CN1495921A - 发光装置 - Google Patents
发光装置 Download PDFInfo
- Publication number
- CN1495921A CN1495921A CNA031549381A CN03154938A CN1495921A CN 1495921 A CN1495921 A CN 1495921A CN A031549381 A CNA031549381 A CN A031549381A CN 03154938 A CN03154938 A CN 03154938A CN 1495921 A CN1495921 A CN 1495921A
- Authority
- CN
- China
- Prior art keywords
- light
- fluorophor
- emitting device
- emitting diode
- emitting
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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Images
Classifications
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- 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
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- C—CHEMISTRY; METALLURGY
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
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- C—CHEMISTRY; METALLURGY
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- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
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- G02B6/0013—Means for improving the coupling-in of light from the light source into the light guide
- G02B6/0023—Means for improving the coupling-in of light from the light source into the light guide provided by one optical element, or plurality thereof, placed between the light guide and the light source, or around the light source
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
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- 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
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- H01L33/502—Wavelength conversion materials
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
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Abstract
本发明提供了一种发光装置(100)，包括一发光半导体元件(102)和一含荧光体的树脂(101)，所述的发光半导体元件发出第一种光，所述的第一种光的发射光谱的峰值波长λ不大于530nm，所述含萤光体的树脂含有，至少吸收一部分发自所述发光半导体元件的第一种光而发出第二种光的荧光体，其特征在于，所述的荧光体是含有一种稀土元素的石榴石且荧光体的颗粒的尺寸是受控制的分布。
Description
本发明是中国专利申请97196762.8的分案申请。
技术领域
本发明涉及一种用于LED显示器、后照光光源、信号机、照光式开关与各种指示器的发光二极管，特别涉及发光装置及使用所述发光装置的显示装置，所述发光装置包括光致发光荧光体，其中发光元件变换所产生的光的波长，并使其发光。
背景技术
发光二极管因小型，可发出效率良好的色彩鲜艳的光，以及系半导体元件，故具有无灯泡烧坏之虞，初始驱动特性和耐震性优越，以及进一步反复开/关点亮方面极强的特点。因此，可广泛用来作为各种指示器与种种光源。最近有人开始分别开发超高亮度、高效率RGB(红、绿、蓝)发光二极管，并使用设有此种发光二极管的大画面LED显示器。这种LED显示器具有以极少电力即可动作，质量轻以及使用寿命长的优点，可预期今后将广泛使用。
此外，最近有人使用发光二极体来进行种种构成白色发光光源的尝试。为了使用发光二极管得到白色光，由于发光二极体具有单色性峰值波长，故例如有将R、G、B三发光元件邻近配置，使其发光而扩散混色的必要。想要藉此构成产生白色光情形下，会有由于发光元件的色调与亮度等的分散而无法产生所需白色的问题。此外，在发光元件分别以不同材料形成情形下，各发光元件的驱动电力等有针对各个不同元件施加预定电压的必要。而且，由于发光元件为半导体发光元件，故会有各个元件的温度特性随时间变化不同，色调随环境而变化，以及无法将由各发光元件所产生的光均匀混合而产生色斑的诸多问题。即，虽然发光二极管作为各个色发光的发光装置有效，但无法成为使用发光元件产生白色光的满意光源。
因此，本申请人于特开平5-152609号公报、特开平7-99345号公报、特开平7-176794号公报、特开平8-8614号公报等文献中公开了一种发光二极管，将原先发光元件产生的光以荧光体作色变换进行输出。所揭示的发光二极管系用一种发光元件可发出白色等其他发光色，其结构如下。
上述公报所揭示的发光二极管，具体而言，系将发光层的能带间隙大的发光元件配置在设于引线框前端的帽部(cap)上，含有荧光体，在覆盖发光元件的树脂模构件中吸收来自发光元件的光。发出与所吸收光波长不同的光(波长变换)。
在上述所揭示的发光二极管中，使用可发出蓝色柔光的发光元件来作为发光元件，由于藉含有荧光体的树脂来模制，且此荧光体吸收所述发光元件所发的光而发出黄色光系，故可制得一种能由混色发出白色光系的发光二极管。
但是，已往的发光二极管有随着荧光体劣化而色调偏差，或荧光体发黑光的外部取出效率低下的情形等问题。此处所谓发黑是指，例如，使用(Cd，Zn)S荧光体等的无机系列荧光体情形下，构成此荧光体的金属元素一部分，一面析出一面变质而着色，再者，在使用有机系列荧光体材料情形下，由于2重结合切断等而着色。特别是指使用具有高能带间隙的半导体为发光元件以提高荧光体变换效率的情形(也即，基于半导体来提高所发光的能量，增加荧光体所可吸收阈值以上的光，而吸收较多的光)下，或荧光体使用量减少的情形(即，相对地，荧光体所照射的能量增多)下，由于荧光体所吸收的光的能量必然会升高，故荧光体显然会劣化。而且，发光元件的发光强度使用更长时间的话，荧光体会进一步加速劣化。
设置在发光元件近傍发荧光体，因发光元件的温度上升与外部环境(例如由于在屋外使用场合的太阳光等)也暴露于高温下，由于这种热而发生劣化的情形。
此外，根据所述荧光体还有由于从外部渗入的水份和制造时内部所含水分和上述的光以及热而促进劣化的情形。
另外，在使用离子性的有机染料的情况下，在芯片附近的直流电场引起的电气移动而使色调变化。
发明内容
因此，本发明目的在于提供一种发光装置以解决上述课题，使在较高亮度、长时间使用环境下，发光光度与发光光率的降低和色偏差极小。
本发明的第1方面提供了一种发光装置(100)，包括一发光半导体元件(102)和一含萤光体的树脂(101)，所述的发光半导体元件发出第一种光，所述的第一种光的发射光谱的峰值波长λ不大于530nm，所述含萤光体的树脂含有，至少吸收一部分发自所述发光半导体元件的第一种光而发出第二种光的萤光体，其特征在于，所述的萤光体是含有一种稀土元素的石榴石且萤光体的颗粒的尺寸是受控制的分布。
本发明还提供了如本发明的第1方面所述的发光装置，其特征在于，所述的萤光体含有YAG:Ce。
本发明还提供了如本发明的第1或2方面所述的发光装置，其特征在于，所述的第二种光的发射光谱实质上比第一种光的发射光谱长。
本发明还提供了如本发明的第1至3方面中的任何一个方面所述的发光装置，其特征在于，所述的发光半导体元件发出篮光。
本发明还提供了本发明还提供了本发明还提供了如本发明的第1至4方面中的任何一个方面所述的发光装置，其特征在于，所述的含有萤光体的树脂被设置在所述的发光半导体元件(102)之上或上面。
本发明还提供了本发明还提供了如本发明的第1至4方面中的任何一个方面所述的发光装置，其特征在于，所述的含有萤光体的树脂，至少直接覆盖所述的发光半导体元件(102)的一部分以及至少一部分与所述的发光半导体元件电气连接(103)。
本发明还提供了如本发明的第5方面所述的发光装置，其特征在于，从所述的发光半导体元件发出的第一种光透过被设置在一透光树脂的光发射侧的表面上的荧光体而辐射。
本发明还提供了如本发明的第5方面所述的发光装置，其特征在于，所述的发光半导体元件(102)的表面的至少一部分被涂上所述的含有萤光体的树脂。
本发明还提供了如本发明的第1至8方面中的任何一个方面所述的发光装置，其特征在于，所述的发光半导体元件(102)在剖视图中呈C状开口，以及来自所述的呈C状开口的第一种光透过所述的含有萤光体的树脂(101)而被辐射。
本发明还提供了如本发明的第1至8方面中的任何一个方面所述的发光装置，其特征在于，所述的发光半导体元件(102)被设置在一壳(204)中，且在所述的壳的开口的至少一部分中填充所述的含有萤光体的树脂(101)。
