Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
  • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
• • 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
  • C23C16/042—Coating on selected surface areas, e.g. using masks 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
  • H10P14/65—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by treatments performed before or after the formation of the materials
  • H10P14/6502—Formation of materials, e.g. in the shape of layers or pillars of insulating materials characterised by treatments performed before or after the formation of the materials of treatments performed before formation of the materials
  • H10P14/6506—Formation of intermediate materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
• • 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]
• • 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
  • H10P14/40—Formation of materials, e.g. in the shape of layers or pillars of conductive or resistive materials
  • H10P14/42—Formation of materials, e.g. in the shape of layers or pillars of conductive or resistive materials using a gas or vapour
  • H10P14/43—Chemical deposition, e.g. chemical vapour deposition [CVD]
  • H10P14/432—Chemical deposition, e.g. chemical vapour deposition [CVD] using selective deposition
• • 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
  • H10P14/61—Formation of materials, e.g. in the shape of layers or pillars of insulating materials 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
• • 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
  • H10P14/6342—Liquid deposition, e.g. spin-coating, sol-gel techniques or spray coating
• • 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
  • H10P14/68—Organic materials, e.g. photoresists
  • H10P14/683—Organic materials, e.g. photoresists carbon-based polymeric organic materials, e.g. polyimides, poly cyclobutene or PVC

Definitions

• the present invention relates to a composition for semiconductor device processing, a method for producing a modified substrate, and a method for producing a laminate.
• a method has been devised in which a coating that inhibits deposition of a material is selectively formed on a specific region of a substrate surface using a material that selectively adsorbs to a specific component, and then an atomic layer deposition (ALD) process is performed to selectively deposit a material in the region where the coating is not present, thereby modifying the substrate.
• ALD atomic layer deposition
• Patent Document 1 discloses a method for selectively modifying a substrate surface, which includes the steps of preparing a substrate having a first region containing a metal atom on its surface, applying to the surface of the substrate a composition containing a first polymer having a group containing a first functional group that bonds to the metal at the end of the main chain or side chain, and a solvent, and heating the coating film formed by the application step.
• the coatings used for selective modification of substrates as described above are required to suppress the amount of material deposited on the coating when atomic layer deposition (ALD) processing is performed on the coating, i.e., to have excellent ALD inhibition properties.
• ALD atomic layer deposition
• an object of the present invention is to provide a composition for semiconductor device treatment capable of forming a coating film having excellent ALD inhibition properties.
• Another object of the present invention is to provide a method for producing a modified substrate and a method for producing a laminate using the composition.
• a composition for treating semiconductor devices comprising: a polymer having at least one functional group that interacts with a substrate at an end of the main chain or at a side chain, and having a repeating unit derived from an aromatic monomer; an aromatic monomer; and a solvent.
• the composition for treating a semiconductor device according to [1] wherein the polymer is a polymer having a repeating unit derived from an aromatic vinyl monomer.
• the content of the aromatic monomer is 1 to 50,000 ppm by mass relative to the content of the polymer.
• composition for treating a semiconductor device according to any one of [1] to [3], wherein the aromatic monomer comprises at least one selected from the group consisting of a compound represented by formula (1) described below and vinylpyridine.
• aromatic monomer comprises at least one selected from the group consisting of a compound represented by formula (1) described below and vinylpyridine.
• polydispersity of the polymer is 1.0 to 1.5.
• R 1 is a hydrogen atom.
• R 2 to R 6 are a hydrogen atom or an alkyl group.
• composition for treating a semiconductor device according to any one of [1] to [7], wherein the solvent comprises at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl lactate, and methyl isobutyl carbinol.
• the composition for treating semiconductor devices according to any one of [1] to [8], wherein a total content of the polymer and the aromatic monomer is 0.1 mass % or more and less than 10 mass % based on a total mass of the composition for treating semiconductor devices.
• a method for producing a modified substrate comprising a step of contacting a substrate with the composition for treating a semiconductor device according to any one of [1] to [9].
• a method for manufacturing a laminate 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.
• the present invention provides a composition for semiconductor device processing that can form a coating with excellent ALD inhibition properties.
• the present invention also provides a method for producing a modified substrate and a method for producing a laminate using the above composition.
• a numerical range expressed using “to” means a range that includes the numerical values before and after “to” as the lower and upper limits.
• ppm means “parts-per-million (10 -6 )
• ppb means “parts-per-billion (10 -9 )
• ppt means “parts-per-trillion (10 -12 ).”
• the “content” of the component means the total content of those two or more components.
• substituents, etc. when there are multiple substituents and linking groups, etc. (hereinafter referred to as "substituents, etc.") indicated by a specific symbol, or when multiple substituents, etc. are specified at the same time, it means that each of the substituents, etc. may be the same or different from each other. This also applies to the specification of the number of substituents, etc.
• (meth)acrylic is a concept that includes either or both of acrylic and methacrylic
• (meth)acrylate is a concept that includes either or both of acrylate and methacrylate
• (meth)acryloyl is a concept that includes either or both of acryloyl and methacryloyl.
• the weight average molecular weight (Mw), number average molecular weight (Mn), and polydispersity index (PDI) (Mw/Mn) of the polymer are defined as polystyrene equivalent values measured by gel permeation chromatography (GPC) measurement using a GPC (Gel Permeation Chromatography) device (HLC-8120GPC, manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 ⁇ L, column: TSK gel Multipore HXL-M (manufactured by Tosoh Corporation), column temperature: 40°C, flow rate: 1.0 mL/min, detector: differential refractive index detector).
• GPC Gel Permeation Chromatography
• compositions for semiconductor device processing The composition for semiconductor device treatment of the present invention (hereinafter also referred to as "the composition") will be described in detail below.
• the composition includes a polymer having at least one functional group capable of interacting with a substrate at the end of the main chain or on a side chain and having repeating units derived from an aromatic monomer, an aromatic monomer, and a solvent.
• the coating that inhibits the deposition of materials during ALD processing is preferably formed densely on the substrate without voids.
• the polymer is adsorbed to the substrate surface by a functional group that interacts with the substrate and is present at the end or side chain of the main chain to form a coating.
• the polymer can form a dense coating due to the repeating unit structure derived from an aromatic monomer with high stacking properties.
• the aromatic monomer that can interact with the polymer and the substrate forms a coating in the voids where the polymer did not form a coating, so that a denser film can be formed overall, and as a result, it is considered that the ALD inhibition is excellent.
• the ability of the composition to form a coating film with superior ALD inhibitory properties is also referred to as "the effect of the present invention is superior.”
