JP6852962B2 - Glass - Google Patents

Description

The present invention relates to glass, and particularly to glass suitable for a chip size package (CSP) substrate.

In recent years, image sensors such as CSP have been made smaller, thinner, and lighter. Conventionally, these sensor portions are protected by a resin package, but in recent years, a method of attaching a glass substrate on a Si chip to protect them has been adopted in order to further reduce the size.

As for this glass substrate, further thinning is required in order to reduce the size of the device, and a thin glass substrate (for example, a glass substrate having a plate thickness of 0.7 mm or less) is being adopted.

Further, in order to prevent the situation where alkaline ions are diffused into the semiconductor film in the heat treatment step, non-alkali glass is usually used for this glass substrate (see Patent Document 1).

Japanese Unexamined Patent Publication No. 2006-344927

As described above, in the case of applications such as CSP, the glass substrate and the Si chip are directly attached. However, if the linear thermal expansion coefficients (CTE) of the glass substrate and Si are inconsistent, the glass substrate will be warped due to the difference in the linear thermal expansion coefficients between the two. In particular, the smaller the thickness of the glass substrate, the more easily the glass substrate is warped.

However, if the coefficient of linear thermal expansion of the glass substrate is lowered so as to match the coefficient of linear thermal expansion of Si, surface defects of the glass substrate are likely to occur. That is, if the glass composition is designed to reduce the coefficient of linear thermal expansion of the glass substrate, the high-temperature viscosity of the molten glass increases and the moldability decreases, so that surface defects such as foaming and devitrification are likely to occur. Become.

In addition, since an image sensor such as a CSP contains information equivalent to several million pixels in a Si chip of about 2 mm, it has a very small defect that cannot be compared with pixels of a liquid crystal display, an organic EL display, or the like. Can be a problem. Further, since the step of bonding the image sensor and the glass substrate is a substantially final step, if the yield of the device is lowered due to the defect of the glass substrate, the productivity of the device is remarkably lowered.

Therefore, the present invention has been made in view of the above circumstances, and is to provide a glass having a linear thermal expansion coefficient consistent with Si and having good meltability and moldability.

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 range and the coefficient of linear thermal expansion, and proposes the present invention. That is, the glass of the present invention has a glass composition of SiO ₂ 65 to 70%, Al ₂ O ₃ 10 to 13%, B ₂ O ₃ 5 to 10%, MgO + CaO + SrO + BaO + ZnO 10 to 13%, P ₂ O. ₅ contains 0-3%, the molar ratio (MgO + CaO + SrO + BaO + ZnO) / Al 2 O 3 is 0.9 to 1.3, the molar ratio CaO / (MgO + CaO + SrO + BaO + ZnO) is 0.4 to 0.8, and 30 the linear thermal expansion coefficient at ~260 _{℃ CTE 30-260} ℃, when the linear thermal expansion coefficient at 30 to 380 ° C. was ^{_{CTE 30-380 ℃, 32 × 10 -7}} / ℃ ≦ CTE 30-260 ℃ ≦ 34 × 10 ^-7 / ° C., the condition of _{^{33 × 10 -7 / ℃ ≦ CTE}} 30-380 ℃ ≦ 35 × 10 -7 /℃,0.95≦CTE 30-380 ℃ / CTE 30-260 ℃ ≦ 1.05 It is characterized by satisfying. Here, "MgO + CaO + SrO + BaO + ZnO" refers to the total amount of MgO, CaO, SrO, BaO and ZnO. "(MgO + CaO + SrO + BaO + ZnO) / Al ₂ O ₃ " refers to a value obtained by dividing the total amount of MgO, CaO, SrO, BaO and ZnO by the content of Al ₂ O _3. "CaO / (MgO + CaO + SrO + BaO + ZnO)" refers to the value obtained by dividing the CaO content by the total amount of MgO, CaO, SrO, BaO and ZnO. The "coefficient of linear thermal expansion at 30 to 260 ° C." refers to a value measured by a dilatometer and refers to an average value in the temperature range of 30 to 260 ° C. The "coefficient of linear thermal expansion at 30 to 380 ° C." refers to a value measured by a dilatometer and refers to an average value in the temperature range of 30 to 380 ° C. "CTE _{30-380 ° C./CTE 30-260 ° C.} " refers to a value obtained by dividing the coefficient of linear thermal expansion at 30 to 380 ° C. by the coefficient of linear thermal expansion at 30 to 260 ° C.

