EP2414482A1 - Europium, yttrium oxide, or gadolinium core/shell composition, phosphor including said composition, and methods for preparing same - Google Patents
Europium, yttrium oxide, or gadolinium core/shell composition, phosphor including said composition, and methods for preparing sameInfo
- Publication number
- EP2414482A1 EP2414482A1 EP10710053A EP10710053A EP2414482A1 EP 2414482 A1 EP2414482 A1 EP 2414482A1 EP 10710053 A EP10710053 A EP 10710053A EP 10710053 A EP10710053 A EP 10710053A EP 2414482 A1 EP2414482 A1 EP 2414482A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- gadolinium
- oxide
- europium
- core
- yttrium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 52
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052693 Europium Inorganic materials 0.000 title claims abstract description 26
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 229910052688 Gadolinium Chemical group 0.000 title claims abstract description 17
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical group [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 title claims abstract description 14
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical group O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title claims description 25
- 238000001354 calcination Methods 0.000 claims abstract description 19
- 239000000725 suspension Substances 0.000 claims abstract description 19
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 19
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000012429 reaction media Substances 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 7
- 150000000918 Europium Chemical class 0.000 claims abstract description 4
- 150000000921 Gadolinium Chemical class 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 32
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 16
- 239000011707 mineral Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 239000002019 doping agent Substances 0.000 claims description 7
- 229910001938 gadolinium oxide Inorganic materials 0.000 claims description 7
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 7
- 150000002910 rare earth metals Chemical class 0.000 claims description 7
- 229940075613 gadolinium oxide Drugs 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910001940 europium oxide Inorganic materials 0.000 claims description 4
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- LQFNMFDUAPEJRY-UHFFFAOYSA-K lanthanum(3+);phosphate Chemical compound [La+3].[O-]P([O-])([O-])=O LQFNMFDUAPEJRY-UHFFFAOYSA-K 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 3
- JAOZQVJVXQKQAD-UHFFFAOYSA-K gadolinium(3+);phosphate Chemical compound [Gd+3].[O-]P([O-])([O-])=O JAOZQVJVXQKQAD-UHFFFAOYSA-K 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims 1
- 229910001928 zirconium oxide Inorganic materials 0.000 claims 1
- 239000011162 core material Substances 0.000 description 39
- 239000002243 precursor Substances 0.000 description 38
- 239000000243 solution Substances 0.000 description 23
- 239000000047 product Substances 0.000 description 22
- 238000004020 luminiscence type Methods 0.000 description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 18
- 230000005284 excitation Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 9
- 238000011282 treatment Methods 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- -1 Ca 2 P 2 O 7 Chemical class 0.000 description 7
- 238000001033 granulometry Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 235000021317 phosphate Nutrition 0.000 description 5
- 238000005424 photoluminescence Methods 0.000 description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000035800 maturation Effects 0.000 description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000029219 regulation of pH Effects 0.000 description 3
- 238000004626 scanning electron microscopy Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-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
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 229910011255 B2O3 Inorganic materials 0.000 description 1
- 229910015999 BaAl Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical class [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- PSHMSSXLYVAENJ-UHFFFAOYSA-N dilithium;[oxido(oxoboranyloxy)boranyl]oxy-oxoboranyloxyborinate Chemical compound [Li+].[Li+].O=BOB([O-])OB([O-])OB=O PSHMSSXLYVAENJ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- VPYVGHGNVQXIEY-UHFFFAOYSA-N gadolinium(3+);oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Y+3].[Gd+3] VPYVGHGNVQXIEY-UHFFFAOYSA-N 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910052590 monazite Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 231100000683 possible toxicity Toxicity 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004441 surface measurement Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 150000003746 yttrium Chemical class 0.000 description 1
- UXBZSSBXGPYSIL-UHFFFAOYSA-K yttrium(iii) phosphate Chemical compound [Y+3].[O-]P([O-])([O-])=O UXBZSSBXGPYSIL-UHFFFAOYSA-K 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- 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
-
- 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
-
- 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
- C09K11/7784—Chalcogenides
- C09K11/7787—Oxides
-
- 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
Definitions
- the present invention relates to a composition based on europium, yttrium oxide or gadolinium, core / shell type, a phosphor comprising this composition and their methods of preparation.
- the yttrium or gadolinium oxides doped with europium are well known for their luminescence properties. They emit a red light when irradiated by UV radiation. Phosphors exploiting this property and based on these oxides are commonly used on an industrial scale, for example in trichromatic fluorescent lamps.
- the object of the invention is a phosphor meeting this need.
- the invention relates to a composition which is characterized in that it comprises:
- the invention also relates to a phosphor which is characterized in that it comprises a composition of the type described above.
- the phosphors of the invention have properties similar to those of currently known phosphors.
- rare earth for rare earth is meant for the remainder of the description the elements of the group consisting of yttrium and the elements of the periodic classification of atomic number inclusive between 57 and 71.
- specific surface is meant the specific surface B. AND. determined by adsorption of krypton.
- the surface measurements given in the present description were carried out on an ASAP2010 device after degassing the powder for 8 hours, at 200 ° C.
- the invention relates to two types of products: compositions which may be called also in the remainder of this description "precursors", and phosphors obtained from these compositions or precursors.
- the luminophores themselves have sufficient luminescence properties to make them directly usable in the desired applications.
- the precursors have no luminescence properties or possibly luminescence properties that are too low for use in these same applications.
- compositions or precursors are provided.
- compositions of the invention are characterized essentially by their specific structure of the core / shell type which will be described in detail below.
- the mineral core is based on a material that can be in particular an oxide or a phosphate.
- oxides mention may in particular be made of oxides of zirconium, zinc, titanium, magnesium, aluminum (alumina) and the oxides of one or more rare earths, one of which may optionally act as a dopant.
- gadolinium oxide As the rare earth oxide, gadolinium oxide, ytthium oxide and cerium oxide may be mentioned more particularly.
- Yttrium oxide, gadolinium oxide and alumina may be chosen preferably.
- Alumina may be chosen even more preferably because it has the particular advantage of allowing a calcination at a higher temperature during the passage of the precursor to the phosphor without there being a diffusion of the dopant in the heart. This thus makes it possible to obtain a product whose luminescence properties are optimal because of a better crystallization of the shell, a consequence of the higher calcination temperature.
- orthophosphates of one or more rare earths one of which may optionally act as a dopant, such as lanthanum (LaPO 4 ), lanthanum and cerium ((LaCe) PO 4 ), yttrium (YPO 4 ), polyphosphates of rare earths or aluminum.
- LaPO 4 lanthanum
- LaCe lanthanum and cerium
- YPO 4 yttrium
- the core material is a lanthanum orthophosphate, a gadolinium orthophosphate or an yttrium orthophosphate.
- alkaline earth phosphates such as Ca 2 P 2 O 7 , zirconium phosphate ZrP 2 O 7 , and alkaline earth hydroxylapatites.
- mineral compounds such as vanadates, in particular rare earth (YVO 4 ), germanates, silicates, in particular zinc or zirconium silicate, tungstates, molybdates, sulphates (BaSO 4) are suitable. ), borates (YBO 3 , GdBO 3 ), carbonates and titanates (such as BaTiO 3 ), zirconates, alkaline earth metal aluminates, optionally doped with a rare earth, such as barium aluminates and / or magnesium, such as MgAl 2 O 4 , BaAl 2 O 4 , or BaMgAl 10O17.
- YVO 4 rare earth
- germanates such as germanates, silicates, in particular zinc or zirconium silicate, tungstates, molybdates, sulphates (BaSO 4)
- borates YBO 3 , GdBO 3
- carbonates and titanates such as BaTiO 3
- zirconates alkaline earth metal
- the core material may have particular optical properties, including reflective properties of UV radiation.
- the mineral core is based on is meant a set comprising at least 50%, preferably at least 70%, and more preferably at least 80% or 90% by weight of the material in question.
- the core may consist essentially of said material (ie at a content of at least 95% by weight, for example at least 98%, or even at least 99% by weight) or entirely constituted by this material. material.
- the core is made of a dense material which corresponds in fact to a generally well-crystallized material or to a material whose surface area is low.
- low specific surface area is meant a specific surface area of at most 5 m 2 / g, more particularly at most 2 m 2 / g, even more particularly at most 1 m 2 / g, and especially from plus 0.6 m 2 / g.
- the core is based on a temperature-stable material.
- a temperature-stable material By this is meant a material whose melting point is at an elevated temperature, which does not degrade to a troublesome by-product for application as a luminophore at the same temperature and which remains crystallized and therefore does not become a material. amorphous still at this same temperature.
- the high temperature referred to herein is a temperature at least greater than 900 ° C., preferably at least greater than 1000 ° C. and even more preferably at least 1200 ° C.
- the third variant consists in using for the core a material which combines the characteristics of the two previous variants, thus a material with a low specific surface area and temperature stability.
- the use of a heart according to at least one of the variants described above has several advantages. Firstly, the core / shell structure of the precursor is particularly well preserved in the resulting phosphor which provides a maximum cost advantage.
- the phosphors obtained from the precursors of the invention in the manufacture of which a core has been used according to at least one of the abovementioned variants have photoluminescence yields which are not only identical but in some cases higher than those of a phosphor of the same composition but which does not have the core-shell structure.
- the core materials can be densified, in particular by using the known technique of molten salts.
- This technique involves wearing the material to be densified at a high temperature, for example at least 900 ° C., optionally under a reducing atmosphere, for example an argon / hydrogen mixture, in the presence of a melting agent which may be chosen from chlorides (sodium chloride, for example), fluorides (lithium fluoride for example), borates (lithium borate), carbonates or boric acid.
- a melting agent which may be chosen from chlorides (sodium chloride, for example), fluorides (lithium fluoride for example), borates (lithium borate), carbonates or boric acid.
- the core may have a mean diameter of in particular between 1 and 10 microns.
- These diameter values can be determined by scanning electron microscopy (SEM) by random counting of at least 150 particles.
- the dimensions of the core, as well as the thickness of the shell which will be described later, can be measured in particular in transmission electron microscopy photographs of sections of the compositions / precursors of the invention.
- compositions / precursors of the invention is the shell.
- This shell homogeneously covers the core to a thickness that is equal to or greater than 300 nm.
- homogeneous is meant a continuous layer, completely covering the core and whose thickness is preferably never less than 300 nm. This homogeneity is particularly visible on scanning electron microscopy photographs. X-ray diffraction (XRD) measurements also reveal the presence of two distinct compositions between the heart and the shell.
- the thickness of the layer may be more particularly at least
- 500 nm and even more particularly at least 700 nm It may be equal to or less than 2000 nm (2 ⁇ m), more particularly equal to or less than 1500 nm and be between 750 nm and 1500 nm.
- the shell is based on or consists of the product with the desired luminescence properties (red phosphor) or capable of giving such properties, that is to say that it is based on or consists of europium oxide and a ytthum (Y 2 O 3 ) or gadolinium (Gd 2 ⁇ 3 ) oxide or a mixed yttrium-gadolinium oxide ((Y, Gd) 2 O 3 ), it being understood that the invention It applies well to the case of the mixed oxide even if the description for the sake of simplification refers thereafter only to an yttrium oxide or a gadolinium oxide.
- the europium plays the role of dopant for the oxide Ln 2 O 3 (Ln denoting yttrium and / or gadolinium) that is to say that it confers luminescence properties to this oxide.
- the amount of europium is generally between 0.01% and 20% by weight of europium oxide relative to the oxide mass Ln 2 ⁇ 3. Depending in particular on the applications of the compositions, this amount may be between 4% and 15%, more particularly between 4% and 7%, especially in the case of applications in the trichromatic lamps.
- the europium doped Ln 2 ⁇ 3 oxide may optionally contain other additional elements chosen from rare earths other than europium, gadolinium and yttrium. These include terbium, samarium or lanthanum. These other elements may be present as dopants in addition to europium, this may be the case in particular terbium or samarium. In such a case, the amount of this additional element is generally at most 1% by mass of oxide of the element relative to the oxide mass Ln 2 ⁇ 3. These other elements may also be present in substitution of gadolinium and / or yttrium. This may be for example the case of lanthanum.
- the amount of this additional element is generally at most 40%, more particularly at most 10%, by weight of oxide of the element relative to the weight of Ln 2 O 3 oxide. It is important to note here that the dopant or substituent functions attributed to the above-mentioned elements have been purely indicative and not limiting and that the invention covers all cases where the shell comprises an oxide Ln 2 O 3 with any of these additional elements regardless of its role or function in this oxide.
- the particles comprising a core and a shell which constitute the compositions / precursors of the invention generally have a mean diameter which is preferably between 1, 6 microns and 15 microns. This diameter may more particularly be between 3 ⁇ m and 10 ⁇ m and even more particularly between 4 ⁇ m and 8 ⁇ m.
- the average diameter referred to is the volume average of the diameters of a particle population.
- the granulometry values given here and for the remainder of the description are measured by the laser granulometry technique, for example by means of a Malvern laser particle size analyzer, on a sample of particles dispersed in ultrasonic water (130 W ) for 1 minute 30 seconds.
- the particles preferably have a low dispersion index, typically at most 0.7, more particularly at most 0.6 and even more particularly at most 0.5.