• the composition contains a polymer, and the polymer has at least one functional group that interacts with a substrate (hereinafter also referred to as an "interactive group") at the end of the main chain or on a side chain, and has a repeating unit derived from an aromatic monomer.
• a substrate hereinafter also referred to as an "interactive group”
• main chain refers to the longest atomic chain among the atomic chains constituting a polymer
• side chain refers to an atomic chain other than the main chain among the atomic chains constituting a polymer.
• terminal refers to an atomic group connected to the terminal of the main chain or the side chain.
• the polymer has at least one interactive group at the end of the main chain or on a side chain. In terms of being able to form a denser coating and thus achieving better effects of the present invention, it is preferred that the polymer has an interactive group at one end (single end) of the main chain or on a side chain.
• the number of interactive groups in the polymer is not particularly limited as long as it is 1 or more, but is preferably 1 to 100, more preferably 1 to 60, more preferably 1 or 2, and even more preferably 1.
• the mode of interaction between the interactive group and the substrate is not particularly limited, and may be binding to the substrate surface or adsorption to the substrate surface.
• Specific examples of the mode of interaction include covalent bonds, coordinate bonds, ionic bonds, hydrogen bonds, acid-base interactions, van der Waals bonds, and metal bonds.
• the mode of the interaction is preferably a coordinate bond or an ionic bond, and more preferably a coordinate bond.
• the mode of the interaction is preferably hydrogen bonding, acid-base interaction, or covalent bonding.
• the interactive group is preferably either a group that interacts with the metal surface A of the substrate (also referred to as “interactive group A”) or a group that interacts with the non-metallic surface B of the substrate (also referred to as "interactive group B”), and is more preferably interactive group A.
• the interactive group A is preferably a functional group capable of forming a coordinate bond with a metal.
• the above-mentioned interactive group A can be appropriately selected depending on the type of metal to be interacted with, and examples thereof include a nitrogen-containing group, an acidic group, a hydroxyl group (-OH), a thiol group (-SH), a cyano group (-CN), a phosphonate ester bond-containing group, a sulfonate ester bond-containing group, an ethylenically unsaturated group, a carbon-carbon triple bond, a boronic acid group (-BO 2 H 2 ), an epoxy group, and a disulfide bond-containing group, with the acidic group, nitrogen-containing group, hydroxyl group, and cyano group being preferred.
• nitrogen-containing group examples include an amino group (-NR N 2 ), a quaternary ammonium group (-N + R N 3 ), a hydrazine group, a guanidine group, and a nitrogen-containing heterocyclic group, and a tertiary amino group or a nitrogen-containing heterocyclic group is preferred.
• Each R N independently represents a hydrogen atom or an alkyl group (preferably having 1 to 5 carbon atoms, more preferably having 1 to 3 carbon atoms).
• nitrogen-containing heterocyclic group examples include nitrogen-containing aromatic heterocyclic groups such as a pyridyl group, an oxazolyl 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, and nitrogen-containing aliphatic heterocyclic groups such as an imidazolidinyl group, a pyrrolidinyl group, a pyrazolidinyl group, a piperidinyl group, and a piperazinyl group, and of which a pyridyl group, an oxazolyl group, an imidazolidinyl group, or a pyrrolidinyl group is preferred.
• aromatic heterocyclic groups such as a pyridyl group, an oxazolyl group, a triazine group, a
• the acidic group examples include a phosphoric acid group (--PO 4 H 2 ), a phosphonic acid group (--PO 3 H 2 ), a carboxylic acid group (--COOH), and a sulfo group (--SO 3 H), with a phosphonic acid group or a carboxylic acid group being preferred.
• the acidic group may form a salt in the composition, for example, a salt with an inorganic metal ion such as an alkali metal ion or an alkaline earth metal ion.
• the hydroxy group may be either an alcoholic hydroxy group (a hydroxy group bonded to an aliphatic group) or a phenolic hydroxy group (a hydroxy group bonded to an aromatic group), with the phenolic hydroxy group being preferred.
• the interactive group B is preferably a group capable of forming a hydrogen bond, an acid-base interaction, or a covalent bond (eg, Si--O bond, Si--C bond, etc.) with a nonmetal.
• Examples of the interactive group B include hydrolyzable silyl groups such as alkoxysilyl groups and chlorosilyl groups, siloxane bond-containing groups, silanol groups, ethylenic double bonds, cyano groups, and thiol groups.
• the polymer contains repeating units derived from an aromatic monomer, which is a monomeric compound having an aromatic group and a polymerizable group.
• the polymerizable group is not particularly limited as long as it is a functional group having polymerizability, but is preferably a radically polymerizable or anionically polymerizable polymerizable group, and more preferably an ethylenically unsaturated group.
• the ethylenically unsaturated group include a vinyl group, an allyl group, a (meth)acryloyl group, and a (meth)acrylamide group, and the like, and is preferably a vinyl group.
• the aromatic group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, with an aromatic hydrocarbon group being preferred.
• the aromatic group may be either monocyclic or polycyclic, and is preferably monocyclic.
• the aromatic group preferably has 5 to 15 ring atoms, more preferably 5 to 10 ring atoms, and even more preferably 5 to 6 ring atoms.
• Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, and a fluorenyl group. A phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
• the aromatic heterocyclic group is preferably a nitrogen-containing aromatic heterocyclic group, more preferably an oxazolyl group, a pyridyl group, a triazine group, a pyrrole group, a pyrazole group, an imidazole group, a pyrazole group, a triazole group, a benzimidazole group, or a benztriazole group, and still more preferably a pyridyl group.
• the aromatic group and the polymerizable group in the aromatic monomer may be the above-mentioned interactive group.
• the nitrogen-containing aromatic heterocyclic group constituting the aromatic monomer may function as the interactive group A present in the side chain in the polymer.
• the aromatic group may have a substituent.
• the above-mentioned substituent is not particularly limited, but examples thereof include an alkyl group, an alkoxy group, an alkyloxycarbonyl group, a halogen atom, and the above-mentioned interactive group.
• the above-mentioned substituent is preferably an alkyl group, an alkoxy group, an alkyloxycarbonyl group, or a halogen atom, more preferably an alkyl group, an alkoxy group, or an alkyloxycarbonyl group, and even more preferably an alkyl group.
• the above-mentioned substituent is preferably the interactive group described above, preferably a carboxy group, a hydroxy group, a cyano group, or a thiol group, and more preferably a carboxy group or a hydroxy group.
