Method for manufacturing a substrate and coating liquid

Abstract

To provide a manufacturing method of a substrate, enabling selective formation of a film that can exert a high blocking performance against a metal oxide formation by an ALD method or a CVD method by a coating method onto the substrate including a region containing an end terminal structure expressed by Si-NH2 in a front layer, and to provide a coating liquid.SOLUTION: A manufacturing method of a substrate is provided, comprising: a step of coating a coating liquid to a base material having a first region including end terminal structure expressed by Si-NH2 in a front layer; and a step of heating a coating film formed by the coating step. The coating liquid contains a chemical compound having a functional group and an aromatic ring structure, and forming a carbon-nitrogen double bond by being reacted with the end terminal structure of the first region.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a substrate and a coating liquid.

Background Art

[0002] With the further miniaturization of semiconductor devices, a technique for forming a fine pattern of 30 nm or less is required. However, in the conventional method using lithography, it has become technically difficult due to optical factors and the like.

[0003] Therefore, forming a fine pattern using a so-called bottom-up technique has been studied. As this bottom-up technique, for example, a substrate having a fine region on the surface layer is selectively chemically modified, and after forming a metal oxide in a region where the substrate is not chemically modified by the ALD (Atomic Layer Deposition) method, the CVD (Chemical Vapor Deposition) method, etc., a method of forming a pattern on the substrate by removing the chemical modification has been studied (International Publication No. 2019 / 023001).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] International Publication No. 2019 / 023001 discloses a method including a step of exposing a substrate having a first surface with hydrogen termination and a second surface with hydroxide termination to a nitriding agent to form a first surface terminated with amine, and a step of exposing the first surface terminated with amine to a blocking molecule to form a blocking layer on the first surface.

[0006] In the above method, a blocking layer is selectively formed on the amine-terminated surface by immersing the substrate in an undecanal solution in DMSO. At this time, it is considered that the Si-NH2 group on the substrate surface reacts with the aldehyde group of undecanal (dehydration condensation reaction) to form a carbon-nitrogen double bond. However, since this reaction is an equilibrium reaction and is very susceptible to the influence of hydrolysis by water in the solution or air, it is considered difficult to stably form a blocking layer on the substrate by the coating method.

[0007] An object of the present invention is to provide a method for manufacturing a substrate and a coating liquid that can form a film having high blocking performance against metal oxide formation by ALD method or CVD method selectively by a coating method on a substrate having a region containing a terminal structure represented by Si-NH2 on the surface layer.

Means for Solving the Problems

[0008] The invention made to solve the above problems includes a step of applying a coating liquid to a substrate having a first region containing a terminal structure represented by Si-NH2 on the surface layer, and a step of heating the coating film formed by the above coating step, and the above coating liquid is a method for manufacturing a substrate containing a compound having a functional group and an aromatic ring structure that react with the terminal structure of the first region to form a carbon-nitrogen double bond.

[0009] Another invention made to solve the above problems is a coating liquid used to be applied to a substrate having a first region containing a terminal structure represented by Si-NH2 on the surface layer, and the coating liquid contains a compound having a functional group and an aromatic ring structure that react with the terminal structure of the first region to form a carbon-nitrogen double bond.

Effects of the Invention

[0010] According to the method for manufacturing a substrate and the coating liquid of the present invention, a film having high blocking performance against metal oxide formation by ALD method or CVD method can be selectively formed by a coating method on a substrate having a region containing a terminal structure represented by Si-NH2 on the surface layer.

Mode for Carrying Out the Invention

[0011] Hereinafter, the method for manufacturing a substrate and the coating liquid of the present invention will be described in detail.

[0012] <Method for Manufacturing Substrate> The method for manufacturing the substrate includes a step of applying a coating liquid to a substrate having a first region including a terminal structure represented by Si-NH2 on the surface layer (hereinafter, also referred to as "coating step"), and a step of heating the coating film formed by the coating step (hereinafter, also referred to as "heating step").

[0013] By having the above configuration, the method for manufacturing the substrate can form a film having high blocking performance against metal oxide formation by ALD method or CVD method selectively by coating method on a substrate having a region including a terminal structure represented by Si-NH2 on the surface layer. Although the reason why the method for manufacturing the substrate exhibits the above effects is not necessarily clear, it can be speculated as follows, for example.

[0014] The coating liquid used in the coating step contains a [A] compound described later. It is considered that a film can be selectively formed in a region having a terminal structure represented by Si-NH2 by forming a carbon-nitrogen double bond between a specific functional group of the [A] compound and the terminal structure represented by Si-NH2. Further, it is considered that the hydrolysis of the carbon-nitrogen double bond can be suppressed because the [A] compound has an aromatic ring structure. Furthermore, since water that causes hydrolysis can be removed by the heating step, it is considered that the hydrolysis of the carbon-nitrogen double bond can be further suppressed. By combining such factors, according to the method for manufacturing the substrate, it is considered that a film having high blocking performance against metal oxide formation by ALD method or CVD method can be selectively formed by coating method on a substrate having a region including a terminal structure represented by Si-NH2 on the surface layer.

[0015] The manufacturing method of the substrate may include a step of cleaning, with a cleaning liquid, the materials existing in the regions other than the first region among the films formed by the heating step (hereinafter, also referred to as the "cleaning step") after the heating step.

