JP2006321921A - alpha-TYPE SIALON PHOSPHOR AND LIGHTING EQUIPMENT USING THE SAME - Google Patents
alpha-TYPE SIALON PHOSPHOR AND LIGHTING EQUIPMENT USING THE SAME Download PDFInfo
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- JP2006321921A JP2006321921A JP2005146917A JP2005146917A JP2006321921A JP 2006321921 A JP2006321921 A JP 2006321921A JP 2005146917 A JP2005146917 A JP 2005146917A JP 2005146917 A JP2005146917 A JP 2005146917A JP 2006321921 A JP2006321921 A JP 2006321921A
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000011164 primary particle Substances 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 26
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 15
- 239000011737 fluorine Substances 0.000 claims abstract description 15
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052796 boron Inorganic materials 0.000 claims abstract description 13
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 9
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- -1 lanthanide metals Chemical class 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 6
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 6
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 5
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 5
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 4
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 4
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 4
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 2
- 230000005284 excitation Effects 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 7
- 230000001678 irradiating effect Effects 0.000 claims description 5
- 208000011117 substance-related disease Diseases 0.000 claims 1
- 238000000034 method Methods 0.000 description 20
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 13
- 229910052581 Si3N4 Inorganic materials 0.000 description 11
- 239000011575 calcium Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 11
- 239000013078 crystal Substances 0.000 description 10
- 239000006104 solid solution Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000011163 secondary particle Substances 0.000 description 8
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000011812 mixed powder Substances 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
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- 238000005245 sintering Methods 0.000 description 6
- 229910052582 BN Inorganic materials 0.000 description 5
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229910052761 rare earth metal Inorganic materials 0.000 description 5
- 238000009877 rendering Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229910018509 Al—N Inorganic materials 0.000 description 4
- 229910018516 Al—O Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910007991 Si-N Inorganic materials 0.000 description 3
- 229910006294 Si—N Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 229910002601 GaN Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 229910001940 europium oxide Inorganic materials 0.000 description 2
- 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 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
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- 238000006467 substitution reaction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000003991 Rietveld refinement Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910002795 Si–Al–O–N Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- UVQJRJGTRAHFPN-UHFFFAOYSA-N europium fluoro hypofluorite Chemical compound O(F)F.[Eu] UVQJRJGTRAHFPN-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011158 quantitative evaluation Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
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- 238000000790 scattering method Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- LGERWORIZMAZTA-UHFFFAOYSA-N silicon zinc Chemical compound [Si].[Zn] LGERWORIZMAZTA-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/4805—Shape
- H01L2224/4809—Loop shape
- H01L2224/48091—Arched
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
- H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
- H01L2224/42—Wire connectors; Manufacturing methods related thereto
- H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
- H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
- H01L2224/481—Disposition
- H01L2224/48151—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
- H01L2224/48221—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
- H01L2224/48245—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
- H01L2224/48247—Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
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Abstract
Description
本発明は、紫外線乃至青色光で励起され、可視光線を発するα型サイアロン蛍光体と、それを利用した照明器具、特に白色LEDに関する。 The present invention relates to an α-sialon phosphor that is excited by ultraviolet or blue light and emits visible light, and a lighting fixture using the α-sialon phosphor, and particularly a white LED.
蛍光体として、母体材料にケイ酸塩、リン酸塩、アルミン酸塩、硫化物を用い発光中心に遷移金属もしくは希土類金属を用いたものが広く知られている。一方、白色LEDについては、紫外線乃至は青色光などの高いエネルギーを有した励起源により励起されて可視光線を発するものが注目され、開発が進んでいる。しかしながら、前記した従来の蛍光体では、励起源に曝される結果として、蛍光体の輝度が低下するという問題がある。輝度低下の少ない蛍光体として、最近、結晶構造が安定で、励起光や発光を長波長側にシフトできる材料であることから、窒化物や酸窒化物蛍光体が注目されている。 As phosphors, silicates, phosphates, aluminates, and sulfides are used as a base material, and transition metals or rare earth metals are used as emission centers. On the other hand, white LEDs that are excited by an excitation source having high energy such as ultraviolet light or blue light and that emit visible light have been attracting attention and are being developed. However, the above-described conventional phosphor has a problem in that the luminance of the phosphor decreases as a result of exposure to the excitation source. Nitride and oxynitride phosphors have recently attracted attention as phosphors with low luminance reduction because they have a stable crystal structure and can shift excitation light and light emission to the longer wavelength side.
窒化物、酸窒化物蛍光体として、特定の希土類元素が付活されたα型サイアロンは、有用な蛍光特性を有することが知られており、白色LED等への適用が検討されている(特許文献1〜5、非特許文献1参照)。
また、希土類元素を付活したCa2(Si、Al)5N8やCaSiAlN3やβ型サイアロンも同様の蛍光特性を有することが見いだされている(特許文献6、非特許文献2,3参照)。
他にも、窒化アルミニウム、窒化ケイ素マグネシウム、窒化ケイ素カルシウム、窒化ケイ素バリウム、窒化ガリウム、窒化ケイ素亜鉛、等の窒化物や酸窒化物を母体材料とした蛍光体が提案されている。 In addition, a phosphor using a nitride or oxynitride such as aluminum nitride, magnesium magnesium nitride, calcium calcium nitride, silicon barium nitride, gallium nitride, or silicon zinc nitride as a base material has been proposed.
α型サイアロンは、α型窒化ケイ素の固溶体であり、結晶格子間に特定の元素(Ca、並びにLi、Mg、Y、又はLaとCeを除くランタニド金属)が格子内に侵入固溶し、電気的中性を保つために、Si−N結合が部分的にAl−N結合とAl―O結合で置換されている構造を有している。侵入固溶する元素の一部を発光中心となる希土類元素とすることにより蛍光特性が発現する。 α-type sialon is a solid solution of α-type silicon nitride, and specific elements (Ca and Li, Mg, Y, or lanthanide metals excluding La and Ce) enter the lattice to form a solid solution between crystal lattices. In order to maintain neutrality, the Si—N bond is partially substituted with an Al—N bond and an Al—O bond. Fluorescence characteristics are exhibited by using a rare earth element as a light emission center for a part of the element that enters and dissolves.
