Glass substrate metallization process, glass substrate manufacturing process comprising same, and metallized glass substrate

Abstract

A glass substrate metallization process according to one embodiment of the present application can uniformly form a metal layer on a high-aspect-ratio glass substrate only through a wet process by performing a glass substrate metallization promotion process using a specific composition.

Description

Glass substrate metallization process, glass substrate manufacturing process including the same, and metallized glass substrate

[0001] The present application relates to a glass substrate metallization process, a glass substrate manufacturing process including the same, and a metallized glass substrate.

[0002] This application claims the benefit of the filing dates of Korean Patent Application No. 10-2024-0118561, filed with the Korean Intellectual Property Office on September 2, 2024, and Korean Patent Application No. 10-2024-0201651, filed with the Korean Intellectual Property Office on December 31, 2024, the contents of which are incorporated herein in their entirety.

[0003] Glass substrates have superior warpage and CTE (coefficient of thermal expansion) compared to existing organic substrates, enabling the implementation of large-area substrates. In addition, the increased number of I / Os is very advantageous for high-speed signaling and heat dissipation.

[0004] However, there is a problem in that direct electroless plating cannot be performed on a glass substrate because the glass substrate has low adhesion to metal.

[0005] Accordingly, research is needed on technologies to improve the adhesion between glass and copper, and in particular, technologies that can ensure reliability even at high temperatures and high humidity are required.

[0006] Conventionally, Cu seeds were formed on the surface of a glass substrate by Cu sputtering, and then electroless copper plating was performed. However, when the thickness of the glass substrate increases or the diameter of the TGV hole (Through Glass Via hole) decreases, in other words, when the aspect ratio increases, there is a disadvantage in that the Cu seed is not formed in the central portion inside the TGV hole.

[0007] Therefore, when electroless plating is performed using conventional methods, it is difficult to improve the aspect ratio of the glass substrate.

[0008] Therefore, it is necessary to develop a metal surface treatment method that enables metal plating on the surface of a glass substrate, especially at high temperature and high humidity, while increasing the aspect ratio of the glass substrate.

[0009] [Prior Art Literature]

[0010] (Patent Document 1) Republic of Korea Patent Publication No. 10-2010-0135603

[0011] The present application seeks to provide a glass substrate metallization process, a glass substrate manufacturing process including the same, and a metallized glass substrate.

[0012] One embodiment of the present application provides a glass substrate metallization process including a glass substrate metallization promotion process; a glass substrate plating process; and an annealing process, wherein the glass substrate metallization promotion process includes a step of surface treating a glass substrate using a glass substrate metallization promotion composition, wherein the glass substrate metallization promotion composition includes a silane coupling agent and a Pd binder, and the Pd binder is a metal ion-containing compound including a functional group capable of bonding with the silane coupling agent.

[0013] Another embodiment of the present application provides a process for manufacturing a glass substrate including the above glass substrate metallization process.

[0014] Another embodiment of the present application provides a metallized glass substrate manufactured by the above glass substrate manufacturing process.

[0015] Another embodiment of the present 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 included between the glass substrate and the metal layer, and the metallization promoting layer includes a silane coupling agent and a Pd coupling agent including a functional group and a metal ion combined with the silane coupling agent.

[0016] Another embodiment of the present application provides a metallized glass substrate comprising a glass substrate having a through hole; and a metal layer provided in the through hole of the glass substrate, wherein a metallization promoting layer is included between the glass substrate and the metal layer, and the metallization promoting layer includes a silane coupling agent and a Pd coupling agent including a functional group and a metal ion combined with the silane coupling agent.

[0017] A glass substrate metallization process according to one embodiment of the present application includes a process for promoting glass substrate metallization using a specific composition, thereby omitting Cu seed formation through Cu sputtering in a conventional electroless plating process of a glass substrate, and thus enabling the glass substrate to be metallized using only a wet process.

[0018] In addition, the glass substrate metallization process according to one embodiment of the present application can be expected to increase the aspect ratio of the glass substrate by increasing the thickness of the glass substrate or reducing the diameter of the TGV hole.

[0019] Moreover, it has the advantage of increasing the adhesion between the glass substrate and the metal layer not only at room temperature but also at high temperature and high humidity, and thus the metal layer thickness is uniform, resulting in an excellent plating coverage ratio.

[0020] Figures 1 and 2 are diagrams showing a conventional glass substrate manufacturing and metallization process.

[0021] Figure 3 is a diagram showing a glass substrate manufacturing and metallization process according to the present invention.

[0022] Figure 4 is a diagram showing a glass substrate metallization process according to the present invention.

[0023] Figure 5 is a diagram showing a reference standard for evaluating the plating uniformity of a glass substrate according to the present invention.

[0024] FIG. 6 is a diagram showing the measurement positions of each thickness measured to evaluate the plating coverage ratio of a glass substrate according to the present invention.

[0025] [Explanation of symbols]

[0026] 10: Silane coupling agent

[0027] 20: Pd binder

[0028] 30: Pd catalyst

[0029] T: Thickness of the glass substrate

[0030] R: Diameter of the through hole in the glass substrate

[0031] A: Position of Pd binder bonded to Pd catalyst

[0032] B: Position where the Pd binder is bonded to the silane coupling agent

[0033] T1: Cu thickness on the glass substrate surface

[0034] T2: Cu thickness at 1 / 4 of the thickness point inside the glass substrate through hole

[0035] T3: Cu thickness at 2 / 4 of the thickness point within the glass substrate through hole

[0036] T4: Cu thickness at 3 / 4 of the thickness point within the glass substrate through hole

[0037] Hereinafter, the present application will be described in more detail.

[0038] When a part in this application is said to "include" a certain component, this does not mean that it excludes other components, but rather that it may include other components, unless specifically stated otherwise.

[0039] In the present application, the glass substrate is not limited to any substrate made of glass used in the art. For example, the glass substrate of the present application may be a glass substrate having a through hole formed therein.

[0040] In the present application, glass substrate metallization refers to plating of a glass substrate, i.e., forming a metal layer on at least one surface 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.

[0041] In this application, “surface of glass substrate” or “on glass substrate” may mean any part of the glass substrate that comes into contact with the outside.

[0042] One embodiment of the present application provides a glass substrate metallization process including a glass substrate metallization promotion process; a glass substrate plating process; and an annealing process.

[0043] In one embodiment of the present application, the process for promoting metallization of a glass substrate includes a step of surface-treating a glass substrate using a composition for promoting metallization of a glass substrate, wherein the composition for promoting metallization of a glass substrate includes a silane coupling agent and a Pd binder, and the Pd binder is characterized in that it is a metal ion-containing compound including a functional group capable of bonding with the silane coupling agent.