- dispersion index of a population of particles is meant, for the purposes of this description, the ratio I as defined below: where: 0 84 is the particle diameter for which 84% of the particles have a diameter less than 0s 4 ;
- 016 is the particle diameter for which 16% of the particles have a diameter less than 0-1 ;
- 050 is the average diameter of the particles, diameter for which 50% of the particles have a diameter less than 0so.
- compositions / precursors according to the invention may optionally have luminescence properties after exposure to certain wavelengths, it is possible and even necessary to further improve these luminescence properties by treating these products with post-treatments. , and this in order to obtain real luminophores directly usable as such in the desired application.
- the luminophores of the invention consist of, or include, the compositions of the invention as described above. As a result, all that has been previously described with regard to these compositions is likewise applicable here for the description of the phosphors according to the invention. These include all the characteristics given above on the structure constituted by the mineral core and the homogeneous shell, on the nature of the mineral core, on that of the shell and in particular the compositions of the oxide Ln 2 ⁇ 3 as well as granulomethane characteristics.
- the luminophores of the invention are obtained from the compositions / precursors by a heat treatment which has the consequence of not substantially modifying the characteristics of these compositions as mentioned above.
- this treatment leads to better crystallization of the Ln 2 ⁇ 3 oxide of the shell, which has the essential consequence of improving the luminescence properties.
- compositions and phosphors of the invention The description of the methods for preparing the compositions and phosphors of the invention will be made below.
- the first step is therefore a step in which a suspension is formed which is generally an aqueous suspension which comprises the mineral core as described above.
- a suspension is formed which is generally an aqueous suspension which comprises the mineral core as described above.
- a heart having a particle size adapted to that of the composition that is to be prepared.
- a core having a mean diameter of in particular between 1 and 10 ⁇ m and having a dispersion index of at most 0.7 or at most 0.6.
- the pH of the suspension should be between 8 and 11, more particularly between 8.5 and 9.5. It is brought to this value by addition to the suspension of a base. Suitable bases include, for example, metal hydroxides (NaOH, KOH, Ca (OH) 2 , ....) or even ammonium hydroxide.
- the second step (b) of the process uses a solution containing a europium salt and, depending on the composition that is to be prepared, a yttrium salt and / or gadolinium. In the case where it is sought to prepare a composition in which, as seen above, the oxide Ln 2 O 3 of the shell comprises other rare earths, this solution then additionally contains a salt. of the one or more rare earths.
- Suitable salts include, for example, chlorides, nitrates, sulphates or acetates. Nitrates can be used more particularly.
- the solution is added to the suspension formed in the previous step (a).
- This addition is preferably progressively, for example over a period which may range from 30 minutes to 1 hour, more particularly from 30 minutes to 2 hours, continuous and with stirring.
- this addition is done by maintaining the pH of the reaction medium at a substantially constant value, generally to the pH value of the suspension just before the addition of the salt solution. This pH value can thus be between 8 and 11, more particularly between 8.5 and 9.5.
- pH maintained at a substantially constant value it is meant that the pH of the medium will vary by not more than 0.5 pH units around the fixed set point and more preferably by at most 0.1 pH units around this value.
- a base as described above can be added to the reaction medium.
- the addition of the solution to the suspension of the second step (b) is carried out at a temperature which can range from ambient (20-25 ° C.) to 60 ° C. or 80 ° C.
- a precipitate which comprises particles of a rare earth compound (Y and / or Gd and Eu) and ammonium deposited in a homogeneous layer on the core. Variations in temperature and feed rate conditions during mixing of the solution and the slurry make it possible to vary the dimensions of these particles.
- the thickness of the layer may vary depending on the respective amounts of salt and heart used.
- the precipitate obtained is separated from the liquid phase of the reaction medium by any solid / liquid separation process such as, for example, filtration, centrifugation, decantation or the like. he can also be subjected to one or more washes, for example, to eliminate soluble salts.
- the precipitate can be dried to evaporate unbound water, for example by a heat treatment between 50 0 C and 100 0 C, by drying under reduced pressure or by spraying.
- step (b) it is possible, after step (b), to ripen the reaction medium.
- the term "ripening step” means maintaining the medium obtained after the end of the addition of the solution under the same temperature and stirring conditions as those of step (b).
- the duration of this maturing step may be for example between 15 minutes and 3 hours, these values being given for purely indicative and not limiting.
- the last step of the process is a calcination step. This step makes it possible to transform the compound of rare earths (Y and / or Gd and Eu) and ammonium of the layer into an oxide of these same rare earths. This calcination is generally done under air.
- the duration of calcination can be determined conventionally, for example by controlling the constant weight. For information only, the duration of calcination can vary between 30 minutes and 6 hours.
- the luminophores of the invention are obtained by calcination at a temperature of at least 1200 ° C. of the compositions / precursors as described above or of the compositions / precursors obtained by the process which has also been described above.
- This temperature may be between 1200 ° C and 1650 ° C, more particularly between 1300 0 C and 1500 ° C.
- the precursors are converted into effective phosphors.
- the precursors themselves may have intrinsic luminescence properties, these properties are generally insufficient for the intended applications and are greatly improved by the calcination treatment. Calcination is usually done under air.
- the calcination can be carried out in the presence of a flux or fluxing agent such as, for example, lithium fluoride, lithium tetraborate, lithium chloride, sodium chloride or barium chloride, lithium, sodium or barium, lithium phosphate, ammonium chloride, boric oxide and boric acid and ammonium phosphates, and mixtures thereof.
- a flux or fluxing agent such as, for example, lithium fluoride, lithium tetraborate, lithium chloride, sodium chloride or barium chloride, lithium, sodium or barium, lithium phosphate, ammonium chloride, boric oxide and boric acid and ammonium phosphates, and mixtures thereof.
- the calcined product is advantageously washed, so as to obtain a phosphor as pure as possible and in a deagglomerated or weakly agglomerated state.
- the heat treatment can be conducted without inducing sensitive phenomena of europium diffusion from the outer phosphor layer to the core.
- the invention covers the phosphor obtainable by the preparation method described above.
- the phosphors of the invention can be used in lighting or visualization systems having an excitation source in the UV range (200-280 nm), for example around
- mercury vapor trichromatic lamps backlighting lamps for liquid crystal systems, in tubular or planar form (LCD Back Lighting). They exhibit a high gloss under UV excitation, and a lack of luminescence loss as a result of thermal post-treatment. Their luminescence is in particular stable under UV at temperatures ranging from ambient to 300 ° C.
- the luminophores of the invention are also good candidates as red phosphors for VUV excitation systems (or "plasma”), such as plasma screens and trichromatic lamps without mercury, including Xenon excitation lamps (tubular or planar).
- VUV excitation systems or "plasma”
- the phosphors of the invention have a strong red emission under VUV excitation (for example, around 147 nm and 172 nm).
- the phosphors are stable under VUV excitation.
- the phosphors of the invention can also be used as red phosphors in LED devices. They can be used especially in systems excitable in the near UV. They can also be used in UV excitation labeling systems.
- the phosphors of the invention can be used in cathode excitation systems of CRT (cathode ray tubes) or FED (field emission display) or SED (surface emission display) type.
- the luminophores of the invention can be used in the manufacture of the devices mentioned above by well-known techniques, for example by screen printing, by spraying, by electrophoresis or sedimentation.
- the invention also relates, in another aspect, to luminescent devices, comprising, as a source of red luminescence, the phosphors as described above or the phosphors obtained from the process also described above.
- the particles prepared have been characterized in terms of granulometry, morphology and composition by the following methods. Quranometric measurements
- Particle diameters were determined using a laser granulometer (Malvern 2000) on a sample of particles dispersed in ultrasonic water (130 W) for 1 min 30 seconds.
- Electron microscopy Transmission electron microscopy is performed on a section (microtomy) of the particles, using a JEOL 2010 FEG high resolution TEM microscope.
- the spatial resolution of the apparatus for the chemical composition measurements by EDS (scattering spectroscopy in energy) is ⁇ 2 nm.
- the correlation of observed morphologies and measured chemical compositions makes it possible to highlight the core-shell structure, and to measure the thickness of the shell on the plates.
- the measurements of chemical composition can also be carried out by EDS on plates made by STEM HAADF.
- the measurement corresponds to an average performed on at least two spectra.
- X diffractograms were made using CuK ⁇ as with copper anti-cathode according to the Bragg-Brendano method.
- the resolution is chosen to be sufficient to separate the lines of the different compounds, preferably it is ⁇ (2 ⁇ ) ⁇ 0.02 °.
- An oxide of formula (Yo, 95 Eu 0, os) 2 O 3 is prepared in the following manner.
- EXAMPLE 2 This example relates to a core / shell precursor according to the invention, the core of which is a lanthanum phosphate.
- the product obtained is densified by calcining it for 2 hours in the presence of 1% by weight of LiF at 1100 ° C. under a reducing atmosphere (Ar / H 2 ). We then obtain a rare earth phosphate monazite phase.
- the average particle size, measured by a statistic of 150 particles on microscope slides (SEM), is 3.2 ⁇ m.
- a solution A is prepared by mixing 275.5 ml of 3.45 mol / l solution of ytthum nitrate and 24.9 ml of a solution of europium nitrate at 2.01 mol / l and then completing at 1 I.
- 22 g of the previously prepared core are dispersed in 650 ml of deionized water, with stirring at 400 rpm, at room temperature.
- the pH is raised to 8.5 by the addition of 6N ammonia.
- 340 ml of solution A, which is still under stirring, are then added, over a period of 1 h 30, and under pH regulation, at a pH of 8.5, with 6N ammonia.
- a maturation of 1 h is carried out at the same temperature.
- the product obtained is then filtered, washed with 2 volumes of water, then dried at 100 ° C. for 5 hours and then calcined at 900 ° C. for 2 hours.
- the core / shell precursor is then obtained, the X-ray diffraction showing the presence of two distinct crystalline phases (Y, Eu) 2 ⁇ 3 and LaPO 4 .
- the product has a mean particle size (D50) equal to 8.3 ⁇ m.
- a TEM plate is made on the resin-coated product, prepared by ultramicrotomy (thickness -100 nm) and placed on a perforated membrane.
- the particles are seen in section. In this photograph, we see a section of particle whose heart is spherical and is surrounded by a shell of average thickness of 800 nm.
- This example relates to a phosphor according to the invention.
- Example 2 The precursor product obtained in Example 2 is calcined for 4 hours at 1300 ° C. in air. A luminophore emitting in the red under UV excitation is obtained.
- This phosphor exhibits a photoluminescence (PL) efficiency of 98% relative to the luminophore obtained by calcination under identical conditions of the precursor oxide of the comparative example.
- PL photoluminescence
- This efficiency is determined by the integration of the emission spectrum under excitation of 254 nm, measured with a spectrofluorimeter in the wavelength range of 500 nm to 750 nm. It is 100% normalized for the comparative phosphor.
- the slight decrease in PL (2%) relative to the comparative phosphor obtained from the precursor of Example 1 and after calcination under conditions identical to that of the present example is entirely acceptable, given the saving of 30%. made in europium.
- This example relates to a core / shell precursor according to the invention, the core of which is an yttrium oxide.
- An oxide of formula Y2O3 is prepared according to a procedure similar to that described in Comparative Example 1.
- a suspension containing a neutral oxalate of yttrium is brought to 45 ° C.
- a solution of 0.255 M ammonium oxalate is added to this suspension in order to obtain oxalate / Y molar ratios of 2.5 and ammonia / Y of 5.
- the reaction medium is stirred for 15 minutes, the precipitate obtained is recovered by filtration, then washed and dried at 100 ° C. Finally, it is calcined at 900 ° C. under air for 2 hours. It has a mean diameter measured in Malvern granulometry of 4 microns.
- the product obtained is then calcined at 1450 ° C. in the presence of 1% by weight of boric acid. It is then deagglomerated with the ball mill for 2 hours, then washed and dried.
- a solution A is prepared by mixing 275.5 ml of 3.45 mol / l yttrium nitrate solution and 24.9 ml of a solution of europium nitrate at 2.01 mol / l, and then completing at 1 I.
- 21 g of the previously prepared core are dispersed in 650 ml of deionized water, with stirring at 400 rpm, at room temperature.
- the pH is raised to 8.5 by the addition of 6N ammonia.
- 340 ml of solution A, which is still under stirring, are then added, over a period of 1 h 30, and under pH regulation, at a pH of 8.5, with 6N ammonia.
- a maturation of 1 h is carried out at the same temperature.
- the product obtained is then filtered, washed with 2 volumes of water, then dried at 100 ° C. for 5 hours and then calcined at 900 ° C. for 2 hours.
- the precursor is then obtained, the X-ray diffraction showing the presence of two distinct crystalline phases (Y, Eu) 2 ⁇ 3 and Y2O3.
- the product has a mean particle size (D50) equal to 7.5 microns.
- D50 mean particle size
- This example relates to a phosphor according to the invention.
- the precursor product obtained in Example 4 is calcined for 4 hours at 1500 ° C. under air and then deagglomerated in order to obtain a mean size (D50) of 7.5 ⁇ m.
