A process for metallizing a glass substrate, a manufacturing process for a glass substrate including the same, and a metallized glass substrate

Abstract

According to one embodiment of this application, the metallization process for a glass substrate uses a specific composition to accelerate the metallization of the glass substrate, thereby enabling the uniform formation of a metal layer on a glass substrate with a high aspect ratio using only a wet process.

Description

[Technical Field]

[0001] This application relates to a process for metallizing a glass substrate, a process for manufacturing a glass substrate including the same, and a metallized glass substrate. This application claims the benefit as of the filing date of Korean Patent Application No. 10-2024-0118561, filed with the Korean Intellectual Property Office on 2 September 2024, and Korean Patent Application No. 10-2024-0201651, filed with the Korean Intellectual Property Office on 31 December 2024, the contents of which are fully incorporated herein. [Background technology]

[0002] Glass substrates offer superior warpage and thermal expansion coefficient (CTE) compared to conventional organic substrates, enabling the creation of large-area substrates. This is also highly advantageous for high-speed signaling and heat dissipation due to the increased number of I / O operations.

[0003] However, glass substrates have poor adhesion to metals, which presents a problem in that electroless plating cannot be directly applied to them. Therefore, research is needed on technologies to improve the adhesion between glass and copper, and in particular, technologies that can ensure reliability even under high temperature and high humidity conditions are required.

[0004] Conventionally, Cu seeds were formed on the surface of a glass substrate by Cu sputtering, followed by electroless copper plating. However, this method has the drawback that if the thickness of the glass substrate increases or the diameter of the TGV hole (Through Glass Via hole) decreases, i.e., if the aspect ratio increases, Cu seeds will not be formed in the central part inside the TGV hole. Therefore, when performing electroless plating using conventional methods, it is difficult to improve the aspect ratio of the glass substrate.

[0005] Accordingly, there is a need to develop a metal surface treatment method that improves the aspect ratio of a glass substrate and enables metal plating on the surface of the glass substrate even particularly under high-temperature and high-humidity conditions. [Prior Art Document] [Patent Document]

[0006] [Patent Document 1] Korean Patent Laid-Open Publication No. 10-2010-0135603 [Summary of the Invention] [Problems to be Solved by the Invention]

[0007] The present application aims to provide a metallization process for a glass substrate, a method for manufacturing a glass substrate including the same, and a metallized glass substrate. [Means for Solving the Problems]

[0008] One embodiment of the present application provides a metallization process for a glass substrate, comprising a metallization promotion step for the glass substrate; a plating step for the glass substrate; and an annealing step, wherein the metallization promotion step for the glass substrate comprises a step of subjecting the glass substrate to surface treatment using a glass substrate metallization promotion composition, the glass substrate metallization promotion composition comprises a silane coupling agent and a Pd binder, and the Pd binder is a metal ion-containing compound comprising a functional group capable of binding to the silane coupling agent.

[0009] Another embodiment of the present application provides a method for manufacturing a glass substrate, comprising the metallization process for the glass substrate. Still another embodiment of the present application provides a metallized glass substrate produced by the method for manufacturing a glass substrate.

[0010] A further embodiment of this application provides a metallized glass substrate comprising a glass substrate and a metal layer provided on the glass substrate, wherein a metallization-promoting layer is provided between the glass substrate and the metal layer, the metallization-promoting layer comprising a silane coupling agent and a Pd binder comprising functional groups and metal ions bonded to the silane coupling agent.

[0011] Further embodiments of this application provide a metallized glass substrate comprising a glass substrate having through holes; and a metal layer provided within the through holes of the glass substrate, wherein the metallization-promoting layer comprises a silane coupling agent and a Pd binder comprising functional groups and metal ions bonded to the silane coupling agent. [Effects of the Invention]

[0012] The metallization process for a glass substrate according to one embodiment of this application includes a metallization acceleration step for the glass substrate using a specific composition, thereby eliminating the need to form Cu seeds by Cu sputtering in the conventional electroless copper plating process for glass substrates, and thus enabling the metallization of the glass substrate using only a wet process.

[0013] Furthermore, the metallization process of the glass substrate according to one embodiment of this application can be expected to improve the aspect ratio of the glass substrate by increasing the thickness of the glass substrate or decreasing the diameter of the TGV holes. Furthermore, because the adhesion between the glass substrate and the metal layer can be enhanced not only at room temperature but also under high temperature and high humidity conditions, the metal layer has a uniform thickness and offers the advantage of an excellent plating coverage ratio. [Brief explanation of the drawing]

[0014] [Figure 1] This diagram shows the conventional manufacturing and metallization processes for glass substrates. [Figure 2]This diagram shows the conventional manufacturing and metallization processes for glass substrates. [Figure 3] This figure shows the manufacturing and metallization process of a glass substrate according to the present invention. [Figure 4] This figure shows the metallization process for a glass substrate according to the present invention. [Figure 5] This figure shows the reference standards used to evaluate the plating uniformity of the glass substrate according to the present invention. [Figure 6] This figure shows the measurement locations for each thickness measured to evaluate the plating coverage rate of the glass substrate according to the present invention. [Modes for carrying out the invention]

[0015] The present application will be described in more detail below. In this application, "including" a certain component means, unless otherwise stated, that a part may include other components rather than excluding them. In this application, the glass substrate is not limited as long as it is used as a substrate for glass materials in the art. For example, the glass substrate in this application may be a glass substrate in which through holes are formed.

[0016] In this application, metallization of a glass substrate refers to plating a glass substrate, that is, forming a metal layer on at least one side of the glass substrate. The type of metal used for plating is not limited, but may be, for example, Cu (copper) or Ni (nickel), and preferably Cu. In this application, "glass substrate surface" or "on the glass substrate" may mean all parts of the glass substrate that are in contact with the outside.

[0017] One embodiment of this application provides a glass substrate metallization process, which includes a process for accelerating the metallization of a glass substrate; a process for plating a glass substrate; and an annealing process. In one embodiment of this application, the step of accelerating the metallization of the glass substrate includes a step of surface treating the glass substrate with a glass substrate metallization accelerating composition, wherein the glass substrate metallization accelerating composition comprises a silane coupling agent and a Pd binder, and the Pd binder is a metal ion-containing compound having a functional group capable of binding with the silane coupling agent.

[0018] Figure 4 shows the metallization process of a glass substrate according to this application. Specifically, hydroxyl groups (-OH) are formed on the surface of the glass substrate after the pretreatment process. When this is treated with the aforementioned glass substrate metallization promoting composition, the oxygen of the silane coupling agent 10 in the composition forms hydrogen bonds with the hydroxyl groups on the surface of the glass substrate, and the chain portion of the silane coupling agent is distributed on the glass substrate in a state where it is bonded to B of the Pd binder 20. A of the Pd binder 20 is bonded to the Pd catalyst 30, and a metal layer (for example, a Cu layer) is formed on the Pd catalyst 30 by the plating process. Subsequently, a Si-O-Si condensation reaction occurs in the annealing process, causing the metal layer to adhere closely to the glass substrate.

