Glass and methods of manufacturing glass

Abstract

The objective of this invention is to suppress flexural deformation. The glass 10 of this invention, expressed in moles (%) based on oxides, contains SiO₂: 35%–60%, B₂O₃: 0.8%–8%, Al₂O₃: 6%–21%, MgO: 17%–44%, and (MgO / Al₂O₃) ≥ 1. The measured Madelung constant m, calculated by equation (1A), is 1.05 or higher, and the ratio of the measured value of the linear thermal expansion coefficient α to the calculated value αcal of the linear thermal expansion coefficient based on the composition, i.e., the coefficient of thermal expansion, is 0.7 or lower. Here, E is the measured value of the Young's modulus of glass 10, Vp is the average atomic filling rate of glass 10, and Gt is the average bond dissociation energy of glass 10.

Description

Technical Field

[0001] This invention relates to a type of glass and a method for manufacturing the glass. Prior 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 supporting glass substrate whose average linear thermal expansion coefficient in the temperature range of 20°C to 200°C exceeds 28×10⁻⁷ / °C but does not reach 50×10⁻⁷ / °C. [Previous Technical Documents] [Patent Literature]

[0003] [Patent Document 1] Japanese Patent No. 6443668 Summary of the Invention

[0004] [The problem the invention aims to solve]

[0005] Here, for example, for glass used as a support for semiconductor components, it is required to suppress flexural deformation.

[0006] The present invention was made in view of the above-mentioned problems, and its object is to provide a glass capable of suppressing deflection and a method for manufacturing the glass. [Technical means to solve the problem]

[0007] To solve the above problems and achieve the objective, the glass of the present invention, expressed in moles (%) based on oxides, contains SiO2: 35%~60%, B2O3: 0.8%~8%, Al2O3: 6%~21%, MgO: 17%~44%, and (MgO / Al2O3) ≥ 1. The measured Madelung constant m, calculated by equation (1A), is 1.05 or higher, and the ratio of the measured value of the linear thermal expansion coefficient α (ppm / K) to the calculated value of the linear thermal expansion coefficient αcal (ppm / K) based on the composition, i.e., the coefficient of thermal expansion, is 0.7 or lower. Here, E is the measured value of the Young's modulus (GPa) of the above glass, Vp is the average atomic filling rate of the above glass, and Gt is the average bond dissociation energy of the above glass.

[0008] m = E / (2·V p·G t)···(1A)

[0009] To solve the above problems and achieve the objective, the glass manufacturing method of the present invention includes the following steps: forming a glass containing, in molar percentage based on oxides, 35%~60% SiO2, 6%~21% Al2O3, and 17%~44% MgO; holding the formed glass at a temperature 0°C to 100°C above the glass transition point Tg for more than 0 hours and less than 10 hours; and cooling the glass at a temperature decreasing rate of 0.5°C / min to 100°C / min. [Effects of the Invention]

[0010] According to the present invention, flexure can be suppressed. Simple Explanation of the Diagram

[0011] Figure 1 is a schematic diagram of the glass in this embodiment. Figure 2 shows the thermal expansion factor for each example and the determination of the Madelung constant. Figure 3 is a schematic diagram used to illustrate flexural evaluation. Implementation

[0012] Hereinafter, suitable embodiments of the present invention will be described in detail with reference to the accompanying drawings. Furthermore, the present invention is not limited to these embodiments, and when multiple embodiments are available, it also includes combinations of these embodiments. Also, numerical values ​​include rounding ranges.

[0013] (Glass) Figure 1 is a schematic diagram of the glass according to this embodiment. As shown in Figure 1, the glass 10 of this embodiment can be used as a glass substrate for manufacturing semiconductor packages, and more specifically, it is a support glass substrate for manufacturing FOWLP (Fan Out Wafer Level Package) and the like. However, the use of glass 10 is not limited to manufacturing FOWLP and the like, and can be used for any purpose, such as a glass substrate for supporting components, or for purposes other than supporting components. Furthermore, FOWLP and the like include Fan Out Wafer Level Package (FOWLP) and Fan Out Panel Level Package (FOPLP).

[0014] (Composition of glass) When the total amount of glass 10 is set to 100% based on oxide moles, glass 10 contains 35% to 60% SiO 2, 0.8% to 8% B 2O 3, 6% to 21% Al 2O 3, and 17% to 44% MgO. Preferably, glass 10 contains at least 0.3% TiO 2 and at least 8% ZrO 2, more preferably based on oxide moles. Furthermore, in terms of the mole ratio based on oxides, the ratio of MgO content to Al₂O₃ content is 1 or more ((MgO / Al₂O₃)≧1), and preferably 1.0 or more and 3.2 or less. Thus, the glass 10 contains an excess of MgO relative to Al₂O₃. By ensuring that SiO2, B2O3, Al2O3, and MgO are within this range, and that the amount of MgO relative to Al2O3 is within this range, the coefficient of thermal expansion can be reduced and the Young's modulus can be increased, thus suppressing deflection. Furthermore, by ensuring that the amount of at least one of TiO2 and ZrO2 is within this range, the coefficient of thermal expansion can be reduced and the Young's modulus increased, thus more appropriately suppressing deflection. Moreover, the numerical range indicated by "~" refers to a range including the values ​​before and after "~" as both the lower and upper limits; the same meaning applies to the use of "~" below.

