Glass substrate metallizationaccelerating composition and preparing method thereof, process and substrate

Abstract

This disclosure aims to provide a composition for accelerating metallization of glass substrates, comprising a silane coupling agent and a palladium binder, wherein the palladium binder is a metal ion-containing compound comprising functional groups capable of binding with the silane coupling agent. A metal layer can be uniformly formed on a glass substrate with a high aspect ratio using only a wet process.

Description

[Technical Field]

[0001] This disclosure relates to a glass substrate metallization acceleration composition, its preparation method, glass substrate metallization acceleration process, and metallized glass substrate.

[0002] This application claims priority to Korean Patent Application No. 10-2024-0118561, filed on September 2, 2024, and Korean Patent Application No. 10-2024-0201651, filed on December 31, 2024, both filed with the Korean Intellectual Property Office, the entire disclosure of which is incorporated herein by reference. [Previous Technology]

[0003] Because glass substrates perform well in terms of warpage and coefficient of thermal expansion (CTE), they can realize large-area substrates and increase the number of I / Os, which is beneficial for high-speed signaling and heat emission.

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

[0005] Therefore, there is a need to study technologies to improve the adhesion between glass and copper, and in particular, there is a need for technologies that can ensure reliability even under high temperature and high humidity conditions.

[0006] According to related technologies, after forming a copper seed on the surface of a glass substrate through copper sputtering, electroless copper plating is performed. However, its disadvantage is that when the thickness of the glass substrate increases or when the diameter of the through glass via (TGV) hole decreases (i.e., when the aspect ratio increases), the copper seed cannot be formed in the central part inside the TGV hole.

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

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

[0009] [References]

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

[0011] [Technical Issues]

[0012] This disclosure aims to provide a glass substrate metallization acceleration composition, its preparation method, glass substrate metallization acceleration process, and metallized glass substrate.

[0013] [Technical Solution]

[0014] An exemplary embodiment of this disclosure provides a glass substrate metallization-accelerating composition, including a silane coupling agent and a palladium binder, wherein the palladium binder includes 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 process for preparing accelerated metallization compositions for glass substrates.

[0016] Another exemplary embodiment of the present disclosure provides a glass substrate metallization acceleration process, including the step of performing surface treatment on the glass substrate using the above-described glass substrate metallization acceleration composition.

[0017] Another exemplary embodiment of the present disclosure provides a metallized glass substrate, comprising: a glass substrate; and a metal layer provided on the glass substrate, wherein a metallization-accelerating layer is included between the glass substrate and the metal layer, and the metallization-accelerating layer includes a silane coupling agent and a palladium binder containing functional groups and metal ions bonded to the silane coupling agent.

[0018] Another exemplary embodiment of the present disclosure provides a metallized glass substrate, comprising: a glass substrate having through holes; and a metal layer provided 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 includes a silane coupling agent and a palladium binder containing functional groups and metal ions bonded to the silane coupling agent.

[0019] [Beneficial Effects]

[0020] A glass substrate metallization accelerating composition according to an exemplary embodiment of the present disclosure is characterized in that it includes at least one silane coupling agent, at least one palladium binder, and at least one phase stabilizer. When using the glass substrate metallization accelerating composition, the copper seed formation performed by copper sputtering in the conventional electroless copper plating process can be omitted, and the metallization of the glass substrate can be completed solely through a wet process.

[0021] Furthermore, by using a palladium binder, plating can be performed using a palladium catalyst without copper seed, thus this plating is unaffected by the thickness of the glass substrate or the through-glass via (TGV) holes. Therefore, an increase in the aspect ratio of the glass substrate can be expected.

[0022] Furthermore, when the glass substrate is metallized using the glass substrate metallization acceleration composition disclosed herein, the adhesion between the glass substrate and the metal layer can be enhanced not only at room temperature, but also under high temperature and high humidity conditions, thereby providing the advantage of excellent plating coverage ratio with uniform metal layer thickness.

Implementation Method

[0024] This disclosure will be explained in detail below.

[0025] In this specification, when a part is described as "include" a component, this does not exclude the existence of other components, but means that more components may be included, unless the context clearly states otherwise.

[0026] In this specification, there are no particular limitations on the glass substrate, as long as it is used as a substrate made of glass in this field. For example, the glass substrate disclosed herein may be a glass substrate with a via-hole.

[0027] In this specification, "glass substrate metallization" generally refers to plating of a glass substrate, that is, forming a metal layer on at least one surface of the glass substrate. The type of metal used for plating is not limited, but specific examples may include copper (Cu) or nickel (Ni), especially copper.

[0028] In 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 world.

[0029] In this disclosure, the alkyl group can be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 1-30. Specific examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, etc.

[0030] In this disclosure, the above-mentioned alkyl group is used to represent alkylene group, except that the alkylene group is divalent.

[0031] In this disclosure, a condensed heterocylic group refers to a monovalent ring having a heterocyclic ring fused with an aliphatic hydrocarbon ring or an aromatic hydrocarbon ring.

[0032] In this disclosure, a heterocycle includes one or more atoms other than carbon, i.e., one or more heteroatoms. Specifically, it may include one or more atoms selected from the group consisting of O, N, Se, and S. There is no particular limitation on the number of carbon atoms, but the number of carbon atoms is preferably 2-30, and the heterocycle may be monocyclic or polycyclic.

[0033] In this disclosure, there are no particular limitations on the aliphatic hydrocarbon ring, but it is preferred to have 3-30 carbon atoms. Specific examples include cyclopropane, cyclobutane, cyclopentane, cyclohexane, bi(cyclohexane), cycloheptane, cyclooctane, etc., but are not limited thereto.

[0034] In this disclosure, there are no particular limitations on the aromatic hydrocarbon ring, but it is preferred to have 6-30 carbon atoms. Specific examples include, but are not limited to, benzene (phenyl), biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, pyrene, fluorene, etc.

[0035] Glass substrate metallization-accelerating composition

[0036] An exemplary embodiment of the present disclosure provides a glass substrate metallization acceleration composition, characterized in that it includes a silane coupling agent and a palladium binder, wherein the palladium binder is a metal ion-containing compound that includes functional groups capable of binding with the silane coupling agent.

[0037] 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 palladium binder through the functional groups in the palladium binder that can bond to the silane coupling agent, and the palladium binder can be bonded to the palladium catalyst through its properties as a metal ion-containing compound.

[0038] Furthermore, by using the glass substrate metallization acceleration composition, the step of forming copper seeds by copper sputtering during plating on the glass substrate can be omitted. Since the step of forming copper seeds by copper sputtering is performed using a dry process, while the subsequent plating process is performed using a wet process, the dry and wet processes must be performed separately. On the other hand, when using the glass substrate metallization acceleration composition, the glass substrate can be metallized using only a wet process.