• the number of substituents that the aromatic group may have is not particularly limited, and is preferably 1 to 3, and more preferably 1.
• the aromatic monomer is preferably an aromatic vinyl monomer. That is, the polymer is preferably a polymer having a repeating unit derived from an aromatic vinyl monomer.
• the aromatic vinyl monomer is a monomer compound in which at least one hydrogen atom of an aromatic ring is substituted with a vinyl group.
• the aromatic vinyl monomer is preferably a compound represented by the following formula (1-1).
• R 1 A represents a hydrogen atom or an alkyl group.
• the alkyl group may be linear, branched, or cyclic, and is preferably linear.
• the alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 carbon atom.
• R A is preferably a hydrogen atom in that the effects of the present invention are more excellent.
• R 1 and R 2 independently represents a hydrogen atom or a substituent.
• the substituent include an alkyl group, an alkoxy group, an alkyloxycarbonyl group, a halogen atom, and the above-mentioned interactive group.
• R Ar is preferably a hydrogen atom, an alkyl group, an alkoxy group, an alkyloxycarbonyl group, a carboxy group, or a hydroxy group, and more preferably a hydrogen atom or an alkyl group.
• the alkyl group may be linear, branched, or cyclic, and is preferably linear or branched.
• the alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 3 carbon atoms.
• the alkyl group of the alkoxy group and the alkyloxycarbonyl group may be linear, branched, or cyclic, and preferably is branched or cyclic.
• the number of carbon atoms of the alkyl group of the alkoxy group and the alkyloxycarbonyl group is preferably 1 to 12, more preferably 3 to 10, and even more preferably 3 to 5.
• the aromatic vinyl monomer is preferably a compound represented by the following formula (1) or vinylpyridine.
• R 1 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
• R 2 to R 6 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkyloxycarbonyl group, a carboxy group, or a hydroxy group.
• the alkyl group may be linear, branched, or cyclic, and is preferably linear or branched.
• the alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 3 carbon atoms.
• the alkyl group in the alkoxy group and alkyloxycarbonyl group may be linear, branched, or cyclic, and is preferably branched or cyclic.
• the alkyl group in the alkoxy group preferably has 1 to 12 carbon atoms, more preferably 3 to 10 carbon atoms, and even more preferably 3 to 5 carbon atoms.
• R 2 to R 6 are each independently preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom. In particular, it is preferable that four or more of R 2 to R 6 are hydrogen atoms, and it is more preferable that R 2 to R 6 are hydrogen atoms.
• aromatic vinyl monomers represented by formula (1) include styrene, ⁇ -methylstyrene, p-octylstyrene, p-hexylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-t-butylstyrene, 2,4,6-trimethylstyrene, p-methoxystyrene, p-t-butoxystyrene, p-ethoxystyrene, o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, p-carboxystyrene (4-vinylbenzoic acid), p-(t-butoxycarbonyl)styrene (t-butyl 4-vinylbenzoate), and p-methoxystyrene, among which styrene, p-
• Aromatic vinyl monomers other than the compound represented by (1) above include, for example, styrene derivatives such as p-chlorostyrene, m-chlorostyrene, p-bromostyrene, p-iodostyrene, and p-cyanostyrene, 2-vinylnaphthalene, 1-vinylnaphthalene, ⁇ -methyl-1-vinylnaphthalene, 9-vinylanthracene, and vinylpyridine, with 2-vinylnaphthalene or vinylpyridine being preferred, and vinylpyridine being more preferred.
• styrene derivatives such as p-chlorostyrene, m-chlorostyrene, p-bromostyrene, p-iodostyrene, and p-cyanostyrene
• 2-vinylnaphthalene 1-vinylnaphthalene
• ⁇ -methyl-1-vinylnaphthalene 9-viny
• aromatic monomers include phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate.
• the polymer may have one type of repeating unit derived from an aromatic monomer alone, or may have two or more types of repeating units in combination, and preferably has one type of repeating unit derived from an aromatic monomer alone.
• the content of the repeating units derived from the aromatic monomer is preferably 25% by mass or more, more preferably 75% by mass or more, and even more preferably 90% by mass or more, based on the total repeating units of the polymer.
• the upper limit is not particularly limited, and may be 100% by mass.
• the content of the repeating unit derived from the monomer selected from the group consisting of the aromatic vinyl monomer represented by formula (1) and vinylpyridine is preferably 50% by mass or more, more preferably 75% by mass or more, and even more preferably 90% by mass or more, based on the total repeating units of the polymer.
• the upper limit is not particularly limited, and may be 100% by mass.
• the content of the repeating units derived from styrene is preferably 50% by mass or more, more preferably 75% by mass or more, and even more preferably 90% by mass or more, based on the total repeating units of the polymer.
• the upper limit is not particularly limited, and may be 100% by mass.
• the polymer may have repeating units other than the repeating units derived from the aromatic monomer.
• the other repeating units include repeating units derived from monomers that do not contain an aromatic group. Specific examples include repeating units derived from (meth)acrylic acid, repeating units derived from (meth)acrylamide, and repeating units derived from (meth)acrylic acid alkyl esters.
• the alkyl group of the (meth)acrylic acid alkyl ester preferably has 1 to 12 carbon atoms, and more preferably 1 to 8 carbon atoms.
• the alkyl group may have a substituent.
• the substituent may be the above-mentioned interactive group or a halogen atom.
• the alkyl group may be, for example, a perfluoroalkyl group.
• (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 1-methylcyclopentyl (meth)acrylate, 2-ethyladamantyl (meth)acrylate, 2-(adamantan-1-yl)propyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxyadamantyl (meth)acrylate, and 3-glycidylpropyl (meth)acrylate.
• Monomers that give repeating units other than those mentioned above include, for example, propene, butene, pentene, vinylcyclopentane, vinylcyclohexane, cyclopentene, cyclohexene, 4-hydroxy-1-butene, and vinyl glycidyl ether.
• the other repeating units may be used alone or in combination of two or more.
• the content of the other repeating units is preferably from 0.1 to 80% by mass, more preferably from 1 to 50% by mass, and even more preferably from 1 to 10% by mass, based on the total repeating units of the polymer.
• the polymer can be synthesized according to a known method, for example, radical polymerization or anionic polymerization, with anionic polymerization being preferred in terms of ease of introducing an interactive group to the terminal of the polymer.
• An example of a method for synthesizing a polymer having an interactive group at its terminal is a method in which anionic polymerization is performed using a compound having an interactive group or a functional group convertible into an interactive group as a terminator, and then the functional group derived from the terminator is converted as necessary.