[0015] Glass 10 may contain at least one of CaO, Na₂O₃, and K₂O as an optional component. When the total amount of glass 10 is set to 100% based on oxides (in moles%), it preferably contains 0% to 8% CaO, more preferably 0% to 7% Na₂O, and more preferably 0% to 6% K₂O. A content of 0% here refers to the absence of this component. Glass 10 more preferably contains 0% to 5% CaO, 0.25% to 5.5% Na₂O, and 0.25% to 4.5% K₂O, and even more preferably 0% to 3% CaO, 0.5% to 4% Na₂O, and 0.5% to 3% K₂O. By keeping the content of these components within the above-mentioned range, flexural deformation can be appropriately suppressed.

[0016] Glass 10 preferably comprises SiO 2, Al 2O 3, MgO, B 2O 3, and TiO 2. In this case, when the total amount of glass 10 is set to 100% based on oxides in moles percent, glass 10 preferably contains 35% to 57% SiO 2, 9.6% to 20% Al 2O 3, and 19.5% to 44% MgO, 0.8% to 7.2% B 2O 3, and 0.3% to 5% TiO 2. By keeping the content of these components within the above range, flexural deformation can be appropriately suppressed.

[0017] When the total amount of glass 10 is set to 100% based on oxides (in moles%), it preferably contains 35% to 52% SiO2, 9.6% to 20% Al2O3, 24% to 44% MgO, 0.8% to 4.5% B2O3, and 0.3% to 5% TiO2. By keeping the content of these components within the above range, for example, even without the slow cooling process described below, the Madelung constant m can be set to 1.05 or higher, and deflection can be appropriately suppressed. The glass 10 with this composition may or may not undergo a slow cooling process.

[0018] Furthermore, glass 10 is preferably free of sintered material. That is, glass 10 is preferably a non-sintered glass. Here, a sintered system refers to a component obtained by heating a plurality of particles at a temperature below their melting point to bond the particles together. Sintered materials contain pores and therefore have a relatively high porosity, but since glass 10 is not a sintered material, its porosity is low, typically 0%. However, the presence of unavoidable trace amounts of pores is permissible. The porosity here refers to true porosity, which is the sum of the volumes of pores (both connected to the outside and pores (both not connected to the outside) divided by the total volume (apparent volume). Porosity can be measured, for example, according to JIS R 1634.

[0019] Furthermore, the glass used for glass 10 is preferably amorphous glass, i.e., amorphous solid. Also, the glass may be a crystalline glass containing crystals on its surface or inside, but from a density perspective, amorphous glass is preferred. In ceramics, ceramics produced by sintering have lower transmittance and higher density, so they are preferably not used.

[0020] (The shape of glass) Next, the shape of glass 10 will be described. As shown in Figure 1, glass 10 is a plate-shaped glass substrate comprising a first surface 12 as one surface and a second surface 14 as another surface. The second surface 14 is the surface opposite to the first surface 12, for example, parallel to the first surface 12. When viewed from above, i.e., from a direction orthogonal to the first surface 12, glass 10 can be a circular plate shape, but is not limited to a circular plate shape; it can also be any shape, such as a rectangular or other polygonal plate.

[0021] Furthermore, the thickness D of the glass 10, i.e., the length between the first surface 12 and the second surface 14, is preferably 0.1 mm to 2.0 mm, and more preferably 0.1 mm to 0.5 mm. By setting the thickness D to 0.1 mm or more, the glass 10 can be prevented from becoming too thin, thereby preventing breakage due to bending or impact. By setting the thickness D to 2.0 mm or less, the increase in weight can be prevented, and by setting the thickness D to 0.5 mm or less, the increase in weight can be further appropriately prevented.

[0022] (Determination of Madelung constant in glass) The parameter represented by formula (1A) for glass 10 is the Madelung constant m, which is 1.05 or more, preferably 1.05 or more and 1.35 or less, more preferably 1.07 or more and 1.30 or less, and even more preferably 1.10 or more and 1.25 or less.

[0023] m = E / (2·V p·G t)···(1A)

[0024] Here, E is the measured Young's modulus (GPa) of glass 10, Vp is the average atomic filling rate of glass 10, and Gt is the average bond dissociation energy of glass 10. In this embodiment, the Young's modulus E of glass 10 is the value measured using an OLYMPUS 38DL PLUS instrument based on ultrasonic propagation.

[0025] The average atomic filling rate Vp is the average (arithmetic mean) of the atomic filling rates Vi of each metal oxide contained in glass 10. The atomic filling rate Vi of the metal oxide is calculated by the following formula (1B).

[0026] V i=6.02·10 23·(4 / 3)·π·(x·r 3 M+y·r 3 O)···(1B)

[0027] Here, the metal oxide contained in glass 10 is denoted as M xO y. M is a metal element, O is an oxygen element, x is the valence of the metal element M, and y is the valence of the oxygen element O. rM is the Shannon ion radius of the metal element M in the metal oxide MxOy, and rO is the Shannon ion radius of the oxygen element O in the metal oxide MxOy.

[0028] The average bond dissociation energy Gt is the average (arithmetic mean) of the bond dissociation energies Gi of each metal oxide contained in glass 10. The bond dissociation energy Gi of the metal oxides is calculated by the following formula (1C).

[0029] G i=di / M i·{x·ΔHf(M gas)+y·ΔHf(O gas)-ΔHf(M xO ycrystal)-(x+y)·RT}···(1C)

[0030] Here, di is the density of the metal oxide MxOy, Mi (g / mol) is the molecular weight of the metal oxide MxOy, ΔHf(M gas) is the standard enthalpy of formation of the metal element M in the gaseous state, ΔHf(O gas) is the standard enthalpy of formation of the oxygen element O in the gaseous state, and ΔHf(MxOy crystal) is the standard enthalpy of formation of the metal oxide MxOy. Also, R is the gas constant, and T is the absolute temperature.

