Method for manufacturing modified substrate and method for manufacturing semiconductor device

Abstract

The invention provides a method for manufacturing a modified substrate and a method for manufacturing a semiconductor device related to the method for manufacturing the modified substrate. The method for manufacturing the modified substrate can manufacture a modified substrate with an ALD coating film formed in a predetermined region with good selectivity through ALD processing. A method for manufacturing a modified substrate according to the present invention comprises: a step 1 for forming a first coating film on a first surface of a substrate having at least two surfaces of the first surface and a second surface made of different materials, by bringing the substrate into contact with a chemical solution, the chemical solution contains a solvent and a compound having a molecular weight of 500 or less and having a functional group bonded or adsorbed to the first surface and a crosslinkable group; and a step 2 for forming a second coating film on the second surface by performing an atomic layer deposition process on the substrate obtained in the step 1.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a modified substrate and a method for manufacturing a semiconductor device. Background Technology

[0002] As semiconductor devices become increasingly miniaturized, there is a growing demand for the fabrication of finer and more precise semiconductor components. Previously, photolithography was used to fabricate semiconductor components, but this method has become insufficient to meet the required precision, particularly in areas such as alignment of the patterns.

[0003] Currently, atomic layer deposition (ALD) is a known technique for forming films in designated areas. As a related technique based on this ALD, Non-Patent Document 1 reports the following: after adsorbing a low-molecular-weight aminosilane compound as an inhibitor onto the silica surface of a substrate, an alumina layer is formed by atomic layer deposition using aluminum dimethyl isopropoxide and water as precursors. This process hinders the growth of the alumina layer in areas where the low-molecular-weight aminosilane is adsorbed.

[0004] Previous technical documents

[0005] Non-patent literature

[0006] Non-patent literature 1: Wanxing Xu, Mitchel GNHaeve, Paul C. Lemaire, Kashish Sharma, Dennis M. Hausmann, and Sumit Agarwal, Langmuir 2022, 38, 2, 652-660. Summary of the Invention

[0007] The technical problem to be solved by the invention

[0008] On the other hand, recently, the following method has been studied: for a substrate having multiple regions on the surface composed of different materials (e.g., a metal region containing metal atoms and an insulating region containing an insulator), after modifying one region to form a film (modification film), an ALD treatment is performed, thereby forming an ALD-based coating (ALD coating) in the region where the modification film is formed, and forming an ALD coating in the region where the modification film is not formed, thereby forming a fine pattern.

[0009] The inventors conducted research on the technology described in Non-Patent Document 1, and found that after forming the modified film using the aforementioned low-molecular-weight aminosilane compound, when attempting to form an ALD coating on areas where the modified film was not formed, a thick ALD coating was also formed on the areas where the modified film was formed (on the modified film). In other words, it was difficult to selectively and effectively form an ALD coating on areas where the modified film was not formed.

[0010] Therefore, the objective of this invention is to provide a method for manufacturing a modified substrate and a method for manufacturing a semiconductor device related to the above-described method for manufacturing a modified substrate, wherein the method for manufacturing a modified substrate is capable of manufacturing a modified substrate having an ALD coating selectively and well formed in a specified area by performing an ALD process.

[0011] means for solving technical problems

[0012] The inventors conducted in-depth research to solve the aforementioned problems, and ultimately completed this invention. Specifically, they discovered that the above-mentioned problems can be solved through the following structure.

[0013] [1] A method for manufacturing a modified substrate, comprising:

[0014] Step 1 involves contacting a substrate with a pharmaceutical solution to form a first coating on a first surface of the substrate. The substrate has at least two surfaces, a first surface and a second surface, each made of different materials. The pharmaceutical solution comprises a compound having functional groups and crosslinking groups bonded or adsorbed onto the first surface and having a molecular weight of 500 or less, and a solvent.

[0015] Step 2 involves performing atomic layer deposition on the substrate obtained in Step 1 to form a second coating on the second surface.

[0016] [2] The method for manufacturing the modified substrate according to [1], wherein,

[0017] The functional groups bonded to or adsorbed on the first surface are selected from nitrogen-containing groups, phosphonic acid groups or their salts, phosphonate esters, phosphate groups or their salts, carboxyl groups or their salts, hydroxyl groups, thiol groups and hydrolyzable silane groups.

[0018] [3] The method for manufacturing the modified substrate according to [1] or [2], wherein,

[0019] The aforementioned crosslinking groups are olefinic unsaturated groups.

[0020] [4] A method for manufacturing a modified substrate according to any one of [1] to [3], wherein,

[0021] The crosslinking groups mentioned above are selected from acryloyl, methacryloyl, vinyl ether, styrene, vinylnaphthyl, and vinyl.

[0022] [5] A method for manufacturing a modified substrate, comprising:

[0023] Step 1 involves contacting a substrate with a pharmaceutical solution to form a first coating on a first surface of the substrate. The substrate has at least two surfaces, a first surface and a second surface, each made of different materials. The pharmaceutical solution comprises a compound having a molecular weight of 500 or less and containing groups selected from nitrogen-containing groups, phosphonic acid groups or their salts, phosphonates, phosphate groups or their salts, carboxyl groups or their salts, hydroxyl groups, thiols, and hydrolyzable silyl groups, as well as crosslinking groups; and a solvent.

[0024] Step 2 involves performing atomic layer deposition on the substrate obtained in Step 1 to form a second coating on the second surface.

[0025] [6] The method for manufacturing the modified substrate according to [5], wherein,

[0026] The aforementioned crosslinking groups are olefinic unsaturated groups.

[0027] [7] The method for manufacturing the modified substrate according to [5] or [6], wherein,

[0028] The crosslinking groups mentioned above are selected from acryloyl, methacryloyl, vinyl ether, styrene, vinylnaphthyl, and vinyl.

[0029] [8] A method for manufacturing a modified substrate according to any one of [1] to [7], wherein,

[0030] At least one of the first surface and the second surface is a metal surface made of metal.

[0031] [9] A method for manufacturing a modified substrate according to any one of [1] to [8], wherein,

[0032] At least one of the first surface and the second surface mentioned above contains at least one metal atom selected from copper atoms, cobalt atoms, titanium atoms, tantalum atoms, tungsten atoms, ruthenium atoms and molybdenum atoms.

[0033]

[10] A method for manufacturing a modified substrate according to any one of [1] to [9], wherein,

[0034] At least one of the first surface and the second surface mentioned above contains at least one metal atom selected from titanium atoms, tungsten atoms, ruthenium atoms and molybdenum atoms.

[0035]

[11] A method for manufacturing a modified substrate according to any one of [1] to

[10] , wherein,

[0036] The second coating mentioned above is a metal film or a metal oxide film.

[0037]

[12] The method for manufacturing the modified substrate according to any one of [1] to

[11] further includes:

[0038] Step 3: Remove the first coating after step 2.

[0039]

[13] A method for manufacturing a decorative substrate according to any one of [1] to [4] and [8] to

[12] , wherein,

[0040] The above-mentioned solution contains a polymerization inhibitor.

[0041]

[14] The method for manufacturing the modified substrate according to

[13] , wherein,

[0042] The above-mentioned polymerization inhibitors include at least one compound selected from phenolic compounds, quinone compounds, free radical compounds, amine compounds and phosphine compounds.

[0043]

[15] The method for manufacturing the modified substrate according to

[13] or

[14] , wherein,

[0044] The content of the above-mentioned polymerization inhibitor is 0.001 to 1.000 parts by mass relative to 100 parts by mass of the above-mentioned compound.

[0045]

[16] The method for manufacturing the modified substrate according to

[13] or

[14] , wherein,

[0046] The content of the above-mentioned polymerization inhibitor is 0.01 parts by mass or more relative to 100 parts by mass of the above-mentioned compound.

[0047]

[17] A method for manufacturing a modified substrate according to any one of [5] to [7], wherein,

[0048] The above-mentioned solution contains a polymerization inhibitor.

[0049]

[18] The method for manufacturing the modified substrate according to

[17] , wherein,

[0050] The above-mentioned polymerization inhibitors include at least one compound selected from phenolic compounds, quinone compounds, free radical compounds, amine compounds and phosphine compounds.

[0051]

[19] The method for manufacturing the modified substrate according to

[17] or

[18] , wherein,

[0052] The content of the above-mentioned polymerization inhibitor is 0.001 to 1.000 parts by mass relative to 100 parts by mass of the above-mentioned compound.

[0053]

[20] The method for manufacturing the modified substrate according to

[17] or

[18] , wherein,

[0054] The content of the above-mentioned polymerization inhibitor is 0.01 parts by mass or more relative to 100 parts by mass of the above-mentioned compound.

[0055]

[21] A method for manufacturing a modified substrate according to any one of [1] to

[20] , wherein,

[0056] The above-mentioned liquid contains water.

[0057]

[22] According to the method for manufacturing the modified substrate described in

[21] , wherein,

[0058] The water content is less than 80% by mass relative to the total mass of the solvent.

[0059]

[23] A method for manufacturing a modified substrate according to any one of [1] to

[22] , wherein,

[0060] The above-mentioned liquid contains three or more of the aforementioned solvents.

[0061]

[24] A method for manufacturing a semiconductor device, comprising the method for manufacturing a modified substrate as described in any one of [1] to

[23] .

[0062] Invention Effects

[0063] According to the present invention, a method for manufacturing a modified substrate and a method for manufacturing a semiconductor device related to the above-described method for manufacturing a modified substrate are provided. The method for manufacturing a modified substrate can manufacture a modified substrate in which an ALD-based coating is selectively and well formed in a specified area by performing an ALD process. Detailed Implementation

[0064] The following explains the meaning of each statement in this specification.

[0065] In this specification, the numerical range indicated by “~” refers to the range including the values ​​before and after “~” as the lower and upper limits.