• Examples of a method for synthesizing a polymer having an interactive group in a side chain include a method in which a monomer having an interactive group or a functional group that can be converted into an interactive group is polymerized, and then the functional group is converted as necessary.
• the polymerization degree of the polymer is preferably 10-100, more preferably 20-80, and even more preferably 30-70.
• the number average molecular weight (Mn) of the polymer is preferably from 500 to 50,000, more preferably from 2,000 to 15,000, and even more preferably from 3,000 to 10,000.
• the weight average molecular weight (Mw) of the polymer is preferably from 1,000 to 70,000, more preferably from 2,000 to 20,000, and even more preferably from 3,000 to 10,000.
• the polydispersity (Mw/Mn, PDI) of the polymer is preferably 5.0 or less, more preferably 2.0 or less, further preferably 1.5 or less, particularly preferably 1.3 or less.
• the lower limit is usually 1.0, and preferably 1.05 or more.
• the polymers may be used alone or in combination of two or more.
• the content of the polymer is preferably from 0.01 to 10% by mass, more preferably from 0.1 to 5% by mass, and even more preferably from 0.5 to 3.0% by mass, based on the total mass of the composition.
• the content of the polymer is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 93% by mass or more, based on the total mass of all components in the composition excluding the solvent.
• the upper limit is less than 100% by mass, and preferably 99.9999% by mass or less.
• the composition includes an aromatic monomer.
• the definition and preferred embodiments of the aromatic monomer contained in the present composition are the same as those of the aromatic monomer constituting the repeating unit contained in the above polymer.
• an aromatic vinyl monomer is preferable, the compound represented by the above formula (1-1) is more preferable, the compound represented by the above formula (1) or vinylpyridine is further preferable, and styrene is particularly preferable.
• the aromatic monomer constituting the repeating unit contained in the above-mentioned polymer may be the same as or different from the aromatic monomer contained in the present composition, but it is preferable that they are the same in terms of high affinity between the polymer and the monomer and the ease of forming a denser film.
• the aromatic monomers may be used alone or in combination of two or more.
• the content of the aromatic monomer is preferably 0.1 ppm by mass or more, more preferably 1 ppm by mass or more, and even more preferably 10 ppm by mass or more, relative to the content of the polymer, in that the effects of the present invention are more excellent.
• the content of the aromatic monomer is preferably 100,000 ppm by mass or less, more preferably 50,000 ppm by mass or less, and even more preferably 10,000 ppm by mass or less, relative to the content of the polymer, in that a coating having more excellent heat resistance can be formed.
• the heat resistance refers to the property that the components forming the film are difficult to remove from the film formed using the composition under high temperature conditions (e.g., 200°C).
• the heat resistance is excellent in order to prevent contamination of the ALD processing equipment and to suppress the deterioration of the film and ensure stable ALD inhibition.
• the content of the aromatic monomer in the composition satisfies the above range, the amount of aromatic monomer removed during heat treatment is suppressed, and the heat resistance is more excellent.
• the content of the aromatic monomer can be determined by known methods such as gas chromatography and liquid chromatography.
• the composition comprises a solvent.
• the solvent includes water and organic solvents, with organic solvents being preferred.
• organic solvent include alcohol-based solvents, ether-based solvents, ester-based solvents, ketone-based solvents, amide-based solvents, sulfur-containing solvents, and hydrocarbon-based solvents.
• Examples of the alcohol-based solvent include monoalcohol-based solvents, polyol-based solvents, and glycol monoether-based solvents.
• Examples of monoalcohol solvents include aliphatic monoalcohol solvents having 1 to 18 carbon atoms, such as methanol, ethanol (EtOH), 1-propanol, 2-propanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, isopentyl alcohol, and 4-methyl-2-pentanol (methyl isobutyl carbinol); alicyclic monoalcohol solvents having 3 to 18 carbon atoms, such as cyclohexanol; aromatic monoalcohol solvents, such as benzyl alcohol; and ketone monoalcohol solvents, such as diacetone alcohol.
• polyol-based solvents examples include glycol-based solvents having 2 to 18 carbon atoms, such as ethylene glycol, propylene glycol (1,2-propanediol), 1,3-propanediol, diethylene glycol, and dipropylene glycol.
• glycol monoether solvents examples include glycol monoether solvents having 3 to 19 carbon atoms, such as propylene glycol monomethyl ether (PGME), 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 mono-n-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol
• ether solvents include dialkyl ether solvents such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, dihexyl ether, and cyclohexyl methyl ether, cyclic ether solvents such as tetrahydrofuran and tetrahydropyran, anisole, and diphenyl ether.
• dialkyl ether solvents such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, dihexyl ether, and cyclohexyl methyl ether
• cyclic ether solvents such as tetrahydrofuran and tetrahydropyran, anisole, and diphenyl ether.
• ester-based solvents examples include glycol ester-based solvents, monocarboxylic acid ester-based solvents such as n-butyl acetate and ethyl lactate, lactone-based solvents such as ⁇ -butyrolactone (GBL) and ⁇ -valerolactone, and carbonate-based solvents such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate.
• monocarboxylic acid ester-based solvents such as n-butyl acetate and ethyl lactate
• lactone-based solvents such as ⁇ -butyrolactone (GBL) and ⁇ -valerolactone
• carbonate-based solvents such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate.
• glycol ester solvents examples 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 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 glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate.
• glycol dicarboxylate solvents having 6 to 22 carbon atoms
• glycol diacetate such as ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, tetraethylene glycol diacetate, propylene glycol diacetate,
• glycol monoether carboxylate solvents examples include glycol monoether carboxylate solvents having 5 to 21 carbon atoms, such as ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl 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.
• the ester solvent preferably has 3 to 22 carbon atoms, and more preferably has 4 to 12 carbon atoms.
• 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.
• Ketone solvents include, for example, chain ketone solvents such as methyl isobutyl ketone, acetone, methyl ethyl ketone, diethyl ketone, methyl n-butyl ketone, 2-heptanone, ethyl n-butyl ketone, methyl n-ketone, diisobutyl ketone, and trimethylnonane, cyclic ketone solvents such as cyclohexanone, cyclopentanone, cycloheptanone, and methylcyclohexanone, and acetophenone.
• chain ketone solvents such as methyl isobutyl ketone, acetone, methyl ethyl ketone, diethyl ketone, methyl n-butyl ketone, 2-heptanone, ethyl n-butyl ketone, methyl n-ketone, diisobutyl ketone
• 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.
