WO2022244523A1 - 蛍光体、その製造方法、発光素子および発光装置 - Google Patents
蛍光体、その製造方法、発光素子および発光装置 Download PDFInfo
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 236
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 174
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 144
- 229910052788 barium Inorganic materials 0.000 claims abstract description 140
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 114
- 239000000203 mixture Substances 0.000 claims abstract description 48
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 23
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 22
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 13
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 11
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 11
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 11
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 11
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 11
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 10
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims description 220
- 229910052757 nitrogen Inorganic materials 0.000 claims description 128
- 229910052782 aluminium Inorganic materials 0.000 claims description 125
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- 238000002050 diffraction method Methods 0.000 claims description 5
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- 229910018250 LaSi Inorganic materials 0.000 claims description 3
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 3
- 229910004122 SrSi Inorganic materials 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 150000002222 fluorine compounds Chemical class 0.000 claims 1
- 239000011575 calcium Substances 0.000 description 152
- 239000011777 magnesium Substances 0.000 description 135
- 239000000843 powder Substances 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
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- 229910052581 Si3N4 Inorganic materials 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 238000000295 emission spectrum Methods 0.000 description 9
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- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 229910052582 BN Inorganic materials 0.000 description 7
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 7
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- 230000015572 biosynthetic process Effects 0.000 description 6
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 5
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- 239000000463 material Substances 0.000 description 4
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 description 4
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
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- AYCPARAPKDAOEN-LJQANCHMSA-N N-[(1S)-2-(dimethylamino)-1-phenylethyl]-6,6-dimethyl-3-[(2-methyl-4-thieno[3,2-d]pyrimidinyl)amino]-1,4-dihydropyrrolo[3,4-c]pyrazole-5-carboxamide Chemical compound C1([C@H](NC(=O)N2C(C=3NN=C(NC=4C=5SC=CC=5N=C(C)N=4)C=3C2)(C)C)CN(C)C)=CC=CC=C1 AYCPARAPKDAOEN-LJQANCHMSA-N 0.000 description 2
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- 229910052727 yttrium Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 102100032047 Alsin Human genes 0.000 description 1
- 101710187109 Alsin Proteins 0.000 description 1
- 229910000980 Aluminium gallium arsenide Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910017414 LaAl Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
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- 150000001649 bromium compounds Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910019990 cerium-doped yttrium aluminum garnet Inorganic materials 0.000 description 1
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- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 229910001940 europium oxide Inorganic materials 0.000 description 1
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 1
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- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
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- 239000002932 luster Substances 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
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- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
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- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
- C09K11/77348—Silicon Aluminium Nitrides or Silicon Aluminium Oxynitrides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
- H01L33/504—Elements with two or more wavelength conversion materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
- H01L2933/0008—Processes
- H01L2933/0033—Processes relating to semiconductor body packages
- H01L2933/0041—Processes relating to semiconductor body packages relating to wavelength conversion elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01S—DEVICES USING THE PROCESS OF LIGHT AMPLIFICATION BY STIMULATED EMISSION OF RADIATION [LASER] TO AMPLIFY OR GENERATE LIGHT; DEVICES USING STIMULATED EMISSION OF ELECTROMAGNETIC RADIATION IN WAVE RANGES OTHER THAN OPTICAL
- H01S5/00—Semiconductor lasers
- H01S5/005—Optical components external to the laser cavity, specially adapted therefor, e.g. for homogenisation or merging of the beams or for manipulating laser pulses, e.g. pulse shaping
- H01S5/0087—Optical components external to the laser cavity, specially adapted therefor, e.g. for homogenisation or merging of the beams or for manipulating laser pulses, e.g. pulse shaping for illuminating phosphorescent or fluorescent materials, e.g. using optical arrangements specifically adapted for guiding or shaping laser beams illuminating these materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Definitions
- the present disclosure provides Sr 6x (Si, Al) 27-12x (O, N) 31-6x Li 3y with 0.4 ⁇ x ⁇ 0.8 and 0 ⁇ y ⁇ 0.35.
- the crystal represented hereinafter referred to as the present crystal
- a crystal having the same crystal structure as Sr 3 Si 12.432 Al 8.568 O 1.608 N 26.392 Li 0.96 hereinafter referred to as the present same crystal
- the present invention relates to a phosphor containing an inorganic compound as a host crystal, a method for producing the same, and uses thereof.
- Phosphors are fluorescent display tubes (VFD (Vacuum-Fluorescent Display)), field emission displays (FED (Field Emission Display) or SED (Surface-Conduction Electron-Emitter Display)), plasma display panels (PDP (Plasma Display) ), cathode-ray tubes (CRTs), liquid-crystal display backlights, and white light-emitting diodes (LEDs).
- VFD Voluum-Fluorescent Display
- FED Field Emission Display
- SED Surface-Conduction Electron-Emitter Display
- PDP Plasma display panels
- CRTs cathode-ray tubes
- LCD liquid-crystal display backlights
- LEDs white light-emitting diodes
- sialon phosphors have been developed as phosphors that exhibit less brightness degradation even when excited by high energy.
- oxynitride phosphors, nitride phosphors, and the like which are based on inorganic crystals containing nitrogen in the crystal structure, have been proposed.
- sialon phosphor is manufactured by the manufacturing process outlined below. First, silicon nitride (Si 3 N 4 ), aluminum nitride (AlN), calcium oxide (CaO), and europium oxide (Eu 2 O 3 ) were mixed in a predetermined molar ratio and placed in nitrogen at 1 atmosphere (0.1 MPa). at a temperature of 1700° C. for 1 hour and fired by a hot press method (see, for example, Patent Document 1). The Eu 2+ ion-activated ⁇ -sialon obtained by this process is reported to be a phosphor that emits yellow light of 550 to 600 nm when excited by blue light of 450 to 500 nm. In addition, it is known that the emission wavelength changes by changing the ratio of Si and Al and the ratio of oxygen and nitrogen while maintaining the crystal structure of ⁇ -sialon (see, for example, Patent Documents 2 and 3). ).
- a green phosphor obtained by activating ⁇ -sialon with Eu 2+ is known (see Patent Document 4). It is known that in this phosphor, the emission wavelength is changed to a shorter wavelength by changing the oxygen content while maintaining the crystal structure (see, for example, Patent Document 5). It is also known that activating Ce 3+ results in a blue phosphor (see, for example, Patent Document 6).
- a blue phosphor As an example of an oxynitride phosphor, a blue phosphor (see Patent Document 7) is known in which Ce is activated using a JEM phase (LaAl(Si 6-z Al z )N 10-z O z ) as a host crystal. ing. In this phosphor, it is known that by substituting a portion of La with Ca while maintaining the crystal structure, the excitation wavelength is lengthened and the emission wavelength is also lengthened.
- a JEM phase LaAl(Si 6-z Al z )N 10-z O z
- a blue phosphor is known in which Ce is activated using La—N crystal La 3 Si 8 N 11 O 4 as a host crystal (see Patent Document 8).
- a red phosphor in which CaAlSiN 3 is used as a host crystal and Eu 2+ is activated (see Patent Document 9) is known.
- the use of this phosphor has the effect of improving the color rendering properties of the white LED.
- a phosphor added with Ce as an optically active element is reported to be an orange phosphor.
- the luminescent color of the phosphor is determined by the combination of the matrix crystal and the metal ions (activated ions) dissolved therein. Furthermore, the combination of host crystals and activated ions determines the emission characteristics such as the emission spectrum and excitation spectrum, chemical stability, and thermal stability. considered different phosphors. In addition, materials with the same chemical composition but different crystal structures are regarded as different phosphors because they have different emission characteristics and stability due to different host crystals.
- phosphors in many phosphors, it is possible to replace the types of constituent elements while maintaining the crystal structure of the host crystal, thereby changing the emission color.
- a phosphor obtained by adding Ce to YAG emits green light
- a phosphor obtained by substituting part of Y in the YAG crystal with Gd and part of Al with Ga emits yellow light.
- it is known that in a phosphor obtained by adding Eu to CaAlSiN 3 by substituting a portion of Ca with Sr, the composition is changed while maintaining the crystal structure, and the emission wavelength is shortened. In this way, phosphors in which element substitution is performed while maintaining the crystal structure are regarded as materials of the same group.
- Fluorescence properties are expressed by activating metal ions responsible for light emission in such host crystals.
- by changing the constituent elements of the novel crystal it is possible to produce a crystal with a different composition while maintaining the crystal structure.
- novel phosphors with certain emission properties are provided.
- New phosphors are expected to have different emission properties (emission color, excitation properties, emission spectrum). In particular, it may have luminescence in the red and near-infrared regions above 600 nm upon irradiation with visible or ultraviolet light.
- emission properties emission color, excitation properties, emission spectrum
- it may have luminescence in the red and near-infrared regions above 600 nm upon irradiation with visible or ultraviolet light.
- an LED 600 nm or less
- the present inventors conducted detailed research on a new crystal containing nitrogen and a phosphor whose matrix is a crystal in which a metal element or N in the crystal structure is replaced with another element, and the present invention
- crystals and inorganic materials containing this same crystal as a host or host crystal emit fluorescence with high brightness. It was also found that certain compositions exhibit red or near-infrared luminescence.
- the present inventor succeeded in providing a phosphor capable of exhibiting a high luminance luminescence phenomenon in a specific wavelength region by adopting the configuration described below.
- the inventors succeeded in producing a phosphor capable of exhibiting excellent luminescence properties by the following method.
- the present inventors have succeeded in providing a light-emitting element and a light-emitting device having excellent characteristics by using this phosphor and adopting the configuration described below. More details are provided below.
- the phosphor contains at least A element, M element, D element and E element (where A is at least one or two elements selected from the group consisting of Mg, Ca, Sr and Ba).