本发明还提供了如本发明的第2方面所述的发光装置，其特征在于，第二种光的峰值波长比第一种光的第一峰值波长要长。
本发明还提供了如本发明的第1至11方面中的任何一个方面所述的发光装置，其特征在于，所述的含有萤光体的树脂含有环氧树脂、尿素树脂或硅。
本发明还提供了如本发明的第1至12方面中的任何一个方面所述的发光装置，其特征在于，所述的含有萤光体的树脂(101)及/或一模构件材料(104)含有分散剂。
本发明还提供了如本发明的第1至13方面中的任何一个方面所述的发光装置，其特征在于，所述的萤光体吸收和转换第一种光的蓝色区。
本发明还提供了如本发明的第1至12方面中的任何一个方面所述的发光装置，其特征在于，所述的含有萤光体的树脂含有数种不同的无机发光材料。
本发明还提供了一种LED显示器，包含如本发明的第1至15方面中的任何一个方面所述的发光装置。
本发明还提供了一种用于汽车或航空工业的光源，包含如本发明的第1至15方面中的任何一个方面所述的发光装置。
本发明还提供了一种用于液晶显示的照明，包含如本发明的第1至15方面中的任何一个方面所述的发光装置。
本发明还提供了本发明还提供了如本发明的第13方面所述的发光装置，其特征在于，所述的分散剂含有钛酸钡、氧化钛、氧化铝与二氧化硅一组中所选出的一种或多种物质。
本发明还提供了如本发明的第2方面所述的发光装置，其特征在于，所述YAG:Ce含有Gd。
本发明还提供了如本发明的第1方面所述的发光装置，其特征在于，所述的峰值波长不小于400nm。
本发明还提供了如本发明的第1方面所述的发光装置，其特征在于，所述的稀上元素为Ce。
本发明还提供了如本发明的第1方面所述的发光装置，其特征在于，所述的萤光体包含含有Y和Al的石榴石以及至少由铈(Ce)做为激活剂。
本发明为达到此目的，在包括发光元件与荧光体的发生装置中，
(1)作为发光元件可作高亮度发光，而且对于长时间使用其发光特性稳定；
(2)作为荧光体，接近上述高亮度发光元件而设置，即使在长时间使用在来自所述发光元件的强光情形下，特性变化极小，而在对耐光性与耐热性方面甚为优异(特别是邻近发光元件而配置的荧光体，根据我们的研究，因具有比太阳光强达30倍-40倍的光，故作为发光元件，若使用高亮度，在使用方面，荧光体所要求的耐候性非常严格)；
(3)作为发光元件与荧光体的关系，荧光体可发出一种光，其发光波长有效吸收且有效异于带有来自发光元件的光谱宽度的单色性峰波长的光。
即，本发明的发光装置是包括发光层为半导体的发光元件和吸收所述发光元件所发出的光的一部分并发出所具有的波长与所吸收的光波长不同的光的光致发光荧光体的发光装置。
上述发光元件的发光层由氮化物系列化合物半导体制成，并且上述光致发光荧光体含有自Y、Lu、Sc、La、Gd与Sm所组成的元素组中所选出的至少一种元素，以及自Al、Ga与In所组成的元素组中所选出的至少一种元素，而且，含有以铈活化的石榴石系列荧光体为其特征。
这里，氮化物系列化合物半导体(一般式为IniGajAlkN，其中0≤i，0≤j，0≤k，i+j+k＝1)始于掺杂有InGaN和各种不纯物的GaN而含有种种物质。
此外，上述光致发光荧光体始于Y3Al5O12:Ce、Gd3In5O12:Ce而含有如上所定义的种种物质。
本发明的发光装置由于使用由可用高亮度发光的氮化物系列化合物半导体制成这种发光元件，故可作高亮度的发光。且在所述发光装置中，所使用的上述光致发光荧光体即使长时间暴露于强光下，荧光特性的变化也极小，而且在耐光性上极为优异。因此，能提供一种发光装置，可针对长时间使用，减少其特性劣化，可减少不仅因来自发光元件的强光，也因野外环境等外来光(含有紫外线的太阳光等)所造成的劣化，使色斑与光亮度降低的情形变得极少。此外，本发明的发光装置，由于所使用的上述光致发光荧光体为短残光，故也可用在需要120n秒这样的较快反应速度的用途方面。
在本发明的发光二极管中，上述光致发光荧光体最好是含有具有Y与Al的钇铝石榴石系列荧光体，由此，可提高发光装置的亮度。
在本发明的发光装置中，作为上述光致发光荧光体，可使用一般式以(Re1-rSmr)3(Al1-sGas)5O12:Ce来表示的荧光体(其中，0≤r＜1，0≤s≤1，而Re是从Y、Gd中所选出的至少的一种)，以获得与使用钇铝石榴石系列荧光体的场合同样优异的特性。
此外，本发明的发光装置为了缩小发光特性(发光波长与发光强度等)的温度依赖性，作为上述光致发光荧光体，最好使用一般式以(Y1-p-q-rGdpCeqSmr)3(Al1-sGas)5O12来表示的荧光体，(其中，0≤p≤0.8、0.0003≤q≤0.2、0.0003≤r≤0.08、0≤s≤1)。
此外，在本发明的发光装置中，上述光致发光荧光体也最好具有分别含Y与Al而组成互异的二个以上以铈活化的钇铝石榴石系列荧光体。由此，即可对应于发光元件的特性(发光波长)，调整光致发光荧光体的发光光谱，发出所要的发光色。
此外，在本发明的发光装置中，为了将发光装置的发光波长设定于设定值，上述光致发光荧光体最好含有分别用(Re1-rSmr)3(Al1-sGas)5O12:Ce(其中，0≤r＜1，0≤s≤1，而Re是从Y、Gd中所选出的至少一种)的一般式来表示，以包含相互组成不同的二个以上荧光体为佳。
此外，在本发明的发光装置中，为了调整发光波长，上述光致发光荧光体也最好含有一般式以Y3(Al1-sGas)5O12:Ce来表示的第1荧光体，以及一般式以Re3Al5O12:Ce来表示的第2荧光体。
其中，0≤s≤1，而Re是从Y、Gd、La中所选出的至少一种。
此外，在本发明的发光装置中，为了调整发光波长，上述光致发光荧光体也最好包含分别在钇铝石榴石系列荧光体中的使钇的一部分与钆置换且相互置换量不同的第1荧光体与第2荧光体。
甚而，在本发明的发光装置中，最好上述发光元件的发光光谱的主峰值设定在400nm至530nm范围内，且上述光致发光荧光体的主发光波长设定成比上述发光元件的主峰值长。由此，即可有效发出白色系列的光。
而且，最好在上述发光元件中，所述发光元件的发光层含有含In的氮化镓系列半导体，而上述光致发光荧光体是一种钇铝石榴石系列荧光体材料，在钇铝石榴石系列荧光体中，Al的一部分以Ga在Ga∶Al＝1∶1至4∶6的比率范围内置换，并且可以在钇铝石榴石系列荧光体中Y的一部分以Gd在Y∶Gd＝4∶1至2∶3的比率范围内置换。如此调整的光致发光荧光体的吸收光谱可使具有作为发光层的含In的氮化镓系半导体的发光元件所发出的光波长非常一致，而增进变换效率(发光效率)。此外，所述发光元件的蓝色光与所述荧光荧光的混色光可成为光效性品质极佳的白色，从而提供在这方面极优异的发光装置。
本发明的一实施例的发光装置，将上述发光元件经由上述光致发光荧光体设置在其一侧面，并且除其一主表面外的表面具备有实质上以反射构件来覆盖的大致呈矩形的导光板，上述发光元件经由上述光致发光荧光体与导光板使所发出的光成为面状，而且从上述导光板的上述的一主表面输出。
本发明其他实施例的发光装置特征在于，上述发光元件设于其一侧面，上述光致发光荧光体设于其一主表面上，包括有用一个以一个反射构件实质上覆盖除所述一主表面外的表面而大体上呈矩形的导光板，上述发光元件经由导光板与上述光致发光荧光体使所发出的光成为面状，而且由上述导光板的上述一主表面发出。
此外，本发明的LED显示装置包括有矩阵状配置本发明发光装置的LED显示器，以及依输入所述LED显示器的显示数据来驱动的驱动电路，由此提供可作为精细显示且视觉上色斑极少的较廉价LED显示装置。
本发明一实施例的发光装置是一种发光二极管，包括
具有帽部与引线部安装引线；
配置在所述安装引线的帽部内，且其一侧的电极电气连接于安装引线的LED芯片；电气连接于所述LED芯片的另一侧电极的内引线；
以覆盖所述LED芯片的方式充填在所述帽部内的透光性涂覆构件；以及
模构件，所述模构件含有所述安装引线的帽部、所述内引线与连接于所述LED芯片的另一侧电极的连接部分，并且覆盖由以所述涂覆构件覆盖的LED芯片；
其特征在于，所述LED芯片是作为氮化物系列化合物半导体，且所述涂覆构件含有光致发光荧光体，所述光致发光荧光体由含有从Y、Lu、Sc、La、Gd与Sm所组成的一组中所选出的至少一种元素与从Al、Ga与In所组成的一组中所选出的至少一种元素，并且由以铈活化的石榴石系列荧光体组成。
在本发明的发光二极体中，上述光致发光荧光体最好具有含Y与Al的钇铝石榴石系列荧光体。
此外，本发明的发光二极管若为上述光致发光荧光体，最好使用一般式以(Re1-rSmr)3(Al1-sGas)5O12:Ce来表示的荧光体(其中0≤r＜1，0≤s≤1，而Re是从Y、Gd中所选出的至少一种)。
此外，本发明的发光二极管若为上述光致发光荧光体，也可使用一般式以(Y1-p-q-rGdpCeqSmr)3(Al1-sGas)5O12来表示的荧光体，(其中，0≤p≤0.8、0.003≤q≤0.2、0.0003≤r≤0.08、0≤s≤1)。
在本发明的发光二极管中，为了将发光波长调整成所要的波长，上述光致发光荧光体最好包括二个以上分别含有Y与Al的相互之间组成相异的以铈活化的钇·铝石榴石系列荧光体。
为了将发光波长调整或所要的波长，本发明的发光二极管同样地，最好使用一般式分别以(Re1-rSmr)3(Al1-sGas)5O12:Ce来表示(其中0≤r＜1，0≤s≤1，而Re是从Y、Gd中所选出的至少一种)而相互之间组成相异的二个以上的荧光体来作为上述光致发光荧光体。
同样地，本发明的发光二极管为了将发光波长调整成所要的波长，最好使用一般式以Y3(Al1-aGas)5O12:Ce表示的第一荧光体和一般式以Re3Al5O12:Ce表示的第二荧光体来作为前述光致发光荧光体。其中，0≤s≤1，而Re是从Y、Ga、La中所选出的至少一种。
同样地，本发明的发光二极管为了将发光波长调整成所要的波长，上述光致发光荧光体也最好在钇铝石榴石系列荧光体中使用第1荧光和第2荧光体材料，分别使第1荧光体材料和第2荧光体材料钇的一部分与钆置换而相互置换量不同。
