Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/04—Coating on selected surface areas, e.g. using masks
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
  • H10P14/63—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by the formation processes
  • H10P14/6326—Deposition processes
  • H10P14/6328—Deposition from the gas or vapour phase
  • H10P14/6334—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
  • H10P14/6339—Deposition from the gas or vapour phase using decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
  • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
  • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/02—Pretreatment of the material to be coated
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/02—Pretreatment of the material to be coated
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
  • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
  • C23C16/40—Oxides
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
  • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
  • C23C16/40—Oxides
  • C23C16/403—Oxides of aluminium, magnesium or beryllium
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
  • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
  • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
  • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
  • C23C16/45523—Pulsed gas flow or change of composition over time
  • C23C16/45525—Atomic layer deposition [ALD]
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
  • H10P14/24—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using chemical vapour deposition [CVD]
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
  • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating materials
  • H10P14/69—Inorganic materials
  • H10P14/692—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses
  • H10P14/6938—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides
  • H10P14/6939—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides characterised by the metal
  • H10P14/69391—Inorganic materials composed of oxides, glassy oxides or oxide-based glasses the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides characterised by the metal the material containing aluminium, e.g. Al2O3

Definitions

• the present invention relates to a method for manufacturing a modified substrate and a method for manufacturing a semiconductor device.
• Non-Patent Document 1 reports that a low molecular weight aminosilane compound is adsorbed onto the silicon dioxide surface on a substrate as an inhibitor, and then an aluminum oxide layer is formed by atomic layer deposition using dimethylaluminum isopropoxide and water as precursors, thereby inhibiting the growth of the aluminum oxide layer in the area where the low molecular weight aminosilane is adsorbed.
• a method has been considered for forming a fine pattern on a substrate having a plurality of regions made of different materials on its surface (for example, a metal region containing metal atoms and an insulating region containing an insulator), in which one of the regions is modified to form a film (modified film), and then an ALD process is performed, thereby forming an ALD film in the region where the modified film is not formed, without forming a coating by ALD (ALD coating).
• ALD coating ALD coating
• the present inventors have studied the technology described in Non-Patent Document 1, and after forming the modified film using the low molecular weight aminosilane compound, they tried to form an ALD coating on a region where the modified film was not formed. However, a thick ALD coating was formed even on the region where the modified film was formed (on the modified film). In other words, it was difficult to form an ALD coating with good selectivity on the region where the modified film was not formed.
• the present invention aims to provide a method for manufacturing a modified substrate, which can perform ALD processing to produce a modified substrate on which an ALD coating is formed with good selectivity in a specified area, and a method for manufacturing a semiconductor device related to the method for manufacturing the modified substrate.
• a method for producing a modified substrate comprising: a step 2 of subjecting the substrate obtained in the step 1 to an atomic layer deposition process to form a second coating on the second surface.
• a method for producing a modified substrate comprising: a step 2 of subjecting the substrate obtained in the step 1 to an atomic layer deposition process to form a second coating on the second surface.
• [20] The method for producing a modified substrate according to [17] or [18], wherein the content of the polymerization inhibitor is 0.01 parts by mass or more relative to 100 parts by mass of the compound.
• [21] The method for producing a modified substrate according to any one of [1] to [20], wherein the chemical solution contains water.
• [22] The method for producing a modified substrate according to [21], wherein the content of the water is 80 mass % or less based on the total mass of the solvent.
• a method for producing a semiconductor device comprising the method for producing a modified substrate according to any one of [1] to [23].
• the present invention provides a method for producing a modified substrate in which an ALD treatment is performed to produce a modified substrate on which an ALD coating is formed with good selectivity in a specified area, and a method for producing a semiconductor device related to the modified substrate production method.
• a numerical range expressed using “to” means a range that includes the numerical values before and after "to” as the lower and upper limits.
• the compounds described herein may contain structural isomers, optical isomers, and isotopes.
• the compounds may contain one or more structural isomers, optical isomers, and isotopes.
• the bonding direction of a divalent group (for example, -COO-) may be either "X-O-CO-Z" or "X-CO-O-Z" when Y in a compound represented by "X-Y-Z” is -COO-.
• the molecular weight of a compound having a molecular weight distribution is the weight average molecular weight.
• a first embodiment of the method for producing a modified substrate of the present invention is a method for producing a modified substrate, comprising: step 1 of contacting a substrate having at least two surfaces, i.e., a first surface and a second surface, made of different materials, with a chemical solution containing a compound (hereinafter also referred to as "specific compound 1") having a functional group bonded to or adsorbed on the first surface and a crosslinkable group, and having a molecular weight of 500 or less, and a solvent, to form a first coating on the first surface; and step 2 of performing atomic layer deposition treatment on the substrate obtained in step 1 to form a second coating on the second surface.
• a compound hereinafter also referred to as "specific compound 1"
• a second embodiment of the method for producing a modified substrate of the present invention is a method for producing a modified substrate, comprising: a step 1 of contacting a substrate having at least two surfaces, i.e., a first surface and a second surface, each of which is made of a material different from each other, with a chemical solution containing a compound having a molecular weight of 500 or less (hereinafter also referred to as a "specific compound 2”) and a group selected from the group consisting of 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 crosslinkable group (hereinafter also referred to as a "specific group”), and a solvent, to form a first coating on the first surface; and a step 2 of performing an atomic
• the chemical solution used in the method for producing a modified substrate of the present invention contains specific compound 1 having a functional group that bonds to or is adsorbed to the first surface, or specific compound 2 having a specific group, so that the functional group in specific compound 1 that bonds to or is adsorbed to the first surface, or the specific group in specific compound 2, bonds to or is adsorbed to the first surface, and as a result, a first coating is easily formed on the first surface.
• the first coating contains a component derived from specific compound 1 or specific compound 2.
• the first embodiment of the method for producing a modified substrate of the present invention includes step 1.
• Step 1 is a step of contacting a substrate having at least two surfaces, a first surface and a second surface, each of which is made of a different material, with a chemical solution (hereinafter also referred to as "chemical solution 1") containing a compound (specific compound 1) having a functional group and a crosslinkable group that bonds to or adsorbs to the first surface and a molecular weight of 500 or less, and a solvent, to form a first coating on the first surface.
• chemical solution 1 used in step 1 will be described in detail below.