[0016] The manufacturing method of the substrate may include a step of depositing a pattern on the surface of the substrate by CVD method or ALD method (hereinafter, also referred to as the "depositing step") after the heating step or after the cleaning step.

[0017] The manufacturing method of the substrate may include a step of peeling, with a peeling liquid, the film formed by the heating step (hereinafter, also referred to as the "peeling step") after the heating step. The film formed by the manufacturing method of the substrate can be easily peeled by the peeling liquid.

[0018] Hereinafter, each step included in the manufacturing method of the substrate will be described.

[0019] [Coating step] In this step, a coating liquid is coated on a substrate having a first region including a terminal structure represented by Si-NH2 on the surface layer. By this step, a coating film is formed on the substrate.

[0020] The coating method of the coating liquid is not particularly limited, and examples thereof include a spin coating method, a roll coating method, a bar coating method, etc.

[0021] (Substrate) The substrate has a first region including a terminal structure represented by Si-NH2 (hereinafter, also referred to as a "primary amino group terminal structure") on the surface layer. The shape of the substrate is not particularly limited, and it can be, for example, a plate shape (substrate), a spherical shape, etc., as appropriate to a desired shape.

[0022] The substrate may have a region other than the first region (hereinafter, also referred to as the "second region") on the surface layer. When the substrate has the second region on the surface layer, a blocking film can be selectively formed on the first region.

[0023] When the base material has the second region on the surface layer, the existing shapes of the first region and the second region are not particularly limited, and examples thereof include planar, dot-like, stripe-like shapes, etc. in a plan view. The sizes of the first region and the second region are not particularly limited, and regions of desired sizes can be set as appropriate.

[0024] Examples of the second region include a region containing non-metal atoms, a region containing metal atoms, etc. The second region may be one type or two or more types.

[0025] Examples of the inclusion form of non-metal atoms include non-metal simple substances, non-metal oxides, non-metal nitrides, non-metal oxide nitrides, etc.

[0026] Examples of non-metal simple substances include simple substances such as silicon and carbon. Examples of non-metal oxides include silicon oxide, etc. Examples of non-metal oxide nitrides include SiON, etc. Among these, non-metal oxides are preferable, and silicon oxide is more preferable.

[0027] The metal atoms are not particularly limited as long as they are atoms of metal elements. Note that silicon is a non-metal atom and does not correspond to metal atoms. Examples of metal atoms include copper, iron, zinc, cobalt, aluminum, tin, tungsten, zirconium, titanium, tantalum, germanium, molybdenum, ruthenium, gold, silver, platinum, palladium, nickel, etc. Among these, copper, cobalt or tungsten is preferable.

[0028] Examples of the inclusion form of metal atoms include metal simple substances, alloys, conductive nitrides, metal oxides, silicides, etc.

[0029] Examples of the simple metal include simple metals such as copper, iron, cobalt, tungsten, and tantalum. Examples of the alloy include nickel - copper alloy, cobalt - nickel alloy, and gold - silver alloy. Examples of the conductive nitride include tantalum nitride, titanium nitride, iron nitride, and aluminum nitride. Examples of the metal oxide include tantalum oxide, aluminum oxide, iron oxide, and copper oxide. Examples of the silicide include iron silicide and molybdenum silicide. Among these, the simple metal is preferred, and simple copper, simple cobalt, or simple tungsten is more preferred.

[0030] In this step, the primary amino group - terminal structure in the first region of the substrate surface reacts with the functional group of the [A] compound described later to form a carbon - nitrogen double bond.

[0031] Examples of the substrate include a substrate that has been subjected to a pretreatment for converting the terminal structure represented by Si - H on the surface layer (hereinafter also referred to as "hydrogen - terminal structure") to a primary amino group - terminal structure with respect to a substrate containing silicon nitride. The type of the pretreatment is not particularly limited, and examples include wet treatment and dry treatment. Examples of the wet treatment include treatment using concentrated acetic acid, dilute hydrofluoric acid, etc. Examples of the dry treatment include plasma treatment.

[0032] Further, the method for manufacturing the substrate may include a step (hereinafter also referred to as "pretreatment step") of performing a pretreatment for converting the hydrogen - terminal structure in the surface layer of the substrate containing silicon nitride to a primary amino group - terminal structure before the coating step.

[0033] (Coating liquid) The coating liquid used in this step will be described in the section <Coating liquid> below.

[0034] [Heating step] In this process, the coating film formed by the above coating process is heated. By this process, the reaction between the primary amino group terminal structure and the functional group of the [A] compound is promoted. Further, since water in the system can be removed by this process, hydrolysis of the carbon-nitrogen double bond formed by the above reaction can be suppressed.

[0035] The heating means is not particularly limited and known heating means can be adopted. For example, an oven, a hot plate, etc. can be mentioned. The heating temperature and heating time can be appropriately determined in consideration of various factors such as the presence or absence of a solvent in the coating liquid, the structure of the [A] compound, the type of the functional group of the [A] compound, etc. As the lower limit of the heating temperature, 80°C is preferable, 100°C is more preferable, and 130°C is even more preferable. As the upper limit of the heating temperature, 400°C is preferable, 300°C is more preferable, and 200°C is even more preferable. As the lower limit of the heating time, 10 seconds is preferable, 1 minute is more preferable, and 2 minutes is even more preferable. As the upper limit of the heating time, 60 minutes is preferable, 10 minutes is more preferable, and 5 minutes is even more preferable.

