WO2012034625A1 - Silicophosphat-leuchtstoffe - Google Patents
Silicophosphat-leuchtstoffe Download PDFInfo
- Publication number
- WO2012034625A1 WO2012034625A1 PCT/EP2011/004104 EP2011004104W WO2012034625A1 WO 2012034625 A1 WO2012034625 A1 WO 2012034625A1 EP 2011004104 W EP2011004104 W EP 2011004104W WO 2012034625 A1 WO2012034625 A1 WO 2012034625A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- phosphor
- range
- compound
- mixture
- formula
- Prior art date
Links
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 229910052909 inorganic silicate Inorganic materials 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 85
- 239000000203 mixture Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 28
- 238000002360 preparation method Methods 0.000 claims description 17
- 239000011575 calcium Substances 0.000 claims description 16
- 229910052712 strontium Inorganic materials 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 239000004065 semiconductor Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 150000004767 nitrides Chemical class 0.000 claims description 7
- -1 ammonium halides Chemical class 0.000 claims description 6
- 229910052788 barium Inorganic materials 0.000 claims description 6
- 238000007669 thermal treatment Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 229910052693 Europium Inorganic materials 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 3
- 239000004973 liquid crystal related substance Substances 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- BKQMNPVDJIHLPD-UHFFFAOYSA-N OS(=O)(=O)[Se]S(O)(=O)=O Chemical class OS(=O)(=O)[Se]S(O)(=O)=O BKQMNPVDJIHLPD-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229910001637 strontium fluoride Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 150000002222 fluorine compounds Chemical class 0.000 claims 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 239000010410 layer Substances 0.000 description 17
- 238000000576 coating method Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000000919 ceramic Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 230000005855 radiation Effects 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229920001296 polysiloxane Polymers 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 238000000295 emission spectrum Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000005118 spray pyrolysis Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000009877 rendering Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 229910002601 GaN Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 206010021143 Hypoxia Diseases 0.000 description 2
- 241000023320 Luma <angiosperm> Species 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000000695 excitation spectrum Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 150000004673 fluoride salts Chemical class 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000000462 isostatic pressing Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000001694 spray drying Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- 206010001497 Agitation Diseases 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000001856 aerosol method Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010616 electrical installation Methods 0.000 description 1
- 238000009429 electrical wiring Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229940110728 nitrogen / oxygen Drugs 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000004038 photonic crystal Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001902 propagating effect Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/7734—Aluminates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/0883—Arsenides; Nitrides; Phosphides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
- C09K11/71—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus also containing alkaline earth metals
- C09K11/712—Halogenides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/77347—Silicon Nitrides or Silicon Oxynitrides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/77348—Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7792—Aluminates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/77922—Silicates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
- C09K11/7795—Phosphates
- C09K11/7796—Phosphates with alkaline earth metals
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
- F21V9/00—Elements for modifying spectral properties, polarisation or intensity of the light emitted, e.g. filters
- F21V9/30—Elements containing photoluminescent material distinct from or spaced from the light source
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
Definitions
- the invention relates to silicophosphate compounds, processes for
- Inorganic phosphors are used in fluorescent light sources, emissive screens and as scintillator crystals or ceramics for the
- Ce 3+ doped garnets of the general composition 3 (Ali -a- b Ga a SC b) 5 0i 2 (Yi -wx- y z GdxLuyTb. 2): Ce Wl wherein the variation of the composition for
- white-emitting LEDs contain a blue-emitting (ln, Ga) N semiconductor chip, which is coated with a luminescent screen consisting of a ceramic Ce 3+ doped garnet.
- Ce 3+ or Eu 2+ doped nitrides and oxynitrides are currently the focus of attention here, since these actiVators show luminescence in the green to red spectral range due to the high zentroid shift in these host lattices, while in most purely oxidic materials both Ce 3+ and Eu 2+ luminesce especially in the UV or in the blue spectral range.
- Phosphors based on the eulytine structure were first described by G. Blasse [J. Sol. State Chem. 2, 27-30 (1970)]. However, only compounds doped with Eu3 + or Ce3 + have been studied so far. However, these are not suitable for the excitation with blue LEDs.
- the object of the present invention was to develop silicophosphate phosphors which have a yellow-orange luminescence and are particularly suitable for use in high-power pcLEDs for producing cold-white light.
- these phosphors are particularly suitable for the production of cold white light. They are distinguished from the known Ba 2 Y 2 (PO 4 ) 2 (SiO) phosphors doped with Eu 3+ or Ce 3+ by the higher absorption strength in the blue spectral range.
- a, c, d independently represent a value in the range of
- 0 to 1 x is a value in the range of 0 to 0.8.
- x is a value in the range 0.05 to 0.5 and particularly preferably in the range 0.1 to 0.3.
- a is a value in the range 0 to 0.5
- b stands for a value from the range 0 ⁇ b ⁇ 0.1.
- c and d independently represent a value in the range of 0 to 0.8.
- LED quality is over usual parameters, such as the Color Rendering Index or the
- the Color Rendering Index or CRI is a known to the expert, unitless photometric size, the color fidelity of an artificial light source with that of sunlight or
- Filament light sources compare (the latter two have a CRI of 100).
- CIE x and CIE y stand for the coordinates in the CIE standard color diagram familiar to the person skilled in the art (here standard observer 1931), with which the color of a light source is described.