[0044] FIG. 4 is a diagram illustrating a glass substrate metallization process according to the present application. Specifically, a hydroxyl group (-OH) is formed on the surface of a glass substrate that has undergone a 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 a hydrogen bond with the hydroxyl group 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 of being bonded to B of the Pd binder (20). The A of the Pd binder (20) is bonded to the Pd catalyst (30), and a metal layer (e.g., a Cu layer) is formed on the Pd catalyst (30) through a plating process. Thereafter, a Si-O-Si condensation reaction occurs in an annealing process, so that the metal layer adheres to the glass substrate.

[0045] In one embodiment of the present application, the glass substrate metallization promotion process and the glass substrate plating process may be wet processes.

[0046] In one embodiment of the present application, the glass substrate metallization process may be a wet process.

[0047]

[0048] Glass substrate metallization promotion process

[0049] In one embodiment of the present application, the glass substrate metallization promotion process includes a step of surface-treating the glass substrate using a glass substrate metallization promotion composition.

[0050] In one embodiment of the present application, the glass substrate metallization promoting composition includes a silane coupling agent and a Pd binder, and the Pd binder may be a metal ion-containing compound including a functional group capable of bonding with the silane coupling agent.

[0051] In one embodiment of the present application, the process for promoting the metallization of the glass substrate may include a step of bonding the hydroxyl group formed on the surface of the glass substrate by the glass substrate pretreatment process to the silane coupling agent; and a step of bonding the silane coupling agent to the Pd binding agent.

[0052] In one embodiment of the present application, the method of treating the glass substrate with the metallization promoting composition may use a spraying or dipping method.

[0053] In one embodiment of the present application, the glass substrate metallization promotion process can be performed under temperature conditions of 10°C to 50°C.

[0054] In one embodiment of the present application, the glass substrate metallization promotion process may further include a step of applying a Pd catalyst.

[0055] In one embodiment of the present application, the glass substrate metallization promotion process may include a glass substrate Pd catalyst bonding preparation process; and a glass substrate Pd catalyst bonding process.

[0056] In one embodiment of the present application, the glass substrate metallization promoting composition can be used in the glass substrate Pd catalyst bonding preparation process.

[0057] In one embodiment of the present application, the step of surface treating a glass substrate using the glass substrate metallization promoting composition may be a glass substrate Pd catalyst bonding preparation process.

[0058] In one embodiment of the present application, the glass substrate Pd catalyst bonding preparation process can be performed for 2 to 10 minutes at a temperature condition of 15°C to 30°C.

[0059] In one embodiment of the present application, the glass substrate Pd catalyst bonding preparation process may be a process of manufacturing a glass substrate in which a Pd bonding agent is bonded and distributed on the surface of the glass substrate by treating a glass substrate having a hydroxyl group formed on the surface with the aforementioned glass substrate metallization promoting composition.

[0060] In one embodiment of the present application, the glass substrate Pd catalyst bonding process may be a process of applying a Pd catalyst on a glass substrate having a Pd binder bonded to the surface.

[0061] In one embodiment of the present application, the method of applying the Pd catalyst may use a dipping method.

[0062] In one embodiment of the present application, the glass substrate Pd catalyst bonding process can be performed for 2 to 10 minutes at a temperature condition of 30°C to 50°C.

[0063] In one embodiment of the present application, the Pd catalyst is Pd 2+ It may be a catalyst including a ligand, but is not limited to a type used in the art.

[0064] In one embodiment of the present application, the Pd catalyst is [Pd-X] 2+ It may include a structure represented by, wherein X may include 2-vinylpyridine or 2-methylpyridine.

[0065] In one embodiment of the present application, the Pd catalyst may include the following structure.

[0066]

[0067] By treating the glass substrate with the Pd catalyst having the Pd binder bonded to the surface, the Pd binder is separated from the Pd catalyst. 2+ It can bind to ions or bind directly to the Pd catalyst.

[0068] In one embodiment of the present application, the glass substrate metallization promotion process may further include a Pd catalyst reduction process.

[0069] Specifically, the Pd catalytic reduction process is performed by reducing the Pd of the Pd catalyst. 2+ It may be a process of reducing ions to Pd metal.

[0070] In one embodiment of the present application, any method known in the art can be applied to the Pd catalytic reduction process.

[0071] In one embodiment of the present application, the Pd catalyst reduction process can be performed at a temperature of 20°C to 40°C for 1 to 10 minutes.

[0072] In one embodiment of the present 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 including a functional group capable of bonding with the silane coupling agent.

[0073] Specifically, by surface-treating a glass substrate using the above-described composition for promoting metallization of the glass substrate, the glass substrate and the silane coupling agent are bonded, the silane coupling agent and the Pd coupling agent are bonded through a functional group of the Pd coupling agent that can be bonded to the silane coupling agent, and the Pd coupling agent can be bonded to a Pd catalyst through the characteristic that it is a metal ion-containing compound.

[0074] In addition, by using the composition for promoting metallization of a glass substrate, the process of forming a Cu seed by Cu sputtering can be omitted when plating a glass substrate. The process of forming a Cu seed by Cu sputtering is performed as a dry process, and the subsequent plating process is performed as a wet process. While the dry process and the wet process are performed separately, when the composition for promoting metallization of a glass substrate is used, the glass substrate can be metallized by only the wet process.

[0075] FIGS. 1 and 2 illustrate a conventional glass substrate manufacturing process. Specifically, FIG. 1 uses a sputtering method, in which a through hole is formed in a glass substrate, and when the glass substrate with the through hole formed is plated, electroless plating is performed through Cu seed formation, and then electroplating is performed. However, in this process, there is a problem that Cu is not well deposited in the central part inside the hole when the thickness of the glass substrate is increased or the hole diameter is reduced to increase the aspect ratio. FIG. 2 illustrates a liquid phase deposition method, which is a method for increasing the adhesion between the glass substrate and the metal using a metal oxide, but has a longer tact time, lower adhesive strength, and uneven formation of a thin film compared to the glass substrate manufacturing process of the present application.

[0076] On the other hand, Fig. 3 illustrates a glass substrate manufacturing process according to the present application, wherein the metal surface treatment / electroless plating integrated process, i.e., the metallization process of the present invention, is entirely performed as a wet process, and Cu deposition is performed well even at high aspect ratios, and a plating layer of uniform thickness can be formed. In addition, the shorter tact time compared to existing processes can improve productivity.

[0077] In particular, since the composition used in the metallization promotion process among the metallization processes of the present application includes the silane coupling agent and the Pd binder, one end of the silane coupling agent and the -OH group formed on the glass substrate that has undergone the pretreatment process form a hydrogen bond, the other end of the silane coupling agent is bonded to the Pd binder, and the Pd catalyst is bonded to the Pd binder, thereby forming a Pd catalyst on the glass substrate, and Cu plating is possible due to the excellent bonding strength between Pd and Cu.

[0078] Hereinafter, the specific composition of the above composition will be described in detail.

[0079] First, with respect to the chemical formula described below, the substituents are defined as follows.

[0080] In the present 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, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group.

