Glass substrate metallization acceleration composition, method for preparing same, glass substrate metallization acceleration method, and metallized glass substrate

Abstract

The present disclosure is directed to providing a glass substrate metallization accelerating composition comprising a silane coupling agent and a Pd binder, wherein the Pd binder is a metal ion containing compound comprising a functional group capable of binding to the silane coupling agent. A metal layer may be uniformly formed on a glass substrate having a high aspect ratio only by a wet process.

Description

Technical Field

[0001] This disclosure relates to glass substrate metallization acceleration compositions, methods for preparing the same, glass substrate metallization acceleration methods, and metallized glass substrates.

[0002] This application claims the benefit of Korean Patent Application No. 10-2024-0118571, filed with the Korean Intellectual Property Office on September 2, 2024, and Korean Patent Application No. 10-2024-0201693, filed with the Korean Intellectual Property Office on December 31, 2024, the entire disclosure of which is incorporated herein by reference. Background Technology

[0003] Because glass substrates are excellent in terms of warpage and coefficient of thermal expansion (CTE), they enable the realization of large-area substrates and facilitate high-speed signal conduction and heat dissipation through the increase in the number of I / Os.

[0004] However, the problem with glass substrates is that they exhibit low adhesion to metals and do not allow for direct electroless plating.

[0005] Therefore, research is needed on technologies for improving the adhesion between glass and copper, and in particular, technologies that can ensure reliability even under high temperature and high humidity conditions are needed.

[0006] According to relevant technologies, electroless copper plating is performed after a Cu seed is formed on the surface of a glass substrate by Cu sputtering. However, a drawback is that when the thickness of the glass substrate increases or the diameter of the through-glass via (TGV) hole decreases (i.e., when the aspect ratio increases), a Cu seed does not form in the center of the TGV hole.

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

[0008] In these cases, there is a need to develop a metal surface treatment method that enables metal plating on the surface of the glass substrate, especially under high temperature and high humidity conditions, when increasing the aspect ratio of the glass substrate.

[0009] [Quote]

[0010] (Patent Document 1) Korean Patent Publication No. 10-2010-0135603 Summary of the Invention

[0011] Technical issues

[0012] This disclosure aims to provide glass substrate metallization acceleration compositions, methods for preparing the same, glass substrate metallization acceleration methods, and metallized glass substrates.

[0013] Technical solution

[0014] An exemplary embodiment of this disclosure provides a glass substrate metallization acceleration composition comprising a silane coupling agent and a Pd binder, wherein the Pd binder comprises functional groups capable of binding with the silane coupling agent and is a metal ion-containing compound.

[0015] Another exemplary embodiment of this disclosure provides a method for preparing glass substrate metallization accelerated compositions.

[0016] Another exemplary embodiment of this disclosure provides a method for accelerating metallization of a glass substrate, which includes the step of surface-treating a glass substrate using the aforementioned glass substrate metallization accelerating composition.

[0017] Another exemplary embodiment of this disclosure provides a metallized glass substrate comprising: a glass substrate; and a metal layer disposed on the glass substrate, wherein a metallization acceleration layer is included between the glass substrate and the metal layer, and the metallization acceleration layer comprises a silane coupling agent and a Pd binder comprising functional groups and metal ions bonded to the silane coupling agent.

[0018] Another exemplary embodiment of this disclosure provides a metallized glass substrate comprising: a glass substrate having through-holes; and a metal layer disposed in the through-holes of the glass substrate, wherein a metallization acceleration layer is included between the glass substrate and the metal layer, and the metallization acceleration layer comprises a silane coupling agent and a Pd binder comprising functional groups and metal ions bonded to the silane coupling agent.

[0019] Beneficial effects

[0020] An exemplary embodiment of the glass substrate metallization acceleration composition according to this disclosure is characterized in that it comprises at least one silane coupling agent, at least one Pd binder, and at least one phase stabilizer. When using the glass substrate metallization acceleration composition, Cu seed formation by Cu sputtering during the conventional electroless copper plating process of the glass substrate can be omitted, and the metallization of the glass substrate can be completed solely by wet processing.

[0021] Furthermore, plating can be performed without Cu seed by using a Pd binder and a Pd catalyst, thus such plating is unaffected by the thickness of the glass substrate or the pore size of the through-glass via (TGV). Therefore, an increase in the aspect ratio of the glass substrate can be expected.

[0022] Furthermore, when a glass substrate is metallized using the glass substrate metallization acceleration composition according to this disclosure, the adhesion between the glass substrate and the metal layer can be enhanced not only at room temperature but also at high temperature and high humidity, and thus provides the advantage of excellent coating coverage due to the uniform metal layer thickness. Attached Figure Description

[0023] Figure 1 This is a schematic diagram illustrating the process of manufacturing a glass substrate and the glass substrate metallization process according to related technologies.

[0024] Figure 2 This is a schematic diagram illustrating the process of manufacturing a glass substrate and the glass substrate metallization process according to the present disclosure.

[0025] Figure 3 A schematic diagram illustrating the glass substrate metallization process according to this disclosure.

[0026] Figure 4 The standard used to evaluate the coating uniformity of the glass substrate according to this disclosure is shown.

[0027] Figure 5 The measurement locations for each thickness, measured to evaluate the coating coverage of a glass substrate according to this disclosure, are shown.

[0028] [Explanation of reference numerals in the attached figures]

[0029] 10: Silane coupling agent

[0030] 20: Pd adhesive

[0031] 30: Pd catalyst

[0032] T: Thickness of the glass substrate

[0033] R: Diameter of the through-hole in the glass substrate

[0034] A: The location where the Pd binder and Pd catalyst are bonded.

[0035] B: The location where the Pd binder and silane coupling agent bond.

[0036] T1: Cu thickness on the glass substrate surface

[0037] T2: Cu thickness at the point corresponding to 1 / 4 of the thickness inside the through-hole of the glass substrate.

[0038] T3: Cu thickness at the point corresponding to 2 / 4 of the thickness inside the through-hole of the glass substrate.

[0039] T4: Cu thickness at the point corresponding to 3 / 4 of the thickness inside the through-hole of the glass substrate. Detailed Implementation

[0040] The contents of this disclosure will be explained in detail below.

[0041] Throughout this specification, unless the context clearly indicates otherwise, when a part is described as "including" a component, this does not exclude the presence of another component, but rather implies that it may include another component.

[0042] Throughout this specification, there are no particular limitations on the glass substrate, as long as it is one used in the art as a substrate made of glass. For example, the glass substrate disclosed herein may be a glass substrate with through holes.

[0043] Throughout this specification, “glass substrate metallization” generally refers to the coating of a glass substrate, i.e., the formation of a metal layer on at least one surface of a glass substrate, and there is no limitation on the type of metal used for coating, but specific examples may include copper (Cu) or nickel (Ni), especially Cu.

[0044] Throughout this specification, "the surface of the glass substrate" or "on the glass substrate" may refer to any part of the glass substrate that is in contact with the outside.

