Substrate processing method and substrate production method

Abstract

A substrate processing method according to the present invention comprises: a preparation step for preparing a substrate that has, on a surface thereof, a first surface which contains Si and a second surface which has a different chemical composition from the first surface and which contains Si; a surface modification step for, after performing a silylation treatment in which a silylating agent is brought in contact with the first surface and the second surface, performing a water repellency adjustment treatment in which the water repellency of the second surface is selectively decreased, with respect to the first surface; and a processing step for selectively performing processing with respect to the second surface after the surface modification step.

Description

Method for treating substrate and method for manufacturing substrate

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

[0002] Conventionally, fine patterning has been achieved by multiple lithography and etching processes to obtain semiconductor devices. However, in recent years, semiconductor devices have tended to become more highly integrated and miniaturized, and in order to meet these demands, lithography processes have become more complex and costly, creating a need for alternative technologies to lithography.

[0003] As an alternative to lithography, a technology using a self-assembled monolayer (SAM) is being considered. Specifically, this technology involves selectively depositing a self-assembled monolayer (hereinafter simply referred to as a "monolayer") as a masking material or protective material on regions of a substrate that are not to be processed, and then forming or depositing a desired film material on the remaining regions of the substrate (i.e., regions that are to be processed), or performing an etching process.

[0004] Various methods have been investigated for selectively depositing the monolayer, including a method for selectively forming a monolayer based solely on the chemical properties of the substrate surface. Since this method does not limit the combination of non-processing targets and processing targets as long as a monolayer can be selectively formed, various methods for forming a monolayer corresponding to the combination have been investigated. Examples of such techniques include those described in Patent Documents 1 to 3.

[0005] For example, Patent Document 1 discloses a method of supplying a protective film forming gas containing an amine gas to a substrate having a first film and a second film on its surface, each of which is etchable by an etching gas, thereby causing the amine to adsorb to the first film and selectively protect it, and then selectively etching the second film. The claims of this document disclose combinations of the first film and the second film, such as a silicon oxide film and a silicon film, and a SiOCN film and a silicon oxide film, and exemplified protective film forming gases such as hexylamine, dipropylamine, n-octylamine, butylamine, tert-butylamine, decylamine, dodecylamine, dicyclohexylamine, and tetradecylamine.

[0006] Patent Document 2 discloses a method for forming a SAM as a block material on vertical spacers, selectively depositing a high-k film on nanowires between the vertical spacers, and a metal-containing gate electrode layer on the high-k film. This document describes that the vertical spacers include a SiCOH material, a dielectric material having a relative permittivity of less than about 7, or an air gap spacer, and that the nanowires are composed of Si, SiGe, or both Si and SiGe. Furthermore, examples of the end groups of the molecules that form the SAM include thiol, silane, and phosphonate.

[0007] Patent Document 3 discloses a method for silylating a surface by exposing a substrate having a silicon-containing surface such as Si, SiN, or silicon thermal oxide, and a silicon-free surface such as W, Co, TiN, or TaN, to a surface treatment agent containing a silylating agent and a nitrogen-containing heterocyclic compound. This document proposes that a water-repellent film is formed on the surface by silylation, but that the water contact angle after silylation varies depending on the surface material, and that this difference in water contact angle be utilized to form a film on the desired surface, i.e., a surface on which a water-repellent film is difficult to form, by atomic layer deposition (hereinafter simply referred to as "ALD").

[0008] JP 2021-163775 A JP 2021-528859 A JP 2019-121777 A

[0009] The method of forming a water-repellent film as a monolayer by surface silylation, as described in Patent Document 3, is useful because it is easy to form a film on a surface containing silicon (hereinafter referred to as an "Si-based surface"). However, when selectively forming a water-repellent film between a first surface and a second surface that are Si-based surfaces (e.g., a silicon surface and a silicon oxide surface, or a silicon oxide surface and a silicon nitride surface), such as by forming a water-repellent film on one Si-based surface (a first surface) and not forming a water-repellent film on the other Si-based surface (a second surface) with a different chemical composition, the selective formation of a water-repellent film tends to be difficult because these two surfaces each have reactivity with the silylation agent.

[0010] An object of the present invention is to provide a method for treating a substrate that is excellent in selective processability between a first surface and a second surface, both of which are Si-based surfaces.

[0011] According to one aspect of the present invention, there is provided the following method for treating a substrate and method for manufacturing a substrate. 1. A method for treating a substrate, comprising: a preparation step of preparing a substrate having, on its surface, a first surface containing Si and a second surface containing Si and having a different chemical composition from the first surface; a surface modification step of performing a silylation treatment by bringing a silylating agent into contact with the first surface and the second surface, and then performing a water-repellency adjustment treatment on the first surface to selectively reduce the water repellency of the second surface; and a processing step of selectively performing a processing treatment on the second surface after the surface modification step. 2. The method for treating a substrate according to 1., wherein the surface modification step performs a pretreatment before the silylation treatment, and the pretreatment includes at least a treatment A-1 of removing a native oxide film from the first surface and / or a treatment A-2 of bonding OH to at least a portion of the Si on the first surface. 3.2. 4. The method for treating a substrate according to 3., wherein the treatment A-2 is treatment A-2a of contacting at least the first surface with an active species containing oxygen element and / or a gas containing oxygen element, or treatment A-2b of contacting with an oxidizing agent containing oxygen element. 4. The method for treating a substrate according to 3., wherein the treatment A-2a is treatment A-2b of contacting at least the first surface with a plasma treatment using a plasma containing oxygen element, UV / O ３5. The method for treating a substrate according to 3., wherein the oxidizing agent is at least one selected from the group consisting of a treatment in which the substrate is exposed to a gas containing an oxygen element, and a gas treatment in which the substrate is exposed to a gas containing an oxygen element. ２ O ２and / or ozone water. 6. A method for treating a substrate according to any one of 1. to 5., wherein the water repellency adjustment treatment includes a removal treatment 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. 7. A method for treating a substrate according to 6., wherein the remover includes at least one selected from the group consisting of ammonia, organic amine, quaternary ammonium hydroxide, and hydrogen fluoride. 8. A method for treating a substrate according to any one of 1. to 7., wherein, after the surface modification step and immediately before the processing step, when the value of the water contact angle of the first surface is S1 and the value of the water contact angle of the second surface is S2, (S1-S2) / S2 is 1.0 or greater. 9. 1. to 8. 10. The method for treating a substrate according to any one of 1. to 9., 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 a metal element, or an oxide of said 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 a metal element, or an oxide of said compound; and 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 said compound. 11. The method for treating a substrate according to any one of 1. to 9., wherein, in the processing step, the processing treatment includes a film formation treatment for forming a film on the second surface by atomic layer deposition, and / or an etching treatment for etching the second surface. 12. The method for treating a substrate according to any one of 1. to 11., wherein the silylation treatment uses the silylating agent or a silylation composition containing the silylating agent. 13. The method for treating a substrate according to 11., wherein the silylation composition contains at least one of a solvent, a diluent gas, and a catalytic compound.13. A method for treating a substrate according to any one of 1. to 12., wherein the surface modification step comprises a cleaning treatment of cleaning at least a portion of the second surface using a cleaning agent. 14. A method for treating a substrate according to 13., wherein the cleaning agent comprises an aqueous cleaning solution and / or a rinse solution. 15. A method for producing a substrate, comprising a step of obtaining a substrate that has been subjected to each step in the method for treating a substrate according to any one of 1. to 14.

[0012] According to the present invention, there are provided a method for treating a substrate that is excellent in selective processability between a first surface and a second surface that are Si-based surfaces, and a method for manufacturing a substrate using the same.

[0013] Fig. 1 is a process cross-sectional view schematically showing each step of the substrate treatment method of the present embodiment. Fig. 2 is a process cross-sectional view schematically showing each step of the substrate treatment method of the present embodiment. Fig. 3 is a process cross-sectional view schematically showing each step of the substrate treatment method of the present embodiment.

[0014] Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all drawings, similar components are designated by similar reference numerals, and descriptions thereof will be omitted where appropriate. Furthermore, the drawings are schematic diagrams and do not correspond to actual dimensional proportions.

[0015] <Substrate Treatment Method> An outline of the substrate treatment method of this embodiment will be described.

[0016] The method for treating a substrate of this embodiment includes a preparation step of preparing a substrate having a first surface containing Si and a second surface having a different chemical composition from the first surface and containing Si; a surface modification step of performing a silylation treatment in which a silylating agent is brought into contact with the first surface and the second surface, and then performing a water-repellency adjustment treatment on the first surface to selectively reduce the water repellency of the second surface; and a processing step of selectively performing a processing treatment on the second surface after the surface modification step.

[0017] According to the findings of the present inventors, it has been found that a surface modification process in which two Si-based surfaces (first and second surfaces) containing Si elements but different chemical compositions are subjected to a silylation treatment, and then a water-repellency adjustment treatment is performed on one of the first surfaces to selectively reduce the water repellency of the other second surface, makes it possible to perform selective processing on the second surface, such as selective film formation using an ALD method or selective etching. In this specification, the term "different chemical compositions" of Si-based surfaces refers to cases in which the elements other than silicon contained in the first surface are different from the elements other than silicon contained in the second surface, or cases in which the content ratios of elements contained in the first surface and the second surface are substantially different.

[0018] Typically, the first and second Si-based surfaces each have reactivity to a silylation agent, making it difficult to form a water-repellent film on only one of the surfaces. In contrast, according to this embodiment, by performing a water-repellency adjustment treatment that selectively reduces the water repellency of a desired Si-based surface, it is possible to create a state in which a Si-based surface (first surface) on which a water-repellent film is formed and a Si-based surface (second surface) on which no water-repellent film is formed or which has very low water repellency coexist between two or more Si-based surfaces. Furthermore, the inventors' studies have found that when the water repellency is very low, the presence or absence of a water-repellent film is unclear, but its function as a protective film is also very low. Therefore, by creating such a coexistence state, the water-repellent film functions as a protective film, so that the Si-based surface with the lower water repellency is selectively processed, thereby realizing a substrate processing method with excellent selective processability between the first and second Si-based surfaces. In this specification, the term "water-repellent film" refers to both a compound having a silyl group derived from a silylating agent chemically bonded to a Si-based surface and a group of such compounds, regardless of whether or not the compounds interact with each other or are bonded to each other. The water-repellent film may also contain a compound derived from a silylating agent physically bonded (adsorbed, attached, etc.) to the Si-based surface. The bond does not necessarily have to be direct, and may also be formed via other elements, substituents, etc.

[0019] (Water repellency) In this specification, the water repellency is defined as the water contact angle obtained by the following measurement. Details of cleaning and drying before each measurement will be described later. First, the substrate was placed horizontally with the desired Si-based surface facing up, and a 2 μl droplet of pure water was placed on the surface. In order to reduce the effect of the surface shape on the water contact angle, a substrate with a smooth surface on which the water droplet was placed was used. Next, in accordance with JIS R 3257:1999 "Test method for wettability of substrate glass surfaces," the temperature during measurement was set to room temperature (25°C), and the angle between the water droplet and the substrate was measured using a contact angle meter (CA-X model, manufactured by Kyowa Interface Science Co., Ltd.), and the obtained value was defined as the water contact angle.

[0020] Each step included in the method for treating a substrate will be described in detail below.

[0021] An example of the substrate processing method of this embodiment includes a preparation step, a surface modification step, and a processing step, and will be described with reference to Figures 1 to 3. Figures 1 to 3 are cross-sectional views schematically illustrating each step of the substrate processing method.

[0022] (Preparation Step) In the preparation step, as shown in FIG. 1, a substrate 1 having a first surface 11 and a second surface 12 on its surfaces is prepared.

[0023] The material of the substrate 1 is not particularly limited as long as it is a substrate used in a semiconductor manufacturing process, and may be made of, for example, silicon, silicon carbide, a plurality of components containing silicon element, sapphire, various compound semiconductors, etc. Furthermore, the substrate 1 may be, for example, a wafer.

[0024] The substrate 1 may have a relief structure (not shown) formed on the substrate surface. The relief structure may be, for example, a three-dimensional structure having one or more structures arranged along the vertical direction of the substrate surface 1a and / or one or more structures arranged along a horizontal direction perpendicular to the vertical direction. Examples of such three-dimensional structures may constitute at least a part of a logic device, a memory device, a gate electrode, etc., such as a FinFET, a nanowire FET, a nanosheet FET, or other multi-gate FET, a three-dimensional memory cell, etc.

[0025] The first surface 11 and the second surface 12 may be disposed along the planar direction of the substrate surface 1 a, or along a direction perpendicular to the substrate surface 1 a. According to this embodiment, not only two-dimensional selective processing on a plane but also three-dimensional selective processing on a three-dimensional structure (three-dimensional film formation, three-dimensional etching, etc.) is possible.

