CN107406300A - Glass - Google Patents

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Publication number
CN107406300A
CN107406300A CN201680012773.9A CN201680012773A CN107406300A CN 107406300 A CN107406300 A CN 107406300A CN 201680012773 A CN201680012773 A CN 201680012773A CN 107406300 A CN107406300 A CN 107406300A
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China
Prior art keywords
less
glass
mgo
cao
content
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CN201680012773.9A
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Inventor
齐藤敦己
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Nippon Electric Glass Co Ltd
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Nippon Electric Glass Co Ltd
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Application filed by Nippon Electric Glass Co Ltd filed Critical Nippon Electric Glass Co Ltd
Priority to CN202310080491.4A priority Critical patent/CN116040940A/en
Priority to CN202310085917.5A priority patent/CN115974404A/en
Publication of CN107406300A publication Critical patent/CN107406300A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/02—Other methods of shaping glass by casting molten glass, e.g. injection moulding
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
    • C03B5/16—Special features of the melting process; Auxiliary means specially adapted for glass-melting furnaces
    • C03B5/18—Stirring devices; Homogenisation
    • C03B5/187—Stirring devices; Homogenisation with moving elements
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/02422—Non-crystalline insulating materials, e.g. glass, polymers

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Glass Compositions (AREA)

Abstract

Present invention discover that a kind of heat resistance and thermal coefficient of expansion are high and are capable of being shaped to the glass of writing board shape.The glass of the present invention, it is characterised in that contain SiO in terms of mole %255~80%, Al2O311~30%, B2O30~3%, Li2O+Na2O+K2O 0~3%, MgO+CaO+SrO+BaO 5~35% form as glass, and strain point is higher than 700 DEG C.

Description

Glass
Technical field
The present invention relates to a kind of glass of high-fire resistance, and in particular to for example for making LED semiconductors at high temperature The glass substrate of crystal.
Background technology
Film forming, characteristic of semiconductor more improve semiconductor crystal used in known LED etc. at high temperature.
In the purposes, the general sapphire substrate for using high-fire resistance.In other purposes, when in high temperature (example Such as more than 700 DEG C) under in the case of film forming semiconductor crystal, also using sapphire substrate.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 11-243229 publications
The content of the invention
The invention problem to be solved
But in recent years, energetically study the technology of the semiconductor crystal of film forming large area.Think that the technology also has Hope the face illuminating source as giant display.
But sapphire substrate is difficult to large area, be not suitable for such use.
If glass substrate is used instead of sapphire substrate, then it is assumed that substrate large area can be made, it is still, just conventional For glass substrate, because heat resistance is insufficient, therefore thermal deformation easily occurs under the heat treatment of high temperature.
And, if it is desired to the heat resistance of conventional glass substrate is improved, then the thermal coefficient of expansion of glass substrate can be undeservedly Reduce, it is difficult to the matched coefficients of thermal expansion with semiconductor crystal, after semiconductor crystal is made the easy warpage of glass substrate or Easily cracked in semiconductor film.And then, if it is desired to the heat resistance of glass substrate is improved, then devitrification resistance is reduced and is difficult to It is configured to the glass substrate of writing board shape.
The invention that the present invention is in view of the foregoing and completed, its technical task are invention heat resistance and thermal coefficient of expansion It is high and be capable of being shaped to the glass of writing board shape.
Means for solving the problems
Various experiments are repeated in the present inventor, and as a result find can be by being limited in prescribed limit to solve by glass composition Certainly above-mentioned technical task, thus complete the present invention.That is, glass of the invention, it is characterised in that contain SiO in terms of mole %2 55~80%, Al2O311~30%, B2O30~3%, Li2O+Na2O+K2O 0~3%, MgO+CaO+SrO+BaO 5~ 35% forms as glass, and strain point is higher than 700 DEG C.Here, " Li2O+Na2O+K2O " refers to Li2O、Na2O and K2O's is total Amount." MgO+CaO+SrO+BaO " refers to MgO, CaO, SrO and BaO total amount.Here, " strain point " refers to be based on ASTMC336 Method determine obtained value.