[0045] In this disclosure, alkyl groups can be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably from 1 to 30. Specific examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, etc.

[0046] In this disclosure, the above examples of alkyl groups apply to alkylene groups, except that the alkylene group is divalent.

[0047] In this disclosure, a fused heterocyclic group refers to a monovalent ring having a heterocyclic ring fused with an aliphatic or aromatic hydrocarbon ring.

[0048] In this disclosure, the heterocycle comprises one or more atoms other than carbon, i.e., one or more heteroatoms, and specifically, may comprise one or more atoms selected from O, N, Se, and S. The number of carbon atoms is not particularly limited, but is preferably between 2 and 30, and the heterocycle may be monocyclic or polycyclic.

[0049] In this disclosure, there are no particular limitations on the aliphatic hydrocarbon ring, but it is preferred to have 3 to 30 carbon atoms, and specific examples include, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane, bis(cyclohexane), cycloheptane, cyclooctane, etc.

[0050] In this disclosure, there are no particular limitations on the aromatic hydrocarbon ring, but it is preferred to have 6 to 30 carbon atoms, and specific examples include, but are not limited to, benzene (phenyl), biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, pyrene, fluorene, etc.

[0051] Glass substrate metallization accelerated composition

[0052] An exemplary embodiment of this disclosure provides a glass substrate metallization acceleration composition, characterized in that it comprises a silane coupling agent and a Pd binder, wherein the Pd binder is a metal ion-containing compound containing functional groups capable of binding with the silane coupling agent.

[0053] Specifically, when the glass substrate is surface-treated using a glass substrate metallization acceleration composition, the glass substrate can be bonded to a silane coupling agent. The silane coupling agent can be bonded to the Pd binder through the functional groups of the Pd binder that can bond to the silane coupling agent, and the Pd binder can be bonded to the Pd catalyst through the properties of the Pd binder as a compound containing metal ions.

[0054] Furthermore, when depositing on a glass substrate using a glass substrate metallization accelerating composition, the step of forming Cu seeds by Cu sputtering can be omitted. Since the step of forming Cu seeds by Cu sputtering is performed using a dry process, followed by a wet process for the subsequent depositing process, the dry and wet processes are performed separately. On the other hand, when using a glass substrate metallization accelerating composition, the glass substrate can be metallized solely by a wet process.

[0055] Figure 1 A process for manufacturing a glass substrate according to related technology is illustrated. When a through-hole is formed in the glass substrate and the glass substrate with the through-hole is subjected to a plating process, electroless plating is performed by forming a Cu seed followed by electroplating. However, in such a process, a problem exists that when the aspect ratio is increased by increasing the thickness of the glass substrate or by decreasing the diameter of the hole, Cu cannot be deposited well in the center of the hole.

[0056] on the contrary, Figure 2 The process for manufacturing a glass substrate according to the present disclosure is shown, wherein the integrated process of metal surface treatment / electro-free plating, i.e. the metallization process according to the present disclosure, is carried out entirely by wet process, Cu deposition is appropriately completed, and a coating layer with uniform thickness can be formed even at high aspect ratios.

[0057] Specifically, since the composition according to this disclosure comprises a silane coupling agent and a Pd binder, the -OH groups formed on the glass substrate undergoing the pretreatment process form hydrogen bonds with one end of the silane coupling agent, the other end of the silane coupling agent bonds with the Pd binder, and the Pd catalyst bonds with the Pd binder. In this way, when the Pd catalyst is formed on the substrate, Cu plating is achieved through the excellent adhesion between Pd and Cu.

[0058] The composition of the composition will be described in detail below.

[0059] 1) Silane coupling agent

[0060] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition may contain one or more silane coupling agents.

[0061] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition may contain two or more silane coupling agents.

[0062] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition may contain one or two silane coupling agents.

[0063] In one exemplary embodiment of this disclosure, the silane coupling agent may be represented by the following chemical formula 2:

[0064] [Chemical Formula 2]

[0065]

[0066] In chemical formula 2,

[0067] R1 to R3 may be the same or different, and each is independently a C1 to C5 alkyl group.

[0068] L 11 and L 12 They may be the same or different, and each is independently a C1 to C5 alkylene group.

[0069] n is 0 or 1, and

[0070] Q is -SH, -NH2, or a fused heterocyclic group containing O.

[0071] In one exemplary embodiment of this disclosure, at least one of R1 to R3 in Formula 2 above can form a hydrogen bond with -OH on the surface of the glass substrate.

[0072] In one exemplary embodiment of this disclosure, Q in Formula 2 can be bonded to the Pd binder.

[0073] In one exemplary embodiment of this disclosure, R1 to R3 may be the same or different, and may each be independently methyl, ethyl, propyl, butyl or pentyl.

[0074] In one exemplary embodiment of this disclosure, R1 to R3 may be the same or different, and may each be methyl or ethyl independently.

[0075] In one exemplary embodiment of this disclosure, L11 and L 12 They may be the same or different, and each can be methylene, ethylene, propylene, butylene, or pentylene independently.

[0076] In one exemplary embodiment of this disclosure, L 11 and L 12 They may be the same or different, and each may be an alkylene group from C2 to C4 independently.

[0077] In one exemplary embodiment of this disclosure, L 11 and L 12 They may be the same or different, and each can be ethylidene, propyleneide or butylide independently.

[0078] In one exemplary embodiment of this disclosure, Q can be -SH, -NH2, or a C2 to C60 fused heterocyclic group containing O.

[0079] In one exemplary embodiment of this disclosure, Q can be -SH, -NH2, or a fused cycloalkanes of ethylene oxide and cyclohexane.

[0080] In one exemplary embodiment of this disclosure, Q can be -SH or a fused cycloalcoholic group of an ethylene oxide ring and a cyclohexane ring.

[0081] Referring to the silane coupling agents according to this disclosure, when an aminosilane coupling agent in which Q of Formula 2 is -NH2 is used alone, it can form hydrogen bonds with the -OH groups of the glass substrate, thereby reducing the bonding force between the silane coupling agent and the Pd binder, resulting in reduced adhesion under high accelerated stress testing (HAST) conditions. Therefore, Q is preferably -SH or a C2 to C60 fused heterocyclic group containing O.

[0082] In one exemplary embodiment of this disclosure, n can be 0.

[0083] In one exemplary embodiment of this disclosure, n can be 1.

[0084] In one exemplary embodiment of this disclosure, the silane coupling agent may be represented by the following chemical formula 2-1 or 2-2:

[0085] [Chemical Formula 2-1]

[0086]

[0087] [Chemical Formula 2-2]

[0088]

[0089] In chemical formulas 2-1 and 2-2,

[0090] R1 to R3 may be the same or different, and each is independently a C1 to C5 alkyl group.

[0091] L 11 and L 12 They may be the same or different, and each is independently a C1 to C5 alkylene group, and

[0092] Q is -SH, -NH2, or a fused heterocyclic group containing O.

