Method for manufacturing glass substrate equipped with through electrode, and copper film forming composition

Abstract

Provided is a copper film forming composition and a method, for manufacturing a glass substrate equipped with a through electrode, where a seed layer also having properties of an adhesion layer can be formed on a glass wall surface in a through-hole of the glass substrate. The method for manufacturing a glass substrate equipped with a through electrode comprises: a seed layer forming step for bringing a copper film forming composition directly into contact with a glass wall surface in at least a through-hole of a glass substrate having the through-hole, and forming a seed layer on the glass wall surface in the through-hole; and a through electrode forming step for forming a through electrode in the through-hole in which the seed layer was formed. The copper film forming composition contains a copper compound, a nitrogen-containing organic compound, and a solvent.

Description

Method for manufacturing glass substrate with through electrodes and composition for forming copper film

[0001] The present invention relates to a method for producing a glass substrate with through electrodes and a composition for forming a copper film.

[0002] When electrically connecting a semiconductor element to a printed circuit board, an intermediate substrate (substrate for mounting semiconductor elements) called an interposer is used to match the connection pitch between the two. Although substrates made of organic materials have been widely used as interposers, they are prone to deformation due to humidity and heat, which can make it difficult to accommodate higher density mounting of semiconductor elements and finer wiring.

[0003] Therefore, glass interposers, which can reduce the effects of the above-mentioned environment and have excellent workability and insulation properties, have attracted attention. In response to this, various methods for forming through electrodes that connect the wiring on the front and back surfaces of the glass interposer in the thickness direction of the substrate have been investigated (see JP 2016-134392 A).

[0004] JP 2016-134392 A

[0005] The adhesion between the conductive metal material for forming the through electrode and the glass substrate is often insufficient. Therefore, including the above-mentioned formation method, a procedure of forming an adhesion layer followed by a seed layer on the glass wall of the through hole before forming the through electrode is generally adopted. To further improve production efficiency, one method is to omit the formation of either the adhesion layer or the seed layer, but this is not easy because the remaining layer must have the properties of both.

[0006] The present invention aims to provide a method for manufacturing a glass substrate with through electrodes, which is capable of forming a seed layer that also has the properties of an adhesive layer on the glass wall surface inside the through hole of the glass substrate, and a composition for forming a copper film.

[0007] As a result of extensive research into solving the above problems, the present inventors have found that the above object can be achieved by employing the following configuration, and have thus completed the present invention.

[0008] In one embodiment, the present invention relates to a method for manufacturing a glass substrate with through electrodes, comprising: a seed layer forming step of contacting a copper film forming composition directly with at least a glass wall surface within a through hole of a glass substrate having through holes to form a seed layer on the glass wall surface within the through hole; and a through electrode forming step of forming a through electrode in the through hole on which the seed layer has been formed, wherein the copper film forming composition contains a copper compound, a nitrogen-containing organic compound, and a solvent.

[0009] In another embodiment, the present invention relates to a composition for forming a copper film, which is used to form a seed layer directly on a glass wall surface in a through hole of a glass substrate having a through hole, and which contains a copper compound, a nitrogen-containing organic compound, and a solvent.

[0010] In this specification, the term "hydrocarbon group" includes linear hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. This "hydrocarbon group" includes saturated hydrocarbon groups and unsaturated hydrocarbon groups. The term "linear hydrocarbon group" refers to a hydrocarbon group that does not contain a ring structure and is composed only of a linear structure, and includes both linear hydrocarbon groups and branched hydrocarbon groups. The term "alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic structure as a ring structure and does not contain an aromatic ring structure, and includes both monocyclic alicyclic hydrocarbon groups and polycyclic alicyclic hydrocarbon groups (however, it does not have to be composed only of an alicyclic structure and may contain a linear structure as part of it). The term "aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as a ring structure (however, it does not have to be composed only of an aromatic ring structure and may contain an alicyclic structure or a linear structure as part of it).

