Chemical solution, method for manufacturing modified substrate, method for manufacturing laminate

Abstract

The objective of this invention is to provide a semiconductor manufacturing solution that, when in contact with a substrate having a metal region, can form a film exhibiting a high water contact angle on the metal region. The semiconductor manufacturing solution of this invention comprises a solvent and two or more specific compounds, wherein the specific compounds are compounds having polar groups and vertically oriented groups.

Description

Technical Field

[0001] This invention relates to a pharmaceutical solution, a method for manufacturing a modified substrate, and a method for manufacturing a laminate. Prior Technology

[0002] As semiconductor devices become increasingly miniaturized, there is a growing demand for even finer and more precise devices. Photolithography has traditionally been used in semiconductor device fabrication, but its limitations in achieving the required precision, particularly in areas such as pattern alignment, have rendered it inadequate.

[0003] Therefore, as a method for forming semiconductor devices, a method has been studied in which a film composed of the aforementioned compound is selectively formed by selectively adsorbing a compound onto a region formed of a specific material, and the film is used to process regions other than the specific material. For example, Patent Document 1 discloses a composition containing a corrosion inhibitor, which describes how the corrosion inhibitor forms an insoluble film on the surface of copper to prevent corrosion of the copper and remove other components.

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2016-040382

[0005] As described above, films formed on areas made of a specific material (e.g., metal areas) are required to exhibit a high water contact angle depending on the processing performed. The inventors studied films formed using the composition described in Patent Document 1 and found that the water contact angle of the formed films was not necessarily high, requiring further improvement. Summary of the Invention

[0006] Therefore, the objective of this invention is to provide a semiconductor manufacturing solution that, when in contact with a substrate having a metal region, can form a film exhibiting a high water contact angle on the metal region. Furthermore, the present invention also provides a method for manufacturing a modified substrate using the above-mentioned pharmaceutical solution and a method for manufacturing a laminate.

[0007] The inventors conducted in-depth research to solve the aforementioned problems, thus completing this invention. Specifically, they discovered that the above-mentioned issues can be resolved through the following structure.

[0008] [1] A semiconductor manufacturing solution comprising a solvent and two or more specific compounds, wherein The aforementioned specific compounds are compounds with polar groups and vertically aligned groups. [2] The medicinal solution as described in [1], wherein The aforementioned polar group is selected from one or more groups selected from the group consisting of nitrogen-containing groups, phosphate groups or their salts, phosphonic acid groups or their salts, sulfonic acid groups or their salts, carboxyl groups or their salts, thiol groups and hydroxyl groups. [3] The medicinal solution as described in [1] or [2], wherein The aforementioned pharmaceutical solution comprises: a first specific compound having a nitrogen-containing group as a polar group and a vertically aligned group as described above; and a second specific compound having a polar group other than a nitrogen-containing group and a vertically aligned group as described above. [4] The medicinal solution as described in [3], wherein The polar group of the second specific compound is a phosphonate group or its salt, a carboxyl group or its salt, or a thiol group. [5] The medicinal solution as described in [1] or [2], wherein The above-mentioned drug solution contains two or more third specific compounds, having the above-mentioned polar groups and the above-mentioned vertical alignment groups selected from the group consisting of nitrogen-containing groups, phosphonic acid groups or their salts, carboxyl groups or their salts, and thiol groups, wherein the above-mentioned polar groups are the same in the two or more above-mentioned third specific compounds. [6] A semiconductor manufacturing solution comprising a solvent and two or more specific compounds, wherein The aforementioned specific compounds have polar groups and specific groups selected from the group consisting of hydrocarbon groups and polyoxyalkylene groups that may have halogen atoms. [7] The medicinal solution as described in [6], wherein The aforementioned polar group is selected from one or more groups selected from the group consisting of nitrogen-containing groups, phosphate groups or their salts, phosphonic acid groups or their salts, sulfonic acid groups or their salts, carboxyl groups or their salts, thiol groups and hydroxyl groups. [8] The medicinal solution as described in [6] or [7], wherein The aforementioned liquid comprises: a fourth specific compound having a nitrogen-containing group as a polar group and the aforementioned specific group; and a fifth specific compound having the aforementioned polar group other than a nitrogen-containing group and the aforementioned specific group. [9] The medicinal solution as described in [8], wherein The polar group of the aforementioned fifth specific compound is a phosphonate group or its salt, a carboxyl group or its salt, or a thiol group.

[10] The medicinal solution as described in [6] or [7], wherein The above-mentioned liquid contains two or more sixth specific compounds, having the polar groups and the specific groups selected from the group consisting of nitrogen-containing groups, phosphonic acid groups or their salts, carboxyl groups or their salts, and thiol groups, wherein the polar groups are the same in the two or more sixth specific compounds.

[11] The liquid medicine as described in any one of [1] to

[10] , wherein One or more of the above-mentioned specific compounds have a molecular weight of 600 or less.

[12] The solution described in any one of [1] to

[11] is used for the treatment of a substrate having a metal region.

[13] The medicinal solution as described in

[12] , wherein The aforementioned metallic region contains tungsten or ruthenium.

[14] The liquid medicine described in any one of [1] to

[13] is used to form a film containing two or more of the above-mentioned specific compounds only on the metal region described above.

[15] The liquid medicine described in any one of [1] to

[14] is used to form a film containing two or more of the above-mentioned specific compounds that function as a mask when forming a film on the substrate by chemical vapor deposition.

[16] A method for manufacturing a modified substrate, comprising the step of contacting a substrate having a metal region with a liquid medicine described in any one of [1] to

[15] to form a film containing two or more specific compounds on the metal region to obtain a modified substrate.

[17] The method for manufacturing the modified substrate as described in

[16] , wherein The above steps are steps to obtain a modified substrate containing a film, wherein the film contains two or more specific compounds formed on the metal region by contacting the above-mentioned liquid medicine with the above-mentioned substrate, heating the above-mentioned substrate in contact with the above-mentioned liquid medicine, and performing a rinsing treatment on the heated above-mentioned substrate.

[18] A method for manufacturing a multilayer, further comprising the steps of performing atomic layer deposition on a modified substrate manufactured by the method described in

[16] or

[17] , and forming a metal film or metal oxide film on a region other than the metal region.

[19] The method for manufacturing a laminate as described in

[18] further includes a step of removing a film containing two or more of the specific compounds formed on the metal region. [Invention Effects]

[0009] According to the present invention, a semiconductor manufacturing solution can be provided, which, when in contact with a substrate having a metal region, can form a film exhibiting a high water contact angle on the metal region. Furthermore, according to the present invention, a method for manufacturing a modified substrate using the above-mentioned pharmaceutical solution and a method for manufacturing a laminate can also be provided. Implementation

[0010] The present invention will now be described in detail. The following description of the constituent elements is sometimes based on a representative embodiment of the present invention, but the present invention is not limited to that embodiment.

[0011] The following explains the meaning of each statement in this specification. In this specification, the numerical range represented by "~" refers to the range including the values ​​before and after "~" as the lower and upper limits. In this specification, unless otherwise specified, the bonding direction of the divalent group (e.g., -COO-) can be either "XO-CO-Z" or "X-CO-OZ" if Y in the compound represented by "XYZ" is -COO-.

[0012] The semiconductor manufacturing solution of the present invention (hereinafter also simply referred to as "solution") comprises a solvent and two or more specific compounds. In a first embodiment of the pharmaceutical solution, the specific compound includes a compound having a polar group and a vertically aligned group (hereinafter also referred to as "Compound 1"). In a second embodiment of the pharmaceutical solution, the specific compound includes a compound having a polar group and a specific group selected from the group consisting of hydrocarbon groups and polyoxyalkylene groups that may have halogen atoms (hereinafter also referred to as "Compound 2"). When the liquid of the present invention (first embodiment and second embodiment) comes into contact with a substrate having a metal region, the mechanism by which a film exhibiting a high water contact angle can be formed on the metal region is not yet clear, but the inventors speculate as follows. Because the solution of the present invention contains specific compounds, and these specific compounds have polar groups, the polar groups of the specific compounds readily adsorb onto the surface of the metal regions when in contact with a substrate having metal regions. Furthermore, because the specific compounds have vertically oriented groups or specific groups, the specific compounds are arranged substantially perpendicularly to the surface of the metal regions, and a dense film containing the specific compounds is easily formed. Moreover, it is believed that the solution of the present invention, by containing two or more specific compounds, readily forms an even denser film containing the specific compounds. In the film containing the formed specific compounds, because the polar groups of the specific compounds readily align towards the surface side of the metal regions, and a dense film is formed, as a result, a film exhibiting a high water contact angle can be formed on the metal regions.

