Primer for semiconductor substrate and pattern forming method

Abstract

To provide a primer for a semiconductor substrate that is a novel surface modifier for a resist pattern having high adhesion with a resist film, capable of forming an excellent resist pattern with a thin film, a laminated substrate with the surface modifier and the resist pattern laminated sequentially on the substrate, a pattern forming method, and a manufacturing method of a semiconductor device.SOLUTION: A resist pattern surface modifier that is applied to a substrate before forming a resist pattern of 0.10 μm or less on the substrate to enhance the adhesion between the substrate and the resist pattern, and is represented by the following average composition formula (1): a surface modifier for a resist pattern, comprising at least one compound of a hydrolyzate thereof, or a hydrolytic condensate thereof. (Wherein, R1 is a -(CH2)nY group, Y is a cyclohexenyl group or the like, n is an integer of 0 to 4, R2 is a C1 to 4 monovalent hydrocarbon group, and X is a hydrogen atom or a C1 to 4 monovalent hydrocarbon group, a is 1 to 2, b is 0 to 1, c is 0 to 2, and a+b+c≤4.)SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a primer for semiconductor substrates which is a surface modifier for resist patterns, a laminated substrate in which a surface modifier and a resist pattern are laminated in this order on a substrate, a pattern forming method, and a method for manufacturing a semiconductor device. [Background technology]

[0002] Conventionally, in the manufacture of semiconductor devices, lithography processes using resist compositions have been carried out. In recent years, with the increasing integration of semiconductor devices, there has been a demand for finer patterns such as wiring. With the finer patterns, light sources with shorter wavelengths such as far ultraviolet light, vacuum ultraviolet light, electron beams (EB), and X-rays have come to be used. Particularly recently, short-wavelength light such as KrF excimer lasers (wavelength 248 nm) and ArF excimer lasers (wavelength 193 nm) have been adopted to form resist patterns.

[0003] Accordingly, the diffuse reflection of actinic rays from the semiconductor substrate and the influence of standing waves have become major problems, and therefore, in order to solve these problems, a method of providing an anti-reflective coating (Bottom Anti-Reflective Coating: BARC) between the resist and the semiconductor substrate has been widely studied. As such an anti-reflective coating, many studies have been conducted on organic anti-reflective coatings formed from compositions containing polymers having light-absorbing groups (chromophores) because of their ease of use (for example, Patent Document 1).

[0004] On the other hand, with EUV (extreme ultraviolet, wavelength 13.5 nm) which is applied to further fine processing technology, there is no problem of reflection from the semiconductor substrate, but as patterns become finer, there is an issue of resist pattern collapse, so research is being conducted on resist underlayer films that have high adhesion to the resist. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Special Publication No. 2008-501985 Summary of the Invention [Problem to be solved by the invention]

[0006] Conventional resist underlayer films have a problem in that they are prone to etching defects such as side etching during the etching process. Therefore, if it becomes possible to modify the substrate surface using a primer layer that is thinner than conventional underlayer films, it is expected that the adhesion of the photoresist will be improved without causing etching defects such as side etching, and the photoresist resolution will be improved in advanced lithography processes.

[0007] The present invention has been made to improve the above-mentioned circumstances, and has an object to provide a primer for semiconductor substrates, which is a novel surface modifier for resist patterns that has high adhesion to resist films and is capable of forming a thin, good resist pattern; a laminated substrate in which a surface modifier and a resist pattern are laminated in that order on a substrate; a pattern forming method; and a method for manufacturing a semiconductor device. [Means for solving the problem]

[0008] The present invention encompasses the following: [1] A surface modifier for resist patterns that is applied to a substrate prior to forming a resist pattern having a size of 0.10 μm, preferably 0.05 μm or less, on the substrate to enhance adhesion between the substrate and the resist pattern, A compound represented by the following average composition formula (1): A hydrolysate of a compound represented by the following average composition formula (1): A hydrolysis condensate of a compound represented by the following average composition formula (1): A surface modifier for resist patterns, comprising at least one of the following: [ka] (In the formula, R 1has the general formula: -(CH2) n Y is a monovalent organic group, Y represents a hydrogen atom, an acetoxy group, a γ-butyrolactone group, a C1-C6 carbinol group optionally substituted with a halogen atom, a norbornene group, a toluyl group, a C1-C3 alkoxyphenyl group, a C6-C30 aryl group optionally substituted with a halogen atom or a C1-C3 alkoxysilyl group, a C1-C4 alkyl group optionally interrupted by an oxygen atom, a phenylsulfonamide group, a monovalent group derived from a cyclic amide optionally substituted with a C1-C3 alkyl group or a C2-C5 alkenyl group, a monovalent group derived from a cyclic imide optionally substituted with a C1-C3 alkyl group or a C2-C5 alkenyl group, a C3-C6 cyclic alkenyl group optionally substituted with a C1-C3 alkyl group or a C2-C5 alkenyl group, a phenylsulfone group, a p-tolylsulfonyl group, a p-toluenesulfonyl group, or a monovalent group represented by the following formula (1-1) or (1-2), [ka] [ka] n is an integer from 0 to 4; R 2 is a C1-4 monovalent hydrocarbon group, X represents a hydrogen atom or a C1-4 monovalent hydrocarbon group; a is 1~2, b is 0 to 1, c is a number between 0 and 2, a+b+c≦4. [2] R 1 is an acetoxy group, a γ-butyrolactone group, a di(trifluoromethyl)hydroxymethyl group, a cyclohexenyl group, a toluyl group, a C1-C3 alkoxyphenyl group, a pentafluorophenyl group, a phenanthrenyl group, a C1-C3 alkoxysilylphenyl group, a phenylsulfonamide group, or a monovalent group represented by the following formula (1-1), (1-2) or (1-3): [ka] [ka] [ka] The surface modifier according to [1], characterized in that it is any one of the following: [3] The surface modifier according to [1] or [2], wherein the substrate is a metal or inorganic anti-reflective coating substrate. [4] The surface modifier according to any one of [1] to [3], wherein the substrate comprises glass which may be vapor-deposited with Si, SiN, SiON, TiSi, TiN or Cr. [5] A laminated substrate comprising a substrate, the surface modifier according to any one of [1] to [4], and a resist pattern laminated thereon in this order. [6] The laminated substrate according to [5], further comprising a silicon hard mask layer on the substrate. [7] A pattern forming method, comprising applying the surface modifier according to any one of [1] to [4] onto a substrate, baking the applied surface, and then applying a photoresist composition thereon to perform patterning. [8] The pattern forming method according to [7], wherein the patterning includes a step of exposing to ArF, EUV or EB. [9] A method for manufacturing a semiconductor device, comprising the steps of applying the surface modifier according to any one of [1] to [4] onto a substrate, baking the substrate, applying a photoresist composition thereon, patterning the substrate, and then etching the substrate.

[10] The laminate substrate according to [5], further comprising a spin-on carbon or amorphous carbon layer on the substrate, followed by a silicon hard mask layer. Effect of the Invention

[0009] According to the present invention, the adhesion of the photoresist is improved by modifying the wafer surface with the silane coupling agent, and the photoresist resolution in the advanced lithography process is improved. In addition, since the film thickness of the silane coupling agent is thinner than that of the conventional underlayer film, there is an advantage that etching defects such as side etching are less likely to occur in the etching process.

[0010] That is, conventional organic primers have weak bonds with the substrate and between primers, and are easily decomposed by moisture, but the compound represented by the average composition formula (1) according to the present invention, its hydrolysate, or its hydrolysis condensate is Si-based, and therefore has strong bonds with the substrate and between primers, and is not easily decomposed by moisture. As a result, the surface modifier according to the present invention exhibits high surface modification ability due to strong adhesion to the substrate and improved adhesion due to crosslinking between primers.

