CN106459752A - 无机发光材料 - Google Patents
无机发光材料 Download PDFInfo
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- CN106459752A CN106459752A CN201580022810.XA CN201580022810A CN106459752A CN 106459752 A CN106459752 A CN 106459752A CN 201580022810 A CN201580022810 A CN 201580022810A CN 106459752 A CN106459752 A CN 106459752A
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- 150000001875 compounds Chemical class 0.000 claims abstract description 79
- 239000000463 material Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000000126 substance Substances 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 30
- 230000007704 transition Effects 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 14
- 229910052788 barium Inorganic materials 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 229910052701 rubidium Inorganic materials 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 229910052712 strontium Inorganic materials 0.000 claims description 7
- -1 aluminium gallium nitrogen compound Chemical class 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910017464 nitrogen compound Inorganic materials 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 2
- 239000004973 liquid crystal related substance Substances 0.000 claims description 2
- 230000009257 reactivity Effects 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims 3
- 229910002601 GaN Inorganic materials 0.000 claims 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims 1
- 235000006408 oxalic acid Nutrition 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000011572 manganese Substances 0.000 description 56
- 239000011575 calcium Substances 0.000 description 37
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 26
- 239000011734 sodium Substances 0.000 description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 239000000843 powder Substances 0.000 description 10
- 230000003595 spectral effect Effects 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- 229910052681 coesite Inorganic materials 0.000 description 9
- 230000000875 corresponding effect Effects 0.000 description 9
- 229910052906 cristobalite Inorganic materials 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- 229910052682 stishovite Inorganic materials 0.000 description 9
- 229910052905 tridymite Inorganic materials 0.000 description 9
- 238000001354 calcination Methods 0.000 description 8
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 8
- 229910001634 calcium fluoride Inorganic materials 0.000 description 8
- 239000004570 mortar (masonry) Substances 0.000 description 8
- 230000005855 radiation Effects 0.000 description 8
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 8
- 229910017623 MgSi2 Inorganic materials 0.000 description 7
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 229910052573 porcelain Inorganic materials 0.000 description 7
- 229910052925 anhydrite Inorganic materials 0.000 description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 229910052882 wollastonite Inorganic materials 0.000 description 6
- 230000004907 flux Effects 0.000 description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 5
- 229910052909 inorganic silicate Inorganic materials 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 150000004767 nitrides Chemical class 0.000 description 5
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 229910052844 willemite Inorganic materials 0.000 description 5
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 5
- 229910000164 yttrium(III) phosphate Inorganic materials 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 229910052688 Gadolinium Inorganic materials 0.000 description 4
