Substrate processing method and substrate manufacturing method

Abstract

This method for treating a substrate comprises: a preparation step for preparing a substrate having, on the surface thereof, a first surface containing Si and a second surface containing Si and having a chemical composition different from that of the first surface; a surface modification step for applying a water repellency adjustment treatment for selectively reducing the water repellency of the second surface with respect to the first surface after applying a silylation treatment in which a silylation agent is brought into contact with the first surface and the second surface; and a processing step in which, after the surface modification step, a processing treatment is selectively applied to the second surface.

Description

Technical Field

[0001] The present invention relates to a method for treating a substrate and a method for manufacturing the substrate. Background Art

[0002] In the past, semiconductor devices have been finely patterned through multiple photolithography and etching processes. However, in recent years, semiconductor devices have tended to be more integrated and miniaturized. To meet these requirements, photolithography processes tend to become complicated and expensive, and an alternative to photolithography is sought.

[0003] As an alternative to photolithography, a technology using a self-assembled monolayer (SAM) has been studied. Specifically, it is a technology that selectively deposits a self-assembled monolayer (hereinafter referred to as a "monolayer") as a mask material or protective material on a non-processing target area of ​​a substrate, and forms or deposits a desired film material, or performs an etching process, on the remaining area of ​​the substrate (i.e., the processing target area).

[0004] As a method for selectively depositing the above-mentioned monomolecular film, various methods have been studied, for example, there is a method of selectively forming a monomolecular film based only on the chemical properties of the surface of the substrate. In this method, as long as the monomolecular film can be selectively formed, the combination of the non-processed object and the processed object is not particularly limited, so various studies have been conducted on methods for forming a monomolecular film corresponding to the combination. As such a technology, for example, the technology described in Patent Documents 1 to 3 is known.

[0005] For example, Patent Document 1 discloses a method in which a protective film forming gas containing an amine gas is supplied to a substrate having a first film and a second film on the surface thereof that are etchable by an etching gas, so that the amine is adsorbed on the first film for selective protection, and then the second film is selectively etched. In the claims of this document, a silicon oxide film and a silicon film, and a SiOCN film and a silicon oxide film are disclosed as combinations of the first film and the second film, respectively, and as protective film forming gases, hexylamine, dipropylamine, n-octylamine, butylamine, tert-butylamine, decylamine, dodecylamine, dicyclohexylamine, tetradecylamine, and the like are exemplified.

[0006] Patent document 2 discloses the following method: SAM is formed on a vertical spacer as a bulk material, and a high-k film is selectively formed on the nanowires between the vertical spacers, and a metal gate electrode layer is selectively formed on the high-k film. The document describes the following: the vertical spacer includes a SiCOH material, a dielectric material having a relative dielectric constant of less than about 7, or an air gap spacer; and the nanowire is composed of Si, SiGe, or both Si and SiGe. In addition, as the terminal group of the molecule forming the SAM, thiol, silane, or phosphate ester is exemplified.

[0007] Patent document 3 discloses the following method: silylation of the surface is performed by exposing a substrate having a surface containing silicon such as Si, SiN, silicon thermal oxide, and a surface not containing silicon such as W, Co, TiN, TaN, etc. to a surface treatment agent having a silylating agent and a nitrogen-containing heterocyclic compound. In this document, it is proposed that a water-repellent film is formed on the surface by silylation, but the water contact angle after silylation varies depending on the material of the surface. By utilizing the difference in the water contact angle, a film based on the atomic layer deposition (Atomic Layer Deposition: hereinafter referred to as "ALD") method is formed on the desired surface, that is, the surface on which the water-repellent film is not easily formed.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application No. 2021-163775

[0011] Patent Document 2: Japanese Patent Publication No. 2021-528859

[0012] Patent Document 3: Japanese Patent Application Publication No. 2019-121777 Summary of the invention

[0013] Problem that the invention aims to solve

[0014] The method of forming a water-repellent film as a monomolecular film by silylation of the surface as described in Patent Document 3 is useful because the film can be easily formed on a surface having silicon (hereinafter referred to as "Si-based surface").

[0015] However, in the case where a water-repellent film is formed on one of the Si-based surfaces (the first surface) and no water-repellent film is formed on the other Si-based surface (the second surface) having a different chemical composition, or in the case where a water-repellent film is selectively formed between the first surface and the second surface (e.g., a silicon surface and a silicon oxide surface, a silicon oxide surface and a silicon nitride surface, etc.) which are Si-based surfaces, the two surfaces each have reactivity with a silylating agent, and thus there is a tendency that it becomes difficult to form a selective water-repellent film.

[0016] The present invention aims to realize a method for treating a substrate having excellent selectivity between a first surface and a second surface which are Si-based surfaces.

[0017] Solutions for solving problems

[0018] According to one aspect of the present invention, the following substrate processing method and substrate manufacturing method are provided.

[0019] 1. A method for treating a substrate, comprising:

[0020] A preparation step of preparing a substrate having a first surface and a second surface on the surface, wherein the first surface contains Si, and the second surface has a chemical composition different from that of the first surface and contains Si;

[0021] a surface modification step of applying a silylation treatment in which a silylating agent is brought into contact with the first surface and the second surface, and then applying a water repellency adjustment treatment in which the water repellency of the second surface is selectively reduced relative to the first surface; and

[0022] The processing step is to selectively perform processing on the second surface after the surface modification step.

[0023] 2. The method for treating a substrate according to 1., wherein:

[0024] The surface modification step is a step of applying a pretreatment before the silylation treatment.

[0025] The pretreatment includes treatment A-1 of removing at least the natural oxide film on the first surface and / or treatment A-2 of bonding OH to at least a portion of Si on the first surface.

[0026] 3. The method for treating a substrate according to 2., wherein:

[0027] The above-mentioned treatment A-2 is treatment A-2a of bringing at least the first surface into contact with an active species containing oxygen element and / or a gas containing oxygen element, or treatment A-2b of bringing at least the first surface into contact with an oxidant containing oxygen element.

[0028] 4. The method for treating a substrate according to 3., wherein:

[0029] The treatment A-2a is at least one selected from the group consisting of a plasma treatment using plasma containing oxygen, a UV / O3 treatment, and a gas treatment of exposure to a gas containing oxygen.

[0030] 5. The method for treating a substrate according to 3., wherein:

[0031] The aforementioned oxidant includes a solution containing H2O2 and / or ozone water.

[0032] 6. The method for treating a substrate according to any one of 1. to 5., wherein

[0033] The water repellency adjustment treatment includes a removal treatment of removing at least a portion of the compound derived from the silylation agent chemically or physically bonded to the second surface using a remover.

[0034] 7. The method for treating a substrate according to 6., wherein:

[0035] The remover includes at least one selected from the group consisting of ammonia, organic amines, quaternary ammonium hydroxide and hydrogen fluoride.

[0036] 8. The method for treating a substrate according to any one of 1. to 7., wherein

[0037] When the value of the water contact angle of the first surface after the surface modification step and immediately before the processing step is defined as S1 and the value of the water contact angle of the second surface is defined as S2,

[0038] (S1-S2) / S2 is greater than 1.0.

[0039] 9. The method for treating a substrate according to any one of 1. to 8., wherein

[0040] When the first surface is silicon oxide, the second surface is silicon or a compound of Si and at least one selected from the group consisting of N, C and metal elements, or an oxide of the compound;

[0041] When the first surface is silicon, the second surface is a compound of Si and at least one selected from the group consisting of N, C and metal elements, or an oxide of the compound;

[0042] When the first surface is a compound or oxide of Si and at least one selected from the group consisting of N and C, the second surface is a compound of Si and a metal element or an oxide of the compound.

[0043] 10. The method for treating a substrate according to any one of 1. to 9., wherein

[0044] In the processing step, the processing includes: a film forming process of forming a film on the second surface by atomic layer deposition, and / or an etching process of etching the second surface.

[0045] 11. The method for treating a substrate according to any one of 1. to 10., wherein

[0046] In the aforementioned silylation treatment, the aforementioned silylation agent or a silylation composition containing the aforementioned silylation agent is used.

[0047] 12. The method for treating a substrate according to 11., wherein:

[0048] The silylation composition comprises at least one of a solvent, a diluent gas and a catalytic compound.

[0049] 13. The method for treating a substrate according to any one of 1. to 12., wherein:

[0050] The surface modification step includes a cleaning treatment of cleaning at least a portion of the second surface using a cleaning agent.

[0051] 14. The method for treating a substrate according to 13., wherein:

[0052] The cleaning agent includes an aqueous cleaning solution and / or a rinse solution.

[0053] 15. A method for producing a substrate, comprising the step of obtaining a substrate subjected to each of the steps in the method for treating a substrate according to any one of 1. to 14.

[0054] Effects of the Invention

[0055] According to the present invention, a method for treating a substrate having excellent selectivity between a first surface and a second surface which are Si-based surfaces, and a method for producing a substrate using the same can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] Figure 1 The following are process cross-sectional views schematically showing each process of the substrate processing method according to the present embodiment.

[0057] Figure 2 The following are process cross-sectional views schematically showing each process of the substrate processing method according to the present embodiment.

[0058] Figure 3 The following are process cross-sectional views schematically showing each process of the substrate processing method according to the present embodiment. DETAILED DESCRIPTION

[0059] The following is an explanation of the implementation of the present invention using the accompanying drawings. It should be noted that in all the accompanying drawings, the same components are marked with the same symbols and their description is appropriately omitted. In addition, the drawings are schematic diagrams and are not consistent with the actual size ratios.

[0060] <Substrate Treatment Method>

[0061] The outline of the substrate processing method according to the present embodiment will be described.

[0062] The substrate treatment method of the present invention comprises: a preparation step of preparing a substrate having a first surface and a second surface on the surface, wherein the first surface contains Si, and the second surface has a chemical composition different from that of the first surface and contains Si; a surface modification step of applying a silylation treatment in which a silylating agent is brought into contact with the first surface and the second surface, and then applying a water repellency adjustment treatment to selectively reduce the water repellency of the second surface relative to the first surface; and a processing step of selectively applying a processing treatment to the second surface after the surface modification step.

[0063] According to the findings of the present inventors, it was discovered that after applying a silanization treatment to two Si-based surfaces (a first surface and a second surface) containing Si elements but having different chemical compositions, a surface modification step such as a water repellency adjustment treatment that selectively reduces the water repellency of the other second surface relative to one of the first surfaces is performed, and thus the second surface can be selectively processed using selective film formation using an ALD method or the like, selective etching treatment, etc.

[0064] It should be noted that, in this specification, the “different chemical composition” of the Si-based surface includes: the case where the elements other than silicon contained in the first surface are different from the elements other than silicon contained in the second surface, the case where the content ratio of the elements contained in the first surface is substantially different from the content ratio of the elements contained in the second surface, etc.

[0065] Generally, since the first surface and the second surface, which are Si-based surfaces, are reactive with a silylation agent, respectively, it tends to be difficult to form a water-repellent film on only one surface.

[0066] In contrast, according to the present embodiment, it is possible to selectively reduce the water repellency of the desired Si-based surface by applying a water repellency adjustment treatment, so that between two or more Si-based surfaces, a Si-based surface (first surface) with a water repellent film formed thereon and a Si-based surface (second surface) with very low water repellency and no water repellent film formed thereon coexist. It should be noted that, through the research of the inventors and others, it is known that when the water repellency is very low, although the presence or absence of the water repellent film is unclear, the function as a protective film is also very small. From the above content, since the above-mentioned coexistence state is made, the water repellent film will function as a protective film, and thus the Si-based surface with low water repellency is selectively processed, and a processing method for selecting a substrate with excellent processability between the first surface and the second surface as the Si-based surface can be realized.

[0067] It should be noted that the "water-repellent film" in this specification refers to any compound having a silyl group derived from a silylating agent chemically bonded to a Si-based surface and any group of such compounds, regardless of the presence or absence of interaction between the compounds and the presence or absence of bonding. In addition, the water-repellent film may also include a compound derived from a silylating agent physically bonded to a Si-based surface (adsorption, attachment, etc.). It should be noted that the above bonding does not need to be direct bonding, and also includes bonding with the aid of other elements, substituents, etc.

[0068] (Water repellency)

[0069] The water repellency in this specification uses the water contact angle obtained by the following measurement. In addition, the details of washing, drying, etc. before each measurement are described later.

[0070] First, place the substrate horizontally with the desired Si-based surface facing upward, and place a 2μL drop of pure water on the surface. It should be noted that in order to suppress the influence of the surface shape on the water contact angle, a substrate with a smooth surface for placing the water drop is used. Secondly, based on JIS R 3257:1999 "Test method for wettability of glass substrate surface", the measurement temperature is room temperature (25°C), and the angle formed by the water drop and the substrate is measured by a contact angle meter (Kyowa Interface Science: CA-X model), and the obtained value is used as the water contact angle.

[0071] The details of each step included in the method for treating a substrate are described below.

[0072] An example of a substrate treatment method according to the present embodiment includes a preparation step, a surface modification step, and a processing step. Figure 1 to Figure 3 To explain. Figure 1 to Figure 3 The following are process cross-sectional views schematically showing each process of the method for treating a substrate.

[0073] (Preparation process)

[0074] The above preparation steps are as follows Figure 1 As shown in FIG. 1 , a substrate 1 having a first surface 11 and a second surface 12 is prepared.

[0075] The material of the substrate 1 is not particularly limited as long as it is a substrate used in semiconductor manufacturing processes, and may be composed of, for example, silicon, silicon carbide, multiple components containing silicon, sapphire, various compound semiconductors, etc. In addition, the substrate 1 may be, for example, a wafer.

[0076] The substrate 1 may also include a concavo-convex structure (not shown) formed on the surface of the substrate.

[0077] The concave-convex structure may also be composed of a three-dimensional structure having, for example, one or more structures arranged in the vertical direction along the substrate surface 1a and / or one or more structures arranged in the horizontal direction orthogonal to the vertical direction. As an example of such a three-dimensional structure, it may also constitute at least a part of a logic device, a storage device, a gate electrode, etc., such as: FinFET, nanowire FET, nanolayer FET or other multi-gate FET, three-dimensional storage cell, etc.

[0078] The first surface 11 and the second surface 12 can be arranged along the planar direction of the substrate surface 1a, respectively, or can be arranged along the vertical direction relative to the substrate surface 1a. According to this embodiment, not only can two-dimensional selective processing be performed on the plane, but also three-dimensional selective processing (three-dimensional film formation, three-dimensional etching, etc.) can be performed on the three-dimensional structure.

