Substrate treating method and substrate manufacturing method

Abstract

A substrate treating method according to the present disclosure includes: a preparation step for preparing a substrate having a first surface containing Si element and a second surface containing a metal element but not containing Si element; a surface modification step for selectively improving the water repellency of the first surface relative to the second surface by supplying a chemical solution containing a silylating agent, a catalytic compound, and an aprotic solvent to the first surface and the second surface; and a film formation step for selectively forming a film by supplying a film material in a vapor phase to the second surface. The chemical solution does not contain a nitrogen-containing heterocyclic compound, or satisfies the blending conditions that Cn is 0.05 mass% or less and Cn / Cc is 0.01 or less, where Cc is the content (mass%) of the catalytic compound contained in 100 mass% of the chemical solution, and Cn is the content of the nitrogen-containing heterocyclic compound.

Description

Method for treating substrate and method for manufacturing substrate

[0001] The present disclosure relates to methods for treating and manufacturing substrates.

[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 for selectively depositing the monolayer have been investigated, including, for example, 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. One such technique is described in Patent Document 1.

[0005] Patent Document 1 describes a method of exposing the surface of a substrate with a surface treatment agent containing a silylating agent (A) and a nitrogen-containing heterocyclic compound (B) (see, for example, claim 1 of Patent Document 1). The document also describes that, when the surface treatment agent contains the nitrogen-containing heterocyclic compound (B), the silylation reaction of the silylating agent (A) and bonding to the substrate surface can be promoted, and that the substrate surface can be activated by abstracting hydrogen from hydroxyl groups present on the substrate surface, resulting in selective improvement of hydrophobicity between two or more adjacent regions of different materials on the substrate surface (paragraph 0065).

[0006] Japanese Patent Application Laid-Open No. 2019-121777

[0007] However, as a result of investigations by the present inventors, it was found that a nitrogen-containing component remains on the metal surface of a substrate when a surface of a substrate on which a predetermined amount of such a nitrogen-containing component remains is subjected to a film formation treatment, and there is a concern that the nitrogen-containing component may be incorporated as an impurity in an amount greater than the allowable amount in the formed film.

[0008] As a result of further investigation, the present inventors have found that by using a chemical solution containing a silylating agent that is substantially free of nitrogen-containing heterocyclic compounds and by appropriately selecting the surface compositions of the first surface and the second surface, it is possible to suppress the residue of nitrogen-containing components on the second surface, which has a relatively lower water repellency than the first surface, and have thus completed the present invention.

[0009] According to one aspect of the present disclosure, the following substrate treatment method and substrate manufacturing method are provided: 1. A substrate treatment method comprising: a preparation step of preparing a substrate having a first surface containing Si element and a second surface containing no Si element but a metal element; a surface modification step of supplying a chemical solution containing a silylating agent, a catalytic compound, and an aprotic solvent to the first surface and the second surface to selectively improve the water repellency of the first surface relative to the second surface; and a film formation step of supplying a film material in a gas phase to the second surface to selectively form a film, wherein the chemical solution does not contain a nitrogen-containing heterocyclic compound, or satisfies the following formulation conditions: when the content (mass %) of the catalytic compound contained in 100 mass % of the chemical solution is Cc and the content (mass %) of the nitrogen-containing heterocyclic compound is Cn, Cn is 0.05 mass % or less and Cn / Cc is 0.01 or less. The method for treating a substrate according to the above item (1), wherein the catalytic compound comprises at least one selected from the group consisting of a carboxylic acid derivative represented by the following general formula

[17] and a sulfonic acid derivative represented by the following general formula [4]. ２９’ -C(=O)O-Si(H) ３－ｈ (R ３０ ) ｈ

[17] [In the above general formula

[17] , R ２９’ 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 ３０ 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 h is an integer of 1 to 3. 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 from 1 to 3.] 3. The method for treating a substrate according to 1. or 2., wherein the catalytic compound comprises one or more selected from the group consisting of 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. 4. 1. to 3. The method for treating a substrate according to any one of the above items, wherein the silylating agent contains a silicon compound represented by the following general formula [1]: １ ａ Si(H) ｂ X ４－ａ－ｂ [1] (In the above general formula [1], R １are 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, and X is each independently a monovalent organic group in which the atom 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. 5. The method for treating a substrate according to 4., wherein the silicon compound is a silicon compound represented by the R １are each independently an organic group containing a hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms. 6. A method for treating a substrate according to any one of 1. to 5., wherein the first surface contains one or more elements selected from the group consisting of Si, N, C, and O (including at least Si), and the second surface contains one or more elements selected from the group consisting of W, Co, Al, Ni, Ru, Cu, Ti, Ta, Hf, and Ge. 7. A method for treating a substrate according to any one of 1. to 6., wherein the film formation step is a step of forming a film by atomic layer deposition. 8. A method for treating a substrate according to any one of 1. to 7., wherein a cleaning treatment is performed to clean the substrate between the surface modification step and the film formation step. 9. A method for treating a substrate according to any one of 1. to 8. 10. A method for treating a substrate according to any one of 1. to 9., wherein a drying process for drying the substrate is carried out between the surface modification process and the film formation process. 11. A method for treating a substrate according to any one of 1. to 9., wherein the surface modification process supplies the chemical solution in a liquid state to the first surface and the second surface. 12. A method for treating a substrate, comprising: a preparation step of preparing a substrate having a first surface containing Si element and a second surface containing no Si element but a metal element; a surface modification step of supplying a chemical solution containing a silylating agent, a catalytic compound, and an aprotic solvent to the first surface and the second surface to selectively improve the water repellency of the first surface relative to the second surface; and a film formation step of supplying a film material in a gas phase to the second surface to selectively form a film, wherein the chemical solution contains 8% by mass or more of a silylating agent in 100% by mass of the chemical solution, and does not contain a nitrogen-containing heterocyclic compound, or satisfies the following formulation conditions: when the content (mass %) of the catalytic compound contained in 100% by mass of the chemical solution is Cc and the content (mass %) of the nitrogen-containing heterocyclic compound is Cn, Cn is 0.05% by mass or less, and Cn / Cc is 0.01 or less. 2. The method for treating a substrate according to claim 1 , wherein the surface modification step includes supplying vapor of the chemical solution to the first surface and the second surface.13. A method for treating a substrate, comprising: a preparation step of preparing a substrate having a first surface containing Si element and a second surface containing no Si element but a metal element; and a surface modification step of supplying a chemical solution containing a silylating agent, a catalytic compound, and an aprotic solvent to the first surface and the second surface to selectively improve the water repellency of the first surface relative to the second surface, wherein the chemical solution does not contain a nitrogen-containing heterocyclic compound, or satisfies the following formulation conditions: when the content (mass %) of the catalytic compound contained in 100 mass % of the chemical solution is Cc and the content (mass %) of the nitrogen-containing heterocyclic compound is Cn, Cn is 0.05 mass % or less and Cn / Cc is 0.01 or less. 15. A method for treating a substrate, comprising: a preparation step of preparing a substrate having a first surface containing Si element and a second surface containing no Si element but a metal element; a surface modification step of supplying a chemical solution containing a silylating agent, a catalytic compound, and an aprotic solvent to the first surface and the second surface to selectively improve the water repellency of the first surface relative to the second surface; and an etching step of performing wet etching or dry etching on the second surface, wherein the chemical solution does not contain a nitrogen-containing heterocyclic compound, or satisfies the following formulation conditions: when the content (mass %) of the catalytic compound contained in 100 mass % of the chemical solution is Cc and the content (mass %) of the nitrogen-containing heterocyclic compound is Cn, Cn is 0.05 mass % or less and Cn / Cc is 0.01 or less. 15. A method for treating a substrate, comprising the method for treating a substrate according to any one of 1. to 14.

[0010] According to the present disclosure, there are provided a method for treating a substrate that is excellent in suppressing the remaining nitrogen-containing components, and a method for manufacturing a substrate using the same.

[0011] 1A to 1C are cross-sectional process views schematically illustrating a preparation step of a method for treating a substrate according to an embodiment of the present disclosure; 1B to 1C are cross-sectional process views schematically illustrating a surface modification step of a method for treating a substrate according to an embodiment of the present disclosure; 1C to 1D are cross-sectional process views schematically illustrating a film formation step of a method for treating a substrate according to an embodiment of the present disclosure;

[0012] Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. In all drawings, similar components are denoted by similar reference numerals, and descriptions thereof will be omitted as appropriate. The drawings are schematic diagrams and do not correspond to actual dimensional proportions.

[0013] A method for treating a substrate according to an embodiment of the present disclosure will now be described.

[0014] 1: First Embodiment The first embodiment will be described below.