- yellow-orange light such light whose intensity maximum is between 560 and 590 nm wavelength and as red light whose maximum is between 600 and 670 nm wavelength.
- a further subject of the invention is a process for the preparation of a compound of the formula I comprising the following steps:
- step c) the conversion usually takes place at one
- the reducing conditions are e.g. adjusted with carbon monoxide, forming gas or hydrogen or at least VAkuum or oxygen deficiency atmosphere, preferably below
- calcination is carried out again at a temperature> 1000 ° C., preferably between 1100 and 1300 ° C., preferably under forming gas N 2 / H 2 stream and particularly preferably in N 2 / H 2 stream (90-70: 10-30) ).
- inorganic or organic substance is a substance from the group of ammonium halides, preferably ammonium chloride, alkaline earth fluorides such as calcium, strontium or barium fluoride, borates, Boric acid, carbonates, preferably ammonium bicarbonate,
- Alcoholates such as oxalates and / or silica such as tetraethyl orthosilicate (TEOS) used.
- TEOS tetraethyl orthosilicate
- the preparation of the phosphors according to the invention can either by a conventional solid-state diffusion method (starting from the oxides, nitrates, carbonates or halides of the corresponding alkaline earth metals, semimetals, metals or rare earths) or
- the invention is the
- Co-precipitation also called co-precipitation
- an NH 4 HCO 3 solution see, for example, Jander, Blasius Textbook of the Analytical and Preparatory Anorg. Chem.
- chloride solutions of the corresponding phosphorus are mixed with a TEOS / NH 4 HCO 3 solution, whereby forms the phosphor precursor, which is then converted by a single or multi-stage thermal treatment in the phosphor.
- the spray pyrolysis belongs to the aerosol method, by spraying solutions, suspensions or dispersions in a through
- the yellow-orange-emitting phosphors according to the invention can also be mixed with red-emitting phosphors, resulting in Such mixtures are very well suited for general lighting applications (eg for warm white LEDs) and LCD backlighting.
- a further embodiment of the present invention is therefore a mixture containing at least one compound of the formula I and at least one red-emitting phosphor, which is preferably selected from Ce-doped garnets, Eu-doped thiogallates, Eu-doped sulfoselenides and Eu and / or Ce-doped nitrides,
- the red-emitting phosphor may be selected from the nitride phosphors, preferably (Ca.Sr.BahSisNeiEu, (Ca, Sr) AISiN 3 : Eu, (Ca, Sr; Ba) SiN 2 : Eu, (approx , Sr, Ba) 6 Si 3 O 6 N 4: Eu, (A 2- o, 5y-x Eu x Si 5 N 8-y O y , wherein A represents one or more elements selected from Ca, Sr, Ba and x for a value in the range of 0.005 to 1 and y stands for a value in the range of 0.01 to 3 or VArianten of said compounds, in which individual lattice positions by other chemical elements, such as alkali metals, aluminum, gallium, or gadolinium, or such further elements
- Aluminosiliconitrides such as the (Ca, Sr) AISiN 3 : Eu 2+ (K. Uheda et al.
- the compound A2-o, 5y-x Eu x Si 5 Ne -y O y wherein A represents one or more elements selected from Ca, Sr, Ba and x represents a value in the range of 0.005 to 1 and y for a value in the range of 0.01 to 3 is described in the patent application EP10000933.1 and is called in the following compound of formula II. It can the Compound be present as a pure substance or in a mixture with at least one further silicon and oxygen-containing compound, it being preferred if the at least one further silicon and oxygen-containing compound is a reaction by-product of the preparation of the compound of formula II and this the application-relevant optical properties of the compound of formula II is not adversely affected.
- a mixture containing a compound of formula II which is obtainable by a process in which in a step a) suitable starting materials selected from binary nitrides, halides and oxides or corresponding reactive forms are mixed thereto and the mixture in a step b) thermally treated under reductive conditions is another subject of the invention.
- Embodiments represents a value in the range of 0.01 to 0.8, preferably in the range of 0.02 to 0.7, and more preferably in the range of 0.05 to 0.6 and more preferably in the range
- Range 0.1 to 0.4 and y in preferred embodiments is for a value in the range of 0.1 to 2.5, preferably from
- Range 0.2 to 2 and more preferably from 0.22 to 1.8.
- step a) For the preparation of phosphors of the formula II, suitable starting materials selected from binary nitrides, halides and oxides or corresponding reactive forms are mixed in step a) and the mixture is thermally treated in a step b) under reductive conditions. In the case of the abovementioned thermal treatment, it is preferred if these are at least partially reduced
- step b) the reaction is usually carried out at a temperature above 800 C, preferably at a temperature above 1200 ° C, and more preferably in the
- the reductive conditions are eg carbon monoxide, forming gas or hydrogen or at least Adjusted vacuum or oxygen deficiency atmosphere, preferably in a stream of nitrogen, preferably in the N 2 / H 2 stream and particularly preferably in the N 2 / H2 / NH 3 stream adjusted. If the compounds of the formula II are to be prepared in pure form, this can be done either by precise control of the educt stoichiometry or by mechanical separation of the crystals of the compounds of the formula II from the glassy fractions. The separation can be done, for example, via the different density,
- the compound (or phosphor) according to formula I and the at least one red emitting phosphor are present
- the at least one phosphor of the formula I and the at least one red-emitting phosphor to be present in a weight ratio of 10: 1 to 3: 1 and particularly preferably 6: 1 to 4: 1.