α型サイアロンは、窒化ケイ素、窒化アルミニウム、必要に応じて酸化アルミウム、及び侵入固溶する元素の酸化物等からなる混合粉末を窒素中の高温で焼成することにより得られる。窒化ケイ素とアルミニウム化合物との比率と、侵入固溶させる元素の種類、並びに発光中心となる元素の割合等により、多様な蛍光特性が得られる。 The α-type sialon is obtained by firing a mixed powder composed of silicon nitride, aluminum nitride, aluminum oxide as required, and an oxide of an intruding solid solution element at a high temperature in nitrogen. Various fluorescent characteristics can be obtained depending on the ratio of silicon nitride and aluminum compound, the type of element that enters and dissolves, the ratio of the element that becomes the emission center, and the like.
ところで、現在までに得られている白色LEDは、発光効率が蛍光ランプに及ばないという事情がある。蛍光ランプよりも発光効率に優れるLED、特に白色LEDが産業上で省エネルギーの観点から強く要求されている。 By the way, the white LED obtained until now has the situation that luminous efficiency does not reach a fluorescent lamp. There is a strong demand in the industry from the viewpoint of energy saving for LEDs that are superior in luminous efficiency to fluorescent lamps, especially white LEDs.
白色は、単色光とは異なり複数の色の組み合わせが必要であり、一般的な白色LEDは、紫外LED又は青色LEDとそれらの光を励起源とし、可視光を発する蛍光体との組み合わせにより構成されている。従って、白色LEDの効率向上のためには、紫外LED又は青色LEDのLED自体の発光効率向上と共に、そこに用いられる蛍光体の効率向上、更には、発せられた光を外部に取り出す効率の向上が必要である。白色LEDの一般照明用まで含めた用途拡大のためには、これら全ての効率向上が必要である。 Unlike white light, white requires a combination of multiple colors, and a general white LED is composed of a combination of an ultraviolet LED or a blue LED and a phosphor that emits visible light using such light as an excitation source. Has been. Therefore, in order to improve the efficiency of the white LED, the luminous efficiency of the ultraviolet LED or the blue LED itself is improved, the efficiency of the phosphor used therefor, and the efficiency of extracting emitted light to the outside are improved. is required. In order to expand the application including the general illumination of the white LED, it is necessary to improve all of these efficiencies.
従来技術においては、α型サイアロン蛍光体の発光効率改善は、主として結晶の骨格となるα型窒化ケイ素へのAl−N、Al−O結合の置換量や結晶格子内へ侵入固溶する元素の種類、量、割合といった固溶組成に着目して進められてきており、組成以外の要因についてはあまり検討されていない。 In the prior art, the luminous efficiency of α-type sialon phosphors is mainly improved by the substitution amount of Al—N and Al—O bonds into α-type silicon nitride, which is the skeleton of the crystal, and the element that dissolves into the crystal lattice. Progress has been made with a focus on solid solution compositions such as types, amounts, and proportions, and factors other than the composition have not been studied much.
また、白色LED用蛍光体は、一般的に、エポキシ樹脂等の封止材料中にミクロンサイズの粒子として分散して使用される。樹脂中への分散性や発色のバラツキといった観点からも粒子サイズを決める必要がある。α型サイアロン蛍光体は、細かな一次粒子が複数個焼結した二次粒子から構成されている。通常、粒度分布測定で得られる粒度情報はこの二次粒子に関するものであり、蛍光体への適用に際して前記二次粒子について検討されてはいるが、一次粒子に関しては着目されていなかった。 Further, the phosphor for white LED is generally used by being dispersed as micron-sized particles in a sealing material such as an epoxy resin. It is necessary to determine the particle size from the viewpoint of dispersibility in the resin and variation in color development. The α-type sialon phosphor is composed of secondary particles obtained by sintering a plurality of fine primary particles. Normally, the particle size information obtained by the particle size distribution measurement relates to the secondary particles, and the secondary particles have been studied when applied to the phosphor, but the primary particles have not been noted.
本発明は、α型サイアロン蛍光体に関していろいろ検討し、550〜600nmの範囲の波長にピークを持ち、発光効率に優れる白色LED、特に青色LEDまたは紫外LEDを光源とする発光効率に優れる白色LEDを提供することを目的になされたものである。 The present invention has been studied variously with respect to the α-type sialon phosphor, and a white LED having a peak in a wavelength range of 550 to 600 nm and excellent in luminous efficiency, particularly a white LED excellent in luminous efficiency using a blue LED or an ultraviolet LED as a light source. It was made for the purpose of providing.
本発明者は、α型サイアロンを母体材料とする蛍光体について検討を行い、α型サイアロンの組成とその一次粒子のサイズと形状が特定のものにおいて、550〜600nmの範囲の波長にピークを持ち、発光効率に優れる蛍光体が得られ、これを用いて優れた発光特性の照明器具が得られることを見いだし、本発明に至ったものである。加えて、本発明者は、前記の特定のα型サイアロン蛍光体に於いて、微量のフッ素不純物やホウ素不純物の存在によって更に蛍光特性が改善できるとの知見を得て、本発明に至ったものである。 The present inventor has studied a phosphor using α-sialon as a base material, and has a peak in a wavelength range of 550 to 600 nm when the composition of α-sialon and the size and shape of the primary particles are specific. Thus, the present inventors have found that a phosphor excellent in luminous efficiency is obtained, and that it is possible to obtain a luminaire having excellent luminous characteristics by using the phosphor. In addition, the present inventor has obtained the knowledge that the above-mentioned specific α-sialon phosphor can further improve the fluorescence characteristics due to the presence of a small amount of fluorine impurity or boron impurity, and has led to the present invention. It is.
