JP2005142037A - Light emitting apparatus - Google Patents
Light emitting apparatus Download PDFInfo
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- JP2005142037A JP2005142037A JP2003377704A JP2003377704A JP2005142037A JP 2005142037 A JP2005142037 A JP 2005142037A JP 2003377704 A JP2003377704 A JP 2003377704A JP 2003377704 A JP2003377704 A JP 2003377704A JP 2005142037 A JP2005142037 A JP 2005142037A
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- ultraviolet light
- glass
- phosphor
- light
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229910052751 metal Inorganic materials 0.000 claims abstract description 44
- 239000002184 metal Substances 0.000 claims abstract description 44
- 230000000737 periodic effect Effects 0.000 claims abstract description 18
- 239000005368 silicate glass Substances 0.000 claims abstract description 18
- 239000005373 porous glass Substances 0.000 claims description 48
- 239000011521 glass Substances 0.000 claims description 42
- 239000005388 borosilicate glass Substances 0.000 claims description 27
- 239000003513 alkali Substances 0.000 claims description 26
- 238000010304 firing Methods 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 15
- 238000010306 acid treatment Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 238000005191 phase separation Methods 0.000 claims description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 10
- 239000002585 base Substances 0.000 claims description 9
- 229910001385 heavy metal Inorganic materials 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052771 Terbium Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052743 krypton Inorganic materials 0.000 claims description 3
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical group [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 28
- 239000012071 phase Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 17
- 238000002834 transmittance Methods 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000012298 atmosphere Substances 0.000 description 12
- 239000010949 copper Substances 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 10
- 239000004327 boric acid Substances 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 9
- -1 alkaline earth metal aluminosilicate Chemical class 0.000 description 9
- 239000011651 chromium Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000011572 manganese Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
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- 230000008018 melting Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- 229910052693 Europium Inorganic materials 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000001747 exhibiting effect Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 239000003929 acidic solution Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000005611 electricity Effects 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052747 lanthanoid Inorganic materials 0.000 description 3
- 150000002602 lanthanoids Chemical class 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000075 oxide glass Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910015999 BaAl Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 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 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000004673 fluoride salts Chemical group 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
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- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Glass Compositions (AREA)
- Luminescent Compositions (AREA)
- Gas-Filled Discharge Tubes (AREA)
- Vessels And Coating Films For Discharge Lamps (AREA)
Abstract
Description
本発明は、真空紫外光を利用する発光器具に関する。 The present invention relates to a light emitting device using vacuum ultraviolet light.
従来より、波長２００ｎｍ以下の紫外光、すなわち真空紫外領域の紫外光で励起される真空紫外光用蛍光体が種々提案されている。これら各種真空紫外光用蛍光体は、希ガスランプ等の照明装置やプラズマディスプレイ等の表示装置に広く用いられている。 Conventionally, various phosphors for vacuum ultraviolet light that are excited by ultraviolet light having a wavelength of 200 nm or less, that is, ultraviolet light in the vacuum ultraviolet region, have been proposed. These various phosphors for vacuum ultraviolet light are widely used in illumination devices such as rare gas lamps and display devices such as plasma displays.
このような用途に用いる真空紫外光用蛍光体としては、様々な種類のものが知られており、ほとんどは無機物質から構成されている。これらの真空紫外光用蛍光体のうち、いくつかの種類のものは水銀線用蛍光体を改良することによって得られている。 Various types of phosphors for vacuum ultraviolet light used in such applications are known, and most are composed of inorganic substances. Among these phosphors for vacuum ultraviolet light, some types are obtained by improving the phosphor for mercury rays.
水銀線用蛍光体とは、水銀線（２５４ｎｍ）の波長域の紫外光で励起される蛍光体であり、これを改良して得られる真空紫外光用蛍光体としては、たとえば、緑色に発光するＢａＡｌ12Ｏ19：Ｍｎ2+、Ｚｎ2ＳｉＯ4：Ｍｎ2+等、赤色に発光する（Ｙ．Ｇｄ）ＢＯ3：
Ｅｕ3+、Ｙ2Ｏ3：Ｅｕ3+等、青色に発光するＢａＭｇＡｌ10Ｏ19：Ｅｕ2+などが一般的に良く用いられている。その他にも、真空紫外領域で励起されやすい工夫を凝らした、アルカリ土類金属のアルミノケイ酸塩蛍光体（特許文献１）、希土類酸化物蛍光体（特許文献２）、希土類リン酸蛍光体（特許文献３）、などの真空紫外光用蛍光体が知られている。
The phosphor for mercury rays is a phosphor excited by ultraviolet light in the wavelength region of mercury rays (254 nm). As a phosphor for vacuum ultraviolet light obtained by improving this, for example, it emits green light. BaAl 12 O 19 : Mn 2+ , Zn 2 SiO 4 : Mn 2+, etc., which emits red light (Y.Gd) BO 3 :
In general, BaMgAl 10 O 19 : Eu 2+ that emits blue light, such as Eu 3+ and Y 2 O 3 : Eu 3+ , is often used. Besides, alkaline earth metal aluminosilicate phosphors (Patent Document 1), rare earth oxide phosphors (Patent Document 2), and rare earth phosphate phosphors (Patents) A phosphor for vacuum ultraviolet light such as literature 3) is known.
しかしながら、これらの蛍光体は、一般に母材が紫外光をあまり透過しないため、まず粉体状に加工する必要がある。しかも発光に寄与するのが粉体の最表面層（数十ｎｍ程度）のみであり、通常の水銀線の紫外光を照射した場合と比較して、輝度が著しく低いという問題がある。また、照射された紫外光を母材が吸収するため、蛍光体の照射欠陥などを生じやすく、材料劣化が激しいという問題もある。特に、上記の蛍光体をプラズマディスプレイで使用した場合、イオン衝撃が大きいため、材料劣化が非常に激しく、プラズマディスプレイの寿命が短くなるなどの問題を生じさせている。 However, these phosphors generally need to be processed into a powder form first because the base material does not transmit much ultraviolet light. In addition, only the outermost surface layer (about several tens of nm) of the powder contributes to light emission, and there is a problem that the luminance is remarkably low as compared with the case of irradiating ultraviolet light of a normal mercury beam. In addition, since the base material absorbs the irradiated ultraviolet light, there is a problem that the phosphor is likely to cause irradiation defects and the material is severely deteriorated. In particular, when the above-described phosphor is used in a plasma display, since the ion bombardment is large, material deterioration is extremely severe, and problems such as shortening the life of the plasma display are caused.
さらに、上記した従来の蛍光体は、真空紫外光によって励起されると、温度劣化しやすいという欠点がある。特に、青色蛍光体であるＢａＭｇＡｌ10Ｏ19：Ｅｕ2+は、有機バインダーを３００〜５００℃でベーキング処理する際に表面のＥｕ2+（二価ユーロピウムイオン）が酸化されるために、劣化しやすいという欠点がある。 Furthermore, the above-described conventional phosphor has a drawback that it is susceptible to temperature degradation when excited by vacuum ultraviolet light. In particular, the blue phosphor BaMgAl 10 O 19 : Eu 2+ deteriorates because the surface Eu 2+ (divalent europium ion) is oxidized when the organic binder is baked at 300 to 500 ° C. There is a drawback that it is easy.
そこで、これらの蛍光体における問題点の解消を図るべく、様々な新規蛍光体が提案されている。具体的には、上記のような照射欠陥、材料劣化、温度消失等の不具合を防ぐことを目的として、表面に酸化物皮膜を形成した真空紫外光用蛍光体がいくつか提案されている（下記特許文献４〜６等参照）。また、蛍光の輝度を根本的に増加させることを目的として、母材に紫外光透過率の高いフッ化物を使用した真空紫外光用蛍光体（下記特許文献７参照）も提案されている。 Therefore, various new phosphors have been proposed in order to solve the problems in these phosphors. Specifically, several phosphors for vacuum ultraviolet light in which an oxide film is formed on the surface have been proposed for the purpose of preventing such defects as irradiation defects, material deterioration, and temperature loss (described below). (See Patent Documents 4 to 6). For the purpose of fundamentally increasing the luminance of fluorescence, a phosphor for vacuum ultraviolet light (see Patent Document 7 below) using a fluoride having a high ultraviolet light transmittance as a base material has been proposed.
しながら、上述した新規な蛍光体においても、実用上、未だ克服すべき種々の課題が残されている。例えば、表面に酸化物皮膜を形成した真空紫外光用蛍光体では、母材自体の紫外光透過率を向上する工夫がなされている訳ではない。そのため、発光するのは蛍光体の最表面層のみであることに変わりはない。したがって、発光強度が低いことなどの、従来の真空紫外光用蛍光体が抱える問題点を根本的に解決するには至っていない。 However, various problems to be overcome still remain in practical use even in the above-described novel phosphor. For example, in a phosphor for vacuum ultraviolet light having an oxide film formed on the surface, a device for improving the ultraviolet light transmittance of the base material itself has not been devised. Therefore, only the outermost surface layer of the phosphor emits light. Therefore, the problems of the conventional phosphor for vacuum ultraviolet light, such as low emission intensity, have not been fundamentally solved.
また、フッ化物を使用した真空紫外光用蛍光体は、母体がフッ化物であるため、酸化物
を母材とした真空紫外光用蛍光体に比べると、化学的・機械的にはるかに不安定であり、実用性に欠けるという欠点がある。また、フッ化物等は環境に対しても悪影響を及ぼす等問題が多い。
本発明は、上記した従来技術の問題点に鑑みてなされたものであり、その主な目的は、上記した問題点を解消し得る、優れた性能を有する真空紫外光用蛍光体を開発すると共に、その特性を利用した新規な発光器具を提供することである。 The present invention has been made in view of the above-mentioned problems of the prior art, and its main purpose is to develop a phosphor for vacuum ultraviolet light having excellent performance capable of solving the above-mentioned problems. An object of the present invention is to provide a novel light emitting device utilizing the characteristics.
本発明者は、上記した目的を達成すべく鋭意研究を重ねてきた。その結果、重金属及び希土類元素からなる群から選ばれた少なくとも一種の元素を酸化物として含むアルカリホウケイ酸塩ガラスに熱処理を施してＳｉＯ2を主成分とする不溶相と、Ｂ2Ｏ3を主成分と
する可溶相とに分相させ、その後酸処理を施すと、非常に高い紫外線透過率を有する高ケイ酸質の多孔質ガラスが得られることを見出した。そして、該多孔質ガラスに特定の金属成分を吸着させた後焼成することによって、化学的・機械的安定性に優れ、且つ真空紫外領域の光を照射すると強く蛍光を発する蛍光体を得ることができ、この蛍光体を発光体とすることによって、各種用途に有効に利用できる優れた性能の発光器具が得られることを見出し、ここに本発明を完成するに至った。
The present inventor has intensively studied to achieve the above-described object. As a result, an alkali borosilicate glass containing at least one element selected from the group consisting of heavy metals and rare earth elements as an oxide is subjected to a heat treatment to mainly contain an insoluble phase mainly composed of SiO 2 , and B 2 O 3 as a main component. It was found that a high siliceous porous glass having a very high ultraviolet transmittance can be obtained by phase separation into a soluble phase as a component, followed by acid treatment. And, by adsorbing a specific metal component to the porous glass and then firing, it is possible to obtain a phosphor that is excellent in chemical and mechanical stability and strongly emits fluorescence when irradiated with light in the vacuum ultraviolet region. Thus, it has been found that by using this phosphor as a light emitter, a light emitting device having excellent performance that can be effectively used for various applications can be obtained, and the present invention has been completed here.