- a further subject of the invention is a process for the preparation of a phosphor mixture in which at least one compound (or
- Phosphor is mixed.
- the particle size of the phosphors according to the invention is
- the phosphors in particle form have a closed surface coating consisting of SiO 2 , TiO 2 , Al 2 O 3, ZnO , ZrO 2 and / or Y 2 O 3 or mixed oxides thereof.
- Luminescent decreases and a greater proportion of the light can penetrate into the phosphor and absorbed and converted there.
- a closed layer is advantageous if the phosphor has to be encapsulated. This may be necessary to one
- closed shell is a thermal decoupling of the actual phosphor from the heat that arises in the chip. This heat leads to a reduction in the fluorescent light output of the phosphor and may also affect the color of the fluorescent light. Finally, it is possible by such a coating to increase the efficiency of the phosphor by preventing lattice vibrations arising in the phosphor from propagating to the environment.
- the phosphors are porous
- Phosphor particles have a surface which carries functional groups, which allows a chemical connection to the environment, preferably consisting of epoxy or silicone resin.
- These functional groups may e.g. oxo group-attached esters or other derivatives that can form linkages with components of the epoxy-based and / or silicone-based binders.
- Such surfaces have the advantage that a homogeneous mixing of the phosphors is made possible in the binder.
- the rheological properties of the system phosphor / binder and also the pot life can be adjusted to a certain extent. This simplifies the processing of the mixtures.
- Phosphor layer preferably consists of a mixture of silicone and homogeneous phosphor particles, which is applied by volume casting, and the silicone has a surface tension, this phosphor layer is not uniform at the microscopic level or the thickness of the layer is not consistently constant. This is usually also the case when the phosphor is not applied by the volume casting method, but in the so-called chip-level conversion method in which a highly concentrated, thin phosphor layer is applied directly to the surface of the chip by means of electrostatic methods.
- platelet-shaped phosphors as a further preferred embodiment is done by conventional methods from the corresponding metal and / or rare earth salts.
- the manufacturing process is described in detail in EP 763573 and DE 102006054331, which are fully in the context of the present application by
- platelet-shaped phosphors can be prepared by a natural or synthetically produced highly stable support or a substrate of, for example mica, SiO 2 , Al 2 0 3 , ZrO 2 , glass or TiO 2 platelets, which is a very has high aspect ratio, has an atomically smooth surface and an adjustable thickness, can be coated by precipitation reaction in aqueous dispersion or suspension with a phosphor layer.
- the platelets can also consist of the phosphor material itself, or be composed of a material.
- the wafer itself merely serves as a carrier for the phosphor coating, it must be made of a material which is transparent to the primary radiation of the LED, or absorbs the primary radiation and transfers this energy to the phosphor layer.
- the platelet-shaped phosphors are dispersed in a resin (eg, silicone or epoxy resin), and these
- Dispersion is applied to the LED chip.
- the platelet-shaped phosphors can be produced on a large scale in thicknesses of 50 nm up to about 20 ⁇ m, preferably between 150 nm and 5 ⁇ m.
- the diameter is from 50 nm to 20 pm. It usually has an aspect ratio (ratio of diameter to particle thickness) of 1: 1 to 400: 1, and more preferably 3: 1 to 100: 1.
- the platelet expansion (length x width) is from the assembly
- Platelets are also suitable as scattering centers within the conversion layer, especially if they are particularly small
- the surface of the platelet-shaped phosphor according to the invention facing the LED chip can be provided with a coating which acts in an anti-reflection manner with respect to the primary radiation emitted by the LED chip. This leads to a reduction in backscatter the primary radiation, whereby it can be better coupled into the phosphor body according to the invention.
- Ceramic bodies are analogous to the method described in DE 102006037730 (Merck), which is fully incorporated by reference in the context of the present application.
- the phosphor is prepared wet-chemically by mixing the corresponding reactants and dopants, then isostatically pressed and applied in the form of a homogeneous thin and non-porous platelets directly on the surface of the chip.
- Phosphor bodies can e.g. be produced industrially as platelets in thicknesses of a few 100 nm to about 500 ⁇ .
- Platelet expansion depends on the arrangement.
- the size of the wafer according to the chip size (from about 100 m * 100 m to several mm 2 ) with a certain excess of about 10% - 30% of the chip surface with a suitable chip arrangement (eg Flip Chip arrangement) or to choose accordingly.
- a suitable chip arrangement eg Flip Chip arrangement
- the side surfaces of the ceramic phosphor body can be mirrored with a light or noble metal, preferably aluminum or silver. The mirroring causes no light to escape laterally from the
- ceramic phosphor body takes place in a process step after the isostatic pressing to bars or plates, which may be done before the mirroring a tailor of the rods or plates in the required size.
- the side surfaces are for this purpose e.g. wetted with a solution of silver nitrate and glucose and then exposed at elevated temperature to an ammonia atmosphere.
- a silver coating on the side surfaces e.g. a silver coating on the side surfaces.
- the ceramic phosphor body may, if necessary, with a
- Waterglass solution to be fixed on the substrate of an LED chip.
- the ceramic has
- Phosphor body has a patterned (e.g., pyramidal) surface on the side opposite an LED chip. Thus, as much light as possible can be coupled out of the phosphor body.
