Substrate with thin film, and semiconductor substrate

Abstract

A substrate having a thin film, wherein the thin film has a Si-R1 group in a compound represented by the following formula (1), and the substrate has the thin film having the Si-R1 group disposed on its surface. Si(R1)(R2)n(R3)3-n··· Formula (1) (wherein in the above formula (1), R1 represents a monovalent organic group bonded to Si, R2 represents a monovalent organic group bonded to Si, R3 represents an alkoxy group, an acyloxy group, or a halogen atom bonded to Si, and n represents an integer from 0 to 2, where n is 2, R2 may be the same or different, and where n is 0 or 1, R3 may be the same or different. Where n is 1, R1 and R2 may form a ring structure together.)

Description

Technology Field

[0001] The present invention relates to a substrate having a thin film, a semiconductor substrate, a method for manufacturing a substrate having a thin film, a method for manufacturing a semiconductor substrate, and a compound used therein. Background Technology

[0002] Several methods for fabricating thin films on a substrate are known, other than the coating method of applying a liquid onto the substrate. One widely used technique is Chemical Vapor Deposition (CVD). CVD is a method that fabricates a thin film by supplying a source gas containing the components of the target film onto a substrate and causing a chemical reaction on the substrate surface or in the gas phase.

[0003] Recently, atomic layer deposition (ALD) and molecular layer deposition have been proposed as CVD techniques.

[0004] Using these techniques, the formation of gallium nitride thin films (e.g., Patent Document 1) or organic polymers (e.g., Patent Document 2) has been proposed. Prior art literature

[0005] Patent Document 1: International Publication Pamphlet No. 2020 / 170853 Patent Document 2: Japanese Published Patent Application No. 2014-129606 The problem to be solved

[0006] The present invention aims to provide a substrate having a thin film, wherein a novel thin film is formed on the substrate, a semiconductor substrate, a method for manufacturing a substrate having a thin film capable of forming a novel thin film on the substrate, a method for manufacturing a semiconductor substrate, and additionally, a compound used therein. means of solving the problem

[0008] As a result of conducting a thorough review to solve the above problem, the inventors discovered that the problem could be solved and completed the present invention having the following gist.

[0009] That is, the present invention includes the following.

[0010] [1] As a substrate having a thin film,

[0011] Si-R in the compound represented by the following formula (1) 1 The above thin film having a cell, and

[0012] The above Si-R on its surface 1 The substrate on which the thin film having the above has

[0013] A substrate having a thin film having

[0014] [Chemical Formula 1]

[0015]

[0016] (Among the above formula (1), R 1 represents a monovalent organic group bonded to Si, and R 2 represents a monovalent organic group bonded to Si, and R 3 represents an alkoxy group, acyloxy group, or halogen atom bonded to Si, n represents an integer from 0 to 2, and when n is 2, R 2 may be the same or different, and if n is 0 or 1, R 3 may be the same or different. When n is 1, R 1 and R 2 They may also form a ring structure together.)

[0017] [2] A substrate having a thin film as described in [1], formed by contacting the surface of the substrate with a compound represented by the formula (1) and further chemically reacting the compound.

[0018] [3] R 1A substrate having a thin film as described in [1] or [2], wherein the monovalent organic group in the above is a monovalent organic group having 1 to 20 carbon atoms having an oxygen atom.

[0019] [4] Among the above equation (1), R 1 represents a monovalent group expressed by the following formula (2), and R 2 represents a monovalent group represented by the above formula (2), or an organic group having an alkyl group, an aryl group, an aralkyl group, an alkyl halide group, an aryl halide group, an aralkyl halide group, an alkenyl group, an epoxy group, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, or an organic group having a cyano group, or a combination of two or more of these.

[0020] A substrate having a thin film as described in any one of [1] to [3].

[0021] [Chemical Formula 2]

[0022]

[0023] (Among the above formula (2), R 4 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an epoxy group, a sulfonyl group, or a monovalent organic group comprising two or more of these, and R 5 represents an alkylene group, a hydroxyalkylene group, a sulfide bond, an ether bond, an ester bond, or a combination of two or more of these having 1 to 10 carbon atoms, and X 1 represents a divalent group represented by the following formula (3), a divalent group represented by the formula (4), or a divalent group represented by the formula (5).

[0024] [Chemical Formula 3]

[0025]

[0026] (Among the above equations (3), (4) and (5), R 6 ~R 10Each represents independently a hydrogen atom, or a monovalent organic group comprising an alkyl group, alkenyl group, epoxy group, sulfonyl group having 1 to 10 carbon atoms, or two or more of these. *1 and *3 are bonded to the carbon atom of the carbonyl group in Formula (2). *2 and *4 are bonded to the nitrogen atom in Formula (2).)

[0027] [5] A substrate having a thin film as described in any one of [1] to [4], and

[0028] A resist film disposed above the above thin film

[0029] A semiconductor substrate having

[0030] [6]

[0031] By contacting the surface of a substrate with a gaseous compound represented by formula (1) and further chemically reacting the compound, the Si-R in the compound 1 A process in which a thin film having a group is formed on the surface of the substrate

[0032] A method for manufacturing a substrate having a thin film, comprising

[0033] [Chemical Formula 4]

[0034]

[0035] (Among the above formula (1), R 1 represents a monovalent organic group bonded to Si, and R 2 represents a monovalent organic group bonded to Si, and R 3 represents an alkoxy group, acyloxy group, or halogen atom bonded to Si, n represents an integer from 0 to 2, and when n is 2, R 2 may be the same or different, and if n is 0 or 1, R 3 may be the same or different. When n is 1, R 1 and R 2 They may also form a ring structure together.)

[0036] [7] The process of forming the above thin film on the surface of the substrate is performed in a film formation chamber, and

[0037] Additionally, the above Si-R 1 A method for manufacturing a substrate having a thin film as described in [6], comprising the process of removing the substrate having the thin film formed on its surface from the film formation chamber.

[0038] [8] R 1 A method for manufacturing a substrate having a thin film as described in [6] or [7], wherein the monovalent organic group in the above is a monovalent organic group having 1 to 20 carbon atoms having an oxygen atom.

[0039] [9] Among the above equation (1), R 1 represents a monovalent group expressed by the following formula (2), and R 2 represents a monovalent group represented by the above formula (2), or an organic group having an alkyl group, an aryl group, an aralkyl group, an alkyl halide group, an aryl halide group, an aralkyl halide group, an alkenyl group, an epoxy group, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, or an organic group having a cyano group, or a combination of two or more of these.

[0040] [6] A method for manufacturing a substrate having a thin film as described in any one of [6] to [8].

[0041] [Chemical Formula 5]

[0042]

[0043] (Among the above formula (2), R 4 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an epoxy group, a sulfonyl group, or a monovalent organic group comprising two or more of these, and R 5 represents an alkylene group, a hydroxyalkylene group, a sulfide bond, an ether bond, an ester bond, or a combination of two or more of these having 1 to 10 carbon atoms, and X 1represents a divalent group represented by the following formula (3), a divalent group represented by the formula (4), or a divalent group represented by the formula (5).

[0044] [Chemical Formula 6]

[0045]

[0046] (Among the above equations (3), (4) and (5), R 6 ~R 10 Each represents independently a hydrogen atom, or a monovalent organic group comprising an alkyl group, alkenyl group, epoxy group, sulfonyl group having 1 to 10 carbon atoms, or two or more of these. *1 and *3 are bonded to the carbon atom of the carbonyl group in Formula (2). *2 and *4 are bonded to the nitrogen atom in Formula (2).)

[0047]

[10] A method for manufacturing a substrate having a thin film as described in any one of [6] to [9], comprising a process in which the compound represented by the above formula (1) becomes a gas.