[0079] The first surface 11 and the second surface 12 may be formed adjacent to each other, or may be formed at a distance from each other. The first surface 11 and the second surface 12 may also be composed of one region or more than two regions. In each surface, multiple regions may also be formed at a distance from each other.

[0080] As materials constituting the first surface 11 and the second surface 12 , the following can be cited.

[0081] Examples of such materials include (1) silicon (polycrystalline silicon, single crystal silicon), (2) silicon oxide, and (3) compounds of Si and at least one selected from the group consisting of N, C, and metal elements, or oxides of the above compounds.

[0082] The metal element in (3) refers to any metal element or semi-metal element generally used in semiconductor materials, and examples thereof include W, Co, Al, Ni, Ru, Cu, Ge, Ti, Hf, Ta, etc. In addition, examples of compounds containing N and C with Si include compounds such as silicon nitride, silicon carbide, and silicon carbonitride, and compounds of these compounds with the above metal elements, and examples of oxides include oxides of these compounds.

[0083] Each of the materials (1) to (3) may contain elements other than Si, N, C and O (H, P, B, etc.).

[0084] It should be noted that the above-mentioned "oxide" refers to a state in which oxygen is bonded to other constituent materials (especially Si) and contained to a degree that affects certain properties, and does not include a case in which a small amount exists to a degree that does not affect physical properties. In addition, a "compound" refers to a state in which an element other than oxygen is bonded to other constituent materials (especially Si) and contained to a degree that affects certain properties, and does not include a case in which a small amount exists to a degree that does not affect physical properties.

[0085] In the preparation process of the present disclosure, when the surface layer of each material of (1) or (3) is inadvertently naturally oxidized, a material that is not naturally oxidized (for example, naturally oxidized silicon is regarded as silicon) may be used.

[0086] An example of a combination of constituent materials of the first surface 11 and the second surface 12 is given below.

[0087] For example, when the first surface 11 is silicon oxide, the second surface 12 may be composed of a compound of silicon or Si and at least one selected from the group consisting of N, C and metal elements, or an oxide of the compound.

[0088] Furthermore, when the first surface 11 is silicon, the second surface 12 may be composed of a compound of Si and at least one selected from the group consisting of N, C, and metal elements, or an oxide of the compound.

[0089] In addition, when the first surface 11 is a compound or oxide of Si and at least one selected from the group consisting of N and C, the second surface 12 may be composed of a compound of Si and a metal element or an oxide of the compound.

[0090] The first surface 11 and the second surface 12 may be constituted by the surface of a component made of the above-mentioned material, or may be constituted by the surface of a film formed of the above-mentioned material. In particular, when the surface is constituted by a film, two or more elements other than Si of the above-mentioned materials may also be contained. As films containing two or more elements other than Si, for example, common low-k films such as SiON, SiCN, SiCO, SiCOH, and SiOCN can be listed. It should be noted that the composition of the above-mentioned film is only a representative record, and the stoichiometric ratio may not be an integer ratio as recorded. Specifically, in the case of SiON, it is not limited to Si:O:N=1:1:1.

[0091] The water repellency of each of the first surface 11 and the second surface 12 is usually an inherent property of the constituent materials constituting the surface, but can be adjusted by pre-treatment, silylation treatment and removal treatment described later. For example, if silylation treatment is performed, the original water repellency (water contact angle, etc.) tends to be further improved, and if removal treatment is performed, the water repellency improved by silylation treatment is reduced. In addition, the effect of the above-mentioned silylation treatment and removal treatment can be strengthened or weakened by pre-treatment. Since the above-mentioned tendency is different due to the constituent materials of each surface, the first surface 11 as the protection object of the processing treatment and the second surface 12 as the object of the processing treatment can be appropriately adopted by considering the combination of each treatment and the water repellency just after these treatments. It should be noted that a water-repellent film is formed on the surface by silylation treatment of the first surface 11 and the second surface 12, even if "the water repellency of the surface" actually refers to "the water repellency of the water-repellent film", it is also recorded as "the water repellency of the first surface" and "the water repellency of the second surface". Even when at least a portion of the surface layer of each surface is oxidized or reduced due to a pretreatment, a removal treatment, or the like described later, these surfaces are regarded as the first surface 11 and the second surface 12 prepared in the preparation step.

[0092] It should be noted that, in the first surface 11 and the second surface 12, and in the substrate 1 in the peripheral area below the first surface 11 and the second surface 12, one or more dopants (such as P, N, B, Al, etc.) used for n-type source and drain and p-type source and drain may be contained in trace amounts. Since the above-mentioned dopants can affect electrical properties by adding a trace amount relative to the content of Si element, it can be inferred that as long as the content is the degree to which it functions as a dopant, it will not affect the silylation on the first surface 11 and the second surface 12.

[0093] The substrate 1 may further have a third surface and / or a fourth surface (not shown) on the substrate surface 1 a.

[0094] The third surface contains Si and is a surface having a chemical composition different from those of the first surface 11 and the second surface 12 .

[0095] The fourth surface is a surface that does not contain Si, and is composed of elements such as amorphous carbon, W, Co, Al, Ni, Ru, Cu, Ti, Ta, or compounds, oxides, nitrides, etc. of these elements. The fourth surface may also be a film surface of a High-k film.

[0096] The third surface and the fourth surface may be adjacent to or spaced from the first surface 11 and / or the second surface 12. In addition, the third surface and the fourth surface may be composed of one region or two or more regions.

[0097] (Surface modification process)

[0098] The surface modification process comprises a silylation treatment of the substrate surface and a water repellency adjustment treatment after the aforementioned silylation treatment. As previously mentioned, by the water repellency adjustment treatment, the water repellency of the second surface of the substrate is selectively reduced relative to the water repellency of the first surface. In other words, the water repellency of the first surface of the substrate may also be suppressed or maintained from being reduced. At this time, in order to enhance the effect of the silylation treatment of the first surface or to make the water repellency of the second surface more easily reduced, additional treatment may also be performed before and after the silylation treatment. In addition, in the case where the water repellency of the first surface is higher than the water repellency of the second surface at the time point just after the silylation treatment, the water repellency of the second surface is further reduced by performing the water repellency adjustment treatment, so that the second surface can be easily subjected to selective processing in the processing steps described later.

[0099] As an example of the surface modification process, there can be mentioned Figure 1 After the substrate 1 is pre-treated, Figure 2 and Figure 3 As shown, silylation treatment and removal treatment are performed.

[0100] In this specification, pretreatment / silylation treatment / removal treatment may be referred to as pretreatment A / silylation treatment B / removal treatment C or treatment A / treatment B / treatment C, respectively.

[0101] It should be noted that part or all of these treatments A to C may be implemented by a wet manufacturing process or a dry manufacturing process. In addition, the above-mentioned treatments A to C may be those in which the first surface 11 and the second surface 12 are processed separately or simultaneously. Figure 1 It is convenient and preferred to carry out the treatments simultaneously as shown.

[0102] In addition, if good results can be obtained by the silylation treatment B and the removal treatment C even without the pretreatment A, the pretreatment A may not be performed.

[0103] When the surface modification step includes applying pretreatment A before silylation treatment B, pretreatment A may include: treatment A-1 for removing at least the natural oxide film on the first surface 11 , and / or treatment A-2 for bonding OH to at least a portion of Si on the first surface 11 .

[0104] Pretreatment A only needs to be performed on at least the first surface 11, but may also be performed on the first surface 11 and the second surface 12. However, even if treatment A is applied, depending on the constituent materials, the natural oxide film may not be removed on a part or all of the second surface 12, and OH groups may not be formed on the surface.

[0105] In addition, the above-mentioned treatment A-2 may also include: treatment A-2a of bringing at least the first surface 11 into contact with an active species containing oxygen elements and / or a gas containing oxygen elements; or treatment A-2b of bringing at least the first surface 11 into contact with an oxidant containing oxygen elements.

[0106] Treatment A-1 is not particularly limited as long as it is a treatment that can remove the natural oxide film. Usually, in the process of semiconductor manufacturing process, a natural oxide film is formed on the surface of polysilicon, silicon oxide, etc. Since the natural oxide film can be removed by treatment A-1, it is preferred. It should be noted that in the case of a surface where a natural oxide film is not formed, treatment A-1 is not required, but the same operation can be performed as a part of cleaning.

[0107] As a specific method for processing A-1, for example, can be listed: a method in which hydrofluoric acid (HF) is contacted to the first surface 11 and the second surface 12, a method in which a diluted hydrofluoric acid aqueous solution (DHF) is contacted to the first surface 11 and the second surface 12, a method in which a mixed gas comprising HF gas and NH3 gas reacts with the first surface 11 and the second surface 12, etc. The specific method of contact can be a known method, for example, can be listed: the same method as the silylation treatment B described later, known dry manufacturing process treatment, etc. It should be noted that, after it is contacted with hydrofluoric acid, the cleaning treatment utilizing a cleaning agent described later can also be implemented.

[0108] Treatment A-2 is not particularly limited as long as it is a method for forming OH groups on the surface of the first surface 11. Since the ease of silylation caused by the silylation treatment B and the ease of reduction of water repellency caused by the removal treatment C may be different depending on the strength of the oxidizing power when the OH groups are formed, it is ideal to adopt a suitable treatment for the desired Si-based surface. As treatment A-2, for example, the aforementioned treatment A-2a, the aforementioned treatment A-2b, etc. can be listed. Through treatment A-2, a new OH group-containing region can also be formed on the first surface 11, and a film (Si-OH coating) having OH groups can also be formed. The OH groups on the first surface 11 become reaction sites with the silylating agent in the subsequent silylation treatment B.

[0109] The aforementioned treatment A-2a is a treatment that is easier to oxidize the Si-based surface than the aforementioned treatment A-2b. The treatment A-2a is to contact at least the first surface 11 with an active species containing an oxygen element and a gas containing an oxygen element. As a specific method of the aforementioned treatment A-2a, a known oxidation treatment used in a dry manufacturing process can be appropriately used, for example, at least one selected from the group consisting of a plasma treatment using a plasma containing an oxygen element, a UV / O3 treatment, and a gas treatment exposed to a gas containing an oxygen element. Since the aforementioned treatment A-2a is easy to oxidize the Si-based surface, even if a natural oxide film is formed on the surface, an OH group can be formed on the first surface 11 without going through the aforementioned treatment A-1.

[0110] The plasma treatment may be a known method, for example, O 3 plasma treatment, O 2 plasma treatment, CO 2 plasma treatment, CO plasma treatment, NO 2 plasma treatment, NO plasma treatment, H 2 O plasma treatment, etc.

[0111] The UV / O3 treatment is a treatment for generating free radicals containing oxygen elements to perform oxidation, and a known treatment apparatus can be used.

[0112] In addition, as the gas used in the above-mentioned gas treatment, for example, there can be mentioned gases such as O3, O2, CO2, and H2O2. For the purpose of efficient oxidation, heated gas can also be used.

[0113] The treatment A-2b is a treatment that can oxidize the Si-based surface more stably than the treatment A-2a. The treatment A-2b is to bring at least the first surface 11 into contact with an oxidant containing oxygen.

[0114] As the above-mentioned oxidant, a gas containing oxygen elements that does not have the oxidizing power of the above-mentioned treatment A-2a or the same gas under weak oxidizing conditions can be used, but in terms of easy adjustment of the intensity of oxidation, it is preferred to use a liquid oxidant. As the above-mentioned liquid oxidant, for example, there can be listed: a solution containing H2O2 and / or ozone water. In addition, as a solution containing H2O2, for example, there can be listed: a cleaning agent used in the cleaning of silicon wafers, etc. (an alkaline mixed solution of H2O2 and ammonium hydroxide (SC-1 solution), an acidic mixed solution of H2O2 and hydrochloric acid (SC-2 solution)), an aqueous solution of H2O2, etc. The specific method of contact can be a known method, for example, there can be listed: the same method as the silanization treatment B described later, etc.

[0115] It should be noted that, before the treatment A-2b, the treatment A-1 may be performed if necessary to remove the natural oxide film in advance. In addition, the above-mentioned treatment A-2a and treatment A-2b may be used in combination.

[0116] Silylation treatment B Figure 2 As shown in (a), the silylating agent described later is brought into contact with at least the first surface 11 and the second surface 12. In the silylating treatment B, the silylating agent can be used alone, but a silylating composition comprising a silylating agent and a solvent, a diluent gas, or a silylating composition comprising a silylating agent and a catalytic compound, and if necessary, a solvent, a diluent gas can also be used. The silylating agent and the silylating composition can be used in a liquid or gaseous state.

[0117] In the case of a wet manufacturing process, a liquid of the silylating agent 20 or the silylating composition 20 is supplied to the first surface 11 and the second surface 12. The supply method may be a known method, for example, when supplied in a liquid state, a single-sheet method such as a spin coating method, a batch method such as a dipping method, etc. may be cited. In addition, when supplied in a vapor state and becomes a liquid after contacting with the first surface 11 and the second surface 12, a known vapor spraying method may be used.

[0118] In the case of a dry manufacturing process, the silylating agent is supplied to the first surface 11 and the second surface 12 in the form of a gas. The supply method can use known means, for example, a method of supplying the silylating agent by gasifying the silylating agent in advance using a vaporizer or the like; a method of supplying the silylating agent by flowing it simultaneously with an inert gas such as N2 or Ar, etc. In addition, two or more gases may be supplied simultaneously or mixed in advance.

[0119] The water repellency of at least the first surface 11 can be improved by the silylation treatment B. In addition, the water repellency of the second surface 12 may also be improved at this time.

[0120] By the above-mentioned silylation treatment B, a structure in which the silyl group derived from the silylating agent is chemically bonded to the OH group of the first surface 11, i.e., a water-repellent film, is formed on the first surface 11, and the water repellency is improved. In addition, a water-repellent film is sometimes formed on the second surface 12 as well, and even in the case where a water-repellent film is not formed, the water repellency is sometimes increased due to a structure in which a compound derived from the silylating agent is physically bonded (e.g., attached or adsorbed) to the surface.

[0121] As an example, Figure 2 As shown in (b), a water-repellent film 21 may be formed on the first surface 11, and a water-repellent film 22 may be formed on the second surface 12. The water-repellent film 21 and the water-repellent film 22 may be composed of films covering at least a portion or all of each surface.

[0122] It should be noted that the second surface 12 does not necessarily have to form a water-repellent film 22. In order to easily reduce the water repellency of the second surface 12 by the water repellency adjustment treatment, it is preferred to form a water-repellent film 22 on a portion of the second surface 12, or to make a state to the extent that the compound derived from the silylating agent is physically bonded to the second surface 12.