即ち、本発明は、下記の発光器具を提供するものである。
１． 少なくとも一部が真空紫外光によって発光する蛍光体により形成された密閉容器と、該密閉容器に設けられた真空紫外光の照射源とを有する発光器具であって、
該蛍光体が、ＳｉＯ2を９６重量％以上、Ｂ2Ｏ3を０．５〜２重量％、Ａｌ2Ｏ3を０．
１〜０．８重量％、並びに周期表３Ａ族、４Ａ族、５Ａ族、６Ａ族、７Ａ族、８族、１Ｂ族、２Ｂ族及び４Ｂ族の各族に属する元素からなる群から選ばれた少なくとも一種の金属成分を５０〜２０００ｐｐｍ含有し、Ｆｅの存在量が５ｐｐｍ以下の高ケイ酸ガラスであることを特徴とする発光器具。
２． 蛍光体が、高ケイ酸多孔質ガラスを焼成して得られる高ケイ酸ガラスを母材として、該多孔質ガラスの細孔部の焼結によって形成されるシリカ相の界面部分に、周期表３Ａ族、４Ａ族、５Ａ族、６Ａ族、７Ａ族、８族、１Ｂ族、２Ｂ族及び４Ｂ族の各族に属する元素からなる群から選ばれた少なくとも一種の金属成分が分散した構造のガラスである上記項１に記載の発光器具。
３． 蛍光体が、下記（ｉ）〜（iv）の工程で得られる高ケイ酸ガラスであることを特徴とする上記項１又は２に記載の発光器具：
（i）重金属及び希土類元素からなる群から選ばれた少なくとも一種の元素を酸化物とし
て含むアルカリホウケイ酸塩ガラスに熱処理を施して分相させる工程、
（ii）上記（ｉ）工程で分相処理が施されたアルカリホウケイ酸ガラスに対して酸処理を行い、多孔質ガラスとする工程、
（iii）上記（ii）工程で得られた多孔質ガラスに、周期表３Ａ族、４Ａ族、５Ａ族、６
Ａ族、７Ａ族、８族、１Ｂ族、２Ｂ族及び４Ｂ族の各族に属する元素からなる群から選ばれた少なくとも一種の金属成分を吸着させる工程、
（iv）上記(iii)工程で金属成分を吸着させた多孔質ガラスを焼成する工程。
４． アルカリホウケイ酸塩ガラスが、ＭｎＯ2、ＣｅＯ2、Ｃｒ2Ｏ3、Ｃｏ2Ｏ3及びＣｕＯからなる群から選ばれた少なくとも一種の酸化物を０．１〜２重量％含有するものである上記項３に記載の発光器具。
５． 多孔質ガラスに吸着させる金属成分が、Ｖ、Ｃｒ、Ｍｎ、Ｃｏ、Ｎｉ、Ｃｕ、Ａｇ、Ｅｕ、Ｃｅ及びＴｂからなる群から選ばれた少なくとも一種である上記項３又は４に記載の発光器具。
６． 真空紫外光の照射源が、該密閉容器中に封入された希ガス及び該密閉容器に設けられた紫外光発生用電極からなるものである上記項１〜５のいずれかに記載の発光器具。
７． 密閉容器内に封入された希ガスが、キセノン、クリプトン、アルゴン又はヘリウムである上記項６に記載の発光器具。
８． 真空紫外光の照射源が、密閉容器外で発生させた真空紫外光を閉容器中に導入して照射する構造の真空紫外光照射装置である上記項１〜５のいずれかに記載の発光器具。
９． 密閉容器の少なくとも一部を構成する蛍光体が、管状、湾曲面状、矩形状、平板状又はレンズ状である上記項１〜８のいずれかに記載の発光器具。
１０．上記項１〜９のいずれかに記載の発光器具を複数個配置した照明装置。
That is, this invention provides the following light-emitting device.
1. A light emitting device having a sealed container formed of a phosphor that emits light by vacuum ultraviolet light, and a vacuum ultraviolet light irradiation source provided in the sealed container,
The phosphor has a SiO 2 content of 96% by weight or more, a B 2 O 3 content of 0.5 to 2% by weight, and an Al 2 O 3 content of 0.1%.
1 to 0.8% by weight and selected from the group consisting of elements belonging to groups 3A, 4A, 5A, 6A, 7A, 8, 1B, 2B and 4B A light-emitting device characterized by being a high-silicate glass containing at least one metal component in an amount of 50 to 2000 ppm and an Fe content of 5 ppm or less.
2. The phosphor is made of high silicate glass obtained by firing high silicate porous glass as a base material, and the periodic table 3A is formed on the interface portion of the silica phase formed by sintering the pores of the porous glass. A glass having a structure in which at least one metal component selected from the group consisting of elements belonging to each group of Group 4, Group 4A, Group 5A, Group 6A, Group 7A, Group 8, Group 1B, Group 2B and Group 4B is dispersed. Item 2. The light emitting device according to Item 1 above.
3. Item 3. The light emitting device according to Item 1 or 2, wherein the phosphor is high silicate glass obtained by the following steps (i) to (iv):
(I) a step of subjecting an alkali borosilicate glass containing at least one element selected from the group consisting of heavy metals and rare earth elements as an oxide to heat treatment to cause phase separation;
(Ii) a step of performing acid treatment on the alkali borosilicate glass subjected to the phase separation treatment in the step (i) to form a porous glass;
(Iii) The porous glass obtained in the step (ii) is added to the periodic table 3A group, 4A group, 5A group, 6
Adsorbing at least one metal component selected from the group consisting of elements belonging to groups A, 7A, 8, 1B, 2B and 4B;
(Iv) A step of firing the porous glass in which the metal component is adsorbed in the step (iii).
4). The above, wherein the alkali borosilicate glass contains 0.1 to 2% by weight of at least one oxide selected from the group consisting of MnO 2 , CeO 2 , Cr 2 O 3 , Co 2 O 3 and CuO. Item 4. A light emitting device according to Item 3.
5). Item 5. The light emitting device according to Item 3 or 4, wherein the metal component adsorbed on the porous glass is at least one selected from the group consisting of V, Cr, Mn, Co, Ni, Cu, Ag, Eu, Ce, and Tb. .
6). Item 6. The light emitting device according to any one of Items 1 to 5, wherein the irradiation source of vacuum ultraviolet light comprises a rare gas sealed in the sealed container and an ultraviolet light generating electrode provided in the sealed container.
7). Item 7. The light-emitting device according to Item 6, wherein the rare gas sealed in the sealed container is xenon, krypton, argon, or helium.
8). Item 6. The light emitting device according to any one of Items 1 to 5, wherein the irradiation source of vacuum ultraviolet light is a vacuum ultraviolet light irradiation device having a structure in which vacuum ultraviolet light generated outside a sealed container is introduced into the closed container and irradiated. .
9. Item 9. The light-emitting device according to any one of Items 1 to 8, wherein the phosphor constituting at least a part of the sealed container is tubular, curved surface, rectangular, flat, or lens-shaped.
10. The illuminating device which has arrange | positioned two or more the light-emitting fixtures in any one of said items 1-9.
本発明の発光器具は、少なくとも一部が真空紫外光によって発光する蛍光体（以下、「真空紫外光蛍光体」ということがある）により形成された密閉容器と、該密閉容器中に備えられた紫外光の照射源とを有するものである。 The light-emitting device of the present invention is provided with a sealed container formed of a phosphor that emits at least a part by vacuum ultraviolet light (hereinafter sometimes referred to as “vacuum ultraviolet phosphor”), and the sealed container. And an ultraviolet light irradiation source.
まず、本発明の発光器具で用いる蛍光体及びその製造方法について説明する。
蛍光体及びその製造方法
発光器具の材料とする真空紫外光用蛍光体は、紫外線透過率の高い高ケイ酸ガラスを母材として、その中に特定の金属成分が凝集することなく分散したものである。この様な真空紫外線用蛍光体は、高い紫外光透過率を有し、耐熱性、化学的耐久性、機械的強度などに優れ、更に、真空紫外領域の紫外線の放射により強い蛍光を発するものである。
First, a phosphor used in the light emitting device of the present invention and a method for manufacturing the phosphor will be described.
Phosphor and its manufacturing method The phosphor for vacuum ultraviolet light used as the material of the light emitting device is a high silicate glass having a high ultraviolet transmittance, and a specific metal component is dispersed without agglomeration therein. is there. Such a phosphor for vacuum ultraviolet rays has high ultraviolet light transmittance, excellent heat resistance, chemical durability, mechanical strength, etc., and emits strong fluorescence due to ultraviolet radiation in the vacuum ultraviolet region. is there.
（１）原料ガラス：
該真空紫外光用蛍光体を製造する際には、原料として、重金属及び希土類元素からなる群から選ばれた少なくとも一種の元素を酸化物として含むアルカリホウケイ酸塩ガラスを用いる。この様なアルカリホウケイ酸ガラスによれば、後述する分相工程において、該アルカリホウケイ酸ガラスに熱処理を施してＳｉＯ2を主成分とする不溶相（ケイ酸相）と
、Ｂ2Ｏ3を主成分とする可溶相（ホウ酸相）とに分相させる際に、該ガラス中に不可避的に含まれる低価数の鉄イオン（Ｆｅ2+）をＦｅ3+としてホウ酸相に濃縮させることができる。
(1) Raw glass:
When manufacturing the phosphor for vacuum ultraviolet light, an alkali borosilicate glass containing at least one element selected from the group consisting of heavy metals and rare earth elements as an oxide is used as a raw material. According to such an alkali borosilicate glass, in the phase separation step described later, the alkali borosilicate glass is subjected to a heat treatment to mainly contain an insoluble phase (silicate phase) containing SiO 2 as a main component, and B 2 O 3 as a main component. When splitting into a soluble phase (boric acid phase) as a component, low-valent iron ions (Fe 2+ ) inevitably contained in the glass are concentrated in the boric acid phase as Fe 3+ . be able to.
