Water-repellent agent for conductor surfaces, method for making conductor surfaces water-repellent, method for selectively making a region having a conductor surface water-repellent, surface treatment method, and method for selectively forming a film on a region of a substrate surface

Abstract

To provide a water repellent agent for an electroconductor surface, which can satisfactorily make an electroconductor surface water-repellent; a method for making the electroconductor surface water-repellent, which uses the water repellent agent for the electroconductor surface; a method for selectively making a region having the electroconductor surface water-repellent; a surface treatment method; and a method for forming a film on a selective region of a substrate surface.SOLUTION: A water repellent agent for an electroconductor surface includes a compound (P1) that contains: an aromatic ring; an adsorptive group which is bonded to the aromatic ring and is selected from the group consisting of an amino group, a phosphonate group, an anhydride group, a thiol group, and an acid chloride group; and a straight-chain or branched-chain alkyl group, or a straight-chain or branched-chain fluoroalkyl group, any of which is bonded to the aromatic ring.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a water repellent agent for a conductor surface, a method for making a conductor surface water repellent, a method for selectively making a region having a conductor surface water repellent, a surface treatment method, and a method for selectively forming a film on a region of a substrate surface. [Background technology]

[0002] In recent years, there has been an increasing trend toward higher integration and miniaturization of semiconductor devices, and organic patterns used as masks and inorganic patterns fabricated by etching processes are becoming increasingly finer, which requires film thickness control at the atomic layer level. Atomic layer deposition (ALD) is a well-known method for forming thin films on a substrate at the atomic layer level. Compared to conventional chemical vapor deposition (CVD) methods, ALD offers superior step coverage and film thickness control.

[0003] The ALD method is a thin-film formation technology in which two types of gases, each containing the same element as the film to be formed, are alternately supplied onto a substrate, and a thin film is formed on the substrate in atomic layer units, repeatedly, to form a film of the desired thickness. In the ALD method, while the source gas is being supplied, only one or a few layers of the source gas components are adsorbed onto the substrate surface, and excess source gas does not contribute to growth; this utilizes the growth's self-limiting function. For example, when forming an Al2O3 film on a substrate, a source gas consisting of TMA (TriMethyAlAlUminum) and an oxidizing gas are used. When forming a nitride film on a substrate, a nitriding gas is used instead of the oxidizing gas.

[0004] In recent years, attempts have been made to form films on substrate surfaces in a region-selective manner using the ALD method. Accordingly, there is a demand for substrates whose surfaces are region-selectively modified so that they can be suitably applied to region-selective film formation methods on substrates using the ALD method. By utilizing the ALD method in film formation methods, it is expected that film thickness control at the atomic layer level, step coverage, and miniaturization of patterning can be achieved. For example, Non-Patent Document 1 describes that the formation of a self-assembled monolayer (SAM) of octadecylphosphonic acid can be used to region-selectively inhibit film formation by the ALD method. [Prior art documents] [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 [Problem to be solved by the invention]

[0006] In the ALD method for selectively depositing films on a substrate surface, the substrate surface is generally made water-repellent in a selective manner, thereby inhibiting film formation on the water-repellent substrate surface. For example, when a substrate surface contains both conductive and insulating surfaces, if a film is to be selectively deposited on the insulating surface, it is necessary to selectively make the conductive surface water-repellent.

[0007] The present invention has been made in view of the above circumstances, and has as its object to provide a water-repellent agent for the surface of a conductor that can effectively make the surface of a conductor water-repellent, a method for making the surface of a conductor water-repellent using the water-repellent agent for the surface of a conductor, a method for selectively making a region having a conductor surface water-repellent, a surface treatment method, and a method for selectively forming a film on a region of a substrate surface. [Means for solving the problem]

[0008] In order to solve the above problems, the present invention employs the following configuration.

[0009] A first aspect of the present invention is a water repellent for a conductor surface, which contains a compound (P1) including an aromatic ring, an adsorptive group bonded to the aromatic ring and selected from the group consisting of an amino group, a phosphonic acid group, an acid anhydride group, a thiol group, and an acid chloride group, and a linear or branched alkyl group or a linear or branched fluorinated alkyl group bonded to the aromatic ring.

[0010] A second aspect of the present invention is a method for making a conductor surface water-repellent, which comprises exposing the conductor surface to the water-repellent agent for conductor surfaces of the first aspect.

[0011] A third aspect of the present invention is a method for selectively making a region having a conductive surface water-repellent in a substrate having a surface including two or more regions made of different materials, at least one of the two or more regions having a conductive surface, the method comprising exposing the surface of the substrate to the water-repellent agent for conductive surfaces of the first aspect.

[0012] A fourth aspect of the present invention is a surface treatment method for a substrate having a surface including two or more regions made of different materials, at least one of which has a conductive surface, the surface treatment method comprising exposing the surface to the water repellent for conductive surfaces of the first aspect.

[0013] A fifth aspect of the present invention is a method for selectively depositing a film on a substrate surface, comprising treating the surface of the substrate by the surface treatment method of the fourth aspect, and forming a film on the surface-treated surface of the substrate by atomic layer deposition, wherein the amount of film-forming material deposited by the atomic layer deposition method varies selectively in different areas. [Effects of the Invention]

[0014] According to the present invention, there are provided a water-repellent agent for the surface of a conductor that can effectively impart water-repellency to the surface of a conductor, a method for making the surface of a conductor water-repellent using the water-repellent agent for the surface of a conductor, a method for selectively making a region having a conductor surface water-repellent, a surface treatment method, and a method for selectively forming a film on a region of a substrate surface. DETAILED DESCRIPTION OF THE INVENTION

[0015] In this specification and claims, the term "aliphatic" is defined as a relative concept to aromatic, and refers to groups, compounds, etc. that do not have aromaticity. Unless otherwise specified, the term "alkyl group" includes linear, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to alkyl groups in alkoxy groups. Unless otherwise specified, the term "alkylene group" includes linear, branched and cyclic divalent saturated hydrocarbon groups. The "halogen atom" includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0016] In this specification and claims, some structures represented by chemical formulas may have asymmetric carbon atoms, and may exist as enantiomers or diastereomers. In such cases, a single chemical formula represents all isomers. These isomers may be used alone or as a mixture.

[0017] <First Aspect: Water Repellent Agent for Conductor Surfaces> A first aspect of the present invention is a water repellent for use on the surface of a conductor. The water repellent for use on the surface of a conductor of this aspect contains a compound (P1) including an aromatic ring, an adsorptive group bonded to the aromatic ring and selected from the group consisting of an amino group, a phosphonic acid group, an acid anhydride group, a thiol group, and an acid chloride group, and a linear or branched alkyl group or a linear or branched fluorinated alkyl group bonded to the aromatic ring.

[0018] (Compound (P1)) Compound (P1) is a compound including an aromatic ring, an adsorptive group bonded to the aromatic ring and selected from the group consisting of an amino group, a phosphonic acid group, an acid anhydride group, a thiol group, and an acid chloride group, and a linear or branched alkyl group or a linear or branched fluorinated alkyl group bonded to the aromatic ring.

[0019] The aromatic ring contained in the compound (P1) is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be a polycyclic group or a monocyclic group. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Examples of heteroatoms contained in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of aromatic heterocyclic rings include a pyridine ring and a thiophene ring. The aromatic ring is preferably an aromatic hydrocarbon ring, more preferably an aromatic ring containing one or two benzene rings. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, and a biphenyl ring.

[0020] The aromatic ring is bonded to an adsorptive group selected from the group consisting of an amino group, a phosphonic acid group, an acid anhydride group, a thiol group, and an acid chloride group, and a linear or branched alkyl group or a linear or branched fluorinated alkyl group. The adsorptive group is directly bonded to a carbon atom constituting the aromatic ring. The alkyl group or fluorinated alkyl group is directly bonded to a carbon atom constituting the aromatic ring.

