Glass member, glass member manufacturing system, and glass member manufacturing method

Abstract

This glass member (100) comprises a glass substrate (10), and a copper-containing conductive layer (20) formed on the glass substrate (10). In the conductive layer (20), the number of blisters having a longest diameter of 5 μm or more is 5 blisters / cm2 or less. This glass member manufacturing system is provided with an electroless plating apparatus that forms a first metal film containing copper on a glass substrate, by electroless plating at a deposition rate of 1.3 μm / hour or less.

Description

Glass component, glass component manufacturing system, and glass component manufacturing method

[0001] This invention relates to a glass component, a glass component manufacturing system, and a method for manufacturing a glass component.

[0002] Because glass plates can be processed with fine holes, TGV (Through Glass Via) substrates, which have through-hole vias or blind vias drilled into the glass plate, are being considered as an alternative to TSV (Through Silicon Via) substrates. TGV substrates are being considered for use in glass interposers, antenna glass substrates, RF (Radio Frequency) modules, optical sensor modules, and optical sensor substrates. Therefore, in order to mount electronic components on glass materials, including glass plates, it is necessary to form fine wiring on the glass material.

[0003] For example, Patent Document 1 discloses a glass wiring substrate in which titanium, copper, and electroless nickel-phosphorus plating are laminated.

[0004] Patent No. 7183582

[0005] However, in the glass wiring substrate disclosed in Reference 1, titanium, copper, and electroless nickel-phosphorus plating are laminated on the glass substrate. Therefore, when wiring is formed on this glass wiring substrate, the electrical resistance of the wiring becomes higher compared to when a copper film is directly deposited on the glass substrate and then wiring is formed. When forming a copper film on a glass substrate by wet plating, it is necessary to form a copper film on the glass substrate by electroless plating and then form a copper film by electrolytic plating. When a copper film is formed on a glass substrate by electroless plating, there is a problem of blistering. If blistering occurs with electroless plating, it becomes difficult to form fine wiring on the copper film formed on the glass substrate.

[0006] The present invention was made to solve the above-mentioned problems, and aims to provide a glass component having a copper film with minimal blistering formed by electroless plating, a glass component manufacturing system, and a method for manufacturing a glass component.

[0007] To achieve the objectives of the present invention, one form of the glass member according to the present invention comprises a glass substrate and a conductive layer containing copper formed on the glass substrate, wherein the conductive layer has five blisters with a longest diameter of 5 μm or more per 1 cm. ２ The following characteristics apply.

[0008] To achieve the objectives of the present invention, one embodiment of the glass component manufacturing system according to the present invention is characterized by comprising an electroless plating apparatus that forms a first metal film containing copper on a glass substrate by electroless plating at a deposition rate of 1.3 μm / hour or less.

[0009] To achieve the objectives of the present invention, one embodiment of the method for manufacturing a glass member according to the present invention is characterized by comprising an electroless plating step of forming a first metal film containing copper on a glass substrate by an electroless plating method at a deposition rate of 1.3 μm / hour or less.

[0010] According to the present invention, it is possible to provide a glass member having a copper film with minimal blistering formed by electroless plating, a glass member manufacturing system, and a method for manufacturing a glass member.

[0011] This is a diagram showing a glass member according to the embodiment. This is a cross-sectional view taken along line II-II in Figure 1. This is a diagram showing a manufacturing system for a glass member according to the embodiment. This is a diagram showing a UV irradiation device according to the embodiment. This is a flowchart showing a method for manufacturing a glass member according to the embodiment. (A) to (C) are photographs of the surface of a glass substrate on which electroless plating has been formed according to the example, and (D) is a photograph of the surface of a glass substrate on which electroless plating has been formed according to the comparative example.

[0012] Hereinafter, a glass member, a manufacturing system for the glass member, and a method for manufacturing the glass member according to embodiments of the present invention will be described with reference to the drawings.

[0013] As shown in Figures 1 and 2, the glass member 100 according to the embodiment comprises a glass substrate 10 and a conductive layer 20, with the conductive layer 20 patterned on the glass substrate 10, and can be used as a glass wiring board used as a glass interposer, an Athena glass substrate, an RF (Radio Frequency) module, an optical sensor module, or an optical sensor substrate.

