WO2013054901A1 - 酸窒化物蛍光体粉末、酸窒化物蛍光体粉末製造用窒化ケイ素粉末及び酸窒化物蛍光体粉末の製造方法 - Google Patents
酸窒化物蛍光体粉末、酸窒化物蛍光体粉末製造用窒化ケイ素粉末及び酸窒化物蛍光体粉末の製造方法 Download PDFInfo
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- WO2013054901A1 WO2013054901A1 PCT/JP2012/076485 JP2012076485W WO2013054901A1 WO 2013054901 A1 WO2013054901 A1 WO 2013054901A1 JP 2012076485 W JP2012076485 W JP 2012076485W WO 2013054901 A1 WO2013054901 A1 WO 2013054901A1
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- oxynitride phosphor
- phosphor powder
- powder
- silicon nitride
- oxynitride
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- 239000000843 powder Substances 0.000 title claims abstract description 369
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 54
- 239000000126 substance Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 59
- 229910021419 crystalline silicon Inorganic materials 0.000 claims abstract description 55
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 54
- 239000001301 oxygen Substances 0.000 claims abstract description 52
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 51
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000011261 inert gas Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 264
- 239000002245 particle Substances 0.000 claims description 101
- 239000011575 calcium Substances 0.000 claims description 39
- 239000002994 raw material Substances 0.000 claims description 39
- 239000013078 crystal Substances 0.000 claims description 38
- 229910052710 silicon Inorganic materials 0.000 claims description 33
- 239000010703 silicon Substances 0.000 claims description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 27
- 229910052782 aluminium Inorganic materials 0.000 claims description 22
- 238000010304 firing Methods 0.000 claims description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 18
- 229910052791 calcium Inorganic materials 0.000 claims description 18
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 13
- 229910052693 Europium Inorganic materials 0.000 claims description 13
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 13
- 238000009826 distribution Methods 0.000 claims description 12
- 230000005284 excitation Effects 0.000 claims description 10
- 229910003564 SiAlON Inorganic materials 0.000 abstract 1
- 238000007669 thermal treatment Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 35
- 238000005259 measurement Methods 0.000 description 28
- 229910001873 dinitrogen Inorganic materials 0.000 description 21
- 229910021417 amorphous silicon Inorganic materials 0.000 description 20
- -1 lanthanide metals Chemical class 0.000 description 18
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 238000013461 design Methods 0.000 description 11
- 238000002189 fluorescence spectrum Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000012535 impurity Substances 0.000 description 9
- 229910000077 silane Inorganic materials 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 8
- 229910000071 diazene Inorganic materials 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- 238000004438 BET method Methods 0.000 description 5
- PSBUJOCDKOWAGJ-UHFFFAOYSA-N azanylidyneeuropium Chemical compound [Eu]#N PSBUJOCDKOWAGJ-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000000634 powder X-ray diffraction Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 238000000992 sputter etching Methods 0.000 description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002524 electron diffraction data Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 229920003196 poly(1,3-dioxolane) Polymers 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- JHGCXUUFRJCMON-UHFFFAOYSA-J silicon(4+);tetraiodide Chemical compound [Si+4].[I-].[I-].[I-].[I-] JHGCXUUFRJCMON-UHFFFAOYSA-J 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910018509 Al—N Inorganic materials 0.000 description 1
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- UDGPSUJHSJAIAU-UHFFFAOYSA-N N(Cl)Cl.[Si] Chemical compound N(Cl)Cl.[Si] UDGPSUJHSJAIAU-UHFFFAOYSA-N 0.000 description 1
- 238000003991 Rietveld refinement Methods 0.000 description 1
- 229910007991 Si-N Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910006294 Si—N Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- XCNGEWCFFFJZJT-UHFFFAOYSA-N calcium;azanidylidenecalcium Chemical compound [Ca+2].[Ca]=[N-].[Ca]=[N-] XCNGEWCFFFJZJT-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000001579 optical reflectometry Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 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
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- AIFMYMZGQVTROK-UHFFFAOYSA-N silicon tetrabromide Chemical compound Br[Si](Br)(Br)Br AIFMYMZGQVTROK-UHFFFAOYSA-N 0.000 description 1
- CFTHARXEQHJSEH-UHFFFAOYSA-N silicon tetraiodide Chemical compound I[Si](I)(I)I CFTHARXEQHJSEH-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/77348—Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides
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- C01B21/0826—Silicon aluminium oxynitrides, i.e. sialons
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- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/597—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon oxynitride, e.g. SIALONS
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Definitions
- the present invention relates to an oxynitride phosphor powder composed of an ⁇ -sialon and aluminum nitride activated with a rare earth metal element, suitable for ultraviolet to blue light sources, silicon nitride powder for production of the oxynitride phosphor powder, and production It is about the method.
- an oxynitride phosphor powder showing a practical external quantum efficiency and fluorescence intensity in a fluorescence peak wavelength range of 595 to 605 nm a silicon nitride powder for producing the oxynitride phosphor powder, and a production method It is about.
- LEDs blue light emitting diodes
- white LEDs using these blue LEDs have been vigorously developed.
- White LEDs have lower power consumption and longer life than existing white light sources, and are therefore being used for backlights for liquid crystal panels, indoor and outdoor lighting devices, and the like.
- the white LED that has been developed is one in which YAG (yttrium, aluminum, garnet) doped with Ce is applied to the surface of a blue LED.
- YAG yttrium, aluminum, garnet
- the fluorescence peak wavelength of Ce-doped YAG is around 530 nm, and when this fluorescent color and blue LED light are mixed into white light, white light with a slight bluish color is obtained. Has the problem of poor color rendering.
- the ⁇ -sialon phosphor activated by Eu has a peak wavelength of about 580 nm, which is longer than the fluorescence peak wavelength of Ce-doped YAG ( (Yellow to orange) is known to generate fluorescence (see Patent Document 1), and a white LED is formed using the ⁇ -type sialon phosphor or in combination with a Ce-doped YAG phosphor.
- a white LED with a light bulb color having a lower color temperature than a white LED using only YAG doped with Ce can be produced.
- Patent Document 2 ⁇ -sialon powder synthesized in advance as raw material powder is added as a seed crystal for grain growth, whereby particles larger and smoother than before can be obtained, and pulverized from the synthesized powder.
- a phosphor having a fluorescence peak at a wavelength of 595 nm or more, which is excellent in luminous efficiency, by obtaining a powder having a specific particle size, and a method for producing the same are disclosed.
- this document does not show a specific example having a luminous efficiency that can be used with a phosphor having a fluorescence peak wavelength smaller than 599 nm and a phosphor larger than 601 nm.
- Patent Document 3 the general formula: (Ca ⁇ , Eu ⁇ ) (Si, Al) 12 (O, N) 16 (where 1.5 ⁇ + ⁇ ⁇ 2.2, 0 ⁇ ⁇ 0.2, O /N ⁇ 0.04), a light-emitting device characterized by using a phosphor having a specific surface area of 0.1 to 0.35 m 2 / g as a main component and ⁇ -sialon represented by A vehicular lamp and a headlamp are disclosed.
- this document does not show a specific example having a luminous efficiency that can be used with a phosphor having a fluorescence peak wavelength smaller than 592 nm and a phosphor larger than 600 nm.
- Patent Document 4 a metal compound mixture that can constitute a sialon phosphor by firing is fired in a specific temperature range in a gas at a specific pressure, and then pulverized and classified to a specific particle size.
- a sialon phosphor having a characteristic that emits light with higher brightness than conventional ones by performing heat treatment and a method for producing the same are disclosed.
- An object of the present invention is to provide an oxynitride phosphor having a fluorescence peak wavelength of 595 to 605 nm, preferably a novel oxynitride phosphor having an external quantum efficiency higher than conventional ones.
- Another object of the present invention is to provide a silicon nitride powder for producing an oxynitride phosphor powder for providing the above oxynitride phosphor.
- the present inventors have Composition formula: Ca x1 Eu x2 Si 12- (y + z) Al (y + z) O z N 16-z (However, in the formula, 0 ⁇ x1 ⁇ 3.40, 0.05 ⁇ x2 ⁇ 0.20, 4.0 ⁇ y ⁇ 7.0, 0 ⁇ z ⁇ 1) Is a phosphor obtained by mixing and firing a substance serving as a silicon source, a substance serving as an aluminum source, a substance serving as a calcium source, and a substance serving as a europium source so that the composition represented by The phosphor is an oxynitride phosphor powder containing ⁇ -sialon and aluminum nitride, and is excited by light having a wavelength of 450 nm, and emits fluorescence in a wide wavelength range from 595 nm to 605 nm.
- the inventors have found that an oxynitride phosphor powder with suitable
- the present invention Composition formula: Ca x1 Eu x2 Si 12- (y + z) Al (y + z) O z N 16-z (Where x1, x2, y, z are 0 ⁇ x1 ⁇ 3.40, 0.05 ⁇ x2 ⁇ 0.20, 4.0 ⁇ y ⁇ 7.0, 0 ⁇ z ⁇ 1)
- a composition represented by the following it is obtained by mixing a material serving as a silicon source, a material serving as an aluminum source, a material serving as a calcium source, and a material serving as a europium source, followed by firing.
- the present invention relates to an oxynitride phosphor powder comprising ⁇ -sialon and aluminum nitride.
- x1, x2, y, and z are: 0 ⁇ x1 ⁇ 3.40, 0.05 ⁇ x2 ⁇ 0.20, 4.50 ⁇ y ⁇ 5.50, 0 ⁇ z ⁇ 1.00 It is related with the oxynitride fluorescent substance powder characterized by these.
- x1, x2, y, and z are 1.37 ⁇ x1 ⁇ 2.60, 0.16 ⁇ x2 ⁇ 0.20, 4.50 ⁇ y ⁇ 5.50, 0 ⁇ z ⁇ 0.30 It is related with the oxynitride fluorescent substance powder characterized by these.
- x1, x2, y, and z are 1.70 ⁇ x1 ⁇ 2.60, 0.16 ⁇ x2 ⁇ 0.20, 4.50 ⁇ y ⁇ 5.05, 0 ⁇ z ⁇ 0.30 It is related with the oxynitride fluorescent substance powder characterized by these.
- x1, x2, y, and z are 1.70 ⁇ x1 ⁇ 2.60, 0.16 ⁇ x2 ⁇ 0.20, 4.50 ⁇ y ⁇ 5.05, 0 ⁇ z ⁇ 0.10 It is related with the oxynitride fluorescent substance powder characterized by these.
- the present invention also relates to an oxynitride phosphor powder characterized in that, in the composition formula, the content of aluminum nitride is greater than 0% by mass and less than 32% by mass.
- the present invention also relates to an oxynitride phosphor powder containing ⁇ -sialon and aluminum nitride, characterized in that the external quantum efficiency of fluorescence emitted when excited by light having a wavelength of 450 nm is 60% or more.