[0031] Since (2·Vp·Gt) in equation (1A) corresponds to the calculated value of the Young's modulus (GPa) of glass 10 based on its composition, the measured Madelung constant m can be considered as the ratio of the actual measured value of the Young's modulus of glass 10 to the calculated value of the Young's modulus of glass 10. In this embodiment, the measured Madelung constant m of glass 10 is within the above-mentioned range, thereby the Young's modulus is greater than the calculated value expected based on the composition, and thus deflection can be appropriately suppressed.

[0032] Furthermore, the Young's modulus E of glass 10 is preferably 95 GPa to 150 GPa, more preferably 100 GPa to 130 GPa, and even more preferably 105 GPa to 125 GPa. By making the Young's modulus E so high, flexural bending can be appropriately suppressed.

[0033] (Coefficient of thermal expansion of glass) The coefficient of thermal expansion of glass 10 is 0.7 or less, preferably 0.45 or more and 0.7 or less, more preferably 0.5 or more and 0.65 or less, and even more preferably 0.55 or more and 0.6 or less. The coefficient of thermal expansion is the ratio (i.e., α / α cal) of the measured value α (ppm / K) of the linear thermal expansion coefficient of glass 10 to the calculated value α cal (ppm / K) of the linear thermal expansion coefficient calculated based on the composition of glass 10. The measured value α of the linear thermal expansion coefficient is the average thermal expansion coefficient within the range of 50°C to 200°C, and it is the value measured according to DIN-51045-1 as the specification for thermal expansion measurement. For example, using a dilatometer (DIL 402 Expedis) from NETZSCH as the measuring device, measurements are taken within the range of 30°C to 300°C, and the average thermal expansion coefficient within the range of 50°C to 200°C can be used as the measured value α of the linear thermal expansion coefficient.

[0034] The calculated value of the linear thermal expansion coefficient αcal of glass 10 will be explained. Hereinafter, the thermal expansion parameter αpi of each oxide contained in glass 10 will be set as the value calculated by equation (2A). Furthermore, the calculated value of the linear thermal expansion coefficient αcal1 of glass containing only monovalent elements of the modified oxides contained in glass 10 will be set as the value calculated by equation (2B). Furthermore, the calculated value of the linear thermal expansion coefficient αcal2 of glass containing only divalent elements of the modified oxides contained in glass 10 will be set as the value calculated by equation (2C). Furthermore, the calculated value of the linear thermal expansion coefficient αcal3 of glass containing only trivalent elements of the modified oxides contained in glass 10 will be set as the value calculated by equation (2D). The αp in equations (2B), (2C), and (2D) is obtained by adding the values ​​obtained by multiplying equation (2A) by the cation ratio of each oxide. That is, for example, αp in formula (2B) is the sum of the values ​​obtained by multiplying the thermal expansion parameter αpi of the modified oxide of the monovalent element contained in glass 10 by the cation ratio in the modified oxide for each monovalent element contained in glass 10. Also, for example, αp in formula (2C) is the sum of the values ​​obtained by multiplying the thermal expansion parameter αpi of the modified oxide of the divalent element contained in glass 10 by the cation ratio in the modified oxide for each divalent element contained in glass 10. Also, for example, αp in formula (2D) is the sum of the values ​​obtained by multiplying the thermal expansion parameter αpi of the modified oxide of the trivalent element contained in glass 10 by the cation ratio in the modified oxide for each trivalent element contained in glass 10. Furthermore, the cation ratio refers to the ratio of the number of cations to the total number of cations and anions contained in the modified oxide (number of cations / (number of cations + number of anions)).

[0035] α pi={ni / (ni-1)}·(Z +i·Z -i / r eqi) -1···(2A) α cal1=(290·α p-89.6) / 10···(2B) α cal2=(300·α p-49.1) / 10···(2C) α cal3=(848·α p-234) / 10···(2D)

[0036] Here, ni is the Born index, Z+i is the cation charge of the modified oxide, Z-i is the anion charge of the oxide, and reqi is the equilibrium value of the average distance between ion pairs of the oxide at temperature 0 (K). Furthermore, regarding the thermal expansion parameter αpi, the result calculated by equation (2A) is recorded in the literature "Hirohisa Masuda et al., Calculation of Thermal Expansion Coefficient of Silicate Glasses Using Compositional Parameters, Journal of the Japan Society for Metals, Vol. 62, No. 5 (1998) 444-448". For example, the thermal expansion parameter αpi of Al₂O₃ is 0.368, and the thermal expansion parameter αp of MgO can be 0.601. Furthermore, the modified oxide composition of monovalent elements contained in glass 10 refers to M 2O (e.g., K 2O), the modified oxide composition of divalent elements contained in glass 10 refers to MO (e.g., MgO), and the modified oxide composition of trivalent elements contained in glass 10 refers to M 2O 3 (e.g., Y 2O 3).

[0037] In this case, the calculated value of the linear thermal expansion coefficient αcal of glass 10 is obtained by the following formula (2E).

[0038] α cal=(M1·α cal1+M2·α cal2+M3·α cal3) / {10·(M1+M2+M3)···(2E)

[0039] M1 is the cation ratio (%) of the modified oxide of monovalent elements, M2 is the cation ratio (%) of the modified oxide of divalent elements, and M3 is the cation ratio (%) of the modified oxide of trivalent elements.

