Perforated glass substrate, glass substrate, and method for producing perforated glass substrate

Abstract

Provided are a perforated glass substrate, a glass substrate, and a method for manufacturing a perforated glass substrate, which are suitable for forming a through-hole close to a straight shape, have excellent productivity, and do not tend to cause deformation of the substrate when mounting a semiconductor element. A perforated glass substrate G according to the present invention comprises a first main surface G1, a second main surface G2 that is the reverse surface of the first main surface G1, and a through-hole 1 that penetrates between the first main surface G1 and the second main surface G2. The perforated glass substrate G has a glass composition containing, in mol%, 65.0-85.0% of SiO2, 0-10.0% of Al2O3, 0.1-25.0% of B2O3, 0-5.0% of Li2O, 0-20.0% of Na2O, and 0-20.0% of K2O.

Description

Perforated glass substrate, glass substrate, and method for manufacturing a perforated glass substrate

[0001] The present invention relates to a perforated glass substrate, a glass substrate, and a method for manufacturing a perforated glass substrate.

[0002] Development is underway for package substrates that mount multiple semiconductor elements on a single electronic substrate (core substrate). Glass has excellent dimensional stability and low dielectric properties, and using glass as the material for the core substrate or the interposer that connects the semiconductor elements to the core substrate can improve the performance of the package substrate. When using a glass substrate as a glass core substrate or glass interposer, it is necessary to form fine through-holes and fill the inside of the through-holes with conductive material in order to make the front and back surfaces of the glass substrate electrically conductive.

[0003] A known method for precisely forming through holes in a glass substrate involves irradiating the glass substrate with a pulsed laser to create a modified area where the through hole is to be formed, and then etching the glass substrate to remove the modified area and form the through hole. Through holes formed by this method have a tapered shape, but in order to mount semiconductors at high density, it is preferable to reduce the diameter of the through hole on the glass surface, that is, to reduce the taper angle of the through hole so that it is close to a straight shape.

[0004] To form through holes that are close to a straight shape, the SiO of the glass substrate ２ Increasing the content, Al ２ O ３ , B ２ O ３ Such SiO ２ It is known to be effective to regulate the content of glass skeleton-forming components other than (see, for example, Patent Documents 1 and 2).

[0005] Japanese Patent Publication No. 2023-018034 Japanese Special Publication No. 2022-531500

[0006] By the way, in order to make it easier to form through holes that are close to a straight shape in the glass substrate, SiO in the glass ２Increasing the content of [substance] deteriorates the meltability and formability and raises the production cost. However, there is no description in Patent Document 1 and Patent Document 2 regarding the glass composition range that can form through-holes close to a straight shape and has excellent meltability.

[0007] Further, when mounting a semiconductor element on a glass substrate, if the difference in the coefficient of thermal expansion between the mounted semiconductor element and the glass substrate is large, there is a risk of damage to the semiconductor element or the glass substrate when the temperature is raised and lowered during the mounting of the semiconductor element. Therefore, when mounting a semiconductor element on a core substrate or an interposer using a glass substrate, the coefficient of thermal expansion is particularly important, but there is no description in Patent Document 1 and Patent Document 2 regarding a preferable coefficient of thermal expansion.

[0008] In view of the above problems, an object of the present invention is to provide a porous glass substrate, a glass substrate, and a method for manufacturing a porous glass substrate that are suitable for forming through-holes close to a straight shape, have excellent productivity, and are less likely to cause deformation of the substrate when mounting a semiconductor element.

[0009] As a result of repeating various experiments, the present inventor has found that the above technical problems can be solved by strictly regulating the glass composition of the glass substrate, and proposes the present invention.

[0010] (1) The porous glass substrate of the present invention devised to solve the above problems is a porous glass substrate including a first main surface, a second main surface opposite to the first main surface, and a through-hole penetrating between the first main surface and the second main surface, wherein the glass composition contains, in mol%, SiO ２ 65.0 to 85.0%, Al ２ O ３ 0 to 10.0%, B ２ O ３ 0.1 to 25.0%, Li ２ O 0 to 5.0%, Na ２ O 0 to 20.0%, K ２ O 0 to 20.0% and is characterized by this.

[0011] (2) In the configuration of (1) above, the glass substrate has a glass composition containing, in mol%, SiO ２ 65.0 to 85.0%, Al２ O ３ 0-10.0%, B ２ O ３ 0.1-20.0%, Li ２ O 0-3.0%, Na ２ O 0-20.0%, K ２ It is preferable that it contains 0 to 20.0% of O.

[0012] (3) In the configuration of (1) above, the glass composition is SiO in mol% ２ 65.0-85.0%, Al ２ O ３ 0-10.0%, B ２ O ３ 5.0-25.0%, Li ２ O 0-5.0%, Na ２ O 0-20.0%, K ２ It is preferable that it contains 0 to 5.0% of O.

[0013] (4) In the configuration of (1) above, the glass composition is SiO in mol% ２ 65.0-85.0%, Al ２ O ３ 0-10.0%, B ２ O ３ 0.1% or more and less than 5.0%, Li ２ O 0-5.0%, Na ２ O 0-20.0%, K ２ It is preferable that it contains 0 to 20.0% of O.

[0014] (5) In the configuration of (1) above, the glass composition is SiO in mol% ２ 65.0-85.0%, Al ２ O ３ 0-10.0%, B ２ O ３ 0.1-25.0%, Li ２ O 0-5.0%, Na ２ O 0-20.0%, K ２ It is preferable that the product contains more than 5.0% and no more than 20.0% of O.

[0015] (6) In the configuration of (1) above, the glass composition is SiO in mol% ２ 65.0-85.0%, Al２ O ３ 0-10.0%, B ２ O ３ 0.1-25.0%, Li ２ O 0-5.0%, Na ２ O 1.0-20.0%, K ２ It is preferable that it contains 0 to 20.0% of O.

[0016] (7) In any of the above configurations (1) to (6), the glass composition is SiO in mol% ２ 75.0-85.0%, Al ２ O ３ 0-5.0%, B ２ O ３ 0.1-25.0%, Li ２ O 0-5.0%, Na ２ O 1.0-20.0%, K ２ It is preferable that it contains 0 to 20.0% of O.

[0017] (8) In any of the above configurations (1) to (7), the glass composition is 0.001 to 3.0% Cl and SnO in mol%. ２ Preferably, it further contains at least one of 0.01 to 1.0%.

[0018] (9) In any of the above configurations (1) to (8), it is preferable that the glass composition contains 0.05 to 1.0% of Cl in mol%.

[0019] (10) In any of the above configurations (1) to (9), the glass composition is SnO in mol% ２ It is preferable that it contains 0.05 to 0.5%.

[0020] (11) In any of the configurations (1) to (10) above, it is preferable that the thickness of the perforated glass substrate is 0.03 mm or more and 2.00 mm or less, the TTV of the perforated glass substrate is 20 μm or less, and the warpage of the perforated glass substrate is 60 μm or less.

[0021] (12) In any of the above configurations (1) to (11), it is preferable that the HF etching rate is 1.00 μm / min or less.

[0022] (13) In any of the above configurations (1) to (12), the average coefficient of thermal expansion in the temperature range of 30 to 380°C is 20 × 10 －７ ~100 x 10 －７ It is preferable that the temperature is / ℃.

[0023] (14) In any of the configurations (1) to (13) above, it is preferable that the side surface of the through hole is inclined with respect to the plate thickness direction, and the average taper angle of the side surface is 0 to 13.0°.

[0024] (15) In any of the configurations (1) to (14) above, the through hole preferably has a constricted portion in the center of the thickness direction of the perforated glass substrate, the constricted portion having a smaller diameter than the diameter of the through hole on the first main surface and the second main surface, and the diameter of the constricted portion is preferably 5% or more and 99% or less of the diameter of the through hole on the first main surface and the diameter of the through hole on the second main surface.

[0025] (16) In any of the configurations (1) to (15) above, it is preferable that the diameter of the first main surface of the through hole is 5 μm or more and 200 μm or less, and the diameter of the second main surface of the through hole is 5 μm or more and 200 μm or less.

[0026] (17) In any of the configurations (1) to (16) above, it is preferable that at least the inner surface of the through hole is an etched surface.

[0027] (18) The glass substrate of the present invention, which was devised to solve the above problems, has a glass composition of SiO in mol%. ２ 65.0-85.0%, Al ２ O ３ 0-10.0%, B ２ O ３ 0.1-25.0%, Li ２ O 0-5.0%, Na ２ O 0-20.0%, K ２ It is characterized by containing 0 to 20.0% of O.

[0028] (19) In the configuration of (18) above, the glass substrate has a glass composition of SiO in mol%. ２ 65.0-85.0%, Al ２ O３ 0 to 10.0%, B ２ O ３ 0.1 to 20.0%, Li ２ O 0 to 3.0%, Na ２ O 0 to 20.0%, K ２ It is preferable to contain 0 to 20.0% of O.

[0029] (20) In the structure of the above (18), the glass substrate, as a glass composition, in mol%, SiO ２ 65.0 to 85.0%, Al ２ O ３ 0 to 10.0%, B ２ O ３ 5.0 to 25.0%, Li ２ O 0 to 5.0%, Na ２ O 0 to 20.0%, K ２ It is preferable to contain 0 to 5.0% of O.

[0030] (21) In the structure of the above (18), the glass substrate, as a glass composition, in mol%, SiO ２ 65.0 to 85.0%, Al ２ O ３ 0 to 10.0%, B ２ O ３ 0.1% or more and less than 5.0%, Li ２ O 0 to 5.0%, Na ２ O 0 to 20.0%, K ２ It is preferable to contain 0 to 20.0% of O.

[0031] (22) In the structure of the above (18), the glass substrate, as a glass composition, in mol%, SiO ２ 65.0 to 85.0%, Al ２ O ３ 0 to 10.0%, B ２ O ３ 0.1 to 25.0%, Li ２ O 0 to 5.0%, Na ２ O 0 to 20.0%, K ２ It is preferable to contain more than 5.0% and 20.0% or less of O.

[0032] (23) In any of the configurations (18) to (22) above, the glass substrate has a glass composition of 0.001 to 3.0% Cl and SnO in mol%. ２ Preferably, it further contains at least one of 0.01 to 1.0%.

[0033] (24) In any of the configurations (18) to (23) above, the glass substrate is preferably a glass substrate for manufacturing perforated glass substrates.

[0034] (25) A method for manufacturing a perforated glass substrate of the present invention, devised to solve the above problems, is characterized by comprising: a preparation step of preparing a glass substrate having any of the configurations (18) to (24) above; a laser irradiation step of irradiating a portion of the glass substrate where through holes are to be formed with laser light to form a modified portion; and an etching step of etching the glass substrate having the modified portion to form a perforated glass substrate having through holes.

[0035] (26) Another aspect of the glass substrate manufacturing method of the present invention, which was devised to solve the above problems, is SnO ２ , Cl, F, Br, I, C, metal Al, metal Si, As ２ O ３ Sb ２ O ３ SO ３ NO ３ Fe ２ O ３ , and CEO ２ The process comprises a blending step of blending a glass batch containing two or more types selected from the group consisting of; a melting step of melting the blended glass batch to obtain molten glass; and a molding step of shaping the molten glass to obtain a glass substrate, wherein the glass substrate has a glass composition of SiO in mol%. ２ 65.0-85.0%, Al ２ O ３ 0-10.0%, B ２ O ３ 0.1-25.0%, Li ２ O 0-5.0%, Na ２ O 0-20.0%, K ２ It is characterized by containing 0 to 20.0% of O.

[0036] (27) Another aspect of the method for manufacturing a perforated glass substrate according to the present invention, which was devised to solve the above problems, is SnO ２ , Cl, F, Br, I, C, metal Al, metal Si, As ２ O ３ Sb ２ O ３ SO ３ NO ３ Fe ２ O ３ , and CEO ２ The process comprises: a compounding step of compounding a glass batch containing two or more types selected from the group consisting of; a melting step of melting the compounded glass batch to obtain molten glass; a molding step of shaping the molten glass to obtain a glass substrate; a laser irradiation step of irradiating the portion of the glass substrate where through holes are to be formed with laser light to form a modified portion; and an etching step of etching the glass substrate having the modified portion to form a perforated glass substrate having through holes, wherein the perforated glass substrate has a glass composition of SiO in mol%. ２ 65.0-85.0%, Al ２ O ３ 0-10.0%, B ２ O ３ 0.1-25.0%, Li ２ O 0-5.0%, Na ２ O 0-20.0%, K ２ The result is glass containing 0-20.0% of O.

