obtain a silicon-containing resin solution precursor. Then, the mixture is heated and aged at 90°C for 12h, and propylene glycol ethyl ether is added and the temperature is lowered to dilute the mixture to obtain a silicon-containing resin solution with a solid content of 8%, wherein the silicon-containing resin includes a Q structural unit and a T structural unit, and the T structural unit includes T 101 and T 102 , the specific chemical structures of the Q structural unit and the T structural unit are shown below:

[0088]

[0089] Let Q n for the reason 29 The integrated area of ​​the nuclear magnetic peak corresponding to the Q structural unit measured by the Si nuclear magnetic resonance spectrum, wherein n represents the number of oxygen atoms bonded to other silicon atoms in the Q structural unit; T m for the reason 29 The integrated area of ​​the nuclear magnetic peak corresponding to the T structural unit measured by the Si nuclear magnetic resonance spectrum is: wherein m represents the number of oxygen atoms bonded to other silicon atoms in the T structural unit. 20 parts by mass of the silicone resin solution prepared above, 70 parts by mass of propylene glycol ethyl ether, 10 parts by mass of water, and 1 part by mass of triphenylsulfonium nitrate were mixed uniformly and filtered through a 0.02 μm fluororesin filter to obtain composition (A1).

[0090] The weight average molecular weight (Mw) of the composition (A1) was characterized by GPC, and the result was 3400 g / mol.

[0091] use 29 The Si NMR spectrum was used to characterize the composition (A1). 29 Si NMR spectrum is as follows Figure 1 As shown, according to Figure 1 Attributing and integrating the areas yields:

[0092] T2 101 (δ=-55ppm):1.00;T3 101 (δ=-62ppm):3.70;T2 102 (δ=-71ppm): 0.28; T3 102 (δ=-78ppm): 0.82;

[0093] Q2 (δ=-90ppm): 0.50; Q3 (δ=-99ppm): 4.51; Q4 (δ=-107ppm): 3.52; T2=T2 101 +T2 102 =1.28; T3=T3 101 +T3 102 =4.52; calculated branching degree DB = (2Q4 + Q3 + T3) / (2Q 4+ 4 / 3(Q3+T3)+2 / 3(Q2+T2))=0.80.

[0094] Example 2

[0095] The only difference from Example 1 is that the heat aging temperature is 100° C. and the heat aging time is 24 h, to obtain composition (A2).

[0096] The weight average molecular weight (Mw) of the composition (A2) was characterized by GPC, and the result was 4600 g / mol.

[0097] use 29 The Si NMR spectrum of the composition (A2) was characterized and the branching degree DB was calculated based on the attribution and integrated area = 0.83.

[0098] Example 3

[0099] The only difference from Example 1 is that the heat aging temperature is 110° C. and the heat aging time is 24 h, to obtain composition (A3).

[0100] The weight average molecular weight (Mw) of the composition (A3) was characterized by GPC, and the result was 6100 g / mol.

[0101] use 29 The Si NMR spectrum of the composition (A3) was characterized and the branching degree DB was calculated based on the attribution and integrated area = 0.86.

[0102] Example 4

[0103] 5.0g of phenyltrimethoxysilane, 11.8g of 3-glycidyloxypropyltrimethoxysilane, 17.0g of methyltrimethoxysilane and 62.5g of tetraethoxysilane were mixed evenly and then gradually added dropwise to a mixed solution of 0.33g of 68% nitric acid, 49g of isopropanol and 54g of water. After the addition, the mixture was reacted at room temperature (25°C) for 8h, and then 250g of propylene glycol ethyl ether was added. The mixture was then subjected to reduced pressure distillation to remove water and by-product alcohol, etc. to obtain a silicon-containing resin solution precursor. The mixture was then heated and aged at 70°C for 12h, and propylene glycol ethyl ether was added and the temperature was lowered to dilute the mixture to obtain a silicon-containing resin solution with a solid content of 8%, wherein the silicon-containing resin includes a Q structural unit and a T structural unit, and the T structural unit includes T 201 、T 202 T 203 , the specific chemical structure of the T structural unit bracketing the Q structural unit is as follows:

[0104]

[0105] Let Q n for the reason 29 The integrated area of ​​the nuclear magnetic peak corresponding to the Q structural unit measured by the Si nuclear magnetic resonance spectrum, wherein n represents the number of oxygen atoms bonded to other silicon atoms in the Q structural unit; T m for the reason 29 The integrated area of ​​the nuclear magnetic peak corresponding to the T structural unit measured by the Si nuclear magnetic resonance spectrum, where m represents the number of oxygen atoms bonded to other silicon atoms in the T structural unit. 20 parts by mass of the silicone resin solution prepared above, 60 parts of propylene glycol ethyl ether, 20 parts of propylene glycol monomethyl ether acetate, and 2 parts of benzyltriethylammonium chloride were mixed uniformly and filtered through a 0.02 μm fluororesin filter to obtain composition (A4).

[0106] The weight average molecular weight (Mw) of the composition (A4) was characterized by GPC, and the result was 3200 g / mol.