[0015] A first embodiment of a substrate treatment method includes a preparation step of preparing a substrate having a first surface containing Si and a second surface containing a metal element but not Si; a surface modification step of supplying a chemical solution containing a silylating agent, a catalytic compound, and an aprotic solvent to the first surface and the second surface to selectively improve the water repellency of the first surface relative to the second surface; and a film formation step of supplying a film material in a gas phase to the second surface to selectively form a film. In this substrate treatment method, the chemical solution satisfies formulation condition A, which is that the chemical solution does not contain a nitrogen-containing heterocyclic compound, or satisfies formulation condition B, in which, when the content (mass %) of the catalytic compound contained in 100 mass % of the chemical solution is Cc and the content (mass %) of the nitrogen-containing heterocyclic compound is Cn, Cn is 0.05 mass % or less and Cn / Cc is 0.01 or less. Note that the above "substantially free of nitrogen-containing heterocyclic compounds" means that either formulation condition A or formulation condition B is satisfied. When the chemical is substantially free of the component, the content is preferably less than 0.001% by mass in 100% by mass of the chemical solution, and more preferably may be less than the measurement limit of gas chromatography, for example, less than 0.0001% by mass.

[0016] According to the findings of the present inventors, it has been found that by using a chemical solution that does not contain a nitrogen-containing heterocyclic compound as a surface treatment agent for a substrate having a first surface containing Si and a second surface containing a metal element, it is possible to suppress the residual nitrogen-containing component on the second surface after the surface modification process, which results in a relatively low water repellency. Furthermore, it has been found that even when a trace amount of a nitrogen-containing heterocyclic compound is contained in the chemical solution, the residual nitrogen-containing component on the second surface after the surface modification process can be suppressed by using the chemical solution in combination with a catalytic compound and satisfying the above-mentioned formulation condition B. In this case, a chemical solution containing a nitrogen-containing heterocyclic compound in combination with a catalytic compound can have a higher nitrogen-containing heterocyclic compound content tolerance than a chemical solution containing only the nitrogen-containing heterocyclic compound (without the catalytic compound). Although the detailed mechanism is unclear, it is presumed that the catalytic compound acts as an acid, thereby suppressing the adhesion of the nitrogen-containing heterocyclic compound to the substrate surface. Therefore, the substrate treatment method of this embodiment can suppress the incorporation of impurities into the film formed in the film formation process, thereby reducing variation in the quality of the substrate.

[0017] 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 the first surface and a group of such compounds, regardless of whether or not the compounds interact with each other or bond with each other. The above bond does not necessarily have to be direct, and may also be formed via another element, a substituent, or the like.

[0018] (Water repellency) In this specification, water repellency will be explained using 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 each 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 was measured using a contact angle meter (CA-X model, manufactured by Kyowa Interface Science Co., Ltd.), and the obtained value was taken as the water contact angle.

[0019] Each step of the substrate processing method according to the first embodiment will be described in detail below with reference to Figures 1 to 3. Figures 1 to 3 are cross-sectional views that schematically illustrate the preparation step, the surface modification step, and the film formation step, respectively.

[0020] (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.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] 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. Each of the first surface 11 and the second surface 12 may be composed of one region or two or more regions. The multiple regions in each surface may be formed spaced apart from each other, and the materials of the surfaces constituting the multiple regions may be the same or different from each other.

[0025] The first surface 11 is a surface containing Si elements, and is a surface whose water repellency is selectively improved by a silylation agent. Examples of materials containing Si elements include silicon oxide, silicon nitride, silicon carbide, single crystal silicon, polysilicon, silicon germanium, and low-k materials. Also, oxides, nitrides, carbides, and other compounds of Si and at least one element selected from the group consisting of N, C, and metal elements may be used. The above low-k materials are those having a relative dielectric constant of SiO ２ This refers to a material with a lower insulating property, such as SiON, SiCN, SiCO, SiCOH, or SiOCN. The composition of the low-k material is merely representative, and the stoichiometric ratio does not have to be the integer ratio described. Specifically, in the case of SiON, the ratio is not limited to Si:O:N=1:1:1. The first surface 11 preferably contains one or more elements (including at least Si) selected from the group consisting of Si, N, C, and O. The above ranges facilitate bond formation by the silylating agent, further improving water repellency. Furthermore, it is preferable for the surface to contain many regions with Si—OH bonds, and a surface on which Si—OH bonds have been formed by surface treatment may be used. More preferably, the first surface 11 may contain Si and O, and the total amount of Si and O relative to the elements constituting the first surface 11 may be 80 mol% or more. Furthermore, the first surface 11 may contain elements other than Si, N, C, and O (H, P, B, etc.) as long as the water repellency imparted by contact with a chemical solution is not significantly impaired.

[0026] The second surface 12 is a surface that does not contain Si but does contain a metal element, and is less likely to be imparted with water repellency by a silylation agent than the first surface 11, or is not imparted with water repellency by a silylation agent. Furthermore, a film is formed on the second surface 12 through a film formation process. Materials that do not contain Si but contain a metal element may be metal elements or semimetal elements typically used in semiconductor materials, such as W, Co, Al, Ni, Ru, Cu, Ge, Ti, Hf, Ta, and alloys containing two or more of these elements. Further examples include oxides, nitrides, oxynitrides, and the like of these metal elements, semimetal elements, and alloys. The second surface 12 preferably contains one or more elements selected from the group consisting of W, Co, Al, Ni, Ru, Cu, Ti, Ta, Hf, and Ge. Furthermore, the second surface may be a surface that does not have Si—OH bonds. More preferably, the second surface 12 may contain one or more elements selected from the group consisting of W, Co, Al, Ni, Ru, Cu, Ti, and Ta. With the second surface 12 described above, the silylating agent is unlikely to form a bond, or the silylating agent does not form a bond, making it difficult to impart water repellency, thereby making it possible to selectively improve the water repellency of the first surface 11. Furthermore, the second surface 12 may contain other elements (O, N, C, H, P, B, etc.) to the extent that they do not adversely affect film formation in the film-forming process. Note that the above phrase "not containing Si element" means that the element does not increase the water repellency of the second surface 12, and may be present in trace amounts that do not affect the water repellency.

[0027] First surface 11 and second surface 12 may be the surface of a member made of the above-mentioned materials, or may be the surface of a film formed from the above-mentioned materials. Also, both the surface of a member made of the above-mentioned materials and the surface of a film formed from the above-mentioned materials may exist.

[0028] The water repellency imparted to the first surface 11 and the second surface 12 by the silylation agent is usually an inherent property of the material that constitutes the surface, but it can be adjusted by the pretreatment described below and the desilylation treatment of the silyl groups, etc. For example, the effect of the silylation treatment described above can be strengthened or weakened by the pretreatment. 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 the "water repellency of the surface" 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" will be used.

[0029] (Surface Modification Step) The surface modification step includes a silylation treatment in which at least the first surface 11 of the substrate surface is silylated with a chemical solution containing a silylating agent, a catalytic compound, and an aprotic solvent, and substantially free of a nitrogen-containing heterocyclic compound. This makes it possible to selectively improve the water repellency of the first surface 11 relative to the second surface 12. In other words, the water contact angle of the first surface 11 can be made relatively larger than the water contact angle of the second surface 12.

[0030] In the silylation treatment, as shown in Fig. 2, a chemical solution described below is brought into contact with at least the first surface 11 and the second surface 12. In the silylation treatment, the chemical solution may be supplied once or twice or more times, but from the viewpoint of improving the efficiency of the manufacturing process, it is preferable to supply the chemical solution once. When the chemical solution is supplied twice or more times, the silylating agent contained in the chemical solution supplied the first and second times may be the same or different, but using the same silylating agent is preferable because it may be easier to suppress variation and improve work efficiency.

[0031] A water-repellent film 21 is formed on the first surface 11 by the silylation treatment. The water-repellent film 21 on the first surface 11 may be composed of a film that covers at least a portion or the entire surface. The water-repellent film 21 formed on the first surface 11 preferably has a high water contact angle, and may be, for example, 75° or greater. It may be preferably 78° or greater, more preferably 80° or greater, and even more preferably 84° or greater. Furthermore, if the second surface 12 exhibits a water contact angle that is 10° or greater lower than the water contact angle of the first surface 11, the water repellency of the first surface may be selectively improved. It may be more preferably 15° or greater, and even more preferably 20° or greater.

[0032] The chemical solution can be supplied in a liquid or vapor state, but is preferably supplied in a liquid state because this makes it easier to suppress fluctuations in the chemical solution composition upon contact with first surface 11 and second surface 12. Known means can be used as the supply method, and examples of the supply method include a single-wafer method such as spin coating and a batch method such as immersion when supplying in a liquid state. Furthermore, when supplying in a vapor state and turning it into a liquid after contact with first surface 11 and second surface 12, known vapor injection methods can be used.

[0033] The silylation treatment can improve the water repellency of at least the first surface 11. Alternatively, it may be preferable to form a water repellent film on the first surface 11 by the silylation treatment, but not form a water repellent film on the second surface 12. The silylation treatment 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, thereby improving the water repellency.

[0034] Furthermore, because the second surface 12 is essentially a surface that does not have Si—OH bonds, a water-repellent film is hardly formed. However, even if a water-repellent film is not formed, the water-repellent property may be increased by having a structure in which a compound derived from the silylation agent is physically bonded (e.g., attached or adsorbed) to the surface. Furthermore, if a small amount of Si—OH bonds is contained, the silylation agent may bond to the surface using those sites as reaction sites, resulting in the local formation of a water-repellent film. In either case, the occurrence of the partial water-repellent property described above can be eliminated or reduced by various cleaning methods or the desilylation treatment described below.

