Glass

Abstract

The present invention provides a glass which has a Young's modulus of 80 GPa or more, is suppressed in deflection, and is easy to manufacture by setting a parameter A represented by formula (1) to 0.817 or less, a parameter B represented by formula (2) to 0.898 or more, and a ratio of the content of MgO, expressed in mol% on the basis of oxides, to the total content of divalent oxides RO, to 0.65 or more, and which is an alkali-free glass. A = 1.747 to 0.022 * [SiO2] + 0.006 * [Al2O3] + 0.018 * [B2O3] + 0.013 * [MgO]-0.010 * [CaO]-0.003 * [SrO] + 0.012 * [B2O3] + 0.015 * [ZnO] (1) B = 1.315 to 0.010 * [SiO2] + 0.005 * [Al2O3] + 0.023 * [B2O3] + 0.004 * [MgO]-0.016 * [CaO]-0.007 * [SrO] + 0.011 * [BaO] + 0.010 * [ZnO] (2).

Description

Technical Field

[0001] This invention relates to glass. Background Technology

[0002] In the manufacturing process of semiconductor devices, glass is sometimes used as a component to support the semiconductor device. For example, Patent Document 1 describes a support glass substrate with a high Young's modulus that is manufactured to suppress deflection.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2021-20840 Summary of the Invention

[0006] Glasses with high Young's modulus, which are made to suppress flexural deformation, often exhibit viscosity curves that are unsuitable for manufacturing due to the components added to achieve the high Young's modulus, i.e., temperature dependence of viscosity. Therefore, it is necessary to make the manufacturing process easier.

[0007] The purpose of this invention is to provide a glass that suppresses flexural deformation and is easy to manufacture.

[0008] Regarding the glass disclosed herein, parameter A shown in formula (1) is 0.817 or less, parameter B shown in formula (2) is 0.898 or more, the ratio of MgO content expressed as mol% based on oxides to the total content of divalent oxide RO is 0.65 or more, Young's modulus is 80 GPa or more, and it is alkali-free glass.

[0009] A=1.747-0.022×[SiO2]+0.006×[Al2O3]+0.018×[B2O3]+0.013×[M gO]-0.010×[CaO]-0.003×[SrO]+0.012×[BaO]+0.015×[ZnO]···(1)

[0010] B=1.315-0.010×[SiO2]+0.005×[Al2O3]+0.023×[B2O3]+0.004×[M gO]-0.016×[CaO]-0.007×[SrO]+0.011×[BaO]+0.010×[ZnO]···(2)

[0011] According to the present invention, flexural deformation can be suppressed and the invention is easy to manufacture. Attached Figure Description

[0012] Figure 1 This is a schematic diagram of the glass in this embodiment. Detailed Implementation

[0013] Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. It should be noted that the present invention is not limited to these embodiments; furthermore, when multiple embodiments exist, embodiments combining various embodiments are also included. Additionally, numerical values ​​include rounding ranges. Furthermore, the numerical range indicated by "~" refers to a range of values ​​including the values ​​before and after "~" as both the lower and upper limits; the use of "~" thereafter carries the same meaning. Furthermore, the upper and lower limits expressed as numerical ranges can be appropriately combined.

[0014] (Glass)

[0015] Figure 1 This is a schematic diagram of the glass in this embodiment. (As shown) Figure 1 As shown, the glass 10 in this embodiment is used as a glass substrate for manufacturing semiconductor packages, and more specifically, as a support glass substrate for manufacturing FOWLPs, etc. However, the use of glass 10 is not limited to manufacturing FOWLPs, etc., but is arbitrary; it can be a glass substrate used to support components, or it can be used for purposes other than supporting components. It should be noted that FOWLPs, etc., include Fan-Out Wafer Level Packages (FOWLPs) and Fan-Out Panel Level Packages (FOPLPs).

[0016] (Composition of glass)

[0017] Next, the preferred composition of glass 10 will be described.

[0018] (Parameter A)

[0019] The parameter A of glass 10 is shown in the following formula (1).

[0020] A=1.747-0.022×[SiO2]+0.006×[Al2O3]+0.018×[B2O3]+0.013×[M gO]-0.010×[CaO]-0.003×[SrO]+0.012×[BaO]+0.015×[ZnO]···(1)

[0021] It should be noted that the oxide A contained in glass 10 is indicated by mol% on an oxide basis. x O y (A is the element constituting the oxide, and x and y are arbitrary integers) the content in terms of [A x O y [This indicates the content, expressed as a percentage (mol%) of oxide A.] x Oy The content of [SiO2] is the ratio of the content of [SiO2] to the total content of glass 10. That is, for example, in formula (1), [SiO2] refers to the ratio of the content of [SiO2] to the total content of glass 10 in mol% on an oxide basis.

[0022] In addition, glass 10 may not contain all the oxides shown in formula (1). In formula (1), the content of oxides not contained in glass 10 is treated as 0. In addition, glass 10 may contain components other than the oxides shown in formula (1).

[0023] The parameter A of the glass 10 is preferably 0.817 or less, more preferably 0.813 or less, more preferably 0.809 or less, more preferably 0.802 or less, more preferably 0.796 or less, and more preferably 0.789 or less. Furthermore, parameter A is also preferably 0.781 or more, preferably 0.781 to 0.817, preferably 0.783 or less, preferably 0.776 or less, and preferably 0.770 or less. By keeping parameter A within this range, the temperature difference between the melting temperature and the forming temperature of the glass 10 is suppressed from becoming too high, thereby suppressing the increase in energy loss during the transfer from the melting process to the forming process, and facilitating manufacturing. Additionally, by keeping parameter A within this range, the temperature difference between the forming temperature and the softening temperature is suppressed from becoming too small, making it easier to control the viscosity during forming, and facilitating manufacturing.