Secondly, the glass of the present invention preferably has a Li ₂ O + Na ₂ O + K ₂ O content of 0.5 mol% or less in the glass composition. Here, "Li ₂ O + Na ₂ O + K ₂ O" refers to the total amount of _{Li 2} O, Na ₂ O and K _{2 O.}

Third, the glass of the present invention preferably has a Young's modulus of 70 GPa or more. Here, "Young's modulus" can be measured by a well-known resonance method.

Fourth, the glass of the present invention preferably has a specific Young's modulus of 30 GPa / (g / cm ³ ) or more. Here, the "specific Young's modulus" refers to a value obtained by dividing the Young's modulus by the density. "Density" refers to a value measured by the well-known Archimedes method.

Fifth, the glass of the present invention is preferably formed by an overflow down draw method or a slot down draw method. In this way, the surface quality of the glass substrate can be improved.

Sixth, the glass of the present invention preferably has a flat plate shape.

Seventh, the glass of the present invention is preferably used in chip size packages.

Eighth, the glass of the present invention is preferably used for organic EL displays. Since the glass of the present invention has excellent heat resistance, it does not easily shrink due to heat in the manufacturing process of p-Si / TFT, and is suitable for this application.

Ninth, the glass of the present invention is preferably used as a cover glass for a display device.

Tenth, the laminate of the present invention is a laminate in which a Si chip is attached on a glass substrate, and the glass substrate is preferably made of the above-mentioned glass. The Si chip and the glass substrate can be attached using a known adhesive.

The reasons for limiting the content of each component in the glass composition in the glass of the present invention as described above are shown below. In addition, the following% display refers to mol% unless otherwise specified.

The content of SiO ₂ is 65 to 70%, preferably 66 to 70%, more preferably 67 to 69.5%, still more preferably 68 to 69%. If _{the content of SiO 2} is small, it becomes difficult to reduce the density of the glass. On the other hand, when _{the content of SiO 2} is high, the high-temperature viscosity becomes high, the meltability decreases, and defects such as devitrified crystals (cristobalite) are likely to occur in the glass.

If _{the content of Al 2} O ₃ is small, it becomes difficult to increase the heat resistance, the high temperature viscosity becomes high, and the meltability tends to decrease. In addition, Young's modulus tends to decrease. Therefore, _{the lower limit range of Al 2} O ₃ is 10% or more, preferably 10.5% or more, more preferably 10.7% or more, and particularly preferably 11% or more. On the other hand, when _{the content of Al 2} O ₃ is large, the liquidus temperature becomes high and the devitrification resistance tends to decrease. Therefore, _{the upper limit range of Al 2} O ₃ is 13% or less, preferably 12.7% or less, and particularly preferably 12.5% or less.

B ₂ O ₃ is a component that acts as a flux, lowers high-temperature viscosity, and enhances meltability, and its content is 5 to 10%. If _{the content of B 2} O ₃ is small, the function as a flux is insufficient and the high-temperature viscosity becomes high. In addition, it becomes difficult to reduce the density of glass. The preferred lower limit range of B ₂ O ₃ is 5.5% or more, 6% or more, 6.5% or more, and particularly 7% or more. On the other hand, when _{the content of B 2} O ₃ is large, the heat resistance and Young's modulus tend to decrease. A suitable upper limit range for B ₂ O ₃ is 9% or less, particularly 8% or less.

MgO, CaO, SrO, BaO and ZnO are components that lower the liquidus temperature to make it difficult for crystalline foreign substances to be generated in the glass, and are components that enhance meltability and moldability. The content of MgO + CaO + SrO + BaO + ZnO is 10 to 13%, preferably 10.5 to 12.5%, more preferably 11 to 12.5%, and particularly preferably 11.5-12.5%. If the content of MgO + CaO + SrO + BaO + ZnO is small, the function as a flux cannot be sufficiently exerted, the meltability is lowered, and the coefficient of linear thermal expansion becomes too low, so that it is difficult to match with the coefficient of linear thermal expansion of Si. Become. On the other hand, when the content of MgO + CaO + SrO + BaO + ZnO is large, the density increases, it becomes difficult to reduce the weight of the glass, the Young's modulus tends to decrease, and the coefficient of linear thermal expansion becomes too high. The content of MgO is preferably 0 to 10%, more preferably 0.1 to 7%, and particularly preferably 0.5 to 4%. The CaO content is preferably 0-12%, more preferably 4-10%, and particularly preferably 5-9%. The content of SrO is preferably 0 to 6%, more preferably 0.1 to 4%, and particularly preferably more than 1 to 3%. The content of BaO is preferably 0 to 6%, more preferably 0.1 to 4%, and particularly preferably more than 1 to 3%. The ZnO content is preferably 0 to 3%, more preferably 0 to 1%, and particularly preferably 0 to 0.2%.