[0093] In one exemplary embodiment of this disclosure, the silane coupling agent may be represented by the above chemical formula 2-1.

[0094] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition may comprise one or two silane coupling agents represented by the above chemical formula 2.

[0095] 2) Pd adhesive

[0096] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition may contain one or more Pd binders.

[0097] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition may contain two or more Pd binders.

[0098] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition may contain one or two Pd binders.

[0099] In one exemplary embodiment of this disclosure, the Pd binder may be a compound containing metal ions.

[0100] In one exemplary embodiment of this disclosure, the Pd binder may be a lithium-ion-containing compound.

[0101] In one exemplary embodiment of this disclosure, the Pd binder contains functional groups capable of binding with a silane coupling agent.

[0102] In one exemplary embodiment of this disclosure, the Pd binder may include a carboxyl group as a functional group capable of binding with a silane coupling agent.

[0103] In one exemplary embodiment of this disclosure, the Pd binder may be represented by the following chemical formula 1:

[0104] [Chemical Formula 1]

[0105]

[0106] In chemical formula 1,

[0107] L1 to L3 may be the same or different, and each is independently a C1 to C5 alkylene group.

[0108] X1 is -NH2, -OH, -C(=O)OH, or -P(=O)(OH)2.

[0109] X2 and X3 may be the same or different, and each is independently -NH2, -OH, -C(=O)OH, or -C(=O)O. - M + , -P(=O)(OH)2, -P(=O)(OH)(O - M + ) or -P(=O)(O - M + )2,

[0110] M is Li or Na, and

[0111] At least one of X2 and X3 is -C(=O)O - M + -P(=O)(OH)(O) - M + ) or -P(=O)(O - M + )2.

[0112] The Pd binder according to this disclosure is characterized in that it contains an amino, hydroxyl, carboxyl or phosphonic acid group in its tertiary amine structure, and contains at least one metal ion.

[0113] In one exemplary embodiment of this disclosure, the functional group of the Pd binder that can bind to the silane coupling agent may be X1 of the above chemical formula 1.

[0114] Because the Pd binder represented by chemical formula 1 contains -C(=O)O - M + -P(=O)(OH)(O) - M + ) or -P(=O)(O - M + Therefore, it possesses high ionic properties and can readily dissociate in the composition, with corresponding sites selectively reacting with the Pd catalyst. In other words, the Pd binder represented by Formula 1 exhibits excellent binding force with the Pd catalyst and can form a uniform metal layer during the plating process.

[0115] Furthermore, when the linking groups (L1 to L3) of the Pd binder represented by Formula 1 contain heteroatoms (S, N, etc.), it is difficult to control the binding sites with the Pd binder. However, since the Pd binder represented by Formula 1 contains hydrocarbon linking groups (L1 to L3) of sufficient length, a stable three-dimensional structure can be formed.

[0116] In one exemplary embodiment of this disclosure, L1 to L3 may be the same or different, and may each be methylene, ethylene, propylene, butylene, or pentylene.

[0117] In one exemplary embodiment of this disclosure, L1 to L3 may be the same or different, and may each be an alkylene group of C1 to C3 independently.

[0118] In one exemplary embodiment of this disclosure, L1 to L3 may be the same or different, and may each be methylene, ethylene or propylene independently.

[0119] In one exemplary embodiment of this disclosure, when the alkylene groups of L1 to L3 have increased lengths, there is a problem that the reaction is difficult to carry out in the aqueous phase.

[0120] In one exemplary embodiment of this disclosure, X1 can be -C(=O)OH or -P(=O)(OH)2.

[0121] In one exemplary embodiment of this disclosure, X1 can be -C(=O)OH.

[0122] In one exemplary embodiment of this disclosure, X1 can be -P(=O)(OH)2.

[0123] In one exemplary embodiment of this disclosure, X2 and X3 may be the same or different, and may each be independently -C(=O)OH or -C(=O)O. - Li + , -P(=O)(OH)2, -P(=O)(OH)(O - Li + ) or -P(=O)(O - Li + )2, and at least one of X2 and X3 can be -C(=O)O - Li + -P(=O)(OH)(O) - Li + ) or -P(=O)(O - Li + )2.

[0124] In one exemplary embodiment of this disclosure, X2 and X3 can be -C(=O)O - Li + -P(=O)(OH)(O) - Li + ) or -P(=O)(O - Li + )2.

[0125] In one exemplary embodiment of this disclosure, M can be Li or Na.

[0126] In one exemplary embodiment of this disclosure, M is preferably Li, and in this case, a higher binding force with Pd can be provided compared to the case where M is Na.

[0127] In one exemplary embodiment of this disclosure, when M is K or Cu, it exhibits lower ionic properties compared to Li, and therefore has lower Pd adhesion, making it difficult to form a uniform coating.

[0128] In one exemplary embodiment of this disclosure, the Pd binder may be represented by the following chemical formula 1-1 or 1-2:

[0129] [Chemical Formula 1-1]

[0130]

[0131] [Chemical Formula 1-2]

[0132]

[0133] In chemical formulas 1-1 and 1-2,

[0134] L1 to L3 may be the same or different, and each is independently a C1 to C5 alkylene group;

[0135] Z is -OH or -O - M + ,

[0136] Y1 to Y3 may be the same or different, and each is independently -OH or -O. - M + ,as well as

[0137] M is either Li or Na.

[0138] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition may comprise one or two Pd binders represented by the above chemical formula 1.

[0139] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition may comprise a Pd binder represented by the above chemical formula 1.

[0140] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition may further include an additional Pd binder besides the Pd binder represented by the above chemical formula 1.

[0141] In one exemplary embodiment of this disclosure, the additional Pd binder may not contain metal ions.

[0142] In one exemplary embodiment of this disclosure, the additional Pd binder may not be a compound containing metal ions.

[0143] In one exemplary embodiment of this disclosure, the additional Pd binder may be represented by the following chemical formula 3:

[0144] [Chemical Formula 3]

[0145]

[0146] In chemical formula 3,

[0147] L 21 To L 23 They may be the same or different, and each is independently a C1 to C5 alkylene group, and

[0148] X 21 To X 23 They may be the same or different, and each is independently -C(=O)OH or -P(=O)(OH)2.

[0149] 3) Phase stabilizers

[0150] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition may further comprise a phase stabilizer selected from hydrochloric acid, sulfuric acid, methanol, ethanol, isopropanol, and sodium hydroxide.

[0151] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition may contain one or more phase stabilizers.

[0152] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition may contain two or more phase stabilizers.

[0153] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition may contain one or two phase stabilizers.

[0154] In one exemplary embodiment of this disclosure, when a phase stabilizer is used, the pH of the composition can be controlled to a range of 0.5 to 5 or 9 to 12, so that hydrogen bonding between the -OH groups of the glass substrate and the silane coupling agent can proceed smoothly.