[0011] According to this method for manufacturing a glass substrate with through electrodes, a seed layer having the properties of an adhesion layer can be directly formed without forming an adhesion layer on the glass wall surface inside the through hole of the glass substrate, thereby significantly improving production efficiency while maintaining the adhesion of the through electrode. According to this copper film-forming composition, a seed layer having the properties of an adhesion layer can be directly formed on the glass wall surface inside the through hole. Therefore, these can contribute to improving the productivity of manufacturing glass substrates with through electrodes, which require high reliability and high functionality.

[0012] Fig. 1 is a cross-sectional view schematically showing one step of a method for manufacturing a glass substrate with through electrodes; Fig. 2 is a cross-sectional view schematically showing one step of a method for manufacturing a glass substrate with through electrodes; Fig. 3 is a cross-sectional view schematically showing one step of a method for manufacturing a glass substrate with through electrodes; Fig. 4 is a cross-sectional view schematically showing another step of a method for manufacturing a glass substrate with through electrodes; Fig. 5 is a cross-sectional view schematically showing another step of a method for manufacturing a glass substrate with through electrodes.

[0013] Hereinafter, the method for manufacturing a glass substrate with through electrodes and the composition for forming a copper film according to each embodiment of the present invention will be described in detail with reference to the drawings. A combination of preferred aspects in each embodiment is also preferred.

[0014] <Method for manufacturing glass substrate with through electrodes> The method for manufacturing a glass substrate with through electrodes includes a seed layer formation step of contacting a copper film-forming composition directly with at least a glass wall surface within a through hole of a glass substrate having a through hole to form a seed layer on the glass wall surface within the through hole, and a through electrode formation step of forming a through electrode in the through hole with the seed layer formed therein.

[0015] In the method for manufacturing a glass substrate with through electrodes, the copper film-forming composition described below can be suitably used as the copper film-forming composition. By using the copper film-forming composition, a copper film (seed layer) having excellent adhesion to the glass substrate can be suitably formed.

[0016] The copper film-forming composition used in the production method will be described below, followed by a description of each step.

[0017] <Composition for forming copper film> The composition for forming copper film contains a copper compound, a nitrogen-containing organic compound, and a solvent. The composition for forming copper film may contain optional components within a range that does not impair the effects of the present invention. Each component contained in the composition for forming copper film will be described below.

[0018] [Copper Compound] The copper compound is a compound containing at least copper atoms (including ionized copper atoms; the same applies to other atoms). The copper compound may contain one or more other metal atoms in addition to the copper atoms. The above copper compounds may be used alone or in combination of two or more.

[0019] The copper compound is preferably a copper salt, a copper complex, or a combination thereof. Copper salts and copper complexes also include hydrates unless otherwise specified. For example, even when simply referring to "copper formate," it should be understood that the hydrate is also included.

[0020] The copper salt is not particularly limited, but examples thereof include organic acid copper, inorganic acid copper, copper halide, copper hydroxide, and the like, or hydrates thereof, or combinations thereof.

[0021] Examples of the organic acid constituting the organic acid copper include carboxylic acids and sulfonic acids, with carboxylic acids being preferred as the organic acid.

[0022] Suitable examples of the organic acid copper include carboxylate copper and its hydrates. Examples of the carboxylic acid constituting the carboxylate copper include monocarboxylic acids such as formic acid, acetic acid, propionic acid, and butanoic acid, and dicarboxylic acids such as oxalic acid and malonic acid. The carboxylic acid is preferably a monocarboxylic acid, more preferably formic acid and acetic acid, and even more preferably formic acid.

[0023] Specific examples of the organic acid copper salt include copper formate, copper acetate, and hydrates thereof, more preferably copper formate, copper acetate, and hydrates thereof, and even more preferably copper formate and hydrates thereof.

[0024] Examples of inorganic acids that constitute the inorganic acid copper include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, hydrofluoric acid, etc. Preferred inorganic acids are sulfuric acid and nitric acid.