[0024] (Parameter B)

[0025] The parameter B of glass 10 is shown in the following formula (2).

[0026] B=1.315-0.010×[SiO2]+0.005×[Al2O3]+0.023×[B2O3]+0.004×[M gO]-0.016×[CaO]-0.007×[SrO]+0.011×[BaO]+0.010×[ZnO]···(2)

[0027] Glass 10 may not contain all the oxides shown in Formula (2). In Formula (2), the content of oxides not contained in glass 10 is treated as 0. In addition, glass 10 may contain components other than the oxides shown in Formula (2).

[0028] The parameter B of glass 10 is preferably 0.898 or higher, more preferably 0.901 or higher, more preferably 0.904 or higher, more preferably 0.907 or higher, more preferably 0.911 or higher, more preferably 0.915 or higher, more preferably 0.921 or higher, more preferably 0.926 or higher, and even more preferably 0.931 or higher. Furthermore, the parameter B of glass 10 is also preferably 0.935 or lower, and more preferably 0.903 to 0.935. By keeping parameter B within this range, the temperature difference between the molding temperature and the softening temperature is prevented from becoming too small, making it easier to control the viscosity during molding and facilitating manufacturing.

[0029] (SiO2)

[0030] Glass 10 preferably contains SiO2 (the SiO2 content is higher than 0 mol%). In order to appropriately suppress the rise in melting temperature and liquidus temperature, the SiO2 content in glass 10, expressed as mol% based on oxides, is preferably 55.0% to 65.0%, more preferably 55% to 65%, more preferably 57% to 64.5%, more preferably 59% to 64%, more preferably 61% to 63.5%, and even more preferably 61.5% to 62.5%. By keeping the SiO2 content within this range, flexing can be suppressed and manufacturing is easy.

[0031] (Al2O3)

[0032] Al2O3 has the effect of increasing Young's modulus, thus suppressing flexure and phase separation in glass. Therefore, glass 10 preferably contains Al2O3. In glass 10, the content of Al2O3, expressed as mole % based on oxides, is preferably 3% to 13.0%, more preferably 5% to 11%, more preferably 7% to 9%, more preferably 7.0% to 8.5%, more preferably 7.2% to 8.5%, more preferably 7.4% to 8%, and even more preferably 7.5% to 7.7%. By keeping the Al2O3 content within this range, flexure can be suppressed and manufacturing is easy.

[0033] (B2O3)

[0034] B2O3 has the effect of suppressing devitrification caused by glass crystallization, thus facilitating manufacturing and controlling Young's modulus. Therefore, glass 10 preferably contains B2O3. In glass 10, the content of B2O3, expressed as mole % based on oxides, is preferably 1.0% to 10.0%, more preferably 2% to 9%, more preferably 3% to 8.5%, more preferably 4% to 8%, more preferably 5.5% to 7.5%, more preferably 5.8% to 6.8%, and even more preferably 6% to 6.5%. By keeping the content of B2O3 within this range, flexural deformation can be suppressed and manufacturing can be facilitated.

[0035] (MgO / RO)

[0036] MgO increases Young's modulus without increasing density, thus improving the specific modulus of elasticity among IIA elements. The ratio of MgO content to RO content (MgO / RO) is important for controlling the specific modulus of elasticity. Therefore, in glass 10, the ratio (MgO / RO) is preferably 0.65 or higher, more preferably 0.65 to 0.9, more preferably 0.68 to 0.9, more preferably 0.7 to 0.85, more preferably 0.72 to 0.8, and even more preferably 0.74 to 0.77. Here, R refers to divalent metal, RO refers to oxide of divalent metal R, and the RO content refers to the total content of divalent oxides. When multiple divalent oxides are contained, the total content of divalent oxides refers to the total content of these divalent oxides; when only one divalent oxide is contained, it refers to the content of that divalent oxide. By maintaining the ratio (MgO / RO) within this range, flexural deformation can be suppressed and manufacturing is easier.

[0037] (RO)

[0038] In glass 10, the total content of divalent oxide RO, expressed as a mole % based on oxides, is preferably 10.0% to 40.0%, more preferably 15% to 35%, more preferably 17.5% to 30%, more preferably 20% to 27.5%, more preferably 22% to 26%, more preferably 23.5% to 25%, and even more preferably 24% to 24.5%. By keeping the total RO content within this range, flexural deformation can be suppressed and manufacturing is easier.

[0039] (MgO)

[0040] MgO is a component that can increase Young's modulus, i.e., increase specific elastic modulus, without increasing density; therefore, glass 10 preferably contains MgO. Furthermore, among components that increase Young's modulus, MgO is also a component that easily adjusts the viscosity of the glass. For example, while rare earth oxides increase Young's modulus, they reduce the temperature dependence of viscosity in high-temperature regions, resulting in a larger temperature difference between melting temperature and forming temperature. Al2O3 also increases Young's modulus and suppresses flexural deformation, but its effect on increasing glass viscosity is high, sometimes impairing melting characteristics and formability. MgO also contributes to the viscosity of glass, but by adjusting its content, it becomes an excellent component in both suppressing flexural deformation and ease of manufacturing. In glass 10, the MgO content, expressed as a mole percent based on oxides, is preferably 10.0% to 25.0%, more preferably 12% to 22%, more preferably 14% to 22%, more preferably 16% to 22%, more preferably 16.5% to 22%, more preferably 16.5% to 20%, more preferably 16.6% to 18.6%, more preferably 16.7% to 18%, and even more preferably 17% to 17.7%. By maintaining the MgO content within this range, flexing can be suppressed and manufacturing is easier.