即ち、本発明のα型サイアロン蛍光体は、一般式:(M1)X(M2)Y(Si,Al)12(O,N)16(但し、M1はLi、Mg、Ca、Y及びランタニド金属(LaとCeを除く)からなる群から選ばれる1種以上の元素であり、M2はCe、Pr、Eu、Tb、Yb、Erから選ばれる1種以上の元素で、0.3<X+Y<1.5、0<Y<0.7)で示されるα型サイアロンからなる粉末状蛍光体であって、当該粉末を構成する一次粒子の平均アスペクト比が3以下であり、しかも前記一次粒子の80%(個数百分率)以上のものの直径が3〜10μmであることを特徴とする。また、本発明のα型サイアロン蛍光体は、好ましくは、フッ素を5〜300ppm、及び/又はホウ素を10〜3000ppm含有している。 In other words, the α-sialon phosphor of the present invention has a general formula: (M1) X (M2) Y (Si, Al) 12 (O, N) 16 (where M1 is Li, Mg, Ca, Y and lanthanide metal) (Excluding La and Ce) is one or more elements selected from the group consisting of M2 is one or more elements selected from Ce, Pr, Eu, Tb, Yb, Er, and 0.3 <X + Y < 1.5, 0 <Y <0.7), which is a powdered phosphor composed of α-sialon, wherein the primary particles constituting the powder have an average aspect ratio of 3 or less, and the primary particles A diameter of 80% (number percentage) or more is 3 to 10 μm. The α-sialon phosphor of the present invention preferably contains 5 to 300 ppm of fluorine and / or 10 to 3000 ppm of boron.
更に、本発明の蛍光体は、好ましくは、M1が少なくともCaを含み、M2が少なくともEuを含み、しかも、0.01<Y/(X+Y)<0.3であり、100〜500nmの波長を持つ紫外線又は可視光を励起源として照射することにより、550〜600nmの範囲の波長域にピークを持つ発光特性を示す。 Furthermore, in the phosphor of the present invention, preferably, M1 contains at least Ca, M2 contains at least Eu, and 0.01 <Y / (X + Y) <0.3, and has a wavelength of 100 to 500 nm. Irradiation characteristics having a peak in a wavelength range of 550 to 600 nm are exhibited by irradiating with ultraviolet light or visible light having an excitation source.
本発明は、発光光源と蛍光体から構成される照明器具において、少なくとも前記蛍光体を用いることを特徴とする照明器具であって、好ましくは、M1が少なくともCaを含み、M2が少なくともEuを含み、しかも、0.01<Y/(X+Y)<0.3であり、100〜500nmの波長を持つ紫外線又は可視光を励起源として照射することにより550〜600nmの範囲の波長にピークを持つ発光する前記蛍光体と、100〜500nmの波長を持つ紫外線又は可視光を励起源として照射することにより500〜550nmの範囲の波長にピークを持つ発光特性を有する蛍光体とを用いることを特徴とする照明器具である。 The present invention provides a lighting fixture including a light emitting light source and a phosphor, wherein at least the phosphor is used. Preferably, M1 includes at least Ca, and M2 includes at least Eu. In addition, 0.01 <Y / (X + Y) <0.3, and light emission having a peak at a wavelength in the range of 550 to 600 nm by irradiation with ultraviolet light or visible light having a wavelength of 100 to 500 nm as an excitation source. And the phosphor having emission characteristics having a peak at a wavelength in the range of 500 to 550 nm by irradiating with ultraviolet light or visible light having a wavelength of 100 to 500 nm as an excitation source. It is a lighting fixture.
本発明の蛍光体は、100〜500nmの波長を持つ紫外線又は可視光を励起源として照射することにより550〜600nmの範囲の波長域にピークを持つ発光特性を示すので、青色LED又は紫外LEDを光源とする白色LEDに好適である。また、本発明の照明器具は、前記蛍光体を用いているので、優れた発光特性を有し、従ってエネルギー効率が高い。 The phosphor of the present invention exhibits emission characteristics having a peak in a wavelength range of 550 to 600 nm by irradiating ultraviolet light or visible light having a wavelength of 100 to 500 nm as an excitation source. Suitable for white LED as light source. Moreover, since the lighting fixture of this invention uses the said fluorescent substance, it has the outstanding light emission characteristic, Therefore, energy efficiency is high.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
α型サイアロンは、α型窒化ケイ素におけるSi−N結合の一部がAl−N結合及びAl−O結合に置換し、電気的中性を保つために、特定の陽イオンが格子内に侵入した固溶体であり、一般式:Mz(Si,Al)12(O,N)16で表される。ここで、Mは格子内への侵入可能な元素であり、Li、Mg、Ca、Y及びランタニド金属(LaとCeを除く)である。Mの固溶量Z値は、Si−N結合のAl−N結合及びAl−O結合の置換率により決まる数値である。 In α-type sialon, a part of Si—N bond in α-type silicon nitride is replaced by Al—N bond and Al—O bond, and a specific cation enters the lattice in order to maintain electrical neutrality. It is a solid solution and is represented by the general formula: M z (Si, Al) 12 (O, N) 16 . Here, M is an element that can enter the lattice, and is Li, Mg, Ca, Y, and a lanthanide metal (excluding La and Ce). The solid solution amount Z value of M is a numerical value determined by the substitution rate of Al—N bonds and Al—O bonds of Si—N bonds.
蛍光特性を発現させるためには、Mの一部を固溶可能で発光中心となる元素とする必要があり、可視光発光の蛍光体を得るためにはCe、Pr、Eu、Tb、Yb、Erを使用することが好ましい。格子内に侵入固溶する元素の内、発光に寄与しない元素をM1、発光中心となる元素をM2とすると、一般式は(M1)X(M2)Y(Si,Al)12(O,N)16となる。ここで、α型サイアロン単相を得ると共に蛍光特性を発現させるためには、0.3<X+Y<1.5、0<Y<0.7の範囲にあることが好ましい。 In order to express the fluorescence characteristics, it is necessary to use a part of M as an element capable of forming a solid solution and serving as an emission center. To obtain a phosphor emitting visible light, Ce, Pr, Eu, Tb, Yb, It is preferable to use Er. When the element that does not contribute to light emission among the elements that enter and dissolve in the lattice is M1, and the element that is the emission center is M2, the general formula is (M1) X (M2) Y (Si, Al) 12 (O, N ) 16 Here, in order to obtain an α-type sialon single phase and to exhibit fluorescence characteristics, it is preferable that the range is 0.3 <X + Y <1.5 and 0 <Y <0.7.