[0025] Specific examples of suitable inorganic acid copper include copper sulfate, copper nitrate, and hydrates thereof.

[0026] The copper halides include copper chloride, copper bromide, copper iodide, and hydrates thereof. The copper hydroxides include copper hydroxide.

[0027] As the copper salt, two or more organic acid copper salts may be used in combination, one or more organic acid copper salts may be used in combination with one or more inorganic acid copper salts, or two or more inorganic acid copper salts may be used in combination. As the copper salt, a combination of two or more organic acid copper salts, or a combination of one or more organic acid copper salts with one or more inorganic acid copper salts is preferred, a combination of two or more carboxylic acid copper salts, or a combination of a carboxylic acid copper salt and an inorganic acid copper salt is more preferred, a combination of copper formate and copper acetate, a combination of copper formate and copper sulfate, or a combination of copper formate and copper nitrate is even more preferred, and a combination of copper formate and copper acetate is particularly preferred.

[0028] The copper compound contains copper formate, and the lower limit of the copper formate content in the copper compound is preferably 20 mol%, more preferably 30 mol%, even more preferably 40 mol%, and particularly preferably 50 mol%. The upper limit of the content may be 100 mol%, but is preferably 90 mol%, more preferably 80 mol%, more preferably 70 mol%, and particularly preferably 60 mol%.

[0029] Copper complexes are compounds in which a copper atom and a ligand are bound by a coordinate bond. Examples of the ligand include monodentate and polydentate ligands. Examples of the monodentate ligand include hydroxo ligands, carboxy ligands, amide ligands, and ammonia. Examples of the polydentate ligand include hydroxy acid esters, β-diketones, β-ketoesters, β-dicarboxylic acid esters, hydrocarbons having a π bond, and diphosphines.

[0030] The lower limit of the content of the copper compound in all components contained in the copper film-forming composition is preferably 0.1 mass%, more preferably 1 mass%, and even more preferably 3 mass%, in terms of the mass concentration of copper atoms in the copper compound. The upper limit of the content is preferably 20 mass%, more preferably 15 mass%, even more preferably 10 mass%, and particularly preferably 6 mass%. By setting the content of the copper compound within the above range, it is possible to improve the adhesion to the glass substrate and the conductivity of the obtained film.

[0031] [Nitrogen-containing organic compound] The copper film-forming composition contains a nitrogen-containing organic compound. This nitrogen-containing organic compound acts as a solubilizer or fluidizer for the copper compound, thereby further improving the adhesion of the copper film formed from the copper film-forming composition to a glass substrate. The nitrogen-containing organic compound may be used alone or in combination of two or more.

[0032] The nitrogen-containing organic compound is not particularly limited as long as it is an organic compound containing a nitrogen atom, but may be an organic compound containing a nitrogen atom such as —OH, —NH ２ and —NH— (hereinafter also referred to as “group (α)”). The unshared electron pair of group (α) in the nitrogen-containing organic compound enhances the interaction between the copper compound and the nitrogen-containing organic compound, thereby further improving the adhesion to the glass substrate and the conductivity of the resulting copper film.

[0033] Nitrogen-containing organic compounds include those with a structure in which -NH- is inserted between carbon atoms constituting hydrocarbons, and those with some or all of the hydrogen atoms of hydrocarbons replaced with -OH or -NH. ２ or a combination thereof is preferred.

[0034] Examples of the hydrocarbon include chain hydrocarbons having 2 to 20 carbon atoms, alicyclic hydrocarbons having 3 to 20 carbon atoms, aromatic hydrocarbons having 6 to 20 carbon atoms, and combinations thereof.

[0035] The chain hydrocarbon having 2 to 20 carbon atoms is preferably a linear or branched chain hydrocarbon having 2 to 20 carbon atoms, and examples thereof include alkanes such as ethane, propane, n-butane, i-butane, n-pentane, isopentane, and neopentane; alkenes such as ethylene, propene, and butene; and alkynes such as acetylene, propyne, and butyne.