[0013] The following describes the components that can be included in each embodiment of the pharmaceutical solution of the present invention. In addition, when in contact with a substrate having a metal region, the film formed on the metal region that displays a high water contact angle is also called a "high contact angle film". When the water contact angle of the high contact angle film is even larger, it is also simply referred to as "larger contact angle".

[0014] <First Implementation Form of the Liquid> The first embodiment of the pharmaceutical solution of the present invention comprises a solvent and two or more specific compounds. Furthermore, as mentioned above, the specific compound is compound 1.

[0015] [solvent] The first embodiment of the pharmaceutical solution of the present invention includes a solvent. However, even if it is a solvent, it is not included in the case of a specific compound described in detail later. Examples of solvents include water and organic solvents. Examples of organic solvents include hydrocarbon solvents, alcohol solvents, polyol solvents, glycol ether solvents, ether solvents, ketone solvents, amide solvents, sulfur-containing solvents, and ester solvents.

[0016] Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents such as n-pentane and n-hexane; alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane; and aromatic hydrocarbon solvents such as toluene and xylene.

[0017] Examples of alcohol solvents include, for example, aliphatic alcohols with 1 to 18 carbon atoms such as methanol, ethanol, 1-propanol, 2-propanol (also known as isopropanol (IPA)), 2-butanol, isobutanol, tributanol, isoamyl alcohol, and 4-methyl-2-pentanol (also known as methyl isobutyl methanol (MIBC)); alicyclic alcohols with 3 to 18 carbon atoms such as cyclohexanol; aromatic alcohols such as benzyl alcohol; and ketols such as diacetone alcohol. For alcohol-based solvents, a carbon number of 1 to 8 is preferred, 2 to 7 is even better, and 3 to 6 is further preferred.

[0018] Examples of polyol solvents include ethylene glycol solvents with 2 to 18 carbon atoms. Examples of ethylene glycol-based solvents include ethylene glycol, propylene glycol (1,2-propanediol), 1,3-propanediol, diethylene glycol, and dipropylene glycol.

[0019] Examples of glycol ether solvents include ethylene glycol monoether solvents with 3 to 19 carbon atoms. Examples of ethylene glycol monoether solvents include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol, 2-ethoxy-1-propanol, propylene glycol monomethyl ether, propylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobenzyl ether, and diethylene glycol monobenzyl ether. The number of carbon atoms in glycol ether solvents is preferably 2 to 8, more preferably 2 to 7, and even more preferably 3 to 6.

[0020] Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

[0021] Examples of ether solvents include diethyl ether, diisopropyl ether, dibutyl ether, tributyl methyl ether, cyclohexyl methyl ether, and tetrahydrofuran.

[0022] Examples of acetamide solvents include methylamine, monomethylmethylamine, dimethylmethylamine, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide, and N-methylpyrrolidone.

[0023] Examples of sulfur-containing solvents include dimethyl sulfide, dimethyl sulfide, and cyclobutane.

[0024] Examples of ester solvents include n-butyl acetate, ethyl lactate, propylene glycol acetate, propylene glycol monomethyl ether acetate, γ-butyrolactone, and δ-valerolactone.

[0025] Among them, organic solvents are preferred, and alcohol-based solvents are even better.

[0026] In the first embodiment of the pharmaceutical solution, the solvent content in the pharmaceutical solution is preferably 90-99.9% by mass relative to the total mass of the pharmaceutical solution, more preferably 95-99.9% by mass, and further preferably 97-99.5% by mass. Two or more solvents can also be used together. When using two or more solvents, it is preferable that the total content is within the above range.

[0027] [Specific compound] The first embodiment of the pharmaceutical solution of the present invention comprises two or more specific compounds. Compound 1 is an example of a specific compound. A drug solution containing two or more specific compounds refers to a drug solution containing two or more specific compounds with different structures. Different structures mean that the two specific compounds have different structures. For example, the two specific compounds may have different types of polar groups or different types of perpendicularly aligned groups. The following section explains polar groups and vertically aligned groups.

[0028] (Polar group) The polar groups in a specific compound refer to groups that produce polarization, and groups that interact with the atoms on the surface of the metal region are preferred. From the viewpoint of being able to interact with the atoms on the surface of the metal region, it is preferable that the polar group is selected from one or more groups including nitrogen-containing groups, phosphate groups (-PO4H2) or their salts, phosphonic acid groups (-PO3H2) or their salts, sulfonic acid groups (-SO3H) or their salts, carboxyl groups (-COOH) or their salts, thiol groups (-SH) and hydroxyl groups (-OH).

[0029] Examples of nitrogen-containing groups include primary amino groups (-NH2), secondary amino groups (-NRTH), tertiary amino groups (-NRT2), and quaternary ammonium groups (-N+RT3). Furthermore, RT represents an alkyl group having 1 to 3 carbon atoms, and multiple RT groups can be different from each other. Moreover, multiple RT groups can bond together to form a ring. The formed ring is a ring containing a nitrogen atom; examples include pyrrolidine rings, piperidine rings, and piperidine rings. Furthermore, the nitrogen-containing group can be a nitrogen-containing heteroaryl group, which can be monocyclic or polycyclic. Examples of nitrogen-containing heteroaryl groups include pyridyl, triazolyl, pyrroleyl, pyrazolyl, imidazoleyl, pyrazolyl, triazolyl, benzimidazoleyl, and benzotriazolyl.

[0030] The salts of phosphate groups refer to the group represented by -PO42-Ctn+2 / n. Furthermore, Ctn+ indicates an n-valent cation, where n represents 1 or 2. Examples of monovalent cations include Li+, Na+, K+, and NH4+. When Ctn+ represents a monovalent cation, there are 2 of them. Examples of divalent cations include Mg+ and Ca+. When Ctn+ represents a divalent cation, there is 1 of them. In addition, compounds containing phosphoric acid groups are also simply referred to as "phosphoric acid compounds," and as a functional group name, they are also called "-phosphoric acid."

[0031] Phosphonic acid salts refer to the group represented by -PO32-Ctn+2 / n. Ctn+ indicates an n-valent cation, where n represents 1 or 2. The same cations as those described in the above-mentioned phosphate salts can be listed as both monovalent and divalent cations, and the number of each cation is also the same. In addition, compounds containing phosphonic acid groups are also called "phosphonic acid compounds".

[0032] Salts of sulfonic acid groups represent the group represented by -SO3-Ct+. Ct+ represents a monovalent cation, and examples can be made of the same monovalent cations described in the salts of phosphate groups above.

[0033] Salts of carboxyl groups are represented by the group represented by -COO-Ct+. Ct+ represents a monovalent cation, and examples can be made of the same monovalent cations described in the salts of phosphate groups above.

[0034] From the viewpoint of having a larger contact angle, it is preferable that the polar group is selected from one or more groups selected from the group consisting of primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium groups, phosphate groups, phosphonic acid groups, sulfonic acid groups, carboxyl groups, thiol groups and hydroxyl groups; it is even more preferable that the polar group is selected from one or more groups selected from the group consisting of primary amino groups, phosphonic acid groups, carboxyl groups, thiol groups and hydroxyl groups; and it is even more preferable that the polar group is selected from one or more groups selected from the group consisting of primary amino groups, phosphonic acid groups, carboxyl groups and thiol groups.

[0035] It is preferred that a particular compound has 1 to 4 polar groups, 1 or 2 is more preferred, and 1 is even more preferred. As will be described later, in the case that the polar groups of a particular compound are vertically aligned groups with a straight-chain structure, it is preferable that they are bonded to the end of the straight-chain structure.

[0036] (Vertical alignment group) The vertically oriented groups of a specific compound refer to the following groups: when a liquid containing the specific compound is brought into contact with a substrate having a metal region to form a film containing the specific compound on the metal region, the specific compound itself is oriented vertically relative to the surface of the metal region.