Molar ratio (MgO + CaO + SrO + BaO + ZnO) / Al 2 O 3 molar ratio CaO / (MgO + CaO + SrO + BaO + ZnO) _{regulates CTE 30-380 ℃} / _{CTE 30-260 ℃,} the _{CTE 30-260 ℃} and _{CTE 30-380 ℃} the desired range It is an important component ratio for this. The molar ratio (MgO + CaO + SrO + BaO + ZnO) / Al ₂ O ₃ is 0.9 to 1.3, preferably 0.95 to 1.2, more preferably more than 1.00 to 1.15, and particularly preferably 1.02 to 1.02. It is 1.12. The molar ratio CaO / (MgO + CaO + SrO + BaO + ZnO) is 0.4 to 0.8, preferably 0.44 to 0.76, more preferably 0.6 to 0.75, and particularly preferably 0.65 to 0.73. is there. When the molar ratio (MgO + CaO + SrO + BaO + ZnO) / Al ₂ O ₃ and the molar ratio CaO / (MgO + CaO + SrO + BaO + ZnO) are out of the above range, CTE _{30-380 ° C} / CTE _{30-260 ° C} , CTE _{30-260 ° C} and CTE _{30-380 ° C} are desired. It becomes difficult to regulate within the range of.

P ₂ O ₅ is a component that enhances devitrification resistance, but if it is contained in a large amount in the glass composition, phase separation and opalescence occur in the glass, and water resistance is remarkably lowered. Therefore, _{the content of P 2} O ₅ is preferably 0 to 3%, more preferably 0 to 2%, and particularly preferably 0.1 to 0.9%.

SnO ₂ is a component having a good clarification effect in a high temperature range and a component that lowers high temperature viscosity. The content of SnO ₂ is preferably 0 to 1%, more preferably 0.001 to 1%, still more preferably 0.01 to 0.5%, and particularly preferably 0.05 to 0.2%. When the content of _{SnO 2 is high, devitrified crystals of SnO 2} are likely to be precipitated in the glass. If the SnO ₂ content is less than 0.001%, it becomes difficult to enjoy the above effects.

ZrO ₂ is a component that enhances Young's modulus. The content of ZrO ₂ is preferably 10 to 2000 ppm (mass), more preferably 20 to 1000 ppm (mass), and particularly preferably 50 to 500 ppm (mass). When _{the content of ZrO 2} is large, the liquidus temperature rises, and devitrified crystals of zircon are likely to precipitate.

TiO ₂ is a component that lowers high-temperature viscosity and enhances meltability, and is a component that suppresses solarization. However, if it is contained in a large amount in the glass composition, the glass is colored and the transmittance tends to decrease. Therefore, _{the content of TiO 2} is preferably 10 to 2000 ppm (mass), more preferably 30 to 1000 ppm (mass), and particularly preferably 50 to 300 ppm (mass).

Li ₂ O, Na ₂ O and K ₂ O are components that deteriorate the semiconductor film in the heat treatment process. The content of Li ₂ O + Na ₂ O + K ₂ O is preferably 0 to 1%, more preferably 0 to 0.5%, and particularly preferably 0.01 to 0.2%. The content of Li ₂ O is preferably 0 to 100 ppm (mass), more preferably 1 to 50 ppm (mass), and particularly preferably 5 to 20 ppm (mass). The content of Na ₂ O is preferably 10 to 500 ppm (mass), more preferably 50 to 300 ppm (mass), and particularly preferably 100 to 200 ppm (mass). The K ₂ O content is preferably 0 to 100 ppm (mass), more preferably 5 to 50 ppm (by weight), particularly preferably 10 to 30 ppm (by weight). When _{the contents of Li 2} O, Na ₂ O and K ₂ O are made too small, a high-purity raw material must be used, and the raw material cost tends to rise.