[0026] The first surface 11 and the second surface 12 may be formed adjacent to each other, or may be formed spaced apart from each other. The first surface 11 and the second surface 12 may each be composed of one region or two or more regions. In each surface, the multiple regions may be formed spaced apart from each other.

[0027] Examples of materials constituting the first surface 11 and the second surface 12 include the following. Examples of such materials include (1) silicon (polysilicon, single-crystal silicon), (2) silicon oxide, and (3) a compound of Si with at least one selected from the group consisting of N, C, and a metal element, or an oxide of such a compound. The metal element (3) may be any metal element or semi-metal element typically used in semiconductor materials, such as W, Co, Al, Ni, Ru, Cu, Ge, Ti, Hf, and Ta. Examples of compounds of Si containing N or C include compounds such as silicon nitride, silicon carbide, and silicon carbonitride, as well as compounds of these compounds with the above metal elements. Examples of oxides include oxides of these compounds. Each of the materials (1) to (3) may contain elements other than Si, N, C, and O (e.g., H, P, B). The term "oxide" refers to a state in which oxygen is bonded to other constituent materials (particularly Si) and is present to an extent that it affects some properties, but does not include a state in which it is present in such a small amount that it does not affect physical properties. The term "compound" refers to a state in which an element other than oxygen is bonded to other constituent materials (particularly Si) and is present to an extent that it affects some properties, but does not include a state in which it is present in such a small amount that it does not affect physical properties. In the preparation process of the present disclosure, if the surface layer of each material in (1) or (3) above is unintentionally naturally oxidized, it may be used as a non-naturally oxidized material (for example, naturally oxidized silicon is treated as silicon).

[0028] An example of a combination of materials constituting the first surface 11 and the second surface 12 is given below. For example, when the first surface 11 is silicon oxide, the second surface 12 may be composed of silicon, a compound of Si and at least one selected from the group consisting of N, C, and a metal element, or an oxide of such a compound. Alternatively, 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 a metal element, or an oxide of such a compound. Alternatively, 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 such a compound.

[0029] The first surface 11 and the second surface 12 may be the surface of a member made of the above-mentioned material, or the surface of a film formed from the above-mentioned material. In particular, when the surface is made of a film, the above-mentioned material may contain two or more elements other than Si. Examples of films containing two or more elements other than Si include general low-k films such as SiON, SiCN, SiCO, SiCOH, and SiOCN. Note that the compositions of the above-mentioned films are merely representative, and the stoichiometric ratios do not have to be integer ratios as described. Specifically, in the case of SiON, the ratio is not limited to Si:O:N=1:1:1.

[0030] The water repellency of each of the first surface 11 and the second surface 12 is typically an inherent property of the constituent materials of the surfaces, but can be adjusted by pretreatment, silylation treatment, removal treatment, etc., as described below. For example, silylation treatment tends to improve the original water repellency (e.g., water contact angle), while removal treatment may reduce the water repellency improved by the silylation treatment. Furthermore, pretreatment can strengthen or weaken the effects of the silylation treatment and removal treatment. Because the above tendency differs depending on the constituent materials of the surfaces, by considering the combination of each treatment and the water repellency immediately after these treatments, it is possible to appropriately select the first surface 11, which is the object of the processing treatment, and the second surface 12, which is the object of the processing treatment. Note that even when a water-repellent film is formed on the surface by the silylation treatment of the first surface 11 or the second surface 12, and "surface water repellency" actually means "the water repellency of the water-repellent film," the terms "water repellency of the first surface" and "water repellency of the second surface" are used. Furthermore, even if at least a portion of the surface layer of each surface is oxidized or reduced by the pretreatment, removal treatment, etc. described below, they are still treated as the first surface 11 and the second surface 12 prepared in the preparation process.

[0031] Substrate 1 in the first surface 11 and second surface 12, and in the peripheral regions below first surface 11 and second surface 12, may contain a small amount of one or more dopants (e.g., P, N, B, Al, etc.) used for n-type source / drain and p-type source / drain. The dopants can affect the electrical properties when added in small amounts relative to the Si element content, and therefore, it is presumed that the dopants will not affect the silylation at first surface 11 or second surface 12 as long as they are contained in an amount sufficient to function as a dopant.

[0032] The substrate 1 may further have a third surface and / or a fourth surface (not shown) on the substrate surface 1a. The third surface contains Si and has a chemical composition different from that of the first surface 11 and the second surface 12. The fourth surface does not contain Si and is composed of, for example, amorphous carbon, elements such as W, Co, Al, Ni, Ru, Cu, Ti, and Ta, or compounds, oxides, or nitrides of these elements. The fourth surface may be a film surface of a high-k film. The third surface and the fourth surface may be adjacent to the first surface 11 and / or the second surface 12, respectively, or may be formed separately from each other. Furthermore, the third surface and the fourth surface may each be composed of one region or two or more regions.

[0033] (Surface Modification Step) The surface modification step includes a silylation treatment of the substrate surface and a water-repellency adjustment treatment performed after the silylation treatment. As described above, the water-repellency adjustment treatment selectively reduces the water-repellency of the second surface of the substrate relative to the water-repellency of the first surface. In other words, the reduction in the water-repellency of the first surface of the substrate may be suppressed or maintained. In this case, a separate treatment may be performed before or after the silylation treatment to improve the effect of the silylation treatment of the first surface or to facilitate further reducing the water-repellency of the second surface. Furthermore, even if the water-repellency of the first surface is higher immediately after the silylation treatment than that of the second surface, the water-repellency adjustment treatment can be performed to further reduce the water-repellency of the second surface, making it easier to selectively process the second surface in the processing step described below.

[0034] An example of the surface modification process involves pretreating the substrate 1 shown in FIG. 1 and then performing a silylation treatment and a removal treatment, as shown in FIGS. 2 and 3. In this specification, the pretreatment, silylation treatment, and removal treatment are sometimes referred to as pretreatment A, silylation treatment B, and removal treatment C, respectively, or treatment A, treatment B, and treatment C. Note that some or all of these treatments A to C may be performed by a wet process or a dry process. Furthermore, the above treatments A to C may treat the first surface 11 and the second surface 12 separately or simultaneously, but simultaneous treatment as shown in FIG. 1 is preferred for simplicity. Furthermore, if good results can be obtained with the silylation treatment B and removal treatment C without performing pretreatment A, pretreatment A may not be performed.

[0035] In the surface modification step, when pretreatment A is performed before silylation treatment B, pretreatment A may include treatment A-1 for removing at least a native oxide film on first surface 11 and / or treatment A-2 for bonding OH to at least a portion of Si on first surface 11.

[0036] Pretreatment A may be performed on at least first surface 11, but may also be performed on first surface 11 and second surface 12. However, even if treatment A is performed, depending on the composition material, it is not necessary for the native oxide film to be removed from part or all of second surface 12, and it is not necessary for OH groups to be formed on the surface.

[0037] Furthermore, the above-mentioned treatment A-2 may include treatment A-2a in which active species containing oxygen and / or a gas containing oxygen are brought into contact with at least the first surface 11, or treatment A-2b in which an oxidizing agent containing oxygen is brought into contact with the first surface 11.

[0038] Treatment A-1 is not particularly limited as long as it is a treatment capable of removing a native oxide film. Normally, a native oxide film is formed on the surface of polysilicon, silicon oxide, etc. during the semiconductor manufacturing process. Treatment A-1 is preferable because it can remove this native oxide film. Note that, for surfaces on which a native oxide film is not formed, treatment A-1 does not need to be performed, but the same operation may be performed as part of cleaning. Specific methods for treatment A-1 include, for example, a method of bringing hydrofluoric acid (HF) into contact with the first surface 11 and the second surface 12, a method of bringing a diluted hydrofluoric acid aqueous solution (DHF) into contact with the first surface 11 and the second surface 12, and a method of mixing HF gas and NH ３ and a method of reacting a mixed gas containing a gas with first surface 11 and second surface 12. Specific contacting methods may be known methods, such as a method similar to silylation treatment B described below, known dry processing, etc. After contacting with hydrofluoric acid, cleaning treatment may be performed with a cleaning agent described below.

[0039] 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. However, since the ease of silylation by silylation treatment B and the ease of reducing water repellency by removal treatment C may differ depending on the strength of the oxidizing power when forming the OH groups, it is desirable to adopt a treatment appropriate for the desired Si-based surface. Examples of treatment A-2 include treatment A-2a and treatment A-2b. Treatment A-2 may newly form an OH group-containing region on the first surface 11, or may form a film having OH groups (Si—OH film). The OH groups on the first surface 11 serve as reaction sites with the silylation agent in the subsequent silylation treatment B.

[0040] The treatment A-2a is a treatment that is more likely to oxidize the Si-based surface than the treatment A-2b. The treatment A-2a involves contacting at least the first surface 11 with an activated species containing an oxygen element or a gas containing an oxygen element. Specific methods for the treatment A-2a include well-known oxidation treatments used in dry processes, such as plasma treatment using a plasma containing an oxygen element, UV / O ３and a gas treatment in which the first surface 11 is exposed to a gas containing oxygen. The treatment A-2a is likely to oxidize the Si-based surface, so even if a native oxide film is formed on the surface, it is possible to form OH groups on the first surface 11 without going through the treatment A-1. The above 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. ３ The treatment is a process of generating radicals containing oxygen elements to oxidize the surface, and a known treatment device can be used. ３ , O ２ , CO ２ , H ２ O ２ For the purpose of efficient oxidation, heated gas may be used.

[0041] The treatment A-2b is a treatment that can oxidize the Si-based surface more gently than the treatment A-2a. The treatment A-2b brings an oxidizing agent containing oxygen element into contact with at least the first surface 11. As the oxidizing agent, a gas containing oxygen element that does not have as much oxidizing power as the treatment A-2a may be used, or the same gas may be used under weak oxidation conditions, but it is preferable to use a liquid oxidizing agent because it is easy to adjust the strength of oxidation. As the liquid oxidizing agent, for example, H ２ O ２ and / or ozone water. ２ O ２ The solution containing, for example, a cleaning agent (H ２ O ２ and ammonium hydroxide alkaline mixture (SC-1 liquid) and H ２ O ２ Acidic mixture of acetic acid and hydrochloric acid (SC-2 solution, etc.), ２ O ２Examples of the contacting method include a known method, such as the same method as the silylation treatment B described below. Note that, if necessary, treatment A-1 may be carried out before treatment A-2b to remove the native oxide film. Furthermore, the above treatments A-2a and A-2b may be used in combination.

[0042] In silylation treatment B, as shown in Fig. 2(a), a silylating agent (described below) is brought into contact with at least the first surface 11 and the second surface 12. In silylation treatment B, a silylating agent may be used alone, or a silylation composition containing a silylating agent, a solvent, and a diluent gas, or a silylation composition containing a silylating agent, a catalytic compound, and, if necessary, a solvent and a rare gas, may be used. The silylating agent and silylation composition may be used in the form of a liquid or gas.

[0043] In the case of a wet process, a liquid of the silylation agent 20 or silylation composition 20 is supplied to the first surface 11 and the second surface 12. Known methods can be used for supplying the silylation agent 20 or silylation composition 20. For example, when the agent is supplied in a liquid state, a single-wafer method such as a spin coating method or a batch method such as a dipping method can be used. When the agent is supplied as a vapor and becomes a liquid after contacting the first surface 11 and the second surface 12, a known vapor injection method can be used.

[0044] In the case of a dry process, the silylation agent is supplied as a gas to the first surface 11 and the second surface 12. A known method can be used for the supply method, but for example, a method in which the silylation agent is gasified in advance using a vaporizer or the like and then supplied; ２ In addition, two or more kinds of gases may be supplied simultaneously or may be mixed in advance and supplied.

[0045] The silylation treatment B can improve the water repellency of at least the first surface 11. At this time, the water repellency of the second surface 12 may also be improved. The silylation treatment B forms a structure on the first surface 11 in which silyl groups derived from the silylating agent are chemically bonded to OH groups on the first surface 11, i.e., a water-repellent film, improving the water repellency. A water-repellent film may also be formed on the second surface 12 in a similar manner. Even if a water-repellent film is not formed, the water repellency may be improved by having a structure in which a compound derived from the silylating agent is physically bonded (e.g., attached or adsorbed) to the surface.

[0046] As an example, as shown in FIG. 2( 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 films 21 and 22 may each be composed of a film that covers at least a portion of or the entire surface. Note that the water-repellent film 22 does not necessarily have to be formed on the second surface 12. In order to make it easier to reduce the water repellency of the second surface 12 by the water-repellency adjustment treatment, it is preferable to form the water-repellent film 22 on a portion of the second surface 12, or to leave the compound derived from the silylating agent in a state where it is physically bound to the second surface 12.