[0011] In the present invention, when a surface modifier containing a compound represented by the average composition formula (1) is applied, the coating film can be subjected to hydrolysis or hydrolysis condensation after it is formed. In addition, when a surface modifier containing a hydrolyzate of a compound represented by the average composition formula (1) is applied, the coating film can be subjected to hydrolysis condensation after it is formed. In general, these can make the film thinner after baking compared to the case where a surface modifier containing a hydrolysis condensate of a compound represented by the average composition formula (1) is applied.

[0012] Furthermore, the final film thickness and the degree of surface modification of the coating film obtained from any of the surface modifiers can be controlled by changing the baking conditions, removing with a solvent, etc. Furthermore, regardless of the thickness of the coating film immediately after coating, any of the coating films obtained from any of the surface modifiers remains on the substrate surface in the same manner after the solvent is removed, has good film thickness uniformity, and exhibits excellent lithography properties. The coating film of the present invention may be a monomolecular film of the compound represented by the average composition formula (1).

[0013] Therefore, according to the present invention, surface treatment is possible with a film thickness of, for example, about 0.1 nm to 5 nm (1 to 50 Å).

[0014] The surface modifier according to the present invention has an effect of preventing resist collapse by improving adhesion to the substrate and adhesion by crosslinking between primers. 1 By appropriately selecting R, various other effects can be obtained. For example, 1 By selecting a group that generates an acid upon photolysis as R, it is possible to change the shape of the resist. 1 It is also possible to change the shape of the resist by selecting a group that becomes hydrophilic upon photolysis or thermal decomposition as R. 1 By selecting a group that generates a base upon photolysis as R, it is possible to enhance the effect of preventing resist collapse. 1 By selecting a group that hydrophobicizes the substrate as the aryl group, it is possible to obtain the effect of preventing pattern collapse.

[0015] The degree of surface modification by the surface modifier of the present invention can be evaluated, for example, by measuring the water contact angle by the method described in the Examples. The greater the difference between the water contact angles before and after application, the greater the degree of surface modification.

[0016] The surface modifier according to the present invention can be used as a film that functions as an etching mask for a semiconductor substrate, and also as a surface treatment agent.

[0017] The surface modifier according to the present invention can be applied not only to glass substrates, but also to bare-Si and other oxide films, nitride films, such as SiO, SiN, SiON, and TiN, and metal substrates, and can also be applied to coating or deposition type SiHM (silicon hard mask), BARC, coating type SOC (spin-on carbon, film with high carbon content), or deposition type carbon film (amorphous carbon film, etc.).

[0018] The surface modifier according to the present invention is applicable to the formation of a resist pattern using short wavelength light such as ArF, electron beam (EB), and extreme ultraviolet (EUV). [Brief description of the drawings]

[0019] [Figure 1] This is an SEM image showing the results of forming a primer layer and a photoresist on SiON, exposing it using an EUV exposure tool, and patterning it. [Diagram 2] This is an SEM image showing the results of forming a primer layer and a photoresist on SiON, exposing it using an EUV exposure tool, and patterning it. [Diagram 3] This is an SEM photograph showing the results of forming a photoresist without forming a primer layer on SiON, exposing it using an EUV exposure tool, and patterning it. [Figure 4] This is an SEM photograph showing the results of forming a primer layer and a photoresist on SiON, exposing the layer using an EUV exposure tool, and then drawing using an EB drawing tool. [Diagram 5] This is an SEM photograph showing the result of forming a primer layer and a photoresist on SiON and performing drawing using an EB drawing machine. [Figure 6] This is an SEM photograph showing the result of forming a photoresist on SiON without forming a primer layer, and then performing drawing using an EB drawing machine. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] [Surface modifier] The present invention relates to a surface modifier for resist patterns that is applied to a substrate prior to forming a resist pattern having a size of 0.1 μm or less, preferably 0.05 μm or less, on the substrate, thereby enhancing adhesion between the substrate and the resist pattern.

[0021] The surface modifier according to the present invention contains at least one of a compound represented by the following average composition formula (1), a hydrolysate of a compound represented by the following average composition formula (1), or a hydrolysis condensate of a compound represented by the following average composition formula (1). [ka] (In the formula, R 1 Ha-(CH2) n is a Y group, Y represents a hydrogen atom, an acetoxy group, a γ-butyrolactone group, a C1 to C6 carbinol group optionally substituted with a halogen atom, a norbornene group, a toluyl group, a C1 to C3 alkoxyphenyl group, a C6 to C30 aryl group optionally substituted with a halogen atom or a C1 to C3 alkoxysilyl group, a C1 to C4 alkyl group optionally interrupted by an oxygen atom, a phenylsulfonamido group, a cyclic amide group optionally substituted with a C1 to C3 alkyl group or a C2 to C5 alkenyl group, a cyclic imido group optionally substituted with a C1 to C3 alkyl group or a C2 to C5 alkenyl group, a C3 to C6 cyclic alkenyl group optionally substituted with a C1 to C3 alkyl group or a C2 to C5 alkenyl group, a phenylsulfone group, a toluylsulfone group, or a monovalent group represented by the following formula (1-1) or (1-2), [ka] [ka] n is an integer from 0 to 4; R 2 is a C1-4 monovalent hydrocarbon group, X represents a hydrogen atom or a C1-4 monovalent hydrocarbon group; a is 1~2, b is 0 to 1, c is a number between 0 and 2, a+b+c≦4.

[0022] The molecular weight of the compound represented by the average composition formula (1) is 100 to 999, for example.

[0023] Typical alkyl groups in the above "C1-C4 alkyl group optionally interrupted by an oxygen atom", "cyclic amide group optionally substituted with a C1-C3 alkyl group or a C2-C5 alkenyl group", "cyclic imido group optionally substituted with a C1-C3 alkyl group or a C2-C5 alkenyl group", and "cyclic alkenyl group optionally substituted with a C1-C3 alkyl group or a C2-C5 alkenyl group" are linear or branched alkyl groups having 1 to 3 or 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, i-propyl, etc. Cyclic alkyl groups can also be used, such as cyclopropyl, etc.

[0024] Examples of the C1-C4 alkyl group interrupted by an oxygen atom include a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, an ethoxymethyl group, and an ethoxyethyl group.

[0025] Examples of the C2 to C5 alkenyl group include an allyl group, a vinyl group (ethenyl group), a propenyl group, and a butenyl group, with an allyl group being preferred.

[0026] Examples of the monovalent group derived from a cyclic amide include monovalent groups derived from an α-lactam (three-membered ring), a β-lactam (four-membered ring), a γ-lactam (five-membered ring), and a δ-lactam (six-membered ring).

[0027] An example of the monovalent group derived from a cyclic imide is an isocyanuric group. The monovalent group derived from a cyclic imide of the present application is preferably an isocyanuric group in which the substituents on the nitrogen atoms at the 2- and 4-positions are hydrogen atoms, methyl groups, or C2-C5 alkenyl groups. More preferably, it is a monovalent group having a structure of the following formula (1-3): [ka]

[0028] Typical cyclic alkenyl groups in the above "C3 to C6 cyclic alkenyl group optionally substituted with C1 to C3 alkyl group or C2 to C5 alkenyl group" include 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-methyl-2-cyclopentenyl group, 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, cyclopentenyl group, 2-methyl-5-cyclopentenyl group, 2-methylene-cyclopentyl group, 3-methyl-1-cyclopentenyl group, 3-methyl-2-cyclopentenyl group, 3-methyl-3-cyclopentenyl group, 3-methyl-4-cyclopentenyl group, 3-methyl-5-cyclopentenyl group, 3-methylene-cyclopentyl group, 1-cyclohexenyl group, 2-cyclohexenyl group and 3-cyclohexenyl group. Examples of the "cyclic alkenyl group optionally substituted with a C1 to C3 alkyl group or a C2 to C5 alkenyl group" include the above-mentioned cyclic alkenyl groups in which one hydrogen atom is substituted with the above-mentioned C1 to C3 alkyl group or C2 to C5 alkenyl group.