• the drug solution 1 contains a specific compound 1 and a solvent.
• specific compound 1 is a compound having a functional group capable of binding to or adsorbing to the first surface and a crosslinkable group, and having a molecular weight of 500 or less.
• the functional group bound or adsorbed to the first surface may form any bond or interaction with the first surface, such as a covalent bond, a coordinate bond, an ionic bond, a hydrogen bond, a van der Waals bond, and a metallic bond.
• the first surface preferably contains metal atoms, and therefore the functional group that bonds to or is adsorbed onto the first surface is preferably a functional group that bonds to or is adsorbed onto a surface that contains metal atoms.
• Examples of functional groups that bond to or are adsorbed to the first surface include nitrogen - containing groups, phosphonic acid esters, phosphate groups (-PO4H2 ) or salts thereof, phosphonic acid groups ( -PO3H2 ) or salts thereof, sulfo groups ( -SO3H ) or salts thereof, carboxy groups (-COOH) or salts thereof, hydroxy groups (-OH), thiol groups (-SH), and hydrolyzable silyl groups.
• the functional group bonded to or adsorbed onto the first surface is preferably a group selected from the group consisting of 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 carboxy group or a salt thereof, a hydroxy group, a thiol group, and a hydrolyzable silyl group, more preferably a group selected from the group consisting of a nitrogen-containing group, a phosphonic acid group or a salt thereof, a phosphonic acid ester, a carboxy group or a salt thereof, a hydroxy group, a thiol group, and a hydrolyzable silyl group, and even more preferably a group selected from the group consisting of a nitrogen-containing group, a phosphonic acid group or a salt thereof, and a phosphonic acid ester.
• nitrogen-containing group examples include a primary amino group (-NH 2 ), a secondary amino group (-NR T H), a tertiary amino group (-NR T 2 ), and a quaternary ammonium group (-N + R T 3 ), with a primary amino group, a secondary amino group, or a tertiary amino group being preferred, and a primary amino group being more preferred.
• R 1 T represents an alkyl group having 1 to 3 carbon atoms, and multiple R 1 T may be different from each other. Multiple R 1 T may be bonded to each other to form a ring.
• the ring formed is a ring containing a nitrogen atom, and examples of the ring include a pyrrolidine ring, a piperidine ring, and a piperazine ring.
• the nitrogen-containing group may be a nitrogen-containing heteroaryl group, which may be a single ring or a multiple ring.
• Examples of the nitrogen-containing heteroaryl group include a pyridyl group, a triazine group, a pyrrole group, a pyrazole group, an imidazole group, a pyrazole group, a triazole group, a benzimidazole group, and a benztriazole group.
• the salt of a phosphate group refers to a group represented by -PO 4 2- Ct n+ 2/n .
• Ct n+ represents an n-valent cation, where n represents 1 or 2.
• monovalent cations include Li + , Na + , K + , and NH 4 + .
• divalent cations include Mg 2+ and Ca 2+ .
• Ct n+ represents a divalent cation, the number is one.
• a compound having a phosphate group is also called a "phosphate compound" and the functional group name is also called "-phosphate".
• the salt of a phosphonic acid group refers to a group represented by -PO 3 2- Ct n+ 2/n , where Ct n+ represents an n-valent cation, where n is 1 or 2.
• Examples of the monovalent cation and the divalent cation include the same cations as those explained above for the salt of a phosphate group, and the numbers thereof are also the same.
• the phosphonate ester refers to a group represented by -PO 3 R P 2. Each R P independently represents a hydrogen atom or an organic group. However, at least one of the two R Ps present represents an organic group.
• the phosphonate ester is preferably a monoester.
• one of the two R Ps present is a hydrogen atom and the other is an organic group.
• the organic group is preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms, more preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms.
• the aliphatic hydrocarbon group and alkyl group may be linear, branched, or cyclic.
• a compound having a phosphonic acid group is also called a "phosphonic acid compound.”
• the salt of a sulfo group refers to a group represented by -SO 3 - Ct + , where Ct + represents a monovalent cation, and examples of the monovalent cation include the same cations as those explained above for the salt of a phosphate group.
• the salt of a carboxy group refers to a group represented by -COO - Ct + , where Ct + represents a monovalent cation, and examples of such a cation include the same monovalent cations as those explained above for the salt of a phosphate group.
• the hydroxy group may be either an alcoholic hydroxy group (a hydroxy group bonded to an aliphatic hydrocarbon) or a phenolic hydroxy group (a hydroxy group bonded to an aromatic hydrocarbon), with an alcoholic hydroxy group being preferred.
• the hydrolyzable silyl group refers to a group that has a silicon atom and is converted into a group capable of forming a bond with the first surface by reacting with water.
• Examples of the hydrolyzable silyl group include an alkoxysilyl group and a chlorosilyl group (a group having a -Si-Cl structure).
• the number of alkoxy groups bonded to a silicon atom (Si atom) is not particularly limited, but is preferably 2 or more, and more preferably 3.
• the number of carbon atoms in the alkoxy group bonded to the Si atom is preferably 1 to 6, and more preferably 1 to 3.
• the alkoxysilyl group is preferably a trimethoxysilyl group or a triethoxysilyl group.
• the number of chlorine atoms bonded to the Si atom is preferably 1 to 3, and more preferably 1.
• the chlorosilyl group is preferably a dialkylmonochlorosilyl group or a monoalkyldichlorosilyl group.
• the alkyl group may be linear, cyclic or branched, but is preferably linear. Of these, the alkyl group is preferably a methyl group.
• the number of functional groups that specific compound 1 has that are bonded to or adsorbed on the first surface is not particularly limited as long as it is 1 or more, but 1 to 3 is preferable, and 1 is more preferable.
• the crosslinkable group is not particularly limited as long as it can form a bond between the crosslinkable groups by heating.
• the crosslinkable group include a radical polymerizable group, a cationic polymerizable group, and an anionic polymerizable group, and an ethylenically unsaturated group is preferred.
• a group selected from the group consisting of an acryloyl group, a methacryloyl group, a vinyl ether group, a styryl group, a vinyl naphthyl group, and a vinyl group is preferable, and a styryl group, a vinyl naphthyl group, or a vinyl group is more preferable.
• the vinyl naphthyl group is preferably a group obtained by removing the hydrogen atom at the 6-position from 2-vinylnaphthalene.