- D50 mean size
- a luminophore emitting in the red under UV excitation is obtained.
- This phosphor has a PL of 100%.
- the yield is therefore identical to that of the comparative phosphor obtained from the precursor of Example 1 and after calcination under conditions identical to that of the present example for a saving of 30% in europium.
- This example relates to a precursor heart / shell according to the invention whose core is alumina.
- the product obtained is then filtered, washed with 2 volumes of water, then dried at 100 ° C. for 5 hours and then calcined at 900 ° C. for 2 hours.
- the precursor sought is then obtained.
- X-ray diffraction reveals the presence of two distinct crystalline phases (Y, Eu) 2 O 3 and Al 2 O 3 .
- the product has a mean particle size (D 5 o) equal to 6.5 microns.
- This example relates to a luminophore according to the invention obtained from the precursor of Example 6.
- Example 6 The precursor of Example 6 is calcined for 4 hours at 1550 ° C. under air. A luminophore emitting in the red under UV excitation is obtained. The Luminescence efficiency is measured by integrating the photoluminescence spectrum between 550 nm and 780 nm.
- This phosphor exhibits a luminescence efficiency of 100% relative to the luminophore obtained by calcination under equivalent conditions of the precursor of Example 1, for a granulometry (D 5 o) equal to 7.2 ⁇ m.
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Abstract
The invention relates to a composition, as well as to a phosphor containing said composition, including an inorganic core and a europium and yttrium oxide or gadolinium shell uniformly covering the inorganic core at a thickness greater than or equal to 300 nm. The composition is produced by: forming a suspension including the inorganic core and the pH of which is 8 to 11; adding a solution containing a europium salt and an yttrium or gadolinium salt to the suspension and maintaining the pH of the reaction medium at a constant value; and separating the formed solid and calcining same to a temperature of 1000°C at most.
Description
COMPOSITION A BASE D'EUROPIUM, D'OXYDE D'YTTRIUM OU DE COMPOSITION BASED ON EUROPIUM, YTTRIUM OXIDE OR
GADOLINIUM, DE TYPE CŒUR/COQUILLE, LUMINOPHORE COMPRENANT CETTE COMPOSITION ET PROCEDES DE PREPARATIONGADOLINIUM, CORE / SHELL TYPE, LUMINOPHORE COMPRISING THIS COMPOSITION AND PROCESSES FOR PREPARING THE SAME
La présente invention concerne une composition à base d'europium, d'oxyde d'yttrium ou de gadolinium, de type cœur/coquille, un luminophore comprenant cette composition ainsi que leurs procédés de préparation.The present invention relates to a composition based on europium, yttrium oxide or gadolinium, core / shell type, a phosphor comprising this composition and their methods of preparation.
Les oxydes d'yttrium ou de gadolinium dopés à l'europium sont bien connus pour leurs propriétés de luminescence. Ils émettent une lumière rouge lorsqu'ils sont irradiés par des rayonnements UV. Des luminophores exploitant cette propriété et à base de ces oxydes sont couramment utilisés à l'échelle industrielle, par exemple dans des lampes fluorescentes trichromatiques.The yttrium or gadolinium oxides doped with europium are well known for their luminescence properties. They emit a red light when irradiated by UV radiation. Phosphors exploiting this property and based on these oxides are commonly used on an industrial scale, for example in trichromatic fluorescent lamps.
Ces luminophores contiennent des terres rares dont le prix est élevé et est aussi soumis à des fluctuations importantes. La réduction du coût de ces luminophores constitue donc un enjeu important.These phosphors contain rare earths that are expensive and also subject to significant fluctuations. Reducing the cost of these luminophores is therefore an important issue.
De plus la rareté de certaines terres rares comme l'europium conduit à chercher à réduire la quantité de celles-ci dans les luminophores.Moreover the rarity of some rare earths such as europium leads to seek to reduce the amount of these in phosphors.
Il y a donc un besoin important en luminophores à quantité réduite en terres rares coûteuses, étant entendu bien sûr que cette réduction de la quantité ne doit pas se faire au détriment des propriétés de luminescence des luminophores, ces propriétés devant être du même ordre que celles des luminophores actuels.There is therefore a significant need for reduced-quantity rare-earthed phosphors, it being of course understood that this reduction in the quantity must not be to the detriment of the luminescence properties of the luminophores, these properties having to be of the same order as those current phosphors.
L'objet de l'invention est un luminophore répondant à ce besoin. Dans ce but, l'invention concerne une composition qui est caractérisée en ce qu'elle comprend :The object of the invention is a phosphor meeting this need. For this purpose, the invention relates to a composition which is characterized in that it comprises:
- un cœur minéral; et- a mineral heart; and
- une coquille à base d'oxyde d'europium et d'un oxyde d'yttrium ou de gadolinium et recouvrant de façon homogène le cœur minéral sur une épaisseur égale ou supérieure à 300 nm.a shell based on europium oxide and an yttrium or gadolinium oxide and homogeneously covering the mineral core to a thickness equal to or greater than 300 nm.
L'invention concerne aussi un luminophore qui est caractérisé en ce qu'il comprend une composition du type décrit ci-dessus.The invention also relates to a phosphor which is characterized in that it comprises a composition of the type described above.
Compte tenu de la présence spécifique du cœur minéral, qui occupe une bonne partie du volume du luminophore, la quantité de terre rare utilisée est réduite par rapport aux luminophores massifs actuellement connus, ce qui diminue son coût.
Néanmoins, hormis cette différence de structure interne, les luminophores de l'invention présentent des propriétés analogues à celles de luminophores actuellement connus.Given the specific presence of the mineral core, which occupies a large part of the volume of the phosphor, the amount of rare earth used is reduced compared to currently known solid phosphors, which reduces its cost. Nevertheless, apart from this difference in internal structure, the phosphors of the invention have properties similar to those of currently known phosphors.
En particulier, il s'avère que la présence du cœur non luminophore n'a pas d'influence significative sur les propriétés luminescentes des luminophores de l'invention. Dans la plupart des cas, on obtient des propriétés de luminescence similaires à celles obtenues avec des produits de l'art antérieur.In particular, it turns out that the presence of the non-phosphor core has no significant influence on the luminescent properties of the phosphors of the invention. In most cases, luminescence properties similar to those obtained with products of the prior art are obtained.
D'autres caractéristiques, détails et avantages de l'invention apparaîtront encore plus complètement à la lecture de la description qui va suivre, ainsi que des divers exemples concrets mais non limitatifs destinés à l'illustrer.Other features, details and advantages of the invention will appear even more fully on reading the description which follows, as well as various concrete but non-limiting examples intended to illustrate it.
On précise aussi pour la suite de la description que, sauf indication contraire, dans toutes les gammes ou limites de valeurs qui sont données, les valeurs aux bornes sont incluses, les gammes ou limites de valeurs ainsi définies couvrant donc toute valeur au moins égale et supérieure à la borne inférieure et/ou au plus égale ou inférieure à la borne supérieure.It is also specified for the remainder of the description that, unless otherwise indicated, in all ranges or limits of values that are given, the values at the terminals are included, the ranges or limits of values thus defined thus covering any value at least equal to and greater than the lower bound and / or at most equal to or less than the upper bound.
Par terre rare on entend pour la suite de la description les éléments du groupe constitué par l'yttrium et les éléments de la classification périodique de numéro atomique compris inclusivement entre 57 et 71.For rare earth is meant for the remainder of the description the elements of the group consisting of yttrium and the elements of the periodic classification of atomic number inclusive between 57 and 71.
On entend par surface spécifique, la surface spécifique B. ET. déterminée par adsorption du krypton. Les mesures de surface données dans la présente description ont été effectuées sur un appareil ASAP2010 après dégazage de la poudre pendant 8h, à 2000C.By specific surface is meant the specific surface B. AND. determined by adsorption of krypton. The surface measurements given in the present description were carried out on an ASAP2010 device after degassing the powder for 8 hours, at 200 ° C.
Comme cela a été vu plus haut, l'invention concerne deux types de produits : des compositions qui pourront être appelées aussi dans la suite de cette description « précurseurs », et des luminophores obtenus à partir de ces compositions ou précurseurs. Les luminophores ont, eux, des propriétés de luminescence suffisantes pour les rendre directement utilisables dans les applications souhaitées. Les précurseurs n'ont pas de propriétés de luminescence ou éventuellement des propriétés de luminescence trop faibles pour une utilisation dans ces mêmes applications.As has been seen above, the invention relates to two types of products: compositions which may be called also in the remainder of this description "precursors", and phosphors obtained from these compositions or precursors. The luminophores themselves have sufficient luminescence properties to make them directly usable in the desired applications. The precursors have no luminescence properties or possibly luminescence properties that are too low for use in these same applications.
Ces deux types de produits vont maintenant être décrits plus précisément.These two types of products will now be described more precisely.
Les compositions ou précurseursCompositions or precursors
Les compositions de l'invention se caractérisent essentiellement par leur structure spécifique de type cœur/coquille qui va être décrite en détail ci- dessous.The compositions of the invention are characterized essentially by their specific structure of the core / shell type which will be described in detail below.
Le cœur minéral est à base d'un matériau qui peut être notamment un oxyde ou un phosphate.
Parmi les oxydes, on peut citer en particulier les oxydes de zirconium, de zinc, de titane, de magnésium, d'aluminium (alumine) et les oxydes d'une ou plusieurs terres rares dont une peut éventuellement jouer le rôle de dopant.The mineral core is based on a material that can be in particular an oxide or a phosphate. Among the oxides, mention may in particular be made of oxides of zirconium, zinc, titanium, magnesium, aluminum (alumina) and the oxides of one or more rare earths, one of which may optionally act as a dopant.
Comme oxyde de terre rare on peut mentionner plus particulièrement encore l'oxyde de gadolinium, l'oxyde d'ytthum et l'oxyde de cérium.As the rare earth oxide, gadolinium oxide, ytthium oxide and cerium oxide may be mentioned more particularly.
L'oxyde d'yttrium, l'oxyde de gadolinium et l'alumine pourront être choisis de préférence. L'alumine peut être choisie encore plus préférentiellement car elle présente notamment l'avantage de permettre une calcination à température plus élevée lors du passage du précurseur au luminophore sans que l'on observe une diffusion du dopant dans le cœur. Ceci permet ainsi d'obtenir un produit dont les propriétés de luminescence sont optimales du fait d'une meilleure cristallisation de la coquille, conséquence de la température plus élevée de calcination.Yttrium oxide, gadolinium oxide and alumina may be chosen preferably. Alumina may be chosen even more preferably because it has the particular advantage of allowing a calcination at a higher temperature during the passage of the precursor to the phosphor without there being a diffusion of the dopant in the heart. This thus makes it possible to obtain a product whose luminescence properties are optimal because of a better crystallization of the shell, a consequence of the higher calcination temperature.
Parmi les phosphates, on peut mentionner les orthophosphates d'une ou plusieurs terres rares dont une peut éventuellement jouer le rôle de dopant, telles que le lanthane (LaPO4), le lanthane et le cérium ((LaCe)PO4), l'yttrium (YPO4), les polyphosphates de terres rares ou d'aluminium.Among the phosphates, mention may be made of orthophosphates of one or more rare earths, one of which may optionally act as a dopant, such as lanthanum (LaPO 4 ), lanthanum and cerium ((LaCe) PO 4 ), yttrium (YPO 4 ), polyphosphates of rare earths or aluminum.
Selon un mode de réalisation particulier, le matériau du cœur est un orthophosphate de lanthane, un orthophosphate de gadolinium ou un orthophosphate d'yttrium.According to a particular embodiment, the core material is a lanthanum orthophosphate, a gadolinium orthophosphate or an yttrium orthophosphate.
On peut aussi mentionner les phosphates alcalino-terreux comme Ca2P2θ7, le phosphate de zirconium ZrP2O7, les hydroxyapatites d'alcalino- terreux.Mention may also be made of alkaline earth phosphates such as Ca 2 P 2 O 7 , zirconium phosphate ZrP 2 O 7 , and alkaline earth hydroxylapatites.
Par ailleurs, conviennent d'autres composés minéraux tels que les vanadates, notamment de terre rare, (YVO4), les germanates, les silicates, notamment le silicate de zinc ou de zirconium, les tungstates, les molybdates, les sulfates (BaSO4), les borates (YBO3, GdBO3), les carbonates et les titanates (tel que BaTiO3), les zirconates, les aluminates de métaux alcalino- terreux, éventuellement dopés par une terre rare, comme les aluminates de baryum et/ou de magnésium, tels que MgAI2O4, BaAI2O4, ou BaMgAI 10O17.Furthermore, other mineral compounds such as vanadates, in particular rare earth (YVO 4 ), germanates, silicates, in particular zinc or zirconium silicate, tungstates, molybdates, sulphates (BaSO 4) are suitable. ), borates (YBO 3 , GdBO 3 ), carbonates and titanates (such as BaTiO 3 ), zirconates, alkaline earth metal aluminates, optionally doped with a rare earth, such as barium aluminates and / or magnesium, such as MgAl 2 O 4 , BaAl 2 O 4 , or BaMgAl 10O17.