[0035] Whether a compound derived from a silylation agent has adhered to the second surface 12 or whether a water-repellent film has been formed on the surface can be easily confirmed by estimating the change in water contact angle before and after the surface modification process. If the increase in water contact angle after the surface modification process relative to the water contact angle before the surface modification process is 8° or less, it may be determined that a compound derived from a silylation agent or a water-repellent film has not adhered or been formed. This may be preferably 5° or less, and more preferably 3° or less. Furthermore, if the second surface 12 does not originally contain Si elements, X-ray photoelectron spectroscopy (XPS) may be used to measure peaks derived from Si on the second surface 12 after the silylation process, and confirmation may be made based on whether or not a peak derived from Si can be confirmed.

[0036] In the surface modification step, a pretreatment described below may be carried out before the silylation treatment, if necessary.

[0037] If the number of reactive sites with the silylating agent on first surface 11 can be increased by pretreatment, it is possible to accelerate the silylation reaction in the silylation treatment. Furthermore, increasing the number of Si—OH bonds on first surface 11 makes it easier to form water-repellent film 21. If necessary, known means such as heating, decompression, or drying may be applied to the silylation treatment to accelerate the silylation reaction between the silylating agent and the OH groups on the surface.

[0038] Examples of pretreatment include a treatment to remove a native oxide film from the first surface 11 and a treatment to bond OH groups to at least a portion of the Si in the first surface 11. The pretreatment needs to be performed on at least the first surface 11, but may be performed on both the first surface 11 and the second surface 12 as long as it does not adversely affect the second surface 12. Furthermore, if the second surface 12 is oxidized by the pretreatment treatment to bond OH groups, a known reduction treatment or the like may be performed after the silylation treatment to remove the oxygen bonded by the pretreatment from the second surface 12.

[0039] In the surface modification step, if necessary, a desilylation treatment, which will be described later, may be carried out after the silylation treatment.

[0040] As shown in FIG. 3 , the desilylation treatment may be, for example, a method using a remover to remove the compounds derived from the silylation agent and the water-repellent film attached to the second surface 12 while leaving the water-repellent film 21 on the first surface 11.

[0041] Furthermore, 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 on each surface when a water-repellent film or the like is formed on each surface. The specific method for contacting the remover may be a known method, such as the same method as the silylation treatment described above.

[0042] Between the surface modification step and the film formation step described below, a cleaning treatment may be performed once or twice or more times to clean at least a portion of the substrate surface using a cleaning agent. This cleaning treatment may also be performed before the surface modification step or between each treatment during the surface modification step. For example, one or two or more cleaning treatments may be performed during any of the above pretreatment, silylation treatment, and water-repellent film removal treatment. In the case of multiple cleaning treatments, the type of cleaning agent may be changed for each treatment.

[0043] The cleaning agent may include an aqueous cleaning solution and / or a rinse solution.

[0044] The aqueous cleaning solution is not particularly limited as long as it can leave behind at least the water-repellent film 21 formed on the first surface 11. Examples include water, alcohol, a hydrogen peroxide solution, and ozone water. These may be used alone or in combination of two or more.

[0045] Similar to the aqueous cleaning solution, the rinse solution is not particularly limited as long as it allows at least the water-repellent film 21 formed on the first surface 11 to remain. A cleaning agent different from that used in the aqueous cleaning solution can be used for 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).

[0046] 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.

[0047] Between the surface modification step and the film formation step described below, a drying treatment for drying at least a part of the substrate surface may be performed once or twice or more times. This drying treatment may also be performed before the surface modification step or between each treatment during the surface modification step. For example, the drying treatment may be performed once or twice or more times during any of the above pretreatment, silylation treatment, and removal treatment. The drying treatment and the cleaning treatment may be repeated alternately.

[0048] The drying process may be carried out by known means such as spin drying, IPA (2-propanol) vapor drying, Marangoni drying, heat drying, air drying, hot air drying, vacuum drying, or the like.

[0049] Here, the upper limit of the N area ratio measured by XPS measurement according to the following procedure on the second surface 12 immediately before use in the next film formation process is, for example, 3.8 or less, preferably 2.0 or less, more preferably 1.8 or less, and even more preferably 1.4 or less. This allows the film formation process to be carried out on the second surface 12 in which the residual nitrogen-containing components are practically sufficiently suppressed. The lower limit of the N area ratio measured by XPS measurement is not particularly limited, but may be, for example, 0.5 or more, preferably 0.8 or more, or 0.9 or more. Note that "immediately before use in the film formation process" refers to before the film formation process carried out after the surface modification process. If the surface modification process includes other processes such as a drying process or a cleaning process in addition to the silylation process, this refers to before the film formation process carried out after the last of these processes.

[0050] (Procedure for calculating the N area ratio by XPS measurement) A substrate having a second surface 12, or a coupon obtained by cutting the substrate and having predetermined dimensions of length, width, and thickness, is prepared as a test piece. The surface on which the second surface 12 is formed is designated as the "main surface." The test piece is immersed in 0.5 mass % hydrofluoric acid at 25°C for 1 minute, then immersed in ion-exchanged water at room temperature for 1 minute, and N is applied to the surface for 10 seconds. ２ The substrate is then immersed in a chemical solution at 60°C for 1 minute to carry out a surface modification process. The substrate is then immersed in 2-propanol at room temperature for 1 minute, and then in ion-exchanged water at room temperature for 1 minute. The surface is then immersed in N 2 for 10 seconds. ２ A chemically treated test piece is prepared by blowing gas onto the test piece and drying it (cleaning and drying process). A blank test piece with a second surface 12 is prepared by the same process as above, except that the cleaning and drying process is performed without the surface modification process. Thereafter, XPS analysis is performed on each of the main surfaces of the chemically treated test piece and the blank test piece using an X-ray photoelectron spectrometer (XPS) device (manufactured by ULVAC-PHI, Inc., PHI 5000 VersaProbe II), and the peak area of ​​nitrogen element (N peak area) on the second surface 12 is determined. The N peak area on the second surface 12 of the blank test piece is calculated as N ０ The N peak area on the second surface 12 of the chemical-treated test piece is N １ When N１ / N ０ The above N peak area ratio is calculated from the above. <XPS irradiation conditions> X-ray source used: Al (Kα) ray (1.5 keV) Photoelectron take-off angle: 45° X-ray beam diameter: approximately 100 μm Neutralization gun conditions: 1 V, 20 μA Reference peak position: The environmental carbon 1s peak is set to 284.8 eV. A baseline is drawn for each peak using the analysis software provided with the XPS device, and the peak area (peak integral value) is calculated.

[0051] (Film Forming Step) In the film forming step, after the surface modification step, a film material is selectively supplied in a vapor phase to the second surface 12 shown in FIG. 3 to form a film.

[0052] During the film formation process, film formation is suppressed on the first surface 11, but film material is deposited on the second surface 12 to form a film. If the first surface 11 has good water repellency, the film tends to have a relatively higher density than a water-repellent film formed on a surface with low water repellency, although the detailed mechanism is unclear. Therefore, it is presumed that deposition of the film material is inhibited and film formation is suppressed. On the other hand, it is difficult to form a water-repellent film on the second surface 12, so it is presumed that film formation can be selectively performed on the second surface 12 compared to the first surface 11.

[0053] As a film formation method, known CVD methods, atomic layer deposition methods, etc. can be used. In particular, atomic layer deposition is preferred because of its excellent film thickness control, uniformity, and conformability to the surface shape of the film formation target. As a film formation method using atomic layer deposition, known ALD equipment can be used. For example, a thin film formation method (thermal ALD method) by adsorption using a first gas-phase reactant (film material) and a desired second gas-phase reactant, or a thin film formation method (plasma ALD method) in which a first gas-phase reactant (film material) is adsorbed on a surface and then reacted with 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 film material.

[0054] The first gas phase reactive substance used includes a film 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(CH ３ ) ２ , TMA (trimethylaluminum), TaCl ５ , W.F. ６ , WOCl ４ , CuCl, ZrCl ４ , AlCl ３ , TiCl ４ , SiCl ４ , HfCl ４ etc.

[0055] 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.

[0056] 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 O５ , 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.

[0057] The film-forming step may be repeated multiple times. If the silylation agent in the chemical solution does not form a water-repellent film on the film obtained by the film-forming step, the surface modification step may be performed again to improve the water repellency of first surface 11, and then the film-forming step may be repeated multiple times to form a film on the film formed on second surface 12.

[0058] If the water-repellent film 21 remaining on the first surface after the above-described film-forming process is unnecessary, the water-repellent film 21 may be removed. The removal method is not particularly limited as long as it is a method capable of removing a known silylating agent or silyl group. 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, a sulfuric acid aqueous solution, or hydrofluoric acid.

[0059] 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.

[0060] Each component of the chemical solution used in the above substrate processing method will now be described.

[0061] (Silylating Agent) The silylating agent may be a known silylating agent. For example, the silylating agent may be a silicon compound represented by the following general formula [1]. These may be used alone or in combination of two or more.