[0037] There are no particular restrictions on the vertical alignment group, but it is preferred to select groups from the group that can have halogen atoms, including hydrocarbon groups and polyoxyalkylene groups (hereinafter also referred to as "specific groups"). As a hydrocarbon group, aliphatic hydrocarbon groups are preferred, and alkyl groups are preferred. There are no particular restrictions on the number of carbon atoms in the hydrocarbon group, but 3 to 20 is preferred, 6 to 20 is even better, and 10 to 18 is even more preferred. Hydrocarbon groups can contain halogen atoms. When hydrocarbon groups contain halogen atoms, there is no particular limitation on the number of halogen atoms, but 1 to 10 is preferred, and 1 to 5 is even better. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. It is preferable that the hydrocarbon group is linear. For example, n-butyl and 3-chloro-n-butyl are linear, while isobutyl is not.

[0038] Polyoxyalkylene groups are groups having a plurality of oxyalkylene groups, such as polyoxyethylene and polyoxypropylene. There is no particular limitation on the number of repeating units of the oxidized alkenyl group in the polyoxyalkylene group, but 2 to 20 is preferred, and 3 to 10 is even better.

[0039] As a specific compound included in the first embodiment of the liquid, the compound represented by formula (A) is preferred. Formula (A) Xa-Ya In formula (A), Xa represents a polar group, and Ya represents a hydrocarbon group that may have halogen atoms or a group containing polyoxyalkylene groups. The hydrocarbon group that may have the above-mentioned halogen atoms and the group containing polyoxyalkylene groups represented by Ya are vertically aligned groups. The polar group represented by Xa is as described above. The hydrocarbon group represented by Ya that can have halogen atoms is as described above. As for the hydrocarbon group represented by Ya, it is preferable to have an alkyl group that can have halogen atoms, and it is even more preferable to have a straight-chain alkyl group that can have halogen atoms. The group represented by Ya that contains a polyoxyalkylene group is a group that includes the aforementioned polyoxyalkylene group. As a group containing a polyoxyalkylene group, the group represented by formula (B) is preferred. Equation (B) -L-(R1-O)n-R2 L represents a single bond or a divalent linker. Examples of divalent linkers include hydrocarbon groups (e.g., alkyl, aryl), -O-, -S-, -CO-, -SO2-, -N(R3)-, or combinations thereof. R3 represents a hydrogen atom or an alkyl group. R1 represents an enyl group. There is no particular limitation on the number of carbon atoms in the enyl group, but 1 to 5 is preferred, and 1 to 3 is even better. n represents an integer greater than 2, with 2 to 20 being preferred and 3 to 10 being even better. R2 represents a hydrogen atom or an alkyl group. There is no particular restriction on the number of carbon atoms in the alkyl group, but 1 to 20 is preferred.

[0040] It is preferable that the molecular weight of the specific compound contained in the first embodiment of the pharmaceutical solution is 1000 or less, more preferably 600 or less, and even more preferably 300 or less. It is preferable that the lower limit of the molecular weight is 60 or more. In addition, when the aforementioned specific compound contains repeating units, the aforementioned molecular weight refers to the weight average molecular weight. In the first embodiment of the pharmaceutical solution, it is preferable that at least one (preferably two or more) of the specific compounds is a specific compound within the aforementioned preferred molecular weight range (e.g., 600 or less or 300 or less). Alternatively, it is also preferable that all of the specific compounds included in the first embodiment of the pharmaceutical solution are specific compounds within the aforementioned preferred molecular weight range.

[0041] As described above, the first embodiment of the liquid contains two or more specific compounds. From the viewpoint of a larger contact angle, it is preferable to satisfy either requirement 1 or requirement 2. Requirement 1: It includes a first specific compound having a nitrogen-containing group and a vertically aligned group as polar groups, and a second specific compound having polar groups and vertically aligned groups other than nitrogen-containing groups. Requirement 2: It comprises two or more third specific compounds, having polar groups and vertically aligned groups selected from the group consisting of nitrogen-containing groups, phosphonic acid groups or their salts, carboxyl groups or their salts, and thiol groups, wherein the polar groups are identical in the two or more third specific compounds.

[0042] In requirement 1, the compound represented by formula (1) is preferred as the first specific compound. Equation (1) X1-Y1 X1 represents a nitrogen-containing group, and Y1 represents a hydrocarbon group that may have halogen atoms or a group containing polyoxyalkylene groups. The nitrogen-containing group represented by X1 is a polar group, and the hydrocarbon group that may have halogen atoms and the group containing polyoxyalkylene groups represented by Y1 are vertically aligned groups. The nitrogen-containing group represented by X1 is as described above. The meanings of the hydrocarbon groups that can have halogen atoms and the groups containing polyoxyalkylene groups represented by Y1 are the same as those of the hydrocarbon groups that can have halogen atoms and the groups containing polyoxyalkylene groups represented by Ya. As the second specific compound, the compound represented by formula (2) is preferred. Equation (2) X2-Y2 X2 represents a polar group other than a nitrogen group, and Y2 represents a hydrocarbon group that can have a halogen atom or a group containing a polyoxyalkylene group. The hydrocarbon group that can have the above-mentioned halogen atom and the group containing a polyoxyalkylene group represented by Y2 are vertically aligned groups. As a polar group other than the nitrogen-containing group represented by X2, it is a group other than the nitrogen-containing group exemplified by the above polar groups. For example, phosphate group or its salt, phosphonic acid group or its salt, sulfonic acid group or its salt, carboxyl group or its salt, thiol group and hydroxyl group can be mentioned. The meanings of Y2, which can represent hydrocarbon groups with halogen atoms and groups containing polyoxyalkylene groups, are the same as those of Ya, which can represent hydrocarbon groups with halogen atoms and groups containing polyoxyalkylene groups.

[0043] In the case where the first specific compound is the compound represented by formula (1) and the second specific compound is the compound represented by formula (2), Y1 and Y2 may be different or the same. In cases where Y1 and Y2 are different, both can be hydrocarbon groups that have halogen atoms, and it is preferable that the difference in the number of carbon atoms in the hydrocarbon groups of the two is 6 or more.

[0044] If condition 1 above is satisfied, it is preferable that the polar group of the second specific compound is a phosphonic acid group or its salt, a carboxyl group or its salt, or a thiol group, with carboxyl, phosphonic acid group, or thiol group being more preferred. In requirement 1, the ratio of the content of the first specific compound to the total content of the specific compounds is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass. In requirement 1, the ratio of the content of the second specific compound to the total content of the specific compounds is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass.

[0045] In requirement 2, it is preferable that the third specific compound includes the third specific compound A represented by formula (3A) and the third specific compound B represented by formula (3B). Formula (3A) X3A-Y3A X3A represents a polar group selected from the group consisting of nitrogen-containing groups, phosphonic acid groups or their salts, carboxyl groups or their salts, and thiol groups. Y3A represents a hydrocarbon group that may have a halogen atom or a group containing a polyoxyalkylene group. The nitrogen-containing group represented by X3A is as described above. The hydrocarbon group that may have the above-mentioned halogen atom and the group containing a polyoxyalkylene group represented by Y3A are vertically aligned groups. The meanings of Y3A, which can represent hydrocarbon groups with halogen atoms and groups containing polyoxyalkylene groups, are the same as those of Ya, which can represent hydrocarbon groups with halogen atoms and groups containing polyoxyalkylene groups. Formula (3B) X3B-Y3B X3B represents a polar group selected from the group consisting of nitrogen-containing groups, phosphonic acid groups or their salts, carboxyl groups or their salts, and thiol groups. Y3B represents a hydrocarbon group that may have a halogen atom or a group containing a polyoxyalkylene group. The nitrogen-containing group represented by X3B is as described above. The hydrocarbon group that may have the above-mentioned halogen atom and the group containing a polyoxyalkylene group represented by Y3B are vertically aligned groups. The meanings of Y3B, which can represent hydrocarbon groups with halogen atoms and groups containing polyoxyalkylene groups, are the same as those of Ya, which can represent hydrocarbon groups with halogen atoms and groups containing polyoxyalkylene groups.