該アルカリホウケイ酸ガラスとしては、重金属及び希土類元素からなる群から選ばれた少なくとも一種の元素を含有する以外は、公知のアルカリホウケイ酸ガラスと同様の組成のものを用いることができる。この様なアルカリホウケイ酸ガラスは、通常、Ｓｉ、Ｂ、Ｏ、Ｎａ、Ａｌ、Ｃａ等の元素を含むガラスである。 As the alkali borosilicate glass, one having the same composition as the known alkali borosilicate glass can be used except that it contains at least one element selected from the group consisting of heavy metals and rare earth elements. Such alkali borosilicate glass is usually glass containing elements such as Si, B, O, Na, Al, Ca and the like.
具体的には、ガラス全体の重量を基準として、ＳｉＯ2を４５〜６０重量％程度、Ｂ2Ｏ3を２４〜３６重量％程度、アルカリ金属酸化物を５〜９重量％程度、Ａｌ2Ｏ3を１〜４
重量％程度、ＣａＯを２〜６重量％程度含有するガラスを用いることができる。該アルカリホウケイ酸ガラスには、その他の金属酸化物が３重量％程度まで含まれても良い。
Specifically, based on the weight of the whole glass, a SiO 2 about 45 to 60 wt%, B 2 O 3 of about 24 to 36 wt%, about 5 to 9% by weight of alkali metal oxide, Al 2 O 3 to 1-4
A glass containing about 2% by weight and about 2 to 6% by weight of CaO can be used. The alkali borosilicate glass may contain up to about 3% by weight of other metal oxides.
重金属及び希土類元素からなる群から選ばれた少なくとも一種の元素の含有量については、これらの元素を酸化物として換算した量が、ガラス全体の重量を基準として０．１〜２重量％程度であることが好ましい。 For the content of at least one element selected from the group consisting of heavy metals and rare earth elements, the amount of these elements converted as oxides is about 0.1 to 2% by weight based on the weight of the whole glass It is preferable.
アルカリホウケイ酸ガラス中に含まれる重金属及び希土類元素の内で、重金属としては、Ｍｎ、Ｃｒ、Ｃｏ、Ｃｕ等を例示できる。希土類元素としては、Ｃｅ等を例示できる。重金属及び希土類元素は、酸化物の形態として一種又は二種以上が含まれることが必要である。これらの酸化物は、高価数の酸化物としてガラス中に含まれることが好ましい。例えば、Ｍｎ、Ｃｒ、Ｃｏ、Ｃｕ及びＣｅについては、それぞれ、ＭｎＯ2、ＣｅＯ2、Ｃｒ2Ｏ3、Ｃｏ2Ｏ3及びＣｕＯとして含まれることが好ましい。これらの高価数の酸化物は、酸化剤として機能するため、ホウケイ酸ガラス中の鉄をより効果的にＦｅ3+の状態にすることができる。 Among the heavy metals and rare earth elements contained in the alkali borosilicate glass, examples of heavy metals include Mn, Cr, Co, and Cu. Examples of rare earth elements include Ce. It is necessary that the heavy metal and the rare earth element are contained in one or more kinds as oxide forms. These oxides are preferably contained in the glass as an expensive oxide. For example, Mn, Cr, Co, Cu, and Ce are preferably included as MnO 2 , CeO 2 , Cr 2 O 3 , Co 2 O 3, and CuO, respectively. Since these expensive oxides function as an oxidizing agent, iron in the borosilicate glass can be more effectively brought into the Fe 3+ state.
該アルカリホウケイ酸ガラスは、通常のアルカリホウケイ酸ガラス用の原料と同様の原料を用いて、目的とする組成となるように原料を混合し、加熱して溶融させた後、冷却することによって製造することができる。例えば、大気中などの含酸素雰囲気中で、１３５０〜１４５０℃程度で原料を溶融させた後、冷却すればよい。 The alkali borosilicate glass is produced by using the same raw materials as those for ordinary alkali borosilicate glass, mixing the raw materials so as to have a target composition, heating and melting, and then cooling. can do. For example, the raw material may be melted at about 1350 to 1450 ° C. in an oxygen-containing atmosphere such as the air and then cooled.
上記した溶融工程は、２回行うことが好ましい。それぞれの溶融工程の条件は、上記した条件と同様でよい。溶融工程を２回行うことによって、溶融を一回だけ行う場合と比較して、より紫外光透過率の高い真空紫外光用蛍光体を製造することができる。溶融工程を２回行う場合には、ホウ素源となる化合物、例えば、ホウ酸については、２回目の溶融工程において添加することが好ましい。これにより、得られる真空紫外光用蛍光体の母材の紫外光透過率をより高くすることができる。 The melting process described above is preferably performed twice. The conditions for each melting step may be the same as those described above. By performing the melting step twice, it is possible to manufacture a phosphor for vacuum ultraviolet light having a higher ultraviolet light transmittance than in the case of performing melting only once. When performing the melting step twice, it is preferable to add a boron source compound, such as boric acid, in the second melting step. Thereby, the ultraviolet light transmittance | permeability of the preform | base_material of the fluorescent substance for vacuum ultraviolet light obtained can be made higher.
（２）分相及び酸処理工程
上記したアルカリホウケイ酸ガラスに熱処理を施すことによって、該ガラスを、ＳｉＯ2を主成分とする不溶相（ケイ酸相）と、Ｂ2Ｏ3を主成分とする可溶相（ホウ酸相）とに
分相させる。
(2) Phase Separation and Acid Treatment Step By subjecting the alkali borosilicate glass to a heat treatment, the glass is divided into an insoluble phase (silicate phase) containing SiO 2 as a main component, and B 2 O 3 as a main component. Phase separation into a soluble phase (boric acid phase).
熱処理の条件については、十分に分相が進行するように適宜決めればよく、通常、大気中などの含酸素雰囲気中において５５０〜６５０℃程度で２０〜８０時間程度加熱すればよい。 The conditions for the heat treatment may be appropriately determined so that the phase separation proceeds sufficiently. Usually, heating may be performed at about 550 to 650 ° C. for about 20 to 80 hours in an oxygen-containing atmosphere such as the air.
この際、アルカリホウケイ酸ガラス中に不可避的に含まれる低価数の鉄イオン（Ｆｅ2+）が酸化されて高価数の鉄イオン（Ｆｅ3+）の状態となる。高価数の金属イオンは、ホウ酸相に濃縮される傾向があるので、高価数のＦｅ3+となった鉄は、ホウ酸相中に濃縮される。 At this time, low-valent iron ions (Fe 2+ ) inevitably contained in the alkali borosilicate glass are oxidized to be in the state of expensive iron ions (Fe 3+ ). Since expensive metal ions tend to concentrate in the boric acid phase, the iron that has become an expensive Fe 3+ is concentrated in the boric acid phase.
次いで、分相処理を施したアルカリホウケイ酸ガラスに対して酸処理を行う。酸処理を行うことによって、Ｂ2Ｏ3を主成分とする可溶相（ホウ酸相）が溶出して多孔質ガラスとなる。この際、ホウ酸相に分散している鉄イオンが、ホウ素、ナトリウム、カルシウムなどのイオンと共に除去されて、Ｆｅ含有量の低い高ケイ酸質の多孔質ガラスが得られる。 Next, acid treatment is performed on the alkali borosilicate glass subjected to the phase separation treatment. By performing the acid treatment, a soluble phase (boric acid phase) containing B 2 O 3 as a main component is eluted to form a porous glass. At this time, iron ions dispersed in the boric acid phase are removed together with ions such as boron, sodium, and calcium, and a high siliceous porous glass having a low Fe content is obtained.
酸処理については、可溶相が十分に溶出される条件とすればよく、例えば、米国特許第２１０６７４４号に記載された酸処理条件と同様の条件で行うことができる。例えば、硝酸、塩酸、硫酸などの無機酸を０．５〜２規定程度の濃度で含む酸水溶液を用い、分相処理を施したアルカリケイ酸ガラスをこの溶液中に８０〜１００℃程度で１６〜４０時間程度浸漬すればよい。処理時間が不足すると、ホウ酸相を十分に溶出させることができず、一方、処理時間が長くなると、ガラスに割れなどが生じ易くなるので好ましくない。 The acid treatment may be performed under conditions that allow the soluble phase to be sufficiently eluted, and can be performed, for example, under the same conditions as the acid treatment conditions described in US Pat. No. 2,106,744. For example, using an acid aqueous solution containing an inorganic acid such as nitric acid, hydrochloric acid, and sulfuric acid at a concentration of about 0.5 to 2 N, an alkali silicate glass subjected to phase separation treatment is added to this solution at about 80 to 100 ° C. at 16 to 16 ° C. What is necessary is just to immerse for about 40 hours. If the treatment time is insufficient, the boric acid phase cannot be sufficiently eluted. On the other hand, if the treatment time is long, cracks and the like are likely to occur in the glass.
上記した酸処理は、２回以上繰り返しても良い。 The acid treatment described above may be repeated twice or more.
また、上記アルカリホウケイ酸塩ガラスは、酸処理時において、エチレンジアミン四酢酸（ＥＤＴＡ）又はその塩を含有する酸性溶液を用いて、更に、処理を行うことが好ましい。この処理によれば、ＥＤＴＡがアルカリホウケイ酸塩ガラス中の金属と錯塩を形成するため、製造される真空紫外光用蛍光体中のＦｅ濃度をさらに低下させることができる。その結果、波長１８５ｎｍ付近において、母材が石英ガラスとほぼ同程度の紫外光透過率を有する真空紫外光用蛍光体を得ることができる。 The alkali borosilicate glass is preferably further treated with an acidic solution containing ethylenediaminetetraacetic acid (EDTA) or a salt thereof during acid treatment. According to this treatment, since EDTA forms a complex salt with the metal in the alkali borosilicate glass, the Fe concentration in the manufactured phosphor for vacuum ultraviolet light can be further reduced. As a result, it is possible to obtain a vacuum ultraviolet light phosphor whose base material has an ultraviolet light transmittance substantially the same as that of quartz glass in the vicinity of a wavelength of 185 nm.
ＥＤＴＡ又はその塩を含有する酸性溶液による処理の条件については、特に限定的ではないが、例えば、塩酸、硝酸、硫酸などの酸を含む水溶液中に、ＥＤＴＡ及びその塩から選ばれた少なくとも一種の成分を０．１〜０．３重量％程度添加した水溶液を用い、この水溶液中にアルカリケイ酸ガラスを浸漬すればよい。この酸性水溶液のｐＨについては、特に限定的ではないが、通常、１〜３程度のｐＨ値であることが好ましい。処理温度については、特に限定的ではないが、通常８０〜１００℃程度とすればよく、処理時間については、通常、１６〜４８時間程度とすればよい。 The conditions for the treatment with an acidic solution containing EDTA or a salt thereof are not particularly limited. For example, in an aqueous solution containing an acid such as hydrochloric acid, nitric acid, and sulfuric acid, at least one selected from EDTA and a salt thereof is used. What is necessary is just to immerse alkali silicate glass in this aqueous solution using the aqueous solution which added the component about 0.1 to 0.3 weight%. The pH of the acidic aqueous solution is not particularly limited, but usually a pH value of about 1 to 3 is preferable. The treatment temperature is not particularly limited, but is usually about 80 to 100 ° C., and the treatment time is usually about 16 to 48 hours.