[0036] Examples of the alicyclic hydrocarbon having 3 to 20 carbon atoms include cycloalkanes such as cyclopentane and cyclohexane; cycloalkenes such as cyclopropene, cyclopentene and cyclohexene; bridged ring saturated hydrocarbons such as norbornane, adamantane and tricyclodecane; and bridged ring unsaturated hydrocarbons such as norbornene and tricyclodecene.

[0037] Examples of aromatic hydrocarbons having 6 to 20 carbon atoms include benzene, naphthalene, anthracene, and pyrene.

[0038] When the hydrocarbon has a substituent, examples of the substituent include a monovalent chain hydrocarbon group having 1 to 10 carbon atoms, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group, or a propoxy group, an alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group, an alkoxycarbonyloxy group such as a methoxycarbonyloxy group or an ethoxycarbonyloxy group, an acyl group such as a formyl group, an acetyl group, a propionyl group, or a butyryl group, a cyano group, and a nitro group.

[0039] Among these, the nitrogen-containing organic compound is preferably an aliphatic amine, and more preferably a hydroxyaliphatic amine (having —NH together with —OH). ２ and —NH—.) The hydroxyaliphatic amine structure has a chelating effect on the copper atom of the copper compound, which can promote solubilization of the copper compound and, in turn, fluidization of the copper film-forming composition, thereby further improving the adhesion to the glass substrate and the conductivity of the resulting copper film.

[0040] Examples of the nitrogen-containing organic compound include compounds represented by the following formula:

[0041] The lower limit of the content of the nitrogen-containing organic compound is preferably 0.1 mol, more preferably 0.5 mol, even more preferably 1 mol, and particularly preferably 1.5 mol, relative to 1 mol of the copper compound. The upper limit of the content is preferably 5 mol, more preferably 4 mol, even more preferably 3 mol, and particularly preferably 2.5 mol, relative to 1 mol of the copper compound. By setting the content of the nitrogen-containing organic compound within the above range, it is possible to improve the adhesion to the glass substrate and the conductivity of the obtained copper film.

[0042] [Solvent] The solvent preferably contains an organic solvent. Examples of solvents other than organic solvents include water. The lower limit of the content of the organic solvent in the solvent is preferably 40% by mass, more preferably 50% by mass, and even more preferably 60% by mass. The upper limit of the content is preferably 100% by mass (including only the organic solvent as the solvent), but may be 99.9% by mass or even 99% by mass.

[0043] Examples of the organic solvent include alcohol-based solvents, ketone-based solvents, ether-based solvents, ester-based solvents, etc. The metal-containing film-forming composition can contain one or more organic solvents.

[0044] Examples of alcohol solvents include monoalcohol solvents such as methanol, ethanol, n-propanol, and n-butyl alcohol, and polyalcohol solvents such as ethylene glycol, 1,2-propylene glycol, triethylene glycol, and tripropylene glycol.

[0045] Examples of the ketone solvent include chain ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and cyclic ketone solvents such as cyclohexanone.

[0046] Examples of the ether solvent include chain ether solvents such as n-butyl ether, polyhydric alcohol ether solvents such as cyclic ether solvents such as tetrahydrofuran and 1,4-dioxane, and polyhydric alcohol partial ether solvents such as propylene glycol monoethyl ether, tripropylene glycol monomethyl ether, and tetraethylene glycol monomethyl ether.

[0047] Examples of ester-based solvents include carbonate-based solvents such as diethyl carbonate, acetate monoester-based solvents such as methyl acetate and ethyl acetate, lactone-based solvents such as γ-butyrolactone, polyhydric alcohol partial ether carboxylate-based solvents such as diethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate, and lactate-based solvents such as methyl lactate and ethyl lactate.