[0039] Figure 1 shows a process for manufacturing a glass substrate according to related technology. When forming through-holes in a glass substrate and performing plating treatment on the glass substrate with through-holes, electroless plating is performed by forming copper seeds, followed by electroplating. However, in this process, when increasing the aspect ratio by increasing the thickness of the glass substrate or decreasing the diameter of the holes, there is a problem that copper cannot be well deposited in the central part inside the holes.

[0040] Conversely, Figure 2 shows the manufacturing process of a glass substrate according to the present disclosure, wherein the integrated process of metal surface treatment / electrolytic plating, i.e. the metallization process according to the present disclosure, is carried out entirely by a wet process, and copper deposition can be properly completed even in the case of high aspect ratio, and a plating layer with uniform thickness can be formed.

[0041] In particular, since the composition according to this disclosure includes a silane coupling agent and a palladium binder, the hydroxyl groups formed on the glass substrate after the pretreatment process form hydrogen bonds with one end of the silane coupling agent, the other end of the silane coupling agent is bonded to the palladium binder, and the palladium catalyst is bonded to the palladium binder. In this way, when the palladium catalyst is formed on the substrate, copper plating is achieved through the excellent bonding force between palladium and copper.

[0042] The composition of the constituents will be described in detail below.

[0043] 1) Silane coupling agent

[0044] In an exemplary embodiment disclosed herein, the glass substrate metallization acceleration composition may include one or more silane coupling agents.

[0045] In an exemplary embodiment disclosed herein, the glass substrate metallization acceleration composition may contain two or more silane coupling agents.

[0046] In an exemplary embodiment disclosed herein, the glass substrate metallization acceleration composition may include one or two silane coupling agents.

[0047] In an exemplary embodiment disclosed herein, the silane coupling agent may be represented by the following chemical formula 2: [Chemical Formula 2] In chemical formula 2, R1 to R3 are the same or different and are each independently C1-C5 alkyl, L11 and L12 are the same or different and are each independently C1-C5 alkylene, n is 0 or 1, and Q is -SH, -NH2 or an O-containing fused heterocyclic group.

[0048] In an exemplary embodiment disclosed herein, at least one of R1 to R3 in the above-mentioned chemical formula 2 can form a hydrogen bond with -OH on the surface of the glass substrate.

[0049] In an exemplary embodiment disclosed herein, Q in Formula 2 may be combined with a palladium binder.

[0050] In the exemplary embodiments disclosed herein, R1 to R3 may be the same or different, and each may be independently methyl, ethyl, propyl, butyl or pentyl.

[0051] In the exemplary embodiments disclosed herein, R1 to R3 may be the same or different, and each may be independently methyl or ethyl.

[0052] In the exemplary embodiments disclosed herein, L11 and L12 may be the same or different, and each may be independently methylene group, ethylene group, propylene group, butylene group or pentylene group.

[0053] In the exemplary embodiments disclosed herein, L11 and L12 may be the same or different, and each may be independently a C2-C4 alkylene group.

[0054] In the exemplary embodiments disclosed herein, L11 and L12 may be the same or different, and each may be independently ethylidene, propyleneide or butylidene.

[0055] In the exemplary embodiments disclosed herein, Q may be -SH, -NH2 or an O-containing C2-C60 fused heterocyclic group.

[0056] In the exemplary embodiments disclosed herein, Q may be -SH, -NH2, or a condensed cyclic group of an oxirane ring and a cyclohexane ring.

[0057] In the exemplary embodiments disclosed herein, Q may be -SH or a fused cyclic group of an epoxy ring and a cyclohexane ring.

[0058] Referring to the silane coupling agent disclosed herein, when an aminosilane coupling agent with Q of Formula 2 being -NH2 is used alone, it may form hydrogen bonds with the -OH groups of the glass substrate, leading to a decrease in the bonding force between the silane coupling agent and the palladium adhesive, resulting in reduced adhesion under highly accelerated stress test (HAST) conditions. Therefore, Q is preferably -SH or an O-containing C2-C60 fused heterocyclic group.

[0059] In the exemplary embodiments disclosed herein, n may be 0.

[0060] In the exemplary embodiments disclosed herein, n may be 1.

[0061] In the exemplary embodiments disclosed herein, the silane coupling agent may be represented by the following chemical formula 2-1 or 2-2: [Chemical Formula 2-1] [Chemical Formula 2-2] In Chemical Formula 2-1 and Chemical Formula 2-2, R₁ to R₃ are the same or different and are each independently C1-C5 alkyl, L₁₁ and L₁₂ are the same or different and are each independently C1-C5 alkylene, and Q is -SH, -NH₂ or an O-containing fused heterocyclic group.

[0062] In the exemplary embodiments disclosed herein, the silane coupling agent may be represented by the above-described chemical formula 2-1.

[0063] In an exemplary embodiment disclosed herein, the glass substrate metallization acceleration composition may include one or two silane coupling agents represented by the above chemical formula 2.

[0064] 2) Palladium binder (Pd binder)

[0065] In an exemplary embodiment disclosed herein, the glass substrate metallization acceleration composition may include one or more palladium binders.

[0066] In an exemplary embodiment disclosed herein, the glass substrate metallization acceleration composition may include two or more palladium binders.

[0067] In an exemplary embodiment disclosed herein, the glass substrate metallization acceleration composition may include one palladium binder or two palladium binders.

[0068] In an exemplary embodiment disclosed herein, the palladium binder may be a metal ion-containing compound.

[0069] In an exemplary embodiment disclosed herein, the palladium binder may be a lithium-ion compound.

[0070] In an exemplary embodiment disclosed herein, the palladium binder includes functional groups capable of binding with a silane coupling agent.

[0071] In an exemplary embodiment disclosed herein, the palladium binder may include a carboxyl group as a functional group capable of binding with a silane coupling agent.

[0072] In an exemplary embodiment of this disclosure, the palladium binder may be represented by the following chemical formula 1: [Chemical Formula 1] In chemical formula 1, L1 to L3 may be the same or different and are each independently C1-C5 alkylene, X₁ is -NH2, -OH, -C(=O)OH or -P(=O)(OH)2, X2 and X3 may be the same or different and are 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 lithium or sodium, and at least one of X2 and X3 is -C(=O)O-M+, -P(=O)(OH)(O-M+) or -P(=O)(O-M+)2.

[0073] The palladium binder disclosed herein is characterized in that it contains an amino group, a hydroxyl group, a carboxyl group or a phosphonate group in its tertiary amine structure, and contains at least one metal ion.

[0074] In an exemplary embodiment disclosed herein, the functional group of the palladium binder capable of binding with the silane coupling agent may be X1 in the above-described chemical formula 1.

[0075] Because the palladium binder represented by Formula 1 contains -C(=O)O-M+, -P(=O)(OH)(O-M+) or -P(=O)(O-M+)2, it has high ionic properties, can be easily dissociated in the composition, and can selectively react with the palladium catalyst at the corresponding positions. In other words, the palladium binder represented by Formula 1 exhibits excellent binding force with the palladium catalyst and can form a uniform metal layer during the plating process.