Enfin, peuvent être appropriés les composés issus des composés précédents tels que les oxydes mixtes, notamment de terres rares, par exemple les oxydes mixtes de zirconium et de cérium, les phosphates mixtes, notamment de terres rares, et les phosphovanadates. En particulier, le matériau du cœur peut présenter des propriétés optiques particulières, notamment des propriétés réflectrices des rayonnements UV.
Par l'expression "le cœur minéral est à base de", on entend désigner un ensemble comprenant au moins 50%, de préférence au moins 70%, et plus préférentiellement au moins 80%, voire 90% en masse du matériau considéré. Selon un mode particulier, le cœur peut être essentiellement constitué par ledit matériau (à savoir en une teneur d'au moins 95% en masse, par exemple au moins 98%, voire au moins 99% en masse) ou encore entièrement constitué par ce matériau.Finally, compounds derived from the above compounds, such as mixed oxides, in particular rare earth oxides, for example mixed oxides of zirconium and cerium, mixed phosphates, in particular rare earths, and phosphovanadates, may be suitable. In particular, the core material may have particular optical properties, including reflective properties of UV radiation. By the expression "the mineral core is based on" is meant a set comprising at least 50%, preferably at least 70%, and more preferably at least 80% or 90% by weight of the material in question. According to a particular embodiment, the core may consist essentially of said material (ie at a content of at least 95% by weight, for example at least 98%, or even at least 99% by weight) or entirely constituted by this material. material.
Plusieurs variantes intéressantes de l'invention vont être décrites maintenant ci-dessous. Selon une première variante, le cœur est en un matériau dense ce qui correspond en fait à un matériau généralement bien cristallisé ou encore à un matériau dont la surface spécifique est faible.Several interesting variants of the invention will now be described below. According to a first variant, the core is made of a dense material which corresponds in fact to a generally well-crystallized material or to a material whose surface area is low.
Par surface spécifique faible, on entend une surface spécifique d'au plus 5 m2/g, plus particulièrement d'au plus 2 m2/g, encore plus particulièrement d'au plus 1 m2/g, et notamment d'au plus 0,6 m2/g.By low specific surface area is meant a specific surface area of at most 5 m 2 / g, more particularly at most 2 m 2 / g, even more particularly at most 1 m 2 / g, and especially from plus 0.6 m 2 / g.
Selon une autre variante, le cœur est à base d'un matériau stable en température. On entend par là un matériau dont le point de fusion se situe à une température élevée, qui ne se dégrade pas en sous produit gênant pour l'application comme luminophore à cette même température et qui reste cristallisé et donc qui ne se transforme pas en matériau amorphe toujours à cette même température. La température élevée qui est visée ici est une température au moins supérieure à 9000C, de préférence au moins supérieure à 10000C et encore plus préférentiellement d'au moins 1200°C.According to another variant, the core is based on a temperature-stable material. By this is meant a material whose melting point is at an elevated temperature, which does not degrade to a troublesome by-product for application as a luminophore at the same temperature and which remains crystallized and therefore does not become a material. amorphous still at this same temperature. The high temperature referred to herein is a temperature at least greater than 900 ° C., preferably at least greater than 1000 ° C. and even more preferably at least 1200 ° C.
La troisième variante consiste à utiliser pour le cœur un matériau qui combine les caractéristiques des deux variantes précédentes donc un matériau de faible surface spécifique et stable en température.The third variant consists in using for the core a material which combines the characteristics of the two previous variants, thus a material with a low specific surface area and temperature stability.
Le fait d'utiliser un cœur selon au moins une des variantes décrites ci- dessus, offre plusieurs avantages. Tout d'abord, la structure cœur/coquille du précurseur est particulièrement bien conservée dans le luminophore qui en est issu ce qui permet d'obtenir un avantage coût maximum.The use of a heart according to at least one of the variants described above has several advantages. Firstly, the core / shell structure of the precursor is particularly well preserved in the resulting phosphor which provides a maximum cost advantage.
Par ailleurs, il a été constaté que les luminophores obtenus à partir des précurseurs de l'invention dans la fabrication desquels on a utilisé un cœur selon au moins une des variantes précitées, présentaient des rendements de photoluminescence non seulement identiques mais dans certains cas supérieurs à ceux d'un luminophore de même composition mais qui ne présente pas la structure cœur-coquille.Furthermore, it has been found that the phosphors obtained from the precursors of the invention in the manufacture of which a core has been used according to at least one of the abovementioned variants, have photoluminescence yields which are not only identical but in some cases higher than those of a phosphor of the same composition but which does not have the core-shell structure.
Les matériaux du cœur peuvent être densifiés notamment en utilisant la technique connue des sels fondus. Cette technique consiste à porter le
matériau à densifier à une température élevée, par exemple d'au moins 9000C, éventuellement sous atmosphère réductrice, par exemple un mélange argon/hydrogène, en présence d'un agent fondant qui peut être choisi parmi les chlorures (chlorure de sodium, de potassium par exemple), les fluorures (fluorure de lithium par exemple), les borates (borate de lithium), les carbonates ou l'acide borique.The core materials can be densified, in particular by using the known technique of molten salts. This technique involves wearing the material to be densified at a high temperature, for example at least 900 ° C., optionally under a reducing atmosphere, for example an argon / hydrogen mixture, in the presence of a melting agent which may be chosen from chlorides (sodium chloride, for example), fluorides (lithium fluoride for example), borates (lithium borate), carbonates or boric acid.
Le cœur peut avoir un diamètre moyen compris notamment entre 1 et 10 μm.The core may have a mean diameter of in particular between 1 and 10 microns.
Ces valeurs de diamètre peuvent être déterminées par microscopie électronique à balayage (MEB) par comptage statistique d'au moins 150 particules.These diameter values can be determined by scanning electron microscopy (SEM) by random counting of at least 150 particles.
Les dimensions du cœur, de même que l'épaisseur de la coquille qui sera décrite plus loin, peuvent être mesurées notamment sur des photographies de microscopie électronique en transmission de coupes des compositions/précurseurs de l'invention.The dimensions of the core, as well as the thickness of the shell which will be described later, can be measured in particular in transmission electron microscopy photographs of sections of the compositions / precursors of the invention.
L'autre caractéristique de structure des compositions/précurseurs de l'invention est la coquille.The other structure characteristic of the compositions / precursors of the invention is the shell.
Cette coquille recouvre de façon homogène le cœur sur une épaisseur qui est égale ou supérieure à 300 nm. Par "homogène", on entend une couche continue, recouvrant totalement le cœur et dont l'épaisseur n'est de préférence jamais inférieure à 300 nm. Cette homogénéité est notamment visible sur des clichés de microscopie électronique à balayage. Des mesures de diffraction par des rayons X (DRX) mettent en évidence en outre la présence de 2 compositions distinctes entre le cœur et la coquille. L'épaisseur de la couche peut être plus particulièrement d'au moinsThis shell homogeneously covers the core to a thickness that is equal to or greater than 300 nm. By "homogeneous" is meant a continuous layer, completely covering the core and whose thickness is preferably never less than 300 nm. This homogeneity is particularly visible on scanning electron microscopy photographs. X-ray diffraction (XRD) measurements also reveal the presence of two distinct compositions between the heart and the shell. The thickness of the layer may be more particularly at least
500 nm et encore plus particulièrement d'au moins 700 nm. Elle peut être égale ou inférieure à 2000 nm (2 μm), plus particulièrement égale ou inférieure à 1500 nm et être comprise entre 750 nm et 1500 nm.500 nm and even more particularly at least 700 nm. It may be equal to or less than 2000 nm (2 μm), more particularly equal to or less than 1500 nm and be between 750 nm and 1500 nm.
La coquille est à base ou est constituée du produit aux propriétés de luminescence recherchées (luminophore rouge) ou susceptible de pouvoir donner de telle propriétés, c'est à dire qu'elle est à base ou constituée d'oxyde d'europium et d'un oxyde d'ytthum (Y2O3) ou de gadolinium (Gd2θ3) ou encore d'un oxyde mixte d'yttrium et de gadolinium ((Y, Gd)2O3), étant entendu que l'invention s'applique bien au cas de l'oxyde mixte même si la description par souci de simplification ne fait référence par la suite qu'à un oxyde d'yttrium ou à un oxyde de gadolinium. L'europium joue le rôle de dopant pour l'oxyde Ln2O3 (Ln désignant l'yttrium et/ou le gadolinium) c'est-à-dire qu'il confère des propriétés de luminescence à cet oxyde.
La quantité d'europium est généralement comprise entre 0,01 % et 20% en masse d'oxyde d'europium par rapport à la masse d'oxyde Ln2θ3. En fonction notamment des applications des compositions, cette quantité peut être comprise entre 4% et 15%, plus particulièrement entre 4% et 7%, notamment dans le cas des applications dans les lampes trichromatiques.The shell is based on or consists of the product with the desired luminescence properties (red phosphor) or capable of giving such properties, that is to say that it is based on or consists of europium oxide and a ytthum (Y 2 O 3 ) or gadolinium (Gd 2 θ 3 ) oxide or a mixed yttrium-gadolinium oxide ((Y, Gd) 2 O 3 ), it being understood that the invention It applies well to the case of the mixed oxide even if the description for the sake of simplification refers thereafter only to an yttrium oxide or a gadolinium oxide. The europium plays the role of dopant for the oxide Ln 2 O 3 (Ln denoting yttrium and / or gadolinium) that is to say that it confers luminescence properties to this oxide. The amount of europium is generally between 0.01% and 20% by weight of europium oxide relative to the oxide mass Ln 2 θ3. Depending in particular on the applications of the compositions, this amount may be between 4% and 15%, more particularly between 4% and 7%, especially in the case of applications in the trichromatic lamps.
D'une manière connue en soi, l'oxyde Ln2θ3 dopé à l'europium peut contenir éventuellement d'autres éléments supplémentaires choisis parmi les terres rares autres que l'europium, le gadolinium et l'yttrium. On peut citer notamment le terbium, le samarium ou le lanthane. Ces autres éléments peuvent être présents comme dopants en addition de l'europium, ce peut être le cas notamment du terbium ou du samarium. Dans un tel cas la quantité de cet élément supplémentaire est généralement d'au plus 1 % en masse d'oxyde de l'élément par rapport à la masse d'oxyde Ln2θ3. Ces autres éléments peuvent aussi être présents en substitution du gadolinium et/ou de l'yttrium. Ce peut être par exemple le cas du lanthane. Dans un tel cas la quantité de cet élément supplémentaire est généralement d'au plus 40%, plus particulièrement d'au plus 10%, en masse d'oxyde de l'élément par rapport à la masse d'oxyde Ln2O3. II est important de noter ici que les fonctions de dopant ou de substituant attribuées aux éléments précités ne l'ont été qu'à titre purement indicatif et non limitatif et que l'invention couvre tous les cas où la coquille comprend un oxyde Ln2O3 avec un de ces éléments supplémentaires quel que soit son rôle ou sa fonction dans cet oxyde. Les particules comprenant un cœur et une coquille qui constituent les compositions/précurseurs de l'invention présentent généralement un diamètre moyen qui est de préférence compris entre 1 ,6 μm et 15 μm. Ce diamètre peut être plus particulièrement compris entre 3 μm et 10 μm et encore plus particulièrement entre 4 μm et 8 μm. Le diamètre moyen auquel il est fait référence est la moyenne en volume des diamètres d'une population de particules.In a manner known per se, the europium doped Ln 2 θ 3 oxide may optionally contain other additional elements chosen from rare earths other than europium, gadolinium and yttrium. These include terbium, samarium or lanthanum. These other elements may be present as dopants in addition to europium, this may be the case in particular terbium or samarium. In such a case, the amount of this additional element is generally at most 1% by mass of oxide of the element relative to the oxide mass Ln 2 θ 3. These other elements may also be present in substitution of gadolinium and / or yttrium. This may be for example the case of lanthanum. In such a case, the amount of this additional element is generally at most 40%, more particularly at most 10%, by weight of oxide of the element relative to the weight of Ln 2 O 3 oxide. It is important to note here that the dopant or substituent functions attributed to the above-mentioned elements have been purely indicative and not limiting and that the invention covers all cases where the shell comprises an oxide Ln 2 O 3 with any of these additional elements regardless of its role or function in this oxide. The particles comprising a core and a shell which constitute the compositions / precursors of the invention generally have a mean diameter which is preferably between 1, 6 microns and 15 microns. This diameter may more particularly be between 3 μm and 10 μm and even more particularly between 4 μm and 8 μm. The average diameter referred to is the volume average of the diameters of a particle population.
Les valeurs de granulométhe données ici et pour le reste de la description sont mesurées par la technique de granulométhe laser, par exemple au moyen d'un granulométre laser de type Malvern, sur un échantillon de particules dispersées dans l'eau aux ultrasons (130 W) pendant 1 minute 30 secondes.
Par ailleurs, les particules ont de préférence un faible indice de dispersion, typiquement d'au plus 0,7, plus particulièrement d'au plus 0,6 et encore plus particulièrement d'au plus 0,5.The granulometry values given here and for the remainder of the description are measured by the laser granulometry technique, for example by means of a Malvern laser particle size analyzer, on a sample of particles dispersed in ultrasonic water (130 W ) for 1 minute 30 seconds. Moreover, the particles preferably have a low dispersion index, typically at most 0.7, more particularly at most 0.6 and even more particularly at most 0.5.