尚、上記した酸処理及びエチレンジアミン四酢酸（ＥＤＴＡ）又はその塩を含有する酸性溶液による処理の終了後、必要に応じて、得られた多孔質ガラスを大気中等の含酸素雰囲気中で３００〜５００℃程度に加熱して、１〜５時間程度乾燥させてもよい。これにより、多孔質ガラスに吸着した酸、ＥＤＴＡ、硝酸アニオンなどを分解して、より優れた性能のガラスとすることができる。 In addition, after completion | finish of an acid solution containing the above-mentioned acid treatment and ethylenediaminetetraacetic acid (EDTA) or its salt, the obtained porous glass is 300-500 in oxygen-containing atmospheres, such as air | atmosphere, as needed. You may heat to about degreeC and dry for about 1 to 5 hours. Thereby, the acid, EDTA, nitrate anion, etc. which adsorb | sucked to porous glass can be decomposed | disassembled, and it can be set as the glass of the more superior performance.
（３）吸着工程
次いで、上記した方法で得られた多孔質高ケイ酸ガラスに金属成分を吸着させる。金属成分は、金属原子または金属イオンの形態で吸着させればよい。金属原子と金属イオンを同時に吸着させてもよい。
(3) Adsorption process Next, a metal component is adsorbed on the porous high-silicate glass obtained by the above-described method. The metal component may be adsorbed in the form of a metal atom or metal ion. Metal atoms and metal ions may be adsorbed simultaneously.
吸着させる金属成分としては、周期表３Ａ族、４Ａ族、５Ａ族、６Ａ族、７Ａ族、８族、１Ｂ族、２Ｂ族及び４Ｂ族の各族に属する元素からなる群から選ばれた少なくとも一種の金属成分（以下、「発光元素成分」ということがある）を用いる。これらの金属成分は、一種のみ吸着させてもよく、或いは二種以上吸着させても良い。 The metal component to be adsorbed is at least one selected from the group consisting of elements belonging to Groups 3A, 4A, 5A, 6A, 7A, 8, 1B, 2B and 4B Metal components (hereinafter sometimes referred to as “light emitting element components”). One of these metal components may be adsorbed, or two or more of these metal components may be adsorbed.
周期表３Ａ族に属する元素としては、Ｓｃ（スカンジウム）、Ｙ（イットリウム）、およびランタノイド（Ｌａ（ランタン）、Ｃｅ（セリウム）、Ｐｒ（プラセオジム）、Ｎｄ（ネオジム）、Ｐｍ（プロメチウム）、Ｓｍ（サマリウム）、Ｅｕ（ユウロピウム）、Ｇｄ（ガドリニウム）、Ｔｂ（テルビウム）、Ｄｙ（ジスプロシウム）、Ｈｏ（ホルミウム）、Ｅｒ（エルビウム）、Ｔｍ（ツリウム）、Ｙｂ（イッテルビウム）、Ｌｕ（ルテチウム））等が挙げられる。周期表４Ａ族に属する元素としては、Ｔｉ（チタン）、Ｚｒ（ジルコニウム）、Ｈｆ（ハフニウム）等が挙げられる。周期表５Ａ族に属する元素としては、Ｖ（バナジウム）、Ｎｂ（ニオブ）、Ｔａ（タンタル）等が挙げられる。周期表６Ａ族に属する元素としては、Ｃｒ（クロム）、Ｍｏ（モリブデン）、Ｗ（タングステン）等が挙げられる。周期表７Ａ族に属する元素としては、Ｍｎ（マンガン）、Ｔｃ（テクネチウム）、Ｒｅ（レニウム）等が挙げられる。また、周期表８族に属する元素としては、Ｃｏ（コバルト）、Ｎｉ（ニッケル）、Ｒｕ（ルテニウム）、Ｒｈ（ロジウム）、Ｐｄ（パラジウム）、Ｏｓ（オスミウム）、Ｉｒ（イルジウム）、Ｐｔ（白金）等が挙げられる。また、周期表１Ｂ族に属する元素としては、Ｃｕ（銅）、Ａｇ（銀）、Ａｕ（金）等が挙げられる。また、周期表２Ｂ族に属する元素としては、Ｚｎ（亜鉛）、Ｃｄ（カドミウム）、Ｈｇ（水銀）等が挙げられる。また、周期表４Ｂ族に属する元素としては、Ｓｉ（ケイ素）、Ｇｅ（ゲルマニウム）、Ｓｎ（スズ）、Ｐｂ（鉛）等が挙げられる。 Elements belonging to Group 3A of the periodic table include Sc (scandium), Y (yttrium), and lanthanoids (La (lanthanum), Ce (cerium), Pr (praseodymium), Nd (neodymium), Pm (promethium), Sm ( Samarium), Eu (europium), Gd (gadolinium), Tb (terbium), Dy (dysprosium), Ho (holmium), Er (erbium), Tm (thulium), Yb (ytterbium), Lu (lutetium)), etc. Can be mentioned. Examples of elements belonging to Group 4A of the periodic table include Ti (titanium), Zr (zirconium), and Hf (hafnium). Examples of elements belonging to Group 5A of the periodic table include V (vanadium), Nb (niobium), Ta (tantalum), and the like. Examples of elements belonging to Group 6A of the periodic table include Cr (chromium), Mo (molybdenum), and W (tungsten). Examples of elements belonging to Group 7A of the periodic table include Mn (manganese), Tc (technetium), and Re (rhenium). In addition, as elements belonging to Group 8 of the periodic table, Co (cobalt), Ni (nickel), Ru (ruthenium), Rh (rhodium), Pd (palladium), Os (osmium), Ir (ildium), Pt (platinum) ) And the like. Examples of elements belonging to Group 1B of the periodic table include Cu (copper), Ag (silver), and Au (gold). Examples of elements belonging to Group 2B of the periodic table include Zn (zinc), Cd (cadmium), and Hg (mercury). Examples of elements belonging to Group 4B of the periodic table include Si (silicon), Ge (germanium), Sn (tin), and Pb (lead).
これらの内で、特に、周期表第４周期に属する元素、第５周期に属する元素、ランタノ
イドなどが好ましい。これらの元素を金属原子又はイオンとして吸着させることにより、特に発光強度の高い真空紫外光用蛍光体を得ることができる。
Of these, elements belonging to the fourth period of the periodic table, elements belonging to the fifth period, lanthanoids and the like are particularly preferable. By adsorbing these elements as metal atoms or ions, a phosphor for vacuum ultraviolet light having particularly high emission intensity can be obtained.
周期表第４周期に属する元素及び第５周期に属する元素としては、Ｖ、Ｃｒ、Ｍｎ、Ｃｏ、Ｎｉ、Ｃｕ、Ａｇ等が好ましく、ランタノイドとしては、Ｅｕ、Ｃｅ、Ｔｂ等が好ましい。これらの元素は、一種単独又は二種以上混合して用いることができ、金属原子又はイオンとして吸着させればよい。特に、Ｃｕ，Ｓｎ、Ｚｎ、Ｅｕ，Ｇｄ及びＴｂからなる群から選ばれた少なくとも一種の金属成分が好ましい。 V, Cr, Mn, Co, Ni, Cu, Ag and the like are preferable as the element belonging to the fourth period and the fifth period of the periodic table, and Eu, Ce, Tb and the like are preferable as the lanthanoid. These elements can be used singly or in combination of two or more, and may be adsorbed as metal atoms or ions. In particular, at least one metal component selected from the group consisting of Cu, Sn, Zn, Eu, Gd, and Tb is preferable.
多孔質高ケイ酸ガラスに発光元素成分を吸着させるには、具体的には、上記した発光元素成分を含む溶液中に、多孔質高ケイ酸ガラスを浸漬する方法、発光元素成分を含む溶液を多孔質高ケイ酸ガラスに塗布する方法、CVD、スパッタなどの気相法を利用して中に導
入する方法等を採用できる。これらの方法によれば、多孔質ガラスの表面及び細孔中に発光元素成分を十分に吸着させることができる。特に、発光元素成分を含む溶液中に多孔質高ケイ酸ガラスを浸漬する方法によれば、発光元素成分を容易に多孔質ガラスに浸透させることができ、強い発光を呈する真空紫外光用蛍光体を得ることができる。
In order to adsorb the luminescent element component to the porous high silicate glass, specifically, a method of immersing the porous high silicate glass in the solution containing the above luminescent element component, a solution containing the luminescent element component A method of applying to porous high silicate glass, a method of introducing into the inside using a vapor phase method such as CVD, sputtering, etc. can be adopted. According to these methods, the luminescent element component can be sufficiently adsorbed on the surface and pores of the porous glass. In particular, according to the method of immersing the porous high silicate glass in the solution containing the light emitting element component, the phosphor for vacuum ultraviolet light can easily penetrate the porous glass and exhibit strong light emission. Can be obtained.
上記した発光元素成分を含む溶液としては、周期表３Ａ族、４Ａ族、５Ａ族、６Ａ族、７Ａ族、８族、１Ｂ族、２Ｂ族及び４Ｂ族の各族に属する元素からなる群から選ばれた少なくとも一種の金属成分を含む化合物を溶解した溶液を用いることができる。例えば、上記元素を含む硝酸塩、酸化物、塩化物、炭酸塩、硫酸塩、有機金属塩等の化合物、これら化合物の水和物等を含む溶液を用いることができる。該溶液における溶媒については、特に限定はなく、水、有機溶媒などを適宜選択すればよい。 The solution containing the light emitting element component described above is selected from the group consisting of elements belonging to groups 3A, 4A, 5A, 6A, 7A, 8, 1B, 2B and 4B. A solution in which the compound containing at least one metal component is dissolved can be used. For example, a solution containing a compound such as a nitrate, oxide, chloride, carbonate, sulfate, or organic metal salt containing the above element, or a hydrate of these compounds can be used. The solvent in the solution is not particularly limited, and water, an organic solvent, etc. may be appropriately selected.
発光元素成分を含む化合物の濃度については、特に限定的ではなく、使用する金属成分が完全に溶解する濃度であればよく、例えば、０．００２〜０．０６重量％程度の濃度の水溶液を用いることができる。金属成分の濃度が高すぎると、焼成時に表面に析出したり、曇りが発生しやすくなり、一方、濃度が低すぎると吸着量が不足して十分な発光性能が得られないので好ましくない。 The concentration of the compound containing the light emitting element component is not particularly limited as long as the metal component to be used is completely dissolved. For example, an aqueous solution having a concentration of about 0.002 to 0.06% by weight is used. be able to. If the concentration of the metal component is too high, it tends to deposit on the surface during firing or clouding tends to occur. On the other hand, if the concentration is too low, the amount of adsorption is insufficient and sufficient light-emitting performance cannot be obtained.
