Through-via metal wiring substrate and manufacturing method therefor

Abstract

The present invention relates to a through-via metal wiring substrate and a manufacturing method therefor. According to the method of the present invention, it is possible to manufacture a substrate having a through-via metal wiring formed thereon with excellent plating quality, by increasing adhesion between the hole sidewall and a plating layer without a costly sputtering process.

Description

Through-via metal wiring substrate and method for manufacturing the same

[0001] The present invention relates to a through-via metal wiring substrate and a method for manufacturing the same, and more specifically, to a substrate in which through-via metal wiring is formed with excellent plating quality by increasing the adhesion between the hole sidewall and the plating layer without an expensive sputtering process, and a method for manufacturing the same.

[0002] Glass is a widely used material in various electronic devices such as displays, interposers, and sensors. These electronic devices may include vias that extend through the thickness of the glass substrate to transmit electrical signals from one main surface of the glass substrate to another main surface of the glass substrate. Through-glass via (TGV) metal wiring can be formed on the glass substrate by filling the vias with metal. This through-glass via metal wiring can carry electrical signals and power between a circuit network located on the upper side of the glass substrate and a circuit network located on the lower side of the glass substrate.

[0003] Glass substrates with metal wiring through-glass vias are widely used as interposers required for packaging technology, such as in Large-Scale Integration (LSI). An interposer is a type of electronic component that connects chips to each other or between a chip and a printed circuit board (PCB) by forming vias in the substrate to mount or place chips on it. While silicon has traditionally been used as the interposer substrate material, it is recently being replaced by glass due to its advantages of being an electrical insulator and having a low cost.

[0004] A conventional method of forming through-via metal wiring (50) on a glass substrate is performed as shown in FIG. 1 by performing titanium (Ti) sputtering on each of the two surfaces of the glass substrate (10) to form a titanium metal layer (20) on both of the surfaces of the glass substrate and on the sidewalls of the via holes (40), and then performing copper (Cu) sputtering on each of the two surfaces of the glass substrate to form a copper seed layer (30) on the titanium metal layer, and then filling the via holes by electrolytic or electroless plating.

[0005] However, the manufacturing method of such through-via metal wiring substrates has the disadvantage of requiring an expensive sputtering process and being complex. In addition, voids or seams are formed within the via holes due to the influence of the aspect ratio, hole size, and composition of the plating solution, which causes a decrease in electrical characteristics or the reliability of the device package.

[0006] In particular, if the adhesion between the hole sidewall and the plating layer is poor during plating, gap defects are likely to occur between the hole sidewall and the plating layer.

[0007] Therefore, there is a need for the development of a method that can form through-via metal wiring with excellent plating quality by increasing the adhesion between the hole sidewall and the plating layer without an expensive sputtering process.

[0008] The objective of the present invention is to provide a substrate having through-via metal wiring formed with excellent plating quality by increasing the adhesion between the hole sidewall and the plating layer without an expensive sputtering process.

[0009] Another objective of the present invention is to provide a method for manufacturing the substrate.

[0010] On the one hand, the present invention

[0011] (i) A step of bonding a metal foil to one surface of a substrate having through vias formed therein through an adhesive layer;

[0012] (ii) a step of removing the adhesive layer located inside the hole by treating the hole formed by the through via and the metal foil with plasma;

[0013] (iii) a step of forming a primer layer by coating a primer composition on the sidewall of the hole;

[0014] (iv) a step of forming a binder layer by coating a binder composition on the primer layer and heat treating it;

[0015] (v) a step of filling the inside of the hole where the binder layer is formed with metal through a plating process; and

[0016] (vi) A method for manufacturing a through-via metal wiring substrate is provided, comprising the step of removing the metal foil and adhesive layer with an etching solution.

[0017]

[0018] On the other hand, the present invention

[0019] (i') A step of forming a primer layer by coating a primer composition on the sidewall of a through via formed on a substrate;

[0020] (ii') a step of forming a binder layer by coating a binder composition on the primer layer and heat treating it;

[0021] (iii') a step of bonding a metal foil to one surface of the substrate through an adhesive layer;

[0022] (iv') a step of removing the adhesive layer located inside the hole by treating the hole formed by the through via and the metal foil with plasma;

[0023] (v') a step of filling the inside of the hole where the binder layer is formed with metal through a plating process; and

[0024] (vi') A method for manufacturing a through-via metal wiring substrate is provided, comprising the step of removing the metal foil and adhesive layer with an etching solution.

[0025]

[0026] A method for manufacturing a through-via metal wiring substrate according to one embodiment of the present invention may further include a step of cleaning the substrate after step (vi) or (vi').

[0027] In one embodiment of the present invention, the substrate may be a glass substrate, a silicon substrate, or a ceramic substrate.

[0028] In one embodiment of the present invention, the metal foil may be a copper foil.

[0029] In one embodiment of the present invention, the metal foil may have a thickness of 3 to 1,000 μm.

[0030] In one embodiment of the present invention, the adhesive layer may be formed from one or more selected from the group consisting of acrylic adhesives, silicone adhesives, polyurethane adhesives, and rubber adhesives.

[0031] In one embodiment of the present invention, the plasma treatment is O2, CF 4, Ar , N 2, He , SF 4, It can be performed using NF3 or a mixture of gases thereof.

[0032] In one embodiment of the present invention, the primer composition may include a silane coupling agent and a solvent.

[0033] In one embodiment of the present invention, the binder composition may include graphite particles and a solvent.

[0034] In one embodiment of the present invention, the plating process may be an electroplating process performed by a bottom-up filling mechanism.

[0035] In one embodiment of the present invention, the metal filled inside the hole may be copper (Cu).

[0036] In one embodiment of the present invention, the etching solution may include one or more selected from the group consisting of copper chloride, iron chloride, hydrochloric acid, nitric acid, sulfuric acid, persulfate compounds, and hydrogen peroxide.

[0037]

[0038] On the other hand, the present invention

[0039] A wiring substrate comprising a substrate and through-via metal wiring formed in the thickness direction of the substrate,

[0040] The above-described through-via metal wiring provides a wiring substrate comprising a primer layer formed on the sidewall of the through-via, a binder layer formed on the primer layer, and a plating layer filled in contact with the binder layer inside the through-via.

[0041] In one embodiment of the present invention, the primer layer may be formed by coating a primer composition comprising a silane coupling agent and a solvent.

[0042] In one embodiment of the present invention, the binder layer may be formed by coating a binder composition comprising graphite particles and a solvent and heat-treating it.

[0043] In one embodiment of the present invention, the plating layer may include copper (Cu).