- M is one or more elements selected from the group consisting of Mn, Eu, Ce, Nd, Tb, Dy, Ho, Er, Tm and Yb
- D is Si and one or more elements selected from the group consisting of Al
- E is one or more elements selected from the group consisting of O and N)
- G element where G is a Li element
- (A, M) is represented by the composition of a D d E e G g , and the atomic fraction parameters a, d, e, and g are 2.4 ⁇ a ⁇ 4.8 17.4 ⁇ d ⁇ 22.2 26.2 ⁇ e ⁇ 28.6 0 ⁇ g ⁇ 3 may contain an inorganic compound represented by a numerical value of The above problems are solved.
- the parameter g is 0.21 ⁇ g ⁇ 1.05 It may be represented by a numerical value in the range of
- the inorganic compound is (A, M) 6x D 27-12x E 31-6x G 3y (where x and y satisfy 0.4 ⁇ x ⁇ 0.8 and 0 ⁇ y ⁇ 0.35, respectively) ) may be represented by the composition of
- “(A, M) 6x ” means that both A atoms and M atoms are present (that is, each atom has an index greater than 0), and the total number of A atoms and M atoms is “6x”. It can mean something.
- the inorganic compound is a crystal represented by (A, M) 6x D 27-12x E 31-6x G 3y (where 0.4 ⁇ x ⁇ 0.8, 0 ⁇ y ⁇ 0.35) (referred to as the present crystal) ) may be included. Also, it may be a crystal having the same crystal structure as the present crystal (referred to as the present same crystal).
- the inorganic compound may contain a crystal represented by ( Sr ,Eu) 3 (Si,Al) 21 (O,N) 28Li0.96 .
- the inorganic compound may comprise crystals having the same crystal structure as Sr3Si12.432Al8.568O1.608N26.392Li0.96 .
- the present crystal and the present same crystal are hexagonal and have lattice constants a, b, and c of 1.6 ⁇ a ⁇ 1.8 nm.
- b a 0.44 ⁇ c ⁇ 0.52 nm may be
- the present crystal and the present same crystal may be crystals belonging to the P63 space group ( 173 space group in the International Tables for Crystallography).
- the inorganic compound is represented by Sr 6x (Si, Al) 27-12x (O, N) 31-6x Li 3y (0.4 ⁇ x ⁇ 0.8, 0 ⁇ y ⁇ 0.35) It may contain a crystal or a crystal having the same crystal structure as that, and may further contain the M element.
- the A element may be Sr
- the M element may be Eu
- the E element may be one or more elements selected from the group consisting of O and N.
- the D element includes Si and Al, 0.4 ⁇ Al/(Al+Si) ⁇ 0.6 may be satisfied.
- the E element includes O and N, 0.01 ⁇ O/(O+N) ⁇ 0.1 may be satisfied.
- any of the phosphors described above may emit light having a maximum emission peak at a wavelength in the range of 600 nm to 850 nm when irradiated with light having a wavelength in the range of 300 nm to 600 nm.
- the method for producing any of the phosphors described above includes the use of element A (where A is one or more elements selected from the group consisting of Mg, Ca, Sr and Ba ), M element (where M is one or more elements selected from the group consisting of Mn, Eu, Ce, Nd, Tb, Dy, Ho, Er, Tm and Yb), D element (one or more elements selected from the group consisting of Si and Al), optionally nitrides, oxynitrides, and oxides of G element (where G is Li element), A step of mixing one or more raw materials selected from the group consisting of carbonates and fluorides and firing at a temperature of 1400° C.
- a light-emitting device may be provided that includes an excitation source that emits light with a wavelength in the range of 300 nm or more and 600 nm or less, and any of the phosphors described above.
- the excitation source may be a light emitting diode (LED) or laser diode (LD). Any one of the light-emitting elements described above emits fluorescence having a maximum emission peak at a wavelength in the range of 400 nm to 760 nm when irradiated with light having a wavelength in the range of 300 nm to 600 nm.
- One or more phosphors are provided that includes an excitation source that emits light with a wavelength in the range of 300 nm or more and 600 nm or less, and any of the phosphors described above.
- the excitation source may be a light emitting diode (LED) or laser diode (LD). Any one of the light-emitting elements described above emits fluorescence having a maximum emission peak at a
- any of the light-emitting devices described above includes AlN: (Eu, Si), BaMgAl 10 O 17 :Eu, SrSi 9 Al 19 ON 31 :Eu, LaSi 9 Al 19 N 32 :Eu, ⁇ -sialon: Ce, JEM : Ce, ⁇ -sialon: Eu, (Ba, Sr, Ca, Mg) 2 SiO 4 : Eu, (Ca, Sr, Ba) Si 2 O 2 N 2 : Eu, YAG: Ce, ⁇ -sialon: Eu, CaAlSiN3 :Ce, La3Si6N11 :Ce , CaAlSiN3 :Eu, ( Ca,Sr) AlSiN3 : Eu , Ca2Si5N8 : Eu , and Sr2Si5N8 : Eu It may contain one or more phosphors selected from the group.
- the light-emitting device includes any one of the light-emitting elements described above, and is any one of a lighting fixture, a backlight for a liquid phase panel, a lamp for a projector, an infrared illumination, and a light source for infrared measurement. good too. The above problems are solved.
- the phosphor is Sr 6x (Si,Al) 27-12x (O,N) 31-6x Li 3y crystal or Sr 3 Si 12.432 Al 8.568 O 1.608 N 26.
- a crystal having the same crystal structure as 392 Li 0.96 may be contained as a main component. They may emit light with higher brightness than conventional oxide phosphors and oxynitride phosphors. Certain compositions may excel as red or near-infrared phosphors. Even when exposed to an excitation source, such phosphors are less likely to lose brightness.
- FIG. 3 is a diagram showing emission spectra of phosphors synthesized in Experiment 1;
- FIG. 10 is a diagram showing emission spectra of phosphors synthesized in Experiment 2;
- 1 is a schematic diagram showing a lighting fixture (cannonball-shaped LED lighting fixture) according to the present invention;
- FIG. 1 is a schematic diagram showing a lighting fixture (board-mounted LED lighting fixture) according to the present invention;
- the phosphor contains at least elements A, M, D and E, where A is at least Mg (magnesium), Ca (calcium), Sr (strontium) and Ba ( barium), M is Mn (manganese), Eu (europium), Ce (cerium), Nd (neodymium), Tb (terbium), Dy (dysprosium) ), Ho (holminium), Er (erbium), Tm (thulium) and Yb (ytterbium) are one or more elements selected from the group consisting of Si (silicon) and Al (aluminum) one or two or more elements selected from the group consisting of E is one or two or more elements selected from the group consisting of O (oxygen) and N (nitrogen)); Accordingly, it contains a G element (where G is a Li (lithium) element), is represented by a composition of (A, M) a D d E
- G element is a Li element
- having a parameter value of 0.21 ⁇ g ⁇ 1.05 may satisfy the range of In particular, it is preferable because the emission intensity increases.
- An inorganic compound is a crystal represented by (A, M) 6x D 27-12x E 31-6x G 3y (where 0.4 ⁇ x ⁇ 0.8, 0 ⁇ y ⁇ 0.35) (referred to as the present crystal) may include It may also contain a crystal having the same crystal structure as (A,M) 6x D 27-12x E 31-6x G 3y (referred to as the same crystal).
- a phosphor has a high emission intensity.
- the same crystal may be a crystal having the same crystal structure as the Sr 3 Si 12.432 Al 8.568 O 1.608 N 26.392 Li 0.96 crystal.
- a crystal having the same crystal structure means that the positional coordinates of the corresponding atoms in the crystal lattice are the same or close to the original crystal, and the types of the corresponding atoms are partial or partial. All may mean different crystals.
- the present crystal belongs to the hexagonal system, P6 3 It was found to belong to the space group (space group number 173 of the International Tables for Crystallography) and occupy the crystal parameters and atomic coordinate positions shown in Table 1.
- the lattice constants a, b, and c indicate the lengths of the unit cell axes, and ⁇ , ⁇ , and ⁇ indicate the angles between the unit cell axes.
- Atomic coordinates indicate the position of each atom in a unit cell with a value between 0 and 1 in units of the unit cell.
- each atom of Sr, Si, Al, Li, O, and N is present, and an analytical result is obtained that Sr is present in two types of sites A1 to A2.
- an analysis result was obtained in which Si and Al exist in nine types of sites from B1 to B9 without distinguishing between sites.
- N and O exist in 11 types of seats from X1 to X11 without distinguishing between seats.
- FIG. 1 is a diagram showing the crystal structure of the Sr 3 Si 12.432 Al 8.568 O 1.608 N 26.392 Li 0.96 crystal.
- this crystal has the structure shown in FIG. and a structure containing Li elements. Although Sr and (O, N) are shown to coexist in FIG. 1, one of them actually exists.
- A contains at least one or more elements selected from the group consisting of Mg, Ca, Sr and Ba
- M is one or more elements selected from the group consisting of Mn, Eu, Ce, Nd, Tb, Dy, Ho, Er, Tm and Yb
- D is one or more elements selected from the group consisting of Si and Al
- E is one or more elements selected from the group consisting of O and N
- G can form crystals that are Li elements.
- x is a parameter that determines the amount of (A, M) and takes a value in the range of 0.4 ⁇ x ⁇ 0.8.
- y is a parameter that determines the amount of G, and takes a value in the range of 0 ⁇ y ⁇ 0.35. In particular, crystals are easily stabilized in the range of 0.023 ⁇ y ⁇ 0.35.
- the crystal structure of the general formula (A, M) 6x D 27-12x E 31-6x G 3y is the same as the Sr 3 Si 12.432 Al 8.568 O 1.608 N 26.392 Li 0.96 crystal.
- Table 1 the A01 and A02 positions are occupied by the A element and the M element, the B01 to B09 positions are occupied by the D element, the C01 position is occupied by the G element, and the X01 to X11 positions are the E element. occupies.
- the site occupancy and lattice constant change with changes in the type and composition of the elements, the crystal structure and atomic coordinates do not change significantly.
- (A,M) 6x D 27-12x E 31-6x G 3y crystal formation can be determined using the information in Table 1.