- 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 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229910003677 Sr5(PO4)3F Inorganic materials 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 229910052923 celestite Inorganic materials 0.000 description 4
- 229910052589 chlorapatite Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 229910000393 dicalcium diphosphate Inorganic materials 0.000 description 4
- 229910001650 dmitryivanovite Inorganic materials 0.000 description 4
- 238000000295 emission spectrum Methods 0.000 description 4
- 239000002223 garnet Substances 0.000 description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 4
- 229910001707 krotite Inorganic materials 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 150000003891 oxalate salts Chemical class 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 4
- 229910004829 CaWO4 Inorganic materials 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 229910004369 ThO2 Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- JUNWLZAGQLJVLR-UHFFFAOYSA-J calcium diphosphate Chemical compound [Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])([O-])=O JUNWLZAGQLJVLR-UHFFFAOYSA-J 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000000695 excitation spectrum Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011698 potassium fluoride Substances 0.000 description 3
- 238000006862 quantum yield reaction Methods 0.000 description 3
- 238000000985 reflectance spectrum Methods 0.000 description 3
- 239000011775 sodium fluoride Substances 0.000 description 3
- 235000013024 sodium fluoride Nutrition 0.000 description 3
- 229910001637 strontium fluoride Inorganic materials 0.000 description 3
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229910001551 Ca2B5O9Cl Inorganic materials 0.000 description 2
- 229910004647 CaMoO4 Inorganic materials 0.000 description 2
- 229910002971 CaTiO3 Inorganic materials 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910002244 LaAlO3 Inorganic materials 0.000 description 2
- 229910002420 LaOCl Inorganic materials 0.000 description 2
- 229910001477 LaPO4 Inorganic materials 0.000 description 2
- 229910018247 LaSiO3 Inorganic materials 0.000 description 2
- 229910010215 LiAl5O8 Inorganic materials 0.000 description 2
- 229910010092 LiAlO2 Inorganic materials 0.000 description 2
- 229910010881 LiInO2 Inorganic materials 0.000 description 2
- 229910002370 SrTiO3 Inorganic materials 0.000 description 2
- 239000005084 Strontium aluminate Substances 0.000 description 2
- 229910009372 YVO4 Inorganic materials 0.000 description 2
- 229910007486 ZnGa2O4 Inorganic materials 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 description 2
- 229910001632 barium fluoride Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 229910001640 calcium iodide Inorganic materials 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 229910052637 diopside Inorganic materials 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000005424 photoluminescence Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 2
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 2
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229910000018 strontium carbonate Inorganic materials 0.000 description 2
- 150000003438 strontium compounds Chemical class 0.000 description 2
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 229910016064 BaSi2 Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910014779 CaAl4 Inorganic materials 0.000 description 1
- 239000005132 Calcium sulfide based phosphorescent agent Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910020187 CeF3 Inorganic materials 0.000 description 1
- 229910005833 GeO4 Inorganic materials 0.000 description 1
- 229910005835 GeO6 Inorganic materials 0.000 description 1
- 101000694017 Homo sapiens Sodium channel protein type 5 subunit alpha Proteins 0.000 description 1
- 229910020440 K2SiF6 Inorganic materials 0.000 description 1