Fe ₂ O ₃ is a component that colors glass. The content of Fe ₂ O ₃ is preferably 10 to 500 ppm (mass), more preferably 30 to 200 ppm (mass), and particularly preferably 50 to 100 ppm (mass). If _{the content of Fe 2} O ₃ is too small, a high-purity raw material must be used, and the cost of the raw material tends to rise.

Cr ₂ O ₃ is a component that colors glass. The content of Cr ₂ O ₃ is preferably 0 to 5 ppm (mass), more preferably 0.01 to 2 ppm (mass), and particularly preferably 0.05 to 3 ppm (mass). If _{the content of Cr 2} O ₃ is too small, a high-purity raw material must be used, and the raw material cost tends to rise.

Rh ₂ O ₃ is a component that causes Rh lumps. The content of Rh ₂ O ₃ is preferably 0 to 5 ppm (mass), more preferably 0.01 to 2 ppm (mass), and particularly preferably 0.05 to 3 ppm (mass). When _{the content of Rh 2} O ₃ is too small, it becomes difficult to use a Pt-Rh container for the clarification container, the supply container, etc., but in this case, it becomes difficult to secure the strength of the clarification container, the supply container, etc. ..

SO ₃ is a component that generates riboyl bubbles. The content of SO ₃ is preferably 0 to 100 ppm (mass), more preferably 0.1 to 10 ppm (mass), and particularly preferably 0.5 to 5 ppm (mass). If the SO ₃ content is too low, a high-purity raw material must be used, and the raw material cost tends to rise.

The glass of the present invention, as described above, although the addition of SnO ₂ as a fining agent is preferred, so long as the glass properties are not impaired, in place of the SnO _2, or in combination with SnO _{2, CeO} 2, C, Metal powder (eg Al, Si, etc.) can be added up to 1%.

As ₂ O ₃ and Sb ₂ O ₃ also act effectively as fining agents, and the glass of the present invention does not completely eliminate the content of these components, but from an environmental point of view, the content of these components Is less than 0.1%, particularly preferably less than 0.05%, respectively. Further, halogens such as F and Cl have the effect of lowering the melting temperature and promoting the action of the fining agent. As a result, the melting cost of the glass is reduced and the life of the glass manufacturing kiln is extended. be able to. However, if the contents of F and Cl are too large, the metal wiring pattern formed on the glass substrate may be corroded in applications such as CSP. Therefore, the contents of F and Cl are preferably 1% or less, 0.5% or less, less than 0.1%, less than 0.05%, and particularly preferably 0.01% or less, respectively.

The glass of the present invention preferably has the following characteristics.

Less density 2.50 g / cm ^3, less than 2.49 g / cm ^3, especially less than 2.48 g / cm ³ are preferred. When the density is high, it becomes difficult to reduce the weight of the glass, and the glass substrate tends to bend due to its own weight.

CTE _{30-260 ° C.} is 32 × 10 ^{-7 to} 34 × 10 ^-7 / ° C., preferably 32.5 × 10 ^{-7 to} 33.5 × 10 ^-7 / ° C. When CTE _{30-260 ° C.} is out of the above range, the amount of warpage of the glass substrate tends to increase when the glass substrate and the Si chip are bonded to each other. In particular, the smaller the thickness of the glass substrate, the larger the amount of warpage of the glass substrate tends to be.

CTE _{30-380 ° C.} is 33 × 10 ^{-7 to} 35 × 10 ^-7 / ° C., preferably 33.5 × 10 ^{-7 to} 34.5 × 10 ^-7 / ° C. When CTE _{30-380 ° C.} is out of the above range, the amount of warpage of the glass substrate tends to increase when the glass substrate and the Si chip are bonded together. In particular, the smaller the thickness of the glass substrate, the larger the amount of warpage of the glass substrate tends to be.

CTE _{30-380 ° C./CTE 30-260 ° C.} is 0.95 to 1.05, preferably 1.001 to 1.050, more preferably 1.020 to 1.045, and particularly preferably 1.025 to 1.025. It is 1.040. When CTE _{30-380 ° C./CTE 30-260 ° C.} is out of the above range, the amount of warpage of the glass substrate tends to increase when the glass substrate and the Si chip are bonded together. In particular, the smaller the thickness of the glass substrate, the larger the amount of warpage of the glass substrate tends to be.

