JP2013515110A - 蛍光体及びこの種の蛍光体を有する光源 - Google Patents
蛍光体及びこの種の蛍光体を有する光源 Download PDFInfo
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 150000004767 nitrides Chemical class 0.000 claims abstract description 15
- 239000012190 activator Substances 0.000 claims abstract description 10
- 150000001768 cations Chemical class 0.000 claims abstract description 7
- 102100032047 Alsin Human genes 0.000 claims description 20
- 101710187109 Alsin Proteins 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 230000005855 radiation Effects 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 description 53
- 239000011575 calcium Substances 0.000 description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 238000010348 incorporation Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 229910001431 copper ion Inorganic materials 0.000 description 5
- 229910052712 strontium Inorganic materials 0.000 description 5
- 229910052788 barium Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- -1 copper halides Chemical class 0.000 description 4
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000009877 rendering Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910016509 CuF 2 Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 239000002223 garnet Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
- 229910016344 CuSi Inorganic materials 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910012506 LiSi Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910003564 SiAlON Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000005090 crystal field Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000006185 dispersion Substances 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
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical group N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
EP 1 696 016からは、赤色蛍光体としてカルシン(Calsin)を使用する変換型LEDは公知である。カルシンの概念についてはCaAlSiN窒化物を意味している。
本発明の課題は、窒化物系蛍光体の特性を特別な課題に適切に合わせることを可能にする請求項1の上位概念に記載の蛍光体を提供することである。
窒化物系蛍光体、例えばM2-xCuxSi5N8:Eu(式中、M=(Sr,Ca,Ba))、(この蛍光体の基本形はUS 6 682 663から公知である)及び
Ca1-xCuxAlSiN3:Eu(この蛍光体の基本形はEP 1696016から公知である)並びに
酸窒化物系蛍光体、例えばM1-xCuxSi2N2O2:Eu(式中、M=(Sr,Ca,Ba)),(この蛍光体の基本形はWO 2004/030109から公知である)並びに
更にアルファ−SiAlON類、(この蛍光体の基本形はUS 6 657379から公知である)である。詳細には、式Mp/2Si12-p-qAlp+qOqN16-q:Eu2+(式中、M=Caを単独で又はSr及びMgと組み合わせて、q=0〜2.5及びp=0.5〜3)により表される基本形が重要である。pについて高い値を選択する、つまりp=2〜3であるのが好ましく、qについては相対的に低い値を選択する、つまりq=0〜1であるのが好ましい。純粋なAlの代わりに、特にGaの20mol%までの割合を有するAl,Ga混合物を使用することができる。
次に、本発明を、複数の実施例を用いて詳細に説明する。
図1は、自体公知のようなRGBベースの白色光用の変換型LEDの構造を示す。この光源は、435〜455nmのピーク波長、例えば445nmのピーク発光波長を有する、InGaN型の青色発光するチップ1を備えた半導体コンポーネントであり、この半導体コンポーネントは光不透過性のベースハウジング8中の凹所9の範囲内に埋め込まれている。このチップ1は、ボンディングワイヤ14を介して第1の端子3と接続され、かつ第2の電気端子2とは直接接続されている。この凹所9は注型材料5で充填されていて、この注型材料は主成分としてシリコーン(60〜90質量%)及び蛍光体顔料6(約15〜40質量%)を含有する。第1の蛍光体は、緑色発光するガーネット蛍光体Lu3(Al,Ga)5O12:Ce(LuAGaG)であり、第2の蛍光体としては赤色発光するアルミノニトリドシリケートCa0.99Cu0.01AlSiN3:Eu(0.5%)である。この凹所は、壁部17を有し、この壁部17は、チップ1からの一次放射線及び顔料6からの二次放射線のためのリフレクタとして用いられる。
Ca(1-x)CuxAlSiN3:Eu2+(0.5%)である。
(Ca1-xCux)AlSiN3-2/3xF2x:Eu(0.5%)(式中、x=0.012)
を有する本発明による蛍光体である。
1. 少なくとも1種のカチオンM及び付活剤Dを備え、前記カチオンの割合xがCuで置き換えられていて、Dは一連のEu、Ce、Sm、Yb及びTbからの少なくとも1種の元素である、窒化物系又は酸窒化物系蛍光体の種類からなる蛍光体。
Claims (12)
- 少なくとも1種のカチオンM及び付活剤Dを備え、前記カチオンの割合xがCuで置き換えられていて、Dは一連のEu、Ce、Sm、Yb及びTbからの少なくとも1種の元素である、窒化物系蛍光体又は酸窒化物系蛍光体の種類からなる蛍光体。
- 前記蛍光体は、ニトリドシリケート、オキシニトリドシリケート、変性されたCaAlSiN、又はアルファ−サイアロンであることを特徴とする、請求項1記載の蛍光体。
- 前記蛍光体が付活剤としてEuを有することを特徴とする、請求項1記載の蛍光体。
- Mに対するCuの割合が、0.05〜5Mol%の範囲内にあることを特徴とする、請求項1記載の蛍光体。
- 前記付活剤Dの割合が、0.2〜15Mol%の範囲内にあることを特徴とする、請求項1記載の蛍光体。
- 前記蛍光体は、Ca1-xCuxAlSiN3:Eu型のカルシンであることを特徴とする、請求項1記載の蛍光体。
- Mに対するCuの割合が、0.2〜5Mol%の範囲内にあることを特徴とする、請求項1記載の蛍光体。
