TWI462829B - Glass member having sealing material layer and method for manufacturing the same, and electronic device and manufacturing method thereof - Google Patents
Glass member having sealing material layer and method for manufacturing the same, and electronic device and manufacturing method thereof Download PDFInfo
- Publication number
- TWI462829B TWI462829B TW098143641A TW98143641A TWI462829B TW I462829 B TWI462829 B TW I462829B TW 098143641 A TW098143641 A TW 098143641A TW 98143641 A TW98143641 A TW 98143641A TW I462829 B TWI462829 B TW I462829B
- Authority
- TW
- Taiwan
- Prior art keywords
- sealing
- glass
- glass substrate
- material layer
- layer
- Prior art date
Links
- 239000011521 glass Substances 0.000 title claims description 320
- 239000003566 sealing material Substances 0.000 title claims description 156
- 238000004519 manufacturing process Methods 0.000 title claims description 35
- 238000000034 method Methods 0.000 title claims description 26
- 239000010410 layer Substances 0.000 claims description 193
- 239000000758 substrate Substances 0.000 claims description 178
- 238000007789 sealing Methods 0.000 claims description 165
- 239000005394 sealing glass Substances 0.000 claims description 84
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 70
- 229910052799 carbon Inorganic materials 0.000 claims description 69
- 239000000463 material Substances 0.000 claims description 62
- 239000011358 absorbing material Substances 0.000 claims description 29
- 239000000945 filler Substances 0.000 claims description 29
- 239000011247 coating layer Substances 0.000 claims description 21
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 19
- 230000015572 biosynthetic process Effects 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 230000002093 peripheral effect Effects 0.000 claims description 8
- 239000005361 soda-lime glass Substances 0.000 claims description 8
- 229910018068 Li 2 O Inorganic materials 0.000 claims description 7
- 229910052792 caesium Inorganic materials 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052878 cordierite Inorganic materials 0.000 claims description 4
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005388 borosilicate glass Substances 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- -1 zirconium phosphate compound Chemical class 0.000 claims description 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 238000010030 laminating Methods 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 210000004027 cell Anatomy 0.000 claims 1
- 210000003850 cellular structure Anatomy 0.000 claims 1
- 150000003755 zirconium compounds Chemical class 0.000 claims 1
- QUBMWJKTLKIJNN-UHFFFAOYSA-B tin(4+);tetraphosphate Chemical compound [Sn+4].[Sn+4].[Sn+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QUBMWJKTLKIJNN-UHFFFAOYSA-B 0.000 description 19
- 239000005365 phosphate glass Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- 239000011347 resin Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 238000010304 firing Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000020 Nitrocellulose Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 229920001220 nitrocellulos Polymers 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 229910001887 tin oxide Inorganic materials 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000006063 cullet Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004093 laser heating Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QYIJPFYCTROKTM-UHFFFAOYSA-N [Sn].P(O)(O)(O)=O Chemical group [Sn].P(O)(O)(O)=O QYIJPFYCTROKTM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000004031 devitrification Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229940116411 terpineol Drugs 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000002438 flame photometric detection Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229940055577 oleyl alcohol Drugs 0.000 description 1
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000010665 pine oil Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
-
- 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
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
- C03C27/06—Joining glass to glass by processes other than fusing
-
- 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
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
-
- 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
-
- 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/16—Silica-free oxide glass compositions containing phosphorus
- C03C3/17—Silica-free oxide glass compositions containing phosphorus containing aluminium or beryllium
-
- 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
-
- 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
-
- 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
- G02F1/1339—Gaskets; Spacers; Sealing of cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
- H01J11/20—Constructional details
- H01J11/48—Sealing, e.g. seals specially adapted for leading-in conductors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
- H01J9/24—Manufacture or joining of vessels, leading-in conductors or bases
- H01J9/26—Sealing together parts of vessels
- H01J9/261—Sealing together parts of vessels the vessel being for a flat panel display
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
- H05B33/04—Sealing arrangements, e.g. against humidity
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/87—Passivation; Containers; Encapsulations
- H10K59/871—Self-supporting sealing arrangements
- H10K59/8722—Peripheral sealing arrangements, e.g. adhesives, sealants
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Ceramic Engineering (AREA)
- Plasma & Fusion (AREA)
- Glass Compositions (AREA)
- Electroluminescent Light Sources (AREA)
- Joining Of Glass To Other Materials (AREA)
Description
本發明係關於具有密封材料層之玻璃構件和其製造方法、及電子裝置和其製造方法。The present invention relates to a glass member having a sealing material layer, a method of manufacturing the same, an electronic device, and a method of manufacturing the same.
諸如：有機EL顯示器(Organic Electro-Luminescence Display：OELD)、電漿顯示面板(PDP)、液晶顯示裝置(LCD)等平板型顯示器裝置(FPD)，係具有將形成發光元件的元件用玻璃基板、與密封用玻璃基板呈相對向配置，再利用將該等2片玻璃基板施行密封的玻璃封裝件，將發光元件施行密封的構造(參照專利文獻1)。此外，諸如染料敏化太陽電池之類的太陽電池(Dye-sensitized Solar Cell)，亦有就利用2片玻璃基板，將太陽電池元件(光電轉換元件)施行密封的玻璃封裝件之適用進行檢討(參照專利文獻2)。A flat panel display device (FPD) such as an organic electro-luminescence display (OELD), a plasma display panel (PDP), or a liquid crystal display device (LCD) has a glass substrate for an element that forms a light-emitting element, A glass package in which the two glass substrates are sealed is disposed in a direction in which the glass substrate is sealed, and the light-emitting element is sealed (see Patent Document 1). In addition, a Dye-sensitized Solar Cell such as a dye-sensitized solar cell is also reviewed for the application of a glass package in which a solar cell element (photoelectric conversion element) is sealed by using two glass substrates. Refer to Patent Document 2).
將2片玻璃基板間施行密封的密封材料，係有使用諸如密封樹脂或密封玻璃。因為有機EL(OEL)元件等容易因水分而劣化，因而有進展使用耐濕性等優異的密封玻璃。因為利用密封玻璃施行的密封溫度係400~600℃左右，因而當使用普通燒成爐施行加熱處理時，會導致OEL元件等電子元件部的特性劣化。所以，有嘗試在2片玻璃基板周邊部所設置密封區域間中，配置含有雷射吸收材的密封用玻璃材料層，再對其施行雷射光照射，而對密封用玻璃材料層施行加熱，使之熔融而密封(參照專利文獻1、2)。A sealing material for sealing between two glass substrates is used, for example, a sealing resin or a sealing glass. Since an organic EL (OEL) element or the like is easily deteriorated by moisture, a sealing glass excellent in moisture resistance or the like is used. Since the sealing temperature by the sealing glass is about 400 to 600 ° C, when the heat treatment is performed using an ordinary baking furnace, the characteristics of the electronic component such as the OEL element are deteriorated. Therefore, in an attempt to provide a sealing glass material layer containing a laser absorbing material between the sealing regions provided in the peripheral portion of the two glass substrates, laser light is applied thereto, and the sealing glass material layer is heated. It is melted and sealed (see Patent Documents 1 and 2).
利用雷射照射施行的密封(雷射密封)係可抑制對電子元件部的熱影響，但另一方面，就習知密封玻璃(玻璃介質)而言，頗難充分提高密封層與玻璃基板的接著強度，此情形將成為導致諸如FPD、太陽電池等電子裝置的可靠度降低肇因。雷射密封用密封玻璃(玻璃介質)係有就諸如PbO系玻璃粉末、SnO-P2 O5 系玻璃粉末、Bi2 O3 -B2 O3 系玻璃粉末(參照專利文獻3)、以及V2 O5 系玻璃粉末(參照專利文獻1)等的使用進行檢討。該等之中，SnO-P2 O5 系玻璃粉末係就從軟化點低、且對環境與人體的影響較少之觀點，屬於雷射密封用玻璃介質的較佳材料。The sealing (laser sealing) performed by laser irradiation can suppress the thermal influence on the electronic component portion, but on the other hand, in the conventional sealing glass (glass dielectric), it is difficult to sufficiently improve the sealing layer and the glass substrate. Following the intensity, this situation will be a cause of reduced reliability for electronic devices such as FPDs, solar cells, and the like. The sealing glass for a laser seal (glass medium) is, for example, PbO-based glass powder, SnO-P 2 O 5 -based glass powder, Bi 2 O 3 -B 2 O 3 -based glass powder (see Patent Document 3), and V The use of 2 O 5 -based glass powder (see Patent Document 1) and the like is reviewed. Among these, the SnO-P 2 O 5 based glass powder is a preferred material for a glass medium for laser sealing from the viewpoint that the softening point is low and the influence on the environment and the human body is small.
然而，習知僅單純將利用燒成爐施行加熱用的SnO-P2 O5 系玻璃介質，使用為雷射密封用玻璃介質而已，並無法充分提高密封層與玻璃基板間的接著強度。例如專利文獻4中有記載適用於在燒成爐中施行加熱的SnO-P2 O5 系玻璃介質，但此種SnO-P2 O5 系玻璃組成，較難利用雷射加熱處理充分提高對玻璃基板的接著強度。此情形可認為係因為利用燒成爐施行加熱與雷射加熱中所施行的玻璃介質的熔融條件等不同之緣故所致。However, conventionally, a SnO-P 2 O 5 based glass medium for heating by a baking furnace is simply used, and it is used as a glass medium for laser sealing, and the bonding strength between the sealing layer and the glass substrate cannot be sufficiently improved. For example, Patent Document 4 describes a SnO-P 2 O 5 -based glass medium which is applied to heating in a firing furnace. However, such a SnO-P 2 O 5 -based glass composition is difficult to be sufficiently improved by laser heat treatment. The adhesion strength of the glass substrate. In this case, it is considered that the heating by the baking furnace is different from the melting condition of the glass medium which is performed in the laser heating.
專利文獻1：日本專利特表2006-524419號公報Patent Document 1: Japanese Patent Laid-Open Publication No. 2006-524419
專利文獻2：日本專利特開2008-115057號公報Patent Document 2: Japanese Patent Laid-Open Publication No. 2008-115057
專利文獻3：日本專利特開2008-059802號公報Patent Document 3: Japanese Patent Laid-Open Publication No. 2008-059802
專利文獻4：日本專利特開2003-146691號公報Patent Document 4: Japanese Patent Laid-Open Publication No. 2003-146691
本發明目的在於提供：能重現性佳地提高雷射密封時的玻璃基板與密封層間之接著強度的具有密封材料層之玻璃構件及其製造方法，更提供藉由提高密封層與玻璃基板間之接著強度，進而可提升密封可靠度與機械可靠度等的電子裝置及其製造方法。An object of the present invention is to provide a glass member having a sealing material layer capable of reproducibly improving the adhesion strength between a glass substrate and a sealing layer during laser sealing, and a method for producing the same, and further improving the sealing layer and the glass substrate The subsequent strength, which further improves the reliability of the seal, the mechanical reliability, and the like, and the method of manufacturing the same.
本發明態樣的具有密封材料層之玻璃構件，特徵在於具備有玻璃基板與密封材料層，該玻璃基板係具有密封區域；該密封材料層係設置於前述玻璃基板的前述密封區域上，且由含有密封玻璃、低膨脹填充材及雷射吸收材的密封用玻璃材料之燒成層構成；其中，前述密封玻璃依質量比例計，含有：20~68%的SnO、0.5~5%的SnO2 及20~40%的P2 O5 ，且前述密封材料層中的殘留碳量依質量比例計，係在20~1000ppm範圍內。A glass member having a sealing material layer according to an aspect of the present invention is characterized in that a glass substrate and a sealing material layer are provided, the glass substrate having a sealing region; the sealing material layer is disposed on the sealing region of the glass substrate, and The fire-retardant layer of the sealing glass material containing the sealing glass, the low-expansion filler, and the laser absorbing material; wherein the sealing glass contains: 20 to 68% of SnO and 0.5 to 5% of SnO 2 by mass ratio And 20 to 40% of P 2 O 5 , and the amount of residual carbon in the sealing material layer is in the range of 20 to 1000 ppm by mass.
本發明態樣的具有密封材料層之玻璃構件之製造方法，特徵在於包括有：準備具有密封區域之玻璃基板的步驟；在前述玻璃基板的前述密封區域上，將含有密封玻璃、低膨脹填充材及雷射吸收材的密封用玻璃材料之糊劑施行塗佈的步驟，且該密封玻璃依質量比例計，含有：20~68%的SnO、0.5~5%的SnO2 及20~40%的P2 O5 ；以及將前述糊劑的塗佈層施行燒成，形成殘留碳量依質量比例計，係在20~1000ppm範圍內的密封材料層的步驟。A method of manufacturing a glass member having a sealing material layer according to an aspect of the present invention includes the steps of: preparing a glass substrate having a sealing region; and sealing glass and a low expansion filler on the sealing region of the glass substrate And a step of applying a coating of a glass material for sealing a laser absorbing material, wherein the sealing glass comprises: 20 to 68% of SnO, 0.5 to 5% of SnO 2 and 20 to 40% by mass ratio. P 2 O 5 ; and a step of baking the coating layer of the paste to form a sealing material layer having a residual carbon amount in a range of 20 to 1000 ppm by mass.