[0062] R １ ａ Si(H) ｂ X ４－ａ－ｂ [1]

[0063] 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 atom bonding 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.

[0064] R in the above general formula [1] １ may contain not only hydrogen, carbon, nitrogen, oxygen, and fluorine atoms, but also silicon, sulfur, and halogen atoms (other than fluorine). １ R in the above general formula [1] may contain an unsaturated bond, an aromatic ring, or a cyclic structure. １ As each independently, 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, silicon compounds having a trialkylsilyl group can be used.

[0065] The silicon compound is a compound represented by the R １However, it is preferable that each of the long-chain silylating agents independently contains a short-chain silylating agent, which is an organic group containing a hydrocarbon group having 1 to 8 carbon atoms, in which some or all of the hydrogen atoms may be replaced by fluorine atoms. More preferably, the short-chain silylating agent may contain an organic group containing a hydrocarbon group having 1 to 7 carbon atoms. Although a water-repellent film using a long-chain silylating agent has a high water contact angle, when it is formed into a complex pattern, there is a concern that the degree of adhesion may vary depending on the method of application to the surface, resulting in unstable protective performance. A short-chain silylating agent can stabilize such protective performance. Although the detailed mechanism is unclear, it is presumed that this is because short-chain silylating agents are more likely to diffuse over the surface after application than long-chain silylating agents.

[0066] R in the above general formula [1] １ When R contains a silicon atom, it 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 a silicon atom) 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 ) ｐ The methylene chain represented by - may be substituted with a halogen.

[0067] In X in the above general formula [1], the monovalent organic group in which the atom bonded to the Si atom is nitrogen, oxygen, or carbon may contain not only hydrogen, carbon, nitrogen, or oxygen atoms, but also silicon, sulfur, halogen atoms, etc.

[0068] Examples of the monovalent organic group in which the atom bonded to the Si atom is nitrogen include 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 , -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, some or all of whose hydrogen atoms may be replaced by fluorine atoms, and a fluorine atom), -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. 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. ａ３ )-Si(Rａ４ ) (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.

[0069] Examples of the silylating agent in which X in the general formula [1] is a monovalent organic group in which the atom bonded to the Si atom is nitrogen include CH ３ Si(NH ２ ) ３ , C ２ H ５ Si(NH ２ ) ３ , C ３ H ７ Si(NH ２ ) ３ , C ４ H ９ Si(NH ２ ) ３ , C ５ H １１ Si(NH ２ ) ３ , C ６ H １３ Si(NH ２ ) ３ , C ７ H １５ Si(NH ２ ) ３ , C ８ H １７ Si(NH ２ ) ３ , C ９ H １９H 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 ) ２ H 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 H ３ ) 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 H３ ) 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 )NH ２ 、(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 H３ ) 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 ３１ H 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 H５ ) 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 CH ２ 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 H ３ ) 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 CH２ Si(CH ３ ) ２ NH ２ , C ３ F ７ CH ２ CH ２ Si(CH ３ ) ２ NH ２ , C ４ F ９ CH ２ CH ２ Si(CH ３ ) ２ NH ２ , C ５ F １１ CH ２ CH ２ Si(CH ３ ) ２ NH ２ , C ６ F １３ CH ２ CH ２ Si(CH ３ ) ２ NH ２ , C ７ F １５ CH ２ CH ２ Si(CH ３ ) ２ NH ２ , C ８ F １７ CH ２ CH ２ Si(CH ３ ) ２ NH ２ , C.F. ３ CH ２ CH ２ Si(CH ３ ) (H) NH ２ aminosilanes such as aminodimethylvinylsilane, aminodimethylphenylethylsilane, aminodimethylphenylsilane, aminomethyldiphenylsilane, and aminodimethyl-t-butylsilane, or the amino group (—NH ２ group), -N=C=O, dialkylamino group (-N(CH ３ ) ２ , -N(C ２ H ５ ) ２etc.), 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.), —NH—C(═O)—Si(CH ３ ) ３ , -N(S(=O) ２ R ４ ) ２ (R ４ is as described above. For example, N-(trimethylsilyl)bis(trifluoromethanesulfonyl)imide, etc.), —N═C(NR ６ ２ ) ２ , -N=C(NR ６ ２ ) R ６ (R ６ is as described above. For example, 2-trimethylsilyl-1,1,3,3-tetramethylguanidine, etc.), —N(R ａ１ ) R ａ２ (R ａ１ , R ａ２ is as described above.), -N(R ａ３ )-Si(R ａ４ ) (R ａ５ ) (R ａ６ ) (R ａ３ , R ａ４ , R ａ５ and R ａ６are as described above. 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, 1,1,3,3-tetraphenyl-1,3-dimethyldisilazane, nonamethyltrisilazane, pentamethylethyldisilazane, pentamethylvinyldisilazane, pentamethylpropyldisilazane, pentamethylethyldisilazane, pentamethyl-t-butyldisilazane, pentamethylphenyldisilazane, trimethyltriethyldisilazane, etc.), —N(R ａ７ )-C(=O)R ａ８ (R ａ７ , R ａ８ are as described above. For example, N-trimethylsilylacetamide, N-trimethylsilyltrifluoroacetamide, N-methyl-N-trimethylsilylacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide, bis(trimethylsilyl)acetamide, bis(trimethylsilyl)trifluoroacetamide, etc.) may be substituted.

[0070] Examples of the silylating agent in which X in the general formula [1] is a monovalent organic group in which the atom bonded to the Si atom 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 ａ１０ each independently represents a hydrogen atom, a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, a fluorine-containing alkyl group, a chlorine-containing alkyl group, a trialkylsilyl group, a trialkylsiloxy group, an alkoxy group, a phenyl group, a phenylethyl group, or an acetyl group, and ａ１１represents 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. For example, CH 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 ５ H 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 、(C ２ H ５ ) ２ Si(OCH ３ ) ２ 、C ３ H ７ Si(H) ３ )(OCH ３ ) ２ 、(C３ 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 )(OCH３ ) 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 ９ Si(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 ３５ Si(H) ３ ) ２ OCH ３ 、C １８ H ３７ Si(H)３ ) ２ OCH ３ 、(CH ３ ) ２ Si(H)OCH ３ 、CH ３ Si(H) ２ OCH ３ 、(C ２ H ５ ) ２ Si(H)OCH ３ 、C ２ H ５ Si(H) ２ OCH ３ 、C ２ H ５ Si(CH ３ )(H)OCH ３ 、(C ３ H ７ ) ２ Si(H)OCH ３ 等 alkyl methoxysilanes, or, CF ３ CH ２ CH ２ Si(OCH ３ ) ３ 、C ２ F ５ CH ２ CH ２ Si(OCH ３ ) ３ 、C ３ F ７ CH ２ CH ２ Si(OCH ３ ) ３ 、C ４ F ９ CH ２ CH ２ Si(OCH ３ ) ３ 、C ５ F １１ CH ２ CH ２ Si(OCH ３ ) ３ 、C ６ F １３ CH ２ CH ２ Si(OCH ３ ) ３ 、C ７ F １５ CH２ 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 ２ Si(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 、CF ３ CH ２ CH ２ Si(H) ３ )(H)OCH ３or 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.)

[0071] Examples of silylating agents in which X in the general formula [1] is a monovalent organic group in which the atom bonded to the Si atom 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, and 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.

[0072] Examples of the silylating agent in which X in the general formula [1] is a monovalent organic group in which the atom bonded to the Si atom 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.

[0073] Furthermore, examples of the silylating agent in which X in the general formula [1] is a monovalent organic group in which the atom bonded to the Si atom 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.).

[0074] In the general formula [1], b is preferably 0. X is more preferably a monovalent organic group in which the atom bonded to the Si atom is nitrogen or oxygen. １ is preferably a methyl group.

[0075] The silylating agent can include a silazane compound, such as acyclic disilazane compounds such as hexamethyldisilazane, heptamethyldisilazane, tetramethyldisilazane, diethyltetramethyldisilazane, dipropyltetramethyldisilazane, dibutyltetramethyldisilazane, dihexyltetramethyldisilazane, dioctyltetramethyldisilazane, and didecyltetramethyldisilazane.

[0076] More specific examples of suitable silylating agents include one or more selected from the group consisting of hexamethyldisilazane, heptamethyldisilazane, N-(trimethylsilyl)dimethylamine, bis(dimethylamino)dimethylsilane, bis(trimethylsilyl)trifluoroacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide, N-trimethylsilylacetamide, bistrimethylsilyl sulfate, hexamethyldisiloxane, trimethylsilyltrifluoroacetate, trimethylsilyltrifluoromethanesulfonate, trimethylsilylbenzenesulfonate, and trimethylsilyltoluenesulfonate.

[0077] (Catalytic Compound) The catalytic compound does not contain a nitrogen-containing heterocyclic compound and promotes the silylation reaction caused by the silylating agent. As the catalytic compound, it is preferable to use one or more selected from the group consisting of Compound A and acid imides described below. Here, the catalytic compound is a compound that can promote the reaction between the main surface and the silylating agent and improve the water-repellent performance of the formed water-repellent film, and the catalytic compound itself or a modified compound thereof may constitute a part of the water-repellent film.