[0021] An "adsorption group" is a functional group that has adsorptivity to the surface of a conductor. When a conductor surface is treated with compound (P1), compound (P1) is adsorbed to the conductor surface by the adsorption group, forming a SAM. In compound (P1), the adsorption group is selected from the group consisting of an amino group, a phosphonic acid group, an acid anhydride group, a thiol group, and an acid chloride group. An example of the acid anhydride group is a succinic acid anhydride group. As the adsorption group, an amino group, a thiol group, a phosphonic acid group, or an acid anhydride group is preferred, an amino group, a thiol group, or a phosphonic acid group is more preferred, an amino group or a thiol group is even more preferred, and an amino group is particularly preferred.

[0022] The number of adsorptive groups bonded to the aromatic ring may be one or two or more. When the aromatic ring is a benzene ring, the number of adsorptive groups may be 1 to 5, 1 to 4, 1 to 3, 1, or 2. When the aromatic ring is a naphthalene ring, the number of adsorptive groups may be 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 adsorptive groups may be 1 to 9, 1 to 8, 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3, 1, or 2. The number of adsorptive groups is preferably 1 to 4, more preferably 1 to 3, even more preferably 1 or 2, and particularly preferably 1. When a plurality of adsorptive groups are bonded to an aromatic ring, the plurality of adsorptive groups may be the same as or different from one another.

[0023] The linear or branched alkyl group or linear or branched fluorinated alkyl group bonded to the aromatic ring preferably has 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 the alkyl group of the fluorinated alkyl group is branched, it preferably has 3 to 45 carbon atoms, more preferably 3 to 40 carbon atoms, and even more preferably 3 to 35 carbon atoms. The number of carbon atoms of the alkyl group or fluorinated alkyl group is not particularly limited, but 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 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 number of carbon atoms of the alkyl group or fluorinated alkyl group may be in the range of 5 to 45, 5 to 40, 5 to 35, 8 to 35, or 8 to 30. When the adsorptive group is a phosphonic acid group, the alkyl group or fluorinated alkyl group may have 5 or more carbon atoms, preferably 5 to 45 carbon atoms, more preferably 5 to 40 carbon atoms, and even more preferably 5 to 35 carbon atoms.

[0024] Specific examples of the linear or branched alkyl group include, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, an isotridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, an isohexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a heneicosyl group, a docosyl group, and the isomers of the alkyl groups.

[0025] A linear or branched fluorinated alkyl group is a group in which at least a portion of the hydrogen atoms of a linear or branched alkyl group are substituted with fluorine atoms. Examples of the linear or branched fluorinated alkyl group include the above-mentioned linear or branched alkyl groups in which at least a portion of the hydrogen atoms are substituted with fluorine atoms. In the linear or branched fluorinated alkyl group, the proportion of hydrogen atoms substituted with fluorine is not particularly limited. The fluorinated alkyl group may be a perfluoroalkyl group.

[0026] The number of linear or branched alkyl groups or linear or branched fluorinated alkyl groups bonded to the aromatic ring may be one or more. When the aromatic ring is a benzene ring, the number of the alkyl groups or fluorinated alkyl groups may be 1 to 5, 1 to 4, 1 to 3, 1, or 2. When the aromatic ring is a naphthalene ring, the number of the alkyl groups or fluorinated alkyl groups may be 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 alkyl groups or fluorinated alkyl groups may be 1 to 9, 1 to 8, 1 to 7, 1 to 6, 1 to 5, 1 to 4, 1 to 3, 1, or 2. The number of the alkyl groups or fluorinated alkyl groups is preferably 1 to 4, more preferably 1 to 3, even more preferably 1 or 2, and particularly preferably 1. When a plurality of alkyl groups or fluorinated alkyl groups are bonded to an aromatic ring, the plurality of alkyl groups or fluorinated alkyl groups may be the same as or different from one another.

[0027] In the aromatic ring, it is preferable that the alkyl group or fluorinated alkyl group is not bonded to the ortho position of the adsorptive group in order to avoid interference with the adsorptive group.

[0028] The compound (P1) may contain other groups in addition to the above-mentioned adsorptive groups, alkyl groups, or fluorinated alkyl groups. Examples of the other groups include organic groups (excluding linear or branched alkyl groups and linear or branched fluorinated alkyl groups). Examples of the organic groups include hydrocarbon groups which may have a substituent. The hydrocarbon groups may be aliphatic hydrocarbon groups or aromatic hydrocarbon groups. Examples of the number of carbon atoms in the hydrocarbon groups include 1 to 12, 1 to 10, 1 to 8, 1 to 6, 1 to 4, 1 to 3, 1, or 2. The aliphatic hydrocarbon group may be saturated or unsaturated. The aliphatic hydrocarbon group may be linear or branched, or may contain a cyclic structure. The cyclic structure may be monocyclic or polycyclic. The cyclic structure may contain an aliphatic hydrocarbon ring or an aliphatic heterocycle. The aromatic hydrocarbon group may be monocyclic or polycyclic, and may contain an aromatic hydrocarbon ring or an aromatic heterocyclic ring. The substituent that the hydrocarbon group may have includes functional groups other than the above-mentioned adsorptive groups. Specific examples of the substituent include, but are not limited to, a hydroxy group, a carboxy group, a halogen atom, and an alkoxy group.

[0029] Examples of the compound (P1) include compounds represented by the following general formula (P1-1).

[0030] [ka] [In the formula, R 0 represents a linear or branched alkyl group or a linear or branched fluorinated alkyl group; R 1 is an organic group (where R 0A represents a group obtained by removing (n0+n1+nx) hydrogen atoms from a benzene ring, a group obtained by removing (n0+n1+nx) hydrogen atoms from a naphthalene ring, or a group obtained by removing (n0+n1+nx) hydrogen atoms from a biphenyl ring; X represents an adsorptive group selected from the group consisting of an amino group, a phosphonic acid group, an acid anhydride group, a thiol group, and an acid chloride group; n0 and nx each independently represent an integer of 1 or more; and n1 represents an integer of 0 or more. However, when A is a group obtained by removing (n0+n1+nx) hydrogen atoms from a benzene ring, n0+n1+nx≦6; when A is a group obtained by removing (n0+n1+nx) hydrogen atoms from a naphthalene ring, n0+n1+nx≦8; and when A is a group obtained by removing (n0+n1+nx) hydrogen atoms from a biphenyl ring, n0+n1+nx≦10. When n0 is 2 or more, multiple R 0 may be the same or different; when n1 is 2 or more, a plurality of R 1 may be the same or different; when nx is 2 or more, the multiple x's may be the same or different.

[0031] In the formula (P1-1), A represents a group in which (n0+n1+nx) hydrogen atoms have been removed from a benzene ring, a group in which (n0+n1+nx) hydrogen atoms have been removed from a naphthalene ring, or a group in which (n0+n1+nx) hydrogen atoms have been removed from a biphenyl ring.

[0032] In the formula (P1-1), R 0 represents a linear or branched alkyl group, or a linear or branched fluorinated alkyl group. R 0 Examples of the linear or branched alkyl group or linear or branched fluorinated alkyl group in the formula (I) include the same as the linear or branched alkyl group or linear or branched fluorinated alkyl group described above. R 0 R is preferably a linear alkyl group or a linear fluorinated alkyl group, more preferably a linear alkyl group or a linear fluorinated alkyl group having 1 to 30 carbon atoms. 0A specific example of the group is an n-octadecyl group.

[0033] In the formula (P1-1), X represents an adsorptive group selected from the group consisting of an amino group, a phosphonic acid group, an acid anhydride group, a thiol group, and an acid chloride group. Examples of the acid anhydride group include a succinic acid anhydride group.