[0046] If condition 2 above is met, the polar groups of the third specific compound are the same. That is, if the third specific compound A represented by formula (3A) and the third specific compound B represented by formula (3B) are included, X3A and X3B are the same, and Y3A and Y3B are different. In cases where Y3A and Y3B are different, both can have hydrocarbon groups containing halogen atoms, and it is preferable that the difference in the number of carbon atoms in their hydrocarbon groups is 6 or more.

[0047] In requirement 2, the ratio of the content of the third specific compound A to the total content of the specific compounds is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass. In requirement 2, the ratio of the content of the third specific compound B to the total content of the specific compounds is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass. Furthermore, if the number of carbons in the vertically aligned group of the third specific compound A (preferably the number of carbons in the hydrocarbon group that may have halogen atoms, represented by Y3A in formula (3A)) is greater than the number of carbons in the vertically aligned group of the third specific compound B (preferably the number of carbons in the hydrocarbon group that may have halogen atoms, represented by Y3B in formula (3B)), then the ratio of the content of the third specific compound A to the total content of the specific compounds is preferably 10 to 30% by mass.

[0048] In the first embodiment of the pharmaceutical solution, the content of the specific compound relative to the total mass of the pharmaceutical solution is preferably 0.01 to 10.0% by mass, more preferably 0.1 to 5.0% by mass, and even more preferably 0.5 to 3.0% by mass.

[0049] (Other ingredients) The first embodiment of the liquid may contain other components besides those mentioned above. Other components include polymers. Among polymers, acrylic polymers, silicone polymers, and styrene polymers are examples. As a specific example of a polymer, one can cite the polymer described in paragraphs

[0150] to

[0171] of Japanese Patent Application Publication No. 2021-041364.

[0050] <Second Embodiment of the Liquid> The second embodiment of the pharmaceutical solution of the present invention comprises a solvent and two or more specific compounds. Furthermore, as mentioned above, the specific compound is compound 2. Since the solvent in the second embodiment of the liquid is the same as the solvent in the first embodiment of the liquid, the description is omitted.

[0051] [Specific compound] The second embodiment of the pharmaceutical solution of the present invention comprises two or more specific compounds. Compound 2 is an example of a specific compound. A drug solution containing two or more specific compounds refers to a drug solution containing two or more specific compounds with different structures. Different structures mean that the two specific compounds have different structures. For example, the two specific compounds may have different types of polar groups or different types of specific groups. The types of polar groups in the specific compound included in the second embodiment of the pharmaceutical solution are the same as those in the specific compound included in the first embodiment of the pharmaceutical solution, therefore, the description is omitted.

[0052] The specific compound contained in the second embodiment of the liquid has a specific group selected from the group consisting of hydrocarbon groups and polyoxyalkylene groups that may have halogen atoms. Since the definition and preferred state of a hydrocarbon group that can have halogen atoms are the same as the definition and preferred state of a hydrocarbon group that can have halogen atoms, which is an example of a vertically aligned group in the above-mentioned specific compound, the description is omitted. Since the definition and preferred state of polyoxyalkylene groups are the same as those of polyoxyalkylene groups, which are examples of vertically oriented groups in the aforementioned specific compounds, the description is omitted.

[0053] As a specific compound included in the second embodiment of the liquid, the compound represented by formula (C) is preferred. Formula (C) Xc-Yc Xc represents a polar group, and Yc represents a hydrocarbon group that may have halogen atoms or a group containing polyoxyalkylene groups. The polar group represented by Xc is as described above. The hydrocarbon group represented by Yc that can have halogen atoms is as described above. Since the definition and preferred state of the polyoxyalkylene group represented by Yc are the same as those of the polyoxyalkylene group represented by Ya, the explanation is omitted.

[0054] In the second embodiment of the pharmaceutical solution, it is preferable that the molecular weight of the specific compound contained therein is 1000 or less, more preferably 600 or less, and further preferably 300 or less. A lower molecular weight of 60 or more is preferred. In addition, when the aforementioned specific compound contains repeating units, the aforementioned molecular weight refers to the weight average molecular weight. In the second embodiment of the pharmaceutical solution, it is preferable that at least one (preferably two or more) of the specific compounds are within the aforementioned preferred molecular weight range (e.g., 600 or less or 300 or less). Alternatively, it is also preferable that all the specific compounds included in the second embodiment of the pharmaceutical solution are within the aforementioned preferred molecular weight range.

[0055] As described above, the second embodiment of the liquid contains two or more specific compounds. From the viewpoint of a larger contact angle, it is preferable to satisfy either requirement 3 or requirement 4. Requirement 3: Includes a fourth specific compound having a nitrogen-containing group and a specific group as polar groups, and a fifth specific compound having polar groups and specific groups other than nitrogen-containing groups. Requirement 4: It comprises two or more sixth specific compounds, having polar groups and specific groups selected from the group consisting of nitrogen-containing groups, phosphonic acid groups or their salts, carboxyl groups or their salts, and thiol groups, wherein the polar groups are the same in the two or more sixth specific compounds.

[0056] In requirement 3, the compound represented by formula (4) is preferred as the fourth specific compound. Equation (4) X4-Y4 X4 represents a nitrogen-containing group, and Y4 represents a hydrocarbon group that can have halogen atoms or a group containing a polyoxyalkylene group. The nitrogen-containing group represented by X4 is as described above. The meanings of Y4, which can represent hydrocarbon groups with halogen atoms and groups containing polyoxyalkylene groups, are the same as those of Ya, which can represent hydrocarbon groups with halogen atoms and groups containing polyoxyalkylene groups. As the fifth specific compound, the compound represented by formula (5) is preferred. Equation (5) X5-Y5 X5 represents a polar group other than a nitrogen group, and Y5 represents a hydrocarbon group that may have a halogen atom or a group containing a polyoxyalkylene group. As a polar group other than the nitrogen-containing group represented by X5, it is a group other than the nitrogen-containing group exemplified by the above polar groups. For example, phosphate group or its salt, phosphonic acid group or its salt, sulfonic acid group or its salt, carboxyl group or its salt, thiol group and hydroxyl group can be mentioned. The meanings of Y5, which can represent hydrocarbon groups with halogen atoms and groups containing polyoxyalkylene groups, are the same as those of Ya, which can represent hydrocarbon groups with halogen atoms and groups containing polyoxyalkylene groups.

[0057] In the case where the fourth specific compound is the compound represented by formula (4) and the fifth specific compound is the compound represented by formula (5), Y4 and Y5 may be different or the same. In cases where Y4 and Y5 are different, both are hydrocarbon groups that can have halogen atoms, and it is preferable that the difference in the number of carbon atoms in the hydrocarbon groups of the two is 6 or more.

[0058] If condition 3 above is met, it is preferable that the polar group of the fifth specific compound is a phosphonic acid group or its salt, a carboxyl group or its salt, or a thiol group, with carboxyl, phosphonic acid group, or thiol group being more preferred. In requirement 3, the ratio of the content of the fourth specific compound to the total content of the specific compounds is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass. In requirement 3, the ratio of the content of the fifth specific compound to the total content of the specific compounds is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass.

[0059] In requirement 4, it is preferable that the sixth specific compound includes the sixth specific compound A represented by formula (6A) and the sixth specific compound B represented by formula (6B). Formula (6A) X6A-Y6A X6A represents a polar group selected from the group consisting of nitrogen-containing groups, phosphonic acid groups or their salts, carboxyl groups or their salts, and thiol groups. Y6A represents a hydrocarbon group that may have a halogen atom or a group containing a polyoxyalkylene group. The nitrogen-containing group represented by X6A is as described above. The hydrocarbon group that may have the above-mentioned halogen atom and the group containing a polyoxyalkylene group represented by Y6A are specific groups. The meanings of Y6A, which represents hydrocarbon groups that can have halogen atoms and groups containing polyoxyalkylene groups, are the same as those of Ya, which represents hydrocarbon groups that can have halogen atoms and groups containing polyoxyalkylene groups. Formula (6B) X6B-Y6B X6B represents a polar group selected from the group consisting of nitrogen-containing groups, phosphonic acid groups or their salts, carboxyl groups or their salts, and thiol groups. Y6B represents a hydrocarbon group that may have a halogen atom or a group containing a polyoxyalkylene group. The nitrogen-containing group represented by X6A is as described above. The hydrocarbon group that may have the above-mentioned halogen atom and the group containing a polyoxyalkylene group represented by Y6B are specific groups. The meanings of Y6B, which can represent hydrocarbon groups with halogen atoms and groups containing polyoxyalkylene groups, are the same as those of Ya, which can represent hydrocarbon groups with halogen atoms and groups containing polyoxyalkylene groups.