[0040] Furthermore, when glass 10 does not contain any monovalent modified oxide components, the numerator (M1·α cal1) on the right side of equation (2E) is zero, and the denominator M1 on the right side is zero. Also, when glass 10 does not contain any divalent modified oxide components, the numerator (M2·α cal2) on the right side of equation (2E) is zero, and the denominator M2 on the right side is zero. Also, when glass 10 does not contain any trivalent modified oxide components, the numerator (M1·α cal1) on the right side of equation (2E) is zero, and the denominator M3 on the right side is zero. Furthermore, when the glass 10 contains multiple monovalent element modified oxide components, for each monovalent element modified oxide component, the values ​​obtained by multiplying the α cal1 of the monovalent element modified oxide component by the cation ratio of the content of that modified oxide component are summed, and the summed value is treated as (M1·α cal1) in the numerator of the right side of equation (2E). The cation ratio of the total content of each monovalent element modified oxide component is treated as M1 in the denominator of the right side of equation (2E). Similarly, when the glass 10 contains multiple divalent element modified oxide components, for each divalent element modified oxide component, the values ​​obtained by multiplying the α cal2 of the divalent element modified oxide component by the cation ratio of the content of that modified oxide component are summed, and the summed value is treated as (M2·α cal2) in the numerator of the right side of equation (2E). The cation ratio of the total content of each divalent element modified oxide component is treated as M2 in the denominator of the right side of equation (2E). Similarly, when the glass 10 contains multiple types of trivalent element modified oxide components, for each trivalent element modified oxide component, the values ​​obtained by multiplying the α cal3 of the trivalent element modified oxide component by the cation ratio of the content of the modified oxide component are summed, and the summed value is treated as (M3·α cal3) in the numerator of the right side of equation (2E), and the cation ratio of the total content of each trivalent element modified oxide component is treated as M3 in the denominator of the right side of equation (2E).

[0041] The ratio of the measured value α of the linear thermal expansion coefficient of glass 10 to the calculated value αcal of the linear thermal expansion coefficient calculated by the above method is the thermal expansion factor. By keeping the thermal expansion factor of glass 10 within the above range, the linear thermal expansion coefficient is made less than the calculated value expected based on the composition, thermal expansion is suppressed, and heat-induced deflection can be appropriately suppressed.

[0042] Furthermore, the measured value of the linear thermal expansion coefficient α of glass 10 is preferably 3 ppm / K or higher and 6 ppm / K or lower, more preferably 3.1 ppm / K or higher and 5.8 ppm / K or lower, and even more preferably 3.2 ppm / K or higher and 5.6 ppm / K or lower. By making the linear thermal expansion coefficient so low, deflection can be appropriately suppressed in wafers for high-density semiconductor packaging.

[0043] (Methods for manufacturing glass) Glass 10 is manufactured as follows. For example, raw materials such as silica fume or soda ash, which are raw materials for compounds contained in glass 10, are heated to a predetermined temperature (e.g., 1500°C to 1600°C) until they melt. Then, after clarifying the molten raw material (glass), a forming process is performed to form it into a sheet shape. The formed glass has the composition range of glass 10 described above, based on oxides. Then, a slow cooling process is performed on the glass formed in the forming process, thereby manufacturing glass 10. The slow cooling process here includes: a holding process, which holds the formed glass at a predetermined heating temperature for a predetermined holding time; and a cooling process, which cools the glass held at the heating temperature for the holding time to a predetermined temperature at a predetermined temperature reduction rate. The heating temperature during the process is maintained at 0°C to 100°C above the glass transition point (Tg) of glass 10, preferably 10°C to 70°C above, and more preferably 20°C to 40°C above. The holding time during the process is maintained for more than 0 hours and less than 10 hours, preferably 0.25 hours to 6 hours, and more preferably 0.5 hours to 2 hours. The temperature reduction rate (cooling rate) during the cooling process is 0.5°C / min to 100°C / min, preferably 0.75°C / min to 75°C / min, and more preferably 1°C / min to 50°C / min. By performing a slow cooling process under the above conditions, the Madelung constant m of the glass 10 with the composition described in this embodiment can be set to 1.05 or more, which can appropriately suppress deflection. The temperature at which cooling ends during the cooling process, i.e., the predetermined temperature, can be any temperature, such as room temperature (e.g., 20°C).

[0044] Furthermore, the manufacturing method of glass 10 is not limited to the above and can be any manufacturing method. For example, a slow cooling process is not necessary. Also, the forming process when manufacturing glass 10 can adopt various methods, such as: melt casting, downdrawing (e.g., overflow downdrawing, flow hole downdrawing, and redrawing), floating, rolling, and pressurizing.

[0045] Next, an example of the manufacturing process when glass 10 is used in FOWLP manufacturing will be described. In FOWLP manufacturing, multiple semiconductor wafers are bonded to glass 10, and the semiconductor wafers are covered with a sealing material to form a device substrate. Then, glass 10 is separated from the device substrate, and the side of the device substrate opposite to the semiconductor wafer is bonded to another glass 10, for example. Then, wiring or solder bumps are formed on the semiconductor wafer, and the device substrate is separated from glass 10 again. Then, the device substrate is cut for each semiconductor wafer to achieve monolithic assembly, thereby obtaining a semiconductor device.

