JP2005529229A - 発光物質およびこの物質を使用する発光ダイオード - Google Patents
発光物質およびこの物質を使用する発光ダイオード Download PDFInfo
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- JP2005529229A JP2005529229A JP2004539001A JP2004539001A JP2005529229A JP 2005529229 A JP2005529229 A JP 2005529229A JP 2004539001 A JP2004539001 A JP 2004539001A JP 2004539001 A JP2004539001 A JP 2004539001A JP 2005529229 A JP2005529229 A JP 2005529229A
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- blue
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- light source
- phosphor
- luminescent material
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- 239000000126 substance Substances 0.000 title claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 13
- 229910052788 barium Inorganic materials 0.000 claims abstract description 11
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000011575 calcium Substances 0.000 claims abstract 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000000463 material Substances 0.000 claims description 22
- 230000005284 excitation Effects 0.000 claims description 15
- 230000005855 radiation Effects 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- 238000005286 illumination Methods 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 150000001768 cations Chemical class 0.000 abstract description 7
- 229910052693 Europium Inorganic materials 0.000 abstract description 4
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 abstract 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000000295 emission spectrum Methods 0.000 description 13
- 238000001228 spectrum Methods 0.000 description 9
- 229910015999 BaAl Inorganic materials 0.000 description 8
- 150000004645 aluminates Chemical class 0.000 description 8
- 238000000695 excitation spectrum Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000005266 casting Methods 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 229910003668 SrAl Inorganic materials 0.000 description 5
- 238000010348 incorporation Methods 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 3
- 238000002284 excitation--emission spectrum Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910007991 Si-N Inorganic materials 0.000 description 2
- 229910006294 Si—N Inorganic materials 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007850 fluorescent dye Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000009877 rendering Methods 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229910018509 Al—N Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 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
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- -1 silicate nitride Chemical class 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
- 239000000758 substrate Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- 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
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/597—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon oxynitride, e.g. SIALONS
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- H01L2224/42—Wire connectors; Manufacturing methods related thereto
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Abstract
Description
白色LEDに関しては、青色発光ダイオードと黄色発光物質との組合せにより実現されている。このような組合せは貧弱な演色性を有するが、赤緑青システム(RGB)を使用することにより格段に改善することができる。このようなシステムは例えば赤エミッタおよび青エミッタと、例えばSrAl2O4:EuまたはBaAl2O4:Euの緑発光アルミン酸塩蛍光体との組合せを使用する。ただしEuの代わりにMnを添加することもできる。その発光マキシムは約520nm前後である。US−A6278135参照。しかしこれらアルミン酸塩の励起バンドおよび発光バンドの位置は最適ではない。これらは330から400nmの範囲の短波長UVにより励起しなければならない。
本発明の課題は、請求項1の上位概念による新たな発光物質を提供することである。本発明のさらなる目的は、UV/青放射により効率的に励起され、微調整された蛍光体を提供することである。本発明のさらなる課題は、少なくとも1つのLEDを光源として有する照明装置で使用するための蛍光体を提供することであり、このLEDは360から470nmの範囲の一次放射を発生し、この一次放射は部分的にまたは完全に、長波長放射に蛍光体により変換される。この蛍光体はLEDからの一次放射に曝される。さらなる課題は、白色光を放射し、とりわけ高い演色性を有する照明装置を提供することである。さらなる課題は、LEDデバイスのように高効率な照明デバイスを提供することであり、このデバイスは360から470nmの範囲で良好に吸収し、容易に製造できるようにする。