[0060] When condition 4 above is met, the polar groups of the sixth specific compound are the same. That is, when the sixth specific compound A represented by formula (6A) and the sixth specific compound B represented by formula (6B) are included, X6A and X6B are the same, and Y6A and Y6B are different. In cases where Y6A and Y6B are different, both can have hydrocarbon groups containing halogen atoms, and it is preferable that the difference in the number of carbon atoms in their hydrocarbon groups is 6 or more.

[0061] In requirement 4, the ratio of the content of the sixth specific compound A to the total content of the specific compounds is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass. In requirement 4, the ratio of the content of the sixth specific compound B to the total content of the specific compounds is preferably 10-90% by mass, and more preferably 20-80% by mass. Furthermore, if the number of carbons in the specific group of the sixth specific compound A (preferably the number of carbons in the hydrocarbon group that may have halogen atoms, represented by Y6A in formula (6A)) is greater than the number of carbons in the specific group of the sixth specific compound B (preferably the number of carbons in the hydrocarbon group that may have halogen atoms, represented by Y6B in formula (6B)), then the ratio of the content of the sixth specific compound A to the total content of the specific compounds is preferably 10 to 30% by mass.

[0062] In the second embodiment of the pharmaceutical solution, the content of the specific compound relative to the total mass of the pharmaceutical solution is preferably 0.01 to 10.0% by mass, more preferably 0.1 to 5.0% by mass, and even more preferably 0.5 to 3.0% by mass.

[0063] (Other ingredients) The second embodiment of the liquid may contain other components besides those mentioned above. Other components include polymers. Among polymers, acrylic polymers, silicone polymers, and styrene polymers are examples. As a specific example of a polymer, one can cite the polymer described in paragraphs

[0150] to

[0171] of Japanese Patent Application Publication No. 2021-041364.

[0064] <Method for Manufacturing the Liquid Medicine> The method for manufacturing the pharmaceutical solution (first embodiment and second embodiment) of the present invention is not particularly limited. For example, it can be manufactured by mixing the above-mentioned components. The order or timing of mixing the components, as well as the order and timing, are not particularly limited. For example, a method can be given in which two or more specific compounds are added to a mixer or other stirrer containing a refined solvent and then stirred thoroughly to manufacture the pharmaceutical solution. The steps described below can be performed in the manufacturing process of the pharmaceutical solution of the present invention.

[0065] [Metal Removal Steps] The above manufacturing method can include a metal removal step to remove metal components from the above-mentioned ingredients and / or pharmaceutical solutions (hereinafter also referred to as "refined products"). As a metal removal step, step P, in which the purified material is fed to an ion exchange process, can be cited as an example.

[0066] (Step P) In step P, the purified material is subjected to ion exchange. As for ion exchange methods, there are no particular limitations as long as they are methods capable of adjusting (reducing) the amount of metal components in the purified material. From the viewpoint of making the preparation of the solution easier, it is preferable that the ion exchange method includes one or more of the following methods P1 to P3. It is even more preferable that the ion exchange method includes two or more of the following methods P1 to P3, and it is further preferable that it includes all of the following methods P1 to P3. In addition, when the ion exchange method includes all of the following methods P1 to P3, there are no particular restrictions on the order of implementation, but it is preferable to implement them in the order of methods P1 to P3. Method P1: A method of passing the purified material through a first filling section filled with a mixed resin, wherein the mixed resin comprises two or more resins selected from the group consisting of cation exchange resins, anion exchange resins and chelating resins. Method P2: A method of passing the purified product through at least one of a second filling section filled with cation exchange resin, a third filling section filled with anion exchange resin, and a fourth filling section filled with chelating resin. Method P3: A method for passing the purified material through a membrane ion exchanger.

[0067] When the ion exchange resins (cation exchange resins, anion exchange resins), chelating resins, and membrane ion exchangers used in each method are in forms other than H+ or OH-, it is preferable to regenerate them into H+ or OH- forms before use. Furthermore, a space velocity (SV) of 0.01 to 20.0 (L / h) for the refined material in each method is preferred, and a SV of 0.1 to 10.0 (L / h) is even better. Furthermore, the processing temperature in each method is preferably 0~60℃, and even better if it is 10~50℃.

[0068] Furthermore, the forms of ion exchange resins and chelating resins include, for example, granular, fibrous, and porous monolithic forms, with granular or fibrous forms being preferred. The average particle size of ion exchange resins and chelating resins as particles is preferably 10~2000μm, and even more preferably 100~1000μm. For particulate ion exchange resins and chelating resins, a particle size distribution in which the presence rate of resin particles within a range of ±200 μm of average particle size is above 90% is preferred. Regarding the aforementioned average particle size and particle size distribution, for example, a method can be given that uses a particle size distribution measuring device (MICROTRAC HRA3920, manufactured by NIKKISO CO.,LTD.) to measure the particle size distribution using water as the dispersion medium.

[0069] [Filtering Steps] The above manufacturing method preferably includes a filtration step to remove foreign matter and coarse particles from the liquid. There are no particular restrictions on the filtering method; any well-known filtering method can be used. Among them, filtering using filters is preferred.

[0070] Filters used for filtration can be used without particular restrictions as long as they have been used for filtration purposes. Examples of materials that constitute filters include fluorinated resins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, polyolefin resins (including high-density and ultra-high molecular weight) such as polyethylene and polypropylene (PP), and polyarylates. Among these, polyamide resins, PTFE, polypropylene (including high-density polypropylene), and polyarylates are preferred. The critical surface tension of the filter is preferably above 70 mN / m as the lower limit and below 95 mN / m as the upper limit. In particular, the critical surface tension of the filter is preferably 75~85 mN / m. In addition, the value of critical surface tension is the nominal value of the manufacturer.

[0071] The pore size of the filter is preferably around 0.001~1.0μm, more preferably around 0.02~0.5μm, and even more preferably around 0.01~0.1μm. By setting the pore size of the filter within the above range, filter clogging can be suppressed, and fine foreign matter contained in the composition can be reliably removed.

[0072] When using filters, different filters can be combined. In this case, filtration based on the first filter can be performed only once, or it can be performed two or more times. When combining different filters for filtration two or more times, the filters can be of the same type or different types, but it is preferable that they are different types. Typically, it is preferable that at least one of the pore size and constituent materials of the first filter and the second filter are different. It is preferable that the pore size of subsequent filters is the same as or smaller than that of the first filtration. Alternatively, first filters with different pore sizes can be combined within the above range. The pore sizes mentioned here can be found in the filter manufacturer's specifications.

[0073] [Electrostatic removal procedure] The method for manufacturing the liquid medicine may further include a static removal step of removing static electricity from the liquid medicine.

[0074] [container] As a container for containing the liquid medicine, for example, a known container can be used. Regarding containers, semiconductor containers with high cleanliness and minimal leaching of impurities are preferred. For example, examples of containers include the "clean bottle" series (manufactured by AICELLO CHEMICAL CO., LTD.) and the "pure bottle" (manufactured by KODAMA PLASTICS Co., Ltd.). Furthermore, from the perspective of preventing impurities from contaminating raw materials and pharmaceutical solutions, multi-layered containers with a 6-layer structure composed of 6 types of resin or a 7-layer structure composed of 7 types of resin are also preferable. As a multi-layered container, for example, the container described in Japanese Patent Application Publication No. 2015-123351 can be cited, the contents of which are incorporated into this specification. For example, materials used for the inner wall of a container can include at least one first resin selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, a second resin different from the first resin, and metals such as stainless steel, Herstal alloy, Ingalls alloy, and Monel alloy. Furthermore, it is preferable to use the aforementioned materials to form or coat the inner wall of the container.

[0075] As a second resin, fluoropolymer (perfluoropolymer) is preferred. When using fluoropolymers, the leaching of oligomers of ethylene or propylene can be suppressed. Examples of containers described above include the FluoroPure PFA composite drum (manufactured by Entegris, Inc.), page 4 of Japanese Patent Publication No. 3-502677, page 3 of International Publication No. 2004 / 016526, and pages 9 and 16 of International Publication No. 99 / 046309.