[0019] In one embodiment of this application, the metallization acceleration step of the glass substrate and the plating step of the glass substrate may be wet steps. In one embodiment of this application, the metallization process of the glass substrate may be a wet process.

[0020] Metallization acceleration process for glass substrates In one embodiment of this application, the step of accelerating the metallization of the glass substrate includes a step of surface treating the glass substrate with a glass substrate metallization accelerating composition. In one embodiment of this application, the glass substrate metallization promoting composition comprises a silane coupling agent and a Pd binder, wherein the Pd binder may be a metal ion-containing compound having a functional group capable of binding with the silane coupling agent.

[0021] In one embodiment of this application, the metallization acceleration step of the glass substrate may include a step in which the hydroxyl groups formed on the surface of the glass substrate by the glass substrate pretreatment step bond with the silane coupling agent; and a step in which the silane coupling agent bond with the Pd binder.

[0022] In one embodiment of this application, the method of treating the glass substrate with the metallization promoting composition may be a spray or a dipping method. In one embodiment of this application, the metallization acceleration step of the glass substrate may be carried out under temperature conditions of 10°C to 50°C.

[0023] In one embodiment of this application, the step of accelerating the metallization of the glass substrate may further include a step of applying a Pd catalyst. In one embodiment of this application, the metallization acceleration step of the glass substrate may include a Pd catalyst bonding preparation step for the glass substrate and a Pd catalyst bonding step for the glass substrate.

[0024] In one embodiment of this application, the glass substrate metallization promoting composition may be used in the Pd catalyst bonding preparation step for the glass substrate. In one embodiment of this application, the step of surface-treating the glass substrate with the glass substrate metallization promoting composition may be a Pd catalyst bonding preparation step for the glass substrate.

[0025] In one embodiment of this application, the Pd catalyst bonding preparation step for the glass substrate may be carried out for 2 to 10 minutes at a temperature of 15°C to 30°C. In one embodiment of this application, the Pd catalyst bonding preparation step for the glass substrate may be a step of producing a glass substrate in which a Pd binder is bonded and distributed on the surface of the glass substrate by treating a glass substrate on which hydroxyl groups have been formed on its surface with the aforementioned glass substrate metallization promoting composition.

[0026] In one embodiment of this application, the Pd catalyst bonding step of the glass substrate may be a step of coating a Pd catalyst onto a glass substrate on which a Pd binder is bonded to the surface. In one embodiment of this application, a dipping method may be used as the method for applying the Pd catalyst.

[0027] In one embodiment of this application, the Pd catalyst bonding step of the glass substrate may be carried out for 2 to 10 minutes at a temperature of 30°C to 50°C. In one embodiment of this application, the Pd catalyst is Pd 2+ The catalyst may also contain a ligand, but is not limited to any type used in the art.

[0028] In one embodiment of this application, the Pd catalyst is [Pd-X] 2+ The structure may include the form represented by , and X may include 2-vinylpyridine or 2-methylpyridine. In one embodiment of this application, the Pd catalyst may include the following structure.

[0029] [ka]

[0030] By treating the glass substrate on which the Pd binder is bonded to the surface with the Pd catalyst, the Pd binder is converted into Pd that has been detached from the Pd catalyst. 2+ It can bond with ions or directly with the Pd catalyst. In one embodiment of this application, the metallization acceleration step of the glass substrate may further include a Pd catalyst reduction step.

[0031] Specifically, the Pd catalyst reduction step involves the Pd of the Pd catalyst 2+ This may also be a process of reducing ions to Pd metal. In one embodiment of this application, the Pd catalyst reduction step can be any method known in the art.

[0032] In one embodiment of this application, the Pd catalyst reduction step may be performed for 1 to 10 minutes at a temperature of 20°C to 40°C. In one embodiment of this application, the glass substrate metallization promoting composition comprises a silane coupling agent and a Pd binder, wherein the Pd binder is a metal ion-containing compound having a functional group capable of binding with the silane coupling agent.

[0033] Specifically, by surface-treating the glass substrate with the glass substrate metallization promoting composition, the glass substrate and the silane coupling agent bond together, the silane coupling agent and the Pd binder bond together due to the functional groups of the Pd binder that can bond with the silane coupling agent, and the Pd binder can bond with the Pd catalyst due to the characteristic that the Pd binder is a metal ion-containing compound.

[0034] Furthermore, by using the glass substrate metallization promoting composition, the process of forming Cu seeds by Cu sputtering can be omitted when plating a glass substrate. The process of forming Cu seeds by Cu sputtering is performed in a dry process, and then the plating process is performed in a wet process. Thus, the dry and wet processes are performed separately, whereas when using the glass substrate metallization promoting composition, the glass substrate can be metallized in the wet process alone.

[0035] Figures 1 and 2 show a conventional glass substrate manufacturing process. Specifically, Figure 1 uses a sputtering method to form through-holes in the glass substrate. When the glass substrate with through-holes is plated, electroless plating is performed by forming Cu seeds, followed by electrolytic plating. However, in this process, if the thickness of the glass substrate is increased or the diameter of the holes is reduced to increase the aspect ratio, there is a problem that Cu is not sufficiently deposited in the central part of the inside of the holes. Figure 2 uses a liquid-phase deposition method, which is a method that uses metal oxides to increase the adhesion between the glass substrate and the metal. Compared to the glass substrate manufacturing process of this application, this method has problems such as a longer tact time, lower adhesion, and the formation of an uneven thin film.

[0036] In contrast, Figure 3 shows the manufacturing process of a glass substrate according to this application. The integrated metal surface treatment / electroless plating process, i.e., the metallization process of the present invention, is performed as a wet process, allowing for sufficient Cu deposition even at high aspect ratios and the formation of a plating layer of uniform thickness. Furthermore, since the takt time is shorter compared to conventional processes, productivity can be improved.

[0037] In particular, the composition used in the metallization acceleration step of the metallization process of this application contains the silane coupling agent and the Pd binder. As a result, one end of the silane coupling agent forms a hydrogen bond with the -OH group formed on the glass substrate after the pretreatment step, the other end of the silane coupling agent bonds with the Pd binder, and the Pd catalyst bonds to the Pd binder. This forms a Pd catalyst on the glass substrate, enabling Cu plating due to the excellent bonding strength between Pd and Cu.

[0038] The specific composition of the aforementioned composition will be described in detail below. First, in relation to the chemical formula described later, substituents are defined as follows. In this application, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl groups. In this application, the alkylene group is a divalent group, except that the example of alkyl groups described above applies.

