Water-repellent agents for conductive surfaces, methods for water-repellent treatment of conductive surfaces, methods for selectively water-repellentizing areas with conductive surfaces, surface treatment methods, and methods for selective film formation on substrate surfaces.

Abstract

The present invention provides a water-repellent agent for conductive surfaces, which contains a compound (P1). The compound (P1) comprises an aromatic ring, an adsorbent group bonded to the aforementioned aromatic ring and selected from the group consisting of amino, phosphonic, anhydride, hydrogen sulfide and chlorine groups, and a straight-chain or branched alkyl group or a straight-chain or branched fluorinated alkyl group bonded to the aforementioned aromatic ring.

Description

[Technical Field]

[0001] This invention relates to a water-repellent agent for a conductive surface, a method for water-repellent treatment of a conductive surface, a method for selectively water-repellent treatment of a region having a conductive surface, a surface treatment method, and a method for selectively forming a film on a substrate surface. This application claims priority based on Japanese Patent Application No. 2022-008926 filed on January 24, 2022, and its contents are incorporated herein by reference. [Previous Technology]

[0002] In recent years, the trend towards increasing the integration and miniaturization of semiconductor devices has led to advancements in the miniaturization of organic patterns on photomasks or inorganic patterns fabricated through etching processes, requiring atomic-level film thickness control. Atomic layer growth (ALD) is a well-known method for forming thin films on substrates at the atomic level. Compared to conventional chemical vapor deposition (CVD), ALD is known to offer higher step coverage and film thickness control.

[0003] The ALD (Alternating Layer Deposition) method is a thin film formation technique that alternately supplies two types of gases, with the elements constituting the desired film as the main components, to a substrate, and repeats this process several times to form a thin film at atomic layer levels to achieve the desired film thickness. In the ALD method, only one or a few layers of the supplied raw material gases are adsorbed onto the substrate surface; excess raw material gases do not contribute to growth and utilize the self-control mechanism (self-limiting mechanism) of growth. For example, when forming an Al₂O₃ film on a substrate, a raw material gas containing TMA (Trimethoprim Alium) and an oxidizing gas can be used. Furthermore, when forming a nitride film on a substrate, a nitride gas can be used instead of an oxidizing gas.

[0004] In recent years, methods for regionally selective film formation on substrate surfaces using the ALD method have been explored. Consequently, substrates with regionally selectively modified surfaces are known to be suitable for application in ALD methods for regionally selective film formation on substrates. In film formation methods, the use of the ALD method is expected to achieve control over the film thickness at the patterned atomic layer level, improve step coverage, and achieve miniaturization. For example, Non-Patent Literature 1 describes the formation of a self-assembled monolayer (SAM) of octadecylphosphonic acid, thereby achieving regional selective suppression in ALD film formation. [Prior Art Literature] [Non-Patent Literature]

[0005] [Non-patent document 1] Dara Bobb-Semple, Katie Lynn Nardi, Nerissa Draeger, Dennis M. Hausmann, and Stacey F. Bent. Area-Selective Atomic Layer Deposition Assisted by Self-Assembled Monolayers: A Comparison of Cu, Co, W, and Ru. Chem. Mater. 2019, 31, 1635-1645. [Summary of the Invention]

[0006] [The problem this invention aims to solve]

[0007] In the ALD method, a region-selective film formation method on a substrate surface, film formation on the water-repellent substrate surface is generally suppressed by performing region-selective hydrophobication on the substrate surface. For example, it is known that in a substrate surface where a conductor surface and an insulator surface are mixed, when selectively forming a film on the insulator surface, the conductor surface is selectively hydrophobicated.

[0008] In view of the above facts, the present invention aims to provide a water-repellent agent for conductive surfaces capable of effectively repelling the surface of a conductive material, a method for repelling the surface of a conductive material using the aforementioned water-repellent agent, a method for selectively repelling a region having a conductive surface, a surface treatment method, and a method for selectively forming a film on a substrate surface. [Means for Solving the Problem]

[0009] In order to solve the above-mentioned problems, the present invention adopts the following structure.

[0010] The first type of the present invention is a water-repellent agent for conductive surfaces, which contains a compound (P1), the compound (P1) comprising: an aromatic ring, an adsorbent group bonded to the aforementioned aromatic ring and selected from the group consisting of amino groups, phosphonic acid groups, acid anhydride groups, hydrogen sulfide groups and acid chloride groups, and a straight-chain or branched alkyl group bonded to the aforementioned aromatic ring, or a straight-chain or branched fluorinated alkyl group.

[0011] The second aspect of the present invention is a method for water-repellent treatment of a conductive surface, which involves exposing the conductive surface to a conductive surface of the first aspect using a water-repellent agent.

[0012] The third aspect of the present invention is a method for selectively water-repellentizing the regions having conductive surfaces in a substrate having a surface comprising two or more regions having different materials, wherein at least one of the aforementioned two or more regions has a conductive surface, the method comprising exposing the aforementioned surface of the substrate to a conductive surface of the first aspect using a water-repellent agent.

[0013] The fourth aspect of the present invention is a method for surface treatment of a substrate having at least one conductive surface in one of the two or more regions having two or more different materials, which includes exposing the aforementioned surface to the conductive surface of the first aspect using a water-repellent agent.

[0014] The fifth aspect of the present invention is a region-selective film-forming method for a substrate surface, which includes a surface treatment method of the fourth aspect, treating the aforementioned surface of the substrate, and forming a film on the surface of the surface-treated substrate using an atomic layer growth method, wherein the deposition amount of the film-forming material in the aforementioned atomic layer growth method has selective differences in the region. [Effects of the Invention]

[0015] By means of the present invention, it is possible to provide a water-repellent agent for conductive surfaces that can effectively repel water from the surface of a conductive body, a method for repelling the surface of a conductive body using the aforementioned water-repellent agent for conductive surfaces, a method for selectively repelling a region having a conductive surface, a surface treatment method, and a method for selectively forming a film on a substrate surface.

Implementation Method

[0016] In this specification and the scope of this application, "aliphatic" refers to a concept relative to aromatic, and includes groups, compounds, etc., that do not possess aromatic properties. "Alkyl" unless otherwise specified includes linear, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to alkyl groups in alkoxy groups. "Dialkyl" unless otherwise specified includes linear, branched, and cyclic divalent saturated hydrocarbon groups. "Halogen atom" includes fluorine, chlorine, bromine, and iodine atoms.

[0017] In this specification and the claims of this application, the structures represented by chemical formulas may contain amorphous carbons, and may contain enantiomers or diastereomers. In this case, a single chemical formula represents such isomers. These isomers may be used alone or as mixtures.

[0018] <Type 1: Water-repellent agent for conductive surfaces> Type 1 of the present invention is a water-repellent agent for conductive surfaces. The water-repellent agent for conductive surfaces of this type contains a compound (P1), which comprises: an aromatic ring, an adsorbent group bonded to the aforementioned aromatic ring and selected from the group consisting of amino, phosphonic, anhydride, hydrogen sulfide and chlorine groups, and a straight-chain or branched alkyl group bonded to the aforementioned aromatic ring, or a straight-chain or branched fluorinated alkyl group.

[0019] (Compound (P1)) Compound (P1) is a compound comprising an aromatic ring, an adsorbent group bonded to the aforementioned aromatic ring and selected from the group consisting of amino, phosphonic, anhydride, hydrogen sulfide and chlorine groups, and a straight-chain or branched alkyl group bonded to the aforementioned aromatic ring, or a straight-chain or branched alkyl group.

[0020] The aromatic ring contained in compound (P1) is not particularly limited as long as it is a cyclic conjugated system with 4n+2 π electrons, and can be a polycyclic or monocyclic group. The aromatic ring can also be an aromatic hydrocarbon ring or an aromatic heterocycle. Examples of heteroatoms included in an aromatic heterocycle include oxygen, sulfur, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings. It is preferred that the aromatic ring is an aromatic hydrocarbon ring, and even more preferred that it contains one or two benzene rings. Specific examples of aromatic rings include benzene rings, naphthalene rings, and biphenyl rings.

[0021] The aromatic ring is bonded to an adsorbent group selected from the group consisting of amino, phosphonic, anhydride, hydrogen sulfide, and chlorine groups, and to a straight-chain or branched alkyl group, or a straight-chain or branched fluorinated alkyl group. The aforementioned adsorbent group is directly bonded to the carbon atom constituting the aromatic ring. The aforementioned alkyl or fluorinated alkyl group is directly bonded to the carbon atom constituting the aromatic ring.