- the present invention also relates to an oxynitride phosphor powder characterized in that in the above oxynitride phosphor powder, the light reflectance is 80% or more.
- the present invention relates to an oxynitride phosphor powder.
- the 50% diameter (D 50 ) in the particle size distribution curve measured with a laser diffraction / scattering particle size distribution analyzer is 10.0 to 20.0 ⁇ m, and the specific surface area is 0.2 to 0.
- the present invention relates to an oxynitride phosphor powder characterized by being .6 m 2 / g.
- the present invention also relates to an oxynitride phosphor powder characterized in that the amorphous layer on the particle surface is less than 2 nm.
- the present invention is characterized by emitting fluorescence having a peak wavelength in a wavelength range of 595 nm to 605 nm when excited by light having a wavelength of 450 nm, and the external quantum efficiency at that time is 60% or more.
- the present invention relates to an oxynitride phosphor powder.
- x1, x2, y, and z are 1.37 ⁇ x1 ⁇ 2.60, 0.16 ⁇ x2 ⁇ 0.20, 4.50 ⁇ y ⁇ 5.50, 0 ⁇ z ⁇ 0.30
- the present invention relates to an oxynitride phosphor powder characterized in that it emits fluorescence having a peak wavelength in the wavelength range of 602 nm to 605 nm and has an external quantum efficiency of 60% or more.
- the present invention in another aspect, is a crystalline silicon nitride powder used as a raw material for producing the above oxynitride phosphor powder, having an oxygen content of 0.2 to 0.9 mass%
- the present invention relates to a silicon nitride powder for producing an oxynitride phosphor powder.
- the present invention also relates to the silicon nitride powder for producing an oxynitride phosphor powder, wherein the silicon nitride powder for producing the oxynitride phosphor powder has an average particle size of 1.0 to 12.0 ⁇ m. .
- the present invention also provides the silicon nitride powder for producing an oxynitride phosphor powder, wherein the silicon nitride powder for producing the oxynitride phosphor powder has a specific surface area of 0.2 to 3.0 m 2 / g. Relates to powder.
- the present invention is the composition formula, wherein x1, x2, y, z are 1.37 ⁇ x1 ⁇ 2.60, further 1.70 ⁇ x1 ⁇ 2.60, 0.16 ⁇ x2 ⁇ 0.20, 4.50 ⁇ y ⁇ 5.50, 0 ⁇ z ⁇ 0.30, and further 0 ⁇ z ⁇ 0.10
- the silicon nitride powder for producing the oxynitride phosphor powder is a crystalline silicon nitride powder used as a raw material for producing the oxynitride phosphor powder.
- the present invention in another aspect provides a composition formula: Ca x1 Eu x2 Si 12- (y + z) Al (y + z) O z N 16-z (Where x1, x2, y, z are 0 ⁇ x1 ⁇ 3.40, 0.05 ⁇ x2 ⁇ 0.20, 4.0 ⁇ y ⁇ 7.0, 0 ⁇ z ⁇ 1)
- a substance serving as a silicon source, a substance serving as an aluminum source, a substance serving as a calcium source, and a substance serving as a europium source are mixed, and 1500 to 2000 in an inert gas atmosphere.
- the present invention relates to a method for producing an oxynitride phosphor powder.
- the silicon source material is silicon nitride powder
- the silicon nitride powder has an oxygen content of 0.2 to 0.9 mass%, and an average particle size of 1.0 to
- the present invention relates to a method for producing an oxynitride phosphor powder, which is 12.0 ⁇ m and has a specific surface area of 0.2 to 3.0 m 2 / g.
- x1, x2, y, and z are 1.37 ⁇ x1 ⁇ 2.60, 0.16 ⁇ x2 ⁇ 0.20, 4.50 ⁇ y ⁇ 5.50, 0 ⁇ z ⁇ 0.30 It is related with the said manufacturing method of the oxynitride fluorescent substance powder characterized by being a manufacturing method of the oxynitride fluorescent substance powder which is.
- a novel oxynitride phosphor powder that emits fluorescence in a wide wavelength range from 595 nm to 605 nm when excited by light having a wavelength of 450 nm is provided.
- This novel oxynitride phosphor powder is preferably a high-efficiency oxynitride phosphor powder having a characteristic that the external quantum efficiency of fluorescence emitted by light having a wavelength of 450 nm is particularly large. be able to.
- the present invention also provides a silicon nitride powder that can be suitably used for producing the oxynitride phosphor powder, and a method for producing the oxynitride phosphor powder.
- FIG. 1 is a view showing a powder X-ray diffraction pattern of Example 2.
- FIG. 2 shows the powder X-ray diffraction pattern of Example 8.
- FIG. 3 is a view showing a powder X-ray diffraction pattern of Comparative Example 5.
- 4 is a scanning electron micrograph showing the silicon nitride powder for producing the oxynitride phosphor powder of Example 21.
- FIG. 5 is a scanning electron micrograph showing the oxynitride phosphor powder produced using the silicon nitride powder for production of oxynitride phosphor powder of Example 21.
- FIG. 1 is a view showing a powder X-ray diffraction pattern of Example 2.
- FIG. 2 shows the powder X-ray diffraction pattern of Example 8.
- FIG. 3 is a view showing a powder X-ray diffraction pattern of Comparative Example 5.
- 4 is a scanning electron micrograph showing the silicon nitride powder for producing the oxyn
- FIG. 6 is a scanning transmission electron micrograph of the cross section of the particle of the oxynitride phosphor powder produced using the silicon nitride powder for producing the oxynitride phosphor powder of Example 21.
- FIG. FIG. 7 is a scanning transmission electron micrograph of the visual field a in the vicinity of the surface of the cross section of the particle of the oxynitride phosphor powder shown in FIG.
- the present invention comprises a composition formula: Ca x1 Eu x2 Si 12- (y + z) Al (y + z) O z N 16-z
- the oxynitride phosphor represented by: 0 ⁇ x1 ⁇ 3.40, 0.05 ⁇ x2 ⁇ 0.20, 4.0 ⁇ y ⁇ 7.0, 0 ⁇ z ⁇ 1 ⁇ -sialon obtained by mixing and baking a substance serving as a silicon source, a substance serving as an aluminum source, a substance serving as a calcium source, and a substance serving as a europium source so that the composition represented by An oxynitride phosphor powder that emits fluorescence in a wide wavelength range of 595 nm to 605 nm when excited by light having a wavelength of 450 nm by forming an oxynitride phosphor powder containing aluminum and aluminum nitride
- the present invention relates to an oxynitride phosphor powder that has a particularly large
- ⁇ -type sialon particularly Ca-containing ⁇ -type sialon, is that part of Si-N bond of ⁇ -type silicon nitride is replaced by Al—N bond and Al—O bond, and Ca ions penetrate into the lattice and form a solid solution. It is a solid solution that maintains electrical neutrality.
- the ⁇ -type sialon phosphor included in the oxynitride phosphor of the present invention is activated by the blue light when the Ca-containing ⁇ -type sialon is activated by Eu intrusion into the lattice in addition to the Ca ions. When excited, the phosphor emits yellow to orange fluorescence represented by the above general formula.
- General rare earth elements ⁇ type was activated sialon phosphors, as described in Patent Document 1, MeSi 12- (m + n ) Al (m + n) O n N 16-n (Me is Ca, Mg, Y or one or more of lanthanide metals excluding La and Ce), and the metal Me is a large unit cell of ⁇ -sialon containing four formula amounts of (Si, Al) 3 (N, O) 4 From 1 to 3 per unit cell, up to 1 per unit cell.
- the metal element Me is divalent
- the solid solubility limit is 0.6 ⁇ m ⁇ 3.0 and 0 ⁇ n ⁇ 1.5 in the above general formula, and the metal Me is trivalent.
- the present inventors have found that the present invention is more in comparison with the phosphor in the composition range in which the ⁇ -sialon single phase is obtained.
- the luminous efficiency is dramatically improved in a composition region where an ⁇ -sialon single phase cannot be obtained conventionally.
- the oxynitride phosphor powder of the present invention is Composition formula: Ca x1 Eu x2 Si 12- (y + z) Al (y + z) O z N 16-z In 0 ⁇ x1 ⁇ 3.40, 0.05 ⁇ x2 ⁇ 0.20, 4.0 ⁇ y ⁇ 7.0, 0 ⁇ z ⁇ 1 ⁇ -sialon obtained by mixing and baking a substance serving as a silicon source, a substance serving as an aluminum source, a substance serving as a calcium source, and a substance serving as a europium source so that the composition represented by And an aluminum nitride nitride oxynitride phosphor powder.
- X1 and x2 are values indicating the amount of Ca ions and Eu ions penetrating into sialon, and when x2 is smaller than 0.05 or larger than 0.20, and when x1 is larger than 3.40, External quantum efficiency cannot be greater than 60%.
- x1 is preferably 1.37 or more, and more preferably 1.70.
- x2 is preferably 0.16 or more.
- the coefficient 2 of x1 in the formula is from the valence of Ca ions dissolved in the Ca-containing ⁇ -type sialon phosphor
- the coefficient 3 of x2 is from the valence of Eu ions dissolved in the Ca-containing ⁇ -type sialon phosphor. This is the number given.
- y is a value related to the amount of aluminum nitride produced. That is, when the y value exceeds the composition region where the ⁇ -sialon single phase is obtained, aluminum nitride and other aluminum-containing oxynitrides are generated.
- the ranges of y and z are 4.0 ⁇ y ⁇ 7.0 and 0 ⁇ z ⁇ 1.
- y and z have a composition in this range, it is possible to provide a highly efficient oxynitride phosphor powder having an external quantum efficiency of 60% or more.
- y is larger than 7.0, the amount of the aluminum nitride crystal phase to be generated becomes too large, and the external quantum efficiency cannot be made larger than 60%.
- y is smaller than 4.0, the external quantum efficiency cannot be made larger than 60%.
- z is a value relating to the substitutional solid solution amount of oxygen in ⁇ -sialon.
- the emission peak wavelength is smaller than 595 nm.
- the external quantum efficiency may be made larger than 60%.
- the range of 0 ⁇ y ⁇ 1.0 and 0 ⁇ z ⁇ 1.5 ⁇ -type sialon is generated, and the external quantum efficiency cannot be made larger than 60%.
- the ranges of x1, x2, y, and z are independently 1.37 ⁇ x1 ⁇ 3.40, 1.37 ⁇ x1 ⁇ 2.60, 1.70 ⁇ x1 ⁇ 2. .60, 0.16 ⁇ x2 ⁇ 0.20, 4.0 ⁇ y ⁇ 5.5, 4.5 ⁇ y ⁇ 5.5, 4.0 ⁇ y ⁇ 5.05, 4 0.5 ⁇ y ⁇ 5.05, 0 ⁇ z ⁇ 1, 0 ⁇ z ⁇ 0.30, and 0 ⁇ z ⁇ 0.10 are preferable. Therefore, any combination of these x1, x2, y and z ranges is preferred. Depending on the composition of x1, x2, y, and z within these ranges, an oxynitride phosphor powder with suitable external quantum efficiency is provided.