此外，一般而言，荧光体吸收短波长的光而发出长波长的光，较吸收长波长的光而言发出短波的光者效率为佳。与其使用发出紫外光使树脂(模构件与涂覆构件)劣化不如使用发出可见光较佳。因此，在本发明的发光二极管中，为了提高发光效率与延长其寿命，最好将上述发光元件的发光光谱主峰值设定在可见光中较短波长的400nm至530nm范围内，并且将上述光致发光荧光体的主发波长设定成比上述发光元件的主峰值长。此外，依此方式，由荧光体变换的光，由于也较发光元件所发出的光波长还长，所以荧光体等所反射而变换后的光即使照射在发光元件上，也不会为发光元件所吸收(因变换后的光比能带间隙的能量小)。如此，荧光体等反射的光即为载置有发光元件的帽部所反射，并能进一步作有效的发光。
附图说明
图1表示与本发明实施形态有关的引线型发光二极管模式的剖视图。
图2表示与本发明实施形态有关的芯片型发光二极管型式的剖视图。
图3A表示以第一实施形态的以铈活化的石榴石系列荧光体所激励的光谱图。
图3B表示以第一实施形态的以铈活化的石榴石系列荧光体所发出的光谱图。
图4表示第1实施形态的发光二极管的发光光谱图。
图5A表示表示以第二实施形态的以铈活化的钇铝石榴石系列荧光体的激励光谱图。
图5B表示表示以第二实施形态的以铈活化的钇铝石榴石系列荧光体的发光光谱图。
图6表示用于说明第二实施形态的发光二极管发光色的色度图，在图中，A与B点表示发光元件所发出的光，C、D点分别表示来自二种光致发光荧光体的发光色。
图7表示与本发明的其他实施形态相关的面状发光光源模式的剖视图。
图8表示不同于图7的面状发光光源模式的剖视图。
图9表示不同于图7与图8的面状发光光源模式的剖视图。
图10表示本发明应用例的显示装置的方块图。
图11表示图10所示显示装置的LED显示器的平面图。
图12表示使用本发明的发光二极管与RGB的四个发光二极体来构成象素的LED显示器平面图。
图13A表示在25℃下实施例1与比较例1的发光二极管的寿命试验结果图。
图13B表示60℃，90％RH下实施例1与比较例1的发光二极管的寿命试验结果图。
图14A表示相对于经过时间的亮度保护率，实施例9与比较例2的耐候性试验结果图。
图14B表示相对于经过时间的亮度保护率，实施例9与比较例2的耐候性试验结果图，是表示试验前后的色调变化。
图15A表示实施例9与比较例2的发光二极管的可靠性试验结果，亮度保持率与时间的关系。
图15B表示实施例9与比较例2的发光二极管的可靠性试验结果，色调与时间的关系。
图16表示将表1所示荧光体与峰值波长465nm的蓝色LED组合的发光二极管实现的色再现范围的色度图。
图17表示将表1所示荧光体与峰值波长465nm的蓝色LED组合的发光二极管中荧光体含有量变化时的发光色的变化的色度图。
图1 8A表示以(Y0.6Gd0.4)3Al5O12:Ce来表示的实施例2的光致发光荧光体的光谱图。
图18B表示具有发光峰值波长460nm的实施例2的发光元件的发光光谱图。
图18C表示实施例2的发光二极管的发光光谱图。
图19A表示以(Y0.2Gd0.8)3Al5O12:Ce来表示的实施例5的光致发光荧光体的发光光谱图。
图19B表示具有发光峰值波长450nm的实施例5的发光元件的发光光谱图。
图19C表示实施例5的发光二极管的发光光谱图。
图20A表示以Y3Al5O12:Ce来表示的实施例6的光致发光荧光体的发光光谱图。
图20B表示具有发光峰值波长450nm的实施例6的发光元件的发光光谱图。
图20C表示实施例6的发光二极管的发光光谱图。
图21A表示以Y3(Al0.5Ga0.5)5O12:Ce来表示的实施例7光致发光荧光体的发光光谱图。
图21B表示具有发光峰值波长450nm的实施例7发光元件的发光光谱图。
图21C表示实施例7的发光二极管的发光光谱图。
图22A表示以(Y0.8Gd0.2)3Al5O12:Ce来表示的实施例11的光致发光荧光体的发光光谱图。
图22B表示以(Y0.4Gd0.6)3Al5O12:Ce来表示的实施例11的光致发光荧光体的发光光谱图。
图22C表示具有发光峰值波长470nm的实施例11的发光元件的发光光谱图。
图23表示实施例11发光二极管的发光光谱图。
标号对照说明
100 发光二极管 101，201，701 涂覆
102，2302，702 发光元件 103，203 电线
104 模构件 105 安装引线
105a 帽部 106 内引线
205 端子金属 504 框体
505 蔽光构件 506 矽胶
601 LED显示器 602 驱动器
603 RAM 604 色调控制装置
605 驱动电路 702 发光二极管
703 金属基板 704 导光板
705，707 反射构件 706 散射片
具体实施方式
下面，参照附图对本发明的实施形态进行说明。
图1的发光二极管100是具备有安装引线105与内引线106的引线型发光二极管，发光元件102设在安装引线105的帽部105a上，含有规定的光致发光荧光体的涂覆树脂101充填在帽部105a内而覆盖发光元件102后用树脂模制成形而构成。发光元件102的n侧电极与p侧电极分别使用电线103来将安装引线105与内引线106连接。
在如以上所述结构成的发光二极管中，发光元件(LED芯片)102所发光(以下称为LED光)的一部分激励涂覆树脂101内所含光致发光荧光体而产生与LED光的波长不同的光，将光致发光荧光体所产生的荧光与无助于光致发光荧光体激励而发出的LED光混色而输出。其结果是，发光二极管100也发出与发光元件102所发出的LED光的波长不同的光。
图2表示芯片型发光二极管，发光元件(LED芯片)202设在框体204的凹部，含规定的光致发光荧光体的涂覆材料充填于所述凹部以形成涂覆部201而构成该发光二极管。发光元件202用含有诸如Ag的环氧树脂等来固定，而所述发光元件202的n侧电极与p侧电极则分别使用导电电线203连接于设在框体204上的端子金属205。在如上所述构成的芯片型发光二极体中，与图1的引线型发光二极管相同，将光致发光荧光体所产生的荧光与不为光致发光荧光体所吸收的经传送的LED光混色而发出。其结果，发光二极管200也发出与发光元件102所发出LED光的波长不同的光。
具备上述所说明光致发光荧光体的发光二极管具有以下特征。
1.通常，自发光元件(LED)放出的光通过供电给发光元件的电极放出。所放出的光成为发光元件所形成的电极的阴极，具有特定的发光型式，因此不会均匀地在所有方向放出。但是，具备荧光体的发光二极管由于荧光体散射来自发光元件的光而放出光，故不会形成非所要的光型式，而可在广大的范围均匀地放出光。
2.来自发光元件(LED)的光虽然具有单色性的峰值，但由于某种程度的光谱宽度，故光效性高。而这在使用较广范围的波长来作为必要光源情形下尤为不可缺少的优点。例如在使用扫描器的光源的场合，最好使用光谱宽的为佳。
下面说明实施形态1、2的发光二极管。在图1或图2结构的发光二极管中，将一使用可见光频带内光能量较高的氮化物系列化合物半导体的发光元件与一特定的光致发光荧光体组合。因此，具有可作高亮度发光，在长时间使用下无发光效率低下与色斑情形发生良好的特性。
一般而言，在荧光体中，由于吸收短波长的光而放出长波长的光的荧光体比吸收长波长的光而放出短波长的光的荧光体，在变换效率上更优异，故在本发明的发光二极管中，最好使用可发出短波长蓝色系列光的氮化稼系列半导体发光元件(发光元件)。此外，当然以使用高亮度的发光元件为佳。
适合用来与此种氮化镓系列半导体发光元件组合的光致发光荧光体需有以下特性：
1.设置在发光元件102、202邻近，由于暴露在太阳光的约30倍至40倍强的光线下，故在耐光性上极佳，而且可久耐高强度光照射。
2.为了基于发光元件102、202进行激励，发光元件的发光能作有效发光者。特别是，在利用混色情形下，不是紫外线而是监色系列光有效发光。
3.可发出绿色系列至红色系列的光而与蓝色色系列混色成白色。
4.设置在发光元件102、202邻近，而由于会受使所述芯片发光时的发热所造成温度变化的影响，故在温度特性上良好。
5.可基于由色调组合比或多个荧光体的混合化的变化而作连续的变化。
6.发光二极管有对应于使用环境的耐候性。
实施形态1
与本发明有关的实施形态1的发光二极管是具有在发光层的高能带间隙，而将可发出蓝色系列光的氮化稼化合物半导体元件与本身为可发出黄色系列光的光致发光荧光体而以铈活化的石榴石系列光致发光荧光体组合。因此，在实施形态1的发光二极管中，可将发光元件102、202所发出的蓝色系光与被此发光激励的光致发光荧光体的黄色系列光混色，由此而进行白色系列发光。
此外，由于用实施形态1发光二极管的以铈活化的石榴石系列光致发光荧光体具有耐光性与耐候性，故即使长时间将发自发光元件102、202的可见光带中的高能光高亮度照射于其近傍，也可发出发光色的色斑与发光亮度低下极少的白色光。
以下对本实施形态1发光二极管的各构成构件进行说明。
(光致发光荧光体)
本实施形态1的发光二极管所有光致发光荧光体系列是一种以发自半导体发光层的可见光与紫外线来激励而发出具有与经激励的光波长不同的光致发光荧光体。具体而言，以含有自Y、Lu、Sc、La、Gd与Sm中选出的至少一种元素与自Al、Ga与In中所选出的至少一种元素而以铈活化的石榴石系列荧光体来作为光致发光荧光体。本发明最好使用含Y与Al而以铈活化的钇铝石榴石系列荧光体，或一般式以(Re1-rSmr)3(Al1-sGas)5O12:Ce(其中，0≤r＜1，0≤s≤1，而Re是从Y、Gd中所选出的至少一种)表示的荧光体。使用氮化稼系列化合物半导体的发光元件所发出的LED光与本身是黄色的光致发光荧光体所发出的荧光成补色关系情形下，借助于将LED光与荧光混合而发出，即可作为整体发出白色系列的光。
在本实施形态1中，如前所述此光致发光荧光体，由于混合涂覆树脂101与形成涂覆部201的树脂(容后详述)来使用，故借助于对应于氮化稼系列发光元件的发光波长，对与树脂等混合的比率，或填入帽部或框体204的凹部的充填量作种种调整，即可任意将发光二极管的色调设定为含白色的电灯色。
所含光致发光荧光体的分布对混色性与耐久性有所影响。例如，自含有光致发光荧光体的涂覆部与模构件的表面侧向发光元件提供光致发光荧光体的分布浓度提高时，较不容易受到来自外部水份等的影响，可防止水份所造成的劣化。另一方面，若使光致发光荧光体自发光元件向模构件等的表面侧的分布浓度提高，可使来自易受外部环境水份影响的发光元件的发热、照射强度等的影响变得较少，从而可抑制光致发光荧光体的劣化。因此，光致发光荧光体的分布可借助于调整含有光致发光荧光体的构件、形成温度、粘度与光致发光荧光体的形状、粒度分布等来实现种种分布，并考虑发光二极管的使用条件来设定分布状态。