[0123] The water repellency improved by the silylation treatment B can be estimated by comparing the water repellency immediately before the silylation treatment B with the water repellency immediately after the silylation treatment B. Specifically, when the value (°) of the water contact angle immediately after the silylation treatment B is taken as R and the value (°) of the water contact angle immediately before the silylation treatment B is taken as P, if the water repellency is improved by the silylation treatment B, the water repellency is improved by the silylation treatment B.

[0124] (RP) / P

[0125] If the silylation ratio shown is large (e.g., greater than 5.0), it can be inferred that there is a tendency to form a water-repellent film derived from the silylation agent. In addition, if the above-mentioned silylation ratio is small (e.g., less than 5.0), it can be inferred that there is a tendency that only a portion of the water-repellent film derived from the silylation agent is formed or that the proportion of physical bonding of the compound derived from the silylation agent is high. It should be noted that the above-mentioned "water contact angle before the silylation treatment B is about to be performed" is the water contact angle of the unsilylated surface. In the case of multiple silylation treatments B, the water contact angle before the earliest silylation treatment B is used.

[0126] If the reaction sites with the silylating agent on the first surface 11 can be increased by pretreatment A, the silylation reaction can be promoted in the silylation treatment B. In addition, since the above-mentioned silylation ratio can be increased by increasing the Si-OH bonds on the surface through pretreatment A-2a and pretreatment A-2b, it is easier to form a water-repellent film, which is suitable when it is intended to be the first surface.

[0127] If necessary, a known method such as heating treatment, reduced pressure treatment, drying treatment, etc. may be applied in the silylation treatment B to promote the silylation reaction between the silylation agent and the OH groups on the surface.

[0128] For the removal treatment C, for example Figure 3 As shown in (b), it refers to the following treatment: the water-repellent film 21 on the first surface 11 is left, and the compound derived from the silylating agent that is chemically / physically bonded to at least a portion of the second surface 12, such as the water-repellent film 22 present on the second surface 12, is removed. By including such a removal treatment C in the water-repellent adjustment treatment, it becomes possible to selectively reduce the water repellency of the second surface 12 relative to the first surface 11.

[0129] like Figure 3As shown in (a) of FIG. 1 , the removal treatment C may be performed by, for example, using a remover to remove at least a portion of the compound derived from the silylation agent chemically or physically bonded to the second surface 12 .

[0130] The specific method of the removal treatment C includes, for example, a method of bringing a liquid remover into contact with the first surface 11 and the second surface 12. In addition, if the water-repellent film 21 on the first surface 11 can be left, a gaseous remover such as a gas may be used. It should be noted that "bringing it into contact with the first surface 11 and the second surface 12" means that when the water-repellent film 21, the water-repellent film 22, etc. are formed, at least the water-repellent film 21 and the water-repellent film 22 are brought into contact.

[0131] The specific method for bringing the remover into contact may be a known method, and examples thereof include the same method as in the silylation treatment B described above.

[0132] As a remover, for example, a solution containing at least one selected from the group consisting of ammonia, organic amine, quaternary ammonium hydroxide and hydrogen fluoride can be used. In addition, when two or more of the above contents are used, the formation of salts is also included. Among the above, if a solution containing at least one selected from the group consisting of hydrogen fluoride, triethylamine, tert-butylamine, diisopropylamine, N,N-dimethylisopropylamine, N,N-diethylmethylamine, N,N-diisopropylethylamine and tetrabutylammonium hydroxide and a protic solvent is used, it is easy to maintain the water repellency of the first surface 11, so it is preferred.

[0133] Examples of the solvent for the remover include water and alcoholic solvents (for example, at least one selected from alcohols having 3 or less carbon atoms such as methanol, 1-propanol, and 2-propanol (isopropanol)). These solvents may be used alone or in combination.

[0134] When a solution containing a remover is used, its concentration may be appropriately selected so as to selectively reduce the water repellency of the second surface 12. For example, when the concentration of the entire solution containing the remover is 100 mass %, the remover may be contained in a total of 0.001 mass % to 80 mass %, or preferably 0.01 mass % to 50 mass %.

[0135] By removing the treatment C, the water repellency of the first surface 11 is maintained, and the water repellency of the second surface 12 is reduced. Based on the tendency of the effect of the removal treatment C, it can be inferred that when the value of the water contact angle (°) just after the silylation treatment B and before the removal treatment C is performed is R, and the value of the water contact angle (°) just after the removal treatment C is Q, if QR < -10°, the water repellency is reduced and the water-repellent film is also removed.

[0136] Therefore, in order to selectively reduce the water repellency of the second surface, it is preferable that the first surface has QR ≥ -10° and the second surface has QR < -10°.

[0137] One of the modes that can reduce water repellency by removing treatment C can include the case where the above-mentioned silylation ratio is small (less than 5.0). This mode is considered to be easy to remove by a remover because the water-repellent film is only formed in a part or the compound derived from the silylation agent is weakly bonded to the second surface 12. In addition, this mode can make the silylation ratio more than 5.0 by applying pretreatment A or changing the type of pretreatment A, so that it is difficult to remove even after removal treatment. That is, if the above-mentioned silylation ratio of the second surface is less than 5.0, it is possible to selectively reduce water repellency relative to the first surface, so it is preferred.

[0138] In addition, one of the modes other than the above that can reduce water repellency (for example, the silanization ratio can be reduced even if it is above 5.0) is not clear about its detailed mechanism, but as an example, it is believed that by connecting oxygen to the Si-based surface, it becomes easier for the surface and the treatment agent to have some kind of interaction (for example, dissolution, catalysis, etc.).

[0139] As long as the surface modification process is in the range of the water repellency that does not significantly damage the first surface 11, the surface layer of the second surface 12 can also be removed by the above-mentioned removal treatment C. For example, sometimes due to the aforementioned pre-treatment A-2, the surface layer of the second surface 12 has oxygen elements, and these oxygen elements can be removed by removing Si bonded with oxygen elements to make the second surface 12 become a clean state. In addition, more than 2 times of removal treatment C can also be carried out. When removing the surface layer of the second surface 12, hydrogen fluoride can be suitably used in the aforementioned remover. In addition, for the purpose of adjusting the removal performance, buffered hydrofluoric acid (a mixture of hydrofluoric acid and ammonium fluoride) can also be suitably used.

[0140] The surface modification step may include a cleaning process of using a cleaning agent to clean at least a portion of the second surface 12 as necessary. For example, the cleaning process may be performed after the removal process C, but the present invention is not limited thereto.

[0141] In addition, when at least a part of processes A to C is performed by a wet manufacturing process, one or more cleaning processes may be performed between processes A to C or between processes included in processes A to C. In the case of multiple cleaning processes, the type of cleaning agent may be changed successively.

[0142] The cleaning agent may also comprise an aqueous cleaning solution and / or a rinse solution.

[0143] The aqueous cleaning solution is not particularly limited as long as it does not remove the water-repellent film 21 formed on the first surface 11. Examples thereof include water, alcohol, aqueous hydrogen peroxide solution, and ozone water. These may be used alone or in combination of two or more.

[0144] The rinse solution is the same as the above-mentioned aqueous cleaning solution, and is not particularly limited as long as it does not remove the water-repellent film 21 formed on the first surface 11. As the rinse solution, a cleaning agent different from the aqueous cleaning solution can be used, for example, water, an organic solvent, a mixture thereof, or a mixture of these with at least one of an acid, an alkali, a surfactant, and an oxidant.

[0145] Examples of organic solvents used in the rinse solution include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide-based solvents, alcohols, derivatives of polyols, nitrogen-containing solvents, etc. Among these, it is preferred to use at least one selected from alcohols having 3 or less carbon atoms, such as methanol, 1-propanol, and 2-propanol (isopropanol).

[0146] In the present embodiment, the method for bringing the cleaning agent into contact is not particularly limited, and examples thereof include a dipping method, a coating method such as a spin coating method or a spray coating method, and a vapor contact method.

[0147] The surface modification step may be subjected to a drying treatment as necessary.

[0148] When at least a part of the processes A to C is performed by a wet manufacturing process, a drying process may be performed once or twice or more between the processes A to C or between the processes included in the processes A to C.

[0149] (Processing steps)

[0150] The processing steps are after the surface modification steps. Figure 3 The second surface 12 shown in (b) is selectively processed.

[0151] The processing may include, for example, a film forming process of forming a film on the second surface 12 by atomic layer deposition and / or an etching process of etching the second surface 12 .

[0152] When the film formation process is performed, film formation by the atomic layer deposition method is suppressed on the first surface 11 , but film formation by the atomic layer deposition method is completed on the second surface 12 .

[0153] When the first surface 11 has good water repellency, it can be seen that there is a tendency that the film formation using the atomic layer deposition method is hindered. Although the detailed mechanism is uncertain, it can be inferred that if the first surface 11 is protected by a water repellent film, the film formation using the atomic layer deposition method is inhibited. On the other hand, the second surface 12 is treated by water repellency adjustment to remove the water repellent film on the surface and the compound derived from the silylating agent, so it can be inferred that the second surface 12 can be selectively treated for film formation compared to the first surface 11.

[0154] As a film forming method using atomic layer deposition, a known ALD device can be used. For example, preferably used are: a thin film forming method using adsorption of a first gas phase reaction material as a film forming raw material and a desired second gas phase reaction material (thermal ALD method); a thin film forming method in which the first gas phase reaction material as a film forming raw material is adsorbed on the surface and then reacted with plasma of oxygen or the like (plasma ALD method), etc. The film forming temperature and film forming time can be appropriately selected according to the film thickness and the raw material.

[0155] The first gas phase reaction material uses a material containing a film forming material. Examples of the first gas phase reaction material include organic metals, metal halides, metal halides, and the like, and specifically include pentaethoxytantalum, tetrakis(dimethylamino)titanium, penta(dimethylamino)tantalum, tetrakis(dimethylamino)zirconium, tetrakis(dimethylamino)hafnium, tetrakis(dimethylamino)silane, bis(hexafluoroacetylacetonate)copper, Zn(C2H5)2, Zn(CH3)2, TMA (trimethylaluminum), TaCl5, WF6, WOCl4, CuCl, ZrCl4, AlCl3, TiCl4, SiCl4, HfCl4, and the like.

[0156] The second gas phase reaction material may be any material as long as it contains a gas that can react with the first gas phase reaction material or a material that can generate active species such as free radicals, for example, H2, H2O, H2O2, O2, O3, HCl, HF, NH3, H2S, H2Se, PH3, AsH3, CH4, C2H4 or Si2H6.

[0157] There are no particular restrictions on the films formed by atomic layer deposition, and examples include: films containing pure elements (such as Si, Cu, Ta, and W), films containing oxides (such as SiO2, GeO2, HfO2, ZrO2, Ta2O5, TiO2, Al2O3, ZnO, SnO2, Sb2O5, B2O3, In2O3, and WO3), films containing nitrides (such as Si3N4, TiN, AlN, BN, GaN, and NbN), films containing carbides (such as SiC), films containing sulfides (such as CdS, ZnS, MnS, WS2, and PbS), films containing selenides (such as CdSe and ZnSe), films containing phosphides (GaP and InP), films containing arsenides (such as GaAs and InAs), or mixtures thereof.

[0158] When etching is performed as the processing, the etching of the first surface 11 is suppressed, but the second surface 12 is etched further than the first surface. Therefore, the second surface 12 can be selectively etched compared to the first surface 11.

[0159] The detailed mechanism is not clear, but it is estimated that the etching of the first surface 11 is suppressed more than the etching of the second surface 12 because the remaining water-repellent film 21 functions as a shielding material for the etchant.

[0160] The etching process is not particularly limited as long as it is a method capable of etching the second surface 12 , and a known dry etching method or wet etching method can be selected.

[0161] In addition, it is preferred to use an etchant for various etching treatments. In the case of gas, for example, halogen compound gases such as Cl2 gas, F2 gas, ClF3 gas, IF7 gas, NH3 gas, and mixed gases containing these various gases can be listed. In the case of liquid, liquids obtained by diluting at least one of HF, NH4F, NH4HF2, H3PO4 and H2SO4 with a solvent can be listed. In addition, the above-mentioned etchant can also be heated, or used to form plasma or free radicals.

[0162] In addition, when the value of the water contact angle of the first surface after the surface modification step and immediately before the processing step is performed is defined as S1, and the value of the water contact angle of the second surface is defined as S2, the value calculated by "(S1-S2) / S2" is preferably 1.0 or more. By being within this range, the selectivity during the processing step, especially the selectivity during ALD film formation, is likely to be good, so it is suitable. In addition, (S1-S2) / S2 may also be more preferably 1.5 or more.

[0163] In addition, the water contact angle S1 of the first surface 11 is preferably 65° or more. By being within the aforementioned range, the selective processability becomes easy to improve. In particular, it is suitable during etching. The water contact angle S1 may also be preferably 70° or more, and may more preferably be 75° or more. In addition, the water contact angle S2 of the aforementioned second surface 12 is not particularly limited as long as it satisfies (S1-S2) / S2≥1.0. For example, if it becomes 60° or less, it becomes easy to improve the selective processability, so it is preferred. It may also be more preferably 56° or less.

[0164] When the water-repellent film remaining on the first surface after the above processing step is no longer necessary, the water-repellent film may be removed. The removal method is not particularly limited as long as it is a known method capable of removing the silylation group.

[0165] For example, light (ultraviolet) irradiation, heat treatment, ozone exposure, plasma irradiation, corona discharge, etc. It can also be removed by a wet manufacturing process, for example, contact with an aqueous ammonium hydroxide solution, a tetramethylammonium solution, an aqueous hydrochloric acid solution, an aqueous sulfuric acid solution, etc.

[0166] The method for manufacturing a substrate of the present embodiment includes a step of obtaining a substrate subjected to each step in the above-mentioned method for treating a substrate. By the method for manufacturing a substrate, a desired semiconductor wafer or semiconductor device can be obtained.

[0167] <Silylating Agent>

[0168] The silylating agent used for the silylation treatment in the above-mentioned substrate treatment method and the silylation composition containing the silylation agent are described.

[0169] As the silylating agent, a known silylating agent can be used.

[0170] Examples of silylating agents include silicon compounds represented by the following general formula [1]. These may be used alone or in combination of two or more. When two or more are combined, this may be referred to as a "silylating composition". In addition, the silicon compound contained in the silylating composition may be present in R of the following general formula [1]. 1 The carbon numbers of the two radicals may be the same or different.

