Semiconductor device processing composition, method for manufacturing modified substrate, method for manufacturing laminate, and method for manufacturing electronic device

Abstract

The present invention provides: a semiconductor device processing composition capable of forming a film that is formed in a specific region of a substrate and suppresses film formation by atomic layer deposition processing; a method for manufacturing a modified substrate; a method for manufacturing a laminate; and a method for manufacturing an electronic device. The semiconductor device processing composition according to the present invention comprises: a polymer having a first repeating unit derived from a first monomer with a ClogP of 4.0 or greater, and a second repeating unit having a specific functional group that binds to or is adsorbed on a substrate; and a solvent.

Description

Composition for treating semiconductor devices, method for manufacturing modified substrates, method for manufacturing laminates, and method for manufacturing electronic devices

[0001] The present invention relates to a composition for treating semiconductor devices, a method for producing a modified substrate, a method for producing a laminate, and a method for producing an electronic device.

[0002] As semiconductor devices become more powerful, smaller and more precise semiconductor elements are required. Traditionally, top-down photolithography has been used to form semiconductor elements, but achieving the required precision is becoming increasingly difficult due to mechanical and optical factors, etc. Therefore, as a bottom-up method for forming semiconductor elements, a method for selectively modifying a substrate has been considered, in which a film of a compound is formed on a region of a substrate made of a specific material by selectively adsorbing the compound to the specific material, and the film is then used to modify regions of the substrate other than the region made of the specific material. Specifically, for example, a method has been devised in which a material that selectively adsorbs to a specific component is used to selectively form a coating that inhibits material deposition on a specific region of the substrate surface, followed by atomic layer deposition (ALD) processing to selectively deposit material in regions where the coating is not present, thereby modifying the substrate.

[0003] As a method for selectively modifying a substrate as described above, Patent Document 1 discloses a surface treatment method for treating a surface including two or more regions, wherein adjacent regions among the two or more regions are made of different materials, and the surface treatment method and agent can selectively modify at least one region with a good reaction rate, thereby achieving good contrast between the regions made of different materials. The surface treatment method and agent are "a surface treatment agent containing a phosphonic acid diester compound (P) represented by general formula (P-1) and an acid."

[0004] Japanese Patent Application Laid-Open No. 2022-100079

[0005] The coating used for selective modification of a substrate as described above is 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.

[0006] The present inventors formed a coating using the composition disclosed in Patent Document 1 and subjected the coating to an ALD process, and found that there was room for further improvement in ALD inhibition. Therefore, an object of the present invention is to provide a composition for semiconductor device processing that can form a coating that is formed in a specific region of a substrate and suppresses film formation by atomic layer deposition. Another object of the present invention is to provide a method for manufacturing a modified substrate, a method for manufacturing a laminate, and a method for manufacturing an electronic device.

[0007] As a result of extensive research into solving the above problems, the present inventors have found that the problems can be solved by the following configuration.

[0008] [1] A composition for treating semiconductor devices, comprising a polymer having a first repeating unit derived from a first monomer and having a ClogP of 4.0 or more and a second repeating unit having a specific functional group that bonds to or adsorbs to a substrate, and a solvent. [2] The composition for treating semiconductor devices according to [1], wherein the polymer has a polydispersity of 1.5 or less. [3] The composition for treating semiconductor devices according to [1] or [2], wherein the specific functional group is a basic functional group or an acidic functional group. [4] The composition for treating a semiconductor device according to any one of [1] to [3], wherein the second repeating unit is a repeating unit derived from a second monomer having a basic functional group or an acidic functional group as the specific functional group, and when the second monomer has the basic functional group, the acid dissociation constant of the conjugated acid of the second monomer obtained by adding a proton to the basic functional group is 7.0 or more, and when the second monomer has the acidic functional group, the acid dissociation constant of the second monomer when a proton dissociates from the acidic functional group is 5.0 or less. [5] The composition for treating a semiconductor device according to any one of [1] to [4], wherein the polymer is a block copolymer comprising an A block composed of the first repeating unit and a B block composed of the second repeating unit. [6] The composition for treating a semiconductor device according to any one of [1] to [5], wherein the first repeating unit is a repeating unit represented by formula (A1) described below, the second repeating unit is a repeating unit represented by formula (A2) described below, and the polymer is a block copolymer comprising an A block composed of the first repeating unit and a B block composed of the second repeating unit. [7] The composition for treating a semiconductor device according to any one of [1] to [6], wherein the specific functional group is an amino group, a pyridyl group, an imidazole group, a hydrazine group, or a guanidine group. [8] The composition for treating a semiconductor device according to any one of [1] to [7], wherein the specific functional group is a primary amino group, a secondary amino group, or a tertiary amino group. [9] The composition for treating a semiconductor device according to any one of [1] to [6], wherein the specific functional group is a phosphonic acid group, a phosphinic acid group, a phosphate group, a sulfo group, or a carboxy group.

[10] The composition for treating a semiconductor device according to any one of [1] to [6], wherein the specific functional group is a phosphonic acid group, a phosphate group, or a sulfo group.

[11] The composition for treating a semiconductor device according to any one of [1] to

[10] , wherein the content of the first repeating unit is 50 mol % or more based on all repeating units in the polymer.

[12] The composition for treating a semiconductor device according to any one of [1] to

[11] , wherein the number average molecular weight of the polymer is 10,000 or less.

[13] R. ２ is a linear or branched aliphatic hydrocarbon group having 7 or more carbon atoms, which may have a substituent, or a group formed by combining a linear or branched aliphatic hydrocarbon group having 7 or more carbon atoms, which may have a substituent, and an aromatic group, which may have a substituent.

[14] The composition for treating a semiconductor device according to any one of [1] to

[13] , wherein the total amount of the polymer and the solvent is 99.0 mass % or more based on the total mass of the composition for treating a semiconductor device.

[15] The composition for treating a semiconductor device according to any one of [1] to

[14] , wherein a film obtained by applying the composition for treating a semiconductor device has a water contact angle of 60 degrees or more.

[16] A method for producing a modified substrate, comprising the step of contacting a substrate with the composition for treating a semiconductor device according to any one of [1] to

[15] to form a coating on the substrate.

[17] A method for producing a laminate, comprising: Step 1 of contacting a substrate having at least two surfaces, a first surface and a second surface, each made of a different material, with the composition for treating a semiconductor device according to any one of [1] to

[15] to form a first coating on the first surface; and Step 2 of subjecting the substrate obtained in Step 1 to atomic layer deposition to form a second coating on the second surface.

[18] A method for producing an electronic device, comprising the method for producing a modified substrate according to

[17] .

[0009] The present invention provides a composition for semiconductor device processing that can form a coating on a specific region of a substrate to suppress film formation by atomic layer deposition. The present invention also provides methods for producing a modified substrate, a laminate, and an electronic device.

[0010] The present invention will be described in detail below. The following description of the components may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0011] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In this specification, "ppm" means "parts-per-million (10 －６ ) and "ppb" stands for "parts-per-billion (10 －９ ) and "ppt" stands for "parts-per-trillion (10 －１２ In this specification, when two or more types of a component are present, the "content" of the component means the total content of those two or more components.

