Substrates having thin films, and semiconductor substrates

Abstract

Provided are a substrate having a novel thin film formed thereon, 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 therefor. 【Solution means】A substrate 1 having a thin film 2, comprising the thin film having a Si-R group in the compound represented by the following formula (1), and the substrate having the thin film disposed on its surface. 1 The thin film having a Si-R group in the compound represented by the following formula (1), and the substrate having the thin film disposed on its surface. TIFF2026108734000098.tif11134 In formula (1), R 1 represents a monovalent organic group bonded to Si, R 2 represents a monovalent organic group bonded to Si, R 3 represents an alkoxy group, an acyloxy group, or a 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 when n is 0 or 1, R 3 may be the same or different. When n is 1, R 1 and R 2 may together form a ring structure.

Description

Technical 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 therefor.

Background Art

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

[0003] In recent years, as a technique of CVD, Atomic Layer Deposition (ALD), Molecular Layer Deposition, etc. have been proposed. Using these techniques, formation of gallium nitride thin films (for example, Patent Document 1) and formation of organic polymers (for example, Patent Document 2) have been proposed.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] The present invention aims to provide a substrate with a novel thin film formed thereon, a semiconductor substrate, a method for manufacturing a substrate with a thin film capable of forming a novel thin film on the substrate, a method for manufacturing a semiconductor substrate, and further a compound used therein.

Means for Solving the Problems

[0006] As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved and have completed the present invention having the following gist.

[0007] That is, the present invention includes the following. [1] A substrate having a thin film, the thin film having a Si-R 1 group in the compound represented by the following formula (1), and on its surface, the substrate on which the thin film having the Si-R 1 group is disposed, and having, a substrate having a thin film.

Chemical Formula

[10] A method for manufacturing a substrate having a thin film according to any one of [6] to [9], comprising the step of turning the compound represented by formula (1) into a gas. A step of manufacturing the substrate having the thin film using a method for manufacturing the substrate having the thin film described in any of

[11] [6] to

[10] , A step of forming a resist film on top of the thin film, A method for manufacturing a semiconductor substrate, including the method described above.

[12] Manufacturing of a substrate having a thin film as described in any of [1] to [4], [5] Manufacturing of semiconductor substrates as described above, A method for manufacturing a substrate having a thin film as described in any of [6] to

[10] , and

[11] Method for manufacturing a semiconductor substrate as described above A compound represented by formula (1) above, used in any of the following. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a substrate having a thin film in which a novel thin film is formed on the substrate, and a semiconductor substrate, as well as a method for manufacturing a substrate having a thin film that can form a novel thin film on the substrate, a method for manufacturing a semiconductor substrate, and compounds used in the same. [Brief explanation of the drawing]

[0009] [Figure 1] This is a schematic cross-sectional view of an example of a substrate having a thin film. [Figure 2] This is a schematic cross-sectional view of another example of a substrate having a thin film. [Figure 3] This is a schematic cross-sectional view of an example of a manufacturing apparatus for substrates having thin films. [Modes for carrying out the invention]

[0010] (Method for manufacturing a substrate having a thin film) The present invention relates to a method for manufacturing a substrate having a thin film, wherein the Si-R compound represented by the following formula (1) 1 This is a method for manufacturing a substrate having a thin film containing a group. A method for manufacturing a substrate having a thin film includes at least a step of forming a thin film, and optionally a step of turning a compound into a gas and a step of removing the substrate.

[0011] <Process of turning a compound into a gas> This process involves converting the compound represented by the following formula (1) into a gas. The method for converting the compound into a gas is not particularly limited and includes, for example, heating a raw material container containing the compound represented by formula (1), reducing the pressure inside the raw material container containing the compound represented by formula (1), or a combination of these methods to convert the compound represented by formula (1) into a gas (vapor). The compound represented by formula (1) may be converted to a gas within the raw material container as described above, or it may be done using a vaporization chamber instead of the raw material container. The size, material, and structure of the raw material container and vaporization chamber are not particularly limited and may be determined appropriately considering the heating temperature and degree of reduced pressure. The heating temperature is not particularly limited, for example, between 25 and 200°C. The pressure inside the raw material container and the pressure inside the vaporization chamber when the compound represented by formula (1) is converted into a gas is not particularly limited, and is, for example, 1 to 10,000 Pa. The compound represented by formula (1) may be a liquid or a solid at room temperature and pressure.

[0012] <<Formula (1)>> [ka] (In formula (1), R 1 R represents a monovalent organic group bonded to Si, 2 R represents a monovalent organic group bonded to Si, 3 represents an alkoxy group, acyloxy group, or halogen atom bonded to Si, and n represents an integer from 0 to 2. When n is 2, R 2 They may be the same or different, and if n is 0 or 1, R 3 They may be the same or they may be different. When n is 1, R 1 and R 2 They may also form a ring structure together.

[0013] R 1 , and R 2 In this context, a monovalent organic group is, for example, an organic group having 1 to 20 carbon atoms. R 1 , and R2 The monovalent organic group in this compound may have heteroatoms other than carbon and hydrogen atoms. Examples of heteroatoms include nitrogen, oxygen, sulfur, and phosphorus atoms. R 1 , and R 2 The monovalent organic group in this example may be bonded to a silicon atom by a Si-C bond.