[0041] (CaO)

[0042] CaO has the second-highest effect on increasing the specific elastic modulus among oxides of elements in the IIA group, after MgO. Therefore, glass 10 may or may not contain CaO (CaO content is 0 mol%). In glass 10, the CaO content, expressed as mol% based on oxides, is preferably 1.0% to 10.0%, more preferably 1.1% to 7%, more preferably 1.5% to 4.2%, more preferably 1.8% to 3.7%, more preferably 2.2% to 3.4%, more preferably 2.4% to 3%, and even more preferably 2.5% to 2.7%. By keeping the CaO content within this range, flexural deformation can be suppressed and manufacturing is easier.

[0043] (SrO)

[0044] SrO has the effect of increasing density and controlling Young's modulus, and also improves solubility. Glass 10 may or may not contain SrO. In glass 10, the SrO content, expressed as a mole percent (based on oxides), is preferably 0.1% to 5.0%, more preferably 0.1% to 3.4%, even more preferably 0.5% to 3%, even more preferably 0.9% to 2.6%, and even more preferably 1% to 2%. By maintaining the SrO content within this range, flexural deformation can be suppressed and manufacturing is easier.

[0045] (BaO)

[0046] BaO has a greater effect on increasing density than SrO and also improves solubility. Glass 10 may or may not contain BaO. In glass 10, the BaO content, expressed as a mole percent based on oxides, is preferably 0.1% to 5.0%, more preferably 1% to 4.8%, more preferably 1.5% to 4.7%, more preferably 2% to 4.5%, more preferably 2.5% to 4.3%, more preferably 3% to 4.1%, and even more preferably 3.3% to 3.8%. By maintaining the BaO content within this range, flexing can be suppressed and manufacturing is easier.

[0047] (ZnO)

[0048] ZnO has the effect of improving the solubility of glass and increasing Young's modulus. Therefore, glass 10 may or may not contain ZnO. By keeping the ZnO content below 10%, it is possible to suppress the increase of the linear thermal expansion coefficient. In glass 10, the ZnO content, expressed as mole % based on oxides, is preferably 0.1% to 10%, more preferably 0.5% to 8%, more preferably 1% to 7%, more preferably 1.5% to 6%, more preferably 2% to 5%, more preferably 2.5% to 4%, and even more preferably 3% to 3.5%. By keeping the ZnO content within this range, flexing can be suppressed and manufacturing is easier.

[0049] (Alkali metal oxides)

[0050] Glass 10 is preferably alkali-free glass. Alkali-free glass means that it does not substantially contain alkali metal oxides such as Li₂O, Na₂O, and K₂O. Here, "substantially not containing alkali metal oxides" means that it does not contain alkali metal oxides except for unavoidable impurities mixed in from raw materials, etc. That is, it means that it does not intentionally contain alkali metal oxides.

[0051] For example, in glass 10, the content of Li2O is preferably 0%, the content of Na2O is preferably 0%, and the content of K2O is preferably 0%, expressed as mole% based on oxides.

[0052] In addition to the components mentioned above, oxides (by-oxides) other than the oxides listed above may be included to adjust various mechanical properties, melt flowability, and formability. It should be noted that the oxides listed above refer to SiO2, Al2O3, B2O3, RO (divalent oxide), and alkali metal oxides. Examples of by-oxides include metal oxides such as TiO2 and ZrO2, and rare earth oxides such as Y2O3 and La2O3. Expressed as a mole percent based on oxides, the glass 10 may contain less than 5% of by-oxides in total, preferably less than 3%, more preferably less than 2%, more preferably less than 1%, more preferably less than 0.5%, more preferably less than 0.3%, more preferably less than 0.2%, further preferably less than 0.1%, and particularly preferably substantially none.

[0053] (PbO)

[0054] PbO has the effect of improving Young's modulus, but it is an oxide with a high environmental impact. Therefore, glass 10 preferably does not contain PbO. In glass 10, the PbO content, expressed as a mole % based on oxides, is preferably 0.1% or less, more preferably 0.05% or less, and even more preferably 0.01% or less. By keeping the PbO content within this range, the environmental impact can be suppressed.

[0055] (Fe2O3)

[0056] Glass 10 preferably does not contain Fe2O3. In glass 10, the content of Fe2O3, expressed as a percentage by mass based on oxides, is preferably 0.1% or less, more preferably 0.001% to 0.05%, and even more preferably 0.005% to 0.01%. By making the content of Fe2O3 so low, the decrease in light transmittance can be suppressed.

[0057] It should be noted that the Fe2O3 content on an external basis refers to the ratio of the mass of Fe2O3 contained in glass 10 to the total mass of all components of glass 10 other than Fe2O3, in oxide reference.

[0058] (Preferred composition of glass)

[0059] The preferred composition range of glass 10 will be further explained below.

[0060] In order to improve the clarity of the glass, the glass 10 may contain 1.0 wt% or less, preferably 0.5 wt% or less, more preferably 0.3 wt% or less, and even more preferably 0.1 wt% or less, expressed as a mass percentage based on oxides.