[0029] Typical aryl groups in the above "C6 to C30 aryl group optionally substituted with a halogen atom or a C1 to C3 alkoxysilyl group" include aryl groups having 6 to 30 carbon atoms, such as a phenyl group, an o-methylphenyl group, a m-methylphenyl group, a p-methylphenyl group, an o-chlorophenyl group, a m-chlorophenyl group, a p-chlorophenyl group, an o-fluorophenyl group, a pentafluorophenyl group, a p-mercaptophenyl group, an o-methoxyphenyl group, a p-methoxyphenyl group, a p-aminophenyl group, a p-cyanophenyl group, an α-naphthyl group, a β-naphthyl group, an o-biphenylyl group, a m-biphenylyl group, a p-biphenylyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 4-phenanthryl group, a 9-phenanthryl group, and a 4-triethoxysilylphenyl group.

[0030] Typical alkoxy groups in the above "C1 to C3 alkoxyphenyl group" and "C6 to C30 aryl group optionally substituted with a halogen atom or a C1 to C3 alkoxysilyl group" include alkoxy groups having a straight chain, branched or cyclic alkyl moiety having 1 to 3 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, etc., and examples of cyclic alkoxy groups include a cyclopropoxy group, etc. Examples of the "C1 to C3 alkoxyphenyl group" include a 4-methoxyphenyl group, a 4-ethoxyphenyl group, a 4-(methoxymethoxy)phenyl group, and a 4-(1-methoxyethoxy)phenyl group.

[0031] Typical halogen atoms in the above "C1 to C6 carbinol group optionally substituted with a halogen atom" and "C6 to C30 aryl group optionally substituted with a halogen atom or a C1 to C3 alkoxysilyl group" include fluorine, chlorine, bromine, iodine, etc.

[0032] Examples of the C1 to C6 carbinol group optionally substituted with a halogen atom include a di(trifluoromethyl)hydroxymethyl group and a 1,1-di(trifluoromethyl)-1-hydroxyethyl group.

[0033] Preferred R 1 Examples of the aryl group include an acetoxy group, a γ-butyrolactone group, a di(trifluoromethyl)hydroxymethyl group, a cyclohexenyl group, a toluyl group, a C1-C3 alkoxyphenyl group, a pentafluorophenyl group, a phenanthrenyl group, a C1-C3 alkoxysilylphenyl group, a phenylsulfonamide group, and a monovalent group represented by the following formula (1-1), (1-2), or (1-3): [ka] [ka] [ka] Examples include:

[0034] R 2 is a C1 to C4 monovalent hydrocarbon group, specifically a linear or branched alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, or an i-propyl group.

[0035] The compound represented by the average composition formula (1), its hydrolysate, or its hydrolysis condensate may each be one or more kinds, and the compound, its hydrolysate, or its hydrolysis condensate may each be one or more kinds mixed for use, preferably one or two kinds.

[0036] When combining the two, for example, (1a) a compound represented by the above average composition formula (1), in which Y has a toluyl group, a C1-C3 alkoxyphenyl group, a C6-C30 aryl group which may be substituted with a halogen atom or a C1-C3 alkoxysilyl group, a phenylsulfonamido group, a monovalent group derived from a cyclic amide which may be substituted with a C1-C3 alkyl group or a C2-C5 alkenyl group, or a monovalent group derived from a cyclic imide which may be substituted with a C1-C3 alkyl group or a C2-C5 alkenyl group; (2a) A combination of a compound represented by the above average composition formula (1) in which Y has a phenylsulfonamide group, a phenylsulfone group, a p-tolylsulfonyl group, a p-toluenesulfonyl group, or a monovalent group represented by the following formula (1-1) or (1-2): [ka] [ka] When combining two or more types, for example, (1a) A compound represented by the above average composition formula (1), in which Y has a monovalent group derived from a cyclic amide which may be substituted with a C2-C5 alkenyl group; (2a) A combination of a compound represented by the above average composition formula (1) in which Y has a phenylsulfonamide group, a phenylsulfone group, a p-tolylsulfonyl group, a p-toluenesulfonyl group, or a monovalent group represented by the following formula (1-1) or (1-2): [ka] [ka] When combining two or more types, for example, (1a) a compound represented by the above average composition formula (1) having an isocyanuric group in which Y is a C2-C5 alkenyl group; (2a) A combination of a compound represented by the above average composition formula (1) in which Y has a phenylsulfonamide group, a phenylsulfone group, a p-tolylsulfonyl group, a p-toluenesulfonyl group, or a monovalent group represented by the following formula (1-1) or (1-2): [ka] [ka] When combining two or more types, for example, (1a) R above 1 a compound represented by the above average composition formula (1), which has a γ-butyrolactone group, a di(trifluoromethyl)hydroxymethyl group, a cyclohexenyl group, a toluyl group, a C1-C3 alkoxyphenyl group, a pentafluorophenyl group, a phenanthrenyl group, a C1-C3 alkoxysilylphenyl group, a phenylsulfonamide group, or a monovalent group represented by the following formula (1-3): [ka] (2a) Above R 1 is a combination with a compound represented by the above average composition formula (1) having a phenylsulfonamide group or a monovalent group represented by the following formula (1-1) or (1-2). [ka] [ka]

[0037] [Hydrolysate] The hydrolyzate of the compound represented by the average composition formula (1) can generally be obtained by hydrolysis using a known method. The most widely known method is a hydrolysis method in which pure water or a mixed solvent of pure water and a solvent is added dropwise to a solution in which the compound represented by the average composition formula (1) is dissolved in a solvent, and the solution is heated and stirred at a temperature of 40° C. or higher for several hours or more. The amount of pure water used in this method is arbitrarily selected depending on the purpose of complete hydrolysis or partial hydrolysis. Water is usually 0.5 to 100 moles, preferably 1 to 10 moles, based on the total alkoxy groups of the compound represented by the average composition formula (1). The hydrolysis can be performed using a hydrolysis catalyst, but can also be performed without using a hydrolysis catalyst. When a hydrolysis catalyst is used, 0.001 to 10 moles, preferably 0.001 to 1 mole, of the hydrolysis catalyst can be used per mole of the hydrolyzable groups. The reaction temperature when performing hydrolysis and condensation is usually 2 to 150° C. The hydrolysis may be performed completely or partially. That is, the hydrolysis product may contain hydrolyzates or monomers remaining in the hydrolysis condensate.

[0038] The hydrolysate may be one or more of the compound represented by the average composition formula (1), its hydrolysate, or its hydrolyzed condensate, and may be one or more of the compound, its hydrolysate, or its hydrolyzed condensate, and may be used in combination of one or more of the compound, its hydrolysate, or its hydrolyzed condensate. Preferably, one or two of the compound, its hydrolysate, or its hydrolyzed condensate are used.

[0039] A specific example of the combination of two of the above hydrolysates is a combination of the compounds represented by the above average composition formula (1).

[0040] In the above hydrolysis method, an acid catalyst or an alkali catalyst is generally used to promote the hydrolysis reaction. The hydrolysis catalyst may be an acid or a base. Examples of the hydrolysis catalyst include metal chelate compounds, organic acids, inorganic acids, organic bases, and inorganic bases.

