Glass substrate, laminated substrate, and production method for glass substrate
The present invention provides a glass substrate in which in a heat treatment step of sticking a silicon substrate and a glass substrate to each other, an alkali ion is hardly diffused into the silicon substrate, and a residual strain generated in the silicon substrate is small. A glass substrate of the present invention has: an average thermal expansion coefficient α 50/100 at 50° C. to 100° C. of 2.70 ppm/° C. to 3.20 ppm/° C.; an average thermal expansion coefficient α 200/300 at 200° C. to 300° C. of 3.45 ppm/° C. to 3.95 ppm/° C.; a value α 200/300 /α 50/100 obtained by dividing the average thermal expansion coefficient α 200/300 at 200° C. to 300° C. by the average thermal expansion coefficient α 50/100 at 50° C. to 100° C. of 1.20 to 1.30; and a content of an alkali metal oxide being 0% to 0.1% as expressed in terms of a molar percentage based on oxides.
1. A glass substrate having:
an average thermal expansion coefficient α 50/100 at 50° C. to 100° C. of 2.70 ppm/° C. to 3.20 ppm/° C.;
an average thermal expansion coefficient α 200/300 at 200° C. to 300° C. of 3.45 ppm/° C. to 3.95 ppm/° C.; and
a value α 200/300 /α 50/100 obtained by dividing the average thermal expansion coefficient α 200/300 at 200° C. to 300° C. by the average thermal expansion coefficient α 50/100 at 50° C. to 100° C. of 1.20 to 1.30,
wherein:
a content of an alkali metal oxide in the glass substrate is 0% to 0.1% as expressed in terms of a molar percentage based on oxides;
a density of the glass substrate is more than 2.46 g/cm 3 ;
the glass substrate comprises a composition containing, as expressed in terms of a molar percentage based on oxides:
SiO 2 : 50% to 70%,
Al 2 O 3 : 12.1% to 16%,
B 2 O 3 : 0% to 15%,
MgO: 0% to 15%,
CaO: 0% to 13%,
SrO: 0% to 11%, and
BaO: 0% to 9.5%; and
satisfy the following condition (1), condition (2), condition (3), and condition (4):
{0.0177×(content of SiO 2 )−0.0173×(content of Al 2 O 3 )+0.0377×(content of B 2 O 3 )+0.0771×(content of MgO)+0.1543×(content of CaO)+0.1808×(content of SrO)+0.2082×(content of BaO)+0.0344×(12.3±log 10 60−log 10 η)} is 2.70 to 3.00, Condition (1):
{0.0181×(content of SiO 2 )+0.0004×(content of Al 2 O)+0.0387×(content of B 2 O 3 )+0.0913×(content of MgO)+0.1621×(content of CaO)+0.1900×(content of SrO)+0.2180×(content of BaO)+0.0391×(12.3+log 10 60−log 10 η)} is 3.13 to 3.43, Condition (2):
{0.0177×(content of SiO 2 )+0.0195×(content of Al 2 O 3 )+0.0323×(content of B 2 O 3 )+0.1015×(content of MgO)+0.1686×(content of CaO)+0.1990×(content of SrO)+0.2179×(content of BaO)+0.0312×(12.3+log 10 60−log 10 η)} is 3.45 to 3.95, and Condition (3):
{0.0111×(content of SiO 2 )+0.0250×(content of Al 2 O 3 )+0.0078×(content of B 2 O 3 )+0.0144×(content of MgO)+0.0053×(content of CaO)+0.0052×(content of SrO)+0.0013×(content of BaO)−0.0041×(12.3+log 10 60−log 10 η)} is 1.20 to 1.30, Condition (4):
in which
the content of SiO 2 , the content of Al 2 O 3 , the content of B 2 O 3 , the content of MgO, the content of CaO, the content of SrO, and the content of BaO are respectively a content of each of the components contained in the glass substrate as expressed in terms of a molar percentage based on the oxides, and
η is a fictive viscosity (unit: dPa·sec).
2. The glass substrate according to claim 1 , wherein the average thermal expansion coefficient α 200/300 at 200° C. to 300° C. is 3.55 ppm/° C. to 3.85 ppm/° C.
3. The glass substrate according to claim 1 , wherein the composition comprises, as expressed in terms of a molar percentage based on the oxides:
SO 2 : 50% to 70%;
Al 2 O 3 : 12.1% to 16%;
B 2 O 3 : 0% to 15%;
MgO: 0% to 15%;
CaO: 0.1% to 13%;
SrO: 0% to 11%; and
BaO: 0% to 9.5%.
4. The glass substrate according to claim 1 , wherein:
a total content of CaO, SrO, and BaO is 7% or more as expressed in terms of a molar percentage based on the oxides;
a relation of {(content of Al 2 O 3 )≥(content of MgO)}; is satisfied; and
a devitrification viscosity of the glass substrate is 10 3.8 dPa·sec or more.