[0066] Unless otherwise stated, the compounds described in this specification may include structural isomers, optical isomers, and isotopes. Furthermore, structural isomers, optical isomers, and isotopes may consist of one or more individual types.

[0067] 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-.

[0068] Unless otherwise specified, the molecular weight of compounds with molecular weight distribution in this specification is the weight-average molecular weight.

[0069] The manufacturing method of the modified substrate of the present invention will be described in detail below.

[0070] A first embodiment of the method for manufacturing the modified substrate of the present invention includes: step 1, contacting a substrate with a liquid medicine to form a first coating on a first surface, wherein the substrate has at least two surfaces, a first surface and a second surface, which are made of different materials; the liquid medicine includes a compound (hereinafter also referred to as "specific compound 1") having functional groups and crosslinking groups bonded or adsorbed on the first surface and having a molecular weight of 500 or less; and a solvent; and step 2, performing atomic layer deposition on the substrate obtained in step 1 to form a second coating on the second surface.

[0071] Furthermore, a second embodiment of the method for manufacturing the modified substrate of the present invention includes: step 1, contacting a substrate with a liquid medicine to form a first coating on the first surface, wherein the substrate has at least two surfaces, a first surface and a second surface, which are made of different materials; the liquid medicine includes a compound having a group selected from nitrogen-containing groups, phosphonic acid groups or their salts, phosphonate esters, phosphate groups or their salts, carboxyl groups or their salts, hydroxyl groups, thiol groups and hydrolyzable silyl groups (hereinafter also referred to as "specific groups") and crosslinking groups, and having a molecular weight of 500 or less (hereinafter also referred to as "specific compound 2"), and a solvent; and step 2, performing atomic layer deposition on the substrate obtained in step 1 to form a second coating on the second surface.

[0072] Although the mechanism by which the modified substrate manufacturing method of the present invention (first embodiment and second embodiment) can solve the problem of the present invention by adopting the above-described structure is not yet clear, the inventors speculate as follows.

[0073] Furthermore, based on the following speculation, there is no limitation on the mechanism by which the effect can be obtained. In other words, even if the effect is obtained through a mechanism other than that described below, it is still included within the scope of this invention.

[0074] The solution used in the method for manufacturing the modified substrate of the present invention (hereinafter also referred to as "the solution") comprises a specific compound 1 having functional groups bonded or adsorbed onto the first surface, or a specific compound 2 having specific groups. This results in the easy formation of a first coating on the first surface. The first coating contains components derived from either the specific compound 1 or the specific compound 2.

[0075] Furthermore, since specific compound 1 and specific compound 2 have crosslinking groups, the substrate is heated in the ALD process of step 2 after step 1, thereby reacting between the crosslinking groups to form covalent bonds, and the first coating becomes a cured film.

[0076] Therefore, by uniformly forming a first coating on the first surface and covalently bonding the crosslinking groups to each other during the ALD treatment, a cured film with excellent heat resistance and water resistance is formed on the first surface. It is therefore speculated that during the ALD treatment, it becomes difficult to form an ALD coating on the cured film, and as a result, it becomes easy to selectively and well form an ALD coating on the second surface.

[0077] The following describes in detail each step that can be included in the manufacturing method of the modified substrate of the present invention.

[0078] Furthermore, the case where the ALD coating is formed in a specified area with greater selectivity through ALD treatment is also referred to as "the effect of the present invention is even better".

[0079] [Method for manufacturing a modified substrate (First Embodiment)]

[0080] The first embodiment of the method for manufacturing the modified substrate of the present invention includes step 1.

[0081] Step 1 is a step of forming a first coating on the first surface by bringing the substrate into contact with the liquid medicine. The substrate has at least two surfaces, a first surface and a second surface, which are made of different materials. The liquid medicine (hereinafter also referred to as "liquid medicine 1") contains a compound (specific compound 1) having functional groups and crosslinking groups bonded or adsorbed to the first surface and having a molecular weight of 500 or less, and a solvent.

[0082] The following is a detailed description of the medicine solution 1 used in process 1.

[0083] <Medicine Solution 1>

[0084] The drug solution 1 contains a specific compound 1 and a solvent.

[0085] [Specific compound 1]

[0086] As described above, specific compound 1 is a compound having functional groups and crosslinking groups bonded or adsorbed on the first surface and having a molecular weight of 500 or less.

[0087] The functional groups bonded or adsorbed onto the first surface can form any type of bond or interaction with the first surface, such as covalent bonds, coordination bonds, ionic bonds, hydrogen bonds, van der Waals bonds, and metallic bonds.

[0088] As will be described below, from the viewpoint that the first surface preferably contains metal atoms, functional groups that are bonded to or adsorbed onto the first surface are preferably functional groups that are bonded to or adsorbed onto the surface containing metal atoms.

[0089] Functional groups that are bonded to or adsorbed onto the first surface include, for example, nitrogen-containing groups, phosphonates, phosphate groups (-PO4H2) or their salts, phosphonic acid groups (-PO3H2) or their salts, sulfonates (-SO3H) or their salts, carboxyl groups (-COOH) or their salts, hydroxyl groups (-OH), thiols (-SH) and hydrolyzable silyl groups.

[0090] When a specific compound 1 contains a nitrogen-containing group, a phosphonate, a phosphate group (-PO4H2) or a salt thereof, a phosphonic acid group (-PO3H2) or a salt thereof, a sulfonate group (-SO3H) or a salt thereof, a carboxyl group (-COOH) or a salt thereof, a hydroxyl group (-OH) or a thiol group (-SH), the first coating is more easily selectively formed on a substrate of form A described later. When it contains a hydrolyzable silane, the first coating is more easily selectively formed on a substrate of form B described later (especially form B3).

[0091] The functional groups that are bonded or adsorbed onto the first surface are preferably selected from nitrogen-containing groups, phosphonic acid groups or their salts, phosphonate esters, phosphate groups or their salts, carboxyl groups or their salts, hydroxyl groups, thiol groups and hydrolyzable silyl groups, more preferably selected from nitrogen-containing groups, phosphonic acid groups or their salts, phosphonate esters, carboxyl groups or their salts, hydroxyl groups, thiol groups and hydrolyzable silyl groups, and even more preferably selected from nitrogen-containing groups, phosphonic acid groups or their salts and phosphonate esters.

[0092] Examples of nitrogen-containing groups include primary amino groups (-NH2) and secondary amino groups (-NR). T H), tertiary amino (-NR) T 2) and quaternary ammonium groups (-N) + R T 3) Preferably, it is a primary amino group, a secondary amino group, or a tertiary amino group, and more preferably a primary amino group.

[0093] Additionally, R T Indicates an alkyl group having 1 to 3 carbon atoms, with multiple Rs. T They can be different from each other. Furthermore, multiple R1s can bond together to form a ring. The resulting ring is a ring containing nitrogen atoms; examples include pyrrolidine rings, piperidine rings, and piperazine rings.

[0094] 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, triazinyl, pyrroleyl, pyrazolyl, imidazoleyl, pyrazolyl, triazolyl, benzimidazoleyl, and benzotriazolyl.

[0095] The salt of phosphate group refers to -PO4. 2- Ct n+ 2 / n The group represented. Additionally, Ct n+This represents a cation with an n-valent charge, where n represents 1 or 2. An example of a cation with a monovalent charge is Li. + Na + K + and NH4 + etc. Ct n+ When representing a cation with a monovalent charge, there are two of them. Mg can be cited as an example of a divalent cation. 2+ and Ca 2+ etc. Ct n+ In the case of a divalent cation, the number is 1.

[0096] In addition, compounds with phosphate groups are also simply referred to as "phosphate compounds," and as a functional group name, they are also called "-phosphate."

[0097] Phosphonic acid salts refer to -PO3 2- Ct n+ 2 / n The group represented. Ct n+ This indicates a cation with an n-valent charge, where n represents 1 or 2. Examples of cations with a 1-valent charge and those with a 2-valent charge are the same as those described in the above-described phosphate salts, and the number of each cation is also the same.

[0098] Furthermore, phosphonates refer to -PO3R P The group represented by 2. R P Each can independently represent a hydrogen atom or an organic group. Among them, there are two R groups. P At least one of them represents an organic group. Phosphonate esters are preferably monoesters. That is, preferably, two R groups are present. P One of them is a hydrogen atom, and the other is an organic group.

[0099] As the organic group, an aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferred, an aliphatic hydrocarbon group having 1 to 6 carbon atoms is more preferred, and an alkyl group having 1 to 6 carbon atoms is even more preferred. The aforementioned aliphatic hydrocarbon group and alkyl group can be any of the following: straight-chain, branched, and cyclic.

[0100] In addition, compounds containing phosphonic acid groups are also called "phosphonic acid compounds".

[0101] The salt of sulfonium is represented by -SO3. - Ct + The group represented. Ct + The cation with a monovalent charge can be the same cation with a monovalent charge as those described in the salts of the phosphate group above.

[0102] Salts of carboxyl groups are represented by -COO - Ct + The group represented. Ct +The cation with a monovalent charge can be the same cation with a monovalent charge as those described in the salts of the phosphate group above.

[0103] The aforementioned hydroxyl group can be either an alcoholic hydroxyl group (a hydroxyl group bonded to an aliphatic hydrocarbon) or a phenolic hydroxyl group (a hydroxyl group bonded to an aromatic hydrocarbon), with an alcoholic hydroxyl group being preferred.

[0104] The aforementioned hydrolyzable silyl group refers to a group that, by having silicon atoms, reacts with water to form a group capable of forming a bond with the first surface. Examples of hydrolyzable silyl groups include alkoxysilyl groups and chlorosilyl groups (groups having a -Si-Cl structure).