本發明另一態樣的電子裝置，特徵在於具備有：第1玻璃基板、第2玻璃基板、及密封層，該第1玻璃基板係具有：具電子元件的元件形成區域、及設置於前述元件形成區域外周側的第1密封區域；該第2玻璃基板係具有對應於前述第1玻璃基板之前述第1密封區域的第2密封區域；該密封層係將前述第1玻璃基板的前述第1密封區域、與前述第2玻璃基板的前述第2密封區域之間，以在前述元件形成區域上設置間隙之情況下進行密封的方式形成，且前述密封層係由含有密封玻璃、低膨脹填充材及雷射吸收材的密封用玻璃材料之熔融固接層構成；其中，前述密封玻璃依質量比例計，含有：20~68%的SnO、0.5~5%的SnO2 及20~40%的P2 O5 ，且前述密封層中的殘留碳量依質量比例計，係在20~1000ppm範圍內。An electronic device according to another aspect of the present invention includes: a first glass substrate, a second glass substrate, and a sealing layer, wherein the first glass substrate includes an element forming region having an electronic component, and the component is provided on the component a first sealing region on the outer peripheral side of the region; the second glass substrate has a second sealing region corresponding to the first sealing region of the first glass substrate; and the sealing layer is the first surface of the first glass substrate The sealing region and the second sealing region of the second glass substrate are formed to be sealed while a gap is formed in the element forming region, and the sealing layer is made of a sealing glass or a low expansion filler. And a molten fixing layer of a sealing glass material for a laser absorbing material; wherein the sealing glass comprises: 20 to 68% of SnO, 0.5 to 5% of SnO 2 and 20 to 40% of P by mass ratio 2 O 5 , and the amount of residual carbon in the sealing layer is in the range of 20 to 1000 ppm in terms of mass ratio.
本發明另一態樣的電子裝置之製造方法，特徵在於包括有：準備第1玻璃基板的步驟，該第1玻璃基板係具有：具電子元件的元件形成區域、及設置於前述元件形成區域外周側的第1密封區域；準備含有第2密封區域與密封材料層的第2玻璃基板之步驟，該第2密封區域係對應於前述第1玻璃基板的前述第1密封區域；該密封材料層係形成於前述第2密封區域上，且由含有密封玻璃、低膨脹填充材及雷射吸收材的密封用玻璃材料之燒成層構成，且殘留碳量依質量比例計，係在20~1000ppm範圍內，該密封玻璃依質量比例計，含有：20~68%的SnO、0.5~5%的SnO2 及20~40%的P2 O5 ；在前述元件形成區域上形成間隙的情況下，隔著前述密封材料層將前述第1玻璃基板與前述第2玻璃基板進行積層的步驟；以及透過前述第2玻璃基板對前述密封材料層施行雷射光照射，使前述密封材料層熔融，而形成將前述第1玻璃基板與前述第2玻璃基板間進行密封之密封層的步驟。A method of manufacturing an electronic device according to another aspect of the present invention includes the step of preparing a first glass substrate having an element formation region having an electronic component and a periphery of the component formation region a first sealing region on the side; a step of preparing a second glass substrate including a second sealing region and a sealing material layer, wherein the second sealing region corresponds to the first sealing region of the first glass substrate; and the sealing material layer It is formed on the second sealing region, and is composed of a fired layer of a sealing glass material containing a sealing glass, a low-expansion filler, and a laser absorbing material, and the residual carbon amount is in the range of 20 to 1000 ppm in terms of mass ratio. The sealing glass contains: 20 to 68% of SnO, 0.5 to 5% of SnO 2 and 20 to 40% of P 2 O 5 by mass ratio; in the case where a gap is formed in the element forming region, a step of laminating the first glass substrate and the second glass substrate in the sealing material layer; and irradiating the sealing material layer with laser light through the second glass substrate to form the sealing material layer Melting, the step between the first glass substrate and the second glass substrate for sealing of the sealing layer is formed.
根據本發明態樣的具有密封材料層之玻璃構件和其製造方法，當雷射密封時，可重現性佳地提高玻璃基板與密封層間的接著強度。所以，根據本發明態樣的電子裝置及其製造方法，便可提高電子裝置的密封可靠度與機械可靠度。According to the glass member having the sealing material layer and the method of manufacturing the same according to the aspect of the invention, the reproducibility improves the adhesion strength between the glass substrate and the sealing layer when the laser is sealed. Therefore, according to the electronic device of the aspect of the invention and the method of manufacturing the same, the sealing reliability and mechanical reliability of the electronic device can be improved.
第1圖係顯示本發明實施形態的電子裝置之構造的剖視圖。Fig. 1 is a cross-sectional view showing the structure of an electronic device according to an embodiment of the present invention.
第2(a)~(d)圖係顯示本發明實施形態的電子裝置之製造步驟的剖視圖。2(a) to 2(d) are cross-sectional views showing the steps of manufacturing the electronic device according to the embodiment of the present invention.
第3圖係顯示第2圖所示之電子裝置之製造步驟中使用的第1玻璃基板的平面圖。Fig. 3 is a plan view showing a first glass substrate used in the manufacturing steps of the electronic device shown in Fig. 2.
第4圖係沿第3圖中的A-A線的切剖圖。Fig. 4 is a cross-sectional view taken along line A-A in Fig. 3.
第5圖係顯示第2圖所示之電子裝置之製造步驟中使用的第2玻璃基板的平面圖。Fig. 5 is a plan view showing a second glass substrate used in the manufacturing steps of the electronic device shown in Fig. 2.
第6圖係沿第5圖中的A-A線的切剖圖。Fig. 6 is a cross-sectional view taken along line A-A in Fig. 5.
以下，針對供實施本發明的形態，參照圖式進行說明。第1圖係顯示本發明實施形態的電子裝置之構造的圖，第2圖係顯示電子裝置之製造步驟的圖，第3圖至第6圖係顯示用於前述電子裝置的玻璃基板之構造的圖。第1圖所示電子裝置1係構成諸如：OELD、PDP、LCD等的使用FPD、OEL元件等發光元件的照明裝置，或諸如染料敏化太陽電池之類的太陽電池等。Hereinafter, embodiments for carrying out the invention will be described with reference to the drawings. 1 is a view showing a structure of an electronic device according to an embodiment of the present invention, FIG. 2 is a view showing a manufacturing step of the electronic device, and FIGS. 3 to 6 are views showing a configuration of a glass substrate used in the electronic device. Figure. The electronic device 1 shown in Fig. 1 constitutes an illumination device using a light-emitting element such as an FPLD or an OEL element such as an OELD, a PDP, or an LCD, or a solar cell such as a dye-sensitized solar cell.
電子裝置1係具備有：含有具電子元件之元件形成區域2a的第1玻璃基板(元件用玻璃基板)2、及第2玻璃基板(密封用玻璃基板)3。該第1與第2玻璃基板2、3係由例如無鹼玻璃或鈉鈣玻璃等構成。無鹼玻璃係具有35~40×10-7 /℃左右的熱膨脹係數。鈉鈣玻璃係具有85~90×10-7 /℃左右的熱膨脹係數The electronic device 1 includes a first glass substrate (glass substrate for a component) 2 and a second glass substrate (glass substrate for sealing) 3 including an element forming region 2a having an electronic component. The first and second glass substrates 2 and 3 are made of, for example, alkali-free glass or soda lime glass. The alkali-free glass system has a thermal expansion coefficient of about 35 to 40 × 10 -7 /°C. Soda-lime glass has a thermal expansion coefficient of 85~90×10 -7 /°C
第1玻璃基板2的元件形成區域2a中，形成有配合電子裝置1的電子元件，例如若屬於OELD或OEL照明便形成OEL元件，若屬於PDP便形成電漿發光元件，若屬於LCD便形成液晶顯示元件，若屬於太陽電池便形成染料敏化光電轉換部等。諸如OEL元件之類的發光元件、或諸如染料敏化光電轉換部之類的太陽電池元件等電子元件，係具備有各種公知構造，不侷限於該等元件構造。本發明的電子元件較佳係有機EL(OEL)元件或太陽電池元件。In the element forming region 2a of the first glass substrate 2, an electronic component to which the electronic device 1 is incorporated is formed. For example, if it belongs to OELD or OEL illumination, an OEL element is formed, and if it belongs to a PDP, a plasma light-emitting element is formed, and if it belongs to the LCD, a liquid crystal is formed. The display element forms a dye-sensitized photoelectric conversion unit or the like if it belongs to a solar cell. Electronic components such as a light-emitting element such as an OEL element or a solar cell element such as a dye-sensitized photoelectric conversion unit are provided with various known structures, and are not limited to these element configurations. The electronic component of the present invention is preferably an organic EL (OEL) element or a solar cell element.
第1玻璃基板2係如第3圖與第4圖所示，具有在元件形成區域2a外周側設置的第1密封區域2b。第1密封區域2b係設定呈包圍元件形成區域2a狀態。第2玻璃基板3係如第5圖所示，具有第2密封區域3a。第2密封區域3a係對應第1密封區域2b。As shown in FIGS. 3 and 4, the first glass substrate 2 has a first sealing region 2b provided on the outer peripheral side of the element forming region 2a. The first sealing region 2b is set to surround the element forming region 2a. The second glass substrate 3 has a second sealing region 3a as shown in Fig. 5 . The second sealing region 3a corresponds to the first sealing region 2b.
即，設定成當將第1玻璃基板2與第2玻璃基板3呈相對向配置時，第1密封區域2b與第2密封區域3a可相對，且如後述般地，成為密封層4的形成區域(對第2玻璃基板3而言係成為密封材料層5的形成區域)。In other words, when the first glass substrate 2 and the second glass substrate 3 are disposed to face each other, the first sealing region 2b and the second sealing region 3a are opposed to each other, and the formation region of the sealing layer 4 is formed as will be described later. (The formation region of the sealing material layer 5 is the second glass substrate 3).
第1玻璃基板2與第2玻璃基板3係依在元件形成區域2a上形成間隙的方式呈相對向配置。第1玻璃基板2與第2玻璃基板3間的空間係利用密封層4施行密封。即，密封層4係將第1玻璃基板2的密封區域2b、與第2玻璃基板3的密封區域3a之間，以在元件形成區域2a上設置間隙之情況下施行密封的方式來形成。在元件形成區域2a中所形成的電子元件，係利用由第1玻璃基板2、第2玻璃基板3及密封層4構成的玻璃面板施行氣密密封。The first glass substrate 2 and the second glass substrate 3 are arranged to face each other so as to form a gap in the element formation region 2a. The space between the first glass substrate 2 and the second glass substrate 3 is sealed by the sealing layer 4. In other words, the sealing layer 4 is formed by sealing between the sealing region 2b of the first glass substrate 2 and the sealing region 3a of the second glass substrate 3 with a gap formed in the element forming region 2a. The electronic component formed in the element formation region 2a is hermetically sealed by a glass panel composed of the first glass substrate 2, the second glass substrate 3, and the sealing layer 4.
密封層4係由一熔融固接層所構成，該熔融固接層係利用雷射光6使在第2玻璃基板3的密封區域3a上所形成密封材料層5熔融，而固接於第1玻璃基板2之密封區域2b者。即，在電子裝置1之製作所使用的第2玻璃基板3之密封區域3a中，如第5圖與第6圖所示，形成有框狀密封材料層5。藉由利用雷射光6的熱使在第2玻璃基板3的密封區域3a中所形成密封材料層5，如第2(c)與(d)圖所示，熔融固接於第1玻璃基板2的密封區域2b，便形成將第1玻璃基板2與第2玻璃基板3間的空間(元件配置空間)施行密封之密封層4。The sealing layer 4 is composed of a fusion-fixing layer that melts the sealing material layer 5 formed on the sealing region 3a of the second glass substrate 3 by the laser light 6 and is fixed to the first glass. The sealing area 2b of the substrate 2 is. In other words, in the sealing region 3a of the second glass substrate 3 used for the production of the electronic device 1, as shown in Figs. 5 and 6, a frame-shaped sealing material layer 5 is formed. The sealing material layer 5 formed in the sealing region 3a of the second glass substrate 3 is melt-fixed to the first glass substrate 2 as shown in the second (c) and (d) by the heat of the laser light 6. The sealing region 2b forms a sealing layer 4 that seals a space (component arrangement space) between the first glass substrate 2 and the second glass substrate 3.
密封材料層5係含有密封玻璃(玻璃介質)、雷射吸收材及低膨脹填充材的密封用玻璃材料燒成層。密封用玻璃材料係在主成分的密封玻璃中，摻合雷射吸收材與低膨脹填充材。密封用玻璃材料視需要亦可含有除該等以外的添加材料。密封用玻璃材料主成分的密封玻璃可使用依質量比例計，含有：20~68%之SnO、0.5~5%之SnO2 及20~40%之P2 O5 組成的錫-磷酸系(SnO-P2 O5 系)玻璃。密封用玻璃材料主成分的密封玻璃含有量，係如後述，亦依存於雷射吸收材與低膨脹填充材的摻合量，相對於密封用玻璃材料，較佳含有40~90體積%、更佳45~80體積%。此外，密封玻璃(玻璃介質)較佳係粉末狀，最大粒徑較佳係100μm以下、更佳50μm以下。The sealing material layer 5 is a sealing glass material baking layer containing a sealing glass (glass medium), a laser absorbing material, and a low expansion filler. The glass material for sealing is contained in a sealing glass of a main component, and a laser absorbing material and a low expansion filler are blended. The glass material for sealing may contain an additive material other than these as needed. The sealing glass for the main component of the sealing glass material may be a tin-phosphate system (SnO) composed of 20 to 68% of SnO, 0.5 to 5% of SnO 2 and 20 to 40% of P 2 O 5 by mass ratio. -P 2 O 5 series) glass. The sealing glass content of the main component of the glass material for sealing is preferably 40 to 90% by volume, more preferably 40 to 90% by volume, based on the amount of the laser absorbing material to be bonded, depending on the amount of the sealing absorbing material and the low-expansion filler. Good 45~80% by volume. Further, the sealing glass (glass medium) is preferably in the form of a powder, and the maximum particle diameter is preferably 100 μm or less, more preferably 50 μm or less.