一般的にα型サイアロンは、窒化ケイ素、窒化アルミニウム及び侵入固溶する元素の化合物からなる混合粉末を高温の窒素雰囲気中で加熱して反応させることにより得られる。昇温の過程で、窒化ケイ素、窒化アルミニウム、これらの表面酸化物、更に固溶元素の化合物が形成する液相を介して、物質の移動が起こり、α型サイアロンが生成する。そのために、合成後のα型サイアロンは、複数の一次粒子が焼結して二次粒子、更に塊状物を形成するので、それを粉砕等することにより、粉末状とする。 In general, α-sialon can be obtained by heating and reacting a mixed powder composed of silicon nitride, aluminum nitride, and a compound of an intruding solid solution element in a high-temperature nitrogen atmosphere. In the process of raising the temperature, the substance moves through a liquid phase formed by silicon nitride, aluminum nitride, their surface oxides, and a compound of a solid solution element, and α-sialon is generated. For this purpose, the synthesized α-sialon is formed into a powder form by pulverizing it because a plurality of primary particles are sintered to form secondary particles and further a lump.
本発明者は、発光特性と粒子形態との関係を検討した結果、一次粒子のサイズと分布及び形状が発光特性と密接に結びついているという知見を得て、本発明に至ったものである。即ち、本発明の蛍光体においては、前記組成に加えて、蛍光体の粉末を構成する一次粒子について、平均のアスペクト比が3以下であること、更に、個数百分率で80%以上のものの直径が3〜10μmを有することが選択される。 As a result of studying the relationship between the light emission characteristics and the particle morphology, the present inventor has obtained the knowledge that the size, distribution and shape of the primary particles are closely related to the light emission characteristics, and have reached the present invention. That is, in the phosphor of the present invention, in addition to the above composition, the average aspect ratio of the primary particles constituting the phosphor powder is 3 or less, and the diameter of those having a percentage by number of 80% or more. It is selected to have 3-10 μm.
一次粒子のアスペクト比ついては、例えばLED用封止樹脂への分散性やLEDとしての発光強度、更に色調のバラツキの観点から、異方性が小さい方が好ましいが、本発明者検討に基づけば、一次粒子の平均アスペクト比が3以下であれば実用上問題がなく使用できる。一次粒子の平均アスペクト比については、走査型電子顕微鏡(SEM)により、少なくとも500個以上の一次粒子についてアスペクト比(長軸径/短軸径)を測定し、算術平均すれば良い。 As for the aspect ratio of the primary particles, for example, from the viewpoint of dispersibility in an LED sealing resin, light emission intensity as an LED, and variation in color tone, a smaller anisotropy is preferable. If the average aspect ratio of the primary particles is 3 or less, there is no problem in practical use. Regarding the average aspect ratio of the primary particles, the aspect ratio (major axis diameter / minor axis diameter) of at least 500 primary particles may be measured by a scanning electron microscope (SEM), and arithmetic average may be performed.
一次粒子の大きさについては、その分布がシャープであることが好ましい。一次粒子のサイズ分布が幅広い場合、当該蛍光体を使用するときに、発光強度及び色調のバラツキを生じることがある。一方、一次粒子があまりに小さいと、散乱により光の吸収率が低下するとともに、粒子間の焼結が強固に進行するため粉末(二次粒子)として所定の粒度を得るためには過度な粉砕処理が必要となり、粒子表面の欠陥生成により発光特性が悪くなったり、ハンドリング性が悪くなる等の不具合が生じる。上記の理由から本発明に於いては、一次粒子の大きさについて、直径が3〜10μmを有するものが個数百分率で80%以上であることが選択される。尚、個数百分率は、後述する通りに、走査型電子顕微鏡(SEM)により、少なくとも500個以上の一次粒子について円相当径を測定し、その百分率をもって定めれば良い。 Regarding the size of the primary particles, the distribution is preferably sharp. When the size distribution of the primary particles is wide, when the phosphor is used, variations in emission intensity and color tone may occur. On the other hand, if the primary particles are too small, the light absorptance decreases due to scattering, and sintering between the particles proceeds firmly, so that excessive pulverization is required to obtain a predetermined particle size as a powder (secondary particles). And the generation of defects on the particle surface causes problems such as poor light emission characteristics and poor handling properties. For the above reason, in the present invention, the primary particles having a diameter of 3 to 10 μm are selected to be 80% or more in terms of the number percentage. The number percentage may be determined by measuring the equivalent circle diameter of at least 500 primary particles with a scanning electron microscope (SEM), as will be described later, and determining the percentage.
また、本発明に於いて、本発明者がα型サイアロン蛍光体の微量添加元素と発光特性の関係を調べたところ、フッ素を5〜300ppm、或いはホウ素を10〜3000ppm含有する場合に、一層良好な発光特性が得られることを見いだしたものである。この現象は、フッ素については5ppm以上で、ホウ素については10ppm以上で顕著となるが、前者では300ppm、後者では3000ppmを越えた場合にはそれ以上の効果が得られなくなる。 Further, in the present invention, when the present inventor investigated the relationship between the trace amount of element added to the α-sialon phosphor and the light emission characteristics, it was even better when the content of fluorine was 5 to 300 ppm or the content of boron was 10 to 3000 ppm. It has been found that excellent light emission characteristics can be obtained. This phenomenon becomes prominent at 5 ppm or more for fluorine and 10 ppm or more for boron. However, when the concentration exceeds 300 ppm for the former and 3000 ppm for the latter, no further effect can be obtained.
フッ素やホウ素の微量添加方法は特に限定されないが、フッ素については、原料の一部にフッ化物を使用し合成中に過剰のフッ素を揮発させる方法が、ホウ素については、合成の際に原料混合粉末を充填する坩堝に六方晶窒化ホウ素製のものを使用し高温中に坩堝より微量生成するホウ素含有揮発物を利用する方法が、微量且つ均一に添加する手法として好ましい。 The method of adding a small amount of fluorine or boron is not particularly limited, but for fluorine, a method of volatilizing excess fluorine during synthesis by using a fluoride as a part of the raw material, and for boron, raw material mixed powder at the time of synthesis A method of using a hexagonal boron nitride made of a hexagonal boron nitride for the crucible filling and using a boron-containing volatile material generated in a trace amount from a crucible at a high temperature is preferable as a method for adding a trace amount uniformly.