[0044] According to the present invention, a substrate with through-via metal wiring formed with excellent plating quality can be manufactured by increasing the adhesion between the hole sidewall and the plating layer without an expensive sputtering process, using a bottom-up filling mechanism.

[0045] Figure 1 is a cross-sectional view of the process of a conventional method for manufacturing a through-via metal wiring substrate.

[0046] FIG. 2 is a cross-sectional view of the process of a method for manufacturing a through-via metal wiring substrate according to one embodiment of the present invention.

[0047] FIG. 3 is a cross-sectional view of the process of a method for manufacturing a through-via metal wiring substrate according to another embodiment of the present invention.

[0048] Figure 4 is the result of measuring the cross-section of the through-via metal wiring substrate obtained in Example 1 using a field emission scanning electron microscope (FE-SEM) measurement method.

[0049] Figure 5 is a photograph showing the results of the adhesion evaluation of the through-via metal wiring.

[0050] The present invention will be described in more detail below.

[0051]

[0052] One embodiment of the present invention relates to a method for manufacturing a through-via metal wiring substrate.

[0053]

[0054] A method for manufacturing a through-via metal wiring substrate according to one embodiment of the present invention is

[0055] (i) A step of bonding a metal foil to one surface of a substrate having through vias formed therein through an adhesive layer;

[0056] (ii) a step of removing the adhesive layer located inside the hole by treating the hole formed by the through via and the metal foil with plasma;

[0057] (iii) a step of forming a primer layer by coating a primer composition on the sidewall of the hole;

[0058] (iv) a step of forming a binder layer by coating a binder composition on the primer layer and heat treating it;

[0059] (v) a step of filling the inside of the hole where the binder layer is formed with metal through a plating process; and

[0060] (vi) includes the step of removing the metal foil and adhesive layer with an etching solution.

[0061]

[0062] A method for manufacturing a through-via metal wiring substrate according to one embodiment of the present invention can manufacture a substrate with through-via metal wiring formed with excellent plating quality through a bottom-up filling mechanism by increasing the adhesion between the hole sidewall and the plating layer without an expensive sputtering process.

[0063]

[0064] A method for manufacturing a through-via metal wiring substrate according to one embodiment of the present invention is described in detail as follows.

[0065] FIG. 2 is a cross-sectional view of the process of a method for manufacturing a through-via metal wiring substrate according to one embodiment of the present invention.

[0066]

[0067] As illustrated in FIG. 2a, step (i) is a step of forming a hole (140) by bonding a metal foil (130) through an adhesive layer (120) to one side of a substrate (110) in which a through-via is formed.

[0068] The above substrate (110) may be a glass substrate, a silicon substrate, a ceramic substrate, etc., and may be a glass substrate in particular.

[0069] The substrate with the above-mentioned through-vias formed thereon can be manufactured using methods known in the art or commercially available products can be used.

[0070] For example, a glass substrate with through-glass vias can be manufactured by forming vias by irradiating a glass substrate with UV or carbon dioxide laser, forming vias by forming fine holes in a photosensitive glass substrate and then etching with hydrofluoric acid, or forming vias by drilling into a glass substrate with a pair of upper and lower core drills facing each other.

[0071] The above glass substrate may be composed of quartz glass, borosilicate glass, aluminosilicate glass, soda-lime glass, titanium-containing silicate glass, or alkali-free glass.

[0072]

[0073] In one embodiment of the present invention, the inner diameter of the through-via may be 2 to 300 μm. A through-via metal wiring can be formed with excellent plating quality within the inner diameter range.

[0074] In one embodiment of the present invention, the thickness of the substrate may be appropriately selected according to the application and may be, for example, 100 to 1,000 μm.

[0075]

[0076] The above metal foil serves as a seed metal layer for the plating process, and by using it, the sputtering process for forming a separate seed metal layer can be omitted.

[0077] The metal foil may comprise one or more selected from the group consisting of copper (Cu), titanium (Ti), iron (Fe), chromium (Cr), aluminum (Al), nickel (Ni), and alloys thereof, and preferably may be copper foil.

[0078] The metal foil may have a thickness of 3 to 1,000 μm, preferably 5 to 100 μm. If the thickness of the metal foil is less than the above range, workability may be poor during the adhesive application and bonding process with the substrate, and if it exceeds the above range, uniform bonding with the substrate may be difficult.

[0079]

[0080] The adhesive layer may be formed from one or more selected from the group consisting of acrylic adhesives, silicone adhesives, polyurethane adhesives, and rubber adhesives.

[0081] The adhesive layer can be formed by applying and curing the adhesive on one side of a substrate in which the through-via is formed, or by using a commercially available product.

[0082] The application method of the above adhesive is not particularly limited, but examples include spray coating, bar coating, gravure coating, knife coating, air knife coating, curtain coating, die coating, etc.

[0083] The above adhesive can be cured by heat or light, and an appropriate curing method can be selected depending on the type of adhesive.

[0084] If the above adhesive is thermosetting, heat curing can be performed by heating and drying at, for example, 40 to 200°C, preferably 50 to 180°C, more preferably 70 to 170°C.

[0085] If the above adhesive is photocurable, photocuring can be performed by irradiating, for example, ultraviolet and / or short-wavelength visible light at an integrated light intensity of about 100 to 5000 mJ / ㎠. At this time, LED light sources, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, xenon lamps, etc. are preferably used as light sources.

[0086] The above adhesive layer may have a thickness of 50 μm or less, preferably 1 to 50 μm. If the thickness of the above adhesive layer exceeds 50 μm, it may be difficult to remove with plasma and may take a long time.

[0087]

[0088] As illustrated in FIG. 2b, step (ii) is a step of removing an adhesive layer, which is an organic material located inside the hole (140), by treating the hole (140) formed by the through via and the metal foil with plasma so that the plating process described later can proceed smoothly.

[0089] In step (ii) above, the plasma treatment is O2, CF 4, Ar , N 2, He , SF 4, It can be performed using NF3 or a mixture of gases thereof.

[0090]

[0091] As illustrated in FIG. 2c, step (iii) is a step of forming a primer layer (150) by coating a primer composition on the sidewall of the hole (140).

[0092] The primer layer (150) above serves to provide adhesion between the hole sidewall and the binder layer (160) described later.

[0093] In one embodiment of the present invention, in step (iii), the primer layer (150) can be formed by coating a primer composition comprising a silane coupling agent and a solvent.

[0094] The coating of the above primer composition can be performed by dip coating, spray coating, etc. In particular, the dip coating method is preferred because it provides excellent uniformity of the coating surface and enables uniform coating on large areas and non-uniform surfaces.

[0095] When performing the above dip coating, ultrasonic treatment can be applied to the primer composition to uniformly disperse and coat the silane coupling agent.