[0041] Metal chelate compounds as hydrolysis catalysts include, for example, triethoxy mono(acetylacetonate)titanium, tri-n-propoxy mono(acetylacetonate)titanium, tri-i-propoxy mono(acetylacetonate)titanium, tri-n-butoxy mono(acetylacetonate)titanium, tri-sec-butoxy mono(acetylacetonate)titanium, tri-t-butoxy mono(acetylacetonate)titanium, diethoxy bis(acetylacetonate)titanium, di-n-propoxy bis(acetylacetonate)titanium, di -i-propoxy bis(acetylacetonate) titanium, di-n-butoxy bis(acetylacetonate) titanium, di-sec-butoxy bis(acetylacetonate) titanium, di-t-butoxy bis(acetylacetonate) titanium, monoethoxy tris(acetylacetonate) titanium, mono-n-propoxy tris(acetylacetonate) titanium, mono-i-propoxy tris(acetylacetonate) titanium, mono-n-butoxy tris(acetylacetonate) titanium, mono-sec-butoxy tris(acetylacetonate) titanium titanium acetate, titanium mono-t-butoxy tris(acetylacetonate), titanium tetrakis(acetylacetonate), titanium triethoxy mono(ethylacetoacetate), titanium tri-n-propoxy mono(ethylacetoacetate), titanium tri-i-propoxy mono(ethylacetoacetate), titanium tri-n-butoxy mono(ethylacetoacetate), titanium tri-sec-butoxy mono(ethylacetoacetate), titanium tri-t-butoxy mono(ethylacetoacetate), titanium diethoxy bis(ethoxy) di-n-propoxy bis(ethylacetoacetate) titanium, di-i-propoxy bis(ethylacetoacetate) titanium, di-n-butoxy bis(ethylacetoacetate) titanium, di-sec-butoxy bis(ethylacetoacetate) titanium, di-t-butoxy bis(ethylacetoacetate) titanium, monoethoxy tris(ethylacetoacetate) titanium, mono-n-propoxy tris(ethylacetoacetate) titanium, mono-i-propoxy tris(ethylacetoacetate) titanium,Mono-n-butoxy tris(ethylacetoacetate)titanium, mono-sec-butoxy tris(ethylacetoacetate)titanium, mono-t-butoxy tris(ethylacetoacetate)titanium, tetrakis(ethylacetoacetate)titanium, mono(acetylacetonato) tris(ethylacetoacetate)titanium, bis(acetylacetonato) bis(ethylacetoacetate)titanium, tris(acetylacetonato) mono(ethylacetoacetate)titanium, and other titanium chelate compounds; triethoxy mono(acetylacetonato) setonate)zirconium, tri-n-propoxy mono(acetylacetonate)zirconium, tri-i-propoxy mono(acetylacetonate)zirconium, tri-n-butoxy mono(acetylacetonate)zirconium, tri-sec-butoxy mono(acetylacetonate)zirconium, tri-t-butoxy mono(acetylacetonate)zirconium, diethoxy bis(acetylacetonate)zirconium, di-n-propoxy bis(acetylacetonate)zirconium, di-i-propoxy bis(acetylacetonate)zirconium cetylacetonate)zirconium, di-n-butoxy bis(acetylacetonate)zirconium, di-sec-butoxy bis(acetylacetonate)zirconium, di-t-butoxy bis(acetylacetonate)zirconium, monoethoxy tris(acetylacetonate)zirconium, mono-n-propoxy tris(acetylacetonate)zirconium, mono-i-propoxy tris(acetylacetonate)zirconium, mono-n-butoxy tris(acetylacetonate)zirconium, mono-sec- Butoxy tris(acetylacetonate) zirconium, mono-t-butoxy tris(acetylacetonate) zirconium, tetrakis(acetylacetonate) zirconium, triethoxy mono(ethylacetoacetate) zirconium, tri-n-propoxy mono(ethylacetoacetate) zirconium, tri-i-propoxy mono(ethylacetoacetate) zirconium, tri-n-butoxy mono(ethylacetoacetate) zirconium, tri-sec-butoxy mono(ethylacetoacetate) zirconium,Tri-t-butoxy mono(ethylacetoacetate)zirconium, diethoxy bis(ethylacetoacetate)zirconium, di-n-propoxy bis(ethylacetoacetate)zirconium, di-i-propoxy bis(ethylacetoacetate)zirconium, di-n-butoxy bis(ethylacetoacetate)zirconium, di-sec-butoxy bis(ethylacetoacetate)zirconium, di-t-butoxy bis(ethylacetoacetate)zirconium, monoethoxy tris(ethylacetoacetate)zirconium, mono-n-propoxy tris(ethylacetoacetate)zirconium, mono-i-propoxy tris(ethylacetoacetate)zirconium, mono-n zirconium chelate compounds such as 1-butoxy tris(ethylacetoacetate)zirconium, mono-sec-butoxy tris(ethylacetoacetate)zirconium, mono-t-butoxy tris(ethylacetoacetate)zirconium, tetrakis(ethylacetoacetate)zirconium, mono(acetylacetonato) tris(ethylacetoacetate)zirconium, bis(acetylacetonato) bis(ethylacetoacetate)zirconium, and tris(acetylacetonato) mono(ethylacetoacetate)zirconium; and aluminum chelate compounds such as tris(acetylacetonato)aluminum and tris(ethylacetoacetate)aluminum.

[0042] Examples of organic acids usable as hydrolysis catalysts include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linoleic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, and tartaric acid.

[0043] Examples of inorganic acids as hydrolysis catalysts include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.

[0044] Examples of organic bases as hydrolysis catalysts include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclooctane, diazabicyclononane, diazabicycloundecene, and tetramethylammonium hydroxide. Examples of inorganic bases include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide. Among these catalysts, metal chelate compounds, organic acids, and inorganic acids are preferred, and these may be used alone or in combination of two or more.

[0045] Examples of organic solvents used in hydrolysis include aliphatic hydrocarbon solvents such as n-pentane, i-pentane, n-hexane, i-hexane, n-heptane, i-heptane, 2,2,4-trimethylpentane, n-octane, i-octane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, i-propylbenzene, diethylbenzene, i-butylbenzene, triethylbenzene, di-i-propylbenzene, n-amylnaphthalene, and trimethylbenzene; methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, n-pentanol, i-pentanol, 2-methylbutanol, sec-pentanol, t-pentanol, 3-methoxybutanol, n-hexanol, 2-methylpentanol, sec-hexanol, 2-ethylbutanol, monoalcohol solvents such as ethanol, sec-heptanol, heptanol-3, n-octanol, 2-ethylhexanol, sec-octanol, n-nonyl alcohol, 2,6-dimethylheptanol-4, n-decanol, sec-undecyl alcohol, trimethylnonyl alcohol, sec-tetradecyl alcohol, sec-heptadecyl alcohol, phenol, cyclohexanol, methylcyclohexanol, 3,3,5-trimethylcyclohexanol, benzyl alcohol, phenylmethylcarbinol, diacetone alcohol, and cresol; polyhydric alcohol solvents such as ethylene glycol, propylene glycol, 1,3-butylene glycol, pentanediol-2,4, 2-methylpentanediol-2,4, hexanediol-2,5, heptanediol-2,4, 2-ethylhexanediol-1,3, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, and glycerin;Ketone solvents such as acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl i-butyl ketone, methyl n-pentyl ketone, ethyl n-butyl ketone, methyl n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and fenchone; ethyl ether, i-propyl ether, n-butyl ether, n-hexyl ether, 2-ethylhexyl ether, ethylene oxide, 1,2-propylene oxide, dioxolane, 4-methyldioxolane, dioxane, dimethyldioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-n-hexyl ether, ethylene glycol monophenyl ether, ethylene glycol Ether solvents such as mono-2-ethyl butyl ether, ethylene glycol dibutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol mono-n-butyl ether, diethylene glycol di-n-butyl ether, diethylene glycol mono-n-hexyl ether, ethoxytriglycol, tetraethylene glycol di-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetrahydrofuran, and 2-methyltetrahydrofuran;Diethyl carbonate, methyl acetate, ethyl acetate, gamma-butyrolactone, gamma-valerolactone, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, sec-butyl acetate, n-pentyl acetate, sec-pentyl acetate, 3-methoxybutyl acetate, methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, benzyl acetate, cyclohexyl acetate, methylcyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene acetate Examples of suitable solvents include ester-based solvents such as glycol monobutyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, glycol diacetate, methoxytriglycol acetate, ethyl propionate, n-butyl propionate, i-amyl propionate, diethyl oxalate, di-n-butyl oxalate, methyl lactate, ethyl lactate, n-butyl lactate, n-amyl lactate, diethyl malonate, dimethyl phthalate, and diethyl phthalate; nitrogen-containing solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, and N-methylpyrrolidone; sulfur-containing solvents such as dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, sulfolane, and 1,3-propane sultone. These solvents can be used alone or in combination of two or more.