[0171] R 1 a Si(H) b X 4-a-b [1]

[0172] In the above general formula [1], R 1Each of them is independently an organic group of a hydrocarbon group having 1 to 18 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements; each of X is independently a monovalent organic group in which the element bonded to the Si element is nitrogen, oxygen, carbon or halogen, a is an integer of 1 to 3, b is an integer of 0 to 2, and the total of a and b is 1 to 3.

[0173] In the above general formula [1], R 1 , can contain not only hydrogen, carbon, nitrogen, oxygen, and fluorine elements, but also silicon, sulfur, and halogen elements (other than fluorine).

[0174] In addition, R in the above general formula [1] 1 It may also contain an unsaturated bond, an aromatic ring, or a cyclic structure.

[0175] As R in the above general formula [1] 1 , for example, they can be listed as: each independently selected from C e H 2e+1 (e=1~18) and C f F 2f+1 At least one group of CH2CH2 (f=1 to 8) Among these, a silicon compound having a trialkylsilyl group is particularly preferably used.

[0176] It should be noted that in the above general formula [1], R 1 When silicon element is contained, the above general formula [1] may also take the structure of the general formula [1-1] shown below.

[0177] R 1 m X 3-m-n (H) n Si-(CH2) p -Si(H) n X 3-m-n R 1 m [1-1]

[0178] It should be noted that in the above general formula [1-1], R 1 (Among them, in this R 1 does not contain silicon) and X is the same as the above general formula [1], m is an integer of 1 to 2, n is an integer of 0 to 1, the sum of m and n is 1 to 2, p is an integer of 1 to 18, and -(CH2) p -The methylene chains shown may also be substituted by halogen.

[0179] In X in the general formula [1], the monovalent organic group in which the element bonded to the Si element is nitrogen, oxygen or carbon may contain not only hydrogen, carbon, nitrogen and oxygen elements but also silicon, sulfur and halogen elements.

[0180] Examples of the monovalent organic group in which the element bonded to the Si element is nitrogen include an isocyanate group, an amino group, a dialkylamino group, an isothiocyanate group, an azido group, an acetamide group, -NHC(=O)CF3, -N(CH3)C(=O)CH3, -N(CH3)C(=O)CF3, -N=C(CH3)OSi(CH3)3, -N=C(CF3)OSi(CH3)3, -NHC(=O)-OSi(CH3)3, -NHC(=O)-NH-Si(CH3)3, an imidazole ring, a triazole ring, a tetrazole ring, an oxazolidinone ring, a morpholine ring, -NH-C(=O)-Si(CH3)3, -N[S(=O)2R 4 )2(Here, R 4 Each of the substituents is independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally substituted with fluorine elements, and a fluorine element, and has a structure of the following general formula [1-2].

[0181]

[0182] (In the above general formula [1-2], R 5 Each independently represents a divalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements. ), -N=C(NR 6 2) 2, -N=C(NR 6 2) R 6 (Here, R 6 Each of the following is independently selected from a hydrogen group, a -C≡N group, a -NO2 group, and a hydrocarbon group in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and the above hydrocarbon group optionally has oxygen atoms and / or nitrogen atoms. ), -N(R a1 )(R a2 )(Here, the above R a1 represents a hydrogen atom or a saturated or unsaturated alkyl group, R a2 R represents a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group or a saturated or unsaturated heterocycloalkyl group. a1 and R a2 They may also be bonded to each other to form a saturated or unsaturated heterocyclic alkyl group having a nitrogen atom. ), -N(R a3 )-Si(R a4 )(R a5 )(R a6 )(Here, the above R a3 represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, a trimethylsilyl group or a dimethylsilyl group, and the above R a4 , R a5 and R a6 Each independently represents a hydrogen atom or an organic group, R a4 , Ra5 and R a6 The total number of carbon atoms contained is 1 or more. ), -N(R a7 )-C(=O)R a8 (Here, the above R a7 represents a hydrogen atom, a methyl group, a trimethylsilyl group or a dimethylsilyl group, R a8 represents a hydrogen atom, a saturated or unsaturated alkyl group, a fluorine-containing alkyl group or a trialkylsilylamino group. ) and the like.

[0183] Examples of silylating agents in which X in the general formula [1] is a monovalent organic group in which the element bonded to the Si element is nitrogen include CH3Si(NH2)3, C2H5Si(NH2)3, C3H7Si(NH2)3, C4H9Si(NH2)3, C5H 11 Si(NH2)3、C6H 13 Si(NH2)3、C7H 15 Si(NH2)3、C8H 17 Si(NH2)3、C9H 19 Si(NH2)3、C 10 H 21 Si(NH2)3、C 11 H 23 Si(NH2)3、C 12 H 25 Si(NH2)3、C 13 H 27 Si(NH2)3、C 14 H 29 Si(NH2)3、C 15 H 31 Si(NH2)3、C 16 H 33 Si(NH2)3、C 17 H 35 Si(NH2)3、C 18 H 37 Si(NH2)3, (CH3)2Si(NH2)2, C2H5Si(CH3)(NH2)2, (C2H5)2Si(NH2)2, C3H7Si(CH3)(NH2)2, (C3H7)2Si(NH2)2, C4H9Si(CH3)(NH2)2, (C4H9)2Si(NH2)2, C5H 11 Si(CH3)(NH2)2、C6H 13 Si(CH3)(NH2)2、C7H 15 Si(CH3)(NH2)2、C8H 17 Si(CH3)(NH2)2、C9H19 Si(CH3)(NH2)2、C 10 H 21 Si(CH3)(NH2)2、C 11 H 23 Si(CH3)(NH2)2、C 12 H 25 Si(CH3)(NH2)2、C 13 H 27 Si(CH3)(NH2)2、C 14 H 29 Si(CH3)(NH2)2、C 15 H 31 Si(CH3)(NH2)2、C 16 H 33 Si(CH3)(NH2)2、C 17 H 35 Si(CH3)(NH2)2、C 18 H 37 Si(CH3)(NH2)2、(CH3)3SiNH2、C2H5Si(CH3)2NH2、(C2H5)2Si(CH3)NH2、(C2H5)3SiNH2、C3H 7Si(CH3)2NH2、(C3H7)2Si(CH3)NH2、(C3H7)3SiNH2、C4H9Si(CH3)2NH2、(C4H9)3SiNH2、C5H 11 Si(CH3)2NH2、C6H 13 Si(CH3)2NH2、C7H 15 Si(CH3)2NH2、C8H 17 Si(CH3)2NH2、C9H 19 Si(CH3)2NH2、C 10 H 21 Si(CH3)2NH2、C 11 H 23 Si(CH3)2NH2、C 12 H 25 Si(CH3)2NH2、C 13 H 27 Si(CH3)2NH2、C 14 H 29 Si(CH3)2NH2、C 15 H 31 Si(CH3)2NH2、C 16 H 33 Si(CH3)2NH2、C 17 H 35 Si(CH3)2NH2、C18 H 37 Si(CH3)2NH2, (CH3)2Si(H)NH2, CH3Si(H)2NH2, (C2H5)2Si(H)NH2, C2H5Si(H)2NH2, C2H5Si(CH3)(H)NH2, (C3H7)2Si( H)NH2, C3H7Si(H)2NH2, CF3CH2CH2Si(NH2)3, C2F5CH2CH2Si(NH2)3, C3F7CH2CH2Si(NH2)3, C4F9CH2CH2Si(NH2)3, C5F 11 CH2CH2Si(NH2)3、C6F 13 CH2CH2Si(NH2)3、C7F 15 CH2CH2Si(NH2)3、C8F 17 CH2CH2Si(NH2)3, CF3CH2CH2Si(CH3)(NH2)2, C2F5CH2CH2Si(CH3)(NH2)2, C3F7CH2CH2Si(CH3)(NH2)2, C4F9CH2CH2Si(CH3)(NH2)2, C5F 11 CH2CH2Si(CH3)(NH2)2、C6F 13 CH2CH2Si(CH3)(NH2)2、C7F 15 CH2CH2Si(CH3)(NH2)2、C8F 17 CH2CH2Si(CH3)(NH2)2, CF3CH2CH2Si(CH3)2NH2, C2F5CH2CH2Si(CH3)2NH2, C3F7CH2CH2Si(CH3)2NH2, C4F9CH2CH2Si(CH3)2NH2, C5F 11 CH2CH2Si(CH3)2NH2、C6F 13 CH2CH2Si(CH3)2NH2、C7F 15 CH2CH2Si(CH3)2NH2、C8F 17 Aminosilanes such as CH2CH2Si(CH3)2NH2, CF3CH2CH2Si(CH3)(H)NH2, aminodimethylvinylsilane, aminodimethylphenylethylsilane, aminodimethylphenylsilane, aminomethyldiphenylsilane, and aminodimethyltert-butylsilane.

[0184] In addition, examples include those in which the amino group (-NH2 group) of the aminosilane is substituted with the following groups: -N=C=O, dialkylamino (-N(CH3)2, -N(C2H5)2, etc.), tert-butylamino, allylamino, -N=C=S, -N3, -NHC(=O)CH3, -NHC(=O)CF3, -N(CH3)C(=O)CH3, -N(CH3)C(=O)CF3, -N=C(CH3)OSi(CH3 )3, -N=C(CF3)OSi(CH3)3, -NHC(=O)-OSi(CH3)3, -NHC(=O)-NH-Si(CH3)3 (e.g., N,N'-bis(trimethylsilyl)urea, etc.), imidazole ring (e.g., N-trimethylsilylimidazole, etc.), triazole ring (e.g., N-trimethylsilyltriazole, etc.), tetrazole ring, oxazolidinone ring, morpholine ring, -NH-C(=O)-Si(CH3)3, -N[S(=O)2R 4 )2(Here, R 4 Each is independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and a fluorine element. For example, N-(trimethylsilyl)bis(trifluoromethanesulfonyl)imide, etc. ), and a substituent having a structure of the following general formula [1-2].

[0185]

[0186] (In the above general formula [1-2], R 5 Each independently represents a divalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements. For example, N-(trimethylsilyl)-N,N-difluoromethyl-1,3-bis(sulfonyl)imide (etc.), -N=C(NR 6 2) 2, -N=C(NR 6 2) R 6 (Here, R 6 Each independently selected from a hydrogen group, a -C≡N group, a -NO2 group, and a hydrocarbon group in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and the above hydrocarbon group may also have oxygen atoms and / or nitrogen atoms. For example, 2-trimethylsilyl-1,1,3,3-tetramethylguanidine, etc.), -N(R a1 )R a2 (Here, the above R a1 represents a hydrogen atom or a saturated or unsaturated alkyl group, R a2 R represents a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group or a saturated or unsaturated heterocycloalkyl group. a1 and R a2 They may also be bonded to each other to form a saturated or unsaturated heterocyclic alkyl group having a nitrogen atom. ), -N(R a3 )-Si(Ra4 )(R a5 )(R a6 )(Here, the above R a3 represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, a trimethylsilyl group or a dimethylsilyl group, and the above R a4 , R a5 and R a6 Each independently represents a hydrogen atom or an organic group, R a4 , R a5 and R a6 The total number of carbon atoms contained is 1 or more. For example: hexamethyldisilazane, N-methylhexamethyldisilazane, 1,1,3,3-tetramethyldisilazane, 1,3-dimethyldisilazane, 1,3-di-n-octyltetramethyldisilazane, 1,3-divinyltetramethyldisilazane, heptamethyldisilazane, N-allyl-N,N-bis(trimethylsilyl)amine, 1,3-diphenyltetramethyldisilazane and 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane, nonamethyltrisilazane, pentamethylethyldisilazane, pentamethylvinyldisilazane, pentamethylpropyldisilazane, pentamethylethyldisilazane, pentamethyl-tert-butyldisilazane, pentamethylphenyldisilazane, trimethyltriethyldisilazane, etc. ), -N(R a7 )-C(=O)R a8 (Here, the above R a7 represents a hydrogen atom, a methyl group, a trimethylsilyl group or a dimethylsilyl group, R a8 represents a hydrogen atom, a saturated or unsaturated alkyl group, a fluorinated alkyl group or a trialkylsilylamino group. For example: N-trimethylsilylacetamide, N-trimethylsilyltrifluoroacetamide, N-methyl-N-trimethylsilylacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide, bis(trimethylsilyl)acetamide, bis(trimethylsilyl)trifluoroacetamide, etc.).