- the pressing tool has a structured pressing plate and thereby embosses a structure in the surface. Structured surfaces are desired when thin phosphor bodies or platelets are to be produced.
- the excitability of the phosphors according to the invention also extend over a wide range, ranging from about 410 nm to 530 nm, preferably 430 nm to about 500 nm.
- these phosphors are not only suitable for excitation by violet or blue emitting light sources such as LEDs or conventional discharge lamps (eg based on Hg), but also for light sources such as those which exploit the blue ln 3+ line at 451 nm.
- Another object of the present invention is a light source, characterized in that it contains a semiconductor and at least one phosphor according to formula I.
- Another object of the present invention is a light source characterized in that it contains a semiconductor and at least one compound of formula I and at least one red emitting phosphor.
- this lighting unit emits white or emits light with a specific color point (color-on-demand principle).
- This concept is e.g. used to design certain corporate designs, e.g. for illuminated company logos, brands etc.
- the semiconductor is a luminescent one
- Indiumaluminum gallium nitride in particular the formula
- the light source is a luminescent arrangement based on ZnO, TCO (transparent conducting oxide), ZnSe or SiC or else an arrangement based on an organic light-emitting layer (OLED).
- OLED organic light-emitting layer
- the light source is a source which
- Electroluminescence and / or photoluminescence shows.
- the light source may also be a plasma or discharge source.
- the phosphors of the present invention may be dispersed either in a resin (e.g., epoxy or silicone resin) or in suitable ones
- LC display liquid crystal display device
- Backlight which are characterized in that they contain at least one such lighting unit.
- a lighting unit in particular for
- the optical coupling of the illumination unit between the phosphor and the semiconductor is realized by a light-conducting arrangement.
- the lighting requirements adapted lights can only consist of one or
- different phosphors which may be arranged to form a luminescent screen, and a light guide, which is coupled to the light source implement.
- a strong light source at a convenient location for the electrical installation and to install without further electrical wiring, but only by laying fiber optics at any location lights of phosphors, which are coupled to the light guide.
- Another object of the present invention is the use of the phosphors according to the invention for the partial or complete conversion of blue or in the near UV emission of a
- Emitting diode Further preferred is the use of the invention
- Phosphors for conversion of blue or near UV emission into visible white radiation. Furthermore, the use of the phosphors according to the invention for converting the primary radiation into a specific color point according to the "color on demand" concept is preferred.
- Another object of the present invention is the use of the phosphors according to the invention in electroluminescent materials, such as electroluminescent films (also called phosphors or light foils) in which, for example, zinc sulfide or zinc sulfide doped with Mn 2+ , Cu + , or Ag + as an emitter is used, which emit in the yellow-green area.
- electroluminescent materials such as electroluminescent films (also called phosphors or light foils) in which, for example, zinc sulfide or zinc sulfide doped with Mn 2+ , Cu + , or Ag + as an emitter is used, which emit in the yellow-green area.
- Electroluminescent films are e.g. Advertising, display backlighting in liquid crystal displays (LC displays) and
- TFT displays Thin-film transistor displays
- self-illuminating license plate labels floor graphics (in combination with a non-slip and non-slip laminate), in display and / or control elements
- the resulting sinter cake is ground and sieved through a 36 ⁇ m sieve.
- Forming gas N 2 H 2 (90/10) to completely reduce residual Eu 3+ .
- the resulting sinter cake is ground and sieved through a 36 ⁇ m sieve.
- the phosphor is removed and suspended in 100 ml of 1 molar hydrochloric acid. The resulting suspension is stirred for 3 hours, then the stirrer is switched off. After a few minutes, the supernatant is poured off, the remaining residue is taken up in deionized water again, filtered off with suction, neutral with deionized water
- Silica are weighed into a nitrogen-filled glovebox and mixed. The resulting mixture is filled into a molybdenum crucible and transferred to a tube furnace. Subsequently, the mixture is calcined at 1600 ° C for 8 hours under a nitrogen / oxygen atmosphere. After cooling, the crude phosphor is removed, briefly crushed and filled again in a molybdenum crucible, which is then transferred to a high-pressure furnace. In this, the phosphor is again calcined for 8 hours at 1600 ° C under a nitrogen pressure of 65 bar.
- the phosphor is removed and suspended in 100 ml of deionized water. The resulting suspension is stirred for 30 minutes, then the stirrer is switched off. After a few minutes, the supernatant is poured off, the residue remaining is again taken up in demineralized water, filtered off with suction, washed neutral with demineralized water and dried.
- Nitrogen pressure of 500 bar set then the material was heated to 1700 ° C and annealed for 4 hours at this temperature, in this case, the pressure rose to 1740 bar. After cooling and ventilation was the
- a mixture containing the phosphors of Examples 1 and 3A or 1 and 3B or 1 and 3 D is prepared analogously.
- the phosphor mixture from Example 4.1 is mixed in a tumble mixer with a 2-component silicone (OE 6550 from Dow Corning), so that equal amounts of the phosphor mixture in the two
- Components of the silicone are dispersed; the total concentration of the phosphor mixture in the silicone is 8% by weight. 5 ml of each of the two phosphor-containing silicone components are homogeneously mixed together and transferred to a dispenser. With the help of the dispenser, empty LED packages from the company OSA optoelectronics, Berlin, which contain a 100 pm 2 large GaN chip filled. The LEDs are then placed in a heat chamber to solidify the silicone for 1 h at 150 ° C.