[0155] The role of phase stabilizers is to control the pH to a desired range and improve the stability of silane coupling agents. Specifically, pH can be controlled by using phase stabilizers such as hydrochloric acid, sulfuric acid, or sodium hydroxide, and the stability of silane coupling agents can be increased by using phase stabilizers such as methanol, ethanol, or isopropanol.

[0156] In one exemplary embodiment of this disclosure, the phase stabilizer may comprise one selected from methanol, ethanol, or isopropanol.

[0157] In one exemplary embodiment of this disclosure, the phase stabilizer may comprise one selected from hydrochloric acid, sulfuric acid and sodium hydroxide, and one selected from methanol, ethanol and isopropanol.

[0158] In one exemplary embodiment of this disclosure, the phase stabilizer may comprise hydrochloric acid and isopropanol.

[0159] 4) Solvent

[0160] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition may further include a solvent.

[0161] In one exemplary embodiment of this disclosure, the solvent may be water.

[0162] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition further comprises a solvent, and based on the total weight of 100 parts by weight of the glass substrate metallization acceleration composition, it may contain 0.1 to 5 parts by weight of a silane coupling agent and 0.3 to 5 parts by weight of a Pd binder, with the balance being solvent.

[0163] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition further comprises a solvent, and based on the total weight of 100 parts by weight of the glass substrate metallization acceleration composition, it may contain 0.2 to 3 parts by weight of a silane coupling agent and 0.3 to 3 parts by weight of a Pd binder, with the balance being solvent.

[0164] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition further comprises a solvent, and based on the total weight of 100 parts by weight of the glass substrate metallization acceleration composition, it may contain 0.3 to 2 parts by weight of a silane coupling agent and 0.5 to 3 parts by weight of a Pd binder, with the balance being solvent.

[0165] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition further comprises a solvent, and based on the total weight of 100 parts by weight of the glass substrate metallization acceleration composition, it may contain 0.5 to 2 parts by weight of a silane coupling agent and 0.5 to 3 parts by weight of a Pd binder, with the balance being solvent.

[0166] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition may further comprise a solvent and a phase stabilizer, and based on the total weight of 100 parts by weight of the glass substrate metallization acceleration composition, it may comprise 0.1 to 5 parts by weight of a silane coupling agent, 0.3 to 5 parts by weight of a Pd binder, and 1 to 20 parts by weight of a phase stabilizer, with the balance being a solvent.

[0167] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition may further comprise a solvent and a phase stabilizer, and based on the total weight of 100 parts by weight of the glass substrate metallization acceleration composition, it may comprise 0.2 to 3 parts by weight of a silane coupling agent, 0.3 to 3 parts by weight of a Pd binder, and 1 to 15 parts by weight of a phase stabilizer, with the balance being a solvent.

[0168] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition may further comprise a solvent and a phase stabilizer, and based on the total weight of 100 parts by weight of the glass substrate metallization acceleration composition, it may comprise 0.3 to 2 parts by weight of a silane coupling agent, 0.5 to 3 parts by weight of a Pd binder, and 1 to 10 parts by weight of a phase stabilizer, with the balance being a solvent.

[0169] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition may further comprise a solvent and a phase stabilizer, and based on the total weight of 100 parts by weight of the glass substrate metallization acceleration composition, it may comprise 0.5 to 2 parts by weight of a silane coupling agent, 0.5 to 3 parts by weight of a Pd binder, and 1 to 8 parts by weight of a phase stabilizer, with the balance being a solvent.

[0170] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition may further comprise a solvent, a phase stabilizer, and an additional Pd binder, and based on the total weight of 100 parts by weight of the glass substrate metallization acceleration composition, it may comprise 0.1 to 5 parts by weight of a silane coupling agent, 0.3 to 5 parts by weight of a Pd binder, 1 to 20 parts by weight of a phase stabilizer, and 0.1 to 5 parts by weight of an additional Pd binder, with the balance being solvent.

[0171] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition may further comprise a solvent, a phase stabilizer, and an additional Pd binder, and based on the total weight of 100 parts by weight of the glass substrate metallization acceleration composition, it may comprise 0.2 to 3 parts by weight of a silane coupling agent, 0.3 to 3 parts by weight of a Pd binder, 1 to 15 parts by weight of a phase stabilizer, and 0.1 to 4 parts by weight of an additional Pd binder, with the balance being solvent.

[0172] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition may further comprise a solvent, a phase stabilizer, and an additional Pd binder, and based on the total weight of 100 parts by weight of the glass substrate metallization acceleration composition, it may comprise 0.3 to 2 parts by weight of a silane coupling agent, 0.5 to 3 parts by weight of a Pd binder, 1 to 10 parts by weight of a phase stabilizer, and 0.3 to 3 parts by weight of an additional Pd binder, with the balance being solvent.

[0173] Method for preparing glass substrate metallization acceleration compositions

[0174] Another exemplary embodiment of this disclosure provides a method for preparing a glass substrate metallization acceleration composition, comprising the steps of: preparing a mixture by mixing a silane coupling agent with a Pd binder; and stirring the mixture, characterized in that the Pd binder contains functional groups capable of binding with the silane coupling agent and is a metal ion-containing compound.

[0175] In one exemplary embodiment of this disclosure, the mixture may also contain a solvent and a phase stabilizer.

[0176] A method for preparing a glass substrate metallization acceleration composition according to an exemplary embodiment of the present disclosure may include the steps of: preparing a mixture by mixing a solvent, at least one silane coupling agent, at least one Pd binder and at least one phase stabilizer; and stirring the mixture.

[0177] The detailed descriptions of each of the solvent, silane coupling agent, Pd binder, and phase stabilizer are the same as those described above for the glass substrate metallization acceleration composition.

[0178] In one exemplary embodiment of this disclosure, the step of stirring the mixture is performed at a temperature of 15°C to 25°C.

[0179] In one exemplary embodiment of this disclosure, the step of stirring the mixture is carried out for 1 to 3 hours.

[0180] In one exemplary embodiment of this disclosure, the solvent, silane coupling agent, Pd binder, and phase stabilizer can be mixed in any order.

[0181] In one exemplary embodiment of this disclosure, 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 with a solvent.

[0182] In one exemplary embodiment of this disclosure, the step of preparing the mixture may include the following steps: mixing at least one phase stabilizer with a solvent to prepare a first mixture; mixing at least one Pd binder with the first mixture to prepare a second mixture; and mixing at least one silane coupling agent with the second mixture to prepare a third mixture.

[0183] When the mixture is prepared in the order described above, greater stability is achieved.

[0184] The process of manufacturing glass substrates

[0185] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition can be used in the process of manufacturing a glass substrate.

[0186] In one exemplary embodiment of this disclosure, the process of manufacturing a glass substrate may include a process of forming through-holes in the glass substrate and a glass substrate metallization process.

[0187] Specifically, the glass substrate metallization acceleration composition according to this disclosure can be used in the glass substrate metallization process.