The glass of the present invention is in glass composition by Al2O3It is limited in 11 moles of more than %, by B2O3Content be limited in 3 Mole below % and by Li2O+Na2O+K2O content is limited in 3 moles of below %.So, strain point significantly rises, can To greatly improve the heat resistance of glass substrate.
In addition, the glass of the present invention includes 5~25 moles of %MgO+CaO+SrO+BaO in glass composition.So, Thermal coefficient of expansion can be made to increase, and devitrification resistance can be improved.
Second, glass of the invention preferably makes B2O3Less than 1 mole % of content.
3rd, glass of the invention preferably makes Li2O+Na2O+K2O content is 0.2 mole of below %.
4th, glass of the invention preferably makes mol ratio (MgO+CaO+SrO+BaO)/Al2O3For 0.5~5.Here, “(MgO+CaO+SrO+BaO)/Al2O3" be MgO, CaO, SrO and BaO total amount divided by Al2O3Content obtained by value.
5th, glass of the invention preferably makes mol ratio MgO/ (MgO+CaO+SrO+BaO) less than 0.5.Here, " MgO/ (MgO+CaO+SrO+BaO) " for MgO content divided by MgO, CaO, SrO and BaO total amount obtained by value.
6th, the thermal coefficient of expansion of glass of the invention within the temperature range of 30~380 DEG C is preferably 40 × 10- 7/℃ More than.Here, " thermal coefficient of expansion within the temperature range of 30~380 DEG C " refers to be averaged using what thermal dilatometer determined to obtain Value.
7th, the strain point of glass of the invention is preferably more than 800 DEG C.
8th, (the 10 of glass of the invention2.5Temperature-strain point during dPas) it is preferably less than 900 DEG C.Here, " high temperature viscosity 102.5Temperature during dPas " refers to determine obtained value using daraf(reciprocal of farad) on platinum ball.
9th, glass of the invention is 102.5Temperature during dPas viscosity is preferably less than 1750 DEG C.
Tenth, glass of the invention is preferably writing board shape.
11st, glass of the invention is preferably used in the substrate for making semiconductor crystal.
Embodiment
The glass of the present invention contains SiO in terms of mole %255~80%, Al2O311~30%, B2O30~3%, Li2O +Na2O+K2O 0~3%, MgO+CaO+SrO+BaO 5~35% form as glass.Below to limit as described above it is each into The reasons why content divided, illustrates.It is explained, in the explanation of each composition, following % represents to refer to a mole %.
SiO2Suitable lower range be more than 55%, more than 58%, more than 60%, more than 65%, in particular 68% More than, suitable upper range is preferably less than 80%, less than 75%, less than 73%, less than 72%, less than 71%, it is especially excellent Elect less than 70% as.If SiO2Content it is very few, then easily produce by including Al2O3Devitrification crystal caused by the defects of, and should Height is easily reduced.In addition, reducing high temperature viscosity, liquid phase viscosity is easily reduced.On the other hand, if SiO2Content it is excessive, Then thermal coefficient of expansion undeservedly reduces, and high temperature viscosity uprises, and the reduction of meltbility easily occurs, and then easily produce and include SiO2Devitrification crystal etc..
Al2O3Suitable lower range for more than 11%, more than 12%, more than 13%, more than 14%, especially 15% More than, suitable upper range be less than 30%, less than 25%, less than 20%, less than 18%, less than 17%, especially 16% Below.If Al2O3Content it is very few, then strain point is easily reduced or high temperature viscometrics uprise and are easily reduced meltbility.Separately On the one hand, if Al2O3Content it is excessive, then easily produce include Al2O3Devitrification crystal.
From the viewpoint of high strain-point and high devitrification resistance is taken into account, mol ratio SiO2/Al2O3Preferably 2~6,3~ 5.5th, 3.5~5.5,4~5.5,4.5~5.5, particularly preferably 4.5~5.It is explained, " SiO2/Al2O3" it is SiO2Contain Amount divided by Al2O3Content obtained by value.