在雷射密封用密封玻璃(玻璃介質)中，為控制玻璃的熔融溫度，較佳係玻璃本身並不會吸收雷射(屬於透明的玻璃)。藉由利用在密封玻璃中所添加之雷射吸收材料的種類與量等而控制著熔融溫度，便能可靠度佳地實施雷射密封步驟。密封玻璃(玻璃介質)係為抑制對玻璃基板2、3的熱衝擊，最好係熔融溫度屬於較低溫。且，經考慮對環境與人體的影響，最好未含鉛、釩等。錫-磷酸系玻璃介質便符合此種要求。In the sealing glass for laser sealing (glass medium), in order to control the melting temperature of the glass, it is preferred that the glass itself does not absorb the laser (which is a transparent glass). By controlling the melting temperature by the kind and amount of the laser absorbing material added to the sealing glass, the laser sealing step can be performed with reliability. The sealing glass (glass medium) is for suppressing thermal shock to the glass substrates 2 and 3, and it is preferable that the melting temperature is lower. Moreover, it is preferable not to contain lead or vanadium after considering the influence on the environment and the human body. Tin-phosphate glass media meets this requirement.
本實施形態所使用的密封玻璃(錫-磷酸系玻璃介質)中，SnO係為使玻璃呈低熔點化的成分，在密封玻璃中含有20~68質量%範圍內。若SnO含有量未滿20質量%，則玻璃的軟化溫度會變高，低溫下的密封趨於困難。且，發生為使玻璃軟化而必需提高雷射光6輸出的必要，結果玻璃基板2、3便容易發生裂痕等。若SnO含有量超過68質量%，便不會玻璃化。SnO含有量較佳係設為30~65質量%範圍內。In the sealing glass (tin-phosphate type glass medium) used in the present embodiment, the SnO is a component which lowers the melting point of the glass, and is contained in the sealing glass in the range of 20 to 68% by mass. When the SnO content is less than 20% by mass, the softening temperature of the glass becomes high, and sealing at a low temperature tends to be difficult. Further, it is necessary to increase the output of the laser light 6 in order to soften the glass, and as a result, the glass substrates 2 and 3 are likely to be cracked or the like. If the SnO content exceeds 68% by mass, it will not vitrify. The SnO content is preferably in the range of 30 to 65 mass%.
SnO2 係為使玻璃呈安定化的成分，在密封玻璃中含有0.5~5質量%範圍內。若SnO2 含有量未滿0.5質量%，則玻璃安定性會降低、容易發生失透明(devitrification)，在玻璃製造中容易混入失透明物。此外，在雷射加熱時，於呈軟化熔融的玻璃中會有SnO2 分離、析出，而損及流動性，導致氣密性容易降低低。若SnO2 含有量超過5質量%，則在玻璃製造時容易從熔融中析出SnO2 ，無法獲得安定的玻璃。若考慮玻璃的安定性與流動性等因素，SnO2 含有量較佳設為1~3.5質量%範圍。SnO 2 is a component which stabilizes glass and is contained in the range of 0.5 to 5% by mass in the sealing glass. When the content of SnO 2 is less than 0.5% by mass, the glass stability is lowered, devitrification is likely to occur, and an opaque substance is easily mixed in the production of glass. Further, when the laser is heated, SnO 2 is separated and precipitated in the glass which is softened and melted, and the fluidity is impaired, so that the airtightness is easily lowered. When the content of SnO 2 exceeds 5% by mass, SnO 2 is easily precipitated from the melt during glass production, and stable glass cannot be obtained. The SnO 2 content is preferably in the range of 1 to 3.5% by mass in consideration of factors such as stability and fluidity of the glass.
P2 O5 係為形成玻璃骨架用的成分，在密封玻璃中含有20~40質量%範圍內。若P2 O5 含有量未滿20質量%，便不會玻璃化。若P2 O5 含有量超過40質量%，便會有誘發磷酸鹽玻璃特有缺點之耐候性惡化的可能性。若考慮玻璃的安定性與耐候性等，P2 O5 含有量較佳係設為25~40質量%範圍。P 2 O 5 is a component for forming a glass skeleton, and is contained in the range of 20 to 40% by mass in the sealing glass. If the content of P 2 O 5 is less than 20% by mass, it will not vitrify. When the content of P 2 O 5 exceeds 40% by mass, the weather resistance which induces a specific disadvantage of phosphate glass may be deteriorated. In consideration of stability and weather resistance of the glass, the P 2 O 5 content is preferably in the range of 25 to 40% by mass.
此處，玻璃介質中的SnO與SnO2 質量比係可依如下進行求取。首先，將玻璃介質(低熔點玻璃粉末)進行酸分解後，利用ICP發光分光分析測定玻璃介質中所含Sn原子的總量。接著，因為Sn2+ (SnO)係由經酸分解物利用碘滴定法進行求取，因而將從Sn原子總量中扣減掉此處所求得的Sn2+ 量，便可求得Sn4+ (SnO2 )。Here, the mass ratio of SnO to SnO 2 in the glass medium can be determined as follows. First, after the glass medium (low-melting glass powder) was subjected to acid decomposition, the total amount of Sn atoms contained in the glass medium was measured by ICP emission spectrometry. Next, since Sn 2+ (SnO) is obtained by the iodine titration method using the acid decomposition product, Sn 4 can be obtained by subtracting the amount of Sn 2+ obtained here from the total amount of Sn atoms. + (SnO 2 ).
依上述3成分所形成的玻璃係玻璃轉移點較低，適用為低溫用密封材料，但亦可含有例如：SiO2 、ZnO、B2 O3 、Al2 O3 、WO3 、MoO3 、Nb2 O5 、TiO2 、ZrO2 、Li2 O、Na2 O、K2 O、Cs2 O、MgO、CaO、SrO、BaO等任意成分。但，若各成分的個別含有量、或任意成分的合計含有量過多，則玻璃便會呈不安定，在玻璃製造時會發生失透明，且即便未達失透明程度，但玻璃結晶化傾向仍會過於強烈，導致玻璃在加熱途中，未呈軟化流動便結晶化，會有無法與玻璃基板2、3進行密接的可能性。The glass-based glass formed by the above three components has a low transfer point and is suitable for a low-temperature sealing material, but may also contain, for example, SiO 2 , ZnO, B 2 O 3 , Al 2 O 3 , WO 3 , MoO 3 , Nb. 2 O 5 , TiO 2 , ZrO 2 , Li 2 O, Na 2 O, K 2 O, Cs 2 O, MgO, CaO, SrO, BaO, and the like. However, if the individual content of each component or the total content of any component is too large, the glass will be unstable, and the glass will be deficient during the production of the glass, and the glass crystallization tendency will remain even if the degree of transparency is not lost. If the glass is heated, it will crystallize without being softened, and there is a possibility that it cannot be adhered to the glass substrates 2 and 3.
就從此點觀之，上述任意成分的合計含有量較佳設為15質量%以下。任意成分中，SiO2 係形成玻璃骨架的成分，含有量較佳設為10質量%以下。此外，最好以SiO2 為必要成分且含有0.1~5質量%。諸如：ZnO、B2 O3 、Al2 O3 、WO3 、MoO3 、Nb2 O5 、TiO2 、ZrO2 、Li2 O、Na2 O、K2 O、Cs2 O、MgO、CaO、SrO、BaO等係屬於使玻璃呈安定化的成分，各自的含有量分別較佳設定在10質量%以下。若各成分的個別含有量超過10質量%，便會有在玻璃製造時發生失透明情形，且會有玻璃結晶化傾向趨強的可能性。From this point of view, the total content of the above optional components is preferably 15% by mass or less. Among the optional components, SiO 2 forms a component of the glass skeleton, and the content thereof is preferably 10% by mass or less. Further, it is preferable to use SiO 2 as an essential component and 0.1 to 5% by mass. Such as: ZnO, B 2 O 3 , Al 2 O 3 , WO 3 , MoO 3 , Nb 2 O 5 , TiO 2 , ZrO 2 , Li 2 O, Na 2 O, K 2 O, Cs 2 O, MgO, CaO SrO, BaO, and the like are components which stabilize the glass, and the respective contents are preferably set to 10% by mass or less. When the individual content of each component exceeds 10% by mass, devitrification may occur at the time of glass production, and there is a possibility that the glass crystallization tends to be strong.
上述任意成分中，諸如：ZnO、B2 O3 、Al2 O3 、WO3 、MoO3 等係除玻璃安定化之外，尚具有使玻璃熱膨脹係數降低的效果。較佳係以ZnO為必要成分並含有2~6質量%。此外，諸如：Nb2 O5 、TiO2 、ZrO2 等係具有提升化學耐久性的效果。諸如：Li2 O、Na2 O、K2 O、Cs2 O等係具有降低玻璃的軟化點，進而提升流動性的效果。Among the above-mentioned arbitrary components, such as ZnO, B 2 O 3 , Al 2 O 3 , WO 3 , MoO 3 or the like, in addition to glass stabilization, there is an effect of lowering the coefficient of thermal expansion of the glass. It is preferable to use ZnO as an essential component and to contain 2 to 6% by mass. Further, such as Nb 2 O 5 , TiO 2 , ZrO 2 and the like have an effect of improving chemical durability. For example, Li 2 O, Na 2 O, K 2 O, Cs 2 O, etc. have the effect of lowering the softening point of the glass and further improving the fluidity.
諸如：MgO、CaO、SrO、BaO等係具有調整玻璃的黏度，以及調整熱膨脹係數的效果。該等各成分的含有量係依如上述，任意成分的合計含有量較佳設為不超過15質量%範圍、更佳在10質量%以下。For example, MgO, CaO, SrO, BaO, etc. have the effect of adjusting the viscosity of the glass and adjusting the coefficient of thermal expansion. The content of each of the components is preferably as described above, and the total content of the optional components is preferably not more than 15% by mass, more preferably 10% by mass or less.
密封用玻璃材料係含有低膨脹填充材。低膨脹填充材較佳係使用從例如：氧化矽、氧化鋁、氧化鋯、矽酸鋯、菫青石、磷酸鋯系化合物、鈉鈣玻璃及硼矽酸玻璃所構成群組中至少選擇一種。磷酸鋯系化合物係可舉例如：(ZrO)2 P2 O7 、AZr2 (PO4 )3 (A係從Na、K及Ca所構成群組中至少選擇一種)、NbZr2 (PO4 )3 、Zr2 (WO3 )(PO4 )2 、或該等的複合化合物。「低膨脹填充材」係指具有較密封用玻璃材料主成分的密封玻璃更低之熱膨脹係數的材料。The glass material for sealing contains a low expansion filler. The low-expansion filler is preferably at least one selected from the group consisting of cerium oxide, aluminum oxide, zirconium oxide, zirconium silicate, cordierite, zirconium phosphate-based compound, soda lime glass, and borosilicate glass. Examples of the zirconium phosphate-based compound include (ZrO) 2 P 2 O 7 and AZr 2 (PO 4 ) 3 (at least one selected from the group consisting of Na, K, and Ca), and NbZr 2 (PO 4 ). 3 , Zr 2 (WO 3 )(PO 4 ) 2 , or such composite compounds. The "low-expansion filler" means a material having a lower coefficient of thermal expansion than a sealing glass which is a main component of a sealing glass material.
低膨脹填充材的含有量係依密封玻璃的熱膨脹係數，接近玻璃基板2、3的熱膨脹係數之方式適當設定。低膨脹填充材係依照密封玻璃與玻璃基板2、3的熱膨脹係數而異，但相對於密封用玻璃材料，較佳含有1~50體積%範圍內。當玻璃基板2、3係利用無鹼玻璃(熱膨脹係數：35~40×10-7 /℃)形成的情況，較佳係添加較多量(例如30~50體積%範圍)的低膨脹填充材。當玻璃基板2、3係由鈉鈣玻璃(熱膨脹係數：85~90×10-7 /℃)形成的情況，較佳係添加較少量(例如15~40體積%範圍)的低膨脹填充材。此外，低膨脹填充材較佳係粉末狀，最大粒徑較佳係100μm以下、更佳50μm以下。The content of the low-expansion filler is appropriately set depending on the thermal expansion coefficient of the sealing glass and the thermal expansion coefficient of the glass substrates 2 and 3. The low-expansion filler differs depending on the thermal expansion coefficient of the sealing glass and the glass substrates 2 and 3, but is preferably contained in the range of 1 to 50% by volume based on the glass material for sealing. When the glass substrates 2 and 3 are formed of an alkali-free glass (coefficient of thermal expansion: 35 to 40 × 10 -7 /° C.), it is preferred to add a large amount (for example, a range of 30 to 50% by volume) of a low-expansion filler. When the glass substrates 2 and 3 are formed of soda lime glass (coefficient of thermal expansion: 85 to 90 × 10 -7 /° C.), it is preferred to add a small amount (for example, a range of 15 to 40% by volume) of a low expansion filler. . Further, the low-expansion filler is preferably in the form of a powder, and the maximum particle diameter is preferably 100 μm or less, more preferably 50 μm or less.