[0039] In this application, a condensed heterocyclic group means a monovalent ring in which a heterocyclic ring is condensed with an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring. In this application, the heterocycle contains one or more atoms other than carbon, i.e., heteroatoms, and specifically, the heteroatoms may contain one or more atoms selected from the group consisting of O, N, Se, and S. The number of carbon atoms is not particularly limited, but is preferably 2 to 30, and the heterocycle may be monocyclic or polycyclic.

[0040] In this application, the aliphatic hydrocarbon ring is not particularly limited, but preferably has 3 to 30 carbon atoms. Specifically, examples include, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane, bi(cyclohexane), cycloheptane, and cyclooctane. In this application, the aromatic hydrocarbon ring is not particularly limited, but preferably has 6 to 30 carbon atoms. Specifically, examples include, but are not limited to, benzene (phenyl), biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, pyrene, and fluorene.

[0041] <Silane coupling agent> In one embodiment of this application, the glass substrate metallization promoting composition may contain one or more of the silane coupling agents. In one embodiment of this application, the glass substrate metallization promoting composition may contain two or more of the silane coupling agents. In one embodiment of the present application, the glass substrate metallization promoting composition may comprise one or two of the silane coupling agents.

[0042] In one embodiment of the present application, the silane coupling agent may be represented by the following Chemical Formula 2.

Chemical Formula

[0043] In one embodiment of the present application, at least one of R1 to R3 in the Chemical Formula 2 may form a hydrogen bond with -OH on the surface of the glass substrate. In one embodiment of the present application, Q in the Chemical Formula 2 may bind to the Pd binder. In one embodiment of the present application, R1 to R3 may be the same as or different from each other, and each independently may be a methyl group; an ethyl group; a propyl group; a butyl group; or a pentyl group.

[0044] In one embodiment of the present application, R1 to R3 may be the same as or different from each other, and each independently may be a methyl group; or an ethyl group. In one embodiment of the present application, the L 11 and L 12 may be the same as or different from each other, and each independently may be a methylene group; an ethylene group; a propylene group; a butylene group; or a pentylene group. In one embodiment of the present application, the L 11 and L 12These may be identical or different from each other, and each may be an alkylene group having 2 to 4 carbon atoms.

[0045] In one embodiment of this application, the L 11 and L 12 These may be identical or different from each other, and each may independently be an ethylene group; a propylene group; or a butylene group. In one embodiment of this application, Q may be a condensed heterocyclic group having 2 to 60 carbon atoms, containing -SH;-NH2; or O.

[0046] In one embodiment of this application, Q may be -SH;-NH2; or a fused ring group of an oxirane ring and a cyclohexane ring. In one embodiment of this application, Q may be -SH; or a fused ring group of an oxirane ring and a cyclohexane ring.

[0047] In the silane coupling agent of this application, when an aminosilane coupling agent in which Q in chemical formula 2 is -NH2 is used alone, hydrogen bonds may be formed with the -OH group of the glass substrate, reducing the bonding strength between the silane coupling agent and the Pd binder, and as a result, the adhesion strength may decrease under HAST conditions. Therefore, it is preferable that Q is a condensed heterocyclic group having 2 to 60 carbon atoms, containing -SH or O.

[0048] In one embodiment of this application, n may be 0. In one embodiment of this application, n may be 1. In one embodiment of this application, the silane coupling agent may be represented by the following chemical formula 2-1 or 2-2.

[0049] [ka]

[0050] In the above chemical formulas 2-1 and 2-2, R1 to R3 are the same or different from each other, and each independently is an alkyl group having 1 to 5 carbon atoms, L 11 and L 12 are the same or different from each other, and each independently is an alkylene group having 1 to 5 carbon atoms, Q is -SH; -NH2; or a condensed heterocyclic group containing O.

[0051] In one embodiment of the present application, the silane coupling agent may be represented by the above Chemical Formula 2-1. In one embodiment of the present application, the glass substrate metallization promoting composition may contain one or two of the silane coupling agents represented by the above Chemical Formula 2.

[0052] <Pd binder> In one embodiment of the present application, the glass substrate metallization promoting composition may contain one or more of the Pd binders. In one embodiment of the present application, the glass substrate metallization promoting composition may contain two or more of the Pd binders. In one embodiment of the present application, the glass substrate metallization promoting composition may contain one or two of the Pd binders.

[0053] In one embodiment of the present application, the Pd binder is a metal ion-containing compound. In one embodiment of the present application, the Pd binder may be a lithium ion-containing compound.

[0054] In one embodiment of the present application, the Pd binder comprises a functional group capable of bonding to the silane coupling agent. In one embodiment of the present application, the Pd binder may contain a carboxyl group as the functional group capable of bonding to the silane coupling agent.

[0055] In one embodiment of the present application, the Pd binder may be represented by the following Chemical Formula 1. [Chemical Formula] In the aforementioned chemical formula 1, L1 to L3 are either identical or different from each other, and each is an alkylene group having 1 to 5 carbon atoms, independently of the others. X1 is -NH2;-OH;-C(=O)OH; or -P(=O)(OH)2, X2 and X3 are either identical or different from each other, and independently of each other, -NH2;-OH;-C(=O)OH;-C(=O)O - M + ;-P(=O)(OH)2;-P(=O)(OH)(O - M + ); or -P(=O)(O - M + )2, M is either Li or Na. At least one of X2 and X3 is -C(=O)O - M + ;-P(=O)(OH)(O - M + ); or -P(=O)(O - M + )2.

[0056] The Pd binder of this application is characterized by comprising an amino group, a hydroxyl group, a carboxyl group, or a phosphonate group in its tertiary amine structure, and containing at least one metal ion. In one embodiment of this application, the functional group of the Pd binder that can bond with the silane coupling agent may be X1 of the chemical formula 1.

[0057] The Pd binder in the above chemical formula 1 is -C(=O)O - M + ;-P(=O)(OH)(O - M + ); or -P(=O)(O - M + The inclusion of )2 provides excellent ionic properties and facilitates dissociation in the composition, and this position can selectively react with the Pd catalyst. In other words, the Pd binder of chemical formula 1 has excellent bonding strength with the Pd catalyst, allowing for the formation of a uniform metal layer during the plating process.

[0058] Furthermore, if the linkers (L1-L3) of the Pd binder of chemical formula 1 contain heteroatoms (S, N, etc.), it becomes difficult to adjust the bonding position with the Pd binder. The Pd binder of chemical formula 1 can form a stable three-dimensional structure by containing hydrocarbon linkers (L1-L3) of appropriate lengths.

[0059] In one embodiment of this application, L1 to L3 may be the same or different from each other and may be independently a methylene group, an ethylene group, a propylene group, a butylene group, or a pentylene group. In one embodiment of this application, L1 to L3 may be the same or different from each other, and each may be an alkylene group having 1 to 3 carbon atoms.