- the ranges of y and z are 4.6 ⁇ y ⁇ 5.5 and 0 ⁇ z ⁇ 1.
- y and z have a composition in this range, a highly efficient oxynitride phosphor powder having a higher external quantum efficiency is provided.
- one preferable oxynitride phosphor powder of the present invention is the composition formula, wherein x1, x2, y, z are 0 ⁇ x1 ⁇ 3.40, 0.05 ⁇ x2 ⁇ 0.20, 4.50 ⁇ y ⁇ 5.50, 0 ⁇ z ⁇ 1.00 It is.
- another preferable oxynitride phosphor powder of the present invention is the composition formula, wherein x1, x2, y, z are 1.37 ⁇ x1 ⁇ 2.60, 0.16 ⁇ x2 ⁇ 0.20, 4.50 ⁇ y ⁇ 5.50, 0 ⁇ z ⁇ 0.30 It is.
- Yet another preferred oxynitride phosphor powder of the present invention is the composition formula, wherein x1, x2, y, z are 1.37 ⁇ x1 ⁇ 2.60, 0.16 ⁇ x2 ⁇ 0.20, 4.50 ⁇ y ⁇ 5.05, 0 ⁇ z ⁇ 0.10 It is.
- the x1, x2, y, and z are 1.70 ⁇ x1 ⁇ 2.60, 0.16 ⁇ x2 ⁇ 0.20. 4.50 ⁇ y ⁇ 5.05 and 0 ⁇ z ⁇ 0.10 are preferable.
- the crystal phase of the oxynitride phosphor powder of the present invention is identified by an X-ray diffraction (XRD) apparatus using CuK ⁇ rays, the ⁇ -sialon crystal phase classified as trigonal and the aluminum nitride classified as hexagonal It consists of a crystalline phase.
- XRD X-ray diffraction
- the content of the aluminum nitride crystal phase contained in the oxynitride phosphor powder is preferably in the range of more than 0% by mass and less than 32% by mass.
- the content of the aluminum nitride crystal phase is 0.1% by mass or more, further 1% by mass or more. It may be in the range of 2% by mass or more, 4% by mass or more, 10% by mass or more, 30% by mass or less, and 25% by mass or less. It is preferable that no crystal phase other than ⁇ -sialon and aluminum nitride is contained.
- Other crystal phases that may be included include ⁇ -type silicon nitride, silicon oxide, calcium oxide, aluminum oxynitride, aluminum oxide, and the like, and the content is preferably 1% by mass or less.
- the oxynitride phosphor powder of the present invention does not need to contain fluorine or the like as impurities in addition to ⁇ -type sialon and aluminum nitride.
- the amount of impurities, particularly fluorine can be less than 30 ppm, even 20 ppm or less, 10 ppm or less, 1 ppm or less.
- the lattice constants of the ⁇ -type sialon crystal phase and the aluminum nitride crystal phase can be obtained by XRD measurement.
- the lattice constant of the ⁇ -type sialon crystal phase is outside the above range, the external quantum efficiency becomes small.
- the lattice constant of the aluminum nitride crystal phase is within the above range, the external quantum efficiency becomes larger.
- the identification of the crystal phase, the refinement of the lattice constant, and the quantification of the crystal phase in XRD measurement can be performed using X-ray pattern analysis software.
- the analysis software include PDXL manufactured by Rigaku Corporation.
- XRD measurement of the oxynitride phosphor powder, refinement of the lattice constant, and quantification of the crystal phase by the Rietveld method are performed using an X-ray diffractometer (Ultima IV IV Protectus) manufactured by Rigaku Corporation and analysis software (PDXL). went.
- the oxynitride phosphor powder of the present invention has a feature that the peak wavelength of fluorescence emitted when excited by light having a wavelength of 450 nm is 595 nm to 605 nm, particularly 602 nm to 605 nm, further 603 nm to 605 nm, and is a long wavelength. Furthermore, the external quantum efficiency of fluorescence having a long peak wavelength as described above, which is excited by light having a wavelength of 450 nm, can be 60% or more, particularly 62% or more and 64% or more. Its usefulness is remarkable because it is possible.
- the fluorescence emitted when excited by light having a wavelength of 450 nm has a peak wavelength of 602 nm to 605 nm, particularly 603 nm to 605 nm, and can have an external quantum efficiency of 63% or more. .
- the oxynitride phosphor powder of the present invention can have a light reflectance (light reflectance of light having a peak wavelength in the fluorescence spectrum of fluorescence emitted when excited with light of 450 nm) of 80% or more. Furthermore, it can be 81% or more, 83% or more, 84% or more, 85% or more.
- the oxynitride phosphor powder having a high light reflectance is obtained by further heat-treating the manufactured oxynitride phosphor powder, and the heat-treated oxynitride phosphor powder has a significantly improved external quantum efficiency. Therefore, it is preferable.
- This light reflectance can be measured using an ultraviolet / visible spectrophotometer or a spectrofluorophotometer.
- a spectrofluorometer When the reflectance is measured using a spectrofluorometer, it is possible to eliminate the influence of fluorescence, and measurement is possible over a wide wavelength range, which is preferable.
- the reflectance was measured using a measuring apparatus in which an integrating sphere was combined with a spectrofluorometer (FP-6500 manufactured by JASCO Corporation). Specifically, synchronous scanning measurement is performed to measure the intensity of the reflected light having the same wavelength as the incident light, the reflectance of the reflection standard (standard white plate) is set to 100%, and the reflectance of the sample powder is relative to the standard white plate. As a result, the reflectance was measured. The diffuse reflectance from 300 to 800 nm was measured, and the reflectance at the peak wavelength in the fluorescence spectrum was obtained.
- D 50 which is 50% diameter in the particle size distribution curve is 10.0 to 20.0 ⁇ m, and the specific surface area Is preferably 0.2 to 0.6 m 2 / g.
- D 50 is smaller than 10.0 ⁇ m and the specific surface area is larger than 0.6 m 2 / g, the emission intensity may be lowered, D 50 is larger than 20.0 ⁇ m, and the specific surface area is 0.1. If it is smaller than 2 m 2 / g, it is difficult to uniformly disperse in the resin that seals the phosphor, and the color tone of the white LED may vary.
- the particle diameter and specific surface area of the oxynitride phosphor powder of the present invention it is possible to control the particle diameter of the silicon nitride powder as a raw material.
- D 50 of the oxynitride phosphor powder is 10 ⁇ m or more and the specific surface area is 0.2 to 0.6 m 2. / G, which is preferable because the external quantum efficiency is further increased.
- D 50 of the oxynitride phosphor powder is a 50% diameter in a particle size distribution curve measured with a laser diffraction / scattering particle size distribution measuring apparatus.
- the specific surface area of the oxynitride phosphor powder was measured with a flowsorb 2300 type specific surface area measuring device (BET method by nitrogen gas adsorption method) manufactured by Shimadzu Corporation.
- the above-mentioned particle size and particle size distribution of the oxynitride phosphor powder of the present invention can be obtained without crushing (applying strong crushing force) the oxynitride phosphor powder obtained by firing the raw material mixture. It is noted that the powder obtained by so-called crushing treatment (treatment that breaks up the agglomeration between the particles without substantially crushing the primary particles) in order to break up the agglomeration generated during firing is described. It should be. It is known that when the pulverization process exceeds the pulverization, the particle surface is damaged and the fluorescence emission efficiency is lowered.
- the oxynitride phosphor powder of the present invention preferably has an amorphous layer on the particle surface of less than 2 nm, more preferably 1 nm or less. If the amorphous layer on the particle surface of the oxynitride phosphor is less than 2 nm, the external quantum efficiency is further increased.
- the particles of the oxynitride phosphor powder of the present invention preferably have no grain boundary phase in the particles. If the particles of the oxynitride phosphor are only the ⁇ -type sialon crystal phase and the aluminum nitride crystal phase and do not have a grain boundary phase inside the particles, the external quantum efficiency is further increased.
- the oxynitride phosphor powder of the present invention can emit fluorescence having a peak wavelength of 595 nm to 605 nm, particularly 602 nm to 605 nm, and further 603 nm to 605 nm by excitation of light in a wavelength region of 450 nm.
- the external quantum efficiency can be 60% or more, particularly 62% or more, 63% or more, or 64% or more.
- Fluorescent peak wavelength can be measured with a solid quantum efficiency measuring device combining an integrating sphere with FP6500 manufactured by JASCO Corporation. Although the fluorescence spectrum correction can be performed with a sub-standard light source, the fluorescence peak wavelength may cause a slight difference depending on the measurement instrument used and the correction conditions.
- the external quantum efficiency can be calculated from the product of the absorptance and internal quantum efficiency measured by a solid quantum efficiency measuring device combining an integrating sphere with FP6500 manufactured by JASCO Corporation.
- the oxynitride phosphor powder of the present invention can be used in various lighting fixtures as a light emitting element in combination with a light emitting source such as a known light emitting diode.
- an emission source having a peak wavelength of excitation light in the range of 330 to 500 nm is suitable for the oxynitride phosphor powder of the present invention.
- the light emission efficiency of the oxynitride phosphor powder is high, and a light emitting element with good performance can be configured.
- the luminous efficiency is high even with a blue light source, and a good light-white to daylight light-emitting element can be constituted by a combination of yellow to orange fluorescence of the oxynitride phosphor powder of the present invention and blue excitation light.
- the oxynitride phosphor powder of the present invention has a composition formula: Ca x1 Eu x2 Si 12- (y + z) Al (y + z) O z N 16-z In 0 ⁇ x1 ⁇ 3.40, 0.05 ⁇ x2 ⁇ 0.20, 4.0 ⁇ y ⁇ 7.0, 0 ⁇ z ⁇ 1
- a material that is a silicon source, a material that is a europium source, a material that is a calcium source, and a material that is an aluminum source are mixed in an inert gas atmosphere so that the composition represented by It is obtained by firing in the temperature range of ° C.
- the obtained fired product is further heat-treated at 1100 to 1600 ° C. in an inert gas atmosphere.
- the raw material silicon source material is selected from silicon nitride, oxynitride, oxide, or precursor material that becomes oxide by thermal decomposition.
- crystalline silicon nitride is preferable.
- an oxynitride phosphor having high external quantum efficiency can be obtained.
- the raw material that is the source of europium is selected from a europium nitride, oxynitride, oxide, or precursor material that becomes an oxide by thermal decomposition.
- Preferred is europium nitride (EuN).