[0034] In the formula (P1-1), R 1 is an organic group (where R 0 (excluding those that fall under the above). R 1 The organic group in the formula (I) includes the same organic groups as those described above.

[0035] In the formula (P1-1), n0 and nx each independently represent an integer of 1 or greater. n0 and nx are preferably 1 to 4, more preferably 1 to 3, and even more preferably 1 or 2. In the formula (P1-1), n1 represents an integer of 0 or greater. n1 is preferably 0 to 4, more preferably 0 to 3, still more preferably 0 to 2, and particularly preferably 0 or 1. When n0 is 2 or more, multiple R 0 may be the same or different. When nx is 2 or more, the multiple x's may be the same or different. When n1 is 2 or more, the multiple R's may be the same or different. 1 may be the same as or different from each other.

[0036] The compound (P1) is preferably a compound represented by the following general formula (P1-1-1).

[0037] [ka] [In the formula, R 0 represents a linear or branched alkyl group or a linear or branched fluorinated alkyl group; X represents an adsorptive group selected from the group consisting of an amino group, a phosphonic acid group, an acid anhydride group, a thiol group, and an acid chloride group; and n represents 0 or 1.

[0038] In the formula (P1-1-1), R 0 and X is R in the formula (P1-1). 0 and X. In the formula (P1-1-1), n ​​represents 0 or 1. n is preferably 0.

[0039] Preferred examples of the compound (P1) are shown below: 0 and X is R in the formula (P1-1). 0 and X.

[0040] [ka]

[0041] [ka]

[0042] [ka]

[0043] [ka]

[0044] [ka]

[0045] 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-pentadecylaniline, 4-n-hexadecylaniline, 4-methylbenzenethiol, 4-n-propylbenzenethiol, 4-t-butylbenzenethiol, 4-n-pentylbenzenethiol, and 4-n-dodecylbenzenethiol, with 4-n-octadecylaniline or 4-methylbenzenethiol being preferred.

[0046] The compound (P1) may be used alone or in combination of two or more kinds. The content of compound (P1) in the water repellent for electrical conductor surfaces is preferably 0.0001 to 5 mass%, more preferably 0.001 to 4 mass%, even more preferably 0.005 to 3 mass%, and even more preferably 0.008 to 3 mass%, relative to the total mass of the water repellent for electrical conductor surfaces. When the content of the compound (P1) is within the above preferred range, the compound (P1) is easily adsorbed onto the surface of the conductor, and the water repellency of the conductor surface is improved. The water repellent agent for a conductor surface of this embodiment may not contain octadecylphosphonic acid, phenylphosphonic acid, or benzenethiol.The water repellent agent for a conductor surface of this embodiment may not contain any SAM-forming material other than compound (P1).

[0047] (optional ingredient) The water repellent for the surface of a conductor of this embodiment may contain optional components in addition to the compound (P1), such as an organic solvent and water.

[0048] <Organic solvent (S)> The water repellent agent for a conductor surface of this embodiment preferably contains an organic solvent (S). The organic solvent is not particularly limited, but is preferably one having a dielectric constant of 35 or less. Examples of organic solvents include methanol (dielectric constant: 33), diethylene glycol monobutyl ether (BDG) (dielectric constant: 13.70), propylene glycol monomethyl ether (PE) (dielectric constant: 12.71), benzyl alcohol (dielectric constant: 13), 2-heptanone (dielectric constant: 11.74), butyl glycol acetate (dielectric constant: 8.66), tert-butyl alcohol (dielectric constant: 12.5), 1-octanol (dielectric constant: 10.21), isobutanol (dielectric constant: 18.22), benzotrifluoride (dielectric constant: 9.18), decahydronaphthalene (dielectric constant: 2.16), cyclohexane (dielectric constant: 1.99), decane (dielectric constant: 1.99), and isobutyl alcohol (dielectric constant: 1.02). Examples of suitable ethylene glycol monomethyl ether (dielectric constant: 18.22), ethyl lactate (EL) (dielectric constant: 13.22), diethylene glycol monomethyl ether (dielectric constant: 15.76), 1-nonanol (dielectric constant: 9.13), toluene (dielectric constant: 2.37), propylene glycol monomethyl ether acetate (PM) (dielectric constant: 9.4), methyl isobutyl carbinol (MIBC) (dielectric constant: 10.47), 2,6-dimethyl-4-heptanol (dielectric constant: 2.98), 2-ethyl-1-butanol (dielectric constant: 12.6), 2-butanone oxime (dielectric constant: 2.9), n-dibutyl ether (dielectric constant: 3.33), butyl butyrate (dielectric constant: 4.55), and 2,6-dimethyl-4-heptanone (dielectric constant: 9.82). Among them, examples of the organic solvent (S) include, but are not limited to, methanol (dielectric constant: 33), diethylene glycol monobutyl ether (BDG) (dielectric constant: 13.70), polyethylene glycol (PE) (dielectric constant: 12.71), benzyl alcohol (dielectric constant: 12.70), 2-heptanone (dielectric constant: 11.74), butyl glycol acetate (dielectric constant: 8.66), tert-butyl alcohol (dielectric constant: 12.5), 1-octanol (dielectric constant: 10.21), isobutanol (dielectric constant: 18.22), and 4-methyl-2-pentanol (dielectric constant: 10.47). The relative dielectric constant of the organic solvent is preferably 30 or less, 25 or less, 20 or less, 15 or less, 13 or less, 12 or less, 11 or less, 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, or 5 or less. The lower limit of the relative dielectric constant of the organic solvent is not particularly limited, and examples include more than 0, 0.1 or more, 0.5 or more, or 1 or more. The relative dielectric constant of the organic solvent (S) can be measured using a commercially available liquid dielectric constant measuring device (for example, "Rufuto Model 871" manufactured by Nippon Rufuto Co., Ltd.).

[0049] The Hansen solubility parameter (dP) of the organic solvent (S) is preferably from 0 to less than 16, more preferably from 0 to 15, and even more preferably from 0 to 14. When the Hansen solubility parameter (dP) of the organic solvent (S) is within the above preferred range, the water repellency of the surface of the conductor is easily increased.

[0050] The organic solvent (S) may be used alone or in combination of two or more kinds. The water repellent agent for the surface of a conductor of this embodiment may not contain an organic solvent having a relative dielectric constant of more than 35, or may not contain one or more of the organic solvents exemplified above.

[0051] ≪Water≫ The water repellent agent for a conductor surface of this embodiment may contain water to further improve water repellency and increase the contact angle. The water may contain trace components that are inevitably mixed in. As the water, water that has been subjected to a purification treatment, such as distilled water, ion-exchanged water, or ultrapure water, is preferred, and ultrapure water that is commonly used in semiconductor manufacturing is more preferred. When the water repellent agent for the surface of a conductor contains water, the content of water is preferably from 0.01 to 25 mass %, more preferably from 0.03 to 20 mass %, and even more preferably from 0.05 to 15 mass %. When the water content is within the above preferred range, the compound (P1) is more likely to be adsorbed onto the surface of the conductor. The water repellent agent for a conductor surface of this embodiment may not contain water.

[0052] ≪Impurities, etc.≫ The water repellent for conductor surfaces of this embodiment may contain metal impurities including metal atoms such as Fe atoms, Cr atoms, Ni atoms, Zn atoms, Ca atoms, or Pb atoms. The total content of the metal atoms in the water repellent for conductor surfaces of this embodiment is preferably 100 mass ppt or less, relative to the total mass of the water repellent for conductor surfaces. The lower the lower limit of the total metal atom content, the more preferable, and for example, it can be 0.001 mass ppt or more. The total metal atom content can be, for example, 0.001 mass ppt to 100 mass ppt. By setting the total metal atom content to the preferred upper limit or less, the water repellent effect of the water repellent for conductor surfaces is improved. By setting the total metal atom content to the preferred lower limit or more, it is thought that metal atoms are less likely to be isolated and present in the system, which is less likely to adversely affect the overall production yield of the treated object. The content of metal impurities can be adjusted, for example, by a purification treatment such as filtering, etc. The purification treatment such as filtering may be performed on some or all of the raw materials before preparing the water repellent agent for the surface of a conductor, or may be performed after preparing the water repellent agent for the surface of a conductor.