[0081] In the present application, the examples of the alkyl group described above apply, except that the alkylene group is divalent.

[0082] In the present application, a fused heterocyclic group means a monovalent ring in which a heterocyclic ring is condensed with an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring.

[0083] In the present application, a heterocycle is one that includes one or more atoms other than carbon, i.e., a heteroatom, and specifically, the heteroatom may include 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 carbon atoms, and the heterocycle may be monocyclic or polycyclic.

[0084] In the present application, the aliphatic hydrocarbon ring is not particularly limited, but is preferably one having 3 to 30 carbon atoms, and specifically includes, but is not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane, bi(cyclohexane), cycloheptane, cyclooctane, etc.

[0085] In the present application, the aromatic hydrocarbon ring is not particularly limited, but is preferably one having 6 to 30 carbon atoms, and specifically includes, but is not limited to, benzene (phenyl), biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, pyrene, fluorene, etc.

[0086] Silane coupling agent

[0087] In one embodiment of the present application, the glass substrate metallization promoting composition may include one or more types of the silane coupling agent.

[0088] In one embodiment of the present application, the glass substrate metallization promoting composition may include two or more types of the silane coupling agent.

[0089] In one embodiment of the present application, the glass substrate metallization promoting composition may include one or two types of the silane coupling agent.

[0090] In one embodiment of the present application, the silane coupling agent may be represented by the following chemical formula 2.

[0091] [Chemical Formula 2]

[0092]

[0093] In the above chemical formula 2,

[0094] R1 to R3 are the same or different and each independently an alkyl group having 1 to 5 carbon atoms,

[0095] L 11 and L 12 are the same or different and each independently an alkylene group having 1 to 5 carbon atoms,

[0096] n is 0 or 1,

[0097] Q is a fused heterocyclic group containing -SH; -NH2; or O.

[0098] In one embodiment of the present application, at least one of R1 to R3 of the chemical formula 2 can form a hydrogen bond with -OH on the surface of the glass substrate.

[0099] In one embodiment of the present application, Q of the chemical formula 2 can be combined with the Pd binder.

[0100] In one embodiment of the present application, R1 to R3 may be the same as or different from each other and may each independently be a methyl group; an ethyl group; a propyl group; a butyl group; or a pentyl group.

[0101] In one embodiment of the present application, R1 to R3 may be the same as or different from each other and may each independently be a methyl group or an ethyl group.

[0102] In one embodiment of the present application, the L 11 and L 12 are the same or different and can each independently be a methylene group; an ethylene group; a propylene group; a butylene group; or a pentylene group.

[0103] In one embodiment of the present application, the L 11 and L 12 are the same or different and may each independently be an alkylene group having 2 to 4 carbon atoms.

[0104] In one embodiment of the present application, the L 11 and L 12 are the same or different and can each independently be an ethylene group; a propylene group; or a butylene group.

[0105] In one embodiment of the present application, Q may be a condensed heterocyclic group having 2 to 60 carbon atoms, including -SH; -NH2; or O.

[0106] In one embodiment of the present application, Q may be -SH; -NH2; or a condensed ring group of an oxirane ring and a cyclohexane ring.

[0107] In one embodiment of the present application, Q may be -SH; or a condensed ring group of an oxirane ring and a cyclohexane ring.

[0108] In the silane coupling agent of the present application, when the amino silane coupling agent in which Q of the above chemical formula 2 is -NH2 is used alone, the bonding strength between the silane coupling agent and the Pd coupling agent may decrease due to the formation of a hydrogen bond with the -OH group of the glass substrate, and as a result, the adhesion strength under HAST conditions may decrease. Therefore, it is preferable that the Q is a condensed heterocyclic group containing -SH or O and having 2 to 60 carbon atoms.

[0109] In one embodiment of the present application, n may be 0.

[0110] In one embodiment of the present application, n may be 1.

[0111] In one embodiment of the present application, the silane coupling agent may be represented by the following chemical formula 2-1 or 2-2.

[0112] [Chemical Formula 2-1]

[0113]

[0114] [Chemical Formula 2-2]

[0115]

[0116] In the above chemical formulas 2-1 and 2-2,

[0117] R1 to R3 are the same or different and each independently an alkyl group having 1 to 5 carbon atoms,

[0118] L 11 and L 12 are the same or different and each independently an alkylene group having 1 to 5 carbon atoms,

[0119] Q is a fused heterocyclic group containing -SH; -NH2; or O.

[0120] In one embodiment of the present application, the silane coupling agent may be represented by the chemical formula 2-1.

[0121] In one embodiment of the present application, the glass substrate metallization promoting composition may include one or two silane coupling agents represented by the chemical formula 2.

[0122] <Pd 결합제>

[0123] In one embodiment of the present application, the glass substrate metallization promoting composition may include one or more types of Pd binders.

[0124] In one embodiment of the present application, the glass substrate metallization promoting composition may include two or more types of Pd binders.

[0125] In one embodiment of the present application, the glass substrate metallization promoting composition may include one or two types of Pd binders.

[0126] In one embodiment of the present application, the Pd binder is a metal ion-containing compound.

[0127] In one embodiment of the present application, the Pd binder may be a lithium ion-containing compound.

[0128] In one embodiment of the present application, the Pd coupling agent includes a functional group capable of bonding with the silane coupling agent.

[0129] In one embodiment of the present application, the Pd binder may include a carboxyl group as a functional group capable of bonding with the silane coupling agent.

[0130] In one embodiment of the present application, the Pd binder may be represented by the following chemical formula 1.

[0131] [Chemical Formula 1]

[0132]

[0133] In the above chemical formula 1,

[0134] L1 to L3 are the same or different and each independently an alkylene group having 1 to 5 carbon atoms,

[0135] X1 is -NH2; -OH; -C(=O)OH; or -P(=O)(OH)2,

[0136] X2 and X3 are the same or different and each independently, -NH2; -OH; -C(=O)OH; -C(=O)O - M + ; -P(=O)(OH)2; -P(=O)(OH)(O - M + ); or -P(=O)(O - M + )2,

[0137] M is Li; or Na,

[0138] At least one of X2 and X3 is -C(=O)O - M + ; -P(=O)(OH)(O - M + ); or -P(=O)(O - M + )2.

[0139] The Pd binder of the present application is characterized by including an amino group; a hydroxyl group; a carboxyl group or a phosphonate group in a tertiary amine structure, and including at least one metal ion.

[0140] In one embodiment of the present application, the functional group capable of bonding with the silane coupling agent of the Pd binder may be X1 of the chemical formula 1.

[0141] The Pd binder of the above chemical formula 1 is -C(=O)O - M + ; -P(=O)(OH)(O - M + ); or -P(=O)(O - M +)2, it has excellent ionicity, so it is easy to dissociate within the composition, and the corresponding position can selectively react with the Pd catalyst. That is, the Pd binder of the above chemical formula 1 has excellent binding force with the Pd catalyst, so that a uniform metal layer can be formed during the plating process.