- EuN europium nitride
- z can be further reduced and a phosphor having a long peak wavelength can be obtained.
- the raw material calcium source is selected from calcium nitride, oxynitride, oxide, or precursor material that becomes oxide by thermal decomposition. Preference is given to calcium nitride (Ca 3 N 2 ). By using Ca 3 N 2 , z can be further reduced and a phosphor having a long peak wavelength can be obtained.
- Examples of materials that can be used as a raw material aluminum source include aluminum oxide, metal aluminum, and aluminum nitride. Each of these powders may be used alone or in combination.
- the average particle diameter of the silicon nitride powder as a raw material for producing the oxynitride phosphor of the present invention is preferably 1.0 ⁇ m or more and 12.0 ⁇ m or less. More preferably, it is 3.0 ⁇ m or more and 12.0 ⁇ m or less. If the average particle size is less than 1.0 ⁇ m, the oxygen content tends to increase, and the effect of fluorescence characteristics becomes small. If the average particle size exceeds 12.0 ⁇ m, it is difficult to produce and practical. The average particle size of the silicon nitride powder was measured from a scanning electron micrograph of the silicon nitride powder.
- a circle is drawn in a scanning electron micrograph image, and for each particle in contact with the circle, the maximum circle inscribed in the particle is determined, and the diameter of the circle is defined as the particle diameter.
- the average particle diameter of the powder was calculated by taking the average of the diameters.
- the number of target measurement particles was about 50 to 150.
- the specific surface area of the silicon nitride powder is preferably 0.2 to 3.0 m 2 / g. More preferably 0.2 m 2 / g or more and 1.0 m 2 / g or less. Setting the specific surface area of the crystalline silicon nitride powder to less than 0.2 m 2 / g is difficult and impractical for manufacturing, and causes inconvenience for device fabrication. When the specific surface area exceeds 3 m 2 / g, the effect of fluorescence characteristics becomes small, so 0.2 to 3.0 m 2 / g is preferable.
- the specific surface area was measured with a Flowsorb 2300 type specific surface area measuring device (BET method by nitrogen gas adsorption method) manufactured by Shimadzu Corporation.
- crystalline silicon nitride powder can be preferably used as the silicon nitride powder used in the production of the oxynitride phosphor of the present invention, and ⁇ -type silicon nitride powder is preferable.
- crystalline silicon nitride powder and ⁇ -type silicon nitride powder having a low oxygen content can be preferably used as the silicon nitride powder used for producing the oxynitride phosphor of the present invention.
- the silicon nitride powder as a conventional phosphor material has an oxygen content of 1.0 to 2.0% by mass, and according to the present invention, a silicon nitride powder having a low oxygen content of 0.2 to 0.9% by mass is used.
- an oxynitride phosphor powder having higher fluorescence intensity than that of a conventional ⁇ -sialon phosphor can be obtained.
- the oxygen content in silicon nitride is preferably 0.2 to 0.8% by mass, more preferably 0.2 to 0.4% by mass. It is difficult to make the oxygen content less than 0.2% by mass, and when the oxygen content exceeds 0.9% by mass, no significant improvement in the fluorescence characteristics of the oxynitride phosphor powder of the present invention is observed.
- the oxygen content was measured with an oxygen-nitrogen simultaneous analyzer manufactured by LECO.
- the silicon nitride powder that can be preferably used for producing the oxynitride phosphor powder of the present invention can be obtained by thermally decomposing a nitrogen-containing silane compound and / or an amorphous silicon nitride powder.
- the nitrogen-containing silane compound include silicon diimide (Si (NH) 2 ), silicon tetraamide, silicon nitrogen imide, and silicon chlorimide.
- Si (NH) 2 silicon diimide
- silicon tetraamide silicon nitrogen imide
- silicon chlorimide silicon chlorimide.
- the amorphous silicon nitride powder can be obtained by a known method, for example, a method in which the nitrogen-containing silane compound is thermally decomposed at a temperature in the range of 1200 ° C. to 1460 ° C. in a nitrogen or ammonia gas atmosphere. Those produced by a method of reacting silicon halide such as silicon iodide or silicon tetraiodide with ammonia at a high temperature are used.
- the average particle size of the amorphous silicon nitride powder and the nitrogen-containing silane compound is usually 0.003 to 0.05 ⁇ m.
- the nitrogen-containing silane compound and the amorphous silicon nitride powder are easily hydrolyzed and oxidized, these raw material powders are weighed in an inert gas atmosphere.
- the oxygen concentration in the nitrogen gas circulated in the heating furnace used for the thermal decomposition of the nitrogen-containing silane compound can be controlled in the range of 0 to 2.0 vol%.
- the oxygen concentration in the atmosphere during the thermal decomposition of the nitrogen-containing silane compound is regulated to, for example, 100 ppm or less, preferably 10 ppm or less, and amorphous silicon nitride powder having a low oxygen content is obtained.
- the metal impurity mixed in the amorphous silicon nitride powder is reduced to 10 ppm or less by a known method in which the friction state between the powder and the metal in the reaction vessel material and the powder handling device is improved.
- the nitrogen-containing silane compound and / or the amorphous silicon nitride powder is fired at 1300 to 1700 ° C. in a nitrogen or ammonia gas atmosphere to obtain a crystalline silicon nitride powder.
- the particle size is controlled by controlling the firing conditions (temperature and heating rate).
- the crystalline silicon nitride powder obtained in this way has large primary particles in a substantially monodispersed state and almost no aggregated particles and fused particles.
- the obtained crystalline silicon nitride powder is a high-purity powder having a metal impurity of 100 ppm or less.
- a low oxygen crystalline silicon nitride powder can be obtained by chemical treatment such as acid cleaning of the crystalline silicon nitride powder. In this way, the silicon nitride powder for producing a silicon oxynitride phosphor powder having an oxygen content of 0.2 to 0.9% by mass of the present invention can be obtained.
- the silicon nitride powder thus obtained does not require strong pulverization unlike silicon nitride produced by the direct nitridation method of metal silicon, and therefore, the amount of impurities is extremely low at 100 ppm or less.
- Impurities (Al, Ca, Fe) contained in the crystalline silicon nitride powder of the present invention are preferably 100 ppm or less, and preferably 20 ppm or less because an oxynitride phosphor powder having a large external quantum efficiency can be obtained.
- the above-mentioned silicon nitride powder raw material having a low oxygen content can be generally preferably used for producing the oxynitride phosphor of the present invention.
- x1, x2, y, and z are 1.37 ⁇ x1 ⁇ 2.60, 0.16 ⁇ x2 ⁇ 0.20, 4.50 ⁇ y ⁇ 5.50, and 0 ⁇ z ⁇ . It is also useful for producing an oxynitride phosphor powder having a value of 0.30.
- the silicon nitride powder raw material has the above-mentioned low oxygen content, and the average particle diameter is in the range of 1.0 ⁇ m to 12.0 ⁇ m, and further 3.0 ⁇ m to 12.0 ⁇ m, as described above.
- the specific surface area is preferably in the range of 0.2 to 3.0 m 2 / g, more preferably 0.2 m 2 / g to 1.0 m 2 / g.
- a Li-containing compound serving as a sintering aid for the purpose of promoting sintering and generating an ⁇ -sialon crystal phase at a lower temperature.
- the Li-containing compound used include lithium oxide, lithium carbonate, metallic lithium, and lithium nitride. Each of these powders may be used alone or in combination.
- the addition amount of the Li-containing compound is suitably 0.01 to 0.5 mol as the Li element with respect to 1 mol of the oxynitride fired product.
- the method of mixing the silicon source material, the europium source material, the calcium source material, and the aluminum source material is a method known per se, for example, dry mixing.
- a method, a method of removing the solvent after wet mixing in an inert solvent that does not substantially react with each component of the raw material, and the like can be employed.
- the mixing device a V-type mixer, a rocking mixer, a ball mill, a vibration mill, a medium stirring mill, or the like is preferably used.
- a fired oxynitride represented by the composition formula can be obtained. If it is lower than 1500 ° C., it takes a long time to produce ⁇ -sialon, which is not practical. When the temperature is higher than 2000 ° C., silicon nitride and ⁇ -sialon are sublimated and decomposed to generate free silicon, so that an oxynitride phosphor powder with high external quantum efficiency cannot be obtained.
- the heating furnace used for firing there is no particular limitation on the heating furnace used for firing as long as firing in the range of 1500 to 2000 ° C. is possible in an inert gas atmosphere.
- a batch type electric furnace, a rotary kiln, a fluidized firing furnace, a pusher type electric furnace, or the like by a high frequency induction heating method or a resistance heating method can be used.
- a BN crucible, a silicon nitride crucible, a graphite crucible, or a silicon carbide crucible can be used as the crucible for filling the mixture.
- the fired oxynitride obtained by firing is a powder with less aggregation and good dispersibility.
- the oxynitride fired product obtained by the firing is further heat-treated.
- the obtained oxynitride fired product is heat-treated in an inert gas atmosphere or a reducing gas atmosphere at a temperature range of 1100 to 1600 ° C., and is excited by light having a wavelength of 450 nm, whereby a peak wavelength is obtained.
- the heat treatment temperature is preferably in the range of 1500 to 1600 ° C. When the heat treatment temperature is less than 1100 ° C.
- the holding time at the maximum temperature when the heat treatment is performed is preferably 0.5 hours or more. Even if the heat treatment is performed for more than 4 hours, the improvement of the external quantum efficiency with the extension of the time remains little or hardly changes. Therefore, the holding time at the maximum temperature when performing the heat treatment is 0.5. It is preferably in the range of 4 hours.
- the heating furnace used for the heat treatment is not particularly limited.
- a batch type electric furnace, a rotary kiln, a fluidized firing furnace, a pusher type electric furnace, or the like by a high frequency induction heating method or a resistance heating method can be used.
- a BN crucible, a silicon nitride crucible, a graphite crucible, a silicon carbide crucible, or an alumina crucible can be used.
- the fluorescence peak wavelength of the oxynitride phosphor powder of the present invention is calcinated before the heat treatment. As compared with the product, it shifts to the longer wavelength side by about 0.5 to 2.5 nm, and at the same time, the external quantum efficiency and the emission intensity at the fluorescence peak wavelength are improved.
- the oxynitride phosphor powder of the present invention thus heat-treated can have an improved external quantum efficiency.
- the heat-treated oxynitride phosphor powder of the present invention can have a light reflectance of 80% or more, more preferably 83% or more, and 85% or more. Oxynitride phosphor powders with high light reflectivity can have improved external quantum efficiency.
- a preferred embodiment of the oxynitride phosphor powder of the present invention is a phosphor powder obtained by the production method described above, and more specifically, a substance serving as a silicon source, a substance serving as a europium source, and a calcium source. And a material to be an aluminum source are mixed, fired in an inert gas atmosphere at a temperature range of 1500 to 2000 ° C., and then heat-treated in an inert gas atmosphere at a temperature range of 1100 to 1600 ° C.