密封用玻璃材料係更進一步含有雷射吸收材。雷射吸收材係使用諸如：從Fe、Cr、Mn、Co、Ni及Cu中選出之至少一種金屬、或含前述金屬的氧化物等化合物。雷射吸收材的含有量係相對於密封用玻璃材料，較佳設為0.1~10體積%範圍內。若雷射吸收材的含有量未滿0.1體積%，在雷射照射時便無法使密封材料層5充分熔融。若雷射吸收材含有量超過10體積%，在雷射照射時會有在與第2玻璃基板3間的界面附近出現局部性發熱，導致第2玻璃基板3發生斷裂等情形，或者密封用玻璃材料熔融時的流動性降低，導致與第1玻璃基板2間的接著性降低之可能性。雷射吸收材含有量較佳設為1~9體積%範圍內。此外，雷射吸收材較佳係粉末狀，最大粒徑較佳係50μm以下、更佳20μm以下。The glass material for sealing further contains a laser absorbing material. The laser absorbing material uses, for example, at least one metal selected from Fe, Cr, Mn, Co, Ni, and Cu, or a compound containing an oxide of the foregoing metal. The content of the laser absorbing material is preferably in the range of 0.1 to 10% by volume based on the glass material for sealing. If the content of the laser absorbing material is less than 0.1% by volume, the sealing material layer 5 cannot be sufficiently melted at the time of laser irradiation. When the content of the laser absorbing material exceeds 10% by volume, localized heat may be generated in the vicinity of the interface with the second glass substrate 3 during laser irradiation, and the second glass substrate 3 may be broken or the glass for sealing may be used. The fluidity at the time of melting the material is lowered, which may cause a decrease in the adhesion to the first glass substrate 2. The content of the laser absorbing material is preferably in the range of 1 to 9% by volume. Further, the laser absorbing material is preferably in the form of a powder, and the maximum particle diameter is preferably 50 μm or less, more preferably 20 μm or less.
依如上述，本實施形態所使用的錫-磷酸系玻璃介質，因為具有透明且玻璃轉移點較低等特性，因而適用為低溫加熱用密封材料。但，當對密封材料層5施行雷射光6照射而形成密封層4時，僅單純將錫-磷酸系玻璃介質(密封玻璃)使用於雷射密封，並無法充分提高玻璃基板2、3與密封層4間之接著強度。此現象可認為因為利用燒成爐施行加熱與利用雷射加熱施行的情況，就玻璃介質的熔融條件等會有所不同所致。As described above, the tin-phosphate glass medium used in the present embodiment is suitable as a sealing material for low-temperature heating because of its transparency and low glass transition point. However, when the sealing material layer 5 is irradiated with the laser beam 6 to form the sealing layer 4, only the tin-phosphate glass medium (sealing glass) is used for the laser sealing, and the glass substrates 2, 3 and the sealing cannot be sufficiently improved. The bonding strength between layers 4. This phenomenon is considered to be caused by the fact that the melting condition of the glass medium or the like is different due to the heating by the firing furnace and the heating by the laser.
玻璃基板與玻璃介質間之接著強度，係根據該等的熱膨脹差所造成的殘留應變、以及玻璃基板與玻璃介質間的界面反應。一般使用燒成爐施行加熱的情況，將無關於玻璃基板與玻璃介質的種類，均會在玻璃基板與玻璃介質(密封層)間的界面形成反應層，利用化學鍵結將可提高接著強度。換言之，使用由燒成爐施行加熱的密封步驟，因為有在接著界面形成反應層的時間充裕，因而可獲得充分的接著強度。The bonding strength between the glass substrate and the glass medium is based on the residual strain caused by the difference in thermal expansion and the interface reaction between the glass substrate and the glass medium. In general, when heating is performed using a baking furnace, the reaction layer is formed at the interface between the glass substrate and the glass medium (sealing layer) regardless of the type of the glass substrate and the glass medium, and the bonding strength can be improved by chemical bonding. In other words, using the sealing step of heating by the firing furnace, since there is sufficient time for forming the reaction layer at the subsequent interface, sufficient bonding strength can be obtained.
另一方面，使用雷射加熱的密封步驟，係利用沿框狀密封材料層5，一邊施行雷射光6掃描，一邊進行照射而實施。密封材料層5將從雷射光6所照射到的部分開始依序熔融，且會隨著雷射光6的照射完成而急冷固化。依此的話，在雷射密封步驟中並無法充分獲得反應層的形成時間。因而，僅依靠具有SnO、SnO2 及P2 O5 等3成分系組成的玻璃介質，在雷射密封時便無法充分提高玻璃基板2、3與密封層4間之接著強度。On the other hand, the sealing step using the laser heating is carried out by performing irradiation while scanning the laser light 6 along the frame-shaped sealing material layer 5. The sealing material layer 5 is sequentially melted from the portion irradiated with the laser light 6, and is rapidly solidified as the irradiation of the laser light 6 is completed. In this case, the formation time of the reaction layer cannot be sufficiently obtained in the laser sealing step. Therefore, the glass medium having a composition of three components such as SnO, SnO 2 and P 2 O 5 can not sufficiently improve the adhesion strength between the glass substrates 2 and 3 and the sealing layer 4 during laser sealing.
在使用雷射加熱的密封步驟中，為能在玻璃基板2、3與密封層4的接著界面上形成反應層，使密封材料層(密封用玻璃材料的燒成層)5中殘留適量碳係屬有效。即，在使用錫-磷酸系玻璃介質形成的密封材料層5中所殘留的碳，係具有還原劑的機能。所以，即便係短時間實施局部性玻璃介質熔融固化的雷射密封，藉由密封材料層5中的殘留碳而將氧化錫施行還原，便可提升玻璃基板2、3、與錫-磷酸系玻璃介質間的反應性。In the sealing step using laser heating, in order to form a reaction layer on the subsequent interface between the glass substrates 2, 3 and the sealing layer 4, an appropriate amount of carbon is left in the sealing material layer (the fired layer of the sealing glass material) 5. It is valid. In other words, the carbon remaining in the sealing material layer 5 formed using the tin-phosphate glass medium is a function of a reducing agent. Therefore, even if the laser seal is melted and cured in a localized glass medium for a short period of time, the tin oxide can be reduced by the residual carbon in the sealing material layer 5, thereby improving the glass substrates 2, 3, and the tin-phosphate glass. Reactivity between media.
即，在雷射照射時，藉由將錫-磷酸系玻璃介質中的氧化錫(特別係容易還原的SnO)利用殘留碳進行還原，便可將部分的氧化錫變成金屬錫(Sn)。金屬錫(Sn)係具有容易擴散於玻璃基板2、3中的性質。所以，藉由使在經雷射光6照射而熔融的密封材料層5中存在適量金屬錫(Sn)，即便依短時間施行玻璃介質熔融固化的雷射密封步驟，仍可在接著界面形成反應層。所以，雷射密封時，便可提高玻璃基板2、3、與錫-磷酸系玻璃介質(密封層4)間之接著強度。That is, at the time of laser irradiation, a part of tin oxide can be turned into metal tin (Sn) by reducing tin oxide (SnO which is especially easy to reduce) in a tin-phosphate type glass medium by residual carbon. Metal tin (Sn) has a property of being easily diffused into the glass substrates 2 and 3. Therefore, by forming an appropriate amount of metal tin (Sn) in the sealing material layer 5 which is melted by the irradiation of the laser light 6, even if the laser sealing step of the glass medium is melt-solidified in a short time, the reaction layer can be formed at the subsequent interface. . Therefore, the adhesion strength between the glass substrates 2, 3 and the tin-phosphate glass medium (sealing layer 4) can be improved at the time of laser sealing.
在密封材料層5中殘留的碳量(密封材料層5的殘留碳量)依質量比例設定為20~1000ppm範圍。若密封材料層5的殘留碳量未滿20ppm，則作為還原劑的能力嫌不足，無法充分獲得上述氧化錫的還原效果。即，無法充分生成金屬錫，結果便無法充分提高玻璃基板2、3、與密封層4間之接著強度。另一方面，若密封材料層5的殘留碳量超過1000ppm，則金屬錫的生成量將過剩，玻璃的電阻值降低，導致無法確保密封層4的絕緣性。此情形將成為各種不良情況的發生肇因。The amount of carbon remaining in the sealing material layer 5 (the amount of residual carbon of the sealing material layer 5) is set in the range of 20 to 1000 ppm in terms of mass ratio. When the residual carbon amount of the sealing material layer 5 is less than 20 ppm, the ability as a reducing agent is insufficient, and the reduction effect of the above tin oxide cannot be sufficiently obtained. That is, the metal tin cannot be sufficiently formed, and as a result, the adhesion strength between the glass substrates 2, 3 and the sealing layer 4 cannot be sufficiently improved. On the other hand, when the residual carbon amount of the sealing material layer 5 exceeds 1000 ppm, the amount of metal tin generated is excessive, and the electric resistance value of the glass is lowered, so that the insulating property of the sealing layer 4 cannot be ensured. This situation will be the cause of various adverse situations.
即，在第1玻璃基板2的密封區域2b中，形成有將元件形成區域2a中所形成之電子元件的電極拉出於外部的配線。因為過剩的殘留碳會降低密封層4的絕緣性，因而根據此種密封層4，會有在第1玻璃基板2上所形成之配線間發生短路等不良情況的可能性。考慮玻璃基板2、3與密封層4間之接著強度的提升效果、密封層4的絕緣性維持等，密封材料層5的殘留碳量依質量比例計，更佳設為30~500ppm範圍。另外，關於密封材料層5中的殘留碳量的控制方法，容後述。In other words, in the sealing region 2b of the first glass substrate 2, wiring for pulling the electrode of the electronic component formed in the element forming region 2a to the outside is formed. Since the excess residual carbon lowers the insulating property of the sealing layer 4, there is a possibility that a short circuit or the like occurs between the wirings formed on the first glass substrate 2 according to the sealing layer 4. The effect of improving the adhesion strength between the glass substrates 2, 3 and the sealing layer 4, the insulation of the sealing layer 4, and the like are considered, and the residual carbon amount of the sealing material layer 5 is more preferably in the range of 30 to 500 ppm by mass. In addition, the method of controlling the amount of residual carbon in the sealing material layer 5 will be described later.
密封材料層5的厚度T1係配合第1玻璃基板2與第2玻璃基板3間之要求間隙(即密封層4的厚度T2)而設定。本實施形態的電子裝置1及其製造步驟，特別係有效於密封材料層5厚度T1設定達10μm以上的情況。且，更佳將密封材料層5的厚度T1設為10~100pm。當對具有此種厚度T1的密封材料層5照射雷射光6而施行密封時，若根據本實施形態，仍可提升玻璃基板2、3、與密封層4間之接著強度，更可提升玻璃面板的氣密密封性等。The thickness T1 of the sealing material layer 5 is set to match the required gap between the first glass substrate 2 and the second glass substrate 3 (that is, the thickness T2 of the sealing layer 4). The electronic device 1 of the present embodiment and the manufacturing steps thereof are particularly effective in the case where the thickness T1 of the sealing material layer 5 is set to 10 μm or more. Further, it is more preferable to set the thickness T1 of the sealing material layer 5 to 10 to 100 pm. When the sealing material layer 5 having such a thickness T1 is irradiated with the laser light 6 to perform sealing, according to the present embodiment, the bonding strength between the glass substrates 2, 3 and the sealing layer 4 can be improved, and the glass panel can be lifted. Hermetic sealing and so on.
另外，密封材料層5中的殘留碳並不僅侷限於使用錫-磷酸系玻璃介質的情況，就使用其他組成的玻璃介質(密封玻璃)(例如鉍系(Bi2 O3 -B2 O3 系)玻璃介質)的情況亦屬有效。即，當使用依質量比例計含有：70~90%之Bi2 O3 、1~20%之ZnO、及2~12%之B2 O3 的玻璃介質，形成密封材料層的情況，亦是藉由使適量碳殘留，而可期待產生與使用錫-磷酸系玻璃介質的情況相同的效果。Further, the residual carbon in the sealing material layer 5 is not limited to the case of using a tin-phosphate glass medium, and a glass medium (sealing glass) of another composition (for example, a bismuth system (Bi 2 O 3 -B 2 O 3 system) is used. The case of glass medium) is also effective. That is, when a glass medium containing 70 to 90% of Bi 2 O 3 , 1 to 20% of ZnO, and 2 to 12% of B 2 O 3 in terms of mass ratio is used, the sealing material layer is formed. By retaining an appropriate amount of carbon, it is expected to have the same effect as in the case of using a tin-phosphate glass medium.
由如上述密封用玻璃材料所構成的密封材料層5，如下述，係形成於第2玻璃基板3的密封區域3a上。首先，將含有密封玻璃(錫-磷酸系玻璃介質)、雷射吸收材及低膨脹填充材的密封用玻璃材料，與載體(vehicle)相混合，而調製為密封材料糊劑。The sealing material layer 5 composed of the sealing glass material described above is formed on the sealing region 3a of the second glass substrate 3 as follows. First, a sealing glass material containing a sealing glass (tin-phosphate glass medium), a laser absorbing material, and a low-expansion filler is mixed with a vehicle to prepare a sealing material paste.