[0014] R 1 and R 2 The monovalent organic group in this may be, 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.

[0015] R 1 and R 2 For example, each of these groups independently does not have a protected functional group. An example of a protected functional group is a protected amino group.

[0016] The compound represented by formula (1) is, for example, the hydrolyzable organosilane represented by formula (1) in International Publication No. 2011 / 102470.

[0017] R 1 This represents, for example, a monovalent group represented by the following formula (2). [ka] (In formula (2), R 4 R represents a hydrogen atom, or a monovalent organic group containing an alkyl group, alkenyl group, epoxy group, sulfonyl group, or two or more thereof, with 1 to 10 carbon atoms. 5 X represents an alkylene group having 1 to 10 carbon atoms, a hydroxyalkylene group, a sulfide bond, an ether bond, an ester bond, or a combination of two or more of these. 1 This represents a divalent group represented by formula (3), a divalent group represented by formula (4), or a divalent group represented by formula (5). [ka] (In equations (3), (4), and (5), R 6 ~R 10 Each of these independently represents a hydrogen atom, or a monovalent organic group containing an alkyl group, alkenyl group, epoxy group, sulfonyl group, or two or more of these groups having 1 to 10 carbon atoms. *1 and *3 are bonded to the carbon atoms of the carbonyl group in formula (2). *2 and *4 are bonded to the nitrogen atoms in formula (2).

[0018] Preferably, R 2 For example, represents a monovalent group represented by formula (2). Or, R 2 These include, for example, an alkyl group, an aryl group, an aralkyl group, a halogenated alkyl group, a halogenated aryl group, a halogenated aralkyl group, an alkenyl group, an epoxy group, an acryloyl group, an methacryloyl group, an organic group having a mercapto group, an amino group, or an organic group having a cyano group, or a combination of two or more of these.

[0019] Alkyl alkyl groups are, for example, alkyl groups with 1 to 10 carbon atoms. The alkyl group may have a linear structure or a branched structure. Examples of linear or branched alkyl groups having 1 to 10 carbon atoms include 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, Examples include 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, 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, and 1-ethyl-2-methyl-n-propyl group. Furthermore, alkyl groups having cyclic alkyl groups can also be used. Examples of alkyl groups having 1 to 10 carbon atoms and having cyclic alkyl groups include cyclopropyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, cyclopentyl group, 1-methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2-ethyl-cyclopropyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, and 1,2-dimethyl-cyclobutyl group. Examples include 1,3-dimethylcyclobutyl group, 2,2-dimethylcyclobutyl group, 2,3-dimethylcyclobutyl group, 2,4-dimethylcyclobutyl group, 3,3-dimethylcyclobutyl group, 1-n-propylcyclopropyl group, 2-n-propylcyclopropyl group, 1-i-propylcyclopropyl group, 2-i-propylcyclopropyl group, 1,2,2-trimethylcyclopropyl group, 1,2,3-trimethylcyclopropyl group, 2,2,3-trimethylcyclopropyl group, 1-ethyl-2-methylcyclopropyl group, 2-ethyl-1-methylcyclopropyl group, 2-ethyl-2-methylcyclopropyl group, and 2-ethyl-3-methylcyclopropyl group. Furthermore, alkylene groups having 1 to 10 carbon atoms can be exemplified by alkylene groups derived from the alkyl groups mentioned above.

[0020] Aryl groups are, for example, aryl groups having 6 to 20 carbon atoms. Examples of aryl groups having 6 to 20 carbon atoms include phenyl group, o-methylphenyl group, m-methylphenyl group, p-methylphenyl group, o-chlorophenyl group, m-chlorophenyl group, p-chlorophenyl group, o-fluorophenyl group, p-mercaptophenyl group, o-methoxyphenyl group, p-methoxyphenyl group, p-aminophenyl group, p-cyanophenyl group, α-naphthyl group, β-naphthyl group, o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, and 9-phenanthryl group.

[0021] Alkenyl groups are, for example, alkenyl groups having 2 to 10 carbon atoms. Examples of alkenyl groups having 2 to 10 carbon atoms include 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, and 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, 3-cyclopentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hex Cenyl 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 Tyl-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-2-propenyl group, 1-i- Examples include propyl-1-propenyl group, 1-i-propyl-2-propenyl, 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-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, and 3-cyclohexenyl group.

[0022] An aralkyl group is an alkyl group substituted with an aryl group. For example, an aralkyl group is an alkyl group having 1 to 10 carbon atoms substituted with a phenyl group. Examples of aralkyl groups include benzyl, phenylethyl, phenylpropyl, and phenylbutyl groups.

[0023] Furthermore, examples include organic groups (halogenated alkyl groups, aryl groups, and aralkyl groups) in which the 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 carried out for all hydrogen atoms or for some of the hydrogen atoms.

[0024] A hydroxyalkylene group is an alkylene group in which at least one hydrogen atom is replaced by a hydroxyl group. Examples of hydroxyalkylene groups include those with 1 to 10 carbon atoms. Examples of hydroxyalkylene groups include 1-hydroxyethylene, 2-hydroxyethylene, 1-hydroxypropylene, 2-hydroxypropylene, 3-hydroxypropylene, hydroxybutylene, hydroxypentylene, and hydroxyhexylene.