[0061] In glass 10, the ratio of RO content to the total content of SiO2, Al2O3, and B2O3 ((RO) / (SiO2+Al2O3+B2O3)) expressed as mol% based on oxides is preferably 0.2 to 0.5, more preferably 0.22 to 0.48, more preferably 0.27 to 0.44, more preferably 0.29 to 0.38, more preferably 0.31 to 0.34, and even more preferably 0.32 to 0.33. By making the ratio ((RO) / (SiO2+Al2O3+B2O3)) within this range, both Young's modulus and solubility can be obtained.

[0062] In glass 10, the total amount of SiO2, Al2O3, MgO, and CaO (SiO2 + Al2O3 + MgO + CaO), expressed as mole % based on oxides, is preferably 85% to 98%, more preferably 86% to 95%, even more preferably 87% to 93%, and even more preferably 88% to 91%. By making the lower limit of the total amount (SiO2 + Al2O3 + MgO + CaO) so high, the density and Young's modulus can be controlled, and by making the upper limit within this range, the deterioration of solubility can be suppressed.

[0063] In glass 10, the difference (Al2O3-RO), expressed as mole % based on oxides, is preferably -30% to 0%, more preferably -28.5% to -5%, more preferably -25% to -8%, more preferably -22% to -12%, more preferably -20% to -14%, and even more preferably -18% to -16%. By keeping (Al2O3-RO) within this range, both Young's modulus and solubility can be obtained.

[0064] Glass 10 preferably contains, expressed as a mole percent based on oxides:

[0065] SiO2: 60.5%~61.5%

[0066] Al2O3: 7.2%–7.7%

[0067] B2O3: 6.0%~7.0%

[0068] MgO: 17.0%~18.0%

[0069] CaO: 3.5%~4.5%

[0070] SrO: 0.0%~1.0%

[0071] BaO: 2.5%~3.5%.

[0072] By keeping the content of each oxide within this range, flexural deformation can be suppressed and manufacturing can be facilitated.

[0073] It should be noted that when the composition of glass 10 is within the above range, glass 10 preferably does not contain oxides other than the oxides mentioned above, except for unavoidable impurities.

[0074] It should be noted that glass 10 preferably does not contain a sintered body. That is, glass 10 is preferably a non-sintered glass. Here, a sintered body refers to a component obtained by heating multiple particles at a temperature below the melting point to bond the particles together. Since a sintered body contains pores, the porosity will be increased to some extent, but since glass 10 is not a sintered body, the porosity is low, typically 0%. However, the presence of unavoidable trace pores is permissible. Here, porosity refers to the so-called true porosity, which is the value obtained by dividing the sum of the volumes of pores (voids) communicating with the outside and pores (voids) not communicating with the outside by the total volume (apparent volume). Porosity can be determined, for example, according to JIS R 1634:1998 "Method for determination of sintered body density and open porosity of fine ceramics".

[0075] Furthermore, the glass used in glass 10 is generally preferably amorphous glass, i.e., an amorphous solid. Alternatively, the glass may be a crystalline glass containing crystals on its surface and internally, but from a density point of view, amorphous glass is preferred. In ceramics, materials produced by sintering have low transmittance and high density, therefore they are preferably not used.

[0076] (The shape of the glass)

[0077] Next, the shape of glass 10 will be described. For example... Figure 1 As shown, glass 10 is a plate-shaped glass substrate comprising a surface 12 as one main surface and a surface 14 as the opposite main surface of surface 12. Surface 14 may, for example, be parallel to surface 12. When viewed from above, i.e., from a direction orthogonal to surface 12, glass 10 may be in the shape of a circular plate, but is not limited to a circular plate shape; it may be any shape, such as a rectangular or other polygonal plate. It should be noted that shapes with notches, orientation flats, or other notches on the outer periphery are also included in the above-described shapes.

[0078] Furthermore, the thickness D of the glass 10, i.e., the length between surface 12 and surface 14, is preferably 0.1 mm to 5.0 mm, more preferably 0.1 mm to 2.0 mm, and even more preferably 0.1 mm to 0.7 mm. By making the thickness D 0.1 mm or more, it is possible to prevent the glass 10 from becoming too thin, thus suppressing breakage caused by bending and impact. By making the thickness D 2.0 mm or less, it is possible to suppress weight gain, and by making the thickness D 0.7 mm or less, it is possible to further appropriately suppress weight gain.

[0079] (Properties of glass)

[0080] Next, the characteristics of glass 10 will be explained.

[0081] (Young's modulus)

[0082] The Young's modulus E of glass 10 is preferably 75 GPa or higher, more preferably 77 GPa to 120 GPa, more preferably 79 GPa to 100 GPa, more preferably 81 GPa to 90 GPa, more preferably 83 GPa to 87 GPa, and even more preferably 84 GPa to 86 GPa. By keeping the Young's modulus E within this range, deflection can be appropriately suppressed. If the Young's modulus is too high, it becomes difficult to cut, grind, or polish.

[0083] (Young's modulus parameter)

[0084] The Young's modulus parameter Y of the glass 10 calculated based on its composition is preferably 0.9 or higher, more preferably 0.95 to 1.15, more preferably 0.96 to 1.10, more preferably 0.97 to 1.05, more preferably 0.98 to 1.04, more preferably 0.99 to 1.03, and even more preferably 1.00 to 1.02. By setting the Young's modulus parameter Y within this range, the Young's modulus E can be set within the aforementioned range, and deflection can be appropriately suppressed.