• the vinyl group is a group represented by CH 2 ⁇ CH--, but in this specification, an acryloyl group, a methacryloyl group, a vinyl ether group, a styryl group, and a vinyl naphthyl group are all treated as groups different from a vinyl group.
• an acryloyl group, a methacryloyl group, a vinyl ether group, a styryl group, and a vinyl naphthyl group include a structure represented by CH 2 ⁇ CH--, they are treated as groups different from a vinyl group.
• the number of crosslinkable groups possessed by specific compound 1 is not particularly limited as long as it is 1 or more, but 1 to 3 is preferable, and 1 is more preferable.
• the specific compound 1 preferably has a structure exhibiting orientation.
• the structure exhibiting orientation refers to a structure having a function of orienting the specific compound 1 in a direction perpendicular to the first surface when the substrate and the chemical solution 1 are brought into contact with each other to form a first coating on the first surface.
• the structure exhibiting orientation is not particularly limited, and examples thereof include divalent aliphatic hydrocarbon groups which may have an etheric oxygen atom, divalent aromatic ring groups, and groups formed by combining these. Among these, divalent aliphatic hydrocarbon groups which may have an etheric oxygen atom are preferred.
• the divalent aliphatic hydrocarbon group may be linear, branched or cyclic, preferably linear.
• Examples of the divalent aliphatic hydrocarbon group include alkylene groups, alkenylene groups and alkynylene groups, with alkylene groups being preferred.
• the number of carbon atoms in the divalent aliphatic hydrocarbon group is not particularly limited, but 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.
• the divalent aromatic ring group may be either a divalent aromatic hydrocarbon group (arylene group) or a divalent aromatic heterocyclic group (heteroarylene group), with an arylene group being preferred.
• the divalent aromatic ring group may be either a monocyclic or polycyclic group.
• the divalent aromatic ring group preferably has 5 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms.
• An example of the arylene group is a phenylene group.
• An example of a heteroarylene group is a group formed by removing two hydrogen atoms from pyridine.
• a compound represented by formula (S1) is preferable.
• X 1 -L 1 -Y 1 formula (S1) represents a group selected from the group consisting of 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 carboxy group or a salt thereof, a hydroxy group, a thiol group, and a hydrolyzable silyl group.
• Specific and preferred embodiments of each group represented by X1 are as described above for the functional group bonded to or adsorbed on the first surface. Of the groups represented by X1 , a primary amino group is particularly preferred.
• Y1 represents an ethylenically unsaturated group.
• the ethylenically unsaturated group represented by Y1 is preferably a group selected from the group consisting of an acryloyl group, a methacryloyl group, a vinyl ether group, a styryl group, a vinyl naphthyl group, and a vinyl group.
• L 1 represents a divalent aliphatic hydrocarbon group which may have an etheric oxygen atom, a divalent aromatic ring group, or a group formed by combining these.
• the divalent aliphatic hydrocarbon group is preferably an alkylene group which may have an etheric oxygen atom, and more preferably an alkylene group having 6 to 18 carbon atoms which may have an etheric oxygen atom.
• the divalent aromatic ring group is preferably a phenylene group.
• the molecular weight of specific compound 1 is not particularly limited as long as it is 500 or less, but is preferably 50 to 450, more preferably 100 to 450, and even more preferably 150 to 400.
• the content of the specific compound 1 is preferably 0.0001 to 10.0 mass %, more preferably 0.001 to 1.0 mass %, and even more preferably 0.01 to 0.5 mass %, based on the total mass of the drug solution 1.
• the specific compound 1 may be used in combination of two or more kinds. When two or more types of specific compound 1 are used in combination, the total content thereof is preferably within the above range.
• the chemical solution 1 contains a solvent.
• Solvents include water and organic solvents. Examples of the organic solvent include hydrocarbon solvents, alcohol solvents, polyol solvents, glycol ether solvents, ether solvents, ketone solvents, amide solvents, sulfur-containing solvents, and ester solvents.
• 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.
• alcohol-based solvents include aliphatic alcohol-based solvents having 1 to 18 carbon atoms, such as methanol, ethanol, 1-propanol, 2-propanol (also referred to as isopropyl alcohol (IPA)), 2-butanol, isobutyl alcohol, tert-butyl alcohol, isopentyl alcohol, and 4-methyl-2-pentanol (also referred to as methyl isobutyl carbinol (MIBC)); alicyclic alcohol-based solvents having 3 to 18 carbon atoms, such as cyclohexanol; aromatic alcohol-based solvents, such as benzyl alcohol; and ketone alcohol-based solvents, such as diacetone alcohol.
• the alcohol solvent preferably has 1 to 8 carbon atoms, more preferably 2 to 7 carbon atoms, and even more preferably 3 to 6 carbon atoms.
• polyol-based solvents examples include glycol-based solvents having 2 to 18 carbon atoms.
• Glycol solvents include ethylene glycol, propylene glycol (1,2-propanediol), 1,3-propanediol, diethylene glycol, and dipropylene glycol.
• glycol ether solvents include glycol monoether solvents having 3 to 19 carbon atoms.
• glycol monoether solvents include 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, dipropy
• Ketone solvents include, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
• ether solvents include diethyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, cyclohexyl methyl ether, and tetrahydrofuran.
• amide solvents include formamide, monomethylformamide, dimethylformamide, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide, and N-methylpyrrolidone.
• sulfur-containing solvents examples include dimethyl sulfone, dimethyl sulfoxide, and sulfolane.
• ester-based solvents include n-butyl acetate, ethyl lactate, propylene glycol acetate, propylene glycol monomethyl ether acetate, ⁇ -butyrolactone, and ⁇ -valerolactone.
• the ester solvent may be a glycol ester solvent, a monocarboxylate ester solvent such as n-butyl acetate and ethyl lactate, a lactone solvent such as ⁇ -butyrolactone (GBL) and ⁇ -valerolactone, or a carbonate solvent such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate (propylene carbonate).