[0188] In one exemplary embodiment of this disclosure, the thickness of the glass substrate can be from 0.3 mm to 1.2 mm.

[0189] In one exemplary embodiment of this disclosure, the thickness of the glass substrate can be from 0.4 mm to 1.2 mm.

[0190] In one exemplary embodiment of this disclosure, the thickness of the glass substrate can be from 0.6 mm to 1.2 mm.

[0191] In one exemplary embodiment of this disclosure, the glass substrate may include through-holes.

[0192] In one exemplary embodiment of this disclosure, the through-hole can have different shapes depending on the method used to form it, and there are no particular limitations. For example, the through-hole can have a cylindrical shape or an hourglass-like shape.

[0193] In one exemplary embodiment of this disclosure, the glass substrate may be a through-glass via (TGV) substrate.

[0194] In one exemplary embodiment of this disclosure, the diameter of the through-hole in the glass substrate can be from 10 μm to 140 μm.

[0195] In one exemplary embodiment of this disclosure, the diameter of the through-hole in the glass substrate refers to the diameter of the through-hole that can be determined on the outside of the glass substrate. In other words, the diameter of the through-hole can be the diameter of the hole on the top surface of the glass substrate. Specifically, when... Figure 2 As shown, when the through hole has an hourglass shape, the hole can have an irregular diameter, and in this case, the diameter of the through hole can be the diameter of the hole based on the depth direction of the through hole (the direction perpendicular to the top surface of the glass substrate) being in a straight line with the top surface of the glass substrate.

[0196] In one exemplary embodiment of this disclosure, the aspect ratio of the glass substrate may be 1:6 or greater.

[0197] In this disclosure, the aspect ratio of the glass substrate can be the ratio of the diameter of the via to its depth. In other words, the aspect ratio of the glass substrate can be the ratio of the diameter of the via to the thickness of the glass substrate.

[0198] In this disclosure, the aspect ratio of the glass substrate can be the aspect ratio of the through holes in the glass substrate, specifically the ratio of the diameter of the through holes in the glass substrate to the thickness of the glass substrate.

[0199] exist Figure 2 In this context, 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 can be R:T.

[0200] In one exemplary embodiment of this disclosure, the aspect ratio of the glass substrate can be from 1:6 to 1:20.

[0201] When a glass substrate is coated using a glass substrate metallization method according to an exemplary embodiment of the present disclosure, the aspect ratio of the glass substrate can be increased.

[0202] The process will be explained in detail below.

[0203] 1) The process of forming through holes in a glass substrate

[0204] In one exemplary embodiment of this disclosure, the process of forming a via in a glass substrate may include: a glass substrate laser modification process; and a glass substrate via etching process.

[0205] In one exemplary embodiment of this disclosure, the glass substrate laser modification process is a process of inducing deformation in the glass substrate by using laser modification, and any method known to those skilled in the art can be used for this process.

[0206] In one exemplary embodiment of this disclosure, the glass substrate hole etching process is a process in which through holes are formed at locations where deformation occurs in the glass substrate, and any method known to those skilled in the art can be used for this process.

[0207] 2) Glass substrate metallization process

[0208] In one exemplary embodiment of this disclosure, the glass substrate metallization process may include: a glass substrate pretreatment process; a glass substrate metallization acceleration process; a glass substrate coating process; and an annealing process.

[0209] Figure 3 This diagram illustrates the glass substrate metallization process according to the present disclosure. Specifically, after a pretreatment process, hydroxyl groups (-OH) are formed on the surface of the glass substrate. When the glass substrate is treated with the aforementioned glass substrate metallization accelerating composition, the oxygen in the silane coupling agent 10 of 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 while simultaneously bonding with the B of the Pd binder 20. Furthermore, the A of the Pd binder 20 bonds with the Pd catalyst 30, and a metal layer (e.g., a Cu layer) is formed on the Pd catalyst 30 through a plating process. Then, Si-O-Si condensation occurs during the subsequent annealing process, bringing the metal layer into close contact with the glass substrate.

[0210] In one exemplary embodiment of this disclosure, the glass substrate metallization acceleration composition can be used in a glass substrate metallization acceleration method.

[0211] In one exemplary embodiment of this disclosure, the glass substrate metallization method may be a completely wet process.

[0212] In one exemplary embodiment of this disclosure, each of the glass substrate pretreatment process, the glass substrate metallization acceleration process, and the glass substrate coating process can be performed within 2 to 30 minutes.

[0213] Glass substrate pretreatment process

[0214] In one exemplary embodiment of this disclosure, the glass substrate pretreatment process may include a pretreatment process A of cleaning the glass substrate using a pretreatment composition A and a pretreatment process B of forming hydroxyl groups on the surface of the glass substrate using a pretreatment composition B.

[0215] In one exemplary embodiment of this disclosure, pretreatment process A and pretreatment process B may include processes of applying pretreatment composition A and pretreatment composition B, respectively, to a glass substrate. Specifically, pretreatment composition A and pretreatment composition B may be applied to the glass substrate by spraying or dipping methods.

[0216] In one exemplary embodiment of this disclosure, pretreatment composition A may comprise: an amine compound; a polar solvent; a nonpolar solvent; and a pretreatment solvent.

[0217] In one exemplary embodiment of this disclosure, the amine compound may include at least one selected from monoisopropanolamine and monoethanolamine.

[0218] In one exemplary embodiment of this disclosure, the polar solvent may include at least one selected from diethylformamide and N-methylpyrrolidone.

[0219] In one exemplary embodiment of this disclosure, the nonpolar solvent may include at least one selected from butyl diethylene glycol and ethyl diethylene glycol.

[0220] In one exemplary embodiment of this disclosure, the pretreatment solvent may be water.

[0221] In one exemplary embodiment of this disclosure, based on 100 parts by weight of pretreatment composition A, pretreatment composition A may comprise 3% to 20% by weight of an amine compound, 5% to 30% by weight of a polar solvent, 10% to 40% by weight of a nonpolar solvent, and 30% to 80% by weight of a pretreatment solvent.

[0222] In one exemplary embodiment of this disclosure, the pretreatment composition B may comprise: an acidic solution; and a pretreatment solvent.

[0223] In one exemplary embodiment of this disclosure, the acidic solution may include at least one selected from hydrochloric acid and sulfuric acid.

[0224] In one exemplary embodiment of this disclosure, the pretreatment solvent may be water.

[0225] In one exemplary embodiment of this disclosure, the pretreatment composition B may further contain an oxidizing agent.

[0226] In one exemplary embodiment of this disclosure, the oxidant may be hydrogen peroxide.

[0227] In one exemplary embodiment of this disclosure, based on 100 parts by weight of pretreatment composition B, pretreatment composition B may comprise 3% to 10% by weight of an acidic solution, 0% to 20% by weight of an oxidant, and 80% to 97% by weight of a pretreatment solvent.