[0187] Examples of the silylating agent in the general formula [1] in which X is a monovalent organic group in which the element bonded to the Si element is oxygen include, for example, a substance in which the amino group (-NH2 group) of the aminosilane is substituted with the following group: -OC(=A)R a9 (Here, the above A represents O, CHR a10 , CHOR a10 , CR a10 R a10 or NR a11 , R a9 , R a10 Each independently represents a hydrogen atom, a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, a fluorine-containing alkyl group, a chlorine-containing alkyl group, a trialkylsilyl group, a trialkylsiloxy group, an alkoxy group, a phenyl group, a phenethyl group or an acetyl group, and the above Ra11 represents a hydrogen atom, an alkyl group or a trialkylsilyl group. For example: trimethylsilyl acetate, dimethylsilyl acetate, monomethylsilyl acetate, trimethylsilyl trifluoroacetate, dimethylsilyl trifluoroacetate, monomethylsilyl trifluoroacetate, trimethylsilyl trichloroacetate, trimethylsilyl propionate, trimethylsilyl butyrate, etc.), -OC(R a12 )=N(R a13 )(Here, the above R a12 represents a hydrogen atom, a saturated or unsaturated alkyl group, a fluorinated alkyl group or a trialkylsilylamino group, R a13 represents a hydrogen atom, an alkyl group, or a trialkylsilyl group. ), -OC(R a14 )=CH-C(=O)R a15 (Here, the above R a14 and R a15 Each independently represents a hydrogen atom or an organic group. For example: trimethylsilyloxy-3-penten-2-one, 2-trimethylsilyloxypent-2-en-4-one, etc. ), -OR a16 (Here, the above R a16 represents a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, or a fluorinated alkyl group. a16 Silylating agents, such as CH3Si(OCH3)3, C2H5Si(OCH3)3, C3H7Si(OCH3)3, C4H9Si(OCH3)3, C5H 11 Si(OCH3)3、C6H 13 Si(OCH3)3、C7H 15 Si(OCH3)3、C8H 17 Si(OCH3)3、C9H 19 Si(OCH3)3、C 10 H 21 Si(OCH3)3、C 11 H 23 Si(OCH3)3、C 12 H 25 Si(OCH3)3、C 13 H 27 Si(OCH3)3、C 14 H 29 Si(OCH3)3、C 15 H 31 Si(OCH3)3、C 16 H 33 Si(OCH3)3、C 17 H 35 Si(OCH3)3、C 18 H 37<h2 style=";text-align:left;direction:ltr">Si(OCH3)3, (CH3)2Si(OCH3)2, C2H5Si(CH3)(OCH3)2, (C2H5)2Si(OCH3)2, C3H7Si(CH3)(OCH3)2, (C3H7)2Si(OCH3)2, C4H9Si(CH3)(OCH3)2, (C4H9)2Si(OCH3)2, C5H<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(OCH3)2, C6H<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(OCH3)2, C7H<h2 style=";text-align:left;direction:ltr"> 15 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(OCH3)2, C8H<h2 style=";text-align:left;direction:ltr"> 17 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(OCH3)2, C9H<h2 style=";text-align:left;direction:ltr"> 19 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(OCH3)2、C<h2 style=";text-align:left;direction:ltr"> 10 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 21 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(OCH3)2、C<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 23 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(OCH3)2、C<h2 style=";text-align:left;direction:ltr"> 12 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 25 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(OCH3)2、C<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 27 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(OCH3)2、C<h2 style=";text-align:left;direction:ltr"> 14 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 29 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(OCH3)2、C<h2 style=";text-align:left;direction:ltr"> 15 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 31 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(OCH3)2、C<h2 style=";text-align:left;direction:ltr"> 16 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 33 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(OCH3)2、C<h2 style=";text-align:left;direction:ltr"> 17 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 35 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(OCH3)2、C<h2 style=";text-align:left;direction:ltr"> 18 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 37 <h2 style=";text-align:left;direction:ltr"> Si(CH3)(OCH3)2, (CH3)3SiOCH3, C2H5Si(CH3)2OCH3, (C2H5)2Si(CH3)OCH3, (C2H5)3SiOCH3, C3H7Si(CH3)2OCH3, (C3H7)2Si(CH3)OCH3, (C3H7)3SiOCH3, C4H9Si(CH3)2OCH3, (C4H9)3SiOCH3, C5H<h2 style=";text-align:left;direction:ltr"> 11 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2OCH3, C6H<h2 style=";text-align:left;direction:ltr"> 13 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2OCH3, C7H<h2 style=";text-align:left;direction:ltr"> 15 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2OCH3, C8H<h2 style=";text-align:left;direction:ltr"> 17 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2OCH3, C9H<h2 style=";text-align:left;direction:ltr"> 19 <h2 style=";text-align:left;direction:ltr"> Si(CH3)2OCH3, C<h2 style=";text-align:left;direction:ltr"> 10 <h2 style=";text-align:left;direction:ltr"> H<h2 style=";text-align:left;direction:ltr"> 21Si(CH3)2OCH3, C 11 H 23 Si(CH3)2OCH3, C 12 H 25 Si(CH3)2OCH3, C 13 H 27 Si(CH3)2OCH3, C 14 H 29 Si(CH3)2OCH3, C 15 H 31 Si(CH3)2OCH3, C 16 H 33 Si(CH3)2OCH3, C 17 H 35 Si(CH3)2OCH3, C 18 H 37 Si(CH3)2OCH3, (CH3)2Si(H)OCH3, CH3Si(H)2OCH3, (C2H5)2Si(H)OCH3, C2H5Si(H)2OCH3, C2H5Si(CH3)(H)OCH3, (C3H7)2Si(H)OCH3 and other alkylmethoxysilanes; or CF3CH2CH2Si(OCH3)3, C2F5CH2CH2Si(OCH3)3, C3F7CH2CH2Si(OCH3)3, C4F9CH2CH2Si(OCH3)3, C5F 11 CH2CH2Si(OCH3)3, C6F 13 CH2CH2Si(OCH3)3, C7F 15 CH2CH2Si(OCH3)3, C8F 17 CH2CH2Si(OCH3)3, CF3CH2CH2Si(CH3)(OCH3)2, C2F5CH2CH2Si(CH3)(OCH3)2, C3F7CH2CH2Si(CH3)(OCH3)2, C4F9CH2CH2Si(CH3)(OCH3)2, C5F 11 CH2CH2Si(CH3)(OCH3)2, C6F 13 CH2CH2Si(CH3)(OCH3)2, C7F 15 CH2CH2Si(CH3)(OCH3)2, C8F 17 CH2CH2Si(CH3)(OCH3)2, CF3CH2CH2Si(CH3)2OCH3, C2F5CH2CH2Si(CH3)2OCH3, C3F7CH2CH2Si(CH3)2OCH3, C4F9CH2CH2Si(CH3)2OCH3, C5F11 CH2CH2Si(CH3)2OCH3、C6F 13 CH2CH2Si(CH3)2OCH3、C7F 15 CH2CH2Si(CH3)2OCH3、C8F 17 Fluoroalkylmethoxysilanes such as CH2CH2Si(CH3)2OCH3, CF3CH2CH2Si(CH3)(H)OCH3, or compounds obtained by replacing the methyl group of the methoxy group of the above methoxysilane with a monovalent hydrocarbon group having 2 to 18 carbon atoms in which a part or all of the hydrogen element is optionally replaced by a fluorine element, etc.), -OS(=O)2-R a17 (Here, the above R a17 It represents an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group, a phenyl group, a tolyl group, an -O-Si(CH3)3 group (for example: trimethylsilyl sulfonate, trimethylsilyl benzenesulfonate, trimethylsilyl toluenesulfonate, trimethylsilyl trifluoromethanesulfonate, trimethylsilyl perfluorobutanesulfonate, bistrimethylsilyl sulfate, etc.), -OP[-O-Si(CH3)3)2 (for example: tris(trimethylsilyl)phosphite, etc.).

[0188] In addition, examples of the silylating agent in the general formula [1] in which X is a monovalent organic group in which the element bonded to the Si element is oxygen include hexamethyldisiloxane, 1,3-diphenyl-1,3-dimethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, 1,1,1-triethyl-3,3-dimethyldisiloxane, 1,1,3,3-tetra-n-octyldimethyldisiloxane, bis(nonafluorohexyl)tetramethyldisiloxane, 1,3-bis(trifluoropropyl)tetramethyldisiloxane, 1,3-di-n-butyltetramethyldisiloxane, 1,3-di-n-octyltetramethyldisiloxane, 1,3-diethyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, hexa-n-butyldisiloxane, disiloxane, hexaethyl disiloxane, hexavinyl disiloxane, 1,1,3,3-tetraisopropyl disiloxane, vinyl pentamethyl disiloxane, 1,3-bis(3-chloroisobutyl)tetramethyl disiloxane, hexaphenyl disiloxane, 1,1,1-triethyl-3,3,3-trimethyl disiloxane, 1,3-bis(chloromethyl)tetramethyl disiloxane, 1,1,3,3-tetraphenyl dimethyl disiloxane, pentamethyl disiloxane, 1,3-bis(3-chloropropyl)tetramethyl disiloxane, 1,3-dichloro-1,3-diphenyl-1,3-dimethyl disiloxane, n-butyl-1,1,3,3-tetramethyl disiloxane, 1,3-di(tert-butyl) disiloxane, vinyl-1,1,3,3-tetramethyl Disiloxane, 1,1,1-trimethyl-3,3,3-triphenyldisiloxane, 3,3-diphenyltetramethyl trisiloxane, 3-phenylheptamethyl trisiloxane, hexamethylcyclotrisiloxane, n-propylheptamethyl trisiloxane, 3-ethylheptamethyl trisiloxane, 3-(3,3,3-trifluoropropyl)heptamethyl trisiloxane, 1,1,3,5,5-pentaphenyl-1,3,5-trimethyl trisiloxane, octamethyl trisiloxane, 1,1,5,5-tetraphenyl-1,3,3,5-tetramethyl trisiloxane, hexaphenylcyclotrisiloxane, 1,1,1,5,5,5-hexamethyl trisiloxane, 3-phenyl-1,1,3,5,5-pentamethyl trisiloxane, 1,3,5-trivinyl-1,1,3 ,5,5-pentamethyltrisiloxane, 1,3,5-trivinyl-1,3,5-trimethylcyclotrisiloxane, 3-octylheptamethyltrisiloxane, 1,3,5-triphenyltrimethylcyclotrisiloxane, 1,1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,3,3,5,5-hexamethyltrisiloxane, 1,1,1,5,5,5-hexaethyl-3-methyltrisiloxane, furfuryloxytrisiloxane, tetrakis(dimethylsiloxy)silane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, diphenylsiloxane-dimethylsiloxane copolymer, 1,3-diphenyl-1,3-dimethyldisiloxane, octamethylcyclotetrasiloxane, 1,3-bis(trimethylsiloxy)-1,Siloxane compounds such as 3-dimethyldisiloxane, tetra-n-propyltetramethylcyclotetrasiloxane, octaethylcyclotetrasiloxane, decamethyltetrasiloxane, dodecamethylcyclohexasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexaphenylcyclotrisiloxane, polydimethylsiloxane, polyoctadecylmethylsiloxane, decamethylcyclopentasiloxane, poly(3,3,3-trifluoropropylmethylsiloxane), trimethylsiloxy-terminated polydimethylsiloxane, and 1,1,3,3,5,5,7,7,9,9-decamethylpentasiloxane.

[0189] Examples of silylating agents in which X in the general formula [1] is a monovalent organic group in which the element bonded to the Si element is carbon include: 7 )3(Here, R 7 Each is independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and a fluorine element, for example, (trimethylsilyl) tris(trifluoromethanesulfonyl) methyl, etc.

[0190] In addition, as a silylating agent in the general formula [1], X is a monovalent organic group in which the element bonded to the Si element is a halogen, for example, substances in which the amino group (-NH2 group) of the above-mentioned aminosilane is replaced by a chloro group, a bromo group, or an iodine group (for example, chlorotrimethylsilane, bromotrimethylsilane, etc.) can be listed.

[0191] The silylating agent may contain a cyclic silazane compound.

[0192] Examples of the cyclic silazane compound include cyclic disilazane compounds such as 2,2,5,5-tetramethyl-2,5-disilyl-1-azacyclopentane and 2,2,6,6-tetramethyl-2,6-disilyl-1-azacyclohexane; cyclic trisilazane compounds such as 2,2,4,4,6,6-hexamethylcyclotrisilazane and 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane; and cyclic tetrasilazane compounds such as 2,2,4,4,6,6,8,8-octamethylcyclotetrasilazane.

[0193] When the silylating agent is supplied in a gaseous state such as gas, it can also be supplied in the form of a mixed gas used simultaneously with an inert gas. Examples of the inert gas include N2, Ar, He, Ne, and CF4. Preferably, N2, Ar, and He can also be used.

[0194] The silylation composition refers to a composition of a combination of two or more of the above-mentioned silylation agents, or a composition comprising the above-mentioned mixed gas, a silylation agent and compounds other than the above-mentioned mixed gas. In addition to the above-mentioned silylation agent, the above-mentioned silylation composition may also contain a catalytic compound that promotes the silylation reaction based on the silylation agent. As the catalytic compound, it is preferred to use one or more selected from the group consisting of the compound A described later, imide compounds, nitrogen-containing compounds, nitrogen-containing heterocyclic compounds not containing silicon atoms, and silylated heterocyclic compounds.

[0195] Here, the catalytic compound refers to a substance that can promote the reaction between the above-mentioned surfaces and the silylating agent or improve the water repellency of the formed water repellent film, and the catalytic compound itself or a modified product thereof may constitute a part of the water repellent film.

[0196] The concentration of the catalytic compound may be, for example, 0.005% by mass or more and 20% by mass or less, or 0.05% by mass or more and 15% by mass or less, relative to 100% by mass of the silylation composition.

[0197] As a specific example of the above-mentioned compound A, for example, trimethylsilyl trifluoroacetate, trimethylsilyl trifluoromethanesulfonate, dimethylsilyl trifluoroacetate, dimethylsilyl trifluoromethanesulfonate, butyldimethylsilyl trifluoroacetate, butyldimethylsilyl trifluoromethanesulfonate, hexyldimethylsilyl trifluoroacetate, hexyldimethylsilyl trifluoromethanesulfonate, octyldimethylsilyl trifluoroacetate, octyldimethylsilyl trifluoromethanesulfonate, decyldimethylsilyl trifluoroacetate and decyldimethylsilyl trifluoromethanesulfonate can be listed, and one or more selected from these can be included. These can be used alone or in combination of two or more.

[0198] It should be noted that the compound A may also correspond to the silylating agent, but when used as a catalytic compound, it means that the compound A used is used in combination with the silylating agent.

[0199] The compound A may be a compound obtained by reacting a silicon compound represented by the following general formula [2] with one or more acetic acids or sulfonic acids selected from the group consisting of trifluoroacetic acid, trifluoroacetic anhydride, trifluoromethanesulfonic acid, and trifluoromethanesulfonic anhydride.

[0200] The remaining silicon compound represented by the following general formula [2] which is not consumed in the reaction and remains can be used as the above-mentioned silylating agent together with the compound A obtained in the reaction. The silicon compound represented by the following general formula [2] can be reacted in a molar ratio of, for example, 0.2 to 100,000 times, preferably 0.5 to 50,000 times, and more preferably 1 to 10,000 times, relative to the above-mentioned acetic acid or sulfonic acid.

[0201] R2 c (H) d Si-X[2]

[0202] In the above general formula [2], R 2 c (H) d Si-, including: (CH3)3Si-, (CH3)2(H)Si-, (C4H9)(CH3)2Si-, (C6H 13 )(CH3)2Si-,(C8H 17 )(CH3)2Si-、(C 10 H 21 )(CH3)2Si-, etc. In addition, X is the same as in the above general formula [1].

[0203] The compound A may be at least one selected from the group consisting of a sulfonic acid represented by the following general formula [3], an anhydride of the sulfonic acid, a salt of the sulfonic acid, and a sulfonic acid derivative represented by the following general formula [4].

[0204] R 8 -S(=O)2OH[3]

[0205] [In the above general formula [3], R 8 A group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and a hydroxyl group.]

[0206] R 8’ -S(=O)2O-Si(H) 3-r (R 9 ) r [4]

[0207] [In the above general formula [4], R 8’ is a monovalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, R 9 Each independently represents at least one group selected from monovalent hydrocarbon groups having 1 to 18 carbon atoms in which a part or all of the hydrogen elements are optionally substituted with fluorine elements, and r is an integer of 1 to 3.]