- a phosphor obtained by activating light-emitting ions in an inorganic substance has a high emission intensity.
- a phosphor whose base is a crystal belonging to the P63 space group (the 173rd space group of the International Tables for Crystallography) or the same crystal has a high emission intensity.
- a crystal containing Si and Al as the D element and having 0.4 ⁇ Al/(Al + Si) ⁇ 0.6 may have a particularly stable crystal structure. High luminous intensity.
- Crystals in which the E element contains O and N and where 0.01 ⁇ O/(O + N) ⁇ 0.1 may have a particularly stable crystal structure. High luminous intensity.
- a crystal containing a G element and having 0.15 ⁇ y ⁇ 0.3 may have a particularly stable crystal structure. High luminous intensity.
- M is Eu
- the Eu content m represented by (A, M) 6x D 27-12x E 31-6x G 3y is 0.001 ⁇ m ⁇ 0.001 ⁇ m ⁇ 0.001
- Phosphors having a composition of 1 may also be included.
- the above formula may be "A 6x-m M m D 27-12x E 31-6x G 3y ".
- a phosphor whose inorganic compound is an aggregate of single crystal particles or single crystals with an average particle size of 0.1 ⁇ m or more and 20 ⁇ m or less may have high luminous efficiency. Operability may be better when mounted on an LED. It is preferable to control the particle size within this range.
- Fe, Co, and Ni impurity elements contained in inorganic compounds may reduce the emission intensity.
- the sum of these elements in the phosphor may be 500 ppm or less. The influence of the decrease in emission intensity may be reduced.
- a phosphor having a content of 20% by mass or more may be included. This embodiment can be used when the present crystal or the same crystal as a host or a single phosphor containing an inorganic compound using the same crystal as a host crystal cannot obtain predetermined characteristics, or when a function such as conductivity is added. .
- the content of the phosphor containing the present crystal or the present same crystal as a host or an inorganic compound containing the host crystal may be adjusted so as to obtain predetermined characteristics. If it is 20% by mass or less, there is a possibility that the luminous intensity will be low.
- the method of manufacturing the phosphor does not have to be specified.
- a raw material mixture which is a mixture of metal compounds and can be fired to form the present crystal or a phosphor having the present same crystal as a host is heated at 1400° C. or higher and 2200° C. or lower in an inert atmosphere containing nitrogen. may be fired in the temperature range of
- the crystal of the inorganic compound included in the phosphor may belong to the space group P6-3 in the hexagonal system.
- crystals having a different crystal system or space group may be mixed. It can be used as a high-brightness phosphor because the change in emission characteristics is slight.
- Starting materials include A element (where A contains at least one or more elements selected from the group consisting of Mg, Ca, Sr and Ba), M element (where M is Mn , Eu, Ce, Nd, Tb, Dy, Ho, Er, Tm and Yb), D element (one selected from the group consisting of Si and Al or two or more elements), optionally selected from the group consisting of nitrides, oxynitrides, oxides, carbonates and fluorides of G elements (where G is Li element) You may use the raw material which is carried out.
- the furnace used for firing has a high firing temperature and the firing atmosphere is an inert atmosphere containing nitrogen.
- a hot electric furnace is preferred.
- the firing temperature should be 1400°C or higher and 2200°C or lower. If the temperature is lower than 1400°C, the reaction may not proceed sufficiently. If the temperature is 2200° C. or higher, there is a possibility that the raw material powder and the composite will decompose. Although the firing time varies depending on the firing temperature, it is usually about 1 to 48 hours.
- a pressure range of 0.1 MPa or more and 100 MPa or less in the inert atmosphere containing nitrogen is preferable because thermal decomposition of nitrides and oxynitrides, which are starting materials and products, is suppressed.
- the partial pressure of oxygen in the firing atmosphere is preferably 0.0001% or less in order to suppress the oxidation reaction of nitrides and oxynitrides, which are starting materials and products.
- the phosphor in the form of powder or agglomerate In order to manufacture the phosphor in the form of powder or agglomerate, a method of filling the raw material in a container while maintaining the filling rate of the bulk density of 40% or less and then sintering the raw material may be employed.
- the bulk density By setting the bulk density to a filling rate of 40% or less, strong adhesion between particles can be avoided.
- the relative bulk density is the ratio of the value (bulk density) obtained by dividing the mass of the powder filled in the container by the volume of the container and the true density of the powder substance.
- Various heat-resistant materials can be used as a container for holding the raw material mixture when firing the raw material mixture.
- Journal of the American Ceramic Society, Vol. 85, No. 5, 2002, pp. 1229-1234 a container coated with boron nitride as shown in the graphite crucible coated with boron nitride used for the synthesis of ⁇ -sialon, , or a boron nitride sintered body is suitable. If sintering is carried out under such conditions, boron or boron nitride components may be mixed into the product from the container, but if the amount is small, the luminescence characteristics will not deteriorate, so there will be little effect. In addition, the addition of small amounts of boron nitride may improve the durability of the product and may be preferred in some cases.
- the average particle size of the raw material powder particles or aggregates is 500 ⁇ m or less, because reactivity and operability are excellent.
- Sintering methods that do not apply external mechanical pressure, such as normal pressure sintering and gas pressure sintering, are used as methods for obtaining powder or agglomerate products without hot pressing. preferable.
- the average particle diameter of the phosphor powder is preferably 50 nm or more and 200 ⁇ m or less in terms of volume-based median diameter (d50), because the emission intensity is high.
- the volume-based average particle size can be measured, for example, by microtrack or laser scattering.
- the average particle size of the phosphor powder synthesized by firing may be adjusted to 50 nm or more and 200 ⁇ m or less by using one or more methods selected from pulverization, classification, and acid treatment.
- the sintered phosphor powder, the pulverized phosphor powder, or the particle size-adjusted phosphor powder By heat-treating the sintered phosphor powder, the pulverized phosphor powder, or the particle size-adjusted phosphor powder at a temperature of 1000° C. or higher and lower than the sintering temperature, defects contained in the powder and damage due to pulverization are removed. may recover. Defects and damages may cause a decrease in emission intensity, in which case the emission intensity may be recovered by heat treatment.
- the content of inorganic substances that form a liquid phase at a temperature below the firing temperature is reduced, which may increase the emission intensity of the phosphor.
- the phosphor when used for applications such as a light-emitting device, it is preferable to use such a phosphor in the form of being dispersed in a liquid medium. Also, in the embodiments of the present invention, it can be used as a phosphor mixture containing phosphors. In the embodiments of the present invention, a composition in which a phosphor is dispersed in a medium is called a phosphor-containing composition.
- the medium that can be used for the phosphor-containing composition may be one that can suitably disperse the phosphor in the examples of the present invention. Any one can be selected depending on the purpose, as long as it does not cause an unfavorable reaction or the like.
- media include glass, silicone resin, epoxy resin, polyvinyl-based resin, polyethylene-based resin, polypropylene-based resin, polyester-based resin, and the like. One of these media may be used alone, or two or more of them may be used in any combination and ratio.
- the amount of the medium used may be appropriately adjusted according to the application, etc.
- the weight ratio of the medium to the phosphor is usually 3% by weight or more, preferably 5% by weight. In addition, it may be in the range of usually 30% by weight or less, preferably 15% by weight or less.
- the light-emitting element may be configured using at least an excitation source (luminescence light source) and the phosphor in the embodiments of the present invention.
- Light-emitting light sources include light-emitting diodes (LEDs), laser diodes (LDs), organic EL light-emitting elements, fluorescent lamps, and the like. LEDs can be manufactured by known methods such as those described in JP-A-5-152609, JP-A-7-99345, and Japanese Patent Publication No. 2927279, using the phosphors in the examples of the present invention.
- the luminous body or light source preferably emits light having a wavelength in the range of 300 nm or more and 600 nm or less.
- a blue LED light-emitting element that emits light with a wavelength of 500 nm or less, or a green, yellow, or red LED light-emitting element that emits light with a wavelength of 500 nm or more and 600 nm or less can be used.
- Some of these LEDs are made of semiconductors such as GaN, InGaN, and AlGaAs, and by adjusting the composition, they can become light-emitting light sources that emit light of a predetermined wavelength.
- a light having a wavelength in the range of 300 nm or more and 600 nm or less is irradiated to emit light having a wavelength of 400 nm or more and 760 nm or less.
- Such phosphors may include one or more.
- a blue phosphor that emits light with a peak wavelength of 400 nm or more and 500 nm or less by a light emitter or light source is included.
- phosphors include AlN: (Eu, Si), BaMgAl 10 O 17 :Eu, SrSi 9 Al 19 ON 31 :Eu, LaSi 9 Al 19 N 32 :Eu, ⁇ -sialon: Ce, and JEM: Ce. and so on.
- a green phosphor that emits light with a peak wavelength of 500 nm or more and 550 nm or less by a light emitter or light source is included.
- examples of such green phosphors include ⁇ -sialon: Eu, (Ba, Sr, Ca, Mg) 2 SiO 4 : Eu, (Ca, Sr, Ba) Si 2 O 2 N 2 : Eu. be.
- a yellow phosphor that emits light with a peak wavelength of 550 nm or more and 600 nm or less by a light emitter or light source is included.
- Such yellow phosphors include YAG:Ce, ⁇ -sialon:Eu, CaAlSiN 3 :Ce, La 3 Si 6 N 11 :Ce, and the like.
- a red phosphor that emits light with a peak wavelength of 600 nm or more and 700 nm or less by a light emitter or light source is included.
- red phosphors include CaAlSiN 3 :Eu, (Ca,Sr)AlSiN 3 :Eu, Ca 2 Si 5 N 8 :Eu, and Sr 2 Si 5 N 8 :Eu.
- the light-emitting body or the light-emitting source uses an LED emitting light with a wavelength in the range of 320 nm or more and 500 nm or less. be able to.