[0060] In one embodiment of this application, L1 to L3 may be the same or different from each other, and each may be independently a methylene group; an ethylene group; or a propylene group. In one embodiment of this application, when the alkylene group is long in L1 to L3, there is a problem that the reaction in aqueous solution is difficult.

[0061] In one embodiment of this application, X1 may be -C(=O)OH; or -P(=O)(OH)2. In one embodiment of this application, X1 may be -C(=O)OH. In one embodiment of this application, X1 may be -P(=O)(OH)2.

[0062] In one embodiment of this application, X2 and X3 are either identical or different from each other, and independently of each other, -C(=O)OH;-C(=O)O - Li + ;-P(=O)(OH)2;-P(=O)(OH)(O - Li + ); or -P(=O)(O - Li + )2, and at least one of the above X2 and X3 is -C(=O)O- Li + ;-P(=O)(OH)(O - Li + ); or -P(=O)(O - Li + )2 is also acceptable.

[0063] In one embodiment of this application, X2 and X3 are -C(=O)O - Li + ;-P(=O)(OH)(O - Li + ); or -P(=O)(O - Li + )2 is also acceptable. In one embodiment of this application, M may be Li or Na. In one embodiment of this application, M is preferably Li, which can provide a better Pd binding strength compared to when M is Na.

[0064] In one embodiment of this application, when M is K or Cu, compared to Li, it has lower ionicity, inferior Pd bonding strength, and difficulty in forming a uniform plating layer. In one embodiment of this application, the Pd binder may be represented by the following chemical formula 1-1 or 1-2.

[0065] [ka]

[0066] In the above chemical formulas 1-1 and 1-2, L1 to L3 are either identical or different from each other, and each is an alkylene group having 1 to 5 carbon atoms, independently of the others. Z is -OH; or -O - M + And, Y1~Y3 are either identical or different from each other, and each is independently -OH; or -O - M + And, M is either Li or Na.

[0067] In one embodiment of this application, the glass substrate metallization promoting composition may contain one or two Pd binders represented by the chemical formula 1. In one embodiment of this application, the glass substrate metallization promoting composition may contain one Pd binder represented by the chemical formula 1. In one embodiment of this application, the glass substrate metallization promoting composition may further contain additional Pd binders other than the Pd binder represented by chemical formula 1.

[0068] In one embodiment of this application, the additional Pd binder does not need to contain metal ions. In one embodiment of this application, the additional Pd binder does not have to be a metal ion-containing compound. In one embodiment of this application, the additional Pd binder may be represented by the following chemical formula 3.

[0069] [ka]

[0070] In the aforementioned chemical formula 3, L 21 ~L 23 These are alkylene groups having 1 to 5 carbon atoms, which are either identical or different from each other and are independent of one or two carbon atoms. X 21 ~X 23 These are either identical or different from each other, and independently, -C(=O)OH; or -P(=O)(OH)2.

[0071] <Phase stabilizer> In one embodiment of this application, the glass substrate metallization promoting composition may further contain a phase stabilizer selected from hydrochloric acid; sulfuric acid; methanol; ethanol; isopropyl alcohol; and sodium hydroxide.

[0072] In one embodiment of this application, the glass substrate metallization promoting composition may contain one or more of the phase stabilizers. In one embodiment of this application, the glass substrate metallization promoting composition may contain two or more of the phase stabilizers.

[0073] In one embodiment of this application, the glass substrate metallization promoting composition may contain one or two of the phase stabilizers. In one embodiment of this application, the phase stabilizer can be used to adjust the pH of the composition to a range of 0.5 to 5 or 9 to 12, thereby facilitating smooth hydrogen bonding between the -OH groups of the glass substrate and the silane coupling agent.

[0074] The role of the phase stabilizer is to adjust the pH to the desired range and to improve the stability of the silane coupling agent. Specifically, the pH can be adjusted by using phase stabilizers such as hydrochloric acid, sulfuric acid, and sodium hydroxide, and the stability of the silane coupling agent can be enhanced by using phase stabilizers such as methanol, ethanol, and isopropyl alcohol.

[0075] In one embodiment of this application, the phase stabilizer may include one selected from hydrochloric acid; sulfuric acid; and sodium hydroxide, and one selected from methanol; ethanol; and isopropyl alcohol. In one embodiment of this application, the phase stabilizer may include hydrochloric acid and isopropyl alcohol.

[0076] <Solvent> In one embodiment of this application, the glass substrate metallization promoting composition may further contain a solvent. In one embodiment of this application, the solvent may be water. In one embodiment of this application, the glass substrate metallization promoting composition further comprises a solvent, and may contain 0.1 to 5 parts by weight of the silane coupling agent and 0.5 to 5 parts by weight of the Pd binder, with the remainder being the solvent, per 100 parts by weight of the entire glass substrate metallization promoting composition.

[0077] In one embodiment of this application, the glass substrate metallization promoting composition further comprises a solvent, and may contain 0.2 to 3 parts by weight of the silane coupling agent and 0.5 to 3 parts by weight of the Pd binder, with the remainder being the solvent, per 100 parts by weight of the entire glass substrate metallization promoting composition.

[0078] In one embodiment of this application, the glass substrate metallization promoting composition further comprises a solvent, and may contain 0.3 to 2 parts by weight of the silane coupling agent and 0.7 to 3 parts by weight of the Pd binder, with the remainder being the solvent, per 100 parts by weight of the entire glass substrate metallization promoting composition.

[0079] In one embodiment of this application, the glass substrate metallization promoting composition further comprises a solvent, and may contain 0.5 to 2 parts by weight of the silane coupling agent and 1 to 3 parts by weight of the Pd binder, with the remainder being the solvent, per 100 parts by weight of the entire glass substrate metallization promoting composition.

[0080] In one embodiment of this application, the glass substrate metallization promoting composition further comprises a solvent and a phase stabilizer, wherein the composition may contain 0.1 to 5 parts by weight of the silane coupling agent, 0.5 to 5 parts by weight of the Pd binder, 0.1 to 20 parts by weight of the phase stabilizer, and the remainder being the solvent, per 100 parts by weight of the entire glass substrate metallization promoting composition.

[0081] In one embodiment of this application, the glass substrate metallization promoting composition further comprises a solvent and a phase stabilizer, wherein, per 100 parts by weight of the entire glass substrate metallization promoting composition, the composition may contain 0.2 to 3 parts by weight of the silane coupling agent, 0.5 to 3 parts by weight of the Pd binder, 0.1 to 15 parts by weight of the phase stabilizer, and the remainder being the solvent.

[0082] In one embodiment of this application, the glass substrate metallization promoting composition further comprises a solvent and a phase stabilizer, wherein, per 100 parts by weight of the entire glass substrate metallization promoting composition, the composition may contain 0.3 to 2 parts by weight of the silane coupling agent, 0.7 to 3 parts by weight of the Pd binder, 0.1 to 10 parts by weight of the phase stabilizer, and the remainder being the solvent.