[0047] The water repellency improved by silylation treatment B can be estimated by comparing the water repellency immediately before and after silylation treatment B. Specifically, when the value of the water contact angle (°) immediately after silylation treatment B is R and the value of the water contact angle (°) immediately before silylation treatment B is P, it can be inferred that a water-repellent film derived from the silylation agent tends to be formed when the silylation ratio represented by (R-P) / P is large (e.g., 5.0 or more). It can also be inferred that a water-repellent film derived from the silylation agent tends to be formed only partially when the silylation ratio is small (e.g., less than 5.0), or that a high proportion of compounds derived from the silylation agent tend to physically bond. Note that the "water contact angle immediately before silylation treatment B" refers to the water contact angle of an unsilylated surface. When silylation treatment B is performed multiple times, the water contact angle immediately before the first silylation treatment B is used.

[0048] If pretreatment A can increase the number of reactive sites with the silylating agent on the first surface 11, it is possible to promote the silylation reaction in silylation treatment B. Furthermore, by increasing the number of Si—OH bonds on the surface through pretreatment A-2a or pretreatment A-2b, the silylation ratio can be improved, making it easier to form a water-repellent film, and this is therefore suitable when a first surface is desired. If necessary, known means such as heating, decompression, or drying may be applied to silylation treatment B to promote the silylation reaction between the silylating agent and the OH groups on the surface.

[0049] 3( b), the removal treatment C refers to a treatment for removing compounds derived from the silylation agent that are 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, while leaving the water-repellent film 21 on the first surface 11. When the water-repellency adjustment treatment includes this type of removal treatment C, it becomes possible to selectively reduce the water repellency of the second surface 12 relative to the first surface 11.

[0050] As shown in FIG. 3( a), the removal treatment C may be performed by, for example, using a remover to remove at least a portion of the silylation agent-derived compounds chemically or physically bonded to the second surface 12. A specific example of the removal treatment C is a method in which a liquid remover is brought into contact with the first surface 11 and the second surface 12. Alternatively, a gaseous remover such as a gas may be used as long as it is possible to leave the water-repellent film 21 on the first surface 11. Note that "contacting the first surface 11 and the second surface 12" refers to contacting at least the water-repellent film 21 and the water-repellent film 22, if such films are present. The specific method of contacting the remover may be a known method, such as the same method as in the silylation treatment B described above.

[0051] Examples of the remover include a solution containing at least one selected from the group consisting of ammonia, organic amines, quaternary ammonium hydroxides, and hydrogen fluoride. Furthermore, when two or more of the above are used, this also includes cases in which they form salts. Among the above, a solution containing at least one selected from the group consisting of hydrogen fluoride, triethylamine, t-butylamine, diisopropylamine, N,N-dimethylisopropylamine, N,N-diethylmethylamine, N,N-diisopropylethylamine, and tetrabutylammonium hydroxide and a protic solvent is preferred because it facilitates maintaining the water repellency of the first surface 11. Examples of solvents for the remover include water and alcohol-based solvents (e.g., at least one selected from alcohols having 3 or fewer carbon atoms, such as methanol, 1-propanol, and 2-propanol (isopropanol)). These solvents may be used alone or in combination. When using a solution containing a remover, the 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 taken as 100% by mass, the remover may be contained in a total amount of 0.001% by mass to 80% by mass, and preferably 0.01% by mass to 50% by mass.

[0052] By the removal treatment C, the water repellency of the first surface 11 is maintained, while the water repellency of the second surface 12 is reduced. The tendency of the effect of the removal treatment C is that, when the value (°) of the water contact angle immediately after the silylation treatment B and immediately before the removal treatment C is R, and the value (°) of the water contact angle immediately after the removal treatment C is Q, if Q-R<-10°, the water repellency is reduced and the water-repellent film is also removed. Therefore, in order to selectively reduce the water repellency of the second surface, it may be preferable that the first surface satisfy Q-R≧-10°, and that the second surface satisfy Q-R<-10°.

[0053] One example of a pattern in which water repellency can be reduced by removal treatment C is when the silylation ratio is low (less than 5.0). This pattern is thought to be easily removed by a removal agent because the water-repellent film is only partially formed or the bond between the silylation agent-derived compound and the second surface 12 is weak. Furthermore, this pattern can be made more difficult to remove even after removal treatment by subjecting it to pretreatment A or changing the type of pretreatment A to a silylation ratio of 5.0 or higher. That is, a silylation ratio of the second surface less than 5.0 is preferable because it allows selective reduction in water repellency relative to the first surface. Another example of a pattern in which water repellency can be reduced (e.g., when the silylation ratio is 5.0 or higher) is one in which water repellency can be reduced, although the detailed mechanism is unknown. One example is when oxygen or the like binds to a Si-based surface, making some kind of interaction (e.g., dissolution, catalytic action, etc.) more likely to occur between the surface and the treatment agent.

[0054] The surface modification step may involve removing the surface layer of the second surface 12 using the removal treatment C described above, provided that the water repellency of the first surface 11 is not significantly impaired. For example, the pretreatment A-2 described above may cause oxygen elements to be present on the surface layer of the second surface 12. By removing the silicon to which the oxygen elements are bonded, these oxygen elements can be removed, leaving the second surface 12 clean. The removal treatment C may also be performed two or more times. Among the removal agents described above, hydrogen fluoride is preferably used to remove the surface layer of the second surface 12. Buffered hydrofluoric acid (a mixture of hydrofluoric acid and ammonium fluoride) can also be preferably used to adjust the removal performance. The surface modification step may optionally include a cleaning treatment in which at least a portion of the second surface 12 is cleaned using a cleaning agent. For example, a cleaning treatment may be performed after the removal treatment C, but this is not limited to this. Furthermore, when at least a portion of treatments A to C are performed using a wet process, one or more cleaning treatments can be performed between treatments A to C or between individual treatments included in treatments A to C. In the case of multiple cleaning treatments, the type of cleaning agent may be changed for each treatment.

[0055] The cleaning material may include an aqueous cleaning solution and / or a rinse solution.

[0056] 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 include water, alcohol, an aqueous hydrogen peroxide solution, and ozone water. These may be used alone or in combination of two or more.

[0057] Like the aqueous cleaning solution, the rinse solution is not particularly limited as long as it does not remove the water-repellent film 21 formed on the first surface 11. A cleaning agent different from that used in the aqueous cleaning solution can be used as the rinse solution, and examples thereof include 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 oxidizing agent. Examples of organic solvents used in the rinse solution include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide-based solvents, alcohols, polyhydric alcohol derivatives, and nitrogen-containing solvents. Among these, it is preferable to use at least one organic solvent selected from alcohols having 3 or fewer carbon atoms, such as methanol, 1-propanol, and 2-propanol (isopropanol).

[0058] In this embodiment, the method of contacting the cleaning agent is not particularly limited, but examples thereof include immersion, application methods such as spin coating and spray coating, and vapor contact.

[0059] The surface modification step may include a drying treatment, if necessary. When at least some of the treatments A to C are performed by wet processes, one or more drying treatments may be performed between each of the treatments A to C or between the individual treatments included in the treatments A to C.

[0060] (Processing Step) In the processing step, after the surface modification step, processing is selectively performed on the second surface 12 shown in FIG. 3(b).

[0061] The processing may include, for example, a film formation process for forming a film on the second surface 12 by atomic layer deposition, and / or an etching process for etching the second surface 12 .

[0062] When a film formation process is performed, film formation by atomic layer deposition is suppressed on the first surface 11, but film formation by atomic layer deposition is performed on the second surface 12. If the first surface 11 has good water repellency, film formation by atomic layer deposition tends to be inhibited. Although the detailed mechanism is unclear, it is presumed that film formation by atomic layer deposition is suppressed when the first surface 11 is protected by a water-repellent film or the like. On the other hand, it is presumed that film formation can be selectively performed on the second surface 12 compared to the first surface 11 because the water-repellent film and compounds derived from the silylating agent on the second surface 12 are removed by the water-repellency adjustment process.

[0063] A known ALD device can be used as a film formation method using atomic layer deposition. For example, a thin film formation method (thermal ALD) by adsorption using a first gas-phase reactant (a film formation source) and a desired second gas-phase reactant, or a thin film formation method (plasma ALD) in which a first gas-phase reactant (a film formation source) is adsorbed onto a surface and then reacted with a plasma such as oxygen, as described above, is preferably used. The film formation temperature and film formation time can be appropriately selected depending on the film thickness and the source material.

[0064] The first gas phase reactive substance contains a film forming material. Examples of the first gas phase reactive substance include organic metals, metal halides, and metal oxide halides. Specific examples of the first gas phase reactive substance include tantalum pentaethoxide, tetrakis(dimethylamino)titanium, pentakis(dimethylamino)tantalum, tetrakis(dimethylamino)zirconium, tetrakis(dimethylamino)hafnium, tetrakis(dimethylamino)silane, bis(hexafluoroacetylacetonato)copper, Zn(C ２ H ５ ) ２ , Zn(C ２ H ５ ) ２ , Zn(CH ３ ) ２ , TMA (trimethylaluminum), TaCl ５ , W.F. ６ , WOCl ４ , CuCl, ZrCl ４ , AlCl ３, TiCl ４ , SiCl ４ , HfCl ４ etc.

[0065] The second gas phase reactant may contain a gas capable of reacting with the first gas phase reactant or a material capable of generating active species such as radicals. ２ , H ２ O, H ２ O ２ , O ２ , O ３ , HCl, HF, NH ３ , H ２ S, H ２ Se, PH ３ , AsH ３ , C.H. ４ , C ２ H ４ , or Si ２ H ６ etc.

[0066] The film formed by atomic layer deposition is not particularly limited, but may be a film containing a pure element (e.g., Si, Cu, Ta, W), a film containing an oxide (e.g., SiO ２ , GeO ２ , HfO ２ , ZrO ２ , Ta ２ O ５ , TiO ２ , Al ２ O ３ , ZnO, SnO ２ , Sb ２ O ５ , B ２ O ３ , In ２ O ３ , W.O. ３ ), nitride-containing films (e.g., Si3N4, TiN, AlN, BN, GaN, NbN), carbide-containing films (e.g., SiC), sulfide-containing films (e.g., CdS, ZnS, MnS, WS ２ , PbS), selenide-containing films (e.g., CdSe, ZnSe), phosphide-containing films (GaP, InP), arsenide-containing films (e.g., GaAs, InAs), or mixtures thereof.

[0067] When etching is performed as the processing, etching of the first surface 11 is suppressed, but etching of the second surface 12 proceeds more rapidly than that of the first surface 11. Therefore, selective etching of the second surface 12 can be performed compared to the first surface 11.

[0068] Although the detailed mechanism is unclear, it is presumed that the remaining water-repellent film 21 acts as a shield against the etching agent, so that etching of the first surface 11 is suppressed more than etching of the second surface 12.

[0069] The etching process is not particularly limited as long as it can etch the second surface 12, and a known dry etching method or wet etching method can be selected. It is also preferable to perform various etching processes using an etching agent. In the case of a gas, for example, Cl ２ Gas, F ２ Gas, ClF ３ Gas, IF ７ Interhalogen gases such as NH ３ In the case of liquids, HF, NH ４ F, N.H. ４ HF ２ , H ３ P.O. ４ , and H ２ SO ４ The etching agent may be heated or converted into plasma or radicals.

[0070] Furthermore, after the surface modification step and immediately before the processing step, when the value of the water contact angle of the first surface is S1 and the value of the water contact angle of the second surface is S2, it is preferable that the value calculated by "(S1-S2) / S2" is 1.0 or more. By setting the value within this range, selectivity during the processing step, particularly selectivity during ALD film formation, tends to be good, which is preferable. Furthermore, (S1-S2) / S2 may more preferably be 1.5 or more.

[0071] The water contact angle S1 of the first surface 11 is preferably 65° or more. By setting the angle within this range, selective processability is likely to be improved. This is particularly suitable for etching treatments. The water contact angle S1 may be more preferably 70° or more, and even more preferably 75° or more. The water contact angle S2 of the second surface 12 is not particularly limited as long as it satisfies (S1-S2) / S2≧1.0, but is preferably, for example, 60° or less, as this tends to improve selective processability. More preferably, it may be 56° or less.

[0072] If the water-repellent film remaining on the first surface after the above processing step is unnecessary, 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 silylated groups. Examples include light (ultraviolet) irradiation, heat treatment, ozone exposure, plasma irradiation, and corona discharge. Removal by a wet process is also possible, for example, by contacting with an ammonium hydroxide aqueous solution, a tetramethylammonium aqueous solution, a hydrochloric acid aqueous solution, or a sulfuric acid aqueous solution.

[0073] The method for manufacturing a substrate of this embodiment includes a step of obtaining a substrate that has been subjected to each step in the above-described method for treating a substrate. By the method for manufacturing a substrate, a desired semiconductor wafer or semiconductor device can be obtained.