[0036] The average thickness of the formed film can be set to a desired value by appropriately selecting the type and concentration of the [A] compound in the coating liquid, and conditions such as the heating temperature and heating time in the heating process. As the lower limit of the average thickness of the film, 0.1 nm is preferable, 1 nm is more preferable, and 3 nm is even more preferable. The upper limit of the above average thickness is, for example, 20 nm. The average thickness of the film is a value measured using a spectroscopic ellipsometer (「M2000D」 manufactured by J.A.WOOLLAM).

[0037] [Washing Process] In this process, the material present in the region other than the above first region of the film formed by the above heating process is washed with a cleaning liquid. This process is performed after the above heating process. By this process, the material that does not form the terminal structure and the carbon-nitrogen double bond in the first region present on the substrate is removed. This process is particularly advantageous when the substrate has a second region, and the material present on the second region can be removed, and a blocking film can be selectively formed on the first region.

[0038] As the cleaning liquid, an organic solvent is used. For example, solvents exemplified as [B] solvents in the section of <coating liquid> described below can be mentioned. Further, when the coating liquid contains a [B] solvent, a solvent of the same type as the [B] solvent contained in the coating liquid can be used as the cleaning liquid.

[0039] [Deposition step] In this step, a pattern is deposited on the surface of the substrate by CVD method or ALD method. This step is performed after the heating step or the cleaning step. This step is particularly advantageous when the substrate has a second region, and the film formed on the first region has high blocking performance against metal oxide formation by CVD method or ALD method, so that a metal oxide pattern can be selectively formed on the second region.

[0040] [Peeling step] In this step, the film formed by the heating step is peeled off with a peeling liquid. This step is performed after the heating step or the deposition step. This step is particularly advantageous when the substrate has a second region and is performed after the deposition step. By peeling off the film formed by the heating step, a metal oxide pattern can be selectively formed on the second region of the substrate.

[0041] As the peeling liquid, a liquid containing an acid or a liquid containing a base is preferable. Examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and hydrofluoric acid, and carboxylic acids such as acetic acid, citric acid, oxalic acid, maleic acid, isobutyric acid, and 2-ethylhexanoic acid. Among these, carboxylic acids are preferable, and citric acid is more preferable. Examples of the base include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, and tetramethylammonium hydroxide (TMAH). Among these, TMAH is preferable.

[0042] Examples of the stripping solution include an aqueous solution of ammonium hydroxide - hydrogen peroxide (SC-1 cleaning solution), an aqueous solution of hydrochloric acid - hydrogen peroxide (SC-2 cleaning solution), and the like.

[0043] The solvent of the stripping solution preferably has water as the main component. The lower limit of the water content in the solvent is preferably 50% by mass, more preferably 90% by mass, still more preferably 95% by mass. The above content ratio may be 100% by mass.

[0044] <Coating liquid> The coating liquid contains a compound having a functional group that reacts with a terminal structure represented by Si-NH2 (primary amino group terminal structure) in the first region of the substrate to form a carbon - nitrogen double bond and an aromatic ring structure (hereinafter also referred to as "[A] compound"). The coating liquid is liquid at normal temperature and pressure and may contain a solvent (hereinafter also referred to as "[B] solvent") as necessary. The coating liquid can contain other components (hereinafter also referred to as "other components") other than the [A] compound and the [B] solvent as long as the effects of the present invention are not impaired.

[0045] The coating liquid is used to be applied to a substrate having a first region containing a primary amino group terminal structure on the surface layer. Specifically, the coating liquid is used in the coating step in the above-described method for manufacturing the substrate.

[0046] Hereinafter, each component contained in the coating liquid will be described.

[0047] [[A] compound] [A] compound has a functional group (hereinafter also referred to as "functional group (X)") that reacts with a primary amino group terminal structure in the first region of the substrate to form a carbon - nitrogen double bond and an aromatic ring structure.

[0048] [A] The compound may be a polymer (hereinafter also referred to as "[A1] polymer") or a low-molecular compound (hereinafter also referred to as "[A2] compound"). In this specification, "polymer" means a compound having repeating units, and "low-molecular compound" means a compound that is not a polymer, has no molecular weight distribution, and has a molecular weight of 1,000 or less.

[0049] The functional group (X) is a functional group that reacts with a primary amino group terminal structure to form a carbon-nitrogen double bond. As the functional group (X), an aldehyde group or a ketonic carbonyl group is preferable. The [A] compound can have one or more functional groups (X).

[0050] Examples of the aromatic ring structure include an aromatic hydrocarbon ring structure having 6 to 20 ring members and an aromatic heterocyclic ring structure having 5 to 20 ring members. "Number of ring members" means the number of atoms constituting the ring structure, and in the case of a polycyclic ring, it means the total number of atoms constituting the polycyclic ring.

[0051] Examples of the aromatic hydrocarbon ring structure having 6 to 20 ring members include a benzene structure, a naphthalene structure, a biphenyl structure, an anthracene structure, a phenanthrene structure, a fluorene structure, a tetracene structure, a pyrene structure, etc.

[0052] Examples of the aromatic heterocyclic ring structure having 5 to 20 ring members include a furan structure, a benzofuran structure, a pyrrole structure, an indole structure, a thiophene structure, a benzothiophene structure, a dibenzothiophene structure, an imidazole structure, a pyrazole structure, an oxazole structure, etc.