[0037] According to the present invention, it is possible to provide a perforated glass substrate, a glass substrate, and a method for manufacturing a perforated glass substrate that are suitable for forming through holes that are close to a straight shape, have excellent productivity, and are less prone to deformation of the substrate when semiconductor elements are mounted.

[0038] Figure 1 is a schematic diagram showing the annealing temperature profile when measuring the HF etching rate of a glass substrate according to one embodiment of the present invention. Figure 2 is a top view showing a perforated glass substrate according to one embodiment of the present invention. Figure 3 is a cross-sectional view taken along line A-A of the perforated glass substrate in Figure 2. Figure 4 is a schematic cross-sectional view showing a first example of through holes formed in a perforated glass substrate according to one embodiment of the present invention. Figure 5 is a schematic cross-sectional view showing a second example of through holes formed in a perforated glass substrate according to one embodiment of the present invention. Figure 6 is a flow chart showing a method for manufacturing a perforated glass substrate according to one embodiment of the present invention. Figure 7 is a flow chart showing details of the preparation step in the method for manufacturing a perforated glass substrate according to one embodiment of the present invention. Figure 8 is a perspective view showing a laser irradiation step according to one embodiment of the present invention. Figure 9 is a schematic diagram for comparing a glass substrate and a perforated glass substrate according to one embodiment of the present invention.

[0039] Embodiments of the present invention will be described below with reference to the drawings.

[0040] [First Embodiment] First, the glass composition and properties of the glass substrate according to the first embodiment will be described. The glass substrate according to this embodiment comprises a first main surface and a second main surface which is the opposite surface of the first main surface, and is a glass substrate (non-porous glass substrate) in a state before through holes are formed between the first main surface and the second main surface. Furthermore, the glass substrate according to this embodiment is used for semiconductor package substrate applications.

[0041] The glass substrate according to the first embodiment has a glass composition of SiO in mol%. ２ 65.0-85.0%, Al ２ O ３ 0-10.0%, B ２ O ３ 0.1-25.0%, Li ２ O 0-5.0%, Na ２ O 0-20.0%, K ２It is characterized by containing 0 to 20.0% of O. The reasons for limiting the content of each component as described above are shown below. In the description of the content of each component, the percentage indicates mole percent unless otherwise specified. Also, unless otherwise specified, the upper limit value means that it is less than or equal to that value, and the lower limit value means that it is greater than or equal to that value.

[0042] SiO ２ SiO is a component that forms the framework of glass. ２ If the content is too low, chemical resistance decreases. In particular, the HF etching rate increases, which increases the rate of hole diameter expansion when forming through holes, and the taper angle of the through holes becomes larger. In other words, it becomes difficult to form through holes that are close to a straight shape. Therefore, SiO ２ The lower limit is 65.0%, preferably 68.0%, more preferably 69.0%, more preferably 70.0%, more preferably 71.0%, more preferably 72.0%, more preferably 73.0%, more preferably 74.0%, more preferably 75.0%, more preferably 76.0%, more preferably 77.0%, more preferably 78.0%, more preferably 79.0%, and particularly preferably 80.0%. On the other hand, SiO ２ If the content is too high, the high-temperature viscosity increases, requiring more heat for melting, which raises the melting cost, and also increases the SiO content. ２ Undissolved raw materials may remain, potentially leading to a decrease in yield. Furthermore, cristobalite is more likely to precipitate during molding. Therefore, SiO ２ The upper limit of SiO is 85.0%, preferably 84.0%, more preferably 83.5%, more preferably 83.0%, more preferably 82.5%, and particularly preferably 82.0%. ２The content is 65.0% to 85.0%, preferably 68.0% to 85.0%, more preferably 69.0% to 85.0%, more preferably 70.0% to 85.0%, more preferably 71.0% to 85.0%, more preferably 72.0% to 85.0%, more preferably 73.0% to 85.0%, more preferably 74.0% to 85.0%, more preferably 75.0% to 85.0%, more preferably 76.0% to 84.0%, more preferably 77.0% to 83.5%, more preferably 78.0% to 83.0%, more preferably 79.0% to 82.5%, and particularly preferably 80.0% to 82.0%.

[0043] Al ２ O ３ Al is a component that forms the framework of glass. ２ O ３ If the content is too low, chemical resistance will decrease. In particular, the HF etching rate will increase, which will increase the rate at which the hole diameter expands when forming through holes, and the taper angle of the through holes will become larger. In other words, it will become difficult to form through holes that are close to a straight shape. Therefore, Al ２ O ３ The lower limit of the amount is 0%, preferably 0.1%, more preferably 0.5%, more preferably 0.7%, more preferably 0.8%, more preferably 0.9%, more preferably 1.0%, more preferably 1.1%, more preferably 1.2%, and particularly preferably 1.3%. On the other hand, Al ２ O ３ If the content is too high, the high-temperature viscosity will increase, and meltability and moldability will easily decrease. Therefore, Al ２ O ３ The upper limit of the amount is 10.0%, preferably 9.0%, more preferably 8.0%, more preferably 7.0%, more preferably 6.0%, more preferably 5.0%, more preferably 4.0%, more preferably 3.0%, more preferably 2.5%, more preferably 2.0%, more preferably 1.9%, more preferably 1.8%, more preferably 1.7%, and particularly preferably 1.6%. Therefore, Al ２ O ３The content is 0% to 10.0%, preferably 0% to 9.0%, more preferably 0% to 8.0%, more preferably 0% to 7.0%, more preferably 0% to 6.0%, more preferably 0% to 5.0%, more preferably 0.1% to 5.0%, more preferably 0.5% to 4.0%, more preferably 0.7% to 3.0%, more preferably 0.8% to 2.5%, more preferably 0.9% to 2.0%, more preferably 1.0% to 1.9%, more preferably 1.1% to 1.8%, more preferably 1.2% to 1.7%, and particularly preferably 1.3% to 1.6%.

[0044] B ２ O ３ The content is 0.1 to 25.0%, preferably 5.0 to 25.0%, but may be 0.1% or more and less than 5.0%. ２ O ３ This component forms the framework of the glass and also reduces its high-temperature viscosity. ２ O ３ If the content is too low, the high-temperature viscosity will increase, and meltability and moldability will easily decrease. Therefore, B ２ O ３ The lower limit of the amount is 0.1%, preferably 0.2%, more preferably 0.5%, more preferably 0.8%, more preferably 1.0%, more preferably 2.0%, more preferably 3.0%, more preferably 4.0%, more preferably 5.0%, more preferably 8.0%, more preferably 9.0%, more preferably 10.0%, more preferably 11.0%, more preferably 11.5%, more preferably 11.6%, more preferably 11.7%, more preferably 11.8%, more preferably 11.9%, and particularly preferably 12.0%. On the other hand, B ２ O ３ If the content is too high, the chemical resistance decreases. In particular, the HF etching rate increases, so the taper angle when forming through holes becomes larger. Also, the glass becomes more prone to phase separation. When the glass separates, the glass substrate becomes cloudy and the transmittance of the glass substrate decreases. As a result, when a laser is irradiated onto the glass substrate to form through holes, the laser light is scattered, making it difficult to form the modified area. Therefore, B ２ O３ The upper limit of the amount is 25.0%, preferably 24.0%, more preferably 23.0%, more preferably 22.0%, more preferably 21.0%, more preferably 20.0%, more preferably 19.8%, more preferably 19.5%, more preferably 19.3%, more preferably 19.0%, more preferably 18.8%, more preferably 18.5%, more preferably 18.0%, more preferably 17.0%, more preferably 16.0%, more preferably 15.0%, more preferably 14.0%, more preferably 13.5%, more preferably 13.4%, more preferably 13.3%, more preferably 13.2%, more preferably 13.1%, and particularly preferably 13.0%. Therefore, B ２ O ３ The content is 0.1 to 25.0%, preferably 0.1 to 24.0%, preferably 0.1 to 23.0%, preferably 0.1 to 22.0%, preferably 0.1 to 21.0%, preferably 0.1 to 20.0%, preferably 0.2% to 20.0%, more preferably 0.5% to 19.8%, more preferably 0.8% to 19.5%, more preferably 1.0% to 19.3%, more preferably 2.0% to 19.0%, more preferably 3.0% to 18.8%, and even more preferably The amount is 4.0% to 18.5%, more preferably 5.0% to 18.0%, more preferably 8.0% to 17.0%, more preferably 9.0% to 16.0%, more preferably 10.0% to 15.0%, more preferably 11.0% to 14.0%, more preferably 11.5% to 13.5%, more preferably 11.6% to 13.4%, more preferably 11.7% to 13.3%, more preferably 11.8% to 13.2%, more preferably 11.9% to 13.1%, and particularly preferably 12.0% to 13.0%.

[0045] In particular, from the perspective of increasing the Young's modulus of the glass substrate, B ２ O ３ It is preferable that the content of is 0.1% or more and less than 5.0%. By keeping it within this range, it becomes easier to increase the Young's modulus of the glass substrate, and defects caused by deformation of the perforated glass substrate during semiconductor device mounting become less likely to occur. In this case, B ２ O ３The upper limit of is preferably 4.5%, more preferably 4.0%, more preferably 3.5%, and particularly preferably 3.0%. Therefore, from the viewpoint of increasing the Young's modulus of the glass substrate, B ２ O ３ The content is preferably 0.1% to 4.5%, more preferably 0.1% to 4.0%, more preferably 0.1% to 3.5%, and particularly preferably 0.1% to 3.0%.

[0046] Li ２ O is a component that reduces the high-temperature viscosity of glass and increases its meltability. Li ２ If the oxygen content is too low, the high-temperature viscosity will increase, and meltability and moldability will easily decrease. Therefore, Li ２ The lower limit of O is 0%, preferably 0.001%, more preferably 0.005%, and particularly preferably 0.01%. On the other hand, Li ２ If the O content is too high, batch costs will increase, and manufacturing costs will rise. Also, the glass will be more prone to phase separation, and the transmittance of the glass substrate will decrease. As a result, when a laser is irradiated onto the glass substrate to form through holes, the laser light will be scattered, making it difficult to form the modified area. Therefore, Li ２ The upper limit of O is 5.0%, preferably 4.0%, more preferably 3.0%, more preferably 2.0%, more preferably 1.0%, more preferably 0.5%, more preferably 0.3%, more preferably 0.2%, and particularly preferably 0.1%. Therefore, Li ２ The O content is 0% to 5.0%, preferably 0% to 4.0%, more preferably 0% to 3.0%, more preferably 0% to 2.0%, more preferably 0% to 1.0%, more preferably 0% to 0.5%, more preferably 0.001% to 0.3%, more preferably 0.005% to 0.2%, and particularly preferably 0.01% to 0.1%.

[0047] Na ２ O is a component that reduces the high-temperature viscosity of glass and increases its meltability. Na ２ If the O content is too low, the high-temperature viscosity will increase, and meltability and moldability will easily decrease. Therefore, Na ２The lower limit of O is 0%, preferably 1.0%, more preferably 2.0%, more preferably 3.0%, more preferably 3.5%, and particularly preferably 4.0%. On the other hand, Na ２ If the O content is too high, the coefficient of thermal expansion will increase, which may lead to excessive deformation of the perforated glass substrate during semiconductor device mounting and potentially cause the perforated glass substrate to break. Therefore, Na ２ The upper limit of O is 20.0%, preferably 18.0%, more preferably 15.0%, more preferably 14.0%, more preferably 13.0%, more preferably 12.0%, more preferably 11.0%, more preferably 10.0%, more preferably 9.0%, more preferably 8.0%, more preferably 7.0%, more preferably 6.0%, more preferably 5.5%, more preferably 5.4%, more preferably 5.3%, more preferably 5.2%, more preferably 5.1%, and particularly preferably 5.0%. Therefore, Na ２ The O content is 0% to 20.0%, preferably 1.0% to 20.0%, preferably 2.0% to 18.0%, more preferably 3.0% to 15.0%, more preferably 3.5% to 14.0%, more preferably 4.0% to 13.0%, more preferably 4.0% to 12.0%, more preferably 4.0% to 11.0%, more preferably 4.0% to 10.0%, more preferably 4.0% to 9.0%, more preferably 4.0% to 8.0%, more preferably 4.0% to 7.0%, more preferably 4.0% to 6.0%, more preferably 4.0% to 5.5%, more preferably 4.0% to 5.4%, more preferably 4.0% to 5.3%, more preferably 4.0% to 5.2%, more preferably 4.0% to 5.1%, and particularly preferably 4.0% to 5.0%.