[0012] In the present specification, when there are multiple substituents, linking groups, etc. (hereinafter referred to as "substituents, etc.") represented by a specific symbol, or when multiple substituents, etc. are simultaneously specified, this means that the respective substituents, etc. may be the same or different from each other. The same applies to the specification of the number of substituents, etc. The compounds described in the present specification may contain structural isomers, optical isomers, and isotopes, unless otherwise specified. Furthermore, one type of structural isomer, optical isomer, and isotope may be contained alone, or two or more types may be contained. In the present specification, unless otherwise specified, the bonding direction of a divalent group (e.g., -CO-O-) is such that when Y in a compound represented by "X-Y-Z" is -CO-O-, the compound may be either "X-O-CO-Z" or "X-CO-O-Z."

[0013] In this specification, "(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, and "(meth)acryloyl" is a concept that includes either or both of acryloyl and methacryloyl.

[0014] In this specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is a weight average molecular weight. Furthermore, in this specification, unless otherwise specified, the weight average molecular weight (Mw), number average molecular weight (Mn), and polydispersity index (PDI; Poly Dispersity Index) (Mw / Mn) of a polymer are defined as polystyrene equivalent values ​​measured by GPC (Gel Permeation Chromatography) using a GPC (HLC-8120GPC, manufactured by Tosoh Corporation) apparatus (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, 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 (Refractive Index Detector)).

[0015] In this specification, the ClogP value refers to a value obtained by calculating the common logarithm logP of the partition coefficient P between 1-octanol and water. Known methods and software can be used to calculate the ClogP value, but unless otherwise specified, in the present invention, structures are drawn using ChemDraw Professional (version 20.1.1.1) manufactured by PerkinElmer, and values ​​calculated using the above software package 1 are used. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V20.1.1 for Solaris (1994-2007 ACD / Labs)

[0016] In this specification, pKa is a value calculated using the above software package 1 based on a database of Hammett's substituent constants and known literature values. If pKa cannot be calculated by the above method, a value calculated by a molecular orbital calculation method is used. As a specific method using a molecular orbital calculation method, a value obtained using Gaussian 16 based on DFT (density functional theory) is used.

[0017] [Composition] The composition of the present invention (hereinafter also referred to as "the composition") is described in detail below. The composition is a composition for treating semiconductor devices, comprising a polymer having a first repeating unit derived from a first monomer having a ClogP of 4.0 or more and a second repeating unit having a specific functional group that bonds to or adsorbs to a substrate, and a solvent.

[0018] Although the reason why the composition having the above configuration can solve the problems of the present invention is not entirely clear, the inventors speculate as follows. The following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than the one described below, it is still within the scope of the present invention. The specific functional group possessed by the polymer can bind to or adsorb to the surface of a substrate, such as a metal surface, and form a coating. Furthermore, the first repeating unit derived from the first monomer having the ClogP of 4.0 or more possessed by the polymer is relatively hydrophobic and highly effective in inhibiting film formation by ALD processing. Therefore, it is believed that the polymer having the above structure allows the formation of a coating that can effectively inhibit film formation by ALD processing. Hereinafter, the ability of this composition to form a coating that further inhibits film formation by atomic layer deposition processing (hereinafter also referred to as an "ALD-inhibiting film") is also referred to as "excellent effects of the present invention."

[0019] [Polymer] The present composition contains a polymer. The polymer has the first repeating unit and the second repeating unit. The first repeating unit and the second repeating unit will be described in detail below.

[0020] <First Repeating Unit> The polymer has a first repeating unit. The polymer may have one type of first repeating unit alone or multiple types. The content of the first repeating unit in the polymer is preferably 10 mol% or more, more preferably 30 mol% or more, even more preferably 50 mol% or more, and particularly preferably 75 mol% or more, relative to the total repeating units of the polymer. The upper limit is not particularly limited, but examples include 99.9 mol% or less. The first repeating unit is a repeating unit derived from a first monomer having a ClogP of 4.0 or more. When the ClogP value of the first monomer is within the above range, a portion of the polymer exhibits hydrophobicity, and therefore, a coating of the composition can sufficiently suppress film formation by atomic layer deposition. The ClogP of the first monomer is not particularly limited as long as it is 4.0 or more, but is preferably 5.0 or more, more preferably 8.0 or more, and even more preferably 10.0 or more. The upper limit is not particularly limited, but examples include 30.0 or less.

[0021] The first monomer is not particularly limited as long as it has a ClogP value of 4.0 or more, and examples thereof include (meth)acrylate monomers having a hydrophobic group, aromatic vinyl monomers having a hydrophobic group, and trifluoroethylene monomers having a hydrophobic group. Each of the above monomers may have two or more hydrophobic groups. The number of carbon atoms in the hydrophobic group of each of the above monomers is preferably 4 or more, more preferably 5 or more, even more preferably 7 or more, and particularly preferably 10 or more. The upper limit is not particularly limited, and examples thereof include 50 or less.

[0022] More specifically, examples of hydrophobic groups include aliphatic hydrocarbon groups which may have a substituent, aromatic groups which may have a substituent, and groups formed by combining these. The aliphatic hydrocarbon groups may be linear, branched, or cyclic. Examples of aliphatic hydrocarbon groups include alkyl groups, alkenyl groups, and alkynyl groups. The linear or branched aliphatic hydrocarbon groups preferably have 4 to 30 carbon atoms, more preferably 7 to 30 carbon atoms, and even more preferably 10 to 30 carbon atoms. The cyclic aliphatic hydrocarbon groups may be monocyclic, such as a cyclohexane ring, or polycyclic, such as adamantane. The cyclic aliphatic hydrocarbon groups preferably have a structure branched from a ring. Examples of cyclic aliphatic hydrocarbon groups having such a structure include aliphatic hydrocarbon groups formed by removing a hydrogen atom from t-butylcyclohexane. The cyclic aliphatic hydrocarbon groups preferably have 6 to 30 carbon atoms, more preferably 7 to 30 carbon atoms, and even more preferably 8 to 20 carbon atoms.

[0023] Examples of substituents that the aliphatic hydrocarbon group may have include halogen atoms, and among these, fluorine atoms are preferred. The aliphatic hydrocarbon group may also have an oxygen atom between carbon atoms. In other words, the aliphatic hydrocarbon group may have an etheric oxygen atom between carbon atoms.

[0024] The aromatic group may be either monocyclic or polycyclic. The aromatic group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, but an aromatic hydrocarbon group is preferred. The number of carbon atoms in the aromatic group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 15.

[0025] Examples of the substituent that the aromatic group may have include the aliphatic hydrocarbon groups described above. Specific and preferred embodiments of the aliphatic hydrocarbon group are as described above. Of the aliphatic hydrocarbon groups that the aromatic group may have, aliphatic hydrocarbon groups having 1 to 30 carbon atoms are preferred, aliphatic hydrocarbon groups having 1 to 20 carbon atoms are more preferred, and alkyl groups having 1 to 20 carbon atoms are even more preferred. The number of substituents that the aromatic group may have is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2.

[0026] Examples of groups formed by combining an optionally substituted aliphatic hydrocarbon group and an optionally substituted aromatic group include a divalent aliphatic hydrocarbon group-aromatic group, or an aromatic group having an aliphatic hydrocarbon group as a substituent. The divalent aliphatic hydrocarbon group may be linear, branched, or cyclic, but linear or branched is preferred. Examples of divalent aliphatic hydrocarbon groups include alkylene groups, alkenylene groups, and alkynylene groups, with alkylene groups being preferred. The divalent aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. Specific examples and preferred embodiments of the aromatic group are as described above. Specific examples and preferred embodiments of the aliphatic hydrocarbon group as a substituent are also as described above.