[0085] The Young's modulus parameter Y is calculated by the following formula (3).

[0086] Y=(60-0.244[SiO2]+0.27[Al2O3]-0.60[B2O3]+0.63[MgO]+0.48[CaO]-0.56[SrO]-0.22[BaO]+1.37[ZnO]) / 85···(3)

[0087] (density)

[0088] The density ρ of glass 10 is preferably 2.4 g / cm³. 3 ~2.9g / cm 3 More preferably 2.45 g / cm³ 3 ~2.85g / cm 3 More preferably 2.5 g / cm³ 3 ~2.8g / cm 3 More preferably 2.55 g / cm³ 3 ~2.75g / cm 3 More preferably 2.57 g / cm³ 3 ~2.7g / cm 3 More preferably, it is 2.59 g / cm³. 3 ~2.65g / cm 3 Further preferred is 2.6 g / cm³ 3~2.63g / cm 3 .

[0089] (E / ρ)

[0090] The ratio of Young's modulus E to the density ρ of glass 10 (E / ρ) is preferably 30 GPa·cm. 3 / g~40GPa·cm 3 / g, more preferably 30.5GPa·cm 3 / g~38GPa·cm 3 / g, more preferably 31GPa·cm 3 / g~36GPa·cm 3 / g, more preferably 31.5GPa·cm 3 / g~34GPa·cm 3 / g, more preferably 32GPa·cm 3 / g~33.5GPa·cm 3 / g, more preferably 32.2GPa·cm 3 / g~33GPa·cm 3 / g, further optimized to 32.4GPa·cm 3 / g~32.7GPa·cm 3 / g. By keeping the lower limit of the ratio (E / ρ) within this range, weight and deflection can be suppressed, thus facilitating operation. Furthermore, by keeping the upper limit of the ratio (E / ρ) within this range, crack formation during processing can be suppressed.

[0091] (Coefficient of linear thermal expansion)

[0092] The linear thermal expansion coefficient α of glass 10 is preferably below 5.8 ppm / ℃, more preferably 3.6 ppm / ℃ to 5.6 ppm / ℃, more preferably 3.8 ppm / ℃ to 5.2 ppm / ℃, more preferably 4 ppm / ℃ to 5.2 ppm / ℃, more preferably 4.2 ppm / ℃ to 4.8 ppm / ℃, more preferably 4.3 ppm / ℃ to 4.6 ppm / ℃, and more preferably 4.35 ppm / ℃ to 4.5 ppm / ℃.

[0093] By keeping the linear thermal expansion coefficient within this range, deflection can be appropriately suppressed. The linear thermal expansion coefficient α is the average thermal expansion coefficient in the range of 20°C to 300°C, and as a standard for thermal expansion measurement, it is the value measured according to DIN-51045-1. For example, as a measuring device, a thermal expansion meter (DIL 402 Expedis Supreme) manufactured by NETZSCH is used to perform measurements in the range of 0°C to 350°C, and the average thermal expansion coefficient in the range of 20°C to 300°C can be taken as the linear thermal expansion coefficient.

[0094] (Melting temperature T2, operating temperature T3, molding temperature T4, softening temperature T) 7.65 )

[0095] The melting temperature T2 of glass 10 is preferably 1400℃~1650℃, more preferably 1410℃~1620℃, even more preferably 1440℃~1590℃, even more preferably 1470℃~1560℃, even more preferably 1480℃~1550℃, even more preferably 1490℃~1540℃, even more preferably 1500℃~1530℃, and even more preferably 1510℃~1520℃. Melting temperature T2 refers to a temperature where the viscosity η is 10. 2 The temperature at dPa·s. By making the melting temperature T2 lower, melting can be facilitated. Conversely, by making the melting temperature T2 higher, it can be made comparable to the melting temperatures of other commonly used commercial glasses. This makes adjustments to the melting equipment easier when changing glass substrates.

[0096] The operating temperature T3 of glass 10 is preferably 1200℃~1400℃, more preferably 1215℃~1390℃, even more preferably 1240℃~1380℃, even more preferably 1260℃~1370℃, even more preferably 1290℃~1360℃, even more preferably 1315℃~1350℃, and even more preferably 1325℃~1345℃. Operating temperature T3 refers to a viscosity η of 10. 3 The temperature at dPa·s. By making the operating temperature T3 so low, molding can be made easier.

[0097] The molding temperature T4 of glass 10 is preferably 1080℃~1300℃, more preferably 1100℃~1280℃, more preferably 1120℃~1260℃, more preferably 1140℃~1240℃, more preferably 1160℃~1220℃, more preferably 1180℃~1215℃, more preferably 1190℃~1210℃, and more preferably 1200℃~1205℃. Molding temperature T4 refers to a viscosity η of 10. 4 The temperature at dPa·s. By making the molding temperature T4 so low, molding can be made easier.

[0098] The softening temperature T of glass 10 7.65 Preferably, the temperature is 800℃~1000℃, more preferably 830℃~980℃, even more preferably 850℃~960℃, even more preferably 870℃~940℃, even more preferably 890℃~925℃, even more preferably 900℃~920℃, and even more preferably 905℃~915℃. Softening temperature T 7.65 This refers to a viscosity η of 10. 7.65 The temperature at which dPa·s is achieved. This is determined by setting the softening temperature T... 7.65 This lower temperature makes molding easier.