- Tab. 1 shows the optical properties of the invention
- CIE x and CIE y represent the coordinates in the CIE standard color diagram familiar to the person skilled in the art (here standard observer 1931), which describes the color of a light source.
- the lumenal equivalent [Im W] results from the product of the normalized emission spectrum I (lambda) with the eye sensitivity curve
- FIG. 2 shows an excitation spectrum of Ba2.i78Eu 0 .o22Lui.8 (P04) 2.2 (Si04) o.8
- the spectrum were performed on a rudunerium thick powder layer with a Edinburgh Instruments FL900 spectrometer using a
- Fig. 3 shows the normalized emission spectrum
- Fig. 4 shows a reflection spectrum of Ba 2 . 1 78Euo.o22Lui.8 (P04) 2.2 (Si04) o.8 The spectrum was recorded on a semi-infinite thick powder layer using an Edinburgh Instruments F920 spectrometer in an Ulbricht sphere using a high pressure Xe lamp and a Hamamatsu photomultiplier at room temperature.
- Fig. 5 shows a CIE 1931 color chart with the color point of
- FIG. 6 shows an excitation spectrum of Ba2.ii2Eu 0 .o88Lui.8 (P04) 2.2 (Si04) o. 8
- the spectrum was recorded on a semi-infinite thick powder layer using an Edinburgh Instruments FL900 spectrometer using a high-pressure Xe lamp and a Hamamatsu photomultiplier tube
- Fig. 7 shows the normalized emission spectrum
- Fig. 8 shows a reflectance spectrum of Ba 2 .ii 2 Euo.o88 ui.8 (PO 4) 2.2 (SiO 4) o.8
- the spectrum was submerged on a semi-infinite thick powder layer with an Edinburgh Instruments F920 spectrometer in an integrating sphere Using a high-pressure Xe lamp and a Hamamatsu photomultiplier recorded at room temperature.
- Figure 9 shows a CIE 1931 color chart with the color point of
- Ba2.ii2Euo.o88Lui.8 (P04) 2.2 (Si04) o.8 and various blue LEDs (Lumileds Luxeon) and the Black body line (BBL), which represents the color point course of a Planckian radiator with the temperature.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Physics & Mathematics (AREA)
- General Engineering & Computer Science (AREA)
- Luminescent Compositions (AREA)
- Silicon Compounds (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013528533A JP5819967B2 (ja) | 2010-09-14 | 2011-08-16 | ケイリン酸蛍光物質 |
US13/822,701 US8987687B2 (en) | 2010-09-14 | 2011-08-16 | Silicophosphate phosphors |
CN201180044229.XA CN103124779B (zh) | 2010-09-14 | 2011-08-16 | 硅磷酸盐发光材料 |
EP11751816.7A EP2616523B1 (de) | 2010-09-14 | 2011-08-16 | Silicophosphat-leuchtstoffe |
KR1020137009334A KR101849806B1 (ko) | 2010-09-14 | 2011-08-16 | 실리코포스페이트 발광단 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102010045368.4 | 2010-09-14 | ||
DE102010045368A DE102010045368A1 (de) | 2010-09-14 | 2010-09-14 | Silicophosphat-Leuchtstoffe |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012034625A1 true WO2012034625A1 (de) | 2012-03-22 |
Family
ID=44545634
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2011/004104 WO2012034625A1 (de) | 2010-09-14 | 2011-08-16 | Silicophosphat-leuchtstoffe |
Country Status (8)
Country | Link |
---|---|
US (1) | US8987687B2 (de) |
EP (1) | EP2616523B1 (de) |
JP (1) | JP5819967B2 (de) |
KR (1) | KR101849806B1 (de) |
CN (1) | CN103124779B (de) |
DE (1) | DE102010045368A1 (de) |
TW (1) | TWI502052B (de) |
WO (1) | WO2012034625A1 (de) |
Cited By (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103059849A (zh) * | 2013-01-23 | 2013-04-24 | 苏州大学 | 一种Eu2+激活的硅磷酸盐绿色荧光粉、制备方法及应用 |
CN104428395A (zh) * | 2012-07-13 | 2015-03-18 | 默克专利有限公司 | 制备无机发光材料的方法 |
EP2947697A1 (de) | 2013-12-23 | 2015-11-25 | Merck Patent GmbH | Antireflexionsschichten und fotovoltaische Vorrichtungen |
WO2018050526A1 (en) | 2016-09-13 | 2018-03-22 | Merck Patent Gmbh | Light luminescent particle |
WO2018096135A1 (en) | 2016-11-28 | 2018-05-31 | Merck Patent Gmbh | Composition comprising a nanosized light emitting material |
WO2018108767A1 (en) | 2016-12-15 | 2018-06-21 | Merck Patent Gmbh | Semiconducting light emitting nanoparticle |
WO2018146120A1 (en) | 2017-02-10 | 2018-08-16 | Merck Patent Gmbh | Semiconductor nanosized material |