[0025] Examples of organic groups having an epoxy group include glycidoxymethyl group, glycidoxyethyl group, glycidoxypropyl group, glycidoxybutyl group, and epoxycyclohexyl group. Examples of organic groups having an acryloyl group include acryloyloxymethyl group, acryloyloxyethyl group, and acryloyloxypropyl group. Examples of organic groups having a methacryloyl group include methacryloyloxymethyl group, methacryloyloxyethyl group, and methacryloyloxypropyl group. Examples of organic groups containing a mercapto group include mercaptoethyl group, mercaptobutyl group, mercaptohexyl group, and mercaptooctyl group. Examples of organic groups containing a cyano group include cyanoethyl group and cyanopropyl group. Examples of organic groups containing an amino group include aminomethyl, aminoethyl, and aminopropyl groups. Examples of organic groups having a sulfonyl group include methylsulfonyl group, allylsulfonyl group, and phenylsulfonyl group.

[0026] R in equation (1) 3 The 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 alkoxy groups having 1 to 20 carbon atoms that have a linear, branched, or cyclic alkyl moiety. Examples of linear or branched alkoxy groups include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, 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- Examples include methyl-n-pentyloxy group, 4-methyl-n-pentyloxy group, 1,1-dimethyl-n-butoxy group, 1,2-dimethyl-n-butoxy group, 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, and 1-ethyl-2-methyl-n-propoxy group. Furthermore, examples of alkoxy groups having a cyclic alkyl moiety include cyclopropoxy group, cyclobutoxy group, 1-methyl-cyclopropoxy group, 2-methyl-cyclopropoxy group, 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, 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 Examples include the 1,3-dimethylcyclobutoxy group, 2,2-dimethylcyclobutoxy group, 2,3-dimethylcyclobutoxy group, 2,4-dimethylcyclobutoxy group, 3,3-dimethylcyclobutoxy group, 1-n-propylcyclopropoxy group, 2-n-propylcyclopropoxy group, 1-i-propylcyclopropoxy group, 2-i-propylcyclopropoxy group, 1,2,2-trimethylcyclopropoxy group, 1,2,3-trimethylcyclopropoxy group, 2,2,3-trimethylcyclopropoxy group, 1-ethyl-2-methylcyclopropoxy group, 2-ethyl-1-methylcyclopropoxy group, 2-ethyl-2-methylcyclopropoxy group, and 2-ethyl-3-methylcyclopropoxy group.

[0027] R in equation (1) 3The acyloxy group is, for example, an acyloxy group with 2 to 20 carbon atoms. Examples of acyloxy groups with 2 to 20 carbon atoms include 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, and 2-methyl-n-pentyl carbonyloxy group. Examples include the 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, 1-ethyl-2-methyl-n-propylcarbonyloxy group, phenylcarbonyloxy group, tosylcarbonyloxy group, etc.

[0028] R in equation (1) 3 Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0029] Examples of compounds represented by formula (1) are shown below. [ka] [ka] [ka]

[0030] In the following example, T is R in equation (1). 3 That is the case. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

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[0031] In the following examples, R is, for example, an alkyl group. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0032] The following T is R 1 This is an example of a ring structure that it can have. [ka] [ka] [ka]

[0033] The compound represented by formula (1) may be a commercially available product or a synthesized product. R 1 When represents a monovalent group represented by formula (2), the compound represented by formula (1) can be synthesized by referring to the methods described in sections

[0034] to

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

[0034] When converting the compound represented by formula (1) into a gas, the compound represented by formula (1) itself may be used as the gas, or a solution obtained by dissolving the compound represented by formula (1) in an organic solvent may be used as the gas. The organic solvent used is not particularly limited and examples include esters, ethers, hydrocarbons, etc.

[0035] The gaseous compound represented by formula (1) is introduced, for example, into a film deposition chamber for use in the process of forming a thin film. Methods for introducing a compound represented by the gas formula (1) into a film deposition chamber include, for example, gas transport methods and liquid transport methods. The gas transport method involves heating a raw material container containing the compound represented by formula (1) and / or reducing the pressure inside the raw material container to vaporize the compound represented by formula (1) into a gas (vapor), and introducing this gas, along with a carrier gas such as argon, nitrogen, or helium as needed, into a film deposition chamber where a substrate is installed. The liquid transport method involves transporting the compound represented by formula (1) in liquid or solution form to a vaporization chamber, vaporizing the compound represented by formula (1) into a gas (vapor) by heating the vaporization chamber and / or reducing the pressure inside the vaporization chamber, and then introducing the gas into the film formation chamber.

[0036] <Process for forming a thin film> This process involves bringing a compound represented by formula (1), which is in gaseous form, into contact with the surface of a substrate, and then chemically reacting the compound represented by formula (1) to obtain Si-R in the compound represented by formula (1). 1 This is a process in which a thin film containing a matrix is ​​formed on the surface of a substrate. This process is preferably carried out in a film deposition chamber.

[0037] In a preferred embodiment, this step involves contacting a compound represented by formula (1), which is a gas, with the surface of a substrate in a deposition chamber under reduced pressure, and then chemically reacting the compound represented by formula (1) to form Si-R in the compound represented by formula (1). 1 This is a process in which a thin film containing a matrix is ​​formed on the surface of a substrate.