[0027] The hydrophobic group may also be a perfluoroalkyl group which may have an etheric oxygen atom. The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 6. Examples of perfluoroalkyl groups which have an etheric oxygen atom include -O-CF ２ -CF ２ -CF ２ -O-CF ３ Examples of the group include a group represented by the following formula:

[0028] The first repeating unit is preferably a repeating unit represented by the following formula (A1).

[0029]

[0030] In formula (A1), R １ represents a hydrogen atom or a methyl group. １ represents a single bond or an (n+1)-valent linking group. n represents an integer of 1 to 3. n is preferably 1 or 2. Examples of the (n+1)-valent linking group include an (n+1)-valent aliphatic hydrocarbon group, an (n+1)-valent aromatic group, -O- (etheric oxygen atom), -CO- (carbonyl group), and -NR Ｃ - (R Ｃrepresents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ), -N< (nitrogen atom), and groups formed by combining two or more of these groups. Examples of linking groups formed by combining two or more of the above groups include -divalent aromatic ring group-O-divalent aliphatic hydrocarbon group-, -COO- (ester bond), -CONH- (amide bond), -COO-divalent aromatic ring group-, -CONH-divalent aromatic ring group-, -COO-divalent aliphatic hydrocarbon group-, -CONH-divalent aliphatic hydrocarbon group-, -COO-divalent aromatic ring group-N<, -CONH-divalent aromatic ring group-N<, -COO-divalent aliphatic hydrocarbon group-N<, and -CONH-divalent aliphatic hydrocarbon group-N<.

[0031] The divalent aliphatic hydrocarbon group may be linear, branched, or cyclic, but is preferably linear. Examples of the divalent aliphatic hydrocarbon group include an alkylene group, an alkenylene group, and an alkynylene group, with an alkylene group being preferred. The divalent aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 10, even more preferably 1 to 6, and particularly preferably 1 or 2.

[0032] The divalent aromatic 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 group may be either monocyclic or polycyclic. The divalent aromatic group preferably has 4 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms. More specific examples of the arylene group include groups represented by any of the following formulas (2-1) to (2-3). In the formulas, * represents a bonding position.

[0033]

[0034] The divalent aliphatic hydrocarbon group and the divalent aromatic group may have a substituent. Examples of the substituent that the divalent aliphatic hydrocarbon group may have include a halogen atom. Examples of the substituent that the divalent aromatic group may have include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom.

[0035] In the above formula (A1), R ２ R represents an aliphatic hydrocarbon group which may have a substituent and which may have an oxygen atom between carbon atoms, an aromatic group which may have a substituent, or a group formed by combining these. ２ Specific and preferred embodiments of each group represented by R are as described above in detail for the hydrophobic group. ２ is preferably a linear or branched aliphatic hydrocarbon group having 7 or more carbon atoms which may have a substituent, or a group formed by combining a linear or branched aliphatic hydrocarbon group having 7 or more carbon atoms which may have a substituent and an aromatic group which may have a substituent. The number of carbon atoms in the linear or branched aliphatic hydrocarbon group is more preferably 10 or more, and even more preferably 15 or more. There is no particular upper limit, but examples thereof include 50 or less.

[0036] <Second Repeating Unit> The polymer has a second repeating unit. The polymer may have one type of second repeating unit alone or multiple types. The content of the second repeating unit in the polymer is preferably 90 mol% or less, more preferably 50 mol% or less, and even more preferably 10 mol% or less, based on the total repeating units of the polymer. There is no particular lower limit, but an example is 0.1 mol% or more.

[0037] The polymer may contain the first repeating unit and the second repeating unit in any manner, and the polymer may be a random copolymer in which the first repeating unit and the second repeating unit are randomly copolymerized. However, in terms of achieving better effects of the present invention, a block copolymer containing an A block composed of the first repeating unit and a B block composed of the second repeating unit is preferred, and an A-B block copolymer is more preferred. In this specification, an "A-B block copolymer" refers to any copolymer in which the end of a polymer chain (A block) polymerized with the first repeating unit is covalently linked to the end of a polymer chain (B block) polymerized with the second repeating unit. The polymerization mode of each repeating unit in the A block and the B block is not particularly limited. That is, when a polymer has multiple first repeating units, the multiple first repeating units in the A block may be randomly copolymerized or block copolymerized together. Furthermore, when a polymer has multiple second repeating units, the multiple second repeating units in the B block may be randomly copolymerized or block copolymerized together.

[0038] As described above, the second repeating unit is a repeating unit having a specific functional group that bonds to or adsorbs to a substrate. The number of specific functional groups that the second repeating unit has is not particularly limited as long as it is 1 or more, but is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2.

[0039] Specific examples of the bonding or adsorption between the specific functional group and the substrate include, for example, covalent bonding, coordinate bonding, ionic bonding, hydrogen bonding, acid-base interaction, van der Waals bonding, and metallic bonding. When the composition is used to form a coating on a metal surface A of a substrate composed of a material containing metal atoms, coordinate bonding or ionic bonding is preferred, and coordinate bonding is more preferred. When the composition is used to form a coating on a non-metal surface B of a substrate composed of a non-metal material, hydrogen bonding, acid-base interaction, or covalent bonding is preferred. Details of the substrate and the surface of the substrate will be described later.

[0040] The specific functional group is preferably either a group that bonds to or adsorbs onto a metal surface A of the substrate (also referred to as "specific functional group A") or a group that bonds to or adsorbs onto a non-metal surface B of the substrate (also referred to as "specific functional group B"), and is more preferably the specific functional group A. The specific functional group A is preferably a functional group that can form a coordinate bond with a metal.

[0041] Examples of the specific functional group include a basic functional group and an acidic functional group. In addition, examples of the specific functional group include a nitrogen-containing group, a hydroxy 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, or a disulfide bond-containing group, but these groups are preferably basic functional groups or acidic functional groups.

[0042] When the second repeating unit is a repeating unit derived from a second monomer having a basic functional group as the specific functional group, the acid dissociation constant of the conjugate acid of the second monomer obtained by adding a proton to the basic functional group is preferably 7.0 or more, more preferably 8.0 or more, even more preferably 9.0 or more, and particularly preferably 9.5 or more. An upper limit of this constant is, for example, 30.0 or less. Furthermore, when the second repeating unit is a repeating unit derived from a second monomer having an acidic functional group as the specific functional group, the acid dissociation constant of the second monomer when a proton dissociates from the acidic functional group is preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 3.0 or less. A lower limit of this constant is, for example, -5.0 or more.

[0043] Examples of the basic functional group include a nitrogen-containing group. Examples of the nitrogen-containing group include an amino group (—NR Ｎ ２ ), quaternary ammonium group (-N ＋ R Ｎ ３ ), a hydrazine group, a guanidine group, and a nitrogen-containing heterocyclic group. Ｎeach independently represents a hydrogen atom or an organic group (a group containing at least one carbon atom). Ｎ ２ ) in R Ｎ is preferably an alkyl group having 3 or less carbon atoms. Examples of the nitrogen-containing heterocyclic group include nitrogen-containing aromatic heterocyclic groups such as a pyrrole group, an imidazole group, a pyrazole group, an oxazolyl group, a triazole group, a benzimidazole group, a benztriazole group, a pyridyl group, and a triazine group, and nitrogen-containing aliphatic heterocyclic groups such as a pyrrolidinyl group, a piperidinyl group, and a piperazinyl group.