Par "indice de dispersion" d'une population de particules, on entend, au sens de la présente description, le rapport I tel que défini ci-dessous :
où : 084 est le diamètre des particules pour lequel 84% des particules ont un diamètre inférieur à 0s4;By "dispersion index" of a population of particles is meant, for the purposes of this description, the ratio I as defined below: where: 0 84 is the particle diameter for which 84% of the particles have a diameter less than 0s 4 ;
016 est le diamètre des particules pour lequel 16% des particules ont un diamètre inférieur à 0-IΘ; et016 is the particle diameter for which 16% of the particles have a diameter less than 0-1 ; and
050 est le diamètre moyen des particules, diamètre pour lequel 50% des particules ont un diamètre inférieur à 0so.050 is the average diameter of the particles, diameter for which 50% of the particles have a diameter less than 0so.
Bien que les compositions/précurseurs selon l'invention puissent présenter éventuellement des propriétés de luminescence après exposition à certaines longueurs d'onde, il est possible et même nécessaire d'améliorer encore ces propriétés de luminescence en procédant sur ces produits à des post-traitements, et ceci afin d'obtenir de véritables luminophores directement utilisables en tant que tels dans l'application souhaitée.Although the compositions / precursors according to the invention may optionally have luminescence properties after exposure to certain wavelengths, it is possible and even necessary to further improve these luminescence properties by treating these products with post-treatments. , and this in order to obtain real luminophores directly usable as such in the desired application.
On comprend que la frontière entre un précurseur et un réel luminophore reste arbitraire, et dépend du seul seuil de luminescence à partir duquel on considère qu'un produit peut être directement mis en œuvre de manière acceptable par un utilisateur.It is understood that the boundary between a precursor and a real phosphor remains arbitrary, and depends on the single luminescence threshold from which it is considered that a product can be directly implemented in a manner acceptable to a user.
Dans le cas présent, et de manière assez générale, on peut considérer et identifier comme précurseurs de luminophores des compositions selon l'invention qui n'ont pas été soumises à des traitements thermiques supérieurs à environ 10000C, car de tels produits présentent généralement des propriétés de luminescence que l'on peut juger comme ne satisfaisant pas au critère minimum de brillance des luminophores commerciaux susceptibles d'être utilisés directement et tels quels, sans aucune transformation ultérieure. A l'inverse, on peut qualifier de luminophores, les produits qui, éventuellement après avoir été soumis à des traitements appropriés, développent des brillances convenables, et suffisantes pour être utilisés directement par un applicateur, par exemple dans des lampes.In the present case, and in a rather general manner, it is possible to consider and identify as precursors of luminophores compositions according to the invention which have not been subjected to heat treatments greater than approximately 1000 ° C., since such products generally exhibit luminescence properties which can be judged as not satisfying the minimum brightness criterion of commercial phosphors which can be used directly and as such, without any subsequent transformation. Conversely, one can qualify as luminophores, the products which, possibly after being subjected to appropriate treatments, develop suitable glosses, and sufficient to be used directly by an applicator, for example in lamps.
La description des luminophores selon l'invention va être faite ci- dessous.The description of the phosphors according to the invention will be made below.
Les luminophoresThe luminophores
Les luminophores de l'invention sont constitués de, ou comprennent, les compositions de l'invention telles que décrites plus haut.
De ce fait tout ce qui a été décrit précédemment au sujet de ces compositions s'applique de même ici pour la description des luminophores selon l'invention. Il s'agit notamment de toutes les caractéristiques données plus haut sur la structure constituée par le cœur minéral et la coquille homogène, sur la nature du cœur minéral, sur celle de la coquille et notamment la compositions de l'oxyde Ln2θ3 ainsi que les caractéristiques de granulométhe.The luminophores of the invention consist of, or include, the compositions of the invention as described above. As a result, all that has been previously described with regard to these compositions is likewise applicable here for the description of the phosphors according to the invention. These include all the characteristics given above on the structure constituted by the mineral core and the homogeneous shell, on the nature of the mineral core, on that of the shell and in particular the compositions of the oxide Ln 2 θ 3 as well as granulomethane characteristics.
Comme on le verra plus loin, les luminophores de l'invention sont obtenus à partir des compositions/précurseurs par un traitement thermique qui a pour conséquence de ne pas modifier sensiblement les caractéristiques de ces compositions telles que mentionnées ci-dessus. Ce traitement entraine toutefois une meilleure cristallisation de l'oxyde Ln2θ3 de la coquille ce qui a pour conséquence essentielle d'améliorer les propriétés de luminescence.As will be seen below, the luminophores of the invention are obtained from the compositions / precursors by a heat treatment which has the consequence of not substantially modifying the characteristics of these compositions as mentioned above. However, this treatment leads to better crystallization of the Ln 2 θ 3 oxide of the shell, which has the essential consequence of improving the luminescence properties.
La description des procédés de préparation des compositions et des luminophores de l'invention va être faite ci-dessous.The description of the methods for preparing the compositions and phosphors of the invention will be made below.
Les procédés de préparationPreparation processes
Le procédé de préparation d'une composition selon l'invention est caractérisé en ce qu'il comporte les étapes suivantes :The process for preparing a composition according to the invention is characterized in that it comprises the following steps:
- (a) on forme une suspension comprenant le cœur minéral et dont le pH est compris entre 8 et 11 ;(a) forming a suspension comprising the inorganic core and having a pH of between 8 and 11;
- (b) on ajoute à ladite suspension une solution contenant un sel d'europium et un sel d'ytthum ou de gadolinium, avec, le cas échéant, un sel d'une terre rare autre que l'yttrium, l'europium ou le gadolinium, en maintenant le pH du milieu réactionnel à une valeur sensiblement constante; - (c) on sépare le solide du milieu formé à l'étape précédente;(b) adding to said suspension a solution containing a europium salt and a ytthum or gadolinium salt, with, if appropriate, a salt of a rare earth other than yttrium, europium or gadolinium, by maintaining the pH of the reaction medium at a substantially constant value; (c) separating the solid from the medium formed in the preceding step;
- (d) on calcine le solide ainsi obtenu à une température d'au plus 10000C.(d) the solid thus obtained is calcined at a temperature of at most 1000 ° C.
La première étape est donc une étape dans laquelle on forme une suspension qui est généralement une suspension aqueuse qui comprend le cœur minéral tel qu'il a été décrit plus haut. On choisit un cœur ayant une granulométrie adaptée à celle de la composition que l'on cherche à préparer. Ainsi, on peut utiliser notamment un cœur ayant un diamètre moyen compris notamment entre 1 et 10 μm et ayant un indice de dispersion d'au plus 0,7 ou d'au plus 0,6.The first step is therefore a step in which a suspension is formed which is generally an aqueous suspension which comprises the mineral core as described above. We choose a heart having a particle size adapted to that of the composition that is to be prepared. Thus, it is possible to use in particular a core having a mean diameter of in particular between 1 and 10 μm and having a dispersion index of at most 0.7 or at most 0.6.
Le pH de la suspension doit être compris entre 8 et 11 , plus particulièrement entre 8,5 et 9,5. Il est amené à cette valeur par addition à la suspension d'une base. Comme base convenable on peut citer, à titre d'exemples, les hydroxydes métalliques (NaOH, KOH, Ca(OH)2,....) ou bien encore l'hydroxyde d'ammonium.
La deuxième étape (b) du procédé met en œuvre une solution contenant un sel d'europium et, en fonction de la composition que l'on cherche à préparer, un sel d'yttrium et/ou de gadolinium. Dans le cas où l'on cherche à préparer une composition dans laquelle, comme on l'a vu plus haut, l'oxyde Ln2O3 de la coquille comprend d'autres terres rares supplémentaires, cette solution contient alors en outre un sel de la ou de ces terres rares supplémentaires.The pH of the suspension should be between 8 and 11, more particularly between 8.5 and 9.5. It is brought to this value by addition to the suspension of a base. Suitable bases include, for example, metal hydroxides (NaOH, KOH, Ca (OH) 2 , ....) or even ammonium hydroxide. The second step (b) of the process uses a solution containing a europium salt and, depending on the composition that is to be prepared, a yttrium salt and / or gadolinium. In the case where it is sought to prepare a composition in which, as seen above, the oxide Ln 2 O 3 of the shell comprises other rare earths, this solution then additionally contains a salt. of the one or more rare earths.
Parmi les sels convenables, on peut citer à titre d'exemple les chlorures, les nitrates, les sulfates ou acétates. Les nitrates peuvent être plus particulièrement utilisés.Suitable salts include, for example, chlorides, nitrates, sulphates or acetates. Nitrates can be used more particularly.
La solution est ajoutée à la suspension formée à l'étape précédente (a).The solution is added to the suspension formed in the previous step (a).
Cette addition se fait de préférence de manière progressive, par exemple sur une durée qui peut aller de 30 mn à 1 Oh, plus particulièrement de 30 mn à 2h, continue et sous agitation. D'autre part, selon une autre caractéristique importante du procédé de l'invention, qui permet notamment d'obtenir un revêtement homogène des particules du cœur minéral, cette addition se fait en maintenant le pH du milieu réactionnel à une valeur sensiblement constante, généralement à la valeur du pH de la suspension juste avant l'addition de la solution de sel. Cette valeur de pH peut être ainsi comprise entre 8 et 11 , plus particulièrement entre 8,5 et 9,5.This addition is preferably progressively, for example over a period which may range from 30 minutes to 1 hour, more particularly from 30 minutes to 2 hours, continuous and with stirring. On the other hand, according to another important characteristic of the process of the invention, which makes it possible in particular to obtain a homogeneous coating of the particles of the mineral core, this addition is done by maintaining the pH of the reaction medium at a substantially constant value, generally to the pH value of the suspension just before the addition of the salt solution. This pH value can thus be between 8 and 11, more particularly between 8.5 and 9.5.
Par pH maintenu à une valeur sensiblement constant on entend que le pH du milieu variera d'au plus 0,5 unité de pH autour de la valeur de consigne fixée et de préférence encore d'au plus 0,1 unité de pH autour de cette valeur. Pour atteindre ces valeurs de pH et assurer le contrôle de pH requis, on peut additionner au milieu réactionnel une base telle que décrite ci-dessus.By pH maintained at a substantially constant value it is meant that the pH of the medium will vary by not more than 0.5 pH units around the fixed set point and more preferably by at most 0.1 pH units around this value. To reach these pH values and ensure the required pH control, a base as described above can be added to the reaction medium.
L'addition de la solution à la suspension de la seconde étape (b) se fait à une température qui peut aller de l'ambiante (20-250C) jusqu'à 600C ou 80°C.The addition of the solution to the suspension of the second step (b) is carried out at a temperature which can range from ambient (20-25 ° C.) to 60 ° C. or 80 ° C.
La mise en contact de la suspension et de la solution entraine la formation d'un précipité qui comprend des particules d'un composé de terres rares (Y et/ou Gd et Eu) et d'ammonium déposé en couche homogène sur le cœur. Les variations des conditions de température et de vitesse d'introduction pendant le mélange de la solution et de la suspension permettent de faire varier les dimensions de ces particules. L'épaisseur de la couche peut varier en fonction des quantités respectives de sels et de cœur mises en œuvre.Contacting the suspension and the solution results in the formation of a precipitate which comprises particles of a rare earth compound (Y and / or Gd and Eu) and ammonium deposited in a homogeneous layer on the core. Variations in temperature and feed rate conditions during mixing of the solution and the slurry make it possible to vary the dimensions of these particles. The thickness of the layer may vary depending on the respective amounts of salt and heart used.
Dans une étape suivante (c), le précipité obtenu est séparé de la phase liquide du milieu réactionnel par tout procédé de séparation solide/liquide comme par exemple, filtration, centrifugation, décantation ou analogue. Il peut
également être soumis à un ou plusieurs lavages, pour, par exemple, éliminer les sels solubles.In a next step (c), the precipitate obtained is separated from the liquid phase of the reaction medium by any solid / liquid separation process such as, for example, filtration, centrifugation, decantation or the like. he can also be subjected to one or more washes, for example, to eliminate soluble salts.
Le précipité peut subir un séchage pour évaporer l'eau non liée par exemple par un traitement thermique entre 500C et 1000C, par un séchage sous pression réduite ou encore par atomisation.The precipitate can be dried to evaporate unbound water, for example by a heat treatment between 50 0 C and 100 0 C, by drying under reduced pressure or by spraying.
Il est possible, à l'issue de l'étape (b), d'effectuer un mûrissement du milieu réactionnel. On entend par étape de mûrissement le maintien du milieu obtenu après la fin de l'addition de la solution dans les mêmes conditions de température et d'agitation que celles de l'étape (b). La durée de cette étape de mûrissement peut être comprise par exemple entre 15 mn et 3h, ces valeurs étant données à titre purement indicatif et non limitatif.It is possible, after step (b), to ripen the reaction medium. The term "ripening step" means maintaining the medium obtained after the end of the addition of the solution under the same temperature and stirring conditions as those of step (b). The duration of this maturing step may be for example between 15 minutes and 3 hours, these values being given for purely indicative and not limiting.