[0142] In addition, when a heteroatom (S, N, etc.) is included in the linker (L1 to L3) of the Pd binder of the above chemical formula 1, it is difficult to control the bonding position with the Pd binder, and the Pd binder of the above chemical formula 1 can form a stable three-dimensional structure by including a hydrocarbon linker (L1 to L3) of an appropriate length.

[0143] In one embodiment of the present application, L1 to L3 may be the same as or different from each other and may each independently be a methylene group; an ethylene group; a propylene group; a butylene group; or a pentylene group.

[0144] In one embodiment of the present application, L1 to L3 may be the same as or different from each other and may each independently be an alkylene group having 1 to 3 carbon atoms.

[0145] In one embodiment of the present application, L1 to L3 may be the same as or different from each other and may each independently be a methylene group; an ethylene group; or a propylene group.

[0146] In one embodiment of the present application, when the alkylene group in L1 to L3 becomes long, there is a problem that the reaction in the aqueous solution is difficult.

[0147] In one embodiment of the present application, X1 may be -C(=O)OH; or -P(=O)(OH)2.

[0148] In one embodiment of the present application, X1 may be -C(=O)OH.

[0149] In one embodiment of the present application, X1 may be -P(=O)(OH)2.

[0150] In one embodiment of the present application, X2 and X3 are the same or different from each other and are each independently -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 may be possible.

[0151] In one embodiment of the present application, X2 and X3 are -C(=O)O - Li + ; -P(=O)(OH)(O - Li + ); or -P(=O)(O - Li + )2 may be possible.

[0152] In one embodiment of the present application, M may be Li; or Na.

[0153] In one embodiment of the present application, it is preferable that M is Li, and can provide better Pd binding strength compared to when M is Na.

[0154] In one embodiment of the present application, when M is K or Cu, the ionicity is low compared to Li, so the Pd binding force is low, making it difficult to form a uniform plating layer.

[0155] In one embodiment of the present application, the Pd binder may be represented by the following chemical formula 1-1 or 1-2.

[0156] [Chemical Formula 1-1]

[0157]

[0158] [Chemical Formula 1-2]

[0159]

[0160] In the above chemical formulas 1-1 and 1-2,

[0161] L1 to L3 are the same or different and each independently an alkylene group having 1 to 5 carbon atoms,

[0162] Z is -OH; or -O - M + and,

[0163] Y1 to Y3 are the same or different and each independently, -OH; or -O - M + And,

[0164] M is Li; or Na.

[0165] In one embodiment of the present application, the glass substrate metallization promoting composition may include one or two types of Pd binders represented by the chemical formula 1.

[0166] In one embodiment of the present application, the glass substrate metallization promoting composition may include one Pd binder represented by the chemical formula 1.

[0167] In one embodiment of the present application, the glass substrate metallization promoting composition may further include an additional Pd binder other than the Pd binder represented by the chemical formula 1.

[0168] In one embodiment of the present application, the additional Pd binder may not contain a metal ion.

[0169] In one embodiment of the present application, the additional Pd binder may not be a metal ion-containing compound.

[0170] In one embodiment of the present application, the additional Pd binder may be represented by the following chemical formula 3.

[0171] [Chemical Formula 3]

[0172]

[0173] In the above chemical formula 3,

[0174] L 21 Inland L 23 are the same or different and each independently represents an alkylene group having 1 to 5 carbon atoms,

[0175] X 21 Inland X 23 are the same or different and each independently, -C(=O)OH; or -P(=O)(OH)2.

[0176] <Stabilizer>

[0177] In one embodiment of the present application, the composition promoting metallization of the glass substrate may further include a phase stabilizer selected from hydrochloric acid; sulfuric acid; methanol; ethanol; isopropyl alcohol; and sodium hydroxide.

[0178] In one embodiment of the present application, the glass substrate metallization promoting composition may include one or more of the phase stabilizers.

[0179] In one embodiment of the present application, the glass substrate metallization promoting composition may include two or more types of the phase stabilizers.

[0180] In one embodiment of the present application, the glass substrate metallization promoting composition may include one or two types of the phase stabilizer.

[0181] In one embodiment of the present application, by using the phase stabilizer, the pH of the composition can be adjusted to a range of 0.5 to 5, or 9 to 12, thereby helping to smoothly form hydrogen bonds between the -OH group of the glass substrate and the silane coupling agent.

[0182] The role of the above-mentioned phase stabilizer is to control the pH within the desired range and to improve the stability of the silane coupling agent. Specifically, the pH can be controlled by using phase stabilizers such as hydrochloric acid, sulfuric acid, and sodium hydroxide, and the stability of the silane coupling agent can be improved by using phase stabilizers such as methanol, ethanol, and isopropyl alcohol.

[0183] In one embodiment of the present 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.

[0184] In one embodiment of the present application, the phase stabilizer may include hydrochloric acid and isopropyl alcohol.

[0185] Solvent

[0186] In one embodiment of the present application, the glass substrate metallization promoting composition may further include a solvent.

[0187] In one embodiment of the present application, the solvent may be water.

[0188] In one embodiment of the present application, the glass substrate metallization promoting composition further comprises a solvent, and may comprise 0.1 to 5 parts by weight of the silane coupling agent, 0.5 to 5 parts by weight of the Pd binder, and the remainder may be a solvent, based on 100 parts by weight of the total of the glass substrate metallization promoting composition.

[0189] In one embodiment of the present application, the glass substrate metallization promoting composition further comprises a solvent, and may comprise 0.2 to 3 parts by weight of the silane coupling agent, 0.5 to 3 parts by weight of the Pd binder, and the remainder may be a solvent, based on 100 parts by weight of the entire glass substrate metallization promoting composition.

[0190] In one embodiment of the present application, the glass substrate metallization promoting composition further comprises a solvent, and may comprise 0.3 to 2 parts by weight of the silane coupling agent, 0.7 to 3 parts by weight of the Pd binder, and the remainder may be a solvent, based on 100 parts by weight of the entire glass substrate metallization promoting composition.

[0191] In one embodiment of the present application, the glass substrate metallization promoting composition further comprises a solvent, and may comprise 0.5 to 2 parts by weight of the silane coupling agent, 1 to 3 parts by weight of the Pd binder, and the remainder may be a solvent, based on 100 parts by weight of the entire glass substrate metallization promoting composition.

[0192] In one embodiment of the present application, the glass substrate metallization promoting composition further comprises a solvent; and a phase stabilizer, and based on 100 parts by weight of the total of the glass substrate metallization promoting composition, the silane coupling agent is included in an amount of 0.1 to 5 parts by weight, the Pd binder is included in an amount of 0.5 to 5 parts by weight, the phase stabilizer is included in an amount of 0.1 to 20 parts by weight, and the remainder may be a solvent.