• the solvent is preferably an alcohol-based solvent, an ether-based solvent, an ester-based solvent, or a ketone-based solvent, more preferably an aliphatic monoalcohol-based solvent, a glycol monoether-based solvent, a glycol ester-based solvent, a monocarboxylic acid ester-based solvent, an ether-based solvent, or a lactone-based solvent, and even more preferably a glycol monoether-based solvent or a glycol ester-based solvent.
• the solvent preferably contains at least one selected from the group consisting of PGMEA, PGME, cyclohexanone, ethyl lactate, methyl isobutyl carbinol, EtOH, and ⁇ -butyrolactone, and more preferably contains at least one selected from the group consisting of PGMEA, PGME, cyclohexanone, ethyl lactate, and methyl isobutyl carbinol.
• the solvent also preferably contains an ether solvent, and more preferably contains diethyl ether or tetrahydrofuran.
• the solvent may be used alone or in combination of two or more kinds.
• the content of the solvent is preferably 90.00% by mass or more, more preferably 95.00% by mass or more, and even more preferably 97.00% by mass or more, based on the total mass of the composition.
• the upper limit is less than 100% by mass, preferably 99.999% by mass or less, more preferably 99.9% by mass or less, and even more preferably 99.0% by mass or less.
• the content of one type of solvent is preferably 90% by mass or more, more preferably 99% by mass or more, and even more preferably 99.9% by mass or more, based on the total mass of all the solvents.
• the upper limit is not particularly limited, and may be 100% by mass.
• the present composition contains two or more solvents, it is preferable that at least one of them is an ether solvent, and it is more preferable that at least one of them is tetrahydrofuran or diethyl ether.
• the present composition contains two or more types of solvents, it preferably contains at least one ether-based solvent and further contains at least one selected from the group consisting of alcohol-based solvents, ester-based solvents, and ketone-based solvents.
• the content of the ether solvent is preferably from 0.01 to 100,000 ppm by mass, more preferably from 0.1 to 10,000 ppm by mass, and even more preferably from 1.0 to 1,000 ppm by mass, based on the total mass of all the solvents.
• the composition may contain other components in addition to the polymer, aromatic monomer, and solvent.
• the other components include an acid generator, a polymerization inhibitor, and a surfactant.
• the acid generator is not particularly limited as long as it is a compound that generates an acid upon exposure to light or heating, and examples thereof include onium salt compounds, N-sulfonyloxyimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate compounds, carboxylate compounds, phosphate compounds, and sulfonebenzotriazole compounds.
• Examples of the polymerization inhibitor include phenol-based compounds, quinone-based compounds, free radical-based compounds, amine-based compounds, and phosphine-based compounds.
• Examples of the surfactant include cationic surfactants, anionic surfactants, and nonionic surfactants.
• the compounds described in paragraphs [0092] to [0096] of JP 2015-158662 A, paragraphs [0045] to [0046] of JP 2012-151273 A, and paragraphs [0014] to [0020] of JP 2009-147389 A can also be used, and the contents of these are incorporated herein.
• the total content of the polymer and aromatic monomer is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.1% by mass or more, based on the total mass of the composition.
• the upper limit is often less than 15.0% by mass, preferably less than 10.0% by mass, and more preferably less than 5.0% by mass.
• the total content of the polymer and aromatic monomer is preferably 95.0% by mass or more, more preferably 99.0% by mass or more, and even more preferably 99.9% by mass or more, based on the total mass of all components in the composition excluding the solvent.
• the upper limit is not particularly limited, and is 100% by mass.
• the method for producing the composition is not particularly limited, and the composition can be produced, for example, by mixing the above-mentioned components.
• the order or timing of mixing the components is not particularly limited, and the composition can be produced, for example, by adding the polymer and aromatic monomer to a stirrer such as a mixer containing a purified solvent, and then thoroughly stirring the mixture.
• a stirrer such as a mixer containing a purified solvent
• the manufacturing process of the present composition may include a process selected from the group consisting of a distillation process for distilling the raw materials, a dehydration process for dehydrating the present composition, a metal removal process for removing metal components from the present composition, a filtration process for filtering the present composition, and a static elimination process for destaticizing the present composition.
• the composition can be stored, transported and used by filling it into a known container.
• the container is preferably one that is highly clean for semiconductor applications and that suppresses the elution of impurities from the inner wall of the container's storage section into each liquid.
• Examples of such containers include various containers that are commercially available as containers for semiconductor processing liquids, such as the "Clean Bottle” series manufactured by Aicello Chemical Co., Ltd. and the “Pure Bottle” manufactured by Kodama Resin Industry Co., Ltd., but are not limited thereto.
• the containers exemplified in paragraphs [0121] to [0124] of WO 2022/004217 can also be used, the contents of which are incorporated herein by reference.
• the composition is a composition for treating a semiconductor device, and is preferably used for modifying a substrate in a process for manufacturing a semiconductor device.
• the above treatment provides a modified substrate having a coating formed on the substrate surface.
• the composition is also preferably used to produce a laminate by subjecting the modified substrate to an ALD process, whereby material is deposited in the areas not coated by the process.
• ALD process ALD-deposition
• the substrate is not particularly limited, but preferably has at least one of a metal surface A made of a material containing metal atoms and a non-metal surface B made of a non-metal material, and more preferably has a metal surface A.
• the metal atom contained in the metal surface A is not particularly limited, but is preferably a tungsten atom, a copper atom, a ruthenium atom, a cobalt atom, a titanium atom, a tantalum atom, a molybdenum atom, a germanium atom, a zirconium atom, an aluminum atom, a tin atom, a nickel atom, a palladium atom, an indium atom, a zinc atom, a gold atom, a silver atom, or a platinum atom, more preferably a tungsten atom, a ruthenium atom, a tantalum atom, a copper atom, or a cobalt atom, and even more preferably a tungsten atom or a copper atom.
• the form of the metal atoms on the metal surface A is not particularly limited, and examples thereof include an elemental metal, an alloy, a nitride, an oxide, and a silicide, among which an elemental metal or an alloy is preferred.
• the alloy include an alloy containing two or more of the metal atoms contained in the metal surface A described above.
• the method for forming the metal surface A there is no particular limitation on the method for forming the metal surface A, and any known method can be used, such as CVD, plating, and physical vapor deposition.
• non-metallic materials constituting the non-metallic surface B include insulators, for example, non-metallic elements such as silicon and carbon, non-metallic oxides such as silicon oxide, non-metallic nitrides such as silicon nitride, non-metallic oxynitrides such as silicon oxynitride, and organic substances.