- 229910002226 La2O2 Inorganic materials 0.000 description 1
- 229910002248 LaBO3 Inorganic materials 0.000 description 1
- 229910002249 LaCl3 Inorganic materials 0.000 description 1
- 229910014323 Lanthanum(III) bromide Inorganic materials 0.000 description 1
- 229910007536 Li2Si2 Inorganic materials 0.000 description 1
- 229910010227 LiAlF4 Inorganic materials 0.000 description 1
- 229910010924 LiLaO2 Inorganic materials 0.000 description 1
- 229910003016 Lu2SiO5 Inorganic materials 0.000 description 1
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 1
- 229910020073 MgB2 Inorganic materials 0.000 description 1
- 229910017848 MgGa2O4 Inorganic materials 0.000 description 1
- 229910017672 MgWO4 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 241001025261 Neoraja caerulea Species 0.000 description 1
- 241000053208 Porcellio laevis Species 0.000 description 1
- 229910020489 SiO3 Inorganic materials 0.000 description 1
- 229910002412 SrMoO4 Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910003080 TiO4 Inorganic materials 0.000 description 1
- 229910007709 ZnTe Inorganic materials 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001622 calcium bromide Inorganic materials 0.000 description 1
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QZVSYHUREAVHQG-UHFFFAOYSA-N diberyllium;silicate Chemical compound [Be+2].[Be+2].[O-][Si]([O-])([O-])[O-] QZVSYHUREAVHQG-UHFFFAOYSA-N 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052634 enstatite Inorganic materials 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 229910052587 fluorapatite Inorganic materials 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052839 forsterite Inorganic materials 0.000 description 1
- 229910001676 gahnite Inorganic materials 0.000 description 1
- 239000007789 gas Substances 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
- 150000002291 germanium compounds Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- XKUYOJZZLGFZTC-UHFFFAOYSA-K lanthanum(iii) bromide Chemical compound Br[La](Br)Br XKUYOJZZLGFZTC-UHFFFAOYSA-K 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- HDJUVFZHZGPHCQ-UHFFFAOYSA-L manganese(2+);oxalate;dihydrate Chemical compound O.O.[Mn+2].[O-]C(=O)C([O-])=O HDJUVFZHZGPHCQ-UHFFFAOYSA-L 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052605 nesosilicate Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000004762 orthosilicates Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 229910052842 phenakite Inorganic materials 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 229910001774 tsavorite Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
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Abstract
本发明涉及式(I)化合物，(A2‑2nBn)x(Ge1‑ mMm)yO(x+2y):Mn4+，其中参数A、B、M、m、n、x和y具有根据权利要求1的含义之一。此外，本发明涉及一种制备式(I)化合物的方法，所述化合物作为转换无机发光材料的用途和包含至少一种式(I)化合物的发射转换材料。本发明进一步涉及包含至少一种本发明的式(I)化合物的发光装置。
Description
本发明涉及式I化合物，
(A2-2nBn)x(Ge1-mMm)yO(x+2y)：Mn4+ I
其中参数A、B、M、m、n、x和y具有根据权利要求1的含义之一。此外，本发明涉及制备该式I化合物的方法、这些化合物作为转换无机发光材料的用途和包含至少一种该式I化合物的发射转换材料。本发明进一步涉及包含至少一种本发明的式I化合物的发光装置。
可在蓝光和/或UV光谱区中激发的无机荧光粉末作为用于无机发光材料转换LED(简称为pc-LED)的转换无机发光材料非常重要。同时，已知许多转换无机发光材料系统，如碱土金属原硅酸盐、硫代镓酸盐、石榴石、氮化物和氮氧化物，其中各自被Ce3+或Eu2+掺杂。除发射黄光或绿光的石榴石或原硅酸盐之外，基于发射蓝光或UV-A的(In，Ga)N LED实现色温＜4000K的暖白光源需要发射波长大于600nm的发射红光的无机发光材料，其在相应一次辐射波长(370-480nm)处足够强地发射。
目前市售的大部分冷白光LED包含经色度优化的通式(Y，Gd，Lu，Tb)3(Al，Ga，Sc)5O12：Ce的Ce3+掺杂的石榴石无机发光材料。
暖白光LED另外包含第二发射红光的无机发光材料，其为Eu2+掺杂的原硅酸盐无机发光材料或Eu2+掺杂的(氧)氮化物无机发光材料。
除化学不稳定性(尤其对湿气)之外，用于红色光谱区中的包含发射宽带的Ce3+掺杂的石榴石无机发光材料和发射宽带的Eu2+掺杂原硅酸盐无机发光材料或(氧)氮化物无机发光材料的LED光源的主要缺点还有NIR区中的显著辐射再吸收和发射，其使得暖白光LED的流明产率显著低于(大约1/2或以下)相应冷白光LED的流明产率。
与此相关的再吸收意指无机发光材料中产生的一定比例荧光无法离开无机发光材料，因为其在界面完全反射至光更淡环境且经由波传导过程在无机发光材料中迁移且最终损耗。
近红外(NIR)表示在更长波长方向上与可见光相邻的电磁波谱区。该红外光区通常由701nm延伸至3μm。