[0053] The water repellent for a conductor surface of this embodiment may contain, for example, impurities derived from organic substances (organic impurities). The total content of the organic impurities in the water repellent for a conductor surface of this embodiment is preferably 5000 ppm by mass or less. The lower limit of the content of the organic impurities is preferably as low as possible, and may be, for example, 0.1 ppm by mass or more. The total content of the organic impurities may be, for example, 0.1 ppm by mass to 5000 ppm by mass.

[0054] The water repellent agent for conductor surfaces of this embodiment may contain countable particles of a size that can be counted by, for example, a light-scattering liquid-borne particle counter. The size of the countable particles is, for example, 0.04 μm or more. The number of countable particles in the water repellent agent for conductor surfaces of this embodiment is, for example, 1,000 or less per mL of cleaning solution, with the lower limit being, for example, 1 or more. It is believed that by keeping the number of countable particles in the cleaning solution within the above range, the water repellent effect of the water repellent agent for conductor surfaces is improved.

[0055] The organic impurities and / or countable entities may be added to the water repellent for conductor surfaces, or may be inevitably mixed into the water repellent for conductor surfaces during the manufacturing process of the water repellent for conductor surfaces. Examples of inevitable mixing during the manufacturing process of the water repellent for conductor surfaces include when organic impurities are contained in raw materials (e.g., organic solvents) used in the manufacturing of the water repellent for conductor surfaces, and when they are mixed in from the external environment (e.g., contamination) during the manufacturing process of the water repellent for conductor surfaces, but are not limited to these. When the counted substances are added to the water repellent agent for the surface of a conductor, the ratio of the substances present may be adjusted for each specific size, taking into consideration the surface roughness of the object to be treated, etc.

[0056] (storage container) The method for storing the water repellent agent for conductor surfaces of this embodiment is not particularly limited, and a conventionally known storage container can be used. The void ratio within the container and / or the type of gas to fill the voids during storage in the container may be appropriately determined so as to ensure the stability of the water repellent agent for conductor surfaces. For example, the void ratio within the storage container may be about 0.01 to 30% by volume.

[0057] (Object to be treated) The water repellent for conductor surfaces of this embodiment is used to make the conductor surface water repellent. The "conductor surface" refers to the surface of a region composed of a conductor. The conductor is not particularly limited as long as it is a conductive material. Examples of conductors include materials containing metal atoms. Examples of conductors include metals (e.g., simple metal elements), alloys, and metal compounds (e.g., nitrides, etc.). When the conductor is a metal, the conductor surface becomes a metal surface. When the conductor is an alloy, the conductor surface becomes an alloy surface. When the conductor is a metal compound, the conductor surface becomes a conductive metal compound surface. Examples of metals contained in the metal surface include, but are not limited to, tungsten, ruthenium, copper, aluminum, nickel, and cobalt. Examples of metal compounds contained in the conductive metal compound surface include, but are not limited to, titanium nitride and tantalum nitride. The metal surface preferably contains at least one metal selected from the group consisting of tungsten, ruthenium, copper, aluminum, nickel, and cobalt, and more preferably contains ruthenium.

[0058] The surface of the conductor may be pretreated with an oxidizing agent. Examples of oxidizing agents used to pretreat the surface of the conductor (hereinafter sometimes referred to as "pretreatment oxidizing agents") include those capable of removing a natural oxide film present on the surface of the conductor and providing hydroxyl groups to the surface of the conductor. Examples of pretreatment oxidizing agents include peroxides such as hydrogen peroxide, perhalogen acids such as periodic acid, and oxoacids such as nitric acid and hypochlorous acid. Among these, at least one pretreatment oxidizing agent selected from the group consisting of hydrogen peroxide and perhalogen acids is preferred from the viewpoint of the adsorptivity of compound (P1). At least one selected from the group consisting of hydrogen peroxide and perhalogen acids is also preferred from the viewpoint of treating the surface of the conductor without damaging the inorganic material, when the surface of an inorganic material such as SiO2 or Al2O3 coexists with the conductor surface. The pretreatment oxidizing agent may be used alone or in combination of two or more kinds. The surface of the conductor may be treated with ozone, or may be treated with a pretreatment oxidizing agent after the ozone treatment. The surface of a conductor treated with ozone and / or a pretreatment oxidizing agent is modified with hydroxyl groups, and the water repellent for a conductor surface of this embodiment may be used to treat the conductor surface modified with hydroxyl groups.

[0059] The water repellent agent for conductor surfaces of this embodiment may be used to treat a substrate having a surface including two or more regions made of different materials, at least one of which has a conductor surface. At least one region of the substrate surface to be treated may have a conductive surface, and two or more regions may have a conductive surface. When two or more regions have a conductive surface, the regions may contain the same conductive material or different conductive materials. The substrate surface to be processed may include regions that do not have a conductive surface (for example, regions made of an insulator (hereinafter referred to as insulator regions)) in addition to regions that have a conductive surface. The substrate surface to be processed may include one insulator region, or two or more. When there are two or more insulator regions, these regions may be made of the same material or different materials. The surface of the substrate to be treated preferably includes at least one region having a conductive surface and at least one insulator region. The insulator constituting the insulator region is made of an insulating compound, such as oxides such as 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), and carbon-containing silicon oxide (SiOC); nitrides such as silicon nitride (SiN) and boron nitride (BN); carbides such as silicon carbide (SiC); carbonitrides such as silicon carbonitride (SiCN); oxynitrides such as silicon oxynitride (SiON); oxycarbonitrides such as silicon oxycarbonitride (SiOCN); and insulating resins such as polyimide, polyester, and plastic resin.

[0060] The surface of the substrate (surface to be treated) includes the surface of the substrate itself, as well as the surfaces of inorganic and organic patterns provided on the substrate, and the surfaces of unpatterned inorganic or organic layers. Examples of inorganic patterns provided on a substrate include patterns formed by forming an etching mask on the surface of an inorganic layer present on the substrate using a photoresist method, followed by etching. Examples of inorganic layers include the substrate itself, oxide films of elements constituting the substrate, inorganic films or layers formed on the surface of the substrate, such as SiN, SiOx, W, Co, TiN, TaN, Ge, SiGe, Al, Al2O3, Ni, Ru, Cu, tetraethoxysilane (TEOS), low-k materials, and interlayer dielectrics (ILDs). The inorganic film or layer is not particularly limited, but examples thereof include inorganic films or layers formed in the process of manufacturing semiconductor devices.

[0061] Examples of organic patterns provided on a substrate include resin patterns formed on a substrate by photolithography using photoresist or the like. The organic pattern can be formed, for example, by forming an organic layer, which is a photoresist film, on the substrate, exposing the organic layer through a photomask, and developing it. Examples of organic layers include those provided on the surface of the substrate itself, as well as those provided on the surface of a laminate film provided on the surface of the substrate. Examples of such organic layers include, but are not limited to, organic films provided to form etching masks during the production of semiconductor devices.

[0062] The surface to be treated of the substrate includes two or more regions, at least one of which contains a conductive surface, and adjacent regions of the two or more regions may be made of different materials.

[0063] When the surface to be treated includes two regions, the surface to be treated may include a first region containing a conductive surface and a second region (e.g., an insulating region) made of a different material from the first region and adjacent to the first region. In this case, the "adjacent regions" refer to the first region and the second region. The first area and the second area may or may not be divided into a plurality of areas.