[0048]

[11] A process for manufacturing a substrate having a thin film using a method for manufacturing a substrate having a thin film described in any one of [6] to

[10] , and,

[0049] A process in which a resist film is formed on the upper side of the above thin film.

[0050] A method for manufacturing a semiconductor substrate, comprising

[0051]

[12] Manufacturing of a substrate having a thin film as described in any one of [1] to [4],

[0052] [5] Manufacturing of semiconductor substrates,

[0053] [6] A method for manufacturing a substrate having a thin film as described in any one of [6] to

[10] , and

[0054]

[11] Method for manufacturing a semiconductor substrate

[0055] A compound represented by the above formula (1), used in any one of the following. Effects of the invention

[0056] According to the present invention, a substrate having a thin film formed on a substrate, a semiconductor substrate, a method for manufacturing a substrate having a thin film capable of forming a novel thin film on a substrate, and a method for manufacturing a semiconductor substrate, and additionally, a compound used therein can be provided. Brief explanation of the drawing

[0057] Figure 1 is a schematic cross-sectional view of an example of a substrate having a thin film. Figure 2 is a schematic cross-sectional view of another example of a substrate having a thin film. Figure 3 is a schematic cross-sectional view of an example of a manufacturing apparatus for a substrate having a thin film. Specific details for implementing the invention

[0058] (Method for manufacturing a substrate having a thin film)

[0059] The method for manufacturing a substrate having a thin film according to the present invention is to use Si-R in a compound represented by the following formula (1). 1 This is a method for manufacturing a substrate having a thin film having a cell.

[0060] A method for manufacturing a substrate having a thin film comprises at least a process for forming a thin film, and additionally, if necessary, a process for turning a compound into a gas and a process for removing the substrate.

[0061] <Process in which a compound becomes a gas>

[0062] This process is a process in which a compound represented by the following formula (1) becomes a gas.

[0063] The method of turning the compound into a gas is not particularly limited, and examples include heating a raw material receiving container containing the compound represented by formula (1), depressurizing the inside of a raw material receiving container containing the compound represented by formula (1), or a combination thereof, to turn the compound represented by formula (1) into a gas (steam).

[0064] In addition, the process of making the compound represented by Equation (1) into a gas may be carried out in a raw material receiving container as described above, or it may be carried out using a vaporization chamber instead of a raw material receiving container. The size, material, and structure of the raw material receiving container and the vaporization chamber are not particularly limited and may be determined appropriately by considering the heating temperature or the degree of pressure reduction.

[0065] The heating temperature is not specifically limited and is, for example, 25 to 200°C.

[0066] When the compound represented by formula (1) is in gaseous form, the pressure inside the raw material receiving container and the pressure inside the vaporization chamber are not particularly limited, for example, 1 to 10,000 Pa.

[0067] The compound represented by formula (1) may be a liquid or a solid at room temperature and pressure.

[0068] <<Equation (1)>>

[0069] [Chemical Formula 7]

[0070]

[0071] (In Equation (1), R 1 represents a monovalent organic group bonded to Si, and R 2 represents a monovalent organic group bonded to Si, and R 3 represents an alkoxy group, acyloxy group, or halogen atom bonded to Si, n represents an integer from 0 to 2, and when n is 2, R 2 may be the same or different, and if n is 0 or 1, R 3 may be the same or different. When n is 1, R 1 and R 2 They may also form a ring structure together.)

[0072] R 1 and R 2The monovalent organic group in [the context] is, for example, an organic group with 1 to 20 carbon atoms.

[0073] R 1 and R 2 The monovalent organic group in this case may have heteroatoms as atoms other than carbon atoms and hydrogen atoms. Examples of heteroatoms include nitrogen atoms, oxygen atoms, sulfur atoms, phosphorus atoms, etc.

[0074] R 1 and R 2 The monovalent organic group in may be bonded to silicon atoms by Si-C bonds.

[0075] R 1 and R 2 The monovalent organic group in the sample may have, for example, an alkyl group, a carbonyl group, an amide group, an imide group, an amino group, an imino group, or an alkenyl group, or a combination of two or more of these.

[0076] R 1 and R 2 For example, each does not have a protected functional group independently. Examples of protected functional groups include, for instance, a protected amino group.

[0077] The compound represented by formula (1) is, for example, a hydrolyzable organosilane represented by formula (1) of International Publication No. 2011 / 102470.

[0078] R 1 For example, it represents a 1-valent group represented by the following formula (2).

[0079] [Chemical Formula 8]

[0080]

[0081] (In Equation (2), R 4 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an epoxy group, a sulfonyl group, or a monovalent organic group comprising two or more of these, and R 5represents an alkylene group, a hydroxyalkylene group, a sulfide bond, an ether bond, an ester bond, or a combination of two or more of these having 1 to 10 carbon atoms, and X 1 represents a divalent group represented by the following formula (3), a divalent group represented by the formula (4), or a divalent group represented by the formula (5).

[0082] [Chemical Formula 9]

[0083]

[0084] (Among Equations (3), (4) and (5), R 6 ~R 10 Each represents independently a hydrogen atom, or a monovalent organic group comprising an alkyl group, alkenyl group, epoxy group, sulfonyl group having 1 to 10 carbon atoms, or two or more of these. *1 and *3 are bonded to the carbon atom of the carbonyl group in Formula (2). *2 and *4 are bonded to the nitrogen atom in Formula (2).)

[0085] Preferably, R 2 represents a monovalent group, for example, represented by Equation (2). Or, R 2 is, for example, an alkyl group, an aryl group, an aralkyl group, an alkyl halide group, an aryl halide group, an aralkyl halide group, an alkenyl group, an epoxy group, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, or an organic group having a cyano group, or a combination of two or more of these.

[0086] The alkyl group is, for example, an alkyl group having 1 to 10 carbon atoms.

[0087] The alkyl group may have a straight chain structure or a branched structure.

[0088] As an alkyl group having 1 to 10 carbon atoms having a straight chain or branching, for example, a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n-butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1-dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, Examples include 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2-trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, etc.

[0089] In addition, as an alkyl group, an alkyl group having a cyclic alkyl group may also be used. As an alkyl group having 1 to 10 carbon atoms having a cyclic alkyl group, for example, a cyclopropyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, a cyclopentyl group, a 1-methyl-cyclobutyl group, a 2-methyl-cyclobutyl group, a 3-methyl-cyclobutyl group, a 1,2-dimethyl-cyclopropyl group, a 2,3-dimethyl-cyclopropyl group, a 1-ethyl-cyclopropyl group, a 2-ethyl-cyclopropyl group, a cyclohexyl group, a 1-methyl-cyclopentyl group, a 2-methyl-cyclopentyl group, a 3-methyl-cyclopentyl group, a 1-ethyl-cyclobutyl group, a 2-ethyl-cyclobutyl group, a 3-ethyl-cyclobutyl group, a 1,2-dimethyl-cyclobutyl group, a 1,3-dimethyl-cyclobutyl group, Examples include 2,2-dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2,3-trimethyl-cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2-methyl-cyclopropyl group, 2-ethyl-3-methyl-cyclopropyl group, etc.

[0090] In addition, alkylene groups having 1 to 10 carbon atoms can be examples of alkylene groups derived from the alkyl groups described above.

[0091] An aryl group is, for example, an aryl group having 6 to 20 carbon atoms. Examples of aryl groups having 6 to 20 carbon atoms include, for example, 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 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 the like.