載體係可使用例如：將諸如甲基纖維素、乙基纖維素、羧甲基纖維素、氧乙基纖維素、苄基纖維素、丙基纖維素、硝化纖維素等樹脂，溶解於諸如松油醇、丁基卡必醇醋酸酯、乙基卡必醇醋酸酯等溶劑中者，或例如：將諸如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、甲基丙烯酸-2-羥乙酯等丙烯酸系樹脂，溶解於諸如甲乙酮、松油醇、丁基卡必醇乙酸酯、乙基卡必醇乙酸酯等溶劑中者。The carrier may be, for example, a resin such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, oxyethyl cellulose, benzyl cellulose, propyl cellulose, nitrocellulose, or the like, dissolved in, for example, pine. In a solvent such as oleyl alcohol, butyl carbitol acetate or ethyl carbitol acetate, or for example, such as methyl (meth) acrylate, ethyl (meth) acrylate, or (meth) acrylate An acrylic resin such as ester or 2-hydroxyethyl methacrylate is dissolved in a solvent such as methyl ethyl ketone, terpineol, butyl carbitol acetate or ethyl carbitol acetate.
密封材料糊劑的黏度係只要配合塗佈在玻璃基板3上之裝置所對應的黏度便可，可利用樹脂(黏結劑成分)與溶劑的比例、密封用玻璃材料與載體的比例進行調整。在密封材料糊劑中亦可諸如消泡劑、分散劑般地，在玻璃糊劑添加公知添加物。密封材料糊劑的調製可採用使用了具備攪拌翼的旋轉式混合機、輥碎機、球磨機等的公知方法。The viscosity of the sealing material paste can be adjusted by the ratio of the resin (adhesive component) to the solvent and the ratio of the sealing glass material to the carrier, as long as the viscosity corresponding to the device applied to the glass substrate 3 is blended. A known additive may be added to the glass paste in the sealing material paste, such as an antifoaming agent or a dispersing agent. A known method using a rotary mixer equipped with a stirring blade, a roll crusher, a ball mill, or the like can be employed for the preparation of the sealing material paste.
在第2玻璃基板3的密封區域3a施行密封材料糊劑塗佈，經使其乾燥，便形成密封材料糊劑的塗佈層。密封材料糊劑係使用例如網版印刷、凹版印刷等印刷法在第2密封區域3a上施行塗佈、或者使用點膠機等沿第2密封區域3a施行塗佈。密封材料糊劑的塗佈層係依例如120℃以上的溫度施行10分鐘以上的乾燥。乾燥步驟係為將塗佈層內的溶劑除去而實施。若塗佈層內有溶劑殘留，在後續的燒成步驟中，便會有無法充分去除黏結劑成分的可能性。The sealing material paste is applied to the sealing region 3a of the second glass substrate 3, and dried to form a coating layer of the sealing material paste. The sealing material paste is applied to the second sealing region 3a by a printing method such as screen printing or gravure printing, or applied along the second sealing region 3a using a dispenser or the like. The coating layer of the sealing material paste is dried at a temperature of, for example, 120 ° C or higher for 10 minutes or longer. The drying step is carried out by removing the solvent in the coating layer. If a solvent remains in the coating layer, there is a possibility that the binder component may not be sufficiently removed in the subsequent firing step.
將上述密封材料糊劑的塗佈層施行燒成，便形成密封材料層5。燒成步驟係首先將塗佈層加熱至密封用玻璃材料主成分的密封玻璃(玻璃介質)之玻璃轉移點以下的溫度，經將塗佈層內的黏結劑成分除去後，再加熱至密封玻璃(玻璃介質)的軟化點以上的溫度，將密封用玻璃材料熔融並熔執於玻璃基板3上。依此便形成由密封用玻璃材料的燒成層所構成密封材料層5。密封材料糊劑的塗佈層燒成步驟，較佳係依200~500℃的溫度範圍實施、更佳係依230~430℃的溫度範圍實施。The coating layer of the sealing material paste is fired to form the sealing material layer 5. In the baking step, the coating layer is first heated to a temperature lower than the glass transition point of the sealing glass (glass medium) which is the main component of the sealing glass material, and the binder component in the coating layer is removed, and then heated to the sealing glass. The glass material for sealing is melted and melted on the glass substrate 3 at a temperature higher than the softening point of the (glass medium). Thus, the sealing material layer 5 composed of the fired layer of the sealing glass material is formed. The coating layer baking step of the sealing material paste is preferably carried out in a temperature range of 200 to 500 ° C, more preferably in a temperature range of 230 to 430 ° C.
此種密封材料層5的形成步驟中，藉由採用下述方法：(1)將有機物或碳等當作碳源並使之存在於密封玻璃(或密封用玻璃材料)中，且使源自碳源的碳其中一部分殘留；(2)使密封材料糊劑中的黏結劑成分(有機樹脂)、或源自有機溶劑的碳其中一部分殘留等方法，對密封材料層5的殘留碳量進行控制。另外，除該等以外的方法，在能將密封材料層5的殘留碳量，依質量比例設為20~1000ppm範圍的方法前提下，均可適用。In the step of forming the sealing material layer 5, the following method is employed: (1) an organic substance or carbon or the like is used as a carbon source and is present in the sealing glass (or glass material for sealing), and is derived from (2) controlling the residual carbon amount of the sealing material layer 5 by a method in which a part of carbon of the carbon source remains; (2) a method of leaving a binder component (organic resin) in the sealing material paste or a part of carbon derived from the organic solvent . In addition, the method other than these can be applied to the method of setting the residual carbon amount of the sealing material layer 5 in the range of 20-1000 ppm by mass ratio.
關於上述(1)的方法，係在例如粉碎玻璃之際，添加諸如醇等有機物來當作碳源。該方法係因為醇等亦具有粉碎助劑的作用，因而亦可提高玻璃的粉碎效率。在密封玻璃中所添加的碳源並不僅侷限於有機物，亦可為諸如碳黑或石墨等碳。即便相對於密封玻璃，將有機物或碳等碳源的添加量設為一定，但因為殘留碳量仍會依照燒成條件而變化，因而預先求取所添加之碳源經燒成後會有何種程度殘留的相關資料。再根據此資料對密封材料層5的殘留碳量進行控制。此外，亦可將碳源添加量設為一定，並使燒成條件(溫度、時間)產生變化，而對殘留碳量進行控制。In the method of the above (1), for example, when the glass is pulverized, an organic substance such as an alcohol is added as a carbon source. This method is because the alcohol or the like also functions as a pulverization aid, so that the pulverization efficiency of the glass can also be improved. The carbon source added to the sealing glass is not limited to organic matter, and may be carbon such as carbon black or graphite. Even if the amount of carbon source such as organic matter or carbon is constant with respect to the sealing glass, since the amount of residual carbon changes depending on the firing conditions, it is determined in advance whether the carbon source to be added is burned. Relevant information on the extent of the residue. Further, based on this data, the amount of residual carbon of the sealing material layer 5 is controlled. Further, the amount of carbon source added may be constant, and the firing conditions (temperature, time) may be changed to control the amount of residual carbon.
(2)的方法係在密封玻璃中未添加碳源，使源自施行糊化時所使用的黏結劑成分(有機樹脂)或有機溶劑的碳其中一部分殘留之方法。此情況，載體的組成、施行糊化時的密封用玻璃材料與載體之組成比、燒成條件、特別係從樹脂進行燃燒、分解的溫度區域起至密封玻璃進行軟化的溫度範圍中，升溫速度與保持時間均屬重要事項。關於密封材料糊劑製作時所使用的載體，使用(1)之方法的情況並無特別限制，但當使用(2)之方法的情況，較佳係使用將硝化纖維素溶解於諸如：松油醇、丁基卡必醇醋酸酯、乙基卡必醇醋酸酯等有機溶劑中者。The method of (2) is a method in which a carbon source is not added to the sealing glass, and a part of carbon derived from a binder component (organic resin) or an organic solvent used for gelatinization is left. In this case, the composition of the carrier, the composition ratio of the sealing glass material to the carrier at the time of gelatinization, and the firing conditions, particularly in the temperature range from the burning and decomposition of the resin to the softening of the sealing glass, the temperature rising rate And holding time are important matters. Regarding the carrier used in the production of the sealing material paste, the case of using the method (1) is not particularly limited, but in the case of the method of (2), it is preferred to use a method of dissolving nitrocellulose in such as: pine oil. An organic solvent such as an alcohol, butyl carbitol acetate or ethyl carbitol acetate.
(2)之方法所使用的載體，較佳係使0.5~5質量%硝化纖維素，溶解於從松油醇、丁基卡必醇醋酸酯及乙基卡必醇醋酸酯所構成群組中選擇的一種有機溶劑、或二種以上混合溶劑95~99.5質量%者。且，關於密封用玻璃材料的糊化，較佳係將85~93質量%密封用玻璃材料、與7~15質量%載體進行混合而調製成密封材料糊劑。藉由使用此種載體或密封材料糊劑，便可提升密封材料層5的殘留碳量控制性。(2) The carrier used in the method, preferably 0.5 to 5% by mass of nitrocellulose, dissolved in a group consisting of terpineol, butyl carbitol acetate and ethyl carbitol acetate One type of organic solvent or two or more kinds of mixed solvents selected is 95 to 99.5% by mass. Further, the gelatinization of the sealing glass material is preferably carried out by mixing 85 to 93% by mass of the sealing glass material with 7 to 15% by mass of the carrier to prepare a sealing material paste. By using such a carrier or a sealing material paste, the residual carbon amount controllability of the sealing material layer 5 can be improved.
關於密封材料糊劑的塗佈層燒成步驟，一般係依不會使密封用玻璃材料還原的方式，採用可使樹脂成分完全燃燒、分解的條件。具體而言，藉由在樹脂進行燃燒、分解的溫度以上，且未達密封玻璃進行軟化流動的溫度之溫度區域中，使升溫速度變慢，且保持1~15小時左右，便促進樹脂的燃燒、分解。當此用(2)之方法的情況，藉由對樹脂的燃燒、分解步驟進行控制，便可使適量的碳殘留於密封材料層5中。The baking step of the coating layer of the sealing material paste is generally carried out in such a manner that the resin component can be completely burned and decomposed without reducing the glass material for sealing. Specifically, in the temperature region where the resin is burned or decomposed at a temperature higher than the temperature at which the sealing glass is softened and flows, the temperature increase rate is slowed and maintained for about 1 to 15 hours, thereby promoting the combustion of the resin. ,break down. In the case of the method of (2), an appropriate amount of carbon remains in the sealing material layer 5 by controlling the combustion and decomposition steps of the resin.
依如上述，載體中的樹脂成分較佳係硝化纖維素。硝化纖維素係依200~250℃範圍的溫度進行燃燒、分解。本實施形態之密封玻璃進行軟化流動的溫度係260~450℃範圍。因而，200~450℃的溫度範圍便屬重要。如上述具有殘留碳的密封材料層5係藉由對200~450℃的升溫速度進行控制便可獲得。具體而言，較佳係在200~450℃溫度範圍內依10~35℃/min速度進行升溫。利用批次爐等進行燒成時，為使爐內溫度呈均勻，當保持在200~450℃溫度範圍的情況，較佳係將保持時間設為未滿20分鐘。藉由使用此種條件，便可將密封材料層5的殘留碳量控制於所需範圍內。As described above, the resin component in the carrier is preferably nitrocellulose. Nitrocellulose is burned and decomposed according to the temperature in the range of 200 to 250 °C. The temperature at which the sealing glass of the present embodiment softens and flows is in the range of 260 to 450 °C. Therefore, a temperature range of 200 to 450 ° C is important. The sealing material layer 5 having residual carbon as described above can be obtained by controlling the temperature increase rate of 200 to 450 °C. Specifically, it is preferred to raise the temperature at a temperature of from 10 to 35 ° C/min in a temperature range of 200 to 450 ° C. When firing in a batch furnace or the like, in order to make the temperature in the furnace uniform, it is preferable to set the holding time to less than 20 minutes while maintaining the temperature in the range of 200 to 450 °C. By using such conditions, the residual carbon amount of the sealing material layer 5 can be controlled within a desired range.
其次，如第2(a)圖所示，使用第2玻璃基板3(其係具有密封材料層5)、與第1玻璃基板2(其係具有元件形成區域2a，該元件形成區域2a係具有另行製作的電子元件)，製作例如OELD、PDP、LCD等使用FPD、OEL元件的照明裝置、或諸如染料敏化太陽電池之類的太陽電池等電子裝置1。即如第2(b)圖所示，將第1玻璃基板2與第2玻璃基板3，依具有元件形成區域2a之一面、與具有密封材料層5之一面呈相對向狀態進行積層。在第1玻璃基板2的元件形成區域2a上，根據密封材料層5的厚度形成間隙。Next, as shown in Fig. 2(a), the second glass substrate 3 (having a sealing material layer 5) and the first glass substrate 2 (having an element forming region 2a having the element forming region 2a) are used. An electronic device 1 such as an OLED, a PDP, or an LCD that uses an FPD or an OEL element, or an electronic device such as a solar cell such as a dye-sensitized solar cell is produced. In other words, as shown in Fig. 2(b), the first glass substrate 2 and the second glass substrate 3 are laminated on one surface of the element forming region 2a and in a state in which one surface of the sealing material layer 5 is opposed to each other. A gap is formed in the element formation region 2a of the first glass substrate 2 in accordance with the thickness of the sealing material layer 5.