[0076] Furthermore, when the linker (L1 to L3) of the palladium binder represented by Formula 1 contains heteroatoms (S, N, etc.), it is difficult to control the binding site with the palladium binder. However, since the palladium binder represented by Formula 1 contains hydrocarbon linkers (L1 to L3) of appropriate length, a stable three-dimensional structure can be formed.

[0077] In the exemplary embodiments disclosed herein, L1 to L3 may be the same or different, and each may be independently methylene, ethylene, propylene, butylene group or pentylene.

[0078] In the exemplary embodiments disclosed herein, L1 to L3 may be the same or different, and each may be independently a C1-C3 alkyl group.

[0079] In the exemplary embodiments disclosed herein, L1 to L3 may be the same or different, and each may be independently methylene, ethylene or propylene.

[0080] In the exemplary embodiments disclosed herein, when the alkyl length of L1 to L3 increases, there is a problem that the reaction is difficult to carry out in the aqueous solution phase.

[0081] In the exemplary embodiments disclosed herein, X1 may be -C(=O)OH or -P(=O)(OH)2.

[0082] In the exemplary embodiments disclosed herein, X1 may be -C(=O)OH.

[0083] In the exemplary embodiments disclosed herein, X1 may be -P(=O)(OH)2.

[0084] In the exemplary embodiments disclosed herein, X2 and X3 may be the same or different, and each may independently be -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 X2 and X3 may be -C(=O)O-Li+, -P(=O)(OH)(O-Li+) or -P(=O)(O-Li+)2.

[0085] In the exemplary embodiments disclosed herein, X2 and X3 may be -C(=O)O-Li+, -P(=O)(OH)(O-Li+) or -P(=O)(O-Li+)2.

[0086] In the exemplary embodiments disclosed herein, M may be lithium (Li) or sodium (Na).

[0087] In the exemplary embodiments disclosed herein, M is preferably lithium, which provides a higher binding force with palladium (Pd) compared to the case where M is sodium.

[0088] In the exemplary embodiments disclosed herein, when M is potassium (K) or copper (Cu), it exhibits lower ionic properties than lithium, making it difficult to form a uniform coating layer.

[0089] In an exemplary embodiment of this disclosure, the palladium binder may be represented by the following chemical formula 1-1 or 1-2: [Chemical Formula 1-1] [Chemical Formula 1-2] In chemical formula 1-1 and chemical formula 1-2, L1 to L3 are the same or different and are each independently C1-C5 alkyl, Z is -OH or -O-M+, Y1 to Y3 are the same or different and are each independently -OH or -O-M+, and M is lithium or sodium.

[0090] In an exemplary embodiment disclosed herein, the glass substrate metallization acceleration composition may include one palladium binder represented by the above chemical formula 1 or two palladium binders represented by the above chemical formula 1.

[0091] In an exemplary embodiment disclosed herein, the glass substrate metallization acceleration composition may include a palladium binder represented by the above chemical formula 1.

[0092] In an exemplary embodiment disclosed herein, the glass substrate metallization acceleration composition may further include an additional palladium binder in addition to the palladium binder represented by the above chemical formula 1.

[0093] In the exemplary embodiments disclosed herein, the additional palladium binder may not contain metal ions.

[0094] In the exemplary embodiments disclosed herein, the additional palladium binder may not be a metal ion compound.

[0095] In an exemplary embodiment of this disclosure, the additional palladium binder may be represented by the following chemical formula 3: [Chemical Formula 3] In chemical formula 3, L21 to L23 are the same or different and are each independently C1-C5 alkyl, and L21 to L23 are the same or different and are each independently -C(=O)OH or -P(=O)(OH)2.

[0096] 3) Phase stabilizer

[0097] In an exemplary embodiment disclosed herein, the glass substrate metallization acceleration composition may further include a phase stabilizer selected from hydrochloric acid, sulfuric acid, methanol, ethanol, isopropyl alcohol, and sodium hydroxide.

[0098] In an exemplary embodiment disclosed herein, the glass substrate metallization acceleration composition may include one or more phase stabilizers.

[0099] In an exemplary embodiment disclosed herein, the glass substrate metallization acceleration composition may include two or more phase stabilizers.

[0100] In an exemplary embodiment disclosed herein, the glass substrate metallization acceleration composition may include one phase stabilizer or two stabilizers.

[0101] In the exemplary embodiments disclosed herein, when a phase stabilizer is used, the pH of the composition can be controlled within the range of 0.5-5 or 9-12, so that the hydrogen bond formation between the -OH group of the glass substrate and the silane coupling agent can proceed smoothly.

[0102] The function of the phase stabilizer is to control the pH to the desired range and improve the stability of the silane coupling agent. Specifically, the pH can be controlled by using a phase stabilizer (such as hydrochloric acid, sulfuric acid, or sodium hydroxide), and the stability of the silane coupling agent can be increased by using a phase stabilizer (such as methanol, ethanol, or isopropanol).

[0103] In the exemplary embodiments disclosed herein, the phase stabilizer may include one of methanol, ethanol or isopropanol.

[0104] In an exemplary embodiment disclosed herein, the phase stabilizer may include one selected from hydrochloric acid, sulfuric acid and sodium hydroxide, and one selected from methanol, ethanol and isopropanol.

[0105] In an exemplary embodiment disclosed herein, the phase stabilizer may include hydrochloric acid and isopropanol.

[0106] 4) Solvent

[0107] In an exemplary embodiment disclosed herein, the glass substrate metallization acceleration composition may further include a solvent.

[0108] In the exemplary embodiments disclosed herein, the solvent may be water.

[0109] In an exemplary embodiment disclosed herein, the glass substrate metallization acceleration composition further includes a solvent, and based on 100 parts by weight of the total weight of the glass substrate metallization acceleration composition, it may include 0.1-5 parts by weight of a silane coupling agent and 0.3-5 parts by weight of a palladium binder, with the remainder being a solvent.

[0110] In an exemplary embodiment disclosed herein, the glass substrate metallization acceleration composition further includes a solvent, and based on 100 parts by weight of the total weight of the glass substrate metallization acceleration composition, it may include 0.2-3 parts by weight of a silane coupling agent and 0.3-3 parts by weight of a palladium binder, with the remainder being a solvent.

[0111] In an exemplary embodiment disclosed herein, the glass substrate metallization acceleration composition further includes a solvent, and based on 100 parts by weight of the total weight of the glass substrate metallization acceleration composition, it may include 0.3-2 parts by weight of a silane coupling agent and 0.5-3 parts by weight of a palladium binder, with the remainder being a solvent.