• the material constituting the non-metallic surface B is preferably a non-metallic material containing silicon atoms, and more preferably silicon oxide.
• silicon oxides include materials represented by the composition SiO y (wherein y is preferably 0.5 to 2.0, more preferably 1.0 to 2.0) and materials represented by the composition SiO z C w (wherein z is preferably 0.5 to 2.0, more preferably 1.0 to 2.0, and w is preferably 0.5 to 2.0, more preferably 1.0 to 2.0).
• the materials represented by the composition SiO y and the materials represented by the composition SiO z C w may further contain hydrogen.
• Examples of materials represented by the composition SiO z C w include Si(OC 2 H 5 ) 4 (tetraethyl orthosilicate, TEOS).
• the silicon oxide is preferably a material represented by the composition SiO 2 (silicon dioxide) or TEOS.
• the method for forming the nonmetallic surface B is not particularly limited, and examples thereof include a CVD method, a physical vapor deposition method, plasma irradiation, and application of a precursor compound. It is also preferable that the non-metallic surface B is a surface treatment performed on a region made of silicon oxide, such as a treatment by contacting the surface with a treatment liquid such as an aqueous solution containing an acidic compound (preferably hydrogen fluoride water), a plasma treatment, a corona treatment, or an ozone treatment.
• a treatment liquid such as an aqueous solution containing an acidic compound (preferably hydrogen fluoride water), a plasma treatment, a corona treatment, or an ozone treatment.
• the substrate has at least two surfaces, a first surface and a second surface, which are made of different materials.
• the first surface is a surface that interacts with the interactive group of the polymer.
• the second surface may be made of a material different from that of the first surface, but is preferably a surface that does not form a coating when it comes into contact with the composition.
• at least one of the first surface and the second surface is a metal surface A or a non-metal surface B, and it is more preferable that at least one of the first surface and the second surface is a metal surface A.
• a preferred embodiment of the substrate is embodiment 1 in which the first surface is a metal surface A.
• the interactive group possessed by the polymer is the interactive group A described above.
• the metal atoms in the metal surface A which is the first surface are preferably contained in the form of an elemental metal, an alloy, a conductive metal nitride, or a metal silicide, and more preferably in the form of an elemental metal or an alloy.
• the metal element and alloy include the metal elements exemplified as the metal contained in the metal surface A and their alloys.
• the conductive metal nitride include tantalum nitride, titanium nitride, iron nitride, and aluminum nitride.
• the metal silicide include iron silicide, molybdenum silicide, and tungsten silicide.
• the second surface is preferably a metal surface A or a non-metal surface B different from the first surface, and more preferably a non-metal surface B.
• the metal atom-containing form in the metal surface A constituting the second surface is preferably a metal oxide, a metal nitride or a metal oxynitride, and more preferably a metal oxide.
• metal oxides include aluminum oxide, tantalum oxide, iron oxide, and copper oxide.
• a preferred embodiment of the substrate also includes embodiment 2 in which the first surface is the nonmetallic surface B.
• the interactive group possessed by the polymer is the interactive group B described above.
• the second surface is preferably a metal surface A.
• the metal atoms in the metal surface A which is the second surface are preferably contained in the form of an elemental metal, an alloy, a conductive metal nitride, or a metal silicide, and more preferably in the form of an elemental metal or an alloy.
• the shape of the first surface and the second surface is not particularly limited, and examples include a planar shape, a dot shape, and a stripe shape.
• the shape of the substrate is not particularly limited, and any shape that is generally used as a semiconductor substrate can be used.
• the substrate may be a substrate having the above-mentioned surface, and may be a single layer or may have a multi-layer structure.
• the coating formed on a substrate by the present composition is a coating containing components (for example, polymer and aromatic monomer) other than the solvent contained in the present composition.
• the coating preferably functions as a mask when depositing a material in the ALD process. That is, when the ALD process is performed on a modified substrate having a coating formed by the composition on a specific region, the material is not deposited in the region where the coating is formed, and the material is deposited in the region where the coating is not formed to form a film (hereinafter, also referred to as "ALD film"). This results in a laminate in which the ALD film is selectively formed in the region other than the region where the coating is formed.
• the coating also functions favorably as a mask when forming a metal-containing film by chemical vapor deposition (CVD) other than ALD. That is, in a CVD process, deposition of a film by CVD (hereinafter also referred to as a "CVD film”) can be suppressed in the region where the coating is formed, and a CVD film can be deposited in the region where the coating is not formed. This results in a laminate in which a CVD film is selectively formed in the region other than the region where the coating is formed.
• CVD other than ALD that can be preferably applied to the modified substrate include known techniques such as thermal CVD and plasma CVD.
• the raw material of the CVD film used in the CVD process the raw material of the ALD film described later can be used.
• the thickness of the coating is preferably 0.1 to 100.0 nm, more preferably 0.5 to 50.0 nm, and even more preferably 3.0 to 30.0 nm.
• the water contact angle of the coating is preferably 60° or more, more preferably 80° or more, and even more preferably 90° or more. There is no particular upper limit, and in many cases it is 120° or less.
• the water contact angle was measured three times using a contact angle meter (DMs-501, manufactured by Kyowa Interface Science Co., Ltd.) at 500 milliseconds after a droplet of water contacted the surface of the measurement object, and the average value was used to measure the contact angle.
• the method for producing a modified substrate of the present invention includes a step of contacting a substrate with the composition to form a coating on the substrate, thereby obtaining a modified substrate having a coating formed on the substrate.
• the method of contacting the substrate with the composition is not particularly limited, and known methods can be used.
• the composition can be applied (e.g., spin-coated) or sprayed onto the substrate, or the substrate can be immersed in the composition. When the substrate is immersed in the composition, the composition can be caused to circulate.
• the temperature of the composition when it is brought into contact with the substrate is not particularly limited, but is preferably 0 to 50°C, more preferably 10 to 30°C.
• the coating is also preferred to subject the coating to a heat treatment after contacting the substrate with the composition, which promotes interaction (e.g., bond formation) between the substrate surface and the interactive groups of the polymer.
• the heating method is not particularly limited, and any known method can be used, for example, an oven, a hot plate, or the like.
• the heating temperature is preferably from 50 to 400°C, more preferably from 100 to 350°C, further preferably from 130 to 300°C, and particularly preferably from 150 to 250°C.
• the heating time is preferably from 10 seconds to 60 minutes, more preferably from 1 minute to 30 minutes, and even more preferably from 3 minutes to 10 minutes.