[0046] In particular, ketone solvents such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-i-butyl ketone, methyl-n-pentyl ketone, ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-i-butyl ketone, trimethylnonanone, cyclohexanone, methylcyclohexanone, 2,4-pentanedione, acetonylacetone, diacetone alcohol, acetophenone, and fenchone are preferred in terms of storage stability of the solution.

[0047] The heating temperature and heating time can be appropriately selected according to need. For example, a method of heating and stirring at 50°C for 24 hours, a method of heating and stirring under reflux for 8 hours, etc. can be mentioned. As long as the compound represented by the average composition formula (1) is hydrolyzed, a method of stirring at room temperature without heating can also be used.

[0048] [Hydrolysis condensation product] The hydrolysis condensation product of the compound represented by the average composition formula (1) can be obtained by dissolving the compound represented by the average composition formula (1) in a solvent containing water, carrying out a hydrolysis condensation reaction in the presence of a catalyst, and then distilling off the solvent containing water, the catalyst, and the like under reduced pressure. Examples of preferred catalysts include inorganic acids such as hydrochloric acid and nitric acid, and organic acids such as formic acid, oxalic acid, fumaric acid, maleic acid, glacial acetic acid, acetic anhydride, propionic acid, and n-butyric acid. The amount of catalyst used is, for example, 0.001% by mass to 1% by mass based on the total mass of the compound represented by the average composition formula (1). The hydrolysis condensation reaction is carried out, for example, at a temperature condition of 30° C. to 80° C. The pH during the hydrolysis condensation reaction is not particularly limited, but is usually 2 or more and less than 5. In addition, a compound other than the compound represented by the average composition formula (1) can be added to form a hydrolysis co-condensation product as long as it does not impair the effects of the present invention.

[0049] The above hydrolysis condensation product may be one or more of the compound represented by the average composition formula (1), its hydrolysate, or its hydrolysis condensation product, and may be one or more of the compound, its hydrolysate, or its hydrolysis condensation product, and may be used in combination of one or more of the compound, its hydrolysate, or its hydrolysis condensation product, preferably one or two of the compound, its hydrolysate, or its hydrolysis condensation product.

[0050] A specific example of the combination of two types of the hydrolysis condensation products is a combination of the compounds represented by the above-mentioned average composition formula (1).

[0051] The weight average molecular weight (Mw) of the hydrolysis condensate is 1,000 to 50,000. The preferred weight average molecular weight is 1,200 to 20,000. A condensate having a weight average molecular weight of 1,000 to 50,000 can be obtained. The weight average molecular weight of the hydrolysis condensate may be, for example, 300 to 999, for example, 300 to 1,000, for example, 300 to 2,000, or an oligomer having a weight average molecular weight of 300 to 3,000. The weight average molecular weight is a molecular weight obtained by polystyrene conversion by GPC analysis. The GPC measurement conditions are, for example, a GPC apparatus (product name HLC-8220GPC, manufactured by Tosoh Corporation), a GPC column (product names Shodex KF803L, KF802, KF801, manufactured by Showa Denko K.K.), a column temperature of 40°C, an eluent (elution solvent) of tetrahydrofuran, a flow rate (flow velocity) of 1.0 ml / min, and a standard sample of polystyrene (manufactured by Showa Denko K.K.).

[0052] [Preparation of Coating Solution] The coating solution of the surface modifier according to the present invention contains a compound represented by the average composition formula (1), a hydrolyzate of a compound represented by the average composition formula (1), or a hydrolysis condensate of a compound represented by the average composition formula (1), and other components as necessary, and can be prepared by dissolving them in a suitable solvent. In the present invention, as long as such a coating solution can be obtained, the preparation method is not limited. For example, each component may be added and mixed in sequence in the solvent used. In this case, the order of addition of each component is not particularly limited. Also, solutions in which each component is dissolved in the solvent used may be mixed.

[0053] In addition, for the purpose of adjusting the pH of the coating solution of the present invention, an acid can be mixed in advance into the solution. The amount of the acid is preferably 0.01 to 2.5 mol, more preferably 0.1 to 2 mol, per mol of silicon atoms in the compound represented by the average composition formula (1). The acids used above include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; monocarboxylic acids such as formic acid, acetic acid, and malic acid; organic acids such as oxalic acid; and polycarboxylic acids such as citric acid, propionic acid, and succinic acid. Of these, acids in solution can be used as they are, but it is preferable to dilute them with a solvent contained in the coating liquid before use. Other acids are preferably dissolved in the solvent of the coating liquid at an appropriate concentration before use.

[0054] The solvent may be an organic solvent used in preparing the compound represented by the average composition formula (1), the hydrolyzate of the compound represented by the average composition formula (1), or the hydrolysis condensate of the compound represented by the average composition formula (1), or a solvent used in concentrating, diluting, or substituting another solvent for these solutions. The solvent may be one or more types selected arbitrarily for use.

[0055] When preparing a cured film from the coating liquid of the present invention, the coating liquid of the present invention contains the compound represented by the average composition formula (1), the hydrolyzate of the compound represented by the average composition formula (1), or the hydrolysis condensate of the compound represented by the average composition formula (1) and the above-mentioned solvent, and therefore can be used as is for coating on a substrate. In addition, the above-mentioned solvents and various other solvents may be added to the coating liquid for the purpose of adjusting the concentration, ensuring the flatness of the coating film, improving the wettability of the coating liquid to the substrate, adjusting the surface tension, polarity, boiling point, etc. of the coating liquid, and used as a coating liquid.

[0056] [Other ingredients] Other components that may be included in the surface modifier are described below.

[0057] The surface modifier of the present invention may contain a curing catalyst. The curing catalyst acts as a curing catalyst when the coating film containing the hydrolysis condensation product is heated and cured. As the curing catalyst, ammonium salts, phosphines, phosphonium salts, and sulfonium salts can be used. Specific examples are as described in WO2017 / 145809.

[0058] Among them, nitrogen-containing silane compounds are preferred as curing catalysts. Examples of the nitrogen-containing silane compounds include imidazole ring-containing silane compounds such as N-(3-triethoxysilylpropyl)-4,5-dihydroimidazole (IMIDTEOS).

[0059] The compound represented by the average composition formula (1) is hydrolyzed in a solvent using a catalyst, and the hydrolysis condensate (polymer) obtained by condensation can be simultaneously removed of the by-product alcohol, the hydrolysis catalyst used, and water by vacuum distillation or the like. In addition, the acid or base catalyst used in the hydrolysis can be removed by neutralization or ion exchange. In addition, an organic acid, water, alcohol, or a combination thereof can be added to the surface modifier of the present invention in order to stabilize the surface modifier containing the hydrolysis condensate.