迄今为止使用的无机发光材料(Ca,Sr)S:Eu、(Ca,Sr)AlSiN3:Eu和(Ca,Sr,Ba)2Si5N8:Eu均基于活化剂Eu2+，其突出特征为宽吸收光谱以及宽发射带。这些Eu2+活化的材料的主要缺点为它们对光降解的相对高敏感度，因为二价Eu2+倾向于光致电离，尤其在具有相对小带隙的主体材料中。
另一缺点为Eu2+发射带的极高半值宽度，若色点位于深红光谱区中，则其由中度流明当量(<200lm/W)而明显。该观察结果尤其适用于无机发光材料(Ca,Sr)S:Eu2+和(Ca,Sr)AlSiN3:Eu2+。
鉴于上述问题，目前正寻求发射最大值在615nm至700nm之间的用于LED的红光窄带发射体。这里优选发射带在630nm至680nm之间且半峰全宽为至多50nm的窄带发射体。
与此相关，例如US 7,846,350中提出了化合物SrGe4O9:Mn4+。
Mn4+活化的无机发光材料的优点在于基础光跃迁[Ar]3d3-[Ar]3d3，其因此为组态内跃迁。针对Mn4+的Tanabe-Sugano图显示此跃迁一方面位于红光谱区中，另一方面是光学窄的，且因此有助于红无机发光材料具有高颜色饱和度且同时具有可接受的流明当量。
Tanabe-Sugano图为通常来自最低态的能差E相对于系统的所有电子态的晶体场分裂能(△)绘制的图，两个量均标准化至Racah参数。多电子系统中出现的静电排斥可通过Slater电子相互作用积分Fk的三种线性组合(库仑积分、交换积分、排斥积分)来完全描述。这些线性组合的缩写A、B和C称作Racah参数。
与给定△的垂直线相交的曲线数目提供可能的跃迁数和因此经预期的吸收特征的数目。因此，Tanabe-Sugano图为能够解读化合物的吸收光谱的相关图。
因此，本发明目的之一是提供适合的发射红光的无机发光材料，其应出于上述原因经Mn4+活化，应在蓝光或近UV波长区域内可有效地激发且应适于作为用于相应固态光源如(In，Ga)N LED或OLED的辐射转换材料。
出人意料地，发明人已发现式I化合物符合上述要求：
(A2-2nBn)x(Ge1-mMm)yO(x+2y)：Mn4+ I
其中
A对应于选自Li、Na、K和Rb组成的组的至少一种元素，
B对应于(C1-uDu)，
C对应于选自Ca、Ba和Sr组成的组的至少一种元素，
D对应于选自Ca和Ba组成的组的至少一种元素，
M对应于选自Ti、Zr、Hf、Si和Sn组成的组的至少一种元素，
0≤n≤1，优选0或1，
0＜u≤1，优选0.2＜u≤1，特别优选0.5＜u≤1，
0.5≤x≤2，
0≤m＜1且
1≤y≤9。
本发明的化合物可通常在近UV或蓝色光谱区中，优选在约280nm至470nm，尤其优选在约300nm至400nm激发，且通常在约600nm至700nm，优选约620nm至680nm的红色光谱区中具有线发射，其中主发射峰的半峰全宽(FWHM)为至多50nm，优选至多40nm。
半峰全宽(FWHM)为常用于描述峰或函数宽度的参数。其在二维坐标系统(x，y)中由曲线上具有相同y值的两点之间的间距(Δx)限定，在该y值处所述函数实现其最大值的一半(ymax/2)。
在本申请的上下文中，蓝光表示发射最大值在400nm至459nm之间的光，青光表示发射最大值在460nm至505nm之间的光，绿光表示发射最大值在506nm至545nm之间的光，黄光表示发射最大值在546nm至565nm之间的光，橙光表示发射最大值在566nm至600nm之间的光，且红光表示发射最大值在601nm至700nm之间的光。本发明的化合物优选为发射红光的转换无机发光材料。
此外，本发明化合物的特征在于大于80％，优选大于90％，尤其优选大于95％的高光致发光量子产率。
光致发光量子产率(也称作量子产率或量子效率)描述化合物发射与吸收的光子数之间的比率。
另外，本发明的化合物具有高流明当量值(≥250lm/W)，且其另一特征为极好热稳定性和化学稳定性。此外，本发明的化合物极适用于白光LED、按需颜色(COD)应用、TV背光LED和电灯(如荧光灯)，且适用于提高太阳能电池的效率。
在一个优选实施方案中，式I化合物选自以下子式的化合物：
((Sr1-uBau))x(Ge1-mMm)yO(x+2y)：Mn4+ I’
((Sr1-uCau))x(Ge1-mMm)yO(x+2y)：Mn4+ I“
其中参数M、n、u、x、m和y具有对式I所示含义之一。
与已知化合物SrGe4O9：Mn4+(参见US 7,846,350)相比，本发明化合物I′的优点通过在根据本发明制备期间混合例如钡源来提供，其中共晶形成且因此出现熔点的降低，这简化了合成且确保更好的结晶度。
在本发明的另一优选实施方案中，n等于0。
式I化合物优选选自式Ia化合物组成的组，
(A2)x(Ge1-m-zMmMnz)yO(x+2y) Ia
其中A、M、x、y和m具有对式I所示含义之一，且0＜z≤0.01＊y。
优选式I和其子式的化合物，其中0≤m＜0.8，进一步优选其中0≤m＜0.5，此外还优选其中0≤m＜0.3。
更优选式I和其子式的化合物，其中x等于0.5、0.75、1、1.25、1.5、1.75或2，尤其优选其中x等于1或2，尤其其中x等于1。
还优选式I和其子式的化合物，其中y对应于1≤y≤9范围内的整数，即1、2、3、4、5、6、7、8或9，尤其优选其中y等于4。
在另一优选实施方案中，式I化合物选自式Ia-1至Ia-4的化合物组成的组：
A2Ge1-zMnzM3O9 Ia-1
A2Ge2-zMnzM2O9 Ia-2
A2Ge3-zMnzMO9 Ia-3
A2Ge4-zMnzO9 Ia-4
其中M、z和A具有对式Ia所示含义之一。
取决于组合物，尤其是与参数A、M和m的变化有关，红色光谱区中的发射可特定地在600nm至700nm范围内变化。
在另一实施方案中，本发明化合物中的锗部分地由硅替代，其中M等于Si且m＞0。尤其优选式I和其子式的化合物，其中M等于Si，m＞0且同时y等于4，x等于1且0.001≤z≤0.004。
在同样优选的实施方案中，式I化合物选自其中m等于0，同时y等于4，x等于1且0.001≤z≤0.004的化合物。
在一个实施方案中，A表示选自Li、Na、K和Rb组成的组的仅一种元素。然而，同样还优选式I和其子式的化合物，其中A对应于这些元素的混合物，即选自Li、Na、K和Rb组成的组的至少两种元素。
本发明的化合物尤其优选选自以下子式：
A2Ge4-zMnzO9，
进一步优选
Li2Ge4-zMnzO9，
K2Ge4-zMnzO9，
Na2Ge4-zMnzO9，
Rb2Ge4-zMnzO9，
A2SiGe3-zMnzO9，
进一步优选
Li2SiGe3-zMnzO9，
K2SiGe3-zMnzO9，
Na2SiGe3-zMnzO9，
Rb2SiGe3-zMnzO9，
A2Si2Ge2-zMnzO9，
进一步优选
Li2Si2Ge2-zMnzO9，
K2Si2Ge2-zMnzO9，
Na2Si2Ge2-zMnzO9，
Rb2Si2Ge2-zMnzO9，以及
A2Si3Ge1-zMnzO9，
进一步优选
Li2Si3Ge1-zMnzO9，
K2Si3Ge1-zMnzO9，
Na2Si3Ge1-zMnzO9，
Rb2Si3Ge1-zMnzO9，
其中z具有对式Ia所示含义之一，尤其是优选z＝0.01*y。
同样优选其中A表示选自Li、Na、K和Rb组成的组的至少两种元素的上述化合物，如Na1.8Li0.2Ge0.999Mn0.001Si3O9。
本发明的化合物可呈相混合物形式或者纯相形式。在一个优选的实施方案中，本发明的化合物呈纯相形式。
X射线衍射图使得研究结晶粉末的相纯度成为可能，即样品是仅由一种结晶化合物(纯相)还是由多种化合物(多相)组成。在纯相粉末中，可观察到所有反射且可归属于化合物。
本发明化合物的粒度通常在50μm至1μm之间，优选30μm至3μm之间，尤其优选20μm至5μm之间。
本发明进一步涉及制备本发明化合物的方法，其特征在于在步骤a)中混合适合的起始材料，其选自相应氧化物、碳酸盐、草酸盐或相应反应性形式组成的组)，和在步骤b)中热处理混合物。
本发明的方法优选特征在于以下方法步骤：
(a)制备包含至少一种锰源；至少一种锂、钠、钾、铷、钙、钡和/或锶源；至少一种锰源；至少一种锗源；和任选的钛、锆、铪、硅和/或锡源的混合物；
(b)在氧化条件下煅烧所述混合物。
步骤(a)中所用锰源可为任何可想到的用于制备本发明化合物的锰化合物。所用锰源优选为碳酸盐、草酸盐和/或氧化物，尤其草酸锰二水合物(MnC2O4*2H2O)。
步骤(a)中所用锗源可为任何可想到的用于制备本发明化合物的锗化合物。所用锗源优选为氧化物，尤其氧化锗(GeO2)。
步骤(a)中所用锂、钠、钾、铷、钙、钡和/或锶源可为任何可想到的用于制备本发明化合物的锂、钠、钾、铷、钙、钡和/或锶化合物。本发明方法中所用锂、钠、钾、铷、钙、钡和/或锶化合物优选为相应碳酸盐或氧化物，尤其碳酸锂(Li2CO3)、碳酸钠(Na2CO3)、碳酸钾(K2CO3)、碳酸铷(Rb2CO3)、碳酸钙(CaCO3)、碳酸钡(BaCO3)和/或碳酸锶(SrCO3)。