[0064] When the surface to be treated includes three or more regions, the surface to be treated may include a first region containing a conductive surface, a second region (e.g., an insulator region) made of a material different from that of the first region and adjacent to the first region, and a third region made of a material different from that of the second region and adjacent to the second region. In this case, the "adjacent regions" may be the first region and the second region (i.e., adjacent regions), or the first region and the third region (i.e., adjacent regions). When the first region and the third region are made of the same material (i.e., when both the first region and the third region contain a conductive surface), the "adjacent regions" are the first region and the second region, or the second region and the third region (i.e., adjacent regions). Each of the first area, the second area, and the third area may or may not be divided into a plurality of areas. The same concept can be applied to the case where the surface to be treated includes four or more regions. There is no particular upper limit to the number of regions made of different materials as long as the effects of the present invention are not impaired. For example, it is 7 or less, or 6 or less, and typically 5 or less.

[0065] The water repellent agent for the surface of a conductor of this embodiment contains a compound (P1). Compound (P1) is a compound in which an adsorptive group selected from the group consisting of an amino group, a phosphonic acid group, an acid anhydride group, a thiol group, and an acid chloride group, and a linear or branched alkyl group or a linear or branched fluorinated alkyl group are bonded to an aromatic ring. In compound (P1), the alkyl group or the fluorinated alkyl group is hydrophobic and functions as a water-repellent group. Compound (P1) functions as a material that adsorbs to the surface of a conductor via its adsorptive groups and forms a self-assembled monolayer (SAM) (hereinafter referred to as "SAM agent"), while its alkyl or fluorinated alkyl groups provide water-repellent properties. In compound (P1), these groups are bonded to an aromatic ring, and it is believed that they do not interfere with each other, thereby exhibiting excellent adsorptivity to the surface of a conductor and water repellency.

[0066] The water repellent agent for the surface of a conductor of this embodiment has high selectivity for regions including the surface of a conductor, and is therefore particularly suitable for region-selective film formation on a substrate surface using the ALD method.

[0067] <Second Aspect: Method for Making Conductor Surface Water-Repellent> A second aspect of the present invention is a method for making a conductor surface water-repellent, which comprises exposing the conductor surface to the water-repellent agent for conductor surfaces of the first aspect.

[0068] The conductor surface may be the same as those mentioned above, and is preferably a metal surface.

[0069] (Exposure process) The method for exposing the surface of a conductor to the water repellent agent for a conductor surface is not particularly limited, and any known method can be used. Examples of the method for exposing the surface of a conductor to the water repellent agent for a conductor surface include a method of immersing an object to be treated having a conductor surface in the water repellent agent for a conductor surface (immersion method), and a method of applying the water repellent agent for a conductor surface to the surface of a conductor (for example, spin coating, roll coating, doctor blade, etc.). The exposure temperature is, for example, 10°C or higher and 90°C or lower, preferably 20°C or higher and 80°C or lower, more preferably 20°C or higher and 70°C or lower, and even more preferably 20°C or higher and 65°C or lower. The exposure time may be any time sufficient for compound (P1) to be adsorbed onto the surface of the conductor, and may be, for example, 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 is no particular upper limit to the exposure time, but, for example, 2 hours or less is preferable, 90 minutes or less is more preferable, 60 minutes or less is even more preferable, and 45 minutes or less is particularly preferable.

[0070] After the exposure, the substrate may be washed (for example, washed with water, an activator rinse, etc.) and / or dried (dried with nitrogen blow, etc.) as needed. The cleaning method is not particularly limited, and cleaning can be performed using an appropriate cleaning solution depending on the purpose of the conductor surface. For example, if the conductor surface is part of a substrate surface having an inorganic or organic pattern, cleaning solutions that have traditionally been used for cleaning inorganic or organic patterns can be used as is. For example, cleaning solutions for inorganic patterns include SPM (sulfuric acid / hydrogen peroxide solution) and APM (ammonia / hydrogen peroxide solution), while cleaning solutions for organic patterns include water, surfactant rinses, etc. Cleaning may be performed with alcohol such as isopropanol and / or water. The dried treated substrate may be additionally subjected to a heat treatment at 100° C. or higher and 300° C. or lower, if necessary.

[0071] By exposing the surface of a conductor to the water repellent agent for the surface of a conductor of the first embodiment, the compound (P1) is adsorbed onto the surface of the conductor, thereby imparting water repellency to the surface of the conductor.

[0072] (Other processes) The method of this embodiment may include other steps in addition to the exposure step, such as a pretreatment step.

[0073] The pretreatment of the conductor surface is preferably a treatment capable of adding hydroxyl groups to the conductor surface. Examples of pretreatment methods include ozone treatment and treatment with a pretreatment oxidizing agent. Examples of pretreatment oxidizing agents include those similar to those described above. Among these, the pretreatment oxidizing agent is preferably at least one selected from the group consisting of hydrogen peroxide and perhalogen acids, from the viewpoint of improving the water repellency of the conductor surface.

[0074] The treatment temperature for the pretreatment is not particularly limited, but is typically 10 to 35°C, preferably 15 to 30°C, and more preferably 20 to 25°C. When the treatment temperature for the pretreatment is within the above-mentioned preferred range, it is easy to remove the native oxide film on the surface of the conductor and to provide hydroxyl groups to the surface of the conductor.

[0075] The treatment time for the pretreatment is not particularly limited, but is typically 10 seconds to 10 minutes, preferably 20 seconds to 5 minutes, and more preferably 30 seconds to 3 minutes. When the treatment temperature for the pretreatment is within the above-mentioned preferred range, it is easy to remove the native oxide film on the surface of the conductor and to provide hydroxyl groups to the surface of the conductor.

[0076] The water-repellent nature of the conductor surface can be confirmed by measuring the contact angle of water with the conductor surface. The contact angle of water with the conductor surface that has been rendered water-repellent by the method of this embodiment is greater than the contact angle of water with the conductor surface before the water-repellent nature. The contact angle of water with the conductor surface that has been rendered water-repellent 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 upper limit to the contact angle, but it is, for example, 140° or less, typically 130° or less.

[0077] The method for imparting water repellency to the surface of an electric conductor of this embodiment uses the water repellent agent for the surface of an electric conductor of the first aspect, and therefore can impart water repellency to the surface of the electric conductor satisfactorily.

[0078] <Third Aspect: Method for Selectively Making an Area Having a Conductive Surface Water-Repellent> A third aspect of the present invention is a method for selectively imparting water repellency to a region having a conductor surface on a substrate having a surface including two or more regions made of different materials, at least one of which has a conductor surface. The method of this aspect comprises exposing the surface of the substrate to the water repellent agent for conductor surfaces of the first aspect.

[0079] (substrate) The substrate selectively rendered water repellent by the method of this embodiment has a surface including two or more regions made of different materials. At least one of the two or more regions of the substrate has a conductive surface. The conductive surface is preferably a metal surface. Examples of the substrate include those similar to those described above.

[0080] The substrate surface to be treated includes two or more regions, at least one of which contains a conductor surface, and adjacent regions of the two or more regions may be made of different materials. In the method of this embodiment, the substrate surface to be treated is exposed to the water repellent agent for conductor surfaces of the first aspect, thereby selectively adsorbing compound (P1) to the region having the conductor surface. This makes it possible to make the contact angles of water with the surface of the two or more regions different from each other.

[0081] Among the two or more regions, an example of a region that tends to have a higher water contact angle (preferably a lower surface free energy) than the other region is a region containing at least one 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). Among these, it is preferable to contain at least one selected from the group consisting of tungsten, ruthenium, copper, and cobalt, and it is more preferable to contain at least one selected from the group consisting of tungsten and ruthenium. The region having a conductor surface may be a region composed of a conductor containing these.