[0048] K ２ The O content is 0 to 20.0%, preferably 0 to 5.0%, but may be greater than 5.0% and less than or equal to 20.0%. ２O is a component that reduces the high-temperature viscosity of glass and increases its meltability. K ２ If the O content is too low, the high-temperature viscosity will increase, and meltability and moldability will easily decrease. Therefore, K ２ The lower limit of O is 0%, preferably 0.001%, more preferably 0.003%, more preferably 0.005%, more preferably 0.008%, and particularly preferably 0.01%. On the other hand, K ２ If the O content is too high, the coefficient of thermal expansion increases, which can lead to excessive deformation of the perforated glass substrate during semiconductor device mounting and potentially cause damage to the perforated glass substrate. Furthermore, dielectric loss increases, making it easier for the device characteristics of the perforated glass substrate to deteriorate. Therefore, K ２ The upper limit of O is 20.0%, preferably 18.0%, more preferably 15.0%, more preferably 14.0%, more preferably 13.0%, more preferably 12.0%, more preferably 11.0%, more preferably 10.0%, more preferably 9.0%, more preferably 8.0%, more preferably 7.0%, more preferably 6.0%, more preferably 5.0%, more preferably 4.0%, more preferably 3.0%, more preferably 2.0%, more preferably 1.0%, more preferably 0.9%, more preferably 0.8%, more preferably 0.7%, more preferably 0.6%, and particularly preferably 0.5%. Therefore, K ２The O content is preferably 0% to 18.0%, more preferably 0% to 15.0%, more preferably 0% to 14.0%, more preferably 0% to 13.0%, more preferably 0% to 12.0%, more preferably 0% to 11.0%, more preferably 0% to 10.0%, more preferably 0% to 9.0%, more preferably 0% to 8.0%, more preferably 0% to 7.0%, more preferably 0% to 6.0%, more preferably 0% to 5.0%, more preferably 0% to 4.0%, more preferably 0% to 3.0%, more preferably 0% to 2.0%, more preferably 0% to 1.0%, more preferably 0.001% to 0.9%, more preferably 0.003% to 0.8%, more preferably 0.005% to 0.7%, more preferably 0.008% to 0.6%, and particularly preferably 0.01% to 0.5%.

[0049] In particular, from the viewpoint of improving the meltability of glass, K ２ It is preferable that the O content be between 5.0% and 20.0%. By keeping it within this range, the high-temperature viscosity of the glass decreases, and the melting temperature is lowered, thereby reducing the manufacturing cost of the glass substrate. In this case, K ２ The lower limit of O is preferably 5.5%, more preferably 6.0%, more preferably 6.5%, and particularly preferably 7.0%. Therefore, from the viewpoint of improving the meltability of the glass, K ２ The O content is preferably 5.5% to 20.0%, more preferably 6.0% to 20.0%, more preferably 6.5% to 20.0%, and particularly preferably 7.0% to 20.0%.

[0050] MgO is a component that enhances HF resistance and also reduces the high-temperature viscosity of the glass, thereby improving meltability. If the MgO content is too low, the HF etching rate increases, and the taper angle of the through-hole tends to become larger. Also, the high-temperature viscosity increases, and meltability and moldability tend to decrease. Therefore, the lower limit of MgO is preferably 0%, more preferably 0.01%, more preferably 0.1%, more preferably 0.2%, more preferably 0.3%, more preferably 0.4%, and particularly preferably 0.5%. On the other hand, if the MgO content is too high, the glass tends to split into phases, and the transmittance of the glass substrate decreases. As a result, when a laser is irradiated onto the glass substrate to form through-holes, the laser light is scattered, and it becomes difficult to form modified areas. Therefore, the upper limit of MgO is preferably 5.0%, more preferably 4.0%, more preferably 3.0%, more preferably 2.0%, more preferably 1.5%, and particularly preferably 1.0%. Therefore, the MgO content is preferably 0% to 5.0%, more preferably 0.01% to 4.0%, more preferably 0.1% to 3.0%, more preferably 0.2% to 2.0%, more preferably 0.3% to 1.5%, more preferably 0.4% to 1.0%, and particularly preferably 0.5% to 1.0%.

[0051] CaO is a component that reduces the high-temperature viscosity of glass and increases its meltability. If the CaO content is too low, the high-temperature viscosity will increase, and meltability and moldability will tend to decrease. Therefore, the lower limit of the CaO content is preferably 0%, more preferably 0.01%, more preferably 0.1%, more preferably 0.2%, more preferably 0.3%, more preferably 0.4%, and particularly preferably 0.5%. On the other hand, if the CaO content is too high, the mass of residue generated when etching the glass substrate to form through holes will increase. This makes it easier for residue clogging to occur in the etching apparatus, increasing the frequency of residue processing and raising the manufacturing cost of perforated glass substrates. The mass of the residue generated in this case is proportional to the formula weight of the salt composed of alkaline earth metal, Al, and F, so the larger the atomic weight of the alkaline earth metal, the more likely this problem is to become apparent. In particular, when forming through holes by etching, residue equivalent to the volume of the through holes is generated in addition to the amount of reduction in the thickness of the glass substrate. When numerous through-holes are made in a glass substrate, the amount of residue generated increases in proportion to the number of through-holes, which tends to increase manufacturing costs. Furthermore, as the mass of residue increases, when etching the glass substrate to form through-holes, the residue adheres to the inside of the through-holes, hindering the supply of etching solution to the inside of the through-holes. This can lead to an increase in the taper angle of the through-holes (i.e., difficulty in forming straight-shaped through-holes) or an increase in the variation in the diameter of the through-holes. Therefore, the upper limit of CaO is preferably 8.0%, more preferably 7.0%, more preferably 6.0%, more preferably 5.0%, more preferably 4.0%, more preferably 3.8%, more preferably 3.5%, more preferably 3.0%, more preferably 2.0%, more preferably 1.5%, and particularly preferably 1.0%. Therefore, the CaO content is preferably 0% to 8.0%, more preferably 0.01% to 7.0%, more preferably 0.1% to 6.0%, more preferably 0.2% to 5.0%, more preferably 0.3% to 4.0%, more preferably 0.4% to 3.8%, more preferably 0.5% to 3.5%, more preferably 0.5% to 3.0%, more preferably 0.5% to 2.0%, more preferably 0.5% to 1.5%, and particularly preferably 0.5% to 1.0%.

[0052] SrO is a component that reduces the high-temperature viscosity of glass and increases its meltability. If the SrO content is too low, the high-temperature viscosity will increase, and meltability and moldability will tend to decrease. Therefore, the lower limit of SrO is preferably 0%, more preferably 0.01%, more preferably 0.1%, more preferably 0.2%, more preferably 0.3%, more preferably 0.4%, and particularly preferably 0.5%. On the other hand, if the SrO content is too high, the coefficient of thermal expansion will increase, which may lead to greater deformation of the perforated glass substrate during semiconductor device mounting and potentially cause damage to the perforated glass substrate. Furthermore, the mass of residue generated when etching the glass substrate to form through holes will increase, and as mentioned above, problems such as increased manufacturing costs, increased taper angles of through holes, and increased variations in the diameter of through holes are likely to occur. Therefore, the upper limit of SrO is preferably 5.0%, more preferably 4.0%, more preferably 3.0%, more preferably 2.0%, more preferably 1.5%, and particularly preferably 1.0%. Therefore, the SrO content is preferably 0% to 5.0%, more preferably 0.01% to 5.0%, more preferably 0.1% to 4.0%, more preferably 0.2% to 3.0%, more preferably 0.3% to 2.0%, more preferably 0.4% to 1.5%, and particularly preferably 0.5% to 1.0%.

[0053] BaO is a component that reduces the high-temperature viscosity of glass and increases its meltability. It is also a component that improves its resistance to devitrification. If the BaO content is too low, it becomes difficult to enjoy the above effects. Therefore, the lower limit of the BaO content is preferably 0%, more preferably 0.01%, more preferably 0.1%, more preferably 0.2%, and particularly preferably 0.3%. On the other hand, if the BaO content is too high, the coefficient of thermal expansion increases, which may lead to greater deformation of the perforated glass substrate during semiconductor device mounting and potentially cause damage to the perforated glass substrate. Furthermore, the mass of residue generated when etching the glass substrate to form through holes increases, and as mentioned above, problems such as increased manufacturing costs, increased taper angles of through holes, and increased variations in the diameter of through holes are more likely to occur. Therefore, the upper limit of BaO is preferably 5.0%, more preferably 4.0%, more preferably 3.0%, more preferably 2.0%, more preferably 1.5%, more preferably 1.0%, more preferably 0.9%, more preferably 0.8%, more preferably 0.7%, more preferably 0.6%, and particularly preferably 0.5%. Accordingly, the BaO content is preferably 0% to 5.0%, more preferably 0.01% to 4.0%, more preferably 0.1% to 3.0%, more preferably 0.2% to 2.0%, more preferably 0.3% to 1.5%, more preferably 0.3% to 1.0%, more preferably 0.3% to 0.9%, more preferably 0.3% to 0.8%, more preferably 0.3% to 0.7%, more preferably 0.3% to 0.6%, and particularly preferably 0.3% to 0.5%.

[0054] If the total content of MgO, CaO, SrO, and BaO is too low, the high-temperature viscosity will increase, and meltability and moldability will tend to decrease. Therefore, the lower limit of the total content of MgO, CaO, SrO, and BaO is preferably 0%, more preferably 0.01%, more preferably 0.1%, more preferably 0.2%, more preferably 0.3%, more preferably 0.4%, and particularly preferably 0.5%. On the other hand, if the total content of MgO, CaO, SrO, and BaO is too high, the coefficient of thermal expansion will increase, which may lead to greater deformation of the perforated glass substrate during semiconductor device mounting and potentially cause damage to the perforated glass substrate. Furthermore, the mass of residue generated when etching the glass substrate to form through holes will increase, and as mentioned above, problems such as increased manufacturing costs, increased taper angles of through holes, and increased variations in the diameter of through holes are more likely to occur. Therefore, the upper limit of the total content of MgO, CaO, SrO, and BaO is preferably 8.0%, more preferably 5.0%, more preferably 4.0%, more preferably 3.0%, more preferably 2.0%, more preferably 1.5%, and particularly preferably 1.0%. Accordingly, the total content of MgO, CaO, SrO, and BaO is preferably 0% to 8.0%, more preferably 0.01% to 5.0%, more preferably 0.1% to 4.0%, more preferably 0.2% to 3.0%, more preferably 0.3% to 2.0%, more preferably 0.4% to 1.5%, and particularly preferably 0.5% to 1.0%.

[0055] SnO ２ SnO is a component that has good clarifying properties in the high-temperature range, as well as a component that reduces high-temperature viscosity and improves meltability. Therefore, in order to produce glass substrates with good yield, SnO ２ It is preferable that it contains SnO. ２ The lower limit of the amount is preferably 0%, more preferably 0.01%, more preferably 0.05%, and particularly preferably 0.08%. On the other hand, SnO ２ If the content is too high, SnO ２ Devitrified crystals are more likely to precipitate, which may lead to a decrease in yield. Therefore, SnO ２ The upper limit of is preferably 1.0%, more preferably 0.8%, and particularly preferably 0.5%. Therefore, SnO２ The content is preferably 0% to 1.0%, more preferably 0.01% to 0.8%, more preferably 0.05% to 0.5%, and particularly preferably 0.08% to 0.5%.