[0038] The pressure at which the film deposition chamber is reduced in this process is not particularly limited, and is, for example, 1 to 10,000 Pa. From the viewpoint 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 reduced pressure is set appropriately considering the heating temperature.

[0039] The amount of the compound represented by formula (1), which is a gas, to be introduced into the film deposition chamber is not particularly limited and can be determined appropriately considering the desired film thickness, etc.

[0040] The method for bringing the gaseous compound represented by formula (1) into contact with the substrate surface is not particularly limited. For example, the gaseous compound represented by formula (1), introduced into a film deposition chamber, can be blown onto the substrate surface from a direction at a predetermined angle to the substrate surface (for example, perpendicular to it).

[0041] When bringing the gaseous compound represented by formula (1) into contact with the surface of a substrate, it is preferable that the atmosphere inside the substrate and / or the deposition chamber be heated in order to promote the formation of a thin film. The heating temperature of the atmosphere inside the substrate and / or the deposition chamber is usually 25 to 200°C, and from the viewpoint of suitably vaporizing the compound represented by formula (1), it is preferably 50°C or higher, more preferably 70°C or higher, even more preferably 90°C or higher, and still more preferably 110°C or higher. The heating temperature is set appropriately considering whether or not to reduce the pressure and, if so, the degree of reduction. Inside the deposition chamber, the substrate is placed, for example, on a support stand. Heating of the substrate may be performed, for example, by heating the deposition chamber or by heating the support stand.

[0042] The size, material, and structure of the film deposition chamber are not particularly limited and should be determined appropriately considering the size of the substrate used, the heating temperature, etc.

[0043] <<Substrate>> As for the substrate, its surface is Si-R 1The object to which the thin film having the group is formed is not particularly limited. The surface of the substrate may be flat or it may have a three-dimensional structure such as a trench structure. The substrate may have a single-layer structure or a multi-layer structure. The substrate may be, for example, a single-layer silicon wafer, or a multilayer substrate in which an organic film or inorganic film is formed in a single or multilayer configuration on a silicon wafer.

[0044] Examples of substrates include silicon wafer substrates, silicon / silicon dioxide coated substrates, silicon nitride substrates, glass substrates, ITO substrates, polyimide substrates, and low-dielectric material (low-k material) coated substrates. Alternatively, substrates on which an organic or inorganic film is formed in a single or multilayer configuration may be used. An example of such an organic or inorganic film is an anti-reflective coating.

[0045] It is preferable that the substrate placed in the film deposition chamber has been surface-treated beforehand. Surface treatments include cleaning with organic solvents and treatment with UV ozone, etc.

[0046] In this process, the compound represented by formula (1) is subjected to a chemical reaction. An example of this chemical reaction is between a substrate and R 3 This is a chemical reaction between the hydroxyl groups on the surface of the substrate and Si-R. 3 This is a condensation reaction with a group. 3 When the group is an alkoxy or acyloxy group, this chemical reaction involves, for example, the hydroxyl group on the surface of the substrate and the Si-R 3 In cases where the groups directly undergo a condensation reaction, and Si-R 3 Two types of chemical reactions can occur: one in which the group is converted to a Si-OH group, and another in which the Si-OH group reacts with the hydroxyl group on the surface of the substrate in a condensation reaction. Another example of this chemical reaction is when the respective Rs of two compounds represented by formula (1) 3 This involves the formation of siloxane bonds. By chemically reacting the compound represented by the gas formula (1) on the surface of the substrate, Si-R is produced on the surface of the substrate. 1 A thin film having the group is formed.

[0047] Si-R 1 The thickness of the thin film having the group is not particularly limited, for example, 0.1 to 10 nm, preferably 0.5 to 8 nm, and more preferably 0.7 to 5 nm. The thickness of a thin film can be measured using, for example, an optical film thickness gauge such as NanoSpec / AFT5100 (manufactured by Nanometrics), an ellipsoidal film thickness gauge such as ASET-F5 (manufactured by KLA), an ellipsoidal film thickness gauge such as RE3100 / 3500 (manufactured by SCREEN), or an ellipsoidal film thickness gauge such as VUV-VASE (manufactured by JA Woolam).

[0048] <Process of removing the circuit board> This process is Si-R 1 This is the process of removing a substrate, on which a thin film containing a matrix has been formed, from the deposition chamber.

[0049] In the process shown in Figure 3 of Japanese Patent Publication No. 2014-129606, as described in paragraph

[0043] , the surface having hydroxyl groups is exposed to 3-[(1,3-dimethylbutylidene)amino]propyltriethoxysilane (PS). This PS is bonded to the surface by siloxane bonds. The protecting groups conceal the -NH2 functional groups until they are removed. When the PS surface is exposed to water, the protecting groups are removed. The water reacts with the imine moiety to release 4-methyl-2-pentanone. As a result of this reaction, a primary amine remains on the surface. Although Japanese Patent Publication No. 2014-129606 does not explicitly state that these processes are carried out inside a film deposition chamber, these processes are usually carried out as a series of steps inside a film deposition chamber. On the other hand, in one embodiment of the present invention for manufacturing a substrate having a thin film, Si-R 1 Once a thin film containing the group is formed, no further processing is performed on the thin film in the deposition chamber, and Si-R 1A substrate with a thin film containing a matrix formed on its surface is removed from the deposition chamber.