この溶液中に多孔質ガラスを浸漬する際の条件については特に限定的ではないが、通常、室温の溶液中に多孔質ガラスを浸漬すればよい。溶液中への多孔質ガラスの添加量については、特に限定的ではなく、吸着させようとする金属成分量によって適宜決めれば良い。例えば、上記した濃度範囲の溶液１０〜２５ｍｌ中に、多孔質ガラスを０．１〜０．３ｇ程度浸漬して、３０分〜３時間程度放置すればよい。 The conditions for immersing the porous glass in this solution are not particularly limited, but it is usually sufficient to immerse the porous glass in the solution at room temperature. The amount of the porous glass added to the solution is not particularly limited, and may be appropriately determined depending on the amount of the metal component to be adsorbed. For example, about 0.1 to 0.3 g of porous glass may be immersed in 10 to 25 ml of the solution in the concentration range described above and left for about 30 minutes to 3 hours.
また、上記多孔質ガラスに金属成分を吸着させた後、一旦これを乾燥し、再び金属成分を吸着させてもよい。金属成分等を吸着させる工程と乾燥工程は、複数回繰り返すことも可能である。これにより、上記多孔質ガラスに発光元素成分を確実に吸着させることが可能となり、濃度消光を防いでより発光強度の強い真空紫外光用蛍光体を得ることができる。 Alternatively, after the metal component is adsorbed on the porous glass, the metal component may be once dried and adsorbed again. The process of adsorbing the metal component and the like and the drying process can be repeated a plurality of times. As a result, the light emitting element component can be reliably adsorbed on the porous glass, and concentration-quenching can be prevented and a phosphor for vacuum ultraviolet light having higher emission intensity can be obtained.
本発明では、更に、必要に応じて、該多孔質ガラスに、Ｂ，Ｎ，Ｆ，Ａｌ、Ｐ及びＳからなる群から選ばれた少なくとも一種の元素を吸着させることができる。これらの元素は、増感剤として機能するものであり、上記した金属成分の周囲に存在して、金属成分の環境を変えて発光強度を増加させる働きをするものである。 In the present invention, if necessary, at least one element selected from the group consisting of B, N, F, Al, P and S can be adsorbed on the porous glass. These elements function as sensitizers, exist around the above-described metal component, and function to increase the emission intensity by changing the environment of the metal component.
Ｂ、Ｎ、Ｆ、Ａｌ、Ｐ及びＳからなる群から選ばれた少なくとも一種の元素（以下、「増感剤成分」ということがある）を多孔質ガラスに吸着させる方法については、特に限定的ではないが、例えば、増感剤成分を含む溶液中に多孔質ガラスを浸漬する方法、増感剤
成分を含む溶液を多孔質ガラスに塗布する方法等によって行うことができる。
The method for adsorbing at least one element selected from the group consisting of B, N, F, Al, P and S (hereinafter sometimes referred to as “sensitizer component”) to the porous glass is particularly limited. However, it can be performed by, for example, a method of immersing porous glass in a solution containing a sensitizer component, a method of applying a solution containing a sensitizer component to porous glass, or the like.
増感剤成分を含む溶液としては、例えば、増感剤成分を含む可溶性化合物を溶解した水溶液を用いることができる。これらの化合物の濃度については、特に限定的ではないが、例えば、２０〜４５重量％程度、好ましくは３０〜４０重量％程度とすればよい。 As a solution containing a sensitizer component, for example, an aqueous solution in which a soluble compound containing a sensitizer component is dissolved can be used. The concentration of these compounds is not particularly limited, but may be, for example, about 20 to 45% by weight, preferably about 30 to 40% by weight.
この様な濃度範囲の水溶液を用いることによって、発光元素成分の周囲に増感剤成分が配位して有効に作用して、発光強度を増加させることができる。増感剤成分の濃度が高すぎると、ガラスの失透が生じやすくなるので好ましくない。また、この水溶液には、酸を加えることが好ましい。酸を含む水溶液を用いることによって、増感剤成分がガラス表面に析出しやすくなる。酸としては、硝酸、塩酸、硫酸などを用いることができ、特に硝酸が好ましい。酸の濃度は、特に限定的ではないが、通常、０．１〜３規定程度とすればよい。酸濃度が高すぎると、増感剤成分が酸化物として析出しやすくなり、一方、酸濃度が低すぎると増感剤成分の吸着性が低下するので好ましくない。 By using an aqueous solution having such a concentration range, the sensitizer component is coordinated around the luminescent element component and effectively acts to increase the luminescence intensity. If the concentration of the sensitizer component is too high, the glass tends to be devitrified, which is not preferable. Moreover, it is preferable to add an acid to this aqueous solution. By using an aqueous solution containing an acid, the sensitizer component is likely to precipitate on the glass surface. As the acid, nitric acid, hydrochloric acid, sulfuric acid and the like can be used, and nitric acid is particularly preferable. The concentration of the acid is not particularly limited, but is usually about 0.1 to 3 N. If the acid concentration is too high, the sensitizer component tends to precipitate as an oxide, while if the acid concentration is too low, the adsorptivity of the sensitizer component is lowered, which is not preferable.
増感剤成分を含む溶液による処理条件については、特に限定的ではないが、例えば、上記した金属成分を吸着させる条件と同様とすればよい。 The treatment conditions with the solution containing the sensitizer component are not particularly limited, but may be the same as, for example, the conditions for adsorbing the metal component described above.
多孔質ガラスに増感剤成分を吸着させる処理は複数回行っても良い。これにより、容易に増感剤成分を多孔質ガラスに浸透させることができ、より強く発光する真空紫外光用蛍光体を得ることができる。 You may perform the process which makes a porous glass adsorb | suck a sensitizer component in multiple times. Thereby, the sensitizer component can be easily penetrated into the porous glass, and a phosphor for vacuum ultraviolet light that emits light more strongly can be obtained.
多孔質ガラスに増感剤成分を吸着させる工程は、後述する焼成工程の前であれば、どの段階で行ってもよく、回数等の条件も適宜設定可能である。従って、多孔質ガラスに発光元素成分を吸着させる工程の前後どの段階で増感剤成分を吸着させてもよく、発光元素成分と増感剤成分とを上記多孔質ガラスに吸着させる工程を同時に行ってもよい。また、多孔質ガラスに発光元素成分を吸着させる工程と該多孔質ガラスに増感剤成分を吸着させる工程との間に乾燥工程が入ってもよいし、これら２つの吸着工程と乾燥工程とを複数回繰り返すこともできる。 The step of adsorbing the sensitizer component to the porous glass may be performed at any stage as long as it is before the firing step described later, and conditions such as the number of times can be appropriately set. Therefore, the sensitizer component may be adsorbed at any stage before or after the step of adsorbing the luminescent element component on the porous glass, and the step of adsorbing the luminescent element component and the sensitizer component on the porous glass is performed simultaneously. May be. In addition, a drying step may be inserted between the step of adsorbing the luminescent element component on the porous glass and the step of adsorbing the sensitizer component on the porous glass, and these two adsorption steps and drying steps may be performed. It can be repeated multiple times.
（４）焼成工程
上記した方法で多孔質ガラスに発光元素成分を吸着させた後、該多孔質ガラスを焼成する。これにより、細孔が消失して、全体が収縮して透明なガラスとなる。
(4) Firing step After the luminous element component is adsorbed to the porous glass by the method described above, the porous glass is fired. As a result, the pores disappear and the whole contracts to become transparent glass.
焼成温度は、９００〜１６００℃程度とすることが好ましい。この程度の温度範囲で焼成することによって、発光元素成分が吸着した多孔質ガラスの孔径、表面状態等を適切に制御して、紫外光透過性、耐熱性、化学的耐久性、機械的強度等に優れ、強い発光を呈する真空紫外光用蛍光体を得ることができる。 The firing temperature is preferably about 900 to 1600 ° C. By firing in this temperature range, the pore diameter, surface state, etc. of the porous glass adsorbed with the luminescent element component are controlled appropriately, ultraviolet light transmittance, heat resistance, chemical durability, mechanical strength, etc. It is possible to obtain a phosphor for vacuum ultraviolet light that is excellent in light emission and exhibits strong light emission.
これに対して、焼成温度が９００℃を下回ると、十分な発光を呈する真空紫外光用蛍光体が得られず、一方、焼成温度が１６００℃を上回ると、焼成した場合に基質のガラスが軟化することがあるので好ましくない。 On the other hand, if the firing temperature is lower than 900 ° C., a phosphor for vacuum ultraviolet light exhibiting sufficient light emission cannot be obtained. On the other hand, if the firing temperature exceeds 1600 ° C., the glass of the substrate is softened when fired. This is not preferable.
焼成雰囲気については、特に限定はなく、例えば、大気中等の酸素含有雰囲気中、還元雰囲気中等で焼成することができる。例えば、還元雰囲気中で焼成する方法としては、カーボンを入れたアルミナるつぼ中で焼成する方法等が挙げられる。 There is no particular limitation on the firing atmosphere, and for example, firing can be performed in an oxygen-containing atmosphere such as the air, a reducing atmosphere, or the like. For example, a method of firing in a reducing atmosphere includes a method of firing in an alumina crucible containing carbon.
焼成時間については特に限定的ではないが、目的とする焼成の程度に応じて、３０分〜３時間程度の範囲から適宜焼成時間を決めればよい。焼成時間が短すぎると十分に細孔が消失しないので好ましくない。 The firing time is not particularly limited, but the firing time may be appropriately determined from the range of about 30 minutes to 3 hours depending on the intended degree of firing. If the firing time is too short, it is not preferable because the pores do not disappear sufficiently.
焼成後に得られた酸化物ガラスは、放冷しても良いが、急速に冷却することによって、ガラスマトリックスと金属成分との反応を防止することができ、より強い蛍光を発する真空紫外光用蛍光体を製造できる。冷却方法については、特に限定されるものではないが、例えば、一定温度の恒温槽内で冷却する方法、大気中に放置する方法等が挙げられる。冷却速度等は適宜設定可能であるが、通常、５℃／秒程度以上、好ましくは１０℃／秒程度以上の速度で冷却することが望ましい。 The oxide glass obtained after firing may be allowed to cool, but by rapid cooling, the reaction between the glass matrix and the metal component can be prevented, and fluorescence for vacuum ultraviolet light that emits stronger fluorescence. The body can be manufactured. The cooling method is not particularly limited, and examples thereof include a method of cooling in a constant temperature thermostat and a method of leaving in the atmosphere. The cooling rate and the like can be appropriately set, but it is usually desirable to cool at a rate of about 5 ° C./second or more, preferably about 10 ° C./second or more.