[0053] As the aromatic ring structure, an aromatic hydrocarbon ring structure having 6 to 20 ring members is preferable.

[0054] [A] The compound preferably has a molecular weight of 200 or more. Note that "molecular weight" means the weight-average molecular weight Mw described later in the case of an [A1] polymer, and means the sum of the atomic weights of each atom constituting the low-molecular compound in the case of an [A2] compound.

[0055] ([A1] Compound) When the [A] compound is an [A1] polymer, the [A1] polymer has a structural unit containing an aromatic ring structure (hereinafter also referred to as "structural unit (I)") and a functional group (X). The [A1] polymer may have other structural units in addition to the structural unit (I).

[0056] When the functional group (X) is an aldehyde group, the [A1] polymer preferably has the functional group (X) at the end of the main chain or the end of the side chain, and more preferably has the functional group (X) at the end of the main chain. The "main chain" means the longest atomic chain among the atomic chains constituting the [A1] polymer, and the "side chain" means the atomic chain other than the main chain among the atomic chains constituting the [A1] polymer.

[0057] The functional group (X) at the end of the main chain can be introduced, for example, by treating the polymerization end of a living anionic polymer such as polystyrene with an end treatment agent that gives the functional group (X). Examples of the end treatment agent that gives the functional group (X) include N,N-dimethylformamide and the like.

[0058] The [A1] polymer having the functional group (X) at the end of the side chain can be formed, for example, by using a monomer having the functional group (X) at the end and an ethylenic carbon-carbon double bond such as 4-vinylbenzaldehyde.

[0059] When the functional group (X) is a ketonic carbonyl group, the [A1] polymer preferably has the functional group (X) in the main chain. Further, it is preferable that both ends of the ketonic carbonyl group are bonded to the above aromatic ring structure. The ketonic carbonyl group in the main chain can be formed by a Friedel-Crafts reaction by reacting a compound having an aromatic ring structure such as 2,2'-dimethoxybiphenyl with an aromatic dicarboxylic acid such as 4,4'-dicarboxydiphenyl ether in the presence of trifluoromethanesulfonic acid.

[0060] When the [A] compound is an [A1] polymer, the lower limit of the weight average molecular weight Mw of the [A1] polymer is preferably 200, more preferably 1,000, still more preferably 2,000, still more preferably 3,000, and particularly preferably 4,000. The upper limit of the above Mw is preferably 80,000, more preferably 60,000, may be preferably 20,000, and may be preferably 10,000.

[0061] The upper limit of the ratio (Mw / Mn, dispersity) of Mw to the polystyrene-reduced number average molecular weight Mn of the [A1] polymer by GPC is preferably 5, more preferably 2.5, may be preferably 1.5, and may be preferably 1.3. The lower limit of the above ratio is usually 1, and preferably 1.02.

[0062] [Measurement methods of Mw and Mn] The Mw and Mn of the polymer in this specification are values measured by gel permeation chromatography under the following conditions using GPC columns of Tosoh Corporation ("two G2000HXL", "one G3000HXL", and "one G4000HXL"). Eluent: Tetrahydrofuran (FUJIFILM Wako Pure Chemical Corporation) Flow rate: 1.0 mL / min Sample concentration: 1.0 mass% Sample injection volume: 100 μL Column temperature: 40 °C Detector: Differential refractometer Standard substance: Monodisperse polystyrene

[0063] ([A2] compound) When the [A] compound is an [A2] compound, the [A2] compound has an aromatic ring structure and a functional group (X). It is preferable that the functional group (X) is bonded to the aromatic ring structure. In this case, a blocking film can be formed more stably on the substrate by a coating method.

[0064] Examples of the [A2] compound include p-octyloxybenzaldehyde, 3,5-bis(dodecyloxy)benzaldehyde, and the like.

[0065] When the [A] compound is the [A2] compound, the lower limit of the molecular weight of the [A2] compound is preferably 200, more preferably 300. When the molecular weight of the [A2] compound is not less than the above lower limit, the coating property of the coating liquid can be further improved. The upper limit of the molecular weight is 1,000, preferably 700, and more preferably 600.

[0066] [[B] Solvent] The [B] solvent is not particularly limited as long as it can dissolve or disperse the [A] compound and other components, and examples thereof include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, hydrocarbon solvents, and the like. The coating liquid may contain one or more [B] solvents.

[0067] Examples of the alcohol solvent include aliphatic monoalcohol solvents having 1 to 18 carbon atoms such as 4-methyl-2-pentanol and n-hexanol; alicyclic monoalcohol solvents having 3 to 18 carbon atoms such as cyclohexanol; polyhydric alcohol solvents having 2 to 18 carbon atoms such as 1,2-propylene glycol; polyhydric alcohol partial ether solvents having 3 to 19 carbon atoms such as propylene glycol monomethyl ether, and the like.

[0068] Examples of the ether solvent include dialkyl ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, diisoamyl ether, dihexyl ether, and diheptyl ether; cyclic ether solvents such as tetrahydrofuran and tetrahydropyran; aromatic ring-containing ether solvents such as diphenyl ether and anisole (methyl phenyl ether), and the like.

[0069] Examples of ketone solvents include chain ketone solvents such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl isobutyl ketone (MIBK), 2-heptanone (methyl-n-pentyl ketone), ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-iso-butyl ketone, trimethyl nonanone; cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone; 2,4-pentanedione, acetonylacetone, acetophenone, etc.