Young's modulus is preferably 70 GPa or more, more preferably 73 GPa or more, and particularly preferably 75 GPa or more. The specific modulus is preferably 30GPa / (g / cm ³⁾ or more, particularly preferably 31GPa / (g / cm ³⁾ or more. If the Young's modulus or the specific Young's modulus is low, the rigidity of the obtained laminate tends to decrease after the Si chip is attached on the glass substrate. Further, when the adhesive is spin-coated on the glass substrate, the glass substrate tends to be misaligned.

The strain point is preferably 600 ° C. or higher, 620 ° C. or higher, 630 ° C. or higher, 640 ° C. or higher, 650 ° C. or higher, particularly 660 ° C. or higher. If the strain point is low, the glass quality may be impaired when the glass substrate and the Si chip are bonded with a resin. In addition, the glass tends to shrink due to heat in the heat treatment process. Here, the "distortion point" refers to a value measured based on the method of ASTM C336.

High temperature melting increases the burden on the glass melting kiln. For example, refractories such as alumina and zirconia used in glass melting kilns are more violently eroded by molten glass as the temperature rises. When the amount of erosion of this refractory increases, the life cycle of the glass melting kiln becomes short, and as a result, the manufacturing cost of glass rises. Further, when high-temperature melting is performed, it is necessary to use a component having high heat resistance as a component of the glass melting kiln, so that the component of the glass melting kiln becomes expensive, and as a result, the melting cost of glass rises. .. Further, in high temperature melting, it is necessary to keep the inside of the glass melting kiln at a high temperature, so that the running cost is higher than that in low temperature melting. Therefore, the temperature at a high temperature viscosity of 10 ^2.5 dPa · s is preferably 1650 ° C. or lower, 1640 ° C. or lower, 1630 ° C. or lower, 1620 ° C. or lower, and particularly preferably 1610 ° C. or lower. If the temperature at high temperature viscosity 10 ^2.5 dPa · s is too high, low temperature melting becomes difficult, so that the manufacturing cost of glass tends to rise. In addition, the foam quality tends to deteriorate. Here, "temperature at high temperature viscosity 10 ^2.5 dPa · s" refers to a value measured by the platinum ball pulling method.

The liquidus viscosity is 10 ^4.5 dPa · s or more, 10 ^4.7 dPa · s or more, 10 ^4.9 dPa · s or more, 10 ^5.0 dPa · s or more, especially 10 ^5.2 dPa · s or more. preferable. In this way, devitrification crystals are less likely to occur during molding, so that it becomes easier to mold the glass substrate by the overflow downdraw method or the like. The liquidus viscosity is an index of moldability, and the liquidus viscosity is The higher the value, the better the moldability. Here, the "liquid phase viscosity" refers to a value obtained by measuring the viscosity of glass at the liquid phase temperature by the platinum ball pulling method. The "liquid phase temperature" is the temperature at which crystals precipitate by passing the standard sieve 30 mesh (500 μm) and putting the glass powder remaining in 50 mesh (300 μm) into a platinum boat and holding it in a temperature gradient furnace for 24 hours. Refers to the measured value.

By lowering the β-OH value, the strain point and foam quality can be increased without changing the glass composition. The β-OH value is preferably less than 0.40 / mm, 0.35 / mm or less, 0.3 / mm or less, 0.25 / mm or less, 0.2 / mm or less, and particularly 0.15 / mm or less. Is. If the β-OH value is too large, the strain point and foam quality tend to deteriorate. If the β-OH value is too small, the meltability tends to decrease. Therefore, the β-OH value is preferably 0.01 / mm or more, particularly 0.05 / mm or more. The "β-OH value" refers to a value calculated by the following formula 1 by measuring the transmittance using FT-IR.

There are the following methods as a method for lowering the β-OH value. (1) Select a raw material with a low water content. (2) Add a desiccant such as _{Cl or SO 3} to the glass batch. (3) Reduce the amount of water in the atmosphere inside the furnace. (4) performing the _{N 2} bubbling in the molten glass. (5) Use a small melting furnace. (6) Increase the flow rate of the molten glass. (7) Energization heating is performed by the heating electrode.