上記した真空紫外光用蛍光体の製造方法によれば、比較的低廉な原料であるアルカリホウケイ酸ガラスを原料とするために、低コストで真空紫外光用蛍光体を製造することができる。しかも上記した製造方法によれば、比較的簡単な方法で大量に真空紫外光用蛍光体を製造することができる。 According to the above-described method for producing a phosphor for vacuum ultraviolet light, since the alkali borosilicate glass, which is a relatively inexpensive raw material, is used as a raw material, the phosphor for vacuum ultraviolet light can be produced at a low cost. Moreover, according to the manufacturing method described above, it is possible to manufacture a large amount of phosphor for vacuum ultraviolet light by a relatively simple method.
（５）真空紫外光用蛍光体
上記した方法によれば、原料とするアルカリホウケイ酸塩ガラス中に不可避的に含まれるＦｅがホウ酸相に濃縮され、酸処理によって溶出除去されることにより、Ｆｅ濃度の非常に低い多孔質ガラスを得ることができる。この様な多孔質ガラスに特定の金属成分（発光元素成分）を吸着させて焼成することにより、高い紫外光透過率を示し、真空紫外光によって励起されて強い発光を示す真空紫外光用蛍光体を得ることができる。
(5) Phosphor for vacuum ultraviolet light According to the method described above, Fe inevitably contained in the alkali borosilicate glass as a raw material is concentrated in the boric acid phase, and is eluted and removed by acid treatment. A porous glass having a very low Fe concentration can be obtained. A phosphor for vacuum ultraviolet light that exhibits high ultraviolet light transmittance and exhibits strong light emission when excited by vacuum ultraviolet light by adsorbing a specific metal component (light emitting element component) to such porous glass and firing it. Can be obtained.
特に、セリウムまたはクロムを含むアルカリホウケイ酸塩ガラスから作製する場合には、焼成工程の前にＥＤＴＡ又はその塩を含有する酸性溶液で処理することにより、波長１８５ｎｍ付近で石英ガラスとほぼ同程度の紫外光透過率を示す真空紫外光用蛍光体を得ることができる。 In particular, in the case of producing from an alkali borosilicate glass containing cerium or chromium, by treating with an acidic solution containing EDTA or a salt thereof before the firing step, it is approximately the same as quartz glass at a wavelength of around 185 nm. A phosphor for vacuum ultraviolet light exhibiting ultraviolet light transmittance can be obtained.
また、本発明で用いる高ケイ酸質ガラスは、発光元素成分の含有量が比較的少なく、溶融法やＣＶＤ法などによって得られる石英ガラスと比べると低コストである。したがって、本発明によれば、石英ガラスとほぼ同じ紫外光透過率を有する真空紫外光用蛍光体を、石英ガラスよりも低コストで大量に製造することができる。 Further, the high siliceous glass used in the present invention has a relatively small content of the light emitting element component, and is low in cost as compared with quartz glass obtained by a melting method or a CVD method. Therefore, according to the present invention, a vacuum ultraviolet light phosphor having substantially the same ultraviolet light transmittance as quartz glass can be produced in a large amount at a lower cost than quartz glass.
また、本発明で用いる真空紫外光用蛍光体は、従来のいわゆるバイコール法によって製造されたガラスと同様にシリカ多孔質である。このため、透光性と高い表面積をあわせ持つが、更に、バイコール法によって製造したガラスと比較して鉄分の含有量が少なく、Ｈｇフリーランプで使用されるＸｅ光（１７６ｎｍ）等の真空紫外光に対して高い透過性を示す。このため、該真空紫外光用蛍光体は、従来のバイコール法によって製造されるガラスよりも紫外光透過率が高く、真空紫外光を可視域の光へ効率よく変換することができる。 Moreover, the phosphor for vacuum ultraviolet light used by this invention is a porous silica like the glass manufactured by the conventional what is called Vycor method. For this reason, it has both translucency and high surface area, but it has a lower iron content than glass produced by the Vycor method, and vacuum ultraviolet light such as Xe light (176 nm) used in Hg-free lamps. Shows high permeability. For this reason, the phosphor for vacuum ultraviolet light has higher ultraviolet light transmittance than the glass manufactured by the conventional Vycor method, and can efficiently convert vacuum ultraviolet light into visible light.
更に、該真空紫外光用蛍光体は、ガラス母体が安定な酸化物ガラスであるため、耐熱性、化学的耐久性、機械的強度等も良好である。したがって、より短波長の光で励起できるだけでなく、紫外光照射による欠陥も発生し難いという利点を有する。 Further, since the phosphor for vacuum ultraviolet light is a stable oxide glass, the heat resistance, chemical durability, mechanical strength and the like are good. Therefore, it has an advantage that not only can it be excited by light having a shorter wavelength, but also defects due to ultraviolet light irradiation are less likely to occur.
上記した方法で得られる蛍光体は、ＳｉＯ2を９６重量％程度以上、Ｂ2Ｏ3を０．５〜
２重量％程度、Ａｌ2Ｏ3を０．１〜０．８重量％程度、並びに周期表３Ａ族、４Ａ族、５Ａ族、６Ａ族、７Ａ族、８族、１Ｂ族、２Ｂ族及び４Ｂ族の各族に属する元素からなる群から選ばれた少なくとも一種の金属成分を５０〜２０００ｐｐｍ程度含有し、Ｆｅの存在量が５ｐｐｍ以下の高ケイ酸ガラスである。
The phosphor obtained by the above method has a SiO 2 content of about 96% by weight or more and a B 2 O 3 content of 0.5 to 0.5%.
About 2% by weight, about 0.1 to 0.8% by weight of Al 2 O 3 , and periodic table 3A group, 4A group, 5A group, 6A group, 7A group, 8 group, 1B group, 2B group and 4B group This is a high silicate glass containing about 50 to 2000 ppm of at least one metal component selected from the group consisting of elements belonging to each of the above groups and having an Fe content of 5 ppm or less.
この様な蛍光体は、高ケイ酸多孔質ガラスを焼成して得られる高ケイ酸ガラスを母材として、該多孔質ガラスの細孔部の焼結によって形成されるシリカ相の界面部分に、周期表
３Ａ族、４Ａ族、５Ａ族、６Ａ族、７Ａ族、８族、１Ｂ族、２Ｂ族及び４Ｂ族の各族に属する元素からなる群から選ばれた少なくとも一種の金属成分が分散した構造を有するガラスである。この様な構造のガラスは、上記金属成分が凝集することなく、均一性良く分散していることにより、真空紫外光によって励起される際に、非常に強い発光を示すことができる。
Such a phosphor has, as a base material, a high silicate glass obtained by firing a high silicate porous glass, at the interface portion of the silica phase formed by sintering the pores of the porous glass, A structure in which at least one metal component selected from the group consisting of elements belonging to groups 3A, 4A, 5A, 6A, 7A, 8, 1B, 2B and 4B is dispersed in the periodic table It is glass which has. The glass having such a structure can exhibit very strong light emission when excited by vacuum ultraviolet light because the metal component is dispersed with good uniformity without agglomeration.
この様な本発明の真空紫外光用蛍光体は、従来のバイコール法によって製造されるガラスと比べて、より短波長の光で励起させることができ、真空紫外光を含む紫外光、Ｘ線等を可視域の光へ高効率に変換することができる。 Such a phosphor for vacuum ultraviolet light of the present invention can be excited with light having a shorter wavelength than glass produced by the conventional Vycor method, and includes ultraviolet light including vacuum ultraviolet light, X-rays, etc. Can be converted into visible light with high efficiency.
発光器具
本発明の発光器具は、少なくとも一部が上記した真空紫外光によって発光する蛍光体により形成された密閉容器と、該密閉容器中に備えられた真空紫外光の照射源とを有するものである。
Luminescent device The light-emitting device of the present invention comprises a sealed container formed of a phosphor that emits at least part of the above-described vacuum ultraviolet light, and a vacuum ultraviolet light irradiation source provided in the sealed container. is there.
該密閉容器は、発生する蛍光の利用方法に応じて、全体が該蛍光体によって形成されていても良く、或いは、その一部が該蛍光体によって形成されていても良い。例えば、密閉容器の全面が発光する蛍光ランプとする場合には、密閉容器の全体を該蛍光体で形成すればよい。また、一方向にのみ発光させる場合には、発光方向の面のみを該蛍光体によって形成すればよい。 The sealed container may be entirely formed of the phosphor, or a part thereof may be formed of the phosphor, depending on how to use the generated fluorescence. For example, when a fluorescent lamp that emits light from the entire surface of the sealed container is used, the entire sealed container may be formed of the phosphor. Further, in the case where light is emitted only in one direction, only the surface in the light emitting direction may be formed by the phosphor.
該蛍光体の形状については特に限定的ではなく、目的に応じて適切な形態を決めればよい。例えば、管状、湾曲面状、矩形状、平板状、レンズ状などの各種形状とすることができる。該蛍光体を種々の形状に成形するには、例えば、上記アルカリホウケイ酸塩ガラスを溶融させた後に、種々の形状の金型に流し込んで冷却すればよい。 The shape of the phosphor is not particularly limited, and an appropriate form may be determined according to the purpose. For example, various shapes such as a tubular shape, a curved surface shape, a rectangular shape, a flat plate shape, and a lens shape can be used. In order to mold the phosphor into various shapes, for example, after the alkali borosilicate glass is melted, it is poured into a mold having various shapes and cooled.
真空紫外光の照射源は、該密閉容器の内部において真空紫外光を発生させる構造であってもよく、或いは、外部において発生させた真空紫外光を該密閉容器内に導入する構造の真空紫外光照射装置であってもよい。 The irradiation source of vacuum ultraviolet light may be a structure that generates vacuum ultraviolet light inside the sealed container, or vacuum ultraviolet light having a structure that introduces vacuum ultraviolet light generated outside into the sealed container. An irradiation device may be used.
該密閉容器の内部において真空紫外光を発生させる場合には、該密閉容器中に希ガスを封入し、該密閉装置に紫外線発生用電極を設置すればよい。希ガスとしては、キセノン、クリプトン、アルゴン、ヘリウム等を用いることができる。電極は、該密閉容器の内部又は外部に設置することができる。 When vacuum ultraviolet light is generated inside the sealed container, a rare gas may be sealed in the sealed container and an ultraviolet generating electrode may be installed in the sealed device. As the rare gas, xenon, krypton, argon, helium, or the like can be used. The electrode can be installed inside or outside the sealed container.