[0050] The method for removing the substrate from the deposition chamber is not particularly limited and can be determined as appropriate.

[0051] The fabricated thin film has no particular limitations on its use and can be determined as appropriate. For example, it can be used as a resist underlayer, anti-reflective film, photo- and electron-beam reactive resist film, self-assembled film, etc.

[0052] Here, an example of a substrate having a thin film will be explained using a diagram. Figure 1 is a schematic cross-sectional view of an example of a substrate having a thin film. The substrate with the thin film shown in Figure 1 comprises a substrate 1 and a thin film 2. 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.

[0053] Another example of a substrate with a thin film will be explained using a diagram. Figure 2 is a schematic cross-sectional view of another example of a substrate having a thin film. The substrate with the thin film shown in Figure 2 comprises a substrate 1 and a thin film 2. Substrate 1 is a multilayer substrate consisting of a silicon wafer 1a and an organic underlayer film 1b. The thin film 2 is formed on the surface of the organic underlayer film 1b.

[0054] Next, an example of a method for manufacturing a substrate with a thin film will be explained using a manufacturing apparatus for a substrate with a thin film. First, let's describe an example of a manufacturing apparatus. Figure 3 is a schematic cross-sectional view of an example of a manufacturing apparatus for substrates having thin films. The manufacturing apparatus includes a raw material container 11, a film formation chamber 12, a heater 13, piping 14a and 14b, a discharge port 15, a support base 16, a trap 17, and a vacuum pump 18. The raw material container 11, the film deposition chamber 12, and the piping 14a are covered by a heater 13. A support base 16 for supporting the substrate 1 is arranged in the internal space of the film deposition chamber 12. The internal space of the film deposition chamber 12 is depressurized by the vacuum pump 18. To prevent the vaporized gas discharged from the film deposition 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 deposition chamber 12 and the vacuum pump 18.

[0055] The following describes an example of a method for manufacturing a substrate having a thin film using the said manufacturing apparatus. First, the compound represented by formula (1) is placed in the raw material container 11. The compound represented by formula (1) placed in the raw material container 11 may be a liquid or a solid at room temperature and atmospheric pressure. Next, the raw material container 11 is heated by the heater 13 until it reaches a predetermined temperature, and the pressure inside the raw material container 11 is reduced, thereby converting the compound represented by formula (1) inside the raw material container 11 into a gas 2a. Next, the obtained gas 2a is introduced into the film deposition chamber 12 via the piping 14a. A substrate 1 is placed on a support base 16 inside the film deposition chamber 12. The film deposition chamber 12 is heated to a predetermined temperature by a heater 13, and the internal space of the film deposition chamber 12 is reduced to a predetermined pressure by a vacuum pump 18. The gas 2a introduced into the deposition chamber 12 is blown onto the surface of the substrate 1 from the discharge port 15. During this time, the pressure inside the deposition chamber 12 is regulated by the vacuum pump 18. By bringing gas 2a into contact with the surface of substrate 1 and chemically reacting the compound represented by formula (1), which is gas 2a, Si-R is formed on the surface of substrate 1. 1 A thin film having the group is formed.

[0056] (Method of manufacturing semiconductor substrates) The present invention provides a method for manufacturing a semiconductor substrate, which includes at least the steps of manufacturing a substrate having a thin film and forming a resist film, and further optionally includes the steps of forming a resist pattern, processing the thin film, processing the substrate, and so on.

[0057] <Process for manufacturing substrates with thin films> This process uses the manufacturing method for the thin film having the aforementioned thin film according to the present invention to perform Si-R 1 This is a process for manufacturing a substrate having a thin film containing a matrix.

[0058] <Process for forming a resist film> This process is Si-R 1 This is a process in which a resist film is formed on top of a thin film having a matrix. The resist film is formed by a well-known method, namely, Si-R 1 This can be done by coating a resist material onto a thin film having a base and then firing it. The thickness of the resist film is not particularly limited, for example, 50 to 10,000 nm, preferably 100 to 2,000 nm, more preferably 200 to 1,000 nm, and even more preferably 30 to 200 nm.

[0059] Examples of resist materials used for forming resist films include photoresist materials and electron beam resist materials.

[0060] The photoresist material is not particularly limited as long as it is sensitive to the light used for exposure during the formation of the resist pattern; for example, a positive-type photoresist material is used. Examples of positive-type photoresist materials include the following (i) to (iv): (i) A chemically amplified photoresist material containing a binder having a group that decomposes with acid to increase the alkali dissolution rate of the resist film, and a photoacid generator. (ii) A chemically amplified photoresist material containing a low molecular weight compound that decomposes with acid to increase the alkali dissolution rate of the resist film, an alkali-soluble binder, and a photoacid generator. (iii) A chemically amplified photoresist material comprising a binder having a group that decomposes with acid to increase the alkali dissolution rate of the resist film, a low molecular weight compound that decomposes with acid to increase the alkali dissolution rate of the resist film, and a photoacid generator. (iv) DNQ (diazonaphthoquinone)-novolac type non-chemically amplified photoresist material utilizing the difference in alkali dissolution rates between exposed and unexposed areas Examples of commercially available positive-type photoresists include PAR710 (manufactured by Sumitomo Chemical Co., Ltd.), 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.).