また、α型サイアロン中のフッ素含有量は、後述する加熱処理に於いて、揮発性のフッ素含有物として原料中のフッ素化合物の一部を揮発せることにより制御できるし、また、加熱処理後に、塩酸や硫酸などの酸により処理することで、残留フッ素化合物を除去することによっても制御できる。 In addition, the fluorine content in the α-sialon can be controlled by volatilizing a part of the fluorine compound in the raw material as a volatile fluorine-containing material in the heat treatment described later, and after the heat treatment, It can also be controlled by removing residual fluorine compounds by treating with an acid such as hydrochloric acid or sulfuric acid.
α型サイアロンの結晶格子内に固溶する元素としてM1にCa、M2にEuを選択する場合には、100〜500nmの波長を持つ紫外線又は可視光を励起源として照射することにより550〜600nmの範囲の波長域にピークを持ち、黄〜橙色の発光を示す蛍光体が得られる。この蛍光体は、例えば、励起源として青色LEDを使用すると蛍光体から発光する黄色光と励起光の混合により白色LEDが得られることから、白色LED等を初めとする白色光を放つ照明器具を提供できるので好ましい。 When Ca is selected as M1 and Eu as M2 is selected as an element that dissolves in the crystal lattice of α-sialon, it is irradiated with ultraviolet light or visible light having a wavelength of 100 to 500 nm as an excitation source. A phosphor having a peak in the wavelength range of the range and emitting yellow to orange light is obtained. For example, when a blue LED is used as an excitation source, a white LED is obtained by mixing yellow light emitted from the phosphor and excitation light. For this phosphor, a luminaire that emits white light such as a white LED is used. Since it can provide, it is preferable.
α型サイアロンの結晶格子内に固溶する元素に関して、発光中心となるEuの原子量比としては、0.01<Y/(X+Y)<0.3の範囲にあることが好ましい。Y/(X+Y)が0.01以上ならば発光中心が少ないために発光輝度が低下することもないし、0.3未満ならば固溶しているEuイオン間の干渉により濃度消光を起こすことにより発光輝度が低下することもない。 Regarding the element dissolved in the crystal lattice of α-sialon, the atomic weight ratio of Eu serving as the emission center is preferably in the range of 0.01 <Y / (X + Y) <0.3. If Y / (X + Y) is 0.01 or more, the emission center does not decrease because the emission center is small, and if it is less than 0.3, concentration quenching occurs due to interference between solid-solved Eu ions. The light emission luminance is not lowered.
以下、本発明の蛍光体を得る方法として、CaとEuとが固溶したα型サイアロンの合成方法について例示するが、製造方法はこれに限定されるものではない。 Hereinafter, as a method for obtaining the phosphor of the present invention, an example of a method for synthesizing α-sialon in which Ca and Eu are dissolved, the production method is not limited thereto.
窒化ケイ素、窒化アルミニウム、カルシウム含有化合物及び酸化ユーロピウムの粉末を原料として使用する。これらの原料の中でフッ素源としては、フッ化物の沸点が比較的高いことからフッ化カルシウムを使用することが好ましい。しかし、カルシウム源を全てフッ化カルシウムとした場合にはα型サイアロン単相が得難くなるので、炭酸カルシウム等の加熱後に酸化カルシウムとなる化合物と混合することが好ましい。 Silicon nitride, aluminum nitride, calcium-containing compound and europium oxide powder are used as raw materials. Among these raw materials, calcium fluoride is preferably used as the fluorine source because the boiling point of fluoride is relatively high. However, when the calcium source is all calcium fluoride, it is difficult to obtain an α-sialon single phase. Therefore, it is preferable to mix with a compound that becomes calcium oxide after heating, such as calcium carbonate.
前記した各原料を混合する方法については、乾式混合する方法、原料各成分と実質的に反応しない不活性溶媒中で湿式混合した後に溶媒を除去する方法などを採用することができる。尚、混合装置としては、V型混合機、ロッキングミキサー、ボールミル、振動ミル等が好適に使用される。 As a method of mixing the raw materials described above, a method of dry mixing, 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. In addition, as a mixing apparatus, a V-type mixer, a rocking mixer, a ball mill, a vibration mill, etc. are used suitably.
所望組成となるように混合して得た粉末(以下、単に原料粉末という)を、少なくとも当該原料粉末が接する面が窒化ホウ素からなる坩堝等の容器内に充填し、窒素雰囲気中で1600〜1800℃の温度範囲で所定時間加熱することによりα型サイアロンを得る。容器材質に窒化ホウ素を使用するのは、原料各成分との反応性が非常に低いだけでなく、容器から発生するホウ素含有微量揮発成分がα型サイアロンの一次粒子の結晶成長を促進する効果があるためである。尚、原料混合粉末の容器内への充填は、加熱中に粒子間焼結を抑制する観点から、できるだけ嵩高くすることが好ましい。具体的には、原料混合粉末の合成容器への充填率を40体積%以下とすることが好ましい。 A powder obtained by mixing so as to have a desired composition (hereinafter, simply referred to as a raw material powder) is filled in a container such as a crucible having at least a surface in contact with the raw material powder made of boron nitride, and 1600 to 1800 in a nitrogen atmosphere. Α-sialon is obtained by heating for a predetermined time in a temperature range of ° C. The use of boron nitride as the container material is not only very low in reactivity with the raw material components, but also has the effect of promoting the crystal growth of primary particles of α-sialon due to the boron-containing trace volatile components generated from the container. Because there is. The filling of the raw material mixed powder into the container is preferably as bulky as possible from the viewpoint of suppressing interparticle sintering during heating. Specifically, the filling rate of the raw material mixed powder into the synthesis container is preferably 40% by volume or less.
加熱処理の温度が1600℃以上の場合には未反応生成物が多く存在したり、一次粒子の成長が不十分であったりすることがないし、1800℃以下であれば粒子間の焼結が顕著となったりすることもない。 When the temperature of the heat treatment is 1600 ° C. or higher, there are many unreacted products or the primary particle growth is insufficient, and if it is 1800 ° C. or lower, sintering between particles is remarkable. It will never be.