外部において発生させた真空紫外光を導入する場合には、真空紫外光発生装置としては、エキシマランプなどを用いることができる。真空紫外光の導入方法としては、光源を容器に接続して該容器中に真空紫外光を直接導入する方法でもよく、或いは、石英ファイバーなどを用いて外部において発生した真空紫外光を該容器中に導入する方法でもよい。 When vacuum ultraviolet light generated outside is introduced, an excimer lamp or the like can be used as the vacuum ultraviolet light generator. As a method of introducing vacuum ultraviolet light, a method of directly introducing vacuum ultraviolet light into the container by connecting a light source to the container, or vacuum ultraviolet light generated outside using a quartz fiber or the like in the container may be used. It may be a method to be introduced.
以下、本発明の発光器具の実施態様を示す図面を参照して、本発明の発光器具についてより具体的に説明する。 Hereinafter, the light-emitting device of the present invention will be described more specifically with reference to the drawings showing embodiments of the light-emitting device of the present invention.
図１は、少なくとも一部が上記蛍光体によって形成された密閉容器と、その内部に封入された希ガスと、該密閉容器中に備えられた紫外光発生用電極を有する発光器具を模式的に示す図面である。図１の発光器具は、上記蛍光体によって形成された管状の発光部の両端に紫外光発生用電極を設置した構造の密閉容器中に、希ガスが封入された構造である。該発光器具では、両端に設置した電極に通電して希ガスを放電させて真空紫外光を発生させ、これを管状の蛍光体に照射して可視光を発生させて、蛍光ランプとして用いることができる。 FIG. 1 schematically shows a light emitting device having a sealed container at least partially formed of the phosphor, a rare gas sealed therein, and an ultraviolet light generating electrode provided in the sealed container. FIG. The light emitting device of FIG. 1 has a structure in which a rare gas is enclosed in a sealed container having a structure in which electrodes for generating ultraviolet light are installed at both ends of a tubular light emitting portion formed of the phosphor. In the light-emitting device, a rare gas is discharged by energizing electrodes installed at both ends to generate vacuum ultraviolet light, and this is irradiated to a tubular phosphor to generate visible light, which can be used as a fluorescent lamp. it can.
図２は、図１と同様の構造の発光器具において、発光部が、球状の蛍光体によって形成された発光器具である。この様な構造の発光器具によれば、管状の発光部を有する発光器具と比較して、発生する可視光を外部に均一に放出することができる。 FIG. 2 shows a light emitting device having a structure similar to that of FIG. 1, in which the light emitting part is formed of a spherical phosphor. According to the light emitting device having such a structure, visible light generated can be uniformly emitted to the outside as compared with a light emitting device having a tubular light emitting portion.
図３は、セル構造を有する発光器具の一例を模式的に示す図面である。図３の発光器具は、密閉容器の前面（可視光の放射面）が上記した蛍光体により形成され、該密閉容器中に希ガスが封入され、更に、該密閉容器の外部に電極を設置したセル構造の発光器具である。この様なセル構造の発光器具は、例えば、ディスプレー等の平型の発光デバイスとして用いることができる。 FIG. 3 is a drawing schematically showing an example of a light-emitting device having a cell structure. In the light emitting device of FIG. 3, the front surface (visible light emission surface) of the sealed container is formed of the above-described phosphor, rare gas is enclosed in the sealed container, and an electrode is installed outside the sealed container. This is a light emitting device having a cell structure. The light emitting device having such a cell structure can be used as, for example, a flat light emitting device such as a display.
図４は、図３と同様のセル構造の発光器具において、外部において発生させた真空紫外光を導入する構造の真空紫外光照射装置を設けたものである。この様な真空紫外光照射装置を設けた発光器具では、密閉容器の蛍光体で形成される面以外の部分については、真空媒体、シリカガラス等の透明媒体で形成することができる。 FIG. 4 shows a light emitting device having a cell structure similar to that shown in FIG. 3, provided with a vacuum ultraviolet light irradiation device having a structure for introducing vacuum ultraviolet light generated outside. In the light emitting apparatus provided with such a vacuum ultraviolet light irradiation device, portions other than the surface formed of the phosphor of the hermetic container can be formed of a transparent medium such as a vacuum medium or silica glass.
図５は、密閉容器の一部が上記蛍光体によって形成された球面状のレンズであり、該密閉容器の内部に紫外光照射装置を備えた構造の発光器具である。この様な構造の発光器具は、可視光を前面広角度に散乱させて放出することができ、蛍光ランプとして有効に利用できる。紫外線照射装置、透明媒体などは、図４の発光器具と同様でよい。 FIG. 5 shows a light emitting apparatus having a structure in which a part of a sealed container is a spherical lens formed of the above-described phosphor, and an ultraviolet light irradiation device is provided inside the sealed container. The light emitting device having such a structure can scatter visible light at a wide angle on the front and emit it, and can be effectively used as a fluorescent lamp. An ultraviolet irradiation device, a transparent medium, etc. may be the same as that of the light-emitting device of FIG.
図６の（ａ）に示す発光器具は、図５と同様の構造の発光器具において、微小な構造とした蛍光ランプである。この様な微小構造の蛍光ランプは、例えば、図６の（ｂ）に示す様に、複数個を平面状に配置することによって、発光照明装置として利用することができる。 The light emitting device shown in FIG. 6A is a fluorescent lamp having a minute structure in the light emitting device having the same structure as that of FIG. For example, as shown in FIG. 6B, a plurality of such fluorescent lamps having a microstructure can be used as a light-emitting illumination device by arranging a plurality of them in a planar shape.
以上の通り、本発明の発光器具は、その形状に応じて、例えば、蛍光ランプ、ディスプレイ、ＬＣＤのバックライト、プラズマディスプレイ等の表示装置等の光源として有効に利用できる。 As described above, the light-emitting device of the present invention can be effectively used as a light source for display devices such as fluorescent lamps, displays, LCD backlights, and plasma displays, depending on the shape.
本発明の発光器具は、高い紫外光透過率を示し、真空紫外光によって励起されて強い発光を示す高ケイ酸ガラスを蛍光体として用いるものである。この様な高ケイ酸質ガラスは、真空紫外光によって励起できるだけでなく、耐熱性、化学的耐久性、機械的強度等も良好であり、紫外光照射による欠陥も発生し難い材料である。更に、該蛍光体は、石英ガラスとほぼ同様の優れた紫外光透過率を有し、しかも石英ガラスよりも低コストで大量に製造することが可能である。従って、この様な蛍光体を用いることにより、低コストで大型の発光器具を容易に製造することができる。 The light emitting device of the present invention uses a high silicate glass exhibiting high ultraviolet light transmittance and exhibiting strong light emission when excited by vacuum ultraviolet light as a phosphor. Such high siliceous glass is a material that not only can be excited by vacuum ultraviolet light, but also has good heat resistance, chemical durability, mechanical strength, and the like, and does not easily cause defects due to ultraviolet light irradiation. Furthermore, the phosphor has an excellent ultraviolet light transmittance substantially similar to that of quartz glass, and can be manufactured in large quantities at a lower cost than quartz glass. Therefore, by using such a phosphor, a large light emitting device can be easily manufactured at low cost.
以上の通り、本発明によれば、紫外光発生源として水銀を用いることなく、より安全性の高いＸｅガス等の放電により発生する真空紫外光を利用して、低コストで耐久性に優れた各種の発光器具を得ることができる。 As described above, according to the present invention, it is possible to use vacuum ultraviolet light generated by discharge of Xe gas or the like with higher safety without using mercury as an ultraviolet light generation source, and is excellent in durability at low cost. Various light emitting devices can be obtained.
以下、実施例を挙げて本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
実施例１
市販の試薬：Ｎａ2ＣＯ3、ＣａＣＯ3、Ａｌ(ＯＨ)3、ＳｉＯ2及びＣｅ2Ｏ3、を用いて
、Ｎａ2Ｏ：１１．５（ｗｔ％）、ＣａＯ：６．０（ｗｔ％）、Ａｌ2Ｏ3：４．０（ｗｔ
％）、ＳｉＯ2：７７．６（ｗｔ％）、Ｃｅ2Ｏ3：１．０（ｗｔ％）のガラス組成となる
ように各試薬を秤量・混合し、白金坩堝を用いて、１４５０℃で４時間溶融させて、ガラスを得た。
Example 1
Using commercially available reagents: Na 2 CO 3 , CaCO 3 , Al (OH) 3 , SiO 2 and Ce 2 O 3 , Na 2 O: 11.5 (wt%), CaO: 6.0 (wt%) ), Al 2 O 3 : 4.0 (wt
%), SiO 2 : 77.6 (wt%), and Ce 2 O 3 : 1.0 (wt%), each reagent was weighed and mixed so as to have a glass composition at 1450 ° C. using a platinum crucible. It was melted for 4 hours to obtain glass.
このガラスを粗粉砕し、得られた粉砕ガラスにＨ3ＢＯ3を溶融させて混合ガラスを得た。その際、粉砕ガラス１００重量部に対して、Ｂ2Ｏ3に換算して５０重量部となるように、Ｈ3ＢＯ3を加えた。溶融させた混合ガラスを冷却し、厚さ０．８ｍｍ弱の板状ガラスを得た。 This glass was coarsely crushed, and H 3 BO 3 was melted in the obtained crushed glass to obtain a mixed glass. At that time, H 3 BO 3 was added to 100 parts by weight of the pulverized glass so as to be 50 parts by weight in terms of B 2 O 3 . The molten mixed glass was cooled to obtain a plate glass having a thickness of less than 0.8 mm.
得られた板状ガラスを研磨した後、５９０℃の熱処理炉で４０時間熱処理を行い、分相させた。次いで、分相させた板状ガラスと１Ｎ硝酸とを密閉容器中に仕込み、９０℃で２４時間酸処理を行った。酸処理した板状ガラスを、さらに大気中で室温から４００℃まで３時間かけてゆっくり昇温して乾燥させて、多孔質ガラスを得た。 After the obtained plate glass was polished, it was subjected to heat treatment in a heat treatment furnace at 590 ° C. for 40 hours to cause phase separation. Next, the phase-separated plate glass and 1N nitric acid were charged into a sealed container, and acid treatment was performed at 90 ° C. for 24 hours. The acid-treated plate-like glass was further heated in the atmosphere from room temperature to 400 ° C. over 3 hours and dried to obtain porous glass.
この多孔質ガラス０．１ｇを、０．２ｇのＣｕＣｌ2・２Ｈ2Ｏを２５ｍｌの蒸留水に溶解させた水溶液中に入れ、２５℃で６０分間放置した後、３５０℃で乾燥させた。この操作を再度繰り返し、その後、カーボンを入れたアルミナるつぼ中で２℃／分の速度で１１００℃まで温度を上昇させ、２時間大気中で熱処理を行い、金属成分としてＣｕを含有する焼成ガラスを得た。 0.1 g of this porous glass was put in an aqueous solution in which 0.2 g of CuCl 2 .2H 2 O was dissolved in 25 ml of distilled water, left at 25 ° C. for 60 minutes, and then dried at 350 ° C. This operation was repeated again, and then the temperature was raised to 1100 ° C. at a rate of 2 ° C./min in an alumina crucible containing carbon, and heat treatment was performed in the atmosphere for 2 hours to obtain a sintered glass containing Cu as a metal component. Obtained.