实施例1的光致发光荧光体由于与发光元件102、202相接，或作近接配置，即使在照射强度(Ee)为3W·cm-2以上10W·cm-2以下，也具有充份的耐光性，故借助于使用所述荧光体，可构成发光特性优异的发光二极管。
此外，如图3A所示，实施形态1的光致发光荧光体由于具有石榴石结构，故热、光及水份强，使激励光谱的峰值接近450nm。并且发光峰值也如图3B所示，具有接近580nm至700nm的幅度极宽的发光光谱。并且，实施形态1的光致发光荧光体由于在结晶中含有Gd，故可在460nm以上的长波带中提高激励发光效率。借助于增加Gd含量，发光峰值移往长波，而全体发光波长移往长波侧，也即，需要强红发光色情形下，可借助于增加Gd置换量来达成。随着增加Gd，蓝色光所引起的的光致发光的光亮度有低下的倾向。
特别，借助于在具有石榴石结构成YAG系列荧光体的组成内，以Ga来置换Al的一部分，发光波长即往短波侧移动，或借助于以Gd来置换组成中Y的一部分，发光波长往长波侧移动。
表1表示一般式以(Y1-aGda)3(Al1-bGab)5O12:Ce来表示的YAG系列荧光体的组成及其发光特性。
表1
| No | Gd含量A(克分子比) | Ga含量b(克分子比) | CIE色度座标 | 亮度Y | 效率 | |
| X | Y | |||||
| ① | 0.0 | 0.0 | 0.41 | 0.56 | 100 | 100 |
| ② | 0.0 | 0.4 | 0.32 | 0.56 | 61 | 63 |
| ③ | 0.0 | 0.5 | 0.29 | 0.54 | 55 | 67 |
| ④ | 0.2 | 0.0 | 0.45 | 0.53 | 102 | 108 |
| ⑤ | 0.4 | 0.0 | 0.47 | 0.52 | 102 | 113 |
| ⑥ | 0.6 | 0.0 | 0.49 | 0.51 | 97 | 113 |
| ⑦ | 0.8 | 0.0 | 0.50 | 0.50 | 72 | 86 |
表1所示的各特性是以460nm的蓝色光来激励而测定的。在表1中，亮度与效率是以①的材料为100来表示其相对值。
在基于Ga来置换Al情况下，最好考虑发光效率与发光波长将比率设定于Ga∶Al＝1∶1至4∶6之间。同样地，在Gd置换Y的一部分的情况下，可以把比率设定于Y∶Gd＝9∶1～1∶9的范围，设定于4∶1～2∶3范围则更好。Gd置换量的比率若不满2成，绿色成份即由于红色成份减少而增大，Gd置换量的比率若在6成以上，红色成分会增加，而亮度则急剧降低。特别，借助于根据发光元件的发光波长，将YAG系列荧光体中Y与Gd的比率设定于Y∶Gd-4∶1～2∶3范围，可使用一种钇铝石榴石系列荧光体，构成一种可大致沿黑体辐射轨迹发生白色光的发光二极管。此外，若将YAG系列荧光体中的Y与Gd比设定在Y∶Gd＝2∶3～1∶4的范围，即可构成一种可发出低亮度电灯色的发光二极管。而且，借助于将Ce含量(置换量)设定于0.003～0.2的范围，可使发光二极管的相对发光光度在70％以上。含量未满0.003的话，则以Ce来减少光致发光的激励发光中心数，以此降低光度，相反地，若大于0.2，则发生浓度熄光。
如上所述，借助于以Ga来置换组成中的Al的一部分，可使发光波长往短波移动，而藉由以Gd来置换组成中的Y的一部分，则可使发光波长往长波移动。用这种方式变化其组成，即可连续调节发光色。此外，波长为254nm或365nm的话，用Hg辉线几乎不会激励的450nm附近的蓝色系列发光元件的LED光来提高激励效率。峰值波长进一步具备有用来对氮化物半导体发光元件连续地变换Gd的组成比而将蓝色系列发光度变换成白色系列发光的理想条件。
此外，实施形态1借助于组合使用氮化镓系半导体的发光元件，以及以铈活化而在钇铝石榴石系列荧光体(YAG)中含稀土类元素的钐(Sm)的光致发光荧光体，可进一步提高发光二极管的发光效率。
此种光致发光荧光体可使用氧化物或高温下易氧化物作成的化合物来作为Y、Gd、Ce、Sm、Al、Ga的原料，以预定的化学计量比将其充分地混合而制成混合原料，将作为溶剂的氟化铵等氟化物适量混合于制成的混合原料中而装入坩埚中，在空气中1350～1450℃的温度范围内压2～5小时烧成而制得的烘焙品，其次于水中对烘焙品进行球磨，洗净、分离、干燥，最后放入筛子来制得。
在上述制作方法中，混合原料也可以借助于混合共沉氧化物、氧化铝与氧化镓来制造，这种共沉氧化物是将一以草酸共同沉淀一溶解液的共沉物烘焙，而此溶解液是依化学计量比特将Y、Gd、Ce、Sm的稀土类元素溶解于酸。
一般式可用(Y1-p-q-rGdpCeqSmr)3Al5O12来表示的光致发光荧光体可借助于结晶中含有Gd，提高尤其是460nm以上长波带的激励发光效率。借助于增加钆含量，可使发光峰值波长往530nm至570nm的长波移动，且所有发光波长也可往长波侧移动。在需要强红发光情形下，可借助于增加Gd的置换量来达成，随着Gd增加，借助蓝色光所发射的光致发光亮度徐徐降低。但是，p宜在0.8以下，0.7以下较佳，而以0.6以上为更佳。
一般式以(Y1-p-q-rGdpCeqSmr)3Al5O12来表示的含有Sm的光致发光荧光体，即使增加Gd含量，也使其很少有温度特性降低的情形发生。也就是说，借助于含有Sm而大幅改善高温下光致发光荧光体发生亮度的劣化。其改善程度随Gd含量增加而变大。特别是，增加Gd含量使光致发光的发光色调具有红色而组成的荧光体由于温度特性劣化，故使其含有Sm而有效改善温度特性。此外，此处所谓的温度特性是相对于450nm的蓝色光在常温(25℃)下所激励的发光亮度的荧光体在高温(200℃)下的发光亮度的相对值(％)。
Sm含量r在0.0003≤r≤0.08的范围最好，因此，可使温度特性达60％以上。若比此范围r小，温度特性的改善效率会变小。此外，若较此范围r大，则相反地，温度特性会降低。此外，Sm的含量在0.0007≤r≤0.02范围更佳，由此可使温度特性达80％以上。
Ce含量q最好在0.003≤q≤0.2范围，由此可使相对发光亮度达70％以上。此处所谓的相对发光亮度是指在以q＝0.03的荧光体的发光亮度为100％情形下的发光亮度。
Ce含量在0.003以下的话，即会为了减少光致发光由Ce激励的发光中心数，而降低亮度，相反地，比0.2大的话，即会发生浓度熄光。此外，所谓浓度熄光是指为了提高荧光体的亮度，用增加活化剂的浓度在某一最适值以上的浓度，发光强度者降低。
在本发明的发光二极管中，也最好混合Al:Ga、Y、Gd与Sm的含量不同的二种以上的(Y1-p-q-rGdpCeqSmr)3Al5O12的光致发光荧光体来使用。由此可增加荧光发光中RGB的波长成分，此外，也可例如借助于使用彩色滤光器来作为全色液晶显示装置用。
(发光元件102、202)
发光元件如图1与图2所示最好埋设于模构件中。本发明的发光二极管所用的发光元件是使以铈活化的石榴石系列荧光体能极有效激励的氮化镓系列化合物半导体。使用氮化镓系列化合物半导体的发光元件102、202是以MOCVD法等将InGaN等的氮化镓系半导体形成于基板上以形成发光层而制成。现列举具有MIS接合、PIN接合与PN结等的同质构造、异质构造或双异质构造来作发光元件的构造。可根据半导体层的材料及其混晶度来对发光波长可以作种种的选择。并且可作成足以使半导体活性层产生量子效果的薄薄的单一量子井构造与多重量子井构造。特别是，在本发明中，借助于使发光元件的活性层成为InGaN的单一量子井构造，能使光致发光荧光体不劣化，并能作为发光较高的发光二极管来使用。
在使用氮化镓系列化合物半导体情形下，半导体基板上可使用蓝宝石、尖晶石、Sic、Si、ZnO等材料，但，最好使用蓝宝石基板，形成结晶性良好的氮化镓。经由GaN、AlN等的缓冲层将PN结形成于此蓝宝石基板上，而以此方式形成氮化稼半导体层。氮化镓系列半导体在不掺杂不纯物状态下呈N型导电性，为了形成具有所要提高发光效率的特性(载流子浓度等)的N型氮化镓半导体，最好以Si、Ge、Se、Te、C等作为N型掺杂剂来进行适宜的掺杂。另一方面，在形成P型氮化稼半导体情况下，则掺杂Zn、Mg、Be、Ca、Sr、Ba等P型掺杂剂。此外，氮化镓系列化合物半导体由于仅掺杂P型掺杂剂难以P型化，故最好在导入P型掺杂剂后，以炉加热，利用低速电子射线照射与等离子照射来进行P型化。利用蚀刻等使P型与N型氮化镓半导体表面露出后，使用溅射法与真空蒸发法在各半导体层上形成所要形状的各个电极。
接着，使用利用切块直接全断的方法，切入比刃端宽的沟中之后(半切)，即利用外力切割半导体圆片的方法，或利用前端的钻石针往复直线运动的划线器，而在半导体圆片上譬如拉出围棋盘格子状的极细划线(经线)的后，利用外力将圆片切割的方法等，将以上所形成的半导体圆片等切割成芯片状。由此，即可形成由氮化镓系列化合物半导体所制成的发光元件。
在本实施形态1的发光二极管发出的白色系列光的情形下，宜考虑与光致发光荧光体的补色关系以及树脂的劣化等而将发光元件的发光波长设定在400nm以上、530nm以下，设定在420nm以上490nm以下则更佳。为了分别提高发光元件与光致发光荧光体的发光效率，更好的是设定在450nm以上475nm以下。图4示出了实施形态1白色系列发光二极管的一发光光谱例子。所述例示的发光二极管是图1所示的引线型，也是后述使用实施例1的发光元件与光致发光荧光体。在图4中，具有450nm附近峰值的发光系列来自发光元件的发光，而具有570nm附近峰值的发光则是发光元件激励的光致发光发出的光。
图16示出了以表1所示荧光与峰值为465nm的蓝色LED(发光元件)组成的白色系列发光二极管可实现的色再现范围。所述白色系列发光二极管的发光色由于位于蓝色LED起源的色度点与荧光体起源的色度点结合的直线上的各个点，故利用使用表1中①～⑦的荧光体，可全面复盖色度图中央部范围极广的白色领域(图16中加上斜线的部分)。图17示出了白色系列发光二极管中荧光体含量变化时发光色变化的情形。这里荧光体含量是以相对于使用在涂覆部的树脂的重量百分比来表示。由图17可知，若荧光体的量增加，即越近荧光体的发光色，若减少的话，则越近蓝色LED。