[0078] The compound A may be at least one selected from the group consisting of a carboxylic acid represented by the following general formula

[16] , an anhydride of the carboxylic acid, a salt of the carboxylic acid, and a carboxylic acid derivative represented by the following general formula

[17] : ２９ —C(═O)OH

[16] [In the above general formula

[16] , R ２９ 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.] R ２９’ -C(=O)O-Si(H) ３－ｈ (R ３０ ) ｈ

[17] [In the above general formula

[17] , R ２９’ 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 ３０ 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 h is an integer of 1 to 3.

[0079] 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.] R８' -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.

[0080] Furthermore, the compound A may be at least one selected from the group consisting of a sulfonate ester represented by the following general formula [5], a sulfonimide represented by the following general formula [6], a sulfonimide derivative represented by the following general formula [8], a sulfonmethide represented by the following general formula

[10] , and a sulfonmethide derivative 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, some or all of whose hydrogen atoms may be replaced by fluorine atoms, and a fluorine atom. １４ -S(=O) ２ ) ２ N) ｓ Si(H) ｔ (R １５ ) ４－ｓ－ｔ [8] [In the above general formula [8], R １４are each independently 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 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.] (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, some or all of whose hydrogen atoms may be replaced by fluorine atoms, and a fluorine atom. 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, some or all of whose 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.

[0081] Specific examples of the compound A include 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 the compound can contain one or more selected from these.These compounds can be used alone or in combination of two or more.

[0082] A more preferred specific example of compound A may include, for example, one or more selected from the group consisting of trimethylsilyl trifluoroacetate, dimethylsilyl trifluoroacetate, butyldimethylsilyl trifluoroacetate, hexyldimethylsilyl trifluoroacetate, octyldimethylsilyl trifluoroacetate, and decyldimethylsilyl trifluoroacetate.

[0083] A further preferred specific example of compound A may include one or more selected from the group consisting of trimethylsilyl trifluoromethanesulfonate, dimethylsilyl trifluoromethanesulfonate, butyldimethylsilyl trifluoromethanesulfonate, hexyldimethylsilyl trifluoromethanesulfonate, octyldimethylsilyl trifluoromethanesulfonate, and decyldimethylsilyl trifluoromethanesulfonate.

[0084] The use of the compound A can improve the water contact angle on the first surface without leaving any catalytic compound remaining on the second surface, and therefore the compound A can be used effectively.

[0085] Although the above-mentioned compound A may correspond to the above-mentioned silylating agent, when it is used as a catalytic compound, it means that it is used in combination with another silylating agent other than compound A. When used in combination, it is preferable to set the concentration of compound A to be equal to or lower than the concentration of the other silylating agent, because compound A acts more easily as a catalytic compound.

[0086] 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, and more preferably 1 to 10,000 times, the acetic acid or sulfonic acid.

[0087] R ２ ｃ (H) ｄ Si-X ４－ｃ－ｄ [2] [In the above general formula [2], R ２ is the above R １ X is the same as in the above general formula [1], c is an integer of 1 to 3, d is an integer of 0 to 2, and the sum of c and d is 1 to 3.]

[0088] The sum of the above c and d is preferably 3, and more preferably d may be 0. In addition, in the above general formula [2], R ２ ｃ (H) ｄ Examples of Si- include (CH ３ ) ３ Si-, (CH ３ ) ２ (H)Si-, (C ４ H ９ ) (CH ３ ) ２ Si-, (C ６ H １３ ) (CH ３ ) ２Si-, (C ８ H １７ ) (CH ３ ) ２ Si-, (C １０ H ２１ ) (CH ３ ) ２ Si- and the like.

[0089] Examples of the acid imide compounds include compounds having a chemical structure in which an acid such as a carboxylic acid or phosphoric acid is imidized.

[0090] (Aprotic Solvent) An aprotic solvent refers to a solvent that does not contain a group in which a hydrogen atom is bonded to an oxygen atom or a nitrogen atom, such as a hydroxyl group or an amino group. The aprotic solvent is not particularly limited as long as it dissolves the silylating agent and the catalytic compound. Examples of aprotic solvents that can be used include organic solvents such as hydrocarbons, esters, ethers, ketones, halogen atom-containing solvents, sulfoxide solvents, carbonate solvents, polyhydric alcohol derivatives that do not have an OH group, acyclic nitrogen atom-containing solvents that do not have an N—H group, and silicone solvents. Among these, hydrocarbons, esters, ethers, halogen atom-containing solvents, sulfoxide solvents, and polyhydric alcohol derivatives that do not have an OH group are preferred. These aprotic solvents may be used alone or in combination of two or more.

[0091] 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 of these hydrocarbons (e.g., isododecane, isocetane, etc.), cyclohexane, methyl ... Examples of such an alkyl methyl cyclohexane include ethyl cyclohexane, decalin, benzene, toluene, xylene, (ortho-, meta-, or para-)diethylbenzene, 1,3,5-trimethylbenzene, butylbenzene, naphthalene, p-menthane, o-menthane, m-menthane, diphenylmenthane, limonene, α-terpinene, β-terpinene, γ-terpinene, bornane, norbornane, pinane, α-pinene, β-pinene, carane, longifolene, and abietane.

[0092] 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.

[0093] 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.

[0094] 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.

[0095] Examples of the ketones include acetone, acetylacetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, 2-heptanone, 3-heptanone, cyclohexanone, and isophorone.

[0096] Examples of the halogen atom-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 Zeorola 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 AGC Inc.), Novec HFE-7100, Novec Examples of such fluorocarbons include hydrofluoroethers such as HFE-7200, Novec 7300, and Novec 7600 (all manufactured by 3M Japan Ltd.), 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.

[0097] Examples of the sulfoxide solvent include dimethyl sulfoxide.

[0098] Examples of the carbonate solvent include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, and propylene carbonate.

[0099] 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.

[0100] Examples of the acyclic nitrogen atom-containing solvent having no N—H group include N,N-dimethylacetamide and triethylamine.

[0101] Examples of the silicone solvent include hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, and dodecamethylpentasiloxane.

[0102] 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, and propylene glycol. At least one selected from the group consisting of 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 is preferred. Also preferred are propylene carbonate, linear or branched hydrocarbon solvents having 6 to 12 carbon atoms, p-menthane, diphenylmenthane, limonene, terpinene, bornane, norbornane, pinane, and the like.

[0103] Suitable examples of aprotic solvents to be combined with the above-mentioned suitable specific examples of silylating agents include those containing 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. The chemical solution of this embodiment further contains the above-mentioned catalytic compound.

[0104] The chemical solution used in the first embodiment is a composition containing the silylating agent, the catalytic compound, and the aprotic solvent, and is substantially free of a nitrogen-containing heterocyclic compound. Use of this chemical solution can prevent the adhesion of nitrogen-containing heterocyclic residues to the second surface.

[0105] Examples of nitrogen-containing heterocyclic compounds 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, piperidine, silylated imidazole compounds, and silylated triazole compounds. Examples of silylated imidazole compounds and silylated triazole compounds include monomethylsilylimidazole, dimethylsilylimidazole, trimethylsilylimidazole, monomethylsilyltriazole, dimethylsilyltriazole, and trimethylsilyltriazole. Furthermore, the compounds are not limited to those listed above.

[0106] It is preferable that the silylating agent be contained in an amount of 0.5% by mass or more relative to the total amount of the chemical solution. It may be more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 8% by mass or more. By setting the amount within the above range, the water repellency of the first surface is more likely to be improved. Furthermore, the upper limit is not particularly limited, but may be, for example, 90% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less. In this specification, the amount contained relative to the total amount of the chemical solution means the ratio of the content of each component when the total amount of the chemical solution is 100% by mass.

[0107] It is preferable that the catalytic compound be contained in an amount of 0.1% by mass or more relative to the total amount of the chemical solution. It may be more preferably 0.5% by mass or more, even more preferably 1.0% by mass or more, even more preferably 2.0% by mass or more, and even more preferably 2.5% by mass or more. By setting the amount within the above range, the water repellency of the first surface is more likely to be improved. Furthermore, the upper limit of the catalytic compound content is not particularly limited, but may be, for example, 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less, relative to 100% by mass of the chemical solution. This makes it easier to suppress changes in the components of the chemical solution during storage.

[0108] When the content of the silylating agent in terms of mass in 100 mass% of the chemical solution is X and the content of the catalytic compound is Y, the chemical solution may be configured so that X and Y satisfy the relationship 1.0<X / Y≦20. The lower limit of X / Y may be, for example, more than 1.0, preferably 2.0 or more, and more preferably 2.5 or more. The upper limit of X / Y may be, for example, 20 or less, preferably 14 or less, and more preferably 10 or less. As the amount of catalytic compound increases, the value of the water contact angle increases, but on the other hand, even if the catalytic compound is present in excess of the silylating agent, the improvement in the water contact angle tends not to change. Therefore, within the above range, water repellency is likely to be efficiently improved.