[0208] The compound A may also be at least one selected from the group consisting of a sulfonate ester represented by the following general formula [5], a sulfonimide represented by the following general formulas [6] and [7], a sulfonimide derivative represented by the following general formulas [8] and [9], a sulfonylmethylated product represented by the following general formula

[10] , and a sulfonylmethylated product derivative represented by the following general formula

[11] .

[0209] R 10 -S(=O)2OR 11[5]

[0210] [In the above general formula [5], R 10 is a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and fluorine elements, and R 11 It is a monovalent alkyl group having 1 to 18 carbon atoms.]

[0211] (R 12 -S(=O)2)2NH[6]

[0212] [In the above general formula [6], R 12 Each is independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and a fluorine element.]

[0213]

[0214] [In the above general formula [7], R 13 A divalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements.]

[0215] ((R 14 -S(=O)2))2N) s Si(H) t (R 15 ) 4-s-t [8]

[0216] [In the above general formula [8], R 14 are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and a fluorine element, R 15 Each independently represents a monovalent hydrocarbon group having 1 to 18 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, s is an integer of 1 to 3, t is an integer of 0 to 2, and the total of s and t is 3 or less.]

[0217]

[0218] [In the above general formula [9], R 16 are each independently a divalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, R 17 Each independently represents a monovalent hydrocarbon group having 1 to 18 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, u is an integer of 1 to 3, v is an integer of 0 to 2, and the total of u and v is 3 or less.]

[0219] (R 18 -S(=O)2]3CH

[10]

[0220] [In the above general formula

[10] , R 18 Each is independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and a fluorine element.]

[0221] ((R 19 -S(=O)2)]3C) w Si(H) x (R 20 ) 4-w-x

[11]

[0222] [In the above general formula

[11] , R 19 are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and a fluorine element, R 20 Each independently represents a monovalent hydrocarbon group having 1 to 18 carbon atoms in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, w is an integer of 1 to 3, x is an integer of 0 to 2, and the total of w and x is 3 or less.]

[0223] Examples of the imide compound that can be used as the catalytic compound include compounds having a chemical structure obtained by imidizing an acid such as carboxylic acid or phosphoric acid.

[0224] In addition, examples of the nitrogen-containing compound that can be used as the catalytic compound include at least one of the compounds represented by the following general formulas

[12] and

[13] .

[0225] R 21 -N=C(NR 22 2)2

[12]

[0226] R 21 -N=C(NR 22 2) R 22

[13]

[0227] [In the above general formulas

[12] and

[13] , R 21 A hydrocarbon group selected from a hydrogen group, a -C≡N group, a -NO2 group, an alkylsilyl group, and a part or all of the hydrogen elements are optionally replaced by fluorine elements. The above hydrocarbon group may also have oxygen atoms and / or nitrogen atoms, but when containing nitrogen atoms, a non-cyclic structure is adopted. 22 Each independently selected from a hydrogen group, a -C≡N group, a -NO2 group, and a hydrocarbon group in which a part or all of the hydrogen elements are optionally replaced by fluorine elements, and the above hydrocarbon group may also have oxygen atoms and / or nitrogen atoms, but in the case of containing nitrogen atoms, a non-cyclic structure is adopted.]

[0228] Examples of the nitrogen-containing compound include compounds having a guanidine skeleton, such as guanidine, 1,1,3,3-tetramethylguanidine, 2-tert-butyl-1,1,3,3-tetramethylguanidine, 1,3-diphenylguanidine, 1,2,3-triphenylguanidine, N,N′-diphenylformamidine, and 2,2,3,3,3-pentafluoropropionamidine.

[0229] In addition, examples of the nitrogen-containing heterocyclic compound and silylated heterocyclic compound not containing a silicon atom that can be used as a catalytic compound include at least one compound represented by the following general formulas

[14] and

[15] .

[0230]

[0231] [In the above general formula

[14] , R 23 and R 24 Each is independently a divalent organic group composed of carbon and / or nitrogen and hydrogen, the total number of carbon atoms and nitrogen atoms is 1 to 9, and when the total number of carbon atoms is 2 or more, carbon atoms that do not form a ring may exist.]

[0232]

[0233] [In the above general formula

[15] , R 25 is an alkyl group having 1 to 6 carbon atoms in which a part or all of the hydrogen elements are optionally substituted with fluorine, a trialkylsilyl group having an alkyl group having 1 to 8 carbon atoms in which a part or all of the hydrogen elements are optionally substituted with fluorine, an alkenyl group having 2 to 6 carbon atoms in which a part or all of the hydrogen elements are optionally substituted with fluorine, an alkoxy group having 1 to 6 carbon atoms in which a part or all of the hydrogen elements are optionally substituted with fluorine, an amino group, an alkylamino group having an alkyl group having 1 to 6 carbon atoms in which a part or all of the hydrogen elements are optionally substituted with fluorine, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms in which a part or all of the hydrogen elements are optionally substituted with fluorine, an aminoalkyl group having 1 to 6 carbon atoms in which a part or all of the hydrogen elements are optionally substituted with fluorine, a nitro group, a cyano group, a phenyl group, a benzyl group, or a halogen group, and R 26 , R 27 and R 28 Each independently represents an alkyl group having 1 to 6 carbon atoms or a hydrogen group in which a part or all of the hydrogen atoms are optionally replaced by fluorine atoms. ]

[0234] In addition, the nitrogen-containing heterocyclic compound not containing a silicon atom may contain heteroatoms other than nitrogen atoms such as oxygen atoms and sulfur atoms in the ring, may have aromaticity, or may be a compound in which two or more rings are bonded by a single bond or a divalent or more polyvalent connecting group. In addition, it may have a substituent.

[0235] Examples of the nitrogen-containing heterocyclic compound not containing a silicon atom include pyridine, pyridazine, pyrazine, pyrimidine, triazine, tetrazine, pyrrole, pyrazole, imidazole, triazole, tetrazole, oxazole, isoxazole, thiazole, isothiazole, oxadiazole, thiadiazole, quinoline, isoquinoline, cinnoline, phthalazine, quinoxaline, quinazoline, indole, indazole, benzimidazole, benzotriazole, benzoxazole, benzisoxazole, benzothiazole, benzisothiazole, benzoxadiazole, benzothiadiazole, saccharin, pyrrolidine, and piperidine.

[0236] In addition, the silylated heterocyclic compound may include silylated imidazole compounds and silylated triazole compounds. Examples of the silylated heterocyclic compound include monomethyl silylimidazole, dimethyl silylimidazole, trimethyl silylimidazole, monomethyl silylitriazole, dimethyl silylitriazole, trimethyl silylitriazole, and the like.

[0237] It should be noted that the above-mentioned silylated heterocyclic compound may also correspond to the above-mentioned silylation agent, but when used as a catalytic compound, it means that it is used in combination with a silylation agent other than the silylated heterocyclic compound.

[0238] In the above-mentioned silylation composition, the concentration of the above-mentioned silylation agent, or the total concentration of the above-mentioned silylation agent and the above-mentioned catalytic compound, relative to 100 mass % of the above-mentioned silylation composition, may also be, for example, 0.01 mass % to 100 mass %, may preferably be 0.1 mass % to 50 mass %, and may more preferably be 0.5 mass % to 30 mass %.

[0239] Furthermore, when the silylation composition is liquid, the silylation composition may contain a solvent.

[0240] The solvent is not particularly limited as long as it dissolves the silylating agent. As the solvent, for example, organic solvents such as hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide-based solvents, alcohols, carbonate-based solvents, derivatives of polyols, nitrogen-containing solvents, organosilicon solvents, and thiols can be used. Among these, hydrocarbons, esters, ethers, halogen-containing solvents, sulfoxide-based solvents, and derivatives of polyols that do not have an OH group are preferred.

[0241] These may be used alone or in combination of two or more.

[0242] Examples of the hydrocarbons include linear, branched or cyclic hydrocarbon solvents, aromatic hydrocarbon solvents, and terpene solvents, including n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-tetradecane, n-hexadecane, n-octadecane, n-eicosane, and branched hydrocarbons having a carbon number corresponding thereto (e.g., isododecane, isohexadecane, etc.), cyclohexane, methylcyclohexane, decahydronaphthalene, benzene, toluene, xylene, (o-, m- or p-)diethylbenzene, 1,3,5-trimethylbenzene, naphthalene, mesitylene, p-menthane, o-menthane, m-menthane, diphenylmenthane, limonene, α-terpene, β-terpene, γ-terpene, bornane, norbornane, pinane, α-pinene, β-pinene, carene, longifolene, abietane, and terpene solvents.

[0243] Examples of the esters include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isopentyl acetate, n-hexyl acetate, n-heptyl acetate, n-octyl acetate, n-pentyl formate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl n-octanoate, methyl decanoate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-ketobutyrate, dimethyl adipate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, and the like.

[0244] As the above-mentioned esters, cyclic esters such as lactone compounds may also be used. Examples of lactone compounds include β-propiolactone, γ-butyrolactone, γ-valerolactone, γ-caprolactone, γ-heptanolactone, γ-octalactone, γ-nonalactone, γ-decalactone, γ-undecalactone, γ-dodecalactone, δ-valerolactone, δ-caprolactone, δ-octalactone, δ-nonalactone, δ-decalactone, δ-undecalactone, δ-dodecalactone, ε-caprolactone, etc.

[0245] Examples of the above-mentioned ethers include di-n-propyl ether, ethyl-n-butyl ether, di-tert-butyl ether, ethyl-n-pentyl ether, di-n-pentyl ether, ethyl-n-hexyl ether, di-n-hexyl ether, di-n-octyl ether and ethers having branched hydrocarbon groups such as diisopropyl ether and diisopentyl ether corresponding to the number of carbon atoms thereof, dimethyl ether, diethyl ether, methyl ethyl ether, methyl cyclopentyl ether, diphenyl ether, tetrahydrofuran, and dioxane.

[0246] Examples of the ketones include acetone, acetylacetone, methyl ethyl ketone, methyl acetone, methyl butyl ketone, 2-heptanone, 3-heptanone, cyclohexanone, and isophorone.

[0247] Examples of the halogen-containing solvent include perfluorooctane, perfluorononane, perfluorocyclopentane, perfluorocyclohexane, hexafluorobenzene and other perfluoroalkanes; 1,1,1,3,3-pentafluorobutane, octafluorocyclopentane, 2,3-dihydrodecafluoropentane, ZEORORA-H (manufactured by Zeon Corporation) and other hydrofluorocarbons; methyl perfluoropropyl ether, methyl perfluoroisobutyl ether, methyl perfluorobutyl ether, ethyl perfluorobutyl ether, ethyl perfluoroisobutyl ether, methyl perfluorohexyl ether, ethyl perfluorohexyl ether, ASAHIKLIN AE-3000 (manufactured by Asahi Glass Co., Ltd.), Novec HFE-7100, Novec HFE-7200, Novec 7300, Novec 7600 (all manufactured by 3M) and other hydrofluoroethers; chlorinated hydrocarbons such as tetrachloromethane; hydrochlorocarbons such as chloroform; chlorofluorocarbons such as dichlorodifluoromethane; hydrochlorofluorocarbons such as 1,1-dichloro-2,2,3,3,3-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1-chloro-3,3,3-trifluoropropene, 1,2-dichloro-3,3,3-trifluoropropene; perfluoroethers, perfluoropolyethers, etc.

[0248] Examples of the sulfoxide-based solvent include dimethyl sulfoxide and the like.

[0249] Examples of the carbonate-based solvent include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, and propylene carbonate.

[0250] Examples of the alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 4-methyl-1-pentanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 4-methyl-1-pentanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 4-methyl-2-pentanol, 2-methyl-2-butanol, 3 ... 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, benzyl alcohol, 1-octanol, 2-ethyl-1-hexanol, 3-hexanol, 4-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-3-pentanol, 2,2-dimethyl-1-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, benzyl alcohol, 1-octanol, 2-ethyl-1-hexanol, 4-methyl-2-pentanol, etc.

[0251] Examples of the substances which are derivatives of the above-mentioned polyols and do not have an OH group include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol diacetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ... triethylene glycol monobutyl ether acetate, diethylene glycol diacetate, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether, triethylene glycol butyl methyl ether, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, triethylene glycol monobutyl ether acetate, triethylene glycol diacetate, tetraethylene glycol dimethyl ether, tetraethylene glycol diethyl ether, tetraethylene glycol dibutyl ether, tetraethylene glycol monomethyl ether acetate, tetraethylene glycol monoethyl ether acetate, tetraethylene glycol monobutyl ether acetate, tetraethylene glycol di Acetate, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol diacetate, dipropylene glycol dimethyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, dipropylene glycol diacetate, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, Tripropylene glycol dibutyl ether, tripropylene glycol monomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate, tripropylene glycol diacetate, tetrapropylene glycol dimethyl ether, tetrapropylene glycol monomethyl ether acetate, tetrapropylene glycol diacetate, butylene glycol dimethyl ether, butylene glycol monomethyl ether acetate, butylene glycol diacetate, glycerol triacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, etc.

[0252] Examples of the nitrogen-containing solvent include formamide, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-diisopropyl-2-imidazolidinone, diethylamine, triethylamine, pyridine, and the like.

[0253] Examples of the organic silicon solvent include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, and dodecamethylpentasiloxane.

[0254] Examples of the above-mentioned thiols include 1-hexyl mercaptan, 2-methyl-1-pentyl mercaptan, 3-methyl-1-pentyl mercaptan, 4-methyl-1-pentyl mercaptan, 2,2-dimethyl-1-butyl mercaptan, 3,3-dimethyl-1-butyl mercaptan, 2-ethyl-1-butyl mercaptan, 1-heptyl mercaptan, benzyl mercaptan, 1-octyl mercaptan, 2-ethyl-1-hexyl mercaptan, 1-nonyl mercaptan, 1-decyl mercaptan, 1-undecyl mercaptan, 1-dodecyl mercaptan, 1-tridecyl mercaptan, and the like.

[0255] The above-mentioned solvent preferably contains an aprotic solvent. The content of the aprotic solvent is, for example, 80% by mass or more, preferably 90% by mass or more in 100% by mass of the above-mentioned solvent. The above-mentioned solvent is an aprotic solvent, that is, the solvent more preferably contains the aprotic solvent in an amount of 100% by mass in 100% by mass of the solvent.

[0256] Aprotic solvents include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxides, carbonate solvents, polyol derivatives, nitrogen-containing solvents, silicone solvents, etc. These may be used alone or in combination of two or more.

[0257] Among these, it is preferred to use one or two or more selected from the group consisting of polyol derivatives, hydrocarbons, and ethers.