[0092] The alkenyl group is, for example, an alkenyl group having 2 to 10 carbon atoms. As an alkenyl group having 2 to 10 carbon atoms, for example, an ethenyl group, 1-propenyl group, 2-propenyl group, 1-methyl-1-ethenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-ethylethenyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-n-propylethenyl group, 1-methyl-1-butenyl group, 1-methyl-2-butenyl group, 1-methyl-3-butenyl group, 2-ethyl-2-propenyl group, 2-methyl-1-butenyl group, 2-methyl-2-butenyl group, 2-methyl-3-butenyl group, 3-methyl-1-butenyl group, 3-methyl-2-butenyl group, 3-methyl-3-butenyl group, 1,1-dimethyl-2-propenyl group, 1-i-propylethenyl group, 1,2-dimethyl-1-propenyl group, 1,2-dimethyl-2-propenyl group, 1-cyclopentenyl group, 2-cyclopentenyl group, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl-1-pentenyl group, 1-methyl-2-pentenyl group, 1-methyl-3-pentenyl group, 1-methyl-4-pentenyl group, 1-n-butylethenyl group, 2-methyl-1-pentenyl group, 2-methyl-2-pentenyl group, 2-methyl-3-pentenyl group, 2-methyl-4-pentenyl group, 2-n-propyl-2-propenyl group, 3-methyl-1-pentenyl group, 3-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 3-methyl-4-pentenyl group, 3-ethyl-3-butenyl group, 4-methyl-1-pentenyl group, 4-methyl-2-pentenyl group, 4-methyl-3-pentenyl group, 4-methyl-4-pentenyl group, 1,1-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 1,2-dimethyl-1-butenyl group, 1,2-dimethyl-2-butenyl group, 1,2-dimethyl-3-butenyl group, 1-methyl-2-ethyl-2-propenyl group, 1-s-butylethenyl group, 1,3-dimethyl-1-butenyl group, 1,3-dimethyl-2-butenyl group, 1,3-dimethyl-3-butenyl group, 1-i-butylethenyl group, 2,2-dimethyl-3-butenyl group, 2,3-dimethyl-1-butenyl group, 2,3-dimethyl-2-butenyl group, 2,3-dimethyl-3-butenyl group,2-i-propyl-2-propenyl group, 3,3-dimethyl-1-butenyl group, 1-ethyl-1-butenyl group, 1-ethyl-2-butenyl group, 1-ethyl-3-butenyl group, 1-n-propyl-1-propenyl group, 1-n-propyl-2-propenyl group, 2-ethyl-1-butenyl group, 2-ethyl-2-butenyl group, 2-ethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1-t-butylethenyl group, 1-methyl-1-ethyl-2-propenyl group, 1-ethyl-2-methyl-1-propenyl group, 1-ethyl-2-methyl-2-propenyl group, 1-i-propyl-1-propenyl group, 1-i-propyl-2-propenyl group, 1-methyl-2-cyclopentenyl group, Examples include 1-methyl-3-cyclopentenyl group, 2-methyl-1-cyclopentenyl group, 2-methyl-2-cyclopentenyl group, 2-methyl-3-cyclopentenyl group, 2-methyl-4-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, 3-cyclohexenyl group, etc.

[0093] An aralkyl group is an alkyl group substituted with an aryl group. An aralkyl group is, for example, an alkyl group having 1 to 10 carbon atoms substituted with a phenyl group. Examples of aralkyl groups include benzyl groups, phenylethyl groups, phenylpropyl groups, phenylbutyl groups, etc.

[0094] In addition, examples include organic groups (alkyl halides, aryl halides, aralkyl halides) in which hydrogen atoms of these alkyl, aryl, and aralkyl groups are substituted with halogen atoms such as fluorine, chlorine, bromine, and iodine. The substitution of halogen atoms may be performed on all hydrogen atoms or on some hydrogen atoms.

[0095] A hydroxyalkylene group is a group in which at least one hydrogen atom of an alkylene group is substituted with a hydroxyl group. For example, a hydroxyalkylene group is a hydroxyalkylene group having 1 to 10 carbon atoms. Examples of hydroxyalkylene groups include 1-hydroxyethylene group, 2-hydroxyethylene group, 1-hydroxypropylene group, 2-hydroxypropylene group, 3-hydroxypropylene group, hydroxybutylene group, hydroxypentylene group, hydroxyhexylene group, etc.

[0096] Examples of organic groups having an epoxy group include glycidoxymethyl group, glycidoxyethyl group, glycidoxypropyl group, glycidoxybutyl group, epoxycyclohexyl group, etc.

[0097] Examples of organic groups having an acryloyl group include acryloyloxymethyl group, acryloyloxyethyl group, acryloyloxypropyl group, etc.

[0098] Examples of organic groups having a methacryloyl group include the methacryloyloxymethyl group, the methacryloyloxyethyl group, the methacryloyloxypropyl group, etc.

[0099] Examples of organic groups having a mercapto group include mercaptoethyl group, mercaptobutyl group, mercaptohexyl group, mercaptooctyl group, etc.

[0100] Examples of organic groups having a cyano group include cyanoethyl groups, cyanopropyl groups, etc.

[0101] Examples of organic groups having an amino group include aminomethyl groups, aminoethyl groups, aminopropyl groups, etc.

[0102] Examples of organic groups having a sulfonyl group include methylsulfonyl groups, allylsulfonyl groups, phenylsulfonyl groups, etc.

[0103] R in Equation (1) 3The alkoxy group is, for example, an alkoxy group having 1 to 20 carbon atoms. Examples of alkoxy groups having 1 to 20 carbon atoms include, for example, alkoxy groups having 1 to 20 carbon atoms having a straight, branched, or cyclic alkyl group.

[0104] As a straight-chain or branched alkoxy group, for example, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, an n-pentyloxy group, 1-methyl-n-butoxy group, 2-methyl-n-butoxy group, 3-methyl-n-butoxy group, 1,1-dimethyl-n-propoxy group, 1,2-dimethyl-n-propoxy group, 2,2-dimethyl-n-propoxy group, 1-ethyl-n-propoxy group, n-hexyloxy group, 1-methyl-n-pentyloxy group, 2-methyl-n-pentyloxy group, 3-methyl-n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, Examples include 1,3-dimethyl-n-butoxy group, 2,2-dimethyl-n-butoxy group, 2,3-dimethyl-n-butoxy group, 3,3-dimethyl-n-butoxy group, 1-ethyl-n-butoxy group, 2-ethyl-n-butoxy group, 1,1,2-trimethyl-n-propoxy group, 1,2,2-trimethyl-n-propoxy group, 1-ethyl-1-methyl-n-propoxy group, 1-ethyl-2-methyl-n-propoxy group, etc.

[0105] In addition, as an alkoxy group having a cyclic alkyl moiety, for example, a cyclopropoxy group, a cyclobutoxy group, 1-methyl-cyclopropoxy group, 2-methyl-cyclopropoxy group, a cyclopentyloxy group, 1-methyl-cyclobutoxy group, 2-methyl-cyclobutoxy group, 3-methyl-cyclobutoxy group, 1,2-dimethyl-cyclopropoxy group, 2,3-dimethyl-cyclopropoxy group, 1-ethyl-cyclopropoxy group, 2-ethyl-cyclopropoxy group, a cyclohexyloxy group, 1-methyl-cyclopentyloxy group, 2-methyl-cyclopentyloxy group, 3-methyl-cyclopentyloxy group, 1-ethyl-cyclobutoxy group, 2-ethyl-cyclobutoxy group, 3-ethyl-cyclobutoxy group, 1,2-dimethyl-cyclobutoxy group, 1,3-dimethyl-cyclobutoxy group, Examples include 2,2-dimethyl-cyclobutoxy group, 2,3-dimethyl-cyclobutoxy group, 2,4-dimethyl-cyclobutoxy group, 3,3-dimethyl-cyclobutoxy group, 1-n-propyl-cyclopropoxy group, 2-n-propyl-cyclopropoxy group, 1-i-propyl-cyclopropoxy group, 2-i-propyl-cyclopropoxy group, 1,2,2-trimethyl-cyclopropoxy group, 1,2,3-trimethyl-cyclopropoxy group, 2,2,3-trimethyl-cyclopropoxy group, 1-ethyl-2-methyl-cyclopropoxy group, 2-ethyl-1-methyl-cyclopropoxy group, 2-ethyl-2-methyl-cyclopropoxy group, 2-ethyl-3-methyl-cyclopropoxy group, etc.