[0014] The shape of the glass substrate 10 is not particularly limited, and for example, it may have a plate-like shape having a first main surface 11a, a second main surface 11b which is the back surface of the first main surface 11a, and a through hole 12 that penetrates from the first main surface 11a to the second main surface 11b. The thickness T1 of the glass substrate 10 is not particularly limited, but for example, it is 0.1 mm or more and 1.0 mm or less. The shape of the through hole 12 is not particularly limited, but for example, the diameter D1 of the through hole 12 is, for example, a circular hole of 10 μm or more and 10 mm or less. Furthermore, the type of glass material used to manufacture the glass substrate 10 is not particularly limited, and examples include alkali-free glass, quartz glass, sodium glass, and borosilicate glass. When considering an electronic substrate, it is preferable to use quartz glass or alkali-free glass that does not contain alkali ions due to the problem of electrical migration of alkali ions.

[0015] The conductive layer 20 is a copper film containing copper (Cu), with 5 blisters per 1 cm² having a longest diameter of 5 μm or more. ２The conductive layer 20 can be formed by the glass member manufacturing system 200 and glass member manufacturing method described later. The conductive layer 20 is formed on the first main surface 11a, the second main surface 11b, and the inner wall of the through hole 12, and the conductive layer 20 formed on the first main surface 11a and the conductive layer 20 formed on the second main surface 11b are electrically connected via the conductive layer 20 formed in the through hole 12. The conductive layer 20 preferably consists of copper and unavoidable impurities. Specifically, the conductive layer 20 contains 99.99% or more copper. Unavoidable impurities include impurities contained in the plating solution or impurities mixed in during the plating process. Preferably, the conductive layer 20 is patterned with an electrical circuit. The thickness T2 of the conductive layer 20 is not particularly limited, but any thickness that can be used as wiring on a glass wiring substrate is acceptable, for example, 1 μm or more and 100 μm or less.

[0016] Next, a glass member manufacturing system 200 for manufacturing the glass member 100 having the above configuration will be described.

[0017] As shown in Figure 3, the glass component manufacturing system 200 includes a cleaning device 210, a catalyst adsorption device 220, and an electroless plating device 230. Preferably, the glass component manufacturing system 200 further includes an electroplating device 240 and a heating device 250.

[0018] The cleaning apparatus 210 comprises a UV (Ultra Violet) irradiation device 211, a first cleaning tank 212, and a second cleaning tank 213, and is a device for removing oils, salts, and fine particles, whether organic or inorganic, adsorbed on the surface of the glass substrate 10. This allows for the attachment of a uniform and dense catalyst to the glass substrate 10, thereby improving the adhesion between the glass substrate 10 and the conductive layer 20. Preferably, after ultraviolet (UV) irradiation treatment of the surface of the glass substrate 10 using the UV irradiation device 211, the cleaning treatment is performed using a cleaning solution containing a cleaning solution placed in the first cleaning tank 212 and an alkaline solution placed in the second cleaning tank 213. The cleaning solution or alkaline solution may contain alkaline electrolyzed water, ozonated water, a solution containing at least one selected from NaOH, KOH, and LiOH, or a surfactant. As shown in Figure 4, the UV irradiation device 211 preferably includes a UV lamp 211A that irradiates the glass substrate 10 with UV light including a wavelength of 184.9 nm. The UV lamp 211A more preferably further irradiates with UV light including a wavelength of 253.7 nm. It is believed that by cleaning the surface of the glass substrate 10 with UV irradiation, it becomes possible to form a copper film that allows for fine wiring. Furthermore, the cleaning device 210 may also use water washing, hot water washing, inorganic chemical cleaning, organic chemical cleaning, ultrasonic cleaning, UV irradiation, excimer lamp, plasma irradiation, corona discharge, etc. in combination.

[0019] The catalyst adsorption apparatus 220 comprises a first processing tank 221 and a second processing tank 222, and is an apparatus for imparting a catalyst metal to the surface of a glass substrate 10. Specifically, the first processing tank 221 performs sensitizing to impart a catalyst metal ion capture function to the surface of the glass substrate 10. Sensitizing is performed, for example, by immersing the glass substrate 10 in a solution containing Sn chloride placed in the first processing tank 221 and adsorbing it onto the surface of the glass substrate 10. The second processing tank 222 contains a catalyst metal solution, and activating is performed by immersing the glass substrate 10 in the catalyst metal solution to impart the catalyst metal to the surface of the glass substrate 10. The catalyst metal is preferably an ion such as Pd, Cu, Ag, or Au, and the catalyst metal solution is, for example, a dilute solution of palladium chloride, silver nitrate, or copper chloride. Alternatively, the catalyst metal may be imparted by a mixed catalyst method, an alkaline catalyst, or the like. Preferably, the glass substrate 10 is immersed in the solutions placed in the first treatment tank 221 and the second treatment tank 222, respectively. The immersion may be repeated multiple times.