[0076] For the inner wall of a container, in addition to fluoropolymers, materials such as quartz and electrolytically polished metals are also preferred. The metal material used in the electrolytically polished metal material contains at least one element selected from the group consisting of chromium (Cr) and nickel (Ni), and it is preferable that the combined content of Cr and Ni is greater than 25% by mass relative to the total mass of the metal material. Examples include stainless steel and Ni-Cr alloys. The combined Cr and Ni content in the metallic material is preferably 25% by mass or more, and more preferably 30% by mass or more. The upper limit is preferably below 90% by mass relative to the total mass of the metallic material.

[0077] As for stainless steel, for example, well-known stainless steels can be cited. Among them, stainless steel containing more than 8% by mass of Ni is preferred, and stainless steel containing more than 8% by mass of Ni is even better.

[0078] As an example of a Ni-Cr alloy, well-known Ni-Cr alloys can be cited. Among them, Ni-Cr alloys with a Ni content of 40-75% by mass and a Cr content of 1-30% by mass are preferred. Ni-Cr alloys may further include boron, silicon, tungsten, molybdenum, copper, or cobalt, in addition to the aforementioned alloys, as needed.

[0079] As a method for electrolytic polishing of metallic materials, well-known methods can be cited, for example. Specifically, the methods described in paragraphs

[0011] to

[0014] of Japanese Patent Application Publication No. 2015-227501 and paragraphs

[0036] to

[0042] of Japanese Patent Application Publication No. 2008-264929 are cited, and their contents are incorporated into this specification.

[0080] Polishing is preferable for metallic materials. As a method of polishing, well-known methods can be cited, for example. Considering that the surface roughness of metallic materials is more easily minimized, it is preferable to use abrasive grains of #400 or smaller in fine polishing. Polishing is best performed before electrolytic polishing. Alternatively, one or more of the following processes can be combined to treat metal materials: polishing, pickling, and magnetic fluid grinding, which involve multiple stages of polishing, pickling, and magnetic fluid grinding by changing the size and coarseness of the abrasive grains.

[0081] Regarding the container, it is best to clean the inside of the container before filling it with the medicine. The liquid used for cleaning can be appropriately selected according to the purpose, and a liquid containing at least one of the ingredients added to the liquid is preferred.

[0082] From the viewpoint of preventing changes in the composition of the liquid medicine during storage, the container can be purged with an inert gas (e.g., nitrogen and argon) with a purity of 99.99995% by volume or higher. Gases with low water content are particularly preferable. Furthermore, the transport and storage of containers holding the liquid medicine can be carried out at either room temperature or a controlled temperature. From the viewpoint of preventing deterioration, controlling the temperature within the range of -20 to 20°C is preferable.

[0083] <Uses of the medicinal solution> The solution of the present invention is preferably used for treating substrates with metallic regions. As a substrate processing method, it is sufficient to bring the pharmaceutical solution of the present invention into contact with the substrate having a metal region. Through the above processing, a modified substrate with a film (high-contact cornea) formed on the substrate having a metal region can be obtained, the film containing two or more specific compounds contained in the pharmaceutical solution of the present invention. The manufacturing method of the modified substrate will be described later.

[0084] A substrate having metallic regions is a substrate having both metallic and other regions. Metallic regions refer to areas whose surface is composed of metal, while other regions refer to areas whose surface is composed of non-metallic materials. There are no particular limitations on the metal constituting the metallic regions, but transition metals are preferred, elements from groups 6 to 11 are more preferred, elements from groups 6, 8, 9, or 11 are further preferred, and ruthenium or tungsten are particularly preferred. The metal constituting the metallic regions can be an alloy containing the aforementioned metals. Insulators can be used as materials constituting the other regions; examples of insulators include oxides (e.g., metal oxides, metal nitrides, and SiO2). A substrate having the aforementioned metal regions is also preferred if it is a semiconductor substrate having metal regions.

[0085] It is preferable to form a high-contact cornea on a substrate with a metal region by means of the above treatment, and it is even better to form a high-contact cornea only on the metal region. The aforementioned high-contact cornea is preferably used as a mask when forming films on substrates with metallic regions using chemical vapor deposition (CVD). That is, in areas where a high-contact cornea is formed using the solution of this invention, it is less likely that a CVD-based film (hereinafter also referred to as a "CVD film") will be deposited; it is preferable to deposit the CVD film in areas where a high-contact cornea is not formed. When the high-contact cornea functions as a mask for CVD, a laminate in which CVD films are selectively formed in other areas of the substrate can be obtained. The method for manufacturing the laminate will be described later. From the perspective of high-contact corneas easily functioning as a shield for CVD, a contact angle of 60° or higher is preferred, 90° or higher is even better, and 105° or higher is further preferred. There is no particular upper limit, and in most cases it is below 120°.

[0086] <Manufacturing Method of Modified Substrate> The modified substrate containing the high-contact cornea is preferably manufactured by contacting the pharmaceutical solution of the present invention with a substrate having metallic regions. Furthermore, it is preferable that the high-contact cornea is formed only in the metallic regions. Additionally, it is preferable that the high-contact cornea functions as a mask for CVD. The modified substrate with these preferred characteristics is better suited for the manufacture of laminates.

[0087] There are no particular limitations on the contact method; examples include coating or spraying the solution onto a substrate with metallic areas and immersing the substrate with metallic areas in the solution. There are no particular limitations on the method of coating the solution onto the substrate; known methods can be used, such as spin coating. Furthermore, when immersing the substrate in the solution, convection of the solution can be achieved. There are no particular restrictions on the temperature during contact, but 10~50℃ is preferred.

[0088] Furthermore, it is preferable to heat the solution after it comes into contact with the substrate having metallic regions. Heating removes the solvent contained in the solution, resulting in a denser film containing the specific compound. The heating temperature is not particularly limited, but 50~300℃ is preferred, and 60~180℃ is even better. There are no particular limitations on the heating method; examples include methods involving contact with a heating element (e.g., heating based on a heating plate) and methods involving irradiation with infrared radiation.

[0089] Furthermore, rinsing the heated substrate is also preferable. This rinsing process removes specific compounds adhering to the substrate outside the desired area. There are no particular limitations on the rinsing method; for example, a method that brings the rinsing solution into contact with a heated substrate can be cited. As a contact method, a method similar to that used to bring the aforementioned solution into contact with a substrate having metallic regions can be cited. There are no particular limitations on the contact temperature, but 10–50°C is preferred. There are no particular limitations on the rinsing solution; examples include the solvents contained in the solution of the present invention. Solvents contained in the solution used for the formation of the aforementioned high-contact cornea can be used as rinsing solutions.

[0090] <Manufacturing Method of Laminated Materials> When the modified substrate described above is used for CVD processing, a laminate with a CVD film can be obtained in the area where a high contact cornea is not formed (the area other than the metal area). CVD processing can be carried out by known methods, but thermal CVD, plasma CVD, or atomic layer deposition (ALD) are preferred, with ALD being the best. In CVD processing, precursors that will become the raw materials for the CVD film are supplied to the surface of a modified substrate. The materials constituting the formed CVD film can be controlled by the type of precursor supplied, the supply environment, and the oxidant. There are no particular limitations on the materials used to form the CVD film; metals, metal oxides, and metal nitrides are examples. Examples of metals include aluminum, titanium, chromium, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, palladium, lanthanum, cerium, hafnium, tantalum, tungsten, platinum, and bismuth. Examples of metal oxides include aluminum oxide, titanium oxide, zinc oxide, zirconium oxide, hafnium oxide, and tantalum oxide. Examples of metal nitrides include titanium nitride and tantalum nitride. In CVD processing, a treatment can be performed to alter the surface of areas where high contact with the cornea has not formed.

[0091] When a CVD film is formed on an area where a high contact keratosis pilaris (HPT) zone is not formed, the ratio of the thickness of the CVD film on the HPT zone to the thickness of the CVD film on the area where no HPT zone is formed is preferably 0.75 or less, more preferably 0.5 or less, and further preferably 0.25 or less. The lower limit of the above ratio can be 0, or even 0. That is, a CVD film may not be formed on the HPT zone.