B2O3Suitable upper range for less than 3%, less than 1%, less than 1%, especially less than 0.1%.If B2O3's Content is excessive, then existing makes the risk that strain point is greatly reduced.
Li2O+Na2O+K2O suitable upper range is less than 3%, less than 1%, less than 1%, less than 0.5%, especially It is less than 0.2%.If Li2O+Na2O+K2O content is excessive, then the deterioration in characteristics for the semiconductor crystal being formed on glass be present Risk.It is explained, Li2O、Na2O and K2O suitable upper range is respectively less than 3%, less than 1%, less than 1%, Less than 0.5%, less than 0.3%, especially less than 0.2%.
MgO+CaO+SrO+BaO suitable lower range be more than 5%, more than 7%, more than 9%, more than 11%, More than 13%, especially more than 14%, suitable upper range be less than 35%, less than 30%, less than 25%, less than 20%, Less than 18%, less than 17%, especially less than 16%.If MgO+CaO+SrO+BaO content is very few, liquidus temperature significantly on Rise and easily produce devitrification crystal in glass, or high temperature viscometrics uprise and are easily reduced meltbility.On the other hand, if MgO+CaO+SrO+BaO content is excessive, then strain point is easily reduced, and it is brilliant easily to produce the devitrification comprising alkaline earth element Body.
MgO suitable lower range be more than 0%, more than 1%, more than 2%, more than 3%, more than 4%, especially More than 5%, suitable upper range be less than 15%, less than 10%, less than 8%, especially less than 7%.If MgO content mistake Few, then meltbility is easily reduced, or the increased devitrification resistance of the crystal comprising alkaline earth element easily uprises.On the other hand, if MgO's contains Amount is excessive, then promotes to include Al2O3Devitrification crystal precipitation and cause liquid phase viscosity to reduce, or cause strain point significantly to drop It is low.It is explained, MgO has the effect for making thermal coefficient of expansion increase, but its effect is minimum in alkaline-earth oxide.
CaO suitable lower range be more than 2%, more than 3%, more than 4%, more than 5%, more than 6%, especially More than 7%, suitable upper range be less than 20%, less than 15%, less than 12%, less than 11%, less than 10%, especially Less than 9%.If CaO content is very few, meltbility is easily reduced.On the other hand, if CaO content is excessive, liquidus temperature Rise and easily produce devitrification crystal in glass.It is explained, for CaO, compared with other alkaline-earth oxides, does not reduce Strain point and improve the effect of liquid phase viscosity or improve meltbility effect it is big, and thermal coefficient of expansion is than effect that MgO rises Fruit is big.
SrO suitable lower range is more than 0%, more than 1%, especially more than 2%, and suitable upper range is Less than 10%, less than 8%, less than 7%, less than 6%, less than 5%, especially less than 4%.If SrO content is very few, strain Point is easily reduced.On the other hand, if SrO content is excessive, liquidus temperature rises and easily produces devitrification crystal in glass, And meltbility is easily reduced.And then if with CaO coexisting SrO containing quantitative change it is more, exist devitrification resistance reduction incline To.It is explained, SrO is bigger than the effect that MgO or CaO thermal coefficient of expansions rise.
BaO suitable lower range be more than 0%, more than 3%, more than 4%, more than 5%, more than 6%, more than 7%, Especially more than 8%, suitable upper range be less than 15%, less than 12%, less than 11%, especially less than 10%.If BaO Content it is very few, then strain point or thermal coefficient of expansion are easily reduced.On the other hand, if BaO content is excessive, on liquidus temperature Rise and easily produce devitrification crystal in glass.In addition, meltbility is easily reduced.It is explained, in alkaline earth oxide, The BaO effect for making thermal coefficient of expansion or strain point increase is maximum.
From the viewpoint of devitrification resistance is improved, mol ratio MgO/CaO lower range be preferably more than 0.1,0.2 with It is upper, more than 0.3, particularly preferably more than 0.4, upper range is preferably less than 2, less than 1, less than 0.8, less than 0.7, it is especially excellent Elect less than 0.6 as.It is explained, " MgO/CaO " refers to MgO content divided by the value obtained by CaO content.