[0082] Among the two or more regions, the region that tends to have a smaller water contact angle (preferably a higher surface free energy) than the other region may be a region containing at least one material selected from the group consisting of silicon (Si), silicon nitride (SiN), silicon oxide film (SiOx), germanium (Ge), silicon germanium (SiGe), tetraethoxysilane (TEOS), low-k material, and interlayer dielectric (ILD). The insulator region may be a region made of the insulating compound or a material containing these.

[0083] In the method of this embodiment, the surface of the substrate to be treated may include a first region having a conductive surface and a second region made of a different material from the first region and adjacent to the first region. In this case, the "adjacent regions" refer to the first region and the second region. The first area and the second area may or may not be divided into a plurality of areas.

[0084] Examples of the first region and the second region include an embodiment in which the surface of the substrate itself is the first region and the surface of an inorganic layer formed on the surface of the substrate is the second region, an embodiment in which the surface of a first inorganic layer formed on the surface of the substrate is the first region and the surface of a second inorganic layer formed on the surface of the substrate is the second region, etc. Embodiments in which an organic layer is formed instead of forming these inorganic layers can also be mentioned.

[0085] In a preferred embodiment where the surface of the substrate itself is the first region and the surface of an inorganic layer formed on the surface of the substrate is the second region, from the viewpoint of selectively improving the hydrophobicity and increasing the difference in water contact angle between two or more adjacent regions made of different materials on the substrate surface, the first region is the surface of at least one substrate selected from the group consisting of a Si substrate, a SiN substrate, a SiOx substrate, a Ge substrate, a SiGe substrate, TEOS, a low-k material, and an ILD, and the second region is the surface of an inorganic layer formed on the surface of the substrate and containing at least one material selected from the group consisting of TiN, TaN, W, Co, Al, Ni, Ru, and Cu.

[0086] In an embodiment in which the surface of a first inorganic layer formed on the surface of a substrate is the first region and the surface of a second inorganic layer formed on the surface of a substrate is the second region, from the viewpoint of selectively improving hydrophobicity between two or more adjacent regions made of different materials on the substrate surface and thereby improving the difference in water contact angle, a preferred embodiment is one in which the surface of a first inorganic layer formed on the surface of any substrate (e.g., a Si substrate) is the first region and the surface of a second inorganic layer formed on the surface of the substrate is the second region and includes at least one selected from the group consisting of SiN, SiOx, Ge, SiGe, TEOS, low-k material, and ILD.

[0087] <Substrate surface including three or more regions> When the substrate surface includes three or more regions, the substrate surface may include a first region containing a conductive surface, a second region made of a material different from that of the first region and adjacent to the first region, and a third region made of a material different from that of the second region and adjacent to the second region. In this case, the "adjacent regions" may be the first region and the second region (i.e., adjacent regions), or the first region and the third region (i.e., adjacent regions). When the first region and the third region are made of the same material (i.e., when both the first region and the third region contain a conductive surface), the "adjacent regions" are the first region and the second region, or the second region and the third region (i.e., adjacent regions). Each of the first area, the second area, and the third area may or may not be divided into a plurality of areas.

[0088] Examples of the first, second, and third regions include an embodiment in which the surface of the substrate itself is the first region, the surface of a first inorganic layer formed on the surface of the substrate is the second region, and the surface of a second inorganic layer formed on the surface of the substrate is the third region. Embodiments in which an organic layer is formed instead of these inorganic layers can also be mentioned. Embodiments in which both an inorganic layer and an organic layer are included, such as when only one of the second inorganic layer and the third inorganic layer is replaced with an organic layer, can also be mentioned. From the viewpoint of selectively improving the hydrophobicity between two or more adjacent regions made of different materials on the substrate surface and thereby improving the difference in water contact angle, a preferred embodiment is one in which the surface of any substrate (e.g., a Si substrate) itself is defined as the first region, the surface of a first inorganic layer formed on the surface of the substrate and containing at least one selected from the group consisting of SiN, SiOx, Ge, SiGe, TEOS, a low-k material, and an ILD is defined as the second region, and the surface of a second inorganic layer formed on the surface of the substrate and containing at least one selected from the group consisting of TiN, TaN, W, Co, Al, Ni, Ru, and Cu is defined as the third region. The same concept can be applied to the case where the substrate surface includes a fourth or more regions. There is no particular upper limit to the number of regions made of different materials as long as the effects of the present invention are not impaired. For example, it is 7 or less, or 6 or less, and typically 5 or less.

[0089] (Exposure process) The method for exposing the substrate surface to the water repellent agent for the surface of a conductor of the first embodiment is not particularly limited, and any known method can be used. Examples of the method for exposing the substrate surface to the water repellent agent for the surface of a conductor of the first embodiment include the same methods as those exemplified for the method of the second embodiment.

[0090] (Other processes) The method of this embodiment may include other steps in addition to the exposure step. Examples of such other steps include a pretreatment step. The pretreatment step is preferably a treatment capable of providing hydroxyl groups to the substrate surface. Examples of pretreatment methods include the same methods as those described in the second embodiment.

[0091] In the method of this embodiment, by exposing the water repellent agent for conductor surfaces of the first aspect to a substrate surface including two or more regions made of different materials, it is possible to selectively improve the hydrophobicity of the region having a conductor surface between the two or more regions. In the substrate on which the method of the present embodiment has been carried out, the contact angle of water with the surface of the region having a conductive surface 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 upper limit to the contact angle, but it is, for example, 140° or less, typically 130° or less. In a substrate on which the method of this embodiment has been performed, the water contact angle with respect to the surface of the insulator region is not as improved as that of the region having a conductor surface. Therefore, the difference in water contact angle between the region having a conductor surface and the insulator region is usually larger after the method of this embodiment has been performed than before. In a substrate on which the method of this embodiment has been performed, the difference in water contact angle between the region having a conductor surface and the insulator region is, for example, 10° or more, preferably 20° or more, more preferably 30° or more, and even more preferably 40° or more. The upper limit of the contact angle difference is not particularly limited as long as it does not impair the effects of the present invention, and is, for example, 80° or less or 70° or less, and typically 60° or less.

[0092] <Fourth Aspect: Surface Treatment Method> A fourth aspect of the present invention is a surface treatment method for a substrate having a surface including two or more regions made of different materials, at least one of which has a conductor surface. The method of this aspect comprises exposing the surface of the substrate to the water repellent agent for conductor surfaces of the first aspect.

[0093] (substrate) The substrates to be surface-treated by the method of this embodiment include the same substrates as those listed in the third embodiment. The conductive surface is preferably a metal surface.

[0094] (Exposure process) Examples of a method for exposing the water repellent agent for the surface of a conductor of the first embodiment to the surface of a substrate include the same methods as those mentioned in the method of the second embodiment.

[0095] (Other processes) The method of this embodiment may include other steps in addition to the exposure step. Examples of such other steps include a pretreatment step. The pretreatment step is preferably a treatment capable of providing hydroxyl groups to the substrate surface. Examples of pretreatment methods include the same methods as those described in the second embodiment.

[0096] <Fifth Aspect: Region-Selective Film Formation Method on Substrate Surface> A fifth aspect of the present invention is a method for region-selectively forming a film on a substrate surface. The method of this aspect includes treating the surface of the substrate by the surface treatment method of the fourth aspect, and forming a film on the surface-treated surface of the substrate by atomic layer deposition. In the method of this aspect, the deposition amount of the film-forming material by atomic layer deposition varies region-selectively.

[0097] (Surface treatment process) In the method of this embodiment, first, the surface of a substrate is treated by the surface treatment method of the fourth aspect. The substrate to be treated may be the same as the substrate exemplified in the third aspect.

[0098] By subjecting the substrate to surface treatment, the water repellency of the region having a conductive surface among the two or more regions can be selectively improved.