[0096] Specifically, ultrasonic treatment can be performed at 10 to 40°C with an output of 50 to 200 W.

[0097] After the above coating, it can be dried at room temperature and then dried at a high temperature.

[0098] The bonding strength of the primer layer can be strengthened through the above high-temperature drying.

[0099] The above high-temperature drying can be performed in a temperature range of 100 to 150°C.

[0100] The above silane coupling agent may be a silane compound having an alkoxy group capable of bonding with an inorganic material such as glass, silicon, or ceramic that constitutes the hole sidewall, and a reactive functional group capable of bonding with graphite that constitutes the binder layer (160) described later.

[0101] Specifically, the silane coupling agent may be a compound represented by the following chemical formula 1.

[0102] [Chemical Formula 1]

[0103]

[0104] In the above formula,

[0105] X is a C1-C6 alkyl group substituted with one or more functional groups selected from the group consisting of amino groups, (meth)acrylic groups, epoxy groups, and mercapto groups; or a vinyl group, and

[0106] R 1 and R 2 Each is independently a C1-C4 alkyl group, and

[0107] n is an integer from 1 to 3.

[0108]

[0109] For example, the above silane coupling agents may include vinyltrimethoxysilane, vinyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, etc.

[0110]

[0111] The above silane coupling agent may be included in an amount of 0.5 to 1.9 weight%, preferably 0.5 to 1.5 weight%, based on 100 weight% of the total primer composition. Sufficient adhesion can be secured within the above content range. If the content of the above silane coupling agent is below the above range, it is difficult to secure adhesion, which may result in reduced plating quality, and if it exceeds the above range, the viscosity of the primer composition increases and hole clogging may occur.

[0112]

[0113] The above solvent plays a role in helping the silane coupling agent to be uniformly distributed on the surface.

[0114] Examples of the above solvents include water; alcohol-based solvents such as ethanol, isopropanol, methanol, butanol, hexanol, and cyclohexanol; ketone-based solvents such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbon-based solvents such as toluene, benzene, xylene, and mesitylene; hexane-based solvents such as hexane, heptane, and octane; and dimethylformamide.

[0115] The above solvent may be included in the remainder amount so that the total amount of the primer composition is 100% by weight.

[0116]

[0117] The above primer composition may further include a hydrolysis promoter, a surfactant, etc.

[0118] The above hydrolysis accelerator plays a role in increasing the hydrolysis reaction rate of the above silane coupling agent.

[0119] Examples of the above hydrolysis promoters include acidic hydrolysis promoters such as hydrochloric acid (HCl) or acetic acid, and basic hydrolysis promoters such as sodium hydroxide (NaOH) or ammonium hydroxide (NH4OH).

[0120] The above hydrolysis accelerator may be included in an amount of 0.01 to 5.0 weight%, preferably 0.1 to 1.0 weight%, based on 100 weight% of the total primer composition. When within the above content range, the hydrolysis reaction rate of the silane coupling agent can be appropriately increased.

[0121] The above surfactant maintains the uniform dispersibility of the silane coupling agent, enables uniform coating through surface tension control, and prevents aggregation.

[0122] Examples of the above surfactants include anionic surfactants, cationic surfactants, and nonionic surfactants. In particular, cationic surfactants are preferred in terms of the coating uniformity of the primer composition and the adhesion of the primer layer.

[0123] The above anionic surfactant is highly hydrophilic and can increase dispersion stability while minimizing reaction with silane coupling agents.

[0124] Specifically, examples of the above anionic surfactants include sulfonate-based anionic surfactants such as sodium dodecyl sulfate (SDS) and sodium dodecylbenzene sulfonate (SDBS), carboxylate-based anionic surfactants such as sodium stearate, or phosphate ester-based anionic surfactants.

[0125] The above cationic surfactant can control hydrophilicity and / or hydrophobicity by combining with a silane coupling agent.

[0126] Specifically, examples of the above cationic surfactants include quaternary ammonium cationic surfactants such as CTAB (cetyltrimethylammonium bromide), amine cationic surfactants such as dodecylamine and stearylamine, and in particular, CTAB (cetyltrimethylammonium bromide) is preferred in terms of coating uniformity of the primer composition and adhesion of the primer layer.

[0127] The above nonionic surfactant does not carry a charge, so it can stably disperse silane coupling agents in various environments.

[0128] Specifically, examples of the above nonionic surfactants include polyoxyethylene (POE)-based nonionic surfactants such as polyvinyl alcohol (PVA), Tween 20, Tween 80, and Triton X-100, poloxamers such as Pluronic F68, and silicone-based surfactants such as PDMS (poly(dimethylsiloxane)).

[0129] The above surfactant may be included in an amount of 0.1 to 0.2 weight% based on 100 weight% of the total primer composition. When within this content range, it is possible to maintain the uniform dispersibility of the silane coupling agent, enable uniform coating of the primer composition, and prevent aggregation.

[0130] The thickness of the primer layer (150) may be 1 nm to 30 nm. When the thickness of the primer layer (150) is within the above range, the durability of the primer layer is excellent, and surface modification characteristics and adhesion can be secured.

[0131]

[0132] In step (iii) above, before coating with the primer composition, the surface to be coated may be activated to induce the formation of hydroxyl groups (-OH).

[0133] In addition, the surface can be dried to a clean, moisture-free state and cleaned to be free of organic matter or contaminants.

[0134] Specifically, the surface treatment can be performed by using a strong acid such as sulfuric acid or hydrochloric acid at 10 to 40°C for 10 minutes to 1 hour.

[0135]

[0136] As illustrated in FIG. 2d, step (iv) is a step of forming a binder layer (160) by coating a binder composition on the primer layer (150) and heat-treating it.

[0137] The binder layer (160) provides conductivity and improves the adhesion of the metal plating layer during the plating process.

[0138] In one embodiment of the present invention, in step (iv), the binder layer can be formed by coating a binder composition comprising graphite particles and a solvent and heat treating it.

[0139] The coating of the above binder composition can be performed using dip coating, spray coating, etc. In particular, the dip coating method is preferred because it allows for a simple and highly reproducible coating process with excellent uniformity of the coated surface.

[0140] After the above coating, heat treatment is performed.

[0141] Through the above heat treatment, the solvent present in the primer layer and binder layer is removed, the bonding between the silane coupling agent and the material constituting the hole sidewall is stabilized, functional groups such as -OH, -COOH, and C=O present in the graphite within the binder layer are induced to form chemical bonds with the silane coupling agent, and interfacial stress can be stabilized.