From the viewpoint of devitrification resistance is improved, mol ratio BaO/CaO lower range be preferably more than 0.2,0.5 with It is upper, more than 0.6, more than 0.7, particularly preferably more than 0.8, upper range be preferably less than 5, less than 4.5, less than 3,2.5 with Under, particularly preferably less than 2.It is explained, " BaO/CaO " refers to BaO content divided by the value obtained by CaO content.
If in view of the balance of strain point and meltbility, mol ratio (MgO+CaO+SrO+BaO)/Al2O3Lower range it is excellent Elect more than 0.5 as, more than 0.6, more than 0.7, particularly preferably more than 0.8, upper range is preferably less than 5.0, less than 4.0, Less than 3.0, less than 2.0, less than 1.5, less than 1.2, particularly preferably less than 1.1.
Mol ratio MgO/ (MgO+CaO+SrO+BaO) is preferably less than 0.6, less than 0.5, less than 0.4, less than 0.3,0.2 Below, it is particularly preferably less than 0.1.MgO is the composition that strain point is greatly reduced, and in MgO poor region, makes strain The significant effect that point reduces.Therefore, in alkaline earth oxide, MgO content ratio is more few more preferred.
7 × [MgO]+5 × [CaO]+4 × [SrO]+4 × [BaO] is preferably less than 100%, less than 90%, less than 80%, Less than 70%, less than 65%, particularly preferably less than 60%.Alkali earth metal is respectively provided with the effect for reducing strain point, but It is, ionic radius small element that the influence is bigger.Therefore, if limitation 7 × [MgO]+5 × [CaO]+4 × [SrO]+4 × The upper range of [BaO] then can preferentially improve strain point without making the ratio of the small alkaline earth element of ionic radius become big.Give Illustrate, [MgO] refers to MgO content, and [CaO] refers to CaO content, and [SrO] refers to SrO content, and [BaO] refers to BaO's Content.Moreover, " 7 × [MgO]+5 × [CaO]+4 × [SrO]+4 × [BaO] " refer to 7 times [MgO], 5 times of [CaO], 4 times [SrO] and 4 times of [BaO] total amount.
21 × [MgO]+20 × [CaO]+15 × [SrO]+12 × [BaO] is preferably more than 200%, more than 210%, More than 220%, more than 230%, more than 240%, more than 250%, particularly preferably 300~1000%.Alkali earth metal is equal With the effect for improving meltbility, still, the small element of ionic radius, the influence are bigger.Therefore, if limitation 21 × Ratio of [MgO]+20 × [CaO]+15 × [SrO]+12 × [BaO] lower range without making the small alkaline earth element of ionic radius Become big, then can preferentially improve meltbility.But if 21 × [MgO]+20 × [CaO]+15 × [SrO]+12 × [BaO] is excessive, The risk of strain point reduction then be present.It is explained, " 21 × [MgO]+20 × [CaO]+15 × [SrO]+12 × [BaO] " refers to The total amount of 21 times of [MgO], 20 times of [CaO], 15 times of [SrO] and 12 times of [BaO].
In addition to mentioned component, following component can also be introduced into glass composition.
ZnO is the composition for improving meltbility, if largely containing ZnO in glass composition, the easy devitrification of glass, and should Height is easily reduced.Therefore, ZnO content is preferably 0~5%, 0~3%, 0~0.5%, 0~0.3%, particularly preferably 0 ~0.1%.
ZrO2It is the composition for improving Young's modulus.ZrO2Content be preferably 0~5%, 0~3%, 0~0.5%, 0~ 0.2%th, it is particularly preferably 0~0.02%.If ZrO2Content it is excessive, then liquidus temperature rise and easily separate out the devitrification of zircon Crystal.
TiO2It is to reduce high temperature viscometrics and improve the composition of meltbility, and is the composition for suppressing solarization, if in glass Largely contain TiO in glass composition2, then glass easily colour.Therefore, TiO2Content be preferably 0~5%, 0~3%, 0~1%, 0~0.1%, it is particularly preferably 0~0.02%.