[0074] <Silylating Agent> The silylating agent used in the silylation treatment in the above-described method for treating a substrate and the silylation composition containing the silylating agent will now be described.

[0075] Known silylating agents can be used as the silylating agent. Examples of the silylating agent include silicon compounds represented by the following general formula [1]. These may be used alone or in combination of two or more kinds. When two or more kinds are combined, they are sometimes referred to as a "silylated composition." Furthermore, the silicon compound contained in the above silylated composition is represented by R １ may have the same number of carbon atoms or different numbers of carbon atoms.

[0076] R １ ａ Si(H) ｂ X ４－ａ－ｂ [1]

[0077] In the above general formula [1], R １ are each independently an organic group containing a hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms; each X is independently a monovalent organic group in which the element bonded to the Si atom is nitrogen, oxygen, carbon, or halogen; a is an integer of 1 to 3; b is an integer of 0 to 2; and the sum of a and b is 1 to 3.

[0078] R in the above general formula [1] １ may contain not only hydrogen, carbon, nitrogen, oxygen, and fluorine elements, but also silicon, sulfur, and halogen elements (other than fluorine). １ R in the above general formula [1] may contain an unsaturated bond, an aromatic ring, or a cyclic structure. １ For example, each independently represents C ｅ H ２ｅ＋１ (e=1 to 18), and C ｆ F ２ｆ＋１ CH ２ CH ２ (f=1 to 8). Among these, it is particularly preferable to use a silicon compound having a trialkylsilyl group. １ When R contains a silicon element, the general formula [1] may have a structure represented by the following general formula [1-1]: １ ｍ X ３－ｍ－ｎ (H) ｎ Si-(CH ２ ) ｐ -Si(H) ｎ X ３－ｍ－ｎ R １ ｍ [1-1] In the above general formula [1-1], R １ (However, this R １ does not contain silicon element) and X are the same as those in 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 -(CH ２ ) ｐThe methylene chain represented by - may be substituted with a halogen.

[0079] 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, or oxygen, but also silicon, sulfur, a halogen element, etc. Examples of the monovalent organic group in which the element bonded to the Si element is nitrogen include, for example, an isocyanate group, an amino group, a dialkylamino group, an isothiocyanate group, an azide group, an acetamide group, and -NHC(=O)CF ３ , -N(CH ３ )C(=O)CH ３ , -N(CH ３ )C(=O)CF ３ , -N=C(CH ３ )OSi(CH ３ ) ３ , -N=C(CF ３ )OSi(CH ３ ) ３ , -NHC(=O)-OSi(CH ３ ) ３ , -NHC(=O)-NH-Si(CH ３ ) ３ , an imidazole ring, a triazole ring, a tetrazole ring, an oxazolidinone ring, a morpholine ring, —NH—C(═O)—Si(CH ３ ) ３ , -N(S(=O) ２ R ４ ) ２ (where R ４ are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms), and a substituent having a structure of the following general formula [1-2] (In the above general formula [1-2], R ５ are each independently a divalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms), -N=C(NR ６ ２ ) ２ , -N=C(NR ６ ２ ) R ６ (where R６ are each independently a hydrogen group, a —C≡N group, or —NO ２ and a hydrocarbon group in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and the hydrocarbon group may have an oxygen atom and / or a nitrogen atom. ａ１ ) (R ａ２ ) (wherein the above R ａ１ represents a hydrogen atom or a saturated or unsaturated alkyl group, and R ａ２ represents a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, or a saturated or unsaturated heterocycloalkyl group. ａ１ and R ａ２ may be bonded to each other to form a saturated or unsaturated heterocycloalkyl group having a nitrogen atom. ａ３ )-Si(R ａ４ ) (R ａ５ ) (R ａ６ ) (wherein 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 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 in —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, and R ａ８ represents a hydrogen atom, a saturated or unsaturated alkyl group, a fluorine-containing alkyl group, or a trialkylsilylamino group.

[0080] Examples of the silylating agent 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 CH ３ Si(NH ２ ) ３ , C ２ H ５ Si(NH ２ ) ３ , C３ H ７ H ２ ) ３ 、C ４ H ９ H ２ ) ３ 、C ５ H １１ H ２ ) ３ 、C ６ H １３ H ２ ) ３ 、C ７ H １５ H ２ ) ３ 、C ８ H １７ H ２ ) ３ 、C ９ H １９ H ２ ) ３ 、C １０ H ２１ H ２ ) ３ 、C １１ H ２３ H ２ ) ３ 、C １２ H ２５ H ２ ) ３ 、C １３ H ２７ H ２ ) ３ 、C １４ H ２９ H ２ ) ３ 、C １５ H ３１ H ２ ) ３ 、C １６ H ３３ H ２ ) ３ 、C １７ H ３５ H ２ ) ３ 、C １８ H ３７ H ２ ) ３ 、(CH ３ ) ２H ２ ) ２ 、C ２ H ５ H ３ ) ２ ) ２ 、(C ２ H ５ ) ２ H ２ ) ２ 、C ３ H ７ H ３ ) ２ ) ２ 、(C ３ H ７ ) ２ H ２ ) ２ 、C ４ H ９ H ３ ) ２ ) ２ 、(C ４ H ９ ) ２ H ２ ) ２ 、C ５ H １１ H ３ ) ２ ) ２ 、C ６ H １３ H ３ ) ２ ) ２ 、C ７ H １５ H ３ ) ２ ) ２ 、C ８ H １７ H ３ ) ２ ) ２ 、C ９ H １９ H ３ ) ２ ) ２ 、C １０ H ２１ H ３ ) ２ ) ２ 、C １１ H ２３ H３ ) ２ ) ２ 、C １２ H ２５ H ３ ) ２ ) ２ 、C １３ H ２７ H ３ ) ２ ) ２ 、C １４ H ２９ H ３ ) ２ ) ２ 、C １５ H ３１ H ３ ) ２ ) ２ 、C １６ H ３３ H ３ ) ２ ) ２ 、C １７ H ３５ H ３ ) ２ ) ２ 、C １８ H ３７ H ３ ) ２ ) ２ 、(CH ３ ) ３ H ２ 、C ２ H ５ H ３ ) ２ NH ２ 、(C ２ H ５ ) ２ H ３ )NH ２ 、(C ２ H ５ ) ３ H ２ 、C ３ H ７ H ３ ) ２ NH ２ 、(C ３ H ７ ) ２ H ３ )NH２ 、(C ３ H ７ ) ３ H ２ 、C ４ H ９ H ３ ) ２ NH ２ 、(C ４ H ９ ) ３ H ２ 、C ５ H １１ H ３ ) ２ NH ２ 、C ６ H １３ H ３ ) ２ NH ２ 、C ７ H １５ H ３ ) ２ NH ２ 、C ８ H １７ H ３ ) ２ NH ２ 、C ９ H １９ H ３ ) ２ NH ２ 、C １０ H ２１ H ３ ) ２ NH ２ 、C １１ H ２３ H ３ ) ２ NH ２ 、C １２ H ２５ H ３ ) ２ NH ２ 、C １３ H ２７ H ３ ) ２ NH ２ 、C １４ H ２９ H ３ ) ２ NH ２ 、C １５ H ３１H ３ ) ２ NH ２ 、C １６ H ３３ H ３ ) ２ NH ２ 、C １７ H ３５ H ３ ) ２ NH ２ 、C １８ H ３７ H ３ ) ２ NH ２ 、(CH ３ ) ２ H. ２ CH ３ H ２ NH ２ 、(C ２ H ５ ) ２ H. ２ 、C ２ H ５ H ２ NH ２ 、C ２ H ５ H ３ )(H)NH ２ 、(C ３ H ７ ) ２ H. ２ 、C ３ H ７ H ２ NH ２ CF ３ CH ２ CH ２ H ２ ) ３ 、C ２ F ５ CH ２ CH ２ H ２ ) ３ 、C ３ F ７ CH ２ CH ２ H ２ ) ３ 、C ４ F ９ CH ２ CH２ H ２ ) ３ 、C ５ F １１ CH ２ CH ２ H ２ ) ３ 、C ６ F １３ CH ２ CH ２ H ２ ) ３ 、C ７ F １５ CH ２ CH ２ H ２ ) ３ 、C ８ F １７ CH ２ CH ２ H ２ ) ３ CF ３ CH ２ CH ２ H ３ ) ２ ) ２ 、C ２ F ５ CH ２ CH ２ H ３ ) ２ ) ２ 、C ３ F ７ CH ２ CH ２ H ３ ) ２ ) ２ 、C ４ F ９ CH ２ CH ２ H ３ ) ２ ) ２ 、C ５ F １１ CH ２ CH ２ H ３ ) ２ ) ２ 、C ６ F １３ CH ２ CH ２ H３ ) ２ ) ２ 、C ７ F １５ CH ２ CH ２ H ３ ) ２ ) ２ 、C ８ F １７ CH ２ CH ２ H ３ ) ２ ) ２ CF ３ CH ２ CH ２ H ３ ) ２ NH ２ 、C ２ F ５ CH ２ CH ２ H ３ ) ２ NH ２ 、C ３ F ７ CH ２ CH ２ H ３ ) ２ NH ２ 、C ４ F ９ CH ２ CH ２ H ３ ) ２ NH ２ 、C ５ F １１ CH ２ CH ２ H ３ ) ２ NH ２ 、C ６ F １３ CH ２ CH ２ H ３ ) ２ NH ２ 、C ７ F １５ CH ２ CH ２ H ３ ) ２ NH ２ 、C ８F １７ CH ２ CH ２ Si(CH ３ ) ２ NH ２ , C.F. ３ CH ２ CH ２ Si(CH ３ ) (H) NH ２ , aminodimethylvinylsilane, aminodimethylphenylethylsilane, aminodimethylphenylsilane, aminomethyldiphenylsilane, aminodimethyl-t-butylsilane, etc. ２ group), -N=C=O, dialkylamino group (-N(CH ３ ) ２ , -N(C ２ H ５ ) ２ etc.), t-butylamino group, allylamino group, -N=C=S, -N ３ , -NHC(=O)CH ３ , -NHC(=O)CF ３ , -N(CH ３ )C(=O)CH ３ , -N(CH ３ )C(=O)CF ３ , -N=C(CH ３ )OSi(CH ３ ) ３ , -N=C(CF ３ )OSi(CH ３ ) ３ , -NHC(=O)-OSi(CH ３ ) ３ , -NHC(=O)-NH-Si(CH ３ ) 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(CH ３ ) ３ , -N(S(=O) ２ R ４ ) ２ (where R ４are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms. For example, N-(trimethylsilyl)bis(trifluoromethanesulfonyl)imide, etc.), and a substituent having a structure of the following general formula [1-2]: (In the above general formula [1-2], R ５ are each independently a divalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms. Examples include N-(trimethylsilyl)N,N-difluoromethane-1,3-bis(sulfonyl)imide, -N=C(NR ６ ２ ) ２ , -N=C(NR ６ ２ ) R ６ (where R ６ are each independently a hydrogen group, a —C≡N group, or —NO ２ and hydrocarbon groups in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and the hydrocarbon groups may have oxygen atoms and / or nitrogen atoms. For example, 2-trimethylsilyl-1,1,3,3-tetramethylguanidine, -N(R ａ１ ) R ａ２ (Here, the above R ａ１ represents a hydrogen atom or a saturated or unsaturated alkyl group, and R ａ２ represents a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, or a saturated or unsaturated heterocycloalkyl group. ａ１ and R ａ２ may be bonded to each other to form a saturated or unsaturated heterocycloalkyl group having a nitrogen atom. ａ３ )-Si(R ａ４ ) (R ａ５ ) (R ａ６ ) (wherein 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 ａ４ , R ａ５ and R ａ６ each independently represents a hydrogen atom or an organic group, Rａ４ , R ａ５ and R ａ６ 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-t-butyldisilazane, pentamethylphenyldisilazane, trimethyltriethyldisilazane, and the like.), -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, and R ａ８ represents a hydrogen atom, a saturated or unsaturated alkyl group, a fluorine-containing alkyl group, or a trialkylsilylamino group. Examples of such groups include N-trimethylsilylacetamide, N-trimethylsilyltrifluoroacetamide, N-methyl-N-trimethylsilylacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide, bis(trimethylsilyl)acetamide, and bis(trimethylsilyl)trifluoroacetamide.