[0048] As the solvent, alcohol solvents, ether solvents, and combinations thereof are preferred, monoalcohol solvents, polyhydric alcohol solvents, polyhydric alcohol partial ether solvents, and combinations thereof are more preferred, and n-butyl alcohol, propylene glycol, and propylene glycol monomethyl ether are even more preferred.

[0049] The lower limit of the solvent content relative to the total mass of the copper film-forming composition is preferably 30 mass%, more preferably 40 mass%, and even more preferably 50 mass%. The upper limit of the content is preferably 80 mass%, more preferably 70 mass%, and even more preferably 60 mass%. By setting the solvent content within the above range, the fluidity of the composition can be controlled, and the film can exhibit high levels of adhesion to the glass substrate and conductivity.

[0050] [Other Optional Components] The copper film-forming composition may contain other components besides the copper compound, the nitrogen-containing organic compound, and the solvent, such as an acid generator, a polymer additive, a surfactant, and the like.

[0051] <Method for manufacturing a composition for forming a copper film> The method for manufacturing a composition for forming a copper film includes a step of mixing a copper compound, a nitrogen-containing organic compound, and a solvent (hereinafter also referred to as a "mixing step"), and the copper compound is a copper salt or a copper complex.

[0052] In the production method, the copper compound, nitrogen-containing organic compound, and solvent that can be suitably used are the copper compound, nitrogen-containing organic compound, and solvent in the copper film-forming composition.

[0053] In the mixing step, the copper film-forming composition is prepared by mixing a copper compound, a nitrogen-containing organic compound, a solvent, and, if necessary, optional components in a predetermined ratio, and then filtering the resulting mixture through a filter having a pore size of 0.4 μm or less.

[0054] 1A and 1B , in this step, a copper film-forming composition is brought into direct contact with at least a glass wall surface W within a through hole H of a glass substrate 1 having a through hole H, to form a seed layer 2 on the glass wall surface W within the through hole H. Each of FIGS. 1A and 1B is a cross-sectional view schematically illustrating one step of a method for manufacturing a glass substrate with through electrodes. The seed layer 2 may be formed not only within the through hole H, but also on part or all of the front and back surfaces of the glass substrate 1.

[0055] The contact of the copper film-forming composition with the glass wall surface in the through hole is achieved by coating the copper film-forming composition on the glass substrate, immersing the glass substrate 1 in the copper film-forming composition, spraying the copper film-forming composition on the glass substrate, or the like. The contact is preferably achieved by coating the copper film-forming composition on the glass substrate. This results in a film of the copper film-forming composition being formed on the glass wall surface in the through hole of the glass substrate having a through hole. The coating method is not particularly limited, and can be carried out by any appropriate method such as rotary coating, casting coating, or roll coating.

[0056] After coating on the substrate, a drying treatment may be carried out as necessary. A conventionally known method can be used as the drying treatment method. The temperature of the drying treatment is not particularly limited, but is preferably 50°C or higher and 100°C or lower. The time of the drying treatment is also not particularly limited, but is preferably 1 minute or higher and 30 minutes or lower.

[0057] The above contact may be repeated multiple times.

[0058] [Heating Step] The seed layer forming step preferably includes a heating step of heating the copper film forming composition at 150°C or higher and 600°C or lower after contact. The contact is thought to improve the conductivity and strength of the formed film (preferably a coating film). By heating the coating film, metal atoms (mainly copper atoms) in the coating film are reduced to zero valence, and the conductivity of the resulting seed layer is thought to improve.

[0059] The atmosphere in which the coating film is heated is preferably an atmosphere with an oxygen concentration of 30 ppm or less. The upper limit of the oxygen concentration is more preferably 25 ppm, even more preferably 20 ppm, and particularly preferably 10 ppm. The lower the oxygen concentration, the better, and although the lower limit is preferably 0 ppm, it may also be 0.01 ppm or 0.02 ppm. Heating in a low-oxygen-concentration atmosphere can prevent inadvertent oxidation of metal atoms in the coating film, thereby promoting reduction and improving the conductivity of the metal-containing film.