- a light-emitting device includes the above-described light-emitting element, and such light-emitting devices include lighting fixtures, backlights for liquid phase panels, lamps for projectors, infrared illumination, and light sources for infrared measurement. and so on. It has been confirmed that the phosphor in the examples of the present invention emits light when excited by an electron beam, vacuum ultraviolet rays of 100 to 190 nm, ultraviolet rays of 190 to 380 nm, and visible light of 380 to 600 nm. By combining with the phosphor of the present invention, a light-emitting device as described above can be configured.
- the phosphor in the examples of the present invention which consists of an inorganic substance crystal phase having a specific chemical composition, has a red body color and can be used as a pigment or fluorescent pigment. That is, in the examples of the present invention, when the phosphor is irradiated with illumination such as sunlight or a fluorescent lamp, a red object color is observed.
- the phosphors in the inventive embodiments are suitable for inorganic pigments. Therefore, when used in paints, inks, paints, glazes, coloring agents added to plastic products, etc., good color development can be maintained over a long period of time.
- the phosphor is also suitable as an ultraviolet absorber because it absorbs ultraviolet rays. Therefore, when used as a paint, applied to the surface of a plastic product, or kneaded into the interior of a plastic product, it has a high ultraviolet blocking effect and can effectively protect the product from ultraviolet deterioration.
- the other light-emitting device includes a white light-emitting diode, an infrared light-emitting diode, a white and infrared light-emitting diode, or a plurality of these light-emitting diodes containing the phosphor in the embodiment of the present invention. lighting fixtures, backlights for liquid crystal panels, etc.
- the raw material powder used in the synthesis was a silicon nitride powder (SN-E10 manufactured by Ube Industries, Ltd.) having a particle size of 11.2 m 2 /g of specific surface area, an oxygen content of 1.29% by weight and an ⁇ -type content of 95%. grade), an aluminum nitride powder having a specific surface area of 3.3 m 2 /g and an oxygen content of 0.82% by weight (E grade manufactured by Tokuyama Corporation), and a specific surface area of 13.2 m 2 /g.
- Aluminum oxide powder (Tymicron manufactured by Taimei Chemical Industry Co., Ltd.), lithium nitride (Li 3 N; manufactured by Kojundo Scientific Laboratory) powder, magnesium nitride (Mg 3 N 2 ; manufactured by Kojundo Scientific Laboratory), and calcium nitride (Ca 3 N 2 ; manufactured by Kojundo Chemical Laboratory), 99.5% pure strontium nitride (Sr 3 N 2 ; manufactured by Materion), and 99.7% pure barium nitride (Ba 3 N 2 ; manufactured by Materion ), europium nitride (EuN; manufactured by Materion), rare earth nitride (manufactured by Materion), and rare earth oxide (purity 99.9% manufactured by Shin-Etsu Chemical Co., Ltd.).
- 32 and Sr 3 N 2 were weighed at a molar ratio of 1, and mixed for 5 minutes in a nitrogen atmosphere glove box with an oxygen content of 1 ppm using a silicon nitride sintered pestle and mortar. Next, the obtained mixed powder was put into a crucible made of a boron nitride sintered body. The bulk density of the mixed powder (powder) was about 30%.
- the crucible containing the mixed powder was set in a graphite resistance heating type electric furnace.
- the firing atmosphere is made into a vacuum with a pressure of 1 ⁇ 10 -1 Pa or less by a diffusion pump, and heated from room temperature to 800 ° C. at a rate of 500 ° C. per hour, and the purity is 99.999% by volume at 800 ° C.
- Nitrogen was introduced to set the pressure in the furnace to 1 MPa, the temperature was raised to 1900° C. at 500° C./hour, and the temperature was maintained for 2 hours.
- the compound was observed with an optical microscope, and crystal particles with a size of 40 ⁇ m were collected from the compound.
- SEM scanning electron microscope
- EDS energy dispersive elemental analyzer
- the elements contained in the crystal grains were analyzed. Analysis was carried out. As a result, the existence of Sr, Si, and Al elements was confirmed, and it was confirmed that the composition was as designed.
- this crystal was fixed to the tip of the glass fiber with an organic adhesive.
- a single-crystal X-ray diffractometer (SMART APEXII Ultra manufactured by Bruker AXS Co., Ltd.) with a rotating anticathode for MoK ⁇ rays, X-ray diffraction was measured under the condition that the output of the X-ray source was 50 kV and 50 mA. . As a result, it was confirmed that this crystal grain was a single crystal.
- the crystal structure was determined from the X-ray diffraction measurement results using single crystal structure analysis software (APEX2 manufactured by Bruker AXS).
- the obtained crystal structure data is shown in Table 1, and a diagram of the crystal structure is shown in FIG. Table 1 describes the crystal system, space group, lattice constants, atom types and atomic positions, and this data can be used to determine the shape and size of the unit cell and the arrangement of atoms within it. .
- the atomic positions were as shown in Table 1. Si and Al are present at the same atomic position B at a certain ratio, and the ratio was obtained from the EDS atomic ratio. O and N are present at the same atomic position X in a certain ratio, and the ratio was obtained from the electric neutrality condition of the crystal.
- the composition of this crystal determined from single crystal X-ray structure analysis was Sr 3 Si 12.432 Al 8.568 O 1.608 N 26.392 Li 0.96 .
- FIG. 2 is a diagram showing powder X-ray diffraction using CuK ⁇ rays calculated from the crystal structure of the Sr 3 Si 12.432 Al 8.568 O 1.608 N 26.392 Li 0.96 crystal.
- the powder X - diffraction measurement of the compound was performed, and if the measured powder pattern was substantially the same as in FIG . It can be determined that Li 0.96 is produced. Furthermore, if the lattice constant, etc. is changed while maintaining the crystal structure by changing the composition, the powder X-ray pattern is calculated from the lattice constant value obtained by powder X-ray diffraction measurement and the crystal structure data in Table 1. can be calculated, it can be determined that the same crystal is produced by comparing with the calculated pattern.
- the Sr site can be substituted with the A element and the M element.
- the A element is an element selected from the group consisting of Mg, Ca, Sr and Ba
- the M element is Mn, Eu, Ce, Nd, Tb, Dy, Ho, Er, Tm and Yb.
- the present crystal and the present identical crystal can be described by the general formula (A, M) 6x D 27-12x E 31-6x G 3y .
- the E element is O and/or N
- the G element is Li.
- the raw material powders are Si 3 N 4 : 31.281, AlN: 55.0075, Al 2 O 3 : 3.8864, Li 3 N: 2.09268, Sr 3 N 2 : 7.1996, EuN: 0.74479. and mixed for 5 minutes using a silicon nitride sintered pestle and mortar in a nitrogen atmosphere glove box with an oxygen content of 1 ppm.
- the obtained mixed powder was put into a crucible made of a boron nitride sintered body.
- the bulk density of the mixed powder (powder) was about 30%.
- the crucible containing the mixed powder was set in a graphite resistance heating type electric furnace.
- the firing atmosphere is made into a vacuum with a pressure of 1 ⁇ 10 -1 Pa or less by a diffusion pump, and heated from room temperature to 800 ° C. at a rate of 500 ° C. per hour, and the purity is 99.999% by volume at 800 ° C.
- Nitrogen was introduced to set the pressure in the furnace to 1 MPa, and the temperature was raised to 1900° C. at 500° C./hour, and held at that temperature for 2 hours.
- the compound was observed with an optical microscope, and crystal particles with a size of 40 ⁇ m were collected from the compound.
- SEM scanning electron microscope
- EDS energy dispersive elemental analyzer
- the elements contained in the crystal grains were analyzed. Analysis was carried out. As a result, the presence of Sr, Eu, Si, and Al elements was confirmed, and it was confirmed that the composition was as designed.
- this crystal was fixed to the tip of the glass fiber with an organic adhesive.
- a single crystal X-ray diffractometer (SMART APEXII Ultra manufactured by Bruker AXS) with a MoK ⁇ ray rotating anticathode, X-ray diffraction was measured under the condition that the output of the X-ray source was 50 kV and 50 mA. . As a result, it was confirmed that this crystal grain was a single crystal.
- the crystal structure was obtained from the X-ray diffraction measurement results using single crystal structure analysis software (APEX2 manufactured by Bruker AXS).
- the obtained structure was the same as the crystal structure of this crystal.
- Sr and Eu enter at the same atomic positions at a certain ratio, and oxygen and nitrogen enter at the same atomic positions at a certain ratio, and when averaged as a whole, the composition ratio of the crystal is obtained.
- FIG. 3 is a diagram showing emission spectra of phosphors synthesized in Experiment 1.
- the sample of Experiment 1 was a phosphor that emitted red light having a maximum emission peak at a wavelength of 667 nm when excited with light having a wavelength of 410 nm.
- FIG. 4 is a diagram showing emission spectra of phosphors synthesized in Experiment 2.
- the sample synthesized in experiment 2 is (Sr2, Eu1 )( Si12.6 , Al8.4 )( O1.56 , N26.44 ) Li0.84 , and the light with a wavelength of 424 nm It was found to be an infrared-emitting phosphor having an emission peak maximum at a wavelength of 741 nm when excited by .
- At least A element, M element, D element, and E element (where A is at least one selected from the group consisting of Mg, Ca, Sr and Ba, or containing two or more elements, M is one or more elements selected from the group consisting of Mn, Eu, Ce, Nd, Tb, Dy, Ho, Er, Tm and Yb, and D is one or two or more elements selected from the group consisting of Si and Al, and E is one or two or more elements selected from the group consisting of O and N) and, if necessary, G containing an element (where G is a Li element), (A, M) is represented by the composition of a D d E e G g , and the atomic fraction parameters a, d, e, and g are 2.4 ⁇ a ⁇ 4.8 17.4 ⁇ d ⁇ 22.2 26.2 ⁇ e ⁇ 28.6 0 ⁇ g ⁇ 3
- A is at least one selected from the group consisting of Mg, Ca, Sr and Ba, or
- FIG. 5 is a schematic diagram showing a lighting fixture (bullet-shaped LED lighting fixture) according to the present invention.