步骤(a)中所用钛、锆、铪、硅和/或锡源可为任何可想到的用于制备本发明化合物的的钛、锆、铪、硅和/或锡化合物。本发明方法中所用钛、锆、铪、硅和/或锡源优选为相应氮化物和/或氧化物。
这些化合物优选以使得原子数目对应于上述化学式的产物中所需比率的相互比率使用。特别地，这里使用化学计量比。
步骤(a)中的起始化合物优选以粉末形式使用，并且例如借助研钵彼此加工，以得到均质混合物。为此，起始化合物优选可悬浮于熟练技术人员已知的惰性有机溶剂，例如丙酮中。在该情况下，煅烧之前干燥混合物。
步骤(b)中的煅烧在氧化条件下进行。氧化条件意指任何可想到的氧化氛围，如空气或其他含氧氛围。
所用助熔剂可任选为选自下组的至少一种物质：卤化铵，优选氯化铵，碱金属氟化物如氟化钠、氟化钾或氟化锂，碱土金属氟化物如氟化钙、氟化锶或氟化钡，碳酸盐优选碳酸氢铵，或各种醇化物和/或草酸盐。
煅烧优选在700℃至1200℃，尤其优选800℃至1000℃，尤其是850℃至950℃范围内的温度下进行。此处煅烧持续时间优选为2h至14h，更优选为4h至12h，尤其是6h至10h。
煅烧优选通过将所获得混合物引入高温烘箱中例如氮化硼容器中进行。高温烘箱为例如含有钼箔盘的管状烘箱。
煅烧之后，所获得化合物可任选经均质化，其中相应研磨方法可在适合溶剂(例如异丙醇)中湿式进行或干式进行。
煅烧产物可任选在上述条件下再煅烧，且任选添加选自下组的适合助熔剂：卤化铵，优选氯化铵，碱金属氟化物如氟化钠、氟化钾或氟化锂，碱土金属氟化物如氟化钙、氟化锶或氟化钡，碳酸盐，优选碳酸氢铵，或各种醇化物和/或草酸盐。
在另一实施方案中，本发明的化合物可经涂布。本领域技术人员根据已有技术已知的用于无机发光材料的所有涂布方法适用于此目的。特别地，适于涂布的材料为金属氧化物和金属氮化物，尤其是碱土金属氧化物如Al2O3和碱土金属氮化物如AlN以及SiO2。此处涂布可例如通过流化床方法进行。其他适合的涂布方法由JP 04-304290、WO 91/10715、WO99/27033、US 2007/0298250、WO 2009/065480和WO 2010/075908已知。还可以涂覆有机涂层作为上述涂覆无机涂层的替代和/或额外涂层。涂层可对化合物的稳定性和分散性具有有利作用。
本发明进一步涉及本发明化合物作为无机发光材料，尤其作为转换无机发光材料的用途。
本申请范围内的术语“转换无机发光材料”意指吸收电磁谱一定波长范围内，优选蓝光或UV光谱区内的辐射，且在电磁谱另一波长范围内，优选红色或橙色光谱区内，尤其红色光谱区内发射可见光的材料。术语“辐射引发的发射效率”也应理解与此相关地理解，即转换无机发光材料吸收一定波长范围内的辐射且以一定效率发射另一波长范围内的辐射。术语“发射波长的位移”意指转换无机发光材料在不同波长处发光，即与另一或类似转换无机发光材料相比，位移至更短或更长波长。因此发射最大值位移。
本发明还涉及发射转换材料，其包含一或多种根据本发明的上述化学式之一的化合物。发射转换材料可由本发明化合物之一构成，其在此情况下等同于如上所定义的术语“转换无机发光材料”。
除本发明化合物之外，本发明的发射转换材料还可包含其他转换无机发光材料。在此情况下，本发明的发射转换材料包含至少两种转换无机发光材料的混合物，其中这些转换无机发光材料之一为本发明的化合物。尤其优选至少两种转换无机发光材料为发射彼此互补的不同波长光的无机发光材料。由于本发明的化合物为发射红光的无机发光材料，因此，其优选与发射绿光或发射黄光的无机发光材料或也与发射青光或发射蓝光的无机发光材料组合使用。或者，本发明的发射红光的转换无机发光材料也可与发射蓝光和发射绿光的转换无机发光材料组合使用。或者，本发明的发射红光的转换无机发光材料也可与发射绿光的转换无机发光材料组合使用。因此，可优选的是本发明的转换无机发光材料与一或多种其他转换无机发光材料组合用于本发明的发射转换材料中，随后优选一起发射白光。
一般而言，任何可能的转换无机发光材料可用作可与本发明化合物一起使用的其他转换无机发光材料。以下是适合的：Ba2SiO4:Eu2+、BaSi2O5:Pb2+、BaxSr1-xF2:Eu2+、BaSrMgSi2O7:Eu2+、BaTiP2O7、(Ba,Ti)2P2O7:Ti、Ba3WO6:U、BaY2F8:Er3+,Yb+、Be2SiO4:Mn2+、Bi4Ge3O12、CaAl2O4:Ce3+、CaLa4O7:Ce3+、CaAl2O4:Eu2+、CaAl2O4:Mn2+、CaAl4O7:Pb2+,Mn2+、CaAl2O4:Tb3+、Ca3Al2Si3O12:Ce3+、Ca3Al2Si3Oi2:Ce3+、Ca3Al2Si3O2:Eu2+、Ca2B5O9Br:Eu2+、Ca2B5O9Cl:Eu2+、Ca2B5O9Cl:Pb2+、CaB2O4:Mn2+、Ca2B2O5:Mn2+、CaB2O4:Pb2+、CaB2P2O9:Eu2+、Ca5B2SiO10:Eu3+、Ca0.5Ba0.5Al12O19:Ce3+,Mn2+、Ca2Ba3(PO4)3Cl:Eu2+、SiO2中的CaBr2:Eu2+、SiO2中的CaCl2:Eu2+、SiO2中的CaCl2:Eu2+,Mn2+、CaF2:Ce3+、CaF2:Ce3+,Mn2+、CaF2:Ce3+,Tb3+、CaF2:Eu2+、CaF2:Mn2+、CaF2:U、CaGa2O4:Mn2+、CaGa4O7:Mn2+、CaGa2S4:Ce3+、CaGa2S4:Eu2+、CaGa2S4:Mn2 +、CaGa2S4:Pb2+、CaGeO3:Mn2+、SiO2中的CaI2:Eu2+、SiO2中的CaI2:Eu2+,Mn2+、CaLaBO4:Eu3+、CaLaB3O7:Ce3+,Mn2+、Ca2La2BO6.5:Pb2+、Ca2MgSi2O7、Ca2MgSi2O7:Ce3+、CaMgSi2O6:Eu2+、Ca3MgSi2O8:Eu2+、Ca2MgSi2O7:Eu2+、CaMgSi2O6:Eu2+,Mn2+、Ca2MgSi2O7:Eu2+,Mn2+、CaMoO4、CaMoO4:Eu3+、CaO:Bi3+、CaO:Cd2+、CaO:Cu+、CaO:Eu3+、CaO:Eu3+,Na+、CaO:Mn2+、CaO:Pb2+、CaO:Sb3+、CaO:Sm3+、CaO:Tb3+、CaO:Tl、CaO:Zn2+、Ca2P2O7:Ce3+、α-Ca3(PO4)2:Ce3+、β-Ca3(PO4)2:Ce3 +、Ca5(PO4)3Cl:Eu2+、Ca5(PO4)3Cl:Mn2+、Ca5(PO4)3Cl:Sb3+、Ca5(PO4)3Cl:Sn2+、β-Ca3(PO4)2:Eu2 +,Mn2+、Ca5(PO4)3F:Mn2+、Cas(PO4)3F:Sb3+、Cas(PO4)3F:Sn2+、α-Ca3(PO4)2:Eu2+、β-Ca3(PO4)2:Eu2+、Ca2P2O7:Eu2+、Ca2P2O7:Eu2+,Mn2+、CaP2O6:Mn2+、α-Ca3(PO4)2:Pb2+、α-Ca3(PO4)2:Sn2+、β-Ca3(PO4)2:Sn2+、β-Ca2P2O7:Sn,Mn、α-Ca3(PO4)2:Tr、CaS:Bi3+、CaS:Bi3+,Na、CaS:Ce3+、CaS:Eu2+、CaS:Cu+,Na+、CaS:La3+、CaS:Mn2+、CaSO4:Bi、CaSO4:Ce3+、CaSO4:Ce3+,Mn2+、CaSO4:Eu2+、CaSO4:Eu2+,Mn2+、CaSO4:Pb2+、CaS:Pb2+、CaS:Pb2+,Cl、CaS:Pb2+,Mn2+、CaS:Pr3+,Pb2+,Cl、CaS:Sb3+、CaS:Sb3+,Na、CaS:Sm3+、CaS:Sn2+、CaS:Sn2+,F、CaS:Tb3+、CaS:Tb3+,Cl、CaS:Y3+、CaS:Yb2+、CaS:Yb2+,Cl、CaSiO3:Ce3+、Ca3SiO4Cl2:Eu2+、Ca3SiO4Cl2:Pb2+、CaSiO3:Eu2+、CaSiO3:Mn2+,Pb、CaSiO3:Pb2+、CaSiO3:Pb2+,Mn2+、CaSiO3:Ti4+、CaSr2(PO4)2:Bi3+、β-(Ca,Sr)3(PO4)2:Sn2+Mn2+、CaTi0.9Al0.1O3:Bi3+、CaTiO3:Eu3+、CaTiO3:Pr3+、Ca5(VO4)3Cl、CaWO4、CaWO4:Pb2+、CaWO4:W、Ca3WO6:U、CaYAlO4:Eu3+、CaYBO4:Bi3+、CaYBO4:Eu3+、CaYB0.8O3.7:Eu3+、CaY2ZrO6:Eu3+、(Ca,Zn,Mg)3(PO4)2:Sn、CeF3、(Ce,Mg)BaAl11O18:Ce、(Ce,Mg)SrAl11O18:Ce、CeMgAl11O19:Ce:Tb、Cd2B6O11:Mn2+、CdS:Ag+,Cr、CdS:In、CdS:In、CdS:In,Te、CdS:Te、CdWO4、CsF、Csl、CsI:Na+、CsI:Tl、(ErCl3)0.25(BaCl2)0.75、GaN:Zn、Gd3Ga5O12:Cr3+、Gd3Ga5O12:Cr,Ce、GdNbO4:Bi3+、Gd2O2S:Eu3+、Gd2O2Pr3+、Gd2O2S:Pr,Ce,F、Gd2O2S:Tb3+、Gd2SiO5:Ce3+、KAl11O17:Tl+、KGa11O17:Mn2+、K2La2Ti3O10:Eu、KMgF3:Eu2+、KMgF3:Mn2+、K2SiF6:Mn4+、LaAl3B4O12:Eu3+、LaAlB2O6:Eu3+、LaAlO3:Eu3+、LaAlO3:Sm3+、LaAsO4:Eu3+、LaBr3:Ce3+、LaBO3:Eu3+、(La,Ce,Tb)PO4:Ce:Tb、LaCl3:Ce3+、La2O3:Bi3+、LaOBr:Tb3+、LaOBr:Tm3+、LaOCl:Bi3+、LaOCl:Eu3+、LaOF:Eu3+、La2O3:Eu3+、La2O3:Pr3+、La2O2S:Tb3+、LaPO4:Ce3+、LaPO4:Eu3+、LaSiO3Cl:Ce3+、LaSiO3Cl:Ce3+,Tb3+、LaVO4:Eu3+、La2W3O12:Eu3+、LiAlF4:Mn2+、LiAl5O8:Fe3+、LiAlO2:Fe3+、LiAlO2:Mn2+、LiAl5O8:Mn2 +、Li2CaP2O7:Ce3+,Mn2+、LiCeBa4Si4O14:Mn2+、LiCeSrBa3Si4O14:Mn2+、LiInO2:Eu3+、LiInO2:Sm3+、LiLaO2:Eu3+、LuAlO3:Ce3+、(Lu,Gd)2SiO5:Ce3+、Lu2SiO5:Ce3+、Lu2Si2O7:Ce3+、LuTaO4:Nb5+、Lu1-xYxAlO3:Ce3+、MgAl2O4:Mn2+、MgSrAl10O17:Ce、MgB2O4:Mn2+、MgBa2(PO4)2:Sn2+、MgBa2(PO4)2:U、MgBaP2O7:Eu2+、MgBaP2O7:Eu2+,Mn2+、MgBa3Si2O8:Eu2+、MgBa(SO4)2:Eu2+、Mg3Ca3(PO4)4:Eu2+、MgCaP2O7:Mn2+、Mg2Ca(SO4)3:Eu2+、Mg2Ca(SO4)3:Eu2+,Mn2、MgCeAlnO19:Tb3+、Mg4(F)GeO6:Mn2+、Mg4(F)(Ge,Sn)O6:Mn2+、MgF2:Mn2+、MgGa2O4:Mn2+、Mg8Ge2O11F2:Mn4+、MgS:Eu2+、MgSiO3:Mn2+、Mg2SiO4:Mn2+、Mg3SiO3F4:Ti4+、MgSO4:Eu2+、MgSO4:Pb2+、MgSrBa2Si2O7:Eu2+、MgSrP2O7:Eu2+、MgSr5(PO4)4:Sn2+、MgSr3Si2O8:Eu2+,Mn2+、Mg2Sr(SO4)3:Eu2+、Mg2TiO4:Mn4+、MgWO4、MgYBO4:Eu3 +、Na3Ce(PO4)2:Tb3+、NaI:Tl、Na1.23K0.42Eu0.12TiSi4O11:Eu3+、Na1.23K0.42Eu0.12TiSi5O13·xH2O:Eu3+、Na1.29K0.46Er0.08TiSi4O11:Eu3+、Na2Mg3Al2Si2O10:Tb、Na(Mg2-xMnx)LiSi4O10F2:Mn、NaYF4:Er3+,Yb3+、NaYO2:Eu3+、P46(70％)+P47(30％)、SrAl12O19:Ce3+、Mn2+、SrAl2O4:Eu2+、SrAl4O7:Eu3+、SrAl12O19:Eu2+、SrAl2S4:Eu2+、Sr2B5O9Cl:Eu2+、SrB4O7:Eu2+(F,Cl,Br)、SrB4O7:Pb2+、SrB4O7:Pb2+、Mn2+、SrB8O13:Sm2+、SrxBayClzAl2O4-z/2:Mn2+,Ce3+、SrBaSiO4:Eu2+、SiO2中的Sr(Cl,Br,I)2:Eu2+、SiO2中的SrCl2:Eu2+、Sr5Cl(PO4)3:Eu、SrwFxB4O6.5:Eu2+、SrwFxByOz:Eu2+,Sm2 +、SrF2:Eu2+、SrGa12O19:Mn2+、SrGa2S4:Ce3+、SrGa2S4:Eu2+、SrGa2S4:Pb2+、SrIn2O4:Pr3+,Al3+、(Sr,Mg)3(PO4)2:Sn、SrMgSi2O6:Eu2+、Sr2MgSi2O7:Eu2+、Sr3MgSi2O8:Eu2+、SrMoO4:U、SrO·3B2O3:Eu2+,Cl、β-SrO·3B2O3:Pb2+、β-SrO·3B2O3:Pb2+,Mn2+、α-SrO·3B2O3:Sm2+、Sr6P5BO20:Eu、Sr5(PO4)3Cl:Eu2+、Sr5(PO4)3Cl:Eu2+,Pr3+、Sr5(PO4)3Cl:Mn2+、Sr5(PO4)3Cl:Sb3+、Sr2P2O7:Eu2+、β-Sr3(PO4)2:Eu2+、Sr5(PO4)3F:Mn2+、Sr5(PO4)3F:Sb3+、Sr5(PO4)3F:Sb3+,Mn2+、Sr5(PO4)3F:Sn2+、Sr2P2O7:Sn2+、β-Sr3(PO4)2:Sn2+、β-Sr3(PO4)2:Sn2+,Mn2+(Al)、SrS:Ce3+、SrS:Eu2+、SrS:Mn2+、SrS:Cu+,Na、SrSO4:Bi、SrSO4:Ce3+、SrSO4:Eu2+、SrSO4:Eu2+,Mn2+、Sr5Si4O10Cl6:Eu2+、Sr2SiO4:Eu2+、SrTiO3:Pr3+、SrTiO3:Pr3+,Al3+、Sr3WO6:U、SrY2O3:Eu3+、ThO2:Eu3+、ThO2:Pr3+、ThO2:Tb3+、YAl3B4O12:Bi3+、YAl3B4O12:Ce3+、YAl3B4O12:Ce3+,Mn、YAl3B4O12:Ce3+,Tb3+、YAl3B4O12:Eu3+、YAl3B4O12:Eu3+,Cr3+、YAl3B4O12:Th4+,Ce3+,Mn2+、YAlO3:Ce3+、Y3Al5O12:Ce3+、Y3Al5O12:Cr3+、YAlO3:Eu3+、Y3Al5O12:Eu3r、Y4Al2O9:Eu3+、Y3Al5O12:Mn4+、YAlO3:Sm3+、YAlO3:Tb3+、Y3Al5O12:Tb3+、YAsO4:Eu3+、YBO3:Ce3+、YBO3:Eu3+、YF3:Er3+,Yb3+、YF3:Mn2+、YF3:Mn2+,Th4+、YF3:Tm3+,Yb3+、(Y,Gd)BO3:Eu、(Y,Gd)BO3:Tb、(Y,Gd)2O3:Eu3+、Y1.34Gd0.60O3(Eu,Pr)、Y2O3:Bi3+、YOBr:Eu3+、Y2O3:Ce、Y2O3:Er3+、Y2O3:Eu3+(YOE)、Y2O3:Ce3+,Tb3+、YOCl:Ce3+、YOCl:Eu3+、YOF:Eu3+、YOF:Tb3+、Y2O3:Ho3+、Y2O2S:Eu3+、Y2O2S:Pr3+、Y2O2S:Tb3+、Y2O3:Tb3+、YPO4:Ce3+、YPO4:Ce3+,Tb3+、YPO4:Eu3 +、YPO4:Mn2+,Th4+、YPO4:V5+、Y(P,V)O4:Eu、Y2SiO5:Ce3+、YTaO4、YTaO4:Nb5+、YVO4:Dy3+、YVO4:Eu3 +、ZnAl2O4:Mn2+、ZnB2O4:Mn2+、ZnBa2S3:Mn2+、(Zn,Be)2SiO4:Mn2+、Zn0.4Cd0.6S:Ag、Zn0.6Cd0.4S:Ag、(Zn,Cd)S:Ag,Cl、(Zn,Cd)S:Cu、ZnF2:Mn2+、ZnGa2O4、ZnGa2O4:Mn2+、ZnGa2S4:Mn2+、Zn2GeO4:Mn2+、(Zn,Mg)F2:Mn2+、ZnMg2(PO4)2:Mn2+、(Zn,Mg)3(PO4)2:Mn2+、ZnO:Al3+,Ga3+、ZnO:Bi3+、ZnO:Ga3+、ZnO:Ga、ZnO-CdO:Ga、ZnO:S、ZnO:Se、ZnO:Zn、ZnS:Ag+,Cl-、ZnS:Ag,Cu,Cl、ZnS:Ag,Ni、ZnS:Au,In、ZnS-CdS(25-75)、ZnS-CdS(50-50)、ZnS-CdS(75-25)、ZnS-CdS:Ag,Br,Ni、ZnS-CdS:Ag+,Cl、ZnS-CdS:Cu,Br、ZnS-CdS:Cu,I、ZnS:Cl-、ZnS:Eu2+、ZnS:Cu、ZnS:Cu+,Al3+、ZnS:Cu+,Cl-、ZnS:Cu,Sn、ZnS:Eu2+、ZnS:Mn2+、ZnS:Mn,Cu、ZnS:Mn2+,Te2+、ZnS:P、ZnS:P3-,Cl-、ZnS:Pb2+、ZnS:Pb2+,Cl-、ZnS:Pb,Cu、Zn3(PO4)2:Mn2+、Zn2SiO4:Mn2+、Zn2SiO4:Mn2+,As5+、Zn2SiO4:Mn,Sb2O2、Zn2SiO4:Mn2+,P、Zn2SiO4:Ti4+、ZnS:Sn2+、ZnS:Sn,Ag、ZnS:Sn2+,Li+、ZnS:Te,Mn、ZnS-ZnTe:Mn2+、ZnSe:Cu+,Cl或ZnWO4。