[0112] In an exemplary embodiment disclosed herein, the glass substrate metallization acceleration composition further includes a solvent, and based on 100 parts by weight of the total weight of the glass substrate metallization acceleration composition, it may include 0.5-2 parts by weight of a silane coupling agent and 0.5-3 parts by weight of a palladium binder, with the remainder being a solvent.

[0113] In an exemplary embodiment disclosed herein, the glass substrate metallization accelerating composition further includes a solvent and a phase stabilizer, and based on 100 parts by weight of the total weight of the glass substrate metallization accelerating composition, it may include 0.1-5 parts by weight of a silane coupling agent, 0.3-5 parts by weight of a palladium binder and 1-20 parts by weight of a phase stabilizer, with the remainder being a solvent.

[0114] In an exemplary embodiment disclosed herein, the glass substrate metallization accelerating composition further includes a solvent and a phase stabilizer, and based on 100 parts by weight of the total weight of the glass substrate metallization accelerating composition, it may include 0.2-3 parts by weight of a silane coupling agent, 0.3-3 parts by weight of a palladium binder and 1-15 parts by weight of a phase stabilizer, with the remainder being a solvent.

[0115] In an exemplary embodiment disclosed herein, the glass substrate metallization accelerating composition further includes a solvent and a phase stabilizer, and based on 100 parts by weight of the total weight of the glass substrate metallization accelerating composition, it may include 0.3-2 parts by weight of a silane coupling agent, 0.5-3 parts by weight of a palladium binder and 1-10 parts by weight of a phase stabilizer, with the remainder being a solvent.

[0116] In an exemplary embodiment disclosed herein, the glass substrate metallization accelerating composition further includes a solvent and a phase stabilizer, and based on 100 parts by weight of the total weight of the glass substrate metallization accelerating composition, it may include 0.5-2 parts by weight of a silane coupling agent, 0.5-3 parts by weight of a palladium binder and 1-8 parts by weight of a phase stabilizer, with the remainder being a solvent.

[0117] In an exemplary embodiment disclosed herein, the glass substrate metallization accelerating composition further includes a solvent, a phase stabilizer, and an additional palladium binder, and based on 100 parts by weight of the total weight of the glass substrate metallization accelerating composition, it may include 0.1-5 parts by weight of a silane coupling agent, 0.3-5 parts by weight of a palladium binder, 1-20 parts by weight of a phase stabilizer, and 0.1-5 parts by weight of an additional palladium binder, with the remainder being a solvent.

[0118] In an exemplary embodiment disclosed herein, the glass substrate metallization accelerating composition further includes a solvent, a phase stabilizer, and an additional palladium binder, and based on 100 parts by weight of the total weight of the glass substrate metallization accelerating composition, it may include 0.2-3 parts by weight of a silane coupling agent, 0.3-3 parts by weight of a palladium binder, 1-15 parts by weight of a phase stabilizer, and 0.1-4 parts by weight of an additional palladium binder, with the remainder being a solvent.

[0119] In an exemplary embodiment disclosed herein, the glass substrate metallization accelerating composition further includes a solvent, a phase stabilizer, and an additional palladium binder, and based on 100 parts by weight of the total weight of the glass substrate metallization accelerating composition, it may include 0.3-2 parts by weight of a silane coupling agent, 0.5-3 parts by weight of a palladium binder, 1-10 parts by weight of a phase stabilizer, and 0.3-3 parts by weight of an additional palladium binder, with the remainder being a solvent.

[0120] Method for preparing glass substrate metallization accelerated composition

[0121] Another exemplary embodiment of this disclosure provides a method for preparing a glass substrate metallization accelerated composition, comprising the steps of: preparing a mixture by mixing a silane coupling agent and a palladium binder; and stirring the mixture, wherein the palladium binder comprises a functional group capable of binding with the silane coupling agent and is a compound containing metal ions.

[0122] In an exemplary embodiment disclosed herein, the mixture may further include a solvent and a phase stabilizer.

[0123] According to an exemplary embodiment of the present disclosure, a method for preparing a glass substrate metallization acceleration composition may include the steps of: preparing a mixture by mixing a solvent, at least one silane coupling agent, at least one palladium binder and at least one phase stabilizer; and stirring the mixture.

[0124] The solvent, silane coupling agent, palladium binder and phase stabilizer are each described in the same detail as those described in the above reference glass substrate metallization acceleration composition.

[0125] In the exemplary embodiments disclosed herein, the step of stirring the mixture is performed at a temperature of 15-25°C.

[0126] In the exemplary embodiment disclosed herein, the step of stirring the mixture is performed for 1-3 hours.

[0127] In the exemplary embodiments disclosed herein, the solvent, silane coupling agent, palladium binder, and phase stabilizer can be mixed in any order.

[0128] In an 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 palladium binder and at least one phase stabilizer with a solvent.

[0129] In an exemplary embodiment disclosed herein, the step of preparing the mixture may include the steps of: mixing at least one phase stabilizer with a solvent to prepare a first mixture; mixing at least one palladium 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.

[0130] Higher stability is achieved when the mixture is prepared in the order described above.

[0131] Process for manufacturing glass substrate

[0132] In the exemplary embodiments disclosed herein, the glass substrate metallization acceleration composition can be used in the manufacturing process of the glass substrate.

[0133] In an exemplary embodiment disclosed herein, 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.

[0134] Specifically, the glass substrate metallization acceleration composition disclosed herein can be used in glass substrate metallization processes.

[0135] In the exemplary embodiments disclosed herein, the glass substrate may have a thickness of 0.3-1.2 millimeters (mm).

[0136] In the exemplary embodiments disclosed herein, the glass substrate may have a thickness of 0.4-1.2 mm.

[0137] In the exemplary embodiments disclosed herein, the glass substrate may have a thickness of 0.6-1.2 mm.

[0138] In an exemplary embodiment disclosed herein, the glass substrate may include a via-hole.

[0139] In the exemplary embodiments disclosed herein, the through-hole may have different shapes depending on the manufacturing process in which it is formed, and is not particularly limited thereto. For example, the through-hole may have a cylindrical shape or an hourglass-like shape.

[0140] In an exemplary embodiment disclosed herein, the glass substrate may be a through glass via (TGV) substrate.

[0141] In an exemplary embodiment disclosed herein, the through-hole of the glass substrate may have a diameter of 10-140 micrometers (μm).

[0142] In the exemplary embodiments disclosed herein, the diameter of the through-hole in the glass substrate refers to the diameter of the through-hole that can be determined from 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 the through-hole has an hourglass shape as shown in FIG2, the hole can have an irregular diameter. In this case, the diameter of the through-hole can be the diameter of the hole that is in a straight line with the top surface of the glass substrate in the depth direction (the direction perpendicular to the top surface of the glass substrate).

[0143] In the exemplary embodiments disclosed herein, the glass substrate may have an aspect ratio of 1:6 or higher.