[0193] In one embodiment of the present application, the glass substrate metallization promoting composition further comprises a solvent; and a phase stabilizer, and based on 100 parts by weight of the total glass substrate metallization promoting composition, the silane coupling agent is included in an amount of 0.2 parts by weight to 3 parts by weight, the Pd binder is included in an amount of 0.5 parts by weight to 3 parts by weight, the phase stabilizer is included in an amount of 0.1 parts by weight to 15 parts by weight, and the remainder may be a solvent.

[0194] In one embodiment of the present application, the glass substrate metallization promoting composition further comprises a solvent; and a phase stabilizer, and based on 100 parts by weight of the total of the glass substrate metallization promoting composition, the silane coupling agent is included in an amount of 0.3 parts by weight to 2 parts by weight, the Pd binder is included in an amount of 0.7 parts by weight to 3 parts by weight, the phase stabilizer is included in an amount of 0.1 parts by weight to 10 parts by weight, and the remainder may be a solvent.

[0195] In one embodiment of the present application, the glass substrate metallization promoting composition further comprises a solvent; and a phase stabilizer, and based on 100 parts by weight of the total of the glass substrate metallization promoting composition, the composition comprises 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 may be a solvent.

[0196] In one embodiment of the present application, the glass substrate metallization promoting composition further comprises a solvent; a phase stabilizer; and an additional Pd binder, and based on 100 parts by weight of the total of the glass substrate metallization promoting composition, the composition comprises 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 may be a solvent.

[0197] In one embodiment of the present application, the glass substrate metallization promoting composition further comprises a solvent; a phase stabilizer; and an additional Pd binder, and based on 100 parts by weight of the total of the glass substrate metallization promoting composition, the composition comprises 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 may be a solvent.

[0198] In one embodiment of the present application, the glass substrate metallization promoting composition further comprises a solvent; a phase stabilizer; and an additional Pd binder, and based on 100 parts by weight of the total of the glass substrate metallization promoting composition, the composition comprises 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 may be a solvent.

[0199] Another embodiment of the present application provides a method for producing a composition for promoting metallization of a glass substrate, comprising the steps of: preparing a mixture by mixing a silane coupling agent and a Pd binder; and stirring the mixture, wherein the Pd binder includes a functional group capable of bonding with the silane coupling agent and is a metal ion-containing compound.

[0200] In one embodiment of the present application, the mixture may further include a solvent and a phase stabilizer.

[0201] A method for producing a composition for promoting metallization of a glass substrate according to one embodiment of the present application may include a step of producing a mixture by mixing a solvent, at least one silane coupling agent, at least one Pd binder, and at least one phase stabilizer; and a step of stirring the mixture.

[0202] Specific descriptions of the above solvent, silane coupling agent, Pd binder and phase stabilizer are as described in the above glass substrate metallization promoting composition.

[0203] In one embodiment of the present application, the temperature condition in the stirring step is 15°C to 25°C.

[0204] In one embodiment of the present application, the time condition in the stirring step is 1 to 3 hours.

[0205] In one embodiment of the present application, the solvent, silane coupling agent, Pd binder, and phase stabilizer may be mixed in any order.

[0206] In one embodiment of the present application, the step of preparing the mixture may be a step of mixing at least one silane coupling agent, at least one Pd binder, and at least one phase stabilizer into the solvent.

[0207] In one embodiment of the present application, the step of preparing the mixture may include a step of preparing a first mixture by mixing at least one of the phase stabilizers into the solvent; a step of preparing a second mixture by mixing at least one of the Pd binders into the first mixture; and a step of preparing a third mixture by mixing at least one of the silane coupling agents into the second mixture.

[0208] When the mixture is prepared in the above order, the stability is better.

[0209]

[0210] Glass substrate plating process

[0211] In one embodiment of the present application, the glass substrate plating process may be a process of forming a metal layer on the glass substrate.

[0212] In one embodiment of the present application, the metal layer may be, for example, a Cu layer.

[0213] In one embodiment of the present application, the glass substrate plating process may be an electroless plating process.

[0214] In one embodiment of the present application, any method known in the art can be applied to the glass substrate plating process.

[0215] In one embodiment of the present application, the glass substrate plating process can be performed at a temperature of 30°C to 50°C.

[0216] In one embodiment of the present application, an electroplating process can be performed after the glass substrate plating process.

[0217]

[0218] annealing process

[0219] In one embodiment of the present application, the annealing process may be a Si-O-Si condensation process.

[0220] In the above annealing process, a Si-O-Si condensation reaction occurs, causing the metal layer to adhere to the glass substrate.

[0221] Since the annealing process is generally performed at high temperatures (approximately 150°C), high adhesion between the glass substrate and the metal layer is required even under high-temperature conditions.

[0222] In one embodiment of the present application, any method known in the art can be applied to the annealing process.

[0223] In one embodiment of the present application, the annealing process can be performed at a temperature of 100°C to 500°C.

[0224] In one embodiment of the present application, the annealing process can be performed at a temperature of 200°C to 400°C.

[0225] In one embodiment of the present application, the annealing process can be performed for 1 to 2 hours.

[0226]

[0227] Glass substrate pretreatment process

[0228] In one embodiment of the present application, the glass substrate metallization process may further include a glass substrate pretreatment process.

[0229] In one embodiment of the present application, the glass substrate metallization process may include a glass substrate pretreatment process; a glass substrate metallization promotion process; a glass substrate plating process; and an annealing process. That is, the glass substrate pretreatment process may be performed before the glass substrate metallization promotion process.

[0230] In one embodiment of the present application, the glass substrate pretreatment process may include a step of forming a hydroxyl group on the surface of the glass substrate.

[0231] In one embodiment of the present application, the glass substrate pretreatment process may include a pretreatment process A for cleaning the glass substrate using a pretreatment composition A, and a pretreatment process B for forming a hydroxyl group on the surface of the glass substrate using a pretreatment composition B.

[0232] In one embodiment of the present application, the pretreatment processes A and B may each include a process of applying pretreatment compositions A and B onto a glass substrate. Specifically, the pretreatment compositions A and B may be applied onto the glass substrate via a spray or dipping method.

[0233] In one embodiment of the present application, the pretreatment process A can be performed for 2 to 10 minutes at a temperature condition of 40°C to 60°C.

[0234] In one embodiment of the present application, the pretreatment process B can be performed for 1 to 5 minutes at a temperature condition of 15°C to 30°C.

[0235] In one embodiment of the present application, the pretreatment composition A may include an amine compound; a polar solvent; a non-polar solvent; and a pretreatment solvent.

[0236] In one embodiment of the present application, the amine compound may include at least one selected from monoisopropanol amine and monoethanol amine.

[0237] In one embodiment of the present application, the polar solvent may include at least one selected from diethyl formamide and N-methylpyrrolidone.

[0238] In one embodiment of the present application, the non-polar solvent may include at least one selected from butyl diglycol and ethyl diglycol.