P2O5It is the composition for improving devitrification resistance, if but largely containing P in glass composition2O5, then glass easily divide It is phase, milky white, and exist and make the risk that water resistance is greatly reduced.Therefore, P2O5Content be preferably 0~5%, 0~4%, 0~ 3%th, less than 0 and less than 2%, 0~1%, 0~0.5%, particularly preferably 0~0.1%.
SnO2It is the composition in high-temperature area with good clarification, and is the composition for reducing high temperature viscometrics. SnO2Content be preferably 0~1%, 0.01~0.5%, 0.01~0.3%, particularly preferably 0.04~0.1%.If SnO2's Content is excessive, then easily separates out SnO2Devitrification crystal.
As described above, the glass of the present invention is adapted to add SnO2As fining agent, still, as long as not damaging glass performance, More 1%CeO can also be then added to2、SO3, C, metal dust (such as Al, Si etc.) be used as fining agent.
As2O3、Sb2O3, F, Cl also serve as fining agent and effectively play a role, glass of the invention is not precluded from containing this A little compositions, still, from the viewpoint of environment, the content difference preferably less than 0.1% of these compositions, particularly preferably deficiency 0.05%.
Including SnO2In the case of 0.01~0.5%, if Rh2O3Content it is excessive, then glass easily colours.Said It is bright, Rh2O3In the presence of the mixed possibility of manufacture container from platinum.Rh2O3Content be preferably 0~0.0005%, more preferably 0.00001~0.0001%.
SO3It is from the mixed composition of raw material in the form of impurity, still, if SO3Content it is excessive, then melt or shape It is middle to produce the bubble for being referred to as boiling again, the risk for making that defect is produced in glass be present.SO3Suitable lower range be 0.0001% More than, suitable upper range be less than 0.005%, less than 0.003%, less than 0.002%, especially less than 0.001%.
Rare-earth oxide (Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu etc. oxidation Thing) content be preferably less than 2%, less than 1%, less than 0.5%, especially less than 0.1%.Especially make La2O3+Y2O3Contain Amount is preferably less than 2%, less than 1%, less than 0.5%, especially less than 0.1%.La2O3Content be preferably less than 2%, no Sufficient 1%, less than 0.5%, especially less than 0.1%.If the content of rare-earth oxide is excessive, batch of material cost easily increases. It is explained, " Y2O3+La2O3" it is Y2O3With La2O3Total amount.
The glass of the present invention preferably has following characteristic.
Density is preferably 3.20g/cm3Below, 3.00g/cm3Below, 2.90g/cm3Below, it is particularly preferably 2.80g/ cm3Below.If density is too high, it is difficult to the lighting for reaching electronic device.
Thermal coefficient of expansion within the temperature range of 30~380 DEG C is preferably 40 × 10- 7/ DEG C more than, 42 × 10- 7/ DEG C with Above, 44 × 10- 7/ DEG C more than, 46 × 10- 7/ DEG C more than, particularly preferably 48 × 10- 7~80 × 10- 7/℃.If 30~380 Thermal coefficient of expansion within the temperature range of DEG C is too low, then will not make semiconductor crystal (such as nitride semiconductor crystal) and glass The matched coefficients of thermal expansion of substrate, the easy warpage of glass substrate or is easily cracked in semiconductor crystal.
Strain point be preferably more than 700 DEG C, more than 750 DEG C, more than 780 DEG C, more than 800 DEG C, more than 810 DEG C, 820 DEG C with Above, particularly preferably 830~1000 DEG C.If strain point is too low, heat treatment temperature high temperature can not be made, it is difficult to improve semiconductor The characteristic of semiconductor of crystal.