[0044] Among these, the basic functional group is preferably an amino group or a nitrogen-containing aromatic heterocyclic group. The amino group may be any of a primary amino group, a secondary amino group, and a tertiary amino group, but a primary amino group is preferred. When the amino group is a secondary amino group or a tertiary amino group, the number of carbon atoms is preferably 1 to 15, more preferably 1 to 10, still more preferably 1 to 6, and particularly preferably 1 to 3. The nitrogen-containing aromatic heterocyclic group is preferably an aromatic heterocyclic group having 5 or 6 ring atoms, such as an imidazole group or a pyridyl group.

[0045] The acidic functional group may be a phosphonic acid group (-PO ３ H ２ ), phosphinic acid group (-PO ２ H ２ ), phosphate group (-PO ４ H ２ ), sulfo group (—SO ３ Examples of the alkyl group include a phosphonic acid group, a phosphinic acid group, a phosphoric acid group, a sulfo group, and a carboxy group, and more preferably a phosphonic acid group, a phosphoric acid group, or a sulfo group.

[0046] When the specific functional group is the specific functional group B, it is preferably a group capable of forming a hydrogen bond, an acid-base interaction, or a covalent bond (e.g., an Si—O bond, an Si—C bond, etc.) with a nonmetal. Examples of the specific functional 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.

[0047] The second repeating unit is preferably a repeating unit represented by the following formula (A2).

[0048]

[0049] In formula (A2), R ３ represents a hydrogen atom or a methyl group. ２ represents a single bond or an (m+1)-valent linking group. m represents an integer of 1 to 3. m is preferably 1 or 2. L ２ Examples of the (m+1)-valent linking group represented by the formula (A1) include L １ Specific examples of the (n+1)-valent linking group represented by the formula: ２ Regarding the preferred embodiment of the (m+1)-valent linking group represented by １ These are the same as the preferred embodiments of the (n+1)-valent linking group represented by the following formula:

[0050] In formula (A2), X represents a basic functional group or an acidic functional group. Specific examples and preferred embodiments of the basic functional group and acidic functional group represented by X are as described above in detail for the specific functional group. Among these, the basic functional group represented by X is preferably an amino group, a pyridyl group, an imidazole group, a hydrazine group, or a guanidine group. Among these, the acidic functional group represented by X is preferably a phosphonic acid group, a phosphinic acid group, a phosphoric acid group, a sulfo group, or a carboxy group, and more preferably a phosphonic acid group, a phosphoric acid group, or a sulfo group.

[0051] The polymer may have a repeating unit other than the first repeating unit and the second repeating unit described above. The other repeating units may be used alone or in combination of two or more. The content of the other repeating units is preferably 0 to 20 mol %, more preferably 0 to 10 mol %, and even more preferably 0 to 5 mol %, based on the total repeating units of the polymer.

[0052] Among these, the polymer is preferably a block copolymer in which the first repeating unit is a repeating unit represented by the above formula (A1), the second repeating unit is a repeating unit represented by the above formula (A2), and the block A is composed of the first repeating unit, and the block B is composed of the second repeating unit. As described above, the block copolymer is more preferably an A-B block copolymer.

[0053] In order to obtain superior effects of the present invention, the number average molecular weight of the polymer is preferably 30,000 or less, more preferably 20,000 or less, even more preferably 10,000 or less, and particularly preferably 5,000 or less. The lower limit is, for example, 500 or more. The weight average molecular weight of the polymer is preferably 40,000 or less, more preferably 15,000 or less, and even more preferably 6,000 or less. The lower limit is, for example, 500 or more. In order to obtain superior effects of the present invention, the polydispersity (Mw / Mn, PDI) of the polymer is preferably 5.0 or less, more preferably 2.0 or less, even more preferably 1.5 or less, and particularly preferably 1.3 or less. The lower limit is usually 1.0, and preferably 1.05 or more.

[0054] The polymer may be used alone or in combination of two or more. The content of the polymer is preferably 10.00% by mass or less, more preferably 5.00% by mass or less, and even more preferably 3.00% by mass or less, relative to the total mass of the composition. The lower limit is not particularly limited, but is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.10% by mass or more. The total amount of the polymer and the solvent described below is preferably 90.00% by mass or more, more preferably 95.00% by mass or more, and even more preferably 99.90% by mass or more, relative to the total mass of the composition. The upper limit is less than 100% by mass, and preferably 99.9999% by mass or less.

[0055] [Solvent] The present composition contains a solvent. Examples of the solvent include water and organic solvents, with organic solvents being preferred. Examples of the 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.

[0056] Examples of alcohol-based solvents include monoalcohol-based solvents, polyol-based solvents, and glycol monoether-based solvents. Examples of monoalcohol-based solvents include aliphatic monoalcohol-based 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-based solvents having 3 to 18 carbon atoms, such as cyclohexanol; aromatic monoalcohol-based solvents, such as benzyl alcohol; and ketone monoalcohol-based solvents, such as diacetone alcohol. Examples of polyol-based solvents 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. Examples of glycol monoether solvents 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 mono-n-propyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobenzyl ether, and diethylene glycol monobenzyl ether.The alcohol solvent preferably has 1 to 19 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 3 to 8 carbon atoms.

[0057] Examples of 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.

[0058] Examples of ester solvents include glycol ester solvents, monocarboxylic acid ester solvents such as n-butyl acetate and ethyl lactate, lactone solvents such as γ-butyrolactone (GBL) and δ-valerolactone, and carbonate solvents such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate. Examples of 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 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 propylene glycol monomethyl ether acetate. Examples of the ester-based solvent include glycol monoether carboxylate solvents having 5 to 21 carbon atoms, such as ethylene glycol monobutyl ether acetate, diethylene 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 number of carbon atoms in the ester-based solvent is preferably 3 to 22, and more preferably 4 to 12.

[0059] Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents such as n-pentane and n-hexane, alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane, and aromatic hydrocarbon solvents such as toluene and xylene.

[0060] Examples of ketone solvents include 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.

[0061] Examples of amide solvents include formamide, monomethylformamide, dimethylformamide, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide, and N-methylpyrrolidone.

[0062] Examples of sulfur-containing solvents include dimethyl sulfone, dimethyl sulfoxide, and sulfolane.

[0063] The solvent is preferably an alcohol solvent, an ether solvent, an ester solvent, or a ketone solvent, more preferably an aliphatic monoalcohol solvent, a glycol monoether solvent, a glycol ester solvent, a monocarboxylic acid ester solvent, an ether solvent, or a lactone solvent, and even more preferably a glycol monoether solvent or a glycol ester solvent. Among these, the solvent preferably contains at least one selected from the group consisting of PGMEA, PGME, cyclohexanone, ethyl lactate, methyl isobutyl carbinol, EtOH, and γ-butyrolactone, and more preferably contains at least one selected from the group consisting of PGMEA, PGME, cyclohexanone, ethyl lactate, and methyl isobutyl carbinol.

[0064] The solvent may be used alone or in combination of two or more. 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 preferably less than 100% by mass, more preferably 99.999% by mass or less, and even more preferably 99.9% by mass or less. The content of one solvent in the composition 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 amount of all solvents. The upper limit is not particularly limited and may be 100% by mass.