[0060] The heating step is preferably performed in an inert or non-oxidizing gas atmosphere, more preferably in an atmosphere containing nitrogen gas, because the reduction of metal atoms in the coating film can be promoted by using such an atmosphere in the heating step.

[0061] The atmosphere for the heating step may further contain hydrogen gas. When the coating film is heated in an atmosphere containing hydrogen gas, it is believed that the reduction of metal atoms in the coating film is further promoted, and the conductivity of the seed layer is further improved. When the copper compound contains cobalt or nickel as a metal atom, the reduction of these metal atoms can be further promoted by introducing hydrogen gas into the atmosphere for the heating step. Note that when the metal atom is only copper, hydrogen gas may or may not be introduced.

[0062] When the atmosphere in the heating step contains hydrogen gas, the lower limit of the hydrogen gas content in the atmosphere in the heating step is preferably 1000 ppm, more preferably 2000 ppm, even more preferably 5000 ppm, and particularly preferably 10000 ppm. The upper limit of the content is preferably 100000 ppm, more preferably 80000 ppm, even more preferably 60000 ppm, and particularly preferably 40000 ppm. By setting the hydrogen gas content within the above range, the reduction of metal atoms in the coating film can be further promoted, and the conductivity of the seed layer can be further improved.

[0063] The atmosphere in the heating step may further contain water vapor. The inclusion of water vapor can further promote the reduction of metal atoms in the coating film. Water vapor can be introduced by discharging a mixed gas containing nitrogen gas and hydrogen gas into ultrapure water and bubbling it.

[0064] The lower limit of the heating temperature is preferably 150°C, more preferably 200°C, and even more preferably 220°C. The upper limit of the temperature is preferably 600°C, more preferably 500°C, and even more preferably 450°C. The lower limit of the heating time is preferably 100 seconds, more preferably 200 seconds, and even more preferably 300 seconds. The upper limit of the heating time is preferably 2,000 seconds, more preferably 1,000 seconds, and even more preferably 800 seconds.

[0065] Before heating the coating film, it may be preheated at a temperature of 60°C or higher and 200°C or lower. The preheating temperature is usually lower than the temperature in the heating step. The lower limit of the preheating time is preferably 10 seconds, more preferably 30 seconds. The upper limit of the preheating time is preferably 300 seconds, more preferably 180 seconds. The atmosphere in which the coating film is heated may be an atmosphere containing nitrogen gas, an atmosphere containing hydrogen gas, or the air atmosphere.

[0066] In the copper film forming method, exposure and heating can be combined. The radiation used for exposure is appropriately selected from electromagnetic waves such as visible light, ultraviolet light, far ultraviolet light, X-rays, and gamma rays, and particle beams such as electron beams, molecular beams, and ion beams.

[0067] [Through electrode formation process] In this process, a through electrode is formed in the through hole in which the seed layer 2 is formed. As a form of forming the through electrode, a first embodiment in which the through electrode fills the through hole and a second embodiment in which the through electrode does not fill the through hole will be described below.

[0068] First Embodiment In this embodiment, as shown in Fig. 1C, a through electrode 3A is formed by filling a conductive material into a through hole H in which a seed layer 2 has been formed. Fig. 1C is a cross-sectional view schematically showing one step of a method for manufacturing a glass substrate with a through electrode.

[0069] The conductive material is at least one of copper, silver, gold, nickel, platinum, palladium, ruthenium, tin, tin-silver, tin-silver-copper, tin-copper, tin-bismuth-tin-lead, at least one of compounds thereof, or at least one of a mixture of powder of these metals with a resin material.

[0070] Second Embodiment In this embodiment, as shown in Fig. 2A, through electrodes 3B are formed by plating the inside of through holes H in which seed layers 2 have been formed. The thickness of through electrodes 3B formed by plating is determined under conditions that do not block through holes H. Fig. 2A is a cross-sectional view that schematically shows another step in the method for manufacturing a glass substrate with through electrodes.