Il est possible aussi d'effectuer le mûrissement sous pression, par exemple dans un autoclave, à une température qui peut être alors comprise entre 100°C et 2000C, plus particulièrement entre 100°C et 150°C. La dernière étape du procédé est une étape de calcination. Cette étape permet de transformer le composé de terres rares (Y et/ou Gd et Eu) et d'ammonium de la couche en un oxyde de ces mêmes terres rares. Cette calcination se fait généralement sous air.It is also possible to carry out the curing under pressure, for example in an autoclave, at a temperature which can then be between 100 ° C. and 200 ° C., more particularly between 100 ° C. and 150 ° C. The last step of the process is a calcination step. This step makes it possible to transform the compound of rare earths (Y and / or Gd and Eu) and ammonium of the layer into an oxide of these same rare earths. This calcination is generally done under air.
La durée de calcination peut être déterminée de manière classique par exemple par contrôle du poids constant. A titre purement indicatif, la durée de la calcination peut varier entre 30 mn et 6h environ.The duration of calcination can be determined conventionally, for example by controlling the constant weight. For information only, the duration of calcination can vary between 30 minutes and 6 hours.
A l'issue de ce traitement on obtient une composition ou un précurseur selon l'invention.At the end of this treatment, a composition or a precursor according to the invention is obtained.
Les luminophores de l'invention sont obtenus par calcination à une température d'au moins 12000C des compositions/précurseurs tels que décrits plus haut ou des compositions/précurseurs obtenus par le procédé qui a aussi été décrit précédemment. Cette température peut être comprise entre 1200°C et 1650°C environ, plus particulièrement entre 13000C et 1500°C.The luminophores of the invention are obtained by calcination at a temperature of at least 1200 ° C. of the compositions / precursors as described above or of the compositions / precursors obtained by the process which has also been described above. This temperature may be between 1200 ° C and 1650 ° C, more particularly between 1300 0 C and 1500 ° C.
Par ce traitement, les précurseurs sont transformés en luminophores efficaces.By this treatment, the precursors are converted into effective phosphors.
Bien que, comme on l'a indiqué plus haut, les précurseurs puissent eux- mêmes présenter des propriétés intrinsèques de luminescence, ces propriétés sont généralement insuffisantes pour les applications visées et elles sont grandement améliorées par le traitement de calcination. La calcination se fait généralement sous air.Although, as mentioned above, the precursors themselves may have intrinsic luminescence properties, these properties are generally insufficient for the intended applications and are greatly improved by the calcination treatment. Calcination is usually done under air.
De manière connue, la calcination peut se faire en présence d'un flux ou agent fondant comme, par exemple, le fluorure de lithium, le tétraborate de lithium, le chlorure de lithium, de sodium ou de baryum, le carbonate de
lithium, de sodium ou de baryum, le phosphate de lithium, le chlorure d'ammonium, l'oxyde de bore et l'acide borique et les phosphates d'ammonium, ainsi que leurs mélanges.In a known manner, the calcination can be carried out in the presence of a flux or fluxing agent such as, for example, lithium fluoride, lithium tetraborate, lithium chloride, sodium chloride or barium chloride, lithium, sodium or barium, lithium phosphate, ammonium chloride, boric oxide and boric acid and ammonium phosphates, and mixtures thereof.
Il est aussi possible de conduire la calcination en absence de tout flux donc sans mélange préalable de l'agent fondant avec le précurseur ce qui simplifie le procédé et ce qui contribue à diminuer le taux d'impuretés présentes dans le luminophore. De plus on évite ainsi l'utilisation de produits dont la mise en œuvre doit se faire dans des normes strictes de sécurité compte tenu de leur possible toxicité ce qui est le cas d'un nombre important des agents fondants mentionnés plus haut.It is also possible to carry out the calcination in the absence of any flux, thus without prior mixing of the melting agent with the precursor, which simplifies the process and contributes to reducing the level of impurities present in the phosphor. In addition, it avoids the use of products whose implementation must be made in strict safety standards given their potential toxicity which is the case of a large number of melting agents mentioned above.
Après traitement, le produit calciné est avantageusement lavé, de manière à obtenir un luminophore le plus pur possible et dans un état désaggloméré ou faiblement aggloméré. Dans ce dernier cas, il est possible de désagglomérer le luminophore en lui faisant subir un traitement de désagglomération dans des conditions douces.After treatment, the calcined product is advantageously washed, so as to obtain a phosphor as pure as possible and in a deagglomerated or weakly agglomerated state. In the latter case, it is possible to deagglomerate the phosphor by subjecting it to deagglomeration treatment under mild conditions.
Les traitements thermiques précités permettent d'obtenir des luminophores qui conservent une structure coeur/coquille et une distribution granulométrique très proches de celles des particules du précurseur.The aforementioned heat treatments make it possible to obtain luminophores which retain a core / shell structure and a particle size distribution very close to those of the precursor particles.
En outre, le traitement thermique peut être conduit sans induire des phénomènes sensibles de diffusion de l'europium de la couche luminophore externe vers de coeur.In addition, the heat treatment can be conducted without inducing sensitive phenomena of europium diffusion from the outer phosphor layer to the core.
On notera que selon une variante envisageable de l'invention, il est possible de conduire en une seule et même étape les calcinations successives des deux procédés qui ont été décrits, c'est-à-dire obtenir directement le luminophore sans s'arrêter au précurseur.It will be noted that according to one conceivable variant of the invention, it is possible to conduct in a single step the successive calcinations of the two processes which have been described, that is to say to obtain the luminophore directly without stopping at precursor.
Par ailleurs, l'invention couvre le luminophore susceptible d'être obtenu par le procédé de préparation décrit plus haut.Furthermore, the invention covers the phosphor obtainable by the preparation method described above.
De par leurs propriétés les luminophores de l'invention peuvent être utilisés dans les systèmes d'éclairage ou de visualisation présentant une source d'excitation dans la gamme UV (200 - 280 nm), par exemple autour deBy virtue of their properties, the phosphors of the invention can be used in lighting or visualization systems having an excitation source in the UV range (200-280 nm), for example around
254 nm. On notera en particulier les lampes trichromatiques à vapeur de mercure, les lampes pour rétro-éclairage des systèmes à cristaux liquides, sous forme tubulaire ou planaire (LCD Back Lighting). Ils présentent une forte brillance sous excitation UV, et une absence de perte de luminescence à la suite d'un post-traitement thermique. Leur luminescence est en particulier stable sous UV à des températures allant de l'ambiante jusqu'à 3000C.254 nm. Of particular note are mercury vapor trichromatic lamps, backlighting lamps for liquid crystal systems, in tubular or planar form (LCD Back Lighting). They exhibit a high gloss under UV excitation, and a lack of luminescence loss as a result of thermal post-treatment. Their luminescence is in particular stable under UV at temperatures ranging from ambient to 300 ° C.
Les luminophores de l'invention sont également de bons candidats comme luminophores rouges pour les systèmes à excitation VUV (ou
"plasma"), que sont par exemple les écrans plasma et les lampes trichromatiques sans mercure, notamment les lampes à excitation Xénon (tubulaires ou planaires). Les luminophores de l'invention possèdent une forte émission rouge sous excitation VUV (par exemple, autour de 147 nm et 172 nm). Les luminophores sont stables sous excitation VUV.The luminophores of the invention are also good candidates as red phosphors for VUV excitation systems (or "plasma"), such as plasma screens and trichromatic lamps without mercury, including Xenon excitation lamps (tubular or planar). The phosphors of the invention have a strong red emission under VUV excitation (for example, around 147 nm and 172 nm). The phosphors are stable under VUV excitation.
Les luminophores de l'invention peuvent également être utilisés comme luminophores rouges dans des dispositifs à excitation par diode électroluminescente. Ils peuvent être notamment utilisés dans des systèmes excitables dans le proche UV. Ils peuvent être également utilisés dans des systèmes de marquage à excitation UV.The phosphors of the invention can also be used as red phosphors in LED devices. They can be used especially in systems excitable in the near UV. They can also be used in UV excitation labeling systems.
Ils peuvent également être dispersés dans des matrices organiques (par exemple, des matrices plastiques ou des polymères transparents sous UV ...), minérales (par exemple, de la silice) ou hybrides organo-minérales. Les luminophores de l'invention peuvent être utilisés dans des systèmes d'excitation cathodique du type CRT (tubes à rayonnement cathodique) ou FED (field émission display) ou encore SED (surface émission display).They can also be dispersed in organic matrices (for example, plastic matrices or transparent polymers under UV ...), mineral (for example, silica) or organo-mineral hybrids. The phosphors of the invention can be used in cathode excitation systems of CRT (cathode ray tubes) or FED (field emission display) or SED (surface emission display) type.
Les luminophores de l'invention peuvent être mis en œuvre dans la fabrication des dispositifs mentionnés plus haut par des techniques bien connues, par exemple par sérigraphie, par pulvérisation, par électrophorèse ou sédimentation.The luminophores of the invention can be used in the manufacture of the devices mentioned above by well-known techniques, for example by screen printing, by spraying, by electrophoresis or sedimentation.
L'invention concerne aussi, selon un autre aspect, les dispositifs luminescents, comprenant, à titre de source de luminescence rouge, les luminophores tels que décrits plus haut ou les luminophores obtenus à partir du procédé décrit aussi précédemment.The invention also relates, in another aspect, to luminescent devices, comprising, as a source of red luminescence, the phosphors as described above or the phosphors obtained from the process also described above.
Des exemples vont maintenant être donnés.Examples will now be given.
Dans les exemples qui suivent, les particules préparées ont été caractérisées en termes de granulométhe, morphologie et composition par les méthodes suivantes. Mesures qranulométriquesIn the examples which follow, the particles prepared have been characterized in terms of granulometry, morphology and composition by the following methods. Quranometric measurements
Les diamètres de particules ont été déterminés au moyen d'un granulomètre laser (Malvern 2000) sur un échantillon de particules dispersées dans l'eau aux ultrasons (130 W) pendant 1 mn 30 secondes.Particle diameters were determined using a laser granulometer (Malvern 2000) on a sample of particles dispersed in ultrasonic water (130 W) for 1 min 30 seconds.
Microscopie électronique Les clichés de microscopie électronique à transmission sont réalisés sur une coupe (microtomie) des particules, en utilisant un microscope TEM haute résolution de type JEOL 2010 FEG. La résolution spatiale de l'appareil pour les mesures de composition chimique par EDS (spectroscopie à dispersion en
énergie) est < 2 nm. La corrélation des morphologies observées et des compositions chimiques mesurées permet de mettre en évidence la structure cœur-coquille, et de mesurer sur les clichés l'épaisseur de la coquille.Electron microscopy Transmission electron microscopy is performed on a section (microtomy) of the particles, using a JEOL 2010 FEG high resolution TEM microscope. The spatial resolution of the apparatus for the chemical composition measurements by EDS (scattering spectroscopy in energy) is <2 nm. The correlation of observed morphologies and measured chemical compositions makes it possible to highlight the core-shell structure, and to measure the thickness of the shell on the plates.
Les mesures de composition chimique peuvent être réalisées aussi par EDS sur des clichés effectués par STEM HAADF. La mesure correspond à une moyenne effectuée sur au moins deux spectres.The measurements of chemical composition can also be carried out by EDS on plates made by STEM HAADF. The measurement corresponds to an average performed on at least two spectra.
Diffraction aux rayons XX-ray diffraction
Les diffractogrammes X ont été réalisés en utilisant la raie Kα avec du cuivre comme anti-cathode, selon la méthode Bragg-Brendano. La résolution est choisie de manière à être suffisante pour séparer les raies des différents composés, de préférence elle est Δ(2Θ)<0,02°.X diffractograms were made using CuK α as with copper anti-cathode according to the Bragg-Brendano method. The resolution is chosen to be sufficient to separate the lines of the different compounds, preferably it is Δ (2Θ) <0.02 °.
EXEMPLE 1 COMPARATIFEXAMPLE 1 COMPARATIVE
Un oxyde de formule (Yo,95 Euo,os)2θ3 est préparé de la manière suivante. Une suspension contenant un oxalate neutre d'ytthum et d'europiumAn oxide of formula (Yo, 95 Eu 0, os) 2 O 3 is prepared in the following manner. A suspension containing a neutral oxalate of ytthum and europium
(0,095 mole d'ytthum pour 0,05 mole d'europium) est portée à 85°C. Une solution d'oxalate d'ammonium 0,255 M est ajoutée à cette suspension afin d'obtenir des rapports molaires oxalate / (Y+Eu) de 2 et ammoniaque / (Y+Eu) de 2. Le milieu réactionnel est maintenu sous agitation pendant uneh, le précipité obtenu est récupéré par filtration, puis lavé et séché à 1000C. Enfin, il est calciné à 9000C sous air pendant 2h. Il présente un diamètre moyen mesuré en granulométhe Malvern de 6,5 μm.(0.095 mole of ytthum for 0.05 mole of europium) is brought to 85 ° C. A solution of 0.255 M ammonium oxalate is added to this suspension in order to obtain molar ratios oxalate / (Y + Eu) of 2 and ammonia / (Y + Eu) of 2. The reaction medium is stirred for 1h, the precipitate obtained is recovered by filtration, then washed and dried at 100 ° C. Finally, it is calcined at 900 ° C. under air for 2 hours. It has a mean diameter measured in Malvern granulometry of 6.5 microns.