[0106] R in Equation (1) 3The acyloxy group is, for example, an acyloxy group with 2 to 20 carbon atoms. As acyloxy groups having 2 to 20 carbon atoms, for example, methyl carbonyloxy group, ethyl carbonyloxy group, n-propyl carbonyloxy group, i-propyl carbonyloxy group, n-butyl carbonyloxy group, i-butyl carbonyloxy group, s-butyl carbonyloxy group, t-butyl carbonyloxy group, n-pentyl carbonyloxy group, 1-methyl-n-butyl carbonyloxy group, 2-methyl-n-butyl carbonyloxy group, 3-methyl-n-butyl carbonyloxy group, 1,1-dimethyl-n-propyl carbonyloxy group, 1,2-dimethyl-n-propyl carbonyloxy group, 2,2-dimethyl-n-propyl carbonyloxy group, 1-ethyl-n-propyl carbonyloxy group, n-hexyl carbonyloxy group, 1-methyl-n-pentyl carbonyloxy group, 2-methyl-n-pentylcarbonyloxy group, 3-methyl-n-pentylcarbonyloxy group, 4-methyl-n-pentylcarbonyloxy group, 1,1-dimethyl-n-butylcarbonyloxy group, 1,2-dimethyl-n-butylcarbonyloxy group, 1,3-dimethyl-n-butylcarbonyloxy group, 2,2-dimethyl-n-butylcarbonyloxy group, 2,3-dimethyl-n-butylcarbonyloxy group, 3,3-dimethyl-n-butylcarbonyloxy group, 1-ethyl-n-butylcarbonyloxy group, 2-ethyl-n-butylcarbonyloxy group, 1,1,2-trimethyl-n-propylcarbonyloxy group, 1,2,2-trimethyl-n-propylcarbonyloxy group, 1-ethyl-1-methyl-n-propylcarbonyloxy group, Examples include 1-ethyl-2-methyl-n-propylcarbonyloxy group, phenylcarbonyloxy group, tosylcarbonyloxy group, etc.

[0107] R in Equation (1) 3 Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0108] Examples of compounds represented by formula (1) are shown below.

[0109] [Chemical Formula 10]

[0110]

[0111] [Chemical Formula 11]

[0112]

[0113] [Chemical Formula 12]

[0114]

[0115] In the following example, T is R in Equation (1). 3 am.

[0116] [Chemical Formula 13]

[0117]

[0118] [Chemical Formula 14]

[0119]

[0120] [Chemical Formula 15]

[0121]

[0122] [Chemical Formula 16]

[0123]

[0124] [Chemical Formula 17]

[0125]

[0126] [Chemical Formula 18]

[0127]

[0128] [Chemical Formula 19]

[0129]

[0130] [Chemical Formula 20]

[0131]

[0132] [Chemical Formula 21]

[0133]

[0134] [Chemical Formula 22]

[0135]

[0136] [Chemical Formula 23]

[0137]

[0138] [Chemical Formula 24]

[0139]

[0140] [Chemical Formula 25]

[0141]

[0142] [Chemical Formula 26]

[0143]

[0144] [Chemical Formula 27]

[0145]

[0146] [Chemical Formula 28]

[0147]

[0148] [Chemical Formula 29]

[0149]

[0150] [Chemical Formula 30]

[0151]

[0152] [Chemical Formula 31]

[0153]

[0154] [Chemical Formula 32]

[0155]

[0156] [Chemical Formula 33]

[0157]

[0158] [Chemical Formula 34]

[0159]

[0160] [Chemical Formula 35]

[0161]

[0162] [Chemical Formula 36]

[0163]

[0164] [Chemical Formula 37]

[0165]

[0166] [Chemical Formula 38]

[0167]

[0168] [Chemical Formula 39]

[0169]

[0170] [Chemical Formula 40]

[0171]

[0172] [Chemical Formula 41]

[0173]

[0174] [Chemical Formula 42]

[0175]

[0176] [Chemical Formula 43]

[0177]

[0178] [Chemical Formula 44]

[0179]

[0180] [Chemical Formula 45]

[0181]

[0182] [Chemical Formula 46]

[0183]

[0184] [Chemical Formula 47]

[0185]

[0186] [Chemical Formula 48]

[0187]

[0188] [Chemical Formula 49]

[0189]

[0190] [Chemical Formula 50]

[0191]

[0192] [Chemical Formula 51]

[0193]

[0194] [Chemical Formula 52]

[0195]

[0196] [Chemical Formula 53]

[0197]

[0198] [Chemical Formula 54]

[0199]

[0200] [Chemical Formula 55]

[0201]

[0202] [Chemical Formula 56]

[0203]

[0204] [Chemical Formula 57]

[0205]

[0206] [Chemical Formula 58]

[0207]

[0208] [Chemical Formula 59]

[0209]

[0210] [Chemical Formula 60]

[0211]

[0212] [Chemical Formula 61]

[0213]

[0214] [Chemical Formula 62]

[0215]

[0216] [Chemical Formula 63]

[0217]

[0218] In the following examples, R is, for example, an alkyl group.

[0219] [Chemical Formula 64]

[0220]

[0221] [Chemical Formula 65]

[0222]

[0223] [Chemical Formula 66]

[0224]

[0225] [Chemical Formula 67]

[0226]

[0227] [Chemical Formula 68]

[0228]

[0229] [Chemical Formula 69]

[0230]

[0231] [Chemical Formula 70]

[0232]

[0233] [Chemical Formula 71]

[0234]

[0235] [Chemical Formula 72]

[0236]

[0237] [Chemical Formula 73]

[0238]

[0239] [Chemical Formula 74]

[0240]

[0241] [Chemical Formula 75]

[0242]

[0243] [Chemical Formula 76]

[0244]

[0245] [Chemical Formula 77]

[0246]

[0247] [Chemical Formula 78]

[0248]

[0249] [Chemical Formula 79]

[0250]

[0251] [Chemical Formula 80]

[0252]

[0253] [Chemical Formula 81]

[0254]

[0255] [Chemical Formula 82]

[0256]

[0257] [Chemical Formula 83]

[0258]

[0259] [Chemical Formula 84]

[0260]

[0261] The T below is R 1 This is an example of a ring structure that can be formed.

[0262] [Chemical Formula 85]

[0263]

[0264] [Chemical Formula 86]

[0265]

[0266] [Chemical Formula 87]

[0267]

[0268] The compound represented by formula (1) may be a commercially available product or a synthesized one.

[0269] R 1 When representing a monovalent group as indicated by this formula (2), the compound represented by formula (1) can be synthesized by referring to the method described in

[0034] to

[0036] of International Publication No. 2011 / 102470, for example.

[0270] When making a gas from a compound represented by formula (1), the compound represented by formula (1) itself may be used to make a gas, or a solution in which the compound represented by formula (1) is dissolved in an organic solvent may be used to make a gas.

[0271] The organic solvent used is not particularly limited and examples include esters, ethers, hydrocarbons, etc.

[0272] The compound represented by the gaseous formula (1) is introduced, for example, into a film formation chamber to be provided for a process in which a thin film is formed.