[0081] Examples of the silylating agent in which X in the general formula [1] is a monovalent organic group in which the element bonded to the Si element is oxygen include the amino group (—NH ２ group) by —O—C(═A)R ａ９ (wherein A is O, CHR ａ１０ , CHOR ａ１０ , C.R. ａ１０ R ａ１０ , or NR ａ１１ indicates R ａ９ , R ａ１０each 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 phenylethyl group, or an acetyl group, and ａ１１ represents a hydrogen atom, an alkyl group, or a trialkylsilyl group. Examples include trimethylsilyl acetate, dimethylsilyl acetate, monomethylsilyl acetate, trimethylsilyl trifluoroacetate, dimethylsilyl trifluoroacetate, monomethylsilyl trifluoroacetate, trimethylsilyl trichloroacetate, trimethylsilyl propionate, and trimethylsilyl butyrate.), —O—C(R ａ１２ ) = N(R ａ１３ ) (wherein the above R ａ１２ represents a hydrogen atom, a saturated or unsaturated alkyl group, a fluorine-containing alkyl group, or a trialkylsilylamino group; R ａ１３ represents a hydrogen atom, an alkyl group, or a trialkylsilyl group.), —O—C(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-trimethylsiloxypent-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 fluorine-containing alkyl group. ａ１６ Examples of the silylating agent having the formula: ３ Si(OCH ３ ) ３ , C ２ H ５ Si(OCH ３ ) ３ , C ３ H ７ Si(OCH ３ ) ３ , C ４ H ９ Si(OCH ３ ) ３ , C ５H １１ Si(OCH ３ ) ３ 、C ６ H １３ Si(OCH ３ ) ３ 、C ７ H １５ Si(OCH ３ ) ３ 、C ８ H １７ Si(OCH ３ ) ３ 、C ９ H １９ Si(OCH ３ ) ３ 、C １０ H ２１ Si(OCH ３ ) ３ 、C １１ H ２３ Si(OCH ３ ) ３ 、C １２ H ２５ Si(OCH ３ ) ３ 、C １３ H ２７ Si(OCH ３ ) ３ 、C １４ H ２９ Si(OCH ３ ) ３ 、C １５ H ３１ Si(OCH ３ ) ３ 、C １６ H ３３ Si(OCH ３ ) ３ 、C １７ H ３５ Si(OCH ３ ) ３ 、C １８ H ３７ Si(OCH ３ ) ３ ,(H ３ ) ２ Si(OCH ３ ) ２ 、C ２ H ５ Si(H) ３ )(OCH ３ ) ２ 、(C２ H ５ ) ２ Si(OCH ３ ) ２ 、C ３ H ７ Si(H) ３ )(OCH ３ ) ２ 、(C ３ H ７ ) ２ Si(OCH ３ ) ２ 、C ４ H ９ Si(H) ３ )(OCH ３ ) ２ 、(C ４ H ９ ) ２ Si(OCH ３ ) ２ 、C ５ H １１ Si(H) ３ )(OCH ３ ) ２ 、C ６ H １３ Si(H) ３ )(OCH ３ ) ２ 、C ７ H １５ Si(H) ３ )(OCH ３ ) ２ 、C ８ H １７ Si(H) ３ )(OCH ３ ) ２ 、C ９ H １９ Si(H) ３ )(OCH ３ ) ２ 、C １０ H ２１ Si(H) ３ )(OCH ３ ) ２ 、C １１ H ２３ Si(H) ３ )(OCH ３ ) ２ 、C １２ H ２５ Si(H) ３ )(OCH ３) ２ 、C １３ H ２７ Si(H) ３ )(OCH ３ ) ２ 、C １４ H ２９ Si(H) ３ )(OCH ３ ) ２ 、C １５ H ３１ Si(H) ３ )(OCH ３ ) ２ 、C １６ H ３３ Si(H) ３ )(OCH ３ ) ２ 、C １７ H ３５ Si(H) ３ )(OCH ３ ) ２ 、C １８ H ３７ Si(H) ３ )(OCH ３ ) ２ ,(H ３ ) ３ SiOCH ３ 、C ２ H ５ Si(H) ３ ) ２ OCH ３ 、(C ２ H ５ ) ２ Si(H) ３ )OCH ３ 、(C ２ H ５ ) ３ SiOCH ３ 、C ３ H ７ Si(H) ３ ) ２ OCH ３ 、(C ３ H ７ ) ２ Si(H) ３ )OCH ３ 、(C ３ H ７ ) ３ SiOCH ３ 、C ４ H ９Si(H) ３ ) ２ OCH ３ 、(C ４ H ９ ) ３ SiOCH ３ 、C ５ H １１ Si(H) ３ ) ２ OCH ３ 、C ６ H １３ Si(H) ３ ) ２ OCH ３ 、C ７ H １５ Si(H) ３ ) ２ OCH ３ 、C ８ H １７ Si(H) ３ ) ２ OCH ３ 、C ９ H １９ Si(H) ３ ) ２ OCH ３ 、C １０ H ２１ Si(H) ３ ) ２ OCH ３ 、C １１ H ２３ Si(H) ３ ) ２ OCH ３ 、C １２ H ２５ Si(H) ３ ) ２ OCH ３ 、C １３ H ２７ Si(H) ３ ) ２ OCH ３ 、C １４ H ２９ Si(H) ３ ) ２ OCH ３ 、C １５ H ３１ Si(H) ３ ) ２ OCH ３ 、C １６ H ３３ Si(H)３ ) ２ OCH ３ , C １７ H[[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​３ ) ３ 、C ６ F １３ CH ２ CH ２ Si(OCH ３ ) ３ 、C ７ F １５ CH ２ CH ２ Si(OCH ３ ) ３ 、C ８ F １７ CH ２ CH ２ Si(OCH ３ ) ３ 、CF ３ CH ２ CH ２ Si(H) ３ )(OCH ３ ) ２ 、C ２ F ５ CH ２ CH ２ Si(H) ３ )(OCH ３ ) ２ 、C ３ F ７ CH ２ CH ２ Si(H) ３ )(OCH ３ ) ２ 、C ４ F ９ CH ２ CH ２ Si(H) ３ )(OCH ３ ) ２ 、C ５ F １１ CH ２ CH ２ Si(H) ３ )(OCH ３ ) ２ 、C ６ F １３ CH ２ CH ２ Si(H) ３ )(OCH ３ ) ２ 、C ７ F １５ CH ２ CH ２Si(H) ３ )(OCH ３ ) ２ 、C ８ F １７ CH ２ CH ２ Si(H) ３ )(OCH ３ ) ２ 、CF ３ CH ２ CH ２ Si(H) ３ ) ２ OCH ３ 、C ２ F ５ CH ２ CH ２ Si(H) ３ ) ２ OCH ３ 、C ３ F ７ CH ２ CH ２ Si(H) ３ ) ２ OCH ３ 、C ４ F ９ CH ２ CH ２ Si(H) ３ ) ２ OCH ３ 、C ５ F １１ CH ２ CH ２ Si(H) ３ ) ２ OCH ３ 、C ６ F １３ CH ２ CH ２ Si(H) ３ ) ２ OCH ３ 、C ７ F １５ CH ２ CH ２ Si(H) ３ ) ２ OCH ３ 、C ８ F １７ CH ２ CH ２ Si(H) ３ ) ２ OCH ３, C.F. ３ CH ２ CH ２ Si(CH ３ ) (H) OCH ３ or a compound in which the methyl group moiety of the methoxy group of the above methoxysilane is replaced with a monovalent hydrocarbon group having 2 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced with fluorine atoms), —O—S(═O) ２ -R ａ１７ (Here, the above R ａ１７ represents an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group, a phenyl group, a tolyl group, —O—Si(CH ３ ) ３ For example, trimethylsilyl sulfonate, trimethylsilyl benzene sulfonate, trimethylsilyl toluene sulfonate, trimethylsilyl trifluoromethane sulfonate, trimethylsilyl perfluorobutane sulfonate, bistrimethylsilyl sulfate, etc., -O-P(-O-Si(CH ３ ) ３ ) ２ (for example, tristrimethylsilyl phosphite, etc.)

[0082] Furthermore, examples of the silylating agent in which X in the above general formula [1] 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, Siloxane, 1,3-di-n-octyltetramethyldisiloxane, 1,3-diethyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, hexa-n-butyldisiloxane, hexaethyldisiloxane, hexavinyldisiloxane, 1,1,3,3-tetraisopropyldisiloxane, vinylpentamethyldisiloxane, 1,3-bis(3-chloroisobutyl)tetramethyldisiloxane, hexaphenyldisiloxane, 1,1,1-triethyl-3,3,3-trimethyldisiloxane, 1,3-bis(chloromethyl)tetramethyldisiloxane Methyldisiloxane, 1,1,3,3-tetraphenyldimethyldisiloxane, pentamethyldisiloxane, 1,3-bis(3-chloropropyl)tetramethyldisiloxane, 1,3-dichloro-1,3-diphenyl-1,3-dimethyldisiloxane, n-butyl-1,1,3,3-tetramethyldisiloxane, 1,3-di-t-butyldisiloxane, vinyl-1,1,3,3-tetramethyldisiloxane, 1,1,1-trimethyl-3,3,3-triphenyldisiloxane, 3,3-diphenyltetramethyltrisiloxane, 3-phenylheptamethoxane Chiltrisiloxane, hexamethylcyclotrisiloxane, n-propylheptamethyltrisiloxane, 3-ethylheptamethyltrisiloxane, 3-(3,3,3-trifluoropropyl)heptamethyltrisiloxane, 1,1,3,5,5-pentaphenyl-1,3,5-trimethyltrisiloxane, octamethyltrisiloxane, 1,1,5,5-tetraphenyl-1,3,3,5-tetramethyltrisiloxane, hexaphenylcyclotrisiloxane, 1,1,1,5,5,5-hexamethyltrisiloxane, 3-phenyl-1,1,3,5,5-pentamethyltrisiloxane, 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-heptamethyltrisiloxane, 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 Also included are siloxane compounds such as methylsiloxane, octamethylcyclotetrasiloxane, 1,3-bis(trimethylsiloxy)-1,3-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.

[0083] Examples of the silylating agent 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 the amino group (—NH ２ group) to -C(S(=O) ２ R ７ ) ３ (where R ７ are each independently a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms. Examples include those in which hydrogen atoms are replaced by (trimethylsilyl)tris(trifluoromethanesulfonyl)methide, etc.

[0084] Furthermore, examples of the silylating agent in which X in the general formula [1] is a monovalent organic group in which the element bonded to the Si element is halogen include the amino group (—NH ２ group) is replaced with a chloro group, a bromo group, or an iodo group (for example, chlorotrimethylsilane, bromotrimethylsilane, etc.).

[0085] The silylating agent may contain a cyclic silazane compound, such as cyclic disilazane compounds like 2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane and 2,2,6,6-tetramethyl-2,6-disila-1-azacyclohexane, cyclic trisilazane compounds like 2,2,4,4,6,6-hexamethylcyclotrisilazane and 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane, and cyclic tetrasilazane compounds like 2,2,4,4,6,6,8,8-octamethylcyclotetrasilazane.

[0086] When the silylating agent is supplied in the form of a gas, it may be supplied as a mixed gas containing an inert gas. ２ , Ar, He, Ne, CF ４ etc. Preferably, N ２ , Ar, or He may also be used.

[0087] The silylation composition refers to a composition containing two or more of the above-mentioned silylating agents in combination, or a composition containing the above-mentioned mixed gas and a compound other than the silylating agent. The silylation composition may contain, in addition to the silylating agent, a catalytic compound that promotes the silylation reaction caused by the silylating agent. The catalytic compound is preferably one or more selected from the group consisting of Compound A (described below), acid imides, nitrogen-containing compounds, silicon-free nitrogen-containing heterocyclic compounds, and silylated heterocyclic compounds. The catalytic compound here refers to a compound that can promote the reaction between the above-mentioned surfaces and the silylating agent or enhance the water-repellent properties of the resulting water-repellent film, and may itself or a modified compound thereof may constitute part of the water-repellent film.

[0088] 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.

[0089] Specific examples of the compound A include, 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, and can contain one or more selected from them.These may be used alone or in combination of two or more.In addition, the compound A may also correspond to the above-mentioned silylating agent, but when used as a catalytic compound, it means that the compound A used and the above-mentioned silylating agent are used in combination.

[0090] The compound A may be 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. Any excess silicon compound represented by the following general formula [2] that remains unconsumed in the reaction can be used as the silylating agent together with the compound A obtained by the reaction. The silicon compound represented by the following general formula [2] may be reacted, for example, in a molar ratio of 0.2 to 100,000 times, preferably 0.5 to 50,000 times, more preferably 1 to 10,000 times, the acetic acid or sulfonic acid.

[0091] R ２ ｃ (H) ｄ Si-X [2]

[0092] In the above general formula [2], R ２ ｃ (H) ｄ As Si-, (CH ３ ) ３ Si-, (CH ３ ) ２ (H)Si-, (C ４ H ９ ) (CH ３ ) ２ Si-, (C ６ H １３ ) (CH ３ ) ２ Si-, (C ８ H １７ ) (CH ３ ) ２ Si-, (C １０ H ２１ ) (CH ３ ) ２ Si-, etc. X is the same as in the general formula [1] above.