其次，如第2(c)圖所示，透過第2玻璃基板3對密封材料層5照射雷射光6。雷射光6係沿框狀密封材料層5一邊進行掃描一邊照射。雷射光6並無特別的限定，可使用來自諸如半導體雷射、碳酸氣體雷射、準分子雷射、YAG雷射、HeNe雷射等的雷射光。雷射光6的輸出係配合密封材料層5的厚度等而適當設定，宜設定為例如2~150W範圍內。若雷射輸出未滿2W，便會有無法將密封材料層5熔融的可能性；反之，若超過150W，則玻璃基板2、3便容易發生裂痕、斷裂等情形。雷射光的輸出較佳係5~100W範圍內。Next, as shown in FIG. 2(c), the sealing material layer 5 is irradiated with the laser light 6 through the second glass substrate 3. The laser beam 6 is irradiated while scanning along the frame-shaped sealing material layer 5. The laser light 6 is not particularly limited, and laser light from, for example, a semiconductor laser, a carbon dioxide gas laser, a pseudo-molecular laser, a YAG laser, a HeNe laser, or the like can be used. The output of the laser light 6 is appropriately set in accordance with the thickness of the sealing material layer 5, etc., and is preferably set to, for example, 2 to 150 W. If the laser output is less than 2 W, there is a possibility that the sealing material layer 5 cannot be melted. On the other hand, if it exceeds 150 W, the glass substrates 2 and 3 are liable to be cracked or broken. The output of the laser light is preferably in the range of 5 to 100 W.
密封材料層5係從被沿其進行掃描的雷射光6所照射部分開始依序熔融，若雷射光6的照射結束，便急冷固化，而固接於第1玻璃基板2。然後，藉由圍繞密封材料層5全周進行雷射光6照射，便如第2(d)圖所示，形成將第1玻璃基板2與第2玻璃基板3間施行密封的密封層4。因為使用密封玻璃(錫-磷酸系玻璃介質)的密封材料層5係根據殘留碳而提升與玻璃基板2間之反應性，因而即便是在利用雷射光6照射所施行的短時間熔融固化步驟(密封步驟)中，仍可提升玻璃基板2與密封玻璃間之接著性。所以，可提高玻璃基板2、3、與密封層4間之接著強度。The sealing material layer 5 is sequentially melted from the portion irradiated by the laser light 6 scanned along the same, and when the irradiation of the laser light 6 is completed, it is rapidly solidified and fixed to the first glass substrate 2. Then, by irradiating the laser light 6 around the entire sealing material layer 5, as shown in the second (d), the sealing layer 4 for sealing the first glass substrate 2 and the second glass substrate 3 is formed. Since the sealing material layer 5 using a sealing glass (tin-phosphate glass medium) enhances the reactivity with the glass substrate 2 in accordance with residual carbon, even in the short-time melt-solidification step performed by irradiation with the laser light 6 ( In the sealing step), the adhesion between the glass substrate 2 and the sealing glass can still be improved. Therefore, the adhesion strength between the glass substrates 2, 3 and the sealing layer 4 can be improved.
依此的話，便製成利用由第1玻璃基板2、第2玻璃基板3及密封層4所構成之玻璃面板，將在元件形成區域2a上所形成之電子元件施行氣密密封的電子裝置1。另外，內部施行氣密密封的玻璃面板並不僅侷限於電子裝置1，亦可應用於例如電子零件的密封體(封裝)、或如雙層真空玻璃之類的玻璃構件(建材等)。In this case, the electronic device 1 in which the electronic components formed on the element forming region 2a are hermetically sealed by using the glass panel composed of the first glass substrate 2, the second glass substrate 3, and the sealing layer 4 is formed. . Further, the glass panel which is hermetically sealed inside is not limited to the electronic device 1, and can be applied to, for example, a sealing body (package) of an electronic component or a glass member (a building material or the like) such as a double-layer vacuum glass.
電子裝置1的可靠度係依存於諸如由密封層4所施行的氣密密封性、或玻璃基板2、3與密封層4間之接著強度等。根據本實施形態，因為可提高氣密密封性與接著強度，因而可獲得可靠度優異的電子裝置1。此處，密封材料層5中的碳即便在雷射密封後亦會殘留。所以，使用殘留碳量依質量比例計為20~1000ppm範圍的密封材料層5所形成的密封層4，即便碳的存在形態有變化，殘留碳量本身仍與密封材料層5同等。所以，根據殘留碳量依質量比例計為20~1000ppm範圍的密封層4，便可提升電子裝置1的密封可靠度與機械可靠度等。The reliability of the electronic device 1 depends on, for example, hermetic sealing performed by the sealing layer 4, or adhesion strength between the glass substrates 2, 3 and the sealing layer 4, and the like. According to the present embodiment, since the hermetic sealing property and the bonding strength can be improved, the electronic device 1 having excellent reliability can be obtained. Here, the carbon in the sealing material layer 5 remains even after the laser sealing. Therefore, the sealing layer 4 formed of the sealing material layer 5 having a residual carbon amount in the range of 20 to 1000 ppm by mass ratio is equivalent to the sealing material layer 5 itself even if the form of carbon is changed. Therefore, the sealing layer 4 in the range of 20 to 1000 ppm by mass ratio based on the residual carbon amount can improve the sealing reliability and mechanical reliability of the electronic device 1.
實施例Example
其次，針對本發明的具體實施例及其評估結果進行敘述。另外，以下的說明並非將本發明予以限定，亦可在遵循本發明之主旨的形式下進行改變。Next, specific embodiments of the present invention and evaluation results thereof will be described. In addition, the following description is not intended to limit the invention, and may be modified in the form of the gist of the invention.
(實施例1)(Example 1)
製備依質量比例計，含有：SnO：55.7%、SnO2 ：3.1%、P2 O5 ：32.5%、ZnO：4.8%、Al2 O3 ：2.3%、SiO2 ：1.6%組成的錫-磷酸系玻璃介質、作為低膨脹填充材的磷酸鋯((ZrO)2 P2 O7 )粉末、以及依質量比計含有：Fe2 O3 ：35%、Cr2 O3 ：35%、Co2 O3 ：20%、MnO：10%組成的雷射吸收材。此外，將作為黏結劑成分的硝化纖維素4質量%，溶解於由丁基卡必醇醋酸酯所構成溶劑96質量%中，製得載體。Prepared by mass ratio, containing: SnO: 55.7%, SnO 2 : 3.1%, P 2 O 5 : 32.5%, ZnO: 4.8%, Al 2 O 3 : 2.3%, SiO 2 : 1.6% composition of tin-phosphoric acid a glass medium, a zirconium phosphate ((ZrO) 2 P 2 O 7 ) powder as a low expansion filler, and a mass ratio: Fe 2 O 3 : 35%, Cr 2 O 3 : 35%, Co 2 O 3 : 20%, MnO: 10% of the composition of the laser absorption material. In addition, 4% by mass of nitrocellulose as a binder component was dissolved in 96% by mass of a solvent composed of butyl carbitol acetate to prepare a carrier.
錫-磷酸系玻璃介質係依如下進行製作。首先，依成為上述成分比的方式，將玻璃施行溶解而製得碎玻璃。接著，將碎玻璃利用氧化鋁製球磨機施行粉碎。此時，粉碎助劑係相對於玻璃1kg，添加2cc的乙醇。接著，利用氣流分級機依最大粒徑為8μm的方式進行分級，便獲得目標之錫-磷酸系玻璃介質。A tin-phosphate glass medium was produced as follows. First, the glass is dissolved in a manner to achieve the above composition ratio to obtain cullet. Next, the cullet was pulverized by an alumina ball mill. At this time, the pulverization aid was added to 2 kg of ethanol with respect to 1 kg of glass. Next, classification was carried out by means of a gas current classifier so that the maximum particle diameter was 8 μm, and the intended tin-phosphate glass medium was obtained.
其次，將上述錫-磷酸系玻璃介質56體積%、磷酸鋯粉末42體積%、及雷射吸收材2體積%進行混合，製得密封用玻璃材料(熱膨脹係數：47×10-7 /℃)。將該密封用玻璃材料80質量%與載體20質量%進行混合，便調製得密封材料糊劑。接著，在由無鹼玻璃(熱膨脹係數：38×10-7 /℃)構成的第2玻璃基板(尺寸：90×90×0.7mmt)外周區域，將密封材料糊劑利用網版印刷法施行塗佈(線寬：500μm)後，依120℃×10分鐘的條件施行乾燥。Next, 56 wt% of the tin-phosphate glass medium, 42% by volume of zirconium phosphate powder, and 2% by volume of the laser absorbing material were mixed to obtain a glass material for sealing (thermal expansion coefficient: 47 × 10 -7 / ° C) . The sealing material paste was prepared by mixing 80% by mass of the sealing glass material with 20% by mass of the carrier. Next, the sealing material paste was applied by screen printing in the outer peripheral region of the second glass substrate (size: 90 × 90 × 0.7 mmt) composed of alkali-free glass (thermal expansion coefficient: 38 × 10 -7 / ° C). After the cloth (line width: 500 μm), it was dried at 120 ° C for 10 minutes.
將經乾燥後的密封材料糊劑塗佈層，依升溫速度5℃/min升溫至250℃，在該溫度下保持40分鐘而施行脫黏結劑處理後，依升溫速度5℃/min升溫至430℃，在該溫度下保持10分鐘而施行燒成。依此便形成膜厚T1為60μm的密封材料層。密封材料層的殘留碳量係200ppm。另外，密封材料層的殘留碳量係使用碳‧硫分析裝置EMIA-320V(商品名，堀場製作所公司製)進行測定的值。其他實施例亦同。The dried sealing material paste coating layer was heated to 250 ° C at a heating rate of 5 ° C / min, and maintained at this temperature for 40 minutes to perform debonding treatment, and then heated to a temperature of 5 ° C / min to 430. At °C, it was kept at this temperature for 10 minutes and baked. Thus, a sealing material layer having a film thickness T1 of 60 μm was formed. The residual carbon amount of the sealing material layer was 200 ppm. In addition, the residual carbon amount of the sealing material layer is a value measured using a carbon-sulfur analyzer EMIA-320V (trade name, manufactured by Horiba, Ltd.). Other embodiments are the same.
將具有上述密封材料層的第2玻璃基板、與具有元件形成區域(已形成OEL元件的區域)的第1玻璃基板(由與第2玻璃基板同組成、同形狀的無鹼玻璃所構成之基板)進行積層。接著，透過第2玻璃基板對密封材料層，將波長940nm、輸出25W的雷射光(半導體雷射)依10mm/s掃描速度進行照射，藉由使密封材料層熔融並急冷固化，便將第1玻璃基板與第2玻璃基板施行密封。另外，針對密封層的殘留碳量，經如同密封材料層般的進行同樣測定，確認為與密封材料層的殘留碳量同等。在後述特性評估中，提供依此方式利用玻璃面板對元件形成區域施行密封的電子裝置。a second glass substrate having the above-described sealing material layer and a first glass substrate having an element forming region (a region in which an OEL element has been formed) (a substrate composed of an alkali-free glass having the same composition and shape as the second glass substrate) ) Carry out the layering. Next, the laser material (semiconductor laser) having a wavelength of 940 nm and outputting 25 W is irradiated to the sealing material layer through the second glass substrate at a scanning speed of 10 mm/s, and the sealing material layer is melted and quenched and solidified. The glass substrate and the second glass substrate are sealed. In addition, the residual carbon amount of the sealing layer was measured in the same manner as the sealing material layer, and it was confirmed that the residual carbon amount of the sealing layer was the same as that of the sealing material layer. In the characteristic evaluation described later, an electronic device that seals the element formation region by the glass panel in this manner is provided.
(實施例2~4)(Examples 2 to 4)
除將錫-磷酸系玻璃介質的組成、低膨脹填充材、雷射吸收材的種類、該等的調配比，變更為表1所示條件之外，其餘均如同實施例1般的調製密封材料糊劑。除使用該等密封材料糊劑，且將密封材料層的殘留碳量控制方法變更為下示方法之外，其餘均如同實施例1，實施針對第2玻璃基板之密封材料層的形成、第1玻璃基板與第2玻璃基板的雷射密封。在後述特性評估中，提供依此方式利用玻璃面板對元件形成區域施行密封的電子裝置。關於密封材料層的殘留碳量，實施例2係450ppm、實施例3係70ppm、實施例4係850ppm。殘留碳量係如同實施例1般的進行測定。The composition of the tin-phosphoric acid-based glass medium, the type of the low-expansion filler, the type of the laser-absorbent material, and the blending ratio were changed to the conditions shown in Table 1, and the rest of the preparation was as in Example 1. Paste. Except that the sealing material paste was used, and the residual carbon amount control method of the sealing material layer was changed to the method shown below, the formation of the sealing material layer for the second glass substrate was carried out as in the first embodiment, and the first Laser sealing of the glass substrate and the second glass substrate. In the characteristic evaluation described later, an electronic device that seals the element formation region by the glass panel in this manner is provided. The amount of residual carbon in the sealing material layer was 450 ppm in Example 2, 70 ppm in Example 3, and 850 ppm in Example 4. The amount of residual carbon was measured as in Example 1.