[0065] [Other Components] The composition may contain other components in addition to the polymer and the solvent. Examples of the other components include a polymerization inhibitor. Examples of the polymerization inhibitor include a phenolic compound, a quinone compound, a free radical compound, an amine compound, and a phosphine compound.

[0066] [Method for producing the present composition] The method for producing the present 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 to a stirrer such as a mixer containing a purified solvent, followed by thorough stirring. In order to achieve better effects of the present invention, it is preferable that the raw materials for the present composition (e.g., the solvent and the polymer) have been subjected to a purification treatment.

[0067] The production process of the present composition may include a step selected from the group consisting of a distillation step of distilling raw materials, a dehydration step of dehydrating the present composition, a metal removal step of removing metal components from the present composition, a filtration step of filtering the present composition, and a static elimination step of destaticizing the present composition.

[0068] This composition can be filled into a known container for storage, transportation, and use. As a container, a container with a high degree of cleanliness within the container for semiconductor applications and which suppresses the elution of impurities from the inner wall of the container's storage section into each liquid is preferred. Examples of such containers include various containers 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 to these. Furthermore, the containers exemplified in paragraphs

[0121] to

[0124] of WO 2022 / 004217 can also be used as containers, and the contents of these containers are incorporated herein.

[0069] [Uses of the Composition] The composition is a composition for semiconductor device processing, and is preferably used for modifying a substrate in the manufacturing process of a semiconductor device. In the above process, the composition is used to form a coating that inhibits film formation by atomic layer deposition, thereby obtaining a modified substrate having a coating formed on the substrate surface. The composition is also preferably used for manufacturing a laminate in which a material is deposited in areas where no coating has been formed by ALD processing of the modified substrate. Methods for manufacturing a modified substrate and a laminate will be described in detail below.

[0070] <Substrate> 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.

[0071] The metal atoms contained in the metal surface A are not particularly limited, but are preferably tungsten atoms, copper atoms, ruthenium atoms, cobalt atoms, titanium atoms, tantalum atoms, molybdenum atoms, germanium atoms, zirconium atoms, aluminum atoms, tin atoms, nickel atoms, palladium atoms, indium atoms, zinc atoms, gold atoms, silver atoms, or platinum atoms, more preferably tungsten atoms, ruthenium atoms, molybdenum atoms, copper atoms, or cobalt atoms, and even more preferably tungsten atoms or copper atoms. The form of the metal atoms in the metal surface A is not particularly limited, but includes elemental metals, alloys, nitrides, oxides, and silicides, with elemental metals or alloys being preferred. Examples of alloys include alloys containing two or more of the metal atoms contained in the metal surface A described above. The method for forming the metal surface A is not particularly limited, and known methods can be used. For example, CVD, plating, and physical vapor deposition methods can be used.

[0072] Examples of non-metallic materials constituting the non-metallic surface B include insulators, such as 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 materials. The material constituting the non-metallic surface B is preferably a non-metallic material containing silicon atoms, more preferably silicon oxide. Specific examples of silicon oxide include SiO ｙ (wherein y is preferably 0.5 to 2.0, more preferably 1.0 to 2.0), and 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). ｙ and SiO ｚ C ｗ The material represented by the composition may further contain hydrogen. ｚ C ｗ Examples of the material represented by the composition include Si(OC ２ H ５ ) ４(tetraethyl orthosilicate, TEOS). Silicon oxides include SiO ２ A material represented by the formula (silicon dioxide) or TEOS is preferred.

[0073] The method for forming the non-metallic surface B is not particularly limited, and examples thereof include CVD, physical vapor deposition, 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. Examples of the treatment include contact with a treatment liquid such as an aqueous solution containing an acidic compound (preferably hydrogen fluoride water), plasma treatment, corona treatment, and ozone treatment.

[0074] It is also preferable that the substrate has at least two types of surfaces, a first surface and a second surface, which are made of different materials. The first surface is a surface that interacts with a specific functional group of the polymer. The second surface may be made of a material different from the first surface, but is preferably a surface on which a coating does not form when it comes into contact with the composition. In particular, it is preferable that 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.

[0075] A preferred embodiment of the substrate is embodiment 1, in which the first surface is a metal surface A. In embodiment 1, the specific functional group possessed by the polymer is the specific functional group A described above. In embodiment 1, the metal atoms contained in the metal surface A, which is the first surface, are preferably contained in the form of a metal element, an alloy, a conductive metal nitride, or a metal silicide, and more preferably a metal element or an alloy. Examples of the metal element and alloy include the metal elements and alloys thereof exemplified as the metals contained in the metal surface A. Examples of the conductive metal nitride include tantalum nitride, titanium nitride, iron nitride, and aluminum nitride. Examples of the metal silicide include iron silicide, molybdenum silicide, and tungsten silicide.

[0076] In Aspect 1, the second surface is preferably a metal surface A or a non-metal surface B different from the first surface, more preferably a non-metal surface B. In Aspect 1, the metal atoms contained in the metal surface A constituting the second surface are preferably in the form of a metal oxide, a metal nitride, or a metal oxynitride, more preferably a metal oxide. Examples of metal oxides include aluminum oxide, tantalum oxide, iron oxide, and copper oxide.

[0077] A preferred embodiment of the substrate also includes embodiment 2, in which the first surface is a non-metallic surface B. In embodiment 2, the specific functional group possessed by the polymer is the above-described specific functional group B. In embodiment 2, the second surface is preferably a metallic surface A. In embodiment 2, the metal atoms contained in the second surface, that is, the metallic surface A, 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.

[0078] The shape of the first surface and the second surface is not particularly limited, and examples thereof include a planar shape, a dotted shape, and a striped shape.

[0079] The shape of the substrate is not particularly limited, and any shape of substrate generally used as a semiconductor substrate can be used. The substrate may be a substrate having the above-described surface, and may be a single-layer or multi-layer structure.

[0080] <Coating> The coating formed on a substrate using the present composition is a coating containing components other than the solvent contained in the present composition (e.g., a polymer). The coating preferably functions as a mask when depositing a material in an ALD process. That is, when an ALD process is performed on a modified substrate on which a coating using the present composition has been formed in a specific region, the material preferably does not deposit in the region where the coating has been formed, but deposits in the region where the coating has not been formed, forming a film (hereinafter also referred to as an "ALD film"). This results in a laminate in which an ALD film has been selectively formed in regions other than the region where the coating has been formed.

[0081] The coating also preferably functions 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. Examples of CVD other than ALD that can be preferably applied to the modified substrate include known methods such as thermal CVD and plasma CVD. As raw materials for the CVD film used in the CVD process, raw materials for the ALD film described below can be used.

[0082] 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.

[0083] In order to obtain superior effects of the present invention, 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 it is often 120° or less. The water contact angle is the average value of three measurements of the contact angle 500 milliseconds after a water droplet contacts the surface of the measurement object using a contact angle meter (DMs-501, manufactured by Kyowa Interface Science Co., Ltd.).

[0084] [Method for Producing a Modified Substrate] The method for producing a modified substrate of the present invention includes a step of contacting a substrate with the present composition to form a coating on the substrate. This results in a modified substrate having a coating formed on the substrate. The method for producing a modified substrate of the present invention can be suitably used, for example, in the production of electronic devices (semiconductor devices). The method for contacting a substrate with the present composition is not particularly limited, and known methods can be used. Examples include a method of applying (e.g., spin coating) or spraying the present composition onto a substrate, and a method of immersing a substrate in the present composition. When immersing a substrate in the present composition, the present composition may be subjected to convection. The temperature of the present composition when contacting the substrate with the present composition is not particularly limited, but is preferably 0 to 50°C, more preferably 10 to 30°C. The time for contacting the substrate with the present composition is also not particularly limited, but is preferably 30 seconds to 1 hour, more preferably 30 seconds to 30 minutes, and even more preferably 5 to 15 minutes.

