CN107735376A - 显示器用玻璃基板及其制造方法 - Google Patents
显示器用玻璃基板及其制造方法 Download PDFInfo
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- CN107735376A CN107735376A CN201680037857.8A CN201680037857A CN107735376A CN 107735376 A CN107735376 A CN 107735376A CN 201680037857 A CN201680037857 A CN 201680037857A CN 107735376 A CN107735376 A CN 107735376A
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- Prior art keywords
- glass
- glass substrate
- sio
- display
- devitrification
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- 239000011521 glass Substances 0.000 title claims abstract description 273
- 239000000758 substrate Substances 0.000 title claims abstract description 118
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 82
- 238000004031 devitrification Methods 0.000 claims abstract description 79
- 239000000203 mixture Substances 0.000 claims abstract description 59
- 238000010438 heat treatment Methods 0.000 claims abstract description 58
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 52
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 52
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 45
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 45
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 45
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 45
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 45
- 238000002844 melting Methods 0.000 claims abstract description 35
- 230000008018 melting Effects 0.000 claims abstract description 35
- 238000010583 slow cooling Methods 0.000 claims abstract description 24
- 239000005357 flat glass Substances 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 239000000155 melt Substances 0.000 claims abstract description 8
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 claims description 6
- 230000008602 contraction Effects 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 5
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 4
- 239000004065 semiconductor Substances 0.000 claims description 4
- 229920005591 polysilicon Polymers 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 20
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 16
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 15
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 15
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 15
- 229910001928 zirconium oxide Inorganic materials 0.000 description 14
- 239000006025 fining agent Substances 0.000 description 12
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 8
- 238000005530 etching Methods 0.000 description 8
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 6
- 238000005352 clarification Methods 0.000 description 5
- 238000003280 down draw process Methods 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000003723 Smelting Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000006124 Pilkington process Methods 0.000 description 2