[0020] The electroless plating apparatus 230 is a device that forms a first metal film containing copper by electroless plating by contacting or immersing a glass substrate 10 coated with a catalyst metal in an electroless plating solution containing copper ions. The electroless plating solution contains a metal salt, a complexing agent, and a reducing agent, and may further contain a stabilizer, an accelerator, and a film improving agent. If the first metal film is not uniform or if pinholes exist, adhesion will decrease, peeling will occur, and blistering will occur. For this reason, it is preferable that the deposition rate of the electroless plating in the electroless plating apparatus 230 be 1.3 μm / hour or less, and more preferably 1.0 μm / hour or less. This prevents peeling and blistering of the copper plating film. Furthermore, in order to efficiently carry out electroless plating, it is preferable that the deposition rate of the electroless plating be 0.3 μm / hour or more, and more preferably 0.5 μm / hour or more. The deposition rate of electroless plating can be adjusted by controlling the pH, temperature, copper ion concentration, complexing agent concentration, reducing agent concentration, stabilizer concentration, accelerator concentration, and film improving agent concentration of the electroless plating solution.

[0021] As sources of copper ions, copper sulfate, copper halides, copper nitrate, copper oxide, copper acetate, copper pyrophosphate, copper tetrafluoroborate, copper alkylsulfonate, copper arylsulfonate, copper sulfamate, copper perchlorate, copper gluconate, etc., can be used individually or in combination of two or more.

[0022] Complexing agents include ethylenediaminetetraacetic acid (EDTA), N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid (HEDTA), cyclohexanediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethylethylenediaminetriacetic acid, triethylenetetraminehexaacetic acid, ethylenediaminetetrapropionic acid, aminetriacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid, iminodipropionic acid, 1,3-propylenediaminetetraacetic acid, 1,3-diamino-2-hydroxypropanetetraacetic acid, glycol etherdiaminetetraacetic acid, m-phenylenediaminetetraacetic acid, diaminopropionic acid, glutamic acid, and dicarboxymethyl methyl acetic acid. Glutamic acid, ornithine, cysteine, S-carboxymethyl-L-cysteine, N,N-bis(2-hydroxyethyl)glutamic acid, (S,S)-ethylenediaminesuccinic acid and their salts, tartaric acid, gluconic acid, citric acid, malic acid, glucoheptonic acid, glycolic acid, lactic acid, trihydroxybutyric acid, ascorbic acid, isocitric acid, hydroxymalonic acid, glyceric acid, hydroxybutyric acid, leucine, citramalic acid, salicylic acid and their salts, succinic acid, glutaric acid, malonic acid, adipic acid, oxalic acid, maleic acid, citraconic acid, itaconic acid, mesaconic acid and their salts, etc., are used individually or in combination of two or more.

[0023] Reducing agents include formaldehyde, dimethylamine borane (DMAB), boron hydride, glyoxylic acid, glyoxylate, pyrophosphoric acid, phosphinate, subphosphate, boron hydride, hydrazide, carbohydrates, ascorbic acid, hydroquinone, hydrazine, etc., used individually or in combination of two or more.

[0024] Stabilizers include sulfur compounds such as pyridine, bipyridine, phenanthroline, thiazole, thiadiazole, imidazole, diazole, pyrimidine, oxazole, isoxazole, triazole, tetrazole, thiourea, and thiocyanates; nitrogen compounds such as iodide, ethanolamine, benzenediol, tocopherol, hydantoin, caprolactam, cyanide, inorganic cyanide, and 2,2'-bipyridyl; and inorganic compounds such as mercury, vanadium pentoxide, lead, and Ni, used individually or in combination of two or more.

[0025] As accelerators, ammonium salts, molybdates, tungstates, pyridines, cytosine / guanisine hydrochlorides, etc., are used individually or in combination of two or more.