[0070] Examples of amide solvents include cyclic amide solvents such as N,N'-dimethylimidazolidinone, N-methylpyrrolidone; chain amide solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, etc.

[0071] Examples of ester solvents include monocarboxylic acid ester solvents such as n-butyl acetate, ethyl lactate; polyhydric alcohol carboxylate solvents such as propylene glycol acetate; polyhydric alcohol partial ether carboxylate solvents such as propylene glycol monomethyl ether acetate; lactone solvents such as γ-butyrolactone, δ-valerolactone; polycarboxylic acid diester solvents such as diethyl oxalate; carbonate solvents such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, etc.

[0072] Examples of hydrocarbon solvents include Aliphatic hydrocarbon solvents having 5 to 12 carbon atoms such as n-pentane and n-hexane; Examples thereof include aromatic hydrocarbon solvents having 6 to 16 carbon atoms such as toluene and xylene.

[0073] Among these, ester solvents are preferred, polyhydric alcohol partial ether carboxylate solvents, lactone solvents or combinations thereof are more preferred, and propylene glycol monomethyl ether acetate, γ-butyrolactone or combinations thereof are even more preferred.

[0074] [Other components] Examples of other components include acid generators, surfactants, etc. The content ratio of other components in the coating liquid can be appropriately determined according to the types of other components used, etc.

[0075] As the lower limit of the solid content concentration of the coating liquid, 0.1% by mass is preferred, 0.5% by mass is more preferred, and 0.7% by mass is even more preferred. As the upper limit of the solid content concentration, 30% by mass is preferred, 10% by mass is more preferred, and 3% by mass is even more preferred. "Solid content concentration" refers to the concentration (% by mass) of all components other than [B] solvent in the coating liquid.

[0076] [Method for preparing the coating liquid] The coating liquid can be prepared, for example, by mixing [A] compound, [B] solvent and, if necessary, other components in a predetermined ratio, and preferably filtering with a high-density polyethylene filter having pores of 0.45 μm or less.

Examples

[0077] Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. The measurement methods of each physical property value are shown below.

[0078] [Weight average molecular weight (Mw), number average molecular weight (Mn) and dispersity (Mw / Mn)] The Mw and Mn of the polymer were measured according to the conditions described in the section [Measurement Method of Mw and Mn]. The dispersity (Mw / Mn) of the polymer was calculated from the measurement results of Mw and Mn.

[0079] 13 [C-NMR Analysis] 13 C-NMR analysis was performed using a nuclear magnetic resonance apparatus ("JNM-EX400" manufactured by JEOL Ltd.) with CDCl3 as the measurement solvent. The content ratio of each structural unit in the polymer was 13 calculated from the area ratio of the peaks corresponding to each structural unit in the spectrum obtained by C-NMR.

[0080] [Synthesis of Compound [A]] Among the [A] compounds, polymers (A1-1) to (A1-3) were synthesized as the [A1] polymer, and the following compound (A2-1) was synthesized as the [A2] compound. In addition, polymers (a1-1) to (a1-3) were synthesized as controls for the [A1] polymer.

[0081] [Synthesis Example 1] Synthesis of Polymer (A1-1) (BZP-co-BP(OMe)2) To a three-necked flask equipped with a thermometer and a stirrer bar, 7.8 g of 4,4'-dicarboxydiphenyl ether, 7.7 g of 2,2'-dimethoxybiphenyl, and 45 mL of trifluoromethanesulfonic acid were added, and the mixture was heated and stirred at 40 °C for 24 hours under a nitrogen atmosphere. After completion of the reaction, 45 mL of water was slowly added dropwise to precipitate the polymer, which was collected with a Buchner funnel and dried under reduced pressure. This polymer was dissolved in a small amount of N,N-dimethylacetamide and precipitated and purified in 2-propanol, collected with a Buchner funnel, and dried under reduced pressure to obtain 12.8 g of a polymer represented by the following formula (A1-1) (hereinafter also referred to as "polymer (A1-1)" or "BZP-co-BP(OMe)2"). The polymer (A1-1) had an Mw of 50,000, an Mn of 24,800, and an Mw / Mn of 2.02.

[0082]

Chemical Formula

[0083] [Synthesis Example 2] Synthesis of Polymer (A1-2) (PS-r-PStCHO) 10 g of methyl ethyl ketone was placed in a three-necked flask equipped with a thermometer, Dimroth condenser and stirrer bar and maintained at 80°C. A mixed solution of 7.28 g of styrene, 3.96 g of 4-vinylbenzaldehyde, 0.69 g of dimethyl-2,2'-azobis(2-methylpropionate) and 20 g of methyl ethyl ketone was added dropwise from a feeder over 3 hours. After completion of the dropwise addition, the mixture was aged at 80°C for 3 hours. The resulting polymerization solution was precipitated and purified with 5 times the amount of methanol to obtain 7.31 g of a white solid polymer represented by the following formula (A1-2) (hereinafter also referred to as "polymer (A1-2)" or "PS-r-PStCHO"). The Mw of polymer (A-2) was 5,780, Mn was 3,140, and Mw / Mn was 1.84. 13 By 13C-NMR analysis, the molar ratio of the structural unit derived from styrene to the structural unit derived from 4-vinylbenzaldehyde in polymer (A1-2) was 58:42.