WO2018224459A1 (en) | 2017-06-08 | 2018-12-13 | Merck Patent Gmbh | A composition comprising semiconducting light-emitting nanoparticles having thiol functional surface ligands |
WO2019002239A1 (en) | 2017-06-29 | 2019-01-03 | Merck Patent Gmbh | COMPOSITION COMPRISING A SEMICONDUCTOR ELECTROLUMINESCENT NANOPARTICLE |
WO2019105798A1 (en) | 2017-11-30 | 2019-06-06 | Merck Patent Gmbh | Composition comprising a semiconducting light emitting nanoparticle |
WO2019215059A1 (en) | 2018-05-09 | 2019-11-14 | Merck Patent Gmbh | Semiconducting nanoparticle |
WO2019224182A1 (en) | 2018-05-24 | 2019-11-28 | Merck Patent Gmbh | Formulation comprising particles, a polymer and an organic solvent |
WO2019224134A1 (en) | 2018-05-23 | 2019-11-28 | Merck Patent Gmbh | Semiconducting nanoparticle |
WO2020078843A1 (en) | 2018-10-15 | 2020-04-23 | Merck Patent Gmbh | Nanoparticle |
WO2020099284A1 (en) | 2018-11-14 | 2020-05-22 | Merck Patent Gmbh | Nanoparticle |
WO2020127188A1 (en) | 2018-12-20 | 2020-06-25 | Merck Patent Gmbh | Surface modified semiconducting light emitting nanoparticles and process for preparing such |
WO2020156969A1 (en) | 2019-01-29 | 2020-08-06 | Merck Patent Gmbh | Composition |
WO2020208127A1 (en) | 2019-04-12 | 2020-10-15 | Merck Patent Gmbh | Composition |
WO2020216813A1 (en) | 2019-04-26 | 2020-10-29 | Merck Patent Gmbh | Nanoparticle |
WO2021069432A1 (en) | 2019-10-07 | 2021-04-15 | Merck Patent Gmbh | Vertically aligned liquid-crystal element having at least one light converting layer which shifts the wavelength of incident light to longer values |
WO2024028426A1 (en) | 2022-08-05 | 2024-02-08 | Merck Patent Gmbh | Composition |
WO2024079230A1 (en) | 2022-10-14 | 2024-04-18 | Merck Patent Gmbh | Composition |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102012220656A1 (de) * | 2012-11-13 | 2014-05-15 | Siemens Aktiengesellschaft | In-situ Dotierung zur Herstellung strukturierter oder gradierter Leuchtstoffkeramiken |
CN104087300B (zh) * | 2014-03-20 | 2017-03-15 | 王海容 | 一种硫代磷酸盐荧光体及其应用 |
WO2018193838A1 (ja) * | 2017-04-18 | 2018-10-25 | Ntn株式会社 | シンチレータ用セラミックス組成物、シンチレータ及び放射線検出装置、並びにシンチレータの製造方法 |
WO2018235495A1 (ja) * | 2017-06-19 | 2018-12-27 | Ntn株式会社 | ストレージ蛍光体、ストレージ蛍光体の製造方法、放射線検出素子、個人被曝線量計及びイメージングプレート |
CN108300469A (zh) * | 2018-01-29 | 2018-07-20 | 上海纳米技术及应用国家工程研究中心有限公司 | 激光激发稀土掺杂硅磷酸钙高亮度三基色纳米荧光粉的制备及产品和应用 |
CN114164000A (zh) * | 2021-11-16 | 2022-03-11 | 五邑大学 | 一种温度传感材料及其制备方法和应用 |
CN118619218A (zh) * | 2024-07-01 | 2024-09-10 | 广西农业职业技术大学 | 一种Sr2Si5N8:Eu2+纳米粒子的喷雾热解合成方法 |
Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4019884A (en) | 1976-01-22 | 1977-04-26 | Corning Glass Works | Method for providing porous broad-band antireflective surface layers on chemically-durable borosilicate glasses |
US4151443A (en) * | 1977-10-03 | 1979-04-24 | U.S. Philips Corporation | Luminescent materials and discharge lamp containing the same |
EP0763573A2 (de) | 1995-09-14 | 1997-03-19 | MERCK PATENT GmbH | Schuppenförmiges Aluminiumoxid und Perlglanzpigment, sowie deren Produktion |
WO2003027015A1 (de) | 2001-09-21 | 2003-04-03 | Merck Patent Gmbh | Neuartiges hybrid-sol zur herstellung abriebfester sio2-antireflexschichten |
US20060231851A1 (en) * | 2005-04-19 | 2006-10-19 | Gelcore, Llc | Red phosphor for LED based lighting |
CN101029231A (zh) * | 2007-01-11 | 2007-09-05 | 复旦大学 | 一种二价铕激活的碱土金属磷硅酸盐荧光粉及其制备方法 |
WO2007144060A1 (de) | 2006-06-12 | 2007-12-21 | Merck Patent Gmbh | Verfahren zur herstellung von granat-leuchtstoffen in einem pulsationsreaktor |
DE102006037730A1 (de) | 2006-08-11 | 2008-02-14 | Merck Patent Gmbh | LED-Konversionsleuchtstoffe in Form von keramischen Körpern |
DE102006054331A1 (de) | 2006-11-17 | 2008-05-21 | Merck Patent Gmbh | Leuchtstoffkörper basierend auf plättchenförmigen Substraten |
US20090114939A1 (en) * | 2006-04-27 | 2009-05-07 | Koninklijke Philips Electronics N.V. | Illumination system comprising a radiation source and a luminescent material |