[0142] The above heat treatment can be performed at 100 to 200°C. If the heat treatment temperature is below the above range, the adhesion between the primer layer and the binder layer may decrease, and thermal / chemical stability may decrease as bubbles are generated during the plating process due to insufficient evaporation of the organic solvent or water included in the binder composition. If the above range is exceeded, the Si-O-Si bond formed by the silane coupling agent being bonded to the hole wall may be destroyed, and the adhesion between the hole and the silane coupling agent may be weakened due to the decomposition of the organic functional groups (NH2, etc.) of the silane coupling agent.

[0143] The above heat treatment can be performed for 10 minutes to 1 hour.

[0144]

[0145] The above binder composition may be in the form of a colloid in which graphite particles are dispersed in a solvent.

[0146] The above graphite particles are particles with a multilayer structure composed of carbon, capable of providing conductive and wear-resistant properties, forming conductive paths on a substrate, and serving to provide a conductive layer.

[0147] The average particle size of the graphite particles may be 1 to 100 nm, preferably 10 to 50 nm. When the average particle size of the graphite particles is within the above range, electrical conductivity is improved, the surface area is increased, the mechanical reinforcement effect is excellent, and inter-particle connectivity can be improved.

[0148] The graphite particles may be included in an amount of 1 to 2.9 weight percent based on 100 weight percent of the total binder composition. When within this content range, the binder layer can be formed with an appropriate thickness, exhibits excellent adhesion, and ensures plating uniformity. If the content of the graphite particles is below this range, the binder layer is formed too thin, resulting in reduced adhesion and plating uniformity, and peeling of the plating layer may occur after plating. If the content exceeds this range, the binder layer becomes thicker and the surface becomes rough, and localized over-plating or under-plating may occur due to uneven current distribution during electroplating, and uneven thickness of the plating layer may result.

[0149]

[0150] The above solvent serves to disperse graphite particles and maintain them in a liquid form.

[0151] Examples of the above solvents include water-based solvents such as pure water (H2O), ethanol, and isopropanol (IPA), and oil-based solvents such as acetone, toluene, and methyl ethyl ketone (MEK).

[0152] The above solvent may be included in the remainder to make up 100 weight% of the total binder composition. For example, the above solvent may be included in an amount of 60 to 99 weight%, preferably 70 to 99 weight%, more preferably 80 to 99 weight%, and even more preferably 93 to 98 weight% with respect to 100 weight% of the total binder composition.

[0153] The above binder composition may further include a dispersant, a pH adjuster, etc.

[0154] The above-mentioned dispersant acts as a surfactant that prevents the agglomeration of graphite particles.

[0155] As the above-mentioned dispersant, those exemplified as surfactants in the above-mentioned primer composition may be used.

[0156] As the above dispersant, a nonionic surfactant is preferred in terms of preventing the aggregation of graphite particles, coating uniformity of the binder composition, and adhesion of the binder layer, and PVA is particularly preferred.

[0157] The above-mentioned dispersant may be included in an amount of 0.5 to 5 weight%, preferably 0.5 to 3 weight%, and more preferably 0.5 to 1 weight% based on 100 weight% of the total binder composition. When the above-mentioned dispersant is included in an amount within the above content range, the aggregation of graphite particles can be effectively prevented, and plating quality can be ensured.

[0158] The above pH adjuster alkalizes the binder composition, thereby increasing the repulsive force between particles by increasing the negative surface charge of the graphite particles, which can enable the graphite particles to be stably dispersed in the solution.

[0159] As the above pH adjuster, water ammonia (NH4OH), sodium hydroxide (NaOH), potassium hydroxide (KOH), acetic acid, phosphoric acid, etc. may be used.

[0160] The above pH adjuster may be included so that the pH of the binder composition is 9 to 11, for example, in an amount of 0.1 to 2 weight% with respect to 100 weight% of the total binder composition. When the above pH adjuster is included in an amount within the above content range, the dispersibility of the graphite particles is excellent.

[0161] The above binder composition may contain a resin component in an amount of 5% by weight or less, preferably 3% by weight or less, and more preferably 1% by weight or less, relative to 100% by weight of the total binder composition in terms of ensuring coating performance and plating quality. If the content of the resin component falls outside the above range, coating performance may be reduced, it may not be easy to control the thickness of the binder layer, and it may be difficult to form a uniform plating layer during the plating process.

[0162] The thickness of the binder layer (160) may be 50 nm to 200 nm, preferably 90 nm to 160 nm. When the thickness of the binder layer (160) is within the above range, electrical conductivity is improved, the surface area is increased, the mechanical reinforcement effect is excellent, and inter-particle connectivity is improved. If the thickness of the binder layer (160) is less than the above range, adhesion is reduced, plating uniformity is reduced, and delamination of the plating layer may occur after plating; if it exceeds the above range, aggregation or cracking may be induced in the plating layer, plating uniformity is reduced, and delamination of the plating layer may occur after plating.

[0163] The binder layer can form a conductive path. That is, graphite particles can form a conductive layer on the substrate and lay the foundation for a subsequent plating process.

[0164] In addition, the binder layer can provide electrical properties. That is, it has characteristics that facilitate electron movement. Accordingly, the binder layer can be widely used in electrochemical applications and electronic substrates such as PCBs.

[0165] In addition, the binder layer can promote plating. That is, it can act as a seed layer for plating and contribute to forming a uniform plating layer.

[0166]

[0167] As illustrated in FIG. 2e, step (v) is a step of filling the inside of the hole (140) with metal through a plating process.

[0168] In step (v) above, the plating process may be an electroplating process performed by a bottom-up filling mechanism.

[0169] The above electroplating process may be performed by applying current in a current density range of 0.5 ASD to 10 ASD (Ampere per Square Decimere). At this time, the applied current density may be applied in a specific waveform.

[0170] In step (v) above, the metal filled inside the hole (140) may be copper (Cu), gold (Au), silver (Ag), titanium (Ti), nickel (Ni), tin (Sn), cobalt (Co), iron (Fe), or an alloy containing at least one of these components, preferably copper (Cu).

[0171] The plating composition used in the above electrolytic plating process may include a metal salt, a strong acid, and a halogen ion source.

[0172] The above metal salt acts as a metal ion source that dissociates within the composition to supply metal ions, and can be filled inside the hole by being reduced and precipitated through an electrochemical reaction.

[0173] The metal salt can be appropriately selected depending on the type of metal to be filled in the hole, for example, copper (Cu), gold (Au), silver (Ag), titanium (Ti), nickel (Ni), tin (Sn), cobalt (Co), iron (Fe), or an alloy containing at least one of these components, such as inorganic salts, organic salts, oxides, chlorides, etc. When the metal to be filled in the hole is copper (Cu), copper sulfate, copper nitrate, copper acetate, copper oxide, copper chloride, etc. can be used as the metal salt.