[0105] In the alkoxysilane group, the number of alkoxy groups bonded to silicon atoms (Si atoms) is not particularly limited, but is preferably 2 or more, more preferably 3. The number of carbon atoms in the alkoxy groups bonded to the Si atoms is preferably 1 to 6, more preferably 1 to 3.

[0106] Regarding alkoxysilyl groups, trimethoxysilyl or triethoxysilyl groups are preferred.

[0107] In the chlorosilane, the number of chlorine atoms bonded to Si atoms is preferably 1 to 3, more preferably 1. When the number of chlorine atoms is 1 or 2, the chlorosilane is preferably a dialkyl monochlorosilane or a monoalkyl dichlorosilane.

[0108] The alkyl group can be any of the following: straight-chain, cyclic, and branched, preferably straight-chain. Among the alkyl groups, methyl is preferred.

[0109] There is no particular limitation as long as the number of functional groups bonded or adsorbed on the first surface of the specific compound 1 is 1 or more, preferably 1 to 3, and more preferably 1.

[0110] There are no particular limitations as long as the aforementioned crosslinking groups can form bonds between them through heating. Examples of crosslinking groups include free radical polymerizable groups, cationic polymerizable groups, and anionic polymerizable groups, with olefinic unsaturated groups being preferred.

[0111] As a crosslinking group, it is preferably selected from acryloyl, methacryl, vinyl ether, styrene, vinylnaphthyl, and vinyl groups, more preferably styrene, vinylnaphthyl, or vinyl. Vinylina is preferably a group formed by removing the hydrogen atom at the 6-position from 2-vinylnaphthalene.

[0112] Furthermore, the vinyl group mentioned above refers to the group represented by CH2=CH-. In this specification, acryloyl, methacryloyl, vinyl ether, styrene, and vinylnaphthyl are all treated as groups different from vinyl groups. That is, although acryloyl, methacryloyl, vinyl ether, styrene, and vinylnaphthyl contain the structure represented by CH2=CH-, they are treated as groups different from vinyl groups.

[0113] There is no particular limitation on the number of crosslinking groups in a specific compound 1 as long as it is 1 or more, preferably 1 to 3, and more preferably 1.

[0114] The specific compound 1 preferably has a structure that displays orientation. A structure that displays orientation means that, when the substrate is brought into contact with the liquid 1 to form a first coating on the first surface of the substrate, it has the function of oriented the specific compound 1 in a vertical direction relative to the first surface.

[0115] There are no particular limitations on the structure that can exhibit orientation; for example, divalent aliphatic hydrocarbon groups with ether-like oxygen atoms, divalent aromatic cyclic groups, and groups formed by combining them can be cited. Among these, divalent aliphatic hydrocarbon groups with ether-like oxygen atoms are preferred.

[0116] The aforementioned divalent aliphatic hydrocarbon group can be any of the following: straight-chain, branched, and cyclic, but straight-chain is preferred. Examples of divalent aliphatic hydrocarbon groups include alkylene, alkenylene, and ynylene, with alkylene being preferred.

[0117] There is no particular limitation on the number of carbon atoms in the divalent aliphatic hydrocarbon group. From the viewpoint of improving the stability of the first coating on the first surface, it is preferably 1 to 25, more preferably 3 to 20, and even more preferably 6 to 18.

[0118] The divalent aromatic cyclic group can be any one of a divalent aromatic hydrocarbon group (arylene) and a divalent aromatic heterocyclic group (heteroarylene), preferably an arylene.

[0119] The divalent aromatic ring group can be either monocyclic or polycyclic.

[0120] The number of carbon atoms in the divalent aromatic ring group is preferably 5 to 25, more preferably 6 to 20, and even more preferably 6 to 10.

[0121] As an arylene group, for example, phenylene can be cited.

[0122] As a heteroarylene, for example, a group obtained by removing two hydrogen atoms from pyridine can be cited.

[0123] As a specific compound 1, wherein the compound represented by the preferred formula (S1) is a compound.

[0124] X 1 -L 1 -Y 1 Formula (S1)

[0125] In formula (S1), X 1 It indicates a group selected from nitrogen-containing groups, phosphonic acid groups or their salts, phosphonate esters, phosphate groups or their salts, carboxyl groups or their salts, hydroxyl groups, thiol groups and hydrolyzable silyl groups.

[0126] X 1 The specific and preferred forms of each group are as described above for functional groups bonded or adsorbed onto the first surface. Regarding X... 1 The groups represented are preferably primary amino groups.

[0127] In formula (S1), Y 1 This indicates an alkene unsaturated group.

[0128] As Y 1 The olefinic unsaturated group represented is preferably selected from acryloyl, methacryloyl, vinyl ether, styrene, vinylnaphthyl, and vinyl groups.

[0129] In formula (S1), L 1 This indicates a divalent aliphatic hydrocarbon group, a divalent aromatic cyclic group, or a combination thereof that may have an ether-like oxygen atom.

[0130] The specific and preferred forms of the divalent aliphatic hydrocarbon group, the divalent aromatic cyclic group, and the group formed by combining them are as described above.

[0131] Among them, the aforementioned divalent aliphatic hydrocarbon group is preferably an alkylene group having an ether-like oxygen atom, and more preferably an alkylene group having an ether-like oxygen atom with 6 to 18 carbon atoms.

[0132] As the divalent aromatic cyclic group mentioned above, phenylene is preferred.

[0133] There are no particular limitations on the molecular weight of the specific compound 1 as long as it is below 500, preferably 50 to 450, more preferably 100 to 450, and even more preferably 150 to 400.

[0134] The content of specific compound 1 relative to the total mass of the drug solution 1 is preferably 0.0001 to 10.0% by mass, more preferably 0.001 to 1.0% by mass, and even more preferably 0.01 to 0.5% by mass.

[0135] A specific compound 1 can also be used in combination with two or more.

[0136] When two or more specific compounds 1 are used, their total content is preferably within the above range.

[0137] (solvent)

[0138] Solution 1 contains a solvent.

[0139] Examples of solvents include water and organic solvents.

[0140] Examples of organic solvents include hydrocarbon solvents, alcohol solvents, polyol solvents, ethylene glycol ether solvents, ether solvents, ketone solvents, amide solvents, sulfur-containing solvents, and ester solvents.

[0141] 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.

[0142] 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, tert-butanol, 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.

[0143] The number of carbon atoms in the alcohol solvent is preferably 1 to 8, more preferably 2 to 7, and even more preferably 3 to 6.

[0144] Examples of polyol solvents include ethylene glycol solvents with 2 to 18 carbon atoms.

[0145] Examples of ethylene glycol solvents include ethylene glycol, propylene glycol (1,2-propanediol), 1,3-propanediol, diethylene glycol, and dipropylene glycol.

[0146] Examples of ethylene glycol ether solvents include, for example, ethylene glycol monoether solvents with 3 to 19 carbon atoms.

[0147] 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.

[0148] The number of carbon atoms in ethylene glycol ether solvents is preferably 1 to 8, more preferably 2 to 7, and even more preferably 3 to 6.

[0149] Examples of ketone solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

[0150] Examples of ether solvents include diethyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, cyclohexyl methyl ether, and tetrahydrofuran.

[0151] Examples of amide solvents include formamide, monomethylformamide, dimethylformamide, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide, and N-methylpyrrolidone.

[0152] As a sulfur-containing solvent, dimethyl sulfone can be cited as an example.

[0153] Dimethyl sulfoxide and sulfolane.

[0154] Examples of ester solvents include, for example, n-butyl acetate, ethyl lactate, propylene glycol acetate, propylene glycol monomethyl ether acetate, γ-butyrolactone, and δ-valerolactone.

[0155] Ester solvents can include ethylene glycol ester solvents, monocarboxylic acid ester solvents such as n-butyl acetate and ethyl lactate, lactone solvents such as γ-butyrolactone (GBL) and δ-valerolactone, and carbonate solvents such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate.

[0156] Examples of ethylene glycol ester solvents include ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, tetraethylene glycol diacetate, propylene glycol acetate, propylene glycol diacetate, dipropylene glycol diacetate, and methoxybutyl acetate, which have 6 to 22 carbon atoms; and ethylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, tetraethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether acetate, tetrapropylene glycol monomethyl ether acetate, and butylene glycol monomethyl ether acetate, which have 5 to 21 carbon atoms.

[0157] The number of carbon atoms in ester solvents is preferably 3 to 22, more preferably 4 to 12.

[0158] As a solvent, alcohol solvents, ethylene glycol ether solvents, or ester solvents are preferred, more preferably aliphatic alcohol solvents with 1 to 18 carbon atoms, ethylene glycol monoether solvents with 3 to 19 carbon atoms, or ester solvents with 4 to 12 carbon atoms, and even more preferably IPA, propylene glycol monomethyl ether, ethyl lactate, γ-butyrolactone, propylene carbonate, or PGMEA.

[0159] As the ester solvents mentioned above, monocarboxylic acid ester solvents, lactone solvents, or carbonate solvents are preferred.

[0160] Two or more solvents can be used together. Furthermore, three or more solvents can be used. That is, the solution can contain three or more solvents.

[0161] When using two or more solvents, it is preferable to use one or more organic solvents selected from alcohol solvents, glycol ether solvents and ester solvents, and water; more preferably, one or two of the above-mentioned organic solvents and water are used together.

[0162] The preferred form of the organic solvent is as described above, but IPA, propylene glycol monomethyl ether, ethyl lactate, γ-butyrolactone, propylene carbonate or PGMEA are preferred as organic solvents.

[0163] When the solution contains water, the water content is preferably 80% by mass or less, more preferably less than 80% by mass, further preferably 50% by mass or less, and especially preferably 30% by mass or less, relative to the total mass of the solvent contained in the solution. There is no particular limitation on the lower limit; for example, it can be 0% by mass.