[0093] The compound A may be at least one selected from the group consisting of sulfonic acids represented by the following general formula [3], anhydrides of the sulfonic acids, salts of the sulfonic acids, and sulfonic acid derivatives represented by the following general formula [4]: ８ -S(=O) ２ OH [3] [In the above general formula [3], R ８ is a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 8 carbon atoms, some or all of whose hydrogen atoms may be replaced by fluorine atoms, and hydroxyl groups.] R ８' -S(=O) ２ O—Si(H) ３－ｒ (R ９ ) ｒ [4] [In the above general formula [4], R ８' is a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and R ９ are each independently at least one group selected from monovalent hydrocarbon groups having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and r is an integer of 1 to 3.

[0094] Furthermore, the compound A may be at least one selected from the group consisting of sulfonate esters represented by the following general formula [5], sulfonimides represented by the following general formulas [6] and [7], sulfonimide derivatives represented by the following general formulas [8] and [9], sulfonmethides represented by the following general formula

[10] , and sulfonmethide derivatives represented by the following general formula

[11] . １０ -S(=O) ２ OR １１ [5] [In the above general formula [5], R １０ is a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 8 carbon atoms, some or all of whose hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms; R １１ is a monovalent alkyl group having 1 to 18 carbon atoms. １２ -S(=O) ２ ) ２ NH [6] [In the above general formula [6], R １２ are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms. [In the above general formula [7], R １３ is a divalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms. １４ -S(=O) ２ ) ２ N) ｓ Si(H) ｔ (R １５ ) ４－ｓ－ｔ [8] [In the above general formula [8], R １４ are each independently a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms; R １５ are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, s is an integer of 1 to 3, t is an integer of 0 to 2, and the sum of s and t is 3 or less. [In the above general formula [9], R １６are each independently a divalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and R １７ are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, u is an integer of 1 to 3, v is an integer of 0 to 2, and the sum of u and v is 3 or less.] (R １８ -S(=O) ２ ) ３ CH

[10] [In the above general formula

[10] , R １８ are each independently a group selected from the group consisting of a monovalent hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms. １９ -S(=O) ２ ) ３ C) ｗ Si(H) ｘ (R ２０ ) ４－ｗ－ｘ

[11] [In the above general formula

[11] , R １９ are each independently a group selected from the group consisting of monovalent hydrocarbon groups having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and fluorine atoms; R ２０ are each independently a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, w is an integer of 1 to 3, x is an integer of 0 to 2, and the sum of w and x is 3 or less.

[0095] Furthermore, examples of the acid imides that can be used as catalytic compounds include compounds having a chemical structure in which an acid such as a carboxylic acid or phosphoric acid is imidized.

[0096] The nitrogen-containing compound that can be used as the catalytic compound includes at least one of the compounds represented by the following general formulas

[12] and

[13] : ２１ -N=C(NR ２２ ２ ) ２

[12] R ２１ -N=C(NR ２２２ ) R ２２

[13] [In the above general formulas

[12] and

[13] , R ２１ represents a hydrogen group, a —C≡N group, or —NO ２ R is selected from a hydrocarbon group in which some or all of the hydrogen atoms may be replaced by fluorine atoms, an alkylsilyl group, and the hydrocarbon group may contain oxygen atoms and / or nitrogen atoms, but when it contains a nitrogen atom, it is considered to have a non-cyclic structure. ２２ are each independently a hydrogen group, a —C≡N group, or —NO ２ and hydrocarbon groups in which some or all of the hydrogen atoms may be replaced by fluorine atoms, and the hydrocarbon groups may contain oxygen atoms and / or nitrogen atoms, but when they contain nitrogen atoms, they are considered to have a non-cyclic structure.] Furthermore, examples of the nitrogen-containing compounds 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-pentafluoropropylamidine.

[0097] Furthermore, examples of the above-mentioned nitrogen-containing heterocyclic compounds not containing silicon atoms and silylated heterocyclic compounds that can be used as catalytic compounds include at least one of compounds represented by the following general formulas

[14] and

[15] : [In the above general formula

[14] , R ２３ and R ２４ are each independently a divalent organic group consisting of a carbon element and / or a nitrogen element and a hydrogen element, and the total number of carbon atoms and nitrogen atoms is 1 to 9, and when there are 2 or more carbon atoms, there may be carbon atoms that do not constitute the ring.] [In the above general formula

[15] , R ２５is an alkyl group having 1 to 6 carbon atoms in which some or all of the hydrogen atoms may be replaced by elemental fluorine, a trialkylsilyl group having an alkyl group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by elemental fluorine, an alkenyl group having 2 to 6 carbon atoms in which some or all of the hydrogen atoms may be replaced by elemental fluorine, an alkoxy group having 1 to 6 carbon atoms in which some or all of the hydrogen atoms may be replaced by elemental fluorine, an amino group, an alkylamino group having an alkyl group having 1 to 6 carbon atoms in which some or all of the hydrogen atoms may be replaced by elemental fluorine, a dialkylamino group having an alkyl group having 1 to 6 carbon atoms in which some or all of the hydrogen atoms may be replaced by elemental fluorine, an aminoalkyl group having 1 to 6 carbon atoms in which some or all of the hydrogen atoms may be replaced by elemental fluorine, a nitro group, a cyano group, a phenyl group, a benzyl group, or a halogen group; R ２６ , R ２７ and R ２８ are each independently an alkyl group having 1 to 6 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms, or a hydrogen group.

[0098] The silicon-free nitrogen-containing heterocyclic compound may contain heteroatoms other than nitrogen atoms, such as oxygen atoms and sulfur atoms, in the ring, may have aromaticity, and may be a compound in which two or more rings are bonded by a single bond or a polyvalent linking group having a valence of two or more. It may also have a substituent. Examples of the silicon-free nitrogen-containing heterocyclic compound 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.

[0099] In addition, the above-mentioned silylated heterocyclic compounds include silylated imidazole compounds and silylated triazole compounds. Examples of silylated heterocyclic compounds include monomethylsilylimidazole, dimethylsilylimidazole, trimethylsilylimidazole, monomethylsilyltriazole, dimethylsilyltriazole, trimethylsilyltriazole, etc. It should be noted that some of the above-mentioned silylated heterocyclic compounds correspond to the above-mentioned silylating agents, but when used as a catalytic compound, this means that they are used in combination with other silylating agents other than the silylated heterocyclic compounds.

[0100] In the silylation composition, the concentration of the silylating agent, or the total concentration of the silylating agent and the catalytic compound, relative to 100% by mass of the silylation composition, may be, for example, 0.01% by mass to 100% by mass, preferably 0.1% by mass to 50% by mass, and more preferably 0.5% by mass to 30% by mass.

[0101] Additionally, when the silylation composition is a liquid, the silylation composition may include a solvent.

[0102] The solvent is not particularly limited as long as it dissolves the silylating agent. Examples of solvents that can be used include organic solvents such as hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxide-based solvents, alcohols, carbonate-based solvents, polyhydric alcohol derivatives, nitrogen-containing solvents, silicone solvents, and thiols. Among these, hydrocarbons, esters, ethers, halogen-containing solvents, sulfoxide-based solvents, and polyhydric alcohol derivatives that do not have an OH group are preferred. These solvents may be used alone or in combination of two or more.

[0103] Examples of the hydrocarbons include linear, branched, or cyclic hydrocarbon solvents, aromatic hydrocarbon solvents, and terpene solvents, such as n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane, n-dodecane, n-tetradecane, n-hexadecane, n-octadecane, and n-eicosane, as well as branched hydrocarbons corresponding to the carbon numbers thereof (e.g., isododecane, isocetane, etc.), cyclohexane, methylcyclohexane, and the like. Examples of the solvent include cyclohexane, decalin, benzene, toluene, xylene, (ortho-, meta-, or para-)diethylbenzene, 1,3,5-trimethylbenzene, naphthalene, mesitylene, p-menthane, o-menthane, m-menthane, diphenylmenthane, limonene, α-terpinene, β-terpinene, γ-terpinene, bornane, norbornane, pinane, α-pinene, β-pinene, carane, longifolene, abietane, and terpene solvents.

[0104] Examples of the esters include ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl acetate, i-pentyl acetate, n-hexyl acetate, n-heptyl acetate, n-octyl acetate, n-pentyl formate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl n-octanoate, methyl decanoate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate, dimethyl adipate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl ethoxyacetate.

[0105] Furthermore, the esters may be cyclic esters such as lactone compounds. Examples of lactone compounds include β-propiolactone, γ-butyrolactone, γ-valerolactone, γ-hexanolactone, γ-heptanolactone, γ-octanolactone, γ-nonanolactone, γ-decanolactone, γ-undecanolactone, γ-dodecanolactone, δ-valerolactone, δ-hexanolactone, δ-octanolactone, δ-nonanolactone, δ-decanolactone, δ-undecanolactone, δ-dodecanolactone, and ε-hexanolactone.

[0106] Examples of the ethers include di-n-propyl ether, ethyl-n-butyl ether, di-n-butyl ether, ethyl-n-amyl ether, di-n-amyl ether, ethyl-n-hexyl ether, di-n-hexyl ether, di-n-octyl ether, as well as ethers having a branched hydrocarbon group such as diisopropyl ether and diisoamyl ether corresponding to the carbon numbers of these ethers, dimethyl ether, diethyl ether, methyl ethyl ether, methylcyclopentyl ether, diphenyl ether, tetrahydrofuran, and dioxane.

[0107] Examples of the ketones include acetone, acetylacetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, cyclohexanone, and isophorone.

[0108] Examples of the halogen element-containing solvent include perfluorocarbons such as perfluorooctane, perfluorononane, perfluorocyclopentane, perfluorocyclohexane, and hexafluorobenzene; hydrofluorocarbons such as 1,1,1,3,3-pentafluorobutane, octafluorocyclopentane, 2,3-dihydrodecafluoropentane, and Zeorora H (manufactured by Zeon Corporation); 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, and Novec Examples of such hydrocarbons include hydrofluoroethers such as HFE-7200, Novec7300, and Novec7600 (all manufactured by 3M), chlorocarbons 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, and 1,2-dichloro-3,3,3-trifluoropropene, perfluoroethers, and perfluoropolyethers.

[0109] Examples of the sulfoxide solvent include dimethyl sulfoxide.

[0110] Examples of the carbonate solvent include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, and propylene carbonate.

[0111] 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- Examples include methyl-2-pentanol, 3-methyl-2-pentanol, 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, isooctanol, 2-ethyl-1-hexanol, and 4-methyl-2-pentanol.

[0112] Examples of the derivatives of the above polyhydric alcohols that 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 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, and triethylene glycol monoethyl ether acetate. 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 diacetate, 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 methylpropyl 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, glycerin triacetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, etc.

[0113] 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, and pyridine.

[0114] Examples of the silicone solvent include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, and dodecamethylpentasiloxane.

[0115] Examples of the thiols include 1-hexanethiol, 2-methyl-1-pentanethiol, 3-methyl-1-pentanethiol, 4-methyl-1-pentanethiol, 2,2-dimethyl-1-butanethiol, 3,3-dimethyl-1-butanethiol, 2-ethyl-1-butanethiol, 1-heptanethiol, benzylthiol, 1-octanethiol, 2-ethyl-1-hexanethiol, 1-nonanethiol, 1-decanethiol, 1-undecanethiol, 1-dodecanethiol, and 1-tridecanethiol.

[0116] The 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, relative to 100% by mass of the solvent. It is more preferable that the solvent is an aprotic solvent, i.e., the solvent contains the aprotic solvent at a content of 100% by mass relative to 100% by mass of the solvent.

[0117] Aprotic solvents include hydrocarbons, esters, ethers, ketones, halogen-containing solvents, sulfoxides, carbonate solvents, polyhydric alcohol derivatives, nitrogen-containing solvents, silicone solvents, etc. These may be used alone or in combination of two or more. Among these, it is preferable to use one or more selected from the group consisting of polyhydric alcohol derivatives, hydrocarbons, and ethers.

[0118] From the viewpoint of cost and solubility, derivatives of polyhydric alcohols (which do not have an OH group in the molecule) are preferred, such as 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, ethylene glycol dimethyl ether, 3-methoxy-3-methyl-1-butyl acetate, Preferred are 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, and dipropylene glycol diacetate. Also preferred are propylene carbonate, linear or branched hydrocarbon solvents having 6 to 12 carbon atoms, p-menthane, diphenylmenthane, limonene, terpinene, bornane, norbornane, and pinane.