[0174] The concentration of the metal salt is not particularly limited, but, for example, it may be 100 to 300 g / L, and preferably 200 to 250 g / L.

[0175] The above strong acid acts as an electrolyte in addition to pH adjustment, and commonly known substances may be used. Specifically, the strong acid may be one or more selected from the group consisting of sulfuric acid, hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, trifluoromethanesulfonic acid, sulfonic acid, hydrobromide, and fluoroboric acid.

[0176] The concentration of the above strong acid is not particularly limited, but considering the pH of the plating composition, it may be 50 to 150 g / L, and specifically 90 to 110 g / L.

[0177] The above-mentioned halogen ion source supplies halogen ions into the composition, and a commonly known substance may be used. Specifically, the halogen ion source may be a chloride ion source, for example, hydrochloric acid (HCl).

[0178] The concentration of the above halogen ion source is not particularly limited, but, for example, may be 30 to 250 mg / L, and preferably 40 to 200 mg / L.

[0179] In addition, the plating composition may further include one or more of a brightener and a carrier.

[0180] The above brightener promotes plating by increasing the reduction rate of metal ions, and commonly known materials may be used. Specifically, the brighteners are bis-(3-sulfopropyl)disulfide sodium salt, 3-mercapto-1-propanesulfonic acid sodium salt, 3-amino-1-propanesulfonic acid, O-ethyl-S-(3-sulfopropyl)dithiocarbonate sodium salt, 3-(2-benzthiazoly-1-thio)-1-propanesulfonic acid sodium salt, and N,N-dimethyldithiocarbamic-(3-sulfopropyl)ester sodium salt. It may be one or more selected from the group consisting of acid-(3-sulfopropyl)ester, sodium salt).

[0181] The concentration of the brightener is not particularly limited, but considering the plating speed, it may be 0.5 to 10 ml / L, and specifically 1 to 7 ml / L.

[0182] The above carrier is intended to increase the surface flatness of the wiring by controlling the metal reduction rate through inhibiting the movement of metal ions, and commonly known materials may be used. For example, polyethylene glycol, polypropylene glycol, or copolymers thereof may be used as the carrier.

[0183] The concentration of the carrier is not particularly limited, but, for example, may be 1 to 15 ml / L, and preferably 3 to 12 ml / L.

[0184]

[0185] The plating composition may contain a remainder of water. The water may be deionized water.

[0186]

[0187] As shown in FIG. 2f, step (vi) is a step of removing the metal foil and adhesive layer with an etching solution.

[0188] In step (vi) above, the component of the etching solution can be appropriately selected according to the component of the metal foil. For example, if the metal foil is copper foil, a conventional copper-based metal film etching solution can be used as the etching solution.

[0189] Specifically, in step (vi), the etching solution may include one or more selected from the group consisting of copper chloride, iron chloride, hydrochloric acid, nitric acid, sulfuric acid, persulfate compounds and hydrogen peroxide.

[0190] The above etching solution may contain water corresponding to the remainder.

[0191] The above etching solution can be processed by spraying. By processing the etching solution by spraying, the dissolution of the metal filled in the plating process can be prevented, thereby preventing a decrease in the electrical characteristics of the substrate or the reliability of the device package.

[0192]

[0193] According to a manufacturing method according to one embodiment of the present invention, as shown in FIG. 2g, a substrate (110) with through-via metal wiring (170) formed thereon can be manufactured with excellent plating quality by increasing the adhesion between the hole sidewall and the plating layer without an expensive sputtering process.

[0194]

[0195] A method for manufacturing a through-via metal wiring substrate according to another embodiment of the present invention is

[0196] (i') A step of forming a primer layer by coating a primer composition on the sidewall of a through via formed on a substrate;

[0197] (ii') a step of forming a binder layer by coating a binder composition on the primer layer and heat treating it;

[0198] (iii') a step of bonding a metal foil to one surface of the substrate through an adhesive layer;

[0199] (iv') a step of removing the adhesive layer located inside the hole by treating the hole formed by the through via and the metal foil with plasma;

[0200] (v') a step of filling the inside of the hole where the binder layer is formed with metal through a plating process; and

[0201] (vi') includes the step of removing the metal foil and adhesive layer with an etching solution.

[0202]

[0203] A method for manufacturing a through-via metal wiring substrate according to another embodiment of the present invention is described in detail as follows.

[0204] FIG. 3 is a cross-sectional view of the process of a method for manufacturing a through-via metal wiring substrate according to another embodiment of the present invention.

[0205]

[0206] As illustrated in FIG. 3a', step (i') is a step of forming a primer layer (150) by coating a primer composition on the sidewall of the through via of a substrate (110) in which the through via is formed.

[0207] In step (i') above, the substrate on which the through-via is formed may be the same substrate as the substrate used in step (i) above.

[0208] In step (i') above, the primer layer can be formed using the same primer composition as used in step (iii) above.

[0209] A detailed description of the substrate and primer composition in which through-vias are formed is omitted to avoid duplication.

[0210]

[0211] As illustrated in FIG. 3b', step (ii') is a step of forming a binder layer (160) by coating a binder composition on the primer layer (150) and heat-treating it.

[0212] In step (ii') above, the binder layer can be formed using the same binder composition as used in step (iv) above.

[0213] In step (ii') above, the heat treatment can be performed under the same conditions as those performed in step (iv) above.

[0214] A detailed description of the binder composition and heat treatment is omitted to avoid duplication.

[0215]

[0216] As illustrated in FIG. 3c', step (iii') is a step of bonding a metal foil (130) to one side of the substrate through an adhesive layer (120).

[0217] In step (iii') above, the metal foil and adhesive layer can be formed using the same materials as the metal foil and adhesive layer used in step (i) above.

[0218] A detailed description of the metal foil and adhesive layer is omitted to avoid duplication.

[0219]

[0220] As illustrated in FIG. 3d', step (iv') is a step of removing an adhesive layer located inside the hole by treating the hole (140) formed by the through via and the metal foil with plasma.

[0221] In step (iv') above, the plasma treatment can be performed in the same way as in step (ii).

[0222] A detailed explanation of the plasma treatment is omitted to avoid duplication.

[0223]

[0224] As illustrated in FIG. 3e', step (v') is a step of filling the inside of the hole (140) where the binder layer is formed with metal through a plating process.

[0225] The above plating process can be performed in the same way as step (v).

[0226] A detailed explanation of the plating process is omitted to avoid duplication.

[0227]

[0228] As illustrated in FIG. 3f', step (vi') is a step of removing the metal foil and adhesive layer with an etching solution.

[0229] The removal of the adhesive layer can be performed in the same way as in step (vi).

[0230] A detailed explanation regarding the removal of the adhesive layer is omitted to avoid duplication.