[0273] As a method for introducing a compound represented by the gaseous formula (1) into a membrane chamber, examples include gas transport methods and liquid transport methods.

[0274] The gas transport method is a method of vaporizing the compound represented by formula (1) into a gas (steam) by heating a raw material receiving container containing the compound represented by formula (1) and / or depressurizing the inside of the raw material receiving container, and introducing the gas into a film-forming chamber where a substrate is installed, together with a carrier gas such as argon, nitrogen, or helium used as needed.

[0275] The liquid transport method is a method of transporting a compound represented by formula (1) in a liquid or solution state to a vaporization chamber, vaporizing the compound represented by formula (1) into a gas (vapor) by heating the vaporization chamber and / or depressurizing the inside of the vaporization chamber, and introducing the gas into a film-forming chamber.

[0276] <Thin film formation process>

[0277] This process involves contacting a gaseous compound represented by Equation (1) with the surface of a substrate and further chemically reacting the compound represented by Equation (1) to form Si-R in the compound represented by Equation (1). 1 It is a process in which a thin film having a cell is formed on the surface of a substrate.

[0278] This process is preferably performed inside a membrane chamber.

[0279] In a preferred embodiment, this process involves contacting a gaseous compound represented by Equation (1) with the surface of a substrate within a film-forming chamber under reduced pressure, and further chemically reacting the compound represented by Equation (1) to form Si-R in the compound represented by Equation (1). 1 It is a process in which a thin film having a cell is formed on the surface of a substrate.

[0280] In this process, the pressure in the film-forming chamber when the pressure is reduced is not particularly limited, for example, 1 to 10,000 Pa, and in terms of suitably vaporizing the compound represented by Formula (1), it is preferably 5,000 Pa or less, more preferably 3,000 Pa or less, and even more preferably 2,500 Pa or less. The degree of pressure reduction is appropriately set considering the heating temperature.

[0281] The amount of the compound represented by the gaseous formula (1) introduced into the film-forming chamber is not particularly limited and can be determined appropriately by considering the desired film thickness, etc.

[0282] The method of contacting the surface of the substrate with the gaseous compound represented by formula (1) is not particularly limited, and examples include a method of injecting the gaseous compound represented by formula (1) introduced into the film-forming chamber onto the surface of the substrate from a direction having a predetermined angle with respect to the surface of the substrate (e.g., a vertical direction).

[0283] When a gaseous compound represented by formula (1) is brought into contact with the surface of a substrate, it is preferable that the atmosphere within the substrate and / or the film deposition chamber be heated to promote the formation of a thin film. The heating temperature of the atmosphere within the substrate and / or the film deposition chamber is typically 25 to 200°C, and is preferably 50°C or higher, more preferably 70°C or higher, even more preferably 90°C or higher, and even more preferably 110°C or higher in order to suitably vaporize the compound represented by formula (1). The heating temperature is appropriately set by considering whether to reduce the pressure and, if to reduce the pressure, the degree of reduction.

[0284] Inside the film deposition chamber, the substrate is placed, for example, on a support. Heating of the substrate may be performed, for example, by heating the film deposition chamber or by heating the support.

[0285] The size, material, and structure of the film deposition chamber are not particularly limited and may be determined appropriately by considering the size of the substrate used, heating temperature, etc.

[0286] <<Circuit Board>>

[0287] As a substrate, Si-R on its surface 1 It is not particularly limited to any target that forms a thin film having a group.

[0288] The surface of the substrate may be flat or have a three-dimensional structure such as a trench structure.

[0289] The substrate may have a single-layer structure or a multi-layer structure.

[0290] The substrate may be, for example, a single-layer substrate of a silicon wafer, or a multi-layer substrate formed by forming an organic film or an inorganic film in a single layer or multiple layers on a silicon wafer.

[0291] Examples of substrates include silicon wafer substrates, silicon / silicon dioxide coated substrates, silicon nitride substrates, glass substrates, ITO substrates, polyimide substrates, and substrates coated with low-dielectric constant materials (low-k materials). Additionally, organic or inorganic films formed as a single layer or multiple layers on these substrates may be used as substrates. An example of these organic or inorganic films is an anti-reflective film.

[0292] It is preferable that the substrate placed inside the membrane chamber be surface-treated in advance.

[0293] Surface treatments include cleaning with organic solvents, treatment with UV ozone, etc.

[0294] In this process, a compound represented by formula (1) is chemically reacted.

[0295] An example of this chemical reaction is a substrate and R 3 It is a chemical reaction. This chemical reaction occurs, for example, between the hydroxyl groups on the substrate surface and Si-R 3 It is a condensation reaction of gases. R 3 In the case where this is an alkoxy or acyloxy group, in this chemical reaction, for example, between the hydroxyl group on the substrate surface and Si-R 3 The case where the group undergoes a direct condensation reaction, and Si-R 3 Two types of chemical reactions can occur when the hydroxyl group on the substrate surface undergoes a condensation reaction with the Si-OH group after the group is converted to a Si-OH group.

[0296] Another example of this chemical reaction is between the respective R of the two compounds represented by Equation (1). 3 This is the formation of siloxane bonds involved.

[0297] By chemically reacting a gaseous compound represented by formula (1) on the surface of the substrate, Si-R on the surface of the substrate 1 A thin film having a cell is formed.

[0298] Si-R 1The thickness of the thin film having the group is not particularly limited, for example, 0.1 to 10 nm, 0.5 to 8 nm is preferred, and 0.7 to 5 nm is more preferred.

[0299] The thickness of the thin film can be measured by, for example, the optical film thickness gauge NanoSpec / AFT5100 (manufactured by Nanometrics), the ellipsometric film thickness gauge ASET-F5 (manufactured by KLA), the ellipsometric film thickness gauge RE3100 / 3500 (manufactured by SCREEN Semiconductor Solutions Co., Ltd.), the ellipsometric film thickness measuring device VUV-VASE (manufactured by JA Woollam), etc.

[0300] <Process of removing the substrate>

[0301] This process is Si-R 1 It is a process in which a substrate having a thin film formed on its surface is removed from the film formation chamber.

[0302] In the process shown in FIG. 3 of Japanese Patent Publication No. 2014-129606, as described in paragraph

[0043] , a surface having a hydroxyl group is exposed to 3-[(1,3-dimethylbutylidene)amino]propyltriethoxysilane (PS). This PS is bonded to the surface by siloxane bonds. The protecting group hides the -NH2 functional group until it is removed. When the PS surface is exposed to water, the protecting group is removed. The water reacts with the imine portion to release 4-methyl-2-pentanone. As a result of this reaction, a primary amine remains on the surface.

[0303] Japanese Patent Publication No. 2014-129606 does not specify that the related processes are performed within a film deposition chamber, but typically these processes are performed as a series of processes within a film deposition chamber.

[0304] Meanwhile, in one embodiment of the method for manufacturing a substrate having a thin film according to the present invention, Si-R in a film deposition chamber1 When a thin film having a group is formed, no additional treatment is performed on the said thin film inside the deposition chamber, and Si-R 1 A substrate having a thin film formed on its surface is removed from the film formation chamber.

[0305] The method of removing the substrate from the film deposition chamber is not particularly limited and may be determined appropriately.

[0306] The applications of the fabricated thin film are not particularly limited and may be determined appropriately; for example, it can be used as a resist underlayer, an anti-reflective film, a photo-electron beam responsive resist film, a self-organizing film, etc.

[0307] Here, an example of a substrate having a thin film is described using drawings.

[0308] Figure 1 is a schematic cross-sectional view of an example of a substrate having a thin film.

[0309] The substrate having the thin film of FIG. 1 has a substrate (1) and a thin film (2). The substrate (1) is a single-layer substrate made of a silicon wafer (1a). The thin film (2) is formed on the surface of the silicon wafer (1a).