- a cannonball-shaped white light-emitting diode lamp (1) shown in FIG. 5 was manufactured as a light-emitting device.
- the lower electrode of the ultraviolet light emitting diode element (4) and the bottom surface of the recess are electrically connected by a conductive paste, and the upper electrode and another lead wire (3) are electrically connected by a thin gold wire (5). It is connected to the.
- a phosphor (7) is dispersed in resin and mounted near the light emitting diode element (4).
- This phosphor-dispersed first resin (6) is transparent and covers the entire ultraviolet light emitting diode element (4).
- the tip of the lead wire including the recess, the blue light emitting diode element, and the first resin in which the phosphor is dispersed are sealed with a transparent second resin (8).
- the transparent second resin (8) has a substantially columnar shape as a whole, and the tip thereof has a lens-shaped curved surface, which is commonly called a bullet shape.
- Example 114 35% by weight of phosphor powder obtained by mixing the phosphor produced in Experiment 1, JEM:Ce blue phosphor, ⁇ -sialon:Eu, and CaAlSiN 3 :Eu at a mass ratio of 4:4:1:1. It was mixed with an epoxy resin at a concentration, and an appropriate amount of this was dropped using a dispenser to form a first resin (6) in which a phosphor mixture (7) was dispersed. The color of the obtained light-emitting device was white containing light-emitting components from blue to infrared.
- FIG. 6 is a schematic diagram showing a lighting fixture (board-mounted LED lighting fixture) according to the present invention.
- a chip-type light-emitting diode lamp (11) for substrate mounting shown in FIG. 6 was manufactured.
- Two lead wires (12, 13) are fixed to a white alumina ceramics substrate (19) with high reflectance of visible light. It is an electrode that is soldered when mounted on an electric board.
- a blue light-emitting diode element (14) having an emission peak wavelength of 450 nm is placed and fixed on one end of one of the lead wires (12) so as to be located in the center of the substrate.
- the lower electrode of the blue light emitting diode element (14) and the lower lead wire are electrically connected by a conductive paste, and the upper electrode and another lead wire (13) are electrically connected by a thin gold wire (15). properly connected.
- a mixture of the first resin (16) and the phosphor (17) obtained by mixing the phosphor prepared in Experiment 1 and the CaAlSiN 3 :Eu red phosphor at a mass ratio of 1:1 was placed in the vicinity of the light emitting diode element.
- the first resin in which the phosphor is dispersed is transparent and covers the entire blue light emitting diode element (14).
- a wall member (20) having a hole in the center is fixed on the ceramic substrate.
- the wall surface member (20) has a hole in its central portion for receiving the resin (16) in which the blue light emitting diode element (14) and the phosphor (17) are dispersed, and the portion facing the central portion is a slope.
- This slope is a reflecting surface for extracting light forward, and the curved shape of the slope is determined in consideration of the direction of light reflection.
- at least the surface constituting the reflecting surface is a surface having high visible light reflectance with white or metallic luster.
- the wall surface member (20) is made of white silicone resin.
- the hole in the center of the wall member forms a recess as the final shape of the chip-type light-emitting diode lamp.
- 16) is filled with a transparent second resin (18) so as to seal all of them.
- the same epoxy resin was used for the first resin (16) and the second resin (18). Red and infrared emitting LEDs were obtained.
- the nitride/oxynitride phosphor of the present invention has different emission characteristics (emission color, excitation characteristics, emission spectrum) from conventional phosphors, and has high emission intensity even when combined with an LED excitation source. , is chemically and thermally stable, and the brightness of the phosphor is less reduced when exposed to an excitation source. In the future, it can be expected to be widely used in material design for various display devices and contribute to the development of industry.
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Abstract
Description
(A,M)aDdEeGgの組成で表され、原子分率パラメータa、d、e、gが、
2.4 ≦ a ≦ 4.8
17.4≦ d ≦ 22.2
26.2 ≦ e ≦ 28.6
0 ≦ g ≦ 3
の数値で表される無機化合物を含んでもよい。上記課題が解決される。
前記パラメータgが、
0.21 ≦ g ≦ 1.05
の範囲の数値で表されてもよい。
前記無機化合物は、(A,M)6xD27-12xE31-6xG3y(ただし、xおよびyは、それぞれ、0.4≦x≦0.8、0≦y≦0.35を満たす)の組成で表されてもよい。