CN101597493A (zh) * | 2009-07-10 | 2009-12-09 | 孙德春 | 一种碱土金属磷硅酸盐荧光粉及其制造方法和应用 |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6225505B1 (en) | 1998-06-01 | 2001-05-01 | Ihara Chemical Industry Co., Ltd | Trifluoro methylthiomethyl benzene derivatives and process for production same |
JP4892861B2 (ja) | 2005-04-27 | 2012-03-07 | 日亜化学工業株式会社 | 窒化物蛍光体及びそれを用いた発光装置 |
KR100682876B1 (ko) * | 2005-07-06 | 2007-02-15 | 삼성전기주식회사 | 실리코포스페이트계 형광체 및 이를 포함한 led |
DE102007039260A1 (de) * | 2007-08-20 | 2009-02-26 | Merck Patent Gmbh | LCD-Hintergrundbeleuchtung mit LED-Leuchtstoffen |
CN101284990B (zh) * | 2008-06-05 | 2012-11-21 | 复旦大学 | 一种碱土金属磷硅酸盐白色光发射荧光粉及其制造方法 |
-
2010
- 2010-09-14 DE DE102010045368A patent/DE102010045368A1/de not_active Withdrawn
-
2011
- 2011-08-16 EP EP11751816.7A patent/EP2616523B1/de not_active Not-in-force
- 2011-08-16 US US13/822,701 patent/US8987687B2/en not_active Expired - Fee Related
- 2011-08-16 CN CN201180044229.XA patent/CN103124779B/zh not_active Expired - Fee Related
- 2011-08-16 WO PCT/EP2011/004104 patent/WO2012034625A1/de active Application Filing
- 2011-08-16 KR KR1020137009334A patent/KR101849806B1/ko active IP Right Grant
- 2011-08-16 JP JP2013528533A patent/JP5819967B2/ja not_active Expired - Fee Related
- 2011-09-13 TW TW100132888A patent/TWI502052B/zh not_active IP Right Cessation
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4019884A (en) | 1976-01-22 | 1977-04-26 | Corning Glass Works | Method for providing porous broad-band antireflective surface layers on chemically-durable borosilicate glasses |
US4151443A (en) * | 1977-10-03 | 1979-04-24 | U.S. Philips Corporation | Luminescent materials and discharge lamp containing the same |
EP0763573A2 (de) | 1995-09-14 | 1997-03-19 | MERCK PATENT GmbH | Schuppenförmiges Aluminiumoxid und Perlglanzpigment, sowie deren Produktion |
WO2003027015A1 (de) | 2001-09-21 | 2003-04-03 | Merck Patent Gmbh | Neuartiges hybrid-sol zur herstellung abriebfester sio2-antireflexschichten |
US20060231851A1 (en) * | 2005-04-19 | 2006-10-19 | Gelcore, Llc | Red phosphor for LED based lighting |
US20090114939A1 (en) * | 2006-04-27 | 2009-05-07 | Koninklijke Philips Electronics N.V. | Illumination system comprising a radiation source and a luminescent material |
WO2007144060A1 (de) | 2006-06-12 | 2007-12-21 | Merck Patent Gmbh | Verfahren zur herstellung von granat-leuchtstoffen in einem pulsationsreaktor |
DE102006037730A1 (de) | 2006-08-11 | 2008-02-14 | Merck Patent Gmbh | LED-Konversionsleuchtstoffe in Form von keramischen Körpern |
DE102006054331A1 (de) | 2006-11-17 | 2008-05-21 | Merck Patent Gmbh | Leuchtstoffkörper basierend auf plättchenförmigen Substraten |
CN101029231A (zh) * | 2007-01-11 | 2007-09-05 | 复旦大学 | 一种二价铕激活的碱土金属磷硅酸盐荧光粉及其制备方法 |
CN101597493A (zh) * | 2009-07-10 | 2009-12-09 | 孙德春 | 一种碱土金属磷硅酸盐荧光粉及其制造方法和应用 |
Non-Patent Citations (11)
Title |
---|
ANNUAL REVIEW OF MATERIALS RESEARCH, vol. 36, 2006, pages 281 - 331 |
GERTHSEN: "Physik", 1995, SPRINGER VERLAG |
HOLLEMANN-WIBERG: "Lehrbuch der Anorganischen Chemie", WALTER DE GRUYTER VERLAG |
J. KRIEGSMANN: "Technische keramische Werkstoffe", 1998, DEUTSCHER WIRTSCHAFTSDIENST |
J. SOL. STATE CHEM., vol. 2, 1970, pages 27 - 30 |
JANDER: "Blasius Lehrbuch der analyt. u. präp. anorg. Chem.", 2002 |
JAPANESE JOURN. OF APPL. PHYS., vol. 44, no. 21, 2005, pages L649 - L651 |
K. UHEDA ET AL., ELECTROCHEM. SOLID STATE LETT., vol. 9, 2006, pages H22 |
LE TOQUIN, CHEETHAM, CHEM. PHYS. LETT., vol. 423, 2006, pages 352 |
LI ET AL., CHEM. MATER., vol. 15, 2005, pages 4492 |
XIE, SCI. TECHNOL. ADV. MATER., vol. 8, 2007, pages 588 - 600 |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104428395A (zh) * | 2012-07-13 | 2015-03-18 | 默克专利有限公司 | 制备无机发光材料的方法 |
US9580649B2 (en) | 2012-07-13 | 2017-02-28 | Merck Patent Gmbh | Process for production of phosphors |
CN103059849A (zh) * | 2013-01-23 | 2013-04-24 | 苏州大学 | 一种Eu2+激活的硅磷酸盐绿色荧光粉、制备方法及应用 |