即使少量使用，本发明的化合物也产生良好LED质量。此处经由常规参数描述LED质量，如显色指数、相关色温、流明当量或绝对流明或CIEx和CIE y坐标中的色点。
显色指数或CRI为熟练技术人员熟悉的无量纲照明量，其比较的是人工光源的颜色再现忠实性与日光或灯丝光源的颜色再现忠实性(后两者的CRI为100)。
CCT或相关色温为熟练技术人员熟悉的照明量，其单位为开尔文。数值越高，对观测者呈现的来自人工辐射源的白光越冷。CCT遵循黑体辐射器的概念，其色温描述CIE图中所谓的普朗克曲线。
流明当量为熟练技术人员熟悉的照明量，其单位为lm/W，该单位描述在一定辐射量测辐射功率(单位为瓦特)下光度光通量在光源流明中的量值。流明当量越高，光源越有效。
流明为熟练技术人员熟悉的光度照明量，其描述光源的光通量，其为由辐射源发射的总可见辐射的量度。光通量越大，对观测者呈现的光源越亮。
CIE x和CIE y代表熟练技术人员熟悉的标准CIE色图(此处标准观测者1931)中的坐标，通过它们描述光源的颜色。
上述所有量均通过熟练技术人员熟悉的方法由光源的发射光谱计算。
与此相关，本发明进一步涉及本发明化合物或如上所述的本发明发射转换材料在光源中的用途。
光源尤其优选为LED，尤其是无机发光材料转换LED，简称pc-LED。此处发射转换材料尤其优选包含除本发明转换无机发光材料之外的至少一种其他转换无机发光材料，特别是使得光源发射白光或具有一定色点的光(按需颜色原理)。“按需颜色原理”意指用使用一或多种转换无机发光材料的pc-LED实现具有一定色点的光。
因此，本发明进一步涉及包含一次光源和发射转换材料的光源。
这里还优选的是，发射转换材料包含除本发明转换无机发光材料之外的至少一种其他转换无机发光材料，使得光源优选发射白光或具有一定色点的光。
本发明的光源优选为pc-LED。pc-LED一般包含一次光源和发射转换材料。为此，本发明的发射转换材料可分散于树脂(例如环氧树脂或有机硅树脂)中，或被赋予适合尺寸比率，直接排布于一次光源上或者取决于应用而由一次光源远程排布(后一排布也包括“远程无机发光材料技术”)。
一次光源可为半导体芯片、发光光源如ZnO、所谓的TCO(透明导电氧化物)、基于ZnSe或SiC的排布、基于有机发光层(OLED)的排布或等离子体或放电源，最优选为半导体芯片。如由已有技术已知，若一次光源为半导体芯片，则其优选为发光铟铝镓氮化物(InAlGaN)。该类型的一次光源的可能形式是熟练技术人员已知的。此外，激光适用作光源。
为用于光源，尤其是pc-LED，本发明的发射转换材料也可转换成任何所需外部形状，如球形粒子、薄片和结构化材料和陶瓷。这些形状概述于术语“成形体”下。成形体因此为发射转换成形体。
本发明进一步涉及含有至少一种本发明的光源的照明单元。该类型的照明单元主要用于显示设备中，尤其具有背光的液晶显示设备(LC显示器)中。因此，本发明还涉及该类型的显示设备。
在本发明的照明单元中，发射转换材料与一次光源(尤其半导体芯片)之间的光学偶联优选借助光导排布进行。以此方式，一次光源可安装于中心位置，且为此借助光导装置如光纤而光学偶联至发射转换材料。以此方式，可实现由一或多种不同转换无机发光材料组成的符合照明愿望的灯，其可经排布以形成光屏幕和光波导，与一次光源偶联。以此方式，可将强一次光源置于有利于电学安装的位置，并可安装偶联至光波导的包含发射转换材料的灯，而无需其他电缆，仅通过将光波导布置于任何所需位置上。
在此描述的所有本发明的变体可彼此组合，只要相应实施方案不相互排斥。特别地，基于本说明书的教导，作为常规优化的一部分，精确组合此处所述多种变体以获得特定特别优选的实施方案是显而易见的操作。
除非另外指明，否则本申请中所示的参数范围涵盖所有有理数和整数数值，包括所示的参数范围的限值和其误差限值。针对对应范围和特性所指示的上限值和下限值又彼此组合产生另外优选范围。
在本申请的说明书和权利要求书中，词语“包括(include)”和“包含(comprise)”和这些词的变体(如“包括(including)”和“包括(includes)”)解释为“包括，但不限于”且不排除其他组分。词语“包括”还涵盖术语“由……组成”，但不限于此。
以下实施例意欲说明本发明，尤其是说明所描述的本发明变体的这类例示性组合的结果。然而，其决不应被视为限制性的，而是意欲促进普遍化。
所述制备中可用的所有化合物或组分已知且可市购，或可通过已知方法合成。
温度始终以℃表示。此外不言而喻的是，在说明书以及实施例中，组合物中所添加组分的量始终共计为100％。百分比数据应始终视在给定关系中考虑。
实施例
a)Na1.8Li0.2Ge0.999Mn0.001Si3O9
在玛瑙研钵中用丙酮彻底磨碎0.9539g(9.000mmol)Na2CO3、0.0739g(1.000mmol)Li2CO3、1.0453g(9.990mmol)GeO2、1.8025g(30.000mmol)SiO2和0.0018g(0.010mmol)MnC2O4·2H2O。将粉末干燥，转移到经覆盖的瓷坩埚中并在600℃下煅烧1小时。在玛瑙研钵中用丙酮彻底磨碎经煅烧的粉末，与2.5重量％NaF和2.5重量％LiF一起磨。将干燥的粉末转移到经覆盖的瓷坩埚中并在800℃下加热4小时。
b)K2Ge3.996Mn0.004O9
在玛瑙研钵中用丙酮彻底磨碎1.3820g(10.000mmol)K2CO3、4.1814g(39.960mmol)GeO2和0.0072g(0.040mmol)MnC2O4·2H2O。将粉末干燥，转移到经覆盖的瓷坩埚中并在600℃下煅烧1小时。在玛瑙研钵中用丙酮彻底磨碎经煅烧的粉末，与5重量％KF一起磨。将干燥的粉末转移到经覆盖的瓷坩埚中并在800℃下加热4小时。
c)Rb2Ge3.996Mn0.004O9
在玛瑙研钵中用丙酮彻底磨碎2.3095g(10.000mmol)Rb2CO3、4.1814g(39.960mmol)GeO2和0.0072g(0.040mmol)MnC2O4·2H2O。将粉末干燥，转移到经覆盖的瓷坩埚中并在600℃下煅烧1小时。在玛瑙研钵中用丙酮彻底磨碎经煅烧的粉末，与5重量％RbF一起磨。将干燥的粉末转移到经覆盖的瓷坩埚中并在780℃下加热4小时。
d)K2SiGe2.997Mn0.003O9
在玛瑙研钵中用丙酮彻底磨碎1.5202g(11.000mmol)K2CO3、0.6008g(10.00mmol)SiO2、3.1360g(29.970mmol)GeO2和0.0054g(0.030mmol)MnC2O4·2H2O。将粉末干燥，转移到经覆盖的瓷坩埚中并在850℃下煅烧4小时。
e)使用按照本发明制备的组成为K2Ge3.996Mn0.004O9的无机发光材料制造pc-LED
称出4g具有组成K2Ge3.996Mn0.004O9的无机发光材料，将其与1g光学透明硅酮混合且随后在行星式离心混合器中均匀混合，使得总材料中的无机发光材料浓度为80重量％。将以此方式获得的聚硅酮/无机发光材料借助自动分配器涂覆于发射蓝光的半导体LED的芯片上，并通过供热将其固化。在该实施例中用于LED表征的蓝光LED具有442nm的发射波长，并在350mA电流强度下操作。LED的光度表征使用Instrument Systems CAS140光度仪和所附ISP 250积分球进行。LED经由测定波长依赖性光谱功率密度来表征。将LED发射的光的所得光谱用于计算色点坐标CIE x和y。
附图说明
图1 Cu K-α辐射的具有ICCD参照的XRD图
图2 相对于作为白光标准的BaSO4的K2Ge3.996Mn0.004O9反射光谱。
图3 相对于作为白色标准的BaSO4的K2SiGe2.997Mn0.003O9反射光谱。
图4 相对于作为白色标准的BaSO4的Rb2Ge3.996Mn0.004O9反射光谱。
图5 K2Ge3.996Mn0.004O9的激发光谱(λem＝664nm)
图6 K2SiGe2.997Mn0.003O9的激发光谱(λem＝664nm)
图7 Rb2Ge3.996Mn0.004O9的激发光谱(λem＝654nm)
图8 K2Ge3.996Mn0.004O9的发射光谱(λex＝320nm)
图9 K2SiGe2.997Mn0.003O9的发射光谱(λex＝310nm)
图10 Rb2Ge3.996Mn0.004O9的发射光谱(λex＝327nm)
图11 CIE 1931色图的具有K2Ge3.996Mn0.004O9、K2SiGe2.997Mn0.003O9和Rb2Ge3.996Mn0.004O9色点的部分。
图12 实施例e)中所述pc-LED的LED光谱。
Claims (17)
1.式I化合物，