5. The glass substrate according to claim 1 , having an average thermal expansion coefficient α 100/200 at 100° C. to 200° C. of 3.13 ppm/° C. to 3.63 ppm/° C.
6. The glass substrate according to claim 1 , having a content of Fe 2 O 3 being 200 ppm or less as expressed in terms of parts per million mass based on the oxides.
7. The glass substrate according to claim 1 , having a Young's modulus of 80 GPa or more.
8. The glass substrate according to claim 1 , having a thickness of 1.0 mm or less.
9. The glass substrate according to claim 1 , having an area of 0.03 m 2 or more.
10. The glass substrate according to claim 1 , wherein a density of defect having a size of 0.5 μm or more and 1 mm or less contained in the glass substrate is one or less per cm 2 .
11. The glass substrate according to claim 1 , having a fictive viscosity of 10 11.10 dPa·sec to 10 14.1 dPa·sec.
12. The glass substrate according to claim 1 , having a weight loss value relative to a 5 mass % hydrofluoric aqueous solution at 25° C. of 0.05 (mg/cm 2 )/min or more and 0.20 (mg/cm 2 )/min or less.
13. The glass substrate according to claim 1 , having a photoelastic constant of 31 nm/(MPa·cm) or less.
14. The glass substrate according to claim 1 , satisfying the following condition (1), condition (2), condition (3), and condition (4):
{0.0177×(content of SiO 2 )−0.0173×(content of Al 2 O 3 )+0.0377×(content of B 2 O 3 )+0.0771×(content of MgO)+0.1543×(content of CaO)+0.1808×(content of SrO)+0.2082×(content of BaO)+0.0344×(12.3±log 10 60−log 10 η)} is 2.70 to 2.96, Condition (1):
{0.0181×(content of SiO 2 )+0.0004×(content of Al 2 O)+0.0387×(content of B 2 O 3 )+0.0913×(content of MgO)+0.1621×(content of CaO)+0.1900×(content of SrO)+0.2180×(content of BaO)+0.0391×(12.3+log 10 60−log 10 η)} is 3.13 to 3.41, Condition (2):
{0.0177×(content of SiO 2 )+0.0195×(content of Al 2 O 3 )+0.0323×(content of B 2 O 3 )+0.1015×(content of MgO)+0.1686×(content of CaO)+0.1990×(content of SrO)+0.2179×(content of BaO)+0.0312×(12.3+log 10 60−log 10 η)} is 3.45 to 3.95, and Condition (3):
{0.0111×(content of SiO 2 )+0.0250×(content of Al 2 O 3 )+0.0078×(content of B 2 O 3 )+0.0144×(content of MgO)+0.0053×(content of CaO)+0.0052×(content of SrO)+0.0013×(content of BaO)−0.0041×(12.3+log 10 60−log 10 η)} is 1.20 to 1.30. Condition (4):
15. A laminated substrate, comprising:
the glass substrate according to claim 1 ; and
a silicon substrate laminated on the glass substrate.
16. A laminated substrate, comprising:
the glass substrate of claim 1 ; and
a silicon substrate laminated on the glass substrate,
wherein:
a difference Δα 50/100 (=α 50/100 −α Si50/100 ) between an average thermal expansion coefficient α 50/100 at 50° C. to 100° C. of the glass substrate and an average thermal expansion coefficient α Si50/100 at 50° C. to 100° C. of the silicon substrate is −0.25 ppm/° C. to 0.25 ppm/° C.;
a difference Δα 200/300 (=α 200/300 −α Si200/300 ) between an average thermal expansion coefficient α 200/300 at 200° C. to 300° C. of the glass substrate and an average thermal expansion coefficient α Si200/300 at 200° C. to 300° C. of the silicon substrate is −0.25 ppm/° C. to 0.25 ppm/° C.; and
(Δα 200/300 −Δα 50/100 ) is −0.16 ppm/° C. to 0.16 ppm/° C.
17. The laminated substrate according to claim 16 , wherein a difference Δα 100/200 (=α 100/200 −α Si100/200 ) between an average thermal expansion coefficient α 100/200 at 100° C. to 200° C. of the glass substrate and an average thermal expansion coefficient α Si100/200 at 100° C. to 200° C. of the silicon substrate is −0.25 ppm/° C. to 0.25 ppm/° C.
18. A method for producing a glass substrate according to claim 1 , the method comprising:
a melting step of heating glass raw materials to obtain a molten glass;
a refining step of removing bubbles from the molten glass;
a forming step of forming the molten glass into a sheet-like shape to obtain a glass ribbon; and
a cooling step of gradually cooling the glass ribbon to a room temperature state,
wherein the resulting glass substrate has a composition as defined in claim 1 .