[0022] The "adsorbing group" is a functional group with adsorption properties for the surface of a conductive material. When the surface of a conductive material is treated with compound (P1), compound (P1) will be adsorbed onto the surface of the conductive material through the adsorbing group, and SAM can be formed. In compound (P1), the adsorbing group is selected from the group consisting of amino, phosphonic acid, acid anhydride, hydrogen sulfide, and acid chloride. As an acid anhydride, succinic anhydride is given as an example. As an adsorbing group, amino, hydrogen sulfide, phosphonic acid, and acid anhydride are preferred, amino, hydrogen sulfide, and phosphonic acid are even more preferred, amino and hydrogen sulfide are more preferred, and amino is particularly preferred.

[0023] The adsorbent group bonded to the aromatic ring may be one or more. When the aromatic ring is a benzene ring, examples of the number of adsorbent groups include 1 to 5, 1 to 4, 1 to 3, 1 or 2. When the aromatic ring is a naphthalene ring, examples of the number of adsorbent groups include 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3, 1 or 2. When the aromatic ring is a biphenyl ring, examples of the number of adsorbent groups include 1 to 9, 1 to 8, 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3, 1 or 2. It is preferred that the number of adsorbent groups is 1 to 4, further preferred that it is 1 to 3, even more preferred that it is 1 or 2, and particularly preferred that it is 1. When the aromatic ring is bonded to a plurality of adsorbent groups, the plurality of adsorbent groups may be the same or different from each other.

[0024] The linear or branched alkyl or fluorinated alkyl group bonded to the aromatic ring is preferably composed of 1 to 45 carbon atoms, more preferably 1 to 40 carbon atoms, and even more preferably 1 to 35 carbon atoms. When the alkyl group or fluorinated alkyl group is branched, it is preferably composed of 3 to 45 carbon atoms, more preferably 3 to 40 carbon atoms, and even more preferably 3 to 35 carbon atoms. Although there is no particular limitation on the number of carbon atoms of the aforementioned alkyl or fluorinated alkyl group, it may be 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, 9 or more, 10 or more, 12 or more, 14 or more, or 16 or more, or it may be 45 or less, 40 or less, 35 or less, 30 or less, 28 or less, 26 or less, 24 or less, 22 or less, or 20 or less. The aforementioned alkyl or fluorinated alkyl group may have a carbon number in the range of 5-45, 5-40, 5-35, 8-35, or 8-30. When the aforementioned adsorbing group is a phosphonic acid group, the aforementioned alkyl or fluorinated alkyl group may have a carbon number of 5 or more, preferably 5-45, more preferably 5-40, and even more preferably 5-35.

[0025] Specific examples of straight-chain or branched-chain alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isothiadeliyl, tetradecyl, decadecyl, hexadecyl, isohexadeliyl, heptyl, octadecyl, nonadecadecyl, icosyl, icosyl, dodecyl, and various isomers of the aforementioned alkyl groups.

[0026] A straight-chain or branched-chain fluorinated alkyl group is a group in which at least a portion of the hydrogen atoms of the straight-chain or branched-chain alkyl group are substituted with fluorine atoms. Examples of straight-chain or branched-chain fluorinated alkyl groups include those in which at least a portion of the hydrogen atoms of the aforementioned straight-chain or branched-chain alkyl group are substituted with fluorine atoms. The proportion of fluorinated hydrogen atoms in the straight-chain or branched-chain fluorinated alkyl group is not particularly limited. The fluorinated alkyl group may also be a perfluoroalkyl group.

[0027] The number of straight-chain or branched alkyl groups bonded to the aromatic ring, or the number of straight-chain or branched fluorinated alkyl groups, may be one or two or more. When the aromatic ring is a benzene ring, the number of the aforementioned alkyl or fluorinated alkyl groups includes 1 to 5, 1 to 4, 1 to 3, 1, or 2. When the aromatic ring is a naphthyl ring, the number of the aforementioned alkyl or fluorinated alkyl groups includes 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3, 1, or 2. When the aromatic ring is a biphenyl ring, the number of the aforementioned alkyl or fluorinated alkyl groups includes 1 to 9, 1 to 8, 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3, 1, or 2. It is preferred that the number of the aforementioned alkyl or fluorinated alkyl groups is 1 to 4, more preferably 1 to 3, even more preferably 1 or 2, and particularly preferably 1. When multiple alkyl or fluorinated alkyl groups are bonded to an aromatic ring, the multiple alkyl or fluorinated alkyl groups may be the same as or different from each other.

[0028] In the aromatic ring, from the viewpoint of avoiding interference with the adsorbing group, it is preferable that the alkyl or fluorinated alkyl group is not bonded to the ortho position of the adsorbing group.

[0029] Compound (P1) may also contain groups other than the adsorbing group and alkyl or fluorinated alkyl groups mentioned above. Examples of such other groups include organogroups (without straight-chain or branched alkyl groups and straight-chain or branched fluorinated alkyl groups). Examples of such organogroups include hydrocarbon groups that may also have substituents. The aforementioned hydrocarbon groups may be aliphatic hydrocarbon groups or aromatic hydrocarbon groups. Examples of the number of carbon atoms in the aforementioned hydrocarbon groups include 1 to 12, 1 to 10, 1 to 8, 1 to 6, 1 to 4, 1 to 3, 1, or 2. Aliphatic hydrocarbon groups may also be saturated or unsaturated. Aliphatic hydrocarbon groups may also be straight-chain or branched-chain, and may also contain cyclic structures. The aforementioned cyclic structures may also be monocyclic or polycyclic. The aforementioned cyclic structures may also contain aliphatic hydrocarbon rings, or may also contain aliphatic heterocycles. Aromatic hydrocarbon groups may also be monocyclic or polycyclic. Aromatic hydrocarbon groups may also contain aromatic hydrocarbon rings or aromatic heterocycles. Substituents in the aforementioned hydrocarbon groups include functional groups other than the adsorbing groups mentioned above. Specific examples of substituents include, but are not limited to, hydroxyl, carboxyl, halogen, and alkoxy groups.

[0030] As a compound (P1), there are compounds represented by the following general formula (P1-1).

[0031] [In the formula, R0 represents a straight-chain or branched-chain alkyl group, or a straight-chain or branched-chain fluorinated alkyl group; R1 represents an organic group (but, the equivalent of R is removed) 0); A represents a group consisting of a benzene ring with (n0+n1+nx) hydrogen atoms removed, a naphthyl ring with (n0+n1+nx) hydrogen atoms removed, or a biphenyl ring with (n0+n1+nx) hydrogen atoms removed; X represents an adsorbent group selected from the group consisting of amino, phosphonic, anhydride, hydrogen sulfide, and acid chloride; n0 and nx each independently represent an integer greater than 1; n1 represents an integer greater than 0, but when A is a group consisting of a benzene ring with (n0+n1+nx) hydrogen atoms removed, n0+n1+nx ≦ 6; when A is a group consisting of a naphthyl ring with (n0+n1+nx) hydrogen atoms removed, n0+n1+nx ≦ 8; when A is a group consisting of a biphenyl ring with (n0+n1+nx) hydrogen atoms removed, n0+n1+nx ≦ 10; when n0 is 2 or more, the complex number R exists. 0 can be the same or different; when n1 is 2 or more, the complex numbers R1 can be the same or different; when nx is 2 or more, the complex numbers X can be the same or different.

[0032] In the aforementioned formula (P1-1), A represents a group that has removed (n0+n1+nx) hydrogen atoms from a benzene ring, a group that has removed (n0+n1+nx) hydrogen atoms from a naphthalene ring, or a group that has removed (n0+n1+nx) hydrogen atoms from a biphenyl ring.

[0033] In the aforementioned formula (P1-1), R0 represents a straight-chain or branched-chain alkyl group, or a straight-chain or branched-chain fluorinated alkyl group. Examples of straight-chain or branched-chain alkyl groups or straight-chain or branched-chain fluorinated alkyl groups in R0 include those identical to the aforementioned straight-chain or branched-chain alkyl groups or straight-chain or branched-chain fluorinated alkyl groups. It is preferable that R0 is a straight-chain alkyl group or a straight-chain fluorinated alkyl group, and even more preferably, it is a straight-chain alkyl group or a straight-chain fluorinated alkyl group having 1 to 30 carbon atoms. An example of R0 is an n-octadecyl group.