• glycol ester solvents include glycol dicarboxylate solvents having 6 to 22 carbon atoms, such as ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, tetraethylene glycol diacetate, propylene glycol acetate, propylene glycol diacetate, dipropylene glycol diacetate, and methoxybutyl acetate, as well as propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene
• the glycol monoether carboxylate solvent include those having 5 to 21 carbon atoms, such as glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, tetraethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate
• an alcohol-based solvent, a glycol ether-based solvent, or an ester-based solvent is preferable, an aliphatic alcohol-based solvent having 1 to 18 carbon atoms, a glycol monoether-based solvent having 3 to 19 carbon atoms, or an ester-based solvent having 4 to 12 carbon atoms is more preferable, and IPA, propylene glycol monomethyl ether, ethyl lactate, ⁇ -butyrolactone, propylene carbonate, or PGMEA is even more preferable.
• ester-based solvents monocarboxylic acid ester-based solvents, lactone-based solvents, and carbonate-based solvents are preferable.
• Two or more kinds of solvents may be used in combination. Also, three or more kinds of solvents may be used. In other words, the chemical solution may contain three or more kinds of solvents.
• the organic solvents selected from the group consisting of alcohol-based solvents, glycol ether-based solvents, and ester-based solvents in combination with water, and it is more preferable to use one or two of the above organic solvents in combination with water.
• the preferred embodiments of the organic solvent are as described above, and among them, IPA, propylene glycol monomethyl ether, ethyl lactate, ⁇ -butyrolactone, propylene carbonate, or PGMEA is preferred as the organic solvent.
• the content of water is preferably 80% by mass or less, more preferably less than 80% by mass, further preferably 50% by mass or less, and particularly preferably 30% by mass or less, based on the total mass of the solvent contained in the chemical solution.
• the lower limit is not particularly limited, and may be, for example, 0% by mass.
• the content of the organic solvent is A
• the content of water is B
• A+B is 100
• the content ratio A/B of the organic solvent to the water is preferably 20/80 to 100/0, more preferably 30/70 to 90/10, and still more preferably 40/60 to 80/20.
• the content of the solvent in the chemical solution is preferably 90 to 99.999% by mass, more preferably 95 to 99.9% by mass, and even more preferably 97 to 99.9% by mass, based on the total mass of the chemical solution.
• the total content thereof is preferably within the above range.
• the chemical solution 1 contains a polymerization inhibitor.
• the polymerization inhibitor is not particularly limited, and a known polymerization inhibitor may be selected depending on the type of crosslinkable group possessed by the specific compound 1, but a radical polymerization inhibitor is preferable.
• the polymerization inhibitor preferably contains at least one compound selected from the group consisting of phenolic compounds, quinone compounds, free radical compounds, amine compounds, and phosphine compounds, and from the viewpoint of polymerization inhibition ability, free radical compounds are more preferable.
• phenolic compounds include 4-methoxyphenol, hydroquinone, 2-tert-butylhydroquinone, 4-tert-butylcatechol, pentaerythritol tetrakis [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-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4-methoxynaphthol, 2,4-bis(octylthiomethyl)-6-methylphenol, p-nitrosophenol, and ⁇ -nitroso- ⁇ -naphthol.
• the quinone compounds include 1,4-benzoquinone, 1,2-benzoquinone, and 1,4-naphthoquinone.
• Free radical compounds include poly(4-methacryloyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl), 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 2,2,6,6-tetramethylpiperidine 1-oxyl, 2,2-diphenyl-1-picrylhydrazyl, and triphenylphenyldazyl.
• amine compounds include 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- ⁇ -naphthylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, phenothiazine, 2-methoxyphenothiazine, phenoxazine, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, N-nitrosodina
• polymerization inhibitors may include nitrobenzene-based compounds such as nitrobenzene and 4-nitrotoluene, as well as thiol ethers such as dioctadecyl 3,3'-thiodipropionate, dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate.
• nitrobenzene-based compounds such as nitrobenzene and 4-nitrotoluene
• thiol ethers such as dioctadecyl 3,3'-thiodipropionate, dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate.
• 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. There is no particular lower limit to the molecular weight, but it is preferably 80 or more.
• the content of the polymerization inhibitor is preferably 0.0001 parts by mass or more, more preferably 0.001 parts by mass or more, even more preferably 0.005 parts by mass or more, and particularly preferably 0.010 parts by mass or more, relative to 100 parts by mass of the content of the specific compound 1.
• 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 100 parts by mass of the content of the specific compound 1.
• the chemical solution 1 may contain one type of polymerization inhibitor alone or two or more types. When two or more types of polymerization inhibitors are contained, the total amount thereof is preferably within the above range.
• the method for producing the drug solution 1 is not particularly limited, and it can be produced, for example, by mixing the above-mentioned components.
• the order or timing of mixing each component in the drug solution is not particularly limited.
• a method of producing a drug solution by adding specific compound 1 to a stirrer such as a mixing mixer containing a purified solvent and then thoroughly stirring the mixture can be mentioned.
• the chemical solution contains other components in addition to the specific compound 1, the other components may be added simultaneously with the specific compound 1 or at different times.
• the steps described below may be carried out.
• the above production method may include a metal removal step of removing metal components from the above components and/or the chemical solution (hereinafter also referred to as "material to be purified").
• the above-mentioned production method preferably includes a filtration step of filtering the liquid in order to remove foreign matter, coarse particles, and the like from the liquid.
• the filtration method is not particularly limited, and any known filtration method can be used. Among them, filtering using a filter is preferred.
• the method for producing the chemical solution may further include a static elimination step of eliminating static electricity from the chemical solution.
• the substrate used in the first embodiment of the method for producing a modified substrate of the present invention is a substrate (hereinafter also simply referred to as "substrate") having at least two surfaces, a first surface and a second surface, which are made of different materials.
• the material constituting the first surface and the material constituting the second surface are not particularly limited as long as they are different from each other, and may be either an organic material or an inorganic material. However, in terms of better effects of the present invention, it is preferable that at least one of the first surface and the second surface contains metal atoms, and it is more preferable that the first surface contains metal atoms.
• metalloid atoms such as boron, silicon, germanium, arsenic, antimony, and tellurium are also included in the metal atoms.
• the metal atom may be, for example, a metal (e.g., a simple metal) or a metal atom contained in a compound.
• the metal atom may also be a metal atom contained in a pure metal or an alloy.
• the metal atom is preferably a transition metal atom, more preferably at least one metal atom selected from the group consisting of a copper atom, a cobalt atom, a titanium atom, a tantalum atom, a tungsten atom, a ruthenium atom, and a molybdenum atom, still more preferably at least one metal atom selected from the group consisting of a titanium atom, a tungsten atom, a ruthenium atom, and a molybdenum atom, and still more preferably a ruthenium atom or a tungsten atom.