ここで、「(A,M)6x」は、A原子及びM原子が共に存在し(即ち、各原子の添数字は0より大きく)、A原子及びM原子を合計した数が「6x」であることを意味してよい。例えば、パラメータp及びqをp+q=6xとするようにすると、添え数字により上記式は、「(ApMq)D27-12xE31-6xG3y(ただし、p+q=6x、p>0、q>0)」とすることもできる。
前記xは、0.45≦x≦0.55を満たしてもよい。
前記無機化合物が、(A,M)6xD27-12xE31-6xG3y(ただし、0.4≦x≦0.8、0≦y≦0.35)であらわされる結晶(本結晶という)を含んでもよい。また、本結晶と同一の結晶構造を有する結晶(本同一結晶という)であってもよい。
前記無機化合物が、(Sr,Eu)3(Si,Al)21(O,N)28Li0.96であらわされる結晶を含んでもよい。
無機化合物が、Sr3Si12.432Al8.568O1.608N26.392Li0.96と同一の結晶構造を有する結晶を含んでもよい。
前記本結晶および前記本同一結晶が、六方晶系であり、格子定数a、b、cが
1.6 < a < 1.8 nm
b = a
0.44 < c < 0.52 nm
であってもよい。
前記本結晶および前記本同一結晶が、P63空間群(International Tables for Crystallographyの173番の空間群)に属する結晶であってもよい。
前記無機化合物が、Sr6x(Si,Al)27-12x(O,N)31-6xLi3y(ただし、0.4≦x≦0.8、0≦y≦0.35)で表される結晶、または、それと同一の結晶構造を有する結晶を含んでもよく、さらにM元素を含んでもよい。
前記A元素がSrであり、前記M元素がEuであり、前記E元素がOおよびNからなる群から選ばれる1種または2種以上の元素であってもよい。
前記D元素は、SiおよびAlを含み、
0.4 ≦ Al/(Al+Si)≦ 0.6を満たしてもよい。
前記E元素は、OおよびNを含み、
0.01 ≦ O/(O+N)≦ 0.1を満たしてもよい。
上述するいずれかの蛍光体は、300nm以上600nm以下の範囲の波長の光を照射することにより、600nm以上850nm以下の範囲の波長に発光ピークの最大値をもつ発光をしてもよい。
本発明の実施例において、上述されるいずれかの蛍光体を製造する方法は、A元素(ただし、Aは、Mg、Ca、SrおよびBaからなる群から選ばれる1種または2種以上の元素である)、M元素(ただし、Mは、Mn、Eu、Ce、Nd、Tb、Dy、Ho、Er、TmおよびYbからなる群から選ばれる1種または2種以上の元素である)、D元素(SiおよびAlからなる群から選ばれる1種または2種以上の元素である)、必要に応じてG元素(ただし、GはLi元素である)の窒化物、酸窒化物、酸化物、炭酸塩およびフッ化物からなる群から1以上選択される原料を混合し、1400℃以上2200℃以下の温度で焼成するステップを含んでもよい。上記課題が解決される。
300nm以上600nm以下の範囲の波長の光を発する励起源と、上述するいずれかの蛍光体とを含む発光素子が提供されてもよい。上記課題が解決される。
前記励起源が発光ダイオード(LED)またはレーザーダイオード(LD)であってもよい。
上述されるいずれかの発光素子は、300nm以上600nm以下の範囲の波長の光を照射することにより400nm以上760nm以下の範囲の波長に発光ピークの最大値をもつ蛍光を発する、1以上の蛍光体を含んでもよい。
上述されるいずれかの発光素子は、AlN:(Eu,Si)、BaMgAl10O17:Eu、SrSi9Al19ON31:Eu、LaSi9Al19N32:Eu、α-サイアロン:Ce、JEM:Ce、β-サイアロン:Eu、(Ba,Sr,Ca,Mg)2SiO4:Eu、(Ca,Sr,Ba)Si2O2N2:Eu、YAG:Ce、α-サイアロン:Eu、CaAlSiN3:Ce、La3Si6N11:Ce、CaAlSiN3:Eu、(Ca,Sr)AlSiN3:Eu、Ca2Si5N8:Eu、および、Sr2Si5N8:Euからなる群から選ばれる1種または2種以上の蛍光体を含んでもよい。
本発明の実施例において、発光装置は、上述するいずれかの発光素子を含み、照明器具、液相パネル用バックライト、プロジェクター用ランプ、赤外照明、赤外計測用光源のいずれかであってもよい。上記課題が解決される。
本発明の実施例において、蛍光体は、少なくともA元素と、M元素と、D元素と、E元素(ただし、Aは、少なくともMg(マグネシウム)、Ca(カルシウム)、Sr(ストロンチウム)およびBa(バリウム)からなる群から選ばれる1種または2種以上の元素を含み、Mは、Mn(マンガン)、Eu(ユーロピウム)、Ce(セリウム)、Nd(ネオジウム)、Tb(テルビウム)、Dy(ジスプロシウム)、Ho(ホルミニウム)、Er(エルビウム)、Tm(ツリウム)およびYb(イッテルビウム)からなる群から選ばれる1種または2種以上の元素であり、Dは、Si(ケイ素)およびAl(アルミニウム)からなる群から選ばれる1種または2種以上の元素であり、Eは、O(酸素)およびN(窒素)からなる群から選ばれる1種または2種以上の元素である)と、必要に応じてG元素(ただし、GはLi(リチウム)元素である)を含み、(A,M)aDdEeGgの組成で表され、原子分率パラメータa、d、e、gが、
2.4 ≦ a ≦ 4.8
17.4≦ d ≦ 22.2
26.2 ≦ e ≦ 28.6
0 ≦ g ≦ 3
の数値で表される無機化合物を含んでもよい。600nm以下の波長の光を照射することにより、600nm以上の赤色および近赤外域に発光し、蛍光体として機能してもよい。パラメータの数値がこの範囲を外れると、発光強度が低くなる虞がある。なお、A元素として、さらに、Y(イットリウム)、Lu(ルテチウム)およびLa(ランタン)からなる群から選択される元素を含有してもよい。
0.21 ≦ g ≦ 1.05
の範囲を満たしてもよい。特に発光強度が高くなるので好ましい。
(A,M)6xD27-12xE31-6xG3y結晶、
A6xD27-12xE31-6xG3y結晶、
(Sr,Eu)3(Si,Al)21(O,N)28Li0.96結晶、
Sr3Si12.432Al8.568O1.608N26.392Li0.96結晶、
を挙げることができる。これらの結晶は、本発明者らが新たに合成し、結晶構造解析により新規結晶であると確認した。本発明者らが知る限りにおいて、本願より以前において報告されていない結晶である。
ここで、
Aは、少なくともMg、Ca、SrおよびBaからなる群から選ばれる1種または2種以上の元素を含み、
Mは、Mn、Eu、Ce、Nd、Tb、Dy、Ho、Er、TmおよびYbからなる群から選ばれる1種または2種以上の元素であり、
Dは、SiおよびAlからなる群から選ばれる1種または2種以上の元素であり、
Eは、OおよびNからなる群から選ばれる1種または2種以上の元素であり、
GはLi元素である
結晶を構成することができる。
1.6 < a < 1.8 nm
b = a
0.44 < c < 0.52 nm
である無機物質に発光イオンを付活した蛍光体は発光強度が高い。本結晶あるいは本同一結晶がP63空間群(International Tables for Crystallographyの173番の空間群)に属する結晶を母体とする蛍光体は発光強度が高い。
合成に使用した原料粉末は、比表面積11.2m2/gの粒度の、酸素含有量1.29重量%、α型含有量95%の窒化ケイ素粉末(宇部興産(株)製のSN-E10グレード)と、比表面積3.3m2/gの粒度の、酸素含有量0.82重量%の窒化アルミニウム粉末((株)トクヤマ製のEグレード)と、比表面積13.2m2/gの粒度の酸化アルミニウム粉末(大明化学工業製タイミクロン)と、窒化リチウム(Li3N;高純度科学研究所製)粉末と、窒化マグネシウム(Mg3N2;高純度科学研究所製)と、窒化カルシウム(Ca3N2;高純度化学研究所製)と、純度99.5%の窒化ストロンチウム(Sr3N2;マテリオン製)と、純度99.7%の窒化バリウム(Ba3N2;マテリオン製)と、窒化ユーロピウム(EuN;マテリオン製)と、希土類窒化物(マテリオン製)と、希土類酸化物(純度99.9%信越化学工業製)とであった。
Sr3Si12.432Al8.568O1.608N26.392Li0.96結晶を合成して、結晶構造を解析した。
a=b= 1.7416nm、
c= 0.48775nm、
角度α=β= 90°
角度γ=120°
であった。また原子位置は表1に示す通りであった。なお、SiとAlは同じ原子位置Bにある割合で存在し、その比はEDSの原子比から求めた。OとNは同じ原子位置Xにある割合で存在し、その比は結晶の電気的中性の条件から求めた。単結晶X線構造解析から求めたこの結晶の組成は
Sr3Si12.432Al8.568O1.608N26.392Li0.96であった。
(1)SiとAlは同じ席を占めるため置換することができる
(2)OとNは同じ席を占めるため置換することができる
(3)結晶中のSrの席と、(Si,Al)(O,N)4の席は置換することができる
(4)Liの量は変化させることができる
ことが判明したので、この結晶は、パラメータxとyを用いて、
Sr6x(Si,Al)27-12x(O,N)31-6xLi3y
x=0.5
y=0.32
Al/(Al+Si)=8.568/21
O/(O+N)=1.608/28
と記述できることがわかった。様々な組成で合成したところ、得られた結晶はすべて、
Sr6x(Si,Al)27-12x(O,N)31-6xLi3y
で記述できた。また、パラメータxとyは、
0.4≦x≦0.8
0≦y≦0.35
の範囲でこの結晶構造をとることがわかった。
[実験1]
次に、Sr6x(Si,Al)27-12x(O,N)31-6xLi3y;x=0.5、y=0.28を母体結晶とする蛍光体(Sr,Eu)6x(Si,Al)27-12x(O,N)31-6xLi3yを合成した。
図3は、実験1で合成した蛍光体の発光スペクトルを示す図である。
表2に示す組成で混合し、実験1と同じ製造方法で(A,M)6xD27-12xE31-6xG3y蛍光体を合成した。合成物から結晶粒子を採取し、単結晶X線回折装置で結晶相を同定した結果、表1に示すSr3Si12.432Al8.568O1.608N26.392Li0.96と同一の結晶構造であることを確認した。これらの粉末の発光スペクトルを測定した。結果を表3および図4に示す。
図4は、実験2で合成した蛍光体の発光スペクトルを示す図である。
表4および表5に示す組成で混合し、実験1と同じ製造方法で(A、M)6xD27-12xE31-6xG3y蛍光体を合成した。合成物から結晶粒子を採取し、単結晶X線回折装置で結晶相を同定した結果、実験59および実験69で合成した試料を除いて表1に示すSr3Si12.432Al8.568O1.608N26.392Li0.96と同一の結晶構造と同一の結晶構であることを確認した。ここで、実験59および実験69は、参考実験例である。