[0084] [Chemical Formula]

[0085] [Synthesis Example 3] Synthesis of Polymer (A1-3) (PS-w-CHO) After drying the 500 mL flask reaction vessel under reduced pressure, 120 g of tetrahydrofuran (THF) that had been subjected to distillation dehydration treatment was injected under a nitrogen atmosphere and cooled to -78 °C. Next, 2.38 mL of a 1N cyclohexane solution of sec-butyllithium (sec-BuLi) was injected into this THF, and then 13.3 mL of styrene that had been subjected to adsorption filtration with silica gel and distillation dehydration treatment to remove the polymerization inhibitor was dropwise injected over 30 minutes, and it was confirmed that the polymerization system was orange. During this dropwise injection, care was taken so that the internal temperature of the reaction solution did not exceed -60 °C. After completion of the dropwise injection, it was aged for 30 minutes. Thereafter, 0.18 ml of N,N-dimethylformamide was injected to carry out a termination reaction at the polymerization end. The temperature of this reaction solution was raised to room temperature, and the obtained reaction solution was concentrated and replaced with methyl isobutyl ketone (MIBK). 1,000 g of a 2% aqueous solution of oxalic acid was injected into the obtained solution, stirred, allowed to stand, and then the lower aqueous layer was removed. This operation was repeated 3 times to remove metal salts. Thereafter, 1,000 g of ultrapure water was injected, stirred, and the lower aqueous layer was removed. This operation was repeated 3 times to remove oxalic acid, and then the solution was concentrated and dropped into 500 g of methanol to precipitate a polymer, and the solid was recovered with a Buchner funnel. By drying this solid under reduced pressure at 60 °C, 11.9 g of a white polymer represented by the following formula (A-3) (hereinafter, also referred to as "polymer (A1-3)" or "PS-w-CHO") was obtained. Polymer (A1-3) had a Mw of 5,000, a Mn of 4,800, and a Mw / Mn of 1.04.

[0086] [Chemical formula]

[0087] [Synthesis Example 4] Synthesis of Compound (A2-1) (3,5-bis(dodecyloxy)benzaldehyde) 8.37 g of 3,5-dihydroxybenzaldehyde, 44.5 g of 1-bromododecane, 300 g of N,N-dimethylformamide, and 20.7 g of potassium carbonate were added to a 1 L eggplant-shaped flask, and the mixture was heated and stirred at 80 °C for 16 hours under a nitrogen atmosphere. After cooling, potassium carbonate and salts were removed using a Kiriyama funnel (registered trademark), and then washed four times with toluene / ultrapure water. The organic layer was recovered, water was removed using anhydrous sodium sulfate, and then the filtrate was recovered using a pleated filter paper and concentrated under reduced pressure. Next, purification was performed by column chromatography using hexane / methylene chloride = 10 / 1 to obtain 32 g of white solid 3,5-bis(dodecyloxy)benzaldehyde (hereinafter, also referred to as "Compound (A2-1)"). The molecular weight of Compound (A2-1) was 474.

[0088] [Synthesis Example 5] Synthesis of Polymer (a1-1) (PS-w-(CN)2) 10.0 g of the polymer (A1-3) obtained in Synthesis Example 3 was dissolved in 40 g of toluene, 0.21 g of malononitrile, 0.25 g of ammonium acetate, and 0.038 g of acetic acid were added, and the mixture was heated and distilled under a nitrogen atmosphere at 115 °C for 4 hours. The temperature of this reaction solution was raised to room temperature, and the obtained reaction solution was concentrated and replaced with MIBK. 500 g of a 2% aqueous solution of sodium hydrogen carbonate was injected into the obtained solution, stirred, allowed to stand, and then the lower aqueous layer was removed. This operation was repeated three times. Thereafter, 1,000 g of ultrapure water was injected, stirred, and the lower aqueous layer was removed. After repeating this operation three times, the solution was concentrated and dropped into 500 g of methanol to precipitate the polymer, and the solid was recovered using a Buchner funnel. The solid was dried under reduced pressure at 60 °C to obtain 9.8 g of a white polymer represented by the following formula (a1-1) (hereinafter, also referred to as "polymer (a1-1)" or "PS-w-(CN)2"). The polymer (a1-1) had Mw of 5,300, Mn of 5,100, and Mw / Mn of 1.04.

[0089] [Chemical Formula]

[0090] [Synthesis Example 6] Synthesis of Polymer (a1-2) (PS-w-PO3Et2) After drying a 500 mL flask reaction vessel under reduced pressure, 120 g of THF that had been subjected to distillation dehydration treatment was injected under a nitrogen atmosphere and cooled to -78°C. Then, 2.30 mL of a 1N cyclohexane solution of sec-BuLi was injected into this THF. Subsequently, 13.3 mL of styrene that had been subjected to adsorption filtration through silica gel and distillation dehydration treatment to remove the polymerization inhibitor was dropwise injected over 30 minutes while taking care that the internal temperature of the reaction solution did not exceed -60°C, and then stirred for 30 minutes. Thereafter, 0.33 mL of diethyl chlorophosphate was injected to carry out a termination reaction at the polymerization end. The temperature of this reaction solution was raised to room temperature, and the obtained reaction solution was concentrated and replaced with MIBK. Then, 200 g of a 2 mass% aqueous oxalic acid solution was injected and stirred. After standing, the lower aqueous layer was removed. This operation was repeated 3 times to remove the lithium salt. Thereafter, 200 g of ultrapure water was injected and stirred, and the lower aqueous layer was removed. This operation was repeated 4 times to remove oxalic acid. Then, the solution was concentrated and dropped into 400 g of methanol to precipitate a polymer, and the solid was recovered with a Buchner funnel. By drying this solid under reduced pressure at 60°C, 11.5 g of a white polymer represented by the following formula (a1-2) (hereinafter, also referred to as "polymer (a1-2)" or "PS-w-PO3Et2") was obtained. The polymer (a1-2) had an Mw of 5,100, an Mn of 4,900, and an Mw / Mn of 1.04.