[0060] Examples of the organic acid include oxalic acid, acetic acid, trifluoroacetic acid, malonic acid, methylmalonic acid, succinic acid, maleic acid, malic acid, tartaric acid, phthalic acid, citric acid, glutaric acid, citric acid, lactic acid, and salicylic acid. Among them, oxalic acid and maleic acid are preferred. The organic acid to be added is 0.1 to 5.0 parts by mass relative to 100 parts by mass of the hydrolysis condensate of the compound represented by the average composition formula (1). The water to be added can be pure water, ultrapure water, ion-exchanged water, etc., and the amount of the added water can be 1 to 20 parts by mass relative to 100 parts by mass of the surface modifier. The alcohol to be added is preferably one that is easily scattered by heating after application, and examples of the alcohol to be added include methanol, ethanol, propanol, isopropanol, and butanol. The alcohol to be added can be 1 to 20 parts by mass relative to 100 parts by mass of the surface modifier.

[0061] Therefore, the surface modifier may contain one or more selected from the group consisting of water, an acid, and a curing catalyst. In addition to the above components, the surface modifier of the present invention may contain an organic polymer compound, a photoacid generator, a surfactant, and the like, as necessary.

[0062] By using an organic polymer compound, it is possible to adjust the dry etching rate (amount of film thickness reduction per unit time), attenuation coefficient, refractive index, etc. of the film formed from the surface modifier of the present invention.

[0063] Examples of the photoacid generator contained in the surface modifier of the present invention include onium salt compounds, sulfonimide compounds, and disulfonyldiazomethane compounds. Examples of the onium salt compounds include iodonium salt compounds such as diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoronormal butanesulfonate, diphenyliodonium perfluoronormal octanesulfonate, diphenyliodonium camphorsulfonate, bis(4-tert-butylphenyl)iodonium camphorsulfonate, and bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, and sulfonium salt compounds such as triphenylsulfonium hexafluoroantimonate, triphenylsulfonium nonafluoronormal butanesulfonate, triphenylsulfonium camphorsulfonate, and triphenylsulfonium trifluoromethanesulfonate.

[0064] Examples of the sulfonimide compound include N-(trifluoromethanesulfonyloxy)succinimide, N-(nonafluoronormalbutanesulfonyloxy)succinimide, N-(camphorsulfonyloxy)succinimide, and N-(trifluoromethanesulfonyloxy)naphthalimide.

[0065] Examples of the disulfonyldiazomethane compound include bis(trifluoromethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane, bis(2,4-dimethylbenzenesulfonyl)diazomethane, and methylsulfonyl-p-toluenesulfonyldiazomethane.

[0066] The photoacid generator may be used alone or in combination of two or more. When the photoacid generator is used, the proportion is 0.01 to 15 parts by mass, or 0.1 to 10 parts by mass, or 0.5 to 1 part by mass, based on 100 parts by mass of the hydrolysis condensate of the compound represented by the average composition formula (1).

[0067] The surfactant is effective in suppressing the occurrence of pinholes, striations, etc., when the surface modifier of the present invention is applied to a substrate. Examples of the surfactant contained in the surface modifier of the present invention include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkyl allyl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene-polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene Nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; EFTOP (registered trademark) EF301, EF303, and EF352 (manufactured by Tochem Products Co., Ltd.); Megafac (registered trademark) F171, F173, R-08, R-30, R-30N, and R-4 Examples of the surfactant include fluorine-based surfactants such as 0LM (manufactured by DIC Corporation), Fluorad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Limited), Asahiguard (registered trademark) AG710, Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by Asahi Glass Co., Ltd.), and organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.). These surfactants may be used alone or in combination of two or more. When a surfactant is used, the proportion thereof is 0.0001 to 5 parts by mass, or 0.001 to 1 part by mass, or 0.01 to 1 part by mass, relative to 100 parts by mass of the hydrolysis condensate of the compound represented by the average composition formula (1).

[0068] The surface modifier of the present invention may further contain a rheology control agent, an adhesion promoter, etc. The rheology control agent is effective in improving the fluidity of the surface modifier. The adhesion promoter is effective in improving the adhesion between the semiconductor substrate or resist and the underlayer film.

[0069] The solvent used in the surface modifier of the present invention is not particularly limited as long as it is a solvent capable of dissolving the above-mentioned solid content. Examples of such solvents include water (ion-exchanged water, ultrapure water), methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl isobutyl carbinol, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoether ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycol monomethyl ether, ethyl propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate, ethyl propionate,Propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethyl methoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-meth Examples of the solvent include dimethyl ether, ...

[0070] Preferred are propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monomethyl ether, and ultrapure water.

[0071] The surface modifier according to the present invention can be applied to bare-Si, oxide films such as SiO2, SiN, SiON, TiN, nitride films, and metal substrates. Preferably, the substrate is a metal or inorganic anti-reflective substrate. Preferably, the substrate is Si, SiN, SiON, TiSi, TiN, or glass that may be vapor-deposited with Cr.

[0072] Furthermore, the surface modifier of the present invention can be applied to coated or deposited SiHM, BARC, coated SOC (spin-on carbon, a film with a high carbon content), and deposited amorphous carbon.

[0073] [Laminated board] The surface modifier according to the present invention and then a resist pattern may be laminated on a substrate to form a laminate substrate. Preferably, the laminate substrate further includes a silicon hard mask layer on the substrate. The spin-on carbon layer or amorphous carbon layer may be further formed under the silicon hard mask layer. The silicon hard mask layer, the spin-on carbon layer and the amorphous carbon layer each have a thickness of, for example, 5 nm to 2000 nm.

[0074] [Method of forming resist pattern and method of manufacturing semiconductor device] A pattern can be formed by applying the surface modifier of the present invention onto a substrate, baking the surface, applying a photoresist composition, and patterning the surface. Preferably, the method further includes a step of modifying the surface with a solvent after the baking and before applying the photoresist composition. Preferably, the patterning includes a step of exposing the surface to ArF, EUV, or EB. More preferably, the surface is exposed to EUV (wavelength 13.5 nm) or EB (electron beam), and most preferably to EUV (wavelength 13.5 nm).

[0075] The above pattern is preferably a resist pattern.

[0076] The method for producing a semiconductor device according to the present invention includes the steps of applying the surface modifier according to the present invention onto a substrate, baking the substrate, applying a photoresist composition, patterning the substrate, and then etching the substrate.

[0077] The surface modifier according to the present invention is applied onto a substrate to form a coating film. The coating method is a conventional method such as spin coating. After baking this film, a step of forming a resist by applying a photoresist composition thereon can be performed. The baking temperature and time are usually 80 to 300° C. and 0.5 to 5 minutes. After forming a coating film of the surface modifier of the present invention, a step of treating the surface with a solvent may be further included before coating the photoresist composition. The solvent used for this purpose may be any solvent used in a photoresist composition, such as methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl isobutyl carbinol, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoether ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethylene glycol mono Methyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, methyl formate, ethyl formate, propyl formate, isopropyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl acetate, ethyl acetate, amyl acetate, isoamyl acetate, hexyl acetate, methyl propionate,Ethyl propionate, Propyl propionate, Isopropyl propionate, Butyl propionate, Isobutyl propionate, Methyl butyrate, Ethyl butyrate, Propyl butyrate, Isopropyl butyrate, Butyl butyrate, Isobutyl butyrate, Ethyl hydroxyacetate, Ethyl 2-hydroxy-2-methylpropionate, Methyl 3-methoxy-2-methylpropionate, Methyl 2-hydroxy-3-methylbutyrate, Ethyl methoxyacetate, Ethoxyethyl acetate, Methyl 3-methoxypropionate, Ethyl 3-ethoxypropionate, Ethyl 3-methoxypropionate, 3-methoxybutyl acetate, 3-methoxypropyl acetate, 3-methyl-3-methoxy Dibutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, toluene, xylene, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, 4-heptanone, cyclohexanone, N,N-dimethylformamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, 4-methyl-2-pentanol, and γ-butyrolactone are used, but propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cyclohexanone are preferred. After applying the solvent by a conventional method such as spin coating, the solvent may be dried by heating to 80°C to 200°C. It is also possible to prepare a coating film by applying the surface modifier according to the present invention onto a substrate, bake the film, and then form a silicon hard mask thereon, and then form a resist thereon.