Among them, in order to reduce the β-OH value, it is effective to melt the prepared glass batch by heating it with electricity using a heating electrode without heating it with the combustion flame of a burner.

In the glass of the present invention, a glass raw material prepared so as to have a predetermined glass composition is put into a continuous glass melting kiln, the glass raw material is heated and melted, the obtained molten glass is clarified, and then supplied to a molding apparatus. It can be produced by molding it into a flat plate shape or the like.

The glass of the present invention is preferably formed by an overflow down draw method. By doing so, it is possible to obtain a glass substrate that is unpolished and has good surface quality. Here, in the overflow down draw method, the molten glass is overflowed from both sides of the heat-resistant gutter-shaped structure, and the overflowed molten glass is stretched downward while being merged at the lower end of the gutter-shaped structure to form a glass substrate. It is a method of molding. In the case of the overflow down draw method, the surface to be the surface of the glass substrate does not come into contact with the gutter-shaped refractory and is formed in a free surface state, so that the surface quality of the glass substrate can be improved. Since the glass of the present invention has excellent devitrification resistance, a glass substrate can be efficiently molded by an overflow downdraw method.

For the glass of the present invention, various molding methods other than the overflow down draw method can be adopted. For example, a molding method such as a slot down draw method, a float method, or a rollout method can be adopted. If the slot down draw method is used, a thin glass substrate can be efficiently formed.

The glass of the present invention preferably has a flat plate shape, that is, a glass substrate. In this way, it can be applied to a glass substrate for a flat display such as a CSP, a liquid crystal display, and an organic EL display, and a glass substrate for an image sensor such as a CCD or CIS. The thickness of the glass substrate is preferably 0.7 mm or less, 0.6 mm or less, 0.5 mm or less, and particularly preferably 0.4 mm or less. The smaller the plate thickness, the lighter the glass substrate can be, and as a result, the lighter the device becomes. Since the glass of the present invention has a high liquidus viscosity, it is easy to increase the size and thickness by the overflow downdraw method or the like, and it is easy to improve the surface quality.

Hereinafter, the present invention will be described in detail based on Examples. However, the following examples are merely examples. The present invention is not limited to the following examples.

Table 1 shows Examples (Sample Nos. 1 to 8) and Comparative Examples (Sample No. 9) of the present invention. RO in the table represents MgO + CaO + SrO + BaO + ZnO.

As follows, the sample No. 1 to 9 were prepared. First, a glass raw material prepared so as to have the glass composition shown in the table was placed in a platinum crucible, melted at 1600 ° C. for 24 hours, and then poured onto a carbon plate to form a flat plate. Next, for each of the obtained samples, the density, the coefficient of linear thermal expansion at 30 to 380 ° C. CTE _{30-380 ° C.} , the coefficient of linear thermal expansion at _{30 to 260 ° C.} , CTE _{30-260 ° C., CTE 30-380 ° C./CTE 30} The temperature and β-OH value at _{-260 ° C.} , Young's modulus, Young's modulus, strain point, and high temperature viscosity of 10 ^{2.5 dPa · s were evaluated.}

Density is a value measured by the well-known Archimedes method.

The coefficient of linear thermal expansion CTE _{30-260 ° C.} at 30 to 260 ° C. and the coefficient of linear thermal expansion CTE 30-380 ° C. at 30 to 380 ° _C. are average values measured by a dilatometer in the indicated temperature range.

The strain point Ps is a value measured based on the method of ASTM C336.

Young's modulus is a value measured by the resonance method.

The temperature at a high temperature viscosity of 10 ^2.5 dPa · s is a value measured by the platinum ball pulling method.

The β-OH value is a value measured by the above method.

As is clear from Table 1, the sample No. 1 to 8 have a density of 2.39 to 2.48 g / cm ³ , a linear thermal expansion coefficient of CTE _{30-260 ° C at 30} to 260 ° C is 32.2 × ^{10-7 to} 33.9 × ^10-7 / ° C. , CTE 30-380 ° C, linear thermal expansion coefficient CTE _{30-380 ° C} is 33.4 × ^{10-7 to} 35.2 × ^10-7 / ° C, CTE _{30-380 ° C} / CTE _{30-260 ° C} is 1.03 to 1.04, Young's modulus of 72 to 77 GPa, Young's modulus of 30 to 31 GPa / (g / cm ³ ), strain point of 663 to 705 ° C., high temperature viscosity of 10 ^2.5 dPa · s, temperature of 1567 to 1602 ° C. , The β-OH value was 0.15 to 0.30 / mm.