[0099] It should be noted that the melting temperature T2, operating temperature T3, and molding temperature T4 can be determined using methods such as the inner cylinder rotation method. The softening temperature T... 7.65 (°C) can be determined by the method specified in JIS R 3103-1 "Adhesion of glass and adhesion fixation point - Part 1: Determination of softening point".

[0100] (T2-T4)

[0101] In glass 10, the difference (T2-T4) between the melting temperature T2 and the forming temperature T4 is preferably 280℃ to 340℃. Alternatively, the difference (T2-T4) can be below 400℃, 290℃ to 375℃, 295℃ to 360℃, 298℃ to 340℃, 300℃ to 320℃, 305℃ to 315℃, or 307℃ to 310℃. By making the difference (T2-T4) so ​​small, the temperature slope from the melting process to the forming process is reduced. This suppresses the increase in energy loss during process transfer and facilitates manufacturing. If the difference (T2-T4) is too small, the viscosity changes too much with temperature, making it difficult to control the melting and forming temperatures from the melting process to the forming process.

[0102] (T4-T) 7.65 )

[0103] In glass 10, the forming temperature T4 and the softening temperature T 7.65 The difference (T4-T) 7.65 The preferred temperature is 290°C or higher, more preferably 290°C to 300°C. Additionally, the temperature difference (T4-T) is... 7.65 The temperature can be above 250℃, 250℃~350℃, 260℃~335℃, 270℃~315℃, 280℃~305℃, 285℃~300℃, or 290℃~295℃. If the difference (T4-T) 7.65 If the viscosity is small, precise temperature control is required when controlling the glass viscosity during the forming process. Using large-scale manufacturing equipment makes precise temperature control difficult, which may not only prevent the glass from forming the designed shape but also sometimes result in cracks or breakage. By adjusting the temperature difference (T₄-T₅), 7.65 Such a large viscosity makes viscosity control during molding easier, thus simplifying manufacturing.

[0104] (Methods for manufacturing glass)

[0105] Glass 10 can be manufactured by any method, for example, by the following method. First, raw materials such as silica sand or soda ash, which will become the raw materials for the compounds contained in glass 10, are heated to a specified temperature (e.g., 1500°C to 1600°C) and melted. Then, after clarifying the molten raw material (glass), a forming process is performed to shape it into a sheet. The formed glass has the composition range of glass 10 described above, based on oxides. Then, glass 10 is manufactured by performing a slow cooling process on the glass formed in the forming process.

[0106] It should be noted that the manufacturing method of glass 10 is not limited to the above and can be arbitrary. For example, the slow cooling process is not necessary. In addition, the forming process when manufacturing glass 10 can adopt various methods, such as casting, drawing (e.g., overflow drawing, flow hole drawing, and redrawing), float glass, rolling, and pressing.

[0107] Next, an example of the manufacturing process when glass 10 is used to manufacture a FOWLP will be described. In FOWLP manufacturing, multiple semiconductor chips are bonded to glass 10, and the semiconductor chips are covered with a sealing material to form a component substrate. Then, glass 10 is separated from the component substrate, and the side of the component substrate opposite to the semiconductor chips is bonded to, for example, another piece of glass 10. Then, wiring, solder bumps, etc., are formed on the semiconductor chips, and the component substrate is separated from glass 10 again. Then, by cutting the component substrate into individual semiconductor chips, it is monolithically processed to obtain a semiconductor device.

[0108] (Effect)

[0109] As explained above, the glass 10 of the first aspect of this disclosure has parameter A of 0.817 or less, parameter B of 0.898 or more, a ratio of MgO content to the total content of divalent oxide RO (MgO / RO) expressed as mol% based on oxides of 0.65 or more, a Young's modulus E of 80 GPa or more, and is an alkali-free glass.

[0110] Since the glass 10 disclosed herein is an alkali-free glass with a Young's modulus E of 80 GPa or higher, it can appropriately suppress flexural deformation. However, generally speaking, alkali-free glasses with high Young's modulus exhibit a larger difference (T2-T4) between the melting temperature T2 and the forming temperature T4, and a larger difference between the forming temperature T4 and the softening temperature T... 7.65 The difference (T4-T) 7.65 The difference (T2 - T4) tends to decrease. If the difference is large, the temperature must be significantly lowered when transferring from the melting process to the molding process, which will increase energy loss. Additionally, if the difference (T4 - T) is large... 7.65 If the viscosity is small, the temperature range that can be allowed in the molding process will be smaller, making it difficult to control the viscosity and mold.

[0111] The inventors conducted in-depth research on this matter and discovered that by keeping parameters A, B, and the ratio (MgO / RO) within the aforementioned ranges, it is possible to appropriately suppress the situation where the difference (T2-T4) becomes excessively large and the difference (T4-T... 7.65 The condition of insufficient MgO / RO ratio is prevented. That is, by keeping the parameters A, B, and MgO / RO ratio of the glass 10 of this disclosure within the aforementioned ranges, the increase in energy loss transferred from the melting process to the forming process can be suppressed, and the difficulty in controlling viscosity can be prevented. Therefore, according to this disclosure, a glass 10 that can suppress flexural deformation and is easy to manufacture can be provided.

[0112] Furthermore, alkali-free glasses with a Young's modulus E of 80 GPa or higher tend to have a larger specific modulus E / ρ (Young's modulus / density), which may easily cause cracking during processing. Conversely, if the specific modulus E / ρ becomes too small, it is prone to breakage and becomes too heavy, making it difficult to process. To address this, the glass 10 of this disclosure maintains the specific modulus E / ρ within an appropriate range by keeping parameters A, B, and the ratio (MgO / RO) within the aforementioned ranges, thereby suppressing cracking during processing and facilitating process handling.