[0228] Accelerated Metallization Process of Glass Substrates

[0229] Another embodiment of this disclosure provides a glass substrate metallization acceleration process, which includes the step of surface treating a glass substrate using a glass substrate metallization acceleration composition.

[0230] In one exemplary embodiment of this disclosure, the accelerated metallization process of the glass substrate may include: a pre-bonding process of the glass substrate and the Pd catalyst; and a bonding process of the glass substrate and the Pd catalyst.

[0231] In one exemplary embodiment of this disclosure, a glass substrate metallization accelerating composition may be used during the pre-bonding process of the glass substrate and the Pd catalyst.

[0232] In one exemplary embodiment of this disclosure, the pre-bonding process of the glass substrate with the Pd catalyst can be a process in which a glass substrate having hydroxyl groups formed on the surface of the glass substrate is treated with the glass substrate metallization acceleration composition described above to obtain a glass substrate containing a Pd binder that is surface-bonded to and distributed on the surface of the glass substrate.

[0233] In one exemplary embodiment of this disclosure, the glass substrate can be treated with a glass substrate metallization acceleration composition by using a spraying or dipping method.

[0234] In one exemplary embodiment of this disclosure, the process of bonding the glass substrate with the Pd catalyst can be a process of treating a glass substrate containing a Pd binder that is bonded to the surface of the glass substrate with the Pd catalyst.

[0235] In one exemplary embodiment of this disclosure, a glass substrate containing a Pd binder that bonds to the surface of a glass substrate can be treated with a Pd catalyst using an impregnation method.

[0236] In one exemplary embodiment of this disclosure, the Pd catalyst can be a Pd-containing catalyst. 2+ Catalysts with ligands are acceptable, but there are no particular limitations, as long as the Pd catalyst is one used in the art.

[0237] In one exemplary embodiment of this disclosure, the Pd catalyst may comprise [Pd-X] 2+The structure is represented by X, where X may include 2-vinylpyridine or 2-methylpyridine.

[0238] In one exemplary embodiment of this disclosure, the Pd catalyst may include a structure represented by the following structural formula:

[0239]

[0240] When a glass substrate containing a Pd binder bonded to the surface of a glass substrate is treated with a Pd catalyst, the Pd binder can react with the Pd released by the Pd catalyst. 2+ It can be ion-bound, or it can be directly bound to a Pd catalyst.

[0241] In one exemplary embodiment of this disclosure, the accelerated metallization process of the glass substrate may further include a Pd catalyst reduction process.

[0242] Specifically, the Pd catalyst reduction process can be described as reducing the Pd in ​​the Pd catalyst... 2+ The process of reducing ions to Pd metal.

[0243] In one exemplary embodiment of this disclosure, any Pd catalyst reduction process can be used, as long as it is known to those skilled in the art.

[0244] Glass substrate coating process

[0245] In one exemplary embodiment of this disclosure, the glass substrate coating process can be a process of forming a metal layer on a glass substrate.

[0246] In one exemplary embodiment of this disclosure, the metal layer may be, for example, a Cu layer.

[0247] In one exemplary embodiment of this disclosure, the glass substrate coating process can be an electroless coating process.

[0248] In one exemplary embodiment of this disclosure, the glass substrate plating process can be an electroless copper plating process.

[0249] In one exemplary embodiment of this disclosure, any glass substrate coating process can be used, as long as it is known to those skilled in the art.

[0250] In one exemplary embodiment of this disclosure, the electroplating process can be performed after the glass substrate coating process.

[0251] Annealing process

[0252] In one exemplary embodiment of this disclosure, the annealing process can be a Si-O-Si condensation process.

[0253] During the annealing process, Si-O-Si condensation occurs, allowing the metal layer to make close contact with the glass substrate.

[0254] Typically, because the annealing process is carried out at high temperatures (approximately 150°C), high bonding strength is required between the glass substrate and the metal layer, even under high temperature conditions.

[0255] In one exemplary embodiment of this disclosure, any annealing process may be used, as long as it is known to those skilled in the art.

[0256] Metallized glass substrate

[0257] Another exemplary embodiment of this disclosure provides a metallized glass substrate comprising: a glass substrate; and a metal layer disposed on the glass substrate, wherein a metallization acceleration layer is included between the glass substrate and the metal layer, and the metallization acceleration layer comprises a silane coupling agent and a Pd binder comprising functional groups and metal ions bonded to the silane coupling agent.

[0258] Another exemplary embodiment of this disclosure provides a metallized glass substrate comprising: a glass substrate having through-holes; and a metal layer disposed in the through-holes of the glass substrate, wherein a metallization acceleration layer is included between the glass substrate and the metal layer, and the metallization acceleration layer comprises a silane coupling agent and a Pd binder comprising functional groups and metal ions bonded to the silane coupling agent.

[0259] In this disclosure, a metallized glass substrate refers to a structure having a metal layer formed on at least one surface of a glass substrate.

[0260] The metallized glass substrate according to this disclosure is characterized in that the glass substrate is metallized by using a glass substrate metallization acceleration composition instead of a Cu sputtering process. Typically, when a Cu sputtering process is used, the Cu seed is formed by Ti-Cu sputtering, and the metallized glass substrate may contain Ti. On the other hand, the metallized glass substrate according to this disclosure does not use a Ti-Cu sputtering process, and therefore the metallized glass substrate does not contain Ti.

[0261] The metallized glass substrate according to this disclosure can exhibit an adhesive strength of 2B or greater, as assessed at room temperature.

[0262] The metallized glass substrate according to this disclosure can exhibit an adhesive strength of 4B or greater, as assessed at room temperature.

[0263] Metallized glass substrates according to this disclosure can exhibit bond strength of 3B or greater, as evaluated under high accelerated stress test (HAST) conditions.

[0264] The metallized glass substrates according to this disclosure can exhibit bond strengths of 5B or greater, as evaluated under HAST conditions.

[0265] In this disclosure, HAST conditions refer to 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.

[0266] The metallized glass substrates according to this disclosure can exhibit a coating uniformity of 75% or greater, as determined by image analysis.

[0267] The metallized glass substrates according to this disclosure can exhibit 90% or greater coating uniformity, as determined by image analysis.

[0268] The metallized glass substrates according to this disclosure can exhibit a coating coverage of 65% or greater.

[0269] Coating coverage refers to the Cu thickness (T1) on the surface (top surface) of a metallized glass substrate after cutting a cross-section with a focused ion beam (FIB) and measuring the Cu thickness (T2, T3, and T4) according to the location of the vias in the glass substrate (see [reference]). Figure 5 After that, the average of the T2 / T1 ratio, T3 / T1 ratio, and T4 / T1 ratio.

[0270] More specifically, the coating coverage can be calculated using Equation 1 after measuring the metal layer thickness (T1) at a position 100 μm away from the via on the top surface of the glass substrate, the metal layer thickness (T2) at a position 25% of the thickness of the via (where the thickness of the glass substrate is considered to be 100%) away from the top surface of the glass substrate, the metal layer thickness (T3) at a position 50% of the thickness of the via, and the metal layer thickness (T4) at a position 75% of the thickness of the via.