• the rinsing method is not particularly limited, and may be a method of contacting the substrate with a rinsing liquid, which may be the same as the method of contacting the present composition with the substrate.
• the temperature of the rinse solution during contact is not particularly limited, but is preferably 0 to 50°C, more preferably 10 to 30°C.
• a known organic solvent can be used, for example, the above-mentioned alcohol-based solvents, ether-based solvents, ester-based solvents, etc. It is also preferable to use the solvent contained in the present composition as the rinse liquid.
• the method for producing a laminate of the present invention includes step 1 of contacting a substrate (hereinafter also referred to as a "specific substrate") having at least two types of surfaces, a first surface and a second surface, each of which is made of a different material, with the present composition to form a first coating on the first surface, and step 2 of subjecting the substrate obtained in step 1 to an ALD treatment to form a second coating on the second surface.
• a substrate hereinafter also referred to as a "specific substrate” having at least two types of surfaces, a first surface and a second surface, each of which is made of a different material
• Step 1 is a step of contacting a specific substrate with the present composition to form a first coating on a first surface.
• a modified substrate 1 is obtained in which a first coating is formed on the first surface of a specific substrate.
• the first coating is a coating containing a polymer contained in the present composition and an aromatic monomer.
• the coating is also preferred to subject the coating to a heat treatment after contacting the specific substrate with the composition, which promotes interaction (e.g., bond formation) between the surface of the first surface and the interactive group of the polymer.
• the heating method is not particularly limited, and the heating methods in the above-mentioned method for producing a modified substrate can be used.
• the rinsing treatment can remove the composition and/or impurities adhering to regions (e.g., the second surface) of the specific substrate other than the first surface from the specific substrate.
• the rinsing method the rinsing method in the above-mentioned method for producing a modified substrate can be used.
• Step 2 is a step of performing an ALD process on the modified substrate 1 obtained in step 1 above to form a second coating on the second surface.
• a laminate 1 having a first coating formed on the first surface and a second coating formed on the second surface is obtained by step 2.
• the second coating is a film formed by an ALD process (ALD film).
• the modified substrate 1 may be any substrate having a first coating formed on a first surface of a specific substrate by the above-mentioned step 1, and may be subjected to the above-mentioned heating treatment and rinsing treatment, etc., after step 1.
• the method of the ALD treatment is not particularly limited, and any known method can be used.
• a method is mentioned in which a precursor gas, which is a raw material for the ALD film, is supplied to the surface of the modified substrate 1, and then the raw material is decomposed and/or chemically reacted with an oxidizing agent or the like to deposit the material, thereby forming the ALD film.
• the precursor is not particularly limited, and a known precursor can be used depending on the type of ALD film to be formed, for example, an organometallic compound.
• the compounds described in paragraphs [0021] to [0025] of JP-A-2022-080800 can be used.
• the oxidizing agent is not particularly limited, and any known oxidizing agent used in ALD processing can be used, such as water, oxygen, and ozone.
• the material constituting the ALD film can be controlled by the type of precursor supplied, the supply atmosphere, the oxidizing agent, and the like.
• the material of the ALD film to be formed is not particularly limited, and includes metals, metal oxides, and metal nitrides.
• metals 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 include aluminum oxide, titanium oxide, zinc oxide, zirconium oxide, hafnium oxide, and tantalum oxide.
• metal nitrides 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 thickness of the material deposited on the first coating is preferably as thin as possible, and is preferably 4.0 nm or less, more preferably 2.0 nm or less, and even more preferably 1.0 nm or less.
• the lower limit is 0 nm, and may be 0 nm.
• the ratio of the thickness of the material deposited on the region where the first coating is formed to the thickness of the second coating is preferably 0.75 or less, more preferably 0.5 or less, and even more preferably 0.25 or less.
• the lower limit of the ratio is 0 or more, and may be 0.
• the method for producing a laminate of the present invention may include, after step 2, step 3 of removing the first coating formed on the first surface in step 1. By step 3, a laminate 2 is obtained that has no coating on the first surface and has a second coating on the second surface.
• the method for removing the first coating is not particularly limited, and examples thereof include dry etching, wet etching, and a combination thereof.
• dry etching a known method can be used, for example, chemical dry etching in which reactive ions or reactive radicals are supplied to the surface of the laminate 1, and physical dry etching such as sputter etching and ion beam etching can be used.
• wet etching a method of supplying an etching solution to the laminate 1 can be used.
• the etching solution include an etching solution containing an oxidizing agent such as ozone and hydrofluoric acid, and an etching solution containing an organic solvent.
• organic solvent examples include the organic solvents contained in the above-mentioned chemical solutions, and alcohol-based solvents, ester-based solvents, ketone-based solvents, or hydrocarbon-based solvents are preferred. Among these, chemical dry etching or wet etching is preferred.
• the present invention will be described in further detail below with reference to examples.
• the materials, amounts, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples.
• the preparation, filling, storage, etc. of the composition were all carried out in a clean room that satisfied ISO class 2 or lower.
• the containers used for the preparation, filling, storage, etc. of the composition were washed with the solvent used in the preparation or the prepared composition before use.
• Polymer P-1 was synthesized as follows. After drying the flask reaction vessel under reduced pressure, 240 g of tetrahydrofuran (THF) that had been subjected to distillation and dehydration treatment under a nitrogen atmosphere was poured in and cooled to -78°C.
• THF tetrahydrofuran
• the reaction solution was warmed to room temperature, and the resulting reaction solution was concentrated and replaced with methyl isobutyl ketone (MIBK). Then, 400 g of ultrapure water was poured in and stirred, and the lower aqueous layer was removed. This operation was repeated six times to remove the lithium salt, and the solution was then concentrated and dropped into 400 g of methanol to precipitate a polymer, and the solid was collected using a Buchner funnel. The resulting solid was made into a 50 wt % solution of MIBK, and the solution was dropped into 400 g of methanol to precipitate a polymer, and the solid was collected using a Buchner funnel. The polymer was dried under reduced pressure at 60° C. to obtain 19.6 g of a white polymer P-1.
• MIBK methyl isobutyl ketone
• the polymers other than polymer P-1 were synthesized according to the synthesis method for polymer P-1, adjusting the types and amounts of monomers and end-terminators, and reaction conditions to obtain the polymers shown below.
• each polymer used in the compositions of the examples and comparative examples is shown below.
• the numerical value at the bottom right of each repeating unit indicates the polymerization degree of each repeating unit.
• the polydispersity and polymerization degree of each polymer were obtained by GPC measurement under the above-mentioned conditions.