[0113] The glass 10 of the second aspect of this disclosure preferably contains, in the glass 10 of the first aspect, expressed as mol% based on oxides:

[0114] SiO2: 55.0%~65.0%

[0115] Al2O3: 3.0%~13.0%

[0116] B2O3: 1.0%~10.0%

[0117] RO: 10.0%~40.0%.

[0118] According to this disclosure, it is able to suppress flexural deformation and is easy to manufacture.

[0119] The glass 10 of the third aspect of this disclosure preferably contains, in the glass 10 of the first or second aspect, expressed as mole percent based on oxides:

[0120] MgO: 10.0%~25.0%.

[0121] According to this disclosure, it is able to suppress flexural deformation and is easy to manufacture.

[0122] The glass 10 of the fourth aspect of this disclosure preferably contains, in any of the glasses 10 of the first to third aspects, expressed as a mole percent based on oxides:

[0123] CaO: 1.0%~10.0%.

[0124] According to this disclosure, it is able to suppress flexural deformation and is easy to manufacture.

[0125] The glass 10 of the fifth aspect of this disclosure preferably contains, in any of the glasses 10 of the first to fourth aspects, expressed as a mole percent based on oxides:

[0126] SrO: 0%~5.0%.

[0127] According to this disclosure, it is able to suppress flexural deformation and is easy to manufacture.

[0128] The glass 10 of the sixth aspect of this disclosure preferably contains, in any of the glasses 10 of the first to fifth aspects, expressed as a mole percent based on oxides:

[0129] BaO: 0%~5.0%.

[0130] According to this disclosure, it is able to suppress flexural deformation and is easy to manufacture.

[0131] The glass 10 of the seventh aspect of this disclosure is preferably used as a substrate among the glass 10s of any one of the first to sixth aspects. The glass 10 of this disclosure is suitable for use as a substrate.

[0132] The glass 10 of the eighth aspect of this disclosure is the glass 10 of the seventh aspect, and is preferably used for manufacturing at least one of a fan-out wafer-level package and a fan-out panel-level package. The glass 10 is suitable for these applications.

[0133] (Example)

[0134] Next, the embodiments will be described. Tables 1-1 to 1-3 are tables showing the characteristics of the glass in each example. It should be noted that the implementation method can be modified within the scope of achieving the effects of the invention.

[0135] Table 1-1

[0136]

[0137] Table 1-2

[0138]

[0139] Table 1-3

[0140]

[0141] (Example 1)

[0142] In Example 1, glass with the composition shown in Table 1-1 was produced. In Example 1, a blank with a diameter of 320 mm and a thickness of 6 mm was manufactured using a casting method. Then, multiple plates with a diameter of 300 mm and a thickness of 3 mm were cut from the center of the blank. Using cerium oxide as the abrasive, both sides of these plates were double-sided ground to obtain glass with a thickness of 0.7 mm.

[0143] Using the above formula (1), the glass parameter A of Example 1 is calculated.

[0144] Using the above formula (2), the glass parameter B of Example 1 is calculated.

[0145] The density ρ (g / cm³) of the glass in Example 1 was determined. 3 Density is determined using the Archimedes method.

[0146] The Young's modulus E (GPa) of the glass in Example 1 was determined. The Young's modulus was determined using the ultrasonic pulse method as specified in JIS R 1602:1995 "Test Method for Elastic Modulus of Precision Ceramics". The bulk density of the sample was determined using the Archimedes method. The longitudinal and transverse wave velocities were measured using an OLYMPUS 38DL PLUS ultrasonic thickness gauge to calculate the Young's modulus value.

[0147] The linear thermal expansion coefficient α (ppm / °C) of the glass in Example 1 was determined. As the measuring apparatus, a thermal expansion meter (DIL 402 Expedis Supreme) manufactured by NETZSCH was used, and the measurement was performed in the range of 0°C to 350°C. The average thermal expansion coefficient in the range of 20°C to 300°C was taken as the linear thermal expansion coefficient α.

[0148] For the glass in Example 1, the melting temperature T2 (°C), working temperature T3 (°C), and forming temperature T4 (°C) were determined as high-temperature viscosity values. The melting temperature T2, working temperature T3, and forming temperature T4 were determined by the inner cylinder rotation method.

[0149] The softening temperature T of the glass in Example 1 was determined. 7.65 (°C). Softening temperature T 7.65 (°C) is determined by the method specified in JIS R 3103-1 "Adhesion of glass and adhesion fixation point - Part 1: Determination of softening point".

[0150] The measurement and calculation results are shown in Table 1-1.

[0151] (Example 2~Example 60)

[0152] In Examples 2 to 60, the composition of the glass was set as shown in Tables 1-1 to 1-3, and except for this, the glass was manufactured in the same manner as in Example 1. The measurement results and calculation results of each example are shown in Tables 1-1 to 1-3.

[0153] (Evaluation)

[0154] The manufacturability of the glass of each example was determined and the flexure was evaluated.

[0155] In the determination of manufacturability, when the difference (T2 - T4) is 280°C to 340°C and the difference (T4 - T 7.65 ) is 290°C or more, it is judged as acceptable (〇), and when at least one of the differences (T2 - T4) being 280°C to 340°C and the difference (T4 - T 7.65 ) being 290°C or more is not satisfied, it is judged as unacceptable (×).