[0056] As described above, SnO ２ While is suitable as a clarifying agent, as long as the glass properties are not impaired, SnO ２ Instead, or SnO ２ Along with F, SO ３ Metal powders such as C, Al, or Si can be added in amounts up to 1% each (preferably up to 0.8%, particularly up to 0.5%). Additionally, CeO can be used as a clarifying agent. ２ It can also be added, but CeO ２ If the content is too high, the glass will become discolored, and when the glass substrate is irradiated with a laser to form through holes, the heat generated at the laser irradiation site will increase, making it easier for defects such as cracks to occur. For this reason, the upper limit of its content is preferably 0.1%, more preferably 0.05%, and particularly preferably 0.01%. Therefore, F, SO ３ The content of metal powders such as C, Al, or Si is 0% to 1%, preferably 0% to 0.8%, preferably 0% to 0.5%, preferably 0% to 0.1%, more preferably 0% to 0.05%, and particularly preferably 0% to 0.01%.

[0057] Cl is a component that promotes the initial melting of glass batches. Furthermore, the addition of Cl can enhance the action of clarifying agents. As a result, melting costs can be reduced while extending the lifespan of the glass manufacturing furnace. Therefore, the lower limit of Cl is preferably 0%, more preferably 0.001%, more preferably 0.01%, more preferably 0.05%, more preferably 0.08%, and particularly preferably 0.10%. On the other hand, if the Cl content is too high, the strain point tends to decrease, which may lead to a decrease in peel strength and deformation of the glass substrate during the heat treatment process in the plating process. Therefore, the upper limit of Cl is preferably 3.0%, more preferably 2.0%, more preferably 1.0%, more preferably 0.8%, and particularly preferably 0.5%. For example, raw materials such as NaCl can be used as the Cl introduction raw material. Also, since Cl is a volatile component during melting, the Cl content in the batch may be appropriately adjusted during manufacturing so that the amount of Cl in the molded glass substrate satisfies the above range. Therefore, the Cl content is preferably 0% to 3.0%, more preferably 0.001% to 2.0%, more preferably 0.01% to 1.0%, more preferably 0.05% to 0.8%, more preferably 0.08% to 0.5%, and particularly preferably 0.10% to 0.5%.

[0058] In this embodiment, it is preferable to have two or more clarifying components coexist in the glass batch during manufacturing. Specifically, SnO ２ , Cl, F, Br, I, C, metal Al, metal Si, As ２ O ３ Sb ２ O ３ SO ３ NO ３ Fe ２ O ３ , and CEO ２ Preferably, it contains two or more selected from the group consisting of SnO ２ ,Cl,F,C,SO ３ NO ３ Fe ２ O ３ , and CEO ２ It includes two or more types selected from the group consisting of, and SnO２ It is more preferable to include at least one of the following: Cl, F, SO ３ , and NO ３ It includes one or more selected from the group consisting of SnO ２ It is more preferable to include SnO ２ It is particularly preferable that it also contains Cl. Furthermore, the lower limit of the total amount of clarifying components is preferably 0%, more preferably 0.001%, more preferably 0.005%, more preferably 0.01%, and particularly preferably 0.05%, in weight percentage relative to the batch weight. In this way, the clarification effect can be promoted and the melting cost can be reduced. Also, since the melting temperature can be lowered, B ２ O ３ or Na ２ This reduces the amount of volatilization of oxygen (O) and improves the homogeneity of the molded glass substrate. If compositional unevenness occurs in the glass substrate due to volatilization or other factors, regions with different etching rates will occur in the glass substrate when forming through holes by etching, resulting in variations in the resulting hole shape. Therefore, it is important to select the clarifying components in this way, especially for perforated glass substrates. The upper limit of the total amount of clarifying components is preferably 5%, more preferably 4%, more preferably 3%, more preferably 2%, and particularly preferably 1%, as a weight percentage of the batch weight. If the amount of clarifying components in the batch is too high, the amount of volatile components in the glass melting furnace increases, making the melting furnace more susceptible to deterioration due to volatile components, shortening its lifespan, and consequently increasing manufacturing costs. It also increases the environmental burden. Therefore, the total amount of clarifying components is preferably 0% to 5%, more preferably 0.001% to 4%, more preferably 0.005% to 3%, more preferably 0.01% to 2%, and particularly preferably 0.05% to 1%, as a weight percentage of the batch weight.

[0059] In addition to the above components, the following components may be added as optional components. However, from the viewpoint of effectively enjoying the effects of the present invention, the total amount of other components is preferably 5% or less, and particularly preferably 1% or less.

[0060] TiO ２It is a component that lowers high-temperature viscosity and increases meltability, but TiO ２ If a large amount of this substance is included, the glass substrate will become discolored, and when the glass substrate is irradiated with a laser to form through holes, the heat generated at the laser-irradiated area will increase, making it easier for defects such as cracks to occur. Therefore, the content is preferably 0 to 0.1%, more preferably 0.0005 to 0.1%, particularly preferably 0.005 to 0.08%, and most preferably 0.005 to 0.05%.

[0061] ZnO is a component that lowers high-temperature viscosity and increases meltability. However, if a large amount of ZnO is included, the glass substrate will become discolored, and when the glass substrate is irradiated with a laser to form through holes, the heat generated at the laser-irradiated area will increase, making it easier for defects such as cracks to occur. Therefore, the content is preferably 0 to 10.0%, more preferably 0 to 9.0%, more preferably 0 to 8.0%, more preferably 0 to 7.0%, more preferably 0 to 6.0%, more preferably 0 to 5.0%, more preferably 0 to 4.0%, more preferably 0 to 3.0%, more preferably 0 to 2.0%, more preferably 0 to 1.0%, more preferably 0 to 0.5%, more preferably 0 to 0.4%, more preferably 0 to 0.3%, more preferably 0 to 0.2%, and particularly preferably 0 to 0.1%.

[0062] P ２ O ５ This component enhances HF resistance and facilitates the formation of through-holes in the glass substrate that are close to a straight shape. Therefore, P ２ O ５ The lower limit of P is preferably 0%, more preferably 0.0005%, more preferably 0.001%, and particularly preferably 0.005%. On the other hand, P ２ O ５ When a large amount of is included, the glass becomes more prone to phase separation. When the glass separates, the glass substrate becomes cloudy and the transmittance of the glass substrate decreases. As a result, when a laser is irradiated onto the glass to form through holes, the laser light is scattered, making it difficult to form modified areas. Therefore, P ２ O ５The upper limit of P is preferably 2.0%, more preferably 1.5%, more preferably 1.0%, more preferably 0.5%, and particularly preferably 0.3%. Therefore, P ２ O ５ The content is preferably 0% to 2.0%, more preferably 0.0005% to 1.5%, more preferably 0.001% to 1.0%, more preferably 0.005% to 0.5%, and particularly preferably 0.005% to 0.3%.

[0063] CuO is a component that colors glass. If the CuO content is too high, the glass substrate will become colored, and when the glass substrate is irradiated with a laser to form through holes, the heat generated at the laser irradiation site will be excessive, making it easier for defects such as cracks to occur. Therefore, it is desirable to have a low CuO content, preferably 0 to 0.1%, more preferably less than 0 to 0.1%, and particularly preferably 0 to 0.05%.

[0064] Y ２ O ３ , Nb ２ O ５ La ２ O ３ These are components that enhance mechanical properties such as Young's modulus, but if the total amount and individual content of these components are too high, raw material costs tend to increase. Therefore, Y ２ O ３ , Nb ２ O ５ La ２ O ３ The total amount and individual content are preferably 0 to 5%, more preferably 0 to 3%, more preferably 0 to 1%, even more preferably 0 to 0.5%, and particularly preferably less than 0 to 0.5%.

[0065] Fe ２ O ３ Fe is a component that is inevitably mixed in from the glass raw materials and is also a component that colors the glass. It also has the effect of a clarifying agent. ２ O ３ If the content is too low, raw material costs tend to rise. Also, bubble defects are more likely to occur in the glass. On the other hand, Fe ２ O ３If the content is too high, the glass substrate will become discolored, and when the glass substrate is irradiated with a laser to form through holes, the heat generated at the laser irradiation site will be excessive, making it easier for defects such as cracks to occur. Therefore, Fe ２ O ３ The content is preferably 0 to 1000 ppm, more preferably 30 to 800 ppm, and particularly preferably 100 to 200 ppm.

[0066] ZrO ２ ZrO is a component that inevitably gets mixed in from refractories used in glass manufacturing furnaces. ２ If the content is too high, devitrified crystals are more likely to precipitate. On the other hand, ZrO ２ To reduce the content of ZrO, the melting temperature must be lowered, which makes it difficult to melt the glass. Therefore, ZrO ２ The content is preferably 0 to 0.5%, more preferably 0.0001 to 0.5%, more preferably 0.001 to 0.4%, more preferably 0.003 to 0.3%, more preferably 0.005 to 0.2%, and particularly preferably 0.01 to 0.1%.

[0067] The glass substrate according to the first embodiment preferably has the following characteristics.

[0068] The HF etching rate is preferably 1.00 μm / min or less, more preferably 0.90 μm / min or less, more preferably 0.80 μm / min or less, more preferably 0.70 μm / min or less, more preferably 0.60 μm / min or less, more preferably 0.50 μm / min or less, more preferably 0.40 μm / min or less, more preferably 0.30 μm / min or less, and particularly preferably 0.20 μm / min or less. Here, the HF etching rate refers to the value measured by the following method. First, both sides of a glass substrate sample with a thickness of 1 mm and dimensions of 20 mm × 35 mm were optically polished, and then the glass substrate sample was annealed according to the temperature profile shown in Figure 1, and a part of the main surface was masked. Next, the glass substrate sample was immersed in the etching solution for 10 minutes and etching was performed. 300 mL of a 2.5 mol / L HF aqueous solution was used as the etching solution. When etching was performed, a water bath stirrer was set to 30°C and stirred at approximately 600 rpm. Subsequently, the mask was removed, the glass substrate sample was cleaned, and the step difference between the masked area and the eroded area was measured using a SurfCorder (ET4000A: manufactured by Kosaka Laboratory Co., Ltd.). The etching rate was calculated by dividing the height of this step difference by the immersion time.

[0069] If the etching rate is within this range, the etching rate of the unmodified glass substrate is low, making it difficult for the hole diameter on the main surface of the glass substrate to enlarge when forming through holes, and allowing for a smaller taper angle. As a result, it becomes easier to make the glass substrate thicker, and the glass substrate becomes less prone to deformation during film deposition and semiconductor device mounting. Furthermore, the HF etching rate changes not only with respect to the glass composition but also with respect to the virtual temperature and phase state of the glass.

[0070] The lower limit of the average thermal expansion coefficient CTE in the temperature range of 30 to 380°C is preferably 20 × 10⁻⁶ －７ / ℃ or higher, more preferably 30 × 10 －７ / ℃ or higher, more preferably 32 × 10 －７ / ℃ or higher, more preferably 40 × 10 －７ / ℃ or higher, particularly preferably 50 × 10 －７ It is above / °C. The upper limit of the average thermal expansion coefficient CTE in the temperature range of 30 to 380°C is preferably 100 × 10⁻⁶.－７ / ℃ or lower, more preferably 90 × 10 －７ / ℃ or lower, more preferably 80 × 10 －７ / ℃ or lower, more preferably 70 × 10 －７ / ℃ or lower, more preferably 60 × 10 －７ / ℃ or lower, more preferably 55 × 10 －７ It is below / °C. This makes it easier to match the thermal expansion coefficient of Si when mounting semiconductor elements, and reduces deformation of the perforated glass substrate. Therefore, the average thermal expansion coefficient CTE is preferably 20 × 10 －７ / ℃ or higher 100 x 10 －７ / ℃ or lower, more preferably 30 × 10 －７ / ℃ or higher 90 x 10 －７ / ℃ or lower, more preferably 32 × 10 －７ / ℃ or higher 80 x 10 －７ / ℃ or lower, more preferably 40 × 10 －７ / ℃ or higher 70 x 10 －７ / ℃ or lower, more preferably 40 × 10 －７ / ℃ or higher 60 x 10 －７ / ℃ or lower, particularly preferably 50 × 10 －７ / ℃ or higher 55 x 10 －７ It is below / ℃.

[0071] The Young's modulus is preferably 60 GPa or higher, more preferably 63 GPa or higher, more preferably 65 GPa or higher, more preferably 67 GPa or higher, and particularly preferably 70 GPa or higher. If the Young's modulus is too low, defects caused by deformation of the perforated glass substrate are more likely to occur during the mounting of semiconductor devices.