[0092] In the laminate obtained by the above method, high-contact cornea can be further removed. When the high-contact cornea is removed, a laminate with a CVD film can be obtained only in the area outside the metal region. There are no particular limitations on the methods for removing high-contact corneas; examples include dry etching, wet etching, and combinations thereof. As a dry etching method, one example is supplying reactive ions or reactive free radicals to the surface of a laminate with high contact corneal properties. The reactive ions or reactive free radicals can be generated by plasma or the like, and it is preferable to use a mixed gas containing one or more gases selected from the group consisting of oxygen, nitrogen, and hydrogen. The mixed gas may contain rare gases. Furthermore, dry etching can also be a physical etching method utilizing sputtering phenomena. In wet etching, the etching solution is simply supplied to the surface of the laminate with high contact with the cornea. Examples of etching solutions include those containing oxidants such as ozone and those containing organic solvents. Among the organic solvents in etching solutions containing organic solvents, those found in the aforementioned solutions are examples, with hydrocarbon-based solvents being preferred. [Example]

[0093] The present invention will now be described in further detail based on embodiments. The materials, quantities, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention should not be limited by the embodiments shown below.

[0094] <Preparation of the drug solution> The components were mixed in the proportions shown in the table below to prepare the solutions used in the examples and comparative examples. Furthermore, the preparation, filling, and storage of the pharmaceutical solution are all carried out in a cleanroom that meets ISO level 2 or lower. Also, the containers used in the preparation, filling, and storage of the pharmaceutical solution are cleaned with the solvent used in the preparation or the pharmaceutical solution itself.

[0095] <Evaluation Methods> Following the steps below, a film (high contact cornea) containing two or more specific compounds was formed on a substrate using the solutions from the examples and comparative examples, and the water contact angle of the film was evaluated. Furthermore, an oxide film formation process based on the ALD method was performed on the substrate on which the high contact cornea was formed, and the deposition selectivity was evaluated based on the thickness of the formed oxide film.

[0096] [Contact Angle Evaluation] First, as substrates, a W-layer wafer with a tungsten layer formed on one surface of a commercially available silicon wafer (12 inches in diameter) and a Ru-layer wafer with a ruthenium layer formed on one surface were prepared by CVD. The CVD processing time was adjusted so that the thickness of the tungsten and ruthenium layers was 20 nm.

[0097] The obtained W-layer and Ru-layer wafers were cut into 2cm squares and immersed in their respective solutions. While stirring the solutions poured into the container with a magnetic stirrer at 250 rpm, each wafer was immersed in the solution. The solution temperature was set to 25°C and the immersion time was set to 10 minutes. In addition, the above-mentioned impregnation was performed on the W-layer wafer after the following pretreatment. The W-layer wafer was immersed in a 1% (w / w) citric acid aqueous solution. While stirring the solution being poured into the container with a magnetic stirrer at 250 rpm, the wafer was immersed in the citric acid aqueous solution at a temperature of 25°C for 1 minute. After immersion, nitrogen gas was blown onto the W-layer wafer to dry it.

[0098] Next, each wafer immersed in the solution was subjected to heat treatment. A heating plate was used for the heat treatment, with the heating temperature set at 120°C and the heating time set at 5 minutes.

[0099] After heat treatment, the temperature of each wafer was set to 25°C, and then rinsed with isopropyl alcohol (IPA). The heat-treated substrate was immersed in IPA to perform the rinsing process. The IPA was stirred in the container at 250 rpm using a magnetic stirrer while the IPA was being poured in. The temperature of the IPA was set to 25°C and the immersion time was set to 30 seconds. After rinsing, nitrogen gas is blown onto each wafer to dry it. High-contact corneas were formed on each wafer through the above treatment, and samples were obtained.

[0100] The water contact angle of the sample obtained by the above method was measured by the following method. Measurements were performed using a DMs-501 manufactured by Kyowa Interface Science Co.,LTD. at 23°C. The contact angle was calculated by measuring the water droplet's contact angle three times after 500 milliseconds. The surface tension of the water was set at 72.9 mN / m and analyzed. Based on the contact angles obtained from the above measurements, the contact angles were evaluated according to the following criteria. In practical applications, an evaluation of B or higher is considered better. .AA: Water contact angle of 105° or higher A: Water contact angle greater than 90° and less than 105° B: Water contact angle is greater than 60° and less than 90° C: Water contact angle less than 60°

[0101] [Stacked Selectivity Evaluation] Samples were obtained in the same manner as the contact angle described above, and ALD treatment was performed according to the following steps to evaluate packing selectivity. First, an alumina layer was formed on the obtained samples using an atomic layer deposition apparatus (AD-230LP manufactured by Samco Inc.). Trimethylaluminum was used as the organometallic raw material, and water was used as the oxidant. Furthermore, ALD processing was performed on each wafer before the formation of a high-contact cornea at a temperature of 150°C and a film thickness of 5 nm. The alumina film thickness of each ALD-treated sample was measured using a spectroelastic ellipsometry (M-2000XI, manufactured by JA Woollam Japan Co., Inc.). The film thickness was measured at five points on each sample, and the average value was taken as the film thickness. The measurement range was set to 1.2–2.5 eV, and the measurement angles were set to 70° and 75°. In addition, the smaller the film thickness, the less likely the ALD-based film is to accumulate.

[0102] <Results> Table 1 shows the composition and proportion of the drug solution, the results of the contact angle evaluation, and the results of the stacking selectivity evaluation.

[0103] The names of the compounds in Table 1 are as follows.

[0104] [Specific compound] A-1: Octadecylamine A-2: Dodecylamine A-3: Decanamine A-4: Butylamine A-5: Propylamine .B-1: Octadecanoic acid .B-2: Dodecanoic acid .C-1: Octadecylphosphonic acid .C-2: Dodecylphosphonic acid .D-1: Octadecyl alcohol .D-2: Dodecanool E-1: Octadecanthiol E-2: Decathiol .F-1: The following compound (molecular weight 502.82)

[0105] [Chemistry 1]

[0106] .F-2: The following compound (molecular weight 677.06)

[0107] [Chemistry 2]

[0108] .F-3: The following compound (molecular weight 793.22)

[0109] [Chemistry 3]

[0110] [Other compounds] .G-1: Octadecylane .G-2: Decane .H-1: Polymers with the following structures described in paragraphs

[0158] to

[0159] of Japanese Patent Application Publication No. 2021-041364. A polymer with the following structure was synthesized according to the method described in paragraph

[0158] of Japanese Patent Application Publication No. 2021-041364. The synthesized polymer with the following structure has a weight average molecular weight of 6000 and a number average molecular weight of 5600.

[0111] [Chemistry 4]

[0112] H-2: Polymers with the following structures described in paragraphs

[0170] to

[0171] of Japanese Patent Application Publication No. 2021-041364. A polymer with the following structure was synthesized according to the method described in paragraph

[0170] of Japanese Patent Application Publication No. 2021-041364. The synthesized polymer with the following structure has a weight average molecular weight of 6000 and a number average molecular weight of 5600.

[0113] [Chemistry 5]

[0114] H-3: Polymers with the following structures described in paragraphs

[0164] to

[0165] of Japanese Patent Application Publication No. 2021-041364. A polymer with the following structure was synthesized according to the method described in paragraph

[0164] of Japanese Patent Application Publication No. 2021-041364. The synthesized polymer with the following structure has a weight average molecular weight of 5100 and a number average molecular weight of 4800.