- 239000011449 brick Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000005401 electroluminescence Methods 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000000156 glass melt Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910017583 La2O Inorganic materials 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(III) oxide Inorganic materials O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 description 1
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 229910003443 lutetium oxide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 description 1
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium (III) oxide Inorganic materials [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/1218—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition or structure of the substrate
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- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B17/00—Forming molten glass by flowing-out, pushing-out, extruding or drawing downwardly or laterally from forming slits or by overflowing over lips
- C03B17/06—Forming glass sheets
- C03B17/064—Forming glass sheets by the overflow downdraw fusion process; Isopipes therefor
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B25/00—Annealing glass products
- C03B25/04—Annealing glass products in a continuous way
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- C03B25/04—Annealing glass products in a continuous way
- C03B25/06—Annealing glass products in a continuous way with horizontal displacement of the glass products
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- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B5/00—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture
- C03B5/02—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture in electric furnaces, e.g. by dielectric heating
- C03B5/027—Melting in furnaces; Furnaces so far as specially adapted for glass manufacture in electric furnaces, e.g. by dielectric heating by passing an electric current between electrodes immersed in the glass bath, i.e. by direct resistance heating
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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
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- C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
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- 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
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- 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
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- 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
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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
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- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
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- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
- C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
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- 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
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- G—PHYSICS