[0026] As film-improving agents, polyethylene glycol, polypropylene glycol, polyethyleneimine, polyacrylamide, polyacrylic acid, ethylene oxide propylene oxide copolymer, polypropylene glycol-block polyethylene glycol copolymer, and derivatives thereof are used individually or in combination of two or more.

[0027] The electroplating apparatus 240 is a device that performs electroplating of copper to form a second metal film containing copper. As the plating solution used for electroplating, copper sulfate plating solution, copper pyrophosphate plating solution, copper cyanide plating solution, etc., can be used.

[0028] The heating device 250 is a device that performs stress relaxation treatment on the glass substrate 10 and the copper film by heating at a specified temperature for a certain period of time in order to perform stress relaxation treatment. The peak heat treatment temperature of the heating device 250 is preferably 300°C or higher, and particularly preferably 350°C to 600°C. As for the atmosphere inside the furnace, the treatment can be sufficiently performed in an air atmosphere, which is simpler for the device, but it may also be carried out in an inert gas atmosphere such as vacuum, argon gas, or nitrogen gas. This results in a glass member 100 in which a conductive layer 20 is formed on the glass substrate 10. When the glass substrate 10 is heat-treated in air, it is preferable to perform an oxide film removal treatment.

[0029] Next, a method for manufacturing a glass component using the glass component manufacturing system 200 having the above configuration will be described.

[0030] As shown in Figure 5, the method for manufacturing the glass component 100 comprises a cleaning step (step S101), a catalyst adsorption step (step S102), and an electroless plating step (step S103). Preferably, the method for manufacturing the glass component 100 further comprises an electroplating step (step S104) and a heating step (step S105). Examples of the glass substrate 10 include alkali-free glass, quartz glass, sodium glass, and borosilicate glass, and alkali-free glass is preferably used.

[0031] The cleaning step (step S101) is a process of removing oil, salts, and fine particles, whether organic or inorganic, adsorbed on the surface of the glass substrate 10 using a cleaning device 210. This step allows for the adhesion between the glass substrate 10 and the conductive layer 20 by adhering a uniform and dense catalyst to the glass substrate 10. Preferably, the surface of the glass substrate 10 is irradiated with UV light including a wavelength of 184.9 nm using the UV irradiation device 211 of the cleaning device 210, and more preferably, with UV light including a wavelength of 253.7 nm. After the ultraviolet (UV) irradiation treatment, the surface is washed with a cleaning solution in the first cleaning tank 212, and then alkaline degreasing is performed with an alkaline solution in the second cleaning tank 213. By cleaning the surface of the glass substrate 10 with UV irradiation, the wettability is improved, and it is believed that by adhering a uniform and dense catalyst metal to the glass substrate 10 in the catalyst adsorption step (step S102) described later, it becomes possible to apply a copper film with good adhesion. Furthermore, methods such as water washing, hot water washing, inorganic chemical cleaning, organic chemical cleaning, ultrasonic cleaning, UV irradiation, plasma irradiation, and corona discharge may be used in combination.

[0032] The catalyst adsorption step (step S102) is a step in which a catalyst metal is applied to the surface of the glass substrate 10 using a catalyst adsorption device 220. Specifically, first, a sensitizing process is performed using the first processing tank 221 of the catalyst adsorption device 220 to impart a catalyst metal ion capture function to the surface of the glass substrate 10. Sensitizing can be performed, for example, by immersing the glass substrate 10 in a tin salt solution or a surfactant solution and adsorbing it onto the surface. Sn chloride is particularly preferred.

[0033] Next, the glass substrate 10 is immersed in a catalyst metal solution using the second treatment tank 222 of the catalyst adsorption apparatus 220. The catalyst metal is preferably palladium, silver, or copper ions. For example, activation is performed to impart the catalyst metal to the surface of the glass substrate 10 by immersion in a dilute solution of palladium chloride, silver nitrate, or copper chloride. Next, if tin chloride is used to impart the ability to capture catalyst metal ions, a reduction treatment may be performed, although this is not strictly necessary if the metallization of the catalyst metal ions is insufficient. Examples of reduction treatments include chemical solution treatment with sodium hypophosphite, sodium borohydride, potassium borohydride, dimethylamine borane, hydrazine, formalin, etc., or hydrogen reduction treatment, but are not necessarily limited to these. In the catalyst adsorption step (step S102), the glass substrate 10 is preferably immersed in the solutions placed in the first treatment tank 221 and the second treatment tank 222. The catalyst adsorption step may be repeated multiple times.