[0156] In the flexure evaluation, when the Young's modulus is 80 GPa or more, it is judged as acceptable (〇), and when the Young's modulus is less than 80 GPa, it is judged as unacceptable (×).

[0157] As shown in Table 1, for the glasses of Examples 1 to 41 (Examples) where parameter A is 0.817 or less, parameter B is 0.898 or more, and the ratio (MgO / RO) is 0.65 or more, the manufacturability evaluation and the flexure evaluation are acceptable, and it can be seen that flexure can be suppressed and it is easy to manufacture.

[0158] On the other hand, for the glasses of Comparative Examples 42 to 60 which do not satisfy at least one of parameter A being 0.817 or less, parameter B being 0.898 or more, and the ratio (MgO / RO) being 0.65 or more, at least one of the manufacturability evaluation and the flexure evaluation is unacceptable, and it can be seen that flexure cannot be suppressed and it is not easy to manufacture.

[0159] The embodiments of the present invention have been described above, but the embodiments are not limited to the content of the embodiments. In addition, the above constituent elements include elements that can be easily assumed by those skilled in the art, substantially the same elements, and elements within the so-called equivalent range. And, the above constituent elements can be combined appropriately. And, various omissions, substitutions, or changes of the constituent elements can be made without departing from the gist of the above embodiments.

[0160] Symbol Explanation

[0161] 10 Glass

Claims

1. A type of glass, The parameter A shown in equation (1) is below 0.

817. The parameter B shown in equation (2) is 0.898 or higher. The ratio of MgO content to the total content of divalent oxides RO, expressed as mol% on an oxide basis, is 0.65 or higher. The Young's modulus is above 80 GPa. It is alkali-free glass. A=1.747-0.022×[SiO2]+0.006×[Al2O3]+0.018×[B2O3]+0.013×[MgO]-0.010×[CaO]-0.003×[SrO]+0.012×[BaO]+0.015×[ZnO] ···(1) B=1.315-0.010×[SiO2]+0.005×[Al2O3]+0.023×[B2O3]+0.004×[MgO]-0.016×[CaO]-0.007×[SrO]+0.011×[BaO]+0.010×[ZnO] ···(2).

2. The glass according to claim 1, wherein, Expressed as mole percent based on oxides, it contains SiO2: 55.0%–65.0%, Al2O3: 3.0%–13.0%, B2O3: 1.0%–10.0%, and RO: 10.0%–40.0%.

3. The glass according to claim 1 or 2, wherein, Expressed as mol% based on oxides, it contains 10.0% to 25.0% MgO.

4. The glass according to claim 1 or 2, wherein, Expressed as mol% based on oxides, it contains CaO: 1.0% to 10.0%.

5. The glass according to claim 1 or 2, wherein, Expressed as mole percent on an oxide basis, it contains SrO: 0% to 5.0%.

6. The glass according to claim 1 or 2, wherein, Expressed as mole percent based on oxides, it contains BaO: 0% to 5.0%.

7. The glass according to claim 1 or 2, wherein, The parameter A is 0.781 to 0.

817. The parameter B is 0.903 to 0.

935. The ratio of MgO content to the total content of divalent oxide RO, expressed as mol% on an oxide basis, is 0.65 to 0.

9.

8. The glass according to claim 1 or 2, wherein, Expressed as mole percent based on oxides, it contains SiO2: 61.0%–63.5% and Al2O3: 7.0%–8.5%.

9. The glass according to claim 1 or 2, wherein, It contains, in mole percent based on oxides: MgO: 12%–22%, CaO: 1.1%–7%, SrO: 0.1%–5.0%, BaO: 0.1%–5.0%.

10. The glass according to claim 1 or 2, wherein, It does not actually contain alkali metal oxides.

11. The glass according to claim 1 or 2, wherein, The Young's modulus parameter Y shown in equation (3) is 0.9 or higher. Y=(60-0.244[SiO2]+0.27[Al2O3]-0.60[B2O3]+0.63[MgO]+0.48[CaO]-0.56[SrO]-0.22[BaO]+1.37[ZnO]) / 85···(3).

12. The glass according to claim 1 or 2, wherein, The ratio of Young's modulus E to density ρ, E / ρ, is 30 GPa·cm. 3 / g~40GPa·cm 3 / g.

13. The glass according to claim 1 or 2, wherein, The difference between the melting temperature T2 and the molding temperature T4, T2-T4, is below 400℃.

14. The glass according to claim 1 or 2, wherein, Molding temperature T4 and softening temperature T 7.65 The difference is T4-T 7.65 It is above 250℃.

15. The glass according to claim 1 or 2, wherein, The ratio of RO content to the total content of SiO2, Al2O3 and B2O3, i.e. (RO) / (SiO2+Al2O3+B2O3), is 0.2 to 0.

5.

16. The glass according to claim 1 or 2, wherein, Expressed as mole percent based on oxides, the total amount of SiO2, Al2O3, MgO, and CaO, i.e., SiO2 + Al2O3 + MgO + CaO, is 85% to 98%.

17. The glass according to claim 1 or 2, wherein, Expressed as mole % based on oxides, the difference between Al2O3 and RO, obtained by subtracting the RO content from the Al2O3 content, is -30% to 0%.

18. The glass according to claim 1 or 2, wherein, It is used as a substrate.

19. The glass according to claim 15, wherein, It is used to manufacture at least one of a fan-out wafer-level package and a fan-out panel-level package.

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