[0071] Next, as shown in FIG. 2B , the through holes H are filled with potting resin 4. Screen printing or filling with a dispenser can be used for filling. FIG. 2B is a cross-sectional view schematically showing another step in the manufacturing method of a glass substrate with through electrodes. By filling the through holes H with potting resin 4, voids in the through holes H are eliminated, and peeling of the through electrodes 3B inside the through holes H can be prevented.

[0072] If a seed layer is formed on the surface of the glass substrate 1 or if the filling resin 4 protrudes above the through-hole H, these are removed by polishing. By smoothing the surface of the glass substrate 1 through this process, it is possible to improve reliability during the formation and mounting of a wiring layer (not shown).

[0073] 1A to 1C and 2A to 2B, other elements that may be used to form a mounting substrate, such as wiring layers, insulating layers, resists, lands, semiconductor chips, etc. These other elements and manufacturing procedures that use them can suitably employ known techniques.

[0074] Examples will be described below. Note that the examples shown below are representative examples of the present invention, and should not be construed as narrowing the scope of the present invention.

[0075] <Preparation of Copper Film-Forming Composition> [A] Copper compound, [B] Nitrogen-containing organic compound, and [C] Solvent used in the preparation of the copper film-forming composition are shown below.

[0076] [[A] Metal compound] A-1: ​​Copper (II) formate dihydrate A-2: Copper (II) acetate tetrahydrate A-3: Copper (II) sulfate pentahydrate A-4: Copper (II) nitrate trihydrate

[0077] [[B] Nitrogen-containing organic compounds] B-1: A compound represented by the following formula (B-1): B-2: A compound represented by the following formula (B-2): B-3: A compound represented by the following formula (B-3): B-4: A compound represented by the following formula (B-4): B-5: A compound represented by the following formula (B-5): B-6: A compound represented by the following formula (B-6): B-7: A compound represented by the following formula (B-7): B-8: A compound represented by the following formula (B-8): B-9: A compound represented by the following formula (B-9):

[0078]

[0079] [[C] Solvent] C-1: Propylene glycol monoethyl ether C-2: Propylene glycol C-3: Butyl alcohol

[0080] [Example 1-1] Preparation of Copper Film-Forming Composition (J-1) [A] Copper compounds (A-1) (molar ratio 0.3) and (A-2) (molar ratio 0.7) and [C] solvent (C-1) were mixed in a ratio such that the mass concentration of the metal atoms in the copper compound (A) was 4 mass%. Next, [B] nitrogen-containing organic compound (B-6) (molar ratio 2) was mixed, and the resulting solution was filtered through a nylon syringe filter with a pore size of 0.2 μm to prepare a metal-containing film-forming composition (J-1).

[0081] [Examples 1-2 to 1-18 and Comparative Example 1-1] Preparation of copper film-forming compositions (J-2) to (J-18), (j-1) Copper film-forming compositions (J-2) to (J-18) of Examples 1-2 to 1-18 and copper film-forming composition (j-1) of Comparative Example 1-1 were prepared in the same manner as in Example 1-1, except that the types and amounts of each component shown in Table 1 below were used. In the tables, the symbols "-" indicate that the component in question was not used.

[0082]

[0083] <Formation of Copper Film> [Examples 2-1 to 2-18 and Comparative Example 2-1] Each of the copper film-forming compositions (J-1) to (J-18) and (j-1) prepared above was applied onto a glass substrate by a rotary coating method using a spin coater ("MS-B200" manufactured by Mikasa Co., Ltd.) at 1,500 rpm for 30 seconds. The resulting coated film was heated at 400°C for 10 minutes in a nitrogen atmosphere using an RTA furnace ("QHC-P610CP" manufactured by ULVAC, Inc.) and then cooled at 23°C for 60 seconds, thereby obtaining a glass substrate with a copper film.