[0164] Furthermore, when the content of organic solvent is set as A, the content of water is set as B, and A+B is set as 100, the ratio of organic solvent to water content A / B is preferably 20 / 80 to 100 / 0, more preferably 30 / 70 to 90 / 10, and even more preferably 40 / 60 to 80 / 20.

[0165] The solvent content in the drug solution is preferably 90 to 99.999% by mass relative to the total mass of the drug solution, more preferably 95 to 99.9% by mass, and even more preferably 97 to 99.9% by mass.

[0166] When using two or more solvents, it is preferable that their total content is within the above range.

[0167] (polymerization inhibitor)

[0168] From the viewpoint of improving the stability of the solution, solution 1 preferably contains a polymerization inhibitor.

[0169] There are no particular limitations on the type of polymerization inhibitor; any known polymerization inhibitor can be selected based on the type of crosslinking groups possessed by the specific compound 1. However, a free radical polymerization inhibitor is preferred.

[0170] The polymerization inhibitor preferably contains at least one compound selected from phenolic compounds, quinone compounds, free radical compounds, amine compounds and phosphine compounds, and from the viewpoint of polymerization inhibition performance, free radical compounds are more preferred.

[0171] Examples of phenolic compounds include, for example, 4-methoxyphenol, hydroquinone, 2-tert-butylhydroquinone, 4-tert-butylcatechol, pentaerythritol tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4-methoxynaphthol, 2,4-bis(octylthiomethyl)-6-methylphenol, p-nitrosophenol, and α-nitroso-β-naphthol.

[0172] Examples of quinone compounds include 1,4-benzoquinone, 1,2-benzoquinone, and 1,4-naphthoquinone.

[0173] Examples of free radical compounds include poly(4-methacryloyloxy-2,2,6,6-tetramethylpiperidine-N-oxy), 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy, 2,2,6,6-tetramethylpiperidine-1-oxy, 2,2-diphenyl-1-trinitrophenylhydrazine, and triphenyltetrahydrazine.

[0174] Examples of amine compounds include, for example, p-phenylenediamine, 4-aminodiphenylamine, N,N-diethylhydroxylamine, N,N'-diphenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N,N'-di-2-naphthyl-p-phenylenediamine, diphenylamine, N-phenyl-β-naphthylamine, 4,4'-diisopropylphenyl-diphenylamine, 4,4'-dioctyl-diphenylamine, phenothiazine, 2-methoxyphenothiazine, phenothiazine, N-nitrosodiphenylamine, N-nitrosobenzenaphthylamine, p-nitrosodiphenylamine, N-nitroso-N-phenylhydroxylamine, N-nitroso-N-phenylhydroxylamine aluminum, and copper ferroin. The compounds exemplified as amine compounds can form metal salts or metal complexes.

[0175] Phosphorous acid (2,4-di-tert-butylphenyl) can be cited as an example of a phosphine compound.

[0176] In addition, as a polymerization inhibitor, it may include nitrobenzene compounds such as nitrobenzene and 4-nitrotoluene, as well as thiolsalicylate, dilaurylate, dimyristicate, and distearate, etc.

[0177] The molecular weight of the polymerization inhibitor is preferably 1,000 or less, more preferably 800 or less, and even more preferably 500 or less. The lower limit of the above molecular weight is not particularly limited, but is preferably 80 or more.

[0178] The content of the polymerization inhibitor is preferably 0.0001 parts by mass or more, more preferably 0.001 parts by mass or more, further preferably 0.005 parts by mass or more, and especially preferably 0.010 parts by mass or more, relative to 100 parts by mass of the specific compound 1 mentioned above.

[0179] Furthermore, the content of the polymerization inhibitor is preferably 10.0 parts by mass or less, more preferably 1.000 parts by mass or less, and even more preferably 0.100 parts by mass or less, relative to the content of the specific compound 1 described above.

[0180] Solution 1 may contain one type of polymerization inhibitor or two or more types. When it contains two or more polymerization inhibitors, it is preferable that their total amount is within the range described above.

[0181] <Method for manufacturing liquid 1>

[0182] There are no particular limitations on the manufacturing method of the above-mentioned liquid medicine 1. For example, it can be manufactured by mixing the above-mentioned components.

[0183] There are no particular restrictions on the order or timing of the components in the mixed solution. For example, a solution can be prepared by adding a specific compound 1 to a mixer or other stirrer containing purified solvent and then stirring thoroughly.

[0184] If the liquid contains other ingredients besides specific compound 1, the other ingredients may be added to specific compound 1 at the same time or at different times.

[0185] In the manufacturing process of liquid medicine 1, the following steps can be performed.

[0186] (Metal removal process)

[0187] Regarding the above manufacturing method, a metal removal process can be performed to remove metal components from the above-mentioned components and / or pharmaceutical solutions (hereinafter also referred to as "the purified substance").

[0188] (Filtration process)

[0189] The manufacturing method described above preferably includes a filtration step of filtering the liquid to remove foreign matter and coarse particles from the liquid.

[0190] There are no particular restrictions on the filtering method; any known filtering method can be used. Among these, filtration using a filter is preferred.

[0191] (Electrification process)

[0192] The manufacturing method of the liquid medicine may also include a static removal process to remove static electricity from the liquid medicine.

[0193] <Substrate>

[0194] In the first embodiment of the method for manufacturing the modified substrate of the present invention, the substrate used is a substrate having at least two surfaces, a first surface and a second surface, which are made of different materials from each other (hereinafter also simply referred to as "substrate").

[0195] The materials constituting the first surface and the materials constituting the second surface are not particularly limited as long as they are different from each other, and can be any of organic and inorganic materials. From the viewpoint of better effect of the present invention, it is preferred that at least one of the first surface and the second surface contains metal atoms, and more preferably the first surface contains metal atoms.

[0196] In addition, in this specification, quasi-metallic atoms such as boron, silicon, gunpowder, arsenic, antimony, and tellurium are also included in the category of metallic atoms.

[0197] When the first or second surface contains metal atoms, these metal atoms may be contained, for example, as metal atoms contained in a metal (e.g., a metal monomer) or a compound. Furthermore, the metal atoms may be contained as metal atoms contained in a pure metal or an alloy.

[0198] As a metal atom, a transition metal atom is preferred, preferably at least one metal atom selected from copper atom, cobalt atom, titanium atom, tantalum atom, tungsten atom, ruthenium atom and molybdenum atom, more preferably at least one metal atom selected from titanium atom, tungsten atom, ruthenium atom and molybdenum atom, and even more preferably ruthenium atom or tungsten atom.

[0199] In cases where the first surface contains at least one metal atom selected from copper atoms, cobalt atoms, titanium atoms, tantalum atoms, tungsten atoms, ruthenium atoms, and molybdenum atoms, from the viewpoint of achieving better results in this invention, it is preferable that a specific compound 1, as a functional group bonded or adsorbed onto the first surface, has a group selected from nitrogen-containing groups, phosphonates, phosphate groups (-PO4H2) or their salts, phosphonic acid groups (-PO3H2) or their salts, sulfonyl groups (-SO3H) or their salts, carboxyl groups (-COOH) or their salts, hydroxyl groups (-OH), and thiol groups (-SH).

[0200] Furthermore, as another preferred form of the first surface and the second surface, one of the first surface and the second surface is a metallic surface made of metal and the other is a non-metallic surface made of non-metal (hereinafter also referred to as form A).

[0201] As for metals, pure metals or alloys can be cited.

[0202] Examples of nonmetals include metal carbides, metal oxides, metal nitrides, metal oxynitrides, and organic materials.

[0203] As pure metals and alloys, they are preferably composed of the preferred metal atoms as exemplified above.

[0204] Furthermore, the metal carbides, metal oxides, metal nitrides, and metal oxynitrides are preferably metal carbides, metal oxides, metal nitrides, and metal oxynitrides with the preferred metal atoms as exemplified above.

[0205] In form A, preferably, the first surface is a metal surface and the second surface is a non-metallic surface.

[0206] When the first surface is a metallic surface and the second surface is a non-metallic surface, from the viewpoint of achieving better results in this invention, it is preferable that a specific compound 1, as a functional group bonded or adsorbed onto the first surface, has a group selected from nitrogen-containing groups, phosphonates, phosphate groups (-PO4H2), phosphonic acid groups or their salts, sulfonates (-SO3H) or their salts, carboxyl groups (-COOH) or their salts, hydroxyl groups (-OH), and thiol groups (-SH).

[0207] Furthermore, as a preferred embodiment of the first and second surfaces, the following embodiment (hereinafter also referred to as embodiment B) can be cited: the first surface is a surface composed of a material selected from metals (pure metals or alloys), metal carbides, metal oxides, metal nitrides, and metal oxynitrides; and the second surface is a surface composed of a different type of material from the first surface, and is composed of a material selected from metals (pure metals or alloys), metal carbides, metal oxides, metal nitrides, and metal oxynitrides. The first and second surfaces being composed of different types of materials means selecting two materials selected from the five materials of metal, metal carbides, metal oxides, metal nitrides, and metal oxynitrides as the first and second surfaces.

[0208] As for form B, more specifically, examples include a form where the first surface is a metal surface made of metal and the second surface is a metal oxide surface made of metal oxide (hereinafter also referred to as form B1), a form where the first surface is a metal nitride surface made of metal nitride and the second surface is a metal oxide surface made of metal oxide (hereinafter also referred to as form B2), and a form where the first surface is a metal oxide surface made of metal oxide and the second surface is a metal surface made of metal (hereinafter also referred to as form B3).

[0209] In the case of form B1, examples of metals include copper, cobalt, titanium, tantalum, tungsten, ruthenium, and molybdenum.