[0231]

[0232] According to a manufacturing method according to another embodiment of the present invention, as shown in FIG. 3g', a substrate (110) with through-via metal wiring (170) formed thereon can be manufactured with excellent plating quality by increasing the adhesion between the hole sidewall and the plating layer without an expensive sputtering process.

[0233]

[0234] A method for manufacturing a through-via metal wiring substrate according to one embodiment of the present invention may further include a step of cleaning the substrate after step (vi) or (vi').

[0235] The above washing can be performed using deionized water.

[0236]

[0237] One embodiment of the present invention is

[0238] A wiring substrate comprising a substrate and through-via metal wiring formed in the thickness direction of the substrate,

[0239] The above-described through-via metal wiring relates to a wiring substrate comprising a primer layer formed on the sidewall of the through-via, a binder layer formed on the primer layer, and a plating layer filled in contact with the binder layer inside the through-via.

[0240]

[0241] The above primer layer serves to provide adhesion between the through-via sidewall and the binder layer, and may include a silane coupling agent.

[0242] The silane coupling agent of the above primer layer can bond with the material constituting the through-via sidewall and can also bond with functional groups such as -OH, -COOH, C=O present in the graphite particles within the binder layer.

[0243] The above binder layer serves to provide conductivity and improve the adhesion of the metal plating layer during the plating process, and may include graphite particles.

[0244] The above substrate, primer layer, and binder layer are the same as those described in the method for manufacturing a through-via metal wiring substrate described above, so a detailed description is omitted.

[0245] The above plating layer is formed by filling the inside of the through vias with metal.

[0246] The metal filled inside the above penetrating via is the same as the metal used in step (v) or (v').

[0247] Specifically, the metal may be copper (Cu), gold (Au), silver (Ag), titanium (Ti), nickel (Ni), tin (Sn), cobalt (Co), iron (Fe), or an alloy containing at least one of these components, and preferably may include copper (Cu).

[0248]

[0249] The present invention will be explained more specifically below through examples, comparative examples, and experimental examples. These examples, comparative examples, and experimental examples are intended solely to illustrate the present invention, and it is obvious to those skilled in the art that the scope of the present invention is not limited thereto.

[0250]

[0251] Example 1: Formation of through-via metal wiring

[0252] A copper foil with a thickness of 30 μm was bonded to one side of a glass substrate with a thickness of 130 μm having through vias with an internal diameter of 80 μm, via an acrylic adhesive layer (ATL-30, ternary) with a thickness of 2 μm.

[0253] The adhesive layer located inside the glass hole was removed by treating the other side of the glass substrate with plasma using O2 gas.

[0254] Surface activation (formation of -OH groups) was performed by immersing the inside of the glass hole in hydrochloric acid at 25°C for 30 minutes.

[0255] Meanwhile, a primer composition was prepared by mixing 1.0 wt% of γ-aminopropyltriethoxysilane as a silane coupling agent, 0.12 wt% of hydrochloric acid (HCl) as a hydrolysis accelerator, 0.1 wt% of CTAB (cetyltrimethylammonium bromide) as a cationic surfactant, and ethanol as a solvent to make up 100 wt% of the total composition. The primer composition was left for 5 to 30 minutes to induce sufficient hydrolysis of the silane coupling agent to generate silanol groups.

[0256] The inside of the surface-activated glass hole was immersed in the primer composition at 25°C for 30 to 60 minutes to coat the primer composition using a dip coating method. During the dip coating, the primer composition was treated with ultrasonics. The ultrasonic treatment was performed at 25°C with an output of 150W.

[0257] Subsequently, to form a silane layer, the primer layer was formed by natural drying at room temperature for 30 minutes, followed by high-temperature drying at 110°C for 1 to 2 hours. The thickness of the primer layer was 30 nm.

[0258] A binder composition comprising 2.0 wt% of graphite particles with an average particle size of 25 nm, 0.5 wt% of polyvinyl alcohol (PVA) as a dispersant, and the remainder being water, with the pH adjusted to 10 using KOH as a pH adjuster, was applied by dip coating at 32°C for 45 seconds and dried with cold air, then washed with water. Then, the binder composition was applied again by dip coating at 32°C for 90 seconds and dried, then washed with water, then dried with hot air, and heat-treated at 180°C for 30 minutes to form a binder layer. The thickness of the binder layer was 150 nm.

[0259] The inside of the glass hole was filled by performing an electroplating process using a plating composition comprising 230 g / L copper sulfate, 105.7 g / L sulfuric acid, 176 mg / L hydrochloric acid, 6 ml / L bis-(3-sulfopropyl) disulfide sodium salt, 4 ml / L polyethylene glycol, and the remainder being deionized water.

[0260] A glass substrate having through-via metal wiring formed thereon was obtained by spraying an etching solution containing 5 wt% sulfuric acid, 10 wt% hydrogen peroxide, and the remainder deionized water onto the copper foil surface of the glass substrate in which the above plating process was completed, thereby removing the copper foil and the adhesive layer.

[0261]

[0262] Example 2: Formation of through-via metal wiring

[0263] A glass substrate having through-via metal wiring formed thereon was obtained by performing the same method as in Example 1, except that the content of the silane coupling agent in the primer composition was changed to 0.5 wt%. The thickness of the primer layer was 10 nm, and the thickness of the binder layer was 150 nm.

[0264]

[0265] Example 3: Formation of through-via metal wiring

[0266] A glass substrate having through-via metal wiring formed thereon was obtained by performing the same method as in Example 1, except that the content of the silane coupling agent in the primer composition was changed to 1.5 wt%. The thickness of the primer layer was 40 nm, and the thickness of the binder layer was 150 nm.

[0267]

[0268] Example 4: Formation of through-via metal wiring

[0269] A glass substrate having through-via metal wiring formed thereon was obtained by performing the same method as in Example 1, except that the content of the silane coupling agent in the primer composition was changed to 1.9 wt%. The thickness of the primer layer was 50 nm, and the thickness of the binder layer was 150 nm.

[0270]

[0271] Example 5: Formation of through-via metal wiring

[0272] A glass substrate with through-via metal wiring was obtained by performing the same method as in Example 1, except that Triton X-100 was used as a nonionic surfactant instead of CTAB as a cationic surfactant in the primer composition. The thickness of the primer layer was 30 nm, and the thickness of the binder layer was 150 nm.

[0273]

[0274] Example 6: Formation of through-via metal wiring

[0275] A glass substrate with through-via metal wiring was obtained by performing the same procedure as in Example 1, except that Tween 20 was used as a nonionic surfactant instead of CTAB as a cationic surfactant in the primer composition. The thickness of the primer layer was 30 nm, and the thickness of the binder layer was 150 nm.