[0078] The surface modifier according to the present invention can form a coating having a thickness of 1 nm to 1,000 nm on a semiconductor substrate, for example, 1 nm to 500 nm, 0.1 nm to 500 nm, 0.1 nm to 300 nm, 0.1 nm to 200 nm, 0.1 nm to 100 nm, 0.1 nm to 50 nm, 0.1 nm to 30 nm, 0.1 nm to 20 nm, 0.1 nm to 10 nm, and most preferably 0.1 nm to 8 nm.

[0079] The silicon hard mask can be a polysiloxane obtained by hydrolysis of a hydrolyzable silane. For example, polysiloxanes obtained by hydrolysis of tetraethoxysilane, methyltrimethoxysilane, and phenyltriethoxysilane can be exemplified. These can form a coating film with a thickness of 5 to 200 nm on the coating film of the surface modifier according to the present invention.

[0080] The photoresist composition is not particularly limited as long as it is sensitive to the light used for exposure. Either a negative photoresist or a positive photoresist can be used. Examples of the photoresist include a positive photoresist made of a novolac resin and a 1,2-naphthoquinone diazide sulfonic acid ester, a chemically amplified photoresist made of a binder having a group that decomposes with an acid to increase the alkaline dissolution rate and a photoacid generator, a chemically amplified photoresist made of a low molecular compound that decomposes with an acid to increase the alkaline dissolution rate of the photoresist, an alkali-soluble binder, and a photoacid generator, and a chemically amplified photoresist made of a binder having a group that decomposes with an acid to increase the alkaline dissolution rate, a low molecular compound that decomposes with an acid to increase the alkaline dissolution rate of the photoresist, and a photoacid generator. Examples of the photoresist include APEX-E (trade name) manufactured by Shipley, PAR710 (trade name) manufactured by Sumitomo Chemical Co., Ltd., and SEPR430 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd. Further, there can be mentioned fluorine-containing polymer photoresists as described in, for example, Proc. SPIE, Vol. 3999, 330-334 (2000), Proc. SPIE, Vol. 3999, 357-364 (2000), and Proc. SPIE, Vol. 3999, 365-374 (2000).

[0081] In addition, the electron beam resist can be either negative or positive. Chemically amplified resists include those made of an acid generator and a binder having a group that decomposes with an acid to change the alkaline dissolution rate, those made of an alkali-soluble binder, an acid generator, and a low molecular weight compound that decomposes with an acid to change the alkaline dissolution rate of the resist, those made of an acid generator, a binder having a group that decomposes with an acid to change the alkaline dissolution rate, and a low molecular weight compound that decomposes with an acid to change the alkaline dissolution rate of the resist, non-chemically amplified resists made of a binder having a group that decomposes with an electron beam to change the alkaline dissolution rate, and those made of a binder having a site that is cut by an electron beam to change the alkaline dissolution rate. When these electron beam resists are used, a resist pattern can be formed in the same way as when a photoresist is used, with an electron beam as the irradiation source.

[0082] After coating, the resist solution is baked at a temperature of 70 to 150° C. for 0.5 to 5 minutes, and the resist film thickness is obtained in the range of 10 to 1,000 nm. For example, the thickness can be 10 to 50 nm for EUV light (wavelength 13.5 nm) or electron beam, and 50 to 200 nm, preferably 100 to 150 nm for ArF excimer laser (wavelength 193 nm). The surface modifier, resist solution, developer, etc. according to the present invention can be coated by spin coating, dipping method, spraying method, etc., but the spin coating method is particularly preferred. The resist is exposed through a predetermined mask. For exposure, KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), EUV light (wavelength 13.5 nm), electron beam, etc. can be used. After exposure, post-exposure bake (PEB) can also be performed as necessary. The post-exposure baking is carried out at a heating temperature of 70° C. to 150° C. for a heating time of 0.3 to 10 minutes.

[0083] Development can then be performed with a developer, which removes the photoresist in the exposed areas, for example if a positive photoresist is used, to form a photoresist pattern.

[0084] Examples of the developer include an aqueous solution of an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide, an aqueous solution of a quaternary ammonium hydroxide such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, or choline, or an aqueous solution of an amine such as ethanolamine, propylamine, or ethylenediamine. Furthermore, a surfactant or the like can be added to these developers. The development conditions are appropriately selected from a temperature of 5 to 50° C. and a development time of 10 to 600 seconds. In the present invention, an organic solvent can be used as the developer.

[0085] Examples of organic solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether ... butyl formate, propyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl ... Examples of the aryl esters include ethyl esters, propyl esters, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and propyl 3-methoxypropionate.

[0086] The resist pattern can be etched away to reverse the pattern. Dry etching can be performed using gases such as tetrafluoromethane, perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, and chlorine trifluoride. In particular, dry etching is preferably performed using an oxygen-based gas.

[0087] The photoresist film (upper layer) on which the pattern is formed as described above is used as a protective film to remove the silicon hard mask (middle layer) formed on the lower layer of the surface modifier of the present invention by etching or the like to perform patterning, and then the patterned photoresist film (upper layer) and the silicon hard mask (middle layer) are used as a protective film to remove the organic film (lower layer) such as spin-on carbon or amorphous carbon to perform patterning. Finally, the semiconductor substrate is processed using the patterned silicon hard mask (middle layer) and the organic film (lower layer) as protective films. Furthermore, when the organic film is not formed on the substrate, the semiconductor substrate is processed using a film made of a patterned photoresist and the organic film (intermediate layer) as a protective film.

[0088] After the photoresist film is patterned, first, the silicon hard mask (middle layer) from the portion where the photoresist film has been removed is removed by dry etching to expose the organic film (lower layer). For dry etching of the silicon hard mask, gases such as tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane, and dichloroborane can be used. For dry etching of the silicon hard mask, it is preferable to use a halogen-based gas. In dry etching with a halogen-based gas, the photoresist film and the organic film, which are basically made of organic substances, are difficult to remove. In contrast, the silicon hard mask containing a large number of silicon atoms is quickly removed by the halogen-based gas. Therefore, it is possible to suppress the decrease in the film thickness of the photoresist caused by dry etching of the silicon hard mask. As a result, it becomes possible to use the photoresist as a thin film. Dry etching of the silicon hard mask is preferably performed with a fluorine-based gas, such as tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

[0089] Thereafter, the organic underlayer film is removed using the patterned photoresist film and the silicon hard mask as protective films. The organic film (underlayer) is preferably removed by dry etching using an oxygen-based gas. This is because the silicon hard mask contains a large amount of silicon atoms and is difficult to remove by dry etching using an oxygen-based gas.

[0090] It is also possible to remove the resist pattern and form a reverse pattern (inverted pattern) using the compound represented by average composition formula (1) contained in the surface modifier of the present invention, its hydrolysate, or its hydrolyzed condensate. EXAMPLES

[0091] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following embodiments.

[0092] [Preparation of Coating Solution] The Si-containing monomers shown in Formula-1 to Formula-22 or the Si-containing polymers shown in Formula 23 (Mw=2300) were dissolved in a solvent in the ratios shown in Table 1 to obtain preparation solutions of Preparation Examples 1-23.

[0093] [ka] [ka] [ka] [ka] [ka]

[0094] [ka] [ka] [ka] [ka] [ka] [ka]

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[0095]

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[0096]

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[0097]

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[0098]

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[0101] In Table 1, propylene glycol monomethyl ether acetate is abbreviated as PGMEA, propylene glycol monoethyl ether as PGEE, propylene glycol monomethyl ether as PGME, and ultrapure water as DIW. The content of each component is expressed in parts by mass.