- 請求項1から7までのいずれか1項記載の蛍光体を備えた光源。
- 前記光源は、変換型LED、蛍光灯又は高圧放電ランプであることを特徴とする、請求項1記載の光源。
- 一次放射線を発するチップと、前記チップの前方に配置された蛍光体を有する層とを備え、前記層は、前記チップの一次放射線の少なくとも一部を二次放射線に変換し、その際、請求項1から7までのいずれか1項記載の少なくとも1種の第1の蛍光体が使用される、変換型LED。
- 白色を作成するための他の蛍光体として、(Lu,Y,Gd)3(Al,Ga)5O12:Ceを使用することを特徴とする、請求項10記載の変換型LED。
- 第1の蛍光体がCuで変性されたCaAlSiN3:Euであることを特徴とする、請求項10記載の変換型LED。
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DE102009055185A DE102009055185A1 (de) | 2009-12-22 | 2009-12-22 | Leuchtstoff und Lichtquelle mit derartigen Leuchtstoff |
DE102009055185.9 | 2009-12-22 | ||
PCT/EP2010/068102 WO2011085849A2 (de) | 2009-12-22 | 2010-11-24 | Leuchtstoff und lichtquelle mit derartigem leuchtstoff |
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CN104736667B (zh) | 2012-10-16 | 2017-12-12 | 电化株式会社 | 荧光体、发光装置及照明装置 |
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JP2004182780A (ja) * | 2002-11-29 | 2004-07-02 | Nichia Chem Ind Ltd | 窒化物蛍光体及びそれを用いた発光装置 |
WO2006077740A1 (ja) * | 2004-12-28 | 2006-07-27 | Nichia Corporation | 窒化物蛍光体及びその製造方法並びに窒化物蛍光体を用いた発光装置 |
JP2006274265A (ja) * | 2005-03-09 | 2006-10-12 | Philips Lumileds Lightng Co Llc | 放射線源と蛍光物質を含む照明システム |
WO2008015207A1 (de) * | 2006-08-04 | 2008-02-07 | Osram Gesellschaft mit beschränkter Haftung | Leuchtstoff aus der klasse der nitridosilikate und lichtquelle mit derartigem leuchtstoff |
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NL8400660A (nl) | 1984-03-01 | 1985-10-01 | Philips Nv | Luminescerend scherm. |
EP1104799A1 (en) | 1999-11-30 | 2001-06-06 | Patent-Treuhand-Gesellschaft für elektrische Glühlampen mbH | Red emitting luminescent material |
DE10133352A1 (de) | 2001-07-16 | 2003-02-06 | Patent Treuhand Ges Fuer Elektrische Gluehlampen Mbh | Beleuchtungseinheit mit mindestens einer LED als Lichtquelle |
KR100961342B1 (ko) | 2002-03-22 | 2010-06-04 | 니치아 카가쿠 고교 가부시키가이샤 | 질화물 형광체와 그 제조 방법 및 발광 장치 |
EP1413618A1 (en) | 2002-09-24 | 2004-04-28 | Osram Opto Semiconductors GmbH | Luminescent material, especially for LED application |
JP3837588B2 (ja) | 2003-11-26 | 2006-10-25 | 独立行政法人物質・材料研究機構 | 蛍光体と蛍光体を用いた発光器具 |
KR100665299B1 (ko) | 2004-06-10 | 2007-01-04 | 서울반도체 주식회사 | 발광물질 |
DE102007035592B4 (de) * | 2007-07-30 | 2023-05-04 | Osram Gmbh | Temperaturstabiler Leuchtstoff, Verwendung eines Leuchtstoffs und Verfahren zur Herstellung eines Leuchtstoffs |
TW200925250A (en) * | 2007-12-12 | 2009-06-16 | wei-hong Luo | Warm white light emitting semiconductor and yellow-orange silicate phosphor powder thereof |
DE102009037730A1 (de) | 2009-08-17 | 2011-02-24 | Osram Gesellschaft mit beschränkter Haftung | Konversions-LED mit hoher Farbwiedergabe |
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WO2006077740A1 (ja) * | 2004-12-28 | 2006-07-27 | Nichia Corporation | 窒化物蛍光体及びその製造方法並びに窒化物蛍光体を用いた発光装置 |
JP2006274265A (ja) * | 2005-03-09 | 2006-10-12 | Philips Lumileds Lightng Co Llc | 放射線源と蛍光物質を含む照明システム |
WO2008015207A1 (de) * | 2006-08-04 | 2008-02-07 | Osram Gesellschaft mit beschränkter Haftung | Leuchtstoff aus der klasse der nitridosilikate und lichtquelle mit derartigem leuchtstoff |
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EP2491095B1 (de) | 2015-01-07 |
US9263221B2 (en) | 2016-02-16 |
KR101756275B1 (ko) | 2017-07-26 |
JP5606552B2 (ja) | 2014-10-15 |
CN102959045A (zh) | 2013-03-06 |
EP2491095A2 (de) | 2012-08-29 |
CN102959045B (zh) | 2016-02-10 |
KR20120106861A (ko) | 2012-09-26 |
WO2011085849A2 (de) | 2011-07-21 |
DE102009055185A1 (de) | 2011-06-30 |
US20130113364A1 (en) | 2013-05-09 |
WO2011085849A3 (de) | 2011-09-15 |
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