• the effects of the present invention are more excellent, and it is preferable that specific compound 1 has, as a functional group that bonds to or is adsorbed onto the first surface, a group selected from the group consisting of a nitrogen-containing group, a phosphonic acid ester, a phosphate group (-PO 4 H 2 ) or a salt thereof, a phosphonic acid group (-PO 3 H 2 ) or a salt thereof, a sulfo group (-SO 3 H) or a salt thereof, a carboxy group (-COOH) or a salt thereof, a hydroxy group (-OH), and a thiol group (-SH).
• a group selected from the group consisting of a nitrogen-containing group, a phosphonic acid ester, a phosphate group (-PO 4 H 2 ) or a salt thereof, a phosphonic acid group (-PO 3 H 2 ) or a salt thereof, a sulfo group (-SO 3 H) or a salt thereof, a
• first surface and the second surface is an embodiment in which one of the first surface and the second surface is a metallic surface made of a metal, and the other is a non-metallic surface made of a non-metal (hereinafter also referred to as embodiment A).
• Metals include pure metals or alloys.
• Non-metals include metal carbides, metal oxides, metal nitrides, metal oxynitrides, and organic materials.
• the pure metals and alloys are preferably composed of the preferred metal atoms exemplified above.
• metal carbides, metal oxides, metal nitrides, and metal oxynitrides are preferably metal carbides, metal oxides, metal nitrides, and metal oxynitrides of the preferred metal atoms exemplified above.
• the first surface is a metal surface and the second surface is a non-metal surface.
• specific compound 1 has, as a functional group that bonds to or is adsorbed onto the first surface, a group selected from the group consisting of a nitrogen-containing group, a phosphonic acid ester, a phosphate group (-PO 4 H 2 ), a phosphonic acid group or a salt thereof, a sulfo group (-SO 3 H) or a salt thereof, a carboxy group (-COOH) or a salt thereof, a hydroxy group (-OH), and a thiol group (-SH).
• first surface and the second surface is a surface in which the first surface is made of a material selected from the group consisting of metal (pure metal or alloy), metal carbide, metal oxide, metal nitride, and metal oxynitride, and the second surface is made of a material different from the first surface and is made of a material selected from the group consisting of metal (pure metal or alloy), metal carbide, metal oxide, metal nitride, and metal oxynitride (hereinafter, also referred to as embodiment B).
• metal pure metal or alloy
• metal carbide metal oxide, metal nitride, and metal oxynitride
• the first surface and the second surface being made of different types of materials means that two types of materials are selected for the first surface and the second surface out of the five types of materials, metal, metal carbide, metal oxide, metal nitride, and metal oxynitride.
• modes B include a mode in which the first surface is a metal surface composed of a metal, and the second surface is a metal oxide surface composed of a metal oxide (hereinafter also referred to as mode B1), a mode in which the first surface is a metal nitride surface composed of a metal nitride, and the second surface is a metal oxide surface composed of a metal oxide (hereinafter also referred to as mode B2), and a mode in which the first surface is a metal oxide surface composed of a metal oxide, and the second surface is a metal surface composed of a metal (hereinafter also referred to as mode B3).
• metals include copper, cobalt, titanium, tantalum, tungsten, ruthenium, and molybdenum.
• Metal oxides include silicon oxide, silicon oxycarbide (SiOC), and tetraethyl orthosilicate (TEOS).
• the metal nitride includes titanium nitride.
• Metal oxides include silicon oxide, silicon oxycarbide (SiOC), and tetraethyl orthosilicate (TEOS).
• specific compound 1 has, as a functional group that bonds to or is adsorbed onto the first surface, a group selected from the group consisting of a nitrogen-containing group, a phosphonic acid group (-PO 3 H 2 ) or a salt thereof, a phosphonic acid ester, a phosphate group (-PO 4 H 2 ) or a salt thereof, a sulfo group (-SO 3 H) or a salt thereof, a carboxy group (-COOH) or a salt thereof, a hydroxy group (-OH), and a thiol group (-SH).
• a group selected from the group consisting of a nitrogen-containing group, a phosphonic acid group (-PO 3 H 2 ) or a salt thereof, a phosphonic acid ester, a phosphate group (-PO 4 H 2 ) or a salt thereof, a sulfo group (-SO 3 H) or a salt thereof, a carboxy group (-COOH) or a salt thereof, a
• the functional group that bonds to or is adsorbed on the first surface is a nitrogen-containing group, it is more likely to bind to or be adsorbed on a tungsten surface, a ruthenium surface, or a molybdenum surface, and therefore the ALD coating is more likely to be inhibited.
• the functional group that bonds to or is adsorbed on the first surface is a phosphonic acid group (-PO 3 H 2 ) or a salt thereof, or a phosphonic acid ester, it is more likely to bind to or be adsorbed on a copper surface or a cobalt surface, and therefore the ALD coating is more likely to be inhibited.
• the metal oxide includes silicon oxide, silicon oxycarbide (SiOC), and tetraethyl orthosilicate (TEOS). Metals include silicon.
• the specific compound 1 in terms of obtaining a more excellent effect of the present invention, it is preferable that the specific compound 1 has a hydrolyzable silyl group as the functional group that bonds to or is adsorbed on the first surface.
• step 1 is a step of contacting a substrate (hereinafter also referred to simply as "substrate”) having at least two surfaces, a first surface and a second surface, each of which is made of a different material, with a chemical solution (chemical solution 1) containing a compound (specific compound 1) having a functional group that bonds to or adsorbs to the first surface and the crosslinkable group, and a molecular weight of 500 or less, and a solvent, to form a first coating on the first surface.
• a substrate hereinafter also referred to simply as “substrate”
• chemical solution 1 containing a compound (specific compound 1) having a functional group that bonds to or adsorbs to the first surface and the crosslinkable group, and a molecular weight of 500 or less
• the method of contacting the substrate with the chemical solution 1 is not particularly limited, but examples thereof include a method of applying or spraying the chemical solution 1 onto the substrate, and a method of immersing the substrate in the chemical solution 1.
• the method of applying the chemical solution 1 to the substrate is not particularly limited, and a known method can be used, for example, a spin coating method.