[0144] In this disclosure, the aspect ratio of the glass substrate can be the ratio of the diameter of the via-hole 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.

[0145] In this disclosure, the aspect ratio of the glass substrate can be the aspect ratio of the through hole in the glass substrate, specifically the ratio of the diameter of the through hole in the glass substrate to the thickness of the glass substrate.

[0146] In Figure 2, 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.

[0147] In an exemplary embodiment disclosed herein, the glass substrate may have an aspect ratio of 1:6 to 1:20.

[0148] When the glass substrate is plated using the glass substrate metallization process according to the exemplary embodiments of the present disclosure, the aspect ratio of the glass substrate can be increased.

[0149] The following will describe each process in detail.

[0150] 1) Process of forming via-holes in glass substrate

[0151] In an exemplary embodiment disclosed herein, the process of forming a through hole in a glass substrate may include: a glass substrate laser modification process; and a glass substrate hole etching process.

[0152] In the exemplary embodiments disclosed herein, the glass substrate laser modification process is a process that uses laser modification to induce deformation in the glass substrate, and any method known to those skilled in the art can be used for this process.

[0153] In the exemplary embodiments disclosed herein, the glass substrate hole etching process is a process of forming through holes at locations in the glass substrate where deformation occurs, and any method known to those skilled in the art can be used for this process.

[0154] 2) Glass substrate metallization process

[0155] In the exemplary embodiments disclosed herein, the glass substrate metallization process may include: a glass substrate pretreatment process; a glass substrate metallization acceleration process; a glass substrate plating process; and an annealing process.

[0156] Figure 3 is a schematic diagram of the glass substrate metallization process according to the present disclosure. Specifically, after the glass substrate undergoes 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 acceleration composition, the oxygen in the silane coupling agent 10 in the composition forms hydrogen bonds with the hydroxyl groups on the surface of the glass substrate, and the chain portion of the silane coupling agent is distributed on the glass substrate and simultaneously bonded to B of the palladium binder 20. Furthermore, A of the palladium binder 20 bonds to the palladium catalyst 30, and a metal layer (e.g., a copper layer) is formed on the palladium catalyst 30 through a plating process. Then, in the subsequent annealing process, Si-O-Si condensation occurs to bring the metal layer into close contact with the glass substrate.

[0157] In the exemplary embodiments disclosed herein, the glass substrate metallization acceleration composition can be used in the glass substrate metallization acceleration process.

[0158] In the exemplary embodiments disclosed herein, the glass substrate metallization process may be a fully wet process.

[0159] In the exemplary embodiments disclosed herein, each of the glass substrate pretreatment process, the glass substrate metallization acceleration process, and the glass substrate coating process can be performed within 2-30 minutes.

[0160] Glass substrate pretreatment process

[0161] In an exemplary embodiment disclosed herein, 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.

[0162] In an exemplary embodiment disclosed herein, pretreatment process A and pretreatment process B may include processes for applying pretreatment composition A and pretreatment composition B to a glass substrate, respectively. Specifically, pretreatment composition A and pretreatment composition B may be applied to the glass substrate by spraying or dipping methods.

[0163] In an exemplary embodiment disclosed herein, pretreatment component A may include: an amine compound; a polar solvent; a non-polar solvent; and a pretreatment solvent.

[0164] In an exemplary embodiment disclosed herein, the amine compound may include at least one selected from monoisopropanolamine and monoethanolamine.

[0165] In an exemplary embodiment disclosed herein, the polar solvent may include at least one selected from diethyl formamide and N-methylpyrrolidone.

[0166] In an exemplary embodiment disclosed herein, the nonpolar solvent may include at least one selected from butyl diglycol and ethyl diglycol.

[0167] In an exemplary embodiment disclosed herein, the pretreatment solvent may be water.

[0168] In an exemplary embodiment disclosed herein, based on 100 parts by weight of pretreatment composition A, pretreatment composition A may include 3-20% by weight of an amine compound, 5-30% by weight of a polar solvent, 10-40% by weight of a nonpolar solvent and 30-80% by weight of a pretreatment solvent.

[0169] In an exemplary embodiment disclosed herein, the pretreatment component B may include: an acidic solution; and a pretreatment solvent.

[0170] In an exemplary embodiment disclosed herein, the acidic solution may include at least one selected from hydrochloric acid and sulfuric acid.

[0171] In an exemplary embodiment disclosed herein, the pretreatment solvent may be water.

[0172] In an exemplary embodiment disclosed herein, the pretreatment component B may further include an oxidizing agent.

[0173] In the exemplary embodiments disclosed herein, the oxidant may be hydrogen peroxide.

[0174] In an exemplary embodiment disclosed herein, based on 100 parts by weight of pretreatment component B, pretreatment component B may include 3-10% by weight of an acidic solution, 0-20% by weight of an oxidant and 80-97% by weight of a pretreatment solvent.

[0175] Accelerated Metallization Process for Glass Substrates

[0176] Another embodiment of the present disclosure provides a glass substrate metallization acceleration process, which includes the step of performing a glass substrate surface treatment using a glass substrate metallization acceleration composition.

[0177] In an exemplary embodiment disclosed herein, the accelerated glass substrate metallization process may include: a process for preparing binding of a glass substrate with a Pd catalyst; and a process for binding the glass substrate with the Pd catalyst.

[0178] In an exemplary embodiment disclosed herein, the glass substrate metallization acceleration composition can be used in the process of preparing a glass substrate bonded to a palladium catalyst.

[0179] In an exemplary embodiment disclosed herein, the process for preparing a glass substrate bonded to a palladium catalyst can be a processing procedure in which a glass substrate with hydroxyl groups already formed on its surface is treated with the aforementioned glass substrate metallization acceleration composition to obtain a glass substrate containing a palladium binder, the palladium binder being bonded to and distributed on the surface of the glass substrate.

[0180] In an exemplary embodiment disclosed herein, the glass substrate may be processed with a glass substrate metallization acceleration composition by spraying or dipping methods.

[0181] In an exemplary embodiment disclosed herein, the process of bonding the glass substrate with the palladium catalyst may be a process of treating a glass substrate with a palladium binder bonded to its surface using a palladium catalyst.

[0182] In an exemplary embodiment disclosed herein, a glass substrate with a palladium adhesive bonded to its surface can be treated with a palladium catalyst by a dipping method.

[0183] In the exemplary embodiments disclosed herein, the palladium catalyst may be a catalyst containing Pd2+ and a ligand, but there are no particular limitations as long as the palladium catalyst is a catalyst used in the field.

[0184] In an exemplary embodiment of this disclosure, the palladium catalyst may include a structure represented by [Pd-X]2+, wherein X may include 2-vinylpyridine or 2-methylpyridine.

[0185] In an exemplary embodiment disclosed herein, the palladium catalyst may include a structure represented by the following structural formula:

[0186] When a glass substrate with a palladium binder bonded to its surface is treated with a palladium catalyst, the palladium binder can bind to Pd2+ ions released from the palladium catalyst, or it can bind directly to the palladium catalyst.