[0034] In the aforementioned formula (P1-1), X represents an adsorption group selected from the group consisting of amino, phosphonic acid, anhydride, hydrogen sulfide, and chlorine. As an anhydride group, succinic anhydride is an example.

[0035] In the aforementioned formula (P1-1), R1 represents an organic group (but, those equivalent to R0 are excluded). As an organic group in R1, there are examples that are the same as the organic group described above.

[0036] In the aforementioned formula (P1-1), n0 and nx each independently represent integers greater than or equal to 1. It is preferable for n0 and nx to be 1 to 4, even better if they are 1 to 3, and even better if they are 1 or 2. In the aforementioned formula (P1-1), n1 represents integers greater than or equal to 0. It is preferable for n1 to be 0 to 4, even better if it is 0 to 3, even better if it is 0 to 2, and especially better if it is 0 or 1. When n0 is 2 or greater, the complex numbers R0 can be the same or different from each other. When nx is 2 or greater, the complex numbers X can be the same or different from each other. When n1 is 2 or greater, the complex numbers R1 can be the same or different from each other.

[0037] It is preferred that the compound (P1) is represented by the following general formula (P1-1-1).

[0038] [In the formula, R0 represents a straight-chain or branched alkyl group, or a straight-chain or branched fluorinated alkyl group; X represents an adsorption group selected from the group consisting of amino group, phosphonic acid group, acid anhydride group, hydrogen sulfide group and acid chloride group; n represents 0 or 1].

[0039] In the aforementioned formula (P1-1-1), R0 and X are the same as R0 and X in the aforementioned formula (P1-1). In the aforementioned formula (P1-1-1), n ​​represents 0 or 1. It is preferable that n is 0.

[0040] The following represents a preferred example of compound (P1). In the formula, R0 and X are the same as R0 and X in the aforementioned formula (P1-1).

[0041]

[0042]

[0043]

[0044]

[0045]

[0046] Specific examples of compound (P1) include 4-n-octadecylaniline, 4-n-pentylaniline, 4-n-hexylaniline, 4-n-heptylaniline, 4-n-octylaniline, 4-n-nonylaniline, 4-n-decylaniline, 4-n-dodecylaniline, 4-n-tetradecylaniline, 4-n-pentadecaylaniline, 4-n-hexadecylaniline, 4-methylbenzenethiol, 4-n-propylbenzenethiol, 4-n-butylbenzenethiol, 4-n-pentylbenzenethiol and 4-n-dodecylbenzenethiol, with 4-n-octadecylaniline or 4-methylbenzenethiol being preferred.

[0047] Compound (P1) can be used alone or in combination with two or more. In the water-repellent agent for conductive surfaces, the content of compound (P1) relative to the total mass of the water-repellent agent for conductive surfaces is preferably 0.0001 to 5% by mass, more preferably 0.001 to 4% by mass, even more preferably 0.005 to 3% by mass, and even more preferably 0.008 to 3% by mass. If the content of compound (P1) is within the aforementioned preferred range, compound (P1) is easily adsorbed onto the conductive surface, and the water repellency of the conductive surface is improved. The water-repellent agent for conductive surfaces of this embodiment may also include octadecylphosphonic acid, phenylphosphonic acid, and benzenethiol. The water-repellent agent for conductive surfaces of this embodiment may also not contain SAM forming materials other than compound (P1).

[0048] (Any component) In addition to compound (P1), the water-repellent agent for the conductive surface of this embodiment may also contain any component. Examples of such components include organic solvents and water.

[0049] ≪Organic Solvent (S)≫ The water-repellent agent for the conductive surface of this embodiment preferably contains an organic solvent (hereinafter also referred to as "organic solvent (S)"). There are no particular limitations on the organic solvent, but it is preferable that the specific electrophoresis is 35 or less. Examples of organic solvents include methanol (specific electrophoresis: 33), diethylene glycol monobutyl ether (BDG) (specific electrophoresis: 13.70), propylene glycol monomethyl ether (PE) (specific electrophoresis: 12.71), benzyl alcohol (specific electrophoresis: 13), 2-heptanone (specific electrophoresis: 11.74), ethylene glycol butyl acetate (specific electrophoresis: 8.66), tert-butyl alcohol (specific electrophoresis: 12.5), 1-octanol (specific electrophoresis: 10.21), isobutanol (specific electrophoresis: 18.22), benzotrifluoride (specific electrophoresis: 9.18), decahydronaphthalene (specific electrophoresis: 2.16), cyclohexane (specific electrophoresis: 1.99), decane (specific electrophoresis: 1.99), and isobutyl alcohol (specific electrophoresis: 1). 8.22), ethyl lactate (EL) (specific electrophoresis: 13.22), diethylene glycol monomethyl ether (specific electrophoresis: 15.76), 1-nonanol (specific electrophoresis: 9.13), toluene (specific electrophoresis: 2.37), propylene glycol monomethyl ether acetate (PM) (specific electrophoresis: 9.4), methyl isobutyl alcohol (MIBC) (specific electrophoresis: 10.47), 2,6-dimethyl-4-heptanol (specific electrophoresis: 2.98), 2-ethyl-1-butanol (specific electrophoresis: 12.6), 2-butanone oxime (specific electrophoresis: 2.9), n-dibutyl ether (specific electrophoresis: 3.33), butyl butyrate (specific electrophoresis: 4.55), 2,6-dimethyl-4-heptanone (specific electrophoresis: 9.82), etc. Among the organic solvents (S), methanol (specific electrophoresis: 33), diethylene glycol monobutyl ether (BDG) (specific electrophoresis: 13.70), polyethylene glycol (PE) (specific electrophoresis: 12.71), benzyl alcohol (specific electrophoresis: 12.70), 2-heptanone (specific electrophoresis: 11.74), ethylene glycol butyl acetate (specific electrophoresis: 8.66), tert-butyl alcohol (specific electrophoresis: 12.5), 1-octanol (specific electrophoresis: 10.21), isobutanol (specific electrophoresis: 18.22), and 4-methyl-2-pentanol (specific electrophoresis: 10.47) are preferred. The specific electrophoresis of the organic solvent is preferably below 30, 25, 20, 15, 13, 12, 11, 10, 9, 8, 7, 6, or 5. There is no particular limitation on the lower limit of the specific electrophoresis of organic solvents, such as exceeding 0, 0.1 or more, 0.5 or more, or 1 or more. The specific electrophoresis of organic solvents (S) can be measured using commercially available liquid electrophoresis measuring devices (such as the "Rufuto Model 871" manufactured by Rufuto Co., Ltd. of Japan).

[0050] The Hansen solubility parameter (dP) of the organic solvent (S) is preferably 0 to less than 16, 0 to 15 is even better, and 0 to 14 is even better. If the Hansen solubility parameter (dP) of the organic solvent (S) is within the above-mentioned preferred range, the water repellency of the conductive surface is easily improved.

[0051] One organic solvent (S) may be used alone, or two or more may be used together. The water-repellent agent for the conductive surface of this embodiment may not contain an organic solvent with a specific electrophoretic capacity exceeding 35, or may not contain one or more of the aforementioned organic solvents.

[0052] ≪Water≫ The water-repellent agent for the conductive surface of this embodiment may contain water to further enhance water repellency and increase the contact angle. The water may also contain trace amounts of unavoidable contaminants. It is preferable to use purified water such as distilled water, ion-exchanged water, or ultrapure water, with ultrapure water commonly used in semiconductor manufacturing being even more preferable. When the water-repellent agent for the conductive surface contains water, the water content is preferably 0.01~25% by mass, more preferably 0.03~20% by mass, and even more preferably 0.05~15% by mass. If the water content is within the aforementioned preferred range, the compound (P1) will easily adhere to the conductive surface. The water-repellent agent for the conductive surface of this embodiment may also not contain water.

[0053] ≪Impurities, etc.≫ The water-repellent agent for conductive surfaces in this embodiment may also contain metal impurities, such as Fe atoms, Cr atoms, Ni atoms, Zn atoms, Ca atoms, or Pb atoms. In the water-repellent agent for conductive surfaces in this embodiment, the total content of the aforementioned metal atoms is preferably 100 mass ppt or less relative to the total mass of the water-repellent agent for conductive surfaces. The lower the lower limit of the total content of metal atoms, the better, but for example, it is 0.001 mass ppt or more. The total content of metal atoms is, for example, from 0.001 mass ppt to 100 mass ppt. If the total content of metal atoms is set below the aforementioned preferred upper limit, the water-repellent effect of the water-repellent agent for conductive surfaces will be improved. If the total content of metal atoms is set above the aforementioned preferred lower limit, the metal atoms are difficult to exist freely in the system, which will have an adverse effect on the overall manufacturing yield of the processed object. The content of metal impurities can be adjusted by purification treatment such as filtration. Purification processes such as filtration can be performed on part or all of the raw materials before applying the water-repellent agent to the conductive surface, or they can be performed after applying the water-repellent agent to the conductive surface.