[0091] [Chemical formula]

[0092] [Synthesis Example 7] Synthesis of Polymer (a1-3) (PS-w-PO3H2) To 10.0 g of the polymer (a1-2) obtained in Synthesis Example 6, 0.81 g of triethylamine, 4 g of propylene glycol monomethyl ether, and 40 g of propylene glycol monomethyl ether acetate were added, and the mixture was heated and stirred at 80 °C for 6 hours under a nitrogen atmosphere. The temperature of this reaction solution was raised to room temperature, and the obtained reaction solution was concentrated and replaced with MIBK. Then, 200 g of ultrapure water was poured in and stirred, and the lower aqueous layer was removed. This operation was repeated 3 times. After removing triethylamine, the solution was concentrated and dropped into 400 g of methanol to precipitate the polymer, and the solid was recovered with a Buchner funnel. This solid was dried under reduced pressure at 60 °C to obtain 9.2 g of a white polymer represented by the following formula (a1-3) (hereinafter also referred to as "polymer (a1-3)" or "PS-w-PO3H2"). The polymer (a1-3) had Mw of 5,100, Mn of 4,800, and Mw / Mn of 1.06.

[0093] [Chemical formula]

[0094] [Preparation of coating liquid] [B] The solvents used for the preparation of the coating liquid are shown below. Solvent (B-1): Propylene glycol monomethyl ether acetate (PGMEA) Solvent (B-2): γ-Butyrolactone

[0095] [Example 1-1] Preparation of coating liquid (S-1) To 1.30 g of the polymer (A-1) as [A] compound, 79 g of the solvent (B-1) and 19.8 g of the solvent (B-2) as [B] solvents were added, and after stirring, the mixture was filtered through a high-density polyethylene filter having pores of 0.45 μm to prepare a coating liquid (S-1). The solid content concentration of the coating liquid (S-1) was 1.2%.

[0096] [Examples 1-2 to 1-4 and Comparative Examples 1-1 to 1-3] Preparation of coating liquids (S-2) to (S-4) and (CS-1) to (CS-3) Coating liquids (S-2) to (S-4) and (CS-1) to (CS-3) were prepared in the same manner as in Example 1-1 except that each component of the type and blending amount shown in Table 1 below was used. The solid content concentrations of the coating liquids (S-2) to (S-4) and (CS-1) to (CS-3) are shown in accordance with Table 1 below.

[0097] [Table 1]

[0098] [Film formation] [Substrate] The following substrates were used as substrates. th-SiO2: Silicon dioxide substrate with an 8-inch thermal oxide film SiN: 8-inch silicon nitride substrate Cu: 8-inch copper substrate Co: 8-inch cobalt substrate W: 8-inch tungsten substrate Regarding the above substrates, those subjected to plasma treatment (using "Luminous NA-1300" of ULVAC, Inc.) with an N2 / (3%)H2 mixed gas ([conditions] 25°C, chamber pressure: 30 Pa, treatment time: 5 minutes, flow rate: 300 sccm, Microwave: 300 mW) were used. By this plasma treatment, the Si-H terminal structure present on the surface layer of the SiN substrate is converted to the Si-NH2 terminal structure.

[0099] [Example 2-1] Various substrates shown in Table 2 below were cut into 3 cm × 3 cm, and the prepared composition (S-1) was spin-coated under the conditions of 1,500 rpm for 20 seconds using a spin coater ("MS-B300" of Mikasa Co., Ltd.) to form a coating film (coating step). Next, the substrate on which this coating film was formed was baked at 150°C for 180 seconds to form a film (heating step). Then, the substrate was washed using propylene glycol monomethyl ether acetate (washing step). In the washing step, when no film is adsorbed on the substrate surface, the unadsorbed film is removed.

[0100] For the substrate that has undergone a series of processes including the above coating process, heating process, and cleaning process, when the static contact angle of the surface was measured using a contact angle meter ("Drop master DM-501" manufactured by Kyowa Interface Science Co., Ltd.), the th-SiO2 substrate was 38°, the SiN substrate was 85°, the Cu substrate was 36°, the Co substrate was 40°, and the W substrate was 42°. Since the values of the static contact angles of various substrates before the above treatment were 36° for the th-SiO2 substrate, 25° for the SiN substrate, 36° for the Cu substrate, 42° for the Co substrate, and 45° for the W substrate, it can be seen that a film was selectively formed on the SiN substrate, which had a significantly increased static contact angle compared to that before the above treatment.

[0101] [Examples 2-2 to 2-4 and Comparative Examples 2-1 to 2-3] The same treatment as in Example 2-1 was performed except that the coating liquid shown in Table 2 below was used, and the static contact angle was measured. The results are shown in Table 2 below.