[0072] The strain point is preferably 400°C or higher, more preferably 430°C or higher, more preferably 460°C or higher, more preferably 470°C or higher, more preferably 480°C or higher, and particularly preferably 490°C or higher. With such a strain point, the peel strength can be increased by raising the heat treatment temperature in the plating process on the perforated glass substrate, and deformation of the substrate during heat treatment can be suppressed.

[0073] In this invention, the temperature at which the slope of the thermal expansion curve of the glass changes is treated as the glass transition temperature. The glass transition temperature is preferably 480°C or higher, more preferably 500°C or higher, more preferably 520°C or higher, more preferably 530°C or higher, more preferably 540°C or higher, and particularly preferably 550°C or higher. With such a glass transition temperature, thermal strain that occurs during the manufacturing of the glass substrate can be reduced, and heat treatment can be performed in a way that does not easily change the phase separation state.

[0074] The softening point is preferably 815°C or lower, more preferably 810°C or lower, and particularly preferably 805°C or lower. With such a softening point, the process temperature during heat treatment to improve the plate quality and phase separation state of the glass substrate can be lowered, thereby reducing manufacturing costs.

[0075] The liquidus temperature is preferably 1300°C or lower, more preferably less than 1200°C, more preferably 1150°C or lower, and particularly preferably 1100°C or lower. This makes it easier to prevent the formation of devitrified crystals during molding, which can reduce productivity. Furthermore, it makes molding easier using the overflow down-draw method, which improves the surface quality of the glass substrate and reduces the manufacturing cost of the glass substrate. The liquidus temperature is an indicator of devitrification resistance; the lower the liquidus temperature, the better the devitrification resistance.

[0076] The liquid-phase viscosity is preferably 10 ４．０ dPa·s or higher, more preferably 10 ４．２ dPa·s or higher, more preferably 10 ４．４ dPa·s or higher, more preferably 10 ４．６ dPa·s or higher, particularly preferably 10 ４．８ The viscosity is dPa·s or higher. This reduces the likelihood of devitrification during molding and lowers the manufacturing cost of the glass substrate. Liquid-phase viscosity is an indicator of devitrification resistance and moldability; the higher the liquid-phase viscosity, the better the devitrification resistance and moldability.

[0077] High temperature viscosity 10 ２．５The temperature at dPa·s is preferably 1900°C or lower, more preferably 1850°C or lower, more preferably 1800°C or lower, more preferably 1750°C or lower, more preferably 1700°C or lower, more preferably 1680°C or lower, more preferably 1650°C or lower, more preferably 1640°C or lower, and particularly preferably 1630°C or lower. High-temperature viscosity 10 ２．５ If the temperature at dPa·s is too high, it becomes difficult to melt the glass batch, increasing the manufacturing cost of the glass substrate. Also, B from the molten glass ２ O ３ or Na ２ The amount of volatilization of oxygen increases, making it easier for a heterogeneous layer to form on the surface of the molten glass, which tends to reduce the homogeneity of the glass. ２．５ The temperature in dPa·s corresponds to the melting temperature, and the lower this temperature, the better the meltability.

[0078] The β-OH value is an indicator of the water content in the glass. Lowering the β-OH value lowers the dielectric constant and dielectric loss tangent of the glass, which in turn reduces transmission loss in the high-frequency band. Therefore, the β-OH value is preferably 0.70 / mm or less, more preferably 0.65 / mm or less, more preferably 0.60 / mm or less, more preferably 0.55 / mm or less, more preferably 0.50 / mm or less, more preferably 0.45 / mm or less, more preferably 0.40 / mm or less, more preferably 0.35 / mm or less, more preferably 0.30 / mm or less, more preferably 0.25 / mm or less, more preferably 0.20 / mm or less, more preferably 0.15 / mm or less, and particularly preferably 0.10 / mm or less.

[0079] The following methods can be used to lower the β-OH value: (1) Select raw materials with low water content. (2) Add components that lower the β-OH value (Cl, SO) to the glass. ３ (3) Add (etc.). (4) Reduce the amount of moisture in the furnace atmosphere. (5) N in the molten glass. ２ (5) Use a small melting furnace. (6) Increase the flow rate of molten glass. (7) Use an electromelting method.

[0080] Here, the "β-OH value" refers to the value obtained by measuring the infrared light transmittance of the glass using Fourier transform infrared spectroscopy (FT-IR) and using the following equation 1: β-OH value = (1 / X) log (T １ / T ２ ) Formula 1 X: Plate thickness (mm) T １ :Reference wavelength 3846cm －１ Transmittance (%) in T ２ Hydroxyl group absorption wavelength: 3600 cm －１ Minimum transmittance in the vicinity (%)

[0081] In this embodiment, the glass substrate is preferably formed by the overflow downdraw method. The overflow downdraw method is a method of manufacturing a glass substrate by allowing molten glass to overflow from both sides of a heat-resistant trough-shaped structure, and then drawing the overflowed molten glass downwards while it is being merged at the lower end of the trough-shaped structure. In the overflow downdraw method, the surface that will become the surface of the glass substrate does not come into contact with the trough-shaped refractory material and is formed in a free surface state. Therefore, it is possible to manufacture glass substrates with good surface quality without polishing at low cost, and thinning is also easy.

[0082] In addition to the overflow downdraw method, glass substrates can also be formed using other methods such as the downdraw method (slot-down method, etc.), the float method, and the roll-out method.

[0083] The shape of the glass substrate in this embodiment is not particularly limited, but it is preferably rectangular when used for semiconductor package substrate applications. The area of ​​the glass substrate in this case is preferably 200,000 mm². ２ Above, a comfortable 220,000 mm ２ More specifically, 240,000 mm ２ In particular, 260,000 mm is preferred. ２ That concludes the explanation. The length of each side of the glass substrate is preferably, for example, 450 mm x 450 mm or more and 1000 mm x 1000 mm or less, and may be, for example, 510 mm x 515 mm. By setting the area of ​​the glass substrate to such a value, the number of package substrates obtained when the substrate is finally separated into individual pieces can be increased.

[0084] In this embodiment, the length of each side of the glass substrate is preferably (510±10mm)×(515±10mm), more preferably (510±5mm)×(515±5mm), even more preferably (510±3mm)×(515±3mm), and particularly preferably (510±1mm)×(515±1mm), based on a standard of 510mm×515mm. By reducing the dimensional tolerance, the accuracy of positioning the glass substrate during wiring pattern formation can be improved, enabling finer wiring.

[0085] The thickness of the glass substrate in this embodiment is not particularly limited, but is preferably 0.03 mm or more, more preferably 0.05 mm or more, more preferably 0.10 mm or more, more preferably 0.20 mm or more, more preferably 0.30 mm or more, more preferably 0.35 mm or more, more preferably 0.40 mm or more, more preferably 0.45 mm or more, and particularly preferably 0.50 mm or more. The thicker the substrate, the less likely the perforated glass substrate is to deform, and the less likely problems are to occur when mounting semiconductor elements. Furthermore, the thickness of the glass substrate is preferably 2.00 mm or less, more preferably 1.80 mm or less, more preferably 1.60 mm or less, more preferably 1.40 mm or less, more preferably 1.30 mm or less, more preferably 1.20 mm or less, more preferably 1.10 mm or less, more preferably 1.00 mm or less, more preferably 0.90 mm or less, more preferably 0.80 mm or less, and particularly preferably 0.70 mm or less. The thinner the substrate, the smaller the hole diameter can be when forming through holes. By reducing the diameter of the through-holes, the mounting density of semiconductor elements on the perforated glass substrate can be increased, and fine wiring can be formed. The thickness of the glass substrate can be adjusted by the flow rate and drawing speed during molding. Furthermore, processes such as slimming may be performed to adjust the thickness of the glass substrate. Therefore, the thickness of the glass substrate is preferably 0.03 mm to 2.00 mm, more preferably 0.05 mm to 1.80 mm, more preferably 0.10 mm to 1.60 mm, more preferably 0.20 mm to 1.40 mm, more preferably 0.30 mm to 1.30 mm, more preferably 0.35 mm to 1.20 mm, more preferably 0.40 mm to 1.10 mm, more preferably 0.45 mm to 1.00 mm, more preferably 0.50 mm to 0.90 mm, more preferably 0.50 mm to 0.80 mm, and particularly preferably 0.50 mm to 0.70 mm.

[0086] The difference between the maximum and minimum distances between the first and second main surfaces of the glass substrate (TTV = Total Thickness Variation) is preferably 20 μm or less, more preferably 15 μm or less, more preferably 10 μm or less, more preferably 8 μm or less, more preferably 5 μm or less, more preferably 3 μm or less, more preferably 2 μm or less, and particularly preferably 1 μm or less. The smaller the TTV, the higher the surface accuracy and the easier it is to improve the accuracy of the processing. In particular, it is possible to improve the wiring accuracy, making high-density wiring possible.

[0087] The amount of warpage of the glass substrate is preferably 60 μm or less, 55 μm or less, 50 μm or less, 45 μm or less, and particularly preferably 40 μm or less. The lower limit of the amount of warpage is not particularly limited, but may be, for example, 1 μm or more, or 5 μm or more. The smaller the amount of warpage, the easier it is to improve the accuracy of the processing. In particular, it is possible to improve the wiring accuracy, which enables high-density wiring.

[0088] The relative permittivity of the glass substrate at 25°C and a frequency of 10 GHz is preferably 5.0 or less, 4.9 or less, 4.8 or less, 4.7 or less, 4.6 or less, and particularly 4.5 or less. If the relative permittivity at 25°C and a frequency of 10 GHz is too high, the transmission loss when an electrical signal is transmitted through the glass substrate tends to increase when the glass substrate is used in a high-frequency device.

[0089] The dielectric loss tangent of the glass substrate at 25°C and a frequency of 10 GHz is preferably 0.01 or less, 0.009 or less, 0.008 or less, 0.007 or less, 0.006 or less, 0.005 or less, 0.004 or less, and particularly 0.003 or less. If the dielectric loss tangent at 25°C and a frequency of 10 GHz is too high, when the glass substrate is used in a high-frequency device, the transmission loss when an electrical signal is transmitted to the glass substrate tends to be large.

[0090] The linear transmittance of the glass substrate with a thickness of 0.5 mm according to this embodiment at wavelengths of 400 nm to 1100 nm is preferably 80% or more, more preferably 85% or more, and particularly preferably 90% or more. If the absorption coefficient is large in this wavelength range due to the influence of coloring components in the glass, the heat generated at the laser irradiation site will be large when laser light is irradiated to form a modified portion on the glass substrate, making it easier for defects such as cracks to occur. Alternatively, if the scattering coefficient is large in this wavelength range due to the influence of phase separation in the glass, the laser light will be scattered, making it difficult to form a modified portion on the glass substrate.

[0091] The glass substrate according to this embodiment is preferably used to manufacture perforated glass substrates. Perforated glass substrates manufactured using the glass substrate according to this embodiment are particularly preferably used for glass interposers, glass core substrates, and the like. The glass substrate according to this embodiment is suitable for forming through holes that are close to straight in shape, has excellent productivity, and is less prone to deformation during semiconductor mounting, making it suitable for applications such as glass interposers and glass core substrates.

[0092] [Second Embodiment] Next, a perforated glass substrate according to the second embodiment of the present invention will be described.

[0093] The perforated glass substrate according to the second embodiment is manufactured by forming through holes in the glass substrate according to the first embodiment. Therefore, the perforated glass substrate according to the second embodiment has the same glass composition and properties as the glass substrate according to the first embodiment.

[0094] Figure 2 is a top view showing a perforated glass substrate according to this embodiment, and Figure 3 is a cross-sectional view of the perforated glass substrate of Figure 2 taken along line A-A. As shown in Figures 2 and 3, the perforated glass substrate G according to this embodiment comprises a first main surface G1, a second main surface G2 which is the opposite surface of the first main surface G1, and a through hole 1 that penetrates between the first main surface G1 and the second main surface G2. A first example of the through hole 1 includes a constricted portion 1b in the center of the perforated glass substrate G in the thickness direction Z, with a diameter smaller than the diameter of the through hole 1 in the first main surface G1 and the second main surface G2. In other words, the side surface 1a of the through hole 1 is inclined with respect to the thickness direction Z.