[0034] The electroless plating process (step S103) is a process of forming a first metal film containing copper by bringing or dipping the glass substrate 10 provided with a catalytic metal into a plating solution containing copper ions, a complexing agent, and a reducing agent using an electroless plating apparatus 230, and it serves to make the glass substrate 10 conductive and as an adhesion layer between the glass substrate 10. If the first metal film is not a uniform film, problems such as reduced adhesion, peeling, and swelling will occur. Therefore, it is preferable that the deposition rate of the electroless plating is 1.3 μm / hour or less, and it is more preferable that it is 1.0 μm / hour or less. Thereby, peeling and swelling of the copper plating film can be prevented. Also, in order to efficiently carry out the electroless plating process (step S103), it is preferable that the deposition rate of the electroless plating is 0.3 μm / hour or more, and it is more preferable that it is 0.5 μm / hour or more. The deposition rate of the electroless plating can be adjusted by changing the pH of the electroless plating solution, the temperature of the electroless plating solution, the copper ion concentration of the electroless plating solution, the complexing agent concentration, the reducing agent concentration, the additive concentration, etc. If there is peeling or swelling in the first metal film, the subsequent electroplating process (step S104) will become difficult. Also, as the copper film formed by electroless plating becomes thicker, it becomes difficult to form it on the smooth surface of the glass substrate 10, so stable production becomes difficult. Therefore, from the viewpoint of ensuring conductivity, the thickness of the copper film is 5.0×10 －３ μm or more, particularly preferably 1.0×10 －２ to 2.0 μm.

[0035] As the electroless plating solution, the copper ion concentration is preferably 1.0×10 －４ to 1.0 mol / dm ３ , particularly preferably 1.0×10 －３ to 2.0×10 －１ mol / dm ３ . As the copper ion source, a water-soluble copper salt such as copper sulfate or copper chloride is preferable. The complexing agent concentration is 1.0×10 －４ to 10 mol / dm ３ , particularly preferably 1.0×10 －３ to 2.0×10 －１ mol / dm ３It is preferable that... As the complexing agent species, the above-mentioned Rochelle salt, EDTA (ethylenediaminetetraacetic acid), ethylenediamine, etc. are preferable. As the reducing agent concentration, it is 1.0×10 －４ ~1.0 mol / dm ３ , particularly 1.0×10 －３ ~4.0×10 －１ mol / dm ３ and it is preferable that...

[0036] The electroplating step (step S104) is a step of performing electroplating of copper using the electroplating apparatus 240 to form a second metal film containing copper. The thickness of the copper film formed here is preferably 1 μm or more and 100 μm or less, and more preferably 10 μm or more and 50 μm or less. A known plating method can be used as the electroplating method.

[0037] The heating step (step S105) is a step of performing stress relaxation treatment between the glass substrate 10 and the copper film by heating at a prescribed temperature for a certain time using the heating apparatus 250 after the electroplating step (step S104). Specifically, in the heating step (step S105), the heat treatment peak temperature is 300°C or more, particularly preferably 350°C to 600°C. As the atmosphere in the furnace, a simple atmosphere of the apparatus is sufficient for treatment, but it may also be performed in an inert gas atmosphere such as vacuum, argon gas, or nitrogen gas. Thereby, the glass member 100 in which the conductive layer 20 is formed on the glass substrate 10 is obtained. When the glass substrate 10 is heat-treated in the air, it is preferable to perform an oxide film removal treatment. Thereby, the glass member 100 in which the conductive layer 20 is formed on the glass substrate 10 is obtained.

[0038] As described above, the glass member 100 of the present embodiment has 5 bulges with a longest diameter of 5 μm or more per 1 cm ２The following conditions allow for the creation of a copper film capable of fine wiring. Furthermore, the glass component manufacturing system 200 and the glass component manufacturing method allow for the creation of a glass component 100 having a first metal film with minimal blistering by performing electroless plating at the above-described deposition rate. By forming a first metal film with minimal blistering by electroless plating, a good second metal film can then be formed by electroplating. This makes it possible to form circuits with fine copper wiring on the glass substrate 10 surface, which is advantageous in reducing conductor loss during signal propagation and is expected to be useful for high-frequency wiring boards. In addition, since the conductive layer 20 consists of copper and unavoidable impurities, copper wiring with excellent conductivity can be obtained. Normally, electroless plating forms a plating film at a deposition rate of 3.0 μm / hour or more. When a copper film is plated onto a glass substrate at an extraction rate of 3.0 μm / hour or more, blistering and peeling occur.