[0083] In one embodiment of this application, the glass substrate metallization promoting composition further comprises a solvent and a phase stabilizer, wherein, per 100 parts by weight of the entire glass substrate metallization promoting composition, the composition may contain 0.5 to 2 parts by weight of the silane coupling agent, 1 to 3 parts by weight of the Pd binder, 0.1 to 8 parts by weight of the phase stabilizer, and the remainder being the solvent.

[0084] In one embodiment of this application, the glass substrate metallization promoting composition further comprises a solvent; a phase stabilizer; and an additional Pd binder, wherein the composition may contain 0.1 to 5 parts by weight of the silane coupling agent, 0.5 to 5 parts by weight of the Pd binder, 0.1 to 20 parts by weight of the phase stabilizer, 0.1 to 5 parts by weight of the additional Pd binder, and the remainder being the solvent, per 100 parts by weight of the entire glass substrate metallization promoting composition.

[0085] In one embodiment of this application, the glass substrate metallization promoting composition further comprises a solvent; a phase stabilizer; and an additional Pd binder, wherein, per 100 parts by weight of the total glass substrate metallization promoting composition, the composition may contain 0.2 to 3 parts by weight of the silane coupling agent, 0.5 to 3 parts by weight of the Pd binder, 0.1 to 15 parts by weight of the phase stabilizer, 0.1 to 4 parts by weight of the additional Pd binder, and the remainder being the solvent.

[0086] In one embodiment of this application, the glass substrate metallization promoting composition further comprises a solvent; a phase stabilizer; and an additional Pd binder, wherein, per 100 parts by weight of the total glass substrate metallization promoting composition, the composition may contain 0.3 to 2 parts by weight of the silane coupling agent, 0.7 to 3 parts by weight of the Pd binder, 0.1 to 10 parts by weight of the phase stabilizer, 0.3 to 3 parts by weight of the additional Pd binder, and the remainder being the solvent.

[0087] Another embodiment of this application provides a method for producing a glass substrate metallization promoting composition, comprising the steps of: mixing a silane coupling agent and a Pd binder to produce a mixture; and stirring the mixture, wherein the Pd binder is a metal ion-containing compound comprising a functional group capable of binding with the silane coupling agent.

[0088] In one embodiment of this application, the mixture may further include a solvent and a phase stabilizer. A method for producing a glass substrate metallization promoting composition according to one embodiment of this application may include the steps of: mixing a solvent, one or more silane coupling agents, one or more Pd binders, and one or more phase stabilizers to produce a mixture; and stirring the mixture.

[0089] The specific details regarding the solvent, silane coupling agent, Pd binder, and phase stabilizer are the same as those described for the glass substrate metallization promoting composition.

[0090] In one embodiment of this application, the temperature conditions during the stirring step are 15°C to 25°C. In one embodiment of this application, the time conditions in the stirring step are 1 to 3 hours.

[0091] In one embodiment of this application, the solvent, silane coupling agent, Pd binder, and phase stabilizer may be mixed in any order. In one embodiment of this application, the step of producing the mixture may be a step of mixing one or more silane coupling agents, one or more Pd binders, and one or more phase stabilizers with the solvent.

[0092] In one embodiment of this application, the steps of producing the mixture may include: mixing one or more of the phase stabilizers with the solvent to produce a first mixture; mixing one or more of the Pd binders with the first mixture to produce a second mixture; and mixing one or more of the silane coupling agents with the second mixture to produce a third mixture. When the mixture is manufactured in the order described above, it exhibits even greater stability.

[0093] Plating process for glass substrates In one embodiment of this application, the plating step for the glass substrate may be a step of forming a metal layer on the glass substrate. In one embodiment of this application, the metal layer may be, for example, a Cu layer. In one embodiment of this application, the plating process for the glass substrate may be an electroless plating process.

[0094] In one embodiment of this application, any method known in the art can be used for the plating process of the glass substrate. In one embodiment of this application, the plating process of the glass substrate may be carried out under temperature conditions of 30°C to 50°C. In one embodiment of this application, an electrolytic plating process may be performed after the plating process of the glass substrate.

[0095] Annealing process In one embodiment of this application, the annealing step may be a Si-O-Si condensation step. During the aforementioned annealing process, a Si-O-Si condensation reaction occurs, causing the metal layer to adhere closely to the glass substrate. Generally, the annealing process is carried out at high temperatures (approximately 150°C), so a high degree of adhesion between the glass substrate and the metal layer is required even under high-temperature conditions. In one embodiment of this application, the annealing step can be any method well known in the art.

[0096] In one embodiment of this application, the annealing process may be carried out under temperature conditions of 100°C to 500°C. In one embodiment of this application, the annealing process may be carried out under temperature conditions of 200°C to 400°C. In one embodiment of this application, the annealing process may be performed for 1 to 2 hours.

[0097] Glass substrate pretreatment process In one embodiment of this application, the metallization step of the glass substrate may further include a pretreatment step for the glass substrate. In one embodiment of this application, the metallization step of the glass substrate may include a pretreatment step of the glass substrate; a metallization acceleration step of the glass substrate; a plating step of the glass substrate; and an annealing step. That is, the pretreatment step of the glass substrate may be performed before the metallization acceleration step of the glass substrate.

[0098] In one embodiment of this application, the pretreatment step for the glass substrate may include a step of forming hydroxyl groups on the surface of the glass substrate. In one embodiment of this application, the pretreatment step for the glass substrate may include a pretreatment step A in which the glass substrate is cleaned using a pretreatment composition A, and a pretreatment step B in which hydroxyl groups are formed on the surface of the glass substrate using a pretreatment composition B.

[0099] In one embodiment of this application, the pretreatment steps A and B may include steps of applying pretreatment compositions A and B onto a glass substrate, respectively. Specifically, the pretreatment compositions A and B may be applied onto the glass substrate by spraying or dipping.

[0100] In one embodiment of this application, the pretreatment step A may be performed for 2 to 10 minutes at a temperature of 40°C to 60°C. In one embodiment of this application, the pretreatment step B may be performed for 1 to 5 minutes at a temperature of 15°C to 30°C.

[0101] In one embodiment of this application, the pretreatment composition A may include an amine compound; a polar solvent; a nonpolar solvent; and a pretreatment solvent. In one embodiment of this application, the amine compound may include one or more selected from monoisopropanolamine and monoethanolamine.

[0102] In one embodiment of this application, the polar solvent may include one or more selected from diethylformamide and N-methylpyrrolidone. In one embodiment of this application, the nonpolar solvent may include one or more selected from butyl diglycol and ethyl diglycol.

[0103] In one embodiment of this application, the pretreatment solvent may be water. In one embodiment of this application, the pretreatment composition A may contain 3% to 20% by weight of the amine compound, 5% to 30% by weight of the polar solvent, 10% to 40% by weight of the nonpolar solvent, and 30% to 80% by weight of the pretreatment solvent, per 100 parts by weight of the pretreatment composition A.