[0095] Figure 4 is a schematic cross-sectional view showing a first example of a through-hole 1 formed in a perforated glass substrate G according to one embodiment of the present invention. The diameter D1 of the through-hole 1 on the first main surface G1 and the diameter D2 of the through-hole on the second main surface G2 can be measured, for example, by observing the surface of the perforated glass substrate G with a transmission optical microscope and measuring the length from the image. The diameter D3 of the constricted portion 1b of the through-hole 1, the distance t1 between the first main surface G1 and the constricted portion 1b, and the distance t2 between the second main surface G2 and the constricted portion 1b can be measured by scribing the perforated glass substrate G so that the inner surface of the through-hole 1 is not exposed, observing it from the cross-sectional direction with a transmission optical microscope while focusing on the inside of the through-hole 1, and measuring the length from the image. As a transmission optical microscope, for example, a Nikon ECLIPSE LV100ND can be used.

[0096] The diameters D1 and D2 of the through holes 1 in the first main surface G1 and the second main surface G2 are preferably 200 μm or less, more preferably 180 μm or less, more preferably 160 μm or less, more preferably 150 μm or less, more preferably 130 μm or less, more preferably 100 μm or less, more preferably 90 μm or less, more preferably 80 μm or less, more preferably 70 μm or less, more preferably 60 μm or less, and particularly preferably 50 μm or less. If the diameters D1 and D2 of the through holes 1 in the first main surface G1 and the second main surface G2 are too large, the through holes 1 cannot be formed at high density, and the wiring density cannot be increased when the perforated glass substrate G is used in the manufacture of a core substrate or interposer. The diameters D1 and D2 of the through holes 1 in the first main surface G1 and the second main surface G2 are preferably 5 μm or more, more preferably 10 μm or more, more preferably 15 μm or more, more preferably 20 μm or more, more preferably 25 μm or more, and particularly preferably 30 μm or more. If the diameters D1 and D2 of the through holes 1 in the first main surface G1 and the second main surface G2 are too small, when a conductive part is formed inside the through hole 1 by plating, voids may be formed in the conductive material, which may cause a problem in which there is no electrical connection between the first main surface G1 and the second main surface G2 of the perforated glass substrate. Therefore, the diameters D1 and D2 are preferably 5 μm to 200 μm, more preferably 10 μm to 180 μm, more preferably 15 μm to 160 μm, more preferably 20 μm to 150 μm, more preferably 25 μm to 130 μm, more preferably 30 μm to 100 μm, more preferably 30 μm to 90 μm, more preferably 30 μm to 80 μm, more preferably 30 μm to 70 μm, more preferably 30 μm to 60 μm, and particularly preferably 30 μm to 50 μm.

[0097] The ratio of the diameter D3 of the constricted portion 1b to the diameters D1 and D2 of the through-holes 1 in the first main surface G1 and the second main surface G2 is preferably 99% or less, more preferably 95% or less, more preferably 90% or less, more preferably 85% or less, and particularly preferably 80% or less. If the ratio of the diameter D3 of the constricted portion 1b to the diameters D1 of the through-holes 1 in the first main surface G1 and the diameter D2 of the through-holes 1 in the second main surface G2 is too large, it becomes difficult to form a seed layer inside the holes by sputtering when forming a conductive portion inside the through-holes 1 by plating, and the adhesion of the plating tends to decrease. The ratio of the diameter D3 of the constricted portion 1b to the diameter D1 of the through hole 1 in the first main surface G1 and the diameter D2 of the through hole 1 in the second main surface G2 is preferably 5% or more, more preferably 10% or more, more preferably 15% or more, more preferably 20% or more, more preferably 25% or more, more preferably 30% or more, more preferably 35% or more, more preferably 40% or more, more preferably 45% or more, and particularly preferably 50% or more. If the ratio of the diameter D3 of the constricted portion 1b to the diameter D1 of the through hole 1 in the first main surface G1 and the diameter D2 of the through hole 1 in the second main surface G2 is too small, it becomes difficult to fill the conductive material inside the through hole 1 when forming a conductive portion by plating, and there is a risk that a problem will occur in which there is no electrical connection between the first main surface G1 and the second main surface G2 of the perforated glass substrate. Therefore, the ratio of diameter D3 to diameters D1 and D2 is preferably 5% to 99%, more preferably 10% to 95%, more preferably 15% to 90%, more preferably 20% to 85%, more preferably 25% to 80%, more preferably 30% to 80%, more preferably 35% to 80%, more preferably 40% to 80%, more preferably 45% to 80%, and particularly preferably 50% to 80%.

[0098] The average taper angle θ of the through hole 1 in the first example can be evaluated as follows. First, the taper angle θ1 of the side surface of the through hole 1 on the first main surface G1 side and the taper angle θ2 of the side surface of the through hole 1 on the second main surface G2 side are calculated using the following equations 2 and 3. Equation 2: θ1 = arctan((D1 - D3) / (2 × t1)) Equation 2: θ2 = arctan((D2 - D3) / (2 × t2)) Equation 3

[0099] Next, the average taper angle θ of the through hole 1 is calculated using the following equation 4: θ = (θ1 + θ2) / 2 Equation 4

[0100] The average taper angle θ of the through-hole 1 is preferably 13° or less, more preferably 12° or less, more preferably 11° or less, more preferably 10° or less, more preferably 9.0° or less, more preferably 8.0° or less, more preferably 7.0° or less, more preferably 6.0° or less, more preferably 5.0° or less, more preferably 4.5° or less, and particularly preferably 4.0° or less. If the average taper angle θ is too large, the through-hole 1 cannot be formed at high density, and the wiring density cannot be increased when the perforated glass substrate G is used in the manufacture of a core substrate or interposer. Furthermore, the average taper angle θ is preferably 0° or more, more preferably 0.5° or more, more preferably 1.0° or more, more preferably 1.5° or more, more preferably 2.0° or more, more preferably 2.5° or more, and particularly preferably 3.0° or more. If the average taper angle θ is too small, it becomes difficult to fill the conductive material when forming a conductive part inside the through hole 1 by plating, which may result in a failure of electrical conductivity between the first main surface G1 and the second main surface G2 of the perforated glass substrate G. Therefore, the average taper angle θ is preferably 0° to 13°, more preferably 0.5° to 12°, more preferably 1.0° to 11°, more preferably 1.5° to 10°, more preferably 2.0° to 9.0°, more preferably 2.5° to 8.0°, more preferably 3.0° to 7.0°, more preferably 3.0° to 6.0°, more preferably 3.0° to 5.0°, more preferably 3.0° to 4.5°, and particularly preferably 3.0° to 4.0°.

[0101] Figure 5 is a schematic cross-sectional view showing a second example of a through-hole 1 formed in a perforated glass substrate G according to one embodiment of the present invention. As shown in Figure 5, the through-hole 1 of the second example does not have a constricted portion in the center of the thickness direction Z of the perforated glass substrate G. Furthermore, in the through-hole 1 of the second example, the diameter D1 of the through-hole 1 on the first main surface G1 is different from the diameter D2 of the through-hole 1 on the second main surface G2, and the side surface 1a of the through-hole 1 is inclined with respect to the thickness direction Z.

[0102] The average taper angle θ of the through hole in the second example, which does not have a constricted section, is calculated by the following equation 5: θ = arctan((D1 - D2) / (2 × t)) Equation 5

[0103] [Third Embodiment] Next, a method for manufacturing a perforated glass substrate according to the third embodiment of the present invention will be described with reference to Figures 6 to 9. As shown in Figure 6, the method for manufacturing a perforated glass substrate according to this embodiment comprises a preparation step S1 for preparing a glass substrate G0, a laser irradiation step S2 for irradiating the portion of the glass substrate G0 where through holes are to be formed with laser light to form a modified portion Gm, and an etching step S3 for etching the glass substrate G0 having the modified portion Gm to form a glass substrate having through holes (perforated glass substrate).

[0104] In preparation step S1, a glass substrate G0 according to the first embodiment of the present invention is prepared. As shown in Figure 7, preparation step S1 comprises a mixing step S11 for mixing a glass batch, a melting step S12 for melting the mixed glass batch to obtain molten glass, and a molding step S13 for molding the molten glass to obtain the glass substrate G0. In mixing step S11, SnO ２ ,Cl,F,C,SO ３ NO ３ , and CEO ２It is preferable to prepare a glass batch containing two or more types selected from the group consisting of the following. In the melting step S12, the glass batch is supplied into a glass melting furnace, and molten glass is obtained by heating the glass batch with, for example, radiant heat from burner combustion or Joule heat generated by current flow between electrodes. In the molding step S13, the glass substrate G0 may be prepared by cutting a glass plate formed by, for example, the overflow down-draw method to a predetermined size. Alternatively, a glass plate formed by other methods such as the slot down-draw method, float method, or roll-out method may be cut to a predetermined size.

[0105] In the laser irradiation process S2, as shown in Figure 8, the glass substrate G0 is placed flat with the second main surface G2 facing downwards. The glass substrate G0 may also be placed on a surface plate (not shown), for example. The irradiation unit of the laser irradiation device 2 is positioned away from the first main surface G1 so as to face the first main surface G1 of the glass substrate G0. The irradiation unit of the laser irradiation device 2 is configured to be movable in three dimensions by a drive device (not shown).

[0106] Next, the laser irradiation device 2 irradiates the first main surface G1 of the glass substrate G0 with laser light 2a perpendicular to it. The laser irradiation device 2 is, for example, a pulsed laser irradiation device, and it is preferable to irradiate with a pulsed laser. With a pulsed laser, the glass substrate G0 can be heated efficiently by increasing the energy per pulse, and the glass substrate G0 can be prevented from being damaged by heat diffusion by shortening the pulse duration. The laser light 2a is preferably a picosecond laser or a femtosecond laser, and the pulse width is preferably, for example, 50 fs or more and 100 ps or less. Furthermore, the energy per pulse of the laser light 2a is preferably, for example, 10 μJ or more and 300 μJ or less.

[0107] It is preferable to use a wavelength of laser light 2a between 400 nm and 1100 nm. For example, the wavelengths of laser light 2a are 1030 nm and 515 nm.

[0108] The laser irradiation device 2 preferably shapes the laser beam 2a into a Gaussian beam shape or a Bessel beam shape using an optical system (not shown) including, for example, an axicon lens, and the use of a Bessel beam shape is particularly preferred. By shaping the laser beam 2a into a Bessel beam shape, a modified portion Gm can be formed over the entire thickness direction of the glass plate with a single laser irradiation, thereby shortening the time required to form the modified portion Gm. In this embodiment, the focal length of the laser beam 2a is, for example, 0.1 mm or more and 10 mm or less. The spot diameter of the laser beam 2a is, for example, 0.1 μm or more and 10 μm or less.

[0109] When the laser irradiation device 2 irradiates the glass substrate G0 with laser light 2a toward the first main surface G1, modified portions Gm are formed on the glass substrate G0. By repeatedly moving the irradiation position of the laser light 2a on the glass substrate G0 and irradiating with the laser light 2a multiple times, multiple modified portions Gm are formed on the glass substrate G0. In this embodiment, each time the laser irradiation device 2 irradiates with one pulse of laser light 2a, the irradiation position of the laser light 2a on the glass substrate G0 is moved. In other words, each of the multiple modified portions Gm is formed by a single pulse of laser light 2a.

[0110] In etching step S3, the glass substrate G0, on which the modified portion Gm was formed in the laser irradiation step S2 described above, is immersed in an etching solution to remove the modified portion Gm and form through holes 1. The type of etching solution is not particularly limited as long as the etching rate of the modified portion Gm is higher than the etching rate of the unmodified portion; for example, an aqueous HF solution or an aqueous NaOH solution can be used. As an etching solution, an aqueous HF solution is particularly preferred because it has a high etching rate and can shorten the time of etching step S3. In addition, HCl and H are added to the aqueous HF solution. ２ SO ４ HNO ３One or more acids may be added to form a mixed aqueous solution. A surfactant may also be added. In etching step S3, after the modified portion Gm is removed to form the through hole 1, the diameter of the through hole 1 may be widened by etching the unmodified portion around the modified portion Gm until the diameter of the through hole 1 reaches a desired value.