[0187] In an exemplary embodiment disclosed herein, the accelerated metallization process of the glass substrate may further include a palladium catalyst reduction process.

[0188] In particular, the palladium catalyst reduction process can be a process of reducing Pd2+ ions of palladium catalyst to palladium metal.

[0189] In the exemplary embodiments disclosed herein, any palladium catalyst reduction process may be used, as long as it is known to those skilled in the art.

[0190] Glass substrate plating process

[0191] In the exemplary embodiments disclosed herein, the glass substrate plating process may be a process of forming a metal layer on a glass substrate.

[0192] In the exemplary embodiments disclosed herein, for example, the metal layer may be a copper layer.

[0193] In the exemplary embodiments disclosed herein, the glass substrate plating process may be an electroless plating process.

[0194] In the exemplary embodiments disclosed herein, the glass substrate electroplating process may be an electroless copper plating process.

[0195] In the exemplary embodiments disclosed herein, any glass substrate coating process may be used as long as it is known to those skilled in the art.

[0196] In the exemplary embodiments disclosed herein, the electroplating process may be performed after the glass substrate plating process.

[0197] Annealing process

[0198] In the exemplary embodiments disclosed herein, the annealing process may be a Si-O-Si condensation process.

[0199] During the annealing process, Si-O-Si condensation occurs, allowing the metal layer to make close contact with the glass substrate.

[0200] Generally speaking, since the annealing process is carried out at high temperature (about 150°C), even under high temperature conditions, a high adhesion strength is required between the glass substrate and the metal layer.

[0201] In the exemplary embodiments disclosed herein, any annealing process may be used, as long as it is known to those skilled in the art.

[0202] Metallized glass substrate

[0203] Another exemplary embodiment of the present disclosure provides a metallized glass substrate, including: a glass substrate; and a metal layer provided on the glass substrate, wherein a metallization-accelerating layer is included between the glass substrate and the metal layer, and the metallization-accelerating layer includes a silane coupling agent and a palladium binder containing functional groups and metal ions bonded to the silane coupling agent.

[0204] Another exemplary embodiment of the present disclosure provides a metallized glass substrate, including: a glass substrate having through holes; and a metal layer provided 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 includes a silane coupling agent and a palladium binder containing functional groups and metal ions bonded to the silane coupling agent.

[0205] In this disclosure, a metallized glass substrate refers to a structure in which a metal layer is formed on at least one surface of a glass substrate.

[0206] The metallized glass substrate disclosed herein is characterized in that the glass substrate is metallized using a glass substrate metallization acceleration composition, rather than a copper sputtering process. Generally, when a copper sputtering process is used, the copper seed is formed by titanium-copper sputtering, and the metallized glass substrate may contain titanium. On the other hand, the metallized glass substrate disclosed herein does not use a titanium-copper sputtering process, therefore the metallized glass substrate does not contain titanium.

[0207] The metallized glass substrate disclosed herein can show an adhesion strength of 2B or higher when evaluated at room temperature.

[0208] The metallized glass substrate disclosed herein can exhibit an adhesion strength of 4B or higher when evaluated at room temperature.

[0209] The metallized glass substrate disclosed herein can show an adhesion strength of 3B or higher when evaluated under highly accelerated stress test (HAST) conditions.

[0210] The metallized glass substrate disclosed herein, when evaluated under HAST conditions, can show an adhesion strength of 5B or higher.

[0211] In this disclosure, HAST conditions refer to a temperature of 100-150°C, a humidity of 80-90% and a time of 80-100 hours, or a temperature of 110-140°C, a humidity of 83-87% and a time of 90-100 hours.

[0212] According to the metallized glass substrate disclosed herein, image analysis has shown that it can display a plating uniformity of 75% or higher.

[0213] According to the metallized glass substrate disclosed herein, image analysis has shown that it can display a coating uniformity of 90% or higher.

[0214] The metallized glass substrate disclosed herein can exhibit a plating coverage ratio of 65% or higher.

[0215] The plating coverage ratio refers to the average of the ratios of T2 / T1, T3 / T1 and T4 / T1 after measuring the copper thickness (T1) on the surface (top) of the glass substrate and the copper thickness (T2, T3 and T4) at different locations inside the vias of the glass substrate after cutting the cross-section using focused ion beams (FIB) (see Figure 5).

[0216] More specifically, based on the cross-section obtained by cutting a via in a direction perpendicular to the top surface of the glass substrate using a focused ion beam, the thickness of the metal layer at 100 μm from the via on the top surface of the glass substrate (T1), the thickness of the metal layer at the via at 25% thickness (with the glass substrate thickness as 100%), the thickness of the metal layer at 50% thickness (T3), and the thickness of the metal layer at 75% thickness (T4) can be measured using the following formula 1. [Formula 1] Plating coverage ratio (%) =

[0217] The metallized glass substrate according to this disclosure can be used for semiconductor packaging. Specifically, the glass substrate according to this disclosure can be used to package semiconductor chips / devices. More specifically, the term "semiconductor packaging" generally refers to post-processing techniques that dicing processed wafers into chip shapes and then packaging them, in which glass substrates have attracted attention as next-generation semiconductor packaging materials, functioning to physically / electrically connect semiconductor chips to a system. To allow this use as a semiconductor packaging material, several functions are required, including mechanical protection, electrical / mechanical linking, and heat emission. In particular, in the case of TGV via substrates, the glass substrate contains fine electrode paths that facilitate current flow, thus offering the advantage of being able to mount more chips and high-performance chips.

[0218] The metallized glass substrate disclosed herein can be applied to packaging fields that require large areas, such as artificial intelligence (AI), high-performance computers (HPC), data centers, servers, networks, etc., especially generative AI and HPC.

[0219] [Implementation Methods of the Invention]

[0220] Hereinafter, this disclosure is described in detail by way of examples. However, the examples according to this disclosure can be modified in several different forms, and the scope of this disclosure should not be construed as limited to the examples below. The examples in this specification are provided to more fully describe this disclosure to those skilled in the art.

[0221] <Preparation Example 1> Preparation of Palladium Adhesive (LCC-1)

[0222] After placing 90 g (5 mol) of solvent (ultrapure water) and 8.6 g (0.2 mol) of LiOH-H2O into a reaction flask, it was mixed with 19.6 g (0.1 mol) of nitrilotriacetic acid and stirred at room temperature for 2 hours to prepare a solution containing 19.5 g of LCC-1 (solid) (solid content 16.9%).

[0223] <Preparation Example 2> Preparation of accelerated metallization composition for glass substrates

[0224] According to the composition and content (wt%) shown in Table 1 below, silane coupling agent, palladium binder and phase stabilizer were placed in ultrapure water (solvent) and then stirred at room temperature for 2 hours to prepare glass substrate metallization acceleration composition (margin: ultrapure water).