[0239] In one embodiment of the present application, the pretreatment solvent may be water.

[0240] In one embodiment of the present application, the pretreatment composition A may include 3 to 20 wt% of the amine compound, 5 to 30 wt% of the polar solvent, 10 to 40 wt% of the non-polar solvent, and 30 to 80 wt% of the pretreatment solvent, based on 100 wt% of the pretreatment composition A.

[0241] In one embodiment of the present application, the pretreatment composition B may include an acidic solution and a pretreatment solvent.

[0242] In one embodiment of the present application, the acidic solution may include at least one selected from hydrochloric acid and sulfuric acid.

[0243] In one embodiment of the present application, the pretreatment solvent may be water.

[0244] In one embodiment of the present application, the pretreatment composition B may further include an oxidizing agent.

[0245] In one embodiment of the present application, the oxidizing agent may be hydrogen peroxide.

[0246] In one embodiment of the present application, the pretreatment composition B may include 3 to 10 wt% of the acid solution, 0 to 20 wt% of the oxidizing agent, and 80 to 97 wt% of the pretreatment solvent based on 100 wt% of the pretreatment composition B.

[0247] In one embodiment of the present application, the glass substrate pretreatment process; the glass substrate metallization promotion process; and the glass substrate plating process can each be processed within 2 to 30 minutes.

[0248] In one embodiment of the present application, the thickness of the glass substrate may be 0.3 mm to 1.2 mm.

[0249] In one embodiment of the present application, the thickness of the glass substrate may be 0.6 mm to 1.2 mm.

[0250] In one embodiment of the present application, the thickness of the glass substrate may be 0.8 mm to 1.2 mm.

[0251] In one embodiment of the present application, the glass substrate may include a through hole.

[0252] In one embodiment of the present application, the shape of the through hole may vary depending on the through hole formation process and is not particularly limited. For example, the shape of the through hole may be cylindrical or hourglass-shaped.

[0253] In one embodiment of the present application, the glass substrate may be a TGV (Through Glass Via) substrate.

[0254] In one embodiment of the present application, the diameter of the through hole of the glass substrate may be 10 ㎛ to 140 ㎛.

[0255] In one embodiment of the present application, the diameter of the through hole of the glass substrate refers to the diameter of the through hole that can be confirmed 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, when the shape of the through hole is like an hourglass as shown in FIG. 3, the diameter of the hole may not be constant, and in this case, the diameter of the through hole may be the diameter of the hole that is in a straight line with the upper surface of the glass substrate based on the depth direction of the through hole (the vertical direction of the upper surface of the glass substrate).

[0256] In one embodiment of the present application, the aspect ratio of the glass substrate may be 1:3 to 1:20.

[0257] In the present application, the aspect ratio of the glass substrate may be the ratio of the diameter (diameter) and 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 and the thickness of the glass substrate.

[0258] In the present application, the aspect ratio of the glass substrate may be the aspect ratio of the through hole of the glass substrate, and specifically, the diameter of the through hole of the glass substrate may be: the thickness of the glass substrate.

[0259] In Fig. 3, the diameter of the through hole of 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.

[0260] In one embodiment of the present application, the aspect ratio of the glass substrate may be 1:5 or more.

[0261] In one embodiment of the present application, the aspect ratio of the glass substrate may be 1:5 to 1:20.

[0262] In one embodiment of the present application, the aspect ratio of the glass substrate may be 1:6 or more.

[0263] In one embodiment of the present application, the aspect ratio of the glass substrate may be 1:6 to 1:20.

[0264] When plating a glass substrate is performed using a glass substrate metallization process according to one embodiment of the present application, the aspect ratio of the glass substrate can be increased.

[0265]

[0266] Glass substrate manufacturing process

[0267] Another embodiment of the present application provides a process for manufacturing a glass substrate including the above glass substrate metallization process.

[0268] In one embodiment of the present application, the glass substrate manufacturing process may further include a process of forming a through hole in the glass substrate.

[0269] In one embodiment of the present application, the process for forming a through hole in the glass substrate may include a glass substrate laser phase displacement process and a glass substrate hole etching process.

[0270] In one embodiment of the present application, the manufacturing process of the glass substrate may be performed in the following order: the glass substrate laser phase displacement process; the glass substrate hole etching process; and the glass substrate metallization process.

[0271] In one embodiment of the present application, the glass substrate laser phase displacement process is a process of causing deformation inside the glass substrate using laser phase displacement, and methods known in the art can be used.

[0272] In one embodiment of the present application, the glass substrate hole etching process is a process of forming a through hole in a portion of the glass substrate where deformation has occurred, and methods known in the art can be used.

[0273]

[0274] metallized glass substrate

[0275] Another embodiment of the present application provides a metallized glass substrate manufactured by the aforementioned glass substrate manufacturing process.

[0276] Another embodiment of the present 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 included between the glass substrate and the metal layer, and the metallization promoting layer includes a silane coupling agent; and a Pd coupling agent including a functional group and a metal ion combined with the silane coupling agent.

[0277] Another embodiment of the present application provides a metallized glass substrate comprising a glass substrate having a through hole; and a metal layer provided in the through hole of the glass substrate, wherein a metallization promoting layer is included between the glass substrate and the metal layer, and the metallization promoting layer includes a silane coupling agent; and a Pd coupling agent including a functional group and a metal ion combined with the silane coupling agent.

[0278] In the present application, a metallized glass substrate means a structure in which a metal layer is formed on at least one surface of a glass substrate.

[0279] The metallized glass substrate according to the present application is characterized in that the glass substrate is metallized using the aforementioned glass substrate metallization promoting composition rather than using the Cu sputtering method. Typically, when the Cu sputtering method is adopted, the Cu seed is formed by Ti-Cu sputtering, so that the metallized glass substrate can contain Ti. On the other hand, the metallized glass substrate of the present application does not adopt the Ti-Cu sputtering method, and therefore does not contain Ti.

[0280] According to the present application, the metallized glass substrate may have an adhesion strength of 4B or higher when evaluated at room temperature.

[0281] According to the present application, the metallized glass substrate may have an adhesion strength of 5B or higher when evaluated at room temperature.

[0282] According to the present application, the metallized glass substrate may have an adhesion strength of 4B or higher when evaluated under HAST conditions.

[0283] According to the present application, the metallized glass substrate may have an adhesion strength of 5B or higher when evaluated under HAST conditions.

[0284] In the present application, the HAST conditions are a temperature of 100°C to 150°C, a humidity of 80% to 90%, and a time of 80 to 100 hours, or a temperature of 110°C to 140°C, a humidity of 83% to 87%, and a time of 90 to 100 hours.

[0285] According to the present application, the plating uniformity of the metallized glass substrate may be at least 75% plated as measured through image analysis.

[0286] According to the present application, the plating uniformity of the metallized glass substrate may be at least 90% plated as measured through image analysis.