次に、複数の実施形態を参照しながら本発明について詳しく説明する。
図1には、白色光源として用いられる半導体コンポーネント(LED)が注型樹脂を用いた形式(図1a)と注型樹脂を用いてない形式(図1b)とで描かれている。
図2には、本発明による蛍光体を用いた照明装置が示されている。
図3には、本発明による蛍光体の発光スペクトルと反射スペクトルが示されている。
図4から図8には、本発明による別の蛍光体の発光スペクトルと反射スペクトルが示されている。
図9には、ユニットセルの容積とxの値との関係が示されている。
例示のため、白色LEDにおいてInGaNチップとともに使用することに関して、WO 01/40403で用いたのと類似の構造について説明する。図1aには、白色光のためのこのような光源の構造が具体的に描かれている。光源は400nmのピーク発光波長をもつInGaNタイプの半導体コンポーネント(チップ1)をベースとしており、これには第1および第2の電気接続部2および3が設けられていて、これは凹部9の領域で不透明なベースハウジング8中に埋め込まれている。これらの接続部のうち一方の接続部3は、ボンディングワイヤ4を介してチップ1と接続されている。凹部9は壁7を有しており、この壁はチップ1の青色1次放射のための反射器として用いられる。凹部9は注封材料5によって充填されており、これには主成分(有利には重量の少なくとも80%)としてシリコーン注型樹脂(またはエポキシ注型樹脂)が含まれており、さらに(有利には重量の15%よりも僅かに)蛍光色素6を有している。さらに僅かな量としてたとえばメチルエーテルとアエロシルも含まれる。蛍光色素は3つの色素の混合物であり、これは本発明による緑色蛍光体とともに青色光、緑色光および赤色光を発光する。
(1-y)MCO3+(2-x)/2Al2O3+x/4 Si3N4+x/4 SiO2+y/2 Eu2O3 →
M1−yEuyAl2−xSixO4−xNx
ただしM=Ca,Sr,Baの単独または組合せであり、例えばy=0.1である。
MCO3+(2-x)/2 Al2O3+x/4 Si3N4+x/4 SiO2 →
MAl2−xSixO4−xNx{+CO2↑} (M=Ca,Sr,Ba)
BaからCaへ原子半径が低減すると、(SiN)+による(AlO)+の置き換えがこの反応によればいっそう困難になることが判明した。結晶格子パラメータ結果は、トリジマイト構造を有するBaAl2O4へのNの最大溶解度が約x≒0.6であったことを示す。図9は、ユニットセル容積とトリジマイト構造を有するBaAl2−xSixO4−xNxのx値との関係を示す。予想どおり、Al−O間隔と比較して小さなSi−N間隔から、ユニットセル容積はxの上昇と共に減少する。これは図9に示されている。x値が0.6より大きいと、ユニットセル容積はほとんど一定であり、二次相が観察される。
Claims (13)
- 発光物質、有利にはLED適用のための蛍光体であって、該蛍光体は360から470nmの範囲のUV−青色で励起される形式の発光物質において、
Euドープされたホスト格子が一般的組成物MAL2−xSixO4−xNxを備え、ただしMはCa,Sr,Baのグループからのアルカリ希土金属の少なくとも1つであり、x≧0.002かつx≦1.5、有利には0.7以下であり、Euの割合はMの0.1から25%である、ことを特徴とするUV−青色励起発光物質。 - ホスト格子はトリジマイト構造から誘導される、請求項1記載のUV−青色励起発光物質。
- Mは緑色発光を達成するためのストロンチウムおよび/またはバリウムである、請求項1記載のUV−青色励起物質。
- Mは青色発光を達成するためのカルシウムである、請求項1記載のUV−青色励起物質。
- Mは前記物質の少なくとも2つの混合物である、請求項1記載のUV−青色励起物質。
- Mは有利には40mol-%までのZnを付加的に含む、請求項1記載のUV−青色励起物質。
- Alは完全にまたは部分的にGaにより置き換えられる、請求項1記載のUV−青色励起物質。
- Siは完全にまたは部分的に、有利には25%以上がGeにより置き換えられる、請求項1記載のUV−青色励起物質。
- ホスト格子にはさらにMnがドープされており、共ドープされたMnの量は有利にはEuドープの50%までである、請求項1記載のUV−青色励起物質。
- 請求項1から9までのいずれか1つに記載のUV−青色励起発光物質を有する光源(20)。
- 一次放射光は青色であり、請求項1から9までのいずれか1項記載のUV−青色励起発光物質は他の蛍光体、とりわけ赤色発光蛍光体と一次放射光を長波長の二次放射光に変換するために結合されており、これにより白色光を発する、請求項10記載の光源。
- 一次放射光はUVであり、請求項1から9までのいずれか1項記載のUV−青色励起発光物質は他の蛍光体、とりわけ赤色および青色発光蛍光体と一次放射光を長は称の二次放射光に変換するために結合されており、これにより白色光を発する、請求項10記載の光源。
- 光源は少なくとも1つのLEDを備える照明デバイスである、請求項10記載の光源。
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EP20020021177 EP1413619A1 (en) | 2002-09-24 | 2002-09-24 | Luminescent material, especially for LED application |
PCT/EP2003/010598 WO2004029177A1 (en) | 2002-09-24 | 2003-09-23 | Luminescent material and light emitting diode using the same |
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JP2005529229A true JP2005529229A (ja) | 2005-09-29 |
JP3906224B2 JP3906224B2 (ja) | 2007-04-18 |
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US (1) | US7485243B2 (ja) |
EP (2) | EP1413619A1 (ja) |
JP (1) | JP3906224B2 (ja) |
CN (1) | CN1311055C (ja) |
AT (1) | ATE335799T1 (ja) |
DE (1) | DE60307411T2 (ja) |
TW (1) | TWI287566B (ja) |
WO (1) | WO2004029177A1 (ja) |
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WO2004029177A8 (en) | 2004-06-03 |
EP1413619A1 (en) | 2004-04-28 |
CN1311055C (zh) | 2007-04-18 |
EP1438364A1 (en) | 2004-07-21 |
ATE335799T1 (de) | 2006-09-15 |
EP1438364B1 (en) | 2006-08-09 |
US7485243B2 (en) | 2009-02-03 |
JP3906224B2 (ja) | 2007-04-18 |
CN1596292A (zh) | 2005-03-16 |
WO2004029177A1 (en) | 2004-04-08 |
DE60307411D1 (de) | 2006-09-21 |
US20060033081A1 (en) | 2006-02-16 |
DE60307411T2 (de) | 2007-03-29 |
TW200422375A (en) | 2004-11-01 |
TWI287566B (en) | 2007-10-01 |
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