[0046] As explained above, the glass 10 of this embodiment, expressed in moles (%) based on oxides, contains SiO2: 35%~60%, B2O3: 0.8%~8%, Al2O3: 6%~21%, MgO: 17%~44%, and (MgO / Al2O3) ≥ 1. The measured Madelung constant m calculated by formula (1A) is 1.05 or more, and the ratio of the measured value α (ppm / K) of the linear thermal expansion coefficient to the calculated value αcal (ppm / K) of the linear thermal expansion coefficient calculated based on the composition, i.e., the coefficient of thermal expansion, is 0.7 or less.

[0047] In the glass 10 of this embodiment, the contents of SiO2, B2O3, Al2O3, and MgO are within the specified range, with a higher content of MgO than Al2O3. The Madelung constant m is measured to be 1.05 or higher, and the coefficient of thermal expansion is 0.7 or lower. This increases the Young's modulus and decreases the coefficient of linear thermal expansion. Due to the higher Young's modulus, deflection can be suppressed, and due to the lower coefficient of linear thermal expansion, deflection at high temperatures can also be suppressed. Therefore, the glass 10 of this embodiment can appropriately suppress deflection.

[0048] When the thermal expansion parameter αpi of the oxide is set to the value calculated by equation (2A), the calculated value of the linear thermal expansion coefficient αcal1 of the glass containing only the monovalent element modified oxide component contained in glass 10 is set to the value calculated by equation (2B), the calculated value of the linear thermal expansion coefficient αcal2 of the glass containing only the divalent element modified oxide component contained in glass 10 is set to the value calculated by equation (2C), and the calculated value of the linear thermal expansion coefficient αcal3 of the glass containing only the trivalent element modified oxide component contained in glass 10 is set to the value calculated by equation (2D), the calculated value αcal is calculated by equation (2E). By ensuring that the ratio of the measured value α to the calculated value αcal, i.e., the thermal expansion coefficient, is within the above-mentioned numerical range, the linear thermal expansion coefficient can be reduced, thereby appropriately suppressing deflection.

[0049] The Madelung constant m is preferably between 1.05 and 1.35. By keeping the Madelung constant m within this range, the Young's modulus can be increased, thereby appropriately suppressing deflection.

[0050] The coefficient of thermal expansion is preferably between 0.45 and 0.7. By keeping the coefficient of thermal expansion within this range, the linear coefficient of thermal expansion can be reduced, thereby appropriately suppressing deflection.

[0051] Glass 10 preferably contains, in moles (%) based on oxides, CaO: 0%~8%, TiO2: 0%~8%, ZrO2: 0%~8%, Na2O3: 0%~7%, and K2O: 0%~6%. This composition appropriately suppresses flexural deformation.

[0052] Glass 10 preferably contains, in moles (%) based on oxides, SiO 2: 35%~52%, Al 2O 3: 9.6%~20%, MgO: 24%~44%, B 2O 3: 0.8%~4.5%, and TiO 2: 0.3%~5%. With this composition, for example, even without a slow cooling process, the Madelung constant m or the coefficient of thermal expansion can be measured within the aforementioned range, thus appropriately suppressing deflection.

[0053] Furthermore, glass 10 is preferably a non-sintered glass. Since glass 10 is not a sintered body, its density can be prevented from becoming too high, thus achieving lightweighting. Also, since it does not scatter light due to the pores present in sintered bodies, light transmittance can be ensured.

[0054] Furthermore, glass 10 is preferably amorphous glass. Because glass 10 is amorphous glass, it is possible to prevent the density from becoming too high and thus achieve lightweighting.

[0055] The glass 10 is preferably a support glass substrate for manufacturing fan-out wafer-level packaging (FOWLP) or, in other words, a fan-out panel-level packaging (FLP) substrate. By using the glass 10 for manufacturing at least one of fan-out wafer-level packaging and fan-out panel-level packaging, semiconductor packaging can be suitably manufactured.

[0056] The manufacturing method of glass 10 in this embodiment includes the following steps: forming glass containing, in mole percent based on oxides, SiO2: 35%~60%, B2O3: 0.8%~8%, Al2O3: 6%~21%, and MgO: 17%~44%; holding the formed glass at a temperature 0°C to 100°C above the glass transition point Tg for more than 0 hours and less than 10 hours; and cooling the glass at a temperature decreasing rate of 0.5°C / min to 100°C / min. According to this manufacturing method, the Madelung constant m can be set to 1.05 or higher and the coefficient of thermal expansion can be set to 0.7 or lower, thereby suppressing the deflection of the manufactured glass 10. Furthermore, the method for achieving the Madelung constant m of 1.05 or higher and the coefficient of thermal expansion of 0.7 or lower is not limited to implementing this manufacturing method. For example, by studying the composition as described above, even without a slow cooling process, the Madelung constant m can be set to 1.05 or higher and the coefficient of thermal expansion of 0.7 or lower.

[0057] (Example) Next, the embodiments will be described. Furthermore, variations in the embodiments are possible as long as the effects of the invention are achieved. In the embodiments, during the forming process, a raw plate with a diameter of 320 mm and a thickness of 6 mm is manufactured using a melt casting method. Then, a plurality of plates with a diameter of 300 mm and a thickness of 3 mm are cut from the center of the raw plate. Cerium oxide is used as an abrasive material, and both sides of these plates are ground to obtain glass. Furthermore, the composition of the glass in each example differs, as does the presence or absence of a slow cooling process after the forming process. In the slow cooling process, the formed raw plate is held at a temperature 30°C higher than the glass transition point for 1 hour, and then cooled at a cooling rate of 1°C / min. For samples that do not undergo a slow cooling process, the formed raw plate is cooled at a cooling rate of 100°C / min.