[0287] According to the present application, the plating coverage ratio of the metallized glass substrate can be 80% or more.

[0288] The above plating coverage ratio is obtained by cutting a cross-section of a metallized glass substrate with a FIB (Focused Ion Beam) and measuring the Cu thickness (T1) on the surface (top surface) of the glass substrate and the Cu thickness (T2, T3, and T4) according to the position within the glass substrate penetration hole (see Fig. 6), and then means the average value of the T2 / T1 ratio, the T3 / T1 ratio, and the T4 / T1 ratio.

[0289] More specifically, the plating coverage ratio can be calculated by measuring the thickness (T1) of the metal layer at a position 100 ㎛ away from the through hole on the upper surface of the glass substrate based on a cut surface obtained by cutting a through hole of the metallized glass substrate in a direction perpendicular to the upper surface of the glass substrate, the thickness (T2) of the metal layer at a position of the through hole at a thickness of 25% away from the upper surface of the glass substrate when the thickness of the glass substrate is 100%, the thickness (T3) of the metal layer at a position of the through hole at a thickness of 50% away, and the thickness (T4) of the metal layer at a position of the through hole at a thickness of 75% away, and then using the following Equation 1.

[0290] [Formula 1]

[0291]

[0292] The metallized glass substrate according to the present application can be used for semiconductor packaging. Specifically, the glass substrate according to the present application can be used to package semiconductor chips / devices. More specifically, semiconductor packaging refers to a post-processing technology that cuts and packages processed wafers into chip shapes. In this context, the glass substrate is attracting attention as a next-generation semiconductor packaging material that physically and electrically connects semiconductor chips to the system. In order to be used as a semiconductor packaging material, it requires functions such as mechanical protection, electrical and mechanical connection, and heat dissipation. In particular, the TGV hole substrate includes microscopic electrode channels in the glass substrate that facilitate the flow of electricity, which has the advantage of enabling the mounting of more chips and high-performance chips.

[0293] The metallized glass substrate according to the present application can be applied to packaging fields requiring large areas such as AI, high performance computers (HPC), data centers, servers, and networking, and can be applied particularly to generative AI and HPC.

[0294] Hereinafter, examples will be provided to specifically explain the present application. However, the embodiments according to the present application may be modified in various ways, and the scope of the present application is not construed as being limited to the embodiments described below. The embodiments of the present application are provided to more fully explain the present application to those of average skill in the art.

[0295]

[0296] <Example 1> Metallization of glass substrate

[0297] Glass substrate 1 of Table 1 below was used, and the glass substrate was plated using the following process.

[0298] Thickness (T = 1 mm) TGV hole diameter (mm) Aspect ratio Etching (through hole formation) Glass substrate 10.5T0.1mm1:5O Glass substrate 20.64T0.1mm1:6.4O Glass substrate 30.84T0.1mm1:8.4O

[0299] *Aspect ratio: The ratio of the TGV hole diameter to its thickness

[0300] (1) Pretreatment process

[0301] A glass substrate (glass substrate 1) was pretreated by immersing it in pretreatment composition A (5 wt% Monoethanol amine, 15 wt% N-methylpyrrolidone, 10 wt% Ethyl diglycol, balance water) at 50°C for 5 minutes, and then immersing it in pretreatment composition B (3 wt% HCl, balance water) at room temperature (25°C) for 2 minutes.

[0302] (2) Glass substrate metallization promotion process (GCS-AP)

[0303] The pretreated glass substrate was immersed in the metallization promoting composition at room temperature (25°C) for 2 minutes, then immersed in a Pd catalyst at 40°C for 5 minutes, and then immersed in a reducing agent at 30°C for 3 minutes to reduce the Pd catalyst.

[0304] [Metallization promoting composition]

[0305] Silane coupling agent (aminoethylaminopropyltrimethoxysilane, 0.5 wt%), Pd coupling agent (LCC-1(C6H 9-n NO6Li n , n=2)), 1 wt%), a stabilizer (HCl, 0.3 wt%), and a solvent (water, remainder) were mixed and stirred at room temperature for 2 hours to prepare a metallization promoting composition.

[0306] (3) Glass substrate plating process

[0307] A Cu layer was formed on the glass substrate by immersing the glass substrate in a plating composition containing Cu, a leveling agent, and a stabilizer at 40°C for 30 minutes (electroless copper plating).

[0308] (4) Annealing process

[0309] It was dried for 60 minutes under N2 conditions at 400°C using an oven.

[0310] <Example 2>

[0311] The glass substrate was plated in the same manner as in Example 1, except that the glass substrate 2 of Table 1 was used instead of the glass substrate 1 in Example 1.

[0312] <Example 3>

[0313] The glass substrate was plated in the same manner as in Example 1, except that the glass substrate 3 of Table 1 was used instead of the glass substrate 1 in Example 1.

[0314] <Comparative Example 1>

[0315] In Example 1, (1) the pretreatment process and (2) the glass substrate metallization promotion process (GCS-AP) were omitted, and the glass substrate was plated in the same manner as in Example 1, except that Cu seeds were formed on the surface of the glass substrate using a Cu sputtering method (dry).

[0316] Specifically, Cu was placed in a chamber using a thin film deposition method, plasma was induced to form an electric field, and then Cu atoms decomposed through gas decomposition formed a thin film on a glass substrate, thereby forming a Cu seed.

[0317] <Comparative Example 2>

[0318] The glass substrate was plated in the same manner as in Comparative Example 1, except that the glass substrate 2 of Table 1 was used instead of the glass substrate 1 in Comparative Example 1.

[0319] <Comparative Example 3>

[0320] The glass substrate was plated in the same manner as in Comparative Example 1, except that the glass substrate 3 of Table 1 was used instead of the glass substrate 1 in Comparative Example 1.

[0321] <Comparative Example 4>

[0322] In Example 1, (1) the pretreatment process and (2) the glass substrate metallization promotion process were omitted, and the glass substrate was plated in the same manner as in Example 1, except that Cu was deposited using the LPD (metal oxide) method.

[0323] Specifically, Cu was sprayed onto the surface of a glass substrate and deposited while drying.

[0324] Comparative Example 5

[0325] In Comparative Example 4, the glass substrate was plated in the same manner as in Comparative Example 4, except that the glass substrate 2 of Table 1 was used instead of the glass substrate 1.

[0326] <Comparative Example 6>

[0327] In Comparative Example 4, the glass substrate was plated in the same manner as in Comparative Example 4, except that the glass substrate 3 of Table 1 was used instead of the glass substrate 1.

[0328]

[0329] <Experimental Example>

[0330] The characteristics of the glass substrate plated in the above examples and comparative examples are evaluated and shown in Table 2 below. The evaluation method for the characteristics listed in Table 2 below is as follows.

[0331] Electricity supply

[0332] Using an ohmmeter, the conductivity of the plated glass substrate was checked, and the results were indicated as O (conduction) and X (short circuit).