[0039] (Modifications) In the above-described embodiment, an example was given in which the glass member 100 has through holes 12. However, the shape of the glass member 100 is not particularly limited, and non-through holes, protrusions, grooves, etc., may be formed on the glass substrate 10. It may also have a complex three-dimensional shape, including cylindrical or tubular shapes. As described above, the conductive layer 20 is formed by plating, so it can be formed regardless of the complex shape of the glass substrate.

[0040] In the above-described embodiment, a glass member 100 in which a conductive layer 20 is formed on a glass substrate 10 has been explained. Wiring may be formed on the conductive layer 20 formed on the glass substrate 10. In this case, after the heating step (step S105), a patterning step is provided in which a part of the conductive layer 20 is removed in order to obtain a glass member 100 in which the wiring of the conductive layer 20 is patterned on the glass substrate 10. The patterning step can be carried out by subtractive method, for example. Specifically, a dry film resist (DFR) is laminated onto the conductive layer 20, exposed and developed, and the conductive layer 20 is etched with ferric chloride to remove the DFR. As a result, a glass member 100 in which a circuit pattern is formed on the glass substrate 10 is obtained.

[0041] The glass components are demonstrated below by examples. These examples illustrate one embodiment of the present disclosure, and the present disclosure is not limited thereto.

[0042] The glass substrates used in Examples 1-5 and Comparative Example 1 were alkali-free glass (EAGLE XG, Corning, 50 mm x 50 mm x t = 0.5 mm). A copper film, which is a conductive layer, was formed on this glass substrate to obtain the glass members of Examples 1-5 and Comparative Example 1.

[0043] In the cleaning process (step S101), as shown in Table 1, the glass substrates of Examples 1 to 5 and Comparative Example 1 were irradiated with UV light at wavelengths of 184.9 nm and 253.7 nm for 10 minutes using a high-power, low-pressure mercury lamp, and then alkaline degreasing was performed using an alkaline solution. Note that cleaning with the cleaning solution includes ultrasonic cleaning.

[0044] Next, in the catalytic adsorption step (step S102), the glass substrates of Examples 1 to 5 and Comparative Example 1, which were washed in the washing step (step S101), were subjected to sensitizing and activating treatments under the conditions of components, concentrations, temperature, and time shown in Table 1.

[0045] Next, in the electroless plating process (step S103), the glass substrates of Examples 1 to 5 and Comparative Example 1, which had been treated in the catalyst adsorption process (step S102), were subjected to electroless plating using an electroless plating solution under the conditions of components, temperature, time shown in Table 1, and pH and deposition rate shown in Table 2. In this example, the deposition rate was adjusted by pH. In addition, appropriate amounts of Rochelle salt as a complexing agent, formaldehyde as a reducing agent, and polyethylene glycol as a film improving agent were added to the electroless plating solution. After that, they were dried with hot air.

[0046] As a result, glass members with copper films formed on them were obtained in Examples 1 to 5 and Comparative Example 1. In Examples 1 to 5 and Comparative Example 1, all steps except the electroless plating step (step S103) were the same.

[0047]

[0048]