[0099] (ALD film formation process) Next, a film is formed on the surface of the surface-treated substrate by the ALD method. After the surface treatment, the water repellency of the region having a conductive surface among the two or more regions of the substrate surface is selectively improved. As a result, the deposition amount of the material forming the film can be selectively varied between the two or more regions of the substrate surface. The selective improvement in water repellency can be confirmed by measuring the contact angle of water with the surface of the region. Specifically, in the region having a conductive surface among the two or more regions, adsorption (preferably chemical adsorption) of the film-forming material by the ALD method becomes difficult. As a result, a difference occurs in the deposition amount of the film-forming material between the two or more regions. That is, the deposition amount of the film-forming material by the ALD method varies selectively between the regions. Specifically, the deposition amount of the film-forming material in the region having a conductive surface becomes lower than the deposition amount in the insulator region. The chemical adsorption of the film-forming material may be exemplified by chemical adsorption with hydroxyl groups provided on the substrate surface by pretreatment.

[0100] Among the two or more regions, the region that tends to have a larger water contact angle (preferably a smaller surface free energy) than the other region may be a region containing at least one selected from the group consisting of W, Co, Al, Ni, Ru, and Cu. The region having a conductive surface may be a region containing these elements. Among the two or more regions, the region that tends to have a smaller water contact angle (preferably a higher surface free energy) than the other region may be a region containing at least one material selected from the group consisting of Si, Al2O3, SiN, SiOx, Ge, SiGe, TEOS, a low-k material, and an ILD. The insulator region may be a region made of the insulating compound or a material containing these materials.

[0101] <Film formation using the ALD method> Although there are no particular limitations on the film formation method using the ALD method, it is preferable to use a thin film formation method that uses adsorption (preferably chemical adsorption) using at least two gas phase reactive substances (hereinafter simply referred to as "precursor gases"). Specifically, the method includes the following steps (a) and (b), which are repeated at least once (one cycle) until a desired film thickness is obtained. (a) exposing the surface-treated substrate to a pulse of a first precursor gas; and (b) after step (a), exposing the substrate to a pulse of a second precursor gas;

[0102] After the step (a) and before the step (b), a plasma treatment step, a step of removing or evacuating (purging) the first precursor gas and its reactants using a carrier gas, a second precursor gas, etc., may or may not be included. After the step (b), a plasma treatment step, a step of removing or purging the second precursor gas and its reactants with a carrier gas or the like, and the like may or may not be included. Examples of the carrier gas include inert gases such as nitrogen gas, argon gas, and helium gas.

[0103] Preferably, each pulse per cycle and each layer formed is self-limiting, and more preferably, each layer formed is a monolayer. The thickness of the monoatomic layer can be, for example, 5 nm or less, preferably 3 nm or less, more preferably 1 nm or less, and even more preferably 0.5 nm or less.

[0104] Examples of the first precursor gas include organic metals, metal halides, and metal oxide halides, and specific examples include tantalum pentaethoxide, tetrakis(dimethylamino)titanium, pentakis(dimethylamino)tantalum, tetrakis(dimethylamino)zirconium, tetrakis(dimethylamino)hafnium, tetrakis(dimethylamino)silane, copper hexafluoroacetylacetonate vinyltrimethylsilane, Zn(C2H5)2, Zn(CH3)2, TMA (trimethylaluminum), TaCl5, WF6, WOCl4, CuCl, ZrCl4, AlCl3, Al(CH3)3, TiCl4, SiCl4, and HfCl4.

[0105] The second precursor gas may be a precursor gas capable of decomposing the first precursor or removing the ligand of the first precursor, such as HO, HO, O, O, NH, HS, HSe, PH, AsH, CH, or SiH.

[0106] The exposure temperature in step (a) is not particularly limited, but is, for example, 100°C or higher and 800°C or lower, preferably 150°C or higher and 650°C or lower, more preferably 180°C or higher and 500°C or lower, and even more preferably 200°C or higher and 375°C or lower.

[0107] The exposure temperature in step (b) is not particularly limited, but may be a temperature substantially equal to or higher than the exposure temperature in step (a). Films formed by the ALD method are not particularly limited, and examples thereof include films containing pure elements (e.g., Si, Cu, Ta, W), films containing oxides (e.g., SiO2, GeO2, HfO2, ZrO2, Ta2O5, TiO2, Al2O3, ZnO, SnO2, Sb2O5, BO3, In2O3, WO3), films containing nitrides (e.g., Si3N4, TiN, AlN, BN, GaN, NbN), films containing carbides (e.g., SiC), films containing sulfides (e.g., CdS, ZnS, MnS, WS2, PbS), films containing selenides (e.g., CdSe, ZnSe), films containing phosphides (GaP, InP), films containing arsenides (e.g., GaAs, InAs), and mixtures thereof.

[0108] In the method of this embodiment, a film is formed by the ALD method on a substrate that has been surface-treated using the water repellent agent for conductor surfaces of the first aspect. The water repellency of the surface-treated substrate is selectively improved in the region having the conductor surface. Therefore, deposition of film-forming material by the ALD method is inhibited in the region having the conductor surface. As a result, the amount of film-forming material deposited by the ALD method is less in the region having the conductor surface than in the region having the insulator surface. This allows for region-selective film formation by the ALD method on the insulator region. The water repellent agent for the surface of a conductor according to the first aspect has high selectivity for the surface of a conductor, and therefore, by treating the surface of a substrate with the water repellent agent for the surface of a conductor according to the first aspect, it is possible to improve the selectivity of film formation for the insulator region in film formation by the ALD method. [Example]

[0109] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0110] (Preparation of water repellent agent for conductor surfaces) [Examples 1 to 2, Comparative Examples 1 to 3] The water repellent agents for conductor surfaces were prepared for each example shown in Table 1. The concentration of the compound in the water repellent agent for conductor surfaces was adjusted to 0.1 mass % relative to the total mass of the water repellent agent for conductor surfaces. The relative dielectric constant of toluene used as the organic solvent was 2.37.

[0111] [Table 1]

[0112] <Water-repellent treatment (1)> Using each example of the water repellent agent for the surface of a conductor, a water repellent treatment was carried out on a ruthenium substrate according to the following method.

[0113] Pretreatment The substrate was treated with ozone (O3) for 15 minutes. The substrate was then pretreated by immersing it in a 3.59% by mass H2O2 aqueous solution at room temperature for 1 minute. After the pretreatment, the substrate was washed with ion-exchanged distilled water for 1 minute. After washing, the substrate was dried using a nitrogen stream.

[0114] Water-repellent treatment The dried substrate was immersed in the water-repellent agent for conductor surfaces of each example at room temperature for 30 minutes to perform surface treatment. The water-repellent treated substrate was then washed with isopropanol for 1 minute, followed by washing with ion-exchanged distilled water for 1 minute. The washed substrate was then dried under a nitrogen stream to obtain a water-repellent treated substrate.

[0115] <Measurement of water contact angle (1)> The water contact angle of each substrate after the water-repellent treatment was measured. The contact angle of water was measured using a Dropmaster 700 (manufactured by Kyowa Interface Science Co., Ltd.). A pure water droplet (2.0 μL) was dropped onto the surface of the surface-treated substrate, and the contact angle 2 seconds after dropping was measured. The results are shown in Table 2.

[0116]

Table 2

[0117] From the results shown in Table 2, it was shown that the water repellents for the conductor surface in Example 1 and Example 2 had a higher water repellent effect compared to the water repellents for the conductor surface in Comparative Examples 1 to 3.