[0111] The temperature of the etching solution is not particularly limited, but it is preferable to lower the temperature of the etching solution in order to reduce the average taper angle θ. When using an etching solution containing HF, the upper limit of the etching solution temperature is 35°C or less, preferably 30°C or less, more preferably 20°C or less, more preferably 10°C or less, and particularly preferably 5°C or less. Lowering the temperature of the etching solution lowers the etching rate, which reduces the amount of residue generated in etching step S3, and makes it easier to scrape out the residue from inside the hole. As a result, etching of the hole tip is less likely to be hindered by residue during the formation of the through hole 1, and the average taper angle θ of the through hole 1 tends to become smaller. The lower limit of the etching solution temperature is preferably 0°C or higher. By setting the temperature in this way, the possibility of the etching solution freezing can be reduced.

[0112] The concentration of the etching solution is not particularly limited and may be changed as appropriate to obtain the desired shape of the through-hole 1. For example, the concentration of the etching solution may be changed during the formation of the through-hole 1. During the etching process S3, the concentration of the etching solution changes, so it is preferable to circulate or replace the etching solution to maintain a constant concentration.

[0113] In etching step S3, it is preferable to stir the etching solution or apply ultrasonic waves to the etching solution. Alternatively, the glass substrate G0 may be agitated in the etching solution. This makes it easier to scrape out residue from inside the holes, and the average taper angle θ of the through-hole 1 tends to decrease.

[0114] Furthermore, an alkaline chemical solution may be used as the etching solution to create a through-hole 1 that is close to a straight shape; for example, an aqueous solution of NaOH or an aqueous solution of KOH can be used. The etching solution may also be a mixed aqueous solution by adding one or more alkaline hydroxides such as NaOH and KOH, or a surfactant may be added. The concentration of the etching solution in this case is not particularly limited and may be changed as appropriate to obtain the desired shape of the through-hole 1, but it is preferable to increase the alkali concentration of the etching solution in order to shorten the etching time required for the formation of the through-hole. For example, in the case of an aqueous solution of NaOH, it is preferable to use an aqueous solution containing 30 wt% or more of NaOH, and it is more preferable to use an aqueous solution containing 40 wt% or more of NaOH. Furthermore, the concentration of the etching solution may be changed during the formation of the through-hole 1. Note that since the concentration of the etching solution changes during the execution of etching step S3, it is preferable to circulate or replace the etching solution to keep the concentration of the etching solution constant.

[0115] The temperature of the etching solution is not particularly limited, but it is preferable to raise the temperature of the etching solution in order to shorten the etching time required for the formation of through holes. Therefore, when using an etching solution containing NaOH, the lower limit of the etching solution temperature is preferably 70°C or higher, more preferably 80°C or higher, more preferably 90°C or higher, more preferably 100°C or higher, more preferably 105°C or higher, more preferably 110°C or higher, more preferably 115°C or higher, and particularly preferably 120°C or higher. The upper limit of the etching solution temperature is preferably 140°C or lower, more preferably 135°C or lower, and particularly preferably 130°C or lower. By setting the temperature in this way, temperature unevenness in the etching solution can be reduced, and the TTV of the glass substrate after etching can be lowered. Furthermore, by increasing the pressure inside the etching container, the boiling point of the etching solution can be raised, and the glass substrate can be etched at a temperature above the boiling point of the etching solution under atmospheric pressure. Therefore, the temperature of the etching solution is preferably 70°C to 140°C, more preferably 80°C to 135°C, more preferably 90°C to 130°C, more preferably 100°C to 130°C, more preferably 105°C to 130°C, more preferably 110°C to 130°C, more preferably 115°C to 130°C, and particularly preferably 120°C to 130°C.

[0116] Figure 9 is a schematic diagram for comparing the glass substrate G0 before etching process S3 and the perforated glass substrate G after etching process S3. As shown in Figure 9, in etching process S3, the first main surface G1, the second main surface G2, or both the first main surface G1 and the second main surface G2 are etched, so the thickness t of the perforated glass substrate G is smaller than the thickness t0 of the glass substrate G0. In Figure 9, the perforated glass substrate G is shown with a solid line and the glass substrate G0 is shown with a dashed line.

[0117] Furthermore, in the perforated glass substrate G according to one embodiment of the present invention, since through holes 1 are formed by the etching process S3, at least the side surface 1a of the through hole 1 (the inside of the through hole 1) is an etched surface. As a result, the inside of the through hole 1 has excellent surface properties, is free of fine cracks, and has high strength. Therefore, by using the perforated glass substrate G according to this embodiment as a glass core substrate or glass interposer, a package substrate that is resistant to damage can be obtained. On the other hand, when through holes are formed in a glass substrate by methods such as laser ablation, the surface properties inside the through holes are poor, and fine cracks are more likely to occur, resulting in lower strength.

[0118] In etching step S3, if etching is performed from both the first main surface G1 and the second main surface G2 of the glass substrate G0, the through-hole 1 of the first example described above, that is, the through-hole 1 having a constricted portion 1b, is formed. On the other hand, if etching step S3 is performed with a protective film attached to either the first main surface G1 or the second main surface G2, etching is performed only from the main surface without the protective film, and the through-hole 1 of the second example described above, that is, the through-hole 1 without a constricted portion 1b, is formed.

[0119] The present invention will be described below based on examples. Note that the following examples are merely illustrative. The present invention is not limited in any way to the following examples.

[0120] Tables 1 to 4 show the glass composition and glass properties of the examples of the present invention (samples No. 1 to 30). However, sample No. 21 is omitted.

[0121] First, glass batches prepared with glass raw materials to match the glass composition shown in the table were placed in a platinum crucible and melted at 1600-1700°C for 8 hours. During the melting of the glass batches, a platinum stirrer was used to stir and homogenize them. Next, for glass No. 1, the molten glass was rapidly cooled by press molding to form a circular shape, and then slowly cooled at a temperature near the annealing point for 30 minutes. For glasses No. 2-30, the molten glass was poured onto a carbon plate, formed into a plate shape, and then slowly cooled at a temperature near the annealing point for 30 minutes. For each of the obtained samples, the density, average thermal expansion coefficient CTE in the temperature range of 30-380°C, Young's modulus, strain point Ps, annealing point Ta, softening point Ts, and high-temperature viscosity 10 were recorded. ４．０ Temperature and high-temperature viscosity at dPa·s 10 ３．０ Temperature and high-temperature viscosity at dPa·s 10 ２．５ Temperature, liquidus temperature TL, initial phase, viscosity at liquidus temperature TL in dPa·s (log) １０ ηTL, β-OH value, HF etching rate, and linear transmittance at wavelengths of 400 nm to 1100 nm were evaluated. The HF etching rate was measured by the following method. Specifically, glass substrate samples No. 1 to 30, prepared by the method described above, were cut to a size of 1 mm thickness and 20 mm x 35 mm. Both sides were optically polished, and then the glass substrate samples were annealed according to the temperature profile shown in Figure 1, and a portion of the main surface was masked. Next, the glass substrate samples were immersed in an etching solution for 20 minutes to perform etching. 300 mL of a 2.5 mol / L HF aqueous solution was used as the etching solution. During etching, a water bath stirrer was set to 30°C and stirred at approximately 600 rpm. After that, the mask was removed, the glass substrate samples were washed, and the step difference between the masked area and the eroded area was measured using a surfcorder (ET4000A: Kosaka Laboratory Co., Ltd.). The etching rate was calculated by dividing the height of the step difference by the immersion time.

[0122]

[0123]

[0124]

[0125]

[0126] The density was measured using the well-known Archimedes method.

[0127] The average thermal expansion coefficient CTE in the temperature range of 30 to 380°C is the value measured using a dilatometer.

[0128] Young's modulus is a value measured using a well-known resonance method.

[0129] The strain point Ps, annealing point Ta, and softening point Ts were measured according to the ASTM C336 and C338 methods.

[0130] The glass transition temperature Tg is a value measured with a dilatometer.

[0131] High temperature viscosity 10 ４．０ dPa·s, 10 ３．０ dPa·s, 10 ２．５ The temperature in dPa·s was measured using the platinum ball pulling method.

[0132] The liquidus temperature TL is the temperature at which crystals precipitate after the glass powder, which passes through a standard 30-mesh (500 μm) sieve and remains in a 50-mesh (300 μm) sieve, is placed in a platinum boat and held in a temperature gradient furnace for 24 hours. These crystals were then evaluated as the initial phase. In the table, "Cri" refers to cristobalite.

[0133] liquidus viscosity log １０ ηTL is the viscosity of the glass at the liquidus temperature TL, measured using the platinum ball pulling method.

[0134] The HF etching rate is the value measured by the method described above.

[0135] The linear transmittance in the wavelength range of 400 nm to 1100 nm was obtained by preparing a 0.5 mm thick plate sample with both sides mirror-polished, and measuring the linear transmittance of this sample using an ultraviolet-visible-near-infrared spectrophotometer (JASCO V-670).

[0136] Next, through-holes were formed in glass substrate samples No. 1-6, 10-13, 15-20, and 22-28 using the following method. A picosecond pulsed laser, shaped into a Vessel beam, was irradiated onto the glass substrate sample, which had been cut into a rectangular shape of 40 mm x 20 mm, from the first main surface side with an irradiation position spacing of approximately 200 μm, thereby forming approximately 8,000 modified areas on the glass substrate.

[0137] Next, the glass substrate sample was etched under the following conditions. The glass substrate sample was placed in a PP test tube containing the etching solution, and etching was performed by applying ultrasound to the etching solution. At this time, a Teflon® jig was used to fix the glass substrate sample 10 mm away from the bottom of the test tube. An aqueous solution containing 2.5 mol / L of HF and 1.0 mol / L of HCl was used as the etching solution. The temperature of the etching solution was set to 10°C. To prevent the temperature from rising during ultrasound application, the water in the ultrasonic device was circulated using a chiller to maintain the water temperature at 10°C. An ultrasonic cleaner (VS-100III: manufactured by AS ONE Corporation) was used to apply ultrasonic vibrations, and 28 kHz ultrasound was applied to the etching solution.

[0138] The perforated glass substrate samples obtained by this method had through-holes with constricted sections inside. The average taper angle θ of these through-holes was determined by the method described above.

[0139] Tables 5 to 10 show the etching time, the thickness of the glass substrate sample before etching, the thickness of the perforated glass substrate sample after etching, and the shape of the through-holes.

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146] Next, a picosecond pulsed laser, shaped into a Vessel beam, was irradiated onto the No. 1 glass substrate sample, which had been cut into a rectangular shape of 50 mm x 50 mm, from the first main surface side, with the irradiation positions spaced approximately 200 μm apart, to form approximately 10,000 modified areas on the glass substrate. For this glass substrate, an aqueous solution containing 1.5 mol / L of HF and 0.2 mol / L of HCl was used as the etching solution, and the etching solution temperature was set to 33°C. Etching was performed by agitating the glass in the etching solution.

[0147] The perforated glass substrate samples obtained by this method had through-holes with constricted sections inside. The average taper angle θ of the through-holes was determined by the method described above.

[0148] Table 11 shows the etching time, the thickness of the glass substrate sample, the thickness of the perforated glass substrate sample, and the shape of the through-holes.

[0149]

[0150] Next, glass substrate samples No. 1, 6-9, 15-20, and 22-24, which had been cut into 50 mm x 50 mm rectangles, were irradiated from the first main surface side with a picosecond pulsed laser shaped into a Vessel beam, with the irradiation positions spaced approximately 200 μm apart, to form approximately 10,000 modified areas on the glass substrate. For these glass substrates, an aqueous solution containing 30 wt% NaOH was used as the etching solution, the etching solution temperature was set to 80°C, and etching was performed by agitating the glass in the etching solution.

[0151] The perforated glass substrate samples obtained by this method had through-holes with constricted sections inside. The average taper angle θ of the through-holes was determined by the method described above.

[0152] The etching time, the thickness of the glass substrate sample, the thickness of the perforated glass substrate sample, and the shape of the through-holes are shown in Tables 12 and 13.

[0153]

[0154]

[0155] Next, glass substrate samples No. 1, 6, and 9, which had been cut into rectangular shapes of 510 mm x 515 mm, were irradiated from the first main surface side with a picosecond pulsed laser shaped into a Vessel beam, with the irradiation positions spaced approximately 200 μm apart, to form approximately 100,000 modified areas on the glass substrate. For these glass substrates, an aqueous solution containing 48 wt% NaOH was used as the etching solution, and the etching solution temperature was set to 100°C. Etching was performed by agitating the glass in the etching solution.