[0210] Examples of metal oxides include silicon dioxide, silicon oxycarbide (SiOC), and tetraethyl orthosilicate (TEOS).

[0211] In the case of form B2, titanium nitride can be cited as an example of a metal nitride.

[0212] Examples of metal oxides include silicon dioxide, silicon oxycarbide (SiOC), and tetraethyl orthosilicate (TEOS).

[0213] Furthermore, in the case of form B1 or form B2, from the viewpoint of having better effects of the present invention, it is preferable that the specific compound 1 has a functional group selected from nitrogen-containing groups, phosphonic acid groups (-PO3H2) or their salts, phosphonates, phosphate groups (-PO4H2) or their salts, sulfonyl groups (-SO3H) or their salts, carboxyl groups (-COOH) or their salts, hydroxyl groups (-OH) and thiol groups (-SH) as functional groups bonded or adsorbed on the first surface.

[0214] In particular, when the functional groups bonded or adsorbed on the first surface are nitrogen-containing groups, they tend to bond or adsorb onto tungsten, ruthenium, or molybdenum surfaces, thus further hindering ALD coating. Furthermore, when the functional groups bonded or adsorbed on the first surface are phosphonic acid groups (-PO3H2) or their salts or phosphonates, they tend to bond or adsorb onto copper or cobalt surfaces, thus further hindering ALD coating.

[0215] In the case of form B3, examples of metal oxides include silicon oxide, silicon carbide (SiOC), and tetraethyl orthosilicate (TEOS).

[0216] Silicon is an example of a metal.

[0217] In the case of form B3, from the viewpoint of achieving better results in this invention, it is preferable that specific compound 1 has a hydrolyzable silyl group as a functional group bonded or adsorbed onto the first surface.

[0218] [Process 1]

[0219] The method for manufacturing the modified substrate of the present invention (first embodiment) includes step 1.

[0220] As described above, step 1 is a step of contacting the substrate with the liquid medicine to form a first coating on the first surface. The substrate (hereinafter also simply referred to as "substrate") has at least two surfaces, a first surface and a second surface, which are made of different materials. The liquid medicine (liquid medicine 1) contains a compound (specific compound 1) having functional groups bonded or adsorbed to the first surface and the aforementioned crosslinking groups and having a molecular weight of 500 or less, and a solvent.

[0221] There are no particular limitations on the method of bringing the substrate into contact with the solution 1. For example, methods such as coating or spraying the solution 1 onto the substrate and immersing the substrate in the solution 1 can be cited. There are no particular limitations on the method of coating the solution 1 onto the substrate, and known methods can be used, such as spin coating. Furthermore, when immersing the substrate in the solution 1, the solution 1 can be allowed to convect.

[0222] There is no particular limitation on the temperature of the liquid 1 when the substrate comes into contact with the liquid 1, but it is preferably 0 to 50°C, and more preferably 10 to 30°C.

[0223] Preferably, a rinsing process is performed on a substrate on which a first coating is formed by contacting the substrate with the liquid 1. The rinsing process can remove specific compound 1 from the substrate except for the desired area adhering to the substrate.

[0224] The rinsing method is not particularly limited, and any method that brings the rinsing solution into contact with the substrate can be cited. As a contact method, a method similar to the method of bringing the above-mentioned solution 1 into contact with the substrate can be cited. The temperature of the rinsing solution during contact is not particularly limited, but is preferably 0 to 50°C, and more preferably 10 to 30°C.

[0225] There are no particular limitations on the rinsing solution; any solvent contained in solution 1 can be used as an example. Solvents of the same type as those contained in solution 1 can be used as rinsing solutions.

[0226] [Process 2]

[0227] The method for manufacturing the modified substrate of the present invention (first embodiment) includes step 2.

[0228] As described above, step 2 is a step of performing atomic layer deposition (ALD) on the substrate (the substrate having the first coating) obtained in step 1 to form a second coating on the second surface.

[0229] When the substrate obtained in step 1 is subjected to ALD treatment, since the formation of the second coating is hindered by the first coating, a modified substrate in which the second coating is selectively formed can be obtained on the area where the first coating is not formed (the second surface).

[0230] The materials used in the formation of Langmuir-Blodgett films or self-assembled monolayer films (SAM films) are usually low-molecular-weight materials. Therefore, they are very effective at selectively forming modification films on fine areas of the substrate compared to high-molecular-weight materials. On the other hand, the substrate has poor resistance to heating in most cases during ALD processing.

[0231] In contrast, in step 2 of the present invention, although the specific compound 1 is a low molecular weight material, it has crosslinking groups. Therefore, when the substrate is heated in the ALD process, since the first coating becomes a cured film, it can exert sufficient heat resistance. Thus, it can maintain heat resistance and prevent the formation of ALD coatings in fine areas.

[0232] In the ALD process, the precursor that will become the material for the second coating is supplied to the surface of the substrate obtained in step 1. Generally, two or more of the above-mentioned precursors are used.

[0233] The material constituting the second coating can be controlled by the type of precursor supplied, the supply environment, and the oxidant. There are no particular limitations on the second coating formed by ALD treatment, but metal films, metal oxide films, or metal nitride films are preferred, and metal films or metal oxide films are more preferred.

[0234] Examples of metals that can constitute the aforementioned metal film include aluminum, titanium, chromium, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, palladium, lanthanum, cerium, hafnium, tantalum, tungsten, platinum, and bismuth.

[0235] Examples of metal oxides constituting the aforementioned metal oxide films include aluminum oxide, titanium oxide, zinc oxide, zirconium oxide, hafnium oxide, and tantalum oxide.

[0236] Examples of metal nitrides constituting the aforementioned metal nitride films include titanium nitride and tantalum nitride.

[0237] Furthermore, in the ALD process, a treatment can be performed to degrade the surface of areas where the first coating has not been formed.

[0238] The above-mentioned ALD treatment is not particularly limited, but the thermal ALD method is preferred. Furthermore, as described later, step 4 can be additionally provided as a heating step to allow the crosslinking groups to react with each other.

[0239] From the viewpoint that the cross-linking groups can react with each other more effectively, the substrate heating temperature in the ALD process is preferably 100 to 400°C, more preferably 150 to 400°C, and even more preferably 200 to 300°C.

[0240] In step 2, the difference between the thickness of the second coating on the second surface and the thickness of the second coating on the area where the first coating is formed (the thickness of the second coating on the second surface - the thickness of the second coating on the area where the first coating is formed) is preferably 1.0 nm or more, more preferably 1.2 nm or more, and even more preferably 1.5 nm or more.

[0241] There is no particular upper limit to the aforementioned thickness difference; for example, it can be below 100nm.

[0242] [Method for manufacturing a modified substrate (Second Embodiment)]

[0243] As described above, a second embodiment of the method for manufacturing the modified substrate of the present invention includes: step 1, contacting a substrate with a liquid solution to form a first coating on the first surface, wherein the substrate has at least two surfaces, a first surface and a second surface, which are made of different materials; the liquid solution (hereinafter also referred to as "liquid solution 2") includes a compound having a molecular weight of 500 or less (hereinafter also referred to as "specific compound 2") having a group selected from nitrogen-containing groups, phosphonic acid groups (-PO3H2) or their salts, phosphonates, phosphate groups or their salts, carboxyl groups or their salts, hydroxyl groups, thiol groups and hydrolyzable silyl groups, and crosslinking groups; and a solvent; and step 2, performing atomic layer deposition on the substrate obtained in step 1 to form a second coating on the second surface.

[0244] The following is a detailed description of the medicinal solution 2 used in step 1 above.

[0245] <Potion 2>

[0246] Liquid 2 contains a specific compound 2 and a solvent.

[0247] (Specific compound 2)

[0248] As described above, the specific compound 2 is a compound having a group (specific group) selected from nitrogen-containing group, phosphonic acid group (-PO3H2) or its salt, phosphonate ester, phosphate group or its salt, carboxyl group or its salt, hydroxyl group, thiol group and hydrolyzable silyl group and a crosslinking group and having a molecular weight of 500 or less.

[0249] As will be described later, since the first surface of the substrate preferably contains metal atoms, the specific compound 2 forms a strong bond between the first surface containing metal atoms and the specific group by having the specific group, thereby obtaining a stable first coating.

[0250] The specific morphology and preferred morphology of the specific group are the same as the specific morphology and preferred morphology of the functional group bonded or adsorbed on the first surface in the first embodiment.

[0251] As the aforementioned specific groups, preferably selected from nitrogen-containing groups, phosphonic acid groups (-PO3H2) or their salts, phosphonate esters, phosphate groups or their salts, carboxyl groups or their salts, hydroxyl groups, thiol groups and hydrolyzable silyl groups, more preferably selected from nitrogen-containing groups, phosphonic acid groups (-PO3H2) or their salts, phosphonate esters, carboxyl groups or their salts, hydroxyl groups, thiol groups and hydrolyzable silyl groups, and even more preferably selected from nitrogen-containing groups, phosphonic acid groups (-PO3H2) or their salts and phosphonate esters.

[0252] Compound 2 has crosslinking groups. The specific and preferred forms of the crosslinking groups in Compound 2 are the same as those in Compound 1.

[0253] There is no particular limitation as long as the number of crosslinking groups in the specific compound 2 is 1 or more, preferably 1 to 3, and more preferably 1.

[0254] Compound 2 preferably has a structure that shows orientation. The specific and preferred forms of the structure showing orientation in compound 2 are the same as the specific and preferred forms of the structure showing orientation in compound 1.

[0255] As a specific compound 2, the compound represented by the above formula (S1) is preferred.

[0256] There are no particular restrictions on the molecular weight of the specific compound 2 as long as it is below 500, preferably 50 to 450, more preferably 100 to 450, and even more preferably 150 to 400.