[0118] <ALD treatment (1)> Using the water repellent for the conductor surface in each example, the ruthenium substrate was subjected to water repellent treatment according to <Water repellent treatment (1)>. Next, an Al2O3 film was formed on the ruthenium substrate by 18 ALD cycle treatments under the following conditions. · Atomic layer deposition (ALD) apparatus: AT-410 (manufactured by Anric Technologies) · Chamber temperature: 150 °C · Precursors: Trimethylaluminum and H2O

[0119] <Measurement of Al2O膜 formation inhibition rate (1)> For the ruthenium substrate after the formation of the Al2O3 film, the Al2O3 film was measured using a fluorescence X-ray analysis (XRF) apparatus (ZSX Primus manufactured by Rigaku). The Al2O3 film formation inhibition rate was calculated by the following formula (1). The results are shown in Table 3. Al2O3 film formation inhibition rate (%) = (T0 - Tn) / T0 × 100 (1) Tn: Film thickness of the Al2O3 film when ALD treatment was performed after water repellent treatment. T0: Film thickness of the Al2O3 film when ALD treatment was performed without water repellent treatment.

[0120]

Table 3

[0121] From the results in Table 3, it was shown that the ruthenium surface treated with the water repellent for the conductor surface in Example 1 had a higher inhibition rate of Al2O3 film formation compared to the ruthenium surface treated with the water repellent for the conductor surface in the comparative example.

[0122] <Water repellent treatment (2)> Using the water repellent for the conductor surface of each example, the SiO2 substrate was subjected to water repellent treatment according to the following method.

[0123] · Pretreatment The substrate was subjected to ozone (O3) treatment for 15 minutes. Next, the substrate was immersed in an aqueous H2O2 solution with a concentration of 3.59% by mass at room temperature for 1 minute for pretreatment. After the above pretreatment, the substrate was washed with ion-exchanged distilled water for 1 minute. The washed substrate was dried by a nitrogen stream.

[0124] · Water repellent treatment The dried substrate was immersed in the water repellent for the conductor surface of each example at room temperature for 30 minutes for surface treatment of the substrate. After the water repellent treatment, the substrate was washed with isopropanol for 1 minute and then washed with ion-exchanged distilled water for 1 minute. The washed substrate was dried by a nitrogen stream to obtain a water repellent-treated substrate. <000s0572><00OO573><ALD treatment (2)> An Al2O3 film was formed on the water repellent-treated SiO2 substrate under the same conditions as in the above ALD treatment (1) except for the substrate.

[0126] <Measurement of inhibition rate of Al2O3 film formation (2)><0OO0578>For the SiO2 substrate after the formation of the Al2O3 film, the Al2O3 film was measured using a fluorescent X-ray analysis (XRF) apparatus (ZSX Primus manufactured by Rigaku Corporation). The inhibition rate of Al2O3 film formation was calculated by the above formula (1). The results are shown in Table 4.

[0127]

Table 4

[0128] From the results in Table 4, it was shown that the SiO2 surface treated with the water-repellent agent for the conductor surface in Example 1 had a lower inhibition rate of Al2O3 film formation compared to the SiO2 surfaces treated with the water-repellent agents for the conductor surfaces in Comparative Examples 1 and 2. From the results shown in Tables 3 and 4, it was shown that by performing water-repellent treatment with the water-repellent agent for the conductor surface in Example 1, the formation of the Al2O3 film can be selectively inhibited on the ruthenium surface.

[0129] (Preparation of water-repellent agent for conductor surface) [Examples 3 to 8] The water-repellent agents for the conductor surfaces of each example shown in Table 5 were prepared. The concentration of the compound in the water-repellent agent for the conductor surface was adjusted to be 0.1% by mass based on the total mass of the water-repellent agent for the conductor surface.

[0130]

Table 5

[0131] [[ID=二十一]] (Measurement of water contact angle) According to the above <Water-repellent treatment (1)>, the ruthenium substrate was subjected to water-repellent treatment. Then, according to the above <Measurement of water contact angle (1)>, the water contact angle was measured. The results are shown in Table 6.

[0132] (Measurement of Al2O3 film formation inhibition rate) According to the above <Water-repellent treatment (1)>, the ruthenium substrate was subjected to water-repellent treatment. Then, according to the above <ALD treatment (1)>, an Al2O3 film was formed on the ruthenium substrate. According to the above <Measurement of Al2O3 film formation inhibition rate (1)>, the film thickness of the Al2O3 film was measured, and the Al2O3 film formation inhibition rate was calculated. The results are shown in Table 6.

[0133]

Table 6

[0134] All of the ruthenium surfaces treated with the water repellent agents for electrical conductor surfaces of Examples 3 to 8 exhibited good water repellency. The results of the contact angle and inhibition rate suggested that a solvent with a low dielectric constant was preferable.

Claims

1. a compound (P1) containing an aromatic ring, an adsorptive group bonded to the aromatic ring and selected from the group consisting of an amino group, a phosphonic acid group, an acid anhydride group, and an acid chloride group, and a linear or branched alkyl group or a linear or branched fluorinated alkyl group bonded to the aromatic ring; Water repellent for conductive surfaces.

2. 2. The water repellent for a conductor surface according to claim 1, wherein the compound (P1) is a compound represented by the following general formula (P1-1): 【Chemistry 1】 [In the formula, R ０ represents a linear or branched alkyl group or a linear or branched fluorinated alkyl group; R １ represents an organic group (where R ０ A represents a group obtained by removing (n0+n1+nx) hydrogen atoms from a benzene ring, a group obtained by removing (n0+n1+nx) hydrogen atoms from a naphthalene ring, or a group obtained by removing (n0+n1+nx) hydrogen atoms from a biphenyl ring; X represents an adsorptive group selected from the group consisting of an amino group, a phosphonic acid group, an acid anhydride group, and an acid chloride group; n0 and nx each independently represent an integer of 1 or more; and n1 represents an integer of 0 or more. However, when A is a group obtained by removing (n0+n1+nx) hydrogen atoms from a benzene ring, n0+n1+nx≦6; when A is a group obtained by removing (n0+n1+nx) hydrogen atoms from a naphthalene ring, n0+n1+nx≦8; and when A is a group obtained by removing (n0+n1+nx) hydrogen atoms from a biphenyl ring, n0+n1+nx≦10. When n0 is 2 or more, multiple R ０ may be the same or different; when n1 is 2 or more, a plurality of R １ may be the same as or different from each other; when nx is 2 or more, the multiple Xs may be the same as or different from each other.

3. 2. The water repellent for a conductor surface according to claim 1, wherein the compound (P1) is a compound represented by the following general formula (P1-1-1): 【Chemistry 2】 [In the formula, R ０ represents a linear or branched alkyl group or a linear or branched fluorinated alkyl group; X represents an adsorptive group selected from the group consisting of an amino group, a phosphonic acid group, an acid anhydride group, and an acid chloride group; and n represents 0 or 1.

4. The water repellent for a conductor surface according to any one of claims 1 to 3, wherein the conductor surface contains at least one element selected from the group consisting of tungsten, ruthenium, copper, and cobalt.

5. The water repellent agent for a conductor surface according to any one of claims 1 to 4, which is used to treat a substrate having a surface including two or more regions made of different materials, at least one of the two or more regions having a conductor surface.

6. A method for making a surface of an electric conductor water-repellent, comprising exposing the surface of the electric conductor to the water-repellent agent for electric conductor surfaces according to any one of claims 1 to 5.

7. A method for selectively making a region having a conductive surface water-repellent on a substrate having a surface including two or more regions made of different materials, at least one of the two or more regions having a conductive surface, comprising: The surface of the substrate is exposed to the water repellent agent for a conductor surface according to any one of claims 1 to 5. method.

8. A surface treatment method for a substrate having a surface including two or more regions made of different materials, at least one of the two or more regions having a conductive surface, comprising: The surface is exposed to the water repellent agent for a conductor surface according to any one of claims 1 to 5. Surface treatment method.

9. treating the surface of the substrate by the surface treatment method according to claim 8; and forming a film on the surface of the surface-treated substrate by atomic layer deposition, wherein the deposition amount of the film-forming material by the atomic layer deposition method varies selectively in regions; A method for selectively depositing a film on a substrate surface.

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