[0054] The water-repellent agent for conductive surfaces of this embodiment may also contain impurities, such as those from organic matter (organic impurities). In the water-repellent agent for conductive surfaces of this embodiment, the total content of the aforementioned organic impurities is preferably 5000 ppm by mass or less. The lower the lower limit of the organic impurity content, the better, but examples include 0.1 ppm by mass or more. Examples of the total content of organic impurities are 0.1 ppm by mass to 5000 ppm by mass.

[0055] The water-repellent agent for conductive surfaces in this embodiment may also contain, for example, particles of the size counted by a light-scattering liquid particle counter. The size of the particles being counted is, for example, 0.04 μm or more. In the water-repellent agent for conductive surfaces in this embodiment, the number of particles being counted is, for example, 1,000 or less in 1 mL of the cleaning solution, with a lower limit of, for example, 1 or more. By having the number of particles being counted in the cleaning solution within the aforementioned range, the water-repellent effect of the water-repellent agent for conductive surfaces can be enhanced.

[0056] The aforementioned organic impurities and / or the counted substances may also be added to the conductive surface water-repellent agent. During the manufacturing process of the conductive surface water-repellent agent, it is also inevitable that the agent will be mixed in. Examples of unavoidable mixing during the manufacturing process of the conductive surface water-repellent agent include, for example, the presence of organic impurities in the raw materials (e.g., organic solvents) used in the manufacturing of the conductive surface water-repellent agent, and the introduction of impurities from the external environment (e.g., contamination) during the manufacturing process, but are not limited to the above. When the counted substances are added to the conductive surface water-repellent agent, the surface roughness of the object being treated can be considered, and the presence ratio can be adjusted according to a specific size.

[0057] (Storage Container) There are no particular limitations on the storage method of the water-repellent agent for the conductive surface of this embodiment, and conventionally known storage containers can also be used. In order to ensure the stability of the water-repellent agent for the conductive surface, the porosity inside the container and / or the type of gas filling the voids can be appropriately set when storing it in the container. For example, a porosity of about 0.01 to 30% by volume is mentioned as the porosity inside the storage container.

[0058] (The object being treated) The water-repellent agent for the conductive surface of this embodiment is used to repel water from the conductive surface. "Conductive surface" refers to the surface of a region composed of a conductive material. The conductive material can be any material that is conductive and is not particularly limited. Examples of conductive materials include materials containing metal atoms. Examples of conductive materials include metals (e.g., monomers of a metal element), alloys, and metal compounds (e.g., nitrides). When the conductive material is a metal, the conductive surface becomes a metallic surface. When the conductive material is an alloy, the conductive surface becomes an alloy surface. When the conductive material is a metal compound, the conductive surface becomes a conductive metal compound surface. Examples of metals included in the metallic surface include tungsten, ruthenium, copper, aluminum, nickel, and cobalt, but are not limited to these. Examples of metal compounds included in the conductive metal compound surface include titanium nitride and tantalum nitride, but are not limited to these. The metal surface preferably contains at least one metal selected from the group consisting of tungsten, ruthenium, copper, aluminum, nickel and cobalt, with ruthenium being even more preferred.

[0059] The surface of the conductor can also be pretreated with an oxidant. Examples of oxidants used for pretreating the surface of the conductor (hereinafter, sometimes referred to as "oxidants for pretreatment") include those that remove the natural oxide film present on the surface of the conductor and impart hydroxyl groups to the surface. Examples of oxidants for pretreatment include peroxides such as hydrogen peroxide; perhalic acids such as periodic acid; and oxyacids such as nitric acid and hypochlorous acid. Among these, from the viewpoint of the adsorption properties of compound (P1), it is preferable to select at least one from the group consisting of hydrogen peroxide and perhalic acids. It is preferable to select at least one from the group consisting of hydrogen peroxide and perhalic acids so that when the surface of inorganic substances such as SiO2 and Al2O3 coexists with the surface of the conductor, the treatment of the conductor surface does not damage the inorganic substances. One type of oxidant for pretreatment can be used alone, or two or more types can be used in combination. The surface of the conductor can also be treated with ozone. Alternatively, the surface of the conductor can be pretreated with an oxidizing agent after ozone treatment. The surface of the conductor treated with ozone and / or pretreatment oxidizing agent is then modified with hydroxyl groups. The water-repellent agent for the conductor surface of this embodiment can also be used to treat the surface of the hydroxyl-modified conductor.

[0060] The water-repellent agent for conductive surfaces of this embodiment can also be used to treat a substrate having two or more regions of different materials, wherein at least one of the two or more regions has a conductive surface. The substrate surface to be treated only needs to have at least one region with a conductive surface, or it can have two or more regions with conductive surfaces. When there are two or more regions with conductive surfaces, these regions can contain the same type of conductor or different conductors. In addition to regions with conductive surfaces, the substrate surface to be treated can also include regions without conductive surfaces (e.g., regions containing insulators (hereinafter referred to as insulator regions)). The substrate surface to be treated can also include one or more insulator regions. When there are two or more insulator regions, these regions can be made of the same material or different materials. It is preferable that the substrate surface to be treated includes at least one region with a conductive surface and at least one insulator region. The insulator constituting the insulating region is composed of insulating compounds. Examples of insulating compounds include, for instance, aluminum oxide (Al₂O₃), titanium oxide (TiO₂), zirconium oxide (ZrO₂), hafnium oxide (HfO₂), tantalum oxide (Ta₂O₅), silicon oxide (SiOx(1≦X≦2)), fluorine-containing silicon oxide (SiOF), carbon oxide containing silicon oxide (SiOC), etc.; nitrides such as silicon nitride (SiN) and boron nitride (BN); carbides such as silicon carbide (SiC); carbonitrides such as silicon carbonitride (SiCN); acid nitrides such as acid silicon nitride (SiON); acid carbonitrides such as acid silicon carbonitride (SiOCN); and insulating resins such as polyimide, polyester, and plastic resins.

[0061] The surface of the substrate (the surface to be processed) includes, in addition to the surface of the substrate itself, the surfaces of inorganic and organic patterns disposed on the substrate, as well as the surfaces of inorganic or organic layers that are not patterned. Examples of inorganic patterns disposed on the substrate include patterns formed by etching a photoresist layer on the surface of an inorganic layer present on the substrate, which is then etched. Examples of inorganic layers include, in addition to the substrate itself, oxide films of elements constituting the substrate; inorganic films or layers formed on the substrate surface such as SiN, SiOx, W, Co, TiN, TaN, Ge, SiGe, Al, Al₂O₃, Ni, Ru, Cu, tetraethoxysilane (TEOS), Low-k materials, and interlayer insulating films (ILDs). There are no particular limitations on the inorganic film or layer, but examples include inorganic films or layers formed during the fabrication of semiconductor devices.

[0062] Examples of organic patterns disposed on a substrate include resin patterns formed on the substrate using photoresist and photolithography. Organic patterns can be formed by, for example, forming an organic layer of photoresist film on the substrate, exposing and developing this organic layer using a photomask. As an organic layer, in addition to the surface of the substrate itself, examples include organic layers disposed on the surface of a multilayer film disposed on the surface of the substrate. There are no particular limitations on such organic layers, but examples include organic films used to form etching photomasks during the fabrication of semiconductor devices.

[0063] On the surface of the substrate being processed, at least one region includes a region containing two or more conductive surfaces, and the materials of adjacent regions in the two or more aforementioned regions may also be different from each other.

[0064] When the surface to be processed comprises two regions, the surface to be processed may also comprise: a first region containing a conductive surface, and a second region (e.g., an insulating region) that is of a different material from the first region and is adjacent to the first region. In this case, "adjacent regions" means the first region and the second region. The first region and the second region may each be divided into multiple regions, or they may not be divided.