[0049] Next, the appearance of the electroless plating film was observed on the glass substrates on which the electroless plating of Examples 1 to 5 and Comparative Example 1 was formed. Figure 6(A) is a photograph of the surface of the glass substrate on which the electroless plating of Example 2 was formed, Figure 6(B) is a photograph of Example 3, Figure 6(C) is a photograph of Example 5, and Figure 6(D) is a photograph of the surface of the glass substrate on which the electroless plating of Comparative Example 1 was formed. There were 5 blisters with a longest diameter of 5 μm or more per 1 cm. ２ The following conditions were considered normal: The electroless plating films formed on the glass substrates of Examples 2, 3, and 5 were excellent, without blistering, as shown in Figure 6(A). The electroless plating films formed on the glass substrates of Examples 1 and 4 were also excellent, without blistering, similar to Examples 2, 3, and 5. The electroless plating film formed on the glass substrate of Comparative Example 1 was poor, showing large blistering and peeling, as shown in Figure 6(D). From the above, it was found that the deposition rate is preferably 1.3 μm / hour or less, and more preferably 1.0 μm / hour or less. Furthermore, from the viewpoint of productivity, it was found that the deposition rate is preferably 0.46 μm / hour or more, and more preferably 0.65 μm / hour or more. The pH of the electroless plating solution is preferably 12.75 or less, and more preferably 12.50 or less. Furthermore, from the viewpoint of productivity, it was found that the pH of the electroless plating solution is preferably 11.50 or more, and more preferably 12.00 or more. It is believed that by further forming a copper film on the glass substrates that have been electroless plated in Examples 1 to 5 using electroplating, a glass member with a copper film capable of fine wiring can be obtained. In contrast, in Comparative Example 1, the copper film peels off from the glass substrate when treated with electroplating, making it difficult to form a copper film.

[0050] As described above, by electroless plating on a glass substrate at the deposition rate mentioned above, an electroless plated film with minimal blistering was obtained. The ability to obtain an electroless plated film with minimal blistering allows for further electroplating, enabling the formation of a copper film capable of fine wiring. Therefore, the glass components of Examples 1 to 3 are expected to be used in high-frequency wiring boards, as they enable the formation of fine circuits on the glass substrate, which is particularly advantageous for reducing conductor loss during signal propagation, especially in alkali-free glass, a material expected to be in demand in the electronics field. In the above examples, alkali-free glass was used as the glass substrate, but it is believed that copper films can be similarly formed on other types of glass, such as alkali glass or quartz glass. Normally, electroless plating forms a plated film at a deposition rate of 3.0 μm / hour or higher. When a copper film is plated onto a glass substrate at an extraction rate of 3.0 μm / hour or higher, blistering and peeling occur.

[0051] This invention allows for various embodiments and modifications without departing from the broad spirit and scope of the invention. Furthermore, the embodiments described above are for illustrative purposes only and do not limit the scope of the invention. In other words, the scope of the invention is indicated not by the embodiments, but by the claims. Various modifications made within the scope of the claims and the equivalent scope of the meaning of the invention are considered to be within the scope of this invention.

[0052] 10...Glass substrate, 11a...First main surface, 11b...Second main surface, 12...Through hole, 20...Conductive layer, 30...Intermediate layer, 100...Glass component, 200...Glass component manufacturing system, 210...Cleaning device, 211...UV irradiation device, 211A...UV lamp, 212...First cleaning tank, 213...Second cleaning tank, 220...Catalyst adsorption device, 221...First processing tank, 222...Second processing tank, 230...Electroless plating device, 240...Electrolytic plating device, 250...Heating device, D1...Diameter, T1, T2...Thickness

Claims

1. A glass substrate and a conductive layer containing copper formed on the glass substrate, wherein the conductive layer has 5 blisters with a longest diameter of 5 μm or more per 1 cm. ２ A glass member characterized by the following:

2. The glass member according to claim 1, characterized in that the conductive layer consists of copper and unavoidable impurities.

3. A glass component manufacturing system characterized by comprising an electroless plating apparatus for forming a first metal film containing copper on a glass substrate by electroless plating at a deposition rate of 1.3 μm / hour or less.

4. A glass component manufacturing system according to claim 3, further comprising: a cleaning device for cleaning a glass substrate; and a catalyst adsorption device for adsorbing a catalyst onto the glass substrate cleaned by the cleaning device, wherein the electroless plating device forms the first metal film containing copper on the glass substrate onto which the catalyst has been adsorbed by the catalyst adsorption device.

5. A method for manufacturing a glass component, characterized by comprising an electroless plating step of forming a first metal film containing copper on a glass substrate by an electroless plating method at a deposition rate of 1.3 μm / hour or less.

6. A method for manufacturing a glass member according to claim 5, comprising: a cleaning step for cleaning a glass substrate; a catalyst adsorption step for adsorbing a catalyst onto the glass substrate cleaned in the cleaning step, wherein in the electroless plating step, a first metal film containing copper is formed on the glass substrate onto which the catalyst has been adsorbed in the catalyst adsorption step.

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