- composition formula Ca x1 Eu x2 Si 12- (y + z) Al (y + z) O z N 16-z In 0 ⁇ x1 ⁇ 3.40, 0.05 ⁇ x2 ⁇ 0.20, 4.0 ⁇ y ⁇ 7.0, 0 ⁇ z ⁇ 1
- Example 1 Silicon nitride, europium nitride, aluminum nitride, and calcium nitride are weighed in a glove box purged with nitrogen so as to have the oxynitride composition shown in Table 1, and mixed using a dry-type vibration mill. Got.
- the specific surface area, average particle diameter and oxygen content of the raw crystalline silicon nitride powder were 0.3 m 2 / g, 8.0 ⁇ m and 0.29 mass%, respectively.
- After the obtained mixed powder is put into a silicon nitride crucible, charged into a graphite resistance heating type electric furnace, and heated to 1725 ° C. while maintaining normal pressure while circulating nitrogen in the electric furnace. And kept at 1725 ° C. for 12 hours to obtain a fired oxynitride.
- the obtained oxynitride fired product was crushed to obtain a powder having a particle size of 5 to 20 ⁇ m (oxynitride phosphor powder before heat treatment) by classification, and the obtained powder was put in an alumina crucible, This is charged into a graphite resistance heating type electric furnace, heated to 1600 ° C. while maintaining normal pressure while circulating nitrogen in the electric furnace, held at 1600 ° C. for 1 hour, crushed, An oxynitride phosphor powder of the invention (oxynitride phosphor powder after heat treatment; hereinafter, this powder is referred to as oxynitride phosphor powder unless otherwise noted).
- D 50 of the oxynitride phosphor powder of the present invention is a 50% diameter in a particle size distribution curve measured with a laser diffraction / scattering particle size distribution measuring apparatus.
- the specific surface area of the oxynitride phosphor powder was measured by a BET method using a nitrogen gas adsorption method using a flowsorb 2300 type specific surface area measuring device manufactured by Shimadzu Corporation.
- a solid quantum efficiency measurement device combining an integrating sphere with FP-6500 manufactured by JASCO Corporation was used, at an excitation wavelength of 450 nm.
- the fluorescence spectrum was measured, and at the same time, the absorptance and internal quantum efficiency were measured.
- the fluorescence peak wavelength and the emission intensity at that wavelength were derived from the obtained fluorescence spectrum, and the external quantum efficiency was calculated from the absorptance and the internal quantum efficiency.
- the relative fluorescence intensity which is an index of luminance, is the fluorescence peak when the maximum intensity value of the emission spectrum at the same excitation wavelength of a commercially available YAG: Ce phosphor (P46Y3 manufactured by Kasei Optonix) is 100%. The relative value of the emission intensity at the wavelength was used.
- Table 1 The evaluation results of the fluorescence characteristics of the oxynitride phosphor powder according to Example 1 are shown in Table 1, and the generated crystal phase and content, lattice constant, specific surface area, and average particle diameter of the oxynitride phosphor powder are shown in Table 1. It shows in Table 2.
- the fluorescence characteristics of the oxynitride phosphor powder before heat treatment were measured by the above method, and the results are shown in Table 1. Further, the light reflectance of the oxynitride phosphor powder before and after the heat treatment was measured. The results are shown in Table 3.
- the particles of the obtained oxynitride phosphor powder were thinned by Ar ion milling, and the cross section of the particles was observed by STEM. It was confirmed that there were no grain boundaries inside the particles. Further, the region where the crystal lattice existing on the particle surface was not confirmed was confirmed to be amorphous by an electron diffraction pattern. When the thickness of the region was measured at three locations, it was confirmed that the thickness of the amorphous region on the particle surface, that is, the thickness of the amorphous layer was less than 2 nm. Further, the thickness of the amorphous layer on the particle surface was 1 nm or less in all the examples of the present invention.
- Examples 2 to 11 The oxynitride phosphor powder was prepared in the same manner as in Example 1 except that the raw material powders according to Examples 2 to 11 were weighed and mixed so that the oxynitride phosphor powder had the design composition shown in Table 1. Obtained.
- the fluorescence characteristics, average particle diameter, specific surface area, generated crystal phase and content, and lattice constant of the obtained oxynitride phosphor powder were measured in the same manner as in Example 1. The results are shown in Tables 1 and 2.
- the specific surface area, average particle diameter and oxygen content of the raw crystalline silicon nitride powder were 0.3 m 2 / g, 8.0 ⁇ m and 0.29 mass%, respectively.
- the powder X-ray diffraction patterns of Examples 2 and 8 are shown in FIGS. 1 and 2, it can be seen that the generated crystal phase is an ⁇ -type sialon phase and an aluminum nitride phase.
- Example 1 the results of measuring the fluorescence characteristics of the oxynitride phosphor powder before heat treatment are shown in Table 1, and the light reflectance of the oxynitride phosphor powder before and after heat treatment is shown in Table 3.
- Example 12 The specific surface area, average particle diameter, and oxygen content of the crystalline silicon nitride powder as a raw material were 2.5 m 2 / g, 1.5 ⁇ m, and 0.53 mass% in Example 12, and 10.0 m in Example 13.
- An oxynitride phosphor powder was obtained in the same manner as in Example 1 except that 2 / g, 0.2 ⁇ m, and 0.89% by mass were used.
- the fluorescence characteristics, average particle diameter, specific surface area, generated crystal phase and content, and lattice constant of the obtained oxynitride phosphor powder were measured in the same manner as in Example 1. The results are shown in Tables 1 and 2.
- the specific surface area of the oxynitride phosphor powder has an average particle diameter of 1.20 m 2 / g, 8.9 ⁇ m, whereas the specific surface area of the oxynitride phosphor powder is 0.2 to 0. It can be seen that the external quantum efficiencies of Examples 1 and 12, which are 0.6 m 2 / g and the average particle diameter is 10.0 to 20.0 ⁇ m, are large.
- the oxynitride phosphor powder was prepared in the same manner as in Example 1 except that the raw material powders according to Comparative Examples 1 to 13 were weighed and mixed so that the oxynitride phosphor powder had the design composition shown in Table 1. Obtained.
- the fluorescence characteristics, average particle diameter, specific surface area, generated crystal phase and content, and lattice constant of the obtained oxynitride phosphor powder were measured in the same manner as in Example 1. The results are shown in Tables 1 and 2. Further, the powder X-ray diffraction pattern of Comparative Example 5 is shown in FIG. FIG. 3 shows that the generated crystal phase is only the ⁇ -type sialon phase.
- Example 1 the results of measuring the fluorescence characteristics of the oxynitride phosphor powder before heat treatment are shown in Table 1, and the light reflectance of the oxynitride phosphor powder before and after heat treatment is shown in Table 3.
- Example 21 a crystalline silicon nitride powder for producing an oxynitride phosphor powder of the present invention was produced.
- the method is as follows. A solution of toluene having a silicon tetrachloride concentration of 50 vol% is reacted with liquid ammonia to produce a silicon diimide having a powder bulk density (apparent density) of 0.13 g / cm 3 and heated at 1150 ° C. in a nitrogen gas atmosphere. By decomposing, an amorphous silicon nitride powder having a powder bulk density (apparent density) of 0.25 g / cm 3 was obtained.
- the obtained amorphous silicon nitride powder was placed in a carbon crucible and fired in a nitrogen gas atmosphere under the following temperature conditions using a heating furnace to obtain crystalline silicon nitride powder.
- the temperature is raised from room temperature to 1100 ° C. in 1 hour, the heating rate from 1100 ° C. to 1400 ° C. is 10 ° C./h, the temperature is raised from 1400 ° C. to 1500 ° C. in 1 hour and held at 1500 ° C. for 1 hour. did.
- the obtained crystalline silicon nitride powder was crushed and subjected to the following characteristic evaluation.
- FIG. 1 A scanning electron micrograph of the obtained crystalline silicon nitride powder is shown in FIG.
- the specific surface area was 0.3 m 2 / g, the average particle size was 8.0 ⁇ m, and the oxygen content was 0.29% by mass.
- the specific surface area of the crystalline silicon nitride powder was measured by a BET method based on a nitrogen gas adsorption method using a Shimadzu Flowsorb 2300 type specific surface area measuring device.
- the oxygen content of the crystalline silicon nitride powder was measured with an oxygen-nitrogen simultaneous analyzer manufactured by LECO.
- the average particle size of the crystalline silicon nitride powder was measured from a scanning electron micrograph of the crystalline silicon nitride powder. Specifically, a circle is drawn in a scanning electron micrograph image, and about 150 individual particles in contact with the circle, a maximum circle inscribed in the particle is determined, and the diameter of the circle is defined as the diameter of the particle.
- the average particle size of the powder was calculated by taking the average of the particle sizes.
- the crystalline silicon nitride powder and europium nitride, aluminum nitride, and calcium nitride are weighed in a glove box purged with nitrogen so as to have the design composition of the oxynitride phosphor powder of Table 4, and used in a dry vibration mill. And mixed to obtain a mixed powder. After the obtained mixed powder is put into a silicon nitride crucible, charged into a graphite resistance heating type electric furnace, and heated to 1725 ° C. while maintaining normal pressure while circulating nitrogen in the electric furnace. And kept at 1725 ° C. for 12 hours to obtain a fired oxynitride.
- the obtained oxynitride fired product was crushed to obtain a powder having a particle size of 5 to 20 ⁇ m by classification, and the obtained powder was put into an alumina crucible and charged into a graphite resistance heating type electric furnace. While flowing nitrogen through the furnace, the temperature was raised to 1600 ° C. while maintaining normal pressure, and then kept at 1600 ° C. for 1 hour to obtain an oxynitride phosphor powder of the present invention.
- FIG. D50 A scanning electron micrograph of the obtained oxynitride phosphor powder is shown in FIG. D50 was 15.2 ⁇ m and the specific surface area was 0.29 m 2 / g.
- D50 of the oxynitride phosphor powder of the present invention is a 50% diameter in a particle size distribution curve measured with a laser diffraction / scattering particle size distribution measuring device, and was measured using LA-910 manufactured by Horiba Ltd. Further, the specific surface area of the oxynitride phosphor powder was measured by a BET method using a nitrogen gas adsorption method using a flowsorb 2300 type specific surface area measuring device manufactured by Shimadzu Corporation, as in the case of the crystalline silicon nitride powder. .
- the particles of the obtained oxynitride phosphor powder were thinned by Ar ion milling, and the cross section of the particles was observed by STEM.
- grains of oxynitride fluorescent substance powder is shown in FIG. 6 and FIG. It can be seen that there are no grain boundaries inside the particles.