實施例2中，依如下述，對密封材料層的殘留碳量進行控制。當將錫-磷酸系玻璃介質、低膨脹填充材及雷射吸收材進行混合，而製作密封用玻璃材料之際，將摻合入作為還原劑的碳黑。碳黑的摻合量係相對於密封用玻璃材料設為500ppm。除使用此種密封用玻璃材料之外，其餘均如同實施例1般的形成密封材料糊劑的塗佈層(依120℃×10分鐘施行乾燥)。將經乾燥後的密封材料糊劑塗佈層，依升溫速度8℃/min升溫至230℃，在該溫度下保持60分鐘而施行脫黏結劑處理後，再依升溫速度8℃/min升溫至430℃，在該溫度下保持10分鐘而進行燒成。In Example 2, the amount of residual carbon in the sealing material layer was controlled as follows. When a tin-phosphate glass medium, a low-expansion filler, and a laser absorbing material are mixed to produce a glass material for sealing, carbon black as a reducing agent is blended. The blending amount of carbon black was set to 500 ppm with respect to the glass material for sealing. A coating layer for forming a sealing material paste (dried at 120 ° C × 10 minutes) was used in the same manner as in Example 1 except that the glass material for sealing was used. The dried sealing material paste coating layer is heated to 230 ° C according to a heating rate of 8 ° C / min, held at this temperature for 60 minutes, and subjected to debonding treatment, and then heated to a temperature increase rate of 8 ° C / min to The temperature was maintained at 430 ° C for 10 minutes at this temperature.
實施例3中，依如下進行密封材料層的殘留碳量控制。如同實施例1，形成密封材料糊劑的塗佈層。密封材料糊劑係將密封用玻璃材料84質量%與載體16質量%相混合而調製。塗佈層係依120℃×10分鐘的條件施行乾燥。另外，在碎玻璃施行粉碎時並未使用乙醇。將經乾燥後的密封材料糊劑塗佈層，依升溫速度25℃/min升溫至430℃，在該溫度下保持10分鐘而進行燒成。實施例4係依照如同實施例2相同的條件進行殘留碳量控制。此時，碳黑的摻合量係相對於密封用玻璃材料設為1000ppm。實施例2~4中，密封層的殘留碳量係與密封材料層同等。In Example 3, the residual carbon amount of the sealing material layer was controlled as follows. As in Example 1, a coating layer of a sealing material paste was formed. The sealing material paste was prepared by mixing 84% by mass of the sealing glass material with 16% by mass of the carrier. The coating layer was dried at 120 ° C for 10 minutes. In addition, ethanol was not used in the pulverization of the cullet. The dried sealing material paste coating layer was heated to 430 ° C at a temperature increase rate of 25 ° C / min, and held at this temperature for 10 minutes to be baked. In Example 4, residual carbon amount control was carried out in accordance with the same conditions as in Example 2. At this time, the blending amount of carbon black was set to 1000 ppm with respect to the glass material for sealing. In Examples 2 to 4, the residual carbon amount of the sealing layer was equivalent to that of the sealing material layer.
(實施例5~6)(Examples 5 to 6)
製備表1所示之錫-磷酸系玻璃介質、低膨脹填充材及雷射吸收材，藉由將該等依表1所示組成比進行混合，而分別製得密封用玻璃材料。將該等密封用玻璃材料82質量%與如同實施例1的載體18質量%進行混合，而調製得密封材料糊劑。接著，在由鈉鈣玻璃(熱膨脹係數：87×10-7 /℃)構成的第2玻璃基板(尺寸：100×100×0.55mmt)外周區域，將各個密封材料糊劑利用網版印刷法施行塗佈(線寬：500μm)後，再依120℃×10分鐘的條件施行乾燥。The tin-phosphate glass medium, the low-expansion filler, and the laser absorbing material shown in Table 1 were prepared, and the glass materials for sealing were prepared by mixing the composition ratio shown in Table 1. The sealing glass material 82% by mass and the carrier 18% by mass as in Example 1 were mixed to prepare a sealing material paste. Next, in the outer peripheral region of the second glass substrate (size: 100 × 100 × 0.55 mmt) composed of soda lime glass (thermal expansion coefficient: 87 × 10 -7 / ° C), each sealing material paste was applied by screen printing. After coating (line width: 500 μm), drying was carried out under the conditions of 120 ° C × 10 minutes.
將上述密封材料糊劑的塗佈層(乾燥後)分別施行燒成，而分別形成膜厚T1為60μm的密封材料層。關於密封材料層的殘留碳量控制方法，實施例5係如同實施例3，實施例6係如同實施例1。實施例5的密封材料層殘留碳量係100ppm，實施例6係150ppm。Each of the coating layers (after drying) of the above-mentioned sealing material paste was fired to form a sealing material layer having a film thickness T1 of 60 μm. Regarding the method of controlling the residual carbon amount of the sealing material layer, Example 5 is as in Example 3, and Example 6 is as in Example 1. The amount of residual carbon in the sealing material layer of Example 5 was 100 ppm, and Example 6 was 150 ppm.
接著，將具有密封材料層的第2玻璃基板、以及具有元件形成區域(已形成OEL元件的區域)的第1玻璃基板(由與第2玻璃基板同組成、同形狀的鈉鈣玻璃構成之基板)施行積層。接著，透過第2玻璃基板對密封材料層，將波長940nm、輸出40W的雷射光(半導體雷射)依5mm/s掃描速度進行照射，藉由將密封材料層熔融並急冷固化，便將第1玻璃基板與第2玻璃基板施行密封。密封層的殘留碳量係與密封材料層同等。在後述特性評估中，提供依此方式利用玻璃面板對元件形成區域施行密封的電子裝置。Next, a second glass substrate having a sealing material layer and a first glass substrate having a device forming region (a region in which an OEL element has been formed) (a substrate made of soda lime glass having the same composition and shape as the second glass substrate) ) Implementing a layer. Next, the laser material (semiconductor laser) having a wavelength of 940 nm and outputting 40 W is irradiated to the sealing material layer through the second glass substrate at a scanning speed of 5 mm/s, and the sealing material layer is melted and quenched and solidified. The glass substrate and the second glass substrate are sealed. The amount of residual carbon in the sealing layer is equivalent to that of the sealing material layer. In the characteristic evaluation described later, an electronic device that seals the element formation region by the glass panel in this manner is provided.
(比較例1)(Comparative Example 1)
使用與實施例1同組成的錫-磷酸系玻璃介質，如同實施例1般的實施密封用玻璃材料的製作、密封材料糊劑的調製、針對第2玻璃基板之密封材料層的形成、以及第1玻璃基板與第2玻璃基板的雷射密封。關於密封材料層的殘留碳量控制方法，係如同實施例2同樣的，使用在密封用玻璃材料中摻合入碳黑的方法。但，碳黑的摻合量係相對於密封用玻璃材料設為1500ppm。在後述特性評估中，提供依此方式利用玻璃面板對元件形成區域施行密封的電子裝置。Using the tin-phosphate glass medium having the same composition as in Example 1, the production of the glass material for sealing, the preparation of the sealing material paste, the formation of the sealing material layer for the second glass substrate, and the 1 Laser sealing of the glass substrate and the second glass substrate. As a method of controlling the amount of residual carbon in the sealing material layer, a method of incorporating carbon black into the glass material for sealing is used in the same manner as in the second embodiment. However, the blending amount of carbon black was set to 1500 ppm with respect to the glass material for sealing. In the characteristic evaluation described later, an electronic device that seals the element formation region by the glass panel in this manner is provided.
(比較例2)(Comparative Example 2)
製備依質量比例計含有V2 O5 ：44.3%、Sb2 O3 ：35.1%、P2 O5 ：19.7%、Al2 O3 ：0.5%、TiO2 ：0.4%組成的釩系玻璃介質、以及作為低膨脹填充材的磷酸鋯粉末。更，將作為黏結劑成分的硝化纖維素4質量%溶解於二乙二醇單丁醚乙酸脂96質量%中，而製得載體。A vanadium-based glass medium containing V 2 O 5 : 44.3%, Sb 2 O 3 : 35.1%, P 2 O 5 : 19.7%, Al 2 O 3 : 0.5%, and TiO 2 : 0.4% by mass ratio, And a zirconium phosphate powder as a low expansion filler. Further, 4% by mass of nitrocellulose as a binder component was dissolved in 96% by mass of diethylene glycol monobutyl ether acetate to prepare a carrier.
將釩系玻璃介質90體積%與菫青石粉末10體積%進行混合，而製得密封用玻璃材料(熱膨脹係數：74×10-7 /℃)。將該密封用玻璃材料73質量%與載體27質量%進行混合，而調製得密封材料糊劑。接著，在由與實施例1同樣的無鹼玻璃所構成之第2玻璃基板外周區域，將密封材料糊劑利用網版印刷法施行塗佈(線寬W：500μm)後，依120℃×10分鐘的條件施行乾燥。將該塗佈層依450℃×10分鐘的條件施行燒成，便形成膜厚T1為60μm的密封材料層。90% by volume of the vanadium-based glass medium and 10% by volume of the cordierite powder were mixed to obtain a glass material for sealing (thermal expansion coefficient: 74 × 10 -7 / ° C). The sealing glass material was mixed with 73% by mass of the sealing material and 27% by mass of the carrier to prepare a sealing material paste. Next, in the outer peripheral region of the second glass substrate composed of the alkali-free glass similar to that of Example 1, the sealing material paste was applied by screen printing (line width W: 500 μm), and then 120 ° C × 10 Dry in a minute condition. The coating layer was fired at 450 ° C for 10 minutes to form a sealing material layer having a film thickness T1 of 60 μm.
接著，將具有密封材料層的第2玻璃基板、以及具有元件形成區域(已形成OEL元件的區域)的第1玻璃基板(由與第2玻璃基板同組成、同形狀的鈉鈣玻璃構成之基板)施行積層。接著，透過第2玻璃基板對密封材料層，將波長940nm、輸出40W的雷射光(半導體雷射)依5mm/s掃描速度進行照射，藉由將密封材料層熔融並急冷固化，便將第1玻璃基板與第2玻璃基板施行密封。在後述特性評估中，提供依此方式利用玻璃面板對元件形成區域施行密封的電子裝置。Next, a second glass substrate having a sealing material layer and a first glass substrate having a device forming region (a region in which an OEL element has been formed) (a substrate made of soda lime glass having the same composition and shape as the second glass substrate) ) Implementing a layer. Next, the laser material (semiconductor laser) having a wavelength of 940 nm and outputting 40 W is irradiated to the sealing material layer through the second glass substrate at a scanning speed of 5 mm/s, and the sealing material layer is melted and quenched and solidified. The glass substrate and the second glass substrate are sealed. In the characteristic evaluation described later, an electronic device that seals the element formation region by the glass panel in this manner is provided.
其次，針對實施例1~6及比較例1~2的玻璃面板外觀，評估玻璃基板有無裂痕。外觀係利用光學顯微鏡進行觀察並評估。且，測定各玻璃面板的氣密性。氣密性係使用氦氣測漏測試儀施行評估。此外，利用實施例1~6及比較例1~2中所使用之密封用玻璃材料施行的密封層與玻璃基板間之接著強度、及密封層的電阻值，係依如下進行測定。該等的測定、評估結果，如表1與表2所示。表1與表2中合併記載玻璃面板的製造條件。Next, the appearance of the glass panel of Examples 1 to 6 and Comparative Examples 1 and 2 was evaluated for the presence or absence of cracks in the glass substrate. The appearance was observed and evaluated using an optical microscope. Moreover, the airtightness of each glass panel was measured. The airtightness is evaluated using a helium leak tester. In addition, the adhesive strength between the sealing layer and the glass substrate which were carried out by the sealing glass materials used in Examples 1 to 6 and Comparative Examples 1 and 2, and the resistance value of the sealing layer were measured as follows. The results of these measurements and evaluations are shown in Tables 1 and 2. The manufacturing conditions of the glass panel are collectively described in Table 1 and Table 2.
利用密封用玻璃材料施行的玻璃基板接著強度之測定方法係如下。首先，在寬30mm的第1玻璃基板端部附近，使用各例的密封材料糊劑，形成厚度60μm、線寬1mm的密封材料層。糊劑塗佈層係依各自的合適條件進行燒成。接著，將第2玻璃基板端部配置於密封材料層上。第2玻璃基板係依與第1玻璃基板呈不同狀態(以密封材料層為中心，第1與第2玻璃基板係呈直線狀排列狀態)的方式配置。將該等一邊利用10kg荷重施行加壓，一邊對密封材料層依10mm/s掃描速度照射波長940nm雷射光，而施行密封。雷射光的輸出係設為適合各材料的值。將依此所形成的接著強度測定用樣品的其中一玻璃基板利用夾具進行固定，並從另一玻璃基板的密封層，將20mm的部分依1mm/min速度施行加壓，並將密封層崩壞時的荷重視為「接著強度」The method for measuring the strength of the glass substrate to be applied by the glass material for sealing is as follows. First, a sealing material layer having a thickness of 60 μm and a line width of 1 mm was formed in the vicinity of the end portion of the first glass substrate having a width of 30 mm using each of the sealing material pastes. The paste coating layer is fired according to respective suitable conditions. Next, the end of the second glass substrate is placed on the sealing material layer. The second glass substrate is disposed in a state different from the first glass substrate (the first and second glass substrates are linearly arranged around the sealing material layer). These were pressed with a load of 10 kg, and the sealing material layer was irradiated with a laser beam having a wavelength of 940 nm at a scanning speed of 10 mm/s to perform sealing. The output of the laser light is set to a value suitable for each material. One of the glass substrates of the sample for measuring the strength of the subsequent strength formed by the above was fixed by a jig, and a portion of 20 mm was pressed at a speed of 1 mm/min from the sealing layer of the other glass substrate, and the sealing layer was collapsed. The importance of the time is "the strength of the next"
密封層的電阻值測定方法係如下。首先，製備依4.3mm間隔形成2個ITO導電膜的玻璃基板A。在此之外另行製備已形成膜厚60μm、寬1mm、長30mm密封材料層(使用各例密封材料糊劑所形成的密封材料層)的玻璃基板B。接著，將玻璃基板A與玻璃基板B，依密封材料層橫跨於2個ITO導電膜上的方式進行重疊。從玻璃基板B側朝密封材料層，將波長940nm雷射光依10mm/s掃描速度施行照射而密封。The method for measuring the resistance value of the sealing layer is as follows. First, a glass substrate A in which two ITO conductive films were formed at intervals of 4.3 mm was prepared. A glass substrate B having a film thickness of 60 μm, a width of 1 mm, and a length of 30 mm (a sealing material layer formed using each of the sealing material pastes) was separately prepared. Next, the glass substrate A and the glass substrate B were stacked so that the sealing material layer straddles the two ITO conductive films. From the side of the glass substrate B toward the sealing material layer, laser light having a wavelength of 940 nm was irradiated at a scanning speed of 10 mm/s to be sealed.