[0065] When the surface to be processed contains three or more regions, the surface to be processed may also contain: a first region containing a conductive surface, a second region (e.g., an insulating region) that is of a different material from the first region and is adjacent to the first region, and a third region that is of a different material from the second region and is adjacent to the second region. In this case, "adjacent regions" may refer to the first region and the second region (i.e., adjacent regions), or the first region and the third region (i.e., even more adjacent regions). When the first region and the third region are not of different materials (i.e., when both the first region and the third region contain conductive surfaces), "adjacent regions" will become the first region and the second region, or the second region and the third region (i.e., adjacent regions). The first region, the second region, and the third region may each be divided into multiple regions, or they may not be divided. The same approach can be applied when the surface to be processed contains a fourth or more regions. There are no particular restrictions on the upper limit of the number of regions with different materials, as long as it does not impair the effect of the present invention, but it can be, for example, 7 or less or 6 or less, typically 5 or less.

[0066] The water-repellent agent for the conductive surface of this embodiment contains compound (P1). Compound (P1) is a compound having an adsorbent group selected from the group consisting of amino, phosphonic, anhydride, hydrogen sulfide, and chlorine groups bonded to an aromatic ring, and a straight-chain or branched-chain alkyl group or a straight-chain or branched-chain fluorinated alkyl group. In compound (P1), the alkyl or fluorinated alkyl group is hydrophobic and has the function of acting as a water-repellent group. Compound (P1) is adsorbed onto the conductive surface by the adsorbent group and has the function of forming a self-assembled monolayer (SAM) material (hereinafter also referred to as "SAM agent"). On the other hand, the alkyl or fluorinated alkyl group can exhibit water-repellent function. In compound (P1), these groups do not interfere with each other by being bonded to the aromatic ring, and exert excellent adsorption and water-repellent properties on the conductive surface.

[0067] The water-repellent agent for the conductive surface of this embodiment has high selectivity for the area containing the conductive surface, and therefore can be particularly suitable for area-selective film formation on the surface of a substrate using the ALD method.

[0068] <Second Type: Method for Hydrophobicating Conductor Surface> The second type of the present invention is a method for hydrophobicating conductor surface. The method of this type includes exposing the conductor surface to a hydrophobic agent of the first type.

[0069] As a conductive surface, there are examples similar to those described above. A metallic surface is preferred as the conductive surface.

[0070] (Exposure Step) There are no particular limitations on the method of exposing the conductive surface to the conductive surface water-repellent agent, and known methods can be used. Examples of methods for exposing the conductive surface to the conductive surface water-repellent agent include immersing the subject having a conductive surface in the conductive surface water-repellent agent (immersion method), and applying the conductive surface water-repellent agent to the conductive surface (e.g., spin coating, roll coating, scraper coating, etc.). Examples of exposure temperatures include 10°C to 90°C, preferably 20°C to 80°C, even more preferably 20°C to 70°C, and even more preferably 20°C to 65°C. Examples of exposure time include any sufficient time required for the conductive surface to adsorb the compound (P1), such as 30 seconds or more, 1 minute or more, 3 minutes or more, 5 minutes or more, 10 minutes or more, 15 minutes or more, 20 minutes or more, or 25 minutes or more. There are no particular restrictions on the upper limit of exposure time, but it is better to be less than 2 hours, even better to be less than 90 minutes, better to be less than 60 minutes, and especially better to be less than 45 minutes.

[0071] After exposure, the substrate may be cleaned (e.g., cleaned with water, surfactants, etc.) and / or dried (dried by nitrogen blowing, etc.) as necessary. There are no particular limitations on the cleaning method; a suitable cleaning solution can be used depending on the purpose of cleaning the conductive surface. For example, when the conductive surface is part of a substrate surface with inorganic or organic patterns, a cleaning solution that can be used for cleaning inorganic or organic patterns can be directly applied. Examples of cleaning solutions for inorganic patterns include SPM (sulfuric acid-hydrogen peroxide water) and APM (ammonia-hydrogen peroxide water), while examples of cleaning solutions for organic patterns include water and surfactants. Cleaning can also be performed with ethanol such as isopropanol and / or water. After drying, the treated substrate may be subjected to additional heat treatment at 100°C to 300°C, as necessary.

[0072] On the surface of a conductor, by exposing the surface of the conductor of the first type to a water-repellent agent, a compound (P1) is adsorbed on the surface of the conductor. In this way, the surface of the conductor is endowed with water-repellent properties.

[0073] (Other Steps) In addition to the exposure step described above, the method of this embodiment may also include other steps. As an example of other steps, a pretreatment step is given.

[0074] The pretreatment of the conductor surface is preferably a treatment that imparts hydroxyl groups to the conductor surface. Examples of pretreatment methods include ozone treatment and treatment with a pretreatment oxidant. Examples of pretreatment oxidants are the same as those mentioned above. Among these, from the viewpoint of improving the water repellency of the conductor surface, at least one oxidant selected from the group consisting of hydrogen peroxide and perhalic acids is preferred.

[0075] There is no particular limitation on the pretreatment temperature, but it is typically 10~35°C, preferably 15~30°C, and even more preferably 20~25°C. If the pretreatment temperature is within the above-mentioned preferred range, it is easy to remove the natural oxide film on the surface of the conductor and to impart hydroxyl groups to the surface of the conductor.

[0076] There is no particular limitation on the pretreatment time, but it is typically 10 seconds to 10 minutes, preferably 20 seconds to 5 minutes, and even more preferably 30 seconds to 3 minutes. If the pretreatment temperature is within the above-mentioned preferred range, it is easy to remove the natural oxide film on the surface of the conductor and to impart hydroxyl groups to the surface of the conductor.

[0077] The hydrophobicity of a conductive surface can be confirmed by measuring the contact angle of water relative to the conductive surface. The contact angle of water relative to the conductive surface hydrophobicated by the method of this embodiment becomes larger than the contact angle of water relative to the conductive surface before hydrophobication. The contact angle of water relative to the conductive surface hydrophobicated by the method of this embodiment is, for example, 60° or more, 80° or more, 85° or more, 90° or more, 95° or more, or 100° or more. There is no particular limitation on the upper limit of the aforementioned contact angle, but it is, for example, 140° or less, typically 130° or less.

[0078] The water-repellent method for the conductive surface of this embodiment can effectively repel water because it can use the water-repellent agent for the conductive surface of the first type.

[0079] <Third Type: Method for Selectively Water-Repellentizing Regions Having Conductive Surfaces> The third type of the present invention is a method for selectively water-repellentizing regions having conductive surfaces in a substrate having surfaces comprising two or more regions of mutually different materials, wherein at least one of the aforementioned two or more regions has a conductive surface. This method involves exposing the surface of the aforementioned substrate to a conductive surface water-repellent agent of the first type.

[0080] (Substrate) The substrate selectively hydrophobic by the method of this embodiment has a surface comprising two or more regions of different materials. In the aforementioned substrate, at least one of the aforementioned two or more regions has a conductive surface. It is preferable that the conductive surface is a metallic surface. As a substrate, the same as described above can be cited.

[0081] The surface of the substrate to be treated includes two or more regions, at least one of the two or more aforementioned regions contains a conductive surface, and the materials of adjacent regions in the two or more aforementioned regions may also be different. In the method of this embodiment, by exposing the surface of the substrate to be treated in the first type of conductive surface water-repellent agent, the compound (P1) can be selectively adsorbed onto the conductive surface. Thereby, the contact angles relative to the surface of the aforementioned two or more regions can also be different.

[0082] Among the aforementioned two or more regions, the region that tends to have a higher water contact angle than the other region (preferably with a lower surface free energy) includes at least one region selected from the group consisting of tungsten (W), cobalt (Co), aluminum (Al), titanium nitride (TiN), tantalum nitride (TaN), nickel (Ni), ruthenium (Ru), and copper (Cu). It is preferable that the region includes at least one of the group consisting of tungsten, ruthenium, copper, and cobalt, and even more preferable that it includes at least one of the group consisting of tungsten and ruthenium. The region having a conductive surface may also be a region composed of such conductive materials.

[0083] Among the aforementioned two or more regions, the region that tends to have a smaller water contact angle than the other region (preferably with a higher surface free energy) includes at least one region selected from the group consisting of silicon (Si), silicon nitride (SiN), silicon oxide (SiOx), germanium (Ge), silicon germanium (SiGe), tetraethoxysilane (TEOS), low-k materials, and interlayer insulating films (ILDs). The insulating region may be a region composed of materials including the aforementioned insulating compounds.

[0084] In the method of this embodiment, the surface of the substrate to be processed may also include: a first region having a conductive surface, and a second region having a different material from the first region and being adjacent to the first region. In this case, "adjacent region" means the first region and the second region. The first region and the second region may each be divided into multiple regions, or they may not be divided.

[0085] Examples of the first region and the second region include a configuration where the surface of the substrate itself is the first region and the surface of the inorganic layer formed on the substrate surface is the second region, and a configuration where the surface of the first inorganic layer formed on the substrate surface is the first region and the surface of the second inorganic layer formed on the substrate surface is the second region. Similarly, configurations where an organic layer is formed, other than these inorganic layer formations, can also be described.

[0086] As a configuration where the surface of the substrate itself is the first region and the surface of the inorganic layer formed on the substrate surface is the second region, and the hydrophobicity is selectively improved between two or more adjacent regions of different materials on the substrate surface, and the difference in the water contact angle between the regions is increased, it is preferable to use the surface of at least one type of substrate selected from the group consisting of Si substrate, SiN substrate, SiOx substrate, Ge substrate, SiGe substrate, substrate containing TEOS film, substrate containing Low-k film and substrate containing ILD as the first region, and the surface of the inorganic layer formed on the aforementioned substrate surface including at least one type of TiN, TaN, W, Co, Al, Ni, Ru and Cu as the second region.

[0087] As a configuration where the surface of the first inorganic layer formed on the substrate surface is designated as the first region and the surface of the second inorganic layer formed on the substrate surface is designated as the second region, from the viewpoint of selectively enhancing hydrophobicity and increasing the difference in water contact angle between two or more adjacent regions with different materials on the substrate surface, it is preferable to designate the surface of the first inorganic layer formed on the surface of any substrate (e.g., a Si substrate) as the first region and the surface of the second inorganic layer formed on the aforementioned substrate surface as the second region, which includes at least one material selected from the group consisting of SiN, SiOx, Ge, SiGe, TEOS, Low-k materials and ILD.

[0088] ≪Types where the substrate surface includes three or more regions≫ When the substrate surface includes three or more regions, the substrate surface may also include: a first region containing a conductive surface, a second region of a different material from the first region and adjacent to the first region, and a third region of a different material from the second region and adjacent to the second region. In this case, "adjacent regions" may refer to the first region and the second region (i.e., adjacent regions), or it may refer to the first region and the third region (i.e., even more adjacent regions). If the first region and the third region are not of different materials (i.e., both the first region and the third region contain conductive surfaces), "adjacent regions" will be the first region and the second region, or the second region and the third region (i.e., adjacent regions). The first region, the second region, and the third region may each be divided into multiple regions, or they may not be divided.

[0089] Examples of the first region, the second region, and the third region include configurations such as the surface of the substrate itself as the first region, the surface of the first inorganic layer formed on the surface of the substrate as the second region, and the surface of the second inorganic layer formed on the surface of the substrate as the third region. Configurations where an organic layer is formed, different from the formation of such inorganic layers, can also be described in the same way. Configurations including inorganic layers where only one of the second and third inorganic layers is replaced with an organic layer, and configurations where both inorganic and organic layers are replaced, can also be described in the same way. From the viewpoint of selectively enhancing hydrophobicity and increasing the difference in water contact angle between two or more adjacent regions of different materials on a substrate surface, it is preferable to define the surface of any substrate (e.g., a Si substrate) as the first region, the surface of the substrate containing at least one of the following first inorganic layers as the second region, and the surface of the substrate containing at least one of the following second inorganic layers as the third region. The same approach can also be applied to the substrate surface containing a fourth or more regions. There is no particular limitation on the number of regions of different materials, as long as it does not impair the effect of the present invention, but it is typically 7 or less, 6 or less, and usually 5 or less.

[0090] (Exposure Step) There is no particular limitation on the method of exposing the substrate surface to the surface of the first type of conductor using a water-repellent agent, and known methods can be used. As a method for exposing the substrate surface to the surface of the first type of conductor using a water-repellent agent, there are methods that are the same as those described in the method of the second type.

[0091] (Other Steps) In addition to the exposure step described above, the method of this embodiment may also include other steps. One example of such other steps is a pretreatment step. Pretreatment is preferably a process that imparts hydroxyl groups to the substrate surface. As a pretreatment method, a method identical to that described in the second embodiment above is also included.

[0092] In the method of this embodiment, by exposing a first-type conductive surface to a substrate surface comprising two or more regions of different materials, a water-repellent agent is used to enhance the selective hydrophobicity of the regions having conductive surfaces among the aforementioned two or more regions. In the substrate implementing the method of this embodiment, the contact angle of water with respect to the surface of the region having conductive surfaces is, for example, 60° or more, 80° or more, 85° or more, 90° or more, 95° or more, or 100° or more. There is no particular limitation on the upper limit of the aforementioned contact angle, but it is, for example, 140° or less, typically 130° or less. In the substrate implementing the method of this embodiment, the contact angle of water with respect to the surface of the insulating region is hardly enhanced in the region having conductive surfaces. Therefore, the difference in water contact angle between the region having conductive surfaces and the insulating region is generally larger after implementation compared to before implementing the method of this embodiment. In the substrate implementing the method of this embodiment, the difference in the contact angle of water between the region having a conductive surface and the insulating region is preferably 10° or more, preferably 20° or more, preferably 30° or more, and even more preferably 40° or more. There are no particular limitations on the upper limit of the contact angle difference, as long as it does not impair the effect of the present invention; for example, it can be 80° or less, or 70° or less, typically 60° or less.

[0093] <Fourth Type: Surface Treatment Method> The fourth type of the present invention is a method for surface treatment of a substrate having a surface comprising two or more regions of different materials, wherein at least one of the two or more regions has a conductive surface. The method of this type includes exposing the surface of the substrate to a conductive surface of the first type using a water-repellent agent.

[0094] (Substrate) As a substrate for surface treatment by the method of this embodiment, there are examples that are the same as the substrates described in the third embodiment. It is preferable that the conductive surface is a metallic surface.

[0095] (Exposure Step) As an exposure method for the surface of a conductive material of the first type on the substrate surface using a water-repellent agent, there is a method that is the same as the method of the second type.

[0096] (Other Steps) In this embodiment, the method may include other steps besides the exposure step described above. One example of such an example is a pretreatment step. The pretreatment step is preferably a treatment that imparts hydroxyl groups to the substrate surface. As a pretreatment method, a method identical to that described in the second embodiment is also included.

[0097] <Fifth Type: Region-Selective Film Forming Method for Substrate Surface> The fifth type of the present invention is a region-selective film forming method for a substrate surface. This type of method includes treating the aforementioned surface of the substrate using the surface treatment method of the fourth type, and forming a film on the surface of the surface-treated substrate using atomic layer growth. In this type of method, the deposition amount of the film-forming material in the aforementioned atomic layer growth method exhibits region-selective differences.

[0098] (Surface treatment step) In the method of this embodiment, firstly, the surface of the substrate is treated by the surface treatment method of the fourth type. The substrate to be treated may be the same as the substrate mentioned in the third type.

[0099] By surface treatment of the substrate, the water repellency of the area with the conductive surface can be selectively improved in the aforementioned two or more areas.

[0100] (ALD film formation step) Next, a film is formed on the surface of the surface-treated substrate using the ALD method. In the aforementioned surface-treated substrate surface, the water repellency of the regions with conductive surfaces is selectively enhanced among the aforementioned two or more regions. As a result, the amount of material deposited to form the film can selectively differ across the regions of the substrate surface between the aforementioned two or more regions. This selective enhancement of water repellency can be confirmed by measuring the contact angle of water relative to the surface of the region. Specifically, the regions with conductive surfaces are less prone to adsorption (preferably chemisorption) of the film-forming material formed by the ALD method. As a result, there is a difference in the amount of film-forming material deposited between the aforementioned two or more regions. That is, the amount of film-forming material deposited by the ALD method exhibits selective regional differences. Specifically, the amount of film-forming material deposited in the regions with conductive surfaces is lower than the amount deposited in the insulating regions. Examples of chemical adsorption as a film-forming material include chemical adsorption of hydroxyl groups imparted to the substrate surface through pretreatment.

[0101] Among the aforementioned two or more regions, regions where the water contact angle tends to become larger than that of the other region (preferably with a smaller surface free energy) include regions selected from at least one of the group consisting of W, Co, Al, Ni, Ru, and Cu. Regions having a conductive surface may also include such regions. Among the aforementioned two or more regions, regions where the water contact angle tends to become smaller than that of the other region (preferably with a higher surface free energy) include regions selected from at least one of the group consisting of Si, Al₂O₃, SiN, SiOx, Ge, SiGe, TEOS, Low-k materials, and ILD. Insulating regions, in addition to the aforementioned insulating compounds, may also be regions composed of materials including such materials.

[0102] ≪Film Formation by ALD Method≫ There are no particular limitations on the film formation method of ALD method, but it is preferable to use a film formation method that uses the adsorption (preferably chemical adsorption) of at least two gas-phase reactants (hereinafter simply referred to as "precursor gases"). Specifically, there are methods that include the following steps (a) and (b), and repeat the following steps (a) and (b) at least once (1 cycle) until the desired film thickness is obtained. (a) is the step of exposing the surface-treated substrate to a pulse of the first precursor gas, and (b) is the step of exposing the substrate to a pulse of the second precursor gas after the aforementioned step (a).

[0103] The process after step (a) and before step (b) may include a plasma treatment step, a step of removing or venting (expelling) the first precursor gas and its reactants using a carrier gas, a second precursor gas, etc., or it may not include these steps. The process after step (b) may include a plasma treatment step, a step of removing or venting the second precursor gas and its reactants using a carrier gas, etc., or it may not include these steps. Examples of carrier gases include inert gases such as nitrogen, argon, and helium.

[0104] It is preferable that each pulse in each cycle and each layer formed are self-controlled, and it is even more preferable that each layer formed is a single atomic layer. The thickness of the aforementioned single atomic layer can be set to, for example, 5 nm or less, preferably 3 nm or less, even more preferably 1 nm or less, and even more preferably 0.5 nm or less.

[0105] As the first precursor gas, examples include organometallic compounds, metal halides, and metal oxide halides, specifically including tantalum pentoxide, tetra(dimethylamino)titanium, tin(dimethylamino)tantalum, tetra(dimethylamino)zirconium, tetra(dimethylamino)hafnium, tetra(dimethylamino)silane, copper hexafluoroacetate vinyltrimethylsilane, Zn(C2H5)2, Zn(CH3)2, TMA (trimethylaluminum), TaCl5, WF6, WOCl4, CuCl, ZrCl4, AlCl3, Al(CH3)3, TiCl4, SiCl4, HfCl4, etc.

[0106] As the second precursor gas, examples include precursor gases that can decompose the first precursor and remove the precursor gas or the ligand of the first precursor. Specifically, examples include H2O, H2O2, O2, O3, NH3, H2S, H2Se, PH3, AsH3, C2H4 or Si2H6, etc.

[0107] There is no particular limitation on the exposure temperature for step (a), but it is, for example, 100°C or higher and 800°C or lower, preferably 150°C or higher and 650°C or lower, even more preferably 180°C or higher and 500°C or lower, and even more preferably 200°C or higher and 375°C or lower.

[0108] There are no particular restrictions on the exposure temperature in step (b), but there are examples of temperatures that are substantially equal to or higher than the exposure temperature in step (a). There are no particular limitations on the films formed by the ALD method, but examples include films containing pure elements (e.g., Si, Cu, Ta, W), films containing oxides (e.g., SiO 2, GeO 2, HfO 2, ZrO 2, Ta 2O 5, TiO 2, Al 2O 3, ZnO, SnO 2, Sb 2O 5, B 2O 3, In 2O 3, WO 3), films containing nitrides (e.g., Si 3N 4, TiN, AlN, BN, GaN, NbN), films containing carbides (e.g., SiC), films containing sulfides (e.g., CdS, ZnS, MnS, WS 2, PbS), films containing selenides (e.g., CdSe, ZnSe), films containing phosphides (GaP, InP), films containing arsenides (e.g., GaAs, InAs), or mixtures thereof.

[0109] In this embodiment of the method, a film is formed on a substrate that has undergone surface treatment using a conductive surface water-repellent agent of the first type by the ALD method. The water repellency of the regions with conductive surfaces on the surface-treated substrate is selectively enhanced. Therefore, the accumulation of film-forming material formed by the ALD method can be suppressed on the regions with conductive surfaces. As a result, the amount of film-forming material accumulated by the ALD method is less on the regions with conductive surfaces compared to the insulating regions. Therefore, film formation on insulating regions can be selectively performed using the ALD method. The conductive surface water-repellent agent of the first type has higher selectivity for conductive surfaces. Therefore, by surface treating the substrate with the conductive surface water-repellent agent of the first type, the selectivity for film formation on insulating regions can be enhanced in the film formation by the ALD method. [Example]

[0110] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[0111] (Preparation of Water-Repellent Agent for Conductive Surfaces) [Examples 1-2, Comparative Examples 1-3] The water-repellent agents for conductive surfaces shown in Table 1 were prepared. The concentration of the compound in the water-repellent agent for conductive surfaces was adjusted to 0.1% by mass relative to the total mass of the water-repellent agent for conductive surfaces. The specific electrophoresis rate of toluene used as an organic solvent was 2.37.

[0112] [Table 1] compound organic solvents Example 1 4-n-Octadectoaniline Toluene Example 2 4-Methylbenzenethiol Toluene Comparative Example 1 Octadecylphosphonic acid Toluene Comparative Example 2 Phenylophosphonic acid Toluene Comparative Example 3 benzenethiol Toluene

[0113] <Water Repellent Treatment (1)> Using the conductive surface water repellent agent of each example, the ruthenium substrate is subjected to water repellent treatment according to the following method.

[0114] • Pretreatment: The substrate was treated with ozone (O3) for 15 minutes. Then, the substrate was immersed in a 3.59% by mass H2O2 aqueous solution for 1 minute at room temperature for pretreatment. After the above pretreatment, the substrate was washed with ion-exchange distilled water for 1 minute. The washed substrate was dried with a nitrogen stream.

[0115] • Water-repellent treatment: The dried substrate is immersed in the conductive surface of each example of a water-repellent agent for 30 minutes at room temperature to perform surface treatment of the substrate. The substrate after water-repellent treatment is washed with isopropanol for 1 minute, and then washed with ion-exchanged distilled water for 1 minute. The washed substrate is dried with a nitrogen stream to obtain a water-repellent treated substrate.

[0116] <Determination of Water Contact Angle (1)> The water contact angle was measured for each substrate after the above water-repellent treatment. The water contact angle was measured using a Dropmaster 700 (manufactured by Kyowa Interface Science Co., Ltd.). A drop of pure water (2.0 μL) was dropped onto the surface of the surface-treated substrate, and the contact angle was measured 2 seconds after the drop. The results are shown in Table 2.

[0117] [Table 2] compound Contact angle (°) Example 1 4-n-Octadectoaniline 118.4 Example 2 4-Methylbenzenethiol 65.6 Comparative Example 1 Octadecylphosphonic acid 61.7 Comparative Example 2 Phenylophosphonic acid 58.3 Comparative Example 3 benzenethiol 54.4 No water treatment - 14.4

[0118] As shown in Table 2, the water-repellent agents for conductive surfaces of Examples 1 and 2 showed a higher water-repellent effect compared to the water-repellent agents for conductive surfaces of Comparative Examples 1 to 3.

[0119] <ALD Treatment (1)> Using the conductive surface water-repellent agent of each example, the ruthenium substrate was subjected to water-repellent treatment according to <Water Repellent Treatment (1)>. Then, an Al2O3 film was formed on the ruthenium substrate by performing 18 ALD cycles under the following conditions. • Atomic Layer Deposition (ALD) apparatus: AT-410 (manufactured by Anric Technologies) • Chamber temperature: 150°C • Precursors: trimethylaluminum and H2O

[0120] <Determination of Al 2O 3 film formation inhibition rate (1)> The Al 2O 3 film was measured on a ruthenium substrate after film formation using an X-ray fluorescence (XRF) apparatus (ZSX Primus manufactured by Rigaku Corporation). The Al 2O 3 film formation inhibition rate was calculated using the following formula (1). The results are shown in Table 3. Al 2O 3 film formation inhibition rate (%) = (T0-Tn) / T0×100 (1) Tn: The thickness of the Al 2O 3 film after ALD treatment following water removal treatment. T0: The thickness of the Al 2O 3 film after ALD treatment without water removal treatment.

[0121] [Table 3] compound Suppression rate on Ru substrate (%) Example 1 4-n-Octadectoaniline 52.7 Comparative Example 1 Octadecylphosphonic acid 33.9 Comparative Example 2 Phenylophosphonic acid 11.2 Comparative Example 3 benzenethiol 10.9

[0122] As can be seen from the results in Table 3, the ruthenium surface treated with the water-repellent agent in Example 1 showed a higher Al2O3 film formation inhibition rate compared with the ruthenium surface treated with the water-repellent agent in the comparative example.

[0123] <Water Repellent Treatment (2)> Using the conductive surface water repellent agent of each example, the SiO2 substrate is subjected to water repellent treatment according to the following method.

[0124] • Pretreatment: The substrate is treated with ozone (O3) for 15 minutes. Then, the substrate is immersed in a 3.59% by mass H2O2 aqueous solution at room temperature for 1 minute for pretreatment. After the above pretreatment, the substrate is washed with ion-exchange distilled water for 1 minute. The washed substrate is dried with a nitrogen stream.

[0125] • Water-repellent treatment: The dried substrate is immersed in the water-repellent agent on the surface of the conductor in each example for 30 minutes at room temperature to perform surface treatment of the substrate. The substrate after water-repellent treatment is washed with isopropanol for 1 minute, and then washed with ion-exchanged distilled water for 1 minute. The washed substrate is dried with a nitrogen stream to obtain a water-repellent treated substrate.

[0126] <ALD treatment (2)> An Al2O3 film is formed on the SiO2 substrate that has undergone water-repellent treatment, except for the substrate, under the same conditions as the ALD treatment (1) described above.

[0127] <Determination of Al 2O 3 film formation inhibition rate (2)> The Al 2O 3 film was measured on the SiO 2 substrate after Al 2O 3 film formation using a fluorescence X-ray analysis (XRF) device (Rigaku ZSX Primus). The Al 2O 3 film formation inhibition rate was calculated using the above formula (1). The results are shown in Table 4.

[0128] [Table 4] compound Suppression rate on SiO2 substrate (%) Example 1 4-n-Octadectoaniline 1.8 Comparative Example 1 Octadecylphosphonic acid 6.9 Comparative Example 2 Phenylophosphonic acid 7.5 Comparative Example 3 benzenethiol 0.0

[0129] The results in Table 4 show that the SiO2 surface treated with the water-repellent agent on the conductive surface of Example 1 exhibits a lower Al2O3 film formation inhibition rate compared to the SiO2 surfaces treated with the water-repellent agent on the conductive surfaces of Comparative Examples 1 and 2. The results in Tables 3 and 4 show that by performing water-repellent treatment on the conductive surface of Example 1, the formation of Al2O3 films can be selectively inhibited on the ruthenium surface.

[0130] (Preparation of water-repellent agent for conductive surface) [Examples 3-8] The water-repellent agents for conductive surface shown in Table 5 were prepared. The concentration of the compound in the water-repellent agent for conductive surface was adjusted to 0.1% of the total mass of the water-repellent agent for conductive surface.

[0131] [Table 5] compound organic solvents Organic solvents Specific Emission Rate Example 3 4-n-Octadectoaniline Cyclohexane 1.99 Example 4 4-n-Octadectoaniline decane 1.99 Example 5 4-n-Octadectoaniline decahydronaphthalene 2.16 Example 6 4-n-Octadectoaniline Butyl butyrate 4.55 Example 7 4-n-Octadectoaniline 4-Methyl-2-pentanol 10.47 Example 8 4-n-Octadectoaniline 1-Nonol 9.13

[0132] <Determination of Water Contact Angle> Water-repelling treatment was performed on the ruthenium substrate according to the above <Water Repelling Treatment (1)>. Then, the water contact angle was measured according to the above <Determination of Water Contact Angle (1)>. The results are shown in Table 6.

[0133] <Determination of Al₂O₃ Film Formation Inhibition Rate> The ruthenium substrate was subjected to water-repellent treatment according to the above <Water Repellent Treatment (1)>. Then, an Al₂O₃ film was formed on the ruthenium substrate according to the above <ALD Treatment (1)>. The film thickness of the Al₂O₃ film was measured according to the above <Determination of Al₂O₃ Film Formation Inhibition Rate (1)>, and the Al₂O₃ film formation inhibition rate was calculated. The results are shown in Table 6.

[0134] [Table 6] Contact angle (°) Ru substrate Inhibition rate (%) Example 3 117.4 55 Example 4 114.6 54 Example 5 118.2 53 Example 6 100.6 34 Example 7 100.5 28 Example 8 95.0 20

[0135] The ruthenium surfaces treated with the water-repellent agent on the conductive surfaces of Examples 3-8 all exhibited good water repellency. The results of the contact angle and inhibition rate indicate that solvents with low electrophoretic induction are preferable.

[0136] The preferred embodiments of the present invention have been described above, but the present invention is not limited to these embodiments. Additions, omissions, substitutions, and other modifications to the configuration are possible without departing from the spirit of the present invention. The present invention is not limited to the foregoing description, but only to the scope of the appended claims.

Claims

1. A water-repellent agent for conductive surfaces, comprising a compound (P1) comprising: an aromatic ring, an adsorbent group bonded to the aromatic ring and selected from the group consisting of amino, phosphonic, anhydride, hydrogen sulfide and chlorine groups, and a straight-chain or branched alkyl group bonded to the aromatic ring.

2. As in claim 1, the conductive surface is treated with a water-repellent agent, wherein, The aforementioned compound (P1) is represented by the following general formula (P1-1), [wherein, R0 represents a straight-chain or branched alkyl group; R1 represents an organic group (but, the equivalent of R0 is removed); A represents a group having (n0+n1+nx) hydrogen atoms removed from a benzene ring, a group having (n0+n1+nx) hydrogen atoms removed from a naphthalene ring, or a group having (n0+n1+nx) hydrogen atoms removed from a biphenyl ring; X represents an adsorbent group selected from the group consisting of amino, phosphonic acid, anhydride, hydrogen sulfide, and chlorinated acid groups; n0 and nx each independently represent an integer of 1 or more; n1 represents an integer of 0 or more, but A is an adsorbent group having (n0+n1+nx) hydrogen atoms removed from a benzene ring.] When (n0+n1+nx) hydrogen atoms are removed from a base, n0+n1+nx≦6; when A is a base from a naphthalene ring with (n0+n1+nx) hydrogen atoms removed, n0+n1+nx≦8; when A is a base from a biphenyl ring with (n0+n1+nx) hydrogen atoms removed, n0+n1+nx≦10. When n0 is 2 or more, the complex R0s can be the same or different from each other; when n1 is 2 or more, the complex R1s can be the same or different from each other; when nx is 2 or more, the complex Xs can be the same or different from each other.

3. As in claim 1, the conductive surface is treated with a water-repellent agent, wherein, Compound (P1) is represented by the following general formula (P1-1-1), [where R0 represents a straight-chain or branched alkyl group; X represents an adsorption group selected from the group consisting of amino, phosphonic, anhydride, hydrogen sulfide and chlorine groups; n represents 0 or 1].

4. If a water-repellent agent is used on the surface of the conductive material as described in any of claims 1 to 3, wherein, The aforementioned conductive surface contains at least one material selected from the group consisting of tungsten, ruthenium, copper, and cobalt.

5. The conductive surface water repellent of any one of claims 1 to 3 is used to treat a substrate having a surface comprising two or more regions of different materials, wherein at least one of the two or more regions has a conductive surface.

6. A method for water-repellent treatment of a conductive surface, comprising exposing the conductive surface to a conductive surface as described in any one of claims 1 to 3 using a water-repellent agent.

7. A method for selectively repelling water, comprising selectively repelling the regions having conductive surfaces in a substrate having a surface comprising two or more regions having different materials, wherein at least one of the two or more regions has a conductive surface, and comprising exposing the aforementioned surface of the substrate to a conductive surface as claimed in any one of claims 1 to 3 using a water-repellent agent.

8. A method for surface treatment, comprising surface treatment of a substrate having a surface comprising two or more regions of different materials, wherein at least one of the two or more regions has a conductive surface, and exposing the aforementioned surface to a conductive surface of any one of claims 1 to 3 using a water-repellent agent.

9. A method for forming a film on a substrate surface with region selectivity, wherein the deposition amount of film-forming material formed by atomic layer growth on the substrate surface has selective differences in region, and includes treating the aforementioned surface of the substrate by a surface treatment method as described in claim 8, and forming a film on the surface of the surface-treated substrate by atomic layer growth.