[0258] From the viewpoint of cost and solubility, derivatives of polyols (those having no OH group in the molecule) are preferred, and examples thereof include diethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol diacetate, triethylene glycol dimethyl ether, ethylene glycol diacetate, and ethylene glycol dimethyl ether. , 3-methoxy-3-methyl-1-butyl acetate, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol diacetate, dipropylene glycol dimethyl ether, dipropylene glycol methyl propyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, dipropylene glycol diacetate. In addition, propylene carbonate, a linear or branched hydrocarbon solvent having 6 to 12 carbon atoms, p-menthane, diphenylmenthane, limonene, terpene, bornane, norbornane, pinane, etc. are also preferred.

[0259] As an example of a silylation composition comprising a silylation agent and a solvent, for example, the following composition can also be used: the silylation agent comprises a silylation agent selected from the group consisting of hexamethyldisilazane, heptamethyldisilazane, N-(trimethylsilyl)dimethylamine, bis(dimethylamino)dimethylsilane, bis(trimethylsilyl)trifluoroacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide, N-trimethylsilylacetamide, N-trimethylsilylimidazole, trimethylsilyltriazole, bistrimethylsilyl sulfate, 2,2,5,5-tetramethyl The solvent comprises one or more selected from the group consisting of propylene carbonate, a linear hydrocarbon solvent having 7 to 10 carbon atoms, menthane, pinane, γ-butyrolactone, propylene glycol monomethyl ether acetate and 3-methoxy-3-methyl-1-butyl acetate.

[0260] The silylation composition may contain no water, or may contain water in an amount of 2% by mass or less in 100% by mass of the silylation composition. In this manner, a silylation composition substantially containing no water may be used.

[0261] The silylation composition may contain other components other than the above components within the range not hindering the purpose of the present invention. Examples of other components include oxidants such as hydrogen peroxide and ozone, surfactants, and antioxidants such as BHT.

[0262] The silylation composition of the present embodiment can be obtained by mixing the above-mentioned components. The obtained mixed solution can also be purified using an adsorbent, a filter, etc. as needed. In addition, each component can also be purified by pre-distillation, using an adsorbent, a filter, etc.

[0263] The embodiments of the present invention have been described above, but these are examples of the present invention, and various structures other than the above can be adopted. In addition, the present invention is not limited to the above-mentioned embodiments, and modifications and improvements within the scope that can achieve the purpose of the present invention are included in the present invention.

[0264] Example

[0265] The present invention will be described in detail below with reference to Examples, but the present invention is not limited to the description of these Examples.

[0266] <Substrate Treatment>

[0267] Using the combination of substrates and treatment conditions shown in Table 1, the substrate prepared according to the following (1. Substrate preparation process) is subjected to the following (2. Surface modification process) pretreatment A, silylation treatment B and removal treatment C, and the substrate is treated in sequence. It should be noted that "SiOx" represents silicon oxide, SiN and SiGe represent silicon nitride and germanium silicide, respectively, and these composition ratios are not necessarily limited to Si:N=1:1, Si:Ge=1:1. In addition, none of the following is a simulation test in which a substrate having two surfaces is treated, but a substrate as the first surface and a substrate as the second surface are simply prepared for treatment.

[0268] [Table 1]

[0269]

[0270] (1. Base material preparation process)

[0271] The substrates having Si-based surface compositions shown in Table 1 were prepared as follows.

[0272] A smooth silicon substrate with a size of 30 mm×40 mm×1 mm was used as the substrate. When the surface composition used was Si, it was used as it was, and when it was another surface composition, a film with a desired surface composition was formed on the surface of the substrate.

[0273] (2. Surface modification process)

[0274] The treatment conditions of each treatment used in the surface modification step are as follows.

[0275] (2.1) Pre-processing A

[0276] (A-1) Removal of natural oxide film

[0277] The substrate was immersed in a 0.02 to 1 mass % hydrofluoric acid aqueous solution (DHF) at room temperature for 1 minute, then immersed in pure water as a rinse liquid for 1 minute, and then immersed in 2-propanol (IPA) for 1 minute.

[0278] (A-2a) Substrate Surface Oxidation Step

[0279] The substrate was placed in a UV / O3 device (manufactured by Novascan), and the surface of the substrate was subjected to UV / O3 treatment for 30 minutes.

[0280] (A-2b) Removal of natural oxide film and oxidation of substrate surface

[0281] At room temperature, the substrate was immersed in a 0.02-1 mass % hydrofluoric acid aqueous solution (DHF) for 1 minute, then immersed in an APM solution (a mixed solution of NH3OH:H2O2:H2O=1:10:70) for 1 minute, then immersed in pure water for 1 minute, and immersed in IPA for 1 minute.

[0282] (2.2) Silylation treatment B

[0283] The substrate was immersed in a silylating agent prepared by the following method at room temperature to perform silylating treatment on the surface of the substrate. In the case of the silylating agent B-1, B-3 and B-4, the immersion time was set to 60 seconds, and in the case of B-2, the immersion time was set to 20 seconds.

[0284] (Silylating agent B-1)

[0285] The silylating agent B-1 was obtained by weighing 5 g of hexamethyldisilazane (HMDS), 0.1 g of trimethylsilyl trifluoroacetate, and 94.9 g of propylene glycol monomethyl ether acetate (PGMEA) at room temperature and mixing them.

[0286] (Silylating agent B-2)

[0287] The silylating agent B-2 was obtained by weighing and mixing 12 g of HMDS, 4 g of trimethylsilyl trifluoroacetate, and 84 g of PGMEA at room temperature.

[0288] (Silylating agent B-3)

[0289] The silylating agent B-3 was obtained by weighing and mixing 7 g of 1,3-dibutyl-1,1,3,3-tetramethyldisilazane, 0.3 g of butyldimethylsilyl trifluoroacetate, and 92.7 g of PGMEA at room temperature.

[0290] (Silylating agent B-4)

[0291] The silylating agent B-4 was obtained by weighing and mixing 9 g of hexamethyldisilazane (HMDS)-1,3-dioctyl-1,1,3,3-tetramethyldisilazane, 0.5 g of octyldimethylsilyl trifluoroacetate, and 90.5 g of PGMEA at room temperature.

[0292] (2.3) Removal of treatment C

[0293] (C-1) Alkaline aqueous solution treatment

[0294] The substrate was immersed in a 3 mass % triethylamine aqueous solution at room temperature for 30 minutes, then immersed in pure water for 1 minute, and then immersed in IPA for 1 minute. The substrate was then taken out and dried by blowing air to remove IPA.

[0295] (C-2) Diluted Hydrogen Fluoride Water Treatment

[0296] The substrate was immersed in a 0.01-0.5 mass % aqueous solution of hydrogen fluoride at room temperature for 5 minutes, then immersed in pure water for 1 minute, and then immersed in IPA for 1 minute. The substrate was then taken out and dried by blowing air to remove IPA.

[0297] (C-3) Alkaline aqueous solution treatment

[0298] The substrate was immersed in a 3 mass % triethylamine aqueous solution at room temperature for 10 minutes, then immersed in pure water for 1 minute, and then immersed in IPA for 1 minute. The substrate was then taken out and dried by blowing air to remove IPA.

[0299] (C-4) Alkaline aqueous solution treatment

[0300] The substrate was immersed in a 3 mass % diisopropylamine aqueous solution at room temperature for 30 minutes, then immersed in pure water for 1 minute, and then immersed in IPA for 1 minute. The substrate was then taken out and dried by blowing air to remove IPA.

[0301] (C-5) Alkaline aqueous solution treatment

[0302] The substrate was immersed in a 3 mass % N,N-dimethylisopropylamine aqueous solution at room temperature for 30 minutes, then immersed in pure water for 1 minute, and then immersed in IPA for 1 minute. The substrate was then taken out and dried by blowing air to remove IPA.

[0303] (C-6) Alkaline aqueous solution treatment

[0304] The substrate was immersed in a 3 mass % N,N-diethylmethylamine aqueous solution at room temperature for 30 minutes, then immersed in pure water for 1 minute, and then immersed in IPA for 1 minute. The substrate was then taken out and dried by blowing air to remove IPA.

[0305] (C-7) Alkaline aqueous solution treatment

[0306] The substrate was immersed in a 3 mass % N,N-diisopropylethylamine aqueous solution at room temperature for 30 minutes, then immersed in pure water for 1 minute, and then immersed in IPA for 1 minute. The substrate was then taken out and dried by blowing air to remove IPA.

[0307] (C-8) Alkaline aqueous solution treatment

[0308] The substrate was immersed in a 10 mass % tetrabutylammonium hydroxide aqueous solution at room temperature for 1 minute, then immersed in pure water for 1 minute, and then immersed in IPA for 1 minute. The substrate was then taken out and dried by blowing air to remove IPA.

[0309] The following items were evaluated using the substrate during or after the treatment in the above-mentioned <Treatment of substrate>.

[0310] <Measurement and evaluation of water contact angle>

[0311] (Measurement of water contact angle)

[0312] The water contact angle (°) on the surface of the substrate was measured at respective time points immediately after the pretreatment A, immediately after the silylation treatment B, and immediately after the removal treatment C according to the following measurement procedure.

[0313] .Measurement method just after pre-treatment A:

[0314] First, if the substrate is wet after the treatment, air is blown to dry it. Then, the surface of the substrate that has been treated with A is placed horizontally with the surface facing upward, and a 2 μL drop of pure water is placed on the surface. Then, based on JIS R 3257:1999 "Test method for wettability of substrate glass surface", the angle (water contact angle) formed by the water drop and the substrate is measured by a contact angle meter (Kyowa Interface Science: CA-X model). In addition, the temperature during the measurement is room temperature (25°C).

[0315] . Determination method just after silylation treatment B:

[0316] First, the substrate immediately after the treatment was immersed in IPA at 25° C. for 1 minute. Then, air was blown to dry the substrate, and then the water contact angle was measured by the same procedure as the measurement immediately after the pretreatment A.

[0317] .Measurement method just after removal of treatment C:

[0318] The surface subjected to the silylation treatment B was placed horizontally with the surface facing upward, and then the water contact angle was measured in the same procedure as that immediately after the pretreatment A.

[0319] (Evaluation of Silylation Ratio)

[0320] The rate of increase in water repellency on the substrate surface caused by the silanization treatment B is evaluated according to the following evaluation criteria using the water contact angle (P) just before the silanization treatment B (in this embodiment, just after the pretreatment A) and the water contact angle (R) just after the silanization treatment B, and the "silanization ratio" calculated from "(RP) / P".

[0321] Large (A): When the silylation ratio is 5.0 or more

[0322] Small (B): When the silylation ratio exceeds 1.0 and is less than 5.0

[0323] Very small or no (C): When the silylation ratio is 1.0 or less

[0324] (Evaluation of retention / reduction of water repellency)

[0325] The maintenance or reduction of water repellency on the substrate surface caused by removal treatment C is evaluated according to the following evaluation criteria using the "contact angle change (ΔQ-R)" calculated from "water contact angle (Q) just after removal treatment C - water contact angle (R) just after silylation treatment B".

[0326] Maintain (+): When the contact angle change (ΔQ-R) is -10° or more

[0327] Decrease (-): When the contact angle change (ΔQ-R) is less than -10°

[0328] (Evaluation of water repellency after water repellency adjustment)

[0329] The change in water repellency before and after treatment by silylation treatment B and removal treatment C was evaluated. Specifically, the "water repellency improvement rate (Q / P)" calculated from "water contact angle (Q) immediately after removal treatment C / water contact angle (P) immediately before silylation treatment B (in this example, immediately after pretreatment A)" was used to evaluate according to the following evaluation criteria.

[0330] Excellent (A+): When the water repellency improvement ratio (Q / P) is 10.0 or more

[0331] Good (A): When the water repellency improvement ratio (Q / P) is 5.0 or more and less than 10.0

[0332] Acceptable (B): When the water repellency improvement ratio (Q / P) exceeds 1.0 and is less than 5.0

[0333] None or reduced (C): Water repellency improvement ratio (Q / P) is 1.0 or less

[0334] Here, the inventors' speculation regarding the above-mentioned water contact angle is described.

[0335] When the silylation ratio before and after the silylation treatment B is large (A), the Si-based surface is protected by the silyl group, that is, a water-repellent film is formed. In addition, in the case of a small (B), a part of the water-repellent film is formed, or a compound derived from the silylation agent is present. In addition, in the case of an extremely small or absent (C), there is no water-repellent film or the like to a degree that greatly affects the water repellency.

[0336] It can be said that the larger the negative value of the contact angle change (ΔQ-R) before and after the removal treatment C, the more the water-repellent film is removed (-); and the smaller the negative value, the more the water-repellent film is maintained (+).

[0337] When the water repellency improvement ratio (Q / P) before and after the treatment by the silylation treatment B and the removal treatment C is excellent (A+) or good (A), it can be said that the surface is modified in the direction of improving the water repellency. When it is possible (B) or very little or no (C), it can be said that the surface is modified in the direction of maintaining low water repellency or reducing water repellency.

[0338] Based on such speculation, the processing results of each test number are summarized and evaluated.

[0339] From the test No. 1-1 to 1-4 in Table 1, by combining the pretreatment (A-1) and the removal treatment (C-1), the water-repellent film is maintained on the SiOx surface, and the water repellency of other Si surfaces, SiN surfaces, and SiGe surfaces can be reduced by removing the water-repellent film. In addition, it can be said that a water-repellent film is formed on the SiOx surface just after the silylation treatment B, but there is a water-repellent film that can be removed by the removal process C and a compound derived from the silylation agent on the SiN surface and the SiGe surface, and there is less water-repellent film on the Si surface.

[0340] In addition, No. 4-1 and 4-2 are obtained by performing the removal process of No. 1-2 and 1-3 with (C-2) instead of (C-1), but the same results can be obtained.

[0341] In addition, No. 6-1, 6-2 to No. 9-1, 9-2 are the ones in which the removal treatment of No. 1-2, 1-3 is replaced with (C-4) to (C-7) respectively, but the same results can be obtained.

[0342] In addition, although No. 5-1, 5-2, No. 10-1, 10-2 to No. 12-1, 12-2 used a silylating agent and a removal treatment different from those used in No. 1-2 and 1-3, the same results were obtained.

[0343] In addition, from No. 2-1 to 2-4, by combining the pretreatment (A-2a) and the removal treatment (C-1), a water-repellent film is maintained on the Si surface, SiOx surface, and SiN surface, and the water repellency of the SiGe surface can be reduced by removing the water-repellent film. In addition, just after the silylation treatment B, a water-repellent film can be formed on the Si surface, SiOx surface, and SiN surface, and a water-repellent film that can be removed by the removal step C and a compound derived from the silylation agent exist on the SiGe surface. Furthermore, if (A-2a) is used as a pretreatment, the water repellency can be reduced even without the step of removing the natural oxide film of (A-1).