[0225] [Table 1] Silane coupling agent Phase stabilizers Palladium adhesive S1 S2 S3 HCl IPA LCC-1 Q3 Preparation Example 1 1.0 - - - 5.0 1.0 - Preparation Example 2 - 1.0 - 0.3 5.0 1.0 - Preparation Example 3 - 0.5 0.5 0.3 5.0 1.0 - Preparation Example 4 - 0.5 0.5 0.3 5.0 1.0 1.0 Preparation Example 5 - 1.0 - 2.0 1.0 0.5 1.5 Comparative Preparation Example 1 - Comparative preparation example 2 1.0 - - 0.5 5.0 - - Comparative preparation example 3 - 1.0 - 0.5 5.0 - - Comparative preparation example 4 - - 1.0 0.5 5.0 - - Comparative preparation example 5 - - 1.0 0.3 5.0 - 1.0 *S1: 3-Mercaptopropyltrimethoxy silane *S2: Aminoethylaminopropyltrimethoxysilane *S3: Trimethoxy[2-(7-oxabicyclo[4.1.0]hept-3-yl)ethyl]silane *IPA: Isopropyl alcohol *LCC-1: C6H9-nNO6Lin (Preparation Example 1, n=2) *Q3:

[0226] <Experimental Example 1-1> Electrolytic plating (copper) on a glass substrate (0.64 mm thick)

[0227] Internal deformation was generated in a glass substrate (0.64 mm thick) by laser modification, and through-holes (TGV holes 100 μm, aspect ratio = 1:6) were formed by etching. The glass substrate was then pretreated to clean it and form hydroxyl groups (-OH groups) on its surface. Next, the glass substrate was immersed (room temperature, 5 minutes) in the glass substrate metallization acceleration composition shown in Table 2 below to apply the composition.

[0228] After that, the glass substrate is treated with palladium catalyst (immersion, 40°C, 5 minutes), reduced (immersion, 30°C, 3 minutes), electroless copper plating is performed (immersion, 34°C, 20 minutes), and finally, annealing process is performed (230°C, 60 minutes).

[0229] In the case of Comparative Example 1-1, the process of applying the glass substrate metallization acceleration composition was omitted.

[0230] <Experimental Examples 1-2> Electrolytic Copper Plating on Glass Substrates (0.64 mm Thickness)

[0231] Internal deformation was generated in a glass substrate (0.84 mm thick) by laser modification, and through-holes (TGV holes 100 μm, aspect ratio = 1:8) were formed by etching. The glass substrate was then pretreated to clean it and form hydroxyl groups (-OH groups) on its surface. Next, the glass substrate was immersed (at room temperature, for 5 minutes) in the glass substrate metallization acceleration composition shown in Table 3 below to apply the composition.

[0232] After that, the glass substrate is treated with palladium catalyst (immersion, 40°C, 5 minutes), reduced (immersion, 30°C, 3 minutes), electroless copper plating is performed (immersion, 34°C, 20 minutes), and finally, annealing process is performed (230°C, 60 minutes).

[0233] <Experimental Example 2> Evaluation of Glass Substrates

[0234] The glass substrates coated according to Experimental Examples 1-1 and 1-2 were evaluated in terms of their properties. The results are shown in Tables 2 and 3 below. The properties shown in Tables 2 and 3 were evaluated by the following methods.

[0235] Electric conduction

[0236] The conductivity of each coated glass substrate was checked using a resistance meter. The results are shown as O (conductivity) and X (short-circuit).

[0237] Plating uniformity

[0238] The plating uniformity of each coated glass substrate was checked by image analysis. The results showed O (100% plating), □ (at least 75% plating), △ (at least 50% plating) and X (less than 50% plating).

[0239] Specifically, the coating uniformity is evaluated visually with reference to the standard in Figure 4.

[0240] Room temperature adhesion (Adhesion) (cross-cut evaluation)

[0241] At room temperature, a grid was formed on a coated glass substrate using a cross cutter (AT-CC3000 from TOC / ASTM1). Adhesive tape (3M 8981 25 mm x 10 mm (7.6 N), sp3020 from TOC) was tightly applied to the grid and removed from it. The remaining grid shape was then evaluated. Evaluation criteria were based on ASTM D3359-08.

[0242] HAST Adhesion

[0243] The coated glass substrate was placed at a temperature of 130°C and a humidity of 85% for 96 hours and evaluated in the same way as the above-mentioned "room temperature adhesion".

[0244] Plating coverage ratio

[0245] A cross-section of the coated glass substrate was cut using focused ion beams (FIB), and the metal layer thickness (T1) at a position 100 μm away from the via on the top surface of the glass substrate was measured, the metal layer thickness (T2) at a position 25% of the thickness of the via on the top surface of the glass substrate (with the thickness of the glass substrate as 100%) was measured, the metal layer thickness (T3) at a position 50% of the thickness of the via was measured, and the metal layer thickness (T4) at a position 75% of the thickness of the via was measured. The ratios of T2 / T1, T3 / T1, and T4 / T1 were then calculated, and their average value was evaluated as the coating coverage.

[0246] [Table 2] Metallization Accelerator Composition electrical conductivity Coating uniformity Room temperature adhesion HAST Adhesion Plating coverage Example 1-1 Preparation Example 1 O □ 5B 5B 75% Example 1-2 Preparation Example 2 O O 2B 0B 80% Example 1-3 Preparation Example 3 O O 5B 5B 85% Examples 1-4 Preparation Example 4 O O 5B 5B 90% Examples 1-5 Preparation Example 5 O O 5B 5B 85% Comparative Example 1-1 Comparative Preparation Example 1 X X 0B 0B 0% Comparative Examples 1-2 Comparative preparation example 2 O △ 2B 0B <20% Comparative Examples 1-3 Comparative preparation example 3 O △ 0B 0B <20% Comparative Examples 1-4 Comparative preparation example 4 O X 0B 0B 0% Comparative Examples 1-5 Comparative preparation example 5 O O 4B 3B 65%

[0247] As can be seen from the results in Table 2, in Examples 1-1 to 1-5 where the accelerated metallization process for glass substrates was performed using the composition disclosed herein, they performed superiorly in all evaluation items—conductivity, plating uniformity, adhesion, and plating coverage—compared to the comparative examples. In Comparative Example 1-1 where the accelerated metallization process for glass substrates was not performed, the conductivity evaluation showed that plating was not completed. It also showed that plating uniformity, adhesion, and plating coverage could not be determined.

[0248] Comparative Examples 1-2 to 1-4 used glass substrate metallization accelerated compositions without palladium binder. Conductivity evaluation showed that a metal layer was formed. However, due to the inability to perform proper plating, Comparative Examples 1-2 to 1-4 showed 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 evaluation and HAST adhesion evaluation.