- the region where the crystal lattice existing on the particle surface was not confirmed was confirmed to be amorphous by an electron diffraction pattern. When the thickness of the region was measured at three locations, it was confirmed that the thickness of the amorphous region on the particle surface, that is, the thickness of the amorphous layer was 1 nm.
- an excitation spectrum at a detection wavelength of 602 to 605 nm was measured using a solid state quantum efficiency measurement device combining an integrating sphere with FP-6500 manufactured by JASCO Corporation.
- the fluorescence spectrum at an excitation wavelength of 450 nm was measured, and at the same time, the absorptance and internal quantum efficiency were measured.
- the fluorescence peak wavelength and the emission intensity at that wavelength were derived from the obtained fluorescence spectrum, and the external quantum efficiency was calculated from the absorption rate and the internal quantum efficiency.
- the relative fluorescence intensity serving as a luminance index is the fluorescence peak when the maximum intensity value of the emission spectrum at the same excitation wavelength of a commercially available YAG: Ce-based phosphor (P46Y3 manufactured by Kasei Optonix) is 100%. The relative value of the emission intensity at the wavelength was used.
- the evaluation results of the fluorescence characteristics of the oxynitride phosphor powder according to Example 21 are the results of measuring the oxygen content, average particle diameter, and specific surface area of the crystalline silicon nitride powder as the raw material of the oxynitride phosphor powder, The results are shown in Table 4 together with the measurement results of D50 and specific surface area of the oxynitride phosphor powder.
- Example 22 When silicon diimide is thermally decomposed to obtain amorphous silicon nitride powder, except that nitrogen gas is introduced into the heating furnace so that the oxygen concentration in the nitrogen gas passed through the heating furnace is 0.6 vol% A crystalline silicon nitride powder was produced by the same method as in Example 1. The obtained crystalline silicon nitride powder had a specific surface area of 0.3 m 2 / g, an average particle size of 8.0 ⁇ m, and an oxygen content of 0.75 mass%.
- Example 21 Except that the raw material powder containing the crystalline silicon nitride powder according to Example 22 was weighed and mixed so that the oxynitride phosphor powder had the design composition shown in Table 4, it was oxynitrided in the same manner as in Example 21 Phosphor powder was obtained.
- the fluorescence characteristics of the obtained oxynitride phosphor powder were measured by the same method as in Example 21. The results were obtained by measuring the oxygen content, average particle diameter, and specific surface area of the crystalline silicon nitride powder as the raw material of the oxynitride phosphor powder according to Example 22, and the D50 and ratio of the oxynitride phosphor powder. The results are shown in Table 4 together with the measurement results of the surface area.
- Example 23 Introducing nitrogen gas into the heating furnace so that the oxygen concentration in the nitrogen gas circulated through the heating furnace is 0.0006 vol% or less when the silicon diimide is thermally decomposed to obtain amorphous silicon nitride powder.
- a crystalline silicon nitride powder was produced in the same manner as in Example 1 except that the temperature increase rate from 1100 ° C. to 1400 ° C. when firing amorphous silicon nitride was 20 ° C./h.
- the specific surface area was 1.0 m 2 / g
- the average particle size was 3.0 ⁇ m
- the oxygen content was 0.34 mass%.
- Example 21 Except that the raw material powder containing the crystalline silicon nitride powder according to Example 23 was weighed and mixed so that the oxynitride phosphor powder had the design composition shown in Table 4, it was oxynitrided in the same manner as in Example 21 Phosphor powder was obtained.
- the fluorescence characteristics of the obtained oxynitride phosphor powder were measured by the same method as in Example 21. The results were obtained by measuring the oxygen content, average particle diameter, and specific surface area of the crystalline silicon nitride powder as the raw material of the oxynitride phosphor powder according to Example 23, and the D50 and ratio of the oxynitride phosphor powder. The results are shown in Table 4 together with the measurement results of the surface area.
- Example 24 Other than introducing nitrogen gas into the heating furnace so that the oxygen concentration in the nitrogen gas circulated through the heating furnace is 0.5 vol% or less when silicon diimide is thermally decomposed to obtain amorphous silicon nitride powder Produced a crystalline silicon nitride powder by the same method as in Example 23.
- the obtained crystalline silicon nitride had a specific surface area of 1.0 m 2 / g, an average particle size of 3.0 ⁇ m, and an oxygen content of 0.72% by mass.
- Example 21 Except that the raw material powder containing the crystalline silicon nitride powder according to Example 24 was weighed and mixed so that the oxynitride phosphor powder had the design composition shown in Table 4, it was oxynitrided in the same manner as in Example 21 Phosphor powder was obtained.
- the fluorescence characteristics of the obtained oxynitride phosphor powder were measured by the same method as in Example 21. The results were obtained by measuring the oxygen content, average particle diameter, and specific surface area of the crystalline silicon nitride powder as the raw material of the oxynitride phosphor powder according to Example 24, and the D50 and ratio of the oxynitride phosphor powder. The results are shown in Table 4 together with the measurement results of the surface area.
- Example 25 Introducing nitrogen gas into the heating furnace so that the oxygen concentration in the nitrogen gas circulated through the heating furnace is 0.0006 vol% or less when the silicon diimide is thermally decomposed to obtain amorphous silicon nitride powder.
- a crystalline silicon nitride powder was produced in the same manner as in Example 21 except that the temperature increase rate from 1100 ° C. to 1400 ° C. when firing amorphous silicon nitride was 35 ° C./h.
- the specific surface area was 2.5 m 2 / g, the average particle size was 1.5 ⁇ m, and the oxygen content was 0.53 mass%.
- Example 21 Except that the raw material powder containing the crystalline silicon nitride powder according to Example 25 was weighed and mixed so that the oxynitride phosphor powder had the design composition shown in Table 4, it was oxynitrided in the same manner as in Example 21 Phosphor powder was obtained. The fluorescence characteristics of the obtained oxynitride phosphor powder were measured by the same method as in Example 21. The measurement results of the oxygen amount, average particle diameter, and specific surface area of the crystalline silicon nitride powder as the raw material of the oxynitride phosphor powder according to Example 25, and the D50 and ratio of the oxynitride phosphor powder The results are shown in Table 4 together with the measurement results of the surface area.
- Example 26 Other than introducing nitrogen gas into the heating furnace so that the oxygen concentration in the nitrogen gas circulated through the heating furnace is 0.5 vol% or less when silicon diimide is thermally decomposed to obtain amorphous silicon nitride powder Produced a crystalline silicon nitride powder by the same method as in Example 25.
- the obtained crystalline silicon nitride had a specific surface area of 2.5 m 2 / g, an average particle size of 1.5 ⁇ m, and an oxygen content of 0.73 mass%.
- Example 21 Except that the raw material powder containing the crystalline silicon nitride powder according to Example 26 was weighed and mixed so that the oxynitride phosphor powder had the design composition shown in Table 4, it was oxynitrided in the same manner as in Example 21 Phosphor powder was obtained.
- the fluorescence characteristics of the obtained oxynitride phosphor powder were measured by the same method as in Example 21. The results were obtained by measuring the oxygen content, average particle diameter, and specific surface area of the crystalline silicon nitride powder as the raw material of the oxynitride phosphor powder according to Example 26, and the D50 and ratio of the oxynitride phosphor powder. The results are shown in Table 4 together with the measurement results of the surface area.
- Example 27 An oxynitride phosphor powder was obtained in the same manner as in Example 21 except that the heat treatment conditions of the oxynitride fired product were changed as shown in Table 4. The fluorescence characteristics of the obtained oxynitride phosphor powder were measured by the same method as in Example 21. The results are the results of measurement of the oxygen amount, average particle diameter, and specific surface area of the silicon nitride powder as the raw material of each oxynitride phosphor powder according to Example 27, and D50 of each oxynitride phosphor powder. The results are shown in Table 4 together with the measurement results of the specific surface area.
- Example 28 to 29 An oxynitride phosphor powder was obtained in the same manner as in Example 21, except that the raw material powder was weighed and mixed so that the oxynitride phosphor powder had the design composition shown in Table 4.
- the fluorescence characteristics of the obtained oxynitride phosphor powder were measured by the same method as in Example 21.
- the results are the results of measurement of the oxygen content, average particle diameter, and specific surface area of the crystalline silicon nitride powder as the raw material of each oxynitride phosphor powder according to Examples 28 to 29, and the respective oxynitride fluorescence. It shows in Table 4 together with the measurement result of D50 of a body powder, and a specific surface area.
- Comparative Example 21 Except that the raw material powder containing the crystalline silicon nitride powder according to Comparative Example 21 was weighed and mixed so that the oxynitride phosphor powder had the design composition shown in Table 4, it was oxynitrided in the same manner as in Example 21 Phosphor powder was obtained.
- the fluorescence characteristics of the obtained oxynitride phosphor powder were measured by the same method as in Example 21.
- the measurement results of the oxygen amount, average particle diameter, and specific surface area of the crystalline silicon nitride powder as the raw material of the oxynitride phosphor powder according to Comparative Example 21, and the D50 and ratio of the oxynitride phosphor powder The results are shown in Table 4 together with the measurement results of the surface area.