[0109] The aprotic solvent preferably accounts for 10% by mass or more of the total amount of the chemical solution, more preferably 50% by mass or more, even more preferably 70% by mass or more, and even more preferably 80% by mass or more. The upper limit is not particularly limited, but may be the amount obtained by subtracting the content of the silylating agent and the content of the catalytic compound from the total amount of the chemical solution, and is preferably 95% by mass or less, more preferably 92% by mass or less.

[0110] The solvent contained in the chemical solution is preferably substantially only an aprotic solvent. Alternatively, a plurality of aprotic solvents may be used. Specifically, when the total amount of solvents contained in the chemical solution is taken as 100, the aprotic solvent preferably accounts for 90% by mass or more, more preferably 95% by mass or more, even more preferably 98% by mass or more, and even more preferably 99.5% by mass or more.

[0111] It is desirable that the chemical solution be substantially free of water. Furthermore, a chemical solution that is substantially free of water is more preferable, obtained by not adding water during preparation of the chemical solution or by using raw materials for each component that do not contain water or have a low water content. For example, the water content in the chemical solution may be 0.3% by mass or less, preferably 0.1% by mass or less. Furthermore, the water content may be less than the measurement limit of Karl Fischer titration, for example, less than 10 ppm by mass. By using such a chemical solution, it is possible to prevent the silylating agent from being deactivated.

[0112] The chemical solution may contain other components in addition to the above-mentioned components, as long as the components do not impair the objectives of the present disclosure. Examples of such other components include oxidizing agents such as hydrogen peroxide and ozone, surfactants, and antioxidants such as BHT.

[0113] The chemical solution of this embodiment is obtained by mixing and dissolving the above-mentioned components. The obtained mixture (i.e., solution) may be purified using an adsorbent, a filter, or the like, as necessary. Alternatively, each component may be purified in advance by distillation, or by using an adsorbent, a filter, or the like.

[0114] 2. Second Embodiment A second embodiment will be described below. Note that descriptions that overlap with the first embodiment will be omitted, and only the differences will be described below.

[0115] A substrate treatment method according to a second embodiment includes a preparation step of preparing a substrate having a first surface containing Si and a second surface containing a metal element but not Si, a surface modification step of supplying a chemical solution containing the silylating agent, the catalytic compound, and the aprotic solvent to the first and second surfaces to selectively improve the water repellency of the first surface relative to the second surface, and a film formation step of supplying a film material in a gas phase to the second surface to selectively form a film. In this substrate treatment method, the chemical solution contains 8% by mass or more of the silylating agent relative to 100% by mass of the chemical solution, and does not contain a nitrogen-containing heterocyclic compound, or satisfies the following formulation conditions: Cc is the content (mass %) of the catalytic compound contained in 100% by mass of the chemical solution, and Cn is the content (mass %) of the nitrogen-containing heterocyclic compound, Cn is 0.05% by mass or less, and Cn / Cc is 0.01 or less.

[0116] In the second embodiment, the chemical solution used in the second embodiment is substantially free of the catalytic compound described above. When the chemical solution used in the second embodiment is substantially free of a catalytic compound, fluctuations in the chemical solution composition upon contact with the first surface 11 and the second surface 12 are relatively easily suppressed. Therefore, it is preferable to vaporize the chemical solution and then supply the vapor of the chemical solution to the first surface 11 and the second surface 12. The supply method is as described above, and known vapor injection methods can be used. Even when supplied as a vapor, the vapor becomes liquid after contact with the first surface 11 and the second surface 12 and adheres to the first surface 11 and the second surface 12, thereby subjecting at least the first surface to a silylation treatment. It is preferable to adjust the temperature of the vapor, the first surface 11, and the second surface 12, or both, to a temperature above room temperature (20 to 25°C) and below the boiling point of the silylation agent before contact. The temperature may be more preferably 20°C or higher and 80°C or lower, and even more preferably 40°C or higher and 60°C or lower. Adjusting the temperature within this temperature range makes it easy to improve the water repellency of the first surface 11, even with a chemical solution that is substantially free of a catalytic compound. The temperature may be adjusted by a known method, for example, by providing a heater or cooling mechanism for adjusting the temperature inside the device, by using separate hot air or cold air, or by heating or cooling the substrate.

[0117] Furthermore, in the present embodiment, when the chemical solution is substantially free of a catalytic compound, the chemical solution, the first surface 11, and the second surface 12, or both, may be adjusted to a temperature above room temperature and below the boiling point of the silylation agent, and the chemical solution may be supplied as a liquid to the first surface 11 and the second surface 12. The temperature may be more preferably 20°C or higher and 80°C or lower, and even more preferably 40°C or higher and 60°C or lower. By adjusting the temperature within this range, the water repellency of the first surface 11 is likely to be improved even when the chemical solution is substantially free of a catalytic compound. The temperature may be adjusted by a known method, such as by providing a temperature-adjusting heater or cooling mechanism within the device, by using separate hot or cold air, or by heating or cooling the substrate.

[0118] The chemical solution of this embodiment contains a silylating agent in an amount of 8% by mass or more relative to the total amount of the chemical solution. By setting the content within this range, it is possible to improve the water repellency of the first surface. Preferably, the content may be 9% by mass or more.

[0119] 3. Third Embodiment The third embodiment will be described below. Note that descriptions overlapping with the first embodiment will be omitted, and only the differences will be described below. A substrate treatment method in the third embodiment includes a preparation step of preparing a substrate having a first surface containing Si element and a second surface containing a metal element but not Si element, and a surface modification step of supplying a chemical solution containing a silylating agent, a catalytic compound, and an aprotic solvent to the first surface and the second surface to selectively improve the water repellency of the first surface relative to the second surface. In this substrate treatment method, the chemical solution does not contain a nitrogen-containing heterocyclic compound, or satisfies the following formulation conditions: Cc is the content (mass %) of the catalytic compound contained in 100 mass % of the chemical solution, and Cn is the content (mass %) of the nitrogen-containing heterocyclic compound, Cn is 0.05 mass % or less, and Cn / Cc is 0.01 or less. In the third embodiment, the process is not limited to the film-forming process in the first embodiment, and after the surface modification process, known processing steps can be performed on the first or second surface. The processing steps may be any process used in the manufacturing process of a substrate such as a semiconductor substrate, such as a fine pattern formation process, a dicing / grinding process, a film-forming process, a cleaning process, or a drying process. These processes may be included alone or in combination of any two or more, and the order of the processes may be determined arbitrarily. In other words, since the remaining nitrogen-containing components can be suppressed, the processing steps after the surface modification process are not particularly limited, and any process can be performed.

[0120] 4. Fourth Embodiment The fourth embodiment will be described below. Note that descriptions overlapping with the first embodiment will be omitted, and only the differences will be described below. A substrate treatment method in the fourth embodiment includes a preparation step of preparing a substrate having a first surface containing Si element and a second surface containing a metal element but not Si element; a surface modification step of supplying a chemical solution containing a silylating agent, a catalytic compound, and an aprotic solvent to the first surface and the second surface to selectively improve the water repellency of the first surface relative to the second surface; and an etching step of performing wet etching or dry etching on the second surface. In this substrate treatment method, the chemical solution does not contain a nitrogen-containing heterocyclic compound, or satisfies the following formulation conditions: where Cc is the content (mass %) of the catalytic compound contained in 100 mass % of the chemical solution and Cn is the content (mass %) of the nitrogen-containing heterocyclic compound, Cn is 0.05 mass % or less, and Cn / Cc is 0.01 or less. In the fourth embodiment, an etching step is performed instead of the film formation step in the first embodiment. The etching step involves known wet etching or dry etching, but since the remaining nitrogen-containing components can be suppressed, contamination of the surface by the nitrogen-containing components in subsequent processes can be suppressed. Furthermore, in order to selectively improve the water repellency of the first surface relative to the second surface, the second surface may be selectively etched relative to the first surface in a subsequent etching step. For example, the second surface / first surface etching selectivity ratio may be 2.5 or higher, preferably 5 or higher, and more preferably 10 or higher.