[0156] The perforated glass substrate samples obtained by this method had through-holes with constricted sections inside. The average taper angle θ of the through-holes was determined by the method described above.

[0157] Table 14 shows the etching time, the thickness of the glass substrate sample, the thickness of the perforated glass substrate sample, and the shape of the through-holes.

[0158]

[0159] As is clear from Tables 1 to 4, the glass substrate samples of this embodiment have a low temperature at high-temperature viscosity and excellent productivity. Furthermore, they have a low coefficient of thermal expansion, making them less prone to deformation during semiconductor device mounting. Also, as is clear from Tables 5 to 14, the perforated glass substrate samples manufactured using the glass substrate samples of this embodiment have a small average taper angle and form through-holes that are close to a straight shape. Therefore, the glass substrate samples and perforated glass substrate samples of this embodiment can be suitably used as core substrates or interposers for package substrates used in semiconductor device mounting.

[0160] Next, the clarifying agent (i.e., SnO ２ Cl, NO ３ , and SO ３ Glass samples No. 1-1 to 1-17, having substantially the same composition as sample No. 1 described above except for the amount of (), were prepared and their clarity was evaluated. Tables 15 and 16 show the composition of the glass raw materials. In Tables 15 and 16, the batch composition is expressed in mass%, with the total amount of oxides excluding the clarifying agent set to 100% by mass. In addition, NaCl was used as the Cl source, NO ３ Source: NaNO ３SO ３ Na as a source ２ SO ４ The following was used: A glass batch containing the glass raw materials was placed in a platinum crucible, melted at 1500°C for 2 hours, then heated to 1600°C or 1650°C over 30 minutes, held at that temperature for 30 minutes, and then removed from the platinum crucible. The glass was then slowly cooled at a temperature near the annealing point for 30 minutes. The resulting frustoconical glass was cut and mirror-polished from approximately the center of its top and bottom surfaces using a plane perpendicular to the top and bottom surfaces to obtain a glass sample with a top base of approximately 25 mm, a bottom base of approximately 50 mm, a height of approximately 25 mm, and a thickness of approximately 8 mm. The clarity of this glass sample was evaluated by checking the number of bubbles using an image inspection machine.

[0161]

[0162]

[0163] As is clear from Tables 15 and 16, SnO is the clarifying component. ２ Alternatively, the number of bubbles can be reduced by manufacturing the glass substrate using a batch containing Cl. In particular, as in samples No. 1-12 and No. 1-13, SnO ２ By including both and Cl, good clarity can be obtained even at low melting temperatures. Therefore, the glass sample of this embodiment can have a low melting temperature, so B ２ O ３ or Na ２ This reduces the amount of oxygen volatilized, thereby improving the homogeneity of the molded glass substrate. Therefore, when through-holes are formed, the uniformity of the hole diameter can be improved, making it suitable for use as a core substrate or interposer in package substrates used for mounting semiconductor devices.

[0164] Furthermore, samples No. 1-1 to 1-17 were able to produce through-holes similar to those in sample No. 1 using the same method as described above for forming through-holes in sample No. 1.

[0165] G0 Glass substrate G Perforated glass substrate G1 First main surface G2 Second main surface Gm Modified area Z Thickness direction 1 Through hole 1a Side surface of through hole 1b Constricted area 2 Laser irradiation device 2a Laser light D1 Diameter of through hole on the first main surface D2 Diameter of through hole on the second main surface D3 Diameter of through hole in the constricted area θ Average taper angle of through hole θ1 Taper angle on the first main surface side of through hole with constricted area θ2 Taper angle on the second main surface side of through hole with constricted area θ3 Taper angle of through hole without constricted area t0 Thickness of glass substrate t Thickness of perforated glass substrate t1 Distance between first main surface and constricted area t2 Distance between second main surface and constricted area

Claims

1. A perforated glass substrate comprising a first main surface, a second main surface which is the opposite surface of the first main surface, and a through hole penetrating between the first main surface and the second main surface, wherein the glass composition is SiO2 in mol%. ２ 65.0-85.0%, Al ２ O ３ 0-10.0%, B ２ O ３ 0.1-25.0%, Li ２ O 0-5.0%, Na ２ O 0-20.0%, K ２ A perforated glass substrate characterized by containing 0 to 20.0% of O.

2. As the glass composition, in mol%, SiO ２ 65.0 to 85.0%, Al ２ O ３ 0 to 10.0%, B ２ O ３ 0.1 to 20.0%, Li ２ O 0 to 3.0%, Na ２ O 0 to 20.0%, K ２ The porous glass substrate according to claim 1, containing 0 to 20.0%.

3. As for the glass composition, in mol%, SiO ２ 65.0-85.0%, Al ２ O ３ 0-10.0%, B ２ O ３ 5.0-25.0%, Li ２ O 0-5.0%, Na ２ O 0-20.0%, K ２ A perforated glass substrate according to claim 1, characterized by containing 0 to 5.0% of O.

4. As for the glass composition, in mol%, SiO ２ 65.0-85.0%, Al ２ O ３ 0-10.0%, B ２ O ３ 0.1% or more and less than 5.0%, Li ２ O 0-5.0%, Na ２ O 0-20.0%, K ２ A perforated glass substrate according to claim 1, characterized by containing 0 to 20.0% of O.

5. As for the glass composition, in mol%, SiO ２ 65.0-85.0%, Al ２ O ３ 0-10.0%, B ２ O ３ 0.1-25.0%, Li ２ O 0-5.0%, Na ２ O 0-20.0%, K ２ A perforated glass substrate according to claim 1, characterized in that it contains more than 5.0% and 20.0% or less of O.

6. As for the glass composition, in mol%, SiO ２ 65.0-85.0%, Al ２ O ３ 0-10.0%, B ２ O ３ 0.1-25.0%, Li ２ O 0-5.0%, Na ２ O 1.0-20.0%, K ２ A perforated glass substrate according to claim 1, containing 0 to 20.0% of O.

7. As for the glass composition, in mol%, SiO ２ 75.0-85.0%, Al ２ O ３ 0-5.0%, B ２ O ３ 0.1-25.0%, Li ２ O 0-5.0%, Na ２ O 1.0-20.0%, K ２ A perforated glass substrate according to claim 1, containing 0 to 20.0% of O.

8. The glass composition consists of 0.001-3.0% Cl and SnO in mol%. ２ A perforated glass substrate according to any one of claims 1 to 7, further containing at least one of 0.01 to 1.0%.

9. The perforated glass substrate according to claim 8, wherein the glass composition contains 0.05 to 1.0% of Cl in mol%.

10. As for the glass composition, in mol%, SnO ２ A perforated glass substrate according to claim 8, containing 0.05 to 0.5%.

11. The perforated glass substrate according to any one of claims 1 to 7, wherein the thickness of the perforated glass substrate is 0.03 mm or more and 2.00 mm or less, the TTV of the perforated glass substrate is 20 μm or less, and the warpage of the perforated glass substrate is 60 μm or less.

12. A perforated glass substrate according to any one of claims 1 to 7, wherein the HF etching rate is 1.00 μm / min or less.

13. The average coefficient of thermal expansion in the temperature range of 30 to 380°C is 20 × 10⁻⁶. －７ ~100 x 10 －７ A perforated glass substrate according to any one of claims 1 to 7, wherein the temperature is / °C.

14. The perforated glass substrate according to any one of claims 1 to 7, wherein the side surface of the through hole is inclined with respect to the thickness direction of the plate, and the average taper angle of the side surface is 0 to 13.0°.

15. The perforated glass substrate according to any one of claims 1 to 7, wherein the through-hole has a constricted portion in the center of the thickness direction of the perforated glass substrate, the constricted portion having a smaller diameter than the diameter of the through-hole on the first main surface and the second main surface, and the diameter of the constricted portion is 5% or more and 99% or less of the diameter of the through-hole on the first main surface and the diameter of the through-hole on the second main surface.

16. The perforated glass substrate according to claim 15, wherein the diameter of the through hole on the first main surface is 5 μm or more and 200 μm or less, and the diameter of the through hole on the second main surface is 5 μm or more and 200 μm or less.

17. The perforated glass substrate according to any one of claims 1 to 7, wherein at least the inner surface of the through hole is an etched surface.

18. As a glass composition, SiO in mol% ２ 65.0-85.0%, Al ２ O ３ 0-10.0%, B ２ O ３ 0.1-25.0%, Li ２ O 0-5.0%, Na ２ O 0-20.0%, K ２ A glass substrate characterized by containing 0 to 20.0% of O.

19. As a glass composition, SiO in mol% ２ 65.0-85.0%, Al ２ O ３ 0-10.0%, B ２ O ３ 0.1-20.0%, Li ２ O 0-3.0%, Na ２ O 0-20.0%, K ２ A glass substrate according to claim 18, containing 0 to 20.0% of O.

20. As for the glass composition, in mol%, SiO ２ 65.0-85.0%, Al ２ O ３ 0-10.0%, B ２ O ３ 5.0-25.0%, Li ２ O 0-5.0%, Na ２ O 0-20.0%, K ２ The glass substrate according to claim 18, characterized in that it contains 0 to 5.0% of O.

21. As a glass composition, in mol%, SiO ２ 65.0 to 85.0%, Al ２ O ３ 0 to 10.0%, B ２ O ３ 0.1% or more and less than 5.0%, Li ２ O 0 to 5.0%, Na ２ O 0 to 20.0%, K ２ O 0 to 20.0%, and the glass substrate according to claim 18, characterized by containing the same.

22. As a glass composition, in mol%, SiO ２ 65.0 to 85.0%, Al ２ O ３ 0 to 10.0%, B ２ O ３ 0.1 to 25.0%, Li ２ O 0 to 5.0%, Na ２ O 0 to 20.0%, K ２ The glass substrate according to claim 18, characterized in that it contains more than 5.0% and 20.0% or less of K 23. The glass composition consists of 0.001-3.0% Cl and SnO in mol%. ２ A glass substrate according to any one of claims 18 to 22, further containing at least one of 0.01 to 1.0%.

24. The glass substrate according to any one of claims 18 to 22, characterized in that the glass substrate is a glass substrate for manufacturing a perforated glass substrate.

25. A method for manufacturing a perforated glass substrate, comprising: a preparation step of preparing a glass substrate according to any one of claims 18 to 22; a laser irradiation step of irradiating the portion of the glass substrate where through holes are to be formed with laser light to form a modified portion; and an etching step of etching the glass substrate having the modified portion to form a perforated glass substrate having through holes.

26. SnO ２ , Cl, F, Br, I, C, metal Al, metal Si, As ２ O ３ Sb ２ O ３ SO ３ NO ３ Fe ２ O ３ , and CEO ２ The process comprises a blending step of blending a glass batch containing two or more types selected from the group consisting of; a melting step of melting the blended glass batch to obtain molten glass; and a molding step of shaping the molten glass to obtain a glass substrate, wherein the glass substrate has a glass composition of SiO in mol%. ２ 65.0-85.0%, Al ２ O ３ 0-10.0%, B ２ O ３ 0.1-25.0%, Li ２ O 0-5.0%, Na ２ O 0-20.0%, K ２ A method for manufacturing a glass substrate, characterized by containing 0 to 20.0% of O.

27. SnO ２ , Cl, F, Br, I, C, metal Al, metal Si, As ２ O ３ Sb ２ O ３ SO ３ NO ３ Fe ２ O ３ , and CEO ２ The process comprises: a compounding step of compounding a glass batch containing two or more types selected from the group consisting of; a melting step of melting the compounded glass batch to obtain molten glass; a molding step of shaping the molten glass to obtain a glass substrate; a laser irradiation step of irradiating the portion of the glass substrate where through holes are to be formed with laser light to form a modified portion; and an etching step of etching the glass substrate having the modified portion to form a perforated glass substrate having through holes, wherein the perforated glass substrate has a glass composition of SiO in mol%. ２ 65.0-85.0%, Al ２ O ３ 0-10.0%, B ２ O ３ 0.1-25.0%, Li ２ O 0-5.0%, Na ２ O 0-20.0%, K ２ A method for producing a perforated glass substrate, characterized by obtaining glass containing 0 to 20.0% of O.

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