[0061] Negative-type photoresist materials can also be used as photoresist materials. Examples of negative-type photoresist materials include the following (v) to (viii). (v) A chemically amplified photoresist material containing a binder having a group that decomposes with acid to reduce the solvent dissolution rate of the resist film, and a photoacid generator. (vi) A chemically amplified photoresist material containing a binder that is removed by acid and then reacts and polymerizes to reduce the alkali dissolution and solvent dissolution rates of the resist film, and a photoacid generator. (vii) Non-chemically amplified photoresist material containing a binder that is removed by acid and then reacts and polymerizes to reduce the alkali dissolution and solvent dissolution rates of the resist film. (viii) Non-chemically amplified photoresist material containing a metal compound that is desorbed by light and subsequently reacts and polymerizes to reduce the alkali dissolution and solvent dissolution rates of the resist film.

[0062] Examples of electron beam resists include the following (ix) to (x). (ix) An electron beam resist material containing a resin that has Si-Si bonds in its main chain and aromatic rings at its ends, and an acid generator that generates acid upon irradiation with an electron beam. (x) An electron beam resist material containing poly(p-hydroxystyrene) in which the hydroxyl groups are substituted with organic groups containing N-carboxyamine, and an acid generator that generates acid upon irradiation with an electron beam. In the latter electron beam resist material, the acid generated from the acid generator by electron beam irradiation reacts with the N-carboxyaminooxy groups of the polymer side chains, causing the polymer side chains to decompose into hydroxyl groups, which then become alkali-soluble and dissolve in an alkaline developer, forming a resist pattern. Examples of acid generators that produce acid upon irradiation with electron beams include 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.

[0063] <Process for forming a resist pattern> This process involves exposing and developing a resist film to form a resist pattern.

[0064] Exposure is performed, for example, through a mask (reticle) to form a predetermined pattern, and uses such as i-rays, KrF excimer lasers, ArF excimer lasers, EUV (extreme ultraviolet), or EB (electron beams).

[0065] For developing, for example, an alkaline developer is used. Development is carried out, for example, at a development temperature of 5-50°C and a development time of 10-300 seconds. 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 alkaline aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants may be added to these developers. Alternatively, development can be performed using an organic solvent such as butyl acetate instead of an alkaline developer, and the parts of the photoresist film where the alkali dissolution rate has not improved can be developed.

[0066] <Process of processing thin films> This process involves using a resist pattern as a mask to process a thin film, thereby forming a patterned thin film.

[0067] In this process, for example, a resist pattern is used as a mask (protective film) and the thin film is etched. Etching is performed, for example, by dry etching. The etching patterns the thin film, and the surface of the substrate is exposed between the patterned thin films. Examples of gases used in dry etching include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, carbon monoxide, argon, oxygen, nitrogen, sulfur hexafluoride, difluoromethane, nitrogen trifluoride, chlorine trifluoride, chlorine, trichloroborane, and dichloroborane. The gas used in dry etching is Si-R 1 Halogen-based gases are preferred because they allow for rapid removal of thin films containing the group and suppress the reduction in the thickness of the resist film during etching. Fluorine-based gases are preferred among halogen-based gases. Examples of fluorine-based gases include tetrafluoromethane (CF4), perfluorocyclobutane (C4F8), perfluoropropane (C3F8), trifluoromethane, and difluoromethane (CH2F2).

[0068] <Process of processing the circuit board> This process involves processing the substrate using a resist pattern and a patterned thin film as a mask.

[0069] In this process, for example, the substrate is etched using 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. The method of processing the substrate is not particularly limited, and examples include forming grooves and through holes. The gas used for dry etching should be appropriately determined depending on the surface of the substrate in contact with the thin film. For example, if the substrate has an organic film and the thin film is in contact with the organic film, oxygen gas is preferred as the gas used for etching. For example, if 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.

[0070] (Substrate with a thin film) The substrate having the thin film of the present invention comprises at least the thin film and the substrate. The thin film is Si-R in the compound represented by formula (1). 1 It has a base. The thin film is formed, for example, by contacting the surface of a substrate with a compound represented by formula (1), and then chemically reacting the compound represented by formula (1), and the Si-R in the compound represented by formula (1) 1 It has a base. The substrate has a thin film applied to its surface. The substrate with the thin film is, for example, placed outside the deposition chamber. A substrate having a thin film is formed, for example, by contacting the surface of the substrate with a compound represented by formula (1) and then chemically reacting the compound represented by formula (1).

[0071] Details and examples of the thin film and substrate are given in the details and examples described in the method for manufacturing a substrate having the thin film of the present invention.

[0072] 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.

[0073] (Semiconductor substrate) The semiconductor substrate of the present invention comprises at least a substrate having the thin film of the present invention and a resist film. The resist film is positioned above the thin film. Details and examples of the resist film are given in the details and examples described in the semiconductor substrate manufacturing method of the present invention.

[0074] The semiconductor substrate can be suitably manufactured by the semiconductor substrate manufacturing method of the present invention.