[0058] For each example of glass, the density was determined by Archimedes' method, the Young's modulus was determined using the 38DL PLUS manufactured by OLYMPUS, the calculated value of the linear thermal expansion coefficient α cal was calculated, the measured value of the linear thermal expansion coefficient α was measured, the thermal expansion factor was calculated, and the Madelung constant m was determined.

[0059] Tables 1 to 3 show the glass composition for each example. Figure 2 shows the coefficient of thermal expansion and the determination of the Madelung constant for each example.

[0060] [Table 1] (Table 1) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 composition (mol%) SiO2 45.7 47.9 47.5 51.9 57.0 57.0 57.0 52.4 44.0 36.0 37.0 38.0 35.0 52.0 52.0 52.0 52.0 52.0 52.0 52.0 Al 2O 3 13.9 12.1 11.0 13.9 18.5 18.5 18.5 13.4 13.0 10.0 10.0 10.0 11.0 18.0 18.0 18.0 18.0 18.0 18.0 18.0 B 2O 3 4.5 4.5 3.0 2.0 2.0 2.0 2.0 5.0 7.2 0.8 0.8 0.8 0.8 1.0 1.0 1.0 1.0 1.0 1.0 1.0 MgO 34.4 34.0 32.5 28.2 19.5 20.0 19.5 28.7 35.0 44.0 43.0 42.0 44.0 24.0 26.0 26.0 26.0 26.0 26.0 26.0 CaO 1.0 2.3 1.0 8.0 8.0 8.0 80 ZrO2 2.0 0.5 1.0 1.8 0.3 0.5 0.9 0.9 0.9 0.9 TiO2 1.5 1.5 5.0 2.0 0.3 1.5 0.3 0.3 03 0.3 0.3 0.3 0.3 3.0 3.0 2.5 2.0 1.5 2.5 2.0 Na2O 1.5 0.5 0.5 K 2O 0.5 0.5 1.0 1.5 0.5 Slow cooling process have have have have have have have have have have have have have have have have have have have have Density (g / cm³) 2.673 2.653 2.708 2.699 2.592 2.614 2.622 2.588 2.665 2.893 2.882 2.871 2.901 2.718 2.724 2.712 2.700 2.688 2.708 2.696 Young's modulus (GPa) 107.8 103.5 106.9 105.6 100.7 101.7 102.0 99.5 106.4 112.1 111.6 111.1 113.0 106.1 106.7 106.7 106.3 105.4 107.2 106.9 Calculated value of thermal expansion coefficient α cal (ppm / K) 6.8 6.7 6.7 6.3 5.9 5.7 5.8 6.3 6.8 8.5 8.4 8.3 8.5 6.5 6.2 6.3 6.5 6.7 6.3 6.5 Measured value of thermal expansion coefficient α (ppm / K) 3.6 4.3 4.5 3.9 3.4 3.2 3.3 3.8 4.1 5.6 5.6 5.5 5.6 3.6 3.5 3.5 3.7 4.0 3.5 3.7 thermal expansion factor 0.527 0.644 0.676 0.627 0.572 0.559 0.566 0.608 0.598 0.662 0.659 0.656 0.654 0.552 0.561 0.554 0.569 0.601 0.561 0.572 Determination of Madelung constant m 1.10 1.07 1.10 1.10 1.07 1.07 1.07 1.06 1.08 1.13 1.13 1.13 1.13 1.08 1.07 1.08 1.08 1.08 1.08 1.09 Evaluation results A A A A A A A A A A A A A A A A A A A A [Table 2] (Table 2) Example 21 Example 22 Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 Example 29 Example 30 Example 31 Example 32 Example 33 Example 34 composition (mol%) SiO 2 52.0 52.0 52.0 52.0 52.0 52.0 52.0 52.0 52.0 52.0 47.0 46.1 47.0 47.5 Al₂O₃ 20.0 20.0 20.0 20.0 20.0 16.0 12.0 16.0 16.0 16.0 9.8 9.6 9.8 11.0 B 2O 3 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 3.0 MgO 24.0 24.0 24.0 24.0 24.0 28.0 28.0 26.0 26.0 26.0 37.2 34.6 35.3 32.5 CaO 2.0 2.0 1.0 ZrO 2 2.0 2.0 TiO 2 2.5 2.0 2.5 2.0 3.0 1.5 4.0 3.0 2.5 2.0 2.0 1.0 1.0 5.0 Na₂O 0.5 0.5 1.0 1.5 1.5 0.5 0.5 0.5 1.0 3.8 2.0 K 2O 0.5 0.5 1.5 1.5 2.0 2.5 2.0 Slow cooling process have have have have have have have have have have have have have none Density (g / cm³) 2.700 2.688 2.704 2.684 2.716 2.683 2.645 2.735 2.723 2.711 2.783 2.778 2.780 2.708 Young's modulus (GPa) 108.1 108.0 107.6 108.5 107.4 106.4 96.6 103.8 103.2 102.4 107.9 104.6 102.4 103.8 Calculated value of thermal expansion coefficient α cal (ppm / K) 6.2 6.3 6.2 6.3 6.1 6.7 7.3 6.8 7.0 7.2 7.6 8.4 8.4 6.7 Measured value of thermal expansion coefficient α cal (ppm / K) 3.4 3.6 3.4 3.6 3.4 4.2 4.2 3.7 3.9 4.2 4.4 5.1 5.4 4.5 thermal expansion factor 0.558 0.566 0.551 0.572 0.560 0.620 0.580 0.546 0.556 0.585 0.576 0.610 0.637 0.676 Determination of Madelung constant m 1.09 1.09 1.08 1.10 1.07 1.11 1.05 1.06 1.07 1.07 1.12 1.12 1.09 1.07 Evaluation results A A A A A A A A A A A A A A [Table 3] (Table 3) Example 35 Example 36 Example 37 Example 38 Example 39 Example 40 Example 41 Example 42 Example 43 Example 44 Example 45 Example 46 Example 47 Example 48 Example 49 Example 50 Example 51 Example 52 Composition (mol%) SiO 2 71.8 71.7 69.1 67.1 68.9 68.0 66.2 64.3 66.5 55.6 55.5 42.1 51.5 55.5 40.0 57.0 50.6 56.6 Al 2O 3 14.2 14.3 5.1 5.0 5.0 5.0 10.9 8.4 11.5 22.2 14.7 15.4 10.3 14.7 10.0 12.0 20.7 15.1 B 2O 3 12.4 12.0 7.8 12.2 9.3 0.5 6.9 MgO 1.1 1.3 3.3 4.8 22.2 19.6 23.0 18.4 19.6 23.9 18.0 20.7 18.0 CaO 3.8 3.6 3.6 3.6 9.5 2.4 SrO 2.8 BaO 0.6 0.5 Li 2O 9.2 8.1 12.1 ZrO2 1.2 1.2 2.4 1.0 5.6 TiO2 1.6 1.6 3.8 Na2O 0.5 0.4 9.0 11.6 13.9 10.4 15.5 15.2 5.2 10.3 10.0 5.2 12.0 K 2O 0.2 0.2 3.9 1.4 5.0 9.1 9.8 5.0 Y2O3 2.4 10.3 Gd2O3 P₂O₅ 0.6 0.6 3.4 ZnO 0.7 0.7 0.7 0.8 Slow cooling process none none none none none none none none none none none none none none none none none none Density (g / cm³) 2.430 2.430 2.390 2.430 2.470 2.410 2.460 2.540 2.450 2.628 2.540 2.580 2.530 2.540 2.590 2.540 2.890 3.100 Young's modulus (GPa) 80.0 85.0 71.0 74.0 75.0 75.0 75.0 75.0 71.0 101.5 84.3 82.3 75.4 84.3 96.0 82.0 102.0 113.0 Calculated value of thermal expansion coefficient α cal (ppm / K) 4.4 4.2 5.3 6.3 7.5 5.9 5.0 10.5 8.9 6.0 9.0 13.1 12.9 9.0 8.8 9.1 6.0 6.1 Measured value of thermal expansion coefficient α cal (ppm / K) 4.1 3.7 5.9 6.8 7.7 6.4 3.8 10.2 9.1 3.6 6.9 10.1 10.7 6.9 8.0 7.5 5.5 6.8 thermal expansion factor 0.924 0.874 1.118 1.071 1.033 1.093 0.766 0.968 1.022 0.595 0.766 0.775 0.830 0.766 0.914 0.823 0.915 1.123 Determination of Madelung constant m 0.96 1.02 0.94 0.98 1.02 1.00 0.92 1.05 0.96 1.04 1.01 1.03 1.01 1.01 1.02 1.02 1.02 1.21 Evaluation results B B B B B B B B B B B B B B B B B B