[0249] Furthermore, Comparative Examples 1-5 used Q3, which does not contain metal ions, as the palladium binder. It can be seen that even considering the difference in silane coupling agent type, Comparative Examples 1-5 showed a lower plating coverage compared to Examples 1-1 to 1-3, which used LCC-1 (containing lithium ions) as the palladium binder. From the above results, it can be determined which structure is more suitable as a palladium binder. In particular, the evaluation showed that Comparative Examples 1-5 had higher adhesion but provided a lower plating coverage compared to Examples 1-2. It can be inferred that the above results depend on the binder structure.

[0250] Conversely, in the cases of Examples 1-1 to 1-5 using the glass substrate metallization acceleration composition according to the present disclosure, most glass substrates achieved 100% coating, exhibiting excellent coating uniformity and providing 75% or higher coating coverage. Furthermore, Examples 1-1 to 1-5 showed high adhesion not only at room temperature but also under HAST conditions.

[0251] However, in the above examples, in the case of Example 1-1, the coating uniformity is slightly lower compared to other examples. This is believed to be because S1 used as a silane coupling agent in Example 1-1 has inherently lower phase stability compared to other silane coupling agents, and contains only IPA as a phase stabilizer.

[0252] Furthermore, in Examples 1-2 where only the aminosilane coupling agent was used, it provided high plating uniformity and plating 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 hydroxyl groups on the glass substrate surface, resulting in reduced bonding strength with the palladium adhesive, thereby leading to reduced adhesion to the metal layer.

[0253] 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 Comparative Examples 1-3 with Examples 1-2, it can be seen that Examples 1-3, which use a combination of two silane coupling agents, exhibit higher adhesion and coating coverage.

[0254] Examples 1-4, which achieved the best results in the above examples, used two silane coupling agents and an additional palladium binder (Q3) in addition to the palladium binder (LCC-1). It can be seen that when two palladium binders are used, as in Examples 1-4, the binding force with the palladium catalyst can be increased, and the adhesion strength with the metal layer can be further increased.

[0255] In Examples 1-5, an aminosilane coupling agent is used alone, as in Examples 1-2, but two palladium binders are used, as in Examples 1-4. Therefore, it can be seen that Examples 1-5 show increased adhesion and further improved plating coverage.

[0256] [Table 3] Metallization Accelerator Composition electrical conductivity Coating uniformity Room temperature adhesion HAST Adhesion Plating coverage Example 2-1 Preparation Example 3 O O 5B 5B 80% Example 2-2 Preparation Example 4 O O 5B 5B 85% Example 2-3 Preparation Example 5 O O 5B 5B 80% Comparative Example 2-1 Comparative preparation example 5 O O 4B 3B 40%

[0257] Table 3 shows the coating results for a glass substrate with a thickness of 0.84 mm. In the cases of Examples 2-1 to 2-3, even with glass substrates having a high aspect ratio, a coating coverage of 80% or higher was achieved. In contrast, in the case of Comparative Example 2-1, the coating layer was partially formed but the coverage was only 40%, which did not meet the level of the examples.

[0258] As can be seen from the above results, traditional metallization methods are difficult to complete the through-hole plating of glass substrates with a thickness of 0.8T or higher.

[0259] As can be seen from the foregoing, by using the glass substrate metallization acceleration composition according to the present disclosure, uniform plating of a glass substrate having a large thickness and a high aspect ratio of 0.8 T or higher can be achieved.

Brief Description of the Drawings

[0023] FIG. 1 is a schematic diagram of a process for manufacturing a glass substrate and a process for metallizing a glass substrate according to the related art. FIG. 2 is a schematic diagram of a process for manufacturing a glass substrate and a process for metallizing a glass substrate according to the present disclosure. FIG. 3 is a schematic diagram of a process for metallizing a glass substrate according to the present disclosure. FIG. 4 shows a reference standard for evaluating the plating uniformity of a glass substrate according to the present disclosure. FIG. 5 shows the measurement positions of each thickness measured for evaluating the plating coverage of a glass substrate according to the present disclosure.

Claims

1. A glass substrate metallization acceleration composition, comprising: Silane coupling agents; And a binder for palladium, wherein the binder for palladium is a metal ion-containing compound comprising a functional group capable of binding with the silane coupling agent.

2. The glass substrate metallization acceleration composition as claimed in claim 1, wherein the binder for palladium is represented by the following chemical formula 1: [Chemical Formula 1] In chemical formula 1, L1 to L3 are the same or different and are each independently C1-C5 alkylene, X1 is -NH2, -OH, -C(=O)OH or -P(=O)(OH)2, X2 and X3 are the same or different and are 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 lithium or sodium, 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 as claimed in 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 are the same or different and are each independently C1-C5 alkyl, L11 and L12 are the same or different and are each independently C1-C5 alkylene, n is 0 or 1, and Q is -SH, -NH2 or a fused heterocyclic group containing O.

4. The glass substrate metallization accelerating composition as claimed in claim 1 further includes a phase stabilizer selected from hydrochloric acid, sulfuric acid, methanol, ethanol, isopropanol and sodium hydroxide.

5. The glass substrate metallization accelerating composition as claimed in claim 1, further comprising a solvent and a phase stabilizer, wherein based on 100 parts by weight of the glass substrate metallization accelerating composition, the content of the silane coupling agent is 0.1-5 parts by weight, the content of the binder for palladium is 0.3-5 parts by weight, and the content of the phase stabilizer is 1-20 parts by weight.

6. A method for preparing a glass substrate metallization acceleration composition, comprising the steps of: mixing a silane coupling agent with a binder for palladium to prepare a mixture; and stirring the mixture, wherein the binder for palladium is a metal ion-containing compound comprising functional groups capable of binding with the silane coupling agent.

7. The method for preparing a glass substrate metallization accelerated composition as described in claim 6, wherein the step of stirring the mixture is carried out at 15-25°C.

8. The method for preparing a glass substrate metallization accelerated composition as described in claim 6, wherein the step of stirring the mixture is performed for 1-3 hours.

9. A glass substrate metallization acceleration process, comprising the step of performing a surface treatment of the glass substrate using a glass substrate metallization acceleration composition as described in any one of claims 1 to 5.

10. A metallized glass substrate, comprising: Glass substrate; A metal layer is provided on the glass substrate, wherein a metallization acceleration layer is contained between the glass substrate and the metal layer, and the metallization acceleration layer comprises a silane coupling agent and a binder for palladium containing functional groups and metal ions bonded to the silane coupling agent.

11. A metallized glass substrate, comprising: Glass substrate with through holes; A metal layer is provided in the via of the glass substrate, wherein a metallization acceleration layer is contained between the glass substrate and the metal layer, and the metallization acceleration layer comprises a silane coupling agent and a binder for palladium containing functional groups and metal ions bonded to the silane coupling agent.

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