[0104] In one embodiment of this application, the pretreatment composition B may include an acidic solution and a pretreatment solvent. In one embodiment of this application, the acidic solution may include one or more selected from hydrochloric acid and sulfuric acid.

[0105] In one embodiment of this application, the pretreatment solvent may be water. In one embodiment of this application, the pretreatment composition B may further contain an oxidizing agent. In one embodiment of this application, the oxidizing agent may be hydrogen peroxide.

[0106] In one embodiment of this application, the pretreatment composition B may contain 3% to 10% by weight of the acidic solution, 0% to 20% by weight of the oxidizing agent, and 80% to 97% by weight of the pretreatment solvent per 100 parts by weight of the pretreatment composition B.

[0107] In one embodiment of this application, the glass substrate pretreatment step; the glass substrate metallization acceleration step; and the glass substrate plating step may each be performed within 2 to 30 minutes.

[0108] In one embodiment of this application, the thickness of the glass substrate may be 0.3 mm to 1.2 mm. In one embodiment of this application, the thickness of the glass substrate may be 0.6 mm to 1.2 mm. In one embodiment of this application, the thickness of the glass substrate may be 0.8 mm to 1.2 mm.

[0109] In one embodiment of this application, the glass substrate may include through holes. In one embodiment of this application, the shape of the through-hole may vary depending on the through-hole forming process, but is not particularly limited. For example, the shape of the through-hole may be cylindrical or hourglass-shaped.

[0110] In one embodiment of this application, the glass substrate may be a TGV (Through Glass Via) substrate. In one embodiment of this application, the diameter of the through-hole in the glass substrate may be 10 μm to 140 μm.

[0111] In one embodiment of this application, the diameter of the through-hole in the glass substrate refers to the diameter of the through-hole that can be seen from the outside of the glass substrate. That is, the diameter of the through-hole may be the diameter of the hole on the upper surface of the glass substrate. Specifically, as shown in Figure 3, if the shape of the through-hole is an hourglass, the diameter of the hole does not have to be constant, and in this case, the diameter of the through-hole may be the diameter of the hole that lies in a straight line with the upper surface of the glass substrate, with reference to the depth direction of the through-hole (perpendicular to the upper surface of the glass substrate).

[0112] In one embodiment of this application, the aspect ratio of the glass substrate may be 1:3 to 1:20. In this application, the aspect ratio of the glass substrate may be the ratio of the diameter to the depth of the through-hole (via). That is, the aspect ratio of the glass substrate may be the ratio of the diameter of the through-hole to the thickness of the glass substrate.

[0113] In this application, the aspect ratio of the glass substrate may be the aspect ratio of the through-holes in the glass substrate, and more specifically, it may be the ratio of the diameter of the through-holes in the glass substrate to the thickness of the glass substrate. In Figure 3, the diameter of the through-hole in the glass substrate is R, the thickness of the glass substrate is T, and the aspect ratio of the glass substrate may be R:T.

[0114] In one embodiment of this application, the aspect ratio of the glass substrate may be 1:5 or greater. In one embodiment of this application, the aspect ratio of the glass substrate may be 1:5 to 1:20.

[0115] In one embodiment of this application, the aspect ratio of the glass substrate may be 1:6 or greater. In one embodiment of this application, the aspect ratio of the glass substrate may be 1:6 to 1:20.

[0116] When plating a glass substrate using the metallization process for glass substrates according to one embodiment of this application, the aspect ratio of the glass substrate can be improved.

[0117] Glass substrate manufacturing process Another embodiment of this application provides a process for manufacturing a glass substrate, which includes a metallization step for the glass substrate. In one embodiment of this application, the manufacturing process of the glass substrate may further include a process for forming through-holes in the glass substrate. In one embodiment of this application, the through-hole formation step of the glass substrate may include a laser phase displacement step of the glass substrate and a hole etching step of the glass substrate.

[0118] In one embodiment of this application, the manufacturing process of the glass substrate may be carried out in the following order: a laser phase displacement step of the glass substrate; a hole etching step of the glass substrate; and a metallization step of the glass substrate.

[0119] In one embodiment of this application, the laser phase displacement step of the glass substrate is a step of causing deformation inside the glass substrate using laser phase displacement, and a method well known in the art may be used. In one embodiment of this application, the hole etching step of the glass substrate is a step of forming through holes in the deformed portion inside the glass substrate, and a method well known in the art may be used. Metallized glass substrate Another embodiment of this application provides a metallized glass substrate manufactured by the glass substrate manufacturing process described above. A further embodiment of this application provides a metallized glass substrate comprising a glass substrate and a metal layer provided on the glass substrate, wherein a metallization-promoting layer is provided between the glass substrate and the metal layer, the metallization-promoting layer comprising a silane coupling agent and a Pd binder comprising functional groups and metal ions bonded to the silane coupling agent.

[0120] Further embodiments of this application provide a metallized glass substrate comprising a glass substrate having through holes; and a metal layer provided within the through holes of the glass substrate, wherein the metallization-promoting layer comprises a silane coupling agent; and a Pd binder comprising functional groups and metal ions bonded to the silane coupling agent. In this application, a metallized glass substrate means a structure in which a metal layer is formed on at least one side of a glass substrate.

[0121] The metallized glass substrate according to this application is characterized by using the aforementioned glass substrate metallization promoting composition, rather than the Cu sputtering method. Generally, when the Cu sputtering method is adopted, Cu seeds are formed by Ti-Cu sputtering, so the metallized glass substrate may contain Ti. In contrast, the metallized glass substrate according to this application does not employ the Ti-Cu sputtering method, and therefore does not contain Ti.

[0122] The metallized glass substrate according to this application may have an adhesion strength of 4B or higher when evaluated at room temperature. The metallized glass substrate according to this application may have an adhesion strength of 5B or higher when evaluated at room temperature. The metallized glass substrate according to this application may have an adhesion strength of 4B or higher when evaluated under HAST conditions. The metallized glass substrate according to this application may have an adhesion strength of 5B or higher when evaluated under HAST conditions.

[0123] In this application, the HAST conditions are either a temperature of 100°C to 150°C, a humidity of 80% to 90%, and a duration of 80 to 100 hours, or a temperature of 110°C to 140°C, a humidity of 83% to 87%, and a duration of 90 to 100 hours. According to this application, the plating uniformity of the metallized glass substrate may be 75% or more when measured by image analysis.

[0124] According to this application, the plating uniformity of the metallized glass substrate may be 90% or more when measured by image analysis. The plating coverage rate of the metallized glass substrate may be 80% or more according to this application.