EXEMPLE 2 Cet exemple concerne un précurseur cœur/coquille selon l'invention dont le cœur est un phosphate de lanthane.EXAMPLE 2 This example relates to a core / shell precursor according to the invention, the core of which is a lanthanum phosphate.
Synthèse du cœur LaPO4 Synthesis of the heart LaPO 4
Dans 500 mL d'une solution d'acide phosphorique H3PO4 (1 ,725 mol/l) préalablement amenée à pH 1 ,9 par addition d'ammoniaque et portée à 60°C, sont ajoutés, en uneh, 500 ml d'une solution de nitrate de lanthane (1 ,5 mol/l). Le pH au cours de la précipitation est régulé à 1 ,9 par addition d'ammoniaque. A l'issue de l'étape de précipitation, le milieu réactionnel est encore maintenu 1 h à 600C. Le précipité est ensuite aisément récupéré par filtration, lavé à l'eau puis séché à 60°C sous air. La poudre obtenue est ensuite soumise à un traitement thermique à 900°C sous air.500 ml of a phosphoric acid solution H 3 PO 4 (1. 725 mol / l), previously brought to pH 1, 9 by addition of ammonia and heated to 60 ° C., are added in one hour to 500 ml. a solution of lanthanum nitrate (1, 5 mol / l). The pH during the precipitation is regulated to 1.9 by the addition of ammonia. At the end of the precipitation step, the reaction medium is further maintained for 1 h at 60 ° C. The precipitate is then easily recovered by filtration, washed with water and then dried at 60 ° C. in air. The powder obtained is then subjected to a heat treatment at 900 ° C. in air.
Le produit obtenu est densifié en le calcinant 2h en présence de 1 % en poids de LiF, à 11000C, sous atmosphère réductrice (Ar/H2). On obtient alors
un phosphate de terre rare de phase monazite. La taille moyenne des particules, mesurée par une statistique de 150 particules sur des clichés de microscopie (MEB), est de 3,2 μm.The product obtained is densified by calcining it for 2 hours in the presence of 1% by weight of LiF at 1100 ° C. under a reducing atmosphere (Ar / H 2 ). We then obtain a rare earth phosphate monazite phase. The average particle size, measured by a statistic of 150 particles on microscope slides (SEM), is 3.2 μm.
Synthèse du précurseurSynthesis of the precursor
Une solution A est préparée en mélangeant 275,5 ml de solution de nitrate d'ytthum à 3,45 mol/l et 24,9 ml d'une solution de nitrate d'europium à 2,01 mol/l, puis en complétant à 1 I.A solution A is prepared by mixing 275.5 ml of 3.45 mol / l solution of ytthum nitrate and 24.9 ml of a solution of europium nitrate at 2.01 mol / l and then completing at 1 I.
On disperse dans 650 ml d'eau désionisée 22 g du coeur précédemment préparé, sous agitation de 400 T/min., à température ambiante. Le pH est remonté à 8,5 par l'ajout d'ammoniaque 6N. On ajoute ensuite, en 1 h30, 340 ml de la solution A, toujours sous agitation, et sous régulation de pH, à pH de 8,5, par l'ammoniaque 6N. A l'issue de l'addition, un mûrissement d'1 h est effectué à la même température. Le produit obtenu est ensuite filtré, lavé par 2 volumes d'eau, puis séché à 1000C pendant 5h, puis calciné à 9000C pendant 2h.22 g of the previously prepared core are dispersed in 650 ml of deionized water, with stirring at 400 rpm, at room temperature. The pH is raised to 8.5 by the addition of 6N ammonia. 340 ml of solution A, which is still under stirring, are then added, over a period of 1 h 30, and under pH regulation, at a pH of 8.5, with 6N ammonia. At the end of the addition, a maturation of 1 h is carried out at the same temperature. The product obtained is then filtered, washed with 2 volumes of water, then dried at 100 ° C. for 5 hours and then calcined at 900 ° C. for 2 hours.
On obtient alors le précurseur cœur/coquille, la diffraction des rayons X met en évidence la présence de deux phases cristallines distinctes (Y,Eu)2θ3 et LaPO4. Le produit présente une granulométrie moyenne (D50) égale à 8,3 μm.The core / shell precursor is then obtained, the X-ray diffraction showing the presence of two distinct crystalline phases (Y, Eu) 2θ3 and LaPO 4 . The product has a mean particle size (D50) equal to 8.3 μm.
Un cliché de MET est réalisé sur le produit enrobé en résine, préparé par ultramicrotomie (épaisseur -100 nm) et disposé sur une membrane à trous.A TEM plate is made on the resin-coated product, prepared by ultramicrotomy (thickness -100 nm) and placed on a perforated membrane.
Les particules sont vues en coupe. Sur ce cliché, on observe une coupe de particule dont le coeur est sphérique et est entouré d'une coquille d'épaisseur moyenne de 800 nm.The particles are seen in section. In this photograph, we see a section of particle whose heart is spherical and is surrounded by a shell of average thickness of 800 nm.
EXEMPLE 3EXAMPLE 3
Cet exemple concerne un luminophore selon l'invention.This example relates to a phosphor according to the invention.
Le produit précurseur obtenu à l'exemple 2 est calciné pendant 4h à 1300°C sous air. On obtient un luminophore émettant dans le rouge sous excitation UV.The precursor product obtained in Example 2 is calcined for 4 hours at 1300 ° C. in air. A luminophore emitting in the red under UV excitation is obtained.
Ce luminophore présente un rendement de photoluminescence (PL) de 98% par rapport au luminophore obtenu par une calcination dans des conditions identiques de l'oxyde précurseur de l'exemple comparatif. Ce rendement est déterminé par l'intégration du spectre d'émission sous excitation de 254 nm, mesuré avec un spectrofluorimètre dans la gamme de longueur d'onde de 500 nm à 750 nm. Il est normalisé à 100% pour le luminophore comparatif.
La légère diminution du PL (2%) par rapport au luminophore comparatif obtenu à partir du précurseur de l'exemple 1 et après calcination dans des conditions identiques à celle du présent exemple est tout à fait acceptable compte tenu de l'économie de 30% réalisée en europium.This phosphor exhibits a photoluminescence (PL) efficiency of 98% relative to the luminophore obtained by calcination under identical conditions of the precursor oxide of the comparative example. This efficiency is determined by the integration of the emission spectrum under excitation of 254 nm, measured with a spectrofluorimeter in the wavelength range of 500 nm to 750 nm. It is 100% normalized for the comparative phosphor. The slight decrease in PL (2%) relative to the comparative phosphor obtained from the precursor of Example 1 and after calcination under conditions identical to that of the present example is entirely acceptable, given the saving of 30%. made in europium.
EXEMPLE 4EXAMPLE 4
Cet exemple concerne un précurseur cœur/coquille selon l'invention dont le cœur est un oxyde d'yttrium.This example relates to a core / shell precursor according to the invention, the core of which is an yttrium oxide.
Synthèse du cœur Y?OsSynthesis of the heart Y? Os
Un oxyde de formule Y2O3 est préparé selon un mode opératoire similaire à celui décrit dans l'exemple 1 comparatif. Ainsi, une suspension contenant un oxalate neutre d'yttrium est portée à 45°C. Une solution d'oxalate d'ammonium 0,255 M est ajoutée à cette suspension afin d'obtenir des rapports molaires oxalate / Y de 2,5 et ammoniaque / Y de 5. Le milieu réactionnel est maintenu sous agitation pendant 15 mn, le précipité obtenu est récupéré par filtration, puis lavé et séché à 1000C. Enfin, il est calciné à 9000C sous air pendant 2h. Il présente un diamètre moyen mesuré en granulométhe Malvern de 4 μm.An oxide of formula Y2O3 is prepared according to a procedure similar to that described in Comparative Example 1. Thus, a suspension containing a neutral oxalate of yttrium is brought to 45 ° C. A solution of 0.255 M ammonium oxalate is added to this suspension in order to obtain oxalate / Y molar ratios of 2.5 and ammonia / Y of 5. The reaction medium is stirred for 15 minutes, the precipitate obtained is recovered by filtration, then washed and dried at 100 ° C. Finally, it is calcined at 900 ° C. under air for 2 hours. It has a mean diameter measured in Malvern granulometry of 4 microns.
Le produit obtenu est ensuite calciné à 1450°C, en présence de 1 % en poids d'acide borique. Il est ensuite désaggloméré au broyeur à billes pendant 2 h, puis lavé et séché.The product obtained is then calcined at 1450 ° C. in the presence of 1% by weight of boric acid. It is then deagglomerated with the ball mill for 2 hours, then washed and dried.
Synthèse du précurseurSynthesis of the precursor
Une solution A est préparée en mélangeant 275,5 ml de solution de nitrate d'yttrium à 3,45 mol/l et 24,9 ml d'une solution de nitrate d'europium à 2,01 mol/l, puis en complétant à 1 I.A solution A is prepared by mixing 275.5 ml of 3.45 mol / l yttrium nitrate solution and 24.9 ml of a solution of europium nitrate at 2.01 mol / l, and then completing at 1 I.
On disperse dans 650 ml d'eau désionisée 21 g du coeur précédemment préparé, sous agitation de 400 T/min., à température ambiante. Le pH est remonté à 8,5 par l'ajout d'ammoniaque 6N. On ajoute ensuite, en 1 h30, 340 ml de la solution A, toujours sous agitation, et sous régulation de pH, à pH de 8,5, par l'ammoniaque 6N. A l'issue de l'addition, un mûrissement d'1 h est effectué à la même température.21 g of the previously prepared core are dispersed in 650 ml of deionized water, with stirring at 400 rpm, at room temperature. The pH is raised to 8.5 by the addition of 6N ammonia. 340 ml of solution A, which is still under stirring, are then added, over a period of 1 h 30, and under pH regulation, at a pH of 8.5, with 6N ammonia. At the end of the addition, a maturation of 1 h is carried out at the same temperature.
Le produit obtenu est ensuite filtré, lavé par 2 volumes d'eau, puis séché à 1000C pendant 5h, puis calciné à 9000C pendant 2h. On obtient alors le précurseur, la diffraction des rayons X met en évidence la présence de deux phases cristallines distinctes (Y,Eu)2θ3 et Y2O3. Le produit présente une granulométrie moyenne (D50) égale à 7,5 μm.
Sur un cliché MET réalisé comme décrit dans l'exemple 2, on observe une coupe de particule dont le coeur est sphérique et est entouré d'une coquille d'épaisseur moyenne de 800 nm.The product obtained is then filtered, washed with 2 volumes of water, then dried at 100 ° C. for 5 hours and then calcined at 900 ° C. for 2 hours. The precursor is then obtained, the X-ray diffraction showing the presence of two distinct crystalline phases (Y, Eu) 2θ3 and Y2O3. The product has a mean particle size (D50) equal to 7.5 microns. On a TEM shot made as described in Example 2, there is a particle section whose core is spherical and is surrounded by a shell of average thickness of 800 nm.
EXEMPLE 5EXAMPLE 5
Cet exemple concerne un luminophore selon l'invention. Le produit précurseur obtenu à l'exemple 4 est calciné pendant 4h à 15000C sous air, puis désaggloméré afin d'obtenir une taille moyenne (D50) de 7,5 μm. On obtient un luminophore émettant dans le rouge sous excitation UV. Ce luminophore présente un PL de 100%. On a donc un rendement identique à celui du luminophore comparatif obtenu à partir du précurseur de l'exemple 1 et après calcination dans des conditions identiques à celle du présent exemple pour une économie de 30% en europium.This example relates to a phosphor according to the invention. The precursor product obtained in Example 4 is calcined for 4 hours at 1500 ° C. under air and then deagglomerated in order to obtain a mean size (D50) of 7.5 μm. A luminophore emitting in the red under UV excitation is obtained. This phosphor has a PL of 100%. The yield is therefore identical to that of the comparative phosphor obtained from the precursor of Example 1 and after calcination under conditions identical to that of the present example for a saving of 30% in europium.
EXEMPLE 6EXAMPLE 6
Cet exemple concerne un précurseur cœur/coquille selon l'invention dont le cœur est en alumine.This example relates to a precursor heart / shell according to the invention whose core is alumina.
Une solution A est préparée en mélangeant 350 ml de solution de nitrate d'ytthum et d'europium à 2 mol/l (0,665 mol d'ytthum et 0,005 mol d'europium). On disperse dans 650 ml d'eau désionisée 15,3 g d'une poudre d'alumine de granulométhe laser D5o = 3 μm, sous agitation vigoureuse, à température ambiante. Le pH est remonté à 8,3 par l'ajout d'ammoniaque 6N.A solution A is prepared by mixing 350 ml of solution of ytthum nitrate and europium at 2 mol / l (0.665 mol of ytthum and 0.005 mol of europium). 15.3 g of a laser granulometry powder D 5 o = 3 μm, with vigorous stirring, are dispersed in 650 ml of deionized water at room temperature. The pH is raised to 8.3 by the addition of 6N ammonia.