[0107] use 29 The Si NMR spectrum of the composition (A4) was characterized by the following attributes and integrated areas:

[0108] T2 201 +T2 203 (δ=-57ppm):1.00;T3 201 +T3 203 (δ=-62ppm):2.82;T2 202 (δ=-71ppm):0.14;T3 202 (δ=-78ppm):

[0109] 0.36; Q2 (δ=-91ppm): 0.28; Q3 (δ=-99ppm): 4.32; Q4 (δ=-107ppm): 1.95; T2=T2 201 +T2 202 +T2 203 =1.14; T3=T3 201 +T3 202 +T3 203 =3.18; calculated branching degree DB = (2Q4 + Q3 + T3) / (2Q 4+ 4 / 3(Q3+T3)+2 / 3(Q2+T2))=0.77.

[0110] Example 5

[0111] The only difference from Example 4 is that the heat aging temperature is 90° C. and the heat aging time is 24 h, to obtain composition (A5).

[0112] The weight average molecular weight (Mw) of the composition (A5) was characterized by GPC, and the result was 4700 g / mol.

[0113] use 29 The Si NMR spectrum of the composition (A5) was characterized and the branching degree DB was calculated based on the attribution and integrated area = 0.83.

[0114] Example 6

[0115] The only difference from Example 4 is that the heat aging temperature is 120° C. and the heat aging time is 24 h, to obtain composition (A6).

[0116] The weight average molecular weight (Mw) of the composition (A6) was characterized by GPC, and the result was 13200 g / mol.

[0117] use 29 The Si NMR spectrum of the composition (A6) was characterized and the branching degree DB was calculated based on the attribution and integrated area = 0.87.

[0118] In order to highlight the beneficial effects of the embodiments of the present application, the following comparative examples are provided.

[0119] Comparative Example 1

[0120] The only difference from Example 1 is that the silicone resin solution precursor is not subjected to heat aging to obtain composition (B1).

[0121] The weight average molecular weight (Mw) of the composition (B1) was characterized by GPC, and the result was 1500 g / mol.

[0122] use 29 The Si NMR spectrum of the composition (B1) was characterized and the branching degree DB was calculated based on the attribution and integrated area = 0.65.

[0123] Comparative Example 2

[0124] The only difference from Example 4 is that the silicone resin solution precursor is not subjected to heat aging to obtain composition (B2).

[0125] The weight average molecular weight (Mw) of the composition (B2) was characterized by GPC, and the result was 1800 g / mol.

[0126] use 29 The Si NMR spectrum of the composition (B2) was characterized and the branching degree DB was calculated based on the attribution and integrated area = 0.65.

[0127] Comparative Example 3

[0128] After 1.9g of phenyltrimethoxysilane, 2.3g of methyltrimethoxysilane, and 76.0g of tetramethoxysilane are mixed evenly, they are gradually added dropwise to a mixed solution of 0.25g of 68% nitric acid, 48.2g of methanol, and 45.1g of water. After the addition, the mixture is reacted at room temperature (25°C) for 4h, and then 200g of propylene glycol ethyl ether is added. Then, reduced pressure distillation is performed to remove water and by-product alcohol, etc. to obtain a silicon-containing resin solution precursor. Then, heat aging is performed at 110°C for 24h, and propylene glycol ethyl ether is added and the temperature is lowered to dilute to obtain a silicon-containing resin solution with a solid content of 8%.

[0129] 20 parts by mass of the silicone resin solution prepared above, 70 parts by mass of propylene glycol ethyl ether, 10 parts by mass of water, and 1 part by mass of triphenylsulfonium nitrate were mixed uniformly and filtered through a 0.02 μm fluororesin filter to obtain a composition (B3).

[0130] The weight average molecular weight (Mw) of the composition (B1) was characterized by GPC, and the result was 1600 g / mol.

[0131] use 29The Si NMR spectrum of the composition (B3) was characterized and the branching degree DB was calculated based on the attribution and integrated area = 0.96.

[0132] Performance Testing

[0133] The compositions A1-A6 prepared in Examples 1-6 and the compositions B1-B4 prepared in Comparative Examples 1-3 were spin-coated on a silicon wafer substrate to form a thin film, and then baked at 220°C for 60s to obtain respective resist underlayer films. The composition of Comparative Example 3 was difficult to form a film, and the obtained resist underlayer film cracked, making it difficult to test the relevant properties. The refractive index n and absorption coefficient k of these resist underlayer films at a wavelength of 193nm were then tested using an ellipsometer. These resist underlayer films were plasma etched with a fluorine-based gas (composition: CF4:CHF3 = 50%:50%) to obtain the fluorine-based gas dry etching rate. The obtained data are shown in Table 1.

[0134] Table 1

[0135]

[0136] As can be seen from Table 1, compared to Comparative Example 1, Examples 1-3 of the present application significantly improve the fluorine-based gas dry etching rate of the resist underlayer film by increasing the branching degree DB of the silicone-containing resin, with almost no impact on the optical properties (refractive index and absorption coefficient). Compared to Comparative Example 2, Examples 4-6 of the present application significantly improve the fluorine-based gas dry etching rate of the resist underlayer film by increasing the branching degree DB of the silicone-containing resin, with almost no impact on the optical properties (refractive index and absorption coefficient).