[0125] The aforementioned plating coverage rate refers to the average values ​​of the T2 / T1 ratio, T3 / T1 ratio, and T4 / T1 ratio after measuring the thickness of Cu on the glass substrate surface (top surface) (T1) and the thickness of Cu within the through-holes of the glass substrate (T2, T3, and T4) according to their positions (see Figure 6) by cross-cutting the metallized glass substrate with a FIB (Focused Ion Beam).

[0126] More specifically, the plating coverage rate can be calculated using the following formula 1, based on the cross-section obtained by cutting the metallized glass substrate through-holes perpendicular to the upper surface of the glass substrate using a Focused Ion Beam (FIB). This calculation includes measuring the thickness of the metal layer at a position 100 μm away from the through-hole on the upper surface of the glass substrate (T1), the thickness of the metal layer at a through-hole position 25% of the thickness from the upper surface of the glass substrate (T2), the thickness of the metal layer at a through-hole position 50% of the thickness (T3), and the thickness of the metal layer at a through-hole position 75% of the thickness (T4), assuming the thickness of the glass substrate is 100%.

[0127]

number

[0128] The metallized glass substrate described in this application can be used for semiconductor packaging. Specifically, the glass substrate described in this application can be used for packaging semiconductor chips / devices. More specifically, semiconductor packaging is a general term for post-processing technologies that cut processed wafers into chips and package them, and in this context, glass substrates are attracting attention as next-generation semiconductor packaging materials that play a role in physically / electrically connecting semiconductor chips to the system. Thus, in order to be used as a semiconductor packaging material, it is required to fulfill roles such as mechanical protection, electrical / mechanical coupling, and heat dissipation. In particular, in the case of TGV Hall substrates, the glass substrate contains fine electrode passages that facilitate the flow of electricity, which has the advantage of allowing for the mounting of more chips and high-performance chips.

[0129] The metallized glass substrates described in this application are applicable to packaging fields requiring large areas, such as AI, high-performance computing (HPC), data centers, servers, and networking, and are particularly applicable to generative AI and HPC. [Examples]

[0130] The present application will be described in detail below with reference to examples. However, the examples provided in this application may be modified into various other forms, and the scope of this application should not be construed as being limited to the examples described below. The examples provided in this application are provided to give a more complete explanation of this application to a person of average knowledge in the industry.

[0131] <Example 1> Metallization of a glass substrate Using glass substrate 1 shown in Table 1 below, the glass substrate was plated using the following process.

[0132] [Table 1]

[0133] (1) Pretreatment process A glass substrate (glass substrate 1) was pre-treated by immersing it in pre-treatment composition A (5% by weight of monoethanolamine, 15% by weight of N-methylpyrrolidone, 10% by weight of ethyl diglycol, the remainder being water) at 50°C for 5 minutes, and then immersing it in pre-treatment composition B (3% by weight of HCl, the remainder being water) at room temperature (25°C) for 2 minutes.

[0134] (2) Glass substrate metallization acceleration process (GCS-AP) The pre-treated glass substrate was immersed in the following metallization-promoting composition at room temperature (25°C) for 2 minutes, then immersed in a Pd catalyst at 40°C for 5 minutes, and subsequently immersed in a reducing agent at 30°C for 3 minutes to reduce the Pd catalyst.

[0135] [Metallation promoting composition] Silane coupling agent (aminoethylaminopropyltrimethoxysilane, 0.5% by weight), Pd binder (LCC-1(C6H 9-n NO6Li n A metallization-promoting composition was prepared by mixing n=2, 1% by weight, a phase stabilizer (HCl, 0.3% by weight), and a solvent (water, remainder), and then stirring at room temperature for 2 hours.

[0136] (3) Plating process for glass substrates A Cu layer was formed on the glass substrate by immersing it in a plating composition containing Cu, a leveling agent, and a stabilizer at 40°C for 30 minutes (electroless copper plating).

[0137] (4) Annealing process The material was dried in an oven at 400°C under N2 conditions for 60 minutes.

[0138] <Example 2> In Example 1, the glass substrate was plated in the same manner as in Example 1, except that glass substrate 2 from Table 1 was used instead of glass substrate 1.

[0139] <Example 3> In Example 1, the glass substrate was plated in the same manner as in Example 1, except that glass substrate 3 from Table 1 was used instead of glass substrate 1.

[0140] <Comparative Example 1> In Example 1, the glass substrate was plated in the same manner as in Example 1, except that (1) the pretreatment step and (2) the glass substrate metallization acceleration step (GCS-AP) were omitted, and Cu seeds were formed on the surface of the glass substrate by Cu sputtering (dry method). Specifically, using a thin-film deposition method, Cu was placed in a chamber, a plasma was induced to create an electric field, and then Cu seeds were formed by the Cu atoms decomposed by gas decomposition forming a thin film on a glass substrate.

[0141] <Comparative Example 2> In Comparative Example 1, the glass substrate was plated in the same manner as in Comparative Example 1, except that glass substrate 2 from Table 1 was used instead of glass substrate 1.

[0142] <Comparative Example 3> In Comparative Example 1, the glass substrate was plated in the same manner as in Comparative Example 1, except that glass substrate 3 from Table 1 was used instead of glass substrate 1.

[0143] <Comparative Example 4> In Example 1, the glass substrate was plated in the same manner as in Example 1, except that (1) the pretreatment step and (2) the metallization acceleration step of the glass substrate were omitted and Cu was deposited using the LPD (metal oxide) method. Specifically, copper was sprayed onto the surface of a glass substrate and deposited while drying.

[0144] <Comparative Example 5> In Comparative Example 4, the glass substrate was plated in the same manner as in Comparative Example 4, except that glass substrate 2 from Table 1 was used instead of glass substrate 1.

[0145] <Comparative Example 6> In Comparative Example 4, the glass substrate was plated in the same manner as in Comparative Example 4, except that glass substrate 3 from Table 1 was used instead of glass substrate 1.

[0146] <Example of experiment> The properties of the plated glass substrates in the above examples and comparative examples were evaluated and are shown in Table 2 below. The evaluation method for the properties described in Table 2 below is as follows. Electrical power supply A resistance meter was used to check whether the plated glass substrate was energized or not, and the results were indicated with ○ (energized) and × (short circuit).

[0147] Plating uniformity The uniformity of the plating was confirmed by image analysis of the plated glass substrate, and the results are shown as ○ (100% plating), □ (75% or more plating), △ (50% or more plating), and × (less than 50% plating). Specifically, the uniformity of the plating was visually evaluated, referring to the criteria in Figure 5.

[0148] Adhesion strength at room temperature (Cross-cut evaluation) After forming a grid on the plated glass substrate at room temperature using a cross-cutter (TOC Corporation AT-CC3000 / ASTM1), an adhesive tape (3M 8981 25mm x 10m (7.6N), TOC Corporation sp3020) was applied tightly, and the shape of the remaining grid after peeling it off was examined for evaluation. The evaluation criteria referred to the ASTM D3359-08 standard.