• the chemical solution 1 may be caused to convect.
• the temperature of chemical solution 1 when the substrate is brought into contact with chemical solution 1 is not particularly limited, but is preferably 0 to 50°C, and more preferably 10 to 30°C.
• the rinsing process can remove the specific compound 1 adhering to areas other than the desired area on the substrate from the substrate.
• the rinsing method is not particularly limited, but may be a method of contacting the substrate with a rinsing liquid.
• the contacting method may be the same as the method of contacting the substrate with the above-mentioned chemical liquid 1.
• the temperature of the rinsing liquid during contact is not particularly limited, but is preferably 0 to 50°C, more preferably 10 to 30°C.
• the rinse liquid is not particularly limited, and may be the solvent contained in chemical liquid 1. The same type of solvent as that contained in chemical liquid 1 may be used as the rinse liquid.
• step 2 is a step of subjecting the substrate obtained in step 1 (substrate having the first coating) to atomic layer deposition processing (ALD processing) to form a second coating on the second surface.
• ALD processing atomic layer deposition processing
• the formation of the second coating is inhibited by the first coating, and therefore a modified substrate is obtained in which the second coating is selectively formed on the areas (second surface) where the first coating is not formed.
• the materials used to form Langmuir-Blodgett films and self-assembled monolayers (SAM films) are often low molecular weight materials.
• step 2 of the present invention although specific compound 1 is a low molecular weight material, it has a crosslinkable group, and therefore when the substrate is heated in the ALD step, the first coating becomes a hardened film and is able to exhibit sufficient heat resistance, making it possible to inhibit the formation of an ALD coating in a fine area while maintaining heat resistance.
• a precursor that is a raw material for the second coating is supplied to the surface of the substrate obtained in step 1.
• the material constituting the second coating can be controlled by the type of precursor supplied, the supply atmosphere, the oxidizing agent, etc.
• the second coating formed by the ALD process is not particularly limited, but is preferably a metal film, a metal oxide film, or a metal nitride film, and more preferably a metal film or a metal oxide film.
• metals that may form the 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.
• metal oxides constituting the metal oxide film include aluminum oxide, titanium oxide, zinc oxide, zirconium oxide, hafnium oxide, and tantalum oxide.
• the metal nitride constituting the metal nitride film include titanium nitride and tantalum nitride. In the ALD process, a process for modifying the surface of the region where the first coating is not formed may be carried out.
• the ALD treatment is not particularly limited, but is preferably a thermal ALD method. Note that, as described later, step 4 may be separately provided as a heating step for reacting crosslinkable groups with each other.
• the substrate heating temperature in the ALD treatment is preferably 100 to 400°C, more preferably 150 to 400°C, and even more preferably 200 to 300°C.
• the difference between the thickness of the second coating on the second surface and the thickness of the second coating on the region 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.
• the upper limit of the thickness difference is not particularly limited, but may be, for example, 100 nm or less.
• the second embodiment of the method for producing a modified substrate of the present invention is a method for producing a modified substrate, comprising: step 1 of contacting a substrate having at least two surfaces, a first surface and a second surface, each of which is made of a different material, with a chemical solution (hereinafter also referred to as "chemical solution 2 " ) containing a compound having a molecular weight of 500 or less and a group selected from the group consisting of a nitrogen-containing group, a phosphonic acid group (-PO 3 H 2 ) 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 crosslinkable group, and a solvent, to form a first coating on the first surface; and step 2 of performing atomic layer deposition on a chemical solution (hereinafter also referred to as "chemical solution 2
• the drug solution 2 contains a specific compound 2 and a solvent.
• specific compound 2 is a compound having a group (specific group) selected from the group consisting of a nitrogen-containing group, a phosphonic acid group (-PO 3 H 2 ) or a salt thereof, a phosphonic acid ester, a phosphate group or a salt thereof, a carboxy group or a salt thereof, a hydroxy group, a thiol group, and a hydrolyzable silyl group, and a crosslinkable group, and having a molecular weight of 500 or less.
• the first surface of the substrate contains a metal atom.
• the specific compound 2 since the specific compound 2 has the specific group, a strong bond is formed between the first surface containing a metal atom and the specific group, thereby making it possible to obtain a stable first coating.
• Specific and preferred aspects of the specific group are the same as the specific and preferred aspects of the functional group that bonds to or is adsorbed on the first surface in the first embodiment.
• groups selected from the group consisting of nitrogen-containing groups, phosphonic acid groups (-PO 3 H 2 ) or salts thereof, phosphonic acid esters, phosphoric acid groups or salts thereof, carboxy groups or salts thereof, hydroxy groups, thiol groups, and hydrolyzable silyl groups are preferred.
• groups selected from the group consisting of nitrogen-containing groups, phosphonic acid groups (-PO 3 H 2 ) or salts thereof, phosphonic acid esters, carboxy groups or salts thereof, hydroxy groups, thiol groups, and hydrolyzable silyl groups are even more preferred are groups selected from the group consisting of nitrogen-containing groups, phosphonic acid groups (-PO 3 H 2 ) or salts thereof, and phosphonic acid esters.
• Specific compound 2 has a crosslinkable group.
• the specific and preferred embodiments of the crosslinkable group in specific compound 2 are the same as the specific and preferred embodiments of the crosslinkable group in specific compound 1.
• the number of crosslinkable groups possessed by specific compound 2 is not particularly limited as long as it is 1 or more, but 1 to 3 is preferable, and 1 is more preferable.
• Specific compound 2 preferably has a structure that exhibits orientation. Specific and preferred embodiments of the structure that exhibits orientation in specific compound 2 are the same as specific and preferred embodiments of the structure that exhibits orientation in specific compound 1.
• the molecular weight of specific compound 2 is not particularly limited as long as it is 500 or less, but is preferably 50 to 450, more preferably 100 to 450, and even more preferably 150 to 400.
• the content of the specific compound 2 is preferably 0.0001 to 10.0 mass %, more preferably 0.001 to 1.0 mass %, and even more preferably 0.01 to 0.5 mass %, based on the total mass of the chemical solution 2. Two or more of the specific compounds 2 may be used in combination. When two or more types of specific compound 2 are used in combination, the total content thereof is preferably within the above range.