[0084] <Evaluation> The copper film formed above was evaluated by the following methods. The evaluation results are shown in Table 2 below.

[0085] [Adhesion to Glass Substrate] The adhesion between the copper film and the glass substrate was evaluated by a tape peel test using Scotch (registered trademark) #600 Tape, an adhesive tape manufactured by 3M. Since it is difficult to directly perform a peel test on the copper film formed in the through-holes of the glass substrate, the results of the peel test on the copper-film-coated glass substrate prepared as described above, in which a copper film was formed on the surface of the glass substrate, were used as an index of adhesion. Since glass is exposed on both the surface of the glass substrate and the wall surfaces of the through-holes, it can be determined that the degree of adhesion between the two is substantially equivalent. Specifically, in the tape peel test using the above-mentioned adhesive tape (a peel angle of 90° between the adhesive surface of the peeled adhesive tape (10 mm wide) and the substrate surface, a peel speed of 1 cm / s, and a peeled tape length of 5 cm), the following was evaluated: A if no copper film peeled from the glass substrate; B if no peeling but film roughness was observed; C if partial peeling was observed; and D if complete peeling. The evaluation results are summarized in Table 2.

[0086]

[0087] From the results in Table 2, it can be seen that the copper film formed from the copper film-forming composition of the example had superior adhesion to the glass substrate compared to the copper film formed from the copper film-forming composition of the comparative example.

[0088] According to the method for manufacturing a glass substrate with through electrodes of the present invention, a seed layer having the properties of an adhesion layer can be directly formed on the glass wall surface inside the through hole of the glass substrate without forming an adhesion layer, thereby significantly improving production efficiency while maintaining the adhesion of the through electrode. According to the copper film-forming composition of the present invention, a seed layer having the properties of an adhesion layer can be directly formed on the glass wall surface inside the through hole. Therefore, these can contribute to improving the productivity of manufacturing glass substrates with through electrodes, which require high reliability and high functionality.

[0089] REFERENCE SIGNS LIST 1 Glass substrate 2 Seed layer 3A, 3B Through electrode 4 Buried resin H Through hole W Glass wall surface inside the through hole

Claims

1. A method for manufacturing a glass substrate with through electrodes, comprising: a seed layer forming step of contacting a copper film forming composition directly with at least a glass wall surface within a through hole of a glass substrate having through holes to form a seed layer on the glass wall surface within the through hole; and a through electrode forming step of forming a through electrode in the through hole on which the seed layer has been formed, wherein the copper film forming composition contains a copper compound, a nitrogen-containing organic compound, and a solvent.

2. The method for producing a glass substrate with through electrodes according to claim 1, wherein the copper compound contains copper carboxylate.

3. The method for producing a glass substrate with through electrodes according to claim 1, wherein the copper compound contains copper formate.

4. The method for producing a glass substrate with through electrodes according to claim 3, wherein the copper compound contains copper formate in an amount of 50 mol % or more.

5. The method for producing a glass substrate with through electrodes according to any one of claims 1 to 4, wherein the copper compound contains copper acetate.

6. The above nitrogen-containing organic compound is -OH, -NH ２ 5. The method for producing a glass substrate with through electrodes according to claim 1, wherein the compound has at least one group selected from the group consisting of —NH— and —NH—.

7. The method for producing a glass substrate with through electrodes according to any one of claims 1 to 4, wherein the nitrogen-containing organic compound is an aliphatic amine.

8. A method for manufacturing a glass substrate with through electrodes according to any one of claims 1 to 4, wherein the seed layer forming step includes a step of heating at 150°C or higher and 600°C or lower after contacting the copper film forming composition.

9. A composition for forming a copper film, which is used to form a seed layer directly on a glass wall surface inside a through-hole of a glass substrate having the through-hole, and which comprises a copper compound, a nitrogen-containing organic compound, and a solvent.

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