[0276]

[0277] Example 7: Formation of through-via metal wiring

[0278] A glass substrate with through-via metal wiring was obtained by performing the same method as in Example 1 above, except that SDBS was used as an anionic surfactant instead of CTAB as a cationic surfactant in the primer composition. The thickness of the primer layer was 30 nm, and the thickness of the binder layer was 150 nm.

[0279]

[0280] Example 8: Formation of through-via metal wiring

[0281] A glass substrate having through-via metal wiring formed thereon was obtained by performing the same method as in Example 1, except that the graphite content of the binder composition was changed to 1.0 wt%. The thickness of the primer layer was 30 nm, and the thickness of the binder layer was 90 nm.

[0282]

[0283] Example 9: Formation of through-via metal wiring

[0284] A glass substrate having through-via metal wiring formed thereon was obtained by performing the same method as in Example 1, except that the graphite content of the binder composition was changed to 2.5 wt%. The thickness of the primer layer was 30 nm, and the thickness of the binder layer was 180 nm.

[0285]

[0286] Example 10: Formation of through-via metal wiring

[0287] A glass substrate having through-via metal wiring formed thereon was obtained by performing the same method as in Example 1, except that the graphite content of the binder composition was changed to 2.9 wt%. The thickness of the primer layer was 30 nm, and the thickness of the binder layer was 200 nm.

[0288]

[0289] Example 11: Formation of through-via metal wiring

[0290] A glass substrate with through-via metal wiring formed thereon was obtained by performing the same method as in Example 1, except that SDS was used instead of PVA as the dispersant of the binder composition. The thickness of the primer layer was 30 nm, and the thickness of the binder layer was 150 nm.

[0291]

[0292] Example 12: Formation of through-via metal wiring

[0293] A glass substrate with through-via metal wiring was obtained by performing the same method as in Example 1, except that Triton X-100 was used instead of PVA as the dispersant of the binder composition. The thickness of the primer layer was 30 nm, and the thickness of the binder layer was 150 nm.

[0294]

[0295] Example 13: Formation of through-via metal wiring

[0296] A glass substrate having through-via metal wiring formed thereon was obtained by performing the same method as in Example 1, except that after coating the binder composition, heat treatment was performed at 120°C.

[0297]

[0298] Example 14: Formation of through-via metal wiring

[0299] A glass substrate having through-via metal wiring formed thereon was obtained by performing the same method as in Example 1, except that after coating the binder composition, heat treatment was performed at 150°C.

[0300]

[0301] Comparative Example 1: Formation of through-via metal wiring

[0302] A glass substrate with through-via metal wiring formed thereon was obtained by performing the same method as in Example 1, except that a primer layer was not formed.

[0303]

[0304] Comparative Example 2: Formation of through-via metal wiring

[0305] A glass substrate having through-via metal wiring formed thereon was obtained by performing the same method as in Example 1, except that a binder layer was not formed.

[0306]

[0307] Comparative Example 3: Formation of through-via metal wiring

[0308] A glass substrate having through-via metal wiring formed thereon was obtained by performing the same method as in Example 1, except that heat treatment was not performed after coating the binder composition.

[0309]

[0310] Example 15: Formation of through-via metal wiring

[0311] A glass substrate with a thickness of 130 μm having through vias with an internal diameter of 80 μm was prepared.

[0312] Surface activation (formation of -OH groups) was performed by immersing the inside of the through-via of the glass substrate in hydrochloric acid at 25°C for 30 minutes.

[0313] Meanwhile, a primer composition was prepared by mixing 1.0 wt% of γ-aminopropyltriethoxysilane as a silane coupling agent, 0.12 wt% of hydrochloric acid (HCl) as a hydrolysis accelerator, 0.1 wt% of CTAB (cetyltrimethylammonium bromide) as a cationic surfactant, and ethanol as a solvent to make up 100 wt% of the total composition. The primer composition was left for 5 to 30 minutes to induce sufficient hydrolysis of the silane coupling agent to generate silanol groups.

[0314] The inside of the through-via of the surface-activated glass substrate was immersed in the primer composition at 25°C for 30 to 60 minutes to coat the primer composition using a dip coating method. During the dip coating, the primer composition was treated with ultrasonics. The ultrasonic treatment was performed at 25°C with an output of 150W.

[0315] Subsequently, to form a silane layer, the primer layer was formed by natural drying at room temperature for 30 minutes, followed by high-temperature drying at 110°C for 1 to 2 hours. The thickness of the primer layer was 30 nm.

[0316] A binder composition comprising 2.0 wt% of graphite particles with an average particle size of 25 nm, 0.5 wt% of polyvinyl alcohol (PVA) as a dispersant, and the remainder being water, with the pH adjusted to 10 using KOH as a pH adjuster, was applied by dip coating at 32°C for 45 seconds inside the through-via of the glass substrate on which the primer layer was formed, dried with cold air, washed with water, then applied the binder composition again by dip coating at 32°C for 90 seconds, dried, washed with water, dried with hot air, and heat-treated at 180°C for 30 minutes to form a binder layer. The thickness of the binder layer was 150 nm.

[0317] A copper foil with a thickness of 30 μm was bonded to one side of a glass substrate having the above binder layer formed thereon, via an acrylic adhesive layer (ATL-30, 3-way) with a thickness of 2 μm.

[0318] The adhesive layer located inside the glass hole was removed by treating the other side of the glass substrate with plasma using O2 gas.

[0319] The inside of the glass hole was filled by performing an electroplating process using a plating composition comprising 230 g / L copper sulfate, 105.7 g / L sulfuric acid, 176 mg / L hydrochloric acid, 6 ml / L bis-(3-sulfopropyl) disulfide sodium salt, 4 ml / L polyethylene glycol, and the remainder being deionized water.

[0320] A glass substrate having through-via metal wiring formed thereon was obtained by spraying an etching solution containing 5 wt% sulfuric acid, 10 wt% hydrogen peroxide, and the remainder deionized water onto the copper foil surface of the glass substrate in which the above plating process was completed, thereby removing the copper foil and the adhesive layer.

[0321]

[0322] Experimental Example 1: Evaluation of Adhesion of Primer Layer and Binder Layer

[0323] A primer layer and a binder layer were formed on a glass substrate in the same manner as in each of the above examples and comparative examples. The adhesion of the surface coated with the primer layer and the binder layer was evaluated according to ASTM D3359.

[0324] Specifically, the adhesion was evaluated as follows.

[0325] The surface coated with the primer layer and binder layer was cut into a grid shape using a cross cutter. A tape was attached to the cut area and held for 60 seconds, after which the attached tape was quickly peeled off in a 180° direction. The peeled area inside the grid was observed using a magnifying glass, and the adhesion was evaluated according to the following evaluation criteria.