[0075] (compound) The compound of the present invention is the compound represented by formula (1) described above. The compound of the present invention is used in the method for manufacturing a substrate having the thin film described above, or in the method for manufacturing a semiconductor substrate described above. Furthermore, the compound of the present invention is used in the manufacturing of a substrate having the thin film described above, or in the manufacturing of a semiconductor substrate described above. [Examples]

[0076] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples.

[0077] (Example 1) <Fabrication of substrates with thin films> The following compounds were used as raw materials for thin film formation. [ka] In the formula, "Et" represents an ethyl group.

[0078] The manufacturing apparatus shown in Figure 3 was used to produce the substrate with the thin film. The raw materials for thin film formation were placed in the raw material container 11. A silicon wafer (substrate 1) that had been surface-treated with UV ozone was placed on a support stand 16 inside the film deposition chamber 12. The pressure inside the film deposition chamber 12 was set to 20 mbar (2,000 Pa), and the film deposition chamber 12 was heated to 140°C using the heater 13. The temperature of the raw material container 11 was raised to 140°C using the heater 13, and the pressure inside the raw material container 11 was reduced to 20 mbar (2,000 Pa), thereby converting the raw material for thin film formation inside the raw material container 11 into a gas 2a. The thin-film forming raw material, which had turned into a gas 2a in the raw material container 11, was introduced into the film formation chamber 12 via piping 14a, and the gaseous thin-film forming raw material 2a was brought into contact with the surface of the silicon wafer (substrate 1). This operation was carried out for 1 hour to form a thin film having diallyl isocyanurate propylsilyl groups on the silicon wafer (substrate 1). A silicon wafer (substrate 1) with a thin film was removed from the deposition chamber 12. The thickness of the obtained thin film was measured using an ellipsoid-type film thickness analyzer, the ASET-F5 (manufactured by KLA Corporation; the same applies hereafter). The result was 2.0 nm. Furthermore, when the water contact angle was measured using a fully automatic contact angle meter DM-701 (Kyowa Interface Science Co., Ltd.), the water contact angle of a silicon wafer surface-treated with UV ozone was 20° or less, while the water contact angle of a thin film formed on the silicon wafer was 71°. This increase in contact angle indicates that a thin film containing diallyl isocyanurate propylsilyl groups was formed, resulting in increased hydrophobicity.

[0079] <Solvent resistance test> A thin film obtained by the same method as described above was coated onto a silicon wafer with a mixed solvent of propylene glycol monomethyl ether / propylene glycol monomethyl ether acetate (7 / 3 (vol / vol)) and spin-dried at 1,500 rpm / 30 seconds. The thickness of the thin film after spin drying was measured using an ellipsometric film thickness measuring instrument, and the presence or absence of a decrease in the 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, those with a decrease in the film thickness of less than 5% after the application were evaluated as "good", and those with a decrease in the film thickness of 5% or more were evaluated as "bad". The obtained results are shown in Table 1.

[0080]

Table 1

[0081] From these results, it was confirmed that a thin film having solvent resistance was formed.

[0082] <Formation of resist pattern by EUV exposure: Positive-type alkali development> <<Example 1>> On the thin film of a silicon wafer having a thin film obtained by the same method as described above, a resist solution for EUV (methacrylate / polyhydroxystyrene resin-based resist) was spin-coated and heated at 110°C for 1 minute to form an EUV resist film (C layer). Then, using an EUV exposure apparatus (NXE3400) manufactured by ASML, exposure was performed under the conditions of NA = 0.33, σ = 0.63 / 0.84, and Quadropole. After exposure, post-exposure bake (PEB, 105°C for 1 minute) was performed, cooled to room temperature on a cooling plate, developed for 30 seconds using a 2.38% TMAH developer, rinsed, and a resist pattern was formed.

[0083] <<Comparative Example 1>> Also, as Comparative Example 1, an EUV resist was formed on a silicon wafer that had not been subjected to any treatment as described above, and the same exposure and development were performed.

[0084] For each of the obtained patterns, the possibility of forming a line pattern with a pitch of 28 nm and a width of 12 nm was evaluated by confirming the pattern shape through cross-sectional observation of the pattern. In the observation of the pattern shape, the state where there is no significant residue in the space part and the shape between the footing and the undercut is evaluated as "good", and the undesirable state where the resist pattern falls is evaluated as "fallen". The obtained results are shown in Table 2.

[0085]

Table 2

Industrial Applicability

[0086] According to the present invention, since it is possible to form a novel thin film on a substrate, the present invention is useful for the production of a substrate having a novel thin film and the production of a semiconductor substrate having a novel thin film.

Explanation of Reference Numerals

[0087] 1 Substrate 1a Silicon wafer 1b Organic underlayer film 2 Thin film 2a Gas 11 Raw material storage container 12 Film formation chamber 13 Heater 14a, 14b Pipes 15 Discharge port 16 Support stand 17 Trap 18 Vacuum pump

Claims

1. A substrate having a thin film, Si-R in the compound represented by the following formula (1) １ The thin film having a group, On its surface, the SiR １ The substrate on which the thin film having the group is disposed, A substrate having a thin film. 【Chemistry 1】 (In the above formula (1), R １ represents a monovalent organic group bonded to Si, R ２ represents a monovalent organic group bonded to Si, R ３ represents an alkoxy group, an acyloxy group, or a halogen atom bonded to Si, n represents an integer of 0 to 2, and when n is 2, R ２ may be the same or different, and when n is 0 or 1, R ３ may be the same or different. When n is 1, R １ and R ２ may combine to form a ring structure.)