EP2947697A1 (de) | 2013-12-23 | 2015-11-25 | Merck Patent GmbH | Antireflexionsschichten und fotovoltaische Vorrichtungen |
WO2018050526A1 (en) | 2016-09-13 | 2018-03-22 | Merck Patent Gmbh | Light luminescent particle |
WO2018096135A1 (en) | 2016-11-28 | 2018-05-31 | Merck Patent Gmbh | Composition comprising a nanosized light emitting material |
WO2018108767A1 (en) | 2016-12-15 | 2018-06-21 | Merck Patent Gmbh | Semiconducting light emitting nanoparticle |
WO2018146120A1 (en) | 2017-02-10 | 2018-08-16 | Merck Patent Gmbh | Semiconductor nanosized material |
WO2018224459A1 (en) | 2017-06-08 | 2018-12-13 | Merck Patent Gmbh | A composition comprising semiconducting light-emitting nanoparticles having thiol functional surface ligands |
WO2019002239A1 (en) | 2017-06-29 | 2019-01-03 | Merck Patent Gmbh | COMPOSITION COMPRISING A SEMICONDUCTOR ELECTROLUMINESCENT NANOPARTICLE |
WO2019105798A1 (en) | 2017-11-30 | 2019-06-06 | Merck Patent Gmbh | Composition comprising a semiconducting light emitting nanoparticle |
WO2019215059A1 (en) | 2018-05-09 | 2019-11-14 | Merck Patent Gmbh | Semiconducting nanoparticle |
WO2019224134A1 (en) | 2018-05-23 | 2019-11-28 | Merck Patent Gmbh | Semiconducting nanoparticle |
WO2019224182A1 (en) | 2018-05-24 | 2019-11-28 | Merck Patent Gmbh | Formulation comprising particles, a polymer and an organic solvent |
WO2020078843A1 (en) | 2018-10-15 | 2020-04-23 | Merck Patent Gmbh | Nanoparticle |
WO2020099284A1 (en) | 2018-11-14 | 2020-05-22 | Merck Patent Gmbh | Nanoparticle |
WO2020127188A1 (en) | 2018-12-20 | 2020-06-25 | Merck Patent Gmbh | Surface modified semiconducting light emitting nanoparticles and process for preparing such |
WO2020156969A1 (en) | 2019-01-29 | 2020-08-06 | Merck Patent Gmbh | Composition |
WO2020208127A1 (en) | 2019-04-12 | 2020-10-15 | Merck Patent Gmbh | Composition |
WO2020216813A1 (en) | 2019-04-26 | 2020-10-29 | Merck Patent Gmbh | Nanoparticle |
WO2021069432A1 (en) | 2019-10-07 | 2021-04-15 | Merck Patent Gmbh | Vertically aligned liquid-crystal element having at least one light converting layer which shifts the wavelength of incident light to longer values |
WO2024028426A1 (en) | 2022-08-05 | 2024-02-08 | Merck Patent Gmbh | Composition |
WO2024079230A1 (en) | 2022-10-14 | 2024-04-18 | Merck Patent Gmbh | Composition |
Also Published As
Publication number | Publication date |
---|---|
TW201215665A (en) | 2012-04-16 |
US8987687B2 (en) | 2015-03-24 |
DE102010045368A1 (de) | 2012-03-15 |
US20130168574A1 (en) | 2013-07-04 |
CN103124779A (zh) | 2013-05-29 |
CN103124779B (zh) | 2016-05-04 |
EP2616523A1 (de) | 2013-07-24 |
KR20130099097A (ko) | 2013-09-05 |
TWI502052B (zh) | 2015-10-01 |
EP2616523B1 (de) | 2014-09-24 |
JP5819967B2 (ja) | 2015-11-24 |
JP2013545694A (ja) | 2013-12-26 |
KR101849806B1 (ko) | 2018-04-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2616523B1 (de) | Silicophosphat-leuchtstoffe | |
EP2576725B1 (de) | Leuchtstoffe | |
EP2401342B1 (de) | Mit zirkonium und hafnium co-dotierte nitridosilikate | |
EP2129740B1 (de) | Verfahren zur herstellung von leuchtstoffen basierend auf orthosilikaten für pcleds | |
EP2596078B1 (de) | Aluminat-leuchtstoffe | |
EP2528991B1 (de) | Leuchtstoffe | |
EP2324096B1 (de) | Co-dotierte 1-1-2 nitride | |
EP2914688B1 (de) | Eu-aktivierte leuchtstoffe | |
DE102007016229A1 (de) | Verfahren zur Herstellung von Leuchtstoffen basierend auf Orthosilikaten für pcLEDs | |
EP2454340A1 (de) | Co-dotierte silicooxynitride | |
EP2625247B1 (de) | Mn-aktivierte leuchtstoffe | |
EP2596681B1 (de) | Carbodiimid-leuchtstoffe | |
EP2619283B1 (de) | Silicat-leuchtstoffe |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201180044229.X Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 11751816 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011751816 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2013528533 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 13822701 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20137009334 Country of ref document: KR Kind code of ref document: A |