[0149] HAST adhesion The plated glass substrate was left at a temperature of 130°C and a humidity of 85% for 96 hours, and then evaluated in the same manner as described above for room-temperature adhesion strength.

[0150] Plating coverage ratio The plated glass substrate was cross-sectioned using a focused ion beam (FIB), and the thickness of the metal layer at a position 100 μm away from the through-hole on the upper surface of the glass substrate (T1), the thickness of the metal layer at the through-hole position 25% of the thickness from the upper surface of the glass substrate (T2), the thickness of the metal layer at the through-hole position 50% of the thickness (T3), and the thickness of the metal layer at the through-hole position 75% of the thickness (T4) were measured. Then, the T2 / T1 ratio, T3 / T1 ratio, and T4 / T1 ratio were calculated, and their average values ​​were evaluated as the plating coverage rate.

[0151] [Table 2]

[0152] As can be seen from the results in Table 2 above, the plating uniformity, room temperature / HAST adhesion, and plating coverage rate of the glass substrate plated through the metallization acceleration process (GCS-AP) of the present invention are superior to those of the comparative examples. In particular, from Examples 1 to 3, it was confirmed that the plating coverage rate was even higher despite the increased aspect ratio of the glass substrate.

[0153] In contrast, in Comparative Examples 1-3, which used the Cu sputtering method, the plating coverage rate could not exceed 50% even under low aspect ratio (1:5) conditions, and it was confirmed that the performance deteriorated as the aspect ratio increased. It was also confirmed that the performance decreased in the evaluation of electrical conductivity and plating uniformity.

[0154] Similarly, in Comparative Examples 4-6, which used the LPD method, improved performance was observed compared to Comparative Examples 1-3, which employed the Cu sputtering method. However, under the same aspect ratio conditions, the performance was confirmed to be at 30%-60% of that of Examples 1-3.

[0155] Therefore, when a glass substrate is plated using the metallization acceleration process of the present invention, it is possible to achieve uniform plating even on glass substrates with a high aspect ratio, achieve high coverage, and provide high adhesion not only at room temperature but also under HAST conditions. [Explanation of symbols]

[0156] 10. Silane coupling agent 20 ···Pd binder 30 ···Pd catalyst T...thickness of glass substrate R ···Diameter of the through-hole in the glass substrate A...Position where the Pd binder binds to the Pd catalyst B ···Position where the Pd binder binds to the silane coupling agent. T1 ···Thickness of Cu on the surface of the glass substrate T2... The thickness of Cu at 1 / 4 of the thickness inside the through-hole of the glass substrate. T3... The thickness of Cu at 2 / 4 of the thickness inside the through-hole of the glass substrate. T4... The thickness of Cu at 3 / 4 of the thickness inside the through-hole of the glass substrate.

Claims

1. A glass substrate metallization process comprising a glass substrate metallization acceleration process; a glass substrate plating process; and an annealing process, The glass substrate metallization acceleration step includes a step of surface treating the glass substrate with a glass substrate metallization acceleration composition, The glass substrate metallization promoting composition comprises a silane coupling agent and a Pd binder. A metallization step for a glass substrate, wherein the Pd binder is a metal ion-containing compound containing a functional group capable of binding with the silane coupling agent.

2. The Pd binder is represented by the following chemical formula 1, in the metallization step of a glass substrate according to claim 1: 【Chemistry 1】 In the aforementioned chemical formula 1, L １ ~L ３ These are alkylene groups having 1 to 5 carbon atoms, which are either identical or different from each other and are independent of one or two carbon atoms. X １ is, -NH ２ -OH; -C(=O)OH; or -P(=O)(OH) ２ And, X ２ and X ３ are identical to or different from each other, and each independently represents -NH ２ ; -OH; -C(=O)OH; -C(=O)O － M ＋ ; -P(=O)(OH) ２ ; -P(=O)(OH)(O － M ＋ ); or -P(=O)(O － M ＋ ) ２ and is M is Li; or Na, X ２ and X ３ At least one of them is -C(=O)O － M ＋ ;-P(=O)(OH)(O － M ＋ ); or -P (=O) (O － M ＋ ) ２ That is the case.

3. The metallization step for a glass substrate according to claim 1, further comprising a pretreatment step for the glass substrate.

4. The metallization step for a glass substrate according to claim 1, further comprising the step of applying a Pd catalyst to the glass substrate.

5. The metallization step for a glass substrate according to claim 1, wherein the step for accelerating the metallization of the glass substrate and the step for plating the glass substrate are wet steps.

6. The metallization step for a glass substrate according to claim 1, wherein the thickness of the glass substrate is 0.3 mm to 1.2 mm.

7. The metallization step for a glass substrate according to claim 1, wherein the glass substrate includes through holes.

8. The metallization process for a glass substrate according to claim 7, wherein the diameter of the through-hole is 10 μm to 140 μm.

9. The metallization step for a glass substrate according to claim 7, wherein the aspect ratio of the glass substrate is 1:3 to 1:

20.

10. A glass substrate manufacturing process comprising a metallization step for a glass substrate according to any one of claims 1 to 9.

11. The glass substrate manufacturing process according to claim 10, further comprising a step of forming through holes in the glass substrate.

12. The glass substrate manufacturing process according to claim 11, wherein the through-hole formation step of the glass substrate includes a laser phase displacement step of the glass substrate and a hole etching step of the glass substrate.

13. A metallized glass substrate manufactured by the glass substrate manufacturing process described in claim 10.

14. A glass substrate; and a metallized glass substrate including a metal layer provided on the glass substrate, The glass substrate and the metal layer include a metallization promoting layer, The metallization promoting layer comprises a silane coupling agent and a Pd binder containing functional groups and metal ions bonded to the silane coupling agent, and is a metallized glass substrate.

15. A glass substrate having through holes; and a metallized glass substrate including a metal layer provided within the through holes of the glass substrate, The glass substrate and the metal layer include a metallization promoting layer, The metallization promoting layer comprises a silane coupling agent and a Pd binder containing functional groups and metal ions bonded to the silane coupling agent, and is a metallized glass substrate.

16. The metallized glass substrate according to claim 15, wherein the aspect ratio of the glass substrate is 1:5 to 1:

20.

17. The plating coverage rate of the metallized glass substrate is 80% or more. The plating coverage rate is calculated using the following formula 1, based on the cross-section obtained by cutting the metallized glass substrate perpendicular to the upper surface of the glass substrate using a Focused Ion Beam (FIB): the thickness of the metal layer at a position 100 μm away from the through-hole on the upper surface of the glass substrate (T1), the thickness of the metal layer at the through-hole position 25% of the thickness from the upper surface of the glass substrate (T2), the thickness of the metal layer at the through-hole position 50% of the thickness (T3), and the thickness of the metal layer at the through-hole position 75% of the thickness (T4), after measuring these values, according to claim 15: [Math 1] 。

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