[0119] Examples of silylation compositions containing a silylating agent and a solvent include those in which the silylating agent is 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-2,5-disila-1-azacyclopentane, 2,2,4,4,6,6-hexamethyldisilaz ... The catalyst may contain one or more selected from the group consisting of trimethylsilylcyclotrisilazane, hexamethyldisiloxane, trimethylsilyl trifluoroacetate, trimethylsilyl trifluoromethanesulfonate, trimethylsilylbenzenesulfonate, and trimethylsilyl toluenesulfonate, and the solvent may contain one or more selected from the group consisting of propylene carbonate, linear hydrocarbon solvents having 7 to 10 carbon atoms, menthane, pinane, γ-butyrolactone, propylene glycol monomethyl ether acetate, and 3-methoxy-3-methyl-1-butyl acetate.

[0120] The silylation composition may contain no water or may contain water in an amount of 2% by mass or less based on 100% by mass of the silylation composition, making it possible to use a silylation composition that is substantially free of water.

[0121] The silylation composition may contain other components in addition to those described above, provided that the object of the present invention is not impaired. Examples of such other components include oxidizing agents such as hydrogen peroxide and ozone, surfactants, and antioxidants such as BHT.

[0122] The silylation composition of this embodiment is obtained by mixing the above-mentioned components. The obtained mixture may be purified using an adsorbent, a filter, or the like, as necessary. Alternatively, each component may be purified in advance by distillation, or may be purified using an adsorbent, a filter, or the like.

[0123] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations may be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of achieving the object of the present invention are included in the present invention.

[0124] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the descriptions of these examples.

[0125] <Substrate Treatment> Using the combination of substrates and treatment conditions shown in Table 1, substrates prepared based on the following (1. Substrate Preparation Step) were subjected to the pretreatment A, silylation treatment B, and removal treatment C shown in the following (2. Surface Modification Step) in this order to perform substrate treatment. Note that, hereinafter, "SiOx" represents silicon oxide, and SiN and SiGe represent silicon nitride and silicon germanium, respectively, and their composition ratios are not necessarily limited to Si:N = 1:1 or Si:Ge = 1:1. Furthermore, the following is a simulation test in which substrates having two types of surfaces were not treated, but rather a substrate represented as a first surface and a substrate represented as a second surface were separately prepared and treated for simplicity.

[0126]

[0127] (1. Substrate Preparation Step) Substrates having the Si-based surface compositions shown in Table 1 were prepared as follows. A smooth silicon substrate measuring 30 mm x 40 mm x 1 mm was used as the substrate. When the surface composition to be used was Si, it was used as is, and when the surface composition was other than Si, a film with the desired surface composition was formed on the surface of the substrate.

[0128] (2. Surface Modification Step) The treatment conditions for each treatment used in the surface modification step are as follows: (2.1) Pretreatment A (A-1) Removal of native oxide film At room temperature, the substrate was immersed in a 0.02 to 1 mass % aqueous solution of hydrofluoric acid (DHF) for 1 minute, and then immersed in pure water as a rinse solution and then in 2-propanol (IPA) for 1 minute each. (A-2a) Oxidation step of substrate surface The substrate was immersed in a UV / O ３ The substrate was placed in a UV / O device (manufactured by Novascan) and exposed to UV light for 30 minutes.３ (A-2b) Removal of native oxide film and oxidation of substrate surface At room temperature, the substrate was immersed in a 0.02 to 1 mass % aqueous solution of hydrofluoric acid (DHF) for 1 minute, and then in an APM solution (NH ３ OH:H ２ O ２ : H ２ The substrate was then immersed in a mixed solution of 1:10:70 HCl / HCl for 1 minute, followed by immersion in pure water for 1 minute and IPA for 1 minute.

[0129] (2.2) Silylation Treatment B The substrate was immersed in a silylating agent prepared by the following method at room temperature to silylate the surface of the substrate. However, when the silylating agents were B-1, B-3, and B-4, the immersion time was 60 seconds, and when the silylating agent was B-2, the immersion time was 20 seconds. (Silylating Agent B-1) Silylating agent B-1 was obtained by weighing out and mixing 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. (Silylating Agent B-2) Silylating agent B-2 was obtained by weighing out and mixing 12 g of HMDS, 4 g of trimethylsilyl trifluoroacetate, and 84 g of PGMEA at room temperature. (Silylating Agent B-3) Silylating Agent B-3 was obtained by weighing out 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. (Silylating Agent B-4) Silylating Agent B-4 was obtained by weighing out 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.

[0130] (2.3) Removal Treatment C (C-1) Basic Aqueous Solution Treatment The substrate was immersed in a 3% by mass aqueous triethylamine solution at room temperature for 30 minutes. It was then immersed in pure water for 1 minute, and then in IPA for 1 minute. The substrate was then removed, and dried by blowing air onto it to remove the IPA. (C-2) Diluted Hydrogen Fluoride Solution Treatment The substrate was immersed in a 0.01 to 0.5% by mass aqueous hydrogen fluoride solution at room temperature for 5 minutes. It was then immersed in pure water for 1 minute, and then in IPA for 1 minute. The substrate was then removed, and dried by blowing air onto it to remove the IPA. (C-3) Basic Aqueous Solution Treatment The substrate was immersed in a 3% by mass aqueous triethylamine solution at room temperature for 10 minutes. It was then immersed in pure water for 1 minute, and then in IPA for 1 minute. The substrate was then removed, and dried by blowing air onto it to remove the IPA. (C-4) Basic Aqueous Solution Treatment At room temperature, the substrate was immersed in a 3% by mass aqueous solution of diisopropylamine for 30 minutes. It was then immersed in pure water for 1 minute and then in IPA for 1 minute. The substrate was then removed, and dried by blowing air over it to remove the IPA. (C-5) Basic Aqueous Solution Treatment At room temperature, the substrate was immersed in a 3% by mass aqueous solution of N,N-dimethylisopropylamine for 30 minutes. It was then immersed in pure water for 1 minute and then in IPA for 1 minute. The substrate was then removed, and dried by blowing air over it to remove the IPA. (C-6) Basic Aqueous Solution Treatment At room temperature, the substrate was immersed in a 3% by mass aqueous solution of N,N-diethylmethylamine for 30 minutes. It was then immersed in pure water for 1 minute and then in IPA for 1 minute. The substrate was then removed, and dried by blowing air over it to remove the IPA. (C-7) Basic Aqueous Solution Treatment At room temperature, the substrate was immersed in a 3% by mass aqueous solution of N,N-diisopropylethylamine for 30 minutes. The substrate was then immersed in pure water for 1 minute, and then in IPA for 1 minute. The substrate was then taken out, and dried by blowing air onto it to remove the IPA. (C-8) Basic Aqueous Solution Treatment The substrate was immersed in a 10% by mass aqueous solution of tetrabutylammonium hydroxide for 1 minute at room temperature. The substrate was then immersed in pure water for 1 minute, and then in IPA for 1 minute. The substrate was then taken out, and dried by blowing air onto it to remove the IPA.

[0131] The substrates were evaluated for the following items during or after the treatment described above in <Substrate Treatment>.

[0132] <Measurement and Evaluation of Water Contact Angle> (Measurement of Water Contact Angle) The water contact angle (°) on the surface of the substrate was measured immediately after pretreatment A, immediately after silylation treatment B, and immediately after removal treatment C according to the following measurement procedure.

[0133] Measurement method immediately after pretreatment A: First, if the substrate was wet immediately after treatment, it was dried by blowing air onto it. Next, the substrate was placed horizontally with the surface subjected to treatment A facing up, and a 2 μl droplet of pure water was placed on the surface. Next, in accordance with JIS R 3257:1999 "Test method for wettability of substrate glass surfaces," 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). The temperature during measurement was room temperature (25°C). Measurement method immediately after silylation treatment B: First, the substrate immediately after treatment was immersed in IPA at 25°C for 1 minute. Next, it was dried by blowing air onto it, and the water contact angle was measured using the same process as in the measurement immediately after pretreatment A. Measurement method immediately after removal treatment C: The substrate was placed horizontally with the surface subjected to silylation treatment B facing up, and the water contact angle was measured using the same process as in the measurement immediately after pretreatment A.

[0134] (Evaluation of silylation ratio) The rate of increase in water repellency on the substrate surface due to silylation treatment B was evaluated based on the following evaluation criteria using the water contact angle (P) immediately before silylation treatment B (in this example, immediately after pretreatment A) and the water contact angle (R) immediately after silylation treatment B, and the "silylation ratio" calculated from "(R-P) / P". Large (A): When the silylation ratio is 5.0 or more Small (B): When the silylation ratio is more than 1.0 and less than 5.0 Very small or absent (C): When the silylation ratio is 1.0 or less

[0135] (Evaluation of retention / reduction of water repellency) The retention or reduction of water repellency on the substrate surface by removal treatment C was evaluated based on the following evaluation criteria using the "change in contact angle (ΔQ-R)" calculated from "water contact angle (Q) immediately after removal treatment C - water contact angle (R) immediately after silylation treatment B". Retention (+): When the change in contact angle (ΔQ-R) is -10° or more. Reduction (-): When the change in contact angle (ΔQ-R) is less than -10°.

[0136] (Evaluation of water repellency after water repellency adjustment) When the treatment was carried out through silylation treatment B and removal treatment C, the change in water repellency before and after the treatment 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 the water repellency based on the following evaluation criteria: Excellent (A+): When the water repellency improvement rate (Q / P) is 10.0 or more Good (A): When the water repellency improvement rate (Q / P) is 5.0 or more and less than 10.0 Fair (B): When the water repellency improvement rate (Q / P) is more than 1.0 and less than 5.0 None or decreased (C): When the water repellency improvement rate (Q / P) is 1.0 or less

[0137] Here, the inventors' speculation regarding the water contact angle is described. When the silylation ratio before and after silylation treatment B is large (A), the Si-based surface is protected by silyl groups, i.e., a water-repellent film is formed. When the silylation ratio is small (B), a partial water-repellent film is formed, or compounds derived from the silylation agent are present. When the ratio is minimal or absent (C), the water-repellent film is not present to a degree that significantly affects water repellency. The more negative the change in contact angle (ΔQ-R) before and after removal treatment C, the more the water-repellent film is removed (-), and the more negative the change, the more the water-repellent film is retained (+). When the water-repellency improvement rate (Q / P) before and after treatment through silylation treatment B and removal treatment C is excellent (A+) or good (A), it can be said that the surface has been modified in a direction that improves water repellency. When the ratio is fair (B), minimal, or absent (C), it can be said that low water repellency has been maintained or the surface has been modified in a direction that reduces water repellency.

[0138] Based on this inference, the evaluation of the processing results for each test number is summarized. Tests 1-1 to 1-4 in Table 1 show that by combining the pretreatment (A-1) and removal treatment (C-1), a water-repellent film is maintained on the SiOx surface, while the water-repellent film is removed from other Si, SiN, and SiGe surfaces, reducing water repellency. Immediately after silylation treatment B, a water-repellent film is formed on the SiOx surface, but the SiN and SiGe surfaces contain water-repellent films and compounds derived from the silylation agent that can be removed by removal step C, and it can be said that only a small amount of water-repellent film is present on the Si surface. Furthermore, in tests 4-1 and 4-2, the removal treatment of tests 1-2 and 1-3 was performed using (C-2) instead of (C-1), but similar results were obtained. Tests 6-1, 6-2 to 9-1 and 9-2 are similar to those of tests 6-1, 6-2, 6-3, and 9-1, respectively. The removal treatment of Nos. 1-2 and 1-3 was performed using (C-4) to (C-7) instead of (C-1), but similar results were obtained. Furthermore, Nos. 5-1, 5-2, 10-1, 10-2 to 12-1, and 12-2 used different silylation agents and removal treatments than those used in Nos. 1-2 and 1-3, respectively, but similar results were obtained. Furthermore, Nos. 2-1 to 2-4 show that by combining pretreatment (A-2a) and removal treatment (C-1), a water-repellent film is maintained on the Si surface, SiOx surface, and SiN surface, and water repellency can be reduced by removing the water-repellent film from the SiGe surface. Furthermore, immediately after silylation treatment B, a water-repellent film can be formed on the Si surface, SiOx surface, and SiN surface, and compounds derived from the silylating agent and capable of being removed by removal step C are present on the SiGe surface. Furthermore, when (A-2a) is used as a pretreatment, water repellency can be reduced without the step of removing the native oxide film (A-1). Also, from Nos. 3-1 to 3-4, by combining the pretreatment (A-2b) and the removal treatment (C-1), a water-repellent film is retained on the Si surface and the SiOx surface, and the water-repellent film can be selectively reduced from the SiN surface and the SiGe surface by removing the water-repellent film. Furthermore, immediately after the silylation treatment B, a water-repellent film can be formed on the Si surface, the SiOx surface, and the SiGe surface, but the water-repellent film formed by the removal step C and compounds derived from the silylation agent are present on the SiN surface. This is presumed to be the case.