[0310] Another example of a substrate having a thin film is explained using drawings.

[0311] Figure 2 is a schematic cross-sectional view of another example of a substrate having a thin film.

[0312] The substrate having the thin film of FIG. 2 has a substrate (1) and a thin film (2). The substrate (1) is a multilayer substrate consisting of a silicon wafer (1a) and an organic lower layer (1b). The thin film (2) is formed on the surface of the organic lower layer (1b).

[0313] Next, an example of a method for manufacturing a substrate having a thin film is described using a device for manufacturing a substrate having a thin film.

[0314] First, an example of a manufacturing apparatus will be described. Figure 3 is a schematic cross-sectional view of an example of a manufacturing apparatus for a substrate having a thin film.

[0315] The manufacturing device has a raw material receiving container (11), a film forming chamber (12), a heater (13), piping (14a and 14b), a discharge port (15), a support (16), a trap (17), and a vacuum pump (18).

[0316] The raw material receiving container (11), the membrane chamber (12), and the piping (14a) are covered by a heater (13).

[0317] In the internal space of the membrane chamber (12), a support (16) that supports the substrate (1) is arranged.

[0318] The internal space of the membrane chamber (12) is depressurized by a vacuum pump (18).

[0319] In order to prevent the vaporized gas discharged from the film chamber (12) by the vacuum pump (18) from reaching the vacuum pump (18), a trap (17) for capturing the vaporized gas is placed in the middle of the piping (14b) between the film chamber (12) and the vacuum pump (18).

[0320] Below, an example of a method for manufacturing a substrate having a thin film using the said manufacturing apparatus is described.

[0321] First, the compound represented by formula (1) is placed in a raw material receiving container (11). When placed in the raw material receiving container (11), the compound represented by formula (1) may be a liquid or a solid at room temperature and pressure.

[0322] Next, the raw material receiving container (11) is heated by the heater (13) until it reaches a predetermined temperature, and at the same time, the pressure inside the raw material receiving container (11) is lowered, thereby turning the compound represented by Equation (1) inside the raw material receiving container (11) into a gas (2a).

[0323] Next, the obtained gas (2a) is introduced into the membrane chamber (12) through the piping (14a).

[0324] A substrate (1) is placed on a support (16) inside the film-forming chamber (12). The film-forming chamber (12) is heated to a predetermined temperature by a heater (13), and at the same time, the internal space of the film-forming chamber (12) is depressurized to a predetermined pressure by a vacuum pump (18).

[0325] The gas (2a) introduced into the film-forming chamber (12) is expelled from the discharge port (15) onto the surface of the substrate (1). Meanwhile, the pressure in the internal space of the film-forming chamber (12) is controlled by the vacuum pump (18).

[0326] By bringing the gas (2a) into contact with the surface of the substrate (1) and also chemically reacting the gas (2a) with the compound represented by formula (1), Si-R on the surface of the substrate (1). 1 A thin film having a cell is formed.

[0327] (Method for manufacturing a semiconductor substrate)

[0328] The method for manufacturing a semiconductor substrate according to the present invention comprises at least a process for manufacturing a substrate having a thin film and a process for forming a resist film, and additionally, as necessary, a process for forming a resist pattern, a process for processing a thin film, a process for processing a substrate, etc.

[0329] Process for manufacturing a substrate having a thin film

[0330] This process utilizes the method for manufacturing a substrate having the aforementioned thin film of the present invention, Si-R 1 This is a process for manufacturing a substrate having a thin film having a cell.

[0331] <Process of forming a resist film>

[0332] This process is Si-R 1 It is a process in which a resist film is formed on top of a thin film having a group.

[0333] The formation of the resist film is by a well-known method, namely Si-R 1 This can be done by applying a resist material to the upper surface of a thin film having a cell and firing it.

[0334] The thickness of the resist film is not particularly limited, for example, 50 to 10,000 nm, 100 to 2,000 nm is preferred, 200 to 1,000 nm is more preferred, and 30 to 200 nm is even more preferred.

[0335] Examples of resist materials used for forming a resist film include photoresist materials and electron beam resist materials.

[0336] As for the photoresist material, it is not particularly limited as long as it is sensitive to light used for exposure during resist pattern formation, and for example, it is a positive type photoresist material.

[0338] Examples of positive type photoresist materials include those of (i) to (iv) below.

[0339] (i) A chemically amplified photoresist material containing a photo-generating agent and a binder having a group that decomposes by acid to increase the alkali dissolution rate of the resist film.

[0340] (ii) Chemically amplified photoresist material containing a low molecular weight compound that decomposes by acid to increase the alkali dissolution rate of the resist film, an alkali-soluble binder, and a photogenerator

[0341] (iii) A chemically amplified photoresist material containing a binder having a group that decomposes by acid to increase the alkali dissolution rate of the resist film, a low molecular weight compound that decomposes by acid to increase the alkali dissolution rate of the resist film, and a photogenerator.

[0342] (iv) DNQ (diazonaphthoquinone)-novolak type non-chemically amplified photoresist material utilizing the difference in alkali dissolution rates between the exposed and unexposed zones

[0343] Examples of commercially available positive-type photoresists include PAR710 (manufactured by SUMITOMO CHEMICAL COMPANY, LIMITED), TDUR-P3435LP (manufactured by TOKYO OHKA KOGYO CO., LTD.), THMR-iP1800 (manufactured by TOKYO OHKA KOGYO CO., LTD.), and SEPR430 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0344] As a photoresist material, a negative-type photoresist material may also be used.

[0345] Examples of negative-type photoresist materials include those of (v) to (viii) below.

[0346] (v) A chemically amplified photoresist material containing a photo-generating agent and a binder having a group that decomposes by acid to reduce the solvent dissolution rate of the resist film.

[0347] (vi) A chemically amplified photoresist material containing a binder and a photo-generating agent that detach upon acid and subsequently react and polymerize to reduce the alkali dissolution and solvent dissolution rates of the resist film.

[0348] (vii) A non-chemically amplified photoresist material containing a binder that detaches upon acid and subsequently reacts and polymerizes to reduce the alkali dissolution and solvent dissolution rates of the resist film.

[0349] (viii) A non-chemically amplified photoresist material containing a metal compound that detaches upon light and subsequently reacts and polymerizes to reduce the alkali dissolution and solvent dissolution rates of the resist film.

[0350] As electron beam resists, examples include the following (ix) to (x).

[0351] (ix) An electron beam resist material comprising a resin containing Si-Si bonds in the main chain and aromatic rings at the ends, and an acid-generating agent that generates acid upon irradiation with an electron beam.

[0352] (x) An electron beam resist material containing poly(p-hydroxystyrene) in which hydroxyl groups are substituted with organic groups including N-carboxyamines, and an acid-generating agent that generates acid upon electron beam irradiation.

[0353] In the latter electron beam resist material, the acid generated from the acid generator by electron beam irradiation reacts with the N-carboxyamino group of the polymer side chain, and the polymer side chain decomposes into hydroxyl groups to exhibit alkali solubility, dissolving in the alkaline developer to form a resist pattern.

[0354] Examples of acid-generating agents that generate acid upon irradiation with this electron beam include, for instance, halogenated organic compounds such as 1,1-bis[p-chlorophenyl]-2,2,2-trichloroethane, 1,1-bis[p-methoxyphenyl]-2,2,2-trichloroethane, 1,1-bis[p-chlorophenyl]-2,2-dichloroethane, and 2-chloro-6-(trichloromethyl)pyridine; onium salts such as triphenylsulfonium salts and diphenyliodonium salts; and sulfonic acid esters such as nitrobenzyl tosylate and dinitrobenzyl tosylate.