表6に示す組成で混合し、実験1と同じ製造方法で(A、M)6xD27-12xE31-6xG3y蛍光体を合成した。合成物から結晶粒子を採取し、単結晶X線回折装置で結晶相を同定した結果、表1に示すSr3Si12.432Al8.568O1.608N26.392Li0.96と同一の結晶構造と同一の結晶構であることを確認した。
(A,M)aDdEeGgの組成で表され、原子分率パラメータa、d、e、gが、
2.4 ≦ a ≦ 4.8
17.4≦ d ≦ 22.2
26.2 ≦ e ≦ 28.6
0 ≦ g ≦ 3
の数値で表される無機化合物である、蛍光体が提供できるが、以下のようなMがEuである具体的な組成系は特に重要である。
(Mg,Eu)aSidOeLig、(Mg,Eu)aSidOe、(Mg,Eu)aSid(O,N)eLig、(Mg,Eu)aSid(O,N)e、(Mg,Eu)aSidNeLig、(Mg,Eu)aSidNe、(Mg,Eu)a(Si,Al)dOeLig、(Mg,Eu)a(Si,Al)dOe、(Mg,Eu)a(Si,Al)d(O,N)eLig、(Mg,Eu)a(Si,Al)d(O,N)e、(Mg,Eu)a(Si,Al)dNeLig、(Mg,Eu)a(Si,Al)dNe、(Mg,Eu)aAldOeLig、(Mg,Eu)aAldOe、(Mg,Eu)aAld(O,N)eLig、(Mg,Eu)aAld(O,N)e、(Mg,Eu)aAldNeLig、(Mg,Eu)aAldNe、(Ca,Eu)aSidOeLig、(Ca,Eu)aSidOe、(Ca,Eu)aSid(O,N)eLig、(Ca,Eu)aSid(O,N)e、(Ca,Eu)aSidNeLig、(Ca,Eu)aSidNe、(Ca,Eu)a(Si,Al)dOeLig、(Ca,Eu)a(Si,Al)dOe、(Ca,Eu)a(Si,Al)d(O,N)eLig、(Ca,Eu)a(Si,Al)d(O,N)e、(Ca,Eu)a(Si,Al)dNeLig、(Ca,Eu)a(Si,Al)dNe、(Ca,Eu)aAldOeLig、(Ca,Eu)aAldOe、(Ca,Eu)aAld(O,N)eLig、(Ca,Eu)aAld(O,N)e、(Ca,Eu)aAldNeLig、(Ca,Eu)aAldNe、(Sr,Eu)aSidOeLig、(Sr,Eu)aSidOe、(Sr,Eu)aSid(O,N)eLig、(Sr,Eu)aSid(O,N)e、(Sr,Eu)aSidNeLig、(Sr,Eu)aSidNe、(Sr,Eu)a(Si,Al)dOeLig、(Sr,Eu)a(Si,Al)dOe、(Sr,Eu)a(Si,Al)d(O,N)eLig、(Sr,Eu)a(Si,Al)d(O,N)e、(Sr,Eu)a(Si,Al)dNeLig、(Sr,Eu)a(Si,Al)dNe、(Sr,Eu)aAldOeLig、(Sr,Eu)aAldOe、(Sr,Eu)aAld(O,N)eLig、(Sr,Eu)aAld(O,N)e、(Sr,Eu)aAldNeLig、(Sr,Eu)aAldNe、(Ba,Eu)aSidOeLig、(Ba,Eu)aSidOe、(Ba,Eu)aSid(O,N)eLig、(Ba,Eu)aSid(O,N)e、(Ba,Eu)aSidNeLig、(Ba,Eu)aSidNe、(Ba,Eu)a(Si,Al)dOeLig、(Ba,Eu)a(Si,Al)dOe、(Ba,Eu)a(Si,Al)d(O,N)eLig、(Ba,Eu)a(Si,Al)d(O,N)e、(Ba,Eu)a(Si,Al)dNeLig、(Ba,Eu)a(Si,Al)dNe、(Ba,Eu)aAldOeLig、(Ba,Eu)aAldOe、(Ba,Eu)aAld(O,N)eLig、(Ba,Eu)aAld(O,N)e、(Ba,Eu)aAldNeLig、(Ba,Eu)aAldNe、(Mg,Ca,Eu)aSidOeLig、(Mg,Ca,Eu)aSidOe、(Mg,Ca,Eu)aSid(O,N)eLig、(Mg,Ca,Eu)aSid(O,N)e、(Mg,Ca,Eu)aSidNeLig、(Mg,Ca,Eu)aSidNe、(Mg,Ca,Eu)a(Si,Al)dOeLig、(Mg,Ca,Eu)a(Si,Al)dOe、(Mg,Ca,Eu)a(Si,Al)d(O,N)eLig、(Mg,Ca,Eu)a(Si,Al)d(O,N)e、(Mg,Ca,Eu)a(Si,Al)dNeLig、(Mg,Ca,Eu)a(Si,Al、Eu)dNe、(Mg,Ca,Eu)aAldOeLig、(Mg,Ca,Eu)aAldOe、(Mg,Ca,Eu)aAld(O,N)eLig、(Mg,Ca,Eu)aAld(O,N)e、(Mg,Ca,Eu)aAldNeLig、(Mg,Ca,Eu)aAldNe、(Mg,Sr,Eu)aSidOeLig、(Mg,Sr,Eu)aSidOe、(Mg,Sr,Eu)aSid(O,N)eLig、(Mg,Sr,Eu)aSid(O,N)e、(Mg,Sr,Eu)aSidNeLig、(Mg,Sr,Eu)aSidNe、(Mg,Sr,Eu)a(Si,Al)dOeLig、(Mg,Sr,Eu)a(Si,Al)dOe、(Mg,Sr,Eu)a(Si,Al)d(O,N)eLig、(Mg,Sr,Eu)a(Si,Al)d(O,N)e、(Mg,Sr,Eu)a(Si,Al)dNeLig、(Mg,Sr,Eu)a(Si,Al、Eu)dNe、(Mg,Sr,Eu)aAldOeLig、(Mg,Sr,Eu)aAldOe、(Mg,Sr,Eu)aAld(O,N)eLig、(Mg,Sr,Eu)aAld(O,N)e、(Mg,Sr,Eu)aAldNeLig、(Mg,Sr,Eu)aAldNe、(Mg,Ba,Eu)aSidOeLig、(Mg,Ba,Eu)aSidOe、(Mg,Ba,Eu)aSid(O,N)eLig、(Mg,Ba,Eu)aSid(O,N)e、(Mg,Ba,Eu)aSidNeLig、(Mg,Ba,Eu)aSidNe、(Mg,Ba,Eu)a(Si,Al)dOeLig、(Mg,Ba,Eu)a(Si,Al)dOe、(Mg,Ba,Eu)a(Si,Al)d(O,N)eLig、(Mg,Ba,Eu)a(Si,Al)d(O,N)e、(Mg,Ba,Eu)a(Si,Al)dNeLig、(Mg,Ba,Eu)a(Si,Al、Eu)dNe、(Mg,Ba,Eu)aAldOeLig、(Mg,Ba,Eu)aAldOe、(Mg,Ba,Eu)aAld(O,N)eLig、(Mg,Ba,Eu)aAld(O,N)e、(Mg,Ba,Eu)aAldNeLig、(Mg,Ba,Eu)aAldNe、(Ca,Sr,Eu)aSidOeLig、(Ca,Sr,Eu)aSidOe、(Ca,Sr,Eu)aSid(O,N)eLig、(Ca,Sr,Eu)aSid(O,N)e、(Ca,Sr,Eu)aSidNeLi
g、(Ca,Sr,Eu)aSidNe、(Ca,Sr,Eu)a(Si,Al)dOeLig、(Ca,Sr,Eu)a(Si,Al)dOe、(Ca,Sr,Eu)a(Si,Al)d(O,N)eLig、(Ca,Sr,Eu)a(Si,Al)d(O,N)e、(Ca,Sr,Eu)a(Si,Al)dNeLig、(Ca,Sr,Eu)a(Si,Al、Eu)dNe、(Ca,Sr,Eu)aAldOeLig、(Ca,Sr,Eu)aAldOe、(Ca,Sr,Eu)aAld(O,N)eLig、(Ca,Sr,Eu)aAld(O,N)e、(Ca,Sr,Eu)aAldNeLig、(Ca,Sr,Eu)aAldNe、(Ca,Ba,Eu)aSidOeLig、(Ca,Ba,Eu)aSidOe、(Ca,Ba,Eu)aSid(O,N)eLig、(Ca,Ba,Eu)aSid(O,N)e、(Ca,Ba,Eu)aSidNeLig、(Ca,Ba,Eu)aSidNe、(Ca,Ba,Eu)a(Si,Al)dOeLig、(Ca,Ba,Eu)a(Si,Al)dOe、(Ca,Ba,Eu)a(Si,Al)d(O,N)eLig、(Ca,Ba,Eu)a(Si,Al)d(O,N)e、(Ca,Ba,Eu)a(Si,Al)dNeLig、(Ca,Ba,Eu)a(Si,Al、Eu)dNe、(Ca,Ba,Eu)aAldOeLig、(Ca,Ba,Eu)aAldOe、(Ca,Ba,Eu)aAld(O,N)eLig、(Ca,Ba,Eu)aAld(O,N)e、(Ca,Ba,Eu)aAldNeLig、(Ca,Ba,Eu)aAldNe、(Sr,Ba,Eu)aSidOeLig、(Sr,Ba,Eu)aSidOe、(Sr,Ba,Eu)aSid(O,N)eLig、(Sr,Ba,Eu)aSid(O,N)e、(Sr,Ba,Eu)aSidNeLig、(Sr,Ba,Eu)aSidNe、(Sr,Ba,Eu)a(Si,Al)dOeLig、(Sr,Ba,Eu)a(Si,Al)dOe、(Sr,Ba,Eu)a(Si,Al)d(O,N)eLig、(Sr,Ba,Eu)a(Si,Al)d(O,N)e、(Sr,Ba,Eu)a(Si,Al)dNeLig、(Sr,Ba,Eu)a(Si,Al、Eu)dNe、(Sr,Ba,Eu)aAldOeLig、(Sr,Ba,Eu)aAldOe、(Sr,Ba,Eu)aAld(O,N)eLig、(Sr,Ba,Eu)aAld(O,N)e、(Sr,Ba,Eu)aAldNeLig、(Sr,Ba,Eu)aAldNe、(Mg,Ca,Sr,Eu)aSidOeLig、(Mg,Ca,Sr,Eu)aSidOe、(Mg,Ca,Sr,Eu)aSid(O,N)eLig、(Mg,Ca,Sr,Eu)aSid(O,N)e、(Mg,Ca,Sr,Eu)aSidNeLig、(Mg,Ca,Sr,Eu)aSidNe、(Mg,Ca,Sr,Eu)a(Si,Al)dOeLig、(Mg,Ca,Sr,Eu)a(Si,Al)dOe、(Mg,Ca,Sr,Eu)a(Si,Al)d(O,N)eLig、(Mg,Ca,Sr,Eu)a(Si,Al)d(O,N)e、(Mg,Ca,Sr,Eu)a(Si,Al)dNeLig、(Mg,Ca,Sr,Eu)a(Si,Al、Eu)dNe、(Mg,Ca,Sr,Eu)aAldOeLig、(Mg,Ca,Sr,Eu)aAldOe、(Mg,Ca,Sr,Eu)aAld(O,N)eLig、(Mg,Ca,Sr,Eu)aAld(O,N)e、(Mg,Ca,Sr,Eu)aAldNeLig、(Mg,Ca,Sr,Eu)aAldNe、(Mg,Ca,Ba,Eu)aSidOeLig、(Mg,Ca,Ba,Eu)aSidOe、(Mg,Ca,Ba,Eu)aSid(O,N)eLig、(Mg,Ca,Ba,Eu)aSid(O,N)e、(Mg,Ca,Ba,Eu)aSidNeLig、(Mg,Ca,Ba,Eu)aSidNe、(Mg,Ca,Ba,Eu)a(Si,Al)dOeLig、(Mg,Ca,Ba,Eu)a(Si,Al)dOe、(Mg,Ca,Ba,Eu)a(Si,Al)d(O,N)eLig、(Mg,Ca,Ba,Eu)a(Si,Al)d(O,N)e、(Mg,Ca,