[0061] For each example of glass, a flexural evaluation was performed. Those that passed the flexural evaluation were designated A, and those that failed were designated B. As for the glass used in Examples 1 to 34, since the hypothetical Madelung constant m is 1.05 or higher and the coefficient of thermal expansion is 0.7 or lower, these glasses were evaluated as A, indicating that flexural deformation can be suppressed. As for the glass used in Comparative Examples 35 to 52, since they did not meet at least one of the conditions of a hypothetical Madelung constant m being 1.05 or higher and a coefficient of thermal expansion being 0.7 or lower, these glasses were evaluated as B, indicating that flexural deformation could not be suppressed.

[0062] The flexure evaluation is performed based on the Bi-Metal warp calculation defined in S. Timoshenko, J. Opt. Soc. Am. 11(1925)233. Figure 3 is a schematic diagram illustrating the flexure evaluation. Here, regarding the warp amount δ, as shown in Figure 3, after molding the semiconductor substrate with resin, the semiconductor substrate is attached to the first surface 12 side of the glass 10 processed into the shape of Figure 1. During the above process, when cooling from a high temperature of 200°C to a low temperature of 20°C, D / 2 (half the thickness D) is taken as the height reference from the center of the second surface 14. The warp amount δ is defined as the displacement of the end of the glass 10 in any direction in the vertical up and down direction. Specifically, the warp amount δ is calculated by the following formula (3).

[0063] [Number 1]

[0064] Here, as shown in Figure 3, L is the length of the glass 10 in the warp direction (the horizontal direction in Figure 3), α1 is the linear thermal expansion coefficient of the resin substrate 20, α2 is the linear thermal expansion coefficient of the glass 10, T2 is the temperature after cooling (20℃ here), and T1 is the temperature before cooling (200℃ here). Also, m is a1 / a2, h is a1+a2, and n is E1 / E2. Here, a1 is the thickness of the resin substrate 20, a2 is the thickness of the glass 10, E1 is the Young's modulus of the resin substrate 20, and E2 is the Young's modulus of the glass 10.