[0102] In Table 2 below, the numerical values described in parentheses for various substrate names indicate the static contact angles (Blank SCA) of various substrates before treatment.

[0103] [Table 2]

[0104] [Evaluation of wet peelability of film] [Example 3-1] The various substrates that had undergone a series of processes in Example 2-1 were immersed in a petri dish filled with a 2 mass% aqueous citric acid solution for 3 minutes, and then further immersed in a petri dish filled with a 2.38 mass% aqueous tetramethylammonium hydroxide solution for 3 minutes. Subsequently, after washing with propylene glycol monomethyl ether acetate, the static contact angle of the substrate surface was measured using the above contact angle meter. As a result, the th-SiO2 substrate had a contact angle of 38°, the SiN substrate had a contact angle of 24°, the Cu substrate had a contact angle of 32°, the Co substrate had a contact angle of 38°, and the W substrate had a contact angle of 42°. Since the values of the static contact angles of the various substrates before the above wet peeling treatment (Example 2-1) were 38° for the th-SiO2 substrate, 85° for the SiN substrate, 34° for the Cu substrate, 40° for the Co substrate, and 42° for the W substrate, it can be seen that the film formed on the SiN substrate could be wet peeled off.

[0105] [Examples 3-2 to 3-4 and Comparative Examples 3-1 to 3-3] The same processes as in Example 3-1 were carried out except that the various substrates that had undergone a series of processes in Examples 2-2 to 2-4 and Comparative Examples 2-1 to 2-3 were used respectively, and the static contact angle was measured. The results are shown in Table 3 below.

[0106] In Table 3 below, the numerical values described in parentheses for the various substrate names indicate the static contact angles (Blank SCA) of the various substrates before the treatment in the above <Film Formation> section. In Table 3 below, all the values of "before peeling" are the values in Table 2 above.

[0107] [Table 3]

[0108] [Metal Oxide Blocking Evaluation] [Example 4-1] Regarding the surface of the SiN substrate that had undergone a series of processes in Example 2-1, in order to evaluate the film formation state, a metal oxide blocking evaluation was carried out to measure the suppression degree of oxide layer formation by ALD. As a control, the SiN substrate before undergoing a series of processes in Example 2-1 was used.

[0109] [Oxide layer formation by ALD] ALD was carried out using Cambridge Nanotech FIJI within Stanford University under the conditions shown in Table 4 below. Trimethylaluminum was used as the precursor, and water was used as the cocatalyst. The ALD cycle was fixed at 47 cycles.

[0110] [Table 4]

[0111] [ESCA analysis] Regarding the Al component on the surface of the SiN substrate after the above ALD, quantification was performed by ESCA analysis. The ESCA analysis was carried out using "Quantum2000" of ULVAC, Inc. The Al component excluding the film component and the substrate component was quantified at Al2p (72 - 78 eV) under the condition of 100 μmφ. Then, based on the quantified value of the Al component measured for the SiN substrate before performing the series of processes in Example 2 - 1, the blocking rate (%) was calculated as to how much the quantified value decreased from the reference quantified value. As a result, the blocking rate of the SiN substrate when using Coating Liquid S - 1 was 98.6%. Since a larger value of the blocking rate means a film with higher metal oxide blocking performance, it can be seen that the film formed on the SiN substrate has high blocking performance against metal oxide formation by the ALD method.

[0112] [Examples 4 - 2 to 4 - 4 and Comparative Examples 4 - 1 to 4 - 3] The same processes as in Example 4 - 1 were carried out except that the SiN substrates subjected to the series of processes in Examples 2 - 2 to 2 - 4 and Comparative Examples 2 - 1 to 2 - 3 were used respectively, and the blocking rate was calculated. The results are shown in Table 5 below. All the examples had excellent blocking performance, while the comparative examples showed almost no blocking performance.

[0113] [Table 5]

Claims

1. Si-NH ２ A step of applying a coating liquid to a substrate having a first region including a terminal structure represented by A step of heating a coating film formed by the above coating step and comprising A method for manufacturing a substrate, wherein the coating liquid contains a compound having a functional group that reacts with the terminal structure of the first region to form a carbon-nitrogen double bond and an aromatic ring structure.

2. The method for manufacturing a substrate according to Claim 1, wherein the molecular weight of the above compound is 200 or more.

3. The method for manufacturing a substrate according to Claim 1 or Claim 2, wherein the above compound is a polymer having a structural unit containing an aromatic ring structure.

4. The method for manufacturing a substrate according to Claim 3, wherein the above polymer has the above functional group at the end of the main chain or the end of the side chain.

5. The method for manufacturing a substrate according to any one of Claims 1 to 4, wherein the above functional group is an aldehyde group or a ketonic carbonyl group.

6. The method for manufacturing a substrate according to any one of Claims 1 to 5, wherein the above aromatic ring structure is an aromatic hydrocarbon ring structure.

7. The method for manufacturing a substrate according to any one of Claims 1 to 6, wherein the above substrate further has a second region containing silicon oxide on the surface layer.

8. The method for manufacturing a substrate according to any one of Claims 1 to 7, wherein the above coating liquid further contains a solvent.

9. Si-NH ２ A coating liquid for film formation used to be applied to a substrate having a first region including a terminal structure represented by A coating liquid for film formation containing a compound having a functional group that reacts with the terminal structure of the first region to form a carbon-nitrogen double bond and an aromatic ring structure.

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