[0326]

[0327] <Evaluation Criteria>

[0328] 5B: No detached sides

[0329] 4B: Dropped area is 5% or less

[0330] 3B: Dropped side is greater than 5% and less than or equal to 15%

[0331] 2B: The dropped side is more than 15% and less than or equal to 35%

[0332] 1B: The detached side is more than 35% and less than or equal to 65%

[0333] 0B: Dropped surface exceeds 65%

[0334]

[0335] The results are shown in Table 1 below.

[0336]

[0337] Adhesion Example 15B Example 22B Example 34B Example 44B Example 54B Example 64B Example 73B Example 84B Example 94B Example 104B Example 113B Example 124B Example 133B Example 144B Example 155B Comparative Example 10B Comparative Example 21B Comparative Example 31B

[0338]

[0339] Through Table 1 above, it can be confirmed that Examples 1 to 15, in which both a primer layer and a binder layer are formed and heat treatment is performed after coating the binder layer, have excellent adhesion.

[0340] On the other hand, Comparative Examples 1 to 3, in which neither the primer layer nor the binder layer was formed, or in which heat treatment was not performed after coating the binder layer, were found to be unable to secure adhesion.

[0341]

[0342] Experimental Example 2: Cross-sectional Analysis of Through-Via Metal Wiring

[0343] The plating quality was confirmed by measuring the cross-section of the glass substrate with the through-via metal wiring formed in Example 1 above using a field emission scanning electron microscope (FE-SEM) measurement method.

[0344] The results are shown in Figure 4.

[0345] Fig. 4a is a 150x magnification FE-SEM image, and Fig. 4b is a 10,000x magnification FE-SEM image.

[0346] Through FIG. 4, it can be seen that according to the method for manufacturing a through-via metal wiring substrate of the present invention, through-via metal wiring can be formed with excellent plating quality without voids or seams.

[0347] In particular, it can be seen that the adhesion between the hole sidewall and the plating layer is improved, resulting in no gap defects (voids).

[0348]

[0349] Experimental Example 3: Evaluation of Adhesion of Through-Via Metal Wiring

[0350] The plating quality was confirmed by observing the cross-sectional appearance while polishing the cross-section of the glass substrate with the through-via metal wiring formed in Example 1 above.

[0351] The above polishing was performed using 800-grit sandpaper at 50 RPM.

[0352] The results are shown in Figure 5.

[0353] Fig. 5a shows the initial appearance before polishing, Fig. 5b shows the appearance 50 seconds after polishing, Fig. 5c shows the appearance 100 seconds after polishing, and Fig. 5d shows the appearance 150 seconds after polishing.

[0354] Through Fig. 5, it can be seen that during polishing, the plating layer is not detached due to a lack of adhesion, and the plating layer is completely ground away and removed.

[0355]

[0356] As specific parts of the present invention have been described in detail above, it is evident to those skilled in the art that such specific descriptions are merely preferred embodiments and do not limit the scope of the present invention. Those skilled in the art will be able to make various applications and modifications within the scope of the present invention based on the above description.

[0357] Accordingly, the substantial scope of the present invention shall be defined by the appended claims and their equivalents.

[0358] [Explanation of the symbol]

[0359] 110: Substrate 120: Adhesive layer

[0360] 130: Metal foil 140: Hole

[0361] 150: Primer layer 160: Binder layer

[0362] 170: Through-via metal wiring

Claims

(i) A step of bonding a metal foil to one surface of a substrate having through vias formed therein through an adhesive layer; (ii) a step of removing the adhesive layer located inside the hole by treating the hole formed by the through via and the metal foil with plasma; (iii) a step of forming a primer layer by coating a primer composition on the sidewall of the hole; (iv) a step of forming a binder layer by coating a binder composition on the primer layer and heat treating it; (v) a step of filling the inside of the hole where the binder layer is formed with metal through a plating process; and (vi) A method for manufacturing a through-via metal wiring substrate comprising the step of removing the metal foil and adhesive layer with an etching solution. (i') A step of forming a primer layer by coating a primer composition on the sidewall of a through via formed on a substrate; (ii') a step of forming a binder layer by coating a binder composition on the primer layer and heat treating it; (iii') a step of bonding a metal foil to one surface of the substrate through an adhesive layer; (iv') a step of removing the adhesive layer located inside the hole by treating the hole formed by the through via and the metal foil with plasma; (v') a step of filling the inside of the hole where the binder layer is formed with metal through a plating process; and (vi') A method for manufacturing a through-via metal wiring substrate comprising the step of removing the metal foil and adhesive layer with an etching solution. A manufacturing method according to claim 1 or 2, further comprising a step of cleaning the substrate after step (vi) or (vi'). A method of manufacturing according to claim 1 or 2, wherein the substrate is a glass substrate, a silicon substrate, or a ceramic substrate. A manufacturing method according to claim 1 or 2, wherein the metal foil is copper foil. A manufacturing method according to claim 1 or 2, wherein the metal foil has a thickness of 3 to 1000 μm. A manufacturing method according to claim 1 or 2, wherein the adhesive layer is formed from one or more selected from the group consisting of acrylic adhesives, silicone adhesives, polyurethane adhesives, and rubber adhesives. In claim 1 or 2, the plasma treatment is O2, CF 4, Ar , N 2, He , SF 4, A manufacturing method performed using NF3 or a mixture of gases thereof. A method of manufacturing according to claim 1 or 2, wherein the primer composition comprises a silane coupling agent and a solvent. A method of manufacturing according to claim 1 or 2, wherein the binder composition comprises graphite particles and a solvent. A manufacturing method according to claim 1 or 2, wherein the plating process is an electrolytic plating process performed by a bottom-up filling mechanism. A manufacturing method according to claim 1 or 2, wherein the metal filling the inside of the hole is copper (Cu). A manufacturing method according to claim 1 or 2, wherein the etching solution comprises one or more selected from the group consisting of copper chloride, iron chloride, hydrochloric acid, nitric acid, sulfuric acid, persulfate compounds, and hydrogen peroxide. A wiring substrate comprising a substrate and through-via metal wiring formed in the thickness direction of the substrate, The above-described through-via metal wiring comprises a wiring substrate including a primer layer formed on the sidewall of the through-via, a binder layer formed on the primer layer, and a plating layer filled in contact with the binder layer inside the through-via. In claim 14, the wiring substrate wherein the primer layer is formed by coating a primer composition comprising a silane coupling agent and a solvent. In claim 14, the wiring substrate wherein the binder layer is formed by coating a binder composition comprising graphite particles and a solvent and heat treating. In claim 14, the plating layer is a wiring substrate containing copper (Cu).

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