[0271] [Formula 1]

[0272]

[0273] The metallized glass substrates according to this disclosure can be used for semiconductor packaging. Specifically, the glass substrates according to this disclosure can be used to package semiconductor chips / devices. More specifically, the term "semiconductor packaging" generally refers to post-processing techniques for dicing and packaging processed wafers into chip shapes, in which glass substrates have gained attention as next-generation semiconductor packaging materials for physically / electrically connecting semiconductor chips to a system. To allow for such use as a semiconductor packaging material, several functionalities are required, including mechanical protection, electrical / mechanical connections, and heat dissipation. In particular, in the case of TGV via substrates, the glass substrate contains fine electrode paths that facilitate current flow, and therefore offers the advantage of being able to mount more chips and high-performance chips.

[0274] The metallized glass substrates according to this disclosure can be applied to fields requiring large-area packaging, such as artificial intelligence (AI), high-performance computing (HPC), data centers, servers, networks, and especially generative AI and HPC.

[0275] Invention Embodiments

[0276] The present disclosure is described in detail below by way of examples. However, embodiments of the present disclosure may take several different forms, and the scope of the present disclosure is not to be construed as limited to the embodiments described below. Examples of this specification are provided to more fully describe the present disclosure to those skilled in the art.

[0277] <Preparation Example 1> Preparation of Pd Binder (LCC-1)

[0278] After introducing 90 g (5 mol) of solvent (ultrapure water) and 8.6 g (0.2 mol) of LiOH-H2O into the reaction flask, 19.6 g (0.1 mol) of hymentriacetic acid was mixed with it and the resulting mixture was stirred at room temperature for 2 hours to prepare a solution containing 19.5 g of LCC-1 (solid) (solid content 16.9%).

[0279] <Preparation Example 2> Preparation of Glass Substrate Metallization Acceleration Composition

[0280] The silane coupling agent, Pd binder, and phase stabilizer were introduced into ultrapure water (solvent) according to the composition and content (wt%) shown in Table 1 below, and the resulting mixture was then stirred at room temperature for 2 hours to prepare a glass substrate metallization accelerated composition (balance: ultrapure water).

[0281] [Table 1]

[0282]

[0283] *S1: 3-Mercaptopropyltrimethoxysilane

[0284] *S2: Aminoethylaminopropyltrimethoxysilane

[0285] *S3: Trimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]silane*IPA: Isopropanol

[0286] *LCC-1: C6H 9-n NO6Li n (Preparation Example 1, n=2)

[0287] *Q3:

[0288] <Experimental Example 1-1> Electroless plating (Cu) on a glass substrate (0.64 mm thick)

[0289] Internal deformation was generated in a glass substrate (0.64 mm thick) by laser modification, and through-holes (100 μm TGV holes, aspect ratio 1:6) were formed by etching. The glass substrate was then pretreated to clean it and form -OH groups on its surface. The glass substrate was then immersed (at room temperature, for 5 minutes) in the glass substrate metallization acceleration composition shown in Table 2 below to apply the composition.

[0290] Then, the glass substrate was treated with Pd catalyst (immersion, 40°C, 5 minutes), reduced (immersion, 30°C, 3 minutes), electroless copper plating was performed (immersion, 34°C, 20 minutes), and finally annealed (230°C, 60 minutes).

[0291] In Comparative Example 1-1, the process of applying the glass substrate metallization accelerating composition was omitted.

[0292] <Experimental Example 1-2> Electroless plating (Cu) on a glass substrate (0.84 mm thick)

[0293] Internal deformation was generated in a glass substrate (0.84 mm thick) by laser modification, and through-holes (100 μm TGV holes, aspect ratio 1:8) were formed by etching. The glass substrate was then pretreated to clean it and form -OH groups on its surface. The glass substrate was then immersed (at room temperature, for 5 minutes) in the glass substrate metallization acceleration composition shown in Table 3 below to apply the composition.

[0294] Then, the glass substrate was treated with Pd catalyst (immersion, 40°C, 5 minutes), reduced (immersion, 30°C, 3 minutes), electroless copper plating was performed (immersion, 34°C, 20 minutes), and finally annealed (230°C, 60 minutes).

[0295] <Experimental Example 2> Evaluation of Glass Substrates

[0296] The properties of the glass substrates coated according to Experimental Examples 1-1 and 1-2 were evaluated. The results are shown in Tables 2 and 3 below. The properties shown in Tables 2 and 3 were evaluated using the following methods.

[0297] Electrical conduction

[0298] The electrical conductivity of each coated glass substrate was checked using a ohmmeter. The results were shown as O (conductivity) and X (short circuit).

[0299] Coating uniformity

[0300] The uniformity of coating on each coated glass substrate was examined by image analysis. The results were displayed as O (100% coating), □ (at least 75% coating), △ (at least 50% coating), and X (less than 50% coating).

[0301] Specifically, refer to Figure 4 The standard is to assess the uniformity of the coating by visual inspection.

[0302] Adhesion at room temperature (evaluated by cross-cut test)

[0303] At room temperature, a grid is formed on a coated glass substrate using a crisscross pattern maker (AT-CC3000 / ASTM1, available from TOC Co.). Adhesive tape (3M 898125mm × 10mm (7.6N), sp3020, available from TOC Co.) is then firmly adhered to and removed from the grid. The remaining grid shape is then evaluated. For the evaluation criteria, refer to the instructions in ASTM D3359-08.

[0304] HAST adhesive

[0305] The coated glass substrate was left to stand at 130°C and 85% humidity for 96 hours, and the same evaluation as the "adhesion at room temperature" above was performed.

[0306] Plating coverage

[0307] A cross-section of the coated glass substrate was cut using a focused ion beam (FIB), and the metal layer thickness was measured at the following locations: 100 μm from the via on the top surface of the glass substrate (T1); 25% of the thickness of the via on the top surface of the glass substrate (where the thickness of the glass substrate is considered 100%) (T2); 50% of the thickness of the via (T3); and 75% of the thickness of the via (T4). The ratios of T2 / T1, T3 / T1, and T4 / T1 were then calculated, and their average was evaluated as the coating coverage.

[0308] [Table 2]

[0309]

[0310] As can be seen from the results in Table 2, in Examples 1-1 to 1-5, where the glass substrate was subjected to an accelerated glass substrate metallization process using the composition according to this disclosure, the examples demonstrated superior performance in all evaluation items, including electrical conductivity, coating uniformity, adhesion, and coating coverage, compared to the comparative example group. In Comparative Example 1-1, where the accelerated glass substrate metallization process was not performed, the evaluation of electrical conductivity indicated that the coating was not completed. It was also indicated that coating uniformity, adhesion, and coating coverage could not be determined.