[0137] It should be understood that the first, second and various numerical numbers involved in this document are only distinguished for the convenience of description and are not intended to limit the scope of this application.

[0138] In this application, "and / or" describes the relationship between related objects, indicating that three possible relationships exist. For example, "A and / or B" can mean: A exists alone, A and B exist simultaneously, and B exists alone. A and B can be singular or plural. The character " / " generally indicates that the related objects are in an "or" relationship.

[0139] In this application, "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b or c", or "at least one of a, b and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc or abc, where a, b, c can be single or multiple.

[0140] In this application, “-” represents a range value, including the endpoint values ​​at both ends. For example, the value of a can be 0.5-15, which means that the value of a can be between 0.5 and 15, and includes the endpoint values ​​0.5 and 15.

[0141] It should be understood that in the various embodiments of the present application, the size of the serial numbers of the above-mentioned processes does not mean the order of execution. Some or all of the steps can be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

[0142] The above is a preferred embodiment of the present application, but it should not be construed as limiting the scope of the present application. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present application, and such improvements and modifications are also considered to be within the scope of protection of the present application.

Claims

1. A composition, characterized in that The composition includes a silicon-containing resin, a solvent, and an acid, wherein the silicon-containing resin includes a Q structural unit and a T structural unit; the Q structural unit includes one first silicon atom and four oxygen atoms bonded to the first silicon atom; the T structural unit includes one second silicon atom and three oxygen atoms bonded to the second silicon atom; Let Q n The silicone resin 29 The integrated area of ​​the nuclear magnetic peak corresponding to the Q structural unit obtained from the Si nuclear magnetic resonance spectrum, wherein n represents the number of oxygen atoms in the four oxygen atoms in any Q structural unit that are bonded to the silicon atoms in the adjacent structural unit; T m The silicone resin 29 The integrated area of ​​the nuclear magnetic peak corresponding to the T structural unit obtained from the Si nuclear magnetic resonance spectrum, wherein m represents the number of oxygen atoms in the three oxygen atoms in any T structural unit that are bonded to the silicon atoms in the adjacent structural unit; The branching degree of the silicone resin is DB, and DB is defined as (2Q4+Q3+T3) / [2Q 4+ 4 / 3(Q3+T3)+2 / 3(Q2+T2)], the DB satisfies: 0.75≤DB≤0.

90.

2. The composition according to claim 1, wherein The weight average molecular weight of the silicone-containing resin is 2,000-15,000.

3. The composition according to claim 1, wherein In the silicon-containing resin, the molar ratio of the Q structural unit to the T structural unit is (1-9):

1.

4. The composition according to claim 1, wherein In the composition, the mass percentage of the silicone-containing resin is 0.1%-5%; the mass percentage of the solvent is 94.0%-99.8%; and the mass percentage of the acid is 0.001%-5%.

5. The composition according to claim 1, wherein The solvent includes an alcohol ether solvent, and the alcohol ether solvent includes one or more 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 butyl glycol methyl ether; the acid includes one or more of nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, 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.

6. The composition according to claim 5, wherein The solvent also includes a non-alcohol solvent, and the non-alcohol solvent includes one or more of toluene, cyclohexane, tetrahydrofuran, methyl tert-butyl ether, cyclopentyl methyl ether, acetone, cyclohexanone, methyl isobutyl ketone, methyl amyl 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 gamma-butyrolactone; in the composition, the mass of the alcohol ether solvent is greater than or equal to 60% of the total mass of the solvent.

7. The composition according to claim 1, wherein The Q structural unit of the silicone-containing resin is derived from a first monomer, which includes one or more of tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane and tetra-n-butoxysilane; the T structural unit of the silicone-containing resin is derived from a second monomer, which includes a monomer with a structural formula of R1-Si(OR2)3, wherein R1 is a substituted or unsubstituted C1-C20 hydrocarbon group, and R2 is a C1-C6 alkyl group.

8. The composition according to claim 7, wherein The R1 is selected from a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C3-C20 cycloalkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, or a substituted or unsubstituted C6-C20 aryl group; when R1 is a substituted C1-C20 alkyl group, a substituted C3-C20 cycloalkyl group, a substituted C2-C20 alkenyl group, a substituted C2-C20 alkynyl group, or a substituted C6-C20 aryl group, the substituent group is selected from at least one of a halogen atom, an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, a cyano group, -OR3, -SR4, -CONR5R6, an ester group, an isocyanurate group, and a lactone ring, wherein R3 is a hydrocarbon group, R4 is a hydrocarbon group, and R5 and R6 are independently selected from a hydrogen atom, a substituted or unsubstituted hydrocarbon group.

9. A resist underlayer film, characterized in that: The resist underlayer film is formed using the composition according to any one of claims 1 to 8.

10. A semiconductor device, characterized in that: The semiconductor device includes a patterned substrate, wherein the patterned substrate is formed using the composition according to any one of claims 1 to 8.

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