On the other hand, sample No. Since the content of MgO + CaO + SrO + BaO + ZnO is large in No. 9, the coefficient of linear thermal expansion CTE _{30-260 ° C. at 30 to 260 ° C.} is 37.6 × ^10-7 / ° C., and the coefficient of linear thermal expansion CTE _{30-380 ° C. at 30 to 380 ° C.} Was 38.8 × 10 ^-7 / ° C.

In addition to CSP, the glass of the present invention can be used for glass substrates for flat displays such as liquid crystal displays and organic EL displays, and glass substrates for image sensors such as charge-coupled devices (CCD) and 1x proximity solid-state image sensors (CIS). It can be preferably used.

Further, the glass of the present invention can be suitably used for a display device for projection use, for example, a cover glass or spacer of a DMD (Digital Micromirror Device) or LCOS (Liquid Crystal on Silicon). In these devices, an electronic circuit for driving a display or the like is formed on the Si wafer, and a cover glass, a spacer or the like is adhered to the Si wafer by an ultraviolet curable resin, a thermosetting resin, a glass frit or the like. When applied to these applications, it is desirable that the coefficient of linear thermal expansion of the cover glass or the like closely matches the coefficient of thermal expansion of the Si wafer in order to reduce warpage and distortion. The glass of the present invention is suitable for this application because it closely matches the coefficient of thermal expansion of the Si wafer.

Further, the glass of the present invention can be suitably used for a quantum dot silicon type solar cell, a thin film silicon type solar cell substrate or a cover glass. In these devices, a Si film layer is formed on the substrate. When applied to these applications, it is desirable that the coefficient of linear thermal expansion of the glass substrate or the like closely matches the coefficient of thermal expansion of the Si film layer in order to reduce warpage and strain. The glass of the present invention is suitable for this application because it closely matches the coefficient of thermal expansion of the Si film layer. When applied to these applications, it is also required that the spectral transmittance of the glass substrate or the like is very high including the ultraviolet region.

Claims (10)

As the glass composition, in mol%, SiO ₂ 65 to 70%, Al ₂ O ₃ 10 to 13%, B ₂ O ₃ 5.93 to 9%, MgO + CaO + SrO + BaO + ZnO 10 to 12.14%, P ₂ O ₅ 0.1. containing 3%, the molar ratio (MgO + CaO + SrO + BaO + ZnO) / Al 2 O 3 is from 0.95 to 1.3, the molar ratio CaO / (MgO + CaO + SrO + BaO + ZnO) is from 0.44 to 0.8, and from 30 to 260 the linear thermal expansion coefficient at _{℃ CTE 30-260} ℃, when the linear thermal expansion coefficient at 30 to 380 ° C. was ^{_{CTE 30-380 ℃, 32 × 10 -7}} / ℃ ≦ CTE 30-260 ℃ ≦ 34 × 10 - ^{7 / ℃, 33 × 10 -7} / ℃ ≦ CTE 30-380 ℃ ≦ 35 × 10 -7 /℃,0.95≦CTE 30-380 ℃ / CTE 30-260 satisfy conditions of _{° C.} ≦ 1.05 The glass that features. The glass according to claim 1, wherein the content _{of Li 2} O + Na ₂ O + K _{2 O in the glass composition is 0.5 mol% or less.} The glass according to claim 1 or 2, wherein the Young's modulus is 70 GPa or more. The glass according to any one of claims 1 to 3, wherein the Young's modulus is 30 GPa / (g / cm ^{3) or more.} The glass according to any one of claims 1 to 4, wherein the glass is formed by an overflow down draw method or a slot down draw method. The glass according to any one of claims 1 to 5, which has a flat plate shape. The glass according to any one of claims 1 to 6, wherein the glass is used in a chip size package. The glass according to any one of claims 1 to 6, wherein the glass is used for an organic EL display. The glass according to any one of claims 1 to 6, wherein the glass is used as a cover glass of a display device. A laminate in which Si chips are attached on a glass substrate.
A laminate characterized in that the glass substrate is made of the glass according to any one of claims 1 to 7.