[0344] In addition, from No. 3-1 to 3-4, by combining the pretreatment (A-2b) and the removal treatment (C-1), the water-repellent film is maintained on the Si surface and the SiOx surface, and the water repellency can be selectively reduced by removing the water-repellent film on the SiN surface and the SiGe surface. In addition, just after the silylation treatment B, a water-repellent film can be formed on the Si surface, the SiOx surface, and the SiGe surface, but there is a water-repellent film on the SiN surface that can be removed by the removal step C, and a compound derived from the silylation agent.

[0345] It can be inferred as above.

[0346] (Selection policy for reduced water repellency)

[0347] The selection policy for the reduction of water repellency caused by the surface modification process was examined.

[0348] The transition of the water repellency of the surface by the surface modification step is considered to have the following four transition modes I to IV.

[0349] .Transition mode I: formation and maintenance of a water-repellent film.

[0350] .Transition mode II: Although the water-repellent film is formed, it is reduced or removed.

[0351] . Transformation mode III: The silylation ratio is low or the water-repellent film is not formed and is reduced or removed.

[0352] . Transition mode IV: The silylation ratio is low or a water-repellent film is not formed, and its state is maintained.

[0353] Then, by combining the surface modification step of the treatment in “transformation mode I” with the treatment in at least one of other transformation modes II to IV, it is presumed that the water repellency of the second surface can be selectively reduced relative to the first surface.

[0354] On the other hand, the water repellency after these transformation patterns I to IV, that is, the water repellency of the surface after the surface modification step, is evaluated as in the "Water repellency after water repellency adjustment" in Table 1, and is evaluated using the "Water repellency improvement rate (Q / P)", and is classified into the evaluation standards "A+, A, B, C".

[0355] Specifically, it can be considered that transition mode I corresponds to "A, A+", transition mode II corresponds to "B", and transition mode III or IV corresponds to "C".

[0356] Thus, in Table 1, in any of the treatments of Test Examples No. 1-1 to 1-4, Test Examples No. 2-1 to 2-4, Test Examples No. 3-1 to 3-4, Test Examples No. 4-1 to 4-2, Test Examples No. 5-1 to 5-2, Test Examples No. 6-1 to 6-2, Test Examples No. 7-1 to 7-2, Test Examples No. 8-1 to 8-2, Test Examples No. 9-1 to 9-2, Test Examples No. 10-1 to 10-2, Test Examples No. 11-1 to 11-2, and Test Examples No. 12-1 to 12-2, the case of "transition mode I" is combined with the case of at least one of the other transition modes II to IV, so it can be said that the water repellency of the second surface can be selectively reduced relative to the first surface.

[0357] It should be noted that in order to achieve a treatment of "transition mode I", the evaluation standard "A+" or "A" is used as a guideline, and for example, the following can be listed: appropriately selecting pre-treatment A, silylation treatment B, and removal treatment C such as "making the silanization ratio "(RP) / P" greater than 5.0, and then making the "contact angle change (ΔQ-R)" greater than -10°".

[0358] <Elemental composition analysis using X-ray photoelectron spectroscopy (XPS)>

[0359] XPS analysis is performed on the surface of the SiN substrate during or after the treatment process of the above-mentioned <Treatment of the substrate>, and the peak area ratio of the Si element, O element, and N element is calculated from the obtained XPS spectrum. The peak area ratio (%) of each element is used as the existence ratio of each element composition.

[0360] [Table 2]

[0361] Table 2

[0362]

[0363] From the above XPS analysis, it can be inferred that the peak of the O element on the surface of the SiN substrate indicates the presence of the O element derived from the OH group as a reaction site with the silylating agent. That is, if the peak of the O element exists, it is considered that silylation has occurred (that is, there is a water-repellent film on the surface, a compound derived from the silylating agent).

[0364] On the SiN surface, the peak of the O element is almost not confirmed on the surface immediately after the silylation treatment B after the pretreatment (A-1), and the peak of the O element becomes smaller immediately after the removal treatment C. Therefore, it is considered that there is not much silylation group, or even if silylation is performed, it is removed by the removal treatment C.

[0365] In addition, in the case of pretreatment (A-2a), on the surface just after silylation treatment B, the peak of the O element still exists compared to the pretreatment (A-1), and the peak of the O element can also be confirmed to remain on the surface after further removal treatment (C-1). Therefore, it can be said that the SiN surface is protected by the silyl group and maintains the state after further silylation. The above results are consistent with the tendency of the water contact angle in the aforementioned tests No. 1-3 and No. 2-3. From the above content, it can be inferred that on the SiN surface, when the above-mentioned silylation ratio is large, the water repellency obtained can be maintained after removal treatment C.

[0366] <Method for producing substrate>

[0367] (ALD film formation)

[0368] Using an ALD apparatus (manufactured by Picosun Corporation), a titanium oxide film formation test was performed as follows.

[0369] First, on a stage in an ALD device, the substrates obtained in the above-mentioned <Processing of substrates> are arranged in a plurality of designated combinations. It should be noted that any of the following is a simulation test performed by simply arranging the substrates as the first surface and the substrates as the second surface.

[0370] Specifically, in each of Example 1, Examples 3 to 10, Comparative Example 1, and Reference Example 1, two samples of a substrate with a SiOx surface and a substrate with a SiN surface are arranged adjacent to each other on a pedestal within the device; in each of Example 2, Comparative Example 2, and Reference Example 2, four samples of a substrate with a Si surface, a substrate with a SiOx surface, a substrate with a SiN surface, and a substrate with a SiGe surface are arranged adjacent to each other on a pedestal within the device.

[0371] Next, after heating the substrate to 150°C, TiCl4 exposure (supply time: 0.1s, flow rate: 120sccm), rinsing (6s), H2O exposure (supply time: 0.1s, flow rate: 120sccm) and rinsing (6s) were performed in this order as one cycle, and the designated cycle was repeated. This film formation cycle was performed for 25 cycles and 50 cycles.

[0372] [Table 3]

[0373]

[0374] (Measurement of water contact angle (S))

[0375] The water contact angle (S) immediately before the film formation test was measured by the following method.

[0376] First, each substrate was immersed in pure water for 1 minute, and then immersed in IPA (25° C.) for 1 minute. Thereafter, the substrate was taken out and dried by blowing air to remove IPA.

[0377] Next, the substrate was placed horizontally with the desired surface facing upward, and a 2 μL drop of pure water was placed on the surface.

[0378] Next, the angle between the water droplet and the substrate (water contact angle) was measured using a contact angle meter (CA-X model manufactured by Kyowa Interface Science) in accordance with JIS R 3257:1999 "Wettability test method for glass substrate surface". The measurement was performed at room temperature (25°C).

[0379] In Table 3, the water contact angle (°) of the first surface at this time is denoted as S1, and the water contact angle (°) of the second surface is denoted as S2. Using S1 and S2, the value of (S1-S2) / S2 was calculated.

[0380] (Evaluation of water repellency difference)

[0381] The difference in water repellency of the substrate surface immediately before ALD film formation was evaluated according to the following evaluation criteria using the value of "(S1-S2) / S2" measured above.

[0382] Sufficient: (S1-S2) / S2 is 1.0 or more

[0383] Insufficient: (S1-S2) / S2 is less than 1.0

[0384] (Measurement of film formation amount, calculation of film formation rate / film formation inhibition amount)

[0385] The amount of titanium oxide film formed on the substrate (nm) was calculated using an ellipsometer (JA Woollam, M2000-DI) and an XPS device (ULVAC-PHI, PHI5000 VersaProbe II). The amount of film formed was measured after 25 cycles and 50 cycles of ALD film formation.

[0386] Based on the obtained film formation amount, the film formation rate (nm / cycle) and the film formation inhibition amount (%) were calculated.

[0387] The film formation rate was calculated from the slope of the film formation amount at 25 cycles and at 50 cycles.

[0388] The filming inhibition amount was calculated by the following formula.

[0389] Film formation inhibition amount (%) = (film formation rate of the corresponding reference example - film formation rate of the embodiment or comparative example) / (film formation rate of the corresponding reference example) × 100 ... (Formula)

[0390] The so-called "corresponding reference example" is a reference example using a substrate with the same surface composition and applying the same treatment A. For example, the so-called reference example corresponding to Examples 1 and 3 to 10 in which the substrate is SiOx is Reference Example 1 in which the substrate is SiOx.

[0391] (Film formation selectivity)

[0392] The film formation selectivity (selective processability) in each of the Examples, Comparative Examples, and Reference Examples was evaluated according to the following criteria using the above-mentioned film formation inhibition amount.

[0393] High selectivity (high): among substrate samples in the film forming apparatus, the difference in film formation inhibition amount between the substrate surface to be processed (with the smallest film formation inhibition amount) and other substrate surfaces not to be processed is 50% or more.

[0394] Low selectivity (low): Among the substrate samples in the film forming apparatus, the difference in film formation inhibition amount between the substrate surface of the processing target (with the smallest film formation inhibition amount) and the substrate surfaces of other non-processing targets is less than 50%.

[0395] From the above, in each example, the film formation rate is slowed down by more than 90% when the substrate of the reference example which does not have a water repellent surface is used as a standard in the substrate having a high water repellent surface, thereby showing the result that the film formation of the ALD film of titanium oxide or the like can be suppressed. In addition, since the same degree of film formation rate can be achieved when the substrate of the reference example which does not have a water repellent surface is used as a standard in the substrate whose water repellency is selectively reduced by the removal treatment C, the film formation rate of the ALD film of titanium oxide or the like is possible and there is no problem in actual use.

[0396] In addition, if each embodiment and the corresponding comparative example are compared, it can be seen that even if it is not to the extent of the embodiment, any comparative example has a tendency to suppress film formation on the second surface of the processing object. This can be inferred that the film formation is partially suppressed because a water-repellent film and a compound derived from a silylating agent exist on the second surface without the above-mentioned removal treatment C. It is known that since the removal treatment C of the embodiment can selectively reduce the water repellency on the substrate surface (second surface) of the processing object relative to the substrate surface (first surface) of the non-processing object, the difference in the film formation inhibition amount between them can be expanded, and as a result, the film formation selectivity (selective processing) can be improved.

[0397] From the above results, the substrate processing method of each embodiment shows that in a substrate having two or more Si-based surfaces, the water repellency on a specified surface can be selectively reduced compared with the corresponding comparative examples, thereby improving the selective processability during ALD film formation, etc.

[0398] This application claims priority based on Japanese Patent Application No. 2022-090143 filed on June 2, 2022, and all the contents disclosed therein are incorporated herein by reference.

[0399] Description of Reference Numerals

[0400] 1. Substrate

[0401] 1a Substrate surface

[0402] 11 Surface 1

[0403] 12 Surface 2

[0404] 20Silylating agent, silylating composition

[0405] 21 Water repellent film

[0406] 22 Water repellent film

[0407] 30 Remover

Claims

1. A method for treating a substrate, comprising: A preparation step of preparing a substrate having a first surface and a second surface on the surface, wherein the first surface contains Si, and the second surface has a chemical composition different from that of the first surface and contains Si; a surface modification step of applying a silylating treatment in which a silylating agent is brought into contact with the first surface and the second surface, and then applying a water repellency adjustment treatment in which the water repellency of the second surface is selectively reduced relative to the first surface; as well as The processing step is to selectively perform a processing treatment on the second surface after the surface modification step.

2. The method for treating a substrate according to claim 1, wherein: The surface modification step is a step of applying a pretreatment before the silylation treatment; The pre-treatment includes a treatment A-1 of removing at least a natural oxide film on the first surface and / or a treatment A-2 of bonding OH to at least a portion of Si on the first surface.

3. The method for treating a substrate according to claim 2, wherein: The treatment A-2 is treatment A-2a of bringing at least the first surface into contact with an active species containing oxygen and / or a gas containing oxygen, or treatment A-2b of bringing at least the first surface into contact with an oxidant containing oxygen.

4. The method for treating a substrate according to claim 3, wherein: The treatment A-2a is at least one selected from the group consisting of a plasma treatment using plasma containing oxygen element, a UV / O3 treatment, and a gas treatment of exposure to a gas containing oxygen element.

5. The method for treating a substrate according to claim 3, wherein: The oxidant includes a solution containing H2O2 and / or ozone water.

6. The method for treating a substrate according to any one of claims 1 to 5, wherein: The water repellency adjustment treatment includes a removal treatment of removing at least a portion of the compound derived from the silylation agent chemically or physically bonded to the second surface using a remover.

7. The method for treating a substrate according to claim 6, wherein: The remover includes at least one selected from the group consisting of ammonia, organic amines, quaternary ammonium hydroxide, and hydrogen fluoride.

8. The method for treating a substrate according to any one of claims 1 to 7, wherein: When the value of the water contact angle of the first surface after the surface modification step and immediately before the processing step is defined as S1 and the value of the water contact angle of the second surface is defined as S2, (S1-S2) / S2 is greater than 1.

0.

9. The method for treating a substrate according to any one of claims 1 to 8, wherein: When the first surface is silicon oxide, the second surface is silicon or a compound of Si and at least one selected from the group consisting of N, C and metal elements, or an oxide of the compound; When the first surface is silicon, the second surface is a compound of Si and at least one selected from the group consisting of N, C and metal elements, or an oxide of the compound; When the first surface is a compound or oxide of Si and at least one selected from the group consisting of N and C, the second surface is a compound of Si and a metal element or an oxide of the compound.

10. The method for treating a substrate according to any one of claims 1 to 9, wherein: In the processing step, the processing includes: a film forming process of forming a film on the second surface by atomic layer deposition, and / or an etching process of etching the second surface.

11. The method for treating a substrate according to any one of claims 1 to 10, wherein: In the silylation treatment, the silylation agent or a silylation composition containing the silylation agent is used.

12. The method for treating a substrate according to claim 11, wherein: The silylation composition includes at least one of a solvent, a diluent gas, and a catalytic compound.

13. The method for treating a substrate according to any one of claims 1 to 12, wherein: The surface modification step includes a cleaning process of cleaning at least a portion of the second surface using a cleaning agent.

14. The method for treating a substrate according to claim 13, wherein: The cleaning agent comprises an aqueous cleaning solution and / or a rinse solution. 15 . A method for producing a substrate, comprising the step of obtaining a substrate subjected to each step of the method for treating a substrate according to claim 1 .

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