加熱処理における加熱時間ついては、未反応物が多く存在したり、一次粒子が成長不足であったり、或いは、粒子間の焼結が生じてしまったりという不都合が生じない時間範囲が選択され、本発明者の検討に拠れば、2〜24時間程度が好ましい範囲である。 Regarding the heating time in the heat treatment, a time range is selected in which there is no inconvenience that there are many unreacted substances, primary particles are insufficiently grown, or sintering between particles occurs. According to a person's examination, about 2 to 24 hours is a preferable range.
上述した操作で得られるα型サイアロンは塊状なので、これを解砕、粉砕、及び場合によっては分級処理と組み合わせて所定のサイズの粉末にし、いろいろな用途へ適用される粉末状蛍光体となる。 Since the α-sialon obtained by the above-described operation is agglomerated, it is pulverized, pulverized, and optionally classified into a powder of a predetermined size in combination with a classification process, and becomes a powdered phosphor applicable to various uses.
白色LED用蛍光体として好適に使用するためには、一次粒子が複数個焼結してできた二次粒子の平均粒径が3〜20μmにすることが好ましい。平均粒径が3μm以上であれば発光強度が低くなることもなく、平均粒径が20μm以下であればLEDを封止する樹脂への均一分散が容易で、発光強度及び色調のバラツキを生じることもなく、実用上使用可能である。 In order to be suitably used as a phosphor for white LED, it is preferable that the average particle diameter of secondary particles formed by sintering a plurality of primary particles is 3 to 20 μm. If the average particle size is 3 μm or more, the light emission intensity is not lowered, and if the average particle size is 20 μm or less, uniform dispersion to the resin for sealing the LED is easy, resulting in variations in light emission intensity and color tone. There is no practical use.
上述した製法で得られたα型サイアロンからなる塊状物は、比較的易粉砕性に優れ、乳鉢等で容易に所定粒度に粉砕できる特徴を示すが、ボールミルや振動ミル、ジェットミル等の一般的な粉砕機を使用することも当然許容される。 The agglomerates made of α-sialon obtained by the above-mentioned production method are relatively easy to grind and show characteristics that can be easily pulverized to a predetermined particle size with a mortar or the like, but are generally used for ball mills, vibration mills, jet mills, etc. Of course, it is acceptable to use a simple grinder.
本発明の蛍光体は、紫外線から可視光の幅広い励起範囲を有し、可視光を発光することから、照明器具に好適である。特に、α型サイアロンの結晶格子内への侵入元素としてCaとEuとを選択して得られる蛍光体は、ピーク波長が550〜600nmの黄〜橙色光の高輝度発光特性を有している。従い、青色LEDとの組み合わせにより、容易に白色光が得られると言う特徴がある。また、α型サイアロンは、高温にさらしても劣化しないことから耐熱性に優れており、酸化雰囲気および水分環境下での長期間の安定性にも優れている。 The phosphor of the present invention has a wide excitation range from ultraviolet to visible light, and emits visible light, and thus is suitable for a lighting fixture. In particular, the phosphor obtained by selecting Ca and Eu as the intrusion elements into the crystal lattice of α-sialon has high-luminance emission characteristics of yellow to orange light having a peak wavelength of 550 to 600 nm. Accordingly, there is a feature that white light can be easily obtained by combination with the blue LED. In addition, α-sialon is superior in heat resistance because it does not deteriorate even when exposed to high temperatures, and is excellent in long-term stability in an oxidizing atmosphere and moisture environment.
本発明の照明器具は、少なくとも発光光源と本発明の蛍光体を用いて構成される。本発明の照明器具としては、LED照明器具、蛍光ランプなどが含まれ、例えば、特開平5−152609号公報、特開平7−99345号公報、特許第2927279号公報などに記載されているような公知の方法により、本発明の蛍光体を用いてLED照明器具を製造することができる。尚、この場合において、発光光源は350〜500nmの波長の光を発する紫外LED又は青色LEDが好ましく、これらの発光素子としては、GaNやInGaNなどの窒化物半導体からなるものがあり、組成を調整することにより所定の波長の光を発する発光光源となりうる。 The lighting fixture of this invention is comprised using the light-emitting light source and the fluorescent substance of this invention at least. Examples of the lighting fixture of the present invention include LED lighting fixtures, fluorescent lamps, and the like, for example, as described in JP-A-5-152609, JP-A-7-99345, JP-A-2927279, and the like. An LED lighting apparatus can be manufactured using the phosphor of the present invention by a known method. In this case, the light emitting light source is preferably an ultraviolet LED or a blue LED that emits light having a wavelength of 350 to 500 nm. These light emitting elements are made of a nitride semiconductor such as GaN or InGaN, and the composition is adjusted. By doing so, it can be a light emitting light source that emits light of a predetermined wavelength.
照明器具において、本発明の蛍光体を単独で使用する方法以外に、他の発光特性を持つ蛍光体と併用することによって、所望の色を発する照明器具を構成することができる。特に青色LEDを励起源とした場合、本発明の蛍光体とピーク波長が500〜550nmの緑〜黄色光の発光を示す蛍光体との組み合わせるときに、幅広い色温度の白色発光が可能となる。この様な蛍光体としては、Euが固溶したβ型サイアロンが挙げられる。また、更に、CaSiAlN3:Eu等の赤色蛍光体と組み合わせることにより、演色性の向上が達成される。 In addition to the method of using the phosphor of the present invention alone in a lighting fixture, a lighting fixture that emits a desired color can be configured by using it together with a phosphor having other light emission characteristics. In particular, when a blue LED is used as an excitation source, white light emission with a wide color temperature is possible when the phosphor of the present invention is combined with a phosphor exhibiting green to yellow light emission having a peak wavelength of 500 to 550 nm. An example of such a phosphor is β-sialon in which Eu is dissolved. Furthermore, color rendering is improved by combining with a red phosphor such as CaSiAlN 3 : Eu.
次に、実施例、比較例に基づいて、本発明を更に詳細に説明する。 Next, based on an Example and a comparative example, this invention is demonstrated still in detail.