Ba,Eu)a(Si,Al)dNeLig、(Mg,Ca,Ba,Eu)a(Si,Al、Eu)dNe、(Mg,Ca,Ba,Eu)aAldOeLig、(Mg,Ca,Ba,Eu)aAldOe、(Mg,Ca,Ba,Eu)aAld(O,N)eLig、(Mg,Ca,Ba,Eu)aAld(O,N)e、(Mg,Ca,Ba,Eu)aAldNeLig、(Mg,Ca,Ba,Eu)aAldNe、(Mg,Sr,Ba,Eu)aSidOeLig、(Mg,Sr,Ba,Eu)aSidOe、(Mg,Sr,Ba,Eu)aSid(O,N)eLig、(Mg,Sr,Ba,Eu)aSid(O,N)e、(Mg,Sr,Ba,Eu)aSidNeLig、(Mg,Sr,Ba,Eu)aSidNe、(Mg,Sr,Ba,Eu)a(Si,Al)dOeLig、(Mg,Sr,Ba,Eu)a(Si,Al)dOe、(Mg,Sr,Ba,Eu)a(Si,Al)d(O,N)eLig、(Mg,Sr,Ba,Eu)a(Si,Al)d(O,N)e、(Mg,Sr,Ba,Eu)a(Si,Al)dNeLig、(Mg,Sr,Ba,Eu)a(Si,Al、Eu)dNe、(Mg,Sr,Ba,Eu)aAldOeLig、(Mg,Sr,Ba,Eu)aAldOe、(Mg,Sr,Ba,Eu)aAld(O,N)eLig、(Mg,Sr,Ba,Eu)aAld(O,N)e、(Mg,Sr,Ba,Eu)aAldNeLig、(Mg,Sr,Ba,Eu)aAldNe、(Ca,Sr,Ba,Eu)aSidOeLig、(Ca,Sr,Ba,Eu)aSidOe、(Ca,Sr,Ba,Eu)aSid(O,N)eLig、(Ca,Sr,Ba,Eu)aSid(O,N)e、(Ca,Sr,Ba,Eu)aSidNeLig、(Ca,Sr,Ba,Eu)aSidNe、(Ca,Sr,Ba,Eu)a(Si,Al)dOeLig、(Ca,Sr,Ba,Eu)a(Si,Al)dOe、(Ca,Sr,Ba,Eu)a(Si,Al)d(O,N)eLig、(Ca,Sr,Ba,Eu)a(Si,Al)d(O,N)e、(Ca,Sr,Ba,Eu)a(Si,Al)dNeLig、(Ca,Sr,Ba,Eu)a(Si,Al、Eu)dNe、(Ca,Sr,Ba,Eu)aAldOeLig、(Ca,Sr,Ba,Eu)aAldOe、(Ca,Sr,Ba,Eu)aAld(O,N)eLig、(Ca,Sr,Ba,Eu)aAld(O,N)e、
(Ca,Sr,Ba,Eu)aAldNeLig、(Ca,Sr,Ba,Eu)aAldNe、(Mg,Ca,Sr,Ba,Eu)aSidOeLig、(Mg,Ca,Sr,Ba,Eu)aSidOe、(Mg,Ca,Sr,Ba,Eu)aSid(O,N)eLig、(Mg,Ca,Sr,Ba,Eu)aSid(O,N)e、(Mg,Ca,Sr,Ba,Eu)aSidNeLig、(Mg,Ca,Sr,Ba,Eu)aSidNe、(Mg,Ca,Sr,Ba,Eu)a(Si,Al)dOeLig、(Mg,Ca,Sr,Ba,Eu)a(Si,Al)dOe、(Mg,Ca,Sr,Ba,Eu)a(Si,Al)d(O,N)eLig、(Mg,Ca,Sr,Ba,Eu)a(Si,Al)d(O,N)e、(Mg,Ca,Sr,Ba,Eu)a(Si,Al)dNeLig、(Mg,Ca,Sr,Ba,Eu)a(Si,Al、Eu)dNe、(Mg,Ca,Sr,Ba,Eu)aAldOeLig、(Mg,Ca,Sr,Ba,Eu)aAldOe、(Mg,Ca,Sr,Ba,Eu)aAld(O,N)eLig、(Mg,Ca,Sr,Ba,Eu)aAld(O,N)e、(Mg,Ca,Sr,Ba,Eu)aAldNeLig、(Mg,Ca,Sr,Ba,Eu)aAldNe、(Mg,Ca,Sr,Ba,Eu)aSidOeLig、(Mg,Ca,Sr,Ba,Eu)aSidOe、(Mg,Ca,Sr,Ba,Eu)aSid(O,N)eLig、(Mg,Ca,Sr,Ba,Eu)aSid(O,N)e、(Mg,Ca,Sr,Ba,Eu)aSidNeLig、(Mg,Ca,Sr,Ba,Eu)aSidNe、(Mg,Ca,Sr,Ba,Eu)a(Si,Al)dOeLig、(Mg,Ca,Sr,Ba,Eu)a(Si,Al)dOe、(Mg,Ca,Sr,Ba,Eu)a(Si,Al)d(O,N)eLig、(Mg,Ca,Sr,Ba,Eu)a(Si,Al)d(O,N)e、(Mg,Ca,Sr,Ba,Eu)a(Si,Al)dNeLig、(Mg,Ca,Sr,Eu)a(Si,Al、Eu)dNe、(Mg,Ca,Sr,Eu)aAldOeLig、(Mg,Ca,Sr,Ba,Eu)aAldOe、(Mg,Ca,Sr,Ba,Eu)aAld(O,N)eLig、(Mg,Ca,Sr,Ba,Eu)aAld(O,N)e、(Mg,Ca,Sr,Ba,Eu)aAldNeLig、(Mg,Ca,Sr,Ba,Eu)aAldNe。
そして、実験105から実験113(表6)にあるように、Euと共に或いはEuの代わりに、Mn、Ce、Nd、Tb、Dy、Ho、Er、Tm、および/またはYbを含むものも、本発明の実施例に含まれる。
[例114]
図5は、本発明による照明器具(砲弾型LED照明器具)を示す概略図である。
図6は、本発明による照明器具(基板実装型LED照明器具)を示す概略図である。
2、3 リードワイヤ
4 紫外発光ダイオード素子
5 金細線
6、8 樹脂
7 蛍光体
11 基板実装用チップ型発光ダイオードランプ
12、13 リードワイヤ
14 青色発光ダイオード素子
15 金細線
16、18 樹脂
17 蛍光体
19 アルミナセラミックス基板
20 壁面部材
Claims (20)
- 少なくともA元素と、M元素と、D元素と、E元素(ただし、Aは、少なくともMg、Ca、SrおよびBaからなる群から選ばれる1種または2種以上の元素を含み、Mは、Mn、Eu、Ce、Nd、Tb、Dy、Ho、Er、TmおよびYbからなる群から選ばれる1種または2種以上の元素であり、Dは、SiおよびAlからなる群から選ばれる1種または2種以上の元素であり、Eは、OおよびNからなる群から選ばれる1種または2種以上の元素である)と、必要に応じてG元素(ただし、GはLi元素である)を含み、
(A,M)aDdEeGgの組成で表され、原子分率パラメータa、d、e、gが、
2.4 ≦ a ≦ 4.8
17.4≦ d ≦ 22.2
26.2 ≦ e ≦ 28.6
0 ≦ g ≦ 3
の数値で表される無機化合物である、蛍光体。 - 前記パラメータgが、
0.21 ≦ g ≦ 1.05
の範囲の数値で表される、請求項1に記載の蛍光体。 - 前記無機化合物は、(A,M)6xD27-12xE31-6xG3y(ただし、xおよびyは、それぞれ、0.4≦x≦0.8、0≦y≦0.35を満たす)の組成で表される、請求項1に記載の蛍光体。
- 前記xは、0.45≦x≦0.55を満たす、請求項3に記載の蛍光体。
- 前記無機化合物が、(A,M)6xD27-12xE31-6xG3y(ただし、0.4≦x≦0.8、0≦y≦0.35)であらわされる結晶(本結晶という)、または、それと同一の結晶構造を有する結晶(本同一結晶という)である、請求項1に記載の蛍光体。
- 前記無機化合物が、(Sr,Eu)3(Si,Al)21(O,N)28Li0.96である、請求項5に記載の蛍光体。
- 無機化合物が、Sr3Si12.432Al8.568O1.608N26.392Li0.96と同一の結晶構造を有する結晶である、請求項5に記載の蛍光体。
- 前記本結晶および前記本同一結晶が、六方晶系であり、格子定数a、b、cが
1.6 < a < 1.8 nm
b = a
0.44 < c < 0.52 nm
である、請求項5に記載の蛍光体。 - 前記本結晶および前記本同一結晶が、P63空間群(International Tables for Crystallographyの173番の空間群)に属する結晶である、請求項5に記載の蛍光体。
- 前記無機化合物が、Sr6x(Si,Al)27-12x(O,N)31-6xLi3y(ただし、0.4≦x≦0.8、0≦y≦0.35)で表される結晶、または、それと同一の結晶構造を有する結晶に、さらにM元素を含む、請求項1に記載の蛍光体。
- 前記A元素がSrであり、前記M元素がEuであり、前記E元素がOおよびNからなる群から選ばれる1種または2種以上の元素である、請求項1に記載の蛍光体。
- 前記D元素は、SiおよびAlを含み、
0.4 ≦ Al/(Al+Si)≦ 0.6を満たす、請求項1に記載の蛍光体。 - 前記E元素は、OおよびNを含み、
0.01 ≦ O/(O+N)≦ 0.1を満たす、請求項1に記載の蛍光体。 - 300nm以上600nm以下の範囲の波長の光を照射することにより、600nm以上850nm以下の範囲の波長に発光ピークの最大値をもつ発光をする、請求項1に記載の蛍光体。
- A元素(ただし、Aは、Mg、Ca、SrおよびBaからなる群から選ばれる1種または2種以上の元素である)、M元素(ただし、Mは、Mn、Eu、Ce、Nd、Tb、Dy、Ho、Er、TmおよびYbからなる群から選ばれる1種または2種以上の元素である)、D元素(SiおよびAlからなる群から選ばれる1種または2種以上の元素である)、必要に応じてG元素(ただし、GはLi元素である)の、窒化物、酸窒化物、酸化物、炭酸塩およびフッ化物からなる群から1以上選択される原料を混合し、1400℃以上2200℃以下の温度で焼成する、請求項1~14のいずれかに記載の蛍光体の製造方法。
- 300nm以上600nm以下の範囲の波長の光を発する励起源と、請求項1~14のいずれかに記載の蛍光体とを含む、発光素子。
- 前記励起源が発光ダイオード(LED)またはレーザーダイオード(LD)である、請求項16に記載の発光素子。
- さらに、300nm以上600nm以下の範囲の波長の光を照射することにより400nm以上760nm以下の範囲の波長に発光ピークの最大値をもつ蛍光を発する、1以上の蛍光体を含む、請求項16に記載の発光素子。
- さらに、AlN:(Eu,Si)、BaMgAl10O17:Eu、SrSi9Al19ON31:Eu、LaSi9Al19N32:Eu、α-サイアロン:Ce、JEM:Ce、β-サイアロン:Eu、(Ba,Sr,Ca,Mg)2SiO4:Eu、(Ca,Sr,Ba)Si2O2N2:Eu、YAG:Ce、α-サイアロン:Eu、CaAlSiN3:Ce、La3Si6N11:Ce、CaAlSiN3:Eu、(Ca,Sr)AlSiN3:Eu、Ca2Si5N8:Eu、および、Sr2Si5N8:Euからなる群から選ばれる1種または2種以上の蛍光体を含む、請求項16~18のいずれかに記載の発光素子。
- 請求項16に記載の発光素子を含む、照明器具、液相パネル用バックライト、プロジェクター用ランプ、赤外照明、赤外計測用光源のいずれかである発光装置。
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