[0102] [Table 1]

[0103] Next, a pH adjuster and a curing catalyst were added to each preparation example to obtain coating solution 1-23 as shown in Table 2. Maleic acid was used as the pH adjuster, and the curing catalyst was that shown in the following formula 24. The content ratio of each component is expressed in parts by mass.

[0104] [ka]

[0105] [Table 2]

[0106] The evaluation results using the coating solution of the present invention are shown below.

[0107] [Attachment to substrate surface] Coating solution 1-23 was applied to a bare-Si wafer. Specifically, 1 ml of each of coating solutions 1-23 was applied to the wafer using CLEANTRACK (registered trademark) ACT8 (Tokyo Electron), spin-coated at 1500 rpm for 60 seconds, and then baked at 110°C. The adhesion of the material to the substrate surface was evaluated by measuring the film thickness of the bare-Si substrate on which each coating solution 1-23 was formed. The material film thickness was measured using an ellipsometric film thickness measuring device RE-3100 (SCREEN). In addition, as Comparative Example 1, the film thickness of a natural oxide film on a bare-Si wafer was measured for comparison. The measurement results are shown in Table 3 below.

[0108] [Table 3]

[0109] [Substrate surface modification] Each of the coating solutions 1-23 was applied to bare-Si and SiON (50 nm). Specifically, 1 ml of each of the coating solutions 1-23 was applied to a wafer using CLEANTRACK (registered trademark) ACT8 (Tokyo Electron), spin-coated at 1500 rpm for 60 seconds, and then baked at 110°C. The contact angle of water was measured for the bare-Si substrate on which each coating film of the coating solutions 1-23 was formed. The water contact angle was measured using a fully automatic contact angle meter DM-701 (manufactured by Kyowa Interface Science Co., Ltd.) in a constant temperature and humidity environment (23°C ± 2°C, 45% RH ± 5%), with a liquid volume of 3 μl, and was measured after stopping for 5 seconds after the liquid was applied. The measurement results are shown in Table 4 below.

[0110] [Table 4]

[0111] [EUV Patterning] The coating liquid 16 was applied to SiON (50 nm), and a photoresist was formed on the wafer on which a film of the coating liquid 16 was formed. The photoresist used was EUV-PR (EUV-photoresist) manufactured by JSR. A patterning evaluation was performed using an EUV exposure machine. Exposure was performed using NXE3300 (manufactured by ASML), and observation was performed using an SEM (CG4100, manufactured by HITACHI). The evaluation results are shown in Table 5. In Table 5, when the photoresist had pattern collapse in the SEM observation, it was recorded as pattern collapse, and when the photoresist had no pattern collapse and the desired pattern was formed, it was recorded as good. Comparative Example 4 in the table is the result of performing HMDS treatment on a SiON wafer at 100°C for 60 seconds, followed by patterning using an EUV exposure machine.

[0112] [Table 5]

[0113] [EB patterning] Coating solutions 19 and 20 were applied to SiON (50 nm), and a photoresist layer was formed on the wafer on which the coating solutions 19 and 20 were formed. EUV-PR manufactured by TOK was used as the photoresist. Drawing was performed using an EB drawing machine ELS-G130 (manufactured by Elionix), and observation was performed using an SEM (CG4100, manufactured by HITACHI). The evaluation results are shown in Table 6. In Table 6, if the photoresist pattern collapsed in the SEM observation, it is recorded as "pattern collapsed," and if the desired pattern was formed, it is recorded as "good." Comparative Example 5 in the table is the result of performing HMDS treatment on a SiON wafer at 100°C for 60 seconds, followed by patterning using an EUV exposure machine.

[0114] [Table 6] [Industrial Applicability]

[0115] Modification of the wafer surface by silane coupling agents improves the adhesion of photoresists, improving the photoresist resolution in advanced lithography processes. In addition, the thickness of the silane coupling agent is thinner than that of conventional underlayer films, which has the advantage that etching defects such as side etching are less likely to occur during the etching process.

Claims

1. A surface modifier for EUV resist patterns that is applied to a substrate before forming a resist pattern of 0.10 μm or less on the substrate to enhance adhesion between the substrate and the resist pattern, A hydrolysis condensate represented by the following average composition formula (1): A surface modifier for EUV resist patterns, comprising one of the following: 【Chemistry 47】 (In the formula, R １ is represented by the general formula: -(CH ２ ) ｎ is a monovalent organic group represented by Y, Y represents a γ-butyrolactone group, a C1 to C6 carbinol group optionally substituted with a halogen atom, a norbornene group, a C1 to C3 alkoxyphenyl group, a C6 to C30 aryl group optionally substituted with a halogen atom or a C1 to C3 alkoxysilyl group, a C1 to C4 alkyl group optionally interrupted by an oxygen atom, a phenylsulfonamido group, a monovalent group derived from a cyclic amide optionally substituted with a C1 to C3 alkyl group or a C2 to C5 alkenyl group, a monovalent group derived from a cyclic imide optionally substituted with a C1 to C3 alkyl group or a C2 to C5 alkenyl group, a C3 to C6 cyclic alkenyl group optionally substituted with a C1 to C3 alkyl group or a C2 to C5 alkenyl group, a phenylsulfone group, or a p-tolylsulfonyl group; n is an integer from 0 to 4.

2. R １ is a γ-butyrolactone group, a C1 to C6 carbinol group optionally substituted with iodine, a di(trifluoromethyl)hydroxymethyl group, a cyclohexenyl group, a C1 to C3 alkoxyphenyl group, a pentafluorophenyl group, a phenanthrenyl group, a C1 to C3 alkoxysilylphenyl group, a phenylsulfonamide group, or a monovalent group represented by (1-3) 【Chemistry 52】 2. The surface modifier according to claim 1, wherein the surface modifier is any one of the following:

3. A surface modifier for EUV resist patterns that is applied to a substrate before forming a resist pattern of 0.10 μm or less on the substrate to enhance adhesion between the substrate and the resist pattern, The substrate surface modifier comprises a hydrolysis condensate selected from the group consisting of (Formula-1), (Formula-5), (Formula-6), (Formula-8) to (Formula-12), and (Formula-14) to (Formula-22) below, or a polymer represented by (Formula-23). 【Chemical 23】 【Chemical 27】 【Chemical formula 28】 【Chemistry 30】 【Chemical 31】 【Chemical 32】 【Chemical 33】 【Chemical 34】 【Chemical 36】 【Chemical Formula 37】 【Chemical 38】 【Chemical Formula 39】 【Chemistry 40】 【Chemistry 41】 【Chemistry 42】 【Chemistry 43】 【Chemical 44】 【Chemistry 45】

4. The surface modifier according to any one of claims 1 to 3, wherein the substrate is a metal or inorganic anti-reflective coating substrate.

5. The substrate is made of Si, SiO ２ 5. The surface modifier according to claim 1, comprising glass which may be vapor-deposited with SiN, SiON, TiSi, TiN or Cr.

6. A laminated substrate in which the surface modifier according to any one of claims 1 to 5 and then a resist pattern are laminated on a substrate in this order.

7. The laminate substrate of claim 6 , further comprising a silicon hard mask layer on the substrate.

8. A pattern forming method comprising applying the surface modifier according to any one of claims 1 to 5 onto a substrate, baking the applied surface, and then applying a photoresist composition thereon to perform patterning.

9. A method for manufacturing a semiconductor device, comprising the steps of applying the surface modifier according to any one of claims 1 to 5 onto a substrate, baking the surface modifier, applying a photoresist composition thereon, patterning the surface modifier, and then etching the substrate.

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