[0311] Comparative Examples 1-2 to 1-4 used glass substrate metallization accelerated compositions that did not contain Pd binder. Evaluation of electrical conductivity showed that a metal layer was formed. However, due to inadequate plating, Comparative Examples 1-2 to 1-4 exhibited lower plating uniformity and plating coverage than the examples. Furthermore, Comparative Examples 1-2 to 1-4 showed lower adhesion between the glass substrate and the metal layer in both room temperature adhesion and HAST adhesion evaluations.

[0312] Furthermore, Comparative Examples 1-5 used Q3, which does not contain metal ions, as the Pd binder. It can be seen that, even considering the different types of silane coupling agents, Comparative Examples 1-5 exhibited lower plating coverage compared to Examples 1-1 to 1-3, which used LCC-1 (containing lithium ions) as the Pd binder. From these results, it can be determined which structure is more suitable as a Pd binder. Specifically, compared to Examples 1-2, Comparative Examples 1-5 were evaluated to show higher adhesion but provided lower plating coverage. It can be inferred that these results depend on the structure of the Pd binder.

[0313] Conversely, in the cases of Examples 1-1 to 1-5 using the glass substrate metallization acceleration compositions according to this disclosure, most glass substrates were coated to 100%, exhibiting excellent coating uniformity and providing a high coating coverage of 75% or higher. Furthermore, Examples 1-1 to 1-5 demonstrated high adhesion not only at room temperature but also under HAST conditions.

[0314] However, in the case of Example 1-1 of the above embodiments, it exhibits slightly lower coating uniformity compared to other embodiments. This is believed to be because S1, used as a silane coupling agent in Example 1-1, inherently has lower phase stability compared to other silane coupling agents, and contains only IPA as a phase stabilizer.

[0315] Furthermore, in Examples 1-2 where the aminosilane coupling agent was used alone, it provided high plating uniformity and coverage, but exhibited lower adhesion compared to other examples. This indicates that when the aminosilane coupling agent was used alone, the amino groups formed hydrogen bonds with the -OH groups on the glass substrate surface, resulting in reduced adhesion to the Pd binder and consequently reduced adhesion to the metal layer.

[0316] Therefore, it can be inferred that when using an aminosilane coupling agent as a silane coupling agent, it is preferable to use it in combination with another silane coupling agent with a different structure compared to using it alone. In this case, when comparing Examples 1-3 with Examples 1-2, it can be seen that Examples 1-3, which use a combination of two types of silane coupling agents, exhibit higher adhesion and coating coverage.

[0317] Examples 1-4, which achieved the best results in the above embodiments, used two types of silane coupling agents and an additional Pd binder (Q3) besides the Pd binder (LCC-1). It can be seen that when two types of Pd binders are used as in Examples 1-4, the binding force with the Pd catalyst can be increased and the adhesion strength with the metal layer can be further increased.

[0318] In Examples 1-5, an aminosilane coupling agent was used alone (as in Examples 1-2), but two types of Pd binders were used (as in Examples 1-4). Therefore, it can be seen that Examples 1-5 exhibit increased adhesion and further improved plating coverage.

[0319] [Table 3]

[0320]

[0321] Table 3 shows the coating results for a glass substrate with a thickness of 0.84 mm. In Examples 2-1 to 2-3, even with glass substrates having a high aspect ratio, a coating coverage of 80% or higher was achieved. Conversely, in Comparative Example 2-1, a coating layer was partially formed, but the coverage was only 40%, which does not meet the level of the examples. These results demonstrate that conventional metallization methods struggle to complete the coating of through-holes in glass substrates with a thickness of 0.8 mm or greater.

[0322] As can be seen from the foregoing, uniform coating of glass substrates with a large thickness and high aspect ratio of 0.8T or greater can be achieved by using the glass substrate metallization acceleration composition according to the present disclosure.

Claims

1. A glass substrate metallization acceleration composition comprising: a silane coupling agent; and a Pd binder, wherein the Pd binder is a metal ion-containing compound containing functional groups capable of binding with the silane coupling agent.

2. The glass substrate metallization acceleration composition according to claim 1, wherein the Pd binder is represented by the following chemical formula 1: [Chemical Formula 1] In chemical formula 1, L1 to L3 may be the same or different, and each is independently a C1 to C5 alkylene group. X1 is -NH2, -OH, -C(=O)OH, or -P(=O)(OH)2. X2 and X3 may be the same or different, and each is independently -NH2, -OH, -C(=O)OH, or -C(=O)O. - M + , -P(=O)(OH)2, -P(=O)(OH)(O - M + ) or -P(=O)(O - M + )2, M is Li or Na, and At least one of X2 and X3 is -C(=O)O - M + -P(=O)(OH)(O) - M + ) or -P(=O)(O - M + )2.

3. The glass substrate metallization acceleration composition according to claim 1, wherein the silane coupling agent is represented by the following chemical formula 2: [Chemical Formula 2] In chemical formula 2, R1 to R3 may be the same or different, and each is independently a C1 to C5 alkyl group. L 11 and L 12 They may be the same or different, and each is independently a C1 to C5 alkylene group. n is 0 or 1, and Q is -SH, -NH2, or a fused heterocyclic group containing O.

4. The glass substrate metallization acceleration composition according to claim 1 further comprises a phase stabilizer selected from hydrochloric acid, sulfuric acid, methanol, ethanol, isopropanol and sodium hydroxide.

5. The glass substrate metallization acceleration composition according to claim 1, further comprising a solvent and a phase stabilizer, and based on 100 parts by weight of the glass substrate metallization acceleration composition, the silane coupling agent is included in 0.1 to 5 parts by weight, the Pd binder is included in 0.3 to 5 parts by weight, and the phase stabilizer is included in 1 to 20 parts by weight.

6. A method for preparing a glass substrate metallization acceleration composition, comprising the following steps: The mixture was prepared by mixing a silane coupling agent with a Pd binder; and the mixture was stirred. The Pd binder is a metal ion-containing compound containing functional groups capable of binding with the silane coupling agent.

7. The method for preparing a glass substrate metallization acceleration composition according to claim 6, wherein the step of stirring the mixture is carried out at 15°C to 25°C.

8. The method for preparing a glass substrate metallization accelerated composition according to claim 6, wherein the step of stirring the mixture is carried out for 1 hour to 3 hours.

9. A method for accelerating metallization of a glass substrate, comprising the step of surface treatment of a glass substrate using a glass substrate metallization accelerating composition according to any one of claims 1 to 5.

10. A metallized glass substrate, comprising: Glass substrate; and a metal layer disposed on the glass substrate, A metallization acceleration layer is included between the glass substrate and the metal layer, and The metallization acceleration layer comprises a silane coupling agent and a Pd binder containing functional groups and metal ions bonded to the silane coupling agent.

11. A metallized glass substrate, comprising: A glass substrate with through holes; and the metal layer disposed in the through-hole of the glass substrate, A metallization acceleration layer is included between the glass substrate and the metal layer, and The metallization acceleration layer comprises a silane coupling agent and a Pd binder containing functional groups and metal ions bonded to the silane coupling agent.

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