• the chemical solution 2 contains a solvent. Specific and preferred aspects of the solvent are the same as those of the solvent contained in the chemical solution 1.
• the content of the solvent in the chemical solution is preferably 90 to 99.999% by mass, more preferably 95 to 99.9% by mass, and even more preferably 97 to 99.9% by mass, based on the total mass of the chemical solution.
• Two or more kinds of solvents may be used in combination. When two or more kinds of solvents are used in combination, the total content thereof is preferably within the above range.
• the chemical solution 2 contains a polymerization inhibitor.
• Specific and preferred aspects of the polymerization inhibitor are the same as those of the polymerization inhibitor contained in the chemical solution 1.
• the content of the polymerization inhibitor is preferably 0.0001 parts by mass or more, more preferably 0.001 parts by mass or more, even more preferably 0.005 parts by mass or more, and particularly preferably 0.010 parts by mass or more, relative to 100 parts by mass of the content of the specific compound 2.
• 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 100 parts by mass of the content of the specific compound 2.
• the chemical solution 2 may contain one type of polymerization inhibitor alone or two or more types. When two or more types of polymerization inhibitors are contained, the total amount thereof is preferably within the above range.
• the method for producing the chemical solution 2 is not particularly limited, and specific and preferred embodiments are the same as those for producing the chemical solution 1.
• the substrate used in the second embodiment of the method for producing a modified substrate of the present invention is a substrate having at least two surfaces, a first surface and a second surface, which are made of different materials (hereinafter, also simply referred to as "substrate"). Specific and preferred aspects of the substrate are the same as those of the substrate used in the first embodiment.
• step 1 is a step of contacting a substrate having at least two surfaces, a first surface and a second surface, which are made of different materials, with a chemical solution (chemical solution 2) containing a compound (specific compound 2 ) having a molecular weight of 500 or less and a solvent, the compound having a group selected from the group consisting of a nitrogen-containing group, a phosphonic acid group (-PO 3 H 2 ) or a salt thereof, a phosphonic acid ester, a phosphate group or a salt thereof, a carboxy group or a salt thereof, a hydroxy group, a thiol group, and a hydrolyzable silyl group, and a crosslinkable group, to form a first coating on the first surface.
• a chemical solution chemical solution 2
• solvent the compound having a group selected from the group consisting of a nitrogen-containing group, a phosphonic acid group (-PO 3 H
• the method for contacting the substrate with the chemical solution 2 is not particularly limited, and specific and preferred embodiments are the same as those for contacting the substrate with the chemical solution 1. It is also preferable to perform a rinsing process on the substrate having the first coating formed on the first surface by contacting the substrate with the chemical solution 2. Specific and preferred aspects of the rinsing method are the same as those of the rinsing method in step 1 of the first embodiment.
• Step 2 The method for producing a modified substrate of the present invention (second embodiment) includes step 2.
• step 2 is a step of forming a second coating on the second surface by subjecting the substrate (substrate having the first coating) obtained in step 1 to atomic layer deposition (ALD).
• ALD atomic layer deposition
• the method for producing a modified substrate of the present invention may include, after step 2, step 3 of removing the first coating formed on the substrate in step 1. By carrying out step 3 after step 2, a modified substrate in which the second coating is formed only on the second surface can be obtained.
• the method for removing the first coating is not particularly limited, but examples thereof include dry etching, wet etching, and a combination thereof. Dry etching may be a method of supplying reactive ions or reactive radicals to the surface of the modified substrate having the first coating.
• the reactive ions or reactive radicals may be generated by plasma or the like, and are preferably generated by using a mixed gas containing one or more gases selected from the group consisting of oxygen, nitrogen, and hydrogen.
• the mixed gas may contain a rare gas. Dry etching may also be physical etching utilizing a sputtering phenomenon.
• an etching solution may be supplied to the surface of the modified substrate having the first coating. Examples of the etching solution include an etching solution containing an oxidizing agent such as ozone, and an etching solution containing an organic solvent. Examples of the organic solvent in the etching solution containing an organic solvent include the organic solvents contained in the above-mentioned chemical solutions, and a hydrocarbon solvent is preferable.
• the method for producing a modified substrate of the present invention may include step 4 of heating the modified substrate.
• Step 4 is preferably carried out before step 2.
• the heating temperature is not particularly limited, but is preferably from 100 to 400°C, more preferably from 150 to 400°C, and even more preferably from 200 to 300°C.
• the heating method is not particularly limited, and examples thereof include a method of contacting the substrate with a heating element (for example, heating with a hot plate) and a method of irradiating the substrate with infrared rays.
• the present invention also relates to a method for producing a semiconductor device, which includes the method for producing the modified substrate described above.
• the method for producing a modified substrate of the present invention can be used in any step for producing a semiconductor device, for example, in the step of treating a semiconductor substrate in a method for producing a semiconductor device.
• the silicon wafer, and the W layer wafer, Ru layer wafer, TiN layer wafer, and TEOS layer wafer obtained by the film formation as described above were each cut into 2 cm squares, rinsed with isopropyl alcohol (IPA), and then dried by spraying nitrogen gas onto each wafer.
• the rinsing process was performed by immersing the substrate in IPA. The immersion was performed while stirring the IPA in a container with a magnetic stirrer at 250 rpm, the IPA temperature was 25° C., and the immersion time was 30 seconds.
• each wafer after the rinsing process was immersed in each of the chemical solutions.
• the immersion of each wafer was performed while stirring the chemical solution in a container at 250 rpm with a magnetic stirrer, the temperature of the chemical solution was 25° C., and the immersion time was 10 minutes.
• each wafer was rinsed with IPA using the same procedure as above, and then dried with nitrogen gas to obtain a sample (evaluation sample) with a first coating formed on each wafer.
• ALD coating An aluminum oxide layer (ALD coating) was formed on the sample (evaluation sample) obtained in [Preparation of evaluation sample substrate (first coating formation method)] and on a sample (untreated sample) in which the first coating was not formed, using an atomic layer deposition apparatus (Samco AD-230LP). Trimethylaluminum was used as the organometallic raw material, and water was used as the oxidizing agent.
• the ALD processing temperature was set to 200° C., and the ALD processing of each sample was performed under conditions such that the film thickness was 5 nm compared to each sample in which the first coating was not formed (untreated sample).