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Abstract
Description
一般式:
CaxEuySi12-(m+n)Al(m+n)OnN16-n
で表されるEuにより賦活された、Ca含有α型サイアロン蛍光体は、実用に値する高輝度な蛍光体は開発されていなかった。
組成式:
Cax1Eux2Si12-(y+z)Al(y+z)OzN16-z
(ただし、式中、
0<x1≦3.40、
0.05≦x2≦0.20、
4.0≦y≦7.0、
0≦z≦1)
で表される組成となるように、ケイ素源となる物質と、アルミニウム源となる物質と、カルシウム源となる物質と、ユーロピウム源となる物質とを混合し、焼成して得られる蛍光体であり、該蛍光体はα型サイアロンと窒化アルミニウムとを含む酸窒化物蛍光体粉末とすることで、450nmの波長の光により励起されて、ピーク波長が595nmから605nmの広い波長域で蛍光を発し、その際の外部量子効率が好適な、酸窒化物蛍光体粉末が得られることを見出し、本発明に至った。
組成式:
Cax1Eux2Si12-(y+z)Al(y+z)OzN16-z
(ただし、式中、x1、x2、y、zは、
0<x1≦3.40、
0.05≦x2≦0.20、
4.0≦y≦7.0、
0≦z≦1)
で表される組成となるように、ケイ素源となる物質と、アルミニウム源となる物質と、カルシウム源となる物質と、ユーロピウム源となる物質とを混合し、焼成して得られ、
α型サイアロンと窒化アルミニウムとを含むことを特徴とする酸窒化物蛍光体粉末に関する。
0<x1≦3.40、
0.05≦x2≦0.20、
4.50≦y≦5.50、
0≦z≦1.00
であることを特徴とする酸窒化物蛍光体粉末に関する。
1.37≦x1≦2.60、
0.16≦x2≦0.20、
4.50≦y≦5.50、
0≦z≦0.30
であることを特徴とする酸窒化物蛍光体粉末に関する。
1.70<x1≦2.60、
0.16≦x2≦0.20、
4.50≦y≦5.05、
0≦z≦0.30
であることを特徴とする酸窒化物蛍光体粉末に関する。
1.70<x1≦2.60、
0.16≦x2≦0.20、
4.50≦y≦5.05、
0≦z≦0.10
であることを特徴とする酸窒化物蛍光体粉末に関する。
1.37≦x1≦2.60、
0.16≦x2≦0.20、
4.50≦y≦5.50、
0≦z≦0.30
であり、ピーク波長が602nm~605nmの波長域にある蛍光を発し、その際の外部量子効率が60%以上であることを特徴とする酸窒化物蛍光体粉末に関する。
1.37≦x1≦2.60、さらには1.70≦x1≦2.60、
0.16≦x2≦0.20、
4.50≦y≦5.50、
0≦z≦0.30、さらには0≦z≦0.10
である酸窒化物蛍光体粉末を製造するための原料として使用する結晶質窒化ケイ素粉末であることを特徴とする前記酸窒化物蛍光体粉末製造用窒化ケイ素粉末に関する。
Cax1Eux2Si12-(y+z)Al(y+z)OzN16-z
(ただし、式中、x1、x2、y、zは、
0<x1≦3.40、
0.05≦x2≦0.20、
4.0≦y≦7.0、
0≦z≦1)
で表される組成となるように、ケイ素源となる物質と、アルミニウム源となる物質と、カルシウム源となる物質と、ユーロピウム源となる物質とを混合し、不活性ガス雰囲気中、1500~2000℃の温度範囲で焼成することにより、前記一般式で表される酸窒化物焼成物を得る第1工程と、
前記酸窒化物焼成物を、不活性ガス雰囲気中、1100~1600℃の温度範囲で熱処理する第2工程と、
を有することを特徴とする酸窒化物蛍光体粉末の製造方法に関する。
1.37≦x1≦2.60、
0.16≦x2≦0.20、
4.50≦y≦5.50、
0≦z≦0.30
である酸窒化物蛍光体粉末の製造方法であることを特徴とする酸窒化物蛍光体粉末の前記製造方法に関する。
Cax1Eux2Si12-(y+z)Al(y+z)OzN16-z
で表される酸窒化物蛍光体において、
0<x1≦3.40、0.05≦x2≦0.20、4.0≦y≦7.0、0≦z≦1で表される組成となるように、ケイ素源となる物質と、アルミニウム源となる物質と、カルシウム源となる物質と、ユーロピウム源となる物質とを混合し、焼成して得られる蛍光体であり、該蛍光体はα型サイアロンと窒化アルミニウムとを含む酸窒化物蛍光体粉末とすることにより、450nmの波長の光により励起されることで、ピーク波長が595nmから605nmの広い波長域で蛍光を発する新規な酸窒化物蛍光体粉末が提供される。この新規な酸窒化物蛍光体粉末は、好適には、450nmの波長の光により励起されて発する蛍光の外部量子効率が特に大きいという特徴を有し、高効率な酸窒化物蛍光体粉末であることができる。また、本発明は、その酸窒化物蛍光体粉末の製造に好適に用いることができる窒化ケイ素粉末、及びその酸窒化物蛍光体粉末の製造方法が提供される。
Cax1Eux2Si12-(y+z)Al(y+z)OzN16-z
で表される酸窒化物蛍光体において、
0<x1≦3.40、
0.05≦x2≦0.20、
4.0≦y≦7.0、
0≦z≦1
で表される組成となるように、ケイ素源となる物質と、アルミニウム源となる物質と、カルシウム源となる物質と、ユーロピウム源となる物質とを混合し、焼成して得られる、α型サイアロンと窒化アルミニウムとを含む酸窒化物蛍光体粉末とすることにより、450nmの波長の光により励起されることで、ピーク波長が595nmから605nmの広い波長域で蛍光を発する酸窒化物蛍光体粉末に関し、とりわけ、その発光の際の外部量子効率が特に大きい、酸窒化物蛍光体粉末に関するものである。
組成式:
Cax1Eux2Si12-(y+z)Al(y+z)OzN16-z
において、
0<x1≦3.40、
0.05≦x2≦0.20、
4.0≦y≦7.0、
0≦z≦1
で表される組成となるように、ケイ素源となる物質と、アルミニウム源となる物質と、カルシウム源となる物質と、ユーロピウム源となる物質とを混合し、焼成して得られる、α型サイアロンと窒化アルミニウムとを含む酸窒化物蛍光体粉末である。
0<x1≦3.40、
0.05≦x2≦0.20、
4.50≦y≦5.50、
0≦z≦1.00
である。
1.37≦x1≦2.60、
0.16≦x2≦0.20、
4.50≦y≦5.50、
0≦z≦0.30
である。
1.37≦x1≦2.60、
0.16≦x2≦0.20、
4.50≦y≦5.05、
0≦z≦0.10
である。
α型サイアロンと窒化アルミニウム以外の結晶相は含まないことが好ましい。含まれる可能性があるその他の結晶相としては、α型窒化ケイ素、酸化ケイ素、酸化カルシウム、酸窒化アルミニウム、酸化アルミニウムなどが挙げられ、その含有量は1質量%以下が好ましい。
7.93Å≦a=b≦7.99Å、
5.75Å≦c≦5.80Å
の範囲であることが好ましい。α型サイアロン結晶相の格子定数が、前記範囲外である場合には、外部量子効率が小さくなる。
7.96Å≦a=b≦7.99Å、
5.77Å≦c≦5.80Å
の範囲であることがより好ましい。この範囲内にある場合には、より外部量子効率が大きくなる。
3.11Å≦a=b≦3.12Å、
4.97Å≦c≦4.99Å
の範囲であることが好ましい。窒化アルミニウム結晶相の格子定数が、前記範囲内である場合には、外部量子効率がより大きくなる。
Cax1Eux2Si12-(y+z)Al(y+z)OzN16-z
において、
0<x1≦3.40、
0.05≦x2≦0.20、
4.0≦y≦7.0、
0≦z≦1
で表される組成となるように、ケイ素源となる物質と、ユーロピウム源となる物質と、カルシウム源となる物質と、アルミニウム源となる物質とを混合し、不活性ガス雰囲気中、1500~2000℃の温度範囲で焼成することにより得られる。好ましくは、得られた焼成物を、さらに、不活性ガス雰囲気中、1100~1600℃の温度範囲で熱処理する。
Cax1Eux2Si12-(y+z)Al(y+z)OzN16-z
において、
0<x1≦3.40、
0.05≦x2≦0.20、
4.0≦y≦7.0、
0≦z≦1
で表される酸窒化物蛍光体粉末である。
窒化ケイ素と窒化ユーロピウム、窒化アルミニウム、窒化カルシウムを、表1の酸窒化物の設計組成となるように窒素パージされたグローブボックス内で秤量し、乾式の振動ミルを用いて混合して、混合粉末を得た。原料の結晶質窒化ケイ素粉末の比表面積、平均粒子径及び酸素量は、それぞれ、0.3m2/g、8.0μm及び0.29質量%であった。得られた混合粉末を窒化ケイ素製のるつぼに入れて、黒鉛抵抗加熱式の電気炉に仕込み、電気炉内に窒素を流通させながら、常圧を保った状態で、1725℃まで昇温した後、1725℃で12時間保持して、酸窒化物焼成物を得た。
さらに、熱処理前後の酸窒化物蛍光体粉末の光反射率を測定した。結果を表3に示す。
<光反射率の評価方法>
分光蛍光光度計(日本分光社製FP―6500)に積分球を組み合わせた測定装置を用いて光反射率を測定した。具体的には、入射光と同波長の反射光の強度を測定する同期走査測定を行い、反射基準(標準白板)の反射率を100%とし、試料粉末の反射率を標準白板に対する相対反射率として光反射率を測定した。300~800nmまでの拡散反射率の測定を行い、蛍光スペクトルにおけるピーク波長の光の反射率を求めた。
また、粒子表面の非晶質層の厚みは本発明の実施例ではすべて1nm以下であった。
酸窒化物蛍光体粉末が表1の設計組成になるように、実施例2~11に係る原料粉末を秤量し混合したこと以外は、実施例1と同様の方法で酸窒化物蛍光体粉末を得た。得られた酸窒化物蛍光体粉末の蛍光特性、平均粒子径、比表面積、生成結晶相および含有量、格子定数を実施例1と同様の方法で測定した。その結果を、表1および表2に記載した。原料の結晶質窒化ケイ素粉末の比表面積、平均粒子径及び酸素量は、それぞれ、0.3m2/g、8.0μm及び0.29質量%であった。また、実施例2及び8の粉末X線回折パターンを図1及び2に示している。図1及び2より、生成結晶相はα型サイアロン相と窒化アルミニウム相であることが分かる。
原料の結晶質窒化ケイ素粉末の比表面積、平均粒子径及び酸素量を、実施例12は、2.5m2/g、1.5μm及び0.53質量%と、実施例13は、10.0m2/g、0.2μm及び0.89質量%とした以外は、実施例1と同様の方法で酸窒化物蛍光体粉末を得た。得られた酸窒化物蛍光体粉末の蛍光特性、平均粒子径、比表面積、生成結晶相および含有量、格子定数を実施例1と同様の方法で測定した。その結果を、表1および表2に記載した。酸窒化物蛍光体粉末の比表面積、平均粒子径が、1.20m2/g、8.9μmである実施例13に対して、酸窒化物蛍光体粉末の比表面積が、0.2~0.6m2/gで、且つ、平均粒子径が10.0~20.0μmである実施例1および12の外部量子効率が大きくなっていることが分かる。