[0139] (Guidelines for selecting a method for reducing water repellency) We will now consider guidelines for selecting a method for reducing water repellency through a surface modification process. It is believed that the transition of surface water repellency through a surface modification process can occur in the following four transition patterns I to IV. Transition pattern I: A water-repellent film is formed and maintained. Transition pattern II: A water-repellent film is formed but is reduced or removed. Transition pattern III: The silylation ratio was low, or a water-repellent film is not formed, and is reduced or removed. Transition pattern IV: The silylation ratio was low, or a water-repellent film is not formed, and this state is maintained. It is therefore presumed that a surface modification process that combines a process that results in "transition pattern I" with a process that results in at least one of the other transition patterns II to IV can selectively reduce the water repellency of the second surface relative to the first surface. On the other hand, the water repellency after these transition patterns I to IV, i.e., the water repellency of the surface after the surface modification process, is evaluated using the "water repellency improvement rate (Q / P)" as evaluated in "Water repellency after water repellency adjustment" in Table 1, and is classified into the evaluation criteria "A+, A, B, C." Specifically, it can be considered that transition pattern I corresponds to "A, A+," transition pattern II corresponds to "B," and transition pattern III or IV corresponds to "C." Therefore, in Table 1, the treatments of Test Example Nos. 1-1 to 1-4, 2-1 to 2-4, 3-1 to 3-4, 4-1 to 4-2, 5-1 to 5-2, 6-1 to 6-2, 7-1 to 7-2, and 8-2 correspond to the treatments of Test Example Nos. 1-2 to 1-4, 2-1 to 2-4, 3-1 to 3-4, 4-1 to 4-2, 5-1 to 5-2, 6-1 to 6-2, 7-1 to 7-2, and 8-2 correspond to the treatments of Test Example Nos. 1-3 to 1-4, 2-1 to 2-4, 3-1 to 3-4, 4-1 to 4-2, 5-1 to 5-2, 6-1 to 6-2, 7-1 to 7-2, and 8-2 correspond to the treatments of Test Example Nos. 1-2 to 1-4, 2-1 to 2 ...5, 2-1 to 2-5, 2-1 to 2-6, 2 In any of the treatments of Test Examples Nos. 8-1 to 8-2, 9-1 to 9-2, 10-1 to 10-2, 11-1 to 11-2, and 12-1 to 12-2, a case where "Transition Pattern I" occurs is combined with a case where at least one of the other transition patterns II to IV occurs, and therefore it can be said that it is possible to selectively reduce the water repellency of the second surface relative to the first surface.In order to achieve "Transition Pattern I," the evaluation criteria should be set to "A+" or "A," and the pretreatment A, silylation treatment B, and removal treatment C should be appropriately selected so that the silylation ratio "(R-P) / P" is 5.0 or more and the "change in contact angle (ΔQ-R)" is -10° or more.

[0140] <Elemental Composition Analysis by X-ray Photoelectron Spectroscopy (XPS)> XPS analysis was performed on the surface of the SiN substrate during or after the treatment described in <Substrate Treatment> above. From the obtained XPS spectrum, the peak area ratios of the Si element, the O element, and the N element were calculated, and the peak area ratio (%) of each element was defined as the abundance ratio of each element composition.

[0141]

[0142] From the above XPS analysis, it is inferred that the O element peak on the surface of the SiN substrate indicates the presence of O element derived from OH groups, which are reaction sites with the silylating agent. In other words, the presence of an O element peak is considered to indicate silylation (i.e., the surface has a water-repellent film or a compound derived from the silylating agent). On the SiN surface, almost no O element peak was observed on the surface immediately after silylation treatment B after pretreatment (A-1), and the O element peak became even smaller immediately after removal treatment C. This suggests that there are not many silylated groups, or that even if silylation was performed, it was removed by removal treatment C. Furthermore, in the case of pretreatment (A-2a), the O element peak was more present on the surface immediately after silylation treatment B than in pretreatment (A-1), and it was confirmed that the O element peak remained on the surface after removal treatment (C-1). Therefore, it can be said that the SiN surface is protected by silyl groups, and further, the silylated state is maintained. The above results are consistent with the above-mentioned Tests No. 1-3 and No. This coincides with the tendency of the water contact angle in 2-3. From the above, it is presumed that the water repellency obtained on the SiN surface is maintained even after removal treatment C when the silylation ratio is high.

[0143] <Substrate Manufacturing Method> (ALD Film Formation) A titanium oxide film formation test was conducted using an ALD apparatus (manufactured by Picosun) as follows. First, a predetermined combination of substrates obtained in the above <Substrate Treatment> was arranged on a pedestal inside the ALD apparatus. Note that the following is a simulation test conducted by arranging a substrate simply representing the first surface and a substrate simply representing the second surface. Specifically, in each of Examples 1, 3 to 10, Comparative Example 1, and Reference Example 1, two samples, one with a SiOx surface and one with a SiN surface, were arranged adjacent to each other on a pedestal inside the apparatus. In each of Example 2, Comparative Example 2, and Reference Example 2, four samples, one with a Si surface, one with a SiOx surface, one with a SiN surface, and one with a SiGe surface, were arranged adjacent to each other on a pedestal inside the apparatus.

[0144] The substrate was then heated to 150°C, after which TiCl ４ Exposure (supply time: 0.1s, flow rate: 120sccm), purge (6s), H ２ One cycle consisted of O exposure (supply time: 0.1 s, flow rate: 120 sccm) and purging (6 s), and this cycle was repeated for a predetermined number of cycles. This film formation cycle was performed 25 times and 50 times.

[0145]

[0146] (Measurement of Water Contact Angle (S)) The water contact angle (S) immediately before the film formation test was measured by the following method. First, each substrate was immersed in pure water for 1 minute, and then in IPA (25°C) for 1 minute. The substrate was then removed and dried by blowing air onto it to remove the IPA. Next, the substrate was placed horizontally with the desired surface facing up, and a 2 μl droplet of pure water was placed on the surface. Next, in accordance with JIS R 3257:1999 "Test Method for Wettability of Substrate Glass Surfaces," 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 Co., Ltd.). The temperature during measurement was room temperature (25°C). In Table 3, the water contact angle (°) of the first surface at this time was designated S1, and the water contact angle (°) of the second surface was designated S2, and the value of (S1-S2) / S2 was calculated using S1 and S2.

[0147] (Evaluation of Water Repellency Difference) The water repellency difference on the substrate surface immediately before ALD film formation was evaluated based on the following evaluation criteria using the value of "(S1-S2) / S2" measured above. Sufficient: (S1-S2) / S2 is 1.0 or more. Insufficient: (S1-S2) / S2 is less than 1.0.

[0148] (Measurement of film formation amount, calculation of film formation rate and film formation suppression amount) The film formation amount (nm) of titanium oxide on the substrate was calculated using an ellipsometer (M2000-DI, manufactured by J.A. Woollam) and an XPS device (PHI 5000 VersaProbe II, manufactured by ULVAC-PHI, Inc.). The film formation amount was measured after 25 cycles and after 50 cycles of the ALD film formation. Based on the obtained film formation amount, the film formation rate (nm / cycle) and film formation suppression amount (%) were calculated.

[0149] The film formation rate was calculated from the slope of the film formation amount at 25 cycles and at 50 cycles. The film formation suppression amount was calculated from the following formula: Film formation suppression amount (%) = (film formation rate of corresponding Reference Example - film formation rate of Example or Comparative Example) / (film formation rate of corresponding Reference Example) x 100 ... (formula) A "corresponding Reference Example" is a Reference Example in which a substrate having the same surface composition is used and the same Treatment A is applied; for example, a Reference Example corresponding to Examples 1 and 3 to 10 in which the substrate is SiOx would be Reference Example 1 in which the substrate is SiOx.

[0150] (Film formation selectivity) The film formation selectivity (selective processability) in each of the Examples, Comparative Examples, and Reference Examples was evaluated based on the following criteria using the above-mentioned film formation suppression amount. High selectivity (high): When, among the substrate samples in the film formation device, the difference in film formation suppression amount between the substrate surface to be processed (with the smallest film formation suppression amount) and the surfaces of other substrates that are not to be processed is 50% or more. Low selectivity (low): When, among the substrate samples in the film formation device, the difference in film formation suppression amount between the substrate surface to be processed (with the smallest film formation suppression amount) and the surfaces of other substrates that are not to be processed is less than 50%.

[0151] From the above, in each example, the substrate having a highly water-repellent surface had a film formation rate that was 90% or more slower than the reference substrate having no water-repellent surface, which showed that the formation of an ALD film of titanium oxide, etc. could be suppressed. Furthermore, the substrate in which the water-repellency was selectively reduced by removal treatment C achieved a film formation rate that was about the same as the reference substrate having no water-repellent surface, making it possible to form an ALD film of titanium oxide, etc., without any practical problems.

[0152] Furthermore, when comparing each example with the corresponding comparative example, it was found that all comparative examples tended to suppress film formation on the second surface of the object to be processed, although not as much as the examples. This is presumably because the water-repellent film and compounds derived from the silylating agent were present on the second surface without undergoing the above-mentioned removal treatment C, which partially suppressed film formation. The removal treatment C of the example can selectively reduce the water repellency on the substrate surface (second surface) to be processed relative to the substrate surface (first surface) not to be processed, thereby widening the difference in the amount of film formation suppression between them, and as a result, it was found that the film formation selectivity (selective processability) can be improved.

[0153] The above results show that the substrate treatment methods of the examples are capable of selectively reducing the water repellency of a specific surface of a substrate having two or more types of Si-based surfaces, compared to the corresponding comparative examples, thereby improving selective processability during ALD film formation, etc.

[0154] This application claims priority based on Japanese Patent Application No. 2022-090143, filed on June 2, 2022, the disclosure of which is incorporated herein in its entirety.

[0155] DESCRIPTION OF SYMBOLS 1 Substrate 1a Substrate surface 11 First surface 12 Second surface 20 Silylation agent, silylation composition 21 Water-repellent film 22 Water-repellent film 30 Remover

Claims

1. a preparation step of preparing a substrate having a first surface containing Si and a second surface having a chemical composition different from that of the first surface and containing Si; a surface modification step of subjecting the first surface and the second surface to a silylation treatment in which a silylating agent is brought into contact with the first surface and the second surface, and then subjecting the first surface to a water repellency adjustment treatment in which the water repellency of the second surface is selectively reduced; a processing step of selectively processing the second surface after the surface modification step; A method for treating a substrate, comprising:

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

3. 3. The method for treating a substrate according to claim 2, The method for treating a substrate, wherein the treatment A-2 is treatment A-2a in which an active species containing oxygen element and / or a gas containing oxygen element is brought into contact with at least the first surface, or treatment A-2b in which an oxidizing agent containing oxygen element is brought into contact with at least the first surface.

4. 4. The method for treating a substrate according to claim 3, The treatment A-2a is a plasma treatment using a plasma containing oxygen element, a UV / O ３ and gas treatment involving exposure to a gas containing an oxygen element.

5. 4. The method for treating a substrate according to claim 3, The oxidizing agent is H ２ O ２ and / or ozone water.

6. A method for treating a substrate according to any one of claims 1 to 5, A method for treating a substrate, wherein the water repellency adjustment treatment includes a removal treatment using a remover to remove at least a portion of the compound derived from the silylating agent that is chemically or physically bound to the second surface.

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

8. A method for treating a substrate according to any one of claims 1 to 5, When the value of the water contact angle of the first surface after the surface modification step and immediately before the processing step is S1 and S2, respectively, A method for treating a substrate, wherein (S1-S2) / S2 is 1.0 or more.

9. A method for treating a substrate according to any one of claims 1 to 5, when the first surface is silicon oxide, the second surface is silicon, a compound of Si and at least one selected from the group consisting of N, C, and a metal element, or an oxide of such a 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 a metal element, 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. Methods for treating substrates.

10. A method for treating a substrate according to any one of claims 1 to 5, A method for treating a substrate, wherein in the processing step, the processing treatment includes a film formation treatment for forming a film on the second surface by atomic layer deposition, and / or an etching treatment for etching the second surface.

11. A method for treating a substrate according to any one of claims 1 to 5, A method for treating a substrate, wherein the silylation treatment uses the silylating agent or a silylation composition containing the silylating agent.

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

13. A method for treating a substrate according to any one of claims 1 to 5, The method for treating a substrate, wherein the surface modification step includes a cleaning treatment of cleaning at least a portion of the second surface with a cleaning agent.

14. 14. A method for treating a substrate according to claim 13, comprising: A method of treating a substrate, wherein the cleaning agent comprises an aqueous cleaning solution and / or a rinse solution.

15. A method for producing a substrate, comprising the steps of obtaining a substrate that has been subjected to each step in the method for treating a substrate according to any one of claims 1 to 5.