(実施例1)原料粉末として、電気化学工業(株)社製α型窒化ケイ素粉末(NP200グレード)、トクヤマ(株)社製窒化アルミニウム粉末(Fグレード)、関東化学(株)社製炭酸カルシウム粉末(特級試薬)、和光純薬(株)社製フッ化カルシウム粉末(特級試薬)、信越化学工業(株)社製酸化ユーロピウム粉末(RUグレード)を用いて、合成後にα型サイアロン単相となる様に、表1に示す配合とした。 (Example 1) As raw material powder, α-type silicon nitride powder (NP200 grade) manufactured by Denki Kagaku Kogyo Co., Ltd., aluminum nitride powder (F grade) manufactured by Tokuyama Co., Ltd., calcium carbonate manufactured by Kanto Chemical Co., Ltd. Using a powder (special grade reagent), calcium fluoride powder (special grade reagent) manufactured by Wako Pure Chemical Industries, Ltd., and europium oxide powder (RU grade) manufactured by Shin-Etsu Chemical Co., Ltd. Thus, the composition shown in Table 1 was adopted.
配合した原料用粉末を、イソプロピルアルコールを溶媒として、プラスチック製ポットと窒化ケイ素質ボールを用いて、湿式ボールミル混合を行い、ロータリーエバポレータによる溶媒除去を行い、混合粉末を得た。 The blended raw material powder was subjected to wet ball mill mixing using isopropyl alcohol as a solvent and a plastic pot and silicon nitride balls, and the solvent was removed by a rotary evaporator to obtain a mixed powder.
前記混合粉末約50gを内径80mm、高さ50mmの十分に緻密な窒化ホウ素質るつぼ(電気化学工業(株)社製、N−1グレード)にかさ密度がおおよそ0.3g/cm3となる様に充填した。このるつぼに同材質の蓋をし、カーボンヒーターの電気炉内において、窒素大気圧雰囲気中で加熱処理を行った。加熱時の最高温度及び保持時間を表1に示す。得られた試料は、目開き75μmの篩を通過するまで、瑪瑙乳鉢を用いて解砕した。 About 50 g of the mixed powder is placed in a sufficiently dense boron nitride crucible (N-1 grade, manufactured by Denki Kagaku Kogyo Co., Ltd.) having an inner diameter of 80 mm and a height of 50 mm so that the bulk density is approximately 0.3 g / cm 3 . Filled. The crucible was covered with the same material, and heat treatment was performed in a nitrogen atmospheric pressure atmosphere in an electric furnace of a carbon heater. Table 1 shows the maximum temperature and holding time during heating. The obtained sample was crushed using an agate mortar until it passed through a sieve having an opening of 75 μm.
上記操作で得られた粉末に対して、X線回折(XRD)法による結晶相の同定及びリートベルト解析による結晶相の定量評価、並びにレーザー回折散乱法による二次粒子の粒度分布測定を行った。また、走査型電子顕微鏡(SEM)により、粉末の観察を行い、得られた観察像から一次粒子の円相当径及びアスペクト比(長軸径/短軸径)を測定し、円相当径の分布(3〜10μmの円相当径の一次粒子個数が全一次粒子個数に占める割合)及び平均アスペクト比を算出した。尚、評価は少なくとも500個以上の一次粒子に対して行った。 The powder obtained by the above operation was subjected to identification of crystal phase by X-ray diffraction (XRD) method, quantitative evaluation of crystal phase by Rietveld analysis, and measurement of particle size distribution of secondary particles by laser diffraction scattering method. . In addition, the powder is observed with a scanning electron microscope (SEM), the equivalent circle diameter and aspect ratio (major axis diameter / minor axis diameter) of the primary particles are measured from the obtained observation image, and the equivalent circle diameter distribution is measured. (The ratio of the number of primary particles having an equivalent circle diameter of 3 to 10 μm to the total number of primary particles) and the average aspect ratio were calculated. The evaluation was performed on at least 500 primary particles.
また、分光蛍光光度計を用いて、青色光励起(波長460nm)における蛍光スペクトルを測定し、スペクトルのピーク強度とピーク波長を求めた。尚、ピーク強度は測定装置や条件によって変化するため、単位は任意単位であり、同一条件で測定した実施例及び比較例での比較を行った。 Moreover, the fluorescence spectrum in blue light excitation (wavelength 460nm) was measured using the spectrofluorometer, and the peak intensity and peak wavelength of the spectrum were calculated | required. In addition, since the peak intensity varies depending on the measuring apparatus and conditions, the unit is an arbitrary unit, and comparison was made between Examples and Comparative Examples measured under the same conditions.
合成粉末中のホウ素量はICP発光分析法により測定し、フッ素量は次の方法により測定した。試料0.5gを1200℃の反応管内に導入し、95〜96℃の水蒸気で加水分解し、発生ガスを0.05質量%NaOH溶液10mlに吸収したのち、イオンクロマトグラフ法により測定した。上記の評価結果を表2に示す。 The amount of boron in the synthetic powder was measured by ICP emission analysis, and the amount of fluorine was measured by the following method. A 0.5 g sample was introduced into a reaction tube at 1200 ° C., hydrolyzed with steam at 95 to 96 ° C., and the generated gas was absorbed in 10 ml of 0.05 mass% NaOH solution, and then measured by ion chromatography. The evaluation results are shown in Table 2.
XRD測定の結果、合成粉末はα型サイアロン単相であり、平均粒径(二次粒子)は10μmであった。SEM観察の結果、粒子形態はミクロンサイズの比較的等軸状の一次粒子が複数個焼結していた。一次粒子のうち、円相当径が3〜10μmに含まれる割合は92%であり、平均アスペクト比は1.5であった。ホウ素含有量は590ppmで、フッ素含有量は40ppmであった。波長460nmの青色光で励起するとピーク波長587nmの黄橙色発光を示した。 As a result of XRD measurement, the synthetic powder was an α-type sialon single phase, and the average particle size (secondary particles) was 10 μm. As a result of SEM observation, a plurality of relatively equiaxed primary particles having a micron size were sintered. Of the primary particles, the ratio of the equivalent circle diameter contained in 3 to 10 μm was 92%, and the average aspect ratio was 1.5. The boron content was 590 ppm and the fluorine content was 40 ppm. When excited with blue light having a wavelength of 460 nm, yellow-orange light having a peak wavelength of 587 nm was emitted.