[0257] The content of the specific compound 2 relative to the total mass of the drug solution 2 is preferably 0.0001 to 10.0% by mass, more preferably 0.001 to 1.0% by mass, and even more preferably 0.01 to 0.5% by mass.

[0258] It is also possible to use two or more specific compounds together.

[0259] When using two or more specific compounds 2, it is preferable that their total content is within the above range.

[0260] (solvent)

[0261] The drug solution 2 contains a solvent. The specific form and preferred form of the solvent are the same as those of the solvent contained in the drug solution 1.

[0262] The solvent content in the drug solution is preferably 90 to 99.999% by mass relative to the total mass of the drug solution, more preferably 95 to 99.9% by mass, and even more preferably 97 to 99.9% by mass.

[0263] Solvents can also be used in combination with two or more.

[0264] When using two or more solvents, it is preferable that their total content is within the above range.

[0265] (polymerization inhibitor)

[0266] From the perspective of improving the stability of the pharmaceutical solution, pharmaceutical solution 2 preferably contains a polymerization inhibitor. The specific and preferred forms of the polymerization inhibitor are the same as those of the polymerization inhibitor contained in pharmaceutical solution 1.

[0267] The content of the polymerization inhibitor is preferably 0.0001 parts by mass or more, more preferably 0.001 parts by mass or more, further preferably 0.005 parts by mass or more, and especially preferably 0.010 parts by mass or more, relative to 100 parts by mass of the specific compound 2 mentioned above.

[0268] Furthermore, the content of the polymerization inhibitor is preferably 10.0 parts by mass or less, more preferably 1.000 parts by mass or less, and even more preferably 0.100 parts by mass or less, relative to the content of the specific compound 2 described above.

[0269] Solution 2 may contain one type of polymerization inhibitor or two or more types. When it contains two or more polymerization inhibitors, it is preferable that their combined amount is within the range described above.

[0270] <Method for manufacturing the medicinal liquid>

[0271] There are no particular limitations on the manufacturing method of the above-mentioned liquid medicine 2, and the specific form and preferred form are the same as those of the above-mentioned liquid medicine 1.

[0272] <Substrate>

[0273] In the second embodiment of the method for manufacturing the modified substrate of the present invention, the substrate used is a substrate having at least two surfaces (hereinafter also simply referred to as "substrate") having a first surface and a second surface made of different materials. The specific shape and preferred shape of the substrate described above are the same as those of the substrate used in the first embodiment.

[0274] [Process 1]

[0275] The method for manufacturing the modified substrate of the present invention (second embodiment) includes step 1.

[0276] As described above, step 1 is a step of contacting the substrate with the liquid medicine to form a first coating on the first surface. The substrate has at least two surfaces, a first surface and a second surface, which are made of different materials. The liquid medicine (liquid medicine 2) contains a compound (specific compound 2) with a molecular weight of 500 or less, having a group selected from nitrogen-containing groups, phosphonic acid groups (-PO3H2) or their salts, phosphonates, phosphate groups or their salts, carboxyl groups or their salts, hydroxyl groups, thiol groups and hydrolyzable silyl groups and crosslinking groups, as well as a solvent.

[0277] There are no particular limitations on the method of bringing the substrate into contact with the liquid medicine 2, and the specific and preferred forms are the same as the method of bringing the substrate into contact with the liquid medicine 1.

[0278] Furthermore, it is also preferable to perform a rinsing process on a substrate on which a first coating is formed by contacting the substrate with the liquid 2. The specific form and preferred form of the rinsing method are the same as those of the rinsing method in step 1 of the first embodiment.

[0279] [Process 2]

[0280] The method for manufacturing the modified substrate of the present invention (second embodiment) includes step 2.

[0281] As described above, step 2 involves performing atomic layer deposition (ALD) on the substrate (the substrate having the first coating) obtained in step 1 to form a second coating on the second surface. The specific form and preferred form of step 2 in the second embodiment of the method for manufacturing the modified substrate of the present invention are the same as those in the first embodiment.

[0282] [Other processes]

[0283] [Process 3]

[0284] The method for manufacturing the modified substrate of the present invention (first embodiment and second embodiment) may include step 3, which removes the first coating formed on the substrate in step 1 after step 2. By performing step 3 after step 2, a modified substrate having a second coating formed only on the second surface is obtained.

[0285] There are no particular limitations on the method for removing the first coating; examples include dry etching, wet etching, and combinations thereof.

[0286] As a dry etching method, one example is supplying reactive ions or reactive radicals to the surface of a modified substrate having a first coating. The reactive ions or reactive radicals can be generated by plasma or the like, and preferably by using a mixed gas containing one or more gases selected from oxygen, nitrogen, and hydrogen. This mixed gas may contain rare gases. Furthermore, the dry etching can be a physical etching method utilizing sputtering phenomena.

[0287] In wet etching, the etching solution is simply supplied to the surface of the modified substrate having the first coating. Examples of etching solutions include those containing oxidants such as ozone and those containing organic solvents. Examples of organic solvents in etching solutions containing organic solvents include those found in the aforementioned solutions, with hydrocarbon solvents being preferred.

[0288] [Process 4]

[0289] The method for manufacturing the modified substrate of the present invention (first embodiment and second embodiment) may include step 4, in which the modified substrate is heated. Step 4 is preferably performed before step 2.

[0290] There are no particular limitations on the heating temperature, but it is preferably 100 to 400°C, more preferably 150 to 400°C, and even more preferably 200 to 300°C.

[0291] There are no particular limitations on the heating method; examples include methods involving contact with a heating element (e.g., heating using a heating plate) and methods involving irradiation with infrared radiation.

[0292] [Semiconductor device manufacturing methods]

[0293] The present invention also relates to a method for manufacturing a semiconductor device, which includes the method for manufacturing the above-described modified substrate.

[0294] The method for manufacturing the modified substrate of the present invention can be used in any process for manufacturing semiconductor devices, for example, in the process of processing semiconductor substrates in the manufacturing method of semiconductor devices.

[0295] Example

[0296] The present invention will now be described in further detail based on embodiments.

[0297] 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.

[0298] [Preparation method of the drug solution]

[0299] The components were mixed in the proportions shown in the table below to prepare the solutions used in the examples and comparative examples.

[0300] Furthermore, the preparation, filling, and storage of the pharmaceutical solution are all carried out in a cleanroom that meets ISO Class 2 or lower standards. Moreover, the containers used in the preparation, filling, and storage of the pharmaceutical solution are cleaned with the solvent used in the preparation or the prepared pharmaceutical solution itself.

[0301] [Rating A]

[0302] Following the steps described below, a substrate was prepared to form a first coating on a substrate consisting only of the first surface using the solution described later, and the ALD barrier properties were evaluated.

[0303] [Preparation of the sample substrate for evaluation (first coating formation method)]

[0304] First, as a substrate, a W-layer wafer with a tungsten layer formed by CVD, a Ru-layer wafer with a ruthenium layer formed by CVD, a TiN-layer wafer with a titanium nitride layer formed by CVD, and a TEOS-layer wafer with a tetraethyl orthosilicate (Si(OC2H5)4) layer formed by plasma CVD are prepared on one surface of a commercially available silicon wafer (12 inches in diameter). The film deposition conditions are adjusted so that the thicknesses of the W-layer, Ru-layer, TiN-layer, and TEOS-layer are all 20 nm.

[0305] The silicon wafers described above, as well as the W-layer wafers, Ru-layer wafers, TiN-layer wafers, and TEOS-layer wafers obtained by film formation as described above, were cut into 2cm squares. After being rinsed with isopropanol (IPA), nitrogen gas was blown onto each wafer for drying.

[0306] The substrate was immersed in IPA to perform a rinsing process. The IPA was stirred in the container with a magnetic stirrer at 250 rpm while the substrate was immersed. The temperature of the IPA was set to 25°C and the immersion time was set to 30 seconds.

[0307] After rinsing, each wafer was immersed in its respective chemical solution. While stirring the chemical solution poured into the container at 250 rpm, each wafer was immersed in the solution. The temperature of the chemical solution was set to 25°C, and the immersion time was set to 10 minutes.

[0308] After performing IPA-based rinsing on each wafer after the above impregnation treatment using the same steps as described above, the wafers are dried with nitrogen gas to obtain samples (evaluation samples) on which the first coating is formed.

[0309] [AID Obstacles]

[0310] An alumina layer (ALD coating) was formed on a sample obtained through the fabrication of an evaluation sample substrate (first coating formation method) (evaluation sample) and a sample without the first coating (untreated sample) 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.

[0311] In addition, the ALD treatment temperature was set to 200°C, and ALD treatment was performed on each sample (untreated sample) before the first coating was formed, with a film thickness of 5 nm.

[0312] The thickness of the ALD coating in the samples treated with ALD was measured using an X-ray fluorescence (XRF) instrument (AZX400 manufactured by Rigaku Corporation). The thickness of the ALD coating was measured at five points on the sample, and the average value was taken as the coating thickness.

[0313] The ALD barrier value (nm) will be evaluated by comparing the value obtained from Equation (A) below with the following criteria. The larger the ALD barrier value (nm), the more difficult it is to deposit a coating based on the ALD treatment.

[0314] Equation (A): ALD barrier (nm) = (thickness of ALD coating on untreated sample (5nm)) - (thickness of ALD coating on evaluation sample (nm))

[0315] (Evaluation Criteria)

[0316] A: The ALD barrier is above 2.0nm.

[0317] B: The ALD impedance is greater than 1.0nm and less than 2.0nm.

[0318] C: ALD barrier is less than 1.0 nm.

[0319] [result]

[0320] Table 1, described below, shows the components used in the preparation of the medicinal solution and their content ratios (mass ratios).

[0321] In Table 1, the molecular weight of a specific compound is shown in the "Molecular Weight" column. Additionally, for compound C-1, the molecular weight is the weight-average molecular weight.