[0121] The above describes embodiments of the present disclosure, but these are merely examples of the present disclosure, and various other configurations can be adopted. Furthermore, the present disclosure is not limited to the above-described embodiments, and modifications, improvements, etc. are included within the scope of achieving the objectives of the present disclosure. Examples of reference embodiments are listed below. 1. A substrate treatment method, comprising: a preparation step of preparing a substrate having a first surface containing Si element and a second surface containing a metal element but not Si element; a surface modification step of supplying a chemical solution (hereinafter simply referred to as "chemical solution") containing a silylating agent, a catalytic compound, and an aprotic solvent, but not containing a nitrogen-containing heterocyclic compound, to the first surface and the second surface to selectively improve the water repellency of the first surface relative to the second surface; and a film formation step of supplying a film material in a vapor phase to the second surface to selectively form a film. 2.1. 2. A method for treating a substrate according to 1. or 2., wherein the catalytic compound comprises one or more compounds selected from the group consisting of 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. 3. A method for treating a substrate according to 1. or 2., wherein the silylating agent comprises a silicon compound represented by the following general formula [1]: １ ａ Si(H) ｂ X ４－ａ－ｂ [1] (In the above general formula [1], R １are 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, and X are each independently a monovalent organic group in which the atom 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. 4. The method for treating a substrate according to 3., wherein the silicon compound is a silicon compound represented by the R １are each independently an organic group containing a hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms. 5. A method for treating a substrate according to any one of 1. to 4., wherein the first surface contains one or more elements selected from the group consisting of Si, N, C, and O (including at least Si), and the second surface contains one or more elements selected from the group consisting of W, Co, Al, Ni, Ru, Cu, Ti, Ta, Hf, and Ge. 6. A method for treating a substrate according to any one of 1. to 5., wherein the film formation step is a step of forming a film by atomic layer deposition. 7. A method for treating a substrate according to any one of 1. to 6., wherein a cleaning treatment is performed to clean the substrate between the surface modification step and the film formation step. 8. A method for treating a substrate according to any one of 1. to 7. 9. A method for treating a substrate according to any one of 1. to 8., wherein a drying treatment is performed to dry the substrate between the surface modification step and the film formation step. 9. A method for treating a substrate according to any one of 1. to 8., wherein the surface modification step involves supplying the chemical solution in a liquid state to the first surface and the second surface. 10. A method for treating a substrate, comprising: a preparation step of preparing a substrate having a first surface containing Si element and a second surface containing no Si element but a metal element; a surface modification step of supplying a chemical solution containing a silylating agent and an aprotic solvent, but not a nitrogen-containing heterocyclic compound, to the first surface and the second surface to selectively improve the water repellency of the first surface relative to the second surface; and a film formation step of supplying a film material in a gas phase to the second surface to selectively form a film, wherein the chemical solution contains 8 mass % or more of a silylating agent relative to the total amount of the chemical solution. 12. A method for treating a substrate according to any one of items 1 to 11, wherein the surface modification step supplies vapor of the chemical solution to the first surface and the second surface.

[0122] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited to the descriptions of these examples.

[0123] (Examples 1 to 11, Comparative Examples 1 to 5) Chemical solutions were obtained by dissolving Compound 1 (a silylating agent) and Compound 2 (a catalytic compound and / or a nitrogen-containing heterocyclic compound) in a solvent (aprotic solvent) so as to obtain the components and contents shown in Table 1. The contents in Table 1 refer to the ratio of the content of each component when the total amount of the chemical solution is 100% by mass.

[0124]

[0125] The following abbreviations are used in Table 1: HMDS: 1,1,1,3,3,3-hexamethyldisilazane PGMEA: propylene glycol monomethyl ether acetate DOTMDS: 1,3-Di-n-octyl-1,1,3,3-tetramethyldisilazane ODMSTFA: octyldimethylsilyl trifluoroacetate TMSDMA: trimethylsilyldimethylamine TFAA: trifluoroacetic anhydride TMSTFA: trimethylsilyl trifluoroacetate

[0126] (SiO ２ Measurement of water contact angle on surface (first surface) A silicon wafer having no uneven pattern on its surface and a 1 μm thick silicon oxide film on its surface was cut to prepare multiple coupons (test pieces) made of silicon substrates with length, width, and thickness dimensions of 4 cm, 1 cm, and 0.75 mm. The surface on which the silicon oxide film was formed was regarded as the "main surface," and the following evaluations were carried out. [Immersion method: Examples 1 to 10, Comparative Examples 1 to 5] The obtained coupons were immersed in 0.5 mass % hydrofluoric acid at 25°C for 1 minute, then immersed in ion-exchanged water at room temperature for 1 minute, and N ２ The substrate was then immersed in the prepared chemical solution at 60°C for 1 minute to carry out a surface modification process. The substrate was then immersed in 2-propanol at room temperature for 1 minute, and then in ion-exchanged water at room temperature for 1 minute. The surface was then immersed in N 2 for 10 seconds. ２The coupon was then dried by spraying gas onto it to prepare a coupon for evaluation (cleaning and drying step). [Vapor Method: Example 11] In Example 11, the coupon was placed horizontally in a vapor treatment chamber, and the solution-state composition prepared above was vaporized under the following vapor supply conditions, and the vapor was supplied to the vapor treatment chamber. Vapor supply conditions for the composition: 2 dm3 of nitrogen gas was blown into the vaporization chamber heated to 165°C. ３ The prepared solution composition was dripped at a drip rate of 0.01 g / sec while flowing at a flow rate of 1 / min. The entire dripped amount was vaporized. The vapor was immediately supplied to the vapor treatment chamber with a nitrogen gas flow. This treatment was carried out for 40 seconds. The vapor supplied to the coupon surface was then converted to a liquid state to carry out the surface modification process. Next, the coupon was immersed in 2-propanol at room temperature for 1 minute, then in ion-exchanged water at room temperature for 1 minute, and the surface was then immersed in N gas for 10 seconds. ２ The coupon was dried by blowing gas onto it, and an evaluation coupon was prepared (cleaning and drying process).

[0127] Each of the dried coupons obtained by the immersion method or the vapor method was placed on a horizontal surface, and 2 μl of pure water was placed on the main surface of each coupon at room temperature. The angle between the water droplet and the main surface of the coupon (water contact angle) was measured using a contact angle meter (CA-X model, manufactured by Kyowa Interface Science Co., Ltd.) in accordance with JIS R 3257:1999.

[0128] (Measurement of Water Contact Angle on Cu Film Surface (Second Surface)) A silicon wafer having a Cu film with a thickness of 100 nm on its surface was used, and the surface on which the Cu film was formed was used as the main surface. ２ The water contact angle was measured in the same manner as for the surface.

[0129] (Measurement of Water Contact Angle on Blank) The SiO ２ The water contact angle was measured in the same manner as for the surface. ２ The water contact angle was measured in the same manner as for the Cu surface, except that the cleaning and drying steps were carried out without carrying out the surface modification step, and the Cu surface (second surface) was used as a blank.

[0130] (Calculation of N area ratio by XPS measurement) XPS analysis was performed using an X-ray photoelectron spectrometer (XPS) (ULVAC-PHI, PHI 5000 VersaProbe II). <XPS irradiation conditions> X-ray source used: Al (Kα) ray (1.5 keV) Photoelectron take-off angle: 45° X-ray beam diameter: approximately 100 μm Neutralization gun conditions: 1 V, 20 μA Reference peak position: environmental carbon 1s peak was set to 284.8 eV. A baseline was drawn for each peak using the analysis software provided with the XPS instrument, and the peak area (peak integral value) was calculated. Measurement coupons were prepared using the same procedure as for each coupon used to measure the water contact angle, and measurements were performed on each main surface. Specifically, a silicon wafer having no uneven surface pattern and a 1 μm thick silicon oxide film on its surface was cut to prepare multiple coupons (test pieces) made of silicon substrates with length, width, and thickness dimensions of 4 cm, 1 cm, and 0.75 mm. The surface on which the silicon oxide film was formed was regarded as the "main surface" for evaluation. [Immersion method: Examples 1 to 10, Comparative Examples 1 to 5] The obtained coupons were immersed in 0.5 mass % hydrofluoric acid at 25°C for 1 minute, then immersed in ion-exchanged water at room temperature for 1 minute, and N 2 was applied to the surface for 10 seconds. ２ The substrate was then immersed in the prepared chemical solution at 60°C for 1 minute to carry out a surface modification process. The substrate was then immersed in 2-propanol at room temperature for 1 minute, and then in ion-exchanged water at room temperature for 1 minute. The surface was then immersed in N 2 for 10 seconds. ２ The coupon was then dried by spraying gas onto it (cleaning and drying process) to prepare a coupon for measurement. [Vapor Method: Example 11] In Example 11, the coupon was placed horizontally in a vapor treatment chamber, and the solution-state composition prepared above was vaporized under the following vapor supply conditions, and the vapor was supplied to the vapor treatment chamber. Vapor supply conditions for the composition: 2 dm3 of nitrogen gas was blown into the vaporization chamber heated to 165°C. ３The prepared solution composition was dripped at a drip rate of 0.01 g / sec while flowing at a flow rate of 1 / min. The entire dripped amount was vaporized. The vapor was immediately supplied to the vapor treatment chamber with a nitrogen gas flow. This treatment was carried out for 40 seconds. The vapor supplied to the coupon surface was then converted to a liquid state to carry out the surface modification process. Next, the coupon was immersed in 2-propanol at room temperature for 1 minute, then in ion-exchanged water at room temperature for 1 minute, and the surface was then immersed in N gas for 10 seconds. ２ The coupons were then dried by spraying gas onto them to prepare evaluation coupons (cleaning and drying process). Coupons with Cu surfaces as their main surfaces and blank coupons were also prepared in the same manner as the coupons used to measure the water contact angle. The nitrogen peak area (hereinafter referred to as the "N peak area") was determined from the XPS spectrum of each film surface obtained using the immersion method or vapor method. The N peak area ratio was calculated for each film, assuming the N peak area on the blank substrate surface to be 1.0. The results are shown in Table 1.