此外，本发明加设可产生激励荧光体的光的发光元件，也可一并使用不激励荧光体的发光元件。具体地说，加设可激励荧光体的氮化物系列化合物半导体，而同时配置有实质上不激励荧光体，发光层为镓化磷、镓化砷、铝、镓化砷磷与铟化铝磷等的发光元件。由此，来自不激励荧光体的发光元件的光就不会被荧光体吸而放到外部。由此则可作为发出红白光的发光二极管。
以下说明图1与图2的发光二极管的其他结构要素。
(导电性电线103、203)
作为导电性电线103、203，需在电阻性、机械连接性、电气传导性与导热性上极佳。导热性宜为0.01卡/(秒)(cm2)(℃/cm)以上，较佳者为0.5卡/(秒)(cm2)(℃/cm)以上。而且考虑到作业性的话，最好电线的直径在10微米以上45微米以下。特别是，即使使用同一材料于含有荧光体的涂覆部与模构件，由于荧光体进入任何一方所引起的热膨胀系数不同，故导电性电线容易于其界面断线。因此，导电性电线的直径为25微米以上最好，从发光面积与操作是否容易的观点考虑35微米以下为好。作为导电性电线的材质有金、铜、白金、铝等金属与其合金。由于使用此种材质、形状所制成的导电性电线，故利用电线粘接装置，即可容易地与各发光元件的电极、内引线与安装引线连接。
(安装引线105)
安装引线105是由帽部105a与引线105b组成，帽部105a上以装片装置载置发光的102的部分要足够大。并且在将多个发光元件设于帽部内而以安装引线来作为发光元件的共通电极的场合，由于有使用不同电极材料情形，所以必须分别有充分的导电性以及焊线等的连接性。此外，在将发光元件配置于安装引线上的帽部内同时将荧光体充填于帽部的内部情形下，即使来自荧光体的光是其本身所放出，由于由帽部朝所要方向反射，故可防止来自近接配置的其他发光二极管的光所造成的模拟点灯情形。所谓模拟点灯是指即使未供电给接近配置的其他发光二极管，也可看到有发光的现象。
发光元件102与安装此安装引线105的帽部105a的接合可用环氧树脂、丙烯基树脂与亚胺树脂等的热硬化性树脂。此外，使用背面发光元件(是从基板侧发光取出，使发光电极与帽部105相对向地安装)情形下，为了在使所述发光元件与安装引线连接而同时导电，可使用Ag涂浆、碳涂浆与金属拼片等。此外，为了提高发光二极管的光利用效率，最好发光元件也使所配置的安装引线的帽部表面成镜面状而具有表面反射功能。此情形的表面糙度最好为0.1S以上0.8S以下。安装引线的具体的电阻宜为300μΩ·厘米以下，较佳者为3μΩ·厘米以下。安装引线上叠置有多个发光元件情形下发热量大，因此热导度必需良好，所述热导度宜为0.01卡/(秒)(cm2)(℃/cm)，较佳者为0.5卡/(秒)(cm2)(℃/cm)以上。满足此等条件的材料有铁、铜、掺铁的铜、掺锡的铜、金属化型式的陶等。
(内引线106)
内引线106以导电性电线连接于安装引线105上所配置的发光元件102一方的电极。在发光二极管在安装引线上设有多个发光元件情形下，须设有多个内引线106，并配有各导电性电线彼此不接触的各内引线。例如，因为从安装引线离开，所以借助于各内引线的各电线接合端的面积依次加大，可隔开式接合导电性电线间的间隔以防止导电性电线间的接触。考虑内引线与导电性电线连接的端面糙度最好设定在1.6S以上10S以下。
内引线可依所要作成的形状以使用型框的钻孔加工等来形成。内引线钻孔加工形成后，最好进一步借助于从端面方向加压，调整所要端面的面积与端面高度。
内引线与导电性电线即连接电线等的连接必须有良好的连接性与导电性。具体的电阻宜为300μΩ·厘米以下，较佳者为3μΩ·厘米以下。满足所述条件的材料有铁、铜、掺铁的铜、掺锡的铜以及镀有铜、金、银的铝、铁、铜等。
(涂覆部101)
涂覆部101系与模构件104分开而设在安装引线的帽部上，就本实施例形态1而言，是含有用来变换发光元件的发光的光致发光光荧光体。作为涂覆部的具体材料适用者的环氧树脂、尿素树脂、硅酮等耐候性优异的透明树脂与玻璃。并且与光致发光荧光体一起含有扩散剂较佳。最好使用钛氧钡、氧化钛、氧化铝、氧化硅等。此外，在利用喷溅形成荧光体情形下，可省略涂覆部。这种情形，可一面调整膜厚，一面设开口部与荧光体层形成能混色显示的发光二极管。
(模构件104)
模构件104具有自发光元件102、导电电线103与含有光致发光荧光体的涂覆部101等的外部进行保护的功能。本实施形态1最好进一步含有扩散剂于模构件部104中，由此可缓和来自发光元件102的指向性并增加视野角。模构件104在发光二极管中具有一面将来自发光元件的发光聚焦一面扩散的透镜功能。因此，模构件104通常为凸透镜状、进一步为凹透镜状，在形状上作成从发光观测面的为椭圆形状与其形状的多个组合。并且模构件104也最好在构造上将各个不同的材料作为多个叠层。作为模构件104主要的具体材料有环氧树脂、尿素树脂、硅酮树脂等耐候性优异的透明树脂与玻璃。可使用钛氧钡、氧化钛、氧化铝、氧化硅等来作为扩散剂。本发明也最好进一步含有加有扩散剂而放入模构件中的光致发光荧光体、也即，本发明也最好含有光致发光荧光体于涂覆部中，以及于模构件中。借助于含有光致发光荧光体于模构件中，可进一步增大视野角。并且，也最好含在涂覆部分构件二者中。此外，使用含有光致发光荧光体的树脂来作成涂覆部，使用与涂覆部不同材料的玻璃来形成模构件也较佳，利用这种构成，即可制造很少受到水份等的影响而在生产性上极佳的发光二极管。根据其用途，为了使折射率一致，也最好使用相同构件来形成模构件与涂覆部。在本发明中，利用模构件中含有扩散剂与着色剂，可使自发光观测面看得到的荧光体着色隐而不见，同时可提高混色性。即，荧光体在强外光中吸收蓝色成份可发出光，看起来就像是着上黄色。此外，在模构件中所含的扩散剂使模构件成乳白色，而着色剂则进行所要颜色的着色。因此，自发光观侧面观测不到荧光体的颜色。发光元件的主发光波长在430nm以上的话，最好含有作为光安定剂的紫外线吸收剂。
发明的实施2
与本发明有关的实施形态2的发光二极管使用具备有氮化镓系列半导体的元件来作为发光元件，此氮化镓系列半导体具有高能带间隙，并使用含有相互组成不同的二种以上不同的光致发光荧光体，最好是含以铈活化的钇铝石榴石系列荧光体的荧光体来作为光致发光荧光体。由此，实施形态2的发光二极管即使在由发光元件所发LED的发光波长不是依制造色散所得的所要值，也可借助于调整二种以上的荧光体含量来制得有所要色调的发光二极管者。在此情形下，相对于发光波长较短的发光元件，使用发光波长较短的荧光体，借助于使用发光波长较长的荧光体于发光波长较长的发光元件，可使发自发光二极管的发光色恒定。
就有关于荧光体而言，可使用一般式以(Re1-rSmr)3(Al1-sGas)5O12:Ce其中，0≤r＜1，0≤s≤1，而Re则是从Y、Gd与La所选出的至少一种。由于由此在发自发光元件的可见光带中，即使为具有高能量的光长时间作高亮度的照射以及在种种外部环境下使用，荧光体也极少变质，故所构成的发光二极管极少发生发光色色斑与发光亮度降低的情形，并且具有所要高亮度的发光成分。
实施形态2的光致发光荧光体
现详细说明实施形态2的发光二极管所使用的光致发光荧光体。
在实施形态2中，如上所述，光致发光荧光体除使用组成不同的二种以上的以铈活化的光致发光荧光体外，也以相同于实施形态1的方式来构成，且荧光体的使用方法与实施形态1相同。
与实施形态1相同，由于可对光致发光荧光体的分布作种种的变化(按照自发光元件离开情形加上浓度梯度)，故利用使发光二极体具有耐候性极强的特性。这种分布利用由调整含光致发光荧光体的构件、形成温度、粘变与光致发光荧光体的形状、粒度分布等来作种种的调整。此外，实施形态2对应于使用条件，设定荧光体的分布浓度。且实施形态2可借助于对各个发光元件所发出的光进行二种以上荧光体的配置(例如依序从接近发光元件处予以配置)来提高发光效率。
与实施形态1相同，如以上结构的实施形态2发生二极管，构成一种即使在与照度强度为(Ee)＝3W*cm-2以上10W*cm-2以下的高输出发光元件，连接或近接配置情形下，也具有高效率且耐光性充分的发光二极管。
与实施形态1相同，实施形态2所用以铈活化的钇铝石榴石系列荧光体(YAG系列荧光体)，由于具有石榴石的结构，故热、光与水份上极强。且如图5A的实线所示，实施形态2的钇铝石榴石系列荧光体，将激励光谱的峰值设定于450nm附近，并可如图5B的实线所示，将发光光谱的峰值设定于510nm附近，如此即可在频宽上将发光光谱扩展至700nm。由此即可发出绿色系列光。可如图5A的虚线所示，实施形态2的另一以铈活化的钇铝石榴石系列荧光体，使激励光谱的峰值接近450nm，且发光光谱的峰值可如图5B的虚线所示设定于600nm附近，由此即可在频宽上将发光光谱扩展至750nm。由此即发可发生红色系光。
在具有石榴石组成的YAG系列荧光体内，以Ga置换Al的一部分来使发光波长往短波侧移动，且以Gd与/或La置换Y的一部分来使发光波长往长波侧移动。Al对Ga置换最好考虑发光效率与发光波长为Ga∶Al＝1∶1至4∶6。同样地，以Gd与/或La置换Y的一部分，Y∶Gd与/或La＝9∶1至1∶9，较佳者为Y∶Ga与/或La＝4∶1至2∶3。置换比率不满2成的话，绿色成份会增大而红色成份则缩小。且比率是6成以上的话，红色成份会增大而亮度则急递降低。
这种光致发光荧光体可使用以Y、Gd、Ce、La、Al、Sm与Ga作为原料的氧化物与高温下易氧化的氧化物所组合的化合物，并按化学计量比将其混合而制得原料。并且以共沉氧化物、氧化铝与氧化镓混合而制得混合原料，所述共沉氧化物是以草酸共同沉淀一溶解液的共沉物烘焙，而所述溶解液是依化学计量比将Y、Gd、Ce、La、Sm的稀土类元素溶解于酸中。将作为助熔剂的氟化铵等氟化物适量混合而放入坩埚中，在空气中1350～1450℃温度下压2～5小时烘焙而制得烘焙品，其次在水中球磨烘焙品、洗净、分离、干燥，最后通过筛子可制得。在本实施形态中，组成不同的二种以上以铈活化的钇铝石榴石系列荧光体既最好混合使用，并且最好独立配置(譬如叠层)使用。在二种以上荧光体混合使用情况下，形成产量性佳的色变换部较简单，而二种以上的荧光体独立配置情形下，可借助于形成所要颜色或使其混合，而在形成后予以色调整。此外，在荧光体各自独立配置情形下，最好接近LED元件处设有易于在较高波长侧吸收光而发光的荧光体，并在离LED较远处配置易于在较长波侧吸收发光的荧光的荧光体。由此可有效吸收并发光。
如上所述，本实施形态2的发光二极管使用组成不同的二种以上钇铝石榴石系列荧光体。由此可构成一种所欲发光色可有效发光的发光二极管。即，半导体发光元件所发的光的发光波长在图6所示色变图的A点至B点线上的位置情况下，即可发出组成不同的二种以上的钇铝石榴石系列荧光体色度，即图6的A点、B点、C点及D点所围住的斜线内的任一发光色。实施形态2可借助于LED元件、荧光体的组成或其量作种种选择来调节。特别是，对应于LED元件的发光波长，借助于由对荧光体的选择来补偿LED元件的发光波长的色散，由此可构成发光波长的色散极少的发光二极管。此外，可借助于由选择荧光体的发光波长来构成含高亮度的RGB发光成份的发光二极管。
此外，由于实施形态2所用的钇铝石榴石系(YAG系)荧光体是由石榴石组成，故实施形态2的发光二极管可长时间高亮度的发光。而且，实施形态1与2的发光二极管从发光观测面看，经由荧光体设有发光元件。由于所使用荧光物质于比来自发光元件的光的波长侧发光，故可有效发光。此外，变换过的光由于也变成在较发自发光元件的光长的波长侧，故也比发光元件的氮化物半导体层的带间隙小，而难以为所述氮化物半导体层所吸收。为了使荧光体等向发光，所发出的光虽也朝向LED元件，但由于荧光体所发出的光不为LED元件所吸收，故不会降低发光二极管的发光效率。
(面状发光光源)
图7表示有关于本发明的另一实施形态的面状发光光源例子。
图7所示面状发光光源是涂覆部701所含实施例1或2所用的光致发光荧光体。由此，氮化镓系列发光元件所发蓝色系光藉涂覆部作色变换后，即经由导光板704与散射片706成面状发出。
详细地说，在图7的面状发光光源中，发光元件702固定于绝缘层与导电晶体点阵(未表示)所形成的コ字形金属基板703内。发光元件的电极与导电晶体点阵导通的后，即将光致发光荧光体与环氧树脂混合而充填于载装有发光元件702的コ字基金属基板703内部。如此固定的发光元件702以环氧树脂等固定在具有丙烯基性质的导光板704的一侧端面。在未形成有导光板704一侧的主面上的散射板706的部分上形成含有白色散射剂的膜状反射构件707，以防止点状发光的荧光现象。
同样地，在结构上，在导光板704的另一侧整个主表面(里面侧)以及未配置有发光元件的另一侧端面上，设有反射构件705以提高发光效率。由此可构成一种例如LCD背光用而具有充分明亮度的面状发光的发光二极管。
使用这种面状发光的发光二极管的液晶显示器系例如经由在透光性导电液晶点阵所形成的玻璃基板间(未表示)注入液晶的液晶装置，将偏光板配置于导光板704的一侧主面上而构成。
图8、9表示有关于本发明的其他实施形态的面状发光装置实例。图8所示的发光装置是以经由光致发光荧光体所含有的色变换构件701变换成白色系光后，借助于导光板704将发光二极管702所产生的蓝色系列光成面状发出的方式构成。
图9所示的发光装置是按以导光板704形成面状后，借助于导光板704一侧的主表面上所形成具有光致发光荧光体的散射片706，将发光元件702所发射的蓝色系光变换成白色光而发出面状白色光的方式构成。此外，光致发光荧光体也最好含于散射片706内，或者，也最好与粘合剂树脂一起涂覆在散色片706上而形成片状。此外，也最好不将在导光板704上的含光致发光荧光体的粘合剂形成为片状，而直接形成为点状。
<应用例>
(显示装置)
接着说明有关于本发明的显示装置。图10表示有关于本发明的显示装置结构的方块图。所述显示装置如图10所示，由LED显示器601以及具备有驱动电路602、影像数据存储装置603与色调控制装置604的驱动电路610所构成。LED显示器601，如图11所示，是被用来作为于框体504成矩阵状排列有图1或图2所示的白色系列的发光二极管501的黑白LED。与框体504一体形成的蔽光构件505。
如图10所示，驱动电路610，可包括有：
影像资料存储装置(RAM)603，暂时存储所输入的显示数据；色调控制装置604，根据自RAM603读出的数据，运算而输出LED显示器601的各个发光二极管成预定亮度点灯用的色调信号；以及驱动器602，根据输出自色调控制装置604的信号，将发光二极管点亮。色调控制装置604取出存储于RAM603的数据，运算LED显示器601的发光二极管点灯时间，并于LED显示器601输出闪烁脉冲信号。在如上所述结构的显示装置中，LED显示器601可根据从驱动电路输入的冲动信号，显示对应于显示数据的影像，从而具有以下优点。
即，使用RGB的三个发光二极管而作白色系列显示的LED显示器，由于有必要调节显示RGB的各发光二极管的发光输出，故须考虑各发光二极管的发光强度、温度特性等，而控制各发光二极管，因此，驱动所述LED显示器的驱动电路有过于复杂的问题。此外，在本发明的显示装置中，LED显示器601并不使用RGB的三种发光二极管，由于结构上所使用的有关于本发明的可发出白色系光的发光二极管501，故驱动电路无需对RGB的各个发光二极管作个别的控制，故可使驱动电路结构成简单，并使显示装置价廉。
使用RGB的三种发光二极管而显示白色系列的LED显示器，为了将RGB的三种发光二极管组合而作白色显示于每一象素，必须同时分别使三种发光二极管发光而将其混色，故相当于一象素的显示领域会加大而无法作极精细的显示，此外，本发明的显示装置中LED显示器，由于可用一个发光二极管来作白色显示，故可作较高度精细的白色系显示。借助于三种发光二极管的混色来显示的LED显示器依所见方向与角度而变化，各RGB的发光二极管会有某一部分被蔽光而显示色产生变化的情形发生，本发明的LED显示器则无这种现象。
如上所述LED显示器使用本发明的可发白色系列光的发光二极管，包括所述LED显示器的显示器具有较高度精细化，可作安定的白色显示，并可使色斑减少的特长。用本发明的可作白色显示的LED显示器与已知仅用红色、绿色的LED显示器相比，对人体眼睛的刺激极少而适合长时间的使用。
(使用本发明的发光二极体的其他显示装置实例)
如图12所示，借助于使用本发明的发光二极管，即可构成以本发明的发光二极管加上RGB的三种发光二极管者作为一象素的LED显示器。而借助于使所述LED显示器与规定的驱动电路连接，即可构成一种能显示种种图像的显示装置。与单色显像的显示装置一样，本显示装置中的驱动电路包括：一影像数据存储装置(RAM)，暂时存储所输入的显示数据；色调控制装置，根据RAM所存储的数据，运算使各发光二极管而预定亮度点高用的色调信号；以及驱动器，切换色调控制电路的输出信号来而将各发光二极管点亮。此外，所述驱动电路需有分别控制RGB与发射白色系光的各发光二极管的专用控制电路。色调控制电路由RAM所存储的数据来运算各个发光二极管的点灯时间，并将闪烁的脉冲信号输出。在进行白色系列显示情形下，使点亮RGB各发光二极管的脉冲信号的脉冲宽度缩短，或者使脉冲波信号的主峰值降低，以至于不输出全部的脉冲波信号。另一方面，供给脉冲波信号到白色系列发光二极管，(即，对其进行补偿即缩短冲波信号的脉冲宽度，降低冲波信号的峰值，以至于不输出全部冲波信号的部分予以补偿)。由此作LED显示器的白色显示。
这样，借助于由追加白色发光二极管于RGB的发光二极管，即可提高显示器的亮度。以RGB的组合来进行白色显示的话，虽然无法根据目视角强调RGB中的各一或二色而显示纯粹的白色，借助于由追加用于本显示装置的白色发光二极管，即可解决这一问题。
此种显示装置中的驱动电路最好以CPU作为色调控制电路来演算白色系列发光二极管或所要亮度点亮用的脉冲波信号。输出白色调控制电路脉冲波信号到输入白色系列发光二极管的驱动器而将使驱动器切换。如果驱动器导通，则白色系列发光二极管则点亮，关闭的话，则熄灭。
(信号机)
使用本发明的发光二极管来作为本身为显示装置的一种的信号机所具的特点为，除可长时间稳定发光外，而且，即使发光二极管的一部分熄灭，也不会产生色斑。使用本发明发光二极管的信号机的概略结构，是依预定排列方式将白色发光二极管配置在导电晶体点阵所形成的基板上，以串联或串并联连接此种发光二极管的发光二极管电路为发光二极管组。使用二个以上发光二极管组而分别成螺旋状配置发光二极管。如果所有发光二极管给予配置的话，则全面配置成圆形。分别以焊料将各发光二极管与从基板与外部电力连接的电源线焊接后，即固定于铁道信号用的框体内。LED显示器配置在装有蔽光构件的铝铸框体内而以硅胶充填材料固于表面上。框体的显示面设有白色透镜。且LED显示器的电气配线为了自框体里面将框体密闭，经由橡胶相通而密闭于框体。如此即可形成白色系信号机。可将本发明的发光二极管配置成自分开多组的中心部向外勾勒轮子的螺旋形，借助于由并联连接构成可靠度高的信号机。在这种情形下，可借助于由自由中部向外勾勒轮子而构成可靠度高的信号机。自中心部向外侧勾勒轮子，包括在连接勾勒轮子与断续的配置。此外，考虑到LED显示器的显示面积等，可对所配置的发光二极管的数目与发光二极管组的数目作种种的选择。因此，信号机，即使因一方发光二极管组与一部分发光二极管中任一个有问题而造成熄灯，也可借助于由另一方发光二极管组与剩下的发光二极管使信号机作均匀的圆形发光，而不致于产生色斑。由于螺旋状配置，故能紧密配置在中心部，不管电灯发光信号为何，均可作协调的驱动。
<实施例>
下面，虽然对本申请的发明的实施例进行说明，但本发明并不限于下述的实施例，现说明如下。
(实施例1)
实施例1是以用于GaInN半导体的发光峰值系450nm、半宽度300nm的发光元件用来作为发光元件的例。实施例1的发光元件是在洗净的蓝宝石基板上使TMG(三甲基镓)气体、TMI(三甲基铟)气体、氮气及掺杂气体来与载体气体一起滚动，以MOCVD法使氮化镓系列化合物半导体成膜而制造。成膜时，借助于转换Si，H4与Cp2Mg来作为掺杂气体，形成具有N型导电性的氮化镓半导体与具有P型导电性的氮化镓半导体。实施例1的LED元件具备一有N型导电性的氮化镓半导体的接触层、一有P型导电性的氮化镓铝作为包覆层以及一有P型导电性的氮化镓半导体层的接触层，形成一由非掺杂InGaN所形成的活性层，以构成在具有N型导电性的接触层与具有P型导电性的包覆层之间的厚度约为3nm的单一量子井，且在蓝宝石基板上在低温下形成氮化镓半导体层来作为缓冲层。而且，P型氮化镓半导体成膜后在400℃以上的温度进行热焙(anneal)。
借助于蚀刻使P型与N型的各半导体表面露出后，再借助于溅射分别形成n侧p侧的各电极。在如此作成的半导体圆片上划线的后，即施加外力切割成各个发光元件。
以环氧树脂将如上所述制成的发光元件接合于镀银安装引线的帽部后，即用直径为30微米的金线分别对发光元件的各电极、安装引线与内引线进行线接合而制成引线型发光二极管。
光致发光荧光体是以草酸来与一以预定化学计量比将Y、Gd、Ce等稀土元素溶解于酸的溶解液共同沉淀，锻烧沉淀物而获得的共同沉淀氧化物与氧化铝混合，将作为熔剂的氟化铵混合于此混合原料，而放入坩埚中，在空气中400℃温度下锻烧3小时后，使用球磨湿式粉碎、洗净、分离、干燥后，最后通过筛子而制成。
其结果，如果光致发光荧光体为Y用约2成的Gd来置换的铟、铝氧化物的话，则形成为(Y0.8Gd0.2)3Al5O12:Ce。且Ce的置换为0.03。
其结果，形成为(Y0.8Gd0.2)3Al5O12:Ce荧光体80重量部分与环氧树脂100重量部分充分混合成浆料，在将此浆料注入到载装发光元件的安装引线的帽部内后，即在130℃温度下硬化一小时。而后则在发光元件上形成含有120微米厚的光致发光荧光体的涂覆部。本实施例1是在涂覆部中光致发光荧光体向着发光元件逐渐增多的方式分布而构成的。照射强度约为3.5W/cm2。此后即进一步在外部应力、水份与尘埃等方面保护发光元件与光致发光荧光体的目的下，形成透光性环氧树脂来作为模构件。就此点而言，模构件系在炮弹型的型框中接合于引线框，将覆盖在含光致发光荧光体的涂覆部上的发光元件插入，注入透光性环氧树脂后，150℃下硬化5小时而形成。
要点是，所形成的发光二极管的自发光观测正面的是着色成依光致发光荧光体的体色中央部分带有黄色。
而后，所获得的白色系列经测定可发光的发光二极管的色度点、色温度与光效性指数的结果显示接近色度点(X＝0.302、Y＝0.280)、色温度8080K、光效性指数(Ra)＝87.5的三波长型荧光体的性能。且发光效率若为9.51m/w则系白色电灯的类型。而且，即使在温度25℃ 60mA通电、温度25℃ 20mA通电、温度60℃90％RH的情况下20mA通电的各寿命试验中观测不到荧光体所造成的变化，也可确定与一般蓝色发光二极管寿命特性上并无差别。
(比较例1)
除了由(Y0.8Gd0.2)3Al5O12:Ce荧光体将光致发光荧光体作成(ZnCd)S:Cu、Al外，均与实施例1一样，形成发光二极管与进行寿命试验。所形成的发光二极管通电后，马上跟实施例1一样，确认出白色系列的发光，但亮度则减低。在寿命试验中，约100小时输出为零。劣化原因解析结果是荧光体黑化。
根据发光元件所发出的光与附着于荧光体的水份或自外部环境进入的水份进行光分解而在荧光体结晶表面析出胶状亚铅金属，兹认为这是外观上变成黑色的东西。图13示出了将温度25℃ 20mA通电、温度60℃90％RH下的20mA通电的寿命试验结果与实施例1的结果。亮度显示有作为基准的初期值与各个相对值。图13中，实线表示与实施例1，而波状线则表示比较例。
(实施例2)
实施例2的发光二极管借助于在发光元件的氮化物系列化合物半导体的In含量比实施例1的发光元件增多，故使发光元件的发光峰值为460mm，并且光致发光荧光体的Gd含量增加也比实施例1多而作成(Y0.6Gd0.4)3Al5O12:Ce外，也与实施例1一样制造发光二极管。
如以上所制成的发光二极管可发白色系列光，测定其色度点、色温度与光效性指数，分别为，色度点(X＝0.375、Y＝0.370)，色温度4400K，光效性指数(Ra)＝86.0。
图18A、图18B与图18C分别表示实施例2的光致发光荧光体、发光元件与发光二极管的各发光光谱。
制造100个实施例2的发光二极管，相对于初期光度发光1000小时后调整光度。结果，以初期(寿命试验前)的光度为100％，历经1000小时后的平均光度经确认平均为98.8％，特性上并无差别。
(实施例3)
实施例3的发光二极管除使用在Y、Gd、Ce稀土类元素中进一步含有Sm，一般式为(Y0.39Gd0.57Ce0.03Sm0.01)3Al5O12荧光体来作光致发光荧光体外，也与实施例1一样来制造。制造100个发光二极管，在130℃高温下评价结果，与实施例1的发光二极管比较，平均温度特性到8％左右是良好的。
(实施例4)
实施例4的LED显示器实施例1的发光二极管成16×16矩阵状排列在如图11所示形成铜图形的陶瓷基板上而构成。并且，就实施例4的LED显示器而言，排列有发光二极管的基板配置在由酚树脂制成而使蔽光构件505一体成形的框体504内，并且以色料着上黑色的硅胶506充填除发光二极管的前端部外的框体、发光二极管、基板与蔽光构件的一部分。且基板与发光二极管的连接是用自动焊接安装装置来进行焊接。
经确认，以具备如以上结构的LED显示器、即可以其作为黑白LED显示装置来使用，所述结构是：暂时存储所输入显示数据的RAM、取出RAM的存储数据而演算发光二极管成预定亮度点灯用的色调信号的色调控制电路以及以色调控制电路的输出信号切换而使发光二极管点亮的驱动器的驱动装置予以驱动，即可以其作为黑白LED显示装置来使用。
(实施例5)
实施例5的发光二极管除使用以一般式为(Y0.2Gd0.8)3Al5O12:Ce的荧光体来作为光致发光荧光体外，其他均与实施例1一样来制造。制造100个实施例5的发光二极管来测定诸特性。
其结果，色度点(平均值)为(X＝0.450、Y＝0.420)而可发出电灯色的光。
图19A、图19B与19C分别表示实施例5的光致发光荧光体、发光元件与发光二极管的各发光光谱。
实施例5的发光二极管比实施例1的发光二极管亮度约低40％，寿命试验显示与实施例1一样具有极佳耐候性。
(实施例6)
实施例6的发光二极管除使用一般式以Y3Al5O12:Ce表示的荧光体来作为光致发光荧光体外，其他均与实施例1一样来制造。制造100个实施例6的发光二极管来测定其特性。
其结果，与实施例1比较，可发出略带一点黄绿色的白色光。
图20A、20B与20C分别表示实施例6的光致发光荧光体、发光元件与发光二极管的各发光光谱。
实施例6的发光二极管在寿命试验中显示与实施例1同样有极佳耐候性。
(实施例7)
实施例7的发光二极管除使用一般式以Y3(Al0.5Ga0.5)5O12:Ce来表示的荧光体来作为光致发光荧光体外，其他均与实施例1一样来制造。制造100个实施例7的发光二极管来测定其特性。
其结果，实施例7的发光二极管可发出亮度低而带有一点绿色的白色光，并且在寿命试验中显示与实施例1相同有极佳耐候性。
图21A、图21B与图21C分别表示实施例7的光致发光荧光体、发光元件与发光二极管的各发光光谱。
(实施例8)
实施例8的发光二极管除使用一般式以Gd3(Al0.5Ga0.5)5O12:Ce表示而不含Y的荧光体来作为光的发光荧光体外，其他均与实施例1一样来制造。制造100个实施例8的发光二极管来测定其特性。
其结果，实施例8的发光二极管亮度低，在寿命试验中显示与实施例1相同有极佳耐候性。
(实施例9)
实施例9的发光二极管是具有如图7所示结构的面状发光的发光装置。
使用发光峰值为450nm的In0.05Ga0.95N半导体来作为发光元件。发光元件是使TMG(三甲基镓)气体、TMI(三甲基铟)气体、氮气与掺杂剂气体与载体气体一起流动于洗净的蓝宝石基板上，而以MOCVD法使氮化镓系列化合物半导体成膜而形成。借助于将SiH4与Cp2Mg掺杂剂气体进行转换，形成具有N型导电性的氮化镓半导体与具有P型导电性的氮化镓半导体而形成PN结。形成具有N型导电性的氮化镓半导体接触层、具有N型导电性的氮化镓半导体包覆层、具有P型导电性的氮化镓半导体包覆层与具有P型导电性的氮化镓接触层者来作为半导体发光元件。在具有N型导电性的包覆层与具有P型导电性的包覆层的间形成双异质接合的Zn掺杂InGaN的活性层。且在蓝宝石基板上低温形成氮化镓半导体而用来作为缓冲层。P型氮化物半导体层在成膜后在400℃以上温度进行烘焙。
在各半导体成膜后，利用蚀刻使PN各半导体表面露出，然后，利用溅射分别形成各电极，接着对作好的半导体圆片划线，再以外力切割而形成发光元件。
以环氧树脂将发光元件接合在具有帽部于镀银的铜制引线框前端的安装引线上。分别以直径为30微米的金线，对发光元件的各电极与安装引线及内引线作线接合而使其电气导通。
模构件是在将炮弹型的型框中配置有发光元件的引线框插入而混入透光性环氧树脂后，在150℃下压5小时予以硬化而形成蓝色系列发光二极管。将蓝色光二极管连接于整个端面研磨过的丙烯基导光板的一端面，丙烯基板的板面与侧面若作为白色反射构件则以分散于丙烯基系列粘合剂中的钛酸钡来网印并硬化。
光致发光荧光体按化学计量比，将绿色系与红色系分别所需的Y、Gd、Ce、La稀土类元素溶解于酸中，而使草酸与此溶解液共同沉淀。将烘焙而得的氧化物与氧化铝、氧化镓混合而分别获得混合原料。将作为助熔剂的氟化铵混合于此等原料而放入坩埚中，在空气中1400℃温度范围内烘焙3小时而得烘焙品。在水中分别球磨烘焙品、洗净、分离、干燥，最后通过筛子形成。
将如以上所制成一般式为Y3(Al0.6Ga0.4)5O12:Ce而可发绿色光的第1荧光体的120重量、按同样方式制成一般式为(Y0.4Gd0.6)3Al5O12:Ce而可发红色光的第2荧光体的100重量部分、与环氧树脂的100重量部分充份混合成为浆料，使用多重涂覆器在0.5毫米厚的丙烯基层上将此浆料均匀涂布、干燥来形成30微米厚的作为色变换构件的荧光膜。将荧光体层切成与导光板的主发光面同样大小，而配置在导光面上，由此作成面状发光装置。如上所制成的发光装置其色度点与光效性指数经测定结果显示，色度点(X＝0.29，Y＝0.34)，光效性指数(Ra)92.0，具有接近三波长型荧光灯的性能。且发光效率若为121m/w，即属白色电灯的类型。此外，若作耐候性试验，也无法在室温60mA通电、60℃90％RH下20mA通电的各试验中观测到荧光体所造成的变化。
(比较例2)
除了分别使用二萘嵌苯系列锈导体的绿色有机荧光体(SINLOIHI化学制FA-001)与红色有机荧光颜料(SINLOIHI化学制FA-005)代换实施例9中一般式以Y3(Al0.6Ga0.4)5O12:Ce表示的可发绿色系列光的第1荧光体与一般以(Y0.4Gd0.6)3Al5O12:Ce表示的可发红色系光的第2荧光体而同量混合搅拌外，与实施例9相同制造发光二极管，并与实施例9相同进行耐候试验。所制造比较例1发光二极管的色度点为(X＝0.34，Y＝0.35)。若是耐候性试验，则测定大约等于太阳光一年份的200小时碳电弧紫外线下随着时间的亮度保持率与色调。此结果与实施例9分别表示于图14与图15中。由图14、15可知，在各试验中，实施例9劣化较比较例2少。