[0065] The flexural evaluation assumes a high-density semiconductor encapsulation on a resin substrate 20 bonded to glass 10, with a thickness of 0.3 mm, a Young's modulus of 31.5 GPa, and a coefficient of linear thermal expansion of 2.38 ppm / K. Alternatively, the glass 10 thickness is set to 0.5 mm, the Young's modulus to 95 GPa, and the coefficient of linear thermal expansion to 10 ppm / K for calculation and evaluation. L is set to 300 mm.

[0066] As a criterion for flexural evaluation, the following condition is defined as Evaluation A: the standardized warpage δ / δstd obtained using the calculated warpage δstd when both the Madelung constant m and the coefficient of thermal expansion are 1 is 0.600 or less, and the warpage reduction rate (warpage reduction / change in coefficient of thermal expansion) when changing the coefficient of thermal expansion relative to a certain calculated Madelung constant does not reach 1.300. On the other hand, the condition that does not meet at least one of these criteria is defined as Evaluation B. By using glass that meets the criteria of Evaluation A to fabricate semiconductor substrates, warpage is effectively reduced, and high-density packaging with good precision can be achieved.

[0067] While embodiments of the present invention have been described above, the embodiments are not limited to these embodiments. Furthermore, the aforementioned constituent elements include constituent elements readily conceived by those skilled in the art, substantially identical constituent elements, and constituent elements within a so-called equal range. Moreover, the aforementioned constituent elements can be appropriately combined. Furthermore, various omissions, substitutions, or modifications of the constituent elements can be made without departing from the spirit of the aforementioned embodiments.

[0068] 10: Glass 12: First surface 14: Surface 2 20: Resin substrate α: Measured value a 1: Thickness a 2: Thickness α cal: Calculated value D: Thickness L: Length m: Determination of Madelung constant T1: Temperature before cooling T2: Temperature after cooling δ: Warpage

Claims

1. A glass, expressed in moles (%) based on oxides, contains: SiO2: 35%–52%, B2O3: 0.8%–4.5%, Al2O3: 9.6%–20%, MgO: 24%–44%, TiO2: 0.3%–5%, and (MgO / Al2O3) ≥ 1, wherein the measured Madelung constant m calculated by formula (1A) is 1.05 or more, and the ratio of the measured value of the linear thermal expansion coefficient α (ppm / K) to the calculated value of the linear thermal expansion coefficient αcal (ppm / K) calculated based on the composition, i.e., the coefficient of thermal expansion, is 0.7 or less; m = E / (2・Vp・Gt)・・・(1A) Here, E is the measured value of the Young's modulus (GPa) of the glass, Vp is the average atomic filling rate of the glass, and Gt is the average bond dissociation energy of the glass.

2. For the glass of claim 1, wherein the thermal expansion parameter αpi of the oxide is set to the value calculated by the following formula (2A), the calculated value of the linear thermal expansion coefficient αcal1 of the glass containing only the monovalent element modified oxide component contained in the above glass is set to the value calculated by the following formula (2B), the calculated value of the linear thermal expansion coefficient αcal2 of the glass containing only the divalent element modified oxide component contained in the above glass is set to the value calculated by the following formula (2C), and the calculated value of the linear thermal expansion coefficient αcal3 of the glass containing only the trivalent element modified oxide component contained in the above glass is set to the value calculated by the following formula (2D), the calculated value αcal is calculated by the following formula (2E): αpi={ni / (ni-1)}・(Z+i・Zi / reqi)-1・・・(2A) αcal1=(290・αp-89.6) / 10・・・(2B) αcal2=(300・αp-49.1) / 10・・・(2C) αcal3=(848・αp-234) / 10・・・(2D) αcal=(M1・αcal1+M2・αcal2+M3・αcal3) / {10・(M1+M2+M3)}・・・(2E) Here, ni is the Born index, Z+i is the cation charge of the oxide, Zi is the anion charge of the oxide, reqi is the equilibrium value of the average distance between ion pairs of the oxide at temperature 0 (K), αp in equations (2B), (2C), and (2D) is the sum of the values ​​obtained by multiplying equation (2A) by the cation ratio of each oxide, M1 is the cation ratio (%) of the content of the modified oxide of the above monovalent element, M2 is the cation ratio (%) of the content of the modified oxide of the above divalent element, and M3 is the cation ratio (%) of the content of the modified oxide of the above trivalent element.

3. For the glass described in request item 1 or 2, the measured Madelung constant m is 1.35 or less.

4. The glass of request item 1 or 2 has a coefficient of thermal expansion of 0.45 or higher.

5. The glass of claim 1 or 2, expressed in moles (%) based on oxides, contains: ZrO2: 0.3% or more.

6. The glass of claim 1 or 2 contains, in moles % based on oxides: CaO: 0%–8%, ZrO2: 0%–8%, Na2O3: 0%–7%, K2O: 0%–6%.

7. The glass in claim 1 or 2 is amorphous glass.

8. The glass of claim 1 or 2 is a support glass substrate for manufacturing at least one of fan-out wafer-level packaging and fan-out panel-level packaging.

9. A method for manufacturing glass, comprising the following steps: forming a glass containing, in moles (%) based on oxides: SiO2: 35%–52%, B2O3: 0.8%–4.5%, Al2O3: 9.6%–20%, MgO: 24%–44%, TiO2: 0.3%–5%; holding the formed glass at a temperature 0°C to 100°C above the glass transition point (Tg) for a time of 0 hours to 10 hours; and cooling the glass at a temperature decreasing rate of 0.5°C / min to 100°C / min.

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