針對依此所形成的電阻值測定用樣品，在2個ITO導電膜上連接著電極，利用將偏壓電壓設為100V的微小電流計施行微小電流的測定，並求取電阻值。測定係在氮環境中實施。在將作為參照樣品的雷射密封前之玻璃基板A的2個ITO導電膜間的電阻值進行測定的情況下，結果為2.0×1012 Ω。關於由各例所獲得之電阻值，將測定值達2.0×1011 Ω以上的情況評為「良好(○)」，將測定值未滿2.0×1011 Ω的情況評為「不良(×)」，並記於表1與表2中。With respect to the sample for measuring the resistance value thus formed, an electrode was connected to the two ITO conductive films, and a minute current was measured by a minute current meter having a bias voltage of 100 V to obtain a resistance value. The assay is carried out in a nitrogen environment. When the resistance value between the two ITO conductive films of the glass substrate A before the laser sealing as the reference sample was measured, it was 2.0 × 10 12 Ω. The resistance value obtained from each example was rated as "good (○)" when the measured value was 2.0 × 10 11 Ω or more, and "bad (×) when the measured value was less than 2.0 × 10 11 Ω. And recorded in Table 1 and Table 2.
由表1與表2中得知，依照實施例1~6所製得之玻璃面板均屬於外觀與氣密性優異，且可獲得良好接著強度。相對於此，密封材料層殘留碳量超過1000ppm的比較例1之玻璃面板，得知雖接著強度良好，但密封層絕緣性卻降低。此情況，玻璃基板上所形成之配線發生諸如短路等不良情況的可能性頗大。且，使用釩系玻璃介質的比較例2之習知玻璃面板，係接著強度較低，且玻璃面板(電子裝置)的可靠度差。It is understood from Tables 1 and 2 that the glass panels obtained in accordance with Examples 1 to 6 are excellent in appearance and airtightness, and good adhesion strength can be obtained. On the other hand, in the glass panel of Comparative Example 1 in which the amount of residual carbon in the sealing material layer exceeded 1000 ppm, it was found that although the strength of the bonding was good, the insulating property of the sealing layer was lowered. In this case, there is a high possibility that the wiring formed on the glass substrate is in a bad condition such as a short circuit. Further, the conventional glass panel of Comparative Example 2 using a vanadium-based glass medium has a low bonding strength and a poor reliability of the glass panel (electronic device).
本發明係可利用於諸如具有密封材料層之玻璃構件、以及諸如有機EL顯示器、電漿顯示面板、液晶顯示裝置等平板型顯示器裝置、或染料敏化太陽電池等電子裝置的製造。The present invention can be utilized for the manufacture of an electronic device such as a glass member having a sealing material layer, and a flat panel display device such as an organic EL display, a plasma display panel, a liquid crystal display device, or a dye-sensitized solar cell.
另外，將2008年12月19日所提出申請的日本專利申請案出願2008-323422號的說明書、申請專利範圍、圖式及摘要等的全部內容，爰引於本案中，並融入為本發明的說明書揭示。In addition, the entire contents of the specification, the patent application scope, the drawings and the abstract of the Japanese Patent Application No. 2008-323422 filed on Dec. 19, 2008, are incorporated herein by reference. The instructions are disclosed.
1．．．電子裝置1. . . Electronic device
2．．．第1玻璃基板2. . . First glass substrate
2a．．．元件形成區域2a. . . Component forming area
2b．．．第1密封區域2b. . . First sealing area
3．．．第2玻璃基板3. . . Second glass substrate
3a．．．第2密封區域3a. . . Second sealing area
4．．．密封層4. . . Sealing layer
5．．．密封材料層5. . . Sealing material layer
6．．．雷射光6. . . laser
T1,T2．．．厚度T1, T2. . . thickness
第1圖係顯示本發明實施形態的電子裝置之構造的剖視圖。Fig. 1 is a cross-sectional view showing the structure of an electronic device according to an embodiment of the present invention.
第2(a)~(d)圖係顯示本發明實施形態的電子裝置之製造步驟的剖視圖。2(a) to 2(d) are cross-sectional views showing the steps of manufacturing the electronic device according to the embodiment of the present invention.
第3圖係顯示第2圖所示之電子裝置之製造步驟中使用的第1玻璃基板的平面圖。Fig. 3 is a plan view showing a first glass substrate used in the manufacturing steps of the electronic device shown in Fig. 2.
第4圖係沿第3圖中的A-A線的切剖圖。Fig. 4 is a cross-sectional view taken along line A-A in Fig. 3.
第5圖係顯示第2圖所示之電子裝置之製造步驟中使用的第2玻璃基板的平面圖。Fig. 5 is a plan view showing a second glass substrate used in the manufacturing steps of the electronic device shown in Fig. 2.
第6圖係沿第5圖中的A-A線的切剖圖。Fig. 6 is a cross-sectional view taken along line A-A in Fig. 5.
1．．．電子裝置1. . . Electronic device
2．．．第1玻璃基板2. . . First glass substrate
2a．．．元件形成區域2a. . . Component forming area
3．．．第2玻璃基板3. . . Second glass substrate
4．．．密封層4. . . Sealing layer
5．．．密封材料層5. . . Sealing material layer
6．．．雷射光6. . . laser
Claims (15)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008323422 | 2008-12-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201034846A TW201034846A (en) | 2010-10-01 |
| TWI462829B true TWI462829B (en) | 2014-12-01 |
Family
ID=42268845
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW098143641A TWI462829B (en) | 2008-12-19 | 2009-12-18 | Glass member having sealing material layer and method for manufacturing the same, and electronic device and manufacturing method thereof |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP5500079B2 (en) |
| TW (1) | TWI462829B (en) |
| WO (1) | WO2010071176A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011057477A (en) * | 2009-09-08 | 2011-03-24 | Nippon Electric Glass Co Ltd | Sealing material |
| JP5494831B2 (en) * | 2010-12-27 | 2014-05-21 | 旭硝子株式会社 | Glass member with sealing material layer, electronic device using the same, and manufacturing method thereof |
| WO2013008724A1 (en) * | 2011-07-08 | 2013-01-17 | 旭硝子株式会社 | Double glazed glass and method for producing same |
| JP2013097195A (en) * | 2011-11-01 | 2013-05-20 | Tokyo Institute Of Technology | Display device and manufacturing method for the same |
| US9441416B2 (en) * | 2012-09-27 | 2016-09-13 | Guardian Industries Corp. | Low temperature hermetic sealing via laser |
| JP2015074595A (en) * | 2013-10-11 | 2015-04-20 | 旭硝子株式会社 | Sealing material and vacuum multiple glass |
| CN106014124A (en) * | 2016-07-15 | 2016-10-12 | 常熟市赛蒂镶嵌玻璃制品有限公司 | Anti-explosion luminescent glass |
| CN115636584A (en) * | 2018-03-09 | 2023-01-24 | Ａｇｃ株式会社 | Alkali-free glass substrate |
| CN109693056B (en) * | 2019-02-25 | 2021-05-25 | 西安明科微电子材料有限公司 | Insulator solder for aluminum silicon carbide tube shell and preparation method thereof |
| CN111484254B (en) * | 2020-04-22 | 2022-07-05 | 中国建筑材料科学研究总院有限公司 | High-temperature sealing glass and preparation method and application thereof |
| CN114516720A (en) * | 2020-11-18 | 2022-05-20 | 财团法人金属工业研究发展中心 | Bioactive glass and method for manufacturing bioactive glass three-dimensional product |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09235136A (en) * | 1995-12-25 | 1997-09-09 | Asahi Glass Co Ltd | Low-melting point class composition and glass ceramics composition for sealing |
| JPH1179783A (en) * | 1997-09-08 | 1999-03-23 | Asahi Glass Co Ltd | Phosphate based glass paste composition |
| JP2003012328A (en) * | 2001-06-29 | 2003-01-15 | Asahi Techno Glass Corp | Method for manufacturing seal glass |
| JP2004010405A (en) * | 2002-06-05 | 2004-01-15 | Nippon Electric Glass Co Ltd | Tin phosphate-based glass and composite material |
| KR20080085087A (en) * | 2006-07-11 | 2008-09-22 | 니폰 덴키 가라스 가부시키가이샤 | Glass composition for sealing and sealed material |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3877500B2 (en) * | 2000-06-30 | 2007-02-07 | 旭テクノグラス株式会社 | Manufacturing method of glass for sealing material |
| JP3748533B2 (en) * | 2001-11-15 | 2006-02-22 | 旭テクノグラス株式会社 | Low melting glass and method for producing the same |
| US6998776B2 (en) * | 2003-04-16 | 2006-02-14 | Corning Incorporated | Glass package that is hermetically sealed with a frit and method of fabrication |
| JP2008037740A (en) * | 2006-07-11 | 2008-02-21 | Nippon Electric Glass Co Ltd | Glass composition for sealing and sealing material |
| JP4795897B2 (en) * | 2006-08-29 | 2011-10-19 | 国立大学法人 東京大学 | Panel body manufacturing method |
-
2009
- 2009-12-17 JP JP2010543002A patent/JP5500079B2/en active Active
- 2009-12-17 WO PCT/JP2009/071045 patent/WO2010071176A1/en active Application Filing
- 2009-12-18 TW TW098143641A patent/TWI462829B/en not_active IP Right Cessation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09235136A (en) * | 1995-12-25 | 1997-09-09 | Asahi Glass Co Ltd | Low-melting point class composition and glass ceramics composition for sealing |
| JPH1179783A (en) * | 1997-09-08 | 1999-03-23 | Asahi Glass Co Ltd | Phosphate based glass paste composition |
| JP2003012328A (en) * | 2001-06-29 | 2003-01-15 | Asahi Techno Glass Corp | Method for manufacturing seal glass |
| JP2004010405A (en) * | 2002-06-05 | 2004-01-15 | Nippon Electric Glass Co Ltd | Tin phosphate-based glass and composite material |
| KR20080085087A (en) * | 2006-07-11 | 2008-09-22 | 니폰 덴키 가라스 가부시키가이샤 | Glass composition for sealing and sealed material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5500079B2 (en) | 2014-05-21 |
| JPWO2010071176A1 (en) | 2012-05-31 |
| WO2010071176A1 (en) | 2010-06-24 |
| TW201034846A (en) | 2010-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI462829B (en) | Glass member having sealing material layer and method for manufacturing the same, and electronic device and manufacturing method thereof | |
| TWI526413B (en) | A sealing glass, a glass member having a sealing material layer, and an electronic device and a manufacturing method thereof | |
| JP5716743B2 (en) | SEALING PASTE AND ELECTRONIC DEVICE MANUFACTURING METHOD USING THE SAME | |
| JP5673102B2 (en) | Glass member with sealing material layer, electronic device using the same, and manufacturing method thereof | |
| JP5418594B2 (en) | Glass member with sealing material layer, electronic device using the same, and manufacturing method thereof | |
| JP5692218B2 (en) | Electronic device and manufacturing method thereof | |
| US20110209813A1 (en) | Process for producing glass member provided with sealing material layer and process for producing electronic device | |
| JP5598469B2 (en) | Glass member with sealing material layer, electronic device using the same, and manufacturing method thereof | |
| US20150037594A1 (en) | Glass composition, sealing material, and sealed package | |
| TW201246527A (en) | Glass member with sealing material layer, electronic device using same and method for producing same | |
| JP2011011925A (en) | Glass member with sealing material layer, electronic device using the same and method for producing the electronic device | |
| JP2011057477A (en) | Sealing material | |
| JP2012014971A (en) | Electronic device and its manufacturing method | |
| WO2010137667A1 (en) | Glass member with sealing material layer attached thereto, electronic device produced using same, and process for producing same | |
| JP5370011B2 (en) | Method for producing glass member with sealing material layer and method for producing electronic device | |
| JP5516194B2 (en) | Light heat sealing glass, glass member with sealing material layer, electronic device and method for producing the same | |
| JP5489061B2 (en) | Filler powder and sealing material using the same | |
| KR101236373B1 (en) | Manufacturing method for organic el display | |
| JP2014221695A (en) | Sealed package |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |