KR100715579B1 - 발광 소자를 포함하는 광원 - Google Patents

발광 소자를 포함하는 광원 Download PDF

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KR100715579B1
KR100715579B1 KR1020057016223A KR20057016223A KR100715579B1 KR 100715579 B1 KR100715579 B1 KR 100715579B1 KR 1020057016223 A KR1020057016223 A KR 1020057016223A KR 20057016223 A KR20057016223 A KR 20057016223A KR 100715579 B1 KR100715579 B1 KR 100715579B1
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South Korea
Prior art keywords
light source
light
alkaline earth
luminofo
sio
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KR1020057016223A
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KR20050093871A (ko
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스테판 타스치
피터 페치럴
군둘라 로쓰
월터 테우스
울프갱 켐프퍼르트
데트레프 스타릭크
Original Assignee
트리도닉 옵토엘렉트로닉스 게엠베하
리텍 게베에르
로이히트슈토프베르크 브라이퉁엔 게엠베하
토요다 고세이 캄파니 리미티드
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Application filed by 트리도닉 옵토엘렉트로닉스 게엠베하, 리텍 게베에르, 로이히트슈토프베르크 브라이퉁엔 게엠베하, 토요다 고세이 캄파니 리미티드 filed Critical 트리도닉 옵토엘렉트로닉스 게엠베하
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    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
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    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7795Phosphates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C09K11/00Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7734Aluminates
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    • C09K11/7728Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/774Borates
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/0001Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems
    • G02B6/0011Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form
    • G02B6/0033Means for improving the coupling-out of light from the light guide
    • G02B6/0035Means for improving the coupling-out of light from the light guide provided on the surface of the light guide or in the bulk of it
    • G02B6/00362-D arrangement of prisms, protrusions, indentations or roughened surfaces
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    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
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    • G02B6/0011Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form
    • G02B6/0066Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings specially adapted for lighting devices or systems the light guides being planar or of plate-like form characterised by the light source being coupled to the light guide
    • G02B6/0073Light emitting diode [LED]
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    • H01L33/50Wavelength conversion elements
    • H01L33/501Wavelength conversion elements characterised by the materials, e.g. binder
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21LIGHTING
    • F21YINDEXING SCHEME ASSOCIATED WITH SUBCLASSES F21K, F21L, F21S and F21V, RELATING TO THE FORM OR THE KIND OF THE LIGHT SOURCES OR OF THE COLOUR OF THE LIGHT EMITTED
    • F21Y2105/00Planar light sources
    • F21Y2105/10Planar light sources comprising a two-dimensional array of point-like light-generating elements
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    • H01L33/26Materials of the light emitting region
    • H01L33/30Materials of the light emitting region containing only elements of group III and group V of the periodic system
    • H01L33/32Materials of the light emitting region containing only elements of group III and group V of the periodic system containing nitrogen
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    • H01L33/00Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
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Abstract

본 발명은 제 1 스펙트럼 영역에서 방사하는 발광 소자, 및 알칼리토류오르토실리케이트 그룹으로부터 유래하고 광원에 의해 방출된 광의 일부분을 흡수하여 다른 스펙트럼 영역으로 방출하는 루미노포를 구비한 광원에 관한 것이다. 본 발명에 따라, 루미노포는 (2-x-y)SrO·x(Ba,Ca)O·(1-a-b-c-d)SiO2·aP2O5 bAl2O3 cB2O3 dGeO2: y Eu2+ 및/또는 (2-x-y)BaO·x(Sr,Ca)O·(1-a-b-c-d)SiO2·aP2O5 bAl2O3 cB2O3 dGeO2: y Eu2+의 조성을 갖고, 2가의 유러퓸으로 활성화된 알칼리토류오르토실리케이트이다. 원하는 칼라(칼라 온도)는 전술한 유형의 루미노포를 사용함으로써 쉽게 조절될 수 있다. 광원은 2가의 유러퓸 및/또는 망간으로 활성화되고 알칼리토류알루미네이트 그룹으로부터 선택된 추가의 루미노포, 및/또는 그룹 Y(V, P, Si)O4: Eu 그룹으로부터 선택된 적색을 방출하는 다른 추가 루미노포 또는 알칼리토류-마그네슘-디실리케이트를 포함한다.
알칼리토류오르토실리케이트, 유러품, 루미노포

Description

발광 소자를 포함하는 광원 {LIGHT SOURCE COMPRISING A LIGHT-EMITTING ELEMENT}
도 1 내지 도 6은 본 발명에 따른 다양한 LED-광원의 스펙트럼(파장에 의존하는 상대적인 강도 I)을 보여준다;
도 7 내지 도 10은 본 발명에 따른 LED-광원의 여러가지 실시예를 보여준다.
본 발명은 제 1 스펙트럼 영역, 바람직하게는 광학 스펙트럼의 청색 및/또는 자외선 영역에서 방사하는 발광 소자, 및 알칼리토류오르트실리케이트 그룹으로부터 유래하거나 또는 상기 발광 재료 그룹으로부터 적어도 일부분을 함유하고 발광 소자의 방출의 일부분을 흡수하며, 다른 스펙트럼 영역, 바람직하게는 황-녹색, 황색 또는 오렌지색 영역에서 방사하는 루미노포를 구비한 광원에 관한 것이다. 선택된 루미노포는 또한 상기 그룹의 다른 루미노포와의 혼합에 의해서 및/또는 상기 그룹에 속하지 않는 다른 발광 재료와의 혼합에 의해서도 사용될 수 있다.
발광 소자는 바람직하게 무기 LED이지만, 유기 LED, 레이저 다이오드, 두꺼운 층의 무기 전기 발광 박막 또는 얇은 층의 무기 전기 발광 소자일 수도 있다.
무기 LED는 무엇보다도 긴 수명, 적은 공간 수요, 진동에 대한 불감성 및 스펙트럼상 좁은 대역의 방출을 특징으로 한다.
(특히 스펙트럼상 넓은 대역의) 수많은 방출 칼라는 LED 내에 있는 활성 반도체 재료 고유의 방출로 인해 전혀 구현될 수 없거나 또는 구현된다 할지라도 비효율적이다. 무엇보다 이와 같은 단점은 백색광의 형성에 적용된다.
WO 00/33390에는, 청색만을 방출하는 LED 또는 발광 재료 혼합물과 함께 작용하는 레이저 다이오드를 포함하는 발광 장치를 보여준다. 이 경우 420 내지 470nm의 스펙트럼 영역에서 방출하는 LED는 백색광을 형성하기 위해 적어도 2개의 발광 재료로 이루어진 발광 재료 혼합물과 조합된다. 필수적인 2가지 발광 재료는 상기 목적을 위해 상이한 스펙트럼으로 방출해야 한다. 사용되는 발광 재료 혼합물은 언제나 하나의 적색 성분 및 녹색 성분을 포함한다. LED로부터 방출되는 청색 광선과의 칼라 혼합에 의해 백색광이 형성된다.
선행 기술에 따라 반도체로 고유하게 구현될 수 없는 방출 칼라가 색 변환에 의해서 형성된다.
실제로 칼라 변환 기술은, 적어도 하나의 루미노포가 LED-다이 위에 배치되는 원리를 기초로 한다. 상기 루미노포는 다이로부터 방출되는 광선의 일부분을 흡수하는 동시에 포토 발광으로 여기된다. 그 경우 소스의 방출 칼라 및 광 칼라는 다이의 투과성 광선과 발광 재료의 방출 광선의 혼합으로부터 얻어진다.
루미노포로서는 기본적으로 유기 및 무기 계통이 사용될 수 있다. 무기 색소의 중요한 장점은 유기 계통에 비해 보다 높은 화학적 안정성, 온도 안정성 및 광에 대한 안정성이다. 무기 LED의 긴 수명과 관련하여, 수명이 긴 무기 루미노포는 2가지 성분으로 이루어진 광원의 높은 색 위치 안정도를 보장해준다.
청색을 방출하는 LED로부터 송출되는 광선이 백색광으로 변환되면, 상기 청색광(450-490nm)을 효과적으로 흡수하고 고효율로 대부분 황색인 형광 광선으로 변환시키는 발광 재료가 필요하다. 물론 상기 요구 조건을 충족시키는 무기 루미노포는 다만 소수이다. 현재 대부분의 재료들은 YAG-발광 재료 부류로부터 청색 LED를 위한 색 변환 색소로서 사용된다(WO 98/05078; WO 98/05078; WO 98/12757). 물론 상기 재료에는 560nm보다 작은 최대 방출시에만 충분히 높은 효과를 갖는다는 단점이 있다. 이와 같은 이유에서 청색 다이오드(450-490nm)와 조합된 YAG-색소에 의해서는 6000 내지 8000K의 칼라 온도를 갖고 칼라 재현이 비교적 낮은(칼라 재현율(Ra)에 대한 통상적인 값은 70 내지 75) 청-백색의 광 칼라만이 구현될 수 있다. 그로부터 심하게 제한된 적용 가능성들이 얻어진다. 한편으로 일반 조명에 백색 광원을 적용하는 경우에는 일반적으로 발광 재료의 칼라 재현 품질에 대해 보다 높은 요구 조건이 제기되고, 다른 한편으로 특히 유럽 및 북미의 소비자는 2700 내지 5000K의 칼라 온도를 갖는 더 고온의 광 칼라를 선호한다.
WO 00/33389호에는 또한, 특히 Ba2SiO4:Eu2+를 청색 LED의 광 변환을 위한 루미노포로서 사용하는 것이 공지되어 있다. 그러나 발광 재료 Ba2SiO4:Eu2+의 최대 방출값이 505nm이기 때문에, 결과적으로 상기와 같은 안전 수단과의 조합에 의해서는 백색광이 형성될 수 없다.
S.H.M Poort 등의 논문 "Optical properties of Eu2+-activated orthosilicates and orthophospates", Journal of Alloys and Compounds 260 (1997), Pages 93-97에는 Eu-활성화된 Ba2SiO4 그리고 KBaPo4 및 KSrPO4와 같은 포스페이트의 특성이 검사된다. 이 논문에서도 Ba2SiO4의 방출은 대략 505nm에서 이루어진다는 것이 확인된다.
본 발명의 과제는, 높은 광수율 및 높은 칼라 재현 품질을 갖는 동시에 고온의 칼라 온도를 갖는 백색광이 형성될 수 있도록, 특히 일반 조명용의 CIE에 의해서 확인된 공차 타원 내부에 있는 칼라 위치가 얻어질 수 있도록 서문에 언급한 방식의 광원을 개선하는 것이다.
상기 목적은 서문에 언급한 광원에 의해 본 발명에 따라, 루미노포가 하기와 같은 조성의 또는 상기 조성으로 이루어진 혼합물의 2가 유러퓸으로 활성화된 알칼리토류오르토실리케이트이고:
a) (2-x-y)SrO·x(Bau,Cav)O·(1-a-b-c-d)SiO2·aP2O5 bAl2O3 cB2O3 dGeO2: y Eu2+, 이 경우에는
0 ≤ x < 1.6
0.005 < y < 0.5
x + y ≤ 1.6
0 ≤ a, b, c, d < 0.5
u + v = 1이 적용되고,
b) (2-x-y)BaO·x(Sru,Cav)O·(1-a-b-c-d)SiO2·aP2O5 bAl2O3 cB2O3 dGeO2: y Eu2+, 이 경우에는
0.01 < x < 1.6
0.005 < y < 0.5
0 ≤ a, b, c, d < 0.5
u + v = 1
x·u ≥ 0.4가 적용되며;
이 경우 바람직하게 상기 값들 a, b, c 및 d 중에서 적어도 하나의 값이 0.01 보다 크다. 상기 2가지 일반식에서 실리콘의 일부분은 갈륨으로 대체될 수 있다.
놀랍게도, 본 발명에 따른 유러퓸 활성화된 알칼리토류오르토실리케이트의 그룹으로부터 선택되고 전술한 조성을 갖는, 루미노포와 청색 LED의 조합에 의해 우수한 칼라 재현 및 높은 광수율을 갖는 백색광이 구현될 수 있다는 사실이 발견되었다. 즉, 순수한 바륨오르토실리케이트를 기재로 하고 청-녹색 광을 방출하는 루미노포와 달리 바륨-스트론튬-오르토실리케이트-혼합 결정에 의해서는 황-녹색, 황색 내지 황-오렌지색 및 칼슘을 오르토실리케이트 격자 내에 혼입하여 얻어지는 완전히 오렌지색의 형광색이 형성됨으로써, 청색 LED의 투과성 광과 선택된 루미노포의 방출된 형광의 혼합에 의해 높은 칼라 재현 및 높은 효율을 갖는 백색광이 발생될 수 있다. Ba를 오르토실리케이트내에 있는 Sr로 대체함으로써 이루어지는 방출 칼라의 이동은 지금까지 다만 전술한 Poort 등의 논문에 기술된 강한 UV-광선(254nm-여기)에 의한 여기용으로만 공지되었다; 그와 달리 상기 효과가 놀랍게도 440-475nm의 범위에서 청색광으로 방사할 때 강화되어 나타났다는 사실은 아직까지 기술되지 않았다. Ba-Sr-Ca-오르토실리케이트혼합 결정 및 긴 파장의 UV-광선 또는 청색광으로 여기할 때의 상기 결정의 강한 방출 능력은 지금까지 완전히 공지되지 않았다.
선택된 루미노포는 상기 그룹의 다른 루미노포와의 혼합에 의해서 및/또는 상기 그룹에 속하지 않는 추가 루미노포와의 혼합에 의해서도 사용될 수 있다. 마지막으로 언급한 루미노포에는 예를 들어 청색을 방출하고 2가의 유러퓸 및/또는 망간으로 활성화된 알칼리토류알루미네이트, 및 적색을 방출하고 하기 일반식의 그룹 Y(V, P, Si)O4:Eu,Bi, Y2O2S:Eu,Bi 또는 유러퓸 및 망간 활성화된 알칼리토류-마그네슘-디실리케이트:Eu2+,Mn2+으로부터 선택된 루미노포가 속한다:
Me(3-x-y)MgSi2O8 : xEu, yMn,
상기 식에서
0.005 < x < 0.5
0.005 < y < 0.5이고,
Me = Ba 및/또는 Sr 및/또는 Ca.
하기에서 기술되는 실시예가 보여주는 바와 같이, 백색광을 발생시킬 수 있기 위해서는, 본 발명에 따른 혼합-결정-루미노포 내에 함유된 Sr-함량이 지나치게 적어서는 안된다.
놀랍게도, P2O5, Al2O3 및/또는 B2O3를 오르토실리케이트 격자내에 추가로 혼입하고, 일부의 실리콘을 게르마늄으로 치환하는 것이 마찬가지로 개별 루미노포의 방출 스펙트럼에 대해 상당한 영향을 끼침으로써, 상기 방출 스펙트럼이 개별 적용예를 위해 바람직하게 더 변경될 수 있다는 사실도 또한 발견되었다. 이 경우 Si(IV) 보다 크기가 작은 이온은 일반적으로 보다 긴 파장 영역으로 방출 최대값이 이동되게 하는 한편, 크기가 더 큰 이온은 보다 짧은 파장으로 방출 중심을 이동시킨다. 또한, 예를 들어 할로겐화물 및/또는 알칼리금속이온과 같은 적은 양의 1가 이온이 추가로 루미노포 격자 내에 혼입되면, 상기 방출 스펙트럼이 결정성, 방출 능력 및 특히 본 발명에 따른 루미노포의 안정성을 위해서도 바람직할 수 있다고 나타났다.
본 발명의 추가 바람직한 실시예에 따라 광원은 적어도 2개의 상이한 루미노포를 가지며, 이 경우 적어도 하나의 루미노포는 알칼리토류오르토실리케이트 발광 재료이다. 이와 같은 방식에 의해, 개별 적용을 위해 필요한 백색조가 매우 정확하게 조절될 수 있고, 특히 80 이상의 Ra-값에 도달할 수 있다. 본 발명의 추가의 바람직한 변형예는 스펙트럼의 자외선 영역, 예컨대 370 내지 390nm 영역에서 방출하는 LED와 적어도 3개의 발광 재료의 조합인데, 상기 3개의 발광 재료 중에서 적 어도 하나의 재료는 본 발명에 따른 알칼리토류오르토실리케이트 발광 재료이다. 추가의 발광 재료로서는 상응하는 발광 재료 혼합에 의해 청색을 방출하는 알칼리토류알루미네이트가 사용될 수 있으며, 상기 알루미네이트는 그룹 Y(V, P, Si)O4:Eu,Bi, Y2O2S:Eu,Bi으로부터 선택되거나 또는 유러퓸 및 망간 활성화된 알칼리토류-마그네슘-디실리케이트 그룹으로부터 선택되고 적색을 방출하는 루미노포 및/또는 유러퓸 및/또는 망간에 의해 활성화된다.
본 발명에 따른 광원의 기계적인 실시예를 위해서는 다수의 가능성이 존재한다. 한 실시예에 따라, 하나 이상의 LED-칩이 반사기 내부에 있는 프린트 회로 기판 상에 배치되고, 루미노포가 반사기 위에 배치된 광 디스크 내에서 분산되는 것이 제안된다.
그러나, 하나 이상의 LED-칩이 반사기 내부에 있는 프린트 회로 기판 상에 배치되고 루미노포가 반사기 상에 제공되는 것도 또한 가능하다.
바람직하게 상기 LED-칩은 둥근 지붕 형상을 갖는 투과성 캡슐화제로 주조된다. 상기 캡슐화제는 한편으로는 기계적 보호부를 형성하고, 다른 한편으로는 상기 재료의 광학 특성을 또한 개선시킨다(LED-다이로부터 광의 우수한 배출).
루미노포는 프린트 회로 기판 상에 있는 LED-칩 장치 및 폴리머 렌즈를 가급적 가스 영향 없이 결합시키는 캡슐화제 내에서도 분산될 수 있으며, 상기 폴리머 렌즈 및 캡슐화제는 최대 0.1만큼 차이가 나는 굴절율을 갖는다. 상기 캡슐화제는 LED-다이에 직접 포함될 수 있지만, 상기 재료가 투과성 캡슐화제로 주조되는 것도 가능하다(그 경우에는 투과성 캡슐화제 및 루미노포를 갖는 캡슐화제가 존재한다). 유사한 굴절율에 의해 경계면에서는 반사에 의한 손실이 거의 없다.
폴리머 렌즈가 바람직하게 구 형태 또는 타원 형태의 리세스를 가지고, 상기 리세스가 캡슐화제로 완전히 채워짐으로써, LED-어레이는 폴리머 렌즈에 대해 작은 간격으로 고정된다. 이와 같은 방식에 의해 기계적 구조물의 높이가 줄어들 수 있다.
루미노포를 균일하게 분배하기 위해서는, 루미노포가 바람직하게 무기 매트릭스 내에서 현탁되는 것이 바람직하다.
적어도 2개의 루미노포를 사용하는 것은, 적어도 2개의 상기 루미노포가 광 확장에 의해 연속으로 배치된 매트릭스 내에서 개별적으로 분산되는 것이 바람직하다. 그럼으로써, 루미노포의 농도는 여러가지 루미노포의 통일된 분산에 비해 감소될 수 있다.
하기에는 본 발명의 한 바람직한 변형예에서 루미노포를 제조하기 위한 주요 단계들이 도시되어 있다:
알칼리토류오르토실리케이트-루미노포의 제조를 위해서는, 선택된 조성에 상응하게 출발 물질인 알칼리토류카보네이트, 실리콘산화물 및 유러퓸 산화물의 화학량론적인 양이 균일하게 혼합되어, 1100℃ 내지 1400℃의 온도 및 환원 분위기에서, 발광 재료를 제조하기 위한 통상의 고체 반응에 의해 원하는 루미노포로 변환된다. 이 경우에는 반응 혼합물에 바람직하게는 0.2 몰 미만의 암모늄클로라이드 또는 다른 할로겐화물이 추가되는 것이 결정성에 장점이 된다. 본 발명의 의미에서는 실리콘의 일부분도 게르마늄, 붕소, 알루미늄, 인으로 대체될 수 있으며, 이 것은 열에 의해 산화물로 분해될 수 있는 전술한 원소들의 상응하는 량의 화합물을 첨가함으로써 구현된다. 유사한 방식에 의해, 적은 양의 알칼리금속 이온이 각각의 격자 내에 혼입될 수 있다.
함유된 본 발명에 따른 오르토실리케이트 루미노포는 대략 510nm 내지 600nm의 파장에서 방출하고, 110nm까지의 절반값 폭을 갖는다.
반응 파라미터를 상응하게 형성하고 예를 들어 1가의 할로겐화물 및/또는 알칼리금속 이온을 소정 첨가함으로써, 본 발명에 따른 루미노포의 입자 크기 분배는 개별 적용예의 요구 조건에 맞추어 조절될 수 있으며, 이 경우에는 손상적인 기계적 분쇄 공정이 실행될 필요가 없다. 이와 같은 방식에 의해, 대략 2㎛ 내지 20㎛의 평균 입자 크기로, 길고 폭이 넓은 입자 크기 분배가 이루어질 수 있다.
본 발명의 추가 장점은 실시예 및 도면을 참조하여 하기에서 설명된다.
도 1은 2700 K의 칼라 온도를 갖는 백색 LED의 방출 스펙트럼을 보여주며, 상기 칼라 온도는 464 nm의 중심 파장을 갖는 제 1 스펙트럼 범위에서 방출하는 청색 LED 및 Sr1.4Ca0.6SiO4:Eu2+의 조성을 갖는 본 발명에 따른 루미노포(Luminophor)의 조합에 의해 형성되며, 상기 루미노포는 596 nm의 최대값을 갖는 제 2 스펙트럼 범위에서 방출한다.
본 발명에 따른 각각 하나의 오르토실리케이트루미노포와 464 nm에서 방출하는 LED의 조합에 대한 추가 예는 도 2 및 도 3에 도시되어 있다. Sr1.90Ba0.08Ca0.02SiO4:Eu2+의 조성을 갖고 황색을 방출하는 루미노포가 색 변환을 위해 사용되면, 4100 K의 칼라 온도를 갖는 백색광 칼라가 세팅될 수 있는 한편, Sr1.84Ba0.16SiO4:Eu2+의 조성을 갖는 루미노포를 사용하는 경우에는 예를 들어 6500 K의 칼라 온도를 갖는 백색광원이 제조될 수 있다.
본 발명에 따른 2개의 오르토실리케이트루미노포와 464 nm - LED의 조합을 위한 전형적인 스펙트럼은 도 4가 보여준다. 사용된 발광 재료는 Sr1.4Ca0.6SiO4:Eu2+ 및 Sr1.00Ba1.00SiO4:Eu2+의 조성을 갖는다. 도 4에 도시된 구체적인 스펙트럼을 위해서는 5088 K의 칼라 온도 및 82의 칼라 재현율(Ra)이 얻어진다. 물론 루미노포의 선택된 양 비율에 따라 모든 칼라 온도는 대략 3500 K 내지 7500 K의 범위에서 구현될 수 있으며, 이 경우 본 발명에 따른 알칼리토류오르토실리케이트-루미노포로 이루어진 상기와 같은 혼합물의 큰 장점은 무엇보다도 동시에 Ra-값이 80 이상에 도달될 수 있다는 데 있다.
이것은 도 5에 예로 제시되어 있다. 도시된 스펙트럼은 Sr1.6Ca0.4Si0.98Ga0.02O4:Eu2+및 Sr1.10Ba0.90SiO4:Eu2+의 조성을 갖는 2개 루미노포로 이루어진 혼합물과 464 nm - LED의 조합을 대표하고, 5000 K의 칼라 온도에서 82의 RA-값을 제공한다.
*370-390 nm의 최대값을 갖는 제 1 스펙트럼 범위에서 방출하는 UV-LED가 광 선 방출 소자로서 사용되면, 도 4의 본 발명에 따른 루미노포 및 동시에 청색-녹색 방출 바륨-마그네슘-알루미네이트 발광 재료:Eu, Mn의 소정 부분을 함유하는 발광 재료 혼합물과 상기 LED의 조합에 의해서 90 이상의 Ra-값이 실현될 수 있다. 도 6은 6500 K의 칼라 온도에서 91의 Ra를 갖는 상응하는 백색광원의 방출 스펙트럼을 보여준다.
추가의 예는 하기 기록에서 알 수 있다. 하기 기록에서는, 사용된 무기 LED의 방출 파장 및 본 발명에 따른 루미노포의 개별 조성 외에, 결과적으로 얻어지는 칼라 온도 및 Ra-값 그리고 광원의 칼라 위치가 지시되어 있다:
T = 2778 K (464 nm + Sr1.4Ca0.6SiO4:Eu2+); x = 0.4619, y = 0.4247, Ra = 72
T = 2950 K (464 nm + Sr1.4Ca0.6SiO4:Eu2+); x = 0.4380, y = 0.4004, Ra = 73
T = 3497 K (464 nm + Sr1.6Ba0.4SiO4:Eu2+); x = 0.4086, y = 0.3996, Ra = 74
T = 4183 K (464 nm + Sr1.9Ba0.08Ca0.02SiO4:Eu2+); x = 0.3762, y = 0.3873, Ra = 75
T = 6624 K (464 nm + Sr1.9Ba0.02Ca0.08SiO4:Eu2+); x = 0.3101 y = 0.3306, Ra = 76
T = 6385 K (464 nm + Sr1.6Ca0.4SiO4:Eu2+ + Sr0.4Ba1.6SiO4:Eu2+) x = 0.3135, y = 0.3397, Ra = 82
T = 4216 K (464 nm + Sr1.9Ba0.08Ca0.02SiO4:Eu2+); x = 0.3710, y = 0.3696, Ra = 82
3954 K (464 nm + Sr1.6Ba0.4SiO4:Eu2+ + Sr0.4Ba1.6SiO4:Eu2+ + YVO4:Eu3+); x = 0.3756, y = 0.3816, Ra = 84
T = 6489 K (UV-LED + Sr1.6Ca0.4SiO4:Eu2+ + Sr0.4Ba1.6SiO4:Eu2+ + 바륨-마그네슘-알루미네이트: Eu2+); x = 0.3115, y = 0.3390, Ra = 86
T = 5097 K (464nm + Sr1.6Ba0.4(Si0.98B0.02)O4:Eu2+ + Sr0.6Ba1.4SiO4:Eu2+); x = 0.3423, y = 0.3485, Ra = 82
T = 5084 K (UV-LED + Sr1.6Ca0.4(Si0.99B0.01)O4:Eu2+ + Sr0.6Ba1.4SiO4:Eu2+ + 스트론튬-마그네슘-알루미네이트: Eu2+); x = 0.3430, y = 0.3531, Ra = 83
T = 3369 K (464nm + Sr1.4Ca0.6Si0.95Ge0.05O4:Eu2+); x = 0.4134, y = 0.3959, Ra = 74
T = 2787 K (466nm + Sr1.4Ca0.6Si0.98P0.02O4.01:Eu2+); x = 0.4630, y = 0.4280, Ra = 72
T = 2913 K (464nm + Sr1.4Ca0.6Si0.98Al0.02O4:Eu2+); x = 0.4425, y = 0.4050, Ra = 73
T = 4201 K
본 발명의 바람직한 변형예에서 색 변환은 하기와 같이 실행된다:
하나 이상의 LED-칩(1)(도 7 참조)은 프린트 회로 기판(2) 상에 어셈블링된다. LED 바로 위에는 (한편으로는 LED-칩을 보호하기 위해서 그리고 다른 한편으로는 LED-칩 내에서 형성된 광의 더 우수한 해체를 가능하게 하기 위해서) 반구 혹은 반타원 형태의 캡슐화제(3)가 배치된다. 상기 캡슐화제(3)는 각각의 다이를 개별적으로 포함할 수 있거나, 또는 모든 LED에 공통적인 형상일 수 있다. 이와 같이 장착된 프린트 회로 기판(2)은 반사기(4) 내에 삽입되거나, 또는 반사기가 LED-칩(1) 위로 인출된다.
반사기(4) 상에는 광디스크(5)가 올려진다. 상기 광디스크는 한편으로는 장치를 보호하기 위해서 이용되고, 다른 한편으로는 상기 광디스크 내에 루미노포(6)가 혼합된다. 상기 광디스크(5)를 관통하는 청색 광(또는 자외선)이 루미노포(6)를 부분적으로 통과할 때 제 2 스펙트럼 영역으로 변환됨으로써, 전체적으로 백색 효과가 나타난다. 평탄-병렬 플레이트에서 나타나는 것과 같은 도파관-효과에 의 한 손실은 상기 디스크의 불투명한 소산 특성에 의해 감소된다. 또한 반사기(4)는, 다만 미리 정렬된 광만이 광디스크(5) 상에 충돌하여 전체 반사 효과가 처음부터 감소되도록 작용한다.
도 8에 도시된 바와 같이 루미노포(6)를 반사기(4) 상에 올려 놓는 것도 가능하다. 그 경우에는 광디스크가 필요없다.
대안적으로는, 각 LED-칩(1) 상에 (도 9 참조) 반사기(4')가 올려질 수 있고, 상기 반사기는 커플러 형태로 주조될 수 있으며(캡슐화제(3')), 광디스크(5)는 각 반사기(4') 위에 또는 전체 장치 위에 배치될 수 있다.
조명원을 제조하기 위해서는, 개별-LED 대신에 LED-어레이를 사용하는 것이 바람직하다. 본 발명의 바람직한 변형예에서는, LED-칩(1)이 프린트 회로 기판(2) 바로 위에 어셈블링되도록 구성된 LED-어레이(1')(도 10 참조) 상에서 색 변환이 하기의 형태로 실행된다:
LED-어레이(1')(도 10 참조)는 캡슐화제(3, 예컨대 에폭시드)에 의해 다른 재료(예컨대 PMMA)로 이루어진 투과성 폴리머 렌즈(7)에 접착된다. 폴리머 렌즈(7)의 재료 및 캡슐화제(3)는, 상기 재료들이 가급적 유사한 굴절율을 갖도록 - 즉 위상이 매칭되도록 선택된다. 캡슐화제(3)는 최대로 구 형태 또는 타원 형태인 폴리머 렌즈(7)의 리세스 내에 있다. 상기 리세스의 형상은, 캡슐화제(3) 내에서 색 변환 재료가 분산되어 상기 형상에 의해 각도와 무관한 방출 칼라가 형성될 수 있기 때문에 중요하다. 대안적으로는, 어레이가 먼저 투과성 캐스팅 재료로 주조되고, 그 다음에 색 변환 재료를 함유하는 캐스팅 재료에 의해 폴리머 렌즈에 접착될 수 있다.
적어도 2개의 상이한 루미노포가 사용되고 매우 우수한 칼라 재생 능력을 갖춘 백색의 LED를 제조하기 위해서는, 상기 루미노포가 하나의 매트릭스 내에서 공통으로 분산되지 않고, 오히려 상기 루미노포가 별도로 분산 및 제공되는 것이 유리하다. 이것은 특히 최종적인 광 칼라가 다단계의 색 변환 프로세스에 의해 형성되는 조합에 적용된다. 즉, 하기에서 진행되는 바와 같은 방출 프로세스에 의해 파장이 가장 긴 방출 칼라가 형성된다: 제 1 루미노포에 의한 LED-방출의 흡수 - 제 1 루미노포의 방출 - 제 2 루미노포에 의한 제 1 루미노포의 방출의 흡수 및 제 2 루미노포의 방출. 특히 상기와 같은 프로세스를 위해서는 개별 재료를 광확장 방향으로 연속으로 배치하는 것이 선호되는데, 그 이유는 그럼으로써 다양한 재료의 통일적인 분산에 비해 재료의 농도가 감소될 수 있기 때문이다.
본 발명은 기술된 예에 제한되지 않는다. 루미노포는 폴리머 렌즈(또는 다른 광학 수단) 내에도 제공될 수 있다. 또한, 루미노포를 직접 LED-다이 위에 또는 투과성 캡슐화제 표면 상에 배치하는 것도 가능하다. 또한 루미노포는 확산 입자와 함께 매트릭스 내에 제공될 수도 있다. 그럼으로써, 매트릭스 내에서의 함몰이 저지되고, 균일한 광배출이 보장된다.
전술한 바와 같이, 본 발명에 따른 루미노포와 청색 LED의 조합에 의해 우수한 칼라 재현 및 높은 광수율을 갖는 백색광이 구현될 수 있다.
또한 루미노포가 확산 입자와 함께 매트릭스 내에 제공됨으로써, 매트릭스 내에서의 함몰이 저지되고, 균일한 광배출이 보장된다.

Claims (9)

  1. 근자외선과 청색 사이의 범위에서 방사하는 LED,
    근자외선 내지 청색 방사의 일부를 흡수하고 또다른 스펙트럼 영역에서 방사하는 루미노포를 포함하며,
    상기 루미노포가 2가 유러퓸으로 활성화된 알칼리토류 오르토실리케이트, 및 적색 방사 루미노포를 포함하는 것을 특징으로 하는 백색광을 형성하는 광원.
  2. 제1항에 있어서, 상기 LED는 370 내지 390nm 사이의 범위에서 방사하는 것을 특징으로 하는 백색광을 형성하는 광원.
  3. 제2항에 있어서, 상기 루미노포는 청색 방사 루미노포를 더 포함하는 것을 특징으로 하는 백색광을 형성하는 광원.
  4. 제1항에 있어서, 상기 적색 방사 루미노포는 Y(V, P, Si)4:Eu,Bi, Y2O2S:Eu,Bi, 및 유러퓸 또는 망간으로 활성화된 알칼리토류 마그네슘 디실리케이트로부터 선택되는 것을 특징으로 하는 백색광을 형성하는 광원.
  5. 제3항에 있어서, 상기 청색 방사 루미노포는 유러퓸 및 망간으로 활성화된 알칼리토류 알루미네이트를 포함하는 것을 특징으로 하는 백색광을 형성하는 광원.
  6. 제1항에 있어서, 2가 유러퓸으로 활성화된 알칼리토류 오르토실리케이트는 다음의 조성물 중의 하나인 것을 특징으로 하는 백색광을 형성하는 광원.
    a) (2-x-y)SrO·x(Bau,Cav)O·(1-a-b-c-d)SiO2·aP2O5 bAl2O3 cB2O3 dGeO2:y Eu2+, 이 경우,
    0 ≤ x < 1.6 0.005 < y < 0.5 x + y ≤ 1.6
    0 ≤ a, b, c, d < 0.5 u + v = 1이 적용되고,
    b) (2-x-y)BaO·x(Sru,Cav)O·(1-a-b-c-d)SiO2·aP2O5 bAl2O3 cB2O3 dGeO2: y Eu2+, 이 경우,
    0.01 < x < 1.6 0.005 < y < 0.5
    0 ≤ a, b, c, d < 0.5 u + v = 1 x·u ≥ 0.4가 적용.
  7. 제6항에 있어서, 상기 값들 a b, c, 및 d 중에서 적어도 하나는 0.01보다 큰 것을 특징으로 하는 백색광을 형성하는 광원.
  8. 제6항에 있어서, 상기 루미노포 내에서 실리콘의 일부는 갈륨으로 대체되는 것을 특징으로 하는 백색광을 형성하는 광원.
  9. 제1항에 있어서, 상기 루미노포는 확산 입자를 포함하는 것을 특징으로 하는 백색광을 형성하는 광원.
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