On ajoute ensuite, en 1 h30, la solution A, toujours sous agitation, et sous régulation de pH (pH à 8,3). A l'issue de l'addition, un mûrissement d'1 h est effectué à la même température.Then, in 1 h 30, solution A is added, still under stirring, and under pH regulation (pH at 8.3). At the end of the addition, a maturation of 1 h is carried out at the same temperature.
Le produit obtenu est ensuite filtré, lavé par 2 volumes d'eau, puis séché à 1000C pendant 5h, puis calciné à 900°C pendant 2h.The product obtained is then filtered, washed with 2 volumes of water, then dried at 100 ° C. for 5 hours and then calcined at 900 ° C. for 2 hours.
On obtient alors le précurseur recherché. La diffraction des rayons X met en évidence la présence de deux phases cristallines distinctes (Y, Eu)2O3 et AI2O3.The precursor sought is then obtained. X-ray diffraction reveals the presence of two distinct crystalline phases (Y, Eu) 2 O 3 and Al 2 O 3 .
Le produit présente une granulométrie moyenne (D5o) égale à 6,5 μm.The product has a mean particle size (D 5 o) equal to 6.5 microns.
EXEMPLE 7EXAMPLE 7
Cet exemple concerne un luminophore selon l'invention obtenu à partir du précurseur de l'exemple 6.This example relates to a luminophore according to the invention obtained from the precursor of Example 6.
Le précurseur de l'exemple 6 est calciné pendant 4h à 15500C sous air. On obtient un luminophore émettant dans le rouge sous excitation UV. Le
rendement de luminescence est mesuré par intégration du spectre de photoluminescence entre 550 nm et 780 nm.The precursor of Example 6 is calcined for 4 hours at 1550 ° C. under air. A luminophore emitting in the red under UV excitation is obtained. The Luminescence efficiency is measured by integrating the photoluminescence spectrum between 550 nm and 780 nm.
Ce luminophore présente un rendement de luminescence de 100% par rapport au luminophore obtenu par une calcination dans des conditions équivalentes du précurseur de l'exemple 1 , pour une granulométhe (D5o) égale à 7, 2 μm.
This phosphor exhibits a luminescence efficiency of 100% relative to the luminophore obtained by calcination under equivalent conditions of the precursor of Example 1, for a granulometry (D 5 o) equal to 7.2 μm.
Claims
REVENDICATIONS
1- Composition caractérisée en ce qu'elle comprend : - un cœur minéral; et1- Composition characterized in that it comprises: - a mineral heart; and
- une coquille à base d'oxyde d'europium et d'un oxyde d'yttrium ou de gadolinium et recouvrant de façon homogène le cœur minéral sur une épaisseur égale ou supérieure à 300 nm.a shell based on europium oxide and an yttrium or gadolinium oxide and homogeneously covering the mineral core to a thickness equal to or greater than 300 nm.
2- Composition selon la revendication 1 , caractérisée en ce que le cœur minéral est à base d'un matériau dont la surface spécifique est d'au plus 5 m2/g, plus particulièrement d'au plus 1 m2/g.2- Composition according to claim 1, characterized in that the mineral core is based on a material whose specific surface area is at most 5 m 2 / g, more particularly at most 1 m 2 / g.
3- Composition selon la revendication 1 ou 2, caractérisée en ce que le cœur minéral est à base d'un orthophosphate de lanthane, d'un orthophosphate de gadolinium ou d'un orthophosphate d'yttrium ou d'un oxyde choisi parmi l'oxyde d'yttrium, l'oxyde de gadolinium, l'oxyde de zirconium et l'alumine.3- Composition according to claim 1 or 2, characterized in that the mineral core is based on a lanthanum orthophosphate, a gadolinium orthophosphate or an orthophosphate of yttrium or an oxide selected from yttrium oxide, gadolinium oxide, zirconium oxide and alumina.
4- Composition selon l'une des revendications précédentes, caractérisée en ce que la coquille comprend en outre, à titre de dopant de l'oxyde d'yttrium ou de gadolinium ou de substituant de l'élément yttrium ou gadolinium, au moins une terre rare autre que l 'yttrium, l'europium ou le gadolinium, qui peut être plus particulièrement le terbium, le samahum ou le lanthane.4- Composition according to one of the preceding claims, characterized in that the shell further comprises, as a dopant of yttrium oxide or gadolinium or substituent of the yttrium or gadolinium element, at least one earth rare other than yttrium, europium or gadolinium, which may be more particularly terbium, samahum or lanthanum.
5- Composition selon l'une des revendications précédentes, caractérisée en ce que la coquille recouvre le cœur sur une épaisseur égale ou inférieure à 2000 nm, plus particulièrement comprise entre 750 nm et 1500 nm.5. Composition according to one of the preceding claims, characterized in that the shell covers the core to a thickness equal to or less than 2000 nm, more particularly between 750 nm and 1500 nm.
6- Composition selon l'une des revendications précédentes, caractérisée en ce qu'elle est constituée de particules présentant un diamètre moyen comprise entre 1 ,6 et 15 μm.6. Composition according to one of the preceding claims, characterized in that it consists of particles having a mean diameter of between 1, 6 and 15 microns.
7- Luminophore, caractérisé en ce qu'il comprend une composition selon l'une des revendications précédentes.7- phosphor, characterized in that it comprises a composition according to one of the preceding claims.
8- Procédé de préparation d'une composition selon l'une des revendications 1 à 6, caractérisé en ce qu'il comporte les étapes suivantes :
- (a) on forme une suspension comprenant le cœur minéral et dont le pH est compris entre 8 et 11 ;8- Process for preparing a composition according to one of claims 1 to 6, characterized in that it comprises the following steps: (a) forming a suspension comprising the inorganic core and having a pH of between 8 and 11;
- (b) on ajoute à ladite suspension une solution contenant un sel d'europium et un sel d'ytthum ou de gadolinium, avec, le cas échéant, un sel d'une terre rare autre que l'yttrium, l'europium ou le gadolinium, en maintenant le pH du milieu réactionnel à une valeur sensiblement constante;(b) adding to said suspension a solution containing a europium salt and a ytthum or gadolinium salt, with, if appropriate, a salt of a rare earth other than yttrium, europium or gadolinium, by maintaining the pH of the reaction medium at a substantially constant value;
- (c) on sépare le solide du milieu formé à l'étape précédente;(c) separating the solid from the medium formed in the preceding step;
- (d) on calcine le solide ainsi obtenu à une température d'au plus 10000C.(d) the solid thus obtained is calcined at a temperature of at most 1000 ° C.
9- Procédé selon la revendication 8, caractérisé en ce que la suspension formée à la première étape (a) présente un pH compris entre 8,5 et 9,5.9- Method according to claim 8, characterized in that the suspension formed in the first step (a) has a pH between 8.5 and 9.5.
10- Procédé selon la revendication 8 ou 9, caractérisé en ce qu'il comprend une étape de mûrissement du milieu réactionnel à l'issue de l'étape (b).10- Method according to claim 8 or 9, characterized in that it comprises a step of maturing the reaction medium at the end of step (b).
11 - Procédé selon l'une des revendications 8 à 10, caractérisé en ce que lors de l'étape (b) le pH du milieu réactionnel est maintenu à une valeur constante comprise entre 8 et 11 , plus particulièrement entre 8,5 et 9,5.11 - Method according to one of claims 8 to 10, characterized in that during step (b) the pH of the reaction medium is maintained at a constant value between 8 and 11, more particularly between 8.5 and 9 5.
12- Procédé selon l'une des revendications 8 à 11 , caractérisé en ce que lors de l'étape (a) l'addition de la solution contenant les sels à la suspension se fait de manière progressive et sous agitation.12- Method according to one of claims 8 to 11, characterized in that during step (a) the addition of the solution containing the salts to the suspension is done gradually and with stirring.
13- Procédé de préparation d'un luminophore selon la revendication 7, caractérisé en ce qu'on calcine à une température d'au moins 12000C une composition selon l'une des revendications 1 à 6 ou une composition obtenue par le procédé selon l'une des revendications 8 à 12.13- A process for preparing a phosphor according to claim 7, characterized in that calcined at a temperature of at least 1200 0 C a composition according to one of claims 1 to 6 or a composition obtained by the method according to one of claims 8 to 12.
14- Procédé selon la revendication 13, caractérisé en ce que la calcination a lieu en présence d'un agent fondant.14- Method according to claim 13, characterized in that the calcination takes place in the presence of a fluxing agent.
15- Dispositif luminescent, caractérisé en ce qu'il comprend ou en ce qu'il est fabriqué en utilisant un luminophore selon la revendication 7 ou un luminophore obtenu par le procédé selon l'une des revendications 13 ou 14.
15- luminescent device, characterized in that it comprises or in that it is manufactured using a phosphor according to claim 7 or a phosphor obtained by the method according to one of claims 13 or 14.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR0901534A FR2943682B1 (en) | 2009-03-30 | 2009-03-30 | COMPOSITION BASED ON EUROPIUM, YTTRIUM OXIDE OR GADOLINIUM, HEART / SHELL TYPE, LUMINOPHORE COMPRISING THE SAME, AND PROCESSES FOR PREPARING THE SAME |
PCT/EP2010/053896 WO2010112394A1 (en) | 2009-03-30 | 2010-03-25 | Europium, yttrium oxide, or gadolinium core/shell composition, phosphor including said composition, and methods for preparing same |
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EP10710053A Withdrawn EP2414482A1 (en) | 2009-03-30 | 2010-03-25 | Europium, yttrium oxide, or gadolinium core/shell composition, phosphor including said composition, and methods for preparing same |
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US (1) | US9045679B2 (en) |
EP (1) | EP2414482A1 (en) |
JP (1) | JP6038648B2 (en) |
KR (1) | KR101350548B1 (en) |
CN (1) | CN102356142B (en) |
CA (1) | CA2752664C (en) |
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WO (1) | WO2010112394A1 (en) |
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US20130082207A1 (en) * | 2011-09-29 | 2013-04-04 | General Electric Company | Core-shell phosphor and method of making the same |
JP5613822B2 (en) | 2011-12-26 | 2014-10-29 | パナソニック株式会社 | Rare earth phosphovanadate phosphor and method for producing the same |
US20150165072A1 (en) * | 2012-08-06 | 2015-06-18 | University Of Iowa Research Foundation | Contrast imaging applications for lanthanide nanoparticles |
US20140124703A1 (en) * | 2012-09-02 | 2014-05-08 | Global Tungsten and Powders Corporation | BRIGHTNESS OF CE-TB CONTAINING PHOSPHOR AT REDUCED Tb WEIGHT PERCENTAGE |
US8851950B2 (en) | 2012-09-26 | 2014-10-07 | General Electric Company | Recyclability of fluorescent lamp phosphors |
WO2014122992A1 (en) * | 2013-02-05 | 2014-08-14 | コニカミノルタ株式会社 | Core/shell-type inorganic particles |
US10184051B2 (en) * | 2014-03-13 | 2019-01-22 | The Regents Of The University Of California | Solar energy absorbing coatings and methods of fabrication |
US9999907B2 (en) * | 2016-04-01 | 2018-06-19 | Applied Materials, Inc. | Cleaning process that precipitates yttrium oxy-flouride |
TW201925419A (en) | 2017-09-18 | 2019-07-01 | 德商馬克專利公司 | Multicomponent luminophores as colour converters for solid-state light sources |
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WO2008012266A1 (en) * | 2006-07-28 | 2008-01-31 | Rhodia Operations | Luminophore and core-shell luminophore precursors |
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US5518808A (en) * | 1992-12-18 | 1996-05-21 | E. I. Du Pont De Nemours And Company | Luminescent materials prepared by coating luminescent compositions onto substrate particles |
GB9911781D0 (en) * | 1999-05-20 | 1999-07-21 | Isis Innovations Ltd | Process for preparing phosphor particles |
JP3956095B2 (en) * | 2000-12-22 | 2007-08-08 | 信越化学工業株式会社 | Method for producing rare earth element oxide |
JP2004137482A (en) * | 2002-09-27 | 2004-05-13 | Fuji Photo Film Co Ltd | Method for coating particle surface |
DE102005000918A1 (en) * | 2005-01-06 | 2006-07-20 | Basf Ag | Process for the preparation of aqueous composite-particle dispersions |
WO2006077256A1 (en) * | 2005-01-24 | 2006-07-27 | Cinvention Ag | Metal containing composite materials |
US20060222757A1 (en) * | 2005-03-31 | 2006-10-05 | General Electric Company | Method for making phosphors |
JP4415972B2 (en) * | 2005-09-22 | 2010-02-17 | ソニー株式会社 | Method for producing metal oxide nanoparticles |
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KR20110122215A (en) | 2011-11-09 |
CN102356142B (en) | 2016-04-13 |
JP2012521953A (en) | 2012-09-20 |
FR2943682A1 (en) | 2010-10-01 |
US20120032113A1 (en) | 2012-02-09 |
WO2010112394A1 (en) | 2010-10-07 |
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