得られたＣｕ含有ガラスは、ＳｉＯ2を９８．４重量％、Ｂ2Ｏ3を１．３２重量％、Ａ
ｌ2Ｏ3を０．２１重量％、Ｃｕを０．０５８重量％含有し、鉄の存在量は１ｐｐｍ未満であった。
The obtained Cu-containing glass was 98.4% by weight of SiO 2 , 1.32% by weight of B 2 O 3 , A
It contained 0.21% by weight of l 2 O 3 and 0.058% by weight of Cu, and the abundance of iron was less than 1 ppm.
このようにして得たＣｕ含有ガラスを、Ｘｅが数Ｔｏｒｒ封入されたガイスラー管中に入れ、１００Ｖの電圧をかけて、テスラーコイルを用いて放電を行った。すると、電気を消した昼間の部屋において、Ｘｅの放電光によって励起された、可視光の緑色の発光を肉眼で観察できた。 The Cu-containing glass thus obtained was put into a Geisler tube in which Xe was enclosed in several Torr, and a voltage of 100 V was applied to perform discharge using a Tessler coil. Then, the green light emission of visible light excited by the Xe discharge light was observed with the naked eye in the daytime room where the electricity was turned off.
実施例２
実施例１と同様にして得た多孔質ガラス０．１ｇを、０．２ｇのＥｕ(ＮＯ3)3・ｘＨ2
Ｏを１０ｍｌの蒸留水に溶解させた水溶液中に入れ、２５℃で６０分間放置した後、３５０℃で乾燥させた。この操作を再度繰り返し、その後、カーボンを入れたアルミナるつぼ中で２℃／分の速度で１１００℃まで温度を上昇させ、２時間大気中で熱処理を行い、金属成分としてＣｕを含有する焼成ガラスを得た。
Example 2
0.1 g of porous glass obtained in the same manner as in Example 1 was added to 0.2 g of Eu (NO 3 ) 3 .xH 2.
It was put in an aqueous solution in which O was dissolved in 10 ml of distilled water, allowed to stand at 25 ° C. for 60 minutes, and then dried at 350 ° C. This operation was repeated again, and then the temperature was raised to 1100 ° C. at a rate of 2 ° C./min in an alumina crucible containing carbon, and heat treatment was performed in the atmosphere for 2 hours to obtain a sintered glass containing Cu as a metal component. Obtained.
得られたＥｕ含有ガラスは、ＳｉＯ2を９８．３重量％、Ｂ2Ｏ3を１．３０重量％、Ａ
ｌ2Ｏ3を０．２０重量％、Ｅｕを０．０４５重量％含有し、鉄の存在量は１．２ｐｐｍであった。この様にして得たＥｕ含有ガラスを、Ｘｅが数Ｔｏｒｒ封入されたガイスラー管中に入れ、１００Ｖの電圧をかけて、テスラーコイルを用いて放電を行った。すると、電気を消した昼間の部屋において、Ｘｅの放電光によって励起された、可視光の青色の発光を肉眼で観察できた。
The obtained Eu-containing glass, a SiO 2 98.3 wt%, the B 2 O 3 1.30 wt%, A
It contained 0.20% by weight of l 2 O 3 and 0.045% by weight of Eu, and the abundance of iron was 1.2 ppm. The Eu-containing glass thus obtained was placed in a Geisler tube in which Xe was sealed in several Torr, and a voltage of 100 V was applied to perform discharge using a Tessler coil. Then, in the daytime room where the electricity was turned off, visible light emission of blue light excited by the Xe discharge light could be observed with the naked eye.
実施例３
実施例１と同様にして得た多孔質ガラス０．１ｇを、０．５ｇのY（NO3）3・６H2Oと０．５ｇのＥｕ(ＮＯ3)3・ｘＨ2Ｏを１０ｍｌの蒸留水に溶解させた水溶液中に入れ、２５
℃で６０分間放置した後、３５０℃で乾燥させた。この操作を再度繰り返し、その後、カーボンを入れたアルミナるつぼ中で２℃／分の速度で１１００℃まで温度を上昇させ、２時間大気中で熱処理を行い、金属成分としてEuとYを含有する焼成ガラスを得た。
Example 3
0.1 g of porous glass obtained in the same manner as in Example 1 was distilled from 10 g of 0.5 g of Y (NO 3 ) 3 .6H 2 O and 0.5 g of Eu (NO 3 ) 3 .xH 2 O. Put in an aqueous solution dissolved in water, 25
After leaving at 60 ° C. for 60 minutes, it was dried at 350 ° C. This operation was repeated again, and then the temperature was raised to 1100 ° C. at a rate of 2 ° C./min in an alumina crucible containing carbon, and heat treatment was performed in the atmosphere for 2 hours, and firing containing Eu and Y as metal components Glass was obtained.
得られたＥｕ含有ガラスは、ＳｉＯ2を９８．３重量％、Ｂ2Ｏ3を１．3０重量％、Ａｌ
2Ｏ3を０．２０重量％、Euを０．０８９重量％、Yを０．０９０重量％含有し、鉄の存在
量は１ｐｐｍ以下であった。
The obtained Eu-containing glass, a SiO 2 98.3 wt%, the B 2 O 3 1.30 wt%, Al
2 O 3 was contained at 0.20% by weight, Eu was contained at 0.089% by weight, Y was contained at 0.090% by weight, and the abundance of iron was 1 ppm or less.
この様にして得たＥｕ含有ガラスを、Ｘｅが数Ｔｏｒｒ封入されたガイスラー管中に入れ、１００Ｖの電圧をかけて、テスラーコイルを用いて放電を行った。すると、電気を消した昼間の部屋において、Ｘｅの放電光によって励起された、可視光の赤色の発光を肉眼で観察できた。 The Eu-containing glass thus obtained was placed in a Geisler tube in which Xe was sealed in several Torr, and a voltage of 100 V was applied to perform discharge using a Tessler coil. Then, in the daytime room where the electricity was turned off, visible red light emitted by the Xe discharge light could be observed with the naked eye.
Claims (10)
該蛍光体が、ＳｉＯ2を９６重量％以上、Ｂ2Ｏ3を０．５〜２重量％、Ａｌ2Ｏ3を０．
１〜０．８重量％、並びに周期表３Ａ族、４Ａ族、５Ａ族、６Ａ族、７Ａ族、８族、１Ｂ族、２Ｂ族及び４Ｂ族の各族に属する元素からなる群から選ばれた少なくとも一種の金属成分を５０〜２０００ｐｐｍ含有し、Ｆｅの存在量が５ｐｐｍ以下の高ケイ酸ガラスであることを特徴とする発光器具。 A light emitting device having a sealed container formed of a phosphor that emits light by vacuum ultraviolet light, and a vacuum ultraviolet light irradiation source provided in the sealed container,
The phosphor has a SiO 2 content of 96% by weight or more, a B 2 O 3 content of 0.5 to 2% by weight, and an Al 2 O 3 content of 0.1%.
1 to 0.8% by weight and selected from the group consisting of elements belonging to groups 3A, 4A, 5A, 6A, 7A, 8, 1B, 2B and 4B A light-emitting device characterized by being a high-silicate glass containing at least one metal component in an amount of 50 to 2000 ppm and an Fe content of 5 ppm or less.
（i）重金属及び希土類元素からなる群から選ばれた少なくとも一種の元素を酸化物とし
て含むアルカリホウケイ酸塩ガラスに熱処理を施して分相させる工程、
（ii）上記（ｉ）工程で分相処理が施されたアルカリホウケイ酸ガラスに対して酸処理を行い、多孔質ガラスとする工程、
（iii）上記（ii）工程で得られた多孔質ガラスに、周期表３Ａ族、４Ａ族、５Ａ族、６
Ａ族、７Ａ族、８族、１Ｂ族、２Ｂ族及び４Ｂ族の各族に属する元素からなる群から選ばれた少なくとも一種の金属成分を吸着させる工程、
（iv）上記(iii)工程で金属成分を吸着させた多孔質ガラスを焼成する工程。 The phosphor according to claim 1 or 2, wherein the phosphor is a high silicate glass obtained by the following steps (i) to (iv):
(I) a step of subjecting an alkali borosilicate glass containing at least one element selected from the group consisting of heavy metals and rare earth elements as an oxide to heat treatment to cause phase separation;
(Ii) a step of performing acid treatment on the alkali borosilicate glass subjected to the phase separation treatment in the step (i) to form a porous glass;
(Iii) The porous glass obtained in the step (ii) is added to the periodic table 3A group, 4A group, 5A group, 6
Adsorbing at least one metal component selected from the group consisting of elements belonging to groups A, 7A, 8, 1B, 2B and 4B;
(Iv) A step of firing the porous glass in which the metal component is adsorbed in the step (iii).
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| JP2010006664A (en) * | 2008-06-30 | 2010-01-14 | National Institute Of Advanced Industrial & Technology | Green fluorescent glass |
| JP2010018460A (en) * | 2008-07-09 | 2010-01-28 | National Institute Of Advanced Industrial & Technology | Red fluorescent glass |
| JP2010059018A (en) * | 2008-09-04 | 2010-03-18 | Hoya Corp | Preform lot and method for producing optical element |
| CN102730967A (en) * | 2012-06-29 | 2012-10-17 | 中国科学院上海光学精密机械研究所 | Preparation method for sensitization-enhanced green light-emitting high-silica glass |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8637415B2 (en) | 2008-03-28 | 2014-01-28 | Hoya Corporation | Fluorophosphate glass, precision press molding preform, optical element blank, optical element and methods of manufacturing the same |
| US8642490B2 (en) | 2008-03-28 | 2014-02-04 | Hoya Corporation | Fluorophosphate glass, precision press molding preform, optical element blank, optical element and method of manufacturing the same |
| JP2010006664A (en) * | 2008-06-30 | 2010-01-14 | National Institute Of Advanced Industrial & Technology | Green fluorescent glass |
| JP2010018460A (en) * | 2008-07-09 | 2010-01-28 | National Institute Of Advanced Industrial & Technology | Red fluorescent glass |
| JP2010059018A (en) * | 2008-09-04 | 2010-03-18 | Hoya Corp | Preform lot and method for producing optical element |
| US8633121B2 (en) | 2009-08-26 | 2014-01-21 | Hoya Corporation | Fluorophosphate glass, glass material for press molding, optical element blank, optical element, processes for production of same, and process for production of glass moldings |
| CN102730967A (en) * | 2012-06-29 | 2012-10-17 | 中国科学院上海光学精密机械研究所 | Preparation method for sensitization-enhanced green light-emitting high-silica glass |
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