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/1222—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or crystalline structure of the active layer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/1222—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or crystalline structure of the active layer
- H01L27/1225—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs with a particular composition, shape or crystalline structure of the active layer with semiconductor materials not belonging to the group IV of the periodic table, e.g. InGaZnO
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/12—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body
- H01L27/1214—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being other than a semiconductor body, e.g. an insulating body comprising a plurality of TFTs formed on a non-semiconducting substrate, e.g. driving circuits for AMLCDs
- H01L27/1259—Multistep manufacturing methods
- H01L27/1262—Multistep manufacturing methods with a particular formation, treatment or coating of the substrate
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
- H01L29/78603—Thin film transistors, i.e. transistors with a channel being at least partly a thin film characterised by the insulating substrate or support
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- H—ELECTRICITY
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Abstract
本申请提供一种将失透温度抑制得较低并且满足高应变点的玻璃基板及其制造方法。显示器用玻璃基板包含以下玻璃,该玻璃含有SiO2、Al2O3,以质量%表示,B2O3为0%以上且未达3%,BaO为5~14%,实质上不含有Sb2O3,失透温度为1235℃以下,且应变点为720℃以上。或者包含以下玻璃,该玻璃含有SiO2、Al2O3,以质量%表示,B2O3为0%以上且未达3%,MgO为1.8%以上,BaO为5~14%,实质上不含有Sb2O3,(SiO2+MgO+CaO)-(Al2O3+SrO+BaO)未达42%,失透温度为1260℃以下,且应变点为720℃以上。显示器用玻璃基板的制造方法包含:熔解步骤,至少使用直接通电加热使调制成特定组成的玻璃原料熔解;成形步骤,使在所述熔解步骤中熔解所得的熔融玻璃成形为平板状玻璃;及缓冷步骤,使所述平板状玻璃缓冷,并且以降低所述平板状玻璃的热缩率的方式控制所述平板状玻璃的冷却条件。
Description
技术领域
本发明涉及一种显示器用玻璃基板及其制造方法。本发明特别涉及一种低温多晶硅薄膜晶体管(以下,记载为LTPS-TFT(Low-Temperature-Polycrystalline-SiliconThin-Film-Transistor))显示器用玻璃基板。此外,本发明涉及一种氧化物半导体薄膜晶体管(以下,记载为OS-TFT(Oxide-Semiconductor Thin-Film-Transistor))显示器用玻璃基板。更详细来说,本发明涉及一种所述显示器为液晶显示器的显示器用玻璃基板。或本发明涉及一种所述显示器为有机EL(Electroluminescence,电激发光)显示器的显示器用玻璃基板。而且,本发明涉及一种所述显示器为平板显示器的平板显示器用玻璃基板。
[相关申请的相互参照]
本申请主张2015年6月30日申请的日本专利特愿2015-131780号的优先权其全部记载尤其作为揭示而被援用于本文中。
背景技术
就可降低功耗等理由来说,移动设备等所搭载的显示器期待将LTPS应用于制造薄膜晶体管(TFT),在LTPS-TFT的制造中,需要在400~600℃的相对高温下进行热处理。另一方面,近年来逐渐要求小型移动设备的显示器高精细化。因此,引起像素的间距偏差的制造显示器面板时所产生的玻璃基板的热缩成为问题。此外,即便在形成有OS-TFT的玻璃基板中,同样地抑制热缩也成为课题。
玻璃基板的热缩率通常可通过提高玻璃的应变点、提高玻璃转移点(以下称为Tg)、或者减缓缓冷速度而降低。根据此种情况,揭示有为了降低热缩率而提高玻璃的应变点的技术(专利文献1)。此外,揭示有调整缓冷点至应变点附近的温度区域下的平均密度曲线的斜率与平均线膨胀系数的比而减少热缩的技术(专利文献2)。此外,揭示有为了降低热缩率而提高Tg的技术(专利文献3)。而且,由于近年来逐渐要求显示器面板的高精细化,因此专利文献3的技术成为不充分的热缩率的降低。为此,也揭示有将玻璃的应变点设为725℃以上的技术(专利文献4)。
专利文献1:日本专利特开2010-6649号公报
专利文献2:日本专利特开2004-315354号公报
专利文献3:日本专利特开2011-126728号公报
专利文献4:日本专利特开2012-106919号公报
专利文献1~4的全部记载尤其作为揭示而被援用于本文中。
发明内容
[发明所要解决的问题]
近年来,由于逐渐要求高精细化,因此要求进一步缩小热缩率。在为了进一步缩小热缩率而提高玻璃基板的应变点的情况下,必须使玻璃中的SiO2或Al2O3的含量增多,结果,有熔融玻璃的比电阻上升的倾向。近年来,存在为了使玻璃在溶解槽中有效率地熔解而使用直接通电加热的情况。在使用直接通电加热的情况下,若熔融玻璃的比电阻上升,则电流并非流过熔融玻璃而是流过构成熔解槽的耐火物,结果很明显有可能会导致产生熔解槽熔损。然而,在所述专利文献1所记载的发明中,关于熔融玻璃的比电阻并未做任何考虑。因此,在欲经过基于直接通电加热的熔融制造专利文献1所记载的玻璃的情况下,严重担心会产生所述熔解槽熔损的问题。而且,由于近年来逐渐要求高精细化,进一步要求提高玻璃的应变点,因此所述问题变得更加显著。