[0115] [Chemistry 6]

[0116] [solvent] .S-1: Methyl isobutyl methanol .S-2: Isopropanol

[0117] [Table 1] Example Comparative example 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 twenty one 1 2 3 4 medicine Specific compounds (parts by weight) A-1 0.5 0.75 0.4 0.25 0.5 0.5 0.5 0.5 0.5 0.5 A-2 0.5 0.25 0.3 0.75 0.5 0.5 0.5 0.45 0.45 0.45 0.5 A-3 0.3 A-4 0.5 1.0 A-5 0.5 B-1 0.5 0.5 0.5 0.5 0.45 0.45 0.45 B-2 C-1 0.5 0.5 C-2 0.5 D-1 0.5 0.5 D-2 0.5 E-1 0.5 E-2 0.5 0.5 F-1 0.5 F-2 0.5 0.5 F-3 0.5 Other compounds (parts by weight) G-1 0.5 G-2 0.5 0.5 H-1 0.1 H-2 0.1 H-3 0.1 solvent (parts by weight) S-1 99.0 99.0 99.0 99.0 99.0 99.0 99.0 99.0 99.0 99.0 99.0 99.0 99.0 99.0 99.0 99.0 99.0 99.0 100.0 99.0 99.0 99.0 S-2 99.0 99.0 99.0 evaluate W-layer wafer Contact angle (°) 100 109 111 108 110 110 111 60 60 110 85 110 107 100<00​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​ 0.7 2.5 0.7 0.9 2.3 0.7 0.7 3.0 3.2 0.9 0.9 0.8 5.0 5.0 4.2 5.0 Ru layer wafer Contact angle (°) 90 91 90 108 110 111 100 70 81 110 80 105 106 90 110 111 68 65 106 106 108 55 51 57 55 Contact angle evaluation A A A AA AA AA A B B AA B AA AA A AA AA B B AA AA AA C C C C AlOx film thickness (nm) 2.2 2.1 2.2 0.8 0.7 0.6 2.3 3.6 2.6 0.7 2.7 0.9 0.9 2.2 0.7 0.6 3.7 3.8 0.9 0.9 0.8 5.0 5.0 5.0 5.0

[0118] The results in Table 1 confirm that when the liquid of the present invention (Examples 1-16) is brought into contact with a substrate having a metal region, a film exhibiting a high water contact angle is formed on the metal region. On the other hand, Comparative Examples 1 and 2, which do not contain the specific compound, did not exhibit the above-mentioned effect. Furthermore, Comparative Examples 3 and 4, which contain only one specific compound, also did not exhibit the above-mentioned effect. A comparison of Examples 1-7 and Examples 12 with Examples 8 and 11 confirms that when a particular compound has a polar group selected from one or more groups including nitrogen-containing groups, phosphonic acid groups, carboxyl groups and thiol groups, the contact angle is larger. A comparison of Examples 1-4 with Example 9 confirmed that when the vertically oriented groups of a particular compound, i.e., the alkyl groups, have 10 or more carbon atoms, the contact angle is larger. It was confirmed from the comparison of Embodiments 5-7 and Embodiment 10 with other embodiments that The contact angle is larger when the compound contains a first specific compound having a nitrogen-containing group as a polar group and a second specific compound having a phosphonate group or its salt, a carboxyl group or its salt, or a thiol group as a polar group. The comparison of Examples 1-4, Example 7, and Example 12 with Example 8 confirmed that there are two or more third specific compounds, which have polar groups selected from the group consisting of nitrogen-containing groups, phosphonic acid groups or their salts, carboxyl groups or their salts, and thiol groups. In the case where the polar groups are the same in the two or more third specific compounds, the contact angle is larger. A comparison of Examples 17 and 18 confirmed that when the molecular weight of one or more of the specific compounds is less than 600, the contact angle is larger.

Claims

1. A semiconductor manufacturing solution comprising a solvent and two or more specific compounds, wherein the specific compounds are compounds having polar groups and vertically oriented groups, the semiconductor manufacturing solution being used for processing a substrate having metal regions, and forming a film comprising the two or more specific compounds only on the metal regions.

2. The pharmaceutical solution as claimed in claim 1, wherein the aforementioned polar group is selected from one or more groups selected from the group consisting of nitrogen-containing groups, phosphate groups or their salts, phosphonic acid groups or their salts, sulfonic acid groups or their salts, carboxyl groups or their salts, thiol groups and hydroxyl groups.

3. The pharmaceutical solution as described in claim 1, wherein, The aforementioned drug solution comprises: a first specific compound having a nitrogen-containing group as the aforementioned polar group and the aforementioned vertically aligned group; and a second specific compound having the aforementioned polar group other than the nitrogen-containing group and the aforementioned vertically aligned group.

4. The pharmaceutical solution as claimed in claim 3, wherein the aforementioned polar group of the second specific compound is a phosphonate group or its salt, a carboxyl group or its salt, or a thiol group.

5. The pharmaceutical solution as described in claim 1, wherein, The aforementioned pharmaceutical solution comprises: two or more third specific compounds having the aforementioned polar groups and the aforementioned vertically aligned groups selected from the group consisting of nitrogen-containing groups, phosphonic acid groups or their salts, carboxyl groups or their salts, and thiol groups, wherein the aforementioned polar groups are the same in the two or more aforementioned third specific compounds.

6. A semiconductor manufacturing solution comprising a solvent and two or more specific compounds, wherein the aforementioned specific compounds have polar groups and polyoxyalkylene groups.

7. The pharmaceutical solution as claimed in claim 6, wherein the aforementioned polar group is selected from one or more groups selected from the group consisting of nitrogen-containing groups, phosphate groups or their salts, phosphonic acid groups or their salts, sulfonic acid groups or their salts, carboxyl groups or their salts, thiol groups and hydroxyl groups.

8. The pharmaceutical solution as described in claim 6, wherein, The aforementioned liquid comprises: a fourth specific compound having a nitrogen-containing group as the aforementioned polar group and the aforementioned polyoxyalkylene group; and a fifth specific compound having the aforementioned polar group other than the nitrogen-containing group and the aforementioned polyoxyalkylene group.

9. The pharmaceutical solution as claimed in claim 8, wherein the aforementioned polar group of the fifth specific compound is a phosphonate group or its salt, a carboxyl group or its salt, or a thiol group.

10. The pharmaceutical solution as described in claim 6, wherein, The aforementioned liquid contains: two or more sixth specific compounds having the aforementioned polar groups and the aforementioned polyoxyalkylene groups selected from the group consisting of nitrogen-containing groups, phosphonic acid groups or their salts, carboxyl groups or their salts, and thiol groups, wherein the aforementioned polar groups are the same in the two or more aforementioned sixth specific compounds.

11. The liquid medicine as described in claim 1 or 6, wherein the molecular weight of one or more of the aforementioned specific compounds is 600 or less.

12. The solution as described in claim 6, used for processing a substrate having a metal region.

13. The liquid medicine as described in claim 1 or 12, wherein the aforementioned metal region comprises tungsten or ruthenium.

14. The liquid solution as described in claim 1 or 12, used to form a film containing two or more of the aforementioned specific compounds only on the aforementioned metal region.

15. The liquid solution as described in claim 1 or 6, used to form a film comprising two or more of the aforementioned specific compounds that function as a mask when forming a film on the aforementioned substrate by chemical vapor deposition.

16. A semiconductor manufacturing solution comprising a solvent and two or more specific compounds, wherein the specific compounds are compounds having polar groups and vertically oriented groups, the solution comprising: a first specific compound having a nitrogen-containing group as the aforementioned polar group and the aforementioned vertically oriented group; and a second specific compound having the aforementioned polar group other than the nitrogen-containing group and the aforementioned vertically oriented group, wherein the aforementioned polar group of the second specific compound is a phosphonate group or its salt, a carboxyl group or its salt, or a thiol group, and the aforementioned vertically oriented group of the second specific compound is a hydrocarbon group that may have halogen atoms, and the number of carbon atoms of the aforementioned hydrocarbon group is 3 to 20, and the ratio of the content of the first specific compound to the total content of the aforementioned specific compounds is 10 to 90 by mass.

17. A method for manufacturing a modified substrate, comprising: The step of contacting a substrate having a metal region with a liquid medicine as described in any one of claims 1 to 16 to form a film containing two or more of the aforementioned specific compounds on the aforementioned metal region to obtain a modified substrate.

18. A method for manufacturing a modified substrate as claimed in claim 17, wherein the aforementioned step is a step of obtaining a modified substrate comprising a film, the film comprising two or more specific compounds formed on the aforementioned metal region by contacting the aforementioned liquid with the aforementioned substrate, heating the aforementioned substrate in contact with the aforementioned liquid, and performing a rinsing treatment on the heated aforementioned substrate.

19. A method for manufacturing a laminate, comprising: The step of performing atomic layer deposition on a modified substrate manufactured by the manufacturing method described in claim 17 or 18, and forming a metal film or metal oxide film on a region other than the aforementioned metal region.

20. A method for manufacturing a laminate as described in claim 19, further comprising: The step of removing the film, wherein the film comprises two or more of the aforementioned specific compounds formed on the aforementioned metal region.

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