[0322] Furthermore, the evaluation results of ALD obstruction are shown in Tables 2-5 below.

[0323] Additionally, Table 2 shows the results assuming that the W layer is used as the first surface and the TEOS layer is used as the second surface.

[0324] Table 3 shows the results assuming a Ru layer is used as the first surface and a TEOS layer is used as the second surface.

[0325] Table 4 shows the results assuming a TiN layer is used as the first surface and a TEOS layer is used as the second surface.

[0326] Table 5 shows the results assuming a TEOS layer is used as the first surface and a Si layer is used as the second surface.

[0327] In Tables 2-5, the "Film Thickness" column shows the film thickness of the ALD coating formed using each evaluation sample. Furthermore, the "ALD Resistance" column shows the ALD resistance calculated according to formula (A) above.

[0328] Table 1 shows the structure or name of each component used in the preparation of the drug solution.

[0329] <Specific compound>

[0330] The structures of specific compounds (A-1 to A-10) are shown below.

[0331] In addition, a specific compound is a compound equivalent to specific compound 1 or specific compound 2.

[0332] [Chemical Formula 1]

[0333]

[0334] <Other Compounds>

[0335] •B-1: The following compounds

[0336] [Chemical Formula 2]

[0337] CH3(CH2) 16 CH2NH2

[0338] • C-1: Polymers with the following structures described in paragraphs

[0135] to

[0136] of International Publication No. 2019 / 167704

[0339] The polymer with the following structure was synthesized according to the method described in paragraph

[0135] of International Publication No. 2019 / 167704. The synthesized polymer with the following structure has a weight-average molecular weight of 5200 and a number-average molecular weight of 4900.

[0340] [Chemical Formula 3]

[0341]

[0342] Solvent

[0343] S-1: Propylene glycol monomethyl ether

[0344] S-2: Methyl isobutyl methanol

[0345] [Table 1]

[0346]

[0347] [Table 2]

[0348]

[0349] [Table 3]

[0350]

[0351] [Table 4]

[0352]

[0353] [Table 5]

[0354]

[0355] In Table 2, in Examples 1A to 15A where the manufacturing method of the present invention was used, the ALD resistance of the W-layer wafer was evaluated as A or B, while the ALD resistance of the TEOS-layer wafer was evaluated as C. From these results, it can be seen that because a first coating is formed on the W layer but not on the TEOS layer, during ALD processing, the formation of the ALD coating on the W layer is hindered by the first coating, while an ALD coating is formed on the TEOS layer without hindrance.

[0356] Therefore, it is believed that when a modified substrate is manufactured using a substrate having a W layer as the first surface and a TEOS layer as the second surface, a substrate with an ALD coating selectively and well formed on the TEOS layer can be obtained.

[0357] Examples 1B to 16B, which evaluated the Ru layer and the TEOS layer, Examples 1C to 15C, which evaluated the TiN layer and the TEOS layer, and Example 1D, which evaluated the TEOS layer and the Si layer, can also be considered the same as Examples 1A to 15A.

[0358] Regarding the evaluation of the embodiments, in Comparative Example 1A, where no specific compound was used, the ALD barrier value was rated as C for both the W layer and the TEOS layer. That is, in Comparative Example 1A, since the coating as in the embodiment was not formed on both the W layer and the TEOS layer, an ALD coating was formed on both the W layer and the TEOS layer. Therefore, when using the solution R-1 to perform the above steps 1 and 2 on a substrate having a W layer as the first surface and a TEOS layer as the second surface, the ALD coating was formed on both the first and second surfaces, and the desired effect was not obtained.

[0359] Furthermore, in Comparative Example 2A, the ALD barrier value was rated as A for both the W layer and the TEOS layer. That is, in Comparative Example 2A, the coating as in the embodiment was formed on both the W layer and the TEOS layer, making it difficult to form an ALD coating on either the W layer or the TEOS layer. Therefore, when using the solution R-2 to perform the above steps 1 and 2 on a substrate having a W layer as the first surface and a TEOS layer as the second surface, the formation of the ALD coating on both the first and second surfaces was suppressed, and the desired effect was not achieved.

[0360] The same tendency was also observed in Comparative Examples 1B-2B and 1C-2C.

[0361] Furthermore, comparisons of Examples 1A to 13A have confirmed that the effects of the present invention are even better when the crosslinking group in a specific compound 1 or a specific compound 2 is styrene or vinyl.

[0362] It was confirmed from comparisons of Examples 6A to 8A with Examples 14A and 15A that the effects of the present invention are even better when a specific compound 1 or specific compound 2 has a divalent aliphatic hydrocarbon group with 6 to 18 carbon atoms that can have ether-like oxygen atoms.

[0363] Furthermore, the substrate (substrate 1) is brought into contact with each of the pharmaceutical solutions listed in Table 1. The substrate (substrate 1) has at least one of the W layer, Ru layer and TiN layer as the first surface and a TEOS layer as the second surface. Then, the ALD treatment is performed with the same steps as the ALD treatment performed in the above-mentioned [ALD barrier], and it is confirmed that it has the same tendency as the evaluation results shown in Tables 2 to 4, and a substrate 1 with an ALD coating selectively and well formed on the TEOS layer is obtained.

[0364] Furthermore, when substrate 1 is replaced by substrate 2, which has a TEOS layer as the first surface and a Si layer as the second surface, and when the solution described in Table 1 is used, it is confirmed that there is a tendency to have the same evaluation results as shown in Table 5, and substrate 2 with ALD coating selectively and well formed on the Si layer can be obtained.

[0365] [Rating B]

[0366] For Examples 101–132, ALD resistance and drug solution stability were evaluated.

[0367] [ALD Obstructive]

[0368] The ALD barrier properties of the aforementioned W-layer wafer and TEOS-layer wafer were evaluated using solutions Y-1 to Y-32 having the compositions described later. The ALD barrier properties were evaluated using the same procedures as those described above for [ALD barrier properties].

[0369] [Evaluation of drug solution stability]

[0370] The stability of the solutions Y-1 to Y-32, which have the compositions described below, was evaluated according to the following steps.

[0371] The turbidity of each drug solution was measured after being stored at 45°C for one month. The turbidity was measured using a Mitsubishi Chemical Analytech Co., Ltd. PT-200 integrating sphere turbidimeter.

[0372] The stability of the drug solution was evaluated based on the measured turbidity and according to the following evaluation criteria. The lower the turbidity, the better the stability of the drug solution.

[0373] -Evaluation Criteria-

[0374] A: Turbidity is less than 0.1 ppm.

[0375] B: Turbidity is above 0.1 ppm.

[0376] [result]

[0377] The evaluation results of ALD resistance and drug solution stability in Examples 101 to 132 are shown in Tables 6 to 9 below.

[0378] The solutions Y-1 to Y-32 used in each embodiment were prepared by mixing 100 parts by mass of each specific compound with the polymerization inhibitors shown in Tables 6 to 9, and then adding solvent S-1 to make the solid component concentration 0.1% by mass. The solid component refers to the specific compound and the polymerization inhibitor.

[0379] The names of the polymerization inhibitors used in the preparation of the pharmaceutical solution are listed in Tables 6-9 below. Additionally, the structures or names of the specific compounds used in the preparation of the pharmaceutical solution and solvent S-1 are as described in [Evaluation A].

[0380] <Polymerization inhibitors>

[0381] D-1: 4-Methoxyphenol

[0382] D-2: N-nitroso-N-phenylhydroxylamine aluminum

[0383] • D-3: Poly(4-methacryloyloxy-2,2,6,6-tetramethylpiperidine-N-oxy)

[0384] D-4: 4-tert-butylcatechol

[0385] D-5: 1,4-Benzoylene

[0386] D-6: Phenothiazine

[0387] D-7: N,N-Diethylhydroxyamine

[0388] D-8: 4-Hydroxy-2,2,6,6-Tetramethylpiperidine-1-oxy

[0389] D-9: Copper Iron Spirit

[0390] D-10: 2,4-bis(octylthiomethyl)-6-methylphenol

[0391] In Tables 6-9, entries separated by " / " in the "Type" column indicate that the substance contains multiple compounds, and entries separated by " / " in the "Content" column indicate the contents of the multiple compounds in sequence. For example, the "polymerization inhibitor" in Example 128 contains "D-1" and "D-5", and the contents are expressed as "0.01" and "0.01" parts by mass, respectively.

[0392] [Table 6]

[0393]

[0394] [Table 7]

[0395]

[0396] [Table 8]

[0397]

[0398] [Table 9]

[0399]

[0400] The results in Tables 6-9 confirm that the manufacturing method of the modified substrates in Examples 101-132 is the same as that in Examples 1A-15A. The formation of the ALD coating in the W layer is hindered by the first coating, while the ALD coating is formed without hindrance in the TEOS layer and the ALD coating can be formed selectively and well.

[0401] [Rating C]

[0402] Following the steps described in Tables 10-13 below, a substrate on which a first coating is formed on a substrate consisting only of the first surface was prepared, and the ALD barrier properties were evaluated.

[0403] [Preparation of the sample substrate for evaluation (first coating formation method)]

[0404] First, a commercially available silicon wafer (12 inches in diameter) is prepared as a substrate. Cu-layer wafers, Co-layer wafers, SiOC-layer wafers, W-layer wafers, Ru-layer wafers, and Mo-layer wafers are prepared by forming copper (Cu), cobalt (Co), silicon carbide (SiOC), tungsten (W), ruthenium (Ru), and molybdenum (Mo) layers on one surface of the silicon wafer, respectively. (Hereinafter, these are also referred to as "layered wafers").

[0405] In addition, the Cu and Co layers are formed by sputtering, the SiOC layer is formed by plasma CVD (chemical vapor deposition), and the W, Ru, and Mo layers are formed by CVD.