(实施例10)
实施例10的发光二极管为引线型发光二极管。
实施例10的发光二极管与实施例9相同使用，具有制成450nm的In0.05Ga0.95的发光的发光元件。以环氧树脂将发光元件接合于镀银的铜制安装引线前端的帽部上，然后由金线接合使发光元件的各电极与安装引线即内引线电气导通。
另一方面，光致发光荧光体分别如以下混合使用一般式以Y3(Al0.5Ga0.5)5O12:Ce来表示的可发绿色系光的第1荧光体与一般式以(Y0.2Gd0.8)3Al5O12:Ce来表示的可发红色系光的第2荧光体。即，用草酸以化学计量比，使必要的Y、Gd、Ce稀土类元素溶解于酸的溶解液共同沉淀。若将其烘焙而得的共沉氧化物，则混合氧化铝、氧化镓而分别获得混合原料。混合作为熔剂的氟化铵而放入坩埚中。在空气中1400℃温度范围内烘焙而分别制得烘焙品。在水中球磨烘焙品、洗净、分离、干燥，最后通过筛子，而制成预定粒度的第1与第2荧光体。
将以上所制成的第1荧光体与第2荧光体的分别的40重量部分与环氧树脂的100重量混合成浆料，将此浆粒注入配置有发光元件的安装引线上的帽部。注入后，即将含有所注入光致发光荧光体的光致发光荧光体以130℃压1小时硬化。而后在发光元件上形成含有厚度为120μ的光致发光荧光体的涂覆构件。并且，所述涂覆构件以在接近发光元件处徐徐增加光致发光荧光体量的方式形成。然后，则进一步在保护发光元件与光致发光致发光荧光体使其免于外部压力、水份与尘埃的目的下形成作为模构件的透光性环氧树脂。模构件是在插入炮弹型型框中形成有光致发光荧光体的涂覆部的引线框而混入环氧树脂后，以150℃压5小时予以硬化。如此制成的实施例10自发光观测正面看的，中央部分是按光致发光荧光体色着色成略带黄色。
如上所制成的实施例2的色度点、色温度、光效性指数经测定结果，色度粘为(X＝0.32，Y＝0.34)，光效性指数为(Ra)＝89.0，发光效率为101m/w。且若进一步作耐候试验，即使在室温60mA通电、室温20mA通电、60℃90％RH下20mA通电的各试验中也观测不到光致发光荧光体所引起的变化，可确认与一般的蓝色系列发光二极管在寿命特性上并无差别。
(实施例11)
使用发光峰值为470nm的In0.4Ga0.6半导体来作为LED元件。发光元件是使TMG(三甲基镓)气体、TMI(三甲基铟)气体、氮气与搀杂气体在洗净的蓝宝石基板上流动，而借助于MOCVD法使氮化镓系列化合物半导体成膜而制成。借助于替换作为掺杂气的SiH4与Cp2Mg形成具有N型导电性的氮化镓半导体与具有P型导电性的氮化镓半导体，从而形成PN结。形成是具有P型导电性的氮化镓铝半导体的包覆层和是具有P型导电性的氮化镓半导体的接触层来作为LED元件。借助于在具有N型导电性的接触层与具有P型导电性的包覆层之间形成3nm的非掺杂InGaN的活性层来形成单一井结构。并在蓝宝石基板上低温形成氮化镓半导体作为缓冲层。
如上形成各层后，利用蚀刻使PN各半导休表面露出，利用喷溅形成p侧与n侧的各电极。而后，将作好的半导体圆片划线，利用外力切割而形成发光元件。
使用环氧树脂将所述发光元件接合于镀银的铜制安装引线的帽部。分别以直径30微米的金线使发光元件的各电极与安装引线与内引线实现线接合而电气导通。
模构件是在将炮弹型型框中配置有发光元件的引线框插入并混入透光性环氧树脂后，以150℃压5小时予以硬化而形成蓝色系列发光二极管，将蓝色系列发光二极管连接于整个端面经研磨的丙烯基导光板的一端面。丙烯基板的板面与侧面将分散于丙烯基系列粘合剂中的作为白色反射构件的钛酸钡网印并硬化而形成膜状。
另一方面，光致发光荧光体以后述方式制造并混合，使用一般式以(Y0.8Gd0.2)3Al5O12:Ce表示而可发较短波侧的黄色系列光的荧光体与一般式以(Y0.4Gd0.6)3Al5O12:Ce表示可发较长波侧的黄色系列光的荧光体。这种荧光体以草酸使按化学计量比将各个必要的Y、Gd、Ce稀土类元素溶于酸中的溶解液共同沉淀。若将其烘焙而制得的其沉氧化物，则混合氧化铝而制得混合原料。混合作为助熔剂的氟化铝而放入坩埚内，在空气中1400℃温度范围压清洗3小时烘焙而制得烘焙品。在水中分别球磨烘焙品、洗净、分离，最后通过筛子而制成。
将以上方式所制成较短波长侧黄色系列荧光体100重量、较长波长侧黄色系列荧光体100重量与丙烯基树脂1000重量混合压出成形，形成180微米厚的作为色变换构件用的荧光体膜。将荧光体膜切割成与导光板主发光面同样大小而配置在导光板上以制成发光装置。用这种方式所制成实施例3的发光装置其色度点、光效性指数经测定结构显示，色度点为(X＝0.33，Y＝0.34)，光效性指数为(Ra)＝88.0，而发光效率则为101m/w。
图22A、图22B和图22C分别表示实施例11所用一般式以(Y0.8Gd0.2)3Al5O12:Ce表示的荧光体、一般以(Y0.8Gd0.2)3Al5O12:Ce表示的荧光体与发光元件的各发光光谱。图23表示实施例11发光二极管的发光光谱。进一步作耐候试验，即在室温60mA通电、室温20mA通电、60℃90％RH下20mA通电的各试验中，也观测不到起因于荧光体的变化。同样地，即使来自发光元件的波长有所变化，也可借助于对所述荧光体的含量作种种变化来维持所欲色度点。
(实施例12)
实施例12的发光二极管除使用一般式以Y3In5O12:Ce来表示而不含铝的荧光体来作为光致发光荧光体外，也与实施例1相同，制造100个这样的发光二极管。实施例9的发光二极管在亮度低的寿命试验中显示与实施例1同样优异的耐候性。
(工业实用性)
如以上说明所示，本发明的发光二极管可发出具有所要颜色的光，即使长时间高亮度使用发光效率也极少劣化，且耐候性极佳。因此，不限于一般电子设备，也可作需要，高可靠度的车载用、航空产业用、港内浮标显示用及高速公路标识照明等的屋外显示与照明，并能开发其新的用途。
Claims (23)
1.一种发光装置(100)，包括一发光半导体元件(102)和一含萤光体的树脂(101)，所述的发光半导体元件发出第一种光，所述的第一种光的发射光谱的峰值波长λ不大于530nm，所述含萤光体的树脂含有，至少吸收一部分发自所述发光半导体元件的第一种光而发出第二种光的萤光体，其特征在于，所述的萤光体是含有一种稀土元素的石榴石且萤光体的颗粒的尺寸是受控制的分布。
2.如权利要求1所述的发光装置，其特征在于，所述的萤光体含有YAG:Ce。
3.如权利要求1或2所述的发光装置，其特征在于，所述的第二种光的发射光谱实质上比第一种光的发射光谱长。
4.如权利要求1至3中任意一项所述的发光装置，其特征在于，所述的发光半导体元件发出篮光。
5.如权利要求1至4中任意一项所述的发光装置，其特征在于，所述的含有萤光体的树脂被设置在所述的发光半导体元件(102)之上或上面。
6.如权利要求1至4中任意一项所述的发光装置，其特征在于，所述的含有萤光体的树脂，至少直接覆盖所述的发光半导体元件(102)的一部分以及至少一部分与所述的发光半导体元件电气连接(103)。
7.如权利要求5所述的发光装置，其特征在于，从所述的发光半导体元件发出的第一种光透过被设置在一透光树脂的光发射侧的表面上的荧光体而辐射。
8.如权利要求5所述的发光装置，其特征在于，所述的发光半导体元件(102)的表面的至少一部分被涂上所述的含有萤光体的树脂。
9.如权利要求1至8中任意一项所述的发光装置，其特征在于，所述的发光半导体元件(102)在剖视图中呈C状开口，以及来自所述的呈C状开口的第一种光透过所述的含有萤光体的树脂(101)而被辐射。
10.如权利要求1至8中任意一项所述的发光装置，其特征在于，所述的发光半导体元件(102)被设置在一壳(204)中，且在所述的壳的开口的至少一部分中填充所述的含有萤光体的树脂(101)。
11.如权利要求2所述的发光装置，其特征在于，第二种光的峰值波长比第一种光的第一峰值波长要长。
12.如权利要求1至11中任意一项所述的发光装置，其特征在于，所述的含有萤光体的树脂含有环氧树脂、尿素树脂或硅。
13.如权利要求1至12中任意一项所述的发光装置，其特征在于，所述的含有萤光体的树脂(101)及/或一模构件材料(104)含有分散剂。
14.如权利要求1至13中任意一项所述的发光装置，其特征在于，所述的萤光体吸收和转换第一种光的蓝色区。
15.如权利要求1至12中任意一项所述的发光装置，其特征在于，所述的含有萤光体的树脂含有数种不同的无机发光材料。
16.一种LED显示器，包含如权利要求1至15中任意一项所述的发光装置。
17.一种用于汽车或航空工业的光源，包含如权利要求1至15中任意一项所述的发光装置。
18.一种用于液晶显示的照明，包含如权利要求1至15中任意一项所述的发光装置。
19.如权利要求13所述的发光装置，其特征在于，所述的分散剂含有钛酸钡、氧化钛、氧化铝与二氧化硅一组中所选出的一种或多种物质。
20.如权利要求2所述的发光装置，其特征在于，所述YAG:Ce含有Gd。
21.如权利要求1所述的发光装置，其特征在于，所述的峰值波长不小于400nm。
22.如权利要求1所述的发光装置，其特征在于，所述的稀上元素为Ce。
23.如权利要求1所述的发光装置，其特征在于，所述的萤光体包含含有Y和Al的石榴石以及至少由铈(Ce)做为激活剂。
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| CN97196762A Expired - Lifetime CN1133218C (zh) | 1996-07-29 | 1997-07-29 | 发光装置及显示装置 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102456294A (zh) * | 2010-11-02 | 2012-05-16 | 展晶科技(深圳)有限公司 | Led显示装置 |
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