2. A substrate having a thin film according to claim 1, formed by contacting the surface of the substrate with a compound represented by formula (1) and further causing a chemical reaction of the compound.

3. R １ A substrate having a thin film according to claim 1 or 2, wherein the monovalent organic group in is a monovalent organic group having 1 to 20 carbon atoms and an oxygen atom.

4. In the above formula (1), R １ R represents a monovalent group represented by the following formula (2), ２ This represents a monovalent group represented by formula (2) above, or an organic group having an alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group, alkenyl group, epoxy group, organic group having an acryloyl group, organic group having a methacryloyl group, organic group having a mercapto group, organic group having an amino group, or organic group having a cyano group, or a combination of two or more of these. A substrate having a thin film according to any one of claims 1 to 3. 【Chemistry 2】 (In formula (2) above, R ４ R represents a hydrogen atom, or a monovalent organic group containing an alkyl group, alkenyl group, epoxy group, sulfonyl group, or two or more thereof, with 1 to 10 carbon atoms. ５ X represents an alkylene group having 1 to 10 carbon atoms, a hydroxyalkylene group, a sulfide bond, an ether bond, an ester bond, or a combination of two or more of these. １ This represents a divalent group represented by formula (3), a divalent group represented by formula (4), or a divalent group represented by formula (5). 【Transformation 3】 (In formulas (3), (4), and (5) above, R ６ ~R １０ Each of these independently represents a hydrogen atom, or a monovalent organic group containing an alkyl group, alkenyl group, epoxy group, sulfonyl group, or two or more of the same, having 1 to 10 carbon atoms. *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).

5. A substrate having a thin film according to any one of claims 1 to 4, A resist film disposed above the thin film, A semiconductor substrate having the following characteristics.

6. By bringing a compound represented by formula (1), which is in gaseous form, into contact with the surface of a substrate, and further chemically reacting the compound, the Si-R in the compound is obtained. １ A step of forming a thin film having a group on the surface of the substrate, A method for manufacturing a substrate having a thin film, including the method described above. 【Chemistry 4】 (In formula (1) above, R １ R represents a monovalent organic group bonded to Si, ２ R represents a monovalent organic group bonded to Si, 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 They may be the same or different, and if n is 0 or 1, R ３ They may be the same or different. When n is 1, R １ and R ２ They may be together forming a ring structure.

7. The process of forming the thin film on the surface of the substrate is carried out in a film deposition chamber. Furthermore, the Si-R １ A method for manufacturing a substrate having a thin film according to claim 6, comprising the step of removing the substrate, on which the thin film having the group has been formed on its surface, from the film formation chamber.

8. R １ A method for producing a substrate having a thin film according to claim 6 or 7, wherein the monovalent organic group in is a monovalent organic group having 1 to 20 carbon atoms and an oxygen atom.

9. In the above formula (1), R １ R represents a monovalent group represented by the following formula (2), ２ This represents a monovalent group represented by formula (2) above, or an organic group having an alkyl group, aryl group, aralkyl group, halogenated alkyl group, halogenated aryl group, halogenated aralkyl group, alkenyl group, epoxy group, organic group having an acryloyl group, organic group having a methacryloyl group, organic group having a mercapto group, organic group having an amino group, or organic group having a cyano group, or a combination of two or more of these. A method for manufacturing a substrate having a thin film according to any one of claims 6 to 8. 【Transformation 5】 (In formula (2) above, R ４ R represents a hydrogen atom, or a monovalent organic group containing an alkyl group, alkenyl group, epoxy group, sulfonyl group, or two or more thereof, with 1 to 10 carbon atoms. ５ X represents an alkylene group having 1 to 10 carbon atoms, a hydroxyalkylene group, a sulfide bond, an ether bond, an ester bond, or a combination of two or more of these. １ This represents a divalent group represented by formula (3), a divalent group represented by formula (4), or a divalent group represented by formula (5). 【Transformation 6】 (In formulas (3), (4), and (5) above, R ６ ~R １０ Each of these independently represents a hydrogen atom, or a monovalent organic group containing an alkyl group, alkenyl group, epoxy group, sulfonyl group, or two or more of the same, having 1 to 10 carbon atoms. *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).

10. A method for manufacturing a substrate having a thin film according to any one of claims 6 to 9, comprising the step of turning the compound represented by formula (1) into a gas.

11. A step of manufacturing the substrate having the thin film using a method for manufacturing the substrate having the thin film described in any one of claims 6 to 10, A step of forming a resist film on top of the thin film, A method for manufacturing a semiconductor substrate, including the method described above.

12. Manufacturing of a substrate having a thin film according to any one of claims 1 to 4, Manufacturing of a semiconductor substrate according to claim 5, A method for manufacturing a substrate having a thin film according to any one of claims 6 to 10, and Method for manufacturing a semiconductor substrate according to claim 11 A compound represented by formula (1) above, used in any of the following.

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