[0406] The film formation conditions were adjusted so that the thickness of each layer was 20 nm.

[0407] Next, the solutions described in Tables 10 to 13 were used on the silicon wafer and the wafer with the layer prepared in the above steps to prepare samples with the first coating formed on each wafer. As a specific step, the samples were prepared according to the steps described in Evaluation A above in "Preparation of Evaluation Sample Substrate (Method for Forming the First Coating)".

[0408] [AID Obstacles]

[0409] Titanium nitride (ALD coating) layers were formed using an atomic layer deposition apparatus (Flex-AL, manufactured by Oxford Corporation) on samples obtained through the fabrication of an evaluation sample substrate (first coating formation method) (evaluation sample) and samples without the first coating (untreated sample). TDMAT (tetra(dimethylamino)titanium) was used as the organometallic raw material, and ammonia was used as the reducing agent.

[0410] In addition, the ALD treatment temperature was set to 300°C, and ALD treatment was performed on each sample (untreated sample) before the first coating was formed, with a film thickness of 5 nm.

[0411] The thickness of the ALD coating in the samples treated with ALD was measured using an X-ray fluorescence (XRF) instrument (AZX400 manufactured by Rigaku Corporation). The thickness of the ALD coating was measured at five points on the sample, and the average value was taken as the coating thickness.

[0412] The ALD barrier value (nm) will be evaluated by comparing the value obtained from Equation (A) below with the following criteria. The larger the ALD barrier value (nm), the more difficult it is to deposit a coating based on the ALD treatment.

[0413] Equation (A): ALD barrier (nm) = (thickness of ALD coating on untreated sample (5nm)) - (thickness of ALD coating on evaluation sample (nm))

[0414] (Evaluation Criteria)

[0415] A: The ALD barrier is above 2.0nm.

[0416] B: The ALD impedance is greater than 1.0nm and less than 2.0nm.

[0417] C: ALD barrier is less than 1.0 nm.

[0418] [result]

[0419] Tables 10-13, described below, show the components used in the preparation of the pharmaceutical solution and their content ratios (mass ratios). Additionally, as a component not listed in the tables, each pharmaceutical solution, as a polymerization inhibitor, contains 100 ppm by mass of 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxy.

[0420] In Tables 10-13, the "Mw" column shows the molecular weight of a specific compound.

[0421] Furthermore, the evaluation results of ALD obstruction are shown in Tables 14-17.

[0422] In addition, Tables 14 and 16 show the results when a surface consisting of at least one of a Cu layer and a Co layer is used as the first surface, and a surface consisting of at least one of a SiOx (silicon wafer) layer and a SiOC layer is used as the second surface.

[0423] Tables 15 and 17 show the results when a surface consisting of at least one of a W layer, a Ru layer, and a Mo layer is used as the first surface, and a surface consisting of at least one of a SiOx (silicon wafer) layer and a SiOC layer is used as the second surface.

[0424] [Table 10]

[0425]

[0426] [Table 11]

[0427]

[0428] [Table 12]

[0429]

[0430] [Table 13]

[0431]

[0432] [Table 14]

[0433]

[0434] [Table 15]

[0435]

[0436] [Table 16]

[0437]

[0438] [Table 17]

[0439]

[0440] [Table 18]

[0441]

[0442] [Table 19]

[0443]

[0444] As shown in the table, the manufacturing method of the modified substrate according to the present invention confirms that a modified substrate with a selectively good ALD coating formed in a specified area can be manufactured by performing ALD processing.

[0445] Furthermore, when it is confirmed from comparisons of Examples Y-1 to Y-9 that the crosslinking group in a specific compound 1 or specific compound 2 is styrene, vinylnaphthyl, or vinyl, the effects of the present invention are even more superior.

[0446] The effects of the present invention are even better when it is confirmed from comparisons of Examples X-1 to X-5 and Examples X-6 to X-8 that a specific compound 1 or specific compound 2 has a divalent aliphatic hydrocarbon group that can have ether oxygen atoms with 6 to 18 carbon atoms.

[0447] When it is confirmed, through comparisons of Examples Y-1 to Y-8 and Examples Y-10 to Y-11, that a specific compound 1 or specific compound 2 has a primary amino group, the effects of the present invention are even more superior.

[0448] It has been confirmed from comparisons of Examples X-12 to X-22 or Examples Y-15 to Y-24 that the present invention is more effective when the water content is less than 80% by mass relative to the total mass of the solvent.

[0449] Furthermore, even when PDMAT (penta(dimethylamino)tantalum) was used instead of TDMAT in the above-described [ALD resistance] process to form a tantalum nitride layer on each evaluation sample, the same results as those in Tables 14-17 were confirmed when evaluating the ALD resistance amount in the above-described [ALD resistance] process.

Claims

1. A method for manufacturing a modified substrate, comprising: Step 1, contacting a substrate with a chemical solution to form a first coating on a first surface of the substrate, wherein the substrate has at least two surfaces, the first surface and the second surface, which are made of different materials, and the chemical solution contains a compound having a functional group and a cross-linking group bonded to or adsorbed on the first surface and having a molecular weight of 500 or less, and a solvent; and In step 2, an atomic layer deposition process is performed on the substrate obtained in step 1 to form a second coating on the second surface.

2. The method for manufacturing a modified substrate according to claim 1, wherein: The functional group bonded or adsorbed to the first surface is selected from a nitrogen-containing group, a phosphonic acid group or a salt thereof, a phosphonate ester, a phosphoric acid group or a salt thereof, a carboxyl group or a salt thereof, a hydroxyl group, a thiol group, and a hydrolyzable silyl group.

3. The method for manufacturing a modified substrate according to claim 1, wherein: The crosslinking group is an ethylenically unsaturated group.

4. The method for manufacturing a modified substrate according to claim 1, wherein: The crosslinking group is selected from an acryloyl group, a methacryloyl group, a vinyl ether group, a styrene group, a vinyl naphthyl group and a vinyl group.

5. A method for manufacturing a modified substrate, comprising: Step 1, contacting a substrate with a chemical solution to form a first coating on a first surface of the substrate, wherein the substrate has at least two surfaces, the first surface and the second surface, which are made of different materials, and the chemical solution contains a compound having a group selected from a nitrogen-containing group, a phosphonic acid group or a salt thereof, a phosphonic acid ester, a phosphoric acid group or a salt thereof, a carboxyl group or a salt thereof, a hydroxyl group, a thiol group, and a hydrolyzable silyl group, and a crosslinking group and having a molecular weight of 500 or less, and a solvent; and In step 2, an atomic layer deposition process is performed on the substrate obtained in step 1 to form a second coating on the second surface.

6. The method for manufacturing a modified substrate according to claim 5, wherein: The crosslinking group is an ethylenically unsaturated group.

7. The method for manufacturing a modified substrate according to claim 5, wherein: The crosslinking group is selected from an acryloyl group, a methacryloyl group, a vinyl ether group, a styrene group, a vinyl naphthyl group and a vinyl group.

8. The method for producing a modified substrate according to any one of claims 1 to 7, wherein: At least one of the first surface and the second surface is a metal surface made of metal.

9. The method for producing a modified substrate according to any one of claims 1 to 7, wherein: At least one of the first surface and the second surface includes at least one metal atom selected from the group consisting of copper atoms, cobalt atoms, titanium atoms, tantalum atoms, tungsten atoms, ruthenium atoms, and molybdenum atoms.

10. The method for manufacturing a modified substrate according to claim 9, wherein: At least one of the first surface and the second surface includes at least one metal atom selected from the group consisting of titanium atoms, tungsten atoms, ruthenium atoms, and molybdenum atoms.

11. The method for producing a modified substrate according to any one of claims 1 to 7, wherein: The second coating is a metal film or a metal oxide film.

12. The method for manufacturing a modified substrate according to any one of claims 1 to 7, further comprising: Step 3, after step 2, removing the first coating.

13. The method for manufacturing a modified substrate according to claim 1, wherein: The drug solution contains a polymerization inhibitor.

14. The method for manufacturing a modified substrate according to claim 13, wherein: The polymerization inhibitor comprises at least one compound selected from phenolic compounds, quinone compounds, free radical compounds, amine compounds and phosphine compounds.

15. The method for manufacturing a modified substrate according to claim 13, wherein: The content of the polymerization inhibitor is 0.001 to 1.000 parts by mass based on 100 parts by mass of the compound.

16. The method for manufacturing a modified substrate according to claim 13, wherein: The content of the polymerization inhibitor is 0.01 parts by mass or more based on 100 parts by mass of the compound.

17. The method for manufacturing a modified substrate according to claim 5, wherein: The drug solution contains a polymerization inhibitor.

18. The method for manufacturing a modified substrate according to claim 17, wherein: The polymerization inhibitor comprises at least one compound selected from phenolic compounds, quinone compounds, free radical compounds, amine compounds and phosphine compounds.

19. The method for manufacturing a modified substrate according to claim 17, wherein: The content of the polymerization inhibitor is 0.001 to 1.000 parts by mass based on 100 parts by mass of the compound.

20. The method for manufacturing a modified substrate according to claim 17, wherein: The content of the polymerization inhibitor is 0.01 parts by mass or more based on 100 parts by mass of the compound.

21. The method for manufacturing a modified substrate according to claim 1 or 5, wherein: The medical solution contains water.

22. The method for manufacturing a modified substrate according to claim 21, wherein: The content of the water is 80% by mass or less relative to the total mass of the solvent.

23. The method for manufacturing a modified substrate according to claim 1 or 5, wherein: The drug solution contains three or more of the solvents. 24 . A method for manufacturing a semiconductor device, comprising the method for manufacturing a modified substrate according to claim 1 and claim 13 .

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