The SiO of the present invention2- Al2O3- RO (RO refers to alkaline earth oxide) is that glass is typically difficult to melt.Therefore, The raising of meltbility turns into problem.If improving meltbility, mitigate the fraction defective caused by bubble, foreign matter etc., therefore can be a large amount of And inexpensively supply the glass substrate of high-quality.On the other hand, if high temperature viscosity is too high, it is difficult to promote to take off in process is melted Bubble.Therefore, high temperature viscosity 102.5Temperature during dPas is preferably less than 1750 DEG C, less than 1700 DEG C, less than 1680 DEG C, 1670 Below DEG C, less than 1650 DEG C, particularly preferably less than 1630 DEG C.It is explained, high temperature viscosity 102.5Temperature phase during dPas When in melting temperature, the temperature is lower, and meltbility is more excellent.
From the viewpoint of high strain-point and low melting glass is taken into account, (102.5Temperature-strain point during dPas) preferably For less than 900 DEG C, less than 850 DEG C, particularly preferably less than 800 DEG C.
In the case where being configured to writing board shape, devitrification resistance becomes more important.If consider the SiO of the present invention2- Al2O3The forming temperature of-RO systems glass, then liquidus temperature be preferably less than 1450 DEG C, less than 1400 DEG C, particularly preferably 1300 Below DEG C.In addition, liquid phase viscosity is preferably 103.0More than dPas, 103.5More than dPas, particularly preferably 104.0dPa·s More than.It is explained, " liquidus temperature " refers to：By the mesh of standard screen 30 (500 μm) and the glass of 50 mesh (300 μm) will be residued in Glass powder is added in platinum boat, is kept for 24 hours in thermal gradient furnace, and determines the value of the temperature of crystal precipitation." liquid phase viscosity " refers to Utilize the viscosity of glass of the daraf(reciprocal of farad) measure under liquidus temperature on platinum ball.
The glass of the present invention can be shaped using various manufacturing process.Such as it can utilize under overflow downdraw, discharge orifice Draw method, draw method, float glass process down again, offset the molding glass substrate such as method.It is explained, if utilizing overflow downdraw molding glass base Plate, then easily make the high glass substrate of surface smoothness.
The present invention glass be writing board shape in the case of, its thickness of slab be preferably below 1.0mm, below 0.7mm, Below 0.5mm, particularly preferably below 0.4mm.Thickness of slab is smaller, more easily makes electronic device lighting.On the other hand, thickness of slab is got over Small, the easier flexure of glass substrate, glass of the invention is not likely to produce by scratching because Young's modulus or specific Young's modulus are high Unfavorable condition caused by song.It is explained, thickness of slab can be adjusted using flow when shaping, plate pull rate etc..
In the glass of the present invention, if making the reduction of β-OH values, strain point can be improved.β-OH values are preferably 0.45/ Below mm, below 0.40/mm, below 0.35/mm, below 0.30/mm, below 0.25/mm, below 0.20/mm, particularly preferably Below 0.15/mm.If β-OH values are excessive, strain point is easily reduced.It is explained, if β-OH values are too small, meltbility is held Easily reduce.Therefore, β-OH values are preferably more than 0.01/mm, particularly preferably more than 0.05/mm.
As the method for reducing β-OH values, following method can be enumerated.(1) the low raw material of water content is selected.(2) add Make composition (Cl, SO of the amount of moisture reduction in glass3Deng).(3) reduce the amount of moisture in furnace atmosphere.(4) in melting glass N is carried out in glass2Bubbling.(5) small-sized melting furnace is used.(6) flow of melten glass is accelerated.(7) electric fusion method is used.
Here, " β-OH values " refers to：The transmissivity of glass, and the value tried to achieve using following formula are determined using FT-IR.
β-OH value=(1/X) log (T1/T2)
X：Glass wall thickness (mm)
T1：With reference to wavelength 3846cm- 1Under transmissivity (%)
T2：Hydroxyl group absorption wavelength 3600cm- 1Minimum transmittance (%) under nearby
Embodiment
Hereinafter, the present invention is described in detail based on embodiment.Be explained, following embodiment only exemplified by Show.The present invention is simultaneously not limited in any way the following examples restriction.
Table 1~4 represents embodiments of the invention (sample No.1~63).