[0085] After contacting the substrate with the composition, the coating film may be subjected to a heat treatment. The heating method is not particularly limited, and known methods can be used, such as an oven or a hot plate. The heating temperature is preferably 50 to 400°C, more preferably 100 to 350°C, even more preferably 130 to 300°C, and particularly preferably 150 to 250°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 1 to 30 minutes, and even more preferably 3 to 10 minutes.

[0086] After contacting the substrate with the present composition, it is also preferable to perform a rinsing treatment. The rinsing treatment can remove at least one of the present composition and impurities adhering to regions on the substrate other than the desired region (e.g., the region that interacts with the specific functional group contained in the polymer) from the substrate. The rinsing method is not particularly limited, and examples include a method of contacting the substrate with a rinsing liquid. As the contact method, the same method as the method of contacting the present composition with the substrate can be used. 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. As the rinsing liquid, a known organic solvent can be used, such as the alcohol-based solvents, ether-based solvents, and ester-based solvents described above.

[0087] [Method for Producing Laminate] The method for producing a laminate of the present invention includes step 1 of contacting a substrate having at least two surfaces, a first surface and a second surface, each made of a different material (hereinafter also referred to as a "specific substrate") 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. This results in a laminate having a second coating (ALD film) on the second surface.

[0088] [Step 1: Method for producing modified substrate] Step 1 is a step of bringing a specific substrate into contact with the present composition to form a first coating on the first surface. Step 1 results in a modified substrate 1 in which a first coating is formed on the first surface of the specific substrate. The first coating is a coating containing the polymer contained in the present composition. The method for bringing the specific substrate into contact with the present composition is not particularly limited, and the method of bringing the present composition into contact with the substrate in the above-mentioned method for producing a modified substrate can be used.

[0089] After contacting the specific substrate with the composition, the coating film may be subjected to a heat treatment. The heating method is not particularly limited, and the heating methods in the above-mentioned method for producing a modified substrate can be used.

[0090] It is also preferable to perform a rinse treatment on the modified substrate 1 having the first coating formed on the first surface. The rinse treatment can remove at least one of the composition and impurities adhering to regions other than the first surface (e.g., the second surface) of the specific substrate from the specific substrate. The rinse method can be the same as the rinse method in the method for producing a modified substrate described above.

[0091] [Step 2: ALD Treatment] Step 2 is a step of subjecting the modified substrate 1 obtained in step 1 to ALD treatment to form a second coating on the second surface. Step 2 results in a laminate 1 having a first coating formed on the first surface and a second coating formed on the second surface. The second coating is a film formed by ALD treatment (ALD film). Note that the modified substrate 1 may be any substrate having a first coating formed on the first surface of the specific substrate in step 1, and may be subjected to the above-mentioned heating treatment, rinsing treatment, etc. after step 1.

[0092] The ALD process method is not particularly limited, and known methods can be used. For example, a method can be used in which a precursor gas serving as 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 a reducing agent, etc., to deposit the material, thereby forming an ALD film. The precursor is not particularly limited, and known precursors can be used depending on the type of ALD film to be formed, such as organometallic compounds. Examples of precursors that can be used include alumina, tantalum nitride, and titanium nitride. The oxidizing agent is not particularly limited, and known oxidizing agents used in ALD processes can be used, such as water, oxygen, and ozone.

[0093] The materials constituting the ALD film can be controlled by the type of precursor supplied, the supply atmosphere, the oxidizing agent, etc. The materials of the formed ALD film are not particularly limited, and include metals, metal oxides, and metal nitrides. Examples of metals include aluminum, titanium, chromium, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, palladium, lanthanum, cerium, hafnium, tantalum, tungsten, platinum, and bismuth. Examples of metal oxides include aluminum oxide, titanium oxide, zinc oxide, zirconium oxide, hafnium oxide, and tantalum oxide. Examples of metal nitrides include titanium nitride and tantalum nitride. In the ALD process, a treatment for modifying the surface of the region where the first coating is not formed may be performed.

[0094] After the ALD process, the thickness of the material deposited on the first coating is preferably as thin as possible, 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. 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 0.50 or less, and even more preferably 0.25 or less. The lower limit of the ratio is 0 or more.

[0095] [Step 3: Removal of Coating] 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. Step 3 results in a laminate 2 that has no coating on the first surface and has the second coating on the second surface.

[0096] The method for removing the first coating is not particularly limited, and examples thereof include dry etching, wet etching, and a combination thereof. Known methods can be used for dry etching, such as chemical dry etching, which supplies reactive ions or reactive radicals to the surface of the laminate 1, and physical dry etching, such as sputter etching and ion beam etching. Wet etching can be performed by supplying an etching solution to the laminate 1. Examples of the etching solution include etching solutions containing oxidizing agents such as ozone and hydrofluoric acid, and etching solutions containing an organic solvent. Examples of the organic solvent 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.

[0097] The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below. The preparation, filling, storage, etc. of the composition were all carried out in a clean room meeting ISO Class 2 or lower. Furthermore, 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.

[0098] [Preparation of the present composition] [Method of synthesizing polymer] Polymer E-15 was synthesized as follows.

[0099]

[0100] [Synthesis of 1-undecyl-4-vinylbenzene] 1-undecyl-4-vinylbenzene, which corresponds to the first monomer in polymer E-15, was synthesized as follows. 1-Undecene (2.5 g, 16.1 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a three-neck flask under a nitrogen flow (0.1 L / min). A 0.5 M solution of 9-BBN in tetrahydrofuran (THF) (37 mL, 18.4 mmol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was slowly added in an ice bath, and the mixture was stirred at 25°C for 2 hours. The mixture was then heated and refluxed for 5 hours while stirring. Tetrakistriphenylphosphine palladium (0.9 g, 0.8 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), a 2.0 M aqueous sodium hydroxide solution (43 mL), and 4-bromostyrene (2.8 g, 15.3 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the resulting reaction solution, and the mixture was stirred under reflux for 12 hours. After cooling to room temperature, the solid was removed using a funnel packed with Celite. The solvent was distilled off under reduced pressure at 40°C / 10 hPa, and methylene chloride (100 mL, Fujifilm Wako Pure Chemical Industries, Ltd.) was added thereto for extraction. The obtained organic phase was concentrated under reduced pressure at 40°C / 10 hPa. The obtained crude product was purified by silica gel column chromatography to obtain 1-undecyl-4-vinylbenzene.

[0101] [Synthesis of Polymer E-15] Under a nitrogen flow (0.1 L / min), 2-cyano-2-propyl dodecyl trithiocarbonate (6.91 g, 20.0 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), 1-undecyl-4-vinylbenzene (45.0 g, 174.1 mmol), and PGMEA (150 g, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a three-neck flask and stirred. AIBN (azobisisobutyronitrile, 0.66 g, 4.0 mmol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the resulting mixed solution, and the mixture was heated and stirred at 60°C for 3 hours. Next, 2-(dimethylamino)ethyl acrylate (11.3 g, 78.6 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) and AIBN (0.66 g, 4.0 mmol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added, and the mixture was heated and stirred at 60°C for 3 hours. After the reaction was completed, the polymerization reaction solution was cooled to room temperature and slowly added dropwise to methanol (700 g, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and the resulting precipitate was dried under reduced pressure to obtain polymer E-15.