(実施例2、3)実施例1と同様の手法、手順に基づいて、実施例2と3を行った。原料粉末配合組成及び合成条件を表1に、合成品の評価結果を表2に示す。 (Examples 2 and 3) Examples 2 and 3 were carried out based on the same method and procedure as in Example 1. Table 1 shows the raw material powder composition and synthesis conditions, and Table 2 shows the evaluation results of the synthesized products.
(比較例1〜3)実施例1と同様の手法、手順に基づいて、比較例1〜3を行った。但し、比較例2では、実施例1の原料粉末以外に和光純薬(株)社製酸化ホウ素粉末を外割で1質量%添加した。 (Comparative Examples 1 to 3) Comparative Examples 1 to 3 were carried out based on the same method and procedure as in Example 1. However, in Comparative Example 2, in addition to the raw material powder of Example 1, Wako Pure Chemical Industries, Ltd. boron oxide powder was added in an amount of 1% by mass.
比較例1では、合成粉末を構成する一次粒子のサイズはサブμm〜数μmと幅広く、円相当径で3〜10μmに含まれる一次粒子の割合は40%であった。発光スペクトルのピーク波長は590nmと実施例1に近いが、発光強度は約半分であった。比較例2では、ホウ素含有量が4520ppmであり、発光スペクトルのピーク波長は、588nmであるが、発光強度は実施例1の約70%であった。比較例3では、フッ素含有量が1200ppmであり、X線回折の結果、α型サイアロン以外に、未反応の窒化ケイ素、窒化アルミニウム並びにユーロピウムの酸フッ化物の存在が確認された。SEM観察の結果、一次粒子は少数のミクロンサイズの粒子と多数のサブミクロン粒子から構成されており、円相当径が3〜10μmに含まれる一次粒子の割合は20%と低い。発光強度は実施例1の約60%であった。 In Comparative Example 1, the size of the primary particles constituting the synthetic powder was wide, from sub μm to several μm, and the proportion of primary particles contained in 3 to 10 μm with an equivalent circle diameter was 40%. The peak wavelength of the emission spectrum was 590 nm, which is close to Example 1, but the emission intensity was about half. In Comparative Example 2, the boron content was 4520 ppm and the peak wavelength of the emission spectrum was 588 nm, but the emission intensity was about 70% of Example 1. In Comparative Example 3, the fluorine content was 1200 ppm. As a result of X-ray diffraction, the presence of unreacted silicon nitride, aluminum nitride and europium oxyfluoride was confirmed in addition to α-sialon. As a result of SEM observation, the primary particles are composed of a small number of micron-sized particles and a large number of submicron particles, and the ratio of primary particles contained in an equivalent circle diameter of 3 to 10 μm is as low as 20%. The emission intensity was about 60% of Example 1.
(実施例4)実施例1で得られたα型サイアロン蛍光体10gを水100gにエポキシシランカップリング剤(信越シリコーン(株)社製、KBE402)1.0gと共に加え、撹拌しながら一晩放置した。その後、ろ過乾燥したシランカップリング剤で処理されたα型サイアロン蛍光体の適量をエポキシ樹脂(サンユレック(株)社製NLD−SL−2101)10gに混練し、発光波長460nmの青色LEDの上にポッティングし、真空脱気し、110℃で前記樹脂を加熱硬化し、表面実装LEDを作製した。 (Example 4) 10 g of α-sialon phosphor obtained in Example 1 was added to 100 g of water together with 1.0 g of an epoxy silane coupling agent (KBE402, manufactured by Shin-Etsu Silicone Co., Ltd.) and left overnight with stirring. did. Thereafter, an appropriate amount of α-sialon phosphor treated with a filtered and dried silane coupling agent is kneaded with 10 g of an epoxy resin (NLD-SL-2101 manufactured by Sanyu Rec Co., Ltd.) and placed on a blue LED having an emission wavelength of 460 nm. Potting, vacuum deaeration, and heat curing of the resin at 110 ° C. produced a surface-mounted LED.
図1に前記白色LEDの概略構造図を示す。この表面実装LEDに10mAの電流を流して発生する光の発光スペクトルを測定した。発光特性及び平均演色評価数を表3に示す。高輝度で相関色温度の低い(電球色)照明器具が得られた。 FIG. 1 shows a schematic structural diagram of the white LED. An emission spectrum of light generated by applying a current of 10 mA to the surface-mounted LED was measured. The light emission characteristics and the average color rendering index are shown in Table 3. A luminaire with high brightness and low correlated color temperature (bulb color) was obtained.
(実施例5)蛍光体として、実施例1のものと波長460nm励起でピーク波長が535nmの黄緑色発光を示すEuをドープしたβ型サイアロンの二種類を適量混合し、実施例4と同様の手法により、表面実装LEDを作製した。発光特性及び平均演色評価数を表3に示す。昼光色で、実施例4よりも演色性の高い照明器具が得られた。 (Example 5) As a phosphor, an appropriate amount of two kinds of phosphors of Example 1 and Eu-doped β-sialon which emits yellow-green light with a wavelength of 460 nm when excited at a wavelength of 460 nm is mixed. Surface mount LED was produced by the method. The light emission characteristics and the average color rendering index are shown in Table 3. A luminaire with daylight color and higher color rendering than Example 4 was obtained.
本発明の蛍光体は、100〜500nmの波長を持つ紫外線又は可視光を励起源として照射することにより550〜600nmの範囲の波長域にピークを持つ発光特性を示すので、青色LED又は紫外LEDを光源とする白色LEDに好適である。また、本発明の照明器具は、前記蛍光体を用いているので、優れた発光特性を有しエネルギー効率が高い、また、優れた演色特性を有しているので、産業上非常に有用である。 The phosphor of the present invention exhibits emission characteristics having a peak in a wavelength range of 550 to 600 nm by irradiating ultraviolet light or visible light having a wavelength of 100 to 500 nm as an excitation source. Suitable for white LED as light source. In addition, since the lighting apparatus of the present invention uses the phosphor, it has excellent light emission characteristics, high energy efficiency, and excellent color rendering characteristics, so it is very useful industrially. .
1. 青色LEDチップ
2. 蛍光体
3. ワイヤーボンド
4. 樹脂層
5. 容器
6、7. 導電性端子
1. 1.
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