[0333] Plating uniformity

[0334] The plating uniformity was confirmed through image analysis of the above-mentioned plated glass substrate, and the results were indicated as ○ (100% plating), □ (75% or more plating), △ (50% or more plating), and X (less than 50% plating).

[0335] Specifically, the above plating uniformity was visually evaluated and the standard of Fig. 5 was referenced.

[0336] Room temperature adhesion (cross-cut evaluation)

[0337] At room temperature, the above-mentioned plated glass substrate was formed into a grid using a cross-cutter (TOC AT-CC3000 / ASTM1), and then an adhesive tape (3M 8981 25mmX10m (7.6N), TOC sp3020) was applied and then removed to determine the shape of the remaining grid. The judgment criteria were based on the ASTM D3359-08 standard.

[0338] HAST adhesion

[0339] The above-mentioned plated glass substrate was left for 96 hours under conditions of 130°C and 85% humidity, and then the evaluation of room temperature adhesion was performed in the same manner.

[0340] Plating coverage ratio

[0341] The plated glass substrate was cut in cross-section using FIB, and the thickness (T1) of the metal layer at a position 100 ㎛ away from the through hole on the upper surface of the glass substrate, the thickness (T2) of the metal layer at a position of the through hole at a thickness of 25% away from the upper surface of the glass substrate when the thickness of the glass substrate is 100%, the thickness (T3) of the metal layer at a position of the through hole at a thickness of 50% away, and the thickness (T4) of the metal layer at a position of the through hole at a thickness of 75% away were measured. Then, the ratio of T2 / T1, the ratio of T3 / T1, and the ratio of T4 / T1 were each calculated, and the average value thereof was evaluated as the plating coverage ratio.

[0342] Glass substrate metallization promotion process Electric conduction plating uniformity Room temperature adhesion HAST adhesion Plating coverage ratio Example 11 GCS-AP 005 B 5 B 8 1% Example 22 005 B 5 B 8 6% Example 33 005 B 4 B 9 4% Comparative example 11 Cu sputtering 004 B 3 B 4 3% Comparative example 22 X □ 4 B 3 B 3 9% Comparative example 33 X □ 4 B 3 B 2 5% Comparative example 41 LPD 004 B 3 B 5 3% Comparative example 52 004 B 3 B 3 8% Comparative example 63 X □ 4 B 3 B 3 1%

[0343] *Comparative Examples 1 to 6: Instead of the metallization promotion process (GCS-AP) of the present invention, the conventional Cu sputtering method or LPD method was used.

[0344] As can be seen from the results in Table 2 above, it can be seen that the plating uniformity, room temperature / HAST adhesion, and plating coverage ratio of the glass substrate plated through the metallization acceleration process (GCS-AP) of the present invention are superior to those of the comparative example group. In particular, it was confirmed that the plating coverage ratio was further increased despite the increase in the aspect ratio of the glass substrate through Examples 1 to 3.

[0345] On the other hand, in the case of comparative examples 1 to 3 using the Cu sputtering method, the plating coverage ratio did not exceed 50% even under low aspect ratio (1:5) conditions, and it was confirmed that it further decreased as the aspect ratio increased, and it was confirmed that the performance was also deteriorated in the evaluation of electric conduction and plating uniformity.

[0346] In addition, in the case of Comparative Examples 4 to 6 using the LPD method, improved performance was shown compared to Comparative Examples 1 to 3 using the Cu sputtering method, but it was confirmed to be at the level of 30% to 60% of that of Examples 1 to 3 under the same aspect ratio conditions.

[0347] Therefore, when a glass substrate is plated through the metallization promotion process of the present invention, it can be seen that even a glass substrate with a high aspect ratio can be plated uniformly and with a high coverage ratio, and high adhesion is provided not only at room temperature but also under HAST conditions.

Claims

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

2. In claim 1, the Pd binder is represented by the following chemical formula 1: A glass substrate metallization process: [Chemical Formula 1] In the above chemical formula 1, L1 to L3 are the same or different and each independently an alkylene group having 1 to 5 carbon atoms, X1 is -NH2; -OH; -C(=O)OH; or -P(=O)(OH)2, X2 and X3 are the same or different and each independently, -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 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.

3. A glass substrate metallization process according to claim 1, wherein the glass substrate metallization process further includes a glass substrate pretreatment process.

4. A glass substrate metallization process according to claim 1, wherein the glass substrate metallization promotion process further includes a step of applying a Pd catalyst.

5. A glass substrate metallization process according to claim 1, wherein the glass substrate metallization promotion process and the glass substrate plating process are wet processes.

6. A glass substrate metallization process according to claim 1, wherein the thickness of the glass substrate is 0.3 mm to 1.2 mm.

7. A process for metallizing a glass substrate according to claim 1, wherein the glass substrate includes a through hole.

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

9. A process for metallizing a glass substrate according to claim 7, wherein the aspect ratio of the glass substrate is 1:3 to 1:

20.

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

11. A glass substrate manufacturing process according to claim 10, wherein the glass substrate manufacturing process further includes a glass substrate through-hole forming process.

12. A glass substrate manufacturing process according to claim 11, wherein the glass substrate through-hole forming process includes a glass substrate laser phase displacement process and a glass substrate hole etching process.

13. A metallized glass substrate manufactured by a glass substrate manufacturing process according to claim 10.

14. A metallized glass substrate comprising a glass substrate; and a metal layer provided on the glass substrate, A metallization promoting layer is included between the glass substrate and the metal layer, A metallized glass substrate, wherein the metallization promoting layer comprises a silane coupling agent and a Pd coupling agent including a functional group and a metal ion bonded to the silane coupling agent.

15. A metallized glass substrate comprising a glass substrate having a through hole; and a metal layer provided within the through hole of the glass substrate, A metallization promoting layer is included between the glass substrate and the metal layer, A metallized glass substrate, wherein the metallization promoting layer comprises a silane coupling agent and a Pd coupling agent including a functional group and a metal ion bonded to the silane coupling agent.

16. In claim 15, A metallized glass substrate having an aspect ratio of 1:5 to 1:

20.

17. In claim 15, The plating coverage ratio of the above metallized glass substrate is 80% or more, The above plating coverage ratio is calculated by using the following Equation 1, which is obtained by cutting a through hole of the metallized glass substrate in a vertical direction with respect to the upper surface of the glass substrate using a Focused Ion Beam, and measuring the thickness (T1) of the metal layer at a position 100 ㎛ away from the through hole on the upper surface of the glass substrate, the thickness (T2) of the metal layer at a position of the through hole at a thickness of 25% away from the upper surface of the glass substrate, the thickness (T3) of the metal layer at a position of the through hole at a thickness of 50% away, and the thickness (T4) of the metal layer at a position of the through hole at a thickness of 75% away, when the thickness of the glass substrate is 100%: [Formula 1]

Images