[0131] (Evaluation of Film Formation) Using the chemical solution of Example 1, SiO ２ A sample in which the film (first surface) and Cu surface (second surface) had been subjected to the <Substrate Treatment> described below was placed on a pedestal in the apparatus, and an ALD apparatus (manufactured by Picosun) was used to perform a film formation process under the <Film Formation Conditions> described below. <Substrate Treatment> A silicon wafer having no uneven surface pattern and a 1 μm-thick silicon oxide film on its surface was cut to prepare multiple coupons (test pieces) made of silicon substrates with length, width, and thickness dimensions of 4 cm, 1 cm, and 0.75 mm. The surface on which the silicon oxide film was formed was regarded as the "main surface" for evaluation. [Immersion Method: Examples 1 to 10, Comparative Examples 1 to 5] The obtained coupon was immersed in 0.5 mass % hydrofluoric acid at 25°C for 1 minute, then immersed in ion-exchanged water at room temperature for 1 minute, and N 2 was applied to the surface for 10 seconds. ２ The substrate was then immersed in the prepared chemical solution at 60°C for 1 minute to carry out a surface modification process. The substrate was then immersed in 2-propanol at room temperature for 1 minute, and then in ion-exchanged water at room temperature for 1 minute. The surface was then immersed in N 2 for 10 seconds. ２The coupon was then dried by spraying gas onto it to prepare a coupon for evaluation. [Vapor Method: Example 11] In Example 11, the coupon was placed horizontally in a vapor treatment chamber, and the solution-state composition prepared above was vaporized under the following vapor supply conditions, and the vapor was supplied to the vapor treatment chamber. Vapor supply conditions for the composition: 2 dm3 of nitrogen gas was blown into a vaporization chamber heated to 165°C. ３ The prepared solution composition was dripped at a drip rate of 0.01 g / sec while flowing at a flow rate of 1 / min. The entire dripped amount was vaporized. The vapor was immediately supplied to the vapor treatment chamber with a nitrogen gas flow. This treatment was carried out for 40 seconds. The vapor supplied to the coupon surface was then converted to a liquid state to carry out the surface modification process. Next, the coupon was immersed in 2-propanol at room temperature for 1 minute, then in ion-exchanged water at room temperature for 1 minute, and the surface was then immersed in N gas for 10 seconds. ２ The silicon wafer having a Cu film of 100 nm on its surface obtained by the above-mentioned immersion method or vapor method was used, and the surface on which the Cu film was formed was used as the main surface, and the other surface was covered with SiO ２ A coupon for film formation evaluation was prepared in the same manner as for the surface. <Film formation conditions> After heating the substrate to 150°C, 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.

[0132] From Table 1 above, it was shown that the substrate treatment methods of Examples 1 to 11 can reduce the amount of nitrogen-containing components remaining on the metal surface (second surface) that does not contain Si but contains metal, compared to Comparative Examples 1 to 5. Furthermore, from the evaluation results of the film formation, it was found that the substrate treatment methods of Examples 1 to 11 can reduce the amount of nitrogen-containing components remaining on the metal surface (second surface) that does not contain Si, compared to Comparative Examples 1 to 5. ２ The deposition of the metal film (first surface) was suppressed, while deposition of the metal film was observed on the Cu surface (second surface). This demonstrates that the substrate treatment methods of Examples 1 to 11 enable selective deposition of the metal film on the second surface, which does not contain Si, compared to the first surface, which contains Si.

[0133] This application claims priority based on Japanese Patent Application No. 2022-212245, filed December 28, 2022, the disclosure of which is incorporated herein in its entirety.

[0134] REFERENCE SIGNS LIST 1 substrate 1a substrate surface 11 first surface 12 second surface 20 chemical solution 21 water-repellent film

Claims

1. a preparation step of preparing a substrate having a first surface containing Si elements and a second surface containing a metal element but not Si elements; a surface modification step of supplying a chemical solution containing a silylating agent, a catalytic compound, and an aprotic solvent to the first surface and the second surface to selectively improve the water repellency of the first surface relative to the second surface; a film forming step of selectively forming a film by supplying a film material in a vapor phase to the second surface, The chemical solution is Does not contain nitrogen-containing heterocyclic compounds, or When the content (mass%) of the catalytic compound contained in 100 mass% of the chemical solution is Cc and the content of the nitrogen-containing heterocyclic compound is Cn, the chemical solution satisfies the blending conditions that Cn is 0.05 mass% or less and Cn / Cc is 0.01 or less. Methods for treating substrates.

2. 2. The method for treating a substrate according to claim 1, The method for treating a substrate, wherein the catalytic compound comprises at least one selected from the group consisting of a carboxylic acid derivative represented by the following general formula [17] and a sulfonic acid derivative represented by the following general formula [4]: R ２９’ -C(=O)O-Si(H) ３－ｈ (R) ３０ ) ｈ [17] [In the above general formula [17], R ２９’ 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 ３０ 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 h is an integer of 1 to 3. 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.

3. 3. A method for treating a substrate according to claim 1 or 2, comprising: A method for treating a substrate, wherein the catalytic compound comprises one or more compounds selected from the group consisting of 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.

4. 3. A method for treating a substrate according to claim 1 or 2, comprising: The method for treating a substrate, wherein the silylating agent contains a silicon compound represented by the following general formula [1]: R １ ａ Si (H) ｂ X ４－ａ－ｂ [1] (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 atom 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.

5. 5. The method for treating a substrate according to claim 4, The silicon compound is the R １ are each independently an organic group containing a hydrocarbon group having 1 to 8 carbon atoms in which some or all of the hydrogen atoms may be replaced by fluorine atoms.

6. 3. A method for treating a substrate according to claim 1 or 2, comprising: the first surface contains one or more elements selected from the group consisting of Si, N, C, and O (including at least Si); A method for treating a substrate, wherein the second surface comprises one or more elements selected from the group consisting of W, Co, Al, Ni, Ru, Cu, Ti, Ta, Hf, and Ge.

7. 3. A method for treating a substrate according to claim 1 or 2, comprising: The method for treating a substrate, wherein the film forming step is a step of forming a film by atomic layer deposition.

8. 3. A method for treating a substrate according to claim 1 or 2, comprising: A method for treating a substrate, comprising carrying out a cleaning treatment for cleaning the substrate between the surface modification step and the film formation step.

9. 3. A method for treating a substrate according to claim 1 or 2, comprising: A method for treating a substrate, comprising carrying out a drying treatment for drying the substrate between the surface modification step and the film formation step.

10. 3. A method for treating a substrate according to claim 1 or 2, comprising: The surface modification step is a method for treating a substrate, wherein the chemical solution is supplied in a liquid state to the first surface and the second surface.

11. a preparation step of preparing a substrate having a first surface containing Si elements and a second surface containing a metal element but not Si elements; a surface modification step of supplying a chemical solution containing a silylating agent, a catalytic compound, and an aprotic solvent to the first surface and the second surface to selectively improve the water repellency of the first surface relative to the second surface; a film forming step of selectively forming a film by supplying a film material in a vapor phase to the second surface, The chemical solution is The chemical solution contains 8% by mass or more of a silylating agent in 100% by mass of the chemical solution, and The chemical solution does not contain a nitrogen-containing heterocyclic compound, or satisfies the blending conditions that, when the content (mass%) of the catalytic compound contained in 100 mass% of the chemical solution is Cc and the content of the nitrogen-containing heterocyclic compound is Cn, Cn is 0.05 mass% or less and Cn / Cc is 0.01 or less. Methods for treating substrates.

12. 12. A method for treating a substrate according to claim 11, comprising: The surface modification step is a method for treating a substrate, wherein vapor of the chemical solution is supplied to the first surface and the second surface.

13. a preparation step of preparing a substrate having a first surface containing Si elements and a second surface containing a metal element but not Si elements; a surface modification step of supplying a chemical solution containing a silylating agent, a catalytic compound, and an aprotic solvent to the first surface and the second surface, thereby selectively improving the water repellency of the first surface relative to the second surface; The chemical solution is Does not contain nitrogen-containing heterocyclic compounds, or When the content (mass%) of the catalytic compound contained in 100 mass% of the chemical solution is Cc and the content of the nitrogen-containing heterocyclic compound is Cn, the chemical solution satisfies the blending conditions that Cn is 0.05 mass% or less and Cn / Cc is 0.01 or less. Methods for treating substrates.

14. a preparation step of preparing a substrate having a first surface containing Si elements and a second surface containing a metal element but not Si elements; a surface modification step of supplying a chemical solution containing a silylating agent, a catalytic compound, and an aprotic solvent to the first surface and the second surface to selectively improve the water repellency of the first surface relative to the second surface; an etching step of wet etching or dry etching the second surface, The chemical solution is Does not contain nitrogen-containing heterocyclic compounds, or When the content (mass%) of the catalytic compound contained in 100 mass% of the chemical solution is Cc and the content of the nitrogen-containing heterocyclic compound is Cn, the chemical solution satisfies the blending conditions that Cn is 0.05 mass% or less and Cn / Cc is 0.01 or less. Methods for treating substrates.

15. A method for manufacturing a substrate, comprising the method for treating a substrate according to claim 1, 11, 13 or 14.