此外,由于所述专利文献2所揭示的玻璃的应变点为682~699℃,因此为了设为比如使热缩充分地缩小的平均密度曲线的斜率,必须使缓冷速度极慢,存在生产性降低的问题。而且,专利文献2所揭示的玻璃由于失透温度为1287℃以上,因此也存在容易产生失透的问题。此外,所述问题在使用下拉法进行成形的情况下变得特别显著。
而且,在使用玻璃基板的显示器的制造中要求提高生产性,例如也要求提高将形成有薄膜晶体管的玻璃基板制成薄板的步骤的生产性。将玻璃基板制成薄板的步骤的生产性较大地依赖于玻璃基板的蚀刻所耗的时间。因此,要求显示器玻璃基板同时实现蚀刻速率的上升所带来的生产性的提高及热缩率的降低。然而,关于所述专利文献4所记载的玻璃基板,应变点虽较高,但仍存在并未顾虑到蚀刻速率的问题。
因此,本发明的目的在于提供一种将失透温度抑制得较低并且满足高应变点的玻璃基板、及其制造方法。本发明的目的尤其在于提供一种适合使用LTPS-TFT或者OS-TFT的显示器的显示器用玻璃基板及其制造方法。
[解决问题的技术手段]
本发明如以下所述。
[1]
一种显示器用玻璃基板,包含以下玻璃,该玻璃含有SiO2、Al2O3,
以质量%表示,
B2O3为0%以上且未达3%,
BaO为5~14%,
实质上不含有Sb2O3,
失透温度为1235℃以下,且
应变点为720℃以上。
[2]
一种显示器用玻璃基板,包含以下玻璃,该玻璃含有SiO2、Al2O3,
以质量%表示,
B2O3为0%以上且未达3%,
MgO为1.8%以上,
BaO为5~14%,
实质上不含有Sb2O3,
(SiO2+MgO+CaO)-(Al2O3+SrO+BaO)未达42%,
失透温度为1260℃以下,且
应变点为720℃以上。
[3]
如[1]至[2]中任一项的玻璃基板,其中所述玻璃基板在500℃的温度下保持30分钟,然后放冷至常温的情况下的由下述式所表示的热缩率为15ppm以下。
热缩率(ppm)={热处理前后的玻璃的收缩量/热处理前的玻璃的长度}×106
[4]
如[1]至[3]中任一项的玻璃基板,其中所述玻璃基板的蚀刻速率大于75μm/h。
[5]
如[1]至[4]中任一项的玻璃基板,在玻璃基板表面形成有使用低温多晶硅或氧化物半导体而形成的薄膜晶体管的平板显示器用玻璃基板。
[6]
一种显示器用玻璃基板的制造方法,制造如[1]至[5]中任一项的玻璃基板,且包含:
熔解步骤,至少使用直接通电加热使调制成特定组成的玻璃原料熔解;
成形步骤,使在所述熔解步骤中熔解所得的熔融玻璃成形为平板状玻璃;及
缓冷步骤,使所述平板状玻璃缓冷,并且以降低所述平板状玻璃的热缩率的方式控制所述平板状玻璃的冷却条件。
[发明的效果]
根据所述本发明的玻璃基板,可制造将失透温度抑制得较低并且满足高应变点的玻璃基板。由此,可以较高的生产性提供可减少制造显示器时的热缩的显示器用玻璃基板、尤其是适合使用LTPS-TFT或OS-TFT的平板显示器的显示器用玻璃基板。
具体实施方式
在本申请说明书中,关于玻璃的组成,只要未特别说明,则含量以质量%表示,以%表示含量是指质量%。构成玻璃组成的成分的比以质量比表示。
本发明的显示器用玻璃基板(第一形态)包含以下玻璃,
该玻璃含有SiO2、Al2O3,
以质量%表示,
B2O3为0%以上且未达3%,
BaO为5~14%,
实质上不含有Sb2O3,
失透温度为1235℃以下,且
应变点为720℃以上。
本发明的显示器用玻璃基板(第二形态)包含以下玻璃,
该玻璃含有SiO2、Al2O3,
以质量%表示,
B2O3为0%以上且未达3%,
MgO为1.8%以上,
BaO为5~14%,
实质上不含有Sb2O3,
(SiO2+MgO+CaO)-(Al2O3+SrO+BaO)未达42%,
失透温度为1260℃以下,且
应变点为720℃以上。
以下,对本实施方式的显示器用玻璃基板的实施方式进行说明。另外,只要未特别说明,则以下的说明对本发明的第一形态及第二形态共通。
构成本发明的显示器用玻璃基板的玻璃含有SiO2及Al2O3。
SiO2是玻璃的骨架成分,因此为必需成分。若含量减少,则有应变点降低、热膨胀系数增加的倾向。此外,若SiO2含量过少,则难以使玻璃基板低密度化。另一方面,若SiO2含量过多,则有熔融玻璃的比电阻上升、熔融温度显著增高而难以熔解的倾向。而且,若SiO2含量过多,则蚀刻速率减慢。就此种观点来说,可适当调整SiO2的含量。玻璃的SiO2含量例如优选为40~80%的范围。SiO2的含量更优选为50~75%或者50~70%、进一步优选为52~68%、进一步更优选为55~65%的范围。
Al2O3是提高应变点的必需成分。若Al2O3含量过少,则应变点降低。而且,若Al2O3含量过少,则有杨氏模量及利用酸进行的蚀刻速率也降低的倾向。另一方面,若Al2O3含量过多,则玻璃的失透温度上升,耐失透性降低,因此有成形性变差的倾向。就此种观点来说,可适当调整。玻璃的Al2O3的含量例如为10~35%的范围。Al2O3的含量优选为13~30%,更优选为15~25%,更优选为15~23%,进一步优选为16~22%的范围。
B2O3是使玻璃的高温粘性降低而改善熔融性的成分。即,使熔融温度附近下的粘性降低,因此改善熔解性。此外,B2O3也是使失透温度降低的成分。若B2O3含量较少,则有熔解性及耐失透性降低的倾向。若B2O3含量过多,则应变点及杨氏模量降低。此外,因玻璃成形时的B2O3的挥发而容易产生失透。尤其是应变点较高的玻璃具有成形温度增高的倾向,因此促进所述挥发而产生失透会成为显著的问题。此外,因玻璃熔解时的B2O3的挥发而导致玻璃的不均质变得显著,从而容易产生脉理。就此种观点来说,B2O3含量为0%以上且未达3%。B2O3含量优选为0~2.8%,更优选为0~2.6%,进一步优选为0.1~2.4%、进一步优选为0.3~2.2%、进一步更优选为0.5~2.0%的范围。
MgO是提高熔解性的成分,在本发明的第二形态中是必需成分。此外,在碱土金属中是难以使密度增加的成分,因此若使其含量相对地增加,则容易实现低密度化。若含有MgO,则可降低熔融玻璃的比电阻及熔融温度。但是,若MgO的含量过多,则玻璃的失透温度急剧上升,因此特别容易在成形步骤中失透。就此种观点来说,在本发明的第二形态中,MgO含量为1.8~15%,优选为1.8~13%、更优选为1.9~10%、进一步优选为1.9~7%的范围。或者,在本发明的第一形态中,MgO含量优选为0~15%、更优选为0~13%、进一步优选为0~10%的范围。
CaO是并非为必需,但若含有,则对不会使玻璃的失透温度急剧上升并使玻璃的熔解性提高有效的成分。此外,在碱土金属氧化物中是难以使密度增加的成分,因此若使其含量相对地增加,则容易实现低密度化。若含量过少,则有产生熔融玻璃的比电阻的上升及耐失透性降低的倾向。若CaO含量过多,则有热膨胀系数增加、密度上升的倾向。就此种观点来说,CaO含量优选为0~20%、更优选为0~15%、进一步优选为0~10%的范围。
SrO是可降低玻璃的失透温度的成分。SrO虽并非必需,但若含有,则耐失透性及熔解性提高。然而,若SrO含量过多,则密度会上升。就此种观点来说,SrO含量为0~15%,优选为0~10%、更优选为0~7%、进一步优选为0~5%、进一步优选为0~3%的范围。
BaO是可使玻璃的失透温度及熔融玻璃的比电阻有效地降低的必需成分。若含有BaO,则耐失透性及熔解性提高。然而,若BaO的含量过多,则密度上升。此外,就环境负担的观点、及具有热膨胀系数增大的倾向的方面来说,BaO含量为5~14%的范围。BaO含量优选为6~13.5%,更优选为7~13%,进一步优选为8~12%,进一步优选为8.5~12%的范围。
MgO、CaO、SrO及BaO是使熔融玻璃的比电阻及熔融温度降低而提高熔解性的成分。若MgO、CaO、SrO及BaO的含量的总量即MgO+CaO+SrO+BaO(以下表示成RO)过少,则熔解性变差。若RO过多,则应变点及杨氏模量降低、密度及热膨胀系数上升。就此种观点来说,RO优选为5~35%的范围,更优选为9~30%、进一步优选为10~27%、进一步优选为12~25%的范围。
Li2O及Na2O是增大玻璃的热膨胀系数而在热处理时有使基板破损的可能的成分。此外,Li2O及Na2O也是使应变点降低的成分。另一方面,由于可使熔融玻璃的比电阻降低,因此若含有便可抑制熔解槽被侵蚀。就以上观点来说,Li2O的含量优选为0~0.5%,更优选为实质上不含有。Na2O的含量优选为0~0.5%,更优选为0~0.2%。另外,Na2O是与Li2O相比不易使应变点降低的成分,因此优选为Na2O>Li2O。另外,就防止从玻璃基板溶出而使TFT特性劣化的观点来说,Li2O及Na2O优选为实质上不含有。
K2O是提高玻璃的碱性度、促进澄清性的成分。此外,K2O是使熔融玻璃的比电阻降低的成分。若含有,则熔融玻璃的比电阻降低,因此可防止电流流过构成熔解槽的耐火物,从而可抑制熔解槽被侵蚀。此外,在构成熔解槽的耐火物含有氧化锆的情况下,可抑制熔解槽被侵蚀而氧化锆从熔解槽溶出至熔融玻璃,因此也可抑制因氧化锆而导致的失透。此外,由于可使熔解温度附近下的玻璃粘性降低,因此熔解性与澄清性提高。另一方面,若K2O含量过多,则有热膨胀系数增大及应变点降低的倾向。就此种观点来说,K2O含量优选为0~0.8%、更优选为0.01~0.6%、进一步优选为0.1~0.5%的范围。
Li2O、Na2O及K2O是提高玻璃的碱性度、使澄清剂的氧化容易而发挥澄清性的成分。此外,Li2O、Na2O及K2O是使熔融温度下的粘性降低而提高熔解性的成分。此外,Li2O、Na2O及K2O也是使熔融玻璃的比电阻降低的成分。若含有Li2O、Na2O及K2O,则熔融玻璃的比电阻降低,澄清性及熔解性提高。尤其是可防止电流过度流过构成熔解槽的耐火物,从而可抑制熔解槽被侵蚀。此外,在熔解槽含有氧化锆的情况下,可抑制氧化锆从熔解槽溶出至玻璃,因此也可抑制因氧化锆而导致的失透。此外,由于使熔解玻璃的粘性降低,因此熔解性与澄清性提高。然而,若Li2O、Na2O及K2O的含量的总量过多,则有从玻璃基板溶出而使TFT特性劣化的可能。此外,有应变点降低、热膨胀系数增大的倾向。Li2O、Na2O及K2O的含量的总量(以下表示成R2O)优选为1.0%以下,进一步优选为0.01~1.0%,进一步优选为0.01~0.8%,进一步更优选为0.1~0.5%。
ZrO2及TiO2是使玻璃的应变点提高的成分。然而,若ZrO2量及TiO2量变得过多,则失透温度明显上升,因此有耐失透性降低的倾向。尤其是ZrO2的熔点较高而难熔,因此会引起原料的一部分堆积在熔解槽的底部等问题。若这些未熔解的成分混入至玻璃生坯,则会作为内含物引起玻璃的质量变差。此外,TiO2是使玻璃着色的成分,因此对显示器用基板来说不佳。就此种观点来说,在本实施方式的玻璃基板中,ZrO2及TiO2的含量分别优选为0~10%、更优选为0~5%的范围,进一步优选为实质上不含有。
ZnO是使熔解性提高的成分。但是,并非为必需成分。若ZnO含量变得过多,则有失透温度上升、应变点降低、密度上升的倾向。就此种观点来说,ZnO含量优选为0~5%、更优选为0~2%的范围,进一步优选为实质上不含有。
本实施方式的玻璃基板可包含澄清剂。作为澄清剂,只要环境负担小且玻璃的澄清性优秀,则并无特别限制,例如可列举选自Sn、Fe、Ce、Tb、Mo、及W的金属氧化物的群中的至少1种。本实施方式的玻璃基板实质上不包含Sb2O3。通过实质上不包含Sb2O3,可减少环境负担。作为澄清剂,优选为SnO2。若澄清剂的含量过少,则泡质量变差,若过多,则存在导致失透或着色等的情况。澄清剂的含量也取决于澄清剂的种类或玻璃的组成。例如SnO2及Fe2O3的总量优选为0.05~0.50%,更优选为0.05~0.40%。
SnO2是即便在1600℃以上也可获得澄清效果的澄清剂,且是可用于制造仅可含有微量的Li2O、Na2O及K2O的平板显示器用玻璃基板(例如Li2O、Na2O及K2O的总量为0.01~0.8%)的少数澄清剂。然而,SnO2本身为容易产生失透的成分,并且是会促进其它成分产生失透的成分,因此就抑制失透的观点来说,不宜大量添加。
此外,应变点较高的玻璃(例如应变点为720℃以上的玻璃)与应变点较低的玻璃(例如应变点未达720℃的玻璃)相比具有失透温度容易增高的倾向,因此为了抑制失透,存在与应变点较低的玻璃相比不得不提高成形步骤中的熔融玻璃的温度的情况。此处,就耐蠕变性、耐热性的观点来说,溢流下拉法所使用的成形体优选为包含含有氧化锆的耐火物而构成。在采用溢流下拉作为成形方法的情况下,越要提高成形步骤中的熔融玻璃的温度,必须也使成形体的温度上升。然而,若成形体的温度增高,则存在氧化锆从成形体溶出而容易产生该氧化锆的失透的问题。此外,尤其是在大量含有SnO2的玻璃中,具有容易产生因该氧化锆而导致的SnO2的失透、因SnO2而导致的氧化锆的失透的倾向。
而且,应变点较高的玻璃(例如应变点为720℃以上的玻璃)与应变点较低的玻璃(例如应变点未达720℃的玻璃)相比,有使玻璃原料熔解的温度也容易增高的倾向。此处,就耐侵蚀性的观点来说,进行熔解步骤的熔解槽优选为包含含有氧化锆的高氧化锆系耐火物而构成。此外,就能量效率的观点来说,优选为通过电熔融或者电熔融与其它加热方法的组合而使玻璃原料熔解。然而,在使本实施方式所记载般的高应变点且仅可含有微量的Li2O、Na2O及K2O的玻璃熔解的情况下,由于熔融玻璃的比电阻较大,因此电流会流过高氧化锆系耐火物,而容易产生氧化锆溶出至熔融玻璃中的问题。若氧化锆溶出,则有容易产生所述氧化锆的失透及SnO2的失透的倾向。
即,就抑制氧化锆及SnO2的失透的观点来说,在本实施方式的玻璃基板中,含有的SnO2不宜超过0.8%。就此种观点来说,SnO2含量例如优选为0.01以上且0.8%以下,优选为0.02~0.6%,更优选为0.05~0.50%、进一步优选为0.05~0.40%的范围。
Fe2O3是除具有作为澄清剂的作用以外也会使熔融玻璃的比电阻降低的成分。优选为为了使熔融玻璃的比电阻降低而在高温粘性较高、难熔解性的玻璃中含有。然而,若Fe2O3含量变得过多,则玻璃着色而透过率降低。因此Fe2O3含量为0~0.1%的范围,优选为0~0.08%、更优选为0.001~0.06%、进一步优选为0.001~0.05%、进一步优选为0.001~0.04%的范围。
在本实施方式中,澄清剂优选为将SnO2与Fe2O3组合。就抑制失透的观点来说,如上所述,不宜大量含有SnO2。然而,为了充分地获得澄清效果,要求含有特定值以上的澄清剂。因此,通过将SnO2与Fe2O3并用,可在不使SnO2的含量多至产生失透的程度的情况下获得充分的澄清效果,从而可制造泡较少的玻璃基板。SnO2与Fe2O3的总量优选为0.05~0.50%的范围,更优选为0.05~0.45%、进一步优选为0.05~0.40%的范围。
若SnO2的含量相对于SnO2与Fe2O3的总量的质量比(SnO2/(SnO2+Fe2O3))过大,则容易产生失透,若过小,则存在无法获得充分的澄清效果而导致玻璃着色的情况。因此,优选为0.6~1.0的范围,更优选为0.7~0.98的范围。
就环境负担的问题来说,本实施方式的玻璃基板优选为实质上不含有As2O3。就环境负担的问题来说,本实施方式的玻璃基板实质上不含有Sb2O3。
就环境方面的原因来说,本实施方式的玻璃基板优选为实质上不含有PbO及F。
另外,在本说明书中,所谓“实质上不含有”,是指在所述玻璃原料中未使用成为这些成分的原料的物质,并不排除以杂质的形式包含在其它成分的玻璃原料中的成分、从熔解槽、成形体等的制造装置溶出至玻璃的成分的混入。
若SiO2的含量与Al2O3的1/4的含量的差SiO2-(1/4×Al2O3)的值过大,则有蚀刻速率降低的可能。就此种观点来说,SiO2-(1/4×Al2O3)为65以下。另一方面,若SiO2-(1/4×Al2O3)的值过小,则有耐失透性降低的可能。就此种观点来说,SiO2-(1/4×Al2O3)优选为40%~65%,进一步优选为45%~60%,进一步优选为50%~55%。
SiO2、MgO及CaO的总量与Al2O3、SrO、BaO的差即(SiO2+MgO+CaO)-(Al2O3+SrO+BaO)成为蚀刻速率的指标,若值过大,则蚀刻速率降低。另一方面,若值过小,则耐失透性降低。就此种观点来说,(SiO2+MgO+CaO)-(Al2O3+SrO+BaO)优选为未达42%,更优选为41%以下、进一步优选为25~41%、进一步优选为30~40%的范围。
质量比(SiO2+Al2O3)/(B2O3+RO)主要成为应变点与耐失透性的指标。若值过小,则应变点降低。另一方面,若值过大,则熔解性及耐失透性降低。因此,质量比(SiO2+Al2O3)/(B2O3+RO)优选为1~8、更优选为2~7、进一步优选为2.5~6.5、进一步优选为3~6的范围。
B2O3+RO+ZnO主要成为溶解性的指标。若值过小,则溶解性降低。另一方面,若值过大,则应变点降低、热膨胀系数增加。就此种观点来说,B2O3+RO+ZnO优选为5~35%的范围,更优选为9~30%、进一步优选为12~28%、进一步优选为15~25%的范围。
若SiO2的含量与Al2O3的含量的总量即SiO2+Al2O3过少,则有应变点降低的倾向,若过多,则有耐失透性变差的倾向。因此SiO2+Al2O3优选为70~90%,优选为73~88%、更优选为75~85%、进一步优选为77~83%的范围。
质量比B2O3/(SiO2+Al2O3)主要成为溶解性、耐失透性、应变点的指标。若B2O3/(SiO2+Al2O3)过大,则应变点降低。另一方面,若B2O3/(SiO2+Al2O3)过小,则具有溶解性及耐失透性变差的倾向。B2O3/(SiO2+Al2O3)优选为0~0.050、更优选为0~0.045、进一步优选为0.001~0.040、进一步优选为0.005~0.035的范围。
若质量比SiO2/Al2O3的值过大,则有蚀刻速率降低的可能,若值过小,则有耐失透性降低的可能。就此种观点来说,质量比SiO2/Al2O3优选为1.5~4.5,更优选为2.0~4.0、进一步优选为2.5~3.7的范围。另外,在具有SiO2+Al2O3的值接近的组成的玻璃中,蚀刻速率更显著地依赖SiO2/Al2O3。就兼顾高应变点、耐失透性、蚀刻速率的观点来说,优选为SiO2+Al2O3为70~90%且SiO2/Al2O3为1.5~4.5,更优选为SiO2+Al2O3为73~88%且SiO2/Al2O3为2.0~4.0的范围。
B2O3及RO均为使溶解性良化的成分。B2O3具有使耐失透性良化的效果,但若过多,则应变点降低。另一方面,RO具有使玻璃的比电阻降低的效果,但若过多,则耐失透性降低。就兼顾溶解性与耐失透性的观点来说,质量比B2O3/RO优选为处于0~0.5的范围,更优选为0~0.4、进一步优选为0.01~0.3、进一步优选为0.02~0.2的范围。
质量比BaO/RO的值过小或过大,失透温度均会上升。此外,若BaO/RO的值增大,则杨氏模量下降,进一步密度上升,比电阻也上升。因此,质量比BaO/RO优选为0~0.9,优选为0.1~0.85、更优选为0.2~0.8的范围。
质量比(3×BaO)/(MgO+CaO+SrO)的值过小或过大,失透温度均会上升。另一方面,若(3×BaO)/(MgO+CaO+SrO)的值增大,则杨氏模量下降,进一步密度上升,比电阻也上升。因此,质量比(3×BaO)/(MgO+CaO+SrO)优选为5.0以下、优选为0.5~5、更优选为1~5的范围。
为了不过分增大密度并使失透温度有效地降低,质量比CaO/RO优选为0~0.8、更优选为0.1~0.7、进一步优选为0.15~0.6、进一步优选为0.2~0.5的范围。
若质量比(MgO/(RO+ZnO))的值较小,则具有失透温度降低、杨氏模量下降的倾向。而且,密度上升,比电阻也上升。另一方面,若值较大,则失透温度上升,杨氏模量下降。因此,质量比(MgO/(RO+ZnO))优选为0.01~0.8、优选为0.02~0.6、0.03~0.4的范围。
若质量比SrO/CaO的值较小,则具有失透温度降低、杨氏模量下降的倾向。而且,密度上升,比电阻也上升。另一方面,若值较大,则失透温度上升,杨氏模量下降。因此,质量比(MgO/(CaO+SrO))为0.6以下,优选为0.36以上,优选为0.4以上。
质量比(SiO2+Al2O3)/(B2O3+RO+(10×R2O))主要成为应变点与熔解性的指标。若值过小,则应变点降低。因此,质量比(SiO2+Al2O3)/(B2O3+RO+(10×R2O))为1.0以上,优选为2.0以上的范围。另一方面,若值过大,则熔解性及耐失透性降低。因此,质量比(SiO2+Al2O3)/(B2O3+RO+(10×R2O))优选为1.0~10、更优选为2.0~7的范围。(SiO2+Al2O3)/(B2O3+RO+(10×R2O))优选为2.5~5。
所谓RE2O3,是稀土类金属氧化物的总量,作为稀土类金属氧化物,可列举Sc2O3、Y2O3、La2O3、Pr2O3、Nd2O3、Sm2O3、Eu2O3、Gd2O3、Tb2O3、Dy2O3、Ho2O3、Er2O3、Tm2O3、Yb2O3、Lu2O3为例。RE2O3是使密度及热膨胀系数增加的成分。此外,RE2O3是成本也较高的成分。因此,RE2O3为0以上且未达1.0%(包含0),更优选为0~0.5%(包含0)的范围,尤其优选为实质上不含有。
就防止密度及热膨胀系数的增加且降低成本的观点来说,优选为实质上不含有Y2O3及La2O。
在本发明的第二形态中,玻璃基板的失透温度为1260℃以下。优选为1250℃以下,更优选为1240℃以下,进一步优选为1230℃以下,进一步优选为1220℃以下。另一方面,在本发明的第一形态中,玻璃基板的失透温度为1235℃以下,优选为1230℃以下,更优选为1225℃以下,进一步优选为1220℃以下,进一步优选为1210℃以下。失透温度越低,越容易利用溢流下拉法使玻璃板成形。通过应用溢流下拉法,可省略对玻璃基板表面进行研磨的步骤,因此可提高玻璃基板的表面质量。此外,也可降低生产成本。若失透温度过高,则容易产生失透,因此具有难以应用于溢流下拉法的倾向。
本实施方式的玻璃基板的100℃~300℃下的平均热膨胀系数(100-300℃)为50.0×10-7℃-1以下,优选为28.0~50.0×10-7℃-1,更优选为33.0~47.0×10-7℃-1、进一步优选为33.0~46.0×10-7℃-1、进一步优选为35.0~44.0×10-7℃-1、进一步更优选为38.0~43.0×10-7℃-1的范围。若热膨胀系数较大,则具有在热处理步骤中热冲击或热缩率增大的倾向。此外,若热膨胀系数较大,则难以降低热缩率。另外,热膨胀系数较大或较小,均难以获得形成在玻璃基板上的金属、薄膜等周边材料与热膨胀系数的匹配而有周边构件剥离的可能。
通常,若玻璃基板的应变点较低,则在制造显示器时的热处理步骤中容易产生热缩。本实施方式的玻璃基板的应变点为720℃以上,优选为725℃以上,更优选为730℃以上,进一步优选为735℃以上。
本实施方式的玻璃基板的热缩率优选为15ppm以下。若热缩率变得过大,则会引起像素的较大的间距偏差,从而无法实现高精细的显示器。为了将热缩率控制在特定范围,优选为将玻璃基板的应变点设为720℃以上或者730℃以上。另外,若欲使热缩率为0ppm,则要求极度延长缓冷步骤或在缓冷、切断步骤后实施热缩降低处理(脱机缓冷),在此情况下,生产性降低、成本增高。若鉴于生产性及成本,则热缩率例如优选为0.1ppm~15ppm、或者0.5ppm~15ppm,更优选为1ppm~15ppm,进一步优选为1ppm~13ppm,进一步优选为2ppm~10ppm。
另外,热缩率是由实施了将玻璃基板在500℃的温度下保持30分钟,然后放冷至常温的热处理后的下述式所表示。
热缩率(ppm)={热处理前后的玻璃的收缩量/热处理前的玻璃的长度}×106
此时,所谓“热处理前后的玻璃的收缩量”,是“热处理前的玻璃的长度-热处理后的玻璃的长度”。
就玻璃基板的轻量化及显示器的轻量化的观点来说,本实施方式的玻璃基板的密度优选为3.0g/cm3以下,更优选为2.8g/cm3以下,进一步优选为2.65g/cm3以下。若密度变得过高,则玻璃基板的轻量化变得困难,显示器的轻量化也难以实现。
若玻璃的转移点(以下记载为Tg)降低,则具有在显示器制造的热处理步骤中容易产生热缩的倾向。本实施方式的玻璃基板的Tg优选为770℃以上,更优选为775℃以上,进一步优选为780℃以上。为了将玻璃基板的Tg设为所述范围,优选为在本实施方式的玻璃基板的组成的范围中,使例如SiO2及Al2O3等成分增多或者使B2O3、RO、R2O的成分减少。
本实施方式的玻璃显示出黏度为102.5[dPa·s]的温度(以下记为熔融温度)优选为1680℃以下,更优选为1500~1680℃的范围,进一步优选为1520~1660℃、进一步优选为1540~1640℃的范围。熔融温度较低的玻璃的应变点容易降低。为了提高应变点,也需要将熔融温度提高至某一程度。但是,若熔融温度较高,则对熔解槽的负荷增大。此外,由于大量使用能源,因此成本也增高。此外,在将电熔解应用于玻璃熔解的情况下,有电流并非流过玻璃而是流过形成熔解槽的耐热炼砖而导致熔解槽破损的可能。为了将玻璃的熔融温度设为所述范围,优选为在本实施方式的玻璃基板的组成的范围内,在所述范围内含有使黏度降低的例如B2O3、RO等成分。
制造本实施方式的玻璃基板时的熔融玻璃的比电阻(1550℃下)优选为30~700Ω·cm、更优选为30~400Ω·cm、进一步优选为30~300Ω·cm、进一步优选为50~300Ω·cm的范围。若比电阻变得过小,则存在熔解所需的电流值变得过大而产生设备上的限制的情况。此外,也有电极的消耗增多的倾向。若熔融玻璃的比电阻变得过大,则也存在电流并非流过玻璃而是流过形成熔解槽的耐热炼砖而导致熔解槽破损的情况。熔融玻璃的比电阻主要可通过控制RO、R2O、Fe2O3的含量而调整为所述范围。
构成本实施方式的玻璃基板的玻璃的蚀刻速率优选为50μm/h以上。若蚀刻速率变快,则生产性提高。尤其是在将TFT侧与彩色滤光片侧的玻璃基板贴合后进行玻璃基板的蚀刻而实现轻量化的情况下,蚀刻速率影响生产性。然而,若蚀刻速率变得过高,则制造显示器时的生产性虽提高,但玻璃的耐失透性降低。此外,热缩率也容易增大。蚀刻速率优选为60~140μm/h,更优选为70~120μm/h,进一步优选为大于75且120μm/h以下,进一步优选为77~120μm/h。为了提高玻璃的蚀刻速率,只要使SiO2+MgO+CaO-(Al2O3+SrO+BaO)、SiO2-(1/4×Al2O3)、或者SiO2/Al2O3的值缩小即可。在本实施方式中,所述蚀刻速率定义成在以下条件下所测得者。所谓本说明书中的蚀刻速率(μm/h),是将玻璃基板浸渍在以HF浓度成为1mol/kg、HCl浓度成为5mol/kg的方式进行了调整后的40℃的蚀刻液中1小时的情况下的每单位时间(1小时)的玻璃基板的一表面的厚度减少量(μm)。
本实施方式的玻璃基板的板厚例如可为0.1~1.1mm、或者0.3~1.1mm的范围。但是,并无意图限定为该范围。板厚例如也可为0.3~0.7mm、0.3~0.5mm的范围。若玻璃板的厚度过薄,则玻璃基板本身的强度降低。例如容易产生制造平板显示器时的破损。若板厚过厚,则对于要求薄型化的显示器来说不佳。此外,由于玻璃基板的重量变重,因此难以实现平板显示器的轻量化。而且,在形成TFT后进行玻璃基板的蚀刻处理的情况下,蚀刻处理量增多而耗费成本与时间。
本实施方式的玻璃基板用于制造例如在阵列彩色滤光片贴合后对玻璃基板表面进行蚀刻处理的平板显示器。本实施方式的玻璃基板适合显示器用玻璃基板(其中,CRT(布朗管)显示器除外)。本实施方式的玻璃基板特别适合形成有LTPS-TFT或OS-TFT的平板显示器用玻璃基板。具体来说,适合液晶显示器用玻璃基板、有机EL显示器用玻璃基板。特别适合LTPS-TFT液晶显示器用玻璃基板、LTPS-TFT有机EL显示器用玻璃基板。其中,适合要求高精细的移动终端等的显示器用玻璃基板。
<平板显示器>
本实施方式包含在玻璃基板表面形成有LTPS-TFT或OS-TFT的平板显示器,该平板显示器的玻璃基板是所述本实施方式的玻璃基板。本实施方式的平板显示器例如可为液晶显示器或有机EL显示器。
<玻璃基板的制造方法>
本实施方式的显示器用玻璃基板的制造方法具有:熔解步骤,例如至少使用直接通电加热使调制成特定组成的玻璃原料熔解;成形步骤,使在所述熔解步骤中熔解所得的熔融玻璃成形为平板状玻璃;及缓冷步骤,使所述平板状玻璃缓冷。
所述缓冷步骤尤其优选为以降低所述平板状玻璃的热缩率的方式控制所述平板状玻璃的冷却条件的步骤。
[熔解步骤]
在熔解步骤中,例如使用直接通电加热及/或燃烧加热使以具有特定组成的方式进行调制而成的玻璃原料熔解。玻璃原料可从公知的材料中适当选择。就能量效率的观点来说,优选为在熔解步骤中至少使用直接通电加热使玻璃原料熔解。此外,进行熔解步骤的熔解槽优选为包含高氧化锆系耐火物而构成。所述特定组成例如可在玻璃的各成分满足所述含量的范围内进行适当调整。
[成形步骤]
在成形步骤中,使在熔解步骤中熔解所得的熔融玻璃成形为平板状玻璃。成形为平板状玻璃的方法例如优选为下拉法,尤其优选为溢流下拉法,并形成玻璃带作为平板状玻璃。此外,可应用浮式法、再拉法、滚压法等。通过采用下拉法,与使用浮式法等其它成形方法的情况相比,所获得的玻璃基板的主表面是以仅接触氛围的自由表面形成,因此具有极高的平滑性,且无需成形后的玻璃基板表面的研磨步骤,因此可降低制造成本,进一步也可提高生产性。而且,使用下拉法而成形的玻璃基板的两主表面具有均匀的组成,因此在进行蚀刻处理时,可无关成形时的正背面而均匀地进行蚀刻。
[缓冷步骤]
通过适当调整缓冷时的条件,可控制玻璃基板的热缩率。尤其优选为以降低所述平板状玻璃的热缩率的方式控制所述平板状玻璃的冷却条件。玻璃基板的热缩率如上所述为15ppm以下,优选为13ppm以下,更优选为1~13ppm。为了制造具有此种数值的热缩率的玻璃基板,例如在使用下拉法的情况下,优选为以使作为平板状玻璃的玻璃带的冷却速度在Tg至(Tg-100℃)的温度范围内成为30~300℃/min的方式进行缓冷。若冷却速度过快,则无法充分降低热缩率。另一方面,若冷却速度过慢,则会产生生产性降低并且玻璃制造装置(缓冷炉)大型化的问题。冷却速度的优选范围为30~300℃/min,更优选为50~200℃/min,进一步优选为60~120℃/min。通过将冷却速度设为30~300℃/min,可更确实地制造本实施方式的玻璃基板。另外,在缓冷步骤的下游将平板状玻璃切断后,另外脱机进行缓冷,由此也可降低热缩率,在此情况下,除进行缓冷步骤的设备以外,也需要另外脱机进行缓冷的设备。因此,如上所述,就生产性及成本的观点来说,优选为以可省略脱机缓冷的方式且可在缓冷步骤中降低热缩率的方式进行控制。另外,在本说明书中,所谓玻璃带的冷却速度,表示玻璃带的宽度方向中央部的冷却速度。
[实施例]
以下,基于实施例对本实施方式更详细地进行说明。但是,本实施方式并不限定于实施例。在下述所示的实施例、比较例中,测量以下要说明的物性。
(应变点)
使用弯梁测定装置(东京工业股份有限公司制造)进行测定,并根据弯梁法(ASTMC-598)通过计算求出应变点。
(失透温度)
将玻璃粉碎,使其通过2380μm的筛网,并将残留在1000μm的筛网上的玻璃粒放入至铂舟。将该铂舟在具有1050~1380℃的温度梯度的电炉内保持5小时,然后从炉中取出,利用50倍的光学显微镜对玻璃内部所产生的失透进行观察。将观察到失透的最高温度设为失透温度。
(100~300℃的范围内的平均热膨胀系数α及Tg的测定方法)
使用示差热膨胀计(Thermo Plus2TMA8310)进行测定。此时的升温速度设为5℃/min。基于测定结果求出100~300℃的温度范围内的平均热膨胀系数及Tg。
(热缩率)
关于90mm~200mm×15~30mm×0.3~1mm的大小的玻璃,利用划线法求出热缩率。作为热缩测定的热处理,使用空气环流炉(Nabertherm制造的N120/85HA),在500℃的温度下保持30分钟,并放冷至室温为止。
热缩率(ppm)={热处理下的玻璃的收缩量/热处理前的玻璃的划线间距离}×106
另外,在测定将玻璃原料在铂坩锅中熔解后使其流出至铁板上并进行冷却固化而获得的玻璃的热缩的情况下,使用以成为0.5mm的厚度的方式实施切断、研削、研磨,并使用电炉在Tg+15℃的温度下保持30分钟后,以降温速度150~250℃/min的速度取出至炉外的玻璃。
(密度)
玻璃的密度是通过阿基米得法进行测定。
(蚀刻速率)
蚀刻速率(μm/h)是通过测定将玻璃(12.5mm×20mm×0.7mm)浸渍在以HF浓度成为1mol/kg、HCl浓度成为5mol/kg的方式进行了调整后的40℃的蚀刻液(200mL)中1小时的情况下的厚度减少量(μm),并算出每单位时间(1小时)的玻璃基板的一表面的厚度减少量(μm)而求出。
以下,对实施例的组成与评价进行说明。
以成为表1所示的玻璃组成的方式根据以下顺序制作实施例1~63的玻璃。对于所获得的玻璃,求出应变点、失透温度、Tg、100~300℃的范围内的平均热膨胀系数(α)、热缩率、密度、蚀刻速率。
[表1-1]
[表1-2]
[表1-3]
[表1-4]
[表1-5]
[表1-6]
[表1-7]
[表1-8]
[表1-9]
[表1-10]
[表1-11]
以成为表1所示的玻璃组成的方式调制各成分的原料并进行熔解、澄清、成形。
以所述方式而获得的玻璃中的实施例1~63的失透温度为1260℃以下,且应变点为720℃以上(如技术方案2的玻璃基板的实施例)。其中,实施例1~6、9、15~18、21、25、29~31、34~45、47~57、59~60的失透温度为1235℃以下,且应变点为720℃以上(比如技术方案1的玻璃基板的实施例)。此外,在使用直接通电加热使玻璃原料熔解并利用溢流下拉法制造玻璃基板的情况下,也获得同样的结果。因此,通过使用这些玻璃,可利用溢流下拉法制造可用于应用有LTPS-TFT的显示器的玻璃基板。此外,这些玻璃基板也适合作为OS-TFT用玻璃基板。
Claims (6)
1.一种显示器用玻璃基板,包含以下玻璃,该玻璃含有SiO2、Al2O3,
以质量%表示,
B2O3为0%以上且未达3%,
BaO为5~14%,
实质上不含有Sb2O3,
失透温度为1235℃以下,且
应变点为720℃以上。
2.一种显示器用玻璃基板,包含以下玻璃,该玻璃含有SiO2、Al2O3,
以质量%表示,
B2O3为0%以上且未达3%,
MgO为1.8%以上,
BaO为5~14%,
实质上不含有Sb2O3,
(SiO2+MgO+CaO)-(Al2O3+SrO+BaO)未达42%,
失透温度为1260℃以下,且
应变点为720℃以上。
3.根据权利要求1或2所述的玻璃基板,其中所述玻璃基板在500℃的温度下保持30分钟,然后放冷至常温的情况下的下述式所表示的热缩率为15ppm以下,
热缩率(ppm)={热处理前后的玻璃的收缩量/热处理前的玻璃的长度}×106。
4.根据权利要求1至3中任一项所述的玻璃基板,其中所述玻璃基板的蚀刻速率大于75μm/h。
5.根据权利要求1至4中任一项所述的玻璃基板,在玻璃基板表面形成有使用低温多晶硅或氧化物半导体而形成的薄膜晶体管的平板显示器用玻璃基板。
6.一种显示器用玻璃基板的制造方法,制造权利要求1至5中任一项所述的玻璃基板,且包含:
熔解步骤,至少使用直接通电加热而使调制成特定组成的玻璃原料熔解;
成形步骤,使在所述熔解步骤中熔解所得的熔融玻璃成形为平板状玻璃;及
缓冷步骤,使所述平板状玻璃缓冷,并且以降低所述平板状玻璃的热缩率的方式控制所述平板状玻璃的冷却条件。
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