酸窒化物蛍光体粉末が表1の設計組成になるように、比較例1~13に係る原料粉末を秤量し混合したこと以外は、実施例1と同様の方法で酸窒化物蛍光体粉末を得た。得られた酸窒化物蛍光体粉末の蛍光特性、平均粒子径、比表面積、生成結晶相および含有量、格子定数を実施例1と同様の方法で測定した。その結果を、表1および表2に記載した。また、比較例5の粉末X線回折パターンを図3に示している。図3より、生成結晶相はα型サイアロン相のみであることが分かる。
はじめに、本発明の酸窒化物蛍光体粉末製造用結晶質窒化ケイ素粉末を作製した。その方法は次の通りである。
四塩化ケイ素濃度が50vol%のトルエンの溶液を液体アンモニアと反応させ、粉体嵩密度(見掛け密度)0.13g/cm3のシリコンジイミドを作製し、これを窒素ガス雰囲気下、1150℃で加熱分解して、0.25g/cm3の粉体嵩密度(見掛け密度)を有する非晶質窒化ケイ素粉末を得た。なお、シリコンジイミドの加熱分解操作においては、同操作に使用する加熱炉に流通させる窒素ガス中の酸素濃度が0.0005vol%以下になるように、加熱炉に窒素ガスを導入した。得られた非晶質窒化ケイ素粉末に混入する金属不純物は、反応容器材質および粉末取り扱い機器における粉末と金属との擦れ合い状態を改良する公知の方法により、10ppm以下に低減された。
シリコンジイミドを加熱分解して非晶質窒化ケイ素粉末を得る際に、加熱炉に流通させる窒素ガス中の酸素濃度が0.6vol%になるように、加熱炉に窒素ガスを導入したこと以外は、実施例1と同じ方法によって、結晶質窒化ケイ素粉末を作製した。得られた結晶質窒化ケイ素粉末の比表面積は0.3m2/g、平均粒子径は8.0μm、酸素量は0.75質量%であった。
シリコンジイミドを加熱分解して非晶質窒化ケイ素粉末を得る際に、加熱炉に流通させる窒素ガス中の酸素濃度が0.0006vol%以下になるように、加熱炉に窒素ガスを導入したことと、非晶質窒化ケイ素を焼成する際の1100℃から1400℃までの昇温速度を20℃/hとした以外は、実施例1と同じ方法によって、結晶質窒化ケイ素粉末を作製した。この場合の比表面積は1.0m2/g、平均粒子径は3.0μm、酸素量は0.34質量%であった。
シリコンジイミドを加熱分解して非晶質窒化ケイ素粉末を得る際に、加熱炉に流通させる窒素ガス中の酸素濃度が0.5vol%以下になるように、加熱炉に窒素ガスを導入したこと以外は、実施例23と同じ方法によって、結晶質窒化ケイ素粉末を作製した。得られた結晶質窒化ケイ素の比表面積は1.0m2/g、平均粒子径は3.0μm、酸素量は0.72質量%であった。
シリコンジイミドを加熱分解して非晶質窒化ケイ素粉末を得る際に、加熱炉に流通させる窒素ガス中の酸素濃度が0.0006vol%以下になるように、加熱炉に窒素ガスを導入したことと、非晶質窒化ケイ素を焼成する際の1100℃から1400℃までの昇温速度を35℃/hとしたこと以外は、実施例21と同じ方法によって、結晶質窒化ケイ素粉末を作製した。比表面積は2.5m2/g、平均粒子径は1.5μm、酸素量は0.53質量%であった。
シリコンジイミドを加熱分解して非晶質窒化ケイ素粉末を得る際に、加熱炉に流通させる窒素ガス中の酸素濃度が0.5vol%以下になるように、加熱炉に窒素ガスを導入したこと以外は、実施例25と同じ方法によって、結晶質窒化ケイ素粉末を作製した。得られた結晶質窒化ケイ素の比表面積は2.5m2/g、平均粒子径は1.5μm、酸素量は0.73質量%であった。
酸窒化物焼成物の熱処理条件を表4に示すように変更したこと以外は、実施例21と同様の方法で酸窒化物蛍光体粉末を得た。得られた酸窒化物蛍光体粉末の蛍光特性を実施例21と同様の方法で測定した。その結果を、実施例27に係る、それぞれの酸窒化物蛍光体粉末の原料の窒化ケイ素粉末の酸素量、平均粒子径、比表面積の測定結果、また、それぞれの酸窒化物蛍光体粉末のD50及び比表面積の測定結果と併せて、表4に示す。
酸窒化物蛍光体粉末が表4の設計組成になるように、原料粉末を秤量し混合したこと以外は、実施例21と同様の方法で酸窒化物蛍光体粉末を得た。得られた酸窒化物蛍光体粉末の蛍光特性を実施例21と同様の方法で測定した。その結果を、実施例28~29に係る、それぞれの酸窒化物蛍光体粉末の原料の結晶質窒化ケイ素粉末の酸素量、平均粒子径、比表面積の測定結果、また、それぞれの酸窒化物蛍光体粉末のD50及び比表面積の測定結果と併せて、表4に示す。
酸窒化物蛍光体粉末が表4の設計組成になるように、比較例21に係る結晶質窒化ケイ素粉末を含む原料粉末を秤量し混合したこと以外は、実施例21と同様の方法で酸窒化物蛍光体粉末を得た。
酸窒化物蛍光体粉末が表4の設計組成になるように、原料粉末を秤量し混合したこと以外は、実施例21と同様の方法で酸窒化物蛍光体粉末を得た。得られた酸窒化物蛍光体粉末の蛍光特性を実施例21と同様の方法で測定した。その結果を、酸窒化物蛍光体粉末の原料の窒化ケイ素粉末の酸素量、平均粒子径、比表面積の測定結果、また、酸窒化物蛍光体粉末のD50及び比表面積の測定結果と併せて、表4に示す。
Claims (19)
- 組成式:
Cax1Eux2Si12-(y+z)Al(y+z)OzN16-z
(ただし、式中、x1、x2、y、zは、
0<x1≦3.40、
0.05≦x2≦0.20、
4.0≦y≦7.0、
0≦z≦1)
で表される組成となるように、ケイ素源となる物質と、アルミニウム源となる物質と、カルシウム源となる物質と、ユーロピウム源となる物質とを混合し、焼成して得られる、α型サイアロンと窒化アルミニウムとを含む酸窒化物蛍光体粉末。 - 前記x1、x2、y、zは、
0<x1≦3.40、
0.05≦x2≦0.20、
4.5≦y≦5.5、
0≦z≦1
であることを特徴とする請求項1記載の酸窒化物蛍光体粉末。 - 前記x1、x2、y、zが、
1.37≦x1≦2.60、
0.16≦x2≦0.20、
4.50≦y≦5.50、
0≦z≦0.30
であることを特徴とする請求項2記載の酸窒化物蛍光体粉末。 - 前記x1、x2、y及びzが、
1.70≦x1≦2.60、
0.16≦x2≦0.20、
4.50≦y≦5.05、
0≦z≦0.10
であることを特徴とする請求項3記載の酸窒化物蛍光体粉末。 - 前記組成式において、窒化アルミニウムの含有量が、0質量%より大きく32質量%より小さいことを特徴とする請求項1~4のいずれか一項に記載の酸窒化物蛍光体粉末。
- 450nmの波長の光により励起されて発する蛍光の外部量子効率が60%以上であることを特徴とする請求項1~5のいずれか一項に記載のα型サイアロンと窒化アルミニウムとを含む酸窒化物蛍光体粉末。
- 光反射率が80%以上であることを特徴とする請求項1~6のいずれか一項に記載のα型サイアロンと窒化アルミニウムとを含む酸窒化物蛍光体粉末。
- 酸窒化物蛍光体粉末を構成するα型サイアロン結晶相の格子定数が、7.93Å≦a=b≦7.99Å、5.75Å≦c≦5.80Åの範囲であることを特徴とする請求項1~7のいずれか一項に記載の酸窒化物蛍光体粉末。
- レーザー回折/散乱式粒度分布測定装置で測定した粒度分布曲線における50%径(D50)が10.0~20.0μmであり、かつ、比表面積が0.2~0.6m2/gであることを特徴とする請求項1~8のいずれか一項に記載の酸窒化物蛍光体粉末。
- 粒子表面の非晶質層が2nm未満であることを特徴とする請求項1~8のいずれか一項に記載の酸窒化物蛍光体粉末。
- 450nmの波長の光により励起されることで、ピーク波長が595nm~605nmの波長域にある蛍光を発し、その際の外部量子効率が60%以上であることを特徴とする請求項1~10のいずれか一項に記載の酸窒化物蛍光体粉末。
- 前記x1、x2、y、zが、
1.37≦x1≦2.60、
0.16≦x2≦0.20、
4.50≦y≦5.50、
0≦z≦0.30
であり、ピーク波長が602nm~605nmの波長域にある蛍光を発し、その際の外部量子効率が60%以上であることを特徴とする請求項11に記載の酸窒化物蛍光体粉末。 - 請求項1~12のいずれか一項に記載の酸窒化物蛍光体粉末を製造するための原料として使用する結晶質窒化ケイ素粉末であり、酸素含有量が0.2~0.9質量%であることを特徴とする酸窒化物蛍光体粉末製造用窒化ケイ素粉末。
- 平均粒子径が1.0~12.0μmであることを特徴とする請求項13に記載の酸窒化物蛍光体粉末製造用窒化ケイ素粉末。
- 比表面積が0.2~3.0m2/gであることを特徴とする請求項13または14に記載の酸窒化物蛍光体粉末製造用窒化ケイ素粉末。
- 前記x1、x2、y、zが、
1.37≦x1≦2.60、
0.16≦x2≦0.20、
4.50≦y≦5.50、
0≦z≦0.30
である酸窒化物蛍光体粉末を製造するための原料として使用する結晶質窒化ケイ素粉末であることを特徴とする請求項13~15のいずれか一項に記載の酸窒化物蛍光体粉末製造用窒化ケイ素粉末。 - 組成式:
Cax1Eux2Si12-(y+z)Al(y+z)OzN16-z
(ただし、式中、x1、x2、y、zは、
0<x1≦3.40、
0.05≦x2≦0.20、
4.0≦y≦7.0、
0≦z≦1)
で表される組成となるように、ケイ素源となる物質と、アルミニウム源となる物質と、カルシウム源となる物質と、ユーロピウム源となる物質とを混合し、不活性ガス雰囲気中、1500~2000℃の温度範囲で焼成することにより、前記一般式で表される酸窒化物焼成物を得る第1工程と、
前記酸窒化物焼成物を、不活性ガス雰囲気中、1100~1600℃の温度範囲で熱処理する第2工程と、
を有することを特徴とする、請求項1~12いずれか一項に記載の酸窒化物蛍光体粉末の製造方法。 - 前記ケイ素源となる物質が窒化ケイ素粉末であり、前記窒化ケイ素粉末の酸素含有量が0.2~0.9質量%であり、平均粒子径が1.0~12.0μmであり、比表面積が0.2~3.0m2/gであることを特徴とする請求項17に記載の酸窒化物蛍光体粉末の製造方法。
- 前記x1、x2、y、zが、
1.37≦x1≦2.60、
0.16≦x2≦0.20、
4.50≦y≦5.50、
0≦z≦0.30
である酸窒化物蛍光体粉末の製造方法であることを特徴とする請求項18に記載の酸窒化物蛍光体粉末の製造方法。
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WO2013118329A1 (ja) * | 2012-02-09 | 2013-08-15 | 電気化学工業株式会社 | 蛍光体及び発光装置 |
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JP7416995B1 (ja) | 2023-03-31 | 2024-01-17 | デンカ株式会社 | α型サイアロン蛍光体および発光装置 |
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