[0102] Polymers other than the above polymer E-15 were synthesized according to the synthesis method for polymer E-15, with the raw materials and reaction conditions appropriately adjusted so as to obtain the following polymers.

[0103] The materials used in the preparation of the compositions of the Examples and Comparative Examples are listed below. For each polymer listed below, a repeating unit marked "(1)" indicates the first repeating unit, and a repeating unit marked "(2)" indicates the second repeating unit. Furthermore, repeating units marked "(1-1)" and "(1-2)" indicate the first and second first repeating units, respectively, and repeating units marked "(2-1)" and "(2-2)" indicate the first and second second repeating units, respectively. The content (mol %) of the first repeating unit, when the total number of repeating units in the polymer is taken as 100 mol %, the number-average molecular weight of the polymer, and the ClogP value of the first monomer (the monomer constituting the first repeating unit) are listed in the table below. The polydispersity of each polymer was 1.3 or less. The number-average molecular weight and polydispersity were obtained by GPC measurement under the conditions described above.

[0104] [Polymer]

[0105]

[0106]

[0107]

[0108] [Comparative Compounds]

[0109]

[0110] [Solvent] PGMEA: Propylene glycol monomethyl ether acetate

[0111] [Liquid Preparation] The compositions of each of the Examples and Comparative Examples were prepared by mixing the polymer or comparative compound with a solvent so as to obtain the composition shown in the table below.

[0112] [Preparation of modified substrate] A commercially available silicon wafer (diameter 12 inches) was prepared as a substrate. A tungsten (W) layer, a ruthenium (Ru) layer, a molybdenum (Mo) layer, a copper (Cu) layer, and a cobalt (Co) layer were formed on one surface of the silicon wafer, respectively, to prepare a W-layer wafer, a Ru-layer wafer, a Mo-layer wafer, a Cu-layer wafer, and a Co-layer wafer (hereinafter, these are also collectively referred to as "layered wafers"). The W layer, Ru layer, and Mo layer were formed by CVD, and the Cu layer and Co layer were formed by sputtering. The film formation conditions were adjusted so that the thickness of each layer was 20 nm. The silicon wafer and each layered wafer were cut into 2 cm squares and washed by immersion in isopropyl alcohol (IPA). The cleaning was performed while stirring the IPA at a stirring speed of 250 rpm, the IPA temperature was 25° C., and the cleaning time was 30 seconds. After cleaning, the wafer was dried by blowing nitrogen gas onto it.

[0113] Next, each of the cleaned wafers was immersed in each of the compositions to perform a modification treatment. The immersion was performed while stirring the composition at a stirring speed of 250 rpm, with the composition temperature at 25°C and the immersion time at 10 minutes. After the immersion, each wafer was immersed in IPA to perform a rinse treatment. The rinsing treatment was performed while stirring the IPA at a stirring speed of 250 rpm, with the IPA temperature at 25°C and the rinsing time at 30 seconds. After the rinsing, the wafer was dried by spraying nitrogen gas onto it. A modified substrate was obtained by the above procedure.

[0114] [Evaluation] [Evaluation of contact angle with pure water after substrate modification] For each of the modified substrates (silicon wafer and wafer with each layer) obtained in [Preparation of modified substrates], and for the substrates (unmodified substrates) before immersion in each composition, the contact angle was measured three times using a contact angle meter (DMs-501, manufactured by Kyowa Interface Science Co., Ltd.) at 23°C, 500 milliseconds after a water droplet contacted the surface of the measurement object, and the average value was taken as the contact angle (deg.). The surface tension of pure water was assumed to be 72.9 mN / m for the analysis.

[0115] [Evaluation of ALD Inhibition (Deposition Inhibition)] A tantalum nitride (TaN) layer (ALD film) was formed by ALD using an atomic layer deposition system (AD-230LP, manufactured by Samco) on each of the modified substrates (wafers with each layer) obtained by [Preparation of Modified Substrates] and on substrates (unmodified substrates: Comparative Examples CA1 to CE1) before immersion in each composition. PDMAT (pentakis(dimethylamino)tantalum) was used as the organometallic source and ammonia as the reducing agent, and the ALD treatment temperature was 300°C. Other conditions were adjusted so that the thickness of the ALD film formed on the unmodified substrate would be 5 nm. For example, in Table 1, an ALD film was formed on the modified substrate under conditions such that the thickness of the ALD film formed on the W layer wafer before immersion in the composition would be 5 nm. The thickness of the ALD film of each sample after ALD processing 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. From the obtained film thickness, ALD inhibition (deposition inhibition) was evaluated according to the following evaluation criteria. The smaller the film thickness, the more difficult it is for a film to deposit by ALD processing, i.e., the better the ALD inhibition. ALD inhibition of H or higher is preferred, with S being most preferred.

[0116] S: The thickness of the ALD film is less than 0.5 nm. A: The thickness of the ALD film is 0.5 nm or more and less than 1.0 nm. B: The thickness of the ALD film is 1.0 nm or more and less than 1.5 nm. C: The thickness of the ALD film is 1.5 nm or more and less than 2.0 nm. D: The thickness of the ALD film is 2.0 nm or more and less than 2.5 nm. E: The thickness of the ALD film is 2.5 nm or more and less than 3.0 nm. F: The thickness of the ALD film is 3.0 nm or more and less than 3.5 nm. G: The thickness of the ALD film is 3.5 nm or more and less than 4.0 nm. H: The thickness of the ALD film is 4.0 nm or more and less than 4.5 nm. I: The thickness of the ALD film is 4.5 nm or more.

[0117] [Results] The composition and evaluation results of each composition are shown in Tables 1 to 5. Table 1 shows the results assuming a W layer as the first surface, Table 2 shows the results assuming a Ru layer as the first surface, Table 3 shows the results assuming a Mo layer as the first surface, Table 4 shows the results assuming a Cu layer as the first surface, and Table 5 shows the results assuming a Co layer as the first surface, and all the results assuming a Si layer (silicon wafer) as the second surface.

[0118] In the tables, the "amount (parts by mass)" of the polymer or comparative compound represents the content (unit: parts by mass) of the polymer or comparative compound when the total mass of the composition is 100 parts by mass. In the tables, the content of the solvent is the remainder after subtracting the content of the polymer or comparative compound from the total mass of the composition. In the tables, the values ​​in the "mol % (1)" column indicate the content (mol %) of the first repeat unit when the total number of repeat units in the polymer is 100 mol %. In addition, the values ​​in the "mol % (1-1) / ((1-1)+(1-2))" column indicate the content (mol %) of the repeat unit marked with (1-1) when the total number of all first repeat units in the polymer is 100 mol %, and the values ​​in the "mol % (2-1) / ((2-1)+(2-2))" column indicate the content (mol %) of the repeat unit marked with (2-1) when the total number of all second repeat units in the polymer is 100 mol %. In the tables, the values ​​in the "Mn" column indicate the number average molecular weight of the polymer. In the tables, the "Structure" column indicates the structure of the polymer. "Random" indicates that the first repeating unit and the second repeating unit have a random structure. "Diblock" indicates that the polymer is an A-B block copolymer composed of an A block formed by polymerizing the first repeating unit and a B block formed by polymerizing the second repeating unit. In the tables, the values ​​in the "pKa(2) or (2-1)" and "pKa(2-2)" columns indicate, for the second monomer corresponding to each repeating unit marked "(2)," "(2-1)," or "(2-2)," if the second monomer has the basic functional group, the acid dissociation constant of the conjugated acid of the second monomer obtained by adding a proton to the basic functional group; if the second monomer has the acidic functional group, the value indicates the acid dissociation constant of the second monomer when a proton dissociates from the acidic functional group. In the "pKa(2) or (2-1)" column, the numerical value "<7.0" indicates that the acid dissociation constant was less than 7.0. In the table, the numerical values ​​in the "ClogP(1) or (1-1)" column and the "ClogP(1-2)" column indicate the ClogP values ​​of the first monomers corresponding to each repeating unit marked "(1)," "(1-1)," or "(1-2)." The acid dissociation constant and ClogP were calculated as described above.