• ALD inhibition amount (nm) (thickness of ALD film of untreated sample (5 nm))-(thickness of ALD film of evaluation sample (nm))
• Table 1 described later shows the components used in preparing the drug solutions and their content ratios (mass ratios).
• the column "Molecular Weight” indicates the molecular weight of a specific compound.
• the molecular weight indicates the weight average molecular weight.
• the evaluation results of ALD inhibition are shown in Tables 2 to 5 described later.
• Table 2 shows the results assuming that a W layer is used as the first surface and a TEOS layer is used as the second surface.
• Table 3 shows the results assuming that a Ru layer is used as the first surface and a TEOS layer is used as the second surface.
• Table 4 shows the results assuming that a TiN layer is used as the first surface and a TEOS layer is used as the second surface.
• Table 5 shows the results assuming that a TEOS layer is used as the first surface and a Si layer is used as the second surface.
• film formation amount indicates the film thickness of the ALD film formed using each evaluation sample
• ALD inhibition amount indicates the ALD inhibition amount calculated according to the above formula (A).
• the structures of the specific compounds (A-1 to A-10) are shown below.
• the specific compound is a compound corresponding to specific compound 1 or specific compound 2.
• a substrate can be obtained in which an ALD coating is formed with good selectivity on the TEOS layer.
• Examples 1B to 16B in which a Ru layer and a TEOS layer were evaluated
• Examples 1C to 15C in which a TiN layer and a TEOS layer were evaluated
• Example 1D in which a TEOS layer and a Si layer were evaluated.
• the ALD inhibition amount was evaluated as C in both the W layer and the TEOS layer.
• Comparative Example 1A since a coating like that in the Example 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 the above-mentioned steps 1 and 2 are carried out using a substrate having a W layer as the first surface and a TEOS layer as the second surface and using the R-1 chemical solution, an ALD coating is formed on both the first surface and the second surface, and the desired effect cannot be obtained. In Comparative Example 2A, the ALD inhibition amount was evaluated as A for both the W layer and the TEOS layer.
• Comparative Example 2A the coating film as in the Example was formed on both the W layer and the TEOS layer, and it was difficult to form the ALD coating film on both the W layer and the TEOS layer. Therefore, when the above-mentioned steps 1 and 2 were performed using a substrate having a W layer as the first surface and a TEOS layer as the second surface and using the R-2 chemical solution, the formation of the ALD coating film on both the first surface and the second surface was suppressed, and the desired effect was not obtained. The same tendency as above was observed in Comparative Examples 1B to 2B and Comparative Examples 1C to 2C.
• substrate 1 having at least one surface selected from the group consisting of a W layer, a Ru layer, and a TiN layer as a first surface and a TEOS layer as a second surface was brought into contact with each of the chemical solutions shown in Table 1, and then an ALD process was carried out in the same procedure as the ALD process carried out in the above [ALD inhibition], it was confirmed that a substrate 1 was obtained in which an ALD coating was formed on the TEOS layer with good selectivity, with the same tendency as in the evaluation results shown in Tables 2 to 4.
• substrate 2 having a TEOS layer as a first surface and a Si layer as a second surface was used instead of substrate 1, and the chemical solution shown in Table 1 was used, it was confirmed that substrate 2 in which an ALD coating was formed with good selectivity on the Si layer could be obtained, with a tendency similar to that of the evaluation results shown in Table 5.
• the W layer wafer and the TEOS layer wafer were evaluated for ALD inhibition using the chemical solutions Y-1 to Y-32 having the compositions described below.
• the ALD inhibition was evaluated in the same manner as in the above [ALD inhibition].
• D-1 4-Methoxyphenol
• D-2 N-Nitroso-N-phenylhydroxylamine
• D-3 Poly(4-methacryloyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl)
• D-4 4-tert-butylcatechol
• D-5 1,4-benzoquinone
• D-6 phenothiazine
• D-7 N,N-diethylhydroxylamine
• D-9 cupferron
• D-10 2,4-bis(octylthiomethyl)-6-methylphenol
• a commercially available silicon wafer (diameter 12 inches) was prepared as a substrate, and a copper (Cu) layer, a cobalt (Co) layer, a silicon oxycarbide (SiOC) layer, a tungsten (W) layer, a ruthenium (Ru) layer, and a molybdenum (Mo) layer were formed on one surface of the silicon wafer, to prepare a Cu-layered wafer, a Co-layered wafer, a SiOC-layered wafer, a W-layered wafer, a Ru-layered wafer, and a Mo-layered wafer (hereinafter, these are collectively referred to as "wafers with layers").
• the Cu layer and the Co layer were formed by sputtering, the SiOC layer was formed by plasma CVD (Chemical Vapor Deposition), and the W layer, the Ru layer, and the Mo layer were formed by CVD.
• the film formation conditions were adjusted so that the thickness of each layer was 20 nm.
• samples were prepared by forming a first coating on each wafer using the chemical solutions shown in Tables 10 to 13. Specifically, the samples were prepared according to the procedure described in [Preparation of evaluation sample substrate (first coating formation method)] in Evaluation A above.
• a titanium nitride layer was formed on the sample (evaluation sample) obtained in [Preparation of evaluation sample substrate (first coating formation method)] and on a sample without the first coating (untreated sample) using an atomic layer deposition apparatus (Flex-AL manufactured by Oxford Corporation).
• TDMAT tetrakis(dimethylamino)titanium
• ammonia was used as the reducing agent.
• the ALD processing temperature was set to 300° C., and the ALD processing of each sample was performed under conditions such that the film thickness was 5 nm compared to each sample in which the first coating was not formed (untreated sample).
• ALD inhibition amount (nm) (ALD film thickness of untreated sample (5 nm))-(ALD film thickness of evaluation sample (nm))
• Tables 14 and 16 show the results assuming that 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.
• Tables 15 and 17 show the results assuming that the first surface is a surface made of at least one of a W layer, a Ru layer, and a Mo layer, and the second surface is a surface made of at least one of a SiOx (silicon wafer) layer and a SiOC layer.
• the method for producing a modified substrate of the present invention makes it possible to produce a modified substrate on which an ALD coating is formed with good selectivity in a predetermined region by performing an ALD treatment.
• the effects of the present invention are more excellent when the crosslinkable group in Specific Compound 1 or Specific Compound 2 is a styryl group, a vinylnaphthyl group, or a vinyl group.

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