[0355] <Process of forming a resist pattern>

[0356] This process forms a resist pattern by exposing and developing a resist film.

[0357] Exposure is performed, for example, through a mask (reticle) to form a predetermined pattern, and, for example, i-ray, KrF excimer laser, ArF excimer laser, EUV (extreme ultraviolet), or EB (electron beam) is used.

[0358] For the development, for example, an alkaline developer is used.

[0359] The development is performed, for example, at a development temperature of 5 to 50°C and a development time of 10 to 300 seconds.

[0360] Examples of alkaline developers include aqueous solutions of alkali metal hydroxides such as potassium hydroxide and sodium hydroxide; aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. In addition, surfactants may be added to these developers. Alternatively, instead of an alkaline developer, a method may be used to develop parts of the photoresist film where the alkali dissolution rate is not improved by performing development with an organic solvent such as butyl acetate.

[0361] Thin film processing process

[0362] This process utilizes a resist pattern as a mask to process a thin film, thereby forming a patterned thin film.

[0363] In this process, for example, a resist pattern is used as a mask (protective film) to etch the thin film. The etching is performed, for example, by dry etching. As the thin film is patterned by etching, the surface of the substrate is exposed between the patterned thin films.

[0364] Gases used for dry etching include, for example, tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane, dichloroborane, etc.

[0365] As a gas used for dry etching, Si-R 1Halogen-based gases are preferred in that the removal of the thin film containing the group is performed quickly and the reduction in the thickness of the resist film during etching is suppressed. As halogen-based gases, fluorine-based gases are preferred. Examples of fluorine-based gases include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

[0366] <Process of substrate processing>

[0367] This process involves processing a substrate using a resist pattern and a patterned thin film as a mask.

[0368] In this process, the substrate is etched using, for example, a resist pattern and a patterned thin film as a mask (protective film). Etching is performed, for example, by dry etching. The substrate is processed by etching.

[0369] The methods of processing the substrate are not particularly limited and may include, for example, the formation of grooves or through holes.

[0370] As for the gas used for dry etching, it is acceptable to determine it appropriately depending on the surface of the substrate in contact with the thin film.

[0371] For example, when a substrate has an organic film and a thin film is in contact with the organic film, oxygen gas is preferred as the gas used for etching.

[0372] For example, when the substrate is a silicon wafer and the thin film is in contact with the surface of the silicon wafer, a fluorine-based gas is preferred as the gas used for etching.

[0373] (Substrate having a thin film)

[0374] The substrate having a thin film according to the present invention has at least a thin film and a substrate.

[0375] The thin film is Si-R in the compound represented by Equation (1). 1 Possess energy.

[0376] A thin film is formed, for example, by contacting a compound represented by formula (1) with the surface of a substrate and further chemically reacting the compound represented by formula (1), and Si-R in the compound represented by formula (1). 1 Possess energy.

[0377] A thin film is placed on the surface of the substrate.

[0378] A substrate having a thin film is placed, for example, outside the film formation chamber.

[0379] A substrate having a thin film is formed, for example, by contacting a compound represented by formula (1) to the surface of a substrate and further chemically reacting a compound represented by formula (1).

[0380] Details and examples of the thin film and substrate may be those described in the method for manufacturing a substrate having a thin film according to the present invention.

[0381] A substrate having a thin film can be suitably manufactured by the method for manufacturing a substrate having a thin film according to the present invention.

[0382] (Semiconductor substrate)

[0383] The semiconductor substrate of the present invention has at least a substrate having a thin film of the present invention and a resist film.

[0384] The resist film is positioned above the thin film.

[0385] Details and examples of the resist film may be those described in the method for manufacturing a semiconductor substrate of the present invention.

[0386] A semiconductor substrate can be suitably manufactured by the method for manufacturing a semiconductor substrate of the present invention.

[0387] (compound)

[0388] The compound of the present invention is a compound represented by the aforementioned formula (1).

[0389] The compound of the present invention is used in a method for manufacturing a substrate having the aforementioned thin film or in a method for manufacturing a semiconductor substrate. Additionally, the compound of the present invention is used in the manufacturing of a substrate having the aforementioned thin film or in the manufacturing of a semiconductor substrate.

[0390] Examples

[0391] The present invention will be explained more specifically below with reference to examples, but the present invention is not limited to the following examples.

[0392] (Example 1)

[0393] <Fabrication of a substrate having a thin film>

[0394] The compounds shown below were used as raw materials for forming thin films.

[0395] [Chemical Formula 88]

[0396]

[0397] In the formula, "Et" represents an ethyl group.

[0398] For the manufacture of a substrate having a thin film, the manufacturing apparatus shown in Fig. 3 was used.

[0399] The raw material for forming a thin film was placed in the raw material receiving container (11).

[0400] A silicon wafer (substrate (1)) surface-treated with UV ozone was placed on a support (16) inside a membrane chamber (12).

[0401] At the same time, the pressure inside the membrane chamber (12) was set to 20 mbar (2,000 Pa), and the membrane chamber (12) was heated to 140°C using a heater (13).

[0402] At the same time, the temperature of the raw material receiving container (11) is raised to 140°C using a heater (13), and the pressure inside the raw material receiving container (11) is reduced to 20 mbar (2,000 Pa), thereby making the raw material for forming a thin film inside the raw material receiving container (11) into a gas (2a).

[0403] The raw material for forming a thin film, which has become gas (2a) in the raw material receiving container (11), is introduced into the film forming chamber (12) through the pipe (14a), and the raw material for forming a thin film, which is gas (2a), is brought into contact with the surface of the silicon wafer (substrate (1)). This operation is performed for 1 hour to form a thin film having diallyl isocyanurate propylsilyl groups on the silicon wafer (substrate (1)).

[0404] A silicon wafer (substrate (1)) having a thin film was removed from the film formation chamber (12).

[0405] The thickness of the obtained thin film was measured using an ellipsometric film thickness gauge, the ASET-F5 film thickness gauge (KLA product, hereinafter the same). The result was 2.0 nm.

[0406] In addition, the water contact angle was measured using the fully automatic contact angle meter DM-701 (Kyowa Interface Science Co., Ltd). While the water contact angle of the silicon wafer surface-treated with UV ozone was 20° or less, the water contact angle of the thin film formed on the silicon wafer was 71°. This increase in contact indicates that the hydrophobicity was increased due to the formation of a thin film having diallyl isocyanurate propylsilyl groups.

[0407] Solvent Resistance Test

[0408] A mixed solvent (7 / 3 (vol / vol) of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate) was applied to a thin film of a silicon wafer having a thin film obtained by the same method as described above, and spin-dried at 1,500 rpm / 30 seconds.

[0409] The thickness of the thin film after spin drying was measured using an ellipsometric film thickness gauge, and the presence or absence of a decrease in film thickness before and after the application of the mixed solvent was evaluated. Based on the film thickness before the application of the mixed solvent, a decrease in film thickness of less than 5% after application was evaluated as "good," and a decrease in film thickness of 5% or more was evaluated as "poor."

[0410] The obtained results are shown in Table 1.

[0411]

[0412] From this result, it was confirmed that a thin film with solvent resistance was formed.

[0413] <EUV 노광에 의한 레지스트 패턴의 형성: 포지티브형 알칼리 현상>

[0414] <<Example 1>>

[0415] On a thin film of a silicon wafer having a thin film obtained by the same method as described above, an EUV resist solution (methacrylate-polyhydroxystyrene resin-based resist) was spin-coated, and an EUV resist film (layer C) was formed by heating at 110°C for 1 minute, and then exposed under conditions of NA=0.33, σ=0.63 / 0.84, and Quadropole using an ASML product EUV exposure device (NXE3400).