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[0126] The results in Tables 1 to 5 confirm that the composition of the present invention can form a coating film that has excellent ALD inhibitory properties.

[0127] Furthermore, a comparison of Examples A5 to A7 confirmed that the ALD inhibitory properties were superior when the second repeating unit was a repeating unit derived from a second monomer having a basic functional group as a specific functional group, and when the acid dissociation constant of the conjugate acid of the second monomer obtained by adding a proton to the basic functional group was 7.0 or higher. A comparison of Examples A2 to A6 confirmed that the ALD inhibitory properties were superior when the first repeating unit was a repeating unit represented by Formula (A1), the second repeating unit was a repeating unit represented by Formula (A2), and the polymer was a block copolymer comprising an A block composed of the first repeating unit and a B block composed of the second repeating unit. A comparison of Examples A5 to A7 confirmed that the ALD inhibitory properties were superior when the specific functional group was an amino group, a pyridyl group, an imidazole group, a hydrazine group, or a guanidine group. Comparison of Examples A7 and A8 etc. confirmed that when the content of the first repeating unit is 50 mol% or more relative to the total repeating units in the polymer, the ALD inhibitory properties are more excellent. Comparison of Examples A8 and A9 etc. confirmed that when the number average molecular weight of the polymer is 10,000 or less, the ALD inhibitory properties are more excellent. Comparison of Examples A1 and A9 etc. confirmed that when R ２is a linear or branched aliphatic hydrocarbon group having 7 or more carbon atoms, which may have a substituent, or a group formed by combining a linear or branched aliphatic hydrocarbon group having 7 or more carbon atoms, which may have a substituent, and an aromatic group, which may have a substituent. Comparisons of Examples A10 to A14 and the like confirmed that, for a polymer, when the first monomer has a C log P of 8.0 or higher, the ALD inhibitory properties are more excellent. Comparisons of Examples A11 to A17 and the like confirmed that, when the specific functional group is a primary amino group, the ALD inhibitory properties are more excellent.

[0128] Furthermore, from a comparison of Examples D2 to D4, it was confirmed that the ALD inhibitory properties are superior when the second repeating unit is a repeating unit derived from a second monomer having an acidic functional group as the specific functional group, and when the acid dissociation constant of the second monomer when a proton dissociates from the acidic functional group is 5.0 or less.

Claims

1. A composition for semiconductor device processing, comprising a polymer having a first repeating unit derived from a first monomer with a ClogP of 4.0 or more and a second repeating unit having a specific functional group that binds or adsorbs to a substrate, and a solvent.

2. The composition for semiconductor device processing according to claim 1, wherein the polydispersity of the polymer is 1.5 or less.

3. The composition for semiconductor device processing according to claim 1, wherein the specific functional group is a basic functional group or an acidic functional group.

4. The second repeating unit is a repeating unit derived from a second monomer having a basic functional group or an acidic functional group as the specific functional group. When the second monomer has the basic functional group, the acid dissociation constant of the conjugate acid of the second monomer obtained by adding a proton to the basic functional group is 7.0 or more. When the second monomer has the acidic functional group, the acid dissociation constant of the second monomer when a proton dissociates from the acidic functional group is 5.0 or less. The composition for semiconductor device processing according to claim 1.

5. The composition for semiconductor device processing according to claim 1, wherein the polymer is a block copolymer containing an A block composed of the first repeating unit and a B block composed of the second repeating unit.

6. The first repeating unit is a repeating unit represented by the formula (A1), and the second repeating unit is a repeating unit represented by the formula (A2), and the polymer is a block copolymer including an A block composed of the first repeating unit and a B block composed of the second repeating unit. The composition for semiconductor device processing according to claim 1. In the formula (A1), R １ represents a hydrogen atom or a methyl group. L １ represents a single bond or an (n + 1)-valent linking group. n represents an integer of 1 to 3. R ２ may have a substituent and represents an aliphatic hydrocarbon group that may have an oxygen atom between carbon-carbon atoms, an aromatic group that may have a substituent, or a group formed by combining these. In the formula (A2), R ３ represents a hydrogen atom or a methyl group. L ２ represents a single bond or an (m + 1)-valent linking group. m represents an integer of 1 to 3. X represents a basic functional group or an acidic functional group.

7. The composition for semiconductor device processing according to claim 1, wherein the specific functional group is an amino group, a pyridyl group, an imidazole group, a hydrazine group, or a guanidine group.

8. The composition for semiconductor device processing according to claim 1, wherein the specific functional group is a primary amino group, a secondary amino group, or a tertiary amino group.

9. The composition for semiconductor device processing according to claim 1, wherein the specific functional group is a phosphonic acid group, a phosphinic acid group, a phosphate group, a sulfo group, or a carboxy group.

10. The composition for semiconductor device processing according to claim 1, wherein the specific functional group is a phosphonic acid group, a phosphate group, or a sulfo group.

11. The composition for semiconductor device processing according to claim 1, wherein the content of the first repeating unit is 50 mol% or more based on all the repeating units in the polymer.

12. The composition for semiconductor device processing according to claim 1, wherein the number average molecular weight of the polymer is 10,000 or less.

13. R ２ is a linear or branched aliphatic hydrocarbon group having 7 or more carbon atoms which may have a substituent, or a group formed by combining a linear or branched aliphatic hydrocarbon group having 7 or more carbon atoms which may have a substituent and an aromatic group which may have a substituent, the composition for treating a semiconductor device according to claim 6.

14. The composition for semiconductor device processing according to claim 1, wherein the total amount of the polymer and the solvent is 99.0% by mass or more based on the total mass of the composition for semiconductor device processing.

15. The composition for semiconductor device processing according to claim 1, wherein the water contact angle of the film obtained by applying the composition for semiconductor device processing is 60 degrees or more.

16. A method for manufacturing a modified substrate, comprising a step of forming a film on the substrate by bringing the substrate into contact with the composition for semiconductor device processing according to any one of claims 1 to 15.

17. A method for manufacturing a laminate, comprising: a step 1 of bringing a substrate having at least two surfaces of a first surface and a second surface made of different materials into contact with the composition for semiconductor device processing according to any one of claims 1 to 15 to form a first film on the first surface; and a step 2 of subjecting the substrate obtained in step 1 to an atomic layer deposition process to form a second film on the second surface.

18. A method for manufacturing an electronic device, comprising the method for manufacturing a modified substrate according to claim 16.

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