• polymer P-5 the content of repeating units derived from 4-t-butoxystyrene was 30 mol % relative to all repeating units, and the content of repeating units derived from styrene was 70 mol %.
• polymer P-11 the content of repeating units derived from t-butyl 4-vinylbenzoate was 50 mol % relative to all repeating units, and the content of repeating units derived from 4-vinylbenzoic acid was 50 mol %.
• Polymer P-13 the content of repeating units derived from 4-t-butoxystyrene was 60 mol %, and the content of repeating units derived from styrene was 40 mol %, based on all repeating units.
• Polymer P-16 the content of repeating units derived from 4-t-butoxystyrene was 60 mol %, and the content of repeating units derived from 2-(perfluorohexyl)ethyl acrylate was 40 mol %, based on all repeating units.
• polymer P-5, polymer P-11, polymer P-13 and polymer P-16 were all random copolymers.
• a W-layer wafer in which a tungsten layer was formed by CVD on one surface of a commercially available silicon wafer (diameter 12 inches) and a Cu-layer wafer in which a Cu layer was formed by sputtering were prepared.
• the film formation conditions were adjusted so that the thicknesses of the W layer and the Cu layer were each 20 nm.
• the silicon wafer, W layer wafer, and Cu layer wafer were cut into 2 cm squares and washed by immersing them in isopropyl alcohol (IPA). The washing was performed while stirring the IPA at a stirring speed of 250 rpm, the IPA temperature was 25° C., and the washing time was 30 seconds.
• IPA isopropyl alcohol
• the washed wafer was dried by blowing nitrogen gas onto it.
• the W layer wafer is a substrate having a metallic surface A with tungsten atoms as the metallic atoms
• the Cu layer wafer is a substrate having a metallic surface A with copper atoms as the metallic atoms
• the silicon wafer (Si substrate) is a substrate having a non-metallic surface B with silicon oxide.
• each of the washed wafers was immersed in each of the compositions to perform a modification treatment on the wafers.
• the immersion was performed while stirring the composition at a stirring speed of 250 rpm, the temperature of the composition was 25° C., and the immersion time was 10 minutes.
• each wafer was rinsed by immersing it in IPA.
• the rinsing was performed while stirring the IPA at a stirring speed of 250 rpm, the IPA temperature was 25° C., and the rinsing time was 30 seconds.
• the wafer was dried by blowing nitrogen gas onto it. By the above procedure, a modified substrate was obtained.
• ALD film An aluminum oxide (Al 2 O 3 ) layer (ALD film) was formed by the ALD method using an atomic layer deposition apparatus (AD-230LP, manufactured by Samco) on each of the modified substrates obtained by [Preparation of modified substrates] and on the substrates (unmodified substrates ) before being immersed in each composition.
• Trimethylaluminum was used as the organometallic raw material, and water was used as the oxidizing agent, and the ALD treatment temperature was set to 200° C. Other conditions were adjusted so that the thickness of the ALD film formed on the unmodified substrate was 5 nm.
• the thickness of the ALD film of each sample after the ALD process was measured using an X-ray fluorescence (XRF) analyzer (AZX400 manufactured by Rigaku Corporation). Measurements were performed at five points on the substrate, and the average value was taken as the film thickness.
• the ALD inhibitory property was evaluated based on the obtained film thickness according to the following evaluation criteria. The smaller the film thickness, the less likely a film is to be deposited by ALD treatment on the film formed by the composition, i.e., the better the ALD inhibitory property.
• the ALD inhibitory property is preferably C or higher.
• the thickness of the ALD film is less than 1.0 nm.
• A The thickness of the ALD film is 1.0 nm or more and less than 1.5 nm.
• B The thickness of the ALD film is 1.5 nm or more and less than 2.0 nm.
• C The thickness of the ALD film is 2.0 nm or more and less than 2.5 nm.
• D The thickness of the ALD film is 2.5 nm or more.
• Tables 1 to 3 show the composition and evaluation results of each composition.
• the “content (mass %)" of the polymer indicates the content (unit: mass %) relative to the total mass of the composition.
• the “content (ppm by mass)” of the aromatic monomer represents the content relative to the polymer content (unit: ppm by mass).
• the content of the solvent is the remainder obtained by subtracting the contents of the polymer and aromatic monomer from the total mass of the composition.
• Example A1 to A3 From a comparison of Examples A1 to A3, it was confirmed that when the content of the aromatic monomer in the composition is 1 to 50,000 ppm by mass relative to the content of the polymer, the ALD inhibition property and heat resistance are more excellent.
• Comparison of Example A4 with Examples A1, A12, and A13 confirmed that when the aromatic monomer is at least one selected from the group consisting of the compound represented by formula (1) and vinylpyridine, the ALD inhibition property and heat resistance are more excellent. From a comparison between Example A5 and Example A1, it was confirmed that the effect of the present invention is more excellent when the polydispersity of the polymer is 1.0 to 1.5.
• Example A6 with Example A1 and comparison of Examples A10 to A11 with Example A4, confirmed that the heat resistance was superior when the solvent contained at least one selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl lactate, and methyl isobutyl carbinol.
• Example A7 and Example A1 it was confirmed that when the total content of the polymer and the aromatic monomer was 0.1 mass % or more, the ALD inhibition property and heat resistance were superior.
• Example A8 and Example A1 it was confirmed that when the aromatic monomer is a compound represented by formula (1) in which R 1 is a hydrogen atom, the heat resistance is more excellent.
• Comparison of Examples B3 and B4 with Examples B1 and B2 confirmed that when the aromatic monomer is a compound represented by formula (1) in which R 2 to R 6 are hydrogen atoms or alkyl groups, the ALD inhibition properties and heat resistance are superior.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Materials For Photolithography (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Formation Of Insulating Films (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Related Child Applications (1)

Publications (1)

Family

ID=92904683

Family Applications (1)

Country Status (5)

Citations (5)

Family Cites Families (1)

• 2024
  • 2024-03-15 JP JP2025510488A patent/JPWO2024203436A1/ja active Pending
  • 2024-03-15 WO PCT/JP2024/010174 patent/WO2024203436A1/ja not_active Ceased
  • 2024-03-15 KR KR1020257027907A patent/KR20250140563A/ko active Pending
  • 2024-03-25 TW TW113110969A patent/TW202440821A/zh unknown
• 2025
  • 2025-08-28 US US19/312,488 patent/US20250376760A1/en active Pending

Patent Citations (5)

Also Published As

Similar Documents

Legal Events