[table 1]
[table 2]
[table 3]
[table 4]
It is as follows to make each sample like that.First, the glass batch of frit will be concocted according to the glass composition in table Material is added in platinum crucible, is melted 24 hours at 1600~1750 DEG C.In the melting of glass batch materials, stirred using platinum agitator Mix, and homogenized.Then, melten glass is flowed out onto carbon plate, is configured to writing board shape.Each sample of gained is evaluated Density p, thermalexpansioncoefficientα, strain point Ps, annealing point Ta, softening point Ts, high temperature viscosity 104.0Temperature, height during dPas Warm viscosity 103.0Temperature, high temperature viscosity 10 during dPas2.5Temperature, liquidus temperature TL, liquid phase viscosity log η during dPas TL。
Density p is the value that the Archimedes method known to determines to obtain.
Thermalexpansioncoefficientα is to determine obtained average value using thermal dilatometer within the temperature range of 30~380 DEG C.
Strain point Ps, annealing point Ta, softening point Ts are the values that foundation ASTM C336 or ASTM C338 determines to obtain.
High temperature viscosity 104.0Temperature, high temperature viscosity 10 during dPas3.0Temperature, high temperature viscosity during dPas 102.5Temperature during dPas is to determine obtained value using daraf(reciprocal of farad) on platinum ball.
Liquidus temperature TL is：Each sample will be crushed and by the mesh of standard screen 30 (500 μm) and after residuing in 50 mesh (300 μm) Glass powder be added in platinum boat, kept for 24 hours in thermal gradient furnace after, take out platinum boat, confirm in glass devitrification (lose Saturating crystal) temperature.Liquid phase viscosity log η TL are to utilize viscosimetric analysis of the daraf(reciprocal of farad) to the glass under liquidus temperature TL on platinum ball Obtained value.
β-OH values are the value calculated based on above-mentioned formula.
From table 1~4：For sample No.1~63, strain point and thermal coefficient of expansion are high, possess and are capable of being shaped to put down The devitrification resistance of plate shape.It is therefore contemplated that sample No.1~63, which are suitable as being used for crystal growth at high temperature, goes out semiconductor die The substrate of body (such as nitride semiconductor crystal, especially gallium nitride semiconductor crystal).
Industrial applicability
For the glass of the present invention, its strain point and thermal coefficient of expansion are high, and possess good devitrification resistance.Cause This, glass of the invention is also adapted to OLED display, liquid crystal in addition to the substrate for making semiconductor crystal at high temperature The base plate for displaying such as display, it is particularly suitable as the base plate for displaying driven under LTPS, oxide TFT.

Claims (11)

1. a kind of glass, it is characterised in that contain SiO in terms of mole %255%~80%, Al2O311%~30%, B2O3 0%~3%, Li2O+Na2O+K2O 0%~3% and MgO+CaO+SrO+BaO 5%~35% forms as glass, and strains Point is higher than 700 DEG C.
2. glass according to claim 1, it is characterised in that B2O3Less than 1 mole % of content.
3. glass according to claim 1 or 2, it is characterised in that Li2O+Na2O+K2O content be 0.2 mole of % with Under.
4. according to glass according to any one of claims 1 to 3, it is characterised in that mol ratio (MgO+CaO+SrO+BaO)/ Al2O3For 0.5~5.
5. according to glass according to any one of claims 1 to 4, it is characterised in that mol ratio MgO/ (MgO+CaO+SrO+ BaO) less than 0.5.
6. according to glass according to any one of claims 1 to 5, it is characterised in that within the temperature range of 30 DEG C~380 DEG C Thermal coefficient of expansion be 40 × 10- 7/ DEG C more than.
7. according to glass according to any one of claims 1 to 6, it is characterised in that strain point is more than 800 DEG C.
8. according to glass according to any one of claims 1 to 7, it is characterised in that (102.5Temperature-strain during dPas Point) it is less than 900 DEG C.
9. according to glass according to any one of claims 1 to 8, it is characterised in that 102.5Temperature during dPas viscosity For less than 1750 DEG C.
10. according to glass according to any one of claims 1 to 9, it is characterised in that it is writing board shape.
11. according to glass according to any one of claims 1 to 10, it is characterised in that it is used in partly leads for making In the substrate of body crystal.
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