[0416] After exposure, post-exposure heating (PEB, 105°C for 1 minute) was performed, the material was cooled to room temperature on a cooling plate, developed for 30 seconds using TMAH 2.38% developer, and rinsed to form a resist pattern.

[0417] <<Comparative Example 1>>

[0418] In addition, as Comparative Example 1, an EUV resist was formed as described above on a silicon wafer that had not undergone any treatment, and the same exposure and development were performed.

[0419] And for each obtained pattern, whether a line pattern of 28 nm pitch and 12 nm was formed was evaluated by confirming the pattern shape through observation of the pattern cross-section.

[0420] In observing the pattern shape, a condition in which the shape is between the footing and the undercut and there is no significant residue in the spaced area was evaluated as "good," and an undesirable condition in which the resist pattern collapses was evaluated as "collapsed." The results obtained are shown in Table 2.

[0421]

[0422] From the above, it was confirmed that a thin film capable of effectively resolving EUV resist was formed.

[0423] Industrial applicability

[0424] According to the present invention, since it is possible to form a novel thin film on a substrate, the present invention is useful for manufacturing a substrate having a novel thin film and for manufacturing a semiconductor substrate having a novel thin film. Explanation of the symbols

[0425] 1: Substrate 1a: Silicon wafer 1b: Organic lower layer 2: Thin film 2a: Gas 11: Raw material receiving container 12: Tabernacle Chamber 13: Heater 14a, 14b: Piping 15: Discharge port 16: Support 17: Trap 18: Vacuum Pump

Claims

Claim 1 As a semiconductor substrate, Si-R in a compound represented by the following formula (1) 1 A thin film having a group, and the above Si-R on its surface 1 A semiconductor substrate having a substrate on which the above-mentioned thin film having a group is disposed, and a resist pattern formed above the thin film. [Chemical Formula 1] (Among the above formula (1), R 1 represents a monovalent organic group bonded to Si, and R 2 represents a monovalent organic group bonded to Si, and R 3 represents an alkoxy group, acyloxy group, or halogen atom bonded to Si, n represents an integer from 0 to 2, and when n is 2, R 2 may be the same or different, and if n is 0 or 1, R 3 may be the same or different. When n is 1, R 1 and R 2 They may also form a ring structure together.) Claim 2 A semiconductor substrate according to claim 1, wherein the thin film is formed by contacting a compound represented by formula (1) with the surface of the substrate and further chemically reacting the compound. Claim 3 In paragraph 1 or 2, R 1 A semiconductor substrate in which the monovalent organic group is a monovalent organic group having 1 to 20 carbon atoms having an oxygen atom. Claim 4 In paragraph 1 or 2, R 1 A semiconductor substrate in which the above monovalent organic group is an organic group having heteroatoms and is bonded to silicon atoms by Si-C bonding. Claim 5 In any one of paragraphs 1 to 4, in the above formula (1), R 1 represents a monovalent group expressed by the following formula (2), and R 2 A semiconductor substrate that represents a monovalent group represented by the above formula (2), or an organic group having an alkyl group, an aryl group, an aralkyl group, an alkyl halide group, an aryl halide group, an aralkyl halide group, an alkenyl group, an epoxy group, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, or an organic group having a cyano group, or a combination of two or more of these. [Chemical Formula 2] (Among the above formula (2), R 4 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an epoxy group, a sulfonyl group, or a monovalent organic group comprising two or more of these, and R 5 represents an alkylene group, a hydroxyalkylene group, a sulfide bond, an ether bond, an ester bond, or a combination of two or more of these having 1 to 10 carbon atoms, and X 1 ...represents a divalent group represented by the following formula (3), a divalent group represented by the formula (4), or a divalent group represented by the formula (5). [Chemical Formula 3] (Among the above equations (3), (4) and (5), R 6 ~R 10 Each represents independently a hydrogen atom, or a monovalent organic group comprising an alkyl group, alkenyl group, epoxy group, sulfonyl group having 1 to 10 carbon atoms, or two or more of these. *1 and *3 are bonded to the carbon atom of the carbonyl group in Formula (2). *2 and *4 are bonded to the nitrogen atom in Formula (2).) Claim 6 By contacting the surface of a substrate with a gaseous compound represented by formula (1) and further chemically reacting the compound, the Si-R in the compound 1 A method for manufacturing a semiconductor substrate, comprising: a process of forming a thin film having a group on the surface of the substrate; a process of forming a resist film on top of the thin film; and a process of forming a resist pattern by exposing and developing the resist film. [Chemical Formula 4] (Among the above formula (1), R 1 represents a monovalent organic group bonded to Si, and R 2 represents a monovalent organic group bonded to Si, and R 3 represents an alkoxy group, acyloxy group, or halogen atom bonded to Si, n represents an integer from 0 to 2, and when n is 2, R 2 may be the same or different, and if n is 0 or 1, R 3 may be the same or different. When n is 1, R 1 and R 2 They may also form a ring structure together.) Claim 7 In claim 6, the process of forming the thin film on the surface of the substrate is performed in a film deposition chamber, and additionally, the Si-R 1 A method for manufacturing a semiconductor substrate, comprising a process in which the substrate having the above-mentioned thin film formed on its surface is removed from the above-mentioned film formation chamber. Claim 8 In paragraph 6 or 7, R 1 A method for manufacturing a semiconductor substrate, wherein the monovalent organic group in the above is a monovalent organic group having 1 to 20 carbon atoms having an oxygen atom. Claim 9 In paragraph 6 or 7, R 1 A method for manufacturing a semiconductor substrate in which the above-mentioned monovalent organic group is an organic group having heteroatoms and is bonded to silicon atoms by Si-C bonding. Claim 10 In any one of paragraphs 6 to 9, in the above formula (1), R 1 represents a monovalent group expressed by the following formula (2), and R 2 A method for manufacturing a semiconductor substrate, wherein the group is a monovalent group represented by the above formula (2), or an organic group having an alkyl group, an aryl group, an aralkyl group, an alkyl halide group, an aryl halide group, an aralkyl halide group, an alkenyl group, an epoxy group, an organic group having an acryloyl group, an organic group having a methacryloyl group, an organic group having a mercapto group, an organic group having an amino group, or an organic group having a cyano group, or a combination of two or more of these. [Chemical Formula 5] (Among the above formula (2), R 4 represents a hydrogen atom, or an alkyl group having 1 to 10 carbon atoms, an alkenyl group, an epoxy group, a sulfonyl group, or a monovalent organic group comprising two or more of these, and R 5 represents an alkylene group, a hydroxyalkylene group, a sulfide bond, an ether bond, an ester bond, or a combination of two or more of these having 1 to 10 carbon atoms, and X 1 ...represents a divalent group represented by the following formula (3), a divalent group represented by the formula (4), or a divalent group represented by the formula (5). [Chemical Formula 6] (Among the above equations (3), (4) and (5), R 6 ~R 10 Each represents independently a hydrogen atom, or a monovalent organic group comprising an alkyl group, alkenyl group, epoxy group, sulfonyl group having 1 to 10 carbon atoms, or two or more of these. *1 and *3 are bonded to the carbon atom of the carbonyl group in Formula (2). *2 and *4 are bonded to the nitrogen atom in Formula (2).) Claim 11 A method for manufacturing a semiconductor substrate, comprising, in any one of claims 6 to 10, a process in which the compound represented by the formula (1) becomes a gas. Claim 12 A compound represented by the formula (1) used in any one of the manufacturing of a semiconductor substrate described in any one of claims 1 to 5, and any one of the manufacturing methods of a semiconductor substrate described in any one of claims 6 to 11.

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