(A2-2nBn)x(Ge1-mMm)yO(x+2y)：Mn4+ I
其中
A对应于选自Li、Na、K和Rb组成的组的至少一种元素，
B对应于(C1-uDu)，
C对应于选自Ca、Ba和Sr组成的组的至少一种元素，
D对应于选自Ca和Ba组成的组的至少一种元素，
M对应于选自Ti、Zr、Hf、Si和Sn组成的组的至少一种元素，
0≤n≤1，
0＜u≤1，
0.5≤x≤2，
0≤m＜1，且
1≤y≤9。
2.根据权利要求1的化合物，其特征在于n等于0。
3.根据权利要求1或2的化合物，其特征在于式I化合物选自式Ia化合物组成的组，
(A2)x(Ge1-m-zMmMnz)yO(x+2y) la
其中
A、M、x、y和m具有权利要求1中所示含义之一，且0＜z≤0.01＊y。
4.根据权利要求1至3中一项或多项的化合物，其特征在于x等于1。
5.根据权利要求1至4中一项或多项的化合物，其特征在于y等于4。
6.根据权利要求1至5中一项或多项的化合物，其特征在于该化合物选自式Ia-1至Ia-4化合物组成的组，
A2Ge1-zMnzM3O9 la-1
A2Ge2-zMnzM2O9 la-2
A2Ge3-zMnzMO9 la-3
A2Ge4-zMnzO9 la-4
其中
M、z和A具有权利要求1中所示含义之一。
7.根据权利要求1至6中一项或多项的化合物，其特征在于M等于Si。
8.根据权利要求1至7中一项或多项的化合物，其特征在于0.001≤z≤0.004。
9.根据权利要求1至8中一项或多项的化合物，其特征在于A对应于选自Li、Na、K和Rb组成的组的至少两种元素。
10.用于制备根据权利要求1至9中一项或多项的化合物的方法，其特征在于在步骤a)中混合适合的起始材料或相应反应性形式，和在步骤b)中热处理混合物。
11.根据权利要求10的方法，其中步骤a)中的起始材料选自相应氧化物、碳酸盐和草酸盐组成的组。
12.根据权利要求1至9中一项或多项的化合物用于使蓝光或近UV发射部分或完全地转换成具有更长波长的可见光的用途。
13.发射转换材料，其包含至少一种根据权利要求1至9中一项或多项的化合物和一或多种其他转换无机发光材料。
14.具有至少一个一次光源的光源，其特征在于该光源包含至少一种根据权利要求1至9中一项或多项的化合物或根据权利要求13的发射转换材料。
15.根据权利要求14的光源，其特征在于一次光源对应于发光铟铝镓氮化物和/或铟镓氮化物。
16.照明单元，特别是用于显示设备的背光的照明单元，其特征在于其含有至少一个根据权利要求14或15的光源。
17.显示设备，特别地是具有背光的液晶显示设备(LC显示器)，其特征在于其含有至少一个根据权利要求16的照明单元。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108102648A (zh) * | 2017-12-25 | 2018-06-01 | 广东工业大学 | 一种颜色可调的长余辉材料及其制备方法 |
| CN109054830A (zh) * | 2018-07-17 | 2018-12-21 | 延边大学 | 用于白光led的多种钛锗酸盐的荧光材料及制备方法 |
| CN109545932A (zh) * | 2017-09-22 | 2019-03-29 | 三星显示有限公司 | 发光二极管 |
| CN113667472A (zh) * | 2021-07-12 | 2021-11-19 | 广东工业大学 | 一种Bi3+掺杂的紫外长余辉发光材料及其制备方法和应用 |
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| CA2990334A1 (en) * | 2015-03-25 | 2016-09-29 | Vitabeam Ltd. | Method and apparatus for stimulation of plant growth and development with near infrared and visible lights |
| TWI589036B (zh) * | 2016-07-25 | 2017-06-21 | 林孝正 | 用於發光晶體的覆晶螢光鏡片、具有其的發光模組、生物培養裝置及發光模組改造方法 |
| TWI589035B (zh) * | 2016-07-25 | 2017-06-21 | 林孝正 | 生物培養裝置及其發光模組改造方法 |
| JP6799682B2 (ja) | 2016-11-17 | 2020-12-16 | ゼネラル・エレクトリック・カンパニイ | 被覆赤色線放出蛍光体 |
| KR102048678B1 (ko) * | 2016-12-29 | 2019-11-26 | 중앙대학교 산학협력단 | 산화물계 형광체, 그의 제조 방법, 및 상기 형광체를 포함하는 발광 다이오드 |
| DE102018126246A1 (de) * | 2018-10-22 | 2020-04-23 | Osram Opto Semiconductors Gmbh | Verbesserung der klebstoffschicht bei led flipchip anwendungen |
| US20220403450A1 (en) | 2021-06-03 | 2022-12-22 | Illumina Software, Inc. | Systems and methods for sequencing nucleotides using two optical channels |
| KR20240049214A (ko) | 2021-09-01 | 2024-04-16 | 일루미나, 인코포레이티드 | 가속 염기 호출을 위한 진폭 변조 |
| US20230183799A1 (en) | 2021-12-10 | 2023-06-15 | Illumina, Inc. | Parallel sample and index sequencing |
| WO2023175018A1 (en) | 2022-03-15 | 2023-09-21 | Illumina, Inc. | Concurrent sequencing of forward and reverse complement strands on separate polynucleotides |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109545932A (zh) * | 2017-09-22 | 2019-03-29 | 三星显示有限公司 | 发光二极管 |
| CN109545932B (zh) * | 2017-09-22 | 2024-03-08 | 三星显示有限公司 | 发光二极管 |
| CN108102648A (zh) * | 2017-12-25 | 2018-06-01 | 广东工业大学 | 一种颜色可调的长余辉材料及其制备方法 |
| CN108102648B (zh) * | 2017-12-25 | 2020-03-10 | 广东工业大学 | 一种颜色可调的长余辉材料及其制备方法 |
| CN109054830A (zh) * | 2018-07-17 | 2018-12-21 | 延边大学 | 用于白光led的多种钛锗酸盐的荧光材料及制备方法 |
| CN109054830B (zh) * | 2018-07-17 | 2021-06-18 | 延边大学 | 用于白光led的多种钛锗酸盐的荧光材料及制备方法 |
| CN113667472A (zh) * | 2021-07-12 | 2021-11-19 | 广东工业大学 | 一种Bi3+掺杂的紫外长余辉发光材料及其制备方法和应用 |
| CN113667472B (zh) * | 2021-07-12 | 2022-06-10 | 广东工业大学 | 一种Bi3+掺杂的紫外长余辉发光材料及其制备方法和应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20170051201A1 (en) | 2017-02-23 |
| WO2015165567A1 (de) | 2015-11-05 |
| EP3137576A1 (de) | 2017-03-08 |
| KR20160147936A (ko) | 2016-12-23 |
| JP2017521503A (ja) | 2017-08-03 |
| DE102014006003A1 (de) | 2015-10-29 |
| TW201602310A (zh) | 2016-01-16 |
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